> REPLACE THIS LINE WITH YOUR PAPER IDENTIFICATION NUMBER (DOUBLE-CLICK HERE TO EDIT) <
Methanol Synthesis over
Cu and Cu-oxide-containing ZnO/Al2O3
using Dielectric Barrier Discharge
Antonius Indarto, Jae W. Choi, Hwaung Lee, and Hyung K. Song, Member, IEEE
Abstract—Initially developed for more than 20 years ago, the
copper over zinc and aluminum oxide (ZnO/Al2O3) catalyst
system is used for low pressure methanol synthesis. Recently, the
Cu/ZnO/Al2O3 showed to be active in a dielectric barrier
discharge (low-temperature plasma). In this present study, the
investigation on the copper as the active site of the catalyst was
discussed on the basis of experimental result and its
characterization analysis. The catalyst was attempted to aid the
reaction performance of partial oxidation of methane in order to
produce methanol. All CZA-based catalysts were successfully
increased the methanol selectivity and the Cu-oxide performed
better than metallic copper catalyst.
Index Terms—Catalytic plasma, methanol, dielectric barrier
discharge
I.INTRODUCTION
T
HE use of Cu/ZnO/Al2O3 (CZA) based catalyst for
methanol synthesis has been known for long period. In
the beginning of 19, ICI has developed the catalyst which
able to convert synthesis gas (mixture of CO, CO2, and H2) to
methanol with yield c.a. 99% [1]. Even though the process of
methanol is already well-established, still, there are many
plenty rooms for the process development, e.g. methanol from
direct methane conversion, or the application of new process
system, e.g. plasma-aided reaction.
The combination of plasma with catalyst has been
intensively investigated to enable the production methanol
from direct methane conversion. Recent result of our
investigation indicates that the CZA showed to be a very
promising catalyst for this type of chemical process using
dielectric barrier discharge (DBD) [2]. Moreover, it proposed
that the Cu and Zn synergy was also occurred in the low-
temperature plasma environment. In the thermal process,
Cu2+ or Cu+ have been suspected as the main active center
while ZnO could help to disperse the copper metal
distribution on the surface of the catalyst [3].
In this research, we would like to focus the study on the
effect of the two different Cu forms, i.e. metallic copper (Cu0)
and Cu-oxide forms (Cu+ and Cu2+), employed for the

Manuscript received October 26, 2007. This work was supported by the
Global R&D Program of the Korea Foundation for International Cooperation of
Science and Technology (KICOS).
A. Indarto was with Korea Institute of Science and Technology, Seoul Korea.
He is now with the Department of Organic Chemistry, Università di Torino,
Turin, 10145 Italy (corresponding author, phone: 349-351-3904; e-mail:
antonius.indarto@unito.it).
J. W. Choi, H. Lee, and H. K. Song are with the Environmental Process
Division, Korea Institute of Science and Technology, Seoul, Korea.
1
methanol synthesis from methane and oxygen in the low-
temperature plasma environment.
II.EXPERIMENTAL SETUP
A.Plasma Reactor and Instrumental Devices
The research was conducted using a dielectric barrier
discharge. The plasma reactor was a quartz cylindrical tube
with inside diameter of 2 cm and the active length of the
plasma zone was 20 cm. The catalyst was packed at the end
of the plasma zone in order to avoid the destruction of
catalytic reaction products by plasma. In all experiments, we
used only 0.5 gram and the supplied powers were between 60
and 80 W. The ratio of methane to oxygen was maintained at
5:1 by volume basis. To increase the temperature of the
catalyst-zone as well as to activate the catalyst, an additional
heater was installed. By using the heater, the catalyst-pack
temperature reached 80 to 120oC when the plasma was turned
off. The product line was connected to the gas chromatograph
(GC), covered by heating bend to avoid the liquid products’
condensation. The GC was able to detect eight different
hydrocarbons and the column material used for analysis was
chosen to be resistance in the present of water and acid
compounds.
B.Catalyst Preparation and Characterization
The catalyst was prepared following the co-precipitation
method [2]. To obtain the Cu-oxide form, the catalyst was
calcined in mild-temperature below 200oC for 2 hr in
atmospheric open-air condition (A-type catalyst). Then, some
portions of calcined catalyst were reduced by flowing 2
ml/min of H2 and He mixture (1:2) in DBD-plasma (B-type
catalyst). This method was used to avoid the change of
catalyst structure and morphology due to high-temperature
effect, e.g. sintering, when the catalyst was reduced using
thermal method. DBD treatment will allow us to maintain the
catalyst morphology as the treatment occurred at temperature
of as low as room temperature, c.a. 25oC.
The resulted catalysts obtained the surface area in the
range between 92 and 108 m 2/g while the pore volume was
around 0.25 – 0.35 cm3/g. The XRD patterns of the different
catalysts are shown in Fig. 1 which indicates the two different
forms of Cu in the catalyst. In the calcined-catalyst (A-type),
the Cu presented in two oxide forms (CuO and Cu 2O). In
contrast, the Cu-oxide was drastically transformed into
metallic copper (Cu0) after plasma reduction shown by
> REPLACE THIS LINE WITH YOUR PAPER IDENTIFICATION NUMBER (DOUBLE-CLICK HERE TO EDIT) < 2

