Chemical Engineering Science 57 (2002) 4877 4882

www.elsevier.com/locate/ces

Direct hydration of propylene in liquid phase and under supercritical

conditions in the presence of solid acid catalysts
S. M. Mahajani, M. M. Sharma, T. Sridhar
Department of Chemical Engineering, Monash University, Clayton 3168, Vic., Australia

Abstract
Hydration of propylene has been studied in both liquid phase conditions and above the critical temperature and pressure of propylene.
There is a signi+cant rise in initial rate while switching over from sub-critical to supercritical conditions, mainly because of the increase
in solubility of propylene in water. Substantial amount of isopropanol exists in the supercritical phase. This suggests the possibility of
the enhancement in equilibrium conversion under supercritical conditions. The reaction pressure has negligible e.ect on reaction kinetics
under these conditions (4080 atm; temperature 373393 K).
? 2002 Elsevier Science Ltd. All rights reserved.

1. Introduction
The direct hydration of propylene to produce isopropanol
has been commercialised way back in early 1970s (Neier &
Wollner, 1973). This process has several advantages over
the indirect two-step hydration process that manufactures
isopropanol through the formation of the corresponding
sulphate via reaction with 7080% sulphuric acid. This
sulphate on subsequent hydrolysis gives isopropanol and
dilute sulphuric acid has to be concentrated for recycle.
The direct hydration with solid acid catalysts obviates the
use of sulphuric acid and minimises the waste disposal
problems, and in addition, allows the use of non-corrosive
environment.
The direct hydration in the presence of cation exchange
resin catalyst has been studied in the past by several investigators (Heistand, 1961; Kaiser, Beuther, Moore, & Odioso,
1962; Petrus, DeRoo, Stamhuis, & Joosten, 1986; Hirata and
Ogawa, 1998). Propylene being a non-polar compound possesses very low solubility in water and tends to form a second
phase if used in high concentrations. Depending on the reaction conditions employed, this second phase can be vapour
phase, liquid phase or a supercritical phase. Hence, apart
from the studies by Petrus et al. (1986) who investigated reacting system composed of a single liquid phase along with
solid catalyst, all other experimental investigations deal
Corresponding author. Tel.: +61-3-9905-3427;
fax: +61-3-9905-9649.
E-mail address: tam.sridhar@eng.monash.edu.au (T. Sridhar).

with a reacting system in which most of the propylene exists

in a separate phase.
The reaction conditions in practice are such that a slight
modi+cation may result in the existence of a supercritical
phase in a batch reactor. Propylene has critical properties
(Tc =364 K and Pc =44 atm) close to the reaction conditions
of the direct hydration. It is possible that by performing the
reaction over the critical temperature and pressure of propylene, one can deliberately allow the formation of a separate
supercritical phase in the reactor. The supercritical Fuids are
known for their eGcient solvent characteristics. The product
isopropanol can be simultaneously extracted out to enhance
the conversion and rates of this reversible reaction that takes
place on a hydrophilic catalyst surrounded by the aqueous
phase. The simultaneous extraction also partially reduces
the load on downstream processing of the reaction mixture
for the separation of isopropanol from water. The separation of isopropanol from the organic supercritical phase is
much easier than that from the aqueous phase. Moreover,
because of the highly non-ideal characteristics of the reacting system one may anticipate a favourable change in solubility of propylene in the reacting aqueous phase. Hence, the
present work is directed towards investigating the reaction
under the supercritical conditions for propylene. It covers
comparison of subcritical (vapourliquid) and supercritical
conditions and e.ect of di.erent parameters, especially the
reaction pressure, on the rate of the reaction under supercritical conditions. The rate constants are validated against
those reported in the literature.

