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Petrochemical Synthesis

the synthesis of chemical products from petroleum and hydrocarbon gases. Hydrocarbons of
petroleum, natural gases, casinghead gases, and petroleum refining gases are the main raw
materials for the manufacture of the most important high-volume synthetic products—plastics,
rubbers and fibers, nitrogen fertilizers, surface-active agents, detergents, lubricants and lubricant
additives, plasticizers, fuels, solvents, and extractants. All these products are widely used in
various branches of industry and in the household, and the development of many new areas of
technology, such as space exploration and atomic power engineering, is related to them.

In the industrially developed countries, petrochemical synthesis has made possible the
establishment of a large and rapidly expanding petrochemical industry. The hydrocarbons of
petroleum and gases, which are readily available, cheaper, and more technologically efficient
raw materials, are replacing other types of raw materials (coal, oil shale, vegetable oil, and
animal fat) in almost all processes of organic synthesis.

Petrochemical synthesis is based on advances in organic chemistry, catalysis, physical chemistry,


and chemical engineering and is related to the extensive study of the composition of petroleum
and the properties of its components. Numerous reactions of organic chemistry, including
pyrolysis, oxidation, alkylation, dehydrogenation and hydrogenation, halogenation,
polymerization, nitration, and sulfonation, are the basis of the processes for converting
hydrocarbon raw materials into finished products. Catalytic reactions are the most important of
these reactions. The preparation of the hydrocarbon raw material and the production of primary
initial hydrocarbons, including alkanes (paraffins), unsaturated hydrocarbons (olefins, dienes,
and acetylene), aromatics, and naphthenes, are of great importance in the production of
petrochemical products. Most of these primary products are converted into derivatives with
functional groups containing oxygen, nitrogen, chlorine, fluorine, sulfur, and other elements.

Alkanes. Alkanes are important because of the large volume of their use in petrochemical
synthesis. The lower gaseous hydrocarbons (methane, ethane, propane, butane, and the pentanes)
and the liquid or solid paraffins (from C6 to C40) are used to make various chemical products. The
lower paraffin hydrocarbons are isolated from natural and casinghead gases. Petroleum by-
product gases and gases produced by petroleum stabilization contain C2-C5 alkanes in amounts
from 83 to 97 percent by volume. The ethane-propane fraction, isobutane, N-butane, and pentane
are isolated from the gases. Natural gas containing 96–97 percent methane is used as industrial
methane, primarily for the production of ammonia, acetylene, methanol, chlorine derivatives,
carbon disulfide, and hydrocyanic acid. Liquid and solid normal C6-C40 paraffins are obtained
from products of petroleum refining (gasoline-kerosine, diesel, and oil distillates) by
crystallization upon cooling, by carbamide deparaffination, and by means of molecular sieves.
The refining of paraffin raw materials satisfies the ever-increasing demand of petrochemical
synthesis for unsaturated hydrocarbons (olefins, dienes, and acetylene). The main method for the
production of olefins (ethylene, propylene, and butylenes) is high-temperature pyrolysis of
various raw materials, from ethane and natural gasoline to heavy petroleum fractions and crude
petroleum. Olefins are also obtained as by-products in petroleum refining. Catalytic
dehydrogenation is used for the conversion of butane into butadiene and of isopentane into
isoprene. Butadiene and isoprene are the main monomers used in the production of synthetic
rubbers.

The conversion of paraffin hydrocarbons into producer gas (a mixture of carbon monoxide and
hydrogen) has great industrial importance. The raw material may be natural gases, casinghead
gases, petroleum refining gases, or any petroleum fraction. Low-cost hydrogen, which is
consumed in large quantities for the production of ammonia, for hydrorefining of petroleum
products, and for hydrocracking, is obtained from producer gas. Ammonia is the raw material for
the preparation of fertilizers (ammonium nitrate and urea) and hydrocyanic acid. The two-stage
conversion of methane also yields concentrated carbon monoxide, which is used in many
processes of petrochemical synthesis. Producer gas is widely used in the oxo process, which is
based on the reactions of olefins with carbon monoxide and hydrogen. Methanol, which is the
raw material for the production of formaldehyde, an important product in the manufacture of
plastics, varnishes, and adhesives, is produced from carbon monoxide and hydrogen.

