Pergamon Chemical Engineering Science, Vol. 52, No. 10, pp.

1609-1622, 1997
1997 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
PII: $1111O9- 25119( 91~) 11@511- 8 0009-2509/97 $17.00 + 0.00
The fluidized-bed membrane reactor for
steam methane reforming: model
verification and parametric study
A. M. Adris,* C. J. Lim and J. R. GracC
Depar t ment of Chemical Engineering, University of British Col umbi a, Vancouver, BC,
Canada V6T 1Z4
(Received 19 April 1996; in revised form 25 November 1996; accepted 27 November 1996)
Abs t r aet - - A new appr oach is presented for the modelling of a fluidized-bed membr ane react or
(FBMR). The model considers the t wo-phase nat ure of the fluidized-bed react or system and the
parallel reactions t aki ng place in stream met hane reforming, as well as selective permeat i on
t hr ough the walls of membr ane tubes immersed in the bed. The model is based on the
t wo-phase bubbl i ng bed model with allowance for some gas flow in the dense phase. Pl ug flow
is assumed for the combi ned sweep gas and permeating hydr ogen flowing t hr ough the mem-
brane tubes. Fr eeboar d non-i sot hermal effects and reactions are also t aken i nt o account. The
coupl ed differential equat i ons for the fluidized bed and membr ane tubes are solved numerically.
The model is in very good agreement with experimental data, bot h with and wi t hout per-
meation, obt ai ned in a pilot-scale react or system. Paramet ri c investigations demonst rat e the
effect of key operat i ng variables and design paramet ers over a wide range, The model is also
tested for its sensitivity t o changes in hydr odynami c parameters. Increasing the permeat i on of
hydr ogen t hr ough the membr ane tubes is of key i mport ance in achieving high met hane
conversions and in minimizing adverse reactions in the freeboard region. Hydr odynami c and
kinetic properties have limited influence for the conditions studied. 1997 Elsevier Science
Ltd. All rights reserved
K e y w o r d s : Fluidization; membranes; permeation; reforming; hydrogen; react or modelling.
1. INTRODUCTION
Steam reforming of light hydr ocar bons, especially
nat ural gas, is an industrially i mpor t ant chemical re-
act i on and a key step for produci ng hydr ogen and
syngas for ammoni a and met hanol product i on, hy-
drocracki ng and hydrot reat i ng, oxo-al cohol and
Fi scher - Tr opsch synthesis and ot her i mpor t ant pro-
cesses in the pet rol eum and petrochemical industries.
However, industrial fixed-bed steam reformers suffer
from several probl ems which seriously affect their
operat i on and performance. These include low cat a-
lyst effectiveness due t o internal mass transfer resist-
ance in the large catalyst particles, low heat transfer
rates, large t emperat ure gradients and t her modyn-
amic equilibrium constraints. These probl ems with
convent i onal reformers can be alleviated by using
a fluidized-bed membr ane react or (FBMR) system for
steam met hane reforming (SMR) (Adris e t a l . , 1994).
This new react or system combi nes several advant ages
* Present address: Department of Research and Techno-
logy Support, SABIC R&D, P.O. Box 42503, Riyadh 11551
Saudi Arabia.
, Corresponding author.
of fluidized beds as chemical reactors, in part i cul ar
catalyst bed temperature uniformity, i mproved
heat transfer and virtual elimination of intracatalyst
diffusional limitations, with advant ages offered by
permselective membr ane technology, in part i cul ar
shifting the convent i onal t her modynami c equilibrium
and i n s i t u separation and removal of a desirable
reaction pr oduct in a very pure state.
I n a related st udy (Adris, 1994), a pilot-scale reform-
ing pl ant of internal diameter 102 mm with a hydr o-
gen capaci t y of 6 m3[ STP] / h, able t o operat e at tem-
peratures up t o 750C and pressures up t o 1.5 MPa,
was commi ssi oned t o examine the concept of the new
fluidized-bed membr ane react or system for steam re-
forming of nat ural gas and t o st udy its properties. The
present paper considers the modelling of the FBMR-
SMR reactor.
The first at t empt t o model the FBMR system was
conduct ed by Adris e t al . (1991), who simulated an
industrial-scale fluidized-bed membr ane reformer in
order t o explore the potential of this new react or
system and compar e it with convent i onal reforming
units. This earlier model was based on the Orcut t
model with perfect mixing of the dense phase gas
(Orcut t e t al . , 1962) and with a number of simplifying
1609
1610 A.M. Adris et al.
assumptions which made the system of equat i ons sim-
ilar t o those for a CSTR. Those simplifications were
adequat e for ' gross' prediction of the overall react or
performance.
