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Journals Menu Engineering (journalarticles.aspx?journalid=64) > Vol.14 No.8, August 2022 (home.aspx?
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Renewable Methanol Production Using Captured Carbon Dioxide and
journalid=64) Hydrogen Generated through Water-Splitting
 Archive Dima Al Hashar (articles.aspx?searchcode=Dima++Al+Hashar&searchfield=authors&page=1)
(../journal/home.aspx? OQ, Muscat, Omen (articles.aspx?searchcode=OQ%2c+Muscat%2c+Omen&searchfield=affs&page=1&skid=0)
journalid=64) DOI: 10.4236/eng.2022.148027 (https://doi.org/10.4236/eng.2022.148027) PDF
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 Aims & Scope paperid=119270&JournalID=64)
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Abstract
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The global warming issues associated with fossil fuels have forced the world to shift towards environment-friendly
 Editorial Board
alternatives. The studies on the capture and storage of CO2 have gained significant research attention, and to attrac
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world towards CO2 capturing and storing, it is necessary to find suitable applications for this captured CO2
journalid=64)
one of the products which can be produced by utilizing the captured CO2 and hydrogen that can be produced by wat
 For Authors
splitting. Keeping in view both these green fuel production processes, this study proposes a combined application of
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these technologies for the production of methanol, which is an important chemical used in manufacturing industries.
journalid=64)
review paper presents a brief study of both carbon capture and hydrogen production technologies. It also provides
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research trends, economic aspects, and methods of incorporating both these technologies to produce methanol.
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Additionally, the prospects of the approach in Oman have also been presented.
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Keywords

Related Articles Renewable Energy (articles.aspx?searchcode=Renewable+Energy&searchfield=keyword&page=1&skid=0)

Carbon Dioxide (articles.aspx?searchcode=+Captured+Carbon+Dioxide&searchfield=keyword&page=1&skid=0)

Modeling Operational
Hydrogen Production (articles.aspx?searchcode=+Hydrogen+Production&searchfield=keyword&page=1&skid=0)
Parameters for Uranium Dioxide
Electrolysis (articles.aspx?searchcode=+Electrolysis&searchfield=keyword&page=1&skid=0), Green Methanol
Production Reactor through
Uranium Trioxide Reaction (articles.aspx?searchcode=+Green+Methanol&searchfield=keyword&page=1&skid=0)

Using Hydrogen
Share and Cite:
(paperinformation.aspx?
paperid=68111) Al Hashar, D. (2022) Renewable Methanol Production Using Captured Carbon Dioxide and Hydrogen Generated throu

Conversion of Carbon Dioxide to Water-Splitting. Engineering, 14, 339-359. doi: 10.4236/eng.2022.148027 (https://doi.org/10.4236/eng.2022.1480
Methanol Using Solar Energy - A
Brief Review 1. Introduction
(paperinformation.aspx?
paperid=7931) According to International Energy Agency (IEA), fossil fuels are still considered the primary source of the current wo
Hydrogen from Sunlight Water energy system. A large amount of carbon dioxide can be produced by this colossal use of fossil fuels, leading to an
Splitting: Is It Our Future? increase in climate change. Therefore, to reduce the emissions of CO2 associated with fossil fuels, it is necessary to
(paperinformation.aspx? technology that enables the capture of CO2 and reuses it to produce value-added compounds or an alternative energ
paperid=38228)
source instead of fossil fuels. According to IEA, the most attractive product that can be produced from CO
The Prospects for Renewable
Where the first renewable methanol production plant started operation in 2011 by Carbon Recycling International (C
Energy through Hydrogen
where it used CO2 conversion to produce methanol, which is different from natural gas-based production. However,
Energy Systems
(paperinformation.aspx? same catalysts such as Cu/ZnO/Al2O3 or Cu/Zn/SiO2 are used in both methods. Still, methanol production from CO

paperid=55659) resulted in higher purity [1]. In addition to the low cost of methanol, it degrades faster than fuel. It meets the latest

Solar Water Splitting by

Semiconductor Nanocomposites
:
 and Hydrogen Storage with emissions standards and can be used as a feedstock in manufacturing gasoline, biodiesel, MTBE, DME. As the price o
Quinoid Systems and gas fluctuates and greenhouse gas emissions increase, the interest in methanol production from renewable ene
(paperinformation.aspx?
sources has increased [2].
paperid=24696)

The purpose of this current work is to present an overview of the various methods of producing methanol. The main

Open Special Issues efforts focus on renewable methanol production using captured carbon dioxide and electrolyzed hydrogen, highlighti

recent development of chemical conversion methods and the processes of CO2 hydrogenation. Major studies on the
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improvement of new catalyst system targeting Cu-ZnO-Al2O3 Catalysts. It also provides an overview of the differenc

journalid=64&PubState=false) between using syngas and chemical conversion to produce methanol.

