Chemical Engineering Science, Vol. 53, No. 22, pp.

3821—3834, 1998
( 1998 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
PII: S0009–2509(98)00189–4 0009—2509/98/$—See front matter

Ethylene epoxidation in a catalytic packed-

bed membrane reactor
Miguel A. Pen8 a,* David M. Carr, King Lun Yeungs
and Arvind Varmat
Department of Chemical Engineering, University of Notre Dame, Notre Dame, IN 46556,
U.S.A.
(Received 8 January 1998; acepted 12 June 1998)
Abstract—The performance of different membrane reactors for the epoxidation of ethylene was
compared with that of a conventional fixed-bed reactor (FBR), under identical overall reaction
conditions, using a cesium-doped silver catalyst supported on a-alumina. Two packed-bed
membrane reactor configurations were used, one using oxygen as permeate with ethylene
flowing over the catalyst bed (PBMR-O), and the other using ethylene as permeate with oxygen
flowing over the catalyst bed (PBMR-E). The study of the FBR showed that high oxy-
gen/ethylene ratio increases ethylene oxide selectivity. The behavior of the membrane reactor
was different depending on the configuration, with the PBMR-O exhibiting smaller and the
PBMR-E larger ethylene oxide selectivity, as compared to the FBR. While maintaining the
overall reaction conditions fixed, ethylene oxide production in the membrane reactor could be
increased further by manipulating the residence time of the reactants over the catalyst bed, and
the maximun value was obtained for the largest possible residence time. The results demon-
strate the operational flexibility and potential attractiveness of membrane reactors, since local
reactant concentrations and residence times can be tuned to optimize reactor performance.
( 1998 Elsevier Science Ltd. All rights reserved.
Keywords: ethylene epoxidation; ethylene oxide; silver catalyst; membrane reactor; fixed-bed
reactor; inorganic membranes

