Energy Conversion and Management 103 (2015) 886894

Contents lists available at ScienceDirect

Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

Effect of hierarchical mesomacroporous alumina-supported copper

catalyst for methanol synthesis from CO2 hydrogenation
Thongthai Witoon a,b,c,d,, Sittisut Bumrungsalee a, Metta Chareonpanich a,b,c,d, Jumras Limtrakul b,c,e
a

Center of Excellence on Petrochemical and Materials Technology, Department of Chemical Engineering, Faculty of Engineering, Kasetsart University, Bangkok 10900, Thailand
Center for Advanced Studies in Nanotechnology and Its Applications in Chemical Food and Agricultural Industries, Kasetsart University, Bangkok 10900, Thailand
c
NANOTEC-KU-Center of Excellence on Nanoscale Materials Design for Green Nanotechnology, Kasetsart University, Bangkok 10900, Thailand
d
PTT Group Frontier Research Center, PTT Public Company Limited, 555 Vibhavadi Rangsit Road, Chatuchak, Bangkok 10900, Thailand
e
Department of Materials Science and Engineering, Institute of Molecular Science and Engineering Vidyasirimedhi Institute of Science and Technology, Rayong 21210, Thailand
b

a r t i c l e

i n f o

Article history:
Received 22 May 2015
Accepted 11 July 2015
Available online 23 July 2015
Keywords:
CO2 hydrogenation
Hierarchical mesomacroporous alumina
Methanol
Catalyst
Deactivation
Stability

a b s t r a c t
Effects of pore structures of alumina on the catalytic performance of copper catalysts for CO2 hydrogenation were investigated. Copper-loaded hierarchical mesomacroporous alumina (Cu/HAl) catalyst exhibited no signicant difference in terms of CO2 conversion with copper-loaded unimodal mesoporous
alumina (Cu/UAl) catalyst. However, the selectivity to methanol and dimethyl ether of the Cu/HAl catalyst was much higher than that of the Cu/UAl catalyst. This was attributed to the presence of macropores
which diminished the occurrence of side reaction by the shortening the mesopores diffusion path length.
The Cu/HAl catalyst also exhibited much higher stability than the Cu/UAl catalyst due to the fast diffusion
of water out from the catalyst pellets, alleviating the oxidation of metallic copper to CuO.
2015 Elsevier Ltd. All rights reserved.

1. Introduction
Concerns over depletion of fossil fuels and rising CO2 emissions
are driving the need for recycling CO2 into alternative fuels. The
catalytic hydrogenation of CO2 to methanol is considered one of
the most promising processes because methanol can be used as
an energy carrier for fuel cell application [13]. Moreover, methanol can be converted to dimethyl ether (DME) [4,5] which is considered as a feasible fuel for diesel engines [6,7], or into higher
hydrocarbons according to methanol-to-olens (MTO) process
[811].
The catalysts contained Cu as a main component together with
different promoters such as Zn, Zr, Ga, Al, Si and Mg [1214] were
found to be active for CO2 hydrogenation toward methanol. Along
with main component, an appropriate support is of imperative
importance because it can act not only as dispersant but also as
stabilizer for the main component. Moreover, the interface contact
between the main component and the support can cause synergetic effect which provides the active centers for adsorption of
reactants and products, enhancing the catalytic performance. As
a consequence, most of recent studies have focused on the
Corresponding author at: Center of Excellence on Petrochemical and Materials
Technology, Department of Chemical Engineering, Faculty of Engineering, Kasetsart
University, Bangkok 10900, Thailand. Tel.: +66 2579 2083; fax: +66 2561 4621.
E-mail address: [email protected] (T. Witoon).
http://dx.doi.org/10.1016/j.enconman.2015.07.033
0196-8904/ 2015 Elsevier Ltd. All rights reserved.

development of Cu-based catalysts at the nanoscale by means of

incorporating promoters [1215], ne tuning catalyst compositions [12,16] and improving preparation procedure [13,17,18].
Another important impact of supports is the transport of reactants and products. Although the nanoporous catalysts have a large
internal surface area which contributes to their high intrinsic catalytic activity per unit catalyst weight, they usually contain small
pore size, limiting the molecules accessibility to the active sites
[1921]. It was reported that the hierarchical mesomacropore
structure could diminish diffusion limitations [19,22,23] and
extend catalyst lifetime [2426]. In addition to the activity, the
transport of reactants and products within the catalyst pellets might
also inuence the product selectivity [19,27]. Iglesia [27] proposed
that, for FischerTropsch synthesis reaction, the long chain hydrocarbon selectivity was increased by diffusion-enhanced a-olen
re-adsorption phenomena. Despite the signicant number of papers
reporting the benecial effect of the hierarchical porous material, its
application as supported copper catalyst for methanol synthesis
from CO2 hydrogenation has not yet been studied.
Herein, we report the diffusion-enhanced effects of the hierarchical mesomacroporous structure of Cu/Al2O3 catalyst for CO2
hydrogenation reaction. Cu-loaded unimodal porous alumina
catalyst was employed for the purpose of comparison. The physicochemical properties of the catalysts were characterized by means
of scanning electron microscope (SEM), N2-physisorption, mercury
porosimetry, X-ray diffraction (XRD), N2O chemisorption,

T. Witoon et al. / Energy Conversion and Management 103 (2015) 886894

H2-temperature-programmed reduction, pyridine-temperatureprogrammed desorption.

