ETHYLENE OXIDE

INTRODUCTION:

Ethylene oxide, also known as oxirane, is a flammable, colourless gas with a pleasant odour. It is
a raw material used in the manufacture of lubricants, plasticizers, ethylene, glycol, and other
petroleum-based products. Other compounds derived from ethylene oxide include those used to
make plastics, textiles, adhesives, detergents, and cosmetics. A significant application of EO is
the sterilisation of medical equipment, particularly suits worn by medical personnel and
hospitals. Ethylene oxide is estimated to sterilise 20 billion medical devices each year, assisting
in the fight against illness and infection. Ethylene oxide is a highly reactive and versatile
chemical. The sterilisation process is closely monitored, and the items are decontaminated from
ethylene oxide gas prior to use. Ethylene oxide is manufactred by direct catalytic ethylene
oxidation with air or oxygen supported.

PROCESS SELECTION:

Commercially, ethylene oxide is produced using two primary processes: ethylene chlorohydrin
and natural oxidation.

1. Ethylene Chlorohydrin:

Previously, the chlorohydrin process was used to produce ethylene oxide. Until 1937, the
chlorohydrin process was developed in Germany during World War I. Ethylene oxide and
calcium chloride are produced by the reaction of ethylene with hypochlorous acid, and ethylene
oxide and calcium chloride are produced by dehydrochlorination with lime. This method,
however, is no longer widely used.

2. Direct Oxidation:
WURTZ, the discoverer of ethylene oxide, attempted but failed to produce it by direct oxidation
of ethylene with oxygen as early as 1863. Before LEFORT discovered in 1931 that metallic
silver catalysed the formation of ethylene oxide from ethylene and oxygen, many other failed
attempts were made. When compared to the chlorohydrin process, direct oxidation reduces the
need for huge amounts of chlorine.

PROCESS DESCRIPTION:

Air-Based Direct Oxidation Process:

The procedure is easily divided into three major sections: the reaction system, oxide recovery,
and oxide purification.

In the first section, compressed air is filtered, purified, and fed individually with ethylene into a
recycle gas stream. This recycle stream supplies one or more parallel primary multitubular
reactors. The heat of reaction is removed by circulating or boiling an organic oil on the shell side
or other high boiling materials in the packed-bed converters, which oxidise ethylene to ethylene
oxide, carbon dioxide, and water. 

At the reactor input, ppm concentrations of vapor-phase oxidation inhibitors like vinyl chloride,
ethylene dichloride, or other halogenated chemicals are introduced. One to three moles percent
ethylene oxide may be present in the process stream that leaves the reactor. Using the cold
recycle reactor feed stream gas from the primary absorber, this hot effluent gas is subsequently
cooled in a shell-and-tube heat exchanger to around 35–40 C.

The recovery of ethylene oxide from the crude product gas is the second critical step in the
process. This is achieved in the main absorber by countercurrent scrubbing with cold water in a
column. The reactor's ethylene oxide disperses in the absorber water, along with some nitrogen
and carbon dioxide and traces of ethylene, ethane, and aldehydes. The water - soluble stream is
drawn from the base of the absorber and directed to a desorber. The unabsorbed gas from the
above-mentioned main absorber is divided into two parts.

The third crucial stage in the process is the purification of ethylene oxide. In this part of the
procedure, a number of column sequences have been practised. After heat exchange, the ethylene
oxide-rich water streams from the main and purge absorbers are mixed and sent to the top part of
a desorber, where the absorbate is steam stripped. The almost oxide-free lean water from the
desorber's bottom part is recirculated to the main and purge absorbers. The concentrated ethylene
oxide vapour is received overhead by the resultant stripper for further purification. If the
desorber is used under vacuum, a compressor is necessary.

