Journal of CO2 Utilization 3–4 (2013) 56–64

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Journal of CO2 Utilization

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Modeling and kinetic analysis of CO2 hydrogenation using a Mn and K-promoted

Fe catalyst in a fixed-bed reactor
Heather D. Willauer a,*, Ramagopal Ananth b, Matthew T. Olsen c, David M. Drab c,
Dennis R. Hardy d, Frederick W. Williams e
a
Materials Science & Technology Division, Code 6300.2, Naval Research Laboratory, 4555 Overlook Avenue, SW, Washington, DC 20375, United States
b
Chemistry Division, Code 6185, Naval Research Laboratory, 4555 Overlook Avenue, SW, Washington, DC 20375, United States
c
NRC Postdoctoral Research Associate, Materials Science & Technology Division, Code 6300.2, Naval Research Laboratory, 4555 Overlook Avenue, SW, Washington, DC 20375, United
States
d
Nova Research Inc., 1900 Elkin Street, Alexandria, VA 22308, United States
e
Chemistry Division, Code 6104, Naval Research Laboratory, 4555 Overlook Avenue, SW, Washington, DC 20375, United States

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

Article history: Hydrogenation of CO2 to hydrocarbons is investigated over g-alumina-supported modified iron-based
Received 24 April 2013 catalysts under fixed-bed reactor conditions to produce unsaturated hydrocarbons as feedstock
Received in revised form 8 August 2013 chemicals for jet-fuel synthesis. The results are compared to those obtained in a continuously stirred
Accepted 7 October 2013
tank/thermal reactor (CSTR) environment. It is shown that the maximum C2–C5+ yield obtained in the
Available online 13 November 2013
fixed-bed experiments is 49% higher than those obtained by CSTR at lower gas hourly space velocity
(GHSV) of 0.000093 liters per second gram (L/s-g). However, at much higher GHSV (0.0015 L/s-g), C2–
Keywords:
C5+ yield is reduced by 47% in the fixed-bed environment. Modeling and kinetic analysis of the data
CO2 hydrogenation
obtained under fixed-bed reactor conditions is expanded upon by including the formation of methane as
Fixed-bed reactor
Kinetics a by-product and providing kinetic constants. The results show that our Fischer–Tropsch (FT) reaction
Modeling rate is much slower than the reverse water gas shift (RWGS) reaction rate. Therefore the FT reaction
GHSV (gas hourly space velocity) becomes the rate-controlling step in overall conversion of CO2 to olefins. The model was further
expanded to show the potential beneficial effects of water removal from the reactor on CO2 conversion
and product yield.
Published by Elsevier Ltd.

1. Introduction
The US Department of Defense (DoD) is the single largest buyer
and consumer of middle-distillate fuel in the world [1]. On average,
the DoD used approximately 9.2 million gallons/day or 3.4 bil-
lion gallons of fuel in 2010 [1]. Though historical data show the
DoD’s average fuel use has steadily decreased from a high of
4.6 billion gallons/year in 2004, the average annual fuel cost has
continued to rise [2,3]. The Defense Logistics Agency reports a fuel
cost per gallon of $0.60 in 2000. In 2011 this cost rose to over $3.40
per gallon [2,3]. This price does not include the additional costs of
logistical storage and delivery of the fuel, which in many cases is 2–
3 times the initial price of the fuel [4]. With the global demand for
fossil fuel increasing and its availability decreasing [5], the DoD is
subjected to large price fluctuations. Thus, any production of fuel at
or near the point of use would significantly reduce dependence on
* Corresponding author. Tel.: +1 202 767 2673; fax: +1 202 767 171.
E-mail address: Heather.Willauer@nrl.navy.mil (H.D. Willauer).
foreign oil supplies, costs, and fuel logistic tails and their
vulnerabilities resulting from fuel delivery. While technologies
currently exist to produce liquid hydrocarbon fuel given sufficient
primary energy resources such as coal and natural gas, most of
these technologies are not CO2-neutral and they are only practical
for land-based operations [6,7]. Thus, there is still a need for more
favorable and cost-effective methods to produce hydrocarbon fuel
from other resources.
Carbon dioxide (CO2) is a relatively abundant natural carbon
resource. As a result of increasing anthropogenic levels and the
foreseeable impact it will have on the environment, research
efforts have focused on capturing CO2 and then sequestering or
catalytically converting it to energy-rich hydrocarbons [8–13].
Since the total carbon content of the world’s oceans is roughly
38,000 GtC (gigaton of carbon), it represents a potential resource
for carbon feedstock. Over 95% of this carbon is in the form of
dissolved bicarbonate ion (HCO3) [14] which, along with the
carbonate ion (CO32), is responsible for buffering and maintaining
the ocean’s pH [14,15]. The sum of these ions and dissolved CO2 gas
represent the total carbon dioxide concentration [CO2]T of

2212-9820/$ – see front matter . Published by Elsevier Ltd.

