Journal of Industrial and Engineering Chemistry 15 (2009) 665–669

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Journal of Industrial and Engineering Chemistry

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

Influence of Ga addition on the methanol synthesis activity of Cu/ZnO catalyst in

the presence and absence of alumina
Suk-Hwan Kang a,1, Jong Wook Bae a, P.S. Sai Prasad a, Jong-Hyeok Oh a, Ki-Won Jun a,*,
Seok-Lyong Song b, Keh-Sik Min b
a
Petroleum Displacement Technology Research Center, Korea Research Institute of Chemical Technology (KRICT), P.O. BOX 107, Yuseong, Daejeon 305-600, South Korea
b
Hyundai Heavy Industries, 1, Cheonha-dong, Dong-ku, Ulsan 682-792, South Korea

A R T I C L E I N F O A B S T R A C T

Article history: The influence of Ga addition to Cu/ZnO (CZ) methanol synthesis catalyst was investigated in the presence
Received 27 October 2008 (CZA-Ga) and absence (CZ-Ga) of alumina. The reducibility of CZA-Ga was found to be more facile than
Accepted 18 March 2009 CZ-Ga. The acidic strength of CZA-Ga was considerably decreased compared to CZA and CZ-Ga. In the
presence of alumina, the addition of Ga to CZ improved the textural properties, resisted agglomeration of
Keywords: copper and showed higher activity and stability in methanol synthesis reaction from syngas. The easy
Methanol synthesis reducibility and the appropriate acidity can be ascribed to the higher activity with high yield to methanol
Cu/ZnO/Al2O3
observed on CZA-Ga.
Gallium
Promoter
ß 2009 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V.
Co-precipitation All rights reserved.

1. Introduction Cu/ZnO/Al2O3. The copper-based catalysts for low temperature

methanol synthesis are generally prepared by precipitation of the
Methanol is widely used as a feedstock for the production of metal salts in basic medium. The functions of ZnO in the co-
chemicals and is considered as a viable source for the generation of precipitated Cu/ZnO catalyst are many folds: (i) it favors higher
hydrogen for fuel cell application [1]. Commercially, methanol can dispersion of Cu; (ii) in the presence of Al2O3, it prevents
be produced from hydrogen and carbon monoxide (along with agglomeration of Cu particles which takes place during a long-
some amount of carbon dioxide), obtained from feedstocks term operation; (iii) it improves the resistance of Cu particles to
including natural gas, coal or biomass [2]. poisoning by feed gas impurities, such as sulfides and chlorides and
The synthesis of methanol from syngas can be represented by (iv) ZnO, as a basic oxide, partially neutralizes the acidity of the
the following reactions: catalyst, preventing the transformation of methanol to dimethyl
ether (DME). Al2O3, the widely used third component in Cu-based
CO þ 2H2 , CH3 OH; DH ¼ 90:8 kJ=mol (1)
catalysts, stabilizes the highly dispersed Cu/ZnO structure. Thus, it
acts as structural promoter. But, the acidic sites on Al2O3 can cause
CO2 þ 3H2 , CH3 OH þ H2 O; DH ¼ 49:6 kJ=mol (2)
the transformation of methanol to dimethyl ether (DME), even
though it is mostly neutralized by ZnO [4]. The activity of CZA
CO þ H2 O , CO2 þ H2 ; DH ¼ 41:2 kJ=mol (3)
catalysts is often improved by other promoters such as ZrO2 and
Methanol is formed by CO and CO2 hydrogenation (reactions (1) SiO2 to prevent attrition particularly in slurry phase synthesis [5]
and (2)). The water formed in reaction (2) reacts with CO to form and Cr, for improving the selectivity or stability [6]. The catalyst
CO2 and H2 (reaction (3)), which is known as the water gas shift promoted by trivalent metal ions such as Al3+, Sc3+ and Cr3+ could
(WGS) reaction [3]. In general, reactions (1)–(3) are proceeding on also enhance the formation of monovalent cationic defects on the
a well-known three-component methanol synthesis catalyst, crystal surface of ZnO, which might accelerate both enrichment
and stabilization of Cu+ on the surface during the reduction and
reaction processes [7,8].
* Corresponding author at: Alternative Chemicals/Fuel Research Center, Korea It is surprising that even though the influence of Ga2O3 has been
Research Institute of Chemical Technology (KRICT), P.O. BOX 107, Yuseong, Daejeon extensively studied in CO2 hydrogenation, its effect on the activity
305-600, South Korea. Tel.: +82 42 860 7671; fax: +82 42 860 7388.
E-mail address: [email protected] (K.-W. Jun).
and methanol selectivity in CO hydrogenation is not well under-
1
Current address: Plant Engineering Center, Institute for Advances Engineering stood. Further, the effect of addition of Ga2O3 to the Cu/ZnO system
(IAE), Suwon 443-749, Republic of Korea. on the performance of the catalyst in the presence and absence of

