T.C.

GAZI UNIVERSITY

FACULTY OF ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

CHE452 CHEMICAL ENGINEERING DESIGN II

ASSIGNMENT I

Ethylene Oxide Production

GROUP A:

Umut Ozan SEVİNDİK 201142041 (Leader)

Hazal KOÇAK 201142018

Kerem YAYTOKGİL 201140041

Zeynep Yaren PAMUK 181140063

Instructor: Prof. Dr. Dilek VARIŞLI & Res. Teach. Asst. Doğa ŞAHİN ALICI
Due date: 16.10.2024
ANKARA
2024
 ABSTRACT

This project investigates the production of ethylene oxide (EO), a key intermediate in various
chemical processes, with a specific focus on its applications in antifreeze production. The
study begins by examining the physical and chemical properties of ethylene oxide,
highlighting its characteristics as a colorless, flammable gas with high solubility in water and
organic solvents. The investigation identifies the production methods available for ethylene
oxide, including processes utilizing ethanol, methanol, ethane, methane, and ethylene. While
the production of ethylene oxide from methanol presents the highest economic value, it has
been excluded from consideration due to significant environmental concerns and process
complexity. Instead, the direct oxidation of ethylene is determined to be the most feasible and
environmentally responsible production method.

A comprehensive market analysis reveals the growing demand for ethylene oxide, particularly
in Turkey, where imports totaled $1.98 million in 2022, contrasted by exports of $415,000.
This disparity indicates substantial opportunities for domestic production, driven by the
increasing need for ethylene glycol in antifreeze and other applications. The project also
evaluates potential plant locations, ultimately selecting Kocaeli for its logistical advantages
and market accessibility. Sustainability and safety considerations are emphasized throughout
the investigation, ensuring compliance with environmental regulations and safety standards.
This project highlights the significance of balancing economic viability with environmental
responsibility in the ethylene oxide production landscape, paving the way for future research
and development in the field.
 ASSIGNMENT 1

Due Date: 16/10/2024

Ethylene oxide (systematically named epoxythane or oxirane), with the chemical formula
C2H4O, is a colorless and flammable gas. This compound has a sharp, sweet odor. It is
widely used in the industry and commonly serves as an intermediate in the production of
polyethylene and other organic compounds.

Ethylene oxide is highly reactive, which allows it to be used in a broad range of applications
such as polymers, detergents, antifreeze, and sterilization agents. It is widely utilized for
sterilizing medical equipment, food products, and other heat-sensitive materials. Additionally,
it plays a crucial role in the production of ethylene glycol, which is used in automotive
antifreeze and industrial cooling fluids.

You are working in a company as a chemical engineer and your boss asks you to prepare a
feasibility report starting from the market survey. Your report should contain:

✓ The physicochemical properties of Ethylene oxide

✓ Product specifications,

✓ Needs for Ethylene oxide

✓ Market analysis (supply and demand, forecast for production of EO, the situation in our
country, competitive firms in the market, possible customers, unit prices, etc.),

✓ Possible production techniques,

✓Possible reaction conditions,

✓ The capacity of the EO plant etc

Table of Contents
1. INTRODUCTION...............................................................................................................1
2. LITERATURE SURVEY....................................................................................................2
2.1. Ethylene Oxide Properties............................................................................................2
2.2. Product Specifications, Areas of Usage and Needs for EO..........................................4
2.3. Market Analysis of Ethylene Oxide.............................................................................7
2.3.1. Global Production Data and Capacities................................................................8
2.3.2. Future Outlook......................................................................................................9
2.4. Plant Location Selection.............................................................................................10
2.5. Consideration of Plant Capacity.................................................................................10
2.6. Possible Production Techniques, Reaction Conditions and Process Selection of EO10
2.6.1. Chlorohydrin Process..........................................................................................10
2.6.2. The Direct Oxidation Process.............................................................................11
2.6.3. From Ethanol (C2H5OH).....................................................................................13
2.6.4. From Ethane........................................................................................................14
2.6.5. From Methane.....................................................................................................16
2.6.6. From Methanol....................................................................................................17
2.7. By-Products and Sustainability in Ethylene Oxide Production: Analysis and
Evaluation of CO₂ Utilization...............................................................................................19
2.7.1. CCU Technologies..............................................................................................19
2.7.2. Summary of Current and Future Opportunities in Carbon Capture and
Utilization (CCU)..............................................................................................................21
2.7.3. Example Research Summary: Detailed Analysis of a Facility Designed for the
Electrochemical Conversion of Carbon Dioxide (CO2) to Ethylene................................22
2.7.4. CO₂ Recycling in Ethylene Oxide Plants: A Potential Paradigm Shift for the
Chemical Industry’s Decarbonization...............................................................................25
3. RESULT AND DISCUSSION...........................................................................................27
4. CONCLUSION.................................................................................................................29
5. REFERENCES..................................................................................................................30
List of Figures

Figure 1..Use of ethylene oxide market 2020-2030....................................................................5

Figure 2.Use of ethylene oxide in USA......................................................................................6
Figure 3.Ethylene oxide in TURKEY.........................................................................................8
Figure 4.Forecasts Until 2030 for Ethylene Oxide Market.........................................................9
List of Tables

Table 1.Physical Properties of Ethylene Oxide...........................................................................3

Table 2 Feasibility Analysis......................................................................................................19
 1. INTRODUCTION

A successful plant design must ensure that the facility can produce a profitable product, which
requires an initial commitment of capital to build all necessary components. To achieve net
profit—total income minus all associated expenses—it's vital for chemical engineers to
understand the range of costs at every step of the manufacturing process. Financial resources
must cover both direct expenses, like raw materials, labor, and utilities, and indirect costs,
including administrative salaries, marketing, and distribution [1].

