Petroleum Science and Technology

ISSN: 1091-6466 (Print) 1532-2459 (Online) Journal homepage: https://www.tandfonline.com/loi/lpet20

Kinetic Modeling of the Catalytical Reaction of

Syngas to Light Olefins

F. Shayegh & A. Farshi

To cite this article: F. Shayegh & A. Farshi (2015) Kinetic Modeling of the Catalytical
Reaction of Syngas to Light Olefins, Petroleum Science and Technology, 33:8, 928-935, DOI:
10.1080/10916466.2015.1031347

To link to this article: https://doi.org/10.1080/10916466.2015.1031347

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Petroleum Science and Technology, 33:928–935, 2015
Copyright 
C Taylor & Francis Group, LLC
ISSN: 1091-6466 print / 1532-2459 online
DOI: 10.1080/10916466.2015.1031347

Kinetic Modeling of the Catalytical Reaction of Syngas

to Light Olefins

F. Shayegh1 and A. Farshi2

1
Technology and Innovation Department, Research Institute of Petroleum Industry (RIPI), Tehran,
Iran
2
Refining Technology Development Department, Research Institute of Petroleum Industry (RIPI),
Tehran, Iran

Nowadays converting synthesis gas to makes olefins is an important issue and researcher has been focused
on it. The kinetic experiments for synthesis gas reactions over RIPI-Co/Mn catalyst to light olefin are
carried out in a micro-fixed-bed reactor under the following conditions: temperature 220–300◦ C, pressure
1–5 atm, H2 /CO feed ratio 1–3, and space velocity of 450-600 h−1. In order to obtain the parameters of the
kinetic model, the optimum values of the kinetic parameters have been obtained. The global minimum
for the optimized function has been achieved, with using the genetic algorithm. The data of this study
were best fitted by a Langmuir-Hinshelwood (LH) rate form Rco = kPco PH2 1/2/ (1+aPco +bPH2 1/2)2.
Keywords: synthesis gas, converting, light olefins, kinetics, CO/Mn/Tio2 catalyst, reaction

1. INTRODUCTION

As olefins are one of the most important feedstocks for petroleum industries, direct production of
light olefins from synthesis gas has been the subject of intense academic study. To achieve the
optimum performance of the complete process, the catalyst and the reactor should be optimized
comprehensively. This requires an appropriate kinetic model that can fulfill the engineering require-
ments of reactor and process simulation and optimization. The Fischer-Tropsch process is known
to produce a wide range of hydrocarbon molecules (C1 -C30 ). The aim of this work is study kinetics
of selective catalytic production of C2 -C4 olefins in Fischer-Tropsch process. In the previous work
(Shayegh et al., 2010), it has been shown that Co/Mn/TiO2(RIPI-Co/Mn) catalyst exhibit high ac-
tivity, stability (in 1000 h continuous operation) and good selectivity to produce light olefins such
as C2-C4 = at the optimum operating condition. In this work kinetics model for conversion of CO to
olefin on the RIPI-Co/Mn catalyst has been investigated. The main objective of this paper is to find
an appropriate kinetic model that can accurately represent the experimental data obtained from the
performance of the developed catalyst (Shayegh et al., 2010).

Address correspondence to A. Farshi, Refining Technology Development Department, Research Institute of Petroleum
Industry (RIPI), P.O. Box 14665–1998, West Boulevard of Azadi Sport Complex, Tehran, Iran. E-mail: farshia@ripi.ir

928
 CATALYTICAL REACTION OF SYNGAS TO LIGHT OLEFINS 929

2. BACKGROUND OF KINETICS MODEL STUDIES

In 1959 Anderson for the first time proposed the following form for the rate of FTS reactions (RFT )
in cobalt catalyst:
KPco PH 2
RF T = . (1)
1 + Pco
Wojciechowski (1989) and Sarup and Wojciechowski (1989) developed six different rate equations
for cobalt catalyst, which finally reduced to the following two equations:
1/2 1/2
KPco PH 2
−Rco = 1/2 1/2
(2)
(1 + K1 Pco + K2 PH 2 )2