http://dx.doi.org/10.1016/j.jcou.2013.10.003
 H.D. Willauer et al. / Journal of CO2 Utilization 3–4 (2013) 56–64
seawater, as shown in the following equation.
S½CO2 T ¼ ½CO2 ðaqÞ þ ½HCO3  ðaqÞ þ ½CO3 2 ðaqÞ
The [CO2]T in seawater on a weight per volume basis is 100 mg/L,
where approximately 2–3% is dissolved gas and, of the remaining
CO2, 97–98% is chemically bound as bicarbonate and 1% as
carbonate [14,15]. When compared to the concentration in air
(370 ppm or 0.7 mg/L), CO2 is approximately 140 times more
concentrated in seawater [6]. This is mainly due to the difference in
densities of air (0.001204 g/mL) and sea water (1.025 g/mL).
Processes are currently being developed to take advantage of this
higher concentration in seawater as a potential source of feedstock
[10,16]. Since CO2 in the atmosphere is in constant equilibrium
with the ocean, it is envisioned that CO2 extracted from seawater
would re-equilibrate from the atmosphere back to the oceans.
Thus, hydrocarbons made from this feedstock using nuclear
electricity or a renewable energy source such as OTEC (ocean
thermal energy conversion), solar, tidal, or wind could be
considered as CO2-neutral [3].
One limitation of using CO2 as a feedstock for hydrocarbon
production concerns the high energy barrier for polymerization
and the need for a source of hydrogen. While reports suggest
electrochemical and photochemical catalytic CO2 conversion
processes continue to improve in efficiencies [11], thermal
processes remain one of the few proven methods for producing
high yields of hydrocarbons greater in carbon number than
methane [12,13,17–20]. To take advantage of this approach, a two-
step synthesis process that involves converting CO2/H2 to olefins
and subsequent oligomerization over nickel-supported catalyst to
jet fuel is being pursued. To date, we have reported CO2 conversion
levels as high as 50.2% and an olefin/paraffin ratio of 4.4 using an
optimized bifunctional K/Mn/Fe catalysts impregnated on Al2O3
containing ceria in a continuously stirred tank/thermal reactor
(CSTR) [17].
The CSTR simulates conventional slurry phase reactors that are
used for large scale industrial applications [7,21]. The challenge
Fig. 1. Schematic of the experimental fixed bed catalytic reactor for making jet fuel.
57
remains to find mechanisms to scale down the size of reactor
systems while maintaining sufficient capacity at low costs. To meet
(1) these challenges, companies have developed microchannel units
as modular solutions for off-shore and remote synthetic hydro-
carbon fuel production [22,23]. Thus, there has been growing
interest to integrate and transition our two-step approach for
producing liquid hydrocarbons from CO2 and hydrogen to reactor
systems that have been modeled computationally as microchannel
reactors. In these studies, the effects of space velocity on CO2
conversion and product selectivity were evaluated in a fixed-bed
tubular reactor, where the results were compared with those
obtained using similar catalyst compositions in a CSTR. In addition,
the results were used to modify the multi-step chemical kinetics of
computational models being designed to predict optimal reactor
size and conditions for hydrocarbon production.
2. Experimental
2.1. Catalyst preparation
Gamma alumina (Matheson Coleman & Bell Manufacturing
Chemists, Norwood, Ohio 45212) with a surface area and pore
radius of 218.3 m2/g and 1.2–3.7 nm, respectively, and a particle
size distribution of 80–100 mesh was used as support material. An
incipient wetness impregnation method was used for catalyst
preparation. In a flask Fe(NO3)9H2O, KMnO4, and KNO3 were
added to boiling deionized H2O to obtain the desired weight ratios.
The hot mixed metal nitrate salts solution was then impregnated
onto the alumina and then dried at 80–90 8C in ambient air with
continuous agitation to a pasty consistency before additional
drying overnight at 110 8C. Samples were calcined at 350 8C for
87 h, under static air conditions.
2.2. Characterization
BET surface areas were measured using a Micromeritics
ASAP2010 accelerated surface area and porosimetry system. An
58 H.D. Willauer et al. / Journal of CO2 Utilization 3–4 (2013) 56–64

appropriate amount (0.11 g) of sample was taken and heated to
120 8C for 17 h under vacuum (50 mTorr). The sample was then
transferred to the adsorption unit, and the N2 adsorption was
measured at the boiling temperature of nitrogen.
2.3. Fixed-bed reactor synthesis
CO2 hydrogenation reactions were conducted in a 900 stainless
steel tube (3/800 ID, 1/200 OD) FT reactor as shown in Fig. 1. In a typical
experiment, 20 g of a mixture of calcined catalyst and 80–200 mesh
Al2O3 was prepared to obtain different space velocities of catalyst
(Table 1). The mixtures were dried under N2 stream for an hour
(100 mL/min, 300 8C, 265 psig) followed by in situ reduction using
CO at 265 psig and 300 8C for 2 h. Fig. 1 shows three mass flow
controllers (Sierra Instruments, USA) which were used to control the
flow of all the different gases into the reactor (pictured H2, CO2, N2,
not pictured CO). Immediately after pre-treatment and reduction,
hydrogenation of CO2 was conducted at 300 8C, 265 psig, and
different space velocities of catalyst with a H2/CO2 ratio of 3:1. A
10 mL/min flow of nitrogen gas was used as a reference gas in each
reaction. The effluent gases were passed through a cold trap, which
was placed in an ice bath to condense the water vapor and any heavy
liquid hydrocarbons that might have formed in the reactor. The
gases leaving the cold trap were passed through a cylinder
containing 500 g of 3 Å molecular sieves (Molecular Sieve UOP
Type 3Å, Sigma–Aldrich, Saint Louis, MO 63103 USA) to dry before
online analysis by GC as shown in Fig. 1. The effluent gases were
analyzed online using a chromatographic analyzer (Agilent Tech-
nologies, Fast RGA analyzer) for gas analysis. Hydrocarbons were
separated using an HP-Al/S column (Agilent Technologies, 19091P-
512, 25 mm  320 mm  8 mm) and detected with an FID detector.
Fixed gases (H2, CO2, CO, N2) were separated on a Unibead IS column
(4 ft, 60/80 mesh in UltiMetal) and a 5 Å molecular sieve column
(8 ft, 60/80 mesh) and detected with a TCD detector. The GC was
calibrated using a mixture of gases with known molar ratio (MESA
Specialty Gas, USA). Time-on-stream (TOS) for the catalyst was 48 h.
3. Results and discussion
Previous results report CO2 conversion levels as high as 41%
with an olefin/paraffin ratio of 4.2 using an optimized iron-based
supported catalyst (Fe/Mn/K-alumina) in a continuously stirred
tank/thermal reactor (CSTR) [18]. The incorporation of reverse
water–gas-shift (RWGS) activity by the addition of ceria prior to
the deposition of the CO2 hydrogenation catalyst increased the CO2
conversion levels to 50% and the olefin/paraffin ratio to 4.4 [17]. In
those studies CO2 hydrogenation reactions were conducted in a
CSTR slurry reactor, where the catalyst was dispersed in mineral
oil. The gases dissolve in the liquid phase (slurry) under pressure,
diffuse in the liquid phase to the catalyst particle, before coming in
contact with the active catalyst sites. CSTR bench top reactor
processes are proven scalable mechanisms for studying traditional
Fischer–Tropsch (FT) reactions [7,21].
The objective of the present study is to transition CO2
hydrogenation from a CSTR to a fixed-bed process. CSTR and fixed
bed reactors have fundamentally different flow patterns. In CSTR,
the liquid and gases are well stirred. In the fixed bed, gas and liquid
flow down the bed of catalyst from the top of the reactor to the
bottom, without any stirring. Further, in the fixed-bed reactor, H2
and CO2 gases are brought in to direct contact with the catalyst
particles dispersed in a support material (alumina) unlike the CSTR
process. In a CSTR, the gases are bubbled through mineral oil
(solvent) containing the catalyst. The gases dissolve and diffuse to
the catalyst sites dispersed in the mineral oil so that reaction at
catalyst sites can take place [17]. In a fixed-bed, the gases diffuse
through the support material to reach the active catalyst sites,
where the reactions occur. Clearly, there are differences in the
phase behavior of the reactant and product gases between CSTR
and the fixed-bed reactor. Differences in the transport of the gases
and the catalyst particle characteristics could lead to differences in
the resulting reaction kinetics. It is well established that a strong
relationship exists between catalyst composition and reaction
conditions (reactor type, GHSV, reactor temperatures and pres-
sures) which leads to changes in kinetic rate equations and the
kinetic parameters obtained by these equations [19,24]. Using a
previously designed and tested catalyst composition, we varied the
reactor conditions, rather than catalyst composition [18]. In this
work, we quantify the effects of gas hourly space velocity (GHSV)
on CO2 conversion, hydrocarbon product selectivity and yield, and
compare with those previously reported in a CSTR for a fixed
catalyst composition.
Data were collected on the conversion of CO2 over a 17 weight
percent (wt%) iron-alumina catalyst doped with approximately
8 wt% potassium and 12 wt% manganese for 48 h. CO2 conversion
under eight different GHSV is reported. Initially in the first four
studies with the gas ratio of CO2/H2 1:3, the mass of the catalyst,
reactor tube dimensions (length, inner diameter (ID) and outer
diameter (OD)) were fixed, and the GHSV was adjusted by
changing the flow rate of CO2 and H2 into the reactor. The GHSV
was changed in the remaining studies by lowering the active
catalyst amount in the bed. The support material, gamma-alumina,
was used to maintain a constant (20 g) mass of material in the
reactor when varying the active catalyst amount.
Table 1 provides the product selectivity, olefin/paraffin ratio,
and CO2 conversion as a function of GHSV based on the GC analysis.
Figs. 2 and 3 specifically show the trends in hydrocarbon

