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Modelling and optimization of FischereTropsch

products through iron catalyst in fixed-bed reactor

Hossein Atashi*, Fatemeh Rezaeian

Department of Chemical Engineering, University of Sistan and Baluchestan, P.O. Box 98164-161, Zahedan, Iran

article info abstract

Article history: The most important issue for alternative renewable energy source instead of fossil fuels is
Received 15 February 2017 environmental concern. Human energy supply from carbon waste has an important role in
Received in revised form environmental health. FischereTropsch synthesis is a reaction whereby carbon waste such
20 April 2017 as woods, foodstuffs, sewage, and any material that contains carbon in their structure,
Accepted 21 April 2017 produces all oil derivatives including gasoline, diesel, etc. In this paper, the products model
Available online xxx and the effective parameters of the model and also, the interaction between the parame-
ters were investigated. PH2 and T*PH2 are effective parameters and interaction in the model,
Keywords: respectively. Finally, the optimization of products was discussed. The best operating
FischereTropsch synthesis conditions for minimizing CO2 and CH4 and maximizing C2H4 and C2H6 were investigated.
Iron catalyst This method can be suitable for environmental purposes.
Waste materials © 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Selectivity
Environment
Products model

gas (H2 þ CO). As can be seen in Fig. 1, synthesis gas is a

Introduction
Increase in greenhouse gasses resulting from fossil fuel pro-
cesses including transportation fuels induces a lot of climate
changes, which, is inevitable from environmental point of
view. Also, declining oil reserves, rising price of crude oil, and
increasing energy demand especially for transport, have
caused scientists to think about alternative sources [1,2]. On
the contrary, the wastes including urban, agricultural, and
industrial waste which are harmful to the environment, can
be utilized into gasification process and to produce synthesis
feedstock for FischereTropsch synthesis [3,4].
Products like olefins, diesel, gasoline, kerosene, and
methanol are the result of FischereTropsch reaction.
FischereTropsch reaction is a catalytic reaction which can
produce a variety of products by changing the nature of the
catalyst. The importance of these products is that they do not
contain any harmful substances like sulfur and aromatics.
Therefore, these products have been remarkable in terms of
the environment and are in competition with fossil fuels
[5e7]. Transition metals which are active in FischereTropsch
synthesis are listed according to the average molecular weight
of hydrocarbons produce as follows:

Ruthenium > Iron > Cobalt > Rhodium > Nickel > Iridium > Platinum > Palladium

* Corresponding author.
E-mail addresses: h.ateshy@hamoon.usb.ac.ir (H. Atashi), ch.engineering87@gmail.com (F. Rezaeian).
http://dx.doi.org/10.1016/j.ijhydene.2017.04.224
0360-3199/© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: Atashi H, Rezaeian F, Modelling and optimization of FischereTropsch products through iron catalyst
in fixed-bed reactor, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.04.224
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0
Fig. 1 e Strategies for production of oil derivatives from biomass [4].
The catalyst of Iridium (Ir), Platinum (Pt), and Palladium (Pd)
produce more methane. Cobalt (Co) and iron (Fe) are the most
frequently used for commercial scale production while Nickel
(Ni), Ruthenium (Ru) are preferred for academic research [8,9].
The advantage of using iron catalyst can be noted as follows:
low cost, excellent performance in Water Gas Shift reaction
(WGS), high selectivity of olefins products, low selectivity of
methane, and have high activity in FTS [10,11].
Several research have been carried out for improving the
activity, stability, and selectivity of catalyst by adding pro-
moters. For instance, potassium is a very common metal that
can be used as a promoter because it enhances the
FischereTropsch synthesis and Water Gas Shift reaction
catalyst. In addition, it shifts the products to the higher mo-
lecular weight of hydrocarbons [12,13].
Copper has the same result and increases isomerization of 1-
alkenes to 2-alkenes and hydrogenation of olefins while potas-
sium prevents any of these reactions [14]. Potassium increases
the selectivity of olefins and suppression of methane and the
formation of light hydrocarbons [15]. Fe/Cu/K/SiO2 catalyst with
different molecular weight is mostly utilized than the other
catalysts. Bukur used three types of this catalyst to determine
their performance [16] and Hai-Jun also used different supports
to enhance the performance of the catalyst, he also prepared Fe/
Cu/K/SiO2 and Fe/Cu/K/Fe2O3 catalysts and it was concluded
that the catalyst with SiO2 has low deactivation and high activity
of FTS and also, increase the Cþ 5 selectivity [17].
Recently, many studies have been conducted on products
distributions and many factors such as operating conditions
have effect on products distributions. Manipulation of oper-
ating conditions like temperature, pressure, space velocity,
H2/CO ratio, time on stream, etc. can change product selec-
tivity. Increase in temperature causes the products to shift to
higher hydrocarbons and increase the conversion of CO but Cþ 5 The drying was done for 16e24 h and also the calcination
is reduced. Increase in pressure causes the products to shift to
heavier hydrocarbons. Increase in H2/CO ratio causes the
products to shift to heavier hydrocarbons. Decrease in space
velocity causes increase in the conversion of CO and de-
creases the selectivity of methane [18e20].
Kinetic and selectivity of Fischer Tropsch products
constitute two pillars in the reaction. Many studies have been
proposed on selectivity and variety of methods. Dragomir
investigated olefin selectivity and the reaction conditions over
Fe catalyst [21]. Haghtalab studied the ability of his catalyst to
increase selectivity of long-chain hydrocarbons and reduce
the lighter hydrocarbons [22]. Shawane by employing Taguchi
method provided optimal conditions and investigated cata-
lytic activity [23]. Forghani et al. investigated the selectivity of
Please cite this article in press as: Atashi H, Rezaeian F, Modelling and optimization of FischereTropsch products through iron catalyst
in fixed-bed reactor, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.04.224
Fischer Tropsch products in membrane reactor and conven-
tional Fischer Tropsch reactor [7]. Atashi et al. studied ther-
modynamic analysis which is combine with RSM [24]. One of
the advantage of selectivity models in industry is, determining
the optimal conditions for reaction products. This can maxi-
mize the desirable products and decrease the production of
undesirable products as much as possible.
As mentioned earlier, many studies have been carried out
to study the effect of these parameters quantitatively, but few
efforts have been made to present a model which can express
the importance of these factors. The aim of this study is to
present a model for the products selectivity of iron catalyst
with promoters with the component amount of 100Fe/5Cu/4K/
16SiO2 and examine the importance of factors such as tem-
perature, time on stream, and partial pressure of H2 and CO. In
addition, the importance of parameters using the constant
coefficients was determined. It also determines the interac-
tion between these parameters via a statistical model and
finally discusses the optimal conditions which are very useful
for increasing the desirable products.
Experimental
In this paper, the experimental data were taken from Ref. [25].
Catalyst construction was performed using values presented
in Table 1. Brunner which was used for preparing the catalysts
with various conditions was also used to name them. For
instance, for the intended catalyst (100Fe/5Cu/4K/16SiO2) was
named as 2UH. The number 2 indicates that it quickly adds
promoter after sedimentation or drying. The letter U indicates
that the catalyst does not require washing while the letter H
indicates drying at high temperature (100  C).
was done at 300  C by air flow for 6e16 h. An amount of 0.251 g
of catalyst was tested in the fixed bed reactor and the data is
presented in Table 2 [25].
Data analysis
In FischereTropsch synthesis, there are factors which can
affect the quality and selectivity of products. For example,
temperature, the partial pressure of CO and H2, and time on
stream are variables which have effect on the products
selectivity like methane (CH4), ethylene (C2H4), ethane (C2H6),
and carbon dioxide (CO2). In this work, the impact of four
parameters (temperature, the partial pressure of CO and H2,
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0 3

Table 1 e Materials masses for catalyst preparations. All

P_value
0.007
0.026
0.046
0.002
0.027
0.034

0.057
0.082

0.024
0.019

0.022
numbers are grams of specified moiety [25].

e
e

e
Product model for S(CO2)
Catalyst Fe(NO3)3a Cu(NO3)2b KHCO3 SiO2 NH4HCO3

R2adj ¼ 93:64%
2UH 72.492 1.836 1.077 1.611 43.799

Tvalue

3.13

5.87
3.11

2.46
2.17
a
Fe(NO3)3$9H2O.

