PETROLEUM REFINING AND PETROCHEMICALS (3170507), Sem- VI (CHEM)

Chapter Name: C1 AND C2 PETROCHEMICALS

DEFINITION OF PETROCHEMICAL
 Petrochemical is a chemical compound or element recovered or derived partially or entirely from
petroleum or natural gas hydrocarbons and intended for chemical markets.
 Petroleum and natural gas are made up of hydrocarbon molecules, which comprises of one or more
carbon atoms, to which hydrogen atoms are attached.

PETROCHEMICAL SECTOR- PRESENT AND FUTURE & CHALLENGES

 Petrochemical products are everywhere and are integral to modern societies. They include plastics,
fertilisers, packaging, clothing, digital devices, medical equipment, detergents, tires and many others.
They are also found in many parts of the modern energy system, including solar panels, wind turbine
blades, batteries, thermal insulation for buildings, and electric vehicle parts.
 The Future of Petrochemicals takes a close look at the consequences of growing demand for these
products, and what we can do to accelerate a clean energy transition for the petrochemical industry.
 Already a major component of the global energy system, the importance of petrochemicals is
continuing to grow. Demand for plastics – the most familiar group of petrochemical products – has
outpaced that of all other bulk materials (such as steel, aluminium or cement), and has nearly
doubled since 2000.
 Advanced economies, such as the United States and Europe, currently use up to 20 times as much
plastic and up to 10 times as much fertiliser as developing economies such as India and Indonesia, on
a per capita basis. This underscores huge potential for growth worldwide.
 Increasing global competition in the industry is driven by new supply dynamics for chemical
feedstocks.
 After two decades of stagnation and decline, the United States has returned to prominence as a low-
cost region for chemical production thanks to the shale gas revolution.
 Today, the United States is home to around 40% of the global capacity to produce ethane-based
petrochemicals. Led by Saudi Arabia and Iran, the Middle East remains the low-cost champion for
key petrochemicals, with a host of new projects announced across the region. China and Europe each
account for around a quarter of the global capacity for naphtha-based, high-value chemicals, but they
have only very small shares of capacity based on lighter feedstocks as a result of limited availability.
 China’s burgeoning coal-based chemical industry, once a speculative proposition, now embodies
steady technological improvements. India is poised to grow strongly from its current level of only
4% of global capacity to satisfy increasing domestic demand.

 Petrochemicals are all around us:

 Plastic packaging for food and other commercial products can be made from a range of
petrochemical products, including polyethylene and polystyrene
 Globally, more than half of ammonia is converted to urea, which is in turn mainly used as
a fertiliser used to increase crop yields and boost food production
 Synthetic rubber is a major component of tires for cars, trucks and bicycles, and is mainly derived
from the petrochemical butadiene
 Many of the laundry detergents and items of clothing in our washing machines are derived from
petrochemicals, such as surfactants and polyester fibre

 Plastics pollution in oceans & policy recommendations:

 When plastic waste finds its way into the ocean, it breaks down into small pieces that are commonly
ingested by marine life. As the mass of larger debris – including containers, bottle caps, crates and
old fishing gear – continues to degrade over time, the quantity of microplastics could increase
significantly. This is an urgent environmental problem garnering much attention around the world.

 Petrochemicals are rapidly becoming the largest driver of global oil demand

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PETROLEUM REFINING AND PETROCHEMICALS (3170507), Sem- VI (CHEM)
Chapter Name: C1 AND C2 PETROCHEMICALS
 The growth in demand for petrochemical products means that petrochemicals are set to account for
over a third of the growth in oil demand to 2030, and nearly half to 2050, ahead of trucks, aviation
and shipping. Petrochemicals are also poised to consume an additional 56 billion cubic metres of
natural gas by 2030, equivalent to about half of Canada’s total gas consumption today.

 Challenges:
 Petrochemicals face a number of climate, air quality, and water pollution challenges. Petrochemical
products provide substantial benefits to society, including a growing number of applications in
various cutting-edge, clean technologies critical to a sustainable energy system.
 However, the production, use and disposal of these products poses a variety of sustainability
challenges that need to be addressed. Even though the chemical sector consumes roughly as much
energy as the steel and cement sectors combined, it emits less CO2 than either sector.
 Still, this amounts to around 1.5 GtCO2, which is 18% of all industrial-sector CO2 emissions, or 5%
of total combustion-related CO2 emissions. This is in part because the chemical industry consumes
more oil and gas than other heavy industries, which tend to rely more on coal.
 Another contributing factor is that the carbon contained in chemical feedstocks is mostly locked into
final products (such as plastics) and released only when the products are burned or decompose.

SYNTHETIC ORGANIC CHEMICAL INDUSTRIES

 The definition of an organic chemical is a compound containing carbon, oxygen, and hydrogen as
principal constituent elements.
 Synthetic organic chemicals usually have a fairly low molecular weight and a relatively simple
structure.
 Synthetic organic chemicals can be categorized as primary, intermediate, or end chemicals.