Oxygen-Based Direct Oxidation Process:

Despite the fact that the underlying reaction and the final outcome are the same, the details of
air- and oxygen-based processes differ significantly. Almost bulk of the changes occur from
transitioning from air to pure oxygen (>95 mol% O2). Because of the poor per pass conversion,
the necessity for full elimination of ethylene oxide via absorption, and the building of nitrogen in
the cycle, the air process demands a considerable purge stream. The air-based process requires
the previously mentioned tiered reaction absorption system as a result of the purge stream. The
oxygen-based method employs a high proportion of pure oxygen, minimises the quantity of inert
gases brought into the cycle, and achieves virtually full recycling of the unconverted ethylene.
This eliminates the requirement for a purge reactor system in an oxygen-based process.
However, similar to the air-based process, the volume of carbon dioxide generated is around half
that of the volume of ethylene that reacts at a catalyst selectivity of 70 80%. This CO2 must be
removed continually in order to maintain an appropriate level of concentration in the cycle. CO2
concentrations more than 15 mol% have a deleterious effect on catalyst activity.

As a result, in an oxygen-based system, some of the recycling gas exiting the absorber must be
treated in a CO2 removal unit before returning to the main reaction cycle. To prevent argon
accumulating in the cycle, an extra process vent is necessary in addition to the CO2 removal unit
purge stream. Argon is a substantial contaminant in the oxygen supply, and if no purposeful
purge is utilised, it can build to 30-40 mol% in the cycle gas. Despite this additional purge, the
overall vent stream in an oxygen-based operation is much smaller than in an air-based unit.
Sustainable Manufacturing:

A vast and rising number of enterprises profit from sustainable manufacturing methods in terms
of financial, environmental, and product quality. In a nutshell, sustainable Ethylene Oxide
manufacture is inextricably related to economically viable procedures that have little
environmental impact and are extremely energy efficient. Ethylene Oxide manufacture that is
sustainable also leads to greater manufacturing safety requirements, which increases compliance
standards. The rising demand for ecological materials to fulfil societal demands, as well as the
related emissions, is fast outstripping the environment's capacity. To prevent reaching a tipping
point when natural systems are no longer available, we must think about a sustainable road
ahead, especially in the chemical business. Sustainability in the chemical business necessitates
minimising material and energy consumption, as well as finding less wasteful ways to satisfy
demands by boosting energy efficiency, reusing resources, and applying sustainable technology
while considering both economic and environmental issues.

Since the discharge of very dangerous chemical components as well as the high energy
requirement, the environmental costs of ethylene oxide synthesis are rising. Scenarios based on
natural gas/biomass are one option to alleviate its environmental implications throughout the
energy transition phase. Natural gas, however, is not the best option for this specific case,
according to this Life Cycle Assessment (LCA) study, because natural gas-based scenarios are
less sustainable than residual fuel oil-based scenarios in terms of fossil depletion (93%),
freshwater ecotoxicity (76%), marine ecotoxicity (59%), human ecotoxicity (53%), terrestrial
acidification (51%), and particulate matter formation (40% The LCA analysis, on the other hand,
demonstrates that decreasing environmental loads using biomass is doable without changing the
core of the process technology.).

Uses:

Ethylene oxide is one of the most essential raw materials utilised in large-scale
chemical synthesis. The bulk of ethylene oxide is used to make ethylene glycols like
diethylene glycol and tri ethylene glycol, which contribute up to 75% of global
usage.

While ethylene glycol production is the most prevalent application of ethylene oxide,
its proportion varies substantially by area, ranging from 44% in Western Europe,
63% in Japan, and 73% in North America to 90% in the rest of Asia and 99% in
Africa.

Its principal use is in the manufacturing of ethylene glycol and its oligomers, glycol
ethers, and ethanolamines. Minor but major direct applications include a fumigant
 for foods and textiles, an agricultural fungicide and pesticide, and a sterilant for
medical equipment.

Since it has non-damaging effects on sensitive tools and devices that require
sterilisation, as well as its wide spectrum of material compatibility, ethylene oxide is
one of the most regularly utilised sterilisation procedures in the healthcare business.

Ethylene oxide is employed as a fungicide and an accelerator of tobacco leaf

maturity. Ethylene oxide is also used in thermobaric weaponry (fuel-air explosives).

