6518 Ind. Eng. Chem. Res.

2003, 42, 6518-6530

REVIEWS

Recent Advances in Catalysts for Methanol Synthesis via

Hydrogenation of CO and CO2
Xin-Mei Liu,†,‡ G. Q. Lu,† Zi-Feng Yan,†,‡ and Jorge Beltramini*,†
Department of Chemical Engineering, University of Queensland, Brisbane 4072, Australia, and
State Key Laboratory for Heavy Oil Processing, Key Laboratory of Catalysis, CNPC,
University of Petroleum, Dongying 257062, China

Since the start of last century, methanol synthesis has attracted great interests because of its
importance in chemical industries and its potential as an environmentally friendly energy carrier.
The catalyst for the methanol synthesis has been a key area of research in order to optimize the
reaction process. In the literature, the nature of the active site and the effects of the promoter
and support have been extensively investigated. In this updated review, the recent progresses
in the catalyst innovation, optimization of the reaction conditions, reaction mechanism, and
catalyst performance in methanol synthesis are comprehensively discussed. Key issues of catalyst
improvement are highlighted, and areas of priority in R&D are identified in the conclusions.

1. Introduction as reactant feedstock should be of importance in metha-

With the rapid changes and development in modern
industry, the energy and environmental issues have
become two major concerns. Methanol has been a
common chemical feedstock for several important chemi-
cals such as acetic acid, methyl tert-butyl ether (MTBE),
formaldehyde, and chloromethane for over 30 years.1
Methanol, being a clean liquid fuel, could provide
convenient storage of energy for fuel cell applications,
particularly in transportation and mobile devices. When
used as a fuel, it is a cleaner energy compared with most
other sources. For these reasons, methanol synthesis is
still attracting interest despite the fact that the current
technology process was developed a long time ago.
Commercially, methanol has been produced from
syngas using natural gas or coal, mainly containing CO
and H2 along with a small amount of CO2.2 Methanol
synthesis through hydrogenation of carbon dioxide has
attracted continuous worldwide research interest in the
past 15 years because of its environmental impact. The
potential use of CO2, the most important greenhouse
gas, as an alternative feedstock replacing CO in the
methanol production has received attention as an ef-
fective way of CO2 utilization. A recent study showed
that a mixture with a proper proportion of CO2 and CO
not only can increase the yield of methanol but also
decreases the apparent activation energy of the reaction.
Of special interest is that the presence of CO2 could
maintain the active copper sites in the oxidation state
or prevent an over-reduction of the ZnO component3-5
when Cu/Zn catalysts are used during methanol syn-
thesis. Therefore, the use of mixtures of CO2 and CO
nol synthesis.
At present the key to methanol synthesis is to develop
the most efficient catalyst. Many research groups are
engaged in catalyst preparation using different catalyst
compositions and preparation methods. New catalysts
based on nickel, copper, and alloys have been reported.
Recently, ultrafine particle catalysts have also been
proposed. Deng et al.6 reported that the ultrafine
Cu/ZnO/Al2O3 ternary catalyst prepared with an oxalate
gel coprecipitation exhibited high activity. Tanaka et
al.7 obtained a Cu/ZnO binary catalyst using ethylene
glycol as the solvent. They found that the methanol
selectivity was higher when the ratio of copper to zinc
was 1 and the active sites were ascribed to the copper
atoms in contact with the oxide crystallites. Nitta et al.8
reported that the proper addition of certain amounts of
ZnO to the Cu/ZrO2 catalyst could greatly enhance its
activity. Liaw and Chen9 obtained ultrafine Cu-based
catalysts using a reduction method in which the disper-
sion and stability of Cu could be enhanced by doping
Cr, Zr, and Th. Other groups10,11 confirmed that doping
the trivalent metal ions or rare-earth elements such as
La and Y onto the catalysts could improve its perfor-
mance. No matter what method is used for the catalyst
to possess higher activity, selectivity, and long life, it is
important to obtain a catalyst with larger surface area,
fine particle size, and a high dispersion of active sites.
Although extensive studies have been carried out for
over 2 decades, controversies still remain concerning the
role of active sites involved in the catalysts, the effect
of the addition of various promoters, and the reaction
mechanism.

* To whom correspondence should be addressed. Tel.: 61 7 2. Catalyst Innovation for Methanol Synthesis
33654316.Fax: 61733654199.E-mail: jorgeb@cheque.uq.edu.au.
† University of Queensland. E-mail: m.lu@uq.edu.au. 2.1. Active Site. Although the properties of catalysts
‡ University of Petroleum. E-mail: zfyan@hdpu.edu.cn (Z.- used in the synthesis of methanol has been extensively
F.Y.) and lxmei@mail.hdpu.edu.cn (X.-M.L.). studied for many years, Cu still remains as an impor-
10.1021/ie020979s CCC: $25.00 © 2003 American Chemical Society
Published on Web 11/11/2003

tant active catalyst component, even though the nature
of the active site is yet to be fully understood. It is
generally accepted that the coordination, chemisorption,
and activation of carbon monoxide and the homogeneous
splitting of hydrogen take place on Cu0 or Cu+ and that
the heterogeneous splitting of hydrogen, which provides
Hδ+ and Hδ- in the catalytic process, takes place on
ZnO.12 However, different points of view on the nature
and valence of copper sites still exist.
Some researchers13-15 pointed out that metallic Cu
atoms were uniformly active for methanol synthesis.
Pan et al.16 found that the activity of the catalyst is
directly proportional to the surface area of metallic Cu
and methanol is formed on a metallic Cu surface of a
Cu-based catalyst. Similarly, Deng et al.6 reported that
the catalytic activity of a Cu/ZnO/Al2O3 ternary catalyst
for carbon dioxide hydrogenation increases with an
increase in the metallic copper surface area, reached a
maximum, and then decreased at a Cu/ZnO molar ratio
of 8. Rasmussen et al.17,18 investigated methanol syn-
thesis by hydrogenation of CO2 on Cu(100) at total
pressures of 1-4 bar and reported that metallic copper
is actual an active site. They formulated a kinetic model
for the elementary steps of methanol synthesis. It
indicated that the calculated reaction rate and the
activation energy for methanol synthesis were in accord
with those measured on Cu(100). They excluded the
possibility of Cu+ active sites because only metallic
copper was observed on the Cu(100) surface used.
Similarly, Askgaard et al.19 supported the metallic Cu
model by applying a kinetic model based on experimen-
tal data to the methanol synthesis reaction using a Cu
single crystal.