PETROCHEMICALS-THE KEY GROWTH AREA

 Prior to 1951 Indian organic chemical production was limited to primary chemicals such as alcohol,
acetone, benzene, and toluene. Various other chemicals were imported and converted to end-
products, principally drugs, dyes, and plastics.
 By the end of the Second Plan (1961), a number of organic chemical products were indigenously
produced, notably DDT, BHC, acetic acid, acetic anhydride, polyethylene and polyvinyl chloride.
These were based on industrial alcohol, benzene from coal carbonization, and acetylene derived from
calcium carbide.
 During the Third Plan (1961-1966), organic chemical industries showed growth prospects and
potential target achievements so that the conventional raw materials cited above will no longer
suffice.
 Petroleum feedstocks took over as the major raw material in the Fourth Plan (1969-1974) and thus
petrochemicals began to play a major role in Indian economy, a situation which existed in the U.S.
and UK after World War II (1946 onwards). The prediction has been made that 65% would be
derived from petroleum and the remaining 35% from non-petroleum products (fermentation alcohol,
coke oven by-products, and calcium carbide).

REASONS FOR STUDYING PETROCHEMICAL INDUSTRIES

 As pointed out in the previous section, the future organic chemical industry of India will depend
more and more on petroleum sources as raw materials.

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PETROLEUM REFINING AND PETROCHEMICALS (3170507), Sem- VI (CHEM)
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 Aromatic raw materials from coal are geared to steel production which does not have sufficient
growth rate to match the organics and ammonia-based fertilizer yearly percentage gain in production.
 It is uneconomic to expand the higher cost alcohol supplies.
 A second disadvantage of alcohol is the lack of consolidation of producing units with very limited
capacity. The availability of large bulk feedstocks at one location, i.e., a refinery to supply a
petrochemical-type plant, is a distinct advantage in terms of critical economic plant size.
 Different products such as ethylene, propylene, etc., being simultaneously produced in one refinery,
enable integration of a number of consuming industries utilizing these various raw material streams.

PRINCIPAL RAW MATERIALS AND THEIR RESOURCES

(1) Natural Gas (largely methane)
 Major raw material in U.S., not available in quantity in India. Could be shipped economically by
refrigerated tanker from Middle East.
 Ethane (-4% in natural gas) is the most valuable product since ethylene can be produced by thermal
cracking.

(Cracking)
 Ethane --------------Ethylene (75% yield)
 cracking However, most of the ethylene comes from refinery gases.

(2) Liquefied Petroleum Gas (LPG)

 Easily extracted from natural gas
 Can be transported in tank cars or pipelines as a liquid
 Contains propane and butane which can be easily cracked to olefins

(3) Refinery Off-Gases

 From catalytic and reforming operations.
 Paraffinic and olefinic fractions used for petrochemicals
 Hydrogen used for NH3 production
 Sulfur by-product obtained from H₂S by oxidation process

(4) Hydroforming of Petrochemical Stocks

 Produces benzene, toluene, and xylene (BTX)
 Gives large quantities of hydrogen

(5) Naphtha and Fuel Oil

 Accumulate in large quantities in Indian refineries due to lack of end use
 Used to make (1) synthesis gas by catalytic reforming or partial combustion,(2) petrochemical
starting materials such as ethylene, acetylene, and propylene by steam cracking

(6) Petroleum Coke

 Source of carbon for calcium carbide and acetylene or electrodes for aluminum industry

BASIS FOR STUDY: TYPICAL FEEDSTOCKS TO PETROCHEMICAL PROCESSES

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PETROLEUM REFINING AND PETROCHEMICALS (3170507), Sem- VI (CHEM)
Chapter Name: C1 AND C2 PETROCHEMICALS
 Petrochemicals refers to all those compounds that can be derived from the petroleum refinery
products
 These raw materials contain one or several predominant hydrocarbons separated so that compounds
are synthesized as follows:
A. Chemicals From C1 Compounds (Methane and Synthesis Gas)
B. Chemicals From C2 Compounds (Ethylene and Acetylene)
C. Chemicals From C3 Compounds (Propylene)
D. Chemicals From C4 Compounds (Butanes and Butenes)
E. Chemicals From Aromatics (Benzene, Toluene and Xylene)
F. Pesticides
G. Pharmaceutical Industry
 It can be seen that petrochemicals are produced from simple compounds such as methane, ethylene
and acetylene but not multicomponent products such as naphtha, gas oil etc.

PETROCHEMICALS INDUSTRY IN GUJARAT

1. Guj Info Petro Ltd(GIPL), Infocity, Gandhinagar
2. Gujarat State Petronet Ltd(GSPL), UdyogBhavan, Sector 11, Ahmedabad
3. Nova Petrochemicals Ltd (CHIRIPAL GROUP),Sarkhej - Bavla Highway, Ahmedabad
4. Arham Petrochem Pvt Ltd, Elis Bridge C.G.Road, Ahmedabad
5. Jaihind Projects Ltd., Venus atlantis corporate park, Ahmedabad
6. Nova Petrochemicals Limited. Moraiya, Ahmedabad. ...
7. Hindustan Chemicals. Amraiwadi, Ahmedabad.
8. Reliance Industries Ltd (Baroda Manufacturing Division)(IPCL), Vadodara
9. PositronicsPvt Ltd (Positronics Group), Makarpura, Vadodara.
10. Industrial & Allied Chemicals. Shivaji Road, Vadodara.
11. Gujarat Narmada Valley Fertilizers Co. Ltd, Narmada Nagar, Bharuch
12. Reliance Industries Ltd, Hazira
13. Reliance Export Oriented Unit, Hazira
14. JBF Industries Ltd, Vapi
15. Shree ChalthanVibhagKhandUdhyogSahkariMandali Ltd, Chalthan, Surat

