Petrochemical Industries Lec.

2. Vinyl Chloride Monomer (VCM) Production Process

Vinyl chloride monomer (VCM) is a colorless gas with a sweet odor. It is highly toxic,

flammable, and carcinogenic. However, VCM is among the top twenty largest petrochemicals in

world production. VCM is an important industrial chemical chiefly used to produce

the polymer polyvinyl chloride (PVC).

VCM is produced by the thermal cracking of ethylene dichloride (EDC). EDC is produced by

direct chloronation or oxychloronation of ethylene. The chlorine used in the manufacture of

EDC is derived from common salt (NaCl) by electrolysis, so 43 % by weight of PVC originates

from crude oil.

CH2=CH2 + Cl2 → ClCH2CH2Cl

ClCH2CH2Cl → CH2=CHCl + HCl

In the direct chlorination section, ethylene is directly chlorinated to produce ethylene dichloride

(EDC). In the oxychlorination section hydrogen chloride (HCl) is reacted with ethylene and

oxygen to yield EDC and water. Both processes are often effected in separate stand-alone units

to produce high-purity EDC.

The EDC produced by direct chlorination is fed straight into the cracking section without any

further purification.

The crude EDC from the oxychlorination sections passes through a purification stage (EDC

distillation).

In the next process section, the cracking unit, EDC is thermally cracked to yield VCM, HCl and

unreacted EDC.
Pure VCM is then separated from the other pyrolysis products in the VCM distillation section

and these are then recycled to either the oxychlorination (HCl) or the cracking section

(unconverted EDC).

Direct chlorination

C2H4 + Cl2 C2H4Cl2

Oxychlorination

C2H4 + 2 HCl + 1/2 O2 C2H4Cl2 + H2O

EDC cracking

C2H4Cl2 C2H3Cl + HCl

The individual sections, which comprise direct chlorination, oxychlorination and EDC cracking

processes, are combined into the so-called "balanced" process which only produces VCM and

water:

VCM synthesis

2 C2H4 + Cl2 + 1/2 O2 2 C2H3Cl + H2O

over a mercuric chloride catalyst :

C2H2 + HCl → CH2=CHCl

Also, VCM could be by direct conversion of ethane.

and mono-vinyl acetylene can have adverse effects upon the polymerization kinetics even at very

low levels (mg per kg) and thus must be stringently controlled. VCM storage can either be under

pressure or refrigerated at approximately atmospheric pressure. A chemical inhibitor, such as a

hindered phenol, is sometimes added to prevent polyperoxide formation.

Production process of Vinyl Chloride Monomer (VCM)

3. STYRENE PRODUCTION PROCESS

Styrene is one of the most important monomers in modern petrochemical industry. It is colorless

to yellow oily liquid, its density 0.909 g/cm³ , Boiling point 145 °C, with Penetrating odor.

Styrene is mainly used for the production of many different polymeric materials, the most

important being polystyrene, styrene-acrylonitrile and acrylonitrile-butadiene-styrene (ABS).

Another important application is in producing styrene-butadiene latex.

over potassium promoted iron oxide catalyst. The accounts for more than 90% of the worldwide

capacity.

The process can be run industrially either adiabatically or isothermally. The energy needed for

the reaction is supplied by superheated steam (at about 720 °C) that is injected into a vertically

mounted fixed bed catalytic reactor with vaporized ethylbenzene. The catalyst is iron oxide

based and contains Cr2O3 and a potassium compound (KOH or K2CO3) which act as reaction

promoters.

Typically, 2.5-3 kg steam are required for each kilogram of ethylbenzene to ensure sufficiently

high temperatures throughout the reactor. The superheated steam supplies the necessary reaction

temperature of 550-620 °C throughout the reactor. Ethylbenzene conversion is typically 60-65%.

The three significant byproducts are toluene, benzene, and hydrogen.

After the reaction, the products are cooled rapidly (perhaps even quenched) to prevent

polymerization. The product stream (containing styrene, toulene, benzene, and unreacted

ethylbenzene) is fractionally condensed after the hydrogen is flashed from the stream. The

hydrogen from the reaction is used as fuel to heat the steam (boiler fuel). After adding a

polymerization inhibitor (usually a phenol), the styrene is vacuum distilled in a series of four

columns (often times packed columns) to reach the required 99.8% purity. The separation is

difficult due to the similar boiling points of styrene and ethylbenzene. Typical capacity per plant

ranges from 70,000 to 100,000 metric tonnes per year in each reactor and most plants contain

multiple reactors or units.