Published Special Issues

2. Methanol
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Methanol is used in commercial industries as a raw material in many fuels, and chemical products include the produ
journalid=64&PubState=true) of aromatics, ethylene, formaldehyde, methyl tertiary butyl ether (MTBE), acetic acid, and other chemicals [
methanol is flexible liquid, different feedstocks can be used in methanol production, such as waste, natural gas, cap
Special Issues Guideline
CO2 with green hydrogen. Moreover, according to the methanol institute, methanol is considered as a sustainable an
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clean fuel rather than a petrochemical. It is aligned with climate change policies and becomes a net carbon-neutral f

journalid=64) that can lower greenhouse gas emissions. Nevertheless, methanol is liquid at room temperature and at everyday

pressures. It has a small molecule, unlike LNG and hydrogen, that takes a more significant amount of energy to be

produced compared to methanol [4]. It is considered a harmless fuel as it has lower emissions while the combustion
E-Mail Alert process in marine or land vehicles as reported by the methanol institute.
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However, methanol is also considered a toxic chemical that can be harmful to the skin and must be handled carefull
ENG Subscription Besides, it is relatively expensive to be produced as it requires electricity, and the equipment used needs significant
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investment [4].
journalid=64)

Publication Ethics & OA Statement In general, there are five primary sources of renewable feedstocks that are used to produce renewable methanol, na
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forestry residues, municipal solid waste (MSW), agriculture waste, carbon dioxide (CO2), and renewable hydrogen [
journalid=64)
Using two different routes: electricity or sustainable biomass (called bio-methanol) [5] (Figure 1).
Frequently Asked Questions
(../journal/faq.aspx?journalid=64) In the biomass method, the organic matter is fermented in a reactor with a high temperature in the absence of air t

Recommend to Peers produce synthesis gas, which is then formed into bio-methanol. While in the electro-fuel, hydrogen is extracted from
(../journal/recommendtopeers.aspx? by electrolysis and reacts with the captured carbon dioxide to create methanol [5]. Researchers find green methano
journalid=64)
produced by captured carbon dioxide and hydrogen is the most attractive option for stabilizing the earth’s climate be
Recommend to Library it reduces the amount of carbon dioxide in the atmosphere and forms a clean and safe fuel time.
(../journal/recommendtolibrary.aspx?
journalid=64)
The first technique used in methanol production is the distillation of vinegar on wood; after that dry wood distillation
Contact us technique was used. After that, the catalytic processes have been discovered and developed, e.g., partial oxidation
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biomass (wood or solid waste) used commonly as it is relatively cheaper than the other expensive and harmful tech
journalid=64)
at the same time. The amount of methanol produced by this method is comparatively large as it is estimated to be 1

per metric ton of solid waste [6].

Sponsors, Associates,
and Links In the 1920s, the German chemical company BASF started to study the catalytic processes for methanol production;

where the first methanol was produced as by-products in the ammonia production plant with an iron-oxide catalyst
Journal of Power and Energy
led the researchers in BASF to invest more in the catalytic methanol production process and they created a selective
Engineering
catalyst made of zinc and chromium that works under high pressure of 350 bar and a temperature of 400˚C [
(http://www.scirp.org/journal/j
pee/)
Imperial Chemical Industry (ICI) has developed a catalytic process using copper instead of chromium with lower pre

ranges between 25 to 55 bar and a temperature of 200 to 300˚C. Nowadays, Cu/ZnO/Al2O3 is considered the highe

most selective catalyst for methanol production, and it is used frequently in methanol production from hydrogen and

carbon dioxide. As shown in Table 1, all the catalysts used in methanol production are made of zinc oxide, copper ox
and more stabilizer compounds [6].

Figure 1. (a) Bio-methanol production processes (b) Renewable methanol production processes from different feed
:
 Reproduced from: [5].

Producer Cu (%) Zn (%) Al (%)

SUD CHEMIE 65 - 75 18 - 23 5 - 10
BASF 65 - 75 20 - 30 5 - 10
DUPONT 61 30
HALDOR TOPSOE 50 - 60 21 - 25 15 - 28

Table 1. Typical composition of methanol synthesis catalysts (Reproduced from: [6]).

(http://www.scirp.org/journal/j
pee/) Methanol is the world’s most-shipped chemical commodity, with more than 95 billion liters Per year of products usin
Open Journal of Civil methanol such as plastics, cosmetics, paints, and fuels. It can be produced by the conventional method using fossil
Engineering
e.g., natural gas or coal (Methanol Institute, 2019). However, the main drawback of the conventional method is tha
(http://www.scirp.org/journal/o
fuels are non-renewable materials and it is expected to deplete in the near future. Nevertheless, burning fossil fuels
jce/)
causes an increase in the amount of acid rain and photochemical smog, which increases the value of carbon dioxide

results in global warming. Yet, it is still the most common and commercialized technology used [7].

