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JIEC-2432; No. of Pages 7


Journal of Industrial and Engineering Chemistry xxx (2015) xxxxxx

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Journal of Industrial and Engineering Chemistry


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Methanol synthesis from CO2 hydrogenation over Cu/g-Al2O3 catalysts


modied by ZnO, ZrO2 and MgO
Hong Ren, Cheng-Hua Xu *, Hao-Yang Zhao, Ya-Xue Wang, Jie Liu, Jian-Ying Liu
Air Environmental Modeling and Pollution Controlling Key Laboratory of Sichuan Higher Education Institutes, Chengdu University of Information Technology,
Chengdu 610225, PR China

A R T I C L E I N F O

Article history:
Received 17 October 2014
Received in revised form 2 March 2015
Accepted 2 March 2015
Available online xxx
Keywords:
CO2 hydrogenation
Methanol
Cu-based catalyst
Modication

A B S T R A C T

Cu/g-Al2O3 catalysts for methanol synthesis from CO2 are prepared and modied by metal oxides via
impregnation in the present work. Results indicate that promoters modication leads to the formation of
small Cu0 particles with a high dispersion, improves catalytic performance of Cu-based catalysts in
methanol synthesis. Moreover, the activation temperature is another important factor on affecting the
Cu0 dispersion and particle size. The investigation on CO2 hydrogenation shows that methanol is mainly
from hydrogenation of activated CO2 with active hydrogen on Cu0 particles, which is inhibited by high
reaction temperature due to improvement on reverse water-gas shift reaction and methanation.
2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Introduction
Carbon dioxide (CO2) has been considered as one of the main
greenhouse gases, and its increasing emissions arguably lead to the
global warming and climate changes. Simultaneously, the emitted
CO2 is also a cheap, nontoxic and abundant C1 feedstock. Therefore,
the utilization of CO2 as a raw material in the synthesis of valuable
chemicals has attracted more and more attentions as a technology
to control its emissions, but also provide a grand challenge in
exploring new concepts and opportunities for catalytic and
industrial development [13]. Among them, CO2 catalytic hydrogenation to methanol (MeOH) has been recognized as one of the
most effective and economical ways to x and utilize the emitted
CO2. It is mainly because that MeOH can be used as a fuel additive
or clean fuel, also converted as a starting feedstock to high-octane
gasoline, aromatics, olens and other chemicals such as formaldehyde, acetic acid and methyl tertiary-butyl ether so on [13].
As well known, Cu-ZnO-Al2O3 catalysts have been widely
applied in MeOH synthesis from syngas [46]. In Cu-ZnO-based
catalysts, ZnO is regarded to provide active sites for hydrogen
spillover, or as a structure-directing support controlling the
dispersion of metallic copper particles [79]. The synergetic
interactions of Cu and ZnO can improve the hydrogenation of

* Corresponding author. Tel.: +86 28 85967101; fax: +86 28 85966089.


E-mail address: xch@cuit.edu.cn (C.-H. Xu).

syngas containing H2, CO and a small amount of CO2. Therefore, the


similar catalysts system has been also used in CO2 direct
hydrogenation to MeOH [10,11]. However, it has been found that
the Cu-ZnO exhibits a poor activity for CO2 conversion and MeOH
formation, the space-time yield of MeOH is less than
9 g kgCat 1 h 1 [1113]. Other researchers [8,10,14,15] have
discovered that Cu-based catalysts supported on ZnO-Al2O3 mixed
oxides exhibit a high catalytic activity for MeOH synthesis from
CO2. Moreover, it has been also found that the introduction of ZrO2
can further improve the Cu dispersion and catalytic performance of
Cu-Zn-Al catalysts [16,17]. Therefore, ZnO-ZrO2 mixed oxides have
been directly used as the supports for Cu-based catalysts, and the
obtained catalysts exhibit an excellent catalytic performance in
CO2 hydrogenation to MeOH [2,10,15,18,19].
Among the above investigations, it is generally agreed that the
Cu0 nano-particles in catalysts are active phase for CO2 hydrogenation, and the metal oxide supports can disperse the active
copper species on the surface of catalysts. And most of the reported
Cu-based catalysts for CO2 hydrogenation are almost prepared
through co-precipitation. Recently, Urakawa and co-workers [20]
have adopt g-Al2O3 as support to prepare Cu-based catalysts via
impregnation and investigate the effect of promoters such as K and
Ba on the catalytic performance of catalysts in MeOH synthesis.
The impregnation is a well-known process with an easy operation
and controlling for catalysts preparation. It can distribute the
introduced components over the support surface with a low
amount and no loss. Therefore, the present work uses commercial