1226-086X/$ – see front matter ß 2009 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.jiec.2009.09.041
666 S.-H. Kang et al. / Journal of Industrial and Engineering Chemistry 15 (2009) 665–669

alumina has not been studied as well. In the present investigation Table 1
Physical properties of the methanol synthesis catalysts.
we report the performance of the Ga-promoted Cu/ZnO(/Al2O3)
catalyst in terms of its CO hydrogenation activity, methanol Notation Surface area Pore volume Pore diameter
selectivity and the catalytic stability. The changes in the textural, [m2/g] [cm3/g] [nm]
acidic and reducibility properties of the Ga-promoted Cu/ZnO CZA 106.9 0.779 27.9
catalyst in the presence and absence of alumina are also reported. CZA-Ga 136.7 0.905 25.1
Characterization techniques like nitrogen adsorption for BET CZ-Ga 32.2 0.316 31.6

surface area and pore size distribution, temperature-programmed

desorption of NH3 (NH3-TPD) and X-ray diffraction (XRD) studies column and FID for hydrocarbons, DME and CH3OH with a GS-Q
have been used to elucidate the variation of catalytic activities capillary column.
with the variation of the physicochemical properties of the
catalysts. 3. Results and discussion

2. Experimental The data on BET surface area, pore volume and average diameter
of the calcined catalysts are shown in Table 1. It can be observed that
2.1. Catalyst preparation without the addition of alumina, even after Ga promotion, the CZ-Ga
catalyst shows very low surface area of 32.2 m2/g. The surface area
The catalysts were synthesized by the co-precipitation method increases threefold and fourfold when alumina is included in Cu/ZnO
using an aqueous solution containing copper acetate, zinc acetate, and further promoted by Ga, respectively. This result reiterates the
aluminum nitrate and gallium nitrate of required quantities such role of alumina as a structural promoter in providing a highly
that the weight ratio of CuO/ZnO = 2. The required quantity of dispersed Cu/ZnO structure. The increase in surface area of CZA in
Al2O3 and Ga2O3 was added during the co-precipitation step with the presence of Ga is possibly due to further enhancement in
the weight ratio of 3.3 wt.% and 3.7 wt.%, respectively at the fixed dispersion of copper. Similar trends are also observed in the pore
ratio of CuO/ZnO. The precipitant, Na2CO3, was dissolved in volume data. The mean pore diameter however, decreases
deionized water and two separate solutions of precipitant and progressively giving a minimum value of 25.1 nm for CZA-Ga
metal precursors were simultaneously dropped with a controlled catalyst. The unimodal distribution of the pores is visible from Fig. 1.
feeding rate of around 10 ml/min at 70 8C. The final pH of the Jin et al. [9] have reported that the pore structure is very critical in
solution was maintained at around 7. The precipitate was further maintaining the stability of the catalysts in the DME and methanol
aged for 3 h at 70 8C followed by calcination at 300 8C for 5 h. The syntheses. Saito et al. [10] developed a high performance multi-
catalyst notation of CZA-Ga stands for the co-precipitated CuO/ component catalyst Cu/ZnO/ZrO2/Al2O3/Ga2O3 following a co-