Table 1
Product selectivity, olefin/paraffin ratio, CO2 conversion, and ASF values over K/Mn/Fe catalysts, impregnated on Al2O3 support under fixed-bed conditions after 48 h of run
time.

GHSV Mass Reactor Selectivity (%, Carbon Based) Olefin/ Conversion a a Yield
(L/s-g) catalyst (g) type paraffin CO2 (%) C1–C6+ C1–C5 C2–C5+ (%)
C1 C2–C5+ CO
(methane)

0.0015 10–15 CSTR 26 62.4 11.5 4.2 41.4 0.47 – 25.8

0.000047 17.82 Fixed-bed 22.4 62.3 15.2 4.6 54.8 0.41 0.43 34.1
0.000093 17.82 Fixed-bed 22.4 64.2 13.4 5.6 60.0 0.47 0.57 38.5
0.00019 17.82 Fixed-bed 19.8 58.5 21.7 5.9 53.7 0.50 0.54 31.4
0.00037 17.82 Fixed-bed 16.1 56.0 28.0 5.9 50.6 0.51 0.55 28.3
0.00075 8.91 Fixed-bed 24.4 32.0 43.4 4.8 46.2 0.45 0.46 14.8
0.0015 4.46 Fixed-bed 22.2 30.5 47.3 4.6 44.7 0.48 0.50 13.6
0.0029 2.23 Fixed-bed 21.0 34.6 44.8 4.9 40.7 0.49 0.46 14.1
0.006 1.11 Fixed-bed 17.9 19.0 63.1 5.1 27.8 0.45 0.40 5.3

