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Kinetics of the Fischer-Tropsch reaction in fixed-bed reactor over a nano-

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DOI: 10.1016/j.jngse.2015.06.036

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 Journal of Natural Gas Science and Engineering 26 (2015) 940e947

Contents lists available at ScienceDirect

Journal of Natural Gas Science and Engineering

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

Kinetics of the FischereTropsch reaction in fixed-bed reactor over

a nano-structured FeeCoeCe catalyst supported with SiO2
Amir Eshraghi a, Ali Akbar Mirzaei a, *, Hossein Atashi b
a
Department of Chemistry, Faculty of Sciences, University of Sistan & Baluchestan, Zahedan 98135-674, Iran
b
Department of Chemical Engineering, Faculty of Engineering, University of Sistan & Baluchestan, P.O. Box 98164-161, Zahedan, Iran

a r t i c l e i n f o a b s t r a c t

Article history: The kinetic of carbon monoxide hydrogenation over the SiO2 supported nano-structured FeeCoeCe
Received 15 March 2015 catalyst was studied in a fixed-bed reactor under the conditions as follows: temperature of 523.15
Received in revised form e603.15 K, pressure of 2e10 bar, H2/CO feed ratio of 1:1 and gas hourly space velocity of 4500 h
1.
13 June 2015
Characterization of both precursor and calcined catalysts was carried out using Scanning Electron Mi-
Accepted 19 June 2015
Available online 29 June 2015
croscopy (SEM) and BrunauereEmmetteTeller (BET) specific surface area measurements. 35 rate equa-
tions for CO consumption were derived based on various mechanisms, Langmuir-Hinshelwood-
Houngen-Watson (LHHW) and the EleyeRideal type rate equation. The discrimination of the kinetic
Keywords:
FeeCoeCe catalyst
models and parameters estimation were carried out by using kinetic data measured in this study. Finally,
Fixed-bed reactor the best fitted model (FT-XI) was derived from EleyeRideal kinetics model. In this model rate deter-
Kinetic model mining step is formation of CH2 monomer and the activation energy was obtained 41.14 kJ/mol.
Activation energy © 2015 Elsevier B.V. All rights reserved.

1. Introduction
FischereTropsch synthesis (FTS) is a heterogeneously catalyzed
reaction that can be produced mixture of hydrocarbons involving of
alkanes (linear and branched), alkenes and oxygen containing
products through hydrogenation of carbon monoxide
(Bartholomew and Farrauto, 2010). Using processes such as: partial
oxidation, catalytic partial oxidation, steam reforming and carbon
dioxide reforming, synthesis gas (mixture of CO þ H2) can be pro-
duced from biomass, peat, coal and natural gas. In the process of
GTL (gas-to-liquid) technology for transformation of biomass, peat,
coal and natural gas to liquid transportation fuels, FischereTropsch
synthesis (FTS) has important role because in the mixture of hy-
drocarbons n-paraffins and 1-olefins are major products
(Bartholomew and Farrauto, 2010; Richardson et al., 2012). The FTS
is heterogeneously catalyzed by group VIII metal. The specific ac-
tivity in this group increasing in the following order (Vannice,
1975): Ir < Pt < Pd < Rh < Fe < Co < Ru. Among the above
metals, iron, cobalt and ruthenium are active catalysts for
FischereTropsch synthesis (FTS) but the product distribution is
different for each of them (Anders Blekkan et al., 2007). Fe is high
active for the water gas shift reaction (WGS). Low boiling
* Corresponding author.
E-mail address: mirzaei@hamoon.usb.ac.ir (A.A. Mirzaei).
hydrocarbons and alcohols are main products over the Fe-based
catalysts (Anders Blekkan et al., 2007; Kraum, 1999). Co-based
catalysts is little active for the water gas shift reaction. Most
products over the Co based catalysts are n-alkanes and 1-alkenes
(Anders Blekkan et al., 2007; Newsome, 2006). On ruthenium the
formation of polyethylene was found by Pichler (Kraum, 1999). To
obtain a detailed kinetic model for FTS, we have to know mecha-
nism of that. The FischereTropsch synthesis is surface polymeri-
zation reaction with the following steps: (1) reactant adsorption,
(2) chain initiation, (3) chain growth, (4) chain termination, (5)
product desorption, (6) re-adsorption and further reaction but the
exact mechanism is unknown (Adesina, 1996; Davis, 2001; Jacobs
and Davis, 2014; Yang et al., 2003; Griboval-Constant et al., 2002).
Over the Cobalt catalysts, first C1 (without oxygen) intermediate
over metal is formed and then hydrogenated to other hydrocar-
bons. In other word, we can say that FT reaction includes the two
following mechanism: (1) CO hydrogenation reaction, (2) poly-
merization reaction. Monomer formation step is the rate deter-
mining step (RDS) (Van Dijk, 2001). The iron catalysts, the reaction
rate decreases with increasing H2O partial pressure and rises with
increasing partial pressure of H2 (Satterfield et al., 1986; Van Der
Laan and Beenackers, 1999). With regard to the formation of
monomeric species in CO and H2 (synthesis gas) consumption as
the rate determining step, mechanistic kinetic rate expressions
were obtained for the iron catalysts (Satterfield et al., 1986; Van Der