However, in the presence of CO2 and with a large
fraction of the Cu0 surface covered by oxygen-containing
species, the catalytic activity toward methanol synthesis
is found to be independent of the Cu0 surface area.20,21
This finding can be explained by the fact that the Cu+
sites might be acting as active sites in methanol
synthesis. Subsequently, Herman et al.22 reported that
active Cu+ ion sites are dissolved on the surface of the
ZnO matrix. They based their findings on the fact that
there was not any new phase other than the normal
crystal structure of Cu metal and zinc oxide that
coexisted in the mixed Cu/ZnO catalysts and that the
activity of the rodlike networked catalyst containing
more Cu+ was higher than that of the platelets. It can
be deduced that the promotion effect could only stem
from the catalytic activity of a solid solution such as
Cu+/ZnO and active centers of the Cu-based catalyst
should be Cu+ ions dissolved in ZnO. On the basis of
apparent activation energy measurements, X-ray pho-
toelectron spectroscopy, and scannin electron micros-
copy results, Sheffer and King23 stipulated that activity
differences among unsupported copper catalysts pro-
moted by group IA elements could be attributed to
differences in the concentration of Cu+ species. It was
observed24 that the addition of alkali metals such as
potassium or cesium could positively promote methanol
synthesis on nonsupported Cu catalysts and with cat-
ionic Cu as the active site. Szanyi and Goodman,25 while
comparing the activity for methanol synthesis on clean
Cu(100) and oxidized Cu(100), concluded that the Cu
ion is the active site. In another study, Van Santen et
al.26 stated that anything else that stabilizes the pres-
ence of Cu+ indiscriminately enhances the activity of
the catalyst.
Ind. Eng. Chem. Res., Vol. 42, No. 25, 2003 6519
More recently, a synergetic effect between Cu and the
promoter was reported.27-33 Chen et al.27 found that the
coexistence of ZnO with Cu enhanced the ability of Cu
to adsorb CO and ZnO enhanced synergistically the
subsequent hydrogenation to form ethanol, while Cu
improved the ability of Zn2+ to adsorb H. Obviously, CO
is bound to Cu sites and H to ZnO sites. It was also
observed that the methoxy intermediates were first
found on Zn sites. Burch et al.28-32 thought that the
synergistic effect might involve the migration of spill-
over adsorbed species such as H+ on Cu to ZnO sites to
hydrogenate the formate species to methanol. Whereas
Kanai et al.33 reported that the interaction between Cu
and Zn sites is achieved by the way that ZnO impacts
the creation of active sites such as Cu+ by the ZnOx
fractioned on the Cu surface, Fujitani and Nakamura34
proposed that the creation of a Cu-Zn surface alloy on
Zn/Cu(111) could be responsible for the formation of
active sites. Cu-Zn sites are basically metallic, in which
the Cu atoms catalyze the hydrogenation in methanol
synthesis; therefore, aurichalcite should be an excellent
precursor in the preparation of Cu/ZnO catalyst. Of
special interest is that copper alone could not be an
independent active site in effective methanol synthesis.
Electronic interactions and geometrical effects are
exerted on copper sites with coexistent components in
the catalysts. In fact, since 1979, Herman and co-
workers22 had already indicated that the catalytic
activity of the binary catalyst was at least 3 orders of
magnitude greater than that of the pure copper metal
or zinc oxide, the resulting differences bearing the
consequence of the synergistic interaction between Cu
and ZnO.
Burch and co-workers clearly summarized the hy-
potheses about the synergistic interactions between
copper and zinc oxide33-40 into six categories as fol-
lows: (a) the formation of Cu+ ions in ZnO; (b) electronic
interactions between Cu and ZnO; (c) Schottky Junction
effects at the Cu/ZnO interface; (d) the formation of a
Cu/Zn pair; (e) a specific reaction at the Cu/ZnO
interface; (f) stabilization of Cu in a morphologically
active form by ZnO. Surprisingly, they concluded that
direct contact between the active sites and support is
not necessary for higher activity. Synergy might be due
to the presence of carbon dioxide.
In addition, there are other opinions about the active
sites for methanol synthesis. Chen et al.27 proposed that
the activity of a copper-based catalyst is directly pro-
portional to the total copper exposed (Cu0 and Cu+) and
that the activity did not depend on special copper sites.
On the other hand, Jackson and Frost36,41,42 established
that the active sites of CO hydrogenation over ZrO2 or
Y2O3-doped ZrO2 could result from oxygen anion vacan-
cies, in which higher mobility of oxygen vacancies
represents higher reaction rate. On the condition of
absence of copper, a catalyst promoted by silver and gold
oxides also possessed a high activity for methanol
formation. This means that the above noble metals could
adjust the electronic properties of their oxides and thus
modify the nature of the active centers, which results
in surface oxygen vacancies.
Obviously, from the above information presented,
there are still controversies regarding the role of the
active site of catalysts for methanol synthesis. However,
synergy between the main catalyst and promoter or
support does now seem to be a rather well-established
phenomenon. This synergy is due to the transfer of
6520 Ind. Eng. Chem. Res., Vol. 42, No. 25, 2003
species among the catalyst components, which need not
even be in direct physical or chemical contact.28 The
interaction among various catalyst compositions results
in differences in the morphology and electronic effect
of each catalyst investigated. Accordingly, it may cause
them to have small particle size and larger surface area.
Small particle size can reduce the diffusion resistance
of reactant molecules entering the catalyst pore, while
the active site at the inner pore can be adequately used.
This means that small particle size can promote higher
activity. The larger surface area can improve the
dispersion of the active component, which resists the
sintering among the metal particles. Simultaneously,
a change of the electronic effect can modulate the
adsorption strength between the reactant molecules and
the catalyst surface, which strongly influences catalyst
selectivity. Namely, the electronic effect indirectly af-
fects the catalyst selectivity. In addition, the synergy
among the components can achieve the transformation
of the hydrogen atom to carry out a hydrogenation
reaction. This is discussed in detail next in the Support
Effect section.
2.2. Support Effect. An appropriate support not only
provides a good configuration but also must have some
function in modulating the interactions between the
primary components of the catalyst and promoter. In
addition, the basicity/acidity characteristics of the cata-
lyst can also be affected. Metal oxides are the more
common supports used for the preparation of a methanol
synthesis catalyst. Their properties greatly affect the
catalyst activity as a result of the aspects mentioned in
the previous section. Of all metal oxides ZnO, ZrO2, and
SiO2 are the most typical materials used as supports in
methanol synthesis catalysts.
