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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
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Chem. Eng. Comm. 1990, Vol. 88, pp. 31-47
Reprints available directly from the publisher.
Photocopying permitted by license only.
1990 Gordon and Breach Science Publishers S.A.
Printed in the United States of America
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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FEED PRODUCT
(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) :
catalyst
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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
(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)
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)
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)
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
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
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
EXPERIMENTAL
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
~ 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.
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.
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
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 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
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
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
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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