3. Carbon Dioxide Capture

As stated by International Renewable Energy Agency (IRENA), the amount of CO2 needs to be reduced by more tha

from 35 Gt (in the current levels) to 9.7 Gt by 2050. Consequently, to reduce the emissions of CO2 associated with

fuels, it is necessary to find a technology that enables the capture of CO2 and reuses it to produce value-added
(http://www.scirp.org/journal/o compounds [8]. To reach this target, 7% - 32% of CO2 generated from the energy production using fossil fuels mus
jce/) reutilized by 2050, which means that 155 megatons of CO2 emissions will be reduced by 2030. Many chemical produ
Modern Mechanical Engineering
the industrial scale can be produced using CO2 as a feedstock, e.g., methanol, formaldehyde, methanol, carbamates
(http://www.scirp.org/journal/
polymer-building blocks, and methanol formic acid. The synthesis of methanol and urea are the chief consumers of C
mme/)
with more than 110 megatons of CO2 annually used in the production industries of these two chemicals [8

Carbon dioxide can be produced from exhaust streams, for instance, power plants, cement and steel factories, distil

and others. In 2016, around 32.045 billion metric tons of CO2 were released into the atmosphere, and it raised by 1

2017, which is equivalent to having 170 million cars on the road [5]. Carbon dioxide is considered the most dangero

greenhouse gas that absorbs solar energy and keeps heat close to the earth instead of being released to space [

Nevertheless, the emission of carbon dioxide in 2018 reached 6677 million metric tons (Figure 2).

(http://www.scirp.org/journal/ Carbon dioxide emissions driven by human activities pose a threat to the whole planet, where the average surface
mme/) temperature has risen about 1.18 degrees Celsius in the last two years [10]. This has led government institutions, s
World Journal of Engineering
and industry to search for clean fuels produced by using renewable feedstocks to reduce greenhouse gas emissions.
and Technology
Therefore, they turn to using green methanol that is produced by renewable raw materials as a clean alternative sou
(http://www.scirp.org/journal/w
for fossil fuels [5].
jet/)

Many technologies have been used to capture CO2 from an industrial source, including post-combustion capture, pre
combustion capture, and oxygen fuel or oxyfuel combustion. Other new technologies are under research and develo

e.g., adsorption, absorption, solid sorbent, and membrane separation technologies [11]. Nevertheless, CO

captured directly from the atmosphere, called Direct Air Capture (DAC). Currently, there are 15 direct air capture pl

around the world, capturing more than 9000 metric tones of CO2 per year, including Carbon Recycling International

which produces 4000 metric tons of renewable methanols by mixing up 5600 metric tons of captured carbon dioxide

year with renewable hydrogen [5]. According to Sustainable Development Scenario (SDS), this amount will be scale
(http://www.scirp.org/journal/w
by 2030, where 10 million metric tons of carbon dioxide per year will be captured using DAC technology. Figure 3
jet/)
CO2 capture by direct air capture in the SDS, 2010-2030 [12].
Computational Water, Energy,
and Environmental Engineering
(http://www.scirp.org/journal/c
Figure 2. Overview of greenhouse gas emissions (Reproduced from: [9]).
weee/)

After CO2 is extracted from the air, it can be stored in deep geological formations or used in food processing, or com
with hydrogen to form value-added chemicals such as methanol. There are two different types of systems used to ca

carbon dioxide from the atmosphere: liquid and solid direct air capture technologies. In the liquid system, the air pa
:
 through chemical solutions, e.g., a hydroxide solution that absorbs carbon dioxide, and the rest of the gases are tur

back into the atmosphere. The solid technology uses sorbent filters that bind with carbon dioxide chemically, where
filters are heated to collect the concentrated CO2, which can then be captured for use or storage [12].

Figure 3. CO2 capture by direct air capture in the SDS, 2010-2030. Reproduced from: [12].

4. Hydrogen Production: Electrolysis

(http://www.scirp.org/journal/c
weee/) Hydrogen fuel has shown great potential in helping the world tackle the global warming issue and, at the same time

meet the global energy requirements effectively, using a sustainable approach. Although there are several approach

Follow SCIRP available for the production of hydrogen, such as electrical, solar-based electrical, biological and chemical, currently

electrolysis or electrical hydrogen production systems are the most profitable and sustainable. The study justified th
claim by using 3S mode of evaluation for hydrogen production technologies [13].
(https://www.facebook.com/Scientific-
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Electrolysis is the easiest and the most appropriate option for hydrogen production
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In this process,
267429817016644/) water is split into oxygen and hydrogen by using electricity. The reaction occurs in an electrolyzer u
can differ in size from large-scale, central production facilities to small-scale distributed hydrogen production [

Contact us any fuel cell, electrolysers consist of a cathode and an anode separated by an electrolyte. There are many electrolys
types, e.g., alkaline electrolysers, solid oxide electrolysers, polymer electrolyte membrane electrolysers, etc. These
electrolysers
customer@scirp.org
work differently depends on the type of electrolyte material involved [14]. Not minding the type of

technology
(mailto:customer@scirp.org)
employed, the electrolysis process involves the introduction of water into the reaction environment. The
solution
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then subjected to an electrical current, causing dissociation. The separated hydrogen and oxygen atoms a

(http://wpa.qq.com/msgrd? made
1655362766
to accumulate
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in their individual physical streams by putting them through an ionic transfer mechanism [
v=3&uin=1655362766&site=qq&menu=yes)
Figure
v=3&uin=1655362766&site=qq&menu=yes)
4, it presents a diagrammatic example of an electrolyzer.

