50

TECHNICAL

PAPER

Isopropyl

Alcohol

by

Direct

Hydration

of Propylene*

by Yasuharu Onoue**, Yukio Mizutani**, Sumio Akiyama**,

Yusuke Izumi** and Hirofumi Ihara***
Summary:
TokuyamaSoda has developeda new processfor direct hydration of propyleneto
isopropanolin liquidphase. Thisprocessemploysa highly active and selectivecatalyst system
which essentially comprisesan aqueoussolutionof polytungstencompoundswithin a selectivepH
range.
Thefirst commercial
plant, havinga capacityof 30,000 metrictons of isopropanolper annum,
has beensuccessfullyin operationsince the beginningof June 1972 at TokuyamaSoda Co., Ltd.
The features of the processare simpleness,low valuefor propyleneconsumptionand freedom
from environmentalpollutionproblems. These advantagesmake TokuyamaProcess byfar more
economicalthan the conventionalprocessfor the manufactureof isopropanol.
1

Introduction
Isopropanol

is an important

pylene
in petrochemical
as solvent, dehydrating
well

as a

and

other

Since

base

industry.
It is used
agent and disinfectant
as

the

manufacture

first

in

commercial

1920,

most

of acetone

production

methods

propylene
to isopropanol
the use of concentrated
stage

of pro-

compounds.

the

propanol

for

derivative

have
sulfuric

esterification-hydrolysis

cess, although

resulting

for
been
acid

of isohydrating

process.

This

pro-

processes

in one step
studied

of direct

hydration

in the presence

in order

the sulfuric

acid

conversion

of

to avoid
process

of propylene

of catalyst
the

and

propylene

have

to obtain
to

been

disadvantages
the

isopropanol

of
rapid
with

the lowest possible amount

of by-products.
It is quite lately, however,
that some economical direct
isopropanol

hydration
production

Now,

the

with

economic
by

direct
Recently

new
*
**

rising

importance
hydration

processes
have
market

process

been
Soda
for

commercial
developed.

of isopropanol,

of isopropanol
has

Tokuyama

economical

for
been

well

of

Propylene

Reaction
Direct

hydration
presence

lowing

of propylene

of catalyst

reversible

is carried

according

out

to the fol-

equation:

C3H6+H2OCH3CH(OH)CH3

acid.

Many

Hydration

in the

conversion

of propylene,
has the problems
of severe
corrosion and disposal or reconcentration
of dilute
spent

2
2.1

based
on
in a two-

in substantial

propylene to isopropanol in liquid phase. The

first commercial plant of this process, having a
capacity of 30,000 metric tons of isopropanol
per annum, has been successfully in operation
since the beginning of June 1972 at Tokuyama
Soda Co., Ltd.

the

production
recognized.

has

developed

direct

hydration

of

Received December 9 , 1972.

Research & Development , Tokuyama Soda Co.,
Ltd. (1-1, Mikage-cho, Tokuyama 745)
*** Development & Marketing , Tokuyama Soda Co.,
Ltd. (1-4-5, Nishi-Shinbashi, Minato-ku, Tokyo,
Japan)

The reaction is exothermic, and the heat of

reaction calculated from available thermochemical
data1) is about 12kcal/mol over a range of 400
to

600K

in

vapour

phase.

The equilibrium constants by direct measurements2),3) for hydrating propylene are reported
as follows:
1og10Kp=(1950/T)-6.06(vapour
phase)
1og10Kc=(2045/T)-5.08(liquid
phase)
For the hydration with liquid and vapour
phases simultaneously present, the equilibrium
compositions of both phases can be estimated4)
by thermochemical data, together with vapourliquid equilibrium data.
Although the formation of isopropanol is favored by low temperatures and high pressures,
optimum combination of reaction conditions is
selected in consideration of both rate limitation
and equilibrium limitation.

The major by-products in the direct hydration

of propylene are di-isopropyl ether, n-propanol
Bulletinof The Japan PetroleumInstitute

Onoue, Mizutani,
and

propylene

Akiyama, Izumi and Ihara:

oligomers.

propylene
water
to

Catalyst
and Process
In commercial
realization

2.2

it is important

of direct

to develop

active

processes
suitable
for the
of the catalyst
systems.
In recent
years,
various
cesses5)9)

been

for

direct

effective

of

and

for a better

Process

to

vapour-phase
direct
mineral
acids such
acids

1 through

on

to

to

are
he-

silica

statc.

