Effect of the Nature of Catalysts on Their Properties in the Hydrogenation of Carbon Dioxide

Article abstract of DOI:10.1134/S0036024418100345

Abstract: The effect the nature of a metal has on the activity and selectivity of the catalysts in hydrogenation of carbon dioxide into carbon oxide and hydrocarbons under high pressure is studied for the catalysts containing Au, Pt, Fe, and Co. Based on

Full text of DOI:10.1134/S0036024418100345

ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2018, Vol. 92, No. 10, pp. 1889–1892. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © A.L. Tarasov, E.A. Redina, V.I. Isaeva, 2018, published in Zhurnal Fizicheskoi Khimii, 2018, Vol. 92, No. 10, pp. 1544–1547.
CHEMICAL KINETICS
AND CATALYSIS
Effect of the Nature of Catalysts on Their Properties
in the Hydrogenation of Carbon Dioxide
a,
a
a
A. L. Tarasov *, E. A. Redina , and V. I. Isaeva
a
Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, 119991 Russia
*
e-mail: atarasov@ioc.ac.ru
Received January 18, 2018
Abstract—The effect the nature of a metal has on the activity and selectivity of the catalysts in hydrogenation
of carbon dioxide into carbon oxide and hydrocarbons under high pressure is studied for the catalysts con-
taining Au, Pt, Fe, and Co. Based on a comparison of measured values of СО conversion and calculated
2
data, it is concluded that only the catalysts containing Fe and Co display pronounced bifunctional properties.
These catalysts exhibit activity in both hydrogenation and subsequent CO conversion to С hydrocarbons,
2+
shifting the equilibrium toward the formation of products.
Keywords: carbon dioxide, hydrogenation, thermodynamics, carbon oxide, Fischer–Tropsch process
DOI: 10.1134/S0036024418100345
INTRODUCTION
the reverse reaction of СО hydrogenation (RWGS),
2
which results in the formation of carbon oxide and
The catalytic transformation of carbon dioxide is of
great importance to the organic synthesis industry [1].
Carbon dioxide is the main greenhouse gas, and its
emissions should be reduced to a stable minimum.
possibly hydrocarbons, since Fischer–Tropsch pro-
cess CO + 2H = –(CH )– + H O (∆H
=
2
2
2
300C
‒
166 kJ/mol) with the formation of different hydro-
carbons, liquid and otherwise, can accompany the
main reaction of hydrogenation, CO + H
The problem is not only to capture and store CO
2
=
2
emissions but to find attractive ways of using CO to
2
2
CO + H O (∆H
= +38 kJ/mol). However, CO
2
obtain valuable products, including carbon oxide and
2
300C
hydrogenation should be conducted at high pressures
above 20 atm) required for Fischer–Tropsch process,
while the catalyst should be sufficiently active in the
different types of hydrocarbon fuels [2, 3]. One way of
(
solving the problem of utilizing СО is its hydrogena-
2
tion with the formation of a more reactive gas—carbon
oxide, which can in turn participate in the Fischer–
Tropsch process, resulting in the formation of different
gaseous and liquid hydrocarbons [4, 5].
conversion of СО into carbon oxide (Fe O –K O
fused catalyst is one of such catalysts [7]).
2
2
3
2
The Fischer–Tropsch process is now widely stud-
ied in connection with its application in the produc-
tion of synthetic fuel [9]. Catalysts containing Co
based on aluminum oxide, which is characterized by
high thermal stability, mechanical strength, large sur-
face areas, and large pore sizes are most promising for
this reaction [10, 11]. Co nanoparticles exhibit high
activity and selectivity toward linear hydrocarbons in
combination with low activity toward the WGS reac-
tion [12]. However, strong interaction between metals
leads to the formation of cobalt–aluminum spinels,
which are not active in the Fischer–Tropsch process.
This problem can be solved using other carriers char-
acterized by large specific surfaces, e.g., porous
metal–organic frameworks (MOFs) [13–17]. The
It is known that several metals can selectively trans-
form carbon dioxide into CO, but not into methane. It
was therefore established in investigating different
copper-containing and bimetallic Cu-Ni/Al O cata-
2
3
lysts in the hydrogenation of СО that Cu predomi-
2
nately catalyzes the formation of CO, while Ni is in
contrast effective in the formation of methane [6]. In
[
7], we studied a range of fundamentally different
metal-containing catalysts in the hydrogenation of
СО under atmosphere pressure in the range of 200–
2
2
4
−
5
00°С. We showed that Au/SO –ZrO catalysts and
2
Fe O –K O fused catalysts exhibit high activity and
2
3
2
more than 95% selectivity toward CO formation. It is
2
4
−
known [8] that Au/SO –ZrO catalysts are highly authors of [18] showed that using 15% cobalt-contain-
2
active in water–gas shift (WGS) reaction. We may ing catalyst based on the metal–organic MIL-53(Al)
therefore assume that the catalysts that are active in framework in Н /СО = 2 mixture allows to obtain val-
the WGS reaction are also promising for application in ues of carbon oxide conversion of up to 60.2% and
2
1889

1890
TARASOV et al.
kmol
1% Pt/ZrO –CeO Catalyst
2
2
3
2
1
2
H (g)
This catalyst was obtained by depositing platinum
on a surface of Ce Zr O , synthesized according to
0.6
0.4
2
[
6
20]. The catalyst has a specific surface area of
2
5.4 m /g. The deposition of platinum from a Н PtCl
2 6
aqueous solution at controlled pH was performed as
described in [19].
СO (g)
2
10% Co/MIL-53(Al) Catalyst
This catalyst was obtained according to [18, 21] via
the incipient wetness impregnation of MIL-53(Al)
metal–organic framework carrier with an aqueous
solution of cobalt acetate, followed by drying for 15 h
at 80°С. The catalyst precursor was reduced in a
hydrogen flow (2000 mL/(g h) at 400°С for 1 h
directly in the reactor before the experiments.
СO(g)
H
2
O(g)
0
100
200
300
400
500
T, °C
Fig. 1. Thermodynamic equilibrium concentrations of
products and reagents in our 2.7Н /СО mixture at
2
2
30 atm.
Catalytic Tests
A mixture of hydrogen and СО was supplied to a
2
flow reactor (a metal tube 8 mm in diameter) at a pres-
sure of 30 atm; the flow rate was 12 mL/min. The
molar ratio was Н /СО = 2.7. The catalyst load was
selectivity toward С5+ hydrocarbons of up to 73% at a
pressure of 20 atm.
2
2
3
The aim of this work is a comparative study of the 1 cm . Catalytic tests were performed in the 300–
catalytic properties of fundamentally different types of 500°С range of temperatures; each temperature step
catalysts in the two-stage hydrogenation conversion of was 100 K. A trap cooled to −10°С and used to con-
СО into СО (the first stage) and the subsequent con- dense the liquid products was mounted at the reactor
2
output. Gas from the trap output was analyzed with
model 3700 chromatograph (NPO Granat) equipped
version of a mixture of the resulting carbon oxide and
Н into hydrocarbons in the Fischer–Tropsch process
2
with two columns packed with HayeSep-Q (Н + СО,
2
at high pressures.
CH , СО , С ) and 5А molecular sieves (H , CH ,
4
2
2
2
4
СО). Liquid products were analyzed with the same
chromatograph with a flame-ionization detector using
an SE-30 capillary column (50 m) in the isothermal
mode at 65°С. Helium served as the carrier gas.
EXPERIMENTAL
Catalysts and Their Preparation
A number of the most promising catalysts for the
hydrogenation of carbon oxides, including the
Fischer–Tropsch process, was selected for investiga-
tion.
RESULTS AND DISCUSSION
Figure 1 presents the calculated thermodynamic
equilibrium concentrations of reagents and products for
СО hydrogenation in the gaseous phase with the for-
2
mation of CO. Our calculations were performed using
the НCS-4 program (Haldor Topsøe).
Fe–K Fused Catalyst
Figure 1 shows that СО hydrogenation is a high-
2
The traditional catalyst for the Fischer–Tropsch
process was prepared by fusing iron oxide (magnetite)
temperature reaction. High temperatures (300–
5
00°С) are needed for the efficient conversion of СО
2
with chemical promoter K O and structural promoters
2
into CO; considerably lower temperatures are required
MgO and Al O in an electric arc furnace at ~1650°C.
2
3
for the subsequent conversion of CO into gaseous С –
2
2
The surface area measured via BET was 95 m /g.
С and liquid С hydrocarbons according to the
4
5+
Fischer–Tropsch process. It is known [22] that the
traditional iron and cobalt catalysts of the Fischer–
Tropsch process are efficient up to 350 and 240°С,
respectively, where the activity of cobalt is higher than
2
% Au/S–ZrO Catalyst
2
The industrial catalyst for the WGS reaction, pro- that of iron [23]. From a thermodynamic viewpoint,
duced by Chevron using the technique described in the formation of С hydrocarbons during СО hydro-
19], is characterized by a surface area of 140 m /g.
2+
2
2
[
genation is thus somewhat contradictory.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
Vol. 92
No. 10
2018

EFFECT OF THE NATURE OF CATALYSTS ON THEIR PROPERTIES
1891
Table 1. Conversion of СО and selectivity toward hydrocarbons in the Fischer–Tropsch process on different metal-con-
2
taining catalysts at 30 atm and 300–500°С
Conversion into (С, mol %) Selectivity towards hydrocarbons, %
Catalyst
Т, °С
KCO2 , %
СО
НС
С1
С –С
С5+
2
4
2
% Au/S–ZrO2
300
12.1
22.4
39.6
14.0
27.0
43.9
24.8
33.5
45.5
30.4
38.9
36.0
10.8
17.9
27.6
7.1
18.3
23.5
18.6
24.9
27.4
5.9
1.3
4.5
12.0
6.9
8.7
20.4
6.2
100
99.1
—
0.1
0.4
5.9
3.8
0.9
24.9
27.8
35.6
24.6
19.9
9.5
—
—
—
—
—
4
5
00
00
99.6
94.1
96.2
99.1
73.0
68.1
64.4
44.6
76.1
90.5
1% Pt/ZrO –CeO2
300
2
4
5
00
00
—
Fe–K fused
300
2.1
4.1
Trace
30.8
4.0
—
4
5
00
00
8.6
18.1
24.5
21.7
14.5
10% Co/MIL-53(Al)
300
4
5
00
00
17.2
21.5
Our results on the catalytic transformations of СО
400°С) range, where the efficient formation of С
2+
2
in a Н /СО = 2.7 (molar) mixture on different metal- hydrocarbons is observed. The obtained value of con-
2
2
containing catalysts in the 300–500°С range of tem- version for 10% Co/MIL-53(Al) catalyst, which is the
peratures at a pressure of 30 atm and gas volume feed one most efficient for obtaining С5+ liquid hydrocar-
−1
rate of 720 h are given in Table 1.
bons, is thus more than 6% higher than is thermody-
namically possible under these conditions (at 300°C).
In our opinion, this clearly shows that iron- and
cobalt-containing catalysts exhibit bifunctional prop-
Table 1 shows that gold-containing catalyst
2
% Au/S–ZrO , which displayed high activity and
2
selectivity toward the formation of CO (K
СО
≈ 30%,
CO2
erties. The equilibrium of СО hydrogenation then
2
С
≈ 90% at 500°С) in [7], exhibits considerably
shifts toward the formation of CO which simultane-
ously participates rapidly in the Fischer–Tropsch pro-
cess, resulting in the formation of С hydrocarbons
lower selectivity toward CO (~70%) at a higher pres-
sure (30 atm). At the same time, it is completely inef-
2+
fective in the formation of gaseous С –С and liquid
2
4
and improving the selectivity and efficiency of hydro-
carbon formation.
С hydrocarbons. Methanation proceeds more inten-
5
+
sively at high pressure.
The absence of С5+ hydrocarbons is also observed
for platinum-containing 1% Pt/ZrO –CeO catalyst;
ACKNOWLEDGMENTS
2
2
This work was supported by the Russian Science
Foundation, project no. 14-50-00126.
however, it is more efficient for the formation of С –
2
С hydrocarbons than 2% Au/S–ZrO . Figure 1
4
2
shows the СО conversions calculated from thermo-
2
dynamics, which are 24.2, 35.1, and 48% at 300, 400,
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RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
Vol. 92
No. 10
2018