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Journal of the Taiwan Institute of Chemical Engineers 000 (2014) 1–7

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Journal of the Taiwan Institute of Chemical Engineers

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Preparation and characterization of Co–Fe nano catalyst for

Fischer–Tropsch synthesis: Optimization using response
surface methodology
Behnam Sedighi, Mostafa Feyzi, Mohammad Joshaghani∗
Faculty of Chemistry, Razi University, P. O. Box: +98–67149, Kermanshah, Iran

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

Article history: A Co–Fe–resol/SiO2 nano catalyst was prepared by a simple and cheap co-precipitation method for the
Received 28 September 2014 Fischer–Tropsch synthesis (FTS) and characterized by X-ray diffraction (XRD), scanning electron microscopy
Revised 13 December 2014
(SEM), temperature programmed reduction (TPR), Fourier transform infrared (FT-IR), energy dispersive
Accepted 16 December 2014
X-ray (EDX), and N2 adsorption–desorption. The effect of calcination conditions was investigated and it was
Available online xxx
found that the catalyst calcined at 650 °C for 6 h is almost free of resol. The TPR spectrum showed lower
Keywords: reduction temperatures respect to similar Co–Fe catalysts. After the Fischer–Tropsch reaction, a sintered
Fischer-Tropsch synthesis irregular surface with lower surface area, pore volume, and pore diameter was obtained which may be due
Nano catalyst to diffusion of reactants and products into the pores. Analysis of variance (ANOVA) for FTS was carried out
Cobalt–iron catalyst by the central composite design (CCD) using response surface methodology (RSM). Four operational factors
Central composite design namely; pressure, H2 /CO molar ratio, gas hourly space velocity (GHSV), and temperature were selected for
Response surface methodology
design of experiments. As GHSV increases, the CO conversion and selectivity toward light hydrocarbons
(LHCs) decrease while selectivity toward heavy hydrocabons (HHCs) and alcohols (ROH) increases because
the contact time between the feed and catalyst surface decreases.
© 2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction
Progressive investigations are carrying in order to improve the
catalyst performance and reaction conditions of the Fischer–Tropsch
synthesis (FTS) [1–4]. Cobalt and iron are the most important
and commercial transition metal catalyst used either as individ-
ual monometallic [5–7] or composed bimetallic systems [8–11]. The
bimetallic Co–Fe catalysts are generally highly active mainly due to
presence of cobalt. On the other hand, iron is more suitable for poor
hydrogen-to-carbon ratio feedstock which makes the performance of
the water-gas shift reaction inevitable [12,13].
Application of high-surface-area inorganic supports such as silica
results in higher activity and mechanical stability of these active met-
als [14,15]. However in most practical uses, the increase in surface
area is not sufficient enough for significant activity and selectivity.
Application of organic polymers is one of the newest and most effi-
cient methods to increase the porosity of the catalysts. The polymer
is exhausted during a well-designed calcination without breakdown
of the catalyst texture and results in a very porous catalyst with high
surface area and pore volume [16,17]. For example, it was reported
that the presence of resorcinol formaldehyde resin gel during the
preparation of Co/SiO2 catalysts played important roles in increasing
the pore diameter of catalysts and the reducibility and dispersion of
supported cobalt, leading to the more surface active cobalt sites and
larger pores of the catalysts and therefore the higher activity for the
Fischer–Tropsch reactions to produce heavy hydrocarbons [18].
With these effects on hands, we decided to add resol gel during
the preparation of Co–Fe/SiO2 catalysts and investigate their activity
in FT reactions. We used the central composite design (CCD) and re-
sponse surface methodology (RSM) for analysis and optimization of
operational conditions namely temperature, pressure, H2 /CO molar
ratio, and gas hourly space velocity (GHSV). RSM is a useful statisti-
cal technique for optimization and evaluation of interactive effects of
independent variables in several chemical processes [19]. However,
using RSM to optimize FT reactions and evaluation of interactive ef-
fects between variables is still rare [20–22].
2. Experimental