A wide variety of products is produced from paraffins by oxidation, halogenation, nitration, and
sulfonation. Acetic acid is produced in large quantities by direct liquid-phase air oxidation of the
light fractions of direct-distillation gasoline (boiling limits, 30°-90°C) at 150°-210°C and 4
meganewtons per sq m (40 technical atmospheres) in the presence of cobalt acetate or
manganese acetate. Liquid-phase air oxidation of solid normal paraffins to higher fatty acids
(C10-C20) is a large-scale process. The oxidation of N-paraffins (C 10-C20) is used in industry for
the production of higher alcohols, which are converted into surface-active agents and detergents
of the alkyl sulfate type.

Halogen derivatives of paraffins are produced on an industrial scale. Methyl chloride, methylene
chloride, chloroform, and carbon tetrachloride are produced from methane. Methylene chloride
and carbon tetrachloride are good solvents. Chloroform is used in the synthesis of
tetrachloroethylene, chlorofluorine derivatives, and the valuable monomer tetrafluoroethylene.
Chlorination of ethane yields hexachloroethane and other chloro derivatives. Chloroparaffin-40
(about 40 percent CI), a product of chlorination of solid paraffins, is used as a plasticizer;
chloroparaffin-70 (about 70 percent CI) is used for the impregnation of fire-resistant paper and
fabrics. Products of the complete fluorination of narrow fractions of kerosine and gas oil are
valuable lubricants and hydraulic fluids with high thermal and chemical stability. They can
perform for extended periods at 250°-300°C in highly aggressive media. Freons—chlorofluorine
derivatives of methane and ethane—are used as refrigerants. A mixture of nitroparaffins is
obtained by nitration with nitric acid of propane and paraffins that boil above 160°-180°C. Such
mixtures are used as solvents and intermediates in the production of nitro alcohols, amino
alcohols, and explosives. Surface-active agents of the alkylsulfonate type are obtained by
sulfochlorination and sulfoxidation of kerosine fractions and N-paraffins from C12 to C20.

Unsaturated hydrocarbons. Because of their great reactivity, unsaturated hydrocarbons are


widely used in petrochemical synthesis. Many products are synthesized from olefins, diene
hydrocarbons, and acetylene.

OLEFINS. Ethylene occupies first place among the olefins in terms of industrial use. Propylene
and butenes are being used in increasing quantities. The most important higher olefins are
straight-chain α-olefins obtained by thermal cracking of solid or soft paraffin at about 550°C and
by catalytic oligomerization of ethylene using organoaluminum catalysts. Macromolecular
substances such as polyethylene and polypropylene are obtained by polymerization of olefins.
Polyethylene is the plastic produced in greatest quantities. Its production is increasing very
rapidly, and it is widely used in all sectors of industry. The production of vinyl chloride by
oxidative chlorination of ethylene or a mixture of ethylene with acetylene is expanding rapidly.
Vinyl chloride is widely used for the production of many polymer materials. Polyvinyl chloride
is used for making films and tubes.

Ethylene oxide and propylene oxide have acquired great importance in petrochemical synthesis;
they are used for the production of glycols, surface-active agents, and ethanolamines. A
considerable quantity of ethylene is consumed in the alkylation of benzene for the production of
styrene and oxidation to acetaldehyde and acetic acid, and also for the production of vinyl acetate
and ethyl alcohol. The oxo process is used for the preparation of alcohols and aldehydes. Many
important solvents and insecticides are produced by chlorination of olefins. Alkyl sulfates and
petroleum product additives are produced from higher olefins.