Additionally, it’s essential for engineers to consider the ethical implications of their designs
and prioritize environmental sustainability. A responsible plant design minimizes negative
environmental impacts, conserves resources, and aligns with sustainable practices to meet the
needs of the present without compromising future generations. This approach not only
safeguards the environment but also builds trust with the community and supports long-term
business viability.

Ethylene oxide (systematically named epoxythane or oxirane), with the chemical formula
C2H4O, is a colorless and flammable gas. This compound has a sharp, sweet odor. It is widely
used in the industry and commonly serves as an intermediate in the production of
polyethylene and other organic compounds. Ethylene oxide is highly reactive, which allows it
to be used in a broad range of applications such as polymers, detergents, antifreeze, and
sterilization agents. It is widely utilized for sterilizing medical equipment, food products, and
other heat-sensitive materials. Additionally, it plays a crucial role in the production of
ethylene glycol, which is used in automotive antifreeze and industrial cooling fluids.

Exposure to ethylene oxide has been reported predominantly in workers in sterilization units,
and should be kept as low as feasible. Health personnel working in close proximity to
ethylene oxide should be given information about its dangers, and should be informed of the
known and uncertain risks of exposure [2].

In this report, it has been examined whether the production of ethylene oxide in Turkey is
economically viable.
 2. LITERATURE SURVEY

In this section, some information such as physicochemical properties of Ethylene oxide,

product specifications, needs for Ethylene oxide, market analysis, possible production
techniques, possible reaction conditions, the capacity of the EO plant etc. are presented. Based
on this information, the specifications of the facility to be established were determined.

2.1. Ethylene Oxide Properties

Ethylene oxide or oxirane (C₂H₄O) is a colorless, toxic, and highly flammable gas with a
faintly sweet odor. This compound is a cyclic ether and the simplest epoxide, consisting of a
three-membered ring made up of two carbon atoms and one oxygen atom. Its strained ring
structure allows ethylene oxide to readily undergo ring-opening reactions in various chemical
reactions.

The danger of ethylene oxide primarily stems from its high reactivity, but this property also
makes it a valuable compound in industry. While it is unsuitable for home use, it is a key raw
material in the production of many consumer products and industrial chemicals. It is used in
the manufacture of various chemical compounds, such as detergents, solvents, plastics,
ethylene glycol, ethanolamines, and various glycols. Additionally, it plays an important role
in the production of products like polysorbate 20 and polyethylene glycol (PEG), which are
generally less toxic and more effective alternatives.

However, ethylene oxide is an extremely flammable, carcinogenic, mutagenic, irritating, and

anesthetic gas at room temperature. In the medical field, it is commonly used for sterilizing
heat-sensitive instruments and equipment, especially in hospitals and the medical device
industry, replacing steam sterilization.[3]
Table 1.Physical Properties of Ethylene Oxide

Synonyms Oxirane; ethylene oxide; 1,2-Epoxyethane; Ethylene oxide;

EO
CAS No
75-21-8
Molecular Weight 44.05 g/mol

Chemical Formula C₂H₄O

Flash Point -20 °C

Auto-ignition 429 °C
Temperature
Boiling Point 10.7 °C

Melting Point
-111.3 °C
Hazard Symbols
 2.2. Product Specifications, Areas of Usage and Needs for EO

Ethylene oxide (EO) has a wide range of industrial applications. The most common use of EO
is as an intermediate in the production of monoethylene glycol (MEG). MEG is widely
preferred in the production of PET bottles and polyester fibers in the textile industry.
Additionally, MEG is a common component in products such as antifreeze and coolant fluids.

The sterilization and disinfection properties of EO are also extremely important. EO is

preferred in applications where heat-sensitive materials need to be hygienically processed,
such as the sterilization of medical devices and the disinfection of spices and food products.
In the medical sector, EO is particularly advantageous compared to alternative sterilization
methods due to its ability to penetrate deeply.

The main applications of EO include:

 Medical Sterilization: Sterilization of medical devices and equipment.

 Food and Agriculture: Sterilization of spices and grains.

 Fumigation of Warehouses and Silos: Used as a broad-spectrum fumigant against

pests.

 Industrial Production: Used as an intermediate in the production of MEG and other

EO derivatives.

Applications of Monoethylene Glycol (MEG)

Monoethylene glycol (MEG) is the largest derivative of ethylene oxide and plays a critical
role in numerous industries. Its most common applications include:

 Polyethylene Terephthalate (PET): Used in the production of PET bottles and

polyester fibers. Polyesters are widely used in various applications, especially in the
textile sector.

 Antifreeze and Coolant Fluids: MEG is preferred in antifreeze and cooling fluids
due to its low freezing point and high boiling point.

 Industrial Applications: MEG is used in various industrial applications such as

solvents, humectants, and heat transfer fluids.
Other EO Derivatives and Applications

Other important derivatives obtained from EO production include:

 Ethoxylates: Commonly used in detergents, surfactants, and cosmetic products.

 Ethanolamines: Found in cleaning agents, cosmetic products, and agricultural

chemicals.

 Diethylene Glycol (DEG) and Triethylene Glycol (TEG): Used as humectant

solvents in various industrial applications.

 Polyols: Used as a significant raw material in the production of polyurethane foams.

[4]

Figure 1..Use of ethylene oxide market 2020-2030

Figure 2.Use of ethylene oxide in USA
 2.3. Market Analysis of Ethylene Oxide

North America:

 Increased Demand and Stable Supply in 2024: Ethelyne oxide prices in the North
American market have risen due to increased demand, particularly for Monoethylene
Glycol (MEG) and ethoxylates. Despite stable supply, the surge in demand during the
second quarter of 2024 caused upward price movements.

