1.

0 TASK SPECIFICATION

 Describe different technology to produce Ethylene

Oxide.

 Based on one technology, describe the process (i.e.

separation/reaction/absorption etc) occur in every
single unit operation to make whole plant complete
from the feedstock to the end product.

 Please explain the input and output for each unit

operation. Please draw the flow diagram individually
for each unit operation and overall plant.

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2.0 Acknowledgement
While performing our assignment, we had to take the help and guideline from some
respected people, who deserve our greatest gratitude. The completion of this assignment
gives us much pleasure. We would like to show our gratitude to Prof Dr.Abdul Latif Ahmad
for giving us a good guideline about an impressive introduction of different unit operations in
a chemical plant, that assist us to complete this term paper. We would also like to expand our
deepest gratitude to all those who have directly and indirectly guided us in writing this
assignment.

Moreover, we want to thank our classmates and team members itself, have made
valuable comment and suggestions on this term paper which gave us an inspiration to
improve our work. We thank all the people for their help directly or indirectly to complete
our term paper.

Last but not least, we would like to thank our family member for giving us their moral
support in doing this assignment

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3.0 Abstract

The primary objectives of the assignment are to differentiate technology to produce ethylene
oxide and investigate each unit operation. There are three technologies to produce ethylene
oxide. First is the oxygen-based direct oxidation, second is the air-based direct oxidation and
third is chlorohydrin process. We identify that oxygen-based direct oxidation process is more
effective than other because more product will be produced, costly and eco-friendly and gas
released to the environment not as dangerous compare to other.

The technology that we choose to investigate is oxygen-based oxidation. There are 10 unit
operations which are mixer, heat exchange 1, reactor, heat exchange 2, ethylene oxide
absorber, carbon dioxide absorber, ethylene oxide desorber, carbon dioxide desorber, stripper
and distillation column. Each unit operations have their own function.

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4.0 INTRODUCTION

Ethylene oxide, C2H4O, with molecular weight 44.05, is one of the epoxide families of
chemicals. In addition to its International Union of Pure and Applied Chemistry (IUPAC)
name, oxirane, it is also called dihydrooxirene; dimethyleneoxide; 1,2- epoxyethane;
oxacyclopropane; oxane; oxidoethane; and a, b-oxidoethane. It is normally handled under
pressure as a colourless liquid, but at ambient conditions it is a colourless gas with a pungent,
irritating, ether-like odour. Due to its molecular structure in which its highly strained ring can
be opened easily, ethylene oxide is one of the most versatile chemical intermediates.

Ethylene oxide was first described in 1859 by WURTZ , who prepared it by

eliminating hydrochloric acid from ethylene chlorohydrin using potassium hydroxide
solution. Based on WURTZ’s discovery, the industrial production of chlorohydrin process
began in 1914. Since then, the production and importance of ethylene oxide have steadily
grown. However, in 1931, LEFORT discovered the direct catalytic oxidation of ethylene
which gradually replaced the chlorohydrin process. Currently, almost all ethylene oxide
production plants are based on the direct oxidation process with air or oxygen.

Figure 1: Molecule of ethylene oxide

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5.0 Discussion

5.1 Chlorohydrin Process

Chlorohydrin process which known as Wurtz-process. Production of ethylene oxide began in
1914 by the chlorohydrin process, the main method used until 1937, in which ethylene
chlorohydrin is converted to ethylene oxide by reaction with calcium oxide.

In the first step, ethene reacts in the liquid phase with an alkalized, aqueous chlorine solution
in order to form the chlorohydrin.

