Chemical Engineering

Science,
Printed in Great Britain.

Vol.

43, No.

KINETICS

OF

G.H.

-Department
Groningen,

R, pp. 2161-2168.

THE

Graaf,
and

rxl0%2509/88
$3.00+0.00
Pergamon Press plc

1988.

THREE

J.G.M.
A.A.C.M.

of
Chemical
Nijenborgh
16,

PHASE

XBTHANOL

Winkelman,
Beenackers-.

E.J.

Engineering,
The
9747
AG Groningen,

SYNTHESIS

Stamhuis

State
University
The
Netherlands

of

ABSTRACT
starting
from
carbon
The
kinetics
of the
three-phase
methanol
synthesis,
Cu-Zn-Al
catalyst
carbon
dioxide
and
hydrogen
over
a commercial
monoxide,
as
the
slurry
liquid,
were
studied
in
a well-mixed,
suspended
in
squalane
and
T = 210
- 260
OC.
A kinetic
agitated
slurry
reactor
at p = 15 - 40 bar
mechanism
and
three
based
on
a
dual-site
adsorption
model
is
selected,
water-gas-shift
methanol
from
CO=
and
the
reactions:
methanol
from
CO,
is the
most
important
reaction
It turns
out
that
methanol
from
CO=
reaction.
This
kinetic
model
gives
a good
agreement
with
under
three-phase
conditions.
the
experimental
results.
Keywords:
kinetics,
methanol
synthesis,
slurry
reactor,
three-phase
systems.
INTRODUCTION
In
Chem
Systems
(Sherwin
&
Frank,
1976;
Sherwin
&
Blum,
1978)
1976
described
a three
phase
methanol
synthesis
process.
A three-phase
fluidised
bed
was
used,.
in
which
small
catalyst
particles
were
suspended
in an
inert
paraffinic
liquid.
Chem
Systems
claimed
as
advantages
in
with
comparison
quenched
bed
reactors:
excellent
conventional
temperature
control;
high
reaction
rates;
low
recycle
ratio
and
efficient
energy
economy.
Despite
Chem
Systems
based
its
conclusions
on
extensive
sets
of
bench
scale
experiments
and
pilot
plant
experiments,
the
kinetics
of
methanol
the
three-phase
synthesis
were
described
with
simplified
rate
expressions.
The
same
holds
for
other
publications
on
three
phase
methanol
synthesis
(Kafarov
et
a1.,1982;
Brown,
1984;
Ledakowicz
et al.,
1984,
a; Galtier
et a1.,1986).
However,
it is
most
likely
that
the methanol
synthesis
reaction
kinetics
for
the
three-phase
system,
will
not
be
less
complex
as has
been
found
for
the
conventional
twophase
methanol
synthesis
(Graaf
et al.,
a).
The
objective
of this
paper
is to
present
the
kinetics
of
the
three-phase
methanol
synthesis
based
on
an
extensive
set
of accurate
kinetic
experiments.
THEORY
In three-phase
methanol
synthesis
the
overall
kinetics
are
determined
by
the
following
steps:
1. Mass-transfer
from
gas-phase
to gas-liquid
interface.
2. Mass-transfer
from
gas-liquid
interface
to liquid
bulk.
3. Bulk
liquid
transport.
4. Mass-transfer
from
liquid
bulk
to liquid-solid
interface.
and
diffusion
in the
porous
catalyst.
5. Reaction
The
reactants
undergo
steps
1, 2, 3 and
4 in order
to reach
the
catalyst
where
reaction
and
diffusion
take
place
(step
5).
Since
we
are
dealing
with
equilibrium
reactions
in
methanol
synthesis,
we
should
also
look
at
the
reaction
products,
which
undergo
the
same
transport
steps
but
in the
opposite
direction.
In practice,
not
all
transport
resistances
are
important.
In this
study
experiments
were
designed
such
that
all
mass
transfer
resistances
(including
intra-particle
diffusion
limitations)
were
negligible
(see
appendix
A).
This
makes
reaction
kinetic
investigations
much
simpler,
because
we now
may
assume
that
the
gas
phase
and
the
liquid
phase
are
in thermodynamical
equilibrium,
according
to:
fG
=
fL
(1)
i
1
With
this
eqn.
in
mind
it
would
be
logical
to
base
the
kinetic
rate
expressions
on partial
fugacities.
However,
in engineering
calculations
(e.g.
material
balances)
it
is
preferred
to
use
concentrations
instead
of
fugacities.
Therefore
the
gas-liquid
solubilities
of CO,
CO=,
Hz,
CH~OH
and
Hz0
in the
slurry
liquid
(squalane)
are
needed.
In the
temperature
range
of
interest
in
this
study
(210
- 260
"C)
and
for
squalane
as
the
solvent
the
Henry
coefficients
as
taken
from
Graaf
et
al.
(to
be
published,
b)
can
be
very
well
approximated
by:
Hco-r.X
Hcoz-rp
Hnz-*q
HCH30l.s-~p
HHSO-PQ
With
fugacities
For
previous