1/2
KPco PH 2
−Rco =  2 (3)
1/2
1 + K1 Pco + K2 PH 2

Whiters et al. (1990) measured the FTS kinetics with a cobalt catalyst. The Syn-Gas consumption
rate with cobalt-based catalysts was studied and finally came up with the following overall rate
expression.
KPco PH2 2
RF T = (4)
Pco PH 2 + aPH 2o
Yates and Satterfield (1991) studied the kinetics of a cobalt catalyst in a slurry reactor. Following
rate expression for the FTS reactions were suggested:
KPco PH 2
RF T = (5)
(1 + bPco )2
Keyser et al. (2000) estimated reaction rate constants for the cobalt-manganese oxide catalyst,
which concluded that FTS reaction rate equations of Anderson as well as Sarup and Wojchiechowski
are distinctly better than the other combinations. The reactions were carried out at 210–250◦ C and
6–26 bar. In another study, Zennaro et al. (1999) worked on titania-supported cobalt in a differential
fixed bed reactor. The simple power law equation in order to represent the experimental data
was obtained. Identification of the exact mechanism of the reaction is very complicated and time
consuming task and the resulting of kinetic equations may be so complex that it cannot be used for
engineering purposes. In this case, utilization of simple kinetic models is preferable. The criterion
for preference of one model is its ability to be fitted better with the experimental data. This criterion
has been used in the present work for finding the most suitable form of the kinetic equations

3. EXPERIMENTAL

The kinetic tests were carried out in a fixed bed stainless steel micro reactor at various operating
conditions (Figure 1).
A stainless steel tubing fixed bed reactor with internal diameter of 16 mm (1/8}a) located in a
two zone tubular furnace (with 25 cm length). The amount of catalyst that used in each reaction
test was 2 h (20–60 mesh). The temperature inside the catalyst bed was controlled by temperature
controller and also inlet gases (CO and H2 with purity of 99.99%) flow rate was adjusted with three
calibrated mass flow controllers that equipped with four channel Reactor pressure was adjusted by
a back pressure regulator. Previous work has shown that an optimum temperature for reduction of
930 F. SHAYEGH AND A. FARSHI

◦
Co catalysts is 400 C (Shayegh et al., 2010). Hence, all catalysts were pre-reduced at atmospheric
pressure in a flowing H2 stream (gas flow rate was 20 mL/min) at 400◦ C for 16–18 h before being
exposed to synthesis gas. The synthesis gas with different ratios of H2 /CO (H2 /CO = 1, 2, 3) was
fed into the reactor, and CO-hydrogenation was carried out at 220–300◦ C. For most of the catalysts,
pressure and GHSV were in the range of 0.1–0.5 MPa and 450–1200 h−1, respectively, also light
liquid products were collected in a cold trap at –3◦ C. Reactant and product streams were analyzed
in an on-line manner using a gas chromatograph (Varian CP- 3800) equipped with TCD and FID
detectors. The CO, CO2, N2, and O2 were analyzed through two-packed column in series.

4. SYNTHESIS CATALYST FOR KINETICS MODEL INVESTIGATION

The RIPI catalyst with support of TIO2 for production of olefins was synthesis.

4.1 Investigation Internal Diffusion Effect in Catalyst

In many studies the effect of internal diffusion in FTS reaction has been investigated. The researcher
showed that internal diffusion has effect in kinetic of FTS reaction. Anderson (1959) proposed

FIGURE 1 Experimental reactor setup. Kinetics modeling of olefin synthesis on existing of RIPI-Co/Mn catalyst.
1, 2: CO, H2 gas cylinders; 3, 4: regulators; 5, 6: on-off valves; 7, 8: mass flow controllers; 9: control systems; 10:
three-way valve; 11: temperature controller; 12: fixed bed reactor; 13: furnace; 14, 15: hot and cold condensers; 16:
back pressure regulator (controller); 17: three-way valve; 18: on-line GC; 19: personal computer; 20: glass calibration
soap flow meter column.
 CATALYTICAL REACTION OF SYNGAS TO LIGHT OLEFINS 931

kinetics model with considering of internal diffusion phenomena effects. The investigation of this
models shows that particles with diameter lower than of 2 mm with ordinary kinetics rate do not
have internal diffusion effect. So according to this guideline the particle with diameter of 2 mm was
used in kinetics investigation.

