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Ethane-1,2-diol,
(ethylene glycol, monoethylene glycol,
MEG) which is manufactured from ethene
via epoxyethane, is used to make
polyester fibres, resins and films although
it is probably better known for its use as a
coolant in cars. It is miscible with water
and it lowers the freezing point of water so
it is used as an antifreeze.

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Figure 1 Uses of ethane-1,2-diol.

Data for 2013 from a variety of sources including IHS Markit,

2016.

By far the most important uses of the diol is in

the manufacture of polyesters, particularly PET
(polyehylene terephthalate), used widely for
clothes and for packaging. Indeed 45% of the
polyester is used for bottles1.
1. Global Processing, 2016.

Another important use is as a coolant in

engines. In modern engines, higher running
temperatures mean better fuel efficiency and
reduced emissions. Water is by far the best
coolant, having a low viscosity, high specific
heat capacity and high thermal conductivity, but
is limited in its use because of its relatively high
freezing point, low boiling point and it corrodes
metals. Ethane-1,2-diol (antifreeze) mixed with
water up to 60% volume gives a solution with a
freezing point down to 223 K. The boiling point
of the mixture also increases.

The corrosion problem is addressed with

corrosion inhibitors. If only cast iron had to be
protected, a simple pH adjustment with sodium
hydroxide and sodium borate as a buffer could
suffice, but engines are complex systems of
many metals and alloys so inhibitors are
packages of a number of compounds each of
which has a particular function. A traditional
European package might contain sodium
hydroxide and sodium borate for pH control to
7-9 (corrosion is much slower under alkaline
conditions), sodium nitrate, sodium silicate,
tolyltriazole, an organic acid (such as benzoic,
sebacic or citric), and sometimes a compound
which prevents foaming.

The globalisation of the car industry is leading

manufacturers to search for a 'world coolant',
acceptable everywhere.

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World 18 million tonnes

Europe 5 million tonnes

North America 3 million tonnes

US 1.1 million tonnes1

1. 2015, Business of Chemistry, American Chemistry Council,

2016

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Epoxyethane, produced from ethene, reacts
with water to form ethane-1,2-diol:

The hydration takes place under a variety of

conditions, neutral, acid-catalysed and base-
catalysed. Usually the reaction in industry is
carried out in neutral conditions or is catalysed
by acid (0.5% sulfuric acid) at 320-340 K, under
pressure.

Formation of higher homologues is inevitable,

because epoxyethane reacts faster with diols
than with water. This can be minimised by using
a large excess of water. A 20-fold molar excess
is not unusual. In practice, up to 90% of the
epoxyethane can be converted to ethane-1,2-
diol. Recently, over 93% yields have been
obtained.

After leaving the reactor, the product is distilled

at lower pressures to remove water which is
returned to the reactor. Ethane-1,2-diol is then
purified by vacuum distillation. Heat from the
reactor is used to heat the distillation columns.

This production method is simple but has some

disadvantages, such as requiring corrosion
resistant materials for the plant, the removal of
the acid from the product and the distillation of
large volumes of water.

A process has been developed recently for

converting epoxyethane to ethane-1,2-diol with
a yield of well over 99%. It is based on
technology from Mitsubishi Chemicals and
further developed by Shell Chemicals.

The conversion from epoxyethane to the diol

takes place in two stages. First the epoxide
reacts with carbon dioxide to form 1,3-dioxolan-
2-one (ethene carbonate):

An organophosphorus compound is used as the

catalyst.

Ethene carbonate is then reacted with water to

form ethane-1,2-diol and regenerates carbon
dioxide.

At first sight, it might be expected that the one

stage process from epoxyethane to the diol
would be more cost-effective than a two-stage
process involving carbon dioxide. However, the
selectivity of the one stage direct hydration
process, in terms of producing ethane-1,2-diol
rather than other by-products (higher diols), is at
best 93%. Whereas with the two stage process,
the selectivity increases to over 99.5% which is
sufficiently high for there to be no need for a
further stage of purification of the diol from the
by-products .Further, once the two stage
process is running, the carbon dioxide is
recycled very efficiently.

Figure 2 As with all chemical processes used in industry, th

conditions on the gram scale to a full scale industrial plant
produced annually, is very painstaking work for chemists a
photograph shows an intermediate stage in which a small p
to mimic large scale conditions for the OMEGA Process to
With kind permission of Shell International Ltd.

Shell now sells a combined EO/MEG

technology as an integrated Omega (only
mono-ethylene glycol advanced) process
package taking ethane and converting it to
ethane-1,2-diol.

The Omega process not only has lower capital

costs because there is no need for the
purification equipment to remove by-products,
but the operating costs are also reduced as it
uses much less water, consequently lowering
power and water treatment costs.

The first plant using the Omega Process was

commissioned in South Korea in 2008.

Figure 3 A new integrated refinery and petrochemicals facil

Singapore, known as the Shell Eastern Petrochemicals Com
steam cracker to produce ethene together with additions to
Island. A new plant to produce ethane-1,2-diol using the Sh
nearby Jurong Island. Bukom and Jurong Ilands are close t
the tip of Singapore.
With kind permission of Shell International Ltd.

Date last amended: 8th November 2016

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