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ELSEVIER Journal of Membrane Science 90 ( 1994) 1 l- 19

Ethane dehydrogenation using a high-temperature catalytic

membrane reactor
E. Gobina, R. Hughes*
Department of Chemical Engineering, Universityofsalford, Salford h4.5 4 W, UK

(ReceivedAugust 27, 1993; accepted in revised form December 17, 1993)

Abstract

Experiments have been conducted for the dehydrogenation of ethane to ethylene using a high-temperature cat-
alytic membrane reactor under isothermal conditions. Typically, conversions of up to 7 times (cocurrent mode)
and 8 times (countercurrent mode) higher than the equilibrium value achievable in conventional fixed-bed reac-
tors have been attained at high sweep flow rates. The membrane used in this study was a thin layer of Pd-23 wt%
Ag on porous Vycor glass. The significant improvement in the ethane conversion is attributed to the exclusive and
continuous permeation of hydrogen through the membrane.

Key words: Catalytic dehydrogenation; Metal membranes; Membrane reactors; Gas separations

1. Introduction availability of high-temperature, porous, ce-

Membrane reactors are unique in that they are
capable of combining chemical reaction and sep-
aration in a single-unit operation. The mem-
brane, being selective to one or more of the prod-
uct or reactant species, can be used to improve
the yields of thermodynamically limited reac-
tions. Although the basic concept of membrane
reactors has been known for almost three dec-
ades [ l-3 1, it is only recently that the applica-
tion of the concept is being recognised [ 4-6 1.
Low-temperature applications ( < 1OOoC)
were the first to benefit from this concept and an
extensive review has been carried out by Chang
and Furusaki [ 7 1. Most of the low-temperature
applications utilise organic membranes. The
*Correspondingauthor. Tel: 61-745-5081, Fax: 61-745-5999,
Email: R. Hughes @ Chemistry. Salford. ac.uk.
ramic and metallic membranes has opened up
new avenues to researchers and engineers for
carrying out catalytic processes at elevated tem-
peratures. This is because ceramic and metallic
membranes in contrast to their organic counter-
parts, are robust, can function for prolonged pe-
riods at high temperatures with great stability,
possess improved pore size controllability and
have higher rates of heat transfer. This develop-
ment has renewed interest in the use of high-
temperature catalytic membrane reactors and is
the subject of recent reviews [ 8,9]. Table 1 pre-
sents a selection of experimental studies, for gas-
phase reactions, utilising porous ceramic and
metallic membranes, attempted by several work-
ers to enhance the conversion of equilibrium-
limited reactions.
One particular class of reactions of industrial
importance is the dehydrogenation of lower al-

0376-7388/94/$07.00 0 1994 Elsevier Science B.V. All rights reserved

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12 E. Gobina, R. Hughes /Journal of Membrane Science 90 (1994) I I- 19

Table 1
Experimental studies of gas-phase reactions using membranes

Membrane Catalyst Chemical reaction Temperature Enhancement Ref.

material studied range ( “C) achieved

Porous A1203 MoSz in pores of membrane Decomposition of H2S 800 Two-fold increase on the 10
to form H2 and S equilibrium conversion
Porous A1203 Cr209 (20 wtl) Al,Os Dehydrogenation of 575 Conversion increased from an II
propane to propene equilibrium value of 40.1 to
58.7%
Microporous glass Pt/A1203 Dehydrogenation of 215 Conversion increased from 35% 12
cyclohexane without membrane to 80% with
membrane
Porous supported Dehydrogenation of 600-640 Conversion of ethylbenzene in 13
multrlayer A1203 ethylbenzene to styrene the presence of the membrane
were 15% higher than those in
the absence of the membrane
Porous Vycor glass Pt cat. within pores of the Dehydrogenation of 270 Conversion from an equilibrium 14
membrane (34 wt% Pt ) cyclohexane value of 26 to 56% in the
membrane
Microporous Thin dense film (20 pm) of Water gas shift reaction 400 Complete conversion of CO 15
glass/thin Pd film Pd coating the external attained in the membrane
surface of the glass reactor compared to the
equilibrium conversion of 60%
Dense Pd tube Pt/Al,O, (0.5 wt% Pt) Dehydrogenation of 200 Conversion of C6Hr2 was 99.7% 16
cyclohexane in the membrane reactor
compared with an equilibrium
conversion of only 18.7%
Non-porous Pd/Ag Gas-phase decomposition Decomposition of 500 The conversion of HI was 4%, a 17
tube hydrogen iodide twenty-fold increase from a
value of 0.2% in the absence of a
membrane