http://dx.doi.org/10.1016/j.jiec.2015.03.001
1226-086X/ 2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.

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g-Al2O3 particles as support to prepare Cu-based catalysts via


impregnation. And the promoters such as ZnO, ZrO2 or alkali
species MgO are introduced by the same method to further
disperse copper species in order to obtain the MeOH synthesis
catalysts with a high catalytic performance.
Experimental

stream and isothermally exposed to 30 ml min 1 of N2O for 30 min


to ensure complete oxidation of Cu0 to Cu+. The samples were then
ushed with Ar to remove the physically-adsorbed N2O, after
which a pulse of pure H2 was passed over samples to reduce the
surface Cu+. The dispersion, particle size and metallic surface area
of Cu on catalysts were calculated by quantifying the consumed H2
amount according to methods reported in references [10,21].
Catalytic test

Catalysts preparation
Cu/g-Al2O3 catalysts modied by ZnO, ZrO2 and MgO were
prepared via the impregnation method. Typically, ZrOCO3 was rst
solved in 10% nitric acid aqueous solution, in which the desired
amount of Cu(NO3)23H2O, Zn(NO3)26H2O Mg(NO3)26H2O and
water were then added to obtain about 165 ml mixture liquid
containing Cu2+, Zn2+, Zr4+ and Mg2+ ions with a molar ratio of
2:1:0.9:0.1. 150 g of dried g-Al2O3 (2060 mesh) particles were
then impregnated in the above-obtained metal ions aqueous
solution for 2 h at room temperature. The used amount of metal Cu
was 10 wt% relative to the weight of support Al2O3. The obtained
samples were dried at 80 8C in an oven, calcined at 600 8C for 6 h in
air, and denoted as CZZMA. For comparison, other four catalysts
such as CZZA (ions solution contained 2Cu:1Zn:1Zr), CZrA
(2Cu:1Zr), CZnA (2Cu:1Zn) and CA (only containing Cu) were
prepared according to the above method, and their Cu amount was
also 10 wt%.
Catalysts characterization
BET Surface area and pore volume of samples were obtained
from N2 adsorptiondesorption isotherms ( 196 8C) on an SSA4200 micromeritics instrument (Builder Co., Beijing). X-ray
diffraction (XRD) patterns of catalysts were recorded on a
DX-1000 powder diffractometer (Dandong Fangyuan Co., China)
operated at 40 kV and 25 mA and a scan step of 0.06 8C min 1,
using Cu Ka radiation (l = 0.15406 nm).
H2 temperature-programmed reduction (H2-TPR) of catalysts
(0.2 g) was performed on a TP-5080 adsorption instrument
(Tianjing Xianquan Co., China) with a 5% H2N2 mixture gas
(30 ml min 1) in the temperature range 20800 8C at rate of
10 8C min 1, the H2 consumption was monitored with a thermal
conductivity detector (TCD). H2 or CO2 temperature-programmed
desorption (H2-TPD or CO2-TPD) characterizations of catalysts
were performed on the above apparatus from 30 to 850 8C. 0.4 g
samples were rst pre-reduced with H2 at 350 8C for 30 min, and
then cooled to room temperature, following that a H2 or CO2
stream was introduced for adsorption (30 min). After adsorption,
the examined samples were ushed with Ar (H2-TPD) or He (CO2TPD) stream (30 ml min 1) for 30 min to remove weakly adsorbed
H2 or CO2, and at last they were heated from 20 to 700 8C at a rate of
10 8C min 1. The desorbed H2 or CO2 was also detected by TCD.
The dispersion and metallic surface area of Cu were determined
by N2O-H2 titration on the same instrument as TPR. 0.2 g catalysts
were rst reduced in H2 for 1 h at 350 8C, then cooled to 90 8C in Ar

