Chemical Engineering

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D.Sen
(f.U NEW AGE INTERNATIONAL PUBLISHERS

CONTENTS
Preface (uii)
1. Fertilisers 1
2. Heat Transfer 25
3. Pulp and Paper 37
4. ehlor Alkali Industry 45
5. Cellulosic Fibres (Rayon) 50
6. Selected Process Equipment Design 63
7. Petroleum Re finery 70
8. Active Carbon 75
9. Refrigeration 78
10. Coal Tar Chemicals 96
11. Refractory Bricks 103
12. Explosives and Detonators 107
13. Water Treatment 111
14. Metal Cleaning Process 128
15. Mangane!!le Dioxide 130
16. Wind 'furbine for Power Generation 133
17. Centrifugal Pumps 13S
18. Industrial and Town Gases 143
19. LNG Production 159
20. Products Manufactured from Benzene, Ethyl Ben2ene,
Ethylene. Ethylene Oxide, Ethanol and Others 162
21. Synthetic Iron Oxide Pigment 167
22. Dyes, Intermediates and Dyeing 170
23. FlourCl;cent or Optical Whitening Agent (FWA) 172
24A. Flame Retardants, Halans, Fire AlarmsIHydrants
and Rubber and Expanded Plastics 174
24B. Float Glass , Carbon Black, Electrophoresis, Dry Ice
and Technological Development in Iron and Steel Industry
and Electrolytic Chlorinator 179
25. Ceramic Colouring Materials 185
(x)
26. Glass Fi bres for Insulation and Other Uses 187

27 . Plastics 190
28. Flocculation 195
29. Phosphoric Acid 198
30. Electroplating Process 207
3J. Couling Towers 212
32. Paints and Painting 217
33. Biogas Pl ant (Domestic Use) 223
34. Sugars 225
35. Phenols for Disinfection 230
36. Ferrous Alloys 232
37. High Carbon Charge Chrome 234
38. Characteristics of Valves Used in Chemical Process Industry 236
39. Boiler Feed Pumps and Standard Values for Boiler Feed
and Circulating Water 237
40. Crystallizer Classification 240
4J. Brief on Offshore Oil Exploration and Transportation Pipeline 242
42. Insecticide or Pesticide 243
43. Critical Path Method WPM) 254
44. Psychrometry 255
45. Glasses and Textile Glass Fibres 258
46. Environment and Pollution Air and Water 260
47. Vegetable Oil Refining 275
48. Furfural 282
49. Polyethylene Terephthalate Resin (Bottle Grade) 285
50. Process Evaluation of a Chemical Plant 288
51. Detail Project Cost Estimation 298
52. Types of Contract 307
53. Proj ect Financial Management 309
54. ISO.90oo Series Quality Assurance System 320
55. Conversion Factors 328
Index 336
Chapter
1
FERTILISERS
1. GENERAL INORGANIC FERTILISERS
These are plant nutrients which are grouped as nitrogenous, Phosphatic and mixed fertilisers
with or without potassium chloride (muriate of potash, MOP). Among nitrogenous fertilisers, urea
containing 46–46.5% (wt) nitrogen is most important because of high nutrient content and is widely
produced and used. Di-ammonium Phosphate (DAP) single super phosphate (SSP), mono ammonium
phosphate (MAP) and dicalcium phosphate (DCP) are common phosphatic fertilisers. CAN is
Ammonium nitrate mixed with lime. Mixed fertilisers are balanced nutrients for plants as they contain
nitrogen, phosphorous and potash in various proportions. Fertilisers are generally termed as containing
N : P2O5 : K2O or simple N : P : K where N stand for % nitrogen, phosphate as % P2O5 or simple
P and Potassic as % K2O or simple K. The ratio is % by wt.
Types of Inorganic Fertilisers
Type Constituents, % by wt Remarks

Nitrogenous Fertilisers use as prills and industrial
Urea, NH2CONH2 N = 46–46.5% Use as crystals or Prills
Ammonium Nitrate, N = 34.5% Explosives and fertiliser use
NH4NO3
UAN soln. N = 20% or NH3 = 23% UAN is urea mixed with ammonium
nitrate
Nitrolime or CAN N = 25% Mix. of 60% amm. nitrate and 40%
lime stone (CaCO3)
Ammonium Sulphate, N = 21% Fertiliser use
(NH4)2SO4
Phosphatic and Potassic:
Monoammonium Phosphate N = 11%, P2O5 = 52% Fertiliser use
MAP (NH4H2PO4H2O)
Diammonium N = 18%, P2O5 = 46% Fertiliser use
Phosphate, DAP or 21% = N, 53.5% = P2O5
(NH4)2HPO4H2O
1
2 REFERENCE BOOK ON CHEMICAL ENGINEERING
Dicalcium Phosphate, P2O5 = 51% Fertiliser use

(CaHPO)4
Single Super Phosphate P2O5 = 16–18% Fertiliser use
(Mixture of mono calcium
phosphate and Gypsum)
Tripple Super Phosphate P2O5 = 46–48%
TSP (mix of tricalcium
phosphate and Gypsum)
Liquid spray fertilizer (i) 24% AqNH3 soln. Fertiliser use
Developed after (ii) Ammonia nitrate or urea
(1950 in USA) aq. soln with liquid NH3
upto 50%
(iii) Non press. Appln 32%
aq. soln of urea and ammon.
nitrate
Mixed Fertilisers
NPK 15 : 15 : 15 Fertiliser use
12 : 12 : 12
8:8:8
N P 18 : 46
16 : 20
20 : 20
N P K (other type) 17 : 17 : 17 Fertiliser use
10 : 22 : 26
14 : 28 : 14
19 : 19 : 19
N P K (foliar grades) 12 : 4 : 6 Foliar spray
6 : 12 : 6
5 : 8 : 10
Controlled release urea aldehyde Slow release to soil
fertiliser
2. BY DANGER CRITERIA, THERE ARE FOUR TYPES OF FERTILISER

A type explosive fertilisers, exm. Ammonium nitrate-storage conditions are stringent.
B type fertilisers are self-sustaining progressive thermal decomposition.
C and D type fertilisers are not self-sustaining as well as do not subject to progressive thermal
decomposition.
Group B fertilizers are more important for storage.
FERTILISERS 3
3. RAW MATERIALS FOR FERTILIZERS PRODUCTION

Nitrogenous Fertilisers
For manufacture of nitrogenous fertilizers, ammonia as intermediate product, is manufactured
first.
Raw Materials
Natural gas (N.G) containing mainly methane and other higher hydrocarbon stock. (LSHS) is
also used where natural gas is not available. Other oil refinery distillation product like Naptha is also
used as starting raw material although it is costlier. Even low sulphur and low ash bituminous coal
is used in some plant (South Africa) as raw material.
Process Steps
(i) These involve production of raw gas (CO + H2) with pre or post desulphurisation depending
on type of raw material used. For N.G, pre-disulphurisation is carried out first followed by steam-
air reforming (two stage) using compressed air and compressed natural gas. H.P. steam generation
from reformed gas (R.G.), H.T. CO conversion and L.T CO conversion for generation of equivalent
H2 from CO, CO2 gases in the raw gas are absorbed in a CO2 absorber using pot. Carbonate with
anticorrosion chemicals viz V2O5 or As2 O3 or using MEA/DEA absorption for CO2 followed by
methanation to convert residual CO and CO2 to methane. CO2 from CO2 absorbing solution is
recovered in a desorption tower using heat for regeneration of CO2. The byproduct CO2 from CO2
desorption tower, containing over 96% CO2, is sent to urea plant for production of urea. The
synthesis gas obtained after methanation and having H2 and N2 in 3 : 1 molor ratio, is used for
ammonia synthesis and compressed to 200–250 Kg/Cm2g and synthesized to produce ammonia in
the H.P ammonia reactor with recycle in the synthesis loop having synthesis gas compressor with
recycle gas circulator, primary and secondary condensation using cooling water and ammonia
refrigeration respectively. The ammonia produced as liquid is about 99% (wt) and stored in horton
sphere for sending to urea plant for urea production. The conversion of H2 to NH3 in synthesis loop
is about 14–16% (Vol) and inert gases from synthesis loop is sent to ammonia recovery section. Only
make up synthesis gas (H2 + N2) is fed to the NH3 reactor using KM1 and KM2 catalyst, to the extent
ammonia is produced due to catalytic conversion of H2 and N2 into NH3.
3H2 + N2 = 2NH3 ∆H = –22400 Btu/1b mole
The overall energy required per ton of ammonia various from 5–10 Geiga calories/ton depending
on patented process of Haldor Topsoe, Texaco, Kellog, etc.
(ii) In case of LSHS, desulphurisation by cold methanol is carried out after raw gas generation
in gasifier using oxygen from air separation unit and O2 compressed to 28 Kg/sq.cm. In the gasifier
partial oxidation reaction takes place in the flame with generation of raw gas (H2 + CO).
When refinery naphtha (boiling range 170°C) is used as raw material, two stage desulphurisation
is carried out first prior to gasification in a reactor. The rest of the process like CO conversion, CO2
absorption using hot Pot. Carbonate soln. with V2O5/As2O3 as corrosion inhibitor, (As2O3) is normally
not used now due to pollution) and methanation followed by high pressure ammonia synthesis. By
product carbon pellets is obtained when LSHS is used for gasification.
Fuel used in reforming section is same as starting raw material viz N.G. or naptha (Vaporised).
Texaco, USA is the licensor for gasification section. Other process licensors are ICI, KELLOG etc.
4. DETAIL PROCESS DESCRIPTION FOR AMMONIA PRODUCTION USING N.G.

AS FEED STOCK
Natural gas is compressed to 41 ata and preheated to 400°C in N.G. fired heaters and sent for
desulphurisation using comox catalyst (Cobalt – moly and Zinc oxide) catalyst. The type of catalyst
required depends on inlet sulphur concentration as H2S and organic sulphur. The gas is then mixed
with H.P. steam at 40 ata and 370°C. The mixed N.G. is then (further) heated in mixed gas heater
upto 500°C and fed to primary reformer at 32 Kg/Cm2g containing primary reformer catalyst in
nickel tubes of HK-40 material. For 600 MT per day ammonia plant 240 nos. tubes of 6" diameter
in vertical row are required. The primary reformer furnace is generally having side fired N.G. burners
where N. G. is burnt as fuel (top and side fired burners are also used in primary reformer). The
reformer furnace temp. is kept at 1000°C and steam carbon ratio is maintained in the primary
reformer tubes between 3–4. The tubes expand upwards and gas flows from top to bottom. Primary
reformation of N.G. takes place inside the tubes at 700–800°C in presence of nickel based catalyst.
The tube life is around 100,000 hours.
The exit gases from P.R. at 30 Kg/sq.cm and 795°C is further reformed in secondary reformer
at 950°C. In the secondary reformer in the presence of catalyst, further reformation takes place at
31 ata when some H2 burns to produce heat necessary to convert most remaining feed stock to H2,
CO and CO2. Air is fed to S.R so as to provide necessary N2 in synthesis gas in the molar ratio
of 1:3 (N2 : H2). The exit heat from S.R gases is recovered in super heaters, N.G. heaters and air
heater and mix gas heater in the reformation section. The hot S.R exit gas, containing 12% CO at
1000°C, is then sent to R.G boiler to generate H.P. steam followed by two stage catalytic CO
conversion when equivalent H2 is produced from CO in raw synthesis gas, (H2 + CO).
CO + H2O CO2 + H2
General Reaction in Primary Reformer
CnH2n+2 + nH2O → nCo + (2n + 1)H2 General reaction
CH4 + H2O → CO + 3H2 1
CH4 + 2H2O → CO2 + 4H2 2
C2H6 + 4H2O → 2CO2 + 7H2 3
C3H8 + 6H2O → 3CO2 + 10H2 4
C4H10 + 8H2O → 4CO2 + 13H2 5
C5H12 + 10H2O → 5CO2 + 16H2 6
C2H6 + 2H2O → 2CO + 5H2 7
C3H8 + 2H2O → 2CO + 7H2 8
C4H8 + 2H2O → 4CO + 8H2 9
C5H10 + 5H2O → 5CO + 10H2 10
Reactions 1 to 6 are major reactions. Other reactions possible in varying conditions of pressure
and temp. in the primary reformer are:
COS + H2O → CO2 + H2S
2CO → C + CO2
C + H2O → CO + H2
FERTILISERS 5
CO2 + C → 2CO
CH4 + CO2 → 2CO + 2H2
2CH4 → C2H6 + H2
H.T. CO conversion is carried out at 327°C/427°C when CO at exit is around 2–3% and LT
CO conversion at 210°C/330°C. The CO and CO2 content of L.T. converter is 0.30% and 18.5%
respectively. The heat in exit gases from H.T. converter is used to preheat boiler feed water heaters
and L.T. converter outlet is used to produce, L.P. steam. The L.T. exit gas is then sent to decarbonation
tower to remove CO2 with either Vetrocoke soln. or Benfield soln. (Pot. Carbonate with V2O5). Both
the CO2 removal processes are proprietory items. Now a days Vetrocoke soln. (hot potash with
As2O3) in not used due to pollution problems. Corrosion in-hibitors As2O3/V2O5 forms a stable
passive oxide film in towers which prevents corrosion; absorption of CO2 by Pot. Carbonate soln.
takes place as per the following reaction :
K2CO3 + H2O + CO2 
→ 2KHCO3
Regeneration of the bicarbonate is done by heating of the soln. in the desorption tower with
reboiler :
2KHCO3 
→ K2CO3 + CO2 + H2O
Heat supply to reboiler is by steam. The generated CO2 gas from desorption tower/regenerator
top is cooled in a cooler to remove condensate and sent to urea plant.
The decarbonated gas at 60°C and 26 ata pressure is preheated by hot methanator outlet gas
and partial H.T. CO converter gas upto 315°C and feed to methanator where remaining CO and CO 2
are converter catalytically by iron oxide catalyst to methane.
2CO + 5H2O 
→ 2CH3 + 2H2O
The heat recovery as well as operating parameters in reformation section to methanator varies
according to process licensor scheme. Methanator is often deleted and in its place liquid N2 wash
is carried out in process licensor e.g., C.F. Brown Process.
The hot gas from methanator after heat exchange, cooling and condensate separation is the
synthesis gas having H2, N2 ratio within 3 (molar) and CO + CO2 within 5ppm, CH4 = 0.75%. The
synthesis gas is sent to compressor at 45°C and 25 ata pressure for compression to 200–250 Kg/
sq. cm. The total pressure drop to primary reformer to methanator is designed at 5–6 Kg/cm2.
In the synthesis loop, make up pure synthesis gas mixture along with recirculated synthesis gas
is compressed and cooled in cold exchanger (Tube side) and in the ammonia cooled condenser and
ammonia separated in secondary cold ammonia separator. The gas then enters shell side of cold
exchanger and then shell side of hot exchanger and then to ammonia converter packed with KM1
(often KM2 also) iron catalyst where NH3 is formed at a temp. of 425°C–500°C. Reactor temp. is
controlled by by-pass gas valve in each of 3 catalyst beds.
H.P. steam is generated in boiler coil inside the NH3 reactor. The converted exit gas is then
cooled in primary water cooled condenser from 70°C to 38°C and then to sec. ammonia cooled
condenser. The liquid ammonia condensed is separated in primary separator, sec. separator and
unconverted gas is recycled to the recirculator and a small part is purged to ammonia recovery sec.
from recycled gas to keep inerts, Argon, CH3 within limit. Liquid ammonia from primary and two
secondary separators is put in let down tank from where it is taken to Horton sphere for storage.
H .P.
A u xiliary Prim ary reform ation

b oiler
M .P. S ervice
boile r
To Pla n t
n etwork
Steam netw ork
A ir se con dary
reform a tion
H .T. C O .-conversion
L.P. boiler for steam

generation
L.T.C O -conversion
C O 2 absorption
C O 2 desorption
C O 2 to u rea
M ethanation
Am m onia synthesis
and refrigeration sec.
Am m onia storage
Lig am m onia to
consum ing plants
Fig. 1. N.G. steam reformation (HTAS) for ammonia synthesis in (HTAS) process.
The flow scheme of gases in the synthesis section also varies as per process licensor’s design
depending on the extent of waste heat recovery from syn. converter. Often two syn. converters are
required for greater conversion to ammonia as in C.F. Braun’s Process as well as some design of
Uhde. CO2 absorption also varies – pressure swing absorption (ICI) and regeneration by flashing and
physical absorption using selexol/sepesol and MDEA Process (BSAF) and more common Process of
CO2 removal by DEA and MEA depending on process adopted by process licensor.
FERTILISERS 7
5. SYN. GAS (CO + H2) GENERATION BY NONCATALYTIC FUEL

OIL/LSHS GASIFICATION
There are two process licensors Texaco and Shell for production of raw syn. gas by non-
catalytic gasification of Fuel Oil/LSHS using oxygen by the partial oxidation route. Texaco had,
however, developed a gasification process using these feeds stocks with enriched air (with oxygen).
General Formula
CmHnSr + mO2 
→ m/2 CO + (n/2 – r) H2 + rH2S.
Side Reaction
CmHnSr + (r – n/2 + 2) H2 
→ CH4 + (m – 1) C + rH2S.
H2O + C 
→ H2 + CO
H2O + CH4 
→ 3H2 + CO
H2O + CO 
→ H2 + CO2
Partial Oxidation of Heavy Fuel Oil (feed stock)
C15H24S2 + 15/2 O2 → 15CO + (24/2 – 2) H2 + 2H2S
or C15H24S2 + 7.5 O2 → 15CO + 10H2 + 2H2S
In Case of Full Oxidation
C15H24S2 + 20O2 
→ 15CO2 + 10H2O + 2H2S
Side Reactions
C15H24S2 + (2 – 24/2 + 2) H2 
→ CH4 + (15 – 1) C + 2H2S
or C15H24S2 + 8 H2 
→ CH4 + 14C + 2H2S
H2O + C 
→ H2 + CO
CH4 + H2O 
→ 3H2 + CO
CO + H2O 
→ H2 + CO2
Process
Oxygen gas from Air Separation Plant is compressed to 52 Ata, mixed with H.P. steam and
the mixed gas is led into partial oxidation gun along with preheated heavy fuel oil inside the gasification
reactor where flame reaction takes place producing raw syn. gas (H2 + CO). The nitrogen in fuel
oil is converted to molecular N2 and sulphur to H2S and small amount of COS. The gases are then
quenched with water to remove unreacted fuel oil. The carbon water from quench vessel in then
sent to carbon recovery section where carbon is separated and pelletised for use in service boiler
and water slurry recirculated with the make up water to quench vessel. The H2S in raw syn. gas
at 51 ata and 48°C is then sent to rectisol section for desulphurisation with cold methanol at –20°C.
Due to presence of considerable sulphur compound (H2S, COS) etc. cold methanol is used in this
process (Rectisol) using ammonia refrigeration. Sulphur is reduced to 0.1 ppm.
The gases are then led into HT CO conversion after heating where shift reaction takes place
at 327/420°C and most of CO is converted to H2.
CO + H2O 
→ CO2 + H2
The exist gases from HT CO converter contain 0.3% CO and CO2 gases are absorbed with
cold methanol at (–50°C) in Rectisol section where most of CO2 is physically absorbed in cold
methanol which is then regenerated by heat and flashing. The generated CO2, about 96%, is sent to
Urea Plant and other consuming plant. The regenerated methanol soln. is sent to CO2 absorber. The
exit gases from absorber still contain some CO and CO2 along with Methane and Argon. The gases
are then first adsorbed in molecular sieve vessel where CO2 is adsorbed (below 10 ppm) and methane
below 50 ppm. The purified gases are then sent to liquid Nitrogen wash tower where CO, CH4 and
Argon are removed and after regeneration of liquid Nitrogen containing CO, CH4 are Flashed out and
stored for use as a fuel. The purified mixture of Hydrogen gas and Nitrogen, in the ratio of 3 : 1,
is then compressed to 200 – 250 Kg/cm2 along with recycle gas containing unreacted Hydrogen,
Nitrogen and some Ammonia is sent to syn. reactor where after preheating enters the catalysts beds
in ammonia converter where ammonia is produced at 500°C.
3H2 + N2 = 2NH3 ∆H = –22400 BTU/1b mole
H.P. Steam is produced in the syn. reactor, flashed in syn. boiler and used in the process.
S e rvice LSH S (Storage)

b oiler
C arbon pellets
Shell gasification
n etw ork
S tea m
D esulphurisation
by cold m ethanol
C O 2 absorption
by rectisol process
C O 2 d eso rption
C O 2 to u rea
O2
H .T. C O conversion
Tail gas
Liq. N 2 w a sh
Air
L iq .
N2
Am m onia synthesis
and refrigeration sec.
Air separation
Lig. am m onia storage
Lig. am m onia to
consum ing plants
Fig. 2. Shell gasification (partial oxdn.) ammonia synthesis process.
FERTILISERS 9
Table 1
CO2 Removal Process
Plant Supplier Uhde activated MDEA of Uhde low heat hot potash
BASF UOP
H.P. Boiler FW preheating 31.2% 29.2%
L.P. steam generation 14.9% –
Heat for CO2 removal 31.4% 49.9%
Demineralised → water 22.5% 20.9%
preheating
Total heat available 100%
Table 2
CO2 Removal Process
Process MDEA (BASF) Low heat hot

potash (UOP)
Absorber outlet CO2 100 ppm 1000 ppm

Kcal/NM3 368 777
CO2 recovered in 96.51 99.52
regenerator, %
CO2 purity (dry), % 99.75 99.06
Table 3
UHDE Ammonia Synthesis Loop Data
H2/N2 ratio 2.95

No. of syn. reactor One
Mu. syn. gas 27 bar, 6°C
Ammonia separation temperature –10°C
125 bar steam generation t/t NH3 1.17
Waste heat used in H.P. steam 60%
raising%
Waste heat removal in cooling water 14.81%
Chiller duty 25.01%
Total heat available 100%
Table 4
Energy Consumption for Ammonia Plant (N.G. based)
Process Reformation and syn. –HTAS, HTAS

CO2 shift (Two stage PDIL) and
Methanator (PDIL)
Plant capacity 600 MT/day 1000 MT/day

Location India Europe
N.G. (feed stock Fuel*) 8.49 7.641 Gcal/Te
G.cal/Te
N.G. Methane content 78–91% (Vol) Over 90% (Vol)
N.G. per ton ammonia 1218 SM3 N.A.
Electrical Power (excl. CT) 61.20 KWH/Te 28.6 KWH/Te
Polished water 4.302 M3/Te 4.31 M3/Te
CO2 Production rate 1.132 Te/Te N.A.
Cooling water 643 M3/Te 210 M3 (sea water)/Te
M.U. water for C.T. 13.8 M3/Te N.A.
CO2 removal process Benfield N.A.
Energy per ton ammonia, 10.875 7.02
G.cal/Te
*Correspond to full enthalpy of steam and water at 0°C.
6. DEVELOPMENT IN AMMONIA PRODUCTION

(1) Raw Syn Gas Generation
Most of the fertilizer plants in the world use steam methane reforming process followed by
partial oxidation of heavy fuel oil (LSHS) as feed stock. One smaller plant uses coal gasification to
produce raw gas. MW Kellog of U.S.A. had developed reforming exchanger system for raw syn.
gas generation. The reforming exchanger contains open tube catalyst tubes hanging from exchanger
top. Oxygen mixed with air, steam and NG feed (2/3rd) are 1st fed to catalytic adiabatic reformer
where certain amount of reforming takes place at a temp. of 954–1010°C. Nearly 1/3rd of balance
process feed NG and steam enter the reforming exchanger from top while adiabatic reformer effluent
also enters the shell side of reforming exchanger providing recovery of heat for reforming reaction.
The outlet gases from reforming exchanger goes to feed/effluent H.E. where mixed gases are
preheated and reformed gases then follow the heat recovery system of CO shift converters, CO2
removal and methanation and compressed prior to entering ammonia synthesis loop.
Table 5
Process Data for Reforming Exchanger (Kellog)
O2 in enriched air Upto 30%
Mixed feed pre heat temp. 480° – 620°C
Overall, steam/carbon ratio 3.3 – 3.8
Adiabatic reformer exit temp. 925° – 1040°C
Design methane slip 0.5 – 0.7% (vol) dry
FERTILISERS 11
However, the reforming exchanger system, where no secondary reformer is used, changes the
conventional heat balance system of the process. Most of the high temp. heat, via the heat exchanger
reformer is returned to the process and will thus not be available for H.P. steam production and
excess of low temp. heat will be available for med. or L.P. steam production which can not be utilized
in ammonia plant and H.P. steam must be generated in auxiliary boiler or service boiler for use in
H.P. steam turbine drive of syn. gas compressor. The overall energy efficiency will entirely depend
upon the efficiency of auxiliary steam generation.
(2) CO2 Removal Process
There are several proprietory processes viz Vetrokoke hot potash system using arsenic oxide,
Benfield process using V2O5, Catacarb process, MDEA process of BSAF, Hot Potash process of
UOP, low temp. (–50°C) Rectisol process. In addition, MEA and DEA of CO2 process is also used.
In all these processes, absorbed CO2 rich soln. from packed absorber is regenerated by heating and
flashing to low pressure (0.15 Bar). The efficiency depends on heat economy for regeneration of
soln. as well as power recovery by soln. turbine in the absorber outlet soln. to recover part of power
reqd. for pumping the regenerated soln. to absorber. About 40% recovery is possible. Heat required
for regeneration of soln. varies from 370–800 Kcal/NM3 CO2. CO2 conc. from 96–99% (vol) is
recovered CO2.
(3) CO Shift Conversion
Generally two stage (HT and LT) shift reactor is used with L.P. steam (3.5 ata) generation at
outlet of HT converter. The temp. at HT converter is maintained at 330°–425°C and that of L.T.
converter, 210°–330°C.
Shift reaction : CO + H2O 
→ CO2 + H2
(4) Methanation
The remaining CO (0.3%) and CO2 in raw syn. gas after CO2 removal is removed in catalytic
methanator working at 315°/220°C.
Methanation reaction: 2CO + 5H2 
→ 2CH3 + 2H2O
CO2 + 3½H2 
→ CH3 + 2H2O
Instead of methanation often cryogenic separation is used to remove residual CO, CO2 Methane
and Argon and molecular sieve is used for adsorption of CO2 for plants having air separation unit
for oxygen requirement in partial oxidation process.
(5) Ammonia Synthesis
The pure syn. gas with H2/N2 ratio of 2.95 CO and CO2 maxm. 5 to 10 ppm each is
compressed in syn. gas compressor to 200–250 Kg/sq. cm pressure and sent to syn. loop for
conversion to ammonia in catalytic ammonia converter having 3 beds of KMI and KMII catalyst. The
conversion to ammonia is 15–20% and considerable heat is produced which is utilized to generate
H.P. steam. The reactor effluent after heat recovery for H.P. steam generation is cooled first by water
cooling and separation of ammonia followed by 1–2 steps ammonia cooling when remaining ammonia
is separated. The vapour refrigerent ammonia is sent to ammonia compressor where ammonia is
compressed, liquefied and sent to synthesis section. The unconverted syn. gas is recycled to reactor
via recirculator where it is pre-heated for further conversion along with make up gas. H.P. steam
generation, as per modern trend, is to generate H.P. steam at 110–125 ata.
Steam Net Work

A stable steam net work is key to operating stability in ammonia plant; normally H.P. steam is
used in syn. gas compressor turbine and part of it is extracted at 38–40 ata for process air
compressor and refrigeration compressor drives. L.P. steam from CO conversion is used in condensate
stripping and regenerator heat duty in CO2 recovery section.
Plant Capacity
Modern ammonia plant is constructed as large tonnage plant with capacities ranging from min.
600 Te/day to 1000–3000 Te/day and is mainly based on N.G. or naphtha or LSHS as feed stock.
The price of N.G./LSHS/Napfha per million Kcal/BTU is a key factor in economics of ammonia plant
and fixes the criteria of plant design basis and economics, of payout time, I.R.R, R.O.I. etc. In Fig.
1 and Fig. 2 block diagrams for ammonia synthesis process based on N.G. and LSHS is given.
7. UREA PLANT
Now a days most urea plants are designed, based on Stamicarbon’s CO2 stripping process or
Snadom’s ammonia stripping process. Toyo Engg. Corpn’s total soln. recycle, ACES process is used
in many plants and also Technimont’s IDR process which uses both CO 2 and ammonia stripping
finds its use in some plants.
Process : Conventional Total Soln. Recycle
Preheated liquid ammonia and CO2 gases under 190–200 Kg/cm2 press are reacted in an
adiabatic reactor at 180–190°C in presence of recycled unconverted carbamate soln. The reactor feed
ratio of NH3 : CO2 : H2O is 3.5–4 : 1 : 0.5 to 0.6.
Reaction : 2NH3 + CO2 
→ NH4 COONH2 ∆H = –38 Kcal/Kgmole
NH4COONH2 = NH2CONH2 + H2O ∆H = 5 Kcal/Kgmole
Urea
Overall reaction :
2NH3 + CO2 = NH2CONH2 + H2O ∆H = –33 Kcal/Kgmol
A CO2 conversion efficiency of 60–70% is achieved in the reactor and the unconverted
ammonium carbamate decomposed in 2/3 stages. The decomposed gases (NH3, CO2 and H2O) are
absorbed in corresponding absorbers with rectification for separation of excess ammonia at 2nd stage
(16–17) Kg/cm2; recycle soln. from 3rd stage absorber is successibly sent to next higher stages and
finally pumped from 1st stage condensor to reactor by H.P. carbamate recycle pump. Excess
ammonia vapour recovered from 2nd stage absorber rectification stage at top is condensed and
recycled back to reactor by H.P. NH3 feed pump along with makeup NH3 duly preheated. Make up
CO2 gas is compressed in centrifugal/reciprocating compressor and fed to reactor. The 70–75%
dilute urea solution from 3rd stage distiller is concentrated in two stage vacuum concentration to
98.5–99% urea melt and prilled in a I.D. prilling tower having rotating (370–380 rpm) bucket sprayer
(1–1.3 mm hole). The specific load in a prilling tower is 0.17– 0.19 tonnes/m2 and air rate = 1000
NM3/te with air velocity of about 0.47 m/sec.
FERTILISERS 13
Stamicarbon CO2 Stripping Process

1st developed by Stamicarbon NV in 1965. It is based on Henry’s law.
The equation which governs the principle of stripping gases, CO2/ammonia in decomposition
of unconverted carbamate, is given below:
2NH3 + CO2 NH4OCONH2 ∆H = –38 Kcal/Kgmol.
Eqn. Ccarb . = Keq. C NH 2 C CO 2
3
where Keq. is the equilibrium constant for the above reaction and Ccarb CNH 2 CCO are the concentrations
3 2
of carbamate, NH3 and CO2 respectively.
If CO2 gas is passed through the solution containing unconverted carbamate, the above reaction
becomes
Ccarb = Keq × O2 × CCO2 (due to high CO2 conc. ion, NH3 concentrate becomes 0 or negligible)
= 0
Therefore, carbamate conc. will be 0 or nearly so when CO2 is used as a stripping gas. The
operating pressure in the syn. loop consisting of reactor, stripper and carbamate condensers is 150
atm and NH3 : CO2 ratio in reactor is 2.8 and conversion of CO2 to urea is around 58–60%. The
NH3 : CO2 ratio is the syn. loop is 2 which ensures smaller NH3 feed pump. The overall CO2
conversion efficiency is 80–85%. The stripper is having vertical titanium tubes through which reactor
effluent descends in a thin film and the tubes are heated outside with steam at 160–180°C. All CO2
gases at 150 Kg/cm2 are passed upwards through the tubes from bottom and the stripped reactor
effluent is devoid of 90% CO2 and NH3 and hence carbamate. The stripped NH3 and CO2 gases along
with water vapour are led into carbamate condenser which is also fed with an amount of ammonia
through an ejector which draws reactor effluent equivalent to the amount of CO2 introduced into the
stripper bottom. The ejector effluent containing make up ammonia and reactor effluent flows to the
falling film type carbamate condenser where condensation takes place and the heat evolved is used
for waste heat steam generation at low pressure. The outlet stream from HP condenser containing
recycle carbamate solution together with NH3 and CO2 gases, flows into the reactor. The stripper
exit solution after pressure reduction, is led to rectifying column at low pressure where urea solution
is removed of residual carbamate and dilute urea sol. 72–75% is led into two stage vacuum concentrators
at prilling top and 99% urea melt from 2nd stage concentrator is prilled using spinning buckets
sprayer in prilling tower with induced airflow. There is only one recycle stage after HP syn. loop.
Since the process works on low excess ammonia, corrosion in HP syn. loop is prevented by
introducing 2–3% oxygen along with make up CO2 gas. The better corrosion resistant material
(Titanium tubes) in stripper and condensor is used; inert gases are removed from reactor top in inert
washing tower and condensed NH3 and CO2 is recycled to H.P. condenser.
Condenser. The vapours from rectifying column are condensed in a condenser and remaining
NH3 and CO2 along with inerts are washed in inert washing column with condensate from vacuum
section. A part of condensate from vacuum section is hydrolysed in a urea hydrolyser and ammonia
and carbon dioxide vapours are recovered.
The reactor volume is slightly bigger and vapour pocket exits at top. The reactor is provided
with sieve trays for better vapour liquid mixing and to prevent back flow. Stamicarbon CO2 stripping
process is being used in a large number of urea plants in the world. The plant is economical as capital
cost and variable cost are lower.
Snam Progetti NH3 Stripping Process
The principle of the process is given by the following equations :
(A) NH2COONH4 
→
←
 CO(NH2)2 + H2O
ammon. carbamate urea

→ NH2COONH4
(B) 2NH3 + CO2 ←

Ammon. carbamate
0.53 Ps
(C) P =
3 [NH3 ]2 .[CO2 ]
where P = dissociation Pressure of liquid carbamate.

In this process pressure in the syn. loop using ammonia as stripping agent of reactor, NH 3
stripper (titanium tubes) and H.P. carbamate condenser, is maintained at 150 atm; NH3 : CO2 in the
reactor is 3 : 8 and temperature 185°C with conversion efficiency of 65–67%. Due to high NH3 :
CO2 ratio, there is high residual NH3 content in the stripped solution leaving the stripper. The overall
CO2 conversion efficiency in the syn. loop is 85%. Two carbamate decomposition and recovery
stages, down stream of syn. loop, and a separate NH3 recovery unit as pure component have been
provided.
Two H.P. condensers have been provided with steam recovery at 4.5 atm and 6 atm respectively.
All CO2 with 0.3% oxygen for condensers passivation-with little by pass to stripper (as more heat
is produced than required to maintain reactor temp.) to which reactor effluent from top enters. The
reactor effluent passes through the stripper against an ascending stream of NH3 vapour from NH3
evaporation section. Steam at 25 atm is passed in the shell side of stripper operating at 170–180°C.
The stripper effluent contains only 2% carbamate and followed by two stages of decomposition and
recovery at 17 and 3.5 atm and the 75% urea solution obtained is concentrated in 2 stage vacuum
concentrator to get 99.5% urea melt which is sprayed from a rotating bucket (300 rpm) in an
induced draft prilling tower and prills at 50°C is obtained from bottom. Free fall of urea melt in
P/T is 30 m and overall ht. of P.T with vacuum concentrators and dedusting system at top of P.T
is about 44 m.
The stripped NH3, CO2 and H2O gases are condensed in 1st H.P. condenser with steam raising
at 6 atm, and outlet condensed carbamate, along with uncondensed vapour, is fed into 2nd H.P.
condenser where full condensation of gases occur and then recycled to recover via H.P. ejector
operated by H.P. ammonia feed from ammonia pump. The 1st stage recycle solution from H.P.
absorber is pumped to no. 1 H.P. condenser and L.P. condenser weak solution is pumped to H.P.
condenser. NH3 and CO2 is absorbed from vacuum condensate and recycled back to L.P. condenser.
Fig. 3.
FERTILISERS 15
Snam Progetti U rea Stripper

Synthesis-loop C arbam ate
C ondenser
R eactor
Inert Vent
PRC
LRC
Steam
L.P. C ond.
Steam
WH NH3
boiler
Ejector
LRC
(Tw o stage
U rea solution decom position
NH3 recovery section)
Fig. 3
8. TEC’S ACES (ADVANCED COST AND ENERGY SAVING) PROCESS

The process uses an isobaric syn. loop consisting of reactor with two strippers at 185/187°C
and H.P. carbamate condenser working at 175 atm pressure. The reactor temp. is 190°C and NH3
CO2 feed ratio is 4.0 and CO2 conversion efficiency is 68%. Most of CO2, after compression in a
centrifugal compressor, is passed through stripper, having sieve plates at top, and tube bundle
through which reactor effluent falls as a failing film layer. In the effluent, NH3 and CO2 content is
12 and 14% respectively. The tube bundle is heated by medium pressure steam (25 atm). Most of
the unconverted carbamate is decomposed at high partial pressure of CO2 and the gases move
upwards through sieve plates thus reducing moisture in NH3, CO2 gases which move into 1st H.P.
condensor where it is condensed in presence of carbamate soln. from H.P. scrubber where reactor
outlet gases are washed with recycle carbamate from H.P. scrubber. The steam at 5 atm is raised
in 1st decomposer. A part of stripper outlet gases is also sent to 2nd H.P. decomposer to the extent
heat is required to heat up the stripper outlet solution to decompose residual carbamate.
The urea solution with low carbamate content from shell side of 2nd H.P. decomposer is sent
to H.P. decomposer where it is heated by steam in shell side. The solution outlet of H.P. decomposer
is then sent to LP decomposer with CO2 stripping introduced at bottom. It is a packed tower with
bubble cap plates at top. The gases from L.P. decomposer top is condensed in shell and tube L.P.
absorber and absorbed solution is recycle back to H.P. absorber. The carbamate solution from H.P.
absorber is recycled to 2nd H.P. condenser and H.P. scrubber.
The off gases, with inert from air injection in H.P. scrubber are further absorbed in inert
washing column after pressure reduction. The dilute urea solution from L.P. decomposer is sent to
two stage vacuum concentrators and 99.5% urea melt is sprayed into prilling tower top. The urea
prills at the bottom of the tower is cooled in a fluidized bed cooling system. The vacuum condensate
from vacuum section is stripped in plate tower and stripped gases are sent to L.P. decomposer. No
NH3 recovery as pure component is considered and all NH3 is fed to reactor.
9. MONTEDISION’S IDR (ISOBARIC DOUBLE RECYCLE) PROCESS

Here reactor, NH3 stripper, CO2 stripper both working at 200°C and H.P. carbamate condenser
and a post condensor operate at 200 atm pressure. The CO2 conversion efficiency in reactor is 70%
and corresponding NH3 : CO2 feed ratio is 4.25 with water: CO2 ratio 0.55. The reactor is divided
into two section by a partition plate. The reactants are fed to the bottom of upper section, raised
to top and through down comes to the bottom of lower section and flows upwards to outlet to the
1st H.P. CO2 stripper. The NH3, CO2 stripped vapour flows to reactor upper section where these
are condensed and keep reactor temp. at 185–190°C.
The stoichiometric NH3 feed is arranged at different temperature levels to reactor upper section,
to 1st H.P. decomposer and to reactor lower section. The last stream is meant to establish the zone
design ratio of NH3/CO2 not yet converted.
In the last H.P. NH3 stripper, most of residual carbamate is decomposed and recycled to the
reactor in vapour phase. The heat required is supplied by M.P. stream. The solution from the stripper
is conveyed to the 2nd H.P. stripper where whole of make up CO2 is fed as stripping agent. By
supplying heat (M.P. steam), the 2nd stripper outlet contain 40% CO2 and 14% ammonia is sent to
the M.P. stage purification section, working at 23 atm after pressure reduction where it is heated by
recovery steam at 157°C. The vapours from 2nd H.P. stripper are sent to H.P. condenser together
with most recycle carbamate solution from M.P. carbamate condenser. Steam is generated in M.P.
carbamate condenser at 7 bar. The carbamate solution from H.P. carbamate condenser flows by
gravity into the reactor. The non condensable gases from H.P. carbamate condenser are cooled and
partially condensed in a post carbamate condenser which also flows by gravity into the reactor and
unabsorbed gases from post carbamate condenser is sent to inert washing column after pressure
reduction. Waste heat from post carbamate condenser is used to generate 3.5 atm steam. The vapour
from M.P. condenser is sent to concentrator for heating and concentration of urea solution from L.P.
decomposer and carbamate solution at 120°C is recycled to H.P. carbamate condenser and post
carbamate condenser. L.P. decomposer is heated by 7 atm steam at 146°C. Urea solution from L.P.
decomposer is concentrated to 99.5% concentration in 2 stage vacuum concentrators usually at the
top of prilling tower to reduce biuret and prilled in a rotary spinning bucket (holes–1.3 mm). Air is
used along with make up CO2 gas (0.2% oxygen) as well as a small injection of air +H2O2 in H.P.
stripper is made to passivate stainless steel to prevent corrosion.
10. STORAGE FOR FERTILISER

Silo volume to surface area ratio is kept smaller. Usually RCC parabolic silo is constructed with
air conditioning plant to keep R.H. less than humidity of stored fertilizer. Usually critical humidity,
around 65–70% in silo, is to be maintained to prevent moisture absorbtion to prevent caking.
Air conditioning is required when R.H. is higher than 70–80%. Bagging is usually done in bagging
plant.
FERTILISERS 17
Table 6
Specific Consumption of Raw Materials and Utilities in Large Tonnage Urea Plant.
Process NH3 t/te CO2 t/te Steam Export Process Ele- Cooling water
t/te Steam t/te ctricity kwh/te m 3/te
Stamicarbon 0.57 0.75 0.775 – 15 62.5
CO2 stripping 25 bar ∆t = 10°C
Snam 0.57 0.74 0.83 – 20 70
Projetti NH3 23 bar ∆t = 10°C
Stripping
TEC-ACES 0.57 0.75 0.70 0.09 30 60
Process 100 bar 6 bar ∆t = 10°C
Montedison 0.568 0.736 0.71 – 18 75
IDR process 105 bar ∆t = 10°C
Table 7
CO2 By Product Gas from Ammonia Plant
Constituents Values
CO2 98.5%, saturated at 45°C and 500 mm W.G. Pressure
CO 0.60
H2 0.65
N2 + Ar 0.1
Sulphur < 0.5 ppm
Table 8
N.G. Analysis
Constituents Values
CH4 78–91%
C 2H 6 6–10
C 3H 8 5–6
ISO Butane (C4H10) 1–1.5
N Butane 1.3–1.4
ISO Pentane (C5H12) 0.3–0.4
N Pentane 0.14–0.25
NCV 10377 Kcal/m3
Table 9
Comparative Statement on Energy Consumption
Kellog UHDE PDIL MHI-CHIYODA

1. Ammonia Plant
(i) Process route Kellog’s steam ICI steam PDIL/HTAS HTAS
reforming reforming
(ii) CO2 removal Benfield MEA Benfield Catacarb
(iii) Synthesis Kellog UHDE Ammonia converter CCC
(HTAS) rest PDIL
(iv) Rated plant 900 MTD 900 MTD 600 MTD 900 MTD
capacity
2. Feed Stock Fuel NG NG NG NG
Energy Mkcal/MT
Guaranteed
(i) Feed + Fuel 10.0569 9.97 10.933 9.59
(ii) Steam 0.0216 (-) 1.008 – 1.37
import/export (export)
(iii) Elec. power 0.099 0.12557 0.2185* 0.05
(excluding C.T.)
(iv) Total energy 10.1715 9.0875 11.1515 11.01
(excluding C.T.)
3. Uure Plant Stami-carbon Stami-carbon PDIL Stami-carbon
conventional
(i) Process route CO2 CO2 stripping 3 stage total CO2 stripping
stripping solution recylce
with steam reco-
very in 1st cycle
(ii) Rated plant 1620 MTD 1550 MTD 1167 MTD 1600 MTD
capacity
4. Raw Material
Consumption
(Guaranteed)
(i) Liquid NH3 MT/ 0.58 0.58 0.590 0.592
MT urea
(ii) CO2 MT/MT 0.77 0.77 0.77 0.775
urea
5. Energy,
Mkcal/MT
(i) Feed ammonia 5.899 5.2707 6.5794 6.517
(ii) Import steam 0.8205 0.7998 1.0376 1.0
with pressure and (39 ata, (110 ata, (45 ata, 360°C) (66 ata, 43°C)
temperature 380°C) 550°C)
Table Contd.
FERTILISERS 19
(iii) Electric power 0.0215 0.0258 0.3586 0.03

excluding (CT)
(iv) Export steam Used in Used in Used in 3.5 ata Used in silo
(4 ata. satd.) deaeration in desulphurisa- network in urea dehumidification
ammonia tion for NG plant – 4.2 Te/hr 10 Te/hr
plant, 10 Te/hr preheating,
16.2 Te/hr
(v) Total energy 6.741 6.0963 7.9756 6.7072
(excluding C.T.)
6. Net Process 812 722 792 692
Heat, Kcal/kg
Urea
7. C.W., m3/MT 106 80 198 100
8. Turn Down 70% 70% 65% 70%
Ratio
9. Energy for 0.9827 0.8635 1.5 0.9068
Off-site
Facilities mk
cal/mt Urea
10. Ovarall 7.7237 6.9598 8.438 7.614
Energy for
the Complex,
Mkcal/mt Urea
Fig. 4
FERTILISERS 21
Fig. 5
Fig. 6
FERTILISERS 23
Fig. 7
Fig. 8
Chapter
2
HEAT TRANSFER
1. INTRODUCTION
Heat is transmitted in the direction of the temperature drop by convection (contact), radiation
and conduction. In many cases all these types of heat transmission takes place simultaneously. In
shell and tube heat exchangers and other types of exchangers, the predominate phenomenon is
transmission of heat by contact convection. In furnace and air heaters where gases are burnt to heat
a gas or other surface, both radiation and convection are to be considered. Heat conduction is the
flow of heat with a material (solid, liquid or gas). In most cases a wall is concerned and the heat
is flowing through it from one face to the other face as in a pipe through which a hot fluid is flowing.
Heat transfer considerations are of prime consideration in chemical process industry including
waste heat recovery.
1.1 Convective Heat Transfer
In convection (contact) mode of heat transfer is as per Fourier law, the quantity of heat
transferred is given by eqn.
Q = U.A. ∆tm where U = overall heat transfer co-eff, kcal/hr.m2.°C, where A = area of heat
transfer, m2 based on O.D. of tubes, ∆tm = mean/logarithm temperature diff. in °C between heat
emitting and heat absorbing media and Q = total quantity of heat transferred in the exchanger, kcal/hr.
However, overall heat transfer co-eff. is the sum of reciprocal of undivided film co-eff. is called
resistances to heat flow along the conduit (pipe) and resistance of metal wall plus fouling resistances
due to foreign material depositing on both tube surfaces (inside and outside). For simplicity, for a
single layer wall (tube), the overall heat transfer co-eff. of heat transfer.
1
U=
1 t 1
+ + + fouling resistance
u1 λ u2
1 1 1 t
or = + + + fouling resistances for
U u1 u2 λ inside and outside tubes
where, U = over-all heat transfer co-eff., Kcal/hr.m2°C
u1 = individual film co-eff. on the side of hot fluid
u2 = individual film co-eff. on the side of cold fluid
t= wall thickness, m and λ = co-eff. of thermal conductivity for
the metal tube material, kcal/hr.m.°C.
25
The coefficient of heat transfer U depends on flow conditions, the type and temperature of
heating or cooling medium and configuration of areas of contact.
Temperature Difference (mean)
The temperature difference between hot and cold fluids is the driving force of heat transfer in
a H.E. The flow of fluids (cold and hot) in the H.E. may be either countercurrent or parallel current;
usually counter current flow is desirable as the quantity of heat exchanged remains constant. If ∆t1
is the higher temperature difference and ∆t2 is the lower temperature difference at either end of H.E.
∆t1 + ∆t2 ∆t1
then arithmetic mean temperature is to be considered; if the ratio
2 ∆t2 is less than 2 or
∆t1
2, while log mean temperature difference (LMTD) is to be considered if the ratio of
∆t2 is more
than 2
∆t1 − ∆t2
∆tm = LMTD =
∆t
2.303 log 1
∆t2
LMTD can be found from nomograph in Fig. 6 and ∆t1 and ∆t2 in Fig. 5.
1.2 Shell Side/Tube Fluid
In H.E. generally the fluid which is more fouling is put in tube side due to ease of cleaning
and the other cooling or heating medium is put in shell side. A fluid having moderate to high press
and temperature is also passed through tube side to avoid high shell thickness of H.E.; viscous and
condensing fluids are passed through shell side.
1.3 Baffle Cut and Baffle Spacing
For making multipasses in shell side for better heat transfer in shell side fluid, 20–30% cut in
baffles are made for flow of fluid across tube bundle length. The extent of baffle cut and no. of
baffles determine shell side fluid velocity as per design requirement. Increasing velocity in shell side
for better heat transfer is by proper spacing of baffles. Baffles may be of annular or segmented cut
types. The baffle spacing is usually equally spaced over the length between tube sheets ends. Baffle
spacing is usually 1/5th of shell id.
1.4 Tube Pitch
Tubes are laid in tube sheet for triangular pitch or square pitch or diamond pitch as per
requirement of shell diameter, tube spacing for heat transfer and fluid properties. The individual tube
ends at both sides are sealed with tube sheet by tube expanders. In Fig. 3, layout of tubes for
triangular pitch is shown as well as formulae for square pattern layout are stated.
Mech. Design Code
Heat exchangers are generally designed as per TEMA class/ASME code/DIN standard.
Equations for determining heat transfer film co-effs.:-
Dvρ
Reynolds no =
µ
HEAT TRANSFER 27
(i) For turbulent flow (Re no. > 4100 inside a clean tube; usually Dittus–Boltier equation is used
to determine surface or film co-effs.
0.8
λ  Dvρ   Cpµ 
0.4
u = 0.023 
D  µ 
. 
 λ 
(for heating fluid)
0.8 0.3
λ  Dvρ  .  Cpµ 
or u = 0.023   (for fluid being cooled)
D µ   λ 
Cpµ Dvρ µD
N.B. is Prandtl no., is Reynolds no. and is Nusselt no., Nu and Re no. depend
λ µ λ
on flow conditions and Prandtl no. indicated thermo-physico conditions of fluid.
(ii) For gases in forced convection, perpendicular to banks of staggered tubes:
0.7
λ  Dv 
u = 0.13 . 
D  µ 
(iii) For condensing vapours in horizontal tube
( )
1/ 4
u = 0.73 λ3 . ρ2 . g
1/ 4
 λ3 . ρ2 . g.K 
And for vertical tubes u = 0.94  
 L µ ′ ∆t 
Where u = Surface or film co-efficient kcal/hr m2°C
λ = Thermal conductivity of fluid, kcal/m hr°C
v = Velocity, m/sec
D = Tube O.D. or I.D., m
µ = Absolute viscosity of fluid, kg/m.sec or Pa.S
Cp = Specific heat of fluid, kcal/kg°C
ρ = Density of fluid kg/m3
λ′ = Thermal conductivity of metal kcal/m.hr.°C
K = Latent heat of vapour, kcal/kg
L = Length of pipe, m
∆t = Temperature difference between vapour and metal, °C
g = Accln. due to gravity m/sec2
µ' = Viscosity of cold film kg/m.sec or Pa.S
1.5 Tube Wall Heat Flow Quantity
T1 − T2
Q=
 r /r 
2.303 log  1 2 
 2 πL λ' 
where Q = Heat Flow, kcal/hr

T1 and T2 = Temp. of inner wall and outer wall, °C
r1 and r2 = Raddii of inner and outer wall, m
L = Length of tube, m
λ′ = Thermal conductivity of metal wall, kcal/m.hr.°C
(i) For multipurpose heat exchangers having tube O.D., and tube I.D. diameter in meter the
overall heat transfer co-efficient is given by
1
U=
1 do do d d
+ . 2.303 log + o + ψ0 + ψ1 o
u0 2λ' di di ui di
where,
uo and ui = outside and inside film co-efficient kcal/hr.m2.°C
do and di = outside and inside dia. of tube, m
λ′ = thermal conductivity of metal wall, kcal/m.hr.°C and
and ψo and ψi = fouling factors for outside and inside of tube
(ii) In case of boilers and evaporator heating surface, overall co-efficient is given by
U = u1 + u s
where, u1 = film co-eff. for hot water side
us = film co-eff. for tube metal wall
(iii) For air heaters and super heaters u is given by:
u1 . u2
u= kcal/hr.m2.°C
u1 + u2
where u1 = film co-eff. for hot gas side of tube/coil
u2 = film co-eff. for cold gas side of tube/coil
Note : 1. Normally 60% more area is taken over calculated area due to uncertainties of mean data taken
for densities, sp. gravity, thermal conductivities, viscosity and sp. heat. Theoretically, R-S-S (root-sum-sq.)
system is considered, actual A (area) = ∑ ( ∆A) 2
1.6 Fouling Factor

In actual service, addln. resistance to flow of heat from hot side to cold side through metal
wall takes place resulting in reduction of respective film co-eff. with reduction of overall co-eff.
Therefore, suitable fouling resistances (reciprocal of surface co-eff.) both hot and cold fluids are
reqd. to be considered. Fouling resistances for different types of water are as follows:
m 2 hr °C
Kcal
Distilled water = 0.0005
Treated C.W. = 0.0005
Tube well water = 0.0003
Sea-water = 0.004
HEAT TRANSFER 29
BFW = 0.001
River water = 0.004
Appln. Range:
Temp. = 115–205°C range
Water vel. = 3'/sec
Water temp. = + 52°C
2. TYPES OF HEAT TRANSFER EQUIPMENT

2.1 Single or Multipurpose H.E
In multipurpose H.Es, pr. Drop of fluid through shell side increases as the fluid moves in
restricted space over baffle cuts but overall heat transfer co-eff. increase due to increased velocity
of shell side fluid in the shell. Channel covers have reqd. compartments for directing tube side fluid
depending on no. of passes. Expansion it, if reqd. it is provided on shell.
2.2 Floating Head H.Es
To prevent unequal expansion of tube bundle resulting in tube leakage failure for fixed channel
covers, floating head tube bundle is provided with separate channel cover at floating head end.
2.3 Side/Top Fired Furnace for Indirect Heating of Gases/Water Inside Vertical
Tubes
In reformation of hydrocarbon gases, side or top fired furnace heaters are used. In boiler
furnace with side fired burners are used for heating of water in tube along vertical wall. The tubes
are connected to boiler drum. These furnaces are used in refinery, fertilizers and other plants.
2.4 Evaporators and Re-boilers
These are shell and tube H.Es and located either externally or internally with or without natural
or forced circulation. Steam is generally in shell side.
2.5 Condensers
Shell and tube H.Es for condensable vapours or steam is usually kept in shell side. Non-
condensable gases are purged from top of vessel or in case of steam, steam ejector is used. In
contact condensation, steam is condensed by water spray inside the empty condenser.
2.6 Regenerative H.Es
In a regenerative exchanger, where heat is alternatively stored and removed. The hot and cold
fluid passes through same route through the same exchanger. Two exchangers are required as one
gets heated up by hot fluid and the other gets cold by fluid which gets heated up. Flows are reversed
by auto change-over mechanism which operates inlet and outlet valves of exchangers. They are used
mainly for waste heat recovery from furnace fuel gases for primary air heating for furnace heating.
Also in air separation, these are used for cooling of air and removal of impurities in inlet air, which
gets deposited in cold exchanger and in reverse cycle these impurities are removed by hotter air.
2.7 Finned Tube H.Es
The external heat exchanger surface area in finned tube H.Es are increased considerably by
fixing fins arranged either in circular fashion or horizontally along the external diameter of tubes.
2.8 Double Pipe
These are used for cooling of hot liquid by C.W. or cold fluid in annular space of the tubes,
which are arranged vertically or horizontally. The fluids flow counter currently.
In Trombone coolers, hairpin type cooling tubes are arranged horizontally and C.W. is a
splashed from perforated trough at top and C.W. falls on an open tank below.
2.9 Cascade Coolers for Liquefaction
Treated natural gas, after CO2 removal, is usually cooled and methane is liquefied by cascade
process using 3 refrigerants, propane, ethylene and methane successively. Propane has the highest
B.P. (–44.5°C) followed by ethylene, (B.P. = –103.9°C and finally by methane (B.P. = –164°C) which
gets liquefied when its temp. falls below critical temp. through 9 stages of cooling. Liquefied propane
gets evaporated in propane evaporator by heat from incoming methane gas which evaporates propane
(latent heat of evaporation propane is 101.8 Kcal/kg) thereby, cooling methane gas above B.P. of
propane i.e., –44.5°C; methane is further cooled to above –103.9°C (B.P. of ethylene) by evaporation
of ethylene in ethylene evaporator (latent heat of evaporation of ethylene is 125 Kcal/Kg). Finally
methane gets further cooled to below –82.5°C (critical temp.) when it gets liquefied, the pressure
being above 47.3 Kg/cm2 (critical pressure). The liquid methane gets further cooled to near –164°C
(B.P.) by its own refrigeration (latent heat is 121.9 Kcal/Kg) when it is flashed in methane evaporator.
The respective refrigerants follow the vapour compression cycle, after coiling process so as to
produce cooled liquid methane i.e., LNG.
3. OVERALL HEAT TRANSFER

Overall heat transfer co-eff. for some H.Es have been given in Fig. 1 and 2 for quick estimate
of U. However, it is advisable to calculate U based on first principles. Often a U is considered in
calculation followed by confirmatory determination of U.
3.1 Tubes Layout
In a heat exchanger tubes can be laid out in triangular diamond and square pitches and no. of
tubes in a shell depends on shell dia. and tube pitch. In Fig. 3 calculation for no. of tubes in a ∆
pitch and square pitch H.E is given.
4. RADIANT HEAT TRANSFER

The transmission of heat by radiation through space from a surface gas burner to another
cooler surface or gas is governed by Stefan-Boltzman law
4 4
 T1   T2 
Q = F.C   −  Kcal/hr
 100   100 
= F.h (t1 – t2) Kcal/hr.
where, h = Surface (film co-eff. of heat transfer by radiation Kcal/m2.hr.°C
C = Co-eff. of radiation Kcal/m2.hr.(°C)4
F = Area of heat transfer, by radiation
T 1 = Temp. °K of hotter body
T 2 = Temp. °K of colder body
t1 and t2 = Temp. °C of hotter and colder body respectively
 T 4  T 4 
C .  1  −  2  
 100   100   , Kcal/m 2 .hr.°C
and h=
t1 − t2
HEAT TRANSFER 31
The eqn. is useful in calculating fired heaters and furnaces where heat (convection) mode of
heat transfer is also required to be considered. The heat output from burners is to be considered so
as to balance the total heat distribution. Also heat loss through wall is to be taken into consideration.
5. HEAT TRANSFER BY CONDUCTION

Heat transfer by conduction takes place within a material (solid, liquid or gas), in majority of
cases a wall is involved and the heat, flowing through it from one face to the other, is given by:
λ
Q= A. . (t1 − t2 ), Kcal / hr.
S
where, A = Area of heat conduction, m2
λ = Co-eff. of thermal conductivity of material Kcal/m.hr.°C
t1, t2 = Surface temp. of hotter face and colder face in °C, respectively
Q = Quantity of heat flow, Kcal/hr.
S = Wall thickness m
If the wall consists of no. of layers of thickness S1 and S2 and co-eff. of thermal conductivities,
λ1 and λ2, then the heat flow will be:
1
Q= . (t1 − t2 ) Kcal/hr.
S1 S2
+
λ2 λ2
6. DATA REQD. FOR HEAT EXCHANGER CALCULATION : CRITERIA

A large no. of physical data are reqd. for calculation of a H.E. viz fluid properties–density,
specific thermal conductivities, fouling resistance etc. The design criteria are to be fixed as per
process requirement. If there is uncertainties in these data, then surface area is calculated by
considering R-S-S (roof, sum and square) method. In H.E. data sheet often both clean and design
over all co-eff. (based on fouling factor consideration) is mentioned and other process and mechanical
design data. Apart from shell and tube exchangers, specific equation for film and overall heat transfer
co-eff. for other types of heat exchangers should be consulted in heat transmission books and
Perry’s Hand book. Assumption made should be reasonable. Units of physical properties of fluids to
be correctly ascertained in calculation of U.
7. HEAT DUTY
It is found out from process material balances and heat balance. The C.W. temp. rise is the
limiting point for heat output of an exchanger. The C.W. quality will also determine the fouling factors
to be taken in the determination of individual film co-eff. and overall co-eff. of heat transfer. An
example of H.E. calculations is given in Chapter 6.
8. SELECTED PROCESS EQUIPMENT DESIGN

This is given in Chapter 6. For condensing vapors, if sensible heat of vapor is required to,
detemrine Q by multiplying flow by latent heat of vaporization, K.
di
(i) For conversion of U based on o.d. of tube, multiply U by d for U based on avarage dia.
avg
of tube. All tube dia. in mm.
di
(ii) For conversion of U based on i.d. of tube, multiply U by
do for U based on o.d. of tube.
di
(iii) For conversion of U based on i.d. of tube, multiply U by d for U based on avg dia. of tube.
avg
Som e H eat Exchanger Types and Average Values for O verall coefficient of heat Transfer, U
Type Exchange
conditions
H eat Exchanger w ith N ested Tubes G as to gas 10–50

(a) Straight tube (low pressures)
Internal tube
G as to gas at high 100–400

pressure
Tubular shell
Baffle
N um ber of Passes
Liquid to 200–1000
1 inner (through the tubes)
liquid
1 outer (round the tubes)
(b) U tube Liquid to gas 20–70

(low pressures)
G as at high pressure 200–1000

(inner) to liquid
(outer)
Fig. 1 Source : Borsig pocket book 3rd edn. 1970.