∗
2.1. Catalyst preparation
Corresponding author. Tel.: +98 83 34274559, +988314274559; fax: +98 83
34274559, +98-831-4274559.
E-mail address: mjoshaghani@razi.ac.ir, joshaghanim@yahoo.com, Dalahoo2011@ The Co–Fe–resol/SiO2 catalyst was prepared using the fol-
yahoo.com (M. Joshaghani). lowing co-precipitation method: A mixture of metal nitrates of

http://dx.doi.org/10.1016/j.jtice.2014.12.017
1876-1070/© 2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article as: B. Sedighi et al., Preparation and characterization of Co–Fe nano catalyst for Fischer–Tropsch
synthesis: Optimization using response surface methodology, Journal of the Taiwan Institute of Chemical Engineers (2015),
http://dx.doi.org/10.1016/j.jtice.2014.12.017
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2 B. Sedighi et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2014) 1–7
Scheme 1. Schematic representation of the catalyst test system and used reactor.
Co(NO3 )2 .6H2 O (8.8 g, 0.03 mol) and Fe(NO3 )3 .9H2 O (4.1 g, 0.01 mol)
was dissolved in ethanol (40 ml) in a beaker. Then, tetraethoxysilane
(TEOS) (2.1 g, 0.01 mol) was added and the resulting solution was
heated to 70 °C. Fresh samples of a resol phenolic resin (1.3 g) [23,24]
and H2 C2 O4 .2H2 O (8.9 g, 0.07 mol) were dissolved in ethanol sepa-
rately and were added drop wise to the mixture while with stirring.
After aging for 3 h, the resulting precipitate was washed, filtered and
dried in oven-dried at 120 °C for 20 h and then calcined at 650 °C in
air for 6 h.
2.2. Catalyst characterization
The X-ray diffraction (XRD) patterns were measured using an inel,
model Equinox 3000 (40 kV, 30 mA). X-ray diffractometer scans inten-
sities were recorded with a 2θ step size of 0.02 from 3 to 70°, a count-
ing time of 1.0 s using a Cu Kα radiation source (λ = 1.542 Å) and a
nickel filter. The specific surface area (using BET and BJH methods), the
total pore volume and the mean pore diameter were measured using
a N2 adsorption–desorption isotherm at liquid nitrogen temperature
(−196 °C), using a NOVA 2200 instrument (Quantachrome, USA). Prior
to the adsorption–desorption measurements, all the samples were
degassed at 110 °C in a N2 flow for 3 h to remove the moisture and
other adsorbates. The scanning electron microscopy (SEM) images
of the catalyst and its precursor were observed by AIS2300C micro-
scope. Energy dispersive X-ray (EDX) analysis was performed with an
IXRF model 550i that attached to SEM instrument. Temperature pro-
grammed reduction (TPR) profile of the catalyst before FTS test was
recorded using a micromeritic TPD-TPR 290 system. The TPR for each
sample (50 mg) was performed using a mixture gas of 5%H2 /95%Ar
(v/v) as the reductant. The sample was heated from 25 to 820 °C
at a heating rate of 4 °C/min. The flow rate of the mixture gas was
50 ml/min. Laser particle size analyzer (LPSA) HPPS5001, Malvern, UK
was used for determination of particle size. Fourier transform infrared
(FT-IR) spectra were recorded on an ALPHA, Bruker, Germany in the
range of 400–4000 cm−1 .
Please cite this article as: B. Sedighi et al., Preparation and characterization of Co–Fe nano catalyst for Fischer–Tropsch
synthesis: Optimization using response surface methodology, Journal of the Taiwan Institute of Chemical Engineers (2015),
http://dx.doi.org/10.1016/j.jtice.2014.12.017
[m5G;December 31, 2014;17:13]
2.3. Catalyst testing
The catalytic tests were carried out in a stainless steel fixed bed
reactor (30 cm length and internal diameter is 7 mm) loaded with
1 g of the catalyst sample. A schematic representation of the catalyst
test system is shown in Scheme 1. All gas flow were regulated with a
mass flow controller (MFC) and the reaction pressure was controlled
by a back pressure regulator (BPR).
In the first stage, the catalyst was reduced at 450 °C using H2
(30 ml/min) for 16 h under 1 bar pressure. After reduction, the reac-
tor temperature, pressure, molar ratio H2 /CO, and GHSV were main-
