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Adsorption-Enhanced Steam-Methane
Reforming
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Chemical Engineering Science 55 (2000) 3929}3940
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
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 Reforming reactions (1) and (2) are strongly endothermic,
a purge gas for regeneration, the e!ective separation of so the forward reaction is favoured by high temperatures,
the primary adsorbate from other non- or weakly adsor- while the water}gas shift reaction (3) is moderately
bing species can be achieved. Some examples of recent exothermic and is therefore favoured by low temper-
works employing chemical acceptors or adsorbents for atures. The reforming reactions will also be favoured at
reaction enhancement are now summarised. low pressures, whereas the water}gas shift reaction is
Han and Harrison (1994) studied hydrogen production largely una!ected by changes in pressure. In the presence
via the water}gas shift reaction using CaO as a CO of a selective CO adsorbent, the conversion of CH to
acceptor in a tubular reactor. CO conversions were CO though reaction (2) is favoured, as is the production
reported which exceeded that of the thermodynamic of CO through CO intermediate. For a reaction which
equilibrium conversion under the speci"ed operating is not kinetically limited, the use of an adsorbent will thus
conditions. Brun-Tsekhovoi, Zadorin, Katsobashvili and enable a lower operating temperature for a desired con-
Kourdyumov (1986) showed a very signi"cant enhance- version. However, on equilibration of the adsorbent, the
ment of CH conversion to H in a #uidised bed reactor separation e!ect is, of course, lost. This necessitates the
containing Ni-based catalyst balls, and a specially treated periodic regeneration of the adsorbent and thus, for
form of dolomite as adsorbent. Typical industrial operat- example, the pressure and concentration swing type op-
ing conditions were considered in this work, i.e. pressure erations mentioned above. In other words, sorption-en-
levels of 10}10 kPa, and an operating temperature of hanced reaction processes are inherently dynamic in
6273C. Goto, Tagawa and Oomiya (1993) studied the operation. Adequate design and scale-up of such pro-
dehydrogenation of cyclohexane over a Pt}alumina cata- cesses will thus require information on the kinetics of
lyst and CaNi alloy as a hydrogen acceptor. The adsorption and desorption, as well as reaction kinetic
workers showed that at 150}1903C and ambient pres- models under transient conditions in the presence of an
sure, the overall conversion of cyclohexane to benzene adsorbent.
could be exceeded by three-fold when compared to the Research work on the kinetics of the SMR process
catalyst-only case. Most recently, Carvill, Hufton and dates back to the 18th century (see Sabatier, 1922; Marek
Sircar (1996) and Hufton, Mayorga and Sircar (1999) & Hahn, 1932), with the "rst extensive study by Akers
describe the general concept of the Sorption Enhanced and Camp in 1955. A good review of the work up until
Reaction Process (SERP), which utilises pressure and 1970 is given by Van Hook (1980), which covers kinetic
concentration swing adsorption principles for reaction studies over porous nickel catalysts and nickel foil
enhancement; see also Vaporciyan and Kadlec (1989) and over large temperature (260}10003C) and pressure
Alpay, Chatsiriwech and Kershenbaum (1995). CO pro- (100}5000 kPa) ranges. A considerable amount of work
duction via the reverse water}gas shift reaction was spe- on the kinetic aspects of the SMR process has been
ci"cally considered by Carvill et al. (1996), in which NaX carried out since 1970; see, for example, Schnell (1970),
zeolite was used as an adsorbent for water. The authors Ross and Steel (1973), Allen (1975), Phung Quach and
showed that at 2503C and 480 kPa, a CO conversion of Rouleau (1975), Munsted and Grabke (1981), De Deken,
36% could be achieved; a conventional plug #ow reactor Deves and Froment (1982), and Xu and Froment (1989a,
required an operating temperature of 5653C for the same b). To date, the rate models proposed by Xu and Fro-
conversion. Furthermore, the process generated a high ment (1989a) are considered to be the most general in
purity (#99% (v/v)) CO stream as product. Hufton et al. form, and have been extensively tested under typical
(1999) applied the SERP concept to H production via industrial operating conditions (see, also, Elnashaie,
the steam}methane reforming (SMR) reactions. In speci- Adris, Al-Ubaid & Soliman, 1990). However, like most
"c, using a hydrotalcite-based CO adsorbent, and previous work, the models are applicable to steady-state
a commercial Ni-based catalyst, the authors showed that kinetics, and untested for forced-dynamic operation. It is
at 4503C and 480 kPa, #95% (v/v) H could be produc- interesting to note, however, that where some attention
ed directly from reactor. The CH to H conversion was has been given to the transient kinetics, ideal surface
82%, which could only be achieved at approximately conditions were maintained though vacuum operations;
6503C with a conventional SMR reactor. see, for example, Ross and Steel (1973). This, of course,
The present work also considers the sorption-en- limits the applicability of such models for process design
hanced steam}methane reforming (SE-SMR) process. applications.
