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Chemical Engineering and Processing 82 (2014) 150172

Contents lists available at ScienceDirect

Chemical Engineering and Processing:


Process Intensication
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
b

School of Chemical and Petroleum Engineering, Department of Chemical Engineering, Shiraz University, Shiraz 71348, Iran
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

Article history:
Received 15 January 2014
Received in revised form 24 April 2014
Accepted 15 June 2014
Available online 20 June 2014
Keywords:
Dimethyl ether
Direct synthesis
Indirect synthesis
Syngas conversion
Catalyst
Reactor

a b s t r a c t
Dimethyl ether (DME) is a well-known propellant and coolant, an alternative clean fuel for diesel engines
which simultaneously is capable of achieving high performance and low emission of CO, NOx and particulates in its combustion. It can be produced from a variety of feed-stocks such as natural gas, coal or
biomass; and also can be processed into valuable co-products such as hydrogen as a sustainable future
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
focuses on conventional processes and innovative technologies in reactor design and employed catalysts. In this context, synthesis methods are classied according to their use of raw material type as
direct and indirect methods as well as other routes, since different methods need their own operating
condition. Also, the available data for the selectivity to DME and its yield as a function of H2 /CO and CO2
content of the feed is discussed.
2014 Elsevier B.V. All rights reserved.

Contents
1.
2.

3.

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

151
151
151
152
152
153
154
154
154
154
154
154
155
156
156
156
158

Abbreviations: AF-SPMR, axial-ow spherical packed-bed membrane reactor; ATR, autothermal reforming; CapEx, capital expenditure; CD, catalytic distillation; CDR,
carbon dioxide reforming; CFC, chlorouorocarbon; CPO, catalytic partial oxidation; CZA, CuOZnOAl2 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, liqueed petroleum gas; MTG, methanol to gasoline; MTH,
methanol to hydrocarbons; MTO, methanol to olens; 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.

4.

5.

6.
7.

Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150172

151

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

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169

1. Introduction
The inordinate use of oil-based fuels for transportation purposes
is one of the major reasons of the rapid depletion of petroleum
which causes major environmental problems. These issues have
necessitated the development of clean non-petroleum based alternative transportation fuels. In recent years, the application of
dimethyl ether (DME) as a potential diesel substitute used in compression ignition engines has attracted considerable attention [1,2].
DME is a volatile substance which forms a liquid phase when
pressurized above 0.5 MPa; therefore, it is commonly handled and
stored as liquid (see the physical property of DME in Table 1). Burning with a visible blue ame and with similar properties as propane
and butane, DME may hence be used as liqueed 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
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,
and since it contains about 35% oxygen, its combustion products
such as carbon monoxide and unburned hydrocarbon emissions
are less than those of natural gas. (3) Owing to its high cetane number, DME is considered to be an excellent alternative to the present
transportation fuel with no emission of particulate matter and toxic
gases such as NOx at burning [1,2,4,5]. (4) Moreover, it has a similar
vapor pressure to that of LPG, and hence can be used in the existing
infrastructures for transportation and storage [6]. Thus, the significant future perspective of DME can be counted as an alternative
energy.
Furthermore, DME is widely recommended as environmentally
friendly aerosol and green refrigerant since it has zero ozone depletion potential and lower global warming potentials compared with

traditional chlorouorocarbons (CFCs, Freon) and R-134a (HFC134a) [7]. In addition, DME can be used as pesticide, polishing
agent, and anti-rust agent. It can also be considered as an attractive
material for producing alkyl-aromatics, a suitable source for the
hydrogen used in fuel cells, as well as a key intermediate for producing dimethyl sulfate, methyl acetate, light olens, and so many
other important chemicals [810].
DME can be produced from a variety of feed-stock including
natural gas, crude oil, residual oil, coal and waste products [11].
Among potentially interesting raw materials, natural gas appears
to be the most promising one due to its wide availability and the
fact that producing DME from natural gas allows production costs
to be independent of the swings in the oil price [12].
1.1. Scope of the current review
Extensive works have been undertaken to improve DME synthesis methods and the employed catalysts, but the DME subject
is still suffering from the lack of a critical review. The underlying
goal of this paper is to present an extensive review considering
the valuable works accomplished over the years 19652013 on
dimethyl ether synthesis. The trend of related publications on DME
over the years 19962013 is shown in Fig. 1. As obvious, the number of published papers rises gradually and has a peak within the
year of 2011. It is concluded from Fig. 2 that these publications are
drastically concentrated on catalyst and then on reactor technology. Thus, taking these results into account, this paper focuses on
production methods and a discussion on their wide variety of reactors and catalyst congurations while also investigating effective
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.
Properties
Molecular formula
Molar mass
Appearance
Odor
Density
Melting point
Boiling point
Solubility in water
log P
Vapor pressure

C2 H6 O
46.07 g mol1
Colorless gas
Typical
1.97 g cm3
141 C, 132 K, 222 F
24 C, 249 K, 11 F
71 g dm3 (at 20 C)
0.022
>100 kPa

As shown in Fig. 3 and mentioned before, DME can be produced


in two distinct ways: the rst called the indirect route uses the produced methanol to promote its dehydration; the second way which
is arguably more efcient is known as the direct route, in which
DME is produced in a single stage using bi-functional catalysts. The
technology of this single step method belongs to companies such as
Haldor Topsoe, JFE Holdings, Korea Gas Corporation, Air Products,
and NKK [13,14]. Moreover, Toyo, MGC, Lurgi and Udhe have their
own indirect processes for DME production [13].
One of the main steps in DME synthesis is the production of syngas, which is a mixture of hydrogen and carbon monoxide and has

152

Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150172

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

RT

pmethanol

(2)

where k0 = 1.21 106 (pressure of methanol (kPa) kmol)/(m3 reactor h kPa), Ea = 80.48 kJ/mol, and pmethanol is the partial pressure of
methanol (kPa).
Theoretically, methanol dehydration is favored at lower temperatures because it is an exothermic reaction and the formation of
by-products such as ethylene, carbon monoxide, hydrogen, and/or
coke is signicant at higher temperatures.
2.2. Direct synthesis method

Fig. 2. Percentage of publications on (a) the subject of DME and (b) different synthesis methods.

been manufactured industrially from hydrocarbon fuels-typically


natural gas either by steam reforming (SR) or gasication [1517].
In the following sections, essential information about two basic
methods of DME synthesis will be presented and other routes of
DME production will then be pointed out.

