PETROCHEMICALS

I.

Introduction

II.

Crude Oil Distillation

III.

Hydrocarbon Steam Cracking

IV.

Petrochemicals Production from Hydrocarbon Intermediates

1. Petrochemicals from Methane
1.1.

Direct Reaction of Methane

1.1.1. Carbon Disulfide

1.1.2. Hydrogen Cyanide
1.1.3. Chloromethanes
1.1.4. Synthesis Gas
1.1.4.a. Ammonia
1.1.4.b. Methanol
2. Petrochemicals from Ethylene
2.2. Vinyl Chloride

INTRODUCTION
The crude oil which is pumped out of the worlds oil fields is the result of
the slow decomposition of plant material in the absence of oxygen. As a
consequence, the products are dominated by hydrocarbons: a complex mixture
of mainly alkanes and cycloalkanes, with small amounts of alkenes, aromatic
compounds, compounds containing sulfur or nitrogen, as well as various
inorganic substances. It contains literally thousands of compounds, ranging
from low molecular gases to very large compounds with very high melting
points.
More than 90% of the petroleum produced is used for fuels for heating
and transportation. However, petroleum is also an extremely valuable source of
petrochemicals, which serve as raw materials for the manufacture of a wide
variety of plastics, synthetic fibers, paints and coatings, adhesives, piping, and
other products of modern society. 90% of the production of synthetic organic
chemicals comes from crude oil and natural gas sources.
After desalting to remove acids and salts, the crude oil is transferred to a
distillation

tower

where

various

fractions

are

separated

by

fractional

distillation.

CRUDE OIL DISTILLATION

Crude oil distillation is the front end of every refinery, regardless of size
or overall configuration. It has a unique function that affects all the refining
processes downstream of it.
Crude distillation separates raw crude oil feed (usually a mixture of
crude oils) into a number of intermediate refinery streams (known as crude
fractions or cuts), characterized by their boiling ranges (a measure of their
volatility, or propensity to evaporate). Each fraction leaving the crude
distillation unit is defined by a unique boiling point range and is made up of
hundreds or thousands of distinct hydrocarbon compounds, all of which have
boiling points within the cut range. These fractions include (in order of

increasing boiling range) light gases, naphthas, gasoline, kerosaene, Diesel oils,
lubricating oils, heavy oils and residual oil. Each goes to a different refinery
process for further processing.

Each crude oil fractions will undergone various processes to be converted

into various petrochemicals as shown in the next figure.

HYDROCARBON STEAM CRACKING FOR PETROCHEMICALS

In

industrial

processes,

hydrocarbons

are

contacted

with

H2O,

depending upon the desired effect. When hydrocarbon vapors at very high
pressures are contacted with water, water which has a very high latent heat of
vaporization quenches the hydrocarbon vapors and transforms into steam. In
such an operation, chemical transformations would not be dominant and
energy lost from the hydrocarbons would be gained by water to generate steam.
The quenching process refers to direct contact heat transfer operations
and therefore has maximum energy transfer efficiency. This is due to the fact
that no heat transfer medium is used that would accompany heat losses. The
steam cracking of hydrocarbons is an anti-quenching operation, and will
involve the participation of water molecule in reactions in addition to the
cracking of the hydrocarbon on their own.
Since steam and the hydrocarbons react in the vapor phase the reaction
products can be formed very fast. Therefore cracking of the hydrocarbons on
their own as well as by steam in principle is very effective. When steam
cracking is carried out, in addition to the energy supplied by the direct contact
of steam with the hydrocarbons, steam also takes part in the reaction to
produce wider choices of hydrocarbon distribution along with the generation of
H2 and CO.
Reaction:
CxHy + H2O + O2

C2H4 + C2H6 + C2H2 + H2 + CO + CO2 + CH4 + C3H6 + C3H8

+ C4H10 + C4H8 + C6H6 + C+ Heavy oils

Steam Cracking of Naphtha

Naphtha is mixed with superheated steam and fed to a furnace fuel gas +
fuel oil as fuels to generate heat. The superheated steam is generated from the
furnace itself using heat recovery boiler concept. The C2-C4 saturates are fed
to a separate furnace fed with fuel gas + fuel oil as fuels to generate heat.
In the furnace, apart from the steam cracking, steam is also generated.
After pyrolysis reaction, the products from the furnace are sent to
another heat recovery steam boiler to cool the product streams (from about 700
800 C) and generate steam from water.
After this operation, the product vapors enter a scrubber that is fed with
gas oil as absorbent. The gas oil removes solids and heavy hydrocarbons.

