The influence of Mn, Zr and Pb promoters on the performance of
Cu/ZnO/SBA-15 Catalyst for Hydrogenation of CO
2
to methanol
Sara Faiz Hanna Tasfy
1,a
, Noor Asmawati Mohd Zabidi
2,b
,
Maizatul Shima Shaharun
2,c
, Duvvuri Subbarao
1,d
1
Department of Chemical Engineering, Universiti Teknologi PETRONAS, Bandar Seri Iskandar,
31750 Tronoh, Perak, Malaysia.
2
Department of Fundamental and Applied Science, Universiti Teknologi PETRONAS, Bandar Seri
Iskandar, 31750 Tronoh, Perak, Malaysia.
a
miss25208@gmail.com,
b
noorasmawati_mzabidi@petronas.com.my,
c
maizats@petronas.com.my,
d
duvvuri_subbarao@petronas.com.my
Keywords: CO
2
hydrogenation, methanol synthesis, promoter
Abstract. The present work investigates the hydrogenation of CO
2
to methanol via a promoted
Cu/ZnO/SBA-15 catalyst. In order to understand the effect of Mn, Zr and Pb promoters on the
catalytic activity of Cu/Zn/SBA-15 catalysts, the hydrogenation of CO
2
was performed in a stirred
high-pressure reactor at 483K, 22.5bar, and a H
2
/CO
2
ration of 3. The physicochemical properties of
the catalysts were studied using N
2
physical adsorption, TEM and H
2
-TPR. The characteristics of
catalysts depended on the type of promoter and it influenced their catalytic performance. The Mn
and Zr promoters resulted in a larger surface area of the catalyst and improved catalytic activity and
methanol selectivity. However, an opposite effect was found for the Pb promoter. A 10%
improvement on the CO
2
conversion and 20% on the methanol selectivity was achieved due to the
double promotion effect of Mn and Zr on Cu/ZnO-SBA-15 catalyst.
Introduction
The rising concerns about global warming and imbalance in the carbon cycle urge for a rapid
development of an efficient CO
2
conversion process [1, 2]. The greenhouse effect is regarded as a
serious threat to the global environment [3, 4]. The mitigation of carbon dioxide, a major
greenhouse gas is an urgent issue. As a countermeasure, through catalytic hydrogenation of CO
2
a
significant amount of CO
2
can be effectively converted into valuable products, such as methanol,
which is a starting material for several chemicals, a medium for the storage and transportation of
hydrogen and alternative energy source as well. The current commercial process is based on a
Cu/ZnO/Al
2
O
3
catalyst which was introduced by ICI in 1966. Cu/ZnO/Al
2
O
3
catalysts have long
been used in industrial methanol synthesis because of their high catalytic activity, long life time,
high poison resistance, and relatively low reaction temperature and pressure [5]. Nevertheless,
finding a better catalyst for methanol synthesis is still a subject of intense investigations. One of the
methods to enhance the catalytic activity is by using promoters. Promotion of a heterogeneous
catalyst (adding small amounts of one or more extra elements to a proven catalytic system) can have
a huge impact on the catalytic properties. Promoters have been used to facilitate the reduction of the
catalyst in addition to the adsorption and dissociation of the reactant which consequently affects the
activity and selectivity of the product.
The majority of the catalysts for CO
2
hydrogenation contained Cu and Zn as the main
components together with different modifiers (Zr, Ga, Si, Al, B, Cr, Ce, V, Ti, etc.) [6, 7]. Xu et al.
[8] studied the structure and catalytic performance of CuMnZrO
2
modified with Fe. They found that
the presence of iron led to a decrease of the copper–zirconia interactions and reduced the methanol
synthesis activity. Meshkini, et al. [9] investigated the effect of the metal oxide additives (Mn, Mg,
Zr, Cr, Ba, W, and Ce) on the Cu/ZnO/Al
2
O
3
catalytic properties using a design of experiment
approach (1/16 full factorial design) and they found that the addition of oxide metals influenced the
catalytic activity, dispersion of Cu, Cu crystallite size, surface composition of catalyst and stability
Defect and Diffusion Forum Vol 365 (2015) pp 178-182
© (2015) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/DDF.365.178
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