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J. CHEM. SOC. FARADAY TRANS., 1992, 88(19), 2943-2947 2943

Reaction Kinetics of Propane Dehydrogenation over Partially

Reduced Zinc Oxide supported on Silicalite
Ben-Zu Wan and Hui Min Chu
Department of Chemical Engineering, National Taiwan University, Taipei, Taiwan, ROC
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The kinetics of propane dehydrogenation to produce propene over partially reduced zinc oxide supported on
silicalite have been investigated over t h e temperature range 753-823 K at atmospheric pressure. It was found that
hydrogen concentration had no influence on t h e dehydrogenation rate, while the presence of propene inhibited
t h e reaction. A mechanism involving hydrogen-atom dissociation from propane is proposed for the propane
dehydrogenation kinetics. Based on t h e kinetic analysis, it is suggested that propane adsorption is t h e rate-
determining step in the overall reaction mechanism. The activation energy for t h e reaction was 29 kcal mol-'.

The transformation of propane into aromatics hydrocarbons, Experimental

which are more valuable chemicals, has attracted worldwide
Catalyst Preparation and Characterization
interest. In the past, two processes have been developed ta
achieve this purpose. One is the decomposition of propane to Silicalite was synthesized according to the procedures re-
produce methane and ethene through cracking or hydrogen ported in the literature.'" The as-synthesized crystalline pro-
transfer ; l ethene is subsequently oligomerized to form larger ducts were washed with deionized water, dried at room tem-
hydrocarbons, which are then transformed into aromatic perature and calcined at 773 K in air for 6 h. After they had
hydrocarbons through cyclization and dehydrogenation. been exchanged three times with 0.5 mol d m P 3 ammonium
Generally, acid-type zeolites (i.e. HZSM-5) are used as cata- sulfate solution at room temperature, the samples were
lysts in this process. However, the high yield of methane, washed, dried and calcined once again in air at 773 K. From
which is of low value, is a drawback. Another process is the the results of atomic absorption spectroscopy (GBC PL-906),
dehydrogenation of propane to produce propene, which sub- the final form of silicalite contains only a trace of aluminium
sequently oligomerizes to the larger hydrocarbons, and is (0.01%). The BET surface area (measured with a Micro-
then transformed into aromatic hydrocarbons. This process is meritic Accusorb 2100D) of this sample was 435 m2 g - ' . The
favoured because the yield of methane is reduced. In this X-ray diffraction pattern (measured with a Philips Diffrac-
latter process, transition metals, such as Ga, Zn, Pt, Mo or tometer, PW 1729) was the same as that reported elsewhere.'"
Cr, were added to the acid-type catalysts. These metal species Two samples of different zinc oxide loadings on silicalite
are considered responsible for the dehydrogenation reaction. were prepared by the incipient wetness technique. Zinc
Much research work concerning the aromatization of nitrate (Janssen Chimica) was the source of zinc. After
propane through the reaction steps of dehydrogenation and impregnation, the samples were dried at 353 K and calcined
oligomerization has been published. Csiscery2-' examined in air for 4 h at 823 K. The zinc loadings were also measured
the conversion of C,-C, alkanes over the platinum-group with atomic absorption spectroscopy. The sample with 2.0%
metals and the oxides of Cr, Mo, V and W supported on zinc loading was used in the study of temperature-
alumina. The principle product was aromatic hydrocarbons, programmed reduction, and the sample with 1.1% zinc
but coke formation on these catalysts was found to be loading was used as the catalyst for propane dehydro-
extremely fast. Later, other authors*-" reported a method genation. The BET surface area of the latter sample was 356
reducing the coking rate by impregnating HZSM-5 with m2 g-'. The sample, in powder form, was pressed, crushed
platinum. The reduction in the coking rate was attributed to and sieved (45-70 mesh) prior to being used in the catalytic
the low density of acid sites and the steric constraints within reaction.
the porous structure of HZSM-5. Recently, HZSM-5 zeolites
modified with gallium oxide or zinc oxide have also been
Apparatus and Procedure
claimed to give high selectivity to the aromatics from
propane.'.' '-15 Summarizing these studies, either metals or Temperature-programmed reduction (TPR) of zinc oxide
metal oxides can play an important role in the dehydro- supported on silicalite was carried out in a flow-type system
genation of propane to form propene, which then undergoes with a quartz reactor (9 mm 0.d.). The temperature was mon-
cyclization and aromatization to form aromatic hydrocar- itored by a K-type thermocouple in quartz thermowell
bons in the presence of acidic catalysts, such as HZSM-5. located at the centre of the catalyst bed. The reduction
The objective of this work is through a kinetic study to process was monitored by a TCD detector. In general, prior
understand the mechanism of propane dehydrogenation to to the TPR study the catalysts were pretreated at 473 K
propene over zinc oxide supported on HZSM-5. Because under a 25 cm3 min-' argon flow for 4 h. After the sample
hydrogen is one of the main products from propane aromati- was cooled to room temperature, the carrier gas was changed
zation, zinc oxide should be partially or nearly completely to a mixture gas of 90 mol% nitrogen and 10 mol% hydro-
reduced under the reaction conditions. Therefore, partially gen. The temperature of the reactor was raised at a rate of 10
reduced zinc oxide samples were used. On the other hand, K min- from 373 to 1073 K. A trap positioned immediately
silicalite was used instead of HZSM-5 as the support to mini- after the quartz tube reactor was kept at ca. 178 K with a
mize secondary reactions, such as oligomerization and cycli- liquid nitrogen and acetone low-temperature bath to con-
zation of propene, because silicalite has approximately the dense water vapour produced during zinc oxide reduction.
same structure and channel dimensions as HZSM-5 zeolite Propane dehydrogenation was carried out in a fixed-bed
but only a trace amount of aluminium and very few acidic type reactor (9 mm 0.d. quartz tube). A schematic diagram of
sites in the framework. the experimental apparatus is shown in Fig. 1. The flow rates
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2944 J. CHEM. SOC. FARADAY TRANS., 1992, VOL. 88