=
=
=
=
=

0.175
0.402
0.0782
1.49
0.330

exp(638/RT)
exp(-6947/RT)
exp(4875/RT)
exp(-17235/RT)
exp(-8633/RT)

I:{
(4)
I:;

these
equations
the
kinetic
rate
expressions
based
on
partial
can
be transformed
to expressions
based
on liquid
concentrations.
the
conventional
(two-phase)
methanol
synthesis
we
showed
in
a
paper
(Graaf
et al.,
a) that
the
following
reactions
take
place.

2161

G2

G. H. GRAAF~~~~.

2162

A:
B:
c :

CO
coz
COZ

+
+
+

2H2
Ha
3 Hz?

=
_=
=

CH30H
Cb
CHzzOH

+
+

Ha0
Hz0

(9)

Kinetic
rate
expressions,
all
based
on a dual-site
LangmuirHinshelwood
were
derived
for
these
three
reactions.
mechanism,
Assuming
that
adsorption
and
desorption
were
not
steps
ratecontrolling
48
models
kinetic
of
kinetic
rate
expressions
(combinations
for
reactions
A,
B and
C)
were
Based
on
experimental
derived.
results,
and
statistics
a physico-chemical
constraints
test
a final
kinetic
model
could
be selected.
In this
study
we assume
that
the
same
reaction
schemes
are
applicable
for
the
three-phase
kinetics.
Therefore,
the
theoretical
approach
in the
present
kinetic
study
is
very
similar
to the
one
we
presented
earlier
for
the
twomethanol
synthesis
kinetics
(For
details
see:
Graaf
et
,;a=
(g as-solid)

- ,a).
EXPERIYEWTAL
- Equipment.
The
study
was
carried
out
with
a well-mixed
agitated
reactor,
see
Figure
1.
Both
the
liquid
phase
(squalane:
2.6.10.15~~~~~~
hexamethyltetra-cosane)
and
the
dispersed
solid
phase
(crushed
and
kept
in batch.
For
Haldor
Topsoe
MK
101
catalyst,
40 pm
< d,
< 60 urn) were
properties
of the
catalyst,
see:
Dybkjaer
(1981).
Only
1.50
g of catalyst
in
130
g squalane
was
used
to assure
that
gas-liquid
mass-transfer
limitations
Variation
of the
stirrer
speed
from
8.3
s-1
to 33.3
8-l
did
not
were
absent.
the
observed
production
rate,
change
thus
confirming
external
that
mass-transfer
limitations
and
deviations
from
perfect
mixing
were
negligible
(see
Appendix
A).
The
reactor
vessel
(l)_, made
of
stainless
steel
316
was
connected
to a
magnetic
stirrer
(2) and7;ightenezhzy
an annealed
copper
r;;;
(3).
z&e
z;z;
diameter
reactor
was
inner
height
was
mm
mm,
approximately
one-half
was
occupied
by the
slurry.
To reduce
the
freeboard
a
metal
block
(4) was
placed
in the
upper
section.
It contained
spacings
to the
gas
outlet
and
for
the
stirrer
shaft
(5).
A twelve
bladed
turbine
stirrer
(6)
with
d = 40 mm,
four
vertical
baffles
(7) with
d = 7 mm
and
a
conical
foam
separator
(8)
placed
on
the
stirrer
shaft,
were
the
internals.
The
reactor
was
heated
electrically
by
a heating
coil
(9)
and
insulated
with
glasswool
The
reactor
was
with
a
temperature
measured
Pt-100
resistance
(10).
thermometer
(11).
A porous
filter
(12)
just
below
the
stirrer
was
used
for
the
gas
distribution.
A filter
(13)
was
placed
in the
gas
outlet
to prevent
liquid
or
catalyst
to
leave
the
reactor.
The
present
reactor
was
placed
in
the
same
equipment
as described
by:
Graaf
et al,
a).
For
details
on chemical
analysis
see
also
that
paper.
- Measurements.
Preliminary
experiments
showed
that
the
catalyst
activity
with
changed
time.
To
correct
for
these
activitychanges,
"standard"
were
carried
out
experiments
regularly.
A
broad
range
of
experimental
was
conditions
investigated
to
obtain
a
complete
picture
of
the
reaction
kinetics,
see:
Table
1. It was
assumed
that
the
catalyst
activity
decreased
increased)
linearly
from
day
to
between
succesive
"standard"
(or
day
experiments
(usually
carried
out
once
per
week).
RESULTS
- Catalyst
Activity.
gas
flowrates
(see
activity
catalyst
varied
experiments
directly
related
to
activity
is related
constant
as defined

