Journal of CO₂ Utilization xxx (xxxx) xxx–xxx

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 II- analysis of reactor systems and
industrial processes
Ujjal Mondal, Ganapati D. Yadav
⁎

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

ARTICLE INFO ABSTRACT

Keywords: In Part I of this review article, the significance of DME as fuel and the various types of catalysts used for different
Dimethyl ether (DME) feedstocks were considered. However, the industrial processes using a variety of reactor configurations affect the
Syngas overall capex and opex. The production of syngas, irrespective of the source, is the first step in DME synthesis,
CO2 which is then followed by conversion into DME using a battery of reactors and separators. A critical analysis is
Catalysis
presented and future scope outlined.
Fuel
LPG
Multiphase reactors
Methanol

1. Introduction
Catalytic DME synthesis by using both indirect and direct methods
was covered in Part I of this review [1]. Not only the nature of the
catalyst but types of reactors and separators and their configuration will
influence the process economics. In both the methods, either CO2 or
syngas is the feedstock for making DME no matter whether coal, pet-
roleum, natural gas or biomass is the primary source. CO2 comes from
power plants and is the greenhouse gas. Syngas is the most industrially
popular source for DME synthesis [2]. The reversible nature of the re-
actions in DME synthesis from carbonaceous gases makes the whole
reaction thermodynamically limited. The unconverted reactants are
separated downstream of the synthesis reactor and partially recycled
into the DME synthesis reactor after recompressing. The reactor design
is an important parameter for direct DME synthesis as the reaction
temperature, feed composition, and pressure play a very important role
in reactant conversion and product selectivity. In the past few decades,
direct synthesis of DME by bifunctional catalysts has been studied.
Direct DME synthesis process in a single reactor combines methanol
synthesis and methanol dehydration reactions. Single pot synthesis of
DME in a slurry reactor, introduced by JFE Corporation, Air Products
and Tsinghua University [2] is among the most promising technologies
for large scale DME production. Other than slurry reactor many re-
searchers have evaluated the DME synthesis process from syngas in
different types of reactors such as fixed bed reactor [3,4], internal
recycle type reactor [5], fluidized bed reactor [6], and back mixed
slurry reactor [7]. Because of the importance of syngas in DME synth-
esis, a comprehensive review of different production technologies of
syngas from various sources is also covered to put DME synthesis in
perspective. Thereafter innovative reactor technologies for direct and
indirect DME synthesis process are discussed.
2. Syngas production from different sources
Syngas is a major requirement for the DME industry. Syngas can be
synthesized from a number of natural resources, which include coal,
methane, and biomass. Various gasification technologies have been
used to produce syngas from biomass and coal. This gasification process
involves reforming techniques (steam and/or oxygen), syngas clean-up
process to remove various contaminants such as sulfur, ash, mercury,
arsenic, and tar for the biomass gasification process.
2.1. Coke from coal and petroleum
The purpose of the gasification process is to convert maximum
chemical energy stored in the fuel into chemical energy in gases such as
CO, hydrogen, and light hydrocarbons. Coal gasification is an estab-
lished technology for the production of syngas and it has matured over
the years regarding the handling of feed, energy efficiency and the in-
troduction of entrained flow gasifier for rapid feed conversion and high

DOI of original article: https://doi.org/10.1016/j.jcou.2019.02.003

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

https://doi.org/10.1016/j.jcou.2019.02.006

2212-9820/ © 2019 Elsevier Ltd. All rights reserved.

Please cite this article as: Ujjal Mondal and Ganapati D. Yadav, Journal of CO₂ Utilization, https://doi.org/10.1016/j.jcou.2019.02.006
U. Mondal and G.D. Yadav
throughput. Bituminous coal is the most suitable source for gasification
but due to the abundance of low-grade coal such as sub-bituminous coal
and lignite, most of the gasification units are operating on low-grade
coal. Petroleum refineries around the world are producing a huge
amount of petroleum coke which can be an alternative cheap source for
syngas generation. During the coal gasification process, crude coal is
reacted with steam and oxygen/air to produce CO2 and CO. There are
three well known main types of gasifiers to pyrolyze and gasify the
carbon and hydrogen from coal in a continuous automated process.
2.1.1. Fixed bed gasifier
Fixed bed consists of a fuel bed, through which air or oxygen is
blown for gasification purpose. Lurgi is well known for large-scale fixed
bed gasifier in the industry [8] and most of the power plants are con-
sidering British Gas/Lurgi (BGL) fixed bed gasifier [9]. The BGL gasifier
is superior in many areas such as higher gasification rate, better in
terms of energy efficiency and the slag produced is a high strength
material along with low leachability.
2.1.2. Fluidized bed gasifier
Coal is grounded to the size of few millimeters to form fluidized bed
which is suspended by blowing air or oxygen through the particles [10].
High-quality coal is required to achieve a high conversion rate for this type
of gasifier [11]. Uhde-Prenflo have installed the world’s largest gasifica-
tion plant in Spain based on fluidized bed technology and it operates with
50% mixture of each petroleum coke and coal. This type of gasifier is
favored by power plants because of their low conversion efficiency. Char
produced from this process is utilized by another unit of the power plant.
British Coal and Westinghouse have been involved in the development of
an improved version of this kind of gasifier [11]. Co-gasification of various
types of biomass, and plastic waste with coal in the fluidized bed reactor
has been investigated by many researchers [12–14].
2.1.3. Entrained gasifier
This type of gasifier utilizes pulverized coal which blows into the
gasifier in a similar manner to a pulverized coal-fired system and then
oxidized by reaction with oxygen or highly oxygen enriched air [15].
Other than coal, this technology can be utilized for petroleum coke and
oil feedstock. Krupp Koppers, Dow, Texaco, and Shell are the leading
companies which are working with entrained gasifier [11]. This type of
gasifier is quite popular as it can handle a wide variety of solid or liquid
fuels despite high installation cost and high wastage of energy in terms
of heat [16].
2.2. Natural gas
A number of technologies have been developed to convert natural
gas into syngas such as steam methane reforming (SMR), partial oxi-
dation (POX), CO2 reforming, auto-thermal reforming (ATR), and
combined reforming [17].
2.2.1. Steam methane reforming (SMR)
Light hydrocarbons are reacted with steam in the presence of nickel
catalyst to produce CO, H2, and CO2 via an endothermic reaction [17].
This process is operated in a direct–fired furnace where catalysts are
loaded in tubes, through which preheated methane and steam mixture
is blown. Higher hydrocarbons are not suitable to use as a feedstock in
SMR due to the presence of high sulfur content, which results in catalyst
deactivation, tar and coke deposition. The produced syngas leaves the
reactor at high temperatures (800–900 °C). Many companies are de-
veloping new technologies to make this process more energy efficient
and include United Technology Corporation, Haldor Topᴓse, and KTI
[18]. Lurgi is the market leader in building SMR plants and a few en-
gineering companies were or continue to build also building SMR such
as Howe-Baker, Foster Wheeler, M. W. Kellogg, Kvaener, and the erst-
while ICI.
2
Journal of CO₂ Utilization xxx (xxxx) xxx–xxx
2.2.2. Partial oxidation (POX)
It is the second most popular process for producing syngas from
methane. As this is an exothermic reaction, no external energy is re-
quired to produce hydrogen and CO gas mixture. A refractory lined
pressure vessel is utilized and it is fed with preheated natural gas and
oxygen. The gases are mixed in a burner at elevated pressure (40 bar)
and immediately the partial oxidation reaction occurs in the combus-
tion zone below the burner [19]. The produced syngas leaves the re-
actor at 1200–1300 °C. Various kinds of hydrocarbons (from natural gas
to heavy hydrocarbons) can be utilized for syngas production by POX
method and 100% conversion is achieved in this process. Catalytic POX
method also has been developed which requires less volume and con-
sumes less oxygen. Texaco and Shell Technologies are the most popular
companies to build POX plant. Other companies which are also working
in the same field are Koppers, Lurgi, Foster Wheeler, Starchem, and
British Gas [20].
2.2.3. CO2 reforming
In this type of reforming process syngas is produced with a lower
H2/CO ratio (1:1) [21]. This process is also referred to as dry reforming
as steam is not used in this process. The overall reaction mechanism and
kinetics is similar to SMR but the rate of formation of carbon is much
higher. Nickel and Ni/SiO2 catalysts are generally used for this reaction
but noble metal catalyst such as rhodium and iridium also have been
employed. After removing sulfur from methane gas, it is mixed with
CO2 and purged into the catalyst tubes of reforming vessel, which is the
same as SMR. The product gases are CO, H2, CO2 with less amount of
CH4, but 100% conversion can be achieved with this process while
changing the process parameters [22,23].
2.2.4. Autothermal reforming (ATR)
This process is a combination of partial oxidation and steam me-
thane reforming process in a single vessel [24]. In this process, the
energy required to convert hydrocarbons is supplied by POX reaction.
From the top of the reactor, a preheated mixture of methane, steam,
and oxygen is introduced. POX reaction proceeds at the upper portion
of the reactor and then the gas mixture is traveled through the catalyst
filled bed of the vessel, where final reforming occurs. The produced
syngas is having a high mole ratio of H2/CO (1.6–2.6). Lurgi, Haldor
Topᴓse, Foster Wheeler, and ICI are the license holders of these pro-
cesses.
2.2.5. Combined reforming
Since the conversion efficiency of SMR process is not 100%, it is
sometimes combined with a secondary reformer such as ATR or POX
unit to reach complete methane conversion and improved H2/CO ratio.
Thus this process is also known as “oxygen-enhanced reforming” or
“two-step reforming”. This technology is offered by the main process
developers of syngas industry like M. W. Kellogg and Haldor Topᴓse,
etc.
2.3. Biomass gasification
Biomass is an important renewable energy source and thermo-
chemical conversion also known as gasification of biomass produces
syngas and a solid product, char. The gasification process involves
partial oxidation of carbon present in biomass and the gasification is
generally carried out in the presence of carrier gases such as oxygen,
air, CO2 or steam (Fig. 1). The produced syngas is a mixture of CO, H2,
CO2 and also includes light hydrocarbons. Some unwanted gases are
also released with syngas such as sulfide (H2S) and chloridic (HCl) acids
along with inert nitrogen gas. Most of the principal reaction of biomass
gasification is endothermic and the required energy is provided by
oxidation of biomass through either allo-thermal or auto-thermal pro-
cess. The allo-thermal process requires external energy supply and auto-
thermal process uses the energy produced by partial oxidation. Biomass
U. Mondal and G.D. Yadav Journal of CO₂ Utilization xxx (xxxx) xxx–xxx

