Journal of CO₂ Utilization 32 (2019) 299–320

Contents lists available at ScienceDirect

Journal of CO2 Utilization

journal homepage: www.elsevier.com/locate/jcou

Review article

Perspective of dimethyl ether as fuel: Part I. Catalysis T

Ujjal Mondal, Ganapati D. Yadav
⁎

Department of Chemical Engineering, Institute of Chemical Technology, Nathalal Parekh Marg, Mumbai 400019, India

ARTICLE INFO ABSTRACT

Keywords: Dimethyl ether (DME) is heralded as the cleanest high-efficiency compression ignition fuel as a substitute for
Dimethyl ether (DME) diesel. DME's autoignition property and high octane number are favorable to use it as a substitute for diesel and
Syngas also LPG as a cooking fuel. DME can be synthesized from different routes such as coal, petroleum and biomass
CO2 including various greenhouse gases. Huge amounts of greenhouse gases (CO and CO2) are generated in coal or
Catalysis
petroleum operated thermal power plants and released in the atmosphere. Roughly 5–10% of total CO2 emission
Multi-metal catalysts
can be utilized for fuel and chemical production. CO2 capture and sequestering (CCS) plants only can be sus-
Fuel
Methanol tainable if supported by DME synthesis plant with a capacity of 3000–7500 TPD. DME can be produced from CO2
LPG using innovative catalysts, reactors and separators. Part I of this review is a representation of the innovative
CCS strategies which have been reported for the production of DME from different sources of raw materials, catalysts
Multi-phase reactors and influence of operational parameters on DME selectivity and yield. The critical gaps are identified and fur-
ther, research potentials are given in Part I. However, the industrial processes using a variety of reactor con-
figurations affect the overall capex and opex. The production of syngas, irrespective of the source, is the first step
in DME synthesis, which is then followed by conversion into DME using a battery of reactors and separators. A
critical analysis is presented and future scope is outlined in Part II.

1. Introduction
The UN Sustainable Development Goals for the world are indeed
challenging and consequently finding reliable and economic resources
for energy will depend on the science and technology of converting
different waste products, waste energy and finding new resources. The
energy and environment problems are intertwined due to the fast de-
pletion of natural resources and a huge build-up of greenhouse gases in
the atmosphere. Among different natural energy resources such as crude
oil, coal, and natural/shale gases, crude oil is depleting very fast. The
transportation industry happens to be the primary cause of oil delpetion;
it consumes roughly 57% of total petroleum production. According to
some estimates (e.g., BP Energy), the crude oil supply will run out by
∼2055. Electric cars are introduced to restrain air pollution but the
problem is still unsolved as most of the power plants are operating on
coal and petroleum as the primary non-renewable energy sources. The
power plants are releasing a huge amount of greenhouse gases (COX,
SOX, NOX) into the environment. The lifetime of the natural resources has
been reduced dramatically and their overuse will lead to energy supply
shortages for future generations. These problems have propelled to re-
search and innovation in the development of new clean energy
alternatives, which have to be renewable and can be utilized in the in-
dustry without any major modification of the present infrastructure.
The three main characteristics of the energy supply chain which are
essential for any type of energy infrastructure are the energy genera-
tion, storage, and distribution and utilization [1]. Dimethyl ether
(DME), or methoxymethane (IUPAC name) is the cleanest high-effi-
ciency compression ignition fuel because of its autoignition property. It
is the simplest and safer aliphatic ether which is known to be far from
being toxic, carcinogenic, teratogenic, mutagenic compound and cor-
rosive. DME is an environmentally benign compound and upon release
it is photochemically degraded to CO2 and H2O a within few hours and
will not deplete the ozone layer or build up greenhouse gas [2]. Apart
from its use as fuel, DME is a higher grade propellant used for the
synthesis of many safer healthcare products vis-à-vis conventional
petroleum-based routes. It is estimated that the total worth of the DME
industry will be approximately $ 9.7 billion by 2020 [1] which is di-
vided in mainly four categories mainly, (1) LPG blend, (2) diesel re-
placement as a transportation fuel, (3) gas turbine fuel in power gen-
eration sector, and (4) chemical precursor for different chemicals (for
instance, olefins and petrochemicals). China is the largest DME pro-
ducer utilizing 90% of total DME production for LPG blending. Other

DOI of original article: https://doi.org/10.1016/j.jcou.2019.02.006

⁎
Corresponding author.
E-mail addresses: gdyadav@yahoo.com, gd.yadav@ictmumbai.edu.in (G.D. Yadav).

https://doi.org/10.1016/j.jcou.2019.02.003
Received 24 January 2019; Accepted 7 February 2019
Available online 23 April 2019
2212-9820/ © 2019 Elsevier Ltd. All rights reserved.
U. Mondal and G.D. Yadav Journal of CO₂ Utilization 32 (2019) 299–320

Fig. 1. The overall trend of papers published in the area of DME synthesis.
countries such as Egypt, Indonesia, South Korea, Vietnam, and India
have also started evaluating or establishing manufacturing DME units.
A number of research articles have been published over the years on
DME synthesis (Fig. 1), particularly during the last two decades. The
highest number of articles were published in 2011 due to its perceived
great potential as a fuel inviting the attention of researchers in academia
and industry. It is thus timely to review the scope of DME and its potential
as a fuel and precursor for a number of chemicals, and industrial processes.
The current review is thus written in two parts highlighting all areas
concerning DME synthesis using various catalysts, and the reactor and
separation strategies. The scope of Part I is to highlight the recent ad-
vancement of DME synthesis which includes various innovative reac-
tion systems, catalysts and their synthetic protocols to get high activity,
and effect of operational parameters on DME selectivity and yield.
2. DME properties and applications
A comparison of the physico-chemical properties of different con-
ventional fuels which could be replaced by DME is shown in Table 1.
According to the World LP Gas Association (WLPGA), DME can be
used as a mixture or separately as a substitute in the LPG industry [4].
About 15–20 vol.% of DME blending in LPG will not affect the current
LPG infrastructure for storage, distribution, and usage [5]. DME gas can
be liquefied by pressurizing at 0.57 MPa at 20 °C or by cooling to
−25 °C at atmospheric pressure. The similar physical properties of LPG
and DME, allow DME to be used as a substitute for propane and butane
in LPG as a cooking fuel. The well established LPG industry infra-
structure can be also used for DME without difficulty [6,7]. Around the
world, the number of vehicles running on LPG is increasing. Currently,
there are more than 10 million LPG operated cars on the road. DME can
be synthesized from biomass and, especially bio-DME can be used as a
blending agent with LPG (15–20 vol.) [8].
DME with the addition of a very little methanol and water is a good
alternative to diesel for transportation sector and small-scale power
generation industry. Based on Lower Heating Value (LHV), 1.2 L of
DME is equivalent to 1 L of diesel. Because of higher octane number
(55–60) with a low boiling point (−25 °C), it requires little modifica-
tion of existing diesel engine to utilize DME as a fuel. Inside diesel
engine, DME burns without sooting which is similar to an oxygenated
fuel additive and it also enhances favorable air/fuel mixture inside the
engine.
DME has a very low vapor pressure and is chemically and physically
stable. Thus, DME can be used as an aerosol propellant and can replace
chlorofluorocarbon (CFC), Freon and R-134, which are the main con-
tributors to ozone layer depletion. DME is used as a feedstock for a
variety of chemicals such as acetic acid [9,10], methyl acetate [11–13],
aromatics [14,15], gasoline [11], light olefins [16–18], higher ethers,
oxygenates, etc. [19,20]. As the fuel cell technology matures, the op-
portunity of DME as fuel in a hybrid vehicle is very high. DME is a
hydrogen carrier and it can be reformed to produce syngas (H2 + CO)
at a lower temperature (120–150 °C) when compared with other fuels
like diesel, gasoline, and methane (above 650 °C). DME can be cataly-
tically converted to other useful chemicals by reacting with syngas such
as formaldehyde [21], methyl acetate [22], and ethanol [23]. Other
usages of DME include as solvent, kiln fuel for ceramics, and for
welding and cutting plus brazing applications.
3. History of DME production
DME was developed as an aerosol propellant in 1963 by Akzo Nobel.
From 1970 global oil prices started to increase and Amoco was the first
company to invest in R and D of DME [24]. Until 1975 DME was pro-
duced as a by-product (3–5%) along with methanol in a high-pressure
production process [25]. A German patent filed in 1980 mentioned that
DME was present in methanol based fuel [26]. In 1990 a US patent was
published on the operation of a diesel engine with 95% DME [27].
National Institute for Petroleum and Energy Research laboratories
at Bartlesville in the US was the first to test DME in diesel engines in the
1980s [5]. In 1995, Haldor Topsoe, Amoco, and Navistar International
Corporation jointly started an investigation on the large-scale synthesis
of DME and concluded that methanol dehydration is a suitable tech-
nology for DME production. Amoco consortium was the first to justify
the use of DME as a non-polluting ultra-clean fuel with diesel engines,
which can meet the 1995 ULEV (California Ultra Low Emissions Ve-
hicle) regulations in the category of medium-duty vehicles. In Europe,
Volvo was the first company to carry out trials on buses with bio-DME.
DME blending in LPG (20% vol./vol.) is more convenient than using
DME as a diesel replacement because for the latter purpose, engines
have to be modified accordingly. Enhancement of blending of DME
from 20 to 30% does not need any major infrastructure other than the
storage capacity of LPG industry [5,28].
The use of DME as a gas turbine fuel was started by Toyo
Engineering, Haldor Topsoe Chiyoda Corporation and Snamprogetti/

Table 1
Comparison of properties of different fuels (information extracted from [3,4]).
Properties DME MeOH Methane LPG Gasoline Diesel

Chemical formula CH3OCH3 CH3OH CH4 C2-C5 C4-C12 C3-C25

Molecular weight (Da) 46.07 32.04 16.04 44.09 100–105 ≈200
Boiling Point (°C) −24.9 64.6 −161.5 −42 35–200 180–360
Vapour pressure at 20 °C 5.1 – – 8.4 – –
Liquid density at 20 °C g/cm3 0.67 0.79 0.42 0.49 0.71–0.77 0.832
Specific gravity (25 °C/4 °C) 0.661 0.786 0.55 0.51 0.739 0.82–0.95
Flammability limits in Air, Vol% 3.4–17 5.5–36 5–15 0.94–2.1 1.9–8.4 0.6–7.5
Wobbe Index, kJ/m3 46198 – 48530 69560 – –
Cetane No. 55–60 5 0 5 4–20 40–55
Calorific Value LHV, kcal/kg 6925 4800 12000 11950 11110 10800

300
U. Mondal and G.D. Yadav
ENI [8,24], and also due to a joint effort of three major institutions,
namely, Electric Power Development Corporation of Japan (EPDC), BP
Amoco and General Electric Co. of US [29]. In Japan, a 1.15 MW DME
fueled diesel power plant was established by FE Holdings, Daihatsu and
Iwatani Corporation [30]. Haldor Topsoe has developed advanced solid
oxide fuel cell technology which can use DME directly which eventually
increases the thermal efficiency of small-scale power generation plant
[8]. Chinese companies are converting coal into olefins such as ethylene
and propylene via methanol to olefins (MTO) process. Others include
Lurgi's methanol to propylene (MTP) process and Honeywell's advanced
MTO process. Both processes utilize coal gas as a raw material to pro-
duce methanol followed by DME production and finally, DME is reacted
to produce olefins. In 2001 International DME Association was estab-
lished followed subsequently by China DME Association (CDA), Japan
DME Forum (JDF) and Korea DME Forum (KDF). In 2016 Shenhuya
group and Dow Chemical Company of China announced to invest US
$10 billion to produce olefins from MTO process. Amoco along with
Indian Oil Corporation Limited (IOCL) and Gas Authority of India
Limited (GAIL) formed a joint venture in 1998 to promote DME in the
Indian power market which was less competitive and less risky for in-
vestment at that time. Biomass derived catalytic DME synthesis is being
pursued by Indian researchers.
4. DME synthesis
Coal or petroleum operated thermal power plants generate huge
quantities of CO and CO2 greenhouse gases and technologies must be
developed for CO2 capture and sequestering (CCS) facility. The
economy of the CCS plant only could be sustainable when it is sup-
ported by DME synthesis plant with a capacity of 3000–7500 TPD [28].
DME can be synthesized via two synthesis routes: (1) indirect
synthesis or two-step process, (2) direct synthesis or single step process.
The direct synthesis process comprises a single reactor process
where both reactions occur over a bifunctional catalyst. Linde/Lurgi,
Haldor Tospoe, Uhde, Toyo Engineering, and Mitsubishi Gas Chemical
Company are holding the licenses for the single-step DME synthesis
technology.
4.1. Indirect method
The indirect process is a dual-step catalytic process in which me-
thanol is synthesized from syngas or CO2 in the first reactor and then it
is dehydrated to produces DME in the second reactor. MGC, Toyo,
Udhe, and Lurgi are the companies which are developing DME pro-
duction technology by indirect synthesis [28].
In the presence of an acidic catalyst, methanol is dehydrated to DME
wherein the by product water acts as a reaction inhibitor by competing
with methanol for protons (Fig. 2). Kinetic modeling of methanol de-
hydration has been reported in the literature and a majority concludes
that the methanol dehydration reaction (Eq. (1)) follows either
Eley–Rideal kinetic model or Langmuir–Hinshelwood [31–33].
2CH3 OH CH3 OCH3 + H2 O °
H298 = 23.5 kJ/mol (1)
According to Bandiera and Naccache [34], the mechanism of DME
formation by methanol dehydration involves two adjacent sites on the
catalyst surface, i.e., one acidic site (H+) and another adjacent basic
site (O2−). Methanol is protonated on the acidic site to form
[CH3·OH2]+ which is instantly converted to CH3+ and H2O (Eq. (2)).
One methanol molecule is converted to CH3O− and OH− on the ad-
jacent basic site (Eq. (3)). Finally, DME is formed by combining two
activated species (CH3+ and CH3O−) (Eq. (4)).
CH3OH + H+ ↔ [CH3·OH2]+ → CH3+ + H2O (2)
2− − −
CH3OH + O ↔ CH3O + OH (3)
CH3+ −
+ CH3O ↔ CH3OCH3 (4)
301
Journal of CO₂ Utilization 32 (2019) 299–320
On the contrary according to Gates and Johanson [35], methanol
molecules are absorbed on the two adjacent acid sites of the catalyst.
Kiviranta-Paakkonen et al. proposed Eley–Rideal (ER) model for the
methanol dehydrogenation reaction, where one molecule of methanol
is absorbed on the acidic site of catalyst while other reacting molecule
remains in the bulk phase [32].
Ha et al. [36] studied a number of methanol dehydration reactions
and concluded that at the beginning of the reaction two methanol
molecules are non-dissociatively adsorbed on two acidic sites of an
acidic catalyst (m-ZSM-5). Then those two adsorbed methanol mole-
cules form an intermediate which instantly rearranges itself to form
methyl carboxyneum ion and carbenium ion or two methyl carbox-
yneum ions. The second step was regarded as the rate determining step
[36]. DME formation from methanol is also demonstrated by associa-
tive and dissociative pathways and both the reactions are proposed to
carry out on the Brønsted acid site [37–39]. Methanol to dimethyl ether
(MTD) reaction with ZSM-22 catalyst has been studied on the basis of
density function theory (DFT) by Moses and Nørskov [40] who pro-
posed that both the associative and dissociative pathways are re-
sponsible for methanol conversion but the dissociative pathway is faster
than the former with similar dependency on acidic site. They have es-
tablished a linear correlation between the strength of acidic site and
activation energy and proposed that weaker acid sites produce higher
activation energies. In the case of two-step dissociative pathway, DME
synthesis step is a bit slower than the water releasing step. Hence, DME
formation is the rate determining step for the dissociative pathway.
Cassone et al. [41] have done computational analysis based on ab initio
molecular dynamics method to study a novel electrochemical pathway
to produce DME from methanol.
The indirect process of DME synthesis from CO2 is shown in Fig. 3.
For the methanol synthesis process, matured methanol-synthesis cata-
lysts are used and a majority of them are copper based catalysts. While
for the methanol dehydration process, acidic catalysts like zeolite,
alumina and sulphuric acid have been used. Thus with the existing
catalyst technology setting up a DME plant is rather cheap but the
output is a mixture of methanol, water, and DME which has to be
distilled for purification, separation, and recycling. Methanol cost is one
of the deciding factors for DME price which it is generally double the
cost of methanol [3,42].
Despite disadvantages, most of the DME plants operate with indirect
synthesis process where a solid acid catalyst (usually alumina) is used
for vapour phase dehydration of methanol. H2SO4 is also used as an
acid catalyst by some industries, e.g. Jiutai Energy Group of China. and
the reaction mechanism is shown below (Eqs. (5) and (6)). The ad-
vantages of this process are that the sulphuric acid can be recycled
several times and the weakened acid is used as a raw material in the
fertilizer industry; this liquid phase catalytic dehydration process can
reduce the process cost by one-third of actual cost [43].
CH3OH + H2SO4 → CH3HSO4+H2O (5)
CH3HSO4 + CH3OH → CH3OCH3+H2SO4 (6)
4.2. Direct method
Though the direct or one-pot synthesis of DME from syngas is a one-
step process, it involves three reactions, i.e. methanol formation by
syngas hydration, methanol dehydration and water-gas shift (WGS)
reaction (Eqs. (7)–(9)). Hydrogen produced in the WGS reaction is used
in the methanol synthesis reaction and methanol (Eq. (7)) is thereafter
dehydrated to DME. These reactions are conducted in a single reactor
packed with a bifunctional catalyst for the simultaneous occurrence of
the reactions. The overall reaction of the syngas to dimethyl ether (STD)
process can be expressed as Eq. (10).
CO + 2H2 CH3 OH °
H298 = 90.6 kJ/mol (7)
U. Mondal and G.D. Yadav Journal of CO₂ Utilization 32 (2019) 299–320

Fig. 2. Indirect method of DME synthesis via methanol dehydration reaction [32,35].

2CH3 OH CH3 OCH3 + H2 O °

H298 = 23.4 kJ/mol (8) is produced via syngas hydration. The single step conversion method is
getting more attention in the industry because of the higher one pass
H2 O + CO H2 + CO2 °
H298 = 23.4 kJ/mol (9) conversion of syngas and it requires a lower supply of hydrogen to
produce DME in comparison to dual step process. Thermodynamic
3CO + 3H2 CH3 OCH3 + CO2 °
H298 = 245.8 kJ/mol (10) analysis of direct DME synthesis from syngas and CO2 reaction has been
CO2 is hydrogenated to produce DME and like in the STD process, done by Moradi et al. [44] and Ateka et al. [45]. By comparing the heat
methanol is formed as an intermediate product followed by DME generation between Eqs. (9) and (14), it can be concluded that the use
synthesis through methanol dehydration. Both methanol synthesis and of CO2 in the direct synthesis process produces less heat and thus the
methanol etherification reactions occur in parallel (Eqs. (11) and (12)) reaction is more thermodynamically stable and the catalyst bed over-
along with the reverse water-gas shift (rWGS) reaction as a side reaction heating problem with syngas can be avoided. However, H2O formation
(Eq. (13)). The overall reaction of CO2 hydrogenation to produce DME during the reaction promotes the catalyst deactivation and reduces
is given by Eq. (14). DME yield. Another advantage of using CO2 is its higher oxidation
power compared to syngas and the presence of CO2 in the supplied
CO2 + 3H2 CH3 OH + H2 O °
H298 = 49.4 kJ/mol (11) reaction gas mixture influences the active site of catalyst to produce
more methanol [46].
2CH3 OH CH3 OCH3 + H2 O °
H298 = 23.4 kJ/mol (12) Commercialization of DME production from syngas is not econom-
ically viable as it requires a higher amount of energy and releases
H2 + CO2 H2 O + CO °
H298 = 41.4 kJ/mol (13) greenhouse gases into the atmosphere via water-gas shift reaction. DME
production has to adopt new technologies to be more energy efficient
2CO2 + 6H2 CH3 OCH3 + H2 O °
H298 = 122.2 kJ/mol (14)
and environment-friendly. Utilization of CO2 for the purpose of DME
The direct method of DME synthesis is more practical as both the production can be a noble way to prevent accumulation of greenhouse
reactions are performed in a single reactor and thus the operational cost gas in the environment. The present technology is not mature enough to
will be less (Fig. 4). Integration of methanol formation and methanol convert CO2 into DME with higher conversion rate and selectivity. This is
esterification reaction makes the whole process more thermo- an equilibrium limited reaction and if the produced water can be with-
dynamically favorable as the methanol formation from syngas hydro- drawn from the reactor, the equilibrium can shift toward DME synthesis.
genation is exothermic and reversible (Eq. (1)). The formation of water
molecules during methanol dehydration reaction (Eq. (8)) is also ben- 4.3. Other routes
eficial for hydrogen generation in WGR reaction (Eq. (9)). The reactions
(Equations (7), (8) and (9)) produce a synergic effect on reaction Methane has a high potential to be used as a precursor for DME
equilibrium and as more methanol is converted to DME, more methanol production via a dual-step synthesis process. Firstly methane is

Fig. 3. The indirect process of DME synthesis from the gaseous mixture of CO2 and H2.