2.2.1. ZnO. ZnO is an n-type semiconductor, with a
wurtzite structure in which Zn+ ions are located in
tetrahedral sites in a close-packed array of O2- ions. Its
surface reactivity is defined by particle morphology.43
It possesses lattice oxygen vacancies, consisting of an
electron pair (2e-) in a ZnO lattice structure, which is
considered to be one kind of active site for methanol
synthesis. Zn2+-2e- pairs move interstitially, leaving
cation and anion lattice vacancies, which is beneficial
to the adsorption and transformation of the reactant.
Simultaneously, zinc oxide can improve copper disper-
sion of a Cu-based catalyst.
Traditionally, zinc oxide is a good hydrogenation
catalyst that activates hydrogen by heterogeneous split-
ting, giving rise to ZnH and OH. Furthermore, hydrogen
spillover has been observed with ZnO acting as a
reservoir of hydrogen for the hydrogenation of CO over
Cu surfaces. Dennison et al.44 observed that hydrogen
is adsorbed on ZnO to a much greater extent when Cu
is present in the catalyst. On the other hand, Burch and
co-workers28 found that hydrogen spillover from Cu to
ZnO occurs very rapidly from a partially oxidized Cu
surface but only to a very small extent from a fully
reduced copper surface. Moreover, the hydrogen atoms
were trapped at surface defects or at interstitial sites
of ZnO, but they were not held too strongly. This means
that a possible role of ZnO might serve as a reservoir
to provide H atoms for subsequent hydrogenation of
adsorbed reaction intermediates. Similarly, Spencer45
thought that synergistic effects are the result of H
spillover produced from ZnO to Cu metal.
A morphology effect was also postulated to state the
role of the zinc oxide support in a Cu-based catalyst.
Figure 1. Model of the active site for methanol synthesis over a
physical mixture of Cu/SiO2 + ZnO/SiO2 (from ref 49).
The ZnO support may optimize the dispersion of the Cu
particles and stabilize many active sites by attenuating
the unavoidable agglomeration of Cu particles, which
takes place during a long-term operation, and by
restraining Cu particles to be poisoned by feed gas
impurities. Yoshihara and Campbell46 using a batch
microreactor attached to an ultrahigh-vacuum chamber
for pre- and postreaction surface analysis determined
the relations between the surface area of Cu(110) single
crystal and catalytic activity. They were able to prove
that the active sites in methanol synthesis on Cu/ZnO
catalysts are metallic Cu and the role of the ZnO
support is to stabilize more metallic Cu sites. On the
other hand, Ovesen et al.47 correlated the changes in
particle morphology and the number of oxygen vacancies
at the Zn-O-Cu interface. They showed that the
interaction between copper and zinc oxides is important
for the dynamic spreading of the copper particles on the
support.
To further challenge the above explanation, Fujitani
and co-workers48,49 suggested that the ZnO support is
also an active component in methanol synthesis. They
observed that Zn species could migrate to the Cu surface
in a physical mixture of Cu/SiO2 and ZnO/SiO2 upon
reduction with H2. The quality of the active sites was
not changed, but the quantity of the active sites
increased with the increasing reduction temperature.
This meant that the role of ZnO is to create Cu-Zn
active sites on the Cu surface. Moreover, the catalytic
activity of a Zn-deposited Cu(111) surface was much
higher than that of Cu(111) alone. They also postulated
a model for the function of ZnO sites during methanol
synthesis. As we can see in Figure 1, the model explains
that the role of ZnO was not to improve the morphology
of Cu sites but to create the Cu-Zn active sites for
methanol synthesis. In this context, ZnO modifies the
electronic properties of Cu sites by an electron exchange
and interaction with Cu particles.
At the same time, ZnO have the ability to adsorb
poison species that are present in syngas streams.
Traditionally, copper catalysts are extremely sensitive
to very low levels of sulfur poisoning. ZnO as a support
could effectively remove H2S components from the gas

feed by forming zinc sulfide, which is a favorable
thermodynamic reaction in methanol synthesis condi-
tions. Twigg and Spencer50 corroborated that Cu/ZnO/
Al2O3 catalysts retained a higher activity and even
accumulated quite a large amount of sulfur. With an
average of 2% sulfur, the methanol synthesis activity
of Cu/ZnO/Al2O3 catalysts was approximately dropped
to 80% of the fresh catalyst. In contrast, Cu/Al2O3
catalysts were completely deactivated with only 0.2%
sulfur in the feed. In addition, ZnO can form a special
interface or surface defects between Cu and ZnO, which
might be an active surface domain. As a basic oxide,
ZnO can partially neutralize the acidity of Al2O3,
preventing the transformation of methanol to dimethyl
ether.50
2.2.2. ZrO2. The fluorite-type oxides, such as ceria,
zirconia, and thoria, have face-centered-cubic (fcc) crys-
tal structure in which each tetravalent metal ion is
surrounded by eight equivalent nearest O2- ions form-
ing the vertexes of a cube. Oxygen vacancies that serve
as active sites for some reactions are created when a
fluorite oxide is doped by divalent or trivalent impurity
ions.51
Zirconium oxide has also been investigated as a
promoter or support for the methanol synthesis cata-
lyst.52,53 Zirconia, a strong and thermal-resistant mate-
rial, is a very promising catalyst support because it
bears high stability under reducing or oxidizing atmos-
pheres;53-56 it was observed that catalytic activity using
ZrO2 as the support is better than that using Al2O3,
SiO2, and other materials. On the other hand, CuO can
be uniformly dispersed on a ZrO2 surface, forming a
specific interface that might be favorable for the metha-
nol synthesis reaction.
The synergistic effect between copper and ZrO2 was
the subject of many studies. Liu et al.,57 using aerogel
zirconia as the support, found that the binding energy
of Cu 2p3/2 of CuO/ZrO2 is higher than that of the pure
CuO. Moreover, the lower the copper oxide loading, the
larger the binding energy is. They also showed that CuO
and ZrO2 were not simply physically mixed, but some
interactions between them occurred, changing the elec-
tronic distributions. X-ray diffraction (XRD) character-
ization51 showed that, on ZrO2 with no copper loading,
the major peak found is mainly the monoclinic-ZrO2
crystal phase. After loading of CuO, the tetragonal-ZrO2
crystal phase appears in strong peaks and increases
with copper loading. The monoclinic-ZrO2 crystal phase
even fully disappears when CuO loading is higher than
10 wt %. This means that an interaction between copper
oxide and zirconium oxide should exist, which inhibits
the phase transformation of ZrO2. This metal-support
interaction is due to the oxygen vacancies of the support,
which causes a geometric effect that can affect the
dispersion and alter the morphology of the supported
metal. Koeppel and Baiker58,59 reported that efficient
methanol synthesis catalysts were found to consist of
microcrystalline copper particles that are stabilized
through interaction with an amorphous zirconia matrix,
resulting in a high interfacial area.