DIENES. The main monomers in the production of synthetic rubbers are 1, 3-butadiene and 2-
methyl-l, 3-butadiene (isoprene). In industry, butadiene is obtained as a by-product of the
pyrolysis of petroleum products and dehydrogenation of butane, the butylene fraction of the
pyrolysis of petroleum raw material in the production of ethylene. The dehydrogenation of
isoamy-lenes isolated from light cracked gasoline and the dehydrogenation of isopentane
contained in casinghead gases and obtained by the isomerization of N-pentane are promising
methods of producing isoprene. Part of the butadiene produced is used in making chloroprene
and 1, 5, 9-cyclododecatriene, an intermediate in the production of polyamide fibers.

ACETYLENE. Large quantities of acetylene are produced from methane and other paraffin
hydrocarbons by oxidizing pyrolysis, electrocracking, and pyrolysis of various petroleum raw
materials in hydrogen plasma. Dimerization of acetylene in the presence of cuprous chloride
yields vinylacetylene, which is mainly used for the production of chloroprene. Acrylonitrile,
vinyl chloride, and acetaldehyde are also obtained from acetylene, but in these cases acetylene is
gradually being replaced by cheaper ethylene and propylene.

AROMATIC HYDROCARBONS. Benzene, toluene, xylenes, trimethylbenzene and


tetramethylbenzene, and naphthalene are valuable raw materials for the synthesis of many
products. Aromatic hydrocarbons are formed by catalytic re-forming of gasoline and ligroin
fractions. Such compounds are obtained in considerable quantities as by-products in the pyrolytic
production of ethylene. Benzene and naphthalene are also obtained by dealkylation of their alkyl
derivatives in the presence of hydrogen. For this method of producing benzene, alkyl aromatic
hydrocarbons (toluene, xylenes, and higher alkyl derivatives) and pyrolytic gasolines are used.
Heavy re-forming fractions and gas oil obtained by catalytic cracking are raw materials for the
production of naphthalene. Alkylation of benzene by ethylene yields ethylbenzene, and
alkylation by propylene yields isopropylbenzene; ethylbenzene and isopropylbenzene are
converted by dehydrogenation into styrene and α-methylstyrene, which are valuable monomers
for the production of rubber. Air oxidation of isopropylbenzene yields phenol and acetone in
large quantities. Alkyl aromatic compounds are the basis for the synthesis of plasticizers,
lubricants, lubricant additives, and surface-active agents. Oxidation of aromatic hydrocarbons
yields terephthalic acid, which is used in the production of fibers (lavsan), and maleic and
phthalic anhydrides, which are valuable plasticizers and components of heat-resistant plastics,
such as polyimides. Chlorination and nitration of aromatic hydrocarbons are used to a lesser
extent. Effective herbicides, solvents, and insulating oils for transformers are produced from
chlorophenols and chloro-naphthalenes. Benzyl chloride is used in the production of a number of
compounds containing the benzyl group (benzyl alcohol and its esters).

Naphthenes. Of the naphthenes, only cyclohexane has acquired great importance in


petrochemical synthesis. Cyclohexane is isolated in small quantities by careful rectification of
the gasoline fractions of petroleum (which contain 1–7 percent cyclohexane and 1–5 percent
methylcyclopentane). Methylcyclo-pentane is converted into cyclohexane by isomerization with
aluminum chloride. The industrial demand for cyclohexane is satisfied mainly by hydrogenation
of benzene in the presence of a catalyst. Oxidation of cyclohexane by atmospheric oxygen yields
cyclohexanone and adipic acid, which are used in the synthesis of synthetic polyamide fibers
(kapron and nylon).

Adipic acid and the other dicarboxylic acids obtained in the oxidation of cyclohexane are used
for the preparation of esters that serve as lubricants and plasticizers. Cyclohexanone is used as a
solvent, and also as a camphor substitute.

A great deal of attention is being devoted to the development of microbiological synthesis using
petroleum raw material. Concentrates containing protein and vitamins are produced from
paraffin hydrocarbons and are used in feeding livestock.

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