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Adsorption-Enhanced Steam-Methane
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Article in Chemical Engineering Science September 2000

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 Chemical Engineering Science 55 (2000) 3929}3940

Adsorption-enhanced steam}methane reforming

Y. Ding, E. Alpay*
Department of Chemical Engineering and Chemical Technology, Imperial College of Science, Technology and Medicine, Prince Consort Road,
London SW7 2BY, UK
Received 8 September 1999; received in revised form 6 December 1999; accepted 13 December 1999

Abstract

Experimental and theoretical studies of steam}methane reforming in the presence of a hydrotalcite-based CO adsorbent are

presented. Attention is given to the analysis of the transient behaviour of a tubular (integral) reactor when an Ni-based catalyst is
admixed with the adsorbent. Considerable enhancement of the methane conversion is experimentally demonstrated. Enhancement
arises from the favourable shifts in the reaction equilibria of the reforming and water}gas shift reactions towards further CO

production. As predicted, the potential for conversion enhancement is shown to increase under the conditions of a high reactor space
time, high operating pressure, or a low steam-to-methane feed ratio, i.e. when reaction equilibrium limitations are important.
A mathematical model, accounting for mass transfer limited adsorption kinetics, non-linear (Langmuirian) adsorption equilibria and
a general reaction kinetic model, is shown to accurately predict the observed elution pro"les from the reactor, and thus the degree of
conversion enhancement.  2000 Elsevier Science Ltd. All rights reserved.

Keywords: SMR; Sorption enhancement; Transient kinetics; Ni-catalyst; Hydrotalcite; CO adsorbent; Mathematical modelling


1. Introduction hydrogen can permeate) and, more recently, polymeric,

The advantages of coupling reaction systems with
some form of in situ separation have been widely re-
ported in the literature. Such hybrid con"gurations may
substantially improve reactant conversion or product
selectivity and, for reversible reactions, establish a more
favourable reaction equilibrium than that which could be
achieved under conventional reactor operation. Reaction
enhancement may enable a lower temperature of opera-
tion, which in turn may alleviate the problems associated
with catalyst fouling, high process energy requirements
and poor energy integration within the plant environ-
ment. For gas-phase catalytic reactions, the separation
can be based on adsorption, selective permeation
through a membrane, or through simultaneous reaction
of the targeted molecule (e.g. the reaction inhibitor) with
a chemical acceptor.
A comprehensive review on membrane-based reaction
systems has been given by Armor (1995). Advances have
been made in the use of metallic membranes (often
Group VIII metals which only small molecules like
* Corresponding author. Tel.: 0044-171-594-5625; fax: 0044-171-594-
5604.
E-mail address: e.alpay@ic.ac.uk (E. Alpay).
ceramic and zeolitic membranes. The membranes may
act as permselective barriers, or as an integral part of the
catalytically active surface. Practical issues such as mem-
brane pore blockage, thermal and mechanical stability,
and the dilution caused by the need for sweep (i.e. per-
meate purge) gases, have limited the usefulness of the
membrane reactor systems. Nevertheless, the bene"ts of
the membrane systems have been demonstrated though
a wide number of experimental reaction studies, exam-
ples of which include the dehydrogenation of ethane
(Tsotsis, Champagnie, Vasileiadis, Zraka & Minet, 1992),
cyclohexane (Sun & Khang, 1988), ethylbenzene (Wu,
Gerdes, Pszczolowski, Bhave & Liu, 1990), and acetylene
(Itoh, Xu & Sathe, 1993), CO production via the
water}gas shift reaction (Uemiya, Sato, Ando & Kikuchi,
1991), and steam}methane reforming (Adris, Lim
& Grace, 1994, 1997).
In comparison to the membrane reactors, a relatively
small amount of work has been carried out on systems
combining reaction with adsorption or chemical accep-
tor-based separation processes. Even so, such processes
o!er distinct advantages to the membrane-based systems
in terms of the material tolerance to high temperatures
and pressures, and the wide choice and availability of
adsorbents for achieving the desired separations under

0009-2509/00/$ - see front matter  2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 9 9 ) 0 0 5 9 7 - 7
3930 Y. Ding, E. Alpay / Chemical Engineering Science 55 (2000) 3929}3940
reaction conditions. Furthermore, even through use of
a purge gas for regeneration, the e!ective separation of
the primary adsorbate from other non- or weakly adsor-
bing species can be achieved. Some examples of recent
works employing chemical acceptors or adsorbents for
reaction enhancement are now summarised.
Han and Harrison (1994) studied hydrogen production
via the water}gas shift reaction using CaO as a CO
 
acceptor in a tubular reactor. CO conversions were
reported which exceeded that of the thermodynamic
equilibrium conversion under the speci"ed operating
conditions. Brun-Tsekhovoi, Zadorin, Katsobashvili and
Kourdyumov (1986) showed a very signi"cant enhance-
ment of CH conversion to H in a #uidised bed reactor
 
containing Ni-based catalyst balls, and a specially treated
form of dolomite as adsorbent. Typical industrial operat-
ing conditions were considered in this work, i.e. pressure
levels of 10}10 kPa, and an operating temperature of
6273C. Goto, Tagawa and Oomiya (1993) studied the
dehydrogenation of cyclohexane over a Pt}alumina cata-
lyst and CaNi alloy as a hydrogen acceptor. The