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PETROLEUM REFINING AND PETROCHEMICALS (3170507), Sem- VI (CHEM)
Chapter Name: C1 AND C2 PETROCHEMICALS
CHEMICALS FROM C1 COMPOUNDS (METHANE AND SYNTHESIS GAS) or RANGE OF
PETROCHEMICALS PRODUCED FROM C1, C2 HYDROCARBON AND BENZENE.

Fig. 1: Synthetic chemical intermediates and products from methane or other sources of synthesis gas.

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PETROLEUM REFINING AND PETROCHEMICALS (3170507), Sem- VI (CHEM)
Chapter Name: C1 AND C2 PETROCHEMICALS
RANGE OF PETROCHEMICALS PRODUCED FROM C2 HYDROCARBON AND BENZENE.

Fig.2: Synthetic chemical intermediates and products from propylene.

RANGE OF PETROCHEMICALS PRODUCED FROM BENZENE.

Fig.3 : Synthetic chemicals and intermediates from benzene.

C1 PETROCHEMICALS
METHANOL PRODUCTION
 Properties of Methanol (CH3OH)
Mol. wt. 32.04
M.P. - 97.8 ˚C
B.P. 64.7 ˚C
Density 0 .788 @ 20 ˚C
Explosive limits Lower 6.0 vol. % in air
Upper 36.5 vol. % in air
Toxicity limits 200 ppm

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PETROLEUM REFINING AND PETROCHEMICALS (3170507), Sem- VI (CHEM)
Chapter Name: C1 AND C2 PETROCHEMICALS
Grades Pure (99.8%, acetone-free), CP (95%), USP(97%)

 Uses of Methanol
 Methanol can be used as a fuel, both directly and through blending with gasoline.
 to produce other fuel additives such as MTBE.
 in the production of biodiesel
 in the production of dimethyl ether
 it is use as a green diesel substitute.
 Use as chemical building block for hundreds of everyday products, including plastics, paints, car
parts and construction materials.
 Use as a clean energy resource used to fuel cars, trucks, buses, ships, fuel cells, boilers and cook
stoves.
 Methanol can also lower the freezing point of a water-based liquid and increase its boiling point,
therefore, it is used as an antifreeze to keep cleaning fluids from freeing.

 Methods of Methanol Production

 Catalytic hydrogenation of carbon monoxide (accounts for -75% of production)
 Oxidation of LPG to give oxygenated hydrocarbon co-products of which methanol is a major
fraction
 Catalytic hydrogenation of carbon monoxide

 Chemical Reactions of Methanol Production

(a) CO+ 2H₂CH3OH;
(b) Side reactions to methane
 CO + 3H₂CH4 + H2O;
 2CO + 2H₂CH4+ CO₂;
(c) Side reaction to higher mol. wt. compounds
 XCO+ yH₂higher mol. wt. alcohols and hydrocarbons

 all above reactions are exothermic

 Catalyst: Mixed catalyst made of oxides of Zn, Cr, Mn, Al.

 Flow Sheet of Methanol Production: Figure:4

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PETROLEUM REFINING AND PETROCHEMICALS (3170507), Sem- VI (CHEM)
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Fig. 4: Methanol Production via synthesis gas route

 Process Description of Methanol Production:

 H2 and CO adjusted to molar ratio of 2.25.
 The mixture is compressed to 200 – 350 atms.
 Recycle gas (Unreacted feed) is also mixed and sent to the compressor.
 Then eventually the mixture is fed to a reactor. Steam is circulated in the heating tubes to maintain a
temperature of 300 – 375°C.
 After reaction, the exit gases are cooled.
 After cooling, phase separation is allowed. In this phase separation operation methanol and other
high molecular weight compounds enter the liquid phase and unreacted feed is produced as the gas
phase.
 The gas phase stream is purged to remove inert components and most of the gas stream is sent as a
recycle to the reactor.
 The liquid stream is further depressurized to about 14 atms to enter a second phase separator that
produces fuel gas as the gaseous product and the liquid stream bereft of the fuel gas components is
rich of the methanol component.
 The liquid stream then enters a mixer fed with KMNO4 so as to remove traces of impurities such as
ketones, aldehydes etc.
 Eventually, the liquid stream enters a distillation column that separates dimethyl ether as a top
product.
 The bottom product from the first distillation column enters a fractionator that produces methanol,
other high molecular weight alcohols and water as three different products.

 Major Engineering Problems of Methanol Production

(a) Thermodynamic and kinetic considerations of synthesis gas.
 This process is similar to NH, in design because of the unfavorable equilibrium constant under
normal pressure conditions for an exothermic reaction

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PETROLEUM REFINING AND PETROCHEMICALS (3170507), Sem- VI (CHEM)
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Temp., °C Kp
260 1.5 x 10-3
300 3.1 x 10-4
340 8.7 x 10-5
380 2.7 x 10-6
 For temperatures less than 260°C, reaction rates, even on active catalysts, are too low to be
economic. The choice of pressure is also economic, the balance existing between pressurized reactor
costs and recycle costs. Under optimum conditions, a 50% conversion per pass at 240 atms. and
300°C is typical.

(b) Reactor design

 Thick-walled pressure vessels are constructed of relatively cheap steel, but must be lined with Cu to
avoid the formation of iron carbonyl Fe(CO)5, a volatile compound which poisons the catalysts in
addition to creating a severe corrosion problem.
 Heat exchange to control the highly exothermic reaction is accomplished in several ways. In the
Uhde design, the compressed gas enters an annulus along the shell wall which serves to preheat the
gas and cool the heat treated steel pressure shell.
 The gases then move in the opposite direction through the shell side of a tubular array, picking up
more heat. The last pass is through the catalyst on the inside of the tubes. The catalyst is placed in
zones with further temperature control accomplished by direct bleed of cold reactant gases which
bypass the preheat zone.
 A second alternate is the simpler Montecatini-Fauser design in which the combination of a
circulating high pressure water and waste heat boiler acts as the principal heat control. This is shown
in Figure 4.

(c) Catalyst fouling

 Excess hydrogen over the minimum theoretical 2:1 H2/CO ratio is used to avoid fouling the catalyst
with higher mol. wt. material which adsorbs on the catalyst under higher CO partial pressures.
 Synthesis gas from steam reforming has a satisfactory H₂/CO ratio whereas partial combustion gas
has about a 2:1 H₂CO ratio and must be butted up with extra H2 from the water gas shift reaction
(CO+H₂O).

(d) Inert gas accumulation

 In carrying high recycle loads, the possibility of accumulating inert gas is avoided by maintaining a
side-stream purge on the recycle gas.

FORMALDEHYDEPRODUCTION (HCHO)
 Properties of Formaldehyde (HCHO)
Mol. wt. 30.03
M.P. - 118 ˚C
B.P. -19 ˚C
Density 0 .815 @ -20 ˚C
Explosive limits Lower 7.0 vol. % in air
Upper 73 vol. % in air

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PETROLEUM REFINING AND PETROCHEMICALS (3170507), Sem- VI (CHEM)
Chapter Name: C1 AND C2 PETROCHEMICALS
Toxicity limits 10 ppm
Solubility Soluble in water, alcohol and polar solvents, slightly soluble in
hydrocarbons, chloroform, ether
Grades CP gas, 37% aqueous solutions,trioxane polymer (CH₂O)3,
paraformaldehyde, (CH₂O)n, nH2O, where n=10-50

 Uses of Formaldehyde
 Used as a disinfectant in industries,
 Usedas sterilization, and
 Used in car manufacture, explosives, plastic, resins, chemicals and other artificial materials. It is also
used in sanitary products like paper towels, napkins and tissues.
 Uses in medicine:it kills many bacteria, fungi etc so used as an antiseptic.
 Uses in building and construction:
 Formaldehyde resins are used to manufacture wooden products used widely in furniture, cabinetry,
mouldings, flooring, shelving, counter tops and other household furnishings. Wood panels are made
from the wood which will be either disposed or burned hence minimizing wood wastage
 Uses in food and others:
 It is used as preservative in food, paints and cosmetics.
 Used as an antiseptic in medicine, disinfectant in funeral home, used in making rdx.
 To improve the yield of fuels it is used in petroleum and natural gas industries
 Used in the manufacture of ink.
 In the manufacture of phenolic, urea, and melamine

 Classification of Methods of Formaldehyde Production

 Catalytic oxidation-dehydrogenation of methanol
 Oxidation of methane or LPG to give oxygenated hydrocarbon co-products in which formaldehyde is
separated with difficulty

 Chemical reactions of Formaldehyde Production

(a)Oxidation: CH3OH + ½O2  HCHO+ H₂O;
(b) Pyrolysis: CH3OHHCHO + H2;
(c)Undesired Side reaction-complete combustion: CH3OH + (3/2)O2 2H₂O + CO₂;
 In the above reactions, the first and third are exothermic reactions but the second reaction is
endothermic. The reactions are carried out in vapour phase.
 Catalyst: Silver or zinc oxide catalysts on wire gauge are used.
 Operating temperature and pressure: Near about atmospheric pressure and 500 – 600°C

 Flow Sheet of Formaldehyde Production: Figure:4

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PETROLEUM REFINING AND PETROCHEMICALS (3170507), Sem- VI (CHEM)
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Figure 4: Flow sheet of Formaldehyde production

 Process Technology description (Figure 4):

 Non-purified air, compressed to about 0.2 atm. gage is preheated heat exchange with reacting gases
and then conveyed to a methanol evaporator.
 Conditions are set to keep the CH3OH: O₂ ratio in the 30-50% range.
 The mixed gases are preheated, sent to a reactor where silver or copper gauze or their oxides are
catalysts.
 Catalyst activity is controlled to maintain a balance between the endothermic dehydrogenation and
exothermic oxidation reactions at reaction conditions of 450-600°C. Some complete combustion
takes place.
 The product gases are absorbed in a water scrubber which is cooled by external circulation, and then
fractionated to recover approximately 15% unreacted methanol for recycle.
 Ultimate yields of 85-90 wt. % based on methanol are typical.

C2 PETROCHEMICALS
STEAM CRAKING OF PETROLEUM HYDROCARBONS
Or
ETHYLENE, PROPYLENE, AND ACETYLENE PRODUCTION

 Reaction of Ethylene production (CH2=CH2)

 CxH2X+2+ H2O + O2 (Optional) → C2H4 (4-5%)+ C2H6 + C2H2 (7-13%)+ H2 (25-30%)+ CO + CO2 +
CH4 + C3H6 + C3H8 + C4H10 + C4H8 + C6H6 + C + Heavy oils
 Reaction temperature is about 700 – 800°C (Vapor phase reaction).

 Process Description of Ethylene production

 Typical feed stocks are Naphtha & LPG.

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 The process to be detailed here is high temperature thermal reforming using ethane, propane, butane
and/or liquid naphtha.
 Superheated steam is mixed with the hydrocarbon and fed through the heated coils of a pyrolysis
furnace.
 The C1-C2 feed is pyrolyzed in a separate furnace because different residence time-temperature
conditions are required.
 The pyrolyzed gases are quenched in a waste heat steam boiler and then scrubbed with gas oil to
remove solids and heavy hydrocarbons before sending to compressors to boost pressure to 35 atms.
 The compression station may also handle refinery off-gases which can be separated in the same
system. Flash vaporization removes the C₁-C₂ fractions which are caustic-scrubbed to remove CO₂,
dried with activated alumina, and then separated into acetylene and ethylene by a combination of
absorption, extraction, and fractionation steps.
 Ethane is recycled for pyrolysis and the CH4, CO, and H₂ can be further processed to obtain
synthesis gas or used for fuel.
 The liquid fraction from the flash chamber (C3 and higher) is split by fractionation into a number of
products as indicated on the flow sheet.
 Extractive distillation is required to separate butane-butylene and butadiene because of the close
boiling point range of the three compounds under pressure.

 Flow Sheet of Ethylene production: Figure:5

Figure 5(a) : Flow sheet of ETHYLENE, PROPYLENE, and acetylene production by steam cracking
of hydrocarbons.

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PETROLEUM REFINING AND PETROCHEMICALS (3170507), Sem- VI (CHEM)
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Fig.5 (b): Flow sheet of ETHYLENE production by steam cracking of hydrocarbons.

(NOTE: You can also draw & discribe this figure only in PRDUCTION OF ETHYLENE)

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PETROLEUM REFINING AND PETROCHEMICALS (3170507), Sem- VI (CHEM)
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 Major Engineering Problems of Ethylene Production
(1) Choice of process
 There are numerous process modifications possible in pyrolysis of hydrocarbons as
(a) Feed type
 CH4 or natural gas-gives mainly CO, H₂, C₂H₂
 C₂, C3-gives CO, H2, C2H₂ and C₂H4
 C4 and higher-gives a spectrum of products as described in process description, but mainly controlled
for C2H4 and C₂H₂
(b) Choice of pyrolysis agent
 Heat only; non-catalytic-original process no longer attractive
 Heat + catalyst;-used in dehydrogenation of butylene to butadiene
 Heat+steam, non-catalytic;-thermal reforming, also called steam cracking
 Heat + steam, catalytic; -catalytic reforming, used for synthesis gas preparation
 Oxygen, non-catalytic;-partial combustion process, used for synthesisgas and acetylene production
 Oxygen + steam, non-catalytic;-modified partial combustion to givehigher yields of C2 fractions, also
called steam cracking
 Oxygen + steam, catalytic-oxydehydrogenation for butadiene, etc.
(c) Choice of pyrolysis equipment:
 Tubular, indirect fired-used for catalytic reactions
 Coiled pipe furnace-used for non-catalytic reactions in the absenceof oxygen
 Combustion-type burner-used for reaction where oxygen is introduced

 The design of pyrolysis equipment must provide a balance between temperature, contact time, and
quench time for optimum cracking to the correct product ratio and yield without carbon formation.

(2) Steam economy:

 Heat added in the pyrolysis section can be recovered in part by incorporating stack and quench boiler
heat transfer surface, the latter recovering heat that would otherwise be wasted in water or oil
quenching.
 The resulting high pressure steam makes the plant completely self-sufficient for process and heating
steam needs.

(3) Product ratio control:

 The product effluent composition is controlled by steam-hydrocarbon mole ratio and residence time.
 The ethylene/acetylene rates can be varied from 0.3 to 2.0.
 If no acetylene is desired, the light ends gas is split at the C2 level and acetylene is mildly
hydrogenated to ethylene.

ETHYLENE DICHLORIDE PRODUCTION (ClCH2.CH2Cl)

 Reactions of Ethylene Dichloride production
 CH2=CH2 + Cl2 → ClCH2.CH2Cl
 Undesired products: Propylene dichloride and Polychloroethanes.