1. INTRODUCTION one of the reactants is distributed along the catalyst

Recent developments in preparation of inorganic
membranes have opened the potential of their ap-
plications to improve the performance of catalytic
reactors, since they can be used at more severe operat-
ing conditions than are possible for polymeric mem-
branes. Several recent reviews describing the benefits
of inorganic membrane reactors, with catalytic and
inert membranes, are available in the literature
(Saracco and Spechia, 1994; Soria, 1995; Tsotsis et al.,
1993; Zaman and Chakma, 1994). Regarding applica-
tions of inert membranes to catalytic reactors (i.e.
Packed-Bed Membrane Reactors, PBMR), two differ-
ent configurations are the most widely used. In one,
the membrane is used for the selective separation of
one of the products, producing a shift of the reaction
equilibrium and increasing productivity. In the other,
* Present address: Instituto de Catálisis y Petro-
leoquı́mica, CSIC, Campus UAM, Cantoblanco, 28049
Madrid, Spain.
s Present address: Department of Chemical Engineering,
The Hong Kong University of Science and Technology,
Clear Water Bay, Kowloon, Hong Kong, PRC.
tCorresponding author. Tel.: 1-219-631-6491; Fax: 1-219-
631-8366; E-mail: avarma@darwin.cc.nd.edu.
3821
bed, segregating the components of the feed, which
allows a control of how the reactants contact each
other. The latter configuration has been applied to
partial oxidation of hydrocarbons, where the oxygen
is fed along the membrane, and the control of selectiv-
ity is achieved by changing the local partial pressure
of oxygen. The segregation of reactants reduces
explosion risk and avoids side-reactions arising from
pre-mixing. Dense membranes transporting atomic
oxygen can be applied for this purpose, but they yield
relatively small oxygen fluxes, resulting in low pro-
ductivity. An attractive approach is the use of porous
membranes, that can provide a high reactant flux,
while maintaining a homogeneous distribution. They
have been applied to both oxidative coupling of meth-
ane and oxidative dehydrogenation (Coronas et al.,
1994, 1995; Pantazidis et al., 1995; Tonkovich et al.,
1996a, b). Porous membranes allow the controlled
distribution not only of oxygen, but also of any reac-
tant used in the reaction, and hence provide greater
flexibility.
The epoxidation of ethylene to produce ethylene
oxide is one of the most studied catalytic processes
due to the importance of the latter as an intermediate
in the chemical industry (Berty, 1983; Sachtler et al.,
3822 M. A. Pen8 a et al.
1981; Sajkowski and Boudart, 1987; Van Santen and
Kuipers, 1987). The process has been practiced com-
mercially since the 1930s, and some seven billion
pounds of ethylene oxide are produced annually in the
U.S. alone (Kirschner, 1996). It is remarkable that
silver is the main ingredient of all the active and
selective catalysts, and that ethylene is the only olefin
that can be epoxidized with high yields. The catalyst
performance can be improved by support selection and
modification, use of alkaline promoters in catalyst
composition, use of chlorinated hydrocarbons as feed
additives, and optimal distribution of catalyst in pellets
(Berty, 1983; Gavriilidis and Varma, 1992; Yeung et al.,
1998). The reaction network is widely accepted, with
the following parallel and consecutive reactions:
However, there is no general agreement either
about the reaction mechanism on the surface of the
silver catalyst, or about the reaction kinetics. Three
different oxygen species (molecular, atomic and sub-
surface) can be found on the catalyst surface, and
although molecular oxygen is usually considered to be
responsible for epoxidation and atomic oxygen for
combustion, their role has not been clearly assigned
(Van Santen and Kuipers, 1987). There is also not
a definite consensus about the influence of partial
pressure of reactants on the reaction kinetics, and very
different values of the reaction orders for both oxygen
and ethylene (from negative to positive) can be found
in the literature (Sachtler et al., 1981). There are sev-
eral descriptions of the inhibition effect of the different
reaction products, ethylene oxide (Borman and Wes-
terterp, 1995; Stoukides and Pavlou, 1986), carbon
dioxide (Bulushev and Khasin, 1991; Eliyas and Pet-
rov, 1990), and water (Borman and Westerterp, 1995;
Liu et al., 1990), and indeed some discrepancies exist
between different authors (Schouten et al., 1996). Fi-
nally, various models have been used to fit kinetic
data, with both Langmuir—Hinshelwood and Eley—
Rideal mechanisms, using different active species and
limiting step assumptions, without any definitive con-
clusions at the present. Thus, it is not unusual that
papers with new data about ethylene epoxidation
kinetics continue to appear in the literature (cf.,
Khasin 1993; Kung 1992; Schouten et al., 1996).
Therefore, with all these uncertainties, it is not easy to
predict the behavior of a new reactor design when
applied to this reaction.
The objective of this work is an experimental study
of ethylene epoxidation over a silver-based catalyst,
using a Packed—Bed Membrane Reactor (PBMR).
The catalytic reactor uses the membrane for control-
led addition of reactants, oxygen or ethylene, and
a porous inert membrane is selected for this purpose.
The performance of the reactor is compared with that
of a conventional Fixed-Bed Reactor (FBR), and their
behavior at different temperatures and feed reactant
concentrations is analyzed. The membrane is also
used to manipulate the residence times of the re-
actants, using the same overall feed conditions. The
results are examined for obtaining the largest value of
ethylene oxide selectivity, at a fixed ethylene conver-
sion, and the different reactor configurations are com-
pared in this regard.
2. EXPERIMENTAL
2.1. Catalyst preparation and characterization
The catalyst was prepared based on the procedure
outlined by Bhasin et al. (1990). Pretreated a-Al O
2 3
right-cylindrical pellets (Norton SA 5102, 3 mm OD,
1.13 m2/g) were used as catalyst support. The pre-
treatment consisted of acid leaching (1 N HCl), fol-
lowed by calcination at 1100°C for 24 h. The pellets
(30 g) were dried and outgassed in vacuum for 30 min
prior to impregnation with warm solution (85°C) con-
taining 25 g silver oxide, 0.8 ml of 0.008 g/ml CsOH
solution (Aldrich Chemical Co.), 53 g lactic acid and
1 ml hydrogen peroxide. After 30 min, the solution
was drained and the pellets were dried in vacuum.
The dried catalyst was calcined in N at 500°C for
2
5 h to decompose the lactic acid, and pretreated in
two oxidation—reduction cycles at 350°C (3 h O and
2
3 h H ) to obtain stable catalyst activity. The final
2
catalyst had loadings of 13.54 wt% Ag and 0.005 wt%
Cs. The catalyst loadings were calculated based on the
dried weight of the support and reduced catalyst, and
were similar to experimental values obtained by
atomic absorption spectroscopy analysis of the im-
pregnating solution, before and after impregnation
(Perkin—Elmer 2280).
The silver surface area was measured using a pulse
chemisorption apparatus (Gavriilidis et al., 1993), fol-
lowing the procedure described by Lemaitre et al.
(1984). Oxygen chemisorption was conducted with
helium (UHP grade) carrier gas at 200°C after catalyst
pretreatment with oxygen (UHP grade) at 200°C for
2 h, followed by hydrogen (UHP grade) at 200°C for
another 2 h. Monolayer oxygen coverage, with close
to one oxygen atom per silver surface atom (Smetzer
et al., 1956; Czanderna, 1964), was obtained under
these conditions. A site density of 1.15]1015 Ag /cm2
S
(Satterfield, 1991) was used for the surface area
calculation. The silver surface area obtained was
925 cm2 Ag/g cat. Scanning electron micrographs
(JEOL JSM 6300) show that the alpha alumina sup-
port is densely covered with 0.3—0.5 lm silver crystal-
lites.
Chemical analyses of alumina support and catalyst
surfaces were conducted using X-ray photoelectron
spectroscopy (XPS, 5600 ESCA, Physical Electronics
Inc.) equipped with an aluminum anode mono-
chromator (400 W) and operated at 187.5 eV. The
surface composition of the samples is summarized in
Table 1. The support contains carbon, sodium and
 Ethylene epoxidation in a catalytic packed-bed membrance reactor 3823
Table 1. XPS analysis of a-alumina support and Ag/a-alumina catalyst

