Journal of CO2 Utilization 17 (2017) 284–289

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Journal of CO2 Utilization

journal homepage: www.elsevier.com/locate/jcou

Simulation of novel process of CO2 conversion to liquid fuels

Nora Meiri, Roman Radus, Moti Herskowitz*
Chemical Engineering Department, Blechner Center for Industrial Catalysis and Process Development, Ben-Gurion University of the Negev, Beer-Sheva, 84105,
Israel

A R T I C L E I N F O A B S T R A C T

Article history:
Received 19 June 2016 Carbon dioxide utilization by conversion with hydrogen into liquid fuels was simulated based on the
Received in revised form 10 November 2016 experimental data of a novel process using CHEMCAD. A detailed kinetic model of the novel iron-based
Accepted 20 December 2016 spinel catalyst that included reverse water gas shift (RWGS), Fischer-Tropsch synthesis (FTS), C5+
Available online xxx hydrocarbons and oxygenates, oligomerization of olefins, as well as hydrogenation of light olefins
(C2

C4) was employed. The RWGS reaction rate was significantly inhibited by steam produced in the
Keywords: process because of the chemical equilibrium limitation and apparent strong adsorption. Therefore,
CO2 utilization periodical water removal is critical in the process, which required operation in several reactors in series
CO2 conversion
or in a reactor with recycle. Those system configurations were examined and compared over a range of
Simulation
temperatures, pressures, weight hourly space velocities and carbon dioxide with hydrogen feed ratios.
Liquid fuels
Oligomerization The other aspect of this process which has a significant impact on performance is the oligomerization of
light olefins. Both reactors-in-series and single reactor with recycle improved dramatically the
productivity and the selectivity to C5+.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction Fe catalyst in a fixed-bed reactor indicated that water removal from

Carbon dioxide is a major greenhouse gas resulting from human
activities. Its increasing content in the atmosphere poses a critical
threat to the environment being a major cause of global warming
and climate change [1]. Various methods were proposed to capture
CO2 by well-established commercial methods as well as novel
methods and materials being studied and developed toward
commercialization [2–4]. Although sequestration has gained
significant support [2], recycling CO2 as feedstock in processes
for the production of liquid fuels and chemicals is the basis for a
sustainable eco-system [2–4]. In spite of major efforts, little
progress was reported.
CO2 hydrogenation to renewable chemicals and fuels, with a Fe-
based catalyst, is a promising viable process [5–10]. This process
consists of the reverse water-gas shift reaction (RWGS) followed by
CO hydrogenation, i.e., Fischer-Tropsch synthesis (FTS). Both
reactions produce water that inhibits the conversion of CO2 which
was reported in a number of studies with different catalysts [6–8]
to be well below 60%. Studies of CO2 hydrogenation with the use of
* Corresponding author.
E-mail address: herskow@bgu.ac.il (M. Herskowitz).
the reactor may significantly increase the hydrocarbon yield and
CO2 conversion [5,9,11]. The critical role of reactor configuration
was clearly identified. Applying a system of three packed-bed
reactors in series with the interim removal of water and condensed
hydrocarbons increased CO2 conversion to as much as 89% [5,11].
Models and simulations of the FTS kinetics and process were
published [12–15]. Recent studies presented FTS kinetics models,
emphasizing the important role of WGS reaction and kinetics on
iron catalysts [16,17]. The kinetic expressions are based on
mechanistic, semi-empiric and empirical power law models.
However, essentially all those models cover relatively low H2/CO
molar ratios in the reactors thus cannot be directly applied in our
case with H2/CO molar ratios higher than 10.
CO2 utilization by conversion to liquid fuel was investigated in
this study by simulating the Fe-based spinel catalytic process
[5,11]. The novelty in this simulation is combining the detailed
kinetic model of the catalytic reactions of this process and
potential reactor configurations. The kinetic model includes RWGS,
CO hydrogenation, oligomerization and hydrogenation of light
olefins (C2-C4). The scope of the simulations is to understand the
effects of the key parameters on CO2 and H2 conversions, C5+
selectivity and methane selectivity providing the basis for the
optimization of the process.