In order t o represent the hydrodynami cs better, the
simulation work in the present paper is based on the
two-phase bubbling bed react or model (Grace, 1984) (7)
with allowance for some gas flow (assumed t o be in
plug flow) in the dense phase. This assumpt i on was (8)
also used in a second version of the Orcut t model
(Orcutt e t al., 1962). Bot h versions of the model con-
sider selective removal of hydrogen by permeat i on
t hr ough membr ane tubes immersed in bot h the dense
bed and the dilute phase. Reaction taking place over
entrained catalyst particles in the freeboard zone is
also taken into account in the present model.
2. MODEL DEVELOPMENT
2.1. M o d e l a s s u m p t i o n s
The phases considered in the present model are
illustrated schematically in Fig. 1. The model is based
on the following assumptions:
(1) Steady-state conditions are assumed.
(2) The dense catalyst bed is considered t o be
composed of two phases, a bubble phase and
a dense phase.
(3) Axial dispersion of gas is i gnored in bot h
phases.
(4) Reaction occurs most l y in the dense phase.
However, the bubbles cont ai n some solids
which cont ri but e t o the overall reaction.
(5) In view of their small size, the diffusional resist-
ance inside the catalyst particles is neglected.
(6) The interior of the membr ane tube is t aken as
a separate region which exchanges hydrogen
(9)
(10)
(11)
(12)
with bot h the bubble phase and the dense
phase. A 'sweep gas' such as steam is used
inside the membr ane tubes t o mai nt ai n a low
partial pressure of hydr ogen there, helping t o
pr omot e permeat i on of hydrogen t hr ough the
walls of the tubes.
Sweep and permeating gases are in plug flow
inside the membr ane tubes.
Gases leaving the bed surface travel in plug
flow and undergo chemical reaction in the
freeboard region over the surface of entrained
catalyst particles.
The concent rat i on of solids in the dilute free-
boar d phase decays exponentially with height.
Hydr ogen is the onl y species which permeates
t hr ough the membr ane tube walls.
Ideal gas behavi our is assumed.
The temperature is assumed t o be const ant in
the dense bed region, but it may vary in the
freeboard region.
2.2. M o d e l f o r m u l a t i o n
2.2.1. D e n s e c a t a l y s t b e d e q ua t i on s . A mole balance
on component i (where i equals 1 for methane, 2 for
steam, 3 for car bon monoxi de and 4 for car bon diox-
ide) in the bubble phase gives
dnib
d h = k i q ab eb A ( Ci d - - C i b ) + ~ b P s A R i b . (1)
For i = 5 (hydrogen), the component mass balance in
the bubble phase is given by
dnib
d h = klqabg'bA(Cia - - Cib)
P n o s _
+ ( ~ b PsARi b - - ~ e ( - - ~ H ) Cevlg, b ( P r l ~ po~s)
(2)
_ _ [ _ h y d r o g e n a n d
Permbate ~sweep gas

o o z=o
ph~sel D I
Permeate ..~.F_ .~. ~ ~ . ~ ~ h=H
i
i g a s
Membrane
tubes
o t h e r
~L_ product
. ~ stream
= Lr----J Fr e e b o a r d
z o n e
~
h=O
reactants
I ~ l l S e
bed
z o n e
Fig. 1. Schematic showing phases considered in the fluidized-bed membrane reactor model.
Modelling of a fluidized-bed membrane reactor
where C~pz is t he equi val ent per meat i on capaci t y per fr eeboar d r egi on gives
uni t l engt h of t he membr ane t ube, defi ned as t he
ext er nal surface ar ea of t he me mbr ane t ubes di vi ded
by t he t ube wal l t hi ckness per uni t length.
Si mi l arl y, a mol e bal ance on c ompone nt i (i = 1- 4)
in t he dense phase gives
dnia
dh = kiqab~'bA(Cib - - Cid) "q- Oa p , A R i a . (3)
Fo r hydr ogen, t he cor r es pondi ng equat i on is
dnid
dh - k i q ab eb A( Ci b - - C i d )
, { p H ' ~
+ ~ t p s A R i d - e \ M H / ]
x C , t , , ( l - - e b ) ( P a s - - p O ; S ) . ( 4 )
Fi nal l y, a mol e bal ance on hydr ogen ( component
i = 5) in t he s epar at i on phase (i.e. i nsi de t he mem-
br ane t ubes) gives
dh MHH {(1 - - e b ) ( P d 5 - - pO~5)
+ eb(pO.b5 _ pO;5)}. (5)
Boundar y condi t i ons at h = 0 ar e n~b =n~,
( Uo - Um i ) / Uo , nld = n i i U ~ f / U o and ni~ = 0, where it
is assumed t hat t he gas flow t hr ough t he dense phase
is t hat needed for mi ni mum fl ui di zat i on.
