Iron-Based Fischer-Tropsch Synthesis for the Efficient Conversion of Carbon Dioxide into Isoparaffins

Article abstract of DOI:10.1002/cctc.201600058

Iron-based Fischer-Tropsch (FT) synthesis in combination with hydroisomerization in the presence of zeolites for the synthesis of isoparaffins from CO₂/H₂ was conducted in a fixed-bed reactor. Relative to supported iron catalysts, th

Full text of DOI:10.1002/cctc.201600058

DOI: 10.1002/cctc.201600058
Communications
Iron-Based Fischer–Tropsch Synthesis for the Efficient
Conversion of Carbon Dioxide into Isoparaffins
[
a]
Shunshun Geng, Feng Jiang, Yuebing Xu, and Xiaohao Liu*
Iron-based Fischer–Tropsch (FT) synthesis in combination with
hydroisomerization in the presence of zeolites for the synthesis
of isoparaffins from CO /H was conducted in a fixed-bed reac-
by remaining fossil fuels but from splitting water by electroly-
[
15–19]
sis or other cleavage reactions.
The aim to reach CO2 production of fuels has prompted
2
2
tor. Relative to supported iron catalysts, the precipitated one
efficiently converted intermediate CO into hydrocarbons by
supplying a high density of FT active sites on the catalyst sur-
face. Removing water by interstage cooling and promoting the
CO conversion step in the FT synthesis were effective ap-
some researchers to focus on FTS by using CO in place of
2
[
20–26]
CO.
Iron catalysts are no doubt the best choice for CO2-
based FTS, because they also catalyze the reverse water-gas
shift (RWGS) reaction to cleave one of the oxygen atoms in
CO to make CO [Eq. (1)]. The CO thus generated can then be
2
proaches in achieving a high CO conversion, because of an in-
combined with H to make a combination known as renewable
2
2
crease in the driving force to the reaction equilibrium. Particle
mixing of 92.6Fe7.4K with either 0.5Pd/b or HZSM-5 zeolite ef-
fectively hydroisomerized the resulting FT hydrocarbons into
gasoline-range isoparaffins. Particularly, HZSM-5 displayed
a higher isoparaffin selectivity at approximately 70%, which re-
sulted from easier hydrocracking and hydroisomerization of
the olefinic FT primary products.
syngas, which can be converted into hydrocarbons by FTS
[Eq. (2)]. As the chain propagation mechanism of FTS is to syn-
thesize a wide distribution of normal hydrocarbons unsuitable
as gasoline fuel, it is desired that a highly selective synthesis of
gasoline-range isoparaffins with high octane numbers could be
achieved from CO -based FTS followed by subsequent hydro-
2
isomerization with a zeolite catalyst [Eq. (3)].
CO þ H ! CO þ H O
DH573 K ¼ 38 kJ molÀ1
ð1Þ
2
2
2
The high energy density and ease of transport of gasoline and
other liquid hydrocarbons have made them the mainstay of
the world’s transportation infrastructure. Although researchers
continue to pursue the use of low-carbon gases such as meth-
ane and hydrogen as transportation fuels and even though
electric cars are proliferating, there is no good alternative to
liquid fuels for long-distance trucks and other heavy vehicles,
DH573 K ¼ À166 kJ molÀ1 ð2Þ
CO þ 2 H ! ð1=nÞðC H Þ
2
n
2n
CnH2n ! isomerized hydrocarbons
CO þ H O ! CO þ H
ð3Þ
DH573 K ¼ À38 kJ molÀ1 ð4Þ
2
2
2
In the case of CO-based FTS by iron catalysts, the water-gas
shift (WGS) reaction [Eq. (4)] may not be avoided under the re-
action conditions, and it is directly responsible for the forma-
[
1]
as well as aviation. Given the limited availability of crude oil
and the conversion of coal into synthetic liquid fuel by syngas
(
(
a mixture of CO and H ) followed by Fischer–Tropsch synthesis
tion of stable CO
in low carbon efficiency of converting CO into premium fuels.
