ETHYLENE OXIDE

Ethylene oxide, called oxirane by IUPAC, is an organic compound with

the formula C2H4O. It is a cyclic ether and the simplest epoxide: a three-membered
ring consisting of one oxygen atom and two carbon atoms. Ethylene oxide is a
colorless and flammable gas with a faintly sweet odor.

PROCESS SELECTION:
The process selected for the preparation of ethylene oxide is “Direct oxidation of
Ethylene”. It was patented by Lefort in 1931. This method was repeatedly modified
for industrial use, and at least four major variations are known. They all use
oxidation by oxygen or air and a silver-based catalyst, but differ in the technological
details and hardware implementations.
Union Carbide (currently a division of Dow Chemical Company) was the first
company to develop the direct oxidation process.

PROCESS DESCRIPTION:
1) Oxygen Based Oxidation Process:
The production of ethylene oxide on a commercial scale is attained with the
unification of the following unit processes:

 Main reactor
 Ethylene oxide scrubber
 Ethylene oxide de-sorber
 Stripping and distillation column
 CO2 scrubber and CO2 de-scrubber
Main Reactor:
The main reactor consists of thousands of catalyst tubes in bundles. These tubes
are generally 6 to 15 m (20 to 50 ft) long with an inner diameter of 20 to 50 mm
(0.8 to 2.0 in). The catalyst packed in these tubes is in the form of spheres or rings
of diameter 3 to 10 mm (0.12 to 0.39 in). The operating conditions of 200–300 °C
(390–570 °F) with a pressure of 1–3 MPa (150–440 psi) prevail in the reactor. To
maintain this temperature, the cooling system of the reactor plays a vital role. With
the aging of the catalyst, its selectivity decreases and it produces more exothermic
side products of CO2.
Ethylene oxide scrubber:
After the gaseous stream from the main reactor, containing ethylene oxide (1–
2%) and CO2 (5%), is cooled, it is then passed to the ethylene oxide scrubber.
Here, water is used as the scrubbing media which scrubs away majority of ethylene
oxide along with some amounts of CO2, N2, CH2=CH2,
CH4 and aldehydes (introduced by the recycle stream). Also, a small proportion of
the gas leaving the ethylene oxide scrubber (0.1–0.2%) is removed continuously
(combusted) to prevent the buildup of inert compounds (N2, Ar, and C2H6), which
are introduced as impurities with the reactants.
Ethylene oxide de-sorber:
The aqueous stream resulting from the above scrubbing process is then sent to
the ethylene oxide de-sorber. Here, ethylene oxide is obtained as the overhead
product, whereas the bottom product obtained is known as the glycol bleed. When
ethylene oxide is scrubbed from the recycle gas with an aqueous solution, ethylene
glycols (viz. mono-ethylene glycol, di-ethylene glycol and other poly-ethylene
glycols) get unavoidably produced. Thus, in-order to prevent them from building
up in the system, they are continuously bled off.
Stripping and distillation column: Here, the ethylene oxide stream is stripped
off its low boiling components and then distilled in-order to separate it into water
and ethylene oxide.
CO2 scrubber:
The recycle stream obtained from the ethylene oxide scrubber is compressed
and a side-stream is fed to the CO2 scrubber. Here, CO2 gets dissolved into the hot
aqueous solution of potassium carbonate (i.e., the scrubbing media). The
dissolution of CO2 is not only a physical phenomenon, but a chemical phenomenon
as well, for, the CO2 reacts with potassium carbonate to produce potassium
hydrogen carbonate.
K2CO3 + CO2 + H2O → 2 KHCO3
CO2 de-scrubber:
The above potassium carbonate solution (enriched with CO2) is then sent to the
CO2 de-scrubber where CO2 is de-scrubbed by stepwise (usually two steps)
flashing. The first step is done to remove the hydrocarbon gases, and the second
step is employed to strip off CO2.
2) Air Based Oxidation Process:
The air based process is similar to the oxygen process, but some differences
exist. Air introduces a large amount of nitrogen into the recycle gas, which means
that a large amount of purge gas must be vented to maintain a constant nitrogen
concentration in the recycle stream. The quantity of gas that is vented removes
sufficient CO2 to make CO2 scrubbing unnecessary. However, the off gas leaving
the primary reactor still contains so much ethylene that it must be further converted
in a subsequent secondary or purge reactor before it can be vented into the
atmosphere. The reaction conditions cannot be tailored to the needs of ethylene
oxide formation as optimally as in the oxygen-based process. The conversion of
ethylene is higher than in the oxygen based process, especially in the secondary
reactors, so as to obtain an acceptable level of ethylene loss in the purge gas. Since
selectivity is inversely related to ethylene conversion, it follows that the air-based
process has a lower selectivity.

