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Background to Petroleum Chemicals

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

Source of Typical organic chemicals


From petroleum

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*

From oils and


fats
Fatty acids
Fatty alcohols*
Soaps
Glycerine*

Sources of typical inorganic chemicals


From petroleum
Hydrogen based :
Ammonia
Nitric acid
Nitrogen fertilizers

From other sources


Chlorine/caustic soda
Potash and phosphate fertilizers
Sulphur/sulphuric acid*
Titanium dioxide
Metal salts
Pyrites
Chalk/lime
Soda ash
Bleaching powder
Fluorine/bromine/iodine
Bauxite
Calcium carbide
Salt

Sulphur based :
Recovered sulphur *
Sulphuric acid*
Carbon based :
Hydrogen cyanide
Carbon black
Oxides of carbon

Notes : The source indicated is predominant except for those marked *


which have more than one significant source.

Petroleum chemical manufacture is concerned to produce


chemical products from raw materials of petroleum origin.
The chemical products made from petroleum do not differ
in any significant way from those made using alternative
raw materials. Differences relate to minor impurities
present.
Petroleum industry original function limited to
separation of petroleum into its different fractions by
distillation.
A stage was reached where gasoline fractions was
required in large quantity and better quality than provided
by simple separation resulting in introduction of thermal
cracking and thermal reforming processes.
Cracking processes creates streams of olefinic gases of no
immediate use to petroleum industry. After considerable
research these olefinic gases were found suitable for a
range of chemical products hence prompted the industry
in 1920s.
In the beginning, policy of petroleum industry was to
establish the refinery capacity in close proximity to oil
fields. Then policy was changed by locating the oilrefining capacity in regions of major consumption.
The production of petroleum chemicals no longer leans
very heavily on refinery gas streams for its raw materials
but the spread of refinery capacity tended to stimulate the
development of chemical production from petroleum.

European developments in petroleum chemical


manufacture did not follow at all exactly the pattern set in
the USA. The main difference was the use of liquid (usu.
Naphtha) feedstocks for the production of the olefinic
base materials, rather than the natural gas liquids and the
major refinery sources available in the USA.
Feedstock trend in the US is towards liquids as raw
materials for the lower olefins, whereas Europe make use
of natural gas liquids from the North Sea.

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)

some companies which do not make large-scale


demands for raw materials and which usually make
use of natural gas, liquefied petroleum gas, refinery
gas and naphtha.
5)
some chemical companies team up with oil
companies to carry out joint activities.
6)
chemical companies also have a tendency to buy
up plastic manufacturing plants and the like. In this
manner they guarantee themselves an outlet for some
of their products at the same time as they acquire
technological and practical experience in the field in
question.
7)
some companies pool their resources in order to
create affiliates. The main advantages of such
associations lie in the following points :
possibility of building a large-capacity unit which
is competitive on the international market but
which avoids harmful competition with small
producers on the domestic market.
reduction of investments for each of the companies,
thus enabling them to become involved in new
fields of activity at the same time.
The petroleum industry has its own cherished traditions.
A medium-size refinery is likely to consume at least 10
million tonnes of crude oil each year. The capacity of
individual plant units is huge by the standards of most
industries but will represent quite a modest proportion of
the total market for the appropriate products in the market
area serviced.

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

Economics and Uses


Economic factors : Elements of operating cost of
installations and manufacturing cost of products
These elements contribute in determining the operating
cost of units and in calculating the manufacturing cost of
products. They depend upon specific conditions prevailing
in different industrialized or developing countries. Their
analysis is of prime importance for it constitutes the basis
for different studies to be undertaken when establishing
new industrial projects.
They include :
cost of raw materials
cost of utilities (steam, electricity, fuel, etc.)
cost of labor and supervision;
cost of construction;
taxes
Cost of raw materials
a)
Natural Gas
The price of natural gas is usually known at the well head.
Its price when delivered as a raw material to a
petrochemical plant depends on several factors such as :
Location of consuming centers (which enables the
distance from the well to the plant to be evaluated)
Amounts consumed (which enables the diameter of the
pipe line to be determined); thus making it possible to
calculate the cost of transportation natural gas from the
fields to consuming centers.

This cost is quite low in the case of large quantities


transported over rather small distances. It gets higher,
when the rate of flow is low or when the distances are
very long, and it becomes very high if special liquefaction
facilities and liquid methane transportation in special
refrigerated tankers. If adequate port facilities do not
exist, their cost should be taken into account when
calculating the transportation cost of natural gas.
b)
Liquefied Gas
Prices of liquefied gas used as raw materials for
petrochemicals depend mainly on the quantities
consumed, that is on possible markets for petrochemical
products based on LPG. In developing countries when
LPG may be available in large quantities, possibilities of
exporting propane and butane may help to lower cost of
recuperation and of transportation from fields to the coast.
This may be quite important because the petrochemical
industry consumes rather small amounts of such
feedstocks.
c)
Liquid hydrocarbons : Naptha and Condensate
Naptha is available in Europe and in many other countries
such as India whose consumption of petroleum products is
largely based on middle distillates such as kerosene and
gas oil.
Condensate is produced in association with natural gas.