2. Experimental
2.1. Preparation of alumina supports
Hierarchical mesomacroporous alumina (HAl) was prepared
following the method described by Tokudome et al. [28]. In brief,
0.08 g poly(ethylene oxide) (PEO), having viscosity-averaged
molecular weight of 1  106, was dissolved in a mixture of
4.0 mL ethanol and 5.5 mL deionized water at room temperature
for 12 h. Then 4.32 g aluminum chloride hexahydrate
(AlCl36H2O) was added to the PEOwaterethanol solution that
was being stirred at room temperature until the homogeneous
solution was achieved. 3.75 mL propylene oxide (PO) was added
into the solution in order to initiate the hydrolysis-condensation
reaction. After stirring for 1 min, the resultant homogeneous solution was transferred into the glass tube, sealed and kept at 40 C for
gelation. Subsequently, the wet gel was aged for 24 h and dried at
40 C. The obtained alumina monolith was calcined at 600 C in air
at heating rate of 10 C/min for 12 h. Unimodal mesoporous alumina (UAl) was prepared using the similar procedure as mentioned
above except the addition of PEO.
2.2. Preparation of copper-loaded alumina catalysts
In order to clearly distinguish the effects of the presence of
macropores, the alumina supports were ground and sieved into
two fractions, 0.0750.090 mm and 0.8502.000 mm denoted as
-S and -L, respectively. 10 wt% copper-loaded alumina catalysts
were prepared by incipient wetness impregnation method. The
calcined unimodal and hierarchical porous alumina supports were
impregnated with the desired amount of copper nitrate trihydrate
(Cu(NO3)23H2O) in aqueous solution. The slurry mixture was stirred at 60 C for 2 h, dried at 100 C for 12 h and calcined at 600 C
and a heating rate of 2 C/min for 2 h. The copper-loaded unimodal
and hierarchical alumina catalysts were designated as Cu/UAl and
Cu/HAl, respectively.
2.3. Characterization of copper-loaded alumina catalysts
The surface morphology of the alumina supports was assessed
with the application of a scanning electron microscope (SEM; FEI
Quanta 450) equipped with energy-dispersive X-ray spectroscopy
(EDS). The SEM measurement was taken at 20.0 kV. The samples
were sputtercoated with gold prior to analysis.
The elemental analysis of the catalysts was tested with inductively coupled plasmaoptical emission spectroscopy (ICPOES,
Optima 4300 DV, Perkin-Elmer).
The macropores size distribution was measured with a mercury
porosimetry (PoreMaster 33). The BET surface area, mesopores size
distribution and pore volume of the alumina supports and the
Cu-loaded alumina catalysts were determined by N2-sorption measurement with a Quantachrome Autosorb-1C instrument at
196 C. The copper (Cu0) surface area of the catalysts was obtained
by N2O-titration measurements as described elsewhere [12].
X-ray diffraction (XRD) patterns of the alumina supports and
the Cu-loaded alumina catalysts were attained on a diffractometer
(Bruker D8 Advance) with Cu Ka radiation. The measurements
were made at temperatures in a range of 1575 on 2h with a step
size of 0.05. The diffraction patterns were analyzed according to
the Joint Committee on Powder Diffraction Standards (JCPDS).
Temperature programmed reduction (TPR) experiments were
conducted using a DSCTGA 2960 thermal analyzer. A 10 mg

887

sample was pretreated in a ow of N2 (100 mL/min) at a rate of

10 C/min until 400 C was achieved; the 400 C temperature was
maintained for 30 min, then the sample was cooled to 100 C.
Once the 100 C temperature was reached and stabilized, the sample was heated under owing 10% v/v H2 (He as a balance gas) at a
heating rate of 4 C/min from 100 C to 400 C.
Temperature programmed desorption (TPD) experiments were
performed with the same apparatus as the TPR measurement using
pyridine as a probe molecule following the method described by
Mohamed and Abu-Zied [29]. Prior to pyridine adsorptions, the
alumina supports and the Cu-loaded alumina catalysts were calcined at 400 C to remove physically and chemically adsorbed
water from their surface. Then the samples were transferred into
desiccator containing liquid pyridine. The samples were maintained in contact with pyridine vapor at room temperature for a
week, prior to acidity measurements. The pyridine desorption
measurement was conducted in a ow of N2 (100 mL/min) at a
heating rate of 4 C/min from room temperature to 600 C. The
amount of acidity was determined from the weight loss due to
the desorption of pyridine.
2.4. Catalytic activity test
CO2 hydrogenation was carried out in a xedbed stainless steel
reactor (7.75 mm inner diameter). In a typical experiment, 0.5 g
catalyst was diluted with 0.5 g inert silica sand. The catalyst was
reduced in situ under atmospheric pressure with owing H2
(60 mL/min) at 350 C and a heating rate of 2 C/min for 4 h.
After the reduction, the temperature was cooled to 200 C under
owing N2; subsequently a ow of CO2 and H2 mixture (CO2:H2
molar ratio of 1:3) was fed through the reactor. The feed ow rate
was set at 60 mL/min. The reactor pressure was slowly raised to
30 bars, and the reactor was heated to a variety of temperatures
(240, 260, 280, 300 and 320 C). The efuent gaseous products
were analyzed by using gas chromatography. Analysis of H2, CO,
CO2, and N2 was performed using GC2014 gas chromatography
equipped with a thermal conductivity detector (TCD) and a
Unibead-C column. Methanol, DME and other hydrocarbon products were analyzed by using GC 8A equipped with a ame ionization detector (FID) and a Chromosorb WAW (20% PEG) column. The
activityselectivity data were calculated by mass balance from an
average of three independent measurements. The selectivity has
been calculated taking into account three major products, including methanol, CO and DME, i.e. only a trace amount of methane
was observed at 320 C which was excluded for selectivity calculation. The errors were within 3%. CO2 conversion, selectivity to
methanol, CO and DME are dened as follows:
CO2 conversion %

moles methanol 2  moles DME moles CO  100

moles CO2;in

Methanol selectivity %

CO selectivity %

moles methanol  100

moles methanol 2  moles DME moles CO

moles CO  100
moles methanol 2  moles DME moles CO

DME selectivity %

2  moles DME  100

moles methanol 2  moles DME moles CO

3. Results and discussion

The apparent morphology of alumina supports was examined
by means of SEM. Hierarchical mesomacroporous alumina (HAl)
sample (Fig. 1a) exhibited the presence of 3-dimentionally