http://dx.doi.org/10.1016/j.jngse.2015.06.036
1875-5100/© 2015 Elsevier B.V. All rights reserved.
 A. Eshraghi et al. / Journal of Natural Gas Science and Engineering 26 (2015) 940e947
Laan and Beenackers, 1999). Two formation methods of monomers
are: (1) surface carbide mechanism: CO is adsorbed and dissociated
on the metal surface to form an active surface carbon species, and
methylene species is formed by hydrogenation of carbon inter-
mediate. Methylene is monomer of the carbide mechanism (Van
Der Laan and Beenackers, 1999; Van Santen and Neurock, 1995),
(2) Combined enol/carbide mechanism: proposes that the methy-
lene groups are formed by eliminating water from the enol in the
rate determining step (Withers et al., 1988). Surface carbide
mechanism is the base of Dixit and Tavlarides,s kinetic equations. In
this mechanism the monomers to form (CHX) are polymerized to
form intermediate hydrocarbons over the metal surface. Hydroge-
nation of carbon as the rate determining step was considered (Dixit
and Tavlarides, 1983). Many researchers groups studied the kinetics
of CO hydrogenation and water gas shift reaction over the iron-
based catalysts (Nakhaei Pour et al., 2010a,b; Teng et al., 2005a,b;
Wang et al., 2003). In general, we can say that these reactions
occur in the iron catalysts various active sites. FTS and WGS re-
actions only affect each other by gas phase (Nakhaei Pour et al.,
2010a,b). The overall goal of this research, the kinetic and mecha-
nism investigation of the FischereTropsch synthesis on SiO2 sup-
ported FeeCoeCe nano-catalyst which was prepared by
impregnation technique. The best kinetic model was obtained and
the kinetic parameters were estimated with non-linear regression
method.
2. Experimental
2.1. Catalyst preparation
In the present study, at first the SiO2 support and then the nano-
structured FeeCoeCe catalyst supported with SiO2 were prepared
using solegel and impregnation procedures, respectively.
2.1.1. The SiO2 support preparation
For synthesis of SiO2 support were used from hydrochloric acid
(1 M) and sodium silicate solutions. 20% sodium silicate solution
was prepared and then titrated by HCl by stirring in a mixer at
500 rpm. The mixture obtained from titration, was stirred in a
mixer at 500 rpm for 10 h. Then it washed with 8 L distilled water.
Precipitated gelation was filtered and dried in oven at 80  C for 45 h
and calcined in the electric furnace in static air at 500  C for 6 h (Ui
et al., 2014). Finding, silica powder was formed.
2.1.2. The nano-structured FeeCoeCe catalyst supported with SiO2
preparation
Certain amounts of Fe(NO3)3$9H2O, Co(NO3)2$6H2O and Ce(N-
O3)3$6H2O salts were mixed together in distillated water
completely. Then, calcined SiO2 support that was prepared in the
Section 2.1.1 added into mixture of salts. Rotary evaporator was
used to rotate the obtained suspension (device was set up in 80  C
for 4 h). The aged suspension was filtered and then it was dried for
6 h at 120  C in oven. The calcination is performed in electric
furnace in static air at 400  C for 4 h. The final formed nano-
structured catalyst is included 10wt%Fe-10wt%Coe10%Ce/70%wt
SiO2, and kept in desiccator.
2.2. Characterization of catalyst
2.2.1. BET surface area analysis
To measure BET surface area of SiO2 support and catalyst sam-
ples (precursor, fresh calcined and used calcined) was used Quan-
tachrome Nova 2000 automated system (USA). Before to analysis,
all of the catalyst samples and SiO2 support were degassed at
300  C for 4 h under nitrogen atmosphere.
941
2.2.2. Scanning electron microscopy (SEM)
A Cambridge S-360 scanning electron microscope device was
used for determine the morphology and particle size of the catalyst
samples that operating at 15 kV.
2.3. Catalyst testing
The detailed set up, equipment and system of the reactor was
reported by Mirzaei and his co-workers (Mirzaei et al., 2015; Vahid
and Mirzaei, 2014). To summarize differential fixed-bed reactor was
used to measure reaction kinetics of the FischereTropsch. Fig. 1
shows a schematic representation of the fixed-bed reactor. H2
and CO with purity of 99.99% were fed from separate cylinders and
through gas lines to the reactor bed. Mass flow controllers were
used to control the flow rate. The gases (CO þ H2) were mixed in a
container before entering the reactor bed. The reactor pressure and
temperature were controlled by an electronic back pressure regu-
lator and thermocouple inserted into catalyst bed. The catalyst was
reduced in a flow (30 ml/min) of hydrogen (purity 99.99%) for 3 h at
400  C and at ambient pressure before reaction start up. The
catalyst was tested at pressure reaction between 2 and 10 bar,
temperature reaction between 250 and 330  C, the feed gas
included of H2, CO at ratio of 1:1 and GHSV ¼ 4500 h
1. In each
experiment, 1.0 gr calcined catalyst (FeeCoeCe/SiO2) was placed to
a fixed bed reactor and for certify steady state operations, reactor
operated nearly 12 h. The on-line gas chromatograph (Thermo
ONIX UNICAM PROGCþ) equipped with sample loop, two Thermal
Conductivity Detector (TCD) and one Flame Ionization Detector
(FID) was applied for FTS products and reactant analysis. C1 to C8
hydrocarbons and CO, H2 were separated by on-line analysis, also
for optimum sensitivity Helium was used as a carrier gas. The tests
were performed in differential fixed-bed reactor. At the low con-
versation of CO and shallow small reactors, can assume that the rate
is constant at all points within the reactor. The following equation is
used to calculate the molar flow rate of CO in synthesis gas for the
all tests in a differential reactor.
0
n0 PCO
0
FCO ¼ (1)
RT
Here is in the following the plug-flow equation in a differential
reactor:
Zxout
W dx xout
xin xout
0
¼ ¼ ¼ (2)
0
FCO
rCO
rCO
rCO
xin
Fig. 1. The structure and different parts of fixed-bed reactor.
942 A. Eshraghi et al. / Journal of Natural Gas Science and Engineering 26 (2015) 940e947

