Chemical Process Technology:

Prof. Vimal Katiyar

Department of Chemical Engineering
Indian Institute of Technology Guwahati
 CL 402-Chemical Process Technology (3-0-0-6)
❑ Syllabus
Raw materials and principles of production of olefins and aromatics; typical intermediates from
olefins and aromatics such as ethylene glycol, ethyl benzene, phenol, cumene and DMT, dyes, and
pharmaceuticals; chemical processes based on raw materials sugar, starch, alcohol, cellulose,
paper, glyceride, oils, soaps, detergents; industrial processes for the production of inorganic heavy
chemicals such as acids, alkalis, salts, and fertilizers such as sulphuric, nitric, and phosphoric acids,
soda ash, ammonia, etc.

❑ Text:
1. C. L. Dryden, Outlines of Chemical Technology, Edited and Revised by M.Gopala Rao and S.
Marshall , 3rd Ed., Affiliated East West, New Delhi, 1997.

❑ References:
1. T. G. Austin and S. Shreve, Chemical Process Industries, 5th Ed., McGraw Hill, New Delhi, 1984.

2. R. E. Kirk, and D. F. Othmer, Encyclopaedia of Chemical Technology, 4th Ed., Interscience, New
York, 1991.

3. P. H. Groggins, Unit Processes in Organic Synthesis, 5th Ed., McGraw Hill, 1984.
Chemical Processing and the Work of the
Chemical Engineer:
 Chemical Technology

▪ Products include both consumer goods and intermediates for further chemical
and physical modifications

❑
▪ Basic chemistry involved
▪ Equipment in which the reactions take place
▪ Costs of the reaction materials, energy used in the process, and the effect of
efficiency
❑
Structure of the Chemical Industry
Evolution of the Chemical Industry
 Chemical Industry
❑

1746 Production of moderately concentrated sulfuric acid in the lead chamber

process on an industrial scale
1789 Process for converting sodium chloride to sodium carbonate was
developed
1831 Process for manufacturing concentrated sulfuric acid was developed

1850 The first oil refinery was built

1856 The first synthetic aniline dye, mauveine was developed from coal tar

1863 Better process for production of sodium carbonate

1864 Alkali Works Act passed by British government, the first example of
environmental regulation
1874 Development of the Deacon process for converting hydrochloric acid into
chlorine
~1900 Birth of chlor-alkali industry

1905 Development of the Haber process for producing ammonia

1907 Hydrogenation of fats

 Chemical Industry
❑

1909 Patent on Bakelite, the first commercially important plastic

1920 Large-scale industrial production of isopropanol from oil

1923 Development of a high-pressure process to produce methanol and

development of the Fischer–Tropsch process, a method for producing
synthetic liquid fuels from coal gas.
1926 Development of a process for commercial fluidized-bed coal gasification

1930 First commercial steam reforming plant development, first commercial

manufacture of polystyrene and discovery of nylon
1931 Development of ethene epoxidation process for the production of ethene
oxide
1933 Polyethene discovery

1934 First American car tire produced from a synthetic rubber, neoprene

1936 Development of a method of industrial scale catalytic cracking of oil

fractions
1938 Commercialization of the alkylation process for the production of high-
octane alkylate and discovery of the hydroformylation for the formation of
aldehydes from alkenes
 Chemical Industry
❑

1939 Start of large-scale low-density polyethene (LDPE) production and start of

large-scale poly(vinyl chloride) (PVC) production
1940 Development of catalytic reforming to produce higher octane gasoline

1953 Introduction of the Ziegler catalyst for the production of high-density

polyethene (HDPE).
1954 Introduction of chromium-based catalysts for the production of HDPE

1955 Start of large-scale production of poly(ethene terephthalate) (PET)

1957 First commercial production of isotactic polypropene

1960 Commercialization of two industrially important processes: ethene to

acetaldehyde (Wacker), and acrylonitrile production (SOHIO)
1963 Development of the first commercial methanol carbonylation process for
the production of acetic acid based on a homogeneous cobalt catalyst
1964 Many new catalysts and processes are developed, for example, a zeolite
catalyst for catalytic cracking and the metathesis of alkenes
1966 First low-pressure methanol synthesis commercialized
 Chemical Industry
❑

1970s Birth of environmental catalysis. Development of a catalytic converter for

Otto engine exhaust gas, Energy crises (1973 and 1979), Start of large-scale
bioethanol production
1980s The selective catalytic reduction (SCR) for controlling NOx emissions.
Development of a process for the production of linear low-density
polyethene (LLDPE)
1990s Discovery of carbon nanotubes. Improved NOx abatement in exhaust gases
by NOxtrap
2000s Introduction of soot abatement for diesel engines. Ultra-efficient
production of bulk chemicals. Green chemistry and sustainability, including
biomass conversion, become hot topics. New paradigms and concepts,
Product Technology, Process Intensification
 Chemical Industry
❑
Petrochemical Industry
Market of the Chemical Industry
 Principal Chemical Conversions
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 Energy Consumption
❑
 Alternative of Fossil Fuels

Energy Flow Remarks Years reserve

TW EJ/a (R/P)
Radiation reaching earth 125 000 4 000 000 1 kW/m2 sustainable

Natural photosynthesis 130 4000 sustainable

Energy consumption (2005) 14 440 mainly cooking,
heating
Biomass 1.5 50 sustainable
Coal 4.4 140 190
Oil 5.2 170 42
Natural gas 3.6 110 63
Energy consumption (2050 49 1550 3.5 times that of 2005
estimate)
 Alternative of Fossil Fuels
❑

Oils and fats

Sugars

Lignocellulosic biomass
 Chemical Engineering Functional Areas

 Product engineering
 Maintenance
 Quality Control
 Other
 Role of Process Engineer

❑
 Process Economics

An economic flowchart has to

be prepared based on:
▪ Financial sources
▪ Cost of finished product
▪ Market demand and sales
▪ Fixed and movable assets
▪ Operational cost
▪ Labor
▪ Cash outflow (tax, dividend etc.)
 Chemical Process Selection, Design and Operation

▪ Mass & Energy Balance

▪ Thermo chemistry
▪ Unit Operations
▪ Plant Equipment
▪ Ancillary Equipment
▪ Process Plant Diagram
▪ Instrumentation & Control
▪ Economics
▪ Safety
❑
 Chemical Process Selection, Design and Operation

This involves the kinetics of the reaction - whether it's first order or second

order; based on the chemical reaction engineering considerations, the design of the

reactor must provide sufficient residence time for the required degree of reaction,

and therefore, maximum conversion to product.

The reaction rate of homogeneous reactions may be controlled by the rate of

diffusion of reactants rather than by the chemical kinetics of Langmuir

isotherms and Freundlich isotherms.

 Chemical Process Selection, Design and Operation

These describe whether the reaction is exothermic or endothermic. In

Exothermic, heat is released to the environment, and in Endothermic, heat is

absorbed by the reactants. The value of heat of reaction is necessary to

operate the chemical reactor.

This involves the control and confinement of any hazardous reactants and

products as well as the control of reaction and process conditions.

 Utilities
Water Conditioning
 Water Conditioning

❑
▪ Quantity

▪ Quality

▪ Reuse

▪ Pollution

❑
▪ Carbonate (temporary)
❖ Caused by bicarbonates of calcium and magnesium
❖ Can be reduced by heating
▪ Noncarbonate (permanent)
❖ Caused by sulfates and chlorides of calcium and magnesium
❖ Requires chemical agents for reduction
❑
 Methods

❑
▪ Softening

Process to remove or reduce hardness

▪ Purification

Process to remove organic matter and microorganisms from water

❑
▪ Ion exchange
▪ Lime-Soda processes
▪ Phosphate conditioning
▪ Silica removal
▪ Deaeration
▪ Demineralization and desalting
❑
 Ion Exchange

❑
▪ Zeolites

▪ Organic ion exchangers

▪ Sulfonated organic ion exchangers

❑
▪ Softening
Ca/ Mg((HCO3)2 / SO4/ Cl2) + 2NaR (Ca/ Mg)R2 + Na2((HCO3)2/ SO4/ Cl2)
(soluble) (insoluble) (insoluble) (soluble)
R – cation exchange radical
▪ Regeneration
(Ca/ Mg)R2 + 2NaCl 2NaR + (Ca/ Mg)Cl2
❖ Polystyrene divinylbenzene (SDVB) sulfonated synthetic resins are used for the
application (pH 6-8 for regeneration)
❖ It has high temperature stability (up to 150°C) and pH stability (pH 0 to 14)
 Ion Exchange

❑
 Ion Exchange

▪ Softening

Ca/ Mg/ Na2(HCO3)2 + 2HR (Ca/ Mg/ Na2)R2 + 2H2O + CO2

(soluble) (insoluble) (insoluble) (soluble)

Ca/ Mg/ Na2(HCO3)2 + 2HR (Ca/ Mg/ Na2)R2 + 2H2(SO4/ Cl2)

(soluble) (insoluble) (insoluble) (soluble)

▪ Regeneration

(Ca/ Mg/ Na2)R2 + H2SO4 2HR + (Ca/ Mg/ Na2)SO4

(insoluble) (soluble) (insoluble) (soluble)

❖ It can be employed to remove all cations
❖ Acidic water after regeneration is not desirable and either neutralized or
blended with sodium Zeolite treated water
 Ion Exchange

▪ Softening

H2SO4 + 2R4NOH (R4N)2SO4 + 2H2O

(soluble) (insoluble) (insoluble) (soluble)

R4N- anion exchanger radical
▪ Regeneration

(R4N)2SO4 + 2NaOH 2R4NOH + Na2SO4

(insoluble) (soluble) (insoluble) (soluble)

❖ Two types of anion exchangers highly basic or weekly basic are used
❖ Both can be used to remove strongly ionized acids
❖ Only highly basic anion exchangers can remove weakly ionized acids
❖ Highly basic anion exchangers are regenerated by caustic soda, while weakly
ones are regenerated by caustic soda, soda ash, or ammonium hydroxide
 Lime-Soda Process

Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O

Mg(HCO3)2 + Ca(OH)2 MgCO3 + CaCO3 + 2H2O

MgCO3 + Ca(OH)2 Mg(OH)2 + CaCO3

MgCl2 + Ca(OH)2 Mg(OH)2 + CaCl2

CaCl2 + Na2CO3 CaCO3 + 2NaCl

CaSO4 + Na2CO3 CaCO3 + Na2SO4

MgSO4 + Na2CO3 + Ca(OH)2 Mg(OH)2 + CaCO3 + Na2SO4

▪ Cold-lime-soda and hot-lime-soda are the two processes available
▪ Cold-lime-soda process is employed for partial softening and ordinarily uses
▪ Disposal of high amount of sludge formed in the process is expensive and
 Lime-Soda Process

Output: 20-25 ppm

 Lime-Soda Process

❑
▪ Hot-lime-soda process is mostly employed for conditioning of boiler feed water
▪ The process is carried out in the following sequence:
❖ Analysis of the raw water
❖ Heating of the raw water by exhaust steam
❖ Mixing and proportionating of the lime and soda ash in conformance with the raw
water analysis
❖ Pumping of the lime slurry and soda
❖ Reaction of the lime and soda is facilitated by mixing with or without previous
heating
❖ Coagulation or release of the supersaturation by slow agitation or contact with
seeds (fresh surface) by sludge recirculation
❖ Settling or removal of the precipitate with or without filtration
❖ Pumping away the softened water
❖ Periodic washing way of the sludge from the tank bottom
 Other Conditioning Methods

▪ Used in conjunction with one of the previous method

▪ Used for internal conditioning of the boiler water as well as conditioning of

cooling and process water

▪ Orthophosphates and complex phosphates are used in steam boilers to

precipitate the amount of calcium present

▪ Complex phosphate sodium hexametaphosphate is advantageous for boiler

systems which tends to become alkaline, as it can revert back to an acid

orthophosphate

▪ Sodium hexametaphosphate helps in iron removal and corrosion prevention as

well
 Other Conditioning Methods

▪ Silica is removed by dolomitic lime or activated magnesia in the softener

▪ Ferric coagulates are also used for preliminary coagulation and settling

▪ Demineralization is used to have only trace amount of silica

❑
▪ Deaeration is done to condition water for industrial boiler
▪ Presence of oxygen increases the corrosion rate by various reactions depending
upon conditions
▪ Corrosion of iron due to formation of OH‾ by O2 and H2O reaction is well known
▪ Removal of the dissolved oxygen can inhibit it
▪ Deaeration is done by spraying or cascading the water down over a series of
trays contained in a pressurized vessel
▪ Remaining trace amount of oxygen is removed by oxygen scavengers such as
sodium sulfite hydrazine hydrate
 Demineralization and Desalting

▪ Demineralization is employed to various processes including conditioning of

water for high pressure reactors

▪ Ion exchange system for demineralization is chosen based on:

❖ Volume and composition of the raw water

❖ The effluent quality requirement

❖ Comparative capital and operating cost

▪ Demineralization system with silica removal will consists of:

▪ Hydrogen cation exchange unit

▪ Strongly basic anion exchanger unit

▪ Degasifier between the units

Demineralization and Desalting
 Demineralization and Desalting

▪ Desalting or desalinization is applied to partial or complete demineralization of

highly saline waters

▪ Methods used for desalting are:

❖ Electrodialysis

❖ Reverse osmosis

❖ Multistage flash evaporation

❖ Vertical tube evaporation

❖ Vapor compression

❖ Vacuum freeze vapor compression

▪ Desalting by reverse osmosis is 20-30% less costlier than thermal desalting

units
 Demineralization and Desalting

▪ Electrodialysis utilizes ion exchange membranes in electric field, which under

electric field provides less desalinated water in one compartment

▪ Reverse osmosis uses the pressure above osmotic pressure to force pure water

through a semipermeable membrane from concentrated brine solution

▪ Cellulose acetate or polyamide is used for membrane in reverse osmosis

 Purification

▪ Coagulation and filtration through sand or hard coal

▪ Oxidation by aeration

▪ Treatment with chlorine

 Purification

▪ Purification is done in sequence to softening of the water

▪ Aeration is done to remove iron, odor and taste

▪ The aerated water is partly softened by lime and the precipitate coagulated and

filtered

▪ Chlorine is added to destroy the pathogenic microorganisms

▪ Activated carbon is employed to remove odors and to improve the flavor

 Water in Petroleum Refinery

▪ Cooling (91% of the water in refinery is required for cooling)

▪ Boiler feed

▪ Processing

▪ Sanitary services

▪ Fire protection

▪ Miscellaneous purposes

▪ Most of the part of cooling system does not require high quality water

▪ Mostly high quality demineralized water is used for high pressure boilers

▪ But complete treating and softening of all cooling water is profitable

 Water in Petroleum Refinery

❑
 Water in Petroleum Refinery

❑
Water in Petroleum Refinery
 Water in Petroleum Refinery

Hardness as CaCO3 50

Iron 0.5

Manganese 0.5

Iron plus manganese 0.5

Turbidity 50

Corrosiveness None

Slime formation None

 Water in Petroleum Refinery

Figures refer to frequency of use of various types of water treatment

 Water in Petroleum Refinery

❑
 Water in Petroleum Refinery

Figures refer to frequency of use of various types of water

 Water in Steam Power Plant

▪ Carryover to the turbine components

▪ Corrosion

▪ Scale formation/deposition in the boiler turbine systems

▪ To prevent the fast aging

▪ To achieve higher operational efficiency

▪ Better environmental conservation

 Water in Steam Power Plant

❑
 Water in Steam Power Plant

❑
 Water in Steam Power Plant

❑
 Water in Steam Power Plant
❑
 Water in Steam Power Plant

pH 8.5-9.3 (9.0)

Iron (μg/l) 2 or less (1 or less)

Dissolved oxygen (μg/l) 20-200 (50 ± 30)

Electrical conductivity (mS/m) 0.02 or less

( ): Target value