 Production Disruption: An unscheduled outage at Dow Chemical Company's facility

in Louisiana negatively affected production in the first quarter of the year. However,
recovery efforts were completed by June 2024, resulting in FOB Gulf Coast prices
increasing by 3% to 1,390 USD/MT.

Asia-Pacific:

 Weak Demand: In the Asia-Pacific region, particularly in Japan, ethylene oxide prices
have decreased due to weak demand. The decline in ethylene prices and limited supply
further amplified this trend.

 Price Drop: As of June 2024, FOB Ex-Osaka prices in Japan fell to 865 USD/MT due
to low demand.

Europe:

 Stagnant Market: In Europe, weak trade activities and market uncertainties led to a
decline in ethylene oxide prices in 2024. High production costs and weak demand for
MEG contributed to the drop in prices, with FOB Hamburg prices falling to 1,343
USD/MT in June.

Middle East:

 Low Demand: In the Middle East, particularly in Saudi Arabia, despite low production
costs, weak demand pushed prices down. As of June 2024, FOB Al Jubail prices were
recorded at 1,282 USD/MT. [5]
Turkey Market Overview:

 Imports: Turkey's ethylene oxide market is import-dependent. According to 2022 data,

Turkey imported ethylene oxide worth a total of 1.98 million USD, with its largest
supplier being Belgium, accounting for 585,000 USD of the imports.

 Exports: Turkey's ethylene oxide exports totaled 415,000 USD, ranking 17th globally.
Exports to countries such as Thailand and Ecuador showed growth [6]

Figure 3.Ethylene oxide in TURKEY

2.3.1. Global Production Data and Capacities

As of 2023, global ethylene oxide production reached approximately 36 million metric tons
annually. This growth has been largely driven by high demand and investments in the Asia-
Pacific region.

 North America: The United States is the largest ethylene oxide producer globally,
with an annual production of 4,009 thousand tons.
 Asia-Pacific: China and Japan stand out as the main production hubs in the Asia-
Pacific region.
 Europe: Germany and Belgium are among Europe’s significant ethylene oxide
producers.
 Middle East: Saudi Arabia is the largest producer in the region, benefiting from low-
cost production advantages.
 Turkey: Turkey has a production capacity of 115 thousand tons, contributing a small
share to global production. However, efforts to increase capacity are ongoing.
 2.3.2. Future Outlook

The ethylene oxide and derivatives markets are expected to continue growing, especially with
the rising demand for Monoethylene Glycol (MEG). MEG, which is used in PET bottle
production, is undergoing a transformation towards recycling and biologically-based raw
material solutions, considering its environmental impact. In this context, ethylene oxide
producers are expected to adopt more eco-friendly and innovative production processes.
Macro-economic factors such as energy costs, supply chain disruptions, and global inflation
will also shape the future dynamics of the market.

In 2024, varying trends have been observed in the ethylene oxide market across different
regions. Despite production disruptions, demand remained strong in North America, leading
to price increases. Conversely, weak demand and high production costs have put downward
pressure on prices in the Asia-Pacific and European markets. While Turkey continues to rely
heavily on imports from Belgium, it is also working to expand its exports to Southeast Asia
and Latin American markets. In the coming years, global inflation, energy costs, and
sustainability-focused innovations will be key factors shaping the market's direction. [7]

Figure 4.Forecasts Until 2030 for Ethylene Oxide Market

 2.4. Plant Location Selection

2.5. Consideration of Plant Capacity

2.6. Possible Production Techniques, Reaction Conditions and Process

Selection of EO

Ethylene oxide can be produced through several methods, each with unique processes and
considerations. Historically, the chlorohydrin process was the primary method, involving the
reaction of ethylene with hypochlorous acid to form ethylene chlorohydrin, which is then
converted to ethylene oxide with a base. However, the direct oxidation process is now the
most widely used method, where ethylene reacts with oxygen in the presence of a silver
catalyst. Other production techniques include the oxidation of ethanol, where ethanol is
dehydrogenated to produce ethylene oxide, and the conversion of ethane or methane, both of
which require multi-step processes involving oxidative coupling or selective oxidation. Also,
methanol can be converted to ethylene oxide through complex synthesis routes involving
methanol-to-olefins (MTO) technology. Each method has distinct advantages and challenges,
making process selection important for efficiency and environmental considerations.

2.6.1. 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 second reaction is that of the chlorohydrin with a base, usually calcium hydroxide, to
form ethylene oxide.

HOCH2CH2Cl + ½ Ca(OH)2 → CH2CH2O + ½ CaCl2 + 2H2O (2)

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 (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 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. [8]

2.6.2. The Direct Oxidation Process

The first commercial EO process using direct oxidation was developed in the United States by
Carbide and Carbon Chemicals Corp. (today Union Carbide Corp.) which started its first plant
in 1937 based on the use of air. In 1953 the Scientific Design (SD) air based process was
commercialized and by the late 1950s the direct oxidation process started to replace the
chlorohydrin process. In 1958 Shell Development introduced the first oxygen based process
for direct oxidation of ethylene. In subsequent years the oxygen based process was
commercialized by SD/Halcon (1969), Nippon Shokubai (1976), and Union Carbide (1976).
[8]

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. [8] The main disadvantage and inefficiency of the direct oxidation process is the
lower selectivity of ethylene oxide per unit of feed ethylene consumed, results from the loss
of 20-25% of the ethylene to carbon dioxide and water. [9]

All ethylene oxide direct oxidation plants are based on the original process chemistry
discovered by Lefort in 1931. [9] The direct vapor-phase oxidation of ethylene to ethylene
oxide over a silver catalyst at 220-300°C and 10-30 bar pressure produces few bi-products
other than carbon dioxide and water.