Separate set of waste heat recovery boiler and scrubbers are used for the
LPG furnace and Naphtha steam cracking furnaces
After scrubbing, both product gases from the scrubbers are mixed and
fed to a compressor. The compressor increases the system pressure to 35 atm.
The compressed vapor is fed to a phase separation that separates the
feed into two stream namely the vapor phase stream and liquid phase stream.
The vapor phase stream consists of H2, CO, CO2 C1-C3+ components in
excess. The liquid phase stream consists of C3 and C4 compounds in excess.
Subsequently, the vapor phase and liquid phase streams are subjected to
separate processing.
Gas stream processing:
CO2 in the vapor phase stream is removed using NaOH scrubber.
Subsequently gas is dried to consist of only H2, CO, C1-C3 components only.
This stream is then sent to a demethanizer which separates tail gas (CO + H2 +
CH4) from a mixture of C1-C3 components. The C2-C3 components enter a
dethanizer which separates C2 from C3 components.
Here C2 components refer to all kinds of C2s namely ethylene, acetylene
etc. Similarly, C3 the excess of propylene, and propane. The C2 components
then enter a C2 splitter which separates ethane from ethylene and acetylene.
The ethylene and acetylene gas mixture is fed to absorption unit which is
fed with an extracting solvent (such as N-methylpyrrolidinone) to extract
Acetylene from a mixture of acetylene and ethylene.
The extractant then goes to a stripper that generates acetylene by
stripping. The regenerated solvent is fed back to the absorber.
The ethylene stream is fed to a topping and tailing still to obtain high
purity ethylene and a mixture of ethylene and acetylene as the top and bottom
products. The mixture of ethylene and acetylene is sent back to the C2 splitter
unit as its composition matches to that of the C2 splitter feed.
Liquid stream processing:
The liquid stream consists of C3,C4, aromatics and other heavy oil
components is fed to a NaOH scrubber to remove CO2

Eventually it is fed to a pre-fractionator. The pre-fractionator separates

lighter components from the heavy components. The lighter components are
mixed with the vapor phase stream and sent to the NaOH vapor phase
scrubber unit.
The pre-fractionator bottom product is mixed with the deethanizer
bottom product. Eventually the liquid mixture enters a debutanizer that
separates C3, C4 components from aromatics and fuel oil mixture. The bottom
product eventually enters a distillation tower that separates aromatics and fuel
oil as top and bottom products respectively.
The top product then enters a depropanizer that separates C3s from C4
components. The C4 components then enter an extractive distillation unit that
separates butane + butylene from butadiene. The extractive distillation unit
consists of a distillation column coupled to a solvent stripper. The solvent
stripper produces butadiene and pure solvent which is sent to the distillation
column.
The C3 components enter a C3 splitter that separates propylene from
propane + butane mixture. The saturates mixture is recycled to the saturates
cracking furnace as a feed stream.

PETROCHEMICALS FROM METHANE

Methane is the first member of the alkane series. It is the main
component of natural gas and also a by-product in all gas streams from
processing crude oils. It is a colorless, odorless gas that is lighter than air.
As a chemical compound, methane is not very reactive. It does not react
with acids or bases under normal conditions. It reacts, however, with a limited
number of reagents such as oxygen and chlorine under specific conditions. For
example, it is partially oxidized with a limited amount of oxygen to a carbon
monoxide-hydrogen mixture at high temperatures in presence of a catalyst. The
mixture (synthesis gas) is an important building block for many chemicals.

As mentioned, methane is a one-carbon paraffinic hydrocarbon that is

not very reactive under normal conditions. Only a few chemicals can be
produced

directly

from

methane

under

relatively

severe

conditions.