302
U. Mondal and G.D. Yadav
Fig. 4. the Direct process of DME synthesis from the gaseous mixture of CO2 and H2.
transformed into methyl halide (such as CH3Cl, CH3Br) by reacting with
hydrogen halide via oxidative halogenation reaction and then methyl
halide is converted to higher hydrocarbons including DME via hydro-
lysis and carbonylation reactions [47–52]. Yang et al. [47] have re-
ported the conversion of methane into methyl bromide by reacting with
oxygen and hydrogen bromide over Rh/SiO2 catalyst. One of the pro-
blems associated with this reaction is that ony ∼10% methane is
converted to CO and CO2. You et al. [48] co-fed CO and CO2 along with
methane and HBr/H2O in the oxidative halogenation reactor to produce
CH3Br and avoided generation of CO2.Then the produced methyl bro-
mide was hydrolyzed to produce DME over a metal chloride catalyst
supported on silica (ZnCl2/SiO2). Corrosion of the reactor is a common
problem when methyl halide is used as a precursor. This issue was re-
solved by Prakash et al. [49] who utilized poly(4-vinyl pyridine) as a
catalyst in the place of liquid amines. Methyl halide is also used to
synthesize DME and methyl acetate as a by-product via oxidative car-
bonylation reaction by reacting with CO and Cu2O in the presence of
SbF5/graphite as a catalyst [50]. Methanol and DME were produced
when the mixed oxide was used as a catalyst for the oxidative carbo-
nylation of methyl bromide [51,52].
5. Catalysts for DME synthesis
Many challenges still exist for DME production despite several ef-
forts during the last few years. The development of a highly active and
efficient catalyst for CO and CO2 hydrogenation is still a distant dream.
One pot DME synthesis (direct method) from either syngas or CO2 in-
volves two separate reactions (methanol formation and methanol de-
hydrogenation). The catalyst should perform as a redox function which
first turns gases into alcohol which is dehydrated to the ether on an acid
site. As stated earlier the indirect method of DME synthesis involves
both the reactions in separate reactors whereas the direct method is
more attractive since it alleviates the thermodynamic constraints of
methanol synthesis from CO2 or CO and leads to higher conversion as
well as selectivity [53–55]. It is highly recommended by the industry to
use a single pot synthesis technique for DME synthesis to reduce pro-
duction cost [55,56].
Other than the metal function and acid function of the of bi-func-
tional catalyst, some other important factors also influence the pro-
ductivity of the one-pot process, such as (i) preparation method of the
catalyst, (ii) sintering of the copper particle, and (iii) catalyst deacti-
vation. It is very important to know that the product distribution of
direct DME synthesis reaction does not only depend on the thermo-
dynamics of the reaction but also on the reaction kinetics. The heat
conduction properties of the bi-functional catalyst are very low and the
reaction process is carried out in the range of 523–673 K and pressure of
10–50 bar [57,58]. In the case of the indirect process, irrespective of the
process followed, the productivity is highly dependent on the catalyst
properties. In the following section, the effect of metal function and
acid function on the DME synthesis is discussed.
303
Journal of CO₂ Utilization 32 (2019) 299–320
5.1. Methanol formation reaction
5.1.1. Copper based catalysts
BASF was the first company to commercially produce methanol from
syngas containing CO2 by using ZnO-Cr2O3 as a hydrogenation catalyst.
In 1960 ICI introduced copper zinc oxide alumina catalyst for selective
production of methanol from naphtha/natural gas under milder reaction
conditions. Thereafter a lot of research was done on Cu-ZnO based cat-
alyst combined with other metals. Among them Cu-ZnO based catalysts
prepared by co-precipitation method have shown higher conversion and
selectivity. The metallic Cu clusters in Cu-ZnO-Al2O3 are the active sites
for methanol synthesis and WSG reactions; and the conversion and se-
lectivity are dependent on copper dispersion and metal surface area
[58–60]. A typical example of the commercial catalyst is Cu-ZnO-Al2O3,
which is usually composed of 50–70 mol% of CuO, 20–50 mol% of ZnO
and 5–20 mol% Al2O3. According to Chinchen et al. [61], ZnO is the best-
performing oxide among MnO, Cr2O3, and SiO2 in terms of various
functionalities and it shows a good promoting effect for methanol
synthesis but not for rWSR reaction [62]. The primary role of ZnO is to
provide an optimum dispersion of metallic Cu, by acting as a geometric
spacer between the Cu nanoparticles which leads to higher number of
active sites on which syngas conversion to methanol takes place [55].
The other functions of zinc oxide are to hinder sintering of copper par-
ticles as well as to disperse catalyst poison such as Cl and S to reduce
poisoning. The ratio of Cu+/Cu° is also appropriately maintained by ZnO
by creating Cu+-O-Zn active sites, as both the Cu states are important in
methanol formation. da Silva et al. [63] concluded that ZnO is re-
sponsible for the strong metal-support interaction with Cu nanoparticles,
which were referred to as “methanol active copper”. The size of the
copper particle and its dispersion over the support material are greatly
varied with the type of precipitant, Cu/Zn molar ratio, calcination tem-
perature, etc. although excessive ZnO is responsible for deactivation of
the catalyst. Thorhauge et al. [64] have demonstrated the role of Zn
particles on Cu dispersion and its influence on syngas to methanol con-
version. Le Valent et al. [65] have developed a mathematical model of
methanol synthesis reaction on core-shell Cu-ZnO catalyst to correlate
successfully the number of Cu-ZnO contact points with observed catalytic
activity. Further addition of trivalent ions (M3+) such as Al3+ in Cu/ZnO
catalyst leads to the enhanced thermal and chemical stability of the
catalyst, higher Cu dispersion and metal surface area [66]. Based on
previous studies Sugawa et al. [67] have proposed the following order of
activity of different metals for methanol formation from CO2:
Cu ≫ Co = Pd = Re > Ni > Fe ≫ Ru = Pt > Os > Ir = Ag = Rh >
Au
Water generation during hydrogenation of CO2 for methanol pro-
duction leads to the unsatisfactory performance of Cu-ZnO-Al2O3, since
alumina possesses strong hydrophilic property; and in order to solve
this problem, lower hydrophilic promoters have been adopted such as
ZrO2 [68,69]. Various Cu based zirconia catalysts have been reviewed
by Raudaskoski et al. [70] who have described how Zr promoted high
U. Mondal and G.D. Yadav
Cu dispersion results in higher conversion and more methanol se-
lectivity. To further enhance the performance of ZrO2 containing Cu
based ternary catalyst, additional promoters have been incorporated
such as Ti [68]. Cu-ZnO-ZrO2-TiO2 quaternary catalyst prepared by
oxalate precipitation method led to higher conversion and selectivity
due to the presence of both the promoters Zr and Ti. The addition of Zr
and Ti in the catalyst structure led to a decrease in crystallite size of
CuO, ZnO and increased CuO-ZnO interaction [68]. Angelo et al. [71]
have studied the effect of CeO2 as a promoter in Cu-ZnO-Al2O3 catalyst
and found that CeO2 addition decreases the Cu crystalline size and does
not benefit the reaction in any way. Garciani et al. [72] have introduced
a new site for CO2 activation and hydrogenation on the ceria-copper
interface. They have shown that the hydrogenation reaction on CeOx/
Cu (100) is 200 times higher than Cu (100) and 14 times higher than
Cu-ZnO. Fornero et al. [73] have shown that Cu-Ga2O3-ZrO2 catalyst
performed better than Cu-Ga2O3 and Cu-ZrO2 catalysts.
Other than the foregoing metal promoters, various other metal and
non-metal promoters have been added in to the Cu-ZnO bi-metallic
system for methanol synthesis; these include Mn [74], Cr [75], Au [76],
La [77], Ce [77], V [78], graphene [79], carbon [74,80] or mixture
[77,81,82] among them. It was observed that Zr, Al, and Ga showed the
maximum activity in terms of conversion and selectivity [83]. Among a
number of catalysts studied, LaCr0.5Cu0.5O3 and Cu-ZnO-Ga2O3/SiO2
have shown better methanol formation rate with high selectivity (as
high as 99.5%), but their stability and scalability have not been tested
[84]. Martin et al. [85] have studied the activity of In2O3/ZrO2 catalyst
for methanol synthesis from CO2 hydrogenation at very low pressure
compared to conventional system. They have achieved 100% methanol
selectivity compared to Cu-ZnO catalyst and shown 1000 h time on
stream (TOS) stability.
5.1.2. Palladium-based catalysts
A number of Pd based catalysts have also been developed for me-
thanol synthesis by hydrogenation of CO and CO2 such as Cu/SiO2 [86],
Li-Pd and Na-Pd [87], Pd-Ga2O3 [88], Pd-βGa2O3 [89], Ga2O3 pro-
moted Pd-SiO2 [90,91], Pd-Cu/SiO2 [69], and Pd-ZnO [92]. Koizumi
et al. [93] have reported that methanol synthesis from CO2 by Pd cat-
alyst can be further improved by adopting two strategies such as (i)
using uniform mesoporous support for the catalyst (SBA-15, MCM-41),
and (ii) use of alkali/alkaline earth metal additives.
5.2. Methanol Dehydration to DME
5.2.1. Alumina
The second step of indirect DME synthesis is the dehydration of
methanol for which generally solid acid catalysts are employed, and the
most desired properties of the solid acid catalyst require them to be
hydrophobic, stable at high temperature, highly active and selective for
the desired product. One of the earliest studies reported that DME was
formed by methanol dehydration using alumina as a catalyst at the
temperature range of 300–400 °C [94]. Methanol dehydration process
has several licensors around the globe such as Linde/Lurgi, Haldor
Tospoe, Toyo Engineering, Mitsubishi Gas Chemical Company (Japan),
Uhde, China Southwestern Research Institute of Chemical Industry and
China Energy. This reaction can be carried out in either the liquid or
vapor phase, depending on the catalyst used, at suitable reaction tem-
perature (100–300 °C) and pressure (1–20 bar). Among the solid acid
catalysts applied for methanol dehydration, alumina and zeolites are the
most popular as they are stable at high temperature and pressure, having
a high surface area, low cost and most of the acid sites have lower acidity
(Lewis acid site). Sung et al. [95] have investigated different crystalline
phases of alumina for the methanol dehydration reaction and concluded
that γ-Al2O3 showed the second highest catalytic activity among other
phases and the order of activity of different phases was as follows:
304
Journal of CO₂ Utilization 32 (2019) 299–320
η-Al2O3 > γ-Al2O3 ≫ θ-Al2O3 ≫ (χ + γ)-Al2O3 ≫ δ-Al2O3 > α-
Al2O3 ≈ κ-Al2O3
γ-Al2O3 forms Lewis acid site during the calcination process and al-
though it is very active, it strongly binds to water molecules and gets
deactivated instantly. Xu et al. [96] studied the effect of water content,
reaction temperature, and catalyst acidity on methanol conversion and
in this regard, a number of catalysts with different acidity (different
silica content) such as γ-Al2O3, amorphous alumina-silica, titania
modified zirconia, and HZSM-5 have been considered. Water molecules
block the active sites of the catalyst, and it was reported that γ-Al2O3
was the most affected whereas HZSM-5 the least. More acidic catalyst
shows an increase in the activity of the catalyst. γ-Al2O3 is affected by
water content because it possesses the most number of strong Lewis
acid sites to adsorb water molecules [97].
5.2.2. Zeolites and modified zeolies
Considerable attention is focused on the use of zeolites as a solid
acid catalyst for methanol dehydration reaction. Zeolites are crystalline
aluminosilicates which are widely studied for their shape selectivity
which comes from their well-defined microporous structure. The shape
selectivity can be further tuned as per the reaction by turning the
opening and special orientation of the channels, size, and location of
the cases. Zeolites possess both Brosted and Lewis acid sites and the
distribution, number, position and strength of these acid sites are the
main deciding factors for catalytic activity [98]. The main advantage of
zeolite is the stronger acid sites, which allows the reaction to be carried
out at low reaction temperature [99,100] Vishwanathan et al. [99]
reported 80% conversion of methanol to DME at 230 °C by HZSM-5
catalyst, while γ-Al2O3 required a higher temperature of 320 °C to reach
the same conversion [99]. Olefins and coke formed through some un-
desired side reactions at the high strength acid sites of zeolites and
blocking of pore structure by coke molecules were the main reasons for
deactivation of zeolites [101].
Catizzone et al. [102] have investigated several types of zeolites for
methanol dehydration reaction based on the channel openings (8–12
membered rings) and channel orientation (1-,2- and 3-dimensional
channel orientations). One dimensional zeolite such as MTW or MOR
have shown high DME selectivity at 240 °C but deposition of coke leads
to early deactivation of the catalyst. With medium pore opening the 1-D
zeolite turn over number (TON) was better and it showed good re-
sistance to coke deposition. SAPO-34, MFI, and BEA are 3-D channel
zeolites which have been investigated by the same research group who
found that despite the small channel openings (3.8 Å) of SAPO-34, it
showed high DME selectivity, but it rapidly got deactivated by coke
deposition [102,103]. When channel intersection and channel openings
have a similar size such as MFI and BAE structure, higher stability was
observed with coke deposition [104]. Tang et al. [105] have studied
ZSM-5-MCM-41 composite catalyst which is both microporous and
macroporous, having a better activity for methanol dehydration [106].
Several studies on FER zeolites for the methanol dehydration reaction
have shown high DME yield. Catizzone et al. [107] have investigated
FER zeolites with different acidity (governed by Si/Al ratio) for me-
thanol dehydration reaction. Higher aluminum content increases me-
thanol conversion and Lewis acid sites are more active at a lower
temperature (240–160 °C) than Bronsted acid sites [108].
The activity of zeolites can be further improved by decreasing sur-
face acid strength or decreasing total number of acid sites of the cata-
lyst. The strength of acidic sites of the solid acid catalyst is of great
importance, as DME formation occurs at the low acidic side (Lewis acid)
and DME is further converted to olefins on strong acid sites. Several
reports have appeared on Na, Mg, Zn, Zr impregnated HZSM-5 catalyst
for DME synthesis from methanol and it was demonstrated that with
these metal impregnation strong acidity was decreased which reduced
coke deposition [109]. Khandan et al. [110] have shown with
U. Mondal and G.D. Yadav
incorporation Zr in HZSM-5 framework DME yield increases from 53 to
92%. Kim et al. [111] have studied γ-Al2O3 impregnated HZSM-5 cat-
alyst for methanol dehydration reaction and obtained 50% conversion
with 99% DME selectivity.
5.2.3. Heteropolyacid (HPA)
Heteroplyacids (HPAs) are also used as catalysts in methanol de-
hydration reaction. Keggin-type HPAs, which are represented as
H8−n[Xn+M12O40], where “X” is heteroatom (such as Al3+, P5+, Si4+,
etc.), “n” is the oxidation state and “M” is the metal ion, are the most
commonly used. The heteroatom in the HPAs possesses highly acidic
Bronsted acid site. Thus HPA performs better at lower reaction tem-
perature compared to zeolites. Carr et al. [38] have done methanol
dehydration reaction over Keggin type HPA clusters with different
heteroatoms (X = P5+, Si4+, Al3+, and Co2+) and proposed that the
reaction mechanism follows associative reaction pathway. Alharbi et al.
[112] have studied the activity of HPA in methanol dehydration reac-
tion and compared results with zeolite with different acidity (Si/
Al = 10–120) in terms of the turn over reaction frequency (TOF) and
acid strength of the catalyst. HPA containing tungsten/phosphorus
(HPW) showed TOF of 53 h−1 whereas the most active zeolite, HZSM5
had TOF of 1 h−1. Ladera et al. [113] have proposed that the activity of
HPAs can be further enhanced by using TiO2 as support as it enhances
the accessibility of the methanol molecules to the proton site of HPAs.
5.2.4. Ion exchange resin (IER)
Ion exchange resins (IER) are also employed for methanol dehy-
dration reaction. IER is a copolymer of divinyl benzene/styrene and
sulfonic acid is present in the IER structure. The main advantage of
using IER as an acid catalyst is the use of low reaction temperature in
the range of 30–150 °C [114,115]. The activity can be further improved
by incorporation of Lewis acid site through reaction with aluminum
chloride or boron trifluoride [116]. Hosseininejad et al. [117] have
shown that Amberlyst 35 has the highest catalytic activity among other
IERs, γ-alumina, and zeolites (HY, HZSM5, HM zeolites) at the tem-
perature range of 110–135 °C.
5.2.5. SBA-15 and HMS supported catalysts
Tokey et al. [118] have synthesized alumina impregnated SBA-15, a
mesoporous structure aluminosilicate, by one-pot hydrothermal synth-
esis and used it for DME production by the methanol dehydration re-
action demonstrating methanol conversion value close to equilibrium
conversion with 100% DME selectivity. Al-HMS with different Si/Al
ratio has been synthesized by Sabour et al. [119] and tested for DME
production by methanol dehydration reaction. Al-HMS with Si/Al ratio
of 10 showed the best catalytic activity with methanol conversion of
89% with 100% DME selectivity. When the Si/Al ratio was increased,
the conversion increased but DME selectivity decreased.
5.3. Direct method of DME production
One pot conversion of CO and CO2 to DME is challenging and en-
ergetically unfavorable. Suitable reaction conditions and efficient cat-
alyst are required to carry out such reactions. During DME synthesis
reaction from CO2, CO and water are produced by reverse water gas
shift (rWGS) reaction and other hydrocarbons are also formed from
methanol. A large quantity of water formation which is a big problem
during DME synthesis from CO2, as it creates a thermodynamic lim-
itation for methanol formation and methanol dehydration reaction, and
thus the DME yield is lower when CO2 is used as compared to CO.
Many reports can be found on syngas to DME (STD) reactions with
physical mixtures of catalysts used for methanol synthesis and me-
thanol dehydration (e.g. Cu/ZnO/Al2O3 and γ-Al2O3). It was reported
that CO conversion increased from 50 to 93% and DME selectivity from
34 to 52% when the reaction temperature was elevated to 240–290 °C
with CO: H2 mole ratio of 2 [120–123]. Cu/ZnO/Al2O3 (CZA) catalyst is
305
Journal of CO₂ Utilization 32 (2019) 299–320
an industrially applied mature catalyst which is well researched. Like
syngas, CO2 is also converted to DME by a physical mixture of CZA and
γ-Al2O3 catalysts [124–126]. Takeguchi et al. [127] have studied DME
synthesis from a mixture of CO and H2 by physically mixed Cu/ZnO/
Al2O3/Cr2O3/Ga2O3 and silica-modified γ-Al2O3 catalysts. Silica
loading increases the Bronsted sites and catalyst surface area. Other
studies have reported that when γ-Al2O3 was modified with niobium
sulfate (Nb2(SO4)3) and treated with 0.1 mol NH4F solution, both the
surface area and acidity of the catalyst increased [128]. Joo et al. [129]
have suggested that strong acidic sites on γ-Al2O3 converted methanol
and DME into CO through reforming reaction and thus prior treatment
of γ-Al2O3 and HZSM-5 with sodium carbonate and formaldehyde
would increase the number of weak acid sites.
A huge number of studies have been reported on the effect of dif-
ferent promoters on the Cu-metal functions in the hybrid bi-metal
catalyst such as Ga [130], Mn [131], Pd [132], La [133], Zr [82–84], Y
[134], magnesia [130], as well as carbon nanotubes [135], etc. and the
effect of different promoters on Cu dispersion, activity, and selectivity
of DME have been discussed. According to Venugopal et al. [134]
among the different promoters (Ga, Zr, La, Y) in CZA catalyst, yttrium
(Y) showed the highest CO conversion (70%) and DME selectivity of
47.7% which was due to Cu particle grain growth and surface area.
Different functionalities of various promoters enhance the catalyst ac-
tivity of CZA catalyst; for instance, Ga increases the inverse spillover of
hydrogen [130], and Zr increases the crystalline size of Cu [136], etc.
MgO modified γ-Al2O3 dehydration catalysts in hybrid form also have
been studied to witness better CO conversion and DME activity [130].
When alumina content is more than 50 wt% in Cu/ZrO2 and calcination
temperature is more than 500 °C, CZA catalyst itself can be used as a
hybrid catalyst [137]. Gel type slurry catalyst made up of CZA with
AlOOH binder showed good catalytic activity for DME synthesis as
AlOOH acts as methanol dehydration catalyst [138].
Various mesoporous catalysts also have been extensively reported
for the one-pot synthesis of DME from CO and CO2. Jiang et al. [139]
prepared a mesoporous Cu-γ-Al2O3 catalyst with different Cu mol ratio
by evaporation induced self-assembly method and it showed excellent
CO conversion (72%) and DME selectivity (69%) at 310 °C and 50 bar
pressure. Wang et al. [140] prepared mesoporous Al2O with highly
dispersed Cu by combustion synthesis method and it showed good ac-
tivity with high DME selectivity for 56 h time on stream (TOS).
Zeolite-based catalysts have been used as an acid function in a bi-
functional catalyst as the hydrophobic nature of zeolite is responsible
for the higher activity at the lower reaction temperature, which makes
the methanol formation step thermodynamically more favorable
[141–143]. Zeolites of proton and non-proton form (HZSM-5 and ZSM-
5), ferrierite, zeolite-Y, and mordenite are among the most famous
zeolites used as an acid function in DME synthesis. Ramos et al. [144]
investigated different solid acid catalysts mixed with a commercially
available methanol synthesis catalysts such as porous alumina (alu-
mina-C), non-porous alumina (alumina-D), tungstated zirconia (W-
ZrO2), sulfated zirconia (S-ZrO2), and HZSM-5. HZSM-5 was the most
active catalyst among the rest when employed for DME synthesis from
CO, which was due to the higher number of Bronsted acid sites present
on HZSM-5. Cu-Mn-Zn supported on HY zeolites, modified via ion ex-
change with rear earth (Nd, La, Ce, Sm, Pr, and Eu) [145] and transition
(Ni, Co, Fe, Cr, and Zr) [145] metals, as hybrid catalysts have been
utilized for DME synthesis. The effect of Si/Al (30, 80, 280) ratio of
HZSM-5 and HY catalyst in CZA-zeolite on CO conversation and DME
selectivity has been studied by Xie et al. [146]. In their case, the lowest
CO conversion of 46.7% and the highest DME selectivity 70.4% were
observed with HZSM-5 (Si/Al = 280) whereas the highest CO conver-
sion of 87.7% and the lowest DME selectivity of 65.9% was achieved
with HZSM-5(Si/Al = 30). García-Trenco et al. [147] and others have
shown that CZA-zeolite catalysts are deactivated due to Cu sintering as
Cu2+ ions (and sometimes Zn ions also) migrate to the HZSM-5 and
increase the number of Lewis acid sites. In order to modify and study
U. Mondal and G.D. Yadav
the influence of acid sites of zeolites, modification of HZSM-5 catalyst
with a number of basic oxides (i.e., MgO, ZnO, CaO, and Sb2O3) and
transition metals (Zr and Fe) was carried out and it was found that due
to acid sites being shifted to weaker strength, DME selectivity was
improved [148,149]. Pure and modified ferrierite has become quite
popular for the direct DME synthesis from CO, as modified ferrierite is
highly DME selective and stable at high reaction temperature. Mon-
tesano et al. [150] studied the influence of zeolite structure and to-
pology on DME yield and concluded that the main reason for ferrierite
activity was that it provides a path for small molecule diffusion (i.e.
MeOH and DME). Prasad et al. [151] also reported higher activity and
stability of CZA/HFER catalyst for DME synthesis compared to HZSM-5,
HY, and NaY. Many studies have shown that CZA/Zr incorporated
HFER catalyst showed higher catalytic activity than HZSM-5 and Y-
zeolites. Zr modification of FER has resulted in low Cu surface area with
presence of a required number of acid sites for DME synthesis
[123,152].
Naik et al. [124] compared the catalytic activity of γ-Al2O3 and
HZSM-5 (Si/Al = 60) by mixing with CZA catalyst for direct conversion
of CO2 to DME in a fixed bed reactor at 260 °C and 5 MPa. HZSM-5 was
more active in terms of CO2 conversion (30% vs 20%) and DME se-
lectivity (75% vs 5%) and it also possessed better catalyst stability. So it
was concluded that the use of γ-Al2O3 acid function in the hybrid cat-
alyst is very disadvantageous when single pot CO2 to DME conversion
reaction is considered. Ge et al. [153] observed that for good conver-
sion and yield of DME, both the active sites of catalyst should be in
close proximity. Frusteri et al. have investigated the function of an acid
catalyst in the hybrid catalytic system, which was prepared via gel-
oxalate precipitation of CuZnZr precursors on HZSM-5 (Si/
Al = 27–127) [154]. It was found out that acidity of zeolite has to be
tuned accordingly to achieve highest DME selectivity along with good
resistance to water deactivation. HZSM-5 with Si/Al ratio of 127 gave
the highest methanol conversion but poor resistance to water deacti-
vation. HZSM-5 with Si/Al of 27 offered poor methanol conversion but
good water resistance and that HZSM-5 with Si/Al ratio 38 was the best
for one step CO2 to DME conversion and water resistance [154].
Other than the acidic property, the textual properties of zeolites also
influence the catalytic activity for CO2 conversion. Therefore Frusteri
et al. [155] prepared hybrid grains of the catalyst by co-precipitating
CuZnZr on different zeolites with different channel supports (FER,
MOR, MFI) for direct synthesis of DME from CO2. During the catalyst
testing, the following trend of catalyst activity was observed,
CuZnZr/FER > CuZnZr/MOR > CuZnZr/MFI
Lower mass transfer limitation was offered by FER as metal oxide
anchored on the lamellar crystals of the FER zeolite generates more
number of Lewis acid and CO2 gets activated on those sites. There are
several other reasons for the deactivation of zeolite catalysts, among
which the most common mechanisms are: (i) coke deposition on the
active site of the catalyst, and (ii) pore blockage inside the zeolite
channels by carbonaceous compounds. It is experimentally proved that
coke deposition in zeolite is very much dependent on the shape of the
channels [156] and zeolites with large pores are more prone to coke
formation compared to medium pore size zeolites [157]. Deactivation
of zeolite can be controlled by incorporation of Na into the zeolite
structure; it leads to moderate number of Bronsted acid sites and de-
creases the acid strength of the HZSM-5 [121]. One of the other
methods for enhancing the resistance to carbon formation is by creating
a silicalite shell around the HZSM-5 [158,159]. Ateka et al. [160] have
established a kinetic model of direct synthesis of DME from syngas and
CO2 using CuO-ZnO-MnO/SAPO-18 bifunctional catalyst in a fixed bed
isothermal reactor. The kinetics was established by considering that all
reactions occurred during both methanol synthesis and methanol de-
hydration reaction.
306
Journal of CO₂ Utilization 32 (2019) 299–320
6. Effect of catalyst preparation method
A number of methods for synthesizing hybrid catalysts have been
reported in the literature such as co-precipitation [131,161], sol–gel
[137], precipitating sedimentation [162], impregnation [163], and wet
chemical methods [164]. Among them, the co-precipitation and phy-
sical mixing methods are the most widely used preparation methods for
hybrid catalysts. Co-precipitation method involves the co-precipitation
of active functions of methanol synthesis catalyst (MSC) over an aqu-
eous or organic solution of precursors of methanol dehydration catalyst
(MDC). The physical mixing of both the MSC and MDC functions is the
other method. There are a few drawbacks of this method however such
as the uncontrolled size distribution of the particles, random active site
distribution on the catalyst surface and aggregation of catalyst particles
during precipitation. Ahmad et al. [164] have compared the hybrid
catalyst preparation method for STD reaction including impregnation,
co-precipitation, co-precipitation-impregnation, co-precipitation sedi-
mentation, and oxalate methods. According to their study oxalate, co-
precipitation and co-precipitation sedimentation are better performing
methods of hybrid catalyst preparation among the rest. In recent years,
a number of innovative STD catalyst preparation methods have been
proposed and developed; among them, sonochemical assisted, physical
sputtering, and core-shell catalyst are the most popular. When the co-
precipitation method is coupled with the ultrasound irradiation, the
ultrasound waves lead to a high nucleation rate limiting particle growth
and enhance the interaction between particles and fragments of ag-
gregates of the catalyst [165]. Allahyari et al. [166] have prepared
CuO-ZnO-Al2O3/HZSM-5 nanocatalyst by the sonochemical method
and it was reported that longer irradiation time led to bigger CuO
crystals, higher surface area along with smaller particle aggregates and
uniform active site distribution. Khosbin et al. [167] compared the
activity of STD nanocatalyst prepared by co-precipitation-ultrasound
and co-precipitation- physical mixing method. It was found that catalyst
prepared by the former method showed better catalytic activity (50.5%
CO conversion and 55% DME selectivity) in comparison to the latter
method (CO conversion 16.5% and DME selectivity of 38%) at identical
reaction conditions. Hosseini et al. [168] prepared nanocrystalline γ-
Al2O3 by sol–gel method and found that catalyst prepared by the sol–gel
method showed higher activity than that prepared with precipitation
method. The non-aqueous sol–gel method showed even better activity
than aqueous sol–gel one. Some other advantages of the sol–gel method
include low-temperature preparation method, a high degree of purity,
ability to control pore volume and pore size distribution.
Irrespective of the catalyst preparation method adopted, the cata-
lytic activity decreases with TOS due to the migration of copper par-
ticle, sintering [169], oxidation, coke deposition [144,170], the strong
interaction between the CZA and methanol dehydration catalyst [171]
and partially with the impurities present in syngas [172]. Therefore,
many scientists have proposed a different approach to maximizing the
stability of the Cu-based catalyst. Garciá-Trenco et al. [173] confined
Cu nanoparticles inside the pores of zeolite to improve the stability of
catalyst in DME synthesis. In a different approach, Cu-ZnO particles
were confined inside the pores of mesoporous silica (SBA-15) to avoid
direct contact between CZA and SBA-15 surface [174]. This approach
eliminated any kind of detrimental interaction, as well as sintering of
Cu particles from the catalyst structure and further analysis with
HRTEM, showed the presence of Cu nanoparticles size of 5–6 nm. This
catalyst preparation approach has been proved to be more effective
than physical grinding or mixing method.
Millimeter size capsule catalyst is also employed for STD reaction
where CZA core is covered by a thin layer of acidic zeolite shell [175].
This method is advantageous as very less amount of by-product is
formed and high DME selectivity achieved, because the active sites on
the surface of CZA catalyst and the acid sites of MDC do not much
U. Mondal and G.D. Yadav
interact. Methanol produced on CZA catalyst has to diffuse through the
acidic sites of HZSM-5 on the shell side to get converted into DME
[176]. This coated capsule catalyst is not the perfect catalyst for direct
DME synthesis as multiple defects and cracks are formed on the zeolite
shell side during acidic hydrothermal synthesis which leads to a de-
crease in CO conversion. A second layer of silicate-1 zeolite on the
HZSM-5 shell was given as a protective layer [175,177] for HZSM-5
layer. Pd/SiO2 core encapsulated with dual layer coating has shown
good catalytic activity for DME synthesis. SiO2 has been used as ad-
hesive for the preparation of SAPO encapsulated MSC cores (Cr/ZnO
[178], CZA [54]). Urea hydrolysis assisted simple homogeneous pre-
cipitation method was also reported to prepare core-shell structure of
Cu-ZnO@HZSM-5 catalyst for STD reaction [179]. Sánchez-Contador
and coworkers [180] have investigated the advantage of the core-shell
structure of CZZ@SAPO11 over simple physically mixed catalyst CZZ-
SAPO-11 for DME synthesis from the mixture of CO and CO2 gases in
fixed bed reactor. The core-shell structure enables separation of the
methanol synthesis and methanol dehydration reactions and therefore
H2O produced in the dehydration reaction will not affect the methanol
formation on metallic function. As a result, methanol while diffusing
out of the core, will be converted to DME in the shell side of the cat-
alyst.
Nowadays a number of innovative capsule catalysts have been
synthesized for STD reaction [182,183]. Zeng et al. [163] proposed a
dry sputtering method which is an alternative to a wet chemical method
and is environmentally benign. They have synthesized a highly dis-
persed Cu-Zn nano-alloy coated HZSM-5 catalyst via the physical
sputtering method. A wide range of particle size distribution of im-
pregnated catalyst was observed from 5 to 15 nm and after calcination
followed by reduction, active Cu5Zn8 nanolayer was formed. This nano
alloyed and well-dispersed catalyst showed good syngas conversion and
high DME selectivity.
7. Effect of operating parameters on DME selectivity
7.1. Water production during DME synthesis
Direct DME synthesis processes utilizing CO-rich or CO2-rich feed-
stock have different extent of water generated during the course of the
reaction. DME synthesis from methanol dehydration process is re-
sponsible for water generation. The produced water is often consumed
by the water gas shift (WGS) reaction (Eq. (9)) when CO-rich feed gas is
used and H2 is produced from the WGS reaction, which is again utilized
in CO hydrogenation reaction [19]. WSG acts as a chemical wheel
which gives the syngas based DME synthesis process extra kinetic
flexibility to reduce water accumulation and accelerate the methanol
hydrogenation reaction [184]. But in the case of CO2 rich feed, reverse
water-gas shift (rWGS) reaction is responsible for additional water
generation and CO production [185] (Eq. (13)). Therefore it is essential
to remove water from the system, otherwise decrease in DME selectivity
is inevitable. The higher water content in the system is also unsuitable
for methanol generation step by hydrogenation reaction, as CO and CO2
have to compete with water molecules to get adsorbed on the metallic
sites of MSC [123,186]. In situ removal of water can accelerate rWGS
reaction to produce more CO from CO2 and DME synthesis will be
improved. In the case of CO-rich feed gas, removal of water can ac-
celerate the methanol dehydration reaction and enhance the DME se-
lectivity [187]. Carvill et al. [188] have shown that sorption-enhanced
reaction process could be useful for water removal by adsorption and
Iliuta et al. [189] have also adopted sorption-enhanced reaction method
for in situ water removal for DME synthesis in fixed bed reactor and
studied the effect of different parameters. DME synthesis with in situ
water removal can improve DME selectivity compared to that without
water removal [189]. But according to Sierra et al. [123] removal of
water can lead to deactivation of Cu-ZnO-Al2O3 catalyst as coke
307
Journal of CO₂ Utilization 32 (2019) 299–320
deposition occurs on the catalyst surface. Some other studies have
proved that the presence of water attenuates coke formation on metal
sites. The main origin of the coke is the adsorbed methoxy ions on metal
sites and water content controls the presence of methoxy ion on the
catalyst surface [60,123].
7.2. Effect of different feed compositions
Direct DME synthesis process is reported to be more thermo-
dynamically advantageous compared to two-step process and the
equilibrium conversion of feed gas (CO and/or CO2) depends upon the
reaction temperature and feed gas composition [190]. Syngas can be
tailor-made according to the required composition of H2 and CO, for a
different use. Among the different syngas production methods catalytic
partial oxidation (CPO) produces the required H2/CO ratio for the ap-
plication in DME synthesis. The increase in H2 proportion in the feed
gas mixture enhances CO conversion but for WGS reaction the opposite
trend is observed, because the reaction order for methanol synthesis
reaction is 2 and for WGS reaction it is 1. Moradi et al. [191] have
reported that CO conversion is increased from 48.23% to 78.40% at
constant space velocity (SV) of 1100 mLN/(g-cat.h) when H2/CO ratio
is changed from 1 to 2. In the STD process, CO conversion is not de-
pendent on the methanol dehydration step when the intrinsic methanol
formation rate is much slower than the methanol dehydration rate [46].
With increasing H2/CO ratio, methanol synthesis rate is accelerated and
CO conversion enhanced as H2 rich environment favors methanol for-
mation and is the highest at 2:1 ratio [184]. At a low content of H2 in
syngas (H2/CO = 1:1), H2 becomes the limiting reactant and the me-
thanol formation rate becomes very slow with overall low DME yield.
Higher H2/CO ratio (2:1) suppresses the WGS reaction, which consumes
the produced water in a methanol dehydration reaction. Thus by in-
creasing the H2 proportion results into the accumulation of water mo-
lecules which leads to deactivation of catalyst [191]. Along with H2,
CO2 is also produced in the WGS reaction. Some studies reported that
CO2 removal before DME synthesis enhances the yield and high purity
CO2 can also be achieved [192]. Otherwise, CO2 is adsorbed on the
catalyst surface faster than CO and H2 [157]. Thus the presence of CO2
in the reactor has to be regulated as both CO conversion and DME se-
lectivity are decreased in high CO2 concentration [193,194].
Bayat and Dogu [190] have investigated the effect of CO/CO2 ratio
on overall DME yield and carbonaceous gas (CO + CO2) conversion by
keeping H2/(CO + CO2) ratio constant. They have achieved a very high
DME selectivity of 90% at 275 °C with a feed gas composition of 4:1
(CO/CO2). Erene et al. [195] investigated the effect of H2/CO2 ratio on
CO2 conversion and DME selectivity. The highest DME selectivity is
observed at 8:1 ratio and the lowest at 1:1. At H2/CO2 ratio of 1:1,
significant coke deposition was observed on the acid function and the
transformation of oxygenates (methanol and DME) depended on the
acid function of the catalyst. Thus the increased quantity of hydrogen
increases the yield of oxygenates. Ateka et al. [196] investigated the
valorization of CO2 for DME synthesis from the feed gas (a mixture of
H2, CO, and CO2) on CZA/S-18 bifunctional catalyst. The CO2 content
in the feed is varied with the molar ratio of CO2/COx, from 0.0 to 0.5.
According to their findings, DME yield is decreased with the co-feeding
of CO2, which is in a good agreement with other studies. With the
syngas feed, the DME yield is reported to reach as high as 14.6%, and
when CO2 is introduced at a CO2/COx molar ratio of 0.25, the DME
yield reduced to 6.6%. The presence of CO2 has a very moderate effect
on the product distribution, the selectivity of oxygenates remained re-
markably high (< 95%) with paraffin selectivity less than 1%. When
the H2/COx molar ratio is varied from 3 to 4 in the feed gas (CO2/
COx > 0.4), the DME yield is slightly enhanced, but for lower value
CO2/COx ratio, the opposite trend was observed (Fig. 5). Maximum CO2
conversion of 10% is achieved at CO2/COx of 0.4 and H2/COx ratio of 4.
U. Mondal and G.D. Yadav
Fig. 5. Effect of the CO2/COX ratio in the feed on the product yield (a) and selectivity (b) and effect of the H2/COX ratio on the yield of DME (c) and selectivity (d) for
different CO2/COX molar ratios in the feed. Reaction conditions: 275 °C; 30 bar; 10.18 (g-cat) h (molC)−1; feed, H2 + CO + CO2. Reproduced from [196].
7.3. Effect of feed supply rate
Feed supply rate is an important parameter for DME synthesis in any
reactor system and it is represented by many units such as space velocity
(SV), gas hourly space velocity (GHSV), and space-time (ST). At constant
H2/CO ratio, CO conversion increases when space velocity (SV) is de-
creased but when SV is reduced beyond a certain point CO conversion
cannot be enhanced. At higher SV, the fast feeding of reactant gas mix-
ture promotes high mass transfer rate, but it comes with the cost of the
contact time between the reacting species and the catalyst. Moradi et al.
[191] observed that CO conversion is increased from 71.51% to 89.52%,
when SV was reduced from 1000 mLN/(g-cat.h) to 500 mLN/(g-cat.h) at
constant H2/CO ratio (2:1). However, further increase in CO conversion
was not reported for SV less than 500 mLN/(g-cat.h). Hayer et al. [58]
investigated DME synthesis in a microchannel reactor from syngas. Ex-
perimentally they confirmed that with increasing the space velocity from
4500 to 60000 mLN/(g-cat-h), the CO conversion decreased. Initially, it
increased to maximum at 9000 mLN/(g-cat-h) as the corresponding feed
rate increased, but after that, it decreased due to short residence time.
Increase in SV also decreases the selectivity of DME due to the con-
secutive product formation from methanol. Kumar and Srivastava [197]
studied syngas conversion into DME in fluidized bed reactor and reported
that DME productivity initially increased with an increase in GHSV from
80 to 1000 h−1, but it decreased above 1400 h−1. It was reported that at
turbulent flow the CO conversion, DME selectivity, and yield were
higher. CO conversion was very low at bubbling bed flow regime
(GHSV = 80 h−1). Beyond GHSV of 1000 h−1 flow regime changed to
turbulent flow and both CO conversion as well as DME selectivity in-
creased. Ateka et al. [196] investigated the effect of space-time
(2.5–20 g-cat h (molc)−1) by varying the catalyst mass at different molar
flow rates on DME yield from syngas in a high pressure fixed bed reactor.
They observed that by increasing the space-time CO conversion and DME
yield were increased with negligible paraffin selectivity and little
308
Journal of CO₂ Utilization 32 (2019) 299–320
methanol selectivity (1.5%).
Liu et al. [198] investigated the effect of various space velocities
(1500 to 3000 mLN g-cat−1 h−1) on CO2 conversion and DME se-
lectivity. It was reported that when SV was increased to 3000 mLN/ (g-
cat h), CO2 conversion is decreased along (27.9 to 22.3%) with DME
selectivity (64.6 to 58.5%). Similar observations were also made by
Zhao et al. [199] who reported that when SV was increased to
3500 mLN. g-cat−1 h−1 from 1500 mLN g-cat−1 h−1, then DME se-
lectivity was decreased to 47.5 from 63.1%.
7.4. Effect of reaction temperature
The reaction temperature plays a big role in reversible exothermic
reactions such as DME synthesis from syngas or mixture of CO2 and H2.
In the beginning, the reaction is under kinetic control at low temperature
and by increasing the reactor temperature, the reaction rate can be en-
hanced. As the reaction progresses and tends to achieve reaction equi-
librium, the reactor temperature starts to increase and as a result, the
overall conversion is reduced. Thus any reaction process involving exo-
thermic reversible reaction should be operated in such a way that along
the reactor length the reactor temperature should decrease. Kumar and
Srivastava [197] studied the effect of temperature on DME synthesis
from syngas in a slurry phase reactor at 230 and 250 °C. A similar con-
version was achieved at both reaction temperatures, although at the end
of the reaction, a minor difference in productivity was observed. Reac-
tion at 250 °C showed better selectivity than at 230 °C along most of the
reactors. Lu et al. [184] have concluded that DME synthesis catalyst
should not be exposed to a temperature higher than 270 °C otherwise the
catalyst activity will be reduced due to sintering of Cu metallic sites
which was also confirmed by others [200,201]. Kumar and Srivastava
[197] explained that with increasing the temperature, the selectivity also
increases because at higher temperatures activity of methanol dehydra-
tion catalyst is higher than that of methanol synthesis catalyst. It was
U. Mondal and G.D. Yadav Journal of CO₂ Utilization 32 (2019) 299–320