The activity of methanol formation using zirconia as
the support is slightly lower than when zinc oxide is
used as the support. Even though zirconia is still a more
preferred support for the methanol synthesis catalyst,
more and more researchers are inclining to investigate
its catalytic effect because of its special structure and
stability.
Ind. Eng. Chem. Res., Vol. 42, No. 25, 2003 6521
2.2.3. SiO2. As a catalyst support, silica possesses
predominant properties, such as acid-base nature,
porosity texture, and stable thermal stability. It is
commonly used for catalyst preparation by a wetness
impregnation method. However, copper supported on
high-purity silica was found to be nearly inactive in
methanol synthesis60-62 and selectivity toward methanol
was also low. Most of the catalysts prepared using silica
as the support needed the addition of other metal oxides
as the promoter to improve its activity.34,62,63
2.3. Promoter Effect. Because methanol synthesis
on a Cu-based catalyst is a structurally sensitive reac-
tion, it is useful to modify its performance using various
promoters, which could improve the activity, selectivity,
or stability of the catalyst.
It is well-known that Al2O3 is the widely used third
component in a Cu-based catalyst because it is a good
promoter. It not only can form zinc aluminate to prevent
the agglomeration of active sites but also accelerates the
adsorption and activation of CO because of its disorder
and defect surface domain. Furthermore, it can also
stabilize the highly dispersed Cu/ZnO structure. Chen
et al.11 reported that doping with trivalent metal ions
such as Al3+, Sc3+, and Cr3+ could also enhance the
formation of monovalent cationic defects on the crystal
surface of ZnO, which might accelerate both enrichment
and stabilization of Cu+ on the surface during the
reduction and reaction processes. Simultaneously, the
doping of Sc3+ positively increases the specific surface
area and greatly enhances the methanol yield.
Chromia in a skeletal copper catalyst could prevent
the rearrangement of Cu sites and improve the pore
structure and active surface of the catalyst.64 An
important observation is that loading chromia on skel-
etal copper can partially inhibit the reverse water gas
shift reaction, improving the bulk activity and selectivity
for methanol synthesis from CO2 and H2 and accelerat-
ing simultaneously the reduction of CuO species. Doping
copper catalyst with Pd showed a promotion effect
similar to that of Cr and positively prevented the
rearrangement of Cu species. In addition, the formation
of a special intersurface or surface defects between Cu
and ZnO might contribute to the fast adsorption and
high stability effects of a highly dispersed Cu/ZnO
structure.65
Zirconia also acts as a favorable promoter in methanol
synthesis as explained previously. The dissolution of
zirconium ions in a copper catalyst results in the
presence of a new copper oxide phase and promotes the
formation of Cu+ ions,66 which enhances the activity of
the catalyst for methanol synthesis at low temperatures
and pressures. The optimum amount of ZrO2 is 15 wt
%, resulting in maximum CO conversion and optimum
methanol selectivity (see Figure 2). This means that the
addition of ZrO2 improves the surface area of Cu species
and adjusts the ratio of Cu+/Cu0 in the surface, increas-
ing specifically CO conversion.
Other elements such as B, Ga, Co, and Mg were also
used as copper-based catalyst promoters in methanol
synthesis.9,67-69 They can modify the physical-chemical
properties just like the above elements. Recently, many
researchers are engaged in searching for new promoters
to improve the performance of the methanol synthesis
catalyst. However, a magic promoter does not seem to
be in sight yet.
2.4. Methods of Catalyst Preparation. As men-
tioned previously, it is well-known that methanol syn-
6522 Ind. Eng. Chem. Res., Vol. 42, No. 25, 2003
Figure 2. Effect of the ZrO2 content in Cu/ZnO/ZrO2 catalysts
on CO conversion (s) and methanol selectivity (t), respectively
(from ref 66).
thesis catalysts are structurally sensitive. The differ-
ences in preparation methods as well as pretreatment
conditions showed remarkable influences on the struc-
ture of the catalysts, ultimately affecting the catalytic
performance. Catalyst preparation methods were ex-
tensively reviewed as follows:
2.4.1. Coprecipitation Methods. Coprecipitation
methods are the most widely used methods to prepare
copper-based catalysts. Precipitators such as sodium
carbonates and oxalates are added to a solution of the
desired salt concentration to coprecipitate and form the
catalyst precursors. Then, the coprecipitates are sepa-
rated by centrifugal or evaporation methods.
2.4.1.1. Effect of the Reaction Conditions. Previ-
ous studies70-73 indicate that precipitation parameters
strongly affect the performance of a CuO-ZnO-based
catalyst, in which Cu/ZnO catalysts are prepared using
precursors such as hydrozincite Zn5(CO3)2(OH)6, au-
richalcite (Cux,Zn1-x)5(CO3)2(OH)6, malachite Cu2(CO3)-
(OH)2, rosasite (Cux,Zn1-x)2(CO3)(OH)2, or their mix-
tures.70,71 Only catalysts prepared using the aurichalcite
precursor are more active to CO hydrogenation.
Interestingly, the structure of the precursor varied
with the Cu/Zn ratio. At a low ratio (about 30/70), the
precursor produced using a solution mixture of nitrates
consists only of the aurichalcite phase, while a mixture
of aurichalcite and malachite phases is found at higher
ratios.
In the coprecipitation, the pH value plays an impor-
tant role in determining the composition of the precipi-
tates. When the precipitation was conducted at pH )
7, the precipitates mainly consisted of the malachite-
like phase and the catalysts were more active. Precipi-
tation at pH ) 6 favored the formation of hydroxy-
nitrate, which led to less active catalysts. It seems that
the pH value exerts its effect through alteration of the
phase composition of the precursors.
The temperature plays also a key factor during the
preparation of the optimum catalyst precursor. Wu et
al.73 suggested that the temperature of coprecipitation
should be less than 313 K. The crystallite size of the
precipitate prepared at higher than 313 K was slightly
larger, reflecting in a decrease of the catalytic activity.
It was also stressed that temperature also affects the
precipitation kinetics of the precursors.
2.4.1.2. Effect of the Precipitation Species. Koep-
pel et al.59 reported that the catalyst prepared using
Figure 3. TEM photographs of the catalyst prepared with
different precipitators (from ref 74).
ammonium carbonate as a precipitator showed lower
activity than the catalyst made by hydroxide precipita-
tion. Acetate-modified precursors resulted in dramati-
cally increased activity compared to the oxide precursor.
