SATHYABAMA

INSTITUTE OF SCIENCE AND TECHNOLOGY

DEPARTMENT OF CHEMICAL ENGINEERING

COURSE MATERIAL

PETROLEUM AND PETRO CHEMICAL TECHNOLOGY UNIT IV SCH1308

UNIT IV CHEMICALS FROM METHANE AND ETHANE

1.0 Petrochemicals: Overview

1.1Introduction
In this lecture, we present a brief overview of petrochemical technologies and discuss upon the
general topology of the petrochemical process technologies.
Petrochemicals refers to all those compounds that can be derived from the petroleum
refinery products
Typical feedstocks to petrochemical processes include
C1 Compounds: Methane & Synthesis gas
C2 Compounds: Ethylene and Acetylene
C3 Compounds: Propylene
C4 Compounds: Butanes and Butenes
Aromatic Compounds: Benzene
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.
Definition : These are the chemicals that are made from petroleum and natural gas.
Petroleum and natural gas are made up of hydrocarbon molecules, which comprises of one
or more carbon atoms, to which hydrogen atoms are attached.
About 5 % of the oil and gas consumed each year is needed to make all the petrochemical
products. Petrochemicals play an important role on our food, clothing, shelter and leisure.
Because of low cost and easy availability, oil and natural gas are considered to be the main
sources of raw materials for most petrochemicals.
Classification: Petrochemicals can be broadly classified into three categories-

a. Light Petrochemicals: These are mainly used as bottled fuel and raw materials for other
organic chemicals. The lightest of these -- methane, ethane and ethylene -- are gaseous at
room temperature.The next lightest fractions comprise petroleum ether and light naphtha
with boiling points between 80 and 190 degrees Fahrenheit.

b. Medium Petrochemicals: Hydrocarbons with 6 – 12 carbon atoms are called

"gasoline", which are mainly used as automobile fuels. Octane, with eight carbons,
is a particularly good automobile fuel, and is considered to be of high quality.
Kerosene contains 12 to 15 carbons and is used in aviation fuels, and also as
solvents for heating and lighting.

c. Heavy Petrochemicals: These can be generally categorized as diesel oil,

heating oil and lubricating oil for engines and machinery. They contain around 15
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and 18 carbon atoms with boiling points between 570 and 750 degrees Fahrenheit.
The heaviest fractions of all are called "bitumens" and are used to surface roads or
for waterproofing.

Bitumens can also be broken down into lighter hydrocarbons using a process
called "cracking."

1.2 Process Topology

Reactors: Reactors are the most important units in petrochemical processes. Petrochemicals
are manufactured by following simple reactions using relatively purer feedstocks. Therefore,
reaction chemistry for petrochemicals manufacture is very well established from significant
amount of research in this field. Essentially all petrochemical processes need to heavily
depend upon chemical transformation to first product the purification.
Separation: With distillation being the most important unit operation to separate the
unreacted feed and generated petrochemical product, the separation processes also play a
major role in the process flow sheet. Where multiple series parallel reactions are involved,
the separation process assumes a distillation sequence to separate all products from the feed.
A characteristic feed recycle will be also existent in the process topology. Apart from this,
other separation technologies used in petrochemical processing units include phase
separators, gravity settling units and absorption columns. Therefore, the underlying physical
principle behind all these separation technologies is well exploited to achieve the desired
separation.
Dependence on Reaction pathway: A petrochemical can be produced in several ways from
the same feedstock. This is based on the research conducted in the process chemistry. For
instance, phenol can be produced using the following pathways
o Peroxidation of Cumene followed by hydrolysis of the peroxide
o Two stage oxidation of Toluene
o Chlorination of Benzene and hydrolysis of chloro-benzene
o Direct oxidation of Benzene
We can observe that in the above reaction schemes, there are two reaction pathways for
phenol from benzene i.e., either chlorination of benzene or oxidation of benzene. Therefore,
choosing the most appropriate technology for production is a trivial task.
Complexity in pathway: In the above Cumene example case, it is interesting to note that
toluene hydrodealkylation produces benzene which can be used to produce phenol.
Therefore, fundamentally toluene is required for the generation of various petrochemicals
such as benzene and phenol. In other words, there is no hard and fast rule to say that a
petrochemical is manufactured using a suggested route or a suggested intermediate

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petrochemical. Intermediate petrochemicals play a greater role in consolidating the

manufacture of other downstream petrochemicals.

