GAZI UNIVERSITY

FACULTY OF ENGINEERING

CHEMICAL ENGINEERING DEPARTMENT

CHE 452 CHEMICAL ENGINEERING DESIGN II

PRODUCTION OF DIMETHYL ETHER VIA INDIRECT

PROCESS

Associate: Prof. Dr. Hüseyin Arbağ

Assistant: Nida Arasan

TEAM C

22114040036 Zeynep Sena Duran

22114040038 Nedim Etka Genç

22114040069 Muhammet Emre Yöntem

22114040081 Beyza Işık

Due Date: 04.03.2026

ANKARA,2026
Abstract
The transition toward sustainable energy systems and low-carbon chemical production
pathways has intensified interest in carbon utilization technologies and alternative clean fuels.
Dimethyl ether (DME) has emerged as a promising candidate due to its high cetane number,
soot-free combustion characteristics, absence of sulfur content, and compatibility with existing
LPG infrastructure. In addition to its application as an alternative diesel and LPG substitute,
DME serves as an important intermediate in the chemical industry. Within this context, the
indirect production of DME from carbon monoxide (CO) and carbon dioxide (CO₂) represents
a strategically important process, combining carbon valorization with fuel synthesis.

This project offers a process evaluation of an indirect DME synthetic pathway based on the
synthesis of methanol and subsequent dehydration of the product. In this pathway, the primary
reactants are a mixture of carbon monoxide, carbon dioxide, and hydrogen gas, denoted
collectively by the term "syngas." In the first step of the process, the mixture of carbon dioxide
and carbon monoxide reacts with hydrogen under high pressure and moderate temperature to
produce methanol. This reaction, like the DME synthesis, is an exothermic, equilibrium-
constrained reaction for which the conditions have to be carefully controlled for optimal
reaction performance and thermal stability of the process. In the next step, the synthesized
methanol reacts with water under the influence of an acidic catalyst, producing DME and water,
which is also an exothermic, equilibrium-constrained reaction. Material and energy balance
equations were also developed to determine the level of conversion, product yield, and process
efficiency. The effect of important process parameters such as temperature, pressure, and
H₂/COx on the process was also analyzed from a thermodynamic point of view. Special
emphasis was given to the heat management in the methanol synthesis reactor and the design
of the separation steps for DME purification and methanol recycle integration. Finally, the
indirect route was assessed in terms of process flexibility, controllability of the reactions, and
opportunities for integration with other CO₂ utilization options. Based on the market survey the
capacity selected as 35,000 ton/year.

The results show that the indirect DME synthesis route has advantages in terms of process
controllability and modular design, but also faces issues in terms of hydrogen consumption,
equilibrium limitations, and heat management. This study shows that the process is technically
viable and that the design aspects are critical to the efficient synthesis of DME.

2
Table of Contents

Abstract ...................................................................................................................................... 2
Table of Contents........................................................................................................................ 3
List of Figures ............................................................................................................................ 6
List of Tables .............................................................................................................................. 7
List of Appendices ...................................................................................................................... 8
[Link] ............................................................................................................................. 9
2. Project Management and Risk Assessment .......................................................................... 11
[Link] to Process Chemicals ........................................................................................ 13
[Link] Properties of Carbon Dioxide............................................................. 14
[Link] of Carbon Dioxide ................................................................................................. 15
[Link] Properties of Carbon Monoxide ......................................................... 16
[Link] Properties of Hydrogen ...................................................................... 17
3.5. Physicochemical Properties of Methanol ...................................................................... 19
3.6. Physicochemical Properties of Dimethyl Ether ........................................................... 20
[Link] of DME ........................................................................................................... 21
[Link] Pathways for Indirect DME Synthesis ............................................................ 22
[Link]₂ and CO to Methanol & DME .......................................................................... 22
[Link] Reverse Water-Gas Shift (rWGS) Reaction ..................................................... 23
[Link] Effect of Temperature on Selectivity ............................................................... 23
4. DME Production Methods ................................................................................................... 25
4.1. Direct DME Production ................................................................................................ 25
[Link] Section ............................................................................................... 25
4.1.2. Reforming Section.................................................................................................. 26
4.1.3. DME Synthesis Section .......................................................................................... 27
4.1.4 Separation, Purification and Recycle Sections ........................................................ 28
[Link] DME Production ............................................................................................... 29
4.2.1 Pretreatment Section ............................................................................................... 29
4.2.2 Reforming Section................................................................................................... 29
4.2.4 Methanol Synthesis Section .................................................................................... 33
4.2.5 Methanol Synthesis Reaction .................................................................................. 33

3
 4.2.6 DME Synthesis Section ........................................................................................... 34
4.2.7 Separation, Purification and Recycle Sections ........................................................ 34
[Link] Pricing: Definition, Market Trends, Economic Importance and Future Outlook ..... 35
[Link] Pricing Methods................................................................................................. 37
[Link] Market Trends and Expansion Dynamics ........................................................... 38
[Link] Price Levels and Market Valuation .................................................................... 39
[Link] and Strategic Importance of Carbon Pricing ................................................. 40
[Link] Pricing Developments in Türkiye ...................................................................... 40
[Link] Outlook ............................................................................................................... 41
6. Method of Calculation .......................................................................................................... 42
6.1. Mass Balances ............................................................................................................... 42
6.2. Energy Balances ............................................................................................................ 43
7. Selected Process Description ............................................................................................... 44
[Link] Section .................................................................................................. 44
[Link] Section ....................................................................................................... 44
[Link]-Liquid Seperation.................................................................................................... 45
[Link] Synthesis Section ........................................................................................... 46
[Link] Purification Section ........................................................................................ 47
[Link] Synthesis Section .................................................................................................. 48
[Link] Purification Section .............................................................................................. 48
[Link]-Liquid Seperation.................................................................................................... 49
[Link] Flow Diagram and Mass Balance ............................................................................ 50
9. Market Survey ...................................................................................................................... 57
9.1. Demand and Supply in Turkey, Europe and World ....................................................... 57
9.2. Production in Turkey, Europe and World ...................................................................... 60
9.3. Imports and Exports ...................................................................................................... 62
9.4. Availability of Raw Materials........................................................................................ 64
9.5. Price in Turkey and In World Market ............................................................................ 64
9.6. Future Expectations ....................................................................................................... 65
9.7. Capacity Determination................................................................................................. 68
9.8 Feasibility ....................................................................................................................... 68
10. Sample Calculations ........................................................................................................... 70
11. Results ................................................................................................................................ 80

4
 11.1. Design Basis and Final Operating Conditions............................................................. 80
11.2. Mass Balance Results .................................................................................................. 80
11.3. Energy Balance Results ............................................................................................... 82
11.4. Economic Results ........................................................................................................ 84
[Link] ........................................................................................................................... 86
[Link] ........................................................................................................................... 92
14. Recommendations .............................................................................................................. 94
15. References .......................................................................................................................... 96
16. Appendices ......................................................................................................................... 98

5
List of Figures
Figure 1. Simplified Block Diagram of Direct Synthesis of DME .......................................... 25
Figure 2. General Gas Processing Flow Diagram .................................................................... 26
Figure 3. Nitrogen Removal Process ........................................................................................ 26
Figure 4. Direct Synthesis Route of DME ............................................................................... 29
Figure 5. Simplified Block Diagram of Indirect Route ............................................................ 29
Figure 6. Effect of Temperature on Equilibrium ...................................................................... 30
Figure 7. Effect of Temparature On Steam Reforming ............................................................ 31
Figure 8. Effect of Temperature on Dry Reforming ................................................................. 32
Figure 9. Product Time Plot of Products .................................................................................. 34
Figure 10. Indirect Synthesis Route ......................................................................................... 35
Figure 11. Exchange Traded Carbon Credit Prices by Project Types ...................................... 37
Figure 12. Share of Global Greenhouse Gas Emissions Covered by an ETS or Carbon Tax .. 38
Figure 13. Global Total Carbon Price for the Period ............................................................... 39
Figure 14. Block Diagram of our Process ................................................................................ 44
Figure 15. Process Flow Diagram of our Process .................................................................... 51
Figure 16. Projected Global DME Demand for 2050 .............................................................. 57
Figure 17. Dimethyl Ether Market Size ................................................................................... 58
Figure 18. Total DME Usage in 2031 ...................................................................................... 58
Figure 19. Total DME Usage in 2050 ...................................................................................... 59
Figure 20. Total DME Usage in 2050 With Increased Europe Share ....................................... 59
Figure 21. Top Exporters of HS2909.19 .................................................................................. 62
Figure 22. Türkiye Import and Export Values for DME .......................................................... 63
Figure 23. Türkiye Net Trade Balance From HS2909.19 ........................................................ 63
Figure 24. Dimethyl Ether Market Share ................................................................................. 65
Figure 25. Potential for Corporate Sourcing of Renewable Electricity ................................... 66
Figure 26. Inter Sectoral Comparison of Renewable Electricity Sourcing .............................. 66
Figure 27. Dme Scope Analysis for 2050 as Value and Volume .............................................. 67
Figure 28. Cost Analysis for Purchased Hydrogen .................................................................. 85
Figure 29. Cost Analysis for Bi-forming .................................................................................. 85

6
List of Tables
Table 1. Project Management and Risk Assessment ................................................................ 11
Table 2. Physicochemical Properties of CO2 ........................................................................... 15
Table 3. Physicochemical Properties of CO ............................................................................. 17
Table 4. Physicochemical Properties of H2.............................................................................. 18
Table 5. Physicochemical Properties of Methanol ................................................................... 19
Table [Link] Properties of DME........................................................................... 21
Table 7. Syngas to Methanol Process Conditions .................................................................... 33
Table 8. Methanol to DME Process Conditions ....................................................................... 34
Table 9. Components,mole fractions and Enthalpys ................................................................ 43
Table 10. Components and their Cp coefficients ..................................................................... 43
Table 11. Stream Summary Table ............................................................................................. 52
Table 12. Equipment Summary Table ...................................................................................... 53
Table 13. Component Values in Outlet of Biforming Reactor ................................................. 54
Table 14. Component Values in Outlet of Methanol Reactor ................................................... 55
Table [Link] Table for Capacity........................................................................................ 56
Table 16. Advantages of DME to MTBE as Pricing ................................................................ 67
Table 17. Reactor Operating Conditions .................................................................................. 80
Table 18. Mass Balance Calculations for Equipments ............................................................. 81
Table 19. Needed Amount for 1 ton of DME ........................................................................... 82
Table 20. Energy Requirements of Equipments ....................................................................... 82
Table 21. Aspen Plus Simulation Result .................................................................................. 83
Table 22. Calculation Comparison ........................................................................................... 83
Table [Link] for Producing 1 ton of DME ........................................................................... 84
Table 24. Estimated Values for Raw Materials ........................................................................ 84
Table 25. Different Scenarios for Production ........................................................................... 85

7
List of Appendices
Appendice 1. Physicochemical Properties ............................................................................... 98
Appendice [Link] Properties contd. ..................................................................... 99
Appendice 3. Physicochemical Properties contd. .................................................................. 100
Appendice 4. Physicochemical Properties contd. .................................................................. 101
Appendice 5. Physicochemical Properties contd. .................................................................. 102
Appendice 6. Different catalyst for biforming reactor ........................................................... 103
Appendice 7. Effect of Pressure for Carbon Conversion ....................................................... 103
Appendice 8. Methanol Conversion over 4 Different Amberlyst .......................................... 104

8
[Link]
The rising global demand for sustainable sources of energy and the urgent need to mitigate
greenhouse gas emissions have prompted scientists to accelerate research on carbon use and
alternative fuel sources. Among the many synthetic fuels that scientists have proposed as
environmentally friendly substitutes for conventional sources of energy, dimethyl ether (DME)
has received considerable attention for its environmentally friendly properties. DME has a high
cetane number, zero particulate matter, and relatively lower nitrogen oxide emissions compared
to conventional diesel fuels. In addition, DME contains no sulfur. These properties make DME
a promising replacement for diesel fuel in compression ignition engines and an alternative to
liquefied petroleum gas for domestic and industrial use. In addition to being a fuel, DME has
found use as a chemical intermediate for aerosol propellants and petrochemical synthesis.

On the other hand, carbon monoxide (CO) and carbon dioxide (CO2) are readily available in
large quantities, making them strategic resources. CO is usually supplied from synthesis gas,
which is produced through a gasification or a reforming reaction, while CO2 is readily available
in large quantities as a byproduct of various human activities. The use of CO and CO2 gases in
the production of valuable chemicals not only promotes resource optimization but also plays a
role in carbon management strategies through the utilization of CO2 in a more valuable product.
Hydrogen, which is a clean fuel, further boosts the sustainability of the reactions. The process
of dimethyl ether synthesis can be achieved either through direct or indirect synthesis. In the
direct method, methanol synthesis and dehydration reactions are carried out simultaneously.
However, the indirect method, on which the basis of this design project is established, divides
the process into two separate reactions. In the first stage, the hydrogenation reactions involving
syngas, comprising CO, CO2, and H2, produce methanol. These reactions are exothermic,
equilibrium-controlled reactions, generally carried out at high pressures and moderate
temperatures. The ratio of hydrogen to carbon content in the feed gas is critical for the overall
process efficiency.

In the second step, dehydration of methanol occurs through an acidic catalyst, resulting in the
formation of dimethyl ether and water. Although this reaction has a favorable thermodynamic
balance at a specific temperature, it is still an equilibrium-dependent reaction, requiring proper
thermal management for the catalyst’s stability and DME yield maximization. The two-step
structure of the indirect process enables the optimization of the two stages of the chemical
reaction, enhancing the flexibility of the process compared to the direct approach. Nevertheless,
the process becomes more complicated by the additional separation requirements.

9
From the process design viewpoint, the indirect method of DME synthesis poses many
important process design considerations. In particular, the strong exothermic nature of methanol
synthesis dictates the importance of effective heat removal techniques to prevent catalyst
deactivation. In addition, the reactor configuration, temperature, and pressure conditions are
critical factors that affect the equilibrium conversion. Finally, the design of the separation
equipment, such as flash vessels and distillation columns, must ensure the production of DME
with high purity while minimizing the energy consumption. In particular, the unreacted
methanol must be recycled to maximize the yield.

The objective of the present design study is to propose and assess a conceptual process for the
indirect synthesis of dimethyl ether from CO and CO2 through methanol synthesis and
dehydration. By integrating thermodynamic considerations with process engineering principles,
the work aims to assess the technical feasibility of the proposed system and to highlight the
opportunities and limitations associated with indirect DME production within the broader
context of sustainable chemical manufacturing.

