by
Sadettin S. Ozturk
and
Yatish T. Shah
Chemical and Petroleum Engineering Department
University of Pittsburgh
Pittsburgh, PA 15261
CONTENTS
Section
IC
1172
I n t r o d u c t i o n ............................................
1173
Model
1178
D e s c r i p t i o n .......................................
FixedBed
Reactor
Parameter
Effect
SlurryBed
Design
for Methanol
on Reactor
1180
Performance .................
1195
Synthesis ........
1210
Performance .................
1221
1239
Parameter
Estimation
for FixedBed
Reactor ..............
1243
Parameter
Estimation
for S l u r r y  B e d
Reactor .............
1260
Parameter
Reactor'Deslgn
Synthesis .........
Effect
for Methanol
on Reactor
N o m e n c l a t u r e ............................................
1265
R e f e r e n c e s ..............................................
1268
Appendix
ICI
IC ............................................
1168
LIST OF FIGURES
Page
lCi
1176
IC2
1177
IC3
1197
IC4
1198
1199
1201
1202
IC8
1203
IC9
1204
IC10
1205
ICIf
1206
IC12
1208
IC!3
1209
lC14
IC15
1222
IC16
1223
IC17
1225
IC18
1226
IC19
1227
IC20
1228
IC21
1229
IC22
1230
lC5
IC6
IC7
1169
IC23
1231
IC24
1233
IC25
1234
IC26
1235
IC27
1236
IC28
1237
IC29
1238
IC30
1240
IC31
124L
1170
LIST O~ W ~ L ~ S
Page
iC1
1171
1175
SUMMARY
The synthesis
of methanol
advantages
of easy temperature
resistances.
methanol
Recently,
In this report,
heterogeneous
dimensional
been carried
a plug from model for the gas phase and the axial dispersion model for the
slurry phase.
estimated by literatuLe
model equations
of reactor,
correlations.
properties
underlying
phase velocities,
such as temperature,
simulators.
the
pressure,
with the
presented.
1172
is
introduction
Methanol is a basic industrial chemical that is produced at an annual
rate of over ten millions tons.
there is the possibility that its use, chiefly as a fuel, will eventually
require large additional amounts of methanol (Brainard et el., 1984).
There are many reasons why methanol is an important key to a syngas based
fuels and chemical industry.
Syngas is a costly
raw material for the production of the hydrocarbons obtained in the FT
reaction where oxygen is eliminated as water or CO 2.
Third, methanol
This route
some 14,000 barrels per day of high octane gasoline from methanol will go on
stream in New Zealand in 1985.
),
CO + 2H 2
CH30H .................................
1173
(i)
CO + 2H 2
Although,
several
CH3OH
(I)
side reactions
the following
two are of
importance:
CO 2 + H 2
CO 2 + 3H 2
CO + H20
(2)
CH3OH + H20
(reaction
in volume,
highest
(3)
high temperatures
of having
limited yield
lowtemperature
catalyst
In 1966,
tonnage
(Kung,
ICI introduced
plants,
based on a
is highly desirable
It is apparent
because
the yield
low pressure
methanol
process
Zinc
of high
1980).
their
taking advantage
Later a catalyst
(high pressure
reaction rate.
of
the thermodynamically
that an active
used.
of methanol are
Several generations
to get a reasonable
limited
is greatly
For
Initially,
in the technology
1174
in low
process
it
Now it Is used
The composition of
syngas before and after the shift is given in Table 1Ci, for Texaco
gasification.
Table ICI:
Lurg!
Balanced C~s
Mole %
C~slfler Type
Mole %
H2
35
55
50
CO
51
19
25
CO 2
13
i0
21
15
H2/CO ratio
0.69
2.89
2.00
Ba lance Ratio
H2/(CO+I.5CO 2)
0.50
2.08
1.25
Inerts
The ICi lowpressure process utilizes a single bed of catalyst and quench
cooling by "lozenge" distributors especially designed to obtain good gas
distribution and gas mixing and to permit rapid loading and unloading of
catalyst.
1175
MAKE UP WATER
GAS EXIT GASIFIER
PROCESIS SI"EAM
,c d
r
I
METHANOL
Figure ICl:
Figure IC2:
pressure,
Various
projects sponsored by EPRI at ChemSystems and Air Products and Chemical Co.,
on the three phase synthesis clarified some of the important economic factors
(Sherwln and Blum, 1979; Bonnell and Weimer, 1984).
CO, CO 2 and H 2 is passed upward Into the bubble column slurry reactor
concurrent with the inert hydrocarbon (Witco40 or FreezenelO0) which serves
to both fluidlze the catalyst and absorb the exothermlc heat of reaction.
Due
been analyzed and the results of the simulations are compared with a
discussion on the reactor perfor~nce.
Model Description
This part includes the model developments for fixed and slurry bed lowpressure methanol synthesis reactors, and descriptions of the mathemtical
procedures to predict the performance of the units.
differences in the design and operation of these two reactor systems, analyses
1178
systems (gas and liquid phrase reactor system) are estimated by correlations
and these methods are also included in this part of the report.
The main
assumptions underlying the model equations are stated and solution techniques
for final form of the equations are described.
presented.
1179
Synthesis
reaction.
or pellets
(Froment and
1979).
Twophase boundaries
transport processes
in flxedbed
in reactor design.
restrictions
should
because of
is lower on the
the heat
resistances
the particle.
resistances
require that
The resistances
reactors
inherent
restrictions.
On the
of the reactants
particle will be lower than for bulk phase and for an exothermlc
temperature will be higher than the bulk gas temperature.
rate is affected by concentrations
and temperature,
1180
reaction the
As the reaction
the intrinsic
and temperature.
rate cannot
1974).
always lowered by the internal and external mass transfer resistances end the
temperature at the catalyst site differs from the bulk temperature, the last
mentioned model is known to be less appropriate and should be avoided in most
c~ses,
terms of gas phase conditions and they can directly be used in the axial
integration of mass and energy balance differential equations.
The overall effectiveness factor is now introduced as a quantitative
measure of the combined effects of transport restrictions.
It is defined as
the ratio of the average rate o f reaction, which would have been obtained, if
there had been no transport resistance, i.e. as if the temperature and gas
composition had been the same inside the particle as in the bulk gas phase.
Once this factor is known, the overall rate can easily be obtained by
multiplying it with the rate evaluated at bulk conditions.
The calculation of
such a factor involves a solution of solid phase differential mass and energy
balance equations with appropriate boundary conditions.
In this procedure,
1181
Due to the complex nature of the rate expressions, the presence of two
reactions (reaction I and 2) and the large heat effects, the overall
ef~ectlveness factor calculation for methanol synthesis is not an easy
rustier.
1972).