http://dx.doi.org/10.1016/j.jcou.2016.12.008
2212-9820/© 2016 Elsevier Ltd. All rights reserved.
 N. Meiri et al. / Journal of CO2 Utilization 17 (2017) 284–289
2. Methods
The chemical process simulation software CHEMCAD 6.5.7 was
used to perform the simulations. The simulated process of a single
reactor unit employed in this study includes a mixer, a heat
exchanger to heat the feed of the reactor, a fixed-bed reactor, a
cooler, a separator and splitter. The other simulated configuration
consists of three reactors in series, each reactor followed by a
cooler kept at 40  C, based on industrial coolers temperature
performance and a gas-liquid separator to separate water and the
condensable organic phase, as shown in Fig. 1. The Soave-Redlich-
Kwong (SRK) method was used to model the different unit
operations considered in this study. This method is very effective
for predicting K-values for hydrocarbon systems at medium to high
pressures. The reactor model used for the simulation of the plug
flow (PFR) is Kinetic Reactor (KREA). The simulations were
conducted with a feed containing H2 and CO2 at molar ratios of
2.0–3.5. The reactor was simulated at a weight-hourly-space-
velocity (WHSV) of 1–3 gCO2/[h*gcat], 300–340  C and 20–30 bar.
The reactor model used in these simulations is Kinetic Reactor
(KREA). The kinetic model consists of 20 reactions listed in
Supporting information (SI) Table S1. The kinetic model is a
modified version of the original model [11], developed based on
experimental data measured with the novel Fe-based catalyst, as
explained somewhere else [5].
Conversion of the reactants Xi, selectivity of the products Si and
the recycle ratio RR were calculated as:
F in
F out
X¼
F in
mc;i
Si ¼
mc;reacted
mrecycle
RR ¼
mef f luent
Where F represent the mole flow, mc is carbon mass flow of
component i, mr is the stream mass flow.
3. Results and discussion
The detailed kinetic model employed in this study consists of
the CO2 RWGS reaction and the CO conversion reactions (FTS) to
hydrocarbons and oxygenates including light olefins which are
further converted by oligomerization as well as hydrogenation.
Olefins oligomerization reactions, determined in the kinetic study,
Fig. 1. Simulation system.
285
play an important role in determining the products distribution.
Specifically, their impact on the performance of the reactor with
recycle is significant.
3.1. CO2 conversion by RWGS and FTS reactions in a single reactor
RWGS, the key reaction in this process, is strongly limited by
chemical equilibrium. The CO2 conversion at equilibrium was
estimated to be about 74% [6,18] at stoichiometric H2 to CO2 molar
ratio of 3, 320  C and 10 bar. Changing this ratio to 2.7, as tested in
several simulations, reduced the equilibrium CO2 conversion to
67%, as calculated by the minimization of the Gibbs free energy,
using CHEMCAD. Besides the equilibrium limitation, RWGS is
strongly inhibited by the steam produced in the process. This is
illustrated in Fig. 2 where the RWGS reaction rate decreases
significantly with CO2 conversion mainly as a result of the increase
in the mole fraction of steam, depicted in Fig. 3. Actually, the RWGS
rate decreases by about one order of magnitude at 20% CO2
conversion and another order of magnitude as the CO2 conversion
approaches 55%. The rate of CO conversion combined with the rate
of production of hydrocarbons and oxygenates (FTS) and the rate of
methane production (methanation) is depicted in Fig. 2.
As expected, those rates reach a maximum at about 10% CO2
conversion (Fig. 2), where the limiting reactant CO reaches
maximum as it is reflected in the H2 to CO molar ratio (Fig. 3).
The FTS rate is about one order of magnitude higher than the
methanation rate. It is important to note that the H2 to CO molar
ratio is by far higher than the stoichiometric value of 2, reaching a
ð1Þ minimum value of about 20 at about 10% CO2 conversion, as
depicted in Fig. 3. The level of performance determined by key
rates of reaction clearly indicates that the CO2 conversion per pass
through the reactor should be limited, pointing to the need for
ð2Þ periodical water removal from the reactor either by operating in a
system with several reactors in series [5] or employing recycle.
The kinetic model indicates that oligomerization of light olefins
(C2–C4) is an important reaction producing C5+ hydrocarbons. The
ð3Þ lumped rate of oligomerization depends on the concentration of
light olefins which in turn depends on the rate of light olefins
production, both depicted in Fig. 4. Since the rate of light olefins
production depends on the partial pressure of CO which is a
product of RWGS, it reaches a maximum value at CO2 conversion of
about 15%. Oligomerization of light olefins depends on the partial
pressure of the light olefins, thus, its rate increases with CO2
conversion reaching a maximum level at about 50% conversion.
The analysis of the reactor performance was conducted at the
stoichiometric H2 to CO2 molar feed ratio. Reducing this ratio has a
critical impact on the performance. While the CO2 conversion is
expected to decrease, the selectivity to C5+ increases, decreasing
Fig. 2. RWGS and CO conversion rates change dramatically with CO2 conversion.
Operating conditions: 320  C, 20 bar, feed H2/CO2 = 3.
286 N. Meiri et al. / Journal of CO2 Utilization 17 (2017) 284–289