tained at designed conditions according to Scheme 1. The gas prod-
ucts were analyzed on-line using a Varian gas chromatograph (star
3600CX) equipped with a thermal conductivity detector (TCD) and a
chromosorb column. The heavy hydrocarbon products were analyzed
off-line using a Varian CP 3800 with a petrocol TM DH100 fused silica
capillary column and a flame ionization detector (FID). Conversion
of carbon monoxide and selectivity toward all separated products
were measured after steady-state conditions were reached, typically
within a time period of 12–20 h. The conversion of CO and selectivity
for products were calculated according to the normalization method:
mol COin − mol COout
CO conversion (%) = × 100
mol COin
ni Mi
Si (%) = × 100
mol COin − mol COout
where ni and Mi represent the number of carbon atoms and mole
number of product i, respectively.
2.4. Design of experiments
Design of experiments and analysis of variance (ANOVA) for FTS
were carried out using Box center response surface methodology
by Design Expert Software (Stat-Ease Inc., version 7.0.0). CCD was
applied to design of experiments for four parameters namely the total
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Scheme 2. Simplified representation of phase transformation during calcination and FT reaction.
pressure (from 1 to 13 bar), feed molar ratio (from 1.0 to 3.0 H2 /CO),
GHSV (from 3 to 15 min−1 ) and temperature (from 300 to 400 °C)
in five levels. In total 30 experiments were designed from which 6
experiments were the central points. The studied responses were CO
conversion and selectivity toward light hydrocarbons (LHCs), heavy
hydrocarbons (HHCs) and alcohols (ROH).
3. Results and discussion
3.1. Catalyst characterization
The specific surface area (BET and BJH methods), pore volume and
pore diameter of the precursor and catalyst before and after the test
are given in Supplementary Table S1. A relatively high surface area
of the precursor is mainly due to solvent evaporation which makes
a porous surface of high surface area. The surface area, pore volume
and pore diameter of the catalyst before the test were very higher
than the precursor which is mainly due to exit of gasses resulted in
a very porous surface. After the FT synthesis, however, all textural
parameters significantly decrease. This change may be due to either
diffusion of FTS reactants and products into the pores or phase change
during the reaction [18].
The precursor and catalyst before and after the test were exam-
ined with XRD to investigate the effect of calcination and catalyst
performance on the phase structure (Supplementary Fig. S1). The pre-
cursor was largely found to be amorphous and silicate phases. These
amorphous phases make the other phases such as iron phases unde-
tectable. In contrast, the catalyst before the test contains mainly high
oxidation states oxides of cobalt and iron. However, the catalyst after
the test was found to be mainly metallic, carbides and low oxidation
state oxides of iron and cobalt. The average catalyst particle size was
calculated by the modified Scherer equation 45.9 and 38.9, for the
catalysts before and after the test, respectively [25].
The EDX spectrum of the catalyst before the test indicates the
purity of the catalyst (Supplementary Fig. S2). There are some mi-
nor signals below 2 kV which may be due to remained resol in the
catalysts.
The TPR spectrum of Co–Fe–resol/SiO2 catalyst indicates three
peaks (Supplementary Fig. S3) which may be assigned based on sim-
ilar Co–Fe systems [8,9]. However, exact identification of these peaks
is usually difficult because of the overlapping of iron oxide reduction
peaks with cobalt oxide ones. The first peak starts at 270 °C which
may be assigned for reduction of Fe2 O3 to Fe3 O4 and/or Co3 O4 to CoO
[26]. The second peak starting at 420 °C may be due to second reduc-
tion of iron phases from Fe3 O4 to FeO and/or reduction of CoO to Co.
