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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 has
been 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 19th century, ICI developed the catalyst which
able to convert synthesis gas (mixture of CO, CO2, and H2) to
methanol with yields 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,
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
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 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 of catalyst and the supplied powers to the reactor 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
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treatment will allow us to maintain the catalyst morphology
because the treatment occurred at temperature of as low as
room temperature, c.a. 25oC.
The final catalysts have the surface area in the range between
92 and 108 m2/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 Cu2O). In contrast, the Cu-oxide
was drastically transformed into metallic copper (Cu0) after
plasma reduction shown by dominant peaks of 2θ = 43o, 50o.
We failed to obtain the peak for Ga and Cr as the concentration
of those metals was relatively small. The purpose of Ga and Cr
addition is to enhance the catalyst performance as those metals
were reported to give a positive effect on the methanol
production [4].
700
600
Intensity / a.u.
feature of the surface morphology shown by SEM is rather
enough to present the similarity of those two types of catalyst.
III. RESULTS AND DISCUSSION
Fig. 3 shows the performance of the catalyst in the partial
oxidation of methane reaction to produce methanol. Compared
to the non-catalytic plasma reaction, the addition of CZA-based
catalysts gave almost double increment of methanol selectivity
(Fig. 3). Our previous investigation resulted that non-catalytic
plasma reaction of partial methane oxidation produced
synthesis gas (mixture of CO, CO2, and H2) and water as the
most dominant products [2]. This means that non-catalytic
plasma process acted similar to steam methane reforming
(SMR) which known as the most common method of producing
syngas in the industrial synthesis of methanol. Then, in the
CuO ZnO
Cu2O Al2O3 present of CZA catalyst, syngas could be converted further into
methanol.

Ga/A-type
500
400 The durability of A and B -type catalyst shows very good
300 Cr/A-type performance. For almost 3 hr operation, the production of
200 methanol was stable. We did not find any significant
100 A-type
morphology changes of the catalyst after it was used for the
0
0 10 20 30 40 50 60 70 80 90 plasma experiment.
2theta / degree
700 Cu(111) Cu ZnO
Al2O 3
Methanol selectivity / %

600
Intensity / a.u.

Cu(200) Cr/B-type 25
500
400 20
300 15
200 A-type
Ga/B-type 10
100 Cr/A-type
0
5 + catalyst Ga/A-type
0 10 20 30 40 50 60 70 80 90 0
2theta / degree
40 90 140 190 240 290 340 390
Sampling time / min
Fig. 1. The X-Ray Diffraction (XRD) spectra: (above) The Cu-oxide catalyst
(A-type) and (below) the Cu 0 catalyst (B-type) 25
Methanol selectivity / %

20
The catalyst characterization was done by thermal
15
gravimetric analysis (shown in Fig. 2a). The analysis was
conducted by flowing the mixture of He and H2 (9:1) to measure 10 B-type
Cr/B-type
the weight changes while the temperature elevated. The 5 + catalyst Ga/B-type
investigation of the catalyst morphology by SEM analysis 0
40 90 140 190 240 290 340 390
showed similar surface texture of both catalysts; formed a small Sampling time / min
cubic-like structure. We did not analyze thoroughly the
crystallinity structure of the catalyst; however the similar Fig. 3. Methanol selectivity of catalytic plasma process using A-type catalyst
(above) and B-type catalyst (below).

100
(a) (b) The interesting result was found as the A-type catalyst
Weight loss / %

98
produced more methanol than the B-type catalyst at the same
96
methane conversion. The conversion of methane was mostly
94
affected by supplied power to the reactor and the presence of
92 CuO/ZnO/Al2 O3
Cu/ZnO/Al2 O3
catalyst did not give a significant influence [2]. The selectivity
90
0 100 200 300 400 500 600 700 800 of methanol in A-type catalyst was in the region between 19
Temp. / oC 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
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. effect on the reaction of methanol synthesis. This result also
clearly indicated that the Cu ion forms (Cu+ or Cu2+) could be
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more active species than metallic copper (Cu0). Although this

idea is a controversy and still debatable, Günter et al. showed
evidence that Cu-oxide forms gave slightly higher methanol
production by Cu-phase cycle method at 523K [5]. This seems
to have occurred in the low thermal plasma process, such as
DBD in this experiment. Recently, Shishido and co-workers
proposed that Cu+ could be the active site for water-shift gas
reaction [6]. It was reported that the migration of ZnO on top of
Cu was followed by the formation of a (partly) oxidized Cu in a
Cu+/ZnO surface with oxygen vacancies worked as the active
sites for methanol synthesis. An old work by Lee et al. found
that Cu+ and Cu2+ could exist in the CuO lattice with Cu+
concentration was higher than Cu2+ [7].
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.

IV. CONCLUSIONS
The present study demonstrated that CZA-based catalyst was
also active for methanol synthesis in the plasma environment.
In order to distinguish the active form of 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.

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