1.3 Manufacture of Methanol from Synthesis Gas

Introduction
Synthesis gas is H2 + CO
When synthesis gas is subjected to high pressure and moderate temperature conditions, it
converts to methanol.
Followed by this, the methanol is separated using a series of phase separators and
distillation columns.
The process technology is relatively simple

Reactions

Desired: CO + 2H2 CH3OH

Side reactions: CO + 3H2 CH4 + H2O

2CO + 2H2 CH4 + CO2
All above reactions are exothermic

Undesired reaction: zCO + aH2 alchohols + hydrocarbons
Catalyst: Mixed catalyst made of oxides of Zn, Cr, Mn, Al.

Process Technology

Figure: Flow sheet of manufacture of Methanol from Synthesis Gas

H2 and CO adjusted to molar ratio of 2.25

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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 oC

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.

Methane and synthesis gas are important petrochemical feedstock for manufacture of
a large number of chemicals, which are used directly or as intermediates, many of these
products are number of which are finding use in plastic, synthetic fiber, rubber,
pharmaceutical and other industries. ‘Synthesis gas’ is commonly used to describe two basic
gas mixtures - synthesis gas containing CO, hydrogen and synthesis gas containing
hydrogen and nitrogen for the production of ammonia. Major requirements of synthesis gas
in world scale petrochemical are given.
Some of the emerging technologies in utilization of synthesis gas and methane for the
production of petrochemicals, are Fischer-Tropsch synthesis, oxidative coupling of methane
with chlorine to yield ethane and ethylene, methanol to olefin technology (MTO). Fischer-
Tropsch synthesis is being studied in great detail world over and it is promising to be a
future technology for manufacture of olefins from synthesis gas. CO that can be separated

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from synthesis gas either by cryogenic or by pressure swing adsorption is a promising

feedstock for production of a variety of products. Product profile of methane, synthesis gas
and CO based building blocks are given in Figure BELOW

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Figure: Methane, Synthesis Gas and CO

Building Blocks
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1.4 SYNTHESIS GAS

Methane and synthesis gas are important petrochemical feedstock for the manufacture of a large
number of chemicals, which are used directly or as intermediates, a number of which are finding
use in plastic, synthetic fiber, rubber, pharmaceutical and other industries. ‘Synthesis gas’ is
commonly used to describe two basic gas mixtures - synthesis gas containing CO, hydrogen and
synthesis gas containing hydrogen and nitrogen for the production of ammonia.
Petrochemical derivatives based on synthesis gas and carbon monoxide have experienced steady
growth due to large scale utilization of methanol and development of a carbonylation process for
acetic acid and Oxo synthesis process for detergents, plasticizers, and alcohols. Recent market
studies show that there will be a dramatic increase in demand of CO and syngas derivatives .
Methanol is the largest consumer of synthesis gas. The reformed gas is to meet certain
requirements with regard to its composition. It is characterized by the stoichiometric conversion
factor, which differs from case to case

1.5 RAW MATERIALS FOR SYNTHESIS GAS

Various raw materials for synthesis gas production are natural gas, refinery gases, naphtha, fuel
oil/residual heavy hydrocarbons and coal. Although coal was earlier used for production of
synthesis gas, it has now been replaced by petroleum fractions and natural gas. Petrocoke is the
emerging source for Synthesis gas. Coal is again getting importance alone are with combination of
petroleum coke. Various Routes for Synthesis gas and Ammonia and Methanol manufacture is
shown in Figure. Reactions in the manufacture of synthesis gas by Steam reforming and Partial
oxidation in Table