ZnO/Al2O3/Ga2O3 (weight ratio of 62/31/3.3/3.7) catalyst and CZA precipitation method. They also reported that the addition of
for CuO/ZnO/Al2O3 (62/31/3.3) and CZ-Ga for CuO/ZnO/Ga2O3 (62/ Al2O3 to Cu/ZnO increases the total surface area as well as the
31/3.7) at a fixed ratio of CuO/ZnO. dispersion of Cu particles on the surface [11].
The XRD patterns of the calcined catalysts and the catalysts
2.2. Characterization and activity test collected after reaction, are shown in Fig. 2. The patterns in Fig. 2(a)
reveal sharp reflection peaks corresponding to CuO and ZnO
BET surface area and BJH pore size distribution of catalysts were phases. The reflections of CuO are observed in the range of
determined by N2-physisorption using Micromeritics ASAP 2400 358 < 2u < 378 and 478 < 2u < 498 and those assigned to ZnO could
apparatus at liquid-N2 temperature (196 8C). be seen at 318 < 2u < 328. No peaks due to Ga2O3 were observed,
The powder X-ray diffraction (XRD) patterns were obtained possibly due to its well-dispersed nature. The particle sizes of CuO
with a Rigaku diffractometer using Cu-Ka radiation to identify the present in various catalysts, as calculated using the Scherrer’s
crystalline phases on the catalysts and the particle size of copper equation, are reported in Table 2. The catalyst without alumina
species (before reaction, after reduction and reaction). shows larger particle size of CuO around 13.6 nm. The CuO particle
The temperature-programmed reduction (TPR) experiments size in CZA-Ga is the lowest among the three catalysts, suggesting
were performed to determine the reducibility of the surface oxides. higher dispersion due to the character of structural promoter,
Prior to the TPR experiments, the samples were pre-treated in a He Al2O3, which is in accordance with the surface area data. The
flow up to 200 8C and kept for 2 h to remove the adsorbed water
and other contaminants followed by cooling to 100 8C. The
reducing gas containing 5%H2/Ar mixture was passed over the
samples at a flow rate of 30 ml/min, with the heating rate of 10 8C/
min up to 500 8C and kept at that temperature for 30 min.
The NH3-TPD experiments (Micromeritics, Autochem 2920)
were performed to determine the acidity of calcined and used
catalysts by using GC equipped with TCD. About 0.1 g of the sample
was flushed initially with a He flow at 250 8C for 2 h, cooled to
100 8C and saturated with NH3. Purging the sample with He flow
was continued until equilibrium, and then TPD was carried out
with a heating rate of 10 8C/min.
Catalytic activity tests were carried out in a tubular fixed bed
reactor (12.7 mm OD) with a catalyst weight of 1.0 g. Prior to the
reaction, the catalyst was reduced for 4 h at 250 8C in a flow of 5%
H2 balanced with nitrogen. After reduction, the synthesis gas (H2/
CO = 2) was fed into the reactor. The reaction conditions were
T = 250 8C, P = 5.0 MPa and SV = 4000 ml/gcat h. The products were
analyzed on an on-line chromatograph (Donam model DS 6200)
using TCD to analyze Ar, CO and CO2 with a carbosphere packed Fig. 1. Pore size distribution of methanol synthesis catalysts.
 S.-H. Kang et al. / Journal of Industrial and Engineering Chemistry 15 (2009) 665–669 667

Fig. 3. H2-TPR profiles of calcined catalysts.