Fig. 1. Schematic diagram of DME/methanol plant operated on biomass gasification. Modified from [27].

gasification system includes four main stages, i. e. (i) oxidation (exo-

thermic stage), (ii) drying (endothermic stage), (iii) pyrolysis (en-
dothermal stage), and (iv) reduction (endothermic stage). And finally, a
tar decomposition stage is included to convert the big tar molecules into
small light hydrocarbons [25]. A number of firms are setting up com-
mercial bio-gas manufacturing plants which use air combined with
oxygen, only for combined heat and power (CHP) application. Andritz/
Carbona fluidized-bed gasification technology of USA, The Energy Re-
search Centre of Netherlands (ECN), Chemrec/Volvo/Haldor Topsoe
and Uhde of Sweden, Guangzhou Energy Institute of China, and
BioMCN of Netherlands are the leading firms which have already setup
commercial plants to produce bio-gas from raw biomass, black liquor
collected from pulp and paper plant, glycerol, etc. [26].
The foregoing analysis shows that production of syngas is very
important for which different technologies have been introduced in the
market. Now let us turn our attention to the reactors which influence
over economics of the DME manufacture.
3. DME synthesis reactors
DME synthesis from syngas or CO2 is a highly exothermic reaction
and in order to avoid the runaway of the synthesis process, the tem-
perature inside the reactor must be controlled. In recent times focus has
been shifted to reactor technology to minimize the generated entropy of
any chemical process. Initially, fluidized bed reactor was used for the
highly exothermic reactions such as DME synthesis [6]. Many re-
searchers have evaluated the DME synthesis process from syngas in
different types of reactors such as fixed bed reactor [4,3], internal re-
cycle type reactor [5], fluidized bed reactor [6], and back mixed slurry
reactor [7]. Lu et al. [6] have done a comparative study among flui-
dized bed, fixed bed and slurry reactors for the direct DME synthesis
process and found the slurry reactor to be the best choice. In the fol-
lowing section, different reactor systems are discussed which have been
either modified or directly used for DME production from syngas or
mixture of CO2 and H2.
3.1. Fixed bed reactor
Adiabatic fixed bed reactors are quite popular in the refinery and
chemical process industries for their ease of operation and maintenance
(Fig. 2). Based on the number of DME production steps involved, the
fixed bed reactor is designed accordingly. When the indirect process is
adopted, then the separate stages of syngas hydrogenation and me-
thanol dehydration are held in separate reactors. Unlike the indirect
Fig. 2. Fixed bed reactor for DME synthesis. Modified from [31].
process, the direct process requires a single reactor and by continuously
converting methanol to DME over a bifunctional catalyst, the thermo-
dynamic limitation associated with methanol producing reaction is al-
leviated [4]. Gas-solid contactors are usually employed in some fixed
bed reactors to enhance mass transfer rates. When the reactions are
endothermic and exothermic in nature, this type of reactor is not sui-
table to carry out the reaction due to catalyst sintering. The most im-
portant factor which affects the performance of a fixed bed reactor is
the formation of hot spots inside the reactor and these overheating
zones can deactivate the catalyst irreversibly [28]. For the economic
operation, a high recycle rate of syngas is needed to overcome low
conversion due to these thermodynamic limitations and catalyst deac-
tivation. CO2 is also used as an alternative to syngas as a starting ma-
terial for DME synthesis and it requires an additional step, i.e. reverse
water shift gas (r-WSG reaction) to hydrogenate CO2. The r-WSG step
can influence the whole process significantly as the rates of methanol
formation and methanol dehydration reaction are affected by in situ
water formation. Many studies have been conducted for modeling and
feasibility of DME synthesis by methanol dehydration in fixed bed re-
actor. Ghavipour and Behbahni [29] have done simulation study on
industrial fixed bed reactor system at steady state conditions for DME
synthesis by methanol dehydration. Farsi et al. have also developed a
model of an industrial adiabatic fixed bed reactor for DME synthesis
with preheated feed supply and simulated it at dynamic conditions
[30].

3
U. Mondal and G.D. Yadav
Fig. 3. Shell and tube type of reactor configuration for DME synthesis. Figure is
taken from [34].
3.2. Isothermal adiabatic reactor
Isothermal reactors are a type of fixed bed reactors which are em-
ployed for DME synthesis. The isothermal adiabatic reactor is a com-
bination of heat exchanger and conventional reactor, in which reactions
occur at the tube side and the heat of the reaction is removed with using
a cooling medium from the shell side of the reactor (Fig. 3). In com-
parison with the conventional adiabatic reactor, the isothermal reactor
is more controllable and higher yield generator. Reversible and exo-
thermic reaction operated in plug flow or batch reactor leads to dif-
ferent optimal temperature distribution which is the main deciding
factor for product selectivity among DME, methanol, and ammonia.
Shell and tube fixed bed reactors have been employed for the DME
synthesis from methanol [32], CO2 rich feedstock [33] and syngas [34].
Hu et al. [35] have built a mathematical model of the shell and tube
reactor system based on the global kinetics of the direct DME produc-
tion from syngas in the presence of a bifunctional catalyst and opti-
mized the reactor structure and operating conditions for achieving the
highest yield of DME at operational economic conditions. Farsi et al.
[32] also have optimized and modeled indirect DME production from
methanol in shell and tube fixed bed reactor based on the energy and
mass conversion equations. They have reported maximum DME yield
by adjusting the temperature profile along the length of the isothermal
reactor by using a genetic algorithm. Methanol conversion of the
modified reactor reached 85.75% from 81.9% of the conventional re-
actor and therefore DME production increased by 4.3%. Bai et al. [36]
have simulated DME synthesis through methanol dehydration in a
vapor phase adiabatic fixed bed reactor with a capacity of 1000 KTPY.
They have compared their simulated results with industrial DME pro-
duction plant with 2 MTPA capacity. In their follow-up paper, a five-
bed industrial adiabatic reactor battery fitted with heat exchangers (for
inter-stage cooling) is reported [37]. They also simulated a three-bed
adiabatic reactor with interstage cooling, which is provided by injecting
a fraction of fresh cold reaction feed.
3.3. Slurry phase reactor
Slurry bubble column reactor is a type of multiphase pneumatic
contactor. Other than adiabatic fixed bed reactor, it is one of the most
promising reactor systems for DME synthesis. There are several reasons
for the better performance of slurry bubble phase reactor than fixed bed
reactor such as simple construction, uniform temperature distribution
inside the reactor for highly exothermic reaction, easy catalyst addition,
and separation process, good control of the reactor temperature which
helps to avoid catalyst sintering and low energy requirement for ade-
quate mass transfer between phases [38]. In the traditional slurry re-
actors catalyst particles are introduced by dispersing them in inert
solvent inside the reactor (Fig. 4). This creates problems such as non-
4
Journal of CO₂ Utilization xxx (xxxx) xxx–xxx
Fig. 4. A schematic diagram of slurry phase reactor. Modified from [47].
wettability of the catalyst because of the mismatch between hydrophilic
catalyst surface and hydrophobic organic solvent. Several other pro-
blems are also encountered such as aggregation, misdistribution, and
rheological deterioration of catalyst particles and therefore the catalyst
is poisoned and deactivated. Gao et al. [39] have claimed a proper
procedure and environment to prepare a catalyst for slurry reactor. Liu
et al. [40] prepared an efficient slurry catalyst by following complete
liquid-phase technology from AIP for production of DME from me-
thanol in a slurry phase reactor. Syngas flows upward in the form of
bubbles inside the slurry phase reactor, where catalyst particles are
dispersed in the inert oil medium. First, the syngas has to get dissolved
in the solvent to reach the surface of the catalyst and get converted.
Methanol synthesis occurs first followed by methanol dehydration re-
action. The water generated by dehydration reaction quickly reacts
with CO and is removed from the system. Unlike fixed bed reactor there
is no hotspot generation inside the reactor because heat conductivity of
the slurry is very high and heat is homogeneously distributed inside the
reactor. Heat transfer from the heat exchanger tubes to the slurry is
very efficient and thus heat removal from the reactor for the highly
exothermic reaction is very easy. Thus this type of reactor has several
mass transfer limitations and the productivity of the reactor is affected
greatly [41–44]. Papari et al. [45] have simulated a large scale slurry
bubble column reactor for the production of DME from syngas. In their
study, the catalyst deactivation is also taken into account for the tran-
sient conversion of syngas and DME yield. They evaluated the optimum
temperature profile and under the uniform catalyst distribution inside
the reactor, the positive effect of catalyst concentration and reaction
pressure has been predicted. Aoki et al. [46] have established a pilot
plant of 100 TPD for DME synthesis from syngas in a slurry phase re-
actor.
3.4. Fluidized- bed reactor
According to many studies, fluidized bed reactor is the ideal reactor
for DME synthesis [48]. Use of fine catalyst particles makes this kind of
reactor free from mass transfer resistance in comparison with fixed bed
and slurry reactors. Other advantages of fluidized bed reactors (FBR)
are: (a) high mixing enables superior temperature control and very fast
to attain isothermal condition, (b) less pressure drop, (c) catalyst re-
generation and recycling process is very easy, and (e) more quantity of
catalyst can be used leading to higher rates. When the three type of
reactors are compared based on different parameters such as CO con-
version, DME selectivity and DME productivity, respectively, the flui-
dized bed reactor shows the highest performance (48.5%,97%,0.45 g.g-
cat−1.h−1) followed by slurry reactor (7%, 70%, 0.2 gg-cat−1.h−1) and
FBR (10.7,91.9,0.5 gg-cat−1.h−1) [17,6,49,50]. Despite these ad-
vantages and potentials, the application of FBR for DME synthesis has
U. Mondal and G.D. Yadav
Fig. 5. A schematic diagram of fluidized-bed reactor. Reproduced from [51].
not been properly investigated. Abashar et al. [51] have explored the
potential of multiphase fluidized bed catalytic reactor for the use of
DME synthesis through simulation studies. Their simulation studies
indicated that dual–phase fluidized bed reactor showed a substantial
increase in DME yield with almost 100% selectivity. They concluded
that catalyst bed composition of the second bed controls the perfor-
mance of the reactor and multistage fluidized bed reactor can be a
better option to employ for DME synthesis in industry (Fig. 5). Rand-
hava et al. [52] have patented a technology to produce DME from
syngas in the presence of catalyst in a fluid pluralized bed reactor op-
erated in the gas phase. As the DME synthesis from syngas is a highly
exothermic reaction, the removal of reaction heat generated inside the
reactor is necessary for higher yield. Uniform temperature profile was
achieved inside the reactor by removing reaction heat from the reactor
which also resulted in the reduction of the flow rate of recycling syngas
within the DME synthesis loop. Elimination of the diffusion resistance
and shift of the equilibrium to more favorable reaction conditions, i.e.
product diffusion from concentrated region to bubble phase, are among
the other reasons behind the higher efficiency of fluid pluralized bed
reactor. Catalysts which are used in fluidized bed reactor are very prone
to attrition because of the collision between the wall of reactor and
catalyst particles, which is the prime reason for deactivation and loss of
catalyst [53]. Teng [54] has developed a suitable attrition resistant
catalyst for DME synthesis in fluidized bed reactor and introduced silica
sol as a binder for active components (methanol synthesis and dehy-
dration catalyst) followed by spray drying to achieve low attrition with
a minimum decrease in catalytic activity.
3.5. Dual type reactor
DME synthesis from the hydrogenation of CO and/or CO2 is a re-
versible exothermic reaction, and strong effect of temperature profile
variation has been observed on the final conversion of this type of re-
action. Initially, the reaction is kinetically controlled, and as the reac-
tion progresses, the reaction rate also increases with the surge in tem-
perature. On the contrary, increasing temperature can harm the
equilibrium conversion of the reversible exothermic reaction. Thus, in
order to achieve higher conversion involving this reaction, the reaction
temperature should be decreased as the reaction proceeds towards the
equilibrium. So, in the case of single step DME reaction, it is necessary
to increase the reaction temperature at the beginning to achieve higher
5
Journal of CO₂ Utilization xxx (xxxx) xxx–xxx
reaction rate and then at a later stage of the reaction, the temperature
should be decreased to get higher equilibrium conversion [55].
The implication of multifunctional reactor is an efficient and com-
pact way to reduce the operating and production cost of a conventional
reactor, operating with a reversible endothermic reaction and it is
widely used as a process intensifier in many industries. In this reactor,
the heat is generated by an exothermic reaction and used as a heat
source for other endothermic reaction [56,57]. In the last few years,
there are several reports published in the literature regarding multi-
functional reactors [58]. Hunter and Mcguire [59] are one of the first
researchers to investigate this type of reactor system. They have utilized
heat exchangers to harness the heat produced in catalytic combustion
or any other exothermic reactions to sustain other endothermic reac-
tions. Similarly many other reports are available on multifunctional
reactors [60–63]. Glockler et al. [64] have proposed a simple theory to
design and analyze the process of combining endothermic and exo-
thermic reactions in an adiabatic fixed bed reactor operated in a reverse
flow mode. Farsi et al. [65] have done simulation study of DME for-
mation from methanol dehydration and cyclohexane dehydrogenation
in a dual reactor which is a combination of two fixed beds configured as
a heat exchanger. Vakili et al. [66] have built a steady-state one di-
mensional model of direct DME synthesis from syngas coupled with
cyclohexane dehydrogenation reaction in a coupled reactor. The results
showed several improvements over conventional reactor systems such
as reduction in reactor size, wherein hydrogen and benzene had been
produced as additional products and a low outlet temperature of the
product stream was achieved. This reactor configuration appears to
have a very high potential in the industry as 15,000 and 19,000 TPA of
benzene and hydrogen can be produced along with 600 TPA of DME
production.
Yusefi et al. [31] have studied the direct DME synthesis process in
an innovative system composed of a couple of shell and tube reactors,
where the standard commercially utilized DME synthesis catalyst has
been placed in the tube side of the first reactor and the shell side of the
second reactor (Fig. 6). In order to the break the thermodynamic barrier
of direct DME synthesis, the first reactor is cooled by a cold water
present in the shell side and the second reactor is gas cooled. Preheated
syngas will enter in the tube side of the first reactor and the cold water
present in the shell side of the reactor, will absorb the heat produced in
the tube side and therefore, heat energy is recovered in the form of
water vapor from the first reactor. The reacting gaseous stream will
enter the shell side of the second reactor and fresh cold feed will enter
the tube side of the second reactor. This flow of two gases at different
temperatures causes a continuous reduction of temperature along the
length of the second reactor. Co-current and counter-current are the
two possible flow patterns of the cold feed gas and the hot reacting gas
that have been studied. The product is collected from the downstream
of the second reactor [31]. Vakili et al. [66] have concluded that the
counter-current flow pattern in the second reactor offers better DME
synthesis rate. According to the simulation results, the reactors which
are operated according to the proposed optimum conditions, can pro-
duce 60 TPA DME.
3.6. Catalytic distillation
As DME production in a conventional reactor system neither
achieves complete conversion nor high purity, a number of improve-
ments of reactor system has been proposed by researchers. Current
industrial approach for the DME synthesis involves an FBR system
followed by two distillation columns to achieve ultra-pure DME
(> 99%) [67]. A number of research studies have been conducted to
investigate the possibility of using reactive distillation (RD) as an al-
ternative to methanol dehydration reaction for DME production
[68,69] (Fig. 7). Reactive distillation is a process which intensifies a
reaction by combining reaction and product separation process (dis-
tillation) in one unit to felicitate continuous product synthesis followed
U. Mondal and G.D. Yadav
Fig. 6. A schematic diagram of dual reactor system. Modified from [31].
by separation. It is also known as catalytic distillation (CD) when the
solid catalyst is used [70]. Dehydration-of-methanol like equilibrium
limited reactions are already implemented with reactive distillation
reactor system in the industry and it was found to be more economically
beneficial, process intensifier, and energy efficient with low investment
cost [70–72]. One CD tower can replace the dehydration reactor and
distillation columns in conventional DME process. Catalytic distillation
reaction conditions are mild in comparison to other methods such as
moderate reaction temperature (40–180 °C) and pressure
(800–1200 kPa) [66,73,74]. The mechanism of methanol dehydration
in CD tower is very simple. The reactant methanol has an intermediate
boiling point between water and DME. Thus methanol is concentrated
at the middle of the reactor, where the catalyst is loaded. Water and
DME can be withdrawn from the bottom and top of the CD tower, re-
spectively. The design pressure is low in the tower for methanol de-
hydration reaction because of the high boiling point difference betwe-
water and DME. Thus tower operation becomes cheap as low-cost heat
source and sink can be utilized in the CD tower [75]. There are also
other alternative technologies available for the DME synthesis such as
simultaneous synthesis and separation of DME in fully thermally cou-
pled distillation column, dividing wall column (DWC) replacing the
direct distillation sequence, heat-integrated distillation or cyclic dis-
tillation, self-heat recuperation, and reactive dividing-wall column
[76–80]. Petlyuk et al. [76] have designed a DWC which consists of two
thermally coupled distillation columns and it was implemented di-
viding a single tower into two sections by inserting a single wall at
proper position. This type of reactor holds many advantages over
conventional systems since it can separate more compounds in a single
unit and thus saving the cost of the additional unit along with reboiler
and condenser. Kiss et al. [77] have proposed an innovative DME
synthesis method based on reactive (R)- DWC tower, which combines
reactive distillation with DWC in a single vessel. They were able to
produce DME at lower cost and with a lower carbon footprint within a
single unit. They have compared their improved R-DWC system with
conventional and RD systems and reported that their optimized system
could save energy up to 12–58%, and CO2 emission could be reduced to
60%; and all of these was possible with 30% lower operating cost. Lei
et al. [68] have investigated DME synthesis from methanol dehydration
by an improved synthesis process consisting of FBR and catalytic dis-
tillation column. A kinetic model based on the Eley–Rideal mechanism
and the empirical power-rate law have been proposed for DME
6
Journal of CO₂ Utilization xxx (xxxx) xxx–xxx
synthesis from methanol dehydration reaction over macroporous sul-
phonic acid ion exchange resin as catalyst. Su et al. [75] have explored
the designing parameters of a CD tower for DME synthesis and designed
a dual catalytic system to minimize the tower temperature, and catalyst
deactivation rate. They have modeled the CD tower and validated the
model based on the VLE data and pilot test data. They have designed
the CD tower in such a way that the low-temperature catalyst and high-
temperature catalyst are kept in upper and lower portion of the tower,
respectively and the produced DME is condensed through normally
available cooling water. Bîldea et al. [81] have done a rigorous design
simulation study of DME synthesis in a reactive distillation reactor and
proposed an optimum plant design based on RD which can significantly
improve existing reaction-distillation-recycle approach of DME pro-
duction. The new 100 KTPY capacity plant is promised to operate with
lowest opex, and capex, though the energy consumption of the plant is
2.43 MJ/kg DME) only. Tong et al. [82] have explored the possibility of
combining methyl acetate hydrolysis reaction with methanol hydration
reaction in an RD tower and the effect of different operating parameters
such as methyl acetate conversion, methanol conversion and DME mole
fraction have been optimized. It was realized that the rate of methanol
hydration in the RD column was the rate-limiting step. Kaewwisetkul
et al. [83] have designed an RD column for DME synthesis from de-
hydration of methanol in crude glycerol, which is a by-product in a
biodiesel plant. They have used RADFRAC module in Aspen Plus to
study the reaction parameters on RD column such as reboiler duty,
reflux ratio, the number of stages required in the RD column for high
yield and RD column conjugation is also optimized using a total annual
operation cost.
3.7. Membrane reactor
In recent years, process intensification of DME synthesis has been
achieved by adding membrane sieve for water removal with the cata-
lysis process within the reactor. One mole of water is produced along
with one mole of DME from two moles of methanol. Therefore, if the
produced water can be selectively withdrawn from the system, then
according to the Le Chatelier’s principle the reaction equilibrium will be
shifted towards selective DME synthesis. The inclusion of selective
membranes in the catalytic reactor system has shown promising results
[84–87] and the reactor configuration is called Membrane Reactor
(MR). Hydrophilic selective membranes are of many types depending
U. Mondal and G.D. Yadav Journal of CO₂ Utilization xxx (xxxx) xxx–xxx

properties (such as selective H2O permeation and high temperature

tolerance) to be used in MR for DME synthesis. To overcome this issue,
a solid-acid catalyst F-4SF resin has been utilized in catalytic membrane
reactor to convert methanol into DME, which attains 36% methanol
conversion with 100% DME selectivity [33,89]. Fedosov et al. [90]
have synthesized a thermally resistant metal-ceramic supported layered
zeolite membrane which achieves similar conversion and selectivity. De
Falco and coworkers [91] have studied all aspects of DME synthesis by
CO2 valorization process, such as thermodynamic analysis, simulation
of the performance of the direct process of the MR, which is integrated
with microporous zeolite membrane. Lee et al. [92] have claimed that
DME yield increased to 83% from 63% when the silica-alumina mem-
brane was used in the reactor. Another report by Farsi et al. [30]
mentions that methanol conversion is increased from 80 to 86% when
the silica-alumina membrane is used for in situ water removal. Iliuta
et al. [93] have done a numerical analysis of the effect of in situ water
removal, from the fixed bed membrane reactor under DME synthesis
conditions, on the rate of DME synthesis from the mixture of CO, CO2,
and H2. It was found that a fixed bed membrane reactor with water
removal process through the hydrophilic membrane leads to a higher
yield than conventionally fixed bed reactor.
Zhou et al. [94] have employed a catalytic dual membrane system
for DME synthesis, which is a sandwich of a reactive membrane (zeolite
H-FAU) for methanol conversion and a water-penetrable membrane
(zeolite Na-LTA) for selective water removal (Fig. 8). Methanol is
converted to DME on the catalytically active zeolite H-FAU membrane.
Thereafter water produced in the reaction permeates through the next
layer of hydrophilic zeolite Na-LTA membrane. The zeolite FAU–LTA
double-layer membrane was prepared on α-Al2O3 support. The pore
size of the Na-LTA membrane is smaller than the kinetic diameter of
DME (0.43 nm), and thus selectively allows passing of water molecules.
This double layer membrane was able to achieve 91% methanol con-
version with 100% DME selectivity.
Diban et al. [95] have demonstrated a DME synthesis process
combined with CO2 capture and recovery process in a packed bed
catalytic membrane reactor (PBMR) and a “non-ideal” zeolite mem-
brane was incorporated in the reactor for in situ water removal from the
reactor. A mathematical model has also been developed to investigate
the influence of flow rate, sweep gas recirculation rate to enhance the
CO2 conversion and DME yield. The PBMR configuration has shown
higher performance than conventional PBR; for instance, as CO2 con-
version increased to 85%, DME yield increased to 55% from 16.3%
(PBR), and the recirculation of sweep gas stream is responsible for the

Fig. 7. Schematic representation of various improved DME synthesis processes:

(a) fixed-bed reactor (FBR) is followed by a catalytic distillation column; (b) a
fixed-bed reactor (FBR) is followed by two ordinary distillation columns; and
(c) a catalytic distillation (CD) column followed by an ordinary distillation
column. Adapted from [68].

upon their constituent material and pore structure, such as (i) micro-
porous zeolite membrane, (ii) polymeric membranes, and (iii) amor-
phous microporous membranes. It was found that the microporous
zeolite membranes can withstand temperature of more than 200 °C and
give satisfactory water molecule permeation (the range of H2O per-
meance was within 10−7−10−6 mols−1 m−2 Pa−1) with an H2O/H2
selectivity more than 10 [88]. Despite the advantages of zeolite mem-
branes, some studies have found that when the CO2 rich feedstock is
used for DME synthesis, then lower DME yield has been observed due to
the permeation of reactants through the membrane such as methanol Fig. 8. A schematic representation of membrane reactor (MR). Reproduced
[87]. But till now no zeolite membrane is developed with suitable from [94].

7
U. Mondal and G.D. Yadav Journal of CO₂ Utilization xxx (xxxx) xxx–xxx

Fig. 9. A schematic diagram of thermally double-coupled two-membrane reactor (TDCTMR). Reproduced from [97].

Fig. 10. A schematic diagram of thermally double coupled double membrane heat exchanger reactor (TDMHR). Reproduced from [99].

8
U. Mondal and G.D. Yadav
Fig. 11. A schematic diagram of axial-flow spherical packed-bed (AF-PSR) reactor for DME production. Reproduced from [100].
Fig. 12. A computational element in the axial flow sperical packed bed membrane reactor (AF-SPMR). Reproduced from [100].
reduction methanol loss which permeates through zeolite membrane
and increases in DME yield. Falco et al. [96] demonstrated a basic
design of a DME plant which works upon a membrane reactor to con-
vert CO2 at higher conversion. A unique DME synthesis process con-
figuration, named Double Recycling Loop DME (DRL-DME) was
adopted, which enables pure CO2 gas to be used as a sweeping gas in
the permeation site and a double recycling loop to reintroduce un-
converted syngas as well as the permeation side gases. A mathematical
model of the DME plant was also developed to study the effects of
different process parameters on the plant productivity and it was ob-
served that with this DRL-DME process configuration, 60% conversion
of CO2 along with 60% DME yield was achieved.
Farniaei et al. [97] have studied a thermally double-coupled two-
membrane reactor (TDCTMR) with H-SOD (eliminating water from
methanol side) and Pd/Ag (transferring unreacted H2 to DME side)
membranes for the simultaneous synthesis of hydrogen, DME and me-
thanol via different cycle systems (Fig. 9). TDCTMR is a multi-tubular
reactor where dehydrogenation of cyclohexane takes place in the cen-
tral tube (endothermic reaction) and exothermic reactions such as
methanol, DME generation takes place in the inner and outer tubes,
respectively. Three different types of recycled steams have been tried
and when a mixture of DME and methanol outlet steam was recycled
into DME side, the highest yield of hydrogen, methanol, and DME was
observed. A steady-state one-dimensional heterogeneous catalytic
model was also developed to investigate this innovative reaction pro-
cess. Samini et al. [98] also investigated the thermally coupled dual
membrane reactor to investigate the concept of combining exothermic
reaction (methanol synthesis and methanol dehydration) with
9
Journal of CO₂ Utilization xxx (xxxx) xxx–xxx
endothermic reaction (cyclohexane dehydrogenation) for energy effi-
cient operation. The multi-tubular reactor was combined with two
water permeable membranes and the membranes were fitted at the
inner and outer tubes for water removal from the exothermic side of the
reactor.
Bakhtyari et al. [99] studied the simultaneous synthesis of DME and
methanol from syngas along with methyl formate from methanol in a
double membrane reactor with a catalytic heat exchanger reaction
setup (Fig. 10). In the reaction setup, three catalytic beds were placed in
the concentric tubes and two water permeable membranes were fitted
at the inner and outer surfaces. Heat produced in DME formation re-
action was used as heat source for the methyl formate formation from
the methanol. A generic algorithm was proposed to optimize the reac-
tion conditions to get the highest yield. Methanol conversion to DME
and methyl formate enhanced respectively to 97% from 76% and 66%
from 62% in the optimized TDMHR (Thermally Double Coupled Double
Membrane Heat Exchanger Reactor) compared to THR (conventional
Heat Exchanger Reactor).
3.8. Spherical reactors
Samini et al. [100] have proposed use of a spherical membrane
reactor instead of the conventional tubular reactor to address a few
issues of DME synthesis from methanol such as undesirable pressure
drop, high reactor fabrication cost, water generation, low production
capacity, low diffusion through the catalyst bed due to large catalyst
particle size. Spherical reactor with lower pressure drop configuration
has the potential to overcome all above problems. Spherical reactors are
U. Mondal and G.D. Yadav Journal of CO₂ Utilization xxx (xxxx) xxx–xxx

of two types, radial-flow packed bed reactor (RF-SPR) and axial flow-
packed bed reactor (AF-PSR). AF-PSR is superior and more efficient
than the former because of better feed distribution and application of
membrane inside the reaction. A unique axial–flow spherical packed
bed membrane reactor (AF-SPMR) has been fabricated for methanol
dehydration to DME synthesis (Figs. 11 and 12). The AF-SPMR consists
of two concentric spheres and the inner sphere surface is coated with a
water-permeable selective membrane. Methanol is introduced axially
into the inner sphere through the packed bed. Water vapor permeated
through the H-SOD membrane is removed by the sweep gas introduced
in the outer sphere. This type of reactor configuration develops a lower
pressure drop and generates higher yield. The operational parameters
and length per radius of AF-PSR for methanol dehydration have been
optimized by a differential evaluation method for achieving the highest
DME yield. Total eleven process parameters have been considered for
optimization including molar flow rates, inlet temperatures, inlet
pressure of the reaction side, length per radius (L/R) of the reactor,
composition of all components in the permeation and reaction sides.

3.9. Temperature gradient reactor

A number of reactor configurations and designs have been in-

Fig. 13. The configuration of temperature gradient reactor (TGR) reactor.
Modified from [105].
vestigated to overcome the equilibrium limitation of methanol dehy-
dration reaction for DME synthesis. In order to restrict the produced
methanol from decomposing into syngas, Berty et al. [101] proposed
solvent methanol process (SMP), where the produced methanol is in-
stantly quenched into the inert solvent in order to increase conversion
and eliminate gas recycle. Selective methanol permeable membranes
(Li-Nafion) have been utilized by many researchers to remove methanol
from the reaction mixture. A condenser is also fitted inside the multi-
functional reactor to drive the equilibrium composition towards the
desired product [102]. The same strategy was opted by Li et al. [103]
for DME synthesis, which showed a 30% higher DME yield. Normally in
the quench type catalytic reactor, the catalyst bed temperature varies
with time and the increasing temperature profile of the catalyst bed of
DME synthesis reactor is optimized by injection of cool reactant gases

Fig. 14. Graphical illustration of (a) the stacking of reaction and heat exchange oil slits in the three different micro packed bed reactor-heat exchangers, (b) internal
pillar structure inside the reaction slits of reactors A and B, and (c) pillar structure inside the slits of reactor C. Reproduced from [112].

10
 Table 1
Effect of different reactors, catalysts and process parameters on selectivity for DME synthesis.
Synthesis method Types of reactor catalyst temp, °C pressure, MPa Others essential factor Conversion & yield Authors

Direct method Fixed bed CuO-ZnO-MnO / SAPO-18 275 3 H2:COx = 3; CO2:COx = 0-0.5; Space time = 5.2 gcat. h CCOx = 47% Ateka et al. [115]
(molC)−1 YDME = 21.
Direct method Micro reactor Cu-ZnO-Al2O3- Li2O/HZSM-5 250 3 H2/CO/CO2/N2 = 36/36/18/10 (vol%) CCOx = 61.1% Zuo et al. [116]
U. Mondal and G.D. Yadav

SV = 2400 ml/gcat/h YDME = 38.7%

Direct method Multistage fluidized CuO–ZnO–Al2O3/HZSM-5 250-260 5 H2:CO2 = 1; Sv = 3000 ml/gcat/h; CCOx = 48.6% Abashar et al.
bed YDME = 32.67% [51]
Direct method Slurry Bed Cu/Zn/Al slurry catalysts 280 4 H2:CO = 1:1, Syngas CCO = 54.32% Sun et al. [117]
SDME = 69.74%
Direct method High pressure high Cu-infiltrated Zr doped SBA-15 250 3.3 H2:CO2 = 3:1 CCO2 = 15% Atakan et al.
temperature cell [118]
Indirect method Dual-type catalytic CuO/ZnO/ Al2O3 & ℽ-Al2O3 277 2-4 H2/CO = 0.75-2.15; CCO = 61% Yousefi et al. [31]
fluidized bed reactor Gas superficial velocity = 0.0624 m/s
Direct synthesis A fixed bed and 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 CCO2 = 69.5% Su et al. [119]
plasma reactor GHSV = 1500–3500 mL.gcat−1 h−1 YDME = 16.9%
Direct method Fixed bed reactor Cu.ZnO/ Al2O3 or Nb2O5 250/270 3 H2/CO2 = 3 CCO2 = 9% Silva et al. [120]
SV = 10 h−1 S DME = 31%
Direct synthesis Multitubular fixed bed Cu-Zn-A1/γ-Al2O3 220-260 2.2–2.5 Biomass to Syngas CCOx = 45% Wang et al. [121]
reactor GHSV 1200−h
Direct synthesis High-pressure CuO-ZnO-MnO/SAPO-18 270-350 3 H2/CO = 3; CCOx = 36% Ateka et al. [122]
isothermal fixed-bed space time (2.5–20 gcat h (molC)−1) YDME = 13%
reactor
−1
Indirect synthesis Fixed bed micro Nano-sized γ-Al2O3 250-400 0.2 MeOH = 0.84 ml/min; WHSV 20 CMeOH = 82.6% Hosseini et al.
reactor SDME = 99.9% [123]
YDME = 82.5%
Direct synthesis autoclave reactor Cu-ZnO colloidal catalysts + ℽ-Al2O3 260 5 syn-gas (70% H2/24% CO/6% CO2) CCOx = 66% García-Trenco

11
(Parr) SV = 7.4 l syngas/gCuZn/h SDME = 68% et al. [124]
Direct synthesis Pilot scale plant with Cu/Zn/Al/HZSM-5 200-230 4-4.2 Bio syngas= H2 26-28 vol%ˈN2 16-21 vol%ˈCO 26- Yuping et al.
fixed bed tubular 31 vol%ˈCH4 3- 4 vol%ˈCO2 19-24 vol%ˈ C2˜3 < 0.7 vol% [125]
reactor GHSV = 1000 h−1
Indirect synthesis vertical reactor (Pyrex Zeolite (BEA, MFI, FER) 180-300 0.1 mixture of methanol (0.056 mol/mol) and nitrogen Catizzone et al.
vessel) (60 N mL/min) [126]
WHSV = 2 gMetOH/(gcat h)
Direct synthesis stainless steel micro Cu/ZnO/Al2O3 hybrid with γ-Al2O3 or NaZSM- 210-270 1-5 Syngas1 (H2:CO:CO2:CH4:N2) = 42:42:5:6:5 Dadgar et al.
packed bed reactor- 5 or HZSM-5 Syngas2 (H2:CO:CO2:CH4:N2) = 56:28:5:6:5 [127]
heat exchanger SV = 150–800 N cm3/min/g catalyst
Direct synthesis Micro packed bed Core-shell catalyst(CuO/ZnO/ Al2O3@H-ZSM- 250-280 4 (H2: CO : CO2 = 57.6 % : 28.8 % : 3.6 %) Ding et al. [128]
reactor 5) SV = 900 mLSTPg cat–1 h–1
Direct synthesis fixed-bed micro- Pd-CeO2-nMxOy/γ- Al2O3 300 3 H2:CO:N2:CO2:H2S = 50:25:19.95:5:0.5 CCOx = 63.2% Meng et al. [129]
reactor (M = Zr2+, Ca2+, or Zn2+) SV = 1600 L·(kg·h)−1 SDME = 68.5%
Time space
–1
yield = 30.92 mmol.(ml.h)
Direct synthesis Two stage reactor First stage = Cu–Zn–Al 300 0.98 H2/ CO2 = 3/1 Fujiwara et al.
system Second stage = Cu–Zn–Al mixed with HB [130]
Zeolite
Direct synthesis Slurry reactior Bi-function catalyst (C301/ P-γ-Al2O3) 270 4.3 Syngas(H2/CO = 2) CCO = 93% Yin et al. [131]
SV = 600 mL/h·gcat SDME = 60%
Direct synthesis Fixed bed reactor Multi-walled carbon nanotubes promoted 262 3 H2/ CO2 = 3/1 CCO2 = 46.2% Zha et al. [132]
CuO–ZnO–Al2O3/HZSM-5. GHSV = 1800 ml gcat−1 h−1 SDME = 45.2%
YDME = 20.9%
Direct synthesis Three phase slurry Cu–ZnO–ZrO2/Al-modified H-mordenite 220-270 5 Syngas(H2/CO = 2) CCO = 68% Khandan et al.
reactor (Autoclave) Cat = 3 g SDME = 82% [133]
Feed rate = 100-400 ml/min
Indirect synthesis Fixed bed micro Nano size γ-Al2O3 320 0.1 Methanol = 0.01-9.99 ml/min; CMeOH = 84% Rahmanpour
reactor GHSV = 15 h−1 SDME = 82% et al. [134]
(continued on next page)
Journal of CO₂ Utilization xxx (xxxx) xxx–xxx
 Table 1 (continued)

Synthesis method Types of reactor catalyst temp, °C pressure, MPa Others essential factor Conversion & yield Authors

Direct synthesis three integrated micro physical mixtures of CuO–ZnO–Al2O3 and γ- 220-320 5-7 Syngas = CCOx = 70-80% Hayer et al. [112]
packed bed reactor- Al2O3 (H2:CO:CO2:N2:CH4 = 56:28:5:5:6 (mol%) YDME = 25%
heat exchangers GHSV = 7500 Nml/gcat/h
Direct synthesis Down flow Fixed bed CuO-ZnO-Al2O3-La2O3/HZSM-5 with various 250 3 5 vol.% N2, 23.7 vol.% CO2 and 71.2 vol.% H2 CCO2 = 43.8% Wengui et al.
U. Mondal and G.D. Yadav

reactor La loadings GHSV = 3000 h−1 SDME = 71.2% [135]

Direct synthesis Fixed bed reactor Pd/CNT-promoted Cu-ZrO2 / HZSM-5 250 5 H2 / CO2/N2 = 69/23/8 CCO2 = 18.9% Zhang et al. [136]
GHSV = 25,000 mLSTP/(h g-hydr. catal.) SDME = 51.8%
Indirect synthesis Slurry reactor Highly porous nanocrystalline alumina 250 3 MeOH = 1.2 mol CMeOH = 92.3% Zaherian et al.
SDME = 66.4% [137]
Indirect Synthesis Slurry reactor Slurry catalyst (AlOOH) 230-290 0.1 MeOH flow rate = 0.1 ml/min CMeOH = 84.4% liu et al. [138]
SDME = 100%
Indirect synthesis Fixed bed reactor with Macro porous sulphonic acid ion exchange 118-150 2 MeOH = 0.20 ml min−1 CMeOH = 35% Lei et al. [68]
a catalytic distillation resign
column
Direct synthesis Fixed bed reactor CuO–ZnO–Al2O3 /HZSM-5 with various 260 4 The syngas (premixed) CCO = 70% Mao et al. [139]
contents of antimony oxide (0–30 wt.%) H2:CO:CO2:N2 = 61.4:28.5:2.8:7.3 (vol.%) YDME = 95%
GHSV = 1500 ml h−1 gcat−1
Indirect synthesis Two neck continuous Ionic liquids incorporating an alkane sulfonic 180,200, 220 0.1 Atkins et al. [140]
stir tank reactor acid as a part of the cation, a complex acidic
anion, [A2H]−, or both
Direct Slurry reactor with a CuZnAl slurry catalyst 280 4 H2/CO = 1:1 CCO = 33% Gao et al. [141]
mechanical magnetic GHSV = 250 mL/gcat h SDME = 93%
stirrer
Direct synthesis Fixed bed micro Hydrotalcite derived Cu-Zn-Cr + γ- Al2O3 280 4.13 H2/CO = 1.5 CCO = 63% Venugopal et al.
reactor GHSV = 6000 h−1 YDME = 43% [113]
Direct synthesis Slurry reactor a Cu-based methanol synthesis catalyst (C301 260 5 H2/CO ≈ 2 CCO = 52.6% Wang et al. [142]

12
MSC)/ γ-Al2O3methanol dehydration GHSV = 4000 h−1
Direct synthesis high-pressure tubular CuO − ZnO − Al2O3 / SiO2−Al2O3 260 5. Syngas comp. = 47% CO, 47% H2, and 6%CO2. CCO = 20% Naik et al. [143]
stainless steel fixed- GHSV = 5000 ml gcat−1 h−1 SDME = 96%
bed reactor
Direct synthesis Slurry phase autoclave CuO/ZnO/ Al2O3 + H-ZSM-5 200-240 2-5 H2/CO ≈ 1-2 CCO = 89.1% Moradi et al.
reactor SV = 500-1300 mLn (g of catalyst)−1 h−1 SDME = 57.6% [144]
YDME = 50.4%
Direct synthesis Fluidized bed reactor Attrition resistance CuO/ZnO/Al2O3- HZSM-5 260 3 H2/CO ≈ 1-2 CCO = 68% Teng et al. [145]
GHSV = 3000 ml/(g·h) SDME = 46%
Indirect synthesis Fixed bed reactor Commercial γ-Al2O3 300 1.6 MeOH flow rate = 0.55 mL/min CMeOH = 90% Mollavali et al.
WHSV = 26.07 h−1 SDME = 100% [146]
Direct synthesis shell-and-tube type CuO/ZnO/Al2O3 for methanol forming, γ- 280 5 H2/CO ratio = 1.5:1 CCO = 39.4% Song et al. [4]
fixed bed reactor Al2O3 for methanol dehydration GHSV = 2000 h−1 SDME = 50.2%
Direct synthesis shell-and-tube type Cu–Zn–Cr/ γ- Al2O3 240-270 4.13 H2–CO ratio of 1.5, GHSV of 6000 h-1 CCO = 50% Venugopal et al.
fixed bed reactor SDME = 70% [113]
Direct synthesis Autoclave reactor CuO − ZnO − Al2O3/γ-Al2O3 225-325 1-4 (H2 + CO) and (H2 + CO2) = 4:1 SDME= > 60% Aguayo et al.
[147]
Direct synthesis Temperature gradient Cu-Zn-X oxide and γ-alumina 100-289 1 H2/CO/CO2/N2) 60/30/ 5/5) CCO = 70% Omata et al.
reactor (X = Al-Ti-Nb-V-Cr) GHSV = 500 mmol h-1 g of cat.-1 [106]
Direct synthesis Autoclave reactor Mn was added by impregnating co-precipitated 260 5 syngas (H2/CO = 2.1) CCO = 67.5% Tan et al. [148]
CuZnAl and γ-Al2O3 SDME = 74.1%
Direct synthesis Autoclave reactor Cu/ZnO/ Al2O3 and γ-Al2O3 250 7 H2:CO:CO2:CH4 = 37.4 : 46.3 : 7.7 : 8.6 SDME = 95% Lee et al. [149]
Flow rate = 1 SLPM
Direct synthesis Slurry autoclave C301(Cu/ZnO/Al2O3) and 260 5 H2/CO = 1 Jia et al. [150]
reactor γ-Al2O3 SV = 10,000 h−1
Direct synthesis Fluidized bed reactor Cu − ZnO − Al2O3/HZSM-5 230-270 3 H2/CO = 1 CCO = 65% Lu et al. [151]
GHSV = 3000
(CuO-ZnO-Al2O3-Ga2O3-MgO) and (γ-Al2O3 or 4 C
ZrO2·Al2O3) GHSV = 6000 h−1
Journal of CO₂ Utilization xxx (xxxx) xxx–xxx

(continued on next page)

U. Mondal and G.D. Yadav Journal of CO₂ Utilization xxx (xxxx) xxx–xxx

for better conversion. Omata et al. [104] have designed and applied a
temperature-gradient reactor (TGR) to eliminate the equilibrium con-

Moreno-Castilla

Shikada et al.
Hirano [152]

Ng et al. [5]
version limit for DME synthesis at a higher temperature and the low

et al. [153]
activity of catalyst at a low temperature. In TGR temperature of the
Authors

[154]
catalyst bed gradually decreases along the length of the reactor with
downflow of the reaction gas mixture. Equilibrium conversion is
achieved fast at the high-temperature zone near the inlet and then the
conversion increases gradually along the temperature-equilibrium
curve as the reaction mixture flows through the low-temperature zone.
The catalyst bed is divided into a series of five zones and all the zones
Conversion & yield

are optimized for the highest syngas conversion. At 3 MPa of opera-

CMeOH = 40%

tional pressure and fixed temperature profile of TGR, they have si-
SDME = 40%

multaneously achieved high one pass conversion of syngas and high

space-time yield of DME of 1.1 kg-MeOH-equiv.kg-cat−1h−1. For im-
proving the CO conversion at lower pressure, the reactor temperature
needed to be optimized by adopting an artificial neuron network (ANN)
(CO = 16.2%, CO2 = 1.8%, H2 = 72% and He = 10%)

and genetic algorithm (GA). The five zones of the catalyst bed were
Syngas composition COx : H2 ratio = 1 : 1 to 1 : 4

encoded as “gene,” and the fitness of each gene was evaluated by the
MeOH and He gas mixture = 3.6 vol% of MeOH

CO conversion achieved according to the temperature set to the gene.

After adopting the GA and ANN, the temperature profile was optimized
and accelerated to achieve 71% conversion at 1 M P pressure [105].
Omata et al. [106] adopted an improved catalyst and optimized TGR;
one pass conversion of CO at 82% was attained at 1 MPa, W/F = 50 g-
cat·h/mol (Fig. 13).
Others essential factor

3.10. Micro reactor

Flow = 63 ml/min
CH3OH:H2O = 1:1

SV = 27,500 h−1
SV = 3000−1

SV = 0.41−1

There are multiple advantages of miniaturization of chemical re-

H2/CO = 1

actors, such as high mass transfer and heat transfer rates due to increase
in surface area to volume ratio and very short characteristic dimensions
[68]. Therefore microchannel reactors are often used for the study of
pressure, MPa

both exothermic (Fischer-Tropsch reaction) and endothermic reactions

(methane reforming) [107,108]. Another advantage of the micro-
channel reactor is the better control of reaction process even under
0.6

0.1

failed operation (leak, run away), as microreactor occupies a small

5

volume and a small number of chemicals inside the microchannels of

the rector. These safety features enable the use of the microchannel
temp, °C

250-300

260-280

reactor for high-risk processes [109,110]. Microchannel reactor has

180

250

become a unique solution for those processes which were previously

operated in batch mode. The continuous mode of operation and ease of
Activated carbon oxidised with (NH4)2S O8 and
SiO2・Al2O3, SiO2・TiO2, ZrO2・TiO2), and

scale-up from laboratory scale to plant scale is easy. Catalytic bed and
packed bed micro-reactors are two types of microchannel reactors,
CuO-ZnO-Al2O3 and y-alumina-supported

which have been investigated for gas-solid heterogeneous reactions

γ-Al2O3 modified with (ZrO2・Al2O3,

Cu − ZnO − Al2O3/ γ-Alumina (2:1)

[111]. Hayer et al. [112] have done a detailed study of differently

packed bed micro-reactors connected with heat exchangers for the
Cu/ZnO/AI2O3 and γ-Al2O3

synthesis of DME and the effect of a cross-section of slits, the number of

reaction slits and the slit geometry on the conversion and selectivity
have been studied (Fig. 14). They have achieved 95% of CO conversion
and 55% of DME yield. Venugopal et al. [113,114] have investigated
DME synthesis in a microreactor with different catalyst compositions
and achieved total 70–80% of CO conversion and 25% of DME yield
catalyst

copper
ZSM-5

HNO3

with Cu-Zn-Cr/γ-Al2O3 and 70 of CO conversion and 45% of DME yield

with Cu-Zn-Al-Y/γ-Al2O3.
Slurry bubble column
2. Micro flow reactor

4. Comparison of different reactors

Types of reactor

Plug flow micro

Internal recycle

Table 1 presents the types of catalysts and process parameters and

1. Pulse
Reactor

reactor

reactor

reactor

reactors used for DME synthesis. Thereafter a detailed comparison of

different reactor systems is presented in Table 2. A further better un-
Table 1 (continued)

derstanding of the direct DME synthesis process employed in different

Synthesis method

Indirect synthesis

Indirect synthesis

reactors is needed, which should focus more on heat recovery generated

Direct synthesis

Direct synthesis

in the exothermic reaction, and catalyst performance, recovery and

reusability. A graphical representation of the number of reactor systems
that have been used for DME synthesis irrespective of the raw material
is shown in Fig. 15.

13
U. Mondal and G.D. Yadav Journal of CO₂ Utilization xxx (xxxx) xxx–xxx

Table 2
Comparison of different reactors systems have been used for DME synthesis.
Reactor Type Operation Advantages Disadvantages

Fixed Bed reactor (FBR)
Fixed bed adiabatic reactor
Slurry phase reactor
Dual type reactor
Catalytic distillation
reactor and dividing
wall column reactor
Membrane reactor
Spherical reactors
Temperature gradient
reactor
Microreactor
Catalytic heterogeneous gas phase reaction.
Reactions with low or intermediate heat
generation are best suited.
It is an isothermal reactor and the exothermal
reaction can be carried out at the optimal
temperature depending on the thermodynamics
and kinetics of the reaction.
Combination of a conventional reactor and heat
exchanger.
It is a special type of multiphase pneumatic
contactor.
Coupling of highly exothermic and endothermic
reactions to intensify both the reactions.
Intensification of methanol dehydration reaction
by combining reaction process with the
distillation process (CD or RD).
Dividing-wall column (DWC) reactor is a single
tower divided into two section by inserting a
single wall at the proper position.
Reactive dividing-wall column (r-DWC) is a
combination of reactive distillation with DWC in
a single vessel
The hydrophilic water permeable membrane is
added inside the reactor to continuously remove
water molecules generated in the reactor from
the direct and indirect method of DME synthesis.
Two types of spherical reactors are used for DME
synthesis from methanol dehydration reaction,
such as radial-flow packed bed reactor (RF-SPR)
and axial flow-packed bed reactor (AF-PSR).
The temperature of the catalyst bed gradually
decreases along the length of the reactor with
downflow of the reaction gas mixture.
Used for the study of both exothermic and
endothermic reactions.
Very simple and low-cost operation, easy to Not suited for exogenous reactions, hot-spot
recover catalyst and reuse it. generation inside the reactor.
Catalyst sintering is a common phenomenon
due to excessive heat generation.
High syngas recycle ratio needed for the higher
conversion.
Reactor operation is very simple and the High initial investment.
operational cost is minimum. High-pressure drop across the catalyst bed.
Extracted heat can be utilized.
Reactor operation at optimum temperature
can lead to higher yield and more selectivity.
Simple construction, uniform temperature Usage of traditional solid catalyst leads to
distribution ever for a high exothermic several problems such as aggregation,
reaction, easy catalyst addition and recovery, misdistribution and rheological deterioration of
minimum catalyst sintering and low energy catalyst particles inside the reactor and thus
requirement for adequate mass transfer catalyst also get deactivated and poisoned.
between phases
Reduced operation and production cost,
can be used as a process intensifier for many
industries, highly energy efficient.
More economically beneficial, process CD requires moderate reaction temperature but
intensifier, energy efficient with low conventional methanol dehydration catalyst
investment cost. gets activated at a higher temperature.
DWC can separate more compounds in a
single unit and thus saving the cost of the
additional units along with reboiler and
condenser.
R-RWC makes the process more energy
efficient, reduces CO2 emission, and reduces
operation cost.
Higher DME yield. Sometimes produced HCs can block the pores of
Continuous removal of water molecules the membranes.
prevents the deactivation of the catalyst. Thermal and mechanical stability is a minor
Packed bed catalytic membrane reactor issue.
(PBMR) has shown higher conversion of CO2
and reduces methanol loss compared to
normal PBR reactor system.
Thermally Double-coupled two-membrane
reactor (TDCTMR) is economically viable,
energy efficient and generates the highest
yield of H2, MeOH and DME.
AF-SPMR generates lower pressure drop and Sometimes produced HCs can block the pores of
higher yield of DME. the membranes.
Thermal and mechanical stability is a minor
issue.
Equilibrium conversion is attained very fast; Complicated reactor setup; reactor operation
overall conversion and DME yield are high. and maintenance are high.
High mass transfer and heat transfer rates, Laminar flow of reactants inside the
high-risk reactions also can be operated; good microchannels.
control of the process

5. Conclusions
As the consumption of oil has increased by many folds, DME
synthesis from coal, petroleum and biomass has become very important
for energy needs. In the past few decades, significant advancements in
DME synthesis have been achieved via a combination of reactor and
catalyst development. Syngas is a major requirement of any DME in-
dustry, and the derivation of syngas from a variety of natural resources
requires an efficient technology. Some reactor systems have been ex-
perimented for DME synthesis via direct or indirect route. The fixed bed
reactor is the most used system for DME synthesis for its simplicity. For
large-scale DME production in fixed bed reactor, a high investment cost
and huge energy input are required. There are several criteria for a
reactor system to be ideal for DME synthesis process such as: (i) simple
construction, (ii) uniform temperature distribution inside the reactor
for high exothermic reaction, (iii) easy catalyst addition, and separation
process, (iv) good control of the reactor temperature to avoid catalyst
sintering, and (v) low energy requirement for adequate mass transfer
between phases. There are some innovative reactor systems that have
recently been adopted for DME synthesis such as catalytic distillation,
spherical reactor, dual type reactor, reactive dividing-wall column (R-
DWC). Dual type reactors are very energy efficient as the exothermic
DME synthesis reaction can be coupled with another endothermic re-
action and eventually the DME yield will be enhanced. Microchannel
catalytic reactors can be an ideal solution for downsizing and in-
tensifying DME synthesis process. Improving the catalyst activity is also
an important aspect of process intensification. It is envisioned that DME
would be an ideal fuel and feedstock for some chemicals provided
convenient and cost effective process technologies are provided. This
review will encourage further research and innovation.

14
U. Mondal and G.D. Yadav
Fig. 15. Usage of different reactor systems used for DME synthesis in industry.
Permissions for reproduction of figures
Necessary permissions for reproduction of some of the figures are
taken from the respective publishers.
Conflict of interest statement
The authors declare no conflict of interest.
Acknowledgement
UM got financial support as D.S. Kothari Post-Doctoral Fellow 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).
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