The last peak starting at 580 °C may be due to reduction of FeO to
Fe [27].
The reduction temperatures of Co–Fe–resol/SiO2 are significantly
lower than previous reports on similar Co–Fe catalysts supporting
Please cite this article as: B. Sedighi et al., Preparation and characterization of Co–Fe nano catalyst for Fischer–Tropsch
synthesis: Optimization using response surface methodology, Journal of the Taiwan Institute of Chemical Engineers (2015),
http://dx.doi.org/10.1016/j.jtice.2014.12.017
[m5G;December 31, 2014;17:13]
3
higher activity of our catalyst [28,29]. The lower reduction temper-
ature increases the amount of metallic and active lower-oxidation
state oxides such as FeO and CoO which are responsible for higher
CO conversion. The surface area of the last two peaks are significantly
more than the first peak indicating complete reduction of initially
oxides and supports the XRD results.
According to XRD and TPR studies, it seems that during the reduc-
tion step before FT reaction, oxide phases of iron and cobalt (Fe2 O3
and Co3 O4 ) reduce to the corresponding lower oxidation state oxides
(Fe3 O4 and CoO) as well as metallic phases (Scheme 2). During the
FT reaction, these metallic phases are partially converted to the cor-
responding carbides which are the most likely active phases for FTS
performance and selectivity toward light olefins [30,31].
FT-IR experiments were used to investigate the change of catalyst
during the calcination conditions and performance test (Supplemen-
tary Fig. S4a). A broad band over 3000 cm−1 was observed for the
precursor which could be assigned to the water of crystallization of
nitrate salts. A sharp strong band at 1641 cm−1 was assigned to aro-
matic vibrations of the resol [23,24]. These bands were almost com-
pletely disappeared for the catalyst before the test indicates that resol
almost was decomposed completely upon the calcination at 650 °C. In
addition, two vibration bands for the calcined catalyst appeared at 570
and 670 cm–1 , which could be attributed to the vibrations of Co3 O4
[32]. These bands disappeared in the catalyst after the test indicates
the complete conversion of Co3 O4 . This result confirms the results of
XRD investigation. In the catalyst after the test, there are some bands
at lower frequencies which may be attributed to the vibrations of
present oxides.
The effect of calcination time and temperature was examined us-
ing two different conditions. In the case of calcination at 550 °C for
5 h, a band belonging to resol at 1641 cm−1 , remains indicating in-
sufficient calcination time and/or temperature (Supplementary Fig.
S4b). This band disappears in the catalyst calcined at 650 °C for 6 h,
therefore this condition was used for preparation of the catalyst.
SEM analysis indicates the relatively large difference between the
precursor and the catalyst before and after the test. The electron mi-
crograph, obtained from catalyst precursor, depicts several agglom-
eration of irregularly shaped particles of different sizes most of which
are nearly spherical and constitute high dense agglomeration (Supple-
mentary Fig. S5a). In agreement with BET results, the catalyst before
the test shows high surface area (Supplementary Fig. S5b). After the
FTS, the morphology becomes completely different (Supplementary
Fig. S5c) and a more condensed irregular surface with lower surface
area is obtained.
In addition, a fine sticky and sintered texture contain small parti-
cles has been pasted on the surface. Comparing to the XRD results for
the catalyst after the test, the upper fine sintered texture seems to be
an in situ prepared carbide and lower oxidation state oxides.
The size distribution of the catalyst before and after the test were
shown in Supplementary Fig. S6. A very sharp peak at 50.7 nm with
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Table 1
Catalytic performance of the Co–Fe–resol/SiO2 catalyst under different operational conditions during FTS.