Bold values are from CSTR and fixed-bed experiments at same GHSV.
 H.D. Willauer et al. / Journal of CO2 Utilization 3–4 (2013) 56–64
70
60
50
(% ) CO2, CO
40
30
20
10
0 reaction step for converting CO2 to CO. Indeed, the kinetic model
0.000 0.001 0.002 0.003 0.004 0.005 0.006 0.007
GHSV (L/s g)
Fig. 2. Comparison of experimental data with model predictions for CO2 conversion
and CO selectivity and the effects of varying GHSV. CO2 conversion experimental
(*), model (*), CSTR (~), and Riedel (!), CO selectivity experimental (&), model
(&), and CSTR (^).
selectivity, unreacted carbon monoxide, and CO2 conversion as a
function of GHSV. The product hydrocarbons produced from each
reaction condition consisted predominantly of methane and light
olefins. A smaller fraction of the hydrocarbons were found to be
paraffins, generally resulting in an olefin/paraffin ratio ranging from
4.6 to 5.9. It was noticed that there was some liquid hydrocarbon
collected in the cold trap along with condensed water. But, the liquid
hydrocarbon collected in the cold trap was small and was neglected
in the calculations reported in the present work.
At the lowest GHSV tested in the fixed-bed reactor, CO2
conversion reached 54.8% with an olefin/paraffin ratio of 4.6.
Unreacted CO was 15.2% and the formation of unwanted methane
was 22.4%. When the GHSV was increased from 4.7  105 L/s-g to
9.3  105 L/s-g, CO2 conversion increased from 54.8% to 60% and
the hydrocarbon selectivity (without methane) rose to 64.2%.
These were the highest conversion levels measured in these
studies. The olefin to paraffin ratio increased to 5.6 and more CO
was consumed in the reaction process.
80
60
(% ) CH4, C2-C5 +
40
20
0 yield reported by Riedel et al. [19] are consistent with the present
0.000 0.001 0.002 0.003 0.004 0.005 0.006 0.007
GHSV (L/s g)
Fig. 3. Comparison of experimental data with model predictions for hydrocarbon
(C3H6 or C2–C5+), CH4 selectivities (C basis) and the effects of varying GHSV. C3H6 or
C2–C5+ experimental (&), model (&), CSTR (^), and Riedel experiments (!), CH4
selectivity experimental (*), model (*) and CSTR (~).
59
Since methane formation is widely considered to be the most
thermodynamically favored product in CO2 hydrogenation [19],
the reaction conditions that favored its lowest selectivity are ideal.
Table 1 and Fig. 3 show that, on average over a wide range of GHSV
reaction conditions, methane formation was 21% with the lowest
amount produced at a GHSV of 0.00037 L/s-g, and the highest
amount at 0.0075 L/s-g. The methane selectivity is on average 19%
lower than previously reported using a CSTR process. As the GHSV
was increased, a shift in hydrocarbon selectivity away from C2–
C5+ hydrocarbons was seen in favor of much more carbon
monoxide formation whereas CO2 conversion was reduced. The
increase in formation of CO has been considered evidence of a two-
step reaction mechanism for formation of hydrocarbons from CO2
[20]. The increase in CO might indicate that the FT step for
converting CO to hydrocarbon is slow relative to the RWGS
parameters obtained from these experimental data show that the
RWGS to be faster than FT.
Yield is calculated by multiplying the C2–C5+ hydrocarbon
selectivity values with the CO2 conversion values in Table 1.
Table 1 shows that the highest C2–C5+ yield is 38.5% by weight on a
carbon basis. This means 38.5% of CO2 fed into the reactor is
converted to C2–C5+ molecules. The maximum yield of 38.5% in the
fixed-bed reactor is significantly higher than that in the slurry CSTR,
which was 25.8%. It appears that the yield improved by almost 50%
by transitioning from CSTR to the fixed-bed reactor. Furthermore,
Table 1 shows that the yield increases from 34.1% to 38.5% as GHSV is
increased from 4.7  105 L/s-g to 9.3  105 L/s-g. As GHSV is
increased further, the yield decreases due to decreasing CO2
conversion. At a fixed GHSV of 1.5  103 L/s-g, the yield in the
fixed-bed reactor is 13.6%, which is significantly less than the 25.8%
measured in the CSTR. The precise reason for this trend is not well
understood. However, to explain this trend, three possibilities are
postulated. First, the catalyst composition used in the fixed-bed and
CSTR are different though the catalysts were prepared following
similar incipient wetness impregnation methods [18]. On 100 g
Al2O3 basis, the catalyst compositions for K/Mn/Fe/Al2O3 are 7.3/8.2/
11.6/100 and 10.5/12/17/100 by mass for the fixed-bed and CSTR
respectively. Clearly, the fixed-bed catalyst has less Fe, K, and Mn
compared to the CSTR. Second, the catalyst is dispersed in mineral oil
in the CSTR and in alumina powder in the fixed-bed. The resistances
to the transport of species to the catalyst sites could be very different.
Third, the composition of liquid hydrocarbon formed in CSTR and
fixed-bed could be different and each reactor media (mineral oil vs.
alumina, respectively) have different effects on the transport of
species to and from the catalyst sites.
Figs. 2 and 3 also provide a comparison of our measurements for
CO2 conversion, hydrocarbon and CO yields with those reported in
the literature for the fixed bed reactor. The figures show that our
data are consistent with those measured by Riedel et al. [19] at low
values of GHSV. Riedel et al. [19] report their data in terms of t g-s/
cm3 which is related to GHSV as 1/(1000  t) L/g-s, which is only
nominal because it does not account for differences between the
study of Riedel et al. [19] and ours in the composition of the final
powder and especially in the calculation of ‘‘catalyst mass’’, Mc.
Despite these differences in the calculation method for GHSV values
between the present study and that of Riedel et al. [19], Figs. 2 and 3
show that the maximum conversion and maximum hydrocarbon
study. However, as GHSV is increased CO2 and hydrocarbon yields
were reported to approach zero by Riedel et al. [19]. In contrast,
Figs. 2 and 3 show our measured CO2 conversion and HC selectivity
as high as 28% and 18% at a GHSV over 3 times higher than that
reported by Riedel et al. [19]. The difference in CO2 conversion,
selectivity’s, and yields of species at higher GHSV may be due to
differences in the catalyst used. Riedel et al. used K/Cu/Fe/Al2O3 in
60 H.D. Willauer et al. / Journal of CO2 Utilization 3–4 (2013) 56–64
the ratio 67/80/752/100. Riedel et al. dilute 2.5 g (Mc) of catalyst with
25 g of silica (1 to 10 ratio). So, the final powder has 6.8% Fe, 0.72% Cu,
0.61% K in the support consisting of Al2O3 and silica, which is also
equivalent to 0.66/0.8/7.4/100 for K/Cu/Fe/(Al2O3 + silica). We use
Mn instead of Cu in the ratio 7.3/8.2/11.6/100 for K/Mn/Fe/Al2O3
respectively. In a typical run, about 17.8 g (Mc) of the catalyst is
mixed with 2.2 g of alumina to make the final powder that was used
to form the fixed bed in our tubular reactor. The final powder
contains 8.1% Fe, 5.7% Mn, 5.1% K in Alumina support by mass as
calculated based on the ratios for K/Mn/Fe/Al2O3 7.3/8.2/11.6/100.
The final powder we use in the fixed-bed has significantly lower Fe
and K loading in relation to Al2O3 than those of Riedel et al. [19].
There are also significant differences in catalyst preparation. Riedel
et al. [19] uses co-precipitated catalyst while we use an impregna-
tion method. This could lead to differences in the particle size and
distribution. For example, larger particle sizes can lead to slower
diffusion of reactants and products formed inside the pores of
catalyst particle. These results highlight how the changes in catalyst
composition and reactor environment (CSTR vs. fixed-bed) from one
study to the next produce significantly different CO2 hydrogenation
results. Therefore the kinetic analysis of CO2 hydrogenation should
impact the kinetic parameters from one set of experimental
conditions to the next.
The total hydrocarbon product distribution under eight
different GHSV can be described by means of Anderson–Schulz–
Flory (ASF) growth distribution plots, where ln(WN/N) (WN is the
weight fraction of HC containing N Carbon) is plotted as a function
of carbon number (N). The chain growth probability, a, is inferred
by the slope [25]. Table 1 shows these values initially increase with
increasing GHSV and they range from a = 0.41 to 0.51 for C1–C6+.
These values are in excellent agreement with those obtained for
comparable catalysts used in a CSTR (Table 1) [17,18]. The weight
fraction of C6+ hydrocarbons is small relative to C1–C5 hydro-
carbons, thus analysis of for C1–C5 shows values as high as a = 0.57
under the most favorable fixed-bed reactor conditions. These
values are similar to those reported for iron catalysts used in
typical FT processes [25], where results indicate the feasibility of a
two-step approach to hydrogenation of CO2 to liquid fuel.
Table 1 shows that, while the GHSV does not greatly affect the
chain growth probability (0.43–0.57 C1–C5+), it has a significant
impact on CO2 and CO conversion. In particular, their conversion
can be significantly improved by lowering the GHSV and thus
increasing the residence time of the reagents CO2, CO, and H2 in
contact with the active catalyst bed. Initially such low GHSV
appears to be impractical for scale-up since the inverse relation-
ship between catalyst mass and GHSV necessitates the need for
very large amounts of catalyst to achieve higher conversion. Since
extremely low GHSV is impractical, kinetic analysis of CO2
hydrogenation is used to determine kinetic parameters needed
to further facilitate CO2 and CO conversion in fixed-bed micro-
channel reactor conditions.
The mechanism of CO2 hydrogenation has been proposed to
occur in two steps [19]. The first step (Eq. (2)) is the RWGS, which is
endothermic and produces carbon monoxide. This carbon monox-
ide is then carried forward in an exothermic FT step (Eq. (3)),
producing predominantly monounsaturated hydrocarbons
(Eq. (4)).
nCO2 þ nH2 @ nCO þ nH2 O
nCO þ 2nH2 ! ðCH2 Þn þ nH2 O
nCO2 þ 3nH2 ! ðCH2 Þn þ 2nH2 O
A thermodynamically favorable side reaction associated with
CO2 hydrogenation is the highly competitive methanation
reaction (Eq. (5)), and for many years this was the widely
reported reaction [19].
CO2 þ 4H2 ! CH4 þ 2H2 O (5)
Another deleterious side reaction is the Boudard reaction
(Eq. (6)) [19,26,27]
2CO @ C þ CO2 (6)
There is a limited kinetic analysis of Eqs. (2)–(4) involved in
CO2 hydrogenation [19]. While Eqs. (2)–(6) have been reported to
be involved in CO2 hydrogenation, our gas chromatographic
analysis of the product stream shows few major species produced
under the reaction conditions provided in Table 1. These species
include propylene, methane, CO and H2O. There are many other
species present but in quantities that are less than 20% of the
major species measured in the product stream. Therefore the
following reactions (Eqs. (7)–(9)) are considered as the basis for
the development of our one dimensional fixed-bed kinetic reactor
model:
Reverse water gas shift ðRWGSÞ CO2 þ H2 @ CO þ H2 O (7)
FischerTropschðFTÞ CO þ 2H2 ! 1=3C3 H6 þ H2 O (8)
FischerTropschðside reactionÞ CO þ 3H2 ! CH4 þ H2 O (9)
Since methane formation is a thermodynamically favored
reaction in CO2 hydrogenation, a reaction that describes methane
formation was added to the model in Eq. (9). We will show the
methanation reaction given by Eq. (9) in our computational results.
This reaction was not shown in the computational results
presented in the literature [19]. There are direct hydrogenation
reactions with CO2 taking place, but these are generally considered
to be slower than the hydrogenation reactions with CO [19]. Eq. (7)
was reported to be an equilibrium reaction unlike Eqs. (8) and (9)
in the literature [19]. However, Norval suggests that indeed Eqs. (8)
and (9) could be considered reversible to explain the product
distribution data in traditional FTS [28]. However we follow
Riedel’s kinetic approach and treat the kinetic constants as
parameters of the model [19].
Next, we developed a one dimensional plug flow, fixed-bed
catalytic, reactor model for the reaction scheme (Eqs. (7)–(9))
shown above. We considered 1 mole of CO2 and R moles of H2
present in the system initially. We also consider  moles of CO2 are
converted to CO following reaction (7), y moles of CO are converted
to unsaturated hydrocarbons following reaction (8), and z moles of
CO are converted to saturated hydrocarbons including methane
following reaction (9). We also consider a case when w moles of
water are removed from the reactor at a specified rate, kw. As
illustrated in Eqs. (7)–(9) water formation is a dominate product of
these reactions. From the equations, water should affect the RWGS
reaction equilibrium and there is evidence that it also affects the
catalyst active sites in CO2 hydrogenation [29,30]. Even though
water removal from the reactor in these studies has not been
attempted experimentally, it is important to understand its effect
on conversion and selectivity by considering a constant removal
rate of water, kw. In these studies water is varied as a parameter of
the model to determine if experiments should be performed in the
future to examine this effect. In the base case, kw is set to zero (no
water removal) and is set to 0.1 s1 for the case in which water is
(2)
removed from the reactor. The concentrations of species can be
(3) expressed in Eqs. (10)–(15) as:
CO2 ¼ 1  x (10)
(4)
CO ¼ x  y  z (11)
H2 ¼ R  x  2y  3z (12)
 H.D. Willauer et al. / Journal of CO2 Utilization 3–4 (2013) 56–64 61

