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Introduction (History)
Chemical Industry :
ancient origin
founded on a wide variety of sources of raw materials
eg. coal, molasses, fats and oils, salt, metalliferous ores,
water and the atmosphere
apperarance of petroleum as significant source of
chemicals dates back to mid 1920s
Petroleum :
a mixture of hydrocarbons
chemicals made from it are nearly all organic chemicals
but can also be inorganic for specific reasons
Carbon black and hydrogen cyanide classed as
inorganic on arbitrary basis
Sulphur present as undesirable impurity in crude oils
and natural gas can be recovered as element or
sulphuric acid.
Hydrogen from petroleum is used in ammonia
production
From coal
From fermentation
Ethylene and
derivatives
Benzene*
Toluene*
Propylene and
derivatives
Naphtalene*
Pyridine*
Ethyl alcohol*
Food acids*
Monosodium
glutamate
Pharmaceuticals*
C4 hydrocarbons
and derivatives
Synthesis gas
derivatives
Aromatics
Cyclic
compounds
Acetylene*
Anthracene
Acetylene*
Phenol*
Sulphur based :
Recovered sulphur *
Sulphuric acid*
Carbon based :
Hydrogen cyanide
Carbon black
Oxides of carbon
Characteristics of Petrochemical
Manufacture
As a general rule, the petroleum producers supply the
chemical products companies with the raw materials, the
latter manufacture finished products.
However, many exceptions to this rule and the integrating
of petroleum and chemical activities is carried to greater
or lesser degrees, depending on the case. The same
company can also be engaged in several activities.
1)
some oil companies supply the chemical industry
with raw materials and intermediate products.
2)
some chemical companies depend on the oil
industry for large quantities of raw materials and
intermediates. They devote most of their efforts to
manufacturing complex products and are specialized
in organic chemistry products.
3)
other oil companies extend their activities beyond
basic products to include intermediate products and
their derivatives and even end-products.
4)
Petroleum products :
handled in a fluid form.
very rarely identifiable chemical compounds
commonly prepared as blended products, required to
meet a series of physical specifications, with occasional
chemical interpolations as to impurities
provides oil-refining operations with a significant
degree of flexibility
eg. blended products are prepared for markets whose
standards of acceptance are well known and of long
standing
Refineries present a spectacular array of pipe tracks and
tank farms for the handling of raw material and finished
products.
The chemical industry is rather more diverse. It ranges all
the way from large-scale plants (still pretty small by
petroleum standards) to small untidy batch-operated units.
Petroleum chemical manufacture commonly requires the
application of typically petroleum processing techniques
to typically chemical finished products.
Petroleum chemical units:
usually continuous, elaborate, operating with catalytic
promotion and highly automated
require large scale of operation to secure economic
advantage, otherwise little purpose in the development
of petroleum raw materials to serve the chemical
industry in any particular instance
subject to consideration of min. economic size
Cost of utilities
The petrochemical industry is a rather large consumer of
electricity. The power consumed is about 15000 20000
kw for an ammonia or a butadiene unit of medium size.
In industrialized countries, power is often produced in
very large thermal or hydro-electric power stations, and it
can be purchased at different rates from one country to
another depending on the power consumed and length of
utilization.
If power is not available, it must be produced within the
petrochemical plant itself. Its cost would then depend, for
manufacturing units, on the cost of construction, price of
fuel (natural gas, fuel gas, fuel oil), cost of labor, etc. and
would change from one country to another. The same is
valid for the cost of steam and cooling water which are
usually produced in the plant itself.
Cost of Labor
The cost of construction labor in developing countries is
usually higher than industrialized countries, although
wages are lower. This is due to factors such as lower
productivity and lack of qualified technicians and skilled
workmen (such specialists would have to be imported
from abroad at very high cost).
It is difficult to specify the real maintenance and
operational labor costs for the manufacturing units of a
specific plant without going into details. Nevertheless,
taking into account the following factors:
training of local operators, foremen and engineers
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Raw materials
Notes on Petroleum and Natural gases
The basic raw materials for chemical manufacture are
natural gas, refinery gases and liquid hydrocarbon
fractions.