addition of Ga to CZA is evident from the TPR peaks. This supports the
information obtained from XRD and nitrogen adsorption studies.
Fierro and co-workers [13] also reported one reduction peak
centered at 223 8C in the TPR of Cu/ZnO/Al2O3 catalysts prepared by
co-precipitation, which was assigned to the reduction of CuO to Cu:
CuO + H2 ! Cu0 + H2O. The difference in the Tmax value could be the
manifestation of the difference in the method of preparation or the
aging time. The shift in the Tmax to lower temperatures indicates the
easy reducibility of the copper phase, which is probably due to the
formation of well-dispersed CuO particles in contact with the
surface of ZnO particles. It has been reported that ZnO promotes the
copper reducibility in the overall range of composition of CuO/ZnO
binary system [14].
The activities of the catalysts over a period of 15.5 h (under the
reaction conditions: P = 5.0 MPa, SV = 4000 ml/gcat h and
Fig. 2. XRD patterns of calcined catalysts (*, CuO; &, ZnO) and catalysts after
T = 250 8C), are shown in Fig. 4. The CO conversion on CZA-Ga
reaction for 15.5 h (*, Cu; *, CuO; &, ZnO). records a high initial value of 48.4% and subsequently attains a
value of 35.9% at steady-state. In the case of CZA catalyst, the CO
particle of copper after reduction reveals the smallest size in CZA- conversion also shows a high initial value of 44.2%, but decreases
Ga around 8.1 nm and largest in CZ-Ga around 10.5 nm. The sharply to the value of 26.8% during the time-on-stream. CZ-Ga on
particle size of metallic copper after reaction also reveals the the other hand, also stabilizes faster even though the conversion
sintering of copper species in all samples and its aggregation is values are low. Cu-based catalysts for methanol synthesis and
much severe on the CZ-Ga catalyst. hybrid catalysts for direct DME synthesis display an induction
The TPR profiles of the catalysts shown in Fig. 3 exhibit only one period for stabilization due to the oxidation–reduction cycles of
reduction peak appearing in the range of 150–470 8C. The CZ-Ga, the active species [15]. Also, the initial activity of the catalyst
without alumina, exhibits a broad peak with its maximum intensity
at 342 8C. A higher Tmax implies much difficult reducibility of Cu
species. Without Ga, the CZA shows better reducibility compared to
CZ with a decreased Tmax. However, the doubly promoted CZA-Ga
offers well-defined peaks of reduction with the Tmax further
decreasing to 310 8C and revealing that the copper oxide in CZA-
Ga could be reduced more easily to copper metal. In general, a
distinct reduction peak, indicates that the CuO is better dispersed on
the catalyst surface [12]. Thus, the higher dispersion of Cu with the

Table 2
Particle size of copper oxide and metallic coppera.

Notation Before reaction After reduction After reaction

CuO [nm] Cu [nm] Cu [nm]

CZA 11.6 8.4 11.7

CZA-Ga 10.9 8.1 10.8
CZ-Ga 13.6 10.5 18.6
a
The particle size of copper oxide and metallic copper was calculated from
FWHM values of XRD diffraction peaks at 2u = 35.5 and 43.3 separately. Fig. 4. Methanol synthesis activity as a function of time-on-stream (TOS).
668 S.-H. Kang et al. / Journal of Industrial and Engineering Chemistry 15 (2009) 665–669

