Methanal (formaldehyde) is usually used as an aqueous solution containing 37%

(w/w) methanal, known as formalin. It contains a small amount of methanol and an

inhibitor (often an ethenyl (vinyl) polymer) to prevent the aldehyde from forming
long chain polymers on storage.

Uses of methanal (formaldehyde)

By far the largest use of methanal is in the production of the methanal resins. The
principal ones are made from methanal and phenol from methanal and
carbamide (urea) and from methanal and melamine.

Manufacture of methanal (formaldehyde)

Most methanal is produced from methanol by a process that involves both
dehydrogenation and oxidation:
A mixture of methanol vapour and air at ca 1000 K and just above atmospheric
pressure is passed over a catalyst of finely divided silver or molybdenum(VI) oxide
on an inert support.
The resulting methanal is absorbed in water. The byproduct, hydrogen, is used as a
fuel for the process.

Polyoxymethylene resins (polyacetal resins)

The polymerization of anhydrous methanal leads to the formation of the
polyoxymethylene (or acetal) resins, which are thermoplastics.
They are either made as a homopolymer, to which ethanoic acid is added to
terminate the chains:
Both the homopolymer and co-polymer are very tough and resistant to abrasion.
They are used, instead of metals, in, for example, bearings and gears and in
plumbing.
The photograph shows the black casing that holds a fuel filter for an Audi car and on
the right it shows how the filter fits into the fuel system. The plastic used to make
the casing, as well as being suitably strong when moulded into the required shape,
must also have good electrical conductivity. Fuel moving through the filter could
cause the build up of an electrostatic charge that could lead to sparking unless the
casing can safely conduct away the charge. The casing is a composite made from a
polyoxymethylene resin, which has carbon nanotubes dispersed throughout the
resin matrix to enhance its electrical conductivity.

Methanol is produced from synthesis gas (carbon monoxide and hydrogen), itself
derived from oil,coal or, increasingly, biomass. It may become central to the
development of biorefineries as an intermediate in the conversion of biomass to
useful products.

Uses of methanol
The largest use for methanol is as a feedstock for the plastics industry. It is used to
make methanal and hence a variety of plastics, based on reactions with phenol,
carbamide (urea) and melamine.
Polymers such as the polyesters (e.g. Terylene) and poly(methyl-2methylpropenoate) (e.g. Perspex) use methanol as the original feedstock. Methanol
is now the principal source for the manufacture of ethanoic acid.

Manufacture of methanol
Methanol is manufactured from synthesis gas which is a mixture of carbon
monoxide and hydrogen.
Synthesis gas is catalytically converted to methanol at elevated temperatures and
pressures in a fixed bed reactor. The catalyst is an alumina pellet coated with
copper and zinc oxides.
From considering the energetics of the reactions, it can be seen that the yield of
methanol is favoured by high pressures and low temperatures.
Figure 4 The converter in which methanol is being produced from synthesis gas.
Methanol is converted into alkanes and aromatic hydrocarbons suitable for petrol
(hydrocarbons with 5 to 8 carbon atoms), by passing the vapour over alumina at ca
600 K. An equilibrium mixture of methanol, dimethyl ether and steam is produced,
containing about 25% methanol:

Methyl t-butyl ether (2-methoxy-2-methylpropane), often referred to as simply

MTBE, has been widely used over the last 30 years to improve the burning
characteristics of petrol.
When oil is distilled, the fraction that can be used as petrol (the naphtha fraction) is
made up mainly of C4 to C10 straight chain alkanes, which have suitable volatility.
However, these burn in a way that leads to explosion in the engine cylinder at the
wrong time (knock). One way to improve the performance of the petrol (indicated
by its octane rating) is to add compounds whose molecules contain oxygen (known
as oxygenates) such as ethanol and some ethers. MTBE is widely used in Europe for
this purpose and also, increasingly, is its homologue ethyl t-butyl ether (ETBE).

Uses of methyl t-butyl ether

There are three ways of improving the octane rating of petrol. One is to add a
volatile lead compound, usually lead tetraethyl, Pb(C2H5)4. However, there is great
concern that when lead compounds are released into the atmosphere from the
exhaust, they damage our health and their use is now prohibited. They
also poison the metal catalysts in catalytic converters.
A further way to improve the octane rating is to add an oxygenated compound.
Methyl t-butyl ether, MTBE, has been most widely used and its production grew
over 20 years from almost zero to 16 million tonnes a year.
However, the second reason for using MTBE in petrol is also important. MTBE burns
very effectively to carbon dioxide and water and there are very few other sideproducts, even in small amounts. With the very stringent anti-pollution legislation
in the US, Europe and other developed countries, MTBE was added thus reducing
the proportion of hydrocarbons in petrol which in turn means an overall reduction of
polluting gases (carbon monoxide and unburnt hydrocarbon) in the exhaust.

