Methanol Synthesis from Carbon Dioxide and

science technique
Hydrogen over CuO/ZnO/ZrO2 promoted catalysts
Maria MADEJ-LACHOWSKA Institute of Chemical Engineering, Polish Academy of Sciences,
Gliwice; Department of Applied Chemistry and Mechanics, Opole University of Technology, Poland;
Aleksandra KASPRZYK-MRZYK*, Henryk MOROZ Institute of Chemical Engineering, Polish
Academy of Sciences, Gliwice, Poland; Andrzej I. LACHOWSKI Department of Applied Chemistry
and Mechanics, Opole University of Technology, Poland; Hildegarda WYGO Institute of Chemical
Engineering, Polish Academy of Sciences, Gliwice, Poland

Please cite as: CHEMIK 2014, 68, 1, 6168

Introduction
Methanol is an important feedstock for the production of many
chemicals. It is the key material for the C1 chemistry. It is used for
manufacturing other chemicals such as formaldehyde, acetic acid,
chloromethane and many others. Moreover, it is an outstanding solvent
and recently it is used as a clean synthetic fuel [1, 2, 3]. Methanol can
be also converted via the steam reforming to the hydrogen-rich gas,
which can be fed to a fuel cell to generate electric power.
A breakthrough in the synthesis of methanol occurred when
it was found that the presence of CO2 in the reaction mixture is
favorable for methanol synthesis.The main reactions that occur in
carbon dioxide hydrogenation are following:
CO2 + 3H2 CH3OH + H2O (1)
a direct synthesis of methanol from carbon dioxide and hydrogen
CO2 + H2 CO + H2O (2)
the reverse water gas shift reaction.
Both reactions are exothermic and reversible.
However, the cost of such process, where CO2 hydrogenated
is higher than the cost of using CO+CO2 mixture. On the other
hand, there is a need of utilization of CO2, which is a waste gas
in many chemical processes. Methanol synthesis by hydrogenation
of CO2 gives great opportunity to achieve this goal. The industrial
methanol synthesis catalysts developed for the synthesis gas
containing hydrogen, carbon monoxide and only small amounts of
carbon dioxide in the presence of larger quantities of carbon dioxide
deactivate. Accordingly, there is a need for develop a new methanol
synthesis catalyst useful for carbon dioxide gas rich. This is evidenced
by a number of works on this subject that appeared in the scientific
journals. In numerous studies have been attempted to increase the
efficiency and improve selectivity of industrial methanol synthesis
catalyst from CO2 rich gas [4]. Most researchers consider that not
copper but Cu/ZnO system is responsible for the activity of copper
catalysts [5, 6]. The molar compositions of Cu:Zn in the industrial
Cu/ZnO-based catalysts, prepared by a co-precipitation method,
is about 70:30 [6]. Fujitani et al. found linear relationship between
methanol synthesis activity and copper surface area.
Many authors have found that the Cu catalysts containing zirconia
are active in the synthesis of methanol from CO2 and H2 [4, 8, 9]. Ortelli
et al. [9] considered zirconia supported catalysts as mechanically and
thermal stable, with relatively high specific surface area.
Development of a new, active in the presence of carbon dioxide
catalyst demands not only selecting appropriate components
(promoters) but also estimating their concentration. Among the
number of literature reports we selected: gallium [4, 7, 1014],
cerium [1518], palladium [19], lanthanum [2022] and chromium
[1724] as additions to CuO/ZnO/ZrO2 catalyst.
Corresponding author:
Aleksandra KASPRZYK-MRZYK, M.Sc., e-mail: a.kasprzyk@iich.gliwice.pl
Ma et al. [4] in their review paper report that the addition of Ga
or Cr to Cu/Zn/Al catalyst increases catalyst activity with respect
to Cu surface area. Fornero et al.[10] obtained the highest methanol
synthesis activity for 2wt% Cu/6 wt%Ga2O3/ZrO2 catalyst while
Toyir et al. [14] during investigating gallium promoted copper-based
catalyst chose ZnO as the better then SiO2 support. Fujitani et al. [7]
claim that copper surface area of Cu/ZnO/Ga2O3 catalyst containing
2030 wt% of Ga2O3 is about 40% higher than the copper surface
area of Cu/ZnO and Cu/ZnO/Al2O3 catalysts. Huang et al. [24]
described the significant improvements of the activity of skeletal
copper catalyst for the methanol synthesis reaction by adding small
amount of Cr2O3 to the surface of copper. Nonetheless, overloading
the Cu surface with Cr2O3 reduced the copper surface area and the
positive catalytic effect.
The literature reports refer to completely different catalytic systems,
so it is difficult or practically impossible to predict how the above-men-
tioned promoters affect for the activity of CuO/ZnO/ZrO2 catalyst.
The aim of this work is the study of the influence of promoters
on the activity of the CuO/ZnO/ZrO2 catalyst in the process of
methanol synthesis from CO2.
Preparation and characterization of the catalysts
The homogenization method using citric acid was selected in
order to prepare the catalysts. The oxide precursors of the catalysts
containing CuO, ZnO, ZrO2 and one of the promoters Ce, Cr, Ga,
La, Pd were obtained by decomposing the citrate complex of the
metals according to the method described by Courty et al. [25]. The
required amounts of nitrates of Cu, Zn, Zr and promoter were added
in small portions under intense stirring to 2 M solution of citric acid.
The solution was evaporated in a revolving flask in vacuum at 380K,
up to get the solid phase. The catalyst decomposition took place in
Buechi oven, in order to obtain oxides. Then it was calcinated at
temperature from 373 to 573 K.
Photo 1. Tubular Buechi oven decomposition of catalyst
The calcinated catalyst was turned into pills by using the
hydraulic press. Then the pills were crashed and sieved to a range
of 0.81.0 mm to perform the reaction.