Given that CO is relatively unreactive and is formed as one of
2
with a high level of selectivity, which results
2
[
2–9]
FTS),
this dependence poses major security and environ-
[
10]
mental problems. Arguably, the conversion and utilization of
such carbon-rich fossil fuels are the main contributors to the
2
the final products, it is easier to control the CO conversion of
the CO-based FTS according to the necessity of the reaction.
emission of the greenhouse gas CO , which leads to climate
2
[
11]
change. Reducing CO emissions must indeed be an urgent
The direct synthesis of isoparaffins starting from CO/H
2
has
However, research on the
synthesis of the isoparaffins concentrated in the gasoline frac-
tion by using CO is rare. On the basis of the catalytic mecha-
nism of the hydroisomerization of Fischer–Tropsch (FT) prod-
ucts, the overall performance of CO conversion into isoparaf-
fins mainly relies on how CO -FTS can be optimized consider-
2
[
27–31]
and long-term task for sustainable development in the energy
been intensively investigated.
[12,13]
and environmental sectors.
It has been confirmed for
many years that the hydrogenation reaction is amongst the
most important chemical conversions of highly concentrated
2
[
11,14]
CO2.
However, we point out that, authentically, to realize
2
the recycling of CO , hydrogen sources cannot be generated
2
2
ing the catalytic activity and selectivity of the CO feed gas.
2
CO -FTS is significantly different from CO-based FTS. First,
2
the feed of the reaction starts from very stable CO molecules.
2
[
a] S. Geng, Dr. F. Jiang, Dr. Y. Xu, Prof. Dr. X. Liu
The Key Laboratory of Food Colloids and Biotechnology
Ministry of Education
Moreover, in the reversible RWGS reaction, the return of CO2
from the CO that is formed is a thermodynamically favorable
School of Chemical and Material Engineering
Jiangnan University
Wuxi 214122, Jiangsu Province (P.R. China)
E-mail: liuxh@jiangnan.edu.cn
process, and this limits the CO2 conversion to a low level.
Therefore, on the basis of the points mentioned above for the
CO -based synthesis of isoparaffins by iron-based FTS, we fo-
2
cused on understanding how the CO conversion could be en-
Supporting Information for this article can be found under http://
dx.doi.org/10.1002/cctc.201600058.
2
hanced with a high carbon efficiency towards renewable iso-
ChemCatChem 2016, 8, 1303 – 1307
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Communications
paraffins. Thus, the formation of CO and CH should be sup-
4
pressed as much as possible. To realize these targets, we inves-
tigated K-promoted supported and unsupported iron catalysts
and different reaction conditions, reactor systems, and zeolites
for the catalytic conversion of CO2.
All catalytic tests for the selected iron catalysts were con-
ducted in a single fixed-bed reactor. As listed in Table 1, under
À1 À1
the reaction conditions of 4008C, 1 MPa, and 1120 mLgcat h ,
iron supported on different supports by K-promotion displayed
undesirably high selectivities to CO ranging from 23.2 to
5
4.5% and selectivities to CH ranging from 22.4 to 41.2% at
4
Table 1. Results measured over supported and unsupported iron-based
catalysts in a fixed-bed reactor with H /CO =3.
2 2
[a]
Catalyst
CO
%]
2
conversion Selectivity
[Cmol%]
[
=
=
o
o
CO CH
4
C
2
–C
4
C
2
–C
4
C
5+
[
b]
1
1
1
1
1
9
5Fe5K/SiO
2
16.5
40.7
39.5
35.9
17.4
41.7
83.1 6.4 0.7
23.2 41.2 4.7
31.9 25.4 3.5
54.5 22.4 9.4
58.8 3.3 4.6
6.0 10.3 21.6
0.7
23.4
21.1
3.2
1.9
6.2
9.0
7.4
18.1
10.6
31.4
56.0
[b]
2 3
5Fe5K/g-Al O
[
b]
5Fe5K/AC
[
[
b]
5Fe5K/b-SiC
5Fe5K/b-SiC
c]
[c]
2.6Fe7.4K
Figure 1. TEM images of the as-prepared a) supported 15Fe5K/b-SiC and
b) precipitated 92.6Fe7.4K catalysts.
