1

Methanol synthesis over Cu and Cu-oxide-containing ZnO/Al O Antonius Indarto1,2

2 3
1
using dielectric barrier discharge Dipartimento di Chimica Generale
ed Organica Applicata ,Universita
2
degli studi di Torino, Corso Massimo D’Azeglio 48, Turin Division of Process and Environment, Korea Institute of Science and
Technology, PO BOX 131, Seoul

(Received <Month> <Date>, <Year>; CL-<No>; E-mail: <antonius.indarto@unito.it>)

Initially developed for more than 20 years ago, the
copper over zinc and aluminum oxide (ZnO/Al2O3) 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 was
successfully increased the of methanol selectivity which the
Cu-oxide performed better than metallic copper catalyst.
The use of Cu/ZnO/Al2O3 (CZA) based catalyst for
methanol synthesis has been known for long period. In the
beginning of 19, the 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
chosen to be resistance in the present of water and acid
compounds.
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 h 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 changes of
catalyst structure and morphology due to high-temperature
effect, e.g. sintering, if the catalyst was reduced using thermal
method. DBD will allow us to maintain the catalyst
morphology as the treatment was conducted at temperature of
as low as room temperature, c.a. 25oC.
700 C uO
C u 2O
ZnO
A l2 O 3
600
G a /A -ty p e
Intensity / a.u.

500
methanol is already well-established, still, there are many
400
plenty rooms for the process development, e.g. methanol from C r/A -ty p e
300
direct methane conversion, or the application of new process
200
system, e.g. plasma-aided reaction. 100 A -ty p e
The combination of plasma with catalyst has been 0
intensively investigated to enable the production methanol 0 10 20 30 40 50
2 th e ta / d e g re e
60 70 80 90

from direct methane conversion. Recent result of our

700 C u(1 1 1 ) Cu ZnO
investigation indicates that the CZA showed to be a very A l2 O
600 3

promising catalyst for this type of chemical process using C u (2 0 0 )

Intensity / a.u.

500 C r/B -ty p e

dielectric barrier discharge (DBD) [2]. It proposed that the Cu 400
and Zn synergy was also occurred in the low-temperature 300
plasma environment. In the thermal process, Cu2+ or Cu+ have 200
G a /B -ty p e
been suspected as the main active center while ZnO could 100
help to disperse the copper metal distribution on the surface of 0
0 10 20 30 40 50 60 70 80 90
the catalyst [3]. 2 th e ta / d e g re e
In this research, we would like to focus the study on the
Figure 1.  The X-Ray Diffraction (XRD) spectra: (above) The Cu-oxide
effect of the two different Cu forms, i.e. metallic copper (Cu0) catalyst (A-type) and (below) the Cu0 catalyst (B-type)
and Cu-oxide forms (Cu+ and Cu2+), employed for the
methanol synthesis from methane and oxygen in the low-
The resulted catalysts obtained the surface area in the
temperature plasma environment.
range between 92 and 108 m2/g while the pore volume was
The research was conducted using a dielectric barrier
around 0.25 – 0.35 cm3/g. The XRD patterns of the different
discharge. The plasma reactor was a quartz cylindrical tube
catalysts are shown in Fig. 1 which indicates the two different
with inside diameter of 2 cm and the active length of the
forms of Cu in the catalyst. In the calcined-catalyst (A-type),
plasma zone was 20 cm. The catalyst was packed at the end of
the Cu presented in two oxide forms (CuO and Cu2O). In
the plasma zone in order to avoid the destruction of catalytic
contrast, the Cu-oxide was drastically transformed into
reaction products by plasma. To increase temperature in the
metallic copper (Cu0) after plasma reduction shown by
catalyst-zone as well as to activate the catalyst, an additional
dominant peaks of 2θ = 43o, 50o. We could not able to obtain
heater was installed. By using the heater, the catalyst-pack
the peak for Ga and Cr as the concentration of those metals
temperature reached 80 to 120oC when the plasma was turned
was relatively small. The purpose of Ga and Cr addition is to
off. The product line was connected to the gas chromatograph
enhance the catalyst performance as those metals were
(GC), blanket by heating bend to avoid the liquid products
reported to give a positive effect on the methanol production
condensation. The GC was able to detect eight different
[4].
hydrocarbons and the column material used for analysis was
 2

The catalyst characterization was also done by TGA Figure 3. The methanol selectivity for the process using (above)
analyst (Fig. 2a). The analysis was conducted by flowing the A-type catalyst and (below) B-type catalyst.
mixture of He and H2 (9:1) to measure the weight changes
while the temperature elevated. The investigation of the The interesting result was found as the A-type catalyst
catalyst morphology by SEM analysis showed similar surface produced more methanol than B-type catalyst at almost
texture of both catalysts; formed a small cubic-like structure. similar methane conversion. The conversion of methane is
We did not analyze thoroughly the structure crystallinity of mostly affected by supplied power to the reactor and the
the catalyst; however the similar feature of the surface present of catalyst did not give significant influence [2]. The
morphology shown by SEM is rather enough to present the selectivity of methanol in A-type catalyst was in the region
similarity of those two types of catalyst. between 19 to 23% while B-type catalyst was only 15 to 18%.
It shows that the different of Cu form in the catalyst gives a
100 significant effect on the reaction of methanol synthesis. This
(a ) (b )
result also clearly indicates that the Cu ion forms (Cu+ or C2+)
Weight loss / %

