Professional Documents
Culture Documents
Initially developed for more than 20 years ago, the chosen to be resistance in the present of water and acid
copper over zinc and aluminum oxide (ZnO/Al2O3) system is compounds.
used for low pressure methanol synthesis. Recently, the
Cu/ZnO/Al2O3 showed to be active in a dielectric barrier The catalyst was prepared following the co-precipitation
discharge (low-temperature plasma). In this present study, the method [2]. To obtain the Cu-oxide form, the catalyst was
investigation on the copper as the active site of the catalyst calcined in mild-temperature below 200oC for 2 h in
was discussed on the basis of experimental result and its atmospheric open-air condition (A-type catalyst). Then, some
characterization analysis. The catalyst was attempted to aid portions of calcined catalyst were reduced by flowing 2
the reaction performance of partial oxidation of methane in
order to produce methanol. All CZA-based catalysts was ml/min of H2 and He mixture (1:2) in DBD-plasma (B-type
successfully increased the of methanol selectivity which the catalyst). This method was used to avoid the changes of
Cu-oxide performed better than metallic copper catalyst. 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
The use of Cu/ZnO/Al2O3 (CZA) based catalyst for morphology as the treatment was conducted at temperature of
methanol synthesis has been known for long period. In the as low as room temperature, c.a. 25oC.
beginning of 19, the ICI has developed the catalyst which able
to convert synthesis gas (mixture of CO, CO2, and H2) to 700 C uO
C u 2O
ZnO
A l2 O 3
600
methanol with yield c.a. 99% [1]. Even though the process of 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
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
could be more active species than metallic copper (Cu0).
96
Although this idea is still debatable and controversy, Günter et
94 al. showed evidence that Cu-oxide forms gave slightly higher
92 C u O /Z n O /A l2 O 3
methanol production by Cu-phase cycle method at 523K [5].
90
C u / Z n O / A l2 O 3 This seems also occurred in the low thermal process, such as
0 100 200 300 400 500 600 700 800 DBD in this experiment. Recently, Shishido and co-workers
T e m p . / oC
proposed than Cu+ could be the active site water-shift gas
Figure 2. (a) The TGA analysis and (b) the SEM images of the A-type
reaction [6]. It was reported that the migration of ZnO on top
(above) and B-type catalyst (below). The bar is equal to 600 nm. 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
Figure 3 shows the performance of the catalyst in the al. found that Cu+ and Cu2+ could be existed in the CuO lattice
partial oxidation of methane reaction to produce methanol. in which Cu+ concentration was higher than Cu2+ [7].
Comparison to the non-catalytic plasma reaction, the addition In conclusion, the present study demonstrated that CZA-
of CZA-based catalysts gave almost double increment of based catalyst was also active for methanol synthesis in the
methanol selectivity (Fig. 3). Our previous investigation plasma environment. In order to distinguish the active form of
results that non-catalytic plasma reaction of partial methane copper, the Cu-oxide and metallic Cu in the catalyst were used
oxidation produced synthesis gas (mixture of CO, CO 2, and for the experimental variable. The result showed that Cu-
H2) and water as the most dominant products [2]. In the oxide resulted higher methanol selectivity than that by
present of CZA catalyst, the syngas could be converted further metallic copper, means that Cu+ and Cu2+ could be the active
to methanol. forms in the low-temperature plasma process.
The durability of A and B -type catalyst shows very good
performance. For almost 3 h operation, the production of This study was supported by the Global R&D Program
methanol was stable. We did not find any significant of the Korea Foundation for International Cooperation of
morphology changes of the catalyst after it was used for the Science and Technology (KICOS). The author thanks the
plasma reaction. International R&D Academy, Korea Institute of Science and
Technology for the study supports.
Methanol selectivity / %
25
Graphical Abstract
Textual Information
Description (if any)
Title Methanol synthesis over Cu and Cu-oxide-containing ZnO/Al2O3 using dielectric barrier discharge
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