4. BUTADIENE PRODUCTION PROCESS

Butadiene is a flammable, colorless gas with a mild aromatic odor and it is highly reactive. It’s It

is colorless gas that has a mild gasoline-like odor. Butadiene is soluble in alcohol and ether,

insoluble in water and polymerizes readily, particularly if oxygen is present.

One major use of butadiene has been in the making of synthetic rubber (styrene-butadiene and

nitrile butadiene rubbers. Butadiene is also used extensively for various polymerizations for

plastics manufacturing.
There are two sources of butadiene in world: Extractive distillation from Crude C4 stream

produced as a co-product of ethylene production, and “on-purpose” production by

dehydrogenation o n-Butane or n-Butenes.

Up to 50% of the produced volume of butadiene is taken up by SBR and polybutadiene.

Butadiene is used to manufacture rubber for tires, hoses, gaskets, paints and adhesives. It is also

used in the production of nylon clothing, carpets and engineering plastic parts.

Flow diagram for butadiene plant

Description of the process

The crude C4 and the DMF solvent are fed to 1st extractive distillation column where the C4

stream is separated into the C4 raffinate-1 from top and the bottom stream which contains

Butadiene/acetylene in the DMF solvent. The Butadiene/acetylene rich solvent is fed to 2nd

extractive distillation column where mainly vinyl acetylene is removed. The top stream is sent to
the Butadiene purification section where the remaining acetylene is removed and purified 1,3-

Butadiene is produced using two distillation columns. The lean solvent from two strippers is

cooled via heat recovery prior to being sent back to the extractors.

II. BTX Production

In the petroleum refining and petrochemical industries, BTX refers to mixtures

of benzene, toluene, and the three xylene isomers, all of which are aromatic hydrocarbons. The

xylene isomers are distinguished by the designations ortho – (or o –), meta – (or m –), and para –

(or p –). If ethylbenzene is included, the mixture is sometimes referred to as BTEX.

The BTX aromatics are very important petrochemical materials. Global consumption of BTX

showed an unprecedented growth. Toluene is a valuable petrochemical for use as a solvent and

intermediate in chemical manufacturing processes and as a high octane gasoline component

Benzene, toluene, and xylenes can be made by various processes. However, most BTX

production is based on the recovery of aromatics derived from the catalytic

reforming of naphtha in a petroleum refinery.

Catalytic reforming usually utilizes a feedstock naphtha that contains non-

aromatic hydrocarbons with 6 to 11 or 12 carbon atoms and typically produces

a reformate product containing C6 to C8 aromatics (benzene, toluene, xylenes) as well

as paraffins and heavier aromatics containing 9 to 11 or 12 carbon atoms.

Another process for producing BTX aromatics involves the steam cracking of hydrocarbons

which typically produces acracked naphtha product commonly referred to as pyrolysis

gasoline, pyrolysis gas or pygas. The pyrolysis gasoline typically consists of C6 to C8 aromatics,
heavier aromatics containing 9 to 11 or 12 carbon atoms, and non-aromaticcyclic

hydrocarbons (naphthenes) containing 6 or more carbon atoms. The adjacent table compares the

BTX content of pyrolysis gasoline produced at standard cracking severity or at medium cracking

severity with the BTX content of catalytic reformate produced by either a continuous catalytic

regenerative (CCR) reformer or by a semi-regenerative catalytic reformer. About 70 percent of

the global production of benzene is by extraction from either reformate or pyrolysis gasoline.

BTX content of Pyrolysis Gasoline and Reformate

Pyrolysis Gasoline Reformate

Standard Medium
CCR SR
severity severity

BTX content, wt % 58 42 51 42

Benzene, wt % of BTX 48 44 17 14

Toluene, wt % of BTX 33 31 39 39

Xylenes, wt % of BTX 19 25 44 47

CCR = Continuous catalytic regenerative reformer

SR = Semi-regenerative catalytic reformer

many different methods. Most of those methods, but not all, involve the use of a solvent either

for liquid-liquid extraction or extractive distillation. Many different solvents are suitable,

including sulfolane (C4H8O2S), furfural (C5H4O2), tetraethyleneglycol (C8H18O5),

dimethylsulfoxide (C 2H6OS), and N-methyl-2-pyrrolidone(C5H9NO).Below is a schematic flow

diagram of one method, involving extractive distillation, for extraction of the BTX aromatics

from a catalytic reformate.

BTX production Flow diagram