The important reactions that occur are:

Ethylene is oxidized with oxygen over a silver alumina catalyst to form ethylene oxide.
CH2=CH2 + ½ O2 → CH2-CH2O (ΔH = -106,7 kJ/mol) [8]

Ethylene is totally oxidized to form carbon dioxide and water.

CH2CH2 + 3O2 → 2CO2 + 2H2O (ΔH = -1323 kJ/mol) [8]

Ethylene oxide is further oxidized to form carbon dioxide and water.

CH2CH2O +5/2 O2→ 2CO2 + 2H2O (ΔH = -1323 kJ/mol)[8]

To prevent further oxidation of ethylene oxide, the ethylene conversion of the commercial
process is typically between 10-20% resulting in a recirculated gas loop that is explained
further in subsequent chapter. [7] In direct oxidation processes a few ppm of ethyl chloride
(2,5-3,0 ppm) or vinyl chloride (4-6 ppm) is added to the gaseous feed to inhibit the complete
oxidation reaction and increase selectivity to ethylene oxide. [13] Although small traces of bi-
products, usually less than 0,1 % of acetaldehyde and even smaller amount of formaldehyde
are also produced. [8]

CH2CH2O → CH3-CHO (Acetaldehyde)

CH3-CHO + 2 1/2O → 2CO2 + 2H2O

CH2=CH2 + O2 → 2CH2O (Formaldehyde)

The direct oxidation (EO) process can be divided into air- and oxygen based processes.

2.6.2.1. Air-Based Direct Oxidation Process

Compressed air is first purified to remove contaminants and then mixed with recycled gas and
fresh ethylene. [8] 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. [9] The gas is fed to a multitubed 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. The effluent gas from the main reactor, which now contains ethylene
oxide, is cooled in a shelland-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. [8]

2.6.2.2. 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. [8] 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 30-40% 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. [9]

2.6.3. From Ethanol (C2H5OH)

The primary reaction occurring in the production of ethylene oxide from ethanol is
dehydrogenation. This involves the removal of hydrogen from ethanol to form ethylene and
water:

C2H5OH → C2H4 + H2O

However, it's important to note that the reaction may also produce byproducts such as
acetaldehyde and diethyl ether. These byproducts can be formed through side reactions or
through the further reaction of ethylene oxide.

The specific reactions involved in the formation of byproducts can vary depending on the
reaction conditions and the catalyst used.

Here are some possible side reactions:

• Formation of acetaldehyde:

• C2H4O → CH3CHO

• Formation of diethyl ether:

• 2C2H5OH → (C2H5)2O + H2O

To minimize the formation of byproducts and maximize the yield of ethylene oxide, it is
important to optimize the reaction conditions and select appropriate catalysts.

2.6.4. From Ethane

Direct conversion of ethane to ethylene oxide is a challenging process that has been the
subject of extensive research and development. While it offers the potential for a more
efficient and integrated production route, significant technical challenges remain.

Reaction Mechanisms

The conversion of ethane to ethylene oxide involves a multi-step process. One possible
mechanism involves the following steps:

1. Dehydrogenation: Ethane is dehydrogenated to form ethylene.

2. Oxidation: Ethylene is oxidized to form ethylene oxide.

Challenges

• Selectivity: The primary challenge is to achieve high selectivity for ethylene oxide
production, minimizing the formation of unwanted byproducts such as carbon dioxide, carbon
monoxide, and water.

• Catalyst development: Developing catalysts that are active, selective, and stable under
the harsh reaction conditions is crucial.

• Energy efficiency: The process is energy-intensive, requiring high temperatures and

pressures.

• Environmental impact: The production of ethylene oxide from ethane may have
environmental implications, particularly in terms of greenhouse gas emissions.
Current Research and Development

Despite the challenges, research and development efforts continue to explore new catalysts,
process conditions, and reactor technologies for the production of ethylene oxide from ethane.
Some promising approaches include:

• Membrane reactors: Using membranes to separate products from reactants can

improve selectivity and efficiency.

• Plasma-assisted processes: Utilizing plasma to activate the reaction can lower the
energy barrier and improve selectivity.

• Hybrid processes: Combining different technologies (e.g., oxidative coupling, direct

oxidation) to optimize the overall process.

While the direct conversion of ethane to ethylene oxide remains a challenging target,
advancements in catalyst development and process engineering may eventually lead to a
commercially viable process.

The primary reaction involved in the production of ethylene oxide from ethane is a two-step
process:

1. Dehydrogenation:

C2H6 → C2H4 + H2

2. Oxidation:

C2H4 + O2 → C2H4O

However, it's important to note that the overall process can be more complex, involving
multiple side reactions and intermediate species. For example, ethane can also undergo
oxidative coupling to form butane and ethylene:

2C2H6 + O2 → C4H10 + 2H2O

Additionally, ethylene can be further oxidized to form carbon dioxide and water:

C2H4 + 3O2 → 2CO2 + 2H2O

To achieve high selectivity for ethylene oxide production, it is necessary to minimize these
side reactions and optimize the reaction conditions. This can be achieved through careful
catalyst selection, process design, and control.
 2.6.5. From Methane
Direct conversion of methane to ethylene oxide is a highly challenging process that has
received significant attention due to the abundance of methane as a natural gas component.
However, it remains a subject of ongoing research and development.