Activity measurements of catalysts in CO2 hydrogenation were


performed in a high-pressure xed-bed reactor. 5 g catalysts
(about 7.2 ml) were placed in a stainless steel tube reactor
(in = 12 mm). Prior to reaction, the catalysts were activated at a
desired temperature in an 80 ml min 1 of pure H2 for 6 h under
atmospheric pressure. The reactor was then cooled to room
temperature. CO2 hydrogenation was carried out under reaction
conditions of 230310 8C, 1632 atm, n(H2): n(CO2) = 3: 1, gas
hourly space velocity (GHSV) = 14005000 h 1. The steady-state
activity measurements were taken after at least 8 h on the stream.
The produced H2, CO, CH4 and CO2 were quantitatively analyzed by
using gas chromatograph (GC) equipped with a TCD and TDX-01
column. MeOH in liquids were quantitatively analyzed by using
another GC with an Agilent CAM capillary column
(30 m  0.32 mm  0.25 mm lm thickness) and ame ionization
detector. CO2 conversion and carbon-based selectivity values for
the hydrogenated products such as CO and CH4 were calculated by
an internal normalization method. The space-time yield of MeOH
(STYMeOH) was dened as the amounts (grams) of MeOH produced
per kg catalyst per hour.
Results and discussion
Physiochemical properties
N2 adsorptiondesorption results (Table 1) of catalysts indicate
that CuO/g-Al2O3 (CA) has a similar BET surface area (234.3 m2 g 1)
to support g-Al2O3 (230.7 m2 g 1), however its pore volume is
decreased. It shows that the introduced copper species rst occupy
the inner surface of support and further interact with support
strongly to possibly form copper sites with a low catalytic activity.
From Table 1, it is also observed that the introduced metal oxides
promoters such as ZrO2, ZnO and MgO can further decrease the
surface area and pore volume of catalysts.
N2O-H2 titration indicates that copper species on Cu/Al2O3
exhibit a low dispersion, it is possibly because that the strong
interaction between metal and support leads to the migration of a
fraction of introduced copper species into support structure to
unreactive copper species. However, the introduction of promoters
can reduce this interaction, the dispersion and metallic surface
area of Cu0 particles on catalysts surface are improved in some
extent. Especially, the simultaneous modication of ZnO, ZrO2 and
MgO will lead to the highest Cu0 dispersion (67.5%) and the biggest
metallic surface area (45.4 m2 g 1).

Table 1
Physiochemical properties of Cu-based catalysts supported on g-Al2O3.
Samples

BET surface areaa (m2 g

g-Al2O3

230.7
234.3
224.8
196.4
181.8
189.7

CA
CZrA
CZnA
CZZA
CZZMA
a
b

Pore volumea (cm3 g


0.51
0.45
0.40
0.39
0.35
0.40

Cu dispersionb (%)

Cu0 particle sizeb (nm)

Cu0 surface areab (m2 g

22.8
26.0
20.3
33.8
67.5

4.56
4.00
5.12
3.08
1.54

15.3
17.5
13.4
22.7
45.4

Tested by N2 adsorptiondesorption at 196 8C.


Calculated from N2O-H2 titration of catalysts reduced at 350 8C.