888

T. Witoon et al. / Energy Conversion and Management 103 (2015) 886894

interconnected macropores with a uniform size of ca. 2 lm

whereas unimodal mesoporous alumina (UAl) sample (Fig. 1b)
showed a dense surface, caused by an aggregation of alumina
nanopartciles, and contained no macropores. Hg-porosimetry was
conducted to complement the SEM analysis. The HAl sample
(Fig. 1c) possessed two different scales of a bimodal pore size distribution: 0.0050.020 lm and 13 lm. The latter scale centered at
1.77 lm corresponding to the macropores as observed by the SEM
image (Fig. 1a). The UAl sample (Fig. 1d) showed a broad peak in
the region 0.0050.020 lm (Fig. 1d) representing the interparticle
spaces between alumina nanoparticles. The pore size in the mesopores region of both samples was further investigated by
N2-sorption measurement.
Fig. 2a and b shows the N2 adsorptiondesorption isotherm and
the corresponding pore size distribution of the UAl and HAl supports and the Cu/UAl and Cu/HAl catalysts. Textural properties of
those samples are summarized in Table 1. Both UAl and HAl samples exhibited a type IV isotherm with a H2 hysteresis loop, indicating that both samples contained mesopores with an ink-bottle
structure. After calcination of copper nitrate-loaded alumina supports (Cu/UAl and Cu/HAl catalysts), the type of isotherm for both
catalysts was remained the same which was an indication for
preservation of the mesopore structure. A monotonic decrease in
BET surface areas, pore volumes and pore diameters of Cu/UAl
and Cu/HAl catalysts compared to the parent ones could be attributed to the deposition of copper oxide in the mesopores of alumina
supports.
XRD pattern of the UAl and HAl samples is shown in Fig. 3. Both
samples exhibited two broad peaks centered at 2h angles of 45.7
and 66.6, characteristics of an amorphous structure. For Cu/UAl
and Cu/HAl catalysts, the XRD patterns were identical to those of
the supports, i.e., no discernible peaks associated with copper
oxide species were detected. Previous studies have reported that
the dispersion capacity of copper oxide on the surface of alumina
is 0.75 mmol Cu2+/100 m2 Al2O3 [30,31]. The actual copper loading

4.0

2.5
2.0

3.0

1.5
2.0
1.0
1.0

0.5

0.0

0.0
0.001 0.01

0.1

10

Pore diameter (m)

100 1000

4.0

2.5

(d)
2.0

3.0

1.5
2.0
1.0
1.0

0.5

0.0

0.0
0.001

Pore volume (cm3/g)

(c)

Cumulative pore volume (cm3/g)

(b)

Pore volume (cm3/g)

Cumulative pore volume (cm3/g)

(a)

determined by ICP analysis of the Cu/UAl and Cu/HAl catalysts was

about 10.24 and 10.54 wt%, which were equivalent to 0.56 mmol
Cu2+/100 m2 Al2O3 and 0.67 mmol Cu2+/100 m2 Al2O3, respectively.
This indicated that copper oxide particles highly dispersed in the
alumina matrix at the atomic level, consequently, no formation
of CuO bulk on the surface of alumina.
The reducibility of CuO over two different supports was
observed by H2-TPR; the result is shown in Fig. 4. The H2-TPR prole of the Cu/UAl and Cu/HAl catalysts appeared the reduction
peak centered at around 261 and 258 C, an indication of a reduction of highly dispersed CuO nanoparticles [3133]. Obviously, CuO
species were continuously reduced from 290 to 400 C, indicating a
strong interaction between CuO species and alumina supports, i.e.,
copper was incorporated into the alumina matrix, possibly a formation of a spinel CuAl2O4 structure [3133].
Fig. 5 shows pyridine-TPD measurement of the alumina supports and Cu-loaded alumina catalysts. Also, the quantitative estimation of acid sites is shown in Table 1. The UAl and HAl supports
exhibited a similar desorption pattern with two distinct regions of
300390 C and 400450 C, indicating the existence of medium
and strong acid sites on the surface of the alumina supports.
Adding Cu onto the alumina supports (Cu/UAl and Cu/HAl catalysts) signicantly reduced the total number of acid sites and the
acid strengths, possibly due to the interaction between CuO and
unsaturated aluminum ion. Also shown in Table 1, the Cu surface
area of the Cu/UAl catalyst was slightly higher than the Cu/HAl catalyst which could be attributed to the higher surface area of the
UAl support. All characterization results clearly indicate that the
major difference between Cu/UAl and Cu/HAl catalysts is the presence of macropores in Cu/HAl catalyst.
Fig. 6 shows CO2 conversion and the production selectivity in
terms of methanol, CO and DME. It was found that CO2 conversion
of all catalysts monotonically increased with ascending reaction
temperature (Fig. 6a). The CO2 conversion at each reaction
temperature of the Cu/HAl-S catalyst was found to be lower than

0.01

0.1

10

100 1000

Pore diameter (m)

Fig. 1. SEM images (a and b) and pore size distribution measured by mercury porosimetry (c and d) of unimodal mesoporous alumina (UAl) and hierarchical meso
macroporous alumina (HAl) supports.

889

400

(a)

UAl
HAl
Cu/UAl
Cu/HAl

300

200

100

0
0.0

0.2

0.4

0.6

0.8

Adsorption dV/d (log D) (cm 3/g)

Volume of gas adsorbed (cm3/g)

T. Witoon et al. / Energy Conversion and Management 103 (2015) 886894

1.0

(b)

3.0

UAl
HAl
Cu/UAl
Cu/HAl

2.0

1.0

0.0
1

10

100

1000

Pore diameter (nm)

Relative pressure (P/P0)

Fig. 2. N2-sorption isotherms (a) and pore size distribution (b) of UAl and HAl supports and Cu/UAl and Cu/HAl catalysts.