Reaction Mechanisms

The conversion of methane to ethylene oxide involves multiple steps, including:

1. Dehydrogenation: Methane is dehydrogenated to form ethylene.

2. Oxidation: Ethylene is oxidized to form ethylene oxide.

Challenges

• Selectivity: Achieving high selectivity for ethylene oxide production is a major hurdle,
as methane can undergo numerous side reactions, including complete oxidation to carbon
dioxide and water.

• Catalyst development: Developing catalysts that are active, selective, and stable under
the harsh reaction conditions is crucial.

• Energy efficiency: The process is energy-intensive, requiring high temperatures and

pressures.

• Environmental impact: The production of ethylene oxide from methane may have
environmental implications, particularly in terms of greenhouse gas emissions.

Current Research and Development

Despite the challenges, research and development efforts continue to explore new catalysts,
process conditions, and reactor technologies for the production of ethylene oxide from
methane. Some promising approaches include:

• Membrane reactors: Using membranes to separate products from reactants can

improve selectivity and efficiency.

• Plasma-assisted processes: Utilizing plasma to activate the reaction can lower the
energy barrier and improve selectivity.
• Hybrid processes: Combining different technologies (e.g., oxidative coupling, direct
oxidation) to optimize the overall process.

While the direct conversion of methane to ethylene oxide remains a challenging target,
advancements in catalyst development and process engineering may eventually lead to a
commercially viable process.

The primary reaction involved in the production of ethylene oxide from methane is a two-step
process:

1. Dehydrogenation:

CH4 → C2H4 + 2H2

2. Oxidation:

C2H4 + O2 → C2H4O

However, it's important to note that the overall process can be more complex, involving
multiple side reactions and intermediate species. For example, methane can also undergo
oxidative coupling to form ethane and ethylene:

2CH4 + O2 → C2H6 + 2H2O

Additionally, ethylene can be further oxidized to form carbon dioxide and water:

C2H4 + 3O2 → 2CO2 + 2H2O

To achieve high selectivity for ethylene oxide production, it is necessary to minimize these
side reactions and optimize the reaction conditions. This can be achieved through careful
catalyst selection, process design, and control.

2.6.6. From Methanol

Direct conversion of methanol to ethylene oxide is a highly challenging process that has
received limited attention due to the inherent difficulty of converting a one-carbon compound
to a two-carbon compound.

Reaction Mechanisms

The conversion of methanol to ethylene oxide would involve multiple steps, potentially
including:
1. Dehydration: Methanol could be dehydrated to form dimethyl ether.

2. Coupling: Dimethyl ether could be coupled to form ethylene.

3. Oxidation: Ethylene could be oxidized to form ethylene oxide.

Challenges

• Selectivity: Achieving high selectivity for ethylene oxide production is a major hurdle,
as methanol can undergo numerous side reactions, including complete oxidation to carbon
dioxide and water.

• Catalyst development: Developing catalysts that are active, selective, and stable under
the harsh reaction conditions is crucial.

• Energy efficiency: The process is likely to be energy-intensive, requiring high

temperatures and pressures.

• Economic viability: The overall process may not be economically competitive

compared to established methods for producing ethylene oxide.

Current Research and Development

While research and development efforts have explored the possibility of producing ethylene
oxide from methanol, the challenges associated with this route have limited its
commercialization. Current focus is primarily on more established methods, such as the direct
oxidation of ethylene.

In conclusion, the direct conversion of methanol to ethylene oxide remains a challenging and
speculative target. While advancements in catalyst development and process engineering may
eventually lead to a viable process, it is unlikely to become a commercially significant method
in the near future.

1. Dehydration:

2CH3OH → CH3OCH3 + H2O

2. Coupling:

2CH3OCH3 → C2H4 + 2H2O

3. Oxidation:
C2H4 + O2 → C2H4O

However, it's important to note that these reactions are highly challenging and have not been
successfully commercialized. There are numerous side reactions that can occur, leading to low
selectivity for ethylene oxide production.

Additionally, the energy requirements for these reactions are significant, making the process
economically unattractive compared to established methods for producing ethylene oxide.

Feasibility Analysis

Table 2 Feasibility Analysis

Reaction path, kg/kg ethylene oxide

Species Price, $/kg 1 2 3 4 5
C2H4 ¥ 1,01 ¥ -0,20 ¥ - ¥ - ¥ - ¥ -
O2 ¥ 0,01 ¥ -0,00 ¥ -0,00 ¥ -0,00 ¥ -0,00 ¥ -0,00
C2H5OH ¥ 0,80 ¥ - ¥ -0,21 ¥ - ¥ - ¥ -
C2H6 ¥ 0,37 ¥ - ¥ - ¥ -0,29 ¥ - ¥ -
CH4 ¥ 29,00 ¥ - ¥ - ¥ - ¥ -26,10 ¥ -
CO ¥ - ¥ - ¥ - ¥ - ¥ -
CO2 ¥ - ¥ - ¥ - ¥ - ¥ -
H2O ¥ 0,00 ¥ - ¥ 0,00 ¥ 0,00 ¥ 0,00 ¥ 0,00
H2 ¥ 6,86 ¥ - ¥ - ¥ - ¥ - ¥ -
CH3OH ¥ 0,36 ¥ - ¥ - ¥ - ¥ - ¥ -0,06
CH3OCH3 ¥ 0,50 ¥ - ¥ - ¥ - ¥ - ¥ -
C2H4O ¥ 0,97 ¥ 0,29 ¥ 0,29 ¥ 0,29 ¥ 0,29 ¥ 0,29

Excess value of products over

raw materials, $/kg ethylene oxide
¥ 0,09 ¥ 0,08 ¥ -0,00 ¥ -25,81 ¥ 0,23

2.7. By-Products and Sustainability in Ethylene Oxide Production: Analysis

and Evaluation of CO₂ Utilization

2.7.1. CCU Technologies

2.7.1.1. Framework of CCU Technologies

Carbon Capture and Utilization (CCU) aims to absorb carbon dioxide (CO2) within industrial
supply chains, contributing to a circular carbon economy. This process helps reduce, reuse,
recover, and remove carbon emissions, making it vital for addressing global emissions and
carbon-intensive manufacturing. CCU plays a crucial role in synthesizing value-added
compounds and enhancing oil recovery while focusing on resource efficiency. Although
promising, many laboratory-scale CCU technologies face technical and economic barriers.
The CCU process comprises four key steps: CO2 capture, utilization, storage, and
transportation, with particular emphasis on capture and utilization.