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From XRD results (Fig. 1), it is found that the supports of all
samples exhibit g-phase Al2O3 (Pdf No. 1-1308). Both CuO/Al2O3
and CuO-ZnO/Al2O3 catalysts give weak diffraction signals
characteristics of CuO species (Pdf No. 1-1117) at 2u of 35.88,
37.48 and 49.18, respectively. However, the modication of ZrO2,
ZrO2-ZnO and ZrO2-ZnO-MgO can make these diffraction peaks
weaken or disappear. The presence of ZrO2 leads to the
disappearance of diffraction peaks characteristic of ZnO (Pdf No.
1-1136) at 2u of 31.88. But no diffraction signals assigned to ZrO2 or
MgO species are observed for CuO/Al2O3 samples modied by ZrO2,
ZrO2-ZnO and ZrO2-ZnO-MgO. It is possible because that the
introduced MgO species is too low, and ZrO2 species are dispersed
in the state of amorphous phase. No matter whether ZrO2, ZnO and
MgO can be detected, it is certain that the modication of ZrO2,
ZrO2-ZnO, and especially ZrO2-ZnO-MgO will promote the formation of amorphous CuO species with a high dispersion. It is possibly
due to the fact that the introduced alkaline MgO rst interacts with
the acidic sites of support g-Al2O3, and both ZrO2 and ZnO species
act as dispersing agents. These can give rise to the decrease on the
amount of CuO species strongly interacted with support.
H2-TPR proles of ve calcined CuO/Al2O3 catalysts (CA, CZnA,
CZrA, CZZA and CZZMA) are presented in Fig. 2. For CuO/Al2O3, a
main reduction peak and a wide shoulder peak are observed at
about 200 8C and 250 8C, respectively. The former peak is assigned
to the reduction of the highly dispersed CuO phases [20,22,23], and
the latter one is attributed to that of CuO species located in the
support structure due to the strong interaction between metal and
support [20,24]. It is also discovered that the high-temperature
reduction peak becomes weak for samples modied by ZnO and

ZrO2 (CZnA, CZrA), and even disappears for these modied by


ZnO-ZrO2 and ZnO-ZrO2-MgO mixed oxides (CZZA, CZZMA).
However, the intensities of the low-temperature reduction peaks
are increased slightly. It is further proved that the modication of
these promoters can lead to the improvement on the dispersion of
CuO species on catalysts surface through decreasing the interaction between CuO and support, which prevents the migration
metal Cu species into support structure. Simultaneously, the
reduction temperature of the highly-dispersed CuO species for
CZnA, CZrA and CZZA is slightly higher than that for CA. It is
possibly because that the introduced copper oxides exhibit
aggregation phenomenon besides migration. And the peaks
slightly shift to lower temperature as the following promoters
order: ZnO < ZrO2 < ZnO-ZrO2 < ZnO-ZrO2-MgO, and their peak
intensities also increase successively. It indicates that the
modication of promoters especially ZnO-ZrO2-MgO can give rise
to the increase on the amount of highly-dispersed CuO species
[16,25]. It is just the reason that CZZMA exhibits the highest copper
dispersion and the biggest metallic Cu0 surface area, which is in
accordance with N2O-H2 titration results.
H2-TPD (a) and CO2-TPD (b) proles of ve catalysts are
presented in Fig. 3. From Fig. 3(a), it is found that all samples
display a H2 desorption peak in the range of 30100 8C, which is
assigned to the desorption of atomic hydrogen adsorbed on the
surface of metallic Cu0 sites [16,26,27]. And another strong H2
desorption peak located in the range of 400600 8C, is also discovered
for the samples except Cu/Al2O3. It represents the desorption of
strongly-adsorbed hydrogen on either the ZnO or ZrO2 surface
through spillover from Cu0 to promoters [16,26,28]. Meanwhile,

(a)
CZZMA
TCD signal (mV)

Fig. 1. XRD patterns of CuO/Al2O3 catalysts modied by different promoters.

CZZA
CZnA

CZrA
CA
0

100

200

300
400
500
o
Heating temperature ( C)

600

700

(b)

TCD signal (mV)

CZZMA

CZZA
CZnA
CZrA
CA

Fig. 2. H2-TPR proles of the calcined CuO/Al2O3 catalysts modied by different


promoters.

100

200

300
400
500
600
o
Heating temperature ( C)

700

800

Fig. 3. H2-TPD (a) and CO2-TPD (b) results of CuO/Al2O3 catalysts modied by
different promoters.

