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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
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.
Please cite this article in press as: H. Ren, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.03.001
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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
Table 1
Physiochemical properties of Cu-based catalysts supported on g-Al2O3.
Samples
g-Al2O3
230.7
234.3
224.8
196.4
181.8
189.7
CA
CZrA
CZnA
CZZA
CZZMA
a
b
Cu dispersionb (%)
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
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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
(a)
CZZMA
TCD signal (mV)
CZZA
CZnA
CZrA
CA
0
100
200
300
400
500
o
Heating temperature ( C)
600
700
(b)
CZZMA
CZZA
CZnA
CZrA
CA
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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80
-1
-1
STYMeOH (gkgCat h )
24
STYMeOH
30
CCO2
SCO
SCH4
20
20
SMeOH
10
16
60
40
28
70
(6)
(5)
(4)
(3)
(2)
(1)
195 C
0
12
0.0
0.1
0.2
0.3
0.4
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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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
Table 2
Catalytic properties of ve catalysts in CO2 hydrogenation to methanol.a
Catalysts
CA
CZrA
CZnA
CZZA
CZZMA
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.
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Table 3
Physical and catalytic properties of CZZMA catalysts activated at different temperatures.
Activation temperature (8C)
Cu dispersiona (%)
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
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.
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
Conclusions
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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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