Fig. 6. Effect of temperature on CO conversion and DME selectivity. Reaction condition: catalyst CZA/HZSM-5 (prepared by impregnation, co-pre-
cipitation–physically mixing and co-precipitation–ultrasound methods), H2/CO molar ratio of 2, GHSV of 600 cm3N/(g-cat.h) [167].

Fig. 7. Effect of pressure on CO conversion and DME selectivity. Reaction condition: catalyst CZA/HZSM-5 (prepared by impregnation, co-precipitation–physically
mixing and co-precipitation–ultrasound methods), H2/CO molar ratio of 2, GHSV of 600 cm3N/(g-cat.h) [167].

suggested that 250 °C was the best reaction temperature for DME
synthesis in slurry phase reactor. DME synthesis from syngas in fixed bed
reactor has been studied in the presence of CuO-ZnO-MnO/SAPO-18
bifunctional catalyst, and the reaction temperature was varied in the
range of 250–350 °C. It was reported that the highest DME yield was
obtained at 275 °C and above 300 °C an increase in paraffin yield (me-
thane is most selective among all C1–C3 molecules) was observed. In the
temperature range of 250–275 °C DME selectivity was found to
be > 95% but it was reduced to 65% when the reaction temperature was
increased to 350 °C [202]. Khosbin and Haghighi [167] investigated
DME synthesis from CO in the range of 200–300 °C and their results are
shown as CO conversion and DME selectivity in Fig. 6. It shows that CO
conversion increases up to 275 °C but thereafter it decreases when the
temperature is increased to 300 °C. DME selectivity decreases as the re-
action temperature is increased. Zhau et al. [199] examined the effect of
temperature on CO2 conversion and DME selectivity. It was found that
with the increase in temperature from 240 to 260 °C, CO2 conversion and
DME selectivity were also increased (20.9% and 63.1%, respectively).
But further increase up to 280 °C decreased both CO2 conversion and
DME selectivity. The hydrogenation of CO2 is a reversible reaction and
therefore an increase in temperature causes enhancement of reverse re-
action and a decrease in DME selectivity. Zha et al. [203] had reported
that when the temperature was increased to 282 °C from 262 °C, DME
selectivity was decreased to 30.9% from 45.1%. Liu et al. [198] also had
reported that when reaction temperature was increased from 240 to
260 °C DME selectivity was increased to 64.5%, but a sharp decrease in
DME selectivity (47.5%) was observed when the temperature was in-
creased to 280 °C.
7.5. Effect of operational pressure
According to the thermodynamic analysis of DME synthesis reac-
tion, the reaction pressure has a positive effect on overall DME yield.
Many researchers have reported that with increasing reaction pressure
both the CO conversion and DME selectivity increase. So it is evident
that the equilibrium conversion of CO for the methanol synthesis re-
action is enhanced by the consumption of methanol in the methanol
dehydration reaction. The negative effect of elevated pressure on direct
DME synthesis has also been reported as water is produced in both
methanol synthesis and methanol dehydration reactions. Increase in the
partial pressure of water suppresses the CO conversion by blocking the
active sites for methanol dehydration reaction. Erena et al. [201] in-
vestigated the effect of pressure from 10–50 bar on the direct DME
synthesis from a mixture of CO, CO2, and H2 gases. CO conversion was
increased when operating pressure was elevated to 50 bar. Hydro-
genation of CO and CO2 leads to a decrease in a number of moles, and
consequently, when pressure is elevated, hydrogenation reactions are
favored over WGS reaction. The methanol synthesis reaction is the
limiting step of this process. Thus it can be understood that by in-
creasing pressure, the rate of methanol dehydration reaction is also
elevated. The composition of the hydrocarbons in the product stream is
also affected by the variation of pressure, and the fraction of C1–C4
paraffin increased in comparison to C5* paraffin [195]. Therefore it is
very clear that at elevated pressure (up to 50 bar) the hydrogenation of
light olefins (intermediate products obtained methanol and DME) pre-
dominates over single condensation reactions (aromatization, alkyla-
tion, oligomerization). Jia et al. [204] investigated DME synthesis

309
 Table 2
Effect of different catalysts and process parameters on selectivity for DME synthesis in fixed bed reactor.
Synthesis method Catalyst Temperature, °C Pressure, MPa Others essential factor Conversion & yield Authors

Direct method CuO-ZnO-MnO/SAPO-18 275 3 H2:COx = 3; CO2:COx = 0–0.5; Space time = 5.2 gcat. h (molC)−1 CCOx = 47% Ateka et al.
[206]
Direct method Cu-ZnO/γ-Al2O3 220–260 5 H2:CO2:Ar:N2 = 15:15:60:10 YDME = 21. Henrich et al.
U. Mondal and G.D. Yadav