Table 1
Textural properties, copper surface area, and surface acidic properties of the alumina supports and the Cu-loaded alumina catalysts.
BET surface area
(m2/g)

Pore volume
(cm3/g)

Copper surface area

(m2/g)

Medium acid sites

(mmol/g)

Strong acid sites

(mmol/g)

Total acid sites

(mmol/g)

UAl
HAl
Cu/UAl
Cu/HAl

324
275
154
124

0.51
0.45
0.29
0.24

1.87
1.50

0.37
0.22
0.15
0.12

0.87
0.75
0.14
0.12

1.24
0.97
0.29
0.24

258

Catalysts

Cu/HAl
HAl

UAl

-Al2O3: PDF 00-050-0741

CuO: PDF 01-073-6023

10

20

30

40

50

60

70

Cu/HAl
261

H2 consumption (a.u.)

Intensity (a.u.)

Cu/UAl

80

2-Theta (degree)
Fig. 3. XRD patterns of UAl and HAl supports and Cu/UAl and Cu/HAl catalysts.

the Cu/UAl-S catalyst due to a lower Cu surface area (Table 1) of the

Cu/HAl-S catalyst so that the activity was re-calculated and was
dened as CO2 conversion per Cu surface area which represented
the intrinsic activity and the inherent property of the catalysts;
the result is shown in Fig. 1S. The slight difference in CO2 conversion at each reaction temperature was observed when comparing
between the Cu/HAl and the Cu/UAl catalysts at the identical particle size. This indicates that the mesopores (7 nm) of the Cu/HAl
and Cu/UAl catalysts are large enough to facilitate diffusion of gas
molecules from bulk uid to active sites located inside the mesopores, i.e., no existence of pore diffusion (internal diffusion) resistance. In other words, the presence of macropores does not
signicantly contribute to the CO2 conversion. However, the effect
of macropores becomes more pronounced by comparing the
results in terms of selectivity. Comparing between the Cu/HAl-S
and the Cu/UAl-S catalysts, the Cu/HAl-S catalyst exhibited higher

Cu/UAl
150

200

250

300

350

400

Temperature (oC)
Fig. 4. H2-TPR proles of Cu/UAl and Cu/HAl catalysts.

methanol (Fig. 6b) and DME (Fig. 6d) selectivities and lower CO
selectivity at any reaction temperature (Fig. 6c). The similar trend
was also observed when the catalysts with the larger particle size
(Cu/HAl-L and Cu/UAl-L) were compared.
In fact, CO2 hydrogenation over methanol synthesis catalyst
involves two competitive reactions. The rst one is the targeted
methanol synthesis (Eq. (1)) and the second one is reverse
watergas shift (RWGS) reaction (Eq. (2)). Methanol formed in
Eq. (1) can undergoes dehydration to produce DME and water
(Eq. (3)) over acidic sites, that present on the surface of the alumina

T. Witoon et al. / Energy Conversion and Management 103 (2015) 886894

supports as indicated by pyridine-TPD. In addition, methanol can

subsequently decompose to produce carbon monoxide and hydrogen at a temperature above 200 C (Eq. (4)) [34,35]. The occurrence
of these different pathways strongly inuences the product
distribution.

404

333

890

Cu/HAl
Cu/UAl

418

CO2 3H2 $ CH3 OH H2 O

370

Pyridine desorption (a.u.)

CO2 H2 $ CO H2 O

400

500

600

Temperature (0C)
Fig. 5. Pyridine-TPD proles of Cu/UAl and Cu/HAl catalysts.

50

30

Cu/UAl-S
Cu/UAl-L
Cu/HAl-S
Cu/HAl-L

20

(a)

(b)
Methanol selectivity (%)

CO2 conversion (%)

It should be mentioned again that the active species between

the Cu/HAl and Cu/UAl catalysts are very similar in nature. This
indicates that the transport of reactant and products within the
catalyst pellet affects the product selectivity. Bonura et al. [35]
reported that the space velocity played a vital role on the product
selectivity from CO2 hydrogenation reaction. Increasing the space
velocity from 10,000 to 80,000 h1 led to the progressive increase
of the methanol selectivity at expense of carbon monoxide which
could be due to the potential occurrence of side reactions, i.e.,
methanol decomposition (Eq. (4)). The similar trend was also
observed by Zhang et al. [36] and Gao et al. [37].
Similar to the increase of space velocity, the macropores provided a fast diffusion of methanol out from the catalyst pellets.
In addition, the diffusion distance inside the mesopores of the
Cu/HAl-S catalyst was shorter than that of the Cu/UAl-S catalyst
when compared at the same particle size (see Scheme 1). These

UAl
300

1

DH 90:6 kJ mol

1
2

1

HAl

200

1

DH 41:2 kJ mol

2CH3 OH $ CH3 OCH3 H2 O DH 23:4 kJ mol

CH3 OH $ CO 2H2

100

1

DH 49:4 kJ mol

10

40

Cu/UAl-S
Cu/UAl-L
Cu/HAl-S
Cu/HAl-L

30

20

10

0
220

240

260

280

300

320

340

220

240

260

280

300

320

340

Temperature (oC)

Temperature (oC)
100

15

(c)

(d)
DME selectivity (%)

CO selectivity (%)

90
80
70
60

Cu/UAl-S
Cu/UAl-L
Cu/HAl-S
Cu/HAl-L

50

10

Cu/UAl-S
Cu/UAl-L
Cu/HAl-S
Cu/HAl-L

40
220

240

260

280

300

Temperature (oC)

320

340

220

240

260

280

300

320

340

Temperature (oC)

Fig. 6. CO2 conversion (a), methanol selectivity (b), CO selectivity (c) and DME selectivity (D) as a function of reaction temperature of Cu/UAl-S, Cu/UAl-L, Cu/HAl-S and
Cu/HAl-L catalysts. S and L are denoted as the average pellet size of 0.0825 and 1.425 mm, respectively.

891

T. Witoon et al. / Energy Conversion and Management 103 (2015) 886894

both molecular diffusion and Knudsen diffusion are important.

Thus, the diffusion coefcient in mesopore is calculated by Eq. (6).

CO2

1
1
1

Dpore D0A DK

H2

Mesopore
CO2
H2

where D0A and DK are molecular diffusion coefcients of component

A (cm2/s) with respect to the total gas mixture and Knudsen diffusion coefcient (cm2/s), respectively. D0A and DK could be calculated
from the following equations:

Cu/UAl catalyst

D0A

Metallic
copper

CO2
H2

DAB 0:001858

Table 2
Effective diffusion coefcients in mesopores and macropores of different catalysts.
Effective diffusion coefcients  103 (cm2/s)
Mesopores
CO2

H2

CH3OH

CO2

H2

CH3OH

240
260
280
300
320

1.02
1.03
1.06
1.08
1.10

2.94
3.08
3.23
3.36
3.49

0.97
1.01
1.05
1.09
1.12

Cu/HAl

240
260
280
300
320

0.82
0.84
0.86
0.88
0.90

2.38
2.49
2.61
2.71
2.82

0.79
0.82
0.85
0.88
0.91

10.80
11.06
11.42
11.91
12.36

11.54
12.42
13.36
14.29
15.23

5.64
6.12
6.61
7.09
7.58

probably lessen methanol decomposition reaction (Eq. (4)), and

thus provided the higher methanol selectivity compared to the
Cu/UAl-S catalyst. With increasing the average catalyst pellet size
(from 0.0825 mm to 1.425 mm), the decrease in CO2 conversion
was observed for both Cu/UAl and Cu/HAl catalysts, indicating
the existence of diffusion limitation in pores of catalysts. To gain
more information, the effective diffusion coefcients (De) of reactant and product molecules in mesopores and macropores are calculated by using Eqs. (5)(10) as shown below [38,39]; and the
results are given in Table 2.

where e is catalyst porosity; s is catalyst tortuosity; and Dpore represents diffusion coefcient of gas in either mesopores or macropores.
Knudsen number was pre-determined to justify the most suitable
equation for calculating diffusion coefcient in mesopores and
macropores. Knudsen number in mesopores of the reactants and
products was found to be in the range of 0.51.1, indicating that

1
MA

M1B

Pr2AB XAB

12
9

where T is temperature (K); MA and MB are molecular weight of

components A and B, respectively; P is total pressure (atm); rAB is
effective collision diameter (); XAB is collision integral. The diffusion coefcient in macropores can be calculated by Eq. (7) because
the macropore size is much larger than the mean free path of gas
molecules. The catalyst tortuosity (s) can be calculated from Eq.
(10), given by Beckman [40] for heterogeneous catalysts.

Macropores

Cu/UAl

e
s

 12
T
M

Scheme 1. Illustration of gas diffusion inside mesopores of the Cu/UAl and Cu/HAl
catalysts.

De Dpore

T2

Cu/HAl catalyst

Reaction
temperature
(C)

1  yA
D
DyACC DyAD


where DAB, DAC, DAD are respective binary diffusion coefcients; and
yA, yB, yC, are mole fractions of the components in the mixture; T is
temperature (K); M is molecular weight of gas molecules; and rp is
pore radius (cm). The binary diffusion coefcient (cm2/s) can be calculated by the following equation:

Macropore

Catalysts

yB
DAB

DK 9700rP

CO2
H2

Mesopore

e
1

1  1  e3

10

Due to the fact that the diffusion coefcient in mesopores of CO2

was 3-fold lower than that of H2, this implied the depletion of CO2
along the intra-pellet pores. In other words, the slower molecular
transport of CO2 to active sites inside the mesopores resulted in
lowering the catalyst performance, including the decrease of CO2
conversion. For the catalyst without macropores (Cu/UAl), methanol selectivity of the catalyst with larger pellet size (Cu/UAl-L) was
considerably lower than that of the smaller one (Cu/UAl-S) when
compared at the same reaction temperature. This could be attributed to the increase in the residence time of methanol diffusion
inside the catalyst pellets, and thus increasing the probability of
methanol decomposition. In contrast, for the Cu/HAl-L catalyst
with macropores, the methanol selectivity was slightly lower than
that of the Cu/HAl-S catalyst when compared at reaction temperature of 240 and 260 C, suggesting the shorter residence time of
methanol diffusion inside the catalyst pellets. However the difference in methanol selectivity between the Cu/HAl-L and Cu/HAl-S
catalysts was larger when the temperature was further increased
(280 C, 300 C, and 320 C). This could be explained by the fact
that methanol decomposition became kinetically more favored at
the higher temperature. At higher temperature, the methanol
decomposition rate increased more rapidly than the diffusion rate,
resulting in the lower methanol selectivity. The CO2 conversion
and methanol selectivity of the Cu/UAl and Cu/HAl catalysts were
compared with those of previous works using copper-loaded commercial Al2O3 support as the catalyst. The results are shown in
Table 3. It was found that the Cu/HAl catalyst possessed a superior
performance in terms of methanol selectivity which was 2.4
5.5-fold greater than those catalysts.
Fig. 7 shows the CO2 conversion and selectivity of methanol, CO
and DME versus the time-on-stream over the Cu/UAl-S and

892

T. Witoon et al. / Energy Conversion and Management 103 (2015) 886894

Table 3
Comparison of catalytic performance of Cu/HAl and Cu/UAl catalysts and other Cu/Al2O3 catalysts for the synthesis of methanol from CO2 hydrogenation.
Catalysts

Operating conditions

CO2 conversion (%)

Methanol selectivity (%)

Refs.

Temperature (C)

Pressure

10 wt%Cu/Al2O3

250

20 atm

5 wt%Cu/Al2O3

8.98

13.44

[14]

220

30 bar

n/a

7.5

[41]

12 wt%Cu/Al2O3

240
260

30 bar
30 bar

10.7
15.6

16.9
10.7

[42]

10 wt%Cu/UAl

240
260
280

30 bar
30 bar
30 bar

6.4
13.5
18.8

35.7
23.1
16.1

This work

10 wt%Cu/HAl

240
260
280

30 bar
30 bar
30 bar

5.6
10.5
15.0

41.7
30.3
21.7

This work

n/a: not available.

Fresh catalysts

15

10

Cu/UAl-S
Cu/HAl-S

30

Regenerated catalysts

Methanol selectivity (%)

CO2 conversion (%)

20

Cu/UAl-S
Cu/HAl-S

Regenerated catalysts

Cu/UAl-S
Cu/HAl-S

Cu/UAl-S
Cu/HAl-S

25
20
15
10
5

(a)

(b)

0
0

20 40 60 80 100 120 140 160 180 200

Time on stream (h)

90

Fresh catalysts

15

Regenerated catalysts

80

70

Cu/UAl-S
Cu/HAl-S

Cu/UAl-S
Cu/HAl-S

20 40 60 80 100 120 140 160 180 200

Time on stream (h)

DME selectivity (%)

CO selectivity (%)

Fresh catalysts

Regenerated catalysts

Cu/UAl-S
Cu/HAl-S

Cu/UAl-S
Cu/HAl-S

10

(c)

60

Fresh catalysts

0
0

20 40 60 80 100 120 14 0 160 180 200

Time on stream (h)

(d)

20 40 60 80 100 120 140 160 180 200

Time on stream (h)

Fig. 7. CO2 conversion (a), selectivity of methanol (b), CO (c) and DME (d) as a function of time-on-stream of fresh and spent catalysts. Reaction conditions: T = 280 C, P = 30
bars, ow rate = 60 mL min1.

Cu/HAl-S catalysts. The CO2 conversion of the Cu/UAl-S catalyst

was rst increased from 12.92 to 17.44 within 2 h and then substantial loss its activity ca. 6.2% during the 100 h time-on-stream
experiment, while the Cu/HAl-S catalyst exhibited much greater
durability, experiencing only a 2.77% (14.81% ? 12.04%) reduction
under identical reaction conditions. This indicated that the
Cu/HAl-S catalyst had a higher stability than the Cu/UAl-S catalyst.
Regarding the selectivity of methanol and CO, the Cu/UAl-S catalyst
lost its selectivity to methanol approximately 4.13% of its initial
selectivity while its selectivity to CO progressively increased from
76.48% to 82.24% during the 100 h time-on-stream experiment. For
the Cu/HAl-S catalyst the selectivity to methanol and CO were
found to be almost constant. The change in product selectivity with

time-on-stream suggests the change in the active sites of the

catalysts.
The XRD was used to verify phase of the reduced and spent catalysts (Fig. 8). The XRD pattern of the reduced catalysts (Cu/HAl-S
and Cu/UAl-S) appeared the peak at 2h angles of 43 corresponded
to the presence of metallic copper (JCPDS 01-089-2838), which
was the active phase for methanol synthesis from CO2 hydrogenation. After the 100 h time-on-stream experiment, the peaks at 2h
angles of 35.5 and 38.6, which were indexed to the CuO crystal
phase, were observed along with the reduction of peak intensity
of the metallic copper, indicating the transformation of the metallic copper to the CuO. This could be explained by the fact that a
large amount of water produced by the Eqs. (1)(3) oxidized the

T. Witoon et al. / Energy Conversion and Management 103 (2015) 886894

importance of transport of reactants and products in pores of the

catalysts for methanol synthesis from CO2 hydrogenation

CuO
Cu

Acknowledgements

Intensity (a.u.)

Spent Cu/HAl catalyst

This work was nancially supported by the Thailand Research

Fund (Grant No. TRG5780258), the Center of Excellence on
Petrochemical and Materials Technology (PETROMAT), the
National Research University Project of Thailand (NRU), the
Nanotechnology Center (NANOTEC), NSTDA, Ministry of Science
and Technology, Thailand through its program of Center of
Excellence Network, Rayong Institute of Science and Technology
Foundation, and the Kasetsart University Research and
Development Institute (KURDI). Financial support for Mr. Sittisut
Bumrungsalee from Faculty of Engineering, Kasetsart University
is also appreciated.

Spent Cu/UAl catalyst

Reduced Cu/HAl catalyst

Reduced Cu/UAl catalyst

10

15

20

25

893

30

35

40

45

50

55

2-Theta (degree)
Fig. 8. XRD patterns of reduced and spent catalysts.

metallic copper sites to CuO [43,44]. The XRD pattern of the spent
Cu/HAl-S catalyst exhibited the lower peak intensity of CuO and
higher peak intensity of Cu compared to those of the spent
Cu/UAl-S catalyst, indicating the faster oxidation rate of metallic
copper over the Cu/UAl-S catalyst. This is consistent with the faster
deactivation of this catalyst. In addition to partial oxidation of
metallic copper by water, water has a negative effect for dehydration of methanol over Al2O3 catalyst as water molecules could
strongly adsorb on the active sites [4547]. As a result, both
Cu/UAl-S and Cu/HAl-S catalysts are commonly deactivated
through water poisoning. Interestingly the DME selectivity was
almost constant in the case of Cu/HAl-S catalysts, in contrary; it
was gradually decreased with time-on-stream over the Cu/UAl-S
catalyst. We therefore concluded that the presence of macropores
could promote the rate of water removal from catalyst pellets, and
thus prolong the lifetime of the catalysts.
As a detectable change of metallic copper to copper oxide in
accordance with the substantial decrease of catalytic activity was
observed, the spent catalysts after 100 h time-on-stream experiment were reduced with owing H2 (60 mL/min) at 350 C and a
heating rate of 2 C/min for 4 h in order to regenerate and perform
the activity test. Note that the efuent gases were analyzed by gas
chromatography which would enable to see if carbonaceous species on the catalysts surface are converted to methane during the
regeneration process. As a result, no methane formation was
observed, indicating that the partial oxidation of metallic copper
was the main reason for catalyst deactivation. After regeneration
(Fig. 7), almost similar CO2 conversion and catalyst deactivation
trend were observed compared to those of the fresh catalysts.
Notably, methanol and DME selectivities over the spent catalysts
were restored after regeneration with H2, indicating that the deactivation phenomena of both catalysts were almost fully reversible.
4. Conclusion
The catalytic activity for methanol synthesis from CO2 hydrogenation was strongly affected by the pore structure of the catalysts. Cu-loaded hierarchical mesomacroporous alumina catalyst
(Cu/HAl) exhibited the higher methanol selectivity and stability
than Cu-loaded unimodal mesoporous alumina catalyst (Cu/HAl).
The enhanced methanol selectivity and stability can be assigned
to the inhibited undesirable reactions induced by the shortened
mesopore diffusion path length. This nding emphasizes the

