Department of Chemical and Petroleum Engineering, Sharif University of Technology, Tehran, Iran
National Iranian Petrochemical Company, Research and Technology Division, Tehran, Iran
KEYWORDS
Propane dehydrogenation;
Side reactions;
Platinum catalyst;
Kinetics.
Abstract The kinetics of side reactions in the dehydrogenation of propane over a supported platinum
catalyst modified by tin, were investigated. Catalytic dehydrogenation over a commercial Pt-Sn/ -Al2 O3
was carried out in a laboratory-scale plug-flow reactor at 580620 C under atmospheric pressure. Several
kinetic models derived from different reaction mechanisms were tested using experimental data obtained
under a range of reaction conditions. It was found that the kinetics of the main dehydrogenation reaction
was best described in terms of a LangmuirHinshelwood mechanism, where the adsorption of propane
was the rate controlling step. Simple power low rate expressions were used to express the kinetics of side
reactions.
2011 Sharif University of Technology. Production and hosting by Elsevier B.V. All rights reserved.
1. Introduction
The current chemical scenario shows an increased interest
in the production of light olefins as starting materials for some
of the most important chemical products including polymers,
synthetic rubbers and oxygenated compounds for reformulated
fuels [1,2]. Propylene is a major co-product from steam crackers
and the economics of the process are highly dependent on the
supply/demand situation for both propylene and ethylene. In
some geographic areas, propylene demand is increasing faster
than ethylene demand. The dehydrogenation of propane with
high selectivity to propylene gives the chance to de-couple the
productions of ethylene and propylene, and will be of great
interest in the coming years if the trend in the market for
polymers persists [1].
Corresponding author.
E-mail address: khorashe@sharif.edu (F. Khorasheh).
(R1)
C3 H8 CH4 + C2 H4 ,
(R2)
C2 H4 + H2 C2 H6 ,
(R3)
C3 H8 + H2 CH4 + C2 H6 .
(R4)
A. Farjoo et al. / Scientia Iranica, Transactions C: Chemistry and Chemical Engineering 18 (2011) 458464
459
1.8 mm
g
0.65 cm3
Catalyst Density (c )
1.12
200
g
cm3
m2
g
Catalyst
weight (g)
1
1.2
1.5
1.6
QC3
(cc/min)
39.96
44.36
55.45
59.3
QH2
(cc/min)
WHSV
(1/h)
Conversion
(%)
31.968
35.488
44.36
47.44
4
4
4
4
20.45
23.07
23.32
23.35
460
A. Farjoo et al. / Scientia Iranica, Transactions C: Chemistry and Chemical Engineering 18 (2011) 458464
1
2
3
4
5
Catalyst
weight
(g)
0.75
0.75
0.75
0.75
0.75
QC3
Catalyst
(cc/min) diameter
(mm)
QH2
WHSV
(cc/min) (1/h)
Conversion
(%)
55
55
55
55
55
44
44
44
44
44
13.72
23.1
23.9
24.1
24.3
1.8
1
0.71
0.50
0.35
9
9
9
9
9
C3 H6 Produced
Input(C3 H8 ) Output(C3 H8 )
(1)
A. Farjoo et al. / Scientia Iranica, Transactions C: Chemistry and Chemical Engineering 18 (2011) 458464
461
ri ,
i = C3 H8 , C3 H6 , C2 H4 , C2 H6 , CH4 ,
Figure 8: Molar ratio of side products to all products at different WHSV and
reaction temperatures.
expressions [13], where either an adsorption, surface reaction, or desorption step is considered as the rate controlling
step. Based on experimental data, Airaksinen et al. (2002) indicated that desorption of propylene from the surface sites was
not likely to be the rate controlling step and suggested several mechanisms for propane dehydrogenation, where either
adsorption or surface reaction was rate controlling [14]. A recent study, where the same commercial catalyst as that used in
the current investigation was employed, suggested that mechanisms involving propane adsorption either on single or dual
sites as the Rate Controlling Step (RCS) were most consistent
with experimental data [15].