HEAT TRANSFER 33
Som e H eat Exchanger Types and Average Values for O verall coefficient of heat Transfer, U
Type Exchange
conditions
(c) H igh-pressure feed w ater preheater w ith

desuperheating condensation and subcooling
zones on the steam side.
Water (inner) to 1500–2500

superheated steam
at high pressure
(outer)
(d) D ouble-tube heat-exchanger G as to gas 10–50

(low pressure)
G as to gas 100–400
(high pressure)
Liquid to liquid 300–1200
G as at high pressure 200–500

(inner) Liquid (outer)
Fig. 2
N um ber of Tubes in Tubular H eat-Exchangers as a Function of

Shell diam etre and Tube Spacing-Triangular
Z D ’/t Z D ’/t
7 2.00 451 22.27

13 3.46 463 22.54
D’ 19 4.00 475 22.72
31 5.29 499 23.07
37 6.00 511 23.58
43 6.93 517 24.00
55 7.21 535 24.25
61 8.00 547 24.33
73 8.72 559 24.58
85 9.17 571 24.98
91 10.00 583 25.06
97 10.39 595 25.53
109 10.58 613 26.00
a 121 11.14 625 26.15
Di
127 12.00 637 26.23
60° 139 12.17 649 26.46
151 12.49 661 26.91
163 13.11 673 27.06
169 13.86 685 27.50
187 14.00 691 27.71
199 14.42 703 27.78
211 15.10 721 28.00
223 15.62 733 28.21
235 15.87 745 28.35
241 16.00 757 28.84
253 16.37 769 29.05
265 17.09 793 29.46
271 17.32 805 29.60
283 17.44 817 29.87
295 17.78 823 30.00
301 18.00 835 30.20
D ’ = D i – 2a 313 18.33 847 30.27
t = spacing (betw een tube centres) 337 19.08 859 30.79
z = num ber of tubes 349 19.29 871 31.05
D i = shell diam etre 361 19.70 877 31.18
If D ’/t lies betw een tw o values, the sm aller should 367 20.00 889 31.24
be adopted. 379 20.30 913 31.43
For a square nesting pattern w ith the sam e tube 385 20.78 925 31.75
spacing, w e have approxim ately: 397 20.88 931 32.00
1. W ith the sam e no. of tubes z: 409 21.07 955 32.19
(D ’/t) 1.08 (D ’/t) 421 21.17 967 32.74
2. W ith the sam e D i an hence the sam e D ’/t 433 21.63 979 32.82
z 0.86 z 439 22.00 1003 33.05
Fig. 3 Source : Borsig pocket book 3rd edn. 1970

HEAT TRANSFER 35
2
Surface in R elation to Heat-Exchanger Length (m /m )
(referred to external diameter d a of tube (m m ) for the follow ing nom inal bores d i)
di 20 25 32 40 50 di 20 25 32 40
da 25 30 38 44.5 57 da 25 30 38 44.5
z z
7 0.55 0.66 0.836 0.98 1.253 451 35.4 42.5 53.9 63.1
13 1.02 1.225 1.552 1.82 2.33 463 36.4 43.6 55.3 64.7
19 1.49 1.79 2.27 2.66 3.40 475 37.3 44.7 56.7 66.4
31 2.44 2.92 3.70 4.33 5.55 499 39.2 47.0 59.6 69.8
37 2.91 3.49 4.42 5.17 6.62 511 40.1 48.2 61.0 71.5
43 3.38 4.06 5.14 6.01 7.70 517 40.6 48.7 61.8 72.4
55 4.32 5.19 6.57 7.69 9.85 535 42.0 50.4 63.9 74.8
61 4.79 5.75 7.29 8.54 10.92 547 42.9 51.6 65.4 76.5
73 5.74 6.88 8.72 10.21 13.09 559 43.8 52.6 66.7 78.1
85 6.68 8.01 10.15 11.89 15.22 571 44.8 53.8 68.3 79.9
91 7.15 8.58 10.88 12.72 16.30 583 45.7 54.9 69.6 81.5
97 7.61 9.14 11.60 13.57 17.39 595 46.7 56.1 71.0 83.2
109 8.56 10.28 13.02 15.23 19.52 613 48.1 57.7 73.2 85.7
121 9.50 11.40 14.44 16.91 21.7 625 49.1 58.9 74.6 87.4
127 9.97 11.98 15.18 17.74 22.8 637 50.0 60.0 76.1 89.0
139 10.92 13.10 16.60 19.42 24.9 649 50.9 61.1 77.5 90.6
151 11.87 14.23 18.03 21.1 27.0 661 51.9 62.3 79.0 92.5
163 12.80 15.38 19.47 22.8 29.2 673 52.8 63.4 80.4 94.1
169 13.30 15.92 20.2 23.6 30.3 685 53.8 64.5 81.9 95.8
187 14.70 17.62 22.3 26.1 33.5 691 54.3 65.1 82.5 96.7
199 15.65 18.77 23.8 27.8 35.6 703 55.2 66.2 84.0 98.3
211 16.58 19.88 25.2 29.5 37.8 721 56.6 68.0 86.1 101.0
223 17.50 21.0 26.6 31.2 40.0 733 57.5 69.0 87.5 102.4
235 18.45 22.2 28.1 32.8 42.1 745 58.5 70.2 89.0 104.2
241 18.93 22.7 28.8 33.7 43.1 757 59.4 71.3 90.5 105.9
253 19.88 23.8 30.2 35.4 45.3 769 60.3 72.4 91.8 107.4
265 20.8 25.0 31.6 37.0 47.5 793 62.2 74.7 94.6 110.9
271 21.3 25.6 32.4 37.9 48.5 805 63.1 75.9 96.2 112.8
283 22.2 26.7 33.8 39.6 50.7 817 64.1 77.0 97.6 114.2
295 23.2 27.8 35.2 41.2 52.9 823 64.6 77.5 98.3 115.1
301 23.6 28.4 36.0 42.1 53.9 835 65.6 78.5 99.7 116.9
313 24.6 29.5 37.4 43.7 56.0 847 66.5 79.8 101.2 118.4
337 26.5 31.8 40.3 47.1 60.4 859 67.4 80.9 102.5 120.1
349 27.4 32.9 41.6 48.8 62.5 871 68.4 82.1 104.1 121.9
361 28.4 34.40 43.1 50.5 64.6 877 68.9 82.6 104.8 122.9
367 28.8 34.6 43.8 51.3 65.7 889 69.7 83.7 106.1 124.2
379 29.8 35.7 45.2 53.0 67.9 913 71.6 86.0 109.0 127.8
385 30.2 36.3 46.0 53.8 69.0 925 72.6 87.1 110.5 129.3
397 31.2 37.4 47.4 55.5 71.1 931 73.1 87.8 111.2 130.2
409 32.1 38.6 48.8 57.2 73.3 955 75.0 90.0 114.0 133.7
421 33.1 39.7 50.3 58.9 75.5 967 76.0 91.1 115.5 135.2
433 34.0 40.8 51.7 60.5 77.5 979 76.8 92.1 116.9 136.9
439 34.40 41.3 52.4 61.4 78.6 1003 78.8 94.6 120.0 140.4

∆t 1 : La rge te m pe rature d iffe rence

∆t 2 ∆t 2 : S m all te m pe ra ture d iffe rence
Th e no m og ram is use d for de term ining
th e m e a n log arith m ic te m p e rature differe n ce :
∆t 1 – ∆t 2
Tem p.
∆t m =
ln ( ∆t 1 / ∆t 2 )
Fo r a p ara llel or co u nte r flo w hea t-excha ng e r ∆t 1

a nd ∆t 2 in dica te te m pe rature d ifferen ce in the fo ll-
o w in g m e dia at eithe r e nd o f the he a t e xch an ge r.
R e la ted value s of ∆t1 , ∆t2 , ∆t m are join e d o n th e
n om og ra m by a stra ig ht lin e
∆t 1
Exchange Surface
Fig. 5
M ea n L o g a rith m ic Tem p eratu re D iffe re n ce ∆t m for P a ra llel an d C o u nter F lo w H e at E x ch an g e rs
100 100 100
90 90 90
80 80 80
70 70 70
60 60 60
55 55 55
50 50 50
45 45 45
40 40 40
35 35 35
30 30 30
25 25 25
20 20 20
p le
15 E xam 15 15
10 10 10
9 9 9
8 8 8
7 7 7
6 6 6
5 5 5
4 4 4
3 3 3
2 2 2
1 1 1
∆t2 ∆t m ∆t 1
Chapter
3
PULP AND PAPER
1. GRADES OF PAPER
There are several grades of paper depending on and use, type of pulp, pulp usage and wt. of
paper. These are classified as follows:
Type Pulp used wt. in gms/m2
(i) Fine Paper Bleached kraft or sulfite softwood
pulps. Some hard wood pulp is also
used for opacity.
(ii) News print High mech. pulp and a small % of 48.8
chem; pulp.
(iii) Bond paper Bleached chem pulp and cotton fibres 48, 60, 75, 90
water marking possible.
(iv) Uncoated soft Kraft or sulfite soft wood pulp with
wood paper limited amount of mech. pulp or
recycled paper.
(v) Magazine paper Coated ground wood pulp
(vi) Coated wood Kraft or sulfite soft wood pulp with
free paper coating on both sides. Min 50% mech. pulp.
(vii) Tissue paper Bleached chemical soft wood or hard 15–60
wood pulp with some mechanical pulp.
(viii) Wrapping or bag Kraft soft wood pulp 50–134
paper
(ix) Cast coated paper, MG. Kraft, high glossy paper.
machine glazed
(x) Speciality paper Refined chemical pulp used in electronics,
cigarettes, currency making, tea bags etc.
(xi) Linear board Unbleached Kraft soft wood used for 205, 220, 330
corrugation.
(xii) Kraft paper Bleached/unbleached from kraft pulp
boards
(xiii) Corrugating Unbleached semi chem. pulp and recycled 127
medium paper fiber
(xiv) Grease proof From very refined chem. Pulp
37
2. PAPER SIZE STANDARDS

Size Purpose Wt. in gms/m2
24" × 36" News print 1.6275
17" × 22" Printing 3.7596
19" × 24" Blotting 3.0836
20" × 26" Cover 2.7041
22" × 28" Card board 2.2827
22.5" × 28.5" Bristol 2.1928
25" × 38" Book 1.9801
3. TEST PARAMETERS FOR PAPER

(i) Brightness (0 for black to 100% to MgO standard which has on absolute brightness of 96%
by the reflectance of blue light 457 nm from paper)
Burst
Burst index
Stiffness
Flat crush
Tear value
Tear strength
Tensile strength
Toughness index and
Thickness or Caliper (for paper board)
(ii) Test parameters for wood = Kappa no (indicated lignin in wood) and determines consumption
of oxidation chemical, Pot. permanganate.
4. RAW MATERIALS FOR PAPER MANUFACTURING

(i) Soft wood: Fir, Pine, Cedar, Larch, Red wood, Spruce (a type of fir) and some others.
Broadly soft wood contains 55–74% holocellulal (α cellulose 38–50%) and 9–11% pentosans (lignin).
Soft wood is obtained from coniferous trees.
(ii) Hard wood: Birch, Eucalyptus, Maple, Oak, Poplar and some others. Holocellulal content
in hard wood is 70–74% (α cellulose 41–48%) and that of Pentosons is 16–21% (lignin). Hard wood
is obtained from deciduous trees.
(iii) Non wood fibres for pulping: Bamboos, Bagasse, Espartograss, reeds, rice and wheat
straws, ramic and papyrus, corn oat stalks and barley stalks.
(iv) Textile fibres for pulping: Cotton linters, Flam, Manila hemp (abaca) and sisal.
Soft woods are preferred material for pulping due to its longer cellulose fibres (approx. 3–4
mm long and dia of 25–30 µ). Low lignin content hard woods are used for special paper making
where smoothness and softness are desired.
PULP AND PAPER 39
Table 1
Typical analysis of soft wood and hard wood and their pulps.
Constituents Soft wood Hard wood Soft wood Hard wood

% wt. % wt. pulp % wt. pulp % wt.
Cellulose 52 54 85 84
Hemicellulose 17 21 12 14
(Carbohydrates)
Lignin 28 22 3 1
Extractives (resins, 3 3 - -
gums, fats, waxes
and colouring matter)
5. MANUFACTURING PROCESSES
(i) Pulp manufacturing process principles consists of dissolving cellulosic binding material,
lignin by certain chemical and thus releasing the individual fibres. In the process, extractives are also
removed.
The four process steps for wood pulping are:
A. Kraft or Sulfate process at pH 13–14
B. Sulphite process–it is further subdivided into
(a) Commonly used sulfite or bisulfate process at pH 1.5–5.
(b) Neutral sulfite or semi-chemical process at pH 7–10.
(c) Mechanical pulping process.
(d) Chem. Mechanical process using mild action of NaOH or NaHSO3.
Kraft Process is comparatively new chemical pulping process developed in 1940s while Sulfite
Process is the oldest, developed since 1900.
(ii) Chemical pulping stages broadly consist of
(a) Wood preparation
(b) Digestion with reqd. process chemicals
(c) Washing of pulp
(d) Bleaching, washing and screening
(e) Pulp beating
(f) Paper making
(g) Chemical recovery from black or brown spent liquor from digester.
A. Kraft or Sulfate Process
5.1 Wood Pre-treatment
Wetted hard wood or a mix of hard and soft wood are cut into 4' or 8' long logs and fed in-
to the debrarking mill which consists of rotating large horizontal drum of steel bars. Debarked log
is removed from the other end of the drum. Modern method consists of using high pressure water
jets at 1400 PSI at perpendicular to wooden logs for debarking.
The debarked wooden logs are then cut into chips (5/8"–7/8"in length × 1/16"–1/8" thickness
and 1/2"–1") width in a chipping machine.
5.2 Digestion
The chips are then fed into the digester or pressure vessels of capacity 1500-3500 cft and
recovered cooking liquor is added. The composition of kraft cooking liquor is as follows:
NaOH = 70 gm Na2O/lit
Na2S = 30 gm Na2O/lit
Na2CO3 = 20 gm Na2O/lit
The amount of sulfide is defined as “sulfidity” which is Na2S content divided by sum of NaOH
and Na2S all expressed as Na2O. Sulfidity is maintained at 25–28%. Na2CO3 present acts as an inert
material in cooking liquor after recovery of spent black liquor from digester. Make up Sod. Sulfate
is added to black liquor from recovery furnace for use as cooking liquor depending on active material
conc.; caustic efficiency is determined by ratio of NaOH/(NaOH + Na2CO3). In paper mills Sod.
sulphate soln. is prepared by melting sulphur with soda ash in air.
2Na2CO3 + 2S + 3O2 
→ 2Na2SO4 + 2CO2 
H2 O
→ Sod. Sulphate soln.
Pressure in autoclave is kept at 13–14 PSI. Solid consistency in autoclave is 24–30%. The
digester is heated with steam at 100–115 PSI which gives a cooking temp. at 170–175°C. Digestion
time varies between 4–6 hours. The colour of cooking liquor gradually changes to black as cooking
progresses. Initially dissolution of carbohydrates (soluble hemi-cellulose) is faster than lignin.
After the digestion is over the autoclave pr. (steam) is reduced to 80 PSI and contents
discharged into a tank. Only 1/2 of Na2S is effectively available.
5.3 Filtering, Washing and Screening of Pulp
From the dumping tank, pulp is separated from spent liquor in cyclindrical washers with
washing of pulp. Screening is done in two stages, firstly in common screen (V.K. roller) that removes
undigested chips and secondly in screen which removes uncooked fibres. The pulp output is
46–48% of original wood. The colour of Kraft pulp is light greyish brown.
5.4 Bleaching of Pulp
For good quality white paper, the pulp thus obtained, is bleached. Initially chlorine bleaching
which was discovered in 1930s is followed by Cl2O and H2O2 bleaching which was introduced a
decade later. Oxygenated bleaching agent is used in 1960s. Bleaching is for destruction of chromophore
in organic and inorganic compounds remaining in pulp. Bleaching involves oxidation or reduction or
both. The oxidative removal of chromosphore is irreversible, whereas reductive bleaching can be
reversible in presence of oxygen in air. Bleaching removes residual lignin from pulp and also purifies
cellulose. Now a days bleaching process is subdivided into several steps with washing of pulp in
between to reduce chemicals. Use of lesser quantities in greater no. of steps reduces danger of
cellulose detoriation by bleaching. Initially less selective chemicals are used and finally selective
bleaching agents are used.
Bleaching is carried out in several towers with washing drums or displacement (diffusion)
washers in between the steps. Kraft pulp is difficult to bleach. For bleaching with Cl2 gas or soln.,
pulp consistency reqd. is 3–4%.
PULP AND PAPER 41
Bleaching steps in kraft pulp:

(a) Cl2–alkaline extraction–hypo-chlorite–Cl2O
(b) Same as in (a) followed by alkaline extraction–Cl2O
(c) O2–Cl2–alkaline extraction–Cl2O–H2O2–Cl2O
(d) O2–Cl2–Oxygen/alkaline extraction–Cl2O
(e) H2O2, Cl2O
The no. of steps used for bleaching depends on type of product desired. Paper mills produce
their hypo-chloride by reacting Cl2 with NaOH:
Cl2 + 2NaOH 
→ NaOCl + NaCl + H2O
or Cl2 + Ca(OH)2 
→ CaOCl2 + H2O
However, use of lime is decreasing. Hydrogen Peroxide is produced by reacting Sod. Peroxide
with water:
Na2O2 + 2H2O 
→ H2O2 + 2Na+ + 2OH–
Chlorine dioxide, Cl2O is an explosive agent. It is gas at STP but explodes spontaneously at
partial pressure of > 40 KPa, decomposing to Cl2 and O2. If heated or exposed to light it can
exploded even at lower conc. In paper mills it is usually prepared at site from Sod. Chlorate:
4NaClO3 + 4HCl 
→ 4ClO2 + 2H2O + 4NaCl
2NaClO2 + Cl2 
→ 2ClO2 + 2NaCl
Bleaching with H2O2 requires stabilishing agent, Sod. Silicate chelating agent (heavy metal ion
chelating), dispersants and magnesium salts. Oxygen bleaching is done in NaOH presence.
5.5 Pulp Beating and Filtration
Pulp refiners called beaters are used to treat bleached pulp to improve paper making properties.
Originally Jordon/Hollander beaters were used and now replaced by disc refiners. The beater machine
lacerate or cut pulp fibres. The disc is made of hardened Ni-white iron. Use of conical disc is
subsidising. After wood pulp is diluted to 1.5% congistency and filtered in vacuum filters pulp is
obtained. The pulp cake has 10–20% consistency.
5.6 Paper Making through Bleached or Unbleached Pulp
Purified pulp is used in various paper making machines to produce final paper, dried and packed
automatically.
After beating operation of the pulp, there is large increase in surface area, sliminess, and good
dispersion, increasing in equilibrium moisture/Cu no. and zeta potential.
5.7 Chemical Recovery
The digester spent black liquor pulp and filter washings are treated to recover valuable chemicals,
which are reused in digester after addition of make up chemical (Sod. Sulfate). The spent black liquor
contg. 10–15% solids (about 40% inorganic, 60% organic) is concentrated to 48–50% solids in a
series of counter current evaporates (4–6 stages) with vacuum (8–23 mm Hg) at feed end and Pr.
operations (45–15 PSI) at outlet end. Tall oil is separated from 2nd stage outlet. The concentrated
liquor contg. 50% solids is black liquor which is further concentrated to 65–73% solids in a heater
and finally sprayed with steam in a recovery boiler using 20% excess air (50% of which is preheated
to 150°C). The organic material in atomized spray dries as it falls and burns and salt gets melted
and flows to the outlet. Air flow is controlled so that all sulphur compounds are reduced to sulfide.
Steam is produced in recovery boiler top steam coils.
Make up Sod. Sulfate is added to feed the stream to recovery boiler so that it also reduces to
Sod. Sulfide. The molten chemical is taken out from the furnace and led into a re-circulating water
settling tank where it dissolves to form green liquor. The dross, about 0.1%, settles at bottom and is
periodically removed. The green liquor is then transferred to causticizing tank where lime is added. The
clear liquid from top is sent to digester and settled lime mud is burnt to make Calcium Oxide for reuse.
Na2SO4 + 4C 
→ Na2S + 4CO
NaOH + CO2 
→ Na2CO3 + H2O
Na2CO3 + Ca(OH)2 
→ 2NaOH + CaCO3
Typical data for chemical recovery:
Chemical recovery = 90%
Caustification eff = 85–90%
Reduction of Sulphur Compounds = 90–95%
Steam economy in evaporator 6 stage is possible which will enable 14 lbs of steam at 45 PSI
to remove 70 lbs of water from 100 lbs of black liquor containing 15 lbs of solids and 85 lbs of
water to a conc. of 30 lbs of solids (50% concentration).
6. SULFITE PROCESS
This process differs from kraft process in digestion procedure, bleaching of pulp and chemicals
recovery. Normally soft wood is used.
6.1 Digestion Method and Chemical Recovery
Digester capacity is 3500–12000 cft, chemicals reqd. are sodium sulfite and soda ash. A total
of 6.5% SO2 (free 5.3% and combined 1.2%) is reqd. for digestion to dissolve lignin with the
formation of Sulfonate and removal of lignin bonds. Some dolomite is also used. In paper mills
Sodium Sulfite is prepared by melting sulphur, absorption of SO2 in water to form Sulphurous acid
followed by reaction with base, NaOH:
S + O2 
→ SO2
SO2 + H2O 
→ H2SO3
H2SO3 + NaOH 
→ NaHSO3 + H2O
NaHSO3 + NaOH 
→ Na2SO3 + H2O
An alkaline pH upto 10 is maintained in autoclave heated with steam at 80 PSI. Recovered
cooking liquor from chemical recovery section is added into the autoclave after chips are transferred.
Cooking time is 7 hrs. Temp. is raised initially to 110°C in 4 hrs. The temp. is again is raised to 135–
140°C and kept for 3 hrs. At the end of cooking period, pr. is brought down to 30 PSI and autoclave
effluent discharged into a pit. After separation of pulp and washing, the grayish white pulp is sent
for bleaching and subsequent operation and the spent brownish liquor is sent for chemical recovery.
PULP AND PAPER 43
6.2 Chemical Recovery

Similar method for kraft process is used where recovery of chemicals upto 50% is achieved.
The conc. brown liquor is burnt in a recovery boiler. The make up Sod. Sulfite is added to the conc.
brown liquor before it is atomized with steam and burnt in boiler. The melt from boller is put in water
tank with re-circulation. The green liquor is transferred to causticizing tank where lime is added. The
clarified, filtered clear liquor is then sent to digester for use as cooking liquor. The lime mud is
vacuum filtered and cake dried in a rotary kiln to obtain lime, which is reused.
6.3 Bleaching of Sulfite Pulp
Bleaching sequence is as follows:
Chlorine .......... alkali extraction .......... hypo-chlorite
Chlorine .......... alkali extraction .......... hypo-chlorite .......... Cl2O
Chlorine .......... H2O2 .......... alkali extraction .......... hypo-chlorite .......... Cl2O
Oxygen .......... Chlorine alkali extraction .......... Cl2O .......... H2O2
O2/H2O2 .......... Cl2O .......... H2O2
7. MECHANICAL PULPING PROCESS

Here, a no. of chemicals are used and the process is suitable for Hard wood and light colored
soft woods, like spruce, balsam, fir and hemlock.
Wet soft wood is debarked, cut into small pieces and ground in a rotating disc to powder form,
followed by pulping and bleaching with H2O2. The yield of mechanical pulp is 92-96% of wood
treated. Paper produced is used for newspaper and magazines; very often 30–40% waste paper is
used in this process.
Apart from this process, TMP and CTMP processes are also used.
8. DE-INKING OF WASTE PAPER

Recycling of waste paper is a very necessary step for conservation of forest products and for
paper manufacture it is essential that ink and other impurities be removed from recycle paper. There
are two processes:
(i) Wash deinking process.
(ii) Floatation deinking process.
Both the process involved alkali treatment of waste paper by immersing waste paper baskets
in caustic soda solution followed by bleaching with H2O2. Deinked newspaper is used mostly with
hard wood pulp for newspaper and magazines.
9. SPECIALITY PAPER
Here unused non-wood based raw materials are used to get good quality chemical pulp due to
low lignin content. Leaf cellulose also yields good quality pulp suitable for currency note.
9.1 Bamboo Pulp
Here NaOH and Soda ash is used as chemicals for pulping. After crushing, the bamboo is cut
into chips and digested with alkali in a two-stage counter current alkali digestor. High quality pulp
is obtained which is better than cereal pulp.
9.2 Bagasse and Corn Stalk Pulp

Here a rod mill is used as a 1st stage digester in series with a 2nd stage digester with alkaline
cooking liquor. High-grade pulp is produced which is suitable for light wt. paper making.
9.3 Cereal Pulp
Here rice, wheat, oat and barley straws are used as raw materials. Cooking liquor used is milk
of lime (10% CaO) or 13% burnt dolomite. The digester is spherical or rotary. Cooking is carried
out at 115°C for 8–10 hrs. using steam at 45 PSI. The pulp is suitable for corrugated paper.
9.4 Details of Pulp Bleaching (Cl2 alkaline extraction-Hypochlorite-H2O2-O2/Cl2O)
Normally chlorine bleaching is done with alkali extraction with soda ash at a temperature of
65°C for about an hour and hypo chloride bleaching using Sod. or Cal hypo chlorite at ambient temp.
(30°C) for 2–4 hrs. in 2–3 stages with mild alkaline wash in between stages. Subsequent stages of
bleaching are with H2O2. Oxygen and Cl2O are used for better quality paper-making. In all types of
bleaching, calculated quantity of bleaching agent is used. The bleachability test or TAPPI permanganate
(O.IN) test indicates amount of chlorine in the form of hypo chlorite reqd. to bleach 100 gm. of
pulp to standard brightness. Actually it measures the amount of 0.1 N KMnO4 soln. that reacts with
chlorinated soln., consumed by one gm. of pulp under standard condition.
10. PAPER MAKING BY HOLLANDER MACHINE

The bleached pulp is subjected to beating operation in Hollander machine when cellulosic fibres
swells (expanded) spilt, bruished and deformed. The machine consists of an oval shaped trough
divided in two segments. The bedplate is placed in one section and is made up of projected bars or
blades (bronze or steel) of 3/4" dia × 3" thick. A big roller is placed over the blades and bars fixed
on the bedplate. The clearance between the roller blades and those fixed on the bedplate is small and
can be adjusted. The roller moves at a peripheral speed of 2000 ft/min. The slurry (5–8% conc.)
is circulated around the trough by the padding action of the roller. As the pulp moves through the
clearance it is subjected to rubbing, splitting, brushing and deformation along with swelling of the
pulp. The clearance is gradually reduced as beating continues. The time of beating varies from 1 hr.
to several hrs. depending on the nature of pulp required.
After pulp beating, it is filtered and used for paper making in various automatic machines.
11. Neutral sulfite semi chemical pulping yields black liquor from which acetic acid and formic acid
can be extracted.
Paper pulping liquor is a source of hemi cellulose fraction of wood and from which lignin
chemicals can be obtained.
Tall oil
It is obtained from Kraft wood pulping process and it is a mixture of resin and a group of fatty
acids.
Chapter
4
CHLOR ALKALI INDUSTRY
Chlor-alkali industry is one of the key chemicals industry for producing caustic soda (as Pellets,
flakes) and chlorine by electrolysis. Pure Hydrogen is produced as a by-products. There are 3
processes. Each process uses different method of keeping the Cl2, produced at anode, separate from
NaOH and H2 produced directly or indirectly at cathode. Saturated and purified brine is used at raw
material. DC voltage is applied to battery of cells in series.
The cell voltage is kept above the theoretical requirement due to secondary reaction and current
leakages.
(a) Mercury Cell (Castner Kellner Cell-1892)
(b) Diaphragm Cell (Greshiem Cell-1885)
(c) Membrane Cell (1970)
Reactions :
2NaCl + 2H2O 
→ Cl2 + H2 + 2NaOH
Cathode reaction:
2Na+ + 2OH– 
→ 2NaOH
or 2NaHg + 2H2O 
→ 2NaOH + H2(g) + 2Hg
Anodic reaction:
2Cl– 
→ 2Cl– + 2e 
→ Cl2
Equation for electrolysis:
Q = I× t
where Q = coulombs of electricity, I = Current in amps, t = time in seconds.
Theoretically 96544 coulombs of electricity will produce 1 gm equivalent wt, which are 35.45
gms of Cl2, Hydrogen (1.005) and NaOH (40.01 gm). This output is based on First law of electrolysis
(Faraday).
Mercury Cell
Here Sod. amalgam (NaHg) is produced at cathode which is reacted with water in a separate
reactor called decomposer to produce NaOH soln. and Hydrogen gas and regeneration of Hg takes
45
place. Brine is re-circulated and NaCl salt is reqd. for re-saturation. Brine used is purified-first,
dechlorinated and then purified by straight precipitation and filtration process. The products obtained
are very pure. The Cl2 along with little oxygen is used to produce HCl by burning chlorine in air.
NaOH contg. little chloride leaves the decomposer with as much as 50% (wt.) concentration. This
process requires maximum power for electrolysis but no steam is reqd. for conc. of NaOH soln.
Hg requirement is maximum and requires environmental facility for treatment of Hg leakages from
cell. H2 gas and chlorine must be freed from Hg.
Liberated hydrogen at cathode is carried through electrically insulated pipe from decomposer
or cathode compartment and is cooled in a vessel filled with water seal. If Hg and air mixture is
formed due to shut down or breakdown, the seal allows the H2-air mixture to escape. A demister
is put to ensure Hydrogen is free from water droplets or NaOH soln. The hydrogen gas is compressed
in roots blower or compressor, cooled in an after cooler and sent to consuming points. Hydrogen
is about 99.5% pure. The oxygen in hydrogen can be removed by palladium/platinum catalyst and
Hg by spl. catalyst if necessary for end use. Typical Hg content after cooler in Hydrogen gas is
15 mg/NM3 and O2 content is 500 ppm. Cell circuit voltage varies from 1300–2500v and applied
D.C. voltage in each cell is 3.1 volt and operating voltage 4–4.25 volts.
Because of very old process with high consumption of utility as well as Hg loss resulting in
Hg pollution, this process is obsolete now.
Membrane Cell
In membrane cell, anode and cathode are separated by a cation permeable ion exchange
membrane which can be polar or non polar. Here only cations, Na ions and little water pass through
membrane brings brine purified by de-chlorination and re-circulated which is required for solid NaOH
to saturate the brine. Since the life of membrane depends on purity of brine, brine after precipitation
for Mg++ and Ca++, ions are removed by sod. carbonate treatment and filtration. A high purity brine
is reqd. It is further purified by ion exchange. NaOH soln. produced at cathode is 35% concentrated
and is further concentrated by steam in evaporator to 50% conc. or converted to fused NaOH. The
consumption of electricity is 25%–40% less than that of mercury cell. The consumption of steam
for conc. of NaOH is also less than diaphragm cell. O2 consumption by electrodes is less. No
environmental pollution occurs and the cells are easy to operate. The cells are relatively less costly
and insensitive to current density changes. Power consumption is about 2100 Kwh/Te in the membrane
cell.
Mercury Cell (Krebs type)
Cathode area = 20.2m2
Cathode size = 14.4 × 1.61 m2
Slope of cell = 1.8%
Current = 300 A
Maxm. Current density = 13 KA/m2
Cell D.C. voltage at 10 KA/m2 = 4.25 V
Stems per anode = 4
Qty. of mercury per cell = 2750 Kg
Energy (DC) reqd. Kwh/Te = 3000
CHLOR ALKALI INDUSTRY 47
C l2 ga s H 2 gas C l2 ga s H 2 gas
To c ath oly tic c ham ber

to cath oly tic c ham ber
ch am be r (an aly te)
D ep lated brine to
N aO H so ln.
D eplated brine to
analy tic ch am be r
N aO H s oln.
M e m brane
M e m brane
A nod e
A nod e
e lem ents
C athod e
C athod e
C e ll
C e ll
B rine W a ter B rine W a ter
Fig. 1. Membrane cell : Bipolar elements arrangement.

Membrane cell technology came in around 1970. The process is most energy efficient as well
as pollution free.
Saturated pure brine soln. (310 GPI) is fed into anode compartment and water in cathode
compartment of electrolyser where DC voltage above theoretical limit is passed. Sodium ions with
some OH-ions pass through membrane, made of per-fluoro-sulphoric acid or others whose life is
about 4 years and forms NaOH soln. in cathode chamber. Water is added to cathode chamber and
NaOH soln. from cathodic cell top is sent to catholyte chamber.
H2 generated, is a very pure type and sent for compression and use elsewhere. The NaOH soln.
(~ 35%) soln. form cathodic chamber is sent for concentration.
Chlorine, generated in anodic compartment with oxygen content 0.5–0.7%, is sent for other
uses in the plant of HCl production. Purified brine @ 310 GPI is fed to anode compartment and
deplated brine from anode chamber is taken to anolyte chamber from where it is sent to brine
purification section for saturation with brine soln.
Mono Polar and Bi-polar Electrolyser
Depending on the mode of DC connection to electrolyser cells, they are classified as bi-polar
or mono-polar. Bi-polar cells are having min. voltage drops between cells and electrolysers are
connected in parallel. The monopolar cells have simple structure and easy for maintenance. Each cell
unit in one electrolyser is connected in parallel and each electrolyser is connected in series of 100
electrolysers. Electrolyser operates as per Faraday’s law.
The electrolysers consists of plate type cells. The cathode is made of activated nickel and anode
is of Titanium and both have operating life of 8 years each.
Diaphragm Cell
In this process (also called Nelson Process) the cell is U-shaped with graphite anode at center
and perforated steel cathode covering the outer surface of asbestos, which acts as diaphragm.
The cell is in an outer casing in which steam is put to heat the cell to reduce the resistance
and also to keep the pores of asbestos diaphragm clean.
Purified brine, after causticizing and removal of iron and other metals is kept in the cell at
constant level and electrolysis takes place as it percolates through the asbestos diaphragm.
Cl– ion is discharged at anode as Cl2 and is let off. H+ ions are discharged at cathode where
Na+ and OH– i.e., NaOH accumulation takes place in water which diffuses through porous diaphragm
from anode compartment. The NaOH conc. is 10–12% and liquor containing NaCl (14–16%) which
is separated by conc. and separates out. The NaOH soln. is further concentrated by evaporation,
fused and flaked. No re-circulation of brine takes place. The power consumption is less than mercury
cell and product yield contains much NaOH. Actual DC voltage applied in each cell is 3.8 V. Series
cells circuit voltage is 800 V.
Brine Purification Steps
The impurities in brine is given in table 1 below:
Table 1
Sea salt Rock salt

Insolubles 0.1–0.3% ≤ 2%
Water 2–6 ≤3
Calcium 0.2–0.3 0.1–0.3
Magnesium 0.08–0.3 0.03–0.1
Sulphate 0.3–1.2 ≤ 0.8
Potassium ≤ 0.04 0.02–0.12
Purification steps for brine depend on type of cells used and impurities in salt (sea or rock).
In membrane and mercury cells HCl is added to brine to lower pH 2–2.23 (Cl2 = 400–1000
mg/lit). Brine is sprayed in a packed column or brine sprayed in a vacuum, de-chlorination vessel
at 50–60 Kpa which reduces the chlorine conc. to 10–30 mg/lit; vacuum is maintained by steam jet
ejector or a liq. ring pump. The water from de-chlorinator is condensed in a cooler and further
reduction in chlorine is done by either activated carbon or chemical treatment with hydrogen sulphite/
hydrogen thiosulphite salts. Conc. of sod. chloride is determined by vibration techniques, radioactive
isotopes or density measurement.
Precipitation by adding chemicals
1. With Na2CO3:
CaCl2 + Na2CO3 
→ CaCO3 + 2NaCl
MgCl2 + Na2CO3 
→ MgCO3 + 2NaCl
2. With NaOH:
MgCl2 + 2NaOH 
→ Mg(OH)2 + 2NaCl
FeCl2 + 2NaOH 
→ 2NaCl + Fe(OH)2
3. With Barium Chloride:
BaCl2 + Na2SO4 
→ 2NaCl + BaSO4
CHLOR ALKALI INDUSTRY 49
If Mg++ is high in brine, lime soda process is used for its removal which removes Ca also:
MgCl2 + Na2CO3 
→ MgCO3 + 2NaCl
Mg(HCO3)2 + Ca(OH)2 
→ MgCO3 + CaCO3 + 2H2O
Ca(HCO3)2 + Ca(OH)2 
→ 2CaCO3 + 2H2O
Ca(HCO3)2 + Na2CO3 
→ CaCO3 + 2NaHCO3
Dilute solns. of the dosing chemicals are added to weak brine soln. followed by adding fresh
NaCl salt to bring NaCl soln. to the reqd. level. Brine soln. is further purified by ion exchange resin.
Chapter
5
CELLULOSIC FIBRES (RAYON)
Rayon or artificial silk is regenerated cellulose from cellulose xanthate obtained from xanthation
of cellulosic raw materials. Natural cellulose is a polysaccharide (carbohydrate) having the empirical
formula C6H10O5.
There are four main processes for the manufacture of cellulosic fibres or rayon:
(a) Viscose process
(b) Cupraammonium process
(c) Cellulose nitrate process
(d) Cellulose acetate process (non regenerative)
The process at (d) is used in 50% of manufacturing units.
(a) Viscose manufacturing process
Here cotton linters is used as the raw material source for cellulose. The residual cotton left in
cotton seeds after the lint or cotton has been removed is used for textile manufacture.
The cellulosic raw material thus obtained is subjected to steeping operation using 18% caustic
soda soln. at 18°C for 30–90 mins. Excess caustic soda soln. is drained off and the cellulose is
pressed until final wt. is about 3 times the original wt. of cotton linters.
Reaction: C6H7O2[(OH)3]n + n NaOH 

→ [C6H7O2(OH)(NaO)2]n + (n–2)H2O
The wet cellulose is then disintegrated in shredders at temp of 20–30°C. Temp. control is
important as at higher temp. residual caustic will react with cellulose thereby reducing the length of
cellulose chains. The fluffy cellulose material is stored in cans at 25–30°C for 18 hrs., when the
length of cellulose is shortened as per desired length. This ageing process controls the viscosity of
viscose soln., formed at a later stage, and the final strength of finished viscose fiber. Ageing time
and temp. are carefully controlled to achieve desired finished product.
The aged alkali cellulose is then put into revolving drums called barattes each having a capacity
of 500–1000 gallons (U.S.) and carbon disulphide is added in the proportion of 50 lbs or less per
100 lb of alkali cellulose and reacted for 2–4 hrs. Alkali cellulose is converted to dithiocarbonate
cellulose, granular or jelly like mass and the colour changes to bright orange.
50
CELLULOSIC FIBRES (RAYON) 51
Reaction:
This xanthation reaction is exothermic and the barattes are, therefore cooled to keep the temp.
at 25–30°C. The gases evolved are also removed. The cellulose xanthate is then transferred to water
jackated dissolvers or mixers in which dil. caustic soda is added along with a delustering agent
(Titanium oxide or White Oil) which reduces the brightness of fiber. The cellulose to caustic soln.
ratio is maintained at cellulose = 6–9% and caustic = 4–7%. The temp. of this reaction is controlled
at 16.7°C. The orange coloured xanthate soln. thus formed is called viscose.
The viscose soln. is then transferred to evacuated blending tanks and allowed to ripen until it
becomes suitable for spinning process for making viscose rayon fibres.
The controlling factors for hydrolysis, carried out in ripening process, are temp., residence time
and ripening process is carried out for 48 hrs. at 17–22°C. Increased residence time or higher temp.
accelerates the ripening process.
In the next step, cellulose xanthate is regenerated to cellulose in the spinning bath where it is
filtered and extruded through cup-shaped spinnerets made of Pt-irridium of Pt-gold alloy having holes
(0.002 to 0.006 in dia.). For staple fibers, no. of holes could be several thousands. The spinning bath
contains some chemicals also (H2SO4 = 8–12%, Sod. sulphate 0.5–2%, zinc sulphate and glucose).
The spinning bath is kept at about 43°C. Sod. sulphate helps in co-agulation in fiber formation and
liberation of H2S. Glucose is used to prevent salt formation during precipitation or co-agulation
reaction. Sulphuric acid is the regenerating agent which co-agulates the cellulose xanthate and breaks
down the xanthate releasing cellulose. Sod. sulphate is formed in the reaction as also free NaOH is
always present. Zinc sulphate helps which is formed on the filament and increased the tensile strength
in fine filaments.
There are two types of spinning machines–one is pot or bucket type and the other spool or
bobbin type. The viscose soln. soon after coming through spinnerets in the form of threads as it
passes through the spinning bath where it is co-agulated and formed into cellulose fiber which travels
upwards through a guide (in bucket type spinning machine, movement is downwards through a feed
wheel and then through glass funnel). The revolving bucket speed is 2000–9000 rpm and it gives
twist as the bucket rotates. The spinning operation takes 20–30 mins. After spinning, the yarn is
subjected to stretching, washing, de-sulphurising, bleaching, finishing (oiling), drying and twisting
operation.
(b) Cuprammonium Process
In cupraammonium process, cotton linters are dissolved in copper hydroxide and ammonium
hydroxide (25° Baume'). The dissolved cellulose soln. is taken to 2nd mixing tank where it is diluted
to 4% cellulose with water–filtered in vacuum filter–blended with other charges and de-aerated. The
filtered viscose soln. is then pumped to spinning machine where 4% NaOH is used in spinning bath.
The yarns are treated with 1–3% H2SO4 followed by washing with soft water and drying.
Raw materials reqd. per lb. of rayon =
Cotton linters = 0.92 lb
Copper sulphate = 0.75 lb
Ammonia = 0.5 lb
NaOH = 0.80 lb
(c) Cellulose nitrate process
In cellulose nitrate process for yarn making, cotton linters are mixed with ether and alcohol.,
filtered and subjected to ageing process.
After ageing the cellulose soln. is subjected to dry spinning. The soln., as it comes out of
spinnerets of spinning machine, it passes through warm air which evaporates the solvents and helps
in coagulation of filament. The individual yarns are combined when a slight twist is given, followed
by de-nitration by treating the filament with sod. sulphate or ammonium sulphide soln. The yarn is
regenerated into cellulose during de-nitration, washed and bleached.
There is very little use of this process as it is more expensive and dangerous also.
(d) Cellulose acetate process
In this process cellulose is not regenerated but involves the production of cellulose ether. The
process consists of acetylation of cotton linters with combined acetic acid (over 50%) followed by
hydrolysis with dil. acetic acid under controlled temp. condition. Water reacts with part of acetyl
group of triacetate liberating acetic acid. When the combined acetic acid content, by hydrolysis, is
reduced to 54.5%, the mass is diluted so as to precipitate secondary acetate when entire cellulose
acetate is precipitated. This is washed with water to remove acetic acid. The precipitated cellulose
acetate is then dissolved in acetone in large enclosed mixers, filtered with stirrers and agitated for
12–24 hrs. depending on derived viscosity of cellulose soln. The soln. is then blended in blending
links when it is mixed with previous value of quality controlled material. The soln. is then filtered
under press. in cotton filters. Filtration is carried out several times and the cellulose soln. is stored
in evacuated vessels for de-aeration.
The soln. is then sent to spinning machine similar to spinning process for cellulose nitrate yarn.
The yarn obtained is bright unless some delustreing agent is added in the spinning bath.
Cellulosic Polymers–Rayon, cellulose acetate, cellulose esters, cellophane and modified cellulose
are in stiff competition from petrochemicals.
Chapter
6
SELECTED PROCESS EQUIPMENT
DESIGN
1. Process material balance of the selected process route has to be carried out followed by heat
balance of each equipment calculated with available material balance and various physical data
and data on heat of reactions for various reactions in the process equipment.
A thorough knowledge of reaction kinetics, thermodynamics is essential for designing of a
chemical process along with types of equipment required for the process route adopted. Similar
available processes are also to be studied while making material and heat balance.
2. Once material balance and heat balance are ready and checked for Hazop-I (Hazards of
operations), designing of process equipment starts. Hazop II analysis is to be done after process
and equipment design is over and much erection is completed. Hazop III analysis is done with
problems faced during commissioning.
3. A FEW SELECTED PROCESS DESIGN PROCEDURES ARE GIVEN BELOW:

3.1 Sizing of Vapour—Liquid Separators
l1
D= D iam eter of separator, m m
L
D N D1 l1 = D mm
l2 = 0.3 D
l2
L= l1 + l2
H= H t. of bottom storage of separator, depends on residence tim e
in secs; For 12 secs residense tim e, H = 500 m m .
4 5° N D 1 = Inlet nozzle nom inul dia, m m
N d 2 = O utlet nozzle = N D 1
H
N D2
Fig. 1 Impingement type

vapour-liquid separator.
53
These are impingement type separators used to separate a liquid from vapours from preceding
process vessels.
Exm: Design a vapour liquid separator for the following gas liquid mixture from the material
balance of a plant for urea production.
Flow Kg/hr Kg mole/hr
NH3 4094 240
CO2 1377 31.3
H2O 1905 106
7376* 377.3
The gas Pressure is 3 Kg/Cm2 abs at 150°C
Flow of gas Q = 377.3 × 22.4 × 1/ 3 × 423

273
= 8450 × 0.515 = 4360 m3/hr
= 1.21 m3/sec
7376
Density of gas, ρG = = 1.69 Kg/m3
4360
Density of liq. soln. ρS = 1100 Kg/m3 (assumed)

The theoretical speed of vapour Vt as per Pastonisi’s book, volume-1
ρS
Vt = 0.22 −1
ρG
1100
= 0.22 × − 1 = 0.22 × 25.4
1.69
= 5.6 ft/sec = 1.71 m/sec.
Design speed, V = 0.4, Vt = 0.4 × 1.71 = 0.684 m/sec.
(40% of Vt)
Free cross-section of the separator assuming 20% oversize :
A = Q/V × 1.20
1.21 × 1.20
= = 2.12 m 2
0.684
The separator inside pipe has an o.d equal to
406.4 – 2 × 3.5 = 400 mm
Π
I.D. of separator is = [D 2 − (0.4) 2 ] = 2.12
4
Π 2
D = 0.125 + 2.13 = 2.245
4
D = 1.905 m = 1900 mm
* Excluding urea wt.
SELECTED PROCESS EQUIPMENT DESIGN 55
The lower tank part having level indicators is sized for a residence time of 12 secs. l1 is
assumed to be D and l2 = 0.3D, and h (assumed) = 500 mm for residence time of 12 secs.
The out following urea soln. from separator, as per material balance is 30904* kg/hr and density
is 1100 kg/m3. The volume of tank (lower) is
1.2 12
V = 30904 × × = 0.112 m 3 (20% oversize of tank)
1100 3600
Inside diameter of tank:
Π 2
[φ − (0.4)2 ] × 0.5 = 0.112 m3
4
Π 2
φ = 0.224 + 0.125 = 0.349
4
φ = 669 say 670 mm
l1 = D = 1900 mm
l2 = 0.3 D = 570 mm,
L (overall length) = 1900 + 570 = 2470 mm
3.2 Sizing of a Steam Heater (H.E)
Example: Size up a 13 Kg/cm2 abs. steam heater (steam in shell side) shell and tube heat
exchanger having S.S tube for decomposition of ammonium carbonate soon in tube side. The heat
duty required is 2,600,000 Kcal/hr and soln. flow rate is 38000 Kg/hr which is to be heated up in
H.E. from 130°C to 150°C.
Calculations–Flow rates in an hour and overall heat transfer co-efficient assumed is 1000 Kcal/
hr.m2.°C which has to be verified later.
Heat to be exchanged = 2,600,000 Kcal/hr.
Steam saturated at control valve inlet is 13 Kg/cm2 abs. and effective steam pressure in H.E.
(shell side) is assumed 7 Kg/cm2 abs. having condensation temp of 164.2°C.
(a) Calculation of ∆tm:
t1 − t2
∆tm =
2.303 log (t1 / t2 )
34.2 − 14.2 20
= 2.303 log 2.41 = 0.80 = 22.70°C
(b) Exchanger surface area:

Q = U.A. ∆tm
Q
A = U×∆
tm
2, 600,000
= 1000 × 22.7 = 114.5 m
2
Say 116 m2
* Considering urea wt. in ammonium carbonate soln. undecomposed in preceding steam distiller.
1000 Kcal
U = (assumed) which will be verified.
m 2 .hr.°C
Considering 10 × 1.5 tubes, triangular pitch = 15 mm and Tube length of 6000 mm (commercially
available):
116
No. of tubes = 11 . 8.5 × 10 −3 . 6 = 724 tubes say 730
Total pipe cross sectional area

Π
= 730 × (0.7) 2 = 280 cm 2
4
(Considering effective i.d. as 7mm due to fouling.)
Flow of soln wt
Mass velocity in tubes =
Sectional area
38000
= = 135.7 Kg/cm 2 hr
280
No oversizing considered as steam press. in shell is considered as 7 Kg/cm2 abs.
(c) Velocity of Soln. in tubes:
Soln. flow rate = 38000 Kg/hr
Density of Soln. = 1100 Kg/m3 (assumed)
38000
Volumetric flow = = 34.54 m3 / hr
1100
Pipe passage area = 280 cm2 = 0.028 m2
34.54
Velocity of Soln. = = 1233 m/hr = 0.342 m/sec
0.028
(d) Determination of shell inside diameter:
From Table in Borsig Pocket book data in Fig. 3 in Ch-2 we have the eqn. for triangular pitch
corresponding to 730 tubes.
D'
= 28.21
t
where D' = C.L. distance of tubes in center line of H.E.
t = tube pitch
D' = 28.21 × 15 = 423.15 mm
Also D' = Di – 2a – tube o.d.
where D i = shell diameter
a = tube o.d.
Then Di = D' + 2a + tube o.d.
= 423.15 + 2 × 10 + 10
= 453.15 mm = 460 mm say.
(e) Baffles:
Segmental cut baffles are considered,
Min. placement of baffles should be 1/5th of shell i.d.
= 1/5 × 460 = 92 mm
Actual baffle spacing considered = 300 mm
6000
No. of baffles = − 1 = 20 − 1 = 19 nos
300
(f) φ, (shell dia) = 460 mm
460 460
No. of pipes in center = = = 30.66 say 30
pitch 15
Total sectional area of exchanger shell
Π
= × (0.46) 2 = 0.166 m 2
4
II
Area occupied by pipes = × (10 × 10 −3 ) 2 . 730 = 0.0573 m2
4
Passage area of steam in shell = 0.1087 m2
Sectional area for steam passage perpendicular to the tubes is
0.30 (0.460 – 30 × 10 × 10–3) = 0.30 (0.460 – 0.30)
= 0.30 × 0.16 = 0.048 m2
2,600,00
steam flow =
Latent heat at 7 Kg/cm 2
2, 600, 00
= = 5264 Kg/hr
493.9
Sp. Volume of steam a at 13 Kg/cm2 abs.
= 0.1541 m3/Kg
Volumetric flow of steam = 5264 × 0.1541 = 811 m3/hr
Steam velocity perpendicular to tubes:
811
V = = 4.69 m/sec
3600 × 0.048
(g) Baffle cut (segmental)
0.166
AT = 0.048 × = 0.0733 m 2
0.1087
R = 0.230 m
R2 = 0.0529
H eat Exchanger Baffles
(i) Annular Type:
D A i = 0.785 (φi)2
a = 0.785 (d) 2
A = 0.785 (D )2
a = A = 1/3 A i
d = φi / 3
φi D = φi / 3/2
(ii) Segm ental C ut Type:
At H
R Baffle spacing should be m in.
O n shell dia.
φi Tube Length
–1
N o. of Baffles =
spacing
Area occupied by pipes = xi and Area of id of shell = X

Free area = X–xi.
Assum e H at 25% or 30% cut, Find H /R and A t /R 2
Basis: Area of passage of shell side fluid perpendicular
to the pipes shall be nearly equal to area of passage of
shell side fluid parallel to the pipes.
Fig. 2
AT 0.0733
2 =
= 1.38
R 0.0529
H
Assuming = 0.7
R
H 0.7R 0.7 × 0.23
= = 0.35
φ1 = 0.460 0.46
H = 0.35 × φ1 = 0.35 × 0.46 = 0.161 m say 160 mm
160
% baffle cut = × 100 = 34.8% say 35%
460
(h) Verification of overall heat transfer co-eff:

(a) Shell side (steam) film co-eff:
0.8 0.4
λ  Dvρ  C µ
u0 = 0.023 × ×  × P 
D0  µ   λ 
Dvρ
Re. no. =
µ
here D0 = 10 × 10–3 m
1
ρ =
sp. vol. of steam at 7 kg/cm 2 a
= 3.60 kg/m3
µ = abs. viscosity of steam at 164°C = 0.015 cp
= 0.015 × 10–3 kg/m.sec.
10 × 10−3 × 4.69 × 3.60
Re. no. = = 11256
0.015 × 10−3
Now (11256)0.8 = 0.8 log 11256 = 1742
CP µ
Pr. no. =
λ
here λ = Thermal conductivity of steam
= 0.0199 B.T.U./hr.ft°F
= 0.0199 × 1.488 Kcal/hr.m°C
= 0.0296 Kcal/hr.m°C
CP = Specific enthalpy of satd. steam at 7 ata
= 659.5 Kcal/kg (considered because the steam is condensing)
659.5 × 0.015 × 10 −3 × 3600
Pr. no. = = 1203
0.0296
Now (1203)0.4 = 17.06
λ 0.0296
= = 2.96
D0 10 × 10 −3
u0 = 0.023 × 2.96 × 1742 × 17.06
= 2023 Kcal/hr.m2°C
(b) Tube side (carbonate soon) film co-eff:
0.8 0.3
λ  Di vρ  C µ
u1 = 0.023 × ×  × P 
Di  µ   λ 
Here D i = Tube id, m, 7 × 10–3

v = Vel. of soln. = 0.342 m/sec
ρ = 1100 kg/m3
µ = 0.8 CP = 0.8 × 10–3 kg/m.sec
CP = 0.8 Kcal/kg°C
λ = Thermal conductivity of soln. = 0.45 Kcal/hr.m°C
λ' = T.C. of metal tube
= 14 Kcal/hr.m°C
Di vρ
Re. no. =
µ
7 × 10−3 × 0.342 × 1100

= = 3282
0.8 × 10−3
(Re. no.)0.8 = (3282)0.8 = 650
CPµ
Pr. no. =
λ
0.8 × 0.8 × 10 −3 × 3600
= = 5.12
0.45
(C P µ) 0.3
= (5.12)0.3 = 1.63
λ
λ 0.45
Also, = 7 10 −3 = 64.28
Di ×
ui = 0.023 × 64.28 × 650 × 1.63 = 1565 Kcal/m2hr°C
(c) Wall resistance,
t 1.5 × 10−3
= = 0.1071 × 10−3 m 2 hr°C/Kcal
λ′ 14
where t = tube thickness, mm
λ' = T.C. of metal wall
(d) Fouling resistance:
m 2 . hr . °C
Total considered = 0.0003
Kcal
Overall co-eff of heat transfer U,
1 1 1 t
= + + + total fouling resistance
U U 0 Ui λ ′
1 1
= + + 0.1071 × 10 −3 + 0.0003
2023 1565
= 0.00049 + 0.00064 + 0.00010 + 0.0003

= 0.00153
1
U = = 653.6 Kcal/hr.m 2 .°C
0.00153
Remarks: Another trial needed with rev. thermal conductivity of steam at 7 ata.
Eqns. for annular baffles, if considered :
6000
No. of annular baffles reqd. = = 8 −1 = 7
750
Baffle spacing considered = 750 mm
We have, Ai = area of shell
Π
= × 0.4602 = 0.1697 m 2
4
Π
a = area of annulas = × d2
4
Π
A = area of disc = × D2
4
1 1
Also a = A= A i = × 0.1697 = 0.0565 m 2
3 3
φi 0.460
d = = = 0.265 m2
3 1.732
φi 0.460
D = = = 0.375 m2
3/ 2 1.2249
For symbols see Fig. 2
(e) Nozzles of H.E
(i) Soln. inlet 38000 Kg/hr
Velocity = 1.3 m/sec
38000
Flow = = 36.2 m3 / hr (den. = 1050 Kg/m3 )
1050
Nozzle size = DN 100
(ii) Soln. outlet flow as per material balance
30.9
= 4360 + = 4388 m 3 /hr
1.1
Velocity = 18 m/sec
(iii) Steam inlet

Steam flow = 5264 Kg/hr
Sp. Vol. = 0.1541 m3/Kg
Vol. flow = 811 m3/hr
Velocity = 14 m/sec
(iv) Condensate outlet
Flow = 5.264 m3/hr
Velocity = 0.78 m/sec.
3.3 Combustion Calculation for NG Fired Boiler Furnace:
Problem–120 ton/hr. steam generation at 90 kg/cm2. Pressure 350°C with NG (mainly CH4)
having NCV = 9001 Kcal/Nm3. Calculate the NG flow rate, gas composition and flow rates for fan
and chimney ratings. Consider 80% combustion efficiency.
Enthalpy of steam = 706.9 Kcal/Kg
Total heat in steam = 120 × 103 × 706.9 = 84.83 × 106 Kcal/hr.
84.3 × 106
NG flow reqd. = = 11.78 × 103 Nm3 /hr
0.8 × 9001
11.78 × 103
Kg moles of NG burned = = 525.9 Kg moles
22.4
Products flow and composition
Reaction: CH4 + 2O2 = CO2 + 2H2O
1 mole 2 moles 1 mole 2 moles
Reactants Calculation Moles Products Calculations Moles % Dry
CH4 - 525.9 CO2 - 525.9 11.11
O2 (5% 525.9 × 2 × 1.05 1104.4 H2O 2 × 525.9 1051.8 -
excess air)
N2 525.9 × 2 × 1.05 × 79/21 4154.6 O2 2 × 525.9 × 0.05 52.59 1.11
N2 - 4154.6 87.78
Total moles (dry) 4733.09
Total moles (wt.) 5784.89
Expected flue gas composition (dry):
CO2 = 11.11% vol.
O2 = 1.11
N2 = 87.78
Fan and chimmey flow rates considering temp. 25°C:

273 + 25
Methane flow = 525.9 × 22.4 ×
273 + 0
= 12859 m3/hr at 1.033 Kg/cm2 and 0°C
Air flow rate
100 298
525.9 × 2 × 22.4 × × = 122466 m3/hr at 1.033 Kg/cm2 and 0°C
21 273
273 + 210
flue gas (wet) flow rate = 5784.89 × 22.4 × 273 + 10
= 229259 m3/hr at 1.033 Kg/cm2 and 210°C
Fans and blowers need to be sized as above with safety margins.
Dew pt. of waste flue gas:
Partial pressure of water in fuel gas
1051.8
= × 1.033 = 0.1878 Kg/cm2 a
5784.89
Corresponding to partial pressure of 0.1878 Kg/cm2 a, Dew point from steam table is 58.5°C.
3.4 Run-off Rate of Rain Water in cft/sec
Ramser formula: Q = G.C.A.
where G = rainfall in inches/hr
run off rate
C = run-off co-eff =
rain fall rate
(1 in 5 or 5 in 10 slope and agri. land, the co-eff is approx. 0.50 or 0.60)
A = area of rainfall acres
Q = Run-off rate, cft/sec
3.5 Bubble Cap Plate Tower
Formula for gas velocity per cap
For triangular slots:
NC
 B  2g
V = 0.001068   × h05/ 2
 2A  ρ
where V = Gas volume per cap, cft/sec
N = No. of slots per cap
C = orifice co-eff (0.51)
W = width of slot, in
A = ht. of triangular slot, in
B = Base of triangular slot, in
ρG
ρ = (ρ − ρ ) where ρG and ρL are densities of gas and liquid/ft3
L G
g = 32.2 ft/sec2
h0 = slot ht., in
Ref : Cross and Dryder (1952)
3.6 Bernoulli’s Theorem for Determination of Pumping Head Reqd. in Fluid Flow
The theorem is based on the principle of conservation of energy as applied to flow of fluids,
between points 1 and 2; the theorem gives the overall equation as:
Static head + velocity head + Pressure head + Friction head
= work input by the pump + external heat input
V22 − V12
or, H2 – H1 + + P2 – P1 + F = W + Q
2g
where, H2 and H1 = static head in ft from an arbitrary horizontal datum

V2, V1 = linear velocity, ft/sec
P2, P1 = Pressure of fluids. lbs/ft2
F = Friction drop, ft of fluid
and W = Work input, ft-lb/lb
Q = External heat input Btu/lb
3.7 Friction Drop is Usually Calculated from Fanning Eqn.
In a circular cross section of pipe at isothermal condition. The determination of fanning friction
factor, f depends on Reynolds no.
2 f LV 2 2 f LG 2 4 f LH V
We have, F = = =
gc D gc .Dρ2 D
DVρ  DG 
The Reynolds no. or   is determined so as to ascertain whether the flow is
µ  µ 
turbulent (Reynolds no. > 4100) or the flow is in streamline zone (Reynolds no. < 2100 or in the
transition zone, Reynolds no. in between 2100 – 4100). The friction factor, f is determined from
Fanning friction factor chart in Perry’s Chemical Engg. Handbook.
The nomenclature of above equation is as follows:
F = Pipe friction loss, ft of fluid
f = Fanning friction factor as per Reynolds no. from
Chart in Perry
L = Length of pipe, ft
V = Linear velocity of fluid, ft/sec
G = Mass velocity of fluid lb/sec.ft2

gc = gravitational constant, 32.2 ft/sec2
HV = velocity head, ft
µ = viscosity of fluid at pumping temp. CP/1488 lb/ft.sec
D = pipe dia., ft, ρ = Fluid density, lb/ft3
An alternate simplied formula has been given in Perry’s handbook when Reynold is > 4100 as:
0.27
 µ 
f = 0.0014 + 0.090   consideration of velocity,
 DG  roughness factor is reqd.
Often two unknown quantities, viz. pipe dia. and F are involved when a trail and error method
is to be adopted by assuming the pipe dia and then calculation of the F; pipe dia. can be assumed
from chart for economic pipe dia. chart. The standard equivalent length tables, should be used for
fittings.
3.8 Estimation of H.E areas and volume of a vessel when these figures are known for a certain
plant capacity for area/volume at some other capacity of an identical new plant by the rule of
three.
We have the equation,
S2
A2 = A1 ×
S1
Where, A2 = Area or volume in metric units for new plant of capacity S2
A1 = Area or volume in metric units for known plant capacity, S1
S 2 = New plant capacity/annum or day
S 1 = Known plant capacity/annum or day
3.9 Estimation of nozzles of equipment of a plant: when plant capacity and nozzle diameter, are
known,
S2
d2 = d1
S1
Where, d1 = Nozzle size in mm or inch for known plant capacity, S1
d2 = Nozzle size in mm or inch for a new identical plant capacity
S 1 = Known plant capacity or nozzle size
S 2 = New plant capacity or nozzle size
3.10 Six Tenth Rule
By this rule approximate estimated cost of a new plant or equipment can be determined based
on FOR/FOB costs when cost of an identical plant or equipment is known.
0.6
 S2 
C2 =   × C1
 S1 
Where, C1 = Cost of plant or equipment (known capacity or volume) of a known plant or
equipment is available
C2 = Cost of plant for a new plant or equipment for an identical plant.
S 1 = Known plant capacity or equipment size
S 2 = New plant capacity or equipment size.
3.11 Determination of Steam Jacket Pressure of a Crystallization Recirculation
Line
E.t 3 (n2 − 1)
We have, Pcr =
12r 3 (1 − v 2 )
where, Pcr = Limited ext. steam pr. Kg/cm2 a
v = Poisson ratio = 1/3
r = Radius of pipe, cm
E = Young’s modulus, 2 . 1 . 106 Kg/cm2 (steel)
t = Wall thk. of pipe, cm
n = Internal pr of circulating line, (Kg/cm2 a)
Chimney Draught
Static draught hst = H(γL – γG) mm water column (kp/m2)
where H = Chimney height . m
γL = density of air . kg/m3 at tL°C
γG = density of flue-gas. kp/m3 at an average flue-gas temperature tGM°C in chimney
The curves are valid for flue-gases produced by bituminous coal and having a density of
γOG = 1.34 kg/nm3
The cooling of flue-gases in brick chimneys may be assumed to be at the rate of 0.2 °C per metre
of chimney height.
For flue-gases produced by brown coal, wood and peat the values shown in the diagram Fig. 3
should be multipled by 1.04
G R A PH FO R C H IM N EY H T
70
0
30
400°C
60
e
0
tu r
20
Static draught h s t (m m w ater-colum n)
ra
pe
em
50
st
ga
e-
fl u
15 0
an
40
Me
30
1 00
20
10
0
0 20 40 60 80 100 120 140
C him ney H eight H (m )
Example : Chimney height H = 80 m
Average flue-gas temperature t Gm = 160°C
Static draught hst = 29 mm water-column (kp/m2)
Source : Borsig pocket book 3rd edn.
Fig. 3
Vapour Pressure of Paraffin H ydrocarbons
100
8
6
4 ne
E th y le
2
ane
10 E th
8
6
4
e
pan
2 P ro
1 e
u ta n
8 Is o b
6
e
4 u ta n
n -B
2
0.1 ne
8 e nta
n -P
6
4 e
e xan
n -H e
2 p ta n
n- He
0.01 ne
8 c ta
6 n -O e e
n an can
n- No D e 26
30
4 n- 2H
H
34
1
14
C
6H
C
2
C1
0.001
–50 –40 –30 –20 –10 0 20 40 60 80 100
Tem perature (°C )
Fig. 4
Evacuation of a Vessel as a Function of Tim e
1
0.8 V.60
Q= (–lnp)
0.6 t
0.5
0.4
0.3
0.2 Q
V =
10
0.1
Vaccuum p (ata)
0.08
0.06
0.05
0.04 15
0.03
0.02
0.01 20
.0080
.0060
.0050
.0040
.0030
2 00
50
.0020
25
150
60
30
80
70
40
100
.0015
0 2 4 6 8 10 12 14 16 18
Tim e t [m in]
Q = Effective capacity of a vacuum pump, m3/hr.
V = cubic capacity of vessel . m3
t = times . minutes
D = required final pressure . ata (note : ata-atm abs)
Example : A vessel of capacity V = 20 m 3 is required to be evacuated in 12 min to a 99.5% vaccum =
0.00516 ata. What must the hourly suction volume of the vaccum pump be ?
Pressure and time lines interest at Q/V = 26.4
Required suction volume Q = 26.4.20 = 528 m3/h
Source : Borsig pocket book 3rd edn.
Fig. 5
Chapter
7
PETROLEUM REFINERY
1. Crude oil, a mix of Paraffinic, naphthenic, aromatic and asphaltic hydrocarbons.
2. The grades are called asphaltic base 60%, paraffinic base 75%, naphthenic base 75% and
aromatic base 60% or mixed base according to residue obtained. Other impurities present are
Sulphur 0.5–3%, Nitrogen 0.1–0.5% and Oxygen compound 0.1–2% as hydrocarbons derivatives.
3. Asphalt or Bitumen is found in crudes, rich in aromatic hydrocarbons.
4. Crudes are also called wax base (>5%), asphalt base (2–5%) and mixed base (<2%).
5. Products from crude oil:
(i) N.G. casing head gas (mix of lighter hydrocarbons upto butane with N2, CO, H2S and higher
hydrocarbons.
(ii) LPG mixture of liquefied Propane and butane (C3 – C4)
(iii) Natural gasoline (from N.G. by stripping of heavier constituents.
(iv) Straight run gasoline – The yield is for Aromatics crude (6–22%) Naphthenic crude (20-
50%), Paraffinic crude (50–70%).
(v) Kerosine – 8–15% C4–C12
(vi) Gas oil (Diesel oil) – C15–C25
(vii) Paraffinic base – C5–C30
Lube oil – Deficient in hydrogen of fused ring type.
(viii) Fuel oil or heavy fuel oil.
(ix) Asphalt or Bitumen.
6. BRIEF CRUDE OIL REFINING PROCESS STEPS

Various products are separated for production of LPG, Gasoline, Kerosine, Gas oil by primary
fractionation of crude oil which is carried out in two stages called stabilization in which crude is
distilled under 3-5 atm pressure to get a top product of C4, C5 and a lighter hydrocarbons responsible
for giving high V.P and a bottom product. The bottom product is subjected to atm. pressure
secondary fractionation to get light gasoline (B.P. 170°C) as top product and naphthas (med. and
heavy) (B.P. 220°C) as side stream product and a bottom reduced crude product which is again
distilled under vacuum (sometimes with steam) to get gas oil and a residue contg. wax cut, lube oil,
fuel oil and pitch.
70
PETROLEUM REFINERY 71
This residue is further distilled under high vacuum to separate wax, lube oil, fuel oil and pitch/
bitumen.
The top product consisting of hydrocarbons upto C5 obtained in stabilization operation is further
fractionated into individual hydrocarbons (Methane, ethane, propane, N-butane, isobutene, n-pentane
and isopentane.)
The intermediate products in secondary fractionation are subjected to further refinery operation
to get purer products or new compounds.
7. CHEMICAL ENGINEERING OPERATION