2.7.1.2. CO2 Capture Methods

CO2 emissions primarily arise from burning fossil fuels in industries such as hydrogen
production, cement manufacturing, and chemical production. Capture methods are
categorized into two main types: CO2 capture techniques and CO2 separation techniques.
Carbon capture technologies can be classified into three approaches:

Post-combustion Capture: The most widely used approach, it involves isolating CO2 from
flue gas through methods like absorption, adsorption, and membranes.
Oxy-fuel Combustion: Uses pure oxygen for combustion, producing CO2 with less flue gas
for direct storage.
Pre-combustion Capture: Involves producing syngas (H2 and CO) and then separating CO2
from the resultant mixture.

Absorption-Based CO2 Capture

Absorption methods isolate CO2 using liquid absorbents, forming a solution or compound.
While this method is cost-effective and stable, it has high energy demands for solvent
regeneration and can be corrosive. Alternative solutions include amino acid-based and ionic
liquid technologies, which show potential for lower toxicity and energy requirements but face
economic feasibility challenges.

Adsorption-Based CO2 Capture

Involves transferring CO2 molecules from flue gas to solid surfaces at high temperatures.
This method is attractive due to its low energy consumption and simplicity. Adsorbents used
vary in temperature characteristics, with materials like zeolites and carbon-based materials
proving effective. Physisorption and chemisorption are the main adsorption mechanisms, with
both having distinct energy requirements and efficiencies.

Membrane-Based CO2 Separation

This technique utilizes pressure differentials to separate gases through membranes, combining
high mass transfer efficiency with operational simplicity. However, it faces challenges such as
high costs and durability issues.
Chemical Looping-Based CO2 Capture

This method involves a two-stage process where fossil fuels are combusted indirectly,
separating combustion reactions to minimize direct contact with air. The process generates
pure CO2 streams, offering a clean capture method.

2.7.1.3. Recent Developments and Potential Uses

CO2 is utilized across various sectors, with the chemical and petroleum industries leading in
its usage potential. Enhanced oil recovery (EOR), urea synthesis, and polymer manufacturing
represent significant opportunities. Current industrial approaches to transform CO2 into
consumer products include catalytic, photocatalytic, electrochemical, and biological
processes. Recent studies highlight advancements in CO2 capture technologies, including the
development of efficient adsorbents and innovative conversion methods that emphasize
sustainability and reduced environmental impact.

2.7.2. Summary of Current and Future Opportunities in Carbon Capture and

Utilization (CCU)

Recent advancements in Carbon Capture and Utilization (CCU) technologies highlight their
potential to mitigate carbon dioxide (CO2) emissions while promoting a circular carbon
economy. Various processes have been proposed, such as recycling desalination wastewater to
produce calcium carbonate (CaCO3) and magnesium carbonate (MgCO3) using captured
CO2, achieving approximately 91% CO2 capture efficiency. This process has demonstrated a
maximum global profit of $73.23 per ton of CO2, indicating its economic viability for large-
scale applications.

Innovations by Baena-Moreno et al. focus on using potassium and calcium wastes as low-
energy alternatives for carbon capture in small and medium-sized applications. Furthermore,
Hernandéz et al. presented a novel method for converting CO2 into cyclic carbonate,
enhancing catalytic activity without relying on energy-intensive technologies. The steel sector
also benefits from CCU processes, where CO2 reduction methods such as photocatalytic
reduction and the use of nanocrystals are explored. Photocatalytic methods are particularly
promising due to their direct use of photons, despite their complexity.

Research on electrochemical methods, notably involving quinones, has also made significant
strides. Hemmatifar et al. showcased a bipolar cell method that captures CO2 using redox-
active quinone moieties. Additionally, machine learning (ML) techniques have emerged as
valuable tools for optimizing CCU processes, identifying new solvent candidates, and
estimating CO2 levels in solvents through regression models.

Life Cycle Assessment (LCA) plays a crucial role in evaluating the environmental impacts
and economic viability of CCU technologies. Several studies have demonstrated the
significant reduction of greenhouse gas emissions associated with CCU processes, particularly
when powered by renewable energy sources.

In conclusion, ongoing developments in CCU technologies, including photocatalysis,

biocatalysis, and electrochemistry, along with the integration of ML and LCA, are expected to
further advance the field. As these technologies evolve, CCU will be instrumental in
transitioning toward a circular carbon economy, ultimately contributing to global
sustainability goals.[10]

2.7.3. Example Research Summary: Detailed Analysis of a Facility Designed for the
Electrochemical Conversion of Carbon Dioxide (CO2) to Ethylene

This study presents a comprehensive analysis of a facility designed for the electrochemical
conversion of carbon dioxide (CO2) into ethylene. Conducted with the aim of reducing
carbon emissions, this research is considered a significant step towards sustainable chemical
production processes. The following sections will discuss the main components of the study,
its design, economic evaluation, and future potential in detail.