Appendix A. Supplementary material

Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.enconman.2015.
07.033.
References
[1] Karim NA, Kamarudin SK. An overview on non-platinum cathode catalysts for
direct methanol fuel cell. Appl Energy 2013;103:21220.
[2] Yan XH, Zhao TS, An L, Zhao G, Zeng L. A crack-free and super hydrophobic
cathode micro-porous layer for direct methanol fuel cells. Appl Energy
2015;138:3316.
[3] Baneshi J, Haghighi M, Jodeiri N, Abdollahifar M, Ajamein H. Homogenous
precipitation synthesis of CuOZrO2CeO2Al2O3 nanocatalyst used in
hydrogen production via methanol steam reforming for fuel cell
applications. Energy Convers Manage 2014;87:92837.
[4] Witoon T, Permsirivanich T, Kanjanasoontorn N, Akkaraphataworn C, Seubsai
A, Faungnawakij K, et al. Direct synthesis of dimethyl ether from CO2
hydrogenation over CuZnOZrO2/SO2
4 ZrO2 hybrid catalysts: effects of
sulfur-to-zirconia ratios. Catal Sci Technol 2015;5:234757.
[5] Ladera RM, Ojeda M, Fierro JLG, Rojas S. TiO2-supported heteropoly acid
catalysts for dehydration of methanol to dimethyl ether: relevance of
dispersion and support interaction. Catal Sci Technol 2015;5:48491.
[6] Park SH, Lee CS. Applicability of dimethyl ether (DME) in a compression
ignition engine as an alternative fuel. Energy Convers Manage
2014;86:84863.
[7] Wei Y, Wang K, Wang W, Liu S, Chen X, Yang Y, et al. Comparison study on the
emission characteristics of diesel- and dimethyl ether-originated particulate
matters. Appl Energy 2014;130:35769.
[8] Li J, Miao P, Li Z, He T, Han D, Wu J, et al. Hydrothermal synthesis of
nanocrystalline H[Fe, Al]ZSM-5 zeolites for conversion of methanol to gasoline.
Energy Convers Manage 2015;93:25966.
[9] Aghamohammadi S, Haghighi M. Dual-template synthesis of nanostructured
CoAPSO-34 used in methanol to olens: effect of template combinations on
catalytic performance and coke formation. Chem Eng J 2015;264:35975.
[10] lvaro-Muoz T, Sastre E, Mrguez-lvarez C. Microwave-assisted synthesis of
plate-like SAPO-34 nanocrystals with increased catalyst lifetime in the
methanol-to-olen reaction. Catal Sci Technol 2014;4:43309.
[11] Chen J, Li J, Yuan C, Xu S, Wei Y, Wang Q, et al. Elucidating the olen formation
mechanism in the methanol to olen reaction over AlPO-18 and SAPO-18.
Catal Sci Technol 2014;4:326877.
[12] Arena F, Barbera K, Italiano G, Bonura G, Spadaro L, Frusteri F. Synthesis,
characterization and activity pattern of CuZnO/ZrO2 catalysts in the
hydrogenation of carbon dioxide to methanol. J Catal 2007;249:18594.
[13] Cai W, de la Piscina PR, Toyir J, Homs N. CO2 hydrogenation to methanol over
CuZnGa catalysts prepared using microwave-assisted methods. Catal Today
2015;242:1939.
[14] Ren H, Xu CH, Zhao HY, Wang YX, Liu J, Liu JY. Methanol synthesis from CO2
hydrogenation over Cu/cAl2O3 catalysts modied by ZnO, ZrO2 and MgO. J
Ind Eng Chem 2015;28:2617.
[15] Natesakhawat S, Lekse JW, Baltrus JP, Ohodnicki PR, Howard JrBH, Deng X,
et al. Active sites and structureactivity relationships of copper-based
catalysts for carbon dioxide hydrogenation to methanol. ACS Catal
2012;2:166776.
[16] Schumann J, Lunkenbein T, Tarasov A, Thomas N, Schlgl R, Behrens M.
Synthesis and characterization of a highly active Cu/ZnO: Al catalyst.
ChemCatChem 2014;6:288997.
[17] Frusteri F, Cordaro M, Cannilla C, Bonura G. Multifunctionality of CuZnO
ZrO2/H-ZSM5 catalysts for the one-step CO2 to DME hydrogenation reaction.
Appl Catal B Environ 2015;162:5765.