System Physical treatment
1. Liq. Vapour system – Distillation
2. Liq. stream – Extraction
3. Cracking and Reforming thermal – Heat treatment and new compound
and catalytic formation
4. Plat forming – ”
5. Hydroforming – ”
6. Catalytic desulphurisation – ”
7. Alkylation and polymerization – ”
8. Isomerisation – ”
The fuels in conversion process above (3 to 6) may vary from gaseous streams to residual fuel
oil. The type of intermediate products obtained will vary depending on crude-viz a paraffinic base
crude will give a wax residue containing lube oil and an asphaltic base crude will give asphalt residue.
Cracking and reforming operations are main steps carried out either in vapour or liquid stage
thermal or catalytic cracking.
8. REFINERY CATEGORY
(a) Simple (b) Complex (c) Integrated types
Simple refinery consists of crude distillation unit, catalytic reforming units and subsequent
treatment plants. The products are mainly LPG gasoline, kerosene and ATF, diesel oils. Kerosine is
a mix of light gas oil and heavy naptha.
Complex refinery contains in addition to units in simple refinery, vacuum distillation unit for lube
oils, catalytic cracking accessories units for converting cracked gases to get improved gasoline and
ATF by alkylation and polymerization or utilization of cracked gases for manufacture of various
petrochemical and products. The feed gas is naphtha or surplus fuel oil. Bitumen manufacture is also
practiced. Integrated refinery–it is integrated to produce all types of petroleum products. These
contain elaborate vacuum fractionation units for different lube oils and followed by treatment plant,
deashphalting units, solvent (furfural) extraction and dewaxing unit. In addition, it contains all units
in complex refinery.
9. REFORMING PROCESS
Naphthas are subjected to catalytic reforming to improve antiknocking property so as to
produce higher octane value in petrol. Process involves heating naphtha under controlled condition
in presence of hydrogen (to reduce coke formation) and a catalyst is used. The process routes
available are (1) non-regenerative platinum catalyst (0.3–0.7%) platinum on silica-Alumina in H.P.
fixed bed multiple reactors. (2) Regenerative non-platinum catalyst (10% moly, or 30% Chromium)
in fluidized bed reactors and (3) using cyclic regenerative Pt. Catalyst at moderate pressure (200–
300 PSI) in fixed bed multiple reactors.
Light hydrocarbon
gases
G asoline cut
Prim ary
distillation
colum n
C rudeoil N aptha cut
feed
H eater Light gas

oil Secondary distillation
colum n
H eavy gas
Vacuum tow er oil
Long residue Bottom product

Fig. 1. Flowsheet for Primary Crude Distillation.
Catalytic Reforming Reaction
Feed naphthas are mixture of paraffins and naphthas
nC7H16 = C6H6CH3 + 4H2 ∆H + ve
Paraffins also under go isomerisation, hydrocracking and to a small extent dehydration.
n.C6H14 = Methyl Pentane isomerisation ∆H – ve
C10H12 + H2 = C6H14 + C4H10 ∆H – ve
C8H18 = C8H16 + H2
C6 naphthenes are converted to corresponding aromatics:
C6H12CH3 = C6H6CH3 + 3H2
desulphurisation also occurs
C6H6CH3 + 4H2 = C5H12 + H2S
Fluid hydroforming process is also used.
Non regenerative platinum reforming process is widely used. Thermal reforming process is
used for high octane no. Gasoline. Cracking of gas oils and fuels oils either thermally or catalytically
yields gasoline of higher octane no. using catalytic route; often thermal cracking is also done using
steam.
PETROLEUM REFINERY 73
Coking Process
The coking process is performed under extreme conditions to manufacture gas, naphtha heating
oil (mazor products) and coke from pitch and tar is used as feed stock. Coke particles and steam
are used as fluidising agent. Steam is passed at bottom of reactor to fluidise the bed. Pitch top fed
at 260–370°C in the form of a spray from top into the fluidized bed at 480–1270°C. The feed partly
vaporizes and partly collects on the coke particles. The hot pitch on the coke surfaces cracks and
vaporizes leaving a non-soluble residue, which forms coke. The vapour coke stream is passed in
cycles at the top of the reactor where entrained coke is removed. The cracked vapour is then cooled
and fractionated when a top product, containing gas, and naphtha, is obtained. The bottom product
from fluidiser containing heavy tar mixed with residual coke particles is recycled to the coking
reactor.
The stripping and fluidisation steam displaces products vapour from coke surfaces and stripped
coke, then flows to the burner at 590–650°C temp. at 5–25 Psi pressure by burning part of product
coke. There remaining coke is then returned to the reactor. The flue gases are discharged to the
atmosphere after separation of coke particles in a cyclone.
C ondenser for further
fractionation
Flare stack
G as oil
R ecycle
C oking C oking reactor

cham ber
Petroleum
coke
Feed
(Tar or pitch) Fluidiser
Steam
Air
H eavy tar and coke particles

Fig. 2. Flowsheet for Coking Process.
10. DESULPHURISATION
Sulphur is removed from low boiling distillates upto 200°C and middle distillates, 250–400°C
are stripped of sulphur by catalytic hydrodesulphurisation process by hydrogen from catalytic reforming
process or hydrogen generated in the process itself by dehydrogeneration reaction.
Alkylation is done to obtain high octane gasoline from paraffins or olefines.
Lubricating Oils
The long residue after primary distillation of crude oil is subjected to high vacuum distillation
when a short residue is obtained. The long residue constituted asphalt wax, aromatics, naphthenic
acid, dark constituents and chemically unstable compound, Good quality lube oil is made by refining
so as to remove these undesireable materials from short residue. The deasphalting step is carried out
using propane. The aromatics and resins are removed by liquid extraction. MEK/Benzene dewaxing
process or propane dewaxing process are also used.
Sweating process manufactures petroleum wax. Lubrication grease and soap grease are also
manufactured.
Bitumen soluble in CS2 is obtained from residue from asphaltic and mix base crude when used
for refining. The primary distillation of heavy long residue is heated to 300°C at atm. pressure.
Chapter
8
ACTIVE CARBON
1. INTRODUCTION
Active carbon has turbostratic carbon structure and a large porous structure with pore diameter
ranging from 1–0.8 nm (less than 2 nanometer) and specific vol. = 0.25 – 0.4 cm3/gm. It has
microcystallites–only a few layers in thickness and less than 1000 in width. The surface area is 1000
m2/gm due to high porosity, which gives it excellent adsorption capacity. All types of active carbon
has small amount of bound oxygen and H2 in the form of Carbonyl group, Carboxyl, Phenol etc.
derived from raw materials. It also contains 20% mineral salts. Convential raw materials give active
carbon a pore size 0.8–1 nm; active carbon from coke gives pore size of 0.5–0.7 nm and molecular
sieve active carbon is made from anthracite and it is having pore size of 0.2–0.3 nm. Adsorption
capacity of active carbon is determined by microscope.
2. MANUFACTURE
It involves charring of raw materials by burning depending on nature of active Carbon desired.
Low carbon raw materials used are coconut shells, saw dust, wood charcoal, bone charcoal, paper
mill waste liquor. High carbon raw materials are calcined coke/H.T. Coke and anthracite (used for
molecular sieves).
When low carbon raw materials are used, it is first charred and formed into briquettes and then
activated. High carbon raw materials, coal anthracite, are directly activated.
(a) Charring Process – It is partial oxidation of low carbon containing raw materials during
heating at temp. 600–1000°C. The carbon contents is increased to 90%. After charring, the material
is formed into briquettes for activation.
(b) Coking Process – The high carbon raw materials are sized as per requirement and heated
in a furnace in inert atmosphere (oxygen free) using CO2 gas at a high temp. ≥ 1000°C to drive
off all non carbon components of carbonaceous materials using bound oxygen for self oxidation.
3. OXIDATION PROCESS
The carbon materials are then subjected to high gas phase exposure to oxidation atmosphere
(O2, CO2) at about 200°C or alternatively the carbon materials are then treated with conventional
oxidizing agent solution.
4. ACTIVATION PROCESS
There are two processes viz.
75
(a) Gas activation and

(b) Chemical activation
There are three variables in activation process:
(i) Nature of starting materials
(ii) Composition of activation atmosphere
(iii) Time and temp. of activation process
Item (ii) and (iii) affect surface chemistry and adsorption by active carbon for various uses
and item (i) will give the nature of active carbon product.
Gas Activation Process
The carbon after coking or charring is subjected to heating at 800–1000°C in super heated
steam CO2 atmosphere or both. This results in some loss of active carbon. Before heating, usually
5% caustic potash or Pot. Carbonate is used to moisten the active carbon charge. This addition
accelerates activation process.
Side reactions H2O + C = CO + H2∆H = 117 KJ
2H2O + C = CO2 + 2H2 ∆H = 75 KJ
CO2 + C = 2CO ∆H = 159 KJ
A high degree of activation gives 20% yield of active carbon whereas a lower degree of
activation gives 60% yield.
Chemical Activation
It is done by dehydrating chemicals–starting materials phosphoric acid or ZnCl2–the latter is
used usually for chemical activation of mostly uncarbonised viz. finely divided saw dust and pit coal
mixed with phosphoric acid solution when a pulp is formed. This is then heated in a rotary furnace
to 400–600°C; the excess H3PO4 is removed by extraction, neutralized with phosphate salt and dried
up. Activation with stream and phosphoric acid also can be done. The dried up active carbon is then
coked or charred. This process is popular and economy depends on recovery or phosphoric acid.
For pharmaceutical use of active carbon low ash content active carbon is made by washing
the activated carbon with water or HCl/H2SO4. Lignite or coal base active carbon when activated by
precise thermal and chemical treatment can prduce carbon with specific pore system.
5. PROPERTIES OF ACTIVE CARBON

Apart from large pore size distribution and surface area, chemical reactivity of surface area is
important. For many applications of active carbon it does not require to reactivate the spent active
carbon but it is necessary to remove adsorbed material in order to bring carbon to its virgin form.
Adsorption from solution does not involve multilayer formation and depends on chemical
activity of surface. Adsorption for gas phase purification involves multilayer formation and capillary
condensation in pores of the active carbon. Physical properties of various active carbons are given
in (Vol.-II A).
Regeneration of spent active carbon–It is done by passing super heated steam or inert gas
through active carbon base, which takes out the adsorbed gases from intergranular spaces. Exhausted
active carbon from gas purification is heated to red heat for regeneration by decomposing the
adsorbed gases and thus desorbing the masses.
ACTIVE CARBON 77
6. USES OF ACTIVE CARBON

1. For liquid and gas purification process–active carbon is used in granular or pelletised form.
2. For molecular sieve, active carbon in proper size is made form anthracite.
3. For water purification and decolourisation, grounded active carbon is used.
4. For food processing, pelletised active carbon is used.
5. Catalyst preparation.
6. Active carbon of high ignition temp. and high resistance to abrasion is suitable for industrial
use for removing sulphur and nitrogen oxides from flue gases from power plant, separation of mixer
of gases and in solvent recovery.
7. In gold purification.
8. Active carbon is used in the manufacture of sucrose, glucose, maltose, lactose, soft drinks,
edible oils, paraffin wax, phosphoric acid, plasticizers, glycerol, gelatin, pectin, caffeine, quinine,
vitamin C, lactic acids etc. Also used in Fruit juices, wine and alcohol manufacture.
9. Powdered active carbon is also used in liquid phase reaction. Grains of active carbon are
also used in gas phase reaction.
10. For odour removal.
Chapter
9
REFRIGERATION
There are two types of refrigeration principles used in industry and domestic services:
A. Vapour compression type
B. Absorption type
A. VAPOUR COMPRESSION TYPE

In vapour compression, the refrigeration cycle works on reverse Rankine (or carnot) cycle.
The refrigerant vapour is compressed by a compressor which increases the pressure so that the
compressed vapour attains temp. higher than the cooling water or air and the vapour gives out heat
to cooling water/air thereby the vapour condenses to liquid in the condenser as the saturation temp.
is reached due to cooling.
The condensed liquid then flows through an expansion valve where partial flashing of liquid
takes place, thus cooling the remaining liquid to below the temp. of product to be cooled. The temp
difference facilitates heat to be transferred from product to refrigerant, which causes the cooling of
product and the refrigerant to evaporate. The hotter products give out heat for evaporation of
refrigerant thereby cooling the product in refrigerated space. Heat of evaporation of refrigerant is the
key factor. For refrigerators, compressor with motor is inside a sealed unit, condensation by air-
cooling and refrigerant liquid flashes in freezer body tubes. The vapour of refrigerant is removed by
compressor suction which causes the flow of liquid to maintain and also maintain low pressure in
evaporator. The simple circuit given in Fig. 1 and layout in Fig. 2.
Refrigerants
Three types–halogenated hydro-carbons, hydro-carbons and inorganic compounds. These are
generally substances having higher latent heats and low specific heats with the objective of reducing
quantity of refrigerant in circulation and minimizing losses, which occur in expansion valve and other
fittings. The boiling point of refrigerant establishes the refrigeration temp. at which it could be used
in the particular refrigeration system. Normally refrigerants are non-inflammable or slightly inflammable
and non toxic or slightly toxic.
Coefficient of performance of a refrigerant
It is the ratio of
refrigeration effect Q0
= = 5.75
Works expended Qk − Qo
78
REFRIGERATION 79
where Q0 = net heat extracted per unit mass, and

Qk – Qo = work of compression per unit mass
Fig. 1. Vapour compression refrigeration circuit.

This ratio indicates efficiency under certain conditions of the refrigerant selected. It is often
given at standard conditions i.e., –15°C (5°F) evaporation and +30°C (86°F) condensation. The
maximum value is 5.75, which is obtained on working with a, reverse Rankine cycle (or Carnot
cycle) and is independent of refrigeration. For vapour compression machine, the coefficient is of the
order of three, for air cycle refrigeration application one and for vapour absorption systems, it is well
below one.
H.P. 4.71
=
TR µe (Imp H.P.)
H.P. 4.78
and = µe (metric H.P.)
TR
Refrigerant Number R
In a numerical cooling system which defines the molecular structure of refrigerant as per
designation ABCD (applicable to halo and hydrocarbons refrigerants only where A, number of double
bonds: B, number of carbon atoms less one, C, the number of hydrogen atoms + one and D, the
number of fluorine atoms.
Example : For R-12, A = 0, B = 1 – 1 = 0, C = 0 + 1 and D = 2.
Therefore the refrigerant number becomes R-12 (Dichloro Difluoro methane.)
Inorganic refrigerants are designated differently. They are given digits number, the first is 7 and
following two numbers gives its molecular number.
Lay-O ut of a Vapour C om pression-Type R efrigeration System
Evaporator
Brine (C old)
b a R eturn
O il
Separator
c
C ooling w ater
C ondensor
C ooling w ater d
f
C ooling w ater
g
R eceiver
Suction line
D ischarge line
Liquid
(a) Float value (e) Expansion value and R efrigeration

(b) O il collector charging device C om pressor
(c) Safety oil drain (f) Liquid level gauge
(d) N on-condensable gas (g) Filter
purging device
Source : Borsig pocket book 3rd edn. 1970

Fig. 2
REFRIGERATION 81
Example : Ammonia-R 717

US’s ASHRAC standard 34–94 (2) classify refrigerants in 6 groups:
Group A1 = non inflammable and non toxic.
Group B1 = non inflammable but slightly toxic.
Group B2 = same as above but moderately toxic.
Group A3 = highly inflammable but non toxic.
Group B3 = highly inflammable and highly toxic.
Ozone Depletion
Both CFC and HFCs contribute ozone depletion in stratosphere and as a result, ozone hole was
detected in Antarctica. Ozone depletion potential (ODP) has been fixed as 1.0 for CFC–1 and all other
CFCs and HFCs are grouped accordingly.
The production of such ozone depletion compounds was decided to be phased out in 1987 as
per Montreal protocol as per the following schedule:
CFCs phase out by 1.1.96 (Developed countries)
HFCs phase out by 1.1.2020 (Developed countries).
However, developing countries were given further extension of 10-15 years from above dates.
In view of the above stipulations developed countries are on the look out for alternate CFCs and
HFCs. Some HFC refrigerants like R 134 a, hydro-carbons, propane (R-290) and ethane (R-170) are
reportedly found better replacements for CFCs and HFCs.
Table 1
Name Code Range Volume refrigerant Effect

Hydro fluoro- R-134 a –15°C evaporation 1062 (KJ/m3)
Carbons and 30°C condensation
Ethane R-170 –15°C evaporation 1811 (KJ/m3)
and 30°C condensation
Propane R-290 –15°C evaporation 2238 (KJ/m3)
and 30°C condensation
Normally mineral oil is used as a lubricant in compressor, which is miscible with refrigerant
and return back to compressor for lubrication. About 2–3% lubricating oil is reqd. Details given in
Table-5.
However, R-134a requires a synthetic oil, called polyster oil, which is miscible with refrigerant.
DIN 51503 gives refrigeration oil specification. For applications of various refrigerants see Table 126
in Vol. IIA.
Table 2
Refrigerant TLV. ppm ODP** GWP* 100 yr. Atmospheric Life yr.
CFC-11 1000 1 4000 60
CFC-12 1000 1 8400 130
CFC-13 1000 – 11700 400
HCFC-22 1000 – 1500 15
(Contd.)
(Table Contd.)
Refrigerant TLV. ppm ODP** GWP* 100 yr. Atmospheric Life yr.
HCFC-23 1000 0 – 310
HCF-134a 1000 0 1200 16
HFC-152a 1000 0 140 2
Propane (R-290) – 0 3 4
Ammonia (R-717) 25 0 1 1
*Global warming potential
**Ozone depletion potential
Units of Refrigeration
It varies from country to country. Care should be taken as to know the type of refrigeration
unit followed in the country.
A few are as follows:
1 US ton of refrigeration, TR = 200 BTU/min or 12000 BTU/hr
= 3024 Kcal/hr
1 U.K. ton of refrigeration, TR = 220 BTU/min
= 3340 Kcal/hr
1 lb/hr TR = 9 kg/hr per 1000 Kcal/hr
1 lb/min TR = 0.15 kg/min per 1000 Kcal/hr
1 BTU/min TR = 5 Kcal/hr per 10000 Kcal/hr
1 TR (Euorpe) = 211 kg/min
B. ABSORPTION REFRIGERATION
The system works on continuous basis using ammonia liquor as refrigerant. Separated ammonia
after generator and condenser is taken into expansion coils and dissolved in the absorption vessel
having water when the pressure falls. The refrigerant is separated by applying heat to refrigerator
and its water content is reduced by rectification, and then liquefied by ammonia condenser using
cooling water and collected in storage tank. The liquid ammonia is passed through expansion coils
when its pressure falls and partial flashing of liquid occurs with the fall of temp. The flashed
refrigerant cools the cooling media (brine solution) flowing in a coil in the brine cooler. The cold brine
is circulated in the storage through coils for lowering the temp. of stored products in storage
bunkers/ice plant. The vapour ammonia refrigerant, which absorbs heat from brine solution is then
absorbed in the absorber and the heat is removed by cooling water. The aq. ammonia is pumped to
exchanger and finally the strong aq. ammonia is sent to rectifier for separation of ammonia from
water. The heat required in the aq. ammonia exchanger is supplied by circulating weak aq. ammonia
from generator. The process is elaborate and generally finds use in cold storages for vegetables and
other products. In place of brine solution, calcium chloride solution is used in some process. For
evaporating temps. of secondary cooling fluids, see Table 127 Vol. IIA for properties of secondary
cooling media, Brine soln. (NaCl) and CaCl2 soln; ethylene glycol soln. etc. in vol-IIA. see Fig. 3.
N.B. (i) Safety Precaution-ISO-1662 gives safety precautions to be taken in refrigeration
systems.
REFRIGERATION 83
(ii) A heat pump (refrigeration) using a refrigerant having maximum COP in a vapour
compression circuit, pumps out 35 Kw of heat from (say) 7°C to 55°C, will consume 15 Kw of
electrical energy and gives 50 Kw of heat output.
Lay o ut of an A bsorptio n-typ e R e frigeration system
M LRV
B J
C
J
D
S J
b A RV
K d
O
d E
c
N
i i
h
L
P
F d
B rin e S o lu tion G
NH3
Liquid N H 3 H
d R
S tron g S olution g
W eak S olution
C ooling W ate r
Fig. 3
A Generator Heating Surface K Solution Receiver
B Analyzer with Rectifier L Solution Pumps
C Condenser M Rectifier
D Liquid Ammonia Receiver N Solution Heat Exchanger
E Ammonia Subcooler O Solution Preheater
(Liquid to Gas Heat Exchanger) P Solution Reservoir
F Vapour Dome R Auxiliary Solution Pump
G Evaporator RV Expansion valve
H Solution Collector LRV Solution Expansion valve
I Absorber f Flowmeter for liquid ammonia
a Heating steam admission g Drain valve for evaporator
b Condensate Outlet h Screen
c Two-cham condensate trap i Non-return valve
d Liquid Level gauge
e Flowmeter for liquid ammonia
Source : Borsig pocket book 3rd edn. 1970.
Table 3
Working and Test Pressures (above atmospheric)1)
as per DIN (Ed of May 1967)
Maximum Admissible Test Pressure Test of finished

Working Pressure for Individual Installation with
Components Air or Refrigerants
with water
Groups Refrigerant High Low High Low High Low Test Pressure
Pressure Pressure Pressure Pressure Pressure Pressure with Liquids
Side Side Side Side Side Side per AD
Kp/cm2 Kp/cm2 Kp/cm2 Kp/cm2 Kp/cm2 Kp/cm2 Pamphlets2
Carbon dioxide 95 67 142 100
Trichloro-mon- 1 1 1.5 1.5
ofluro Methane
R11
Dichloro- 13 9 20 13.5
difluoro Meth-
ane R12
1 Chloro-trifluoro 53 40 80 60
Methane R13
Difluoro mono- 16 13 24 20
chlor Methane 223) 333)
R22
Trichloro-trifl- 1 1 1.5 1.5
uoro ethane
R113
Dichloro 4.4 2.6 7 4
Tetrafluoro
ethane R114
Ammonia 16 13 24 20 Same Same 1.3 times
223) 333) max. max. max.
2 Methyl chlo- 12 8 18 12 admissible admissible admissible
ride working working working
Sulphur 9 5.4 13.5 8 Pressure Pressure Pressure
dioxide
Ethane 67 50 100 75
Ethylene 80 67 120 100
3 Propane 19 12 29 18
Isobutane 7 4.6 10.5 7
Butane 5.4 3.4 8 5
(1) Lower working and test pressure are possible in low-temperature installations, provided that the whole plant is
so designed and protected by safety that there is no risk of the specified pressure being exceeded.
(2) The pressure ratings and test pressure shown in DIN 2401 apply to pipes and fittings. Calculation of wall thickness
as per DIN 2413.
(3) Permitted in high-pressure side under arduous working conditions.
REFRIGERATION 85
Table 4
Physical Properties of Common Refrigerants
Refri- Ethane R 13 Carbon Propane R 22 Ammo- R 12 Methyl R 114 R 11 R113
gerant (R170) Dioxide nia Chloride
(R744) (R290) (R717) (R40)
Chemical C2H6 CF3Cl CO2 C3H8 CH2Cl NH3 CF2Cl2 CH3Cl C2F4Cl2 CFCl3 C2F3Cl3
Formula
Molecular 30.06 104.47 44.01 44.09 86.47 17.03 120.92 50.49 170.93 137.38 187.39
Mass
Gas consta- 28.22 8.12 19.26 19.23 9.81 49.79 7.01 16.80 4.96 6.17 4.525
nt Kpm/kg°K
Boiling –88.6 –81.5 –78.5 –42.5 –40.8 –33.4 –29.8 –24.0 +4.1 +23.7 +47.6
temp °C at
760 Torr
Soldification –183.6 –181 –58.6 –189.9 –160 –77.9 –155 –91.5 –94 –111 –36.5
Point °C
Critical temp 32.1 28.8 31.0 96.9 96.0 132.4 112.0 143.1 146 198 214.1
°C
Critical pres- 50.3 39.5 75.2 43.4 50.3 115.2 40.9 68.1 33.3 44.6 34.8
sure ata**
X = Cp/Cv 1.202 1.15 1.30 1.153 1.19 1.312 1.148 1.27 1.106* 1.124 1.075*
at 0°C
Heat of
evapora-
tion kcal/ 83.1 25.08 65.3 95.1 52.0 313.5 38.6 100.4 33.88 46.66 38.9
Kg at–15°C
Specific vol.
of saturated
Vapour 0.033 0.012 0.017 0.156 0.078 0.509 0.093 0.279 0.263 0.772 1.649
m3/kg
Density of
Liquid kg/ 0.412 1.12 0.925 0.53 1.285 0.639 1.39 0.96 1.54 0.652 1.62
at 0°C
Volumetric
Refrigerating
capacity Kcal/
m3 at –15°C
Evap. Temp.
and + 25°C
upstream of
expansion
valve 1443 1000 2434 458 519 529 319 307 89.4 51.2 18.3
From “Rules for Refrigeration Machines”, 5th Edition 1958, Veriag C.F. Muller. Karisruhe
*at +25°C **ata = atm.abs.
N.B. For vapour press.–temp. relation of refrigerants see curves in Fig. 7.
Table 5
Discharge Temperatures in Single-Stage Compression with Ammonia Compressor
Evaporation Condensing Temperature
Temperature (Discharge Gauge Reading)
(Suction Gauge °C
Reading)
°C 10 12.5 15 17.5 20 22.5 25 17.5 30 32.5 35 37.5 40
+10 10 16 22 28 35 41 47 53 58 64 70 76 82
+5 17.5 24 30 36 43 49 56 62 67 72 79 84 91
+0 26 32 39 45 52 59 65 71 76 82 88 94 100
–5 35 42 48 55 61 68 75 81 86 91 98 105 111
–7.5 40 47 53 60 66 73 80 86 91 96 103 110 117
–10 45 52 58 65 71 78 85 91 96 102 108 114 123
–12.5 50 57 64 70 77 84 91 96 102 108 114 121 129
–15 55 62 69 76 82 89 96 102 108 114 121 127 135
–20 66 73 80 87 94 101 108 115 121 126 127
–25 78 85 92 99 107 113 121 126 132 140
–30 90 97 104 112 120 127 133 140
–40 116 124 133 140
Source: Borsig Pocket Book, 3rd edition 1970.
Power Requirement for Refrigeration Plant using Reciprocating Compressor
Diagram 1 of Fig 4 shows the effective power requirement as a function of the refrigerating
capacity of single and two-stage ammonia-compressors on the basis of the following reference
conditions:
(a) Single-stage compressors:
Evaporation temperature –10°C, condensing temperature +25°C;
(b) Two-stage compressors:
Evaporation temperature –40°C, condensing temperature +30°C.
These are average value and apply approximately to other refrigerants also.
Example 1.
Given: Refrigerating capacity Q0 = 600,000 kcal/hr
Evaporation temperature = –10°C corresponding to reference
Condensing temperature = +25°C} conditions for Diagram 1 and 2
Required : Effective power requirement:
From Diagram 1 we have Ne = Nc –10 = 140 KW
Example 2.
Given: Refrigerating capacity Q0 = 600,000 kcal/h
Evaporation temperature = 0°C
Condensing temperature = +32.5°C
REFRIGERATION 87
Required : Effective power requirement:

From Diagram 1 we obtain the effective power requirement Ne (–10) = 140 KW
From Diagram 2 we find for ±0/32.5°C
Refrigerating capacity = 150%, effective power requirement = 130%
as compared with the reference values –10%, +25%. Therefore effective power requirement
140 . 1.3
Ne = ≈ 122 KW
1.5
Power Requirement For Reciprocating Compressors for Refrigeration Plant.
Diagram 1 shows the effective power requirement as a function of the refrigerating capacity of single
and two stage ammonia compressors on the basis of the following reference conditions:
(a) Single stage compressors:
Evaporation temperature –10°C, condensing temperature +25°C;
(b) Two-stage compressors:
Evaporation temperature –40°C, condesing temperature +30°C;
There are average values and apply approximately to other refrigerants also
D iagram 1
600
E ffec tiv e p ow er r equire m ent N e (K W )
500
400
300
200
N e –1 0°C
Q 0 –1 0°C
100
0
0 200 400 600 800 100 0 120 0 140 0 160 0 180 0 200 0 220 0
R efrigerating c apac ity Q 0 [10 3 kc al/h]
Fig. 4
D iagram s 2 and 3 show the percentage variation in refrigerating capacity and effective pow er requirem ent
for single-and tw o stage am m onia com pressors under operating conditions differing from the reference
conditions.
+20 Co
nd
en
+2 s in
5+ gt
em
30 pe
ra t
200 +3 ure
( °C
5+
R efrigerating capacity Q 0 [% ]
)
40
(° C )
-5
D iagram 2 150
ra tu re
C haracteristic curves of a single-stage
-7.5
m pe
am m onia refrigerating com pressor.
o n te
R eference point 100% : -10
o ra ti
Evaporation Tem perature t 0 = –10°C -2.5
100
Evap
condensing tem perature -15
t° = + 25°C -20
50 -25
Pow er R equirem ent N o. [% ]
Co
nd
200 +10 + 2 s in g te m
en
R efrigerating capacity Q 0 [% ]
-3 0 0 + pe
3 0 + ra tu re (°
-3 2 4 0 + C)
D iagram 3 .5 50
(° C )
C haracteristic curves of a tw o-stage

tu re
am m onia refrigerating com pressor. 150 -3 5

p e ra
R eference point 100% : -3 7

o n te
.5
Evaporation Tem perature t 0 = –40°C -40
o ra ti
condensing tem perature

E vap
t = + 30°C 100 0
-4 5
-50
-5 5
50
50 100 150 180

Pow er R equirem ent N o. [% ]
Fig. 5. Gives diagram 2 and 3 which shows % variation of refrigeration capacity and effective power
consumption.
REFRIGERATION 89
Example : (Cooling water running in series through condenser and absorber):

Refrigerating capacity 100,000 kcal/h Heat requirement 220,000 kcal/h
Evaporation temperature –20°C (or heating steam consumption 410 kg/h)
Cooling water temperature +20°C of heating medium 129°C.
Cooling water consumption 16 m3/h Power requirement, solution pump 2.7 KW
Fig. 6.
Vapour Pressure Curves for R efrigerants
90
70
50
40
30
20 e
ne an
le E th
E th y
10 2
CO
7 13
R 2
5 R1
4
3
3 31
2 R1
ne
pa
P ro
1
4
11
R
0.7
11
R
Vapour Pressure (kp/cm 2 )

2
0.5 SO
3
0.4 21 11
R R
22 C ritical points
0.3 R
Cl
C H3 Solidification points
0.2
0.1
0.07
0.05
3
0.04 NH
0.03
-100 -95 -90 -85 -75 -70 -65 -60 -50 -40 -30 -20 -10 0 10 20 40 60 80 100
REFERENCE BOOK ON CHEMICAL ENGINEERING
Tem perature (°C ) Fig. 7.

REFRIGERATION 91
Table 6
Procedures for Measuring Refrigerating Capacity
Type of refrige- Type of When Cooling When freezing Tolerance
rating Capacity Condenser Liquid Cold Air or ice etc.
rooms Gas Streams
As desired 1 1 1 1 ± 6%
9 ± 7%
Overall Refrigera- Water-cooled 2 2 2 ± 5%
ting Capacity without evapo- 3 3 3 ± 8%
rative effect
Water-cooled
with Evaporative 3 3 3 ± 8%
Effect
Useful 4 7 ± 10%
Refrigerating` As disired 5 6 ± 6%
Capcity 8 ± 5%
Different procedures are employed for measuring refrigerating capacity, depending on the type
of condenser and the material to be cooled.
By definition, distinction between:
(a) The overall refrigerating capacity, as the product of the refrigerant flow and the enthalpy
difference between compressor intake and condenser liquid outlet: and
(b) The useful refrigerating capacity, as the product of the flow-rate (of the refrigerant, cooling
medium, etc.) and its enthalpy difference at two points in the refrigerating plant defined in the
Contract, at which the cold is utilized.
The individual measuring procedures, together with the tolerances permitted, are shown in the
table 6 above:
1. Measurement of the overall refrigerating capacity Q0 as the product of the refrigerant flow
Gk and the enthalpy difference;
Q0 = Gk . (i1 – i3)
In this case the refrigerant flow Gk is measured by means of an orifice plate nozzle, meter, etc.
Where measurement is made on the gas side, the vapour must be superheated and as free as possible
from oil; pulsating flow is avoided. When measurement is made on the liquid side, injection must be
continuous and no displacement of the refrigerant charge must occur.
2. Determination of refrigerant flow from the condenser duty Qc, this being calculated from
the cooling water flow Gw and the cooling water temperature at the inlet and outlet (tw1 and tw2):
Qc = Gk (i2 – i3) = GwCw . (tw2 – tw1) ± Qu
Using the refrigerant flow Gk thus obtained, the overall refrigerating capacity can be then
calculated by procedure (1).
The term Qu = k.F (tm – tR) is a correction which may be positive or negative depending on
the ambient temperature tR, although as a rule it amounts to only a few percent; for this reason, the
mean condenser-wall temperature tm, needed on an average, be taken as K = 7 kcal/m2h deg C.
3. Determination of refrigerant flow from the subcooler duty QNK:

QNK = Gk (i3 – i4) = Gw . Cw (tw2 – tw1) ± Qu
The water through flow should be taken as small as possible in order to obtain a minimum
temperature difference of 3°C.
4. Measurement of the flow of cooled liquid Gs and its cooling under steady-state conditions:
Q0 = Gs . Cs (ts1 – ts2)
Measurement of the liquid flow is made by weighing or by flow-metering. At the end of the
test all temperatures should agree as closely as possible with the initial temperatures. Otherwise
correction must be made using the water equivalent of all components situated within the measuring
section: variations in the temperature difference should, however, not exceed ± 5% of the mean
value.
5. Measurement under steady-state conditions of the heat required in the cooled liquid to cancel
the refrigerating capacity:
Using steam heating, it is most convenient to weigh the condensate yield Gc per hour. The
condition ID of the steam as it enters and that of the condensate as it leaves (Ic) must be known
accurately.
Q0 = Gc (ID – Ic)
Using heating by means of water, having an inlet temperature of th1 and an outlet temperature
of th2, we have:
Q0 = Gh . Cw (th1 – th2)
If the refrigerating capacity is cancelled by means of electrical energy, the current I and voltage
U are measured. For direct current, we then have:
Q0 = 0.86 U.I.
6. Determination of the useful refrigerating capacity by heating the cooled space and measuring
the heat required under steady-state conditions:
Stable conditions must be accurately maintained for a sufficiently long period and the cold
losses must be known. This method is thus suitable for refrigerators but not recommended for large
cold-rooms.
7. Determination of the useful refrigerating capacity by measuring the air or gas flow GL and
the cooling and drying obtained under steady-state conditions.
Q0 = GL (iL1 – iL2) – GL (XL1 – XL2) iw
where
iL1, iL2 are the enthalpy of the air at the inlet and outlet, and
iw that of the precipitated, moisture
XL1, XL2 are the water-vapour content at the inlet and outlet.
This method is acceptable only if the conditions, specified in the “Regulations for Refrigerating
Machines”, are observed carefully; no great accuracy should be expected.
8. Ice-production test to determine the useful refrigerating capacity:
Q0 = GE (t1 + 80 – 0.5 tsm/2)
REFRIGERATION 93
where
t1 is the mean temperature of water when placed in the ice cans.
tsm is the mean brine temperature.
The quantity of ice GE produced per hour is obtained from the weight of the resulting ice-cubes
immediately after removal from the can, not less than 10% of the cubes being weighed on each
occasion. Strict attention must be paid for the maintenance of steady-state conditions; the brine
temperature at the end must agree exactly with that at the start.
9. If it is desired to determine the overall refrigerating capacity from the ice-product test,
proceed as under (8), In addition allowance must be made for the incidence of heat from environment
and for the heat equivalent of the work of the stirrer. The quantity of ice produced per hour is, in
this case, determined by measuring the quantity of water introduced.
Note:
The subscripts relating to enthalpy values in the refrigerant circuit are designated as follows (as
per standard rating cycle):
The subscript 1 is used for the entry of water, brine, air, etc. and the subscript 2 for their exit.
Source: “Rules for Refrigerating Machines”, 5th Edition 1958
Table 7
Oils for Refrigeration Machinery
as per DIN 51 503
1. FIELD OF APPLICATION
This Standard applies to oils suitable for use with evaporation temperatures down to –30°C.
Where even lower evaporation temperatures are involved, special agreements should be made between
manufacturer and user and these will often cover testing procedures in addition to maximum and
minimum values.
2. TERMINOLOGY
Refrigeration-type oils are lubricating oils used in refrigeration machinery and therefore exposed
to the influence of the liquid and gaseous refrigerant.
Note:
Oils for lubricating the running gear of open-type refrigeration machinery need not satisfy this
Standard provided that it is impossible for them to enter the refrigerant circuit. Such oils are covered
by DIN 51 501 and DIN 51 504.
3. CLASSIFICATION
Refrigeration oils are divided into two groups to some extent differentiated by the relevant
maximum and minimum values:
Group A
Oil for refrigeration machinery using:
Refrigerant NH3 to DIN 8960
Refrigerant CO2 to DIN 8960
Group B is obsolete, refrigerant SO2 being no longer used
Gruop C
Oils for refrigeration machinery using fluorinated and/or chlorinated hydro-carbons as the
refrigerant, e.g.,
Refrigerant R 11 to DIN 8960
Refrigerant R 21 (dichloro-monofluoro methane, CHFCl2) to DIN 8960
4. DESIGNATION
Designation of a Group A refrigeration-type oil:
Refrigeration-type Oil A DIN 51 503
5. PROPERTIES
Requirement Group A Group C Test as per:
Appearance Clear -
Flash point °C min. 160 Din 51 584
Neutralisation number 0.08
Nz, mg KOH/g oil, max. (free of mineral acid and alkali) DIN 51 558
Saponification number 0.20 DIN 51 559
Vz, mg KOH/g oil, max.
Ash, weight % max. 0.01 DIN 51 575
Able to flow in U-tube For refrigeration
at or below °C machinery with
evaporation temp.
betweeen –20°C
and –30°C –30
For refrigeration –25 DIN 51 568
machinery with eva-
poration temperature
above –20°C –20
Water content in as- Oils delivered in tank wagons should
delivered condition content no settled water after 101 of
the tank contents have been run off.
Oil supplied in drums should contain
no settled water at room temperature
Oil in small water vapour-tight barrels
should not contain more than 30 mg
of water p.kg.
Resistance to refrigera- - 96 DIN 51 593
nts (using R12) hrs.
minimum
REFRIGERATION 95
Matter insoluble in - 0.05 DIN 51 590

Freon-12 weight %,
max.
Kinematic Viscosity, For refrigeration machinery with DIN 51 561
cSt minimum evaporation temperatures between
–20°C and –30°C
33 at 20°C 76 at 20°C
10 at 50°C 17 at 50°C
For refrigeration machinery with DIN 51 562
evaporation temperatures above
–20°C –
53 at 20°C
14 at 50°C
Chapter
10
COAL TAR CHEMICALS
Coal tar obtained from coal carbonization for production of coke, is a source of various
aromatic chemicals and pitch (residue). Coke oven tar is rich in naphthalene and anthracine. The coal
gases from coke oven battery or retorts, containing tar and other chemicals are separated in stages.
The yields of tar and other coals chemicals depends on type of coal use, mode of coal carbonisation
method via continuous coke oven battery, retorts as well as type of carbonisation whether high
temperature (1200°C).
Carbonisation or low temperature carbonization (600-800°C) is used. Atmospheric distillation
of H.T. coke oven tars yields 50–60% pitch. CVR tar gives 40–50% pitch and tars from L.T.
carbonization yields 26–30%
Table 1
Composition of crude tars
Item H.T. Coke oven L.T. Coke oven CVR
Yield, Lit/Mt 26–33 75–130 70.9
Carbonisation temperature °C 1200 600–800
Density at 20°C 1.169–1.175 1.029 1.074
gm/cc
Water, wt% 2.5–4.9 2.2 4.0
Carbon, wt% 90.3–91.4 84 86
H2, wt% 5.25–5.5 8.3 7.5
N2 ,wt% 0.86–0.95 1.08 1.21
Sulphur, wt% 0.75–0.84 0.74 0.9
Ash. wt% 1.15–1.24 0.10 0.09
Toluene insoluble wt% 5.5–6.7 1.2 3.1
The chief constituent chemicals from coal tar fractionation are benzene and its homologues,
phenols, cresols, naphthalene, or carbolic oil, cresols and their homologues and anthracine from
heavy oil (green oil). Tars also contain aniline, pyridine, quinoline and thiophne. Cresols–a pale brown
yellowish liquid-become darker with age on exposure to light, contains ortho, meta and para cresols.
O-cresols-colourless Deliquescent solid become yellow on exposure to light : m.p. 30°C : m cresols
colourless or yellow liquid : m.p. 10°C. Para cresols-crystalline solid m.p. 30°C. It is a disinfectant
fluid.
96
Table 2
Fractions in continuous H.T. coke oven tar distillation
Item B.P. range °C wt% of crude tar (dry)
Crude Benzol/light oil 99–180 0.5–1.0
Phenolic/Carbolic oil 180–205 3–4
Naphthalene Oil 200–230 10–12
Wash oil (Benzole absorbing 240–290 6–8
oil/light creosote oil)
Light Anthracine oil 260–310 12–15
Anthracine oil (heavy green oil) 323–372 95
Residue-medium soft pitch – 53–58
Liquor losses – 4.5
Light oil contains benzene 65% toluene, 3%, ethyl benzene and xylene 8% and remainders are
balance items.
Primary distillation of crude tar upto 150°C yields crude benzole or light oil. Further distillation
of crude benzene will yield crude benzene, toluene and xylenes together with some higher aromatic
hydrocarbons, paraffin, naphthalene, phenol and sulphur and nitrogen compounds. Crude benzene is
further subjected to hydro refining.
Second product, naphtha and light oil from primary distillation in B.P. range of 150–200°C gives
the important products viz. pyridine bases, naphtha and coumarene resins and creosote oil residue.
Third product naphthalene oil of primary distillation in B.P. range of 200–230°C gives phenols
and naphthalene.
Fourth product wash oil of primary distillation in B.P. range of 240–290°C yields wash oil or
benzene absorbing oil.
Fifth product anthracine oil of primary distillation in B.P. ranges 260–350°C gives light
anthracine oil and heavy creosote oil.
The last fraction, heavy oil is distilled at B.P. range of 323–373°C. The residue is medium soft
pitch, having softening point (Ring and Ball method) of 60–75°C.
Pitch is a complex heterogeneous mixture of H resins 2.8–14% and M resins 3.8–28.2%.
Table 3
Type of pitch Softening point °C
Refined/base tar below 50°C
Medium soft pitch 60–75°C
Soft pitch 50–60°C
Medium hard pitch 75–110°C
Hard pitch above 140–150°C
Medium hard pitch is made by air blowing of medium soft pitch containing heavy tar oil.
Road tar : BS–1964 specifies two types of tar.
Type A for surface dressing and Type B for tar macadam. Heavy tar oil bitumen (medium soft
pitch mixture is used as a binder for stone chips in road construction and the viscosity of tar bitumen
should be 50 secs by standard tar viscometer. The disadvantage of road tar is that the temperature
difference between R and B (Ring and Ball) method of softening point and brittle point is only 46°C
due to which tar tends to flow in hot weather and suffer from brittleness in winter. Its internal
cohesive strength is low. The disadvantage of high temperature coefficient of viscosity can be over
come by blending with petroleum bitumen (pitch). Such medium soft pitch-petroleum bitumen blends
along with 1–2% PVC or certain synthetic rubber are used in advance countries for road making.
Pitch for Electrode Binder used in AI Smelter
A paste of 70% petroleum coke or pitch coke and 30% medium hard coke oven pitch was used
as electrode binder earlier. Now a days, the electrodes after binder appln. is baked at specified
temperature.
Refined tar products constitute about 10–12% of crude tar distilled. The bulk product is pitch
and creosote oil and blends of pitch and creosote oil i.e., road tar and coal tar fuels.
Table 4
Yields of Refined products from tar distillation fractions
Refined Product H.T. Coke Oven L.T. Coke Oven CVR
Wt% dry tar
Benzene 0.25–0.42 0.01 0.22
Toluene 0.22–0.3 0.12 0.22
O Xylene 0.04 0.05 0.06
m Xylene 0.11–0.2 0.10 0.13
p Xylene 0.04 0.04 0.05
Ethyl benzene 0.02 0.02 0.03
Styrene 0.04 0.01 0.02
Phenol 0.5–0.57 1.44 0.99
o Cresol 0.2–0.32 1.48 1.38
m Cresol 0.4–0.45 0.98 1.01
p Cresol 0.2–0.28 0.87 0.86
Xylenols 0.48 6.3 3.08
Tar acids (High boiling) 0.91 12.8 8.09
Naphtha 1.18 3.6 3.21
Naphthalene 9-10 0.65 3.18
α Methyl Naphthalene 0.5–0.72 0.23 0.54
β Methyl Naphthalene 1.32–1.5 0.19 0.68
Fluorine 0.88–2.0 0.13 0.51
Diphenylene Oxide 1.4–1.5 0.19 0.68
Anthracene 1–1.8 0.06 0.26
Phenanthrone 5.7–6.3 1.60 1.75
Carbazole 1.23–1.5 1.29 0.89
Tar bases 0.99–2.00 2.09 2.09
Med. soft pitch 54–60 26.0 43.7
COAL TAR CHEMICALS 99
Tar Distillation Processes

Smaller size tar distillation plants of capacity 30–70 MT/batch with fractionation column (wt.
10–30 MT) are used in small works while continuous stills of capacity 100–700 MT/day are better
to install.
Crude tar containing NH3 liquor and suspended solids, is first filtered to remove large solid
particle. The liquor is taken into tanks fitted with screen. Some light oil separates by gravity. It is
then heated in a pipe still having a brick lined rectangular chamber divided into a combustion chamber
and a convection chamber. In the combustion process, coke oven gas or heavy tar oil or fuel oil
is burnt through burners. Hot flue gases are extracted by a blower through apertures in the partition
wall and heat pipe in the chamber, carrying tar.
The exhausted gases are released through the chimney. The heating tar tubes are arranged
horizontally and parallel to the furnace walls. Normally, heating tubes consist of two separates coils–
a waste heat coil and a longer main coil. The waste heat coil is used to heat the tar upto a temperature
to vaporize moisture and light tar oils. The main heating coils may be mostly in convection chamber
or partly both in combustion and convection chamber. The tar is finally heated to 360°C when
moisture and volatile matters get separated from nonvolatile pitch. The separated tar oil is fed to a
fractionating column where distillation products of increasing B.P. range are separated by fractional
distillation followed by condensation. Instead of one distillation column a series of column is also
used. The distillation column has bubble cap type trays, 10-15" apart.
Precaution for Overheating in Pipe Still
Since tar on over heating will deposit coke due to decomposition on tube surface resulting in
blockage of flow, the tar is pumped at a back pressure of 10 Kg/sq. cm. The tubes are either
screened from radiant heat or use twin tube coils to reduce flux. Flow gas recirculation is also used
to reduce fluegas temperature. Hot pitch can also be circulated with dehydrated tar to reduce
vaporization and increase flow rate through tubes for better heat transfer.
Corrosion: Free ammonia salt decomposes to HCl after dehydration and decomposition products
of phenol attack carbon steel resulting in corrosion. Use 10% sod. carbonate soln. in crude tar fed
to minimize corrosion.
Latest designers for tar distillation plant. 1. Clairton refinery of U.S. Steel Corporation and 2.
Teer Verwertung, Germany (Koppers design).
Types of Tar Distillation Plants
Major differences in plants lie in furnace design in which crude tar is heated, either single pass
with a flash vessel or multiple pass with flash vessel, and using or no using recirculation of residue
tar and in the no. of fractionating column and their efficiencies. The processes employing the above
techniques are called pro-abid, GFT Koppers and Wilton process.
Pro-abid process: In this process, crude tar is screened in a wire mesh, treated with caustic
soda soln. and pumped through a series of heat exchangers in the furnace and through waste heat
heaters in the convection chamber. The temperature of tar increased to 150–160°C at which the tar
is fed into hydrator flash vessel where water and light oils are flashed off which are cooled,
condensed and water is decanted off from light oil in a decanter. The light oils are then returned to
dehydrator or in some cases, to distillation column as reflux. The dehydrated tar is heat exchanged
with hot pitch and sent through main furnace coil by a pump and heated to 350–400°C at 2–3 Kg/
cm2 pressure and led to a flash vessel. The super heated steam is injected into base of flash chamber.
Remaining volatile oil is degassed from tar. The mixture of steam and volatile oil is fed into fractionating
column from which various fractions are taken off and products separated out after cooling and
condensation.
To va cu u m p um p
H e a vy w a sh o il
C o oler
Light A nthrac ine O il

H eav y A nth ra cine
Vacu u m colum n
Fig. 1. Flow for Kopper’s Tar Distillation unit.

O il
N aphthaline
O il
P itc h
P itch F la sh cha m b er
Light W as h
Se con d Atm osp he ric colum n
O Il
S trip p er
First A tm o sph e ric co lu m n

D e c an ta tio n
Liq uo r
C oolers
lig h t o il
C ru d e ta r fee d
D e h yd ra to r
Fu rn a ce
COAL TAR CHEMICALS 101
Refined Products from Tar Distillation

1. Primary distillation upto 150°C gives coal tar light oil or crude benzene. Further distillation
of light oil will give benzene, toluene, xylenes together with some higher aromatic hydrocarbon,
paraffin, naphthalene and sulphur and nitrogen compounds.
The first stage of refining of benzene or light oil is a defronting process in which steam
distillation is carried out to remove compounds boiling below benzene i.e., forerunnings containing
CS2 and some low boiling unsaturated hydrocarbons and paraffins. However, in coal gas works light
oil is less suitable for production of pure benzene or toluene and is used as motor benzol with petrol
in some countries where it is allowed. Mild treatment of benzol with sulphuric acid is carried out
to reduce sulphur to 0.4% and unsaturated compounds and waste with alkali water before fractioning
column.
The defronted benzol is fractionated to produce BTX fractions and heavy fractions and further
fractionation gives pure benzene and toluene. The fraction is combined with that from first distillation
to form zylole/naphtha fraction which is then further fractionated to give various xyloles and naphtha.
However, instead of H2SO4 treatment of benzene, catalytic disulphurisation is also used in some
plant, benzene and toluene fractions are made thiophene free and benzene refined to 5–9°C freezing
point.
2. Primary fraction, distilling in the range of 150–200°C, after further refining gives Pyridine
bases, naphtha and coumarene resins.
(a) For Pyridine bases, the distillate is freed from phenols by washing with 10% Na2CO3 soln.
The dephenolated oil is treated with 25–35% aq. H2SO4 which reacts with bases to form Pyridine
base sulphate layer separated from waste oil and allowed to stand when resinous matter floats to the
surface. Steaming or boiling removes coextracted neutral oils. The soln. is then cracked by additional
NaOH, soda ash or ammonia when sodium or ammon. sulphate is formed in which pyridine bases
are substantially insoluble. The crude basis are separated either by adding solid NaOH or by azeotropic
distillation with benzene and dried.
The dried bases are then fractionated in a column, batch or continuous when various yields are
obtained (1) small quantity of pyridine water azeotrope which is returned to drying (2) Pyridine (3)
Picoline (4) mix of ρ and γ picoline fraction, and 2,6 lubidine (termed as 90/140) bases) and (5)
higher boiling mixture 99/160 and 90/180 bases–the figure 90 indicates 90% distils upto 140°C,
160°C and 180°C respectively.
β picoline can be separated by azeotropic distillation with water. The other tar bases occurring
in high boiling fractions upto 250°C viz. quinoline, isoquinoline and quinaldin. The quinoline is
separated by fractionation.
β coumarene resin- coal tar naphtha is fractionated to give a narrow boilling range fraction
(170–180°C) which is concentrated to coumarene and indene. This is treated with strong H2SO4 to
remove unsaturated compounds–washed with water and redistilled. The distillate is heated with a
catalyst, usually boron fluoride to polymerize indene and part of coumarene content. Unpolymerised
oil is drained off. The coumarene resin thus obtained varies in colour from pale amber to dark brown
and used in paints, polished and flooring colours. The product can also be called indene resins.
Primary distillation range 200–250°C produces fractions of phenol and naphthalene. Here 1st
phenols are removed from distillate and then the dephenolated oils are treated for naphthalene
recovery.
(b) Phenol Recovery

The oil is treated with some excess of 8–10% aq. soda soln. at a temperature just high enough
to prevent naphthalene from crystallising out. The phenols react with NaOH to give crude sod.
phenate, phenolate or carbolate. The crude phenolates are separated and the extracted oil, dephenolated
is steam distilled or washed with a solvent to remove neutral oils (1%) and bases (upto 0.5%). The
purified phenate is decomposed or “sprung” in a tall lower, packed with coke or steel R/Ring,
operating counter current to a gas containing 10–24% CO 2 or a gas containing 30–37% CO 2,
specially produced by calcining mix of coke and limestone in a kiln.
The product from bottom of packed tower is separated in a separating tank into two layers-
an aq. soln. bottom layer of sod. carbonate and an upper layer of crude tar acid layer. The bottom
layer is drained off.
The crude tar is further refined. Sod. carbonate/bicarbonate is then added to bottom layer from
separating tank and passed to a recausticizing tank where treatment with quick lime or slaked lime
converts sod. carbonate to caustic soda and precipated CaCO3. The regenerated caustic is recycled
for extraction of crude tar acid from fresh oil.
Subsequent refining of crude tar fraction is done in depitching column which separates oil in
the over head product containing phenol and water and residue of phenolic pitch. The overhead
product is subjected to vacuum distillation using two or more efficient columns and finally distilled
in batch still. The products obtained are pure phenol, pure orthocresol and cresylic acids (mix of
cresols and xylelols).
However, manufacturing phenol synthetically is cheaper.
(c) Naphthalene Recovery
The dephenolated naphthalene oil contains 85–95% of total naphthalene. There are two processes
for recovery of naphthalene:
(i) Old Process: The naphthalene oil is cooled slowly in open pans to ambient temperature when
crude naphthalene crystallizes and mother liquor is allowed to drain by gravity. The naphthalene
crystals are then centrifuged and then further separated from mother liquor in a hot filter pressure
at 400 atm. pressure and temperature of 60°C. This gives a naphthalene of 96% purity having
crystallization pt. 79–78.5°C. Impurities present are thionaphthlenes which cannot be separated by
distillation or crystallisation and chemical process is used for pure naphthalene.
(ii) New Process: Naphthalene oil, having paraffines substantially removed, is fed to a dehydrating
column where it is mixed with some overhead product from 2nd front column. The dehydrated
naphthalene from dehydrator column is passed to front column near top and fitted with bubble cap
plates. Components boiling below naphthalene are removed as overhead products, part of which is
sent to dehydrating column. Residue from front column goes to middle of naphthalene fractionating
column. The top naphthalene product is of hot process quality. The bottom product together with
reminder of overheads from front column is allowed to cool in pans. The crude naphthalene crystals
are drained off from pans and recycled with fresh feed.
(iii) Pure naphthalene by chemical process: The liquid naphthalene (96%) is agitated with 10%
of 94–95% H2SO4 and washed with water and alkali and further distilled in a naphthalene column
when 99% naphthalene is obtained which is cooled, crystallised and filter pressed to get solid pure
naphthalene having crystallisation point of 79–80°C.
Chapter
11
REFRACTORY BRICKS
There are various types of refractory bricks:
1. Silica bricks
2. Dolomite bricks
3. Chromite bricks
4. Chrome-Magnesite bricks
5. Alumina-Silicate bricks
6. Sillimanite bricks
7. High alumina bricks (70%)
8. Low alumina bricks (42%) or fire bricks
9. Magnesite bricks
10. 54% silica fire clay bricks
Properties, uses and raw materials for refractory bricks:
(i) Silica Bricks
Bulk density = 1.73–1.78 gm/cc
Porosity = 22–25%
Temperature = 1710°C
Uses : O.H.F. roof lining
Molasses or sulphite lye is added to ground raw materials before moulding of bricks to increase
green strength. Sulphite lye is from paper making sulphite process.
(ii) Dolomite Bricks CaMg (CO3)2
Dolomite is a mixture of Ca and Mg oxides, 25% CaO and 21% MgO. On heating the reaction
is : CaMg(CO3 )2 heat
→ CaO + MgO + 2CO2
Properties of dolomite bricks:
Uses : In cupola and rotary kiln.
103
(iii) Chromite Bricks

Avg. composition of Indian chrome ores,
SiO2 = 1.27% CaO = 0.57
Al2O3 = 12.75% MnO = 13.51
TiO2 = 0.37% Cr2O3 = 45.33
FeO = 7.12% CO2 = 0.22
Fe2O3 = 15.97% H2O = 2.67
Properties of chromite bricks:
Bulk density = 3.10 – 2.84 gm/cc
Porosity = 22%
Temperature = < 1250°C
Uses : Steel, O.H. (non ferrous), Cu converter
(iv) Chrome–Magnesite Bricks
Properties of chrome–magnesite bricks (> 50% chrome):
Porosity = 25–23%
Temperature = < 1300°C
Uses. Open hearth furnace, re-heating furnace hearth and soak pits.
(v) Alumino–Silicate Bricks (38.1% Alumina and 57.8% SiO2)
Raw materials, bauxite and fire clay
Properties of alumino – silicate bricks:
Porosity = 30–24%
(vi) Sillimanite (Al2O3, SiO2) Bricks
Properties of sillimanite bricks:
Bulk density = 2.4–2.47 (A10) and 2.5–2.58 gm/cc
Porosity = 9–13% (ASTM – A10) and 12–16% (ASTM A11)
Sillimanite mineral is found in Khasi hills of Meghalaya in India.
Uses: Glass melting tank lining.
(vii) High Alumina Bricks (70%)
Raw materials, 98% Bauxite and clay
Properties of high alumina bricks:
Bulk denisty = 2.9–2.96 gm/cc
REFRACTORY BRICKS 105
Porosity = 14 – 18% (ASTM C4)

Uses: Steel plant
(viii) Alumina Bricks (42%) or Fire Bricks
Properties of alumina bricks:
Bulk density = 1.97 (BSI code C4) gm/cc
Porosity = 19 – 22.1%
Uses. In acid Bessemer tuyers, non ferrous and glass melting furnaces and coke ovens etc.
(ix) Magnesite Bricks
Properties of magnesite bricks:
Bulk density = 2.86 gm/cc
Porosity = 14.5 – 19.8%
Temperature = >1730°C
Uses. Mostly used where resistance to strongly basic slags is required, under hearth and lining
of O.H.F. and re-heating furnace.
(x) Fire Clay Bricks (54% SiO2)
Properties of fire clay bricks
Pprosity = 16.5%
Uses: Excellent general purpose bricks for re-heating furnaces, furnace doors, boiler soaking
pit etc.
(xi) Mullite Bricks (65 – 75% Al2O3)
Properties of mullite bricks:
Porosity = 17 – 23%
Table 1
Thermal Expansion of refractory bricks
Type of bricks % Thermal expansion Clearance expansion
(200 – 1000°C) in laying
Fire Clay bricks 0.5 – 0.7 1/16" – 3/32" per ft.
Chrome bricks 0.8 – 0.9 5/32" per ft.
Chrome-Magnesite bricks 0.8 – 0.9 3/16" per ft.
Dolomite bricks 1.3 –
Silica bricks 1.2 – 1.4 1/8" – 3/16" per ft.
Shapes of Refractory Bricks

Various sizes and shapes – One size is L = 9", W = 4.5" and thickness = 3"
GLOSSARY
Flux – A chemical, which lowers the fusion point of a refractory material.
Grog – Non plastic materials, usually prefired and added to bricks to reduce drying and firing
shrinkages or to obtain special properties i.e., high thermal shock resistance.
Porocity – Ratio of volume of pores in a refractory body to the volume of entire body and
expressed in percentage.
Plasticity – It is the property of a material by virtue of which it can be shaped (moulded) into
any form and which can be retained when the pressure of moulding is released.
Green strength – The strength of ceramic body in moulded but unfired state.
Modulus of rupture – Transfer strength of material.
3 wl
Eqn. M=
2 bd 2
where w = total load, lb.
l = distance between supports, inches
b = width of test pieces inches
d = thikness of test piece, in
M = MOR, lb/in2.
Chapter
12
EXPLOSIVES AND DETONATORS
An explosion is a violent noisy outburst accompanied with sudden build up of high pressure
and release of pressure associated with a chemical change liberating heat and light.
GASEOUS EXPLOSION
A gaseous explosion is generally non-detonation type which takes place (i) when the flammable
or explosive mixture is within the flammable limits i.e., in between lower and upper limits of
explosion in air and (ii) a source of ignition in the form of (a) hot surface or (b) electric spark or
(c) spark due to friction (d) naked light or (e) ignition by shock waves.
Lower the explosive limit, greater is the explosive energy release. At near higher explosive or
flammable limit, the mixture burns with long flame. The ignition temperature of a flammable vapour
or gas depends on pressure of the gas itself. The ignition temperature decreases as the pressure of
gas/vapour increases.
EXPLOSION DUE TO PRESSURE VESSEL RUPTURE

It is a mechanical failure of vessel under pressure due to excessive pressure or corrosion,
resulting in thinning out of vessel wall/heads and the metal is unable to bear the tensile strength
required to withstand the internal pressure of the vessel. Since it is a physical explosion, no chemical
changes occurs and release of heat and light do not occur. However, for a chemical plant, the fluids
handled in many cases are flammable, which may cause generation of sparks due to friction of flying
metal objects from the ruptured vessel and its supports, hitting other objects in vicinity, causing
sparks and ignition of gases, if flammable.
DETONATION
It is caused by mere impact or detonation shock waves or electric sparks. Powerful explosives
or explosive gases having lower limit of flammability producing shock waves having very high
detonation speed, sometimes as high as MACH 10 (10 times speed of sound), due to violent changes.
The speed of shock wave is above 330 m/sec or so. In the case of ethane-air mixture, the flame
velocity is 63 cm/sec and detonation wave speed is 1734 m/sec. In detonation, shock wave initiates
chemical reaction which propagates through the explosives charge. Detonation is carried forward
on the peak of a shock wave. Gaseous detonation is dependent on pressure, volume, energy and
velocity and also the time taken for detonation. For an explosion to occur, the reaction must be
exothermic. A fraction of chemical energy is used to propagate a shock wave.
107
DETONATORS
These are devises viz. a small amount of very sensitive primary explosive charge is embedded
in a high explosive material and mechanical or electrical devices used to set off the main high
secondary explosive. Often fuse wire is used for detonation, which consists of a train of black gun
powder wrapped in tube of tissue paper or a woven waxed fabric. In mining, high explosive fuse
wire is used. Often the blasting cap of a detonator usually contains a small charge of PETN to
transmit a powerful shock wave, ignited by fuse wire and serves to touch off the primary explosive.
Gas detonation velocity is calculated from the following formula:
Det. Velocity = V1 tan θ
where V1 = volume of detonating gas
tanθ = angle of tangent to equilibrium line with no reaction curve
for detonating as per Hogoniot curve for the particular
detonating gas.
Gasoline has a detonation velocity of 1/106 meter/sec, for high explosive it is 6000–8000 m/
sec and solid propellant 1/102 m/sec. The detonation pressure may rise upto 200,000 atm. in case
of high explosives.
Table 1
Gases and other Calculated detonation Actual detonation

velocity, m/sec velocity, m/sec
2H2 + O2 2806 2819
2H2 + O2 + 5N2 1810 1822
C2H2 + O2 2960 2920
Nitroglycerine 81 80
(liquid)
TNT (solid) 6480 6700
CATEGORY OF EXPLOSIVES
EXPLOSIVES FOR INDUSTRIAL USES

Blasting gelatine – 8% nitrocellulose in nitroglycerine (mining)
Other explosives
TNT – Trinitro toluene; Amatol–Ammon. nitrate and TNT
ANFO – Ammon. Nitrate – fuel oil mixture (IED), Nitroglycerine [C5H5O9N3 (Liq)]
RDX – Research and Development explosive, Hexogen or cyclonite
EXPLOSIVES AND DETONATORS 109
PETN – Pentaerythritol tetranitrate

HMX – Cyclotetra methylene tetra nitramine
HMS – Hexa nitrostilbene
TATB – 1, 3, 5 triammino –2, 4, 6 trinitrobenzene
TNP – Trinitro phenol
Tetryl – (NO2)3 C6H2N(NO2)CH3 also known as Tetralite
N.B. RDX is used with wax or TNT due to high sensitive nature. Chemical name of RDX is
cyclo trimethylene trinitramine.
Table 2
Properties of Explosives
Name M.P. V.P. Crystal Detonation Lead block

O°C Pa density gm/cc velocity m/sec test 10gm, sm3
Nitroglycerine 13.5 1 1.591(liq.) 7700 520
RDX 204 0.05 1.82 8850 480
at 110°C
TNT 80.8 6 1.654 6960 300
PETN 141.3 0.1 1.77 8340 520
HMX 283 – 1.907 9100 520
TATB 7550 – 1.94 7970 –
(decom.)
TNP 122.5 1 1.767 7500 315
Tetryl 129.4 – 1.73 7570 –
Some Primary Explosives

Mercury fulminate
Lead azide
DDNP (Diazodinitro phenol)
Ammonium nitrate
Table 3
Impact Sensitivity of Secondary Explosives
Insensitive Value
TATB 72.5
TNT 1
Moderately Sensitive
TNP 0.7 – 0.9
Tetryl 0.4
HMS 0.6
(Contd.)
(Contd.)
Sensitive – high explosive

HMX, RDX 0.3
PETN 0.15 – 0.2
Nitroglycerine 0.1
Functional groups in explosives
(a) Nitro gr. – Salts of HNO3, derivatives etc.
(b) O nitroderivatives – nitroesters (RONO2) – PETN
(c) C nitroderivatives – aliphatic and cryclodiphelic nitrocresols
(d) N nitroderivatives – RDX and HMX
TREND IN THE USE OF BLASTING EXPLOSIVES