workers showed that at 150}1903C and ambient pres-
sure, the overall conversion of cyclohexane to benzene
could be exceeded by three-fold when compared to the
catalyst-only case. Most recently, Carvill, Hufton and
Sircar (1996) and Hufton, Mayorga and Sircar (1999)
describe the general concept of the Sorption Enhanced
Reaction Process (SERP), which utilises pressure and
concentration swing adsorption principles for reaction
enhancement; see also Vaporciyan and Kadlec (1989) and
Alpay, Chatsiriwech and Kershenbaum (1995). CO pro-
duction via the reverse water}gas shift reaction was spe-
ci"cally considered by Carvill et al. (1996), in which NaX
zeolite was used as an adsorbent for water. The authors
showed that at 2503C and 480 kPa, a CO conversion of

36% could be achieved; a conventional plug #ow reactor
required an operating temperature of 5653C for the same
conversion. Furthermore, the process generated a high
purity (#99% (v/v)) CO stream as product. Hufton et al.
(1999) applied the SERP concept to H production via

the steam}methane reforming (SMR) reactions. In speci-
"c, using a hydrotalcite-based CO adsorbent, and

a commercial Ni-based catalyst, the authors showed that
at 4503C and 480 kPa, #95% (v/v) H could be produc-

ed directly from reactor. The CH to H conversion was
 
82%, which could only be achieved at approximately
6503C with a conventional SMR reactor.
The present work also considers the sorption-en-
hanced steam}methane reforming (SE-SMR) process.
The key reactions of the SMR process are given as:
CH #H O 0 CO#3H , *H "206 kJ/mol, (1)
   
CH #2H O 0 CO #4H , *H "164.9 kJ/mol,
    
(2)
CO#H O 0 CO #H , *H "!41 kJ/mol. (3)
   
Reforming reactions (1) and (2) are strongly endothermic,
so the forward reaction is favoured by high temperatures,
while the water}gas shift reaction (3) is moderately
exothermic and is therefore favoured by low temper-
atures. The reforming reactions will also be favoured at
low pressures, whereas the water}gas shift reaction is
largely una!ected by changes in pressure. In the presence
of a selective CO adsorbent, the conversion of CH to

CO though reaction (2) is favoured, as is the production

of CO through CO intermediate. For a reaction which

is not kinetically limited, the use of an adsorbent will thus
enable a lower operating temperature for a desired con-
version. However, on equilibration of the adsorbent, the
separation e!ect is, of course, lost. This necessitates the
periodic regeneration of the adsorbent and thus, for
example, the pressure and concentration swing type op-
erations mentioned above. In other words, sorption-en-
hanced reaction processes are inherently dynamic in
operation. Adequate design and scale-up of such pro-
cesses will thus require information on the kinetics of
adsorption and desorption, as well as reaction kinetic
models under transient conditions in the presence of an
adsorbent.
Research work on the kinetics of the SMR process
dates back to the 18th century (see Sabatier, 1922; Marek
& Hahn, 1932), with the "rst extensive study by Akers
and Camp in 1955. A good review of the work up until
1970 is given by Van Hook (1980), which covers kinetic
studies over porous nickel catalysts and nickel foil
over large temperature (260}10003C) and pressure
(100}5000 kPa) ranges. A considerable amount of work
on the kinetic aspects of the SMR process has been
carried out since 1970; see, for example, Schnell (1970),
Ross and Steel (1973), Allen (1975), Phung Quach and
Rouleau (1975), Munsted and Grabke (1981), De Deken,
Deves and Froment (1982), and Xu and Froment (1989a,
b). To date, the rate models proposed by Xu and Fro-
ment (1989a) are considered to be the most general in
form, and have been extensively tested under typical
industrial operating conditions (see, also, Elnashaie,
Adris, Al-Ubaid & Soliman, 1990). However, like most
previous work, the models are applicable to steady-state
kinetics, and untested for forced-dynamic operation. It is
interesting to note, however, that where some attention
has been given to the transient kinetics, ideal surface
conditions were maintained though vacuum operations;
see, for example, Ross and Steel (1973). This, of course,
limits the applicability of such models for process design
applications.
In this work, attention is given to the analysis of SMR
reaction kinetics under transient conditions depicting
SERP-type operation, both in the presence and absence
of a selective absorbent for CO . Particular attention is

given to the transient analysis of the Xu and Froment
(1989a) kinetic model. The work then considers the in#u-
ence of operating parameters on the degree of separation
 Y. Ding, E. Alpay / Chemical Engineering Science 55 (2000) 3929}3940
enhancement. In doing so, mathematical models of the
process are veri"ed, which can ultimately be used in the
design, analysis or scale-up of pressure or concentration
swing based adsorptive reactors.
2. Experimental
A commercial Ni-based catalyst (United Catalyst Inc.)
containing 25}35% Ni, 25}35% NiO, 5}15% MgO and
15}25% sodium silicate, was used in this work. The
original catalyst (1/8 cylindrical pellets; BET area of
137.6 m/g) was crushed and sieved into two particle size
groups: 0.11}0.25 and 0.25}0.5 mm. The CO adsorbent

consisted of an industrially supplied potassium promoted
hydrotalcite, which was previously measured for its capa-
city and stability under wet gas conditions (see Ding
& Alpay, 2000). The adsorbent was also crushed and
sieved into the particle size groups mentioned above. As
a catalyst diluent, e.g. in the absence of adsorbent, silicon
carbide particles were employed. High-purity methane
(99.95% (v/v)) and hydrogen (99.995% (v/v)) gases were
supplied from gas cylinders; steam supply to the SMR
reactor was generated from distilled water.
A schematic diagram of the experimental apparatus is
given in Fig. 1. The reactor consisted of a stainless-steel
tubular column of internal diameter 12.4 mm and length
220 mm, packed with a mixture of catalyst and adsorbent
(or silicon carbide) particles. The reactor was "tted with
inlet and outlet lines for introducing feed gas (CH and

H O), purge as (H /He and H O) and reducing gas (H ).
   
The inlet CH #ow rate was controlled by a Brooks

5850E mass#ow controller. An HPLC pump was used to
supply water to the reactor via a vaporiser (i.e. a heated
tubular column packed with silicon carbide particles);
both the reactor and water vaporiser were mounted in
Fig. 1. Schematic representation of the experimental system, MFC
* mass#ow controller, PC * personal computer.
3931
a convection oven. The outlet #ow rate from the reactor
was monitored with an Aalborg GFM-17 mass #ow
meter and a soap-bubble #owmeter. The catalyst bed
temperature was detected with a type K thermocouple
(positioned at the centre of the reactor along the central
axis), and a back pressure regulator used to maintain
a constant reactor pressure. The reactor e%uent #ow was
split into sample and vent lines, each equipped with
a water condenser. For the former, time delays in the
sample analysis were minimised by use of 1/16 transfer
lines, and a low-volume condenser unit. The sample line
was connected to a Valco 16-loop valve, the operational
schedule of which was computer controlled. The sample
line and the sample valve were heat traced, and the
temperature controlled at 1103C by a PID controller.
A Shimadzu gas chromatograph (GC-14B), equipped
with a TCD detector and a Porapak-Q column, was used
for sample analysis. In addition, two on-line Telegan
CO analysers (0}30 and 0}5%FSD) were used to moni-

tor the reactor e%uent CO concentration.

For the reaction studies in the absence of adsorbent,
approximately 7.2 g of catalyst was admixed with dense
silicon carbide particles (&1 : 3 mass ratio), and packed
into the reactor. For the sorption-enhanced reaction
studies, approximately 7.2 g of catalyst was admixed with
14.8 g of CO adsorbent. Reactor operating conditions

for both the adsorbent and adsorbent-free systems are
summarised in Table 1.
As mentioned above, conversion enhancement arises
prior to the equilibration of the adsorbent. In this work,
transient operation was imposed by means of step cha-
nges in feed concentration. Due to the negligible resi-
dence time of methane in the reactor, even in the presence
of adsorbent (i.e. typically less than 0.2 s), the conversion
enhancement factor at any given time (E(t)) can be quan-
ti"ed by the normalised conversion of methane (X  ) in
!&
the presence (ad) and absence (nad) of adsorbent, i.e.
(X ) !(X  )
E(t)" !&  !&   100. (4)
(X  )
!&  
Thus, values of E(t)'0 indicate conversion enhance-
ment in the presence of adsorbent. At steady state, and
for similarly packed reactors (i.e. catalyst mass loading
and distribution), E(t) should approach 0. A typical ex-
perimental cycle involved the following steps: (i) heat-up
of the reactor at atmospheric pressure under a hydrogen
environment to the preset temperature, (ii) water supply
to the system so that the molar ratio of H O to H is
 
approximately the same as the desired H O-to-CH
 
ratio in the reaction step, (iii) pressurisation of the system
to the preset pressure, (iv) switch from H to CH to
 
initiate the reaction step, (v) depressurisation of the unit,
(vi) low-pressure purge of the unit with H and steam,

and (vii) reduction of the catalyst with H at 4803C for

3 h. Steps (vi) and (vii) were carried out as precautions
3932 Y. Ding, E. Alpay / Chemical Engineering Science 55 (2000) 3929}3940

Table 1
List of experimental

Run type
Space time H O/CH Pressure Temperature Particle size

 
(g-cat h/mol-CH ) (kPa) (3C) (mm)

WA/NA 5.37}17.9 3 445.72 455 0.25}0.5
WA/NA 10.7 2}6 445.72 455 0.25}0.5
WA/NA 10.7 3 308}721.5 457.5 0.25}0.5
WA/NA 10.7 3 445.72 428}467.5 0.25}0.5
WA 10.7 3 445.72 459 0.11}0.25

Initial reactor environment: H O : H (He)"H O : CH

   

WA * with adsorbent, NA * no adsorbent.

towards any carbonaceous deposits on the catalyst, and
thus to ensure a reproducible catalyst activity from one
experiment to the next. Reproducibility was subsequently
con"rmed through repetition of the experiments. The
measurement of the reactor e%uent concentration pro-
"les in the reaction step (step (iv)) enabled both transient
and steady-state reaction kinetics to be tested. Note that
due to non-isothermal nature of the SMR process, the
where i denotes CH , H O, H , CO CO, and He. the
   
semi-empirical correlation proposed by Edwards and
Richardson (1968) was used to estimate the axial disper-
sion coe$cient D . The catalyst e!ectiveness factor, g ,
X G
was set as unity for the crushed catalyst used in this work;
see Section 4 for details. The reaction kinetic model of Xu
and Froment (1989a) can be summarised as


measured wall temperature at the middle point of the k P P
R "  P  P  ! & !- (DEN), (6a)
reactor is taken as the characteristic temperature in this ' P  !& & - K
& '
work.


k P P
R "  P  P  ! & !- (DEN), (6b)
'' P  !& & - K
& ''
3. Mathematical modelling


k P P
R "  P P  ! & !- (DEN), (6c)
3.1. Governing equations ''' P !- & - K
& '''
DEN"1#K P #K  P  #K  P 
A dynamic model accounting for non-isothermal, !- !- & & !& !&
non-adiabatic, and non-isobaric operation, was de-
#K P /P , (6d)
veloped to describe both the SMR and SE-SMR & - & - &
processes. For the SE-SMR process, the reactions and where R ( j"I!III) denotes the reaction rate of the
adsorption were assumed to take place on the surfaces of H
SMR reactions (1) and (2) and the water}gas shift reac-
the catalyst and adsorbent, respectively. A Langmuir tion (3). The formation rate of component i, r , was
model was used to describe the adsorption equilibria of G
then calculated by using Eqs. (1)}(3) and (6a)}(6d);
CO , and a linear driving force (LDF) model for the for example, r  "!(R #R ), r  "3(R #R )#
 !& ' '' & ' '''
intraparticle mass transfer of the adsorbent; further de- (R #R ). The rate constants k (i"1}3) and the ad-
tails of equilibria and kinetic measurements, and math- '' ''' G
sorption constants K ( j"I}III) are function of temper-
ematical model development under non-reacting H
ature, details of which are given by Xu and Froment
conditions, are given by Ding and Alpay (2000). As men- (1989a).
tioned above, the general reaction kinetic model pro- Pressure distribution in the packed-bed reactor was
posed by Xu and Froment (1989a) was considered in this described by the Ergun equation (Ergun, 1952)
work. Other principal model assumptions can be sum-
marised as: axially dispersed plug #ow, perfect gas behav- *P
"!K u!K u, (7)
iour, no radial concentration or temperature gradients, *z " 4
and a catalyst/adsorbent packing of uniform voidage and
particle size. where K and K are parameters corresponding to the
" 4
Based on the above assumptions, component mass viscous and kinetic pressure loss terms, respectively.
balances for the packed-bed reactor can be written as Semi-empirical relationships for K and K have been
" 4
derived by Ergun (1952) (see also MacDonald, El-Sayed,


* * *C *(uC )
(e C #o q )" D G ! G #g o r, Mow & Dullien, 1979).
*t R G @  G *z X *z *z G @  G
For compressible #ow, the energy balance for the
(5) reactor is given by (see, for example, Bird, Stewart &
 Y. Ding, E. Alpay / Chemical Engineering Science 55 (2000) 3929}3940 3933

Lightfoot, 1960) 3.2. Boundary and initial conditions

*
(o C e #o C ) For the simulation of the reaction step, initial condi-
*t E NE R @ NQ
tions (t"0, z3(0, )) were set to depict a clean and


*P * * * isothermal bed, but with a pre-imposed pressure pro"le:
"e # K ! (o uC )
R *t *z X *z *z E NE q "0, (14a)
G


*q
!o H G # (R o gH ) *P
@  G *t G @  G 0G "!K u !K u , (14b)
G G *z "  4 
4;
#  ( !). (8) *P/*t"0, (14c)
Dr U
" , (14d)
The bed e!ective conductivity, K , can be expressed as
X 
(see Yagi & Kunii, 1957; Kunii & Smith, 1960; De Wasch C "P /(R ) (14e)
& Froment, 1972; Li & Finlayson, 1977; Wakao G G 
& Kaguei, 1982) At the onset of the reaction step (i.e. the point at which
CH is supplied to the reactor), the following boundary
K K 
X " X #a(Pr) (Re ), (9) conditions were used in the simulations:
k k N (i) Reactor entrance (z"0)
E E
where K is the static e!ective conductivity accounting
X !D (*C /*z)"u(C !C ),
X G DG G
(15a)
for the e!ects of conduction and radiation, see Kunii and
Smith (1960) and Ding and Alpay (2000). !K (*/*z)"uo C ( !), (15b)
X E NE D
For a bed packed with spherical particles, the wall}bed u"Q /A. (15c)
heat transfer coe$cient, ; , in Eq. (8) is given by Li and D

Finlayson (1977) as (ii) Reactor outlet (z")

 *C /*z"0,
; D 6d (15d)
 P "2.03Re
 exp ! N G
k N D
E P */*z,0, (15e)
(Re "20}7600, d /D "0.05}0.3). (10)
N N P P"P . (15f )
*
Eq. (10) is not applicable to very low feed #ow rates, as
Q in Eq. (15c) is the feed volumetric #ow rate measured
; should approach a "xed value where Re P0. How- D
 N under the local conditions.
ever, De Wasch and Froment (1972) give the following
correlation for ; at very low Re :
 N
K
; " N "6.15 X (11) Table 2
 0C  D Parameters (constants) used in the simulations
P
which can be linearly combined with Eq. (10) to approx- Parameters (constants) Value Unit
imate ; over the entire range of Re relevant to this
 N b  SE-SMR: 2.36;10\; SMR:0 Pa\
work. !-
The Langmuir model for CO adsorption can be d (average) 1.8;10\, 3.57;10\ m
N
 D 1.27;10\ m
written as P
C 42 J/mol K
NE
m b P C 850 J/kg K
NQ
qH  " !- !- !- . (12) e 0.35
!-
*
1#b  P 
!- !- k
E
0.09 J/m K
k 0.3 J/m K
Other reaction components were considered to be non- Q
H SE-SMR: !17000, SMR: 0 J/mol
adsorbing. The LDF model is given by  !-
(reactor length) 0.22 m
m  SE-SMR: 0.65, SMR: 0 mol/kg
*q !-
G "k (qH!q ), (13) b

0.95 *
*t G G G e 0.47
@
*
e 0.64
R
*
where k is the e!ective mass transfer coe$cient. Note that U 0.2 *
*q /*t"0 for non-adsorbing species in the SE-SMR pro- c 0.667
G
*
cess, and *q /*t"0 for all species in the SMR process. As j 1.0
Q
*
G k 2.87;10\ Pa s
mentioned above, Langmuir and LDF parameters have E
o SE-SMR: 609.3, SMR:0 kg/m
been previously measured for the CO }H O-hydro- @ 
  o
@ 
139.0 kg/m
talcite system; see Ding and Alpay (2000).
3934 Y. Ding, E. Alpay / Chemical Engineering Science 55 (2000) 3929}3940
Eqs. (5)}(15) were simultaneously solved in the
gPROMS modelling environment (Process Systems En-
terprises Ltd.). The spatial discretisation method of or-
thogonal collocation on "nite elements was employed.
Second-order collocation on 100 elements was found to
give a converged solution in which component balance
errors (associated with the numerical integration) did not
exceed 1%. A summary of parameters (constants) used
for the simulations is given in Table 2.
4. Results and discussion
Typical reactor e%uent concentration pro"les mea-
sured in the SMR and SE-SMR experiments under
similar operating conditions (4503C, 445.7 kPa, H O/

CH "6) are shown in Fig. 2(a) and (b), respectively. It

can be seen that in the presence of CO adsorbent, the

transient period (&5 min) is much longer than that of
Fig. 2. E%uent concentration (mole fraction) pro"les on a water-free
basis: comparison between experiments and simulations (reactor
pressure"445.7 kPa, temperature"450$23C, feed #ow rate of
CH "250 ml/min (STP), molar ratio of H O to CH "6, cata-
   
lyst/adsorbent (or carbide) particle size"0.25}0.5 mm).
the SMR run (&1.5 min). However, since the experi-
mental conditions are nearly identical, the steady-state
concentrations of CH , H , and CO are approximately
  
equal, indicating no strong direct catalyst/adsorbent in-
teraction. The measured e%uent CO concentrations were
found to be very low ((0.2% (v/v)) for all these runs.
The longer transient time of the SE-SMR run is mainly
due to the interaction between the adsorption and reac-
tion processes, i.e. the retention of CO and its sub-

sequent in#uence on local reaction kinetics and
equilibria. Adsorption of CO not only decreases the

gas-phase CO partial pressure, but also releases some

heat, both of which are favourable for the reforming
reactions (1) and (2). On the other hand, an increase in the
SMR reaction rate will result in a decrease in the reactor
temperature due to the endothermic nature of the re-
forming reactions; see below for further discussions on
the reactor temperature pro"les in the presence and ab-
sence of adsorbent. Also shown in Fig. 2(a) and (b) are the
simulated e%uent concentration pro"les. The excellent
agreement between the experiments and simulations for
both the SMR and SE-SMR processes indicates that the
rate expressions proposed by Xu and Froment (1989a)
are suitable for both the transient and steady-state peri-
ods of operation, even in the presence of adsorbent. This
suggests that the microkinetic dynamics of reaction are
relatively fast, and that the physically admixed nature of
catalyst and adsorbent precludes any local e!ect of ad-
sorption on reaction intermediates, and hence on mo-
lecular kinetic steps.
Fig. 3 shows typical measured temporal pro"les of
methane conversion and CO exit concentration. Corre-

sponding measured and calculated enhancement factors
are shown in Fig. 4. It can be seen that there exists a peak
in conversion enhancement, which disappears on the
Fig. 3. Comparison of methane conversion pro"les and CO break-

through curve (reactor pressure"445.7 kPa, temperature"
450$23C, feed #ow rate of CH "250 ml/min (STP), molar ratio

of H O to CH "6, catalyst/adsorbent (or carbide) particle

size"0.25}0.5 mm).
 Y. Ding, E. Alpay / Chemical Engineering Science 55 (2000) 3929}3940
Fig. 4. Conversion enhancement: comparison between experiments
and simulations (reactor pressure"445.7 kPa, temperature"
450$23C, feed #ow rate of CH "250 ml/min (STP), molar ratio
 
of H O to CH "6, catalyst/adsorbent (or carbide) particle
 
size"0.25}0.5 mm, measured steady-state conversion"23.98%).
onset of the breakthrough of CO . A slight negative

enhancement (of 1}2%) after the sorption-enhancement
peak is also observed in both experiments and simula-
tions. This negative enhancement may be attributed to
the propagation of a weak thermal (cold) wave prior the
approach to the steady state. Thus, whilst CO adsorp-
 
tion enhances overall reaction rates through favourable
equilibria shifts, as the adsorbent becomes equilibrated,
a slightly lower temperature pro"le in the reactor results
in a small (and temporary) reduction in the conversion
relative to the catalyst-only reactor. This e!ect is demon-
Fig. 5. Temperature distribution: Comparison between SMR and SE-SMR (4503C, 445.7 kPa, feed #ow rate of CH "250 ml/min (STP) H O to
CH "6, catalyst/adsorbent (or carbide) particle size"0.25}0.5 mm).

3935
strated in Fig. 5, in which calculated axial temperature
pro"les for the SMR and SE-SMR processes are shown
at di!erent times from the onset of the reaction step.
The complex interaction of adsorption and reaction
precludes any intuitive design of forced-periodic adsor-
ptive reactors. However, some insight into favourable
operating regimes can be gained by considering the speci-
"c e!ects of key operating and design parameters on the
enhancement factor and the overall yield of product. In
this work, the following parameters have been considered
in turn: space time (g-cat h/mol-CH ), H O-to-CH feed
  
molar ratio, temperature, pressure and adsorbent/cata-
lyst particle size. Fig. 6 shows the e!ect of space time on
these enhancement factor; other operating conditions are
set as 445.7 kPa, 4553C, H O : CH "3 mol/mol. Under
 
these conditions, higher conversions are achieved, and
approach the equilibrium conversion of approximately
20% at 4553C. The bene"cial e!ects of local CO adsorp-
tion are realised as the reaction equilibrium conversion is
approached. For a relatively low space time, the reaction
kinetics dictate a low production rate of CO , and adsor-

bent equilibration (i.e. CO breakthrough) occurs rela-

tively rapidly. Where conversions are so low that the
backward reaction rates are small, the advantages of
CO removal from the reaction zone will be minimised.

Thus, a low space time will generally lead to poor conver-
sions, for which the advantages of in situ separation will
not be realised due to the rapid propagation velocity of
the CO concentration front, and the diminished inhibi-
tion of CO on the net reaction rates. It is important to

note however, that in this case, reactor space time (i.e.
feed #ow rate) has a signi"cant in#uence on heat transfer
rates and subsequently on the reactor temperature pro-
"le. In speci"c, a high space time will lead to poor heat
 
3936 Y. Ding, E. Alpay / Chemical Engineering Science 55 (2000) 3929}3940
Fig. 6. E!ect of space time on the conversion enhancement (reactor
pressure"445.7 kPa, reactor temperature"455$53C, molar raito of
H O to CH "3, catalyst/adsorbent size"0.25}0.5 mm, measured
 
steady-state conversions"14.50%, 17.0%, 14.90%, 15.2%, 16.50%,
15.75% and 18.10% for space times"17.89, 13.50, 10.7, 8.96, 7.68, 6.72
and 5.37 g-cat h/mol-CH correspondingly).
 the conventional reactor, some carbon formation via the
Fig. 7. E!ect of feed molar ratio of H O to CH on the conversion
 
enhancement (reactor pressure"445.7 kPa, reactor temperature"
455$43C, space time"10.7 g-cat h/mol-CH , catalyst/adsorbent
 the bene"ts of in situ separation are negligible, even
size"0.25}0.5 mm, measured steady-state conversions"13.0%,
14.87%, 16.65%, 20.50% and 23.70% for H O : CH "2, 3, 4, 5 and
 
6 correspondingly).
transfer, and thus a cooler reactor. Hence, the decrease in
the steady-state conversion with increasing space time
(see "gure caption of Fig. 6) is to expected, although
equilibrium constrains dominate for relatively high space
times.
The e!ect of the feed molar ratio of H O to CH on
 
the enhancement factor is shown in Fig. 7; other operat-
ing conditions are set as 445.7 kPa, 4553C, 10.7 g-cat
h/mol-CH . Methane conversion enhancement is fa-

voured by low H O : CH ratios, i.e. at relatively low
 
partial pressures of feed H O. For low H O partial
 
pressures, the equilibrium conversion is relatively low, i.e.
the backward reactions for methane and water produc-
tion are signi"cant, and thus greater potential for separ-
ation-enhanced conversion exists. Conversely, at high
partial pressures of water, a relatively high equilibrium
conversion exists, and thus the signi"cance of CO ad-

sorption on conversion enhancement decreases. Accord-
ing to reactions (1) and (2), the ideal ratio of H O to CH
 
is between 1 and 2, depending on the desired "nal reac-
tion products. For the production of H , this ratio

should be 2. However, a H O : CH ratio greater than
 
this stoichiometric value is often required to avoid cata-
lyst deactivation due to carbon deposition. Carbon de-
position principally occurs at high temperatures through
the decomposition of methane (CH "C#2H ,
 
*H "75 kJ/mol), and to a smaller extent by the

Boudouard reaction (2CO"C#CO , *H "
 
!173 kJ/mol) which is thermodynamically favoured at
low temperatures (see Rostrup-Nielsen, 1984). Although
sorption-enhanced steam}methane reforming takes place
at a considerably lower temperature than that used in
Boudouard reaction cannot be avoided. Furthermore,
the adsorption of CO is likely to shift the decomposition

of CO to further carbon formation. As a consequence,
whilst it is feasible to operate the SE-SMR at lower
H O/CH ratios, this again will be dictated by the level
 
of catalyst coking. However, in this work, no catalyst
deactivation was apparent, possibly due to relatively
short times-on-stream of catalyst (i.e. &200 h), and the
very low CO partial pressures measured in all experi-
ments.
The e!ect of operating temperature on the enhance-
ment factor is shown in Fig. 8; other operating conditions
are set as 445.7 kPa, H O : CH "3 mol/mol, 10.7 g-cat
 
h/mol-CH . As temperature decreases, the steady-stage

yield of CO decreases, i.e. CH conversions decrease
 
from 16.3 to 12.7% as the temperature is reduced from
467.5 to 4283C. As for the case of low reactor space times,
though the adsorption a$nity of CO is relatively high.

However, at relatively high temperatures of operation,
a high yield of CO is achieved, but further enhancement

of conversion is di$cult due to the relatively low adsorp-
tion a$nity. Thus, as indicated in Fig. 8, an optimal
temperature exists for maximum enhancement. In order
to achieve an equivalent product yield at a temperature
lower than that of an adsorbent-free (conventional) reac-
tor, careful selection of the adsorbent and catalyst is
needed such that the kinetics of reaction and the capacity
of the adsorbent are in accord. When the adsorbent needs
to be operated at a lower temperature, it may be possible
to have a two-stage reactor consisting of a high-temper-
ature catalyst-only stage, and a lower temperature cata-
lyst#adsorbent stage. Further discussion on analytical
criteria for favourable catalyst and adsorbent combina-
tions is given by Sheikh, Kershenbaum and Alpay
(1998).
 Y. Ding, E. Alpay / Chemical Engineering Science 55 (2000) 3929}3940
Fig. 8. E!ect of reactor temperature on the conversion enhancement
(reactor pressure"445.7 kPa, molar ratio of H O to CH "3, space
 
time"10.7 g-cat h/mol-CH , catalyst/adsorbent size"0.25}0.5 mm,
 445.7 kPa, space time"10.7 g-cat h/mol-CH , H O : CH "3).
measured steady-state conversions"12.70%, 14.15%, 14.87% and
16.25% for reactor temperatures"428, 445, 458 and 467.53C corre-
spondingly).
Fig. 9. E!ect of reactor pressure on the conversion enhancement (reac-
tor temperature"445.5$13C, molar ratio of H O to CH "3, space
 
time"10.7 g-cat h/mol-CH , catalyst/adsorbent size"0.25}0.5 mm,

measured steady-state conversions"17.8%, 14.87%, 12.13% and
10.5% for reactor pressures"308, 445.72, 583.68 and 721.5 kPa corre-
spondingly).
Fig. 9 shows the e!ect of reactor pressure on the
enhancement factor; other operating conditions are
set as 457.53C, 10.7 g-cat h/mol-CH , H O : CH "
    
3 mol/mol. It can be seen that the enhancement factor
increases with increasing reactor pressure. Higher pres-
sures will favour greater CO adsorption, and will result
 
in a greater potential for reaction enhancement due to
a reduction in the equilibrium conversion of CH . Thus,

although SMR reactions (1) and (2) are favoured by low
pressures, the above result suggests that the sorption-
enhanced SMR reactor can be operated at higher pres-
sures to achieve the same product yield. This, of course, is
particularly bene"cial where the direct high-pressure de-
livery of H is of economic advantage.

3937
Fig. 10. E!ect of particle sizes of catalyst and adsorbent on the transi-
ent kinetics (reaction temperature"459$13C, reactor pressure"
  
Fig. 10 shows the e!ect of particle size of catalyst and
adsorbent on the methane conversion; other operating
conditions are set as 4593C, 445.7 kPa, 10.7 g-cat h/mol-
CH , H O : CH "3 mol/mol. It can be seen that the
  
methane conversion for experiments with 0.11}0.25 mm
particles can be up to 20% higher than that with
0.25}0.5 mm particles in the transient period. However,
this di!erence diminishes when the reactor approaches
the steady stage. Given that the e!ect of particle size is
only apparent during the transient stage, it is concluded
that the above results are likely to be associated with the
mass transfer resistances inside the adsorbent particles,
i.e. the e!ectiveness factor of the catalyst approaches
unity. As mentioned above, a reduction in the #ow rate of
reactant, or an increase in reactor length, will reduce the
signi"cance of the adsorption and desorption kinetics.
As mentioned in Section 2, the transient experiments in
this work consisted of a step change from a hydro-
gen}steam feed to a methane}steam feed. Experiments
have also been performed in which H is replaced with

He prior to the onset of the reaction step (H O : He

&3 mol/mol), i.e. a reactor environment free of H prior

to the introduction of methane and steam. A comparison
of the CH conversion for the two cases is given in