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PII: S 0 0 0 9 - 2 5 0 9 ( 0 2 ) 0 0 2 9 3 - 2

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S. M. Mahajani et al. / Chemical Engineering Science 57 (2002) 48774882

2. Previous studies

3. Experimental

Petrus et al. (1986) have studied hydration of propylene

with ion exchange resins in a single liquid phase and have
worked out the possible mechanism of the reaction based
on the formation of carbenium ion. They have also determined the intrinsic rate constants for all the elementary
steps of the mechanism. The presence of isopropanol in
the aqueous reacting phase adversely a.ects the reaction
rate at high conversions. This indicates that the simultaneous removal of isopropanol may improve the yield.
The recent computational work by Wyczesany (1993)
on the phase equilibria of this system under supercritical conditions shows substantial amount of alcohol in the
supercritical phase and thus suggests the promising potential of using supercritical ole+ns as a part of the reaction
medium.
Hiestand (1961) and Kaiser et al. (1962) performed
reactions in a trickle bed reactor that consists of solid
ion-exchange catalyst over which a two-phase mixture
of propylene and water is passed. The temperatures and

pressures examined were in the range 120160 C and

60100 bar. The patents by Deutsche Texaco (1973a, b,
c) also claim to have obtained signi+cant rates with similar catalyst under these conditions. A +xed bed reactor
is employed for the reaction and the outgoing product
stream is separated into organic and aqueous phases. The
organic phase after removal of product(s) is recycled back
to the reactor (Neier, Webers, & Ostwald, 1984). Surprisingly, none of these studies seems to have pointed
out the fact that there exists a supercritical phase in the

reactor under such conditions (100 bar and 142 C). The
fact that this separate phase contains substantial amount
of products is responsible for the ease in separation and
improved process eGciency. Another important aspect of
these studies is that they report considerable formation of
di-isopropyl-ether, a side product that is known to form at
higher temperatures. It appears that this is due to the localised hot spots generated in the +xed bed reactor because
of the ineGcient heat removal. This process of formation
of hot spots also leads to lower the catalyst life as is apparent from the patent literature. Hence, there is a need
to develop a thermally stable catalyst. The Asahis patent
(Ishada, 1997) and our previous work (Zhang, Mahajani,
Sharma, & Sridhar, 2002) indicate that zeolites can be
successfully used in an aqueous medium for hydration of
cyclic ole+ns like cyclohexene. Hence, apart from examining the role of supercritical phase in this reaction, the
various zeolite catalysts such as ZSM-5 (with di.erent
SiO2 =Al2 O3 ratio) and mordenite were also investigated
in the present work. Though the use of zeolite for hydration of lower (C3 C4 ) ole+ns has been appeared in some
patents by Mobil Oil Corp. (Chang & Morgan, 1980;
Huag, Laplerre, & Tabuk, 1989), the detailed kinetics and
their comparison with cation exchange resins still requires
attention.

3.1. Materials
Propylene was obtained from Linde Gas Company, Australia. The Amberlyst-15 and isopropanol was supplied by
Sigma-Aldrich Chemical Company. The various zeolites
(ZSM-5 and mordenite), in ammonium form were obtained
from Zeolyst International Pty. Ltd, USA. Zeolites were converted to the H-form by heating them for 34 h in a furnace
at about 823 K.
3.2. Apparatus and procedure
The reactions were conducted in a batch liquidliquid
solid (catalyst) or supercritical-liquidsolid (catalyst)
modes. A stainless-steel reactor of 1 103 m3 capacity,
equipped with speed and temperature monitoring facility
was used. Typically, the known amount of catalyst and
water were charged to the reactor. The liquid propylene
at ambient temperature is transferred from the cylinder to
an intermediate vessel through a Heskel pump. The vessel
is charged with nitrogen so as to maintain the pressure
( 15 atm) that is suGciently higher than the vapour pressure of propylene to avoid any vapour-lock during the
transfer process. A high-pressure syringe pump was used
to charge the liquid propylene from the intermediate vessel to the reactor. The reactor was heated to the desired
temperature and the speed of agitation was increased up to
the desired level; this time was regarded as the zero reaction time. The samples from both supercritical and aqueous
phases were withdrawn at di.erent time intervals to study
the reaction kinetics.
The solubility of propylene in water was measured by
water displacement technique. The aqueous phase samples
were withdrawn from the sample tube dipped in liquid.
The dissolved propylene releases from the sample when
the sample is exposed to the atmospheric pressure. The
released propylene is measured from the corresponding
displacement of water in the inverted cylinder and the
water from the sample is quanti+ed on the basis of the observed increase in the weight of water in the displacement
tank.
3.3. Analysis
The samples of both aqueous and supercritical phases
were analysed on a gas chromatograph (HP 5890) equipped
with a thermal conductivity detector (TCD). A 2 m long
Porapack-Q column was used to separate di.erent components from the reacting system. The oven was operated under isothermal conditions at 383 K throughout
the analysis. The internal and external surface are of the
catalyst samples was measured on a Micrometics BET
apparatus.