I t is c ommon pr act i ce in model l i ng st eam r efor mi ng
r eact or s t o consi der t he conver si on of t wo key com-
ponent s and t hen t o obt ai n t he concent r at i ons of
t he ot her component s by appl yi ng st oi chi omet r i c
r el at i ons (Xu and Fr oment , 1989; Adr i s e t al ., 1991;
Sol i man e t al ., 1992). The pr esent model , however,
consi der s t he change in t he mol ar flow of each compo-
nent separ at el y so t hat differences in diffusivities can
be account ed for ri gorousl y.
The r eact i on rat e t erms, Rib and Rid in eqs (1)-(4),
r epr esent t he rat es of f or mat i on of component i in t he
bubbl e or dense phase, essent i al l y equal t o t he i nt r i n-
sic r at es since t he ext er nal mass t ransfer resi st ance is
negl i gi bl e for t he size of cat al yst par t i cl es consi dered.
Each R~ is t he combi nat i on of t he rat es of f or mat i on
and di s appear ance of this c ompone nt t hr ough t he
t hree pr i nci pal par al l el r eact i ons t aki ng pl ace in st eam
r efor mi ng given in Appendi x A. React i on r at e expres-
si ons and const ant s, equi l i br i um const ant s and ad-
s or pt i on const ant s ar e al so given in Appendi x A. The
Xu and Fr ome nt (1989) r at e expr essi on has been ut i l -
ized due t o its general nat ur e and its abi l i t y t o de-
scri be t he ki net i cs of t he r efor mi ng r eact i on over
a wi de range of oper at i ng condi t i ons (El nashai e e t al .,
1990).
The hydr odynami c par amet er s r equi r ed t o solve
eqs (1)-(5) ar e obt ai ned usi ng s t andar d r el at i ons from
t he l i t er at ur e as summar i zed in Appendi x B.
1611
2.2.2. D i l u t e p h a s e ( i . e . f r e e b o a r d r e g i on ) e q ua -
t i on s. A mol e bal ance on c ompone nt i (i = 1- 4) in t he
dn i , = q J~ A R i z. (6)
d z
Fo r i = 5 (hydrogen) t he di l ut e- phase equat i on is
dn,~dz - VzAR, z - *e ~ Cep,(P.z -- e~; 5) (7)
where z is t he di st ance above t he bed surface. The
boundar y condi t i on at z = 0 is n~ = n~d + n~b, eval u-
at ed at h =/ - / . u?z is t he sol i ds mass concent r at i on in
t he f r eeboar d zone given as: u?z = E z / Uo , while E~ is
t he ent r ai nment flux of sol i ds at a di st ance z above t he
bed surface, given by Wen and Chen (1982) as
Ez = E~ + (Eo - - Eo~)e -"cz (8)
where Eo is t he ent r ai nment flux of sol i ds at t he bed
surface, Eo~ is t he ent r ai nment flux of sol i ds above t he
t r ans por t di sengagement hei ght ( TDH) and a~ is an
overal l decay const ant , t aken here as 4 m- 1 as sug-
gest ed by Ge l dar t (1986). E0 and E~ were al so cal -
cul at ed accor di ng t o t he pr ocedur e given by Ge l dar t
(1986).
The selective s epar at i on of hydr ogen by t he mem-
br ane t ubes in t he fr eeboar d zone is descr i bed by
a modi fi ed form of eq. (5):
dn,~ _ , ( p , "~
dzz e \ M H ] Ce p t ( P ~ - - pO~5). (9)
2.3. S o l u t i o n a l g o r i t h m
The sol ut i on al gor i t hm is compos ed of t hree mod-
ules:
(1) The first modul e solves for r eact i on and per-
meat i on in t he cat al yst bed zone.
(2) The second modul e sol ves for r eact i on and per-
meat i on in t he par t of t he fr eeboar d zone which
i ncl udes membr ane t ubes.
(3) The t hi r d modul e solves for t he r eact i on in any
par t of t he fr eeboar d zone t hat does not i ncl ude
per meabl e membr ane t ubes.