Manufacture of methyl t-butyl ether

(ii) By dehydrogenation of 2-methylpropane, which is also formed as a by-product in
various processes in the petrochemical industry. The vapour is passed over a
catalyst (platinum and palladium on an inert support)
(iii) Another route from 2-methylpropane involves its oxidation to 1,1-dimethylethyl
hydroperoxide (often called t-butyl hydroperoxide
Cracking, as the name suggests, is a process in which large hydrocarbon molecules
are broken down into smaller and more useful ones. Reforming is another process in
which hydrocarbon molecules are rearranged into other molecules, usually with the
loss of a small molecule such as hydrogen. An example is the conversion of an
alkane molecule into a cycloalkane or an aromatic hydrocarbon

Ethyl t-butyl ether (ETBE)

Ethyl t-butyl ether (ETBE) 2-ethoxy-2-methylpropane) is an alternative to MTBE as
an oxygenate to enhance the octane rating of petrol. It is used mainly in Europe,
particularly in France. This accounts for over 90% of the world's annual production
of ca 3 million tonnes.
It is manufactured from 2-methylpropene and ethanol
Figure 1 A plant which has been recently commissioned in Geleen in the Netherlands to
produce ethyl t-butyl ether, ETBE. The reactants are 2-methylpropene and bioethanol.
This product is referred to as bio-ETBE.

The production of phenol from benzene is the first step in the manufacture of some
very important polymers, including polyamides (nylons), polycarbonates and the
phenolic resins.

Uses of phenol
The most important chemical made from phenol is bisphenol A, which is used to
make the polycarbonates. Phenol is also catalytically reduced to cyclohexanol,
which is used in the manufacture of polyamides 6 and 6,6.
Phenol is also used to make a range of thermosetting polymers (resins). It reacts
with methanal in the presence of a catalyst to form phenol-methanal resins.
Among the other uses of phenol is the production of phenylamine (aniline) needed,
for example, for the manufacture of dyes. Antiseptics such as 2,4-and 2,6dichlorophenols are also made from phenol.

Manufacture of phenol
(a) Production of cumene
Cumene is the name often given to (1-methylethyl)benzene (isopropylbenzene). It
is produced by the reaction of benzene and propene, using an acid catalyst; this is
an example of a Friedel-Crafts reaction:
In one process, benzene and propene (3:1) are passed over an acid catalyst, usually
a zeolite such as ZSM-5 at ca 600 K and under pressure (ca 10 atm) in a fixed bed
reactor. The zeolite is more environmentally friendly than traditional acid catalysts
such as aluminium chloride. The effluent is much cleaner and lower temperatures
and pressures can be used.

Figure 2 An aerial view of the plant producing phenol and propanone from
cumene.
Alternatively, propene gas is liquefied under pressure (ca 30 atm) and mixed with
benzene before being passed, still under pressure, through a reactor containing the
solid zeolite at ca 435 K. This process is becoming more popular as it uses even
lower temperatures and thus saves energy.
In some plants, solid phosphoric acid is used as the catalyst, in place of zeolites.
(b) Conversion of cumene to cumene hydroperoxide
Cumene is then oxidized with air to give the hydroperoxide (Figure 3). The reaction
is autocatalyzed by cumene hydroperoxide. The overall reaction can be
represented as:
The reaction takes place at temperatures between 350-390 K and 1-7 atm pressure,
the latter to retain the system in the liquid phase.
Figure 3 Oxidation units in which cumene hydroperoxide is produced.
At higher temperatures, the hydroperoxide is unstable and could decompose
violently. The oxidizers are generally built some distance from the rest of the plant.
c) Decomposition of cumene hydroperoxide
Finally, the hydroperoxide is mixed with sulfuric acid at 313-373 K to give, after
neutralisation, phenol and propanone. This reaction when carried out with small
amounts of sulfuric acid (500 ppm by mass) is termed homogeneous cleavage:
The products are separated by distillation, in up to six columns. Product yield is 8587%, based on benzene.
Figure 4 Distillation units to separate phenol and propanone.

Propanone (acetone) is one of the most important solvents as many organic

compounds dissolve readily in it but it is also miscible with water. It is also a key
intermediate in the manufacture of some polymers.