 Flow Sheet of Ethylene Dichloride Production: Figure:6

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Figure 6:Ethylene Dichloride Production

 Process description of Ethylene Dichloride Production (Figure 6)

 Ethylene (with or without C2H6, CH4 and H₂ diluent) is mixed with chlorine and bubbled through a
liquid phase reactor.
 Ethylene dichloride product serves as the reacting medium.
 Heat of reaction is controlled by external heat exchange and recycle, or by coil or jacket heat
transfer, to hold the reactor at 45 50°C with a pressure of 1.5-2 atms.
 Traces of ferric chloride or ethylene dibromide as catalyst gives 90-95% yield with little dimer
formation.
 The gaseous products are cooled in two stages to strip the acid gas of ethylenedichloride.
 The liquid product is alkali washed and fractionated.

VINYL CHLORIDEMONOMER PRODUCTION (CH2=CHCl)

 Reactions of Vinyl Chloride production
500˚C
 CH2Cl=CH2Cl-------------→ CH2=CHCl + HCl
4 atm

 Industrial uses of vinyl chloride

 Vinyl chloride is used primarily to make polyvinyl chloride (PVC); PVC is used to make a variety of
plastic products, including pipes, wire and cable coatings, and packaging materials.
 to make polyvinyl chloride (PVC) pipes, wire coatings, vehicle upholstery, and plastic kitchen
ware.
 Higher than normal levels of vinyl chloride may be present inside new cars as the chemical
evaporates from new vinyl products
 building and construction, automotive industry, electrical wire insulation and cables, piping,
industrial and household equipment, medical supplies, and is depended upon heavily by the rubber,
paper, and glass industries.

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 Flow Sheet of Vinyl Chloride production: Figure:7

Figure 7:Vinyl Chloride production

 Process description of Vinyl Chloride production

 Ethylene dichloride (EDC) vapor at 4 atms. is dried by silica gel and sent to a stainless steel tubular
cracking furnace.
 This is externally flue gas fired and controlled at 480-520°C.
 The contact surface catalyst within the tubes is pumice or charcoal.
 The conversion per pass is around 50% and the ultimate yield is 95 96%.
 Spray quenching with cold EDC prevents back-reaction.
 Uncondensed gases are sent to a surface heat exchanger to remove the balance of the EDC and vinyl
chloride.
 The non-condensibles containing HCI are either sent to the acetylene-HCI process in an adjacent
process area or water scrubbed to recover HCI as muriatic acid.
 The condensate is fractionated with the EDC bottoms returned for recycleand vinyl chloride
monomer taken from overhead, stabilized and sent to storage.

 Major engineering problems of Vinyl Chloride production

(1) Carbon formation this occurs steadily until reactor has too high a pressure drop, thus causing shut
down and cleaning periodically. Increasing conversion beyond 50% by longer residence time or
higher temperature increases carbon formation and promotes polymerization of monomer. Reactor
conditions had to be worked out to optimize recycle loading versus reactor down time and loss of
yield.
(2) Development of the proper cracking catalyst which prevents polymerization during reaction.
(3) Excessive corrosion unless system is kept free of water vapor.
(4) Stabilization of vinyl chloride monomer-antioxidants must be chosen so that no interference will
occur later in the polymerization process.

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ETHYLENE OXIDE PRODUCTION ( )

 Reactions of Ethylene Oxide production

CH2=CH2 + (1/2) O2(air or oxygen)→ + CO + H2O

 Side reaction products: CO2 , H2O

 Catalyst used in Ethylene Oxide production

 AgO - Silver oxide on alumina

 Process Condition in Ethylene Oxide production

 Temp: 250-300°C
 Pressure: 4-5 Atm

 Industrial uses of Ethylene Oxide

 used in the production of solvents, antifreeze, textiles, detergents, adhesives, polyurethane foam, and
pharmaceuticals.
 Smaller amounts are used in fumigants and in sterilants for spices and cosmetics and during hospital
sterilization of surgical equipment.

 Process description of Ethylene Oxide production

 Ethylene of 95-98% purity and air are compressed separately, mixed together giving 3-10% C₂H4
volume concentration and passed over a catalyst of silver oxide on a porous inert carrier such as
alumina.
 A side reaction suppressing agent such as ethylene dichloride is added to the feed to reduce the
competitive oxidation reaction to CO₂ + H₂O.
 The reaction is highly exothermic and is best carried out in a fixed bed tubular reactor in which heat
transfer salt or Dowtherm is pumped around the tube within the shell to maintain a 250-300°C
temperature.
 Heat is recovered in a waste-heat steam boiler.
 A short residence time of 1 sec in plug flow is the design with an ultimate yield of 60-70%.
 The effluent gases from the reactor are water-washed under pressure.
 The absorbed ethylene oxide is sent to a packed bed desorber-fractionator tower and taken overhead.
 It still contains a large amount of water vapor plus some impurities.
 This stream is compressed to 4-5 atms, and fractionated twice to remove light ends, water, and high
boiling polymers.