Cl2 + 2OH-  Cl- +ClO- +H2O

ClO− +C2H4 +H2O  ClCH2CH2 OH +OH−

In the following step, H-Cl is eliminated in an alkaline solution and ethylene oxide formed:

2ClCH2CH2 OH+CaO 2 C2H4O+CaCl2 +H2O

The chlorohydrin process is carried out in packed towers at 27-43°C and 2-3 atm pressure at
a yield of 85-90%. To avoid formation of byproducts 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 to the chlorohydrin solution. The mixture is then heated to just less
than 100°C 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, byproducts 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 production of ethylene chlorohydrin resulted in the formation of two main

organochlorine by-products, 1,2-dichloroethane and bis(2- chloroethyl)ether. 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 disadvantages of this process are the formation of alkali-chlorides in

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stoichiometric amounts the need for stoichiometric amounts of chlorine and the formation of
chlorinated by products.

5.2 Direct oxidation

All ethylene oxide direct oxidation plants are based on the original process chemistry
discovered by Lefort in 1931. In this process, the oxidation of ethene is performed directly
with oxygen or air and silver as catalyst at 220-300°C and 10-30 bar pressure produces few
bi-products other than carbon dioxide and water. This heterogeneously catalyzed gas phase
oxidation is much easier to handle because air is free of charge in contrast to chlorine.

The important reactions that occur are:

Ethylene is oxidized with oxygen over a silver alumina catalyst to form ethylene oxide.
CH2=CH2 +1/2 O2 → CH2-CH2O
Ethylene is totally oxidized to form carbon dioxide and water.
CH2CH2 + 3 O2 → 2CO2 + 2H2O
Ethylene oxide is further oxidized to form carbon dioxide and water.
CH2CH2O +5/2 O2→ 2CO2 + 2H2O

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The direct oxidation Ethylene Oxide process can be divided into air based and oxygen
based processes. The differences between oxygen based oxidation and air based
oxidation is shown by Table 1 below.

Oxygen based direct oxidation Air based direct oxidation

For all plant capacities and a given type of
catalyst, the oxygen-based reactor yields a
higher selectivity and requires less catalyst.
requires more catalyst, more reactors (to
achieve a comparable selectivity), a multi-
stage compressor, air purification units, a
vent gas treating system, and two to three
reactor train in series .

requires a carbon dioxide removal section, Although the air-based process may cost
more stainless steel, and some expensive lower to run (for small to medium-sized
instrumentation. plants), the initial building costs of the air-
based plant is much more than the oxygen-
based plant.
This extra air pollution is not part of the In spite of the extra equipment for the air-
oxygen-based process. based process, the production level of
ethylene oxide for an air-based process is still
less than the oxygen-based process.
The cycle gas purge stream of the oxygen-
based process is usually small enough to be
burned without too many pollution problems.
the catalyst lasts longer and less is required
for the catalyst charge (more economically).
Table 1: Differences between Oxygen Based Oxidation and Air Based Oxidation

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5.2.1 Air-Based Direct Oxidation Process

1. Compressed air is first purified to remove contaminants and then mixed with recycled
gas and fresh ethylene.

2. Vapour 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.

3. The gas is fed to a multi-tubed catalytic reactor in which the reactor temperature is
controlled with boiling water or circulated non-boiling 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.

4. 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.

5. The cooled gas is then fed in to the main absorber where the ethylene oxide is
absorbed in water, produce a dilute aqueous solution.

6. The scrubbed gas from the absorber is then compressed and the major portion of the
gas is recycled to the main reactor.

7. 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.

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5.2.2 Oxygen-Based Direct Oxidation Process

1. Feed of ethylene and oxygen into the reactor and oxidation of ethylene by passing through
the reactor (bundles of tubes packed with the catalyst material) at 200 to 300 °C. Together
with ethylene oxide, CO2, H2O, and heat is generated as well.
2. Cooling of the gas that leaves the reactor by means of steam generation or direct heating
of the gas inlet of the reactor.
3. Removal of ethylene oxide and CO2 from the gas by scrubbing with first water and second
an aqueous potassium carbonate solution. The ethylene oxide dissolves in the solution
4. Desorption of ethylene oxide from the solution in the desorber and stripping of its low-
boiling components.
5. Final distillation with separation into water and ethylene oxide.
6 .The process runs continuously using a recycled gas stream through the reactors driven by
compressors, and reloaded before entering the reactor again.