[207]
Direct method Pd-Ga NP/γ-Al2O3 250–300 2 Ar:N2:H2:CO = 5:2:1.5:1.5 CCO2 = 60% Gentzen et al.
Total flow = 50 mLNTP/min [208]
Direct method Cu-Zn NP/HZSM-5 250–300 5 Ar:N2:H2:CO = 5:2:1.5:1.5 Gentzen et al.
Total flow = 50 mLNTP/min [209]
Direct method Cu-ZnO-ZrO2/SAPO-11 275 3 H2:COx = 3; CO2:COx = 0.5; Space time = 2.5 gcat. h (molC)−1 CCO = 30% Sánchez-
Contador et al.
[181]
Indirect method SAPO-11 nanocrystals (20–30 nm) 260 0.1 N2: MeOH = 240 (vol ratio) YDME = 19.6 Chen et al. [210]
Direct method CuO-ZnO-Al2O3/SAPO-18 275 3 H2:CO2 = 3; CO2:COx = 0–0.5 CCO = 40% Ateka et al.
St = 10.18 gcat. h (molC)−1; [196]
Direct method Cu-infiltrated Zr doped SBA-15 250 3.3 H2:CO2 = 3:1 YDME = 25 Atakan et al.
[211]
−1
Direct method Cu–Zn/Al2O3; sol-gel method 220 0.9 H2/CO/Ar = 5.0/5.0/1.0 mL min CCOx = 9% Takeishi et al.
[212]
Direct method CuO/ZnO/Al2O3 & HZSM-5 250 1–5 Syngas YDME = 6.5 Dadgar et al.
AV = 800 N cm3/min/g [213]
Direct method CuO/ZrO2 + montmorillonite K10 220–300 4 H2 + CO2 = 6 m ml/min CMeOH = 80% Kornas et al.
(modified by 3 wt% of Ga, Cr, Mn and Ag) [214]
Direct synthesis Cu–Fe–Ce/HZSM-5 with 3.0 wt% CeO2 240–280 2–4 Plasma catalytic reactor = 11.0–15.0 kV, H2: C02 = 4:1 CCOx = 9.5% Su et al. [215]
GHSV = 1500–3500 mL.gcat−1h−1
Direct method Cu.ZnO/Al2O3 or Nb2O5 250/270 3 H2/CO2 = 3 YDME = 14.5% Silva et al. [216]

310
SV = 10 h−1
Direct method Cu based MSC (C18W019) + Silicotungstic acid 275 5 H2/CO/CO2 = 50/40/10, CCO2 = 15% Bayat et al.
impregnated mesoporous alumina (STA@MA) Space time = 0.48 s gcat/mL. [190]
Total flow rate of feed gas = 25 ml/min
Indirect method Diatomite catalysts modified using nitric acid 250–350 0.1 MeOH:N2 = 1:4; total flow rate = 60 ml/min Pranee et al.
[217]
Direct synthesis CuO-ZnO-MnO/SAPO-18 270–350 3 H2/CO = 3; YDME = 8% Ateka et al.
space time (2.5–20 gcat h (molC)−1) [202]
Direct synthesis CuO-Fe2O3-CeO2/HZSM-5 240–280 2–4 H2/CO2 = 4; Zhau et al. [199]
GHSV = 1500–3500 mL gcat−1 h−1
Direct synthesis Cu/mesoAL(HT) 250 5 H2:CO:N2 = 63:31.5:5.5; S DME = 35% Ham et al. [218]
SV = 2000 L/(kgcat.h)
Direct synthesis CuO–ZnO–Al2O3/HZSM-5 260 2 H2/CO = 2 (mole ratio) CCO2 = 69.5% Cai et al. [172]
GHSV = 3600 cm/gcat/h
Indirect synthesis MgO/HZSM-5 200–300 MeOH:EtOH = 3:1 YDME = 16.9% Liu et al. [219]
WHSV = 4 h−1
Direct synthesis Cu-Zn-Zr/MFI Zeolite 180–240 5 SV = 2500 NL/Kgcat/h; CO2:H2:N2 = 3:9:1 CCO2 = 9% Frusteri et al.
[154]
Direct synthesis Cu–Fe–Zr/HZSM-5 240–280 2–4 H2: CO2 = 5:1; S DME = 31% Qin et al. [220]
GHSV = 1500– 3000 mL.gcat−1h−1
Direct synthesis Cu/ZnO/Al2O3 & HZSM-5 (modified with MgO, CaO & 260 4 H2/CO/CO2/N2 = 59.93:27.33:4.12:8.62 (vol%); GHSV = 1500 mL CCOx = 90% Mao et al. [221]
BaO) h−1 g−1 cat
Direct synthesis Cu/Zn/Al citric/TPA- K10 280–360 4 Syngas (CO:CO2:H2 = 5:30:65) YDME = 26.0% Samson et al.
GHSV = 3600 h−1 [222]
Direct synthesis CuO–ZnO–Al2O3 and SiO2-ZSM-5 260 2 H2: CO = 2 SDME = 90% Ordomsky et al.
GHSV = 3600 cm3 gas/g−1 cat h−1 [169]
Direct synthesis Cu–ZnO–Al2O3–ZrO2 (with different Zr ratio) and γ-Al2O3 270 5 Biomass derives syngas(H2/CO/CO2/CH4 = 52/24/23/1), CCOx = 36% Song et al. [223]
GHSV = 1500 h−1
(continued on next page)
Journal of CO₂ Utilization 32 (2019) 299–320
 Table 2 (continued)

Synthesis method Catalyst Temperature, °C Pressure, MPa Others essential factor Conversion & yield Authors

Direct synthesis Core- shell structure catalyst (CuO–ZnO–Al2O3@ 220–320 2–6 Syngas (H2/CO = 2) YDME = 13% Wang et al.
SiO2–Al2O3) GHSV = 1000–4000 mL/(h gcat) [224]
Direct synthesis Cu/ZnO/H-ZSM5 by by sputtering and impregnation 250 5 Syngas (CO: 33.8 v%, CO2: 5.10 v%, Ar: 3.09 v%, balanced with H2; CCOx = 20.9% Sun et al. [225]
methods Wcatalyst/Fsyngas = 10 g h mol−1
U. Mondal and G.D. Yadav

Direct synthesis CuZnAl/zeolite 260 4 Gas mixture = 90% syngas(66% H2/30% CO/4% CO2) + 10% Ar SDME = 63.1% García-Trenco
SV = 2550 cm3/(gcat.h) et al. [226]
Direct synthesis Multi-walled carbon nanotubes promoted CuO–ZnO–Al2O3/ 262 3 H2/CO2 = 3/1 CCOx = 11.5% Zha et al. [203]
HZSM-5. GHSV = 1800 mL gcat−1 h−1
Direct synthesis CuO–Fe2O3–ZrO2/HZSM-5 240–280 2–3.5 H2/CO2 = 5/1 SDME = 76.1% Liu et al. [227]
GHSV=
1500–3000 mL gcat−1 ·h−1
Direct synthesis Cu/ZnO/H-ZSM5 sputtering catalyst 250 5 Syngas (CO: 32.5%, CO2: 5.2%, Ar: 3.1%, balanced with H2) CCOx = 75.0% Zeng et al. [163]
Direct synthesis Cu–ZnO/γ-Al2O3 270 3.5 Syngas= SDME = 69.8% Ahn et al. [228]
H2/CO = 2 along with 5.6 mol% N2
GHSV = 2000 ml/gcat.h
Direct synthesis Core shell CuOZnO Al2O3@Al2O3 260 5 Syngas = H2/CO Wang et al.
GHSV = 1500 mLh−1 gcat−1 [183]
Indirect synthesis Undoped and doped γ-alumina spherical particles (CuO, Up to 350 0.1 2 mol% CH3OH mixed with N2 was fed into the reactor at a flow rate of CCOx = 23.6% Pillai et al. [229]
CuO + ZnO) by sol-gel method 60 mL min−1
Direct synthesis core–shell like silicoaluminophosphate (SAPO-46) 350 5 Syngas = 58.10% H2: 33.80% CO: 5.10% CO2: 3.09% Ar SDME = 49.3% Pinkaew et al.
encapsulated Cr/ZnO capsule catalyst [178]
3 −1
Indirect synthesis Ba2+ impregnated on γ-Al2O3 260 –290 0.1 MeOH flow rate = 0.3–0.9 cm min CCO = 30% Hoda et al.
[230]
Direct synthesis Cu/ZnO/Al2O3 and phosphate on γ-Al2O3 250 5 Syngas (H2/CO) = 2 CCOx = 93.8% Montesano et al.
GHSV = 8400 h−1 [231]
Direct synthesis Mesoporous Cu/γ-Al2O3 280–325 5 Syngas = CO(6 ml/min) + H2 (12 ml/min) + N2 (2 ml/min) SDME = 64.4% Jiang et al.

311
[139]
Direct synthesis Core-shell design CuO-ZnO/HZSM-5 257 3 H2/CO2 = 2 (mol/mol) Li et al. [232]
SV = 1600 h−1
Direct synthesis CuO–ZnO–Al2O3 with acid catalyst NH4ZSM-5, HZSM-5 or 200–260 2 syngas mixture (BOC gases) which contained (62% H2, 31% CO, 4% CCOx = 65% Abu-Dahrieh
γ-Al2O3 CO2 and 3% Ar) et al. [141]
SV = 2400 ml h−1 g−1
cat
Direct synthesis XNC-98/HZSM-5 = 4:1, 220–280 3 H2/CO = 1 SDME = 45% Zhang et al.
GHSV = 3000 ml/gcat.h [233]
Indirect Synthesis aluminum fluoride (AlF3) modified HZSM-5 180 MeOH SV = 40 ml h−h CCO = 74% Yang et al. [234]
N2 SV = 6000 h−1
Direct synthesis CuO-ZnO-Al2O3 to pseudo-boehmite was 2/1 220–260 4 H2:CO: CO2 = 1.0/1.0/0.08 SDME = 69% Liu et al. [235]
Indirect synthesis Al-SBA-15 120–450 0.1 MeOH vapour + He = 44.4 cm3 min−1. CCO = 79.3% Tokey et al.
[118]
Direct synthesis hybrid CuZnAl/ZSM-5 260 4 A mixture of 90 vol% syngas (molar composition: 66%H2/30%CO/ SDME = 85.8% Trenco et al.
4%CO2) and 10 vol% Ar. [171]
SV = 1700 mLsyngas/(gcat. h)
Direct synthesis CuO–ZnO–Al2O3/γ-Al2O3 with excess γ-Al2O3 225–325 2–4 H2/CO2 = 2/1 to 4/1 Space time Erena et al. [60]
ST = 42.0 (g of catalyst) h (mol of carbon)−1 yield = 5.08 mol/L/h
Direct synthesis Cu-Zn/γ-Al2O3 260 5 H2/CO = 1 CCO = 71.1% Park et al. [236]
GHSV = 3000 ml/g-cat.·h
Direct synthesis Double shell capsule catalyst Cr/ZnO–S–Z (S = neutral 300–350 5 Ar 3.02%, CO 32.6%, CO2 5.16%, H2 59.22% in molar base SDME = 61.9% Yang et al. [237]
Silicalite-1 zeolite layer; Z = HZSM-5 layer)
Direct synthesis CuO/ZnO/Al2O3 and γ-alumina 220–260 3–7 H2: 60–75%, N2: 9–12%, CO: 12–20%, CO2: 1–5%. Cheng et al.
GHSV = 1000–2500 mL/g h [238]
Direct synthesis Cu–ZnO/γ-Al2O3 250 5 H2:CO = 2:1; CCO = 13.7% Beak et al. [239]
space velocity (SV) = 4000 mL gcat−1 h−1
(continued on next page)
Journal of CO₂ Utilization 32 (2019) 299–320
 Table 2 (continued)

Synthesis method Catalyst Temperature, °C Pressure, MPa Others essential factor Conversion & yield Authors

Indirect synthesis Macro porous sulphonic acid ion exchange resign 118–150 2.0 MeOH = 0.20 ml/min SDME = 92.1% Lei et al. [240]
Direct synthesis bifunctional catalyst (JC207/HZSM5 [Si/Al = 25, 38, 50, 250–290 3 gas product from biomass gasification containing H2 42.1%, N2 13.4%, Xu et al. [241]
150]) CO 33.9%, CH4 5.0%, CO2 5.6%
SV = 1300 L/(kg. hr)
U. Mondal and G.D. Yadav

Direct synthesis CuO–ZnO–Al2O3 (Cu:Zn:Al ≈ 5:4:1 mass ratio)/γ-Al2O3 210–300 1-6 H2/CO = 2–4; CCO = 87–90% Hayer et al. [58]
SV = 15.000 Nml/gcat/h
Direct synthesis 6CuO–3ZnO–Al2O3/γ-Al2O3 and 6CuO–3ZnO–1Al2O3/ 260 5 reactant gas (CO2/3H2) SDME = 64% Naik et al. [124]
HZSM-5 GHSV = 3000 ml/gcat. h
Direct synthesis bifunctional catalyst (JC207/HZSM5 [Si/Al = 38, MgO, 240–280 3 Biomass pyrolysis gas (H2 42.1%, N2 13.4%, CO 33.9%, CH4 5.0%, CO2 Xu et al. [242]
Cao and ZnO]) 5.6%)
SV = 1300 L/(kg hr)
Indirect synthesis γ-Al2O3 260–380 0.1–1.6 MeOH, CCO2 = 46.2% Moradi et al.
SV = (W/F = 1.724 g/ml·min) [243]
Indirect synthesis novel silicotungstic acid (STA) incorporated nano- 180–350 MeOH = 2.1 mL/hr SDME = 45.2% Ciftci et al.
composite catalysts (silicate structured mesoporous MeOH/He = 0.48 (vol/vol) [244]
catalysts TRC-62(L), TRC-82(L) and TRC-92(L)),
Indirect synthesis mesoporous nanocrystalline γ-Al2O3 300 0.1 MeOH YDME = 20.9% Keshavarz et al.
WHSV, (1.75–9.62 h−1) [245]
Indirect synthesis Nafion-Incorporated Silicate Structured Nanocomposite 120–300 0.1 MeOH = 2.1 ml/min CCO2 = 28.4% Ciftci et al. [89]
Mesoporous Catalysts He = 23 ml/min
Space Time = 0.27 s g cm-3
MeOH: Feed Gas = 0.48
Indirect synthesis γ-Al2O3 derived from Nordstrandite 300 0.1 MeOH, GHSV = 6000 SDME = 64.5% Seo et al. [246]
Direct synthesis Cu–ZnO–Al2O3 promoted with Zr or Ga on γ-Al2O3 250 5 H2:CO = 2:1 Kang et al. [247]
(SV) = 4000 mL gcat−1 h−1
Direct synthesis CuO-ZnO- Al2O3/γ- Al2O3 225–350 1–4 H2/CO = 2–4 CCO = 13% Sierra et al.

312
ST = 0.1–68.0 (g of catalyst) h (mol of reactants)−1 [123]
Reactant flow rate = 1 mmol/min (H2 + CO)
Indirect synthesis 1. Rh-SiO2 catalyst (0.406 wt% Rh in SiO2) 1.660 0.1 1. liquid 48 wt%HBr/H2O was 6.5 ml/h SDME = 93.5% You et al. [248]
2. ZnCl2/SiO2 2.180 (CH4, O2, N2, CO, and CO2 were 20.0 ml/min, 5.0 ml/min, 5.0 ml/min,
3.0 ml/min, and 4.0 ml/min)
2. CH3Br, N2, and H2O (L) are 10.0 ml/min, 10.0 ml/min, and 0.5 ml/h)
Direct synthesis Cu/Zn/Al/HZSM-5 260 4.3 H2/CO = 2 CCO = 47.6% Li et al. [249]
GHSV = 3000 h−1
Tail gas recycled GHSV = 650-3000 h−1
Direct synthesis Cu–ZnO–Al2O3/Zr-ferrierite (CZA–ZrFER) 250 4 CO/CO2/H2 = 41/21/38 (molar feed composition) SDME = 61.1% Bae et al. [250]
SV = 5500 L/(kgcat h)
Direct synthesis CuO–TiO2–ZrO2 (with various Ti and Zr molar 200 3 Feed gas = CO2 (23.3%), H2 (64.5%) and N2 (the rest) CCO = 35.2% Wang et al.
ratios) + HZSM5 [251]
Direct synthesis Cu-Zn-Al-M (M = Ga, La, Y, Zr)/γ- Al2O3 250–280 4.13 H2/CO = 1.5 SDME = 61.1% Venugopal et al.
GHSV = 6000–12000 h−1 [134]
Indirect synthesis γ-Al2O3 and η-Al2O3 260 GHSV = 6000 CMeOH = 100% Seo et al. [252]
from boehmite and bayerite
Direct synthesis CuO–ZnO–Al2O3–ZrO2 + HZSM-5 250 5 H2/CO2 = 3 CCOx = 6.9% An et al. [253]
SV = 6000 mL/(g cat · h)
Direct synthesis CuO/ZnO/Al2O3 for methanol forming, γ-alumina for 260 6 Coal gasification H2/CO = 0.5 YDME = 37% Yoo et al. [254]
methanol dehydration GHSV = 3000 l/kg-cat h
Direct synthesis Cu–ZnO–Al2O3/Zr-modified zeolites (Ferrierite, ZSM-5 and 250 4 CO/H2/CO2 (41/38/21) CMeOH = 27.7–46.33% Kang et al. [255]
Y) SV = 5550 ml/h gcat
Indirect synthesis Cu0.5(1+y)FeyZr2−y(PO4)3 197–397 0.1 MeOH + Ar/Air = 2.4l/h Pet'kov et al.
y = (0, 0.5, 1.0, 1.5 and 2.0) [256]
Indirect synthesis commercially available γ- Al2O3 300 1.6 MeOH = 0.55 ml/min CCO = 72% Mollavali et al.
GHSV = 26.07 h−1 [257]
Direct synthesis CuO-ZnO-Al2O3-ZrO2/HZSM-5 (SiO2:Al2O3 = 25) 250 3 H2/CO2 = 3 SDME = 69% Zhao et al. [258]
GHSV = 1600 h−1
Journal of CO₂ Utilization 32 (2019) 299–320

(continued on next page)

 Table 2 (continued)

Synthesis method Catalyst Temperature, °C Pressure, MPa Others essential factor Conversion & yield Authors

Direct synthesis Cu–Mn–Zn/zeolite Y modified with La, Ce, Pr, Nd, Sm and 245 2 H2/CO = 3/2 and CCO = 81% Jin et al. [259]
Eu SV = 1500 h−1
Direct synthesis Cu/ZnO/Al2O3 and SAPO-34 and -18 260 4.2 H2/CO = 1.5 SDME = 67% Yoo et al. [260]
GHSV = 3000 mL/gcat h
U. Mondal and G.D. Yadav

Indirect synthesis aluminum phosphate catalysts with Al/P = 1 175–275 0.1 MeOH = 2 ml/h Kumar et al.
[261]
Direct synthesis Al2O3 on the Cu-ZnO-Al2O3-SiO2 catalysts prepd. by a 250 3 20%CO2 and 80%H2 CCO = 63.4% Wang et al.
pseudo sol-gel method SV of 3200 h−1 [262]
Indirect two step 1. 0.1 wt% Ru/SiO2 1. 530– 560 0.1 1. HBr/H2O (40 wt% in water) = 4.0 mL/h. SDME = 10.8% Xu et al. [263]
process 2. RuCl3 2. 150– 180 CH4 = 5 ml/min
O2 = 15–20 ml/min
2. CH3Br = 0.5 g
H2O = 0.4-0.7 g
Indirect synthesis aluminum was 850–425 mm (about 18–35 mesh)and 200–325 MeOH = 0.39 kg/dm3 CCO = 70% Usui et al. [264]
magnesium was 20–70 mesh (about 740–210 mm) power
Direct synthesis Copper catalyst (Süd-Chemie Catalysts Japan Inc., MDC-3) 220–290 1–3 Syngas = (H2/CO/CO2/Ar) 60/30/5/5) Omata et al.
and γ-alumina Flow rate = 44 mmol/h [265]
Direct synthesis Cu-Zn-Al/HZSM-5 240 5 H2/CO = 2 CMeOH = 86% Jia et al. [266]
Space velocity = 1000−1
Direct synthesis Cu-ZnO-ZrO2/Al2O3-HZSM-5 260–280 8 Syngas derived from CH4 catalytic partial oxidation CCO = 81% Hengyong [267]
(CPO) = H2:CO:N2:CO2:CH4 = 39.8″14.7:37.2:5.9:2.4
SV = 1500−1
Direct synthesis C301/HZSM-5 230–270 4 H2 to (CO + CO2) equal to 2.6 SDME = 67% Wang et al. [56]
C301/γ-Al2O3 GHSV = 927 ml/gcat.h
Direct synthesis Cu-ZnO-X (X = Al2O3, Cr2O3, ZrO2 or Ga2O3 250 1 Blast furnace gas CMeOH = 52% Akiyama [268]
CO/CO2/H2 = 4/4/1