Based on Eq. (2) the experimental rate of CO consumption is as Table 1

follow: Summary of BET surface area measurements for catalyst samples and SiO2
support.
0
XCO FCO Samples Specific surface area (m2/gr)

rCO ¼ (3)
W Precursor 116.68
Fresh calcined 234.88
Used calcined 203.10
3. Results and discussion SiO2 support 60.08

3.1. Catalyst characterization

SEM technique was carried out to investigate morphology and
particle size of the catalyst samples. Fig. 2 indicates SEM images of
the catalyst samples. The images show that the precursor (Fig. 2a),
fresh calcined, that is the catalyst before FT reaction (Fig. 2b) and
used calcined, that is the catalyst after FT reaction (Fig. 2c) have
different morphologies and also they are in scale of nano-metric
particles. The electron micrograph of catalyst precursor (Fig. 2a)
shows that the precursor particles are dense and agglomerate. The
calcined catalyst agglomerate size is less than catalyst precursor
that may be due to remove volatiles. Morphological features and
texture of the calcined catalyst after FT reaction was changed. The
size of the used catalyst grains grew larger by agglomeration that
may be due to sintering during the kinetics measurements.
The BET measurements of the nano-structured FeeCoeCe cat-
alysts supported with SiO2, at different stages (Table 1) show that
the calcination increases the specific surface area which is in
agreement with the SEM observations. Based on SEM results, the
agglomerate size of precursor is more than the size of the calcined
catalyst, so it leads to a decrease in specific surface area of the
precursor as it shown on BET results. Among all of the catalyst
samples, the fresh calcined catalyst has a maximum amount of
specific surface area.
information achieved are presented in Table 2. Kinetic measure-
ments were repeated 3 times to determine the results repeatability,
and the corrected data were used for the development of kinetic
expressions. Considering the mechanisms mentioned, we offered
18 probable mechanisms and elementary reactions of them are
given in Table 3. We used LHHW and EleyeRideal method to obtain
rate equations for each model by taking possible rate determining
steps while all other steps are assumed at quasi-equilibrium. Then,
the models were fitted by one by, into data that are shown in
Table 2. By taking different rate determining steps for each models,
we obtained a different rate equations that are displayed in Table 4.
The derivation of carbon monoxide consumption rate equation will
be discussed for FT-XI model by considering the reaction between
surface carbon and gas phase hydrogen (step 3) as the rate deter-
mining step. The rate equation of step 3 is:

rFT
XI ¼ kP qC qO PH2 (39)
In Eq. (39) qO and qC are portions of active sites that has been
occupied by the adsorbed oxygen and carbon that were generated
from CO dissociation. qO and qC can be determined from the site
balance, the other steps are at equilibrium:

kads;CO
3.2. Kinetic modeling and derivation rate equation
CO* þ * # C * þ O* (40)
kdes; CO
The complexity of the FT reaction mechanism and the many of
species included is the main problem for completely describe the
kinetics of the FT synthesis (Ojeda et al., 2010). In order to derive
kads;CO PCO CV2
kdes;CO qC qO ¼ 0 (41)
rate equations, the reaction pathway should be accepted. The main
mechanisms for FT reaction are: (1) alkenyl mechanism (Maitlis,
1989), (2) oxygenate (enol) mechanism, (3) carbide mechanism
qO qC ¼ bCO PCO CV2 (42)
(Davis, 2001), (4) alkyl mechanism (Brady and Pettit, 1980). The
main difference between these mechanisms is nature of monomer
species formed and adsorption nature of CO and H2 on the catalyst
qO ¼ qC ¼ ðbCO PCO Þ0:5 CV (43)
surface. The kinetic data collection for laboratory experiments and

Fig. 2. SEM images of precursor (a), fresh calcined (b) and used calcined (c).
 A. Eshraghi et al. / Journal of Natural Gas Science and Engineering 26 (2015) 940e947 943

Table 2
Overview of reaction conditions and results for kinetic experiments at Ptot ¼ 2e10, T ¼ 250e330  C, H2
CO ¼ 1 and GHSV ¼ 4500 h
1.

Test no. T(K) PCO(bar) PH2 ðbarÞ F0CO ðmol=minÞ rCO(mol/min g) Xco (%)

1 603.15 1.76 1.96 6.60869E-04 7.68392E-05 11.63

2 593.15 1.76 1.71 6.82068E-04 7.02836E-05 10.30
3 583.15 1.76 1.66 7.03809E-04 6.33836E-05 9.01
4 573.15 1.73 1.72 7.18502E-04 6.25030E-05 8.70
5 563.15 1.71 1.75 7.36784E-04 5.90129E-05 8.01
6 553.15 1.69 1.71 7.51697E-04 5.87386E-05 7.81
7 543.15 1.66 1.65 7.68091E-04 5.76568E-05 7.51
8 523.15 1.63 1.64 8.13303E-04 4.61012E-05 5.67
9 603.15 1.77 1.82 6.64025E-04 7.44041E-05 11.21
10 573.15 2.59 2.55 1.07498E-03 9.60349E-05 8.93
11 573.15 3.48 3.30 1.44396E-03 1.19226E-04 8.26
12 573.15 4.35 3.97 1.80637E-03 1.47850E-04 8.18
13 573.15 5.23 4.92 2.17130E-03 1.74359E-04 8.03
14 573.15 6.11 5.60 2.53317E-03 2.03429E-04 8.03
15 573.15 6.99 6.41 2.90111E-03 2.27392E-04 7.84
16 573.15 7.87 7.07 3.26654E-03 2.53461E-04 7.76
17 573.15 8.78 7.74 3.64368E-03 2.69586E-04 7.40
18 573.15 2.59 2.71 1.07377E-03 9.70299E-05 9.04

Table 3
Primary elementary reactions scheme for FT synthesis.