 Flow Sheet of Ethylene Oxide production: Figure:8

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Figure 8: Flow sheet of Ethylene Oxide production

 Major engineering problems of Ethylene Oxide production

(1) Volume ratio of air-ethylene
 The 3% lower explosion limit for C₂H4 or C2H4O in air with a high heat of reaction has caused some
designers originally to keep at or below this value in considering process stream concentrations.
 This is done by recycle inerts from the absorber after side stream purge to remove some CO₂ + H₂O.
 The conversion is claimed to be improved at low ethylene concentrations of 3-5% in a N2 carrier
stream.
 The explosion hazard has now been minimized by use of explosion-proof standards and careful
operating procedures so that all ranges of concentrations are being used, depending more on reactor
conversion characteristics desired.

(2) Use of reactors in series

 Two reactors in series are used to convert more of the ethylene with overhead gas from the water
absorber introduced into a second reactor. This is an economic balance between cost of ethylene and
fixed charges on the additional reactor.

(3) Air versus oxygen

 In the case where a plant complex has large tonnage, low-cost oxygen available, it may be
advantageous to consider oxygen since (i) the space-time yield within a given reactor volume is
increased 3-4 times (due to higher O₂ concentrations in the kinetic equation), (ii) the absorber can be
smaller since product concentrations are 6 times greater than with the air system.
 Most ethylene oxide plants are not located near low-cost oxygen sources at present so the majority of
plants are based on air oxidation.

(4) Fluidized bed versus fixed bed

 Fluid bed operation would be ideal from a heat control standpoint.
 The widespread residence time distribution pattern due to mixing in a fluid bed plus the difficulty of
preventing catalyst sintering and transfer of AgO to the vessel wall slowed the development of this
process alternative.

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 One U.S. company now claims to have a process worked out which gives comparative yields without
catalyst regeneration.

(5) Hydration of ethylene oxide to glycol

 The hydration reaction is thermodynamically possible, yet water is used in the absorbing-desorbing
train. This is so because the hydration rate constant is not significant at 20-30°C.
 The commercial hydration process uses temperatures around 150°C.

ETHYLENE GLYCOL PRODUCTION (HOCH2.CH2OH )

 Properties of Ethylene Glycol
Mol. wt. 62.068
M.P. - 12.9˚C
B.P. 197.3˚C
Density 1.1132 @ 20 ˚C
Solubility Soluble in most organic solvents and water
Odour Odorless
Appearance Clear, Colorless liquid

 Uses of Methanol
 Use in antifreeze, hydraulic brake fluids, some stamp pad inks, ballpoint pens, solvents, paints,
plastics, films, and cosmetics. It can also be a pharmaceutical vehicle.
 It is most commonly used as antifreeze in automobiles, brake fluid, HVAC Systems, and some
human-made fibers. It is derived from ethylene oxide, which comes from ethylene.
 Ethylene glycol (antifreeze) is used in the cooling of a car radiator during the winter because it has a
much lower freezing point than water

 Reactions of Ethylene Glycol production

 Ethylene oxide is strictly a chemical intermediate which is used largely in the U.S. for producing
ethylene glycol by the hydration reaction:

 + H2O ---------------------- HOCH2.CH2OH

150-175°C
10-15 atms.
 This is done in a continuous reactor-distillation integral unit.

 Process description of Ethylene Glycol production

 Mono Ethylene Glycol (MEG) is used primarily at low-temperature processing plant for extracting
natural gas liquids. Typically a physical process plant comprises with gas dehydration system which
allows for physical separation of water saturated gas by simple dew point depression and water
condensation brought about by chilling from cross exchange with propane refrigerant.
 The resultant wet gas is prevented from freezing by injection of liquid desiccants to inhibit hydrate
formation.
 The resulting dehydrated gas stream will have a dew point preciously equal to the saturated water
volume of the gas at its coolest temperature.

 Flow Sheet of Ethylene Glycol production: Figure:9

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Figure 9:Flow sheet of Ethylene Glycol production

 Major engineering problems of Ethylene Glycol production

 it has two common characteristic problems in regeneration plant that is fouling of equipment by iron
carbonate, Ca+2/Mg+2 salt deposits and cross contamination of Mono Ethylene Glycol (MEG) and
condensate contamination. MEG in condensate causes condensate specification problems, fouling of
condensate stabilization equipment and contamination of wastewater streams. Condensate in MEG
causes stripping effect due to condensate vaporization, lower operating temperature, higher MEG
purities, and contamination of wastewater streams from MEG Regeneration system and burping of
column due to condensate buildup.
 Another common problem is glycol losses due to carryover with dehydrated gas and which finally
accumulates in pipelines and causes corrosion. Other reasons of glycol losses are higher column
temperature, foaming, leaks at pump or pipe fittings, operated with excessive gas flow rates and
rapid changes in gas flow rates. Column Flooding occurred if feed glycol circulation rate exceeded
design limit and it does not allow proper separation of glycol and water separator and much glycol
losses through vent line.

VINYL ACETATE PRODUCTION (CH3COOCH=CH₂)

 Reactions of Vinyl Acetate production

 C₂H4 + CH3COOH + (1/2) O₂ + H₂O

 Side reaction: C2H4 +O2  2CO2 + 2H2O

 Uses of Vinyl Acetate

 Vinyl acetate monomer (VAM) is a significant intermediate used in the production of a wide range of
resins and polymers for paints & coatings, adhesives, glues & sealants, elastomers, textile finishes, paper
coatings, binders, films, and a myriad of other industrial and consumer applications.