The

in

and

or

molar
at

under

a
the

VEBA

diatomaceous

oxides.
carried

bed

maintain

proposed

in vapour

The vapour-phase
has the substantial
of

propylene

water at a mole
between
10 and

ratio of
15 over

at

a temperature

pressure

from

oxide

This

phase

and

of

200

in the presence
is widely

from

used

to

230

as

an

water,
effective

catalyst14).
Soda
which

catalyst
liquid-phase

has

also

proposed

comprises

an

zirconium

is suitable

for both

processes.

The

active
tung-

vapourexamples

of 0.52.0:

pressure

from

from

10

in

gaseous

reactants

recently

to

em-

production
phosphoric

phase.

direct hydration,
however,
disadvantage
of low converper

pass,

for

example

56%,

resulting in a high recycle rate.

Consequently,
the use of a propylene concentration
of 99%
or more is required for the feed. Moreover, the
disadvantages inherant to supported mineral acid
catalysts are decrease in hydration activity and
the incidence of corrosion13) on the metal surfaces in contact with the product owing to mi-

Fig.

Effect of Temperature
version to Isopropanol
Hydration

on Propylene
Conin Vapour-Phase

gration and depletion

of the acid.
In order
to avoid these difficulties, it is necessary to regenerate the catalyst
duct.
The disadvantages
concomitant
recycle

and

to neutralize

the pro-

of the low conversion and

problems in vapour-phase

processes are overcome by the direct hydration

in the presence of liquid water, since the propy
lene conversion to isopropanol is markedly raised by the increase in solubility of the product
isopropanol in the excess liquid water.
The direct hydration
with a solid catalyst
under a high pressure at a high mole ratio of
water to propylene can be preferably employed
to obtain high per pass conversions of propylene.
The reaction is generally carried out by passing
Volume

15, No.

1, May

1973

Fig. 2

to

300atm.

of liquid

earth,

temperature

proccss10)12)

51

out by passing

ratio

ployed
in commercial
isopropanol
is based on the use of a supported
acid catalyst

typical
the

catalyst

260

some

bed
a

component

state.

for

propylene
the

65atm

sion

have

hydration
of propylene
as phosphoric
acid and

and solid acids of metal

The reaction
is generally
and

and

Tokuyama

understanding

review

hydration
processes briefly.
The catalysts
most widely

steam

270

catalyst15)17)

necessary

of Tokuyama

teropoly

catalyst

tungsten

pro-

propylene

and liquid
propylene

For the hydration

proposed.

It seems

180

and

application

catalysts

hydration

the

hydration,

catalysts

of Propylene

Isopropyl Alcohol by Direct Hydration

Effect of Pressure on Propylene

to Isopropanol
in Liquid-Phase

Conversion
Hydration

Onoue, Mizutani,

52

of the

results

zirconium
liquid

of propylene

tungstate

phase

respectively,

catalyst

are

shown

in

comparison

hydration

with

the

in vapour

phase

and

in Fig.

liquid-phase
hydration
over
talyst by Zabor
et al.18)
The
the

use

of insoluble

difficulties

depletion
with

supported

the severe

acid

eliminates

on

Rate

of Propylene

ca-

migration

and

in the hydration

catalysts.

hydrothermal

Effect of Anion
Hydration

of

catalysts

take place

2,

data
oxide

remarkable

of acid which

Fig.

the

tungsten

solid

of the

1 and

with

Table

Akiyama, Izumi and Ihara:

However,

conditions

under

in the liquid-

phase hydration
under
high pressure,
gradual
depletion
or crystallization
of the effective
components of catalyst
both the decrease
operating

is inevitable,
in hydration

troubles

will

and consequently
rate and some

occur.

Recently,

Deut-

sche Texaco
has developed
a trickle process19)
in vapour
and liquid
phases
applying
cation
exchange

resins

ditions

of

of the

main

the

as

of

of

catalyst

In

sulfonic

in

order

causes

to overcome

hydration

water

acid

con-

atm.

One

is probably

groups

the

of

the

irreversible

loss

activity.

fixed bed processes

phase

milder

60100

in this process

which

catalytic

under

and

problems

hydrolysis

resin

catalysts

130150

can

with

be

the

difficulties

with solid catalysts,

the solid

in

catalyst

employed20)22).

the

the liquid

In

dispersed

this

process,

propylene
is treated
with water at an elevated
temperature
and pressure in the presence
of an
aqueous
suspension
of fine particles
of the catalyst.

