Petrochemical

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Introduction
Industrial Countries
The world petrochemical industry has changed drastically in the last twenty to
thirty years. The United States, Western Europe and Japan previously dominated
production of primary petrochemicals, not only to supply their own domestic
demand but also to export to other world markets. These areas accounted for over
80% of world primary petrochemical production prior to 1980. However, world-
scale construction of petrochemical facilities in other parts of the world has been on
the rise. Countries with vast reserves of crude oil and natural gas (e.g., Saudi
Arabia and Canada) have constructed plants to add value to their resources. Since
these countries generally have smaller domestic demand, a significant share of
petrochemical production is earmarked for the export market.
The need for synthetic rubber and synthetic chemicals for explosives during World
War II prompted the development of the highly specialized petrochemical industry
in America. After 1952 the state's share in the American petrochemical industry
increased dramatically, and during the 1960s played an increasingly diversified role
in all phases of the petrochemical industry: furnishing and processing oil and gas,
producing petrochemicals, and manufacturing commercial commodities. By 1965
200 petrochemical plants in Texas processed such basic petrochemicals as
ethylene, propylene, butadiene, benzene, isoprene, and xylenes, which are the
building blocks for innumerable chemical products spanning the range of the
plastic, rubber, and synthetic fiber industries.
The petrochemical industries in the United States, Western Europe and Japan have
experienced lower growth rates. In 2010, these three regions accounted for only
37% of world primary petrochemicals production.
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Petrochemicals
Petrochemicals in general are compounds and polymers derived directly
or indirectly from petroleum and used in the chemical market. Among the major
petrochemical products are plastics, synthetic fibers, syntheticrubber, detergents,
and nitrogen fertilizers. Many other important chemical industries such as paints,
adhesives, aerosols, insecticides, and pharmaceuticals may involve one or more
petrochemical products withintheir manufacturing steps.
The primary raw materials
In general, primary raw materials are naturally occurring substances that have not
been subjected to chemical changes after being recovered. Natural gas and crude
oils are the basic raw materials for the manufacture of petrochemicals for the
production of petrochemicals are natural gas and crude oil. However, other
carbonaceous substances such as coal, oil shale, and tar sand can be processed
(expensively) to produce these chemicals.
Coal, oil shale, and tar sand are complex carbonaceous raw material sand possible
future energy and chemical sources. However, they must undergo lengthy and
extensive processing before they yield fuels and chemicals similar to those produced
from crude oils (substitute natural gas (SNG) and synthetic crudes from coal, tar sand
and oil shale).
Secondary raw materials, or intermediates, are obtained from natural
gas and crude oils through different processing schemes. The intermediates may be
light hydrocarbon compounds such as methane and ethane, or heavier hydrocarbon
mixtures such as naphtha or gas oil. Both naphtha and gas oil are crude oil fractions
with different boiling ranges.
٢
Two petrochemical classes are olefins including ethylene and propylene, and
aromatics including benzene, toluene and xylene isomers. Oil refineries produce
olefins and aromatics by fluid catalytic cracking of petroleum fractions. Chemical
plants produce olefins by steam cracking of natural gas liquids like ethane and
propane. Aromatics are produced by catalytic reforming of naphtha. Olefins and
aromatics are the building blocks for a wide range of materials such as solvents,
detergents, and adhesives. Olefins are the basis for polymers and oligomers used in
plastics, resins, fibers, elastomers, lubricants, and gels.
Primary petrochemicals are divided into three groups depending on their chemical
structure:
• Olefins includes ethylene, propylene, and butadiene. Ethylene and propylene

are important sources of industrial chemicals and plastics products. Butadiene is
used in making synthetic rubber.
• Aromatics includes benzene, toluene, and xylenes. Benzene is a raw material
for dyes and synthetic detergents, and benzene and toluene for isocyanates MDI
and TDI used in making polyurethanes. Manufacturers use xylenes to produce
plastics and synthetic fibers.
• Synthesis gas is a mixture of carbon monoxide and hydrogen used to make
ammonia and methanol. Ammonia is used to make the fertilizer urea and
methanol is used as a solvent and chemical intermediate.
Factors affecting development and growth of petrochemical

industries:
1-Avaliability of oil and natural gas and development of refining technology and
industries.
2-Great development in production and purification of basic PCs.
٣
3-The characterization properties of PCs produced: Tensile corrosion resistance and
easy of production.
4-Cost of PCs produced equal or less than natural or classical materials.
5-Great demand on commodity product and limited availability of natural product

thus are replaced byPCs product.
Characterization petrochemical industries
1-Different processing stages from oil and NG to final product.
2-Its demand of high developed and complex technology and efficient stuff from
various levels.
3-High capital cost: cost of civil, processing are high on other hand this industry
characterizes by high profit especially final products.
4- High production capacity is considered to be economic due to technological

development in using equipment and also recovery of by-products.
5- By-product associated with basic PCs produced can be utilized in economics of

project: production of Ethylene from Naphtha :by-products are:Proplene and BD.
thus are replaced by PCs product.
Generation of petrochemical industry:
1st Generation PCs:From NG and Petroleum fraction.
Processes: Steam cracking for production of Olefins and Aromatics.
2nd Generation PCs:Intermediate :From Basic PCs .
Processes:Alkylation,Hydrogenation.
3rd Generation PCs,End product. Represent all the commodity used for different
purposes. These may be used alone or composites.
٤
Another feed stocks for PCs industries:
1-Nuclear energy. 2-Radinet

Radinet energy. 3-Electrowater energy
4-Thermal-underground
underground energy.
Ethylene
Application: To produce polymer-grade

polymer ethylene (99.95 vol%). Major byproducts
are propylene (chemical or polymer-grade),
polymer a butadiene-rich
rich C4 stream, C6 to C8
aromatics-rich pyrolysis gasoline and high-purity hydrogen
Description: Hydrocarbon feedstock is preheated and cracked in the presence of

steam in tubular SRT (short residence time) pyrolysis furnaces(1). This approach
features extremely high olefin yields, long run length and mechanical integrity. The
products exit the furnace
furnace at 1,500°F to1,600°F and are rapidly quenched in the
٥
transfer line exchangers (2) that generate super high-pressure (SHP) steam. The
latest generation furnace design is the SRT VI.
Furnace effluent, after quench, flows to the gasoline fractionators(3) where the
heavy oil fraction is removed from the gasoline and lighter fraction (liquids
cracking only). Further cooling of furnace effluents is accomplished by a direct
water quench in the quench tower (4). Raw gas from the quench tower is
compressed in a multistage centrifugal compressor (5) to greater than 500 psig. The
compressed gas is then dried (6) and chilled. Hydrogen is recovered in the chilling
train (7), which feeds the demethanizer (8). The demethanizer operates at about100
psia, providing increased energy efficiency. The bottoms from the demethanizer go
to the deethanizer (9). Acetylene in the deethanizer overhead is hydrogenated (10)
or recovered. The ethylene-ethane stream is fractionated (11) and polymer grade
ethylene is recovered. Ethane leaving the bottom of the ethylene fractionators is
recycled and cracked to extinction. The deethanizer bottoms and condensate
stripper bottoms from the charge compression system are depropanized (12).
Methylacetylene and propadiene are hydrogenated in the depropanizer using
CDHydro catalytic distillation hydrogenation technology. The depropanizer
bottoms is separated into mixed C4 and light gasoline streams (14). Polymer-grade
propylene is recovered in a propylene fractionator (13). A revised flow scheme
eliminates ~25% of the equipment from this conventional flow sheet. It uses CD
Hydrohydrogenation for the selective hydrogenation of C2 through C4 acetylenes
and dienes in a single tower; reduces the cracked-gas discharge pressure to 250
psig; uses a single refrigeration system to replace the three separate systems; and
applies metathesis to produce up to 1/3 of the propylene product catalytically rather
than by thermal cracking, thereby lowering energy consumption by ~15%.
Energy consumption: Energy consumptions are 3,300 kcal/kg of ethylene produced
for ethane cracking and 5,000 kcal/kg of ethylene for naphtha feed stocks. Energy
consumption can be as low as 4,000 kcal/kg of ethylene for naphtha feed stocks
٦
with gas turbine integration. As noted above, the new flow scheme reduces energy
consumption by 14%.
Commercial plants: Approximately 40% of the world’s ethylene plants use
Lummus’ ethylene technology. Many existing units have been significantly
expanded (above 150% of nameplate) using Lummus’ MCET(maximum capacity
expansion technology) approach.
First: Steam cracking process:

treatment of HCS with steam at high temp and low contact time and pressure.:
Mechanism:
1- Dehydrogenation of ethane:
CH3-CH3→CH2=CH2
Ethane Ethylene
CH3CH2CH3 → CH2=CH2+ CH4
Propane Ethylene
2-Dehydrogenation of propane:
CH3CH2CH3 → CH2=CHCH3+ H2
Furance design:
Furances:tubular furance:tube arranged either vertical or horizantal, and made of

S.S:which is alloy of nickel and chrom and cnotain burners mounted in the bottom
or on a side of these burners
NG,reduced crude or fuel oil burns to give heat.
٧
Operating conditions(OC):
Practical design of steaam cracking and operating conditions depends on feed.
If the raw material:Ethane-gas oil :then operating conditions are:
Temp:750-850 oC Resdance time(RT)=0.2-0.3 sec.
Steam:feed 0.2-1 Pressure:1-3 bar.
Effect of Operating conditions(OC):on steam cracking process:
1-RT:low:yield :high and formation of coke:low
In order to lower (RT)a- lower the reactor size(volume) b- reduce pressure c-

increase of temp.Ex.to lower( RT) from sec. to a part of sec.the temp.inside the
tubes must be increase from 750-900 oC :yield of ethylene will increaase from 20-
23% to 30-35% .
Ratio of steam:HCS:
Advantage of use of steam
1-Reduce the vapour pressure and RT oh HCS in the reaction zone which in term
increase %yield.
2-Reduce the partial pressure of aromatic HCS with high molecular weight which
limit the formation of coke on the internal tubes walls.
3-The reaction which takesplace between coke and steam to remove precepiation.
C + H2O →CO +H2
Disadvantages:
1-Reduce the unit capacity. 2-Recovery limited amount of steam.
3- The need of high energy to cool the product.
٨
Second: Cooling:
Effulent from steam cracking furance with temp.800oC contains a lot of active
unsaturated compounds ,thus cooling process(quenching)must carried out for the
following :
1-The gums and polymeric compounds which forms as result of side reaction must
be excluded.
2- Recovery of thermal energy as steam
Cooling stages:
Cooling is carried out in 2-3 stages according to feed as follows:
1-Quenching(rapid and immediate) and production of high pressure steam.
2- Primary fractionation:for product of thermal cracking in case of feed stock and

separation of fuel oil.
Pyrolysis gas
Pyrolysis o
400 C v at 200oC
Gas Gas
650-850oC 350oC
Pyrogas decante
200oC
Steam Pyrogasoline
Fule oil
Quench cooler Prefractionator Scrubber oil or water
Quenching:
Is carried out first in TLE(Transfer line exchanger)
٩
To atemp. of (375-500OC)by using hot water in the apper part of tublar furance and
production of high pressure steam which is used to operate the copressers in the
same comples.
Final cooling:
Cooling is carried out to about 400C as follows:
a-Gas feed: direct treatment in water quanch unit;where pyro gas leaves from the
top of washing tower while pyro gasoline leaves with washing water from the
bottom of the washing tower,pyro gasloine is separated,wash water is recycled after
cooling in heat exchangers.
b-Liquid feed:cooling is carried out first using direct wash with oil such as gas oil
then fractional distillation is carried out to for fuel oil separation from heavy
gasoline fraction.During direct washing products temp.decrease to 200-2200C then
products are introduced to primary disitation tower to separat fuel oil and washing
gas ,temp. of product is reduced to about 100-1100C,Final cooling is about 400C.
Third:Compression:
Pyro.gas contains some impurties with different concentrations differs according
to feed type and operating condions.Impurties are acids gases(H2S,CO2) ,acetylene
and water.
The compression of gas to 34 atm. occur in mulit stages (4-5).condense HCS are
removed from these stages.Acids gases removal is usually carried out during
copression using soda or amine wash unit, then gas is dried to prevent hydrided and
ice formation when the gas is cooled to low temp.during the distillation under
pressure.
١٠
To 2nd stage gases
gas at 200oC gases H2,CH4,C2H6