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I 1 I I I I
3 473 573 673 773 073 973 1 73
TIK
Fig. 2 Temperature-programmed reduction (TPR) curves of (a) sili-
Fig. 1 Schematic diagram of propane dehydrogenation system. 1, calite, (b) zinc oxide supported on silicalite, (c) zinc oxide supported
Molecular sieve; 2, check valve; 3, on-off valve; 4, 3-way valve; 5 , on silicalite pretreated under 10 mol% H,-N, flow at 823 K for 4 h,
needle valve; 6, rotameter; 7, mass flowmeter; 8, mixer; 9, sampling ( d ) zinc oxide supported on silicalite pretreated under 50 mol%
port; 10, heating tape; 11, furnace; 12, quartz reactor; 13, thermo- H,-N, flow at 823 K for 4 h
couple; 14, temperature controller; 15, temperature readout; 16, con-
denser; 17, bubble flowmeter
of hydrogen consumed under curve 3 was much less than that
under curve 2. If a higher concentration of H,-N, flow was
used for prereduction, e.g. 50 mol% H,-N,, then an even
of propane, propene and nitrogen were controlled and read smaller amount of hydrogen was consumed in the TPR
by mass flow controllers and meters (Brooks 5878 and 5850). study, as shown in curve 4. Therefore, we conclude that the
The maximum controlled flow rates of propane and nitrogen reduction of supported zinc oxide can start at temperatures
were 100 cm3 min-', and that of propene was 4 cm3 min-'. as low as 473 K, but the process hardly reaches completion
The hydrogen flow was measured by a calibrated rotameter even if the sample is pretreated under 50 mol% H,-N, flow
and controlled by a needle valve. The gases flowing into the at 823 K for 4 h.
reactor were preheated to 400 K with a heating tape wrapped The kinetics of propane dehydrogenation over partially
around the inlet tubing. The emuent from the outlet of the reduced zinc oxide supported on silicalite (1.1% Zn loading)
reactor was also maintained at 400 K to prevent any product were studied with a differential reactor. The total conversion
condensation. Prior to the reaction, the catalyst was pre- of propane was kept at <3% to maintain good operation in
treated at 823 K overnight under air flow, then reduced with a differential regime. Because of the catalyst decay problem
50 mol% H,-N, flowing for 4 h at 823 K. The products were during propane dehydrogenation, the kinetic data were col-
analysed with a Shimadzu 14A G C equipped with an FID lected as a function of time on stream for each set of reaction
detector. A 30 ftt Chrompak capillary column coated with conditions, and the data used for the kinetic analysis were
fused silica-alumina/KCl was used for the separation. All those extrapolated to the initial run time. In other words, the
kinetic measurements were made within the following ranges : rate law was derived from the initial rates of the reaction. The
total flow rate, 95-130 cm3 min-'; weight of catalyst, 0.2 g; influence of the principal operation variables, i.e. partial pres-
total pressure, 1 atm;$ partial pressure of propane, 0.02-0.68 sures of propane, hydrogen and propene, and reaction tem-
atm, hydrogen, 0.02-0.35 atm, propene 0.015-0.033 atm; perature were examined.
reaction temperature, 753-823 K. The selectivity and yield The primary reaction products were propene and hydro-
were calculated on a carbon basis and were defined as: selec- gen. Methane, ethene, ethane from cracking, trace C,-C,
tivity of a given hydrocarbon = (moles of the given hydro- hydrocarbons and the aromatics from the secondary reac-
carbon x no. of carbon atoms in the molecular formula)/ tions were also found in the products. The total selectivity of
(moles of propane consumed x 3). Yield of a given the latter compounds was <25% (mainly from cracking).
hydrocarbon = (mole of the given hydrocarbon x no. of Because of the low conversion in this study, the possibility of
carbon atoms in the molecular formula)/(mole of propane competing or consecutive reactions on the catalyst surface
fed x 3). from these products was negligible.
The catalytic activity of the silicalite support in propane
Results and Discussion dehydrogenation was examined over 0.2 g of pure silicalite at
a propane partial pressure of 0.10 atm and total flow rate of
The results of temperature-programmed reduction (TPR) are 110 cm3 min-' at 793 K. A 0.08% propene yield was
shown in Fig. 2. Curve 1 shows that no reduction band was obtained, which was much less than the yield (1.21%)
obtained on pure silicalite. Curve 2 is the TPR curve for zinc obtained from zinc oxide supported on silicalite (1.1% Zn)
oxide loaded on silicalite (2.0% Zn), showing that the under the same reaction conditions. Moreover, since the
reduction started at temperatures as low as 473 K and surface area of zinc silicalite (356 m2 g-') is less than that of
extended to high temperature, 1073 K. If the sample of curve pure silicalite (435 m2 g-I), the propene yield from the
2 was prereduced at 823 K for 4 h under a 10 mol% H,-N, surface of silicalite support of zinc silicalite catalyst should be
flow, then cooled to room temperature for TPR study, curve ~ 0 . 0 8 % Therefore,
. it can be concluded that the catalytic
3 shows that the reduction still occurred, though the amount activity from the silicalite support is not significant.
The influence of propane partial pressure on dehydro-
f 1 ft z 0.3048 m. genation rate over partially reduced zinc oxide (supported on
$ 1 atm = 101 325 Pa. silicalite) at different reaction temperatures is shown in Fig. 3.
 View Article Online