313
Feed gas flowrate = 1.O x 10−6m3/sec
Direct synthesis CuO/ZnO/γ-Al2O3 270 3 H2/CO/CO2 = 64/31/5 (mol) SDME = 100% Li et al. [269]
GHSV = 2000 h−1
Based on carbon molecule
Direct synthesis Pd/SiO2, Pd/Al2O3, modified Pd/Al2O3 and hybrid (phys. 230–350 1.1–5.1 H2/CO = 2/1 CCO = 93% Han et al. [270]
mixed) catalysts containing. Pd/SiO2 or Cu-Zn-Al (O) and γ- (5% CO2 was added in the case of methanol synthesis on Cu-Zn-Al
Al2O3 catalyst)
Contact time = 0.3–4.2 g-cat.-hr/mol.
Journal of CO₂ Utilization 32 (2019) 299–320
U. Mondal and G.D. Yadav
reaction up to 100 bar and concluded that there is no significant en-
hancement of CO conversion beyond 50 bar and this result is very much
similar to that of Erena et al. [205]. In slurry reactor, the effect of
pressure has shown an additional effect, with increasing the pressure
the bubble size decreases and as a result mass transfer coefficient in-
creases, which influences the overall conversion. Kumar and Srivastava
[197] also confirmed a similar phenomenon for DME synthesis reaction
in fluidized bed reactor from syngas. Khosbin et al. [167] investigated
the influence of reaction pressure from 10–40 bar on CO conversion and
DME selectivity. A positive effect of reaction pressure has been reported
on CO conversion and DME selectivity, as shown in Fig. 7. Table 2
summarizes different catalysts and operating parameters influencing
the conversion, yield and selectivity of DME studied over recent years.
Zhou et al. [199] varied the reaction pressure from 20–40 bar in one
pot DME synthesis process to investigate the effect on CO2 conversion
and DME selectivity. CO2 conversion was increased when reaction
pressure was elevated to 30 bar, but when it was increased beyond 30 to
40 bar, CO2 conversion was decreased. DME selectivity was also shown
to have a similar relationship with reaction pressure. The one-step CO2
to DME synthesis process is a series of volume decreasing reactions, and
therefore by increasing pressure, the CO2 conversion can be enhanced.
Zhou et al. [199] concluded that the decrease in CO2 conversion (17.2%
from 20.9%) and DME selectivity (55.5% from 60.3%) might be due to
water formation in the reactor when the pressure was elevated from
30 to 40 bar. Based on several studies, it was also concluded that 30 bar
was the optimum pressure for one pot DME synthesis from CO2
[198,199,203].
8. Conclusions
Dimethyl ether (DME) has great potential as fuel and precursor for
chemical manufacture. DME is the cleanest high-efficiency compression
ignition fuel as a substitute for diesel. In order to establish DME pro-
duction and utilization system, it is very important to establish the
required infrastructure for raw material supply chain, DME synthesis
process, and development of necessary machinery. The purpose of this
review was to take stock of DME as fuel and find out the technological
challenges in converting CO2 to DME. Fossil fuels are the largest source
of energy, and the combustion of fossil fuels tends to generate a huge
amount of greenhouse gases in the atmosphere. A large amount of
greenhouse gases (CO and CO2) are generated in coal or petroleum
operated thermal power plants and there is a dire need to provide a CO2
capture and sequestering (CCS) facility to deal with this huge pollution.
However, the economy of the CCS plant only can be sustainable when it
is supported by dimethyl ether synthesis plant with a production ca-
pacity in the range of 3000–7500 metric ton per day. Tremendous work
has been done to explore the most suitable reaction conditions for DME
synthesis. Bio-DME is a very attractive alternative to diesel, which
yields very low tailpipe emissions, near-zero amount of CO2 emission
and thus there is no need to CO2 capture and sequestration in the bio-
DME plant. However, the production cost of DME is higher with pre-
sently available technologies when it is produced from natural gas, coal,
and biomass because the conversion of raw materials to syngas is an
expensive process. Methanol based indirect DME synthesis is com-
paratively safer as methanol production from syngas is a mature and
well-established process. Companies like Linde/Lurgi, Haldor Hospice,
Uhde, Toyo Engineering, and Mitsubishi Gas Chemical Company are
holding the licenses for the single-step DME synthesis technology. MGC,
Toyo, Udhe, and Lurgi are developing DME production technology
based on indirect synthesis. A tabular summary of different studies of
the DME synthesis processes, catalysts, and operating conditions was
presented.
Other routes of DME synthesis process which are already practised
and being developed were discussed in detail.
314
Journal of CO₂ Utilization 32 (2019) 299–320
Some strategies have been taken up for direct DME synthesis process
from syngas and CO2, but it is a two-step process. The main obstacles of
the process are the catalyst deactivation due to water generation and
coke deposition on the surface of the acid catalyst. Copper-based multi-
component catalysts have been studied extensively. The vastly used
CO2 or syngas hydrogenation catalyst is Cu/ZnO/Al2O3 (CZA) and for
the methanol dehydration reaction, acidic catalysts are needed.
Compared to the syngas to DME (STD) process, DME synthesis from CO2
produces more amount of water leading to catalyst poisoning. A vast
array of catalysts have been tested for acid function for methanol de-
hydration reaction. HZSM-5 shows the highest water tolerability and
activity. Catalyst preparation methods also have a profound effect on
catalyst properties, and it is found that co-precipitation- sedimentation
and co-precipitation coupled with ultrasound irradiation were the most
suitable catalyst preparation methods for achieving high catalyst ac-
tivity. Many studies have employed core-shell structure of bifunctional
catalyst wherein CZA catalyst is covered by a thin layer of acidic cat-
alyst (HZSM-5). This type of catalyst configuration shows high DME
selectivity and less amount of by-product formation.
The performance of any DME synthesis process is hugely affected by
several operating parameters. A majority of the DME synthesis study
has been carried out in the temperature range of 200–300 °C and
pressure range up to 70 bar. For the conversion of CO2 to DME, the
optimum operational pressure is 30 bar and temperature 270–275 °C.
Direct conversion of CO2 is very difficult as more amount of water is
produced via rWGS reaction. Therefore co-feeding of CO with the feed
gas can convert water into H2 via WGS reaction and CO2 conversion
will increase. Comparatively syngas conversion is much easier, and the
highest conversion and DME selectivity are achieved in the range of
250–260 °C and at pressure of 40 bar. The molar ratio of H2 and CO2
also has a pronounced effect on DME selectivity and CO2 conversion. At
a higher molar ratio of H2/CO2 (8:1) the highest DME selectivity is
observed but as the molar ratio is decreased to 1:1, then CO2 conversion
is increased, but DME selectivity is decreased as huge coke is deposited
on the catalyst surface. Although a few pilot plant studies on DME
synthesis are reported in recent times, most of the DME synthesis from
various raw materials are only based on laboratory scale studies. To
project DME as a future fuel for our society, new studies encompassing
process optimization and scale-up of one-pot DME synthesis and eco-
nomic aspects of an efficient and practical DME synthesis plant must be
explored. More and more research on the noble catalyst development
has to be taken up for getting the most active, reusable, economical and
highly water tolerant catalyst. Feed type, its cost and supply rate is a
very important factor for DME synthesis process, and its effect on DME
selectivity and syngas gas and/CO2 conversion is dependent on the type
and capacity of the reactor. Therefore optimization of the space velocity
of the feed gas is of great importance for establishing a practical DME
plant. The type of reactors and separators and their configurations have
a great bearing on both fixed and operating costs of DME production.
The production of syngas, irrespective of nature of feed, is critical in
DME synthesis. Part II covers all these aspects. Overall, DME has a great
future.
Conflict of interest statement
The authors declare no conflict of interest.
Acknowledgement
UM got financial support as D.S. Kothari Post-Doctoral Fellowship of
UGC. GDY received support from R.T. Mody Distinguished Professor
Endowment, Tata Chemicals Darbari Seth Distinguished Professor of
Leadership and Innovation, and J.C. Bose National Fellowship, DST,
Govt. of India.
U. Mondal and G.D. Yadav
References
[1] S. Lee, S. Oh, Y. Choi, Performance and emission characteristics of an SI engine
operated with DME blended LPG fuel, Fuel 88 (2009) 1009–1015, https://doi.org/
10.1016/j.fuel.2008.12.016.
[2] D.A. Good, J.S. Francisco, A.K. Jain, D.J. Wuebbles, Lifetimes and global warming
potentials for dimethyl ether and for fluorinated ethers: CH3OCF3 (E143a), CHF2
OCHF2 (E134), CHF2 OCF3 (E125), J. Geophys. Res. Atmos. 103 (1998)
28181–28186, https://doi.org/10.1029/98JD01880.
[3] Y. Adachi, M. Komoto, I. Watanabe, Y. Ohno, K. Fujimoto, Effective utilisation of
remote coal through dimethyl ether synthesis, Fuel 79 (2000) 229–234, https://
doi.org/10.1016/S0016-2361(99)00156-8.
[4] J.-A. Taupy, DME industry and association overview, 4th International DME
Conference Stockholm (2010), http://www.aboutdme.org/aboutdme/files/
ccLibraryFiles/Filename/000000001633/DME4_IDA_Taupy.pdf.
[5] M. Marchionna, R. Patrini, D. Sanfilippo, G. Migliavacca, Fundamental in-
vestigations on di-methyl ether (DME) as LPG substitute or make-up for domestic
uses, Fuel Process. Technol. 89 (2008) 1255–1261, https://doi.org/10.1016/j.
fuproc.2008.07.013.
[6] L. Zhang, H.-T. Zhang, W.-Y. Ying, D.-Y. Fang, Intrinsic kinetic of methanol de-
hydration over Al2O3 catalyst, World Acad. Sci. Eng. Technol. 59 (2011)
1538–1543.
[7] Z. Azizi, M. Rezaeimanesh, T. Tohidian, M.R. Rahimpour, Dimethyl ether: A re-
view of technologies and production challenges, Chem. Eng. Process. Process
Intensif. 82 (2014) 150–172, https://doi.org/10.1016/j.cep.2014.06.007.
[8] T.H. Fleisch, A. Basu, R.A. Sills, Introduction and advancement of a new clean
global fuel: the status of DME developments in China and beyond, J. Nat. Gas Sci.
Eng. 9 (2012) 94–107, https://doi.org/10.1016/j.jngse.2012.05.012.
[9] S. Clara, D.S. Rice, A. Yamasani, S. Jose, J.B. Parks, S. Clara, E. Millar, M. View,
P.C. Richardson, A cetic acid reactive distillation process based on DME/methanol
carbonylation, US 6,175,039 B1, (2012) doi:9168268.
[10] B. Ru, X.B. Li, L.J. Zhu, G.H. Xu, Y.L. Gu, Gas-Phase Methanol Carbonylation for
Dimethyl Ether and Acetic Acid Co-Production, Adv. Mater. Res. 554-556 (2012)
760–763 doi:10.4028/www.scientific.net/AMR.554-556.760.
[11] K.C. Liang, F.M. Yeh, C.G. Wu, H.M. Lee, Gasoline production by dehydration of
dimethyl ether with NH4-ZSM-5 catalyst, Energy Procedia 75 (2015) 554–559,
https://doi.org/10.1016/j.egypro.2015.07.452.
[12] A. Sardesai, S. Lee, T. Tartamella, Synthesis of methyl acetate from dimethyl ether
using group VIII metal salts of phosphotungstic acid, Energy Sources 24 (2002)
301–317, https://doi.org/10.1080/00908310252888682.
[13] S. Wang, W. Guo, L. Zhu, H. Wang, K. Qiu, K. Cen, Methyl acetate synthesis from
dimethyl ether carbonylation over mordenite modified by cation exchange, J.
Phys. Chem. C 119 (2015) 524–533, https://doi.org/10.1021/jp511543x.
[14] Q. Zhang, Y. Tan, C. Yang, H. Xie, Y. Han, Characterization and catalytic appli-
cation of MnCl2 modified HZSM-5 zeolites in synthesis of aromatics from syngas
via dimethyl ether, J. Ind. Eng. Chem. 19 (2013) 975–980, https://doi.org/10.
1016/j.jiec.2012.11.019.
[15] Z. Wang, T. He, J. Li, J. Wu, J. Qin, G. Liu, D. Han, Z. Zi, Z. Li, J. Wu, Design and
operation of a pilot plant for biomass to liquid fuels by integrating gasification,
DME synthesis and DME to gasoline, Fuel 186 (2016) 587–596, https://doi.org/
10.1016/j.fuel.2016.08.108.
[16] A.S. Al-Dughaither, H. De Lasa, Neat dimethyl ether conversion to olefins (DTO)
over HZSM-5: Effect of SiO2/Al2O3 on porosity, surface chemistry, and reactivity,
Fuel 138 (2014) 52–64, https://doi.org/10.1016/j.fuel.2014.07.026.
[17] P. Pérez-Uriarte, A. Ateka, A.G. Gayubo, T. Cordero-Lanzac, A.T. Aguayo,
J. Bilbao, Deactivation kinetics for the conversion of dimethyl ether to olefins over
a HZSM-5 zeolite catalyst, Chem. Eng. J. 311 (2017) 367–377, https://doi.org/10.
1016/j.cej.2016.11.104.
[18] P. Pérez-Uriarte, A. Ateka, A.T. Aguayo, A.G. Gayubo, J. Bilbao, Kinetic model for
the reaction of DME to olefins over a HZSM-5 zeolite catalyst, Chem. Eng. J. 302
(2016) 801–810, https://doi.org/10.1016/j.cej.2016.05.096.
[19] K.L. Ng, D. Chadwick, B.A. Toseland, Kinetics and modelling of dimethyl ether
synthesis from synthesis gas, Chem. Eng. Sci. 54 (1999) 3587–3592, https://doi.
org/10.1016/S0009-2509(98)00514-4.
[20] Z. Nie, H. Liu, D. Liu, W. Ying, Intrinsic kinetics of dimethyl ether synthesis from
syngas, J. Nat. Gas Chem. 14 (2005) 22–28.
[21] H. Liu, P. Cheung, E. Iglesia, Structure and support effects on the selective oxi-
dation of dimethyl ether to formaldehyde catalyzed by MoOx domains, J. Catal.
217 (2003) 222–232, https://doi.org/10.1016/S0021-9517(03)00025-3.
[22] P. Cheung, A. Bhan, G.J. Sunley, E. Iglesia, Selective carbonylation of dimethyl
ether to methyl acetate catalyzed by acidic zeolites, Angew. Chemie - Int. Ed. 45
(2006) 1617–1620, https://doi.org/10.1002/anie.200503898.
[23] X. Li, X. San, Y. Zhang, T. Ichii, M. Meng, Y. Tan, N. Tsubaki, Direct synthesis of
ethanol from dimethyl ether and syngas over combined H-mordenite and Cu/ZnO
catalysts, ChemSusChem. 3 (2010) 1192–1199, https://doi.org/10.1002/cssc.
201000109.
[24] T.H. Fleisch, A. Basu, M.J. Gradassi, J.G. Masin, Natural gas conversion IV, Stud.
Surf. Sci. Catal. 107 (1997) 117–125, https://doi.org/10.1016/S0167-2991(97)
80323-0.
[25] B. Prabowo, M. Yan, M. Syamsiro, R.H. Setyobudi, M.K. Biddinika, State of the art
of global dimethyl ether production and its potentional application in Indonesia,
Proc. Pakistan Acad. Sci. 54 (2017) 29–39.
[26] H.J. Majunke, H. Müller Dr., Treibstoff und eine Verwendung desselben,
DE3307091C2, (1984).
[27] D. John, N. Vancouver, Methyl ether fuels for internal combustion engines,
315
Journal of CO₂ Utilization 32 (2019) 299–320
US4892561A, (1990), https://doi.org/10.1074/JBC.274.42.30033.(51).
[28] T.H. Fleisch, A. Basu, R.A. Sills, Introduction and advancement of a new clean
global fuel: The status of DME developments in China and beyond, J. Nat. Gas Sci.
Eng. 9 (2012) 94–107, https://doi.org/10.1016/j.jngse.2012.05.012.
[29] A. Basu, M. Gradassi, R. Sills, T. Fleisch, R. Puri, Use of DME as a gas turbine fuel,
(2001), https://doi.org/10.1115/2001-GT-0003 V002T01A003.
[30] X. Wang, China MTBE: Risks, opportunities, and challenges, 16th IMPCA 2013
Asian Methanol Conference Global MTBE Overview Mexico South America (2019),
www.methanolmsa.com/wp-content/uploads/2013/11/Wang-Xiaoshu.pdf.
[31] S. Hosseininejad, A. Afacan, R.E. Hayes, Catalytic and kinetic study of methanol
dehydration to dimethyl ether, Chem. Eng. Res. Des. 90 (2012) 825–833, https://
doi.org/10.1016/j.cherd.2011.10.007.
[32] P.K. Kiviranta-Pääkkönen, L.K. Struckmann née Rihko, J.A. Linnekoski,
A.O.I. Krause, Dehydration of the alcohol in the etherification of isoamylenes with
methanol and ethanol, Ind. Eng. Chem. Res. 37 (1998) 18–24, https://doi.org/10.
1021/ie970454d.
[33] M.A. Armenta, V.M. Maytorena, R.G. Alamilla, R. Valdez, A. Olivas,
Thermodynamic and catalytic properties of Cu-and Pd-oxides over mixed
γ–χ–Al2O3 for methanol dehydration toward dimethyl ether, Int. J. Hydrogen
Energy 44 (2019) 7276–7287, https://doi.org/10.1016/j.ijhydene.2019.01.243.
[34] J. Bandiera, C. Naccache, Kinetics of methanol dehydration on dealuminated H-
mordenite: model with acid and basic active centres, Appl. Catal. 69 (1991)
139–148, https://doi.org/10.1016/S0166-9834(00)83297-2.
[35] B.C. Gates, L.N. Johanson, The dehydration of methanol and ethanol catalyzed by
polystyrene sulfonate resins, J. Catal. 14 (1969) 69–76, https://doi.org/10.1016/
0021-9517(69)90357-1.
[36] K.S. Ha, Y.J. Lee, J.W. Bae, Y.W. Kim, M.H. Woo, H.S. Kim, M.J. Park, K.W. Jun,
New reaction pathways and kinetic parameter estimation for methanol dehydra-
tion over modified ZSM-5 catalysts, Appl. Catal. A Gen. 395 (2011) 95–106,
https://doi.org/10.1016/j.apcata.2011.01.025.
[37] R. Blaszkowski, R.A. Van Santen, The mechanism of dimethyl ether formation
from methanol catalyzed by zeolitic protons, J. Am. Chem. Soc. 118 (1996)
5152–5153, https://doi.org/10.1021/ja954323k.
[38] R.T. Carr, M. Neurock, E. Iglesia, Catalytic consequences of acid strength in the
conversion of methanol to dimethyl ether, J. Catal. 278 (2011) 78–93, https://doi.
org/10.1016/j.jcat.2010.11.017.
[39] D. Lesthaeghe, V. Van Speybroeck, G.B. Marin, M. Waroquier, Understanding the
failure of direct C-C coupling in the zeolite-catalyzed methanol-to-olefin process,
Angew. Chemie - Int. Ed. 45 (2006) 1714–1719, https://doi.org/10.1002/anie.
200503824.
[40] P.G. Moses, J.K. Nørskov, Methanol to dimethyl ether over ZSM-22: A periodic
density functional theory study, ACS Catal. 3 (2013) 735–745, https://doi.org/10.
1021/cs300722w.
[41] G. Cassone, F. Pietrucci, F. Saija, F. Guyot, J. Sponer, J.E. Sponer, A.M. Saitta,
Novel electrochemical route to cleaner fuel dimethyl ether, Sci. Rep. 7 (2017) 1–9,
https://doi.org/10.1038/s41598-017-07187-8.
[42] D. Mao, W. Yang, J. Xia, B. Zhang, Q. Song, Q. Chen, Highly effective hybrid
catalyst for the direct synthesis of dimethyl ether from syngas with magnesium
oxide-modified HZSM-5 as a dehydration component, J. Catal. 230 (2005)
140–149, https://doi.org/10.1016/j.jcat.2004.12.007.
[43] K. Takeishi, Dimethyl ether and catalyst development for production from syngas,
Biofuels. 1 (2010) 217–226, https://doi.org/10.4155/bfs.09.16.
[44] G.R. Moradi, J. Ahmadpour, F. Yaripour, J. Wang, Equilibrium calculations for
direct synthesis of dimethyl ether from syngas, Can. J. Chem. Eng. 89 (2011)
108–115, https://doi.org/10.1002/cjce.20373.
[45] A. Ateka, P. Pérez-Uriarte, M. Gamero, J. Ereña, A.T. Aguayo, J. Bilbao, A com-
parative thermodynamic study on the CO2 conversion in the synthesis of methanol