The LangmuirHinshelwood mechanisms that were studied
in the current investigation to describe the kinetics of the
(2)
4
5
k=1 i=1
(FiEexp FiEpre )2 Wi ,
(3)
462
A. Farjoo et al. / Scientia Iranica, Transactions C: Chemistry and Chemical Engineering 18 (2011) 458464
Mechanism II
C3 H8 (g) + 2S C3 H7 S + H S (RCS)
C3 H7 S + S C3 H6 S + H S
C3 H6 S C3 H6 (g) + S
2H S H2 (g) + S
CH4 + S CH4 S
C2 H4 + S C2 H4 S
C2 H6 + S C2 H6 S
S: Active sites on the catalyst
C3 H8 (g) + S C3 H7 S H (RCS)
C3 H7 S H + S C3 H6 S H + H S
C3 H6 S H C3 H6 (g) + H S
2H S H2 (g) + 2S
CH4 + S CH4 S
C2 H6 + S C2 H6 S
C2 H4 + S C2 H4 S
S: Active site on the catalyst
Mechanism III
Mechanism IV
C3 H8 (g) + S C3 H7 S H (RCS)
C3 H7 S H C3 H6 (g) + H S H
H S H H2 (g) + S
CH4 + S CH4 S
C2 H4 + S C2 H4 S
C2 H6 + S C2 H6 S
S: Active sites on the catalyst
C3 H8 (g) + S C3 H8 S
C3 H8 S + S C3 H7 S + H S (RCS)
C3 H7 S + S C3 H6 S + H S
C3 H6 S C3 H6 (g) + S
2H S H2 (g) + 2S
CH4 + S CH4 S
C2 H4 + S C2 H4 S
C2 H6 + S C2 H6 S
S: Active site on the catalyst
Table 5: LangmuirHinshelwood rate expressions for the main propane dehydrogenation reaction.
Model
Equation rate
PPr PH
k PP K 2
1 (I-a)
rA =
2 (II-a)
rA =
3 (III-a)
rA =
4 (IV-b)
rA =
P: Propane (A)
Pr: Propylene (B)
H2 = Hydrogen (C)
k : Rate constant
Keq : Equilibrium constant
K : Adsorption constant
exp
1/2
(1+K PPr PH +KPr PPr +(K PH2 )1/2 +KH2 PH2 +KCH4 PCH4 +KC2 H4 PC2 H4 +KC2 H6 PC2 H6 )2
2
PPr PH
k Pp K 2
eq
1/2
1+KPr H PPr PH +(KH PH )1/2 +K PPr PH +KCH PCH +KC H PC H +KC H PC H
2 6 2 6
2 4 2 4
4
4
2
2
2
2
2
P P
k P B C
A
k Pp
PPr PH
2
Keq
pre
(4)
exp
(FiE FiEpre )2 ,
(5)
k=1
Total error =
Keq
where FiE and FiE are the experimental and predicted molar
flow rates of component i at the reactor exit, Wi are weighting factors, and summation k extends over experimental data at
different WHSV. The optimized parameter values were highly
influenced by the choice of weighting factors, as propane and
propylene were major species, while methane, ethane and
ethylene were present in minor quantities. In the optimization
procedure for parameter estimation, first a preliminary estimate for the kinetic parameter was obtained using a weighing factor of one for each component. Subsequently, the revised
weighting factors were evaluated as follows:
Errori =
eq
Errori .
(6)
i=1
Kinetic equation
r
r
r
r
= k1 PC3 H8
= k2 PC2 H4 PH2
= k2 PC3 H8 PH2
= k4 PC3 H8
The constants are reported in Table 7 for the main reaction using
different reactions [1012]. Proposed LangmuirHinshelwood
rate expressions. Having evaluated the parameters for the main
reaction, the second step involved the estimation of the rate
expressions of the optimized kinetic parameters for the main
reaction, and the rate constants for the side reactions using the
following objective function:
OF =
4
3
(FiEexp FiEpre )2 ,
(9)
k=1 i=1
(7)
(8)
A. Farjoo et al. / Scientia Iranica, Transactions C: Chemistry and Chemical Engineering 18 (2011) 458464
463
Table 7: Kinetic constants for the proposed LangmuirHinshelwood rate expressions, E (kJ/mol), 1H (kJ/mol).
Model 1
Model 2
.79
k = 3.17 10 exp 61
RT
KPr = 7.44 107 exp 89RT.07
.36
KH2 = 2.18 101 exp 9RT
5
.
75
KC2 H6 = 3.60 102 exp RT
16.44
3
KC2 H4 = 6.97 10 exp RT
Model 3
.71
k = 1.21 10 exp 53
RT
42
.
84
KC2 H4 = 5.15 105 exp RT
7.41
2
KPr H2 = 3.70 10 exp RT
9.16
K = 3.47 101 exp RT
3
Model 4
.39
k = 3.71 10 exp 59
RT
KH2 = 9.71 105 exp 52RT.22
.66
k = 4.25 101 exp 70
RT
18.92
RT
KPr = 1.42 105 exp 69RT.31
6
.
83
KCH4 = 1.98 102 exp RT
5.48
2
KC2 H6 = 2.99 10 exp RT
.61
KC2 H4 = 3.39 102 exp 5RT
Table 8: Rate constants for proposed rate expressions for side reactions.
Model 1
k1 = 1.14 exp
Model 2
K1 = 7.53 10 exp
6488
27393
T
14723
T
1598.23
T
k4 = 1.53E + 09 exp
Model 3
273938
T
28187
exp
T
17926
T
1598.23
T
k1 = 3.36 10
17
k4 = 1.53E + 09 exp
Model 4
40451
T
30754
T
8498
T
1598.23
T
.6
k3 = 2.85 109 exp 5757
T
.23
k4 = 1.53E + 09 exp 1598
T
Absolute error %
Model 1
Main species
Side products
4.02
14.68
Model 2
Main species
Side products
6.22
21.74
Model 3
Main species
Side products
7.11
17.74
Model 4
Main species
Side products
12.18
25.98
The kinetic constants reported in Table 7 for the main reaction and in Table 8 for the side reactions were used to predict
the exit molar flow rates of various spices under different reaction conditions. Comparison between the experimental values
and predicted values from each model would serve as a measure
to differentiate between the predictive ability of different models. Table 9 presents the average percent absolute error for each
model for both major species (propane and propylene) and side
products, indicating that model 1, where dual site adsorption
of propane is considered as the rate controlling step, provides
the best agreement with experimental data. A typical comparison of experimental exit molar flow rates, with predicted values
from model 1 as a function of residence time at 580 C, is presented in Figures 10 and 11 for the major species and the side
products, respectively.
Figure 10: Comparison between experimental exit molar flow rates and
predicted values from model 1 for major products at reaction temperature of
580 C.
4. Conclusions
The kinetics of propane dehydrogenation over a commercial
Pt-Sn/ -Al2 O3 catalyst was best described in terms of a LangmuirHinshelwood mechanism, where dual site adsorption of
propane was considered as the rate controlling step. The kinetics of side reactions leading to the formation of methane,
ethylene and ethane as minor products could reasonably be described by simple power-law rate expressions. The proposed kinetic model resulted in an average relative error of 4.0% and
14.7% between predicted and experimental molar flow rates
Figure 11: Comparison between experimental exit molar flow rates and
predicted values from model 1 for side products at reaction temperature of
580 C.
464
A. Farjoo et al. / Scientia Iranica, Transactions C: Chemistry and Chemical Engineering 18 (2011) 458464
Acknowledgments
The authors acknowledge financial support from the Iranian
National Petrochemical Research and Technology Company for
the experimental work involved in this study.