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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import of foreign technicians


one may reasonably consider that there will be an increase
of about 30-50% compared with industrialized countries,
at least during the first years of operations.
Construction costs and financing
The cost of construction in different countries may vary
considerably depending on different factors such as :
cost and availability of equipment
equipment specifications and construction standards
cost of transporting equipment when it is not available
at the size
cost and availability of labor
cost of foreign labor when required
productivity and duration of construction
When comparing construction costs in industrialized and
developing countries, it can readily be seen that several
factors intervene to make them higher in the latter
countries.
Uses

11

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

12

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

13

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

14

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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hydrodesulphurization of heavy fractions and


hydrogenation of (poly-) aromatic components.

the

The reasons behind the utilization of larger and larger


quantities of oil and natural gas as raw materials in the
chemical industry are as follows:
1)
Oil and natural gas can produce purer products
than those from carbochemistry.
2)
Petroleum refining can, by means of normal or
special processing, produce substances which are
difficult to derive from other sources (xylenes)
3)
Oil and natural gas can increase supplies of certain
products which would not otherwise be available in
sufficient quantities (glycerin).
4)
Oil and natural gas can usually provide the
required products at lower prices than can other sources
(plastics).
Raw materials come from sources which are varied and
adapted to local conditions. They are made up either of
primary hydrocarbons obtained by simple separations
from natural gas or oil, or of products which have already
been transformed such as residual gas or petroleum cuts
leftover from refining.
In the US use is made primarily of natural gas as well as
ethane and the liquefied gas extracted from it. Gas from
catalytic cracking, which is rich in olefins, is also an
interesting source. Aromatics are extracted from reformed
gasoline.

16

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
17

(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.

Table 2 Refinery and petrochemical cracking and reforming


operations
Refinery
Thermal cracking
Obsolete, thermal decomposition of
middle/higher fractions to increase
gasoline range hydrocarbons
Thermal
Thermal decomposition of very heavy
cracking/coking
fraction to give mainly gases and a high
(delayed coking etc.) coke yield.
Catalytic cracking
Accelerated decomposition, with some
aromatization, of middle/higher
fractions over solid acidic catalysts
Hydrocracking
Accelerated
hydrogenolysis/decomposition of heavy
fractions to paraffinic hydrocarbons
over metal/acid catalysts
Thermal reforming
Obsolete, thermal rearrangement and
aromatization of napthas under high
pressure
Catalytic reforming
Metal/acid-catalysed rearrangement
(platforming)
and aromatization of napthas
Petrochemical
Steam cracking
Thermal cracking of C2+ hydrocarbon
to olefins in the presence of steam
Thermal/autothermal More general term, including methane
cracking
to acetylene autothermal, with partial
combustion
Steam reforming
Nickel-catalysed formation of synthesis
gases from hydrocarbons

18

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

19

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
20

- reagents pure and dry with slight Xs of hydrogen


chloride
- press. atmospheric or slightly higher
- temp : 100 to 210oC
- exothermic reaction
- rxn. conditions depends on age and cond. of catalyst
Nearly all vinyl chloride polymerized to PVC and small
amount converted to vinylidene chloride.
The emergence of ethylene as a contender for vinyl
chloride production arose from the development of the
oxychlorination processes. The route pursued was the
addition of chlorine to ethylene to give ethylene
dichloride (EDC, 1,2-dichloroethane) and the thermal
cracking of EDC (550oC) to vinyl chloride and HCl.
CH2=CH2 + Cl2 ClCH2CH2Cl CH2=CHCl +
HCl
A snag was that these companies now had to dispose of
hydrogen chloride. The most elegant solution was to react
this with acetylene in a separate stage, to give what became
known as the Balanced Process. This scheme became a
driving force for naphtha cracking to mixtures of ethylene
and acetylene, as exemplified by the Wulff process.
Nevertheless these special crackers proved expensive, and
many gave serious operational problems. The final solution
came with the development of the ethylene oxychlorination
process. The reaction
CH2=CH2 + 2HCl + O2 ClCH2CH2Cl + H2O
21

is carried out at 250-300oC over supported copper chloride


(melt) catalysts. This process may be combined with
chlorine addition and EDC cracking to provide a balanced
operation, if required; the overall stoichiometry then
becomes
2CH2=CH2 + Cl2 + O2 2CH2=CHCl + H2O
The polymer referred to here is rigid PVC. The flexible
material contains appreciable amounts of plasticizers
(mainly phthalate esters), which obviously affects the
overall energy utilization.
2) Vinyl Acetate
The reaction between acetylene and acetic acid
CH3COOH + HCCH CH3COOCH=CH2
vinyl acetate