This showed that the catalyst synthesized under slightly
acidic conditions had a copper surface area similar to
those of the samples prepared under alkaline conditions
while distinctly larger than those of the samples ob-
tained under neutral precipitation conditions. This
means that the pH value in coprecipitation is very
important in order to obtain an optimum catalyst
composition.
A homogeneous Cu and Zn distribution over spherical
particles was obtained when oxalate was used as the
precipitator, whereas irregular particles with Cu ag-
gregates on the surface of the catalyst were found when
conventional carbonate salts were used as coprecipita-
tion agents.74 The transmission electron microscopy
(TEM) photographs in Figure 3 clearly showed the
different shapes of the catalysts prepared using different
precipitator agents. If the precipitator is sodium carbon-
ate, the catalyst cannot exclude the sodium ions, which
remain in the catalyst, reducing the total Cu surface
area and activity of the catalyst. It is worth noting that
the CuO/ZnO ratio obtained for the catalyst prepared
using carbonate as the precipitator is higher than that
obtained with oxalate as the precipitator, which makes
the reduction of catalyst with carbonate easier than that
with oxalate. This means that the process of isomor-
phous substitution between Cu and Zn actually occurred
during coprecipitation with carbonate and that ZnO
exists mainly as amorphous particles in the catalyst
prepared using oxalate. Methanol synthesis activity was
also shown to be higher than that of carbonate by an
order of magnitude.
2.4.1.3. Solvent Effect. Figure 4 shows the morphol-
ogy of the precursor prepared with different solvents.75
The precursor obtained using deionized water as the
solvent mainly consisted of large amorphous clusters.
However, a little quasispherical crystal was also ob-
served. Precursors obtained using dimethylformamide
exhibited a column-shaped crystal phase, whereas in the
case of using ethanol as the solvent, the precursor was
found to be mostly amorphous. When diethylene glycol
was employed as the solvent, the resulting precursor
exhibited both amorphous clusters and a barlike crystal
phase. From the experimental findings, it can be stated
that different coprecipitation mechanisms actually exist
and the significant differences found in the structure
and morphology of the precursors are the consequence
of the different solvents employed during the precipita-

Figure 4. TEM photographs of precursors prepared with different solvents (from ref 75).
tion step. Overall, coprecipitation using ethanol as the
solvent was found to be the most effective route for the
preparation of a highly active and selective catalyst.
The XRD patterns shown in Figure 5 illustrate that
the catalysts prepared with different solvents possess
different particle sizes. A broad diffraction peak for
calcined CuO/ZnO/Al2O3 catalysts prepared using etha-
nol as the solvent is observed. This is indicative of the
catalyst consisting of uniform ultrafine particles. N2
adsorption data showed that the surface area of the
catalyst prepared using ethanol as the solvent is much
higher than that using water.6 Consequently, copper
dispersion and the crystallite size of the catalyst with
ethanol are much higher than those of catalysts with
other solvents. TEM (Figure 6) clearly revealed that
very small quasispherical particles are found in the
catalyst with ethanol.
The effects of different solvents on the texture and
morphology of the catalyst are ascribed to their surface
tension, viscosity, and dielectric constant.75 The weaker
surface tension of the solvent can mitigate the serious
shrinkage in the volume and resist the microstructural
collapsing of the precursor of the catalyst. The catalyst
prepared with the weaker surface tension solvent would
have large surface area and volume, which is beneficial
Ind. Eng. Chem. Res., Vol. 42, No. 25, 2003 6523
to the dispersion of the active sites. The viscosity
influences the nucleation process of the particles. The
more viscous the solvent used, the faster nucleation and
the slower the nucleus growth rate. According to the
nucleation theory, fast nucleation and the slower the
nucleus growth lead to fine crystallites. Hence, the more
viscous solvent can synthesize the finer crystallites. All
in all, the solvent plays an important role in the
preparation of the catalyst. The solvent with small
surface tension and large viscosity contributes to the
preparation of the disordered and isomorphous substi-
tution precursor, which will be of benefit to the activity
of the catalyst.75
2.4.2. Other Preparation Methods. The most com-
mon way to prepare metal-supported catalysts, the
impregnation technique, can also be used to synthesize
methanol catalysts. The characteristics of the impreg-
nated catalysts are determined by the precursor used
and the impregnation conditions. However, for the case
of methanol synthesis catalysts, the performance of the
catalyst prepared using this technique is not as good
as that when a coprecipitate method is employed.69
Silica is commonly used as the support by the
impregnation method. Burch and Chappell37 confirmed
that Al2O3, ZrO2, Ga2O3, and ZnO can be used as the
6524 Ind. Eng. Chem. Res., Vol. 42, No. 25, 2003
Figure 5. Profile of the XRD patterns of calcined CuO/ZnO/Al2O3
prepared with different solvents (from ref 73).
promoter of Cu/SiO2 catalysts where B2O3 and In2O3 can
be poison components. ZnO was proposed to be the
reservoir for atomic hydrogen and to promote hydrogen
spillover. Gotti and Prins76 found that Ca and La oxides
bear strong promoting effects on the silica-supported Cu
and that CO2 is the main carbon source for methanol.
Figure 6. TEM photographs of calcined precursors prepared with different solvents (from ref 73).
Table 1. Effect of the Heating Rate for the Calcination
on the Crystallite Sizes of CuO and ZnO (from Reference
78)
heating rate/(K min-1) CuO/nm ZnO/nm
1 3.5
2 3.3
5 3.9 4.3
10 4.6 4.6
20 8.8 10.6
Toyir and co-workers69 prepared Cu-Ga/ZnO and Cu-
Ga/SiO2 catalysts to verify the effect of the support and
promoter on the conversion of CO2.
Liaw and Chen9 using a reducing technique prepared
the Cu-based ultrafine catalysts. The deposition-
precipitation method of ZrO2-supported catalysts and
the uniform gelation method for Cu/ZnO/Cr2O3/Al2O3/
Ga2O3 were also investigated.57,77
2.4.3. Pretreatment Effect. The structure and cata-
lytic performance of the catalysts also depends on
calcination and subsequently reduction.51,78 The lower
heating rate of calcination benefits the formation of fine
particle size catalysts. Fujita et al.78 observed an
increase in the particle size of CuO or ZnO catalyst
prepared using aurichalcite when the heating rates were
increased from 2 to 20 K min-1 (listed in Table 1). UV-
vis diffusion reflectance spectra showed that the absorp-
tion edge of the samples at lower heating rates shifts
toward a lower wavenumber. This indicates that at
lower heating rates it is feasible to synthesize ultrafine
catalysts. The effects of the heating rate on the CuO or
ZnO particle size should be attributed to the interaction
of water, which could accelerate the growth of metal
oxide crystallites. When calcination was carried out at
a faster heating rate, the decomposition of the precursor
would proceed in a short period. Accordingly, the metal
oxide will interact with water at higher partial pressure
so that calcination at higher heating rates leads to an
increase in the CuO or ZnO size.
