Kinetics of Aqueous-Phase Catalytic Dehydration of 2-Propanol
Kinetics of Aqueous-Phase Catalytic Dehydration of 2-Propanol
Kinetics of Aqueous-Phase Catalytic Dehydration of 2-Propanol
Dehydration of 2-Propanol
Jean-Marc Rivard, Qinglin Zhang and Karl T. Chuang*
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, AB TGG 2GG, Canada
T
he vapour-phase dehydration of 2-propanol is widely used as a
reaction to qualitatively characterize the acidity of solid catalysts The aqueous-phasecatalytic dehydration of 2-propanol
and to study the mechanism of the catalytic dehydration of was investigated in a batch slurry reactor. Alumina,
alcohols over solid acids (lain and Pillai, 1967, as per references; zeolite 13X, SAPO-5 and silicalite are all active in the
Jacobset al., 1977; Cervasini and Auroux, 1991; Cervasini et al., 1997). liquid phase dehydration of 2-propanol at 463 K with
The vapour-phase dehydration of 2-propanol over a gamma alumina silicalite being the most active catalyst. Propylene was
catalyst has also been proposed for propylene production (Fukuhara et found to be the major reaction product, with
diisopropyl ether and acetone formed in trace amounts.
al., 1993), although it is not common practice to do so.
The reaction kinetics over silicalite was determined at a
Several solid acid catalysts have been reported to be active in the
temperature range of 434 to 463 K and at a concentration
vapour phase dehydration of 2-propanol. These catalysts include range of 4 to 10 mol% 2-propanol in water. A single
alumina (Cervasini and Auroux, 1991; Cervasini et al., 1997; Mostafa et site Langmuir-Hinshelwood-Hougen-Watson (LHHW)
al., 1991), zeolite 13X (Bink et al., 1985; Yue and Olaofe, 1984a; 1984b) type mechanism was found to describe the kinetic
and Amberlite I. R. 200 ion exchange resin (Cottifredi et al., 1968). The data well. Water was found to inhibit the dehydration
dehydration reaction is often carried out in a plug-flow reactor system reaction. The activation energy over silicalite was
with no water in the feed. determined to be 226.8 kJ/mol while the heat of
The liquid phase dehydration of 2-propanol has potential application adsorption for 2-propanol and water was 4 5 . 5 and
for wastewater purification where 2-propanol is present as an impurity. -9.6 kJ/mol, respectively.
To design a process for a 2-propanol/water separation, kinetic data for
On a etudie la deshydratation catalytique en phase
2-propanol dehydration in an aqueous media are essential. Although the
aqueuse du 2-propanol dans un reacteur b suspen-
vapour-phase dehydration of 2-propanol has been well studied, there sions discontinu. Les catalyseurs d‘alumine, zeolite
exists no information in the literature on the liquid phase dehydration of 13X, SAPO-5 et silicalite sont tous actifs dans la
2-propanol. Furthermore, the influence of a high concentration of water deshydratation en phase liquide du 2-propanol b 463 K,
on the rate of 2-propanol dehydration was not well understood. la silicalite &ant le plus actif. Le propylhe est apparu
In this study, performances of several well-known acid catalysts iitre le principal produit de reaction, avec formation
including alumina, zeolite 13X, SAPO-5 and silicalite were evaluated with tie diisopropylkther e t d’acetone b I’etat de traces. La
an initial 2-propanol concentration of 10 mol% a t 463 K in a batch slurry cinhtique de reaction sur la silicalite est determinee a
reactor. The kinetic study was carried out a t temperatures ranging from Line gamme de temperatures de 434 b 463 K et b une
gamrne de concentrations de 4 b 10% molaires de 2-
434 to 463 K and initial 2-propanol concentrations of 4 to 10 molYo. The
propanol dans I’eau. On a trouve qu’un mecanisme de
kinetic equation was derived based on a Langmuir-Hinshelwood- type Langumuir-Hinshelwood-Hougen-Watson (LHHW)
Hougen-Watson (LHHW) type reaction mechanism. The influence of b site unique decrivait bien les donnees cinetiques. On
water on the rate of 2-propanol dehydration was also examined. a trouvk que I‘eau inhibait la reaction de deshydratation.
LCnergie d‘activation sur la silicalite a 6te determinee
Experimental b 226,8 kJ/mol alors que la chaleur d’adsorption du
Experimental Apparatus 2-propanol et de I’eau sont de 45,s et -9,6 kJ/mol,
All experimental runs were conducted in a batch slurry reactor system respectivement.
(Figure 1). The reactor was a high pressure Parr reactor (Model 4841,
Parr Instruments Inc. USA) made of SS-316 stainless steel. The vessel has Keywords: 2-propanol dehydration, kinetics, silicalite,
sllJrry reactor.
a volume of 320 mL and is equipped with an impeller. A thermocouple
(]-type) was used to measure and control the reactor temperature. The
heating device/controller was used to maintain a constant reactor
temperature within *1 K. The liquid sampling line consists of a 0.125 m m 0.d. stainless steel tube connected to a stainless steel
sampling valve. A pressure transducer (Foxboro
electronic transmitter, Model 841 CM-D) was used to
meawre the reactor pressure.