Each modul e first cal cul at es t he par amet er s needed
by t he di fferent i al equat i ons descr i bi ng t he phe-
nomena t aki ng pl ace in t hat par t of t he r eact or and
t hen solves t he model di fferent i al equat i ons by cal l i ng
a numer i cal r out i ne NL DE QD which uses t he
Run g e - Kut t a met hod, wi t h var i abl e st ep size t o en-
sure sol ut i on accuracy. All var i abl es are defi ned as
doubl e pr eci si on var i abl es t o i mpr ove t he accur acy
when dependent var i abl es are var yi ng steeply. Due t o
a del i cat e bal ance bet ween t he t hr ee t er ms i nvol ved in
t he di fferent i al equat i ons descr i bi ng t he change in
mol ar rat es in t he bubbl e and dense phases, i nt egr a-
t i on had t o be st ar t ed wi t h a very smal l st ep size,
t ypi cal l y 10 - 1 m. Temper at ur e profi l es were based
on exper i ment al measur ement s i n t he dense bed and
in t he fr eeboar d (Adris, 1994), wi t h t he t emper at ur e
1612
assumed t o be uni form bel ow t he bed surface. An
exper i ment al val ue of t he expanded bed hei ght was
al so used, while t he per meat i on capaci t y was based on
measur ement s car r i ed out on pal l adi um t ubes in
a separ at e per meat i on rig (Adris, 1994). The l i mi t i ng
case of a fl ui di zed-bed r eact or wi t hout membr ane
separ at i on can be sol ved by set t i ng Cept = O.
3. MODEL VALIDATION
3.1. M o d e l p r e d i c t i o n s v s e x p e r i m e n t a l d a t a
Exper i ment al resul t s for t he pi l ot -scal e FBMR-
SMR i nvest i gat i on have been r epor t ed el sewhere
(Adris, 1994; Adr i s e t al . , 1994b) for s t eam- t o- car bon
r at i os from 2.3 t o 4.2, r eact i on t emper at ur es from 720
t o 930 K and pressures from 0.69 t o 0.98 MPa. The
model devel oped above can be t est ed usi ng these
exper i ment al dat a bot h wi t h and wi t hout selective
per meat i on. The vol ume fract i on of t he bed occupi ed
by sol i ds di sper sed in t he bubbl e phase is t aken as
0. 5% of t he vol ume fract i on of t he bed occupi ed by
bubbl es, i.e. ~b = 0.005 eb (see Gr ace, 1986; Kuni i and
Levenspiel, 1991). A very good mat ch bet ween experi -
ment al resul t s and model pr edi ct i ons was obt ai ned
as shown by Fig. 2. Devi at i ons bet ween t he model
pr edi ct i ons and t he exper i ment al dat a are somewhat
l ar ger for t he r eact i on runs wi t hout per meat i on,
where pr edi ct i ons are mor e sensitive t o any er r or in
t emper at ur e, because t emper at ur e is t he maj or fact or
det er mi ni ng conver si on when t here is no selective
separ at i on.
Fo r r e ac t i on- pe r me at i on runs, any er r or in t he
t emper at ur e r eadi ng affects t he pr edi ct i ons t o a lesser
ext ent because t he r eact i ng mi xt ur e is shifted from
equi l i br i um due t o t he i rreversi bl e i n s i t u hydr ogen
separ at i on. The cont r i but i on of per meat i on t o t he
overal l conversi on, t oget her with t he use of effective
per meabi l i t y const ant s measur ed and fi t t ed in t he
exper i ment al st udy (Adri s e t al . , 1994b), expl ai n t he
bet t er mat ch bet ween model pr edi ct i ons and experi -
ment al dat a for t he r e ac t i on- pe r me at i on runs. The
0.8
0.7- No p e r m e a t i o n
>~ 0. 6 -
0 0. 5 -
~1~ 0. 4-
~ 0.2-
~ 0.1
13. 0.0
0. 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Experimental methane conversi on
Fig. 2. Experimental vs predicted methane conversion. For
experimental details, see Adris (1994) and Adris e t al. (1994b).
A. M. Adris e t al.
mean absol ut e val ue of t he devi at i on of t he pr edi ct ed
met hane conver si on from t he exper i ment al conver-
si on was 2. 4% for r e ac t i on- pe r me at i on exper i ment s
and 4. 2% for runs wi t hout per meat i on.
Typi cal compar i s ons bet ween si mul at i on predi c-
t i ons and exper i ment al dat a are given in Tabl e 1 for
a run wi t hout per meat i on and for a r e ac t i on- pe r -
meat i on experi ment . I t is cl ear from this t abl e t hat t he
model pr ovi des good pr edi ct i ons for t he r eact i on con-
versions, t he t ot al hydr ogen yi el d and t he per meat i ng
hydr ogen flow. Ther e are, however, differences in t he
out l et gas composi t i on, especi al l y in t he r at i o bet ween
car bon oxi des pr oduced by t he react i on. Thi s may be
due t o t he difference bet ween t he cat al yst used here
and t hat used by Xu and Fr ome nt (1989) t o devel op
t he ki net i c rat e expressi ons empl oyed in t he si mul a-
tion. Different reformi ng cat al yst s have different abi l -
ities t o cat al yse t he wat e r - gas shift r eact i on ( Rost r up-
Ni el sen, 1984). Therefore, t he fract i on of t he car bon
monoxi de conver t ed t o car bon di oxi de by this reac-
t i on may var y dependi ng on t he cat al yst . However,
this var i at i on shoul d not have a maj or influence on
t he pr edi ct ed overal l met hane conversi on, whet her t o
car bon monoxi de or car bon di oxi de.