4.36

2.68

2.89

3.21
3.40

3.27
b
Cu(NO3)2$2.5H2O.

e
e

R2 ¼ 97:88%
SE coefficient
Table 2 e Experimental data and operating conditions

0.903

0.523
26.2
59.2
2.68

29.8
10.1

3.46

62.2
2.40

3.22
[25].

e
e

e
T ( C) TOS (h) PCO (atm) PH2 (atm) Selectivity (% mol)
CO2 CH4 C2H4 C2H6
249 206 6 6 32.4 5.6 5.6 7

P_value
230 232 6.2 6.4 30.9 4.6 6 4.9

0.171
0.062
0.103
0.246
0.085
0.049

0.181
0.058
0.140
220 267 6.4 6.6 26.2 3.7 5.2 4.2

e
e
e
e

e
e
Product model for S(C2H6)
239 280 6.3 6.3 31.3 4.7 5.7 5.4

R2 ¼ 98:38% R2adj ¼ 96:54%

249 292 6 6 32.7 5.4 5.6 6.8
249 314 6 6 33.1 5.3 5.5 6.9

Tvalue
1.52

1.87
1.27

2.38

2.27
1.66
250 528 6.2 6.3 33.2 4.7 6.4 5.3

2.22

2.01

1.49
e
e
e
e

e
e
259 547 6.1 6.1 33.6 5.3 5.9 5.9
249 363 6.4 5.8 33 4 4.1 6.7
249 391 3.8 4.9 35 4.1 4.6 6.7

SE coefficient
249 404 11.4 4.9 30.4 7.5 4.6 11.9
249 427 4.3 5 33.5 4.5 4.7 7.3

14.8
32.1
1.40
11.6
13.2
3.03

24.7
26.9
3.18
249 448 6 2.5 32 7.4 4.4 11.9

e
e
e
e

e
e
249 468 5.4 5.9 31.1 4.7 3.9 7.3
250 495 11.6 5 31 7.6 4.9 11.9
249 512 6.1 2.6 32.4 7.6 4.8 12.2
P_value

time on stream) were evaluated by using response surface

0.003
0.004
0.004
0.004
0.004
0.005
0.012
0.003
0.003
0.008
0.003
0.004
0.003
0.005
methodology (RSM).

e
Product model for S(C2H4)

Response surface methodology (RSM) is a set of mathe-

R2adj ¼ 98:42%
matical and statistical techniques for constructing an exper-
16.60

16.16

17.70
17.03
10.92
16.93
Tvalue

imental model. The aim of RSM is to achieve a mathematical

17.33

15.46
16.85

14.73

16.04
17.62
14.74
9.18

model that describes the process in which the main factors or

e
Table 3 e Regression coefficient of the RSM modeling for all responses.

their interactions are involved. This model can be achieved to

R2 ¼ 99:79%
the most favorable response by adjusting the factors.
SE coefficient

The polynomial regression model which has acceptable

0.121
0.923
0.956
0.773

appropriateness between experimental data and obtained 0.317

11.2

1.04
4.29
10.5
2.95

9.40
21.1
1.80
23

selectivity model is considered as follows: e

X
n X X
n
f ¼ b0 þ bi zi þ bij zi zj þ bii z2i þε (1)
i¼1 ij i¼1
P_value

where f is the response, b represents the coefficient of

0.003
0.000
0.000
0.000
0.001
0.003

0.000

0.000
0.001
0.000
0.000
0.002

regression, z is variables (e.g. T, PCO , PH2 and TOS) and also, n

e
e

e
Product model for S(CH4)

indicates the number of experiments [26,27]. The accuracy of

R2 ¼ 99:98% R2adj ¼ 99:93%

regression is obtained by coefficients below:

11.12
12.13

14.12
12.68
Tvalue
6.42

6.68

9.27
11.67

19.32

13.90

SSR
8.98

6.93

R2 ¼ (2)
SSR þ SSE
e
e

The modification of R2 is adjusted R2 which is defined as

SE coefficient

follows:
0.0446

0.0717

ð1  R2 Þðn  1Þ
0.112
0.838
0.991
0.229

0.226

0.211

R2adj ¼ 1  (3)
1.11

1.79
2.01

np
2.4

e
e

Pvalue is used for important regression coefficient. The

amount of Pvalue must be lower than 0.05. The Pvalue is a
necessary condition but not sufficient, for this reason, the
PCO (atm)
PH2 (atm)

TOS  PCO
TOS  PH2
TOS*TOS
Constant

PCO *PCO
Terms

PCO *PH2
TOS (h)

PH2 *PH2

other items such as Tvalue and SE coefficient were used [28,29].

T*TOS
T*PCO
T ( C)

T*PH2

The regression coefficient and their analysis are presented in

T*T

Table 3.

Please cite this article in press as: Atashi H, Rezaeian F, Modelling and optimization of FischereTropsch products through iron catalyst
in fixed-bed reactor, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.04.224
4 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0

FischereTropsch products selectivity such as methane,

Results and discussion
As stated above, the aim of this study is to present a new
procedure for examining the effect of various parameters
such as temperature (T), partial pressure of CO (PCO ) and par-
tial pressure of H2 (PH2 ), time on stream (TOS), on the
ethylene, ethane, and carbon dioxide via statistical method.
The selectivity models were improved by Response Surface
Methodology (RSM). The results have acceptable appropri-
ateness between experimental data and obtained model. The
result is presented in Table 4. Finally, the optimization results
are shown in Table 5. The minimum amount of products

Table 4 e Selectivity model of products as well as predicted value by RSM.

No. Responses (experimental) Responses (predicted by RSM)
S(CO2) S(CH4) S(C2H4) S(C2H6) S(CO2) S(CH4) S(C2H4) S(C2H6)
1 32.4 5.6 5.6 7 32.8077 5.6238 5.3274 7.1533
2 30.9 4.6 6 4.9 31.1432 4.6048 5.7577 4.8488
3 26.2 3.7 5.2 4.2 26.1629 3.7073 4.9769 4.2320
4 31.3 4.7 5.7 5.4 30.9237 4.7197 5.4376 5.6532
5 32.7 5.4 5.6 6.8 32.7331 5.3748 5.2329 6.9926
6 33.1 5.3 5.5 6.9 32.7140 5.3111 5.2998 6.9515
7 33.2 4.7 6.4 5.3 33.1982 4.7141 6.1064 5.8804
8 33.6 5.3 5.9 5.9 33.5308 5.3122 5.5939 5.9593
9 33 4 4.1 6.7 32.6822 4.0184 3.7995 5.8779
10 35 4.1 4.6 6.7 34.9419 4.0742 4.3479 6.9949
11 30.4 7.5 4.6 11.9 30.3157 7.5088 4.3113 11.7700
12 33.5 4.5 4.7 7.3 33.5424 4.5467 4.3880 7.6081
13 32 7.4 4.4 11.9 32.2881 7.4108 4.1158 12.2311
14 31.1 4.7 3.9 7.3 31.7502 4.6858 3.6357 6.7656
15 31 7.6 4.9 11.9 31.0922 7.6139 4.6088 11.9887
16 32.4 7.6 4.8 12.2 32.1181 7.6003 4.5212 1.9280

Table 5 e Optimization results.