894

T. Witoon et al. / Energy Conversion and Management 103 (2015) 886894

[18] Witoon T, Permsirivanich T, Donphai W, Jaree A, Chareonpanich M. CO2

hydrogenation to methanol over Cu/ZnO nanocatalysts prepared via a
chitosan-assisted
co-precipitation
method.
Fuel
Process
Technol
2013;116:728.
[19] Witoon T, Chareonpanich M, Limtrakul J. Effect of hierarchical meso
macroporous silica supports on FischerTropsch synthesis using cobalt
catalyst. Fuel Process Technol 2011;92:1498505.
[20] Song D, Li J. Effect of catalyst pore size on the catalytic performance of silica
supported cobalt FischerTropsch catalysts. J Mol Catal A Chem
2006;247:20612.
[21] Khodakov AY, Griboval-Constant A, Bechara R, Zholobenko VL. Pore size effects
in Fischer Tropsch synthesis over cobalt-supported mesoporous silicas. J Catal
2002;206:23041.
[22] Witoon T, Bumrungsalee S, Vathavanichkul P, Palitsakun S, Saisriyoot M,
Faungnawakij K. Biodiesel production from transesterication of palm oil with
methanol over CaO supported on bimodal mesomacroporous silica catalyst.
Bioresour Technol 2014;156:32934.
[23] Possato LG, Diniz RN, Garetto T, Pulcinelli SH, Santilli CV, Martins L. A
comparative study of glycerol dehydration catalyzed by micro/mesoporous
MFI zeolites. J Catal 2013;300:10212.
[24] Tanggarnjanavalukul C, Donphai W, Witoon T, Chareonpanich M, Limtrakul J.
Deactivation of nickel catalysts in methane cracking reaction: effect of
bimodal mesomacropore structure of silica support. Chem Eng J
2015;262:36471.
[25] Ramasamy KK, Zhang H, Sun J, Wang Y. Conversion of ethanol to hydrocarbons
on hierarchical HZSM-5 zeolites. Catal Today 2014;238:10310.
[26] Hu Z, Zhang H, Wang L, Zhang H, Zhang Y, Xu H, et al. Highly stable boronmodied hierarchical nanocrystalline ZSM-5 zeolite for the methanol to
propylene reaction. Catal Sci Technol 2014;4:28915.
[27] Iglesia E. Design, synthesis, and use of cobalt-based FischerTropsch synthesis
catalysts. Appl Catal A Gen 1997;161:5978.
[28] Tokudome Y, Fujita K, Nakanishi K, Miura K, Hirao K. Synthesis of monolithic
Al2O3 with well-dened macropores and mesostructured skeletons via the solgel process accompanied by phase separation. Chem Mater 2007;19:33938.
[29] Mohamed MM, Abu-Zied BM. Acidic properties of sulfated ions oxide
supported molybdenum catalysts: a differential scanning calorimetry,
thermogravimetry and Fourier transform-infrared study. Thermochim Acta
2000;359:10917.
[30] Xia WS, Wan HL, Chen Y. Cluster model study on the surface interactions of alumina-supported metal oxides. J Mol Catal A Chem 1999;138:18595.
[31] Wan H, Wang Z, Zhu J, Li X, Liu B, GaO F, et al. Inuence of CO pretreatment on
the activities of CuO/cAl2O3 catalysts in CO+O2 reaction. Appl Catal B Environ
2008;79:25461.

[32] LuO MF, Fang P, He M, Xie YL. In situ XRD, Raman, and TPR studies of CuO/
Al2O3 catalysts for CO oxidation. J Mol Catal A Chem 2005;239:2438.
[33] Reddy GK, Rao KSR, Rao PK. Effect of support modication by carbon coverage
in the dehydrogenation activity of Cu/Al2O3 catalyst. Catal Lett
1999;59:15760.
[34] Li C, Yuan X, Fujimoto K. Development of highly stable catalyst for methanol
synthesis from carbon dioxide. Appl Catal A Gen 2014;469:30611.
[35] Bonura G, Cordaro M, Cannilla C, Arena F, Frusteri F. The changing nature of the
active site of CuZnZr catalysts for the CO2 hydrogenation reaction to
methanol. Appl Catal B Environ 2014;152153:15261.
[36] Zhang Y, Fei J, Yu Y, Zheng X. Study of CO2 hydrogenation to methanol over CuV/-Al2O3 catalyst. J Nat Gas Chem 2007;16:125.
[37] Gao P, Xie R, Wang H, Zhong L, Xia L, Zhang Z, et al. Cu/Zn/Al/Zr catalysts via
phase-pure hydrotalcite like compounds for methanol synthesis from carbon
monoxide. J CO2 Util 2015. 10.1016/j.jcou.2014.12.008.
[38] McCabe WL, Smith JC, Harriott. Unit operations of chemical engineering. 7th
ed. New York: McGraw-Hill; 2005.
[39] Fairbanks DF, Wilke CR. Diffusion coefcients in multicomponent gas
mixtures. Ind Eng Chem 1950;42:4715.
[40] Beckman JW. Mathematical description of heterogeneous materials. Chem Eng
Sci 1990;45:260310.
[41] Bando KK, Sayama K, Kusama H, Okabe K, Arakawa H. In-situ FT-IR study on
CO2 hydrogenation over Cu catalysts supported on SiO2, Al2O3, and TiO2. Appl
Catal A Gen 1997;165:391409.
[42] Zhang Y, Fei J, Yu Y, Zheng X. Methanol synthesis from CO2 hydrogenation over
Cu based catalyst supported on zirconia modied -Al2O3. Energy Convers
Manage 2006;47:33607.
[43] Arena F, Mezzatesta G, Zafarana G, Truno G, Frusteri F, Spadaro L. How oxide
carriers control the catalytic functionality of the CuZnO system in the
hydrogenation of CO2 to methanol. Catal Today 2013;210:3946.
[44] Choi Y, Stenger HG. Fuel cell grade hydrogen from methanol on a commercial
Cu/ZnO/Al2O3 catalyst. Appl Catal B Environ 2002;38:25969.
[45] Jun KW, Lee HS, Roh HS, Park SE. Highly water-enhanced H-ZSM-5 catalysts for
dehydration of methanol to dimethyl ether. Bull Korean Chem Soc
2003;24:1068.
[46] Xu M, Lunsford JH, Goodman DW, Bhattacharyya A. Synthesis of dimethyl
ether (DME) from methanol over solid-acid catalysts. Appl Catal A Gen
1997;149:289301.
[47] Akarmazyan SS, Panagiotopoulou P, Kambolis A, Papadopoulou C, Kondarides
DI. Methanol dehydration to dimethylether over Al2O3 catalysts. Appl Catal B
Environ 2014;145:13648.