As a clean energy source, H2 can be derived from both renewable and non-renewable sources [17]. Moreover, H

generated using an electrolyzer by connecting the fuel cells in the reverse mode through either water or methanol, o
other hydrogen carrier. An illustrative example of the generation of hydrogen and methane is the dark fermentation

process with anaerobic digestion of residual algae biomass [17]. Even though the electrolysis method of hydrogen
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production is more expensive than the steam reforming of natural gas [15], the transition to a hydrogen economy w

greatly on the electrolysis process.

Figure 4. An electrolyzer (Reproduced from [16]).

This is because, with electrolysis, small facilities can be built and used against what is obtainable with other method

There are two main water electrolysis technologies: proton exchange membrane (PEM) solid polymer and potassium

hydroxide (KOH) technologies. Further researches are also ongoing on other modes of water electrolysis, constructio
cells, construction and selection of electrodes and electrolytes, and other parameters for another improvement of wa

electrolysis systems [18] [19].

5. Methods for Chemical Conversion of CO2 to Methanol

5.1. Electrochemical Reduction of CO2 to Methanol

The electrochemical reduction method is used to convert carbon dioxide to valuable fuels and chemicals using differe
electrocatalysts, conditions, and energy, which is electricity. The effectiveness of the method chosen depends signifi

on the catalyst that is selected and the conditions of the reaction. Therefore, a huge effort must be applied to choos
appropriate electrode for the electrochemical reduction of CO2 to reduce carbon dioxide’s selectivity at high rates an
over potential without lowering water. Whereas water is used as an electrolyte and proton source, metals with a hig

hydrogen evolution reaction (HER) are used as an electrocatalyst.

:
 Table 2 shows the products that can be produced electrochemically from CO2, where the formed product depends on
reaction conditions and selection of catalyst [20].

Electroreduction allows the methanol to be produced in only one step by reducing CO2 directly in the electrolysis cel

can be done by using different types of electrodes such as semiconductors, metal oxide, homogeneous catalysts and
types. In 1983, many semiconductors such as n-GaAs, p-GaAs and p-InP were used to produce methanol directly fro

CO2. However, the current densities and faradaic efficiencies (FEs) are relatively low. Many other studies

Half-cell reaction E˚ Vs. SHE

CO2 + 8H+ + 8e− → CH4 + 2H2O +0.17
CO2 + 6H+ + 6e− → CH3oh + H2O +0.131
CO2 + 4H+ + 4e− → CH2o + H2O −0.028
CO2 + 2H+ + 2e− → Co + H2O −0.10
CO2 + 2H+ + 2e− → hCOOH −0.11

Table 2. Standard potentials for CO2 reduction (Reproduced from [20]).

have been carried out to increase the faradaic efficiency and current density of the process. For example, pyridinium

homogeneous electrocatalys, has been utilized for CO2 reduction, then pyridine was discovered and used as a co-ca
to create the active pyridinium species. Recently, it has been found that the two-electron reduction products like CO

higher current density than the one-electron reduction products of CO2. The direct electrochemical reduction of CO
has not yet been applied in industrial processes successfully but it is used widely on a laboratory scale [20

The electrical chemical reduction has many advantages, e.g., it can be recycled, which significantly reserves chemic

reduce waste. It also has a flexible and controllable reaction. It is considered a green and clean process as it uses a
source of energy, such as tide, wind, and solar power. Nevertheless, this method does not consume a large amount

hydrogen [21] [22].

Many studies have been done on developing the electrocatalysts and the reactor configuration/electrode in methano
production by electrochemical reduction to accelerate the production process and increase the selectivity [

this method has some drawbacks, e.g., the low current density, overpotential, stability, and it have not yet been ap
in the industrial processes successfully. Still, it is used widely on a laboratory scale [20], making it unconvincing for

commercial applications.

5.2. Photochemical Reduction of CO2 to Methanol

The photocatalytic or photochemical method is a combination of photophysical and photochemical processes. Solar e
such as laser or light is used to transfer the captured carbon dioxide into methanol and other various products. This

method is relatively similar to the electrocatalytic method of CO2 reduction, where both ways use molecular catalyst
Recently, the photochemical process has been considered a promising method for CO2 conversion. However, the

selectivity of methanol is low compared to the other methods. The major limitation in this method is the sacrificial h
source that must be added to the solution to substitute the anode, for example, amine, 1-benzyle-1, 4-
dihydronicotinamide, and ascorbic acid. In Figure 5, it presents a simple schematic of the photocatalytic reduction o

[20].

Figure 5. Schematic of photocatalytic reduction of CO2 system [24].

Many experiments have been done to examine the ability of metal oxides and semiconductors to convert CO

including NiO, ZnO, TiO2, silicon carbide, and others. They can be either used alone or by adding them to other
heterogeneous catalysts. However, the main drawback in producing methanol by solar energy and semiconductors i

the formation reaction is reversible. Therefore, it is essential to find other strategies to mitigate methanol oxidation
reach the desired industrial process. Photochemical reduction of CO2 is considered the most attractive method for C

conversion, even if the selectivity of methanol is relatively low in this method [20].
:
 However, many other undesired products such as carbonates, formic acid, elemental carbon, and oxalic acid can be
formed simultaneously in methanol production using photocatalytic CO2 reduction, leading to a lack of selectivity. So

these products can be poisoning for the photocatalyst, quenchers, and even cause degradation and produce CO
the present stage, this method faces a lack of understanding the factors of controlling the products and modifying th
direction of the whole process to produce only one desired product. Thus, the recovery of the non-gaseous products

the product distribution can cause a deactivation on the photocatalysts’ surface. Scientists think that the leading cau
the problem is the differences in the potential products’ chemical and physical properties formed from carbon dioxid

result, the whole CO2 reduction should be mass balanced to avoid any solid phase deposition. Nevertheless, photoca
studies have to focus more on the factors and reasons behind other undesired products’ formation [25].

Photocatalytic reduction is an attractive method to use. Still, at the same time, it constitutes a real challenge as it n

lot of modifications and development in photocatalysts’ effectiveness. The thermodynamics and kinetic requirements
to be developed; for instance, electrons and protons simultaneous transfer.

5.3. Photoelectrocatalytic Reduction of CO2 to Methanol

The Photoelectrocatalytic CO2 reduction method combines the electrocatalytic and photocatalytic techniques. Many

semiconductors have been tested with different materials that are used as photoelectrode to transform CO
applying solar energy in PEC cell. Still, none of them met the desired efficiency and stability. This method uses arou

eV of thermodynamic energy input. Thus, more significant energy input is needed for the PEC cell to make up for th
losses that are caused by the overvoltage potentials, resistance losses, and band bending. Solar irradiance of

semiconductors is used as a photocathode, and it helps generate hydrogen ions and electrons. The electrons will be
excited to transfer it from the semiconductor to the conduction band, then move until it reaches the cathode counte

electrode through an external electrical wire. After that, the produced electron-hole pairs will be split by the
semiconductor to make oxidation and electrochemical reactions injected into the electrolyte. In Figure 6, it shows a

photoelectrocatalytic cell to reduce CO2 [26].

Despite the importance of photoelectrochemical method economically and socially, only a few studies have been don
developing this method. However, the main drawback of the photoelectrochemical CO2 reduction is the susceptibility

semiconductors materials to degrade and oxidize the semiconductors surface, which results in creating holes on the
surface of the semiconductors itself. This leads to thermodynamic instability toward anodic photodegradation [

It is required to understand some mechanisms to get good results in using PEC in CO2 reduction; 1) understand the

mechanisms of CO2 reductions and water oxidation over the surfaces of photocathode and photoanode; 2) the disso
and evolution of carbon dioxide in some organic solvent that can be dissolved in water such as monoethanolamine;

interacting of the photocathode and photoanode materials with polymers; 4) study the corrosion of non-oxide

semiconductors in solar irradiance and the passivation of the materials of semiconductors. 5) understand the behavi
ions and electrons of organics and the catalysts transferring in the photoelectrochemical cells. 6) integrate all the sy

related to the CO2 conversion to methanol in photoelectrochemical cells [28].

5.4. Chemical Conversion

Catalytic hydrogenation of CO2 with hydrogen is the most usable and most straightforward method for methanol
conversion. During the 1920s and 1930s, hydrogen and carbon dioxide were used widely in methanol production pla

the USA and were operated at high pressure and temperature using different oxide catalyst types, especially a mixe

Cr2O3-ZnO material. Then, a new process was developed using a Cu/Zn/Al2O3 catalyst, which operates at lower pres
and temperature, with a desulphurization unit in front to remove sulfur as Cu is very sensitive. The first commercial

that used this type of catalyst was built in 1966 [20]. This method has two different systems, heterogeneous and

homogeneous catalysts systems:

Figure 6. Photoelectrocatalytic cell for CO2 reduction (reproduced from [26]).

5.4.1. Homogenous Catalyst

:
 The first study on the carbon dioxide hydrogenation method by using homogeneous catalysis and the proper type of

used catalyst was carried out in 1995 by [29]. [29] proved that the Ru3(CO)12-K for CO2 conversion works better th
other transition metal carbonyle catalysts, for example, Fe2(CO)9, W(CO)6, Ir4(CO) and RH4(CO)12. Instead of the s

electrons process, the cascade process has been used for CO2 conversion [20].

The Cascade process using homogeneous catalysts includes three steps, which are hydrogenation of CO2 to formic a

then in the next step, formic acid will be esterified to generate formate esters, and in the final step, formate ester w

hydrogenated to produce methanol [30].

The reaction is undergone around 135˚C of temperature and 40bar of pressure. However, these numbers differ on t
catalysts that are used in each step. The main two agents that help reduce the carbon dioxide in homogeneous chem

conversion are silanes and hydrides, with organocatalysts, e.g., N-heterocyclic carbenes (NHC). In addition to the h

cost of silanes, Zhang proved that the NHC-catalyst could reduce carbon dioxide by reducing methoxides under amb

conditions [30].

The application of frustrated Lewis pairs for CO2 reduction to methanol is another example of metal-free catalysis. In
first step of the reaction, that formatoborate derivative is produced by the reaction of CO2 with [TMPH] + [HB(C6F5

Then in the next step, the latter reacts with [TMPH] + [HB(C6F5)3]- to formaldehyde acetal derivative and methano

However, the biggest challenge in the homogeneous catalysts is the separation process; in some cases, the catalyst

cannot be separated from the product as they have the same phase. In other cases, the products are volatile, makin

difficult to separate them by distillation. Moreover, compared to heterogeneous catalysts, homogeneous catalysts’ th
stability is relatively low, where the operating temperature ranges between 80˚C to 100˚C and rarely reaches near

some pincer-based catalysts [31].

Homogeneous CO2 hydrogenation to methanol is still in its infancy and needs to be developed more to become prac

Nonetheless, more studies need to be done to improve homogeneous catalysts’ efficiency, especially non-noble met

(e.g., Fe, Cu, Mn, Co, etc.) to increase the produced quantity of methanol to make this method industrially valid [

5.4.2. Heterogenous Catalyst

Heterogeneous catalysts are more effective than homogeneous catalysts, separating the fluid from solid catalysts ea

can also be recycled and used in various reactors, such as fluidized and fixed reactors. Many studies have proven th

Cu-based catalysts with multiple additives, for example, ZrO and ZrO2 show more stability and efficiency than the o
types [20]. Methanol is produced using the commercial methanol catalyst, a heterogeneous mixture of alumina, cop

and zinc oxide. Consequently, much research focuses on developing the performance of catalysts to increase the am

of produced methanol. Nevertheless, these researches aim to improve catalysts’ activity and stability over time to su

high plant output. CO2 hydrogenation into methanol is an exothermic reaction (∆H 298 k = −49.5 kJ/mol), which in
catalytic conversion at relatively low operating temperatures between 230˚C and 270˚C [20].

Figure 7 presents the heterogeneous catalytic process for converting CO2 to methanol using Cu/ZrO2 and Cu-ZnO/Z

where the formal structure-insensitive character of CO2 transformation can be determined by the dual-site nature of

reaction path [20].

5.5. How Cu-ZnO-Al2O3 Catalysts Work

CuZnAl (Cu/ZnO/Al2O3) was developed firstly by Dalian Reak Science and Technology Co., Ltd. The studies have bee

conducted on hydrogenation of CO2 fixed-bed continuous-flow reactor in high pressure. Before catalysts are placed

stainless-steel floor reactor, it is diluted with quartz sand (0.8 mL, 20 - 40 mesh). Catalysts are also being kept for o

hour at 250˚C with the hydrogen flow of 20 mL·min–1 in a phosphoric pressure. After cooling the vessel, the reactor
introduced with feed gas and H2/CO2 in a ratio of 3/1 with adjusting pressure to 3 MPa, which is further followed by

keeping the temperature at 200˚C initiating their reactions. A thermocouple is used to control reactions by keeping

temperature at 200˚C and pressure at 3 MPa and H2/CO2 = 3 with gas hourly space velocity (GHSV) = 9000 h

collection of data from the reaction from 10 hours of operations using a thermal conductivity detector and using a fl
:
 ionization detector. Reactions in various stages mainly after H2 reduction, after ten h and 720 h, found no diffraction
peaks of Al2O3 during multiple stages of using the CuZnAl catalyst. This is due to the high dispersion of catalysts an

content of Al [33].

Aggregation of Cu particles is the main reason for the deactivation of Cu-based catalyst in methanol synthesis [

10 hours of reaction, the size of Cu particles has decreased from 11.7 to 7.9 nm, and this might be due to the

Figure 7. Heterogeneous catalytic process for conversion of CO2 to methanol using Cu/ZrO2 and Cu-ZnO/ZrO
from [20]).

reconstruction of Cu species [34]. Usage of conventional Cu-ZnO catalysts leads to complete reduction of partial red

of Cu when it contacts with ZnO. The other by-products are also formed as part of methanol synthesis by this conve
catalyst [35]. Creating Cu-ZnO interphases is very important to get an active catalyst in the methanol synthesis pro

Optimization of hydrogen partial pressure, heating rate, the temperature can play a crucial role in determining the o

catalyst [36].