Storage:

Avoid heat, flames, and other sources of ignition. Spills should be diluted with plenty of water.
Provide N2 blanking and, if possible, keep the storage tank refrigerated. Its pressure needs to
remain within safe operating ranges Citric acid can be used to clean equipment. Prevent any
chemicals from entering the EO vessel.The storage tank should be at least 15 meters away from
the plants and the building.
Vehicle collisions should be avoided with fencing and barricades. An impermeable and sloppy
floor should direct spillage to a remote catch pit.
It polymerizes in the presence of iron rust, acids, bases, and chlorides of iron and other metals.
Polymerization is a highly exothermic reaction that can result in an explosion.
Construction material: stainless steel or MS aluminized from the inside. Mineral wool insulation
covered by galvanized or stainless steel cladding.

Handling:

All system lines and equipment should be earth-ground and bonded. All electrical equipment
should be spark-proof or explosion-proof. Make sure you have fire extinguishers on hand. By
introducing nitrogen at sufficient pressure, ethylene oxide stored in liquid form can be kept safe
from an explosion in the gaseous phase. A nitrogen pressure of 32.6 psig (225 kPa) is required at
70◦F (21◦C). Store at temperatures below 130◦F.
Only use stainless steel or nickel. When exposed to potassium, tin, zinc, aluminum, iron oxides,
copper, silver, mercury, magnesium, and their alloys, ethylene oxide decomposes or polymerizes
violently. Caustic soda, hydrated lime, magnesium chloride, ammonia, alcohol, and amines all
react violently with it. Most plastics, rubbers, and coatings will be attacked by ethylene oxide.

Environmental Properties:

Because it is highly reactive, EO does not last in the atmosphere, soil, or water indefinitely. The
following characteristics define EO:
 EO is somewhat persistent in the atmosphere, but evidence suggests that it eventually
degrades through photolysis;
 EO does not readily absorb into sediments or soils and does not persist in soils; if
absorbed, soil organisms will convert EO to glycols over time, eliminating any
persistence in the soil;
 EO has low to moderate aquatic toxicity;
 EO does not persist in water due to conversion to glycol by hydrolysis or degradation of
hydrolysis protons;
 In environmental media, EO does not bioconcentrate.

Environmental Effects of Ethylene Oxide:

Soil does not absorb EO well. In the event of a spill to soil, the majority of the EO will
evaporate, with the remaining infiltrating the ground. Environmental concerns include EO's
downward penetration into the groundwater table. Over time, some of the EO will be
transformed to ethylene glycol by hydrolysis; however, this process is quite slow. It is worth
noting that ethylene glycol degrades quickly (0.2 to 0.9 day half-life) Once the EO has
permeated the soil, evaporation will resume, albeit at a reduced rate. Diluting an EO release with
water raises the viscosity of the resulting mixture, slowing its downward mobility in the soil. If
the soil surface is moist when the EO is released, as it may be after a storm, it will flow off or
pond and gradually evaporate, hydrolyze, or biodegrade.

Following a spill, the waste generator must evaluate if the substance being dumped of is
hazardous waste. Although EO is not listed as a hazardous waste under US environmental rules,
it is combustible in its pure form (D001). As a result, soils and spill residue must be analysed to
establish whether the materials being disposed of fit the criteria for hazardous waste
classification.When EO is poured over water, it volatilizes and expands, combining with the
water. In bodies of water, the EO may hydrolyze and biodegrade simultaneously.

REFERENCES:

http://repo.upertis.ac.id/1636/1/Raymond%20E%20Kirk_%20Donald%20F%20Othmer_
%20Martin%20Grayson_%20David%20Eckroth_%20et%20al-Kirk-Othmer%20Encyclopedia
%20of%20Chemical%20Technology%20Vol%205%20-Wiley%20%20%282004%29.pdf

https://www.researchgate.net/publication/
336241433_Environmental_sustainability_assessment_of_an_ethylene_oxide_production_proce
ss_through_Cumulative_Exergy_Demand_and_ReCiPe

https://www.americanchemistry.com/industry-groups/ethylene-oxide/resources/ethylene-oxide-
product-stewardship-manual-3rd-edition