So far, only two works have been presented in the literature for the
simulation of flxedbed methanol synthesis reactors (Cappelli et al.,
Bakemeler, 1970).
1972;
In the present work, a simulator program has been developed for the
The simulator is
Model Assumptions
and for the reactors where length to diameter ratio is well above unity, axial
dispersion is negligible.
li)
solely by radial variation in axial velocity and since in plugflow case, the
axial velocity is only dependent on the axial direction, radial profiles can
be neglected in an adiabatic plug flow reactor.
Therefore, onedlmensioml
1182
iii)
are also based on the concentrations rather than fugacities, suggesting that
the ideal gas law can be applicable.
will be used but for the rate expressions based on the fugacitles, the
nonideality will be considered.
iv)
equations m~kes the use of the StefanMaxwell equation for the mixture gas
dlffuslvlties difficult.
important.
temperature and total number of moles variations) leading to variable heat and
m~ss transfer parameters and also mixture properties along the reactor length.
1183
b.
Model Equations
Mass Balances:
(a)
Gas Phase
i.
Methanol
il.
CO 2
d
d"'~
(U CC02g ) = (kg)c02 av ((Cc02 s) rfR _ CC02 g)
(b)
(4)
(5)
Solid Balance
i.
Methanol
(DM)e d
dCM s
(6)
II.
CO 2
(Dco2)
r
e d (r2
dr
dCco2
dr
) . r2
(7)
Here effective dlffuslvltles are assumed constant and evaluated at bulk gas
phase c o n d i t i o n s .
1184
2.
Energy Balances:
(a)
Gas Phase
dxd
(b)
([I
S
P Cp Tg) = h a v ((T)r=R
Tg)
(8)
Solid Phase
ke d
2
d~
r
(r 2 dT 2.
'd~) = ((AER)I
rl
+ (AER)2
r2)
Pp
(9)
Boundary Conditions:
@ Z = 0
Clg = Ci,o g
= ~o'
U = UO
@r=0
dCSM
. .
dr
@r=R
dCM s
(kg) M (~cMS)r=R  cMg) = (DM)e (~r~)r=R
(io).
(kg)co 2 ((Cco2 s)
r=R
dCco 2
. . .
dr
dT s
dr
(ID
(12)
(dTs .
h ((TS)r=R  Tg) =  ~e ~ ) r = R
c.
Solution Technique
By solution of solid phase mass and energy equations (6, 7 and 9)
1185
e
dCM
I = (kg)M av ((CMS)r=R  CMg) = "av (DM)e (d~r)
(13)
r=R
and
dCco
(L4)
6(I~)
where
with the help of effective reaction rates, gas phase mass and energy balances
became:
r Ie
eq (4)
~d
eq (5)
d
~~ (U Cco2g) = r2e
(U CMg) =
(15)
(16)
eq (8)
(17)
instead of integrating eq. (17) we can combine it with eq. (15) and (16) to
give:
Tg
uUCP0cpT g+ (AH) I
o
U pCp (U
CHg  uOcM,og )
(AH)2
+ U  p Cp
(u
o C cgo
2,o
UCco2g )
(18)
here, it is assumed that reaction enthalpies do not change very much with the
reactor length and taken as constant.
1186
Use of conversions
Introducting F i : ucig, superficial molar flow rates, we can define
conversions X 1 and X 2 as follows:
o
FMF M
X1 = ~'
FCO
 FCO 2
CO2
X2 =
(19)
FCO
Concentrations
CO
czg = (ZXI+X2)8
(20)
CO 2
(21)
H2
c3g = (e22XIX2)B
(22)
CH3OH
(23)
H20
(24)
N2
c6g = a 5 8
(25)
CH 4
c7g : a 6 B
(26)
Gas velocity
U = U o Coo/ 8
Here pressure is taken constant.
In the above equations:
u4
1187
(27)
In ~erms of conversions
dimensionless
where
form of
eq. (15)
dX
1
d~  = @I
(28)
eq. (16)
dX 2
~z = @2
(29)
eq. (18)
(30)
= rle L/Fco
(31)
(32)
(33)
z  x/L
0 = (T g  T g)/T g
O
(34)
(UCpp)/(UCp p)
a =
(35)
(AH)
rl
(36)
U PCpTog FCO
(~)
r2 =
o
FCO
(37)
U PCpTog
It is clear that integration of eq, (28) and (29) can easily be performed
providing that the effective reaction rates are calculated.
the solution of solid phase balances comes into the picture.
1188
At this point,
i = 1,2, .... g
(38)
I d (r 2 dT
2 dr " ~ )
r
= Z rkPp(AH) k
k
(39)
Dk 12 dr
d (r2 dCk
~)
r
(40)
=VkrkPp
de.
eq. (38)
eq, (39)
1 d
dT
~2 d~ ( { 2 ~ )
eq. (40)
dC i
~21 dat (~2 ~ )
R2
kZ ~ik D?.
l rk pP
=
= _ Rr.rk R 2 (AH) k pp
k
=_
R2
Vk Dkk rk pp
(41)
(42)
(43)
Note that the suffixes indicating effective values for D i and ~ are omitted.
1189
dC.
@
~=O(r:O)
r.:
d~
: 0,~
dT
(44)
dC i
I
(r = R)
i (cIgCi)
( S h )
dT
d~
Nu (TgT)
d~
(z,5)
(46)
where
: r/R, Sh
Nu
i = (k)iR/Di
g
(47)
hR/k
( ~2 dCi
d~
~)
R
=
Vik D k d (~2 dC k ]
D.z d~
~)
kE
[v k
dC i
R Vlk D k dC k
d~
k Vk
integration between
Ci
(48)
(49)
D i d~
1 and
(Ci)~= I 
Vik
Z
k
Vk Di (c k  (Ck)c: I)
Dk
1190
(so)
cig
(ci)g=1 :
elimirmte (Ci)~= 1
(Sh) k
Dk
y 9ik
k 9k
[ckg (Ck)~: I)
Di (Sh) i
(sz)
(Sh) k
(Sh)i (Ckg  (Ck)~:z) ]
Dk
C i = c.g + r ~ik
z
k ~k Di [Ck(Ck) ~=I
(52)
Xk =
CkgC k
g
C1
Or
Dk
Ci : Cig + E Vik
k Vk
[(~)
Di Clg
~=i
[1
(Sh) k
(53)
__d
(~2 dT
d~
"~~)
: r,R (AH) k Dk d
k
d'r
=
vk
d~
(~2 dCk
d~')
R (  a ~ ) k D k dC k
z 
(54)
(55)
T'TC
T  (T) ~:I
R (  a l l ) k Dk
: kr.
