Chemical Engineering Science 57 (2002) 4877 – 4882

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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 (40–80 atm; temperature 373–393 K).
? 2002 Elsevier Science Ltd. All rights reserved.

1. Introduction with a reacting system in which most of the propylene exists

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 70–80% 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 investi-
gators (Heistand, 1961; Kaiser, Beuther, Moore, & Odioso,
1962; Petrus, DeRoo, Stamhuis, & Joosten, 1986; Hirata and
Ogawa, 1998). Propylene being a non-polar compound pos-
sesses very low solubility in water and tends to form a second
phase if used in high concentrations. Depending on the reac-
tion 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 re-
acting 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).
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 propy-
lene, 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 separa-
tion 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 react-
ing system one may anticipate a favourable change in solu-
bility 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 (vapour–liquid) and supercritical
conditions and e.ect of di.erent parameters, especially the
reaction pressure, on the rate of the reaction under super-
critical 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
4878 S. M. Mahajani et al. / Chemical Engineering Science 57 (2002) 4877–4882

2. Previous studies 3. Experimental

Petrus et al. (1986) have studied hydration of propylene 3.1. Materials

with ion exchange resins in a single liquid phase and have
worked out the possible mechanism of the reaction based Propylene was obtained from Linde Gas Company, Aus-
on the formation of carbenium ion. They have also deter- tralia. The Amberlyst-15 and isopropanol was supplied by
mined the intrinsic rate constants for all the elementary Sigma-Aldrich Chemical Company. The various zeolites
steps of the mechanism. The presence of isopropanol in (ZSM-5 and mordenite), in ammonium form were obtained
the aqueous reacting phase adversely a.ects the reaction from Zeolyst International Pty. Ltd, USA. Zeolites were con-
rate at high conversions. This indicates that the simul- verted to the H-form by heating them for 3–4 h in a furnace
taneous removal of isopropanol may improve the yield. at about 823 K.
The recent computational work by Wyczesany (1993)
on the phase equilibria of this system under supercriti-
3.2. Apparatus and procedure
cal conditions shows substantial amount of alcohol in the
supercritical phase and thus suggests the promising poten-
The reactions were conducted in a batch liquid–liquid–
tial of using supercritical ole+ns as a part of the reaction
solid (catalyst) or supercritical-liquid–solid (catalyst)
medium.
modes. A stainless-steel reactor of 1 × 10−3 m3 capacity,
Hiestand (1961) and Kaiser et al. (1962) performed
equipped with speed and temperature monitoring facility
reactions in a trickle bed reactor that consists of solid
was used. Typically, the known amount of catalyst and
ion-exchange catalyst over which a two-phase mixture
water were charged to the reactor. The liquid propylene
of propylene and water is passed. The temperatures and
◦ at ambient temperature is transferred from the cylinder to
pressures examined were in the range 120–160 C and
an intermediate vessel through a Heskel pump. The vessel
60–100 bar. The patents by Deutsche Texaco (1973a, b,
is charged with nitrogen so as to maintain the pressure
c) also claim to have obtained signi+cant rates with sim-
(∼ 15 atm) that is suGciently higher than the vapour pres-
ilar catalyst under these conditions. A +xed bed reactor
sure of propylene to avoid any vapour-lock during the
is employed for the reaction and the outgoing product
transfer process. A high-pressure syringe pump was used
stream is separated into organic and aqueous phases. The
to charge the liquid propylene from the intermediate ves-
organic phase after removal of product(s) is recycled back
sel to the reactor. The reactor was heated to the desired
to the reactor (Neier, Webers, & Ostwald, 1984). Sur-
temperature and the speed of agitation was increased up to
prisingly, none of these studies seems to have pointed
the desired level; this time was regarded as the zero reac-
out the fact that there exists a supercritical phase in the
◦ tion time. The samples from both supercritical and aqueous
reactor under such conditions (100 bar and 142 C). The
phases were withdrawn at di.erent time intervals to study
fact that this separate phase contains substantial amount
the reaction kinetics.
of products is responsible for the ease in separation and
The solubility of propylene in water was measured by
improved process eGciency. Another important aspect of
water displacement technique. The aqueous phase samples
these studies is that they report considerable formation of
were withdrawn from the sample tube dipped in liquid.
di-isopropyl-ether, a side product that is known to form at
The dissolved propylene releases from the sample when
higher temperatures. It appears that this is due to the lo-
the sample is exposed to the atmospheric pressure. The
calised hot spots generated in the +xed bed reactor because
released propylene is measured from the corresponding
of the ineGcient heat removal. This process of formation
displacement of water in the inverted cylinder and the
of hot spots also leads to lower the catalyst life as is ap-
water from the sample is quanti+ed on the basis of the ob-
parent from the patent literature. Hence, there is a need
served increase in the weight of water in the displacement
to develop a thermally stable catalyst. The Asahi’s patent
tank.
(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 3.3. Analysis
cyclic ole+ns like cyclohexene. Hence, apart from exam-
ining the role of supercritical phase in this reaction, the The samples of both aqueous and supercritical phases
various zeolite catalysts such as ZSM-5 (with di.erent were analysed on a gas chromatograph (HP 5890) equipped
SiO2 =Al2 O3 ratio) and mordenite were also investigated with a thermal conductivity detector (TCD). A 2 m long
in the present work. Though the use of zeolite for hydra- Porapack-Q column was used to separate di.erent com-
tion of lower (C3 –C4 ) ole+ns has been appeared in some ponents from the reacting system. The oven was oper-
patents by Mobil Oil Corp. (Chang & Morgan, 1980; ated under isothermal conditions at 383 K throughout
Huag, Laplerre, & Tabuk, 1989), the detailed kinetics and the analysis. The internal and external surface are of the
their comparison with cation exchange resins still requires catalyst samples was measured on a Micrometics BET
attention. apparatus.
 S. M. Mahajani et al. / Chemical Engineering Science 57 (2002) 4877–4882 4879