Uses of propanone (acetone)

The plastics industry uses about half the propanone produced.
It can be converted into bisphenol A, used in the manufacture
of polycarbonates and epoxy resins, used in paints and into methyl 2methylpropenoate used to make poly(methyl 2-methylpropenoate),sold as Perspex.
It is converted into 4-methylpentan-2-one (MIBK) (see below) which is a very useful
solvent for paints.

Manufacture of propanone (acetone)

There are two ways of manufacturing propanone, one via cumene and one via
propan-2-ol (isopropanol). Both of these intermediates are produced from propene.
By far the most important route is the cumene process.
The second route is by dehydrogenation of propan-2-ol. The alcohol vapour is
passed over zinc oxide at ca 600 K or copper at ca 750 K, which act as catalysts:
Bisphenol A
To make bisphenol A, the two products from cumene oxidation are reacted together:
In the past, hydrogen chloride was used as the acid catalyst, and some inevitably
escaped into the atmosphere. Now a solid cation exchange resin is used which is
more environmentally friendly.
Although the main use of bisphenol A is in the manufacture of polycarbonates, it is
also used in the manufacture of fire retardants, including tetrabromobisphenol A.

Propene (often known as propylene), like ethene, is a very important building block
for a large number of chemicals, including the addition polymer, poly(propene).
However, unlike ethene, propene readily undergoes substitution reactions, which
lead to a wide range of important chemicals.

Uses of propene (propylene)

The principal uses of propene are to produce:

poly(propene) (polypropylene)
Propenal (acrolein) which is oxidized to propenoic acid (acrylic acid) which, in
turn, is used to make acrylic polymers
Propenonitrile (acrylonitrile) which is the monomer for poly(propenonitrile)
Cumene ((1-methylethyl)benzene or isopropylbenzene) which is then used to
make phenol and propanone (acetone)
epoxypropane (propylene oxide) which is used to make diols for the
manufacture of polyurethanes and solvent
butanal (butrylaldehyde) and hence butanol, used as a solvent for surface
coatings

Manufacture of propene (propylene)

Propene is manufactured by:

steam cracking of propane and butane (from natural gas and oil)
steam cracking of naphtha (from oil)
catalytic cracking of gas oil (from oil) and propane

Steam cracking accounts for ca 56% and catalytic cracking for 33% of the global
production. Much of the rest is made from the production of oil from coal and from
the cracking of gas oil under vacuum,
Increasingly, propane is being catalytically cracked to form propene, using the
same cat cracker as that used to crack gas oil:
The reason for the increase in production of the alkene from propane is because of
the increasingly large amounts of the feedstock obtained from shale gas in the US.

Urea (carbamide), readily produced from ammonia and carbon dioxide, is a very
important chemical in the agricultural and the polymer industries.

Uses of urea
Urea is the world's most commonly used nitrogen fertilizer and indeed more urea is
manufactured by mass than any other organic chemical. Containing 46% N, it is the
most concentrated nitrogen fertilizer, and is readily available as free-flowing prills
(granules). It is the cheapest form of nitrogen fertilizer to transport and it is also
the least likely to 'cake'. It is therefore favoured in developing countries.
An increasingly important use of urea is in reducing air pollution from diesel engines
in cars, buses and Lorries. Diesel engines run at high temperatures and nitrogen
and oxygen, from the air, are able to react together under these conditions to
produce high concentrations of nitric oxide. One way to remove this pollutant is to
allow it to react with ammonia to form nitrogen.
However it is not possible to use ammonia directly as it is too volatile and is
poisonous. Instead a solution of urea in water is injected into the hot gases
emerging from the engine in the exhaust. Urea is thermally decomposed to
ammonia and carbon dioxide. This is the reverse of the process used to make
ammonia:
Unlike ammonia, urea is safe and easy to handle.
The products, ammonia and carbon dioxide, together with the exhaust gases, are
passed immediately over a catalyst in the exhaust system. Ammonia reduces the
oxides of nitrogen (mainly nitric oxide), formed in the combustion processes, to
nitrogen. The process is complex but the overall reaction can be represented thus:

Manufacture of urea
Ammonia reacts with carbon dioxide to produce urea. Urea is always manufactured
close to an ammonia plant
Ammonia and carbon dioxide are heated together at 450 K and 200 atm pressure.
First ammonium carbamate is formed, which rapidly decomposes to form urea:
Figure 5 An aerial view of a large plant in Alberta, Canada, in which
ammonia is synthesized and then converted to urea.