- carried out in vap. phase using catalyst comprising


zinc or cadmium acetate on charcoal
- temp. about 210oC
- pressure slightly above atmospheric
- Xs acetic acid to red. formation of ethylidene
diacetate by-product
- exit gases cooled to 0oC
- purified by distillation
- polymerized rapidly either alone or with other vinyl
compds.
- Applications : adhesives and emulsion paints

22

Lower olefins (alkenes)and acetylene (alkynes)


The paraffinic hydrocarbons in natural resources show
very low reactivity under moderate conditions. Early
petrochemical processes drew upon the greater reactivity
of olefins, and when refinery supplies failed to meet
demand means of converting alkanes to alkenes were
developed. During the later period, low prices of naphtha
(in Europe and Japan) and natural gas (in the USA and
Europe) also promoted petrochemical routes to acetylene.
The resulting processes all require high temperatures and
are, therefore, both energy-and capacity-intensive, so that
very large scales of operation are desirable for efficiency
and economic viability.
Cracking processes

23

Steam (thermal) cracking for lower olefins. A typical naphtha for


cracking has a carbon number range from 4 to 12 or more. The
uncatalysed cracking reaction is carried out within tubes in a furnace
enclosure at near atmospheric pressure (less than 3 atm). Steam
makes up 30-45% w/w of the total feed to improve heat transfer,
reduce the partial pressure of hydrocarbons (thermodynamically
desirable) and remove carbon by the reaction
C + H20 CO + H2
Cracking temperatures were traditionally 750-850oC, but
temperatures up to 900oC (high severity cracking) are becoming
more common, in conjunction with shorter residence times (about
0.1 second).
Hydrocarbon dehydrogenation and cleavage reactions of the
type
A B + C + D .....
are always strongly endothermic, with H values in the range 120180 kJ for each additional molecule produced.
XXXXXXXXXXX

Cracking processes for acetylene (ethyne)


Minor amounts of acetylene are formed in steam cracking, but
rarely justify separation. However, if cracking temperatures are
increased to over 1100oC acetylene becomes a significant
component, and a different approach to reactor design is necessary.
The Wulff process furnaces contain stacks of tiles, and operate on 1minute heating-cracking cycles. Fuel gas or oil burned in air to heat
the tiles to about 1200oC, and the feed is then switched to naphtha
and steam, the temperature falling to about 1000 oC to complete the
cycle.
At still higher temperatures (over 1500oC), methane can be
partially converted into acetylene. An electric arc process has been
operated, but the most successful and widespread approach is the
BASF or Sachsse partial oxidation process. Typically methane (in
excess) and oxygen are fed to a special burner, in which the
temperature falls from a peak of about 2500oC to 1300oC in a very
short time, at which point the gases enter a quench. A typical
24

product stream (water-free basis) would contain some 8% (molar)


acetylene, 25% carbon monoxide, 55% hydrogen and small amounts
of methane, carbon dioxide and other gases. After acetylene
extraction, the remaining gases may be integrated into a synthesis
gas system.
Finally, BASF have also developed a submerged flame autothermal
cracking process for crude oil. Partial combustion raises the
temperature locally, to the point at which cracking to both ethylene
and acetylene occur.
Ethylene (ethene) and other olefins (alkenes)
We will start with the simpler cracking of ethane according to
the following equation and theoretical energy balance (in MJ/mol
ethylene), based on energy (fuel) values as defined above.
C2H6 (+heat) C2H4 + H2
1.428 + 0.137
1.323 + 0.242
Although absent from the equation, generation of the co-fed steam
requires energy, and extra heat is necessary to raise the temperature
of the reactants to over 800oC. Some of this extra energy is
recovered (by steam generation) from the furnace flue gases and the
reactor outlet gases, but, with additional steam required for product
separation and purification, a net steam consumption results. The
overall yield of ethylene on ethane in modern US plant is about 85%
molar.
Acetylene (ethyne)
Before evaluating the petrochemical routes to acetylene, we should
look first at the long-established process for producing acetylene via
calcium carbide and water:
CaO + 3C CaC2 + CO
CaC2 + H2O C2H2 + CaO (or Ca(OH)2 with excess
water)
Essentially all the energy is consumed in calcium carbide
manufacture. In the electrothermal process, the reaction is carried
out at temperatures in excess of 1850oC.

