BENZENE

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ANNUAL PRODUCTION
Benzene is one of the main building blocks of the petrochemical industry. The global market
grew from 4 million tonnes in 1960 to over 30 million tonnes in 2000.
Most of the benzene produced is from Western Europe, North America and Asia.
World production (million
tonnes)
World production 30

Western Europe 7.53

North America 7.23

South America 0.89

Asia 8.49

Note on Terminology of benzene compounds

Compounds of benzene are often referred to as aromatic compounds. When the benzene
ring is attached to another molecule in place of hydrogen it is called a phenyl group.
 USES
Benzene is an intermediate in the production of many important chemicals used in the
manufacture of plastics, drugs, dyes, detergents and insecticides.

Intermediate End Use/Products

Used to produce the phenylethene (styrene) monomer for
manufacturing polystyrene used in packaging, insulation etc.

Ethylbenzene
Cumene Used in the production of phenol, which in turn is used in the
manufacture of a wide range of products from resins and plastics
to weed killers like 2,4-D (2,4 dichlorophenoxyacetic acid) and
MCPA (2-methyl-4-chlorophenoxyacetic acid).

Cyclohexane Used to make hexanedioic acid (adipic acid) for nylon production.

Maleic This is used in the production of unsaturated polyester resins, used

with glass fibre reinforcement to manufacture boats, translucent
roof sheeting, baths and shower trays. Mixed with powders, such
as calcium carbonate, the resin can be moulded to make synthetic
marble, onyx and granite for wash basins, fire surrounds etc.
anhydride 
These are used to make the "surfactants" in detergent production .

Alkylbenzenes 
Used in the manufacture of insecticides like tetradifon (1,2,4-
trichloro-5-[(4-chlorophenyl)-sulphonyl]-benzene).

Chlorobenzene 

Used to produce aromatic amines (e.g. phenylamine), azo-dyes

and explosives like methyl-2,4,6-trinitrobenzene (TNT).

Nitrobenzene 
Benzene used to be a commonly used solvent, but in many cases safer solvents have now
replaced it (for example methylbenzene or non-aromatic solvents). Research chemists no longer
use it, and its use as a solvent in industry is carefully controlled.
Benzene and Fuel
Aromatics, like benzene, methylbenzene (toluene) and dimethylbenzene (xylene), are
natural components of petrol (commonly 3- 9 %), and are also produced by its combustion.
Concerns over benzene levels in air pollution have led to much stricter limits in many countries (<
1% benzene from 2000 in EU). Much research work is based around developing cleaner fuels for
transport.
ISSUES
Whilst benzene remains a very important building block in the chemical industry, concerns
over its effect on health have led to steps being taken to reduce the amount released into the
atmosphere. Research chemists no longer use it, and its use as a solvent in industry is carefully
controlled.
 Chemical Plant
Plants producing and using benzene regularly test all pipe joints for leaks, and use safety
valves, flanges and gaskets of the highest quality. Emissions on industrial sites are now at very low
levels, and will continue to fall.
Petrol
Benzene has been used in some countries to raise the octane rating of unleaded petrol and
prevent knocking (fuel combustion that occurs at the wrong time, lowering efficiency and increasing
engine wear). Concerns over atmospheric levels of benzene mean that permitted levels are now
low (typically around 2%), but road transport still remains the main source of atmospheric benzene.
Other Sources
Benzene is also found in foods, water, and is present in tobacco smoke. This means the
total intake for an individual will depend on where they live, what they eat and drink, and if they
choose to smoke. A 20 per day smoker living in an urban centre could have a daily intake of up to
1255 mg, which could be up to 10 times that for a non-smoker in a rural location.