Process Technology
Various synthesis gas production technologies are steam methane reforming, naphtha reforming,
auto-thermal reforming, oxygen secondary reforming, and partial oxidation of heavy
hydrocarbons, petroleum coke and coal.
Various steps involved in synthesis gas production through steam reforming are:

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• Desulphurization of gas
• Steam reforming and compression

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• Separation of CO2
Various available synthesis gas generation schemes are:
• Conventional steam reforming
• Partial oxidation
• Combined reforming
• Parallel reforming
• Gas heated reforming

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Various Routes for Synthesis gas and Ammonia and Methanol

manufacture

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Reactions in the manufacture of synthesis gas by Steam reforming and Partial

oxidation
Process steps Reaction Process Condition
Desulphurisat
ion: 1st Stage C2H5SH +H2 H2S + C2H6 Al-Co-Mo
First Stage C6H5SH + H2 H2S + C6H6 Al-Ni-Mo
C4H4SH + 3H2 H2S + C4H9 Catalyst
CS2 +4H2 2H2S + CH4 350-400 oC
COS + H2 H2S + CO
2nd Stage CH3SC2H5 + H2 H2S + CH4 + C2H4 Zinc oxide
Second Stage absorbent
H2S + ZnOZnS + H2O
200-500 0C
Steam CnHm+1/4(4n-m)H2O1/8(4n+m)CH4 + Nickel catalyst 800
reforming two 1/8(4n-m)CO2 o
C
stages CH4 + H2O  CO + 3H2 Endothermic
CO + H2O  CO2 + H2 reaction
Partial CnHm+ [(2n+m)/4 ]O2 nCO + m/2 H2O Exothermic
Oxidation CnHm + nH2O nCO + (n+m/2) H2 reaction

2CO C + CO2
CO + H2 C + H2O

1.6 METHANOL
Methanol was first obtained by Robert Boylein in the year 1661 through rectification of crude
wood vinegar over milk of lime and was named adiaphorous spiritusliglorum. The term methyl
was introduced in chemistry in 1835. 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.

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1.7 METHANOL PROCESS TECHNOLOGY

From the early 1800s until 1920s, the distillation of wood to make wood alcohol was the source of
Methanol. The most common industrially favored method for the production of methanol was first
developed by BASF in 1923 in Germany from synthesis gas utilising high pressure process using
zinc-chromic oxide catalyst. However, due to high capital and compression energy costs
compounded by poor catalyst activity, high-pressure process was rendered obsolete when ICI in
the year 1966 introduced a low-pressure version of the process at 5-10 MPa and 210-270 oC, with
a new copper-zinc oxide based catalyst of high selectivity and stability.

Process steps involved in the production of methanol are:

• Production of synthesis gas using steam reforming or partial oxidation
• Synthesis of methanol
• High-pressure process (25 – 30 MPa)
• Medium pressure (10-25 MPa) process
• Low-pressure process (5-10 MPa)
Figure BELOW illustrate the production of methanol from steam reforming of natural gas and
naphtha.

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Figure : Methanol from steam reforming of Natural gas and Naphtha

The major reactions take place during methanol synthesis converter can be described by following
equilibrium reactions:
CO + 2 H2 CH3OH ΔH298 0K= -90.8 kJ/mol
CO2 + 3 H2 CH3OH + H2O ΔH298 0K= -49.5 kJ/mol
CO2 + H2 CO+H2O ΔH300 0K= 41.3 kJ/mol

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 than that of competing
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2.0 Formaldehyde
Introduction
In this lecture, we present the production technology for formaldehyde .
Formaldehyde is produced from methanol

Formaldehyde production
Reactions

Oxidation: CH3OH + 0.5 O2 HCHO + H2O

Pyrolysis: CH3OH HCHO + H2

Undesired reaction: CH3OH + 1.5 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
o
C
Process Technology :
Air is sent for pre-heating using reactor outlet product and heat integration concept.