Model No. Elementary reaction Model No. Elementary reaction

FT-I 1 CO þ #CO FT-X 1 CO þ #CO

2 CO þ H2 #CHOH 2 CO þ #C þ O
3 CHOH þ H2 #CH2* þ H2 O 3 C þ O þ 2H2 #CH2 þ H2 O þ *
FT-II 1 H2 þ *#H2 FT-XI 1 CO þ #CO
2 CO þ H2 #CH2 O 2 CO þ #C þ O
3 CH2 O þ *#CH2 þ O 3 C þ O þ H2 #CH2 þ O
4 O þ H2 #H2 O þ 2 4 O þ H2 #H2 O þ 
5 O þ CO #CO2 þ 2
FT-III 1 H2 þ #H2 FT-XII 1 CO þ 2#C þ O
2 CO þ H2 #CHOH 2 H2 þ 2#2H
3 CHOH þ H #CH2 þ OH 3 C þ O þ 4H #CH2 þ H2 O þ 5
4 OH þ H #H2 O þ 2
FT-IV 1 CO þ #CO FT-XIII 1 CO þ 2 #C þ O
2 H2 þ 2#2H 2 H2 þ 2#2H
3 CO þ 3H #CH2 OH þ 3 3 C þ O þ 2H #CH2 O þ 3
4 CH2 OH þ #CH2 þ HO 4 CH2 O þ #CH2 þ O
5 OH þ H #H2 O þ 2* 5 O þ H #OH þ *
6 OH þ H #H2 O þ 2*
FT-V 1 H2 þ 2#2H FT-XIV 1 CO þ 2 #C þ O
2 CO þ 2H #CHOH þ * 2 H2 þ #H2
3 CHOH þ #CH þ OH 3 C þ O þ H2 #CH2 þ O þ*
4 CH þ OH þ 2H #CH2 þ H2 O þ 3 4 CH2 þ O þ 2H # CH3 þ HO þ 2*
5 OH þ H #H2 O þ 2*
FT-VI 1 H2 þ 2#2H FT-XV 1 CO þ 2*#C þ O
2 CO þ H #COH 2 C þ H2 #CH2
3 COH þ 2H #CH2 OH þ 2 3 O þ H2 #H2 O þ *
4 CH2 OH þ H #CH2 þ H2 O þ 
1 H2 þ 2 #2H
FT-VII 1 CO þ #CO FT-XVI 1 CO þ #CO
2 H2 þ 2 #2H 2 CO þ #C þ O
3 CO þ H #CHO þ  3 H2 þ 2#2H
4 CHO þ H #CHOH þ  4 C * þ H* #CH* þ *
5 CHOH þ H #CH2 OH þ  5 CH* þ H* #CH2 þ *
6 CH2 OH þ #CH2 þ HO 6 O  þ H  #OH* þ *
7 OH þ H #H2 O þ 2 7 OH þ H #H2 O þ 2
8 O þ CO #CO2 þ 2
FT-VIII 1 CO þ #CO FT-XVII 1 CO þ 2#C þ O
2 H2 þ 2#2H 2 H2 þ #H2
3 CO þ 2H #HCOH þ 2 3 C þ H2 #CH2 þ 
4 HCOH þ #CH þ OH 4 O þ H2 #H2 O þ 2
5 CH þ H #CH2 þ 
6 OH þ H #H2 O þ 2
FT-IX 1 CO þ #CO FT-XVIII 1 CO þ 2 #C þ O
2 H2 þ #H2 2 H2 þ 2 #2H
3 CO þ H2 #CH2 O þ  3 C * þ 2H * #CH2 þ *
4 CH2 O þ  #CH2 þ O 4 O* þ 2H* #CH2 þ *
5 O þ H2 #H2 O þ 
6 O þ CO #CO2 þ 2
944 A. Eshraghi et al. / Journal of Natural Gas Science and Engineering 26 (2015) 940e947

Table 4 Table 4 (continued )