Compression Stages
+ wash oil C2H4,C3H8,C3H6,C4,C5,H2S
Cooling
Flash drum heating
Flash drum
pyrogasoline (liq.)
Fourth:Acid gases removal:
Puirty requirment in low olefins need to reduce the contain of H2S(1-2)ppm and
CO2(10-15)ppm.
Resonces for acid gas removal:
1-To avoid corrosion problems,and limit solid CO2 precepitation at low temp.
2- Prevent catalyst (pd) poisining which is used in acetylene hydrogenation.
Removal process ;
Removal is carried out by multi stages washing with caustic soda solution.Usually
two stages wahing reduce the amount of CO2 to(15-20)ppm while the amount is
further reduced to less than (5)
ppm when three or more stages are used.
The pyro gas is feed in the lower part of washing tower and run up ward in the
reverse direction to soda solution stream(counter current) .The soda solution is
supplied with different concentraions in two separated contact stages in side the
tower. The paritaly exhauted soda solution after the second washing stage is
recycle to the first stage ,then it run outside the tower as rabish.The conentration of
the recycle solution to the second stage is neutralised with new dilute solution of
soda.
١١
15 ppm
NaOH 300ppm water

٧
Pyrogas
100 ppm
Waste Waste Waste
Counter current scrubbing (washing)with dil.NaOH
Washing process :
Treated gas from the second stage is washed with water in a separated region in a
tower contain several trays for contact .The water is recycle with different speed to
obtained effective washing of gas from residual soda and impurities.
Five:Drying:
Pyro gas is saturated with water steam as aresult of its contact with water in
different stages of manufacturing .The HCS gases dissolved amount
of water steam differs according to temp. and pressure thus the drying of the gas is
nessasry for the following:prevent the solidification of water and hydride formation
during distillation at low temp.which result to blockage of pipes and equipment and
reduce the efficiency of separating units.
Drying process:
1-It is carried out by:Adsorption:using suitable solid material ;such as active
aluminum oxide,silica gel,molecular sieves.
١٢
2-Pratically;two towers at least are used in drying units ;one of them in adsorption
stage while the other in activation and cooling stage.
The content of water in gas is reduced to(1-2)ppm.
Anti freeze agent(e.g.methanol)is also added thus hydride formation and freezing
of water is avoided
When gas is subjected to low temp.in copression and distillatio units.
2- Some times gas is cooled by propylene refregerent after washing by soda

inorder to reduce condensation of water and reduce its percentage in gas.
Dry gas Dry gas
Wet air
Adsorption Heating Cooling
wet gas Dry air
Sixth:Acteylene removal:
Pyro. Gas contins acetylene which its compound separated with olefins with
equivalent carbon no. when distillation processes.Thus acetylene must be removed
inorder to get olefins and diolefins with high purity.
Acetylene compound are removed from pyro gas by:1- Selective hydrogenation.
2-Solvent extraction.
Selective hydrogenation :
Used in almost all low olefins production units.
١٣
Olefine
Acetylene H2
H2
Removal process;
Acetylene removal is carried out either:
1-Front end removal;in copression stage.

2-Tail end removal;in poduct separation stage.
Front end removal:Hydrogenation of pyro gas is carried out before product
separation i.e.during compression and in presence of excess of hydrogen
especially the gas contains amount of hydrogen.
Tail end removal: Hydrogenation of pyro gas is carried out after product
separation i.e. after directly after distillation processe and by using equivalent
amount of hydrogen.Most recent units work by tail end removal especially when
liquid feed is used.
Seventh:Product separation:
Pyro gas contains:LO(E,P,B)H2,DO(diolefins)and acetylene.
Separation process :
To separate E and other LO from pyro gas ;distillation under pressure at low
temp, using higher efficency towers thus products with high purity are obtained.
١٤
H2
Feed CH4 C2H4
De-hydroge-
gb De-methan- C2 + De-ethana- C2 C2Spliter
nation
ation tion
H2
C2H6
C3 + C3H6
De-propa-
H2 C3Spliter
noation C3
C4 + C3H8
C4
De-butana-
tion
C5 +
C1 C2 Acetylene ethylene C3 C4
H2 H2 Propylene
Feed H2
Compression
C2-C5 E+Ethylene Ethan

st
1 Demethanator
(CH4) C3-C5 C3
(Ethylene) E ‫و‬ (C5) (C4)
C4-C5
Deethanizer Deproanzer De-Butylene
١٥
Energy requirments:
Energy consumption:
1-Heating :vapourzing and cracking of raw material supplied to the furance about
50%
2-Energy used to operate compressers to compress the gas to 40 atm. About 28-
40%
3-Refrigeration energy in separation and purity units.
4- Thermal energy to produce medium pressure steam with feed.
5-Others :heating of recyle boiler,distillation towers, pumps,compressers operation
furance exhuasers.
Energy recovery:
1-Heat recovered from hot combustion gases emitted from thermal cracking
furance.
2-Heat from hot reaction poduct when they cooled in TLE to about 4000C and it
produced as steam under medium pressure.
3-Final cooling for reaction product either in primary distilation tower or in heat
exchanger and it produce as steam under low pressure or hot water.
١٦
Buytlenes and Butadienes:
Hydrocarbons with carbon no.4: C4 .Its include the followings:
Compound Formula Mwt. Density

1- n-butane CH3CH2CH2CH3 58.12 0.600
2- Isobutane CH3CH2CH3 58.12 0.603
CH3
3- Butylene-1 CH3CH2CH2=CH2 56.1 0.668
4- Butylene-2 cis CH3 CH3 56.1 0.635

CH = CH
5- Butylene-2 Trans CH3 56.1 0.635

CH = CH
CH3
6- Isobutylen CH2=CHCH3 56.1 0.611
CH3
7- 1,3-Butadiene CH2=CH-CH=CH2 54.1 ------
These chemical avilable as amixture with carbon no.-4.Also C4 fraction contains some
unsaturated comp. Such as acetylene also HCS with carbon no. (3,5) in low percentage.
Sources of butylene production:
1-By product in cracking unit of oil fractions.

2-Steam cracking unit in ethylene production.
3-Dehydrogenation processes and other synthsis processes.
Butylene consumption:
In 1985:Total Butylene consumption=28.09 MT
Linear Butylene =2/3 28.09 Iso=1/3 28.09 mt
١٧
Butylene Consumption for engine benzene.
BD consumption =8.3 mt in 2000 %growth=4.5% utilization of DO :in
production of :rubber,solvent and other compounds.
Conversion processes-Dehydrogenation
It is used for production of:
1-LO(low olefins)from paraffins in a method similar to the production of ethylene.
2-HO(higher olefins) from linear paraffins.
3-DO(diolefins)from paraffins and olefins.
Reactions:
C4H10→CH3CH2CH=CH2 +H2
n-butane 1-butene
C4H10→CH3CH=CH2CH3 +H2
n-butane 2-butene:cis
C4H10→CH3CH=CH2CH3 +H2
n-butane 2-butene:trans
C4H10→CH2=CH-CH= CH2 +H2
Reaction characterization:
1-Reversible 2-Endothermic 3-Occur in gas phase :each vol.gives two

vols.:i.e.increase in vol.
4-Takesplace in selective manner in presence of cata. And T=600-8000C.
Catalyst used:
Commercial catalyst :consists of 10-20%Cr2O3+80-90%Al2O3 .The catalyst loses

its activity in presence of steam.
١٨
Note: Dehydrogenation reaction of low paraffin's is a difficult reaction thus 1-
Sever conditions must be used 2-Catalyst must activated periodically.
Catalyst characterization:
1-Higher activity 2-Higher selectivity at higher temp.
BD Separation:
Classical method:
1-Absorption of BD in ammoniac copper acetate solution.
2-Separation:in multi-stages extraction-settling rig.
3-Displacement:BD is displaced from solution when temp.is raised and pressure is

lowered.
4-Purification:by distillation.
1,3 Butadiene (Extraction from mixed C4)
١٩
Application: To produce high-purity butadiene from a mixed C4 stream typically a
byproduct stream from an ethylene plant using liquid feeds (liquids cracker). The
BASF/ Lummus process uses n-methylpyrrolidone (NMP) as the solvent.
Description: The mixed C4 feed stream is fed into the first extractivedistillation
column (1), which produces an overhead butenes stream (raffinate-1) that is
essentially free of butadiene and acetylenes.
The bottoms stream from this column is stripped free of butenes inthe top half of
the rectifi er (2). A side stream containing butadiene anda small amount of
acetylenic compounds (vinyl and ethyl-acetylene) iswithdrawn from the rectifi er
and fed into the second extractive distillationcolumn (3). The C4 acetylenes, which
havehighersolubilities in NMP than 1,3-butadiene, are removed by the solvent in
the bottoms and returnedto the rectifi er. Acrude butadiene (BD) stream, from
theoverhead ofthe second extractive distillation column, is fed into the BD purifi
cationtrain. Both extractive distillation columns have a number of trays abovethe
solvent addition point to allow for the removal of solvent traces from the
overheads. The bottoms of the rectifi er, containing BD, C4 acetylenes andC5
hydrocarbons in NMP, is preheated solvent stripping column (4)). In this column,
solvent vapors are used asthe stripping medium to remove all light hydrocarbons
from NMP. The hot-stripped solvent from the bottom of the degasser passesthrough
the heat economizers (a train of heat exchangers) and is fed tothe extractive
distillation columns. The hydrocarbons leaving the top of the degasser are cooled in
acolumn by direct contact with solvent (NMP and water) and fed to the solvent
than 1,3-butadiene accumulate in the middle zone of the degasser and are drawnoff
as a side stream. This side stream, after dilution with raffi nate-1, isfed to a water
scrubber to remove a small amount of NMP from theexiting gases. The scrubbed
gases, containing the C4 acetylenes, are
purged to disposal. In the propyne column (5), the propyne (C3 acetylene) is
removedas overhead and sent to disposal. The bottoms are fed to the second
٢٠
distillation column (the 1,3-butadiene column (6)), which BD as overhead and a
small stream containing 1,2-butadiene and C5hydrocarbons as bottoms.
Yield: Typically, more than 98% of the 1,3-butadiene contained in the feed is
recovered as product.
Isobutylene Separation:
Extraction of Isobutylene from C4 with H2SO4:

H2SO4+IB C4 free from IB
IB
H 2O
Tower(1)
Tower(2)
Displacement
Concentration
Tower
C4
Acid
H2SO4 45%
65%H2SO4
Extract Steam
1-C4 is supplied to the bottom of tower (1).To the top of tower (1)H2SO4
(conc.65%) +(IB) is supplied from tower(2) to tower(1).
2-Extract from T(1) flow to displacement tower where there the conc. of acid is
lowered to 45% And heating by steam.
3-From the bottom of displacement tower H2SO4
٢١
(45%) flows to concentrated tower .in which the conc. of acid is raised to 65% then
it is resupply to Upper of tower 2.
Other methods:
1-Dilute H2SO4 is used. 2- HCl + metal's salt
3-Adsorption(molecular sieve):Union carbide
4-IB is converted to secondary &tertiary IB in presence of ion exchange with 96%

conv. Bayer Company.
Higher olefins:
Olefins can be classified as:
1- LO:2-4 carbon atom:E,P&B.
2-MO:5-8 carbon.
3-HO:9-18 carbon:Raw&basic materials in PC Industries: for production of

intermediate final
Products.HO Is classified in to:
1-Olefins withC12-18:Use in production of active
Material in detergent.
2-Olefins with C9-15 and particularly C11-12:is used in production of alkyl

benzene :i.e :alkylation of B+Alkyl.
Sources:
1-HO cannot be separated from MO.
٢٢
2-HO found in liquids of cracking process of petroleum products. Their separation
process is not economical.
Uses: 1-Detergent 2-Synthetic oils 3- Solvent 4-Intermediate.
Production of HO
1-Steam cracking of petroleum waxes.
2-Dehydrogenation of n-paraffin's.
3-Selective polymerization ( Oligomerization).
4-Metathesis.
Dehydrogenation of n-paraffin U.O.P:
LP:Linear paraffin –H2 → Linear olefin: LO
R-CH2CH2-R"↔R- CH=CH-R"
H2 Light gases
S
Raffinate S D2
D1
R A
LPD
F V
Feed
Extract
Desorbete Linear
LP recycle
Olefins
LP
٢٣
Liquids
F= Furnace LPD= distillation R= Reactor fix bed S= Storage
F= Flash tank separation vessel V= Valve A= Adsorption
D1= Dis5lla5on of Product S= Storage D2= Dis5lla5on
F:Furance.
R:Fixed bed reactor in presence of H2 under low pressure .Dehydrogenation of

paraffin occur at selectivity of 90%to olefins in presence of cata.e.g.oxide of
Mo,Cu,Pt on Al2O3.Side products are:DO,Ar and light products.
F:Flash tank separating vessel to separate of H2.
LDP:To separate of light HCS product: by
Extraction of LO in special adsorption unit.
S:Storage.
V:Distributer valve: control conversion flow for each current inside and outside
the tower.
A:Adsorption of product .D1:Distillation of product. S:Stoage D2:Distillaton.
Conditions of Dehydrogenation=420-5200C P=Low: To increase yield of LO and

decrease side products or :Diluents gas like H2 on N2 and sometimes steam are used
to decrease partial pressure and reduce side reactions and coke formation.
Selectivity of LO ≈90%.
Steam cracking of petroleum wax:

Paraffinic wax: raw material in steam cracking under mild conditions for
production LO and good yield of HO(linear type).
٢٤
Steam cracking conditions:
Pyro gas
Cyclone Cracking Furnace Quenching
Distillation Tower
Steam
Heating
M w
Light HCs
Water Separate
Recycle Feed Separator
Olefins
T=550-650OC RT=10 Sec. Conv.=25-35%
Raw materials: mixture of linear paraffin's with carbon no. 21-32.
Operating steps: similar to that of classical steam cracking HCS on production of

ethylene and other low olefins. Mix. of paraffin's wax (new and recycle)+steam
tubular furnace→cyclon to isolate unvaporized of wax .Products of cracking are
quenched (HE)and steam is produced, distillation is carried out
And separation of unconverted paraffin wax.
Yield olefins=90% C1-C4+H2 40% C5-C9 15% C10-C13

15%
C14-C20 30% HO Liquid 60% ὰ-olefin.