The key reactions of the SMR process are given as: In this work, attention is given to the analysis of SMR
reaction kinetics under transient conditions depicting
CH #H O 0 CO#3H , *H "206 kJ/mol, (1)
SERP-type operation, both in the presence and absence
CH #2H O 0 CO #4H , *H "164.9 kJ/mol, of a selective absorbent for CO . Particular attention is
given to the transient analysis of the Xu and Froment
(2)
(1989a) kinetic model. The work then considers the in#u-
CO#H O 0 CO #H , *H "!41 kJ/mol. (3) ence of operating parameters on the degree of separation
Y. Ding, E. Alpay / Chemical Engineering Science 55 (2000) 3929}3940 3931
enhancement. In doing so, mathematical models of the a convection oven. The outlet #ow rate from the reactor
process are veri"ed, which can ultimately be used in the was monitored with an Aalborg GFM-17 mass #ow
design, analysis or scale-up of pressure or concentration meter and a soap-bubble #owmeter. The catalyst bed
swing based adsorptive reactors. 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
2. Experimental a constant reactor pressure. The reactor e%uent #ow was
split into sample and vent lines, each equipped with
A commercial Ni-based catalyst (United Catalyst Inc.) a water condenser. For the former, time delays in the
containing 25}35% Ni, 25}35% NiO, 5}15% MgO and sample analysis were minimised by use of 1/16 transfer
15}25% sodium silicate, was used in this work. The lines, and a low-volume condenser unit. The sample line
original catalyst (1/8 cylindrical pellets; BET area of was connected to a Valco 16-loop valve, the operational
137.6 m/g) was crushed and sieved into two particle size schedule of which was computer controlled. The sample
groups: 0.11}0.25 and 0.25}0.5 mm. The CO adsorbent line and the sample valve were heat traced, and the
consisted of an industrially supplied potassium promoted temperature controlled at 1103C by a PID controller.
hydrotalcite, which was previously measured for its capa- A Shimadzu gas chromatograph (GC-14B), equipped
city and stability under wet gas conditions (see Ding with a TCD detector and a Porapak-Q column, was used
& Alpay, 2000). The adsorbent was also crushed and for sample analysis. In addition, two on-line Telegan
sieved into the particle size groups mentioned above. As CO analysers (0}30 and 0}5%FSD) were used to moni-
a catalyst diluent, e.g. in the absence of adsorbent, silicon tor the reactor e%uent CO concentration.
carbide particles were employed. High-purity methane For the reaction studies in the absence of adsorbent,
(99.95% (v/v)) and hydrogen (99.995% (v/v)) gases were approximately 7.2 g of catalyst was admixed with dense
supplied from gas cylinders; steam supply to the SMR silicon carbide particles (&1 : 3 mass ratio), and packed
reactor was generated from distilled water. into the reactor. For the sorption-enhanced reaction
A schematic diagram of the experimental apparatus is studies, approximately 7.2 g of catalyst was admixed with
given in Fig. 1. The reactor consisted of a stainless-steel 14.8 g of CO adsorbent. Reactor operating conditions
tubular column of internal diameter 12.4 mm and length for both the adsorbent and adsorbent-free systems are
220 mm, packed with a mixture of catalyst and adsorbent summarised in Table 1.
(or silicon carbide) particles. The reactor was "tted with As mentioned above, conversion enhancement arises
inlet and outlet lines for introducing feed gas (CH and prior to the equilibration of the adsorbent. In this work,
H O), purge as (H /He and H O) and reducing gas (H ). transient operation was imposed by means of step cha-
The inlet CH #ow rate was controlled by a Brooks nges in feed concentration. Due to the negligible resi-
5850E mass#ow controller. An HPLC pump was used to dence time of methane in the reactor, even in the presence
supply water to the reactor via a vaporiser (i.e. a heated of adsorbent (i.e. typically less than 0.2 s), the conversion
tubular column packed with silicon carbide particles); enhancement factor at any given time (E(t)) can be quan-
both the reactor and water vaporiser were mounted in 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
Fig. 1. Schematic representation of the experimental system, MFC
* mass#ow controller, PC * personal computer. 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
towards any carbonaceous deposits on the catalyst, and where i denotes CH , H O, H , CO CO, and He. the
thus to ensure a reproducible catalyst activity from one semi-empirical correlation proposed by Edwards and
experiment to the next. Reproducibility was subsequently Richardson (1968) was used to estimate the axial disper-
con"rmed through repetition of the experiments. The sion coe$cient D . The catalyst e!ectiveness factor, g ,
X G
measurement of the reactor e%uent concentration pro- was set as unity for the crushed catalyst used in this work;
"les in the reaction step (step (iv)) enabled both transient see Section 4 for details. The reaction kinetic model of Xu
and steady-state reaction kinetics to be tested. Note that and Froment (1989a) can be summarised as
due to non-isothermal nature of the SMR process, the
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
*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 the SMR run (&1.5 min). However, since the experi-
gPROMS modelling environment (Process Systems En- mental conditions are nearly identical, the steady-state
terprises Ltd.). The spatial discretisation method of or- concentrations of CH , H , and CO are approximately
thogonal collocation on "nite elements was employed. equal, indicating no strong direct catalyst/adsorbent in-
Second-order collocation on 100 elements was found to teraction. The measured e%uent CO concentrations were
give a converged solution in which component balance found to be very low ((0.2% (v/v)) for all these runs.
errors (associated with the numerical integration) did not The longer transient time of the SE-SMR run is mainly
exceed 1%. A summary of parameters (constants) used due to the interaction between the adsorption and reac-
for the simulations is given in Table 2. 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
4. Results and discussion gas-phase CO partial pressure, but also releases some
heat, both of which are favourable for the reforming
Typical reactor e%uent concentration pro"les mea- reactions (1) and (2). On the other hand, an increase in the
sured in the SMR and SE-SMR experiments under SMR reaction rate will result in a decrease in the reactor
similar operating conditions (4503C, 445.7 kPa, H O/ temperature due to the endothermic nature of the re-
CH "6) are shown in Fig. 2(a) and (b), respectively. It forming reactions; see below for further discussions on
can be seen that in the presence of CO adsorbent, the the reactor temperature pro"les in the presence and ab-
transient period (&5 min) is much longer than that of 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. 2. E%uent concentration (mole fraction) pro"les on a water-free Fig. 3. Comparison of methane conversion pro"les and CO break-
basis: comparison between experiments and simulations (reactor through curve (reactor pressure"445.7 kPa, temperature"
pressure"445.7 kPa, temperature"450$23C, feed #ow rate of 450$23C, feed #ow rate of CH "250 ml/min (STP), molar ratio
CH "250 ml/min (STP), molar ratio of H O to CH "6, cata- of H O to CH "6, catalyst/adsorbent (or carbide) particle
lyst/adsorbent (or carbide) particle size"0.25}0.5 mm). size"0.25}0.5 mm).
Y. Ding, E. Alpay / Chemical Engineering Science 55 (2000) 3929}3940 3935
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).