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Flow sheet of Formaldehyde production

Eventually heated air and methanol are fed to a methanol evaporator unit
which enables the evaporation of methanol as well as mixing with air. The reactor inlet
temperature is 54 oC.
The feed ratio is about 30 – 50 % for CH3OH: O2
After reaction, the product is a vapour mixture with temperature 450 – 900 oC
After reaction, the product gas is cooled with the heat integration concept and then eventually fed
to the absorption tower.
The absorbent in the absorption tower is water as well as formaldehyde rich water.
Since formaldehyde rich water is produced in the absorption, a portion of the rich water absorbent
solution from the absorber is partially recycled at a specific section of the absorber.
From the absorber, HCHO + methanol rich water stream is obtained as the bottom product.
The stream is sent to a light end stripper eventually to remove any light end compounds that got
absorbed in the stream. The vapors from the light end unit consisting of light end compounds can
be fed at the absorption unit at specific location that matches with the composition of the vapors in
the absorption column.
Eventually, the light end stripper bottom product is fed to a distillation tower that produces
methanol vapour as the top product and the bottom formaldehyde + water product (37 %
formaldehyde concentration).

3.0 Hydrocarbon Steam Cracking for Petrochemicals

Introduction
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 effeiciency. 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 teh cracking of the bnydriocarbond on their own.
Since steam and the hydrocarbons react in the vapour 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
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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.
Hydrocarbons such as Naphtha and LPG have lighter compounds.
When they are subjected to steam pyrolysis, then good number of petrochemicals can be produced.
These include primarily ethyelene and acetylene along with other compounds such as propylene,
butadiene, aromatics (benzene, toluene and xylene) and heavy oil residues.
The reaction is of paramount importance to India as India petrochemical market is dominated by
this single process.

Reaction

CxHy + H2O + O2 C2H4 + C2H6 + C2H2 + H2 + CO + CO2 + CH4 + C3H6 + C3H8 +
C4H10 + C4H8 + C 6H6 + C+ Heavy oils

The reaction is pretty complex as we produce about 10 to 12 compounds in one go

The flowsheet will be reaction-separation-recycle system only in its topology. But the separation
system will be pretty complex.
Almost all basic principles of separation appears to be accommodated from a preliminary look.
Important separation tasks: Elimination of CO and CO2, Purification of all products such as
ethylene, acetylene etc.

The process can be easily understood if we follow the basic fundamental principles of
process technology
Typical feed stocks are Naphtha & LPG
Reaction temperature is about 700 – 800 oC (Vapor phase reaction).

Process technology

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Flow sheet of Hydrocarbon Steam Cracking for Petrochemicals

Naphtha/LPG saturates 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. This is by using waste
heat recovery concept where the combustion gases in the furnace.
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 oC) and generate steam from water.
After this operation, the product vapours 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 atms.

The compressed vapour is fed to a phase separation that separates the feed into
two stream namely the vapour phase stream and liquid phase stream. The vapour 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 vapour phase and liquid phase streams are subjected to separate processing.
Gas stream processing: CO2 in the vapour 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 dethanizerwhich 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.

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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 liqiuid 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
vapour phase stream and sent to the NaOH vapour 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 + butylenes
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.

Why two separate furnaces are used for C2-C4 saturates and Naphtha feed stocks?

Ans: The purpose of steam cracking is to maximize ethylene and acetylene production.
For this purpose if we mix C2-C4 saturates and naphtha and feed them to the same
furnace, then we cannot maximize ethylene and acetylene production. The napntha steam
cracker has its own operating conditions for maximizing ethylene and acetylene and so is
the case for C2-C4 saturates.

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Why the product gases from naphtha and C2-C4 saturates steam cracker processed
separately before mixing them and sending them to the compressor?

Ans: Both crackers produce products with diverse compositions. Both cannot be fed to a
single scrubber and remove the heavy hydrocarbons and oil components. While the
scrubber associated to naphtha steam cracking needs to be remove significantly the oil
and heavy hydrocarbons, this is not the case for steam cracker product vapour
processing.