More recently, a combined methanol synthesis and dehydration


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 watergas
shift reaction taken into account and Eq. (4) without it.
3CO + 3H2 CH3 OCH3 + CO2

(3)

2CO + 4H2 CH3 OCH3 + H2 O

(4)

Eq. (3) involves four basic reactions including [23]:


Methanol synthesis from CO:

CO + 2H2 CH3 OH H298


2.1. Indirect synthesis method

= 90.4 kJ/mol

(5)

Methanol synthesis from CO2 :

Traditionally, DME has been produced from syngas in a two-step


process in which methanol is produced from syngas, puried, and
then converted to DME in another reactor. The schematic of this
process is shown in Fig. 4. The commercialized process reaction of
DME production from methanol dehydration is shown in Eq. (1):

2CH3 OH CH3 OCH3 + H2 O H298

= 23.5 kJ/mol

H298

= 49.4 kJ/mol

(6)

Water gas shift (WGS):


CO + H2 O CO2 + H2

H298

= 41.0 kJ/mol

(7)

Methanol dehydration:
(1)

Many investigations on the kinetics of DME synthesis by dehydration of methanol on solid-acid catalysts have been published.
The majority of them agree that the mechanism follows either
LangmuirHinshelwood [18] or EleyRideal kinetic models [19],
with water and DME both acting as reaction inhibitors [20].

Fig. 3. Dimethyl ether production diagram.

CO2 + 3H2 CH3 OH + H2 O

2CH3 OH CH3 OCH3 + H2 O H298

= 23.0 kJ/mol

(8)

In each reaction, the equilibrium conversion reaches its maximum peak whenever the H2 /CO ratio in the feed stream
corresponds to the stoichiometric value, that is 1.0 for Eq. (3) and
2.0 for both Eqs. (4) and (5).
According to the aforementioned reactions, both methanol synthesis 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 stoichiometry of Eq. (9) with H2 /CO molar ratio of 1.
2CH4 + O2 + CO2 3CO + 3H2 + H2 O

(9)

Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150172

153

Methanol

To DME
Tank

Reactor

To Waste
Water
Treatment

DME Tower

Methanol/Water 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 synthesis 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 purication of DME in the synthesis process.
Through absorption, ash and distillation [25,26], H2 , N2 , CH4 ,
and CO2 are removed; methanol is recovered and the nal 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 difcult when
methanol is present in the system. Thus, in a proposed process
[29], the methanol and water resulted from the one-step reaction
were rst condensed and then absorbed by water; nally the liquid stream containing DME was distilled for nal DME product.
This separation process is demonstrated to be feasible to synthesize 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 synthesis, 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.

In addition, because of the watergas shift reaction which


consumes stoichiometric amount of CO to form CO2 and hydrogen, 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 efcient and environmentally friendly design
solutions are desired to that end [31]. These processes are integrating 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 (usually CH3 Cl or CH3 Br) is prepared from the oxidative bromination
reaction of methane in the presence of hydrogen halide and oxygen 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 hydrolysis 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 Burner
To Gas Pipe
Syngas

Water

To DME Tank

To Methanol
Tank
DME Tower
Reactor
Methanol/Water Tower
Fig. 5. A scheme of direct synthesis process.

To Heat
Exchanger

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Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150172

Fig. 6. A schematic diagram of indirect DME production from natural gas in adiabatic xed-bed reactor.
Source: Modied from [62].

amine catalyst showed maximum efciency according to the capture 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 carbonylation 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 consumption and enhance energy efciency. 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 discussion on reactor design by considering the conventional xed
bed and slurry phase reactors used for DME production, and then
we will investigate the subsequent innovative technologies developed to solve the problems that might arise with the conventional
techniques.

3.1.2. Slurry phase reactors


Besides xed beds, the other type of reactor commonly used in
commercial direct DME synthesis technology is slurry phase reactors [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 xed-bed
reactors owing to the large heat capacity of the solvent, some disadvantages have been reported [4550]. 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 reactors 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. Conventional types


3.1.1. Fixed-beds
Owing to simplicity and lower costs, the reactors most commonly used either at laboratory or pilot scale are xed-beds [39].
For catalytic processes which have low or intermediate heat of reactions adiabatic xed-bed reactors illustrated in Fig. 6 can be the
rst choice [40]. In such systems, diffusional restrictions between
phases are eliminated by gassolid contactors [41]. Moreover, operation in a xed bed reactor is an interesting alternative that allows
for the use of an optimum longitudinal prole 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 thermodynamics); 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 problem of reaction putting out or catalyst sintering [42]. Therefore,
the challenges of thermodynamic limitations and excessive catalyst deactivation in conventional xed 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 perpass conversion as well as larger capital investment and operating
costs [43,44].

3.1.3. Fluidized-bed reactors


Fluidized-bed reactors have been suggested by some
researchers as a perfect reactor conguration for DME synthesis [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 gassolid 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
benet [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 efciency, process integration can be considered. The multifunctional 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) 150172

155

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


Source: Modied 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) [5658]. Some investigators suggest an industrial dual-type reactor for producing DME
directly from syngas [59,60]. In this regard, Vakili et al. [61] investigated 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 ew in the shell side. The boiling water in
the shell side of the rst reactor absorbed the heat of exothermic
reactions and produced water vapor. The production capacity of
the proposed reactor conguration (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 conguration 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 conguration could produce about 60 ton/day DME
more than the conventional DME plant. Furthermore, this new conguration reduced DME production costs by eliminating a separate
unit for methanol production and purication [6163].
Moreover, on the basis of simulation results, Vakili et al. [64]
showed that changing the molar ow 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 synthesis 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 dehydrogenation of cyclohexane to benzene took place in the shell side,
whereas methanol dehydration occurred inside the tube with xed
bed of different catalysts on both sides. Heat is transferred continuously from the exothermic to the endothermic reaction zone. It
was shown that suitable amount of initial molar ow 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
efciency of the process [6567].
Skinner et al. demonstrated a staged reactor for ethanol dehydration to ethylene which achieved a 95% conversion of ethanol
[68]. A similar reactor conguration was applied to dehydrate
methanol into DME using a staged reactor that coupled partial oxidation in the upstream stage with methanol dehydration in the
downstream stage. The staged partial oxidation reactor is capable of integrating decomposition and deoxygenation to upgrade

Fig. 8. The thermally coupled reactor conguration.


Source: Modied from [65].

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Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150172

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 dehydration 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 justify 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 conditions. They also claimed that the innovative reactive DWC process
had better performance compared to the conventional or the reactive distillation process: signicant energy saving of 1258%, 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].
Fig. 9. A schematic diagram of the co-current mode for a recuperative reactor conguration.
Source: Modied 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 distillation 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 operational costs compared to a single reactor [70,71]. CD requires
moderate operational temperature and pressure (40180 C and
8001200 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 highenergy consumption in distillation units are thermally coupled
distillation columns [72], dividing-wall columns (DWC) [71],
heat-integrated distillation or cyclic distillation [73]. The Petlyuk
conguration, 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. Simplied DME production process via CD process.


Source: Modied from [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-tovolume 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 ow behavior, compactness, and parallel processibility [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 catalytic 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 purication are
required [79]. The removal of H2 O during methanol dehydration
by means of the membrane concept can reduce H2 O promoted catalyst deactivation and enhance DME productivity [80]. However,
the enhancement of H2 O ux through the membrane (i.e. by using
higher sweep ow rates) would also produce undesired HC [81].
Consequently, an optimum value for H2 O ux through the membrane 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 benets 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 [8588]. In
light of this new concept, Mardanpour et al. have developed a model
for a shell and tube uidized 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) 150172

157

Fig. 11. Path from conventional setup to reactive dividing-wall column (R-DWC).
Source: Modied from [76].

Fig. 12, hydrogen permeates along the reactor leading to a better


performance and efciency [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 Naon), onto the internal surface of the ceramic ultraltration 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 uidized bed membrane reactor (FBMR) conguration.
Source: Modied from [89].

Although at the temperature range of 70120 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 catalyst. The authors have related this behavior to the strong adsorption
of methanol and the produced water within this temperature interval. Hence, to prevent deactivation of the catalyst and to improve
methanol conversion, it was proposed that the rate of alcohol desorption 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 benecial [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. [9094].
In their proposed conguration, methanol synthesis took place
in the exothermic side which supplied the necessary heat for
the endothermic dehydrogenation of cyclohexane reaction. By cocurrent ow 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
efciency but also it could reduce the cost of syngas production
in DME production unit. The schematic gure of the dual bed
membrane reactor is shown in Fig. 15. In order to enhance the productivity 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: Modied from [82].

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Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150172

Fig. 14. A scheme illustrating a catalytic membrane.


Source: Modied from [82].

the system by means of a hydrophilic membrane tube placed in the


center of the reactor [95].

the pressure drop decreased, but also more production of DME was
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
conguration was studied by Samimi et al. They developed an axialow 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 necessary 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 activity. These should consider the most efcient 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: Modied from [95].

Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150172

159

Table 2
Different types of DME reactors in comparison.
Reactor type

Characteristics/usages

Benets in a DME plant

Cautions

Fixed-beds

Simplicity and lower cost


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
Catalytic heterogeneous gas phase
reactions
Catalytic heterogeneous gas phase
reactions

Catalyst deactivation
High recycle of syngas
High operational investment
High pressure drop

Manageable temperature better heat transfer

Complicated equipment
Loss of catalyst particles
Collision between catalyst particles
and the reactor wall
Loss of catalyst

Slurry phase
Fluidized-bed

Coupled and dual type


reactors

For both highly exothermic and


endothermic reactions

Coupling reactor and


separation units

For methanol dehydration


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)
For both highly exothermic and
endothermic reactions

Micro reactors

Membrane reactors

Has been used in indirect and also


direct methods.

Lower gassolid mass transfer resistance


Excellent temperature control
High conversion and no need for recirculation
Moderate operating pressure
Lowering both capital and operating costs
Highly energy-efcient
Hot spots can be controlled
Higher selectivity/conversion
Reducing operational cost
R-DWC: lowers footprint with milder
operating condition, better performance
(energy saving, reduced CO2 emission, reduced
total annual cost)
High controllability of the reaction conditions
Small holdup value
Avoiding thermal runaway
Compactness and parallel processibility
Good reaction yield
No additional steps of separation and
purication
Prevent the catalyst deactivation
Dual bed membrane reactor:
higher thermal efciency
reduces the cost of syngas production
Spherical membrane reactor:
Decreases the pressure drop
Increases the DME production

4. Catalysts
4.1. Catalyst diversity
Extensive research is conducted on nding better catalysts that
have higher selectivity toward DME formation and a lower tendency 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 temperature of the bi-functional catalysts is in a temperature range
of 523673 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 , modied alumina with silica, TiO2 -ZrO2 , clays, ion exchange resins, Boehmite (AlOOH) and
zeolites such as H-ZSM-5, HY, mordenites, SAPO, MCM, Ferrierite,
chabazite and H-beta [2,7,10,23,30,41,100109]. Meanwhile, the
solid-acid catalysts can be modied with sulfate, zirconium, iron,
silica, phosphorus, B2 O3 , and rare metals to obtain moderate acidity for higher CO conversion and minimal by-product (light olens
and heavy hydrocarbons) formation [7,23,30]. For instance, Jin et al.
prepared a series of zeolite Y modied 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].

CD: requires moderate temperature,


while the employed catalyst is active at
higher temperature

Laminar ow behavior

May produce undesired HC


Pore blockage
Thermal/mechanical stability issues

In CuOZnOAl2 O3 (CZA) catalysts, metallic copper clusters are


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 CuOZnO-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 precipitant and calcination temperature [110,112114]. In a series of
experiments conducted by Wang et al., the effect of different Cu/Zn
molar ratios of CuZn-based catalyst was investigated. The observation showed that low Cu/Zn ratio was more benecial 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 factor 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

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Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150172

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 HZSM-5 zeolite core enwrapped by one layer of CuOZnO 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 catalyst. 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 arrangement 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 250400 C and pressures up to 18 bar can be a proper
candidate to play the role of a solid-acid catalyst in methanol dehydration process [119]. In comparison to other catalysts, zeolites in
general possess high surface area which comes from their microporous 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 catalytic 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 modications to zeolite catalysts. For example, Tang et al. employed a
ZSM-5/MCM-41 composite molecular sieve as the methanol dehydration 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 dehydration 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 CuMo 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 processing catalyst is another zeolite that is of interest owing to its high
catalytic activity in etherication in conversion to olens (MTO).
This property allows for the possibilities of performing both DME
synthesis and MTO technologies in a single reactor only by temperature 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 treatment, thereby increasing the surface area [10].
Stiefel et al. studied various dehydration catalysts in the synthesis of DME directly from carbon monoxide rich syngas. They showed
that pore volumes and specic 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 studied 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 signicant decrease in DME selectivity 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 consequence of increase in H2 concentration, the conversion of CO to
methanol is favored [117].
Recently, polymeric heterogeneous catalysts, namely Naon
resin, have attracted a lot of attention in the conversion of methanol
to DME [122,123]. Experiments were carried out in a vapor
phase ow reactor using Naon resin beds [122] or Naon/silica
nanocomposites of different compositions [123]. The Naon catalysts provide 40% methanol conversion. In this case, no catalyst
activity loss and coke formation were observed. Thus, Naon 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, chemical 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 attention [127129]. MWCNTs possess several unique features such as
graphitized tube-wall, nanometer-size channel, high thermal conductivity 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 lled in the interior of the
MWCNTs. A type of bi-functional hybrid catalyst of Pd-decorated
CNT-promoted CuZrO 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/HZSM-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 specic surface area provided by CuO/ZrO2 catalyst, the
performance of the catalyst is under the inuence of phase transformation. 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 xed Cu surface area, CuO/m-ZrO2
is more active for methanol synthesis than CuO/t-ZrO2 [33]. Furthermore, 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) 150172

several preparation steps resulted in extra costs and more waste


production during the preparation of an effective catalyst. Besides,
it is difcult to limit the dehydration of methanol to the sole formation of DME. Indeed, the presence of an acid catalyst leads to
the consecutive formation of hydrocarbons (methanol to hydrocarbons, MTH) [133135]. More precisely, light olens (methanol
to olens, MTO) or alkanes (methanol to gasoline, MTG) can be
obtained as a function of temperature and pressure [136144].
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 [133,139144]. Song et al. showed that a pool
of adsorbed polymethyl benzenes played a leading role in catalytic
cycles of MTH process [141145]. Moreover, the methylation of
hexa-methyl-benzene to form hepta methyl benzeniumation has
been shown to be the rst 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
articially deactivate the hydrocarbon pool is to carry out catalytic 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 olens 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 signicant effect on the performance of the process
[124,126,131,150152]. Hybrid catalysts used for synthesizing
DME directly from syngas are prepared in different ways including physical mixing of methanol synthesis catalyst and solid-acid
catalyst, co-precipitation (solgel), impregnation, and combined
co-precipitation-ultrasound [30,153]. In the case of the admixed
catalyst, each function is prepared separately and then the powders of both functions are mechanically blended [154160]. The
activity of the catalysts prepared by physical mixing is higher than
the activity of ones prepared by co-precipitation and impregnation [30]. In a study conducted by Hosseini et al. nanocrystalline
-Al2 O3 catalyst was prepared by solgel and precipitation methods. The obtained results showed that the catalysts prepared by the
solgel method have higher activity than catalysts prepared by the
precipitation method. Furthermore, non-aqueous solgel method
offered higher activity in comparison with aqueous solgel one. The
advantages of the solgel 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 component in the catalyst system. If acidity is too low, the amount of
methanol formed cannot be dehydrated with sufcient efciency.
If the acidity of the catalyst is too high, it also catalyzes further the
conversion of DME to hydrocarbons [117]. Hence, according to several 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. modied -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 similar performance in comparison to unmodied -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 concentration 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 acidbase pair and
Bronsted acidLewis base pair sites [39,162].
Concerning the acidity of -Al2 O3 , according to several investigations, it is mainly due to Lewis-acid sites whilst the acidity of
MFI zeolites and AlPO4 in many cases is dominated by Bronstedacid 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 aluminosilicate 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 nd 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 consequently 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 conditions, 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 byproducts. 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

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Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150172

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 efcient method for improving the
resistance toward carbon formation [9].
A comparison between H-form mordenite and Na-form mordenite 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 catalytic 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 regenerate 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 xed bed heterogeneous reactor by using acidic
-alumina in order to investigate the effect of water on the deactivation of -alumina. The mixture of methanolwater 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
methanolwater 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 CuOZnOAl2 O3 /-Al2 O3 bi-functional catalyst, 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 reaction medium formed through the reverse water gas shift reaction in
the case of CO2 rich feed limited coke deposition owing to competitive 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 xed bed ones with
CZA/-Al2 O3 as DME synthesis catalyst. These catalysts deactivate
more quickly in the slurry reactor than in the xed-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 xedbed reactor, it is more difcult to remove H2 O from the surface of
Cu-based catalyst in the slurry reactor because liquid parafn 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 condition 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, Naon resin,
AlPO4 and CuO/ZrO2 , from the viewpoints of activity, yield or selectivity toward DME production, and their possible deactivation.
4.5.1. Activity
It has been shown by Flores et al. [167] that metallic components inuence 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 inuenced its textural and structural properties,
but these changes did not inuence the catalytic activity. For the
methanol synthesis, amongst the dozens of catalytic materials proposed, the largest utilization has the classical methanol synthesis
catalyst CuZnOAl2 O3 , sometimes modied with ingredients contributing to the increase of the copper dispersion and stability. It
is commonly employed in the one-step DME synthesis and usually prepared by the conventional co-precipitation method, the
catalytic activity depending on Cu/Zn/Al ratio and the preparation 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 etherication have the solid acids with moderate acidity (-Al2 O3 , zeolites,
mesoporous materials etc.). A largely used etherication 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 stability. Activity and stability performances of -alumina can also be
improved by promoting with different metal oxides. The Nb2 O5
modied -alumina showed a higher catalytic activity in methanol
etherication 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 catalyst [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 catalyst. 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
H-MOR 90 < H-MFI 400 < -Al2 O3 < H-MFI 90

for T < 240 C


for T > 240 C

AlPO4 : The catalytic activity of AlPO4 in methanol dehydration


is found to be dependent upon the preparation method, chemical composition (Al/P molar ratio) and activation temperature
[124,126].
CuO/ZrO2 : For a xed 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 CuZnOAl2 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 catalyst) 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) 150172

HSY as methanol dehydration components, prepared by coprecipitation method: 99% DME selectivity in organic products were
reported at 290 C, 40 bar, space velocity = 1500 h1 , 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 sulfatedzirconia, which further conrms that methanol is not efciently
dehydrated over weak acidic solids. DME production may be effectively 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 catalyst [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 components and metal ions migration. Particularly, a good temperature
control is necessary, due to the important overall process exothermicity. Results show that the deactivation behavior of the catalyst
is mainly caused by the deactivation of the methanol synthesis catalyst, 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 signicant sintering below 325 C
[168]. Its deactivation is more quickly in the slurry reactor than
in the xed 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 regenerated by the addition of water resulting from removing carbon
deposited on the catalysts [169]. Sic supported ZSM-5 prohibits the formation of HC [132,148]. H-MFI 90 increases its HC
formation when the temperature is above 240 C [117]. The deactivation of H-MOR is irreversible [10].
Naon 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 dehydration 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 benecial effects. Considering 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 initial 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 attractive possibility of in situ H2 O removal by adsorption as shown by
Carvill et al. [174]. Moreover, Iliuta et al. studied the sorptionenhanced reaction process under in situ H2 O removal conditions
for DME synthesis process in a xed bed reactor in order to analyze
the effect of different parameters. By applying the adsorptionenhanced 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 productivity. 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 xed bed reactor with in situ H2 O removal
by adsorption was more efcient in DME synthesis process than
a xed bed reactor without H2 O removal [34]. A possible disadvantage of H2 O removal process is the deactivation of the catalyst
metallic function (CuOZnOAl2 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 produced 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 produce 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 benecial for sequestration [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 nd the optimum value H2 /CO ratio. From the thermodynamic study, the optimum synthesis gas conversion can be obtained

164

Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150172

Equilibrium conversion of syngas (%)

100

80

60

40

20

0
0

0.5

1.5

2.5

H2/CO (molar rao)


3CO+3H2=CH3OCH3+CO2

2CO+4H2=CH3OCH3+H2O

CO+2H2=CH3OH

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, selectivity 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 prole 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 equilibrium conversion of the reaction. Therefore, in reactors involving
exothermic reversible reactions, the temperature prole should
decline as the reactions proceed. Hence, applying a high temperature prole 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 xed bed
reactor over a CZA-based catalyst, at low temperatures the CO conversion is low owing to competitive adsorption between CO and

Conversion of syngas (%), Selecvity (%)

100

80

60

40

20

CO2 on the metallic function of the catalyst [41]. By increasing


temperature, the CO conversion decreases owing, rstly, to the
thermodynamic restrictions of the exothermal reaction and, secondly, to Cu sintering which provokes partial loss of catalyst activity
[2,178]. Erena et al. showed that the highest concentration of oxygenates (methanol and DME) could be obtained in the 250300 C
range. Above 300 C, hydrocracking reactions were dominant leading to a sharp decrease in the selectivity toward DME [41].
For the synthesis of DME directly from syngas in slurry reactors, 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 positive effect of temperature on syngas solubility in liquid parafn
which improves the volumetric mass transfer coefcient while
accelerating methanol synthesis and dehydration rates. Tan et al.
[179] demonstrated that by increasing the reaction temperature
more methane and other hydrocarbons were produced. They also
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 phenomenon occurs at high temperatures [180].
Raoof et al. studied the effect of temperature on catalytic dehydration of methanol to dimethyl ether in an adiabatic xed 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 operating temperature increased relatively linear with an increase in
the feed temperature. This study showed that the methanol conversion 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 temperature 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 synthesis. 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 synthesis 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 formation [8]. In slurry reactors increasing pressure has an additional
effect: it would decrease the bubble size, hence increases the volumetric mass transfer coefcient that leads to a reduction in mass
transfer resistance in the slurry phase [50].
5.5. Space velocity

0
0.25

0.5

0.75

1.25

1.5

1.75

2.25

H2/CO (molar rao)


Syngas Conv.

DME

Methanol

CH4

Fig. 17. Conversion and selectivity as a function of H2 /CO ratio at 260 C and 50 atm.
Source: Data from [177].

Space velocity is a crucial factor which inuences catalyst


performance. In the direct synthesis of DME in xed bed reactors, the conversion of CO dramatically decreases with increasing
space velocity [24,41,117]. A similar behavior is expected for CO
conversion when supercial gas velocity is increased in slurry

Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150172

reactors. Increasing supercial gas velocity decreases both mass


transfer coefcient and mean residence time. Since the inuence
of mean residence time on CO conversion is greater than that of
the mass transfer coefcient, at higher gas velocities, CO conversion 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 inuence of two different behaviors.
By increasing supercial velocity at higher catalyst concentration,
DME production increases according to the enhanced ow 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 supercial 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 signicantly 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 character of H-MFI 90 and H-MOR 90 at higher residence times which
favors the DME conversion to higher hydrocarbons [117].

6. Process intensication (PI)


Traditionally, high purity DME is synthesized by dehydration of
methanol produced from syngas in as conventional gas phase process that involves a catalytic xed-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. reactor, 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 distillation 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 intensication principles to achieve intensied distillation systems to save both energy and capital costs. Catalytic
distillation has become in few decades very popular as demonstrated by the increasing application of this technology to new and
old production processes. The attractiveness of this intensied process is based on the demonstrated potential for capital productivity
improvements, selectivity enhancement, reduced energy and polluting 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) technology [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 purication


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 intensication alternative to produce 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 intensication of the process contributes
to a quantum leap toward the theoretical maximum in terms of
mass, energy, space and time efciency [187]. Consequently, the RDWC 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 intensication
are:
To develop micro-channel catalytic reactors for process intensication and downsizing.
To improve catalyst stability, in particular in the presence of
sulfur and other impurities.
Seeking different techniques for mesoporosity generation in
zeolites, efcient control of acidity, metal dispersion and characterization of the catalyst using a modern set of techniques.
7. Conclusions and future perspectives
Signicant research has been conducted to explore a variety of
methods for DME to be produced efciently. Although the commercially proven technology for DME production is the dehydration of
pure methanol, many researchers are working on the direct conversion 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 200300 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 commonly used methanol dehydration catalysts.
Another conclusion that can be derived from the table is the
great interest of researchers in applying xed 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 intensication, 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-efcient technology such as catalytic distillation (CD), dividing-wall column (DWC) and reactive
dividing-wall column (R-DWC). However, the industrial companies urgently require a comprehensive methodology enabling to
proceed from the design phase to the working process. Proper formulation of bi-functional catalysts related to their strength of acidic
sites is also important to have better process performance. However, 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 inuence
on deactivation of -Al2 O3 . The comparison of catalyst deactivation in xed-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.
Type of reactor

Catalyst

Temperature
( C)

Pressure
(bar)

Other essential factors

Authors

Ref. No.

Direct

Fixed-bed reactor

CuZnOAl2 O3 /ZSM5

200280

40

Chen et al.

[2]

Direct

Micro packed-bed
reactor

Mixture of CuOZnOAl2 O3 and


-Al2 O3

220320

5070

Hayer et al.

[5]

Direct

Slurry phase reactor

Mixture of the methanol catalyst


and -Al2 O3

25240

76.5

Chen et al.

[10]

Direct

Fixed-bed reactor

Cr/ZnOSZ

300, 325, 350

50

Yang et al.

[17]

Direct

Micro-channel reactor

CuOZnOAl2 O3 /-Al2 O3

210300

1050

Hayer et al.

[23]

Direct

Tubular xed-bed

CuOZnO

100250

20

Wang et al.

[24]

Direct

Slurry-bed reactor

Bifunctional catalyst

40105

1.251.7

Yuanyuan et al.

[29]

Direct

Fixed-bed reactor

CZA/HBFZ
CZA/HY

250

50

Wang et al.

[30]

Direct

Fixed-bed reactor

CuZnOAl2 O3 /H-ZSM-5

250

50

Iliuta et al.

[34]

Direct

Isothermal xed-bed
reactor

CuOZnOAl2 O3 /NaH-ZSM-5

275

40

et al.
Erena

[41]

Direct

Fixed-bed reactor

CuOZnOAl2 O3 /-Al2 O3

280

50

Lee et al.

[43]

Direct

Fluidized bed reactor

CuZnOAl2 O3 /HZSM-5

260

30

Lu et al.

[44]

Direct

Slurry Bubble Column

Cu-based C301/-Al2 O3

230270

50

Papari et al.

[52]

Direct

Pipe-shell xed-bed
(thermally coupled
heat exchanger
reactor)
Fixed-bed membrane
reactor
Fluidized bed
membrane reactor

CuOZnOAl2 O3 /-Al2 O3

220

50

Space velocity = 15,000 mL


(gcath)1
H2 /CO/CO2 /N2 =
a. 61/30/5/4
b. 48/32/16/4
H2 /CO/CO2 /N2 /CH4 = 56/28/5/5/6
(mol%)
GHSV = 7500 (Nml/gcat/min)
GHSV = 6000 L/(kgcat h)
H2 /CO = 0.45
CO2 content = 4.8 (mol%)
H2 /CO = 1.82
CO2 content = 5.16 mol%
GHSV = 450060,000 Nml/gcat/h
H2 /CO = 1, 2, 4
Space velocity = 3000, 8000 h1
H2 /CO = 1.8, 2.0, 2.1
H2 /CO = 0.61.5
CO2 content = 0.00090.079
Space velocity = 1500 h1
H2 /CO = 2.24
CO2 content = 4.8%
H2 /(CO + CO2 ) = 1, 1.5, 2
Water removal (volume
fraction) = 0.5
H2 /CO/CO2 = 3/1.5/1
Space time = 8.33, 16.66, 33.33
and 66.66 (g of catalyst) h/mol of
(H2 + CO)
GHSV = 1000 h1
H2 /CO = 2
Space velocity = 3000 ml/g/h
H2 /CO =1.0
H2 /CO = 2.03
CO2 content = 3%mol
H2 /CO = 2.52
CO2 content = 4.09 mol%

Vakili et al.

[62,64]

CuOZnOAl2 O3 /H-ZSM-5

250

50

Iliuta et al.

[84]

220300

Mardanpour
et al.

[89]

Direct

Autothermal dual-bed
membrane

CuZnOAl2 O3 /H-ZSM-5

250

Tube
side: 40
Shell
side: 50
32

Iliuta et al.

[95]

Direct

Fixed-bed
micro-reactor
Fixed-bed reactor

CuOZnOAl2 O3 /-Al2 O3

230300

Hadipour et al.

[96]

Cu/Y
CuMn/Y
CuZn/Y
CuMnZn/Y

245

20

Fei et al.

[111]

Direct
Direct

Direct

H2 /(CO2 + CO) = 1.0, 1.5


Water removal = 0.0-5.0e-10
Space velocity = 3000 ml/gcat/h
H2 /CO = 1

Water removal = 1e-10-5e10 kmol/(sm2 Pa)


H2 /CO = 100
CO2 content = 21.5%mol
CO/CO2 /H2 = 64/32/4 vol.%
Space velocity = 1500 h1
H2 /CO = 1.5

Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150172

Synthesis method

Table 3 (Continued)
Synthesis method

Type of reactor

Catalyst

Temperature
( C)

Pressure
(bar)

Other essential factors

Authors

Ref. No.

Direct

Fixed-bed reactor

CuZnOAl2 O3 /Zr-ferrierite

250

40

Bae et al.

[112]

Direct

Fixed-bed reactor

Up to 450

Up to 100

Stiefel et al.

[117]

Direct

Fixed-bed reactor

CuO/ZnO system
-Al2 O3
zeolites and -Al2 O3
CuZrPdCNTs/HZSM-5

GHSV = 5500 L/(kgcat h)


CO/CO2 /H2 = 41/21/38 (%mol)
Residence time = 1090 s
H2 /CO = 0.67, 1.0

190270

50

Zhang et al.

[130]

Direct

Fixed Micro-reactor

CuOZnOAl2 O3 /H-ZSM-5

200300

1040

Fixed-bed reactor

250280

42

Direct

Tubular reactor

260

40

Mao et al.

[165]

Direct

Slurry phase reactor

CuZnOAl2 O3 /H-ZSM-5
CuZnOAl2 O3 /Na-ZSM-5
HZSM-5 zeolites modied with
various contents of magnesium
oxide
CuOZnOAl2 O3 /-Al2 O3

Khoshbin and
Haghighi
Kim et al.

[153]

Direct

GHSV = 25,000 mL
STP/(h g-hydr.catal.)
H2 /CO2 /N2 = 69/23/8
H2 /CO = 2.0
GHSV = 600 cm3 /grcat h
GHSV = 6000 ml/gcat h
H2 /CO = 1.5
GHSV = 1500 ml (h gcat)
H2 /CO/CO2 = 0.66/0.30/0.04

260

50

Wang et al.

[166]

Direct

Fixed-bed reactor

250

50

Flores et al.

[167]

Direct

Micro-channel reactor

220320

1040

[173]

Isothermal xed-bed
reactor

275

30

Sierra et al.

[175]

Direct

Isothermal plug-ow
reactor

900

3060

Kabir et al.

[176]

Direct
Direct
Direct

Slurry phase reactor


Fixed-bed reactor
Fixed-bed reactor

Bifunctional Catalyst (blend of


methanol dehydration catalyst and
-Al2 O3 )
Mn/CuZnAl
CuOZnOAl2 O3 /-Al2 O3
Mesoporous Cu-Al2 O3

GHSV = 500020000 h1
H2 /CO = 2.0, 3.0
CO2 content = 4 mol%
Space time = 12.8 (g of catalyst) h
(mol of reactants)1
H2 /CO = 3/1
Time on stream = 30 h
Water/syngas molar ratio in the
feed = 00.6
GHSV = 800 ml/gcat h
H2 /CO = 0.81

Hu et al.

Direct

CZZr
CZAZr
Katalco mixed with H-ferrierite
zeolite
F51-8PPT
ZSM-5
Acidic Al2 O3
CuOZnOAl2 O3 /-Al2 O3

H2 :CO = 1:1.5
Space velocity = 4000 h1
H2 /CO = 2.0

240, 260, 280


225325
285325

50
20
50

Tan et al.
et al.
Erena
Jiang et al.

[179]
[189]
[190]

Direct

Fixed-bed reactor

240290

3070

Kim et al.

[192]

Direct

Fixed-bed reactor

Cu/Zn
Cu/Zn/Al
CZ-A (Copper Acetate, Zinc
Acetate)
CZ-N (Copper Nitrate, Zinc
Nitrate)
Al-MCM-41

GHSV = 2.0 L/g cat h, H2 /CO = 2/1


H2 /CO = 2
GHSV = 5500 L/(kgcat h)
CO/CO2 /H2 = 41/21/38
H2 /CO = 0.52.0
Space velocity = 30006000 h1

260

50.7

Naik et al.

[193]

Direct
Direct

Slurry bubble column


Slurry bubble column

250
250

52.7
52

Chen et al.
Peng et al.

[194]
[195]

Direct

Fixed-bed

Cu/Zn/A1/O-based methanol
synthesis
CuZnAl/HZSM-5

240

50

Jia et al.

[196]

Direct

Tubular xed-bed
micro-reactor

Mixtures of Cu/ZnO/Al2 O3 and


-Al2 O3

250

50

GHSV = 2000 mLg1 cat h1


H2 /CO2 = 3
H2 /CO = 2.2
GHSV = 6000 mLg1 cat h1
H2 /CO2 = 1/2.2
Space velocity = 1000 h1
H2 /CO = 2/1
CO2 content = 7.06 (%mol)
GHSV = 8400 h1
H2 /CO = 2/1

Montesano
et al.

[197]

[155]
Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150172
167

168

Table 3 (Continued)
Synthesis method

Type of reactor

Catalyst

Temperature
( C)

Pressure
(bar)

Other essential factors

Authors

Ref. No.

Direct

Fixed-bed

275

40

[198]

Fixed-bed

260

40

Fixed-bed

Mixture of CuOZnOAl2 O3 and


sulfate-modied -Al2 O3

260

40

Garca-Trenco
and Martnez
Mao et al.

[199]

Direct

Space time = 8.33 g catalyst


h/(mol reactants)
H2 /CO = 4/1
GHSV = 1700 mL syngas/(gcat h)
H2 /CO/CO2 = 0.66/0.30/0.04
GHSV = 1500 ml (h gcat)
H2 /CO/CO2 = 0.66/0.30/0.04

Aguayo et al.

Direct

CuOZnOAl2 O3 /-Al2O3 and


CuOZnOAl2 O3 /NaHZSM-5
hybrid catalysts
CZA

Direct and Indirect

Isothermal xed-bed
reactor

CuMnZn/CeHY

245

20

H2 /CO = 3/2
Space velocity = 1500 h1

Jin et al.

[100]

Indirect

Tubular packed reactor

120450

High Bronsted acidity of


Al@SBA-15

Tokay et al.

[1]

Indirect
Indirect
Indirect
Indirect

Fixed-bed reactor
Adiabatic xed-bed
Fixed-bed reactor
Catalytic distillation
column

190300
233303
180320
110135

5
1
1.1
9

LHSV (h1 ) = 8.5

Zhang et al.
Raoof et al.
Rownaghi et al.
Hosseininejad
et al.

[3]
[4]
[9]
[20]

Indirect
Indirect

260
150250

18.2
1

Farsi et al.
Khademi et al.

[60]
[65,90]

H-ZSM5/SiC
-Al2 O3

250
260

1
18.8

Water removal = 5 (%mol)

Liu et al.
Samimi et al.

[77]
[80]

F-4SF Resin

180

Volkov et al.

[82]

Indirect
Indirect

Fixed-bed reactor
Heat exchanger reactor
Adiabatic xed-bed
reactor
Platelet Milli-reactor
Spherical packed-bed
membrane reactor
Catalytic membrane
reactor
Fixed-bed reactor
Fixed-bed reactor

Alumina Impregnated SBA-15


(Al@SBA-15)
Mesoporous Aluminosilicate
-Al2 O3
Al2 O3 -HZSM-5
-Al2 O3
ZSM-5
-Al2 O3
Zeolites (HY, HZSM-5 and HM)
Ion exchange resins (Amberlyst
15, 35, 36 and 70)
-Al2 O3
Pt/Al2 O3
-Al2 O3

Nanocrystalline -Al2 O3
AlPO4

300
150300

1
1

LHSV = 2.8, 11.7, 26.1 h1

[101]
[102]

Indirect

Fixed-bed reactor

300

GHSV = 15,600 h1

Indirect
Indirect

Fixed-bed reactor
Fixed-bed reactor

-Al2 O3
Modied -Al2 O3 with silica
meso--Al2 O3
CuOZnOAl2 O3
HZSM-5

Hosseini et al.
Lertjiamratn
et al.
Yaripour et al.

300
Top
stage = 268
Bottom
stage = 236

80

Absence of an acid catalyst


Space velocity = 1800 h1
H2 /CO = 2.0

Khaleel
Zhu et al.

[191]
[201]

CO2 Hydrogenation

Isothermal xed-bed
reactor
Fixed-bed reactor

CuOZnOAl2 O3 /-Al2 O3

225325

2040

et al.
Erena

[8]

200

30

Wang et al.

[33]

Indirect

CO2 hydrogenation

[161]

CO2 hydrogenation

Fixed-bed reactor

Blend of CuOTiO2 ZrO2 and


H-ZSM-5
CuOZnOAl2 O3 /H-ZSM-5

262

30

Zha et al.

[99]

CH3 Br hydrolysis

Glass tube reactor

ZnCl2 /SiO2

180

You et al.

[31]

CH3 Br hydrolysis

Batch reactor

PVP

50125

ZnCl2 loading from 1.0 mol% to


12 mol%

Prakash et al.

[36]

Note: f = (H2 CO2 )/(CO + CO2 ).

Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150172

Indirect
Indirect

[200]

Z. Azizi et al. / Chemical Engineering and Processing 82 (2014) 150172

has an inhibiting effect on the reaction rate by competing with


methanol molecules over acid sites. Under H2 O removal conditions with hydrophilic membranes, the watergas 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 synthesis through isothermal xed 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 xed bed
reactor, at the expense of DME selectivity. From the stoichiometry
of the reaction it is concluded that pressure increases the conversion of CO and it is specied 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 xed-bed and slurry reactors.
Despite numerous studies on DME production in literature,
there is still lack of an entire research area encompassing economic aspects of the process. Moreover, improving optimization
and scaling up of the one-step synthesis of DME should be considered. 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 dened 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 different 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 optimum value of water removal in the case of membrane reactors.
Developing a long life-time catalyst for CH3 Br hydrolysis reaction in order to make this approach practical and investigating the
efciency of immobilizing catalysts in micro reactors are further
proposed.

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