[
[
5
a] Numbers in the catalysts indicate the loading of elements in wt%.
À1 À1
b] 4008C, 1 MPa, and 1120 mLgcat
h
.
[c] 3008C, 2.5 MPa, and
catÀ1 À1
h .
60 mLg
similar conversions of approximately 40% (except for 15Fe5K/
SiO , which was clearly inactive for CO conversion). However,
2
2
=
=
comparing the selectivity to light olefins, that is, C2 to C4
,
the SiC-supported catalyst seemed to be more favorable in
terms of the formation of olefins to give a preferential selectiv-
=
=
ity of approximately 74.6% for C2 to C4 in total C –C hydro-
2
4
carbons. Furthermore, the 15Fe5K/b-SiC catalyst was tested at
a milder reaction temperature of 3008C, and it also afforded
=
=
a similarly high selectivity to CO and C2 to C4 (58.8 and
7
9
0.8%, respectively). In contrast, the precipitated iron
2.6Fe7.4K catalyst was more beneficial in obtaining overall
2
Scheme 1. Reaction network for isoparaffin synthesis by CO -based FTS fol-
lowed by hydroisomerization of the FT products.
high performance, and it showed significantly higher activity
41.7%), very low selectivity to CO (6%) and CH (10.3%), and
(
4
=
=
desired high C2 to C4 selectivity (77.7%) for CO conversion
supported catalyst and a small number of particularly large
particles approximately 80–100 nm in size were observed.
2
under the same reaction conditions.
The results above indicate that the precipitated iron catalyst
was better suited for further CO reaction to reduce the CO se-
A reaction mechanism for the hydrogenation of CO to hy-
2
drocarbons over an iron catalyst is proposed in Scheme 1. The
iron catalyst directly catalyzes CO2 to form hydrocarbons,
which is attributed to its activity for the RWGS reaction. CO2
hydrogenation has been considered to proceed by a two-step
lectivity. Accordingly, the carbon efficiency for CO conversion
2
into usable fuels was greatly improved along with a substantial
decrease in the selectivity to CO from 58.8 to 6%. To elucidate
how the CO selectivity was effectively suppressed, Figure 1
shows the TEM images of two typical as-prepared 15Fe5K/b-
SiC and 92.6Fe7.4 K catalysts. It is clear that the 15Fe5K/b-SiC
catalyst prepared by impregnation exhibits an average size of
process with the initial conversion of CO into CO by the
2
[
11]
RWGS followed by chain propagation. On the basis of the re-
action approach, the active sites on the iron catalyst should be
divided into two types. One is probably an oxidic iron phase,
which appears to be active for the RWGS reaction (pathway 1)
(
3.4Æ0.7) nm and a homogeneous dispersion of iron oxide
nanoparticles on the SiC support. For the unsupported precipi-
tated 92.6Fe7.4K catalyst, the average size of the iron oxide
particles was much larger at (32.1Æ13.7) nm than that for the
by abstraction of an O atom in CO by a H radical to form CO.
2
Another is the well-known iron carbide phase (Fe C ) for the
5
2
dissociation of CO to carbon–carbon propagation by FTS
[
32,33]
(
pathway 3).
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As illustrated in Scheme 1, the hydrogenation of CO over
It has been demonstrated that cobalt as a second metal can
2
the iron catalyst produces products or intermediates, including
CO, water, and hydrocarbons. CO is the reaction intermediate
formed in the first step by the RWGS reaction. It further reacts
into hydrocarbons as much as possible rather than leaving the
effectively promote the conversion of CO by accelerating the
2
reaction rate towards the FTS. To enhance the conversion of
CO , a higher H /CO ratio can also be advantageous not only
2
2
2
to shift the RWGS reaction to the right side but also to speed
up the irreversible FT reaction step. As shown in Table 3, in-
creasing the H /CO ratio from 3 to 6 led to an increase in the
catalytic surface. Thus, the overall efficiency of utilizing CO in-
2
creases with a lower selectivity to CO. In the case of the pre-
cipitated iron catalyst, the CO selectivity is highly reduced (6%
in Table 1), which might be ascribed to a larger active iron car-
bide surface, which increases the chances of CO-FTS. In con-
trast to the precipitated catalyst, the supported iron catalyst
has a low concentration of FT active sites on the support. It is
thus easier for the formed CO to escape the catalyst surface
before further reaction (see Figure S2, Supporting Information),
which results in a high CO selectivity (58.8% in Table 1).