Run Pointa H2 /CO T P GHSV χ CO b LHCs c HHCs d ROH

(°C) (bar) (min−1 ) (%) (%) (%) (%)

1 F 1.5 [−1]e 325 [−1] 4 [−1] 6 [−1] 60.94 (±1.42)f 50.66 (±0.55) 37.91 (±0.59) 5.17 (±0.09)
2 F 2.5 [+1] 325 [−1] 4 [−1] 6 [−1] 67.87 (±2.36) 53.65 (±0.74) 36.79 (±0.33) 4.92 (±0.04)
3 F 1.5[−1] 325[−1] 4 [−1] 12 [+1] 48.23 (±2.05) 58.52 (±0.83) 31.13 (±0.31) 4.05 (±0.34)
4 F 2.5 [+1] 325 [−1] 4 [−1] 12 [+1] 43.22 (±1.39) 61.32(±0.87) 29.21 (±0.27) 4.17 (±0.15)
5 F 1.5 [−1] 325 [−1] 10 [+1] 6 [−1] 46.86 (±1.93) 41.31 (±0.75) 48.16 (±0.11) 6.75 (±0.16)
6 F 2.5 [+1] 325 [−1] 10 [+1] 6 [−1] 63.25 (±2.76) 42.38 (±1.14) 47.88 (±1.32) 6.28 (±0.03)
7 F 1.5 [−1] 325 [−1] 10 [+1] 12 [+1] 36.83 (±2.33) 49.27 (±1.33) 39.61 (±0.73) 5.61 (±0.07)
8 F 2.5 [+1] 325 [−1] 10 [+1] 12 [+1] 28.79 (±2.23) 50.85 (±0.04) 38.78 (±0.37) 5.29 (±0.09)
9 F 1.5 [−1] 375 [+1] 4 [−1] 6 [−1] 61.21 (±1.77) 44.31 (±3.34) 41.60 (±0.36) 5.78 (±0.37)
10 F 2.5 [+1] 375 [+1] 4 [−1] 6 [−1] 79.80 (±1.05) 52.44 (±1.52) 37.11 (±0.51) 4.92 (±0.19)
11 F 1.5 [−1] 375 [+1] 4 [−1] 12 [+1] 43.23 (±1.34) 56.15 (±0.53) 32.24 (±0.38) 4.56 (±0.06)
12 F 2.5 [+1] 375 [+1] 4 [−1] 12 [+1] 43.22 (±1.65) 58.02 (±0.47) 30.21 (±1.21) 4.12 (±0.04)
13 F 1.5 [−1] 375 [+1] 10 [+1] 6 [−1] 46.86 (±2.12) 38.15 (±0.57) 49.59 (±0.38) 6.44 (±0.03)
14 F 2.5 [+1] 375 [+1] 10 [+1] 6 [−1] 72.70 (±2.77) 41.26 (±0.11) 45.98 (±0.28) 6.21 (±0.04)
15 F 1.5 [−1] 375 [+1] 10 [+1] 12 [+1] 28.83 (±2.21) 46.42 (±0.28) 41.95 (±0.40) 5.64 (±0.11)
16 F 2.5 [+1] 375 [+1] 10 [+1] 12 [+1] 28.79 (±1.96) 49.13 (±0.33) 39.21 (±0.46) 5.47 (±0.25)
17 A 1 [−2] 350 [0] 7 [0] 9 [0] 28.05 (±2.44) 46.42 (±0.75) 43.86 (±0.54) 5.82 (±0.05)
18 A 3 [+2] 350 [0] 7 [0] 9 [0] 36.05 (±1.55) 51.09 (±0.28) 37.28 (±1.18) 5.18 (±0.04)
19 A 2 [0] 350 [0] 7 [0] 3 [−2] 82.89 (±1.46) 46.41 (±1.18) 43.27 (±0.58) 5.84 (±0.07)
20 A 2 [0] 350 [0] 7 [0] 15 [+2] 40.08 (±2.42) 58.62 (±1.66) 29.05 (±0.55) 4.04 (±0.05)
21 A 2 [0] 350 [0] 1 [−2] 9 [0] 64.76 (±1.62) 59.62 (±1.37) 28.34 (±0.74) 4.19 (±0.09)
22 A 2 [0] 350 [0] 13 [+2] 9 [0] 46.59 (±2.31) 39.51 (±0.67) 48.45 (±0.26) 6.30 (±0.18)
23 A 2 [0] 300 [−2] 7 [0] 9 [0] 54.22 (±0.69) 47.75 (±2.37) 40.61 (±0.61) 5.54 (±0.03)
24 A 2 [0] 400 [+2] 7 [0] 9 [0] 53.86 (±0.51) 46.95 (±0.61) 40.82 (±0.86) 5.41 (±0.16)
25 C 2 [0] 350 [0] 7 [0] 9 [0] 65.12 (±1.04) 47.91 (±0.55) 40.67 (±0.25) 5.73 (±0.24)
26 C 2 [0] 350 [0] 7 [0] 9 [0] 65.48 (±0.97) 47.05 (±1.42) 41.57 (±0.66) 5.67 (±0.09)
27 C 2 [0] 350 [0] 7 [0] 9 [−1] 65.19 (±0.86) 47.47 (±1.26) 41.46 (±0.59) 5.60 (±0.04)
28 C 2 [0] 350 [0] 7 [0] 9 [0] 64.76 (±0.53) 47.74 (±0.67) 41.35 (±0.43) 5.53 (±0.02)
29 C 2 [0] 350 [0] 7 [0] 9 [0] 61.49 (±2.45) 50.78 (±2.12) 39.70 (±1.31) 5.26 (±0.34)
30 C 2 [0] 350 [0] 7 [0] 9 [0] 64.39 (±0.14) 48.80 (±0.41) 40.64 (±0.27) 5.59 (±0.06)
a
F, A and C referred to factorial, axial and center points, respectively.
b
Conversion of CO.
c
LHCs: Light hydrocarbons (C1 –C4 ).
d
HHCs: Heavy hydrocarbons (C5+ ).
e
The numbers in bracket are the coded value (alpha numbers).
f
The standard deviations were determined from at least three individual experiments.

