PART II
Organic Chemical Process Industries
Introduction
Unit process : the raw materials undergo chemical change during their processing
into finished products.
Unit Operation: only physical changes and not chemical changes take place.
Organic Chemical Process Industries includes:
1- Soap, surfactants and intermediate
2- Polyethylene industry
3- Rubber industry
4- Sugar industry
5- Dyes , Leather, petrochemical, fertilizer, oil and fat, food, etc.
The main types of reactions in OCPI:
1- Alkylation reaction
Alkylation is the transfer of an alkyl group from one molecule to another[ to
increase octane number &increase molecular size] . An alkyl group can be added
to a benzene molecule by reaction called the Friedel‐Crafts alkylation reaction.
Friedel‐Crafts alkylation is substitution reaction or addition reaction. These
reactions are known to be exothermic reactions.
Catalysts used in Friedel‐Crafts alkylation reaction:
1- Anhydrous AlCl3 is used as catalyst.
2- sulfuric or hydrofluoric acid is used as catalyst.
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Protonic acid
alkylation
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2- Sulfonation reaction
Sulfonation is a reversible highly exothermic reaction in which sulfur trioxide and
fuming sulfuric acid (oleum [H2SO4100%+SO3]) is added to benzene or its
derivatives to from alkyl benzene sulfonic acid. The product alkyl benzene sulfonic
acid is used as intermediate material for detergents and dyes.
The reaction is reversed by adding hot aqueous acid to benzenesulfonic acid to
produce benzene.. Oleum 20% (20gSO3 in 80gH2SO4) is used for sulfonation. The
reaction is characterized by high thermal tenor, thus realizing a liquid reactive film
flowing directly downwards on the internal reactor wall, it benefits of high heat
exchange to the external jacket.
Falling film Sulfonation reactor
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3- Nitration reaction
Sulfuric acid and nitric acid are called mixed acid (53%
H2SO4:39%HNO3,8%H2O) are used as nitration reagent .This reaction is highly
exothermic reaction .
It carried out in ice (to prevent more than one nitro groups being substituted
They are widely used in the production of explosives and chemical intermediates.
All nitration reactions are potentially hazardous because of the explosive nature
of the products and the strong oxidizing tendency. Cooling system is required to
control the explosive nature of nitro compounds.
Multi stages reactor
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4- Oxidation reduction reaction
Reduction is a process which involves; removal of oxygen, addition of hydrogen
Reduction
Oxidation
5- diazotization reaction
An azo coupling is an organic reaction between a diazonium compound and
another aromatic compound that produces an azo compound.
1 aniline 2 diazanium salt (intermediate)
3 β naphthol 4 azo dye
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6- polymerization reaction ( addition , condensation)
6-A. Addition polymerization
6-B. Condensation polymerization
1- Intermediates industry
Process intermediate means any material used in a process which is neither a raw
material nor a product.
Some examples of intermediate materials: aniline, ethyl benzene, styrene
nitrobenzene, terephthalic acid, etc. the famous intermediate will illustrate below:
1- production of ethylene [CH2=CH2]
Ethylene is produced commercially by the steam cracking of a wide range of
hydrocarbon feedstock. It used to produce polyvinyl chloride (PVC), PET
polyethylene terephthalate, cellulose acetate and polyvinyl acetate polymer.
Ethylene is a stable molecule that polymerizes only upon contact with catalysts. The
conversion is highly exothermic. Over 95% of the worldwide annual commercial
production of ethylene is currently based on steam cracking of petroleum
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hydrocarbons. Various feedstock, including ethane, propane, butanes, naphtha and
gas oils. Figure (1) show the production of ethylene by steam cracking of various
feedstock.
Figure (1) show the production of ethylene by steam cracking of various feedstock
Uses of ethylene
1-1 production of poly ethylene [-CH2-CH2-] (PE)
Polyethylene has different production methods which include high
pressure polyethylene and low pressure polyethylene. In general, the
polyethylene produced by the high pressure process is called 'low density'
and the poly ethylene produced by the low pressure process is called 'high
density polyethylene. Polyethylene is made by the reaction of multiple
ethylene molecules in the presence of catalyst.
Three main catalysts are employed commercially: the Phillips
catalyst[chromium oxide supported on silica] , Ziegler–Natta catalysts
[titanium trichloride], and, , metallocene-based catalysts. Fluidized bed
reactor is used for production of polyethylene. Pre polymerization is used
to prevent bubble formation
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Production of PE
Properties of polyethylene
Polyethylene has an excellent low-temperature resistance, a great
chemical resistance, an outstanding power insulation, a good pressure
resistance and a marvelous radiation resistance. Polyethylene has
become the most important polyolefin plastic with excellent mechanical
properties, processing properties and chemical stability. It is used in the
production of film, packaging and pipe.
(Low-density polyethylene) LDPE is formed at pressure (1000–5000 atm)
and high temperature (520 kelvins)
High-density polyethylene HDPE is formed at pressure (6–7 atm) and
low temperature (333–343 K).
Disadvantages of polyethylene
1- The way to dispose of polyethylene is incineration, which can
result in harmful gas emissions.
2- Not Resistant to Oxidizing Acids.
3- Not Resistant to Chlorinated Hydrocarbons.
4- High Thermal Expansion
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2- Production of ethyl benzene (EB)
EB is the key intermediate in the production of styrene and added to gasoline
as an anti-knock agent to reduce engine knocking. Ethyl benzene is obtained
by catalyzed alkylation of benzene with ethylene. Percent conversion is 42%.
Benzene, C6H6 + ethylene, CH2=CH2 === ethyl benzene,C6H5C2H5
EB, B, PEB
Unreacted benzene, B
Poly ethyl benzene, PEB
Simple flow sheet of production of ethyl benzene
3-Production of styrene(C8H8)
Styrene is a chemical used to make latex or synthetic rubber, and polystyrene resins.
These resins are used to make plastic packaging, disposable cups and containers (why)
because it has resistance to bacterial growth and resistance to moisture and heat
Producing styrene involves:
1- Alkylation of benzene with ethylene to produce ethyl benzene.
2- Followed by dehydrogenation of ethyl benzene to styrene.
The direct dehydrogenation of ethyl benzene to styrene over Cr Oxide /Al2O3
at580-630 °C
C6H5 CH2CH3 ======= C6H5CH1=CH2 + H2
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3- distillation process is allowed to obtain pure styrene ( figure 2)
Flow sheet of production of styrene
4- production of nitro compounds
Nitro compounds are a very important class of nitrogen derivatives. They are
used as an intermediate in the reduction processes to get amines. R-NO2 is the
structure formula made by nitration reaction using mixed acid.
4-1 - Preparation of aniline
a. nitration of benzene give nitrobenzene
b. reduction of nitro benzene to aniline
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Nitrobenzene aniline
And aniline used as an intermediate material in rubber industry and dyes.
4-2. Preparation of tri nitro toluene (TNT) (high explosive)
4-3. Preparation of tri nitro glycerin (prevent chest pain (angina)
Glycerin tri nitro Glycerin
4-4 Aliphatic nitro compound R- NO2 ex. CH3NO2, C3H7 NO2 are used as
industrial solvents. they are prepared at 600C o and the reaction is called
vapor phase nitration .
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