dominant peaks of 2θ = 43o, 50o. We could not able to obtain present of CZA catalyst, syngas could be converted further
the peak for Ga and Cr as the concentration of those metals into methanol.
was relatively small. The purpose of Ga and Cr addition is to The durability of A and B -type catalyst shows very good
enhance the catalyst performance as those metals were performance. For almost 3 hr operation, the production of
reported to give a positive effect on the methanol production methanol was stable. We did not find any significant
[4]. morphology changes of the catalyst after it was used for the
The catalyst characterization was done by thermal plasma experiment.
gravimetric analysis (shown in Fig. 2a). The analysis was
conducted by flowing the mixture of He and H2 (9:1) to The interesting result was found as the A-type catalyst
measure the weight changes while the temperature elevated. produced more methanol than the B-type catalyst at the same
The investigation of the catalyst morphology by SEM analysis methane conversion. The conversion of methane is mostly
showed similar surface texture of both catalysts; formed a

Methanol selectivity / %
small cubic-like structure. We did not analyze thoroughly the 25

700 C uO ZnO 20
C u 2O A l2 O 3
600 15
G a /A -ty p e
Intensity / a.u.

500 10 A - ty p e
400 C r/ A - ty p e
5 + c a ta ly s t G a / A - ty p e
300 C r/A -ty p e
0
200 40 90 140 190 240 290 340 390
100 A -ty p e S a m p lin g tim e / m in
0
0 10 20 30 40 50 60 70 80 90 25

Methanol selectivity / %
2 th e ta / d e g re e
700 C u (1 1 1 ) C u ZnO 20
A l2 O
600 3
15
Intensity / a.u.

C u (2 0 0 ) C r/B -ty p e
500
400 10 B - ty p e
300 C r/ B - ty p e
5 + c a t a ly s t G a / B - ty p e
200
G a /B -ty p e 0
100
40 90 140 190 240 290 340 390
0 S a m p lin g t im e / m in
0 10 20 30 40 50 60 70 80 90
2 th e ta / d e g re e
Fig. 3. Methanol selectivity of catalytic plasma process using A-type catalyst
Fig. 1. The X-Ray Diffraction (XRD) spectra: (above) The Cu-oxide catalyst (above) and B-type catalyst (below).
(A-type) and (below) the Cu0 catalyst (B-type)
affected by supplied power to the reactor and the presence of
crystallinity structure of the catalyst; however the similar catalyst did not give a significant influence [2]. The
feature of the surface morphology shown by SEM is rather selectivity of methanol in A-type catalyst was in the region
enough to present the similarity of those two types of catalyst. between 19 and 23% whereas B-type catalyst was only 15 to
18%. It shows that the difference of Cu forms in the catalyst
gives a significant effect on the reaction of methanol
III.RESULTS AND DISCUSSION synthesis. This result also clearly indicated that the Cu ion
Fig. 3 shows the performance of the catalyst in the partial forms (Cu+ or Cu2+) could be more active species than
oxidation of methane reaction to produce methanol. metallic copper (Cu0). Although this idea is a controversy and
Compared to the non-catalytic plasma reaction, the addition still debatable, Günter et al. showed evidence that Cu-oxide
of CZA-based catalysts gave almost double increment of forms gave slightly higher methanol production by Cu-phase
methanol selectivity (Fig. 3). Our previous investigation cycle method at 523K [5]. This seems to have occurred in the
low thermal plasma process, such as DBD in this experiment.
100
(a ) (b ) Recently, Shishido and co-workers proposed that Cu+ could be
the active site for water-shift gas reaction [6]. It was reported
Weight loss / %

