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DIRECT OXIDATION OF ETHYLENE TO ACETALDEHYDE IN


A HOLLOW FIBER MEMBRANE REACTOR
a a
SHIHAN CHEN & YUEN-KOH KAO
a
Department of Chemical and Nuclear Engineering , University of Cincinnati , Cincinnati ,
Ohio , 45221
Published online: 28 Nov 2010.

To cite this article: SHIHAN CHEN & YUEN-KOH KAO (1990) DIRECT OXIDATION OF ETHYLENE TO ACETALDEHYDE IN A HOLLOW
FIBER MEMBRANE REACTOR, Chemical Engineering Communications, 88:1, 31-47, DOI: 10.1080/00986449008940545

To link to this article: http://dx.doi.org/10.1080/00986449008940545

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Chem. Eng. Comm. 1990, Vol. 88, pp. 31-47
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1990 Gordon and Breach Science Publishers S.A.
Printed in the United States of America

DIRECT OXIDATION OF ETHYLENE TO


ACETALDEHYDE IN A HOLLOW FIBER
MEMBRANE REACTOR t
SHIHAN CHEN and YUEN-KOH KAO:j:
Department of Chemical and Nuclear Engineering
University of Cincinnati
Cincinnati, Ohio 45221
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(Received March 22, 1989; in final form July 22, 1989)

A hollow fiber membrane reactor, which resembles a tube-and-shell heat exchanger, was developed
for homogeneous catalytic reactions with gas reactants and products. The gas stream flows through the
tube side while the reaction takes place in the catalyst solution which fills the shell side. The
separation load of product from the catalyst solution can be reduced by using a hollow fiber
membrane reactor instead of a conventional bubble column reactor. The reactor operates in a
plug-flow pattern with a large mass transfer area per unit volume of catalyst solution.
This concept was investigated experimentally using the direct oxidation of ethylene to acetaldehyde
reaction in an aqueous solution of palladium(lI) chloride-cupric chloride with a silicone rubber
membrane reactor and a polypropylene membrane reactor. It was experimentally demonstrated that
membrane reactors could achieve higher production rates per unit volume of catalyst than the
conventional sparged reactor. The experimental data were in good agreement with the predictions by
the mathematical model. The conditions under which the membrane reactor will be more
advantageous than the conventional sparged reactors can be readily ascertained with the analytical
solution of the simplified membrane reactor model.
KEYWORDS Membrane reactor Homogeneous catalysis Ethylene oxidation.

INTRODUCfION
The most attractive feature of homogeneous catalysis processes is the high
selectivity originated in the effective control of the catalyst species. This feature,
however, is often offset by various operational difficulties. When one or more
reactants are in gas phase, a sparged reactor, which behaves like a continuous-
stirred-tank reactor (CSTR), is often used. The mixing in a CSTR makes it
difficult to achieve high conversions without product recycling which consumes
extra energy. The separation of products from the catalyst solution is a difficult
task if the catalyst is thermally sensitive. Attempts have been made to
heterogenize homogeneous catalysts by chemical methods. While some success
has been reported, the possibility of altering catalyst properties during heterogen-
ization remains (Nakamura and Tsutsui, 1980).
It has been recognized that the use of synthetic membranes as an integral
element in chemical reactors, especially in bioreactors, has potential benefits

t Paper prepared for presentation at 1988 AIChE Annual Meeting in Washington, DC, Nov.
28-Dec. 2, 1988.
t To whom the correspondence should be addressed.

31
32 SHIHAN CHEN AND YUEN-KOH KAO
(Michaels and Matson, 1985). In fact, membrane reactors have been used for
bioconversion to enhance productivity (Nakao et al., 1987; Matson and Quinn,
1986; Linko, 1985). Stanley and Quinn (1987a) reported that higher levels of
conversion in a bioreactor could be achieved by minimizing the dilution effects
with appropriate membrane combinations. Stanley and Quinn (1987b) applied the
membrane reactor to phase-transfer catalysis. The membrane played a role of
stabilizing the oil/water interface while affording an efficient mass transfer of the
phase-transfer agent. The enhancement of mass transfer by using hollow fiber
membranes has been reported by Yang and Cussler (1986). Their study has
shown that the hollow-fiber contactor could provide a substantial mass transfer
area without reducing the mass transfer coefficient. Chang (1987) and Sun (1988),
in their experimental studies on membrane reactors with heterogeneous catalysts,
achieved conversions exceeding the thermodynamic limits as a result of selective
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removal of products by membrane.