10
2. Project Management and Risk Assessment
Table 1. Project Management and Risk Assessment

Task # Task Description Date Responsible Priority Risk / Potential

Range Issue
1 Physicochemical 12–14 Feb Beyza Critical Incorrect or
Data Collection inconsistent
— DME, property data
methanol, CO,
CO2 properties
2 Demand & 14–17 Feb Emre High Outdated or
Supply Analysis unreliable data
(Turkey, Europe,
World)
3 Production 15–18 Feb Emre Medium Missing
Analysis industrial
(Turkey, Europe, capacity info
World)
4 Imports & 16–18 Feb Beyza Medium Incomplete
Exports trade statistics
Investigation
5 Raw Material 17–19 Feb Nedim High Underestimating
Availability (CO, supply
CO2, H2 limitations
sources)
6 Price Analysis 18–20 Feb Emre High Incorrect price
(Turkey & World comparison
Market)
7 Future 19–22 Feb Zeynep Critical Unrealistic
Expectations — growth
20 Year assumptions
Projection
(demand, supply,
price, capacity)
8 Capacity 21–23 Feb Zeynep & Critical Oversized or
Determination Nedim undersized plant
(Plant size design
selection)
9 Feasibility Study 22–25 Feb Zeynep Critical Weak economic
(Technical, justification
Economic,
Environmental)

11
10 Process Selection 24–26 Feb All High Selecting non-
Criteria optimal process
Evaluation route
11 Environmental 26–28 Feb Emre & High Missing
Impact Zeynep emission
Assessment scenarios
12 Energy & Utility 27 Feb – 1 Nedim High Underestimated
Requirement Mar utility demand
Evaluation
13 Reaction 13–15 Feb Nedim High Wrong reaction
Thermodynamics heat estimation
& Enthalpy
Calculations
14 Final Review & 2–3 Mar All Critical Inconsistent
Report formatting or
Compilation missing data
15 Submission 4 Mar All Critical Late submission

12
[Link] to Process Chemicals
The indirect synthesis of dimethyl ether (DME) is an integrated process involving two
consecutive steps of chemical reactions, namely, the synthesis of methanol from synthesis gas,
followed by the subsequent dehydration of the synthesized methanol to produce dimethyl ether.
In the first step, the synthesis gas, primarily composed of carbon monoxide (CO), carbon
dioxide (CO₂), hydrogen (H₂), etc., is catalytically transformed into methanol at high
temperature and pressure conditions. In the second step, the synthesized methanol is subjected
to a dehydration reaction in the presence of an acidic catalyst, resulting in the formation of
dimethyl ether (DME) and water.

Thus, the integrated synthesis of dimethyl ether essentially involves several important chemical
species such as CO, CO₂, H₂, methanol (CH₃OH), and dimethyl ether (CH₃OCH₃). These
species have crucial implications in the kinetics, thermodynamic equilibrium, and overall
efficiencies of the integrated synthesis of dimethyl ether, making it essential to have an in-depth
knowledge of the physicochemical properties and industrial characteristics of the species
involved in the synthesis of the desired product [1].

Carbon monoxide and carbon dioxide are the major carbon-containing components of the
synthesis gas mixture. These components play a vital role in determining the reaction path,
equilibrium conversion, and hydrogen consumption for the synthesis process. On the other
hand, hydrogen is the reducing agent for the synthesis process. Excess hydrogen is usually
supplied to favor the forward reaction for methanol synthesis.

The stoichiometric relationship between carbon monoxide, carbon dioxide, and hydrogen is a
major factor that affects reactor volume calculations, design of recycle streams, and overall
material balance calculations for the synthesis process [2].

Methanol is a vital component for the indirect synthesis process for DME synthesis. The rate
of formation, purity, and separation efficiency of methanol determine the efficiency of the
subsequent reactor for dehydration. Since methanol is a product with both economic value and
reactivity, its thermodynamic properties must be considered for a proper analysis. Specifically,
vapor-liquid equilibrium properties and boiling point properties must be considered for a proper
design for distillation columns for separation purposes.

Dimethyl ether, being the end product of this process, is a clean-burning alternative fuel as well
as a chemical intermediate of considerable importance. The low-boiling dimethyl ether, having
a high cetane number, is a potential substitute for conventional LPG and diesel fuels. However,

13
its flammability limits also need to be considered for this process plant design. The precise
knowledge of DME’s critical properties, vapor pressure, and density is essential for this process
simulation.

It is very important to understand the thermodynamic behavior, physicochemical properties,

and safety aspects of these chemicals to simulate this process accurately, design equipment, and
evaluate its economic viability correctly. These properties are likely to affect the operating
conditions, separation, energy, and environmental impacts of this process plant. With this
importance of these chemicals, their properties, and their industrial importance, the key
properties of CO, CO₂, H₂, methanol, and DME are discussed below in detail [3].

[Link] Properties of Carbon Dioxide

In the first reactor, CO2 reacts with hydrogen gas to form methanol and water. The
stoichiometry of the reaction is affected, and the rate of hydrogen gas consumption is
influenced. The amount of hydrogen gas required for the conversion of CO2 is more as
compared to that required for carbon monoxide. The composition of reactants becomes
important. The presence of CO2 has an effect on the thermodynamic equilibrium. The methanol
synthesis reaction is an equilibrium-limited reaction that is temperature and pressure dependent.

In terms of process design, CO2 has an effect on water formation as a byproduct during
methanol synthesis. The physicochemical properties of CO2, such as critical temperature and
pressure, become important under high-pressure conditions. The knowledge of CO2
thermodynamic properties is important for mass balance and energy balance calculation. The
conversion of CO2 into value-added products such as DME makes the overall process more
environment friendly [5].

Carbon dioxide is a colourless, tasteless, odourless gas that is naturally present in the Earth’s
atmosphere. It is produced by all living organisms. In humans it is removed from the body in
air breathed out. It can also be man-made [4].

14
Table 2. Physicochemical Properties of CO2

Property Value Unit

Chemical Formula CO₂ —
Molecular Weight 44.01 g/mol
Physical State (25°C, 1 atm) Gas —
Color Colorless —
Odor Odorless —
Boiling Point (1 atm) −78.5 °C
Melting Point −56.6 °C
Triple Point Pressure 5.18 bar
Critical Temperature (Tc) 31.1 °C
Critical Pressure (Pc) 73.8 bar
Critical Density 467 kg/m³
Gas Density (25°C, 1 atm) 1.84 kg/m³
Liquid Density (near Tc) ~770 kg/m³
Heat Capacity (Cp, gas, 25°C) 37 J/mol·K
Standard Enthalpy of Formation (ΔHf°) −393.5 kJ/mol
Thermal Conductivity (gas) 0.0166 W/m·K
Flammability Non-flammable —
Toxicity Low toxicity but asphyxiant —

[Link] of Carbon Dioxide

Carbon dioxide is produced naturally by living organisms such as humans, animals, plants and
microbes. It plays an important role in various processes that are essential for life.

It can be manufactured and used as solid, gas or liquid (when kept under pressure). Solid carbon
dioxide, which is also known as dry ice, is used to keep things cool and is used in fog machines.
Carbon dioxide is also used to produce bubbles in fizzy drinks, as a refrigerant, a preservative
and used in fire extinguishers.

It is constantly being produced and removed from the environment by oceans and growing
plants in a process known as the carbon cycle. Other natural sources of carbon dioxide include

15
forest fires and volcanoes. Human activities such as burning coal, oil and gas lead to the
production of carbon dioxide; hence it can enter the environment from emissions from factories
or power stations that burn fossil fuels. Other sources that can increase levels include motor
vehicles and the burning of oil and gas in homes for heating.

[Link] Properties of Carbon Monoxide

One of the most important carbon-containing reacting substances in the indirect process for the
production of dimethyl ether is carbon monoxide (CO). In the methanol synthesis reactor,
carbon monoxide undergoes an exothermic catalytic reaction with hydrogen to produce
methanol. Compared to carbon dioxide, carbon monoxide has a lower hydrogen-to-carbon ratio,
making it more hydrogen-efficient in the process.

The influence of the carbon monoxide-to-carbon dioxide ratio in the reacting substances can
also be viewed from a thermodynamic point of view, where the methanol synthesis reaction
containing carbon monoxide is an equilibrium-limited process that occurs at high pressure and
moderate temperatures. Because the process is exothermic, the temperature in the reactor must
be properly controlled to avoid the shift in the equilibrium towards the reactants and to prevent
the deactivation of the catalysts used in the process. The physicochemical properties of carbon
monoxide, such as its gaseous state, low molecular weight, and high diffusion rate, also play an
important role in the design considerations in the reactor, such as the space velocity in the
process [4].

In addition to its chemical role, carbon monoxide presents significant safety concerns. It is a
colorless, odorless, and highly toxic gas that binds strongly to hemoglobin, posing serious risks
in case of leakage. Therefore, continuous monitoring systems, proper ventilation, and leak
detection mechanisms must be incorporated into plant safety design. Despite these hazards, CO
remains an essential feedstock in syngas-based chemical industries due to its high reactivity
and carbon efficiency. In the context of DME production, efficient conversion of CO enhances
carbon utilization and contributes positively to the economic and environmental performance
of the overall process.

16
Table 3. Physicochemical Properties of CO

Property Value Unit

Chemical Formula CO —
Molecular Weight 28.01 g/mol
Physical State (25°C, 1 atm) Gas —
Color Colorless —
Odor Odorless —
Boiling Point (1 atm) −191.5 °C
Melting Point −205.0 °C
Critical Temperature (Tc) 132.9 K (−140.2 °C)
Critical Pressure (Pc) 34.9 bar
Critical Density 303 kg/m³
Gas Density (25°C, 1 atm) 1.14 kg/m³
Heat Capacity (Cp, gas, 25°C) 29 J/mol·K
Standard Enthalpy of Formation (ΔHf°) −110.5 kJ/mol
Thermal Conductivity (gas) 0.024 W/m·K
Flammability Limits (air) 12.5–74 vol %
Autoignition Temperature 609 °C
Toxicity Highly toxic —

[Link] Properties of Hydrogen

The methanol synthesis stage where hydrogen (H₂) is the nucleus reducer in the indirect
production of dimethyl ether. Within the reactor, methanol is formed, and this happens via high
exothermic catalytic reactions, when hydrogen undergoes a reaction with carbon monoxide
(CO), and carbon dioxide (CO₂). In the processes of synthesis gas (syngas), the H₂/COx ratio is
a relevant parameter due to the fact that it has a direct impact with the conversion and
selectivity, the efficiency of the reactor, its size, and the overall efficiency of the processes.
Since the synthesis of methanol is limited to equilibrium, the hydrogen partial pressure has an
effect on the reaction equilibrium and carbon conversion efficiency. Higher concentrations of
hydrogen favors the production of methanol, but an excessive amount of hydrogen can cause
an increase in the recycle load and compression costs. Therefore, accurate control of hydrogen
is economically feasible and is thermodynamically optimized. Hydrogen is operationally

17
challenging from both the safety and the process design perspectives. Its lightweight, high
diffusivity, and a very wide flammable range, as well as other features, lead to increased risks
of leakage and explosive charges; this is of particular concern when operating under high
pressures typical of methanol synthesis operations (50–100 bar). Its high thermal conductivity
impacts the heat removal desired in exothermic reactors. Due to its small molecular size,
hydrogen may cause material embrittlement in certain metals, which must be considered in
reactor and pipeline material selection.

In the context of sustainable DME production, hydrogen source selection (e.g., steam reforming
vs. green hydrogen via electrolysis) significantly impacts the overall carbon footprint and
environmental performance of the plant.

Table 4. Physicochemical Properties of H2

Property Value Unit

Chemical Formula H₂ —
Molecular Weight 2.016 g/mol
Physical State (25°C, 1 atm) Gas —
Color Colorless —
Odor Odorless —
Boiling Point (1 atm) −252.9 °C
Melting Point −259.2 °C
Critical Temperature (Tc) 33.2 K (−240 °C)
Critical Pressure (Pc) 12.8 bar
Gas Density (25°C, 1 atm) 0.0899 kg/m³
Heat Capacity (Cp, gas, 25°C) 28.8 J/mol·K
Standard Enthalpy of Formation (ΔHf°) 0 kJ/mol
Thermal Conductivity (gas) 0.180 W/m·K
Flammability Limits (air) 4–75 vol %
Autoignition Temperature 585 °C
Diffusivity Very high —
Material Compatibility Risk of hydrogen embrittlement —

18
3.5. Physicochemical Properties of Methanol

Methanol is the main intermediate in the indirect synthesis of DME. In the first reactor,
methanol is produced by reacting carbon monoxide, carbon dioxide, and hydrogen through
exothermic catalytic reactions. The effectiveness of the first reactor directly impacts the
efficiency, energy consumption, and economy of the DME process.

As the methanol synthesis is an equilibrium-limited process, it is strongly dependent upon

temperature and pressure conditions. To achieve an optimum process, the conditions are often
set at high pressure (50-100 bar) and moderate temperatures (200-300°C). As the process is
exothermic, it is important to remove the heat to ensure the stability of the catalyst and to avoid
equilibrium limitations. The yield of methanol is crucial in determining the feed composition
to the next reactor, where methanol is dehydrated to produce DME over an acidic catalyst.

From a physicochemical perspective, low boiling point and a high polarity manage downstream
separation design. The distillation columns must be precisely designed to isolate methanol from
water produced during synthesis. Moreover, methanol is a flammable and toxic liquid, and as
such, it requires special handling, storage, and safety measures. Methanol is also highly
documented, and its thermodynamic properties are essential for a precise calculation of mass
and energy balances involved in the design of DME plants.

Table 5. Physicochemical Properties of Methanol

Property Value Unit

Chemical Formula CH₃OH —
Molecular Weight 32.04 g/mol
Physical State (25°C, 1 atm) Liquid —
Color Colorless —
Odor Mild alcohol odor —
Boiling Point (1 atm) 64.7 °C
Melting Point −97.6 °C
Critical Temperature (Tc) 239.4 °C
Critical Pressure (Pc) 80.9 bar
Liquid Density (25°C) 792 kg/m³
Heat Capacity (Cp, liquid, 25°C) 81 J/mol·K

19
 Standard Enthalpy of Formation (ΔHf°) −201 kJ/mol
Heat of Vaporization 35.3 kJ/mol
Thermal Conductivity (liquid) 0.20 W/m·K
Flash Point 11 °C
Flammability Limits (air) 6–36 vol %
Toxicity Toxic if ingested or inhaled —

3.6. Physicochemical Properties of Dimethyl Ether

The final product in the indirect process is dimethyl ether (DME). DME is produced through
the catalytic dehydration of methanol. In the second reactor stage, two methanol molecules react
with each other through an acidic catalyst such as γ-alumina or zeolite-based catalysts. The two
molecules react to form DME and water. The reaction is mildly exothermic and equilibrium-
limited. The reaction's efficiency has a direct impact on plant productivity. DME has gained
considerable interest from industry due to its clean combustion characteristics. DME has a high
cetane number, low sooting tendency, and lacks carbon-carbon bonds. These characteristics
make DME an environmentally friendly alternative to conventional diesel and LPG. In
integrated CO/CO2-to-DME processes, DME synthesis improves the overall carbon utilization
efficiency.

From a physicochemical point of view, DME would behave similarly to LPG under moderate
pressure, as it can be liquefied under relatively low pressures. Vapor pressure, boiling point,
and other physicochemical properties of DME would significantly affect the design of the
storage tanks, compressors, and separation equipment. As DME is flammable, forming
explosive mixtures in air, safety aspects are to be considered during plant design. Furthermore,
thermodynamic and transport property information of DME would be useful for process
simulation, reactor modeling, heat exchanger calculations, and distillation calculations [5].

DME, being used as an alternative clean energy source as well as an intermediate for other
chemicals, like olefins, through DME-based olefins technology, would be considered as a very
valuable product in sustainable chemical engineering [4].