~k " i   ( C k 
1191
(Ck)~:l)
(56)
R (AH) k Dk (Sh)
T g  (T)
=I
eliminate
T=Tg+
(T)~=I
Vk
Nu
(57)
(Ckg  (Ck)~= l)
R (AH) k Dk
r
(Sh)
"R" [(Ck
(Ck)~=1
Nu"
(Ckg  (Ck){=l)]
(58)
R (AH)k Dk
T = Tg + kE
vk
(Sh)k
Nu
] 
Xk])
(59)
Hence the problem becomes to evaluate the conversion profiles along the pellet
radius.
Conversions
=
CH3OH
XI
CO 2 + H 2 = CO + H20
(60)
X2
CCH3OH
xI 
C
CH3OH
(6I)
cc o,
X2 =
gCO 2
CCO 2
(62)
CCog
1192
Component
113
D2
i. co
D1
Cco  Cco g [i  ~
(x2)~= I (i  (~)
i/3
((xl)~= I (i  (~!I)
2, CO 2
(63)
) _ xl)]
(64)
3. H 2
D4
)  x2) + D~
D3
:13
)  x I)
113
D2
+~
4. CH3OH
D3
[(x21~__I (I  (~2)
CCH30 H
= C CH30 Hg +
(65)
)  x21}
(66)
Coog X 2
113
D2
5. H20
D5
[(X21~=t (t  ( ~ )
)  x2l
(67)
Temperature
(Sh) I
T=r ~+A
(68)
(Sh) 2
~uu )  X2]
+ B [(x2)~= l (i
where:
(AH) 1
A = D4
(69)
Cl
1193
(AH) 2
B = D2
in these equations
>,
g
(70),
CI
(Sh)k
(Sh) i
. (~~)113
estimation).
Using the above relationships
be solved.
In dimensionless form
eq, (6)
I d. (C2 dXl
{2 d{
d T ) = ~I
I d
eq. (7)
where
(71)
(~2 dX2
~2 d{
T~ ) : 2
(72)
~I = R2 rl 0p/(D4C1 g)
(73)
2 " R2 r2 Op/(D2Cl g)
(74)
Boundary conditions
dX I
dX 2
d~ = d~ = 0
~=0
dX
{=i
~'
"  ( S h ) 4 XI
dX 2
d T " (8h)l
X2
(75)
(76)
(77)
Clg dX[
r1
= a v D 4
(78)
d~
1194
C 1g dX 2
D2 R d~
e
r2
=av
(79)
where
6 (1e B)
av =
(S0)
P
r1
nl = r I (at bulk conditions')
(8!)
e
r2
n2 = r I (at bulk conditions)
(82)
The solution of eqns. (71) and (72) are performed by COLSYS (Ascher et al.,
1981) while the integration of eq. (28) and (29) are carried out by a Runge
Kutta method.
The program developed calculates the concentration profiles at hulk gas
phase and at the particle center,
The conversions are evaluated at each point and finally the space
time yield, STY in Nm 3 gas converted per kg catalyst per hour is computed.d.
Parameter Effect on Reactor Performance
The effect of operating and design conditions on the reactor
performance is studied to test the simulator.
(overall conversion is used) and the Space Time Yield are presented are
explained based on theroetlcal observations.
1195
In the first
figure only the mole fractions for CO, H 2 and CH30H are given and since
temperature rise was found to be very small (~ I K) it is not included.
It is
clear that diffusional limitations are very strong and should play a very
important role in the design calculations.
resistances, on, the other hand, were found to be negligible since the surface
concentrations (mole fractions for H 2, CO and CH30H are 0.5, 0.25 and 0
respectively) are equal to bulk values.
are 0.87 and 0.43 for methanol and shift reactions respectively.
In Figure IC4 several concentration and temperature profiles are shown
for a reactor length of 0.8 m that corresponds to the first bed in ICl's
quench reactor.
also included.
increases in the gas bulk phase while it shows a maxima for solid phase center
concentrations.
186 K is obtained.
m/s which is very low (normal value is 0.4 m/s) and this temperature rise is
not permitted in a commercial reactor.
The effectiveness factor and effective reaction rates are given in Figure
IC5.
reaction (Eff I) while it behaves in a pecular way for shift reaction (Eff 2);
it goes through a maxima.
1196
0.5
C,.
II
.... ,
'
Gi
h,,i
ii
I . . . .
, , '
"
I'
,I
~  ~ , "
. . . .
0.4
.~ 0.3
Lur{i G~m
CH30~I.
0.2
0.1
0.00
0.2
0.4
O.e
OolB
Dime~sionle3s Le..~th
Figure IC3:
I!97
0.8
I'=500 K, P70 A t m .
Lurgi
i 0.6
Gas,U~=O.l m/s
L=0.8 m
t{2
0.4
CH30]
CO
O~ 0.2
CH30H,GAS
0.0
0
0.2
0.4
0.8
0.8
D i m e n s i o n l e s s Length
1198
U3
T=SG0 E PV0Atzm.
Lur~i GmsoU~=O.1 im/s
L=O.8 :n
>
t~
f3
>
0,~ 
....
!
O.E:
0.~.
0.6
0.8
Dimensionless Length
Figure IC5:
1199
parameters.
syngas composition
type
(Table ICI).
presented
in Figure IC6 and IC7 for conversion and Space Time Yield (STY)
respectively.
also shown in Figure IC6 andit can be seen that the temperature
reaches a limiting value.
Obviously
is
also
IC8.
established
The optimum
as 0.18 m/s.
c. Effect of Pressure
The operating pressure increases
and ICIf) which is not surprising since the concentration of =he reactants
increases.
of 0.4 m/s.
In the calculations
in reactor wall
operates at a pressure
1200
The low
0.~
  ~
i.
Ts~er~ture
(M
0.2
'i"~=50OK P = 8 0 ~ t ~
0
I
0
Figure IC6:
"
'
"
Le_~{th (m)
1201
1.1
0,9
'
0.7
8
u
Tf=5OOK P=BOatm
Dc=2m U=.4m/s LurEi gain
0.1
0.5
1.5
Z.5
3.5
Length (m)
Figure IC7:
1202
:~
,,
,,
. . . . ;
~.
0.4
. ,
,L,I
;,
,i
r,,.
,,
....
.
~t~re
"~ 0.3
=~ 0.2
'1
.~ ~:==_=::
0.05
0.10
0.1,5
0.~)
O.~B
0.~,0
0.@5
0.40
Figure IC8:
1203
2.4
M2.:
I:~ 1.8
1.6
I.Z
05
0.10
0.15
O.ZO
0.25
0.30
Figure ICg:
1204
0.35
0.40
0.11
,, ,,,,,4
rj
C)
0.0?