Reaction rate equations determined for the FTS.
Model Rate equation
Model Rate equation
kCO bCO PCO

rCO ¼ (19)
FT-I 1 þ bCO PCO þ bH2 PH2
RDS2
kP bCO PCO PH2 RDS2

rCO ¼ (4) kH2 bH2 PH2
1 þ bCO PCO
rCO ¼ (20)
1 þ bCO PCO þ bH2 PH2
RDS1
kCO bCO PCO RDS1,2

rCO ¼ (5) kH2 bH2 PH2 þ kCO bCO PCO
1 þ bCO PCO
rCO ¼ (21)
1 þ bCO PCO þ bH2 PH2
FT-II
RDS2 FT-X
kP PCO bH2 PH2 RDS3

rCO ¼ (6)
1 þ bH2 PH2 2 P
kP bCO PH2 CO

rCO ¼  2 (22)
RDS1 1 þ 2ðbCO PCO Þ0:5
kH2 bH2 PH2

rCO ¼ (7) RDS2
1 þ bH2 PH2
kCO bCO PCO

rCO ¼  2 (23)
FT-III
1 þ 2ðbCO PCO Þ0:5
RDS2
kP PCO bH2 PH2

rCO ¼ (8) FT-XI
1 þ bH2 PH2
RDS3
FT-IV kP bCO PCO PH2

rCO ¼  2 (24)
RDS3 1 þ 2ðbCO PCO Þ0:5
 1:5
kP bCO PCO bH2 PH2

rCO ¼   0:5 4 (9) FT-XII
1 þ bCO PCO þ bH2 PH2
RDS3
 2
RDS2 kP bCO PCO bH2 PH2

rCO ¼   0:5 6 (25)
kH2 bH2 PH2 1 þ 2ðbCO PCO Þ0:5 þ bH2 PH2

rCO ¼   0:5 2 (10)
1 þ bH2 PH2
RDS1
FT-V kCO bCO PCO

rCO ¼   0:5 2 (26)
RDS2 1 þ 2ðbCO PCO Þ0:5 þ bH2 PH2
k P b P

rCO ¼  P CO H2 H2 2 (11)
1 þ bH2 PH2
0:5 RDS2
kH2 bH2 PH2

rCO ¼   0:5 2 (27)
FT-VI 1 þ 2ðbCO PCO Þ0:5 þ bH2 PH2
RDS2
 0:5
kP PCO bH2 PH2 RDS1,2

rCO ¼  0:5 (12) kCO bCO PCO þ kH2 bH2 PH2
1 þ bH2 PH2
rCO ¼  (28)
 0:5 2
1 þ 2ðbCO PCO Þ0:5 þ bH2 PH2
FT-VII
RDS3 FT-XIII
 0:5
kP bCO PCO bH2 PH2 RDS3

rCO ¼   0:5 2 (13)
kP bCO PCO bH2 PH2
1 þ bCO PCO þ bH2 PH2
rCO ¼  (29)
 0:5 4
1 þ 2ðbCO PCO Þ0:5 þ bH2 PH2
RDS1
kCO bCO PCO FT-XIV

rCO ¼  0:5 (14)
1 þ bCO PCO þ bH2 PH2 RDS3
kP bCO PCO bH2 PH2

rCO ¼  3 (30)
RDS2
1 þ 2ðbCO PCO Þ0:5 þ bH2 PH2
kH2 bH2 PH2

rCO ¼  0:5 2 (15)
1 þ bCO PCO þ bH2 PH2 RDS1
kCO bCO PCO

rCO ¼  2 (31)
RDS1,2
  0:5  1 þ 2ðbCO PCO Þ0:5 þ bH2 PH2
kCO bCO PCO þ kH2 bH2 PH2 1 þ bCO PCO þ bH2 PH2

rCO ¼   0:5 2 (16)
RDS2
1 þ bCO PCO þ bH2 PH2
kH2 bH2 PH2

rCO ¼ (32)
FT-VIII 1 þ bH2 PH2 þ 2ðbCO PCO Þ0:5
RDS3
RDS1,2
kP bCO PCO bH2 PH2  

rCO ¼   0:5 3 (17) kCO bCO PCO þ kH2 bH2 PH2 1 þ bH2 PH2 þ 2ðbCO PCO Þ0:5
1 þ bCO PCO þ bH2 PH2
rCO ¼  2 (33)
1 þ bH2 PH2 þ 2ðbCO PCO Þ0:5
FT-IX
RDS3 FT-XV
kP bCO PCO bH2 PH2 RDS2

rCO ¼  2 (18)
1 þ bCO PCO þ bH2 PH2 kP PH2 ðbCO PCO Þ0:5

rco ¼ (34)
1 þ 2ðbCO PCO Þ0:5
RDS1
 A. Eshraghi et al. / Journal of Natural Gas Science and Engineering 26 (2015) 940e947 945