kanes. These yield valuable commodity chemi-
cals for the production of alcohols, gasoline
blends and polymers. However, these reactions
are also limited by their thermodynamic equilib-
rium and to obtain higher yields, very high tem-
peratures are required resulting in losses in both
selectivity and overall catalyst activity. An in-
centive therefore exists for a process that has the
capability of overcoming the thermodynamic
equilibrium while maintaining the integrity of the
catalyst and improving the product yield. Mem-
brane reactor technology appears to be promis-
ing since the selective removal of hydrogen from
the reaction products would inevitably tend to
shift the equilibrium towards increased product
yield. The integration of chemical reaction and
separation in a membrane reactor would then re-
sult in better rate control because of shorter con-
tact time and reduced temperature of operation.
When the membrane has also catalytic proper-
ties, even more avenues are opened and, for ex-
ample, one can couple reactions in a membrane
reactor.
Experimental investigations that have been at-
tempted for reactions accompanying membrane
separation with the objective of shifting the
equilibrium towards increased conversion in-
clude amongst others (see Table 1) the decom-
position of hydrogen sulfide [ 18 1, and decom-
position of hydrogen iodide [ 191 using
microporous glass membranes. Microporous al-
umina membranes have been used to investigate
the reaction of propane to propylene [ 201, ethane
to ethylene [ 2 1 ] and for the dehydrogenation of
ethylbenzene to styrene [ 131. In these investi-
gations, the flow of reactant and product species
through the membrane followed a Knudsen dif-
fusion mechanism and reactor performance was
much improved compared with a conventional
catalyst-packed reactor (see Table 1) . However,
 E. Gobina, R. Hughes /Journal of Membrane Science 90 (I 994) I l-1 9
computer simulations and experiments [ 141
have established that there is a limitation on the
performance of microporous membrane reactors
and it is almost impossible to make the reaction
proceed beyond a certain level of conversion
without the need to recycle the unreacted feed
since some ‘slip’ of feed also passes through the
micropores of the membranes into the separa-
tion side.
This limitation can be overcome by using a
membrane that is selective only to product(s).
This principle has been demonstrated by Itoh
[ 161 who succeeded in obtaining almost 100%
conversion for the dehydrogenation of cycloh-
exane when using a palladium membrane in-
stead of microporous glass membrane. A 20-fold
increase was obtained for the decomposition of
hydrogen iodide by using a non-porous palla-
dium/silver tube [ 171, far higher than that ob-
tained by using a porous membrane [ 19 1. This
high increase was attributed to the exclusive sep-
aration of hydrogen.
Palladium and palladium alloys are the cur-
rent preferred methods for removing hydrogen
exclusively. However, existing commercially
available palladium membranes are too thick
( N 53 pm) to provide economic rates of permea-
tion and palladium being an expensive metal, a
great thickness also means more cost. Although
the selectivity of microporous membranes is
limited, they could be employed as substrates on
which a thin metal layer of a dense membrane
material such as palladium may be deposited to
form a coherent layer having exclusive permea-
tion to hydrogen.
We have previously reported on the applica-
tion of a high-temperature membrane reactor for
the selective permeation of hydrogen from an
N2-Hz gaseous mixture [ 22 ] and the character-
isation of Pd-metallised porous Vycor glass pro-
duced by the process of magnetron sputtering
[ 231. In this paper, as part of an ongoing re-
search into membrane reactor applications, we
present results for the catalytic dehydrogenation
of ethane in a high temperature catalytic mem-
brane reactor promoted by 0.5 wt% Pd/A1203
catalysts packed in the tube side of the reactor.
The significant equilibrium shift observed shows
13
that the concept of overcoming thermodynamic
equilibrium limitations with consequent im-
proved product yields is feasible with a careful
choice of membrane.
2. Experimental