The reduction is necessary to obtain optimum catalyst
performance. Unfortunately, the reduction process is
exothermic, which could accelerate the agglomeration
of surface active sites, especially at higher heating rate

Figure 7. Effects of the temperature on the catalytic activity of
methanol synthesis on different compositions of Cu/ZnO/Al2O3
catalysts: (9) 10/80/10; (b) 30/60/10; (O) 60/30/10; (- -) calculated
formation rate of methanol based on thermodynamic equilibrium
(from ref 82).
or high temperature. Fujita et al.79 reported that the
lower reduction temperature is beneficial for improving
copper dispersion and activity for the methanol synthe-
sis and that using methanol as the reducing agent is
better than using hydrogen. During reduction with
methanol, endothermic dehydrogenation to methyl for-
mate inhibits any temperature increase that can dam-
age the catalyst structure.
3. Optimization of the Reaction Conditions
3.1. Temperature. It is well-known that the reaction
rate for CO/CO2 hydrogenation is always increased with
increasing temperature. However, because it is an
exothermic reversible reaction, the product distribution
will be controlled by both thermodynamics and kinetics.
Its equilibrium constant decreases with an increase in
the temperature. Thus, higher temperature is a disad-
vantage to the yield of methanol. Zhang et al.80 reported
that methanol selectivity decreases slowly in the lower
temperature range and quickly at higher temperature.
On the other hand, Bill and co-workers81 observed that
the methanol yield increases with temperature up to
493 K; then it started to decrease above 493 K despite
a continuous increase in the conversion of CO2. Tradi-
tionally, the reaction temperature reported is below 573
K. In this temperature range, the methanol yield is
relatively high. Sun et al.82 investigated the effects of
the temperature on the catalytic activity of methanol
synthesis on Cu/ZnO/Al2O3 catalysts (as shown in
Figure 7). It was observed that there is a maximum of
methanol yield at lower temperature, which is an
indication of the shifting from kinetics- to thermo-
dynamics-limited reactions. The maximum methanol
yields under higher temperature were close to the
thermodynamic equilibrium value.
Methanol synthesis exhibits different optimum opera-
tion temperature ranges when different catalysts were
used. Liaw and Chen9 reported that a 20% mixture of
Zr-Cu is a good catalyst in the lower temperature range
of 473-498 K, while a 20% mixture of Cr-Cu is the
better one in the range of 498-523 K. The Brookhaven
National Laboratory in USA tested a range of temper-
atures of 373-403 K using a mixture of NaOH, alcohol,
and acetate as the catalyst. In addition, Tsubaki et al.83
successfully decreased the reaction temperature to 423-
443 K by changing the reaction pathways through use
of methanol as the reaction solvent. The space yield was
up to 0.17 kg of MeOH/L‚h at 443 K and 30-50 bar. To
obtain a higher one-pass conversion of CO or CO2, the
tendency is to lower the reaction temperature. There-
Ind. Eng. Chem. Res., Vol. 42, No. 25, 2003 6525
fore, there have been many attempts toward the devel-
opment of an active catalyst to be able to operate at low
temperature, where equilibrium is rather favorable.84
3.2. Pressure. The methanol synthesis process has
been operated at high pressures since its invention by
BASF in the 1920s. With the development of newer
catalysts, the operating pressure was obviously de-
creased. In the late 1960s, ICI started operation at 50-
100 atm using a Cu-ZnO/Al2O3 catalyst. Deng et al.6
reported that an oxalate-coprecipitated ultrafine Cu/
ZnO/Al2O3 catalyst can be operated at 20 atm and
methanol selectivity is rather high. Simultaneously, Cu/
hydrophobic silica catalyst prepared by incipient wet-
ness impregnation could also be operated at the pres-
sure of 20 atm. Kilo et al.67 reported that methanol
synthesis could be successfully carried out at 17 atm
using Cu/ZrO2 catalysts modified by chromium and
manganese oxides. Meanwhile, Chen et al.11 even oper-
ated this process at 10 atm using Cu/ZnO/M2O3.
Considering the cost and tendency of the methanol
synthesis process, it should be operated at as much
lower pressure range as possible. Therefore, the search
for novel catalysts that can allow the synthesis to
operate at even lower pressure conditions is continuing.
3.3. Space Velocity. Space velocity is another im-
portant factor that affects the methanol synthesis
reaction. Generally, an increase in the space velocity
can decrease the rate of conversion, but the yield of
methanol and turnover frequency (TOF) of methanol
formation increases with an increase in the hourly space
velocity.82 It is interesting to note that the space velocity
has different effects when using different reactant
gases.85 In the hydrogenation of CO over a Cu/ZnO/
Al2O3 catalyst, CO conversion decreased rapidly with
increasing space velocity, while methanol selectivity
remained unchanged. However, during CO2 hydrogena-
tion, conversion decreased much more slowly and metha-
nol selectivity increased with the space velocity. Using
a Cu/ZrO catalyst, Koeppel et al.59 also investigated the
influence of the space velocity on the selectivity of
methanol. They obtained results similar to those of other
researchers. Simultaneously, they concluded that the
selectivity to methanol tends toward a finite value as
the contact time approaches zero. All of these findings
show that the choice of optimum space velocity should
be determined not only by the conversion and selectivity
but also by the type of reactant gas.
4. Deactivation of the Catalysts
Copper-based catalysts are sensitive to a variety of
deactivation factors. The thermal stability of Cu is only
superior to Ag among the commonly used metal cata-
lysts. Heating can cause easy sintering and agglomera-
tion of copper-based catalysts that have to be used in a
relatively low and narrow temperature range.50,86 To
improve the life of the copper catalyst, it is essential to
add a suitable promoter to increase its thermal stability.
Unfortunately, the loss in activity in the early stage of
the process is so great that it is very difficult to choose
the right promoter. Wu et al.73,87 added a small amount
of colloidal silica-to-copper catalyst to suppress the
agglomeration of copper and zinc sites, consequently
improving greatly the stability of the catalyst.
The life of the catalyst for methanol synthesis is
relevant to the operating pressure, in which the catalyst
deactivation rate becomes higher at higher pressures.