The
"standard"
experiments
were
carried
out
at various
Table
1).
Therefore,
and
because
of
the
changes
in
the
amounts
of
the
methanol
and
water
formed
in
these
too.
Consequently,
the
catalyst
can
activity
not
be
the
reaction
rate.
To cope
with
this
problem
the
catalyst
to the
pseudo
first
order
(with
respect
to hydrogen)
rate
byt

(10)
kps(fH,fCH&,H
/(fCD
fRzKplP))
rCH
OH
=
AlthouGh
the
validity
of eqn.
10 is restricted
to a small
range
of
conditions
only,
it contains
a correction
for
the
reverse
reaction,
thus
providing
a rather
safe
determination
of the
catalyst
activity.
We further
assumed
that
the
activity
corrections
are
the
same
for
both
water
and
methanol.
The
latter
is justified
by the
results
of our
study
on the
conventional
low-pressure
methanol
synthesis
with
the
same
catalyst
(Graaf
et
The
chemical
equilibrium
constant
in eqn.
10 was
taken
from
Graaf
et
al.,a).
al.
(1986).
The
fugacities
were
calculated
using
the
Soave-Redlich-Kwong
eqn.of
state
(Soave,
1972).
In Figure
2 the
relative
catalyst
activity
(k',,/k',,ct-o,)
is plotted
as
a function
of time.
It should
be noted
that
t=O
in this
plot
corresponds
to 3
weeks
at operation
after
initial
catalyst
activation.
All
measured
reaction
rates
were
arbitrarily
corrected
to the
activity
at t=O.

Kinetics of the three phase

G2

methanol

2163

synthesis

- Parameter
Estimation
and
Model
Discrimination.
The
experimental
results
of
feeds
2 - 7 (144
experiments)
were
used
for
the
parameter
estimation.
For
a
description
of the
calculation
methods
(see
Graaf
et al.,
a).
In a first
series
of computations
the
parameter
estimation
was
carried
out
for
all
48
reaction
kinetic
models
at each
temperature.
Based
on the
X2-test
(Bartlett,
1937)
35 models
could
be rejected
at a 95% confidence
level.
In this
test
the
variances
of the
methanol
reaction
rates
were
used.
The
remaining
models
were
employed
in the
parameter
estimation
for
all
4 temperatures
simultaneously,
assuming
all
parameters
followed
an Arrhenius'
temperature
dependency.
Based
on the
X2-test
7 models
were
retained
at a 95%
confidence
level.
It turned
out
that
for
all
these
7 models
the
concentrations
of free
sites
2 (on which
H2 and
Hz0
are
adsorbed)
were
negligible,
just
as was
observed
in the
modeling
of the
two-phase
kinetics
(Graaf
et al.,
a).
The
parameter
estimation
was
repeated
with
the
resulting
simplified
model
equations
and
5
models
remained
at a 95%
confidence
level
based
on the
@-test.
These
models
are
listed
in Table
2.
For
these
5 models,
a thorough
residual
analysis
was
carried
out.
First
of all
the
residuals
should
be normally
distributed
around
zero.
This
was
the
residuals
for
both
the
methanol
true
for
all
5 models.
Furthermore,
production
rates
and
the
water
production
rates
should
have
no trending
effects
as a function
of any
of the
independent
variables
or the
measured
Models
A2BlC4,
A2B2C4
and A3B2C3
showed
no trending
effects.
The
quantities.
residuals
of the
methanol
reaction
rates
of models
A3BlC4
and
A3B2C4
have
see
Figures
3 and
4.
trending
effects
as a function
of the
total
pressure,
In order
to discriminate
between
these
5 rival
models,
the
results
of
These
results
were
obtained
with
a different
batch
of
feed
8 were
used.
these
results
are
not
used
for
the
parameter
estimation.
catalyst.
Therefore,
For
each
run
of feed
8 (8 runs
in total)
the
activities
for
both
methanol
and
using
one
of the
rival
models.
The
activity
is
water
can
be calculated,
defined
as being
the
atio
of the
experimental
reaction
rate
and
the
For
the
correct
model
the
activities
for methanol
calculated
reaction
rate.
and
water
should
be equal.
The
mean
values
of these
activities
and
the
corresponding
standard
deviations
are
listed
in Table
3. From
these
results
it can
be seen
that
model
A3BZC3
gives
the
best
results,
thus
completing
the
model
selection.
It should
be noted
that
independent
from
the
present
study
the
same
model
was
selected
for
the
two-phase
methanol
synthesis
(Graaf
et
al.,
a).
Parity
plots
of the
observed
and
calculated
reaction
rates
for
methanol
and
water
are
presented
in Figures
5 and
6. These
Figures
clearly
show
the
excellent
agreement
between
model
calculations
and
experimental
results.
The
agreement
between
model
and
experiment
is even
somewhat
better
probably
because
of the
here
than
obtained
in the
two-phase
kinetic
study;
separate
measurement
of the
catalyst
activity.
In terms
of partial
fugacities
model
A3B2C3
now
results:
kps,A3KCo(fCof;;3
r&H 3 OH ,A3