Fig. 1. CO conversion as a function of (a) GHSV and pressure (H2 /CO = 2.0, T = 350 °C), (b) H2 /CO and temperature (GHSV = 9 min−1 , P = 7 bar).

100% intensity (PDI = 0.500) is observed for catalyst before the test (a)
which indicates a narrow distribution of nano particle of size 50 ± 5
nm. After the FT synthesis, this band shifts to higher sizes and becomes
broaden (b). The average particle size for the catalyst after the test
was 69 nm (PDI = 0.485).
3.2. Design of experiment
The operation conditions and all studied responses were summa-
rized in Table 1. The range of operation conditions were designed
based on literature review to cover all possible requirements to gain
the best optimal condition. In the other hand, the CO conversion was
selected as a measure of catalyst activity while LHCs, HHCs and ROH
were choiced as a measure of catalyst selectivity.
Evaluation of data by design matrix evaluation showed no aliases
when response surface quadratic model was employed (Supplemen-
tary Table S3). Using this model, the degree of freedom (df) for lack
of fit and pure error were obtained 10 and 5, respectively which
are higher than the minimum amount recommended (3 and 4, re-
spectively). The variance of inflation values (VIF) were very close to
ideal 1.00 value which means that all coefficients are productively
stimated. The Ri-squared values were also very close to ideal 0.00
value indicating a well defined model.

Please cite this article as: B. Sedighi et al., Preparation and characterization of Co–Fe nano catalyst for Fischer–Tropsch
synthesis: Optimization using response surface methodology, Journal of the Taiwan Institute of Chemical Engineers (2015),
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Fig. 2. (a)–(c) Selectivities of LHCs, HHCs and ROH as a function of GHSV and pressure, respectively (H2 /CO = 2.0, T = 350 °C); (d)–(f) and as a function of H2 /CO and temperature,
respectively (GHSV = 9 min−1 , P = 7 bar).