Both nitrocellulose and nitroglycerine are mixed in tankers and pumped to boreholes in open
cast mines and detonated using fuse wires.
Riot Chemicals – These are CN (chloroacetophenone), CS (ortho chlorobenzol metanitrite) and
DM (Diphenyl amino chloroarsine) – the latter being more effective than CN or CS. Riot chemicals
cause skin irritation. Tear gas contains lacrimating compounds (watering of eyes) viz Bromo acetone,
benzyl chloro acetone, ethyl iodoacetate etc. usually put in explosive shell which on firing gives out
aerosol of lacrimating compounds.
Plastic Explosive – A combination of petroleum jelly, latex and RDX, designated as C-C4 and
containing 88.3 to 91% RDX and plasticiser varies from 11.7% to 20%, 22% and 9% (C2 to C4).
Gelatin Dynamite – It contains mainly gell like mass of nitroglycerine with sodium nitrate, meal,
cotton and sodium carbonate. This high explosive can be detonated by fuse wire or a timer or
wireless signal.
Chemicals of Mass Destruction (CMDs) – SARIN, a nerve gas consists, mainly methyl
phosphonofluoridic acid and ethyl ester. Mustard gas is a blister gas, which acts as a cell irritant and
cell poison. CMDs are banned by international treaty.
Chapter
13
WATER TREATMENT
1. GENERAL
Water occurs abundantly in nature as rain water (from evaporation of water) surface water
(lake, river and sea), underground water and spring water. However, water has great solvent property
and as such it cannot be used unless suitably treated for use as potable water or process water or
boiler feed water. Pure water ionizes to a small extent and its conductivity at 18°C is 0.044 µs/cm.
Rain water, after first showers is very pure like distilled water. Underground water, which occurs
in sandy layer is clear and free from organic impurities and nitrogen compounds which are oxidized
by soil bacteria. Spring water contains some special constituents.
2. IMPURITIES
Water, depending on source, contains floating objects, fine silica (silt) which impart turbidity,
dissolved salts of Ca, Mg, Iron and often Manganese. These salts are present as bicarbonates,
Ca(HCO3)2, Mg(HCO3)2, Fe(HCO3)2 ferrous bicarbonates, as sulphates, CaSO4 and MgSO4; as
chlorides CaCl2 and MgCl2 or as nitrates Ca(NO3)2 and Mg(NO3)2. Presence of bicarbonates gives
carbonate hardness called temporary hardness, where as hardness due to chlorides and sulphates of
Ca, Mg and other compounds is known as non-carbonate hardness or permanent hardness. If no
Barium and Strontium salts are dissolved in the water the sum of temporary and permanent hardness
gives the total hardness. Typical impurities in raw water is given in table 1:
Table 1
Cationic Anionic Nonionic Gases

Minerals Alkalinity due to
Ca++ Bicarbonate Turbidity CO 2
Mg++ Carbonate and silt/mud H2 S
Na++ Hydroxide dirt colour O2
K++ SO4= organic matter Chlorine
NH4+ Cl– colloidal silica NH3
Fe++ Nitrate Micro organism and
Mn++ SiO2 Bacteria, Oil
Organic matter algae, suspended
colour vegetation
111
For converting to equivalent CaCO3 divide the Fig. for ions by its equivalent wt. of ions and
then multiply by 50 (e.g., wt. of CaCO3)
Example : (i) for 40 ppm as Ca++ ion conc., equivalent CaCO3
50
= 40× = 100 ppm as CaCO3
20
(ii) 40 ppm Ca as Ca++, divided by 20 to obtain 2 meq/lit
(meq = millieqivalent) calcium expressed as meq.
2.1 pH Value
It is hydrogen ion concentration index and indicates whether a water sample is acidic, neutral
or alkaline (basic) and how many litres, as a power 10, of a soln. contain 1 gm of hydrogen ion.
pH value of neutral water is 7 i.e., 107 lit of water contain 1 gm ion (1.008 gm) of Hydrogen ion.
The total of pH and pOH values at 23°C are always 14.
pH = 7 neutral reaction (pH and pOH conc. are same)
pH < 7 acid reaction
pH > 7 alkaline or basic reaction
pH value is temperature dependent and for neutral pure water its values are :
Water temp°C pH value
0 7.49
23 7.0
50 6.63
100 6.13
200 5.69
300 5.59
370 5.63
3. ALKALINITY
Alkalinity denotes the presence of bicarbonate of calcium, sodium, magnesium and iron, that
of soda ash (Na2CO3), potassium carbonate (K2CO3) or hydroxides (NaOH or KOH or NH4OH,
hydrazine (N2H2) and other substances. It is measured by determining p and m values by titration
of water; p value is given by (use of phenolphthalein indicator) on a 100 c.c. water sample treated
with the quantity in c.c. of 0.1 N HCl at colour change and as of m value is obtained from the
quantity in c.c. of 0.1 N HCL using methyl orange indicator at colour change. This is given in T2.
4. DETAILED PROFORMA
Detailed analysis of water, for ascertaining treatment method for process/boiler/potability, is
required to be carried out. Following detailed analysis are required for this purpose.
Physical
Colour temperature index – APHA unit
Turbidity – Jackson or APHA unit
pH
Conductivity – µs/cm
WATER TREATMENT 113
Table 2
Alkalinity of water as mg CaCO3/l
Water contains
Titration result, ml/c.c Bicarbonates Carbonates Hydroxides
p = 0, M > 0 M nil nil
p < ½ M (2p < M) M – 2p 2p nil
p = ½M (2p = M) nil 2p nil
p > ½M (2p > M) nil 2(M–p) 2p–m
p = M nil nil M
Note: p and M in ml/c.c.
Physical (contd.)
Total suspended solids, mg/lit and size range, mm
Hardness : Ca hardness as CaCO3 mg/l
Mg hardness
Temporary hardness as CaCO3, mg/lit
Permanent hardness
Total hardness
Non-carbonate hardness, as CaCO3, mg/lit
Carbonate hardness, as CaCO3, mg/lit
Nitrous nitrogen OP
Nitrate nitrogen
PP as N, mg/lit
Ammoniacal nitrogen Q
Alkalinity – in p value or M value as CaCO3 mg/lit

Total dissolved solids, mg/lit
Permanaganate value
(4 hrs at 26.6°C)
C.O.D (Chemical Oxygen Demand), mg/lit
Sulphates as CaCO3 mg/lit
Chlorides as CaCO3 mg/lit
Fluorides as CaCO3 mg/lit
Post chlorination, Cl2 content in water.
Minerals
Sodium as Na mg/lit
Magnesium as Mg mg/lit
Iron as Fe mg/lit
Copper as Cu mg/lit
Zinc as Zn mg/lit
Arsenic as As mg/lit
Lead as Pb mg/lit
Bacteriological
B.O.D5, mg/lit
(5 days at 20°C)
Total colliform as M P N/100 ml
Fecal coliform as M P N/100 ml
Note. Permanganate value gives the organic matter present in water, which is also removed by
chlorination.
Raw water having high BOD value, (over 4–6), total/MPN colliform, (10,000), fecal colliform
more than 200, higher pH (over 10), chlorides (over 600), fluorides (over 1.5), along with arsenic,
lead and zinc are not desirable for chemical treatment and to be rejected. Turbidity above 14,000 ppm
is also difficult to remove and requires presettling ponds.
5. WATER SOFTENING
A. Chemical Treatment
(i) For removing temporary hardness due to presence of bicarbonates of calcium and magnesium,
quicklime, CaO or slaked lime (hydrated lime), Ca(OH)2 is used in calculated quantities with excess
amount due to impurity. The bicarbonates react with lime (or its solution, milk of lime).
Ca(HCO3)2 + Ca(OH)2 = 2CaCO3 + 2H2O
Mg(HCO3)2 + Ca(OH)2 = MgCO3 + CaCO3 + 2H2O
2NaHCO3 + Ca(OH)2 = CaCO3 + Na2CO3 + 2H2O
CO2 + Ca(OH)2 = CaCO3 + H2O
(ii) Quantity of quick lime required for softening
If A is the temporary hardness due to calcium and B is due to magnesium expressed in
equivalent CaCO3 in mg/lit unit, then pure quick lime required for above reactions is (A+B) × 0.74
gm per m3 of raw water.
The purity of quicklime is considered to arrive at actual quantity required. Addl. quantity of
quick lime is required if alkalinity due to NaHCO3, is present. Mg alkalinity removal by slaked lime
dosing, the following reaction is also possible:
Mg(HCO3)2 + 2Ca(OH)2 = Mg(OH)2 + 2CaCO3 + 2H2O
In the above case pure quicklime required is 0.765 gm pre m3 of raw water for each mg for
Mg hardness as CaCO3 (mg/lit). Temporary hardness is removed by boiling when insoluble CaCO3
or MgCO3 precipitates:
Ca(ΗCO3 )2 →
heat
CaCO3 + CO2 + H 2 O
Mg(Η CO3 )2 →

heat
MgCO3 + CO2 + H 2 O
WATER TREATMENT 115
(iii) Permanent hardness is determined by difference between total hardness and temporary
hardness. Permanent hardness in water is due to presence of sulphates, chlorides and nitrates of
calcium and magnasium. It is removed by dosing soda ash along with slaked lime. Dual use of slaked
lime and sodium carbonate is useful to remove sulphates and chlorides of magnesium.
CaSO4 + Na 2 CO3 
→ CaCO3 + Na 2SO4
MgCl2 + Na 2CO3 + Ca(OH )2 
→ Mg(OH) 2 + CaCO3 + 2NaCl
MgCl2 + Na 2 CO3 
→ MgCO3 + 2NaCl
MgSO4 + Ca(OH)2 + Na 2 CO3 
→ Mg(OH) 2 + CaCO3 + 2Na 2S
Ca(NO3 ) 2 + Na2 CO3 
→ CaCO3 + 2 NaNO3
Calcium bicarbonate also reacts with soda ash:
Ca(HCO3 ) 2 + Na 2 CO3 
→ CaCO3 + 2NaHCO3
(iv) Quantity of pure sodium carbonate required if C is the permanent hardness due to sulphates,
chlorides and nitrates of Ca, Mg expressed as equivalent CaCO3 in mg/lit = C × 1.06 gms per m3
of water.
B. Sedimentation of Precipitates from Chemical Dosing
Ferric alum containing Aluminium sulphate and ferric sulphate is used as coagulating agent in
the clarification of water, which hastens sedimentation process of reaction products from reaction
of slaked lime and sodium carbonate. In the flocculation chamber of the clarifier, floc. formation
occurs in presence of coagulating agent, ferric aluminium. Aluminium sulphate completely hydrolyses
in water to form insoluble aluminium hydroxide, which is colloidal in nature having negative charge.
Al2 (SO 4 ) 3 + 6 H 2 O 
→ 2 Al(OH )3 + 3H 2SO 4
The precipitates from dosing reactions as above bear positive charge which attract jelly like
precipitate of Al(OH)3 to form bigger particles which settle in the clarification zone of clarifier along
with sediments present in the raw water.
Part of aluminium sulphate reacts with the calcium and magnasium in water forming Al.
Carbonate which immediately hydrolyses to Al(OH)3.
Al2(SO4)3 + 3CaCO3 = Al2(CO3)3 + 3CaSO4
Al2(CO3)3 + 6H2O = 2Al(OH)3 + 3H2CO3
The alum floc produced by coagulation being much heavier settles to the bottom of clarifier
from which it is periodically removed during blow down.
Calcium precipitate sludge, sp. gr. = 1.2 settles at 3 times faster than alum floc.
Al(OH)3 floc is formed according to alkalinity present in water after chemical dosing.
Normal alum dose required = 5 – 10 mg/lit. The min. dose is 5 mg/lit. Extent of alum dose
required is determined by jar test.
Quality of treated water: In lime soda process, total alkalinity must exceed the residual total
hardness. Carbonate alkalinity must exceed magnesium and Ca hardness. Caustic alkalinity can be
increased by increase of lime feed and carbonate alkalinity by increasing soda feed.
Table 3
Settling velocity of particles in water
Settling velocity, m/sec
Diameter of Sand Alum floc
particles Sp. gr. 2.65 Sp. gr. 1.05
mm at 20°C at 20°C
1 12 0.1
0.5 7.8 –
0.1 1.04 –
0.05 0.2 –
0.01 0.013 –
New poly electrolytes have been developed as a coagulant in mid 70’s. Though its cost is much
more than ferric alum, but quantity required is less (dose = 0.1 mg/lit or 0.1 gm/m3). It can be used
with min. alum dose and put into intake channel to flocculator after alum is added and flocculation
is started.
C. Lime Softening Process by Clariflocculator
Usually a sludge blanket type of flocculator is used for water softening. Required quantities of
lime and alum solutions were prepared based on raw water analysis and mixed with water in flash
chamber from where it is sent to central flocculator section of clarifier. This section is provided with
four paddle agitators rotating in opposite directions. Here, chemical reactions between bicarbonates
of Ca and Mg and milk of lime take place and carbonates of these salts precipitate out. The
precipitated carbonates form flocks with Al hydroxide, formed due to hydrolysis of alum become
bigger and flows to outer clarification section. The heavier flocks settle to the bottom conical portion
where the sludge blanket is formed which do not allow any flocks to leave the clarifier clear water
trickles from holes in top periphery of clarifier and is stored in storage tank.
The bottom scraper, which moves very slowly scrapes the heavy sludge, swept in towards
central sludge water discharge valve and the valve is opened usually once in a shift for sludge drain.
The success of this process depends on proper floc. formation, which depends on alkalinity present
in water after dosing of chemicals. Total sludge formation is 2.8 – 3.6 times the wt. of lime added.
The treated water is then subjected to sand gravity filtration to remove any carry over smalls of
flocks/suspended matter. Then chlorination is done in pump discharge line from filtered water storage
tank. Chlorination from large cylinder is usually done through dosing instrument. Often pre-chlorination
is required if organic matter is high.
Removal of Iron and Manganese Salts in Water
Both iron and manganese salt can be removed by aeration. Ferrous salts get oxidized to ferric
state and precipitated out:
4 Fe(HCO3 ) 2 + O2 + H2 O 
→ 4 Fe(OH) 3 + 8CO2
4 FeSO 4 + O2 + 10 H2 O 
→ 4 Fe(OH)3 + 2H2SO4
In case of high carbonate hardness, the liberated sulphuric acid is decomposed as below:
H 2SO 4 + Mg( HCO3 ) 2 

→ MgSO4 + 2H 2O + 2CO2
WATER TREATMENT 117
R iver Water Treatm ent Schem e

R iver W ater
C oarse travelling
screening
R iver w ater pum ps
R iver w ater storage
Wash Water
Fire travelling screening
Acration
(if needed)
Prechlorination
Slurry to river discharge

From chem ical Section
C hem ical m ixing

and coagulant
addition
C larifier
(Flocculator) Sludge
Wash Water
G ravity filters
C lear
Sludge
Water recycle
Process w ater Treatm ent
storage
PH correction and
Post chlorination Sanitary w ater
Water for Water to D .M . plant for

Process use boiler use
Fig. 1. Block diagram for river water treatment scheme.

In case where carbonate hardness is minor, addition of milk of lime is required to precipitate
iron, Fe(OH)2 and the hydroxide is oxidized during aeration:
FeSO 4 + Ca(OH)2 
→ Fe(OH) 2 + CaSO 4
4Fe(OH) 2 + O 2 + 2H 2 O 
→ 4Fe(OH)3
Manganese is converted into manganese dioxide by aeration:
2Mn(HCO3 )2 + O2 + 2H 2 O 
→ 2MnO2 + 4H2 O + 4CO2
2MnSO 4 + O 2 + 2H 2 O 
→ 2MnO 2 + 2H 2SO4
If carbonate hardness is high, liberated H2SO4 decomposes the carbonate as above. Otherwise
alkalinity raising agents like milk of lime is to be used. The insoluble compounds of iron and
Magnesium precipitated as above can be removed by gravity filters.
Quantity of air required for oxidation by aeration:
1 mg Fe/lit = 1 lit air/m3 water
1 mg Mn/lit = 2 lit air/m3 water
Example. For 0.2% Fe or 0.2 × 104 = 2000 ppm Fe, air required = 1 × 2000 lit/m3 or 2m/
m3 of water aerated.
If quantity of water thus treated is 300 m3/hr, air flow required for aeration = 2 × 300 or 600
m3/hr.
Note : If water contains a little O2, addln. 28 lit of air/m3 of water are to be added to form
lime anti corrosive layer to maintain pH at above 6.5.
Removal of ferrous and manganaous ions by sodium hydrogen cation exchangers is possible
if no dissolved air or oxygen is present.
E. Demineralisation by Ion Exchange Method
High quality water required for boilers and other process use, is further treated in ion exchangers
in chemical plants and power generation plants for boiler use.
Process water from water treatment plant after chemical dosing, flocculation and sedimentation
in a clarifier is further treated in demineralisation plant consisting of degassifier, pressure filter and
for removal of dissolved oxygen and carbon dioxide and finally treated in cation, anion and mixed
bed exchangers. Additional pressure filter is required in DM plant to arrest any suspended matter
from process water treatment plant.
Filtration by pr. Sand filters is carried out in filters packed with gravel (non crystalline structure
at bottom and sand layer at top). Water at 2–3 Kg/cm2 pr. is fed at the top and during its downwords
flow, fine suspended matter is arrested in sand bed and clear water is drawn from the bottom. Two
filters are required–one remains in line and other one under back washing to remove the trapped
suspended water. Depending on the capacity of DM plant, a battery of such filters is required.
F. Degasification of Water
(i) Thermal degasification of water removes dissolved gases (O2 and CO2) using live steam in
degasification tower having contact plates. The water temperature is brought to near its boiling point.
the solubility of O2 and CO2 is reduced due to heat as well as partial pressures are reduced to zero.
Thermal degasification is either carried out under vacuum through a vacuum pump or a condenser
cum ejector for exhausting liberated gases and excess steam are released from tower top. When
condenser is used inlet feed water to degasifier is preheated in the condenser for heat recovery before
it is fed to the tower from top through distributors. Pressure degasification is used mostly in power
WATER TREATMENT 119
plants using steam pressure controllers for uniform degasification temperature. In vacuum degasification,
temperature controllers are used for this purpose.
(ii) Chemical degasification of water is usually carried out after demineralization of water by
dosing N2H4, as hydrazine hydrate (purity 75% min.) to remove residual dissolved oxygen. The
mineral content of water is not increased and excess hydrazine is decomposed due to heat in boilers.
NH3 gets mixed with steam and is condensed as condensate where as N2 remains with steam and
is removed as non-condensable gases from process condensers. Hydrazine concentration required for
a typical DM plant is 2–5 ppm; the reactions are:
N 2 H 4 + O2 
→ 2H 2O + N 2
3N 2 H 4 
→ 4NH3 + N2
G. Ion Exchangers for DM water
Boilers, specially medium and high pressure boilers, require feed water of zero hardness and
free from silica. Cation exchangers, filled with suitable resins to remove all +ve ions like Ca, Mg etc.
and anion exchangers are filled with required resin for the removal of –ve ions groups including silica.
Ion exchangers contain fine granules of organic substances, which are styrene based synthetic
resins. Cation exchanger contains strong or weak acid groups and anion exchangers contain either
strong or weak basic groups. Cation exchangers are regenerated after exhaust on suitable period of
exchange of +ve ions in water by either dil. H2SO4 or HCl (5–10%) as per requirement. Similarly
anion exchanger are regenerated after exhuast by weak caustic soda solution (3–5%). After exhaustion
of cation and anion exchanger, backwash with water is carried out to remove suspended matter
followed by regeneration with acid/alkali. First rinsing with water, removes excess regeneration
chemicals and exchangers, thus regenerated, are put in line. All these operations are controlled by
timer operated control valves. Normally 1 + 1 cation exchanger and 1 + 1 anion exchanger are
required for 1 exchanger is in operation and l as stand by after regeneration.
Selection of Type Cation and Anion Exchangers Resin
Depending on the extent of hardness (temporary/permanent or carbonate hardness or non
carbonate hardness or Ca/Mg hardness) present in treated process water or underground water,
suitable type of ion exchange resins is to be selected. For medium and high pressure boiler, instantaneous
removal of silica is required in mixed bed exchanger containing both cation and anion exchange resin.
Cation exchanger (H exchange) removes alkalinity and hardness. The weak cation exchanger is
charged with H ions. All the mineral content in water is reduced by the amount of carbonate
hardness.
Decarbonation (H exchange)
Ca Ca
Mg.(HCO3)2 + A.H2 
→ 2H2O + 2CO2 + A.Mg
Na2 Na2
Regeneration:
Ca Ca
A.Mg + HCl 
→ AH2 + MgCl 2
Na2 Na2
Obtainable value : < 0.5 mval/lit
120
Flow S he e t fo r To tal D em in e ra lisa tio n a n d S ilica-R e m o val P la n t
1 3 2 m 8 9
5
4
O To ta lly
6 D em in era lise d
W a te r
U n tre a nte d W ate r

m
7
14 14 14 14 14
10 12
11 13
m m
1. W eekly acid cation exchanger 8. Strongly basic cation-exchanger

2. Strongly acid cation-exchanger 9. M ixed-bed filter
3. W eakly basic anion-exchanger 10. Acid reservoir
4. Scrubber 11. Acid-m etering pum p
5. Air blow er 12. C austic soda solution reservoir
6. Interm ediate tank 13. C austic soda solution m etering pum p
7. Interm ediate pum p 14. To neutralisation pit
Fig. 2
WATER TREATMENT 121
Quality of acid required per m3 of decarbonated water is 14 gm 100% HCl/°dH carbonate

hardness (German hardness unit).
Debasification (H exchange)
A strongly acid cation exchanger is used which is charged with H ions. All the cations contained
in water are exchanged for H ions. The resulting water contains acids corresponding the anions.
Ca Ca
Mg.(HCO3)2 + A.H2  → 2H2CO3 + 2H2CO3 + A.Mg
Na2 Na2
Ca Ca
Mg.SO4 + A.H2 
→ H2SO4 + A.Mg
Na2 Na2
Ca Ca
Mg.Cl2 + A.H2 
→ 2HCl + A.Mg
Na2 Na2
Regeneration
Ca Ca
AMg + 2HCl 
→ A.H 2 + Mg.Cl2
Na2 Na2
Quantity of acid required per m3 of debasified water is 32 gm 100% HCl/°dH cation hardness.
A.H2 stands for cation exchanger resin.
Anion Exchanger Resin (OH Exchange)
Strongly and weakly basic anion exchanger resins are used which are charged with OH ions.
This type of resins removes acidity from water.
Deacidification
Strongly basic exchanger resin;
H 2 CO3 + A.(OH) 2 
→ 2H 2 O + A.CO3
H 2SiO3 + A.(OH)2 
→ 2H 2 O + A.SiO3
Weakly basic exchanger resin:
2HCl + A.(OH)2 
→ 2H 2 O + A.Cl2
H 2SO4 + A.(OH) 2 
→ 2H 2 O + A.SO4
Regeneration with dilute NaOH solution.
A.CO3 + 2NaOH 
→ A.(OH)2 + Na 2 CO3
A.SiO3 + 2NaOH 
→ A.(OH) 2 + Na 2SiO3
A.Cl2 + 2NaOH 
→ A.(OH) 2 + 2NaCl
A.SO4 + 2NaOH 
→ A.(OH)2 + Na 2SO4
N. B: A (OH)2 stands for anion exchanger resin.
Quantity of dilute NaOH solution per m3 of deacidified water;
(i) Strongly basic, 40–60 gm NaOH 100%/°dH anion hardness.
(ii) Weakly basic, 18–22 gm NaOH 100%/°dH anion hardness.
(b) In case of total demineralization with removal of silica, the above scheme of resin usage
is slightly modified for deleting basic anion exchange resin and entirely strongly basic anion exchange
resin is used which ensures removal of SlO2 and CO2. Often due to initial CO2 content of inlet water
to DM plant, after degasser, is produced in cation exchanger from carbonate hardness; CO2 the size
of anion exchanger can be reduced and regenerating chemical requirement decreased by installing a
CO2 scrubber using air (counter current flow) to bring down CO2 content to 10 ppm (10 mg/lit).
Alternatively a mixed bed exchanger after anion exchanger contains both strongly acid cation exchange
resin and strongly basic anion exchange resin. Mixed bed exchangers are however, always used in
total demineralisation plant and a recycle condensate polishing unit (cation exchanger) is required.
The conductivity of DM water, after mixed bed in a total demineralisation plant, should be below 0.5
µs/cm and the residual silica should be maximum 0.05 mg/lit (0.05 ppm). For super-critical boiler
silica content should be about 0.01 ppm.
(c) Decarbonisaton
When only carbonate hardness is required to be removed, cation exchanger is filled with weakly
acid exchanger resin. The hydrogen carbonate cations are exchanged for H ions. Hardness of salts
imparting non-carbonate hardness and neutral salt remain in water. The mineral content of water is
reduced by the amount of carbonate hardness.
(d) Neutral Exchanger Resin (Na Exchange)
Here all Ca and Mg ions are exchanged for Na ions and thus removed. The minerals content
of the water remain unchanged.
Ca Ca
Mg.(HCO3)2 + A.Na2 
→ 2NaHCO3 + A.Mg
Ca Ca
MgSO4 + A.Na2 
→ Na2SO4 + A.Mg
Ca Ca
MgCl2 + A.Na2  → 2NaCl + A.Mg
Regeneration is by dilute sodium chloride soln.
A.Ca + 2NaCl 
→ A.Na2 + CaCl2
Mg Mg
Possible hardness obtainable depending on composition of feed water is <1.8 mg CaCO3/lit.
(e) Partial Demineralisation
Two strongly acid cation exchangers, connected in parallel – one in Na form and the other in
H – exchange form, are used. The Na exchange resin removes all Ca and Mg ions for Na ions and
NaHCO3 from Na exchanger is decomposed by the acid in H exchanger. The mineral content of
the water is reduced by the amount of carbonate hardness. Regeneration is by HCl & NaCl solutions
respectively.
(i) Series connection of exchanger. Weakly acid cation exchanger in the H form followed by
strongly acid cation exchanger in Na form, the CO2 liberated from carbonate hardness can be
removed by degassing after Na exchanger. Water quality is same as that of partial flow method.
Regeneration is by HCl and NaOH respectively.
(ii) Mixed bed exchanger. A single cation exchanger containing both weakly acid and a
strongly acid exchange resins can be used also. The quality of water is equal to that for parallel flow
WATER TREATMENT 123
method. Regeneration is 1st by dilute HCl and then by NaOH. This method is suitable for water when
non-carbonate hardness comprises 20–40% of total hardness.
(f) Condensate Polishing
For recycle of steam condensate with tolerable limits of impurities, cation exchanger, containing
strong hydrogen resin, is used. Here NH4+ ion in condensate upto a certain limit can be used.
Regeneration is by dilute acid, H2SO4 or HCl.
(g) Zeolites
Initially Na2 zeolite, a cation exchanger was developed for removal of hardness in water.
Chemically zeolite is sodium salt of aluminium orthosilicate.
Na2(Al2Si2O8) + CaCl2 
→ Ca(Al2Si2O8) + 2NaCl
After exhaustion it is regenerated with 10% NaCl soln.
Ca(Al2Si2O8) + 2NaCl 
→ Na2(Al2Si2O8) + CaCl2
6. DESALINOTION OF SEA WATER:

The process is based on reverse osmosis. In case of osmosis, water moves through a semi-
permeable membrane from a low conc. to high conc. of solute due to pressure difference caused
by solute as per Henry’s law. The osmotic pressure is the pressure required to stop the flow of
solvent through the semipermeable membrane.
In case of reverse osmosis, the barrier membrane is usually called semipermeable which is
selective so that solvent can only pass through the membrane while the solute can not pass through
the membrane. This property of the semi-permeable membrane is used in osmotic pressure filtrations.
In order to separate water from dissolved solids by reverse osmosis, the applied pressure of water,
containing dissolved solids, must be greater than osmotic pressure.
The principle of separation of salt (NaCl) from sea-water by reverse osmosis can be calculated
from the following equation;
1 FW = A.(∆P-∆π)
Where, FW = water flux through the cell, gpd/ft2 (Us gallon per day/ft2)
A = water transport co-eff, gpd/ft atmosphere
∆P = pressure difference applied across membrane, atmosphere
∆π = osmotic pressure difference across semi-permeable membrane, atmosphere
The solute flow is given by equation:
2. F S = B. ∆C
Where, FS = salt flux, gpd/ft2
B = salt transport co-efficient
∆C = C1 – C2
C1, C2 = conc. of solute at upstream & down stream of membrane respectively, lb/ft2
Sea water purification plant usually contains, sea water pumping system, filters. Reverse
osmosis battery of cells, desalted water tanks and finally vacuum distillers. Usually some salt is added
to desalted water to impart test to water.
The most critical part of the purification plant is semi-permeable membrane. Usually synthetic
poly amide (nylon fibers) is used for desalination of sea-water. For other reverse osmosis process
natural cellulose acetate or nitrate is used where feed water to cells must be acidic to prevent
hydrolysis of membrane.
Sea water desalination is suitable where fresh water source is scarce for potable water but the
cost factor is quite high. In middle east, such plants in higher capacity range are quite common.
Water Treatment by Magnetic Filtration
Raw water can be treated for separations of suspended & dissolved solids by magnetic filtration
method.
Separation method;
This resorts to magnetic seeding first and then flocculation process separates diamagnetic
suspended solids and dissolved solids.
The paramagnetic suspended solids present in fluids, minerals and pharma items as well as oils
have no magnetic seeding requirement. for separation.
Selection of magnetic filtration depends on various factors viz;
(i) Size of feed materials in water.
(ii) Relative magnetic response.
(iii) Purity requirement of treated water, feed water temperature and point of feed.
(iv) Permanganate strength.
(v) Type of feed-liquid, wet and dry.
(vi) Operating cost.
Process: Seeding of raw water with grounded Ferro magnetic particles, is done followed by
verification. Finally the water is passed through a narrow constriction in a permanent magnet where
remaining impurities are attracted and clear water is obtained.
The principal of magnetic filtration is also used for separation of Ferro magnetic particles/
pieces from ore trailing, coal & coal-washery where the above moving materials are caught using
permanent magnet hung over the conveyor.
Ionic Load
To convert load of a water sample to their ionic equivalent, no. of ions must be divided by its
(Atomic wt.)
equivalent wt. of ions. Exm. : to convert Ca+ + = 40 ppm, dividing by equivalent wt., =20,
valency
we get 2 meq of calcium.
Bacteriological contamination in raw water
Surface water often contains high micro-organisms due to contaminations with human excretion,
untreated waste from municipalities, rain water pouring into rivers/lakes etc. Under ground water is
usually free from bacteriological contamination but contains organic matter.
Quality of raw water
Item Acceptable source
Avg. B. O. D 0.75 – 1.5 mg/lit
WATER TREATMENT 125
(5 days, 30°C)
Maxm. B. O. D. 1–3 mg/lit
Avg. Colliform, MPN 0/100 ml
Maxm, Colliform 0/100 ml
pH 6 – 8.5
Chlorides < 150 mg/lit
Fluorides < 1.5 mg/lit
Arsenic 0.01 mg/lit (max)
Pb ≤ 0.1 ppm
+6
Chromium ≤ 0.05 ppm
Copper ≤ 3 ppm
Iron & Mn ≤ 0.3 ppm
Zn < 15 ppm
N.B MPN stand for most probable number
Typical analysis of safe bottled drinking water: as per IS-14543-98 as amended 2003
pH = 6.5–8.5 Mercury as Hg = ppm 0.001, max
Colour = 2, max Copper as Cu = ppm 0.05, max
–
Cl as Cl = ppm 200 max Manganese as Mn = ppm 0.1, max
=
SO4 as SO4 = ppm 200, max Zinc as Zn = ppm 5, max
-
NO3 as NO3 = ppm 45, max Aluminium as Al = ppm 0.03, max
F- as F = ppm 1.0, max Lead as Pb = ppm 0.01, max
–
HCO3 = ppm 200, max Cromium as Cr = ppm 0.05, max
Alkalinity Nickel as Ni = ppm 0.02, max
Minerals Selenium as Se = ppm 0.01, max
+
Na as Na = ppm 200, max Cadmium as Cd = ppm 0.01, max
K+ as K = ppm - Barium as Ba = ppm 1.0, max
Ca + + as Ca = ppm 75, max Phenolic compounds = ppm 0.001, max
Mg + + as Mg = ppm 30, max (as C6 H5 OH)
Fe + + + as Fe = ppm 0.1, max Arsenic as As = ppm 0.01, max
Colliform = nil Mineral oils = 0.01 ppm
TDS = ppm 500, max Anionic s. active
E. Coli, SRB etc. – absent agent as MBAS = ppm 0.2, max
Turbidity = N TU 2, max PCB = Not detectable
B. O. D5 = nil Polynuclear aromatic = No
Odour = agreeable hydrocarbons = detectable
Total pesticide residue = 0.5 µgm/1 Free chlorine = ppm 0.2, max
Single pesticide = 0.1 µgm/1 Taste = agreeable, NO2 = 0.02 ppm (max)
Arsenic Removal Process

There are several arsenic removal processes:
Process Range of removal
(i) Lime softening 0.2 to 0.03 mg/lit as As
(ii) Charcoal filtration 0.2 to 0.06 mg/lit as As
(iii) Ferric sulphide filter hydroxide 0.8 to 0.05 mg/lit as As
(iv) Co-agulation with ferric hydroxide 25 to 5 mg/lit as As
(v) Precipitation with ferric hydroxide removed upto 0.6 mg/lit as As
(vi) Micro filtration semi-permeable membrane < 0.8 mg/lit
Micro filtration removes pesticides to allowable limit as per EN standard, EN 29000. Arsenic
from arsenic bearing rocks is leached in underground waterstrata which when pumped out by tube
wells for drinking purpose cause the arsenic poisoning in humans and animals.
Chlorination of Water for Disinfection
(i) By direct injection of Cl2 from Cl2 cylinder.
(ii) By bleaching powder spreading in sand/gravel filter.
(iii) By electrolytic chlorinator.
Residual Cl2 in drinking water = 0.2 ppm
Effect of Cl2 : kills bacteria, removes bad odour, reduces BOD & decolourisation.
Water Treatment Basic
1. Turbidity – Due to presence of various sediments viz dirt, mud, clay etc. turbidity of surface
water increase in raw water. If turbidity exceeds 14000- mg/1 pre-settlement pond is necessary
before the water treatment plant, which removes 70% turbidity. Turbidity measured by
Jackson meter or APHA. After settling pond 2.5 – 5 JTU water preferred.
2. Non carbonate hardness – Due to sulphates and nitrates, soda ash removes them.
3. Algae – For prevention of greenish algae growth a 0.3% CUSO4, 5H2O soln is suitable which
acts as a biocide.
4. 1 mg/lit alum will react with 0.45 mg/lit alkalinity expressed as CaCO3 or 0.28 mg/lit lime
as CaO or 0.35 mg/lit slaked lime, Ca(OH)2 or 0.48 mg/lit Na2CO3.
5. The floc formation reaction is reversible and its formation is favorable at pH 6.8 – 7.9.
6. Presence of nitrates and nitrites may be due to decomposition of organic wastes.
7. Above 600 ppm chlorides, a salty taste is developed.
8. Fluorides > 1.5 mg/lit (as F) is undesirable as it can cause mottling of teeth at 3 ppm and
above.
9. Sand gravity filter, filtration rate is 1 m3/m2/min for a bed size of 1.15 m2 and bed depth
30–45 cm of gravel below 60–75 cm sand. Period in between backwash 24–72 hrs and
water required = 6% of filtered water.
10. Water is classified as hard if it is containing more than 120 mg of divalent ions (Ca & Mg)
per lit ( 454 mg/lit) usually expressed as CaCO3.
WATER TREATMENT 127
11. Sodium cycle ion exchange increases the soluble solids content as 2 sodium (2×23 = 46)
are substituted for one calcium (40) or one magnesium (24.3).
12. Hydrogen cycle exchanger replaces 1 calcium or 1 magnesium with 2 hydrogen and this
reduces the total solids but also reduces the pH.
13. In odour scale potable water should be less than 3.
Chapter
14
METAL CLEANING PROCESS
A. METAL DEGREASING
(a) Chemical cleaning is done by trichlorethylene or percholorethylene. Special Vat is required
with heating coils at bottom & cooling coils at top to reduce loss of chemicals due to heating during
degreasing operation. The soiled articles are dipped in the vat and heated for 10–20 minutes.
For heavily greased articles, often dipping in boiling solvent may be required. Degree of
cleanliness test is done by observing wetability, as shown in breaks or spray pattern test.
(b) Alternate to chemical degreasing by the above organic solvent, hot alkaline soln. dipping.
is also done. It is a mix of sodium hydroxide, silicates and phosphates. The soln. saponifies oils and
organic materials. The pH range of such soln. for steel is mildly alkaline or it is neutral for aluminium
& zinc alloys.
B. ACID PICKLING FOR REMOVING SCALES ON METALS

(i) Iron & steel – dilute HCl for minor scale
– hot dilute H2SO4 for thicker scales
(ii) S.S – dilute HNO3
(iii) Al alloys – dilute HF
(iv) Cu and its alloys – hot dilute H2SO4
(v) Brass – mix of H2SO4, HNO3 and little NaCl or Na2Cr2O7 & H2SO4.
C. CLEANING STEEL TUBES/PIPES FOR COMPRESSORS/PUMPS LUBE OIL

CIRCUIT AND REFRIGERATION PIPE LINES
(i) For smaller dia tubes. Dilute HCl (5–6%) is generally used at temperature of 30–40°C with
circulation. Circulation is to be maintained at least for 30 hours or more depending on rust condition.
Dilute H2SO4 (5–6%) could be used for thicker scale deposits. Heating is done by L.P steam. This
is followed by water wash, 2–3% alkali wash and again water wash.
(ii) Dipping process. For large dia steel pipes for refrigeration pipe lines, dipping in 5 – 6%
HCl or H2SO4 could be used. The after treatment with water wash, alkali wash & water wash has
to be followed.
(iii) For S.S pipes/tubes use 5–6% dilute HNO3.
128
METAL CLEANING PROCESS 129
D. ELECTROCLEANING OR CATHODIC CLEANING:

Here the non ferrous items, to be cleaned, form the cathode in water containing electroplating
bath where H2 gas scours the cathode as it evolves at cathode. Anode is made of carbon rod. The
disadvantage is that the cathode, thus cleaned, leaves the cathode surface passive due to H2 pick up.
An additional dilute HCl dip is required for the cathodic articles after electrocleaning.
Anodic cleaning is desirable for soiled ferrous materials since volume of H2 at cathode is twice
the volume of oxygen at anode. The articles to be cleaned form the anode in an electrolytic bath
containing water.
The electrocleaning D.C voltage is to suitably determined.
E. CATHODE COATING
Here the protecting materials are situated below the protected in the e.m.f series of metals.
Example- Tin plated iron. Tin, the protecting metal is placed below iron or steel in the e.m.f or
galvanic series.
F. ANODE COATING
Here the protecting material lies above the protected. Example- Nickel plated copper; Nickel,
being the protecting metal lies above copper in e.m.f series.
G. ELECTRO DEPOSITION
Resins are coated on parts forming anode while resins form the electrolyte - cathode is made
of carbon rod.
H. ANODISING
Al articles form the anode and cathode is SS or carbon rod. Oxygen liberated at anode form
an oxide coating & colour is imparted on the anodized surface from the colour put in bath. The D.C
voltages of the electrolytic bath varies for different electro cleaning or coating processes viz.
Cathode cleaning
Anodic cleaning
Cathode coating
(Tin plating on iron)
Anode coating
(Nickel plated copper)
Resin electro deposition
Anodising
Chapter
15
MANGANESE DIOXIDE
There are three types of manganese dioxides of industrial importance.
A. SPEC. OF ACTIVATED MANGANESE DIOXIDE

MnO2 = 90% wt primarily grade
H2O = 2% wt
Others = 8% wt mainly lower manganous oxides. Other critical impurities viz Cobalt, Nickel,
Copper & Molybdenum and conc. are limited to 0.001%.
Particle Size
80% < 44 µm for Leclanche cell
85% < 44 µm for Zinc. Chloride battery
Activated Manganous Ore Process (Semi-synthetic)
Manganese ore (Pyrolusite) containing 80% Mn is roasted at 600°C to get Manganic oxide,
Mn2O3 which is then reacted with hot sulphuric acid to get activated MnO2.
2MnO2 Roasting
 → Mn2O3 + 1/2 O2
Mn2O3 + H2SO4 Heat
→ MnO2 + MnSO4 + H2O
Activated MnO2
MnSO4 is separated by leaching with water and activated MnO2 is dried. Activated MnO2 is
lesser effective than chemical manganese dioxide (C M D).
B. CHEMICAL MnO2
Sedemar process for CMD: process involves step by step purification of impurities in pyrolusite
(MnO2) ore:
Pyrolusite ore → Crushing → Rotary mill drying
Partial air
Grinding → Reduction with → Rotary cooler → MnO
Heavy fuel oil H.T
→ Leaching with → Neutralisation → thickening with sludge removal
H2SO4 Na2CO3
130
→ Filtering drum → Carbonation with → Filtration in a drum filter
filter NH3 and CO2 to remove
Mn (11) carbonate
→ Drying → Roasting in shelf → Belt cooler → MnO2
roaster at 320°C Tech. grade
(MnO 1.85)
→ Oxidation reaction → washing → Filtration → Drying → CMD
with H2SO4 battery grade
(Y – MnO2)
Reactions
Heavy fuel oil burning

Reduction : MnO2 + [15 MnO2 + C15H24S2 + 7.5O2 →
Withltd.Air
15MnO + 15 CO2 + 10H2O A + 2H S]
2
Leaching : MnO + H2SO4 → MnSO4 + H2O
Na2CO3
Neutralisation : Fe2O3 + 3H2O → Fe(OH)3 + 3H+ B
for Fe2O3 precipitation
Carbonation: MnSO4 + NH3 + CO2 → MnCO3 + (NH4)2SO4 - by product
Roasting
Roasting : MnCO3 MnO1.85 + CO2
320° C
Tech. Grade
H2SO4
Oxidation : Mn1.85 + 2NaClO3 → MnO2 + Cl2 + Na2SO4
(CMD)
C. ELECTROLYTIC MANGANESE DIOXIDE (EMD)

Specification: MnO2 = 91% (wt) – Hexanal modification
MnSO4 = 1–3% – hexanal modification
Fe = 0.02%
H2O = 3–5%
Others = 0.001%
Balance = lower MnO2
Density = 4–4.3 gm/cc
Surface area = 40–50 m2/gm
Particles size = 74 µm (<200 mesh)
Manufacturing Process
Rhodochromite ore concentrate is leached with H2SO4. The acidic MnSO4 is purified by
oxidation with MnO2 and neutralized with lime to pH of 4–6 when heavy metal ions (Fe, Pb, Ni and
Co), present in ore, precipitate. H2S is often used for complete precipitation of heavy metals as
sulphide. After filtration and bringing conc. (filtrate) to 75–160 gm/lit MnSO4 and H2SO4, 50–100
gms/lit MnSO4 soln. is then electrolysed (bath). The cell consists of open steel tank lined with
hypalon, rubber or ceramic. (electrically non conducting). The anode is made of graphite, Ti or hard
lead. The cathode material is manganese.
The paraffin layer over electrolyte is used to reduce evaporation.
Electrolysis parameters :
Cell voltage = 2.2–3.0 v
Anode current density = 70–120 A/m2
Bath temperature = 90–98°C
Yield = 70–90%
EMD is deposited on anode. Cell operation is stopped when solid E M D thickness of about
20 – 30 mm is obtained at anode in 15–20 days. During electrolysis, H2SO4 conc. is increased while
MnSO4 conc. is depleted. Hydrogen is liberated at cathode.
Cell Reaction
Anode : Mn+2 + 2H2O 
→ MnO2 + 4H+ +2e
Cathode: 2H+ + 2e– 
→ H2
Mn+2 + 2H2O 
→ MnO2 + 2H+ H2
E M D after end of electrolysis is removed mechanically, crushed & thoroughly washed with
hot D.M water, dried and finally grounded. The grinded product is again mixed with water and pH
brought to 6.5 – 7 with alkali, dried to specified moisture and packed.
Modern trend is to use Ti anodes and use of passivation retardants (finally grounded MnO2,
Mn2O3 & Mn3O4) in electrolyte bath and use of current density over 150 A/m2.
Uses of Manganese Dioxides
(i) Activated MnO2 is used as a depolariser in dry cell battery.
(ii) Chemical MnO2 (CMD) is used in glass industry, drystuff and varnish. Catalysist, colouring
of bricks and ceramics, welding rod manufacture, metrological products and also as a trace nutrients
for plants.
(iii) Electrolytic manganese dioxide (EMD) is mainly used in dry cells as a depolariser and
ferites manufacture for electronics use.
Chapter
16
WIND TURBINE FOR POWER
GENERATION
In high wind areas like sea coastal places, wind power is generated in wind turbine generators
(WTG) which are usually two or three bladed; modern trend being to use two bladed WTG. Site
selection is through wind mapping of the proposed site for few years and other project related
infrastructure availability, including power evacuation through transmission lines of state electricity
board and power transmission grid.
Generally the wind turbine generator is located high at 30–50 meter above the ground level
(to have access to more wind speed for AC power generator at the WTG, (3 phase AC generator).
The AC power is converted to DC by a rectifier and stored in large Ni-Cd battery house and power
from battery is converted to AC 3 phase in inverter and transmitted to 3 phase AC transmission line
after voltage boost up to grid voltage. The battery storage is used for low demand period. Nickel
–Cadnium battery has higher cycles of operation, charge to discharge, about 2000)
The blade pitch could also be automatically adjusted to suit generation. In direct AC power
transmission, power is transmitted to step up transformer by passing rectifier battery-inverter system
or transmission to grid. A wind power generator farm requires a large area (5–6 acres/MW) as WTG
are to be placed at specified distances. The center line distance between two adjacent WTG should
be 7 times the diameter of WTG blade circles and 2 blade circles center distances should be
minimum 5 times the diameter of blade circles. The minimum wind speed required is 6 miles/hr (9.66
km/hr) and maximum wind velocity allowable is 39 miles/hr (62.79 km/hr) with alternator cut off
speed kept at 40 miles/hr (64.4 km/hr) during storm. The WTG capacity usually varies from 25 KW
to 100 KW and the minimum capacity of a wind power firm could be 250 watt and the annual power
production could be 600 thousand kilo watt-hr. The efficiency of power generation in WTG set is
only 35 to 60 percent. A constant speed WTG spills wind energy at higher wind velocity to allow
generator not to exceed rated capacity upto certain limit during storm before cut-off device is
activated for which blade pitch auto adjustment device is put in two blade turbine.
Kinetic energy of wind, E = 1/2 ρu2 where u = wind velocity in m/sec and ρ = density of air.
For two bladed generators, equation for wind power is given below:
P/AT = 1/2 u3
Since only 8/27/1 2 or 16/27 or 0.593 part of maxm. power can be extracted, the effective
equation for power:
133
Fig. 1. 2 Bladed wind turbine power generator scheme (WTG).
PM/AT = 0.593. ρ.u.3 or PM = o.593.ρ.u.3π R2

Where PM = maximum power extracted
AT = cross section area of wind stream, sq mt. (blade sweep area)
0.593 = Betz co-eff maxm., fraction of power, which can be generated
ρ = Air density (sea level), 1.221 kg/m3 (usually)
u = Initial steady state wind velocity, m/sec
P
And power co-eff cρ =
1/ 2. ρ.u 3 .πR 2
where P = power delivered to the turbine, kg-m/sec or watt
ρ = 1.221 kg/m3 density of air
u = initial wind velocity m/sec
R = radius of blade area, m
Power co-eff, is the ratio between power delivered to the turbine to the power extracted
between the cross sectional area; usually power co-eff is 0.35 to 0.60.
Note. Power density for a 4.50 m/sec wind velocity is 54 W/m2 and the same for 13m/sec wind velocity
is 150 W/m2. Power density is the power per unit cross section of wind stream.
Chapter
17
CENTRIFUGAL PUMPS
A centrifugal pump transfers the input mech. energy through a rotating impeller into kinetic
(velocity) & potential (Pressure) energy to the liquid. This addition of energy will cause it to do
work, such as flow through a pipe or rise to a higher level.
While centrifugal force developed, depends both on the peripheral speed of the impeller and on
the density of fluid pumped, the amount of energy imparted to the fluid per lb of fluid is independent
of the fluid itself i.e its density or sp. gravity so long the liquid viscosity is not higher than that of
water. Pump head is expressed in feet of fluid generated by a centrifugal pump at a given speed and
capacity is usually expressed in m3/hr or cft/sec or GPM. In determining heads, it is required to
convert pressure expressed in Psi or Kg/cm2 into feet or meter of liquid.
CAPACITY
The volume of liquid pumped, is referred to as capacity and is generally measured in gallons
per minute (gpm). Large capacities are frequently rated in cubic feet per second, or millions of
gallons per day. When referring to the pumping of petroleum oils, the capacity is sometimes specified
in barrels (42 US gal) per day.
HEAD
The height to which liquid can be raised by a centrifugal pump is called head and is measured
in feet or meter of liquid. Water performance of centrifugal pumps is used as a standard of
comparison because practically all-commercial testing of pumps is done with water.
System of heads: Head of a centrifugal pump is the energy content of the fluid expressed in ft lb/
lb.
The total head of a system against which a pump must operate is made up of the following
components.
(1) Static head.
(2) Pressure head.
(3) Friction head.
(4) Velocity head.
(5) Entrance and exit head losses.
135
Static head. It is caused by the difference in elevation. Total static head is the difference in
elevation between suction and discharge liquid levels. The static discharge head is the difference in
elevation between the discharge liquid level and pump center line. The static suction head is the
difference in elevation between suction liquid level and pump centerline. If the static suction head
is –ve the suction level is below the pump center line and it is called static suction lift.
Pressure head. It is the head due to pressure exerted by the discharge and suction points.
Friction head. Friction head is the equivalent head expressed in vertical feet of liquid pumped
that is necessary to overcome the friction losses caused by the flow of liquid through this piping
etc. Friction head depends on the type of fluid, quality of fluid, size and type of pipes and fitting
and interior conditions. Roughly it varies as the square of the capacity (flow).
Entrance and exit losses. When suction is from a reservoir, the point of connection of the
suction line and reservoir there is a loss due to sudden contraction and is called entrance loss. A
well designed bell mouth result in the lowest loss of pressure.
Likewise on the discharge side of the system when the discharge line terminates at some body
of the liquid at the end of the piping this is called the exit losses. Generally the end of the piping
is of the same size as of piping and the difference in velocity head is entirely lost. In some cases
the end of discharge piping is a long taper so that velocity can be effectively reduced and the energy
recovered.
Velocity head. It represents the kinetic energy of a liquid per unit mass of fluid at any point,
V2
expressed in ft-lb per lb of liquid of hv = When hv = vel. head in feet (ft lb/lb)
2g
V = vel. in feet/sec
g = 32.2 ft/sec2
In high head pumps the K.E involved is relatively small but in low head pumps, it is relatively
high. Thus in case of high head pumps, failure to consider it in determing head will not appreciably
effect the result.
In determining the head existing at any point, it is necessary to add the velocity head to the
pressure gauge reading as the pressure gauge can indicate only the pressure energy while the actual
head is the sum of the kinetic (velocity) and potential (pressure energy) heads. Only in case where
the suction & discharge line velocities are same (so also the velocity heads), the difference in suction
gauge and discharge gauge readings will show the total head. for a +ve suction pump.
Vapour pressure. The vapour pressure of a liquid at any given temperature is that pressure
at which it will flash into vapour if heat is added to the liquid or conversely that the pressure at which
vapour at the given temperature will condense into liquid if heat is substracted.
Total head. The total dynamic head for a horizontal centrifugal pump is defined as follows.
Vd 2 Vs2
H = Hd − H s + − + Pd − Ps
2g 2g
where Hd is the discharge head as measured at the discharge nozzle and referred to the pump shaft
center line, feet. Hs is the suction head expressed in feet as measured at the suction nozzle and
referred to the pump center line. If the suction head is –ve the term Hs the above equation is positive.
The other two terms in the above equation are the velocity and pressure head at the discharge
and suction points respectively.
CENTRIFUGAL PUMPS 137
The total dynamic head is the energy imparted to the liquid by the impeller of the centrifugal
pump. If the discharge and suction heads can not be determined separately it is done by Bernoulli’s
theorem. For complex systems involving both vacuum and pressure these are converted into absolute
pressure expressed in feet of liquid.
For a vertical pump with the pumping element submerged, the total dynamic head is given by :
Vd 2
H = Hd + H s +
2g
where Hs is the distance from the suction liquid level to the center line of the discharge elbow and
Hd is the discharge head in feet referred to the center of the discharge elbow. The last term in
equation represents velocity head at the discharge.
The various discharge and suction heads are given in figures 1 and 2.
Characteristic Curves
Rising characteristic – head rises as capacity is decreased
Dropping characteristic – head at shut off is less than that at some capacities
Steep characteristic – large head increase as the capacity is decreased.
Flat characteristic – head varies slightly with capacity.
EFFICIENCY
The degree of hydraulic and mechanical perfection of a pump is judged by its efficiency. This
is defined as a ratio of pump energy output to the energy input applied to the pump shaft. The latter
is the same as the driver’s output and is termed brake horsepower (bhp), as it is generally determined
by a brake test.
Pump output W.H.P
Efficiency = =
bhp bhp
QrH
=
550 × bhp
where Q is capacity in cubic feet per second, r is the specific weight of the liquid (for cold water
= 62.4 lb per cu ft) and H is head in fect. Qr is the weight of liquid pumped per second. If the
capacity is measured in gallons (US) per minute, equation becomes as below for water.
gpm × 8.33 × H gpm × H
e= , WHP =
60 × 550 × bhp 3960 × bhp
In above equation (gpm×H) /3960 it is the pump output expressed in horsepower and is
referred to as water horsepower (W.H.P).
If a liquid other than cold water is used, the water horse power should be multiplied by the
specific gravity of the liquid to obtain the pump output or liquid horsepower.
The pump efficiency as defined by above equation is the gross efficiency. This is used by
engineers for the comparison of performance of centrifugal pumps. Besides this, there are a number
of partial efficiencies used by designers and experts, which describe only one phase of pump
performance - hydraulic, mechanical, volumetric - and are of no interest to the users of pumps but
are important to the study of pump performance.
AFFINITY LAWS
These are based on relations between capacity, head and break horsepower. Pump head varies
directly as the square of the speed; the break horsepower varies directly as the cube of the speed
and the capacity varies directly with the speed. The affinity laws are expressed by the following
equations.
Q1 n1 H1 n12 bhp1 n13

= ; = ; =
Q 2 n2 H 2 n22 bhp 2 n23
The affinity laws apply to each point in the characteristic curves. The letter n stands for speed
and post script 1 and 2 stand for no.1 and no.2 pumps following the characteristic curves.
PUMP CONSTRUCTION
A centrifugal pump consists of a casing, impeller, casing wearing ring, gland packing, suction
and discharge nozzles and bearing supports with roller/ ball bearing. The impeller may be backward
vane type and the impeller may be open, semi closed or closed types. In backward vane impeller,
head decreases as the through put increases; for forward vane impeller, head increases as the delivery
increases. Open or semi open impeller is used for slurry handling ; for multi stage centrifugal pumps,
the stage arrangement is made in such a way that the differential pressure between any two adjoining
stage chambers is kept to the minimum possible and several low pressure running joints are to be
preferred to a few number of joints subject to relatively high pressure. Also for multi stage pump,
minimum leakage at running joints is kept and to maintain this for a long period of time and also
the sequence of stages should be such as to avoid excessive complication in the formation of inter
stage passes.
N P S H
In the pumping of liquid, the pressure at any point in the suction line must not be reduced to
the V.P of liquid. The available energy that can be utilised to get the liquid through the suction piping,
suction water way of the pump into the impeller is thus the total suction head less the V.P of liquid.
The available head as measured at the suction opening of the pump has been termed N.P.S.H.
Example (i) water at 62°F and O suction lift (sea level)
N.P.S.H. = 33.9 – 0.6 = 33.3
(ii) Do at 15 suction lift = N.P.S.H. = 33.9 – 0.6 – 15 = 18.3
Required N.P.S.H. It is a function of pump design and represents the min. required margin
between suction head and the V.P at a given capacity. Required N.P.S.H, being a function of velocity
at the suction passages and at the inlet to the impeller, increases as the square of the capacity.
However, the available N.P.S.H. is reduced with increasing capacity due to friction loss in the suction
piping. If suction pressure falls below vapour pressure of pumping fluid, there will be vapourisation
of fluid and noisy operation of pump with drop in discharge pressure. This is called Cavitation
Phenomenon. The priming of a centrifugal pump is done by filling up casing with water till air is
driven out with discharge closed.
SPECIFIC SPEED
The basic definition of specific speed is that it is the speed (rpm) at which a theoretical and
geometrically similar pump would run if proportional to deliver 1 G.P.M against 1 ft total head with
its best efficiency at these service conditions. Specific speed is an index of pump type.
n Q
Formula M s =
H3 4
where Ms = sp. speed, n = r.p.m, Q = G.P.M at speed n and H = total head per stage.
Normal sp. speed range for single suction impeller is 500 – 1500 r.p.m. The lower the specific
speed the higher is the head that can be developed for a total head and suction lift condition the
specific speed should not be below a certain value for successful operation. Limitation chart for
specific speed has been developed by Hydraulic Institute of U.S.A.
MECHANICAL SEALS
These are normally used for gland sealing in place of material like asbestos rope for stuffing
boxes of centrifugal pumps. Mechanical seals reduce gland leakages of fluid to a very low amount
and it is used also when corrosive, hazardous and costly fluids are handled. These are spring loaded,
flexible shaft mounted design and continuously and automatically compensate for shaft run out, axial
end play, vibration & wear. Usually fitted with carbon disks–one rotating and one stationery, which
restricts the gland leakage to a minimum. However a small leakage is desired for lubrication when
handling liquid process fluids.
LOSSES IN CENTRIFUGAL PUMP

Leakage loss: This reduces the volumetric efficiency due to leakage losses through the running
clearance between the rotating impeller and the casing parts. Leakage loss increases with the increase
of specific speed. In practice leakage loss is greater for smaller pumps because the clearance cannot
be reduced below a certain minimum; also because the wearing rings of larger pump are wider and
co-eff. of discharge is smaller.
Disk friction loss: The particles of liquid in the space between the disk (impeller) and stationery
walls acquire a rotary motion. As a result of centrifugal forces, particles start moving outward in
the immediate neighborhood of the disk and new particles approach the disk near the center. The
power consumption increases as the clearance between the disk and the wall is increased.
TECHNICAL LOSSES
Stuffing box and bearing losses. The friction loss in stuffing box is affected by size and depth
of stuffing box, pump speed, pressure and method of packing and lubrication. Friction torque is very
high with a tight gland but decreases rapidly as the gland is loosened and the leakage increases.
Friction power losses increase approximately as the square of the speed. Pumps, with mechanical
seal stuffing box, losses are minimum. Bearing losses using properly lubricated ball bearing or roller
bearing, become minimum. Bearing lubrication and alignment is important to keep bearing losses at
minimum.
HYDRAULIC BALANCING OF CENTRIFUGAL PUMP

For axial and radial balance in multistage centrifugal pump, some form of hydraulic balancing
devices must be used in the form of a balancing disc or a combination of these two. The balancing
disc of drum is nothing but a pressure reducing mechanism so used within the pump that the
pressure differential across leakage joint is equivalent to the total pressure generated by the pump.
For double suction pump, the impeller is balanced by the discharge pressure as well as suction
pressure acting each in opposite direction. Double suction centrifugal pump is usually of high
capacity.
Suction H eads of C entrifugal Pum ps
PS
C ASE 1 A h s = S – h fs – h i + P s
S
A h s = S – h fs – h i
C ASE 2 S
C ASE 3 S –h s = S + h fs + h i
B
PS
h s = D –h fs –h i + P s
C ASE 4
D
A
Fig. 1
Where S = Suction head : hfs = total friction loss in suction pipe, hi = entrance loss at A
D = Suction static head and Ps = Pressure of enclosed place. hs = Suction head.
Remarks : (1) A gage in suction line to a pump measures the total suction head (above
atmospheric)–velocity head at the point of attachment.
(2) As a suction lift is –ve, vacuum gage will indicate the algebraic sum of total suction
lift and (–) velocity head.
(3) If Ps in partial vacuum, the Ps in ft of liquid is to be expressed as –ve.
(4) Suction lift or head are measured below or above atmospheric.
(5) Use a foot value for suction lift with casing plug for air venting.
(6) The components in hs will be in consistent units.
D ischarge H ead of C entrifugal Pum ps
B
C ASE 1 D h d = D + h fd + h e + P d
Pd
D B
C ASE 2 h d = D + h fd + h e
C ASE 3 D h d = D + h fd + h e
C ASE 4 D h d = D + h fd
C ASE 5 D h d = D + h fd + h e
Fig. 2
Where hd = Discharge head (in abs. press, and also Pressure in ft. of fluid)
D = Static discharge head; hc = exit loss at B.Hfd = Total discharge pipe friction loss and Pd =
Pressure gauge reading.
Remarks : (1) For horizontal pump datum for suction and dischrarge in pump centre line.
(2) For vertical pump, datum is centre line of discharge line.
(3) For comparatively short discharge lines, friction loss will be 10–20% of static head.
(4) Discharge head will be given by pump discharge gauge.
(5) The components in he will be in consistent units.
PUMP IMPELLER TYPES

A. Forward curved vane—Head increases as the delivery rate increases
B. Backward curved vane—Head decreases as the through put increases.
The pump direction of rotation being clockwise (pump end). Suction and discharge heads of
centrifugal pumps are given in Fig. 1 and Fig. 2.
Chapter
18
INDUSTRIAL AND TOWN GASES
1. PRODUCER GAS
Producer gas is essentially a mix of CO and N2 together with H2, CO2, CH4 & O2 which are
present in small percentages. The gas is generated by blowing a mixture of air or air enriched with
oxygen and steam through an incandescent bed of coal or coke or anthracite.
There are mainly two types of producer gas generators viz (i) Revolving body generator with
fixed grate (exam. Wellman gas producer) and (ii) Fixed body gas generator with rotating grate.
A. Wellman Gas Producer
The rotating body is made of heat resistant steel and lined with refractory bricks. The ash is
discharged by the ash pan, rotating type, with water seal at the bottom and a stationery water cooled
top cover. An automatic water cooled poker is operated from top to keep the bed in uniform
condition of heat. Coal is fed from top by a mechanical feeder valve.
Pressurised air blast at 10" W.G by a turbo blower is introduced into the generator through a
bottom head. Both generator & ash pan rotate slowly and ash is discharged automatically by ploughs
inserted in ash pan which dump it on the ash boxes. Steam at 0.3–0.5 lb/lb of coal or coke or
anthracite is added to the air flow to (i) control of Clinker formation by increasing the air blast
saturation and (ii) to raise H2 rich gas by the water gas reaction. Major reactions in generator are.
(i) C + O2 = CO2
(ii) H2O + C = CO + H2
(iii) C + 2H2O = CO2 + 2H2
(iv) C + CO2 = 2CO
The producer gas temperature at exit is 1250 – 1500°C and pressure 1" W.G. The fuel bed
is divided into four zones viz
(a) Ash Zone. It is just above the grate and the ash zone serves to preheat the incoming air
blast from bottom.
(b) Oxidation Zone. Above the ash zone is the oxidation zone which is about 6" thick. Here
reaction (i) takes place and the temperature is highest due to combustion reaction. Steam in air helps
to keep a lower temperature to prevent clinker formation. Heat released by combustion reaction must
be sufficient to carry out endothermic reaction and compensate for heat losses by radiation. The
temperature of oxidation zone is 1100–1200°C.
143
(c) Above the oxidation zone is the top reduction zone. Primary and secondary zones which
is practically extend upto top of the fuel bed. The reduction reactions (ii), (iii) and (iv) take place
in reduction zone and absorb potential sensible heat in the producer gas. The reactions (ii) and (iv)
are very fast as the gases enters the reduction zone. As the gases pass, CO2 and steam content
decreases due to endothermic reactions & temperature of bed must be over 800 – 900°C as at this
temperature these reactions stop.
(d) Top heating zone. Here lies the freshly added charge of feed coal/coke/anthracite which
is dried & heated up by the incoming gases from reduction zone to start reaction as it descends to
reduction zone. If coal is used, it is carbonised to coke liberating tar and volatile matter as well as
SO2. Depending on sulphur present in coal, SO2 removal may be necessary to recover from producer
gas in subsequent purification stage. The bed temperature raises constantly apart from sensible and
radiation heat losses.
B. Coppee Gas Producer
It has fixed cylindrical body with rotating water sealed ash pan at the bottom which rotates
at the rate of 1 rev. in 10 minutes by a rack a pinion arrangement. There is no refractory brick in
jacket boiler. Air blast is introduced along with steam from bottom of the grate to increase air blast
saturation so as to generate more H2. Steam is generated from jacket waste heat boiler in annular
space provided in the body of the generator. The thermal efficiency of this generator is more.
1.2 Quality of gas generated depends on (i) air blast pressure (ii) air blast temperature (iii)
fuel size and type of fuel used and its quantity (iv) ash fusion temperature of fuel and steam/air ratio.
1.3 Producer gas output is around 120 MCF/ton of coal and its composition is as
follows
CO = 24–28% (vol)
N2 = 52–55
H2 = 11
CH4 = 0.5
CO2 = 4–5
The gross calorific value is 1068–1335 Kcal/m3 and density about 1.16 Kg/m3
1.4 Specification of Fuels for Producer Gas
Coal. It should be low in sulphur 1–1.2%, low in ash content but higher ash fusion temperature.
High volatile and weakly coking coals are preferable. The tar fog adds as much as 15 B.T.U/cft to
calorific value.
Coke and anthracite – Suitable for clean producer gas.
Typical composition of producer gas when using different feed fuels is given in page 145.
1.5 Operation Problems
Maintaining correct depths of feed through out the fuel bed for uniform gas distribution so as
to prevent channeling and hot spots which lower the efficiency resulting in lower gas quality. In
coppee gas generator no clinker formation occurs due to low shell temperature of jacket boiler. Due
to poor quality of coal, ash discharge in Wellman producer may be problem due to clinker formation.
Ash pan seal water is taken to a settling pond, clear water from pond is recycled along with make
up water. Gas temperature control from producer generator is important as a function of operation
requirement.
INDUSTRIAL AND TOWN GASES 145
Fuels used
Composition Coal Coke Anthracite
CO 24–29% 24–30% 25–27%
H 11–15 11–14 14–18
CH4 0.5–2 0.5 1.2
Hydrocarbons 2–3 3–5 4–6
Nitrogen 52–57 52–55 50–53
Net Cal. Value, 1156–1352 1125–1201 1221–1299
Kcal/m3 at 60°F
at 30"Hg
Sp. gravity (air = 1) 0.9 0.9 0.9
N.B. 1. Air for complete combustion of producer gas and air mix (cold) is about 0.9 – 1.2 cft/cft of
mix.
2. The net calorific value of above mix is 578 – 640 Kcal/m3 and is less than coal gas air mixture
having net calorific net value of 818 - 845 kcl/m3.
1.6 Industrial Use of Producer Gas
Application Type of fuel used Type of producer gas used

Heating coke ovens Coke Cold and clean gas
Regenerative furnace for Coal Hot raw gas
steels and glasses etc. manufacture
Heating retorts Coke Hot raw gas
Dilution for town gas supply with air Coke Cold and clean gas
1.7 Efficiency of Producer Gas Generators

BS-945 standard is normally used to determine the efficiency of producer gas generators as
given below.
Potential heat of gas
Cold gas efficiency = ×100
Total heat of fuel
Total heat of gas

Hot gas efficiency = × 100
Total heat of fuel
Total heat in the gas in the sum of potential heat calculated from gross and net calorific values
plus sensible heat in the gas. All values are expressed as B.T.U/ton of dry fuel.
1.8 Gas Exit Temperature from Generator
This gives the gasification conditions in the generator. For example low gas exit temperature
may be due to one or more parameters as stated below.
(i) Fuel bed too thick
(ii) Wet fuel
(iii) Low gasification rate
(iv) Body surface temperature is too high (normal 50°C)

On the other hand a high gas exit temperature indicates.
(i) Fuel bed too thin or non-uniform fuel bed
(ii) Channeling of hot gases in the bed with localized hot spots
(iii) Producer gas is burning at the top
(iv) Ash zone is non even
(v) High gasification rate due to decrease in fuel cross sectional area because of the accumulation
of clinker on sides and closing of air blast ports by clinker
(vi) Body surface temperature is too low (normal range is about 50°)
1.9 Cleaning of Producer Gas
When coke or anthracite is used, only water cooling in a packed tower is required followed
by filtration in filter boxes packed with wood shaving and wood wool.
The filtering media may be mixed with iron oxide catalyst if H2S is present in producer gas
generator from coke or anthracite. The washing tower is packed with 1-2" coke or lumps and water
is sprayed from top which cools the producer gas by a adiabatic cooling due to evaporation of
scrubbing water. The water removes dust particles from gas entering at the bottom of washing tower
and the water dust mix then flows into a settling pond where m.u water is added and recirculated.
2. SLAGGING ASH PRODUCER

The ash is converted to molten slag due to intense heat generated using air enriched with
oxygen, in up run period. The fuel bed is deeper than conventional process and gasification rate is
higher, 500 lb/sft. Temperature control is effected by adding limestone or BF slag along with coke
charge. The operational problems are more due to molten slag, sticking on acid bricks refractory,
causing choking.
3. WATER GAS OR BLUE WATER GAS

Water gas is primarily a mixture of CO and H2 together other small quantities of gases viz CO2,
N2 and CH4. The gas is made by passing steam on a bed of red hot coke.
3.1 The water gas generator consists of a tall vertical cylindrical vessel made of steel. The vessel
is lined with refractory bricks, except in jacket boiler portion, where insulating bricks do not
insulate it. A rotating grate is provided at the bottom, which continuously removes ash into the
ash box. Air and steam is passed alternatively from bottom to the red hot bed and blow gas
and water gas are obtained respectively from top of generator. The reaction with steam is as
follows.
C + H2O 
→ CO + H2 ∆H = 52110 BTU/mole ...(1)
C + 2H2O 
→ CO2 + 2H2 ∆H = 35420 BTU/mole ...(2)
The steam run is done, consequently, in both up and down directions through the red hot bed
and water gas is collected alternatively from top and bottom of generator, followed by air up run,
when the oxidation gases are vented to the atmosphere.
The reactions during air run are.