0.2
Liquid phase

0.16 supercritical phase

Total

Conversion
0.12

0.08

0.04

0
0 1 2 3 4 5
Time (hrs)

Fig. 1. General course of the reaction: Temperature, 393 K; catalyst loading, 19% w=w of aq. phase; pressure, 70–63 atm.

0.8

0.7 ZSM-5 393 K

ZSM-5; 413 K
Isopropanol gms/gm of catalyst

0.6 Amberlyst-15 393 K

reused ZSM-5 413 K
0.5
mordenite 393 K

0.4

0.3

0.2

0.1

0
0 1 2 3 4 5 6
Time (hrs)

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

3.4. Results and discussion 3.4.2. Comparison of di0erent catalysts

The reaction was studied in the presence of di.erent solid
3.4.1. General course of the reaction catalysts such as cationic exchange resin-Amberlyst-15, ze-
Fig. 1 shows the general course of the reaction per- olites (ZSM-5 with SiO2 =Al2 O3 = 30–400 and mordenite).
formed with ZSM-5 zeolite catalyst at the conditions Fig. 2 compares the results obtained under each case. The
mentioned therein. Typically, 30–40% of the isopropanol cationic exchange resin was found to be the most promising
formed exists in the supercritical phase at a phase ratio of of all the catalysts. It was found that the zeolites, in spite
3:2 vol=vol (aqueous:organic). The concentration of iso- of being stable at high temperatures, get rapidly deactivated
propanol, in both aqueous and supercritical phases, builds due to possible formation of oligomers or carbonaceous ma-
up as the reaction progresses. Under the range of tem- terial. This observation is surprising in view of the claims
perature, pressure and degrees of conversion studied, the made by Mobil Oil Corp. (e.g. Chang & Morgan, 1980) that
formation of di-isopropyl ether (DIPE) is insigni+cant. ZSM-5 is among those zeolites that can be successfully used
However, in the case of the reactions at high temperatures for hydration of lower ole+ns. The BET surface area mea-
a small amount of DIPE was detected in the non-aqueous surements show that the surface area of the catalyst reduced
phase. by a factor of 10, after the reaction time of only about 2 h.
4880 S. M. Mahajani et al. / Chemical Engineering Science 57 (2002) 4877–4882

0.12

0.1 19% w/w of the aq phase

9%w/w of aq phase
0.08

Conversion
0.06

0.04

0.02

0
0 1 2 3 4 5 6
Time (hr)

Fig. 3. E.ect of catalyst loading: mole ratio, water:propylene 5:1; temperature, 383 K; pressure, 69–64 atm.

0.9
373 K
Total isopropanol formed (gm/gm of catalyst)

383 K
393 K

0.6

0.3

0
0 1 2 3 4 5 6
Time (hr)

Fig. 4. E.ect of temperature: pressure, 64–69 atm; catalyst loading 19% w=w.

3.4.3. Elimination of mass transfer resistance 3.5. E0ect of temperature and pressure under
The reaction was performed over a wide range of speed supercritical conditions
of agitation and it was found that over 900 rpm there is
no change in the conversion vs time plot. Hence, all the The reaction was studied over a temperature range of
reactions were performed at 1500 rpm to ensure that there 373–393 K. The rate of formation of isopropanol increases
is no resistance to mass transfer at both solid–liquid and with an increase in temperature as shown in Fig. 4. The
aqueous–organic interfaces. temperature not only inFuences the intrinsic rate constants
in this case but also alters the dissolved propylene concen-
3.4.4. Catalyst loading tration. This is evident in Fig. 5 that shows the solubility
The reaction was performed over a range of catalyst load- behaviour of propylene in water under supercritical con-
ing from 5–18% w=w of the aqueous phase. It was observed ditions. At a given temperature, the reaction pressure can
that the initial rate of the reaction is directly proportional be varied by loading di.erent amounts of propylene to the
to the catalyst loading and varies linearly with the same. batch reactor. Under sub-critical conditions, the increase in
Fig. 3 shows the dependency of the initial rate on the catalyst pressure results in an increase in the solubility of propylene
loading. This +nding indicates that the rate constant for this in water. If the pressure exceeds well beyond the critical
reaction should be expressed per unit weight of the catalyst. pressure of propylene (44 atm) then the non-aqueous phase
 S. M. Mahajani et al. / Chemical Engineering Science 57 (2002) 4877–4882 4881