Sample Al O Ag Cs C Na Ca Cl P Si

Norton SA 5102 29.9 59.5 — — 5.5 2.9 0.4 0.5 0.2 1.0
Catalyst 26.6 56.5 4.3 0.03 8.6 2.3 0.4 0.2 0.3 0.7

silicon as main impurities arising from the manufac-
turing and pelletizing steps. The significant carbon
content of the catalyst probably resulted from de-
composition of lactic acid employed in the catalyst
preparation.
2.2. Fixed-bed reactor and membrane reactor experi-
ments
The performance of fixed-bed (FBR) and packed-
bed membrane (PBMR) reactors for ethylene
epoxidation was studied in a shell-and-tube reactor
configuration, with the membrane or a blank tube
located in the center. The reaction occurred on the
catalyst bed located in the annulus. By maintaining
the same reactor configuration, reaction conditions
and catalyst bed geometry, direct performance com-
parisons between FBR and PBMR could be made.
2.2.1. Experimental apparatus. The membrane re-
actor consisted of a shell and tube with two feed inlets
and one reactor outlet [Fig. 1(a)]. The membrane was
a 45 mm long porous 316 L stainless steel tube (Mott
Metallurgical Corp.; 0.20 lm grade; 10 mm OD)
welded to a non-porous 316 L-SS tube. Porous stain-
less steel was chosen for its thermal properties
and machinability. The permeation flux of helium
through this membrane at room temperature was
58.2 ml(STP)/min bar cm2. The membrane tube con-
tained a stainless steel feedthrough tubing with four
narrow slits to increase the pressure drop [Fig. 1(b)].
The gases were fed through the stainless steel tube,
and the opposite end was plugged with a cap. With
this configuration, the room temperature helium per-
meation rate in the membrane tube was 3750 sccm at
0.69 bar trans-membrane pressure drop, that was still
a high value of flux. In order to reduce the permeabil-
ity of the membrane, a sintering process was carried
out. Figure 2 shows how the permeation is reduced as
the treatment temperature increases. These experi-
ments were carried out using two 80 mm long samples
of membrane that were treated consecutively at in-
creasing temperatures for 12 h. One sample was
heated in helium and the other in air. The treatment in
air reduced the permeability to a larger extent, and

Fig. 1. Schematic diagram of (a) membrane reactor and (b) membrane feedthrough.
3824 M. A. Pen8 a et al.
Fig. 2. Variation of the helium permeance of the stainless
steel membrane with the pretreatment temperature in helium
and air atmospheres. Consecutive treatments of 12 h. He-
lium flow rates were measured at room temperature and
0.69 bar trans-membrane pressure drop.
this reduction was especially effective in the temper-
ature range 800—850°C. The membrane tube used for
all subsequent experiments was heated in air at 800°C
for 12 h, and after this treatment, the room temper-
ature helium permeation rate was 730 sccm at
0.69 bar trans-membrane pressure drop.
The membrane was inserted into a 19 mm OD
quartz tube (17 mm ID) forming a 3.5 mm annulus.
The catalyst was packed uniformly within the annulus
covering the entire membrane region (45 mm long).
Gases were introduced separately on both membrane
and catalytic bed (annulus) sides, and exited together
from the reactor. In order to maintain the same reac-
tor and bed geometry, for fixed-bed reactor (FBR)
studies the membrane feed inlet was simply plugged
off. Similar results were obtained by replacing the
membrane tube with a non-porous tube of the same
dimensions.
The reactant gases used in the experiments were
ethylene (Linde, CP grade), oxygen (Linde, zero grade)
and nitrogen (Linde, pre-purified). The volumetric
flow rates of the individual gases were metered using
Unit UFC-1000 mass flow controllers to provide the
desired overall flow rate and feed gas composition.
The reactor temperature was regulated using a heat-
ing tape, and thermocouples were inserted to monitor
the temperature of the catalyst bed. One was placed at
the external wall of the reactor quartz tube and was
used as the signal for the temperature controller, while
the other was inserted in the center of the membrane
feedthrough. Both thermocouples were placed in the
middle of the catalytic bed (22 mm from the top).
Temperature and limit controllers (Omega) were used
to maintain constant reactor temperature and prevent
high-temperature excursions. The membrane and re-
actor pressures were monitored using Bourdon tube
pressure gauges. The exit lines were heated and
insulated to prevent water condensation prior to
composition analysis of the outlet gases.
An on-line Beckman 565 infrared CO analyzer
2
monitored the carbon dioxide concentration in the
exit stream. Detailed gas composition analysis was
performed using a Hewlett Packard 5890 II gas
chromatograph, equipped with a thermal conducti-
vity detector and a Porapak-Q column (1/8A OD,
1.8 m long). The carrier gas was helium and the tem-
perature of the analysis was 100°C. The data were
collected and analyzed using a Hewlett Packard 3396
II integrator. The response factors for the gas
chromatographic analysis were taken from the litera-
ture (Dietz, 1967). With the chromatographic system,
concentrations of ethylene, ethylene oxide, carbon
dioxide and water in the outlet stream were measured,
while the concentration of oxygen was calculated us-
ing an overall mass balance as well as an oxygen
balance over the reactor. Carbon balances typically
closed to within 2%.
2.2.2. Experimental procedure. The volume of cata-
lyst bed was 6.7 cm3 and occupied the annulus formed
by the membrane (10 mm OD) and quartz reactor
(17 mm ID). For reaction experiments, the catalyst
pellets were crushed to obtain particles in the range
425—850 lm. The catalyst particles were diluted with
the same size particles of pretreated a-alumina, fol-
lowing the same acidic treatment described in Section
2.1 for the catalyst support. Both catalyst and alumina
particles had a packed density of 1.12 g/cm3. In order
to fill the entire 45 mm length of the catalytic bed,
1.0 g of Ag—Cs/a-alumina catalyst particles were uni-
formly mixed with 6.5 g of a-alumina diluent particles.
The catalyst was pretreated in a flowing stream
(200 sccm) of reaction gas mixture containing 6%
C H , 6% O , and balance N at 280°C for 48 h prior
2 4 2 2
to the reaction study. After this pretreatment, the
catalyst demonstrated stable and reproducible acti-
vity and selectivity. Under the reaction conditions,
homogeneous or wall reactions were absent for ethy-
lene. In addition, the only reaction products were
ethylene oxide, carbon dioxide and water. Both fixed-
bed and membrane reactors were operated as single-
pass units under steady-state conditions.
Reaction data were obtained at varying levels of
reactant feed concentrations (C H and O ), residence
2 4 2
time, and temperature to form the basis of the perfor-
mance comparison. All experiments were conducted
using a total flow rate of 200 sccm. The temperature
was varied in the range 210—270°C for each experi-
mental condition. In the first set of experiments, the
oxygen concentration was varied (3—12%), maintain-
ing the concentration of ethylene fixed at 6%. In the
second set, ethylene concentration was varied (3—12%)
with a fixed 6% oxygen. The diluent in all cases was
nitrogen. In the fixed-bed reactor (FBR), the feed
entered the reactor annulus, reacted along the catalyst
bed and exited the reactor as a single stream. In the
packed-bed membrane reactor (PBMR), the overall
feed was divided into two streams where one entered
 Ethylene epoxidation in a catalytic packed-bed membrance reactor 3825
the reactor annulus and the other entered the mem-
brane. The divided feed remained segregated, and was
allowed to combine only along the catalyst bed before
exiting the reactor. One stream contained ethylene
and nitrogen, and the other oxygen and nitrogen. It is
important to note that the ethylene and oxygen con-
centrations reported in this work are based on composi-
tion of the overall feed, and not of the individual streams.
The PBMR was used with two different configura-
tions: in one, the ethylene stream entered the catalytic
bed inlet while the oxygen stream was introduced at
the membrane inlet (oxygen feed from membrane,
PBMR-O); in the second, the oxygen stream entered
the catalytic bed inlet while the ethylene stream was
introduced at the membrane inlet (ethylene feed from
membrane, PBMR-E). In the first and second set of
experiments, the molar ratio between the nitrogen
introduced with ethylene (N ) and oxygen (N ) Fig. 3. Variations of the residence time for ethylene and
E O
streams was maintained fixed at N /N "1.5. In this oxygen, in the two PBMR configurations, as functions of the
E O fraction of nitrogen fed with ethylene.
way, the residence times of ethylene and oxygen (as
defined below) are maintained essentially constant
when the overall gas feed composition is varied.
The membrane provided the medium for controlled
It is easy to vary both mean residence times, for
mixing of the two streams and a way for directly
a fixed total flow rate and reactant concentrations, by
manipulating the reactant concentration profile and
changing the nitrogen distribution that was fixed in
residence time distribution along the catalyst bed. In
the first and second set of experiments as N /N "1.5.
the third set of experiments, while maintaining the E O
Figure 3 displays the variation of the mean residence
overall composition constant, the influence of varying
times for ethylene and oxygen, in the two configura-
the residence time was studied. The residence time in
tions of PBMR, when the fraction of nitrogen fed with
the FBR is fixed for a specific catalyst weight and total
the ethylene stream is changed from 0 to 100% of the
flow rate (q"» /F ; where » is catalyst volume
#!5 T #!5 total nitrogen used. For the PBMR-O, an increase of
and F is total volumetric flow rate). In the FBR used,
T the fraction of nitrogen fed with the ethylene (i.e.
with 0.89 cm3 of catalyst and a total flow rate of
entering the catalytic bed annulus) decreases both
200 sccm, the residence time was 0.27 s. However, in
residence times. The opposite is true for the PBMR-E
a membrane reactor, the situation is different. The
configuration.
residence time of the reactant entering the annulus is
In all the experiments, a temperature gradient be-
not constant, but varies along the catalytic bed due to
tween the internal (center of the membrane) and the
the change in space velocity produced by the feed
external (reactor wall) thermocouples was observed.
entering from the membrane. It is possible to define
This temperature gradient was in the range 6—10°C,
a mean residence time of this reactant as (Tonkovich
with the higher temperature in the inner part because
et al., 1996a)
of the exothermic reactions involved, especially ethy-
» lene combustion. The temperature reported in the
q " #!5 experiments is the average of these two values.
cb F #0.5F
cb m The pressure in the catalytic bed was 1.08—1.10 bar,
where F and F are the volumetric flow rates of the while in the inner membrane it was in the range
cb m 1.21—1.59 bar, depending on the flow conditions.
streams entering the catalytic bed and membrane in-
lets, respectively. The reactant entering the membrane
inlet, in addition to the effect mentioned above, has 3. RESULTS AND DISCUSSION
a distribution of contact times, depending on the We now consider and compare the performance of
position from which the molecules of this reactant fixed-bed (FBR) and packed-bed membrane reactors
permeate (from top to bottom of the catalytic bed). (PBMR). As noted above, the PBMR can be operated
Therefore, it is necessary to compute the mean resi- in two modes, where the oxygen or ethylene are fed to
dence time for a specific permeation point along the the membrane, leading to the PBMR-O and PBMR-E
catalytic bed, and then to average this mean value for configurations, respectively. The comparisons among
different permeation positions. The mean residence the two modes, and with the FBR, are made for
time for the reactant entering the membrane inlet is identical temperatures, overall feed compositions,
then given by (Tonkovich et al., 1996a) total flow rate, and catalyst mass. In addition, the
effect of varying the mean residence time of each