T'i=5OOK Ug=O,4m/s
Dc=~xz:~ L=oBz:~
0.0~60
gas
70
80
90
Pressure
Figure IClO:
Lur~i
(~t~)
1205
100
Tf=500K U g = . 4 m / s
e
o~
J
U
1.5
O.S
60
70
80
90
Pressure
Figure l  C  l l :
(atm)
1206
100
This
increase is, of course, due to the increase of the reaction rates and should
be less pronounced after a certain value of temperature where equilibrium
becomes important.
1207
0.25
P8Oatm Ug=O.4m/s
0.20
0.1 5
0
r~
~1
0.10
>
0
0.05
0.00
400
,
460
,
500
,
520
,
540
Temperature (K)
Figure IC12:
1208
560
P=8Oatm U~=.4m/s
rj
Dc=~m
L=.,Sz~Lur~i ~ e
(D
0
1.5
iC
[c
1
q 7
5o0
"
. . . .
. . . . .
: ]:

5~o
,,11
"lr I
ii
,',
54o
Teznperature (K)
Figure IC13:
1209
T I
~ '"
. . . . .
5~o
SlurryBed
representing
efficient
catalysts,
synthesis
development
of more
thermal deactivation
reactor operation.
In recent years,
in the
conditions and the capacity to dissolve and permit the diffusion of gaseous
reactants to the active sites.
Furthermore,
al.,
[982).
I00.
bubblecolumn
in gasliquldsolld
reaction systems
(Shah et
the economics
reactor.
1210
an
reactor concurrent with the slurry which absorbs the heat liberated during
reaction.
bottom of the reactor via a heat exchanger, where cooling occurs by steam
generation.
The
methanol stream produced is suitable for fuel use directly or can be sent to a
distillation unit (not shown) to produce chemical grade product.
gases are recycled back to the reactor.
Unconverted
limit the buildup of inerts which may be present in the synthesis gas feed
(Sherwin and Frank, 1976).
The primary advantages of this sytem over current technology are:
i)
a simple manner.
iii)
dis~rlbuted across the reactor crosssectlonal area without the necessity for
redistribution and quench along the reactor length.
iv)
1211
SYNTHESIS
GAS FEED
SEPARATOR
RECYCLE GAS
RECYCLE
COMPRESSOR
BFW /
C.W.
PREHEAT
PURGE GAS
LIQUID
ENTRAINED
REACTOR
VLL
SEPARATOR(S)
t"
CIRCULATING OIL
AND ENTRAINED
CATALYST PUMP
Figure IC14:
FUEL GRADE
METHANOL PRODUCT
(TO CONVENTIONAL
PURIFICATION IF
CHEMICAL GRADE
DESIRED)
CONDENSED
OIL RETURN
PUMP
v)
Catalyst can be added and withdrawn from the system without the
necessity of shutdown.
vi)
activity level so that it is not necessary to overdeslgn the reactor size for
the "end of life" catalyst activity level.
Chem Systems Inc. have been developing the LPMeOH technology under the
sponsorship of Electric Power Research Institute (EPR!) since 1975 (Sherwin
and Blum, 1979).
are used and several aspects of the new technology have been investigated.
With all the informmtion available, it is essential to develop a reactor
simulator to predict the performance of such a reactor configuration and this
part of the project aims at this point:
transfer.
several factors; too high a value could result in excessive gas holdup,
1213
Given an allowable gas velocity and design synthesis gas feed flow,
per hour) relates directly to reactor conversion through the kinetics and mass
transfer correlations and this fixes the weight of the slurry loading, which
is expressed in kg of catalyst per m 3 of oil.
will always result in a lower reactor volume, other things being equal.
However, too high a loading will make a highly viscous slurry with increased
risk of plugging lines, valves and heat exchanger tubes.
Given the slurry volume and the specified gas velocity and predicted gas
holdup, the required reactor volume can be calculated.
In the present work, a computer program has been developed for the design
of a bubblecolumn slurry reactor for the methanol synthesis.
The program is
~odel Assumptions
Due to
1214
ii)
It
~es thought the t, the flow rate of gas decreases as the conversion increases,
while it increases as the temperature increases and these effects should
cor~ensate each other.
iv)
For the flow pattern in gas phase, a plug flow model is used.
This corresponds to a general case in bubble column slurry reactors where the
gas phase Bodenstein number is usually very high.
v)
I00 ~m) used the diffusional limitations should be negligible, hence, the
approximation should be reasonable.
vi)
heat and m~ss transfer coefficients and dispersion coefficients are assumed to
be spatially independent.
1215
x)
Owing to the low heat capacity of the gas phase compare to the
slurry phase, a heat balance on the suspension (liquid plus solid) will only
be considered.
xl)
The physicochemical
dlffusivity,
xil)
properties
considered.
b.
Model Equations
Based on he above assumptions
can be written:
I.
Mass Balances:
For i th component where
i = 1 for CO, 2 for CO 2, 3 for H2, 4 for CH30H and 5 for H20
d
d~ (UGCig) + (kLa)i
*
(CigCil)
= 0
(83)
(B3a)
(83b)
(83c)
Z ffi x / L
1216
(StG) i
(kLa)iL
UG
RTf
Hi
(83d)
(83e)
8 = (T  Tf)/Tf
H i Cil
xi
(83f)
dY i
d~+ (i + e)(StG)i(y i  x i) = 0
(b)
(84)
Liquid Phase:
In the coeurrent operation, a differential mass balance yields:
d OiL )
d
(SLDL ~
 ~
(ULCil) + (kLa) i
*
(Cig Cil) + r. ~ikgLCcatrk = 0
k
(85)
be negative.
Using the following definitions and groups:
(StL) i =
(kLa) i L
UG
(85a)
UGL
Bo L = CLD L
(85b)
q = UL/U G
(85c)
1217
(85d)
Ccat/Ccat, f
rkH i
elk = kkP Vik
r~ k
(85e)
eLCca t, f L
UG
kk
ffi
(85f)
1
B L
d2xi
dx i
q ~
+ (StL)i (Yi  xi) + I ~ Da k ik ffi 0
k
dz 2
(86)
d2Ccat
Ds
+ (Uss
dx 2
UL
dCca t
l e G') d~
we
can write:
(87)
Ccat
C
cat,
U
with
~D
s
,
and
BOseXp[(BsBL )(lz)]  Bo L
ss
D
s
*
I~ s
(88)
1~ L
(88a)
ULL
(88b)
Bo L = Ds(I_ G)
1218
3.
