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TECHNICAL
PAPER
Isopropyl
Alcohol
by
Direct
Hydration
of Propylene*
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
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
the
production
recognized.
has
developed
direct
hydration
of
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.
Onoue, Mizutani,
and
propylene
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%,
Fig.
Effect of Temperature
version to Isopropanol
Hydration
on Propylene
Conin Vapour-Phase
and
to neutralize
the pro-
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
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
proposed.
It seems
180
and
application
catalysts
hydration
the
hydration,
catalysts
of Propylene
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
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.
milder
60100
in this process
which
catalytic
under
and
problems
hydrolysis
resin
catalysts
130150
can
with
be
the
difficulties
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
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
stable
strongly
com-
range.
This caand remarkably
to isopropanol.
because
resistant
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
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
solution
liquid
phase
than
in the
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
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-
The
phase
and
catalyst
column
place
propylene
containing
from
the
reactor
flashed
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:
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
the
and
converted
selectivity
propylene
to
isopropanol
is as
much
based
as
98
Mizutani,
Akiyama,
Izumi
and
Ihara:
section.
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
Petroleum Institute
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
1973
19)
20)
21)
22)
23)
24)
25)
26)
27)
28)
29)
30)
31)
32)
33)
34)