A different nanomorphology used for the synthesis has resulted in the best catalytic results from ZnO. Based on this

study, the mechanism that has been widely accepted for bringing improvements in the catalyst is Cu/ZnO/Al
formulation. The use of Cu/ZnO/Al2O3 in methanol synthesis from CO2 brings significant improvements [36

complete production in Cu is observed when Cu-based conventional catalysts get in contact with ZnO or even partia

reduction in ZnOx. The critical role of ZnO is that it helps the stabilization and dispersion of Cu sites and also helps i

absorption of the CO2, which influences the performance of the catalyst [37]. The use of Al2O3 in the catalyst is that
helps improve the stabilization and dispersion under various reaction conditions of Cu-active centers.

The commercial preparation of Cu/ZnO/Al2O3 catalyst is based on a three-stage process, which includes precipitatin

precursors in hydroxy carbonates. These hydroxycarbonate precursors are calcinated in a controlled manner to prod

dispersed CuO-ZnO. This process also produces residual carbonates, which maintain porosity on surface areas. The

stage of ZnO/Al2O3 catalyst precipitation includes reducing the oxidized phases to get active catalysts such as Cu+
nanoparticles or Cu for ZnO [38].

In catalyst synthesis, hydroxycarbonate precursor synthesis is the main stage as the final catalyst depending on the

stages in the progression of the catalyst [39]. Catalyst precursors need to have controlled precipitation which helps

preparing an efficient catalyst for hydrogenating CO2. The final catalyst has desired properties with a large Cu surfac

area, better Cu-ZnO interaction, and even forming surface Cu-Zn partial oxidized materials. In the co-precipitation
process, minimal contamination takes place from alkali metals (Na+). Controlling the parameters is required in the

hydroxycarbonate precursors’ vision progression by considering the aging time, temperature, and pH [39] (

5.6. Feasibility Analysis of Methanol Synthesis

The idea of synthesizing methanol using captured CO2 and hydrogen is a unique approach that is needed for a feasib
analysis as both it is a quite new and expensive technology. In this regard, an important economic study has alread

carried out by researchers in [40], and our entire feasibility portion will be based upon this predictive cost analysis s

The study carried out the economic feasibility analysis of the production of renewable methanol utilizing captured ca

and hydrogen generated through electrolysis of water. The study employed Aspen Hysys 9, a simulation software, to

evaluate technical analysis and predictive cost analysis of the project.

It was found that methanol cost for industrial-scale production of 100 tons per day will cost 0.48 $ per kWh of energ
consumed. The cost of renewable methanol cannot reach the cost of present methanol production facilities which co

around 0.065 $ kWh−1 [40]. The main cost driving parameter for Methanol production is hydrogen which can cost u

$ kgH2−1.

Figure 8. Pathways of methanol production from CO2 hydrogenation over Cu-based catalysts (Reproduced from [
:
 The cost of hydrogen is also a challenging factor that has limited its applicability so far and research is ongoing to re

it to $2 to $3 per kg [41].

However, the added environmental benefits and the ban on fossil fossils in the future can make this technology a go

alternative. Also, with the advancement of research in this field of renewables, the costs will surely decrease in the f

5.7. The Difference between Using Syngas and Chemical Conversion to Produce Methanol

Equation (1) shows the industrial production of methanol by syngas, a combination of monoxide and hydrogen, whe

syngas is produced by using steam reform fossil fuels. It consists of a small percentage of carbon dioxide (CO

second equation is the industrial production of methanol by heterogeneous chemical conversion with using of
Cu/ZnO/Al2O3 as a catalyst at a high temperature of 200˚C - 300˚C and high pressure of 5 - 10 MPa.

CO + 2H2 ≥ CH3OH ∆H = −90.8 kJ·mol−1 (1)

CO2 + 3H2 ≥ CH3OH + H2O ∆H298K = −49.5 kJ·mol−1 (2)

The process of generating methanol is less exothermic in Equation (2) rather than in using syngas. The two significa
differences between producing methanol from pure CO2 or syngas are the exothermicity of both processes and the

formation of water in the synthesis that causes the deactivation of the catalyst prematurely [35]. Methanol synthesi

syngas takes place with higher exothermicity based on Equation (1) which creates the need for considering the reac
design to remove additional heat produced in the reaction. The convention plants producing methanol from syngas a

based on the boiling water reactor type as it facilitates dissipating produced heat. Thermal control can be more acce

due to the low heat generated compared to the other process. There is no need for a boiling water reactor, whereas

simple tube reactor is good enough to control the temperature of methanol, which can improve the operation’s effici
and lower the cost [42]. To carry out methanol synthesis from syngas, the conventional catalysts used are mainly C

combined with ZnO. One of the significant problems with the traditional catalyst is that it is less effective, where it c

only convert 20% or less of CO2 [43].

Additionally, synthesis from CO2 produces a higher level of water and causes problems as it accelerates crystallizatio

ZnO and Cu particles. This leads to the deactivation of the catalyst and produce unwanted substances such as some
hydrocarbons. Cu-ZnO catalysts are commonly used for methanol synthesis and hydrogenation of CO2. However, it

some drawbacks, and most studies are on the improvement in the properties of catalyst in terms of physicochemica

properties that are related to the efficiency of the catalysts [44].