C + O2 = CO2 ...(3)
CO2 + C = 2CO ...(4)
The total cycle of operation lasts for 2.5–5 mins. The valves at the water gas off take lines
at top and bottom of the generator, air valve, exhaust gases valve, steam valves for up and down
run, and rotary coke feeders valves are operated automatically through hydraulic devices. Run with
steam after air run with off gasses purged to vent, is also done in automatic sequence. LP waste
heat boiler steam is used for steam run; bed temperature during air run is 1100–1200°C. The
bed temperature comes down to 800–900°C during steam runs because of endothemic reactions
(i) and (ii) The exit water gas after seal box can be scrubbed with water and gas stored in gas
holder. The dust laden scrubbing water, after settling in a pond, is released with m.u water
addition.
3.2 Composition of Water Gas
H2 ----- = 45.51% (vol)
CO ----- = 45.40%
CO2 ----- = 3 – 6
N2 ----- = 3 – 7
CH4 ----- = 0.1 – 0.5
The water gas burns with a blue flame. The net calorific value is 2580–2758 Kcal/m3.
Sp. gravity (air – 1) = 0.55
Theoretical bed temperature = 1900°C during air run
Actual bed temperature varies from 1100 – 1200°C during air run.
Factors for the quality generation of water gas are, quality of coke or anthracite, clinker
removal efficiency, volatile matter & sulphur content of fuel and O2 enrichment of air can be avoided.
The cycle timing is to be judiciously set.
The thermal efficiency of water gas generator is of the order of 60%.
3.3 Uses of Water Gas
It is used in furnace operations when rapid heating is required. It is also a source of H2 gas.
The gas burns with a blue flame due to CO content.
4. CARBURETED WATER OR TOWN GAS

Here the water gas is enriched with hydrocarbon oil vapours (Diesel). The generator is similar
to water gas generator and water gas generated and oil vapour from a separate carburator, is mixed
with water gas followed by some cracking of some oil vapour in the super heater. Heat is supplied
by burning some oil vapour in carburator as well as in super heater.
In the carburator, preheated diesel oil is vaporised @ 2 US gallons per 1000 cft of carbureted
water gas which is generated by a water cooled burner at the top. Some cracking of oil also takes
place in the carburator whose temperature varies from 600–1000°C. The remaining cracking of oil
vapour takes place in super heater, filled with chequer work. The gas leaves the super heater at about
800°C. The heat required for cracking is generated by combustion of some oil in the super heater
and also by blow gas during the blow period so as to raise the temperature of carburator and super
heater. Super heater top temperature is 650°C and bottom temperature is about 800–900°C. The
outgoing gas is cleaned by water cooling in a scrubber and stored.
The composition of carbureted water gas is.
H2 = 37% (vol)
CH4 = 14
Ethane etc.
CO = 30.5
CnHm = 7
CO2 = 5.6
N2 = 5.5
Oxygen = 0.4
The gross calorific value is 4450 Kcal/m3 and net calorific value is 4075 Kcal/m3.
Sp. gravity (air = 1) is 0.63. The overall thermal efficiency is 80%.
Use of Carbureted water gas.
It is mainly used as a town gas for domestic consumption.
4.1 Semi Water Gas
It contains almost equal concentrations of H2 and CO more than those in water gas or B.W.G
to suit ammonia synthesis gas generation (H2 and N2 in the ratio of 3:1). The gas generator is with
jacket boiler and rotating ash grate. The coke feed mechanism is done by automatic system and
reversing mechanism, by hydraulic controller like those of water gas generator. This has up run
period with auxiliary air to suit the production of necessary N2 for ammonia synthesis after purification
and CO conversion. The composition of the gas is as below.
H2 = 34.2% (vol.)
CO = 36.1
CO2 = 7.4
N2 = 21.5
CH4 = 0.8
H2S = 0.03
Coke/cft SWG = 1.3 – 1.4 kg
Calorific value = 1700 Kcal/m3
Coke used is about 4" size. Cold gas efficiency = 65%.
The cycle of operation of the generator proceeds in the following sequence as per hydraulic
controller.
(a) Blow run – Primary air is blown up from bottom to bring up the temperature of bed to
red-hot. The combustion gases are vented through stack.
(b) Up run steam – Preheated auxiliary air along with L.P steam is blown from bottom & semi
-water gas is collected from top of the generator. Reactions;
C + H2O 
→ CO + H2 ...(i)
C + 2H2O 
→ CO2 + 2H2 ...(ii)
CO2 + C 
→ 2CO ...(iii)
Reaction (i) is very rapid and stops when bed temperature is reduced to 800–900°C.
(c) Down run steam – Here L.P stem is blown downwards and semi-water gas is collected
from bottom.
(d) Final up run. Primary air is blown from bottom to remove remaining CO, H2 etc. and vented
to atmosphere, as well as raising bed temperature uniformly. Ash from slow moving rotating grate
is discharged into ash boxes from where it is periodically removed. The sequence time varies
between 3–5 mins. The primary air, auxiliary air, steam change over and vent stack valves are opened
and closed as per operation sequence by hydraulically controlled automatic controller, working at 850
- 950 psi through cam action, which controls power cylinder operation, attached to each value for
the operation sequence.
The exit gas at 550 – 650°C from generator is passed through a water seal box and then
washed in a Lymn washer tower with 0.7% Sodium Carbonate soln., which removes dust and cools
the gas. The dust laden wash water is passed into a settling pond, which removes ash dust and top
water is sent to a cooling tower after adding make up water and re-circulated. The hy. oil controller
consists of power cylinder, double restriction value, throttle valve and interlock control valve.
For the production of ammonia synthesis gas, the water gas is passed through series of Iron
oxide catalyst boxes, mixed with wood shavings when H2S is absorbed and stored in gas holder.
The water gas for ammonia production is then treated in 2 stage shift reactors for CO removal
in primary and secondary rectors so as to get ammonia synthesis gas with little CO, which is
removed in ammonia plant. The CO conversion catalyst contains Fe2O3 = 93.3%, Cr2O3 = 3 – 8%,
K2O = 2.07% & Al2O3 = 0.8%.
Semi water gas is exclusively used for the production of ammonia synthesis gas.
5.0 BLAST FURNACE GAS. (B.F)

About 60% of the heat in coke comes out in the exit gases from a Blast fumace during pig
iron production. This gas is called blast furnace gas and has the composition as follows.
CO = 27% (vol)
H2 = 2
CO2 = 11
N2 = 60
The net calorific value of the gas is 800–934 kcal/m3. Out of total heat available in B.F gas
upto 80% heat is utillized in the steel plant and remaining 20% of the total heat is available as surplus,
which is generally used in coke oven battery; heating boilers, reheating stoves etc.
5.1 Cleaning of the B.F. gas
The dust, associated with B.F gas, consists of mainly coke, iron oxide and lime. The conc.
of heavy dust can be 1000 gms/100 cft and that of fine dust (< 5 µ) is 5 gms/100 cft. Less vigorous
cleaning of gas is required for use in L.P boilers and reheating stoves.
There are two processes for dust cleaning.
Dry process: The gas from down comers of blast furnace is taken into a dust settling chamber
where heavier dust particles settle down and conc. of dust is reduced to 10–100 grains/100 ft3.
The gas is then filtered in automatic bag filters and dust conc. is further reduced to 1 grain/
100 cft.
Wet process: The gas from the blast furnace is scrubbed with low and high pressure sprays
in a water scrubbers fitted with baffles and cross partitions followed by separation of entrained water
droplets from saturated gas in an electrostatic precipitator. Water requirement for sprays is 24 US
gallons/100 ft3. The scrubbed water slurry is thickened in a thickener and the clear water is
recirculated after make up water addition.
6.0 COAL GAS

Coal gas is produced from H.T., LT and CVR carbonisation of coal for the production of coke.
Coal gas by H.T coal carbonization process.
Crushed bituminious coal to 3 mm size is fed to silica brick lined particular oven of the coke
oven battery by larrycar as per charging and discharge series of coke ovens. The top cover of the
oven is replaced on the top of the oven and heating of coke oven is started through about 31 flues
(depending on capacity) on each side by coke oven gas from both sides of the oven. At the end
of 15–16 hrs of combustion, the temperature inside the oven reached to 1100–1200°C which is the
temperature for H.T carbonization of coal. The typical size of each oven, length between doors ±
12900 mm. width 345–375 mm and height = 3100 mm for a 30 oven standard battery. The width
of oven gives the carbonisation time approximaely @ 1 hr per 25 mm.
Coke oven gas comes out of the ovens at 600–800°C and is cooled to 80–90°C by spray of
self produced ammonia liquor in the hydraulic main when major portion of tar is condensed and gas
and liquor are separated in the separating box. From the separating box tar is sent to storage and
ammonia liquor neutralised with sulphuric acid to produce ammonium sulphate by crystallisation and
is separated by centrifuging.
Coke oven gas then enters the primary cooler when remaining tar and some naphthalene separate
out. The gas is then pressurised in a centrifugal blower which, after cooling and tar separation in a tar
catcher; the coke oven gas is then scrubbed in ammonia scrubbers, packed with R/R.
After separation of ammonia, the gas is sent to benzol tower where it is washed with regenerated
wash oil, which is sent for recovery of coal carbonisation products. The gas after benzol recovery
is sent for coke oven heating or synthesis gas making or any other heating requirement.
After carbonisation, red hot coke is pushed out of oven by combined stamping by ram pusher
machine including door lifting mechanism. The red hot coke is pushed to a quenching car and taken
to a quenching tower where it is cooled by spraying water and coke discharged to wharf.
6.1 Coal Specification
F. Carbon = 51% (vol) by diff.
V.m = 27
Moisture = 4
Ash = 17
Sulphur = 0.7
Calorific value of coal is about 6300 Kcal/kg

Coal per ton of coke = 1.5–4 MT/MT coke
Coke oven gas composition.
H2 = 55.7% (vol)
CO = 5.4
CH4 = 24.0
CnHm = 1.6
CO2 = 2.2
N2 = 5.3
O2 = 0.4
H2S = 2.3 gm/NM3
Coal gas output = 265 NM3/MT coal
The net calorific value = 4029 Kcal/m3
The density of coal gas (air = 1) = 0.49
Analysis of coke.
Moisture = 4.5 %
Ash = 23 – 24
V.m = 1.5 – 2
Sulphur = 0.5
F.C = 73 – 74 (by diff.)
Ash fusion temperature = 1350 – 1410°C
Calorific value of coke = 5890 Kcal/kg
Crude Benzol output = 12.0 lit/MT of coal
Coal tar output = 3.5% of coal carbonized.
Uses of Coke
Gas coke from less coking coal or blends is used for gas generation viz water gas, town gas
etc. Met. coke is used in metallurgy. Met. coke is less combustible than gas coke.
7. NATURAL GAS
Natural gas is obtained is association with crude oil from oil wells (it is also available from gas
wells). After separation of crude oil in a series of separators, natural gas is transported through pipe
lines after compression to desired level in NG fired gas engines coupled to NG compressors. Usually
oil companies use a battery of such NG compressors.
The quality of NG depends on the type and location of source. Usually it contains mainly
methane (CH4), associated higher HC viz ethane (C2H6) (alkanes), Propane (C3H8), butane (C4H10),
pentane (C5H12) and hexane (C6H14), together with Nitrogen, CO2 and sulphur compounds (ppm
level).
Raw natural gas is usually stripped of alkanes upto butane & propane for production of
Liquified Petroleum Gas (LPG) for mainly domestic use by low temperature gas fractionation
process while pentane is separated from N.G by absorption in a solvent. Analysis of treated N.G is
as follows.
CH4 = 85–91%
C2H6 = 6.3
C3H8 = 1.15
CO2 & N2 = 1.55
Sulphur = 20 ppm
The net calorific value of N.G. is 9001 Kcal/NM3. Natural gas is used either as a fuel or as
a source of hydrogen; when propane and butane are not separated from NG it is called associated
gas.
(i) Natural gas thus stipped of LPG constituents & Pentane content, can be liquefied to facilitate
transportation by ocean going refrigerated bulk carriers as liquefied natural gas which is then stored
in shore based refrigerated liquid NG storage facilities in destination country where it can be re-
gasified to natural gas for use mainly as a fuel or other uses. Alkanes upto butane (C4H10) is
gaseous, pentane (from C5H12 to C16H34) are liquids upto 20°C and the rest are solids.
(ii) Liquification of natural gas for LNG.
Because of high critical pressure (47.3 kp/cm2) of methane, liquification of natural gas by usual
compression and cooling method is difficult and uneconomic.
The critical temperature of methane is –82.5°C and B.P and heat of evaporation are –164°C
(at 760 Torr) and 121.9 Kcal/Kg respectively.
There are few processes for LNG manufacture described elsewhere in this book.
(iii) Typical analysis of associated NG without LPG extraction (Upper Assam)
CH4 = 77.9% (vol)
C2H6 = 9.38
C3H8 = 6.01
C4H10 = 2.75
C5H12 = 0.69
N2 = 0.42
CO2 = 2.85
Specific gravity = 0.739
Mol. Weight = 21.43
NCV Kcal/nm3 = 10484.
PHYSICAL DATA/GRAPHS
C alculation of C alorific Values or Solid Fuel

for bitum inous coals containing 5–45% volatile m atter
9000
8500
8000
H u clean coal (Kcal/kg)
7500
7000
10 20 30 40 50
Volatile m atter (% )
Fig. l. Graph for calculation of calorific values of solid fuels.
Hu clean = 8150 + 38.83 (A + W) – 1.1806 (A + W)2
A ash content, %
W water content, %
100 − (A + W)
× volatile matter of clean coal = volatile matter of raw coal.
100
Conversion of gross into net calorific value H0 into Ha (raw coal) for solid and liquid fuels.
Hu raw = HO raw – 5.85 (0.09 H + W) kcal/kg. (H = hydrogen content. %)
When the moisture content alters from w1 to w2 the net calorific value (raw coal) becomes
2 2 100 − A − W
2 100 − W
Hu2 = (Hu1 + 6 w1) 100 − A − W – 6W2 ; A2 = A1 100 − W
1 1 1
For coke, Hu clean = 7,950 kcal/kg

For wood and wood shavings, Hu raw = 4.950–51.9 W
N et calorific values H u (kcal/kg) of C lean and R aw C oal

100 – (A + W )
H u ra w = H u cle a n –6W
100
70
60
Ash + Water content (A + W ) (% )
50
40
Hu
c le
an
=
30
90
00
kc
a l/
20
kg
60
50
70
00
80
00
00
00
10
10
Water content (W ) (% )
20
30
40
50
60
2000 4000 6000 8000 9500
1000 3000 5000 7000 9000
H u for raw coal (kcal/kg)

Fig. 2. Graph for net calorific values of clean and raw coal.
Example : For bituminous coal with Hu clean = 7750 kal/kg, A = 25% and
W = 15% (so that A + W = 40%) we obtain Hu raw = 4,560 kcal/kg
Note : Hu = net calorific value (Ho = gross calorific value).
H a rd co al (B itu m linou s co a l)
C p (true spe c, he a t)
C p m (m ean sp ec, he at be tw e en 0 a nd to c)
0 .42
H u = 7 57 7 kcal/kg
CO 2
S p ecific H e at (kca l/n m 3 °C )
0 .40 16%
12 %
1 6%
8%
0 .38
1 2%
8%
0 .36
400
350
30 0
0 .34 3
m
25 0
a l/n
200
kc
i=
150
100
0 .32
50
0 2 00 4 00 6 00 8 00 1 00 0 1 20 0 1 40 0 1 60 0 1 70 0
G as tem p era tu re (°C )
C o ke -o ve n Ga s
0 .42
H u = 4 68 5 kcal/kg 1. 1
n=
r a tio
S pe cific H e a t (kcal/nm 3 °C )
0 .40 A ir
1.5
1 .9
0 .38
0 .36
400
350
300
0 .34 3
m
250
l /n
k ca
200
i=
150
100
0 .32
0 2 00 4 00 6 00 8 00 1 00 0 1 20 0 1 40 0 1 60 0 1 70 0
Fig. 3. Specific heat-gas temperature relationship for hard bit. Coal and coke oven gas.
Source : Justi, E, Specific Heat, Enthalpy, Entropy and Dissociation of Industrial gases, © Springer Verlag
1938.
Fu el o il
----------C p (tru e sp e c, he at)
----------C p m (m ea n sp ace, h ea t b etw ee n 0 a nd to c)
0 .44
0 .42
H u = 1 08 00 kca l/kg 1 .3
S p ecific H e at (kca l/n m 3 °C )
= 1 .0
0 .40 on
r a ti
A ir
1 .1
0 .38
1 .0 1 .1 .3
600
1
500
0 .36
400
350
30 0
0 .34 3
250
m
l/n
2 00
a
kc
150
100
i=
0 .32
50
0 2 00 4 00 6 00 8 00 1 00 0 1 20 0 1 40 0 1 60 0
N a tural G as
0 .44
0 .42 1 .1
H u = 7 47 5 kcal/n m3 1 .3
S pe cific H ea t (kcal/nm 3 °C )
0
= 1.
0 .40
r a tio n
A ir
1 .1 1.1
0 .38
1 .0
1 .3
600
500
0 .36
4 00
350
1.1
300
0 .34 3
nm
250
l/
k ca
200
i=
150
100
0 .32
0 2 00 4 00 6 00 8 00 1 00 0 1 20 0 1 40 0 1 60 0
Fig. 4. Specific heat-gas temperature relationship for fuel oil and natural gas.
Source : justi, E, Specific Heat, Enthalpy, Entropy and Dissociation of industrial gases © Springer-Verlag.
S p ec ific a ir a n d flue g a s v olum es

fo r h a rd (B itu m in ou s) an d soft (B row n) C o a l
T he g ra ph is v alid w ith a m ean as h co nten t A o f 6% and m ea n C O 2 M a x 1 8.9% .
If A 76% th e v alu e tak en from the d iag ra m m us t b e reduc ed b y a correc tion fac tor
K as follow s : s pec . air v olum e V LO by K = A – 6 and spe c flue g as volum e
A–6 169
V G by K = [3 + (n –1)]. W hen A < 6% the s am e value a re use d for c alc ulation
169
T he c urve s a re not v alid for cok e, w o od pe at.
17 H u + 550
V L 1.01 n nm 3 / kg
16 1000
H u + 550
Vg (1.01 n–0.106) + 1.17 nm 3 / kg
15 1000
C O 2 m ax
0
2.
Air ratio n =
=
14 CO2
N
9
1.
io
at
rr
13
8
Ai
1.
7
1.
12
6
1.
11
5
1.
10
Specific air and Flue-G as Values VL 0 : V G (N M 3/Kg)
4
1.
9
3
1.
2
1.
8
1
1.
7
0
1.
Vg
6
L0
V
5 E xa m ple :
H u = 5 200
n = 1 .4
4 A = 1 0%
L L0 = 5.8 1 - 10 –6 = 5 .7 8 6 n m 3 /kg
16 9
3 V L = 1.4 - 5.78 6 = 8.1 n m 3 /k g
V G = 8.69 - 10 –6 [3 + (1.4 - 1)]
16 9
2 8.5 88 n m 3 /k g
1
2000 3000 4000 5000 6000 7000 8000
N et C alorific value H u (kcal/kg)
Source : Boie, W. Energietechnik. Sept. 1953
Fig. 5 Specific air and flue gas volumes for hard bit and soft (brown) coal.
D e w - p o i n t t e m p e r a t u r e o f f l u e - g a s e s ..............................................................
T h e gra ph b e lo w sh o w s th e flu e-ga s d e w -p o in t te m p eratu re s of v a riou s fue ls, o nly ste am
(w ater v a po u r) c o nd e n sa tion be in g ta ke n into a cc o un t. T h e v alu es a re ba sed o n a n 8 0 %
re lativ e h um id ity of the fu rn a ce a ir a t 20 °C
70 R hin ela nd B ro w n C oal

6 0% w ate r
C en tral G e rm a n
B row n C oal
60
D e w -Po in t (C )
5 2% w ate r
W o od , p eat
50
D rie d B row n C oal 1 5% w ate r
40 B itu m inou s C oal
30 B la st-f urn a ce G as
1 .0 1 .2 1 .4 1 .6 1 .8 2 .0 2 .1
A ir R a tio n
W h e re su lp h ur is pre se n t in th e fue l, the d e w -p o in t is c o nsid e ra b ly a ffe c te d b y th e c om b u stio n o f th e

sulp hu r c on taine d in the flu e - g ase s. T h e d ia g ra m w h ich sh o w th e de w -po int tem pe rature for
d iffe ren t su lph u r-c on te n t va lu e s in th e fu e l-o il.
D ew P o int of the flue gases w ith S O 2
1 50
3%
o il 2.5
ie l
of f
ent
ont 2
ur c
lp h
Su 1.5
D e w-P o in t°C )
1 00
1
0.5 %
50
0 1 2 3 3 .5
F ig . 6 . D e w po int tem p e ra tu re of flu e g as fo r v a riou s so lid fu els/
B F ga s a nd su lp h u r b e a rin g flu e g ase s from fu e l oi ls.
S o urc e fo r w ater d e w -p o in t : G um z, fue l an d firin g te c hn o lo g y,
S p ring e r Ve rla ng 19 6 2 © so u rc e for a c id d e w -p o in t : G la ub itz ,
V G B -H eft 68 . 1 9 60 .
Chapter
19
LNG PRODUCTION
1. Because of high critical pressure of methane, liquified natural gas LNG cannot be produced
by compression and cooling economically. The critical pressure and temperature of methane
are 47.3 Kp/cm2 and –82.5°C respectively and B.P and heat of evaporation being –164°C (at
760 Torr) and 121.9 kcal/Kg. LNG is produced by cryogenic process.
2. Pretreatment of natural gas mainly methane, mixed with other paraffins, is necessary to
remove sulphur compounds and other components that would either freeze out, thus restricting
the flow of natural gas, or will lead to pollution upon combustion after reevaporation of
L N G.
3. N G liquefaction processes.
The commonly used processes are (a) Baseload liquefaction process and (b) Cascade Process
of cooling using three refrigeration loops of propane (B.P = –44.5°C at 760 Torr), ethylene
(B.P = – 103.9°C at 760 Torr) and methane (B.P = –164°C at 760 Torr).
3.1 In base load liquefaction process, heat is to be removed from N G to cool it to –160°C by
rejecting heat to atmosphere or water. This is an efficient process suitable for large scale
L N G production.
3.2 In cascade liquefaction process using 3 refrigerant loops of propane, ethylene and methane,
each refrigerant supplies refrigeration at discrete temp level. This process has nine stage
refrigeration.
Physical data for propane, ethylene and methane are as follows.
Critical temp Critical press B. P Heat of evaporation
°C Kp/cm 2 °C Kcal/kg
Propane : 96.8 43.5 –44.5 101.8
Ethylene : 9.5 51.7 –103.9 125
Methane –82.5 47.3 –164 121.9
4. CASCADE PROCESS
Cascade process of refrigeration uses separate loops and suitable refrigerant for each loop. The
refrigerant in L.P circuit is condensed by evaporating next higher temperature (B.P) circuit refrigerant
in the cascade evaporating cooler or in other words, the refrigerating effect of higher temperature (BP)
circuit is used to remove heat of condensation from lower temperature (B.P) circuit. In short, only the
cascade evaporating cooler with lowest evaporating temperature generates the reqd. refrigerating effect.
159
In natural gas liquefaction, three temperature (B.P) levels form nine cascades using three
refrigerant cycles of propane, ethylene and methane, each of three stages. The methane refrigeration
loop is open due to the fact that it is combined with N.G feed and after final let down in flash vessels
liqued methane forms part of LNG production. The flowsheet is given in Fig 1.
N . G . Fe e d
A fter co oler
Flash co o ler
B
E vap o rating
D rive coo le r E
C
A fter co oler
P ro pa n e
com p ressor
Flash ve sse l M etha ne

D com p ressor
A fter co oler
Flash ve sse l
D rive D
E thyle ne com p ressor
Flash ve sse l
D
E vap o rating
coo le r E
LNG
Fig. 1 Cascade Process for LNG Production.

Each of these three temperature levels (B.P) corresponds to preset pressure let down in flash
vessels (D) for evaporating the refrigerant in heat exchange with N.G feed and separate propane
refrigerant stream in propane evaporating cooler (E) and then to ethylene evaporating cooler (E). In this
process heat is removed from NG at successively lower temperature and heat is rejected to cooling
water or air via warmest refrigerants, generally propane and after compressions and after flash cooling
(B), liq propane refrigerant is stored in tank (c) and compressed ethylene gas, after water cooling, is
sent to propane evaporator for cooling, followed by cooling and condensation in ethylene evaporator
cooler (E).
After ethylene evaporator, N.G is condensed and after flashing in flash vessels (D) temperature
of liquid N.G falls, liquified and separated and stored in refrigerator vessels. The evaporated N.G
from flash vessels is recycled via ethylene evaporator cooler and is fed to methane compressor
suction, compressed and after cooling, N.G meets the make up N.G. stream and the process goes
on.
LNG PRODUCTION 161
Liq. N.G is transported by refrigerator tanker or trucks. For transportation by ships, N.G is
unloaded in on-shore refrigerated LNG storage tanks; from where it is evaporated by steam heating
and NG is distributed to end users through pipe lines.
Processing N.G before LNG Production
Natural gas is freed from CO2, moisture and if sulphur is present and it is to be sweetened.
Sp. enthalpy of evaporation Volumetric refrigerating
at std B.P. kj/kg effect at –15°C to +30°C kg/m3
Propane 439 2238
Ethylene 48 1995
5. STORAGE OF LNG
Double integrity tank with suspended inner tank of concrete lined inside with S.S is used.
Lining material is 9% Nickel and 5000 series Al metal.
6. LNG DATA
(i) 0.035 m3 at 111 °K is derived from 18 m3 of LNG. Storage temperature of LNG is 170°K
at 2.24 Mpa (325 PSIA).
(ii) Heat of vapourisation of LNG is 232 Mj/m3 of LNG at 0.1 Mpa. Heat required for
regasification of LNG is 0.3 KJ/m3 of gaseous NG.
Chapter
20
PRODUCTS MANUFACTURED
FROM BENZENE, ETHYL
BENZENE, ETHYLENE, ETHYLENE
OXIDE, ETHANOL AND OTHERS
A. PRODUCTS MANUFACTURED USING BENZENE AS RAW MATERIAL
1. Styrene → Polystyrene
A B S resin
S B R / Latex
Polyester resins
SAN resin
2. Cyclohexane → Adipic acid → Hexamethylenediamine
↓ ↓
Cyclohexanol Caprolactum → Nylon
Caprolactum
3. Cumene → Phenol → Bisphenol A
Acetone → Methyl metha-crylate
Cellulose acetate (adsorbent)
Methyl isobulyl ketone
Methyl Phenyl ketone
Aldol chemicals (Hexamethylene glycol)
4. Nitrobenzene → Aniline → Aniline isocynate
↓
Polyester resin
5. Malic anhydride → Polyester resins
6. Chlorobenzene → DDT → Insecticides
↓
Phenol
7. Anthraquinone → Dyes
162
PRODUCTS MANUFACTURED FROM BENZENE, ETHYLENE, ETHYLENE OXIDE... 163
8. Dichlorobenzene → hexachlorobenzene (BHC)

9. Dodecyl benzene (for detergent use)
10. Benzene Sulphonic acid
11. Glyoxal
12. Benzaldehyde
13. Propyl benzene → Isopropyl benzene
14. Lindane ( Y isomer of BHC)
B. ALCOHOL, C2H5OH (ETHANOL) GRADES

Purity %Vol.
(i) Industrial alcohol = 96.5
(ii) Denatured* alcohol = 88
(with methanol)
(iii) Fine alcohol (Pharma use) = 96–96.5
(iv) Potable alcohol = 43
(v) Absolute alcohol or rectified spirit = 99.7–99.8
(vi) Gasol (Gasoline with alcohol) = 98% gasoline with 2% alcohol*
*Gasol also used in some south American countries with Methanol in the proportion of
2.5–5% methanol and rest gasoline.
“Proof” of Alcohol
U.K : Proof 87.7 equals 50% concentration at 10°C.
1
of proof at 15°C.
U.S.A.: Concentration is
2
N.B. Indian whisky is 75° proof (42.8% conc.)
C. PRODUCTS MANUFACTURED USING ETHANOL AS RAW MATERIAL

1. Vinegar
2. Acetaldehyde/Acetic acid
3. Ethyl acetate
4. Ethyl chloride/bromide
5. Other Ethyl esters
6. Ethyl amines (for rubber processing)
7. Sodium ethoxide
8. Acetic anhydride
9. Dyes and intermediates
10. Diethyl ether
11. Glycol diethylethers and others
12. Xanthenes
13. Drugs and medicinal chemicals
14. Organo-silicon products
15. Synthetic resins
D. ETHYLENE OXIDE IS USED FOR THE PRODUCTION OF :

(i) Methyl hexanol → Defoaming/wetting agents and plasticiser
(ii) Penta erythritol → Alkyd resins, explosives, Moulding powder
(iii) Trimethyl propane → Alkyd coalings, lube oil additive, Textile finishes & Urethane
foam
(iv) Acetic acid → Acetic anhydride, → Aspirin, Vinyl acetate, Cellulose acetate.
→ Acetyl Chloride → Organic synthesis and dye. Chloroacetic
acid → Sod. carboxy methyl cellulose, ethyl acetate,
Thioglycolic acid herbicides.
→ Cellulose acetate
→ Acetate salts → Flavours, perfumes and solvents.
→ Vinyl acetate → PVC acetate and Poly Vinyl acetate.
(v) Per Acetic acid → Bactericide, Bleaching agent, Fungicide, Organic Synthesis,
Polymerisation and Catalysts.
3. Ethylene dibromide → Dyes, Fumigant, medicines, Tetra ethyl lead (scavengers)
4. Diethyl Ketone → Solvents.
5. Polyethylene → Electrical Cables, Pipes, fittings, containers, etc, monofilament
film and sheet moulding powder and granules.
6. Mono, di-and Tri Ethanol amines.
7. Vinyl toluene → Surface coatings.
8. Ethyl alcohol → Acetaldehyde, ethyl ether, chloroform, Dimethyl amine, ethyl
acetate, Ethyl bromide Ethylene dibromide, glycol ethers.
9. Ethyl Chloride → Anaesthetics, Ethyl cellulose, TEL.
E. ETHYLENE DICHLORIDE
→ Ethylene diamine, adhesive, Corrosion inhibitors, rubber latex
stabilisers and Textile lubricant.
→ Agri-fumigant, vinyl chloride
→ Fibres, plastics.
→ Tichloro ethane → Vinyl iodine chloride → fibres, filaments
and plastics.
→ Ethylene amine → Tri ethylene di-amine, Urathane foam,
Catalyst. Flocculant, pesticides, and surface active agent.
→ Poly ethylene amines, → Adhesive corrosion inhibitors, paper
processing and deemulsifiers
10. D E A → Formalin.
F. PRODUCTS FROM ETHYLENE PRODUCED FROM NAPHTHA

1. Ethyl benzene
2. Ethylene Oxide
PRODUCTS MANUFACTURED FROM BENZENE, ETHYLENE, ETHYLENE OXIDE... 165
3. Ethylene dibromide
4. Diethyl toluene (Solvent)
5. Poly ethylene (Plastics)
6. Ethyl alcohol
7. Ethyl chloride
8. Ethylene dichloride
9. Ethylene amine
G. PRODUCTS FROM ETHYL BENZENE

1. Acetophenone → Perfumes
Pharmaceuticals
Solvent
2. Benzoic acid → Benzyl benzoate
Phenol
Sodium benzoate
Plasticizers
Perfumes
Flavouring chemicals
Pharmaceuticals
3. Styrene → Polystyrene (Plastics)
S B R rubber
Chlorostyrene → Flame retardant resins
Alkyd Polyester resins
SAN (Plastics)
Styrenated oils
4. Diethyl benzene → Drying oils
Elastomers
Resins
5. Ethyl anthraquinone → H2O2 → Peroxide chemicals as bleaching agent
6. Ethylene Oxide → Nonionic detergent
Polyester (Dacron)
Ethyl Glycol (antifreezing agent)
As solvent for quick drying varnishes and enamels
7. Ethylene dibromide → Dyes
Fumigant
Pharmaceuticals
Tetraethyl lead (TEL) scavenger
8. Ethyl alcohol → Hard drinks

Acetaldehyde
Ethyl ether
Chloroform
Diethyl amine
Ethyl acetate
Ethyl bromide
Ethyl chloride → Ethyl cellulose
Ethylene dibromide.
Glycol ether
9. Ethylene dichloride → Ethylene diamine
Vinyl chloride → PVC
Fumigant
Tetrachloromethane → Chloride, vinyldine
10. Ethyleneimine Triethylene diamine
Urethane foam
Flocculant
Plasticizers
Surface active agent
Polyethylene amines
11. Acetaldehyde → Acetic acid → Acetic anhydride
Acetyl chloride (Dye)
Chloroacetic acid
Cellulose acetate
Vinyl acatate
PVA
Acetate esters
(Flavour, Perfume and solvents)
12. Chloroacetic acid → Herbicides
Sod. carboxy cellulose
Ethyl acetate
Thio glycolic acid
13. Ethylene diamine → Adhesive
Corrosion inhibitors
Stabilising agent for rubber latex,
Textile lubricant
14. Polyethylene amines → Demulsifying agents, adhesive
corrosion inhibitor and paper work
Chapter
21
SYNTHETIC IRON OXIDE PIGMENT
Five type of pigments from synthetic iron oxide can be made with varying tints of red, yellow,
orange, violet and red.
A. Manufacture of Iron Oxide Pigments by Roasting Process
Synthetic iron oxide is prepared by (i) roasting iron pyrites for 4 hrs. at 600°C, (ii) roasting
ferrous sulphate for 9 hrs. at 700°C and (iii) Ammon. ferrous sulphate at 700°C and then further
roasting for 3 hrs at 100°C and calcining α Fe2O3 (red haematite ore).
Various colours of synthetic iron oxide can be made by roasting hydrated Ferrous Sulphate salt
mixed with other salts for use as pigments. It is also made by calcining α Fe2O3.
(a) Zinc and Al. sulphate gives orange-red colour.
(b) Calcining FeSO4 at lowest possible temperature gives dull red colour. Two stage calcination
gives brighter colour and by product Na2SO4 can be made by absorbing SO2 gases in soda solution.
(c) Calcining FeSO4 with Mn salts at higher temperature gives blood red colour to darker
colours.
Reactions:
FeS2 + 2H2O + 7O2 
Heat
→ FeSO4 + H2SO4
2FeSO4 
Calcining
→ Fe2O3 + SO2 + SO3
FeSO47H2O 
→ FeSO4 H2O + 6H2O
6FeSO4H2O  → 2Fe2O3 + Fe2(SO4)3 + 6H2O + 3SO2

Heat
650°C
Fe2(SO4)3 
→ Fe2O3 + 3SO3.
Ferrous sulphate is usually made from pickling of iron scraps with sulphuric acid and crystalising
salt:
Fe + H2SO4 = Fe2O4 + H2.
Heating of Ferrous Sulphate in presence of air:
6FeSO4H2O + 3/2 O2 — 3Fe2O3 + 6SO3 + 6H2O.
167
B. Manufacture of synthetic iron oxide pigments having soft pure colours is done
by precipitation and hydrolysis process
Precipitation process gives soft pigments with bright hue. The process consists of removing
excess pickling H2SO4 in mother liquor, left after acid pickling of iron scrap. The liquor is neutralised
with scrap iron. The solution of iron salt (FeSO4) is then mixed with NaOH in an open seed reaction
vessel with oxidation by air at a temperature of 20–25°C. Alkali is used in such a way that the
solution remains acidic pH. The reaction time is 10–100 hrs. depending on temperature, kept
(10–90°C), and desired crystal size of FeSO47H2O is achieved. The precipitate is yellow pigment (α-
FeOOH-Ferrous Oxy Hydroxide) which along with the mother liquor is taken either to a pigment
reactor or a tank, with scrap basket for further neutralisation of acid.
If precipitation is carried out at 90°C in pigment reactor, with air oxidation at pH > 7, black
iron oxide pigment is obtained with a magnetic structure and reaction is stopped at Feo/F2O3 = 1:1.
The exit pigment slurry is filtered in a centrifuge, dried in a furnace and ground in a mill grinder
and further dried in a barrel dryer. Total processing time can be 2–7 days. If yellow nuclei is
produced in pigment reactor, highly consistent yellow iron oxide pigment with pure colour can be
obtained.
By slightly altered route and parameters, red iron oxide pigment can be made. If the pickling
solution contains other metallic ions in large quantities, this has to be removed to get bright colour
pigments. This process, known as Peniron process, is widely used for yellow iron oxide.
C. (i) Calcination of α FeOOH with small quantities of magnesite compounds gives homogeneous
brown (FeMn)2O3 pigment.
(ii) Brown pigment-Controlled oxidation of Fe3O4 at 500°C produces a single phase γ Fe2O3
with a neutral brown hue.
(iii) High quality iron oxide pigment, also called copperas reds, is made by thermal decomposition
of FeSO47H2O in a multistage (3 stage) rotary dryer used for calcining which produces α Fe2O3.
The α Fe2O3 is transferred from a tank filled with agitator and transported to a cyclone to remove
soluble waste and red iron oxide is sent to dryer followed by grinding in pendular mills pin mills and
jet mills depending on hardness accrued.
(iv) Orange iron oxide with (γ-FeOOH) is obtained if dil solution of Ferrous salt is precipitated
with NaOH or other alkalies until almost neutral. The suspension is then heated for a short period,
rapidly cooled and oxidised. The suspension is filtered, dried and ground in rotary mills.
(v) Very red iron oxide pigment, with pure red colour, may be obtained by first preparing α
Fe2O3 nuclei and continously adding of iron (II) salt with atmospheric oxygen addition at 80°C.
Hydrolysis and neutralisation are carried out by adding NaOH and keeping pH constant. The rest of
the process-filtration, drying and grinding are same as in other processes. Some neutral salts are also
produced as by products in the precipitation and hydrolysis process.
D. Properties of Iron Oxide Pigments
The final products is same for all the processes, Fe+3 -α Fe2O3 but properties are dependent
on method of preparation. Thermal dehydration of yellow geothite gives lowest density product (4.5
gm/cc).
The pigment value results from physical properties, determined by physical state (particle size,
crystal structure, particle shape, agglomeration etc. The chemical properties involve composition,
purity and solubility. The most important physical-optical aspect of pigments is its ability to colour
SYNTHETIC IRON OXIDE PIGMENT 169
environment in which they are dispersed and make it opaque. The opacity of a pigment lies in its
ability to prevent transmission of light which is applied. The yellow pigment size is 0.1–0.8 µm and
refractive index of 2.9–3.22.
The maximum dispersion of visible light occurs when pigment particle size range is 0.16–0.28
µm. Red pigment has highest density of 5.2 gm/cc and size = 0.3–4 µm.
E. Test Lab Instruments
(i) Sieve testing facility.
(ii) Refractive index determination instrument.
(iii) Atomic absorption spectro photo meter for crystal structure.
(iv) X-ray florescence analyser.
(v) Chemical analysis for composition and moisture determination.
Uses: In construction materials viz ceramics, cement, roofing granules, coating materials,
plastics colouring, paper and magnetic recording.
Table 1
International specification of iron oxide pigments
ISO ASTM DIN
Black Pigment 1248 D 769 ISO1248
Brown Pigment 1248 D 3722 ISO1248
FeO Content – D 3872 –
Red Oxide Pigment 1248 D 3721 55913T1
Yellow Pigment 1248 D 768 ISO1248
Chapter
22
DYES, INTERMEDIATES AND
DYEING
Dyes are complex organic compounds mostly soluble in water while some dyes are soluble in
dilute mineral acids. They are various types of dyes used for dyeing of textiles and yarns (natural
or synthetic), textile printing, colouring of plastics and other materials. Dyes are classified as under:
1. Basic Dyes–These are cationic dye mainly amino and substituted amino compounds, soluble
in acids only.
2. Acid direct dyes–Anionic dye used for dyeing protein based fibres-wool, silk, synthetic
nylon and some types of polyacrylic fibres, applied from acid dye bath. These dyes are water soluble.
Example–Chlorantine (ciba).
3. Azo dyes–Insoluble dye produced in-situ on fabric by coupling diazotised materials containing
one or more azo groups–N : M–as chromosphore usually with hydroxyl/amino group/oxyquinone
nitrosogr./Zanthene gr. or auxaphoromones gr. Example–Diamond black F. Many azo dyes were
banned both in India and abroad due to health hazards.
4. Reactive dyes–These dyes, under suitable conditions, recat to form a covalent bond between
the dye and cellulose fibres (cotton) and rayon. Example–chromazol.
5. Disperse dye–Forms finely divided solid solution with synthetic material fabrics/yarns viz.
synthetic cellulose acetate, plastics and polyester. These dyes are substantially water insoluble.
6. Vat dyes–Water if soluble dye which are derivatives of anthraquinone or indigoid groups.
These usually contain two keto groups which are manually applied to fibres from alkaline dye both
containing a reducing agent (sod. hdydro-sulphite). This process is called “Vatting” or “solublising”.
Example–Victoria blue.
7. In-grain dyes–These are produced in situ on fibres when cotton impregnated with aniline
and oxidised with an oxidising agent.
8. Vegetable dye–Naturally occurring colouring matter, containing organic dye. Example–
Henna.
9. Solublised vat dyes–There are indigo dyes in acetic acid or ammonium sulphate solvent.
10. Mordant dyes–These dyes are those which receive a mordant (hydroxides or salts) to form
complexes called “Lakes” resulting in satisfactory dyeing on fibres (substrate). Example–anthracene
dye (alizarine).
170
DYES, INTERMEDIATES AND DYEING 171
11. Food colours–These are nontoxic coal tar dyes suitable for adding in food products. These
have stringent standards for food colours. Products for exports to USA require FDA rules compliance.
Eu standards to be followed for exports to Europe.
Dye Intermediates
These are made from coal tar primary compounds viz Benzene, tolune, naphthalene, cresol,
anthracine, xylenes etc. Coal tar itself contains 200 aromotic compounds. The primary compounds
of coal tar are converted to dye intermediates by series of reactions like nitration, sulphonation, alkali
fusion, reduction, chlorination, oxidation and condensation so as to form hydroxyl, amino and other
groups, introduced into the original hydrocarbon materials to form intermediates. Dyes are made
from these intermediates.
Dyes are usually named by the dye compounds or patented name, given by reputed manufacturers.
Germany is pioneer in making dyes.
Dyeing Process
Water requirement–A high quality of soft water, having low hardness, is required in dyeing
process. The amount of water required varies for different materials to be dyed. For example 1 kg
of cotton yarn will require about 5 gallons of water in dye vat. In case of wool the ratio is 1:14.
For dyeing process, involving circulation of dyeing solution, water requirement is less, about 1:10.
Post dyeing process required water for acid/alkali removal from substrate as well as final washing
with water.
The percentage of dyeing materials required is based on wt. of materials to be dyed (substrate)
For example, in case of Acid dyeing on wool, usual % of dyeing materials required are:
(a) H2SO4–4%
(b) Glauber salt–20%
(c) Acid dye–X%
For colour fastness, often post washing with required chemical solution is required.
Dyeing Equipment
Various equipment are required depending on process of dyeing of textiles materials. The
process can be manual, semi continuous or continuous.
Colour Index of Dyes
Basic information in given in colour index international (9 vols) and all dyes are given a C.I.
no. and also a general name. A difference of 5 in between two dyes. Colour wheel is given in Fig.
1 in Chapter 32.
Banned Dyes
Germany has banned 20 azo dyes. India had banned some 65 acid, direct and disperse dyes
and 45 benzidine dyes.
Chapter
23
FLOURESCENT OR OPTICAL
WHITENING AGENT (FWA)
These are complex organic compounds soluble in water and is used to impart excellent whiteness
yellowish tint of textiles is produced by absorption of short wave length ultraviolet light (violet to
blue). Optical brighteners absorbs maximum UV light-in the wave length of 350–575 nm range and
emit the absorbed energy in the blue fluorescent range, having maximum wave length of 415–495
nm in the visible range. The material looks like dazzling white.
Most of the FWAs are derivatives of stilbene (common) or 4,4 diamino stilbene trizoles,
oxazoles, imidazoles which are five members nitrocycles gr. often 6 members FWAs viz coumarines
are used. FWAs are different for particular textile viz cotton, polyester, paper pulp etc. For cotton
and paper bleaching, suitable FWAs are bistrianzinyl and bisstyrylbiphenyl di-sodium salt. For polyester
use. 4 methyl-N-methyl napthalamide can be considered. FWAs are arranged in a series starting from
FWA-1 to FWA-220 and are characterised by groups as R, R1, R2 R3, .......
Example: FWA R, Group
16 OCH3
21 – N(CH2CH2OH)2
26 – N(CH2CH2OH)2
22 – N O
Fluorescence effect of organic FWAs is the fraction of light energy that is absorbed and
emitted; in fluorescence, concentration of whitening agent, to be used, varies from 0.002–0.2%.
Types of FWAs for use in bleaching of different materials
Material FWA FWA no.
1. Cotton Bistrianzinyl 70
2. Polyester 4 methoxyn 74
Methyl naphthalamide 75 and 52–55
3. Wool, Cellulose acetate- coumarins 67
rayon and polyamides 68 and 69
4. PVC and Synthetic fibres 14, 47, 70
172
5. Paper pulp 21, 24, 26
6. Moderate washing temperature (tex.) 20, 22
7. PAN Fibres 50, 51, 52, 72, 73
Often some stabilising materials are required during bleaching. The toxicology of FWA used
must be considered and LD-50 must be high (LD50 above 5000 mg/kg). Also environmental water
pollution must be considered and suitable water pollution treatment method must be utilised.
Uses of FWAs
Detergent 50%, cotton, synthetic textiles (15%), plastics and paper pulp (30%), and for soaps
and biological staining.
Chapter
24
A
FLAME RETARDANTS, HALONS,
FIRE ALARMS/HYDRANTS AND
RUBBER AND EXPANDED PLASTICS
(I) FLAME RETARDANTS
1. Flame retardants are active chemicals (inorganic and organic) applied to fabrics, plastics and
other materials for retarding flame generation when such coated fabrics or other base materials
get ignited due to some reason. The list of such chemicals are given below:
(i) Zinc borate, (ii) Al hydroxide (iii) Molybdenum carbonate (iv) Bromine compounds (v)
Chlorinated alkanes (vi) Halogenated phosphate esters (vii) Aluminium oxide trihydrate (viii)
Magnesium hydroxide (ix) Cyclo aliphatic compounds (x) Ferrocene and (xi) Antimony trioxide.
2. A flame retardant either inhibits or even supresses the combustion process and depending on
the nature of base material, a flame retardant can act physically or chemically in solid, liquid
or gaseous phases. Flame retardants interfere with combustion during a particular stage of
process viz during heating, decomposition, ignition or spread of flame.
3. Physical action of flame retardants by way of:
(a) cooling-endothermic process triggered by a retardant e.g., Aluminium oxide trihydrate,
(b) protective layer formation-gas/solid protective layer e.g., halogenated phosphatic esters
(c) dilution-inert substance (fillers) and additives which arrest gases from decomposition and
dilute the fuel e.g., Aluminium hydroxide.
4. Action of some flame retardants is base material specific viz Ferrocine in polyurethane; Aluminium
oxide trihydrate and Magnesium hydroxide do not generate smoke.
5. Application-After cleaning of fabric, a small portion of retardant chemical solution is sprayed
over the fabric and allowed to dry slowly. Test is to be carried out after cooling to ascertain
the extent of flame retardation viz determination of oxygen index before and after application
of retardant. In case of plastic with flame retardant, it is mixed with plastic during moulding
174
FLAME RETARDANTS, HALONS, FIRE ALARMS... 175
stage and burning characteristics of treated plastic is determined and so also for the virgin
plastic. Halogenated flame retardants are also used in plastics.
Typical composition of a treated plastic is polycarbonate, 93% decarbomo diphenyl ether 5%
and antimony trioxide, 1.9%.
6. Uses-electronic, electricals, toys, tents, carpets and drapers and children sleep ware etc.
(II) HALONS
Halogenated Fire Extinguishing Chemicals
Halon is a trademark for tetra fluoro ethylene polymer. Halons are new fire extinguishing
chemicals designated as 4 digit nos. The chemical compounds contain halogen atoms in addition to
carbon atoms:
(i) 1st digit indicates no. of carbon atoms
(ii) 2nd digit indicates no. of flourine atoms
(iii) 3rd digit indicates no. of chlorine atoms
(iv) 4th digit indicates no. of bromine atoms.
Types of Halons:
Remarks
(a) Halon 1001 (CH3Br)
(b) Halon 1211 (CBr C1 F2) Active agent 6%
(c) Halon 1301 (CF3Br) Active agent 5%
(d) Halon 2402 (C2F4Br2)
Characteristics
Halons are efficient flame extinguishing chemicals which causes flame to sink and stay at the
base of the flame. It removes the active chemical species involved in chain reactions for flame
propagation. Halons are over two and a half times more active than CO2 and suitable for liquid
combustible materials fires. Halons are generally not used in solid combustible fires.
It is self extinguishing and inert to all chemicals and resistant to high and low temperature.
Toxicity: Except Halon 1301, rest are non toxic. Halon 1301 has TLV-TWA = 1000 ppm and
MAC = 6100 mg/m3. Halon concentration above 10% is dangerous to human being.
Application: It is applied by portable fire extinguisher. Fixed installation should be unoccupied.
Concentration upto 4% is tolerable for one minute only.
(III) FIRE DETECTION ALARMS

There are three methods of fire detection, (1) Ionisation detection chamber by α particles and
(2) photo electric detection chamber by difference in photo voltaic cell e.m.f. and (3) fusible alloy
water sprayers.
1. Ionisation Smoke Detection Chamber
The process uses the principle of generating α particles from Radium or any other artificial
Radium isotope or ultra violet rays; α particles in the air (O2 and N2) molecules, thereby knocking
out an electron from air molecules. The molecules, so hit, become ions and move to -vely charged
electrons.
If air particles, containing smoke and dust, enter the chamber, the ionisation chamber conditions
is changed. The solid smoke particles will absorb α particles with the result that fewer no. of
particles are now available for ionisation of air and the current passing through the circuit will be
reduced, thereby triggering a connected alarm circuit. A cold cathode tube (CCT) is usually used for
the smoke alarm detection. The system is used in offices, shops etc.
O P = open ionisation cham ber

C C = closed ionisation cham ber
C C T = cold cathode tube
CC
CCT
OP
Fig. 1. Ionisation smoke detection circuit.

2. Photo Electric Cell for Smoke Detection
The system uses a photo electric cell chamber with air inlet and outlet provision in between
light source and photo cell. Air, containing smoke and dust, while crossing the light to photo cell,
changes the photo voltaic cell e.m.f. This triggers an alarm circuit due to reduced intensity of light
from light source as a result of smoke and dust in air. The system is used in offices, shops etc.
and is less costlier than isotope based detector.
Air
To alarm system
Photo cell
Light source
Fig. 2. Photo electric smoke detection system.
3. Fusible Alloy Water Sprayers
The system is suitable for storages containing combustible materials. The system is a part of
a fire hydrant system and a fire water pipe line grid is placed over head in combustible storage. The
fusible plug sprayers are put in the firewater grid mouths having threaded connections for easy
replacement.
The fusible alloy melts due to heat, whenever there is a fire in the combustible material storage
below, resulting in water at fire hydrant pressure is sprayed on the fire thus putting out the fire. With
the fall in firehydrant pressure due to operation of water spraying system, an alarm circuit is also
triggered. New fusible alloy sprayer nozzles are to be put once such sprayers are activated by fire.
FLAME RETARDANTS, HALONS, FIRE ALARMS... 177
(IV) RUBBERS AND EXPANDED PLASTICS

A. Natural Rubber
Available from 2 species, the Hevea brasili-ensis tree and Parthenium argentatun called guayute
bush. Natural rubber crystillises at below 20°C.
Latex: pH = 6.5 – 7
Density = 0.98 gm/cc
Total solids = 30–40%
Rubber phase = 96% (wt. rubber)
Hydrocarbon = 1%
Protein = 3%
The field latex is processed by adding 0.4% ammonia and then centrifuged. After centrifugation,
the cream rubber concentrate is raised to 1.6% ammonia (wt.).
B. Rubber blends are used in 75% for all elastomars. Heterogeneous blends of natural rubber, SRB
or (cis-butadiene rubber-styrene) are used mainly in tyre treads as it reduces abrasion.
Homogeneous blends of rubber are rarely used; such homogeneous blends are formed if
difference in solubility parameters is smaller than 0.7.
C. Expanded or foamed plastics
These are blends of plastics with air. They are classified according to cell structure, viscosity
and nature of parent plastics. Their uses are mainly for thermal insulation (ps foam) and flexible
foams for damping and cushioning for packaging. Poly ethylene, Poly urethane, Polystyrene and
Plasticised PVC are semi rigid to flexible foams. PS copolymer with acrylonitrile or maleie anhydride
foam has increased resistances to heat and solvent. Surface treatment of such foams with fire
retardants (e.g. hexabromocyclodecane or pentabromo phenyl allyl ether) makes the foam flame
proof (class B1-low combustible as per DIN 4102).
Modulus of elasticity of expanded plastics decreases approximetely proportional to their polymer
content. Tensile strength of Foamed plastics follows the law of simple mixing. The cell structure
could be open, closed or mixed. Open celled foams are always air filled, regardless of blowing or
expanding gases. Trapped gases in closed cell structure can be exchanged by surrounding air by
diffusion only through polymerisation. All plastics can be foamed either by air or N2 or chemical
blowing agents (Azo dicarbo amide, Hexamethylene tetramine).
D. Above glass transition temperature Tg 20°C or more elastomers exhibit rubber like behavior.
The sheer moduli at this temperature range vary between approximetely 0.1 and 100 N/mm2
and exhibit a high visible deformability.
(V) FIRE HYDRANT SYSTEM

1. Every manufacturing and storage facility, large and medium, is to be provided with fire fighting
facilities as per statutory requirement. The designing of such a system by the approved
company is required as per requirement of the factory act as well as TAC requirements. This
is essential for installation’s safety against hazards of fire. Fire insurer of the factory needs to
know whether the factory has a fire licence which is possible if the Fire installation is provided
by a TAC approved co. TAC stand for Tariff Advisory Committee.
2. A composite fire protection system of a factory usually consists of:

2.1 Underground fire hydrant system with loop design and isolation valve.
2.2 Overground fire hydrant system for different floors.
2.3 Hydrants water supply at 8 kg/cm2g press with strategic underground loop isolation valves.
2.4 Fire pumphouse with booster pump (constant running) = (1+1) electric driven and electric
driven fire pumps (1+1) plus a standby diesel operated pump with heavy duty battery with
charger, are usually provided. Water is from fire water reservoir.
2.5 Accessories for hydrant like standpost (4") with hose coupling. Fire hoses with hydrant
coupling, 3" nozzle, Pr. gauges tapping pt. at end points of hydrants. The fire water pump starts
whenever pressure falls to below 7.5 kg/cm2g.
2.6 Foam maker is connected to Fire hydrant system for Foam-water spraying inside Fuel oil
storages as well as water sprinking on tank body.
2.7 A Fire station with a Fire water cum foam tender, Fire hooter alarm system, Remote fire alarm
switches at strategic plant stations to alart Fire station, Fire axes, portable fire extinguishers etc.
are essential requirements for fire station.
2.8 Portable Fire extinguishers, compressed CO2, Soda-acid (CO2), Carbon tetra chloride, dry
powder, and foam fire extinguishers are to be provided for any fire including electrical fires at
strategic locations of plant areas as per TAC requirement. Their nos. and capacity will also
conform to TAC requirement. Trolley mounted compressed CO2 fire extinguishers can also be
used. Foam and Halon fire extinguishers are also put into use. Sand buckets and empty buckets
for water are also to be provided in plant areas.
2.9 Source of reserved water for fire hydrants–This can be a surface water reservour close to Fire
station or an overhead fire water tank coupled with factory drinking water supply from own
W.T. Plant or outside water service provider. Often an overhead fire water tank is provided.
2.10 In addition, (i) the empty bags storage of the end product, if in bulk, is also provided with
fusible alloy fire water spraying system with own alarm system and (ii) fire detection alarm
systems in offices/godowns. Packed goods storages are also provided with fire detection alarm.
3. Classes of fire has been given in Vol. II B, T-34.
FLOAT GLASS, CARBON BLACK, ELECTROPHORESIS.... 179
Chapter
24
B
FLOAT GLASS, CARBON BLACK,
ELECTROPHORESIS, DRY ICE AND
TECHNOLOGICAL DEVELOPMENT IN
IRON AND STEEL INDUSTRY AND
ELECTROLYTIC CHLORINATOR
(I) FLOAT GLASS

1. Float glass is transparent, both sides are flat and parallel and polished so that a clear and
undistorted vision and reflection is obtained. It was discovered in 80’s and process of manufacture
perfected. The glass is made by floating on a heavier molten metal viz molten tin (having greater
density than glass).
2. Pilkington Float Glass Process of Manufacture
The charge raw materials for glass is melted in a glass furnace and conditioned by adding
sodium sillicate, arsenic/antimony trioxide. The melt glass is flown in a molten tin bath where a top
glass layer, typically 9m wide 45m long of desired thickness floats over molten tin. The temperature
of molten tin bath falls in the working range of temperature of glass. Because of extreme good
surface of molten tin, molten glass, as it flows over tin, smoothen sits surface and no further
polishing, smothening of glass surface is necessary. The glass body is rigid enough to travel without
damage, by the time it leaves the bath. Tin is used as a medium of floatation because of its surface
tension of 0.55 N/m and density 5–9 gm/cm3 compared with surface tention and 2.2–2.5 gm/cm3
density of glass. The m.p. of tin is only 505°K.
The float glass is of mirror quality and production capacity is more due to higher velocity which
is 5-10 times more than other float glass manufacturing process like Libbey-Owner’s process.
Pilkington process requires 4 persons/shift for 100 MT/day plant. The glass melting bath capacity
usually is 2 MT of melt per sq. mt per day. Heat input of 10,000 Kj/Kg of glass and temperature
1948°K and cycle of heating 16–17 hrs. (initial slow heating).
179
3. Uses of Float Glass

Mirrors, show cases, display windows, Glass doors etc.
(II) CARBON BLACK

A. Surface Area
Grade Surface area (m2/gm)
Coarse thermal black 10
Fine Pigment grade 1000
Tyre grade reinforcing 80–150
Carbon Black
Carbon black having surface area of 150 m2/gm is of 1.0 nm pore dia. Furnace black CB has
10–25 nm pore dia. and varies from 1–90 nm pore dia. depending on process used.
B. Density
1.8-2.1 gm/cc. (Graphitation increases it) to 2.185.
C. Carbon black Feed Stock (Petroleum) specification (CBFC)
Flash point = 70°C min
Boiling range = 200°C plus
BMC Index = 105–125
(US Bureau of mines corelation index)
Pour point = 50°C (approximetely)
Viscosity =
Temp. of solidfication =
Alkaline Content =
Mid B.P =
Sulphur content = 2–4.5%
C
ratio = 62–332
H
The CBFC usually consists of:
Monocyclic aromatics = 10–15%
Bicyclic aromatics = 50–60%
Tricyclic aromatics = 25–35%
Tetra cyclic aromatics = 5–10%
Note: In India CBFC contains 4–4.5% sulphur which reduces the BMCF yield (BMCI = 82–83).
D. Composition of Carbon Black
Carbon = 80–95% wt.
Hydrogen = 0.3–1.3%
Oxygen = 0.5–1.5%
Nitrogen = 0.1–0.7%
Sulphur = 0.1–0.7%
E. Some grades of carbon black : N 220, N 330 and N 660.
F. ASTM grades of carbon black are SAF, ISAF, HAF, FF. and FEF.
G. Other Types of Carbon Black Raw Materials

Type Raw material
1. Channel black = NG
or Gas black
2. Furnace black = Coal tar
3. Lamp black = CBFC
4. Tyre black = CBFC
5. Pigment grade = CBFC
6. Acetylene black = C2H2
There are two processes of manufacture of Carbon Black by incomplete combustion (Partial
oxidation) and thermal Pyrolysis. Surface area of different carbon blacks varies depending on raw
materials and process.
(III) SEPARATION OF MATERIALS BY ELECTROPHORESIS

This is an advanced technique for separation of ores, plastics and resins, vermicullite-mica
rock, making iron ore superior concentrates and causing removal of silica from iron and chromate ores.
Electrophoresis is caused by applying electric field either from a high voltage DC source or
from charged particles’s own field. The charging of particles could manifest in three forms viz. ion
bombardment, conductive induction or contact charging.
For grannular ores/materials, these materials fall on a grounded roller and charged by corona
discharge placed above the roller surface. Both conductors and non-conductors in ores/materials thus
become charged but only the conductor looses the charge on falling to grounded roller of the crusher
in different heaps. Uniform electric field is produced by corona discharge. In the di-electrophores
application, catalyst fines from Petroleum products and fibres from food stuff (in air media) are
separated.
(IV) DRY ICE