The experimental equipment used in this study
is similar to that employed earlier [ 231 and con-
sists of a feed gas delivery system, a high-temper-
ature membrane reactor, a gas chromatograph
and an on-line data acquisition system. The
membrane is a composite consisting of a porous
Vycor glass tubular substrate ( 10 mm o.d., 1.1
mm thick and pore size of 40 A) onto which a
thin continuous film of Pd-Ag was deposited by
the process of magnetron sputtering. The process
of magnetron sputtering can be used to deposit
very thin films on almost any porous substrate.
It involves ion bombardment of the target, thus
ejecting atoms which then adhere onto the po-
rous substrate. By exposing the substrate to a ra-
dio frequency (rf ) glow discharge (plasma), the
adhesion strength of the film can be enhanced.
Film thickness (and hence deposition rates) were
estimated using additional samples of porous
Vycor glass in the deposition chamber placed ad-
jacent to the actual substrate of interest. Direct
measurement of the film thickness on these sam-
ples was carried out using scanning electron mi-
croscopy (SEM ). The membrane thickness in
this investigation was 6 ,um. Film thickness uni-
formity was measured at various locations along
and across the samples by electrical resistivity.
The variation along the membrane averaged
6.7%. Film stoichiometry was determined by the
electron probe microanalysis technique
(EPMA ) . A total of 50 analyses was carried out
over a randomly selected area, and an average
value obtained. There was very little difference
between the Pd: Ag content in the target (77 : 23
wt%), and that on the substrate (23 + 3 wt% Ag ) .
There was no light transmission across the mem-
branes indicating a dense structure. Over an ex-
tended period of use in the membrane reactor,
there was no physical peeling from the substrate.
14 E. Gobina, R. Hughes /Journal of Membrane Science 90 (1994) 1 I-I 9
This is indicative of the good adherence strength
of the film.
The high-temperature membrane reactor, de-
tails of which are schematically shown in Fig. 1,
consists of an outer stainless steel shell (with
provision for either inflow or outflow of sweep
gas) and an inner tube. The membrane tube is
centralised in the reactor by a set of moulded
graphite rings packed at each end of the reactor.
Careful tightening of stainless steel plugs on both
ends compresses the rings and completes the seal
between the shell and tube. The thickness of the
Pd-Ag film was 6 pm and the area available for
hydrogen permeation was 47.14 cm2.
Three 0.5 mm thermocouples were located
along the axis of the catalyst bed to determine
the temperature profile inside the reactor. A sim-
ilar size thermocouple was located at the mid-
point of the shell side. Steady-state temperature
was attained when the variation in the thermo-
couple readings were within 22°C of the de-
sired temperature.
The catalyst for the dehydrogenation reaction
was located inside the tube and consisted of 2.55
g of 0.5 wt% Pd/A1203 cylindrical pellets (3.35
mm o.d.x3.63 mm long) which were carefully
and uniformly packed in the bed. The catalysts
were characterised by various techniques includ-
Fig. 1. Essential details of the catalytic membrane reactor.
ing BET surface area using nitrogen adsorption,
SEM and EPMA. The catalyst was used mainly
to promote the dehydrogenation reaction.
All experiments were performed at a total feed
pressure of 128.7 kPa ( 1.27 bar) while the shell
pressure was maintained at 10 1.3 kPa ( 1 bar).
The catalytic membrane and the catalyst pellets
were reduced in a flow of pure hydrogen at 2.5
cm3 (STP) /min for 30 min at a temperature of
400°C prior to the reaction experiments. The
feed gas mixture consisting of a single feed of 50
~01% ethane in nitrogen was then allowed to flow
at a predetermined rate over the catalyst pellets;
this continued until temperature stability was
achieved. Due to the endothermicity of the de-
hydrogenation reaction, a small temperature
drop in the catalyst bed was observed. This was
compensated by increasing the heat input to
maintain the desired temperature in the bed.
Temperature variation along the reactor was then
less than 3 “C. Membrane performance was as-