(11)
+
(l

KCOfCO+

KCOnfCOz)(fHz+

kps,B2KC0z(fC0~fHz

KCOfCO+

KCO,fCO,)(fH,

kinetic

k'ps,B2
k'ps,C3
KCO
KCOa
KHzO/

KHz

4
(KH,O'KH,'fH,O)

fCHsOHfHnO/(f~;=Kp~o))
(=

=
(l

k'ps,A3

HsO)

(12)

k&3,C3KCOn(fCO~fiX2

The

%f

/ Kpz")

fH~OfCO
4

(I

C3

(KH,O'KH,)

';r2 0 , B2

&30H,

f,H3,,/(fH~Kp,-))

and

KCOfCO

the

KCOa

adsorption

co2 )(fB;+

constants

are

(2.12

0.23)

lo=

exp((-98800

(2.58

0.66)

lo==

exp((-220000

(1.09

0.05)

101

exp((-48300

(5.15

1.16)

lo-==

exp((91500

(7.83

1.29)

lo-=

(2.30

1.46)

1O-12

The Arrhenius'
Using
equations
concentrations

diagrams
(2) yielding

(KH,G/KBz'fH
described
f

Cl)

(13)

by

500)/RT)
f

';I2,0

(14)

llOO)/RT)

(15)

200)/RT)

(16)

lOOO)/RT)

(17)

exp((41000

700)/RT)

(18)

exp(114100

2100)/RT)

(19)

are
given
in Figures
7 and
8.
(6) the
model
can
be transformed
the
following
results:

into

terms

of

liquid

2164

G. H. GRAAF~~~~.
*

*
kps,A3KC0

=&I

(c

-'=
COCHs

G2

cCH,GR/(cH~

Kc=)

on , A3

(I

*
KCOCCO

*
KCOzCC0z)(CH2+

(20)
4

*
(KH,O

/K;!+R=O)

*
=

'fr2 0 , 32

k'ps,s32Kcop *

*
(l
kf

(cCOzcH=

cH,Oc,&

KNOCKS

KCGICCOa)(CHp+

Kc=)

42

(KHa6'KHa *

(21)

4
)cHzO)

3,s

ps,C3KC02(CCO~CH2

C~H30HCHaO/(cH~'~c~))

=
=&H 3 OH I C3
(l
=
=
=

KCX
Kcz
Kc3
The
original
from
Graaf
*
k'ps,A3
k'*
ps,32
*
kbs,C3
*
KCO
*
I%02
Kg,/

1.72
5.81
Kc=

et

*
KCOCCO
lo-==
10
Kc2

relationships
al.
(1986).

*
KCOzCCOa)(CH%

(=
+

(K;,o/K;%

0 , C3)(22)

'A

)cH,O)

exp(126011/RT)
exp(-33760/RT)
(25)
for

the

chemical

equilibrium

constants

were

1.66

105

exp(-93925/RT)

(26)

7.21

10"

exp(-215130/RT)

(27)

8.52

lo-=

exp(-43425/RT)

(28)

9.01

10-1'

exp(92138/RT)

(29)

3.15

IO-5

exp(34053/RT)

(30)

2.71

lo-==

exp(103030/RT)

(31)