Fig. 3. Steam and H2 to CO2 molar ratio change significantly with CO2 conversion.
Operating conditions: 320  C, 20 bar, feed H2/CO2 = 3. Fig. 5. Conversion and selectivity with different feed H2/CO2 ratio and different
WHSV. Operation conditions: T = 320  C, P = 20 bar, XCO2 = 33%.

the selectivity to other by-products. Those effects are illustrated in

CO2, H2, H2O and C5+ at the inlet and outlet of each reactor were
Fig. 5 which presents the simulation results calculated at 320  C
compared with predictions of the simulation model in Fig. 6,
and 20 bar keeping the CO2 conversion at 33%. At this conversion
indicating a good agreement.
level, conversion of hydrogen is almost complete as the feed H2 to
Removing water and other condensable products sets the feed
CO2 molar ratio reaches unity. As expected, the WHSV decreased
CO2 and H2 concentration to each one of the reactors in series at
significantly with decreasing H2 to CO2 molar feed ratio from 7.4
about the same level. Therefore, RWGS rates profile in each reactor
[h
1] at feed H2/CO2 = 3.5 to 0.4 [h
1] at feed H2/CO2 = 1. In parallel,
are very similar. It means that the more reactors are set in series the
the selectivity to C5+ hydrocarbons increases dramatically from
higher the average RWGS rate in each reactor which leads to a
38% to 68% due to the significant conversion of the light olefins to
dramatically higher WHSV as the number of reactors increases at
C5+ hydrocarbons and the strong reduction in methane.
constant CO2 overall conversion, as depicted in Fig. 7.
The performance characteristics of the CO2 hydrogenation on
The FTS reaction rates in each one of the reactors are quite
the spinel catalyst indicate that the CO2 conversion in the reactor
similar as shown in Fig. 8, although the FTS rates the second reactor
should be limited to <40%. It means that reaching high CO2
is somewhat higher because of the CO content in the feed.
conversion levels can be accomplished by operating in a system
Therefore, the level of C2+ products produced in each reactor is
with several reactors is series or a reactor with recycle. In both
about the same. The dramatic difference is the distribution
cases, the CO2 conversion in each reactor or per pass through the
between the C5+ and the light olefins. As the concentration of
reactor is limited.
light olefins increases in the feed from one reactor to the other, the
rates of oligomerization increase accordingly (Fig. 8). The
3.2. Multiple reactors in series
oligomerization in the first reactor is negligible, increasing
significantly in the second reactor and further in the third reactor.
Periodical water removal, essential to achieve high CO2
Therefore, increasing the number of reactors while keeping the
conversion, can be accomplished in multiple reactors in series
with limited CO2 conversion in each reactor. Experiments were
conducted with three identical reactors in series to illustrate the
significant effect of water removal on conversion and selectivity
(T = 320  C, P = 20 [bar], H2/CO2 = 3, WHSV = 1 [h
1]). The effluent of
each reactor was cooled to 40  C to condense water, oxygenates
and most C5+ hydrocarbons. The experimental mole fractions of