Manufacture
CO2 gas from sources viz. brewery etc. is drawn through a blower and is subjected to water
wash to remove aldehydes, higher alcohols (amyl alcohol), glycerol, H2S etc. After washing, CO2
gas is passed through a cooler and then through active carbon separator for removal of moisture
and hydrocarbons if any. Two active carbon separators are used-one remains in line while the other
one is regenerated by live steaming of bed and water cooling tubes followed by air purging from
previous use. The water cooler is embeded in active carbon separator for removing heat of separation
by cooling water. Since pore diameter of active carbon is 0.3 nm and is less than the molecular
diameter of gases to be removed and the active carbon molecular sieve allows only CO2 gas, to pass
through as its molecular diameter is 0.28 nm only.
After first stage molecular separator, CO2 gas is further treated with Potassium Permaganete
wash to remove organic matters which give bad smell. CO2 gas is then dried in a silica gel drier with
hot air regeneration when moisture in CO2 gas is reduced to low dew point level, usually –50°C.
After drying, CO2 gas is further passed through 2nd stage active carbon separator to remove last
traces of moisture and impurities. In silica gel drying, regeneration temperature is 120–150°C and
heat consumption per kg of water removed is 8000 Kj. In molecular sieve when moisture is removed,
usually 12000 Kj/kg of heat is consummed (for 2 layer ms).
Extremely pure CO2 gas, thus produced from m.s. separator column, is then compressed to
70–76 kg/cm2g, CO2 cooled in after cooler and chilled by refrigeration in chiller—when liquid CO2
is produced. Liquid CO2 is then expanded to atmospheric pressure through nozzles in the chiller when
snow like dry CO2 is formed by its own refrigeration effect. 1/3 rd of CO2 is transformed into dry
ice and remaining cooled CO2 gas is recyled to CO2 compressor suction. The solid dry ice is
compressed in a hydraulic press and moulds of 12–100 kg blocks are usually made. By expanding
liq. CO2 to ambient press, the temperature of CO2 falls below the tripple point of CO2 which is –
56.5°C at 75.1 PSIA (518 Kpa). The heat of formation of dry ice is 573 Kj/kg.
From brew eries
R aw C O 2 gas
Booster
C ooler
Active carbon
m s adsorber-1
H ydrocarbon
Perm anganate O rganic im purities
w ash tow er
Silica gel
dryer M oisture
Active carbon m s O dorous im purities

Separator-2
C O 2 com pressor
C ooler
R ecycle
Liq C O 2
C hiller
Expansion
Press
D ry ice blocks packing

Fig. 1. Block diagram for dry ice maufacture.
Uses of Dry Ice
It is mainly used in food industry for the transportation of deep frozen products and laboratory
chilling or other uses.
(V) TECHNOLOGICAL DEVELOPMENT IN IRON AND STEEL INDUSTRY

1. Blast furnace
Japanese have developed artificial intelligence in determining internal reactions, resulting in
temperature variation in a zone and overcoming this by correcting feed additions for uniform
temperature.
2. PCI (Pulverised Coal Injection) System
By injecting pulverized coal in B.F. coke requirement is reduced. By PCI technology, injecting
1 kg of coal, coke requirement comes down by 0.1 kg and corresponding coal requirement for coke
production reduce by 1.5 kg. Optimum PCI ratio is 100–105 kg of coal/ton of pig iron; lowgrade
coal and iron ore can be used.
3. DIOS Process
Direct iron ore smelting process (trial run NKK in 1993-94).
Here B.F. is in two section with production section at the top of smelting reduction section.
No coke and only low grade coal and lower grade of iron ore, can be used.
Feed is given to bottom section from where it traverses to upper section where it is prereduced
with CO gases from bottom under fluidised condition. The prereduced iron ore falls to the bottom
section through central pipe when molten metal is produced and tapped.
4. Steel Making
(i) Open Hearth process is gradually being phased out in Japan. It is only 15% in operation and
EAF with continuous casting and annealing is used thus saving in cost time and 10% reduction in
manpower has been achieved.
(ii) Scrap charge melting is carried in furnace and refining with alloying materials in laddle. By
this power consumption in furnace heating is reduced by 1/5th and production is increased by
1/3rd. D.C. Arc furnace instead of A.C. induction furnace also saves power.
5. BOF (Basic Oxygen Furnace)
Here, CaO, lime powder is injected in tyre along with oxygen. The power consumption, in steel
making, varies from 4.6 Gcal to and 8 Gcal/ton.
The main objective of the above development is saving in energy, process optimization for more
productivity, computerised control operation and saving in manpower so as to reduce cost and time
of operation.
(VI) ELECTROLYTIC CHLORINATOR

Chlorination by liquid chlorine injestion in circulating cooling water and drinking water are old
methods for disinfection. Modern method of chlorination is by electrolytic chlorinator which is fed
by sodium hypochlorite solution at preset chlorine dose to water for different end uses which require
disinfection. Chlorine kills bacteria and HClO reacts with enzyme.
The sodium hypochlorite solution is prepared in an electrolytic cell by the following reaction
using purified brine solution :
2Cl– 
→ Cl2 + 2e (anode)
Cl2 + H2O 
→ HClO + H+ + Cl– (cathode)
HClO 
→ ClO– + H+
hypochlorite
Cl2 + H2O 
→ HOCl + HCl
ClO– then combines with Na+ ion to give sodium hypochlorite. The cell can be mono polar,
bipolar or once through/recirculating.
The process consists of storing purified brine in a saturation tank from where saturated brine
flows to brine circulation tank. The brine is then pumped to electrolyser cells assembly with a
rectifier. The outlet sodium hypochlorite is divided into two parts—one part goes to hypochlorite
storage tank and the other goes to brine circulation tank. NaClO from storage tank is then taken to
feed points.
Beneficial Effects of Chlorine Apart from Disinfection
Odour control, reduces BOD, control sludge bulking and slime formation etc.
Uses of Electrolytic Chlorinator
Drinking water, swimming pool and cooling water disinfection, Hospital sterilisation, food and
beverages, brewery and bottling plants. NaOH plant, sea water pumping stations etc.
Chapter
25
CERAMIC COLOURING
MATERIALS
1. Industrial ceramic pigments are prepared by solid state reaction with minerals, suitable for
particular reactions. Whiteness or opacity is introduced into transparent ceramic materials, such
as glazes, by the addition of substances called opacifiers that will disperse in those materials
of glazes as discrete particles. There discrete particles scatter and reflect some incident light.
The dispersed substances in glazes must have refractive index that differs appreciably from
clear ceramic materials i.e., glazes. The refractive index ND20, of ceramic materials (glazes) is
1.5–1.6 and refractive index of opacifiers must be greater than that of glazes. In case of glazes
viz. tin oxide (III) (ND20 = 2.04), Zirconia (ND20 = 2.4, Zircon (ND20 = 1.85), titania (ND20
= 2.5) and for anatase and titania-rutile ND20 = 2.7.
2. The glazes and other ceramic coatings in ceramic materials after application of glazes with
opacifiers pigments are then fired in electric furnaces or hot blue gases at a temperature less
than 1000°C. Usually % of opacifiers differs according to type of opacifiers. For example,
finely ground Zircon (as opacifiers) is used at a concentration of 8–10% Zircon. The glazed
porcelain will be colourless if no pigment is used.
When pastel colour is required in porcelain, opacifier, along with a compatible ceramic pigment,
is added to the coating. The pigment chosen, should belong to the same opacifier group. For
example, Zircon opacifier should be used with Zircon or Zirconia pigments. For black colour,
Zinc or Cobalt free ceramic pigment is to be used.
3. COLOUR COMBINATION OF GLAZES

3.1 Yellow Pigment
Three combinations are available for firing temperature, more than 1000°C viz. Zirconia-
Vanadium yellow with Zirconium silicate (opacifier) and Tin oxide with vanadium yellow.
3.2 Pink or Purple Pigment
Chrome-alumina, Pink spinnel is free, from CaO and low concentration lead oxide or basic
oxide. Most stable pigment is Iron-Zircon combination.
185
3.3 Gray Pigment

Diluted black Pigment with white opacifier. Other combination is Tin based opacifier with Tin-
antimony carsilerite.
3.4 Green Pigment
Chromium is basic pigment but it has various limitations. Usually Zircon-Vanadium blue and
Zircon-presscodynrium yellow are used. For bright green colour two parts of yellow pigment and
one part of blue pigment with Zircon (opacifier) are used.
Copper containing pigments with opacifier is not used for making food containing ceramic
articles and non food items are made at lower firing temperature.
3.5 Blue Pigments
Cobalt-Al. oxide (CoAl2O4) or cobalt with SiO2 are used with Zircon based opacifiers.
3.6 Brown Pigments
Zinc, nonchromite brown spinnel or tin oxide (spinnel), iron chromite brown spinnel or chromo-
iron manganese brown spinnel.
3.7 Red Pigment
Cadmium Sulphoselenide or mixture of cadmium sulphide and cad. selenide, in the ratio of 4:1
(orange), 1.7:1 (red) and 1.3:1 (deep red).
4. Segar cone no. and temperatures for firing of glazes is given in vol. IIA.
5. There are 19 spinnel class pigments, Zircon group has 3 pigments, Baddeyte and borate
groups, each has one pigment, Phosphate group has 2 Pigments and Rutile/Cassiterite group
have 12 pigments.
6. APPLICATION OF COLOURS ON CERAMIC MATERIALS

There are five ways (i) As an engrave on a raw body (ii) as a body stain (iii) as an under
glaze colour to a bisque body (iv) as a coloured glaze (Pigment, dispersed in glaze) and (v) as an
over glaze already formed and fired glaze as an overcoat.
Chapter
26
GLASS FIBRES FOR INSULATION
AND OTHER USES
1. The mineral fibres or glass fibres consists of finely divided fibrous glass, highly dispersed with
specific area varying from 0.1–0.2 m2/gm. The fibre is oriented in longitudinal direction only
and the fibre is isotropic in 3rd dimension. Its open-ended Pore system offers little resistance
to flow which forms the basis of its good accoustic and thermal insulation properties. Its Low
Thermal conductivity, is based on fibre diameter and bulk density. The material is unsuitable
for load bearing structure construction. The material is also called glass wool or mineral wool
due to its similarity with wool. Glass wool is generally used for hot insulation.
Table 1
Thermal conductivity of mineral fibres
Thermal conductivity
wm–1°K–1
Type Temp°C Unit
Glass Wool 100 0.07
Glass Wool 200 0.078
Rock Wool 100 0.053
Rock Wool 200 0.090
Spl. rock Wool 100 0.041
Spl. rock Wool 200 0.060
2. MATERIALS USED IN PRODUCTION

(i) Glass Wool
Quartz sand, limestone, dolomite, phanolite, kernite feldspar, nephelime-senite, menite, baryte
and ulexite. Other chemicals used are sodium carbonate, sodium sulphate, barium carbonate along
with recycle glass and resin bonding material.
(ii) Rock Wool
Single material with limestone as additive to increase maleability. Minerals of suitable composition,
such as basalt, rhydite etc. are used.
187
(iii) Slag Wool

Blast furnace slag with limestone is used.
3. BROAD COMPOSITION OF MINERAL FIBRES

Vitreous fibre having dia, 3–6 µm = 90–99.8%
and length 3–10 cm.
Phenol formaldehyde resin modified with = 10% (max)
UF or melamine formaldehyde
Aliphatic mineral material = 1% (max)
Emulsifiers (noniomic Polyethylene, xylene) = 0.2% (max)
Polymethyl siloxanol = 0.5%
4. Chemical composition of mineral wool various with the process used. There are three processes
of manufacture viz. (A) Owen’s rock wool process (B) Rotary Process and (C) Centrifugal
blowing process. Mineral wool is inert to organic solvents even at higher temperature water and
aqueous solution attack glass surface and reduce resin bond. Chemically the fibres are composed
of silicate glass. Slag wool and rock wool are soluble in acids and are easily attacked by acid
flue gases.
Table 2
Chemical analysis of mineral fibres
A. Glass wool B. Rock wool C. Slag wool

Process used Rotary Owen’s Process Centrifugal blowing
Limiting temperature 570°C 700°C 735°C
SiO2 57.3% (wt.) 52.7% (wt.) 46.8% (wt.)
Fe2O3 0.35 1.8 1.0
Al2O3 3.6 8.0 10.2
FeO 0.1 1.4 0.3
TiO2 – 0.6 –
ZrO2 4.0 – –
MgO 4.0 4.0 2.3
CaO 8.6 20.9 37.7
BaO 1.7 – –
Na2O 11.2 10.3 0.9
K 2O 1.7 0.6 0.6
B2O 3 5.0 – –
F 2.3 – –
MnO – – 0.3
5. PROCESS OF MANUFACTURE OF GLASS FIBRES

(i) Melting tank, consisting of reqd. amounts of raw materials, is a cross fired recuperative-
regenerative furnace or 4 steped flame furnaces or electric melting furnaces. Gas or oil is used in
the furnaces whose capacity can be 3.5 t/m3. For rock wool, cupola furnace can be used with fuel,
either coke, oil or gas.
GLASS FIBRES FOR INSULATION AND OTHER USES 189
(ii) Owen’s Process uses steam or compressed air for blowing.

(iii) Rotary Process is a two step process suitable for soft and long filaments.
(iv) Centrifugal type blowing is used for slag wool manufacture.
6. GLASS WOOL AND ROCK WOOL

Glass wool and rock wool (mineral wool) are highly dispersed systems of finely divided fibre
glass with specific surface area of 0.1–0.2 m2/gm; glass wool filament dia. is 5.5 µ; density, 15 kg/m3
and Thermal conductivity (glass wool) at 200°C = 0.078 Wm–1.°K–1. These are suitable for hot
thermal insulation.
The mineral wool is having higher filament dia. and density of 6.5 µ and density = 30 kg/m3
respectively and its thermal conductivity at 200°C is 0.090. A special variety of rock wool has
filament dia. of 5.0 µ; density = 100 kg/m3 and thermal conductivity (rock wool), at 200°C is 0.060
Wm–1.°k–1.
Chapter
27
PLASTICS
1. These are synthetic long chain high mol wt. hydrocarbons and other groups formed by
polymerisation reactions viz. addition polymerisation and condensation polymerisation in presence
of some additives which improve the product quality. The hydrocarbon material, which is
polymerised, is called monomer. Addition polymerisation or free radical addition polymerisation
yields a polymer product of high mol. wt. The condensation polymerisation or ionic polymerisation
is a combination of monomers with elimination of simple molecules viz. H2O or methanol or
others. Linear polymer are having short chain molecules and no branch chains and as such,
molecular wt. of these polymer is lesser. Molecular wt. of plastics varies from 10000 to 100000
or more. Plastics polymers, prior to curing (heating process), is called resins. Monomers of
two different types when polymerise gives condensation polymers viz Styrene acrylonitrile
(SAN) Acrylic Butadiene Styrene (ABS).
2. There are two types of plastics: Thermoplastics and Thermosetting plastics
Thermoplastics can be melted repeatedly without loss of mechanical or physical properties and
reformed.
Thermoplastics
Polyvinyl Chloride (PVC)
Polyvinyl Acetate (PVA)
Polyethylene or polythene, PE (Low density and high density)
Polypropylene (PP)
Polystyrene (PS)
Polyvinyl Alcohol (PVA)
Polymethyl methacrylate (PMMA)
Cellulose Acetate (CA) polymer
Cellulose Nitrate (Celluloid) polymer
Polyacrylo nitrile (PAN)
Polycarbonate (PC)
Polybutadiene (PB)
Styrene acrilonitrile (SAN) and PTFE
190
PLASTICS 191
Thermosetting Plastics
These plastics are formed from certain virgin plastics by heating and cooling process which
cannot be remelted and reformed as it sets to a permanent form on cooling. On reheating it is likely
to decompose or deform.
Examples:
Melamine formaldehyde resin
Polyethylene terepthalate (PET)
Phenol and Urea formaldehyde (PF/UF)
Polyurethane (PUR)
Polymer silicones
Polyall (alkyd resin polymer)
XLPE (Polyethylene cross linked)
Acrylic resin
ABC
Nylon–6, Nylon–66
Polyester resin (Poly condensation of dicarboxylic acid with dihydroxy alcohols)
Furan
Acetal (Polymer of formaldehyde)
Epoxy resin
In addition to the above, there are other plastics, suitable for medical, scientific and industrial uses.
3. PROPERTIES OF PLASTICS
The properties are characterised by the following main physical and mechanical properties as
stated below:
Density and specific gravity. Plastics are generally solids with a few exceptions e.g., polysilicones
which are liquids.
Melting point, Vical softening point (°C) and Glass transition temperature, (°C), GTT gives
ability of a solid plastic material to crystallise and when relevant, indicates crystaline m.p. The ability
of a plastic to crystallise is determined by regulating its molecular structure. Usually GTT/Tg of many
polymers, except co-polymers is 2/3rd of crystalline m.p. In case of amorphous polymer, glass
transition will indicate whether or not the polymer is glass or rubber at a given temperature after
processing. Other properties are Tensile strength, Flexural strength, Modulus of elasticity, Impact
strength, Solvent Chemical, Electrical property (Die-electric constant), Water absorption rate and melt
flow index. Plastics detoriate in heat and sunlight specially when there is no U.V. protection additives.
Virgin plastics are available in solid form (Pellets/granules); few plastics are in fluid form and
powder form.
4. ADDITIVES
For processing of plastics these are used to improve the quality, mechanical and electrical
property. Along with additives, some percentage of used plastics are added to the processing
materials to improve melt properties. The additives are classified in several groups as under:
(i) Fillers (Solids and reinforcement fillers e.g., talc in P.P., usual fillers and reinforcements are :
Talc, Cellulose, Silica, Kaolin, Al(OH)3, Natural and precipitated carbonate, Carbon fibres, mica
powder, glass fibres and spheres etc.
(ii) Antioxidants–These are used to prevent degradation of plastics by chain breaking to prevent
oxidation and synthesis between antioxidants. Chemicals used are Tiophenols, alkylidene-bisphenols
(300–600 mol. wt.) and alkyl phenols.
(iii) Light (UV) stabilisers (UV radiation 360–380 nm wave length-to stop UV absorption from
sun light. Chemical used are Benzophenons, Nickel compounds, Cyanocinnamates, Salicylates, Benzoates
etc.)
(iv) PVC stabilisers–to prevent, detoriation by thermal stress. Chemicals used are Methylene
mercaptide, Butylene carboxylate, Barium-Cadmium or Ca-Zn stabilisers.
(v) Plasticisers–These are high boiling organic compounds usually liquid which gives better
processing properties and imparts flexibility and stretch-ability of plastics/resin or elastomers.
(vi) Electron beam crosslinking of PVC gives higher m.p. PVC.
Thermal conductivity of plastics is low, usually 0.0004 cal-cm/°C.cm2.sec and linear thermal
expansion co-eff. of plastics varies from 30 – 70 × 10–6 m/m°C.
For PVC processing more plasticisers are required until brittle point is exceeded and properties
change from rigid to soft. Type of plasticisers also depends on type of moulding-Injection, extrusion
or blow moulding. Common plasticisers are Phthalates (Phthalic anhydride and isophthalic acid).
Trimettileates, polyester, glutonic acid, acrylic acid, oleates, stearates, benzoates, terephthalic acid
and hexanol etc.
(vi) Lubricants–added to improve viscosity of melt. Examples—Fatty alcohols, dicarboxylic
acid esters, fatty acid esters of glycerol, fatty acid and fatty acid amines.
(vii) Cellulose derivities–used in coatings and adhesives.
(viii) Dye/pigment for colouring–generally azo/anthraquinone based dyes are used as pigments
and metallic oxides and inorganic hydroxides are used in plastics including amorphous carbon. Size
of pigments used varies from .01 to 1 µm.
(ix) Antistatic agent in plastic materials–High electrical charge develops into plastic materials due
to high volume and surface resistance and requires antistatic agent viz. cationic compounds, quaternary
alkyl carbonates and anionic compounds viz. alkyl sulphonate is to be added into the charge. Surface
resistance of a plastic should not be more than 106 ohm. To provide earthing to atmosphere from
processing room, so as to prevent static electricity flash.
5. PLASTIC PROCESSING
The virgin plastic moulding material usually in pellet form is mixed with required additives in
proper quantities in a Banbury mixer. The mixer is then throughly mixed and plastic processing is
done at above the crystalline melting point or in case of amorphous (powder) polymers above its
glass transition temperature. The charge is melted electrically and then led into the kneaders or rollers
maintained at 150–210°C and the melt is taken to moulds for the desired product.
In case of sheets/film products, film/sheeting machines are used. For cast films, cellulose
acetate is used.
Various types of plastics are used in packaging industry. The list of different plastics forms,
types and polymers used are given below:
PLASTICS 193
Forms Types Polymers

Films Blown films Polyolefins, PVC, PET
nylon and EVA
Cast films PP, PS, PET and nylon
Coextruded films Polyolefins, nylon
Oriented films PP
BOPP PS, PP, PET
Strings for sacks LLDPE, HDPE, PP
Lamination Extrusion lamination
on paper/Al foil Polyolefins
Dry bond lamination PET, BOPP, MET
Injection blow moulding Containers, bottles PS, PVC, Polyolefins
(stretched) PET, SAN, PP
Multilayer bottles Polefins, EVOH
Injection moulded Containers PS, PP, HDPE
Transparent Containers HDPE, MMA
Closures PS, LDPE, HDPE, PP, ABS
Foamed Sheets and casting PS, Polyurethane
NB. EVOH is ethylene vinyl alcohol. Compression moulding is no longer used now. Food
products packages are generally irradiated at 1.5 mega rads.
6. OUT LINES OF SOME PLASTIC MANUFACTURE ROUTES

(i) Ethylene → Ethylene Benzene → Styrene → Polystyrene
(ii) Ethylene → dichloroethylene → Vinyl Chloride → PVC
(iii) Ethylene → LLDP/HDP
(iv) Propylene → Cumane → Phenol → nylon
(v) Propylene → Isopropyl alcohol → Acetone → Acrylics
(vi) Propylene → Polypropylene
(vii) Acetone → Acetic anhydride → cellulose acetate
7. FOAMED PLASTICS OR EXPANDED PLASTICS

Foamed polystyrene, polyurethane and polyethylene are common plastics used in insulation,
packaging/lining of shoes soles etc. Process of manufactures involves in heating the polymer in
presence of additives and blowing agent, followed by cooling of the reactor effluent and finally
pouring the effluent into the mould. Blowing agent is different for different polymers.
8. PLASTICS FABRICATION MACHINERIES

(i) Injection moulding machine
(ii) Injection blow moulding machine
(iii) Extrusion machine
(iv) Film making machine
(v) Cast sheeting machine

(vi) Lamination machine
(vii) Sacks making machine on flat/circular looms.
9. PLASTICS FOR PACKAGING

The following plastics resins or polymers are used in packing industries:
PVC, PET, BOPP (Biaxially oriented polypropylene), PP, PE (Low and high density), PS, SAN,
LAN, PAN, EVA (Ethylene Vinyl acetate), EVOH (Ethylene Vinyl Alcohol), EMA and Foamed plastics
etc.
10. PROCESSES FOR PE MANUFACTURE

(i) H.P. process
(ii) Zieglar process
(iii) Philips process
(iv) Standard oil process
Chapter
28
FLOCCULATION
Flocculants are chemical additives for flocculation, used in the separation of suspended particles
in slurry or fluid by agglomeration and thereby help settling. Flocculants are used generally for
beneficiation of ores, purification of water etc.
A. INORGANIC FLOCCULANTS
Alum (Ferric alum, Pot. alum etc.) Poly Al. chloride, Sod. Aluminate, Ferric chloride, Ferrous
sulphate, Ferric sulphate and Sodium silicate.
About 10% solutions are used for inorganic flocculants.
B. ORGANIC FLOCCULANTS
Basically these flocculants are cationic, anionic or amphoteric polymer compounds (mainly
polyacrylamides) of high molecular wt. For neutral suspension of fluid/slurry, anionic or nonionic
organic flocculants are excellent when the slurry contains inorganic solids. The cationic flocculants
are the best for neutral suspensions, containing more organic solids. Most of the organic flocculants
are available in company trade names, some of which are given below:
Trade name Manufacturer
1. Superfloc, Accurac — Amer cyanamid (USA)
2. Calgon, Hydraid — Calgon (USA)
3. Separen, Purifloc — Dow chemicals (USA)
4. Herobloc, Reten — Hercules (USA)
5. Nelco — Nelco chemicals (USA)
6. Polyfloc, Betz — Betz Laboratory (USA)
7. Sedipar, Polymin — BASF (FRG)
8. Magnafloc, Percol, Zetag — Allied chemicals (UK)
9. Praestol — Chemische Fabrik Stockhausen (FRG)
10. Kurifloc — Kurita Kogya (Japan)
11. Di aclear — Mitsubishi chemicals (Japan)
12. Sanpoly — Sankyo chemicals (Japan)
13. Sanfloc — Sanyo chemicals (Japan)
195
14. Rohafloc — Rohm (FRG)

15. Floerger — Soe Nationale de Flocculant (France)
Tests Required for Flocculants
Sedimentation test, Filter Plate test, Buchner funnel test, press. filter test, Determination of
filtration rate etc.
INDUSTRYWISE USE OF FLOCCULANTS

Industry Uses and type of flocculant used
1. Ores beneficiation Floatation process, thickening and filtration
of concentrates etc. Flocculant used is
copolymer of acrylamide and sod. acrylate.
2. Potash mining Classification of Potash solns, dewatering of
tailings. Flocculant is same as in 1.
3. Barytes and Flourites mining Separation of floatation tailings. Flocculant,
same as in 1.
4. Phosphate mining etc. Water recovery in mines, filtration, Gypsum
filtration, Phosphoric acid clarification etc.,
Flocculant used in poly acrylamide and which
is used as in 1.
5. Salt works Classification of raw brines and sludge
dewatering. Flocculant used is poly sod.
acrylate and as used in 1.
6. Kaolin mining Thickening of Kaolin slurries. Flocculant used
is same as in 1.
7. Coal mining/washery Clarification of wash water, floatation tailings
and filtration of concentrated tailings and
filtration/dewatering of tailings. Flocculants
used as in 1, Polyacrylamide and
Polyethylamine.
8. Bauxite beneficiation Thickening of redmud from Bayer process.
Flocculant used is poly Sod. Acrylate.
9. Paper industry Dewatering of slurries and retention of Kaolin
on paper machinery, clarification and
dewatering of pulp recovery effluents.
Flocculants used are polyethylamine, Poly
acrylene polymer, copolymer of acrylamide
and cationic substituted methacrylates.
(neutralised and quaternised)
10. TiO2 Manufacture Clarification of black liquor and filtration of
TiO2. Flocculants used as polyacrylamide,
last flocculant in Sr. 8 and cationic carbonyl
polymers.
FLOCCULATION 197
11. Uranium manufacture Filtration of alkaline or acidic solns. Flocculant

used are polyacrylamide and polyethylene
oxide
12. Sugar processing Clarification of sugar juice and dewatering of
sludge. Flocculant used is same as in 1.
13. Steel works, foundries Clarification of BF gas scrubbing water,
clarification of effluents from sintering and
pickling plants, clarification of electrolytic
effluents and purification of electrolytic solns.
Flocculants used is same as in 1.
14. Bio-technology field Dewatering of biological slurries. Flocculants
used are same as in 8.
15. Water treatment plants Thickening of activated sewage sludge,
effluent purification, floatation of activated
sewage sludge, phosphate precipitation and
mechanical dewatering of sewage sludge.
Flocculants used is inorganic flocculant,
copolymer of acrylamide and sod. acrylate,
polyacrylamide.
16. Potable water works Flocculation of surface water, clarification of
wash water of filters and filter conditioning.
Flocculants used are inorganic flocculants,
copolymer of acrylamide and sodium acrylate,
polyalkalyne polymer and polyethylamine.
Chapter
29
PHOSPHORIC ACID
Phosphoric acid is a key material for the manufacture of other phosphatic and N.P.K fertilizers
or N.P. fertilizers. These are mono ammonium phosphate MAP (N = 11%, P2O5 = 52% wt),
Diammonium Phosphate (N = 18%, P2O5 = 46%), triple superphosphate (P2O5 = 46%) etc. With
addition of Muriate of potash, KCl, N.P.K. grades are manufactured. About 85% phosphatic fertiliser
are made form wet process phosphoric acid.
Commercial wet process phosphoric acid is classified according to the hydrate form in which
Calcium Sulphate crystallizes:
Hemihydrate – CaSO4.1/2H2O
Dihydrate – CaSO4.2H2O
The process is called wet because conc. sulphuric acid is used to digest the rock phosphate
ores. By 1980, hemihydrate and improved dihydrate processes were developed and 30–50% P2O5
wet process phosphoric acid plant, upto 1300 Mt/day, came up.
The other dry process or electric furnace process of Phosphoric acid manufacture is an
efficient process originally came up in 1935. But its use has declined except for the purpose of
manufacture of elemental phosphorous or the acid as an intermediate for making phosphorous element.
Rock Phosphate Ores
These are of various types e.g., fluorapatite, Ca10F2(PO4)6, Chlorapatite 3Ca3(PO4)2CaCl2 and
Phosphorite. Rock phosphate is characterized by BPL (Bone Phosphate of lime) value.
Chemical reaction
When a pure rock phosphate ore, say fluropatite, is reacted with sulphuric acid, the following
reaction takes place. There are various other reactions, as rock phosphate ores generally contain
various other impurities. For simplicity they are not shown below:
Ca10F2(PO4)6 + 10H2SO4 + 10nH2O → 10CaSO4nH2O + nH3PO4 + HF
where n = 0, 1/2 or 2, depending on hydrate form in which Calcium Sulphate crystallizes. The
reaction is the net result of two stages reaction. In the 1st stage, phosphoric acid reacts with
monoclacium phosphate and in the 2nd stage monocalcium phosphate reacts with sulphuric acid to
form phosphoric acid. The two reactions take place in a single reaction.
The impurities in rock phosphate as well as in sulphuric acid, precipitate in many side reactions.
Most rock phosphates have a higher CaO : P2O5 ratio than fluorapatite. The additional CaO consumes
198
PHOSPHORIC ACID 199
more sulphuric acid and forms more calcium sulphate. The HF formed reacts with silica and other
more complex compounds. A variable amount of fluorine is volatilized as SiF4, HF or both. The
amount volatilized and the form it does so depend on phosphate rock composition and process
conditions. Numerous side reaction compounds, some complex are formed in the reaction shown
above.
The heat of reaction, when n = 2 (dihydrate process), is calculated to be 230 or 257 kilo cal/
gm mole of apatite. If the reactants enter the reactor at 25°C and products leave at 82°C, some heat
of reaction is carried out with the reactants, the net heat to be dissipitated is 403 kilo cal/gm mole
if 100% sulphuric used. In case of other acid concentration excess heat dissipitated is:
Sulphuric acid Heat dissipitation
98% 385 kilo cal/gm mole
93 329 kilo cal/gm mole
75 180 kilo cal/gm mole
Table 1
Analysis of Florida Rock Phosphate
Constituent % by wt. Range Median

P2O 5 29–38 32
CaO 46–54 51
SiO2 0.2–8.7 3
Al2O3 + Fe2O3 0.4–3.4 1.4
MgO 0.1–0.8 0.2
Na2O 0.1–0.8 0.5
CO2 0.2–7.5 4.5
F 2.2–4.0 3.7
Cl upto 2.9 1.0
CaO : P2O5 ratio (wt.) 1.35–1.7 1.5
Organic carbon 0.005–1.7 0.3
Recommended quality of R.P. should be as per median analysis.
1. Bulk density (Florida R.P.) = 136.157 Kg/m3
2. Source of R.P. are : USA (Florida and Tennessee Valley), Israel, Jordan, Algiers, and
Morocco. Indian Udaipur R.P. quality is poor as it contains about 10% silica.
Dihydrate Process
This process is widely used because it is relatively simple and adaptable to wide range of grades
and types of rock phosphate ores and gives 26–32% P2O5 conc. of phosphoric acid with reaction
at 70–85°C. The separation stage after reactor, is only one (filtration stage to remove gypsum or by
centrifuging).
Assuming 94% overall P2O5 recovery, the number of tons of rock phosphate required per ton
of P2O5 required as Phosphoric acid is as follows:
Table 2
Type Grade of rock Rock required in

% P2O5 Tons/ton of P2O5
in acid
Low 29 3.67
Medium 33 3.22
High 38 2.80
Selection of Rock Phosphate Ores

Generally Phosphoric acid plants are designed on the basis of some standard rock phosphate.
However, it is better to consider the use of rock phosphate from other countries, having slightly
different specification and to design plant facilities accordingly should it be found necessary to use
rock phosphate from other countries to avail of opportunities of competitive rates or to avoid
disruption to supply due to hostility or non-availability. The extra investment will be more than to
compensate for savings due to freedom of choice.
The extra facilities required in such cases are:
1. Additional grinding facility for harder rock
2. Extra filtration capacity
3. Slurry handling systems that can cope up with acid insoluble impurities in rock
4. More corrosion resistant materials for rocks that have corrosive impurities.
Complete chemical and mineralogical analysis of rock phosphate and trial run for selecting rock
phosphate or changing the source, are required.
Factors to be considered selecting rock phosphate:
(i) R.P. to contain min. 32% phosphate as P2O5 for 16% W.S. P2O5
(ii) BPL values of 68–72% and H2SO4 usually 98% at calculated amount
(iii) Presence of impurities viz. iron pyrites, Al silicates and various fluorides within limits
(iv) Non Fluorides, iron, organic matter, Al silicates gives poor quality product
(v) Acid consumption is more if more Al and iron are present.
Sulphuric Acid Requirement
It can be determined from R.P. analysis. The followings are the typical parameters:
High Medium Low
CaO : P2O5 ratio in rock 1.70 1.50 1.35
H2SO4 reqd., ton/ton of P2O5 3.15 2.78 2.50
Receiving and Storage
1. Rapid unloading and delivery system of R.P.
2. Less loss of R.P.
3. Easy storage with ability to separate shipment of supply storage
4. Efficient retrieval from storage
PHOSPHORIC ACID 201
5. Storage covering against rain, dust and wind

6. Provision for expansion
7. Storage capacity should be one and half times the shipment capacity of tankers.
Rock Grinding
Dry grinding is used in older plants and some new plants, suitable for multi compartment
digesters. Prayon require 60%-200 mesh (Taylor) or 0.074 mm opening. Other new plants require
25%-200 mesh, 60%-100 mesh, all minus 35 mesh. Ring roller mills often used with air classification.
The power requirement depends on rock size, hardness and fineness is about 12–20 Kw per ton of
R.P. including air classification in bag type filters with a automatic shaking. Softer rock requires
2/3–1/2 of the above value. But dust pollution is frequent due to leakage from pneumatic conveying.
Wet grinding is generally found in plants located near R.P. mine. It is done in ball mills. A slurry
containing 62 to 70% solids is produced and fed to the digestors via a surge tanks. Power consumption
is lesser, 11–12 Kw/ton and there is no dust problem. For open circuit wet grinding the power
requirement is 18 KWH/ton. The major disadvantages are, faster erosion of balls and liners of mills,
decrease in amount of recycling water that can be used elsewhere in the plant and close control of
water/solid ratio in grinding.
Calcinating of Rock Phosphate
It is a part of ore beneficiation process, often found necessary to eliminate high organic matter
content or decreased carbonate content or both. For organic matter removal, fluidized kiln at 830°C
is sufficient. The organic matter in R.P. also form part of fuel cost. Calcined R.P. also enhances
production of R.P. by 30–40% and saves antifoaming reagent in digester.
Reaction in Digestors
There are several types of reactions vessels designed by manufacturers. The most important
factor is production of gypsum crystal of such shape and size which will allow rapid filtration of
slurry from digestor.
The losses of P2O5 due to lower recovery of P2O5 are:
1. Unreacted rock
2. P2O5 crystalises with gypsum through isomorphic substitution of HPO4 for SO4
3. Phosphoric acid lost in the gypsum due to incomplete washing
4. Others are spillage, leakages, washing of filter cloth, piping, equipment, scale removal and
losses as sludge.
Digester or Reactor
A multicomponent reaction vessel is used having agitators. Sulphuric acid is poured with
recycled of weak phosphoric acid and discharged into 1st, 2nd or 3rd compartment (no. of
compartment depends on plant capacity) as reaction system is designed not to mix R.P. and sulphuric
acid directly to ensure slow growth of gypsum crystal to a relatively longer size for ease of filtration.
Retention time of reactors varies from 15 hrs. to 3 minutes and usually it is 1.5 hrs. to 12 hrs. or
more. Also, a high concentration of free H2SO4 will result in the coating of R.P. with CaSO4 reaction
product, thus blocking further reaction. A serious block in reaction systems can take hours or even
days to rectify.
The rock slurry from wet grinding is discharged into 1st, 2nd or 3rd compartment or divided
among them. The reaction temperature varies from 85–100°C. A portion of rock slurry is withdrawn
for temperature control and fed to a vacuum flash cooler. Part of cool slurry is fed to attack system
and part to digestor. The slurry moves from last compartment to first compartment. The digestor
tanks permit completion of reaction and lowering of any super saturation under mild agitation. A
small adjustment can be made by adding small R.P. or sulphuric acid as required.
Premixing recycle weak phosphoric acid with conc. H2SO4, evolves much heat and vapours
of H.F., SiF4 which is also carried out, separately in some in plant in flash vacuum cooler to separate
H.F. and SiF4 which can be used to produce hydroflourosilicic acid.
In Swenson Gulf isothermal process, a Swenson crystalliser is used as single reactor suitable
for granules of R.P. (0.42–1.1 mm or smaller) where such R.P. can be used with lower operating
and m/ce cost and control of atmospheric pollution.
A thin spray of conc. H2SO4 acid is sprayed on top of slurry while R.P., mixed with weak
P2O5, is fed from bottom; an agitator agitates reactor fluid so that isothermal condition is maintained.
The reactor slurry is filtered; waste and weak acid is recycled. Reactor cooling is by flash cooling.
Such plants can be built up upto 650 MT per day.
In Rhone poulene process, temperature of reactor is controlled by flow of air on surface of
reactor by evaporative cooling of droplets of slurry picked up by a sprayer system. Sulphuric acid
is also added as a spray at top of reactor. R.P is introduced through center at top zone of maximum
agitation. The process is suitable for 100–80 MT per day P2O5. There are other processes using
single or multiple reactors.
Process Key Parameters
Control of H2SO4 content in liquid phase is very important for close control of reactions, an
optimal values of 1.5% is typical and is difficult to control when reaction time is sort. Most of the
processes used 8 hours reaction time with Kellog-Lopker dihydrate process (used in England) which
requires a short residence time of 1.5 hrs. with two reactors but uses a automatic SO4 control
instrument for close control of sulphate.
Table 3
Crystal form (s) No. of separation Conc. of product Temp. of Recrystallisation
stages acid % P2O5 reactor temp.
Hemihydrate 1 40–50 85–100 –
Hemihydrate- 1 26–30 90–100 50–60
dihydrate
Hemihydrate- 2 40–50 90–100 50–65
dihydrate
Dihydrate- 2 35–38 65–70 90–100
hemihydrate
Hemihydrate Process
In hemihydrate process of phosphoric acid manufacture, a high conc. of acid is obtained, until
that acid may not be further concentrated. Such consideration will depend on whether waste heat
steam from on site sulphuric acid plant can be used elsewhere in the plant. When concentration is
not necessary, both capital and operating cost become less. Product phosphoric acid is also somewhat
sludge free and less aluminium in acid. However, better material of construction is required in reactor,
pump, filtration, centrifuging as reaction temp. is high which enhances corrosion.
PHOSPHORIC ACID 203
Hemihydrate-Dihydrate Process
This process, as developed by Nissan Japan and named Nissan H Process, uses only one
filtration process and gives pure by-product gypsum which can be used in other products of
manufacture without any further treatment. The P2O5 recovery from R.P. is 2-3% or more as losses
of P2O5 in gypsum is very less. However the plant cost is higher due to elaborate process stream.
Hemihydrate-Dihydrate Process with two stage filtration of centrifuging is also provided by Fisons
HDH Process and Nissan C Process. However, extra capital cost, due to additional filtration stage,
is offset by additional recovery of P2O5.
Filtration of Digestor Effluent
The effluent from digestor or reactor is filtered to remove gypsum and any insoluble materials
from rock phosphate or formed in the reaction from phosphoric acid completely and efficiently by
continuous filtration, usually rotary tilting pan type filters, travelling pan filters, horizontal table filters
and even belt filters are used. The cycle of filtration in these filters proceeds as follows:
(a) Deposition of phosphoric acid–gypsum slurry on filter cloth
(b) Collection of phosphoric acid from filter by application of vacuum
(c) Two-Three counter current washers to completely remove the phosphoric acid from
gypsum and from filter cloth
(d) Discharge of washed gypsum
(e) Washing of filter cloth to prevent scale formation.
In the washing stage, successively weaker solution of phosphoric acid is collected. The last
wash is with fresh water or sump water. Very weak phosphoric acid, collected from last section,
is returned to the preceding section. The filtrate from the first section is often returned to the
reactors. In addition, some portion of product acid is also recycled to reactor to control percentage
solids at 40–50% level. The design filtration rate is 6.5 t/m2/day. The filtration rate varies due to
various factors; type of R.P. and impurities including presence of insoluble matters like clay, use of
crystals shape modifiers in reactors, control of reaction conditions viz. temp., conc. and viscosity
of acid and extent of recovery. Filtration rate also varies due to design of filter, % vacuum, type of
cloth and other criteria.
Concentration and Clarification of Phosphoric Acid
Dihydrate Process Phosphoric Acid has a concentration of 26–32% P2O5. This acid can be
used in manufacture of some phosphatic fertilisers but for most other purposes, it is economically
preferable to concentrate it by evaporation. The concentration of P2O5 for phosphatic fertilisers and
other uses as below.
Table 4
Product Phosphoric acid conc. % P2O5
MAP (depending on process) 40–54
DAP 40
Shipment grade 54–60
Superphosphoric acid for shipment 69–72
for fertiliser production
TSP–Den Process 50–54
TSP–Slurry Process 38–40
Precipitates formed in phosphoric acid during or after conc. are usually collected at bottom of
container. The precipitates formed before conc. are mainly calcium sulphates and fluorosilicates.
Accordingly to acid conc. a no. of precipitates can be formed during and after conc. These
precipitates are called sludges and cause problems in handling and use of the acid.
Phosphoric acid concentrators may by termed as indirectly heated concentrators or directly
heated ones (uses are declining due to difficulties of recovery of phosphoric acid mist and fluorine
compounds from exhaust gases). Super phosphoric acid is made by concentration of 54% P2O5 acid
in directly fired concentrator. Prayon, Nordac and others have developed acid concentrators from
30% to 54% P2O5. Fuel requirement for this range of conc. is 140,000 Kcal/t P2O5 and power 70
Kwh/t P2O5. Any liquid or gaseous fuel can be used. For conc. from 54% to 70% P2O5, fuel required
is 600,000-800,000 Kcal/t P2O5.
Indirect heated concentrators are heated by steam or some heating media viz. dowtherm heated
by flue gases from a furnace in an exchanger. Common type of evaporators or concentrators with
forced circulation or evaporator-crystalliser, where precipitates grow into coarse crystals and removed
by centrifugation or settling. For conc. from 30% to 54% P2O5. It can be carried out in 1, 2 or
3 stages. Steam required for conc. is 1.90 t/t P2O5, power 11–16 Kwh/t P2O5 and cooling water 6
m3/t P2O5 for condensers. Fluorine removed during conc. is about 70–80% of original conc. in acid,
most of it is volatilized or condensed in condenser and recovered.
For conc. from 54% to 70% P2O5, H.P. steam (27 ata 230°C), required is 1 ton per t P2O5,
power, 24 KWh/t. Fuel for downtherm heating is 640,000 Kcal/t P2O5. In concentrating Phosphoric
acid to super phosphoric acid 69%–72% P2O5, most of fluorine is volatilized so that F content is
reduced to 0.2–0.3%. Reactive silica is added during conc. to enhance fluorine evaporation and F
can be brought to 0.1%. Such acid is suitable to produce dicalcium phosphate or ammonium
phosphate, used for animal feed also.
Advantage of Super Phosphoric Acid:
1. Saving in freight cost
2. Sludge elimination
3. Acid is less corrosive
4. Suitable for production of clear liquid fertiliser (ammonium polyphosphate solution).
5. The acid can be used to produce compound fertilisers by melting route.
The main disadvantages are higher energy requirement, high viscosity (acid required heating
upto 60°C prior to pumping) and corrosion in concentrator.
Table 5
Chemical composition or Super Phosphoric Acid
Phosphoric acid, as P2O5 = 69–72%
Fluoride as F = 0.2–0.3
When reactive silica is added during concentration of Phosphoric acid, F content can be
brought down to 0.1%.
Uses: For dicalcium phosphate production, ammonium phosphate.
Use of Sludge in Phosphoric Acid
Precipitated sludge in phosphoric acid contains about 38 (Max) distinct Phosphate compounds
depending on impurities present in rock and sulphuric acid. The precipitates appear before, during
PHOSPHORIC ACID 205
and after conc. Precipitation is a continuous process in storage of phosphoric acid. The usual method
of separation of precipitates is by centrifuging/filtration. Sludge formed after conc., contains a high
proportion of complex Al and Fe phosphate compounds e.g., (Al, Fe)3KH14PO4)184H2O. The separated
sludge is mostly citrate soluble and is often used in T.S.P. Production where TSP is sold on the basis
of citrate solubility and not water solubility basis. The sludge can be mixed in the production of
nongranular MAP which is used as an intermediate for the production of compound NPK fertiliser.
Material of Construction
Reaction tanks/ reactors and its agitators are subjected to most severe corrosive action. The
tanks are often made up of lined steel tanks or concrete with carbon brick lining inside. Suitable
concrete mixture with additives are used in case there is carbon brick lining damage. The flash
coolers and circulating pumps as well as filters are subjected to severe corrosion. Abrason is most
prominent in vessels starting from reaction to filtration steps. The quantitative value of corrosion is
the result of chemical and physical factors. The presence of impurities in phosphoric acid enhances
corrosion.
1. Physical Factors
Peripherical speed of process fluids;
The speed, usually considered in a phosphoric acid plant is given below
Filter cell = 30 m/min
Pipes = 60 m/min
Agitators = 250 – m/min
Pump impeller = 1000–1500 m/min
2. Temperature
Although temperature level is lower, corrosion gets enhanced with rising temperature.
3. Chemical Factors
(i) Conc. sulphuric acid in presence of metal cations, Ca++, Al++, Fe++, etc.
(ii) Excess H2SO4 – this causes more corrosion if excess is more than 1.5–2% or H 2SO4 conc.
is beyond 20 gm per lit. in reaction mixture. Pitting, due to chlorides, is enhanced at this conc.
(iii) Presence of Fluorine in R.P. – The conc. varies from 10–14% or P2O5 in R.P. The HF
acid in formed between reaction of R.P. and H2SO4.
(iv) HF has a great affinity for silica:
6HF + SiO2 = H2SiF6 + 2H2O
However, HF is more aggressive acid in corrosion process than H2SiF6 (Fluosilicic acid).
(v) Presence of Chloride in R.P. beyond .01 – .05 limits enhances pitting in metals.
Table 6
Analysis of single super Phosphate
Single super phosphates contain mono, di and tri calcium super phosphates along with iron
and Al sulphates, calcium fluoride and gypsum. Typical analysis of single super phosphate is as
below:
P2O 5 (W.S) = 18% (6% as free acid corresponding to 8.3% H 3PO4)
Water = 5.39 (Water of constitution)

P2O5 (Citrate soluble) = 0.40
P2O5 (insoluble) = 0.46
CaO = 26.6
F = 1.1
SO3 = 31.3
Fe2O3 = 0.48
SiO2 = 1.75
MgO = 0.14
Al2O 3 = 0.25
Capital Cost
The capital cost (1990) of a 600 MT/day phosphoric acid plant is of the order of US dollar
26.9 million + 50% cost for off sites facilities. The break up cost is as follows:
R.P. storage = 4.4%, Phosphate rock grinding = 17.6%, reactions and filtration = 44.9%, acid
conc. = 14.7%, gypsum scrubber and ponds = 15.3% and acid storage = 3.3%. This is as per
European conditions.
TSP contains 46% P2O5 and is also called concentrated super phosphate.
New technology for phosphoric acid manufacture:
Israel Mining Industry has developed a process using HCl for manufacture of phosphoric acid
instead of H2SO4.
Chapter
30
ELECTROPLATING PROCESS
In plating process, metallic ions in the electrolytic bath are reduced and deposited on cathode
as a metallic coating when current of required density and voltage (D.C.) is passed to bath. The
anode can be the pure metal, being deposited in soln. or it can be insoluble anode, usually carbon
rod, when metallic salt of the metal is reqd. to be added to the electrolyte to maintain concentration
of metal ions.
The electrochemical process is controlled by (1) Faraday’s laws of electrolysis (2) Standard
single electrode potential and (3) Ohm’s law. Faraday’s laws gives the quantity of materials deposited,
being directly proportional to the amount of current flow and its duration. It is inversely proportional
to the oxidation state of metal in the electrolyte. Ohm’s law gives the flow of current being directly
proportional to the applied D.C. voltage and inversely proportional to the resistance of the system.
The internal resistance of the electrolyte bath depends on various factors.
Standard single electrode potential of the metal to be deposited, gives min D.C. voltage for
plating. The actual voltage reqd. is determined as per various competing reactions in the bath. Single
electrode potentials are given in table 18 (vol. IIA). A normal H2 electrode is used to determine
potentials of other metals.
As per Faradays Law W = CtZ
where W = wt. of ions deposited, C = Quantity of electricity passed, coulombs (current in
amps × time in secs) t = time in secs, Z = Electro chemical equivalent of metal ion or wt. of ion
deposited by 1 Amp current in 1 sec.
96500 coulombs of electricity (1 Faraday) is reqd. to deposit/liberate 1 gm. equivalent wt. of
any element.
V
As per Ohm’s Law – c =
R
where c = current flow (amps) V = potential difference, (Volts) R = resistance, (Ohms)
Standard single electrode potential of a metal in soln. of its salt containing one gm-ion of the
metal per litre and a normal hydrogen electrode. The e.m.f. of a electroplating bath is the difference
of single electrode potentials of electrodes in the bath.
1. TYPES OF ELECTROPLATING
There are five types of plating processes of coating on base metals:
207
1. Rack Plating
2. Barrel Plating
3. Spot plating or brush plating
4. Pulse plating
5. Non electrolytic deposition
1. Rack Plating
Parts to be plated, are fastened to fixtures (cathode) in the plating bath where it is immersed
either manually or some auto processes. The fixtures carry the plating current to the parts.
2. Barrel Plating
The parts (pins, clips, lip stick cans, buttons etc.) which are small pieces are put in a plastic
hexagonal perforated container which is rotated either manually or automatically through the electrolytic
bath. The parts slowly tumble while the barrel is rotated and all are exposed to the plating action.
Current is supplied through various types of controls into the mass of parts where it is transferred
piece to piece by contact during rotation.
3. Spot Plating or Brush Plating
Here plating is not done by total immersion only. Using anodes, surrounded by absorbent
material that do not require immersion of parts and portable equipment for spot plating is done. The
anode is a saturated soln. which is rubbed over the surface area to be plated. Very high localised
current density is used because of movement and abrasive action on absorbent material. This is a
patented process till 1995. This is suitable for electrodeposition of worn out machine parts.
4. Pulse Plating
This is immersion plating with the difference that current is passed in short intervals of higher
intensity followed by stoppage of current. Each cycle is indicated as ratio of on time/off time duty
cycle in % and the frequency of time length of each cycle. Not all metals can be used here for
deposition as some metals can not tolerate variation in current flow more than 5–10%. The process
was under research till 1996.
5. Non Electrolytic Deposit
There are three types of deposit, namely immersion or displacement deposit, noncatalytic
chemically reduced deposit and catalytic chemically reduced deposits.
2.0 ELECTROPLATING BATH AIDS

Various chemicals are used for pH control, good plating quality, brightness, hardness of deposits
etc.
(a) Rack Gold Plating on Copper or Copper Alloys
Gold plating solution:
Gold chloride = 2 gms/lit (0.27 oz/gallon US)
Pot. cyanide = 0.025 gms/lit
Pot. pyrophospate = 80 gms/lit
Bath temperature = 65–87°C
ELECTROPLATING PROCESS 209
D.C. voltage = 6V
Current density = Amp/cm2
Anode = S.S.
Anode-cathode ratio of area = 3.1
N.B. Technical grades of chemicals should be used for better results.
(b) Tin Plating on Iron
Tin plating solution:
SnCl2H2O = 15 gms/lit (2 oz/gallon US)
NaOH = 19 gms/lit
NaCN = 7.5 gms/lit
Hot boiling soln. is used
D.C. voltage = 6V
anode-cathode ratio of area = 2.1
(c) Cadmium Plating
CdO = 30 gm/lit.
sod. cyanide = 40 gm/lit or
Cd cyanide = 40 gm/lit
Anode-cathode ratio of area = 2.1
D.C. voltage = 4–6 V
Efficiency = 95%
Temp. = 20–35°C
Total NaCN/Cd = 3.75 : 1
D.C voltage = –
(d) Chromium Plating
CrO3 + H2SO4 + catalyst soln. = 250–350 gms/lit
CrO3/SO4 = 75 : 1 or 125 : 1
Temp. = 32–43°C (decorative articles)
37–65°C (hard deposit)
C.d. = 10–20 Amp/dm2 (decoratives)
= 15–35 Amp/dm2 (hard deposit)
(e) Copper Plating
CuCN = 22.5 gms/lit
Sod. cyanide = 34 gms/lit
Sod. chromate = 15 gms/lit
NaOH = as reqd. to adjust pH

Analysis : Cu = 16 gm/lit
Free CN = 7.58 gms/lit
Temp. = 32–43°C
C.d. = 1–1.5 Amp/dm2
Voltage = 6 V
Anode Cathode area ratio = 1.1
Efficiency = 30%
(f) Bright Gold Deposit
KAu (CN)22H2O = 4–16 gm/lit.
KCN = 15–90 gm/lit.
Pot. carbonate = 0–30 gm/lit.
Pot. Phosphate = 0–45 gm/lit.
KOH = 10–30 gm/lit.
Brightner = 0.1–10 gm/lit.
Temp. = 15–25°C
C.d. = 0.1–0.5 Amp/dm2
Agitation = Reqd. (moderate)
Anode = Platinum/SS or gold
DC voltage = 6–12 V
Anode-cathode area ratio = 3.1
(g) Pure Aluminium Metal
Pure Aluminium is made by electrolysis (which forms the cathode where Aluminium is deposited.
The anode is the crude metal rod. The electrolyte is AlCl3. Voltage maintained is 4V D.C.
(h) Aluminium Production
Aluminium production by electrolysis of pure bauxite in a cell house containing a large no. of
cells called “pot” which are connected in parallel at 4V.D.C. Bauxite is mixed with cryolite (Sod. Al
flouride) in reqd. proportion and 8% Calcium flouride is used to reduce melting temp. to 1000–
950°C. Crude Aluminium is deposited on cathode which forms bottom of the pot and oxygen is
liberated on carbon anode rods, suspended in the bath. Oxygen then reacts with carbon of anode
NaF
to form CO2/CO. For maximum current efficiency, wt. ratio of AlF is maintained at optimal level
3
and AlF3 is added at regular interval to compensate the volatility loss. Bath is maintained 12–15°C
over the melting point. The polarities of cells (anode and cathode) are changed at intervals to over
come polarisation.
3. OTHER CONSIDERATION IN ELECTROPLATING

(i) Strike soln.–The sol. is so designed as to deposit thin layer at relatively high c.d.
ELECTROPLATING PROCESS 211
(ii) High over voltage–maintained to overcome high hydrogen deposition potential at cathode.
(iii) Covering power–higher c.d. to deposit metals in recess/bodies.
(iv) Throwing power–ability of soln. to deposit higher coating thickness of metal into low
current density area.
(v) Depositing potential of metal–It should be lower than that of hydrogen.
(vi) Alloy plating–Two or more metals of alloy should be present in electrolyte and their
deposition potential is sufficiently close.
(vii) Stabiliser–It is an additive to electrolyte to prevent oxidation of iron or Fe+2.
(viii) Brightener–Additive to ensure brightness of coating by modifying grain structure.
(ix) Cathode coating–When the protecting metal is situated below the protected metal in the
e.m.f. series. Example–Tin plated iron. Whenever tin losses integrity, bared iron comes
in contact with moisture and a galvanic couple arises where tin serves as cathode (+ve
electrode) and iron as –ve electrode (anode). The electron flow from bare iron surface
to tin where they discharge H ions while iron decays sending more and more iron into
soln.
(x) Anode coating–It is reverse of cathode coating.
3.1 Signs of Cathode and Anode
Signs of cathode and anode terminals are exactly opposite to those in galvanic cells where
anode is –ve electrode and cathode is +ve electrode while in electroplating or electrolysis, on the
contrary, cathode is –ve electrode where ions give out charge and anode is +ve electrode where
metals go into soln. as +ve charged ions.
Chapter
31
COOLING TOWERS
1. Cooling towers and spray ponds are devices for the cooling of water by transfer of heat, from
hot recirculated cooling water from factory plant facilities. The c.w. gains sensible heat from
various heat exchangers; by exposing the surface of hot water to incoming / surrounding air
which cools the water by partly evaporating the hot water so as to remove the latent heat of
water and also a part of sensible heat of hot water is removed. This is due to difference in
temperature between hot water and incoming/ surrounding air to the cooling tower system or
spray pond. The total heat thus removed to the air from the hot recirculated water in the cooling
tower, or spray pond is the sum of latent heat of evaporation and sensible heat. The air
temperature must be lower than the hot water temperature. The cooling of water in cooling
tower or spray pond takes place upto and below the wet bulb temp. of air in warmest summer
months.
Cooling Tower Types
(i) Induced draft mechanical tower.
(ii) Forced draft mechanical tower.
(iii) Parabolic chimney type cooling tower.
(iv) Spray ponds for smaller cooling duty.
Out of two types of mechanical draft cooling towers only Induced draft tower with fan at the
top of tower is widely used because there is no chance of short circuit of moist hot humid air, as
found in forced draft tower, with fan at the bottom of tower. I.D. cooling towers can be grouped
in a row of several towers depending on cooling duty and water rate, per unit cross section, is 2-
3 times more than that of natural draft towers. In I.D. cooling tower maximum approach to W.B.
temperature is economically possible. Running cost of mechanical draft C.T. is higher due to power
cost of fans. Hot water is put into the sump at the top of tower and it flows into C.T. through nozzles
at the top deck. Splash bar fills inside the tower gives the increased area of contact of water with
the air.
Wind velocity below 4 km/hr is suitable for I.D. tower; cooling approach, upto 5 °F. of W.
B. temperature of air is possible during summer months for design purpose. I.D. cooling towers have
double entry of air through lowers at two sides and air and water flows counter currently.
In mechanical draft cooling towers, hot water from plant facilities is directly taken to the top
and flows through two flapper valves into top deck having plastic nozzles for flow of hot water into
the basin. Cooling water level in top deck is kept at 3"–5" height.
212
COOLING TOWERS 213
Natural Draft Cooling Tower

These are hyperbolic tall, usually concrete, towers with hot water spraying arrangement at the
top through which water falls through the empty tower without any splash bars. Air enters at the
bottom of the tower and flows upward by the draft produced due to difference of temperature
between top water zone and bottom zone of cold water. Operation and maintenance cost is low but
drift loss from top is more and cooling approach is lower. Wind velocity, higher than 4 Km/hr is
suitable but precipitation loss is more. First cost is higher.
In natural draft cooling tower hot water pump, at the bottom of the C.T., boosts the pressure
for sending hot water to the top sprayers due to higher head required to lift the hot water. This
increases the operation cost. Cold water pump usually recirculates the cold water to the plant.
Thermometers are used for measuring Hot and Cold water temperature and pitot tube is used for
measurement of cold water flow. Hot and cold water header pressure measurement are usually
provided.
2. SPRAY POND
Here hot water is sprayed through a series of spray nozzles in cold water pond and temperature
of water comes down due to sensible heat transfer and evaporation which removes the latent heat.
The heat duty is less and operational cost is the least. Cold water is recirculated to the plant facilities
from spray pond.
In general for all types of cooling water systems emergency cooling water circulation pumps
with stand by emergency power, are usually required to run the pumps/critical equipment on power
failure. A pit pump provision for draining of cold water basin is usually kept as well as cold water
outlet strainers for cold water outlet to cold water pump, are provided.
3. DESIGN CRITERIA
Cooling approach: It is the difference between cold water and wet bulb temperature of water.
A minimum of 5°F cooling approach during summer months is possible.
Dew point temperature: Temperature at which air-water mixture is saturated with water vapour.
Cooling range: It is the difference between hot water temperature and cold water temperature.
Wet bulb depression: It is the difference between dry bulb and wet bulb temperature.
The following parameters are required for designing a cooling system.
(i) Quantity of water to be cooled, m3/hr.
(ii) Wet and dry bulb design temps. selection.
(iii) Air velocity through the towers. m/sec.
(iv) Maximum and minimum dry bulb temperature.
(v) Hot water and cold water temps required.
(vi) Height of tower, m and tower fill volume, m3.
(vii) psychrometric chart of air at atmospheric pressure.
4. PERFORMANCE COEFFICIENT OF A COOLING TOWER

This is based upon the heat dissipated per square metre of cross-sectional area of cooling tower
per degree C/ degree F cooling approach to the wet bulb temperature.
W ( t w1 − t w2 )
kcal/hr m2 °C
Performance co-eff =
Sa (t w2 − t w.b )
Where W = Cir. rate, m3/hr.
Sa = Packing area. m2
tw1 = Hot water temp. °C.
tw2 = Cold water temp. °C.
tw.b = Wet bulb temp. °C.
5. PSYCHROMETRIC CHART AT ATMOSPHERIC PRESSURE

The relation between dew point, saturation point of air and specific humidity of air is given by
Psychrometric chart. It shows saturation curves for air at different % saturation upto 100% saturation
(dew point curve) at different dry bulb temperatures in horizontal axis vs partial pressure of water
vapour in air as well as specific humidity in vertical axis. See psychrometric chart in chapter 44
Dew Point and Humidity
(i) Dew point temperature can also be found out from steam table by knowing partial pressure.
Dew point remains constant so long air remains unsaturated. Dew point rises if some additional
moisture is added to the air as partial pressure of water vapour rises.
(ii) Wet bulb temperature is the dynamic equilibrium temperature attained by water surface
exposed to air when the sensible heat transfer from air to the water surface is equal to the latent
heat of evaporation of water carried away to the air from the water surface.
(iii) Percentage relative humidity – It is the ratio between partial pressure of water vapour at
any temperature to the difference between total pressure less partial pressure of water vapour at the
same temperature.
(iv) Dry bulb temperature – It is the ambient air temperature.
(v) Percentage humidity of air – It is a ratio between kg of moisture carried in 1 kg of dry
air at the desired temperature to the amount of water vapour carried by 1 kg of dry air at saturation.
6. SIZING OF COOLING TOWER

As per graphical method given in Perry'.
7. COOLING TOWER FAN

These are motor driven axial 4/8 bladed cast aluminium fans with reduction gear box located
at the top of cooling tower (I.D. tower). Air swept volume through the tower is one of the key
factors in proper performance of cooling tower. A medium height chinmey around perimeter of fans
sweep is installed for providing required draft of air.
In F.D. cooling tower fan is located at the base of cooling tower.
8. COOLING TOWER MATERIAL OF CONSTRUCTION

Normally Ascu treated wood (Pine, fur etc.) is used for construction of C.T. structure, splash
bars, desks, fan chimney, stairs etc. S.R.P. grid support is used for splash bars. Two end covers
are made of asbestos sheet and also the louvers at opposite sides. Concrete cooling tower body is
also made.
COOLING TOWERS 215
Cooling tower basin is made of R.C.C. work. Water level is kept at about 6–11 inches above
the wooden support base in C.T. basin. Basin cold water outlet is provided with double S.S. screen.
Make up water is added to the basin through float actuated control valve as per C.T. basin level.
9. WET BULB TEMPERATURE CALCULATION
Formula t′ = t −
kw
h fg
b
× h1 fg W′ − W g
Where t′ = Wet bulb temperature °C.
t = Dry, bulb temperature °C.
Kw = Diffusion co-eff. of water vapour through film of air water
vapour mix, kg/sec. m2.
h1fg = Enthalpy of vapourisation at wet bulb temp. kcal/kg.
hfg = Enthalpy of vapourisation at dry bulb temp. Kcal/kg.
W′ = Spec. humidity at wet bulb temp, kg moistre/kg dry air
W = Spec. humidity at dry bulb temp, kg moistre/kg dry air
10. COOLING TOWER BLOWDOWN

The blowdown rate from a cooling tower depends on allowable concentration build up of a
constituent in make-up water. Usually a conc. cycle of 2–3 is maintained in circulating water.
Formula for concentration ratio.
Concentration of a constituent in cir. C.W.
Concentration ratio =
Concentration of the constituent in m.u. water.
This indicates concentration of one constituent in m.u. water and can go upto twice or thrice
in circulating water. The blowdown rate from cooling tower basin is to be kept accordingly. The
C.T. blowdown valve pit is kept at the back of the cooling tower. The C.T. blowdown water is never
to be discharged into the factory storm water drain. This is taken separately through pipeline to C.W.
treatment plant as C.W. is always treated usually with chromate-phosphate dosing in the range of
10 ppm chromate and 20 ppm phosphate for corrosion control of C.W. pipelines and connected
equipment.
11. M.U. COOLING WATER