=
=
=

K&

taken

Aspects
of the
Three
Phase
Methanol
Svnthesis
and
Comparison
with
the
Two
Phase
Low
Pressure
Methanol
Synthesis.
In Figure
9 typical
reaction
rates
of both
methanol
and
water
are
plotted
The
results
of
feed
4 (see
Table
1) are
as a function
of
the
gas
flowrate.
corrected
with
the
methanol
activity
according
to Figure
used
in this
plot,
high
gas
flowrates
the
reaction
rates
for
methanol
and
water
are
very
2. At
This
indicates
that
reaction
C is the
most
important
often
almost
identical.
conditions.
In
other
words:
methanol
is
almost
reaction
under
these
At
lower
flowrates
the
water-gas-shift
reaction
completely
formed
from
CO=.
is pushed
over
its
chemical
equilibrium
due
to reaction
C. This
effect
can
be
where
the
amount
of water
related
to
the
water-gas-shift
seen
in Figure
10,
equilibrium
is plotted
as a function
of the
gas
flowrate.
Though
we observed
this
behaviour
in the
two-phase
(low-pressure)
methanol
synthesis
too
(Graaf
higher
"overshoot"
of
the
water-gas-shift
equilibrium
et
al.,
a),
a much
This
is caused
by the
fact
that
occurs
in the
three-phase
methanol
synthesis.
reactions
A
and
B
are
lower
relative
to
reaction
C
in
the
the
rates
of
three-phase
methanol
synthesis
than
in the
two-phase
system.
For
comparison,
results
are
plotted
for
both
the
two-phase
kinetics
the
three-phase
kinetics
in Figures
11,
12,
13 and
14.
(Graaf
et al.,
a) and
It
can
be
seen
from
Figures
11
and
12
that
the
total
production
rates
of
methanol
are
quite
comparable
for
the
two
cases.
However,
in
the
two-phase
system
methanol
is primarily
formed
from
CO,
while
in the
three-phase
system
is the
most
important
carbon
source.
Figure
13 shows
the
"overshoot"
of
coa
the
water-gas-shift
equilibrium
for
both
the
two-phase
and
the
three-phase
methanol
synthesis.
Apparently,
the
"overshoot"
for
the
three-phase
system
is
almost
four
times
larger
than
the
"overshoot"
for
the
two-phase
system.
In
figure
14 the
mole-fractions
of methanol
and
water
are
given
for
both
cases.
Another
important
difference
between
the
kinetics
in
the
two-phase
and
the
three-phase
system
is the
influence
of the
temperature;
see
Figure
15,
where
initial
methanol
production
rates
plotted
as
a
the
are
function
of
temperature
for
both
cases.
Clearly,
the
three-phase
system
is
much
less
dependent
on
the
temperature
than
the
two-phase
synthesis.
In
methanol
practice,
however,
the
overall
two-phase
kinetics
will
also
be
influenced
by
intra-particle
diffusion
limitations,
resulting
in
a
lower
temperature
dependency
(Graaf
et
al.,to
be
published,
c).
Though
our
investigations
and
the
resulted
in
an
identical
kinetic
model
for
both
the
two-phase
three-phase
methanol
synthesis,
the
comparison,
given
above,
shows
remarkable
differences
both
in
the
relative
contribution
of
each
of
the
three
overall
reactions
(A, B and
C) involved,
and
in the
influence
of reaction
temperature
on
(initial)
methanol
formation
rate.

Kinetics of the three phase

G2

methanol

synthesis

2165

CORCLUSIONS
In studying
catalytic
methanol
formation
from
synthesis
gas,
periodically
the
catalyst
activity
significantly
contributes
to
an
remeasuring
of.
excellent
agreement
between
experimental
results
and
model
calculations.
kinetic
experiments
it
that
the
From
an
extensive
set
of
follows
three-phase
methanol
synthesis
can
be
described
with
the
very
same
reaction
rate
model
that
governs
the
two-phase
low-pressure
methanol
synthesis
(Graaf
et al.,
a).
The
kinetic
parameters
were
determined
as
function
of
the
temperature
between
210
and
260
OC.
Although
the
reaction
rate
expressions
are
the
same
for
both
the
two-phase
and
the
three-phase
methanol
synthesis,
the
various
kinetic
constants
are
quite
different.
It turns
out
that
the
methanol
from
reaction
is the
fastest
synthesis
reaction
under
three-phase
conditions,
coa
while
the
methanol
from
CO reaction
dominates
in the
two-phase
system.
we

thank

Denmark
cetelyst

Groninge",
mixtures

Haldor

for

free

Mk

101

Topsoe
supply
and
N..

The Netherlands
for calibration

reaction
rate
constant
for reaction
R
ibid
for reaction
B
ibid
for reaction
C
pseudo
first
order
reactie"
rate
constant
pseudo
first
order
reaction
rate
constant
based
"I1 volume
of catalyst
adsorption
equilibrium
constant
chemical
equilibrium
constant
based
on partial
preSS"reS
ibid
based
on concen-

k,,.,=.

n/s,

I.y*cJby,
Copenhagen,
their
methanol
synthesis
Nederlandee
csasunie,

of

for delivering
purposes.

pseudo

k',_.,,
k',,.c3

gas

REFERENCES
Bartlett,
M.S.,
1937,
Properties
of sufficiency
and
statistical
te*ts.
Proc.
Roy.
Sot. London
Ser.
A, 160,
268 - 282.
D.M.
Brown,
1984,
Modelina
of methanol
aw~thesis
in
the
liquid
-phase.
I-"d.
Chem.
En&.
SymP.
Ser.,
87, 699 - 708.
Dybk,.xc,
I., 1981,
Topsoe
merbenol
technology.
Chem.
Eco".
Engng.
RF?"., 13, (6). 17 - 25.
Galtier,
P., Pcreatiere,
A. and P. Trambouze,
1986,
Modeling
of
methanol
synthesis
in
a X-phase
fixed-bed
reactor.
Chem.
Enona.
Sci.. .
41.
4.,
_ _

f&

Graaf

of

Kinetics
synthesis.
Greaf,
G.H.,
Beenackers
methanol
solvents.
Graaf,
G.H.,
A.A.C.H.
diffusion
methanol

P.J.J.M.
1986,
Chall.