٢٥
This process is considered to be economic if LO-HO is utilized
Linear Alkyl Benzene Complex LAB

LAB: Chemical compounds contains two active parts. Part(1)concerning with
cleaning process.
Part(2)concerning with dissolving dirt's in water.
Cleaning process as follows: 1st part surrounds dirt by inactive layer. The 2nd
part pull the dirt and dissolve them in water and prevent its deposition on the
surface.
Example of LAB: Sodium salt of sulfonic acid.
Chemical equation of preparation:
Reaction of LO with Bz(Alkylation)→Alkylbenzene:
n-paraffin - H2→n-olefin: C-C-C-C-C- -H2→ C-C-C=C-C
n-olefin +benzene(from BTX complex)→→(Alkylation)→Alkylbenzene→
.silfonation→Alkylbenzene sulfonate→Neutralization(NaOH)→ABS
٢٦
٢٧
C8-C10 Off gas Iso cyclo
By-Product SO2 paraffins
Q1=Paraffin Unit Q2= Sulfur Q3= Molex unit

removal unit
Linear P C10-C13
Separation of low P Removal of S-SO4 Removal of Cyclo & branched
Bz P H2
LAB
Q5=Alkyla4on Q4=dehydrogen-
Q6=LAB LAB
unit
n-0 ation unit
separation
HAB Bz combine with LO Removal of H2 from Lp
Main units in LAB complex:

1-Paraﬃn unit 2-Alkyla5on unit 3-Aromatics unit
Paraffin unit:
Q1:Paraffin unit Q2:Sulfur removal Q3:Molex unit.
Alkylation unit:
Q4:Dehydrogenation unit Q5:Alkylation Q6:LAB separation.
Aromatics:
Compounds with C6-C8 like benzene, toluene ,and xylene(O.M.&P)Known as
BTX.
٢٨
Raw material for basic for PCs.
Uses: Plastic,rubber,fiber,resin adhesive, ,coating, detergents and plasticizer
World production of BTX:
The BTX aromatics are very important petrochemical materials. Global

consumption of benzene, estimated at more than 40,000,000 tons in 2010, showed
an unprecedented growth of more than 3,000,000 tons from the level seen in 2009.
Likewise, the para-xylene consumption showed unprecedented growth in 2010,
growing by 2,800,000 tons, a full ten percent growth from 2009.
Production of BTX Hydrocarbons
1-catalytic reforming of naphtha in petroleum refinery.
Catalytic reforming usually utilizes a feedstock naphtha that contains non-

aromatic hydrocarbons with 6 to 11 or 12 carbon atomsand typically produces
a reformate product containing C6 to C8 aromatics (benzene, toluene, xylenes) as
well as paraffins and heavier aromatics containing 9 to 11 or 12 carbon atoms.
٢٩
2- steam cracking of hydrocarbons which typically produces a cracked
naphtha product commonly referred to as pyrolysis gasoline, pyrolysis
gas or pygas. The pyrolysis gasoline typically consists of C6 to C8 aromatics,
heavier aromatics containing 9 to 11 or 12 carbon atoms, and non-aromatic cyclic
hydrocarbons (naphthenes) containing 6 or more carbon atoms.
Aromatics separation
1-Solvent extraction:
The BTX aromatics can be extracted from catalytic reformate or from pyrolysis
gasoline by many different methods. Most of those methods, but not all, involve the
use of a solvent either for liquid-liquid extraction.
Raffinate Aromatic
Non aromatic
Extraction Tower
Stripping Tower
Feed
Solvent
Solvent
Liquid–liquid extraction, also known as solvent extraction and partitioning, is a
method used to extract of a substance from one liquid phase into another liquid
phase. Liquid–liquid extraction is a basic technique in chemical laboratories, where
it is performed using a separatory funnel.
٣٠
Solvent extraction can also refer to the separation of a substance from a mixture
by preferentially dissolving that substance in a suitable solvent. In that case, a
soluble compound is separated from an insoluble compound or a complex matrix.
Solvent: from the top of extractor.
Feed: middle of the extractor, countercurrent to solvent. Solvent dissolve Ar. Form
a heavy phase :bottom while non-aromatic :Raffinate :top.
Properties of solvent:
1-Density higher than feed.
2-Higher boiling point than aromatics.
3-Hidher dissolving properties.
4-Higher thermal stability.
5-Does not cause corrosion.
Example :DEG,NMP,DMSO.
2- Extractive distillation. Many different solvents are suitable,

including sulfolane (C4H8O2S), furfural (C5H4O2), tetraethylene
glycol (C8H18O5), dimethylsulfoxide (C2H6OS),
and N-methyl-2- pyrrolidone (C5H9NO).
Below is a schematic flow diagram of one method, involving extractive distillation,

for extraction of the BTX aromatics from a catalytic reformate:
٣١
Schematic flow diagram for the extraction of BTX aromatics from a catalytic
reformate.
Distillation occur in presence of solvent with:
1-high B.pt 2-Selective

Selective for aromatics comps. Solvent reduce the partial pressure
of aromatics more than non-aromatics
non aromatics .Thus the distillation will be easier because
٣٢
the difference in B.pt. Fraction boils 65-920C is separated and supply to Extractive
distillation tower with 102 tower at90 .tray. On-aromatics are isolated from the top
as Raffinate. BTX+solvent to the stripper then to isolate the solvent which is
recycle. Aromatics to the aromatics fractionation section. From which BTX where
separated.
3-Azeotropic distillation
Recycle Solvent non- A
T
Azotropic Distillation Tower
Extraction By H2O
Solvent Distillation
Toluene Distillation
MEK+H2O
Feed
Residue
Treatment with Acid
It a distillation which occur in presence of solvent formed with non-aromatics an
azotropic system at temp.lower than b.pt of aromatics in a mixture.
Separation process:
1-Feed :is supplied to the middle of azotropic distillation tower(ADT).
2-T flows from the bottom of ADT,treated with acid or bleach
٣٣
The clay then distillate to required purity.
3-From the top of ADT ,mixture of non-aromaics+solvent (MEK)
+H2O to extractive and distillation towers where the solvent is extracted ,wash and
concentrated and recycled.
Comprism between Extractive and Azotropic distillation;

Extractive Azotropic
System:Solvent+Aromatics:bottom of Solvent+non-aromatics:top (DT)

distillation tower(DT)
Feed:low aromatics content:less than Aromatics :higher than 40%
40%
Slvent:phenol+H2O,N-methyl Acetone+H2O for Bz
pyrolidine,Formal morpholine Methanol+H2O for T
MEK+H2O fot T
Fraction: need fraction with narrow Fraction: need fraction with narrow
range of b.pt range of b.pt
BTX Separation:
B: B.pt=80oC Mwt:78 T B.pt=110.6 oC Mwt=92
X B.pt=136-144oC Mwt=107 C8: X &EB
To separate BTX : Supper fraction is applied as follows:
٣٤
Super Fractionation
bz T Aromatic C8
1st Process
Bz T C8
Tower Tower Tower
BTX
2nd Process Bz Aromatic C8
C6-7 Bz C8
Tower T T
٣٥
Isomerization of C8:
C8:Aromatics Mwt=106
Isomers of C8:o-xylene,m-xylene,p-xylene and Ethylbenzene.
Source:1-Catlytic reforming of Naptha.
2-Cracking of liquid feed(thermo pyrogasoline).
Isomerization:
Process carried out in presence of selective catalyst and special conditions were
used to produce certain compound over the other.
Catalyst used in Isomerization:
1-Gas phase catalyst: a-compose of metal such as
Mo,W over Al2O3 or b- pt over Al2O3.
2-Liquid phase cata.
Compose of dry AlCl3 or HF on BF3.
Aromatics unit in LAB Complex:
non –A Off gas T,X B
Naphtha T
reformate 07 08 09
Aromatics
Salfunic unit THDA BTX

٣٦
• Salfunic unit: Separation of aromatics from non-aromatics
non aromatics by extraction with
sulfunic solvent.
• THDA:Thermal hydrogentation dealkylation
• Aim:Chang T,X to B thus more benzene is formed.
• Chemical Equation
quation for THDA:
+H2 +CH4
Toluene Benzene
+ 2
Toluene +2H2 2 +2CH4
09:BTX:Separation
Separation of B from T and X.
٣٧
Synthetic gas(syn gas): H2+CO
Importance:
1-Raw material and basic for production of a lot of
Materials such as methanol.
2-Used in process where H2 is required.
Syn gas production:
1940:from coal C + H2O →CO+H2
Coke steam
Now: from petroleum fraction or natural gas
HCs feed:1-NG 2-Pet.fraction
Syn.gas:CO+H2 IF H2 is required only CO →CO2
Source of H2:
1-Cata.reforming 80-85%
2-Cata. Cracking 60-80%
3-Dehydrogentation 90%
4-Electrolysis of water high purity 1m3 required 4940 Kw of electricity.
٣٨
Hydrogen production from HCs feed
Hydrogen by steam reforming
CO2
Steam
T=930 T= 380oC T=22oC
CH4 gas P=25-30atm
Steam reforming furnace
De
-S H2
1st 2nd
Methanation
conv
conv CO2
erter erter
Stri
n 50oC ppi
ng
CO2 Absorption
MEA
s-removal by Shift reaction