Conceptually, the membrane reactor can be applied to homogeneous catalytic
reaction systems to overcome the above-mentioned difficulties. However, very
little attention has been directed to applications in this area. The earliest
literature on the subject, excluding the liquid membrane concept (Wolynic and
Ollis, 1974), is the separation of soluble transition metal complexes from reaction
mixtures. by reverse osmosis (Gosser et al., 1977). Recently, Kim and Datta
(1987) conducted homogeneous catalysis by impregnating the catalyst solution in
a microporous support, which was sandwiched between two polymeric
membranes.
The potential advantages of using a membrane reactor to carry out homoge-
neous catalytic reactions include, but are not limited to, simultaneous reaction
and product separation, selective introduction of reactants, enhanced produc-
tivity, and equilibrium shift. Hollow fibers can provide a large mass transfer area
per unit volume of the reactor. In addition, the membrane reactor operates in a
plug-flow pattern which is preferable for achieving high conversions.
The objective of our work has been to systematically investigate the ap-
plicability of the membrane reactor concept for homogeneous catalytic reactions.
A mathematical model was developed and verified experimentally with a
well-known reaction. An analytical solution of the model was obtained for the
case of equi-molar first-order irreversible reactions. This solution can be used to
judge whether the application of membrane reactor can be beneficial, and also to
provide a preliminary design under certain operating conditions.

REACTOR DESIGN AND REACTION SYSTEM

The membrane reactor used in this study resembles a tube-and-shell heat


exchanger as shown in Figure 1. Hollow fiber membranes are housed in a tube
with the catalyst solution filling the shell side. As the gas feed mixture flows along
the tube side, reactants permeate through the membrane to the catalyst phase
where the reaction takes place. The products then permeate back to the gas phase
and are collected at the exit. The membrane reactor can be designed to
accommodate either single or multiple hollow fiber bundles.
MEMBRANE REACfOR, ETHYLENE OXIDATION 33

FEED PRODUCT

FIGURE 1 The schematic diagram of the membrane reactor.

Two single-bundle membrane reactors, one with nonporous silicone rubber


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(SR) and the other with porous polypropylene (PP) hollow fiber membranes were
fabricated for the series of experiments. Both membrane reactors used Tygon
tubing as the outer shell. The SR membrane reactor used Dow Corning's Silastic
hollow fibers and the PP membrane reactor used Celanese's Celgard X-20
membranes. The dimensions of the two membrane reactors are listed in Table II
and Table III.
In order to elucidate the complex sequence of transport phenomena and
reactions taking place in the membrane reactor, the following relatively simple
and well understood homogeneous direct oxidation of ethylene to acetaldehyde
by aqueous palladium(II) chloride and cupric chloride catalyst (Wacker
synthesis) :

was selected for the study.

MATHEMATICAL DESCRIPTION OF THE MEMBRANE REACfOR

The following processes occur simultaneously in the membrane reactor: 1) the


permeation of reactants from the gas phase through membrane to the liquid
(catalyst) phase, 2) the diffusion of reactants and products in the liquid phase, 3)
the chemical reaction in the liquid phase, and 4) the permeation of products back
to the gas phase. The coupling of the above transport and reaction processes in
the complex reactor geometry can be an overwhelming task to model. However,
in the case of a single-bundle membrane reactor, the following simple model can
be derived.
The geometry of a membrane reactor can be approximated by N identical
capillaries, of which each is surrounded by a coaxial cylindrical layer of catalyst
solution in the amount of one N-th of the total catalyst solution present (see
Figure 2). Consequently, only one capillary, along with its surrounding catalyst
solution, needs to be considered. Also, only one component for each reaction,
namely the key component, needs to be considered in deriving the permeation
equation. For the reaction system selected for this study, ethylene is chosen to be
the key component.
34 SHlHAN CHEN AND YUEN-KOH KAO
gas phase membrane

catalyst
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FIGURE 2 Coordinate system of a capillary element.

A mass balance on the key component A in the gas phase gives


dqYA o,
~+~(P'YA/YA -PA,O)=O (1)

where q is the molar flow rate, ap is the area/unit length of membrane capillary,
YA is the mole fraction, QA is the membrane permeability to component A, and
op is themembrane thickness.
For capillary membranes with an inner radius of R 1 and outer radius of R z ,
o,
--=
2nQA
(2)
s, In(R z/ R I)
Assuming that the activity coefficient, YA, is unity and that the partial pressure of
A at the liquid-membrane interface, PA,O' is related by Henry's Law to the liquid
concentration of A at the membrane-catalyst interface, CA O,
(3)
Equation (1) can be rewritten as
dqYA apQA
~+~(PIYA -HACA,O)=O (4)

If the reaction is not equi-rnolar, the gas mole flow rate in the membrane lumen is
related to the reaction coordinate, E, and the feed rate, qt, by
N
q =qt + 2: ViE (5)
;=1

where Vi is the stoichiometric number of component i of the reaction equation,


defined to be negative for reactants and positive for products. The reaction
coordinate E is related to the mole fraction of the key component by:

(6)
MEMBRANE REACfOR, ETHYLENE OXIDATION 35
The unknown interfacial concentration, CA,lJ can be determined by requiring the
permeation flux and the diffusion flux to be equal at membrane-liquid interface:
apQA dCA I
-,,-(P'YA -HACA;O) = -aDDA - d (7)
Up r r=R2
where a = 2J!R2 ,
Under the constant density condition, the continuity equation for the liquid
phase, neglecting the axial diffusion effect, is
1 d ( dCA)
DA~dr r z:
-RA=O (8)

where RA is the molar dissipation rate of A per unit volume,


The remaining boundary conditions are the feed conditions:
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z =0, (9)
YA = YA,[ (10)
and the no-flux condition at the outer boundary of the catalyst layer:
dCA
-= 0 (11)
dr
In general, the model equations need to be solved numerically, However, in
the case of an equimolar first-order irreversible reaction, they can be solved
analytically by assuming a plenary geometry for the liquid layer. This analytical
solution can be used to provide a preliminary evaluation of membrane reactor
performances, The solution can be arranged into the following conversion
equation:
YA,o
1 -xA=-=exp (TJrmaxf3L ) (12)
YA,! q
where XA is the conversion, YA,lJ and YA,! are the mole fractions of the key
component at the exit and the feed point of the reactor, and, L is the length of
the reactor. The term rma x is the maximum reaction rate within the volume, VI, of
catalyst solution surrounding a unit-length of capillary:
r ma x = kPo VII H A (13)
and TJ is the effectiveness factor which is a function of the Thiele modulus:
<I> = 0DYk/ DA (14)
If the catalyst film can be described by the slab geometry,
tanh( <1
TJ = <I>
(15)

The factor f3 is a measure of reduction in rate due to the permeation resistance:

f3 = [max
(16)
[max + TJrmax
36 SHIHAN CHEN AND YUEN-KOH KAO
where [max is the characteristic permeation rate per unit length of the membrane
capillary,
(17)

The conversion-flow rate relationship of a membrane reactor as represented by


Eq. (12) is similar to that of a conventional plug-flow reactor. This is an
important feature of the hollow fiber membrane reactor. The well-mixed flow
pattern often occurring in a sparged homogeneous catalytic reactor is replaced by
the plug-flow pattern in a membrane reactor. Since the membrane reactor
provides an interfacial area independent of the gas flow rate, this design is the
most suitable for achieving high conversions.
Some insights into the membrane reactor behavior can be gained by examining
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Eq. (12) under various limiting conditions. When the permeation rate of the
reactant across membrane is very small relative to reaction rate, [max T/rmax ,
then
(18)
The conversion will be limited by the permeation rate. Consequently, no
advantage will be gained by using the membrane reactor because the excessive
permeation resistance would greatly reduce the overall reaction rate.
When the membrane introduces very little permeation resistance, rmax [max>
consequently,
f3=1 (19)
is the most desirable situation because both mass transfer resistances, across the
membrane and within the liquid, are negligible.
A quick assessment of the performance of a membrane reactor for a given
homogeneous reaction can be made based on the predictions by Eq. (12) under
the limiting conditions shown above. Figure 3 shows such an assessment for the

1.00
/

0.80 ,-- I
all resistance included
reaction limitin~
I permeation limiting
c I without membrane resistance
.20.60 I
Ul
'-
Q) I
> I
c 0.40
o I
o
I
---
0.20 I

o. 00 -!-"=,--,----~__r-~-----r-_,___-,-__r___,
o 40 80 120 160 200
residence time (sec)
FIGURE 3 Limiting behavior of the membrane reactor.
MEMBRANE REACTOR, ETHYLENE OXIDATION 37
TABLE 1

Physical parameters

Permeability Coefficients (mol mlm' Pa sec)


Silicone rubber membrane Polypropylene membrane
C,H4 6.08 X 10- 13 4.31 x 10- 11
O2 1.71 X 10- 13 3.03 X 10- 11
Diffusivity and Henry's Law Constant
T"C 25 35 45
D (m'/s) 9.33 X 1010 9.64 x 10'0 9.96 x 1010
H (Pa m'/mol) 0.49 x 10' 0.63 x 10' 0.807 x 10'
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SR membrane reactor system used for this study. The operating temperature is at
25C. The reaction rate and the Henry's Law constant for ethylene used in
preparing the figure were estimated based on the work by Henry (1964), which
were found to be 0.00729 S-I and 0.495 x 10- 5 rnol/rrr'Pa, respectively. Diffusivity
of ethylene cannot be used in this calculation because ethylene is present in the
liquid as the [PdCI3~H4r complex. Instead the procedure given by Robinson
and Stokes (1959) was used to estimate the diffusivity of the complex species.
These values are included in Table I. Membrane geometry, reactor size and

TABLE II

Operating conditions of silicone rubber membrane reactor runs

T=25'C
feed rate
("mol/sec) 0.387 0.554 1.014 1.321 1.452 2.429 3.366
feed pressure
(mmHg) 744 745 742 740 744 741 743
feed
composition 0.301 0.292 0.334 0.510 0.424 0.515 0.498
T= 35'C
feed rate
3 a
(umol/sec) 0.506 0.765' 0.890 1.018 1.069 1. 176 1.482 2.926 3.162'
feed pressure
(mmHg) 749 743 741 738 745 742 740 745 744
feed
composition 0.099 0.254 0.070 0.473 0.150 0.411 0.184 0.311 0.284
T=45'C
feed rate
(umol/sec) 0.473 0.736 0.853 1.327 2.081 2.955 3.972
feed pressure
(mmHg) 743 744 745 747 745 747 747
feed
composition 0.256 0.364 0.384 0.335 0.397 0.336 0.356

a The feed is air-ethylene mixture, all others use oxygen-ethylene mixtures.


Membrane: Dow Corning Silastic hollow fibers, to = 0.3 mm, OD ee 0.64 mm. Effective reactor length, L =
1.10 m: number of fibers, N = 22; catalyst volume, Vc = 12 cc.
Catalyst concentrations: PdCI2 0.01016M; CuCI,. 0.8645 M; Cu{OAc),H,O. 0.1221 M.
38 SHIHAN CHEN AND YUEN-KOH KAO
catalyst composition used in this study are listed at the bottom of Table II. The
conversion predicted under the permeation-limiting assumption is much higher
than the conversion predicted under the reaction-limiting (f3 = 1 and 1] = 1)
assumption. This result is an indication that the use of membranes will not impose
significant additional resistance. The effect of the minimal resistance due to the
membrane is shown by the minuscule difference between the solid curve, which
includes all mass transfer resistances, and the short-dash curve, which excludes
the membrane resistance. It can be concluded that the rate-determining step is
the diffusion in the liquid. The small loss in conversion due to the membrane
permeation resistance will be more than offset by the much larger interfacial area
provided by hollow fiber membranes. The conversion of the membrane reactor
can be improved by reducing the diffusion effect which can be accomplished by
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using a tighter membrane packing in the reactor design.

EXPERIMENTAL

Membrane Reactor Experiment


The catalyst solution was prepared by adding palladium(lI) chloride, cupric
chloride and cupric acetate into the distilled water to a composition as listed in
Table II. The feed flow rates were measured by using a mass flow meter (MKS
TABLE III

Operating conditions or polypropylene membrane reactor runs

T = 25'C
reed rate
(/lmol!sec) 0.372 0.617 1.242 1.860 3.720 5.577 7.471
feed pressure
(mmHg) 745 743 743 740 740 740 740
reed
composition 0.420 0.384 0.366 0.364 0.359 0.352 0.351
T = 35'C
reed rate
(/lmol/sec) 0.278 0.558 1.192 3.650 7.416
reed pressure
(mmHg) 745 745 745 744 746
reed
composition 0.374 0.360 0.247 0.279 0.352
T = 45'C
reed rate
(umol/sec) 0.082 0.213 0.260 0.763 1.900 5.427
reed pressure
(mmHg) 753 750 753 755 755 749
reed
composition 0.433 0.481 0.502 0.605 0.616 0.557

Membrane: Celanese Celgard X-20, 1D=0.24mm, OD=0.29mm. Effective reactor length,


L = 1.03 m; number or fibers, N = 200; Catalyst volume, Vc = 33 cc.
Catalyst concentrations: same as in Table II.
MEMBRANE REACfOR, ETHYLENE OXIDATION 39
SR membrane reactor
1.0
a 0 0 oc T = 45C
T = 35C
0.8 h.Af>AA T = 2SoC
calculated
c
o 0.6
Vl
....
Q)

~ 0.4
o
o
0.2
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0.0 -i""'::.......,--...-~-...-~._--,-~---,---,---,
a 40 80 do 1(50 200
residence time (sec) based on feed
FIGURE 4 Conversion vs. residence time results of the silicone rubber membrane reactor.

1159A) and the product flow rates were obtained by a bubble flow meter.
Ethylene concentrations of the feed and the product streams were analyzed by a
gas chromatography (Perkin Elmer Sigma 300) with an integrator (Perkin-Elmer
LCI-lOO) and the conversions were then calculated. Experiments were conducted
at three temperatures, 25, 35 and 45C maintained by a constant temperature
bath. The operating conditions of the SR and the PP membrane reactor runs are
listed in Table II and Table III, respectively. The experimental results are
presented as the conversion vs. residence time based on the feed flow rate in
Figures 4 and 5 and as the conversion vs. feed rate per unit of catalyst solutions in

PP membrane reactor
1.0 00000 T = 45C
T = 35C
T = 25C
0.8 calculated

c
o 0.6
....Q)Vl
~ 0.4
o
o
0.2

0.0
a 200 400 600 800 1000 1200
residence time (sec) based on feed
FIGURE 5 Conversion vs. residence time results of the polypropylene membrane reactor.
40 SHIHAN CHEN AND YUEN-KOH KAO
1.0
0 0 0 0 0 expt., SR membrane reactor
expi., bubble-column reactor
0.8 expt., PP membrane reactor
cnlc., PP membrane reactor
c cclc., SR membrane reactor
0 0.6 colc., bubble-column reoctor
III
....
CIl T = 25C
>
c 0.4
0
o
0.2
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0.0 -t---,.---,---,----,---.---...:...;.
0.00 0.05 0.10 0.15 0.20 0.25 0.30
feed rate per unit catalyst (mol/m 3s)
FIGURE 6 Comparison of membrane reactors with bubble-column reactor at 25C.

Figures 6 to 8. Conversions of these experiments were quite high, reaching 40%


for the SR membrane reactor runs and beyond 90% for the PP reactor runs at
45C.
Membrane permeabilities to pure gases were measured before and after the SR
membrane had been used in the reactor for several months to observe if there is
any membrane property changes. No significant differences were detected and the
measurements were in agreement with the literature data. The results of these
measurements are shown in Table I. No such measurement was done for the PP
membrane reactor after being used for reaction because of the leak which
developed around the potting. The accuracies of the measurements are as

1.0 c c c c c expt., SR membrane reactor


........ .. expt., bubble-column reactor

I lJ.lJ.6lJ.lJ. expt., PP membrane reactor
0.8 I
colc., PP membrane reactor
I
I cclc., SR membrane reactor
C I
cclc., bubble-column reactor
0 0.6 , I
III
.... T = 35C
CIl
I
,,\
>
C 0.4 \'Ole...
0
o ,
, '0

0.2
' .. ~ QJ
.... 0 0
--::--..::-_- - --
- -:-- =-_ =r-.... -

0.0 -t---,.---,---,----,---.------,
0.00 0.05 0.10 0.15 0.20 0.25 0.30
feed rate per unit catalyst (mol/m 3s)
FIGURE 7 Comparison of membrane reactors with bubble-column reactor at 35C.
MEMBRANE REACfOR, ETHYLENE OXIDATION 41
1.0

\
D D D D D expt., SR membrane reactor
expt., bubble-column reactor
\
expt., PP membrane reactor
0.8 ~ ____ calc., PP membrane reactor
__ calc., SR membrane reactor
c cclc., bubble-column reactor
0 0.6
III
..... T = 45'C
'"c
>
0.4
0
c
0.2
----=----=-----=--"'=--= - D
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0.0 -f-----,,-----,-----,--------,-----,-------,
0.00 0.05 0.10 0.15 0.20 0.25 0.30
3
feed rate per unit catalyst (moljm s)
FIGURE 8 Comparison of membrane reactors with bubble-column reactor at 45'C.

following: temperature, 0.2C, flow rate, 0.05 seem, and composition, 0.01
mole fraction.

Bubble-Column Reactor Experiment


Direct oxidation of ethylene was conducted in a bubble-column reactor according
to the procedure described by lira and Freiesleben (1972). The same batch of
catalyst solution used in membrane reactor experiments was used in the bubble
column experiments. A gas dispersion tube was used to ensure an even
distribution of bubbles. The experimental protocol was the same as that used in
the membrane reactor experiments. Operating conditions of these runs are listed
in Table IV and the experimental results are presented in Figure 6 to 8 as
conversion vs. feed rate per unit of catalyst solution. Conversions of these
experiments were quite low, mostly around 10%.

DATA ANALYSIS AND DISCUSSION

Reaction Kinetics
The oxidation of ethylene can be described by the following three steps:
~H4 + PdCl 2 + H20~ CH 3CHO + PdQ + 2HCl
PdQ + CuCI2 - PdCl 2 + 2CuCI
2CuCI + 2HCl + !02~ 2CuCl 2 + H 20
The catalytic center is the palladium-ethylene complex. The metal palladium
produced in the first reaction is immediately reoxidized by the cupric oxide in the
second reaction due to the favorable electrochemical potential (lara and
42 SHIHAN CHEN AND YUEN-KOH KAO
TABLE IV

Bubble-column reactor experiments

T=25'C
feed rate
(pmol/see) 2.062 2.930 4.251 5.099 5.477 10.62 25.30 35.13
feed pressure
(mmHg) 750 751 749 745 749 742 740 750
feed
composition 0.312 0.2979 0.299 0.301 0.299 0.297 0.305 C.353
conversion 0.144 0.133 O.IOS 0.115 O.IOS 0.063 0.036 0.041
T = 35'C
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feed rate
(pmol/see) 2.384 3.486 4.467 6.546 8.721 10.94 16.59 45.11
feed pressure
(mmHg) 745 742 742 745 744 742 740 742
feed
composition 0.562 0.524 0.530 0.548 0.572 0.545 0.520 0.598
conversion 0.194 0.177 0.164 0.137 0.112 0.097 0.074 0.046
T=45'C
feed rate
(pmol/sec) 2.451 4.289 6.712 10.02 13.93 14.07 18.65 30.07 41.01
feed pressure
(mmHg) 745 746 746 746 745 746 746 745 745
feed
composition 0.675 0.490 0.510 0.491 0.488 0.488 0.515 0.465 0.470
conversion 0.226 0.224 0.212 0.179 0.120 0.118 0.103 0.048 0.51

The volume of catalyst solution: 40 ml.


catalyst concentrations: same as in Table II.
Freiesleben, 1972). The reaction kinetics was reported to be first order with
respect to ethylene concentration and zero order with respect to oxygen
concentration (Henry, 1964; Kiryu and Shiba, 1961). Both sets of experiments
were, however, conducted in the absence of oxygen (cupric chloride served as the
oxidant) and the reaction rate was determined by the initial ethylene uptake rate.
Therefore, the applicability of first-order kinetics is questionable for the
membrane reactor under high conversion conditions. In fact, Mitsutani and
Tanaka (1962) observed that the rate would be controlled by oxygen concentra-
tion when CuCI precipitation occurred. The following rate expression was derived
under the assumption that the palladium metal and the cuprous chloride
concentrations are at a quasi-steady state values as the result of rapid reoxidation
of the cuprous ions by the dissolved oxygen:
kt[~H41
r = 1 + k z/[Ozl05 (20)

The above expression includes the oxygen effects on the reaction rate. The
constants k, and k. obtained from the membrane reactor experiments, are listed
in Table V. The oxygen dependency term in the above rate expression is small.
Under low conversion conditions, the rate expression should be very close to the
first order kinetics. It should be noticed, however, that the oxygen dependency
MEMBRANE REACTOR, ETHYLENE OXIDATION 43
TABLE V

Reaction constants

Toe 25 35 45
k, (l/s) 0.0123 0.0321 0.0666
k2 0.205 0.142 0.100

will be significant when oxygen concentration becomes very low, a likely


occurrence when a membrane reactor is operating in the high conversion range.
This rate expression is also in agreement with the observation made by Mitsutani
and Tanaka.
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Performance of Membrane Reactors

Performance of the two membrane reactors can be represented by curves in


Figures 4 to 8 of conversions calculated by the membrane reactor model
presented earlier. The model equations (4) and (8) were solved along with
boundary conditions (7), (9)-(11) by the orthogonol collocation method to obtain
gas flow rate distribution and concentration profiles both in the gas phase and in
the liquid phase. Thus the conversion can be calculated based on the flow rate
and concentration in the gas phase. The conversion-residence time curves as
shown in Figures 4 and 5 resemble that of a plug-flow reactor. These results
demonstrate an important feature of hollow fiber membrane reactors in which the
homogeneous catalyst is heterogenized, thus allow operations in the plug-flow
mode with a large mass transfer area. Therefore, a very high conversion can be
achieved in a membrane reactor by increasing the residence time, which can be
accomplished easily by controlling the feed rate.
There is a considerable amount of date scattering in the very low conversion
range. This is believed to be the result of the very small differences between the
feed and the exit mixture compositions in these runs. The maximum conversion
achieved in the SR membrane reactor is considerably lower than that in the PP
membrane reactor because of the difference in the maximum residence times (cf
Figure 4 and 5, around 200 s for SR and 1200 s for PP). Only 22 capillaries were
used in the SR reactor while 200 capillaries were used in the PP reactor. For
comparable conversions, the SR reactor must be operated at much lower flow
rates which is not possible with the available flow meters. On the other hand, the
SR reactor has a larger mass transfer area than the PP reactor (4127 m2/m3 for
SR vs. 3876 m2/m3 for PP). Therefore, the conversion at the same feed per unit
of catalyst of the SR reactor is higher than that of the PP reactor as shown in
Figures 6 to 8.

Comparison of Membrane Reactor With Bubble-Column Reactor


The conventional bubble-column reactor must be operated at high gas velocities
in order to provide large mass transfer areas. The residence time of a bubble
44 SHIHAN CHEN AND YUEN-KOH KAO
column reactor is limited by the bubble-rise velocity and the height of the liquid.
Thus the single-pass conversion in a bubble-column reactor is generally low.
Higher conversions can only be obtained by the recycling of the product stream.
On the other hand, the residence time in a membrane reactor can be controlled
by the feed rate. Therefore, high conversions can be obtained without a recycle
arrangement.
A key consideration in determining whether a membrane reactor can compete
with conventional devices is its productivity. For homogeneous catalytic reac-
tions, the productivity is usually measured by the production rate per unit volume
of catalyst solution. The productivity of the membrane reactor and of the bubble
column reactor can be compared by examining the theoretical curves obtained
with mathematical models for the three temperatures at which the experiment
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was conducted. The solid curve for the bubble-column reactor was calculated with
the model proposed by Horak and Pasek (1978). At high feed rates, the bubble
column reactor attains higher conversions than the membrane reactor. The
conversions are, in general, low, in the range of 20% or less. At low feed rates,
the membrane reactor offers much higher conversions than the bubble column.
Therefore, the membrane reactor is more preferable for low feed rate, high
conversion requirement applications.
The productivity of a gas-liquid reaction is directly affected by mass transfer
area and mass transfer resistance. In the case of a membrane reactor, the mass
transfer area is fixed by the membrane area provided by design. In the case of a
bubble-column reactor, the mass transfer area is the bubble-liquid interfacial area
which varies with the gas flow rate. The SR membrane reactor has an interfacial
area per unit volume catalyst of 4127 m2/m 3 , and the PP membrane reactor of
3876 m2/m 3 The interfacial area per unit catalyst in the bubble-column reactor
ranges from 50 to 1000 m2/m3 under experimental conditions, usually less than
500 m2/m3 in industrial devices. It is apparent that the primary factor responsible
for the higher productivity of the membrane reactor is the larger mass transfer
area. Therefore, by operating at low feed rates, a membrane reactor can achieve
very high conversions, the typical characteristics of a plug-flow reactor. On the
other hand, the mass transfer area of a bubble-column reactor is proportional to
the gas flow rate. As the feed rate decreases, the conversion attainable in a
bubble-column reactor reaches a finite limit dictated by the bubble-rise time.
While the interfacial area is one factor in determining the productivity, the
mass transfer resistance is the other factor. In a hollow fiber membrane reactor,
the mass transfer resistance is basically independent of feed flow rate because the
major mass transfer resistance resides in the catalyst solution. However, the mass
transfer resistance in a bubble-column reactor varies with feed flow rate. The
turbulence caused by high flow rates results in a lowering of the mass transfer
resistance. The combined effect of the larger mass transfer area and the lower
resistance of the bubbler-column reactor, when it is operated at high feed rates,
produces higher conversions. As the feed flow rate becomes smaller, the mass
transfer resistance increases. When the gas void fraction is less than 1%,
represented by the experimental points on the left-hand side in Figures 6-8, the
conversion levels off. Because the achievable conversion in a bubble-column
MEMBRANE REACTOR, ETHYLENE OXIDATION 45
reactor is limited by the average bubble residence time, higher conversions are
not possible unless the liquid height is increased or a recycle arrangement is used.

CONCLUSIONS

Membrane reactor can be used to heterogenize a homogeneous catalytic reaction


with gas reactants and products. Very large interfacial areas can be provided by
hollow-fiber membranes. The membrane reactor arrangement allows a homoge-
neous catalytic reaction with gas reactants and products to operate like in a
plug-flow reactor, which can achieve high productivity without recycle.
The advantage of the membrane reactor for a given homogeneous reaction can
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be ascertained by a simple analytical solution, such as Eq. (12). If the


permeation-limiting assumption leads to a prediction of much higher conversions
than other rate-limiting assumptions, it will be potentially advantageous to use
the membrane reactor to carry out this reaction. In contrast, the use of
membrane reactor should not be considered if the predicted conversion under the
permeation-limiting assumption is close to that predicted under all-resistance-
considered assumption.
It is possible to achieve simultaneous reaction and separation of the products in
a membrane reactor. Multiple membrane bundles can be used for separate feed
introduction and product removal. This aspect is the current subject of
investigation.

ACKNOWLEDGEMENT

The partial supports (SHe) from SOHIO through Center of Excellence for
Membrane Technology, and from the University Research Council, University of
Cincinnati are gratefully acknowledged.

NOMENCLATURE

aD diffusion area per unit length.


ap permeation area per unit length.
CA concentration of A in catalyst solution, mol/rrr',
CA,o concentration of A at membrane-liquid interface, mol/rrr'.
DA effective diffusivity of A in the catalyst solution, m2/sec.
[max characteristic permeation rate as defined by Eq. (17).
HA Henry's Law constant of A, atm m3/mol.
k rate constant when kinetics is expressed as (-rA) = kCA.
L length of membrane reactor, m.
N total number of components in the reaction system.
46 SHIHAN CHEN AND YUEN-KOH KAO
reference pressure, atm
partial pressure in equilibrium with C A O' atm.
total pressure on tube side, atm.
molar flow rate in each membrane capillary, mol/sec.
permeability of A, mol m/rrr' atm sec.
feed rate to each capillary, mol/s.
coordinate as shown in Figure 2.
inner and outer radii of membrane capillaries, m.
molar dissipation rate of A per unit volume, mol/rrr' s.
characteristic reaction rate as defined by Eq. (13).
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volume of catalyst surrounding each capillary, rrr'.


reactant conversion.
mole fraction of A in gas phase.
feed composition of A.
YA.o composition of A at exit of the reactor.
z axial coordinate, defined as z = 0 at feed inlet.

Greek Letters
f3 parameter as defined by Eq. (16).
DD diffusion layer thickness surrounding each capillary, m.
Dp membrane thickness, m.
e reaction coordinate as defined by Eq. (6).
YA activity coefficient of A in catalyst solution.
4> Thiele modulus as defined by Eq. (14).
T residence time of reactants based on the inlet conditions, sec .
.,., effectiveness factor.
Vi stoichiometric number of species i.

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