Professional Documents
Culture Documents
Isopropyl Alcohol by Direct Hydration of Propylene : Technical Paper
Isopropyl Alcohol by Direct Hydration of Propylene : Technical Paper
TECHNICAL PAPER
It seems necessary for a better understanding state. This catalyst is suitable for both vapour-
of Tokuyama Process to review some typical phase and liquid-phase processes. The examples
hydration processes briefly.
The catalysts most widely proposed for the
vapour-phase direct hydration of propylene are
mineral acids such as phosphoric acid and he-
teropoly acids on silica or diatomaceous earth,
and solid acids of metal oxides.
The reaction is generally carried out by passing
steam and propylene in a molar ratio of 0.5∼2.0:
of the results of propylene hydration with the Table 1 Effect of Anion on Rate of Propylene
Hydration
zirconium tungstate catalyst in vapour phase and
liquid phase are shown in Fig. 1 and Fig. 2,
respectively, in comparison with the data of
liquid-phase hydration over tungsten oxide ca-
talyst by Zabor et al.18)
The use of insoluble solid catalysts eliminates
the difficulties of the remarkable migration and
depletion of acid which take place in the hydration
with supported acid catalysts. However, under
the severe hydrothermal conditions in the liquid-
phase hydration under high pressure, gradual
depletion or crystallization of the effective com-
ponents of catalyst is inevitable, and consequently
both the decrease in hydration rate and some
operating troubles will occur. Recently, Deut-
sche Texaco has developed a trickle process19) pressure in aqueous solution.
Tokuyama Soda studied systematically the ca-
in vapour and liquid phases applying cation
talytic activities and stabilities of aqueous solutions
exchange resins as catalysts under milder con-
of various acid compounds in the direct hydration
ditions of 130∼150℃ and 60∼100 atm. One
of the main problems in this process is probably of olefins, and finally developed an excellent
the hydrolysis of sulfonic acid groups of the catalyst system of a stable aqueous solution under
resin catalyst which causes the irreversible loss high temperature and pressure. It was found
of catalytic activity. from the study that the rate of hydration was
markedly increased by the presence of some
In order to overcome the difficulties in the
kinds of polyatomic anions as shown in Table 1.
fixed bed processes with solid catalysts, the liquid
The activation energy of the propylene hy-
phase hydration with the solid catalyst dispersed
dration with the catalyst solution of polyatomic
in water can be employed20)∼22). In this process,
anions is about 24kcal/mol which is 6kcal/mol
propylene is treated with water at an elevated
higher than that in the case of the catalyst so-
temperature and pressure in the presence of an
aqueous suspension of fine particles of the ca- lution of sulfate anions.
According to the known mechanisms26)∼29) of
talyst. Although high space-time yields based
olefin hydration in very dilute aqueous acid,
on catalyst are obtainable by the suspension pro-
the hydration rate is proportional to the acid
cess, some operational difficulties of separation
concentration, and the counter anions have no
and circulation of the suspended particles can
effect on the rate. Since the medium effect on
not be avoided.
the activity coefficient of each component in
Tokuyama Soda fully examined the disadvan-
very dilute acid solution is considerably small,
tages and difficulties in the typical processes de-
the effect of the polyatomic anion on both the
scribed above through its own extensive experi-
hydration rate and the activation energy is pro-
ments, and attained to a conclusion that the
bably interpreted by assuming an intermediate
liquid-phase direct hydration with an aqueous
of an activated complex containing the anion.
solution of catalyst would be most profitable
for the production of isopropanol. Some ca- 3 Tokuyama Direct Hydration Process
talyst systems in a state of aqueous solution have 3.1 Catalyst System
been ofTered in recent patents23)∼25) The catalyst system employed in Tokuyama
However, these systems have the disadvantages Process30)∼34) essentially comprises a dilute aqueous
of low selectivity for hydration in the case of solution of definite kinds of polytungsten com-
aqueous solution of copper halide catalyst and pounds within a selective pH range. This ca-
low stabilities of catalyst components, such as talyst system is highly active and remarkably
aluminium sulfate, ferric sulfate, chromium sul- selective for hydrating propylene to isopropanol.