2
2
conversion of CO from 41.7 to 63.9%. Moreover, a higher H2
2
concentration also led to the formation of a greater amount of
CH , lower selectivity to olefins, and a decrease in the probabil-
4
ity of chain growth.
Table 3. Effect of H
2 2
/CO ratio on the performance of the hydrogenation
[a]
of CO over a precipitated 92.6Fe7.4K catalyst.
2
Owing to the thermodynamic and chemical stability of CO2
Molar ratio H
2
/CO
2
CO
[%]
2
conversion Selectivity
[Cmol%]
molecules, as shown in Table 1, the conversion of CO is always
2
=
=
o
o
4
limited to approximately 40%, close to the chemical equilibri-
CO CH
4
C
2
–C
4
C
2
–C
C
5+
um, upon performing the hydrogenation of CO under differ-
3.0
4.5
41.7
51.1
63.9
6.0 10.3 21.6
4.7 13.9 24.8
3.1 16.4 21.9
6.2
8.8
13.5
56.0
47.7
45.0
2
ent reaction conditions in a single fixed-bed reactor. Consider-
ing the RWGS as a reversible reaction (pathway 2), the driving
force for the RWGS reaction can be increased by consuming
the CO intermediate to form a hydrocarbon or by decreasing
the steam content in the reactor (pathway 4). Given that it is
difficult for the monometallic iron catalyst to enhance the con-
6.0
catÀ1 À1
h .
[a] Under the conditions of 3008C, 2.5 MPa, and 560 mLg
As described in Scheme 1, a large amount of water was also
produced in both the RWGS reaction and FT reaction steps
version of CO , it might be feasible to design a bimetallic cata-
2
lyst in which the other metal is highly active in converting CO
into hydrocarbons and inactive for the WGS reaction (path-
during the hydrogenation of CO to hydrocarbons. The water
2
content was approximately twofold higher than that in the
[
34]
way 2). On the basis of this principle, cobalt metal was intro-
conventional FT synthesis starting from feed gas of H /CO. The
2
duced into the iron catalyst to investigate the CO hydrogena-
high concentration of water vapor has an inhibiting effect on
2
tion reaction. Table 2 shows the catalytic results over both the
the reaction rate for the conversion of CO , and this is mainly
2
caused by limiting the chemical equilibrium, as the WGS reac-
tion is a favorable process. The chemical equilibrium is affected
to a smaller extent by the reaction temperature, as the temper-
Table 2. K-promoted FeCo bifunctional catalysts tested for the hydroge-
[a]
nation of CO
2
.
ature can clearly not improve the conversion of CO . The
2
RWGS reaction is slightly endothermic, and a higher reaction
temperature is not helpful to shift the equilibrium but is re-
Catalyst
CO
%]
2
conversion Selectivity
[Cmol%]
[
=
=
o
o
4
CO CH
4
C
2
–C
4
C
2
–C
C
5+
quired to activate stable CO molecules on the basis of ther-
2
[
b]
9
8
8
1
1
2.6Fe7.4K
41.7
54.6
57.2
45.6
52.2
6.0 10.3 21.6
2.0 18.9 24.4
1.6 22.4 23.5
6.2
7.4
8.7
4.1
1.3
56.0
47.0
43.8
3.6
modynamic and mechanistic reasons. To drive the conversion
[
[
b]
b]
8.3Fe7.1K4.6Co
4.0Fe6.7K9.3Co
of CO by shifting the equilibrium, the most effective approach
2
might be by removing water from the reactor (pathway 4). As
demonstrated in Figure 2, a two-stage fixed-bed reactor
system in series with interstage cooling to condensate the
water and hydrocarbons (see Figure S3) can efficiently improve
the conversion of CO2 from 41.7 to 62.3%. Moreover, in this
[
c]
5Co/SiO
5Co/SiO
2
0.2 91.8
4.2 92.4
0
0
[
b]
2
2.2
catÀ1 À1
h .