sessed by comparing the shift observed from the
equilibrium conversion of ethane. This equilib-
rium conversion was determined by closing the
shell-side inlet, so that shell-side sweep flow was
absent and continuously monitoring the effluent
from the catalyst bed via an air-activated auto-
matic sampler. This was continued until con-
stant concentrations were obtained as indicated
by identical values of the peak chromatograph
areas. The ethane conversion calculated under
these circumstances was the equilibrium conver-
sion and was then used for comparison with con-
versions obtained when the shell side was opened
and the sweep gas consisting of pure nitrogen was
allowed to flow. Both the permeate and retentate
streams were sampled. The shell-side sweep gas
flow was then varied and flow directions re-
versed for either cocurrent or countercurrent op-
erations while maintaining the temperature and
feed mole fraction of ethane constant.
Reaction experiments were conducted in the
reactor using a single feed consisting of a 50 ~01%
mixture of ethane in nitrogen, the nitrogen serv-
ing as an internal standard for the analysis of gas
composition. All experiments were carried out at
660 K under isothermal conditions.
 E. Gobina, R. Hughes /Journal of Membrane Science 90 (I 994) 1 I-l 9
3. Results and discussion
3.1. Permeability of membrane under non-
reactive conditions
The permeability of the membrane to hydro-
gen was studied using a 60% Ha: 40% Nz gas
mixture, varying the driving force and the tem-
perature in order to obtain quantitative infor-
mation regarding the permeability of the mem-
brane. If the permeate rate of hydrogen gas
through the Pd : Ag membrane [ QH ( cm3 ) ] is as-
sumed to obey the half-power pressure law [ 241,
then:
QH =Qopt” -pi”) (A/d,)
where Q0 is the permeability constant of hydro-
gen gas through the membrane (cm3 cm/cm2 s
atm”‘) ; A is the membrane area available for
flow (cm2); and dt is the film thickness of the
membrane (cm). A typical plot of Qu versus
(P ;I2 -pii ) at various operating temperatures
is given in Fig. 2. The permeation rate of hydro-
gen gas is directly proportional to the difference
1.6 .
Fig. 2. Effect of pressure and temperature on the permeation
rate of hydrogen.
15
in the square roots of the upstream and down-
stream hydrogen partial pressures. This is con-
sistent with Sieve&s law [ 25 1, and indicates that
permeation through the bulk of the metal is the
rate-limiting step. A closer inspection of Fig. 2
also reveals that there is a temperature effect on
the permeability constant. This was further in-
vestigated by maintaining a constant pressure
difference while varying the temperature. The
results correspond to the Arrhenius law and the
permeability constant (Q ) of hydrogen gas
through the film can then be expressed as follows:
Q,,=7.174x 10m5exp( -6.380/RT) (2)
where R is the ideal constant (kJ/mol K) and T
(1) the absolute temperature (K). The activation
energy of 6.38 kJ/mol obtained in this investi-
gation compares well with reported values of 5.73
[26], 6.60 [27], and 5.86 kJ/mol [28]. In these
previous investigations, similar Pd-Ag alloy
membranes were employed.
3.2. Ethane dehydrogenation experiments
The equilibrium conversion of ethane to eth-
ylene was determined twice (before and after ex-
periments in the membrane reactor). An aver-
age value of 2.57% was obtained and used for
comparison with the membrane reactor conver-
sions. This value is simply the maximum con-
version achievable in the absence of hydrogen
separation and may be compared with a value of
0.87% estimated from thermodynamic data for
the same temperature. A similar three-fold in-
crease in the measured equilibrium constant for
this reaction compared to the thermodynamic
value was obtained by Champagnie et al. [ 2 I 1.
Operation of the catalytic membrane reactor was
achieved by varying the flows of the feed and/or
sweep gas at constant temperature using a fixed
weight of catalyst. The overall conversion of
ethane to ethylene, allowing for volume changes
was obtained using the equation,
X=( FA;rOFA)x 100% (3)
where X is the overall ethane conversion to eth-
16 E. Gobina, R. Hughes /Journal ofMembrane Science 90 (1994) 11-I 9