The resul t s present ed in Tabl e I al so i ndi cat e (by
difference) t he cont r i but i on made by t he ent r ai ned
cat al yst part i cl es in t he spl ash zone (i.e. regi on i m-
medi at el y above t he dense bed upper surface) t o t he
r eact i on conversi on. Because of t he heat er desi gn in
our exper i ment al react or, t he spl ash zone t emper at ur e
is hi gher t han t he bed t emper at ur e, and t herefore t he
cat al yst par t i cl es in t he fr eeboar d cont r i but ed posi t -
ively t o t he r eact i on by about 7% of t he overal l
conversi on. In an i ndust r i al reformer, however, t he
effect of t he ent r ai ned cat al yst part i cl es is l i kel y t o be
negat i ve due t o l ower t emper at ur es in t he fr eeboar d
zone, unless an equi l i br i um shift is affected by means
of permsel ect i ve membr anes as di scussed bel ow or
unless t he fr eeboar d regi on is speci al l y heat ed.
The model devel oped and val i dat ed above i ncl udes
s t andar d hydr odynami c equat i ons and cor r el at i ons
for bubbl i ng fl ui di zed beds and utilizes ki net i c r at e
expressi ons from t he l i t er at ur e and exper i ment al l y
measur ed t emper at ur es, bed hei ght s and Cept values.
Ot her wi se t here are no fi t t ed par amet er s. Not e t hat
wi t h t he abundance of cat al yst in this r eact or system,
t he r eact i on conver si on is hi ghl y i nfl uenced by t he
t her modynami c equi l i bri a, as well as by hydr ogen
per meat i on rates.
3.2. S e n s i t i v i t y a n a l y s i s
The model is exami ned here for its sensi t i vi t y t o
four est i mat ed par amet er s: sol i ds concent r at i on in t he
bubbl e phase, di st r i but i on of feed gas bet ween t he
bubbl e and dense phases, cat al yst act i vi t y and bubbl e
size. Per meat i on was omi t t ed at this st age t o avoi d its
cont r i but i on whi ch may obscure t he effect of these
par amet er s. Sensi t i vi t y tests were r est r i ct ed t o
t he cat al yst bed conversi on, excl udi ng t he fr eeboar d
effects which var y from one r eact or t o anot her
dependi ng on t he r eact or confi gur at i on and cat al yst
Modelling of a fluidized-bed membrane reactor
Table 1. Comparison of model predictions with experimental data for two typical runs. Operating
conditions: T = 541C, P = 0.64 MPa, @b = 0.005eb, Ua = Umf
1613
Experimental Model Experimental Model
dat a predictions data predictions
(w/o penn.) (w/o perm.) (with perm.) (with perm.)
Exit methane conversion 0.400 0.391 0.419 0.421
Exit steam conversion 0.182 0.177 0.200 0.183
Methane conversion at bed surface NA 0.363 NA 0.382
Tot al hydrogen yield 1.421 1.471 1.515 1.550
Permeate hydrogen flow, mol / h 0 0 2.31 2.39
Outlet gas composition,
volume % (dry basis):
CH4 24.0 24.8 22.4 22.7
CO 0.8 1.0 0.8 1.2
CO2 16.5 14.9 16.8 15.3
He 58.7 59.3 60.0 60.8
NA: not available.
Table 2. Effects of solids concentration in the bubble phase on the methane conversion:
T = 700C, P = 1.5 MPa, Fc = 60 mol/h, S / C = 3.5
Volume fraction of bed
occupied by bubble phase
solids, qb b 0.0 0.0001 0.0005 0.001 0.005
Methane conversion 0.569 0.570 0.573 0.575 0.579
Table 3. Model sensitivity to gas flow through the dense phase: T = 700C,
P = 1.5 MPa, Fc = 60 mol/h, S / C = 3.5
Fract i on of gas flowing
through dense phase,
Ga/A U,,, s 0.01 O. 1 0.5 1.0 5.0
Methane conversion 0.554 0.555 0.562 0.568 0.579
par t i cl e- si ze di s t r i but i on. Th e bed t e mpe r at ur e was
as s ume d t o be uni f or m i n t hes e t est s, and all var i abl es ,
except t he one unde r i nves t i gat i on, wer e mai nt ai ne d
c ons t ant in each case.