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5.3 Advantages of Oxygen-Based Process
against Air-Based Process

We choose Oxygen–Based Direct Oxidation process plant as our investigate topic due to
currently, most of the plant design is based on the oxygen-based process and it has many
advantages.

1. With the same capacity and same type of catalyst, oxygen-based process requires less
catalyst.
2. The oxygen-based process is more economical than the air-based process. The
oxygen-based process requires a carbon dioxide removal section, more stainless steel,
and some expensive instrumentation while the air-based process requires more
catalyst, more reactors for achieving a comparable selectivity, a multi-stage
compressor, air purification units, a vent gas treating system, and two to three reactor
train in series. Hence, even though the air-based process may cost lower to run for
small to medium-sized plants, the initial building costs of the air-based plant is much
more than the oxygen-based plant.
3. Air-based process has a lower selectivity than oxygen-based process. The reaction
conditions of air-based process cannot be tailored to the needs of ethylene oxide
formation as optimally as in the oxygen-based process. The conversion of ethylene in
air-based process is higher than in the oxygen-based process, especially in the
secondary reactors in order to obtain an acceptable level of ethylene that loss in the
purge gas. And since selectivity is inversely related to ethylene conversion, the
selectivity of air-based process is less than for an oxygen- based process in spite of
additional equipment. The average selectivity for an air based process is 65-75% and
for the oxygen based process around 70-80%.

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5.4 UNIT OPERATIONS AND PROCESSES
Reactor system
Mixer

Ethylene Ethylene
Oxygen Mixer Oxygen
Methane Methane
Argon Argon

Input: oxygen, methane, ethylene, argon

Output: oxygen, methane, ethylene, argon
Process: mixing the reactant
In this process, methane is used as inert gas to affect the explosion limit within the reactor
and the heat capacity of the fluid.

Heat exchange 1

Ethylene Ethylene
Oxygen Heat Exchange Oxygen
Methane 1 Methane
Argon Argon

Input: oxygen, methane, ethylene, argon

Output: oxygen, methane, ethylene, argon
Process: heats up the fluid to the reactor inlet temperature
In this process, the unit operation will preheat the mixture to 140 ᵒ C . It uses the heated
reactor effluent stream to reduce the energy required to raise the feed to temperatures.

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Reactor

Ethylene Oxide
Carbon Dioxide
Ethylene
Oxygen
Oxygen Reactor Methane
Methane
Argon
Argon
Ethylene
Water
Input: oxygen, methane, ethylene, argon
Output: methane, ethylene oxide, carbon dioxide, oxygen, argon, ethylene, water
Process: Oxidation
The reactor is operated at 260ᵒ C and 20 bar .In this process, oxidation of ethylene reaction
occurs over the silver-based catalyst which results in formation of ethylene oxide.
C2H4 +1/2 O2 → C2H4O
C2H4 + 3 O2 → 2 CO2 + 2 H2O
Chlorides like ethylene dichloride (EDC), Vinyl chloride (VC) and ethyl chloride (EC) are
fed to the reactors as inhibitors. An inhibitor is a substance that is used in catalytic processes
to improve the performance of the catalyst and decreases the reaction rate by competing with
reactants on the catalyst activity
The reactor is a shell and tube types, with a couple of thousands tubes, 20-50 mm inner
diameter. The reactor tube length varies between 6-12 meters. The tubes are filled with a
silver-based catalyst supported on a carrier material with a diameter of 3-10 mm
The reaction is exothermic reaction, it will release the heat, therefore it required the coolant.
The reactor can be either oil cooled or boiler water cooled. Circulated boiler water is more
common. Boiling water provides good heat absorption and is safer compared to the oil cooled
reactor.