fate and molybdic acid which are hydrolyzed to This system is also very stable because the ca-
insoluble hydroxides at high temperature and talyst components are strongly resistant to hy-
drolysis. Such high stability of the catalyst sys- Because of large excess of water, the rate is given
tem is well maintained at all times in operation by the following equation via a pseudo-first order
by the careful control of poisons which cause kinetic treatment:
the decomposition of the catalyst. The catalyst γ=kl(Cp-Ci/kl)=kg(Pp-Pi/Pwe.kg)
life is, therefore, very long in continuous operation. where
Tokuyama Process gives, moreover, higher per ki, kg: rates of conversion of propylene to
pass conversions of propylene owing to intimate isopropanol in solution at unit con-
contact between dissolved propylene and the centration of propylene in solution,
catalyst solution in the liquid phase than in the and at unit pressure of propylene in
case where solid catalyst systems are employed. vapour phase, respectively.
Fig. 3 shows an example of the experimental Ki, Kg: equilibrium constants in liquid and
results of propylene hydration with the Tokuyama vapour phases, respectively.
catalyst system by a continuous flow reactor. Cp, Ci: concentrations of propylene and iso-
3.2 Kinetics of Hydration propanol in solution, respectively.
In the hydration of propylene with the To- pp, Pi: partial pressures of propylene and
kuyama catalyst system, the reaction takes place isopropanol in vapour phase, res-
between dissolved propylene and water in an pectively.
aqueous solution. The hydration rate is con- Pwe: equilibrium partial pressure of water
troled by the reaction step, provided equilibrium in vapour phase.
is at all times maintained in the distribution This basic rate equation can be suitably ap-
of propylene between vapour and liquid phases.
plied to calculate conversion or space-time yield
in process design and economic evaluation.
3.3 Process Description
The flow scheme of Tokuyama Process is
shown in Fig. 4.
Liquid propylene is preheated and fed to a
reactor under pressure. The catalyst solution
recovered from the azeotrope column is pre-
heated by heat exchange with the reactor effluent
and fed to the reactor operating at 240∼270℃
section.
liquid is sent to the azeotropic column, from
where azeotropic mixture of isopropanol and water (6) Since the reaction is carried out in aqueous
is drawn off and sent to further distillation steps solution, the heat loss incidental to evaporation
for purification and dehydration. The aqueous and condensation of water can be avoided.
solution containing catalyst from the bottom of (7) Because of absence of corrosion in the sys-
the azeotrope column joins with fresh water and tem, easy operation and maintenance of equip-
is recycled to the reactor. The azeotrope al- ments are possible.
cohol is freed of the light impurities in the first (8) The process is simple. It is also a com-
rectifying column and then dehydrated in two pletely closed system free from waste substances,
further columns with benzene as the dehydrat- and consequently the process can clear all the
ing agent. To obtain a high grade isopropanol environmental protective regulations.
(99.99% purity), another additional distillation 3.5 Quality of Product
step is necessary. Trypical data of the product isopropanol ob-
Under the optimum reaction conditions, the tained in Tokuyama Process are given in Table 2.
range of propylene conversion per pass is about 3.6 Economics
60∼70% and selectivity to isopropanol based The economics of Tokuyama Process are shown
on the converted propylene is as much as 98∼ in Table 3. They include the entire processing
99%. The major by-product is di-isopropyl of propylene to 99.99% isopropanol.
ether. 3.7 Other Applications
In Tokuyama Process, both the spent gas Tokuyama Process is also applicable to the
from the reactor and all the by-products drawn economical production of ethanol and butanols.
off at the purification section are completely 4 Conclusion
utilized as fuel for heating in the system. Besides the low value for propylene consump-
3.4 Features of Process tion, simpleness of process and freedom from
Tokuyama Process has a number of advantages enviromental pollution problems by nature of
based on its own catalyst system and process the process itself make Tokuyama Process by far
design. The features of the process confirmed more economical than the conventional process
in commercial operation are as follows: for the manufacture of isopropanol.