Although

high

space-time

on catalyst

are obtainable

cess,

some

operational

and

circulation

not

be
and

scribed

Soda

ments,
and
liquid-phase
for

difficulties

of separation

suspended

particles

examined

in the

through

the

typical

its own

catalyst

would

production

of

be

most

isopropanol.
of aqueous

been

ofTered

in

patents23)25)

However,

recent

these systems

of low

selectivity

aqueous

solution

stabilities
and

insoluble

de-

experi-

for

have

of

catalyst

sulfate,

ferric

molybdic
hydroxides

acid

the

sulfate,

case

catalyst

components,

high

cahave

such

chromium

are

hydrolyzed

temperature

to

concentration,

and
as
sulto
and

known

mechanisms26)29)

no
on
in

dilute

the effect
hydration

acid

interpreted

of an

activated

solution

by

Direct

Catalyst

System

catalyst

solution

This
talyst

assuming

Hydration

essentially

employed
comprises

kinds

small,

is also

components

propylene
very

are

intermediate
the

anion.

Process

in Tokuyama
a dilute

aqueous

of polytungsten

a selective
pH
is highly
active

for hydrating

system

an

containing

system

of definite

pounds
within
talyst
system
selective

anions

is considerably

complex

Tokuyama

3.1

counter

of the polyatomic
anion
on both the
rate and the activation
energy is pro-

bably

the

aqueous
acid,
to the acid
have

very

and

of

effect on the rate.

Since the medium
effect
the activity
coefficient
of each
component

Process30)34)

of

the

olefin
hydration
in very dilute
the hydration
rate is proportional

The

in

halide

which
at

solution

the disadvantages

hydration

of copper

profitable
Some

in a state

fate

disadvan-

extensive

systems

aluminium

can

processes

talyst

low

pro-

attained
to a conclusion
that
the
direct
hydration
with an aqueous

of

the

fully

difficulties

above

solution

by the suspension

the

According

based

avoided.

Tokuyama
tages

of

yields

pressure in aqueous solution.

Tokuyama Soda studied systematically the catalytic activities and stabilities of aqueous solutions
of various acid compounds in the direct hydration
of olefins, and finally developed an excellent
catalyst system of a stable aqueous solution under
high temperature and pressure. It was found
from the study that the rate of hydration was
markedly increased by the presence of some
kinds of polyatomic anions as shown in Table 1.
The activation energy of the propylene hydration with the catalyst solution of polyatomic
anions is about 24kcal/mol which is 6kcal/mol
higher than that in the case of the catalyst solution of sulfate anions.

stable

strongly

com-

range.
This caand remarkably
to isopropanol.
because
resistant

Bulletin of The Japan Petroleum

the

ca-

to hyInstitute

Isopropyl

Alcohol

drolysis.

Such

by Direct

high

Hydration

stability

53

of Propylene

of the

catalyst

sys-

at all times

in operation

Because of large
by the following

of

which

cause

kinetic

the decomposition
of the catalyst.
The catalyst
life is, therefore,
very long in continuous
operation.

where

tem is well
by

the

maintained

careful

Tokuyama

control

Process

gives,

poisons

moreover,

higher

excess of water, the rate is given

equation
via a pseudo-first
order

treatment:

=kl(Cp-Ci/kl)=kg(Pp-Pi/Pwe.kg)

per

ki, kg:

rates

of conversion

of

propylene

pass conversions
contact
between

of propylene
owing to intimate
dissolved
propylene
and
the

isopropanol

catalyst

in the

and at unit pressure

of propylene
vapour phase, respectively.

solution

liquid

phase

than

in the

case where solid catalyst

systems are employed.
Fig. 3 shows an example
of the experimental
results of propylene

hydration

In

the

kuyama

hydration
catalyst

between
aqueous
troled

by the

is at

all

of propylene

of propylene

system,

dissolved
solution.

step,

maintained

between

vapour

equilibrium

phases,

in

with

the

pp, Pi:

propanol
in solution,
partial
pressures
of

takes

place

Pwe:

equilibrium
This

phases.

basic

rate

The

Process
flow

shown

in

Liquid

heated
and

equation

Description
scheme
of
Fig.

by heat

pressure
can

and

to

15, No. 1, May

1973

of water
ap-

Tokuyama

liquid
water.