Secondary raw materials are derived from basic raw
materials and their derivation are summarized below :
Acetylene
from cracking or partial oxidation, either of
methane in natural gas or higher paraffins
Methane
Major constituent of natural gas
Higher
Ethane, propane and butane separated from
paraffins
refinery gas streams or natural gas. Other
raw materials in this category are paraffinic
naphthas, and n-paraffins of varying carbon
chain length
Ethylene
Present to a limited extent in some refinery
gas streams. Produced by cracking of
ethane, propane or butane (derived from
refinery streams or extracted from natural
gas) or liquid hydrocarbons
Propylene
From refinery gas streams or by thermal
cracking of propane and liquid hydrocarbons
C4
From refinery gas streams or by thermal
hydrocarbon cracking of liquid hydrocarbons
Higher
From
wax
cracking,
n-paraffin
olefins
dehydrogenation, or oligomerization of
ethylene
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Refinery Gases
Refinery gases range from :
hydrogen at the lower or more volatile end
hydrocarbon with 4 carbon atoms in the molecule at the
less volatile end
olefins (ethylene to butylenes)
paraffins (methane to butanes)
small proportions of components such as acetylene,
certain dienes (notablly butadiene)
and, impurities such as hydrogen sulphide and nitrogen.
Refinery gases :
originally used for petroleum chemical manufacture
came from the obsolete process of thermal cracking (eg.
coking, viscosity breaking)
4 main sources are processes of crude oil distillation,
catalytic
cracking,
catalytic
reforming
and
hydrocracking
Crude oil distillation :
Produces volatile fraction of paraffinic gases
Minor component gasoline
Major component separated drg. Distillation, process
stabilization of gasoline
proportion of gas produced varied widely between one
crude oil and another
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Catalytic cracking :
Replacing the old thermal cracking processes
Provide more valuable range of products eg. higher
quality gasoline
Modern fluid bed catalytic cracker uses catalyst in the
form of fine particles of controlled size
Catalyst comprised combination of silica and
aluminium
Molecular sieves introduced 15 years ago and become
predominant today
Technique of passing feed and regenerated catalyst
through riser crackers become established
High temperature (680 760oC) regeneration gives
more complete burn-off of coke deposited on the
catalyst
Cracking reaction takes place at 475-550oC and about 2
atm press
Hydrocracking :
Cracking operation carried out in a strong reducing
environment
Represent an alternative to catalytic cracking as a
means of increasing the yield of gasoline from a barrel
of oil
Cracking function dual function catalyst comprises
hydrogenation/dehydrogenation sites and acidic sites
Catalyst of zeolite type in combination with metal or
metal oxide catalysts
Provides saturated gases including significant quantities
of propane and butanes esp. isobutane
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Catalytic reforming :
Replacing the older thermal reforming processes
Design to improved the quality rather than the volume
of gasoline production
Use for heavy gasoline fraction including naphthenes
Catalyst comprises platinum and rhenium on an
alumina base
Catalyst allow reaction to proceed at lower pressures,
greater throughput, higher yields or higher performance
product
Main function of catalyst isomerization and
dehydrogenation of napthenes to produce aromatics
Most important reaction cyclization and
dehydrogenation of alkanes and dehydrogenation of
naphthenes to aromatics
Other refinery processes. Some of the more intractable
residues of refinery distillations are subjected to thermal
coking to provide small amounts of gas/liquid fuels while
producing a more readily handled coke fuel.
Olefins from cat-cracker operations (or even steam
cracking of natural gas liquids in the USA) may be used to
alkylate branched alkanes, particularly isobutane.
Alternatively, propylene and butenes may be
oligomerized, and the resulting C6+ olefins hydrogenated
to give polygasoline.
The term hydrotreating tends to be used to cover all
refinery hydrogenation processes. These may range from
hydrogenation of olefinic mixtures (liquid cracker
products for example) under mild conditions, to the
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the
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Refinery operations
The term cracking and reforming are often used without
qualification to describe a variety of refinery and primary
petrochemical operations. It is hoped that Table 1 will
provide a general guide to what is meant in a particular
context.