Table 4 (continued ) The rate expressions of the other models are obtained with
Model Rate equation similar manner that are given in Table 4.
RDS1
kCO bCO PCO 3.3. Estimation of the kinetic parameters

rCO ¼  2 (35)
1 þ 2ðbCO PCO Þ0:5
The kinetics data of the CO conversion are presented in (Table 2).
FT-XVI The kinetic data obtained from experiments are used in process of
RDS4 the discrimination between the 18 models and parameters esti-
 0:5
kP ðbCO PCO Þ0:5 bH2 PH2 mation. The LevenbergeMarquardt algorithm is used to better es-

rCO ¼   0:5 2 (36)
1 þ 2ðbCO PCO Þ0:5 þ bH2 PH2 timate of the best fitted model (FT-XI) parameters by minimizing
the following objective function:
FT-XVII
RDS3  2
exp mod
kP ðbCO PCO Þ0:5 bH2 PH2 X
Nexp ri;CO
ri;CO

rCO ¼  2 (37) x2 ¼ (51)
1 þ 2ðbCO PCO Þ0:5 þ bH2 PH2
 2
exp
i¼1 ri;CO
FT-XVIII
RDS3 According to the Arrhenius equation, rate constant is dependent
kP ðbCO PCO Þ0:5 bH2 PH2 on the temperature. To determine the activation energy, rate con-

rCO ¼  0:5 3 (38)
1 þ 2ðbCO PCO Þ0:5 þ bH2 PH2 stant (k) was replaced by Arrhenius equation.
 
Ea
k ¼ k0 exp
(52)
RT
The temperature dependence of the adsorption parameter b is
! evaluated according to following equation. The adsorption enthalpy
kads;CO is determined by using following equation in the model:
bCO ¼ (44)
kdes;CO
 
DH
b ¼ b0 exp
(53)
where bCO is equilibrium constant of CO adsorption step. RT
Assuming that the total number of sites is constant, the con-
The accuracy of the fitted model (FT-XI) relative to the experi-
centration of free active site (CV) can be derived from the site bal-
mental data were obtained from three statistical tests which are R2,
ance equation:
RMSD and MARR that were described as following:
X
n The nonlinear correlation coefficient R2 value that indicates the
CV ¼ 1
qi (45) quantity of variance can be calculated from:
i¼1 !
1 X
Nexp
exp
where qi is portion of active sites filled by absorbed species. In s¼ ri;co (54)
Nexp
comparison with other species, it is proposed a remarkable portion i¼1
of whole sites are filled just by surface carbon and oxygen:
PNexp 
exp mod
2
r
r
CV þ qO þ qC ¼ 1 (46) R2 ¼ 1

i¼1 i;co i;co
(55)
PNexp  exp 2
Substituting Eq. (43) into Eq. (46), the concentration of free i¼1
ri;co

s
active sites will be as follows:
The root mean square deviation (RMSD) measure of the differ-
h i
ences between experimental and calculated consumption rate of
CV ¼ 1
ðqO þ qC Þ ¼ 1
ðbCO PCO Þ0:5 CV þ ðbCO PCO Þ0:5 CV
CO is defined as:
(47)
Nexp 
!2
1 X 2
exp mod
1 RMSD ¼ ri;co
ri;co (56)
CV ¼ h i (48) Nexp i¼1
1 þ 2ðbCO PCO Þ0:5
The mean absolute relative residual (MARR) is defined as:
With substituting of Eq. (48) into Eq. (43), the expressions of qc !
Nexp r exp
r mod
X
and qo can be expressed as: i;CO i;CO 1
MARR ¼ exp   100 (57)
i¼1
ri;CO Nexp
0:5
jbCO PCO j
qO ¼ qC ¼ h i (49)
1 þ 2ðbCO PCO Þ0:5 where Nexp is total number of experiments. As shown in Fig. 3, Eq.
(24) indicates the best fit to the data in this study. The calculated
Finally, by replacing of qO and qC final form into the rate activation energy for the FTS catalytic process was found to be
equation of RDS (Eq. (39)), the final rate equation is derived: 41.14 kJ/mol. The value of activation energy obtained, is in good
agreement with results reported in the literature (Atashi et al.,
kP bCO PCO PH2 2010; Fazlollahi et al., 2013; Kwack et al., 2011; Mirzaei et al.,

rCO ¼  2 (50) 2012; Sarkari et al., 2014). However, the most of the results
1 þ 2ðbCO PCO Þ0:5 shows that the values of activation energy for FTS reaction are
between 63 and 132.3 kJ/mol (Yang et al., 2003; Wang et al., 2003;
946 A. Eshraghi et al. / Journal of Natural Gas Science and Engineering 26 (2015) 940e947