5.8. Prospects in Oman

The economic assessment was based on historical fuel prices, energy expenses, and fuel economy. A life cycle analy

was used to assess carbon dioxide emissions. It was discovered that exclusively using green methanol as a fuel redu

CO2 emissions from well to wheel when compared to fossil fuels [45]. It was established how much methanol could

produced using recycled garbage and wind power. Its yearly output ranges between 7.21 to 40.2 million tonnes [

Renewable methanol decreases carbon dioxide emissions by up to 95%, nitrogen oxide emissions by up to 80%, an
sulphur oxide and particulate matter emissions entirely in Oman as compared to traditional fuels. Methanol is increa

being seen as a clean and sustainable fuel rather than only a petrochemical [46]. Methanol becomes a net carbon-n

fuel when made from renewable feedstocks such as collected CO2 or garbage, aligning with climate change initiative

reduce greenhouse gas emissions.

Oman is a country that earns a large portion of its income through the oil and gas industry. Owning to the shifting t
of the world, because of the harmful environmental effects of fossil fuels such as global warming, the world is shiftin

towards renewable energy sources to fulfill its energy demands. In terms of chemical production, the use of green

chemicals is getting attention and conventional petroleum-based chemicals are also expected to be replaced.
:
 So oil-based countries have to look for alternative income sources, which although they are already doing, such as

increasing tourism, etc., but also have to look for other energy production means to fulfill their energy requirements
Although methanol is already being produced in Oman, this methanol is being produced from natural gas which is no

considered a very environment-friendly way. With the expected ban on petroleum-based chemicals in the coming fu

this method is not long-lasting.

There are several important uses of methanol, such as biodiesel, adhesives, and solvent production, which will incre

demand in the coming future. The demand for the downstream products of methanol such as methyl lactate, which
referred to as a green solvent, is also increasing owing to the trends in the world. But to ensure the sustainability of

downstream products, methanol has to be derived through environment-friendly methods. In other words, the

introduction of this project will open pathways for several other downstream industries, ensuring the sustainability o

processes, and will help Oman not just in terms of the environment but will also help it in playing an important role
supplying green chemicals in the future.

However, there are several companies in Oman that produce methanol using the traditional way; for example, Oma

methanol, Salalah methanol that is owned by OQ, and others. However, there are also projects under review that ai

produce methanol using green hydrogen and carbon dioxide.

5.8.1. Salalah Methanol Co. LLC

Salalah Methanol Company LLC, a subsidiary of OQ Company, was founded in 2006 with the goal of constructing a c

edge methanol manufacturing plant in the Salalah Free Zone. It is a chemical firm with between 201 and 500 people

Methanol is made from dry sweet natural gas, which is provided by the Ministry of Oil and Gas through existing pipe

networks. They already have the underlying infrastructure and the majority of the industrial facilities needed to crea
ammonia in their methanol plants. Ammonia was a commercially appealing product, allowing us to fund the project

through the refinancing of existing Salalah Methanol Company assets rather than depending on shareholder stock [

5.8.2. Oman Methanol Co. LLC

In 2004, Oman Methanol Holding Company LLC, a part of Omar Zawawi Establishment (Omzest), and Methanol Hold
International Limited created a joint venture (MHIL). The OMC Plant is located at the Sohar Port Complex on the Gu

Oman, having maritime access to international markets. The methanol plant and facilities started producing refined

methanol in December 2007 and now produce over 3000 tonnes per day. A team of highly skilled and capable indivi

with vast expertise in the petrochemical industry staffs and runs the company. The bulk of OMC’s employees are Om
nationals who get rigorous training that are tailored to each person [45].

6. Discussion

The concept of renewable methanol production is unique as it employs CO2 captured from industrial processes or th

atmosphere and hydrogen produced by splitting water. Hence, an idea of manufacturing methanol from raw materia

which are not derived from petrochemicals has been presented. This approach will help in resolving the problem of s
a large volume of CO2, which by this approach can be utilized for green fuel production.

Hydrogen fuel, itself can be used as a fuel which by this approach can be utilized for forming a chemical instead of e
which will increase the applications of water-splitting technology in the manufacturing sector increasing the speed o

development of the technology.

This approach will also allow the petroleum-based manufacturers of Methanol, who already have a well-established m

for the product, to shift towards renewable methanol production.

7. Conclusion

As renewable energy sources can help greatly minimize environmental pollution and global warming issues, several

of preparation of renewable energy have been employed by the researchers. Especially the production of renewable
methanol that is used as an alternative where it reduces emissions of manufacturing industries that are caused by fu
:
 combustion as it is considered the main source of climate change. Great progress has been made in the field of elec

and photochemical processes and the processes have attained high efficiencies which are comparable to the comme
processes. Still, significant research is needed on the subject from the effective capturing and separation of CO

manufacturing of methanol, especially on the economics of making renewables feasible for industrial-scale manufact

Conflicts of Interest
The authors declare no conflicts of interest regarding the publication of this paper.

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