Chemical Engineering and Processing 82 (2014) 150–172

Contents lists available at ScienceDirect

Chemical Engineering and Processing:

Process Intensification
journal homepage: www.elsevier.com/locate/cep

Dimethyl ether: A review of technologies and production challenges

Zoha Azizi a,b , Mohsen Rezaeimanesh b , Tahere Tohidian a , Mohammad Reza Rahimpour a,∗

a
School of Chemical and Petroleum Engineering, Department of Chemical Engineering, Shiraz University, Shiraz 71348, Iran
b
Department of Chemical Engineering, College of Chemical Engineering, Mahshahr Branch, Islamic Azad University, Mahshahr, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Dimethyl ether (DME) is a well-known propellant and coolant, an alternative clean fuel for diesel engines
Received 15 January 2014 which simultaneously is capable of achieving high performance and low emission of CO, NOx and par-
Received in revised form 24 April 2014 ticulates in its combustion. It can be produced from a variety of feed-stocks such as natural gas, coal or
Accepted 15 June 2014
biomass; and also can be processed into valuable co-products such as hydrogen as a sustainable future
Available online 20 June 2014
energy. This review, which also can be counted as an extensive, pioneer review paper on this topic,
presents recent developments in synthesis methods of dimethyl ether as an alternative energy while
Keywords:
focuses on conventional processes and innovative technologies in reactor design and employed cata-
Dimethyl ether
Direct synthesis
lysts. In this context, synthesis methods are classified according to their use of raw material type as
Indirect synthesis direct and indirect methods as well as other routes, since different methods need their own operating
Syngas conversion condition. Also, the available data for the selectivity to DME and its yield as a function of H2 /CO and CO2
Catalyst content of the feed is discussed.
Reactor © 2014 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
1.1. Scope of the current review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
2. Synthesis methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
2.1. Indirect synthesis method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
2.2. Direct synthesis method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
2.3. Comparison of methods and seeking other routes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
3. Different types of DME reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
3.1. Conventional types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
3.1.1. Fixed-beds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
3.1.2. Slurry phase reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
3.1.3. Fluidized-bed reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
3.2. Innovative technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
3.2.1. Coupled and dual type reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
3.2.2. Coupling the reactor and separation units . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
3.2.3. Micro-reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
3.2.4. Membrane reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
3.3. Comparison of different reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158

Abbreviations: AF-SPMR, axial-flow spherical packed-bed membrane reactor; ATR, autothermal reforming; CapEx, capital expenditure; CD, catalytic distillation; CDR,
carbon dioxide reforming; CFC, chlorofluorocarbon; CPO, catalytic partial oxidation; CZA, CuO–ZnO–Al2 O3 ; DME, dimethyl ether; DWC, dividing-wall column; GHSV, gas
hourly space velocity; HC, hydrocarbon; H-SOD, hydroxy-sodalite; LHSV, liquid hourly space velocity; LPG, liquefied petroleum gas; MTG, methanol to gasoline; MTH,
methanol to hydrocarbons; MTO, methanol to olefins; MWCNT, multi-walled carbon nanotube; OpEx, operating expense; PEFC, polymer electrolyte fuel cell; POX, partial
oxidation; RD, reactive distillation; R-DWC, reactive dividing-wall column; SR, steam reforming; STD, syngas to DME; WGS, water gas shift.
∗ Corresponding author. Tel.: +98 711 2303071; fax: +98 711 6287294.
E-mail address: rahimpor@shirazu.ac.ir (M.R. Rahimpour).

http://dx.doi.org/10.1016/j.cep.2014.06.007
0255-2701/© 2014 Elsevier B.V. All rights reserved.
 Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150–172 151

4. Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
4.1. Catalyst diversity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
4.2. Catalyst preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
4.3. Surface acidity of methanol dehydration catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
4.4. Catalyst deactivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
4.5. Comparison of different catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
4.5.1. Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
4.5.2. Yield and selectivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
4.5.3. Deactivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
5. Essential factors affecting the performance of DME production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
5.1. Water removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
5.2. H2 /CO ratio and CO2 content of the feed . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
5.3. Operational temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
5.4. Operational pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
5.5. Space velocity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
6. Process intensification (PI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
7. Conclusions and future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169

1. Introduction traditional chlorofluorocarbons (CFCs, Freon) and R-134a (HFC-

134a) [7]. In addition, DME can be used as pesticide, polishing
The inordinate use of oil-based fuels for transportation purposes agent, and anti-rust agent. It can also be considered as an attractive
is one of the major reasons of the rapid depletion of petroleum material for producing alkyl-aromatics, a suitable source for the
which causes major environmental problems. These issues have hydrogen used in fuel cells, as well as a key intermediate for pro-
necessitated the development of clean non-petroleum based alter- ducing dimethyl sulfate, methyl acetate, light olefins, and so many
native transportation fuels. In recent years, the application of other important chemicals [8–10].
dimethyl ether (DME) as a potential diesel substitute used in com- DME can be produced from a variety of feed-stock including
pression ignition engines has attracted considerable attention [1,2]. natural gas, crude oil, residual oil, coal and waste products [11].
DME is a volatile substance which forms a liquid phase when Among potentially interesting raw materials, natural gas appears
pressurized above 0.5 MPa; therefore, it is commonly handled and to be the most promising one due to its wide availability and the
stored as liquid (see the physical property of DME in Table 1). Burn- fact that producing DME from natural gas allows production costs
ing with a visible blue flame and with similar properties as propane to be independent of the swings in the oil price [12].
and butane, DME may hence be used as liquefied petroleum gas
(LPG) for heating and home cooking [3]. For many reasons, DME is
known to be a clean fuel: (1) Unlike other homologous ethers, it has 1.1. Scope of the current review
a safe storage and handling as it does not form explosive peroxides
[4]. (2) Since DME only has C H and C O bond, but no C C bond, Extensive works have been undertaken to improve DME syn-
and since it contains about 35% oxygen, its combustion products thesis methods and the employed catalysts, but the DME subject
such as carbon monoxide and unburned hydrocarbon emissions is still suffering from the lack of a critical review. The underlying
are less than those of natural gas. (3) Owing to its high cetane num- goal of this paper is to present an extensive review considering
ber, DME is considered to be an excellent alternative to the present the valuable works accomplished over the years 1965–2013 on
transportation fuel with no emission of particulate matter and toxic dimethyl ether synthesis. The trend of related publications on DME
gases such as NOx at burning [1,2,4,5]. (4) Moreover, it has a similar over the years 1996–2013 is shown in Fig. 1. As obvious, the num-
vapor pressure to that of LPG, and hence can be used in the existing ber of published papers rises gradually and has a peak within the
infrastructures for transportation and storage [6]. Thus, the signif- year of 2011. It is concluded from Fig. 2 that these publications are
icant future perspective of DME can be counted as an alternative drastically concentrated on catalyst and then on reactor technol-
energy. ogy. Thus, taking these results into account, this paper focuses on
Furthermore, DME is widely recommended as environmentally production methods and a discussion on their wide variety of reac-
friendly aerosol and green refrigerant since it has zero ozone deple- tors and catalyst configurations while also investigating effective
tion potential and lower global warming potentials compared with parameters including water removal, H2 /CO ratio, CO2 content of
the feed, temperature, pressure, and space velocity.

2. Synthesis methods
Table 1
Properties of DME.
As shown in Fig. 3 and mentioned before, DME can be produced
Properties in two distinct ways: the first called the indirect route uses the pro-
Molecular formula C2 H6 O duced methanol to promote its dehydration; the second way which
Molar mass 46.07 g mol−1 is arguably more efficient is known as the direct route, in which
Appearance Colorless gas DME is produced in a single stage using bi-functional catalysts. The
Odor Typical technology of this single step method belongs to companies such as
Density 1.97 g cm−3
Melting point −141 ◦ C, 132 K, −222 ◦ F
Haldor Topsoe, JFE Holdings, Korea Gas Corporation, Air Products,
Boiling point −24 ◦ C, 249 K, −11 ◦ F and NKK [13,14]. Moreover, Toyo, MGC, Lurgi and Udhe have their
Solubility in water 71 g dm−3 (at 20 ◦ C) own indirect processes for DME production [13].
log P 0.022 One of the main steps in DME synthesis is the production of syn-
Vapor pressure >100 kPa
gas, which is a mixture of hydrogen and carbon monoxide and has
152 Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150–172

Fig. 1. The trend of related publications on DME.

Above 250 ◦ C, the rate equation related to Eq. (1) is given by

Bondiera and Naccache [21] as:
 E 
a
−rmethanol = k0 exp − pmethanol (2)
RT

where k0 = 1.21 × 106 (pressure of methanol (kPa) kmol)/(m3 reac-

tor h kPa), Ea = 80.48 kJ/mol, and pmethanol is the partial pressure of
methanol (kPa).
Theoretically, methanol dehydration is favored at lower tem-
peratures because it is an exothermic reaction and the formation of
by-products such as ethylene, carbon monoxide, hydrogen, and/or
coke is significant at higher temperatures.

2.2. Direct synthesis method

More recently, a combined methanol synthesis and dehydration

Fig. 2. Percentage of publications on (a) the subject of DME and (b) different syn-
thesis methods.
process has been developed to synthesize DME directly from syngas
in a single reactor [22].
The direct synthesis of DME from syngas containing H2 , CO and
CO2 follows mainly two overall reactions: Eq. (3) with water–gas
shift reaction taken into account and Eq. (4) without it.

3CO + 3H2 → CH3 OCH3 + CO2 (3)

been manufactured industrially from hydrocarbon fuels-typically
2CO + 4H2 → CH3 OCH3 + H2 O (4)
natural gas – either by steam reforming (SR) or gasification [15–17].
In the following sections, essential information about two basic Eq. (3) involves four basic reactions including [23]:
methods of DME synthesis will be presented and other routes of Methanol synthesis from CO:
DME production will then be pointed out. ◦
CO + 2H2 ↔ CH3 OH H298 K = −90.4 kJ/mol (5)
2.1. Indirect synthesis method Methanol synthesis from CO2 :
◦
Traditionally, DME has been produced from syngas in a two-step CO2 + 3H2 ↔ CH3 OH + H2 O H298 K = −49.4 kJ/mol (6)
process in which methanol is produced from syngas, purified, and
Water gas shift (WGS):
then converted to DME in another reactor. The schematic of this
◦
process is shown in Fig. 4. The commercialized process reaction of CO + H2 O ↔ CO2 + H2 H298 = −41.0 kJ/mol (7)
K
DME production from methanol dehydration is shown in Eq. (1):
◦
Methanol dehydration:
2CH3 OH → CH3 OCH3 + H2 O H298 K = −23.5 kJ/mol (1) ◦
2CH3 OH ↔ CH3 OCH3 + H2 O H298 K = −23.0 kJ/mol (8)
Many investigations on the kinetics of DME synthesis by dehy-
dration of methanol on solid-acid catalysts have been published. In each reaction, the equilibrium conversion reaches its max-
The majority of them agree that the mechanism follows either imum peak whenever the H2 /CO ratio in the feed stream
Langmuir–Hinshelwood [18] or Eley–Rideal kinetic models [19], corresponds to the stoichiometric value, that is 1.0 for Eq. (3) and
with water and DME both acting as reaction inhibitors [20]. 2.0 for both Eqs. (4) and (5).
According to the aforementioned reactions, both methanol syn-
thesis and WGS reactions occur in the syngas to DME (STD) process.
The former is crucial for DME production and the latter produces
CO2 which is the main by-product [24]. CO2 can be used in methane
reforming unit to produce syngas based on the reaction stoichiom-
etry of Eq. (9) with H2 /CO molar ratio of 1.

Fig. 3. Dimethyl ether production diagram. 2CH4 + O2 + CO2 → 3CO + 3H2 + H2 O (9)
 Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150–172
Methanol
Reactor
DME Tower
Fig. 4. A scheme of indirect synthesis process.
The overall reaction of STD process is highly exothermic and,
therefore, the temperature of the process should be controlled
properly in order to avoid run-away. Although the direct syn-
thesis method has minimum waste of natural gas, it is one of
the most complicated chemical reactions of methane conversion.
Operational units of chemical engineering are commonly used for
the separation and purification of DME in the synthesis process.
Through absorption, flash and distillation [25,26], H2 , N2 , CH4 ,
and CO2 are removed; methanol is recovered and the final DME
product is obtained. Moreover, since the methanol synthesis is
a thermodynamically limited process, consumption of methanol
in the consequent reaction to form DME will shift the methanol
synthesis equilibrium toward higher methanol conversion [27,28].
The separation of DME and CO2 becomes more difficult when
methanol is present in the system. Thus, in a proposed process
[29], the methanol and water resulted from the one-step reaction
were first condensed and then absorbed by water; finally the liq-
uid stream containing DME was distilled for final DME product.
This separation process is demonstrated to be feasible to synthe-
size DME with high purity. The schematic of this process is shown
in Fig. 5.
2.3. Comparison of methods and seeking other routes
Compared with the methanol dehydration process for DME syn-
thesis, the direct process allows for a higher CO conversion and a
simple reactor design that results in much lower DME production
costs [30]. However, the separation process for high purity DME is
relatively more complex due to the presence of unreacted syngas
and produced CO2 in the one-step synthesis process.
To Burner
Syngas
Water
Reactor
Fig. 5. A scheme of direct synthesis process.
153
To DME
Tank
To Waste
Water
Treatment
Methanol/Water Tower
In addition, because of the water–gas shift reaction which
consumes stoichiometric amount of CO to form CO2 and hydro-
gen, DME synthesis directly from syngas is not much suitable for
commercialized purposes. Generally, the syngas process for DME
synthesis is an energy consuming and a greenhouse gas emitting
process. More energy efficient and environmentally friendly design
solutions are desired to that end [31]. These processes are inte-
grating the DME synthesis line with hydrocarbon reforming units,
recycling and valorizing CO2 byproduct.
In this regard, considerable attention has been given in literature
to the use of CO2 as a raw material in the synthesis of chemicals
and liquid energy carriers in order to mitigate the accumulation
of CO2 in the atmosphere [8,32,33]. However, the application of
the conventional process is not yet industrially acceptable owing
to low CO2 conversion, low DME yield, and selectivity. Combining
the equilibrium limited reaction with the selective removal of H2 O
allows for an increase in CO2 conversion and could be an interesting
and effective way to by-pass thermodynamic limitations of DME
synthesis [34].
According to a novel method, DME can be synthesized from
methane through a two-step process in which a methyl halide (usu-
ally CH3 Cl or CH3 Br) is prepared from the oxidative bromination
reaction of methane in the presence of hydrogen halide and oxy-
gen over a Rh-SiO2 catalyst. In the second step, methyl halide is
further hydrolyzed to DME over a silica supported metal chloride
catalyst [31,35]. The main by-product of this process is methanol
while the major problem associated with the hydrolysis of organic
halides is corrosion. Surya Prakash et al. [36] studied the hydrol-
ysis of methyl bromide in the presence of PVP as a new catalyst
in a batch reactor. Use of this catalyst as a potential reusable solid
To Gas Pipe
To DME Tank
To Methanol
Tank
DME Tower
To Heat
Exchanger
Methanol/Water Tower
154 Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150–172
Fig. 6. A schematic diagram of indirect DME production from natural gas in adiabatic fixed-bed reactor.
Source: Modified from [62].
amine catalyst showed maximum efficiency according to the cap-
ture of HBr by solid PVP. The major advantage of this process is that
the polymer can be easily regenerated and reused without loss of
activity.
Dimethyl ether can also be produced through oxidative carbony-
lation of methyl bromide. The catalyst of this process can be either
SbF5 /graphite or metal oxide catalyst. The former produces methyl
acetate as by-product while the latter produces methyl alcohol
[36,37].
3. Different types of DME reactors
Pinch analysis designs a process to minimize energy consump-
tion and enhance energy efficiency. In recent years, some works
have been done to minimize generated entropy during a chemical
process by focusing on the reactors that are at the heart of chemical
process technologies. Thus, reactors play a principal role in pinch
analysis [38]. Hence, in the following sections we will start our dis-
cussion on reactor design by considering the conventional fixed
bed and slurry phase reactors used for DME production, and then
we will investigate the subsequent innovative technologies devel-
oped to solve the problems that might arise with the conventional
techniques.
3.1. Conventional types
3.1.1. Fixed-beds
Owing to simplicity and lower costs, the reactors most com-
monly used either at laboratory or pilot scale are fixed-beds [39].
For catalytic processes which have low or intermediate heat of reac-
tions adiabatic fixed-bed reactors illustrated in Fig. 6 can be the
first choice [40]. In such systems, diffusional restrictions between
phases are eliminated by gas–solid contactors [41]. Moreover, oper-
ation in a fixed bed reactor is an interesting alternative that allows
for the use of an optimum longitudinal profile of temperature from
the inlet to the outlet of the reactor. Thus, the reaction rate is
high near the inlet (conversion is far from that limited by ther-
modynamics); and by decreasing temperature along the reactor
high conversion is attained at the outlet [41]. However, in the case
of highly endothermic or exothermic reactions, there is the prob-
lem of reaction putting out or catalyst sintering [42]. Therefore,
the challenges of thermodynamic limitations and excessive cata-
lyst deactivation in conventional fixed bed reactors have led the
DME reactor to operate at a high syngas recycle rate in order to
avoid temperature rise that might further result in a lower per-
pass conversion as well as larger capital investment and operating
costs [43,44].
3.1.2. Slurry phase reactors
Besides fixed beds, the other type of reactor commonly used in
commercial direct DME synthesis technology is slurry phase reac-
tors [42]. In three-phase slurry reactors, synthesis gas is dispersed
as the bubble phase in a solvent used to suspend the catalyst. Having
the merits of lower investment and better heat transfer, one-step
slurry phase DME synthesis has been known as a potential process
for large-scale DME production. For DME synthesis, syngas should
be transferred from gas bubbles to liquid phase solvent and then
to catalyst particles. This process causes severe limitations in mass
transfer between phases and consequently decreases the overall
reaction rate. While controlling the reactor temperature is much
more manageable in slurry reactors than in adiabatic fixed-bed
reactors owing to the large heat capacity of the solvent, some disad-
vantages have been reported [45–50]. For instance, the equipment
required in slurry reactors is complicated because in addition to the
main reactor body, a recycling system and a gas-liquid separator are
needed [41]. Moreover, the loss of catalyst particles from the reactor
is another challenge that limits the reactor’s use in DME production
[46,51]. The optimum values for temperature and space velocity can
be obtained according to Papari et al. [52]. They also reported that
rising pressure and catalyst concentration can enhance the reactor
performance.
3.1.3. Fluidized-bed reactors
Fluidized-bed reactors have been suggested by some
researchers as a perfect reactor configuration for DME syn-
thesis [53,54]. These reactors are at the initial stage of laboratory
testing, and their feasibility has not yet been established [13].
Fluidized bed reactors show better heat removal characteristic
owing to freely moving catalyst particles in the bed. Because of
the intensive mixing of catalyst particles gas–solid mass transfer
resistance decreases, thereby achieving an excellent temperature
control. In addition, achieving high conversion without the need
for recirculation and under moderate operating pressure is another
benefit [41]. However, collision between catalyst particles and the
reactor wall causes loss of catalyst [55].
3.2. Innovative technologies
To reduce both capital and operating costs and to increase
energy efficiency, process integration can be considered. The multi-
functional reactor integration can be used, for example, for coupling
exothermic and endothermic reactions, or coupling reaction and
separation units.
 Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150–172 155

Fig. 7. A schematic diagram of dual-type DME reactor configuration.

Source: Modified from [62].

3.2.1. Coupled and dual type reactors
In this type of reactors, the exothermic reaction becomes the
heat source for the endothermic reaction(s) [56–58]. Some inves-
tigators suggest an industrial dual-type reactor for producing DME
directly from syngas [59,60]. In this regard, Vakili et al. [61] inves-
tigated the design parameters and operating conditions of their
proposed dual-type reactor. In the dual-type reactor, the cold feed
entered the tube side of the second reactor and was preheated by
the reacting gas that flew in the shell side. The boiling water in
the shell side of the first reactor absorbed the heat of exothermic
reactions and produced water vapor. The production capacity of
the proposed reactor configuration (see Fig. 7) was estimated to be
the same as that of the large-scale commercial DME reactor based
on the indirect method. Their results made it clear that the use of a
counter-current configuration in the second reactor was better than
a co-current mode owing to more DME production rate. According
to the simulation results, the process design based on the proposed
optimal reactor configuration could produce about 60 ton/day DME
more than the conventional DME plant. Furthermore, this new con-
figuration reduced DME production costs by eliminating a separate
unit for methanol production and purification [61–63].
Moreover, on the basis of simulation results, Vakili et al. [64]
showed that changing the molar flow rate of the exothermic side
could control hot spots in the aforementioned thermally coupled
heat exchanger reactor.
In the work of Khademi et al. [65], optimal operation conditions
for a thermally coupled reactor in which simultaneous DME syn-
thesis and cyclohexane dehydration occurred have been evaluated.
The reactor, as depicted in Figs. 8 and 9, consisted of two separate
sides for exothermic and endothermic reactions. Catalytic dehy-
drogenation of cyclohexane to benzene took place in the shell side,
whereas methanol dehydration occurred inside the tube with fixed
bed of different catalysts on both sides. Heat is transferred contin-
uously from the exothermic to the endothermic reaction zone. It
was shown that suitable amount of initial molar flow rate and inlet
temperature of both sides could provide the necessary heat to heat
up the mixtures and to drive the endothermic process at the same
time. In addition, the short distance of heat transfer increased the
efficiency of the process [65–67].
Skinner et al. demonstrated a staged reactor for ethanol dehy-
dration to ethylene which achieved a 95% conversion of ethanol
[68]. A similar reactor configuration was applied to dehydrate
methanol into DME using a staged reactor that coupled partial oxi-
dation in the upstream stage with methanol dehydration in the
downstream stage. The staged partial oxidation reactor is capa-
ble of integrating decomposition and deoxygenation to upgrade

Fig. 8. The thermally coupled reactor configuration.