3.2.1. M o d e l s e n s i t i v i t y t o sol i ds c on c e n t r a t i on in t h e
b ub b l e p h a se . Th e v o l ume f r act i on of t he bed occu-
pi ed by bubbl e phas e sol i ds, ~b, was var i e d f r om 0 t o
0.005. Me t h a n e c onve r s i on was pr edi ct ed f or fi ve di f-
fer ent cases as pr es ent ed in Tabl e 2. Th e i ncr ease i n
r e ac t i on c onve r s i on wi t h i ncr eas i ng sol i ds c onc e nt r a-
t i on i n t he bubbl e phas e ma y be at t r i but e d t o a r educ-
t i on in bubbl e by- pas s i ng, i.e. t o c onve r s i on i n t he
bubbl e phas e o v e r t he sur face of t he di s per s ed cat al ys t
part i cl es. Th e i nsensi t i vi t y of t he r esul t s t o ~b
ari ses becaus e t he c onve r s i on r api dl y appr oac he s
an e qui l i br i um val ue, wi t h l i mi t ed i nfl uence of hydr o-
dynami cs .
3.2.2. M o d e l s e n s i t i v i t y t o g a s di s t r i b ut i on b e t we e n
b ub b l e a n d de n se p h a se s. Si mul at i on r esul t s pr es ent ed
a bo v e cons i der ed t he gas fl ow t h r o ug h t he dens e
phas e t o be t hat needed for mi n i mum fl ui di zat i on,
whi ch is t he r efer ence case c ons i de r e d i n t hi s st udy.
The sensi t i vi t y of t he mode l t o t hi s as s umpt i on was
e xami ne d by var yi ng t he gas fl ow t hough t he dens e
phas e at h = 0 f r om fi ve t i mes t o 1% of t he fl ow
needed for mi n i mum fl ui di zat i on. The s i mul at i on re-
sui t s s ummar i ze d i n Tabl e 3 i ndi cat e t hat t he mo d e l is
n o t ver y sensi t i ve t o t hi s par ame t e r . Wh e n t he fl ow
t h r o ug h t he dens e phas e is t ake n as 1% of t hat needed
for mi n i mum fl ui di zat i on, a p p r o xi ma t i n g t he st ag-
nant bed as s umpt i on a d o p t e d by Kuni i and Le ve n-
spi el (1969) and Gr a c e (1984), t he me t h a n e c onve r s i on
is pr edi ct ed t o be r educed, but by ver y little.
Agai n, bubbl e by- pas s i ng ac c ount s for t hi s c hange
i n me t h a n e c onve r s i on up o n c hangi ng t he gas di st ri -
but i on be t we e n t he bubbl e and dens e phases. Th e
s i mul at ed r uns i n t hi s s t udy ar e c har ac t e r i ze d by l ow
super fi ci al gas vel oci t i es, onl y a bo ut six t i mes t he
mi n i mum f l ui di zat i on vel oci t y. I t is ant i c i pat e d t hat
t he sensi t i vi t y of t he mo d e l t o t hi s p a r a me t e r woul d be
1614
even less at higher superficial gas velocities more
typical of i ndust ri al fluidized-bed reactors.
A. M. Adris e t al.
3.2.3. M o d e l s e n s i t i v i t y t o c a t a l y s t a c t i v i t y . The
kinetic rate expressions used to estimate the rates of
reaction were developed (Xu and Fr oment , 1989) for
a different catalyst with a different nickel content. The
catalyst used i n our work mi ght have a different
activity. While the difference i n catalyst activity be-
tween two commercial catalysts is unlikely to affect
the reaction rate est i mat i on by more t han 50% (E1-
nashaie e t al ., 1990), the activity was changed here
over a wide range to examine its effect on the model
predictions. Tabl e 4 compares five cases where the
reaction rate coefficients, kl to k3, were varied from
0.025 to 5.0 times the values predicted by the equa-
tions given in Appendix A.
The predicted met hane conversi on for these five
cases indicates t hat the catalyst activity has a limited
effect on the model predictions, within the range of
activity of commercial catalysts for the catalyst i nven-
tory investigated. When the catalyst activity was re-
duced by 50%, the conversi on decreased onl y from
0.808 to 0.804. Larger changes were predicted when
the activity was varied over a wider range. The
changes in met hane conversi on shown in Tabl e 4 are
due to the i nt eract i on between the chemical reaction
and the mass exchange between the two phases (Adris,
1994), i.e. bot h t hermodynami cs and interphase mass
transfer play i mpor t ant roles.