An alternate way of designing a single scrubber is to design a complex scrubber that has
multiple feed entry points correspond to both product gases entering from various units.
This refers to process intensification and would be encouraging.

Why a tailing and topping still is required for ethylene production?

Ans: The distillation column for separating ethylene from ethylene from C2 components
needs to carry out a difficult separation. This is also due to the fact that the boiling points
of C2 components is very close. Therefore, there needs to be two columns (indicating
good number of trays).
Explain how extractive distillation enables the separation of butadiene?

Ans: Dimethyl formamide (solvent) is fed to the distillation column fed with butadiene,
butane and butylenes. The solvent interacts differently with the components and
therefore adjusts the relative volatility of the mixture which was close to 1 previously.
Thereby, the solvent forms a high boiling mixture at the bottom with butadiene and
thereby enables the difficult separation of butadiene from the C4 compounds. Thereby,
the solvent + butadiene is fed to a stripper which removes butadiene from the DMF. One
important issue here is that the solvent does not form an azeotrope with the butadiene
and is therefore, easy to separate.

When acetylene is not required, what process modifications will exist to the technology?

Ans: When acetylene is not required, then the top product from C2 splitter (which is a
mixture of acetylene and ethylene) is fed to a packed bed column and H2 to convert the
acetylene to ethylene. Eventually, one does not require the absorber-stripper technology
for acetylene purification.

4.0 Vinyl Chloride from Ethylene

Introduction

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In this lecture we study the process technology involved in the production of Vinyl Chloride
from Ethylene
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 selective cracking to form vinyl chloride.
We first present the process technology associated to Ethylene Chloride

Ethylene dichloride
Reactions

C2H4 + Cl2 C2H4Cl2
Undesired products: Propylene dichloride and Polychloroethanes
Reaction occurs in a liquid phase reactor with ethylene dichloride serving as the liquid medium
and reactants reacting the liquid phase
Catalyst is FeCl3 or Ethylene dibromide

Process Technology

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Flow sheet of production of ethylene dichloride

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 50 oC and 1.5 – 2 atms.
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 vapour products are cooled to produce two products namely a vapour product and a liquid
product. The liquid product is partially recycled back to the reactor to maintain the liquid
medium concentration.
The vapour product is sent to a refrigeration unit for further cooling which will further extract
ethylene dichloride to liquid phase and makes the vapour 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.

4.1 Vinyl chloride production

Reaction

C2H4Cl2 CH2CHCl + HCl
Charcoal is used as the catalyst
The reaction is a reversible gas phase reaction

Process Technology

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Flow sheet of production of vinyl chloride

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 oC. 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.

5.0 FORMALDEHYDE
Some major intermediates derived from formaldehyde are chelating agents, acetal resins, 1,4-

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butanediol, polyols, methylene diisocynate. It is also used for the manufacture of wide variety of
chemicals, including sealant, herbicides, fertilisers, coating, and pharmaceutical.
Formaldehyde is commercially available as aqueous solution with concentration ranging from 30-
56 wt.% HCHO. It is also sold in solid form as paraformaldehyde or trioxane. The production of
formaldehyde in India has been growing at a fairly constant rate during last ten years. There are
presently about 17 units in India. Installed capacity and production of formaldehyde during 2003-
04 was 2.72 lakh tonnes and 1.89 lakh tonnes respectively.