Introduction

The research offers a solution for reducing greenhouse gas emissions derived from carbon
dioxide. The reassessment of CO2 is critical for achieving carbon neutrality goals. In this
context, the conversion of CO2 into ethylene using electrochemical processes constitutes the
primary objective of this study.

Electrochemical Reactor Design

The electrochemical reactor designed for the conversion of CO2 into ethylene via electrolysis
is based on experimental setups developed by Dufek et al. (2011).
Reactor Components
Electrolyzer: The electrolyzer is equipped with a silver-based gas diffusion cathode and a
ruthenium (Ru)-based anode.
Ion Exchange Membrane: Nafion-424 is used as a cation exchange membrane to ensure
proton conductivity.

Operating Conditions
Temperature and Voltage: The operating conditions include a temperature of 70 °C and a
voltage of 3.5 V. The current density obtained under the applied voltage decreases at lower
voltage levels, necessitating a larger reactor design.

Production Processes

The research also encompasses the process of converting CO2 into syngas through
electrolysis. The resulting syngas is then utilized for methanol production.

Methanol Production
The syngas is converted into methanol within a reactor. The design employs Lurgi-type quasi-
isothermal steam reactors. Optimization efforts are made to maximize the hydrogen (H2) and
CO2 content in the reactor, achieving a single-pass yield as high as 49%.

Olefin Production
Methanol is converted into olefins, particularly ethylene and propylene, using the UOP-Hydro
process. High yields are obtained at this stage, with olefins constituting approximately 80% of
the total products.

Economic and Environmental Evaluation

The economic analysis of the facility highlights the impact of the high installation cost of the
electrolyzer on the total investment cost.

Energy Costs
The costs associated with renewable energy sources significantly affect the economic
sustainability of the system. The study indicates a positive operating result under a pricing
scenario of $20/MWh.

CO2 Pricing
The price of CO2 used as a feedstock is also a critical factor. In a favorable pricing scenario,
the operational lifespan of the facility ranges from 17 to 18 years.
Electrolyzer Sizing

The total volume of the electrolyzer is determined to be 28,000 m³. The feasibility of this
value is assessed through comparisons with existing hydrogen electrolyzers.

Size and Area

The total area of the electrolyzer offers a viable scaling option in locations with ample open
space. For instance, a 660 MW electrolyzer requires an area of 66 hectares.

Qualitative Assessment

Another important aspect is the quality of the CO2 source. High purity CO2 is crucial for the
efficiency of the electrolysis process.

Pollution Issues
There is a possibility that CO2 obtained from industrial sources may contain harmful
components. This situation could reduce process efficiency and adversely affect equipment
performance.

Conclusion and Future Perspectives

This research outlines the environmental impacts and economic potential of the process for
converting carbon dioxide into ethylene. The high costs associated with electrolyzer design
indicate a need for further R&D in the future.

Future Research

The findings of this study are applicable to the ethylene oxide (EO) production process.
Ethylene oxide is an essential intermediate in industrial chemistry, and its production via such
electrochemical methods could enable lower emissions. In this context, utilizing carbon
dioxide at the reactor inlet and improving energy efficiency may contribute to sustainable
production processes.

This research has the potential to enhance environmental sustainability compared to

traditional methods used in the industry. In the coming years, further investigation and
application of such electrochemical approaches could help us achieve climate targets.[11]
 2.7.4. CO₂ Recycling in Ethylene Oxide Plants: A Potential Paradigm Shift for the
Chemical Industry’s Decarbonization
Rapid action is essential to reduce global greenhouse gas emissions and prevent
environmentally and economically destructive climate disruption. However, the world
economy's reliance on fossil fuel-derived products poses a significant barrier to progress
toward a zero-emission future. Currently, the chemical industry is responsible for
approximately 15% of industrial CO₂ emissions. As long as economies remain dependent on
fossil fuels, these emissions will persist as a harmful byproduct.

A promising pathway to reduce these emissions is to use CO₂ as a feedstock and convert it
into essential chemical products through Carbon Capture and Utilization (CCU) technologies.
CCU not only enables the reuse of CO₂ instead of underground storage but also reduces the
need for extracting fossil fuels. Despite the immense potential of CCU to prevent CO₂
emissions, large-scale deployment has been slow, primarily due to unfavorable process
economics and the need to establish a new supply chain to support CO₂-based production.

A recent study by Dr. Magda Barecka, Professor Joel Ager, and Professor Alexei Lapkin,
published in Energy & Environmental Science, proposes a solution that addresses these
limitations by integrating CO₂ conversion reactors into existing chemical production
processes in an economically viable way. This technology does not require new plants or
factories—it can be retrofitted into existing chemical facilities, avoiding competition with
well-established methods for bulk chemical production.

The recycling concept is based on using an electroreduction reactor where CO₂ is converted
into valuable chemicals like ethylene. While this technology can be applied to any CO₂-
producing facility, using concentrated CO₂ streams is the most economically feasible option
as it eliminates the need for costly procedures to separate CO₂ from flue gas. Therefore, the
researchers chose to redesign a chemical process where such a concentrated CO₂ stream is
already present: ethylene oxide (EO) production. Currently, EO plants often release this
pollutant stream into the atmosphere, but the proposed technology allows it to be converted
back into ethylene. This bulk chemical can then be used as a feedstock for EO production,
meaning the products of CO₂ electrolysis can be directly used in the same facility, minimizing
both direct CO₂ emissions and the need for petrochemical raw materials.