C A B D
2» 2(F #F ) F #F reactant over the catalyst bed, while maintaining the
q " #!5 m cb ln m cb !1 .
m F F F #0.5F overall conditions fixed, is investigated.
m m cb m
3826 M. A. Pen8 a et al.
3.1. Performance of the fixed-bed reactor (FBR)
Figure 4(a) and (b) show the rates for ethylene oxide
and carbon dioxide production as functions of reac-
tion temperature for various feed oxygen levels. The
production rates for carbon dioxide are greater than
those for ethylene oxide over the entire temperature
range, indicating a higher selectivity for combustion
as will be discussed later. In general, both production
rates increase with temperature. In the case of 3%
oxygen, the rate for carbon dioxide reaches a plateau,
while for ethylene oxide production there is a slight
decrease at 270°C. The ethylene oxide production rate
at 6% oxygen also begins to from a plateau at high
temperature. This could be assigned to oxygen being
the limiting reactant, although the maximum oxygen
conversion under the reaction conditions of these
figures was 90% (3% oxygen, 270°C). The decline of
the production rates can also be assigned to the signi-
ficant decrease of reactant concentrations along the
catalytic bed, typical of integral reactors, as well as to
ethylene oxide combustion at higher temperatures.
Figure 4(c) and (d) show the effect of temperature
on the rates for ethylene oxide and carbon dioxide
production for various feed ethylene levels. In general,
the rates again increase with temperature, and the
carbon dioxide production rates are higher than those
for ethylene oxide. The limiting effect of oxygen, as
well as ethylene oxide combustion, are present in the
curves of 9 and 12% ethylene for ethylene oxide
production rate at high temperature, where for 12%
ethylene there is a distinct decrease at 270°C. The
maximum oxygen conversion for these conditions was
again 90%. In the same way as for oxygen, increase of
ethylene concentration in the feed generally increases
the production rates.
Figure 5(a) and (b) plot ethylene oxide selectivity
and yield vs ethylene conversion, for different oxygen
concentrations in the feed. Both quantities increase
with oxygen concentration. In Fig. 5(a), the calculated
limit curve for 100% oxygen conversion has been
included for the experiments with 3% oxygen in the
feed. It is clear that the shape of the selectivity—con-
version plot changes as this limit is approached, with
an abrupt decrease in selectivity for conversions high-
er than about 17%.
Figure 5(c) and (d) display the selectivity—conver-
sion and yield—conversion curves for various ethylene
levels in the feed. We have here the opposite effect,
with a decrease of both selectivity and yield with
ethylene concentration. The 100% oxygen conversion
limit curve has been included in Fig. 5(c) to explain the
sharp decrease of the curve for 12% ethylene. A sim-
ilar feature occurs for 9% ethylene. By comparing
Fig. 5(a) and (c), we observe that the influence of
ethylene concentration on selectivity is smaller than
that of oxygen, especially at low ethylene conversion.
This is more evident in the yield—conversion plots,
where the curves merge [Fig. 5(d)]. Their separation is

Fig. 4. Ethylene epoxidation in a Fixed-Bed Reactor (FBR). Rate of (a) ethylene oxide production and (b)
CO production vs temperature for various feed oxygen levels at constant 6% ethylene. Rates of (c) ethylene
2
oxide production and (d) CO production vs temperature for various feed ethylene levels at constant 6%
2
oxygen.
 Ethylene epoxidation in a catalytic packed-bed membrance reactor 3827

Fig. 5. Ethylene epoxidation in a Fixed-Bed Reactor (FBR). Ethylene oxide selectivity (a,c) and yield (b,d)
vs ethylene conversion for (a,b) various feed oxygen levels at 6% ethylene, and (c,d) various ethylene levels
at 6% oxygen.