98
96
94
92
90
0 100 200 300
T e m p . / oC
Figure 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.
Figure 3 shows the performance of the catalyst in the
partial oxidation of methane reaction to produce methanol.
Comparison to the non-catalytic plasma reaction, the addition
of CZA-based catalysts gave almost double increment of
methanol selectivity (Fig. 3). Our previous investigation
results that non-catalytic plasma reaction of partial methane
oxidation produced synthesis gas (mixture of CO, CO 2, and
H2) and water as the most dominant products [2]. In the
present of CZA catalyst, the syngas could be converted further
to methanol.
The durability of A and B -type catalyst shows very good
performance. For almost 3 h operation, the production of
methanol was stable. We did not find any significant
morphology changes of the catalyst after it was used for the
plasma reaction.
Methanol selectivity / %
could be more active species than metallic copper (Cu0).
Although this idea is still debatable and controversy, Günter et
al. showed evidence that Cu-oxide forms gave slightly higher
C u O /Z n O /A l2 O 3
methanol production by Cu-phase cycle method at 523K [5].
C u / Z n O / A l2 O 3 This seems also occurred in the low thermal process, such as
400 500 600 700 800 DBD in this experiment. Recently, Shishido and co-workers
proposed than Cu+ could be the active site 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 which worked as
the active sites for methanol synthesis. An old work by Lee et
al. found that Cu+ and Cu2+ could be existed in the CuO lattice
in which Cu+ concentration was higher than Cu2+ [7].
In conclusion, 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
for the experimental variable. The result showed that Cu-
oxide resulted higher methanol selectivity than that by
metallic copper, means that Cu+ and Cu2+ could be the active
forms in the low-temperature plasma process.
This study was supported by the Global R&D Program
of the Korea Foundation for International Cooperation of
Science and Technology (KICOS). The author thanks the
International R&D Academy, Korea Institute of Science and
Technology for the study supports.

25

20 References and Notes

15 1 J. M. Thomas, W. J. Thomas, in Principles and Practice of
10 A - ty p e Heterogeneous Catalysis, VCH Publishers, Weinheim,
C r/ A - ty p e 1996, pp. 515–521.
5 + c a ta ly s t G a / A - ty p e 2 A. Indarto, D. R. Yang, J. Palgunadi, J. W. Choi, H. Lee,
0 H. K. Song, Chem. Eng. Process. 2007, in press.
40 90 140 190 240 290 340 390 3 H. Y. Chen, S. P. Lau, L. Chen, J. Lin, C. H. A. Huan,
S a m p lin g t im e / m in K. L. Tan, J. S. Pan, Appl. Surf. Sci. 1999, 152, 193.
25 4 T. Matsuhisa, in Catalysis, Athenaemum Press Ltd,
Methanol selectivity / %

Gateshead, 1996, Vol. 12, Chap. 1, pp. 6.

20 5. M. M. Günter, T. Ressler, R. E. Jentoft, B. Bems, J.
15 Catal. 2001, 203, 133; M. M. Günter, T. Ressler, B. Bems,
C. Büscher, T. Genger, O. Hinrichsen, M. Muhler, R.
10 B - ty p e Schlögl, Catal. Lett. 2001, 71, 37.
C r/ B - ty p e 6. T. Shishido, M. Yamamoto, D. Li, Y. Tian, H. Morioka,
5 + c a t a ly s t G a / B - ty p e M. Honda, T. Sano, K. Takehira, Appl. Catal. A: Gen.
0 2006, 303, 62; T. Shishido, M. Yamamoto, I. Atake, D.
40 90 140 190 240 290 340 390
Li,Y. Tian, H. Morioka, M. Honda, T. Sano, K. Takehira, J.
S a m p lin g t im e / m in Mol. Catal. A: Chem. 2006, 253, 270.
3
7 H. G. Lee, C. S. Han, M. S. Cho, K. S. Rhee, H. Chon,
J. Korea. Chem. Soc. 1986, 30, 415.
 NOTE The diagram is acceptable in a colored form. Publication of the colored G.A. is free of charge.
For publication, electronic data of the colored G.A. should be submitted. Preferred data format is EPS, PS, CDX, PPT, and TIFF.
If the data of your G.A. is "bit-mapped image" data (not "vector data"), note that its print-resolution should be 300 dpi.

Graphical Abstract

Textual Information
Description (if any)

Title Methanol synthesis over Cu and Cu-oxide-containing ZnO/Al2O3 using dielectric barrier discharge

Authors’ Names Antonius Indarto

Graphical Information

CH p la s m a
4
+ C H 3O H
O 2 C Z A c a t a ly s t