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Heat exchange 2

Ethylene Oxide Ethylene Oxide

Carbon Dioxide Carbon Dioxide
Oxygen Heat Exchange Oxygen
Methane 2 Methane
Argon Argon
Ethylene Ethylene
Water Water

Input: methane, ethylene oxide, carbon dioxide, argon, ethylene, oxygen, water
Output: methane, ethylene oxide, carbon dioxide, argon, ethylene, oxygen, water
Process: cools down the reactor outlet stream using cooling water
In this process, it is desirable to remove as much heat as possible from this stream since the
ethylene oxide absorber requires low temperatures. Therefore, heat exchanger will cool the
mixture to 35ᵒ C before entering the ethylene oxide absorber.

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Absorber System
Ethylene Oxide Absorber

Ethylene Oxide Ethylene Oxide

Carbon Dioxide Carbon Dioxide
Oxygen Oxygen
Methane Absorber Methane
Argon Argon
Ethylene Ethylene
Water Water

Input: methane, ethylene oxide, carbon dioxide, argon, ethylene, oxygen, water
Output: methane, ethylene oxide, carbon dioxide, argon, ethylene, oxygen, water
Process: separation
In the ethylene oxide absorber, water acts as the absorbent and the absorption of ethylene
oxide in water take places to remove desired product from the gas mixtures. The absorption
extent dependent on solubility of the components. The solubility of each components in water
at 35ᵒC is shown in table below

Table 1: solubility of each components in water at 35ᵒC

Ethylene oxide is very efficiently separated from the gas mixture by physical absorption into
water due to ethylene oxide has infinity solubility in water. The ethylene oxide absorption is
performed in an adiabatic counter-current flow column at high pressure (13 bar). Increasing
pressure and lowering temperature in the column serves to make all the gases more soluble,
so a balance had to be found that allowed the ethylene oxide to dissolve while the other gases
were still vented out the top. The bottoms of the absorber, containing mainly ethylene oxide
and water, but still consist of some small amounts of the other constituents of the recycle gas
dissolve in the water. are sent to a desorber. Then other will sent to carbon dioxide absorber.

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Carbon dioxide Absorber

Ethylene
Ethylene Carbon Dioxide
Carbon Dioxide Carbon Oxygen
Oxygen dioxide Methane
Methane Absorber Argon
Argon carbonate solution
enriched with carbon
dioxide

Input: Ethylene, carbon dioxide, oxygen, methane and argon

Output: Ethylene, carbon dioxide, oxygen, ethane, argon and carbonate solution enriched
with carbon dioxide
Process: Dissolving carbon dioxide by scrubbing with potassium carbonate solution.
The overhead stream containing ethylene and carbon dioxide from the ethylene oxide
absorber is then sent to carbon dioxide absorber which uses potassium carbonate as an
absorbent. Since the concentration of CO2 will affect the activity of the catalyst and improved
selectivity towards ethylene oxide results in less production of CO2, it is important to
maintain an acceptable CO2 concentration in the circulated reactor gas before it enters the
main recycled gas again. Hence, the function of this carbon dioxide absorber is to partly
remove the CO2 from the recycle gas by scrubbing with hot potassium carbonate solution at a
temperature of 60 °C and 5 atm. CO2 not only will be removed by physical dissolution but
also by reacting with potassium carbonate to give the hydrogen carbonate.

K2CO3 + CO2 + H2O 2 KHCO3

From the carbon dioxide absorber, the overhead recycle ethylene gas is then sent back to the
reactor for a new cycle while the absorbent which is enriched with CO2 is then sent to carbon
dioxide stripper from the carbon dioxide absorber at approximately atmospheric pressure.