evident only at high ethylene conversions, where the
different positions of the 100% oxygen conversion
limit curves deflect the plots in a different manner.
Thus, it appears that the effect of ethylene concentra-
tion is smaller than that of oxygen. From the results of
Fig. 5, we can conclude that ethylene oxide produc-
tion is favored by high oxygen/ethylene molar ratio,
unlike typical partial oxidation reactions (Berty, 1983;
Van Santen and Kuipers, 1987). However, to establish
this ratio in practice, the existence of upper and lower
flammability limits for the mixture must also be con-
sidered (Monroy and Majul, 1977).
3.2. Performance of the packed-bed membrane reactor
3.2.1. Packed-bed membrane reactor with oxygen
feed from membrane (PBMR-O). Figure 6 shows the
rates of production of ethylene oxide and carbon
dioxide as functions of temperature for different levels
of oxygen [Fig. 6(a) and (b)] and ethylene [Fig. 6(c)
and (d)] in the feed. As in the case of FBR, the rates
increase with temperature and concentrations of both
reactants. Also, a plateau (or a small decrease) in the
ethylene oxide production rate can be observed at
high temperature for experiments with low oxy-
gen/ethylene ratios [3 and 6% oxygen in Fig. 6(a);
9 and 12% ethylene in Fig. 6(c)]. This is again a result
of ethylene oxide combustion and of oxygen being the
limiting reactant. The latter occurs even though the
maximum oxygen conversion under these conditions
was 70%, lower than in the FBR (90%).
The effect of the membrane in diminishing the local
partial pressure of oxygen over the catalytic bed leads
to lower production rates than in the FBR (compare
Figs 4 and 6). This may be expected, since both rates
increase with the reactant concentrations. From
Fig. 5, we concluded that high oxygen/ethylene molar
ratios favor the epoxidation reaction. Therefore, the
use of the PBMR-O, that locally reduces this molar
ratio, decreases the selectivity to ethylene oxide. The
reduction in selectivity is illustrated in Fig. 7, which
plots ethylene oxide selectivity and yield vs ethylene
conversion, at different oxygen and ethylene concen-
trations. By comparing Fig. 7 with Fig. 5, the decrease
in ethylene oxide selectivity and yield, for the PBMR-
O as compared to the FBR, is evident. Note that as
a contrast, in other partial oxidation reactions, the
reduction in the combustion rate with decrease in
oxygen concentration is greater, and the use of the
PBMR-O with oxygen as permeate increases the
selectivity (Coronas et al., 1994,1995; Tonkovich et al.,
1996a; Pantazidis et al., 1995).
Regarding the influence of reactant concentrations
in the feed, the same effects as in the FBR are found,
with the oxygen level increasing and the ethylene level
decreasing both selectivity and yield. As noted above,
these curves are far from the 100% oxygen conversion
limit, but there is drop in both selectivity and yield at
ethylene conversion higher than 10%, for curves with
low oxygen/ethylene ratio [3% oxygen in Fig. 7(a)
and (b); 12% ethylene in Fig. 7(c) and (d)].
3828 M. A. Pen8 a et al.

Fig. 6. Ethylene epoxidation in a Packed-Bed Membrane Reactor, oxygen feed from membrane (PBMR-
O). Rates of (a) ethylene oxide production and (b) CO production vs temperature for various feed oxygen
2
levels at constant 6% ethylene. Rates of (c) ethylene oxide production and (d) CO production vs
2
temperature for various feed ethylene levels at constant 6% oxygen.

Fig. 7. Ethylene epoxidation in a Packed-Bed Membrane Reactor, oxygen feed from membrane (PBMR-
O). Ethylene oxide selectivity (a,c) and yield (b,d) vs ethylene conversion for (a,b) various feed oxygen levels
at 6% ethylene, and (c,d) various ethylene levels at 6% oxygen.
 Ethylene epoxidation in a catalytic packed-bed membrance reactor
3.2.2. Packed-bed membrane reactor with ethylene
feed from membrane (PBMR-E). An immediate conse-
quence of the experimental results obtained in the
FBR and PBMR-O is that a different configuration of
the membrane reactor, with ethylene as the permeate,
should improve performance of the epoxidation re-
action. In this configuration, ethylene local partial
pressure over the catalytic bed is lower than in the
FBR and as shown in Fig. 5, the selectivity and yield
of ethylene oxide should be larger.
Figure 8 shows the production rates of ethylene
oxide and carbon dioxide vs temperature for different
oxygen and ethylene concentrations in the feed. As in
the PBMR-O configuration, both production rates
are generally smaller as compared to the FBR (com-
pare with Fig. 4). This effect is similar to the PBMR-O
configuration, since decrease in the local concentra-
tion of any one of the reactants decreases the produc-
tion rate. However there is one notable difference. For
the same reaction conditions, plateaus and maxima in
ethylene oxide production rates observed for the
PBMR-O are not present for the PBMR-E. More-
over, oxygen conversion reaches higher values (80%)
than in the PBMR-O (70%). As expected, the differ-
ences in the two production rates lead to increase of
selectivity to ethylene oxide when the PBMR-E con-
figuration is used. Figure 9 shows the ethylene oxide
selectivity and yield as functions of ethylene conver-
sion, for various oxygen and ethylene levels in the
3829
feed. Comparisons with Figs. 5 and 7 confirm that
both quantities are larger in PBMR-E than in FBR
and PBMR-O. In addition, there is no sharp drop of
selectivity or yield for the reaction conditions of low
oxygen/ethylene ratios [i.e. 3% oxygen in Fig.9(a) and
(b); 12% ethylene in Fig. 9(c) and (d)]. The behavior
regarding the influence of different levels of oxygen
and ethylene in the feed is the same as in the FBR and
PBMR-O, showing increases of selectivity and yield
with increase of oxygen concentration and the oppo-
site for ethylene.
Figure 10 compares the behavior of the three con-
figurations, with plots of selectivity to ethylene oxide
at 12% ethylene conversion vs oxygen [Fig. 10(a)]
and ethylene [Fig. 10(b)] concentrations in feed. For
this conversion value, the selectivity at every reaction
condition in the set of experimental results can be
obtained without any extrapolation. In general, the
differences are maintained at other conversions as
well, and they are indeed larger at higher conversions.
As may be seen, the improvement in absolute value of
selectivity for PBMR-E over the traditional FBR is
4 to 5% for the range of oxygen and ethylene concen-
trations studied. However, the selectivity is lower for
the PBMR-O configuration, and this effect increases
at lower oxygen and higher ethylene concentrations
(i.e. low oxygen/ethylene ratios).
One final point about a comparison between
the PBMR and FBR configurations that deserves