Energy Balance
Considering the slurry phase as pseudohomogeneous, we can write the
d (c %
dT
d~ L ax ~ )
d
 d~ (Ugp C T) + Z ELCcatr k (A~) k = 0
P
k
(sg)
using:
l
(89a)
O = (T  Tf)/Tf
m
Fe = UG P C p L
(89b)
SL~ax
( AHR)kP
Bei, k
(89c)
CpH i TfVik
d20
~ 
Pe dz 2
dO
q ~~ + Z ~
Beik I~ k.~ik = 0
(90)
The final form of the mass and energy balance equations are subject to the
following boundary conditions:
z = 0
Yi = Yl,f
(91)
1 dxl
xl = xi,f + Bo L dz
e=
(92)
d8
(93)
Bo L dz
1219
dxl
dz
z m I
c.
d8
dz
(94)
Solution Technique
The system of eleven differential equations (five for gas and liquid
phase msss balances plus one for energy balance) which presents the design
model is nonlinear and subject to boundary conditions.
NCH3OH
CH3OH
NCO2 NCO2
(95)
and
X 2 = conversion for hydrogermtlon of CO 2
o
NCO 2 NCO
(96)
NCO
where N i represents the total (gas plus liquid) molar flow rate of the
species.
1220
NCH30 H  N~H30 H
Xoveral! = XI + X2 =
o
NCO
(97)
STY in Nm 3
synthesis gas converted per hour and kg catalyst in the reactor were computed.
d.
In this
part a parametric study was performed to test the simu!ater and to investigate
the reactor behavior under a set of operating and design parameters.
The computations were done for a large scale reactor and the results are
presented in graphical forms.
based on theoretical
considerations.
The concentration profiles (mole fractions for gas phase and
dimensionless concentrations for liquid phase) are shown in'Fig. IC15 for a
reactor of i m diameter and 8 m length.
The difference
between gas and liquid phase concentration is small and it can be seen that
the liquid phase is saturated after a dimensionless length of 0.2.
As it will
reaction.
The conversions for methanol formation and shift reaction are presented
in Fig. IC16.
1221
gas
0.,
H2 liq.
~
0
0.35
#m=4
CO gas
0.25 
CO liq.
0.15
0.2
0.4
0.6
0.8
D i m e n s i o n l e s s length
Figure IC15:
1222
0.~0
Methanol
Q~
rxn.
0.10
0.05
Shift rxn
X I0
0.0~
0
0.2
0.4
0.6
0.8
Dh~ez~sio~les~ le~ht
Figure IC16:
1223
A very flat tempertaure profile was observed for temperature (Fig IC17)
while a relatively high dispersion was obtained in catalyst concentration.
general they are very flat and the dispersion should be high enough.
In
Catalyst
concentration is always higher than the feed concentration but it reaches the
feed concentration at the exit of the reactor.
Therefore no accumulation is
expected.
a.
presented in Figs. IC18 and IC19 for conversion and Space Time Yield (STY)
respectively.
As
the dispersion coefficients are mainly affected by diameter, the decrease has
to be attributed to enlarged dispersion in liquid phase.
1985).
and IC21.
c.
performance.
liquid (slurry) phase and the increase in the flow rate decreases the
residence time and the conversion.
of the reactor increases to very high values since the rate of heat removal
!224
1.1B
1.10
1.0~
0.~5 O
0.2
0.~
0.6
0.8
Di~emeionle~s lez~ght
1225
0.18
'
0.15
?500 K, P'/O a t m
:
0.14
O~ 0.13
0.12
0
0.11
0.10
1
1.5
2.5
Column d i a m e t e r (In)
Figure IC18:
1226
3.5
T=500 K, PgO a r m
L=8 =~ u~=o.1=/~
rj
1,4
)
C}
r~ .~
0.~
iC
O,l,
1.5
~.5
'
. . . . .
. . . . . . . . . . .
Figure IC19:
1227
'
t~
3.5
0.30
0.25
0.20 *B.4
4~
0
0.15
pml
p..4
m
L~
0.I0 
0.05
0.00
4
Column Height
Figure IC20:
(m)
10
1228
IZ
,.~
k4
.4(}
I[I
(:
E:
.=~
.2~,
~i ~''''
""
""
'
"
" '
Figure IC21:
1229
I0
12
0.5
0.4
T=500 K, P70 a t m
"~
I,w
Q)
Dc=2m , I ~ 8 m , U  = O . l m / s
0.3
0.2
01 "
0.0
0.00
0.02
0.04
0.08
0.08
Figure IC22:
1230
O.iO
"~'
,(2
rj
"~
:fI l ' l i ' :
0.7
0.~
r~
rd~
0.00
0.0~
Figure IC23:
0.0~
00~
1231
0.08
0.10
decreases,
velocities
d.
It is apparent
in
that
loading increases
can be
The S shaped
Effect of Pressure
The effect of pressure was studied for a pressure
arm.
range of 50 to i00
this behavior.
1232
The increases
rate expressions.
Figs. IC28
0~. 
u,i=~.o25~:::~'=
)
0,3
r~
10
C.1
0,0,
(}.CO
O.C~
0.10
G.15
0.~0
Gse~1o~Cty,U{ z~/B
1233
Oe4
I II
~ 0.$
M 0.2
~ 0.1
i0.01
o.oo
o.o5
o.Io
o.15
o=o
Figure IC25:
+1
"/
BBO
2+ .............~i~ ..............a + ................o~ ......... ; ~ + ..............+; ....................
Figure IC26:
1235
P70 a r m ,
,W
W=30 %
~':o.,[
;
o.,[
i1
,,o
,
,60
Figure IC27:
,80
5;0
5~0
1236
5,0
560
0.15
0.1~
~ 0.12
'i~=500 K, IT=30 %
o
0.11
1(~
. . . . . . . . . . . . .i . . . . . . .
50
68
 I ...........................................................
Ii
70
68
88
Pressure ( ~ )
F~gure IC28:
1237
100
0.6
Tf=5OOK
u
0.5
r.)
W=30 Z'
0.4
0.3
O.Z
p::
Ip
ro
ol
I~,
r ~ o.1
5O
60
70
80
90
Pressure
Figure IC29:
(atm)
1238
100
Although a complete
In
fact a single bed is not possible to achieve the desired conversion and the
reactor should be designed in a way that temperature control can be done.
Operating conditions should also be carefully chosen to avoid equilibrium
limitations.
varied.
In Fig. IC30 the conversion is plotted versus WHSV (weight hourly space
velocity) for both reactors.
1239
] ] = 5 0 0 K P=80 a r m
Fixed Bed L=.8 m
S l u r r 7 Bed L=Om
L u r l i Gas
Fixed Bed
S l u r r y VZOZ
"~ 0.1.
T
r~
j~
o
ry W=2
Slurry W=IOZ
0
wmO
w4
m
J~
i)
0.01
0.7
"
I0
mini i
2.05
T =500 K P=SO
Fi.~ed ;Bed L=.8 m
$4
silurry~_ed L=gm
Lr~,Z_Ga.