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CZZMA gives two weak broader H2 desorption peaks in the range of


100180 8C and 185310 8C, respectively. They are possibly from
desorption of spilled-over hydrogen. These results imply that
Cu/Al2O3 modied by ZnO-ZrO2-MgO will probably exhibit a good
catalytic activity in MeOH synthesis from CO2.
From CO2-TPD results (Fig. 3(b)), it can be observed that
Cu/Al2O3 only exhibits a CO2 desorption peak at about 80 8C, which
is assigned to the weakly-adsorbed CO2. The addition of promoters
such as ZnO, ZrO2 or MgO increases the amount of weaklyadsorbed CO2, and also leads to the emergence of high-temperature desorption peak in the range of 400700 8C, which is assigned
to the strongly-adsorbed CO2 on the strong basic sites
[16,27,29]. From Fig. 3(b), it is clearly found that the simultaneous
modication of ZnO, ZrO2 and MgO makes Cu/Al2O3 catalyst
exhibit the strongest CO2 desorption peaks both in the lowtemperature range and in the high-temperature one, respectively.
It will be advantageous to the activation of CO2 during the
hydrogenation to MeOH.
Comparison on catalytic performance
From the catalytic test of ve reduced catalysts (Table 2), it can
be found that Cu/Al2O3 catalyst gives rise to a low CO2 conversion
(about 9%), a poor MeOH selectivity and STY (only 13.4% and
8 gkgCat 1h 1, respectively). It seems that the modication of ZnO
or ZrO2 has no obvious effect on improving CO2 conversion, and
however can slightly improve the selectivity and STY of produced
MeOH. Moreover, the simultaneous introduction of ZnO, ZrO2 into
Cu/Al2O3 catalyst can obviously improve MeOH formation along
with a small increase on CO2 conversion. According to the above
characterization results, it can be deduced that the improvement
on the catalytic performance of Cu/Al2O3 is due to the increase on
the copper dispersion, metallic Cu0 surface area, adsorption
capacity of H2 and CO2 after the modication of promoters. From
Table 2, Cu-ZnO-ZrO2-MgO/Al2O3 exhibits the smallest Cu0
particles (1.54 nm) with the biggest metallic surface area, highest
dispersion and strongest adsorption capacity toward H2 and CO2,
also gives the highest CO2 conversion (12.1%), MeOH selectivity
(26.0%) and STY (31.0 gkgCat 1h 1). It shows that smaller Cu0
particles are main catalytic active sites for MeOH synthesis. And
from Table 1 and 2 the catalytic performances of Cu-based
catalysts in CO2 hydrogenation to MeOH are observed to exhibit a
linear relationship with copper dispersion, particle size and surface
area of metallic Cu0, the similar results have been also discovered
32

on Cu-based catalysts from co-precipitation reported in references


[12,16,21,26,30].
MgO content
From above results, MgO species in Cu-based catalysts are
found to exhibit an important role on improving MeOH synthesis
from CO2. Therefore, the effect of MgO content on catalytic
performance of Cu/Al2O3 modied by ZnO-ZrO2-MgO is further
investigated. From results (Fig. 4), it is discovered that CO2
conversion, selectivity and STY of MeOH rst increase, and then
decrease with the increasing MgO content in catalysts. However,
CO selectivity exhibits a reverse trend. Cu/Al2O3 catalyst modied
by mixed oxides with a Cu: Zn: Zr: Mg molar ratio of 2: 1: 0.9:
0.1 gives the highest CO2 conversion, selectivity and STY of MeOH.
H2-TPR proles of Cu-ZnO-ZrO2-MgO/Al2O3 with different MgO
contents (Fig. 5) indicate that all samples exhibit an obvious H2
consumption peak at about 200 8C due to the reduction of Cu2+ to
Cu0. The presence of MgO species will make this peak shift toward
a lower temperature, however too much MgO species
(Mg/(Mg + Zr) molar ratio > 0.1) will give rise to the difcult
reduction of Cu2+. It is possibly because that the introduced MgO
species are easily adsorbed on the acid surface of support Al2O3,
which is helpful to the dispersion of copper species. However, the
abundant MgO will possibly promote the strong interaction
between CuO and the introduced oxides promoters such as ZnO,
ZrO2 and even MgO [13,22]. It is disadvantageous to the formation
of highly-dispersed active Cu0, the MeOH synthesis is hence
inhibited. On the other hand, a high MgO content gives rise to
formation of more alkali sites on catalysts, which can prevent the
CH4 formation. It seems difcult that methanation carries out on
alkali sites of catalysts. Anyway, the present data show that
Cu/Al2O3 catalyst modied by ZnO-ZrO2-MgO (CZZMA) with a Cu:
Zn: Zr: Mg molar ratio of 2: 1: 0.9: 0.1 is the optimum catalyst for
MeOH synthesis from CO2. Therefore, the effect of hydrogenation
parameters on the catalytic performance of CZZMA is further
investigated in the following work.
Gas hourly space velocity (GHSV)
Fig. 6 shows the effect of GHSV on catalytic performance of
CZZMA in MeOH synthesis from CO2 hydrogenation. It is
discovered that both CO2 conversion and MeOH selectivity on
CZZMA catalyst slightly decrease with the increasing GHSV,
however CO selectivity exhibits a reverse trend. It is possibly