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 Vinyl acetate is used to make other industrial chemicals. These chemicals are used mainly to make glues
for the packaging and building industries. They are also used to make paints, textiles, and paper.
 Vinyl acetate is also used as a coating in plastic films for food packaging and as a modifier of food
starch.

 Flow Sheet of Vinyl Acetate production: Figure:10

Figure 10: Flow sheet of Vinyl Acetate production

 Process description of Vinyl Acetate production

 As per figure 10, ethylene, acetic acid and air (oxygen and small amount of carbon dioxide) is
vaporized in evaporator.
 Vaporized feed mixture is inserted into reactor.
 Palladium, chloride catalyst is also added.
 After reaction, reaction mixture is collected from the bottom and sent into liquid-gas separator. Here,
Liquids are collected from the bottom of the separator and gases are come together from the top of
the column.
 Collected gases are further sent to flash drum, in which it is separated into carbon dioxide and
ethylene/oxygen.
 Mixture of ethylene/oxygen is recycled and added into evaporator, and carbon dioxide is drawn off
liquid is further separated into Acetic acid and crude vinyl acetate in flash drum. Acetic acid is
further recycled. Crude vinyl acetate is undergoing purification in distillation column to get pure
vinyl acetate.

ETHYLENE ACETIC ACID (CH3COOH)

 Properties of Acetic Acid
Mol. wt. 60.052
M.P. 16.6˚C
B.P. 118˚C

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Density 1.05 @ 20 ˚C
Solubility Soluble in water, alcohol & ether
Odour Pungent Vinegar Odour
Appearance Colorless liquid

 Uses of Acetic Acid

 Industrially, acetic acid is used in the preparation of metal acetates, used in some printing processes;
vinyl acetate, employed in the production of plastics; cellulose acetate,
 It is used in making photographic films and textiles; and volatile organic esters (such as ethyl and
butyl acetates), widely used as solvents.
 It is an important chemical reagent and industrial chemical that is used in the production of plastic
soft drink bottles. photographic film; and polyvinyl acetate for wood glue, as well as mar and fabrics.
 It is used in the production of vinyl acetate, cellulose acetate, acetyl chloride and solvent acetates.
 In households diluted acetic acid is often used as a cleaning agent.
 In the food industry acetic acid is used as an acidity regulator.
 Vinegar is typically 3-7% solution of acetic acid in water. Vinegar is mainly used as a Preservative in
food and in the pickling of vegetables.
 It is used in testing blood in clinical laboratory.
 It is used for the treatment of outer ear infections from the growth of fungus and bacteria

 Reactions of Acetic Acid production

Press.: 10-15 bar, Temp: 175˚C
CH3OH + CO -----------------------------------→ CH3COOH
 The process involves iodomethane as an intermediate, and occurs in three steps. A catalyst, metal
carbonyl, is needed for the carboxylation.
1. CH3OH + HI → CH3I + H2O
2. CH₂I + CO→CH3COI
3. CH, COI + H2O→CH3COOH + HI
 Raw materials: Methanol, Carbon monoxide gas, Rhodium, Hydrogen iodide, activator

 Process description of Acetic Acid production

 As per flow-chart, methanol is inserted from the top of carboxylation reactor and carbon monoxide is
bubbled out from bottom of reactor. The catalyst and activator is also added. Temperature of 170-
180˚C and pressure of 10-15 bar is maintained.
 This reactor provides excellent mass and heat transfer. In this reactor gas is sparged from the bottom
of the reactor.
 Design of the sparger controls the bubble size distribution in the column.
 The exhaust gas from the reactor is coming out from the top and introduced into gas scrubber where
gases coming out from purification section are also scrubbed using methanol and then recycle to
reactor.
 After reaction, acetic acid and other liquid transferred into flash drum, where unreacted catalyst is
separated out from the bottom and sent into reactor.
 Remaining reaction mixture is added into crude acetic acid column. Here, light end are vaporized in
column and send to light ends column where they are removed. Thereafter, water is removed from
acetic acid in dehydration column using methanol and steam.

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 After dehydration, liquid mixture from bottom of column is charged into acetic acid column where
acetic acid is obtained as product.
 Waste acid are removed using stripping operation. The gases came from dehydration and acetic acid
column are added into scrubber.

 Flow Sheet of Acetic Acid production: Figure:11

Carboxylation
Reactor

Methanol Acetic acid

Waste acid

Figure 11: Flow sheet of Acetic Acid production

 Major Engineering Problems of Acetic Acid production

 In this process, a large amount of water (about 14%) is needed to produce hydrogen in the reactor via
the water-gas shift reaction (CO + H₂O ⇌ CO₂ + H₂).
 Water and hydrogen are needed to react with precipitated Rh(III) and inactive [Rh4(CO)₂] to
regenerate the active Rh(I) catalyst. This large amount of water increases the amount of hydrogen
iodide, which is highly corrosive and leads to engineering problems.
 Further, removing a large amount of water from the acetic acid product is costly. Waste removal is
another problem, which is associated with this reaction.

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