Chlorination of methane is only possible by thermal or photochemical

initiation. Methane can be partially oxidized with a limited amount of oxygen or
in presence of steam to a synthesis gas mixture.
Many chemicals can be produced from methane via the more reactive
synthesis gas mixture. Synthesis gas is the precursor for two major chemicals,
ammonia and methanol. Both compounds are the hosts for many important
petrochemical products.

Petrochemicals based on Direct Reactions of Methane

A few chemicals are based on the direct reaction of methane with other
reagents. These are carbon disulfide, hydrogen cyanide, chloromethanes, and
synthesis gas mixture.
CARBON DISULFIDE
Physical Properties
Molecular Formula

CS2

Molar Mass

76.14g/mol

Appearance

Colorless liquid

Density

1.266g/cm3

Melting Point

-111.61C

Boiling Point

46.24C

Conversion Process
Methane
temperatures

reacts
to

with

produce

sulfur

carbon

at

disulfide.

high
The

reaction is endothermic, and an activation energy of

approximately 160 KJ is required. Activated alumina
or clay is used as the catalyst at approximately
675C and 2 atmospheres. The process starts by
vaporizing pure sulfur, mixing it with methane, and
passing the mixture over the alumina catalyst. The reaction could be
represented as:

CH4(g) + 2S2(g)

CS2(g) + 2H2S(g)

H298 = +150 KJ/mol

Hydrogen sulfide, a co-product, is used to recover sulfur by the Claus

reaction. A CS2 yield of 8590% based on methane is anticipated.
Uses of Carbon Disulfide

Carbon disulfide is primarily used to produce rayon and cellophane

(regenerated cellulose). CS2 is also used to produce carbon tetrachloride.

HYDROGEN CYANIDE (HCN)

Hydrogen cyanide (hydrocyanic acid) is a
colorless liquid that is miscible with water,
producing a weakly acidic solution.
It is a highly toxic compound, but a very
useful chemical intermediate with high reactivity.
It is used in the synthesis of acrylonitrile and
adiponitrile, which are important monomers for
plastic and synthetic fiber production.
Physical Properties
Molecular Formula

CHN

Molar Mass

27.03g/mol

Appearance

Very pale, blue, transparent liquid or

colorless gas

Density

0.687g/mL

Melting Point

-14 to -12 C

Boiling Point

25.6 to 26.6 C

Conversion Process
Hydrogen cyanide is produced via the Andrussaw process using
ammonia and methane in presence of air. The reaction is exothermic, and the
released heat is used to supplement the required catalyst-bed energy:

2CH4 + 2NH3 + 3O2

2HCN + 6H2O

A platinum-rhodium alloy is used as a catalyst at 1100C. Approximately

equal amounts of ammonia and methane with 75 vol % air are introduced to
the preheated reactor. The catalyst has several layers of wire gauze with a
special mesh size (approximately 100 mesh).

The Degussa process, on the other hand, reacts ammonia with methane
in absence of air using a platinum, aluminum-ruthenium alloy as a catalyst at
approximately 1200C. The reaction produces hydrogen cyanide and hydrogen,
and the yield is over 90%. The reaction is endothermic and requires 251
KJ/mol.

CH4 + NH3 + 251 KJ

HCN + 3H2

Uses of Hydrogen Cyanide

Hydrogen cyanide is a reactant in the production of acrylonitrile, methyl
methacrylates (from acetone), adiponitrile, and sodium cyanide.
It is also used to make oxamide, a long-lived fertilizer that releases
nitrogen steadily over the vegetation period.
CHLOROMETHANES
The successive substitution of methane hydrogen with chlorine produces
a mixture of four chloromethanes:
Monochloromethane (methyl chloride, CH3Cl)
Dichloromethane (methylene chloride, CH2Cl2)
Trichloromethane (chloroform, CHCl3)
Tetrachloromethane (carbon tetrachloride, CCl4)
Methane is the most difficult alkane to chlorinate. The reaction is
initiated by chlorine free radicals obtained via the application of heat (thermal)
or light (hv). Thermal chlorination (more widely used industrially) occurs at
approximately 350370C and atmospheric pressure. A typical product
distribution for a CH4/Cl2 feed ratio of 1.7 is: mono- (58.7%), di- (29.3%) tri(9.7%) and tetra- (2.3%) chloromethanes.
Reactions:

Chloromethane Production
Methane and Cl2 are mixed and sent to a furnace The furnace has a
jacket or shell and tube system to accommodate feed pre-heating to desired
furnace inlet temperature (about 280 300 C). To control temperature, N2 is
used as a diluent at times. Depending on the product distribution desired, the
CH4/Cl2 ratio is chosen. The product gases enter an integrated heat exchanger

that receives separated CH4 (or a mixture of CH4 + N2) and gets cooled from
the furnace exit temperature (about 400 C).
Eventually, the mixture enters an absorber where water is used as an
absorbent and water absorbs the HCl to produce 32 % HCl. The trace amounts
of HCl in the vapor phase are removed in a neutralizer fed with NaOH. The gas
eventually is compressed and sent to a partial condenser followed with a phase
separator. The phase separator produces two streams namely a liquid stream
consisting of the chlorides and the unreacted CH4/N2.
The gaseous product enters a dryer to remove H2O from the vapour
stream using 98% H2SO4 as the absorbent for water from the vapour. The
chloromethanes enter a distillation sequence. The distillation sequence
consists of columns that sequentially separate CH3Cl, CH2Cl2, CHCl3 and
CCl4.
Uses of Chloromethanes
The major use of methyl chloride is to produce silicon polymers. Other
uses include the synthesis of tetramethyl lead as a gasoline octane booster, a
methylating agent in methyl cellulose production, a solvent, and a refrigerant.
Methylene chloride has a wide variety of markets. One major use is a
paint remover. It is also used as a degreasing solvent, a blowing agent for
polyurethane foams, and a solvent for cellulose acetate.
Chloroform

is

mainly

used

to

produce

chlorodifluoromethane

(Fluorocarbon 22) by the reaction with hydrogen fluoride:

CHCl3 + 2HF

CHClF2Cl + 2HCl

This compound is used as a refrigerant and as an aerosol propellent. It is

also used to synthesize tetrafluoroethylene, which is polymerized to a heat
resistant polymer (Teflon):

2CHClF2

CF2=CF2 + 2HCl

Carbon tetrachloride is used to produce chlorofluorocarbons by the reaction

with hydrogen fluoride using an antimony pentachloride (SbCl5) catalyst:

CCl4 + HF r CCl3F + HCl

CCl4 + 2HF r CCl2F2 + 2HCl
The formed mixture is composed of trichlorofluoromethane (Freon-11)
and dichlorodifluoromethane (Freon-12). These compounds are used as
aerosols and as refrigerants.

SYNTHESIS GAS
Methane is almost as important as ethene, for not only is it the major
component of natural gas, but also as a feedstock for what is known as
synthesis gas, a mixture of hydrogen, carbon monoxide and carbon dioxide. It
is produced by the catalyzed, high-pressure, high temperature reaction of
steam with methane, as shown:

The typical composition of synthesis gas from the process varies, but is
typically 50-60% hydrogen, 40-50% carbon monoxide and 2-4% carbon
dioxide. If pure CO or H2 is required, then simple post-processing is used:
hydrogen the CO is oxidized with more steam to CO2, which is then
removed by absorption
carbon

monoxide

the

CO

is

absorbed

into

solution

of

copper/ammonia complex, then liberated by heat.

Many chemicals are produced from synthesis gas. This is a consequence
of the high reactivity associated with hydrogen and carbon monoxide gases, the
main constituents of synthesis gas.
Synthesis gas is also an important building block for aldehydes from
olefins. The catalytic hydroformylation reaction (Oxo reaction) is used with
many olefins to produce aldehydes and alcohols of commercial importance.

The two major chemicals based on synthesis gas are ammonia and
methanol. Each compound is a precursor for many other chemicals. From
ammonia, urea, nitric acid, hydrazine, acrylonitrile, methylamines and many
other minor chemicals are produced. Each of these chemicals is also a
precursor of more chemicals.
Methanol, the second major product from synthesis gas, is a unique
compound of high chemical reactivity as well as good fuel properties. It is a
building block for many reactive compounds such as formaldehyde, acetic acid,
and methylamine. It also offers an alternative way to produce hydrocarbons in
the gasoline range (Mobil to gasoline MTG process). It may prove to be a
competitive source for producing light olefins in the future.
Manufacturing of Synthesis Gas