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Desorber system
Ethylene Oxide Desorber system

Ethylene Oxide Ethylene Oxide

Water Water
Ethylene Oxide
Small amount Remaining Light
Desorber system
of recycle gas Gas Impurities

Input: Ethylene oxide, water, small amounts of the other constituents of recycle gas
Output: Ethylene oxide, water, remaining light gas impurities
Process: separation
The dilute aqueous solutions of ethylene oxide, water and the other constituents of recycle
gas from the absorbers are combined and fed to the desorber where the ethylene oxide and
dissolved inerts are distilled under reduced pressure.
The desorber, a 24-tray column with a reboiler, is used to remove the large amount of water
added in the absorber. The feed to the desorber is preheated by condensing 175 psi steam in a
heat exchanger. The bottom stream contains water while the top contains the ethylene oxide
and the rest of the impurities. In this column it is favorable to have a lower pressure and
higher temperature, thus it is operated at 3.5 bar. Through this, desorption of ethylene oxide
from the solution in the desorber.

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CO2 desorber system

Carbonate Solution with CO2 Desorber Carbon Dioxide

enriched Carbon Dioxide System Potassium Carbonate

Input: carbonate solution enriched with carbon dioxide

Output: carbon dioxide , potassium carbonate

Process: Separation

The system operates at slight lower pressure 5 atm. In the desorber, the carbonate solution
enriched with carbon dioxide is thermally regenerated and total recovery of the carbon
dioxide is obtained at the top of the stripper. the CO2 is stripped off at atmospheric pressure
and is either released into the atmosphere or fed to a CO2 utilization plant, after optional
catalytic treatment (e.g., supported Pd/ Pt) to remove residual hydrocarbons The effluent
carbonate solution enriched with carbon dioxide is then pump back into the top of the carbon
dioxide absorber for reuse using pump.

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Purification System
Stripper

Ethylene Oxide
Water Crude Ethylene
Stripper
Remaining Lights Gas Oxide
Impurities

Input: Ethylene oxide, water, remaining light gas impurities

Output: Crude ethylene oxide, remaining light gas impurities
Process: separation

The stripper removes all of the remaining light gas impurities. It is a 24-tray column with a
condenser and reboiler. The distillate contains all of the gas contaminants while the bottoms
contains only water and ethylene oxide

The stripper column is heated using the water vapour. By heating the stripper column in such
a manner, ethylene oxide contained in the absorption liquid supplied from the upper part of
the stripper column (usually 99% by weight or more thereof) is stripped and discharged from
the column top part of the stripper column through a conduit.

As for operation conditions of the stripper column, the column top pressure is usually 0.01 to
0.20 MPa gauge, and preferably 0.03 to 0.06 MPa gauge. The smaller the column top
pressure is, the lower the temperature in the column is. As a result, production of ethylene
glycol as a by-product from ethylene oxide in the column tends to be suppressed. However,
ethylene oxide is relatively easily ignitable. Therefore, from a view point of preventing
leakage of oxygen into the system, usually, the operation is not performed at atmospheric
pressure or lower, and is performed at a pressure a little higher than atmospheric pressure. As
for temperature conditions of the stripper column, the column top temperature is usually 85 to
120° C., and the column bottom temperature is usually 100 to 130° C.

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Distillation Column

Distillation Pure Ethylene Oxide

Crude Ethylene
Column +
Oxide
Water

Input: Crude ethylene oxide

Output: Pure ethylene oxide and water

Process: Separation/ Distillation/ Purification of ethylene oxide.

The ethylene oxide in the aqueous stream from the absorber is separated from the stream in a
number of distillation steps in the refining area. The dilute aqueous solution of ethylene oxide
from the ethylene oxide desorber will be distilled into water and ethylene oxide in the
distillation column at a temperature of 65 °C. This process runs continuously using a recycled
gas stream through the reactors driven by compressors and reloaded before entering the
reactor again.

In distillation column, separation of ethylene oxide from water is based on the different
boiling point of water and ethylene oxide in which the boiling point of water is 100°C while
ethylene oxide is 13.7°C.

The final column has 42 trays with a condenser and reboiler. The final product ethylene oxide
is usually very pure (> 99.5 %). It will go out the top as distillate and will be stored under a
nitrogen atmosphere in pressurized tanks.