T ( C) TOS (h) PCO (atm) PH2 (atm) Selectivity (% mol)
CO2 CH4 C2H4 C2H6
Maximization of CH4 259 206 11.6 2.5 46.6771
T
Minimization of CH4 244.5264 227.8380 10.0933 4.3842 0
Maximization of C2H6 259 206 11.6 2.5 105.9774
T
Minimization of C2H6 249.9761 206 3.8 6.5002 0
Maximization of C2H4 220 547 11.6 2.5 1379.0617
T
Minimization of C2H4 220.1515 546.9814 4.2785 6.1449 0
Maximization of CO2 220 547 3.8 2.5 642.2513
T
Minimization of CO2 249.0650 252.3054 11.60 2.5 0
T
is Target (In order to achieve characteristic of selectivity value).

Fig. 2 e The optimization of CO2 for zero target of selectivity. Minitab software was used for all calculation, regression, and
analysis.

Please cite this article in press as: Atashi H, Rezaeian F, Modelling and optimization of FischereTropsch products through iron catalyst
in fixed-bed reactor, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.04.224
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0 5

selectivity is negative, while the aim of this article is to
minimize these amount to zero. Fig. 2 shows the minimization
of carbon dioxide and methane selectivity into the target of
zero.
Selectivity model of methane
Fig. 3 shows the effect of temperature, partial pressure of CO
and H2, and time on stream, on the selectivity of methane. As
can be seen at constant partial pressure of CO and H2, the
selectivity of methane is raised by increasing temperature but
no changes could be seen in selectivity by increasing or
decreasing time on stream. However, at constant partial
pressure of CO and temperature, at high partial pressure of H2,
there are little changes. With constant temperature and par-
tial pressure of H2, the selectivity is increased at high partial
pressure of CO. With decreasing time on stream, the mini-
mum amount of selectivity becomes clearly visible, the min-
imum selectivity can occur at PCO ¼ 11.6 and TOS ¼ 547.
At constant temperature and time on stream, the
maximum selectivity can be obtained by increasing PH2 and
decreasing PCO . It can be seen that the maximum amount of
selectivity occurs at PCO ¼11.6, PH2 ¼2.5. The selectivity model
of CH4 is as follows:

Fig. 3 e Effect of temperature, partial pressure of H2 and CO and also, time on stream on selectivity of methane: T ¼ 239.5  C,
TOS ¼ 376.5 h, PCO ¼7.7 atm, PH2 ¼4.55 atm.

Please cite this article in press as: Atashi H, Rezaeian F, Modelling and optimization of FischereTropsch products through iron catalyst
in fixed-bed reactor, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.04.224
6 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0

SðCH4 Þ ¼ 491:57875 þ 2:96657 T þ 0:041496 TOS Selectivity model of ethane

 79:94073 PCO þ 113:85282 PH2  0:0040222 T*T
The fluctuation of selectivity of ethane with temperature, the
þ 0:20487 PH2 *PH2 þ 0:32697 T*PCO  0:46682 T*PH2
partial pressure of H2 and CO and time on stream is shown in
 0:00479721 TOS*PCO  0:00260139 TOS*PH2
Fig. 4. As can be seen, at constant partial pressure of CO and
þ 0:18310 PCO *PH2 H2, the selectivity of ethane is increased with rise in temper-
(4) ature, while there are no changes of selectivity in time on
stream. With constant time on stream and partial pressure of
TOS*TOS, PCO *PCO and T*TOS have minimum effect on the
CO and also at constant time on stream and partial pressure of
model and due to Pvalue, regardless of their coefficient. As
H2, the selectivity of ethane increases with rise in tempera-
demonstrated by the model, the maximum effect of the
ture. The maximum amount of selectivity occurs at T ¼ 259,
parameter belongs to partial pressure of H2. Besides that, the
PH2 ¼2.5, PCO ¼11.6. At constant temperature and PH2 , by
important interaction is T*PH2 , because it has the most coef-
increasing the TOS, at low partial pressure of CO, the selec-
ficient. In optimization part, the minimization of ethane was
tivity is raised and at high partial pressure, the selectivity is
set as a target and could be found in T ¼ 244.5264  C,
decreased.
TOS ¼ 227.8380 h, PCO ¼10.0933 atm, PH2 ¼4.3842 atm.