I
L55
Fixed lied
qD
qD
To
No
et
L05
S l u r r y I~=30~
0.55
~ l u r r y ]?=20X
~

0.050.7
r y ~Y=RO~
I
g
ii
it
II
li
II
NHSV Nm**3/kg
Figure IC31:
It
IIII
Cathr
I I 
II
UIII
II
II
II
of the reactors.
Although
Obviously,
greater in fixed bed reactors but it may be lower for low space velocities.
1242
Diffusivities:
Binary diffusivities are calculated by FullerSchetterGiddings
1977):
m2/s
= Temperature, K
ffipressure, arm
Component
Mi
v i (em3/gmo!)
CO
28
18.9
CO 2
44
26.9
H2
7.07
CH30H
32
29.9
H20
18
12.7
N2
28
17.9
CR4
16
24.42
1243
I Yi
Di
,m
E
Yi/Dij
J=i
Di ,me
2.
= Di ,In
(..~pT)
Viscosities:
Method of corresponding states is used to calculate the gas viscosities
u i = ( 1 . 9 T r , l  0.29)
~i = Tc,i
10 7 Zc, l
2/3/ ~i
ms
Tr, i = T/Tc, i
e q u a t i o n (Reid et a l . ,
~mix
TM
1977).
Yi Mi
i=l
yi~lj
J=l
1244
where
M
eli
i/2
~
:!(I
+I)M
j
I/4
i/2
[I + (~
M.)
(~)~..
~
Mi
Tc(K )
CO
28
132.9
35.4
0.295
CO 2
44
304.2
72.8
0.274
33.2
12.8
0.305
CH3OH
32
512.6
79.9
0.224
H20
18
647.3
217.6
0.229
N2
28
126.2
33.5
0.290
CH 4
16
190.6
45.4
0.228
H2
3.
Pc (arm)
Zc
Heat Capacities:
Heat capacities are taken from the reference books in the form of
kJ/kmol.K , T: C
Component
bxl02
CO
28.95
.411
CO 2
36.11
4.233
H2
28.84
0.00765
CH30H
42.93
8.301
H20
33.46
.688
cx105
.3548
2.887
.3288
1.89
.760
1245
dxlO 9
2.22
7.465
.8698
8.03
3.593
N2
29.0
CH 4
34.33
.2199
5.711
.5723
2.871
.3363
11.0092
4.
(mass)
=,
Cp,i Yi/Mi
: kJ/kgK
Thermal Conductlvlties:
Thermml conductivity of each species is estimated by Bromley's Method
(Reid et el.,
1977).
IM
~ = 2.5 C v
iM
B
where
1.30 C
+ 3.50  0.70/T
r
iM
~ = 1.30 Cv + 3.66 0.3 Cir
v
thermml conductivity,
viscosity,
Cv
molecular weight
Tr
0.69
T
r
cal/cmsk
1246
1.987 cal/gmolK
T b = boiling point, K
Cir
cal/gmolK
rc
 132.9 K
Cp
= 7a1239 cal/gmolK
Cv
 Cp  1.987
Tb
=81.7
= 3.84 104
M
28
gives
% = 1.59 10 4 kJ/msK
= 304.2 K
Cp
= 10.595 cal/gmol/K
Tb
= 194.7
= 2.995 10 4
M
44
1247
= 33.2 K
Cp
= 6.994 cal/gmol/K
Tb
= 20.4 K
= 2.698 10 4
Methanol
(CH3OH):
Nonlinear Molecule:
Tc
= 512.6 K
Cp
= 14,215 cal/gmolK
Tb
= 337.8
.. 1.572 104
=' 32
AHvb
 8426 cal/gmol
. 0.791 gmol/cm 3
ASvb
 24.94 c a l / g m o l  K
Cir
gives
Water
(H20):
K
P
a
1.20
A = 3.58
Nonlinear
10  6
Molecule:
Tc
 647.3
Cp
Tb
 373.2
1.642
10  4
18
AHvb
= 9717
8.454
kJ/msK
K
cal/gmolK
cal/gmol
1248
0.343
Nitrogen
= 0.998 g m o l / c m 3
ASvb
= 26.04 c a l / g m o l  K
Cir
= i. 20
gives
I = 4.165
10 6 kJ/msK
= 126.2 k
Cp
= 7.07 cal/gmolK
Tb
= 77.4
= 4.05
M~thane
o~ = 0 . 9 0
10 4 P
= 28
gives
I = 1.67
(CH4):
Nonlinear
10 4 k J / m  s  K
molecule:
Yc = 190.6 K
CP = 11.200 c a l / g m o l  K
Tp = 111.7 K
= 2.669
M
10 4
=16
= 0.425 g m o l / c m
a = 0.049
Cir = 2.12
gfves
~k =
1.045
10 5 k J / m  s  K
t
1249
n
Z
iI
Yl ki
n
Z YiAij
i=l
where
I
Hi
Mi
3/4
I12
T + Si
T + Sj ]
2 T + SiJ
T+
Si
where
ui = pure gas viscosity
T
= absolute temperature
S = Sutherland constant
S i = 1.5 Tbi (boiling point)
and
Sij
="
S t (K)
CO
CO 2
H2
CH3OH
H20
N2
H20
5.
122.6
292.1
30.6
506.7
I16.1
167.6
559.8
d G
JD = 0.458E ( + )
0.407
: JH
1250
2/3
U
where
G=U
PM
RT
 _ _
M = 7 MiY i
6.
C
JH = C
2/3
G
P
P~action Enthalpies:
At 298 K
CO + 2H 2 : CH30H
CO + H 2 : H20 + CO 2
o
= 41270 kJ/kmo!
AH298
o
o
+
AHT = &H298
T
dT
f298 ACp
where
A  productsreactants
and hence Cp values are expressed as
Cp = a + bT + CT 2 + dT 3
we can get
,o
o
AB
2
AH T : AH298 + A~ (t  25) + ~  (t
+~(t
4  2.54)
for C
1251
values C is used.
8.
Catalyst Properties:
The following properties are reported in the literature for Cu/ZnO/AI203
9.
Thermal Conductivity
Density
Pp = 1980 kg/m 3
Porosity
Tortousity
= 0.3
= 7
Reaction Kinetics:
Several kinetic studies have been reported in the literature for
different catalysts.
where Cubased catalysts are applied, most of the kinetic rate expressions are
presented here.
They
developed a kinetic expression for the temperature range of about 330 to 390C
1252
 fCH3OH/%q,l
rI =
(A + B fco + CfH 2 + D fCH3OH) 3
where driving forces are expressed in terms of fuEacities and A, B, C, and D
are parameters that are a function of temperature.