C3 H6 ¼ y (13) experiments. The kinetic constants kSH, kFT, kFTs depend on the
activation energies ESH, EFT, EFTs for the RWGS, FT, and methanation
CH4 ¼ z (14) reactions respectively. The parameters kSH0, kFT0, kFTs0 are the pre-
exponential coefficients for the RWGS, FT, and methanation
H2 O ¼ x þ y þ z  w (15) reactions respectively. The parameters aSHH2 O , bSHCO2 , aFTH2 O ,
bFTCO2 , aFTsH2 O , bFTsCO2 are the adsorption constants for the RWGS,
The gases CO2 and H2 enter the vertical fixed-bed catalytic
FT, and methanation reactions respectively. Eq. (20) represents
tubular reactor of length L at a specified total flow rate, F (m3/s), at
rate of water vapor removal from the reactor. It is assumed to be
standard temperature and pressure (STP) conditions as measured
removed at a rate kw. The value of kw is set to zero in determining
by the mass flow controllers. The reactor contains Mc grams of
the kinetic parameters and comparing model predictions with
impregnated catalyst mixed with (20-Mc) grams of un-impregnat-
experimental data. Only the simulations designed to study the
ed alumina. GHSV is determined as F/Mc. The average velocity of
water removal effect, a non-zero value for kw was used.
the feed stream is given by the following equation.
Substituting Eqs. (10)–(15) into Eqs. (17)–(24) gives final equations
FðT=273:5ÞðP atm =PÞ for x, y, and z. The resulting equations are solved using the
U¼ (16)
2
ðpd =4Þ commercial program COMSOL1. COMSOL1 uses a direct, time-
dependent, solver based on Newton’s method. A multi frontal
where T and P are the reactor temperature and pressure massively parallel sparse (MUMPS) direct solver with automatic
respectively. Patm is the atmospheric pressure and d is the diameter matrix symmetry detection was used.
of the tubular plug flow reactor. The reactor is assumed to be The activation energies (EAi, kJ/mol) in Eqs. (21)–(23) were
maintained at isothermal condition. The small pressure drop reported in the literature [19] and are shown in Table 2. Similarly,
across the reactor length is neglected and isobaric conditions are the adsorption constants aSHH2 O , bSHCO2 , aFTH2 O , bFTCO2 were also
assumed. The residence time, t, is defined as s/U, where s is the axial reported by Riedel et al. [19] and are shown in Table 2. The pre-
distance from the entrance of the reactor. Since the reactor tube exponential coefficient, kSH0, in Eq. (21) and the equilibrium
diameter is much smaller than the length of the reactor, plug flow constant, Keq, in Eq. (24) were also reported in the literature [19].
is assumed, and the radial gradients are neglected. One dimen- The pre-exponential coefficient for the FT reaction, kFT0, reported
sional mass balance equations are given in Eqs. (17)–(20) based on by Riedel et al. [19] was found to over predict the hydrocarbon
Eqs. (7)–(9). concentrations in the outlet stream of the reactor when compared
to the experimentally measured values as analyzed by GC.
dx ðCOÞðH2 OÞ
¼ kSH b ðCO2 ðH2 Þ  c (17) Therefore, we determined the pre-exponential coefficient, kFT0,
dt K eq
in Eq. (22) by empirically fitting the computational results for
specie concentrations to the measured values from our experi-
dy
¼ kFT b ðCOðH2 Þ c (18) ments as shown in Table 1. Table 2 shows the value of kFT0 to be
dt
1.29  103, which turns out to be five orders of magnitude smaller
dz than that reported by Riedel et al. [19] This is somewhat surprising
¼ kFTs b ðCOðH2 Þ c (19) because, the CO2 conversion, selectivities and yields of species CO,
dt
C2–C5+ measured in the present work are higher than those
dw reported by Riedel et al. [19] under similar GHSV, temperature, and
¼ kw (20) pressure conditions (Figs. 2 and 3). Therefore, one might have
dt
expected a higher value for the kinetic coefficient for the FT
Expressions for the kinetic parameters are given by Eqs. (21)–
reaction in our case than that for Riedel et al. The reasons for this
(24). These expressions were derived by Riedel who considered
discrepancy might be explained by the following. It is possible that
inhibition due to water, CO, and CO2 adsorption onto the catalyst
Fe exists in much more concentrated form on an individual catalyst
sites [19].
particle in the study of Riedel et al. [19] compared to ours, even
rcat Rg TkSH0 exp½ESH =ðRg TÞ though the Fe content of the final powder forming the fixed bed is
kSH ¼ (21)
½ðCO þ aSHH2 O ðH2 OÞ þ bSHCO2 ðCO2 Þ comparable between our study (8.1% by mass) and that of Riedel
et al. [19] (6.8% by mass). For example, Riedel et al. [19] uses 2.5 g
rcat Rg TkFT0 exp½EFT =ðRg TÞ of catalyst containing Fe and dilutes it with 25 g of silica particles,
kSH ¼ (22) while we impregnate 17.8 g of catalyst with Fe and dilute it by 2.2 g
½ðCO þ aFTH2 O ðH2 OÞ þ bFTCO2 ðCO2 Þ
of alumina. This might have contributed to the differences in rate
rcat Rg TkFTs0 exp½EFTs =ðRg TÞ constants. The significant differences in catalyst composition and
kFTs ¼ (23) results of CO2 hydrogenation suggest that there should be
½ðCO þ aFTsH2 O ðH2 OÞ þ bFTsCO2 ðCO2 Þ
differences in the kinetic analysis of our data as compared to
Riedel et al. [19].
K eq ¼ 10ð2:0292073=TÞ (24)
As discussed earlier, we include the methanation reaction in our
Here T is reaction temperature, Rg is universal rate constant, rcat is model represented by the kinetic constant kFTs in Eq. (23). The
the catalyst density, which is defined as the mass of impregnated activation energy, EFTs, and pre-exponential coefficient, kFTs0, were
catalyst, Mc/bed volume. The bed volume is 14.54 cm3 in our not reported by Riedel et al. [19]. Therefore, they needed to be