Table 3 the three catalysts. Neglecting the very low temperature peak (site I),
Conversion and product distribution on the methanol synthesis catalysts.
the two prominent peaks in the regions of 320–420 8C (site II) and
Notation CO conversion Product distribution (mol%) Yield of 420–700 8C (site III) represent the acidic sites on the catalyst surface
(mol%) a MeOH and that of H2O evolution from the metal oxides, respectively. The
MeOH DME HC
acidic site I is mainly attributed to the desorption peak of weakly
CZA 26.8 91.7 3.5 4.8 24.6
CZA-Ga 35.9 93.6 3.2 3.2 33.6
adsorbed NH3 on alumina surface and the acidic site II could be
CZ-Ga 31.0 91.9 6.2 1.9 28.5 assigned to the acidity derived from the microstructure CZA matrix.
a The number of acid sites (mmol NH3/g) was calculated from the
Hydrocarbons (HC) mainly includes CH4 with a trivial amount of C2–C5
hydrocarbons. integration of each peak in Fig. 5. Further, the number of acid site (II)
of CZA, CZA-Ga and CZ-Ga catalysts is 1.71, 1.54 and 0.43 mmol NH3/
g, respectively. Since the Tmax position of the low temperature peak
depends completely on the operating conditions and its composi- (site II) is 392, 365 and 401 8C for CZA, CZA-Ga and CZ-Ga catalysts,
tion. Many researchers [8,16,17] have reported that the metallic Cu respectively, the acidic strength is much larger on CZ-Ga catalyst. In
atoms are active for methanol synthesis. The activity of the catalyst addition, the acidity of CZA-Ga is lower than that of CZA.
is directly proportional to the surface area of metallic Cu and Interestingly, the addition of Ga in the presence of alumina decreases
methanol is formed on a metallic Cu surface of a Cu-based catalyst the acidic sites compared to the CZA catalyst. As mentioned above,
[18] and the activity increases with increase in the metallic copper ZnO neutralizes the acid sites on alumina. Besides, Ga also is found to
surface area [19]. neutralize the resultant acid sites. This is an important observation of
An important point to be noted at this juncture is that in the this work. Thus, the DME selectivity is reduced from 3.5% to 3.2% after
absence of Ga, the CZA looses its activity continually, whereas the the addition of Ga to CZA.
other two catalysts could attain steady-state. Thus, it can be The influence of Ga is further probed by analyzing the XRD
observed that the presence of Ga stabilizes the catalytic activity patterns of catalysts collected after the reaction. The corresponding
faster. The sharp fall in the activity of CZA can be due to the spectra are shown in Fig. 2b. The reflection peaks of reduced Cu are
deactivation induced by a sintering of copper species or coke observed at 43.38. The particle size of CuO calculated from Scherrer’s
formation on the strong acidic sites which is confirmed by the equation (full width of half maximum (FWHM) at 2u = 35.58 and
variation of copper particle size and acidic strength as reported in 43.38) are recorded in Table 2. Whereas, CZA and CZA-Ga retained
our previous work [12]. their particle size, CZ-Ga shows an increased value for the Cu metal
It is appropriate at this point to understand how the addition of Ga particle size, implying a possible sintering of the active metal. Pan
to CZA helps attain higher activity and the methanol yield. The et al. [18] have reported that the activity of the catalyst for methanol
increased activity comes from better dispersion and higher synthesis is directly proportional to the surface area of metallic Cu.
reducibility, as evidenced from the XRD and TPR data. Stabilization Atake et al. [20] also observed that the Cu–Al–Zn oxide catalyst is
of the activities of CZ-Ga and CZA-Ga is the manifestation of the unstable and gives rise to the sintering of Cu at high temperature.
influence of Ga on the restricted sintering of copper species and Therefore, the effect of Ga is essentially observed in enhancing the
concomitantly enhanced redox properties of Cu. It can be construed CuO reducibility and reduction in the strength of acidic sites, but
that Ga regulates the optimal ratio of Cu+/Cu0 throughout the cannot resist sintering in the absence of alumina. In the presence of
reaction mainly by stabilization of copper species with the alumina this can be controlled and Inui has recognized, through the
suppressed sintering on CZA components. Saito et al. [10] studying investigation of paraffin aromatization, that Ga ingredient has a
the promoting effect of gallium oxide opined that the progressive catalytic property for an inverse-spillover of hydrogen [21]. It has
formation of smaller particles of gallium oxide highly dispersed on been pronounced that both the effects namely, spillover effect with
the surface are responsible for the activity. As revealed from Table 3, Pd and the inverse-spillover effect with Ga, concomitantly balance
CZA-Ga has its DME selectivity intermediate between CZ-Ga and CZA the desired reduction state of the catalyst during the reaction giving
catalysts. The acidic strength of the catalyst significantly changes the maximum methanol yield. Recently, the other group reported a
DME selectivity by the dehydration of methanol formed on the Cu series of Cu–Zn–Ga-supported catalysts as alternative catalysts for
metallic sites on the acid center of the catalyst. Fig. 5 demonstrates CO2 hydrogenation to methanol [22]. The improvement in catalyst
the temperature-programmed desorption of ammonia patterns of performance is mainly related to the modification of copper species
by the presence of small Ga2O3 surface particles. We feel that apart
from the above parameters, moderation of the acidity and acidic
strength, after Ga addition to CZA, is responsible for the maximiza-
tion of methanol yield.

4. Conclusions

Addition of Ga, in presence of alumina, improves the

reducibility of Cu/ZnO catalysts, but CZA catalyst deactivates
faster without Ga addition. The addition of Al and Ga on Cu/ZnO
catalyst during the co-precipitation step acts as a structural
promoter and is responsible for enhancing the copper dispersion
with the formation of much smaller copper particles. In addition,
moderation of the acidity and acidic strength by Ga addition
enhances the methanol yield with low byproduct formation in the
case of CZA-Ga catalyst as well.

Acknowledgements

P.S. Sai Prasad thanks the Director, IICT, Hyderabad for the
Fig. 5. NH3-TPD profiles of calcined catalysts. sanction of sabbatical leave.
 S.-H. Kang et al. / Journal of Industrial and Engineering Chemistry 15 (2009) 665–669 669

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