216.07I013"501921"2921gi0 (0"IT50)]
A[IQ (9"9115180/T)]
C = A[10 (13"9427230/T)]
D = A[10 (II'9018780/T)]
Cappelli and Dente (1965) modified the above expressions for a ZnO
1253
rl
 fCH3oH/Keq'I
k tool
' hrkg
2.78 105
I/3 exp (4167/T)
(5A)
B = 1.33 iO I0 exp (2,003/T)
A =
ca talysts:
c)
A CuO/ZnO catalyst
these derived by Natta and Cappelli and Dente has been presented:
2
fco fH 2
rl
 fCH3oH/Keq,I
with
A = 6.33 1014 exp (15,432/T)
B = 2.28 10 3 exp (4739/T)
1254
kmo I
hrkg
obtained
I = kl( CH 2
CMEOH
K'eq,l CH2Cco)
kmol
; hrkg
CCOCH20
2 = k2(CH2  K" eq,2Cc02 );
kmol
hrkg
exp (9386/T)
2
2
KcoKH 2 (PcoPH2 PMeOH/Deq, I )
K(Pco2/Pco )3
r
kmo i
kI
[l+K(Pco2/Pco ) ]3
(I+KcoPco+Kco2+~2PH2)3
1255
kgsec
and
I
r3 = k3(Pco
K'eq ,3
The rate
PMeOH PH20
3 );
PH 2
kmo 1
kgsec
r 2 = r3  r I
kI
KCO
KH2
f)
3;
(C1+C2 fCO + C3 fco 2 + C4 fH 2)
1256
kmol
kgmin
Both
The
kmol
kgmi n
i0.
Equilibrium Constants:
The equilibrium constants Keq,l, Keq,2, Keq,3 are defined by their
eq,l
= (pH 22 PCo)eq
PCO PH20
Keq,2  (
PCO PH 2
)eq
PCH3OH PH20
Keq,3 (p 3 p
)eq
H2
CO 2
O1"
1257
They are related to the true equilibrium constants Kp, 1 and Kp, 3 (Kp, 2 or
Keq,2 one related by the last relationship) at a total pressure of one
atmosphere through the fugacity ratios Ky, l and Ky, 3
The Kp are functions of temperature only, while the Ky are functions of both
temperature and pressure.
Kp,I = 3.27
I0  1 3 e x p ( I 1 6 7 8 / T )
Ky, I = I  AlP
A 1 = 1.95 10  4 e x p ( 1 7 0 3 / T )
Kp, 3 = 3 , . 8 2 6
15 I I e x p ( 6 8 5 1 / T )
Ky, 3 = ( 1  A l P )
(IA2P)
Fugacit ies :
Fugacity coefficients of the components were calculated by generalized
1971):
In @i
I
0.08. ~
{(I.01961 102
T
2.142 102

2
T
4
T
1258
3.2548 102
r
) Pr +
+( 1.8496 10 3
T
3
r
2.1511 10 3 + 0.91445 10 2
2 +
5
T 7
') Pr
T
r
r
+ (0.4172 10 4
1.5469 10 4
3
+
5
T
T
r
r
+ ( 0.42548 106
T
3
r
0.28052 10 5
5
T
r
fi = ~i Yi P
1259
0.5191 10 4
3 +
7
) Pr
T
r
o.82~51o59Pr4}
T 7
r
PL
2.
Heat Capacity:
Estimated for C18H38 by using the group contribution method of Luria and
Number
Group
C(C)(H) 3
8.459
2.113 103
5.605 105
1.723 107
1.383
7.049 102
2.063 104
2.269 107
16
C(C)2(H) 2
 A +BT + CT 2 + DT 3 cal/gmolK
P
1260
Cp =
3.
ca!
J_/_
k
18549 gmolK or Cp = 31.06 kgK
page 567):
~B Vi
where
I association factor
MB
yC m3/kmol
CO
0.0307
CO 2
0.0340
H2
0.0143
c~3oB
0.02s9
H20
0.0189
1261
4.
Solubilities:
Solubility and llquidvapor eqillbrlum data of the species reported in
Bi/T
H i = Aie
atmm3/kmol,
T in K.
20.73
1015.5
618.39
H2
11.25
849.1
1289.5
CH3OH
352249
4307
H20
993095
4890
For the pressure and temperature range of the conditions used, these values
are found to be applicable
medium.
5.
Properties of suspension:
Density
and
Wcat = Mcat/Msus,
1262
Viscosity
No correlation has been reported in the literature for the slurry
viscosities of Witco40 suspensions.
= ~L (i + 4.5
Vca t) kg/ms
Heat Capacity
6.
1/12
i/8
EG
gD 2c PL
gD c 3
2
D2
(
gDc
c
I.i (~__Li)
0"5
(kLa)i D~ = 0.6 EG
0.31
0.62
PL.)
(%)
VL
7.
Dispersion Coefficients:
Liquid Phase (Shah and Deckwer, 1985)
1263
m2/s
ax
8.
D L 6 ~ p kJlmsK
UGDc
13 Fr
Bo C = ~
.
Ds
! + 8 Fr 0"85
with
Fr = U G g ~ c
0.25
UG
Uss .= 1.2 Ust ( U ~t)
I  Vca t
(I  V*
cat
where
V*
cat
is V
cat
at
= 0.I g/ cm 3
cat
Re = ( A t / 1 3 . 9 )
0"7 if
Re > 0 . 5
where
Ar =,
( Peat
PL
PL ) g
3
P
UstdP
Re =
1264
Nomenclature
6 V
Be
Be L
Bo
L
Bo s
C.zg
Cs
Cil
C T, CG
Ccat
Cp
DG
dp
Particle diameter, m
Ds
Da
~HR
kg
kLa
Length, m
Cij,
Cg
1265
Nu
Nusselt
Pressure,
Pe
Peclet
Radial
Reaction
rate,
Particle
radius,
Universal
Re
Reynolds
number
Sh
Sherwood
number,
St G
Stanton
St L
Temperature,
Tg
Ts
Solid phase
temperature,
U, U G
Superficial
number,
eq. 47
atm
number
coordlnate,
kmol/kgs
m
gas constant
number
eq. 47
in gas phase,
eq. 83d
eq. 85a
K
K
K
UL
Superficial
Uss
Settling v e l o c i t y
of catalyst
Axial coordinate,
Dimensionless
Conversion
Mole
Dimensionless
a x i a l coordinate
Dimensionless
parameter,
Parameter,
eq. 27
Parameter,
eq.
fraction
in swarm,
in gas phase
Greek
&
eq. 83b
eq.
27
1266
35
eq. 83f
m/s.
CB
EG
: "C~s holdup
~L
Liquid holdup
Ep
Particle porosity
Density, k g / m 3
Pp
~X
Stoichiometric coefficient
Subscript
e
Effective
Feed
~s
Ith component
kth reaction
Liquid
Mixture
inlet
.!
solid
1267
Re fere~ces :
Aklta, K., and Yoshida, F., "Gas Holdup and Volumetric Mass Transfer
Coefficient in Bubble Columns", Ind. Eng. Chem. Proc. Des. Dev., 12, 76
(1973).