[
[
a] Under the conditions of 2.5 MPa, H
b] 3008C. [c] 2408C.
2
/CO
2
=3, and 560 mLg
setup the CH selectivity is lowered from 13.5 to 11.4%, and
4
the C5+ selectivity is slightly increased from 56 to 61.7%. Sup-
cobalt-containing and monometallic iron catalysts. One can
see that the introduction of cobalt is notable in promoting the
pressing the formation of CH with a two-stage reactor system
4
results from a secondary reaction of the olefins in which the
uncondensed gas products in the rich olefins are introduced
into the second reactor. Initiating secondary chain growth by
re-adsorption of olefins to decrease the selectivity to light hy-
drocarbons (see Scheme S1) was confirmed in our previous
conversion of CO , which increased with an increase in the
2
loading of cobalt. However, a higher selectivity to CH was ob-
4
tained, despite the increase in the conversion of CO2 by
adding cobalt metal, and this results from the fact that the hy-
drogenation capability of cobalt metal is higher than that of
the iron catalyst. This was confirmed by using the 15Co/SiO2
[
35–38]
publications.
To this end, we studied how to obtain the optimal catalytic
catalyst, by which CH was mainly produced with greater than
activity and selectivity for the conversion of CO by catalyst
4
2
9
0% selectivity at different temperatures.
design, selecting appropriate reaction conditions, and process
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=
=
ed to the promotion effect of the hydrogenation of C2 –C3
and longer-chain olefins into n-paraffins by hydrogen spillover
resulting from the fact that Pd inhibits further chain growth
and/or isomerization (see Scheme S2a). In the case of HZSM-5,
the higher selectivity to olefins is in favor of hydroisomeriza-
tion because of a lower activation energy required to form car-
=
=
bonium ions. Also, light olefins such as C2 and C3 can add
to the carbonium ions to increase the amount of isomers, and
this results in a marked decrease in the C2~3 selectivity (see
Scheme S2b). Interestingly, powder mixing of the 92.6Fe7.4K
and zeolite catalysts not only lowered the conversion of CO2
but also produced a small amount of isoparaffins. The acidic
sites in the zeolite were poisoned by the K alkali metal in the
9
2.6Fe7.4K catalyst owing to their intimate contact, and this is
Figure 2. CO
measured in different reactor systems at 3008C and 2.5 MPa with a molar
/CO ratio of 3 (in the case of reactor D: 3208C, H /CO =4.5). a) single re-
actor, 3 g catalyst; b) single reactor, 6 g catalyst; c) two-stage reactor with in-
terstage cooling, 3 g catalyst in each reactor; d) two-stage reactor with inter-
stage cooling, 3 g catalyst in each reactor.
2
conversion and product selectivity on the 92.6Fe7.4K catalyst
directly responsible for the decrease in the hydroisomerization
activity. At the same time, the 92.6Fe7.4K catalyst was also de-
activated by the acidic sites in the zeolite, which resulted in
H
2
2
2
2
a lower conversion of CO and a higher selectivity to CO.
2
In conclusion, we studied the hydrogenation of CO to liquid
2
fuels (isoparaffins) in a fixed-bed reactor by combining iron-
design, which is a basis for developing a highly efficient pro-
based CO Fischer–Tropsch synthesis (FTS) with subsequent hy-
2
cess of the conversion of CO2 into isoparaffins by CO -FTS.
droisomerization. Owing to the chemical stability of CO mole-
2
2
Moreover, the normal hydrocarbon hydroisomerization reac-
tion is also vital for maximum and tailor-made selectivity to
isoparaffins in a requisite carbon number range. According to
our previous research and as reported in the literature, two
kinds of zeolite catalysts have been applied for the hydroiso-
cules and a limit to the thermodynamic equilibrium, the chal-
lenge was to break the equilibrium to obtain a high conversion
of CO and a high carbon efficiency to liquid fuels. On the
2
basis of the understanding of the chemical reaction network
and the rate-determining step of the CO -FTS, we considered
2
[31,39]
merization of FT products into isoparaffins.