Most of synthesis gas is produced from natural gas. However it can also
be produced using crude oil by means of the fractions of naphtha from crude
oil distillation.
The naphtha is heated to form a vapor, mixed with steam and passed
through tubes, heated at 750 K and packed with a catalyst, nickel supported
on a mixture of aluminium and magnesium oxides. The main product is
methane together with oxides of carbon.
Whichever way the methane is obtained, it will contain some organic
sulfur compounds and hydrogen sulfide, both of which must be removed.
Otherwise, they will poison the catalyst needed in the manufacture of synthesis
gas. In the desulfurisation unit, the organic sulfur compounds are often first
converted into hydrogen sulfide, prior to reaction with zinc oxide. The feedstock
is mixed with hydrogen and passed over a catalyst of mixed oxides of cobalt
and molybdenum on an inert support (a specially treated alumina) at 700 K.

Then the gases are passed over zinc oxide at ca 700 K and hydrogen
sulfide is removed:

Primary steam reforming converts methane and steam to synthesis

gas, a mixture of carbon monoxide and hydrogen

High temperatures and low pressures favor the formation of the products
(Le Chatelier's Principle). In practice, the reactants are passed over a catalyst of
nickel, finely divided on the surface of a calcium oxide/aluminium oxide
support

contained in vertical nickel alloy tubes. The tubes, up to 350 in parallel, are
heated in a furnace above 1000 K and under a pressure of 30 atm. This is an
example of a tubular reactor.
Secondary steam reforming reacts oxygen from the air with some of
the hydrogen present and the resulting mixture is passed over a nickel
catalyst. The steam and heat produced from the combustion reforms most of
the residual methane.
Among the key reactions are:

The Shift Reaction

This process converts carbon monoxide to carbon dioxide, while
generating more hydrogen. It takes place in two stages. In the first, the high
temperature shift reaction, the gas is mixed with steam and passed over an
iron/chromium(III) oxide catalyst at 700 K in a fixed bed reactor. This
decreases
the

carbon
monoxide

concentration from 11%:

In the second stage, the low temperature shift reaction, the mixture of
gases is passed over a copper-zinc catalyst at 500 K. The carbon monoxide
concentration is further reduced to 0.2%.
The reaction is done in two stages for several reasons. The reaction is
exothermic. However, at high temperature, the exit concentration of carbon
monoxide is still quite high, due to equilibrium control. The copper catalyst

used in the low temperature stage is very sensitive to high temperatures, and
could not operate effectively in the high temperature stage.
The gas mixture now contains about 18% carbon dioxide which is
removed by scrubbing the gas with a solution of a base. The carbon dioxide is
released on heating the solution in the carbon dioxide stripper.
The last traces of oxides of carbon are removed by passing the gases over
a nickel catalyst at 600 K. This process is known as methanation. A gas is
obtained of typical composition: 74% hydrogen, 25% nitrogen, 1%methane,
together with some argon.

AMMONIA
Ammonia is one of the most important inorganic
chemicals, exceeded only by sulfuric acid and lime.
This colorless gas has an irritating od or, and is very
soluble in water, forming a weakly basic solution.
Ammonia could be easily liquefied under pressure
(liquid ammonia), and it is an important refrigerant.
Anhydrous

ammonia

is

fertilizer

by

direct

application to the soil. Ammonia is obtained by the

reaction of hydrogen and atmospheric nitrogen, the
synthesis gas for ammonia.
Physical Properties
Molecular Formula

NH3

Molar Mass

17.031g/mol

Appearance

Colorless gas

Density

0.73kg.m3 @15C

Melting Point

-77.73C

Boiling Point

-33.34C

Ammonia Production

(1) Synthesis gas, air and steam are heated by a fired heater using
synthetic natural gas as a fuel. These heated gases are introduced into (2) the
reformer where the methane is converted to carbon monoxide, carbon dioxide
and hydrogen. The exit gases from the reformer enter (3) shift conversion where
the carbon monoxide and water react to form hydrogen and carbon dioxide. In
the (4) carbon dioxide removal vessel, an absorption process is used to remove
the carbon dioxide. The stream from the carbon dioxide removal system still
contains small amounts of carbon monoxide and carbon dioxide so it is sent
through (5) the methanator where they react with hydrogen to form methane. A
gas is obtained of typical composition: 74% hydrogen, 25% nitrogen, 1%
methane, together with some argon. Before the stream can be introduced to the
ammonia synthesis loop, the (6) dryers and cold box remove water and
methane along with excess nitrogen so that the hydrogen and nitrogen ratio