Stamhuis,

CkrnLll

E.J.

in

equilibria

Sci.,

Engng.

41,

and
A.A.C.M.
low-preseure

the

ibid

Beenackers-),
methanol

.E.

1.000,

1982,

a
SSpC3ded
Tech".,
16,
Plenum
Publ.
(198.3,.
Leda);owici,
S.,
Deckwer

of

study

Li-nlng,

w.

sang

Kotmvski,
Methanolsvnthese

1984.

(T

f
H

APPERDIX

A.

ESTIMATION

rnx

PS

OF

-TRANSFER

LIMITATIONS

In this
eqn.
k&:L' and
from
the
concentrations

(cH,
K,,
at

catalyst

298.15

K,

1.013

kg

bar)

m-=

,,,3 s-1

indicates
rate-controlling
step
of the methanol
from CO reaction
(see Graaf
et al.,
a)
ibid
of rhe water-gas-shift
reaction.
ibid
of the methanol
from CO=
reaction.
component:
co
component:
COI
component:
Ha
componenr:
CH30H
compclnent:
ILO
component:
squaLne
component:
CO, CO.,
Ii., CHxn4,
H.0,
sqU.la"e
experiment
"umber
methanol
from
CO reaction
water-gas-shift
reaction
methanol
from
CO, reaction

A4

In' s-1
bar
bar nm-1

k,,"'

days

- Subscripts
Al

diffusion
limitations.
Intra-particle
effectiveness
factor
the
Thiele
modulus
kinetic
rate
expression.
%l:OH

or

K
kg

gas phase
liquid
phase
standard
pressure
(1.013
bar)
calculated
value
indicates
that
kinetic
parameters
are based
on concenrratione

E
0
f

cl-3

MASS

of

volume

W.D.
in

NOTATION
mol
m

s-=

on

catalyst
on

- Superscripts

an*

Sherwin,
M.B.
and
D.
SlUm,
1978,
I.iquid
pIlZt*e
methanol.
EPRI-Al-693
Research
Project
317
2.
Soave,
G.,
1972,
'Equilibrium
constants
from a modified
Redlirzh-K"o"geq".of
state.
Ghan.
Engng.
SCi.,
- 1203.
27. 1197

(liquid)
concentration
particle
diameter
molecular
diffuse"
coefficient
partidl
fugacity
ma-my's
cclnstant

bar-=

effectiveness
factor
densify
tortuosity
of the catalyet
gas flowrate
at standard
&nditions

Dreiphasen-Suspensionsreektor
_ Erdiil
und
Kohle-Erdgas-Petrachemie
vereinigt
mit
Brennstoff-Chemie,
37. (IO),
462 - 465.
Ledakowicz,
s., Nettelhoff,
H. and W.-D.
Deckwer,
1984,
Gas-liquid
mass.
transfer
data
in
a
stirred
auroclave
reactor.
Ind.
Engng.
Chem.
Fundam.,
23, 510 - 512.
Reddy,
K.A.
and L.K.
Doraiswamy,
1967,
Estimating
liquid
diffusivity.
Ind.
Engng.
Chem.
Fundam.,
6, 77 - 79.
Sherwin,
M.S.
and M.E.
Prank,
1976,
Make
methanol
three
phase
reaction.
Hydrocarbon
by
Processing,
(11,.
122 - 124.

a"-1

s--I kg-=

s-=

of Catalyst
mole
fraction
porosity
Of
the

catalyst.

translation:
- 0437607.50

mol

mass--tra"s-

weighi

lll&ZhaOl

644
- 649.
English
0040
- 5795,'82/1605

based

bar-'
bar->
bar-'

bar-l

catalyst
gas constant
(8.314)
Shewood
"umber
time
temperature

submitted
to Chem.
Engng.
sci.
Smit,
K..l., Stamhuia,
e..J. and A.A.C.H.
"),
Gas-liquid
solubilities
of the
sy"thesie
compansnte
in
various
To be published.
Scholtens,
H., Stamhuis,
E.J.
and
Beeneckere
Intra-particle
"1,
limitations
in
tll*
l0W-pBLV.UE?
smtbeeis.
To be oublished.
V.V.,-Ivanov,
V.A.,
B;odekii,
S.Ya.
and

Xafaro,

of

weight
E.J.