‘Author to whom correspondence may be addressed. E-mail address: karlt.chuang@
ua1berta.m
f i A
Peng-Robinson equation of state (Stryjek and Vera, 1986). The
Peng-Robinson equation of state was chosen because of its
ability to accurately reproduce vapour-pressure data for a wide
variety of substances, such as polar, nonpolar and associating
compounds. For the vapour phase, conventional mixing rules
were used with the binary interaction term kii set equal to zero
Liquid Sampling Line He
because the non-idealities associated with polar compounds
and their mixtures are not as pronounced in the vapour-phase as
in the liquid-phase. The liquid phase activity coefficient yi must be
determined experimentally by fitting experimental pressure-
composition data with an excess Cibbs free energy model. Because
%
of the small range in liquid concentration (4 to 10 mol%) used in
Stirrer this study, the van Laar activity coefficient model was used:
Cij
Figure 1. Schematic diagram of experimental setup. lnyi =
(3)
[1+$]2
518 The Canadian Journal of Chemical Engineering, Volume 79, August 2001
The other vapour phase components, 2-propanol mole catalytic dehydration of 2-propanol in the liquid phase. The
fraction, yA and water vapour mole fraction, yw, are determined adsorption/clesorption of 2-propanol and/or water is assumed
using the modified Peng-Robinson equation of state and the to either occur via a single-site mode, where acid sites are
van Laar model. The liquid phase fugacity coefficient is involved or ei dual-site mode, where both acid and basic sites are
determined for a pure component and the vapour phase fugacity involved. The rate of propylene formation is considered to be
is determined for a component in a gas mixture (Stryjek and Vera, either inhibited or unaffected by the presence of water in our
1986). It is sufficient to say that $'!, is a function of all vapour phase model screening process. The chemical equilibrium constant for
composition and the compressibility factor for a gas mixture Z. the liquid-phase dehydration of 2-propanol at a temperature
We are now left with 6 unknowns: xA, yA, yw, L, a and Z. The range of 433 to 463 K ranges from 51.8 to 114.2. Because of
following outlines the set of nonlinear equations that must be the high values of the equilibrium constant, the reaction was
solved for each data point (pressure and temperature). assumed to be irreversible. The derived kinetic equations are
expressed a:i the following:
Compressibility Factor Z
Single-site mode adsorption, water term excluded (SSM - I ) :
Z3 + (5- l)Zz + ( A -3B2 -25)Z + ( B 3 + 52 - A61 = 0 (1 0)
Water component balance: Singlesite mode adsorption, water term included (SSM - 2):
L(I - x A ) + ( M + a~ - L~ ) ~ W= MWO + a kb:AC,q
r=-
1 + KACA + KwCw
0
0 00
> 0 02 004 008 0 08 0 10 0 12
Oudejans et al., 1982; Le Van Mao et al., 1990; Phillips and Datta,
1997). Silicoaluminophosphates (SAPO-5) are known to be
active in reactions requiring strong acids (Hedge et al., 1988).
The results of the catalyst screening are shown in Figure 4.
2PropanoJ Mole Fradion, XA’
The 2-propanol conversion is defined as the mole percent of
2-propanol that is converted to propylene. For all catalysts
Figure 2. The equilibrium pressure versus liquid composition: PRSV tested, propylene is the major reaction product. Only trace
equation of state with the van Laar excess Gibbs free energy model. +: amounts of diisopropyl ether and acetone were found. These
433 K; 0:443 K; A : 453 K; W : 463 K; - : van Laar model fit. results justify our assumption of a negligible amount of other
components in the liquid phase except water and 2-propanol.
Analysis of the liquid samples taken prior to starting of agitation
indicated negligible 2-propanol conversion during heating
period. The amount of 2-propanol converted to propylene over
It should be noted that these parameters were determined 5-115 AI,O, a t 463 K after 1.5 h is 5.1 46, which is far from the
under a relatively small range of 2-propanol concentrations. calculated equilibrium conversion of 35.3% at 463 K for 1.5 h
Caution should be exercised in extrapolating these parameters and an initial 2-propanol concentration of 10 mo146. The
to other concentration ranges. An accurate description of the assumption of an irreversible reaction appears to be justified.
vapour-liquid equilibria for 0 < xA c 1 is outside the scope of this S-115 AI,O, was found to be the most active catalysts of the
paper. The temperature dependence of the van Laar binary screened samples followed by S-115 SO,. In aqueous media,
constants was determined to be: the rate of propylene formation not only depends on the
number and strength of acid sites, but on the hydrophobicity of
the catalyst as well. It has been found previously that silicalite is
both more hydrophobic and more acidic than SAPO-5 (Hedge
c,2 =--2299’1 3.624, r 2 = 0.995 et al., 1988). This explains the higher activity of the silicalite
T
catalysts compared to the SAPO-5 catalyst. It should be noted
that the acidity and hydrophobicity of zeolites, such as silicalite,
depend on the silica/alumina ratio (Olson et al., 1980).