Fig. 4 e Effect of temperature, partial pressure of H2 and CO and also, time on stream on selectivity of ethane: T ¼ 239.5  C,
TOS ¼ 376.5 h, PCO ¼7.7 atm, PH2 ¼4.55 atm.

Please cite this article in press as: Atashi H, Rezaeian F, Modelling and optimization of FischereTropsch products through iron catalyst
in fixed-bed reactor, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.04.224
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0 7

The maximum amount of ethane occurs in constant T and
TOS in PCO ¼11.6, PH2 ¼2.5.
The selectivity model of ethane can be proposed as follows:
SðC2 H6 Þ ¼ 2803:36109 þ 15:95781 T þ 0:045775 TOS
 116:55699 PCO þ 378:28193 PH2  0:018967 T*T
þ 0:48340 T*PCO  1:52555T*PH2
 0:00794059 TOS*PCO
Parameters such as TOS*TOS, PCO *PCO , PH2 *PH2 , T*TOS,
TOS*PH2 and PH2 *PCO have been ignored due to their effects on
the model and the value of Pvalue. As can be seen, the
maximum coefficient belongs to PH2 , so partial pressure of H2
has the most effect on the selectivity of ethane and the
important interaction belongs to T*PH2 , due to its negative
coefficient. In optimization part, the minimization of ethane
was set as a target and could be achieved in T ¼ 249.9761  C,
TOS ¼ 206 h, PCO ¼3.8 atm and PH2 ¼6.5002 atm.
Selectivity model of ethylene
(5)
Ethylene selectivity changes with temperature, partial pres-
sure of CO and H2, and time on stream as shown in Fig. 5. As
can be seen in the figure, at constant partial pressure of CO
and H2, ethylene selectivity decreases with increasing tem-
perature. At constant TOS and PH2 , the selectivity increases

Fig. 5 e Effect of temperature, partial pressure of H2 and CO and also, time on stream on selectivity of ethylene: T ¼ 239.5  C,
TOS ¼ 376.5 h, PCO ¼7.7 atm, PH2 ¼4.55 atm.

Please cite this article in press as: Atashi H, Rezaeian F, Modelling and optimization of FischereTropsch products through iron catalyst
in fixed-bed reactor, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.04.224
8 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0

with decreasing temperature while, at constant TOS, PCO and
also, at constant TOS and PH2 , ethylene selectivity is increased
by reducing the temperature. The minimum selectivity oc-
curs at T ¼ 259, PCO ¼11.6, and PH2 ¼2.5. At constant temper-
ature and partial pressure of H2, by increasing TOS at low PCO ,
the selectivity is decreased poorly and at high PCO , the
selectivity is raised. The ethylene selectivity model is given as
follows:
SðC2 H4 Þ ¼ 16779:86180  95:70111 T þ 0:24492 TOS
þ 518:55481 PCO  2076:37291 PH2 þ 0:11430 T*T
þ 0:0000383254 TOS*TOS  1:07431 PCO *PCO
 3:87612 PH2 *PH2  0:00253839 T*TOS
 2:09376 T*PCO þ 8:44984 T*PH2 þ 0:047781 TOS*PCO
þ 0:013378 TOS*PH2
(6)
PH2 *PCO has the minimum effect on the model, so it has been
omitted. As can be seen, the maximum effect of parameter
belongs to PH2 because it has the most coefficient and also, the
important interaction is T*PH2 . In optimization part, maximi-
zation of ethylene could be achieve in T ¼ 220  C, TOS ¼ 547 h,
PH2 ¼11.6 atm and PCO ¼2.5 atm.
Selectivity model of CO2
Fig. 6 shows the changes in CO2 selectivity with temperature,
the partial pressure of CO and H2, and time on stream. As can
be seen, at constant partial pressure of CO and H2 and also at
constant TOS and PH2 , the CO2 selectivity decreases with
increasing temperature. At constant temperature and TOS and
also, at constant temperature and PCO , the CO2 selectivity
decreases with rise in PH2 . At constant TOS and PCO , by
increasing temperature at low PH2 , the selectivity is decreased
but at high PH2 , the selectivity is raised. In this case, the
maximum selectivity of CO2 occurs at T ¼ 220, PH2 ¼2.5. At