ylene; FAOand FA are the respective flow rates of
ethane in the feed and product in the tube side.
No ethane or ethylene was detected in the shell
side exit confirming that the membrane is selec-
tive only to hydrogen.
3.3. Conversion vs. time factor
The effect of time factor ( W/F,,) defined as
the weight of catalyst in the bed, W (g), divided
by the molar flow rate of ethane, FAO(mol/s),
on the conversion of ethane to ethylene is pre-
sented in Fig. 3. The conversion of ethane de-
pends on the mean residence time of ethane in
the reactor. This means that conversion in-
creases with the time factor as expected. In the
catalytic membrane reactor, at long contact
times, the conversion of ethane to ethylene be-
comes higher than the equilibrium value because
product hydrogen is preferentially and exclu-
sively diffused through the membrane. This se-
lective and continuous removal of hydrogen from
the reaction zone, results in a shift in the equilib-
rium towards increased ethane conversion. At
very short contact times, equilibrium shift is pre-
vented because the mean residence time of ethane
in the reactor is too short.
Under conditions of varying feed flow rate at
constant catalyst weight, the external mass trans-
fer rate changes with the velocity of the gas
JA
0.5 1.5 2.5
TIblE PKTOH
,!4,FA<>i x 105 vi-at Z,WOl
Fig. 3. Influence of time factor ( W/F,,) on the conversion
of ethane in the membrane reactor. Temperature, 600 K; cat-
alyst weight, 2.55 g; flow rate of sweep gas, 300 cm3 (STP)/
min.
stream. The mass transfer flux, N, to the inner
surface of the membrane is given by
N= (~1 -pz)Sh D,,ld (4)
where p1 and p2 are the molar densities of hydro-
gen on the reaction and permeate side, respec-
tive ( mol/cm3), DABis the diffusivity of hydro-
gen in the reaction mixture (cm2/s), d is the
reactor diameter (cm) and Sh is the Sherwood
number (k,d/D) . The permeate-side concentra-
tion of hydrogen was very small due to the pres-
ence of the sweep gas. Under the conditions of
the present study, the flow on the reaction (tube)
side was laminar and the Sherwood number is
given by [ 29 ] :
where Re and SC are the Reynolds and Schmidt
numbers, h and h are the fluid viscosities at av-
erage bulk temperature and the wall, respec-
tively, and L the length of reactor across which
permeation of hydrogen occurred. Using this
correlation for Sh and the flux equation (4)) the
hydrogen mass transfer flux from the bulk gas to
the inner membrane surface was always greater
than the permeation flux and therefore mass
transfer in the tube side was not limiting.
A comparison of the efficiency of the modes of
operation of the catalytic membrane reactor is
shown in Fig. 4. Both countercurrent and cocur-
rent modes of operation were examined. In the
countercurrent mode, the flow of the sweep gas
was in the opposite direction to that of the feed
while in the cocurrent mode both were in the
same direction. Experimental results show that
operation of the membrane reactor in the coun-
tercurrent mode is more desirable compared to
that in the cocurrent mode. This is because higher
conversions can be obtained for the same sweep
flow in the countercurrent mode than for the co-
current mode. This conclusion was also arrived
I
3.5 at by computer simulation results, in a mem-
brane reactor hy Itoh [ 16 ] for the dehydrogena-
tion of I-butene and shown experimentally for
the dehydrogenation of cyclohexane [ 281. In
these studies Pd-Ag membranes similar to that
used in the present study were employed.
 E. Gobina, R. Hughes /Journal of Membrane Science 90 (1994) 11-I 9
Fig. 4. Effect of sweep gas flow rate on ethane conversion.
(-- ) Equilibrium; ( 0 ) cocurrent flow; ( A ) countercurrent
flow. Time factor ( W/F,,) = 1.144 x 10’ g cat s/g mol; tem-
perature, 660 K, space time, 8.4 s.
Fig. 5. Membrane reactor conversion as a function of the
sweep gas/feed gas flow ratio. Temperature, 660 K; cocur-
rent flow.
3.4. Effect of sweepjlow/feedjlow
Fig. 5 shows the conversion of ethane to eth-
ylene at a temperature of 660 K as a function of
the sweep gas ratio; defined as the ratio of the
flow rate of sweep gas in the shell side to the feed
inlet flow rate. The feed-side inlet consisted of a
50 ~01% ethane in nitrogen mixture. Increasing
the sweep ratio increases the ethane conversion.
This is due to the fact that in the catalytic mem-
brane reactor, conversion is increased by the se-
lective and exclusive removal of hydrogen con-
17
tinuously from the reaction zone. Since these Pd-
Ag membranes are selective only to hydrogen, an
increase in the sweep ratio ensures a large hydro-
gen partial pressure difference between the shell
side and tube side. The partial pressure differ-
ence across the membrane is the driving force for
hydrogen permeation which results in an equi-
librium shift towards higher ethane conversion.
At a sweep ratio of 5, for example, the ethane
conversion increases from the equilibrium value
of 2.5 (without any flow of sweep gas) to 17.66%.
This is a 7-fold increase, and is attributed to the
selective and continuous removal of hydrogen
from the reaction zone. This result compares with
a 6-fold increase reported by Champagnie et al.
[ 2 I] who employed a Pt-impregnated porous al-
umina membrane having a pore size of 40 A, for
ethane dehydrogenation. By using a dense metal-
lic membrane in this study, we have thus elimi-
nated the problem of back-permeation of reac-
tant from the permeate side to the feed side at
high conversions and re-equilibration [ 301 often
encountered in porous membrane reactor
systems.
3.5. Performance of the membrane reactor
Table 2 shows the relationship between mem-
brane performance and rate of reaction at high
performance, i.e., at a conversion of N 18%. The
rate of Hz permeation is 6.7 times the produc-
tion rate. This suggests that the membrane has
sufficient capacity to permeate the hydrogen and
that the flow through the membrane is not rate
limiting. Although the hydrogen removal rate is
far in excess of the production rate, Fig. 3 sug-
gests that at sufficiently long contact times the
conversion attains a virtually constant value. The
reason for this is not clear; one possibility is that
Table 2
Estimation of catalytic membrane reactor performance
Temperature Ethane H2 production H2 permeation rate
(K) conversion rate [usingpermeability
W) (gmof/s) Eqs. (2) and (3)]
(gmol/s)
18 4.0x 10-h 26.7X IO-6
660
18 E. Gobina. R. Hughes /Journal of Membrane Science 90 (I 994) I I- 19
readsorption of ethylene and hydrogen on the
surface of the catalyst pellets occurs under these
conditions and this is related to the relative high
surface area of the catalyst employed
(-200 m2/g).
The dehydrogenation of 1 mol of ethane yields
equimolar amounts of ethylene and hydrogen.
The selectivity of ethylene calculated when no
sweep gas was present was 50%. However, when
a sweep gas flow was used this selectivity was
close lOO%, indicating that almost all of the hy-
drogen in the gas phase was removed by the
membrane.
4. Conclusions
It has been shown experimentally that a much
higher level of ethane conversion can be attained
even in a single-stage catalytic membrane reac-
tor. The significant characteristic advantages are
that it is possible to carry out the reaction at a
lower reaction temperature and shorter contact
time. This results in a shorter reactor length and
lower energy requirement for eventual separa-
tion of the product(s) and reactant (s ) from each
other and from the reaction mixture. Such a re-
actor could be applied to study other dehydro-
genation reactions of industrial importance such
as the conversion of ethylbenzene to styrene, bu-
tene to butadiene and methanol to formalde-
hyde. Because the metallic surface is in itself cat-
alytic to a host of hydrogenation reactions, there
exists a possibility of coupling the endothermic
dehydrogenation with an exothermic hydrogen-
ation reaction. This would assist transport of both
hydrogen and heat in the system. Work in this
area is continuing.
5. Acknowledgements
We thank the SERC for continued financial
support in this research. We are also grateful to
Dr. Dermot Monaghan for his assistance in car-
rying out the magnetron depositions in the sub-
strate. Characterisation of the catalyst pellets and
palladium film stoichiometry was undertaken by
Johnson Matthey Research Centre, Sonning
Common to whom we express our thanks.
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