Analysis of variance was carried out on all responses. In the first
step, to achieve an accurate and simple model for each response, all
available process models including linear, 2FI, quadratic and cubic
were used. According to sequential model sum of squre and lack of
fit tests, quadratic model was chosen for optimization studies of all
responses. Although, in the case of ROH and LHCs fragments, the
simplest linear model was also suggested by statistical fits.
Using backward elimination regression process (α = 0.10), the
final revised models were obtained and summarized in Table 2. The
large F-value of all studied responses imply that the selected models
are significant.
For all responses, the F and probabilty values indicating the model
is significant. In addition, the probability values for all significant
terms were smaller than 0.0001. The “Pred R-squared” was in rea-
sonable agreement with the “Adj R-squared”. The “Adeq precision”
which is a measure of the signal to noise ratio indicates an ade-
quate signal and this model could be used to navigate the design
space.

Please cite this article as: B. Sedighi et al., Preparation and characterization of Co–Fe nano catalyst for Fischer–Tropsch
synthesis: Optimization using response surface methodology, Journal of the Taiwan Institute of Chemical Engineers (2015),
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Table 2
Response surface quadratic evaluation of data.a

Response Optimized coded equation F value dF R-Squared Adj R-squared Pred R-squared Adeq precision

CO +64.41 + 2.94 A – 11.83 B – 5.46 C – 5.05 AB + 2.13 AD 115.05 10 0.98 0.98 0.95 40.08
– 2.17 BD – 8.22 A2 – 0.86 B2 – 2.31C2 – 2.72 D2
LHCs +48.50 + 1.40 A + 3.75 B – 4.86 C – 0.99 D + 1.04B2 102.18 5 0.96 0.95 0.92 35.05
HHCs +40.85 – 1.26 A – 3.80 B + 4.80 C + 0.37 D – 0.55 AD 250.44 7 0.99 0.98 0.98 54.68
– 1.14 B2 – 0.58 C2
ROH +5.54 – 0.16 A – 0.47 B + 0.59 C – 0.077 CD – 0.15 B2 95.67 6 0.96 0.95 0.93 33.20
– 0.070 C2
a
A, B, C and D are representive of H2 /CO mol ratio, GHSV, pressure and temperature, respectively. The products terms of the main factors represent the interaction
parameters.

Table 3
The predictability of the optimized model using five independent experimental runs.a

Run 1 2 3 4 5

H2 /CO 1.5 2.5 1.5 2.5 2.5

GHSV (min−1 ) 6 12 6 12 6
Pressure (bar) 4 10 10 4 10
Temperature (°C) 325 375 375 325 325
CO conversion (%) 61.20 (59.81) 33.33 (31.10) 49.24 (48.95) 41.23 (42.10) 59.75 (60.61)
LHCs (%) 51.82 (50.23) 49.76 (48.85) 38.36 (38.55) 59.59 (60.53) 42.12 (43.32)
HHCs (%) 38.25 (38.48) 38.24 (38.71) 50.12 (49.91) 28.87 (29.46) 46.26 (46.65)
ROH (%) 5.84 (5.29) 5.82 (5.21) 6.61 (6.47) 4.83 (4.03) 6.73 (6.30)
a
The predicted value are shown in parenthesis.

Fig. 3. Optimum conditions for obtaining the maximum amount of HHCs (T = 375°C, H2 /CO = 2.2, P = 7.00 bar, GHSV = 6.00 min−1 ).