5. EXPERIMENTAL DATA

Experiments were carried out in a continuous differential fixed-bed reactor over a wide range of
independently varied operating conditions. Kinetic and selectivity models should be developed on
the basis of an extensive set of experimental data at various process conditions (e.g., space velocity,
temperature, CO, and H2 reactor pressure) without significant catalyst deactivation and heat or mass
transfer gradients. The experiments have been performed at intrinsic chemically kinetics controlled
conditions. It should be noted that, the set of operating conditions used in experimental studies were
obtained based on statistical experimental design methods (response surface methodology). In this
study, central composite design methodology (Johansson et al., 2000) has been implemented for
setting the levels and combination of temperature, pressure and H2 /CO and GHSV variables. A
total number of 42 sets of experiments was designed. Among them, sets 1–30 (15 values of data
in Table 1) were designed to cover the rate of the operating conditions and combination of the
mentioned variables and sets 31–42 were considered for the evaluation of the performance of the
obtained kinetic model using first 30 sets of experiments. For accurate kinetic measurements, the
catalyst has stable behavior. For attainment of steady-state conditions it is necessary to evaluate
catalysts over long reaction periods time (20–100 h) that for cobalt catalysts this time can require an
initial 100 h; Hindermann et al., 1993). After 100 h of catalyst stabilization, all experimental data
were taken from a fresh batch of catalyst. For all data quoted, satisfactory mass balances, typically
between 97–100% were observed. As shown in Table 1, some of the experiments were repeated
(e.g., Run No. 1, 8, 12, and 16). So to have reliable data in each run, two or three data sets were
obtained and their average has been used as their representative.

TABLE 1
Experimental Data for Kinetics Model Evaluation RIPI-Co/Mn Catalyst

H2 Conversion CO Conversion
Run Temp., ◦ C P, MPa GHSV, h−1 RCO/H2 % %

1 260 0.3 600 2 25.21 39.69

2 300 0.5 450 3 3.25 20.77
3 220 0.5 450 1 6.99 10.76
4 220 0.1 450 3 4.26 4.04
5 220 0.5 750 3 1.61 3.21
6 300 0.5 750 1 7.22 8.33
7 300 0.1 750 3 0.85 9.92
8 260 0.3 600 2 2.03 29.62
9 300 0.1 450 1 5.87 18.64
10 220 0.1 750 1 0.57 0.58
11 220 0.5 450 3 5.59 37.85
12 260 0.3 600 2 16.26 34.12
13 300 0.5 450 1 12.90 36.74
14 220 0.1 750 3 0.76 0.65
15 300 0.5 750 3 9.39 36.71
932 F. SHAYEGH AND A. FARSHI

TABLE 2
Different Reaction Rate Model Equations Based on Overall Synthesis Gas Consumption Rate, for Cobalt
Catalysts

Kinetic Expression Reference

kPH 2 PCO
(1) (Anderson, 1956)
1 + aPCO
1/2 1/2
kPCO PH 2
(2)   (Wojciechowski, 1989)
1/2 1/2 2
1 + aPCO + bPH 2

1/2
kPCO PH 2
(3)   (Sarup and Wojciechowski, 1989)
1/2 2
1 + aPCO + bPH 2

kPH2 2 PCO
(4) (Whiters et al., 1990)
(PCO PH 2 + aPH 2O )

kPco PH 2
(5) (Yates and Satterfield, 1991)
(1 + aPco )2

6. REACTION RATE AND EVALUATION

A differential reactor model was used to describe the operation of isothermal micro-fixed-bed reactor.
The effects of various kinds of mass transfer can be neglected. To remove the internal mass transfer
resistance, very fine catalyst (250–500 μm) particles have been used. The overall reactions consist
of the following step:

nCO + (2n + 1)H2 −→ Cn H2n+2 + nH2 O n < 8 (I)

nCO + 2nH2 −→ Cn H2n + nH2 O n < 8 (II)

Water-gas shift (WGS) is the following step:

CO + H2 O −→ CO2 + H2 (III)

Kinetic equations can be based on CO consumed to produce hydrocarbon products (R FT = -R

CO -RWGS ).Cobalt catalysts are not very active towards the WGS reaction in contrast to most iron-
based Fischer-Tropsch catalysts (Van der Laan and Beenackers, 1999). Hence, the kinetic model can
be based on the carbon monoxide consumption (-R CO ) so kinetic equation for each obtained data
can be calculated as the following:
in
Flowin yco − Flowout yco
out
Rco = (6)
mcat

In this study based on the reaction mechanisms found in the literature review, according to Table 2
five kinetic models have been selected as the candidate models. The parameters of each candidate
models have been obtained based on the minimization of the root mean square of the errors (RMSE)
in the reaction rates obtained by kinetic model and its corresponding experimental value. The RMSE
 CATALYTICAL REACTION OF SYNGAS TO LIGHT OLEFINS 933

of the errors is estimated based on the following equation (Table 2):

⎛ ⎞
N

exp cal 2
⎜ r − ri ⎟
⎜ i=1 i ⎟
RMSEroo r = ⎜ ⎜ ⎟ ∗ 100 (7)
exp ⎟
⎝ N rave ⎠

The optimum values of the kinetic model parameters have been obtained using Real Encoded
Genetic Algorithm (GA). The reason of using Real Encoded GA as the optimization framework are
as follows:

• None of the decision variables (i.e., kinetic model parameters) is discrete.

• The span and resolution of the decision variable, use of binary GA requires a long chromosome
which results in the low convergence rate.

The results of optimization of parameters are shown in Table 3. The ranges attributed to the
kinetic parameters are selected according to physical consideration (i.e., positive frequency factors,
reasonable maximums for activation energies and heats of adsorption based on literature data). This
guaranties that the kinetic parameters obtained by this method has physical significance.
Negative value of the normalized RMSE has been used as the fitness of the GA.
⎛ N  ⎞
 exp

−RMSError = ⎝ N rave ⎠ ∗ 100

2 exp
ri − rical (8)
i

For obtaining the optimum values for the parameters of each kinetic model, one should rank the
obtained kinetic models based on a statistical criterion, which reflects their appropriate correspon-
dence fitness. According to statistical consideration for each model the standard deviation of model
data is defined as the following:
 N  exp 
 ri − rical  1
Sdiv =  
 r exp  N − m × 100 (9)
i i

Where N represents the number of data points for a particular model and m is number of
parameters in each model. It is obvious, the model that leads to a smaller Sdiv is better. A better
quantitative statistical judgment can be made by the F test. Each model that leads to F values less
than the corresponding value in F test table (Critical F) can be statistically accepted.

TABLE 3
Kinetics Model Parameters Estimation

Model K∗ E a ∗∗
−Had b

(1) 0.0011 70.3 0.051 235

(2) 0.0021 70.0 0.088 79.8 0.063
(3) 0.0035 90.5 0.04 112 0.0078
(4) 0.00125 63.5 0.026 217.6
(5) 0.0023 171 0.82 188

∗k = k0 exp(−E/RT )
∗∗ a = a0 exp(−Had /RT )
934 F. SHAYEGH AND A. FARSHI

TABLE 4
Goodness of Fit of the Kinetic Models

Model Sdiv F

(1) 28.56 3.14 > 2.7

(2) 39.55 2.96 > 2.7
(3) 25.11 1.92 < 2.49
(4) 25.65 2.054 < 2.7
(5) 37.63 5.66 > 2.7

For the present problem F can be defined as:

Mean quare gression SSY − SSE/m
F = = (10)
Mean square residual SSE/(N − m − 1)
In which SSE and SSY are defined as:

N
exp

exp 2
SSY = ri − rmean (11)
i


N
exp
2
SSE = ri − rical (12)
i

Table 4 shows the rank of each kinetic models according to their corresponding F test values. As
can be seen from this table among four tested kinetic models only two models (i.e. models 4 and 3)
have passed the F test and among these two models, model 3 gives the smaller F value. To give a
visual picture of goodness of fit of model 3 the parity plot of calculated and measured rates of CO
conversion was shown as goodness of fit (Shayegh et al., 2010). It was seen from plots that 70% of
predictions lies within ±25% from measured values.