80

-1

-1

STYMeOH (gkgCat h )

24

STYMeOH

30

CCO2
SCO
SCH4

20

20

SMeOH
10

16

TCD signals (a.u.)

60
40

28

Conversion & selectivity (%)

70

(6)
(5)

(4)
(3)
(2)
(1)

195 C
0

12
0.0

0.1

0.2

0.3

0.4

Molar ratio of Mg/(Zr+Mg)


Fig. 4. Effect of MgO content on catalytic properties of Cu-ZnO-ZrO2-MgO/Al2O3
reduced at 350 8C for CO2 hydrogenation at 250 8C, H2/CO2 = 3 and pressure 20 atm.

100

200

300

400

500

600

Heating temperature ( C)
Fig. 5. H2-TPR of Cu-ZnO-ZrO2-MgO/Al2O3 catalyst with a different Mg/(Mg + Zr)
molar ratio of (1) 0, (2) 0.05, (3) 0.1, (4) 0.2, (5) 0.3, (6) 0.5.

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mainly because that GHSV has no obvious effect on both CO2


conversion and MeOH selectivity. However, the high GHSV will
give rise to the obvious increase on the fed amount of reactants.
Catalyst activation temperature

Fig. 6. Effect of GHSV on catalytic properties of CZZMA reduced at 350 8C for CO2
hydrogenation at 250 8C, H2/CO2 = 3 and pressure 20 atm.

because that a high GHSV will give a short contact time of reactant
gas with catalytic active sites. It is found by some researchers
[12,16,21,26,30] that MeOH formation in CO2 hydrogenation has a
linear relationship with metallic Cu0 dispersion and catalysts
basicity. From above results, it is also found that STYMeOH exhibits a
linear relationship with copper dispersion and metallic Cu surface
area in some extent (Tables 1 and 2). Moreover, the presence of
alkali MgO species in Cu-based catalysts is helpful to improve
STYMeOH. Therefore, it is proposed that CO2 during hydrogenation
is rst activated on basic sites to form the formates intermediates
especially HCOOH*, the intermediates are then hydrogenated with
the activated H* on active Cu0 particles to directly produce MeOH.
It has been also proved theoretically that the formation of these
intermediates through activating CO2 needs a lower energy than
that of CO from CO2 hydrogenation according to density functional
theory (DFT) [31,32]. A short contact time will decrease the ratio of
activating CO2 to formates intermediates, which is disadvantageous to CO2 conversion to MeOH. It can be proved by the decrease
on selectivity and STY of MeOH with increasing GHSV. However,
CO formation is possibly from the CO2 reaction with the activated
hydrogen on Cu0, which will be still controlled by internal
diffusion. It can be proved by the relationship between CO
formation and GHSV. Although CO selectivity is discovered to
increase with increasing GHSV, and however it can be found from
Fig. 6 that its yield relative to CO2 conversion give a decreased
trend (from 7.47% to 5.90%). Therefore, it is deduced that the MeOH
formation is carried out mainly through the formates pathway.
From Fig. 6, it can be clearly found that STYMeOH over CZZMA
catalyst exhibits an obvious increase with the increasing GHSV. It is