A continuous flow of make up water is needed to compensate for evaporation loss, drift loss
and blowdown loss of circulating water.
M.U.water flow = evaporation loss + drift loss + blowdown water. Usually evaporation loss
is calculated @ 1% of circulating cooling water flow per 12° F cooling range (difference between
Hot return cooling water temperature and cold cooling water temperature both in same temperature
scale). Drift loss is taken as 0.1–0.2% of circulating water flow. Blowdown rate is as per concentration
cycle adopted.
12. PRESSURE DROP IN CIRCULATING COOLING WATER CIRCUIT

The sum of the pressure drops in various cooling water loops (incoming and outgoing) in the
plant should be zero. This is as per Hagan-Poiseuille’ equaiton. The cooling water pump pressure
should be sufficient to send the cooling water to the remotest plant facility and allow the return
cooling water to rise to the top of cooling tower. C.W. pipeline sizing is to be done considering
proper velocity of water.
13. TREATMENT OF COOLING WATER

Treatment of cooling water is required to keep the rate of corrosion of carbon steel of C.W.
pipelines and connected equipment to min. level. Usual method is to put required quantities of sodium
dichromate and sodium hexametaphosphate so as to keep a concentration of chromate-phosphate in
the ratio of 10 : 20 ppm.
For control of pH of circulating cooling water, usually alkalies are put into cooling water so
as to make the pH at 6.9–7.3. The pH of cooling water will, however, depend on the make up water
pH and presence of sulphate reducing bacteria in a circulating cooling water. Now a days instead
of phosphate-chromate treatment which requires reducing Hexabalent chromium to trivalent chromium
in the blowdown cooling water, the quaternary ammonium compounds are used to control corrosion,
pH, and sulphate reducing, nitrifying and other bacteria, algae and fungi growth. Use of the quaternary
ammonium compounds in required doses depends on test runs with the dosing chemicals. The
chemicals are, however, costly. Manufacturers claim that no treatment of C.T. blowdown is required.
Microbiological analysis of c.w. is to be carried out.
14. RATING OF COOLING TOWER DUTY

It is usually expressed as quantity of cooling water circulation rate in m3/hr at design hot and
cold water temps based on basic data, supplied by customer or as amount of heat to be removed
in KW or MW units (kcal/hr). One KW of heat removal is equal to 856.8 kcal/hr.
Chapter
32
PAINTS AND PAINTING
1. COLOUR SIGNIFICANCE
(i) Attention galling: Various colours of paints cause attention in the following decreasing
order.
Red – orange
Red – blue
Yellow
Pink
and luminous yellow– green.
(ii) Adding coolness or warmth: Red–orange (hottest), reds and yellows. Blues and the
violets convey coolness.
(iii) Creating moods: For stimulation and excitement, warm colour especially red–orange, red
and orange. Blue–violet, violet and blue colours are subdued colours and tranquillizing colours are
yellow–green, green and blue–green.
(iv) Suggesting size: For spaciousness, use. whites and lime blues.
(v) For feeling of closeness and confinement use dark colours.
(vi) Camouflaging: To hide overhead structures, extend wall colour to whole area. To hide
pipes projections etc., paint them with the same colour as their surrounding.
(vii) Saving on light: Use highly reflective colours (ceilings-white), Light reflection factors are
given in table.
2. PAINTS
Paints are homogeneous mixtures of paint vehicles and pigments. Paints are used mainly for
protective treatment of base materials, metals or wood mainly for decorative purpose.
2.1 Typical Components of Paints or Lacquers
2.1.1 Paint vehicles:
(a) Non Volatile –(i) Oils (triglycerides of fatty acids)
(ii) resins
(iii) Dryers
(iv) additives
217
(b) Volatile—aromatics, chem and industrial solvents and lacquer solvents, ketones, esters and
acetates.
2.1.2 Pigments. (A) Opaque
(B) Transparant
(C) Special purpose.
2.1.3 Oils. Alkali refined Kettle bodying linseed oils are mostly used. Soyabean oil, Tung
oil, (china wood oil - Kettle bodying) Tall oil (combination of fatty acids and
resins) are used in some types.
2.1.4 Synthetic resins – (a) Phenolic resins
(b) modified phenolic resins (ester gum and pure phenolics).
(c) maleic resins used in shorter oil lengths (made by reacting maleic acid or anhydrite
with a poly-hydric alcohol such as - glycerine in presence of rosin or ester gum).
(d) Alkyd resins (made by reacting phthalic acid or anhydrite with glycerine and
pentaerythritol which are further modified with drying or nondrying oils which are
mostly used in synthetic enamel paints or industrial paints.
(e) Urea resins (Urea formaldehyde). It is usually combined with alkyd resins or plasticisers
(suitable for metal painting).
(f) Melamine resins (made from malemine and formaldehyde and give better finish than
urea formaldehyde-expensive paint for colour retention.
(g) Vinyl resins (co-polymers PVC and PVA). available as white powder to be dissolved
in strong solvents such as esters or ketones - Paint has maximum resistance to
chemicals, acids, alkalies, solvents and water. Used in cables, swimming pools, cars,
masonry etc.
(h) epoxy resins (These are epichorohydrin bis-phenol resins, have chain structure
compound of aromatic groups, made from aromatic groups and glycerol. Various
modifying agents are used to give epoxies of different properties.
(i) Polyester resins (made by Polymerisation of styrene and lower m.p. resins which are
used in paint suitable for use including, varnishes and water proofing paper etc.).
(j) Polyester resins (polyester polymer with oils have good adhesive to metals - used in
industrial type paints.
(k) Silicone resins (Polymerised resins of organic polysiloxanes have excellent chem.
resistance with high heat or electrical resistance–a very expensive paint.
(l) Rubber brand resins (Synthtic rubber paints have high resistance to water and
corrosion and used in swimming pool concrete floor, asbestos sheeting, exterior
structures.
(m) Urethanes ( resins with alkyds type which are widely used as floor finishes and
exterior clear finishes on wood.
2.1.5 Dryers. Facilitate drying of paints. Mostly dryers are metallic soaps that act as a
polymerisation or oxidation agents or both. Soaps must be soluble in paint vehicle. Tall
oil dryers are less soluble than napthenate based on naphthenic acids. Other dryer normally
used are:
PAINTS AND PAINTING 219
1. Cobalt drier – 6 – 12% cobalt metal in most powerful drier used in industry. It has
an oxidation catalyst. Excessive amount of cobalt drier can result in wrinkling. It is
purple in colour and shall not discolour paint.
2. Lead drier – 24 or 36% lead metal. This drier has been replaced by calcium or
zircomium based drier.
3. Calcium drier – acts as a polymerisation agent and sold as 4,5 or 6% calcium. It is
more popular.
4. Zirconium – 6, 12, 18% Zirconium often used in combination with cobalt and
calcium drier.
2.1.6 Additives. Used in a small quantity, its name and percentage are kept secret by
manufacturers. They belong to the following trade names.
(i) Antisetting agents (gives a gel structure with the vehicle).
(ii) Antiskinning agent – Common name methyl ethyl ketone (used in alkyd paint).
(iii) Bodying and puffing agent – used to increase viscosity.
(iv) Antifloating agent – used to supress separation of colours when two or more colours
are used.
(v) Loss of dry inhibitors – certain colours (black, organic red or TiO2) tend to activate
the drier and paint looses drying agent on ageing. Agents added, try to react slowly
with vehicle and additional drier added to replace what was lost. Now cobalt base
agents are used.
(vi) Levelling agents – special wetting agent is used to cause vehicle to net the pigment
which will not leave any brush or roller mark.
(vii) Foaming prevention – Found in water based paint and debubbling agent is added.
Grinding of pigments – Additives are added during grinding of pigments which help
in melting.
Fungicides – added to prevent its development in exterior paints.
Antisagging agent – to prevent runs or sags of paints.
Glossing agent – to increase gloss.
2.1.7 Lacquers. Dry by evaporation of the solvent – they are either cellulosics, resinous and
plasticizers (non volatile). A combination of cellulosics and resins based lacquers is used.
2.1.8 Solvents. (i) Commonly used petroleum solvents as, for example, white spirit distilation
range, 149–204°C, also called thinner or terpentine; faster evaporation rate is suitable for
all paints except for flat finishes where heavy mineral oils are used. Even faster evaporation
mineral oil (distillation range 93–112°C) is used and often called as VM and p. naphtha
is also used as all purpose thinner, EPA (U.S.) limit is 250 gm of volatile solvent/litre of
paint. Special purpose naphtha with aromatic content reduced is used as thinner for
cleaning. (ii) Paraffinic hydrocarbons – BP 40–60°C, 60–80°C and 80–120°C and specific
gravity 0.645–0.676 and aromatic content 1–5% are also used. (iii) Aromatic solvents
from coal tar distillation are also used in industrial and chemical coatings. They are having
low boiling point chemical. Solvent power increases with increase in aromatic content.
(a) Benzol C6H6 BP 79°C

(b) Toluol C6H3(CH3)- BP 110°C
(c) Xylol (Type-1) C6H4 (CH3) (BR 138 - 144. 5°C). These are three types of Xylenes
– 23°C xylene, 5°C xylene and 10°C xylene (o.m. and para), and naphtha (BR 149
–177°C) – it has slow evaporation rate.
(e) Trimethyl Benzene, high aromatic petroleum fraction having 80–93% aromatic (BR
100–211°C), FP> 32 °C.
(iv) Alcohols – Acetone CH3COCH3 – fast evaporating.
Ethyl Acetate, CH3COO C2H3 – fast evaporating and low cut.
Butyl Acetate, CH3COOC4H9 – good medium boiling solvent for lacquers. It has good
blush resistance.
Isopropyl Alcohol – BP 82.4°C, FP 12°C, S.P. Gravity 0.7925.
Its property is similar to ethyl alcohol.
n-Propyl Alcohol – Azeotrope Compound, 71.7% alcohol and 28.3% water. It dissolves
resin, shellac and Castor oil.
Ethyl Alcohol – C2H5OH containing 5% methanol. – Good latest solvent for lacquers and
also used for dissolving shellac. Methanol added to prevent consumption.
n- Butyl Alcohol - Medium boiling – popular latest solvent for lacquers. BP 118°C, FP
37°C and SP. Grv. 0.811.
2.1.9 Pigments
It gives hiding or obliterating power of paints i.e., coat's property in covering the surface
being painted. It also gives decorative effect of paints.
Relative hiding power of white pigments.
Hiding Unit
Lead Carbonate – 15
Lead Sulphate – 15
ZnO2 – 20
Lithophone – 25
Antimony Oxide – 28
Anatase titanium di-oxide 100
(Crystalline form very less used).
Rutile titanium di-oxide 125 – 135
(Crystaline form mostly used having
density of 240–250 kg/m3).
2.1.10 Extender Pigments
Low cost raw material (RMC) and they are nonhiding pigments such as Calcium Carbonate,
talc and clay; percentage used is more if hiding property is to be imparted. Talc is magnesium silicate.
China clay (Aluminium silicate) – mostly used in water based paint. Other extender is diatomacius
silica used to reduce sheen or gloss.
PAINTS AND PAINTING 221
2.1.10 Protective Paints

Another use of pigments apart from decorative purpose is protection of metal or wood surface
(e.g. Cuprous Oxide and tributyl oxide to give ship’s bottom property to kill barnacles and antimony
oxide gives fire retardant property. Higher the pigment power higher is the gloss property. Other
properties are to control viscosity and to give very specific property of flourescence, phosphorescence
and electrical conductance.
3. TYPES OF PIGMENTS
Apart from white pigments, extender pigments (whiting calcium carbonate (most important),
Talc (magnasium silicate commonly used to give low sheen), China clay (solvent base coating) and
other extenders (silica. diatomacious), black pigments (Carbon black and Lamp black) etc. are made.
The pigment colours are given in table 170 vol IIA.
Metallic Pigments – Aluminium powder; non leafing type used to give high metallic look and
leafing type for silvery look Aluminium paint should not be in acid or alkaline atmosphere. Zinc oxide
and red lead are used as primers.
3.1 Colour wheel
This wheel as given in Fig.1 gives complimentary colour at diametrically opposite to each other.
4. INDUSTRIAL PAINTS
There are three generic types of resinous paints.
(i) Alkyds (ii) epoxies and (iii) Vinyls.
4.1 Industrial Usage
Alkyds – When a polyhydric alcohol reacts with a poly basic acid, an alkyd resin is formed.
In refinery, alkyd paints are used.
Epoxyes – It is made by reacting epichlorhydrin with poly phenolic compounds or mono/
diamines or other compounds, when epoxy resin is formed. It is suitable for solvent atmosphere and
certain types of caustic atmosphere.
Vinyls – Suitable for highly alkaline and acid atmospheres as well as areas subjected to extreme
moisture and condensate.
4.2 Paint Thickness
Paint thickness on applications : Minimum dry coating thickness required, is 2–3 coats of
thickness, 4–5 mils. The instrument is called elcometer.
4.3 Cleaning for Painting
(i) Thorough cleaning of paint surfaces by sand blasting (costly), wire brushes, knives and
emery papers are suitable and solvents are used for oils and grease removal.
(ii) Application of paints is by hand brushes or spray guns, whenever required, in industry.
After 1st coat application, the coating is to be given time for drying so that 2nd coat could be applied,
3rd coat is required in special equipment.
(iii) A good thinner is to be topped up on paints occasionally to restore paint consistency for
the consumption of paints in containers.
(iv) Atmosphere for painting – In humid atmosphere which hampers evaporation of paint
vehicle. Also no painting when the ambient temperature is low.
(v) After each coat of painting application, check for holidays, thin spots, Pinholes, missed area
and general appearance.
(vi) Without proper cleaning of surface, painting will be poor.
4.4 Major cost in painting is cleaning operation which is of the order of 50–60% of cost of paints.
n
ee
Yellow
Gr
w
llo
Ye
en
re
G
G reenish Blue G reen
B lu
eG
ree
n
Fig. 1. Colour Wheel. Complementary Colours are at Diametrically Opposite to each other.
Chapter
33
BIOGAS PLANT (DOMESTIC USE)
Capacity range = 60–3000 cft/day methane gas
A. MAZOR EQUIPMENT
1. Digestor
1. This is the main equipment where bio gas (methane) is produced from cow dung and water
slurry by methanococcus micro organism. It is constructed by brick and cement mortar as a square
or rectangular shaped box of size : 2.50 mH × 2.5 mL × 2.0 mW (suitable for a family of 6–7
persons) with neat cement finish on floor.
Ht
The ratio is kept at 5–6.
depth of slurry
Digestor bottom level should be about 0.5m from grade level. The digestor top is to be covered
with wooden top cover to prevant escape of methane. Gas outlet pipe (pvc) of 1" I.D. to methane
gas holder, where, an inlet valve is to be provided at digestor side near top edge.
2. Drying Tank (1+1)
A small tank of capacity 3m3 of brick and cement mortar at below digestor slurry ht. is to be
made so that spent slurry from digestor falls through a 3" PVC pipe. The tank should have a drain
provision of 2.5" pvc pipe with closure by wooden circular wedge. The spent slurry tank bottom
is to be made by brick work without neat cementing.
3. Gas Holder
1. Circular steel gas holder of size 2 m dia. and ht. 3 m, has a capacity of 9.5 m3 (7–10 days
consumption) for a family of 6–7 adults. The gas holder foundation (circular) is to be constructed
by brick and cement mortar at 1 m above grade level and dia of foundation should be 6" more than
holder dia with 3 equal pockets for bolting of gas holder foundation bolts of 25 mm dia × 300 mm
long with 1:2:4 concrete with the support plate of gas holder. A 1" G.I. vent valve for purging at
top of gas holder and a 1/2" G.I. valve at bottom of gas holder for gas outlet, is to kitchen to be
provided ; and earthing wire (GI – 6 mm dia.) is to be connected from gas holder bottom plate to
a 3 feet deep earthing pit.
B. PROCESS
A slurry of cow dung and water is to be made first by putting 30–35 kg/day cowdung into
digestor in 1–2 days and then made into a slurry at a ratio of 1 : 1 (cowdung–water) by adding water;
223
some cut straw is to uniformly mixed with slurry for better composition of spent slurry in drying
tank. Also pH is adjusted by adding alkali to slurry to make pH 6.8–7.2 maintain slurry level at
0.4–0.5 m in the digestor. If necessary, more cow dung is to be added. Cover the digestor with the
wooden cover. The total hold up time in the digestor is 20–40 days. Aerobic fermentation first starts
with air inside the digestor for 3–4 days, followed by anaerobic fermentation which continues for
17–35 days when methane gas, along with CO2, is generated in the digestor and is led into gas holder
through outlet pipe. Methanococcus micro organism breaks the cowdung cellulose, generating methane
(CH4) gas with some CO2. The top cover edge is to sealed by mud to prevent gas leakage.
The air inside the gas holder is to be purged out initially as methane enters the gas holder with
open purge value in the gas holder top and keeping the gas outlet valve in the gas holder closed after
purging. Purging is to be done for a considerable period of time to prevent explosion, (explosion
range 5–15%). The gas holder outlet line to kitchen is also to be purged for 5–6 mins. After gas
holder is purged and top valve closed, methane pressure develops in the gas holder.
C6 H10 O5 + n H 2 O  → n C6 H12 O6 

→ acidification 
→
hydrolysis
35° C
cowdung by acid bacteria
Methanation
3n CH3 COOH by bacteria
→ 3n CH 4 + 3n CO2 .
carboxylic acid
Thermal efficiency is 30–50%. The calorific value of bio methane gas (with CO2) is 500. BTU
per SCF or 4450 kcal/m3. Some recycling of spent biomass can also be done.
After methane gas generation stops, close the gas inlet from digestor; open spent slurry to
drying tank. One drying tank is to be used and other are kept stand by. The compost manure
removed from drying tank is used for agriculture. Finally the digestor top cover is opened and spent
biomass cleaned – a part of which can be recycled. About 2 months time is required for proper
composting of spent slurry. The methane gas generation rate is about 0.23 m3 per kg of cow dung.
Chapter
34
SUGARS
A. MANUFACTURE OF CANE SUGAR
(i) Preliminary Crushing and Extraction of Juice
The sugar cane is weighed and subjected to crushing to extract juice. Crushing is done in two
stages in juice extractors or roller mills. The roller mills contain 9 rolls in sets of 3. In the beginning
sugar cane is first lebelled and then cut into small pieces followed by crushing in 1st rollers when
50% of juice is extracted. This is followed by crushing in 2nd and 3rd sets of rollers. The
composition of raw cane juice.
Water Sucrose Reducing Other organic Inorganic
sugars compounds compounds
77–88% 7–21 0.3–3 0.5–1
(ii) Screening of Sugar Juices
The raw juice, as it comes from the mills, is contaminated with suspended matter, mainly
bagasse fibres and mud. Separation is carried out by screening either in stationery drags screening
or in vibrating screens, made of brass. The drags screens is a perforated plate (260 – 400 perforations
per sq. inch) screen fitted with a movable rubber scrapper which recycles the bagasse particles to
the crushers through a conveyor. In vibrating screen the openings are smaller usually 0.1mm but
oscillations are more than 600 per minimum. The amount of bagasse that can be separated by
screening varies from 1–10 gms/per litre.
(iii) Removal of Suspended Matter from Screened Juice
The screened juice still contains about 1 – 10% suspended impurities (non-sugars) which
consist of waxy matter (lipids), pentosans, protein matter (non sugars) and Inorganic oxides (CaO,
MgO, Fe2O3, Al2O3, P2O5, SiO2) and insolubles. These are partly filtered out by heating the juice
to its B.P. followed by centrifugation in a high speed centrifuge. About 0.05–0.1 gm/lit. of suspended
matter is removed by this method. Heating removes the dissolved air, coagulates the proteinic
nonsugars and pentosans. Fe2O3 and Al2O3 are partly precipitated and SiO2 is precipited partly in
combination with sesquioxides.
(iv) Clarification of the Raw Sugar Juices
The residual suspended impurities and ionic dispersoids in the raw juice are separated by
clarification with lime. The non-sugar dispersoids, present in the sugar juice, are listed below.
225
% non-Sugars
(a) Hemicelluloses, pentosans (gums) and pectin. 8.5
(b) Proteinic compounds.
(a) Albumin 7.0
(b) Albuminoges and Pectoges 2.0
(c) Asparagine and Glutomin 9.5
(d) Glycine and Aspartic acid 15.5
(c) Organic Acid (Except Amino)
(a) Aconitic, Oxalic, Succinic, Glycolic and Malic 13.0
(d) Colouring matter
(a) Chlorophyl, Saccharetin, tannin etc. 17.0
(e) Waxy material (cane wax) 17.0
(f) Inorganic Salt
Phosphates, Chlorides, Sulphates, Silicates, 7.0
Nitrates of Na, K, Ca, Mg, Al and iron
(g) Silica 2.0
Item (a) to (f) are present as collodial dispersion. Item (g) is present as molecular and ionic
dispersion. Out of the above dispersoids some are removed in the heating and centrifugation operations
mentioned in step (III) above and remaining dispersoids are separated by liming process.
There are several clarification processes available, as stated below.
Lime Clarification Process
Lime clarification process is the oldest process using lime as the clarifying agent. There are
several modification of the process.
(1) Cold liming process
(2) Hot liming process
(3) Fractional liming process
(4) Fractional liming and double heating process
The other two clarification processes viz (5) Carbonation process and (6) Sulphitation process,
are basically similar to lime clarification process since in the above two processes lime is also used
as the clarifying agent.
(i) Cold Liming Process
Lime is made into a slurry with condensate in a rotary slaking machine, or other types of
machine. The rotary slakes consist of slowly revolving, nearly horizontal cylindrical vessel, fitted
with baffles. Lime and water are fed at one end while the milk of lime is discharged from the other
end which is transferred to a settling tank where undissolved impurities collect at the bottom. The
slurry of lime over flows into a sieve (13 mesh) which is constantly sprayed with water.
The filtered milk of lime is stored in a tank, diluted to proper concentration and pumped to feed
tank in the clarification section. The concentration produced depends on the process used – in
Sulphitation process it is 10–15° Be' or less and in carbonation process it is 20° Be'.
SUGARS 227
Measured quantity of milk of lime is added to the cold raw sugar solution in the mixing tank
provided with agitator with manual, automatic or electric metered feeding device.
Some Phosphates are also added. The process is either batch or continuous as in a modern
process. Lime addition is adjusted so that pH is maintained at 7.2–8.6 with constant stirring. Lime,
Ca(OH)2 reacts with the non-sugars in the raw juice so as to (i) precipitate some of them as insoluble
Ca compounds or complexes (ii) Coagulation of the colloidal and coarse dispersoids and (iii) form
soluble Ca compounds and complexes.
The magma is heated in a heater and transferred to classifiers to flocculate and settle the
insoluble reaction product. The quality of phosphate in the raw juice measures the amount of
precipitate to be formed in clarification process since more the phosphate contact, more will be the
amount of precipitate. pH is an important factor in the liming process and the volume of precipitated
mass increased with increasing pH.
The insoluble solids settle to the bottom of the clarifier and are removed as dark coloured
matter (due to tannins). Clear sugar juice from the clarifier is then transferred to carbonation tank.
Feed to clarifier is either at centre of periphery and the flow is also either counter current or
parallel current.
The clarifier used, are of multiple shallow tray types, having capacities ranging from 50–120
cft per short ton of cane per hour.
(ii) In hot liming process the raw juice is first heated to 100–102°C and milk of lime is then
added to maintain a pH of 6–8.0 and the juice is allowed to settle.
(iii) In the fractional liming process, pH level is raised to 7.6–7.8 in two stages-first liming at
6.0 – 6.4 pH and then heated to 100 – 102°c and second liming at 7.6–7.8 pH, followed by settling.
(iv) Fractional liming and double heating process, which is similar to fractional liming process
with the exception that the magma is given a post heating operation after second liming, followed
by settling. The first heating is also done at 93°C.
(v) Carbonation process: The excess lime present in the clarifier as dark coloured sugar juice,
is removed by carbonation since it imparts syrups and molasses a very dark colour and also increases
their viscosities, resulting in difficult crystallization operation, and also, the sugar that is produced,
is of brown in colour.
The carbonation process is carried out either in a single stage or in two stages and consists
of bubbling CO2 through magma. The residual non-sugars are precipitated or adsorbed on the CaCO3
crystals.
In single carbonation process, the sugar juice is mixed with 70 liter of 20° Be' lime per 1000
liter of juice in the carbonator so as to make this sugar juice extremely alkaline. CO2 gas, from lime
kiln, is then bubbled through the mass till the solution shows a neutral reaction of Phenolphthalein.
Carbonation time is 40–60 minutes. The juice is then filtered in filter presses.
In double carbonation process, the juice is heated to 55°C and 100 liter of 20°Be' lime is added
to 1000 liter of juice and the CO2 is then bubbled to the juice till the alkalinity of 400–600 mg CaO
is attained. Most of the non-sugars are precipited in this stage, and filtered in filter presses.
The filtrate is again carbonated till a slight alkaline reaction is observed on Phenolphthalein. Residual
CaO along with some non-sugars are precipitated as Calcium Carbonate in the second carbonation
process. In second carbonation there is no foaming of the juice. The raw juice is again filtered in
filter presses.
(vi) Sulphitation Process

The process consists of adding excess lime as the clarification agent, followed by precipitation
of excess lime by SO2, SO2 is dissolved to form Sulphurous acid which reacts with Ca(OH)2 to give
Ca2(SO3)2 precipitate.
There are two modifications in the process viz (i) single Sulphitation and (ii) Double Sulphitation.
The process is either batch or continuous. In (i) mixed sugar juice is heated to 75°C and taken in
a preliming tank and milk of lime at a concentration of 6–15° Be' is added so as to make the pH
7.4. The mixture is transferred to Sulphitation tank where SO2 is bubbled from the bottom of the
tank which also gives the desired mixing effect. Some provision is made in the tank for circulation
of the mass for good absorption and mixing.
The total filtering area required in single sulphitation process is 35 square metre per 100 ton
of cane per day.
SO2 gas is produced by burning Sulphur in Sulphur burners using excess compressed air.
From prelimer, the juice is pumped to the sulphitation tank by a recirculation pump whose
function is to circulate the juice in the sulphitation tank and to reduce the pH level in the preliming
tank by returning a portion of the limed juice to the preliming tank. pH control in sulphitation tank
is done either by lime control or by SO2 flow adjustment. It is then filtered by sedimentation – the
muddy juice is filtered in filter presses.
The double sulphitation process is a new development and consists of second liming to pH 10.5
after first sulphitation. The juice is then heated to 65°C and filtered. The filtrate is again Sulphited
to neutral reaction followed by second filtration. The total filtration area required in this process is
65 square metre per 100 ton of cane per 24 hour.
Comparison of the different clarification processes:
(A) No-sugars are removed more completely in carbonation process than in sulphitation process
and lime clarification processes. (B) Sugar crystals obtained from carbonation process is more white
than in other processes (C) Out put of sugar is more in carbonation process (D) sulphitation process
requires improvement.
(vii) Evaporation for Crystalization
The classified sugar juices from the sedimentation tanks, as well as from the filter presses, are
screened in a bronze wire mesh having 2000 meshes per cm square. The juice, having a pH of about
7.1, is now concentrated in triple effect vacuum evaporaters with natural circulation and fitted with
down comer at a temperature of 103°C. The concentrated juice or syrup crystallises in U type
crystallizers (Swenson Walker Crystalliser) using fine sugar as seeds. Heat of crystallisation is
removed by circulating cooling water to the crystalliser. The magma is then centrifuged and washed
to separate the sugar crystals. The separated mother liquor or molasses sent to vacuum pan feed
tank. The primary molasses is then mixed with syrup and crystallised, followed by centrifugation.
The separated mother liquor or molasses is sent to the storage tank via weighing scale for
storage and sold as a by product. Sugar crystals are dried in a rotary drier, cooled and directly
bagged.
B. MANUFACTURE OF BEET SUGAR

The important steps in the manufacture of beet sugar are.
(1) Extraction of juice from beet roots by diffusion
SUGARS 229
(2) Clarification in two stages: First by double carbonation followed by Single Sulphitation
(3) Evaporation of clarified juice in five effect evaporators.
(4) Post clarification of syrup by single sulphitation
(5) Crystallization of beet sugar from syrup
(6) Separation of beet sugar from the slurry (beet molasses)
1. The Extration of Sugar Juice from Beet Roots by Diffusion
The beet roots containing sucrose in the cells, are washed and sliced into V shaped pieces,
called cossetes. The freshly cut pieces are put in the last cells of diffusion battery. The battery
consists of 8–16 diffusions cells and work on counter current principle. Hot water is added on the
first vessel and almost exhausted cosset are put into it. The residual sugar in cossetes diffuse into
the hot water and the weak sugar solution thus produced is sent to the second vessel after it is heated
up in a heater. The stronger solution from the second cell is then passed into the remaining vessels
in turns and in the last vessel, the rich solution is contacted with the fresh beet slices. The juice
leaving the last cell is having almost the same concentration as that in the beet itself and is sent for
clarification. The juice obtained is purer than that obtained from cane sugar since gums and albumin
etc., do not pass through the cell wall.
Diffusion process for cane sugar extraction is not possible due to deterrioration on long
standing.
2. Refining of Raw Beet Sugar
The raw beet sugar obtained is not perfectly white due to presence of impurities which are
removed by further clarification and recrystallization. The refining process of beet sugar consists of.
(a) Affination
(b) Re-melting
(c) Clarification treatments (i) liming (ii) Adsorption on bone charcoal.
(d) Re-crystallization
(e) Centrifugation
(f) Drying.
Uses. By product molasses is mainly used for fermentation for alcohol – It is also used in
refractory to increase green strength, and as paste for charge chrome.
Chapter
35
PHENOLS FOR DISINFECTION
Phenols are antiseptics and disinfectants containing phenols (cresylic acid) and cresols.
Black Phenyls are cheap products whose specification is given in BS 2462–1961 (modified
black phenyl and modified white phenyl)
Black Phenyl: Homogeneous solutions of coal tar acids or similar acids derived from petrolium
or any mix. of these with or without hydrocarbons and with a suitable emulsifining agent. Black
fluids are miscible, yielding stable emulsions with artificial hard water in all proportions from 1–5%.
White Phenyl: Finely dispersed emulsions of coal tar acids or any mix. of these, with or
without hydrocarbons.
UK Brand names of white Phenyl: Sal-Hycol, Printol, Pacolin and R Crolin.
Modified black and white fluids may contain, in addition to above, any other ingredients, but
if these are made the type and amount must be disclosed.
Classification as per germicidal value and method of testing employed. There are 6 designations
of black fluids.
(i) BA (Rideal–walker, R–W coefficient not less than 4)
(ii) BB (R–W coefficient not less than 10)
(iii) BC (R–W coefficient not less than 18)
(iv) BE (Chicks Martin, C–M coefficient not less than 1)
(v) BF (C–M coefficient not less than 3)
(vi) BG (C–M coefficient not less than 4.4)
There are 7 designations of white fluids, 6 of these groups WA, WB, WC, WD, WE, WF and
WG has the same minimum R–W or C–M coefficient as the corresponding black fluids and the 7th
white fluid group WD has a minimum crown Agent coefficient of 10 and minimum R–W co-eff.
of 18. For modified Black and White fluids, the Phenol co-eff. (Staphylococcus) determined by a
specified method, must be stated by the manufacturer in addition to R–W co-eff.
Procedure Test norms
1. R–W test – BS – 541 Broth culture of specific micro organism.
2. Chick Martin test, BS 808 Yeast culture
3. Crown Agent's test, BS 2462 For white variety only, requires sterile artificial sea
230
water dilution of disinfectant in presence of soluble
and insoluble organic matter.
4. Phenol co-efficient test, BS 2462 This test is for ensuring that modified black and
modified white phenols are not unduly selective in
their bactericidal activity.
5. Manufacture – There are two important processes –
(1) Cumene oxidation (Hock's Process) and
(2) Toluene oxidation process.
6. Toxicity – It produces skin irritation and causes nervous system
breakdown. LD human = 140 mg/kg body weight.
50
TLV limit is 5 ppm (CIS = 1.5 ppm)
7. Waste water treatment – 1–3% phenol is removed from waste water by
for phenol recovery cumene and acetophane extraction.
Chapter
36
FERROUS ALLOYS
The Ferro alloys have higher percentage of iron. Usual ferro alloys are Ferro-silicon, ferro-
manganese, ferro-chromium, Ferro-titanium, ferro-nickel, ferro-boron, and ferro-molybdenum etc.
These alloys are prepared by direct reduction of respective oxides or technical grade oxides or
concentrates with carbon (carbothermic process) or with Aluminium (alumino thermic process).
Ferro-manganese, ferro chromium and ferro silicon are prepared by carbothermic reduction of
particular oxides in submerged arc electric furnaces. Other raw materials, apart from corresponding
oxides, is metallurgical coke and power requirement for the electric furnace varies from 15–100 MVA.
Ferro-manganese can also be produced in Blast furnace. Ferro-chrome and ferro-manganese
have high affinity for carbon and these alloys contain 7–8% carbon, while Ferro-silicon of 25% Si,
contains 1% C and that containing 75% Si has 0.1% C.
Low carbon ferro-manganese (0.1–2% C) or ferro-chromium (0.02–2% C) is produced first
as a silicon containing ferro alloy using quartzite and coke in a submerged arc electric furnace. These
silicon containing alloys are then used for silicon thermic reduction process using an appropriate
oxide ore in an arc refining furnace to get low carbon ferro-manganese or ferro-chromium.
Silico thermic direct reduction process with addition of Aluminium is used to manufacture
ferro-molybdenum and ferro-nickel. The energy released in the reaction is adequate to melt both
metal and slag. Solidified block of ferro molybdenum or ferro-nickel can be recovered easily.
Ferro-vanadium is produced by using vanadium oxide, iron turning, stampings or rail bits and
Aluminium in a refractory lined open hearth furnace where heat of reaction melts both metal and slag.
Often inert materials are added to lower the peak temperature. Ferro boron and ferro titanium is
produced in a manner similar to Ferro-titanium which contains 70% Titanium and 30% iron; using
scrap Titanium and iron apart from Aluminium and so also Ferro-Zirconium. Ferro-selenium is
produced by exothermic reaction of iron and selenium powder.
Steel industry uses these ferro-alloys to produce particular steel or alloy, containing the alloying
metal with iron in ferro-alloys.
232
FERROUS ALLOYS 233
Table 1
Composition of ferro-alloys
Item Alloying metal Iron Carbon
Ferro-manganese Manganese – 75–92% 25–8%
Ferro-Chromium Chromium – 45–95% 55–5%
Ferro-Titanium Titanium – 20–75% 80–25%
Ferro-Nickel Nickel – 20–60% 80–40%
Ferro-Silicon Silicon – 8–9.5% 92–91%
Ferro-Silicon Silicon – 25% 75% 1%
Ferro-Molybdenum Molybdenum – 62–70% 38–30%
Ferro-Selenium Selenium – 50% 50%
Chapter
37
HIGH CARBON CHARGE
CHROME
1. Charge chrome containing carbon and 50–60% chromium, is required for alloys like stainless
steels. Typical analysis of charge chrome :
Cr = 50–56% or 56–60% wt%
C = 6–8% (max)
Si = 4% (max)
P = 0.03 (max)
S = 0.035 (max)
Size of product : 10–150 mm lumps; standard = IS 11945 (1987)
High carbon charge chrome is required for introduction of chromium in S.S. and special alloys;
raw materials and utilities required are :
Chromite Ore = 2200–2500 kg/Te
Briquette Coke = 330 kg/Te
Lime = 156 kg/Te
Quartzite = 142 kg/Te
Molasses = 600 kg/Te (binder)
(Sugar = 85.5%)
Paste for electrode = 60 kg/Te (molasses)
and power (a) 3000–3100 kwh/Te (for Pelletising and preheating route)
(b) 3800–4100 kwh/Te
2. There are two routes for manufacture – by pellestising and preheating or by Briquette charge
without preheating.
Charge Pelletising Process
Chromite Ore materials as per calculation is ground in ball mills to 80% below 200 mesh and
then formed into 15–20 mm balls in dicc pelletiser, for agglomeration, is used after adding coke and
flux (bentonite 1%) in the charge. The balls are then preheated in a rotary static vertical klin with
234
HIGH CARBON CHARGE CHROME 235
off gases from smelting furnace (to save energy in electric smelting furnace as much as 0.7–0.8
kwh/Te). Preheating of pellets makes it hard. The preheated pellets are then melted at 1600°C in an
electric submerged arc furnace of capacity 30–45 MVA and voltage 150–160 V with circular
stationery hearth with self baking continuous soldering electrode holder assembly as well as electrode
stripping mechanism, copper contact clamps for holding electrodes, water cooled copper bus bars
with copper tubing. Coke reduces the chromite ore at high temperature.
3Cr2O3 + 18/7 C = 4/25 Cr7C3 + 2CO
FeO + C = Fe + CO
1/3 Cr7C3 + 1/3 Cr2O3 = Cr + 3CO
The cast housing provides metals and slag draw outs with guns for closing of tap holes and
refractory lined laddles for holding tapped molten metal and slag.
Slag granulation plant, crushers are available in the facility along with raw material handling and
warehouses. Slag volume is 1.2 to 1.4 times to that of metal. The chromium metal on cooling is
crushed into 10–150 mm lumps for use in alloy steel furnace for chromium addition.
Off gase from submerged arc furnace, after it is used to preheat the pellets, is scrubbed in a
venturi scrubber with alkaline water.
3. FLEXIBILITY
High carbon charge chrome plants are usually designed for flexibility to produce ferro manganese
or ferro silicon.
Power saving
By plasma technology in electric smelter furnace of capacity 30 MW or more. Other power
saving processes by Kwasaki, In-metco and Krupp codir.
Lower capacity 2.5–5 MVA plants are also in use.
4. BREQUETTING OF RAW MATERIALS

The grounded ores, after benificiation, are mixed with binders (molasses and lime) and fed to
a double roll briquetting press to form 50 × 40 × 25 mm shaped bricks.
In the west, molasses binding material is not used for obvious reasons. Beneficiated ores give
better quality charge chrome.
Chapter
38
CHARACTERISTICS OF VALVES
USED IN CHEMICAL PROCESS
INDUSTRY
1. CRITERIA FOR USE
(i) Material of construction; for body and trim (Stem, seat ring, disk)
(ii) Valve standard – codes and type-rising stem or non rising stem.
(iii) Connecting flanges – Flat, raised face and grooved flange.
(iv) Valve functions, on-off, throttling, pressure regulation or relief, preventing back flow or
combination.
(v) Press. drop consideration.
2. (a) Gate valve, if used, in throttling service, produce wire drawing.
(b) Globe valve throttling efficiency is more due to increased resistance to flow for size upto 6".
(c) Plug cock valves are more +ve shut-off than gate valve and can be used for throttling
but characteristics are not as satisfactory as glove valve for such service, with lower
pressure drop. Non-lubricated plug valves work by cam-crank mechanism. Excellent
service, for corrosive service which requires special lining or alloys.
(d) Swing check valves have minimum pressure drops and suitable for liquids and for larger
line size. It is not suitable for pulsating flows. Some types work only in horizontal lines.
(e) Piston check or drop check valves are suitable for vapours, steam, water and pulsating
flows.
(f) Y-type valves produces lower pressure drop and turbulance than globe valve and is
preferred for erosive services.
3. Usually globe valve for flow control is used for sizes upto 2 ½" to 3" and beyond these
sizes, gate valves are used.
4. ASTM A 351 material valves of Ferrite and Austenitic steel castings are used for high
temperature service. ASTM A 182 material forged or rolled alloy steel, are used for pipe
flanges, fittings for high temperature service.
5. Valves in oxygen service use molybdenum disulphide based lubricant to prevent fire
hazards.
236
Chapter
39
BOILER FEED PUMPS AND
STANDARD VALUES FOR BOILER
FEED AND CIRCULATING WATER
BOILER FEED PUMPS

Dimensioning in accordance with the "Technical Regulations for Steam Boilers" governing the
equipment and installation of steam generators, edition of September 1964. German regulation.
Every boiler plant must be fitted with at least two feed pumps driven from two mutually
independent power-sources. In the case of steamdriven feed pumps, however, all pumps may be
connected to the same steam supply system. Electric feed pumps may be driven from the same
power source provided that, in the event of power failure, firing is also disconnected.
Where only two feed pumps are used, each pump must be capable of providing: 1.6 times the
total steam output of all boilers to which it is connected, in the case of boilers not fitted with
automatic feed control up to 32 t/h.
1.25 times of this amount in the case of boilers of above 32 t/h or where there is automatic
feed control;
1.0 times the amount stated above in the case of once-through boilers.
Where more than two feed pumps are used, the pumps remaining in operation after the pump
having the highest output has failed must be capable of providing at least the quantity of feed-water
specified above for one of two pumps.
Feed Pressure
The feed pressure of the pumps must be sufficient, not only in delivering the quantities of feed
water required to overcome the maximum safe operating pressure, but also in delivering the feed
water quantity corresponding to the steam output, 1.1 times the maximum safe operating pressure,
the resistances between feed pump and steam generator to be considered in each case.
In the case of once-through boilers, allowance must also be made for the pressure loss in the
steam generator at maximum steam output.
237
D.P
Power required at pump shaft N = 2.72 ρ.η in kW
where D = feed water quantity, kg/h

P = feed water pressure, atm. gauge
ρ = density of feed water, kg/m3
η = pump efficiency, %, namely:
60–80% for direct coupled centrifugal pumps and
80–90% for reciprocating pumps.
Select a motor rating approximately 15% greater than N.
Table 1
2. Standard Values Feed water
Constituent Unit Fire-tube Water-tube drum type Once-through-type

boilers boilers1 atm. g boilers and spray-
water for super-
< 20 atm.g Heated-steam
202) 402) 642) ≥ 80 coolers
General – clear and colour less
Requirements
mval
Hardness < 0.04 < 0.02 < 0.01 < 0.01 Not detectable
1
Total carbondioxide mg/1 – < 20 < 20 < 20 < 1 <.1
Oxygen mg/1 < 0.5 max. 0.03: for continuous < 0.02
operation
Iron mg/1 if possible < 0.05 < 0.03 < 0.02
Copper mg/1 < 0.01 < 0.005 < 0.005
Silicic acid Sio2 mg/1 Continuous operation without < 0.02
blow–down, max. 0.02; otherwise
only as required for boiler water
Potassium perman- mg/1 If possible < 10 if possible < 5 if possible
ganate (KMnO4) < 5
consumption
Oil mg/1 < 5 If possible < 1 < 0.5 < 0.3
ph.value at 20 °C – For all pressures 7.... 9.5 7..... 9.5
Continuous operation without blow–down
µS
Conductivity < 0.3 <0.2
at 20 °C cm
otherwise only as required for boiler water
(1) Source : VGB Reports 1962. No. 76. pp. 1–3.
(2) With local heat transfers > 2.105 kcal/m2h, the standard values for pressures 80 atm.g should
be used.
BOILER FEED PUMPS AND STANDARD VALUSES FOR BOILDER FEED.... 239
Table 2
3. Standard Values for Boiler Water
Constituent Unit Fire-tube Water-tube boilers1 atm.g

boilers
< 20 atm.g 202| 402| 642| 802| 1252| 160
P value mval/1 5.25 < 10 < 6 < 3 < 1 < 0.3" < 0.1
= 50mg < 15 < 5
CaCo3/lit.
No restr- 3 3
iction if
Silicic acid mg/1 P value and < 70 + 7p3) < 30 + 3p3) <10 < 4 < 1.2 < 0.4
SiO2 P2O5 as
specified
Phosphate P2O54) mg/1 < 25 < 25 < 10 < 3
Conductivity at µs/cm < 8000 < 8000 < 5000 < 2500 < 1500 < 250 < 50
20 °C
(1) See page 238.
(2) With local heat transfers......>2.105 kcal/m2h it is recommended that the standard values for 160
atm. g (apert from SiO2 and p value) be used in all pressure ranges.
(3) p = p value
(4) May even be entirely omitted where the sudden appearance of hardness is reliably prevented.
(5) 1000 µs/cm is equivalent is approx. 500 mg NaC1/1 ∆ approximately 0.05° Be'.
Chapter
40
CRYSTALLIZER CLASSIFICATION
Table A
Mode of operation .... continuous Batchwise
Method of crystal suspention ..... Hydraulic, Mechanical Buoyancy, Fixed support
Method of crystal size control ..... Nucleation rate, Intermediate seed rate
Method of growth inducement ..... Evaporation, Cooling, Salting out effect
Table B
Equipment Type and Temperature – Solubility Relationships
Effect of temp. rise on Equipment reqd. Example
solubility in water
Small increase in solubility Evaporator-crystallizer Sodium chloride
Salting out evaporator
Decrease in solubility Modified evaporator-crystallizer Anhy. sodium sulphate,
Gypsum, Iron sulphate
mono hydrate
Substantial increase in Vacuum crystallizer Water Potash alum, Glauber salt,
solubility or brine cooling crystallizer Coppers, Potassium nitrate
Moderate increase in Modified vacuum or Evaporator- Pot. carbonate, Sodium
solubility crystallizer nitrite, Pot. chloride
Source: Chemical Engineering, Dec. 6 1965
Solubility curves of various inorganic salts are given in Fig. 1 and Fig.2.
240
CRYSTALLIZER CLASSIFICATION 241
Fig. 1. Solubility curve of various salts.
Fig. 2. Solubility curve of Sodium Sulphate.

Chapter
41
BRIEF ON OFFSHORE OIL
EXPLORATION AND
TRANSPORTATION PIPELINE
THE SYSTEM
The two 6.625" O.D. oil/NG lines are fixed inside by spacers (segmented) in a 18" special steel
casing pipe. Both the gas/oil pipes as per ASTM standards are provided. with SECT heat tracings
tubes, methanol control tubes (1.315" O.D.) and hydraulic control tubes (1.315" O.D.). The gas and
oil pipes are provided with 25 mm thick polyurethene foam insulation. The inner pipes are provided
with rollers arrangement for free movement due to various factors – winds and waves, tidal currents,
breaking waves, seabed topography, hydrostatic head. and sea bed soil resist, horizontal and vertical
movements due to environmental forces during installation and operation. The assembled casing pipe
is laid on sea bed by pull from shore or pipe pull from lay barge, close to shore (common); cross
section of pipe is given in Fig. 1.
S p a ce r
M e th a no l co ntro l
tu b e s (1 .3 1 5” o .d .) M e th a no l co ntro l
tu b e s (1 .3 1 5” o .d .)
1 8 ′′ dia o ute r ca sin g

ste e l pip e in se a b e d
P ip e R o lle rs
H e a t tra cin g tub e s
6 .6 2 5” ste e l ga slin e 6 .6 2 5” ste e l oil line in

in se a b e d se a be d
H yd ra u lic co ntro l
tu b e (1 .3 1 5 ” o .d .) 2 5 m m P o lyu re th a ne fo am
in su la tio n
Fig. 1. Offshore Oil/Gas Exploration Pipe line.
242
Chapter
42
INSECTICIDE OR PESTICIDE
GENERAL
1. Insecticides or Pesticides are insect destroying substances of chemical, organic extracts from
medicinal plants. The insecticide action is through stomach poison, contact poison, systemic
and non systemic poison, or act as repellants and attractants. Insecticides are broadly classified
into the following groups based on action on the type of pests.
1. Acaricides (Mites destroying)
2. Insecticides (Kill insects)
3. Molluscicides (Action on snails)
4. Nematocides (Action on underground eel worms)
5. Rodenticides (Action on rats or mices and sqirrels)
6. Slimicides (Remove slimes)
7. Fumigants (Prevent deterioration of fruits and cereals)
8. Fungicides (Kill fungus growth)
9. Herbicides (Destroy unwanted vegetation growth)
Insecticides/pesticides can be solid or liquid and natural or synthetic. As per Indian insecticides
Act 1986 (Rules 1971) and (ammended in 1995) there were 143 pesticides for registration. Pesticide
Board takes about 6 yrs for registration of a new Pesticide molecule. Indian insecticides 1968 Act,
goes on changing due to new items or some listed ones deleted due to harmful effects. India is the
largest producer of pesticides.
Pesticide formulations are usually made by small scale producing units. Some of the new
pesticides, listed in different groups below, have not yet been registered due to old patent Act and
exclusively available in the west.
1.1 There are Six Types of Insecticide Grades
E C = Emulsifiable concentrate.
W P = Finely milled powders that form a suspension with water.
W S C = Water soluble concentrate
A S = Alcohol soluble pesticide
W D P = Water dispersible powder.
G R = Granulated formulation.
243
Powder insecticides are ground with talc or clay with addition of wetting and dispersing agent.
Antifungal pesticides are applied either on soil or as folier spray.
2. THE LIST OF VARIOUS PESTICIDES ARE AS FOLLOWS

2.1 Group A – Acaricides
Name Area and action
1. Nimidane –
2. Amitraz – Fruit and hops
3. Apollo 50C – Top fruit
4. Azocyclolim – Fruit and Vegetable
5. Childien – Contact poison
6. Chexalin – Mites in fruit
7. Damfin – Stored grain
8. Dicofol – Mites killer
9. Dieno-chlor – Ornamental trees
10. Dimethoate – Insecticide and acaricide
11. Devipan – Agri. insecticide
12. Fen properthrin – Fruits and Vegetables
13. Malathion – Non systemic, contact poision and respiratory system attack.
14. Mesurd – Foliar feeding caterpillars and sucking pests.
15. Aqualin/cu. sulphate – Water body application
16. Methamidophos – Sucking and chewing insects.
17. Methomyl – Wide range and spider mite control.
18. Parathion – Systemic insecticide with contact and stomach action. Highly
poisions; suitable for wide range of insects.
19. Quinomethriorate – Fungicidal action
20. Fenovalerate – Termite killer
21. Dichlorophene
22. Fenithrion –
23. Suxon –
24. Para-quate –
25. d-allethrin (4%) – Mosquito repellant.
26. Hexachlorophenol –
27. Sisystox – Seed treatment and foliar spray, systemic.
2.2 Group B–Insecticides
1. Arsenic trioxide
2. Alachlor
INSECTICIDE OR PESTICIDE 245
3. CaO
4. Carbaryl – Contact insecticide for apples.
5. Chlor–fenvinphos – Seed treatment and soil application.
6. Confidor – Systemic, contact and stomach poison.
7. Cupermethrin/ – Non systemic, contact and stomach poison.
Cypermethrin
8. Cupric acetate – Fungicide and insecticide.
9. Diazivon (liquid) –
10. Imidazole – Fabric eating pests and contact poison.
11. Ethion – Cattle lice abatement, non systemic insecticide for citrus,
decidous fruits, cotton and ornamental plants.
12. Kafil – Smoke insecticide (closed space) for white fly,
cockroaches and domestic insects.
13. Oxytheoate – Systemic, with contact stomach poison and also
spidermite. For fruits and vegetable.
14. Propoxur – Nonsystemic, for action on sucking and biting insects
(aphids, mealy bugs, leaf hoppers, caterpiller on cocoa,
rice, oil Palms and others.
15. Rampant – Soil applied for seedling pests and cabbage.
16. Reldon–50 – Organophosphate insecticide for stored grain and rape seeds.
17. Terbufo S – Soil insecticide for vegetable and food crops and nematicide
with stomach and contact poison.
18. Terraour P – Nematicide and soil dweling insects.
19. Terrathinon – Organophosphorous insecticide.
20. Endosulfan/Thioclan – For control of sucking, chewing and boring insects and
(liquid) mites in a wide variety of crops.
21. Thripstick – Pyrethroid insecticide-non systemic for control of many
crops.
22. Dichlorovas/Vapona –
23. Volathion – Foliage and soil application for control of lepido-plerous
larvae, bettles and its larvae and locust on large variety of
crops.
24. Zind – Fungi in fruits and vegetables and ornamental trees.
25. Zolone – Organophosphrous insecticide – for insects and spiders
on fruits and vegetables.
26. Deltamethrin – For mosquito killing.
27. B.H.C. – Insecticide
28. DDT – Used in public health sanitation
29. Methyl parathion –
30. Monochrotophos (liquid)

31. DDVP (Dichlorovos) – Liquid
32. Diuron
33. Canbaryl/Sevin – DDT equivalent
34. Dimethoate –
35. Meta sytox –
36. Al phosphide –
37. Zinc phosphide –
38. Phorate –
39. Chlorobenzilate
40. Cupric pyriphosphate –
41. Butachlor – Liquid
42. Data pon –
43. TEPP –
44. Lindane (Y BHC)
45. Thiram
46. Fenthion
47. Endosulphun
48. Pyrethrun extract
49. Quinal phos
50. Aldrin – For soil bound pests (termites, cut worms, grass hoppers
etc.). Contact and stomach poison – used as dust spray,
WDP.
51. Warfarin – Safer insecticide.
52. Clordane – For crickets, locusts, cockroches, ants and leaf eating
insects.
53. Nicotine sulphate – Plant insecticide active component containing (0.5%)
54. Nim oil – Vegetable tree origin active component (0.5%)
55. Methoxyclor – Safe for plants.
56. Chloropyriphos –
57. B.T. – Bio insecticide.
58. Datopon –
59. Allethrin – Mosquito repellant
60. Malthion –
61. Phosphomidon –
62. Deltamethrin – Mosquito killer
63. Prallethrin – Mosquito killer.
2.3 Group C – Molluscicides

1. Calcium arsenate
2. Melaldehyde
3. Clonitritide
4. Methio-can
5. Mini Slugit pellets
2.4 Group D – Fumigants
1. Al phosphide
2. Ethylene dibromide/dichloride.
3. Ethylene oxide gas (B.P. 12°C) – Cereals, empty building and plant disinfection.
4. Tetrachloromethane – Green house fumigant
2.5 Group E – Fungicides
1. Copper oxychloride
2. Aaterra W P – Soil based or compost
3. Acticide PMA 100 – Has herbicide action also.
4. Afugan
5. Aliette – For horticulture crop
6. Anildazine – Nonsystemic, foliar aplication for potato, tomatoes and
leaf spot.
7. Antifungin –
8. Arsenic trioxide –
9. Akiran – For cereals, rice, cotton and vegetables.
10. Ashlade TCNB – Additionally potato sprouting prevention.
11. Bitertanvol – Control of scab on appel and black spot on roses.
12. Butyl Paraben – Food preservation and in pharma control of powdery
mildew.
13. CaO –
14. Calixin – For cereals and vegetables.
15. Captafol –
16. Carbendazim – For wide variety of cereals, fruits and vegetables.
17. Carboxin – For cereals.
18. Chlorothalonil – Non systemic, wide variety of crop and additives for
marine coating.
19. Mancozeb –
20. Nickel chloride –
21. Sulphur (Collidal) – WDP and Dust.
22. Thiram
23. Zineb
24. Ziram
25. Aurcofungin –
26. Ferbam –
27. Copper (++) hydroxide –
28. Dichlorophen – Moss controlling
29. Diphenyl –
30. Folicor –
31. Fera thinosulf – Soil fungi-cide.
32. Carbendazim –
33. 40% formaldehyde
solution with water – Soil fumigation
2.6 Group F – Herbicides
1. Acifluorfen (LD50 = 1300 mg/kg)
2. Agriphalan –
3. Alachlor (LD50 = 1200 mg/kg)
4. Amcide –
5. Arsenic trioxide (LD50 = 1.46 mg/kg)
6. Aresin (LD50 = 1660 mg/kg)
7. Atrazin (LD50 = 1100 mg/kg)
8. Benzolin (LD50 = 4800 mg/kg)
9. Benlazon –
10. Bifenthrin (LD50 = 1740 mg/kg)
11. Chloroxuron (LD50 = 3700 mg/kg)
12. Datapon (LD50 = (7126 mg/kg) – For control of grass in crop
13. Diuron – – For control of weeds in non crop area.
14. Dowpon (LD50 = 9330 mg/kg) – For control of weeds and mosses in non-
crop areas viz rail roads and rubber
plantations.
15. Butachlor –
16. Isoproturon –
17. Paraquat dichloride –
18. Granoxone –
19. Fluroxypyr – Broad leaf weeds.
20. MEPA –
21. Propanil –
22. Benzonitrates –
2.7 Group G – Slimicides
1. Dodecyl Dimonium chloride – For swiming pool and water treatment plant.
2. Drewbrom –
3. Vanicide – For petrol tanks, C.W. basins, paper plants and cotton
fabrics.
4. Mycocide –
2.8 Group H – Rodenticides
1. Barium carbonate (15–20%) –
2. Comafuryl –
3. Zinc. Phosphide –
4. Alpha Chloralose –
5. Bromediolone –
6. Cupric arsenite –
7. Difenacoum –
8. Drat –
9. Killgerm, Sewarin –
10. Malla – dnite. –
11. Phostoxin –
12. Photo phor –
13. Hydrocyanic acid (prusic acid)–
14. Racumin –
15. Warfarin – 3 –
16. Thallium Sulphates –
17. Aldichlor –
18. Arsenic oxide. –
2.9 Group I – Nemoticides
1. Chloropicrin –
2. Cloetho carb –
3. Etho prophos –
4. DCIP –
5. 1, 3 dichloropropane – Has fumigant action to control nematodes.
6. Dizomel –
7. Fenamiphos –
8. Fensulphothrin – Soil application.
9. Iozofos – Root nematodes control in rice, maize, sugar and vegetables.

10. Phorate – For sour fruits, vegetables, and grain
11. Oxamyl – For fruit trees, vegetables, beat and bananas.
12. Triazophos – For straw-berries, tulips and garlic.
13. CS2
14. Carbofuran –
N.B. Banned pesticides are Aldrin, Chlordane, DDT, Heptachlorendin, Taxo-phane and
dibromopropane. DDT can be used for public health only. Pesticide act does not enlist all the modern
pesticides listed above.
The unit of toxicity of pesticides is usually expressed as LD50 which means, it is lethal to 50%
of test animals, followed by the dose expressed as mg/kg body weight. The test animals are usually
rats and oral (orl.) dose is given. Example LD50 = 1100 mg/kg for Atrazin (herbicides).
3. Pesticides are complex organic molecules, usually chlorinated hydrocarbons and organo
phosphorus compounds which are more toxic than carbamates. There are some inorganic
pesticides also usually of copper, arsenic, barium and calcium compounds. There are some
plant based insecticides, viz neem (margosa) oil from neem seeds, kernel and leaves contg.
active component, Azadiractin Indica and ether extract of which (1.5%) is very effective
against locust and white cotton fly. Plant based insidcides are biodegradeable and insects do
not develop resistance to the insecticide. The residue, neem cake after neem oil extraction, is
used as a bio fertilizer.
Emulsifiable concentrate is one liquid, dispersed in another liquid, each maintaining its original
identity and the two liquids are prevented from reacting with each other by the addition of an
emulsifier. Emulsions are milky. Herbicides are generally soluble in water. There are powder
insecticides also.
4. SOLVENTS FOR PESTICIDES/INSECTICIDES

For application of pesticides, not soluble in water , or plants, crops etc. To form a water
system, it requires the use of an emulsifier (nonionic, cationic/anionic, inorganic and natural). Except
inorganic emulsifier, all other types of emulsifiers are biodegradeable.
An emulsifer (surface active agent) is having a chemical structure in which the molecule is
divided into two moieties–one part of which is hydrophilic (water soluble) and the other part is
hydrophobic (water insoluble), usually hydrophobic part is soluble in organic solvents. Emulsifer
effects wettability by influenoing both surface tension and contact angle. For longer storage of
pesticides, stability of emulsifier is important. Emulsifier pesticides are important because of being
more biologically effective and application is easier and economic. Other dispersal system are also
used. Wet-able pesticides powder also contain surface active agents.
The emulsifier molecule's hydrophobic moiety is always nonpoliar alephatic and/or aromatic
hydrocarbons group, where as the hydrophilic section contents either an ionic group or an accumulation
of OH– group or a poly (Alkenyl Oxide) group e.g., (–CH2 – CH2 – O –)n. The emulsifiers in the
first group above are called anionic surfactants and the second group is called polar surfactants.
Classification is determined based on whether the main moiety that is left behind after disolution, is
negatively charged or positively charged.
Emulsifiers are numbered with a prefix alphabet denoting the type.
Table 1
Nonionic emulsifiers
Aliphatic alcohols (–COO) Sorbitol
Ethylene Glycol (–COOCH2CH2OH) Penta erithritol
Polyethylene glycol Saccharose
Polypropylene glycol Polyglycol ethers.
Glycerol/Polyglycerol Condensed Phenols
Table 2
Cationic emulsifiers
Fatty amine salts,
Salts of alkaline diamine, e.g., alkyl benzyl ammonium
Salts of alkaline, Polyamines
Table 3
Anionic emulsifiers
Alkyl Carboxylates
Alkyl Sulphonates
Alkyl Benzene Sulphonates (Sparingly soluble)
Sulphated alkylamides
Phosphates of phenols
Organic compounds of H3PO4
Table 4
Solid Inorganic emulsifier
Bentonite
Fuller's earth (non plastic clay mainly mineral montrorillo nitrite)
Aluminium salts
Ferric hydroxide
Water glass.
Natural emulsifier (Partially surface active lanolin)
Egg Yolk (cholesterols), Gelatine and casin.
Additives (Promoters) for pesticides : Aliphatic alcohols (2-ethylhexanol), urea and xylene.
Emulsion preservatives – Glyoxal (not biodegradable). Emulsion stabilisers – polyglycol, ethers
of alcohols, fatty acids, glycerides and alkyl phenols.
5. CRITERIA OF SELECTION SPECIFIC EMULSIFIER FOR A PESTICIDE

(i) Solubility: Emulsifier should be sparingly soluble in internal phase and soluble as in external
phase oil. Soluble emulsifiers form w/o emulsions and water soluble emulsifiers tend to form o/w
emulsions as per Bancroft rule.
(ii) Chemical Structure: It should match the chemical structure of internal phase (similar
chemical structure of pesticide desirable).
(iii) Phase volume ratio: It determines the external phase type of emulsion. Excess of oil
proceduces w/o (water in oil) emulsion which requires oil soluble emulsifiers; With excess of water,
o/w (oil in water) emulsion is produced for which water soluble emulsifier is used.
(iv) Nonionic emulsifiers are required for preparation of w/o emulsion. Addition of anionic
emulsifiers gives rise to mixed emulsifiers which are widespread in use.
(v) H.L.B. values: Emulsions are prepared with either one, two or more emulsifiers, usually
with different H.L.B. value (hydrophilic – lipophilic balance). Hydrophilic emulsifiers with high H.L.B
value, gives formation of o/w emulsion. On the other hand, hydrophobic emulsion, with low H.L.B.
value, are more used for preparation of w/o emulsions. H.L.B. values of emulsifiers are given in
table-below
Table 5
H.L.B. value of emulsifiers (non ionic)
Fatty Acid esters of H.L.B. value
Ethylene glycol 1.5–2.9
Polyethylene glycol 1.8–18
Glycerol and polyglycol 0.8–4.5
Sorbitol 1.8–8.6
Saccharose 7–15
Polyglycol ethers of
Alcohols 8.2–16.9
Fatty Acids 8.1–15
Glycerides 8.0–18
Alkil Phenols 9.92–16.5
Trial and error: Based on above stipulations, one/more emulsifiers are selected and a trial sample
of emulsifiers with particulars of pesticide is selected for further test. Quantity of solvent (emulsifier
and others if any) varies from type of pesticides emulsion. The following table gives the percentage
of solvents required for liquid pesticides.
Table 6
Pesticides Solvent % wt.
Endosulfan, 35%
E. C. 62
Butachlor 44
DDVP, 76% 16
Monocrotophos W.S.C. 48
6. WOOD INSECTS
Common insects, which destroy wood, are termed as termites and wood worms (Arobium
pumctalum, teredo, long worm banberia, monteria beetle, lyctus and xeslabium and rufovillo – san).
7. MANUFACTURE OF NEEM BASED PESTICIDES

A. Neem seeds are crushed and extracted by Soxhlet extraction using petroleum ether. The
extract is concentrated to yield paste type residue which is then mixed with more ether. Oil is kept
for about a month when fatty solid matter settles down and separated by decantation. The yellow
coloured liquid is called Neem oil or neemol. Neemol protects about 94.7% of leaf area at concentration
of 1000 ppm.
B. For Nimidin manufacture, crushed seed of neem, and ethyl alcohol are used in Soxhtlet
extractor which yields vermidin. It is then mixed with ethyl acetate and water. The ethyl acetate
soluble part is then concentrated and the resultant residue is again partitioned between a mixture of
petroleum ether and aqua methanol soln (5:95). The aqua methanol soln. is concentrated to get brown
semisolid residue called Nimidin. The solid residue obtained from both of these processes is used
as organic manure.
Chapter
43
CRITICAL PATH METHOD (CPM)
It is a systematic procedure in Industrial engineering for scheduling and managing complicated
projects. The basic factors for CPM are.
(i) A large project consists of a long list of smaller tasks.
(ii) Some of these tasks are of such nature that the next task cannot be done unless some other
one is finished.
(iii) The manpower available at any given period is limited.
(iv) A careful planning can device a system of priorities which ensures that most important
task is always being worked upon by the largest number of people of the project. The manpower
deployed will be as uniform as possible.
(v) The sequence of tasks which is done at least time period one after another without any
interuption is the critical path.
(vi) The procedure is set in diagram depicting all tasks with time periods for completion, floats
if any etc. The shortest route time period for completion of the project is called the critical path for
the project scheduling. The CPM chart is made with the aid of a computer.
N.B. PERT – Evaluation and Reviewing
Technique It is slightly different from CPM technique.
254
Chapter
44
PSYCHROMETRY
The properties of moist air viz. humidity, relative humidity, wet bulb temperature, enthalpy,
humid vol. and saturated volume are dealt in psychrometry. In humidification, evaporation of water
or other liq. takes place in contact with air and dehudification means condensation of water in air
water mixture or a mixture of non condensible gas and a liquid. Specific humidity of an air water
mixture is the lb/kg of water vapour carried by l lb/ 1 kg of dry air and it is dependant on partial
pressure of vapour.
Percentage humidity is the ratio of actual humidity to the saturation humidity at the air/gas
temperature. At all humidities except 0 and 100 percent, the percentage humidity is less than relative
humidity. Percentage R.H. is the ratio of partial pressure of water vapour in air water mixture at
existing temperature to the vapour pressure of water at dry bulb temperature. Dew point temp is the
temp at which a given mixture of air and water) (or a non condensing gas and a liquid) is cooled
at, constant humidity, to become saturated. It is also called adiabatic saturation temperature. Total
enthalpy is the heat content of air water or gas–liquid mixture. Wet bulb temperature is the equilibrium
temp. attained by a water surface in contact with air (or a non condensing gas) such that the latent
heat of evaporation of water or liquid in the interface is equal to sensible heat transferred from air
water mixture to the water surface. Dry bulb temperature is the ambient temperature. The difference
between D.B. temperature and W.B temperature is called wet bulb depression.
Humid volume is the total volume of a unit mass of vapour free gas and that of water vapour
in it at 1 atm and existing temperature of gas. For a saturated gas, humid volume is saturated volume.
From psychrometric chart (Fig.1), humidity, enthalpy, dew point, D.B./W.B. temperatures, enthalpy
etc., can be found when any two of above factors are known. Humid heat is the heat necessary
to increase the temperature of 1 lb or 1 kg of gas and vapour it may contain in it by 1°F or 1°C.
Moisture content of air and its temperature is not only important for human comfort but also
in industry for processing and storage of various products including food and some pharma products
and is the basis of air conditioning. In the process of humidification, cooling of liquid takes place
due to evaporation and this principle is used in cooling towers.
Calculation of various properties of air can be made when some factors are known.
Wet bulb temperature
kw
tw = t − × h′fg ( ww − w)
hfg
255
0
48
1.0 16 F or barom etric P ressure o f
a ir
0 46
0.8 12 29 .92 ln H g
d ry
r
pe 180 0.0 25
E nthap y of w a ter tu
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44
f
do
per lb of dry a ir o is
of
m 0.0 24
un
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ai y a
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Gr dr 20 0.0 23
rp
16
0.2 0
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40 160 0.0 22
.
80
. t .u
32 4 0 50 60 70 80 39 0.0 21
150
nB
Tem pe rature o f w ater added 0.0 20

a t io
38
o r rejecte d deg F 140 0.0 19
tu r
of d ry a ir
Fig. 1 Psychrometric chart at atmospheric pressure.