Fig. 8. Ethylene epoxidation in a Packed-Bed Membrane Reactor, ethylene feed from membrane (PBMR-
E). Rates of (a) ethylene oxide production and (b) CO production vs temperature for various feed oxygen
2
levels at constant 6% ethylene. Rates of (c) ethylene oxide production and (d) CO production vs
2
temperature for various feed ethylene levels at constant 6% oxygen.
3830 M. A. Pen8 a et al.

Fig. 9. Ethylene epoxidation in a Packed-Bed Membrane Reactor, ethylene feed from membrane (PBMR-
E). Ethylene oxide selectivity (a,c) and yield (b,d) vs ethylene conversion for (a,b) various feed oxygen levels
at 6% ethylene, and (c,d) various ethylene levels at 6% oxygen.

mention is related to safety. Hydrocarbon mixtures

with oxygen or air exhibit upper and lower flammabil-
ity limits (cf. Lewis and von Elbe, 1987). For safe
reactor operation, it is necessary that local conditions
throughout the reactor remain outside the flammabil-
ity zone. Owing to the reactant segregation, local
conditions over the catalyst bed in a PBMR are quite
different than in a FBR where the reactants are
premixed. Thus, greater care regarding safety is re-
quired for the PBMR operation.

3.2.3. Influence of the residence time. The third set

Fig. 10. Comparison of the different reactor configurations.
Ethylene oxide selectivity at 12% ethylene conversion vs (a)
oxygen concentration in feed at 6% ethylene, and (b) ethy-
lene concentration in feed at 6% oxygen.
of experiments described in the experimental section
provides a way to vary the residence time of ethylene
and oxygen without changing the overall reaction
conditions (i.e., total flow rate, catalyst weight, overall
feed composition) in the membrane reactor. In these
experiments, constant overall feed concentrations of
6% ethylene and 9% oxygen were used, and the
nitrogen split between the two streams was varied.
For the experiments reported previously at this com-
position (Sections 3.2.1 and 3.2.2), 60% of the total
nitrogen was fed with the ethylene stream, and the
oxygen stream had the same composition as air. In the
current experiments, the fraction of nitrogen fed with
ethylene was either increased or decreased from this
value, thus leading to the oxygen stream concentra-
tions different from air.
Figure 11 shows ethylene oxide selectivity vs ethy-
lene conversion for the PBMR-O [Fig. 11(a)] and
PBMR-E [Fig. 11(b)] configurations. It appears that
the effect of the nitrogen spit and, therefore, of the
 Ethylene epoxidation in a catalytic packed-bed membrance reactor
Fig. 11. Ethylene oxide selectivity vs ethylene conversion at
various fractions of nitrogen introduced with ethylene
stream for (a) Packed-Bed Membrane Reactor, oxygen feed
from membrane (PBMR-O), and (b) Packed-Bed Membrane
Reactor, ethylene feed from membrane (PBMR-E). 6% ethy-
lene, 9% oxygen in feed.
residence time (see Fig. 3), is important in the mem-
brane reactor. For the PBMR-O, this effect is more
important at low conversion, since the curves come
closer at higher conversions. However, for the
PBMR-E, the curves are essentially parallel and the
same difference is maintained over the range of con-
versions studied. The ethylene oxide selectivity at
12% ethylene conversion vs the mean residence time
of ethylene for PBMR-O and oxygen for PBMR-E is
shown in Fig. 12(a) and (b), respectively. In each case,
the reactant of the stream entering the catalytic bed
has been chosen for the abscissa, although the plot
would be equivalent with the other reactant since
mean residence times of both reactants exhibit the
same dependence with the nitrogen split (see Fig. 3).
Figure 12 clearly shows how a manipulation of the
residence time in the membrane reactor can improve
ethylene oxide selectivity. When the residence time is
increased over the range studied, the improvement in
selectivity (in absolute value) is 7% for the PBMR-O,
and 6% for the PBMR-E. With the indicated im-
provement, at the maximum residence time used, the
PBMR-O now performs better than the FBR (com-
3831
Fig. 12. Ethylene oxide selectivity at 12% ethylene conver-
sion as a function of residence time of ethylene or oxygen for
(a) Packed-Bed Membrane Reactor, oxygen feed from mem-
brane (PBMR-O), and (b) Packed-Bed Membrane Reactor,
ethylene feed from membrane (PBMR-E). 6% ethylene, 9%
oxygen in feed.
pare Fig. 10). The PBMR-O is a reactor configuration
that decreases the local oxygen concentration and
increases the local ethylene concentration. Both ef-
fects are negative for the epoxidation reaction, as
determined in the FBR study (see Fig. 5). Thus it
appears that the beneficial effect of increasing the
residence time is more important than the negative
effect of the reactant partial pressures. In a different
context, using a membrane reactor model with series—
parallel reactions, Tonkovich et al. (1996b) describe
how these effects compete, and that the predominant
effect depends on the kinetic parameters involved.
While manipulation of the residence time for ethylene
epoxidation in a membrane reactor is demonstrated
to be favorable from the experimental point of view,
development of a mathematical model, including in-
trinsic reaction kinetics, is necessary for a deeper