Table 1 Petroleum fractions
Methane
Associated gas
Ethane
Propane
Butanes
Liquefied
petroleum
gases (LPG)
C5(>0oC)-70oC
Light gasoline
or light naphtha
70oC-170oC
170oC-250oC
Naphtha (midrange)
Kerosene
250oC-340oC
Gas oil
340oC-500oC
Heavy
distillates
Fluid residues
(from light
crudes)
Semi solid
residues
Bitumen or
asphalt
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(Natural gas)
Natural gas
liquids (NGL)
Feedstocks for
motor spirit, also
known as straightrun gasoline
Vaporising oil, jet
fuel
Diesel fuel, light
fuel oil
Feedstocks for
lubricants and
waxes or heavy
fuel oils.
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Natural Gas
Natural gases :
Dry gas consist largely of CH4
Sour gas containing impurities of sulphur compounds
Associated gas natural gas associated with oil recover
Cracking technology of natural gas liquids does not
differ fr. Naphtha cracking
Acetylene from natural gas
Traditional route fr. Calcium carbide and indirectly fr.
coal
CaO + 3C CaC2 + CO
CaC2 + H2O CaO + C2H2
Limitations :
Carbide production concentrated in areas where coal
and power relatively economical
Transportation of calcium carbide itself is a constraint
3.3 ton CaC2 needed to prod. 1 ton C2H2
Production of acetylene fr. hydrocarbons
2CH4
C2H2 + 3H2
Temp. ~ 1200oC
Problems/Disadvantages :
Heat need to be introduced for reaction to proceed
Reaction products must be cooled very rapidly to
prevent decomposition of acetylene
Acetylene must be separated fr. other reaction products
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Solutions :
To achieve heat input by applying an electric arc to
feed, temp. rise to 1600oC
Rapid quech by introduction of cold secondary HC feed
Processes :
Wulff
BASF
SBA
Liquid Hydrocarbons
Acetylene fr. liquid HCs (using this route usu. with
problems)
Hoechst HTP process :
2 stage flame process
Classification
of
According to Source
Petrochemicals
Acetylene Derivatives
1) Vinyl Chloride
The reaction of acetylene with hydrogen chloride
C2H2 + HCl C2H3Cl
- advantage : no by-product hydrogen chloride was
formed
- carried out in vap. phase using charcoal impregnated
with 10% mercuric chloride as catalyst
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1.4
1.0
2.4
MJ/mol
3.0
4.4
General considerations.
A number of organic products are
potentially producible from either acetylene or a lower olefin, for
example:
C2H2 + H2O
CH3CHO
C2H2 + CH3CO2H CH2=CHO2CCH3
C2H2 + HCN
CH2=CH.CN
C2H4 + O2
C2H4 + O2
+ CH3CO2H
C3H6 + NH3 + 1 O2
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2.2
Methane Derivatives
(C1 production)
directly
into
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HCO2CH3 CO + CH3OH
Hydrogen cyanide
The reported demand for hydrogen cyanide in the USA is 550 kt per
annum. Possibly one quarter is by-product from acrylonitrile
manufacturer; the remainder is produced by the oxidation of
methane/ammonia mixtures over platinum at about 1100oC. The
major use (40-45%) is in DuPonts adiponitrile production, with some
30-35% used for methyl methacrylate (MMA) (methyl 2methylpropenoate) manufacture and 10% sodium cyanide.
Chloromethanes
Passage of methanol and hydrogen chloride over a Lewis acid catalyst
at about 350oC provides methyl chloride.
CH3OH + HCl CH3Cl + H2O
This product can be chlorinated to give the more highly substituted
derivatives. However, more operations are now based on the
oxychlorination of methane, over copper chloride catalysts, at
temperatures of over 500oC.
2CH4 + Cl2 + O2 2CH3Cl + H2O
2CH3Cl + Cl2 + O2 2CH2Cl2 + H2O
Mixtures are obtained with proportions dependent on the initial ratio
of chlorine to methane. Some carbon tetrachloride is also produced by
the chlorinolysis (C-C cleavage) of higher carbon number materials,
and chlorination of carbon disulphide.
The total US production of chloromethanes is over 0.9 Mt per annum.
Chloroform
(trichloromethane)
and
carbon
tetrachloride
(tetrachloromethane) are precursors for fluorocarbons; their
elimination from the aerosol can market has been partially offset by
increased use as refrigerants and intermediates for fluoroplastics.
Methylene dichloride (dichloromethane) has picked up some of the
aerosol business, and is used in paint removal and degreasing. Methyl
chloride (chloromethane) is used for silicones and the waning
production of tetramethyl lead.
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