The effect of catalyst activation temperature on MeOH


synthesis from CO2 over CZZMA is presented in Fig. 7. It can be
easily found that both selectivity and STY toward MeOH increase
with the increasing activation temperature, and however CO
selectivity exhibits a reverse trend at <250 8C. From H2-TPR results
(Fig. 2), the reduction of copper oxides to Cu0 mainly occurs at
about 200 8C, showing that it is difcult for the complete
conversion of Cu2+ to Cu0 through the activation by H2 at
170 8C. It can be concluded that the active centers for CO2
hydrogenation to MeOH are mainly the metallic Cu0 particles.
Therefore, a high temperature is needed for the activation of
copper oxides to metallic Cu0. From Table 3, it can be found that the
activation at 210 8C gives rise to a smaller metallic Cu0 particle size
and a higher Cu dispersion and metallic surface area than that at
250 8C. However, it is found that the CZZMA catalyst activated at
210 8C does not exhibit the highest catalytic activity, it is possibly
because that the formed metallic Cu0 particles are not too stable in
the present high-temperature reaction atmosphere (250 8C), can
be aggregated to larger one. It can be proved by the fact that the
detected Cu dispersion is decreased from 81.22% to 69.56% along
with an increase of Cu particle size (from 1.28 nm to 1.50 nm)
according to N2O-H2 titration results.
From Fig. 7, it can be also observed that both selectivity and STY
of MeOH decrease, however CO selectivity increases with the
increasing activation temperature at >250 8C. It is possibly due to
the fact that the higher temperature during activation by H2 can
give rise to the aggregation of metallic Cu0 particles, resulting in
the increase of particle size and decrease on Cu dispersion and
metallic surface area (see Table 3) which is in accordance with the
results obtained in our previous work [21]. The bigger Cu0 particles
give a low activity on adsorbing and activating hydrogen, which is
disadvantageous to MeOH synthesis through hydrogenation of
formates intermediates especially HCOOH*. However, it is easy
that RWGS reaction occurs on these bigger Cu0 particles. Therefore,
no obvious change is observed for CO2 conversion with the
increasing activation temperature.

Table 2
Catalytic properties of ve catalysts in CO2 hydrogenation to methanol.a
Catalysts

CA
CZrA
CZnA
CZZA
CZZMA

CO2 conversion (%)

8.98
8.85
9.34
10.87
12.12

Selectivity (%)

STYMeOH
(g kgCat 1 h

CO

CH4

MeOH

83.37
82.60
80.22
66.41
61.61

3.19
3.65
2.41
11.2
2.41

13.44
13.75
17.37
22.44
35.98

8.00
8.75
11.02
19.94
31.00

a
Catalytic hydrogenation conditions: 5 g catalysts (about 7.2 ml) reduced by
pure H2 at 350 8C, H2/CO2 molar ratio 3, GHSV 1400 h 1, hydrogenation temperature
250 8C and pressure 20 atm.

Fig. 7. Effect of activation temperature on catalytic properties of CZZMA in CO2


hydrogenation at 250 8C, H2/CO2 = 3, GHSV = 3000 h 1 and pressure 20 atm.

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Table 3
Physical and catalytic properties of CZZMA catalysts activated at different temperatures.
Activation temperature (8C)

Cu dispersiona (%)

Cu0 particle sizea (nm)

Cu0 surface areaa (m2 g

210
250
290
350
390

81.22
74.82
70.72
67.52
56.66

1.28
1.39
1.47
1.54
1.84

54.57
52.78
47.67
45.41
38.07

a
b

Calculated from N2O-H2 titration.