(1) The catalyst system comprises a homogene- In the recent trend of the process for isopro-
ous dilute aqueous solution which maintains high
activity and excellent selectivity for hydrating Table 2 Typical Properties of Product
propylene to isopropanol.
(2) The catalyst solution is so highly stabiliz-
ed that it is circulated repeatedly in the reaction
system without any additional treatments. Ca-
talyst life is, therefore, very long.
(3) Since the reaction is carried out in aqueous
solution under high pressure, the formation of
isopropanol is markadly favoured by equilibrium
effect.
(4) The amount of unconverted propylene to
be recycled is small owing to high conversion Table 3 Economics of Tokuyama Soda
rate of propylene, and consequently this process Direct Liquid-Phase Hydration Process
panol production toward direct hydration, To- 13) Hibernia Chemie, Brit. 1, 106,424 (1968).
14) Kline, C. H. et al., Ind. Eng. Chem., 57, (9), 53
kuyama Soda will greatly contribute to the
(1965).
proceeding of this trend through experience in 15) Tokuyama Soda, Japan 43-6603 (1968).
its own commercial plant. 16) Tokuyama Soda, U. S. 3,450, 777 (1969).
17) Tokuyama Soda, Brit. 1,192,692 (1970).
References 18) Zabor, R. C. et al., Actes Congr. Intern. Catalyse, 2e,
Paris, 1960, 2, 2601 (1961).
1) Stull, D. R. et al., "The Chemical Thermodynamics 19) Europ. Chem. News, Nov. 19, 36 (1971).
of Organic Compounds", (1967) John Wiley & 20) Imperial Chemical Industries Ltd., Brit., 727, 665
Sons, Inc., New York. (1955).
2) Stanley, H. M. et al., J. Soc. Chem. Ind., (London), 21) Montecatini, Brit. 883,039 (1961).
53, 205 (1934). 22) Montecatini, Japan 38-12903 (1963).
3) Majewski, F. M. et al., Ind. Eng. Chem., 30, 203 23) Pullman Incorporated, U. S. 3, 328,469 (1967).
(1938). 24) Japan, Bureau of Industrial Technics, Japan 42-
4) Cope, C. S., J. Chem. Eng. Data, 11, 383 (1966). 2411 (1967).
5) Berkman, S. et al., "Catalysis", (1940), Reinhold 25) Japan, Bureau of Industrial Technics, Japan 43-
Pub. Corp., New York. 27206 (1968).
6) Tapp, W. J., Ind. Eng. Chem., 40, 1619 (1948); 42, 26) Lucas, H. J. et al. J. Am. Chem. Soc., 56, 460 (1934).
1698 (1950); 44, 2020 (1952). 27) Taft, R. W., Jr. et al., ibid., 73, 3792 (1951).
7) Hammer, W. F., ibid., 46, 1841 (1954); 48, 1621 28) Taft, R. W., Jr. et al., ibid., 74, 5372 (1952).
(1956); 50, 1365 (1958); 52, 962 (1960). 29) Nakaya, H. et al., Bull. Chem. Soc. Japan, 44, 1175
8) Winfield, M. E., "Catalysis", Vol. 7, (1960) Rein- (1971).
hold Pub. Corp., New York. 30) Tokuyama Soda, Brit. 1,281, 120 (1972).
9) Ogino, Y., J. Japan Petrol. Inst., 5, 487 (1962). 31) Tokuyama Soda, Ger. 2, 022,568 (1973).
10) HydrocarbonProcessing, 46, (11), 195 (1967). 32) Tokuyama Soda, Japan Open, 47-31908 (1972).
11) Hibernia Chemie, Japan, 43-26846 (1968). 33) Tokuyama Soda, Japan Open, 47-31909 (1972).
12) Europ. Chem. News, July 24, 32 (1970); March 10, 34) Tokuyama Soda, Japan Open, 47-31910 (1972).
22 (1972).