equals three to one. (7) The synthetic gas compressor takes the fresh feed from
the cold box plus the ammonia loop recycle stream and compresses it to 2500
psig. As the stream travels through (8) the radial flow ammonia converter, the
hydrogen and nitrogen react to form ammonia. (9) The ammonia recovery unit
then cools the stream and the liquid ammonia is sent to the 30,000 ton
ammonia tank where it is stored until it is sold. The recycle gases are then
returned to the synthetic gas compressor for reintroduction into the ammonia
converter.
Uses of Ammonia
The major end use of ammonia is the fertilizer field for the production of
urea, ammonium nitrate and ammonium phosphate, and sulfate. Anhydrous
ammonia could be directly applied to the soil as a fertilizer. Urea is gaining
wide acceptance as a slow-acting fertilizer. Ammonia is the precursor for many
other

chemicals

such

as

nitric

acid,

hydrazine,

acrylonitrile,

and

hexamethylenediamine. Ammonia, having three hydrogen atoms per molecule,

may be viewed as an energy source. It has been proposed that anhydrous
liquid ammonia may be used as a clean fuel for the automotive industry.
METHYL ALCOHOL
Methyl

alcohol

(methanol)

is

the

first

member of the aliphatic alcohol family. Methanol

was

originally

produced

by

the

destructive

distillation of wood (wood alcohol) for charcoal

production. Currently, it is mainly produced from
synthesis gas.
Methanol is one of the largest volume
chemicals produced in the world. Methanol consumption can be separated into
three end use categories chemical feedstock, methyl fuels, and miscellaneous
uses. About 71% of the current global consumption of methanol is in the

production of formaldehyde, acetic acid, methyl methacrylate, and dimethyl

terephthalate. The global methanol industry has experienced very fundamental
and structural changes and has settled down considerably.
As a chemical compound, methanol is highly polar, and hydrogen
bonding is evidenced by its relatively high boiling temperature (65C), its high
heat of vaporization, and its low volatility. Due to the high oxygen content of
methanol (50 wt%), it is being considered as a gasoline blending compound to
reduce carbon monoxide and hydrocarbon emissions in automobile exhaust
gases. It was also tested for blending with gasolines due to its high octane
(RON = 112).
Physical Properties
Molecular Formula

CH4O

Molar Mass

32.04g/mol

Appearance

Colorless liquid

Density

0.7918g/cm3

Melting Point

97.6 C

Boiling Point

64.7 C

Production of Methanol

The major reactions take place during methanol synthesis converter can
be described by following equilibrium reactions:

The first two reactions are exothermic and proceed with reduction in
volume. In order to achieve a maximum yield of methanol and a maximum
conversion of synthesis gas, the process must be effected at low temperature
and high pressure.
After cooling to ambient temperature, the synthesis gas is compressed to
5.0-10.0 MPa and is added to the synthesis loop which comprises of following
items circulator, converters, heat exchanger, heat recovery exchanger, cooler,
and separator. The catalyst used in methanol synthesis must be very selective
towards the methanol reaction, i.e. give a reaction rate for methanol production
which is faster. And lastly, the obtained methanol is dilled to obtain purer
methanol.
Applications

PETROCHEMICALS FROM ETHYLENE

Ethylene is sometimes known as the king of petrochemicals because more
commercial chemicals are produced from ethylene than from any other
intermediate. This unique position of ethylene among other hydrocarbon
intermediates is due to some favorable properties inherent in the ethylene
molecule as well as to technical and economical factors. These could be
summarized in the following:
o Simple structure with high reactivity.
o Relatively inexpensive compound.
o Easily produced from any hydrocarbon source through steam cracking
and in high yields.
o Less

by-products

generated

from

ethylene

reactions

with

other

compounds than from other olefins.