Health Effects
 Benzene is volatile, and most ill effects are the result of inhalation of the vapour.
 At low levels it produces drowsiness, headaches and vomiting.
 Higher levels can result in unconsciousness, with very high levels of exposure causing
death within a relatively short time (5 - 10 minutes).
Long term, low level exposure (such as would be possible with workers in the chemical, oil
refinery or waste disposal industries) is of concern as benzene is a known carcinogen (linked to the
development of cancer), and can damage the immune system and cell chromosomes.
 The Future of Benzene
Benzene will remain an important chemical for some time to come, and production levels
are expected to continue to rise. Several processes are in use or development that allow end
products, for which benzene is currently the main feedstock, to be made in other ways.
For example, phenolic resins, which account for about 7-8% of benzene production, can be made
from waste biomass.
PRODUCTION METHODS SUMMARY
Michael Faraday isolated benzene in 1825 by compressing oil gas, the lightest fraction
produced by the distillation of coal tar. Most production today comes from crude oil, using three
main routes. None of these is dedicated primarily to the production of benzene, and the method
used at any one particular time by a company depends on many factors, including:
 The feedstock available
 Demands for other products
Cracking of Oil Products
The distillation of crude oil results in several fractions, with the naphtha (C5 - C10
hydrocarbons) and gas oil (C14 - C20) fractions together making up as much as half the output.
Demand for these hydrocarbons is exceeded, and so these fractions are cracked - which literally
means breaking the larger molecules into smaller ones. Crude oil will usually contain dissolved
ethane and propane too, and these are removed before distillation and used as feedstock for
cracking.
One of the products of cracking is raw pyrolysis gasoline (RPG), which is rich in benzene
and other aromatic compounds. Click here for more on this process.
Reforming of Naphtha
The reforming of naphtha is exactly that Ð the molecules in naphtha, mainly straight chain
alkanes in the C5 to C10 range, are re-formed into molecules with the same number of carbon
atoms but different structures.
Naphtha vapour and hydrogen are passed over a platinum/alumina catalyst, and is
converted into a variety of products, including benzene and other aromatics, which can be
separated from each other. One of the main purposes of catalytic reforming of naphtha is raising
the octane rating of petrol. For more information, click here.
Disproportionation of Methylbenzene
Naphtha reforming generates methylbenzene (toluene) among the aromatic products, but
unfortunately the demand for this is much lower than for dimethylbenzene (xylene), produced in
much smaller quantities by reforming.
Methylbenzene can, however, be converted to dimethylbenzene and benzene using a
catalyst. The benzene can then be separated from the mixture. To find out more, click here.
FEEDSTOCK
The processes that produce benzene are all dependent on fossil fuels, primarily natural gas
and crude oil. A very small quantity of benzene is obtained from distilling the oil from coke ovens
(used to make coke for the iron and steel industry).
Steam cracking uses either the naphtha fraction from the distillation of crude oil, or ethane
found dissolved in oil or in natural gas. In general, naphtha is the main feedstock used in the UK
and Western Europe. Ethane is used in the US, simply because ethane is in abundance in the
natural gas found in that part of the world.
Catalytic reforming also uses the naphtha fraction.
The disproportionation of methylbenzene makes use of one of the products from the
catalytic reforming carried out on the naphtha fraction.
Aromatics plants are generally situated within refineries or petrochemical complexes,
reflecting the interconnection between the feedstocks for these processes. It also allows for the re-
use of hydrocarbon fractions, after aromatics removal, as gasoline or feedstock to steam crackers.
CRACKING OF OIL PRODUCTS
Cracking is used to convert components of crude oil, for which there is insufficient demand,
into smaller molecules, for which a demand exists. Cracking may be carried out:
 At a very high temperature with steam (steam cracking)
 At a high temperature with a catalyst (catalytic cracking)
 Using hydrogen and a high pressure (hydrocracking) The choice partly depends on the
products required
Steam Cracking
The feedstock is vaporised by pre-heating, mixed with steam, and passed into a furnace.
The resulting mixture of products depends on the feedstock, the temperature used (between 700
and 900 °C), and the time spent in the furnace ("residence time"), which ranges from 0.1 and 0.5s.
All feedstock produces significant quantities of ethene, a particularly useful chemical, but
naphtha and gas oil also generate a high proportion of raw pyrolysis gas (RPG), and this is
favoured by lower temperatures and shorter residence times.
RPG is a mixture of C5 to C8 hydrocarbons, including several aromatic compounds,
including benzene. The composition of RPG includes:
 benzene
 methyl benzene
 1,2- 1,3- & 1,4- dimethylbenzene
 aliphatic (non-aromatic) hydrocarbons in the C5 to C10 range, including both alkanes and
alkenes
Naphtha cracking results in about 30% each of ethene and RPG, and significant quantities
of other products.
 Processing RPG
The RPG is reacted with hydrogen, and this results in:
 The hydrogenation of mono-alkenes to saturated alkanes, for example:

 The desulphurisation of the gas mixture (any sulphur present will react with the hydrogen)
 No hydrogenation of any benzene to cyclohexane under these conditions (because of the
stability of the benzene ring)
The benzene and other aromatics are removed by solvent extraction, as these will dissolve
in polar solvents whereas the other hydrocarbons will not.
Desulphurisation produces hydrogen sulphide, which can be removed by dissolving in a
base. The hydrogen sulphide can be recovered and used in other processes (see sulphuric acid
section)
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Separating Benzene
The separation of pure benzene from its feedstock is difficult as it forms azeotropic mixtures
(i.e. constant boiling mixtures) with many C6 - C8 alkanes. Distillation will always produce a
mixture, not the pure compounds. Benzene cannot therefore be separated from these alkanes by
fractional distillation and various other techniques have to be employed, usually solvent
extraction. Click for details of separation methods used.
Question
Why is the removal of sulphur important to achieve?
Answer
Many processes using the products will make use of catalysts, and these are easily
poisoned by the presence of sulphur. The presence of sulphur may also result in sulphur dioxide
being generated in later processes, needing further costly treatment.
 NAPHTHA REFORMING
The Reforming Process
During the reforming of naphtha, mainly straight chain alkanes, with 6 - 10 carbon atoms,
are re-formed into molecules with the same number of carbon atoms but different structures.
The naphtha is first purified to remove sulphur, which would poison the catalyst, and then
mixed with recycled hydrogen and heated to about 500°C, a process known as hydroforming.
This mixture passes into a series of reactors containing a catalyst, normally
platinum/alumina. Older processes operate at 20 atmospheres pressure, but modern plants run at a
lower pressure of 5 atmospheres and use continuous catalyst regeneration. This means the
catalyst is withdrawn on a continuous basis and conveyed through a regeneration system before
being returned to the reactor.
Question
What advantages are there in working at lower pressures?
Answer
The use of lower pressures makes the process safer, and reduces the cost of the plant as
pipe work and reaction vessels do not need to be as thick to withstand the higher pressures.
Products
Naphtha is converted into a series of branched alkanes, cycloalkanes and aromatic
hydrocarbons. Benzene is formed from hexane:

Similarly, methylbenzene and three dimethylbenzene isomers are formed from heptane and
octane respectively:
 Separation
The aromatic compounds are separated from the non-aromatic compounds by solvent
extraction, and are then fractionally distilled into benzene, methylbenzene and the
dimethylbenzenes. Click for more details of separation methods used.
DISPROPORTIONATION OF METHYLBENZENE
Excess Methylbenzene
A major disadvantage of the reforming of naphtha is that the proportions of methylbenzene
and dimethylbenzene produced do not match the demands Ð there is too much methylbenzene,
and not enough dimethylbenzene.
Many sites therefore incorporate a disproportionation plant, which converts methylbenzene
into the dimethylbenzenes and benzene.

All three isomers of dimethylbenzene are produced, though it is the 1,4-dimethylbenzene

isomer (shown in the equation) that is most useful.
 The Process

Methylbenzene and hydrogen are passed over a zeolite catalyst at 15 -25 atmospheres and
at a temperature of 430 -480°C. Further information on zeolite catalysts can be found on the
catalysis site.
Any benzene, methylbenzene and dimethylbenzenes are separated by fractional distillation.
The methylbenzene can be returned to the disproportionation unit, whilst benzene and the
dimethylbenzenes removed.
Excess 1,3- dimethylbenzene can be converted to the more useful 1,4- isomer using the
Zeolite catalyst ZSM-5. It is thought this occurs via an acid catalysed rearrangement within the
pores of the Zeolite structure, where the shape of the 1,4-isomer is a "better fit".
New Catalysts
A new catalyst has been developed that allows methylbenzene to enter, but only the 1,4-
dimethylbenzene isomer can escape. The other isomers remain trapped until they are isomerised
to the 1,4-isomer.
Question
Why is the use of a catalyst that only produces the 1,4 isomer of dimethylbenzene a "more
green" process?
  Answer
The use of lower pressures makes the process safer, and reduces the cost of the plant as
pipe work and reaction vessels do not need to be as thick to withstand the higher pressures.
 The catalyst is based on MCM-41 (Mobile Crystalline Material). This is one of a group of
silicates that can be constructed to contain open hexagonal channels, and they are used as
catalyst supports, catalysts (with modification) or as molecular seives. Changing the length of the
molecules that are used to build the sides of the hexagon can control the diameter of the hexagonal
openings, and so the channels, or "pores", can be made from 2 to 10nm wide.
By adding a "gate" at the end, the size of molecule that can enter and leave the pores is
restricted. In this case the opening is set so that any 1,2- or 1,3- isomers of dimethylbenzene will
not be able to leave the pores, but the 1,4- isomer will.

Separation techniques
Separation of Aromatics
Benzene forms azeotropic mixtures with many C6 - C8 alkanes. This means that the
mixture reaches a constant boiling point with a fixed proportion of benzene and the alkane in both
the liquid and vapour. Benzene cannot therefore be separated from these alkanes by simple
fractional distillation and various other techniques have to be employed.
These mostly involve using solvents that dissolve the aromatic components (mostly
benzene, methylbenzene and dimethylbenzene) but not the alkanes. Very polar solvents are used
for this technique, for example alcohols.
 Separating Benzene
The aromatic compounds, benzene, methylbenzene and dimethylbenzene, which are all
dissolved in the solvent, can be separated using fractional distillation. The solvent recovered by this
distillation is re-used. Any methylbenzene obtained is returned to the disproportionation unit.