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 A tubular, flow, high-pressure, fixed bed reactor, made of stainless Table 1
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steel was used in the experiments. The bed consisted of 2 g of the Composition, specific surface area BET and Cu active area values
catalyst placed between two layers of ceramic grains. The catalyst of tested
was reduced in a steam of diluted hydrogen (7% H2 in N2 under Catalyst CuO ZnO ZrO2 Promoter Promoter SBET Cu active
atmospheric pressure). The catalyst activity in the methanol synthesis concentra-tion area
was determined under the following range of conditions: the %wt %wt %wt %wt m2g-1 m2gkat-1

temperature from 433 to 513 K, the pressure 8 MPa and the reaction Cu/Zn/Zr 62.4 25.0 12.6 20 6.1
gas composition: H266%, N212%, CO222%. After leaving the
reactor, the reaction mixture was analyzed chromatographically Cu/Zn/Zr/Ce 65.3 26.3 4.5 Ce2O3 3.9 15 7.9
with the Varian Star 3800 apparatus. The methanol content was
Cu/Zn/Zr/Cr 65.2 26.3 7.7 Cr2O3 0.7 24 8.7
determined by the flame ionization detector (FID) with CP-Wax
column. Gases were analyzed by the thermal-conductivity detector Cu/Zn/Zr/Ga 65.3 26.3 4.5 Ga2O3 3.9 21 8.7
(TCD) with Carbo Plot column. The pictures of the testing equipment
are presented in Figure 1 and Photo 2. Cu/Zn/Zr/La 65.3 26.3 4.5 La2O3 3.9 16 7.3

Cu/Zn/Zr/Pd 65.2 26.3 4.5 PdO 3.9 24 6.7

Fig. 1. Installation scheme

Fig. 2. Pore volume distribution

The results of the catalytic tests are presented in the form of

graphs: the dependence of CO2 degree of conversion (Fig.3), the
selectivity towards methanol (Fig.4), the methanol efficiency (Fig.5)
and (Tab.2).
Table 2
Selected catalytic test results
Temperature. conversion degree
Catalyst activity
and selectivity for
parameters for T=473 K
Catalyst maximum methanol yield
WMeOH SMeOH T W MeOH SMeOH
% g(kgkath)-1 % K % g(kgkath)-1 %

Cu/Zn/Zr 8 83 61 493 6 68 73

Cu/Zn/Zr/Ce 15 202 69 493 12 146 65

Photo 2. Installation for methanol synthesis
Cu/Zn/Zr/Cr 18 194 68 493 14 148 69
Specific surface area of the oxide precursor and catalyst was
Cu/Zn/Zr/Ga 17 211 71 513 10 120 74
measured with BET method using an Autosorb-1 Quantachrome
apparatus with nitrogen as adsorbate at 77.5 K. The active surface of Cu/Zn/Zr/La 17 205 70 493 13 152 67
copper in reduced catalyst was determined with the use of reactive
adsorption of N2O at 363 K (VG/ Fisons Quartz 200D). Cu/Zn/Zr/Pd 17 199 73 513 10 105 80

Results The CO2 conversion degree and selectivity values were

During the tests, six different catalyst have been prepared. The calculated according the following formulas:
compositions of the catalysts, specific surface area BET and active
area of Cu are presented in Table 1.
The base Cu/Zn/Zr catalyst is characterized by relatively flat
pore volume distribution (Fig. 2) and a maximum mean diameter
where: conversion degree of CO2
20nm. The addition of gallium affects in a visible way on the pore
S selectivity
size distribution change. There appeared pores of the average
inlet stream for component i
diameters ranging from 3 to 11 nm. This significant increase in
outlet stream for compnent i
pore volume (from 0.0812 cm3/g to 0.1014 cm3/g) has changed the
specific surface area SBET.

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Fig. 3. Temperature impact on CO2 conversion degree
The analysis of the catalytic test results shows a significant
improvement of the catalytic properties caused by promoters
introduced to the base catalyst CuO/ZnO/ZrO2.
Figure 3 presents the dependence of CO2 degree of conversion
from temperature. The highest value of conversion degree reach
catalysts with Cr and La.
Fig. 4. Temperature impact on selectivity
Figure 4 shows the temperature dependence of the selectivity. It
gives a noticeable decrease in selectivity with increasing temperature.
The best selectivity show catalyst with palladium promoter and for the
high temperature range 493 to 513 K catalyst containing gallium.
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Fig. 5. Temperature impact on methanol yield
The methanol yield dependence of temperature is presented
in Figure 5. Conversion degree and selectivity have impact on
methanol efficiency. A high temperature has positive effect on
running the parallel reaction (2), more carbon dioxide is converted
into carbon monoxide, thus methanol yield is decreasing [26].For
the most active catalysts with Ce, La and Ga additives, that reach
high degree of conversion at low temperature range, the curves of
methanol yield achieve their maximum. For the rest of catalysts,
the curves have rising tendency in the whole temperature range.
As we noticed, the differences in the methanol efficiency are really
small, they are in the limit of measurement error. The exception
is CuO/ZnO/ZrO2/PdO catalyst , which gives slightly lower values
of methanol yield in whole temperature range. In our opinion
for consideration deserves the catalyst with gallium promoter.
Although the catalyst achieves maximum methanol efficiency at
513 K , it is characterized by high selectivity in high temperature
range (about 70%).
Summary
the addition of suitable promoter has a beneficial impact on
the catalytic properties of copper catalysts. Depending on the
promoter used, the efficiency of catalyst can be twice as high
the highest methanol yields have been obtained for catalysts
with La, Cr or Ce promoter at 493 K
the catalyst with gallium promoter achieves the best parameter
for the upper range of temperatures studied.
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