Ethylene reacts by addition to many inexpensive reagents such as water,
chlorine, hydrogen chloride, and oxygen to produce valuable chemicals. It can
be initiated by free radicals or by coordination catalysts to produce
polyethylene, the largest-volume thermoplastic polymer. It can also be
copolymerized with other olefins producing polymers with improved properties.
Below is the summary the important derivatives of ethylene.

Applications

VINYL CHLORIDE
Vinyl chloride is produced in a two-step
process from ethylene:
Ethylene first reacts with Chlorine to
produce Ethylene dichloride
The purified Ethylene dichloride
undergoes selecti ve cracking to form
vinyl chloride
Physical Properties
Molecular Formula

C2H3Cl

Molar Mass

62.498g/mol

Density

911.00 kg/m3

Melting Point

-153.8C

Boiling Point

-13.4C

Ethylene Dichloride
Reactions:

o C2H4 + Cl2

C2H4Cl2

o Undesired products: Propylene dichloride and Polychloroethanes

o Reaction occurs in a liquid phase reactor with ethylene dichloride serving
as the liquid medium and reactants reacting the liquid phase
o Catalyst is FeCl3 or Ethylene dibromide

Ethylene Dichloride Production

C2H4 and Cl2 are mixed and sent to the liquid phase reactor. Here, the
feed mixture bubbles through the ethylene dichloride product medium. Reactor
operating conditions are 50C and 1.5 2 atm.

The reaction is exothermic. Therefore, energy is removed using either

cooling jacket or external heat exchanger. To facilitate better conversion,
circulating reactor designs are used. FeCl3 traces are also added to serve as
catalyst
The vapor products are cooled to produce two products namely a vapor
product and a liquid product. The liquid product is partially recycled back to
the reactor to maintain the liquid medium concentration.
The vapor product is sent to a refrigeration unit for further cooling which
will further extract ethylene dichloride to liquid phase and makes the vapor
phase bereft of the product.
The liquid product is crude ethylene dichloride with traces of HCl.
Therefore, acid wash is carried out first with dilute NaOH to obtain crude
ethylene dichloride. A settling tank is allowed to separate the spent NaOH
solution and crude C2H4Cl2 (as well liquid). The crude ethylene dichloride
eventually enters a distillation column that separates the ethylene dichloride
from the other heavy end products.
The vapour phase stream is sent to a dilute NaOH solution to remove
HCl and produce the spent NaOH solution. The off gases consist of H2, CH4,
C2H4 and C2H6.
Vinyl Chloride Production
Reaction
o C2H4Cl2

CH2CHCl + HCl

o Charcoal is used as the catalyst

o The reaction is a reversible gas phase reaction

Ethylene dichloride is initially vaporized using a heat exchanger fed with

process steam. Ethylene vapors then enter a dryer that removes traces of water
molecules. After drying, the vapors enter a pyrolysis furnace operated at 4 atm
and 500 C. The furnace is similar to a shell and tube arrangement with the
gases entering the tube side and hot flue gas goes past the tubes in the shell
side.
The product vapors eventually enter a quenching tower in which cold
ethylene dichloride is used to quench the product gases and cool them. The
gases from the quench tower then enter a partial condenser which produces
HCl as a gas and the liquid stream consisting of vinyl chloride, unreacted
ethylene dichloride and polychlorides.
The liquid stream from the quench tower as well as the condenser is fed
to the vinyl still which produces the vinyl chloride product. The product is
stabilized using a stabilizer as vinyl chloride is highly reactive without
stabilizer.
The bottom product from the vinyl still is fed to a distillation column
which separates the ethylene dichloride from the polychlorides. The ethylene
dichloride vapors are recycled back to the cracking furnace and the ethylene

dichloride liquid is sent to the quenching tower to serve as the quenching

liquid.

REFERENCES
Boardman Energy Partners, LLC (2014). Facts About Natural Gas. Date
Retrieved: July 17, 2014 from http://benergypartners.com/Facts_About
_Natural_Gas.html
Dakota Gasification Company. Ammonia Plant. Date Retrieved: July 17, 2014
from http://www.dakotagas.com/Gasification/Ammonia_Plant/index.html
Ammonia. Date Retrieved: July 17, 2014 from http://www.essentialchemical
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