and of DME, Energy. 120 (2017) 796–804.
[46] G. Centi, S. Perathoner, Advances in catalysts and processes for methanol synthesis
from CO2, in: M. De Falco, G. Iaquaniello, G. Centi (Eds.), CO2 A Valuab, Source
Carbon, Springer London, London, 2013, pp. 147–169.
[47] F. Yang, Z. Liu, W.S. Li, T.H. Wu, X.P. Zhou, The oxidative bromination of methane
over Rh/SiO2 catalyst, Catal. Lett. 124 (2008) 226–232, https://doi.org/10.1007/
s10562-008-9462-0.
[48] Q. You, Z. Liu, W. Li, X. Zhou, Synthesis of dimethyl ether from methane mediated
by HBr, J. Nat. Gas Chem. 18 (2009) 306–311, https://doi.org/10.1016/S1003-
9953(08)60122-X.
[49] G.K.S. Prakash, J.C. Colmenares, P.T. Batamack, T. Mathew, G.A. Olah, Poly(4-
vinylpyridine) catalyzed hydrolysis of methyl bromide to methanol and dimethyl
ether, J. Mol. Catal. A Chem. 310 (2009) 180–183, https://doi.org/10.1016/j.
molcata.2009.06.018.
[50] G.A. Olah, J. Bukala, Antimony pentafluoride/graphite catalyzed oxidative car-
bonylation of methyl halides with carbon monoxide and copper oxides (or copper/
oxygen) to methyl acetate, J. Org. Chem. 55 (1990) 4293–4297, https://doi.org/
10.1021/jo00301a017.
[51] X.P. Zou, M. Lorkovic, G.D. Stucky, P.C. Ford, J.H. Sherman, P. Grosso, Integrated
process for synthesizing alcohols and ethers from alkanes, US 6472572B1, (2019).
[52] I.M. Lorkovic, A. Yilmaz, G.A. Yilmaz, X.P. Zhou, L.E. Laverman, S. Sun,
D.J. Schaefer, M. Weiss, M.L. Noy, C.I. Cutler, J.H. Sherman, E.W. McFarland,
G.D. Stucky, P.C. Ford, A novel integrated process for the functionalization of
methane and ethane: Bromine as mediator, Catal. Today. 98 (2004) 317–322,
https://doi.org/10.1016/j.cattod.2004.07.058.
[53] M. Farniaei, M. Abbasi, A. Rasoolzadeh, M. Reza, Enhancement of methanol, DME
and hydrogen production via employing hydrogen permselective membranes in a
novel integrated thermally double-coupled two-membrane reactor, J. Nat. Gas Sci.
Eng. 14 (2013) 158–173, https://doi.org/10.1016/j.jngse.2013.06.010.
U. Mondal and G.D. Yadav
[54] R. Phienluphon, K. Pinkaew, G. Yang, J. Li, Q. Wei, Designing core (Cu/ZnO/
Al2O3)–shell (SAPO-11) zeolite capsule catalyst with a facile physical way for
dimethyl ether direct synthesis from syngas, Chem. Eng. J. 270 (2015) 605–611,
https://doi.org/10.1016/j.cej.2015.02.071.
[55] A.T. Aguayo, J. Ereña, D. Mier, J.M. Arandes, M. Olazar, J. Bilbao, Kinetic mod-
eling of dimethyl ether synthesis in a single step on a CuO–ZnO–Al2O3/γ-Al2O3
Catalyst, Ind. Eng. Chem. Res. 46 (2007) 5522–5530, https://doi.org/10.1021/
ie070269s.
[56] Z. Wang, J. Wang, J. Diao, Y. Jin, The synergy effect of process coupling for di-
methyl ether synthesis in slurry reactors, Chem. Eng. Technol. 24 (2001) 507–511
doi:10.1002/1521-4125(200105)24:5 < 507::AID-CEAT507 > 3.0.CO;2-0.
[57] Y. Hu, Z. Nie, D. Fang, Simulation and model design of pipe-shell reactor for the
direct synthesis of dimethyl ether from syngas, J. Nat. Gas Chem. 17 (2008)
195–200, https://doi.org/10.1016/S1003-9953(08)60051-1.
[58] F. Hayer, H. Bakhtiary-Davijany, R. Myrstad, A. Holmen, P. Pfeifer, H.J. Venvik,
Synthesis of dimethyl ether from syngas in a microchannel reactor-Simulation and
experimental study, Chem. Eng. J. 167 (2011) 610–615, https://doi.org/10.1016/
j.cej.2010.09.080.
[59] H. Bakhtiary-Davijany, F. Hayer, X.K. Phan, R. Myrstad, H.J. Venvik, P. Pfeifer,
A. Holmen, Characteristics of an integrated micro packed bed reactor-heat ex-
changer for methanol synthesis from syngas, Chem. Eng. J. 167 (2011) 496–503,
https://doi.org/10.1016/j.cej.2010.08.074.
[60] J. Ereña, I. Sierra, A.T. Aguayo, A. Ateka, M. Olazar, J. Bilbao, Kinetic modelling of
dimethyl ether synthesis from (H2 + CO2) by considering catalyst deactivation,
Chem. Eng. J. 174 (2011) 660–667, https://doi.org/10.1016/j.cej.2011.09.067.
[61] G.C. Chinchen, K. Mansfield, M.S. Spencer, The methanol synthesis-how does it
work, Chemtech 11 (1990) 692–699.
[62] J. Nakamura, I. Nakamura, T. Uchijima, Y. Kanai, T. Watanabe, M. Saito,
T. Fujitani, Methanol synthesis over a Zn-deposited copper model catalyst, Catal.
Letters. 31 (1995) 325–331, https://doi.org/10.1007/BF00808596.
[63] R.J. da Silva, A.F. Pimentel, R.S. Monteiro, C.J.A. Mota, Synthesis of methanol and
dimethyl ether from the CO2 hydrogenation over Cu·ZnO supported on Al2 O3 and
Nb2O5, J. CO2 Util. 15 (2016) 83–88, https://doi.org/10.1016/j.jcou.2016.01.
006.
[64] M. Thorhauge, S. Kuld, I. Chorkendorff, H. Falsig, C. Elkjaer, S. Helveg,
J. Sehested, Quantifying the promotion of Cu catalysts by ZnO for methanol
synthesis, Science 352 (2016) 969–974.
[65] A. Le Valent, C. Comminges, C. Tisseraud, C. Canaff, L. Pinard, Y. Pouilloux, The
Cu-ZnO synergy in methanol synthesis from CO2, Part 1: Origin of active site ex-
plained by experimental studies and a sphere contact quantification model on Cu
+ ZnO mechanical mixtures, J. Catal. 324 (2015) 41–49, https://doi.org/10.
1016/j.jcat.2015.01.021.
[66] W.H. Chen, B.J. Lin, H.M. Lee, M.H. Huang, One-step synthesis of dimethyl ether
from the gas mixture containing CO2 with high space velocity, Appl. Energy 98
(2012) 92–101, https://doi.org/10.1016/j.apenergy.2012.02.082.
[67] S. Sugawa, K. Sayama, K. Okabe, H. Arakawa, Methanol synthesis from CO2 and
H2 over silver catalyst, Energy Convers. Manag. 36 (1995) 665–668, https://doi.
org/10.1016/0196-8904(95)00093-S.
[68] X. Jiang, N. Koizumi, X. Guo, C. Song, Bimetallic Pd-Cu catalysts for selective CO2
hydrogenation to methanol, Appl. Catal. B Environ. 170-171 (2015) 173–185,
https://doi.org/10.1016/j.apcatb.2015.01.010.
[69] F. Arena, K. Barbera, G. Italiano, G. Bonura, L. Spadaro, F. Frusteri, Synthesis,
characterization and activity pattern of Cu-ZnO/ZrO2 catalysts in the hydro-
genation of carbon dioxide to methanol, J. Catal. 249 (2007) 185–194, https://
doi.org/10.1016/j.jcat.2007.04.003.
[70] R. Raudaskoski, M.V. Niemela, R.L. Keiski, The effect of ageing time on co-pre-
cipitated Cu/ZnO/ZrO2 catalysts used in methanol synthesis from CO2 and H2,
Top. Catal. 45 (2007) 57–60, https://doi.org/10.1007/s11244-007-0240-9.
[71] L. Angelo, K. Kobl, L.M.M. Tejada, Y. Zimmermann, K. Parkhomenko, A.C. Roger,
Study of CuZn MOx oxides (M = Al, Zr, Ce, CeZr) for the catalytic hydrogenation
of CO2 into methanol, C.R. Chim. 18 (2015) 250–260, https://doi.org/10.1016/j.
crci.2015.01.001.
[72] E.L. Fornero, P.B. Sanguineti, D.L. Chiavassa, A.L. Bonivardi, M.A. Baltanás,
Performance of ternary Cu-Ga2O3-ZrO2 catalysts in the synthesis of methanol
using CO2-rich gas mixtures, Catal. Today 213 (2013) 163–170, https://doi.org/
10.1016/j.cattod.2013.03.012.
[74] G. Wang, Y. Zuo, M. Han, J. Wang, Copper crystallite size and methanol synthesis
catalytic property of Cu-based catalysts promoted by Al, Zr and Mn, React. Kinet.
Mech. Catal. 101 (2010) 443–454, https://doi.org/10.1007/s11144-010-0240-9.
[75] S. Mehta, G.W. Simmons, K. Klier, R.G. Herman, Catalytic synthesis of methanol
from COH2: II. Electron microscopy (TEM, STEM, microdiffraction, and energy
dispersive analysis) of the CuZnO and Cu/ZnO/Cr2O3 catalysts, J. Catal. 57 (1979)
339–360, https://doi.org/10.1016/0021-9517(79)90001-0.
[76] N. Pasupulety, H. Driss, Y.A. Alhamed, A.A. Alzahrani, M.A. Daous, L. Petrov,
Studies on Au/Cu-Zn-Al catalyst for methanol synthesis from CO2, Appl. Catal. A
Gen. 504 (2015) 308–318, https://doi.org/10.1016/j.apcata.2015.01.036.
[77] H. Zhan, F. Li, P. Gao, N. Zhao, F. Xiao, W. Wei, L. Zhong, Y. Sun, Methanol
synthesis from CO2 hydrogenation over La-M-Cu-Zn-O (M = Y, Ce, Mg, Zr) cata-
lysts derived from perovskite-type precursors, J. Power Sources 251 (2014)
113–121, https://doi.org/10.1016/j.jpowsour.2013.11.037.
[78] N. Kanoun, M.P. Astier, G.M. Pajonk, Catalytic properties of new Cu based cata-
lysts containing Zr and/or V for methanol synthesis from a carbon dioxide and
hydrogen mixture, Catal. Letters. 15 (1992) 231–235, https://doi.org/10.1007/
BF00765266.
[79] V. Deerattrakul, P. Dittanet, M. Sawangphruk, P. Kongkachuichay, CO2 hydro-
genation to methanol using Cu-Zn catalyst supported on reduced graphene oxide
316
Journal of CO₂ Utilization 32 (2019) 299–320
nanosheets, J. CO2 Util. 16 (2016) 104–113, https://doi.org/10.1016/j.jcou.2016.
07.002.
[80] N. Ahmed, Y. Shibata, T. Taniguchi, Y. Izumi, Photocatalytic conversion of carbon
dioxide into methanol using zinc-copper-M(III) (M = aluminum, gallium) layered
double hydroxides, J. Catal. 279 (2011) 123–135, https://doi.org/10.1016/j.jcat.
2011.01.004.
[81] W. Wang, S. Wang, X. Ma, J. Gong, Recent advances in catalytic hydrogenation of
carbon dioxide, Chem. Soc. Rev. 40 (2011) 3703–3727, https://doi.org/10.1039/
c1cs15008a.
[82] L. Jia, J. Gao, W. Fang, Q. Li, Carbon dioxide hydrogenation to methanol over the
pre-reduced LaCr0.5Cu0.5O3 catalyst, Catal. Commun. 10 (2009) 2000–2003,
https://doi.org/10.1016/j.catcom.2009.07.017.
[83] E. Catizzone, G. Bonura, M. Migliori, F. Frusteri, G. Giordano, CO2 recycling to
dimethyl ether: State-of-the-art and perspectives, Molecules. 23 (2018) 1–28,
https://doi.org/10.3390/molecules23010031.
[84] W. Wang, S. Wang, X. Ma, J. Gong, W. Wang, Recent advances in catalytic hy-
drogenation of carbon dioxide, Chem. Soc. Rev. 40 (2011) 3369–4260, https://
doi.org/10.1039/c1cs15008a.
[85] O. Martin, A.J. Martín, C. Mondelli, S. Mitchell, T.F. Segawa, R. Hauert,
C. Drouilly, D. Curulla-Ferré, J. Pérez-Ramírez, Indium oxide as a superior catalyst
for methanol synthesis by CO2 hydrogenation, Angew. Chem. Int. Ed. 55 (2016)
6261–6265, https://doi.org/10.1002/anie.201600943.
[86] A. Gotti, R. Prins, Basic metal oxides as cocatalysts for Cu/SiO2 catalysts in the
conversion of synthesis gas to methanol, J. Catal. 519 (1998) 511–519.
[87 Y. Kikuzono, S. Kagami, S. Naito, T. Onishi, K. Tamaru, Selective hydrogenation of
carbon monoxide on palladium catalysts, Faraday Discuss. Chem. Soc. 72 (1981)
135–143, https://doi.org/10.1039/DC9817200135.
[88] T. Fujitani, M. Saito, Y. Kanai, T. Watanabe, J. Nakamura, T. Uchijima,
Development of an active Ga2O3 supported palladium catalyst for the synthesis of
methanol from carbon dioxide and hydrogen, Appl. Catal. A Gen. 125 (1995)
199–202, https://doi.org/10.1016/0926-860X(95)00049-6.
[89] S.E. Collins, M.A. Baltanás, A.L. Bonivardi, An infrared study of the intermediates
of methanol synthesis from carbon dioxide over Pd/β-Ga2O3, J. Catal. 226 (2004)
410–421, https://doi.org/10.1016/j.jcat.2004.06.012.
[90] S.E. Collins, J.J. Delgado, C. Mira, J.J. Calvino, S. Bernal, D.L. Chiavassa,
M.A. Baltanás, A.L. Bonivardi, The role of Pd-Ga bimetallic particles in the bi-
functional mechanism of selective methanol synthesis via CO2 hydrogenation on a
Pd/Ga2O3 catalyst, J. Catal. 292 (2012) 90–98, https://doi.org/10.1016/j.jcat.
2012.05.005.
[91] D.L. Chiavassa, S.E. Collins, A.L. Bonivardi, M.A. Baltanás, Methanol synthesis
from CO2/H2 using Ga2O3-Pd/silica catalysts: Kinetic modeling, Chem. Eng. J. 150
(2009) 204–212, https://doi.org/10.1016/j.cej.2009.02.013.
[92] J. Díez-Ramírez, J.L. Valverde, P. Sánchez, F. Dorado, CO2 hydrogenation to
methanol at atmospheric pressure: influence of the preparation method of Pd/ZnO
catalysts, Catal. Letters. 146 (2016) 373–382, https://doi.org/10.1007/s10562-
015-1627-z.
[93] N. Koizumi, X. Jiang, J. Kugai, C. Song, Effects of mesoporous silica supports and
alkaline promoters on activity of Pd catalysts in CO2 hydrogenation for methanol
synthesis, Catal. Today 194 (2012) 16–24, https://doi.org/10.1016/j.cattod.2012.
08.007.
[94] P.D. Adkins, H. Perkins, The behavior of methanol over aluminum and zinc oxides,
J. Phys. Chem. C. (2018) 221–224, https://doi.org/10.1021/j150284a006.
[95] D.M. Sung, Y.H. Kim, E.D. Park, J.E. Yie, Correlation between acidity and catalytic
activity for the methanol dehydration over various aluminum oxides, Res. Chem.
Intermed. 36 (2010) 653–660, https://doi.org/10.1007/s11164-010-0201-y.
[96] M. Xu, J.H. Lunsford, D.W. Goodman, A. Bhattacharyya, Synthesis of dimethyl
ether (DME) from methanol over solid-acid catalysts, Appl. Catal. A Gen. 149
(1997) 289–301, https://doi.org/10.1016/S0926-860X(96)00275-X.
[97] Y. Fu, T. Hong, J. Chen, A. Auroux, J. Shen, Surface acidity and the dehydration of
methanol to dimethyl ether, Thermochim. Acta 434 (2005) 22–26, https://doi.
org/10.1016/j.tca.2004.12.023.
[98] A. Corma, State of the art and future challenges of zeolites as catalysts, J. Catal.
216 (2003) 298–312, https://doi.org/10.1016/S0021-9517(02)00132-X.
[99] V. Vishwanathan, K. Jun, J. Kim, H. Roh, Vapour phase dehydration of crude
methanol to dimethyl ether over Na-modified H-ZSM-5 catalysts, Appl. Catal. A
Gen. 276 (2004) 251–255, https://doi.org/10.1016/j.apcata.2004.08.011.
[100] Z. Azizi, M. Rezaeimanesh, T. Tohidian, M.R. Rahimpour, Dimethyl ether: A
review of technologies and production challenges, Chem. Eng. Process. Process
Intensif. 82 (2014) 150–172, https://doi.org/10.1016/j.cep.2014.06.007.
[101] J.M. Campelo, F. Lafont, J.M. Marinas, M. Ojeda, Studies of catalyst deactivation
in methanol conversion with high, medium and small pore silicoaluminopho-
sphates, Appl. Catal. A Gen. 192 (2000) 85–96.
[102] E. Catizzone, A. Aloise, M. Migliori, G. Giordano, General Dimethyl ether synthesis
via methanol dehydration: Effect of zeolite structure, Appl. Catal. A Gen. 502
(2015) 215–220, https://doi.org/10.1016/j.apcata.2015.06.017.
[103] E. Catizzone, A. Aloise, M. Migliori, G. Giordano, From 1-D to 3-D zeolite struc-
tures: performance assessment in catalysis of vapour-phase methanol dehydration
to DME, Microporous Mesoporous Mater. 243 (2017) 102–111, https://doi.org/
10.1016/j.micromeso.2017.02.022.
[104] N. Khandan, M. Kazemeini, M. Aghaziarati, Determining an optimum catalyst for
liquid-phase dehydration of methanol to dimethyl ether, Appl. Catal. A Gen. 349
(2008) 6–12, https://doi.org/10.1016/j.apcata.2008.07.029.
[105] Q. Tang, H. Xu, Y. Zheng, J. Wang, H. Li, J. Zhang, Appl. Catal. A: Gen. Catalytic
dehydration of methanol to dimethyl ether over micro – mesoporous ZSM-5/MCM-
41 composite molecular sieves, Appl. Catal. A Gen. 413-414 (2012) 36–42,
https://doi.org/10.1016/j.apcata.2011.10.039.
U. Mondal and G.D. Yadav
[106] Z. Bai, H. Ma, H. Zhang, W. Ying, D. Fang, Simulation of a multi-stage adiabatic
reactor with inter-stage quenching for dimethyl ether synthesis, Chem. Ind. Chem.
Eng. Q. 20 (2014) 481–490.
[107] E. Catizzone, A. Aloise, M. Migliori, G. Giordano, The effect of FER zeolite acid
sites in methanol-to-dimethyl-ether catalytic dehydration, J. Energy Chem. 26
(2017) 406–415, https://doi.org/10.1016/j.jechem.2016.12.005.
[108] Y. Hu, Z. Nie, D. Fang, Simulation and model design of pipe-shell reactor for the
direct synthesis of dimethyl ether from syngas, J. Nat. Gas Chem. 17 (2008)
195–200, https://doi.org/10.1016/S1003-9953(08)60051-1.
[109] S. Hassanpour, M. Taghizadeh, Preparation, characterization, and activity eva-
luation of H-ZSM-5 catalysts in vapor-phase methanol dehydration to dimethyl
ether, Ind. Eng. Chem. Res. (2010) 4063–4069, https://doi.org/10.1021/
ie9013869.
[110] N. Khandan, M. Kazemeyni, M. Aghaziarati, Dehydration of methanol to dimethyl
ether employing modified H-ZSM-5 catalysts, Iran. J. Chem. Eng. 6 (2009) 3–11.
[111] S.D. Kim, S.C. Baek, Y.-J. Lee, K.-W. Jun, M.J. Kim, I.S. Yoo, Effect of γ-alumina
content on catalytic performance of modified ZSM-5 for dehydration of crude
methanol to dimethyl ether, Appl. Catal. A Gen. 309 (2006) 139–143, https://doi.
org/10.1016/j.apcata.2006.05.008.
[112] W. Alharbi, E.F. Kozhevnikova, I.V. Kozhevnikov, Dehydration of methanol to
dimethyl ether over heteropoly acid catalysts: The relationship between reaction
rate and catalyst acid strength, ACS Catal. 5 (2015) 7186–7193, https://doi.org/
10.1021/acscatal.5b01911.
[113] R.M. Ladera, J.L.G. Fierro, M. Ojeda, S. Rojas, TiO2-supported heteropoly acids for
low-temperature synthesis of dimethyl ether from methanol, J. Catal. 312 (2014)
195–203, https://doi.org/10.1016/j.jcat.2014.01.016.
[114] A. Ciftci, N.A. Sezgi, T. Dogu, Nafion-incorporated silicate structured nano-
composite mesoporous catalysts for dimethyl ether synthesis, Ind. Eng. Chem. Res.
49 (2010) 6753–6762, https://doi.org/10.1021/ie9015667.
[115] D. Varışlı, T. Doğu, Production of clean transportation fuel dimethylether by de-
hydration of methanol over nafion catalyst, Gazi Univ. J. Sci. 21 (2008) 37–41,
https://doi.org/10.1016/S0140-6701(03)82853-9.
[116] J.J. Spivey, Review: dehydration catalysts for the methanol/dimethyl ether reac-
tion, Chem. Eng. Technol. (2010) 37–41, https://doi.org/10.1080/
00986449108939946.
[117] S. Hosseininejad, A. Afacan, R.E. Hayes, Catalytic and kinetic study of methanol
dehydration to dimethyl ether, Chem. Eng. Res. Des. 90 (2011) 825–833, https://
doi.org/10.1016/j.cherd.2011.10.007.
[118] K.C. Tokay, T. Dogu, G. Dogu, Dimethyl ether synthesis over alumina based cat-
alysts, Chem. Eng. J. 184 (2012) 278–285, https://doi.org/10.1016/j.cej.2011.12.
034.
[119] B. Sabour, M. Hassan, T. Hamoule, M. Rashidzadeh, Catalytic dehydration of
methanol to dimethyl ether (DME) over Al-HMS catalysts, J. Ind. Eng. Chem. 20
(2014) 222–227, https://doi.org/10.1016/j.jiec.2013.03.044.
[120] S. Ren, W.R. Shoemaker, X. Wang, Z. Shang, N. Klinghoffer, S. Li, M. Yu, X. He,
T.A. White, X. Liang, Highly active and selective Cu-ZnO based catalyst for me-
thanol and dimethyl ether synthesis via CO2 hydrogenation, Fuel 239 (2019)
1125–1133, https://doi.org/10.1016/j.fuel.2018.11.105.
[121] M. Stiefel, R. Ahmad, U. Arnold, M. Döring, Direct synthesis of dimethyl ether
from carbon-monoxide-rich synthesis gas: Influence of dehydration catalysts and
operating conditions, Fuel Process. Technol. 92 (2011) 1466–1474, https://doi.
org/10.1016/j.fuproc.2011.03.007.
[122] S. Papari, M. Kazemeini, M. Fattahi, Mathematical modeling of a slurry reactor for
DME direct synthesis from syngas, J. Nat. Gas Chem. 21 (2012) 148–157, https://
doi.org/10.1016/S1003-9953(11)60347-2.
[123] I. Sierra, J. Ereña, A.T. Aguayo, J.M. Arandes, M. Olazar, J. Bilbao, Co-feeding
water to attenuate deactivation of the catalyst metallic function (CuO-ZnO-Al2O3)
by coke in the direct synthesis of dimethyl ether, Appl. Catal. B Environ. 106
(2011) 167–173, https://doi.org/10.1016/j.apcatb.2011.05.021.
[124] S.P. Naik, T. Ryu, V. Bui, J.D. Miller, N.B. Drinnan, W. Zmierczak, Synthesis of
DME from CO2/H2 gas mixture, Chem. Eng. J. 167 (2011) 362–368, https://doi.
org/10.1016/j.cej.2010.12.087.
[125] Q. Zhang, Y.Z. Zuo, M.H. Han, J.F. Wang, Y. Jin, F. Wei, Long carbon nanotubes
intercrossed Cu/Zn/Al/Zr catalyst for CO/CO2 hydrogenation to methanol/di-
methyl ether, Catal. Today 150 (2010) 55–60, https://doi.org/10.1016/j.cattod.
2009.05.018.
[126] F. Zha, J. Ding, Y. Chang, J. Ding, J. Wang, J. Ma, Cu-Zn-al oxide cores packed by
metal-doped amorphous silica-alumina membrane for catalyzing the hydrogena-
tion of carbon dioxide to dimethyl ether, Ind. Eng. Chem. Res. 51 (2012) 345–352,
https://doi.org/10.1021/ie202090f.
[127] T. Takeguchi, K.I. Yanagisawa, T. Inui, M. Inoue, Effect of the property of solid
acid upon syngas-to-dimethyl ether conversion on the hybrid catalysts composed
of Cu-Zn-Ga and solid acids, Appl. Catal. A Gen. 192 (2000) 201–209, https://doi.
org/10.1016/S0926-860X(99)00343-9.
[128] S.H. Lima, A.M.S. Forrester, L.A. Palacio, A.C. Faro, Niobia-alumina as methanol
dehydration component in mixed catalyst systems for dimethyl ether production
from syngas, Appl. Catal. A Gen. 488 (2014) 19–27, https://doi.org/10.1016/j.
apcata.2014.09.022.
[129] O.S. Joo, K.D. Jung, S.H. Han, Modification of H-ZSM-5 and γ-alumina with for-
maldehyde and its application to the synthesis of dimethyl ether from syn-gas,
Bull. Korean Chem. Soc. 23 (2002) 1103–1105, https://doi.org/10.5012/bkcs.
2002.23.8.1103.
[130] S. Asthana, C. Samanta, A. Bhaumik, B. Banerjee, R.K. Voolapalli, B. Saha, Direct
synthesis of dimethyl ether from syngas over Cu-based catalysts: Enhanced se-
lectivity in the presence of MgO, J. Catal. 334 (2016) 89–101, https://doi.org/10.
1016/j.jcat.2015.10.020.
317
Journal of CO₂ Utilization 32 (2019) 299–320
[131] Y. Tan, H. Xie, H. Cui, Y. Han, B. Zhong, Modification of Cu-based methanol
synthesis catalyst for dimethyl ether synthesis from syngas in slurry phase, Catal.
Today 104 (2005) 25–29, https://doi.org/10.1016/j.cattod.2005.03.033.
[132] M.H. Huang, H.M. Lee, K.C. Liang, C.C. Tzeng, W.H. Chen, An experimental study
on single-step dimethyl ether (DME) synthesis from hydrogen and carbon mon-
oxide under various catalysts, Int. J. Hydrogen Energy 40 (2015) 13583–13593,
https://doi.org/10.1016/j.ijhydene.2015.07.168.
[133] Z. Li, J. Li, M. Dai, Y. Liu, D. Han, J. Wu, The effect of preparation method of the
Cu-La2O3-ZrO2/γ-Al2O3 hybrid catalysts on one-step synthesis of dimethyl ether
from syngas, Fuel 121 (2014) 173–177, https://doi.org/10.1016/j.fuel.2013.12.
050.
[134] A. Venugopal, J. Palgunadi, J.K. Deog, O.S. Joo, C.H. Shin, Dimethyl ether
synthesis on the admixed catalysts of Cu-Zn-Al-M (M = Ga, La, Y, Zr) and γ-Al2O3:
The role of modifier, J. Mol. Catal. A Chem. 302 (2009) 20–27, https://doi.org/10.
1016/j.molcata.2008.11.038.
[135] Q. Zhang, Y.Z. Zuo, M.H. Han, J.F. Wang, Y. Jin, F. Wei, Long carbon nanotubes
intercrossed Cu/Zn/Al/Zr catalyst for CO/CO2 hydrogenation to methanol/di-
methyl ether, Catal. Today. 150 (2010) 55–60, https://doi.org/10.1016/j.cattod.
2009.05.018.
[136] J. Toyir, P.R. De la Piscina, J.L.G. Fierro, N. Homs, Catalytic performance for CO2
conversion to methanol of gallium-promoted copper-based catalysts: Influence of
metallic precursors, Appl. Catal. B Environ. 34 (2001) 255–266, https://doi.org/
10.1016/S0926-3373(01)00203-X.
[137] G.R. Moradi, S. Nosrati, F. Yaripor, Effect of the hybrid catalysts preparation
method upon direct synthesis of dimethyl ether from synthesis gas, Catal.
Commun. 8 (2007) 598–606, https://doi.org/10.1016/j.catcom.2006.08.023.
[138] Z. Gao, W. Huang, L. Yin, L. Hao, K. Xie, The structure properties of CuZnAl slurry
catalysts prepared by a complete liquid-phase method and its catalytic perfor-
mance for DME synthesis from syngas, Catal. Letters 127 (2009) 354–359, https://
doi.org/10.1007/s10562-008-9689-9.
[139] H. Jiang, H. Bongard, W. Schmidt, F. Schüth, One-pot synthesis of mesoporous
Cu–γ-Al2O3 as bifunctional catalyst for direct dimethyl ether synthesis,
Microporous Mesoporous Mater. 164 (2012) 3–8, https://doi.org/10.1016/j.
micromeso.2012.08.004.
[140] Y. Wang, Y. Chen, F. Yu, D. Pan, B. Fan, J. Ma, R. Li, One-step synthesis of di-
methyl ether from syngas on ordered mesoporous copper incorporated alumina, J.
Energy Chem. 25 (2016) 775–781, https://doi.org/10.1016/j.jechem.2016.04.
014.
[141] J. Abu-Dahrieh, D. Rooney, A. Goguet, Y. Saih, Activity and deactivation studies
for direct dimethyl ether synthesis using CuO-ZnO-Al2O3 with NH4ZSM-5, HZSM-5
or γ-Al2O3, Chem. Eng. J. 203 (2012) 201–211, https://doi.org/10.1016/j.cej.
2012.07.011.
[142] Y. Tavan, S.H. Hosseini, M. Ghavipour, M.R.K. Nikou, A. Shariati, From laboratory
experiments to simulation studies of methanol dehydration to produce dimethyl
ether - Part I: Reaction kinetic study, Chem. Eng. Process. Process Intensif. 73
(2013) 144–150, https://doi.org/10.1016/j.cep.2013.06.006.
[143] J.J. Spivey, Review: Dehydration catalysts for the methanol/dimethyl ether re-
action, Chem. Eng. Commun. 110 (1991) 123–142, https://doi.org/10.1080/
00986449108939946.
[144] F.S. Ramos, A.M.D. De Farias, L.E.P. Borges, J.L. Monteiro, M.A. Fraga, E.F. Sousa-
Aguiar, L.G. Appel, Role of dehydration catalyst acid properties on one-step DME
synthesis over physical mixtures, Catal. Today 101 (2005) 39–44, https://doi.org/
10.1016/j.cattod.2004.12.007.
[145] J. Fei, Z. Hou, B. Zhu, H. Lou, X. Zheng, Synthesis of dimethyl ether (DME) on
modified HY zeolite and modified HY zeolite-supported Cu-Mn-Zn catalysts, Appl.
Catal. A Gen. 304 (2006) 49–54, https://doi.org/10.1016/j.apcata.2006.02.019.
[146] Q. Xie, P. Chen, P. Peng, S. Liu, P. Peng, B. Zhang, Y. Cheng, Y. Wan, Y. Liu,
R. Ruan, Single-step synthesis of DME from syngas on CuZnAl-zeolite bifunctional
catalysts: The influence of zeolite type, RSC Adv. 5 (2015) 26301–26307, https://
doi.org/10.1039/c5ra02814k.
[147] A. García-Trenco, A. Vidal-Moya, A. Martínez, Study of the interaction between
components in hybrid CuZnAl/HZSM-5 catalysts and its impact in the syngas-to-
DME reaction, Catal. Today 179 (2012) 43–51, https://doi.org/10.1016/j.cattod.
2011.06.034.
[148] D. Mao, X. Guo, Dimethyl ether synthesis from syngas over the admixed Cu/ZnO/
Al2O3 catalyst and alkaline earth oxide-modified HZSM-5 zeolite, Energy Technol.
2 (2014) 882–888, https://doi.org/10.1002/ente.201402071.
[149] Q.-L. Xu, P. Lan, S.-P. Zhang, T.-C. Li, Y.-J. Yan, Effect of modified zeolite on one-
step process of DME synthesis, Pet. Sci. Technol. 29 (2011) 439–448, https://doi.
org/10.1080/10916460903117552.
[150] R. Montesano, A. Narvaez, D. Chadwick, Shape-selectivity effects in syngas-to-
dimethyl ether conversion over Cu/ZnO/Al2O3 and zeolite mixtures: Carbon de-
position and by-product formation, Appl. Catal. A Gen. 482 (2014) 69–77, https://
doi.org/10.1016/j.apcata.2014.05.009.
[151] P.S. Sai Prasad, J.W. Bae, S.H. Kang, Y.J. Lee, K.W. Jun, Single-step synthesis of
DME from syngas on Cu-ZnO-Al2O3/zeolite bifunctional catalysts: The superiority
of ferrierite over the other zeolites, Fuel Process. Technol. 89 (2008) 1281–1286,
https://doi.org/10.1016/j.fuproc.2008.07.014.
[152] S.-H. Kang, J.W. Bae, K.-W. Jun, H.S. Potdar, Dimethyl ether synthesis from syngas
over the composite catalysts of Cu–ZnO–Al2O3/Zr-modified zeolites, Catal.
Commun. 9 (2008) 2035–2039, https://doi.org/10.1016/j.catcom.2008.03.046.
[153] Q. Ge, Y. Huang, F. Qiu, S. Li, Bifunctional catalysts for conversion of synthesis gas
to dimethyl ether, Appl. Catal. A: Gen. 167 (1998) 23–30, https://doi.org/10.
1016/S0926-860X(97)00290-1.
[154] F. Frusteri, G. Bonura, C. Cannilla, G.D. Ferrante, A. Aloise, E. Catizzone,
M. Migliori, G. Giordano, Environmental stepwise tuning of metal-oxide and acid
U. Mondal and G.D. Yadav
sites of CuZnZr-MFI hybrid catalysts for the direct DME synthesis by CO2 hydro-
genation, Appl. Catal. B Environ. 176-177 (2015) 522–531, https://doi.org/10.
1016/j.apcatb.2015.04.032.
[155] F. Frusteri, M. Migliori, C. Cannilla, L. Frusteri, E. Catizzone, A. Aloise,
G. Giordano, G. Bonura, Direct CO2-to-DME hydrogenation reaction: New evi-
dences of a superior behaviour of FER-based hybrid systems to obtain high DME
yield, J. CO2 Util. 18 (2017) 353–361.
[156] H.J. Chen, C.W. Fan, C.S. Yu, Analysis, synthesis, and design of a one-step di-
methyl ether production via a thermodynamic approach, Appl. Energy 101 (2013)
449–456, https://doi.org/10.1016/j.apenergy.2012.08.025.
[157] G.R. Moradi, F. Yaripour, P. Vale-Sheyda, Catalytic dehydration of methanol to
dimethyl ether over mordenite catalysts, Fuel Process. Technol. 91 (2010)
461–468, https://doi.org/10.1016/j.fuproc.2009.12.005.
[158] A.A. Rownaghi, F. Rezaei, M. Stante, J. Hedlund, Selective dehydration of me-
thanol to dimethyl ether on ZSM-5 nanocrystals, Appl. Catal. B Environ. 119-120
(2012) 56–61, https://doi.org/10.1016/j.apcatb.2012.02.017.
[159] F. Raoof, M. Taghizadeh, A. Eliassi, F. Yaripour, Effects of temperature and feed
composition on catalytic dehydration of methanol to dimethyl ether over γ-alu-
mina, Fuel 87 (2008) 2967–2971, https://doi.org/10.1016/j.fuel.2008.03.025.
[160] A. Ateka, J. Ereña, J. Bilbao, A.T. Aguayo, Kinetic modeling of the direct synthesis
of dimethyl ether over a CuO–ZnO–MnO/SAPO–18 catalyst and assessment of the
CO2 conversion, Fuel Process. Technol. 181 (2018) 233–243, https://doi.org/10.
1016/j.fuproc.2018.09.024.
[161] S.C. Baek, S.H. Kang, J.W. Bae, Y.J. Lee, D.H. Lee, K.Y. Lee, Effect of copper
precursors to the activity for dimethyl ether synthesis from syngas over Cu-ZnO/γ-
Al2O3 bifunctional catalysts, Energy Fuels 25 (2011) 2438–2443, https://doi.org/
10.1021/ef200504p.
[162] Q. Ge, Y. Huang, F. Qiu, S. Li, Bifunctional catalysts for conversion of synthesis gas
to dimethyl ether, Appl. Catal. A Gen. 167 (1998) 23–30, https://doi.org/10.
1016/S0926-860X(97)00290-1.
[163] C. Zeng, J. Sun, G. Yang, I. Ooki, K. Hayashi, Y. Yoneyama, A. Taguchi, T. Abe,
N. Tsubaki, Highly selective and multifunctional Cu/ZnO/Zeolite catalyst for one-
step dimethyl ether synthesis: Preparing catalyst by bimetallic physical sputtering,
Fuel 112 (2013) 140–144, https://doi.org/10.1016/j.fuel.2013.05.026.
[164] R. Ahmad, D. Schrempp, S. Behrens, J. Sauer, M. Döring, U. Arnold, Zeolite-based
bifunctional catalysts for the single step synthesis of dimethyl ether from CO-rich
synthesis gas, Fuel Process. Technol. 121 (2014) 38–46, https://doi.org/10.1016/
j.fuproc.2014.01.006.
[165] R. Khoshbin, M. Haghighi, Direct conversion of syngas to dimethyl ether as a green
fuel over ultrasound-assisted synthesized CuO–ZnO–Al2O3/HZSM-5 nanocatalyst:
effect of active phase ratio on physicochemical and catalytic properties at different
process conditions, Catal. Sci. Technol. 4 (2014) 1779–1792, https://doi.org/10.
1039/C3CY01089A.
[166] S. Allahyari, M. Haghighi, A. Ebadi, H. Qavam Saeedi, Direct synthesis of dimethyl
ether as a green fuel from syngas over nanostructured CuO–ZnO–Al2O3/HZSM-5
catalyst: Influence of irradiation time on nanocatalyst properties and catalytic
performance, J. Power Sources 272 (2014) 929–939, https://doi.org/10.1016/j.
jpowsour.2014.07.152.
[167] R. Khoshbin, M. Haghighi, Direct syngas to DME as a clean fuel: The beneficial use
of ultrasound for the preparation of CuO-ZnO-Al2O3/HZSM-5 nanocatalyst, Chem.
Eng. Res. Des. 91 (2013) 1111–1122, https://doi.org/10.1016/j.cherd.2012.11.
017.
[168] Z. Hosseini, M. Taghizadeh, F. Yaripour, Synthesis of nanocrystalline γ-Al2O3 by
sol-gel and precipitation methods for methanol dehydration to dimethyl ether, J.
Nat. Gas Chem. 20 (2011) 128–134, https://doi.org/10.1016/S1003-9953(10)
60172-7.
[169] V.V. Ordomsky, M. Cai, V. Sushkevich, S. Moldovan, O. Ersen, C. Lancelot,
V. Valtchev, A.Y. Khodakov, The role of external acid sites of ZSM-5 in deacti-
vation of hybrid CuZnAl/ZSM-5 catalyst for direct dimethyl ether synthesis from
syngas, Appl. Catal. A Gen. 486 (2014) 266–275, https://doi.org/10.1016/j.
apcata.2014.08.030.
[170] J.H. Kim, M.J. Park, S.J. Kim, O.S. Joo, K.D. Jung, DME synthesis from synthesis
gas on the admixed catalysts of Cu/ZnO/Al2O3and ZSM-5, Appl. Catal. A Gen. 264
(2004) 37–41, https://doi.org/10.1016/j.apcata.2003.12.058.
[171] A. García-Trenco, S. Valencia, A. Martínez, The impact of zeolite pore structure on
the catalytic behavior of CuZnAl/zeolite hybrid catalysts for the direct DME
synthesis, Appl. Catal. A Gen. 468 (2013) 102–111, https://doi.org/10.1016/j.
apcata.2013.08.038.
[172] M. Cai, A. Palčić, V. Subramanian, S. Moldovan, O. Ersen, V. Valtchev,
V.V. Ordomsky, A.Y. Khodakov, Direct dimethyl ether synthesis from syngas on
copper-zeolite hybrid catalysts with a wide range of zeolite particle sizes, J. Catal.
338 (2016) 227–238, https://doi.org/10.1016/j.jcat.2016.02.025.
[173] A. García-trenco, A. Martínez, Direct synthesis of DME from syngas on hybrid
CuZnAl/ZSM-5 catalysts: New insights into the role of zeolite acidity, Appl. Catal.
A Gen. 412 (2012) 170–179, https://doi.org/10.1016/j.apcata.2011.10.036.
[174] A. García-Trenco, A. Martínez, A simple and efficient approach to confine Cu/ZnO
methanol synthesis catalysts in the ordered mesoporous SBA-15 silica, Catal.
Today. 215 (2013) 152–161, https://doi.org/10.1016/j.cattod.2013.03.005.
[175] G. Yang, D. Wang, Y. Yoneyama, Y. Tan, N. Tsubaki, Facile synthesis of H-type
zeolite shell on a silica substrate for tandem catalysis, Chem. Commun. 48 (2012)
1263–1265, https://doi.org/10.1039/c2cc16713a.
[176] G. Yang, N. Tsubaki, J. Shamoto, Y. Yoneyama, Y. Zhang, Confinement effect and
synergistic function of H-ZSM-5/Cu-ZnO-Al2O3 capsule catalyst for one-step con-
trolled synthesis, J. Am. Chem. Soc. 132 (2010) 8129–8136, https://doi.org/10.
1021/ja101882a.
[177] G. Yang, M. Thongkam, T. Vitidsant, Y. Yoneyama, Y. Tan, N. Tsubaki, A double-
318
Journal of CO₂ Utilization 32 (2019) 299–320
shell capsule catalyst with core-shell-like structure for one-step exactly controlled
synthesis of dimethyl ether from CO2 containing syngas, Catal. Today 171 (2011)
229–235, https://doi.org/10.1016/j.cattod.2011.02.021.
[178] K. Pinkaew, G. Yang, T. Vitidsant, Y. Jin, C. Zeng, Y. Yoneyama, N. Tsubaki, A new
core-shell-like capsule catalyst with SAPO-46 zeolite shell encapsulated Cr/ZnO
for the controlled tandem synthesis of dimethyl ether from syngas, Fuel. 111
(2013) 727–732, https://doi.org/10.1016/j.fuel.2013.03.027.
[179] R. Nie, H. Lei, S. Pan, L. Wang, J. Fei, Z. Hou, Core-shell structured CuO-ZnO@H-
ZSM-5 catalysts for CO hydrogenation to dimethyl ether, Fuel. 96 (2012) 419–425,
https://doi.org/10.1016/j.fuel.2011.12.048.
[180] M. Sánchez-Contador, A. Ateka, A.T. Aguayo, J. Bilbao, Direct synthesis of di-
methyl ether from CO and CO2 over a core-shell structured CuO-ZnO-ZrO2@
SAPO-11 catalyst, Fuel Process. Technol. 179 (2018) 258–268, https://doi.org/10.
1016/j.fuproc.2018.07.009.
[181] M. Sánchez-Contador, A. Ateka, P. Rodriguez-Vega, J. Bilbao, A.T. Aguayo,
Optimization of the Zr content in the CuO-ZnO-ZrO2/SAPO-11 catalyst for the
selective hydrogenation of CO + CO2 mixtures in the direct synthesis of dimethyl
ether, Ind. Eng. Chem. Res. 57 (2018) 1169–1178, https://doi.org/10.1021/acs.
iecr.7b04345.
[182] Y. Wang, W. Wang, Y. Chen, J. Zheng, R. Li, Synthesis of dimethyl ether from
syngas using a hierarchically porous composite zeolite as the methanol dehydra-
tion catalyst, J. Fuel Chem. Technol. 41 (2013) 873–880, https://doi.org/10.
1016/S1872-5813(13)60037-7.
[183] Y. Wang, W. Wang, Y. Chen, J. Ma, J. Zheng, R. Li, Core–shell Ccatalyst
CuO–ZnO–Al2O3 @Al2O3 for dimethyl ether synthesis from syngas, Chem. Lett. 42
(2013) 335–337, https://doi.org/10.1246/cl.121099.
[184] W.Z. Lu, L.H. Teng, W. De Xiao, Simulation and experiment study of dimethyl
ether synthesis from syngas in a fluidized-bed reactor, Chem. Eng. Sci. 59 (2004)
5455–5464, https://doi.org/10.1016/j.ces.2004.07.031.
[185] M.P. Rohde, G. Schaub, S. Khajavi, J.C. Jansen, F. Kapteijn, Fischer-Tropsch
synthesis with in situ H2O removal - Directions of membrane development,
Microporous Mesoporous Mater. 115 (2008) 123–136, https://doi.org/10.1016/j.
micromeso.2007.10.052.
[186] A. Erkiaga, G. Lopez, M. Amutio, J. Bilbao, M. Olazar, Influence of operating
conditions on the steam gasification of biomass in a conical spouted bed reactor,
Chem. Eng. J. 237 (2014) 259–267, https://doi.org/10.1016/j.cej.2013.10.018.
[187] J. Ereña, I. Sierra, M. Olazar, A.G. Gayubo, A.T. Aguayo, Deactivation of a CuO -
ZnO - Al2O3/γ-Al 2O3 catalyst in the synthesis of dimethyl ether, Ind. Eng. Chem.
Res. 47 (2008) 2238–2247, https://doi.org/10.1021/ie071478f.
[188] B.T. Carvill, J.R. Hufton, M. Anand, S. Sircar, Sorption-enhanced reaction process,
AIChE J. 42 (1996) 2765–2772, https://doi.org/10.1002/aic.690421008.
[189] I. Iliuta, M.C. Iliuta, F. Larachi, Sorption-enhanced dimethyl ether synthesis-
Multiscale reactor modeling, Chem. Eng. Sci. 66 (2011) 2241–2251, https://doi.
org/10.1016/j.ces.2011.02.047.
[190] A. Bayat, T. Dogu, Optimization of CO2/CO ratio and temperature for dimethyl
ether synthesis from syngas over a new bifunctional catalyst pair containing het-
eropolyacid impregnated mesoporous alumina, Ind. Eng. Chem. Res. (2016),
https://doi.org/10.1021/acs.iecr.6b03001.
[191] G. Moradi, J. Ahmadpour, M. Nazari, F. Yaripour, Effects of feed composition and
space velocity on direct synthesis of dimethyl ether from syngas, Ind. Eng. Chem.
Res. 47 (2008) 7672–7679, https://doi.org/10.1021/ie800888z.
[192] K.B. Kabir, K. Hein, S. Bhattacharya, Process modelling of dimethyl ether pro-
duction from Victorian brown coal-Integrating coal drying, gasification and
synthesis processes, Comput. Chem. Eng. 48 (2013) 96–104, https://doi.org/10.
1016/j.compchemeng.2012.08.008.
[193] N. Diban, A.M. Urtiaga, I. Ortiz, J. Ereña, J. Bilbao, A.T. Aguayo, Influence of the
membrane properties on the catalytic production of dimethyl ether with in situ
water removal for the successful capture of CO2, Chem. Eng. J. 234 (2013)
140–148, https://doi.org/10.1016/j.cej.2013.08.062.
[194] M. Stiefel, R. Ahmad, U. Arnold, M. Döring, Direct synthesis of dimethyl ether
from carbon-monoxide-rich synthesis gas: Influence of dehydration catalysts and
operating conditions, Fuel Process. Technol. 92 (2011) 1466–1474, https://doi.
org/10.1016/j.fuproc.2011.03.007.
[195] J. Erena, R. Garona, J.M. Arandes, A.T. Aguayo, J. Bilbao, Effect of operating
conditions on the synthesis of dimethyl ether over a CuO-ZnO-Al2O3/NaHZSM-5
bifunctional catalyst, Catal. Today 107 (2005) 467–473, https://doi.org/10.1016/
j.cattod.2005.07.116.
[196] A. Ateka, J. Ereña, P. Pérez-Uriarte, A.T. Aguayo, J. Bilbao, Effect of the content of
CO2 and H2 in the feed on the conversion of CO2 in the direct synthesis of dimethyl
ether over a CuO-ZnO-Al2O3/SAPO-18 catalyst, Int. J. Hydrogen Energy 42 (2017)
27130–27138, https://doi.org/10.1021/ie071478f.
[197] M. Kumar, V.C. Srivastava, Simulation of a fluidized-bed reactor for dimethyl
ether synthesis, Chem. Eng. Technol. 33 (2010) 1967–1978, https://doi.org/10.
1002/ceat.201000158.
[198] R. Liu, F. Zhu, Y. Steinberger, Effectiveness of afforested shrub plantation on
ground-active arthropod communities and trophic structure in desertified regions,
Catena 125 (2015) 1–9, https://doi.org/10.1016/j.catena.2014.09.018.
[199] X. Zhou, T. Su, Y. Jiang, Z. Qin, H. Ji, Z. Guo, CuO-Fe2O3-CeO2/HZSM-5 bifunc-
tional catalzyst hydrogenated CO2 for enhanced dimethyl ether synthesis, Chem.
Eng. Sci. 153 (2016) 10–20, https://doi.org/10.1016/j.ces.2016.07.007.
[200] J. Ereña, R. Garoña, J.M. Arandes, A.T. Aguayo, J. Bilbao, Direct synthesis of di-
methyl ether from (H2 + CO) and (H2 + CO2) Feeds. Effect of feed composition,
Int. J. Chem. React. Eng. 3 (2005), https://doi.org/10.2202/1542-6580.1295.
[201] J. Ereña, R. Garoña, J.M. Arandes, A.T. Aguayo, J. Bilbao, Effect of operating
conditions on the synthesis of dimethyl ether over a CuO-ZnO-Al2O3/NaHZSM-5
bifunctional catalyst, Catal. Today. 107-108 (2005) 467–473, https://doi.org/10.
U. Mondal and G.D. Yadav
1016/j.cattod.2005.07.116.
[202] A. Ateka, P. Pérez-Uriarte, M. Sánchez-Contador, J. Ereña, A.T. Aguayo, J. Bilbao,
Direct synthesis of dimethyl ether from syngas on CuO-ZnO-MnO/SAPO-18 bi-
functional catalyst, Int. J. Hydrogen Energy. 41 (2016) 18015–18026, https://doi.
org/10.1016/j.ijhydene.2016.07.195.
[203] F. Zha, H. Tian, J. Yan, Y. Chang, Multi-walled carbon nanotubes as catalyst
promoter for dimethyl ether synthesis from CO2 hydrogenation, Appl. Surf. Sci.
285 (2013) 945–951, https://doi.org/10.1016/j.apsusc.2013.06.150.
[204] M. Jia, W. Li, H. Xu, S. Hou, Q. Ge, An integrated air–POM syngas/dimethyl ether
process from natural gas, Appl. Catal. A Gen. 233 (2002) 7–12, https://doi.org/10.
1016/s0926-860x(02)00120-5.
[205] J. Ereña, R. Garoña, J.M. Arandes, A.T. Aguayo, J. Bilbao, Effect of operating
conditions on the synthesis of dimethyl ether over a CuO-ZnO-Al2O3/NaHZSM-5
bifunctional catalyst, Catal. Today. 107-108 (2005) 467–473, https://doi.org/10.
1016/j.cattod.2005.07.116.
[206] A. Ateka, M. Sánchez-Contador, J. Ereña, A.T. Aguayo, J. Bilbao, Catalyst con-
figuration for the direct synthesis of dimethyl ether from CO and CO2 hydro-
genation on CuO–ZnO–MnO/SAPO-18 catalysts, React. Kinet. Mech. Catal. (2018)
1–18, https://doi.org/10.1007/s11144-018-1344-x.
[207] T. Henrich, J. Abeln, M. Betz, Direct dimethyl ether synthesis: modelling of the
kinetics from isothermal, Exp. Data Chemie Ing. Tech 90 (2018) 307–315, https://
doi.org/10.1002/cite.201600131.
[208] M. Gentzen, D.E. Doronkin, T.L. Sheppard, J.-D. Grunwaldt, J. Sauer, S. Behrens,
An intermetallic Pd2Ga nanoparticle catalyst for the single-step conversion of CO-
rich synthesis gas to dimethyl ether, Appl. Catal. A Gen. 562 (2018) 206–214,
https://doi.org/10.1016/j.apcata.2018.04.018.
[209] M. Gentzen, D.E. Doronkin, T.L. Sheppard, J.-D. Grunwaldt, J. Sauer, S. Behrens,
Bifunctional catalysts based on colloidal Cu/Zn nanoparticles for the direct con-
version of synthesis gas to dimethyl ether and hydrocarbons, Appl. Catal. A Gen.
557 (2018) 99–107, https://doi.org/10.1016/j.apcata.2018.03.008.
[210] Z. Chen, X. Li, Y. Xu, Y. Dong, W. Lai, W. Fang, X. Yi, Fabrication of nano-sized
SAPO-11 crystals with enhanced dehydration of methanol to dimethyl ether, Catal.
Commun. 103 (2018) 1–4, https://doi.org/10.1016/j.catcom.2017.09.002.
[211] A. Atakan, P. Mäkie, F. Söderlind, J. Keraudy, E.M. Björk, M. Odén, Synthesis of a
Cu-infiltrated Zr-doped SBA-15 catalyst for CO2 hydrogenation into methanol and
dimethyl ether, Phys. Chem. Chem. Phys. 19 (2017) 19139–19149, https://doi.
org/10.1039/c7cp03037a.
[212] K. Takeishi, Y. Wagatsuma, H. Ariga, K. Kon, K. Shimizu, Promotional effect of
water on direct dimethyl ether synthesis from carbon monoxide and hydrogen
catalyzed by Cu–Zn/Al2O3, ACS Sustain. Chem. Eng 5 (2017) 3675–3680, https://
doi.org/10.1021/acssuschemeng.6b02915.
[213] F. Dadgar, R. Myrstad, P. Pfeifer, A. Holmen, H.J. Venvik, Catalyst deactivation
during one-step dimethyl ether synthesis from synthesis gas, Catal. Letters 147
(2017) 865–879, https://doi.org/10.1007/s10562-017-1971-2.
[214] A. Kornas, R. Grabowski, M. Śliwa, K. Samson, M. Ruggiero-Mikołajczyk,
A. Żelazny, Dimethyl ether synthesis from CO2 hydrogenation over hybrid cata-
lysts: effects of preparation methods, React. Kinet. Mech. Catal. 121 (2017)
317–327, https://doi.org/10.1007/s11144-017-1153-7.
[215] T. Su, X. Zhou, Z. Qin, H. Ji, Intrinsic kinetics for dimethyl ether synthesis from
plasma activation CO2 hydrogenation over Cu-Fe-Ce/HZSM-5, ChemPhysChem 18
(2017) 299–309, https://doi.org/10.1002/cphc.201601283.
[216] R.J. da Silva, A.F. Pimentel, R.S. Monteiro, C.J.A. Mota, Synthesis of methanol and
dimethyl ether from the CO2 hydrogenation over Cu·ZnO supported on Al2 and
Nb2, Biochem. Pharmacol. 15 (2016) 83–88, https://doi.org/10.1016/j.jcou.2016.
01.006.
[217] W. Pranee, S. Neramittagapong, A. Neramittagapong, Environmental Effects
Dimethyl ether synthesis from methanol over diatomite catalyst modified using
nitric acid treatment, Energy Sources, Part A Recover. Util. Environ. Eff 38 (2016)
2244–2249, https://doi.org/10.1080/15567036.2015.1047065.
[218] H. Ham, J. Kim, S.J. Cho, J. Choi, D.J. Moon, J.W. Bae, Enhanced stability of
spatially con fi ned copper nanoparticles in an ordered mesoporous alumina for
dimethyl ether synthesis from syngas, ACS Catal. (2016), https://doi.org/10.
1021/acscatal.6b00882.
[219] S. Liu, J. Chen, Environmental effects reaction mechanism and kinetics of me-
thanol produced to dimethyl ether reaction mechanism and kinetics of methanol
produced to dimethyl ether, Energy Sources; Part A Recover. Util. Environ. Eff 37
(2015) 1591–1596, https://doi.org/10.1080/15567036.2011.642061.
[220] Z. Qin, T. Su, H. Ji, J. Chen, Experimental and theoretical study of the intrinsic
kinetics for dimethyl ether synthesis from CO2 over Cu – Fe – Zr/HZSM-5, AIChE J.
61 (2015) 11–13, https://doi.org/10.1002/aic.
[221] D. Mao, X. Guo, Dimethyl ether synthesis from syngas over the admixed Cu/ZnO/
Al2O3 catalyst and alkaline earth oxide- modified HZSM-5 Zeolite, Energy Technol.
2 (2014) 882–888, https://doi.org/10.1002/ente.201402071.
[222] K. Samson, A. Żelazny, M. Śliwa, R. Grabowski, M. Ruggiero–Mikołajczyk,
Influence of Montmorillonite K10 modification with tungstophosphoric acid on
hybrid catalyst activity in direct dimethyl ether synthesis from syngas, Catal. Lett.
144 (2014) 1884–1893, https://doi.org/10.1007/s10562-014-1359-5.
[223] F. Song, Y. Tan, H. Xie, Q. Zhang, Y. Han, Direct synthesis of dimethyl ether from
biomass-derived syngas over Effect of Zr-loading, Fuel Process. Technol. 126
(2014) 88–94, https://doi.org/10.1016/j.fuproc.2014.04.021.
[224] Y. Wang, W. Wang, Y. Chen, J. Ma, R. Li, Synthesis of dimethyl ether from syngas
over core – shell structure, Chem. Eng. J. 250 (2014) 248–256, https://doi.org/10.
1016/j.cej.2014.04.018.
[225] J. Sun, G. Yang, Q. Ma, I. Ooki, A. Taguchi, T. Abe, Q. Xie, Y. Yoneyama,
N. Tsubaki, Fabrication of active Cu–Zn nanoalloys on H-ZSM5 zeolite for en-
hanced dimethyl ether synthesis via syngas, J. Mater. Chem. A. 2 (2014)
319
Journal of CO₂ Utilization 32 (2019) 299–320
8637–8643, https://doi.org/10.1039/C3TA14936F.
[226] A. García-trenco, A. Martínez, The influence of zeolite surface-aluminum species
on the deactivation of CuZnAl/zeolite hybrid catalysts for the direct DME synth-
esis, Catal. Today. 227 (2014) 144–153, https://doi.org/10.1016/j.cattod.2013.
09.051.
[227] R. Liu, Z. Qin, H. Ji, T. Su, Synthesis of dimethyl ether from CO2 and H2 using a Cu
– Fe – Zr / HZSM ‑ 5 catalyst system, Ind. Eng. Chem. Res. 52 (2013)
16648–16655, https://doi.org/10.1021/ie401763g.
[228] C.-I. Ahn, J.W. Jeong, J.W. Bae, D.H. Lee, S.H. Um, Effects of Cu – ZnO content on
reaction rate for direct synthesis of DME from syngas with bifunctional Cu – ZnO/
γ-Al2O3 Catalyst, Catal. Lett. 143 (2013) 666–672, https://doi.org/10.1007/
s10562-013-1022-6.
[229] K.T. Pillai, R.V. Pai, S.S. Pathak, S.K. Mukerjee, S.K. Aggarwal, V.V. Vinogradov,
A.V. Agafonov, A.V. Vinograodov, Synthesis of doped and undoped γ-alumina
spherical particles by a new sol – gel hybrid process and their application for
methanol dehydration, J Sol-Gel Sci Technol. 66 (2013) 145–154, https://doi.org/
10.1007/s10971-013-2979-8.
[230] S. Hoda, S. Morteza, F. Cavus, Synthesis of some baria-modified γ -Al2O3 for
methanol dehydration to dimethyl ether, Res. J. Chem. Sci. 3 (2013) 57–62.
[231] R. Montesano, D. Chadwick, Combined methanol and dimethyl ether synthesis
from CO/H2: Phosphorus mediated deactivation, Catal. Comm. 29 (2012)
137–140, https://doi.org/10.1016/j.catcom.2012.09.031.
[232] Z. Li, C. Yang, J. Li, J. Wu, A CuZnAl-based hybrid material for the direct synthesis
of dimethyl ether from syngas, Adavance Materrials Eng. Mater 458 (2012)
261–264 doi:10.4028/www.scientific.net/AMR.457-458.261.
[233] H. Zhang, W. Li, W. Xiao, Attrition resistant catalyst of direct dimethyl ether
synthesis, Appl. Mech. Mater. 177 (2012) 97–101 doi:10.4028/www.scienti-
fic.net/AMM.174-177.97.
[234] Q. Yang, M. Kong, Z. Fan, X. Meng, J. Fei, F. Xiao, Aluminum fluoride modified
HZSM-5 zeolite with superior performance in synthesis of dimethyl ether from
methanol, Energy Fuels 26 (2012) 4475–4480, https://doi.org/10.1021/
ef3006383.
[235] L. Liu, W. Huang, J. Huang, Z. Gao, L. Yin, The Synthesis and catalytic activity of
slurry catalyst for methanol dehydration to dimethyl ether, Energy Sources Part A
Recover. Util. Environ. Eff. 34 (2012) 682–691, https://doi.org/10.1080/
15567030903530582.
[236] N. Park, T.J. Lee, Control of surface area and activity with changing precipitation
rate in preparation of Cu-Zn based catalysts for dimethyl ether direct synthesis,
Korean J. Chem. Eng. 28 (2011) 2076–2080, https://doi.org/10.1007/s11814-
011-0061-1.
[237] G. Yang, M. Thongkam, T. Vitidsant, Y. Yoneyama, A double-shell capsule catalyst
with core–shell-like structure for one-step exactly controlled synthesis of dimethyl
ether from CO2 containing syngas, Catal. Today 171 (2011) 229–235, https://doi.
org/10.1016/j.cattod.2011.02.021.
[238] C. Cheng, H. Zhang, W. Ying, D. Fang, Intrinsic kinetics of one-step dimethyl ether
synthesis from hydrogen-rich synthesis gas over bi-functional catalyst, Korean J.
Chem. Eng. 28 (2011) 1511–1517, https://doi.org/10.1007/s11814-011-0018-4.
[239] S. Baek, S. Kang, J.W. Bae, Y. Lee, D. Lee, K. Lee, Effect of copper precursors to the
activity for dimethyl ether synthesis from syngas over Cu-ZnO/γ-Al2O3 bifunc-
tional catalysts, Energy Fuels 25 (2011) 2438–2443, https://doi.org/10.1021/
ef200504p.
[240] Z. Lei, Z. Zou, C. Dai, Q. Li, B. Chen, Synthesis of dimethyl ether (DME) by cat-
alytic distillation, Chem. Eng. Sci. 66 (2011) 3195–3203, https://doi.org/10.
1016/j.ces.2011.02.034.
[241] Q. Xu, P. Lan, K. Huang, Y. Yan, Effect of different ratios of Si-Al of zeolite HZSM-5
on the activity of bifunctional catalysts upon dimethyl ether synthesis effect of
different ratios of Si-Al of zeolite HZSM-5 on the activity of bifunctional catalysts,
Pet. Sci. Technol. 29 (2011) 1080–1092, https://doi.org/10.1080/
10916460903502472.
[242] Q. Xu, P. Lan, S. Zhang, T. Li, Y. Yan, Effect of modified zeolite on one-step process
of DME synthesis effect of modified zeolite on one-step process of DME synthesis,
Pet. Sci. Technol. 29 (2011) 439–448, https://doi.org/10.1080/
10916460903117552.
[243] G. Moradi, F. Yaripour, H. Abbasian, M. Rahmanzadeh, Intrinsic reaction rate and
the effects of operating conditions in dimethyl ether synthesis from methanol
dehydration, Korean J. Chem. Eng. 27 (2010) 1435–1440, https://doi.org/10.
1007/s11814-010-0238-z.
[244] A. Ciftci, D. Varisli, T. Dogu, Dimethyl ether synthesis over novel silicotungstic
acid incorporated nanostructured catalysts dimethyl ether synthesis over novel
silicotungstic acid incorporated nanostructured catalysts, Int. J. Chem. React. Eng.
8 (2010) 1–15, https://doi.org/10.2202/1542-6580.2151.
[245] A.R. Keshavarz, M. Rezaei, F. Yaripour, Nanocrystalline gamma-alumina: A highly
active catalyst for dimethyl ether synthesis, Powder Technol. 199 (2010) 176–179,
https://doi.org/10.1016/j.powtec.2010.01.003.
[246] C. Won, K. Deok, K. Young, K. Sang, Dehydration of methanol over nordstrandite
based catalysts for dimethyl ether synthesis, J. Ind. Eng. Chem. 15 (2009)
649–652, https://doi.org/10.1016/j.jiec.2009.09.037.
[247] S.H. Kang, J.W. Bae, H.S. Kim, G.M. Dhar, K.W. Jun, Enhanced catalytic perfor-
mance for dimethyl ether synthesis from syngas with the addition of Zr or Ga on a
Cu-ZnO-Al2O3/γ- Al2O3 bifunctional catalyst, Energy Fuels 24 (2010) 804–810,
https://doi.org/10.1021/ef901133z.
[248] Q. You, Z. Liu, W. Li, X. Zhou, Synthesis of dimethyl ether from methane mediated
by HBr, J. Nat. Gas Chem. 18 (2009) 306–311, https://doi.org/10.1016/S1003-
9953(08)60122-X.
[249] Y. Li, T. Wang, X. Yin, C. Wu, L. Ma, H. Li, Y. Lv, L. Sun, 100 t/a-Scale demon-
stration of direct dimethyl ether synthesis from corncob-derived syngas, Renew.
U. Mondal and G.D. Yadav
Energy 35 (2010) 583–587, https://doi.org/10.1016/j.renene.2009.08.002.
[250] J.W. Bae, S.H. Kang, Y.J. Lee, K.W. Jun, Synthesis of DME from syngas on the
bifunctional Cu-ZnO-Al2O3/Zr-modified ferrierite: Effect of Zr content, Appl.
Catal. B Environ. 90 (2009) 426–435, https://doi.org/10.1016/j.apcatb.2009.04.
002.
[251] S. Wang, D. Sen Mao, X.M. Guo, G.Z. Lu, Dimethyl ether synthesis from CO2 hy-
drogenation over CuO-TiO2-ZrO2/HZSM-5 catalysts, Catal. Commun. 27 (2011)
2651–2658, https://doi.org/10.1016/j.catcom.2009.02.001.
[252] C.W. Seo, K.D. Jung, K.Y. Lee, K.S. Yoo, Influence of structure type of Al2O3 on
dehydration of methanol for dimethyl ether synthesis, Ind. Eng. Chem. Res. 47
(2008) 6573–6578.
[253] X. An, Y. Zuo, Q. Zhang, D. Wang, J. Wang, Dimethyl ether synthesis from CO2
hydrogenation on a CuO-ZnO-Al2O3-ZrO2/HZSM-5 bifunctional catalyst, Ind. Eng.
Chem. Res. (2008) 6547–6554, https://doi.org/10.1021/ie800777t.
[254] Y.D. Yoo, S.J. Lee, Y. Yun, Synthesis of dimethyl ether from syngas obtained by
coal gasification, Korean J. Chem. Eng. 24 (2007) 350–353, https://doi.org/10.
1007/s11814-007-5045-9.
[255] S.H. Kang, J.W. Bae, K.W. Jun, H.S. Potdar, Dimethyl ether synthesis from syngas
over the composite catalysts of Cu-ZnO-Al2O3/Zr-modified zeolites, Catal.
Commun. 9 (2008) 2035–2039, https://doi.org/10.1016/j.catcom.2008.03.046.
[256] V. Pet’kov, M. Sukhanov, I. Shchelokov, N. Orekhova, E. Asabina, M. Ermilova,
G. Tereshchenko, Synthesis, surface properties and catalytic activity of phosphates
Cu0.5(1+y)FeyZr2−y(PO4)3 in methanol conversion, Solid State Sci. 10 (2008)
513–517, https://doi.org/10.1016/j.solidstatesciences.2007.12.005.
[257] M. Mollavali, F. Yaripour, H. Atashi, S. Sahebdelfar, Intrinsic kinetics study of
dimethyl ether synthesis from methanol on γ-Al2O3 catalysts, Ind. Eng. Chem. Res.
47 (2008) 3265–3273, https://doi.org/10.1021/ie800051h.
[258] Y. Zhao, J. Chen, Effects of ZrO2 on the performance of CuO-ZnO-Al2O3/HZSM-5
catalyst for dimethyl ether synthesis from CO2 hydrogenation, J. Nat. Gas Chem.
16 (2007) 389–392.
[259] D. Jin, B. Zhu, Z. Hou, J. Fei, H. Lou, X. Zheng, Dimethyl ether synthesis via
methanol and syngas over rare earth metals modified zeolite Y and dual Cu-Mn-Zn
catalysts, Fuel. 86 (2007) 2707–2713, https://doi.org/10.1016/j.fuel.2007.03.
011.
[260] K. Sang, J. Kim, M. Park, S. Kim, O. Joo, K. Jung, Influence of solid acid catalyst on
320
Journal of CO₂ Utilization 32 (2019) 299–320
DME production directly from synthesis gas over the admixed catalyst of Cu/ZnO/
Al2O3 and various SAPO catalysts, Appl. Catal., A Gen. 330 (2007) 57–62, https://
doi.org/10.1016/j.apcata.2007.07.007.
[261] V.S. Kumar, A.H. Padmasri, C.V.V. Satyanarayana, I.A. Kumar, Nature and mode
of addition of phosphate precursor in the synthesis of aluminum phosphate and its
influence on methanol dehydration to dimethyl ether, Catal. Commun. 7 (2006)
745–751, https://doi.org/10.1016/j.catcom.2006.02.025.
[262] J. Wang, C. Zeng, Al2O3 effect on the catalytic activity of Cu-ZnO-Al2O3-SiO2
catalysts for dimethyl ether synthesis from CO2 hydrogenation, J. Nat. Gas Chem.
14 (2005) 156–162.
[263] H.F. Xu, K.X. Wang, W.S. Li, X.P. Zhou, Dimethyl ether synthesis from methane by
non syngas process, Catal. Letters. 100 (2005) 53–57, https://doi.org/10.1007/
s10562-004-3085-x.
[264] Y. Usui, C. Wakai, N. Matubayasi, M. Nakahara, Synthesis of dimethyl ether from
supercritical methanol in the presence of aluminum, Chem. Lett. 33 (2004)
394–395, https://doi.org/10.1246/cl.2004.394.
[265] K. Omata, T. Ozaki, T. Umegaki, Y. Watanabe, N. Nukui, M. Yamada, Optimization
of the temperature profile of a temperature gradient reactor for DME synthesis
using a simple genetic algorithm assisted by a neural network, Energy Fuels 17
(2003) 836–841, https://doi.org/10.1021/ef0202438.
[266] M. Jia, W. Li, H. Xu, S. Hou, Q. Ge, An integrated air – POM syngas/dimethyl ether
process from natural gas, Appl. Catal. A Gen. 233 (2002) 7–12.
[267] X.U. Hengyong, The synthesis of dimethyl ether from syngas obtained by catalytic
partial oxidation of methane and air, Stud. Surf. Sci. Catal. 136 (2001) 33–38,
https://doi.org/10.1016/S0926-860X(02)00120-5.
[268] T. Akiyama, Development of Cu/ZnO/Al2O3 catalyst for dimethyl fther wlixture
synthesis from CO-CO2-H2, ISIJ Int. 38 (1998) 93–97, https://doi.org/10.2355/
isijinternational.38.93.
[269] J. Li, X. Zhang, T. Inui, Improvement in the catalyst activity for direct synthesis of
dimethyl ether from synthesis gas through enhancing the dispersion of CuO/ZnO/
T-A12O3 in hybrid catalysts, Appl. Catal. A Gen 147 (1996) 23–33, https://doi.
org/10.1016/S0926-860X(96)00208-6.
[270] Y.Z. Han, K. Asami, K. Fujimoto, Gas phase dimethyl ether synthesis from syngas,
J. Japan Inst. Energy. 75 (1996) 42–48, https://doi.org/10.3775/jie.75.42.