3.2.4. M o d e l s e n s i t i v i t y t o b ub b l e s i z e e s t i m a -
t i on. The Mori and Wen (1975) equat i on (see Appen-
dix B) for est i mat i ng the bubbl e diameter, like ot her
widely used relations for bubbl e di amet er estimation,
was developed for beds wi t hout internals. In the ex-
peri ment al reactor system (Adris e t al ., 1994b), how-
ever, membr ane tubes are placed vertically i n the
reactor and the bubbl e diameters could well differ
from the estimated ones. I n this section the bubbl e
di amet er predicted by the Mori and Wen equat i on
was multiplied by factors of 0.4, 0.6, 0.8, 1.0 and 1.2 to
st udy the i mpact of bubbl e size on the conversi on
predictions. Tabl e 5 gives the predicted values for
met hane conversi on i n each case. The bubbl e size is
seen to have little influence on the reaction conversi on
for the condi t i ons investigated.
3.3. Ga s di s t r i b ut i on b e t we e n p h a s e s
Account i ng for a change i n the number of moles of
gas due to chemical reaction complicates fluidized-
bed reactor model i ng (Irani e t al ., 1980; Kai and
Furusaki , 1987). This is an i mpor t ant consi derat i on
for steam met hane reforming where, as seen from eqs
(A1) and (A3) in Appendix A, the reactions cause
a significant increase i n mol ar gas flow. A hy-
dr odynami c i nvest i gat i on of the di st ri but i on of addi-
t i onal gas flow resulting from the increase i n the t ot al
number of moles due to reaction (Adris e t al., 1993)
showed that at least some of the addi t i onal flow ends
up in the bubbl e phase. It is not clear, however,
whether the addi t i onal moles generated stay in the
dense phase for some distance or transfer quickly to
the bubbl e phase.
The model out l i ned i n the present study assumes
that the gas flows t hrough bot h the bubbl e phase and
the dense phase change with height due to the increase
i n the t ot al mol ar flow rate caused by the reforming
reactions. Since the reactions occur mostly in the
dense phase, most of the addi t i onal gas vol ume is
generated there. The extra moles are di st ri but ed be-
tween the two phases by i nt erphase mass transfer and,
possibly also, by bul k transfer of excess moles gener-
ated to the bubbl e phase, with some of the extra moles
also removed due to permeation.
The change i n the gas flow t hrough the bubbl e and
dense phases al ong the bed height is pl ot t ed in Fig. 3
for three different situations, calculated based on the
model presented i n this work. The plot shows t hat the
gas flow t hrough bot h phases increases with height
when there is no permeat i on, with the dense phase
share of the excess gas bei ng about 6 5 0 . An increase
followed by a slight decrease is exhibited for reac-
t i on- per meat i on with a limited permeat i on capacity
(Cep = 1.0 km); in this case the dense phase accom-
modat es about 5 0 0 of the excess gas, the bubbl e
Table 4. Model sensitivity to catalyst activity level: T = 800C, P = 1.5MPa,
Fc = 60 mol/h, S / C = 3.5
Rate coefficients, kt to k3,
multiplied by 0.025 0.1 0.5 1.0 5.0
Methane conversion 0.731 0.786 0.804 0.808 0.817
Table 5. Model sensitivity to estimated bubble size: T = 700C, P = 1.5 MPa,
Fc = 60 mol/h, S / C = 3.5
Bubble diameter factor 0.4 0.6 0.8 1.0 1.2
Methane conversion 0.579 0.579 0.577 0.570 0.559
Modelling of a fluidized-bed membrane reactor
0.0
1 . 0
0. 9-
~ 0. 8 ~
e"
tJ~
" 0.7- Q.
( / )
-
0. 6-
"1o
0.5-
2
r ' - '
~ 0 . 4-
~ 0 . 3-
0.2
0. 0
0.1 0.2 0.3 0.4
zx a 4
2.O E
No permeation
- - - W- - Ce p = 1 . 0 km ~ 1. 4
Cep=l 0 km
0 .'1 0 .'2 0 .'3 0.4
R
i -
a .
1.8 "~
J~
--I
J=
' -I
1 . 6 .o
i i =
0
Height coordinate, m
Fig. 3. Change of gas flow through bubble and dense phases along the reactor for no permeation and for
two different permeation capacities: T = 800C, P = 1.5 MPa, Fc = 80 mol/h, S/C = 3.5, Ps = 0.4 MPa,
Fs = 80 mol/h.