S. M. Mahajani et al. / Chemical Engineering Science 57 (2002) 48774882

4879

0.2
Liquid phase
supercritical phase

0.16
Conversion

Total
0.12

0.08

0.04

0
0

Time (hrs)
Fig. 1. General course of the reaction: Temperature, 393 K; catalyst loading, 19% w=w of aq. phase; pressure, 7063 atm.

0.8

Isopropanol gms/gm of catalyst

0.7

ZSM-5 393 K
ZSM-5; 413 K
Amberlyst-15 393 K

0.6

reused ZSM-5 413 K

mordenite 393 K

0.5
0.4
0.3
0.2
0.1
0
0

3
Time (hrs)

Fig. 2. Comparison of di.erent catalysts: mole ratio, water:propylene 5:1.

3.4. Results and discussion

3.4.1. General course of the reaction
Fig. 1 shows the general course of the reaction performed with ZSM-5 zeolite catalyst at the conditions
mentioned therein. Typically, 3040% of the isopropanol
formed exists in the supercritical phase at a phase ratio of
3:2 vol=vol (aqueous:organic). The concentration of isopropanol, in both aqueous and supercritical phases, builds
up as the reaction progresses. Under the range of temperature, pressure and degrees of conversion studied, the
formation of di-isopropyl ether (DIPE) is insigni+cant.
However, in the case of the reactions at high temperatures
a small amount of DIPE was detected in the non-aqueous
phase.

3.4.2. Comparison of di0erent catalysts

The reaction was studied in the presence of di.erent solid
catalysts such as cationic exchange resin-Amberlyst-15, zeolites (ZSM-5 with SiO2 =Al2 O3 = 30400 and mordenite).
Fig. 2 compares the results obtained under each case. The
cationic exchange resin was found to be the most promising
of all the catalysts. It was found that the zeolites, in spite
of being stable at high temperatures, get rapidly deactivated
due to possible formation of oligomers or carbonaceous material. This observation is surprising in view of the claims
made by Mobil Oil Corp. (e.g. Chang & Morgan, 1980) that
ZSM-5 is among those zeolites that can be successfully used
for hydration of lower ole+ns. The BET surface area measurements show that the surface area of the catalyst reduced
by a factor of 10, after the reaction time of only about 2 h.

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S. M. Mahajani et al. / Chemical Engineering Science 57 (2002) 48774882

0.12

19% w/w of the aq phase

0.1

9%w/w of aq phase
Conversion

0.08
0.06
0.04
0.02
0
0

3
Time (hr)

Fig. 3. E.ect of catalyst loading: mole ratio, water:propylene 5:1; temperature, 383 K; pressure, 6964 atm.

Total isopropanol formed (gm/gm of catalyst)

0.9
373 K
383 K
393 K
0.6

0.3

0
0

3
Time (hr)

Fig. 4. E.ect of temperature: pressure, 6469 atm; catalyst loading 19% w=w.

3.4.3. Elimination of mass transfer resistance

The reaction was performed over a wide range of speed
of agitation and it was found that over 900 rpm there is
no change in the conversion vs time plot. Hence, all the
reactions were performed at 1500 rpm to ensure that there
is no resistance to mass transfer at both solidliquid and
aqueousorganic interfaces.
3.4.4. Catalyst loading
The reaction was performed over a range of catalyst loading from 518% w=w of the aqueous phase. It was observed
that the initial rate of the reaction is directly proportional
to the catalyst loading and varies linearly with the same.
Fig. 3 shows the dependency of the initial rate on the catalyst
loading. This +nding indicates that the rate constant for this
reaction should be expressed per unit weight of the catalyst.