Figure: Ethylene oxide by Direct Oxidation of Ethylene

USES:
 ETO is used to sterilize new and reusable medical equipment (eg, surgical
instruments, hypodermic needles/syringes, surgical prosthetic parts,
hemodialysis machines, heart and lung machines, dental instruments,
veterinary instruments, heat labile material, moisture labile material, oral
and inhalation equipment, diagnostic instruments, thermometers, surgical
dressings, first aid equipment).
 ETO is used during the processing of some gums and dyes in manufacturing
cosmetics to reduce microbial activity of organisms that can contaminate
ingredients. In addition, other associated products such as packaging
material for cosmetics may be treated with ETO.
 About 60% of the ethylene oxide is used to produce ethylene
glycol (antifreeze). Other chemicals that are produced from ethylene oxide
include non-ionic surfactants (used in industrial applications, detergents, and
dishwashing formulations), glycol ethers, ethanol amines (used in soaps,
detergents, and textile chemicals), diethylene glycol, tri-ethylene
glycol, polyethylene glycol, and urethane polyols.

SAFETY CONCERNS:
Handling, Storage, and Transportation:
Ethylene oxide has repeatedly caused serious explosions, fires, and accidents. It is
an extremely hazardous substance because it can explode and is both highly
flammable and extremely reactive (exothermic reactions). Aqueous solutions
containing > 4 wt % ethylene oxide are flammable. Furthermore, ethylene oxide is
toxic and poses a danger both to health and to the environment. The inherent
hazards of the product must be known; all prescribed safety measures and legal
requirements must be observed. Personnel handling ethylene oxide must receive
appropriate training.
Handling:
Earth-ground and bond all lines and equipment associated with the system. All
electrical equipment should be non-sparking or explosion proof. Ensure that fire
extinguishers are available. Ethylene oxide stored in the liquid state can be
maintained free of explosion hazard in the gaseous phase by the introduction of
nitrogen at sufficient pressure. At 70ºF (21ºC) a nitrogen pressure of 32.6 psig (225
kPa) is required. Store below 130ºF.

Use only stainless steel or nickel. Ethylene oxide decomposes or polymerizes

violently on contact with potassium, tin, zinc, aluminum, iron oxides, copper,
silver, mercury, magnesium and their alloys. It will also react violently with caustic
soda, hydrated lime, magnesium chloride, ammonia, alcohols and amines. Ethylene
Oxide will attack most forms of plastic, rubber and coatings.

Storage
Consider using leak detection and alarm systems. Store and use in a fume
hood or ventilated gas cabinet free of ignition sources. Follow all applicable
recommendations for storage and handling of compressed gases.

Disposal:
Ethylene Oxide cylinders should be returned to the compressed gas distributor
when emptied or no longer used.

Environmental Effects:
Typically low environmental levels of Ethylene oxide are unlikely to harm the
environment or wildlife. However, Ethylene oxide is toxic and exposure to high
levels may cause significant harm, particularly to aquatic organisms. Ethylene
oxide does not accumulate in the environment, but its breakdown in air and water
is fairly slow. As a VOC, it may be involved in the formation of ground level of
ozone, which can damage crops and materials. However, Ethylene oxide is thought
to be generally only slightly involved in this reaction. It is not considered likely
that Ethylene oxide pollution has any effects on the global environment.
Ethylene oxide exposure mainly occurs in the occupational setting and can enter
the body either by inhalation of air containing ethylene oxide or by accidental
ingestion of, or dermal contact with, ethylene oxide. Inhalation of air containing
low levels of ethylene oxide over long periods of time can cause irritation of the
eyes, skin and respiratory passages. Exposure to ethylene oxide affects the nervous
system and can lead to headaches, memory loss and numbness. Exposure may also
increase the rate of miscarriage. Higher level exposure may result in similar but
more severe effects. Ingestion of ethylene oxide can lead to nausea, vomiting and
diarrhea. Dermal contact with ethylene oxide can cause severe skin burns. The
International Agency for Research on Cancer has designated ethylene oxide as a
carcinogen. However, exposure to ethylene oxide at normal background levels is
unlikely to have any adverse effect on human health.

1) Ethylene oxide-Pollutant Fact Sheet. [Online]. Available:

http://apps.sepa.org.uk. [Accessed: 05-Jan-2020]

2) “Ethylene oxide compound,” About us: PubChem. [Online]. Available:

https://pubchem.ncbi.nlm.nih.gov.

3) S. I. E. G. F. R. I. E. D. REBSDAT and D. I. E. T. E. R. MAYER, “Ethylene

Oxide.” [Online]. Available: https://www.ugr.es