Akita, K., and Yoshida, F., "Bubble Size, Interfaclal Area, and Liquid Phase
Mass Transfer Coefficients in Bubble Columns", Ind. Eng. Chem. Proc. Des.
Dev., 13, 84 (1974).
Ascher, U., Christiansen, J., and Russel, R.D., "Algorithm 569 COLSYS:
Collocation Software for BoundaryValue ODEs", ACM Trans. ~ t h . Softw., 7, 223
(1981).
Bakemeier, H., laurer, P.R., and Schroder, W., Chem. Eng. Prog. Syrup. Set.
(No. 78) 66, I (1970).
Berry, J.M., Lee, S., Sivagnanam, K., and Szelfert, F., "Diffusional Kinetics
of Catalytic VaporPhase Reversible Reactions with Decreasing Total Number of
Moles", I. Chem. E. Symposium Series No. 87 (1981).
Berry, J.M., Lee, S., Parekh, V., Gandhi, R., and Sivagnanam, K., "Diffusional
Kinetics of Low Pressure Methanol Synthesis", Proceedings of PACHEC 83, Vol.
II, 191 (1983).
Bonnell, L.W., and Weimer, R.F., "Slurry Reactor Design for Methanol
Production", paper presented at the 1984 AIChE J Annual Meeting, San
Fransclco, 2530 Nov. (1984).
Bralnard, A., Shah, Y.T., Tierney, J., Wender, I., Albal, R., Bhattacharjee,
S., Joseph, S., and Seshadri, K., "Coal LiquefactlonInvestigatlon of Reactor
Performance, Role of Catalysts, and PCT Properties", Technical Progress
Report, DOE Contract No. DEFG2283PC60056, University of Pittsburgh (1984).
Brown, D.M., and Greene, M.I., "Catalyst Performance in Liquid Phase Methanol
Synthesis", Paper presented at AIChE J Meeting, Philadelphia, 1922 Aug.
(1984).
Cappelli, A., and Dente, M., "Kinetics and Methanol Synthesis", Chim. Ind.
(Milan), 47, 1068 (1965).
Ca ppelll, A., Collina, A., and Dente, M., '~lathematical Model for Simulating
Behavior of FauserMontecatlnl Industrial Reactors for Methanol Synthesis",
Ind. Eng. Chem. Proc. Des. Dev., l__!l
, 185 (1972).
Chang, C.D., "Hydrocarbons from Methanol", M~rcel Dekker, Inc., New York, NY
(1983).
Cova, D.R., Ind. Eng. Chem. Proc. Des. Dev., ~, 21 (1966).
Deckwer, W.D., Lousi, Y., Zaidi, A., Ralek, M., "Hydrodynamic Properties of
FlscherTropsch Slurry Process", Ind. Eng. Chem. Proc. Des. Dev., 19, 699
(1980).
1268
Deckwer, W.D., Nguyentien, K., Kelkar, B.Go, and Shah, Y.T., "Applicability
of Axial Dispersion Model to Analyze ~ s s Transfer Measurements in Bubble
Columns", A!ChE J. 29, 915 (1983).
Ferraris, G,B., and Donati, G., "Analysis of the Kinetic Models for the
Reaction of Synthesis of Methanol", Ing. Chim. Ital., 7 (4), 53 (1971).
Froment, G.F., "FixedBed Catalytic Reactors Technological Fundamentals Design
Aspects", Chem. Eng. Techn., 46__, 374 (1974).
Froment, G.F., and Bischoff, K.B., "Chemical Reactor Analysis and Design",
John Wiley and Sons, Inc. (1979).
Himmelblau, D.M., "Basic Principles and Calculations in Chemical Engineering",
Frentice~ll, 4th Ed., N.J. (1982).
Kato, Y., Nishiwaki, A., Takashi, F., and Tanaka, S., "The Behavior of
Suspended Solid Particles and Liquid in Bubble Columns", J. Chem. Eng. Japan,
5 112 (1972).
Klier, K., Chatkikavanij, V., Herman, R.G., and Simmons, G.W., "Catalytic
Synthesis of Methanol from C0/H2, IV. The Effects of Carbon Dioxide", J.
Catalysis 74, 343 (1982).
Kung, H.H., '~ethanol Synthesis", Catal. Rev.  Sci. Eng., 22, 235259 (1980).
Macnaughton, N.J., Pinto, A., and Rogerson, P.L., "Development of Methanol
Technology for Future Fuel and Chemical Markets", Energy Progress, 4 (i) 232
(1984).
Natta, G., "Catalysis (Emmet, P.H., Ed). Vol. VIII, Reinhold, New York, p. 349
(1955).
Reid, R.C., Sherwood, T.K., and Prausnitz, J., "The Properties of C=~ses and
Liquids", 3rd Ed., McGrawHill, New York (1977).
Shah, Y.T., Kelkar, B.G., Godbole, S.P., and Deckwer, W.D., "Design
Parameters Estimation for Bubble Column Reactors", A!ChE J. 28 (3), 353
(1982).
Shah, Y.T., and Deckwer, W.D., "Scale Up Aspects of FluidFluid Reaction,"
ScaleUp in Chemical Process Industries, ed., R. Kobal and A. Bisio, John
Wiley (to be published, 1985).
Shermuly, 0., Luft, G., "Low Pressure Synthesis of Metahnol in a JetLoopReactor," Ger. Chem. Eng. I._,22 (1978).
Sherwln, M., and Blum, D., "Liquid Phase Methanol," EPRi Report, EPRI AF1291,
Chem. Systems, Inc. (1977).
Sherwin, M.B., and Frank, M.B., '~ake Methanol by Three Phase Reaction,"
Hydrocarbon Processing, p. 122 (Nov. 1976).
1269
3.a[t11,.Y.M., ,qheaieal Enstaeect,1d KinetIc~," McGra~ Hill ~;o., ]rl ei., New
York (1981).
Stiles, A.B., '~Methanol Past, Preseat, a.ld qpec,Jlatto,ls oa the F~it,tre," ~IChE
J. 23 ( 3 ) , 36?_ ( t 9 7 7 ) .
Villa, ~,, Forzatti, P., Ferrarts, G,B., G~rone, G., and PaqqJon, I.,
Synthesis of ~lcoh.~l~ ~ro~ ~ r b o q 0~ides qnd Hydrogen. [. K[qettcs of the
Lo~pre~s,lce "let'~aaol Synt'lesLs," lad. Eng. Chem. Process Des. Dec. 25, 12
(~985).
Wi/ke, C.R., and Lee, C.Y., Ind. Eng. Chem. 47, 1253 ([965).
1270