98

96 that the migration of ZnO on top of Cu was followed by the

94
formation of a (partly) oxidized Cu in a Cu+/ZnO surface with
oxygen vacancies worked as the active sites for methanol
92 C u O / Z n O /A l2 O
C u / Z n O / A l2 O 3
3
synthesis. An old work by Lee et al. found that Cu+ and Cu2+
90
0 100 200 300 400 500 600 700 800 could exist in the CuO lattice with Cu + concentration was
T e m p . / oC higher than Cu2+ [7].
Fig. 2. (a) The TGA analysis and (b) the SEM images of the A-type (above) and
B-type catalyst (below). The bar is equal to 600 nm.
IV.CONCLUSIONS
resulted that non-catalytic plasma reaction of partial methane The present study demonstrated that CZA-based catalyst
oxidation produced synthesis gas (mixture of CO, CO 2, and was also active for methanol synthesis in the plasma
H2) and water as the most dominant products [2]. In the environment. In order to distinguish the active form of
> REPLACE THIS LINE WITH YOUR PAPER IDENTIFICATION NUMBER (DOUBLE-CLICK HERE TO EDIT) < 3

copper, the Cu-oxide and metallic Cu in the catalyst were

used as the experimental variable. The result showed that Cu-
oxide resulted higher methanol selectivity than that of
metallic copper (Cu0), means that Cu+ and Cu2+ could be the
active forms of the catalyst in the low-temperature plasma
process.

ACKNOWLEDGMENT
A. Indarto thanks the International R&D Academy of the
Korea Institute of Science and Technology for the study
supports.

REFERENCES
[1] J. M. Thomas, W. J. Thomas, in Principles and Practice of
Heterogeneous Catalysis, VCH Publishers, Weinheim, 1996, pp. 515–
521.
[2] A. Indarto, D. R. Yang, J. Palgunadi, J. W. Choi, H. Lee, H. K. Song,
“Partial oxidation of methane with Cu-Zn-Al catalyst in a dielectric barrier
discharge,” Chem. Eng. Process., in press.
[3] H. Y. Chen, S. P. Lau, L. Chen, J. Lin, C. H. A. Huan, K. L. Tan, J. S. Pan,
“Synergism between Cu and Zn sites in Cu/Zn catalysts for methanol
synthesis,” Appl. Surf. Sci., vol. 152, pp. 193-199, 1999.
[4] T. Matsuhisa, in Catalysis, Athenaemum Press Ltd, Gateshead, 1996, Vol.
12, Chap. 1, pp. 6.
[5] M. M. Günter, T. Ressler, R. E. Jentoft, B. Bems, “Redox behavior of
copper oxide/zinc oxide catalysts in the steam reforming of methanol
studied in situ X-ray diffraction and absorption spectroscopy,” J. Catal.,
vol. 203, pp. 133-149, 2001; M. M. Günter, T. Ressler, B. Bems, C.
Büscher, T. Genger, O. Hinrichsen, M. Muhler, R. Schlögl, “Implication of
the microstructure of binary Cu/ZnO Catalysts for their catalytic activity in
methanol synthesis,” Catal. Lett., vol. 71, pp. 37-44, 2001.
[6] T. Shishido, M. Yamamoto, D. Li, Y. Tian, H. Morioka, M. Honda, T.
Sano, K. Takehira, “Water-gas shift reaction over Cu/ZnO and
Cu/ZnO/Al2O3 catalysts prepared by homogeneous precipitation,” Appl.
Catal. A: Gen., vol. 303, pp. 62-71, 2006; T. Shishido, M. Yamamoto, I.
Atake, D. Li,Y. Tian, H. Morioka, M. Honda, T. Sano, K. Takehira,
“Cu/Zn-based catalysts improved by adding magnesium for water-gas shift
reaction,” J. Mol. Catal. A: Chem. Vol. 253, pp. 270-278, 2006.
[7] H. G. Lee, C. S. Han, M. S. Cho, K. S. Rhee, H. Chon, “Temperature-
programmed reduction of copper oxide supported on γ-Al2O3 and SiO2,” J.
Korea. Chem. Soc. 1986, 30, 415.

Antonius Indarto was born in Malang, Indonesia,

in 1980. He received the B.S. degree in chemical
engineering in 2002 from Institut Teknologi
Bandung, and M.S. degree in environmental process
from the Korea Institute of Science and Technology,
Seoul, Korea in 2006. He also received another M.S.
degree from the Asian Institute of Technology,
Thailand in 2005.
His research focuses on the methanol
production by non thermal plasma-chemistry
process as well as developing high quality
catalysts for plasma processes.