As shown in
that removing water from the reactor and enhancing the con-
version rate of CO by the Fischer–Tropsch (FT) reaction were
the two most effective approaches to realize the target above.
Table 4, the precipitated 92.6Fe7.4K catalyst for the hydroge-
Therefrom, a high conversion of CO with low selectivities to
2
Table 4. Synthesis of isoparaffins from CO
2
-FTS with
a
precipitated
CO and CH and olefinic hydrocarbon products were achieved
4
9
2.6Fe7.4K catalyst by combining the hydrocracking of the hydrocarbons
over a precipitated K-promoted iron catalyst in a fixed-bed re-
actor system in series with interstage cooling to remove water.
[
a]
by using 0.5Pd/b or HZSM-5.
[b]
Catalyst
CO
%]
2
conversion Selectivity
[Cmol%]
Iso-C4~6
[%]
An improvement in the conversion of CO by removing water
2
[
was attributed to a decrease in the rate of the water-gas shift
reaction. Relative to the impregnated iron catalysts, the pre-
cipitated iron catalyst lowered the CO selectivity remarkably by
supplying a high density of FT active sites on the catalyst sur-
face, which increased its conversion before it could diffuse out
of the catalyst surface. Although adding cobalt metal and in-
CO
CH
4
C
2~3
9
9
9
9
9
2.6Fe7.4K
2.6Fe7.4K+0.5Pd/b
2.6Fe7.4K+HZSM-5
2.6Fe7.4K+0.5Pd/b
2.6Fe7.4K+HZSM-5
41.7
42.7
43.9
32.6
35.1
6.0 10.3 19.3
9.6
[
c]
6.0
6.1
9.8 24.5 51.3
9.5 10.8 69.7
[c]
[d]
11.0 21.7 31.4 10.6
22.2 10.7 30.1 28.7
[d]
creasing the H /CO ratio evidently raised the conversion of
catÀ1 À1
h .
2
2
[
[
a] Under the conditions of 3008C, 2.5 MPa, and 560 mLg
b] Numbers indicate selectivity to isohydrocarbons in total C4~6 hydrocar-
CO , the selectivity to CH also increased owing to an increase
2
4
bons. [c] Particle mixing. [d] Powder mixing.
in the rate of the hydrogenation reaction. For isomerization,
HZSM-5 was more favorable in terms of producing isoparaffins
by virtue of a mechanism involving the dimerization of highly
olefinic FT primary products into higher isomers by carbonium
ions. This study provides an efficient approach for the conver-
sion of CO into renewable energy. In the future, CO recycling
nation of CO2 produced negligible selectivity to isoparaffins
(
9.6% in iso-C4~6). Relative to the iron catalyst only, both the
.5Pd/b and HZSM-5 catalysts introduced by particle mixing
0
2
2
did not markedly improve the conversion of CO or the selec-
for the production of chemicals and energy by CO as a reactive
intermediate and subsequent chemical conversion by catalysis
is bound to attract increasing attention to enable a sustainable
2
tivities to CO and CH . However, the selectivities to C2~3 and
4
iso-C4~6 differed significantly over HZSM-5. As a result, the se-
lectivity to C2~3 remarkably decreased from 19.3 to 10.8% and
a very high selectivity to isoparaffin was obtained (69.7% in
iso-C4~6). In contrast to HZSM-5, the 0.5Pd/b catalyst led to
a higher C2~3 selectivity from 19.3 to 24.5% and lower isoparaf-
fin selectivity (51.3% in iso-C4~6), which is presumably attribut-
society. A key challenge of this strategy for CO utilization is
2
how the selectivity of the products can be controlled under re-
action conditions that are difficult to adjust, including the par-
tial pressures of CO and H and their concentrations on the
2
catalyst surface.
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Communications
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This work was financially supported by the National Natural Sci-
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Received: January 18, 2016
Published online on March 8, 2016
ChemCatChem 2016, 8, 1303 – 1307
www.chemcatchem.org
1307
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim