Introduction:

Ethylene oxide, properly called Oxirane by IUPAC, is the organic

compound with the formula C2H4O. It is a cyclic ether (A cyclic ether
consists of an alkane with an oxygen atom bonded to two carbon atoms
of the alkane, forming a ring.) Ethylene oxide is a colorless flammable gas
at room temperature, with a faintly sweet odor; it is the simplest epoxide:
a three-membered ring consisting of one oxygen atom and two carbon
atoms.[4]

Figure(1) : Molecule of Ethylene Oxide.

The C-C bond is short and the bond angles strained. Ethylene Oxide is
highly reactive because of the strained ring that can easily be opened. The
three-membered ring is opened in most of its reactions. These reactions
are very exothermic because of the tremendous ring strain in ethylene
oxide.[2]
Ethylene oxide is a highly versatile commodity chemical, which is used as
an intermediate for the production of a variety of chemicals. It also kills
bacteria, mold, and fungi, and is therefore used as a sterilant. During
World War I, it gained importance in industry and was produced on a
small scale for its use in the production of ethylene glycol and the
chemical weapon mustard gas.[1]
the Asia-Pacific is the global leader in ethylene oxide demand and
contributed about 64% to total revenues in 2012. Together with Central
Europe, the Middle East and South America, the Asia-Pacific will drive up
demand for ethylene oxide in the next few years. North America and
Western Europe will make only a modest contribution as their mature
markets deliver sluggish growth.[5]

1. Background
Ethylene oxide was first prepared in 1859 by Charles Wutz using a
potassium hydroxide solution to eliminate the hydrochloric acid from
ethylene chlorohydrin. In 1914 the ethylene chlorohydrin process was the
first technology to produce ethylene oxide commercially. The process
involves the reaction of ethylene with hypochlorous acid followed by
dehydrochlorination of the resulting chlorohydrin with lime to produce
ethylene oxide and calcium chloride. Although the selectivity of this
process was approximately 80%, the process itself was very inefficient and
caused pollution problem by generating large quantity of unwanted
chlorinated hydrocarbon byproducts. In 1931, Theodore Lefort
discovered a way to prepare ethylene oxide directly from ethylene and
oxygen with a silver catalyst, the direct oxidation processes. This process
was more economically competitive and soon replaced the ethylene
chlorohydrin process.
The direct oxidation technology is the dominant process to produce
ethylene oxide commercially today. It utilizes the catalytic oxidation of
ethylene with pure oxygen over a silver based catalyst to yield ethylene
oxide.[1]

Physical properties:
is a colourless gas at room temperature, turns liquid below 12C, soluble
in organic solvents and miscible with water in all proportions. It is highly
flammable, with a flam- mable limit in air of 3-100%.[6]

Preparation of ethylene oxide:

1. Chlorohydrin process
One of the two fundamental reactions that are involved in the production
of ethylene oxide by the chlorohydrin process is the reaction of ethylene
with hypochlorous acid to form chlorohydrin:
CH2CH2 + HOCl HOCH2 CH2Cl

(1)