However, more tests need to be performed on the catalyst with
-+ 5.953,
c2, = -2228.6 r 2 = 0.893
respect to its acidity and hydrophobicity in order to make
T
10-
10.
0
.
14.
0
12’
0
10-
..
J 0
08-
..
“‘L
00
2 14 218 210 220 222 224 228 220 230 232
* 0 10 20 30 40 50 60 70 80 90 1W
100011. K
Time. min
520 The Canadian Journal of Chemical Englneerlng, Volume 79, August ZOO1
Table 1. Parameters of the developed LHHW kinetic models.
*%Model Fit = -
definite conclusions with regards to the influence of these The kinetic parameters established using the run with 10 mol%
parameters on the catalytic activity in the aqueous phase. All initial 2-propanol concentration were used to predict the rate of
kinetic runs were carried out with silicalite S-115 AI,O, catalyst. propylene formation at other initial 2-propanol concentrations.
It can be seen in Table 1 that the SSM-2 model, which has
Kinetic Study single-site adsorption of both 2-propanol and water in the rate
True surface reaction rates can only be determined if the experiments model predict well the rate of propylene formation for 2-propanol
are performed under conditions where the observed rate is not concentrations ranging from 4 to 10 mol%. Both models that
limited by diffusional processes. Our preliminary tests with include the water adsorption/desorption parameter predict well
silicalite 5-1 1 5 AI,O, catalyst at an experimental condition of the rate of propylene formation, which indicates a possible
463 K, 1.57 wt% catalyst loading and 10 mol% 2-propanol water inhibiting effect on propylene formation. This partly
indicate that that the reaction rate was not limited by interphase explains the poor dehydration activity of some of the
mass transfer and pore diffusion at stirrer speeds above 1000 hydrophilic catalysts such as zeolite 13X and SAPO-5 found
rpm and over the range of particle sizes tested (20-170 mesh). during the catalyst screening.
No apparent catalyst deactivation was observed in duplicate Figure 5 illustrates the amount of propylene produced with
experiments with the used catalysts. All kinetic experiments varying timi? a t several reaction temperatures with the fitted
were conducted with fresh silicalite S-115 AI,O, catalyst a t stirrer SSM-2 model. The model gives a good fit of the experimental
speeds of 1080 rpm with 30-40 mesh catalyst particle sizes. data for temperatures between 434 and 463 K. The temperature
Typical catalyst concentration was 1.57 wt% in 2-propanol/ dependence of the rate constant, as seen in Equation (20), is
water/catalyst mixture. The experimental data were fitted with shown in Figure 6. As can be seen from Figures 5 and 6, the rate
several LHHW rate equations (Equations 16, 17, 18, and 19). of propylent! formation is strongly dependent on temperature.
Activation energies and heats of adsorption calculated from the The high activation energy confirms that the kinetic data were
above fitted models are given in Table 1. obtained in a region where the diffusion was not rate limiting.
A good kinetic model should not only fit the experimental The temperature dependence of the adsorption constants for
data but also to predict the reaction rates under different the SSM-2 rate model is shown in Figure 7. The adsorption plots
conditions. To this end, additional kinetic runs were carried out have positive slopes, which indicates that the heat of adsorption
at 463 K for 2-propanolfeed concentrations of 4, 6 and 8 molOh. is exothermic. Figure 8 shows a reasonable agreement between
SSM-2 model prediction and experimental rates of propylene
"""I
0 20 40 60 80 100 120 140 160 214 216 218 220 222 224 228 220 230 232
100M. K "
Time, nin
Figure 5 . Comparison of experimental rate data with fitted SSM-2 Figure 6. Teinperature dependence of the kinetic parameters k,
model. *:434 K; A:444 K; 0 :453 K; M: 463 K; -: SSM-2 model fit. determined from the fitted SSM-2 LHHW model.
Subscripts
k = 1 .406.1023exp-
r2Y48) 0
A
C
initial, t = 0
2-propanol
catalyst
EX P experimental
K, = 8.32.10-’exp
Y21
(- H
..
‘,I
P
helium
component
propylene
Kw =1.66.10-2exp(T)
1154 PRED value predicted from model
T total
W water
522 The Canadlan Journal of Chemical Englneerlng, Volume 79, August ZOO1
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m infinite dilution (1 967).
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V vapour phase Aqueous Solution over ZSM-5 Zeolites. Influence of Reaction
Parameters and Catalyst Acidic Properties as Studied by Ammonia
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