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# 2005 Institution of Chemical Engineers
Trans IChemE, Part A, July 2005
Chemical Engineering Research and Design, 83(A7): 811 819
www.icheme.org/journals
doi: 10.1205/cherd.04335
1
Department of Chemical Engineering and Process Plant, TU Dresden, Dresden, Germany
Chemical Reaction Engineering Laboratory (CREL), Washington University, St Louis, Missouri, USA
INTRODUCTION
811
812
BAUER et al.
and Cybulski (1994) compared numerically the performance of a trickle-bed reactor and a monolithic reactor in
terms of space-time yield, selectivity and pressure drop.
Stankiewicz (2001) developed a model for the in-line
monolithic reactor and compared its performance in respect
to mass transfer with a randomly packed reactor. Nijhuis
et al. (2003) evaluated theoretically the performance of a
monolithic reactor and a trickle-bed reactor using the
hydrogenation of styrene. The authors demonstrated that
the monolithic reactor had a three-time higher productivity
while using four-times fewer catalyst. Recently, Roy et al.
(2004b) illustrated a fundamental approach in modelling of
the transport-kinetic interactions in a monolithic catalyst
for operation in film flow mode. However, no studies are
available on whether any comparison between Taylor
flow and film flow modes of operation or any comparison
of monolithic reactors operated in film flow with tricklebed reactors.
The present study provides a mathematical model of the
monolith reactor operated in cocurrent downflow of gas and
liquid for operation in Taylor flow regime and film flow
regime. The proposed model has been validated by comparisons of the calculated results with experimental results.
A comparison of the reactor performance between Taylor
flow and film flow under optimum operating conditions
was carried out. Furthermore, the behaviour of a tricklebed reactor was compared with the monolithic reactor
operated in both Taylor flow regime and film flow
regime. Effect of superficial liquid velocity, flow regime,
monolith geometry, cell density and geometric surface
area has been investigated on the hydrogenation of alphamethylstyrene (AMS) and phenyl acetylene (PA).
REACTOR MODELLING
In order to compare the performance of a monolithic
reactor operated in Taylor and film flow and a tricklebed, reactor models have been developed. The models
were formulated for single pass conversion of the liquid
reactant passing through the reactors. A modified model,
which accounts for multiple-pass flow through the reactor,
was used for the evaluation of model predictions against
experimental data. The partial differential equation systems
for the reactors were solved using the commercial software
tool Aspen Customer Modeler (ACM). The hydrogenation
of a-methylstyrene (AMS) to cumene and the selective
hydrogenation of phenyl acetylene (PA) to styrene were
considered as model reactions.
INTRINSIC KINETICS
The hydrogenation of a-methylstyrene and the consecutive hydrogenation of phenyl acetylene were selected.
The experimental investigation of the kinetics of the hydrogenation of a-methylstyrene was performed by Meille et al.
(2002) and additional details can be found in the associated
publication. The intrinsic reaction rate can be expressed
with the following rate equation:
EA
KH2 cH2
p
r k0 exp
RT (1 KH2 cH2 )2
(1)
r1 k1
(2)
(3)
Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A7): 811819
1WC
@cS (i, x, y)
@ cS (i, x, y)
Deff (i)
@t
@y2
X
nj (i)rj (x, y)
(6)
Boundary conditions
@cS (i, x, y)
0
@y
y0
813
Mass Balances
(7)
kaLS (i) cL (i, x) cS (i, x, y)ytwc
RT
cG (i, x) cS (i, x, y)ytwc
kaGS (i)
He(i)
(8)
(9)
cL (i, x 0) cL (i, x 0 )
i A, B, H2
(10)
TRICKLE-BED REACTOR
@cG (H2 , x)
@2 cG (H2 , x)
Dax,G (H2 )
@t
@x2
@(uG cG (H2 , x))
kaGL (H2 )
@x
RT
cG (H2 , x) cL (H2 , x)
He(H2 )
RT
cG (H2 , x)
kaGS (H2 )(1 weff )
He(H2 )
cS,dry (H2 , x)
(11)
(13)
Table 1. Correlations used for modelling the monolith reactor in Taylor flow mode.
Parameter
Gasliquid mass transfer
Liquidsolid mass transfer
Correlation
n
1:2
0:133uUC
DA
kaGL
DB
L0,5
L
0:7 !
D
CL
kLS 20
1 0:003
dh
ReUC Sc
kGS
D
df
db,sq
0:7 0:5 exp (2:25Ca0:445 )
dh
4(1 bL )
aGS
dh
4bL
aLS
dh
uL
bL
uL uG
Reference
Bercic and Pintar (1997)
Kreutzer et al. (2001)
Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A7): 811819
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BAUER et al.
Table 2. Correlations used for modelling the monolith reactor in film flow mode.
Parameter
Correlation
ShGS
kGS df
0:267(1:5z)1:2
3:4145
DL
1 0:2(1:5z)0:7
with: z
Liquid saturation
Gassolid interfacial area
Liquidsolid interfacial area
LR DL
d2f uL
nj (H2 )rj,dry
(14)
j
1S
@cS (i, x)
kaLS (i)weff (cL (i, x) cS (i, x))
@t
X
X
nj (i)rj,wet
nj (i)rj,dry
j
1S
3 tGL
3 tGL 2
hL
+
df
3uL0
4 rL g
4 rL g
rL g
2
2df
bL 1 1
dh
p
4 (dh 2df )dh
aGS
dh2
4
aLS
dh
1S
Reference
(15)
@cS,wet (H2 , x)
kaLS (H2 )weff (cL (H2 , x)
@t
X
cS,wet (H2 , x))
nj (H2 )rj,wet (16)
DmP
uL0 nA
cA,in MP
XS
tPr oc mcat
LR nP xWC rWC ycat=WC
(21)
i A, B, H2
Reactor outlet, x LR
@cL (i, x)
0
@x xL
@cG (i, x)
0
@x xL
i A, B, H2
(19)
(20)
Equation (21) employs process parameters such as conversion X, selectivity S, superficial liquid velocity uL0 and inlet
concentration of reactant cA0 as well as reactor design
parameters such as reactor length LR and the amount of
catalyst specified with xWC, rWC, ycat/WC. Besides the
often used space time yield, the productivity as well is an
adequate base for comparison of multiphase reactors, as it
considers the amount of product that can be produced in
a certain time by using a defined amount of catalyst.
Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A7): 811819
815
Correlation
Reference
0:46
dR
rL uL 0:14 0:5
ScH2,L
dP
hL
0:82
dR
rL uL 0:9 0:5
kaLS (H2 ) 0:75DH2,L
ScH2,L
dP
hL
r uL 0:56 1=3
Sci,L ; i A, B
kaLS (i) 0:45Di,L L
hL
DH2,G 1=3 1=3
kGS (H2 ) 0:18
1
(1S 1)ReG Sc2=3
H2,G
dP S
0:33
dR
1L 0:16(1 1S )
Re0:14
L
dP
1 (Dp=x)=rL g 1=9
weff 1:104Re1=3
G
GaL
kaGL (H2 ) 0:33DH2,L
Dax,L 0:55ReL0:61
0:78
Dax,G 13ReG
MR (Taylor flow)
MR (film flow)
Pellet
Egg shell
3.3 9.9
Diameter (mm): 2 6
Shell thickness (mm): 14
0.010.5
0.01
0.3
298, 348
15
0.5
298, 348
15
5.3 1023
10.0 1023
0.5
348
15
Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A7): 811819
600 1800
0.4
816
BAUER et al.
x (cpsc)
4
6
8
12
16
31
47
62
78
93
x (cpsi)
dh (mm)
OFA
GSA (m21)
Regime
25
40
50
75
100
200
300
400
500
600
4.40
3.48
3.11
2.54
2.20
1.56
1.27
1.10
0.98
0.90
0.75
0.75
0.75
0.75
0.75
0.75
0.75
0.75
0.75
0.75
682
863
964
1181
1364
1929
2362
2728
3050
3341
FF
FF
FF
FF
FF
TF
TF
TF
TF
TF
Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A7): 811819
817
A variety of industrial gas liquid solid reaction processes is carried out in trickle-bed reactors, mainly due to
simple assembly and achievement of high catalyst load.
However, pressure drop and the related particle size are
the weak points. To reduce the pressure drop over the
packed bed, larger particles are needed, whereas small particles are desirable for achieving high mass transfer rates
due to the higher specific surface area and short intraparticle diffusion paths. The monolithic structure shoes a very
low pressure drop in consequence of the straight channels
and excellent mass transfer rates. For an evaluation of the
reactor performance, a comparison of both reactor types
is necessary. The effect of specific surface area on the conversion of phenyl acetylene (PA) is shown in Figure 4.
Numerical studies are performed for a monolithic reactor
operated in Taylor flow regime and in film flow regime,
respectively, as well as for a trickle-bed reactor at superficial liquid velocities of 0.5 and 1.0 cm s21. As illustrated
in the Figures 4 and 5, the specific surface area has an
impact on conversion and selectivity. In general, increase
in specific surface area results in increase in catalyst loading, thus enhancement in conversion. This effect is
obviously pronounced for the trickle-bed reactor and
Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A7): 811819
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BAUER et al.
lower conversion than for film flow and trickle flow, so
direct comparability is reduced. The formation of intermediate product increases with increasing conversion and
thus the consecutive reaction is enhanced which lowers
the selectivity towards the intermediate product.
CONCLUSIONS
Figure 7. Effect of specific surface area on productivity for the hydrogenation of PA.
The work provides a mathematical model of the monolithic reactor and the trickle-bed reactor as well as numerical process simulations for a range of operating conditions
and reactor configurations. The proposed model was
validated with experimental data obtained from reaction
experiments at different hydrogen partial pressures for
Taylor flow mode. Furthermore, the influence of superficial
liquid velocities, flow regime and bed structures on conversion, selectivity and productivity was studied. It was found
that for the hydrogenation of AMS, film flow gives higher
conversion per pass at same reactor length. However, conversion in Taylor flow regime can be increased if a higher
reactor length or liquid recirculation can be used. Selectivity is also higher in Taylor flow due to lower residence
time, higher mass transfer rates and higher liquid saturation
within the reactor. A comparison between the monolithic
reactor and the trickle-bed reactor has revealed that a
higher conversion can be obtained with the trickle-bed
reactor. But the simulations showed that the monolithic
reactor operated in Taylor flow mode with high cell density
monoliths outperforms the trickle-bed reactor and the
monolithic reactor in film flow mode if selectivity and
productivity are considered. The selection of the type of
reactor and of the flow mode for the monolithic reactor
depends on various factors such as throughput, product
quality and investment costs, and needs optimization for
these parameters in each case.
NOMENCLATURE
a
c
Ca
d
D
Dax
EA
FF
FFMR
g
Ga
GSA
H2
He
k
k
K
L
m
M
MR
OFA
p
Dp
P
PA
r
R
Re
S
Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A7): 811819
Schmidt-number, h . r21 . D 21
Sheerwood-number, k . df . D 21
styrene
thickness, m
time, s
temperature, K
trickle-bed reactor
Taylor flow
Taylor flow monolithic reactor
velocity, m s21
wetting efficiency
axial coordinate
volume fraction
conversion
internal coordinate
weight fraction
Greek letters
b
saturation
d
film thickness, m
1
holdup
h
dynamic viscosity, Pa s
h
catalyst effectiveness factor
n
stoichiometric
r
density, kg m23
s
surface tension, N m21
t
shear stress, N m22
z
reciprocal Graetz-number
x
cell density, cpsc
C
dimensionless length, L/dk
Subscripts
0
A
ax
B
b
cat
dry
eff
f
G
GL
GS
h
H2
i
in
j
L
LS
P
P
Proc
R
S
sq
UC
W
WC
wet
superficial
component A
axial
component B
bubble
catalyst
not wetted catalyst surface
effective
film
gas
gasliquid
gassolid
hydraulic
hydrogen
component i
reactor inlet
reaction j
liquid
liquidsolid
particle
product
process
reactor
solid
square
unit cell (one liquid slug and one gas bubble)
wall
washcoat
wetted catalyst surface
819
REFERENCES
Al-Dahhan, M.H. and Dudukovic, M.P., 1995, Catalyst wetting efficiency
in trickle-bed reactors at high pressure, Chem Eng Sci, 50(15):
23772389.
Bercic, G. and Pintar, A., 1997, The role of gas bubbles and liquid slug
lengths on mass transport in the Taylor flow through capillaries,
Chem Eng Sci, 52(2122): 37093719.
Boger, T., Heibel, A. and Sorensen, C.M., 2004, Monolithic catalyst for
the chemical industry, Ind Eng Chem Res, 43(16): 46024611.
Burghardt, A. and Bartelmus, G., 1996, Hydrodynamics and mass
transfer in three-phase concurrent reactors, Chem Eng Sci, 51(11):
27332738.
Chaudhari, R.V., Jaganathan, R., Kolhe, D.S., Emig, G. and Hofmann, H.,
1986, Kinetic modeling of a complex consecutive reaction in a slurry
ACKNOWLEDGEMENTS
The authors gratefully acknowledge the financial support of the
Chemical Reaction Engineering Laboratory (CREL) and Dresden University of Technology. In addition, two of the authors are grateful to the
Chemical Reaction Engineering Laboratory (CREL) for kind hospitality.
Special thanks to Prof. Dr-Ing. habil. W. Kloden (TU Dresden) for his
valuable suggestions in the handling of ACM.
This paper was presented at the 7th World Congress of Chemical
Engineering held in Glasgow, UK, 1014 July 2005. The manuscript
was received 15 December 2004 and accepted for publication after
revision 18 April 2005.
Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A7): 811819