20
Table [Link] Properties of DME

Property Value Unit

Chemical Formula CH₃OCH₃ —
Molecular Weight 46.07 g/mol
Physical State (25°C, 1 atm) Gas —
Color Colorless —
Odor Faint ether-like odor —
Boiling Point (1 atm) −24.8 °C
Melting Point −141.5 °C
Critical Temperature (Tc) 127 °C
Critical Pressure (Pc) 53.7 bar
Liquid Density (at b.p.) 668 kg/m³
Vapor Pressure (25°C) ~5.1 bar
Heat Capacity (Cp, gas, 25°C) 37 J/mol·K
Standard Enthalpy of Formation (ΔHf°) −184 kJ/mol
Heat of Vaporization 21 kJ/mol
Thermal Conductivity (gas) 0.016 W/m·K
Flash Point −41 °C
Flammability Limits (air) 3.4–27 vol %
Cetane Number 55–60 —
Toxicity Low acute toxicity but inhalation risk —

[Link] of DME

Dimethyl ether (DME) is a promising fuel that is both sustainable and eco-friendly. DME is a
synthetically produced alternative fuel that can be directly used in specially designed
compression ignition diesel engines for various purposes. Under normal atmospheric
conditions, DME is a colourless gas. It is used extensively in the chemical industry and as an
aerosol propellant, solvent, fuel, and refrigerant. DME exhibits comparable calorific value and
similarity of its thermal efficiency to traditional fuels; It is a clean-burning fuel with low
emission and low particulate matter [6].

Most importantly, it has already been used as an ozone-friendly aerosol propellant to replace
ozone-destroying chlorofluorocarbons (CFCs). Therefore, it can also be used as a refrigerant.

21
Also, it is an essential intermediate for producing valuable chemicals such as lower olefins,
dimethyl sulfate, and methyl acetate, which can help to boost the economy of the nation.

DME can be considered as a ‘Second Generation fuel/bio-fuel’ with a slight ethereal odour. It
liquefies under pressure , and these properties of DME are like propane. Moreover, it is
relatively inert, non-corrosive, non-carcinogenic, almost non-toxic, and does not form
peroxides by prolonged exposure to air. Its physio-chemical properties make it a suitable
substitute (or blending agent) for liquefied petroleum gas (LPG, a mixture of propane and
butane). Therefore, DME can be used as a fuel in household cooking gas and industries. In
many test-runs, a heavy-duty truck performed well under real-world driving conditions,
achieving comparable efficiencies to a conventional diesel truck. The results could meet matter
emission standards without using the diesel particulate filter.

[Link] Pathways for Indirect DME Synthesis

[Link]₂ and CO to Methanol & DME
CO2 emissions to the atmosphere increased 15 billion metric tons from 1990 till 2020 because
of the increasing fossil fuel usage in industry, transportation, and electricity generation. After
the 2000s, a decreasing trend in CO2 emissions was observed due to the uses of more
environmentally friendly industrial technologies ; however, CO2 concentration in the
atmosphere continues to increase. As reported by Intergovernmental Panel on Climate Change
(IPCC), the concentration of CO2 in atmosphere is predicted to be nearly 600 pmmv in 2050.

There are several methods for CO2 removal from the atmosphere such as photosynthesis or
biological sequestration by plants and microorganisms and carbon capture and sequestration
(CCS) technology . CCS technology can reduce up to 90% of the carbon dioxide emissions
from power plants; however, CCS is considered to be only a temporary solution. Instead,
efficient utilization of CO2 in chemical industry is considered to be a more desired solution.
Hydrogenation of CO2 to methanol is particularly important considering the potential of
methanol as a feedstock in production of various chemicals such as formaldehyde, dimethyl
ether (DME), ethanol, olefins, and formic acid . CO2 hydrogenation not only reduces the cost
of CO2 disposal, but also provides easier transportation and easier storage through liquid
methanol production. There are two main reactions considered for methanol production through
CO2 hydrogenation (see Eq. (1) and (2)).

22
The hydrogenation of CO2 to methanol and dimethyl ether (DME) faces thermodynamic and
kinetic challenges upon the reduction of pressure from the conventional high pressure of 50-
100 bar to cost-effective atmospheric pressure. Under low pressure, the rate of formation of
methanol decreases significantly with the predominance of the reverse water-gas shift reaction,
resulting in the formation of large amounts of CO. To overcome the thermodynamic limitations
of the reaction, the formation of methanol is combined with the formation of dimethyl ether
(DME) according to the reaction equation 3:

The bifunctional catalyst containing sites for the hydrogenation of CO2 to methanol and solid
acid sites, such as gamma-Al2O3 or H-ZSM-5 zeolites, allows for the formation of dimethyl
ether. Under atmospheric pressure, the conversion of CO2 to methanol is limited to 20% at
277°C with low methanol selectivity. However, the coupling of the formation of dimethyl ether
with the optimization of the CO2:H2 ratio (from 1:3 to 1:9) provides a strategic pathway to
overcome the thermodynamic limitations of the reaction at temperatures ranging from 100 to
400°C [7].

[Link] Reverse Water-Gas Shift (rWGS) Reaction

A major parasitic reaction in this system is the rWGS, where CO2 reacts with H2 to produce
carbon monoxide and water instead of methanol. Unlike the hydrogenation steps, rWGS is
endothermic and becomes dominant at higher temperatures, significantly reducing the
selectivity toward oxygenates (methanol and DME).

Industrial methanol synthesis is traditionally performed at pressures between 50 and 100 bar.
At atmospheric pressure (1 bar), the thermodynamic equilibrium is heavily biased toward the
reactants.

[Link] Effect of Temperature on Selectivity

Thermodynamic analysis reveals a sharp decline in methanol and DME selectivity as
temperature increases under atmospheric conditions. For instance, at 1 bar, methanol selectivity
can reach approximately 48% at 127 °C, but it collapses to a negligible 0.1% by 277 °C.

23
Paradoxically, higher temperatures are often required to achieve industrially relevant reaction
kinetics, creating a "temperature window" dilemma where one must balance rate against
equilibrium yield [8]

24
4. DME Production Methods
In industrial applications, the DME is produced from the syngas by means of two different
configurations:

• Direct DME Production

• Indirect DME Production

4.1. Direct DME Production

Direct DME production process consists of pretreatment, reforming, gas cleaning-recycles,
DME synthesis, and separation and purification of DME sections (Fig 1)

Figure 1. Simplified Block Diagram of Direct Synthesis of DME

[Link] Section
The first step of the production of DME from shale gas is the purification of shale gas. As shown
in Fig.2, shale gas is first sent to acid-gas removal unit and then dehydration process follow the
first step. The nitrogen removal unit is the next step that is membrane separation process. In
this process (Fig.2), two streams are produced that are nitrogen-rich stream to fuel and nitrogen-
reduced stream for later production process. The cooled nitrogen-reduced stream is sent to de-
methanizer and then de-ethanizer to recover natural gas liquids. [9]

25
 Figure 2. General Gas Processing Flow Diagram

Figure 3. Nitrogen Removal Process

4.1.2. Reforming Section

The second section is called reforming. In this unit, gasification process occurs that converts
the methane to syngas (mixture of CO and H2). In general, the range for gasification process is
between 800 °C to 1800 °C. However, type of feedstock and gasifier determines the exact
temperature of process [10].

Dry reforming of methane was selected as a reforming type for direct production method. In
order to produce DME from syngas directly, the ratio of H2: CO should be between 0.7 and 1.
Thus, dry reforming provides the necessary ratio during reformer reactions. Dry reforming is
getting special attention due to environmental problems. Thanks to dry reforming, CO2 can be
converted to valuable syngas by reacting methane. However, the dry reforming of methane is
thermodynamically unfavorable since methane and CO2 are stable molecules. High reaction
temperature is required for formation of syngas. There are many studies and they have showed
increase recently to demonstrate the applicability of dry reforming. As a result, there are some

26
methods for dry reforming such as plasma methods and catalytic methods [11]. In general,
supported noble metals (Pt, Pd, Rh, Ru) and non-noble transition metals (Ni, Co, Fe) are the
two categorized groups of catalysts that are used for dry reforming of methane [12].

4.1.3. DME Synthesis Section

The operating conditions of the direct DME synthesis reactor are typically in the range of 240–
280 °C and 30–70 bar. Since the overall reaction network is exothermic, the thermodynamic
equilibrium is favored at lower temperatures and higher pressures.

In the direct synthesis reactor, DME is produced from synthesis gas through three simultaneous
reactions:

(1) Methanol synthesis reaction

CO + 2H2 ⇌ CH3 OHΔ𝐻 = −91 kJ/mol (4-1)

(2) Methanol dehydration reaction

2CH3 OH ⇌ CH3 OCH3 + H2 OΔ𝐻 = −23 kJ/mol (4-2)

(3) Water–gas shift reaction

CO + H2 O ⇌ CO2 + H2 Δ𝐻 = −41 kJ/mol (4-3)

Overall reaction

3CO + 3H2 ⇌ CH3 OCH3 + CO2 Δ𝐻 = −246 kJ/mol (4-4)

The first reaction corresponds to methanol synthesis, where carbon monoxide reacts with
hydrogen to form methanol. In the second step, methanol dehydration takes place, where two
moles of methanol react to produce one mole of dimethyl ether and one mole of water. The third
reaction is the water–gas shift reaction, which converts carbon monoxide and water into carbon
dioxide and hydrogen, thereby adjusting the H₂/CO ratio within the reactor.

As a result of these simultaneous reactions, the overall conversion of synthesis gas leads to the
formation of dimethyl ether and carbon dioxide as the main products. [9]

27
4.1.4 Separation, Purification and Recycle Sections
The fundamental of this section is to separate CO2 by following reformer, and to send this
recycle CO2 through reformer. There are three locations in system for recycle CO2. The first
comes from acid gas removal unit, the second recycle CO2 is obtained after reforming process
and the third one is the recycle CO2 produced in DME reactor. In system, these three streams
are combined and sent reformer to give reaction with CH4 for syngas production.

Absorption, adsorption, cryogenic and membrane systems are the common technologies for
CO2 separation. The selection of technology depends on the percentage of CO2 in the feed
composition, the conditions of feed such as pressure and temperature, the product purity and
the final destination of the product. All technologies have advantages and disadvantages. The
advantages of absorption are recycling of sorbent and non-dependence on operator. On the other
hand, oxygen causes corrosion on carbon steel facilities and the degradation of the solvent due
to NOx and SOx is the another problem. Recycling of sorbent and high operating flexibility are
the advantages of adsorption. Adsorption technology is not able to deal high concentration of
CO2 and smaller gases can be adsorbed. Another technology is the cryogenic that does not need
absorbent and operates on atmospheric pressure. However, several steps are required to remove
water and this increase the cost of process [13,14].

Membrane systems are the promising candidate on the traditional separation processes.
Especially, it is convenient for streams that contain more than 15% of CO2 and comes from
steel production plant. No moving parts and modularity are needed for 32 the membrane
systems and the system is able to give instantaneous respond to the variations [13,14].

Another issue is the separation of unreacted syngas from reactor yield. Unreacted syngas stream
is divided two streams of to-fuel and recycle to DME reactor. The mixture of DME, methanol
and water is sent to first column of DME distillation and DME is distillated. In second column
of methanol distillation, distillated methanol is sent through to DME reactor as recycle to react.
Fig. 4 shows the direct synthesis route.

28
 Figure 4. Direct Synthesis Route of DME

[Link] DME Production

There are seven main sections to produce DME from shale gas by indirect method (methanol-
to-DME). These steps are pretreatment, reforming, gas cleaning, methanol synthesis,
separation1, DME synthesis and separation2 (Fig. 5).

Figure 5. Simplified Block Diagram of Indirect Route

4.2.1 Pretreatment Section

In this section, the same processes are carried out as the direct production.
4.2.2 Reforming Section
Gasification Reactions
The main composition of syngas consists of CO and H2. The ratio of H2: CO is determined by
reaction temperature, feedstock composition and reforming agent. Steam reforming, partial
oxidation, dry reforming and autothermal reforming are the methods which used in industry for
reforming processes.

29
Partial Oxidation of Methane

Partial oxidation of methane (POX) is an exothermic reaction characterized by a very short

residence time (τ = 3.6–72 ms). The overall reaction between methane and oxygen is given as
follows:

1 ∘
CH4 + O2 ⇌ CO + 2H2 Δ𝐻298K = −36 kJ/mol (4-5)
2

This process typically produces a syngas composition with an H₂/CO ratio close to 2:1, which
is suitable for several downstream applications such as methanol synthesis and Fischer–Tropsch
processes. [9]

The conversion of methane increases with increasing temperature, as illustrated in Figure 6

[11,12].

Figure 6. Effect of Temperature on Equilibrium

Steam Reforming of Methane

Steam reforming of methane (SRM) is an endothermic reaction in which methane reacts with
steam to produce synthesis gas. The overall reaction is expressed as:

∘
CH4 + H2 O ⇌ CO + 3H2 Δ𝐻298K = +206 kJ/mol (4-6)

In addition to the main reforming reaction, the water–gas shift (WGS) reaction occurs
simultaneously:

∘
CO + H2 O ⇌ CO2 + H2 Δ𝐻298K = −41 kJ/mol (4-7)
30
Among the reforming methods, steam reforming provides the highest H₂/CO ratio, typically
approaching 3:1, which makes it particularly suitable for hydrogen-rich applications.

Steam reforming is generally carried out in a multi-tubular fixed-bed reactor, where nickel-
based catalysts are commonly used due to their high activity and economic feasibility.

Temperature plays a critical role in determining the equilibrium composition. Since the main
reforming reaction is endothermic, higher temperatures favor greater methane conversion and
increased hydrogen production [15]. The influence of temperature on methane conversion is
illustrated in Figure 7.

Figure 7. Effect of Temparature On Steam Reforming

Dry Reforming of Methane

Dry reforming of methane (DRM) is an endothermic reaction that typically operates at low
pressure and high temperature. The overall reaction is:

CH4 + CO2 ⇌ 2CO + 2H2 Δ𝐻𝑟 = +247 kJ/mol (4-8)

This reaction produces a syngas with an H₂/CO ratio of approximately 1:1, which is particularly
suitable for processes requiring stoichiometric balance. Similar to steam reforming and partial
oxidation, higher reaction temperatures favor increased conversion of methane and CO₂ to
hydrogen and carbon monoxide. The effect of temperature on equilibrium conversion for dry
reforming (CH₄:CO₂ = 1:1, P = 1 bar) is illustrated in Figure 8 [15].