ZnAl2O4 support could be modified by introducing some
6526 Ind. Eng. Chem. Res., Vol. 42, No. 25, 2003
of the zinc component as zinc spinel or by doping other
promoter, which is not sufficiently refractory as a
support at 100 bar.
The catalyst deactivation caused by poisonous com-
pounds is rarely a problem in methanol synthesis. The
poisonous components such as sulfur and chlorine are
effectively removed in feed pretreatment. Of special
consideration is that copper is very sensitive to the
sulfur, chlorine, and other compounds, in which the
presence of a trace of them can cause a great loss of the
activity of the catalysts.
Methane, long-chain paraffins, or higher alcohols are
usually formed along with methanol formation, as a
result of the presence of other transition metals and
acidic or alkaline impurities in copper catalysts. Twigg
and Spencer50 reported that iron, cobalt, and nickel
catalysts have considerable activity of methanation,
which can cause the formation of methane and other
long-chain paraffins. Simultaneously, the deposition of
the alkaline or acidic impurities can respectively result
in the production of higher alcohol and high molecular
weight waxes.
5. Reaction Mechanism for Methanol Synthesis
Methanol synthesis via hydrogenation of CO or CO2
is a moderately exothermic reaction:
CO(g) + 2H2(g) f CH3OH
(∆H298 ) -91 kJ mol-1,
-1
∆G298 ) -25.34 kJ mol ) (1)
CO2(g) + 2H2(g) f CH3OH + H2O
(∆H298 ) -49.5 kJ mol-1,
∆G298 ) 3.30 kJ mol-1) (2)
Reaction (1) and (2) are all favored thermodynamically
at low temperatures, which limits its one-pass conver-
sion. To avoid the accumulation of a large amount of
reaction heat, one-pass conversion of the reactant gas
is only 15-25% in the commercial process. It is neces-
sary to set up a recycling reactor to reuse the reactant
gas that does not convert and increase the production
cost. Simultaneously, the water gas shift reaction [reac-
tion (3)] occurs as a side reaction in conventional
processes, consuming water that reaction (2) forms,
which might positively contribute to the methanol
production.
H2O + CO f H2 + CO2
(∆H298 ) -41.2 kJ mol-1,
∆G298 ) -28.6 kJ mol-1) (3)
Combination of the water gas shift reactions results in
a strong driving force, which dramatically increases the
synthesis gas conversion.88 Many research projects have
been carried out to elucidate the role of CO2 in methanol
formation. Klier35 stated that CO2 only adjusts or
controls the surface composition, oxidation state, and
dispersion of CuO in the catalyst but not as a direct
reactant. On the contrary, Chinchen et al.89,90 suggested
that carbon dioxide is the sole carbon source for metha-
nol synthesis. Simultaneously, Zhang et al.91 used CO/
H2, CO2/H2, and CO/CO2/H2 respectively as reactant
gases to investigate the function of CO2. They found that
both methanol formation rates for the individual CO
and CO2 hydrogenations were much lower than that for
CO/CO2 mixture hydrogenation and the methanol for-
mation rate for CO hydrogenation is lower than that
for CO2 at 490 K. This means that CO2 remarkably
promoted methanol formation and it is also a carbon
source in methanol synthesis. However, most research-
ers thought that both CO and CO2 could be hydroge-
nated to methanol and the predominant reaction de-
pended on the operating conditions.
Although the reaction for methanol synthesis has
been extensively investigated for nearly 4 decades, the
reaction pathway involving the copper-based catalyst
is still a topic of intensive debate. For a Cu/ZnO catalyst,
a bifunctional mechanism is currently accepted. It is
assumed that CO2 is hydrogenated on the Cu sites to
yield methanol and water and that subsequent gas-
phase transport from the Cu sites leads to the displace-
ment of relatively stable species from ZnO. However,
quite different bifunctional mechanism routes were also
postulated.
Saussey and Lavalley92 proposed the following routes:
ZnO OH(surf) + CO f HCOO(a) (4)
HCOO(a) + 2H(a) f CH3O(a) + O(surf) (5)
Cu CO2 + 3H2 f CH3OH + H2O (6)
ZnO CH3O(a) + H2O f CH3OH + OH(surf) (7)
From this mechanism, it is assumed that the gas-phase
intermediate is H2O and methoxy species are hydrated
on the ZnO sites. This is consistent with the observation
that small amounts of water in the gas feed increase
the catalyst activity.
Fakley and co-workers93 proposed another mechanism
in which methanol reacts with methanoates on the zinc
oxides to produce methyl methanoate, which ultimately
hydrogenated when in contact with copper:
Cu CO2 + 3H2 f CH3OH + H2O (8)
ZnO OH(surf) + CO f HCOO(a) (9)
HCOO(a) + CH3OH f HCOOCH3 + OH(surf) (10)
Cu HCOOCH3 + 4H(a) f 2CH3OH (11)
This route could explain the appearance of traces of
methyl methanoate in the product stream during in-
dustrial synthesis. In addition, this bifunctional mech-
anism can better explain the synergy between the
copper and zinc oxide.
Another bifunctional mechanism is proposed by Her-
man et al.22 whereby the nondissociative Cu+ sites
chemisorb and activate carbon monoxide meanwhile the
hydrogen was activated on the zinc oxide surface. The
model is illustrated in Figure 8. The initial step in the
synthesis of methanol over a Cu/ZnO catalyst is adsorp-
tion and activation of CO on the Cu+ sites and of
hydrogen on the surrounding ZnO surface sites. The
heterogeneous splitting of hydrogen and the bonding of
CO to cationic Cu+ sites represent an electrophilic
attack of the carbon end of CO by protons and a
nucleophilic attack on the oxygen end of CO by hydride
ions. It was suggested that the hydrogenolysis of the
Cu-CH2OH bond is the rate-limiting step.

Figure 8. Mechanism model for methanol synthesis (from ref 22).
Fisher and Bell94 conceived a further bifunctional
mechanism for methanol synthesis from CO/H2 on Cu/
ZrO2/SiO2 in which formate species form on zirconia and
undergo stepwise hydrogenation to methylenebisoxy,
methoxide, and finally methanol, with atomic hydrogen
being supplied through spillover from Cu. The reductive
elimination of methoxide is slow relative to other steps
in the reaction mechanism. The suppressed rate of
methanol synthesis from CO as compared to CO2
hydrogenation is the result of the absence of water
formation, which prevents the more simple release of
methoxide by hydrolysis. At the same time, the authors
compared the rates of methanol synthesis on Cu/ZrO2/
SiO2 and Cu/SiO2 catalysts. They found that the en-
hanced methanol rate on Cu/ZrO2/SiO2 as compared
with that on Cu/SiO2 could be attributed to the reaction
proceeding through the lower energy formate route on
Cu/ZrO2/SiO2, while proceeding through the energy
formyl mechanism on Cu/SiO2.
On the other hand, Tsubaki et al.83 altered the
traditional reaction path to a low temperature using an
organic alcohol (ROH). The new route can use syngas
containing CO2 and/or H2O and can be operated at
significantly low temperature and low pressure, such
as 423-443 K and 30-50 bar. It was assumed that
carbon dioxide and water are utilized as intermediates
in the novel pathway. The reaction route is composed
of several steps as listed below.
CO + H2O f CO2 + H2 (12)
CO2 + 1/2H2 + Cu f HCOOCu (13)
HCOOCu + ROH f HCOOR + CuOH (14)
HCOOR + 2H2 f ROH + CH3OH (15)
CuOH + 1/2H2 f H2O + Cu (16)
In the reaction path, Cu represents the catalytic center
of copper-based catalysts and ROH is the accompanying
alcohol. Here, alcohol acts as the catalytic liquid medium
because it was not consumed while the overall reaction
is accomplished. Involvement of alcohol in the reaction
changes the reaction route from a to b (shown in Figure
9).
Methanol synthesis95,96 from pure CO and H2 involves
carbonylation of methanol to methyl formate followed
Ind. Eng. Chem. Res., Vol. 42, No. 25, 2003 6527
Figure 9. Changing the reaction course from a high-temperature
ICI process (a) to a new low-temperature route (b) by addition of
alcohol (from ref 83).
by heterogeneous hydrogenolysis of methyl formate to
form two methanol molecules. The net result is the
reaction of hydrogen with carbon monoxide to give
methanol via the intermediate methyl formate.
CO + CH3OH f HCOOCH3 (17)
HCOOCH3 + 2H2 f 2CH3OH (18)
CO + 2H2 f CH3OH (19)
For the hydrogenation of CO2 to methanol, the pathways
are similar to those of CO. It also proceeds via formate
and methoxy intermediates. Fujitani et al.97 reported
that formate coverage on the Cu/ZnO catalysts is
proportional to the TOF for methanol formation and
that the formate hydrogenation is the rate-limiting step.
The reaction pathways can be shown as below:
CO2 + 1/2H2 f HCOO(a) (20)
HCOO(a) + 2H(a) f CH3O(a) + O(a) (21)
CH3O(a) + H(a) f CH3OH (22)
6. Discussion
Methanol synthesis from syngas hydrogenation is a
proven process for chemical industries and for the
production of environmentally clean fuels. However, its
production process still poses great challenges. On the
one hand, the syngas conversion per pass is severely
limited by reaction thermodynamics. To resolve the
limitations of thermodynamics on the conversion and
methanol yield, one of the most effective ways is to
remove the reaction heat from the reaction system.
Another measure is to develop an effective catalyst that
has a good performance at low temperatures. While the
nature of the active site and effects of the support and
promoter are still under investigation, the reaction
mechanism still remains an open question. Only when
these issues are truly overcome can the optimum
catalyst with perfect activity and selectivity be synthe-
sized.
Conversely, to develop an optimum catalyst, great
effort must be devoted to the elucidation of the active
site and the effects of the support and promoter. Of most
importance is that the methanol catalyst should possess
higher metal dispersion, larger surface area, and ul-
trafine particle, which could inhibit the deactivation
6528 Ind. Eng. Chem. Res., Vol. 42, No. 25, 2003
caused by agglomeration of the active sites and renders
higher conversion by accelerating the reactant diffusion.
Because the methanol synthesis catalysts are struc-
ture-sensitive catalysts, the differences in preparation
methods, preparation conditions, and pretreatment have
considerable influences on the structures of the cata-
lysts, which finally lead to the disparities in the catalytic
performance. Moreover, to hinder the agglomeration or
fast growth of the particles during the reduction, the
exothermic heat in the reduction of the catalyst should
be quickly taken away. Fujita’s method79 is worth
noting. The ultrafine catalyst is potentially one way to
optimize the catalyst in the future because of the highest
activity requirements for the catalyst components to
coexist in a fine interdispersion. As mentioned above,
some groups6,9,75,82,98 have already prepared ultrafine
catalyst particles that exhibited much higher catalytic
activity and selectivity for methanol synthesis.
In addition, the effect of the feed composition on the
nature of the catalyst surface and on the catalyst
activity must be further investigated. The carbon source
for methanol synthesis is another current controversy.
Using the isotopic labeling studies, some groups76,89,99,100
confirmed that methanol can mainly form from CO2 and
the function of CO in the hydrogenation of CO and CO2
is to scavenge the adsorbed oxygen to produce surface
CO2. It was realized that CO was the dominant reactant
for producing methanol. To enhance the performance
of the catalyst and obtain the optimum methanol yield,
the feed composition needs to be further optimized on
the basis of the surface science technology. Furthermore,
it is essential to prove the role of CO2 and CO in the
syngas hydrogenation reaction.
7. Conclusion
There is an increasing interest in methanol synthesis
from hydrogenation of syngas because of the importance
of natural gas and fuel cell technologies. A vast volume
of literature exists on the process and catalysts; how-
ever, the roles of the active site, the effects of the support
and promoter, and the reaction mechanism are still not
fully understood. In this paper, we have discussed these
issues in light of the latest advances in this area. The
recent prevalent view of the active site is the synergy
between the primary catalyst and support or promoter,
and most researchers accept the bifunctional mecha-
nism. Because the catalyst for methanol synthesis is
sensitive to the structure of the catalyst, the preparation
method, preparation conditions, and component signifi-
cantly influence its performance. The primary prepara-
tion method centers around the coprecipitation method,
and the Cu-based catalyst is widely used in this process.
The following key issues are identified as important to
the successful development of new catalysts for metha-
nol synthesis.
(1) An optimum catalyst should have a high specific
surface area and ultrafine or nanostuctured particles
of the metal active sites.
(2) It is highly desirable to understand the surface
molecule interaction mechanism in elucidating the
methanol synthesis kinetics.
(3) It is important to systematically characterize the
nature of the active sites and interactions among active
components, support, and promoter to be able to tailor
the structure of the catalyst.
(4) The key to increasing the one-pass conversion is
to develop the optimum catalyst active for low-temper-
ature synthesis.
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Received for review December 2, 2002
Revised manuscript received September 19, 2003
Accepted September 22, 2003
IE020979S