kgmL
kg-=
kg-=

e-x

coefficient

Th~ele
modulus
Number
of experiments
foral
pressure
reaction
rate
based

and

e-l
s-z
s-=

mass-transfer

liouid-solid

973

Graaf,

- 979.
G.H..
Sijtsema,
G.E.H.
Jooste,
metha-*
Bynthesis.
2883
2890.
Stamhuis,
G.H.,

rrations

volumetric
coefficient

mol
mol
mol

CCHsOH'

can

For
be

a
rough
calculated

of
the
linearised

(AlI

KPa)

are
pseudo-constants,
the
catalyst
surface

estimate
for
a

which
and

have
the

to be
calculated
rate
expressions

2166

G. H. GRAAF~~U~.

given

in
M.%

this
paper.
Furthermore:
= dS
kp_"'
(K,,
+

7 CH3Ox.I=

((3

M,)

MT

coth(3

G2

(36(E/t)D,,1

) - 1)/(3

l&m)

MS

(A2)

(A3)

The
diffusion
coefficient
(for
methanol)
in squalane
is calculated
from
Reddy
The
ratio
of porosity
and
tortuosity,
E/t
= 0.123,
and
& Doraiswamy
(1967).
the
density
of the
catalyst,/3=
1950
kg m-3, are taken
from
Graaf
et al.
(c).
value
of
the
lowest
the
out
the
equations
given
above,
Checking
effectiveness
factor
for
our
kinetic
experiments
turns
out
to be
0.98.
This
indicates
that
intra-particle
diffusion
limitations
are
negligible.
- Liquid-solid
mass-transfer

(L-S)
mass-transfer.
coefficient
follows
Sh

Again
we
use
reaction
rate
without
L-S
experimental

k,

d,

conservative

estimation

of

the

L-S

fromr
/

mno~

(A4)

(now
defined
as:
the
concept
of
the
effectiveness
factor
the
with
L-S
mass-transfer
limitations
divided
by the
reaction
rate
value
for
limitations).
The
minimum
our
mass-transfer
results
was
0.991.

- Gas-liquid
(G-L)
mass-transfer.
Since
the
bubble-size
and
the
gas-holdup
no calculations
can
be made
with
the
conservative
assumption
Sh
are
unknown.
a value
of kla
can
be calculated
if we
choose
a value-for
the
= 2. However,
factor:
e.g.
p
=
0.95.
For
the
experimental
conditions
of
effectiveness
interest
a value
of
kla
in
the
range
0.005
- 0.02
s-'
is
needed
to
fulfil
value
of
kla
can
be
seen
as
a
total
mass-transfer
condition.
This
this
including
both
the
gas-side
and
the
liquid-side
resistance,
coefficient,
be
much
than
the
latter.
In
reality,
former
will
smaller
although
the
Ledakowicz
et
al.
(1984,b)
are
probably
much
larger,
because
kla-values
at comparable
conditions.
reported
k=a-values
of 0.3
- 1.3
s-~

1.
2

0.151
0.176

0.051
0.019

0.798
0.-?75

::

0.114 0.175
0.049
Cl.088 0.725
0.798

5
6
7
8

0.151
0.074
0.289
0.136

0.013
0.052
0.030
0.066

0.835
0.873
0.681
0.798

Table

2.

499.3

20

20 30 40
15

20
15
15

Kinetic

25
20
20
20

30
25
25

models

483.5 499.3 516.7 532.4

40

499.3
499.3
499.3
499.3
499.3
483.5

483.5
483.5
483.5
483.5
483.5

40

that

passed

A(='

cn,on

516.7
516.7
516.7
516.7
516.7
499.3

532.4
532.4
532.4
532.4
532.4

theX'-test.

)"

a(='

20

AZBlC4
n2e2c4

6.6
7.0

15.8
16.5

A,BZC,

6.9

13.1

A3B1C4
A382C4

7.7
7.6

15.9
16.9

*
ff

For
a description
of
these
referred
to
Graaf
*t
al.
Engng.
Sci.
for publication,
Definitionra(rl)

gable
3.
methanol
standard

i
,=1

Relative
catalyst
activities
and water
(mean
values
and
deviations,.
l

Kinetic

(100/N)

models
the
(submitted
a).