Table 2
Kinetic parameter values used in the model.

Kinetic parameter CO2 shift (SH) FT FTs, methanation

ai, H2O 65 Ref. [19] 33 Ref. [19] 33 Ref. [19]

bi, CO2 7.4 Ref (19) 2.7 Ref. [19] 2.7 Ref. [19]
ki,0, mol/s 1.51  107 Ref. [19] 1.29  103 (present study) 5.16  102 (present study)
EA,i, kJ/mol 55 Ref. [19] 72 Ref. [19] 72 Ref. [19]

i = SH, FT, FTs. Reference (Ref.).

62 H.D. Willauer et al. / Journal of CO2 Utilization 3–4 (2013) 56–64
120
100
(% ) CO2, CO, CH4, C3H6
80
60
40
20
0 FT reactions. After 2 s, the CH4, C3H6, CO2 conversion increase and
0 5 10 15 20
Time, s
Fig. 4. Model predictions for the distribution of CO, CH4, C3H6 (C basis) selectivities
and CO2 conversion with residence time (total flow = 400 mL/min, catalyst mass
17.82 g, GHSV = 0.00037 L/s-g).
determined for this study. We assumed that the EFTs for the
methanation reaction was equal to EFT. We determined the value of
kFTs0 by empirically fitting the computational results to CH4
concentrations measured experimentally in the outlet stream of
the reactor as shown in Table 2. The pre-exponential coefficients
reported in Table 2 show a lower than 1 value for the ratio kFTs0/
kFT0 = 0.4, which means that our catalyst has lower selectivity to
methane compared to propylene.
The solutions of Eqs. (17)–(20) provide the concentrations of
CO2, CO, H2, C3H6, CH4, and H2O (shown in Fig. 4) along with the
RWGS and FT reaction rates (shown in Fig. 5(a) and (b)) for a GHSV
value of 3.7  104 L/s-g (total gas flow of 400 mL/min and active
catalyst mass of 17.82 g), 300 8C temperature and 265 psi. The
reaction rates for RWGS and FT shown in Fig. 5(a) and (b) are
calculated by evaluating the algebraic expressions on the right
hand side of Eqs. (17) and (18) respectively. Fig. 4 shows the CO2
conversion, CO, C3H6, and CH4 selectivities on a weight of carbon
basis rather than the molar basis. This means the percent of carbon
in CO2 reactant is converted to the carbon in different product
species. In Figs. 4 and 5(a) and (b), the residence time, t = s/U, really
represents the distance, s, along the length of the tubular reactor
bed. Fig. 4 shows CO decreases while CO2 conversion and C3H6 and
CH4 increase along the length of the reactor. It takes about 18.7 s
Fig. 5. (a) RWGS reaction rate as a function of residence time. (b) FT reaction rate as a function of residence time (total flow = 400 mL/min, catalyst mass 17.82 g,
GHSV = 0.00037 L/s-g).
for the gases to travel along the entire length of the reactor. Fig. 4
shows a sudden change in slope around 2 s for all species. This
quick change in slope may be explained by the differences in the
reaction rates for the RWGS and FT reactions. Fig. 5(a) shows the
RWGS reaction rate reaches its maximum value (3.5  105 s1)
initially and decreases to 0.032 s1 within 2 s. In Fig. 5(b) the FT
reaction rate is initially at zero and increases to its peak value
(0.032 s1) in about 2 s. After 2 s, the FT reaction rate begins to
decrease smoothly and reaches 4  103 s1 at 18.7 s. After 2 s, the
RWGS reaction rate fluctuates but follows the FT reaction rate
curve with time and stays about equal. Therefore, it is clear from
Fig. 5(a) that the RWGS reaction reaches its equilibrium in about
2 s. This corresponds to about 10% of the reactor length. As a result,
Fig. 4 shows how the equilibrium during the reaction begins to
shift toward CO2 as CO is being consumed relatively slowly by the
CO selectivity decreases relatively slowly with distance along the
tubular reactor. The quick change in slope at 2 s indicates that the
RWGS reaction (Eq. (7)) reaches equilibrium much more quickly
than the FT reaction (Eq. (8)) goes to completion because the
largest magnitude of RWGS reaction rate is seven orders of
magnitude higher than the largest magnitude of FT reaction rate.
The model predictions show that the FT reaction is the rate-
controlling step for the overall conversion of CO2 to olefins.
Table 3 lists the selectivities at the end of the tubular reactor for
different values of GHSV obtained by varying the flow rate and
catalyst mass. Table 3 clearly shows decreased CO2 conversion and
increased CO in the product stream as GHSV is increased. The
model predictions suggest that this is mainly due to a small FT
reaction rate relative to the feed rate of the reactants represented
by GHSV. The RWGS reaction rate was found to be very fast relative
to the feed rate of the reactants. As pointed out in the previous
section, Boudard reaction and catalyst deactivation could become
important especially at later times of the reactor operation. They
could also affect the CO2 conversion. The deactivation could occur
due to carbon deposition and liquid product formation which could
slow the diffusion into the catalyst particle pores. The deactivation
kinetics are not well known in general and especially for the
catalyst at hand [31,32].
Fig. 2 shows CO2 conversion predicted by the model similar to
those measured in the experiments in the outlet stream from the
reactor tube. The CO seems to increase from zero steadily with
GHSV in the model predictions – while the measurements also
show an increase in CO with GHSV, CO values remain 20% or more
at low values of GHSV. Fig. 3 shows a steady decrease in methane
and propylene selectivities (on a carbon basis) predicted by the
 H.D. Willauer et al. / Journal of CO2 Utilization 3–4 (2013) 56–64 63