0.004

Solubility of Propylene (mole fraction)

0.003 373 K
383 K
393 K
0.002

0.001

0
20 25 30 35 40 45 50 55 60 65 70
Pressure (atm)

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

1
25-23 atm (liquid-vapour)
50-45 atm
0. 8 53-47 atm
isopropanol (gm/gm of catalyst)

65-60 atm
69-65 atm
0. 6

0. 4

0. 2

0
0 1 2 3 4 5
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 3.6. Kinetic modelling

to study the behaviour of this phase as a part of the reac-
tion environment. It is anticipated that this phase will ex- The rate of formation of isopropanol for a reversible re-
tract isopropanol out from the aqueous phase and will expe- action is given by the following equation:
dite the forward reaction. Fig. 6 shows the e.ect of pressure
on the rate of the reaction. Under subcritical conditions, a
aq
rol = kf Cne − kb Colaq : (1)
substantial rise in initial rate is realised as a result of an in- The rate constant for the forward reaction can be eval-
crease in pressure. Hence, a noticeable increase in the rate uated by measuring the slope at time equal to zero. The
can be seen when one compares the data at lower pressure initial concentration of propylene in the aqueous phase
(25 atm-subcritical) conditions with that under supercritical was regarded as the solubility of propylene in water at the
conditions (50–70 atm). However, in the supercritical re- reaction temperature and pressure. The solubility data for
gion, at a given temperature the rate does not increase sub- a vapour–liquid system have been reported in the litera-
stantially with an increase in pressure. This again can be ture whereas solubility under supercritical conditions has
explained on the basis of the solubility plot (Fig. 6) which been determined in the present work. With the help of this
shows that solubility is almost insensitive to the change in data the intrinsic rate constant for the forward reaction
pressure under the conditions employed for the present work. are calculated at di.erent temperatures. The large value
4882 S. M. Mahajani et al. / Chemical Engineering Science 57 (2002) 4877–4882

-3

-4

ln(k) for forward reaction -5

-6

-7
0.0025 0.00255 0 .0026 0.00265 0.0027
1/T (1/K)

Fig. 7. Activation energy plot for propylene hydration.

of activation energy (Fig. 7) (∼ 20 kcal=gmol) suggests kf and kb : forward and backward rate constants
the absence of intraparticle di.usion limitations in the ion (l=h g of catalyst)
exchange resins. The rate constant under vapour phase con- rol : rate of formation of isopropanol per gram
ditions match with those reported by Hiestand (1961) and of the catalyst (gmol=h g of catalyst)
Petrus et al. (1986).

References
4. Conclusion
Chang, C. D., & Morgan, M. J. (1980). Hydration of ole+ns using zeolite
The reaction kinetics of propylene to isopropanol was catalysts. US patent 4214107.
studied in the presence of cationic exchange resins and zeo- Deutsche Texaco, (1973a). Brit patent, 1381455.
Deutsche Texaco, (1973b). Brit patent, 1386195.
lites as catalysts. The zeolites su.er from fairly rapid deac- Deutsche Texaco, (1973c). Brit patent, 1390164.
tivation due to formation of oligomers. A proper method of Hiestand, J. H. (1961). Ph.D. thesis, University of Michigan.
catalyst regeneration has to be established to exploit the real Hirata, S., & Ogawa, S. (1998). Process for producing isopropyl alcohol.
potential of the zeolites. The e.ect of supercritical conditions US patent 5763693.
was investigated. A considerable enhancement in the rate Huag, T. J., Laplerre, R. B., & Tabuk, S. A. (1989). Process for production
of ether and alcohol. US patent 4,857,664.
is realised while switching over from subcritical (vapour– Ishada, H. (1997). Liquid phase hydration of cyclohexene with zeolites.
liquid mode) to supercritical conditions (liquid-supercritical Catalysis Surveys of Japan, 1, 241–246.
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Neier, W., Webers, W., & Ostwald, W. (1984). Process for the production
w=w of the total formed) exists in the supercritical organic of lower aliphatic alcohols. US patent 4,45,776.
phase at a phase ratio of 3:2 vol=vol (organic=aqueous). This Neier, W., & Wollner, J. (1973). CHEMTECH, 2, 95–99.
suggests that employing the supercritical conditions may re- Petrus, L., DeRoo, R. W., Stamhuis, E. J., & Joosten, G. E. H. (1986).
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Notation Zhang, H., Mahajani, S. M., Sharma, M. M., & Sridhar, T. (2002).
Chemical Engineering Science, 57, 315–322.

Cne and Col : concentrations of propylene and isopro-

panol in the aqueous phase (gmol=l)