These findings highlight how synergies between established and emerging processes can
accelerate the decarbonization of the chemical industry and demonstrate that more sustainable
chemical production methods can be economically viable in today’s market. Moreover, since
CO₂ conversion reactors are powered by electricity, the CO₂-to-chemicals process can utilize
excess renewable energy, promoting greater integration of renewables into the grid.[12]
 3. RESULT AND DISCUSSION

The investigation into the production of ethylene oxide (EO) has revealed essential insights
into its physical and chemical properties, applications, and production methods. Ethylene
oxide is identified as a colorless, flammable gas with a sweet odor, notable for its high
solubility in both water and organic solvents. With a low boiling point of 10.5 °C and
significant reactivity due to the epoxide functional group, EO can readily undergo ring-
opening reactions, making it a valuable intermediate in various chemical processes,
particularly in the production of antifreeze and other derivatives.

The applications of ethylene oxide, particularly in antifreeze production, have been

emphasized. Ethylene glycol, derived from EO, serves as a key component in antifreeze
formulations, providing effective freezing point depression and corrosion inhibition. The
increasing demand for antifreeze in automotive and industrial sectors presents substantial
commercial potential for the production of ethylene oxide as a precursor for ethylene glycol.

Various production methods for ethylene oxide have been examined, including those from
ethanol, methanol, ethane, methane, and ethylene. While the production of ethylene oxide
from methanol offers the highest excess value of products over raw materials, this method has
been deemed unsuitable due to environmental concerns and the complexity of the production
process. Also production from methanol has lower purity results as it is compared to
production from ethylene since demand of the market is high purity production of EO whixh
is 97%. The direct oxidation of ethylene has been identified as the most feasible method for
producing ethylene oxide. This method is relatively straightforward, has a lower
environmental impact, and allows for continuous production and scalability.

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. [9] 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. [8] 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% [8].
A comprehensive market analysis has indicated significant growth in the global ethylene
oxide market, particularly in regions like Turkey. In 2022, Turkey imported ethylene oxide
valued at $1.98 million, indicating a reliance on foreign sources, while its exports amounted
to $415,000. This disparity highlights potential growth opportunities for domestic production.
The rising demand for ethylene glycol in antifreeze and other applications suggests a
promising outlook for ethylene oxide production in Turkey, driven by domestic consumption
and potential export opportunities.

İzmir has been selected as the optimal location for the production facility, considering factors
such as logistical advantages and proximity to key markets. This location is expected to
enhance the efficiency of operations and reduce transportation costs. The capacity of
production has been chosen as İzmir as it has been investigated that ethylene oxide production
of PETKIM in Turkey.

Sustainability and safety investigations have been integral to this project. Ensuring that the
chosen production methods align with environmental regulations and safety standards is
crucial for the long-term viability of ethylene oxide production. Overall, this project
demonstrates a thorough analysis of the ethylene oxide production landscape, emphasizing the
importance of selecting appropriate methods that balance economic viability with
environmental responsibility.
 4. CONCLUSION

This study has examined the commercial and technical aspects of ethylene oxide (EO)
production, highlighting its significant potential, particularly for the production of ethylene
glycol used in antifreeze. Among the production methods, the direct oxidation of ethylene has
emerged as a more sustainable and efficient option. Oxygen-based processes provide higher
selectivity, while air-based processes can operate at lower costs.

The market analysis for Turkey emphasizes the importance of domestic production, and İzmir
has been identified as an ideal location due to its logistical advantages and proximity to
facilities like PETKIM. Ensuring compliance with sustainability and safety standards is
crucial for the long-term success of this project.
 5. REFERENCES

[1] Peters, M. S., & Timmerhaus, K. D. (1980). Plant design and economics for chemical
engineers. New York: McGraw-Hill

[2] Catherine J. Shelp,Ethylene oxide (EO),Editor(s): Philip Wexler,Encyclopedia of

Toxicology (Fourth Edition),Academic Press,2024,Pages 489-496

[3] https://pubchem.ncbi.nlm.nih.gov/compound/6354#section=InChIKey Accessed on:

October 10, 2024

[4] Rodin, V., Böhm, H., Lindorfer, J., & Paulik, C. (2023). Techno-economic evaluation of
the electrochemical production of renewable ethylene oxide from fluctuating power sources
and CO₂. Journal of CO₂ Utilization, 75, 102554

[5] https://www.chemanalyst.com/Pricing-data/ethylene-oxide-1102 Accessed on: October

14, 2024

[6]https://oec.world/en/profile/bilateral-product/oxirane-ethylene-oxide/reporter/tur?
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[7]https://www.researchgate.net/figure/World-production-of-ethylene-oxide-
2004_tbl5_280308375 Accessed on: October 10, 2024

[8] John J. McKetta, Encyclopedia of Chemical Processing and Design, volume 20

[9] Kirk-Othmer, Encyclopedia of Chemical Technology, volume 9 fourth edition

[10] Peres, C. B., Resende, P. M. R., Nunes, L. J. R., & de Morais, L. C. (2022). Advances in
Carbon Capture and Use (CCU) Technologies: A Comprehensive Review and CO2 Mitigation
Potential Analysis. Clean Technologies, 4(4), 1193-1207.
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[11} Berkelaar, L., van der Linde, J., Peper, J., Rajhans, A., Tiemessen, D., van der Ham, L.,
& van den Berg, H. (2022). Electrochemical conversion of carbon dioxide to ethylene: Plant
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[12] Barecka, M., Ager, J., & Lapkin, A. (2021). CO₂ Recycling in Ethylene Oxide Plants:
Potential Paradigm Shift on How the Chemical Industry Can Start Rapid
Decarbonization. Zero Carbon Research Initiative. Retrieved from
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[13] C.H Bartholomew and R.J. Farrauto, Fundamentals of Industrial Catalytic Processes,
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