J. CHEM. SOC. FARADAY TRANS., 1992, VOL. 88 2945

Table 1 Influence of propene pressure on propene yield over par-

c

'u1 4.0
c
I

c" 3.5
c tially reduced zinc oxide supported on silicalite

pressure at reactor inlet/atm

yield of propene
C3H6 N2 ("/.I
E C3H8

'9 3.0 0.67 0 0.33 0.39

z2 2.5 0.67 0.015 0.32 0.28
c 0.67 0.033 0.30 0.02
2
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5
.-
2.0 Total flow rate = 120 cm3 min-'; 0.2 g of catalyst at 773 K.
c

4 1.5
2
P
Q) 1.0
C those surface sites which are active for hydrogenation-
3 0.5 dehydrogenation, therefore, it decreases the dehydrogenation
rate. This inhibition should be considered in the mathemati-
P
0.0 cal rate expression.
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 The Langmuir-Hinshelwood isotherm was used for the
propane pressure/atm kinetic modelling. By assuming the dissociation of a hydro-
Fig. 3 Influence of propane pressure on propane dehydrogenation gen atom from propane occurring on the zinc surface, the
773; *, 793;
rate over zinc supported on silicalite. T/K: A, 753; 0, following mechanism with five reaction steps was proposed :
0,823
C3H8 + S+C,H,. S (1)
At low propane pressures, especially when the partial pres- C3H8 s + s = C 3 H 7 S + Ha s
* * (2)
sure of propane is close to zero, the rate of production of
C3H7 S + S e C 3 H 6 S + H . S
* * (3)
propene has a linear relationship with propane pressure. This
suggests that the reaction rate is first order with propane con- C3H6 s+C,H, + S
* (4)
centration in the low-pressure range. However, when the
propane pressure becomes higher, the reaction order grad- H s + H s S H , + 2s (5)
ually decreases, which indicates that the propane dehydro- where s represents an active site on the catalyst. Five basic
genation rate may be limited by adsorption processes. rate equations were formulated by assuming that each step
In order to clarify the reaction pathway further, the effect was the rate-determining step in turn. Based on the empirical
of the partial pressure of the reaction products, hydrogen and observation that hydogen concentration has no influence on
propene, on the rate of dehydrogenation was also studied. the reaction rate, it is proposed that the equilibrium constant
For hydrogen, the experiments were carried out by varying for the desorption of hydrogen from the surface is relatively
hydrogen pressure while fixing propane pressure at 0.10 atm large. Therefore, any term containing hydrogen concentration
and total volumetric flow rate at 110 cm3 min-l. The results in the denominator of the rate equation is assumed to be
shown in Fig. 4 indicate that hydrogen pressure had no influ- zero. After this simplification, linear regressions of the five
ence on the propene yield (and the dehydrogenation reaction equations were made at each temperature in order to obtain
rate) at 753 and 823 K. O n the other hand, for propene, the the rate constants and adsorption equilibrium constants.
experiments were carried out at 773 K by varying propene When any of the derived adsorption equilibrium constants
pressure while fixing propane pressure at 0.67 atm and the from regression was negative, that rate equation was elimi-
total volumetric flow rate at 120 cm3 min-'. Table 1 shows nated. Finally, it was found that only one of the five simpli-
that propene can severely retard the rate of dehydrogenation. fied equations remained. This rate equation is based on the
This effect is attributed to the fact that propene competes for adsorption of propane on the catalyst surface being the rate-
determining step and its simplified form is expressed as

f
follows :

2*25
2.00

1.75
1.50
t- where C,is the total number of active sites on the catalyst
surface for dehydrogenation, K is the equilibrium constant

-s
h
for propane dehydrogenation, k , is the propane adsorption
-
1.25 rate constant; and K , is the propene desorption equilibrium
9
.- constant on the catalyst surface. Fig. 5 shows that the rate
;1.00 - data from experiment are in good agreement with those esti-
C
0.75 - mated from this equation. Deviation is defined as the absol-
2 ute value of the difference between the experimental rate and
0.50 -
P
the estimated one divided by the experimental one. The
average deviation is ca. 4.9%, which is acceptable.

0.00
0.25 llIzzzL
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35
The values of klC, and K , at different reaction tem-
peratures obtained from the linear regression are listed in
Table 2. The temperature dependence of these two reaction
parameters can be expressed as
hydrogen pressure/atm
Fig. 4 Influence of hydrogen pressure on propene yield over zinc k, =A exp( - E J R T ) (7)
supported on silicalite. Total flow rate = 110 cm3 min; P(C3H8)=
0.1 atm; 0.2 g catalyst. 0,823 K ; A, 753 K K , = exp(AS/R)exp(- AH/RT) (8)
 View Article Online

2946 J. CHEM. SOC. FARADAY TRANS., 1992, VOL. 88

Table 2 Rate constants and propene desorption equilibrium con- positive values of enthalpy and entropy changes imply that
stants at different reaction temperatures the desorption of propene is an endothermic reaction and the
entropy of the system increases after propene is desorbed
from the surface. This is consistent with the general desorp-
753 1.47 6.94 tion phenomena.
773 2.33 81.43 In the studies of propane and butane conversion over a
793 4.45 95.54 mixture of zinc oxide and HZSM-5, Mao et ~ 1 . 'proposed
~
823 7.37 606.00 that the main role of zinc oxide was to remove hydrogen re-
leased from the acid sites of zeolite. The dehydrogenation
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where A is the Arrhenius constant; E , is the activation energy rate over zeolite was considered to be enhanced by this
of propane adsorption; AS is the entropy change for propene hydrogen-transfer process. In other words, in their point of
desorption and AH is the enthalpy change for propene view no apparent reaction occurred on the zinc oxide surface,
desorption. From the plots of ln(klCJ and ln(K3) us. the but the surface provided only for the removal of hydrogen.
reciprocal of reaction temperature (Fig. 6 ) the parameters From our studies, however, TPR results indicate that zinc
were estimated as E , = 29 kcal mol-', AH = 72 kcal mol-l oxide can be partially reduced in the presence of hydrogen.
'.
and A$ = 82 cal mol- K - The linear correlation factors y, The reaction kinetic studies show that this partially reduced
of these two lines in Fig. 6 are 0.99 and 0.96, respectively, zinc oxide plays the main role in dehydrogenation of propane
which suggests good linear relationship in the plots (y = 1 to produce propene and hydrogen. Hydrogen partial pressure
represents a perfect linear relationship). Furthermore, the has no influence on the dehydrogenation rate, but rather it is
propene partial pressure which dramatically inhibits the reac-

I
tion rate. From the present study, it is concluded that over
/I the partially reduced zinc oxide surface (supported on

//
4.03 silicalite), the removal of propene product from the surface
enhances the rate of propane dehydrogenation rather than
the removal of hydrogen.
Recently, Meriaudeau et al. '
* reported that the activity
'3'

m 3.04 of gallium or zinc for propane dehydrogenation increased

0
5
0
Q,
1
2.04
/ with an increase in the acidity of the zeolite support. A dual
function mechanism was proposed. Based on our results we
propose that the increase in dehydrogenation rate is due to
the strong interaction between electron-rich propene formed
on the metal surface and the electron-deficient acid sites in
i? the zeolite, which in turn removes propene from metal surface
E
1.04 and explores the active sites for further propane dehydro-
Q)
c
genation. The overall dehydrogenation rate is therefore
B increased.

0.035ie
[Link]
1

1.04
,

2.04
I . I

3.04
. I

4.03
.1
Conclusions
rate from experiment/l o - mol
~ g-l s-l From the temperature-programmed reduction study it is con-
cluded that under a hydrogen atmosphere zinc oxide
Fig. 5 Comparison of predicted and observed propane dehydro- (supported on silicalite) can be partially reduced even at tem-
genation rates peratures as low as 473 K. However, the complete reduction
of zinc oxide to zinc metal cannot be achieved even at 823 K
for 4 h under a 50 mol% H,-N, flow.
Under the reaction conditions used in the present work,
the rate equation for propane dehydrogenation over partially
reduced zinc oxide catalyst supported on silicalite was
expressed as the following,

rate = 1ct[P(c3 8) - P(H 2)p(c3 6)iKi

+ P(C,H6)/K3
Propane adsorption was proposed to be the rate-determining
step. The hydrogen concentration was found to have no influ-
ence on the rate of propane dehydrogenation. On the other
hand, propene inhibited the rate due to the strong adsorption
of propene on the surface.

The authors thank Mr. Chao Hsien Lin and Mr. Chin Tso
Lin for doing part of the experimental work. The financial
support from the National Science Council in Taiwan, ROC,
under contract No. NSC 80-0402-E002-12 is gratefully appre-
ciated.
1 0 3 KIT
References
Fig. 6 Arrhenius plots of dehydrogenation rate constant (AE = 29.0
kcal mol-', y = 0.99) and propene desorption equilibrium constant 1 H. Kitagawa, Y. Sendoda and Y. Ono, J . Catal., 1986,101, 12.
(AH = 72.3 kcal mol-', y = 0.96) over zinc surface supported on sili- 2 S. M. Csicsery, J . Catal., 1970, 17, 205.
calite 3 S. M. Csicsery, J . Catal., 1970, 17, 216.
 View Article Online

J. CHEM. SOC. FARADAY TRANS., 1992, VOL. 88 2947

4 S. M. Csicsery, J. Catal., 1970,17,315. 13 M. S. Scurrell, Appl. Catal., 1988,41,89.

5 S. M. Csicsery, J. Catal., 1970,17,322. 14 [Link] and J. J. Wu, J. Chinese I. Ch. E., 1990,21,167.
6 S. M. Csicsery, J . Catal., 1970,18,30. 15 [Link] and C. Naccache, J . Mol. Catal., 1990,59,L31.
7 S. M. Csicsery, Ind. Eng. Chem. Process Des. Dev., 1979,18, 191. 16 [Link] and T. C. Yang, J. Chinese Chem. SOC.,1990,37,255.
8 [Link] and F. Okazumi, J. Catal., 1984,90,366. 17 R. Le Van Mao, L. Dufresne and J. Yao, J. Appl. Catal., 1990,
9 C. W. R. Engelen, J. P. Wolthuizen and J. H. C. Van Hooff, 65,143.
Appl. Catal., 1985,19,153. 18 P. Meriaudeau, G. Sapaly and C. Naccache, in Chemistry of
10 N. [Link] and J. Y. Doyemet, Appl. Catal., 1987,35,93. Microporous Crystals, Tokyo, 1991.
1 1 [Link] and J. R. Anderson, Appl. Catal., 1985,17,141.
12 T. Inui, Y. Makino, F. Okazumi, S. Nagano and A. Miyamoto,
Ind. Eng. Chem. Res., 1987,26,647. Paper 2/01176J; Received 4th March, 1992
Published on 01 January 1992. Downloaded by UNIVERSIDAD DE ANTIOQUIA on 7/26/2019 [Link] PM.