The predicted versus actual plots indicate that all experiomental
data are precisly predicted by the model (Supplementary Fig. S7).
The internally and externally studentized residuals were also settled
between critical line borders. Other statistical diagnostic tools such
as Cook’s distance and difference of fits (DFFITS) were also carried out
and accuracy of all experimental data was proved.
The effect of all studied factors were investigated on all responses.
The CO conversion decreases with increasing GHSV linearly since the
contact time between the feed and catalyst surface decreases with
increasing GHSV [33,34] (Fig. 1a). A similar trend was also observed
with increasing the pressure which may be due to decreaseing in
the bulk diffusivity at high pressures. The CO conversion increases at
first with increasing temperature to about 350 °C and then decreases
gradually. This decrease in CO conversion at high reaction tempera-
ture may be due to diffusion of heavy products such as waxes into the
pores and formation of cock on surface. which resulted in a sintered
surface with lower surface area. Similar trend was also observed for
the H2 /CO molar ratio; the CO conversion increases with increasing
the molar ratio to about 2 and then decreases dramatically (Fig. 1b). It
may be due to more contribution of reverse water-gas shift reaction
in higher H2 /CO molar ratio.
All product selectivities showed a relatively linear realtionship to-
ward all studied factors. (Fig. 2a–f). With increasing the GHSV, the
selectivity toward LHCs increases while, the selectivity toward HHCs
and ROH decreases. Increasing the GHSV results in decreasing the
contact time of feed with catalyst surface and prohibits the chain
propagation. In contrast, increasing the pressure led to the decrease
in LHCs selectivity and HHCs and ROH selectivities.The product selec-
tivities have linear relationships with H2 /CO molar ratio and temper-
ature. The LHCs also increases with increasing the content of H2 in
the feed while other responses decrease. In addition, with increasing
the temperature, the LHCs decreases while HHCs and ROH increase.
The selected models then were optimized for all responses. The
criteria for the process optimization explore the maximum CO con-
version together with one of the fragments depends on the process
target. The maximum amount of HHCs is achieved using H2 /CO, GHSV,
pressure and temperature 2.2, 6.00 min−1 , 7.00 bar, and 375 °C, re-
spectively (Fig. 3).
The predictability of the optimized model was investigated using
five independent experimental runs. Table 3 summarized the results
and indicated excellent confidence between the predicted and ob-
served value.

Please cite this article as: B. Sedighi et al., Preparation and characterization of Co–Fe nano catalyst for Fischer–Tropsch
synthesis: Optimization using response surface methodology, Journal of the Taiwan Institute of Chemical Engineers (2015),
http://dx.doi.org/10.1016/j.jtice.2014.12.017
JID: JTICE
ARTICLE IN PRESS
B. Sedighi et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2014) 1–7
4. Conclusions
Co–Fe–resol/SiO2 catalyst was prepared by modified co-
precipitation method with the addition of resol during the precip-
itation and used in FTS reaction. The addition of resol significantly
increased surface active sites and pore volume that were two impor-
tant factors in determining the FTS activity and selectivity. The TPR
spectrum of the catalyst shows formation of active metallic and car-
bide phases on the surface of the catalyst. In addition, the reduction
temperatures particularly for cobalt are significantly fewer than pre-
vious reports on similar Co–Fe catalysts supporting higher activity of
our catalyst.
The FTS was optimized using CCD and RSM involved four impor-
tant operational factors including pressure, H2 /CO mole ratio, GHSV
and temperature. All responses including CO conversion, LHCs, HHCs
and ROH fragments were optimized using quadratic model although,
LHCs and ROH could be optimized using simpler linear model. There
was good agreement between the experimental and simulated values.
The results show that CO conversion decreases with increase of
GHSV while, increases with increasing the pressure. In addition, with
increase of GHSV selectivity toward the HHCs decreases which sug-
gested that higher GHSV facilitates the desorption of surface Cx Hy
species and decreases the residence time of these species, resulting in
a decreased selectivity of hydrocarbons with higher carbon number.
Acknowledgment
The authors thank Razi University Research Council for support of
this work.
Supplementary materials
Supplementary material associated with this article can be found,
in the online version, at doi:10.1016/j.jtice.2014.12.017.
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