3.5. E0ect of temperature and pressure under

supercritical conditions
The reaction was studied over a temperature range of
373393 K. The rate of formation of isopropanol increases
with an increase in temperature as shown in Fig. 4. The
temperature not only inFuences the intrinsic rate constants
in this case but also alters the dissolved propylene concentration. This is evident in Fig. 5 that shows the solubility
behaviour of propylene in water under supercritical conditions. At a given temperature, the reaction pressure can
be varied by loading di.erent amounts of propylene to the
batch reactor. Under sub-critical conditions, the increase in
pressure results in an increase in the solubility of propylene
in water. If the pressure exceeds well beyond the critical
pressure of propylene (44 atm) then the non-aqueous phase

S. M. Mahajani et al. / Chemical Engineering Science 57 (2002) 48774882

4881

Solubility of Propylene (mole fraction)

0.004

0.003

373 K
383 K
393 K

0.002

0.001

0
20

25

30

35

40
45
50
Pressure (atm)

55

60

65

70

Fig. 5. Solubility of propylene in water under supercritical conditions.

isopropanol (gm/gm of catalyst)

1
25-23 atm (liquid-vapour)
50-45 atm
53-47 atm
65-60 atm
69-65 atm

0. 8

0. 6

0. 4

0. 2

0
0

Time (hr)
Fig. 6. E.ect of pressure on propylene hydration: temperature, 393 K; catalyst loading 19% w=w of the aq. phase.

transforms into a supercritical Fuid phase. It is interesting

to study the behaviour of this phase as a part of the reaction environment. It is anticipated that this phase will extract isopropanol out from the aqueous phase and will expedite the forward reaction. Fig. 6 shows the e.ect of pressure
on the rate of the reaction. Under subcritical conditions, a
substantial rise in initial rate is realised as a result of an increase in pressure. Hence, a noticeable increase in the rate
can be seen when one compares the data at lower pressure
(25 atm-subcritical) conditions with that under supercritical
conditions (5070 atm). However, in the supercritical region, at a given temperature the rate does not increase substantially with an increase in pressure. This again can be
explained on the basis of the solubility plot (Fig. 6) which
shows that solubility is almost insensitive to the change in
pressure under the conditions employed for the present work.

3.6. Kinetic modelling

The rate of formation of isopropanol for a reversible reaction is given by the following equation:
aq
rol = kf Cne
kb Colaq :

(1)

The rate constant for the forward reaction can be evaluated by measuring the slope at time equal to zero. The
initial concentration of propylene in the aqueous phase
was regarded as the solubility of propylene in water at the
reaction temperature and pressure. The solubility data for
a vapourliquid system have been reported in the literature whereas solubility under supercritical conditions has
been determined in the present work. With the help of this
data the intrinsic rate constant for the forward reaction
are calculated at di.erent temperatures. The large value

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S. M. Mahajani et al. / Chemical Engineering Science 57 (2002) 48774882

ln(k) for forward reaction

-3

-4

-5

-6

-7
0.0025

0.00255

0 .0026
1/T (1/K)

0.00265

0.0027

Fig. 7. Activation energy plot for propylene hydration.

of activation energy (Fig. 7) ( 20 kcal=gmol) suggests

the absence of intraparticle di.usion limitations in the ion
exchange resins. The rate constant under vapour phase conditions match with those reported by Hiestand (1961) and
Petrus et al. (1986).

rol :

forward and backward rate constants

(l=h g of catalyst)
rate of formation of isopropanol per gram
of the catalyst (gmol=h g of catalyst)

References

4. Conclusion
The reaction kinetics of propylene to isopropanol was
studied in the presence of cationic exchange resins and zeolites as catalysts. The zeolites su.er from fairly rapid deactivation due to formation of oligomers. A proper method of
catalyst regeneration has to be established to exploit the real
potential of the zeolites. The e.ect of supercritical conditions
was investigated. A considerable enhancement in the rate
is realised while switching over from subcritical (vapour
liquid mode) to supercritical conditions (liquid-supercritical
mode). However, increase in pressure under supercritical
conditions does not help to increase the initial rate of the reaction. A substantial quantity of isopropanol (about 3040%
w=w of the total formed) exists in the supercritical organic
phase at a phase ratio of 3:2 vol=vol (organic=aqueous). This
suggests that employing the supercritical conditions may reduce the separation cost only if high conversion is desired.
Notation
Cne and Col :

kf and kb :

concentrations of propylene and isopropanol in the aqueous phase (gmol=l)

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