7. CONCLUSION

Kinetic data points with forty number of synthesis gas to olefins conversions have been experimen-
tally obtained with using RIPI-CO/Mn-TiO2 catalyst in the 220–300◦ C, 1–5 bar, H2 /CO 1–3 ratio,
and GHSV in 450–600 h−1.The mentioned catalyst and selected operating conditions for reactions
will be produced maximum yield of light olefins. The gathered kinetic data have been used to find the
most suitable kinetic equations to represent the rate of CO consumption on the mentioned catalyst.
The genetic algorithm has been used to tune the kinetic parameters of five classic models that were
proposed in FT reactions. The statistical analysis of the goodness of fit (Table 4) clearly shows that
using the Eq. (3) gave the best fit of data and passed the F test. Moreover the values obtained for
activation energy (E = 90.5 KJ/mol) lies within the range of 70–105 KJ/mol that is obtained by
other researchers.

REFERENCES

Anderson, R. B. (1956). Catalysts for the Fischer-Tropsch synthesis (vol. 4). New York: Van Nostrand Reinhold.
Hindermann, J. P., Hutchings, G. J., and Kiennemann, A. (1993). Mechanistic aspects of the formation of hydrocarbons and
alcohols from CO hydrogenation. Catal. Rev. 35:1–127.
 CATALYTICAL REACTION OF SYNGAS TO LIGHT OLEFINS 935

Johansson, E., Kettaneh-Wold, N., Wikstrom, C., and Ericksson, S. W. L. (2000). Design of experiments-principles and
application, first edition.
Keyser, M. J., Everson, R. C., and Espinoza, R. L. (2000). Fischer-Tropsch kinetic studies with cobalt-manganese oxide
catalysts. Ind. Eng. Chem. Res. 39:48–54.
Sarup, B., and Wojciechowski, B. W. (1989). Studies of the Fischer-Tropsch synthesis on a cobalt catalyst. II. Kinetics of
carbon monoxide conversion to methane and to higher hydrocarbons. Can. J. Chem. Eng. 67:62–74.
Shayegh, F., Ghotbi, C., and Bozorgmehri Boozarjomehri, R. (2010). Effect of operation conditions on the catalytic perfor-
mance of Co/Mn/TiO2 catalyst for conversion of synthesis gas to light olefins. Sci. Iran. 17:168–176.
Van der Laan, G.P., and Beenackers, A. A. C. M. (1999). Kinetics and selectivity of the Fischer-Tropsch synthesis. A
literature review. Catal. Rev.: Sci. Eng. 41:255.
Wojciechowski, B. W. (1988). The kinetics of the Fischer Tropsch synthesis. Catal. Rev.: Sci. Eng. 30:629–702.
Whiters, H. P. Jr., Eleizer, K. F., and Mitchell, J. W. (1990). Slurry-phase Fischer-Tropsch synthesis and kinetic studies over
supported cobalt carbonyl derived catalysts. Ind. Eng. Chem. Res. 29:1807–1814.
Yates, I. C., and Satterfield, C. N. (1991). Intrinsic kinetics of the Fischer-on a cobalt catalyst. Energy Fuels 5:168–173.
Zennaro, R., Tagliabue, M., and Bartholomew, C. H. (2000). Kinetics of Fischer-Tropsch synthesis on titania supported
cobalt, Catal. Today 58:30–319.

NOMENCLATURE

a = Reaction rate constant N = Total number of experimen-

b = Reaction rate constant tal data
E = Activation energy, Kjmol−1 P = Pressure, Mpa
FT = Fischer-Tropsch R = Gas universal constant
GHSV = Gas space velocity, h−1 RFT = Rate of FTS reactions
Enthalpy of adsorption, kj- SSE = Error sum of squares
mol−1 SSY = Sum of squared deviation
K = Reaction rate constant, mol T = Temperature
g−1s−1Mpa−1 WGS = Water-gas-shift reaction
m = Number of optimized pa- x = Composition
rameters k = Kinetics reaction constant