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20
6.0 CONCLUSION

Historically, chlorohydrin is the first technology to produce ethylene oxide. However,

it is gradually replaced by the direct oxidation process which is the air-based process and
oxygen-based process. These two basic types processes play a significant role in the
commercial manufacturing of ethylene oxide. Although these two technologies are very
similar, but the main difference is that air-based process use air for oxidation while for
oxygen-based process, pure oxygen is used. In this term paper, oxygen-based is chosen due to
its lost cost, high selectivity, more eco-friendly and less catalyst is used.

In oxygen-based process, the main input is the ethylene and oxygen. After undergoing
a few processes through different unit operation, ethylene oxide is produced. Besides, CO2 is
the side product.

Since ethylene oxide is both highly flammable and extremely reactive, it can cause
serious explosions, fires, and accidents. Hence, it is an extremely hazardous substance. To
operate with maximum yield and safe conditions, ethylene oxide production requires a
sophisticated process control system. There are a number of constituents in the process that
must be analytically measured in real time. Controlling the concentration of oxygen and
carbon dioxide, temperature, pressure and catalyst selectivity are crucial to obtain maximum
ethylene oxide yield.

In conclusion, ethylene oxide is toxic and poses a danger to health and to the
environment. All prescribed safety measures and legal requirements must be observed.
Personnel handling ethylene oxide must receive appropriate training. Catalyst industry should
do research and continuously develop new catalysts for the ethylene oxide production. For
future work to improve selectivity towards ethylene oxide, the development of catalyst
should be followed. When a new ethylene oxide catalyst is considered, it’s important to study
the process parameters and the specification of required catalyst like operating temperature,
concentrations of ethylene and carbon dioxide. It is crucial as it can improve the overall
process performance which give rise to a more economically and sustainable ethylene oxide
production for the young future engineer.

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7.0 REFERENCES
1) Huang, Janet. "Ethylene Oxide Reactor System". Owlnet.rice.edu.2017. Web. 1
Mar. 2017.
2) SIEGFRIED REBSDAT, DIETER MAYER.(2012).Ullmann’s Encyclopedia of
Industry Chemistry 4th edition [pdf] Federal Republic of Germany: Wiley-VCH
Verlag GmbH & Co. KGaA. Available at
http://www.ugr.es/~tep028/pqi/descargas/Industria%20quimica%20organica/tema_5/
oxido_etileno_a10_117.pdf [Accessed 1 Mar. 2017].
3) industry.usa.siemens.com,(2003)Process Analyzers In Ethylene Oxide Production
Plant.[online] Available at
https://www.industry.usa.siemens.com/automation/us/en/process-instrumentation-
and-analytics/solutions-for-industry/oil-and-gas/documents/ethylenoxid-oilgas-e.pdf
[Accessed 1 Mar. 2017].
4）Hanna Perzon.A Simulation Model of a reactor for Ethylene Oxide production.
Thesis. Department of Chemical Engineering Lund University; 2015
5) Ansgar Kursawe. Partial Oxidation of Ethene to Ethylene Oxide in Microchannel
Reactor. Diploma Thesis. Germany ;2009
6) LOCATING AND ESTIMATING AIR EMISSIONS FROM SOURCES OF
ETHYLENE OXIDE. North Carolina: U.S. Environmental Protection Agency Office
of Air and Radiation Office of Air Quality Planning and Standards Research Triangle
Park, 2017. Print.
7) Kroschwitz, Jacqueline I and Arza Seidel. Kirk-Othmer Encyclopedia Of Chemical
Technology. 1st ed. Hoboken, N.J.: Wiley-Interscience, 2004. Print.
8) Ametek Process Instrument(2014). Use of TDLAS Based Analyzers for Real-Time
Process Control in Ethylene Oxide Production. United State. Available at
http://www.ametekpi.com/download.asbx?AttributeFileId=a6faf30f-0897-4c40-83d8-
507d06c3fce0 [Accessed 4 Mar 2017].

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