34
sa
75 130 0.0 18
at
G rain s of M o isture pe r lb of d ry air.

32 0.0 17
lp y
Loss of w ate r per lb o f dry air.

120
B tu pe r lb
th a
30 0.0 16
70
En
26
28 11 0 0.0 15
24 u re 0.0 14
d e vi a tio n
p e in t
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22 te m p o 0.0 13
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on ew
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at
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el
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b tu
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et 0.0 07
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1B 0.0 03
10 .
20 0.0 02
02
10 0.0 01
03 04 05 0 0.0 00
25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 11 0
D ry B lub Tem pera ture— D eg F B arom etric pre ssure. 29.92 in of H g
256
S ourc e: P erry 's H and book 3rd edn. 1 949
PSYCHROMETRY 257
where t = D.B. temp °C

tw = wet bulb temp °C
k w = diffusion co-eff. of water vapour through film of air water vapour mixture, kg/m2
h′ f g = Enthalpy of vaporisation at wet bulb temperature kcal/kg

hfg = Enthalpy of vaporisation at dry bulb temperature kcal/kg
ww = Specific humidity at wet bulb temp.
w = Specific humidity at dry bulb temp.
If the coefficient, kw is not known, dew point can also be calculated as per the modified
A.P. Jhon equation or carrier equation.
Specific humidity
M v Pv 18.016 Pv Pv
w = M P = 28.966 × P or 0.622 P
a a a a
where, w = specific humidity

Pv = partial pressure of moist air, mm Hg
P a = partial pressure of dry air, mm Hg
Mv, Ma = Mol. wts of water and air respectively
Dew Point
Modified A.P. Jhon equation for dew point temp. calculation
1.8P (t − tw )
Pv = Pv′ −
2700
where, Pv′ = satn. press. at wet bulb temp, mm Hg
Pv = partial pressure of water vapour in air, mm Hg
t = D.B. temp °C
tw = wet. bulb temp °C
P = total pressure (Pair + Pv), mm Hg
Carrier equation for dew point calculation
(P − Pv′ ) (t − tw ) × 1.8
Pv = Pv′ −
2800 − 1.3 (1.80 t + 32 )
Chapter
45
GLASSES AND TEXTILE
GLASS FIBRES
A. CLASSIFICATION
Glass Type Uses
E Glass – Alumino borosilicate For GRP and including
glass containing alkali use in other appliances.
1% (wt)
C Glass – Alkali–lime glass with High acid resistance
high borontrioxide appliances use and
(B2O3) staple fibres.
A Glass – Alkali–lime glass with Spl. applications/acid
little or no B2O3 and resistant, and cement
alkali 1%(wt) reinforcement.
E–CR Glass – Alumino–lime silicate For G R P and flue
glass with alkali 1%. gases pipes.
High acid resistant
R Glass – Alumino–silicate glass Spl. use in G R P
without Ca and Mg oxides– boats of high power.
high much properties.
D Glass – Borosilicate glass-speciality Micro wave heating
glass with high plates and special uses.
dielectric properties.
S Glass – Alumino silicate glass Used in G R P boats of
with MgO = 10% good high power.
tensile strength.
258
GLASSES AND TEXTILE GLASS FIBRES 259
B. DIELECTRIC CONSTANTS OF TEXTILE GLASSES AT 1 MHZ

E glass = 5.8 – 6.4
C glass = 6.8
E–CR glass = 7
R glass = 5.6 – 6.2
S glass = 4.8 – 8.3
D glass = 3.85
Quartz glass = 3.78
C. TEXTILE GLASS FIBRES ARE MADE FROM DIFFERENT GLASSES AS ABOVE

BY FIBERISATION PROCESS DESCRIBED IN CHAPTER 26
N.B. 1. Glass filament yarn – ISO – 2078 and ISO 3599 EC–9–34 where E glass and C glass
contain 9 filament diametres in µm
2. 34 tex (1 tex = 1gm/1000m)
D. USES OF TEXTILE GLASS FIBRES

Textile glass fibres of different glasses is available as glass filament and glass staple fibres of
limited length (spun fibres) of dia. 9 – 13 µm. Uses involve insulation, textile purposes viz decoration,
filtration, reinforcement of a matrix to make a composite. Matrix can be plastics (thermo or thermosets),
bitumen, rubber, cement, gypsum and other materials.
Textile yarns and plied yarns with filament dia of 5–13 µm are mostly woven into fabrics. The
plastic admix products viz mats, rovings etc are made from glass filaments of 9–24 µm dia. Tensile
strength of E glass filament = 3400.Mpa and that of R glass filament is 4400 Mpa.
E. COMPOSITION OF GLASSES
Multi– A glass C glass E–CR Alkali R S D
purpose glass resistance Glass Glass Glass
glass
SiO2 53–55 70 – 72 60–65 58 60 60 60–65 73–74
Al2O3 14–15.5 0 – 2.5 2–5.5 12–13 0.7 24.5 20–25 –
CaO 20–25 5 – 9 14 21 5 6 – 0.5–0.6
MgO 20–25 1 – 4 1–3 4.5 – 9 10 –
B2O 3 6.5–9 0 – 0.5 2–7 <0.1 – – 0–1.2 20–23
F 0–0.07 0.15
Na2O

ZrO2  <1 1 0.4 0.1

K2O  0.3
Fe2O3  2.1
TiO2 
Chapter
46
ENVIRONMENT AND POLLUTION
AIR AND WATER
1. SOLAR ENERGY
About 20% of total solar energy transmitted by sun is lost through space until it reaches about
3–5 km above a city. A polluted city atmosphere can reduce further about 10–20% of sun's energy
out of 80% reaching on the earth. The solar energy thus reaching is sufficient to initiate photochemical
process resulting in smog formation due to complex reactions between oxides of nitrogen and
hydrocarbons present in city air in presence of solar radiation.
The remaining solar energy (short wave radiation) is then absorbed by the earth's surface and
re–emitted as long wave or heat wave radiation. The air layers, close to the radiating surface, soil,
building structures or any other objects, are heated and start to rise as convection air stream. The
air motion thus produced will disperse and dilute air pollutants. The two metrological phenomena,
responsible for high or low pollutants levels in air, are due to atmospheric stability and air flow is
determined by sun's energy reaching the earth.
1.1 Atmospheric Stability
The ground surface heating and resulting in heating of air adjacent to it, produces change in
temperature with height above sea level which is called adiabatic lapse rate @ 5–4 °F per 1000 ft.
When the temp. decreases with height, the lapse rate is +ve and a good dispersion and vertical
transport of pollulants can be expected under this unstable weather condition; conversely, the air is
stable when the adiabatic lapse rate is –ve when the air temperature increases with height. When
lapse rate becomes –ve it is also called an inversion and under this condition no vertical dispersion
of pollutant in air can take place and thus the pollutants remain trapped within the inversion layer
of air at the particular ht. In table 1 temperature above sea level at different zones are given.
1.2 Greenhouse Effect
Earth atmosphere act as a greenhouse in trapping heat from sun after it is reflected from earth
surface as a long wave (infra red) radiation. The absorption of long wave is effected by small
amounts of water vapour. CO2 and ozone gases are called greenhouse gases in the air. The clouds
are opaque to too long wave radiation unless they are extremely thin and cirrous clouds, after clear
sky can increase surface air temp. by a few degrees. The green house gases affect the surface air
temperature which causes unstable weather condition. The burning of fossil fuels, auto emission, and
other combustions increase the CO2 conc. in air. Under Kyoto Protocol (1997), six greenhouse gases
260
ENVIRONMENT AND POLLUTION AIR AND WATER 261
have been identified which are, a part from CO2, CH4, Nitrous oxide, HICs, CFCs and Sulphur
hexafluoride. Also ozone layer over earth atmosphere if broken by greenhouse gases, the natural
protection against ultraviolet rays is removed which pass through ozone hole. This causes more
increase in air temperature with the possibility of more melting of ice and increase in sea water level.
1.3 Composition of Clean Dry Air at Sea Level
N2 = 78% vol.
O2 = 20.94
Argon = 0.93
CO2 = 318 ppm
Neon = 18 ppm
H2 = 0.5–1 ppm
CO = 0.1 ppm
CH4 = 1.5 ppm
Ozone = 0.02 ppm
SO2 = 0.0002 ppm
NOx = 0.001 ppm
2. METHODS OF CONTROL OF LIQUID EFFLUENTS FROM INDUSTRY

There are three main methods of handling liquid effluents.
(i) Chemical treatments
(ii) Mechanical treatments
(iii) Biological treatments
These methods are further subdivided into following categories of treatments :
(a) Various chemical treatment methods available.
COD
(b) Biological treatment to reduce BOD. A high ratio indicates that the effluents
BOD
are not biodegradable which can not be converted to biodegradable even by bacteria.
(c) Air filtration/ pressure filtration
(d) Sedimentation in clarifiers with coagulating agents.
(e) Forced aeration by aerators in lagoons.
(f) Pure oxygen activated sludge process or wet oxidation process.
(g) Activated sludge cum carbon activated process.
(h) Electrodialysis
(i) Semipermeable membrane process.
(j) Dissolved air flotation process.
(k) Biotechnology method.
(l) Anarobic fermentation process using microorganism (bacterial strains)
(m) Ion exchangers
(n) Flocculators
(o) Floating aeration in ponds
(p) Storage of treated effluents in delay ponds (1+1) and slow discharge to outfall through
storm water drains.
(q) Molten Metal Technology.
2.1 Biological Treatment Methods
(i) Special bacteriological strains/cultures (viz thermobac, polybac) which can make metabolic
conversion of poisonous into non-poisonous materials. The cultures are available for HCN, nitrite,
Phenolics, aldehydes, petroleum oils and other organic toxic materials.
(ii) Pure oxygen activated sludge can simultaneously cause biodegradation and chemical
COD
conversion of wastes containing high ratio.
BOD
(iii) Wet oxygen process can destroy wastes from too dilute a stream for incineration and too
concentrated effluent for conventional treatment.
(iv) Activated sludge cum activated carbon process can handle wastes, containing both
biodegradeable materials and wastes, having very high chemicals.
(v) Ion exchange and electrodialysis methods are for removal of ionic wastes.
(vi) Dissolved air floatation process for removal of oil and emulsion wastes. Fine air bubbles
are sparged at the bottom of wastes which carry both oil and emulsions to top as scum which are
periodically removed. Efficiency is over 95%. Suitable also for fine solids and colloids.
(vii) In biotechnology method high and low toxic materials from pesticide units are separately
stored in polythene lined solar evaporation pond. Sun’s rays evaporate water from high and low toxic
tanks. In the high toxic tanks, on concentration, the pollutants become harmless. The technique is
not very convincing. This process is usually used in pesticide plant wastes. The water from pesticide
free tank can be used for land fill after neutralisation with lime, aeration and flocculation. The low
concentrated pond similarly gets pollutant free or the pollutants within limit.
(viii) Floating aeration in lagoons–The process has several floating aerators in lagoons, handling
obnoxious wastes, usually from paper mill, after lime dosing. Oxygen is supplied to wastes by
aereators.
(ix) Anaerobic fermentation of brewery/distillery wastes, containing alcohol are usually carried
out by methanococcus bacteria in a closed fermenter when alcohol is degraded by bacteria to CH4
and CO2 gases which can be used for fuel purpose in the plant.
Methane bacteria has 9 types of strains, each for different substrates (food for bacteria).
Sewage sludge can also be digested by anaerobic treatment.
According to Barker, the 9 strains of methane bacteria are as follows.
Products
(a) Methanobacterium formicicum – Formate, CO2 and H2
(b) – Do – meliaanski – Primary and secondary alcohols, H2
(c) – Do – propionicum – Propionate salt.
(d) – Do – Sohngenii – Acetate and butyrate
(e) – Do – Suboxydans – Butyrate, Valerate

(f) Methanococcus mazei – Acetate, butyrate
(g) – Do – Vanielli – Formate, H2.
(h) Methanosancina methanica
(x) Molten Metal Technology
This was developed in USA. The process disintegrates hazardous wastes into elemental form
in a hermitically sealed unit when wastes are separated into elemental from which can be converted
to useful by products. The details are not available.
(xi) Solid Wastes Disposal
A. Hazardous solids are disposed of by putting in sealed drums which are dumped in concrete
underground tanks.
B. Overground dumping of hazardous wastes on concrete floors.
C. Sedimentation in ponds/lagoons
D. Incineration–mainly for hospital garbage and domestic refuge.
E. Chemical treatment method.
Stipulation of Hazardous wastes, limits of hazardous wastes generation and disposal methods
are elaborated in statutory Hazardous wastes (management and handling) Act 1989. Radio active
wastes are covered under Atomic energy Act 1962.
Water pollution from industrial effluents are covered under the water (prevention and control)
of pollution Act, 1974. Disposal of treated industrial effluents are also controlled by MINAS or State
Pollution control board standards.
In table 2 limits of pollutants as per MINAS/ IS 2490/Assam pollution control board (for
Namrup fertiliser plant) for final discharge of effluents to river is given.
3. WASTE WATER STREAMS

From large chemical processing plants can be grouped as follows
(a) Chemical effluents sewers from process plants
(b) Oil water effluent sewers from compressors.
(c) Cooling water purge sewers.
(d) Steam–water sewers from plant sewers.
(e) Water treatment plant sludge disposal sewer.
(f) Sanitary sewers.
(g) Solid wastes disposal.
3 (a) Chemical Effluent Sewers
The sewers from process plants should be designed to collect contaminated process chemicals
wastes which occur as discharges from process equipment, leakages from pumps glands, spillages
and floor washings. These are separately collected in a pumping pit in the plant through separate
lines and from where it is pumped through a properly designed pipe line to effluent treatment plant,
designed for treatment of such effluents. In case of ammonical effluents, it is stripped with L.P.
steam when ammonia is removed. The remaining ammonia in stripper outlet water is air stripped in
a cooling tower and effluent discharged to delay pond.
Storm water from trenches in the plant goes directly to storm water drains along plant roads
as it does not contain any harmful chemical effluent. Acidic and alkaline effluent from D.M. plant
are mixed in a pond within the plant B.L and pumped to chromate treatment plant or delay pond.
The D.M. plant pond is usually rubber lined and D.M plant floor area, trenches are lined with acid
proof tiles.
3 (b) Oil Water Effluent Sewers
The oil water effluent from compressors in a plant, coming through sewers, are usually treated
at the API oil trap, containing coke and clear water is discharged into the storm water drains. The
operation of oil traps is to be regularly monitored for performance.
3 (c) Purge Cooling Water Sewer
The cooling water is usually treated in chromate treatment plant and contains 10 : 20 ppm of
chromate CrO4 = (+6) and phosphate (TSP) to prevent corrosion of C.W pipelines and equipment
using cooling water. Cr(+6) is to be reduced to Cr(+3) before discharge. The purge water from each
cooling tower is led into a sewer pipe which flows to adjacent purge cooling water treatment plant
using 10% Sodium meta bisulphite solution after C.W is acidified to pH 2.5 and treated with Sod.
meta bisulphite, NaHSO3 which reduces Cr(+6) to (Cr+3).
H2SO4 + NaHSO3 + Na2Cr2O7 → Na2SO4 + Cr2(SO4)3 + 2NaHSO4
The reaction mass from Sodium meta bisulphite reaction tank, having agitator is transferred to
neutraliser, where it is treated with lime solution and pH is brought upto 7.5. Acidic and Alkaline
mixed effluent water from DM plant can be mixed here also. The neutrlised effluent is then pumped
through sewer line to delay ponds from where it is discharged to treated effluent discharge drain
through delay pond overflow point.
3 (d) Steam Condensate Sewer from Plants
The condensate blowdown from boilers are collected in separate sewers as it contains alkaline
wastes and pumped from plants to delay pond.
3 (e) Water Treatment Plant (WTP) Sludge Disposal
The sludge, containing 3–5% suspended solid from water treatment plant, usually contains
Ca(OH)2,CaCO3,A1(OH)3, mud etc. and is drained by pumping to sludge settling tank when suspended
materials settle at the bottom and clear water is discharged to final effluent drain of delay pond.
3 (f) Sanitary Sewers Effluent Treatment
The effluents from septic tanks are taken by 4" lines and combined with other sewer lines to
a 8" sewer line and the sewage taken to septic (treatment) plant. usually, a small concrete pit with
(+) 6" seal between inlet and outlet sewer lines is provided at direction change points of sewer lines.
The pit is covered with concrete grills at top.
3 (g) Solid Wastes Disposal
(i) For hazardous solid wastes, packing etc. are usually put in plastic or metal drums and
lids are sealed. The drums are put in underground concreate bunkers and entrance is covered with
concrete slabs.
(ii) For other solid wastes, like catalysts containing harmful metal salts etc, are dumped in
covered rooms with concrete floor for long storage and if possible, sold to interested parties.
4. SURFACE WATER THROUGH STORM WATER DRAINS

Depending on total area of plant, the run–off water rates from rains are calculated as follows.
(i) Run–off water as 100% for all paved area inside the plant.
(ii) Run–off water as 50% for unpaved areas inside the plant–the other 50% is thought to
have been absorbed in other soil. Rain water from individual plants are discharged to storm water drains.
(iii) Rain water accumulation per inch of rainfall per hour per ft2 area is 0.014 US gallons
per minute (0.0539 lit/min per ft2). In addition consider fire water accumulation of 500 US gallons
per minute for reasonable duration and any other uncontaminated water quality which comes from
plant to storm water drains which ultimately goes to outfall points along with delay ponds over flow.
W.T.P. plant sludge water quantity and individual effluent treatment plant’s treated effluent quantity
also goes to outfall point.
5. OTHER EFFLUENT TREATMENT PROCESSES FOR SOME INDUSTRIES

5.1 Fertiliser Plant Chemical Effluents
5.1.1 Urea Plant
The plant generates (a) Vacuum condensate from Vacuum concentrators containing urea and
NH3 from prilling tower top where the vacuum concentrators are located. The condensate is treated
in urea hydrolyser when urea hydrolyses to NH3 and CO2.
NH2CONH2 + H2O  → 2NH3 + CO2
The vacuum condensate is to be first stripped in upper stripper column containing bubble cap
plates after preheating to 110°C and taken out from bottom of upper section and fed to urea
hydrolyser after preheating to 189°C in feed preheater. Hydrolysis is carried out at 18 ata and 195°C
by indirect steam heating in inbuilt steam heater bundle.
The hydrolysed solution from urea hydrolyser is then fed to bottom section of NH3 stripper
with a kettle type reboiler at bottom using 6 ata steam and NH3 and CO2 recovered are recycled to
process. The Conc. of urea reduces from 0.84% to 380 ppm and that of NH3 Conc. reduces from
3.82% to 140 ppm. The treated effluent from stripper bottom is stored in a 500m3 underground
storage tank along with pump spillages and from there it is pumped to a 500m3 underground storage
tank for air stripping of ammonia after it is made alkaline by adding NaOH solution and pH raised
to 9. The stripped solution at bottom of air stripper may contain upto 30 ppm ammonia which is
then sent to delay pond for slow discharge.
5.1.2 Ammonia Plant (NG based)
5.1.3 The process condensate, generated in purification section contains NH3, CO2 etc and is stripped
in a L.P steam stripper. The condensate contains 500 ppm NH3, 4000 ppm CO2 and 1500
ppm methanol. The condensate is flashed in flash vessel when most of the CO2 is removed
and then stripped to remove NH3 and methanol. The stripped condensate contain NH3 = 10
ppm, CO2 = 10 ppm and 20 ppm methanol which is sent to D M plant for cation polishing.
The purge water from the recovery section of ammonia plant, containing 1% ammonia, is sent
to 500 m3 underground effluent storage tank in urea plant. In Table 2, the analysis of waste water
standards for discharge to Rivers, canal, etc is given for fertilizer plant manufacturing urea and
intermediate product of NH3.
5.1.4 D.M. Plant
The acidic effluent, generated by cation exchanger condensate polishing unit, is to be taken to
D M plant neutralisation tank with rubber lined and with epoxy coating. Similarly, alkaline anion
exchanger effluent and process water gravity filters are to be taken to neutralisation tank where pH
is neutralised and when the tank becomes full, the water from the neutralisation tank is pumped to
delay pond. If necessary, the acidic and alkaline effluent can be pumped separately to chromate
treatment plant.
5.1.5 API Oil Filters
In each compressor house an API oil filter with coke packing is to be provided to remove oil
from condensate and clear water taken to storm water drains.
5.1.6 Steam Utility Plant Effluents
The B F W purge water from boilers is to be separately taken in a header to a pumping pit
and from there, it is to be sent to delay pond for slow discharge.
5.1.7 Sewage Treatment By Anaerobic Fermentation
Sewage is usually having high B.O.D value. The sludge is treated in sludge digestor under
anaerobic condition with agitation when soluble sludge collects at the bottom and removed. CH4 and
CO2 gases are removed from top. Time for digestion is 12–50 days. The supernatant liquid from
digestor is removed from top. There are 9 species of methane bacteria having different substrates
which can be judiciously used for biological effluent treatment. In sludge digestion, percentage of
total solids, conductivity, volume of sludge, pH and BOD value are indicators for efficient digestion.
The digested sludge is then subjected to elutriation.
The fresh sludge suitable for disgestion may contain other alcohol soluble substances, cellulose,
hemi-cellulose, lignin crude protein and ash (24%).
6. PRESSUREISED AIR FLOATATION PROCESS FOR OTHER INDUSTRIAL

WASTE WATER TREATMENT FOR
(i) Removal of pulp and paper fibres from waste water
(ii) Removal of oil from refinery waste.
(iii) Primary clarification of sewage and thickening of sewage sludge.
(iv) Full recovery of coal washery wastes.
(v) Removing oils from metal processing wastes
(vi) Removing fatty acids and soaps from wastes water from soap works and processing of
edible oils.
(vii) Removing suspended solids from cannery wastes
(viii) Clarification of laundry wastes
(ix) Removal of grease and suspended solids from meat packaging units.
(x) Waste water treatment from engine cleaning and paint stripping; etc.
The process consists of dissolving the gases in effluent liquid under high pressure and releasing
the pressure of liquid suddenly in a separator by taking out the effluent fluid by a horizontal discharge
pump at 25-60 psig pressure. Alkali (for pH control) and coagulant is added to mixing tank as well
as to pump discharge. Compressed air is added to pump suction and released from separator top
and separator outlet fluid and is slowly fed to the conical floatation unit by a back pressure control
valve. The bottom scrapper of floatation unit removes sludge and scum is removed from top of
flotation unit and clear treated water over flows from top. About 5–8% free air dissolves.
The process is based on the principle of Henry’s law which states that increase of solubility
of gases dissolved in water varies with the absolute pressure of gas.
6.1 Food industry Waste Water
Ultrafiltration by membrane method is used to retain organic substances in food industry’s
waste water. Pressure required is 10–20 m water column and dissolved materials pass through the
membrane.
BOD Value % retention by membrane
(mg/lit)
18250 99.7
(Carbohydrates)
Potato starch 12700 85.1
Veg. Proteins 21500 99.6
Cheese whey 45000 99.3
Table 1
Atmospheric Temperature above sealevel.
Height, KM NAME Temp°C

250 Thermopause 1027
230 Satellite Level
210 Thermosphere 27
70 Mesosphere – 3
30 Stratosphere – 73
10 Troposphere
Sea Level 7
Table 2
1. Limits of Pollutants as per Minas/IS 2490/Assam Pollution Board
(For Namrup–III) for Final Discharge Effluents to River
Sl. Constituents Minas IS2490–74 Assam Pollution Board
No.
1. pH 6.5 – 8.0 5.5 – 9.0 5.5 to 8.0
2. Temperature – < 40°C Shall not exceed 40°C
3. Ammonical Nitrogen. 50 mg/lit 50 mg/lit –
4. Total Kjeldahl Nitrogen 100 – 50
5. Free Ammonical Nitrogen 4 4.12 4.12

6. Nitrate Nitrogen. 10 – 20 (Nitrite and
7. Nitrite Nitrogen. – –  Nitrate.)
8. Cyanide as CN 0.2 0.2 0.2
9. Venadium as V 0.2 – –
10. Arsenic as As 0.2 0.2 0.2
11. Flouride as F 10 2.0 –
12. Hexavalent chromium as Cr+6 0.1 0.1 0.2
13. Total chromium 2 – 2
14. BOD (5 days at 20°C) – 30 20
15. COD – 250 250
16. Oil and grease – 10 10
17. Total suspended solids – 100 30
18. Sulphate as SO4 – – 100
19. Chloride as Cl. – – 600
20. Dissolved oxygen. – – 3
21. Resedual chlorine – 1.0 1
22. Phenolic compound – 1.0 1
23. Total Dissolved solids – – 2100
24. Sulphides (as S) – 2.0 2.0
Table 3
2. Ambient Air Quality Standard as per Air Act. 1981
Area Category SPM SO2 CO NOX Remarks
Unit = µg/M3
A. Industrial and Mixed use 500 120 5000 120
B. Residential and Rural 200 80 2000 50
C. Sensitive 100 30 1000 30
AIR POLLUTION ABATEMENT

1. Electrostatic Precipitator
When dust/microbial cells pass through an electrified field (D.C), they become ionised with +ve
charge and are collected on a negatively charged plate. The ionising wires are held at 13000 – 14000
volts and the dust collecting plates are kept at 6000 – 7000 volts. The dust removal efficiency is
about 90%. The controlling factors are air flow rate, plate loading, electrostatic field intensity, size
of dust and its dielectric properties.
Larger foreign particles and increased air humidity can cause severe damage due to sparking.
A medium efficiency dust filtration system should precede the electrostatic precipitator and if required
flue gases should be dehumidified. It is mandatory to use E. S. P for large coal based thermal power
plant.
2. Greenhouse Gases Fixation in Air
Reaction : CO2 + H2O + Sunlight chlorophyll

→ (CH 2 O) + O 2
carbohydrate
For each gm mole of carbon fixed, 470 kj (112 kcal) of energy is absorbed in the biomass.
Dissolved organic substances are usually susceptible to Biological degradation where as refractive
substances are not accessible to microbial attack and are characterised by high C O D and contents
of organic carbon.
This is usually treated for removal by combined adsorption or flocculation and activated
charcoal process. Activated charcoal has surface area of 600–1200 m2/gm and when used for
removal of organic matters most of the materials are removed. The active carbon mass is regenerated
by heat at 750–950°C.
6.2 Cement Industry Inorganic Waste Material
Cement dust from clinker kiln and cement grinding are usually removed by electrostatic
precipitators. In case of waste water from the dust scrubbing unit the waste water is taken to large
lagoons for seepage and sedimentation and clear water is discharged from top of lagoons.
6.3 Porcelain Industry Waste
(1) Preliminary screening, done to remove large coarse or broken particles.
(2) Combined chemical–mechanical methods for clarification.
Waste
w ater
Treated efflu ent

Flo cculating
agents
C larifier Filter press
Pum p
Fig. 1 A Porcelain Industry Waste Treatment.
The process consists of addition of flocculating agents (Al. Sulphate, lime or iron salts) in an
additional tank and holding waste for 5–10 mins and then taking into a clarifier or sedimentation tank.
The sediments from bottom of tank is pumped to a filter press. The suspended matter is thus
removed and clear water after filter press. is discharged. (See Fig. 1)
6.4 Waste Water from Iron and Steel Works
The recirculation water from Blast furnace wet gas treatment, cleaning towers and other
operations like flue gas purge water consists of aeration upstream of sedimentation tanks to blow
out carbonic acid followed by sedimentation in tanks. The waste water consists of cyanogen,
sulphur, phenol, ashes, iron oxide, silicic acid slag. Ore particles as well as Al, Carbon, Calcium, Mg
and Zn compounds. By aeration, Calcium/Zinc hydrogen carbonates are converted to carbonates and
precipitated out with addition of flocculating agents–iron or Al salts as well as auxiliary flocculating
agent viz an organic polymer.
The sludges which collect at the bottom of sedimentation tanks, are recovered continuously and
used for land fills.
Toxic materials like alkali cyanides are formed in B.F. gas and flue gases contain HCN or
dicynide. The process of removal of these materials consists addition of formaldehyde to recirculated
water to raise pH to 8–10 and keeping in delay pond for long hold up to convert the cyanides to
harmless polymers.
6.5 Ttreatment of Waste Water from Picking Plants
For treatment of waste water from metal pickling plants, usually one method is for recovery
of Fe+2 or Fe (SO4) 5H2O when HCL or H2SO4 is used for pickling and the 2nd method is by
neutralisation with alkalies when acid pickling is done. Lime is used as a neutralising agent.
6.6 Waste Water from Electroplating Industries
The waste consists of mainly cyanides occurring as alkali cyanides (very poisonous) or as
complex cyanides. The process consists of, reaction with Sodium hypochlorite NaOCl (den.1.21 kg/
lit and contains 12.5% active chlorine, corresponding to approximetely 150 gm of active chlorine (per
lit) when cyanide is oxidised to chlorine cyanide which is then converted to cyanate at pH at about
9.5 using NaOH. Both the temperature is kept below 38°C. The reactions are exothermic:
− −
2CN + 2OCL + 2H2O 
→ 2CNCL + 4OH–
→ 2CNO− + 2C1− + 2H2O

2CNCL + 40H − 
2CN − + 2OCL− 
→ 2CNO− + 2Cl −
Excess Hypochlorite @ 1% is used and residence time in reaction bath is about 20 mins. Air
above bath is exhausted by an exhauster which push the reaction vapours through a water scrubber.
Iron (Fe+2) salts can also be used to form complex salts ferricyanides Fe2 (Fe(CN)6.
6.7 Soda Ash Plant Waste Water
It contains CaCl2 and sludge, containing suspended matters which are treated in a sedimentation
tank for 8–9 hrs when conc. of chlorides are reduced.
6. 8 Waste Water from Pharma Industries
Here various methods viz detoxification, deoiling, neutralisation, treatment with precipitating
agents, decolorisation, sedimentation, biological treatment etc, are used and exact nature of treatment
will depend on specific requirement. When separate treatment methods are to be used for each waste
water from a particular type of product, exact waste water treatment method is to be used.
6.9 Waste Water from Inorganic Dye and Colourant Plants’ Intermediates
The waste water usually contains lead or arsenic compounds which must be detoxified by
using (1) Sodium sulfide to precipitate arsenic sulfide or (2) using (Fe+3) in an alkali solution to
precipitate Ferrous arsenate or adsorptive co-precipitation (3). In case of lead waste water, uses
Sodium Carbonate to precipitate lead carbonate (4) Similarly for barium containing waste water, use
of Sod. Carbonate is to precipitate barium carbonate (5) For chromate containing waste water to
reduce Cr+6 to Cr+3 using Sod. metabisulphite in acid pH and then converting Cr+6 to Cr+3 followed
by neutralisation with lime. (6) For TiO2 containing waste water, treatment with hydrated iron
sulphate is followed by crystallization and reduction to Fe2O3 and H2SO4. The dil. acidified effluent
is then dumped into sea or sent to delay pond.
In all these processes water after detoxification is stored in delay ponds for sedimentation and
slow discharge to surface water.
6.10 Organic Dye and Intermediate Industry
(i) Removal of colours–various methods are used to remove colour viz chlorine, Ferrous
chloride, Sodium hydrogen sulphide. Azo dyes are cracked by reducing agent, land filtration and
biological purification.
The combined method of chemical precipitation with biological purification gives satisfactory
results in some cases of water treatment.
(ii) The waste water, which is more from these industries are first neutralised if necessary. The
segregated streams of waste water are treated individually w.r.t. their composition, treatment method
required and specific type of waste water. The waste water containing toxic substances–cyanide
compounds, arsenic salts, free chlorine, flourine bromine etc are detoxicated by chemical precipitation
method. Oils and fats if present are retained in separators. Waste water containing mainly organic
substances are treated by extraction, concentration by evaporation and other methods.
Strong odours from waste water are removed by aeration with fixed or floating aerators in
tanks, columns etc, by the treatment with Cl2. For all types of waste water neutralisation can be
carried out together with NaOH or lime in aflocculator with built in stirrer for 15–30 minutes before
coarse sludge flakes are sedimented for sludge removal.
For removal of high B. O. D level in waste water the treatment is usually done in digestors
followed by degasifiers to remove CH4 and CO2 gases under 20" vacuum and then separation of
sludge by tickling filtration and finally in clarifiers.
Anaerobic digestion of pulp and paper industry waste is carried out at 0.1 lbBOD/ cft of
digestor/day only if sulfides formed are not allowed to accumulate in the digestor.
6.11 Dairy Effluent Treatment
Waste water from Dairy is first removed of oil in a oil trap and sent to equalisation tank from
where it is sent to anaerobic tank for fermentation. After anaerobic treatment, the effluent is treated
in series in two aeration tanks fitted with air aerator and sent to secondary settling tank. By-pass
arrangement is provided for use in either of the aeration tanks. Settling tank clear effluent from top
is pumped to sludge draining filter and water is recycled to Aeration tank I or aeration tank–II. Heavy
sludge is removed from the bottom of sec. settling tank for disposal.
6.12 Sugar Mill Effluent
The process is similar to above except that lime is added to equalisation tank and a bar screen
is provided before oil trap to remove bagasse fibres.
6.13 Waste Water Containing Mercury
Waste water from caustic chlorine plant using Mercury cell and other processes contains small
quantities of Mercury. There are 3 processes for removal of mercury.
(i) In chemical process, Mercury compounds are reduced with Hydrazine or by precipitating
Mercury as sulphide with thiourea or Sodium sulphide followed by filtration.
air
½ O2 + H2O + 2Na2S + Hg 
→ HgS + 2NaOH
(ii) By reacting Mercury with chlorine and adsorption in an ion exchange resin
Hg + 2HCl → HgCl2 + 2H+
(iii) By Liq–liq extraction when Mercury conc. is reduced to < 0.01 mg/lit.
7. ENVIRONMENT PROTECTION ACT (EPA) 1986

7.1 The prescribed standard for liquid effluents along with parameters for each category of industrial
plants and others are given in schedule–1 of the EPA 1986. Often these standards and parameters
are based on capacity of the factory. In addition MINAS (Min. national standards) for waste
water is applicable for some industries including stack ht. Fertiliser plant treated effluent quality
is given in table – 2.
7.2 The emission standards are also included in the Ambient air quality standard as per Air Act 1981
categorises 3 different areas (industrial and mixed use, residential and rural and sensitive) for
SPM, SO2, CO, NOX as given in table 3. For big projects continuous monitoring of atmospheric
air, over the factory and at some distance along prevalent wind direction. E I A/ E M P report
is necessary for approval of the project either from central pollution control board or state
pollution control board depending on whether the industry is under central govt. or state
authority control. There are 23 projects industries which are under central pollution control
board schedule – I plus all projects with threshold criteria above those specified in schedule –
II under control of state pollution control board.
The schedule – II of the Act gives a list of 46 projects/industries which require state environment
clearance.
In order to get environmental clearance for a big project, it requires submission of E I A
(Environment Impact Assessment) report and E M P (Environment Management Plan) along
with D P R to concerned clearing authority (central and state). Such EIA/EMP reports are to
be prepared by central pollution board approved consultant.
7.3 Treated liquid effluents standard parameters are specified by MINAS or state pollution control
board limits. Often IS standard is also available. The concerned plant authority is required to
maintain these limits, especially SPCB limits. In table–2 these standards for fertilizer plant
effluent discharge limits.
7.4 Delay ponds (1+1) – usually treated effluents from effluent treatment plants are stored in delay
ponds (1+1) having 2 months capacity each from where it is discharged at out fall point after
the rate of effluent discharge is measured in a weir (vnotch or rectangular). Often dilution water
is to be added before discharge to bring the effluent conc. below state pollution board standard
or MINAS.
7.5 Under CPCB notification number S.O 318 (E) dt 10.4.97, the project authority would allow
public views against the proposed project by keeping all project information including pollution
levels (water and air) in concerned district DM’s office or office of central SPCB in the state
capital. District S.D.O will fix hearing dates from public for any complaints which can be
lodged in S.D.O’s office.
8. C.O.D
It is a measure of the components which can be oxidised in chemical reactions. Amount of
Sod. permanganate or Sodium dichromate (oxidants) consumption in reaction determines the value
of COD.
8.1 B.O.D
It is the amount of Oxygen necessary for bacteria to consume organic matter in water and is
determined by means of O2 depletation of a diluted aqueous sample containing microorganisms.
Usually it is determined in 5 days duration at 20°C i.e. B.O.D5.
9. AIR POLLUTION CAUSES

Air Pollution occurs due to dispersal of the pollutants into atmosphere. The pollutants emerge
from chimneys of various furnaces, using fossil fuels, solid or liquid, automobile exhausts, various
chemical processes. The pollution is also due to the dispersion of dust particles which come from
grinding operations, chemical dusts emission, furnace fumes and fumes from solid wastes incinerators
etc. The emitted gases are of varied nature viz smoke particles, CO2, CO, SO2. NOx, HF, NH3 etc. The
so called green house gases viz CO2 etc are responsible for increase in atmospheric temperature which
is responsible for global warming and melting of polar ice caps resulting in rise in sea water levels.
Increased industrial activities and fast increase in automobiles through out the world are responsible
for increase in green house gases in atmosphere. The emission standard is given in Table 3.
10. ANTIPOLLUTION MEASURES TO REMOVE AIR POLLUTANTS, VARY ACCOR-

DING TO THE SOURCES OF POLLUTANTS. SOME OF THESE AIR POLLUTION
ABATEMENT EQUIPMENT ARE AS FOLLOWS.
(i) Gravity settling chambers
(ii) Suction air filters
(iii) Bag filters for dusts
(iv) Electrostatic precipitator for dust laden furnace gases.
(v) Dust cyclones
(vi) Gas scrubbers for removal of fine dusts and soluble gases.
(vii) Pulse jet bag filters for dedusting.
(viii) Venturi scrubbers.
(ix) Air filter houses with reverse cleaning for removal of fine particulate matter.
(x) Dust and fume extractor.
(xi) 4th hole dedusting system for electric arc furnaces.
(xii) Burning of inflammable gases in a flare stack.
(xiii) Use of high rise chimneys for dispersal of residual fly ash in atmosphere from coal
based power plants/cement klin
(xiv) Extension of chimneys with increase in static head of I.D fans where ever feasible.
(xv) Better design of burners for reduction in smoke and NOX.
10.1 (i) Gravity Settling Chambers
For separation of dust particles having diameter lower than 43 µ , gravity settling chamber is
suitable which is used for flow of dust laden air/gases having low degree of turbulance. Rectangular
long chambers are suitable for settling of heavier dust/soots. These gravity filters are rarely used now
and are replaced by more efficient filters.
(ii) Suction Air Filters
These are used for separation of dust of size 1–10 µ from atmospheric air and are placed at
suction of air blowers, boosters or compressors. Atmospheric dust conc. depends of locality, its
industrial units, wind velocity etc. In rural areas dust conc. is the lowest 0.3–0.5 grain/1000 cft, in
industrial area it is about 0.9–1.6 grain and in metro cities it is 0.6–1 grain. Life of air filters is short,
usually 1–3 months.
There are 3 types of air filters, dry, viscous and continuous. Filtering media, is cotton, felt pad,
glass wool, cellulose pulp wire mesh, corrugated fibre board, and cotton/syn. fibre wool etc. In
viscous type filters are coated with mineral oil (having high viscosity and flash pt.) Viscous filters
are having less thickness of filtering medium. Pr. drop across the air filter increases as more dusts
separate out. Maximum allowable pressure drop varies from 0.2 – 0.5 inch water. Dust conc. in an
air filter is normally allowed upto 0.6 – 4 lbs for a 20" × 20" filter. Efficiency of dust collection
is usually 60–85%.
Automatic filters have continuous rotating moving perforated crimped or woven metalic screens.
The washing arrangement is by water spray which is often of viscous type.
(iii) Bag Filters
These are having filtering media of woven cloth for fine dust laden air or gas mixtures which
are allowed to flow through the bags when dust particles separate and form a layer, inside the wall
of the bags which increases the collection efficiency. Once the dust layer is formed, continuous
separation of dust takes place. Excess dusts from the layer fall at the bottom of bags and are taken
out through seal lock. The filtered air/gas goes out of the bags. Automatic arrangement for shaking
of bag filters at regular intervals is done when separated dust falls at the bottom and removed. This
reduces the Pr. drop. A battery of woven bags are placed vertically with hopper and seal lock
provided at the bottom for collection of dusts. Dust particles size to be separated, varies. The
collection efficiency could be 80–90%. Woven cloth has openings larger than dust particle dia. These
filters can have arrangement for automatic shaking for cleaning dust layer from inside the bags.
Chapter
47
VEGETABLE OIL REFINING
1. THERE ARE VARIOUS TYPES OF VEGETABLE OILS VIZ
Coconut oil
Rape seed oil
Groundnut oil
Cotton seed oil
Sunflower oil
Soyabean oil
Rice bran oil
Corn oil
Castor oil
Lin-seed oil etc.
Out of the above oils, crude vegetable oils extracted from oil seeds except Rice bran oil which
is made from bran of paddy while rice dehulling process is carried out – the bran is the outer brown
coating on rice and husk forms the outside hull of rice. Rice bran oil is made from rice bran by n
hexane solvent extraction process. The crude veg. oils from corresponding seeds are usually expelled
by mechanical expellers followed by refining by degumming process, alkali neutralisation process,
bleaching process and deodourisation process. When mech. expeller is not used, rice bran is pelletised
and then solvent extraction is done in a series of 4 solvent extractors which also removes oil from
meals from oil seeds. Vegetable oils can also be extracted by suitable solvent extraction process after
the cooked seeds are flaked in a flaking machine.
2. CRUDE OIL EXTRACTION FROM OIL SEEDS

(i) Oil seeds, as it is received in oil plants, contain naturally occurring seeds, pods, earth and
often metal iron parts. Before storage, the foreign materials are removed by screening and aspiration
and iron removed by electromagnet and sample is analysed for moisture content, oil content etc. The
freshly harvested oil seeds contain as much as 20% moisture and grain must be dried to around 13%
moisture for extended storage. High moisture reduces oil content, decrease in protein, increase in
colour of extracted oil, and refining losses.
275
Oil seed grains, if left unattended and temperature of storage is not checked, grain temperature
will rise spontaneously and damage the seed for which it is to be either processed immediately or
heap is shifted to another location.
(ii) Drying of oil seeds, containing 20–50% oil, is usually done in direct gas fired furnace and
hot gases move upwards and make contact with falling seeds from vertical drying tower. Other heat
source is, indirect steam heating of air in a heater or solar drying units. The drying temperature limit
is 63°C; higher temperature will increase colour of meal and oil, denature the protein and will increase
the phosphatide levels in crude oil and even grain fire may occur. Storage should be of concrete
structure.
(iii) Oil expelling by mechanical expellers: The oil in seeds are lightly bound with the cell and
mechanical pressure is applied to remove the oil by expellers which are located in the seeds preparation
section building. The operation involve cooking, pressing of dried seeds, cake cooling, finishing and
crude oil filtration.
Oil seed or seed flakes (whenever required) are put into vertical stacked agitated cooker when
heat is applied. After cooker, hot meals enter screw presses or multiroller expellers. Modern batch
process uses hydraulic presses at 300 – 500 kg/cm2 press.
In open type haudraulic presses, seeds must be wrapped in pressure standing cloth and the
closed type are provided with pots and cages. In screw presses the applied pressure is very high
(upto 3000 bar) and process is efficient as oil upto 98% can be expelled. Usually oil removed varies
from 60–98%. The oil cake passes through end plate and becomes hard and oil comes out through
drainage bars. After the cake is broken and cooled it is sent to solvent recovery section, if installed
for further recovery of oil. In case solvent recovery of oil from cake is not desired, the expellers
are operated with the highest pressure. The crude oil, after expellers, contain fine meals which is
removed in scheming tank followed by filtration in press leaf or plate and frame filter presses.
Crushed vegetable oil is sent to storage or sent for refining. The quality of oil is higher than solvent
extracted one because less oil soluble impurities (viz phosphatide etc) are removed. Removed fine
meals are sent to pressure flaking operation for further recovery or sent for solvent extraction if
desired. Oil seeds are often subjected to flaking operation by a flaking roller if needed for better oil
extraction in expellers. Mechanical extraction is suitable when oil seeds contain over 20% oil.
3. RICE BRAN OIL

It is a desirable vegetable oil and which is harmless. It is produced from rice bran by n–hexane
solvent extraction. Better solvent is isopropyl alcohol due to its low inflammability. By solvent
extraction very low residual fat content can be achieved. (Apart from rice bran, whenever other
seeds are used for solvent extractions, where oil content is less than 20%, Iso-propyl Alcohol which
is a better solvent due to its low inflammability and having B.P. of 55–70°C which can be steam
stripped-can be used.) Hexane can be removed from oil at temperature below 100°C in vacuum. The
solubility of water in hexane is only 0.1%. The process of crude rice bran oil production by solvent
is given in Fig. 2. The solvent dissolves only glycerides but not undesireable materials viz colouring
matter, gums or phosphatides. Since rice bran contains 8–16% vegetable oil, it is usually processed
by solvent extraction after drying of brans followed by pelletising.
Solvent extraction of seed flakes or rice bran consists of cylindrical vessels of size with high
D/H ratio and fitted with a sweep agitator with scrapper to remove the extracted seed flakes or bran
during solvent stripping with steam (direct and indirect steam heating) solvent inlet/outlet facilities
for pumping and crude oil inlet. A 3–5 m3/hr capacity extractor with 5 such batch extractors in series
VEGETABLE OIL REFINING 277
is capable of producing 600 MT/day rice bran or other veg oils. Hexane required is 50 MT. Often
4 stage solvent extraction of pelletised rice bran or meals from oil expellers after filter pressing is
used. Solvent extractor using 4 stage extractors where meal, rice bran pellets/seed flakes and solvent
from previous extractor is used and fresh solvent enters into 1st extractor and successively move
to last or 4th extractor. Flow sheet using one extractor is given in Fig. 1.
Fig. 1 Block Diagram for Solvent Extraction Process for Oil Seeds
Flow in extractor is counter current where pure solvent comes in contact with, meal/flakes and
pellets which already have been largely extracted or vice versa, in both batch and counter current
process. The solvent rich oil is then steam stripped in a steam stripper to remove solvent and recover
vegetable oil. The solvent is then rectified in a distillation tower in vacuum to remove dissolved oil. The
solid meal from extractor is further treated with hexane to remove residual oil in meal (cake), dried
and cooled and then sizing operation with grinding is done. The fixed meal is then sent to storage. The
crude rice bran oil is then either subjected to miscella refining or further subjected to refining process
which gives a light yellow colour to rice bran oil and is a relatively stable edible oil. Rice bran oil hardens
at 30–35°C and is often used in margarine. The properties of vegetable oils are given in Table 156/158
in vol. IIA and its empirical formulae for physical properties in table 155 in vol. II.A.
4. REFINING OF CRUDE VEGETABLE OILS

The crude vegetable oils contain phosphatides, carbohydrates, protein, fatty acids and toxic
compounds (Pesticides etc.) Therefore, refining operation, are carried out to remove these materials
as far as possible without affecting main constituents, vitamins and poly unsaturated fatty acids.
However, some vegetable oils viz. castor oil, olive oil, linseed oil or cold pressed sunflower oils
are not refined in order to preserve the main properties of these oils. The refining operations are
described briefly as below.
(i) Degumming operation to remove phosphatides from vegetable oils, containing high
phosphorous viz corn and sunflower oils, by water degumming to remove water hydrateable
phosphatides only. For NHP removal, special treatment is necessary. Phosphatides, gums and other
colloidal compounds promote hydrolysis of an oil. In hydration, degumming oil is treated with water
or steam, to form a sludge that is insoluble in oil. This is used to remove lecithin (1–3%) from
soyabeen oil containing 2.5% H2O by mixing with crude oil at 70–80°C with contact time 1–30
mins. The sludge is separated by contrifugation with addition of citric or phosphoric acid after
mixing with crude oil which increase hydration. The process varies depending on crude oil. Preliminary
crude treatment with bleaching agent or other adsorbent, in presence of citric or Phosphoric acid,
can be helpful. Some oils can be degummed by heating upto 240–280°C.
Refining by distillation is possible for low Phosphatide content. Special degumming technique
involves the addition of citric acid, followed by hydration at 70°C for several hours before
centrifugation. The flow sheet is given in Fig. 2.
(ii) Neutralisation Process
Vegetable oils contain 1–3% FFA. It is removed by treatment with caustic lye or distillation,
when soap solution is used. Other undesirable constituents viz oxidation products of fatty acids,
residual phosphatides, gums, phenol and toxins are also washed out.
Fig. 2 Vegetable oil refining process including rice bran oil

(iia) Alkali Neutralisation

Here conc. lye of (4–7 N) with crude oil is used in a reactor fitted with steam heating coil and
live steam heating upto 40–80°C with strong lye which settles at the bottom. For weak lye, it is
sprayed to crude oil at 90°C to neutralise FFA. After neutralisation and discharge from reactor, crude
oil is washed with dil. lye (0.5N) and then with water to reduce residual soap to 500 ppm. conc.
Incomplete removal of soap impairs colour of oil and efficiency of following refining steps. Soyabeen
oil is subjected to post treatment with Na2CO3 and silicate to remove residual traces of oxidised
glycerides and phosphatides. Soap stock can be used in boiler fuel or it can be converted to acid
oil, used as animal feed or other use. The quantity of acid oil (mix of fatty acid and neutral oil) is
variable.
(iii) The method to remove FFA is by distillation or neutralisation in vacuum after degumming
operation. The process is suitable for rape seed, soyabeen and sunflower oils with the technology
available for reducing phosphatide content. Distillation temperature required is 240–270°C when FFA
content become less than 0.1% .
Other process of esterification with a catalyst is also available.
A refining factor of 2 means that for each mass unit of free fatty acid (FFA) in crude oil, 2
mass units of acid free oil is produced. Process flow sheet for alkali neutralisation is given in Fig. 2.
(iii) Bleaching Operation
Degumming and alkali neutralisation do not generally give significant decolourisation. The
process involves the use of Fuller's earth (bleaching earth) and/or activated carbon (charcoal) for
dicolourisation of crude oil. The process of neutralisation and bleaching is usually carried out together
in a vessel fitted with agitator and vessels connected to vacuum. The crude oil is mixed with Fuller's
earth, stirred and filtered off. The bleaching should be done below 100°C through steam coil in
bleacher. Oil retention in bleach is 50% of bleacher or 100%(wt) of activated charcoal when used
in combination with F.R. (Fullers earth).
The operation is carried out under vacuum as bleach catalyzes the oxidation of oil. Process is
carried out in air free atmosphere including filtration, after discharge from bleacher. Some times
bleaching is carried out at 65°C and 100°C and preceded by addition of citric acid and Phosphoric
acid to chealate trace materials and to precipitate hydrated phosphatides. Soap solution and wash
water are introduced from bottom nozzle. Pigments to be removed are condenoids and chlorophyl;
but the bleaching operation also reduces phosphatides, soaps, trace metals and oxidation products
such is H2O2 and non volatile polar decomposition products.
Bleaching earth (mainly Al silicate) containing 5–10% moisture is first activated and dried.
Quantity of activated F.R will be 0.5–1% and activated charcoal (0.1–0.4%) is used when there are
difficulties in bleaching. The crude oil is dried in vacuum for 30 mins at 30 kpa and adsorbent earth
is added and stirred for about 1–30 minutes in vacuum at temperature of 80–90°C. The slurry is
pumped out to special filter presses or closed disc type centrifuge which have limited air access.
Bleaching and centrifugation is done batchwise. The colour in crude oil is mostly removed. The
process is given in flow sheet in Fig. 2.
(iv) Deodourisation Process
Here odours/flavours in crude oil are removed from bleached oil. The process uses steam
distillation under vacuum, when volatile compounds (odour and flavouring agents) are removed from
nonvolatile glycerides. The odour causing compounds in crude oil are primarily aldehydes and
ketones formed by auto oxidation during handling and storage and usually has threshold value of a
few ppm. Other volatile compounds (FFA, sterols or phenols) are also partially removed. The
flavouring compounds can also be formed by hydrolysis and thermal decomposition of crude oil.
Distillation under vacuum is necessary due to low partial pressure of removeable compounds. Steam
consumption rate is 5–10% wt. of crude oil for batch process and 1–5% wt. for continuous process.
Distillation temp. is 190–270°C at press. 0.13 to 0.78 Kpa (1–6 mm Hg). Steam required is 10–20m3/
kg of oil. The distillate removed is about 0.2% of oil and contains very little oil. Time required for
batch process is 4 hrs. The end point is determined organometrically. Steam used must be free from
oxygen and dry. To deactivate peroxide. Like trace metals, aq. citric acid soln. (2–5 mg c. acid/100
gm of oil) is often injected into the oil towards the end of decomposition. The sketch of batch
deodouriser is given in Fig. 2.
5. HYDROGENATION OF VEGETABLE OILS

The double bonds in fatty acid chain can be mostly or partially saturated by adding Hydrogen
in presence of nickel, platinum or palladium catalysts which increases the m.p and make the
vegetable oil solid at room temp.
6. PROPERTIES
Naturally occuring vegetable oils are liquid or semi solids consisting of glycerides. Liquid oils
are termed as liquids vegetable oils and solids as fats. Such oils also contain minor constituents of
free fatty acids, phospho liquids, sterols, hydrocarbons, pigments, waxes and vitamins. The veg. oils
usually contain 97% glycerides i.e. triesters of glycerol with fatty acids, upto 3% diglycerides and
upto 1% monoglycerides. They constitute 3,2 and 1 molecule of fatty acids respectively and triglycerides
contain at least 2 different fatty acids groups. Their physical, chemical, and biological properties are
determined by type of fatty acids group present and their distribution over triglycerides molecules.
M.P of oils increases with the increase in long chain saturated fatty acids or decreasing proportion
of unsaturated or short chain fatty acids.
Fatty acids are generally even numbered, straight chain aliphatic monocarboxylic acids with
chain length ranging from C4–C2. The no. and position of double bonds in unsaturated fatty acids
differ in configuration (i.e. cis or trans isomers)
The common fatty acids are butyric, lauric, palmitic, olive, stearic and linoleic, acid. Crude
fatty acids contain significant quantity of free fatty acids, FFA and most vegetable oils contain
palmitic, linoleic and olive oils.
Glycerides can be hydrolysed, as seen from refining processes, into fatty acids and glycerols.
CH2 OCOR CH2OH
| |
CHOCOR + 3 H 2O 
→ CHOH + 3 RCOOH
| |
CH2 OCOR CH2 OH
Unsaturated fatty acids in oils and fats can be polymerised by heating at 200–300°C forming
dimeric, oligomeric and Polymeric compounds.
Auto oxidation of veg oils develops rancidity, off flavour and reversal of flavours during
production and storage. Oil cake and spent bleaching earth (Fullers earth) can cause sponteneous
combustion.
High moisture content in oil seeds help uptake of oxygen resulting in degradation.
Rice Bran Oil

Saturated fatty Acids
C4 constituent = 0.58 gm/100gm fatty acids
C16 constituent = 13–18 gm/100gm fatty acids
C18 constituent = ~2 gm/100gm fatty acids
C20 constituent = ~0.5–1 fatty acids
C24 constituent = 0.5 fatty acids
Unsaturated fatty acids
C18 : 1 = ~44 gm/100gm fatty acids
C18 : 2 = 30–40 gm/100gm fatty acids
Density of R.B oil vary from 0.916 – 0.921 gm/cc
Sap value = 183–194 (mg KOH)
Iodine value = 92–109
N S M = 3.5 – 5.0 gm per 100 gm oil
MP = ~10°C
R. I (nD40) = 1.466 – 1.469
R. B oil is most suitable edible oil as its saturated fatty acid content is the minimum or so.
Chapter
48
FURFURAL
1. FURFURAL, C5H4O2, MOLECULAR WT 96.08 IS AN INDUSTRIALLY IMPORTANT
CHEMICAL AND A STARTING MATERIAL FOR FURANS.
1.1 Properties
It has excellent thermal stability in absence of oxygen upto 230°C and exposure for considerable
hrs is required to produce detectable changes in its physical properties with the exception of colour.
A fresh distilled furfural is a colourless liquid with a obnoxous aromatic smell similar to almonds.
It darkens in air due to presence of oxygen.
Furfural is an excellent solvent with low viscosity over a wide temperature range. It mixes with
a no. of organic solvents but is slightly miscible with saturated hydrocarbons which makes it a
selective solvent for a no. of industrial uses viz. in petroleum refinery. Chemical properties of furfural
is similar to aromatic aldehyde (Benzaldehyde) with other reactions due to dienic character of furan
ring. The vapour pressure of furfural is given below.
Temp °C 55 75 95 105 130 150
V.P, KPa 1.97 4.60 11.18 19.7 39.5 78.5
Furfural is reduced to furfuryl alcohol and can be oxidised to furoic acid and decarbonated to
furan, catalytic vapour phase oxidation of furfural yields malteic acid.
Flammability of furfural is similar to that of hexane or no. 1 fuel oil. It should not be mixed
with strong alkali or acid and stored near strong oxidising agents. Usually a few pentosan containing
materials (Xylan) are used to manufacture furfural.
1.2 Manufacturing Process
Raw materials – Rice husks, hulls of cotton seed husks, oats hulls and cereal grains. Other raw
materials are, wheat chaff, bagasee, corn cobs and deciduous and coniferous tree woods, sulfite
waste liquor and cellulose waste liquor.
Meterial % pentosan content Avg. Furfural Content,%
Cotton seed husks 23–28 18.6
Bagasse 25–27 17.4
Corn cobs 30–32 23.4
282
FURFURAL 283
Material % Pentosan content Avg. furfural Content, %

Oat husks 40 22.3
Corn stalks 24 –
Birch wood 25 –
(after tannin extraction)
Corn husks 30–33 –
Wheat chaffs 18 –
Pentosan is the main constituent in Xylan–a polysaccharide with β–1, 4– linked D–xylopyransone
units together with small amount of arabiran, a highly branched polysaccharide of 1,3 and 1,5 linked
α–D cerbinofurarone units. Xylan in cereal strawps and grains constitute 23–30% and about 15–25%
in deciduous tree wood and 5–15% in coniferous wood based on dry matter.
Process – The raw material, such as bagasse, is charged in a batch or continuous digestor with
addition of a strong mineral acid and H.P. steam is passed to raise temp of digestor. After operation,
temp. and press. of digestor is attained and the spent reaction material is withdrawn from digestor
and furfural water vapour from the top of the digestor is condensed in a condenser with cooling
water.
The condensed digestor vapour, containing furfural-water mixture is stripped with H.P. steam
stripper and the vapour from top of the stripper is condensed in a cooler and put in a decanter where
furfural containing 6% water, settles at bottom as being heavier than water and water forms the top
layer in decanter.
Liquid furfural is pumped to dehydrator (Rectification Column) to obtain pure furfural (98%
min.) which is tapped out from the bottom of dehydrator while top vapour of moisture with 8%
furfural, is condensed in a condenser and drained to decanter for recycle. Water from the top of
the decanter is periodically drained.
The cellulosic material in digestor undergoes partial degradation during digestion and remains
with lignin and ash in the residue, this is burnt in steam plant as a fuel support for the energy required
for furfural plant.
Reaction in digester:
Another form of reaction:

1.3 Handling, storage and Transportation of furfural in steel tanks, All steel tank trucks and steel
drums are used. Proper packing in valves should be used to make them leak proof because
furfural is an excellent solvent. The storage tanks/drums should be oxygen free. Colour change
of furfural is associated with acidity increase and polymer formation occurs when furfural is
stored for long time in presence of air
1.4 Uses
(i) Extractive distillation of C4 and C5 hydrocarbons for the production of synthetic rubber.
The use has come down due to butadiene availability from ethylene.
(ii) Furfural is selective solvent for separating saturated from unsaturated compounds in Petro
lubricating oils, gas oil and diesel oil.
(iii) It is a solvent for furfural alcohol resin for fibre glass reinforced plastic articles.
(iv) As a flame retardant in plastic articles.
(v) Extractive recovery of butadiene from cracked refinery gas.
(vi) As insecticide, herbicide, fungicide and enbalming fluid.

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(f.U NEW AGE INTERNATIONAL PUBLISHERS

26. Glass Fi bres for Insulation and Other Uses 187

Type Constituents, % by wt Remarks

Dicalcium Phosphate, P2O5 = 51% Fertiliser use

2. BY DANGER CRITERIA, THERE ARE FOUR TYPES OF FERTILISER

3. RAW MATERIALS FOR FERTILIZERS PRODUCTION

4. DETAIL PROCESS DESCRIPTION FOR AMMONIA PRODUCTION USING N.G.

A u xiliary Prim ary reform ation

L.P. boiler for steam

5. SYN. GAS (CO + H2) GENERATION BY NONCATALYTIC FUEL

S e rvice LSH S (Storage)

Lig. am m onia storage

Process MDEA (BASF) Low heat hot

Absorber outlet CO2 100 ppm 1000 ppm

H2/N2 ratio 2.95

Process Reformation and syn. –HTAS, HTAS

Plant capacity 600 MT/day 1000 MT/day

6. DEVELOPMENT IN AMMONIA PRODUCTION

Steam Net Work

Stamicarbon CO2 Stripping Process

where P = dissociation Pressure of liquid carbamate.

Snam Progetti U rea Stripper

8. TEC’S ACES (ADVANCED COST AND ENERGY SAVING) PROCESS

9. MONTEDISION’S IDR (ISOBARIC DOUBLE RECYCLE) PROCESS

10. STORAGE FOR FERTILISER

Kellog UHDE PDIL MHI-CHIYODA

(iii) Electric power 0.0215 0.0258 0.3586 0.03

where Q = Heat Flow, kcal/hr

1.6 Fouling Factor

2. TYPES OF HEAT TRANSFER EQUIPMENT

3. OVERALL HEAT TRANSFER

4. RADIANT HEAT TRANSFER

5. HEAT TRANSFER BY CONDUCTION

6. DATA REQD. FOR HEAT EXCHANGER CALCULATION : CRITERIA

8. SELECTED PROCESS EQUIPMENT DESIGN

H eat Exchanger w ith N ested Tubes G as to gas 10–50

G as to gas at high 100–400

(b) U tube Liquid to gas 20–70

G as at high pressure 200–1000

Fig. 1 Source : Borsig pocket book 3rd edn. 1970.

(c) H igh-pressure feed w ater preheater w ith

Water (inner) to 1500–2500

(d) D ouble-tube heat-exchanger G as to gas 10–50

Liquid to liquid 300–1200

G as at high pressure 200–500

N um ber of Tubes in Tubular H eat-Exchangers as a Function of

7 2.00 451 22.27

Fig. 3 Source : Borsig pocket book 3rd edn. 1970

Fig. 4 Source : Borsig pocket book 3rd edn. 1970

∆t 1 : La rge te m pe rature d iffe rence

Fo r a p ara llel or co u nte r flo w hea t-excha ng e r ∆t 1

2. PAPER SIZE STANDARDS

3. TEST PARAMETERS FOR PAPER

4. RAW MATERIALS FOR PAPER MANUFACTURING

Constituents Soft wood Hard wood Soft wood Hard wood

Bleaching steps in kraft pulp:

6.2 Chemical Recovery

7. MECHANICAL PULPING PROCESS