Various industrial processes for manufacture of formaldehyde using silver and iron- molybdenum
catalyst are given below:

Catalyst Process licensor

Silver catalyst processes Bayer, Chemical construction, Ciba, DuPont, IG
Farben, CdF Chemie process, BASF process, ICI
process,
Iron-molybdenum catalyst Degussa process, Formox process, Fischer-Adler,
processes Hiag-Lurgi, IFP-CdF Chimle Lumus, Motedisous,
Nikka Topsoe, Prolex

Product Profile of Formaldehyde

Product Uses

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Formaldehyde Thermosetting resin: Phenol, Urea Melamine, Formaldehyde resins

Hexamethylenetetramine, Plastic & pharmaceuticals
1,4-Butadiol Methylene
diisocyanate
Fertiliser, Disinfectant, Biocide Preservative, Reducing agent, Corrosion
inhibitor
Polyaceta resin
p-formaldehyde
Pentaerythritol (Explosive-PETN),Alkyl resins
Process diagram for manufacture of formaldehyde using silver and iron-molybdenum catalyst is shown in
Figure

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Figure : Formaldehyde Using Silver Catalyst

Figure : Formaldehyde from Iron Molybdenum Catalyst

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6.0 ACETYLENE
Various Routes for Acetylene:
Calcium Carbide Route: This is the oldest method for production of acetylene and still
acetylene is produced by this process in small scale as well large scale. Calcium carbide is
produced by reacting lime with coke at temperature 2,000-2,100 oCin an electric furnace. Two
processes produce acetylene from calcium carbide process: Wet process and Dry process. Dry
process is preferred as in case of calcium hydroxide, which is produced during the process (is
produced in the form of dry calcium hydrate).

CaC2 +2 H2O  C2H2 + Ca(OH) 2

Acetylene from Cracking of Hydrocarbons: Cracking of hydrocarbons such as methane,

ethane, propane, butane, ethylene, and natural gas can make acetylene.

• 2 CH4  C2H2 +3 H2

• C2H4  C2H2+H2
• C4H10  C2H2+C2H4+2 H2

Product Derived from Acetylene: Acetylene is extremely reactive hydrocarbon and was
initially was used for the manufacture of large number of chemicals which are now being derived
from acetylene route.

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PRODUCT PROFILE OF ACETYLENE

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Acetaldehyde:

r Ac ylor it ile: HC≡CH+HCN HC=CH= CH2=CHCN

Chlorinated solvents:
HC≡CH+2Cl2 CH2Cl2CHCl2 CHCl =CCl2+HCl
CHCl =CCl2+ Cl2 CH2Cl2CCl3 CCl2 = CCl2+HCl
Vinyl acetate:
HC≡CH+CH3COOH CH2 = CHOOCCH3
Chloreprene
HC≡CH+CH3COOH CH2 = CHOOCCH3
CH2 = CHOOCCH3+Cl2 CH2=CClCH=CH2
Vinyl Chloride and Vinylidene Chloride
HC≡CH+HCl CH2 =CHCl
CH2 =CHCl+Cl2 CH2 ClCHCl2
CH2 ClCHCl2 CH2 = CCl2+ HCl
Vinyl fluoride:
HC≡CH+ HF CH2=CHF
Reactions in Acetylene derived Chemicals

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7.0 ETHYLENE GLYCOLS

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8.0 VINYL CHLORIDE

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9.0 VINYL ACETATE

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10.0 MANUFACTURE OF ETHANOL

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REFERENCE
1. www.indiainfoline.com/sect/chor/ch05.html
2. Gunardson, H.H, Abrardo, J.M., “Produce CO rich synthesis gas”, Hydrocarbon Processing,
Volume 66, No. 4, 1998, p. 87.
3. Mall, I.D. “Petrochemical process technology”, first edi., New Delhi, Macmillan India ,2007
4. Huang, Sun-Yi, Lipp, D.W., Farinto, R.S. “Acetylene derived chemicals” in Kirm Othomer
encyclopedia of Chemical technology, Fifth edition volume 1 wiley-Interscience, p.227
5. Chemistry Industry News, March 2004 SRI consulting, World Petrochemicals Program
6. Chemical Industry Digest, July 2012,p.29
7. Chemical Weekly, November 15, P-199, 2011.
8. Dryden C. E., Outlines of Chemical Technology, East-West Press, 2008
9. Kirk R. E., Othmer D. F., Encyclopedia of Chemical Technology, John Wiley
and Sons, 1999-2012

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