Fig. 11; operating conditions for both cases are set as
4453C, 445.7 kPa, 6.27 g-cat h/mol-CH , H O : CH "

3 mol/mol. It can be seen that at early times, the methane
conversion is higher under an initial He}H O environ-

ment. This inhibitive e!ect of H on the reaction kinetics
is well documented; see, for example. Bodrov, Apel'baum
and Tempkin (1967, 1968), Phung Quach and Rouleau
(1975) and Ross and Steel (1973). For example, Phung
Quach and Rouleau (1975) studied the kinetics of SMR
over Ni/a-Alumina catalyst in a continuous stirred tank
reactor at 350}4503C; a Langmuir}Hinshelwood}
Hougen}Watson type rate equation was found to "t their
kinetic data satisfactorily, and the equation obviously
3938 Y. Ding, E. Alpay / Chemical Engineering Science 55 (2000) 3929}3940
Fig. 11. E!ect of reactor initial environment on the transient kinetics
(reaction temperature"4453C, reactor pressure"445.7 kPa, space
time"6.27 g-cat h/mol-CH , H O : CH "3, catalyst/adsorbent size
  
"0.25}0.5 mm).
implied the inhibitive e!ect of the presence of H in the

feed. Nevertheless, the in#uence of the initial presence of
H on the dynamics of conversions is short-lived, i.e. less

than 1 min. This suggests that under pressure and
concentration swing type operations, and for the
temperatures considered in this work, adsorbent regen-
eration can be achieved under a hydrogen-free environ-
ment without adverse e!ect on the catalyst activity, and
thus the dynamics of the in situ separation and reaction
step.
Having validated transient reaction kinetics in the
presence of adsorbent, future work will involve model-
based optimisation methods for the selection and design
of adsorptive reactor con"gurations; see, for example,
Yongsunthon and Alpay (1999). In particular, considera-
tion will be given to process design based on distinct
objectives, such as: (i) the lowest energy utilisation for
a speci"ed product yield, and (ii) the highest concentra-
tion (bulk separation) of hydrogen for a speci"ed conver-
sion. Ultimately, the stability of the adsorbent under
cyclic reactor conditions, i.e. under constant temporal
and spatial variations of gas composition and temper-
ature, will govern the commercial feasibility. Thus, fur-
ther experimental work will be required, at least at
a semi-technical scale, to address such issues under iden-
ti"ed process con"gurations.
5. Conclusions
The steady-state kinetic model of Xu and Froment
/
(1989a) for steam}methane reforming has been shown to
be applicable to transient reactor operation, both in the
presence and absence of adsorbent. In particular, a reac-
tor model accounting for non-isothermal, non-adiabatic
and non-isobaric operation, and mass transfer limited
adsorption, was found to accurately predict the elution
pro"les of the reaction species over an admixture of Ni
catalyst and hydrotalcite adsorbent. Kinetic and equilib-
rium parameters for adsorption and reaction were em-
ployed from previous (independent) measurements; no
model "tting parameters were needed. Comparison of the
elution pro"les of methane for the adsorbent-free and
adsorbent-present cases led to a measure of the reaction
(conversion) enhancement. Thus, direct evidence for the
increase in net reaction rates due to in situ separation
was attained. Furthermore, investigations on the in#u-
ence of some key operating parameters on the degree of
enhancement led to the following conclusions: (i) a high
reactor space time is favourable for minimising the e!ects
of adsorbent intraparticle mass transfer resistances and,
of course, for overcoming kinetic limitation to reaction,
(ii) for a given conversion of CH or yield of CO , the
 
SE-SMR process enables operation with lower steam-
to-methane ratios, and/or higher operating pressures,
and (iii) under the conditions of SE-SMR operation,
negligible deactivation of the catalyst occurs. Currently,
separation-enhanced reaction studies in a semi-technical
scale reactor are under way, in which the typical operat-
ing steps of a pressure swing based adsorption unit are
being imposed. The work will enable the further testing of
kinetic and process models under cyclic operation.
Notation
a constant in the empirical correlation for the ef-
fective thermal conductivity, dimensionless
A cross-sectional area of the reactor, m
b Langmuir model constant for component, i,
G
Pa\
C gas-phase concentration of component i in the
DG
feed, mol/m
C molar concentration of gas-phase component i,
G
mol/m
C gas-phase heat capacity, J/mol K
NE
C solid-phase heat capacity, J/kg K
NQ
d particle diameter, m
N
D inner diameter of the reactor, m
P
D axial dispersion coe$cient, m/s
X
E(t) conversion enhancement, %
H adsorption heat of component i (on adsorbent
G
surface), J/mol
H reaction heat of reaction i, J/mol
0G
k LDF mass transfer coe$cient, s\
k gas-phase thermal conductivity, J/m K
E
k rate constant of reaction i, i"1, 2; mol Pa
G
kg-cat s, i"3: mol/kg-cat s Pa
k solid-phase thermal conductivity, J/m K
Q
K Ergun equation coe$cient, N s/m
"
K equilibrium constant of reactions (1)}(3), i"I,
G
II: Pa, i"III: dimensionless
 Y. Ding, E. Alpay / Chemical Engineering Science 55 (2000) 3929}3940 3939

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