understanding of this behavior.
Figure 13 shows a detailed comparison of the differ-
ent reactor configurations used in this work, at con-
stant feed composition 6% ethylene and 9% oxygen,
as a function of ethylene conversion. The membrane
configurations with air in the oxygen stream are taken
3832 M. A. Pen8 a et al.
Fig. 13. Ethylene oxide selectivity vs ethylene conversion for different reactor configurations. 6% ethylene,
9% oxygen in feed.
from the series of experiments in Sections 3.2.1 and
3.2.2 [Figs. 7(a) and 9(a)], while those with maximum
residence time correspond to the nitrogen split that
yields the highest selectivity (see Fig. 11). The
previously discussed advantageous effects of the
PBMR-E configuration and the residence time are
clear in this figure. It may be observed that, for the
PBMR-O configuration, only at low ethylene conver-
sion the performance is better than for the FBR. For
conversions higher than 22%, the selectivity is lower.
Under these conditions, the deleterious effect of de-
crease in the local concentration of oxygen and
increase in the local concentration of ethylene,
predominates over the beneficial effect of increase in
the residence time, and the FBR configuration is
preferred.
4. CONCLUSIONS
The results obtained in the FBR with a silver cata-
lyst show that the rates of both ethylene epoxidation
and combustion increase with the concentrations of
reactants (i.e. oxygen and ethylene) in the feed, with
the effect of oxygen concentration being higher than
that of ethylene concentration. In the range of concen-
trations used, the relative increases are not identical
for both rates, producing a change in selectivity and
yield to ethylene oxide. Thus, ethylene oxide produc-
tion is favored by high oxygen/ethylene molar ratio in
the feed. The only limitation in increasing this ratio, in
order to increase the yield to ethylene oxide, is the
existence of flammability limits of the mixture, which
should be considered for a safe operation.
The use of a membrane for segregation and con-
trolled addition of the reactants leads to important
changes in the reactor performance. In both mem-
brane configurations used in this work (PBMR-O and
PBMR-E), the local concentration of one of the react-
ants is reduced, and, accordingly, the production rates
decrease. However, the effect on selectivity to ethylene
oxide is different in the two cases. When oxygen is fed
through the membrane (PBMR-O), the selectivity de-
creases with respect to the FBR at the same ethylene
conversion, and the decrease is greater at lower oxy-
gen/ethylene ratios. On the other hand, if ethylene is
fed through the membrane (PBMR-E), selectivity to
ethylene oxide is ca. 5% higher, in absolute value,
than in the FBR. Therefore, the use of the latter
configuration of the membrane reactor presents ad-
vantages for ethylene oxide production relative to the
conventional FBR. The only potential concern in the
use of membrane reactors is that the local concentra-
tions along the catalytic bed, due to the segregation of
reactants, are different from the overall values, and
this should be taken into account when flammability
issues are considered.
When a membrane reactor is used, the residence
time of reactants can be varied, for the same overall
feed conditions, by changing the diluent split between
the catalytic bed and the membrane. When residence
time is manipulated in this way, the selectivity to
ethylene oxide increases with residence time of both
reactants. This occurs for both configurations of
membrane reactor, with the PBMR-E, at the largest
possible residence time, exhibing ca. 7—8% higher
ethylene oxide selectivity, in absolute value, above the
 Ethylene epoxidation in a catalytic packed-bed membrance reactor
FBR. It is remarkable that under similar residence
time conditions, the PBMR-O configuration can also
yield superior performance as compared to the FBR,
at least at low ethylene conversions.
For a deeper analysis of membrane reactors, it is
necessary to develop a mathematical model that in-
cludes intrinsic reaction kinetics. This model will
allow not only a better understanding of reactor be-
havior with respect to the reactant concentrations and
residence time, but will also permit an evaluation of
the effect of additional parameters such as use of
a non-uniform membrane, to optimize the perfor-
mance of the membrane reactor. The reactor perfor-
mance for ethylene oxide production can also be im-
proved by including ppm levels of chlorine com-
pounds (e.g. 1,2-dichloroethane) in the feed mixture,
as is commonly employed in practice with FBRs
(Berty, 1983). It is important to determine if this
improvement is maintained with membrane re-
actors. Work along the directions of modeling, as
well as chlorine compound additions, is currently in
progress.
Acknowledgements
We gratefully acknowledge financial support from Union
Carbide Corporation and the National Science Foundation
(grant CTS-9529172). One of us (MAP) acknowledges finan-
cial support from the Dirección General de Ensen8 anza
Superior, Spain, during the course of this study.
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