3936 Y. Ding, E. Alpay / Chemical Engineering Science 55 (2000) 3929}3940
Fig. 8. E!ect of reactor temperature on the conversion enhancement Fig. 10. E!ect of particle sizes of catalyst and adsorbent on the transi-
(reactor pressure"445.7 kPa, molar ratio of H O to CH "3, space
ent kinetics (reaction temperature"459$13C, reactor pressure"
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. 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
Fig. 9. E!ect of reactor pressure on the conversion enhancement (reac-
signi"cance of the adsorption and desorption kinetics.
tor temperature"445.5$13C, molar ratio of H O to CH "3, space As mentioned in Section 2, the transient experiments in
time"10.7 g-cat h/mol-CH , catalyst/adsorbent size"0.25}0.5 mm, this work consisted of a step change from a hydro-
measured steady-state conversions"17.8%, 14.87%, 12.13% and gen}steam feed to a methane}steam feed. Experiments
10.5% for reactor pressures"308, 445.72, 583.68 and 721.5 kPa corre- have also been performed in which H is replaced with
spondingly).
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
Fig. 9 shows the e!ect of reactor pressure on the of the CH conversion for the two cases is given in
enhancement factor; other operating conditions are Fig. 11; operating conditions for both cases are set as
set as 457.53C, 10.7 g-cat h/mol-CH , H O : CH " 4453C, 445.7 kPa, 6.27 g-cat h/mol-CH , H O : CH "
3 mol/mol. It can be seen that the enhancement factor 3 mol/mol. It can be seen that at early times, the methane
increases with increasing reactor pressure. Higher pres- conversion is higher under an initial He}H O environ-
sures will favour greater CO adsorption, and will result ment. This inhibitive e!ect of H on the reaction kinetics
in a greater potential for reaction enhancement due to is well documented; see, for example. Bodrov, Apel'baum
a reduction in the equilibrium conversion of CH . Thus, and Tempkin (1967, 1968), Phung Quach and Rouleau
although SMR reactions (1) and (2) are favoured by low (1975) and Ross and Steel (1973). For example, Phung
pressures, the above result suggests that the sorption- Quach and Rouleau (1975) studied the kinetics of SMR
enhanced SMR reactor can be operated at higher pres- over Ni/a-Alumina catalyst in a continuous stirred tank
sures to achieve the same product yield. This, of course, is reactor at 350}4503C; a Langmuir}Hinshelwood}
particularly bene"cial where the direct high-pressure de- Hougen}Watson type rate equation was found to "t their
livery of H is of economic advantage. kinetic data satisfactorily, and the equation obviously
3938 Y. Ding, E. Alpay / Chemical Engineering Science 55 (2000) 3929}3940
K adsorption constant for component j (on cata- Alpay, E., Chatsiriwech, D., & Kershenbaum, L. S. (1995). Combined
H reaction and separation in pressure swing processes. Chemical En-
lyst surface), j"CO, H , CH : Pa\, j"H O:
gineering Science, 49, 5845}5864.
dimensionless
Armor, J. N. (1995). Membrane catalysis: What is it now, what needs to
K Ergun equation coe$cient, N s/m
4 be done? Catalysis Today, 25, 199}207.
K static e!ective thermal conductivity, J/m K
X Bird, R. B., Stewart, W. E., & Lightfoot, E. N. (1960). Transport phe-
K e!ective thermal conductivity, J/m K nomena. New York: Wiley.
X Bodrov, N. M., Apel'baum, L. O., & Tempkin, M. I. (1967). Kinetics of
reactor length, m
m Langmuir model constant for component i, the reaction of methane with water vapour catalysed by nickel on
G a porous carrier. Kinetika L Kataliz, 8, 821}828.
mol/kg Bodrov, N. M., Apel'baum, L. O., & Tempkin, M. I. (1968). Kinetics of
P pressure, Pa the reaction of methane with steam on the surface of nickel at
P partial pressure of gas-phase component i, Pa 400}6003C. Kinetika L Kataliz, 9, 1065}1071.
G Brun-Tsekhovoi, A. R., Zadorin, A. N., Katsobashvili, Ya. R., & Kou-
P outlet pressure, Pa
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