Source: Modified from [65].
156 Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150–172
Fig. 9. A schematic diagram of the co-current mode for a recuperative reactor con-
figuration.
Source: Modified from [65].
the energy density of liquid fuels for transportation purposes
[69].
3.2.2. Coupling the reactor and separation units
Catalytic distillation (CD), also known as reactive distillation
(RD), is another example of an integrated process where the dis-
tillation column and the reactor are combined to form a single
unit. The advantages of using CD for methanol dehydration include
higher selectivity toward DME, higher conversion, and lower oper-
ational costs compared to a single reactor [70,71]. CD requires
moderate operational temperature and pressure (40–180 ◦ C and
800–1200 kPa respectively), but most of the catalysts previously
studied for this reaction were solid-acid catalysts (e.g. zeolites)
which tended to be active at higher temperatures (about 250 ◦ C).
Hence, an extensive study is required in order to make this process
operate at milder conditions [20]. A typical RD column followed by
an ordinary distillation column to recover methanol is shown in
Fig. 10.
Other innovative solutions to overcome the drawback of high-
energy consumption in distillation units are thermally coupled
distillation columns [72], dividing-wall columns (DWC) [71],
heat-integrated distillation or cyclic distillation [73]. The Petlyuk
configuration, consisting of two fully thermally coupled distillation
columns [74], evolved to the practical implementation in a DWC
that split the middle section of a single tower into two sections by
Fig. 10. Simplified DME production process via CD process.
Source: Modified from [76].
inserting a vertical wall in the vessel at an appropriate position.
DWC found great appeal in the chemical process industry as it
could separate more components in a single distillation unit,
thereby reducing the cost of building two columns and cutting the
operating cost by using a single condenser and reboiler. In fact,
using DWC can save up to 30% in capital investment and up to 40%
in operating costs and also up to 30% in energy saving [72,75].
On the basis of the integration concept, some researchers
proposed a novel process for DME production by methanol dehy-
dration based on a reactive dividing-wall column (R-DWC) [76].
Fig. 11 simply illustrates the path from CD to R-DWC. Kiss and
Suszwalak concluded that the RD process alone might not jus-
tify investments in revamping existing plants but that in the case
of building a new plant the RD alternative would be a preferable
choice because of its lower footprint and milder operating condi-
tions. They also claimed that the innovative reactive DWC process
had better performance compared to the conventional or the reac-
tive distillation process: significant energy saving of 12–58%, up
to 60% reduced CO2 emissions and up to 30% lower total annual
costs. Consequently, the novel R-DWC process can be considered
as a serious alternative for the production of high-purity DME in
new as well as revamped industrial plants [76].
3.2.3. Micro-reactors
Micro-structured reactors, where chemical reactions take place
in channels or slit-like arrangements of sub-millimeter range of
dimensions, are new alternatives to the synthesis of dimethyl ether
from syngas. A typical micro-reactor provides a high surface-to-
volume ratio and a short distance to the wall, thus enhancing
heat and mass transfer rates greatly [14,23]. Hence, they are
suited for both highly exothermic and endothermic reactions [5].
The microstructured reactors also offer high controllability of the
reaction conditions owing to a small holdup value which allows
for partial or total elimination of hot spots by avoiding thermal
runaway, laminar flow behavior, compactness, and parallel pro-
cessibility [77].
3.2.4. Membrane reactors
Membranes may act as permselective barriers or as an integral
part of catalytically active surfaces [78]. In DME synthesis indirectly
from methanol, if water vapor generated by the catalytic reaction
can be selectively removed from the reaction zone, decrease in cat-
alytic activity can be prevented and hence a good reaction yield
can be obtained even in a mild temperature condition. Further, no
additional steps of dimethyl ether separation and purification are
required [79]. The removal of H2 O during methanol dehydration
by means of the membrane concept can reduce H2 O promoted cat-
alyst deactivation and enhance DME productivity [80]. However,
the enhancement of H2 O flux through the membrane (i.e. by using
higher sweep flow rates) would also produce undesired HC [81].
Consequently, an optimum value for H2 O flux through the mem-
brane should be selected.
Presently available membranes are amorphous silica, F-4SF,
ZSM-5, MOR, SIL, and polymeric membranes [81,82]. However, they
still suffer from pore-blockage, thermal, and mechanical stability;
and the dilution caused by the need for sweep gases have limited
the usefulness of the membrane reactor systems [83]. However,
the benefits of the membrane systems have been demonstrated
through a wide number of experimental and theoretical studies
[78,84].
Another way to increase the yield of reaction is the controlled
addition of reactants. Rahimpour et al. showed in their work that
proper addition of H2 could enhance DME production [85–88]. In
light of this new concept, Mardanpour et al. have developed a model
for a shell and tube fluidized bed membrane reactor in order to
synthesize dimethyl ether. In their proposed model, as depicted by
 Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150–172
Fig. 11. Path from conventional setup to reactive dividing-wall column (R-DWC).
Source: Modified from [76].
Fig. 12, hydrogen permeates along the reactor leading to a better
performance and efficiency [89].
Polymer/ceramic catalytic membranes in the work of Volkov
et al. were prepared by deposition of a polymeric solid-acid catalyst,
namely F-4SF resin (the Russian analog of Nafion), onto the inter-
nal surface of the ceramic ultrafiltration tubular membrane with
an intermediate selective layer of titanium dioxide (see Fig. 13).
They studied vapor phase dehydration of methanol to DME on the
F-4SF/ceramic catalytic membrane reactor as depicted in Fig. 14.
Fig. 12. A schematic diagram of co-current mode for fluidized bed membrane reac-
tor (FBMR) configuration.
Source: Modified from [89].
157
Although at the temperature range of 70–120 ◦ C the F-4SF sample
showed high initial activity in the conversion of methanol to DME,
the reaction was accompanied by the fast deactivation of the cata-
lyst. The authors have related this behavior to the strong adsorption
of methanol and the produced water within this temperature inter-
val. Hence, to prevent deactivation of the catalyst and to improve
methanol conversion, it was proposed that the rate of alcohol des-
orption should be increased and also selective removal of water
from the reaction zone must be provided [82].
Optimal coupling of exothermic and endothermic reactions can
be feasible and beneficial [89]. A distributed mathematical model
followed by optimization for products in a thermally coupled
membrane reactor composed of three sides has been developed
for methanol and benzene synthesis by Khademi et al. [90–94].
In their proposed configuration, methanol synthesis took place
in the exothermic side which supplied the necessary heat for
the endothermic dehydrogenation of cyclohexane reaction. By co-
current flow of sweep gas through the permeation side, selective
permeation of hydrogen through a Pd/Ag membrane was achieved.
Iliuta et al. evaluated the use of glycerol, a source of syngas,
to produce DME in a dual bed membrane reactor involving the
endothermic catalytic glycerol reforming and exothermic DME
synthesis process. Not only did this technology enhance thermal
efficiency but also it could reduce the cost of syngas production
in DME production unit. The schematic figure of the dual bed
membrane reactor is shown in Fig. 15. In order to enhance the pro-
ductivity of the DME synthesis process operated at high CO2 feed
conditions, the reactor had the capability to remove water from
Fig. 13. Catalytic F-4SF/ceramic composite tubular membrane.
Source: Modified from [82].
158 Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150–172

Fig. 14. A scheme illustrating a catalytic membrane.

Source: Modified from [82].

the system by means of a hydrophilic membrane tube placed in the the pressure drop decreased, but also more production of DME was
center of the reactor [95]. obtained [80,97].

3.2.4.1. Spherical reactors. Due to some reported disadvantages of
tubular packed-bed reactors such as high pressure drop along the
reactor, high manufacturing cost and low production capacity,
the feasibility of spherical packed-bed reactor as a novel reactor
configuration was studied by Samimi et al. They developed an axial-
flow spherical packed-bed membrane reactor (AF-SPMR) for the
dehydration of methanol. During the reaction, water vapor was
withdrawn by Hydroxy-sodalite (H-SOD) membrane, a zeolite-like
material, in order to shift thermodynamic equilibrium toward the
production side. The results indicated that in AF-SPMR, not only
3.3. Comparison of different reactors
A comparison of aforementioned reactors is provided in Table 2.
It is worth mentioning that further engineering studies are nec-
essary to identify design solutions for the direct DME synthesis
reactor, providing maximum process intensity, advanced recovery
of heat generated in the process and preservation of catalyst activ-
ity. These should consider the most efficient spatial distribution
of the two catalyst components, along with good temperature and
composition control in the space of catalyst bed.

Fig. 15. Schematic diagram of two-bed reactor system.

Source: Modified from [95].
 Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150–172 159

Table 2
Different types of DME reactors in comparison.

Reactor type Characteristics/usages Benefits in a DME plant Cautions

Fixed-beds • Simplicity and lower cost – • Catalyst deactivation

• Catalytic heterogeneous gas phase
reactions
• For catalytic reactions with low or
intermediate heat of reaction
• High conversion achieved by
decreasing the temperature along the
reactor
Slurry phase Catalytic heterogeneous gas phase
reactions
Fluidized-bed Catalytic heterogeneous gas phase
reactions
Coupled and dual type For both highly exothermic and
reactors endothermic reactions
Coupling reactor and • For methanol dehydration
separation units • CD (or RD): distillation column and
the reactor are combined.
• DWC: split the middle section of a
single tower into two sections.
• R-DWC: reactive dividing-wall
column (based on DWC design)
Micro reactors For both highly exothermic and
endothermic reactions
Membrane reactors Has been used in indirect and also
direct methods.
• High recycle of syngas
• High operational investment
• High pressure drop
Manageable temperature better heat transfer • Complicated equipment
• Loss of catalyst particles
• Lower gas–solid mass transfer resistance • Collision between catalyst particles
• Excellent temperature control and the reactor wall
• High conversion and no need for recirculation • Loss of catalyst
• Moderate operating pressure
• Lowering both capital and operating costs
• Highly energy-efficient
• Hot spots can be controlled
• Higher selectivity/conversion CD: requires moderate temperature,
• Reducing operational cost while the employed catalyst is active at
• R-DWC: lowers footprint with milder higher temperature
operating condition, better performance
(energy saving, reduced CO2 emission, reduced
total annual cost)
• High controllability of the reaction conditions Laminar flow behavior
• Small holdup value
• Avoiding thermal runaway
• Compactness and parallel processibility
• Good reaction yield • May produce undesired HC
• No additional steps of separation and • Pore blockage
purification • Thermal/mechanical stability issues
• Prevent the catalyst deactivation
• Dual bed membrane reactor:
• higher thermal efficiency
• reduces the cost of syngas production
• Spherical membrane reactor:
• Decreases the pressure drop
• Increases the DME production

4. Catalysts In CuO–ZnO–Al2 O3 (CZA) catalysts, metallic copper clusters are

4.1. Catalyst diversity
Extensive research is conducted on finding better catalysts that
have higher selectivity toward DME formation and a lower ten-
dency to generate hydrocarbons and coke. With regard to DME
synthesis by indirect method, the commonly employed catalysts
are solid-acid types. Catalysts for the STD process are bi-functional
catalysts composed of a metallic function for methanol synthesis
and a solid-acid function for the transformation of methanol into
DME [41,96]. It should be noted that the heat conduction of the
bi-functional catalysts is poor; hence, the applied working tem-
perature of the bi-functional catalysts is in a temperature range
of 523–673 K and pressures up to 10 bar [7,23,98]. The metallic
function is mainly composed of such oxides as CuO, ZnO, Al2 O3
and Cr2 O3 [24,41,99]. Moreover, a myriad of solid-acid catalysts
have been explored including ␥-Al2 O3 , modified alumina with sil-
ica, TiO2 -ZrO2 , clays, ion exchange resins, Boehmite (AlOOH) and
zeolites such as H-ZSM-5, HY, mordenites, SAPO, MCM, Ferrierite,
chabazite and H-beta [2,7,10,23,30,41,100–109]. Meanwhile, the
solid-acid catalysts can be modified with sulfate, zirconium, iron,
silica, phosphorus, B2 O3 , and rare metals to obtain moderate acid-
ity for higher CO conversion and minimal by-product (light olefins
and heavy hydrocarbons) formation [7,23,30]. For instance, Jin et al.
prepared a series of zeolite Y modified with La, Ce, Pr, Nd through
ion-exchange. It was found that these rare earth metals resulted in
Y enhanced acidity and thus exhibited higher activity and stability
than did pure HY for methanol dehydration to DME [100].
the active sites for both methanol synthesis and WGS reactions and
conversion of syngas to methanol depends on the copper metal
surface area [8,23,110,111]. ZnO plays a pivotal role in maintaining
the active copper metal in optimal dispersion, thus providing a high
number of active sites exposed to gaseous reactants [2]. However,
Hadipour and Sohrabi observed that excess of ZnO in CZA had a
negative effect on the activity [96]. The purpose of the addition
of M3+ ions (e.g. Al3+ ) into CuO–ZnO-based catalysts is to increase
both surface area and copper dispersion. This trivalent ion has also
an inhibiting effect on the sintering of Cu particles at on-stream
conditions [2]. In contrast to ZnO, Hadipour and Sohrabi expressed
that the presence of CuO and Al2 O3 in excess amount enhanced
the catalyst activity by increasing the dispersion of active sites and
hence promoted the surface area of catalyst [96].
Copper particle size and its dispersion are found to be affected
by preparation conditions such as Cu/Zn molar ratio, type of pre-
cipitant and calcination temperature [110,112–114]. In a series of
experiments conducted by Wang et al., the effect of different Cu/Zn
molar ratios of Cu–Zn-based catalyst was investigated. The obser-
vation showed that low Cu/Zn ratio was more beneficial to the WGS
reaction, because more WGS active centers might be represented at
those ratios. However, catalysts with higher Cu/Zn ratio exhibited
greater activity for methanol synthesis which might be ascribed
to the stronger interaction between CuO and ZnO molecules and
the atomic dispersion between them [24]. Another important fac-
tor for CZA-based catalysts in STD process is the ratio between CZA
and the solid-acid function which was studied by Abu-Dahrieh et al.
[25,115]. Under the conditions they used, it was observed that the
160 Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150–172
most suitable ratio between the metal and acid function was 1:1 for
CZA/␥-Al2 O3 and 3:1 for CZA/HZSM-5 admixed catalyst. In another
work, a special core-shell structured bi-functional catalyst (an H-
ZSM-5 zeolite core enwrapped by one layer of CuO–ZnO shell) was
prepared for the STD process. Characterizations disclosed that these
bi-functional catalysts possessed high Cu surface area as well as
high Cu dispersion, and consequently they would display excellent
catalytic performance [116].
As mentioned before, ␥-Al2 O3 is a methanol dehydration cat-
alyst. It is very attractive since it is cost effective and exhibits
high surface area, excellent thermal and mechanical stability, high
mechanical resistance, and high selectivity toward DME [117,118].
Furthermore, it has high catalytic activity toward DME formation
due to its low content of highly acidic sites which are mostly of the
Lewis type [101]. Although ␥-Al2 O3 is active, it tends to strongly
adsorb water thereby losing activity [119].
Zeolites are crystalline aluminosilicates with periodic arrange-
ment of cages and channels which were found to have extensive
industrial use as catalyst, adsorbent, and ion exchanger. It can be
concluded from literature that zeolite materials in a temperature
range of 250–400 ◦ C and pressures up to 18 bar can be a proper
candidate to play the role of a solid-acid catalyst in methanol dehy-
dration process [119]. In comparison to other catalysts, zeolites in
general possess high surface area which comes from their micro-
porous crystalline interface [10]. However, the zeolites’ narrow
and slender microporous structure may restrain DME from quickly
diffusing through the pores. As a result, zeolites may lose their cat-
alytic activity and selectivity quickly owing to the formation of
by-products and deposition of carbonaceous compounds [30]. To
overcome this disadvantage, researchers have used some modifi-
cations to zeolite catalysts. For example, Tang et al. employed a
ZSM-5/MCM-41 composite molecular sieve as the methanol dehy-
dration catalyst. The results exhibited high activity, selectivity and
stability in the process of methanol dehydration to DME according
to the combination of the channel advantage of the mesoporous
molecular sieve and the acidity advantage of ZSM-5 [30].
Among zeolite-type solid-acid catalysts used for the dehydra-
tion of methanol to DME, H-ZSM-5 which exhibits more activity
and stability than ␥-Al2 O3 catalyst [2,119] is reported to be the
most promising for DME synthesis from syngas [120]. According to
Qi et al. the activity and selectivity of ZSM-5 can be increased by
the use of an H-ZSM-5 supported Cu–Mo oxide catalyst for direct
synthesis of DME [121].
Another effective methanol dehydration catalyst is BFZ, with
Beta zeolite cores and Y zeolite polycrystalline shells. BFZ in the
H-form (HBFZ) exhibits moderate acid strength and meso-porosity
which is responsible for its high activity for CO hydrogenation [30].
In comparison to CZA/HY bi-functional catalyst, CZA/HBFZ shows
higher activity and stability for the direct synthesis of DME from
CO hydrogenation [30].
H-mordenite that can be a very attractive methanol process-
ing catalyst is another zeolite that is of interest owing to its high
catalytic activity in etherification in conversion to olefins (MTO).
This property allows for the possibilities of performing both DME
synthesis and MTO technologies in a single reactor only by temper-
ature adjustment [10]. Moradi et al. showed that acidic mordenite
zeolites in H-form, produced from Na-form through ion-exchange
process, had higher surface area than the Na-form one. They
explained that new pores were generated by ion-exchange treat-
ment, thereby increasing the surface area [10].
Stiefel et al. studied various dehydration catalysts in the synthe-
sis of DME directly from carbon monoxide rich syngas. They showed
that pore volumes and specific areas of zeolites would decrease in
the following order:
H-MOR 90 > H-MFI 400 > H-MFI 90.
Moreover, their experiments introduced H-MOR 90 as a zeolite
with the highest total number of acidic sites among those stud-
ied and their investigation showed a decreasing order of catalyst
acidity as follows [117]:
H-MOR 90 > H-MFI 90 > -Al2 O3 > H-MFI 400
The strongly increasing CO conversion in the case of H-MFI 90 is
achieved at the expense of a significant decrease in DME selectiv-
ity and an increase in the formation of hydrocarbons. In addition,
the CO2 concentration in the product mixture is also considerably
increased. This can be traced back to an enhanced WGS reaction
activity stimulated by a higher water concentration in the reaction
system leading to a pronounced production of CO2 and H2 . In con-
sequence of increase in H2 concentration, the conversion of CO to
methanol is favored [117].
Recently, polymeric heterogeneous catalysts, namely Nafion
resin, have attracted a lot of attention in the conversion of methanol
to DME [122,123]. Experiments were carried out in a vapor
phase flow reactor using Nafion resin beds [122] or Nafion/silica
nanocomposites of different compositions [123]. The Nafion cat-
alysts provide 40% methanol conversion. In this case, no catalyst
activity loss and coke formation were observed. Thus, Nafion is
proved to be an advantageous catalyst for the synthesis of DME
from methanol [122,123].
Aluminum phosphate (AlPO4 ) is also a promising catalyst in
DME synthesis owing to its lower amount of coke deposition,
by-product formation, and its better water resistant property
[124,125]. The catalytic activity of AlPO4 in methanol dehydration
is found to be dependent upon the preparation method, chem-
ical composition (Al/P molar ratio), and activation temperature
[124,126].
In recent years, multi-walled carbon nanotubes (MWCNTs) as a
novel nano-carbon support or promoter have drawn lots of atten-
tion [127–129]. MWCNTs possess several unique features such as
graphitized tube-wall, nanometer-size channel, high thermal con-
ductivity and excellent surface area. MWCNTs can be used as a
catalyst support where metal particles with catalytic activity may
decorate along the external walls or be filled in the interior of the
MWCNTs. A type of bi-functional hybrid catalyst of Pd-decorated
CNT-promoted Cu–ZrO admixed with H-ZSM-5 zeolite has been
developed. Its application to direct synthesis of DME from CO2 /H2
has been studied. The catalyst displayed excellent performance for
the direct DME synthesis from CO2 /H2 in heterogeneous “one-pot”
reactions [130]. From literature, the MWCNT-supported CZA/H-
ZSM-5 catalyst is another appropriate option exhibited higher
catalytic activity and higher DME yield than unsupported one [99].
For the synthesis of DME by CO2 hydrogenation, the methanol
synthesis component of the bi-functional catalysts is usually
CuO/ZrO2 catalyst, besides the traditional CZA one. Although
CuO/ZrO2 catalyst has been reported to be an effective catalyst,
there are still disadvantages of using zirconia support. In addition
to the low specific surface area provided by CuO/ZrO2 catalyst, the
performance of the catalyst is under the influence of phase trans-
formation. Zirconia has three phases including m-ZrO2 , t-ZrO2 and
c-ZrO2 in which the transition between them might change the
properties of the catalyst. For a fixed Cu surface area, CuO/m-ZrO2
is more active for methanol synthesis than CuO/t-ZrO2 [33]. Fur-
thermore, compared with single oxide, mixed oxides have higher
surface area, better thermal stability, mechanical strength, and
stronger surface acidity. Therefore, not only do the mixed oxides
of titania and zirconia have the specialties of both oxides, but also
they improve their disadvantages [77].
Recently, several studies have focused on the design of
newer and more complex catalyst to overcome the catalyst
deactivation [131,132]. However, this induces the addition of
 Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150–172
several preparation steps resulted in extra costs and more waste
production during the preparation of an effective catalyst. Besides,
it is difficult to limit the dehydration of methanol to the sole for-
mation of DME. Indeed, the presence of an acid catalyst leads to
the consecutive formation of hydrocarbons (methanol to hydro-
carbons, MTH) [133–135]. More precisely, light olefins (methanol
to olefins, MTO) or alkanes (methanol to gasoline, MTG) can be
obtained as a function of temperature and pressure [136–144].
Nowadays, the MTO reaction is considered to be a valuable
option for the improvement of stranded gas reserves. Therefore,
several studies are devoted to either the reaction mechanism or the
applied technology [133,139–144]. Song et al. showed that a pool
of adsorbed polymethyl benzenes played a leading role in catalytic
cycles of MTH process [141–145]. Moreover, the methylation of
hexa-methyl-benzene to form hepta methyl benzeniumation has
been shown to be the first step in the carbon pool mechanism
[145,146]. This is highly dependent on the acidity of the zeolite
[146,147]. In order to limit/inhibit the MTH reaction, Ivanova et al.
investigated SiC-supported ZSM-5 zeolite catalysts. The authors
reported that the foam support allowed for the formation of small
zeolite crystals which favored the diffusion of produced DME
throughout the porous network and thus seriously prohibited the
formation of consecutive hydrocarbons. The other possible way to
artificially deactivate the “hydrocarbon pool” is to carry out cat-
alytic tests under the air atmosphere [132,148]. Indeed, Fu and
co-workers demonstrated that over SAPO-34 and ZSM-5 zeolites
the presence of 20% of air in the feed led to a negative impact on
the production of olefins at 350 ◦ C [149]. As seen, the preparation
of the catalyst remains quite complex and costly.
4.2. Catalyst preparation
Researchers are trying to modify the catalyst structure and/or
formulation in order to optimize the DME production as well
as catalyst stability improvement. The preparation method of
the bi-functional catalyst systems in direct DME synthesis
has a significant effect on the performance of the process
[124,126,131,150–152]. Hybrid catalysts used for synthesizing
DME directly from syngas are prepared in different ways includ-
ing physical mixing of methanol synthesis catalyst and solid-acid
catalyst, co-precipitation (sol–gel), impregnation, and combined
co-precipitation-ultrasound [30,153]. In the case of the admixed
catalyst, each function is prepared separately and then the pow-
ders of both functions are mechanically blended [154–160]. The
activity of the catalysts prepared by physical mixing is higher than
the activity of ones prepared by co-precipitation and impregna-
tion [30]. In a study conducted by Hosseini et al. nanocrystalline
␥-Al2 O3 catalyst was prepared by sol–gel and precipitation meth-
ods. The obtained results showed that the catalysts prepared by the
sol–gel method have higher activity than catalysts prepared by the
precipitation method. Furthermore, non-aqueous sol–gel method
offered higher activity in comparison with aqueous sol–gel one. The
advantages of the sol–gel method include the ability of maintaining
a high degree of purity, the possibility of preparing samples at low
temperatures, and changing physical characteristics such as pore
size distribution and pore volume [101].
4.3. Surface acidity of methanol dehydration catalysts
Direct conversion of carbon-monoxide-rich synthesis gas to
DME essentially depends upon the acidity of the dehydration com-
ponent in the catalyst system. If acidity is too low, the amount of
methanol formed cannot be dehydrated with sufficient efficiency.
If the acidity of the catalyst is too high, it also catalyzes further the
conversion of DME to hydrocarbons [117]. Hence, according to sev-
eral studies conducted, DME formation is related to sites with weak
161
and medium acidity and those catalysts with strong acid sites may
be preferable for coke deposition [100].
In order to attain optimal condition for DME production, strong
acid sites must be diluted in order to achieve a high stability against
coke formation [131]. Accordingly, Yaripour et al. modified ␥-Al2 O3
with silica to improve its surface acidity. Their results evidenced
that by modifying alumina with silica, the surface acidity of the
aluminosilicate catalyst increased with increasing silica loading
and reached its maximum peak at silica loading of 6 wt.%. Then
the surface acidity gradually decreased and showed almost simi-
lar performance in comparison to unmodified ␥-Al2 O3 at 15 wt.%
silica loading [161]. Hosseini et al. studied the effect of crystal size
on the acidity of nanocrystalline ␥-Al2 O3 catalyst for the synthesis
of DME through the dehydration of methanol. The results showed
that samples with smaller crystallite size possessed higher concen-
tration of medium acidic sites and consequently higher catalytic
activity [101].
It is well known that the acidic sites on the surface of solid-acid
catalysts are of either Bronsted or Lewis acid type [161]. Methanol
is supposed to be dehydrated over both Lewis acid–base pair and
Bronsted acid–Lewis base pair sites [39,162].
Concerning the acidity of ␥-Al2 O3 , according to several inves-
tigations, it is mainly due to Lewis-acid sites whilst the acidity of
MFI zeolites and AlPO4 in many cases is dominated by Bronsted-
acid sites [102,105,163]. Acidity of H-MOR zeolites can also be
dominated by Bronsted-acid centers; but H-MOR systems with an
approximately equal number of Bronsted and Lewis acid centers
have been also described. Both types of acid sites exhibited high
acid strength [117]. High Bronsted acidity of mesoporous alumi-
nosilicate namely alumina impregnated SBA-15 has also facilitated
the conversion of methanol to values close to equilibrium with
100% dimethyl ether selectivity at temperatures over 300 ◦ C [1].
In fact, authors have proposed that H-ZSM-5 which is currently the
best available methanol dehydration catalyst for the STD process
has large number of moderate strength Bronsted acid sites which is
responsible for its perfect behavior [102,105,164]. However, some
reports did not find a relationship between MeOH dehydration
rates and the number of Bronsted acid sites in HZSM-5 [165]; hence,
more research is needed to prove the validity of this hypothesis.
4.4. Catalyst deactivation
The catalyst systems described in the preceding sections are
generally prone to become deactivated by the sintering of active
copper sites, to coke deposition due to the presence of strong
acid sites, to poisoning because of the contaminants that might
be present in the syngas, and thus to the blockage of acidic sites
[100,117].
For hydrocarbon reactions over zeolites, deactivation is mainly
attributed to two main mechanisms: The acid site coverage which
deactivates the catalyst by coke adsorption; and pore blockage
which is the deposition of carbonaceous compounds in cavities
or channel intersections that make a pore inaccessible and con-
sequently prohibits access to the active sites inside the pores for
the reactants [10]. In addition, it is well known that coke formation
on zeolites is a shape-selective process. Under comparable condi-
tions, large-pore zeolites are more susceptible to deactivation by
coke deposition than medium-pore zeolites [164].
Although H-ZSM-5 is not sensitive to water [2,33], it shows high
activity for the transformation of DME into hydrocarbon byprod-
ucts. These hydrocarbons can further evolve into heavy structures
(coke) and consequently can block the zeolite pores and cause its
deactivation. However, this deactivation is slow due to the high
partial pressure of hydrogen that attenuates the mechanism of coke
formation [41]. This phenomenon can be controlled by employing
a suitable concentration of Na in the zeolite in order to moderate
162 Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150–172
the number of Bronsted sites and to reduce the acid strength of the
H-ZSM-5 zeolite [41]. The addition of silicalite shell to the ZSM-5
zeolite is also considered as an efficient method for improving the
resistance toward carbon formation [9].
A comparison between H-form mordenite and Na-form mor-
denite catalysts carried out by Moradi et al. showed that H-MOR
catalysts possessed higher initial dehydration activity owing to
the strong acidic properties of hydrogenation. However, the cat-
alytic activity decreased rapidly with time on stream in the reaction
that would be attributed to higher concentration of strong acid
sites leading to the formation of coking materials. Moreover, they
reported that the super cage of H-MOR was likely to provide enough
space for complete coking which resulted in entrance blockage of
the super cage. In this case, since water had no opportunity to
eliminate the carbon deposited on the active sites and to regen-
erate mordenite catalysts, the deactivation of H-MOR by carbon
formation was irreversible [10].
Raoof et al. performed the indirect process of DME synthesis
in an adiabatic fixed bed heterogeneous reactor by using acidic
␥-alumina in order to investigate the effect of water on the deacti-
vation of ␥-alumina. The mixture of methanol–water feed showed
a catalyst activity loss of about 12.5 times larger than that of
the pure methanol feed [4]. Decreasing the catalyst activity in
methanol–water feed was reported to be related to the blockage
of the active sites through competitive adsorption of methanol on
the catalyst surface [117].
For the system of CuO–ZnO–Al2 O3 /␥-Al2 O3 bi-functional cat-
alyst, results evidenced that the deactivation level was much
lower for “H2 + CO2 ” feeds than for “H2 + CO” feeds. This result was
explained by the fact that higher concentration of water in the reac-
tion medium formed through the reverse water gas shift reaction in
the case of CO2 rich feed limited coke deposition owing to compet-
itive adsorption between water and coke precursors on the active
sites [8].
As previously mentioned, two types of reactors mostly used in
the production of DME are slurry reactors and fixed bed ones with
CZA/␥-Al2 O3 as DME synthesis catalyst. These catalysts deactivate
more quickly in the slurry reactor than in the fixed-bed reactor.
The deactivation of hybrid catalyst for DME synthesis is caused by
the deactivation of Cu-based methanol synthesis catalyst rather
than methanol dehydration catalyst [166]. Compared with fixed-
bed reactor, it is more difficult to remove H2 O from the surface of
Cu-based catalyst in the slurry reactor because liquid paraffin pose
an additional resistance [8]. Thus, the morphology of the catalyst
might change owing to the existence of water. A part of Cu changes
into Cu2 (OH)2 CO3 due to higher partial pressure of water in DME
synthesis, consequently leads to a decrease in the number of active
sites of the Cu-based catalyst. In addition, under DME synthesis con-
dition in slurry reactors, some ZnO converts into Zn5 (OH)6 (CO3 )2
which weakens the synergistic effect between Cu and ZnO. Metal
loss of Zn and Al, caused by hydrothermal leaching, is also another
aspect of methanol catalyst deactivation in such systems [50].
4.5. Comparison of different catalysts
As described in the preceding sections, solid-acid catalysts are
used in indirect method and also as a component of bifunctional
catalyst for methanol dehydration to DME. Some of them that
will be discussed comparatively are alumina, zeolites, Nafion resin,
AlPO4 and CuO/ZrO2 , from the viewpoints of activity, yield or selec-
tivity toward DME production, and their possible deactivation.
4.5.1. Activity
It has been shown by Flores et al. [167] that metallic compo-
nents influence the direct synthesis of DME from syngas. The role
of this component was related directly to the CO conversion. The
different precipitation conditions used to prepare the methanol
synthesis catalyst influenced its textural and structural properties,
but these changes did not influence the catalytic activity. For the
methanol synthesis, amongst the dozens of catalytic materials pro-
posed, the largest utilization has the classical methanol synthesis
catalyst Cu–ZnO–Al2 O3 , sometimes modified with ingredients con-
tributing to the increase of the copper dispersion and stability. It
is commonly employed in the one-step DME synthesis and usu-
ally prepared by the conventional co-precipitation method, the
catalytic activity depending on Cu/Zn/Al ratio and the prepara-
tion conditions [168]. Catalysts based in Zr as the promoter also
presented changes on the textural and structural properties and
exhibited an increase in the metallic area and CO conversion. The
activity of a solid acid on the methanol dehydration reaction was
also found to be determined mainly by the number of its more
acidic sites. Good activity and selectivity for methanol etherifica-
tion have the solid acids with moderate acidity (␥-Al2 O3 , zeolites,
mesoporous materials etc.). A largely used etherification catalyst is
␥-alumina. Due to its relatively low content of high acidity sites,
this catalyst offers a good selectivity toward DME, while exhibiting
reasonably high activity and high chemical and thermal stabil-
ity. Activity and stability performances of ␥-alumina can also be
improved by promoting with different metal oxides. The Nb2 O5
modified ␥-alumina showed a higher catalytic activity in methanol
etherification than the untreated one [168]. The mixture containing
methanol catalyst and HZSM-5 has also been found to be one of the
most effective amongst the systems evaluated so far. However, over
CZA/HZSM-5 mixtures the reaction is controlled by the methanol
synthesis step, thus changing the HZSM-5 amount cannot affect the
reaction data [154]. The following notes are on activity of different
catalyst discussed earlier in a short review:
• CZA: Negative effect of excess ZnO on the activity of the cata-
lyst [96]. A comparison of two bifunctional catalysts with the
same CZA component but different solid-acid catalyst from their
activity and stability viewpoint: CZA/HBFZ > CZA/HY. MWCNT
supported CZA/HZSM-5 has high activity [30].
• Zeolites: ZSM-5/MCM-41 has higher activity than zeolite cat-
alyst. HZSM-5 > ␥-alumina from their activity and stability
viewpoint. Evaluation of the catalyst activity with respect to CO
conversion [117]:
H-MOR 90 < H-MFI 90 < H-MFI 400 < ␥-Al2 O3 for T < 240 ◦ C
H-MOR 90 < H-MFI 400 < ␥-Al2 O3 < H-MFI 90 for T > 240 ◦ C
• AlPO4 : The catalytic activity of AlPO4 in methanol dehydration
is found to be dependent upon the preparation method, chem-
ical composition (Al/P molar ratio) and activation temperature
[124,126].
• CuO/ZrO2 : For a fixed Cu surface area, CuO/m-ZrO2 is more active
for methanol synthesis than CuO/t-ZrO2 [33].
4.5.2. Yield and selectivity
By changing the hybrid catalyst ratio, the DME/MeOH ratio in the
product mixture can be controlled. If the same amount of methanol
catalyst is used, reaction systems with higher loading of methanol
dehydration catalyst would lead to higher DME yield at the expense
of lower methanol yield [169].
For Cu–ZnO–Al2 O3 /␥-Al2 O3 bi-functional catalyst, maximum
values of DME selectivity (83.4%) were obtained for a molar ratio of
H2 /CO = 6/1, at 275 ◦ C, 40 bar and a space time of 33.33 (g of cata-
lyst) h/(mol of reactants). Under these reaction conditions, the use
of NaHZSM-5 zeolite as acid function allowed a DME selectivity of
77.6% with a lower H2 /CO molar ratio (2/1) [168].
The best results for direct conversion of synthesis gas to DME
were obtained over bi-functional catalysts including HZSM-5 and
 Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150–172
HSY as methanol dehydration components, prepared by copre-
cipitation method: 99% DME selectivity in organic products were
reported at 290 ◦ C, 40 bar, space velocity = 1500 h−1 , using syngas
with molar H2 /CO = 2 and 5% CO2 [168].
DME selectivity is lower over the less active mixtures while an
equivalent production is achieved over both HZSM-5 and sulfated-
zirconia, which further confirms that methanol is not efficiently
dehydrated over weak acidic solids. DME production may be effec-
tively achieved by adding an optimized amount of a solid-acid
catalyst [154]. The following notes are on yield and selectivity to
DME for different catalyst discussed earlier:
• CZA: MWCNT supported CZA/HZSM-5 has high DME yield [30].
• Zeolites: ZSM-5/MCM-41 has higher selectivity than zeolite cat-
alyst [30]. The selectivity of H-MFI 90 decreases when the
temperature is above 240 ◦ C [117].
• Alumina: alumina impregnated SBA-15 has 100% selectivity
toward DME at temperature above 300 ◦ C [1].
4.5.3. Deactivation
An important challenge in the formulation of the bi-functional
catalyst and the reactor design is the prevention or limitation of
deactivating phenomena: copper sintering, coking of acidic com-
ponents and metal ions migration. Particularly, a good temperature
control is necessary, due to the important overall process exother-
micity. Results show that the deactivation behavior of the catalyst
is mainly caused by the deactivation of the methanol synthesis cat-
alyst, which is deeply caused by the synergistic effect [170]. The
following notes are on different DME catalyst deactivation:
• CZA: Experimental data obtained using CuOZnO-Al2 O3 /␥-Al2 O3
catalyst show that there is no significant sintering below 325 ◦ C
[168]. Its deactivation is more quickly in the slurry reactor than
in the fixed bed. However, for CZA/␥-Al2 O3 deactivation is lower
when the feed is H2 + CO, rather than H2 + CO2 [8].
• Zeolites: HZSM-5 is not sensitive to water, but has high activity
for transforming DME to HC [41]. However, it can be regener-
ated by the addition of water resulting from removing carbon
deposited on the catalysts [169]. Sic supported ZSM-5 pro-
hibits the formation of HC [132,148]. H-MFI 90 increases its HC
formation when the temperature is above 240 ◦ C [117]. The deac-
tivation of H-MOR is irreversible [10].
• Nafion resin: No coke formation [122,123].
• AlPO4 : Leave coke deposition [124,125].
5. Essential factors affecting the performance of DME
production
5.1. Water removal
An important parameter in DME synthesis through one-step
method is the CO/CO2 feed composition ratio. A strong synergy
is obtained with CO-rich feed owing to the effective removal of
methanol by the dehydration and elimination of produced water
by means of the water gas shift reaction [22]. Conversely, CO2 -
rich feeds favor high fractions of unconverted methanol due to the
large quantity of H2 O produced in methanol synthesis and dehy-
dration steps, thus inhibiting methanol dehydration and lowering
DME selectivity. Hence, it is anticipated that H2 O in situ removal
during DME synthesis may bring some beneficial effects. Consid-
ering indirect DME production from methanol, water is the side
product in the dehydration reaction. So, the presence of excess
water clearly shifts the equilibrium backward and reduces the ini-
tial methanol dehydration activity of DME as well as selectivity.
Under the equilibrium condition, water competes with methanol
163
for the same sites on the catalyst surface and consequently a higher
reaction temperature is required in order to achieve the same level
of conversion [106,164].
At high CO2 content, in situ H2 O removal accelerates the reverse
water gas shift reaction toward CO formation [171] and it is
expected to improve DME production [172,173]. In the case of H2 -
rich synthesis gas, in situ H2 O removal would favor DME selectivity
[44]. The sorption-enhanced reaction process may offer an attrac-
tive possibility of in situ H2 O removal by adsorption as shown by
Carvill et al. [174]. Moreover, Iliuta et al. studied the sorption-
enhanced reaction process under in situ H2 O removal conditions
for DME synthesis process in a fixed bed reactor in order to analyze
the effect of different parameters. By applying the adsorption-
enhanced concept, CO2 could be utilized as a constituent in the
synthesis gas as in situ H2 O removal that accelerates the reverse
water gas shift reaction. The reason for in situ H2 O removal in this
process displaced the water gas shift equilibrium to enhance the
conversion of CO2 to methanol and to improve the reactor pro-
ductivity. The simulated results indicated that under H2 O removal
conditions, DME yield and selectivity were favored and the fraction
of unconverted methanol was reduced. The role of H2 O removal was
prominent at higher CO2 feed concentration, because a relatively
large amount of water was produced. The preliminary theoretical
results indicated that the fixed bed reactor with in situ H2 O removal
by adsorption was more efficient in DME synthesis process than
a fixed bed reactor without H2 O removal [34]. A possible disad-
vantage of H2 O removal process is the deactivation of the catalyst
metallic function (CuO–ZnO–Al2 O3 ) by coke deposition [175].
5.2. H2 /CO ratio and CO2 content of the feed
Syngas can be produced with different compositions through
steam reforming (SR), carbon dioxide reforming (CDR) and catalytic
partial oxidation (CPO). The desired H2 /CO ratio depends upon the
intended use for the syngas. The SR process produces syngas too
rich in hydrogen while the syngas from CDR is too lean. The pro-
duced syngas from CPO is close to the desired output ratio for DME
production. In principle, the H2 /CO blend can be adjusted by using
the water gas shift reaction [15].
Variation of H2 /CO ratio can change the direction of water gas
shift reaction. In low H2 /CO ratio, the reaction progresses to pro-
duce CO2 that results in enhancement of both methanol and DME
production. In high H2 /CO ratio, CO2 production decreases which
subsequently results in DME reduction. Consequently, there is an
optimum value for H2 /CO ratio. An increase in temperature leads
to a decrease in optimum H2 /CO ratio. This can be attributed to
water gas shift reaction. With increasing temperature, water gas
shift reaction reaches equilibrium conditions rapidly. This, further
results in the reduction of CO2 production [89]. In a recent work,
it was reported that CO2 removal prior to DME reactor greatly
enhances the yield. Separation at this stage would also provide
high-purity CO2 and, therefore, would be beneficial for sequestra-
tion [176]. But from another point of view, CO2 content of the feed
must be under control. CO2 takes part in methanol synthesis and
is produced by WGS reaction. Therefore, CO2 is the bridge relating
methanol synthesis and WGS reaction [8]. CO2 molecules adsorb on
the methanol synthesis catalyst and occupy its active sites quicker
than CO and H2 , results in reduced methanol production [164].
Accordingly, increasing the concentration of CO2 in the feed stream
would be unfavorable to both reactions [24] and would lead to a
decrease in CO and H2 conversion as well as in DME selectivity
[2,81,117].
Since the H2 /CO ratio can affect both synthesis gas conversion
and product selectivity in direct synthesis of DME from syngas, it is
worthy to find the optimum value H2 /CO ratio. From the thermody-
namic study, the optimum synthesis gas conversion can be obtained
164
100
Equilibrium conversion of syngas (%)
80
60
40
20
0 accelerating methanol synthesis and dehydration rates. Tan et al.
0 0.5
3CO+3H2=CH3OCH3+CO2
Fig. 16. Equilibrium conversion of synthesis gas at 280 C and 50 atm.
Source: Data from [177].
at the H2 /CO ratio of 1.0 [177]. As depicted in Figs. 16 and 17, selec-
tivity toward DME decreases slightly with an increase in H2 /CO
ratio while that of methanol has an increasing trend.
5.3. Operational temperature
The temperature profile variations in reversible exothermic
reactions like direct DME synthesis have prominent effect on the
reaction progress. At the beginning of the reaction, the reaction is
under kinetic control at low temperature and, consequently, DME
production is enhanced by increasing temperature [8]. As reaction
proceeds, the increased temperature causes a reduction in equilib-
rium conversion of the reaction. Therefore, in reactors involving
exothermic reversible reactions, the temperature profile should
decline as the reactions proceed. Hence, applying a high temper-
ature profile at the beginning of the one-step DME synthesis for a
higher reaction rate and then reducing the temperature gradually
for increasing the equilibrium conversion are appropriate methods
for more DME production [89].
In the case of direct DME synthesis by an isothermal fixed bed
reactor over a CZA-based catalyst, at low temperatures the CO con-
version is low owing to competitive adsorption between CO and
100
Conversion of syngas (%), Selecvity (%)
80
60
40
20
0 5.5. Space velocity
0.25 0.5
Fig. 17. Conversion and selectivity as a function of H2 /CO ratio at 260 ◦ C and 50 atm.
Source: Data from [177].
Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150–172
CO2 on the metallic function of the catalyst [41]. By increasing
temperature, the CO conversion decreases owing, firstly, to the
thermodynamic restrictions of the exothermal reaction and, sec-
ondly, to Cu sintering which provokes partial loss of catalyst activity
[2,178]. Erena et al. showed that the highest concentration of oxy-
genates (methanol and DME) could be obtained in the 250–300 ◦ C
range. Above 300 ◦ C, hydrocracking reactions were dominant lead-
ing to a sharp decrease in the selectivity toward DME [41].
For the synthesis of DME directly from syngas in slurry reac-
tors, the CO conversion shows a different trend toward temperature
change. The CO conversion and DME productivity are likely to
increase with temperature. This can be attributed to the posi-
tive effect of temperature on syngas solubility in liquid paraffin
which improves the volumetric mass transfer coefficient while
1 1.5 2 2.5 3
[179] demonstrated that by increasing the reaction temperature
H2/CO (molar rao)
more methane and other hydrocarbons were produced. They also
2CO+4H2=CH3OCH3+H2O CO+2H2=CH3OH reported that at higher temperature, the methanol dehydration
proceeded at a relatively high rate; and, consequently, stronger
◦
synergetic effect on syngas conversion resulted. However, the
temperature rise has certain limitations owing to a sintering phe-
nomenon occurs at high temperatures [180].
Raoof et al. studied the effect of temperature on catalytic dehy-
dration of methanol to dimethyl ether in an adiabatic fixed bed
reactor. Since the reaction was exothermic and the reactor was
adiabatic, the temperature of catalyst bed increased from the feed
inlet temperature to a maximum value. Moreover, the reactor oper-
ating temperature increased relatively linear with an increase in
the feed temperature. This study showed that the methanol con-
version to DME was not substantial at feed temperatures below
230 ◦ C and increased to the limit of about 85% at 250 ◦ C [4]. Also,
Rownaghi et al. indicated that although higher reaction tempera-
ture resulted in increased methanol conversion, selectivity toward
DME decreased with increasing the reaction temperature from 270
to 320 ◦ C [9].
5.4. Operational pressure
It can be concluded from literature that pressure is likely to
increase the conversion of CO whereby methanol synthesis is the
limiting step of the overall reaction [2,176]. This can be explained
by mole-number reducing stoichiometry of the methanol synthe-
sis. Since water gas shift and methanol dehydration reactions have
the same number of moles on both sides of the reaction, increasing
pressure has no effect on these reactions and methanol synthe-
sis by the hydrogenation process of both CO and CO2 would be
the only controlling steps [8,164]. Although increased pressure is
associated with increased CO conversion and DME productivity,
reactions at high pressures are limited by high operating costs
[164]. Furthermore, it is observed that in the transformation of
H2 + CO2 into dimethyl ether, CZA/␥-Al2 O3 bi-functional catalyst
undergoes a slight deactivation owing to coke deposition. The
increase in the coke content with pressure is explained by the
enhancement of condensation reactions that leads to coke forma-
tion [8]. In slurry reactors increasing pressure has an additional
effect: it would decrease the bubble size, hence increases the vol-
umetric mass transfer coefficient that leads to a reduction in mass
transfer resistance in the slurry phase [50].
0.75 1 1.25 1.5 1.75 2 2.25
H2/CO (molar rao) Space velocity is a crucial factor which influences catalyst
performance. In the direct synthesis of DME in fixed bed reac-
Syngas Conv. DME Methanol CH4
tors, the conversion of CO dramatically decreases with increasing
space velocity [24,41,117]. A similar behavior is expected for CO
conversion when superficial gas velocity is increased in slurry
 Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150–172
reactors. Increasing superficial gas velocity decreases both mass
transfer coefficient and mean residence time. Since the influence
of mean residence time on CO conversion is greater than that of
the mass transfer coefficient, at higher gas velocities, CO conver-
sion is reduced owing to inadequate time for syngas to diffuse into
the slurry phase and reach the catalyst surface. In such systems,
DME productivity is under the influence of two different behaviors.
By increasing superficial velocity at higher catalyst concentration,
DME production increases according to the enhanced flow rate
of the entering syngas to the column. In contrast, at low catalyst
concentration, the DME productivity decreases at higher velocity
because of the decrease in CO conversion. Taking both of these
effects into account, an optimum superficial gas velocity should
be found [164].
Considering the effect of space velocity on DME selectivity,
there is still no general relation between these two factors. Wang
et al. observed that by increasing the space velocity, the DME/CO2
ratio decreased considerably. This means that selectivity toward
CO2 increases significantly at the expense of DME selectivity [24].
It is observed by Erena et al. that both selectivity and yield of
DME increased sharply at low values of space time and then they
increased monotonically to constant values. These results are in
accordance with the fact that low space time values favor the water
shift reaction while high values of space time favor the methanol
dehydration reaction [41]. In another work by Stiefel et al., it was
shown that while DME selectivity remained constant in the case of
␥-Al2 O3 and H-MFI 400 catalysts, it decreased by employing H-MFI
90 and H-MOR 90. This can be explained by strongly acidic char-
acter of H-MFI 90 and H-MOR 90 at higher residence times which
favors the DME conversion to higher hydrocarbons [117].
6. Process intensification (PI)
Traditionally, high purity DME is synthesized by dehydration of
methanol produced from syngas in as conventional gas phase pro-
cess that involves a catalytic fixed-bed reactor followed by a direct
sequence of two distillation columns. The main problem of this
process is the high investments costs for several units (e.g. reac-
tor, columns, heat exchangers) that require a large overall plant
footprint, as well as the associated energy requirements [181].
The main objective of PI is to improve processes and products to
obtain technologies more safe and economic. Due to the intrinsic
characteristics of distillation separations, efforts to improve distil-
lation technology are still in twofold: one is to reduce the energy
consumption and the other is to reduce the capital investment. This
calls for process intensification principles to achieve intensified dis-
tillation systems to save both energy and capital costs. Catalytic
distillation has become in few decades very popular as demon-
strated by the increasing application of this technology to new and
old production processes. The attractiveness of this intensified pro-
cess is based on the demonstrated potential for capital productivity
improvements, selectivity enhancement, reduced energy and pol-
luting solvent consumption. These advantages are greatest when
the combination of reaction and separation implies a reciprocal
synergetic effect. Besides the industrial production advantages, the
catalytic distillation synthesis of DME has some features, e.g. at the
selected operative conditions, no side reactions is expected and the
only side product is water [182].
A very innovative solution to overcome the drawback of energy
intensive distillation is using dividing-wall column (DWC) technol-
ogy [183] that can save up to 30% in CapEx and up to 40% in OpEx
[184]. DWC technology is very versatile and it can be used also
in extractive distillation [185], azeotropic separations or reactive
distillation [186]. Reactive distillation and dividing-wall column
technology can be effectively used for improving existing and new
165
DME processes. For example, the conventional DME purification
and methanol recovery distillation sequence can be successfully
converted into a single-step separation based on DWC. Compared
to the conventional direct sequence of two distillation columns, the
novel proposed DWC alternative reduces the energy requirements
by 28% and the equipment costs by 20% [181]. Moreover, reactive
distillation is a feasible process intensification alternative to pro-
duce DME by methanol dehydration, using solid acid catalysts. The
innovative reactive DWC process has excellent performance with
the elimination of one process step which implies the reduction
in capital costs and the intensification of the process contributes
to a quantum leap toward the theoretical maximum in terms of
mass, energy, space and time efficiency [187]. Consequently, the R-
DWC process can be considered as a serious candidate for the DME
production in new as well as revamped industrial plants. Other
challenges that are in accordance with DME process intensification
are:
• To develop micro-channel catalytic reactors for process intensi-
fication and downsizing.
• To improve catalyst stability, in particular in the presence of
sulfur and other impurities.
• Seeking different techniques for mesoporosity generation in
zeolites, efficient control of acidity, metal dispersion and char-
acterization of the catalyst using a modern set of techniques.
7. Conclusions and future perspectives
Significant research has been conducted to explore a variety of
methods for DME to be produced efficiently. Although the commer-
cially proven technology for DME production is the dehydration of
pure methanol, many researchers are working on the direct con-
version of syngas to DME (STD) with dual heterogeneous catalysts
over which both catalysts are used in one reactor (bi-functional
catalyst) to perform methanol synthesis and dehydration reactions
simultaneously [188]. A summary of the studies on DME synthesis
methods, applied catalysts and operating conditions are presented
in Table 3. From the table it can be concluded that most of the
studies are conducted in the temperature range of 200–300 ◦ C and
pressures up to 70 bar. According to the table, it is obvious that
researchers have shown strong interest in applying CZA and it can
be understood that ␥-Al2 O3 and ZSM-5 zeolite are the most com-
monly used methanol dehydration catalysts.
Another conclusion that can be derived from the table is the
great interest of researchers in applying fixed bed reactors due
to their simplicity. However, they require high investment costs
for several units as well as the associated energy requirements.
According to the aim of process intensification, development
of dramatically improved process alternatives, as compared to
the present state-of-art is necessary to bring a substantially
smaller, cleaner, and more energy-efficient technology such as cat-
alytic distillation (CD), dividing-wall column (DWC) and reactive
dividing-wall column (R-DWC). However, the industrial compa-
nies urgently require a comprehensive methodology enabling to
proceed from the design phase to the working process. Proper for-
mulation of bi-functional catalysts related to their strength of acidic
sites is also important to have better process performance. How-
ever, the deactivation of catalysts as an area of discussion has not
been neglected; acid site coverage and pore blockage mechanisms
are believed to deactivate the zeolites, while water has influence
on deactivation of ␥-Al2 O3 . The comparison of catalyst deactiva-
tion in fixed-bed and slurry-phase reactors also exhibited stronger
deactivation of Cu-based catalysts in slurry reactors.
Essential factors affecting DME production performance were
also investigated. It has been proved that the presence of water
 166
Table 3
Production conditions for various works on DME synthesis.

Synthesis method Type of reactor Catalyst Temperature Pressure Other essential factors Authors Ref. No.
(◦ C) (bar)

Direct Fixed-bed reactor Cu–ZnO–Al2 O3 /ZSM5 200–280 40 • Space velocity = 15,000 mL Chen et al. [2]
(gcath)−1
• H2 /CO/CO2 /N2 =
a. 61/30/5/4
b. 48/32/16/4
Direct Micro packed-bed Mixture of CuO–ZnO–Al2 O3 and 220–320 50–70 • H2 /CO/CO2 /N2 /CH4 = 56/28/5/5/6 Hayer et al. [5]
reactor ␥-Al2 O3 (mol%)
• GHSV = 7500 (Nml/gcat/min)
Direct Slurry phase reactor Mixture of the methanol catalyst 25–240 76.5 • GHSV = 6000 L/(kgcat h) Chen et al. [10]
and ␥-Al2 O3 • H2 /CO = 0.45
• CO2 content = 4.8 (mol%)
Direct Fixed-bed reactor Cr/ZnO–S–Z 300, 325, 350 50 • H2 /CO = 1.82 Yang et al. [17]
• CO2 content = 5.16 mol%
• GHSV = 4500–60,000 Nml/gcat/h

Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150–172

Direct Micro-channel reactor CuO–ZnO–Al2 O3 /␥-Al2 O3 210–300 10–50 Hayer et al. [23]
• H2 /CO = 1, 2, 4
Direct Tubular fixed-bed CuO–ZnO 100–250 20 • Space velocity = 3000, 8000 h−1 Wang et al. [24]
• H2 /CO = 1.8, 2.0, 2.1
Direct Slurry-bed reactor Bifunctional catalyst 40–105 1.2–51.7 • H2 /CO = 0.6–1.5 Yuanyuan et al. [29]
• CO2 content = 0.0009–0.079
Direct Fixed-bed reactor • CZA/HBFZ 250 50 • Space velocity = 1500 h−1 Wang et al. [30]
• CZA/HY • H2 /CO = 2.24
• CO2 content = 4.8%
Direct Fixed-bed reactor Cu–ZnO–Al2 O3 /H-ZSM-5 250 50 • H2 /(CO + CO2 ) = 1, 1.5, 2 Iliuta et al. [34]
• Water removal (volume
fraction) = 0.5
Direct Isothermal fixed-bed CuO–ZnO–Al2 O3 /NaH-ZSM-5 275 40 • H2 /CO/CO2 = 3/1.5/1 Ereña et al. [41]
reactor • Space time = 8.33, 16.66, 33.33
and 66.66 (g of catalyst) h/mol of
(H2 + CO)
Direct Fixed-bed reactor CuO–ZnO–Al2 O3 /␥-Al2 O3 280 50 • GHSV = 1000 h−1 Lee et al. [43]
• H2 /CO = 2
Direct Fluidized bed reactor Cu–ZnO–Al2 O3 /HZSM-5 260 30 • Space velocity = 3000 ml/g/h Lu et al. [44]
H2 /CO =1.0
Direct Slurry Bubble Column Cu-based C301/␥-Al2 O3 230–270 50 • H2 /CO = 2.03 Papari et al. [52]
• CO2 content = 3%mol
Direct Pipe-shell fixed-bed CuO–ZnO–Al2 O3 /␥-Al2 O3 220 50 • H2 /CO = 2.52 Vakili et al. [62,64]
(thermally coupled • CO2 content = 4.09 mol%
heat exchanger
reactor)
Direct Fixed-bed membrane CuO–ZnO–Al2 O3 /H-ZSM-5 250 50 • H2 /(CO2 + CO) = 1.0, 1.5 Iliuta et al. [84]
reactor • Water removal = 0.0-5.0e-10
Direct Fluidized bed – 220–300 • Tube • Space velocity = 3000 ml/gcat/h Mardanpour [89]
membrane reactor side: 40 • H2 /CO = 1 et al.
• Shell
side: 50
Direct Autothermal dual-bed Cu–ZnO–Al2 O3 /H-ZSM-5 250 32 • Water removal = 1e-10-5e- Iliuta et al. [95]
membrane 10 kmol/(sm2 Pa)
• H2 /CO = 100
• CO2 content = 21.5%mol
Direct Fixed-bed CuO–ZnO–Al2 O3 /␥-Al2 O3 230–300 9 • CO/CO2 /H2 = 64/32/4 vol.% Hadipour et al. [96]
micro-reactor
Direct Fixed-bed reactor • Cu/Y 245 20 • Space velocity = 1500 h−1 Fei et al. [111]
• Cu–Mn/Y • H2 /CO = 1.5
• Cu–Zn/Y
• Cu–Mn–Zn/Y
Table 3 (Continued)

Synthesis method Type of reactor Catalyst Temperature Pressure Other essential factors Authors Ref. No.
(◦ C) (bar)

Direct Fixed-bed reactor Cu–ZnO–Al2 O3 /Zr-ferrierite 250 40 • GHSV = 5500 L/(kgcat h) Bae et al. [112]
• CO/CO2 /H2 = 41/21/38 (%mol)
Direct Fixed-bed reactor • CuO/ZnO system Up to 450 Up to 100 • Residence time = 10–90 s Stiefel et al. [117]
• ␥-Al2 O3 • H2 /CO = 0.67, 1.0
• zeolites and ␥-Al2 O3
Direct Fixed-bed reactor CuZr–PdCNTs/HZSM-5 190–270 50 • GHSV = 25,000 mL Zhang et al. [130]
STP/(h g-hydr.catal.)
• H2 /CO2 /N2 = 69/23/8
Direct Fixed Micro-reactor CuO–ZnO–Al2 O3 /H-ZSM-5 200–300 10–40 • H2 /CO = 2.0 Khoshbin and [153]
• GHSV = 600 cm3 /grcat h Haghighi
Direct Fixed-bed reactor • Cu–ZnO–Al2 O3 /H-ZSM-5 250–280 42 • GHSV = 6000 ml/gcat h Kim et al. [155]
• Cu–ZnO–Al2 O3 /Na-ZSM-5 • H2 /CO = 1.5
Direct Tubular reactor HZSM-5 zeolites modified with 260 40 • GHSV = 1500 ml (h gcat) Mao et al. [165]

Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150–172

various contents of magnesium • H2 /CO/CO2 = 0.66/0.30/0.04
oxide
Direct Slurry phase reactor CuO–ZnO–Al2 O3 /␥-Al2 O3 260 50 • H2 :CO = 1:1.5 Wang et al. [166]
• Space velocity = 4000 h−1
Direct Fixed-bed reactor • CZZr 250 50 • H2 /CO = 2.0 Flores et al. [167]
• CZAZr
• Katalco mixed with H-ferrierite
zeolite
Direct Micro-channel reactor • F51-8PPT 220–320 10–40 • GHSV = 5000–20000 h−1 Hu et al. [173]
• ZSM-5 • H2 /CO = 2.0, 3.0
• Acidic Al2 O3 • CO2 content = 4 mol%
Direct Isothermal fixed-bed CuO–ZnO–Al2 O3 /␥-Al2 O3 275 30 • Space time = 12.8 (g of catalyst) h Sierra et al. [175]
reactor (mol of reactants)−1
• H2 /CO = 3/1
• Time on stream = 30 h
• Water/syngas molar ratio in the
feed = 0–0.6
Direct Isothermal plug-flow Bifunctional Catalyst (blend of 900 30–60 • GHSV = 800 ml/gcat h Kabir et al. [176]
reactor methanol dehydration catalyst and • H2 /CO = 0.81
␥-Al2 O3 )
Direct Slurry phase reactor Mn/CuZnAl 240, 260, 280 50 • GHSV = 2.0 L/g cat h, H2 /CO = 2/1 Tan et al. [179]
Direct Fixed-bed reactor CuO–ZnO–Al2 O3 /␥-Al2 O3 225–325 20 • H2 /CO = 2 Ereña et al. [189]
Direct Fixed-bed reactor Mesoporous Cu–␥-Al2 O3 285–325 50 • GHSV = 5500 L/(kgcat h) Jiang et al. [190]
• CO/CO2 /H2 = 41/21/38
Direct Fixed-bed reactor • Cu/Zn 240–290 30–70 • H2 /CO = 0.5–2.0 Kim et al. [192]
• Cu/Zn/Al • Space velocity = 3000–6000 h−1
• CZ-A (Copper Acetate, Zinc
Acetate)
• CZ-N (Copper Nitrate, Zinc
Nitrate)
Direct Fixed-bed reactor Al-MCM-41 260 50.7 • GHSV = 2000 mLg−1 cat h−1 Naik et al. [193]
• H2 /CO2 = 3
Direct Slurry bubble column – 250 52.7 • H2 /CO = 2.2 Chen et al. [194]
Direct Slurry bubble column Cu/Zn/A1/O-based methanol 250 52 • GHSV = 6000 mLg−1 cat h−1 Peng et al. [195]
synthesis • H2 /CO2 = 1/2.2
Direct Fixed-bed Cu–Zn–Al/HZSM-5 240 50 • Space velocity = 1000 h−1 Jia et al. [196]
• H2 /CO = 2/1
• CO2 content = 7.06 (%mol)
Direct Tubular fixed-bed Mixtures of Cu/ZnO/Al2 O3 and 250 50 • GHSV = 8400 h−1 Montesano [197]
micro-reactor ␥-Al2 O3 • H2 /CO = 2/1 et al.

167
 168
Table 3 (Continued)

Synthesis method Type of reactor Catalyst Temperature Pressure Other essential factors Authors Ref. No.
(◦ C) (bar)

Direct Fixed-bed CuOZnO–Al2 O3 /␥-Al2O3 and 275 40 • Space time = 8.33 g catalyst Aguayo et al. [198]
CuO–ZnO–Al2 O3 /NaHZSM-5 h/(mol reactants)
hybrid catalysts • H2 /CO = 4/1
Direct Fixed-bed CZA 260 40 • GHSV = 1700 mL syngas/(gcat h) García-Trenco [199]
• H2 /CO/CO2 = 0.66/0.30/0.04 and Martínez
Direct Fixed-bed Mixture of CuO–ZnO–Al2 O3 and 260 40 • GHSV = 1500 ml (h gcat) Mao et al. [200]
sulfate-modified ␥-Al2 O3 • H2 /CO/CO2 = 0.66/0.30/0.04

Direct and Indirect Isothermal fixed-bed Cu–Mn–Zn/Ce–HY 245 20 • H2 /CO = 3/2 Jin et al. [100]
reactor • Space velocity = 1500 h−1

Indirect Tubular packed reactor • Alumina Impregnated SBA-15 120–450 1 • High Bronsted acidity of Tokay et al. [1]
(Al@SBA-15) Al@SBA-15

Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150–172

• Mesoporous Aluminosilicate
• ␥-Al2 O3
Indirect Fixed-bed reactor Al2 O3 -HZSM-5 190–300 5 – Zhang et al. [3]
Indirect Adiabatic fixed-bed ␥-Al2 O3 233–303 1 LHSV (h−1 ) = 8.5 Raoof et al. [4]
Indirect Fixed-bed reactor ZSM-5 180–320 1.1 – Rownaghi et al. [9]
Indirect Catalytic distillation • ␥-Al2 O3 110–135 9 – Hosseininejad [20]
column • Zeolites (HY, HZSM-5 and HM) et al.
• Ion exchange resins (Amberlyst
15, 35, 36 and 70)
Indirect Fixed-bed reactor ␥-Al2 O3 260 18.2 – Farsi et al. [60]
Indirect Heat exchanger reactor • Pt/Al2 O3 150–250 1 – Khademi et al. [65,90]
Adiabatic fixed-bed • ␥-Al2 O3
reactor
Indirect Platelet Milli-reactor H-ZSM5/SiC 250 1 – Liu et al. [77]
Indirect Spherical packed-bed ␥-Al2 O3 260 18.8 • Water removal = 5 (%mol) Samimi et al. [80]
membrane reactor
Indirect Catalytic membrane F-4SF Resin 180 1 – Volkov et al. [82]
reactor
Indirect Fixed-bed reactor Nanocrystalline ␥-Al2 O3 300 1 • LHSV = 2.8, 11.7, 26.1 h−1 Hosseini et al. [101]
Indirect Fixed-bed reactor AlPO4 150–300 1 – Lertjiamratn [102]
et al.
Indirect Fixed-bed reactor • ␥-Al2 O3 300 1 • GHSV = 15,600 h−1 Yaripour et al. [161]
• Modified ␥-Al2 O3 with silica
Indirect Fixed-bed reactor meso-␥-Al2 O3 300 – • Absence of an acid catalyst Khaleel [191]
Indirect Fixed-bed reactor • CuO–ZnO–Al2 O3 • Top 80 • Space velocity = 1800 h−1 Zhu et al. [201]
• HZSM-5 stage = 268 • H2 /CO = 2.0
• Bottom
stage = 236

CO2 Hydrogenation Isothermal fixed-bed CuO–ZnO–Al2 O3 /␥-Al2 O3 225–325 20–40 – Ereña et al. [8]
reactor
CO2 hydrogenation Fixed-bed reactor Blend of CuO–TiO2 –ZrO2 and 200 30 – Wang et al. [33]
H-ZSM-5
CO2 hydrogenation Fixed-bed reactor CuO–ZnO–Al2 O3 /H-ZSM-5 262 30 – Zha et al. [99]

CH3 Br hydrolysis Glass tube reactor ZnCl2 /SiO2 180 – • ZnCl2 loading from 1.0 mol% to You et al. [31]
12 mol%
CH3 Br hydrolysis Batch reactor PVP 50–125 – – Prakash et al. [36]

Note: f = (H2 − CO2 )/(CO + CO2 ).

 Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150–172
has an inhibiting effect on the reaction rate by competing with
methanol molecules over acid sites. Under H2 O removal condi-
tions with hydrophilic membranes, the water–gas shift equilibrium
displaced so that the conversion of CO2 into methanol increases
thereby enhancing DME yield and selectivity.
It is shown that there is an optimum value of H2 /CO ratio in
DME synthesis affected by temperature. It is also proved that the
CO2 content of the feed might decrease CO conversion as well as
DME selectivity. Effect of temperature on CO conversion is case
dependent. It would decrease CO conversion in direct DME syn-
thesis through isothermal fixed bed reactors while it is likely to
increase CO conversion and DME productivity in slurry reactors. In
addition, higher methanol conversion is achieved by the catalytic
dehydration of methanol to dimethyl ether in an adiabatic fixed bed
reactor, at the expense of DME selectivity. From the stoichiometry
of the reaction it is concluded that pressure increases the conver-
sion of CO and it is specified that the methanol synthesis is the
limiting step of the overall reaction. The last factor studied was
space velocity which had a decreasing effect on CO conversion in
both fixed-bed and slurry reactors.
Despite numerous studies on DME production in literature,
there is still lack of an entire research area encompassing eco-
nomic aspects of the process. Moreover, improving optimization
and scaling up of the one-step synthesis of DME should be consid-
ered. Relatively few researches have been performed on the leading
role of CO2 in DME synthesis, especially at the conditions of high
space velocity. Moreover, the most favorable CO/CO2 ratio in the
feed stream has not been widely defined yet. More research is
needed for the development of novel catalysts which show better
performance in terms of activity, selectivity and most importantly
stability toward water. Investigating the optimum ratio of catalyst
components to provide DME/MeOH mixtures as required for differ-
ent product requirements is also noteworthy. Verifying whether
Lewis sites can be converted to Bronsted sites in the presence of
water is also suggested. It is also offered to determine the opti-
mum value of water removal in the case of membrane reactors.
Developing a long life-time catalyst for CH3 Br hydrolysis reac-
tion in order to make this approach practical and investigating the
efficiency of immobilizing catalysts in micro reactors are further
proposed.
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