25

If we ignore the lime (recovered), and convert other


consumption/by-product figures to energy values, we obtain (per
mol acetylene equivalent):
Coke
(3.5g-atoms
C/mol)
Electricity-actual input
Primary fuel value

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

The reactions of acetylene are simpler, and were important early


commercial routes to the products indicated, acetaldehyde, vinyl
acetate and acrylonitrile.
The main driving force to discover and develop olefin based routes
was the dramatic increase in scale of steam cracking operations in the
post-war years. Early increases in demand for synthetic ethanol and
ethylene oxide/glycol were followed by a rapid escalation in
polyethylene production, now the major outlet for ethylene. In
contrast, the group of products for which acetylene was the preferred
feedstock grew more modestly, and a disparity in required production
scales and prices developed. The steam cracking of naphtha in Europe
and Japan also gave propylene in large quantities, for which new
outlets had to be found. Thus acetylene was slowly squeezed out,
including later displacement production to acetylene production is
now 100-fold in USA if somewhat less elsewhere.

26

Vinyl Chloride (chloroethene).


The production of vinyl chloride naturally attracted the
attention of those companies already involved in chlorination
processes. The quantities of by-product hydrogen chloride available
were often an embarrassment and the relatively facile production of
vinyl chloride from acetylene and anhydrous HCl, over a supported
mercuric chloride catalyst, provided a valuable outlet.
As the market for vinyl chloride grew, major petrochemical
companies without existing chlorination capabilities looked to other
possible routes. With failing ethylene prices, the route pursued was
the addition of chlorine to ethylene, to give ethylene dichloride (EDC,
1,2-dichloroethane), and the thermal cracking of EDC at about 550 oC
to vinyl chloride and HCl.
CH2=CH2 + Cl2 ClCH2CH2Cl CH2=CHCl + HCl
A snag was that these companies now had to dispose of hydrogen
chloride. The most elegant solution was to react this with acetylene in
a separate stage, to give what became known as the Balanced
Process. This scheme became a driving force for naphtha cracking to
mixtures of ethylene and acetylene, as exemplified by the Wulff
process.
Polyethylene (polyethene) and polypropylene (polypropene)
Low-density polyethylene (LDPE) is produced by a free radical
process, initiated with traces of oxygen or peroxides, at temperatures
of 200oC to over 300oC and pressures up to 3000 atm. Over half of
this low-melting point, flexible product is used for packaging film
manufacture.
High density polyethylene (HDPE) is now produced mainly by
polymer growth on microscopic particles of catalytic materials
(chromium or Ziegler systems) suspended in a non-solvent or carried
along in the gas-phase, at only 70-125oC and 15-40 atm. The product
has a higher melting point and is more rigid, and finds major uses in
containers, moulded items and pipes. Polypropylene, with both
molding and fibre uses, ethylene-propylene copolymers and the
newest product line, linear low-density polyethylene (LLDPE), are
produced by similar methods. A C4/C6 terminal olefin co-monomer is
used in the latter to provide a tough, flexible film forming product.
27

2.2

Methane Derivatives

(C1 production)

For methanol and formaldehyde, see section 3.1


Formic (methanoic) acid and derivative
The modest US requirements for formic acid (30 kilotonnes per
annum) appear to be met mainly by co-product material from butane
oxidation (when available) and imports. Outlets are into a variety of
specialty areas.
In Europe, demand is swollen to over 100 kilotonnes per annum by
use for the preservation of damp silage (grass) and other animal
feedstuffs a means of saving the energy otherwise required for
drying. Co-product material from naptha oxidation is now exceeded
by BASFs recently expanded (200 kilotonnes per annum capacity)
methyl formate (methyl methanoate) production from syn gas. The
selective reaction
CH3OH + CO HCO2CH3
is catalysed by sodium methoxide at 80-100oC and 30-60 atm. BASF
can hydrolyse about 2/3 of the ester directly to formic acid by a
recently improved process. A Finnish plant is based on by-product
CO.
N,N-dimethylformamide (DMF) is an important solvent for acrylic
fibres and polyurethane leather production (and for separating
acetylene from ethylene). Metyl formate reacts readily with
dimethylamine.
HCO2CH3 + (CH3)2NH HCON(CH3)2 + CH3OH
DMF
Alternatively the amine can be introduced
methanol/carbon monoxide reaction systems.

directly

into

Mitsubishi have developed a process for methyl formate by the


dehydrogenation of methanol. However, the major objective is the
production of separate hydrogen and carbon monoxide streams for
other uses from imported methanol.
2CH3OH HCO2CH3 + H2

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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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