Table 3
Kinetic model predictions for product selectivity, olefin/paraffin ratio, and CO2 conversion over K/Mn/Fe catalysts, impregnated on Al2O3 support under fixed-bed conditions
after 48 h of run time.

GHSV Mass Total flow rate Selectivity (%, carbon based) C3H6/CO2 Conversion H2O/H2CO2 Yield C3H6
(L/s-g) catalyst (mL/min @STP) consumed CO2 ratio in feed (%) = 100y
(g) (%) = (%) = (%) = (x + y + z)/3
C1 C3H6 CO 100(y/3x) 100(x)
(methane) (%) = 100 (y/x) (%) = 100 (x  y  z)/x
(%) = 100 (z/x)

0.000047 17.82 37.5 28.5 70.5 1.3 23.5 61 40.2 43

0.000093 17.82 75 28 70 2 23.3 54.5 35.8 38.1
0.00019 17.82 150 27.3 68.5 4 22.7 48 31.4 32.9
0.00037 17.82 300 26.5 66 7.5 22 42 26.8 22.7
0.00075 8.9 300 25 62 12.5 20.7 36 22.4 22.3
0.0015 4.46 300 22.3 56 22 18.7 32.5 19.3 18.2
0.0029 2.23 300 18.6 46.7 34 15.6 27.5 15.1 12.8
0.006 1.11 300 14 35 51 11.7 25 12.5 8.7

model consistent with the experimental data. The model seems to
over-predict the hydrocarbon (other than methane) selectivity.
Slight differences in the activation energies for our catalyst from
those reported in the literature [19] could be responsible for
relatively small differences observed between the model predic-
tions and the experimental data for the species concentrations.
Until this point in the paper, the simulations shown do not
include the water removal from the reactor (Eq. (20)). We will now
examine the effect of removing water from the reactor. Water
formation is a primary product of the reactions conditions shown
in Eqs. (7)–(9). The water formed under typical FT conditions is
known to influence catalyst activity primarily by re-oxidizing the
catalyst [33,34]. This in turn will affect the product selectivity. By
removing or reducing the effects of water vapor on the catalyst
surface, the equilibrium at the catalyst surface should shift
favorably to the production of desired intermediates such as
olefins over the formation of CO or methane (Eqs. (7)–(9)).
Therefore, we performed simulations by including Eq. (20) into the
model. Eq. (20) represents the rate (kw) at which water vapor is
removed from the reactor by some means. This could be achieved
in practice by condensing the water and removing the liquid water
from the fixed bed reactor. Fig. 6 shows the model predictions for
100
(% ) CO2, CH4, C3H6, Water
the effects of water removal (with kw = 0.1 s1) on CO2 conversion,
C3H6 yield, and H2O selectivity. It shows that water reaches peak
value when the RWGS is completed and then begins to decrease
with distance along the reactor because of the water removal from
the reactor. As the water levels decrease, both CO2 conversion and
C3H6 yield increase with distance along the reactor. Indeed,
predicted C3H6 yield increases to 63.3% at the end of the reactor for
the case when the water is removed, while the yield is only 27.5%
without the water removal.
4. Conclusions
In the quest to develop green alternative energy solutions,
anthropogenic CO2 is a unique carbon resource for the production
of energy-rich hydrocarbons. To take advantage of the higher
concentrations of CO2 in both seawater and industrial flue gas,
modular fixed-bed reactors could offer practical cost-effective
systems for onsite conversion of CO2 to higher hydrocarbons. To
benefit from these modular designs in the future, our catalyst
process was transitioned into a fixed-bed tubular reactor. The
results presented show the effects of GHSV on CO2 conversion and
product selectivity under fixed-bed microchannel reactor condi-
tions. The results indicate that the maximum C2–C5+ yield
obtained in these fixed-bed experiments is 49% higher than that
obtained by CSTR. However when the performance of both reactors
is compared under similar GHSV conditions, C2–C5+ yield is
reduced by 47% in the fixed-bed conditions. The C2–C5+ yield

measured in the fixed bed reactor is consistent with those reported

80
by Riedel et al. under similar GHSV, pressure, and temperature
condition. However at higher GHSV our catalyst appears more
active.
60
There was a small amount of liquid hydrocarbon found in the
product stream that was neglected in the analysis of the data.
Modeling and kinetic analysis of the data indeed show the FT
40
reaction rates are much slower than RWGS reaction rate. As a
result, the RWGS reaches equilibrium within 10% of the reactor
length. Subsequently, the equilibrium slowly shifts toward CO
20
formation at the rate the FT reaction proceeds. Therefore, FT
reaction is the rate-controlling step and leads to the formation
of unreacted CO in the product stream as observed in the
0
experiments. This could be due to catalyst preparation, Fe and K
0 5 10 15 20 loading, physical size and properties. An alternate explanation
Time, s may be found in the composition of hydrocarbon product which
might affect the transport of species to the catalyst sites and the
Fig. 6. Comparison of model prediction for CO2 conversion, C3H6 yield, and water
overall rate of the FT reaction. Furthermore, in this evaluation
with and without water removal from the catalytic tubular reactor (total
flow = 400 mL/min, catalyst mass 17.82 g, GHSV = 0.00037 L/s-g). CO2 conversion we expand on the limited kinetic analysis of CO2 hydrogenation
(*), C3H6 yield (&), H2O (~) with water removal. CO2 conversion (*), C3H6 (&), by including the formation of methane as a by-product in our
H2O (~) without water removal. model and by providing kinetic constants. This model is used to
64 H.D. Willauer et al. / Journal of CO2 Utilization 3–4 (2013) 56–64
show how water removal from the reactor may significantly
increase the hydrocarbon yield and CO2 conversion.
The modeling and kinetic analysis in these studies will be
applied to the further tailor catalyst properties and reactor design
in efforts to facilitate greater CO2 conversion and olefin selectivity
at higher GHSV in fixed-bed microchannel reactor conditions.
Acknowledgments
This work was supported by the Office of Naval Research both
directly and through the Naval Research Laboratory. The research
was performed while MTO and DMD held National Research
Council Research Associateships at the Naval Research Laboratory.
References
[1] Petroleum Quality Information System Report (PQIS), Defense Logistics Agency
Energy, DLA Energy-QT, Fort Belvoir Virginia, 2010.
[2] Defense Logistics Agency: Energy, http://www.energy.dla.mil/DLA_finance_e-
nergy/Pages/dlafp03.aspx (accessed 14.11.12).
[3] H.D. Willauer, D.R. Hardy, K.R. Schultz, F.W. Williams, Journal of Renewable and
Sustainable Energy-AIP American Institute of Physics 4 (2012), art. no. 033111-13.
[4] Report of the Defense Science Board Task Force on DoD Energy Strategy, More
Fight-Less Fuel (Office of the Under Secretary of Defense For Acquisition, Tech-
nology, and Logistics. Washington, DC 20301, February 2008).
[5] K. Deffeyes, Hubbert’s Peak: The Impending World Oil Shortage, Princeton Univ.
Press, Princeton & Oxford, 2001.
[6] T. Coffey, D.R. Hardy, G.E. Besenbruch, K.R. Schultz, L.C. Brown, J.P. Dahlburg,
Defense Horizons 36 (2003) 1–11.
[7] B.H. Davis, Topics in Catalysis 32 (2005) 143–168.
[8] G.A. Olah, A. Goeppert, G.K.S. Prakash, Beyond Oil and Gas: The Methanol
Economy, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2006.
[9] V. Nikulshina, C. Gebald, A. Steinfeld, Chemical Engineering Journal 146 (2009)
244–248.
[10] H.D. Willauer, F. DiMascio, D.R. Hardy, M.K. Lewis, F.W. Williams, Industrial and
Engineering Chemistry Research 51 (2012) 11254–11260.
[11] I. Ganesh, Materials Sciences and Applications 2 (2011) 1407–1415.
[12] F.T. Zangeneh, S. Sahebdelfar, M.T. Ravanchi, Journal of Natural Gas Chemistry 20
(2011) 219–231.
[13] R.W. Dorner, D.R. Hardy, F.W. Williams, H.D. Willauer, Energy and Environmental
Science 3 (2010) 884–890.
[14] T. Takahashi, W.S. Broecker, A.E. Bainbridge, The Alkalinity and Total Carbon
Dioxide Concentration in the World Oceans. In Carbon Cycle Modelling, Vol. 16;
SCOPE, John Wiley & Sons, New York, NY, USA, 1981, pp. 271–286.
[15] T. Takahashi, W.S. Broecker, S.R. Werner, A.E. Bainbridge, Carbonate Chemistry of
the Surface of the Waters of the World Oceans, in: E.D. Goldberg, Y. Horibe, S.
Katsuko (Eds.), Isotope Marine Chemistry, Uchida Rokakuho Pub. Co., Tokyo,
Japan, 1980, pp. 291–326.
[16] H.D. Willauer, F. DiMascio, H.R. Hardy, M.K. Lewis, F.W. Williams, Industrial and
Engineering Chemistry Research 50 (2011) 9822–9876.
[17] R.W. Dorner, D.R. Hardy, F.W. Williams, H.D. Willauer, Catalysis Communications
15 (2011) 88–92.
[18] R.W. Dorner, D.R. Hardy, F.W. Williams, H.D. Willauer, Applied Catalysis A:
General 373 (2010) 112–121.
[19] T. Riedel, G. Schaub, K.-W. Jun, K.-W. Lee, Industrial and Engineering Chemistry
Research 40 (2001) 1355–1363.
[20] M.-J. Choi, J.-S. Kim, H.-K. Kim, S.-B. Lee, Y. Kang, K.-W. Lee, Korean Journal of
Chemical Engineering 18 (2001) 646–651.
[21] Y. Zhang, G. Jacobs, D.E. Sparks, M.E. Dry, B.H. Davis, Catalysis Today 71 (2002)
411–418.
[22] S.R. Deshmukh, A-L.Y. Tonkovich, K.T. Jarosch, L. Schrader, S.P. Fitzgerald, D.R.
Kilanowski, J.J. Lerou, J. Mazanec, Industrial and Engineering Chemistry Research
49 (2010) 10883–10888.
[23] Oil & Gasengineer, February 2010, pp. 11–14, www. Engineerlive.com.
[24] R.L. Espinoza, A.P. Steynberg, B. Jager, A.C. Vosloo, Applied Catalysis A 186 (1999)
13–26.
[25] W.-P. Ma, Y.-L. Zhao, Y.-W. Li, Y.-Y. Xu, J.-L. Zhou, Reaction Kinetics and Catalysis
Letters 66 (1999) 217–223.
[26] D.L. Trimm, Catalysis Today 37 (1997) 233–238.
[27] H. Habazaki, M. Yamasaki, B.-P. Zang, A. Kaswashima, S. Kohno, T. Takai, K.
Hashimoto, Applied Catalysis A: General 172 (1998) 131–140.
[28] G.W. Norval, The Canadian Journal of Chemical Engineering 86 (2008) 1062–
1069.
[29] J. Wu, M. Saito, M. Takeuchi, T. Watanabe, Applied Catalysis A 218 (2001) 235–
240.
[30] M. Saito, T. Fujitani, M. Takeuchi, T. Watanabe, Applied Catalysis A: General 138
(1996) 311–318.
[31] J. Barbier, Applied Catalysis A 23 (1986) 225–243.
[32] J.A. Moujlin, A.E. van Diepen, F. Kapteijen, Applied Catalysis A 212 (2001) 3–16.
[33] M. Bayat, M.R. Rahimpour, Journal of Natural Gas Science and Engineering 9
(2012) 73–85.
[34] R. Guettel, U. Kunz, T. Turek, Chemical Engineering and Technology 31 (2008)
746–754.