Escolar Documentos
Profissional Documentos
Cultura Documentos
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
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156
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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.
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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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
152
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.
(3)
(4)
= 90.4 kJ/mol
(5)
= 23.5 kJ/mol
H298
= 49.4 kJ/mol
(6)
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].
= 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)
153
Methanol
To DME
Tank
Reactor
To Waste
Water
Treatment
DME Tower
Methanol/Water Tower
Fig. 4. A scheme of indirect synthesis process.
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
154
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.
155
156
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
157
Fig. 11. Path from conventional setup to reactive dividing-wall column (R-DWC).
Source: Modied from [76].
Fig. 12. A schematic diagram of co-current mode for uidized bed membrane reactor (FBMR) conguration.
Source: Modied from [89].
158
the pressure drop decreased, but also more production of DME was
obtained [80,97].
159
Table 2
Different types of DME reactors in comparison.
Reactor type
Characteristics/usages
Cautions
Fixed-beds
Catalyst deactivation
High recycle of syngas
High operational investment
High pressure drop
Complicated equipment
Loss of catalyst particles
Collision between catalyst particles
and the reactor wall
Loss of catalyst
Slurry phase
Fluidized-bed
Micro reactors
Membrane reactors
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].
Laminar ow behavior
160
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.
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
162
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
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
100
80
60
40
20
0
0
0.5
1.5
2.5
2CO+4H2=CH3OCH3+H2O
CO+2H2=CH3OH
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
100
80
60
40
20
0
0.25
0.5
0.75
1.25
1.5
1.75
2.25
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].
165
166
Table 3
Production conditions for various works on DME synthesis.
Type of reactor
Catalyst
Temperature
( C)
Pressure
(bar)
Authors
Ref. No.
Direct
Fixed-bed reactor
CuZnOAl2 O3 /ZSM5
200280
40
Chen et al.
[2]
Direct
Micro packed-bed
reactor
220320
5070
Hayer et al.
[5]
Direct
25240
76.5
Chen et al.
[10]
Direct
Fixed-bed reactor
Cr/ZnOSZ
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
CuZnOAl2 O3 /HZSM-5
260
30
Lu et al.
[44]
Direct
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
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
Synthesis method
Table 3 (Continued)
Synthesis method
Type of reactor
Catalyst
Temperature
( C)
Pressure
(bar)
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
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
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
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
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
260
50.7
Naik et al.
[193]
Direct
Direct
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
250
50
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)
Authors
Ref. No.
Direct
Fixed-bed
275
40
[198]
Fixed-bed
260
40
Fixed-bed
260
40
Garca-Trenco
and Martnez
Mao et al.
[199]
Direct
Aguayo et al.
Direct
Isothermal xed-bed
reactor
CuMnZn/CeHY
245
20
H2 /CO = 3/2
Space velocity = 1500 h1
Jin et al.
[100]
Indirect
120450
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
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
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
Nanocrystalline -Al2 O3
AlPO4
300
150300
1
1
[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
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
262
30
Zha et al.
[99]
CH3 Br hydrolysis
ZnCl2 /SiO2
180
You et al.
[31]
CH3 Br hydrolysis
Batch reactor
PVP
50125
Prakash et al.
[36]
Indirect
Indirect
[200]
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