Fig. 6. Comparison between simulation and experimental results of CO2, H2, H2O
Fig. 4. Light olefins production and oligomerization rates. Operating conditions: and C5+ mole fractions of three reactors in series. Operation conditions: T = 320  C,
320  C, 20 bar, feed H2/CO2 = 3. P = 20 bar, WHSV = 1 [h
1].
 N. Meiri et al. / Journal of CO2 Utilization 17 (2017) 284–289
Fig. 7. WHSV and C5+ selectivity as a function of the number of reactors in series.
Operation conditions: T = 320  C, P = 20 bar, XCO2 = 85%.
CO2 conversion constant reduces the contribution of the oligo-
merization of light olefins thus leading to a decrease of C5+
selectivity as depicted in Fig.7.
The characteristics of this reaction system reflected in Figs. 7
and 8 yield the significantly improved performance as the number
of reactors in series increases at constant WHSV, as depicted in
Fig. 9. Beyond the fact that reactant conversion increases
considerably, the C5+ selectivity increases while the light olefins
selectivity decreases, respectively. The changes in the other
products are small.
3.3. Effect of recycling
The natural alternative to the case of reactors in series is a single
reactor with recycle, described schematically in Fig. 10, which can
accomplish the critical task of removing water while limiting the
conversion per pass. As increasing the number of reactors
displayed a significant effect, improving the performance of the
system, the recycle ratio is expected to have a similar effect. The
CO2 conversion per pass in the reactor decreases while that in the
system increases with the recycle ratio at constant WHSV to the
system as shown in Fig. 11. The CO2 conversion per pass through
the reactor and in the system are calculated based on the molar
flow rates of streams 2 and 6 and streams 1 and 7 in Fig. 10,
respectively.
As the recycle ratio increases, the mole fractions of CO2 and H2
decrease mainly as a result of the increase in the mole fraction of
the inerts (C1–C4 paraffins) and the light olefins. This is specifically
significant at the high recycle ratio levels, say >0.8. In parallel, the
CO2 conversion per pass decreases as it did in the reactors in series
Fig. 8. FTS and olefins oligomerization reaction rates of first, second and third
reactor in series. Operation conditions: T = 320  C, P = 20 bar, WHSV = 1 [h
1].
287
Fig. 9. Conversion and selectivity for different number of reactors in series.
Operation conditions: T = 320  C, P = 20 bar, WHSV = 1 [h
1].
system. This creates a sharp increase in the CO2 conversion in the
system.
The two major products of this process, C5+ hydrocarbons and
light olefins, display a very significant change with recycle ratio.
Since the other products, light paraffins C1–C4 and oxygenates
remain essentially constant with recycle ratio, the C5 hydrocarbons
selectivity increases to the extent that the light olefins selectivity
decreases (Fig. 12).
3.4. Reactor with recycle compared with reactors in series
Both configuration options, reactors is series and single reactor
with recycle, meet the essential feature of the process, which is
water removal from the system. A comparison between three
reactors in series and single reactor with recycle was performed at
the same CO2 conversion. Two different space velocities of feed to
the system were chosen, WHSV = 1 and 3 [h
1], T = 320  C, P = 20
[bar], H2/CO2 = 3. The recycle ratio in the single reactor was
adjusted so as to achieve a similar conversion to that of three
reactors in series. Furthermore, for WHSV = 1 [h
1], CO2 conversion
set for both systems is 84%, with recycle ratio of 0.85 in the single
reactor. For WHSV = 3 [h
1], CO2 conversion is 64.2%, with recycle
ratio of 0.77. Selectivity of the products depicted in Fig. 13 indicates
the performance level of the two options. Selectivity of light olefins
is higher in three reactors in series and selectivity of C5+
hydrocarbons are lower comparing to a single reactor with recycle.
The selectivity difference of C1–C4 and oxygenates is negligible.
Fig. 10. Process scheme of CO2 conversion system of single reactor with recycle.
288 N. Meiri et al. / Journal of CO2 Utilization 17 (2017) 284–289
Fig. 11. CO2 conversions of the entire system and reactor only vs. recycle ratio.
Conditions: T = 320  C, P = 20 [bar], WHSV = 1 [h
1], H2/CO2 = 3.
Fig. 13. Comparison of selectivity: single reactor with recycle vs. three reactors in
series. Conditions: T = 320  C, P = 20 [bar], H2/CO2 = 3, WHSV = 1 and 3 [h
1] and
XCO2 = 84% and 64.2% respectively.
4. Conclusion
RWGS, CO conversion to hydrocarbons and light olefins
oligomerization are the key players in the process of CO2
conversion into liquid fuels. The reactions rates, calculated based
on the simulation performed in CHEMCAD, decrease extensively
with the water formation. Furthermore, the RWGS reaction rate
limitation was found to be affected by water inhibition rather than
Fig. 12. Products selectivity vs. recycle ratio. Conditions: T = 320  C, P = 20 [bar],
WHSV = 1 [h
1], H2/CO2 = 3.
by chemical equilibrium. As expected, CO2 and CO conversions
rates reach a maximum at about 10% and 15% CO2 respectively,
while CO conversion defers from the traditional FTS by the
significant higher H2 to CO ratio. The dependency of light olefins
oligomerization on the partial pressure of the light olefins leads its
rate to increase and to reach a maximum level at about 50%
conversion of CO2.
H2 to CO2 molar feed ratio has a critical impact on the
performance. With the ratio decrease, CO2 conversion is expected
to decrease as well, the selectivity to C5+ increases, decreasing the
selectivity to other by-products.
Water removal is critical to achieving higher CO2 conversions.
Considering this, two systems were examined: three reactors in
series and single reactor with recycle. The reactors in series keep
high RWGS rates in each reactor, as well as FTS rates. The significant
differences are in C5+ and light olefins distribution. The rates of
oligomerization increase from on reactor to other, following by
increase of C5+. In a single reactor system with recycle, increasing
the recycle ratio led to increasing of C5+ selectivity to the extent
that the light olefins selectivity decreased. Comparing these two
systems, for the same CO2 conversion and same space velocity, the
selectivity of light olefins is higher in three reactors in series and
selectivity of C5+ hydrocarbons are lower than a single reactor with
recycle.
Acknowledgments
This work was supported by Israel
Strategic Alternative
Energy Foundation (I-SAEF), the I-CORE Program of the Planning
and Budgeting Committee and The Israel Science Foundation
(grant No. 152/11) and grant No. 582/13 of the Israel Science
Foundation and Ministry of Science, Technology and Space, Israel.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jcou.2016.12.008.
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