W.H.B
1- Adsorption CO+H2O CO2+H2
Production of H.P.
2- Cate Steam CO +3H2 CH4+ H2O
hydrogenation
3-HCS distillation
٣٩
•
Application: Production of hydrogen (H2) from hydrocarbon (HC) feed stocks by

steam reforming.
Feed stocks: Ranging from natural gas to heavy naphtha as well as potential
refinery off gases. Many recent refinery hydrogen plants have multiple feedstock
flexibility, either in terms of backup or alternative or mixed feed. Automatic
feedstock change-over
over has also successfully been applied by Technip in several
modern plants with multiple feed stock flexibility.
Description: The generic flow sheet consists of feed pre-treatment,
pre treatment, pre reforming
(optional), steam-HC
HC reforming, shift conversion and hydrogen purification by
pressure swing adsorption (PSA). However, it is often tailored to satisfy specific
requirements. Feed pre-treatment
pre treatment normally involves removal of sulfur, chlorine
andother catalyst poisons after preheating to 350 – 400°C. The treated
treat feed gas
mixed with process
ocess steam is reformed in a fired
fired reformer (with adiabatic pre-
pre
reformer upstream, if used) after necessary super-heating.
super heating. The net reforming
٤٠
reactions are strongly endothermic. Heat is supplied by combusting PSA purge
gas, supplemented by makeup fuel in multiple burners in a top-fired furnace.
Reforming severity is optimized for each specific case. Waste heat from reformed
gas is recovered through steam generation before the water-gas shift conversion.
Most of the carbon monoxide (CO) is further converted to hydrogen. Process
condensate resulting from heat recovery and cooling is separated and generally
reused in the steam system after necessary treatment. The entire steam generation
is usually on natural circulation, which adds to higher reliability. The gas flows to
the PSA unit that provides high-purity hydrogen product (up to < 1 ppm CO) at
neart inlet pressures. Typical specific energy consumption based on feed + fuel –
export steam ranges between 3 Gcal/KNm3 and 3.5 Gcal/KNm3 (330 – 370 Btu/
scf) LHV, depending upon the feedstock, plant capacity, optimization criteria and
steam export requirements. Recent advances include integration of hydrogen
recovery and generation and recuperative (post-) reforming, also for capacity
retrofits.
Commercial plants: Technip has been involved in over 240 hydrogen
plants worldwide.
Reactions:
1-CH4+H2O→CO+3H2
2-CO+H2O→CO2+H2 Shift reaction.
3-CO+3H2→CH4+H2O Methanation.
Operating conditions:
T=800-900OC P=25-30 atm. Cata.=Ni(SRF)
H2O/C high ratio
٤١
Partial oxidation
Partial oxidation (POX) is a type of chemical reaction. It occurs when
a substoichiometric fuel-air mixture is partially combusted in a reformer, creating a
hydrogen-rich syngas which can then be put to further use, for example in a fuel
cell.
PO:Advantages:
٤٢
1-Flexibility of use of HCs fuel,pet.fraction,crude oil with high sulfer content and
residue.
2-It is used when NG or light fractions is not aviliable or when its prices are high.
3- Dose need catalyst.
4-Need of oxygen unit to produce oxygen.
Reactions:
CH4+O2→CO2+H2O
CH4+CO2→2CO+2H2
CH4+H2O→CO+3H2
Basic steps:
1-Gasification:
a- process occur in reactor lined with fire bricks without cata.
b-reaction occur between primary heated feed with oxygen,steam and it is supplied
through burners.
c-T=1300-1500oC P=Higher than 10 atm.(40-90 atm.)
2-Cooling:Two types according to companies:
a-Quench system:Texco process .
b- W.H.B.:Shell process.
3- Removal of soot. 4-Conversion of CO to CO2 5-Removal of CO2,H2S.
6-Removal of inert gases like Ar,CO.
7-Compression of resultant gases(H2) or mixture(CO,H2)
٤٣
Comprism between Steam reforming(SR)and Parital oxidation(PO)
Properties SR PO
Feed More important when CH4 Used for heavy pet. Fraction
or NG as feed and residue
Cata. Need Cata. Does not need Cata
Economic More economic due to low Less economic due to high

investment cost, also no investment cost, and the
need to oxygen unit demand of oxygen unit.
٤٤
Petrochemical Engineering fourth class/Branch refinery and gas technology
1-Methanol CH3OH
+ ↔
Application: The One Synergy process is improved low-pressure
methanol process to produce methanol. The new method produces
methanol from natural or associated gas using two-stage steam reforming
followed by compression, synthesis and distillation. Capacities, ranging
from 5,000 to 7,000 mtpd, are practical in a single stream. Carbon dioxide
(CO2 ) can be used as a supplementary feedstock to adjust the
stoichiometric ratio of the synthesis gas.
Description: Gas feedstock is compressed (if required), desulfurized
(1) and sent to the optional saturator (2) where some process steam is
generated. The saturator is used where maximum water recovery is
important. Further process steam is added, and the mixture is preheated
and sent to the pre-reformer (3), using the Catalytic-Rich-Gas process.
١
Steam raised in the methanol converter is added, along with available

CO2 , and the partially reformed mixture is preheated and sent to the
reformer (4). High-grade heat in the reformed gas is recovered as high-
pressure steam (5), boiler feed water preheat, and for reboil heat in the
distillation system (6). The high-pressure steam is used to drive the main
compressors in the plant.
After final cooling, the synthesis gas is compressed (7) and sent to
the synthesis loop. The loop can operate at pressures between 70 to 100
bar. The converter design does impact the loop pressure, with radial-flow
designs enabling low loop pressure even at the largest plant size. Low
loop pressure reduces the total energy requirements for the process.
The synthesis loop comprises a circulator (8) and the converter
operates around 200°C to 270°C, depending on the converter type.
Reaction heat from the loop is recovered as steam, and is used directly as
process steam for the reformer.
A purge is taken from the synthesis loop to remove inerts
(nitrogen, methane), as well as surplus hydrogen associated with non-
stoichiometric operation. The purge is used as fuel for the reformer.
Crude methanol from the separator contains water, as well as traces of
ethanol and other compounds. These impurities are removed in a two-
column distillation system (6). The first column removes the light ends
such as ethers, esters, acetone and dissolved noncondensable gases. The
second column removes water, higher alcohols and similar organic heavy
ends.
Economics: Recent trends have been to build methanol plants in
regions offering low-cost gas (such as Chile, Trinidad and the Arabian
Gulf). In these regions, total economics favor low investment rather than
low-energy consumption. Recent plants have an energy efficiency of 7.2
٢
–7.8 Gcal/ton. A guideline figure to construct a 5,000-mtpd plant is

US$370 – 400 million.
Q:Explain why %methanol decrease with temp. increase?
2-Ethylene oxide CH2 CH2
= + . CH2 CH2
٣
Application: To produce ethylene oxide (EO) from the direct oxidation

of ethylene using the Dow Meteor process.
Description: The Meteor Process, a technology first commercialized
in1994, is a simpler, safer process for the production of EO, having lower
capital investment requirements and lower operating costs. In the Meteor
Process, a-ethylene and oxygen are mixed with methane-ballast recycle
gas and passed through a single-train, multi tubular catalytic reactor (1) to
selectively 0 process is a simpler, safer technology with lower facility
investment costs The special high-productivity Meteor EO catalyst
provides very high efficiencies while operating at high loadings.b- Heat
generated by the reaction is removed and recovered by the direct boiling
of water to generate steam on the shell side of the reactor. Heat is
recovered from the reactor outlet gas before it enters the EO absorber (2)
where EO is scrubbed from the gas by water. The EO-containing water
from the EO absorber is concentrated by stripping (3). The cycle gas
exiting the absorber is fed to the CO2 removal section (4,5) where CO2,
which is co-produced in the EO reactor, is removed via activated, hot
potassium carbonate treatment. The CO2 lean cycle gas is recycled by
compression back to the EO reactor. Most EO plants are integrated with
glycol production facilities. When producing glycols, the EO stream (3) is
suitable for feeding directly to a Meteor glycol process. When EO is the
desired final product, the EO stream (3) can be fed to a single purification
column to produce high-purity EO. This process is extremely flexible and
can provide the full range of product mix between glycols and purified
EO.
Economics: The process requires a lower capital investment and has
lower fixed costs due to process simplicity and the need for fewer
equipment items. Lower operating costs are also achieved through the
٤
high productivity Meteor EO catalyst, which has very high efficiencies at

very high loadings.
Commercial plants: Union Carbide was the first to commercialize the

direct oxidation process for EO in the 1930s. Since 1954, 18 Union
Carbide- designed plants have been started up or are under construction.
Three million tons of EO equivalents per year (approximately 20% of
total world capacity) are produced in Union Carbide-designed plants.
Advantages:
Plant with one reactor work with high selectivity with low conversion for
each cycle. Reactants used with high concentration which reduced the
capital cost.
Disadvantages:
1- The demand for additional units e.g. oxygen separation unit (high
purity).
2- The need of CO2removal from recycle gas.
3- N2 must be removed from recycle gas; additional units.
However oxidation by O2 is more economic when high capacity
production is used.
EO Uses:
1-In production of ethylene glycol(anti freeze agent).
2-Used as surfactant. 3-In production of polyester.
4-In manufacture of Hydraulic fluid.
Other old method utilized air for oxidation:
1-Two reactors and two absorber to complete oxidation of E to
produce EO. T=260-290OC, P=10-13 atm.
٥
Cata: Ag/Al2O3 + Promotor: Ba, K + Inhibitor AgCl ,NaI ,used as
sphere to reduce pressure drop.
3-Acetic acid CH3COOH
+ →
Application: To produce acetic acid using the process, ACETICA.
Methanol and carbon monoxide (CO) are reacted with the carbonylation
reaction using a heterogeneous Rh catalyst.
Description: Fresh methanol is split into two streams and is contacted
with reactor offgas in the high-pressure absorber (7) and light gases in the
low-pressure absorber (8). The methanol, exiting the absorbers, are
٦
recombined and mixed with the recycle liquid from the recycle surge
drum (6). This stream is charged to a unique bubble-column reactor (1).
Carbon monoxide is compressed and sparged into the reactor riser.
The reactor has no mechanical moving parts, and is free from
leakage/maintenance problems. The ACETICA Catalyst is an
immobilized Rh complex catalyst on solid support, which offers higher
activity and operates under less water conditions in the system due to
heterogeneous system, and therefore, the system has much less
corrosivity.
Reactor effluent liquid is withdrawn and flash-vaporized in the
Flasher (2). The vaporized crude acetic acid is sent to the dehydration
column (3) to remove water and any light gases. Dried acetic acid is
routed to the finishing column (4), where heavy byproducts are removed
in the bottom draw off. The finished acetic-acid product is treated to
remove trace iodide components at the iodide removal unit (5).
Vapor streams from the dehydration column overhead contacted
with methanol in the low-pressure absorber (8). Unconverted CO,
methane, other light byproducts exiting in the vapor outlets of the high-
and low-pressure absorbers and heavy byproducts from the finishing
column are sent to the incinerator with scrubber (9).
Feed and utility consumption:
Methanol, mt/mt 0.539
CO,mt/mt 0.517
Power (@CO Supply 0 K/G), kWh/mt 129
Water, cooling, m3/mt 137
Steam @100 psig, mt/mt 1.7
Commercial plant: One unit is under construction for a Chinese
client.
٧
4-Ethanolamines,MEA,DEA &TEA
⋱ + →
MEA (75%)
O
+ →( )
DEA (21%)
+ →( )
TEA(4%)
Application: To produce mono-(MEA), di-(DEA) and triethanolamines

(TEA) from ethylene oxide and ammonia.
Description: Ammonia solution, recycled amines and ethylene oxide
are fed continuously to a reaction system (1) that operates under mild
conditions and simultaneously produces MEA, DEA and TEA. Product
ratios can be varied to maximize MEA, DEA or TEA production. The
٨
correct selection of the NH3 / EO ratio and recycling of amines produces

the desired product mix. The reactor products are sent to a separation
system where ammonia (2) and water are separated and recycled to the
reaction system. Vacuum distillation (4,5,6,7) is used to produce pure
MEA, DEA and TEA. A saleable heavies tar byproduct is also produced.
Technical grade TEA (85 wt%) can also be produced if required.
Yields: Greater than 98% on raw materials.
Economics: Typical performance data per ton amines MEA/DEA/TEA
product ratio of 1⁄3 : 1⁄3 : 1⁄3
Ethylene oxide, t 0.82
Ammonia, t 0.19
Steam, t 5
Water, cooling , m3 300
Electricity, kWh 30
Commercial plants: One 20,000-mtpy original capacity facility.
Uses:
1-Gases softening. 2-Detergent production. 3-Corrosin stabilizers
4- Chlorinated HCs stabilizers :decrease its decomposition.
٩
5-Vinylchloride monomer VCM CH(Cl)=CH2
+ → catalyst FeCl! and C$ H& Br

)
+ + → − + catalyst Cu$ Cl$
Application: Adding a stripping column to existing polyvinyl chloride

(PVC) plants to remove vinyl chloride monomer (VCM) from PVC
slurry. The recovered VCM can be reused in the PVC process, without
any deterioration of PVC polymer quality.
Description: PVC slurry discharged from reactors contains significant
amounts of VCM ( >30,000 ppm) even after initial flashing. This process
effectively removes the remaining VCM so that the monomer is
recovered and reused. Recycling of raw materials drastically reduces
VCM emissions from the following dryer. There is no significant change
in PVC quality after stripping. Residual VCM level in the PVC product
can be lowered below 1 ppm, and, in some cases, below 0.1 ppm.
١٠
The PVC slurry, containing VCM, is continuously fed to the

stripping column (1). The slurry passes counter-currently to steam, which
is fed into the base of the column. The proprietary internals of the column
are specially designed to ensure intimate contact between the steam and
the PVC slurry and to ensure that no PVC particles remain inside the
column. All process operations, including grade change, are
automatically done in a completely closed system.
While steam stripping is widely used, this proprietary technology,
which involves sophisticated design and know-how of the column, offers
attractive benefits to existing PVC plant sites.
The process design is compact with a small area requirement and
low investment cost. The size of the column is 2.5 t / h to 30 t / h.
Economics:
Steam 130 kg/t of PVC
Commercial plants: Chisso has licensed the technology to many PVC
producers worldwide. More than 100 columns of the Chisso process are
under operation or construction, and total capacity exceeds 5 million tpy
of PVC.
١١
6-Ethylene glycol
+ →
O MEG
Application: To produce ethylene glycols (MEG, DEG, TEG) from

ethylene oxide (EO) using Dow’s Meteor process.
Description: In the Meteor Process, an EO/water mixture is preheated
and fed directly to an adiabatic reactor (1), which can operate with or
without a catalyst. An excess of water is provided to achieve high
selectivities to monoethylene glycol (MEG). Diethylene (DEG) and
triethylene (TEG) glycols are produced as coproducts. In a catalyzed
mode, higher selectivities to MEG can be obtained, thereby reducing
DEG production to one-half that produced in the uncatalyzed mode. The
١٢
reactor is specially designed to fully react all of the EO and to minimize

back-mixing, which promotes enhanced selectivity to MEG.
Excess water from the reactor effluent is efficiently removed in a
multi-effect evaporation system (2). The last-effect evaporator overhead
produces low-pressure steam, which is a good low-level energy source
for other chemical units or other parts of the EO/MEG process. The
concentrated water/glycols stream from the evaporation system is fed to
the water column (3) where the remaining water and light ends are
stripped from the crude glycols. The water-free crude glycol stream is fed
to the MEG refining column (3) where polyester-grade MEG, suitable for
polyester fiber and PET production, is recovered. DEG and TEG exiting
the base of the MEG refining column can be recovered as high-purity
products by subsequent fractionation.
Economics: The conversion of EO to glycols is essentially complete.
The reaction not only generates the desired MEG, but also produces DEG
and TEG that can be recovered as coproducts. The production of more
DEG and TEG may be desirable if the manufacturer has a specific use for
these products or if market conditions provide a good price for DEG and
TEG relative to MEG. A catalyzed process will produce less heavy
glycols. The ability to operate in catalyzed or uncatalyzed mode provides
flexibility to the manufacturer to meet changing market demands.
Commercial plants: Since 1954, 18 UCC-designed glycol plants have
been started up or are under construction.
Uses:
1-Polyester(fibers and films).
2-Anti freeze agent.
3-Gas drying.
4-Manufacturing of plastizers.
١٣
7-Acrylonitrile =
, − + + (-./) → = +
Application: A process to produce high-purity acrylonitrile and high-

purity hydrogen cyanide from propylene, ammonia and air. Recovery of
byproduct acetonitrile is optional.
Description: Propylene, ammonia, and air are fed to a fluidized bed
reactor to produce acrylonitrile (ACRN) using DuPont’s proprietary
catalyst system. Other useful products from the reaction are hydrogen
cyanide (HCN) and acetonitrile (ACE). The reaction is highly exothermic
and heat is recovered from the reactor by producing high-pressure steam.
The reactor effluent is quenched and neutralized with a sulfuric solution
to remove the excess ammonia.
The product gas from the quench is absorbed with water to recover
the ACRN, HCN, and ACE. The aqueous solution of ACRN, HCN, and
١٤
ACE is then fractionated and purified into high-quality products. The

products’ recovery and purification is a highly efficient and low-energy
consumption process.
This ACRN technology minimizes the amount of aqueous effluent,
a major consideration for all acrylonitrile producers. This ACRN
technology is based on a high-activity, high-throughput catalyst. The
propylene conversion is 99% with a selectivity of 85% to useful products
of ACRN, HCN, and ACE. The DuPont catalyst is a mechanically
superior catalyst, resulting in a low catalyst loss. DuPont has developed a
Catalyst Bed Management Program (CBMP) to maintain the properties of
the catalyst bed inside the reactor at optimal performance throughout the
operation. The catalyst properties, the CBMP and proprietary reactor
internals provide an optimal performance of the ACRN reactor, resulting
in high yields.
With over 30 years of operating experience, DuPont has developed
know-how to increase the onstream factor of the plant. This knowhow
includes the effective use of inhibitors to reduce the formation of cyanide
and nitrile polymers and effective application of an antifoulant system to
increase onstream time for equipment.
Commercial plants: DuPont Chemical Solution Enterprise,
Beaumont, Texas (200,000 mtpy).
Uses:For production of Acrylic fibers ,flexible plastic ,Rubber
And resins.
١٥
8-Methyl-Tetra-Butyl-Ether (MTBE) ( )
( !) = + →( )
Application: The Uhde (Edeleanu) MTBE process combines methanol

and isobutene to produce the high-octane oxygenate—methyl tertiary
butyl ether (MTBE).
Feeds: C4-cuts from steam cracker and FCC units with isobutene
contents range from 12% to 30%.
Products: MTBE and other tertiary alkyl ethers are primarily used in
gasoline blending as an octane enhancer to improve hydrocarbon
combustion efficiency.
Description: The technology features a two-stage reactor system of
which the first reactor is operated in the recycle mode. With this method,
a slight expansion of the catalyst bed is achieved which ensures very
١٦
uniform concentration profiles within the reactor and, most important,

avoids hot spot formation. Undesired side reactions, such as the formation
of dimethyl ether (DME), are minimized.
The reactor inlet temperature ranges from 45°C at start-of-run to
about 60°C at end-of-run conditions. One important factor of the two
stage system is that the catalyst may be replaced in each reactor
separately, without shutting down the MTBE unit.
The catalyst used in this process is a cation-exchange resin and is
available from several catalyst manufacturers. Isobutene conversions of
97% are typical for FCC feedstocks. Higher conversions are attainable
when processing steam-cracker C4 cuts that contain isobutene
concentrations of 25%.
MTBE is recovered as the bottoms product of the distillation unit.
The methanol-rich C4 distillate is sent to the methanol-recovery section.
Water is used to extract excess methanol and recycle it back to process.
The isobutene-depleted C4 stream may be sent to a raffinate stripper or to
a molsieve-based unit to remove other oxygenates such as DME, MTBE,
methanol and tert-butanol.
Very high isobutene conversion, in excess of 99%, can be achieved
through a debutanizer column with structured packings containing
additional catalyst. This reactive distillation technique is particularly
suited when the raffinate-stream from the MTBE unit will be used to
produce a high-purity butene-1 product.
For a C4 cut containing 22% isobutene, the isobutene conversion
may exceed 98% at a selectivity for MTBE of 99.5%.
Utility requirements, (C4 feed containing 21% isobutene; per metric
ton of MTBE):
Steam, LP, kg 900
Steam, MP, kg 100
١٧
Electricity, kWh 35
Water, cooling, m3 15
Commercial plants: The Uhde (Edeleanu) proprietary MTBE process
has been successfully applied in five refineries. The accumulated licensed
capacity exceeds 1 MMtpy.
Uses: Octane booster.
9-Ethylbenzene C6H5CH2CH3
0 0
CH2=CH2+C6H6 → C6H5CH2CH3
12
Application: Advanced technology to produce high-purity

ethylbenzene (EB) alkylating benzene with ethylene using patented
catalytic distillation (CD) technology. The CDTECH EB process uses a
specially formulated zeolite alkylation catalyst packaged in a proprietary
١٨
CD structure. The process is able to handle a wide range in ethylene feed

composition— from 10% to 100% ethylene.
Description: The CD alkylator stripper (1) operates as a distillation
column. Alkylation and distillation occur in the alkylator in the presence
of a zeolite catalyst packaged in patented structured packing. Unreacted
ethylene and benzene vapor from the alkylator top are condensed and fed
to the finishing reactor (2) where the remaining ethylene reacts over
zeolite catlayst pellets. The alkylator stripper bottoms is fractionated (4,
5) into EB product, polyethylbenzenes and flux oil. The
polyethylbenzenes are transalkylated with benzene over zeolite catalyst
pellets in the transalkylator (3) to produce additional EB. The ethylene
can be polymer grade or, with only minor differences in the process
scheme, dilute ethylene containing as little as 10 mol% ethylene as in
FCC offgas. Reactors are designed for 3 to 6 years of uninterrupted
runlength. The process does not produce any hazardous effluent. Low
operating temperatures allow using carbon steel for all equipment.
Yields and product quality: Both the alkylation and trans-alkylation
reactions are highly selective—producing few byproducts. The EB
product has high purity (99.9 wt% minimum) and is suitable for styrene-
unit feed. Xylene make is less than 10 ppm. The process has an overall
yield of 99.7%.
Economics: The EB process features consistent product yields,
highproduct purity, low-energy consumption, low investment cost and
easy, reliable operation.
Investment (500,000 tpy, ISBL Gulf Coast), US$: 17 million
Raw materials and utilities, based on one metric ton of EB:
Ethylene, kg 265
Benzene, kg 738
١٩
Electricity, kWh 20
Water, cooling m3 3
Steam, mtons (export) 1.3
Hot oil, 106 kcal 0.6
Commercial plants: Three commercial plants are in operation in
Argentina and Canada with capacities from 140,000 to 816,000 mtpy.
They process ethylene feedstocks with purities ranging from 75%
ethylene to polymer-grade ethylene. An 850,000-mtpy unit using dilute
ethylene is currrently under construction.
Uses:
0.5 consumption of B:in EB production: which is used in
production of styrene.
10-Styrene 3 =
3 ↔ 3 = +
٢٠
EB S
Application: To produce polymer-grade styrene monomer (SM) by
dehydrogenating ethylbenzene (EB) to form styrene using the
Lummus/UOP “Classic” styrene process for new plants and the
Lummus/UOP SMART process for revamps involving plant capacity
expansion.
Description: In the Classic SM process, EB is catalytically
dehydrogenated to styrene in the presence of steam. The vapor phase
reaction is carried out at high temperature under vacuum. The EB (fresh
and recycle) is combined with superheated steam, and the mixture is
dehydrogenated in a multistage reactor system (1). A heater reheats the
process gas between stages. Reactor effluents are cooled to recover waste
heat and condense the hydrocarbons and steam. Uncondensed offgas—
containing mostly hydrogen— is compressed and is used as fuel.
Condensed hydrocarbons from an oil/water separator (2) are sent to the
distillation section. Process condensate is stripped to remove dissolved
aromatics.
A fractionation train (3,4) separates high-purity styrene product,
unconverted EB, which is recycled, and the relatively minor byproduct
tar, which is used as fuel. Toluene is produced (5,6) as a minor byproduct
and benzene (6) is normally recycled to the upstream EB process.
Typical SM product purity ranges from 99.85% to 99.95%. The
process provides high-product yield due to a unique combination of
catalyst and operating conditions used in the reactors and the use of a
highly effective polymerization inhibitor in the fractionation columns.
The SMART SM process is the same as Classic SM except that
oxidative reheat technology is used between the dehydrogenation stages
of the multistage reactor system (1). Specially designed reactors are used
٢١
to achieve the oxidation and dehydrogenation reactions. In oxidative

reheat, oxygen is introduced to oxidize part of the hydrogen produced
over a proprietary catalyst to reheat the process gas and to remove the
equilibrium constraint for the dehydrogenation reaction. The process
achieves up to about 80% EB conversion per pass, eliminates the costly
interstage reheater, and reduces superheated steam requirements. For
existing SM producers, revamping to SMART SM may be the most cost-
effective route to increased capacity.
Economics: (Classic) 500,000 mtpy, ISBL, US Gulf Coast:
Investment, US$ million 78
Ethylbenzene, ton/ton SM 1.055
Utilities, US$/mton SM 29
Commercial plants: Currently, 36 operating plants incorporate the
Lummus / UOP Classic Styrene technology. Seven operating facilities
are using the SMART process technology. Many future units using the
SMART process are expected to be retrofits of conventional units, since
the technology is ideally suited for revamps.
٢٢
11-Phenol
3 ( ) + → 3 ( )
3 ( ) → 3 +( )
Phenol acetone
Application: The Sunoco/UOP phenol process produces high-quality
phenol and acetone by liquid-phase peroxidation of cumene.
Description: Key process steps:
Oxidation and concentration (1): Cumene is oxidized to cumene
hydroperoxide (CHP). A small amount of dimethylphenylcarbinol
(DMPC) is also formed, but low-pressure and low-temperature oxidation
results in very high selectivity of CHP. CHP is then concentrated and
unreacted cumene is recycled back to the oxidation section.
Decomposition and neutralization (2): CHP is decomposed to
phenol and acetone, accompanied by dehydration of DMPC to
٢٣
alphamethylstyrene (AMS), catalyzed by mineral acid. This unique

design achieves a very high selectivity to phenol, acetone and AMS
without using recycle acetone. The high total yields from oxidation and
decomposition combine to achieve 1.31 wt cumene/wt phenol without tar
cracking. Decomposed catalyst is
neutralized.
Phenol and acetone purification (3): Phenol and acetone are
separated and purified. A small amount of byproduct is rejected as heavy
residue.
AMS hydrogenation or AMS refining (4): AMS is hydrogenated
back to cumene and recycled to oxidation, or AMS is refined for sale.
Cumene peroxidation is the preferred route to phenol, accounting for
more than 90% of world production. The Sunoco/UOP Phenol process
features low feedstock consumption (1.31 wt cumene/wt phenol) without
tar cracking, avoiding the expense and impurities associated with tar
cracking. High phenol and acetone product qualities are achieved through
a combination of minimizing impurity formation and efficient
purification techniques. Optimized design results in low investment cost
along with low utility and chemicals consumption for low variable cost of
production. Design options for byproduct alphamethylstyrene (AMS)
allow producers to select the best alternative for their market:
hydrogenate AMS back to cumene, or refi ne AMS for sale. No acetone
recycle to the decomposition (cleavage) section, simplified neutralization,
and no tar cracking make the Sunoco/UOP Phenol process easier to
operate.
Commercial plants: The Sunoco/UOP Phenol process is currently
used in 11 plants worldwide having total phenol capacity of more than 1
٢٤
million mtpy. Four additional process units, with a total design capacity
of 600,000 mtpy, are in design and construction.
Uses: Raw materials or intermediate for production of:
1- Phenol-formaldehyde resins 2- Bisphenol(for production of epoxy)
3-Caprolactum(for production of Nylon6 monomer) 4-Adipic acid
(for production of Nylon 66 monomer) 5- Salicylic acid(Aspirin
production) 6-Phenol alkyl (Rubber chemical) or(production of
Detergent).
12-Cyclohexane
3 3 + ↔ 3 )
٢٥
Application: Produce high-purity cyclohexane by liquid-phase

catalytic hydrogenation of benzene.
Description: The main reactor (1) converts essentially all the feed
isothermally in the liquid phase at a thermodynamically-favorable low
temperature using a continuously-injected soluble catalyst. The catalyst’s
high activity allows use of low hydrogen partial pressure, which results in
fewer side reactions, e.g., isomerization or hydrocracking. The heat of
reaction vaporizes cyclohexane product and, using pumparound
circulation through an exchanger, also generates steam (2). With the heat
of reactionbeing immediately removed by vaporization, accurate
temperature control is assured. A vapor-phase fixed-bed finishing reactor
(3) completes the catalytic hydrogenation of any residual benzene. This
step reduces residual benzene in the cyclohexane product to very low
levels. Depending on the purity of the hydrogen make-up gas, the
stabilization section includes either an LP separator (4) or a small
stabilizer to remove the light ends.
A prime advantage of the liquid-phase process is its substantially
lower cost compared to vapor phase processes: investment is particularly
low because a single, inexpensive main reactor chamber is used
compared to multiple-bed or tubular reactors used in vapor phase
processes. Quench gas and unreacted benzene recycles are not necessary
and better heat recovery generates both the cyclohexane vapor for the
finishing step and a greater amount of steam. These advantages result in
lower investment and operating costs. Operational fl exibility and
reliability are excellent; changes in feedstock quality and flows are easily
handled. Should the catalyst be deactivated by feed quality upsets, fresh
catalyst can be injected without shutting down.
Yield: 1.075 kg of cyclohexane is produced from 1 kg of benzene.
٢٦
Economics: Basis: 200,000-tpy cyclohexane complex, ISBL 2005 Gulf

Coast location with PSA hydrogen is US$8 million. Catalyst cost is US$
1.2/metric ton of product.
Commercial plants: Thirty-three cyclohexane units have been licensed.
13-Terephthalic acid (EPTA) COOH(C6H5)COOH

[5]
CH3(C6H5)CH3 →COOH(C6H5)COOH
P-xylene TPA
Application: E PTA (Eastman polymer-grade terephthalic acid) is an

excellent raw material for engineering plastics and packaging materials,
bottles, other food containers including hot fill, as well as films. The
process is proven to be suitable for the production of all kinds of
polyester fibers and containers without limitation, at international first-
grade quality.
٢٧
Description: The general flow diagram to produce E PTA using

Eastman Chemical’s proprietary process comprises three different main
sections — crude terephthalic acid (CTA), polymer-grade terephthalic
acid (EPTA) and catalyst recovery.
Crude terephthalic acid (1,2,3): CTA is produced by the catalytic
oxidation of p-xylene with air in the liquid phase using acetic acid as a
solvent (1). The feed mix— p-xylene, solvent and catalyst— together
with compressed air is continuously fed to the reactor, which is a bubble-
column oxidizer. It operates at moderate temperature and offers an
extremely high yield. The oxidizer product is known as crude terephthalic
acid (CTA) due to the high level of impurities contained. Many impurities
are fairly soluble in the solvent. In the CTA separation step (2), impurities
can be effectively removed from the product by exchanging the reaction
liquor with lean solvent from the solvent recovery system. The reactor
overhead vapor, mainly reaction water, acetic acid and nitrogen is sent to
the solvent-recovery system (3), where water is separated from the
solvent by distillation. After recovering its energy, the offgas is sent to a
regenerative thermal oxidation unit for further cleaning.
Polymer-grade terephthalic acid (5,6): The crude acid is purified to
obtain EPTA in a post-oxidation step, at elevated temperature conditions.
The post oxidizers serve as reactors to increase conversion of the partially
oxidized compounds to terephthalic acid. The level of 4-carboxy
benzaldehyde (4-CBA) ptoluic acid (p-TA) the main impurities in
terephthalic acid is significantly lowered. In a final step (6), E PTA is
separated from the solvent and dried for further processing in the
polyester-production facilities.
Catalyst recovery (4): After exchanging the liquor in the CTA
separation, the suspended solids are separated and removed as CTA
residue, which can be burned in a fluidized-bed incinerator or, if
٢٨
desirable, used as land fill. The soluble impurities are removed from the
filtrate within the filtrate treatment section, and the dissolved catalyst is
recycled.
Economics: The advanced Eastman E PTA technology uses fewer
processing steps. In combination with the outstanding mild-oxidation
technology, this technology leads to considerable capital cost savings and
lower production cost than in other technologies.
Commercial plants: Commercial plants are operating in the US,
Europe and Asia Pacific.
The latest plant with a capacity of 660,000 tpy for Zhejiang
Hualian Sunshine Petro-Chemical Co. Ltd. in Shaoxing, China, is under
construction and will be started up in April 2005, increasing the
worldwide capacity to 2.1 million tpy.
٢٩
Petrochemical Engineering
ng fourth class/Branch refinery and gas technology
14- Cumene
C6H6 + CH3CH=CH2 → C6H5CH(CH3)2

Benzene propylene cumene
Application: To produce high quality

high-quality cumene
(isopropylbenzene) by alkylating benzene with propylene
(typically refinery or chemical grade) using liquid-phase
liquid phase Q-Max
Q
process based on zeolitic catalyst technology.
Description: Benzene is alkylated to cumene over a zeolite
catalyst in a fixed-bed,
bed, liquid-phase
liquid phase reactor. Fresh benzene is
combined with recycle benzene and fed to the alkylation reactor
(1). The benzene feed flows in series through the
the beds, while fresh
propylene feed is distributed equally between the beds. This
reaction is highly exothermic, and heat is removed by recycling a
٣٠
portion of reactor effluent to the reactor inlet and injecting cooled

reactor effluent between the beds. In the fractionation section,
propane that accompanies the propylene feedstock is recovered as
LPG product from the overhead of the depropanizer column (2),
unreacted benzene is recovered from the overhead of the benzene
column (4) and cumene product is taken as overhead from the
cumene column (5). Di-isopropylbenzene (DIPB) is recovered in
the overhead of the DIPB column (6) and recycled to the
transalkylation reactor (3) where it is transalkylated with benzene
over a second zeolite catalyst to produce additional cumene. A
small quantity of heavy byproduct is recovered from the bottom of
the DIPB column(6) and is typically blended to fuel oil. The
cumene product has a high purity (99.96 – 99.97 wt%), and
cumene yields of 99.7 wt% and higher are achieved. The zeolite
catalyst is noncorrosive and operates at mild conditions; thus,
carbon-steel construction is possible. Catalyst cycle lengths are
two years and longer. The catalyst is fully regenerable for an
ultimate catalyst life of six years and longer. Existing plants that
use SPA or AlCl3 catalyst can be revamped to gain the advantages
of Q-Max cumene technology while increasing plant capacity
Economics: Basis: ISBL US Gulf Coast
Investment, US$/tpy 40 – 90
Raw materials & utilities, per metric ton of cumene
Propylene, tons 0.35
Benzene, tons 0.66
Electricity, kW 12
Steam, tons (import) 0.7
Water, cooling, m3 3
The Q-Max design is typically tailored to provide optimal utility
advantage for the plant site, such as minimizing heat input for standalone
operation or recovering heat as steam for usage in a nearby phenol plant.
٣١
Petrochemical Engineering
ng fourth class/Branch refinery and gas technology
15- Aniline C6H5NH2
7
C6H5 + HNO3 →→C6H5NH2
Application: A process for the production of high-quality

high quality aniline from
benzene and nitric acid.
Description: Aniline is produced by the nitration of benzene with nitric
acid to mononitrobenzene (MNB) which is subsequently hydrogenated to
aniline. In the DuPont/KBR process, benzene is nitrated with mixed acid
(nitric and sulfuric) at high efficiency to produce mon
mono
nitrobenzene(MNB) in the unique dehydrating nitration (DHN) system.
٣٢
The DHN system uses an inert gas to remove the water of nitration from
the reaction mixture, thus eliminating the energy-intensive and high-cost
sulfuric acid concentration system.
As the inert gas passes through the system, it becomes humidified,
removing the water of reaction from the reaction mixture. Most of the
energy required for the gas humidification comes from the heat of
nitration. The wet gas is condensed and the inert gas is recycled to the
nitrator. The condensed organic phase is recycled to the nitrator while the
aqueous phase is sent to effluent treatment. The reaction mixture is phase
separated and the sulfuric acid is returned to the nitrator. The crude MNB
is washed to remove residual acid and the impurities formed during the
nitration reaction. The product is then distilled and residual benzene is
recovered and recycled. Purified MNB is fed, together with hydrogen,
into a liquid phase plug-flow hydrogenation reactor that contains a
DuPont proprietary catalyst. The supported noble metal catalyst has a
high selectivity and the MNB conversion per pass is100%.
The reaction conditions are optimized to achieve essentially quantitative
yields and the reactor effluent is MNB-free. The reactor product is sent to
a dehydration column to remove the water of reaction followed by a
purification column to produce high-quality aniline product
Commercial plants: DuPont produces aniline using this technology
for the merchant market with a total production capacity of 160,000
tpyata plant located in Beaumont, Texas. In addition, DuPont’s aniline
technology is used in three commercial units and one new license was
awarded in 2004 with a total aniline capacity of 300,000 tpy.
٣٣
16-Nitrobenzene C6H5NO2
Raw materials:Benzene.nitric acid ,salphuric acid(cata.)

8$95:
C6H6 +HNO3 →C6H5NO2
&;<&&5=
Reaction at liquid phase,Yield:95-98%
17-Adipic acid COOH(CH2)4COOH
Raw materials: Butadiene,CO &H2O.
CH2=CH-CH=CH2 +2CO + 2H2O→HOOC(CH2)4COOH.

Buadiene Adipic acid
T=220OC P=75 atm. Cata:RdCl2/CH3I Yield"49%
Uses:for production of Nylon66 directly or through Hexamethyldiamine

HMDA
18-Benzoic acid C6H5COOH
Raw materials: Toluene ,oxygen
[5]
C6H5CH3 → C6H5COOH.
Toluene Benzoic acid
Oxidation of toluene in liquid phase
Cata.:Cobalt salt at T=165OC.

or Cobalt bromide at T=140-165 OC
P=27 atm
٣٤
Polymers
What is a polymer?
Very Large molecules structures chain-
chain-like in
nature.
Poly mer
many repeat unit
repeat repeat repeat
unit unit unit
H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH3
Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP)
Adapted from Fig. 14.2, Callister 7e.
4.1 Ancient Polymers
Originally natural
polymers were used:
Wood
Rubber
Cotton
Wool
Leather
Silk
Oldest known use:

Rubber balls used by Incas
Noah's pitch gum
Noah used pitch (a natural polymer) for thebased
ark resins
Genesis 6:14 "...and cover it inside and extracted from pine
outside with pitch." trees
2
Polymer Composition
Most polymers are hydrocarbons
– i.e. made up of H and C
Saturated hydrocarbons
Each carbon bonded to four other atoms
H H
H
C C
H H
H
CnH2n+
n+2
2
Polymer chemistry
In polyethylene (PE) synthesis, the monomer is ethylene
Turns out one can use many different monomers
Different functional groups/chemical composition – polymers have very
different properties!
H H F F
C * C *
* C n * C n
Monomers
H H F F
H H F
poly(ethylene) poly(tetrafluoroethylene) F
(PE) (PTFE, teflon) C C C C
H H H H
H H F F
C * C *
* C * C n H H H H
n
Cl H H C C C C
poly(vinylchloride) Cl H H
(PVC)
poly(styrene)
(PS)
Chemistry of Polymers
Free radical polymerization
H H H H
R + C C R C C initiation
H H H H
free radical monomer
(ethylene)
H H H H H H H H
R C C + C C R C C C C propagation
H H H H H H H H
dimer
Initiator:: example - benzoyl peroxide
Initiator
H H H
C O O C 2 C O =2R
H H H
Chemistry of Polymers
Adapted from Fig.
14.1, Callister 7e.
Note: polyethylene is just a long HC

- paraffin is short polyethylene
Bulk or Commodity Polymers
Range of Polymers
Traditionally, the industry has produced
two main types of synthetic polymer –
plastics and rubbers.
Plastics are (generally) rigid materials at
service temperatures
Rubbers are flexible, low modulus
materials which exhibit long-
long-range
elasticity.
Range of Polymers
Plastics are further subdivided into
thermoplastics and thermosets
Range of Polymers
Range of Polymers
Another way of classifying polymers is in
terms of their form or function
4.5 MOLECULAR WEIGHT
Molecular weight, M: Mass of a mole of chains.
low M
high M
Not all chains in a polymer are of the same length

i.e., there is a distribution of molecular weights
16
MOLECULAR WEIGHT
• Molecular weight, Mi: Mass of a mole of chains.
Lower M higher M
total wt of polymer
Mn =
total # of molecules
M n = Σx i M i
M w = Σw i M i
Mw is more sensitive to
higher molecular
weights Adapted from Fig. 14.4, Callister 7e.
Molecular Weight Calculation
Example: average mass of a class
Ni Mi xi wi
# of students mass (lb)
1 100 0.1 0.054
1 120 0.1 0.065 M n = ∑ xi M i
2 140 0.2 0.151
3 180 0.3 0.290
2 220 0.2 0.237
M w = ∑ wi M i
1 380 0.1 0.204 Ni
xi =
∑N
all i
i
Mn Mw
Ni ∗ M i
186 lb 216 lb wi =
∑N ∗M
all i
i i
Molecular weight
The properties of a polymer depend on its
length
synthesis yields polymer distribution of lengths
Define “average” molecular weight
Two approaches are typically taken

Number average molecular weight (Mn)
Weight--average molecular weight (Mw)
Weight
Molecular weight of polymers
1-No. average Mwt Mn
2-Weight average Mwt Mw
Mw=
Degree of Polymerization, n
n = number of repeat units per chain
H H H H H H H H H H H H
H C C (C C ) C C C C C C C C H ni = 6
Mn Mw
nn = ∑ xi ni = nw = ∑ w i ni =
m m
where m = average molecular weight of repeat unit

m = Σfi mi
Chain fraction mol. wt of repeat unit i
Molecular Weight Calculation
Example: average mass of a class
Ni Mi xi wi
# of students mass (lb)
1 100 0.1 0.054
1 120 0.1 0.065 M n = ∑ xi M i
2 140 0.2 0.151
3 180 0.3 0.290
2 220 0.2 0.237
M w = ∑ wi M i
1 380 0.1 0.204 Ni
xi =
∑N
all i
i
Mn Mw
Ni ∗ M i
186 lb 216 lb wi =
∑N ∗M
all i
i i
MOLECULAR WEIGHT DISTRIBUTION
Adapted from Fig. 4.4, Callister & Rethwisch 3e.
total wt of polymer
Mn =
total # of molecules
M n = ΣxiM i
M w = Σw iM i
Mi = mean (middle) molecular weight of size range i

xi = number fraction of chains in size range i
wi = weight fraction of chains in size range i
25
Example Problem 4.1
Given the following data determine the
Number average MW
Number average degree of polymerization
Weight average MW How to find Mn?
1. Calculate xiMi
Number average MW (Mn) 2. Sum these!
MW range (g/mol) Mean (M i)

Min Max xi (g/mol) x iM i (g/mol)
5000 10000 0.05 7500 375
10000 15000 0.16 12500 2000
15000 20000 0.22 17500 3850
20000 25000 0.27 22500 6075
25000 30000 0.20 27500 5500
30000 35000 0.08 32500 2600
35000 40000 0.02 37500 750
M n = 21,150 g / mol
Example Problem 4.1
Number average degree of polymerization
(MW of H2C=CHCl is 62
62..50 g/mol)
M n 21,150 g / mol How to find Mw?
nn = = = 338 1. Calculate wiMi
m 62.50 g / mol 2. Sum these!
Weight average molecular weight (Mw)
M w 23,200 g / mol
= = 1.10 M w = 23,200 g / mol
M n 21,150 g / mol
MW range (g/mol) Mean (M i)
Min Max wi (g/mol) wiM i (g/mol)
5000 10000 0.02 7500 150
10000 15000 0.10 12500 1250
15000 20000 0.18 17500 3150
20000 25000 0.29 22500 6525
25000 30000 0.26 27500 7150
30000 35000 0.13 32500 4225
35000 40000 0.02 37500 750
c04tf04a
Degree of Polymerization, DP
DP = average number of repeat units per chain
H C C (C C ) C C C C C C C C H DP = 6
Mn
DP =
m
where m = average molecular weight of repeat unit

for copolymers this is calculated as follows:
m = Σfi mi
Chain fraction mol. wt of repeat unit i 29
Synthesis of
Polymers
Synthesis of Polymers
There are a number different methods
of preparing polymers from suitable
monomers, these are
step-growth (or condensation)
step-
polymerisation
addition polymerisation
insertion polymerisation.
Types of Polymerization
Chain-growth polymers, also known as
addition polymers, are made by chain
reactions
Types of Polymerization
Step-growth polymers, also called
condensation polymers, are made by
combining two molecules by removing a
small molecule
Addition Vs. Condensation
Polymerization
Polymerisation reactions can generally be
written as
x-mer + y-
y-mer (x +y)-
+y)-mer
In a reaction that leads to condensation
polymers,, x and y may assume any value
polymers
i.e. chains of any size may react together
as long as they are capped with the
correct functional group
Addition Vs. Condensation
Polymerization
In addition polymerization although x
may assume any value, y is confined to
unity
i.e. the growing chain can react only with a
monomer molecule and continue its
growth
Thermodynamics
For polymerization to occur (i.e., to be
thermodynamically feasible), the Gibbs
free energy of polymerization ∆Gp < 0.
If ∆Gp > 0, then depolymerization will be

favored.
THERMOPLASTIC
Organic long chain polymer that usually unsaturated become soft
when heated and can be molded under pressure. They are linear
or branched polymers with little or no cross linking. Growth of
thermoplastic is attributed to certain attractive properties:
1-Lightness in weight.
2-Chemical corrosion resistance.
3-Toughness.
4-Ease of handling.
1-Polyethylene
PE :The most commodity polymers ,and PCs final products(widely used)
Why PE is widely used?
1-Easly in producing monomer (E) from NG or petroleum fractions or

Naphtha.
2-Low cost 3- PE posses especial properties such as resistance to

corrosion and plastering.
Classification of PE;
Low density PE :LDPE

Density:0.915-0.935 gm/cm3.
Mwt=30000-50000.
Branched chain polymer .
Degree of crystallization is low.
Low ability to absorb water.
High resistance to chemicals(acids and bases)
Resistances to impact and electricity thus it is used in insulating.
2-High density PE :HDPE
a-Density=0.95-0.96gm/cm3.
b- Linear polymer(no branches).
c-Highly crystalline.
d-Highly packed molecule, less permeable to gases.
3-Linear low density:LLDPE
It posses good physical and mechanical properties

Application: To produce linear low-density
low density polyethylene (LLDPE) to
high density polyethylene (HDPE)
(HD using the low-pressure,
pressure, gas-phase
gas
UNIPOL PE process.
Description:A wide range of polyethylenes is made in a gas-phase,

gas fl
uidized- bed reactor using proprietary solid and slurry catalysts. The
product is in a dry, free-fl
free fl owing granular form substantially free of fines
as it leaves the reactor and is converted to pellet form for sale. Melt index
and molecular weight distribution are controlled by selecting the proper
catalyst type and adjusting operating conditions. Polymer density is
controlled by adjusting comonomer content of the product. High
productivity of conventional and metallocene catalysts eliminates the
need for catalyst removal The simple and direct nature of this process
results in low investment and operating costs, low levels of
environmental pollution, minimal potential fi re and explosion hazards,
and easy operation and maintenance. Gaseous ethylene, comonomer and
catalyst
talyst are fed to a reactor (1) containing a fluidized bed of growing
polymer particles and operating near 25 kg / cm2 and approximately 100
°C. A conventional, single-stage,
single stage, centrifugal compressor (2) circulates
reaction gas, which fluidizes the reaction bed, provides raw material for
the polymerization reaction, and removes the heat of reaction from the
bed. Circulating gas is cooled in a conventional heat exchanger (3).
The granular product flows intermittently into product discharge tanks (4)
where un reacted gas is separated from the product and returned to the
reactor. Hydrocarbons remaining with the product are removed by
purging with nitrogen. The granular product is subsequently pelletized in
a low-energy system (5) with the appropriate additives for each
application.
Products: Polymer density is easily controlled from 0.915 to 0.970 g/cm.

Depending on catalyst type, molecular weight distribution is either
narrow or broad. Melt index may be varied from less than 0.1 to greater
than 200. Grades suitable for film, blow-molding, pipe, roto-molding and
extrusion applications are produced.
Commercial plants: Ninety-six reaction lines are in operation, under

construction or in the design phase worldwide with single-line capacities
ranging from 40,000 tpy to more than 450,000 tpy
2-Polyethylene, LDPE
Application: The high-pressure
high Lupotech TS or TM tubular reactor
process is used to produce low-density
low density polyethylene (LDPE)
homopolymers and EVA copolymers. Single-train
Single train capacity of up to
400,000 tpy can be provided.
Description: Ethylene, initiator and, if applicable, comonomers are fed

to the process and compressed to pressures up to 3,100 bar before
entering the tubular reactor. In the TS mode, the complete feed enters
the reactor at the inlet after the preheater; in the TM mode, part of the
gas is cooled and quenches the reactor
reactor contents at various points of
injection. The polymer properties (MI, ,, MWD) are controlled by the
initiator, pressure, temperature profile and comonomer content. After
the reactor, excess ethylene is recovered and recycled to the reactor
feed stream. Thehe polymer melt is mixed with additives in an extruder to
yield the final product A range of products can be obtained using the
Lupotech T process, ranging from standard LDPE grades to EVA
copolymers or N-butyl
butyl-acrylate
acrylate modified copolymer. The products can be
applied in (shrink) film extrusion, injection molding, extrusion blow
molding, pipe extrusion, pipe coating, tapes and monofilaments. There is
no limit to the number of reactor grades that can be produced. The
product mix can be adjusted to match market demand and economical
product ranges. Advantages for the tubular reactor design with low
residence time are easy and quick transitions, startup and shutdown.
Reactor grades from MI 0.15 to 50 and from density 0.917 to0.934
g/cm3, with comonomer content up to 30% can be prepared.
Economics: Consumption, permetric ton of PE:

Ethylene, t 1.010
Electricity, kWh 700–1,000
Steam, t –1.2 (export credit)
Nitrogen, Nm3 4
Commercial plants: Many Lupotech T plants have been installed after

the first plant in 1955, with a total licensed capacity of 4.4 million tons.
Basell operates LDPE plants in Europe with a total capacity of close to 1

million tpy. The newest state-of-the-art Lupotech TS unit at Basell’s site
in Aubette, France, was commissioned in 2000; with a capacity of 320
thousand tons, it is the largest single-line LDPE plant.
Note: When tubular reactor is used LDPE produced is used for

production of films while when Autoclaves reactor used LDPE produced
is used for forcoatings
3-Polyethylene, HDPE
Application: To produce high-density polyethylene (HDPE) using the
stirred-tank, heavy-diluent Hostalen process.
Description: The Hostalen process is a slurry polymerization method

with two reactors parallel or in series. Switching from a single reaction to
a reaction
in cascade enables producing top quality unimodal and bimodal

polyethylene (PE) from narrow to broad molecular weight
distribution(MWD) with the same catalyst. Polymerization occurs in a
dispersing medium, such as n-hexane, using a very high-activity Ziegler
catalyst. No deactivation and catalyst removal is necessary because a very
low level of catalyst residue remains in the polymer. For unimodal-grade
production the catalyst, the dispersing medium, monomer and hydrogen
are fed to the reactor (1, 2) where polymerization occurs. In the case of
bimodal grade production, the catalyst is only fed to the fi rst reactor (1);
the second step polymerization occurs under different reaction conditions
with respect to the fi rst reactor. Also ethylene, butene and further
dispersing medium are fed to the second reactor (2). Reactor conditions
are controlled continuously, thus a very high-quality PE is manufactured.
Finally, the HDPE slurry from the second reactor is sent to the
postreactor (3) to reduce dissolved monomer, and no monomer recycling
is needed. In the decanter (4), the polymer is separated from the
dispersing medium. The polymer containing the remaining hexane is
dried in a fluidized bed dryer (5) and then pelletized in the extrusion
section. The separated and collected dispersing medium of the fl uid
separation step(6) with the dissolved co-catalyst and comonomer is
recycled to the polymerization reactors. A small part of the dispersing
medium is distilled to maintain the composition of the diluent.
Products: The cascade technology enables the manufacturing of tailor-

made products with a definite MWD from narrow to broad MWD. The
melt flow index may vary from 0.2 (bimodal product) to over
50(unimodal product). Homopolymers and copolymers are used in
variousapplications such as blow-molding (large containers, small
bottles), extrusion molding (fi lm, pipes, tapes and monofi laments,
functional packaging) and injection molding (crates, waste bins, transport
containers).
Economics: Consumption, per metric ton of PE (based on given product

mix):
Ethylene and comonomer, t 1.015
Electricity, kWh 500
Steam, kg 450
Water, cooling water, T = 10°C, mt 175
Commercial plants: There are 33 Hostalen plants in operation or under

construction
5-Polypropylene:
Application: Spheripol process technology produces propylene-based
polymers including homopolymer PP and many families of random and
heterophasic impact and specialty impact copolymers.
Description: In the Spheripol process, homopolymer and random

copolymer polymerization takes place in liquid propylene within a
tubular loop reactor (1). Heterophasic impact copolymerization can be
achieved by adding a gas-phase reactor (3) in series. Removal of catalyst
residue and amorphous polymer is not required. Unreacted monomer is
flashed in a two-stage pressure system (2, 4) and recycled back to the
reactors. This improves yield and minimizes energy consumption.
Dissolved monomer is removed from the polymer by a steam sparge (5).
The process can use lower-assay chemical-grade propylene (94%) or the
typical polymerization-grade (99.5%).
Yields:Polymer yields of 40,000 – 60,000 kg / kg of supported catalyst are

obtained. The polymer has a controlled particle size distribution and an
isotactic index of 90 – 99%.
Economics: The Spheripol process offers a broad range of products with

excellent quality and low-capital and operating costs.
Consumption, per metric ton of PP:
Propylene and comonomer, t 1.002–1.005
Catalyst, kg 0.016–0.025
Electricity, kWh 80*
Steam, kg 280
Water, cooling, mt 90
* In case of copolymer production, an additional 20 kWh is required.
Products: The process can produce a broad range of propylene-based

polymers, including homopolymer PP, various families of random
copolymers and terpolymers, hetero phasic impact and speciality impact
copolymers(up to 25% bonded ethylene), as well as high-stiffness, high
clarity copolymers.
Commercial plants: Spheripol technology is used for about 50% of

the total global PP capacity. There are 94 Spheripol process plants
operating World wide with total capacity of about 17 million tpy. Single-
line design capacity is available in a range from 40,000 to 550,000 tpy.
6-PVC
PVC (suspension)
Application: A process to produce polyvinyl chloride (PVC) from

vinylchloride monomer (VCM) using suspension polymerization. Many
types of PVC grades are produced including: commodity, high K-value,
K
low K-value,
value, matted type and co-polymer
co polymer PVC. The PVC possesses
excellent product qualities such as easy processability and good heat
stability.
Description: PVC is produced by batch polymerization of VCM

dispersed in water. Standard reactor sizes are 60, 80, 100 or 130 m3. The
stirred reactor (1) is charged with water, additives and VCM. During
polymerization reaction, the temperature is controlled at a defined
temperature depending on the grade by cooling water or chilled water. At
the end of the reaction, the contents are discharged into a blow down tank
(2) where most of the un reacted VCM is flashed off. The reactor is
rinsed and sprayed
yed with an anti-fouling
anti fouling agent, and is ready for the
following batch. The PVC slurry containing VCM is continuously fed to
the stripping column(3). The column has a proprietary design and
effectively recovers VCM from the PVC slurry without any deterioration
deteriorati
of PVC quality. After stripping, the slurry is de-watered
de watered (4), and dried
effectively by the proprietary dryer (5). It is then passed to storage silos
for tanker loading or bagging. Recovered VCM is held in a gas holder
(6), then compressed, cooled and condensed to be reused for the
following polymerization batch.
Economics:
Raw materials and utilities, per ton of PVC:
VCM, t 1.003
Electricity, kWh 160
Steam, t 0.7
AddiCves, for pipe grade, $US 12
Commercial plants: The process has been successfully licensed 15

times worldwide. Total capacity of the Chisso process in the world is
more than 1.5 million tpy. In addition, Chisso VCM removal technology
has been licensed to many PVC producers worldwide.
Synthetic fibers
Fibers":Length/diameter>100: (1)Textiles are main use.
1-Must have high tensile strength.
2-Usually highly crystalline and highly polar.
(2)Formed by spinning:ex.extrude polymer through a spinneret:
Pt plate with 1000"s of holes for nylon. Melt spinning
Ex. Rayon-dissolved in solvent then pumped through die head to make

fibers. Solution spinning
(3) The fibers are drawn .
(4)Lead to a highly aligned chains-febrile structure.
1-Polyesters (polyethylene terephthalate)
Application: To produce polyesters for resin and textile applications

from terephthalic acid (PTA) or dimethyl terephthalate (DMT) and diols
[ethylene glycol (EG) or others], using the UIF-proprietary four-
reactor(4R)- process including DISCAGE-finisher
Description: A slurry composed of PTA and EG, or molten DMT and

EG is fed to the first esterifi cation/ester-interchange reactor (1) in which
main reaction occurs at elevated pressure and temperatures (200°C–
270°C). Reaction vapors—water or methanol— are sent to a low/high
boiler separation column. High boilers are reused as feedstock. The
oligomer is sent to a second cascaded, stirred reactor (2) operating at a
lower pressure and a higher temperature. The reaction conversion
continues to more than 97%. Catalyst and additives may be added.
Reaction vapors are sent to the process column (5). The oligomer is then
prepolymerized by a third cascaded reactor (3) under subatmospheric
pressure and increased temperature to obtain a degree of
polycondensation >20. Final polycondensation up to intrinsic viscosities
of i. V. = 0.9 is done in the DISCAGE-finisher (4). Pelletizing or direct
melt conversion usage is optional. EG is recovered by condensing process
vapors at vacuum conditions. Vacuum generation may be done either by
water vapor as a motive stream or by the diol (EG). The average product
yield exceeds 99%.
Economics: Typical utility requirements per metric ton of PET are:
Electricity, kWh 55.0
Fuel oil, kg 61.0
Nitrogen, Nm3 0.8
Air, Nm3 9.0
Commerical plants:
Thirteen lines with processing capacities ranging
from 100 to 700 mtpd are operating; more than 50 polyester CP

plantshave been built worldwide. Presently, 700 mtpd lines are in
operation as
single-train lines, including a single finisher.

2-Nylon 6
Is a polyamide contain –CONH-
Raw material:Caprolactum.
Additives
Mixing tank
caprolatum
∞ Polymer-
Cooling Pellet
ization
format-
Filtration ion Nylon
T=10-15min. T=250-280 CO pellet
P=18 atm.(Mwt)
3-Nylon 66:
Polymer is produced from hexamethylene adipamide which produced
from condensation polymerization of adipic acid and
hexamethylenediamine.
Water
Acid MIXING
Product
Polymerization
in sticm- Concentrated to 60% or
amine Salt dil.solution of conc. salt solu.
etric ratio salt separation and
In Autoclave
purified by crystallization
T=270-300oC
P=18 am
The press is reduced at end of reaction to atmos.
At the end of the reaction
Polymer melt under press or

Drying EXTRUDER
N2
4-Acrylic :
Uses: Wool replacement.
Production:Copolymerization of acrylonitrile with comonomer in
presence of reaction initiators either free radicals or anionic at low
temperature.
Polymerization on industrial scale:
1-Suspnsion polymerization: in presence of water
2-Solution polymerization: in presence of suitable solvent :DMF or
DMSO.
Catalyst
water Air
AN
Washing Drying Storage
Co monomer ∞ ∞
Polymerization Stop Polymerization
Monomer recovery
To Spinning

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Save from: http://www.uotechnology.edu.iq/dep-chem-eng/index.htm

Petrochemicals in general are compounds and polymers derived directly

The primary raw materials

Secondary raw materials, or intermediates, are obtained from natural

• Olefins includes ethylene, propylene, and butadiene. Ethylene and propylene

Factors affecting development and growth of petrochemical

2-Great development in production and purification of basic PCs.

4-Cost of PCs produced equal or less than natural or classical materials.

5-Great demand on commodity product and limited availability of natural product

Characterization petrochemical industries

1-Different processing stages from oil and NG to final product.

4- High production capacity is considered to be economic due to technological

5- By-product associated with basic PCs produced can be utilized in economics of

thus are replaced by PCs product.

Generation of petrochemical industry:

1st Generation PCs:From NG and Petroleum fraction.

Processes: Steam cracking for production of Olefins and Aromatics.

2nd Generation PCs:Intermediate :From Basic PCs .

1-Nuclear energy. 2-Radinet

Application: To produce polymer-grade

Description: Hydrocarbon feedstock is preheated and cracked in the presence of

First: Steam cracking process:

CH3CH2CH3 → CH2=CH2+ CH4

Furances:tubular furance:tube arranged either vertical or horizantal, and made of

NG,reduced crude or fuel oil burns to give heat.

Practical design of steaam cracking and operating conditions depends on feed.

If the raw material:Ethane-gas oil :then operating conditions are:

Temp:750-850 oC Resdance time(RT)=0.2-0.3 sec.

Steam:feed 0.2-1 Pressure:1-3 bar.

Effect of Operating conditions(OC):on steam cracking process:

1-RT:low:yield :high and formation of coke:low

In order to lower (RT)a- lower the reactor size(volume) b- reduce pressure c-

Advantage of use of steam

C + H2O →CO +H2

1-Reduce the unit capacity. 2-Recovery limited amount of steam.

3- The need of high energy to cool the product.

2- Recovery of thermal energy as steam

Cooling is carried out in 2-3 stages according to feed as follows:

1-Quenching(rapid and immediate) and production of high pressure steam.

2- Primary fractionation:for product of thermal cracking in case of feed stock and

Cooling is carried out to about 400C as follows:

gas at 200oC gases H2,CH4,C2H6

Flash drum heating

Resonces for acid gas removal:

2- Prevent catalyst (pd) poisining which is used in acetylene hydrogenation.

ppm when three or more stages are used.

NaOH 300ppm water

Waste Waste Waste

Counter current scrubbing (washing)with dil.NaOH

The content of water in gas is reduced to(1-2)ppm.

When gas is subjected to low temp.in copression and distillatio units.

2- Some times gas is cooled by propylene refregerent after washing by soda

wet gas Dry air

Used in almost all low olefins production units.

Acetylene removal is carried out either:

1-Front end removal;in copression stage.

C2-C5 E+Ethylene Ethan