31
 Figure 8. Effect of Temperature on Dry Reforming

Autothermal Reforming of Methane

Autothermal reforming (ATR) is a hybrid process that combines partial oxidation and steam
reforming to achieve the desired H₂/CO ratio. The key reactions occurring in ATR are:

Partial oxidation

∘
CH4 + 1.5O2 → CO + 2H2 OΔ𝐻298K = −519 kJ/mol (4-9)

Steam reforming

∘
CH4 + H2 O → CO + 3H2 Δ𝐻298K = +206 kJ/mol (4-10)

Water–gas shift

∘
CO + H2 O ⇌ CO2 + H2 Δ𝐻298K = −41 kJ/mol (4-11)

By combining the exothermic partial oxidation with the endothermic steam reforming, ATR
allows better temperature control within the reactor. Additionally, it provides flexibility to
achieve the desired H₂/CO ratio, which can be adjusted according to downstream process
requirements. [9]

32
4.2.4 Methanol Synthesis Section
Methanol is the one of the most important organic chemical because many other chemicals can
be produced from methanol. Methanol is produced generally from syngas by catalytic reaction.
The equilibrium of methanol reaction is favored by low temperatures and high pressure. The
optimum conditions for methanol reactor are 50 100 atm and 200-280 °C (Table 6). During
methanol production, two types of reaction occur in reactor. First reaction is between water and
carbon monoxide and second reaction is between carbon dioxide and hydrogen. As a result of
these two reactions, one mole methanol is generated for one mole of carbon monoxide and two
moles of hydrogen. [9]

Table 7. Syngas to Methanol Process Conditions

4.2.5 Methanol Synthesis Reaction

The following reactions occur within the methanol synthesis reactor:

Water–Gas Shift Reaction

CO (g) + H2 O (g) ⇌ H2 (g) + CO2 (g)Δ𝐻 = −41 kJ/mol (4-12)

Methanol Formation from CO₂

CO2 (g) + 3H2 (g) ⇌ CH3 OH (l) + H2 O (g)Δ𝐻 = −50 kJ/mol (4-13)

Overall Methanol Synthesis

CO (g) + 2H2 (g) ⇌ CH3 OH (l)Δ𝐻 = −91 kJ/mol (4-14)

33
4.2.6 DME Synthesis Section
The dehydration of methanol is an exothermic and equilibrium reaction. The optimum reaction
conditions for reactor are 220-280 °C and 10-20 atm (Table7).

Table 8. Methanol to DME Process Conditions

Methanol dehydration:

CH3OH ↔ CH3-O-CH3 + H2O ΔH = - 23.4 kJ/mol (4-15)

Silica alumina, γ-alumina, the conventional bimolecular catalysts and different kinds of zeolites
can be used for methanol dehydration [16].

Figure 9. Product Time Plot of Products

4.2.7 Separation, Purification and Recycle Sections

Following the syngas production process, CO2 is separated from syngas and CO2 syngas is sent
to methanol reactor to produce methanol from syngas. After methanol reactor, the unreached

34
syngas is separated and divided two streams that are through to methanol reactor as recycle and
to-fuel. Then, a crude methanol is sent through DME reactor. In separation2 section, the mixture
of DME reactor product goes DME distillation column to separate DME from mixture, then
methanol is distillated in methanol column. Distillated methanol is sent DME reactor again.
Indirect synthesis route is shown in Fig. 10. [9]

Figure 10. Indirect Synthesis Route

[Link] Pricing: Definition, Market Trends, Economic Importance and

Future Outlook
Deterring the burning of fossil fuels is crucial to reducing the accumulation of heat-trapping
greenhouse gases in the earth’s atmosphere. A carbon tax could discourage the use of fossil
35
fuels and encourage a shift to less-polluting fuels, thereby limiting the carbon dioxide (CO2)
emissions that are by far the most prevalent greenhouse gas.

According to the World Meteorological Organization, without measures to reduce greenhouse

gases, global temperatures are projected to rise by about 4°C above preindustrial levels by the
end of the century (temperatures have already increased by 1°C), with rising and irreversible
risks of collapsing ice sheets, disruption of ocean circulatory systems, inundation of low-lying
island states, and extreme weather events.

Carbon taxes, levied on coal, oil products, and natural gas in proportion to their carbon content,
can be collected from fuel suppliers. They in turn will pass on the tax in the form of higher
prices for electricity, gasoline, heating oil, and so on, as well as for the products and services
that depend on them. This provides incentives for producers and consumers alike to reduce
energy use and shift to lower-carbon fuels or renewable energy sources through investment or
behavior.

While addressing climate change by reducing greenhouse gases, carbon taxes can also generate
more immediate environmental and health benefits, particularly by reducing deaths that result
from local air pollution. They can also raise significant revenue for governments, revenue they
can use to counteract economic harm caused by higher fuel prices. For example, governments
could use carbon tax revenue to ease the burden of taxation on workers by lowering personal
income and payroll taxes. Carbon tax revenue could also fund productive investments to help
achieve the United Nations Sustainable Development Goals, including reducing hunger,
poverty, inequality, and environmental degradation.

Other policies are less effective than carbon taxes. For example, incentives for renewable power
generation do not promote switching from coal to gas or from these fuels to nuclear, do not
reduce electricity demand, and, not least, do not promote emission reductions beyond the
power-generation sector. [17]

36
 Figure 11. Exchange Traded Carbon Credit Prices by Project Types

Carbon pricing has become one of the most influential economic policy tools used to combat
climate change and guide the transition toward low-carbon industrial systems. According to the
World Bank report State and Trends of Carbon Pricing 2025, carbon pricing mechanisms now
cover a significant and growing share of global greenhouse gas emissions and generate over
100 billion USD in annual public revenue. This reflects a structural shift in global climate
governance, where environmental externalities are increasingly internalized into economic
decision-making processes.

At its core, carbon pricing assigns a monetary value to each ton of carbon dioxide equivalent
(CO₂e) emitted, thereby creating a financial incentive for firms, governments, and consumers
to reduce emissions. This approach transforms climate change mitigation from a purely
regulatory obligation into a market-based economic signal embedded in production,
investment, and trade systems.

[Link] Pricing Methods

The global carbon pricing market consists of three primary mechanisms: carbon taxes,
emissions trading systems (ETS), and voluntary carbon markets. Carbon taxes directly impose
a fixed price on emissions, while ETS systems create a cap-and-trade structure where emission
allowances can be bought and sold in regulated markets. Voluntary carbon markets, on the other
hand, allow companies to offset their emissions through project-based carbon credits.

As of 2025, there are nearly 80 carbon pricing instruments operating worldwide. These systems
now span multiple regions, including the European Union, China, North America, and several

37
emerging economies. The market has evolved from fragmented regional initiatives into a
globally interconnected policy landscape that directly affects industrial competitiveness, trade
flows, and investment decisions. [17]

Figure 12. Share of Global Greenhouse Gas Emissions Covered by an ETS or Carbon Tax

[Link] Market Trends and Expansion Dynamics

One of the most significant trends in recent years has been the rapid expansion of carbon pricing
coverage. The share of global emissions covered by carbon pricing instruments increased from
approximately 24% to 28% within a year, demonstrating the accelerating adoption of these
mechanisms.

In parallel, carbon pricing is expanding beyond traditional sectors such as electricity generation
and heavy industry into transportation, construction, maritime logistics, and aviation. This
broadening of sectoral scope reflects the growing recognition that economy-wide
decarbonization requires comprehensive price signals across all emission-intensive activities.

Another defining trend is the geographical expansion into middle-income economies. Countries
such as Brazil, India, and Türkiye are actively developing carbon pricing frameworks, signaling
a shift from developed-economy leadership toward global policy convergence. This
transformation is closely linked to international trade instruments such as carbon border
adjustment mechanisms, which incentivize exporting countries to adopt domestic carbon
pricing to maintain market access. [17]

38
Figure 13 provides a summary of the global total carbon price since 2015 using a combination
of collected and estimated data. It highlights the influence of fuel taxes on the carbon price
incentive, but also the negative impact of fossil fuel subsidies.

Figure 13. Global Total Carbon Price for the Period

[Link] Price Levels and Market Valuation

Carbon prices vary widely across regions and policy instruments, reflecting differences in
policy ambition, economic structure, and regulatory design. While the effective global average
carbon price remains relatively low, major systems such as the European Union Emissions
Trading System operate at significantly higher price levels, often fluctuating between 70 and
100 EUR per ton.

Despite this progress, current carbon price levels are still below the estimated range required to
meet the Paris Agreement targets, which is typically assessed at around 60–130 USD per ton of
CO₂. This gap indicates that substantial price increases and policy tightening will be necessary
in the coming decade.

In voluntary carbon markets, price differentiation has become increasingly pronounced. High-
quality, nature-based removal credits command premium prices due to their long-term
sequestration potential, while conventional offset credits—particularly from renewable energy

39
projects—have experienced price declines due to oversupply and market saturation. This
divergence highlights the growing importance of credit integrity, verification standards, and
environmental credibility.

[Link] and Strategic Importance of Carbon Pricing

Carbon pricing plays a central role in correcting market failures associated with greenhouse gas
emissions by internalizing the social cost of carbon. By embedding environmental costs into
market prices, carbon pricing aligns private incentives with public climate objectives.

From an industrial perspective, carbon pricing encourages energy efficiency, low-carbon

process innovation, and the deployment of clean technologies such as hydrogen, carbon capture,
and electrification systems. These dynamics are particularly important for energy-intensive
industries such as cement, steel, and chemicals, which face increasing pressure to decarbonize.

In addition to its environmental benefits, carbon pricing has become a major fiscal policy
instrument. Governments use carbon revenues to finance infrastructure, support renewable
energy investments, and mitigate social impacts through targeted subsidies or tax reductions.
This dual role as both an environmental and economic policy tool makes carbon pricing a
cornerstone of sustainable development strategies. [17]

[Link] Pricing Developments in Türkiye

Türkiye is currently in a transition phase toward the implementation of a national carbon pricing
framework. The government has initiated legislative processes to establish an emissions trading
system, including the creation of a national carbon market authority and an emissions permit
allocation system.

The primary driver behind Türkiye’s carbon pricing strategy is its strong trade relationship with
the European Union. The implementation of the Carbon Border Adjustment Mechanism creates
a direct financial incentive for Türkiye to align its carbon pricing policies with European
standards in order to protect export competitiveness in sectors such as steel, aluminum, cement,
and fertilizers.

Furthermore, Türkiye’s rapidly growing industrial base and energy demand—combined with
its reliance on fossil fuels—make carbon pricing a critical policy tool for managing future
emissions growth. The adoption of carbon pricing is expected to stimulate investments in
renewable energy, improve industrial energy efficiency, and accelerate the country’s long-term
decarbonization pathway.

40
[Link] Outlook
Looking ahead, the carbon pricing market is expected to undergo substantial transformation in
both scale and price levels. As countries strengthen their climate commitments and tighten
emissions caps, carbon prices are projected to rise significantly, potentially exceeding 100 USD
per ton by 2030 in many jurisdictions.

Another key trend will be the integration and linkage of national carbon markets, creating larger
and more liquid trading systems. This integration will improve market efficiency, reduce price
volatility, and facilitate cross-border carbon trade.

In parallel, corporations are increasingly adopting internal carbon pricing mechanisms as part
of their ESG and sustainability strategies. This indicates that carbon pricing is no longer solely
a government policy instrument but is becoming embedded within corporate financial planning
and risk management frameworks.

Carbon pricing has evolved into a fundamental pillar of the global low-carbon transition,
influencing energy systems, industrial production, international trade, and public finance.
Although the market has grown rapidly in recent years, current price levels remain insufficient
to achieve global climate targets, necessitating stronger policy ambition and higher carbon
prices.

For Türkiye and other emerging economies, carbon pricing represents both a regulatory
challenge and an opportunity to modernize industrial systems, enhance competitiveness, and
attract green investment. In the coming decades, carbon pricing is expected to become
increasingly integrated into the global economic system, shaping the trajectory of sustainable
development and climate policy worldwide.

41
6. Method of Calculation
6.1. Mass Balances
To estimate the mass requirements of the dimethyl ether production system, given equations
and assumptions is used.

• Every separation system except the dimethyl ether separator has a yield of %95.
• Dimethyl ether separator has a yield of %99.
• Input ratio to biforming reactor is 1:0.4:0.8 (CH4:CO:H2O)
• Conversion in biforming reactor is %77 CO2 and %82.5 CH4
• Conversion in methanol reactor is %30
• Conversion in Dimethyl Ether reactor is %16 and feed should be at least %95 purity
methanol

Below you can see the mass balance equation used for this system.

𝑖𝑛𝑝𝑢𝑡 − 𝑜𝑢𝑡𝑝𝑢𝑡 + 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 − 𝑐𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 = 𝑎𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛

Since we will work in steady state conditions there will be no accumulation. So the equation
becomes;

𝑖𝑛𝑝𝑢𝑡 + 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 = 𝑜𝑢𝑡𝑝𝑢𝑡 + 𝑐𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛

Also since there is no chemical reaction in the separation systems there shouldn’t be generation
nor consumption. So for separation units equations derives to;

𝑖𝑛𝑝𝑢𝑡 = 𝑜𝑢𝑡𝑝𝑢𝑡

42
6.2. Energy Balances
To calculate the energy requirement of an equipment, the enthalpies of the inlet and outlet
streams are calculated.

Table 9. Components,mole fractions and Enthalpys

Enthalpy of
Components Mole Fractions Formation(j/mol)
CH4 0.048 -74850
CO2 0.025 -393510
CO 0.308 -110540
H2 0.617 0
H2O 0.003 -228770

Table 10. Components and their Cp coefficients

Components Mole Fractions A B C D

CH4 0.048 19.251 5.21E-02 1.20E-05 -1.13E-08
CO2 0.025 19.795 7.34E-02 -5.60E-05 1.72E-08
CO 0.308 30.869 -1.29E-02 2.79E-05 -1.27E-08
H2 0.617 27.143 9.27E-03 -1.38E-05 7.65E-09
H2O 0.003 32.243 1.92E-03 1.06E-05 -3.60E-09

For the enthalpy calculation of streams equation 6.1 will be used.

𝑇
𝐻𝑖 = ∆𝐻𝐹 + ∫ 𝐴 + (𝐵 × 𝑇) + (𝐶 × 𝑇 2 ) + (𝐷 × 𝑇 3 ) (6.1)
𝑇0

43
7. Selected Process Description
Block Diagram of the process is shown in Figure 14

Figure 14. Block Diagram of our Process

[Link] Section
Desulfurization was added to the natural gas/methane feed at the beginning because sulfur
compounds poison reforming and methanol catalysts, reducing activity. This step is critical to
ensure long catalyst life and efficient operation.

[Link] Section
Bi-reforming is the first major reaction step in our DME production process. In this unit,
methane reacts simultaneously with steam (H₂O) and carbon dioxide (CO₂) to produce synthesis
gas (syngas). This method combines steam reforming and dry reforming in a single reactor to
obtain a syngas composition suitable for downstream methanol and DME synthesis.

The main reactions occurring in the bi-reforming reactor are:

44
Steam Reforming (endothermic):
CH₄ + H₂O ⇌ CO + 3H₂

Dry Reforming (endothermic):

CH₄ + CO₂ ⇌ 2CO + 2H₂

In addition, the water–gas shift reaction may occur and influence the final gas composition:

CO + H₂O ⇌ CO₂ + H₂

Both reforming reactions are strongly endothermic, meaning they require high temperatures
and continuous heat input. Therefore, the reactor typically operates at high temperatures
between 700–900°C. In our process design, the bi-reforming reactor operates at approximately
800°C and 1 bar. A nickel-based catalyst (Ni/Al₂O₃) is used because it provides high activity
for methane reforming reactions and is economically feasible for large-scale applications.

The main purpose of bi-reforming is to produce syngas with a controlled H₂/CO ratio suitable
for DME production. Our H₂/CO ratio is 2 because in DME reactions, 2 hydrogen are required
per unit of CO. Using only steam reforming would result in excess hydrogen, while using only
dry reforming would produce too much carbon monoxide. By combining both reactions, the
H₂/CO ratio can be adjusted more effectively for the methanol synthesis step.

Another important advantage of bi-reforming is the direct utilization of CO₂ as a reactant. This
contributes to carbon recycling and reduces the overall environmental impact of the process.
Additionally, the presence of steam helps suppress carbon deposition (coking) on the catalyst
surface, improving catalyst stability and operational reliability.

In summary, the bi-reforming unit provides the required syngas composition for downstream
methanol synthesis while enabling CO₂ utilization, process flexibility, and improved carbon
efficiency. It is therefore a key step in the overall CO/CO₂-to-DME production process.

[Link]-Liquid Seperation
In the third step of the process, a knock-out drum is used to perform gas–liquid separation
before the gas stream enters the compressor. This unit is installed to protect the compressor and
ensure stable operation of the downstream equipment.

After the previous process steps, the gas stream may contain condensed liquid droplets such as
water, methanol, or other heavy components. If these liquids enter the compressor, they can
cause mechanical damage, corrosion, efficiency loss, and even equipment failure. Compressors

45
are designed to handle gas-phase streams, and the presence of liquid can lead to serious
operational problems.

This step is critical for operational safety, equipment protection, and process reliability. By
removing entrained liquids before compression, the knock-out drum prevents potential damage,
reduces maintenance costs, and ensures continuous and efficient plant operation.

[Link] Synthesis Section

In the methanol synthesis section, the purified syngas—primarily composed of hydrogen (H₂),
carbon monoxide (CO), and carbon dioxide (CO₂)—is fed into a fixed-bed reactor containing a
Cu/ZnO/Al₂O₃ catalyst. The reactor operates at elevated pressures of 50–100 bar and
temperatures between 200–300 °C to achieve optimal conversion. In our methanol synthesis
reactor, the conditions were set at 250 °C and 75 bar, with Cu/ZnO/Al₂O₃ as the catalyst.

The main chemical reactions occurring in the reactor are:

1. CO hydrogenation to methanol:

𝐶𝑂 + 2𝐻2 → 𝐶𝐻3 𝑂𝐻 (7.1)

2. CO₂ hydrogenation to methanol:

𝐶𝑂2 + 3𝐻2 → 𝐶𝐻3 𝑂𝐻 + 𝐻2 𝑂 (7.2)

3. Reverse water-gas shift reaction (side reaction):

𝐶𝑂2 + 𝐻2 → 𝐶𝑂 + 𝐻2 𝑂 (7.3)

The first two reactions produce methanol, while the third reaction converts a portion of CO₂
into CO and water. Since the reactions are exothermic, efficient heat removal through reactor
cooling is critical to maintain catalyst activity and prevent hotspots. The methanol product exits
the reactor along with unreacted syngas. This unreacted syngas is separated downstream and
partially recycled to the methanol reactor, enhancing overall process efficiency.

Water produced during methanol synthesis must be minimized before feeding the methanol
stream into the DME reactor, as water can deactivate the acid catalyst used in DME formation.
Therefore, separation steps following methanol synthesis, such as condensation and phase
separation, are essential to ensure the methanol feed meets the DME reactor specification

46
[Link]-Liquid Seperation
The effluent stream leaving the methanol synthesis reactor consists of crude methanol, water,
and unreacted syngas (H₂, CO, and CO₂). Since methanol synthesis reactions are equilibrium-
limited, a significant fraction of syngas remains unconverted. Therefore, an efficient separation
system is required to recover and recycle the valuable reactants.

The separated gas phase, rich in unreacted H₂, CO, and CO₂, is compressed and recycled back
to the methanol reactor. This recycle stream increases overall carbon conversion efficiency and
reduces fresh feed consumption. A small purge stream may be required to prevent the
accumulation of inert components in the recycle loop.

The liquid phase, known as crude methanol, contains mainly methanol and water and is sent to
the next separation step.

[Link] Purification Section

n this step, crude methanol is purified to meet the specifications required for the DME synthesis
reactor. Since water negatively affects the acid catalyst used in DME production, its
concentration must be minimized.

Methanol and water are separated typically by distillation due to their different boiling points
(methanol: 64.7 °C; water: 100 °C at 1 atm). The separation column produces:

• A high-purity methanol stream from the top of the column, which is sent to the DME
reactor.

• A water-rich bottom stream.

The purified methanol is now suitable for the DME synthesis reaction:

2𝐶𝐻3 𝑂𝐻 → 𝐶𝐻3 𝑂𝐶𝐻3 + 𝐻2 𝑂 (7.4)

The separated water stream is not discarded. Instead, it is recycled to the bi-reforming section,
where it serves as a steam source for reforming reactions. This internal water recycle improves
overall process integration, enhances thermal efficiency, and reduces fresh water consumption.

By integrating water recovery into the reforming section, the process achieves better resource
utilization and improved sustainability performance.

47
[Link] Synthesis Section
In the DME synthesis section, high-purity methanol from the previous separation step is fed
into reactor under elevated temperature (250–300 °C) and moderate pressure (20–50 bar). Our
Amberlyst 35 catalyst degrades above 150 °C. Therefore, we chose 120 °C and 9 bar. This
reactor operates in the liquid phase, unlike the other reactors.

Dimethyl ether (DME) is produced via a dehydration reaction of methanol according to the
following main reaction:

2𝐶𝐻3 𝑂𝐻 → 𝐶𝐻3 𝑂𝐶𝐻3 + 𝐻2 𝑂 (7.5)

This reaction is endothermic and equilibrium-limited, requiring precise control of temperature,

pressure, and residence time to maximize DME yield. The water generated during the reaction
is continuously removed to drive the equilibrium toward DME formation.

By integrating methanol recycling and water management, the DME synthesis section achieves
high selectivity and yield while maintaining catalyst stability and process efficiency. This step
effectively converts the methanol produced from syngas into a value-added fuel, completing
the syngas-to-DME process chain.

[Link] Purification Section

The effluent from the DME synthesis reactor contains dimethyl ether (DME), unreacted
methanol, and water. To obtain high-purity DME suitable as a final product, this mixture
undergoes a purification step.

Due to the significant difference in boiling points (DME: −24.8 °C, methanol: 64.7 °C, water:
100 °C at 1 atm), DME is separated as the top product in vapor phase, while the heavier
methanol–water mixture collects at the bottom of the column. The purified DME, free from
methanol and water, is then stored, and prepared for downstream use or distribution as a
chemical feedstock or fuel.

This purification step ensures that the final DME product meets quality specifications, while
integration with methanol and water recycling enhances process sustainability and reduces
operating costs.

48
[Link]-Liquid Seperation
After the DME purification section, the product stream contains methanol, water, and light
gases. This stream undergoes a gas–liquid separation step to efficiently manage the liquid
components and enable process recycling.

The mixture enters a gas–liquid separator, Methanol, being less dense and more volatile than
water, rises to the top of the separator and is directed back to the DME synthesis reactor as a
recycle stream. This recycling increases methanol conversion efficiency and reduces fresh
methanol consumption.

The water-rich phase collects at the bottom of the separator and is sent back to the bi-reforming
section. Here, it acts as a steam source for reforming reactions, supporting process integration
and improving thermal efficiency.

By implementing this gas–liquid separation step, the process ensures optimal feed composition
for the DME reactor and maintains effective utilization of both methanol and water streams
throughout the plant.

49
[Link] Flow Diagram and Mass Balance
Below this page is the process flow diagram of indirect synthesis of DME, a stream summary
table and an equipment summary table.

50
Figure 15. Process Flow Diagram of our Process 51
Stream Temperature(C) Pressure(bar) Molar Flowrates (kmol/h) % Chemical Phase Mass Enthalpy(kj/kg) Molar Enthalpy(kj/kmol)
1 200 200 100 %99 CH4, %1 H2S Vapor -4208.896241 -67522.31226
2 145 80 100 %99 CH4, %1 H2S Vapor -4357.257819 -69902.44144
3 140 80 5 %100 H2S Vapor -487.3356311 -16609.3145
4 145 80 95 %100 CH4 Vapor -4357.257819 -69902.44144
5 100 1 38 %100 CO2 Vapor -8874.914096 -390583.1944
6 130 1 133 %73 CO2,%26 CH4 Vapor -7666.510248 -230735.5009
Table 11. Stream Summary Table

7 800 1 209 %33 CH4,%37 CO2, %30 H2O Vapor -7143.378783 -37271.13733
8 750 1 405.75 %6 CH4,%8.7 CO2,%68 CO,%9.8 H2,%7.2 H2O Vapor -2799.839292 -33805.02627
9 95 1 405.75 %6 CH4,%8.7 CO2,%68 CO,%9.8 H2,%7.2 H2O Vapor-Liquid -4542.339545 -54843.8291
10 95 1 349.144 %6.5 CH4,%9.4 CO2,%74 CO,%11 H2 Vapor -3866.591157 -45525.30874
12 95 1 349.144 %6.5 CH4,%9.4 CO2,%74 CO,%11 H2 Vapor -3866.591157 -45525.30874
13 375.1 5 349.144 %6.5 CH4,%9.4 CO2,%74 CO,%11 H2 Vapor -3135.851903 -36921.57258
14 150 5 349.144 %6.5 CH4,%9.4 CO2,%74 CO,%11 H2 Vapor -3726.093256 -43871.08411
15 583 40 349.144 %6.5 CH4,%9.4 CO2,%74 CO,%11 H2 Vapor -2568.125204 -30237.14897
16 200 40 349.144 %6.5 CH4,%9.4 CO2,%74 CO,%11 H2 Vapor -3597.072287 -42351.98908
18 321 75 349.144 %6.5 CH4,%9.4 CO2,%74 CO,%11 H2 Vapor -3279.041177 -38607.48549
19 250 75 349.144 %6.5 CH4,%9.4 CO2,%74 CO,%11 H2 Vapor -3466.876649 -40819.06346
20 270 75 279.324 %6.5 CH4,%6.5 CO2,%51 CO,%7 H2,%1.5 H2O,%27 CH3OH Vapor -4262.894417 -62814.58925
21 215.7 40 279.324 %6.5 CH4,%6.5 CO2,%51 CO,%7 H2,%1.5 H2O,%27 CH3OH Vapor -4391.73106 -64713.02258
22 200 40 263.435 %8.9 CH4,%9 CO2,%70 CO,%9.6 H2,%0.46 H2O,%1.9 CH3OH Vapor -3733.750485 -46077.85567
23 220 40 47.775 %80 CH3OH,%20H2O Vapor -7365.545853 -204428.2192
24 141 9 47.775 %80 CH3OH,%20H2O Vapor-Liquid -7505.936602 -208324.7167
25 135 9 15.53 %17 CH3OH,%83 H2O, Liquid -13927.69631 -271757.687
26 141 9 32.237 %99 CH3OH,%1H2O Vapor -6187.736591 -196302.9998
27 130 9 32.237 %99 CH3OH,%1H2O Liquid -7159.186127 -227121.7742
28 130 9 32.236 %83 CH3OH,%6H2O,%11 DME Liquid -6681.047878 -211952.9998
29 130 9 2.793 %7 CH3OH,%0.5H2O,%93 DME Liquid -4031.955637 -179045.8709
30 125 9 29.443 %93 CH3OH,%6.4H2O,%0.1 DME Vapor -7611.933908 -232327.38

52
31 120 9 25.077 %99 CH3OH,%0.4H2O,%0.1 DME Vapor -7122.582651 -227681.1043
32 125 9 4.36 %43 CH3OH,%57H2O, Liquid -11834.26129 -263004.4638
Table 12. Equipment Summary Table

Equipment Equipment Code Function

Compressor C-101 Pressurization
Absorption T-101 Separation
Heat exchanger E-101 Cooler
Reactor T-102 Biforming
Heat exchanger E-102 Heater
Knock out drum D-101 Separation
Compressor C-102 Pressurization
Heat exchanger E-103 Heater
Compressor C-103 Pressurization
Heat exchanger E-104 Heater
Compressor C-104 Pressurization
Heat exchanger E-105 Cooler
Reactor T-103 Methanol synthesis
Turbin V-101 Pressure reduction
Distillation T-104 Separation
Turbin V-102 Pressure reduction
Distillation T-105 Separation
Heat exchanger E-106 Cooler
Reactor T-106 DME synthesis
Distillation T-107 Separation
Distillation T-108 Separation

53
Technical and economic assessment follows a step by step scaling approach starting with
100kmol of CH4 basis. For a single cycle of process, since desulfurization separator works
with a yield of %95 percent, base methane decreases to 95kmols.

100𝑘𝑚𝑜𝑙 ∗ 0.95 = 95𝑘𝑚𝑜𝑙 (8.1)

For every 95kmols of methane that enters the biforming reactor we need 38kmols of CO2 and
76kmols of water. Some of those requirements are coming from the recycle systems through
the process.
Since conversion for CH4 is %82.5 and for CO2 %77,
95𝑘𝑚𝑜𝑙 ∗ 0.825 = 78.375𝑘𝑚𝑜𝑙 𝐶𝐻4

38𝑘𝑚𝑜𝑙 ∗ 0.77 = 29.26𝑘𝑚𝑜𝑙 𝐶𝑂2

Total Carbon Monoxide is:

78.375𝑘𝑚𝑜𝑙 + 29.26𝑘𝑚𝑜𝑙 = 107.635 𝑘𝑚𝑜𝑙

For every CO, 2 hydrogen occurs,
107.635 ∗ 2 = 215.27𝑘𝑚𝑜𝑙
Here you can see the outlet of the biforming reactor,
Table 13. Component Values in Outlet of Biforming Reactor

Component Kmol value

CH4 16.625
CO2 8.74
H2O 17.48
CO 107.635
H2 215.27

After the reactor outlet, water is separated with a knock out drum with %95 yield.

17.48𝑘𝑚𝑜𝑙 ∗ 0.95 = 16.606 𝑘𝑚𝑜𝑙 𝑤𝑎𝑡𝑒𝑟 𝑠𝑒𝑝𝑒𝑟𝑎𝑡𝑒𝑑

17.48 ∗ 0.05 = 0.874 𝑘𝑚𝑜𝑙 𝑤𝑎𝑡𝑒𝑟 𝑠𝑡𝑖𝑙𝑙 𝑖𝑛 𝑠𝑦𝑠𝑡𝑒𝑚

Then the streams enter to the methanol reactor after pressurized. Conversion of CO in
methanol reaector is %30.

107.635 ∗ 0.30 = 32.29𝑘𝑚𝑜𝑙 𝐶𝑂 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑

8.74 ∗ 0.30 = 2.62 𝑘𝑚𝑜𝑙 𝐷𝑖𝑜𝑥𝑖𝑑𝑒 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑

32.29 + 2.62 = 34.91 𝑘𝑚𝑜𝑙𝑠 𝑜𝑓 𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝑓𝑜𝑟𝑚𝑒𝑑

Also 2.62 kmols of water will be formed from CO2 reaction.

32.29 ∗ 2 + 2.62 ∗ 3 = 72.44 𝑘𝑚𝑜𝑙𝑠 𝑜𝑓 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑

54
Below you can see the outlet stream of the methanol reactor.

Table 14. Component Values in Outlet of Methanol Reactor

Component Kmol value

H2 142.83
CO 75.345
CH3OH 34.91
CH4 16.625
CO2 6.12
H2O 3.494

After the methanol reactor, methanol and reactor will be separated with a flash distillation
with a yield of %95.

34.91 ∗ 0.95 = 33.165

Then another flash vaporization unit is used to increase the methanol purity.

33.165 ∗ 0.95 = 31.507

With this step, we occurred the target %95 methanol for the dimethyl ether reactor.
We can feed this methanol to the dimethyl ether reactor with %16 conversion:

31.507 ∗ 0.16 = 5.041𝑘𝑚𝑜𝑙 𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑

31.507 − 5.041 = 26.466 𝑘𝑚𝑜𝑙 𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝑠𝑡𝑖𝑙𝑙 𝑖𝑛 𝑡ℎ𝑒 𝑠𝑡𝑟𝑒𝑎𝑚

5.041
= 2.520 𝑘𝑚𝑜𝑙𝑠 𝐷𝑀𝐸 𝑓𝑜𝑟𝑚𝑒𝑑
2
To increase the purity of DME to global standards, we should use a absorber unit with %99
efficiency.

2.520 ∗ 0.99 = 2.495𝑘𝑚𝑜𝑙𝑠 𝐷𝑀𝐸

26.466 ∗ 0.01 = 0.265 𝑘𝑚𝑜𝑙𝑠 𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙

And for the steady state calculations, for every 100kmols of methane and 48kmols CO2 we
put to the reactor, we have to buy 42kmol of water. Rest of the water will be recycled from the
system. With this conditions, 46.55 kmols of DME can be produced every hour. Since we aim
to produce 35000tons every year;
35,000,000𝑘𝑔 4.375𝑘𝑔
= 𝐻𝑜𝑢𝑟𝑙𝑦 𝐷𝑀𝐸 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑖𝑜𝑛
8000ℎ ℎ

55
 4.375𝑘𝑔
ℎ 94.96𝑘𝑚𝑜𝑙
= 𝐻𝑜𝑢𝑟𝑙𝑦 𝑀𝑜𝑙𝑎𝑟 𝐹𝑙𝑜𝑤
46.07 ℎ
𝑘𝑚𝑜𝑙
94.96
= 2.04 𝑈𝑝𝑠𝑐𝑎𝑙𝑒 𝐹𝑎𝑐𝑡𝑜𝑟
46.55
Table [Link] Table for Capacity

Component Factor Hourly Molar Hourly Mass Annual Quantity

Flow kmol/h Flow kg/h ton/yr
Methane 2.04 204 3.264 26.112
Carbon Dioxide 2.04 77.52 3411 27.287
Water 2.04 85.68 1542.2 12.337
DME Produce 2.04 94.96 4375 35000

56
9. Market Survey
9.1. Demand and Supply in Turkey, Europe and World

Global Dimethyl Ether market is characterized by a steady growth trajectory, driven by its
versatility as a clean burning fuel. Market is projected to grow at a CAGR (compound annual
growth rate) of %6.15 between 2021 and 2031.

Global demand is expected to reach 8.99 million tons by 2026 and 12.12 million tons by 2031.
Under aggressive decarbonization scenarios, global demand could surge to 37 million tons by
2050. In this scenario, role of the dimethyl ether could increase and potentially be the next fuel
for the century.

Figure 16. Projected Global DME Demand for 2050

Increasing regulations against fossil fuels and a global push for decarbonization may cause
demand to exceed current projections, particularly in strictly regulated nations. Almost %20 of
the current company’s has a carbon emission regulation by now. And we can assume that this
ratio will be much higher in a few years.

Based on market projections, the demand for dimethyl ether is expected to continue growing.
This is because of its expanding application as an additive for blending LPG as well as an
alternative diesel fuel. Industry reports, as shown in Fig 3, indicate that the global demand for
dimethyl ether is expected to grow to 12.12 million tons by 2031. Additionally, it may grow to
37 million tons by 2050.

57
 Figure 17. Dimethyl Ether Market Size

2031 Total 12.12 Ton Usage

0,8484; 7%
0,4848; 4%

0,7272; 6%

10,0596; 83%

Asia-Pacific Europe North America Others

Figure 18. Total DME Usage in 2031

58
 2050 Total 37.16 M. Ton Usage
2,60; 7%

1,49; 4%

2,23; 6%

30,84; 83%

Asia-Pacific Europe North America Others

Figure 19. Total DME Usage in 2050

2050 Total 37.16 M. Ton Usage With

Europe Increased Percentage

2,60; 7%
2,23; 6%

4,46; 12%

27,87; 75%

Asia-Pacific Europe North America Others

Figure 20. Total DME Usage in 2050 With Increased Europe Share

59
9.2. Production in Turkey, Europe and World

Dimethyl ether (DME) production is currently concentrated in Asia-Pacific, particularly in

China, which accounts for the majority of global capacity. China primarily produces DME from
coal-based synthesis gas (syngas), benefiting from domestic coal availability and established
gasification technologies. This has allowed the region to develop large-scale DME facilities,
mainly for blending with LPG and as an alternative household fuel.

Outside Asia, production capacity remains limited. Europe and North America have relatively
small-scale facilities, mostly focused on specialty chemical applications rather than large-scale
fuel substitution. However, with the acceleration of decarbonization policies and renewable
hydrogen development, Europe is expected to increase its production capacity in the medium
to long term.

Globally, DME is produced through two main routes:

• Indirect synthesis (via methanol dehydration)

• Direct synthesis from syngas (CO/CO₂ + H₂)

Direct synthesis routes are increasingly preferred due to higher process efficiency and reduced
equipment requirements.

Recent declines in solar and wind energy cost trends demonstrate a long-term cost reduction
for renewable electricity sources. This has substantial implications for hydrogen production
routes. Currently, steam methane reforming is still dominant as a hydrogen production route,
which is economically favorable. However, as renewable electricity sources become more cost-
effective, green hydrogen production via water electrolysis is expected to become more
economically viable.

Hydrogen cost is considered to be one of the largest operation cost components for a CO/CO₂
to DME production system. Therefore, a switch to a renewable-based hydrogen production
route would have substantial positive effects on the environmental performance of this
production system, while also reducing long-term CO₂ taxation risks. Although green hydrogen
production is still more expensive compared to reforming-based hydrogen production, cost
reduction trends for green hydrogen production could also render a fully renewable-based DME
production system economically viable.

60
The global transition toward a low-carbon economy has positioned Dimethyl Ether (DME) as
a critical vector for decarbonizing hard-to-abate sectors. Historically categorized under the HS
Code 2909.19 (Other acyclic ethers and their derivatives), DME is transitioning from a
specialized chemical feedstock to a strategic energy commodity. Recent technological shifts
and the declining cost of renewable electricity—specifically solar and wind—have
fundamentally altered the long-term cost reduction trends for renewable electricity sources.
This feasibility study evaluates the integration of green hydrogen and carbon capture
technologies to produce sustainable DME, mitigating long-term CO₂ taxation risks while
addressing energy security.

For the technical standards and quality protocols for the dimethyl ether, there is not a strict one
for specifically dimethyl ether. But for any product traded under HS Code 2909.19 to be used
as a fuel, it must adhere to international quality standards.

The most critical reference is ISO 16861:2015, which specifies the requirements and test
methods for dimethyl ether used as a fuel. Theoretically, dimethyl ethers physical properties
(vapor pressure and density) are similar to LPG, but it is a solvent. This requires a transition in
sealin materials (using EPDM or specialized elastomers instead of standard Buna-N or Viton)
to prevent degradation in the supply chain.

Turkey’s strategic position in the dimethyl ether trade routes is both importer and exporter. In
most of the trade databases, dimethyl ether is below the HS2909.19 code. Since this code
includes many of the most used ethers, with this code we couldn’t specify the dimethyl ether
use or need just from the databases. But for different views, Turkey’s imports for this code in
2024 is reached almost 98 million dollars. Which is much higher than Turkey’s export value
which is about 10 million dollars. Below you can see the top exporters of dimethyl ether in the
year 2024.

61
 Figure 21. Top Exporters of HS2909.19

9.3. Imports and Exports

Dimethyl ether (DME) is classified under HS Code 2909.19, which includes “other acyclic
ethers and their derivatives.” This classification makes it difficult to isolate DME-specific trade
data, as the code also covers other ether products. Nevertheless, trade data under this category
provides an important indication of Türkiye’s dependency on ether-based chemical imports and
the potential market opportunity for domestic DME production.

Türkiye has shown a consistent increase in imports under HS 2909.19 over the past years.
Import value increased significantly after 2021, reaching approximately 299 million USD in
2024. This represents a substantial growth compared to 97 million USD in 2019.

In terms of volume, imports reached approximately 304,255 tons in 2024. The simultaneous
increase in both value and volume indicates not only price effects but also a genuine rise in
domestic demand for ether-based products.

The upward import trend suggests growing industrial consumption, particularly in applications
such as aerosol propellants, polyurethane foam production, and fuel-related uses.

Exports under HS 2909.19 remain relatively limited compared to imports. In 2024, export value
reached approximately 9.7 million USD, while export volume was around 8,513 tons.

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 Türkiye Import Export
$350.000.000,00 350000
$300.000.000,00 300000
$250.000.000,00 250000

Ton/year
$/year

$200.000.000,00 200000
$150.000.000,00 150000
$100.000.000,00 100000
$50.000.000,00 50000
$- 0
2019 2020 2021 2022 2023 2024
Years

import $ export $ import ton export ton

Figure 22. Türkiye Import and Export Values for DME

Although there is a gradual increase in export activity over the years, the scale remains small
compared to import volumes. Export routes are mainly directed toward neighboring Balkan
countries, indicating regional trade potential but limited domestic production capacity.

Türkiye is a clear net importer under HS Code 2909.19. In 2024, the net trade balance in volume
terms was approximately –295,742 tons. Moreover, the trade deficit has widened steadily since
2019.

This widening deficit indicates structural import dependency. Since domestic dedicated DME
production facilities are currently absent, the market relies heavily on foreign supply.

Türkiye Net Trade Balance From

Hs290919
k

-100k
Net Trade

-200k -124k -139k -131k

-186k
-300k -239k
-296k
-400k
2019 2020 2021 2022 2023 2024
Years

net trade ton

Figure 23. Türkiye Net Trade Balance From HS2909.19

63
9.4. Availability of Raw Materials
The availability of raw materials is a key determinant in the feasibility of the proposed dimethyl
ether (DME) production facility. In this project, syngas is generated via bi-reforming, which
combines steam reforming (SR) and dry reforming (DR) reactions within a single reactor.
Therefore, the primary feedstocks are methane (CH₄), carbon dioxide (CO₂), and steam (H₂O).

Methane is the main carbon and hydrogen source in the bi-reforming process. Türkiye has well-
established natural gas import infrastructure and distribution networks, ensuring reliable
methane supply. Methane availability is therefore not considered a limiting factor for the
proposed 35,000 ton/year DME production capacity.

Unlike conventional DME production routes that rely solely on steam reforming, bi-reforming
intentionally utilizes CO₂ as a reactant in the reforming stage. In this configuration, CO₂ is not
treated as waste but as a chemical feedstock. Its utilization improves the H₂/CO ratio of the
produced syngas and enhances overall carbon efficiency. Thus, CO₂ availability in Türkiye
supports the technical feasibility of the bi-reforming route.

9.5. Price in Turkey and In World Market

Price dynamics play a critical role in determining the commercial viability of dimethyl ether
(DME) production. The market price of DME is influenced by feedstock costs, hydrogen
production route, energy prices, and regulatory factors such as carbon taxation. Globally, DME
prices are closely linked to methanol and LPG price trends, as DME is used both as a chemical
intermediate and as a fuel alternative. In recent years, price volatility has been primarily driven
by:

• Natural gas price fluctuations

• Crude oil price variations

• Regional supply-demand imbalances

Since a large portion of global DME production is based on fossil-derived syngas, natural gas
and coal prices directly impact production cost structures.

In Asia-Pacific, where coal-based production dominates, DME prices are relatively

competitive. In contrast, European production costs are generally higher due to stricter
environmental regulations and energy costs.

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Hydrogen cost is one of the most significant operating cost components in DME production.

In conventional systems relying on steam methane reforming (SMR), hydrogen production cost
remains relatively low. However, carbon emissions associated with SMR may increase overall
cost under carbon pricing mechanisms.

In contrast, green hydrogen production via electrolysis is currently more expensive.

Nevertheless, declining renewable electricity costs suggest that hydrogen production costs are
expected to decrease in the medium to long term.

Since the proposed system utilizes bi-reforming for syngas production, hydrogen is generated
internally, reducing dependency on external hydrogen markets and improving cost stability.

Figure 24. Dimethyl Ether Market Share

9.6. Future Expectations

Global DME demand is projected to grow steadily under baseline scenarios, reaching
approximately 12.12 million tons by 2031 and potentially 37 million tons by 2050 under
aggressive decarbonization pathways.

Demand growth will be primarily driven by:

• LPG blending applications

• Diesel substitution in heavy transport

• Industrial fuel switching

• Stricter carbon emission regulations

In particular, countries implementing strong carbon taxation mechanisms may accelerate the
adoption of low-carbon fuels such as DME.

65
For Türkiye, proportional demand estimation suggests increasing domestic need in parallel with
global trends. Additionally, Türkiye’s strategic position between Europe and Asia may allow
regional supply opportunities.

Figure 25. Potential for Corporate Sourcing of Renewable Electricity

The data provided in figure 26, indicating the utilization of renewable energy in different
industrial sectors, reveals that the materials and heavy industry sectors have a significant share
in the total energy demand. In this regard, the alternative fuel that can be considered is DME,
considering its clean burning characteristics and the availability of LPG infrastructure, which
can help in reducing carbon emissions in the energy-intensive industry sectors. Furthermore,
the increasing share of renewable energy in the energy mix for power generation will support
the production of DME by using hydrogen, thereby increasing the sustainability index of the
process.

Figure 26. Inter Sectoral Comparison of Renewable Electricity Sourcing

66
However, it is imperative to note that, as earlier stated, projections based on compound annual
growth rate are assumption-based. As such, they are highly likely to change depending on
different regulatory, technological, and economic scenarios. As earlier mentioned, the increase
in regulations against fossil fuels, coupled with the global push for decarbonization, may mean
that the demand for dimethyl ether will exceed projections, especially in countries that are very
strict about regulations. Below you can see a scope of 2050 for the use of DME.

Figure 27. Dme Scope Analysis for 2050 as Value and Volume

Assuming that Turkey accounts for approximately 2% of global LPG consumption, a

proportional estimation can be applied to projected global DME demand. Based on the 2031
global demand forecast of 12.12 million tons, Turkey’s potential DME requirement may reach
approximately 242,000 tons annually. Similarly, if global demand increases to 37 million tons
by 2050, Turkey’s demand could approach 750,000 tons per year.

These estimations are simplified and assume stable market share. However, given Turkey’s
strategic location, growing energy demand, and potential regulatory alignment with European
carbon policies, domestic DME consumption could exceed these baseline projections.

Table 16. Advantages of DME to MTBE as Pricing

Material karbon dioksit kullanımı ton carbon price(€/ton) MTBE Cost DME Cost Advantage of Dme
1 ton dme 1,91 50 125 95,5 29,5
1 ton mtbe 2,5 80 200 152,8 47,2
120 300 229,2 70,8

The mechanisms for carbon taxation will likely be crucial in determining the competitive
balance for fuels in the future. Fossil fuels will likely experience increasing carbon taxes, while
DME produced with green hydrogen and carbon capture technologies could benefit from tax
exemptions or reduced carbon taxes.

67
The inclusion of carbon capture and renewable hydrogen in the DME supply chain not only
improves the sustainability profile but also provides an additional regulatory advantage for the
DME facility, making it more competitive compared to a facility that uses CO2 as the feedstock
for DME production.

9.7. Capacity Determination

Determining the optimal plant capacity is a crucial step in ensuring both economic feasibility
and market compatibility. The selected production capacity must align with domestic demand,
trade imbalance, and regional export potential while avoiding oversupply risk.

Turkey is a net energy importer, particularly in natural gas and petroleum-derived fuels. The
domestic production of DME could reduce dependency on imported LPG and diesel,
contributing positively to the national trade balance.

Furthermore, if production capacity exceeds domestic demand, Turkey could potentially

become a regional DME exporter, especially to European markets implementing stricter carbon
regulations. This strategic positioning could enhance both energy security and economic
diversification.

With all of the information given in this section, a capacity for our dimethyl ether production
line has been estimated. In this procedure, net trade balance of Türkiye was the first concern.
We aim to produce %10 of the Türkiye’s net trade balance for 2024 with a %10 of growth limit
and with %7 potential export to neighboring countries. According to this estimation, we decided
to produce 35.000 tons/year DME.

9.8 Feasibility
The feasibility of the proposed 35,000 ton/year dimethyl ether (DME) production facility has
been evaluated from technical, economic, strategic, and environmental perspectives. The
assessment indicates that the project is viable under current and projected market conditions.
The selected bi-reforming route enables the simultaneous utilization of methane and carbon
dioxide to produce synthesis gas with an appropriate H₂/CO ratio for direct DME synthesis.

This approach:

• Eliminates the need for external hydrogen supply

• Reduces process complexity by integrating steam and dry reforming

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 • Improves carbon utilization efficiency

• Provides operational flexibility

Additionally, Türkiye possesses:

• Established natural gas infrastructure

• Accessible industrial CO₂ sources

• Mature steam generation capability

These factors confirm the technical practicality of the proposed system.

Even though demand for the dimethyl ether will likely to grow, as responsible engineers, we
decided to aim for the %10 of the required capacity with a modular process. Selected capacity
allows us to enter the market gradually and without any oversupply risk. Moreover, interal
hydrogen generation with the bi-forming improves our cost stability compared to systems that
rely on the purchased hydrogen.

With possible tighter regulations for carbon emissions, we could get carbon credit for using
captured carbon dioxide with biforming. Which can be a side income to our production line.

69
10. Sample Calculations

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74
75
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77
78
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11. Results

11.1. Design Basis and Final Operating Conditions

The process of indirect DME synthesis will have 8 compressors, 7 heat exchangers,3 Plug Flow
Reactors, 3 mixers, 1 knockout drum and 5 separation units. The PFR reactors will perform
steam reforming and dry reforming of methane, methanol synthesis from syngas and DME
production from methanol.

First PFR, which is the biform reactor, will operate at pressure of 1 bar and temperature of 800
degrees Celsius. Second PFR will be used to produce methanol will operate at pressure of 75
bars and temperature of 250 degrees Celsius. Finally, the last PFR which will synthesize DME
will operate at pressure of 9 bars and temperature of 130 degrees Celsius.

Table 17. Reactor Operating Conditions

Equipment Pressure(bar) Temperature(°C) Reactional Behavior

Biform Reactor 1 800 Endothermic
Methanol Reactor 75 250 Exothermic
DME Reactor 9 130 Exothermic

All the separation units other than the DME enriching column will be operated to recover %95
of the desired product. But for the market demand the DME enriching column will operate to
recover %99 percent of the DME.

11.2. Mass Balance Results

The mass calculations for this process are done for the reactors and the [Link] first
reactor which is the biforming reactor has a conversion rate of %90 with the recycle stream.
Second reactor which is the methanol synthesis reactor has a conversion rate of %30 and the
last reactor, DME reactor has a conversion rate of %16 .

For the separation equipments, all of the separation units except the DME enriching column
separates the wanted key by %95 percent. DME enriching column separates the DME by %99
because of the market demands.

80
 Table 18. Mass Balance Calculations for Equipments

Equipment Inlet Composition Outlet Composition

T-102 %33 CH4, %37 CO2, %30 H2O %6 CH4, %8.7 CO2, %68 CO, %9.8 H2, %7.2
H2O

T-103 %6.5 CH4, %9.4 CO2, %74 CO, %6.5 CH4, %6.5 CO2, %51 CO, %7 H2, %1.5
%11 H2 H2O, %27 CH3OH

T-106 %99 CH3OH, %1H2O %83 CH3OH, %6H2O, %11 DME

T-104R %6.5 CH4, %6.5 CO2, %51 CO, %7 %80 CH3OH, %20H2O
H2, %1.5 H2O, %27 CH3OH

T-104C %6.5 CH4, %6.5 CO2, %51 CO, %7 %8.9 CH4, %9 CO2, %70 CO, %9.6 H2, %0.46
H2, %1.5 H2O, %27 CH3OH H2O, %1.9 CH3OH

T-105C %80 CH3OH, %20H2O %99 CH3OH, %1H2O

T-105R %80 CH3OH, %20H2O %17 CH3OH, %83 H2O,

T-107C %83 CH3OH, %6H2O, %11 DME %93 CH3OH, %6.4H2O, %0.1 DME

T-107R %83 CH3OH, %6H2O, %11 DME %7 CH3OH, %0.5H2O, %93 DME

T-108C %93 CH3OH, %6.4H2O, %0.1 %43 CH3OH, %57H2O,

DME

T-108R %93 CH3OH, %6.4H2O, %0.1 %99 CH3OH, %0.4H2O, %0.1 DME
DME

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With an approximation for production of 1 ton DME requires 1.22 tons CO, 0.17 ton H2, 1 ton
CH4 and 2 tons of CO2.
Table 19. Needed Amount for 1 ton of DME

Component Needed Amount (tons)

DME 1.0
CO 1.2
H2 0.2
CH4 1.0
CO2 2.0

11.3. Energy Balance Results

For the equipment in the process flow sheet, the energy requirements are calculated for 100
mol/h basis as follows.

Table 20. Energy Requirements of Equipments

Equipment Energy Requirement (MW)

T-102 0.35
E-102 -2.10
C-102 0.86
E-103 -0.69
C-103 1.36
E-104 -1.21
C-104 0.37
C-105 -0.22
T-103 -2.20
V-101 -0.19
T-104C 1.86
T-104R -13.97
V-102 -0.39
T-105C 1.20
T-105R -6.34
E-106 -3.08
T-106 1.52
T-107C -2.04
T-107R 3.29
T-108C -3.07
T-108R 0.46

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In section 10 of this report, the enthalpies of inlet and outlet streams of equipment E-
103(Cooler) are calculated. The enthalpy for the inlet stream of E-103 was calculated as -37.37
kj/mol and the enthalpy of outlet stream of E-103 was calculated as -44.33 kj/mol. For the E-
103, energy requirement was found at -6.96 kj/mol. To verify the correctness of this, result a
chemical engineering software, Aspen Plus, is used to calculate the enthalpies of inlet and outlet
streams.

Table 21. Aspen Plus Simulation Result

Aspen Plus calculated the enthalpy of inlet stream as -37.4 kj/mol and the enthalpy of outlet
stream as -44.35 kj/mol. When the difference of these enthalpies is taken, the energy
requirement of equipment E-103 is found as -6.95 kj/mol. When the hand calculations and the
Aspen Plus calculations are compared there seems to be around %1 error which is in acceptable
range.

Table 22. Calculation Comparison

Component Hand Calculations Aspen Plus

Inlet Stream Enthalpy(kj/mol) -37.37 -37.4
Outlet Stream Enthalpy(kj/mol) -44.33 -44.35
Energy Requirement for the Equipment E-103(kj/mol) -6.96 -6.95

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11.4. Economic Results
With the analysis done on the section 6.2. Mass Balance section we know that how much of the
reactants we need per ton to produce 1 ton of DME. With market research done in Turkey and
the ton prices for the reactants found as follows:

Table [Link] for Producing 1 ton of DME

Component Price ($/ton)

DME 3210
CO 200
Green H2 4000
CH4 530
CO2 650

Based on these prices and the needed amount of the reactants, to produce 1 ton of DME it
requires 2769 $.

When this amount is expanded to the process’ 35 thousand ton/year following numbers have
been found:

Table 24. Estimated Values for Raw Materials

Component Income-Outcome
DME $ 112,350,000.00
CO $ -8,521,739.13
Green H2 $ -24,347,826.09
Gray H2 $ -6,086,956.52
CH4 $ -18,550,000.00
CO2 $ -45,500,000.00

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Table 25. Different Scenarios for Production

Process Type Income-Outcome Raw Material Expense Aproximate TAC Yearly Annual Income
Gray h2 without biform $ 52,241,304 $ 60,108,696 $ 150,271,739 $ (37,921,739)
Green h2 without biform $ 33,980,435 $ 78,369,565 $ 195,923,913 $ (83,573,913)
CO2 capture gray H2 $ 97,741,304 $ 14,608,696 $ 36,521,739 $ 75,828,261
CO2 capture green H2 $ 79,480,435 $ 32,869,565 $ 82,173,913 $ 30,176,087
Without buying h2 and biform $ 39,778,261 $ 72,571,739 $ 181,429,348 $ (69,079,348)
CO2 capture biform $ 85,278,261 $ 27,071,739 $ 67,679,348 $ 44,670,652

Figure 28. Cost Analysis for Purchased Hydrogen

Co2 capture biforming

$8.521.739,13

$18.550.000,00

CO expense $/year CH4 expense $/year

Figure 29. Cost Analysis for Bi-forming

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[Link]
The first step in producing DME from CO and CO₂ was to assign a group leader and distribute
tasks among team members. Then, to gain knowledge about the topic, we conducted a literature
review and started studying the chemicals, reactions, and physicochemical properties.

Carbon monoxide (CO) and carbon dioxide (CO₂) are gases that create significant risks for both
the environment and human health. CO is colorless and odorless but highly toxic. It poses
serious poisoning risks, especially in closed spaces. CO₂ is not directly toxic, but it is a much
bigger threat globally. CO₂ accumulates in the atmosphere and is one of the main greenhouse
gases, contributing to global warming and climate change. Since the Industrial Revolution,
human activities like fossil fuel use, cement production, and deforestation have increased CO₂
concentrations in the atmosphere. This has led to rising global temperatures, higher sea levels,
more extreme weather events, and ecosystem damage.

At this point, it is very important to consider CO and CO₂ not only as harmful emissions but
also as valuable chemical raw materials. This approach is the basis of Carbon Capture and
Utilization (CCU) strategies.

Dimethyl ether (DME) production is one of the sustainable solutions in this context. DME is an
environmentally friendly fuel with a high cetane number. It burns cleanly and does not produce
particulate matter or SOx emissions. Because it has physical properties similar to LPG, it can
be integrated into existing storage and transport infrastructure. Converting CO and CO₂ into
DME through syngas reduces carbon emissions and creates an alternative, clean energy carrier.
This chemical transformation instead of releasing CO₂ directly into the atmosphere reduces the
net carbon footprint and contributes to a circular carbon economy. Using CO and CO₂ mixtures
through methanol as an intermediate or by direct synthesis allows industrial plants to utilize
waste gases and brings economic benefits. These points show the importance of producing
DME from CO and CO₂.

DME can also be produced from biogas, which is the cheapest method, but the production
capacity is low. In this project, the process was developed especially to provide a solution to
carbon tax issues. Considering the amount of CO₂ released from flue gas, we decided to use
flue gas as the CO₂ source. For this reason, we chose to capture CO₂ from the Kardemir Iron
and Steel Factory in Karabük, which produces large amounts of CO₂, and build our plant there.
Another important step was selecting the plant capacity. During market analysis, import and
export data were collected. By calculating the difference between imports and exports, the need

86
of Turkey was determined. However, it is not correct to meet the whole demand with a single
plant because depending on one producer for the whole market creates a supply risk.
Maintenance or breakdowns could cause serious supply problems. Also, demand fluctuates
throughout the year, so the plant cannot always operate at full capacity, which reduces economic
efficiency. To maintain competition and stable prices, some import share should continue.
Therefore, capacity is usually chosen to meet only part of the total demand, and the remaining
demand is balanced with imports. For this reason, we decided to produce only a part of the total
demand, estimated future needs for 2040–2050, and selected a capacity of 35,000 tons. Capacity
selection was important because if capacity is too high, the cost and size of equipment increase.

For DME production, both direct and indirect methods can be applied technically, but in this
study, the indirect method was preferred. The main reason is that the indirect method is well-
developed, well-known, and proven in industry. It has a two-step structure: methanol synthesis
followed by methanol dehydration. This makes process control easier, reduces operational risks,
and ensures reliable operation. In the direct method, all reactions occur in a single reactor, which
creates problems with catalyst stability, water inhibition, and process control. Although the
direct method has theoretically higher overall conversion, in practice this advantage cannot be
maintained due to catalyst deactivation and process imbalances. In the indirect method,
conversion can be increased with reactor recycling, allowing a more stable, controllable, and
continuous production.

The indirect method also has advantages for raw material access, because methanol production
from syngas has a widespread and established infrastructure. Product quality is higher because
methanol can be purified before DME synthesis. Environmental effects are smaller, by-product
formation is limited, and stream management is easier. From a process design perspective, the
indirect method provides a modular structure suitable for expansion and modification. Although
it uses slightly more equipment than the direct method, the units are standard and well-known,
which makes operation and maintenance easier. Energy integration and heat recovery can
optimize energy and utility requirements. Therefore, even though the direct method offers
higher theoretical conversion, the indirect method was selected for this project because it is
more stable, ensures high product quality, provides safe operation, and allows economic
predictability.

One critical decision in process design was choosing the hydrogen source for DME synthesis.
Buying hydrogen externally is expensive and not economically sustainable for large-scale
production. Green hydrogen from electrolysis is environmentally friendly, but with current
87
energy costs and investment expenses, it is not competitive at this scale. Alternative methods
like coal gasification have high carbon footprints and environmental burdens, so they were not
chosen.

Methane-based reforming alternatives were evaluated, and bi-reforming (methane reforming

with CO₂ and H₂O) was selected as the best option. Bi-reforming includes both steam reforming
and dry reforming reactions. This allows easier adjustment of the syngas composition,
especially the H₂/CO ratio, suitable for DME production. It also recycles CO₂ in the reactor,
reducing environmental impact. In terms of energy and process efficiency, bi-reforming
provides balanced heat demand, lower coking tendency, and higher overall efficiency. Existing
natural gas infrastructure ensures easy raw material access and strong industrial feasibility.
Therefore, bi-reforming was selected as the most suitable hydrogen source in terms of cost,
syngas flexibility, environmental performance, and process integration.

DME yield and selectivity depend largely on the syngas composition and reaction equilibrium.
DME synthesis has two main steps: methanol formation and methanol dehydration. The
performance of these reactions is directly related to the CO, CO₂, and H₂ ratio in the feed gas.
In systems with both CO and CO₂, reaction kinetics and equilibrium improve, which enhances
process performance. CO reacts faster than CO₂ in methanol synthesis and activates more easily
on the catalyst surface. This increases methanol formation, indirectly increasing DME
formation and total carbon conversion. CO also helps maintain the H₂/CO ratio in a suitable
range and shifts the reaction equilibrium toward product formation. In systems with only CO₂,
more water is formed, which inhibits methanol synthesis and the DME dehydration catalyst,
lowering selectivity. Therefore, a feed with both CO and CO₂ provides faster reaction kinetics,
better reaction balance, less water inhibition, and higher DME selectivity and yield.

Desulfurization was added to the natural gas/methane feed at the beginning because sulfur
compounds poison reforming and methanol catalysts, reducing activity. This step is critical to
ensure long catalyst life and efficient operation.

The first step, bi-reforming, is an endothermic reaction where methane reacts with both steam
and CO₂ at high temperature (≈700–900 °C) and medium-high pressure. This produces syngas
with H₂, CO, and some CO₂ in suitable ratios for DME production. Our bi-reforming reactor
was selected to operate at 800 °C and 1 bar, using Ni/Al₂O₃ as the catalyst.

88
The second step is methanol synthesis, an exothermic reaction where CO and CO₂ react with
hydrogen. It typically runs at 200–300 °C and 50–100 bar. In our methanol synthesis reactor,
the conditions were set at 250 °C and 75 bar, with Cu/ZnO/Al₂O₃ as the catalyst.

The final step is DME synthesis (methanol dehydration), also exothermic. Methanol reacts over
an acidic catalyst to form DME and water. This reaction typically runs at 220–280 °C, but our
Amberlyst 35 catalyst degrades above 150 °C. Therefore, we chose 120 °C and 9 bar. This
reactor operates in the liquid phase, unlike the other reactors.

Overall, these three steps ensure the correct syngas composition, produce methanol as an
intermediate, and finally synthesize DME with high selectivity.

Mass balance calculations are fundamental in chemical process design because they allow us
to quantify the flow rates of all components through each unit operation and ensure material
conservation. By performing these calculations, we can verify that the amounts of reactants
entering a reactor match the sum of products, unreacted species, and recycle streams leaving it.
This is crucial for determining the size of equipment, selecting operating conditions, and
assessing overall process efficiency.

In this process, mass calculations were performed for both the reactors and the separation units.
The first reactor, the bi-reforming reactor, achieves a high conversion rate of 90% with the aid
of the recycle stream, which ensures that unreacted gases are efficiently utilized. The second
reactor, methanol synthesis, has a conversion rate of 30%, reflecting the equilibrium-limited
nature of the reaction under the chosen conditions. The final reactor, the DME synthesis reactor,
shows a conversion rate of 16%, consistent with the endothermic and equilibrium-constrained
dehydration reaction of methanol to DME.

For the separation equipment, most units—including condensers, knockout drums, and flash
separators—are designed to recover 95% of the desired key components, ensuring minimal
losses and efficient recycling of unreacted materials. The DME enrichment column, however,
achieves 99% separation of DME due to stringent market specifications for product purity. This
higher separation efficiency guarantees that the final DME product meets quality requirements
while maximizing the recovery and recycling of methanol and water streams.

Overall, these mass balance calculations provide critical insights into process performance,
guide equipment sizing, and help optimize both yield and sustainability in the syngas-to-DME
production process.

89
Energy balance calculations were performed to ensure that the process design is
thermodynamically consistent and that equipment sizing and energy requirements are accurate.
Specifically, the enthalpies of the inlet and outlet streams of equipment E-103 (cooler) were
calculated manually. The enthalpy of the inlet stream was determined as –37.37 kJ/mol, while
the outlet stream enthalpy was –44.33 kJ/mol. From this, the energy requirement of E-103 was
found to be –6.96 kJ/mol.

To validate the accuracy of the manual calculations, the same system was modeled using Aspen
Plus. The software calculated the enthalpy of the inlet stream as –37.4 kJ/mol and the outlet
stream as –44.35 kJ/mol. The resulting energy requirement from Aspen Plus was –6.95 kJ/mol.
Comparison of the hand calculations with Aspen Plus results shows an error of approximately
1%, which is well within an acceptable range for chemical process design.

This confirms both the reliability of the manual energy balance calculations and the correct
implementation of process conditions in the simulation. This is critical to ensure that the heat
duties, reactor temperatures, and separation energy requirements are accurately represented,
which is essential for safe, efficient, and economically viable operation of the syngas-to-DME
process.

When the market analysis and technical evaluation are considered together, the production of
DME from CO/CO₂ appears to be a strategically and economically reasonable investment
option. The global DME market shows a steady growth trend, and with the acceleration of
decarbonization policies, demand may even exceed current projections. In Europe, increasing
carbon regulations and the transition to alternative fuels strengthen the regional export potential
of such a facility.

Turkey’s position as a net importer in this product group creates a clear market opportunity for
domestic production. However, meeting the entire domestic demand with a single plant would
create supply security and operational efficiency risks. Therefore, the selected capacity of
35,000 tons per year represents a balanced and realistic approach. This capacity allows partial
substitution of imports while maintaining flexibility for future demand growth.

In terms of raw material availability, the existing natural gas infrastructure and the possibility
of capturing CO₂ from industrial facilities provide important advantages for the process. The
integration of carbon capture technologies may also offer a competitive advantage against
future carbon taxation mechanisms. This is particularly significant for potential exports to
European markets with stricter environmental regulations.

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From a feasibility perspective, hydrogen cost is the most critical factor. Reforming-based
hydrogen production is currently more economical; however, fluctuations in energy prices and
future carbon costs may affect profitability. In the long term, decreasing renewable energy costs
and the integration of green hydrogen could improve both the environmental and economic
sustainability of the process.

In conclusion, considering increasing global demand, Turkey’s import dependency, raw

material accessibility, and tightening carbon regulations, the CO/CO₂-to-DME production
process is technically viable and strategically reasonable. Its economic feasibility largely
depends on hydrogen costs, carbon taxation mechanisms, and future market prices. With proper
integration and appropriate capacity selection, the process can be considered feasible in the
medium and long term.

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[Link]
In this project, our main objective is designing a realistic and feasible production system for the
production of dimethyl ether (DME). Based on market research and trade analysis, the plant
capacity was determined according to Türkiye’s trade deficit in ether imports. The selected
capacity aims to reduce import dependency while creating the potential for export to
neighboring countries.

The design process started with establishing complete mass balances. Based on stoichiometric
calculations and reaction conversions-selectivity’s, a consistent material balance is done.
System was then scaled up from theoretical calculations to industrial production capacity. With
this scale up procedure, our system is technically grounded and not only conceptual.

For the hydrogen source, instead of using separate steam and dry reforming units, a combined
bi-reforming reactor was selected. The reason for this choice is process simplification and better
control of the H2/CO ratio in a single unit. Using one reactor reduces the equipment count,
lowers capital cost, and minimizes operational complexity. It also improves thermal integration
and overall process efficiency. Since bi-reforming is a well developed and industrially studied
method, it provides both technical reliability and design flexibility.

Although some DME production systems operate with four reactors, this design was optimized
to use three reactors. This decision was made to reduce capital investment while maintaining
process efficiency. Reactor configuration was carefully selected to balance cost and
performance.
With properly design recycle streams, high methane conversion and high overall DME yield
were achieved. Unreacted gases are redirected back into the system, minimizing raw material
losses and improving overall process efficiency. This recycle structure strengthens both
economic and environmental performance.

Another important advantage of this project is the integration of carbon capture. Since CO2 is
captured and utilized within the process, the plant avoids direct carbon emissions. This reduces
the risk of carbon taxation and may even create opportunities for carbon credits in future
regulations from the government.

On a global scale, DME demand is increasing due to stricter emission standards and the search
for cleaner fuels. Its compatibility with LPG infrastructure and its cleaner combustion
properties support its market growth. Türkiye with its strategic geographical location, has the

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potential to not only to reduce its own trade gap but also to supply nearby markets in Europe,
Middle East and surrounding regions.

In conclusion, this project demonstrates that DME production is technically feasible,

economically reliable and strategically meaningful. Selected capacity is aligned with national
trade needs. The process’s design based on mass balance consistency and industrially proven
technology. Reactor optimization and recycle integration improve cost and efficiency. Carbon
capture integration strengthens environmental compliance.

Overall, the proposed DME plant presents a realistic and competitive industrial investment for
both domestic supply and regional export potential.

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14. Recommendations
Based on the technical, economic, and environmental evaluation of the indirect dimethyl ether
(DME) production process, several recommendations can be proposed to enhance the
performance, sustainability, and long-term feasibility of the plant.

First, hydrogen sourcing should be strategically optimized. Since hydrogen cost represents a
significant portion of the operating expenses, future studies should evaluate alternative
hydrogen production routes such as green hydrogen via water electrolysis powered by
renewable electricity. Although initial investment costs may be higher, the long-term benefits
include reduced carbon footprint, avoidance of carbon taxation, and potential eligibility for
carbon credits.

Second, heat integration within the process should be further improved. Both the bi-reforming
and methanol synthesis reactions involve significant thermal effects. Advanced heat exchanger
network optimization (e.g., pinch analysis) could reduce external heating and cooling
requirements, thereby lowering energy consumption and operating costs.

Third, reactor performance optimization should be investigated in more detail. The relatively
low conversion values in methanol (30%) and DME (16%) reactors indicate the importance of
recycle streams. Future work may include kinetic modeling studies, catalyst activity
improvements, or multi-bed reactor configurations to enhance single-pass conversion and
reduce recycle compression loads.

Fourth, catalyst development and stability studies are strongly recommended. Especially in the
bi-reforming section, carbon deposition (coking) may reduce catalyst lifetime. Long-term
catalyst performance evaluation and regeneration strategies should be analyzed to ensure
operational reliability.

Fifth, carbon capture and utilization integration should be expanded. Since the process already
incorporates CO₂ as a reactant in bi-reforming, future designs may evaluate direct integration
with industrial CO₂ sources such as cement plants or steel mills. This would strengthen the
environmental positioning of the project and improve its competitiveness under carbon pricing
mechanisms.

Sixth, dynamic simulation and control analysis should be conducted. The current study focuses
on steady-state conditions; however, industrial plants operate under fluctuating loads. A detailed

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dynamic model would improve process safety, controllability, and start-up/shutdown
performance.

Finally, market flexibility should be considered. Since DME demand is projected to increase
significantly toward 2050, modular plant design could allow gradual capacity expansion.
Additionally, evaluating co-production strategies (e.g., methanol export or integration with
DME-to-olefins technology) may improve overall profitability.

In conclusion, while the indirect DME production process is technically viable and
economically promising under selected assumptions, further optimization in hydrogen
sourcing, heat integration, catalyst stability, and economic modeling will significantly enhance
the competitiveness and sustainability of the proposed plant design.

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15. References
[1] Liu, C., & Liu, Z. (2022). Perspective on CO₂ hydrogenation for dimethyl ether economy.
Catalysts, 12(11), 1375.

[2] State of the art and perspectives about the production of methanol, dimethyl ether and
syngas by carbon dioxide hydrogenation. (2018). Journal of CO₂ Utilization, 27, 326–
354.

[3] Afokin, M. I. (2021). Process solutions for recovery of dimethyl ether produced through
one-step synthesis and their assessment. Petroleum Chemistry, 61, 1043–1054.
[4] Linstrom, P. J., & Mallard, W. G. (Eds.). (2023). NIST Chemistry WebBook, NIST
Standard Reference Database Number 69. National Institute of Standards and
Technology.

[5] Haynes, W. M. (Ed.). (2023). CRC Handbook of Chemistry and Physics (104th ed.). CRC
Press.

[6] Semelsberger, T. A., Borup, R. L., & Greene, H. L. (2006). Dimethyl ether (DME) as an
alternative fuel. Journal of Power Sources, 156(2), 497–511.

[7] Tuygun, C., & İpek, B. (2021). CO₂ hydrogenation to methanol and dimethyl ether at
atmospheric pressure using Cu-Ho-Ga/γ-Al₂O₃ and Cu-Ho-Ga/ZSM-5: Experimental
study and thermodynamic analysis. Turkish Journal of Chemistry, 45(1), 231–247.

[8] Pekmezci Karaman, B., Oktar, N., & Doğu, T. (2022). Heteropolyacid incorporated
bifunctional core-shell catalysts for dimethyl ether synthesis from carbon
dioxide/syngas. Catalysts, 12(10).

[9] Karagoz, S. (2014). Process design, simulation and integration of dimethyl ether (DME)
production from shale gas by direct and indirect methods [Yüksek lisans tezi, Texas
A&M University]. OAKTrust Digital Repository.

[10] P.-C. Chen, H.-M. Chiu, Y.-P. Chyou, and C.-S. Yu, Processes simulation study of coal to
methanol based on gasification technology, World Acad. Sci. Eng. Technol., 65 (2010)
988–996.
[11] Y. Sun, Y. Nie, A. Wu, D. Ji, F. Yu, and J. Ji, Carbon dioxide reforming of methane to
syngas by thermal plasma, Plasma Sci. Technol., 14 (2012) 252–256.

[12] M. A. Naeem, A. S. Al- Fatesh, W. U. Khan, A. E. Abasaeed, and A. H. Fakeeha, Syngas

production from dry reforming of methane over nano Ni polyol catalysts, Int. J. Chem.
Eng. Appl., (2013) 315–320.

[13] Brunetti A., Scura F., Barbieri G., Drioli E., Membrane technologies for CO2 separation,
Journal of Membrane Science, 359 (2010) 115–125.

[14] Brunetti A., Bernardo P., Drioli E., Barbieri G., chapter 14 in "Membrane gas
separation", Wiley & Sons, Edited by Yampolskii Y., Freeman B., 281- 312. (ISBN
978 0 470 74621-9)
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[15] M. M. B. Noureldin, N. O. Elbashir, and M. M. El-Halwagi, Optimization and selection
of reforming approaches for syngas generation from natural/shale gas, Ind. Eng.
Chem. Res., 53 (2014) 1841–1855.

[16] S. Hosseininejad, A. Afacan, and R. E. Hayes, Catalytic and kinetic study of methanol
dehydration to dimethyl ether, Chem. Eng. Res. Des., 90 (2012) 825–833.

[17] World Bank. (2025). State and trends of carbon pricing 2025. World Bank Group.

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16. Appendices

Appendice 1. Physicochemical Properties

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Appendice [Link] Properties contd.

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Appendice 3. Physicochemical Properties contd.

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Appendice 4. Physicochemical Properties contd.

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Appendice 5. Physicochemical Properties contd.

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Appendice 6. Different catalyst for biforming reactor

Appendice 7. Effect of Pressure for Carbon Conversion

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Appendice 8. Methanol Conversion over 4 Different Amberlyst

104