Fig. 6 e Effect of temperature, partial pressure of H2 and CO and also, time on stream on selectivity of carbon dioxide:
T ¼ 239.5  C, TOS ¼ 376.5 h, PCO ¼7.7 atm, PH2 ¼4.55 atm.

Please cite this article in press as: Atashi H, Rezaeian F, Modelling and optimization of FischereTropsch products through iron catalyst
in fixed-bed reactor, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.04.224
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0
constant T and PH2 by increasing TOS, at high PCO , the CO2
selectivity is raised. The maximum selectivity of CO2 can be
achieved at PCO ¼3.8, TOS ¼ 547. The selectivity model of CO2 is
proposed as follows:
SðCO2 Þ ¼ 12324:46682  68:30447 T þ 0:48846 TOS
 11:97525 PCO  1247:59629 PH2 þ 0:077145 T*T
 0:30574 PH2 *PH2  0:0022604 T*TOS þ 4:98943 T*PH2
þ 0:012252 TOS*PCO þ 1:31925 PCO *PH2
(7)
In the model, the parameters such as PCO *PCO , TOS*TOS,
T*PCO and TOS*PH2 have been omitted because their Pvalue were
higher than the other parameter and have less effect on the
model. As can be seen in the model, the main parameter is PH2
and has the most effect on the model and also, the important
interactions belong to T*PH2 . In optimization part, the mini-
mization of CO2 was set as a target and it was found in
T ¼ 249.0650  C, TOS ¼ 252.3054 h, PCO ¼11.60 atm and
PH2 ¼2.5 atm.
Conclusions
As mentioned earlier, a lot of works have been carried out on
the kinetics and product selectivity of FischereTropsch syn-
thesis. However, there are very few scholars who offer a
model which can predict the selectivity of the products. This
method can be used within any temperature ranges based on
FischereTropsch reaction.
Considering the importance of optimizing the reactor with
respect to the valuable materials, this article determined the
products model which can predict the selectivity of products
based on temperature, the partial pressure of CO and H2, and
time on stream. Four models were obtained for the selectivity
of products such as methane, ethane, ethylene, carbon diox-
ide using RSM. As shown by the model, the most important
parameter which has effect on the selectivity model, is PH2 . In
addition, the main interaction belongs to T*PH2 , because its
coefficient has the highest amount. Finally by these models,
the optimal conditions were calculated and the maximum
conditions for ethylene were found as T ¼ 220  C, TOS ¼ 547 h,
PCO ¼11.6 atm and PH2 ¼2.5 atm. Also, the conditions that can
minimize the amount of CO2 were determined as
T ¼ 249.065  C, TOS ¼ 252.3054 h, PCO ¼11.60 atm and
PH2 ¼2.5 atm.
In industries, the application of these models has partic-
ular importance because it is used to achieve maximum pro-
duction by manipulating the operating parameters. So they
can produce the products which are very useful for environ-
mental purpose.
Acknowledgement
The authors express gratitude for the financial assistance
given by Iran's Ministry of Science and Research (NT19451827).
They are also grateful for further funding given by the Uni-
versity of Sistan and Baluchestan (NP1323102).
Please cite this article in press as: Atashi H, Rezaeian F, Modelling and optimization of FischereTropsch products through iron catalyst
in fixed-bed reactor, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.04.224
9
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