References
[1] Miracca, I. and Piovesan, L. Light paraffin dehydrogenation in a fluidized
bed reactor, Catalysis Today, 52, pp. 259269 (1999).
[2] Loc, L.C., Gaidai, N.A., Kiperman, S.L., Thoang, H.S. and Novikov, P.B.
Kinetics of side reactions in the dehydrogenation of n-butane and ISObutane over platinumpotassium catalyst, Kinetics and Catalysis, 36(4),
pp. 504510 (1995).
[3] Pop, E., Goidean, N., Giodean, D. and Serban, G. DE 2401955 (17 July 1975).
[4] Schramm, B., Kern, J., Schwahn, H., Preuss, A.W., Gottlieb, K. and
Bruderreck, H. DE 3739002 A1 (24 May 1989).
[5] Kirner, J.F. GB 2162082 A1 (29 January 1986).
[6] Box, E. US 3692701 (19 September 1972).
[7] Wilhelm, F.C. US 3998900 (21 December 1976).
[8] Barri, S.A.I. and Tahir, R. EP 351066 A1 (17 January 1990).
[9] Cottrell, P.R. and Fettis, M.E. US 5087792 (11 February 1992).
[10] Zhang, Y., Zhou, Y., Qiu, A., Wang, Y., Xu, Y. and Wu, P. Propane
dehydrogenation on PtSn/ZSM-5 catalyst: effect of tin as a promoter,
Catalysis Communications, 7, pp. 860866 (2006).
[11] Bobrov, V.S., Digurov, N.G. and Skudin, V.V. Propane dehydrogenation
using catalytic membrane, Journal of Membrane Science, 253, pp. 233242
(2005).
[12] Guo, J., Lou, H., Zhao, H., Zheng, L. and Zheng, X. Dehydrogenation
and aromatization of propane over rhenium-modified HZSM-5 catalyst,
Journal of Molecular Catalysis A: Chemical, 239, pp. 222227 (2005).
[13] Fogler, H.S., Elements of Chemical Reaction Engineering, 2nd ed., p. 581.
Prentice Hall International, New York, US (1999).
[14] Airaksinen, S.M.K., Harlin, M.E. and Krause, A.O.I. Kinetic modeling of
dehydrogenation of isobutane on chromia/alumina catalyst, Industrial &
Engineering Chemistry Research, 41, pp. 56195627 (2002).
[15] Mohagheghi, M. and Bakeri, G. Kinetic studies of propane dehydrogenation over Pt-Sn/ -Al2 O3 catalyst, in: Presented at International Conference
on Chemical Reactors, CHEMREACTOR-18, Malta (29 September3 October
2008).
Afrooz Farjoo was born in 1985. She obtained her B.S. degree from Isfahan
University of Technology in 2007 and her M.S. degree in 2009 from the
Department of Petroleum and Chemical Engineering at Sharif University of
Technology in the area of Thermo Kinetics and Catalysis.
Farhad Khorasheh was born in 1961. He took his B.S. degree in Chemical
Engineering in 1983 from Queens University, Ontario, Canada and his M.S.
and Ph.D. degrees in Chemical Engineering, in 1986 and 1992, respectively,
from the University of Alberta, Edmonton, Canada. He is now a Professor in
the Department of Petroleum and Chemical Engineering at Sharif University of
Technology. His research interests include Modeling and Reactor Design.
Saeed Niknaddaf was born in 1985. He obtained his B.S. and M.S. degrees from
the Department of Petroleum and Chemical Engineering at Sharif University of
Technology in 2007 and 2009, respectively, in the area of Thermo Kinetics and
Catalysis.
Mahnaz Soltani was born in 1974. She obtained her B.S. and M.S. degrees from
the Department of Chemical Engineering at Tehran University in 1996 and 1998,
respectively. She is now working as a Chemical Engineer in the National Iranian
Petrochemical Company.