The chlorohydrin process is carried out in packed towers at 27-43C and

2-3 atm pressure at a yield of 85-90%. To avoid formation of by products

(ethylene dichloride, dichlorodiethyle ether etc.) the concentration of

chlorohydrin in the chlorohydration reaction solution is maintained below
7 wt.%.
The second step of the process, dehydrochlorination, is accomplished by
adding 10 wt.% aqueous slurry of lime, usually calcium hydroxide, to the
chlorohydrin solution to form ethylene oxide.
HOCH2CH2Cl + Ca(OH)2 CH2CH2O + CaCl2 + 2 H2O (2)
The mixture is then heated to just less than 100C in the hydrolyzer, a
cylindrical vessel with a reflux condenser operating at essentially
atmospheric pressure. As the chlorohydrin reacts with the dissolved lime
ethylene oxide, by- products and some water is formed. The ethylene
oxide is removed as a vapor from the partial condenser. The vapor stream
from the hydrolyzer is passed through a cooler and partially condensed
and then fed to the fractionated section. The purification of
the crude ethylene oxide is difficult and requires a number of distillation
towers.
The chlorohydrin process is no longer in use but has a historical value. The
main reason why chlorohydrin process is no longer in use is the
economical factor. It is 3-4 times more expensive to produce ethylene
oxide by chlorohydrin process than by direct oxidation process. Another
disadvantage of the chlorohydrin process is the problem of treating the
large waste stream containing calcium chloride and amounts of
chlorinated hydrocarbons and glycols.[2]
2. The direct oxidation process
In 1931, the direct gas phase oxidation of ethene to ethene oxide was
discovered by Lefort .In this process, the oxidation of ethene is performed
directly with oxygen or air and silver as catalyst.
oxidation is more cost efficient than the chlorohydrin route. Therefore,
the chlorohydrin route was abandoned in the 1950s.
there have been two types of direct oxidation processes used for the
production of ethylene oxide.[7]
1- Air-Based Direct Oxidation Process.
2- Oxygen-Based Direct Oxidation Process.

Air-Based Direct Oxidation Process:

Compressed air is first purified to remove contaminants and then mixed
with recycled gas and fresh ethylene. Vapor phase oxidation inhibitors
such as ethylene dichloride or vinyl chloride or other halogenated
compounds are added in the inlet of the reactor to retard carbon dioxide
formation. The gas is fed to a multitubed catalytic reactor in which the
reactor temperature is controlled with boiling water or circulated nonboiling organic oil on the shell side. If oil is used, it is cooled in a steam
generator, producing high pressure steam which is used in the process.
The effluent gas from the main reactor, which now contains ethylene
oxide, is cooled in a shell- and-tube heat exchanger with cold reactor feed
gas. The cooled gas is then fed in to the main absorber where the ethylene
oxide is absorbed in water, produce a dilute aqueous solution. The
scrubbed gas from the absorber is then compressed and the major
portion of the gas is recycled to the main reactor. A part of the gas flow is
sent to secondary (or purge) reactor system to purge both the nitrogen
introduced in the air feed and also the carbon dioxide produced in the
reactor.[2]

Oxygen-Based Direct Oxidation Process:

High purity oxygen is mixed with recycled gas and fresh ethylene and the
combined gases are the fed into a multitube reactor similar to the one in
the air based process. The effluent gas, containing ethylene oxide is heat
exchanged with cold reactor fed gas before it enters the absorber. In the
absorber the ethylene oxide is dissolved in the absorber water to produce
a dilute aqueous solution. The scrubbed gas is then compressed and
recycled to the reactor. A part of the recycle gas is first sent to a CO2
absorber where carbon dioxide produced in the reactor is chemically
absorbed in a recirculated solution of hot potassium carbonate. The CO2
lean gas is then returned to the recycled gas and back to the reactor. The
CO2-rich carbonate solution is regenerated in the CO2 stripper using
steam and the desorbed carbon dioxide is vented out in the top of the
column. [1] To avoid accumulation of other inert such as argon which is
an impurity in the oxygen supply a small purge of cycle gas is vented to
atmosphere or incinerator. If argon is not vented out it can build up to 3040% in the cycle gas. Because of the lower heat capacity of the argon, the

cycle gas may enter the flammable region, and as a result of that the
oxygen concentration needs to be decreased in the cycle gas.[2]

Air vs Oxygen Process Differences and Economics:

The differences for all air and oxygen based plants with the same capacity
and same type of catalyst are that the oxygen based process yields a
higher selectivity and requires less catalyst. The air based process has a
higher initial building cost but most of the small to medium plants has a
lower run cost. The oxygen based processes need a carbon dioxide
removal section, more stainless steel and some expensive
instrumentation. For the air based process to achieve the same selectivity
it requires more catalyst, more reactors, a multi-stage compressor, air
purification unit, and a vent gas treating system and two to three reactor
train in series. In spite additional equipment for the air based process the
selectivity is less than for an oxygen based process. In 1970 the average
selectivity for an air based process is 65-75% and for the oxygen based
process around 70-80%.[2]