Catalytic reaction conditions: H2/CO2 molar ratio 3, GHSV 3000 h

MeOH selectivity (%)b

STYMeOH (g kgCat

35.48
37.99
36.78
34.82
20.86

53.50
66.25
60.90
55.25
34.00

1 b

, 5 g catalysts (about 7.2 ml), hydrogenation temperature 250 8C and pressure 20 atm.

that the high reaction temperature is helpful to the CO2


hydrogenation, however possibly lead to the aggregation of
metallic Cu0 particles to a larger size [1,2,12,16,30]. From Fig. 8,
it can be also found that CO selectivity exhibits a slow increase,
however CH4 selectivity gives a rapid increase with the increasing
reaction temperature in the high temperature range. It indicates
that the formation of Cu0 particles with larger size is helpful to the
RWGS reaction and methanation possibly through the further
hydrogenation of CO.
Hydrogenation pressure

Fig. 8. Effect of hydrogenation temperature on catalytic properties of CZZMA


activated at 250 8C in CO2 hydrogenation under the conditions of H2/CO2 = 3,
GHSV = 3000 h 1 and pressure 20 atm.

Hydrogenation temperature
The present work also investigates the effect of hydrogenation
temperature on the catalytic performance of CZZMA catalyst
activated by H2 at 250 8C. From Fig. 8, it can be observed that the
increase on CO2 conversion with the increasing hydrogenation
temperature is rapid in the low-temperature region (<270 8C) and
becomes slow in the high-temperature one (>270 8C). It indicates

The effect of hydrogenation pressure on MeOH synthesis from


CO2 over CZZMA activated by H2 at 250 8C, is present in Fig. 9. It is
found that CO2 conversion increases slowly, both STY and
selectivity of MeOH are increased rapidly with the increasing
reaction pressure. It is because that a high pressure promotes the
formation of formates intermediates on the alkali sites of catalysts
surface [15,20], which will accelerate the formation of MeOH
through the further hydrogenation with the activated H2 on
metallic Cu0 particles. Moreover, it is also found that the reaction
pressure has no obvious inuence on the CH4 formation through
methanation, and a high pressure can inhibit RWGS reaction.
When reaction pressure reaches up to 28 atm, CZZMA catalyst
gives STY and selectivity toward MeOH of 121.5 g kgCat 1 h 1 and
46.19%, respectively. Further increasing hydrogenation pressure
seemingly has no obvious function on improving MeOH formation.
From all above results, it can be deduced that during CO2
hydrogenation the MeOH formation is mainly from the interaction
of formates intermediates produced by the activated CO2 with
active hydrogen adsorbed on the metallic Cu0 particles with a
proper size; small part of CO produced from RWGS reaction can be
directly converted by H2 to MeOH [20,33]. The latter is a slow
process for MeOH synthesis. Simultaneously, direct CO2 hydrogenation to MeOH, RWGS reaction and methanation are carried out
as parallel reactions on the corresponding active sites of catalysts.
The metallic Cu0 particles with larger size exhibit a positive
function for RWGS and methanation reactions.

Conclusions

Fig. 9. Effect of hydrogenation pressure on catalytic properties of CZZMA activated


at 250 8C in CO2 hydrogenation at 270 8C, H2/CO2 = 3, GHSV = 3000 h 1.

The simultaneous modication of ZnO, ZrO2 and MgO is found


to be able to increase the copper dispersion and metallic Cu0
surface area, promote the formation of Cu0 particles with a small
size for Cu/Al2O3 catalyst prepared by impregnation. The Cu0 sites
on the Cu-based catalysts are the catalytic active centers for CO2
hydrogenation to MeOH. The activation temperature is also an
important factor affecting the metallic Cu0 particle size. The
investigation on the catalytic hydrogenation to MeOH synthesis
over Cu-ZnO-ZrO2-MgO/Al2O3 catalyst shows that a higher
reaction temperature will inhibit MeOH synthesis, and however
increase the reverse water-gas-shift and methanation reactions.
The high gas hourly space velocity and reaction pressure are
advantageous to the increase on the space-time yield of MeOH.

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Acknowledgement
This work was supported by the Major Natural Science Project of
Sichuan Provincial Department of Education under Grant No. 13Z171
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