(t3

reader
is
to
Chem.

r5

with
respect
corresponding

to

water
activity

methanol
activity

model

r3)

AlBlC4

1.06

* 0.17

(t

169)

1.36

* 0.21

(*

15%)

A282C4

1.04

* 0.17

(*

16%)

1.35

* 0.21

(t

15%)

A382C3

0.97

* 0.12

(*

12%)

1.09

* 0.15

(*

14%)

A3BlC4

1.16

* 0.24

(*

21%)

1.39

f 0.22

(*

16%)

A3B2C4

1.16

* 0.23

(*

20%)

1.46

f 0.24

(*

16%)

* FO= a description
to Graaf
et al.

of

+heee

models

rhe

reader

is

referred

12

I3- 23
8
8
8
B
8
4

23
23
23
23
23
15

Kinetics

G2

of the three

phase

Figure
1:
reactor
use*.
Slurry
1 reactor
vessel;
2 magnetic
atirrer;
3 coppersealing
ring;
4 filling
block:
5 stirrer
shaft:
6 12blade*
turbine
stirrer;
7 baffles;
8 foam
separator;
9 electrical
heating
coil;
10
ineulation;
11
Pt-100
sesiarance
themometer;
12 gas
distributor:
13
filter.

methanol

Figure

vity

3rReaiduals

rates

reaction
tc.ta1
0 i

of

as

for

pressure

residuala.

of
the
Function
model
: mean

residuals belonging

mately)
dashed

the
lines:

deviation
experimental

Figure

reaction

6:

same

methanol
of
the
xaBlC4.
of a group
to
(appraxithe

and

plot

for

the

activi-

ty determined
from standard
experi0
:
calculafed
from experimental
reaction
rates
of
methanol
and
the
selected
kinetic
model
(each
point
ia an average
of
several
experiments
carried
out
at
the
same
day).
lines : the
assumed
catalyst
activity
a

of

function

4:Residals
of the
methanol
rate.3
as
a function
of
pressure
for model 2.3~2~4.
0
:
residuals.
0
:
mean
Of
a
of residuals
belonging
to
mately)
the
same
pressure.
dashed
lines:
indicate the mean
deviation
between
this
model
and
the
experImenta
results.

time.

Figure

the
group

(approxi-

the

reeulfs.

Parity
rates.

acti-

catalyst

time during

mentB.

reacrion

mean

model

relative

total

pressure.

indicate
between
this

2:The

as a function
of
kinetic
experiments.

the

as

Figure

2167

synthesis

wafer

Figure

versus
*:

7:

symbols:

rate

Reacfion

temperature.
k,m.s
;
0
regression
lines
2
regression
ratures.

constants

0
: k o-.2.3
k,,,c..
.
per
temperature.
with
all
tempe-

Figure
versus

8:

Adsorption

temperature.
KC&
: o :
symbols:
regression
:
3 :

lines

constants

K,,,,&

regression

per
with

%Q ;
temperature.
all
temperatures

2168

G.

H.

GRAAF

et al.

G2

A___-_----

,b

,;

l&,W
n?z*p

Figure
nol

an*

o,.:
A<

bar;

reaction

Reaction

9:

water
p=
I:

at

37Lmr;o,.:
p = 20

=
bar;

for

rates

with
feed
4
(see
symbols:
reaction
results
ith
feed

for

rates
532.4

30
symbols:
results
closed

open

methanol,
Table

1).

xates
4

(see

metha-

K.
p=

for

water,

Table

I.).

linest
calculated
with model A382C3
after correcring
for the difference
solid
in the catalyst
activity:
lines are used for methanol reaction
for water
JIdtes dashed lines
(gas flowrate
at
mL\ctLl
rates.
the T?sa.cto7z outlet).

10:
eater
formation in the
phase methanol synthesis.
. : T = 483.5 EC: . * T _ 499.3 K;
symbols: resulfs with feed 8

Figure

three
(see

Table

Wifh
for

model

1). lines: calculated

A3B2C3
after
correcting

the difference
in catalyst
activity
of the catalyst
used in
feed 8 (with respect
to methanol).
(gas flowrate
at the reactor
outlet)

13:Water
formation
in threephase and two-phase
methanol synthesis.
Conditions:
see Figure 9.
Solid line:
three-phase
metharwl
Figure

synthesis.
methanol

Figure
15:
for methanol
two-phase
p _ 20
bar;
Y=I&S:
GS:

Initial
in
methancll
feed

= 0.15;
three-phase
two-phase

yeas.

rates

reactioll
three-phase
synthesis.
composition:

= 0.05:
methanol
methanol

and

y,,

0.80.

synthesis;

synthesis.

Dashed
synthesis.

line:

two-phase

figure
11:
Reaction
rates
in threephase mertlano1 synrhesir.
T = 499.3 x;
p = 20 bar: feed composition:
YCO = 0.15; ycon - 0.05; yrrz - 0.80.
A: merhdnol reaction
rate COP reaction A. B: atel
reaction
rate for
reaction
B. c: mefhanol and water
reaction
rate for raaction
C.

Figure
14:
Mole-fractions
of water
and
methanol
(reactor
outlet)
in
three-phase
and
two-phase
methanol
synthesis.
conditions
: see
Fig.
9.
Solid
line
: three-phase
mefhanol
synthesis.
dashed
line:
two-phase
methan
synthesis.