Process

is

reactor

The
and

fed

reaction

between
aqueous

catalyst

at

effluent

240270
takes

dissolved
solution

is withdrawn

to a

solution
is pre-

with the reactor

operating

The

phase

and
catalyst
column

place

propylene
containing
from

the

reactor
flashed

and cooled by heat exchange

and then
under reduced pressure in a gas separator

where

the

the

of

exchange

the

isopropanol
Data obtained with Tokuyama catalyst
system at 200kg/cm2.G.
Fig. 3 Effect of Temperature on Propylene Conversion to Isopropanol in Liquid-Phase
Hydration

Volume

res-

be suitably

is preheated

150250atm.

in the

Diagram

phase,

4.

propylene

fed

and

Flow

iso-

phase.

reactor
under
pressure.
The
recovered
from
the azeotrope

and

plied to calculate
conversion
or space-time
yield
in process
design
and
economic
evaluation.
3.3

Fig.

and

respectively.
propylene
and

vapour

partial

in vapour

distribution
liquid

in

pectively.
equilibrium

in

liquid

of propylene

isopropanol

water
in an
rate
is con-

con-

solution,

respectively.

concentrations

To-

unit

in

constants

Cp, Ci:

the

and

vapour

at

propylene

reactor.

provided
in

of

flow

reaction

propylene
and
The hydration

reaction

times

the

Ki, Kg:

with the Tokuyama

catalyst
system
by a continuous
3.2 Kinetics
of Hydration

in solution

centration

to

unconverted

solution

Tokuyama

is

Prricrs,

separated

propylene
and

dissolved
recycled.

in
The

Onoue,

54

liquid is sent to the azeotropic column, from

where azeotropic mixture of isopropanol and water
is drawn off and sent to further distillation steps
for purification and dehydration. The aqueous
solution containing catalyst from the bottom of
the azeotrope column joins with fresh water and
is recycled to the reactor. The azeotrope alcohol is freed of the light impurities in the first
rectifying column and then dehydrated in two
further columns with benzene as the dehydrating agent. To obtain a high grade isopropanol
(99.99% purity), another additional distillation
step is necessary.
Under the optimum reaction conditions, the
range of propylene conversion per pass is about
6070%
on

the

and
converted

selectivity
propylene

to

isopropanol
is as

much

based
as

98

99%. The major by-product is di-isopropyl

ether.
In Tokuyama Process, both the spent gas
from the reactor and all the by-products drawn
off at the purification section are completely
utilized as fuel for heating in the system.
3.4 Features
of Process
Tokuyama Process has a number of advantages
based on its own catalyst system and process
design. The features of the process confirmed
in commercial operation are as follows:
(1) The catalyst system comprises a homogeneous dilute aqueous solution which maintains high
activity and excellent selectivity for hydrating
propylene to isopropanol.
(2) The catalyst solution is so highly stabilized that it is circulated repeatedly in the reaction
system without any additional treatments. Catalyst 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
rate of propylene, and consequently this process
does not require highly concentrated propylene
feed. Commercial propylene of about 95% concentration is normally used.
(5) The amount of by-products is remarkably
small because the reaction takes place in an
aqueous solution of highly selective catalyst . Organic acids and aldehydes are hardly detectable
in the reaction product . A high grade isopropanol is easily obtained at the purification

Mizutani,

Akiyama,

Izumi

and

Ihara:

section.

(6) Since the reaction is carried out in aqueous

solution, the heat loss incidental to evaporation
and condensation of water can be avoided.
(7) Because of absence of corrosion in the system, easy operation and maintenance of equipments are possible.
(8) The process is simple. It is also a completely closed system free from waste substances,
and consequently the process can clear all the
environmental protective regulations.
3.5 Quality of Product
Trypical data of the product isopropanol obtained in Tokuyama Process are given in Table 2.
3.6 Economics
The economics of Tokuyama Process are shown
in Table 3. They include the entire processing
of propylene to 99.99% isopropanol.
3.7 Other Applications
Tokuyama Process is also applicable to the
economical production of ethanol and butanols.
4

Conclusion
Besides the low value for propylene consumption, simpleness of process and freedom from
enviromental pollution problems by nature of
the process itself make Tokuyama Process by far
more economical than the conventional process
for the manufacture of isopropanol.
In the recent trend of the process for isopro-

Direct

Table

Typical

Table

Economics

Liquid-Phase

Properties

of Product

of Tokuyama

Hydration

Soda

Process

Bulletin of The Japan

Petroleum Institute

Isopropyl Alcohol by Direct Hydration of Propylene

55

panol production
toward
direct hydration,
Tokuyama
Soda
will greatly
contribute
to the

13)
14)

proceeding
of this
its own commercial

15)
16)
17)
18)

trend
plant.

through

experience

in

References

1)

2)
3)
4)
5)
6)
7)
8)
9)
10)
11)
12)

Volume

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