Mogalicherla and Elbashir, 2011; Nakhaei Pour et al., 2010; Todic Table 5
et al., 2013) which value of activation energy obtained at the pre- Values of kinetic parameters of FT-XI model.

sent study is not in this range. In the other word, the difference Parameter Value Dimension
between two series reported the activation energies for FTS reac- k0 0.877 (mol/min.g.bar)
tion, is significant. The activation energy is affected by diffusion Ea 41.14 (kJ/mol)
limitations and it has been shown before that the presence of DHCO
19.81 (kJ/mol)
diffusion limitation lowers the activation energy from 120 kJ/mol to b0 0.289 (bar
1)
R2 0.98 e
60e70 kJ/mol (Post et al., 1989). It is therefore concluded that
RMSD 2.776E-06 e
diffusion limitation effects are present in our research work. The MARR (%) 6.22 e
calculated enthalpy of CO adsorption for the FTS reaction was found
to be
19.81 kJ/mol. The observed enthalpy of CO adsorption in the
present study is close to the results reported in the literature
(Atashi et al., 2010; Hunpinyo et al., in press; Kaiser et al., 2014; Van
Steen and Schulz, 1999). The activation energy, kinetic parameters
and values of statistical tests obtained for the best fitted model (FT-
XI) are given in Table 5. Fig. 4 shows the comparison between
experimental and the predicted (by Eq. (24)) consumption rate of
CO (rCO) for FT-XI model. This model (FT-XI) is developed from the
carbide surface mechanism that composed of elementary reaction
steps as following:

1. CO adsorbed and dissociated over the surface catalyst (without

involvement of hydrogen) and surface carbon and oxygen are
formed, and must be considered this step similar to the results
reported by (Pham et al., 2014).
2. Surface carbon reacted with gas phase hydrogen (H2) and CH2-
surface species is formed. Eq. (24) is of the EleyeRideal type and
assumes that the rate-determining step (RDS) is the reaction of
carbon intermediate with gas phase hydrogen.
One of the main defect to the carbide mechanism is that does
not explain the formation of oxygenated hydrocarbons (alcohols
and aldehydes) (Kraum, 1999). Oxygenated products mentioned
were not found in any of the study steps that increase the accept-
ability of (FT-XI) model.
4. Conclusion
The kinetics of CO hydrogenation process was investigated over
SiO2 supported the nano-structured FeeCoeCe catalyst in fixed-
bed reactor over a range of operating conditions (H2:CO ¼ 1:1,
pressure: 2e10 bar, temperature; 250e330  C and GHSV:
4500 h
1). The catalyst was prepared by means of impregnation
method. The characterization of both precursor and calcined cata-
lysts using SEM and BET showed that based on SEM results, the
Fig. 4. Parity graph of predicted and experimental CO consumption rate.
agglomerate size of precursor is more than the size of the calcined
catalysts. So, it leads to a decrease in specific surface area of the
precursor as it shown on BET results and also, the fresh calcined
catalyst has a maximum amount of specific surface area. The
intrinsic kinetics data at low conversion percent (5e12%) of mon-
oxide carbon are best fitted by the EleyeRideal method rate of the
kP bCO PCO PH2
form
rCO ¼ which was developed based on carbide
ð1þ2ðbCO PCO Þ0:5 Þ2
surface mechanism. The Rate determining step is an EleyeRideal
reaction between surface carbon and gas phase hydrogen. The non-
linear regression method was applied to estimate the kinetic pa-
rameters from experimental data. The activation energy for the best
model (FT-XI) was obtained 41.14 kJ/mol. From the results pre-
sented in this study it is clear that our new prepared ternary
catalyst of FeeCoeCe/SiO2 has been found to be an active catalyst
for FischereTropsch synthesis. In particular, the kinetics results
over this catalyst show that the synergistic effect between three

Fig. 3. Comparison between experimental rates versus predicted rates using Eq. (24). (Reaction conditions: T ¼ 250e330  C, P ¼ 2e10, H2:CO ¼ 1:1, and GHSV ¼ 4500 he1).
 A. Eshraghi et al. / Journal of Natural Gas Science and Engineering 26 (2015) 940e947 947

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