1615
Table 6. Model predictions for reforming reaction with and without permeation considering variable gas
flow in both phases and constant dense-phase gas flow assumptions: Fc = 80 mol/h, S/C = 3.5, T = 800C,
P = 1.5 MPa, Ps = 0.4 MPa, Fs = 80 mol/h (freeboard reaction ignored)
Permeation capacity, km 0 0 10 1.0
Variable gas Constant Variable gas Constant
flow in both dense phase flow in both dense phase
Model assumption phases gas flow phases gas flow
Methane conversion 0.774 0.752 0.803 0.781
Steam conversion 0.323 0.314 0.337 0.328
phase about 35%, with the bal ance bei ng removed as
hydrogen by the membr ane tubes. When the per-
meat i on capacity is increased to 10 km, the gas flow
steeply decreases after an i ni t i al increase, with most of
the excess gas removed by hydrogen permeat i on
t hr ough the membr ane tubes.
In a var i ant of the model presented above, the gas
flow t hrough the dense phase was mai nt ai ned con-
stant, i.e. Ud was mai nt ai ned const ant , so t hat all
the excess gas generated i n the dense phase and
not removed by the permeabl e membr ane tubes was
accommodat ed by the bubbl e phase. An adj ust ment
was carried out between each step i n the i nt egrat i on.
Tabl e 6 gives the model predictions for two cases
consi deri ng this ' const ant dense phase gas flow'
assumpt i on compared with the predi ct i ons of the
original model.
It is clear from Tabl e 6 t hat the division of excess
gas di st r i but i on between the bubbl e and dense phases
can affect the model predi ct i ons t o a small but ap-
preciable extent. Gi ven the available experimental
results which are domi nat ed by reaction equi l i bri um
and permeability, it woul d be difficult, if not imposs-
ible, to di scri mi nat e between the two models based on
react i on experiments. Separate experiments designed
to det ermi ne the gas flow i n the separate phases are
required to discriminate between these two rival as-
sumpt i ons, i.e. to det ermi ne how extra moles of gas
generated by the reactions are di st ri but ed between the
two phases.
4. P A R A ME T R I C I N V E S T I GA T I O N
A paramet ri c i nvest i gat i on was conduct ed to ob-
t ai n better insights i nt o the effect of maj or operat i ng
variables and design paramet ers i nfl uenci ng the per-
formance of the reactor. In addi t i on, the performance
of the FBMR system was explored beyond the range
of paramet ers which coul d be studied experimentally
due to l i mi t at i ons imposed by economi c and safety
considerations.
The r eact i on- per meat i on opt i on has been used for
the predictions i n this section, with the cont r i but i on of
1616 A. M. Adris et al.
t he fr eeboar d i gnor ed and t he t emper at ur e assumed
1.00 -
t o be uni form, except where expl i ci t l y specified ot her -
wise. The model wi t h var i abl e gas flow in bot h phases e- 0.95-
is used. Vari abl es and par amet er s st udi ed and t hei r .o,^
ranges are as follows: t emper at ur e: 400-800C; pres- ~ 0.90-
sure: 0. 3-2. 7 MPa; s t eam- t o- car bon mol ar feed r at i o: ~> "
1.5-5.5; met hane mol ar feed rat e: 20- 100 mol / h; per- oo 0.a5-
meat i on capaci t y, Cep: 0. 4-7. 0 km; sweep gas flow 0.a0.
t -
rate: 40- 120mol / h; separ at i on side pressure: t~
t - -
0. 1-0. 9 MPa. . , 0.75.
The i nvest i gat i on focused on t he effect of changi ng ~ 0.70-
these par amet er s and var i abl es on t he conver si on of
met hane. Anot her par amet er , t he fract i on of hydr o- 0.0
gen separ at ed from t he r eact i on domai n t hr ough t he
membr ane t ubes, is al so useful here in i ndi cat i ng t he
ext ent of t he equi l i br i um shift. Thi s par amet er is re-
sponsi bl e for al t eri ng t he compos i t i on of t he r eact i ng
mi xt ur e by changi ng i t s hydr ogen cont ent . The ext ent
of this change depends on t he por t i on of t he hydr ogen
pr oduced whi ch is r emoved from t he r eact i on syst em 1.0
by per meat i on. It is referred t o here as t he ' hydr ogen
fract i on separ at ed' .
4.1. Ef f e c t o f op er at i ng v ari ab l es
4.1.1. Op er at i ng p ressure. In convent i onal re-
formers, hi gher reformi ng r eact i on conversi ons are
favour ed by l ower r eact or pressures, an obvi ous con-
sequence of LeChat el i er ' s pri nci pl e. In an FBMR
system, t he SMR r eact i on is accompani ed by a separ -
at i on process which is favour ed by hi gher pressures.
Therefore, t he net effect of i ncreasi ng t he r eact or pres-
sure depends on t he bal ance bet ween t he r eact i on and
per meat i on processes. Fac t or s l i ke t he per meat i on
capaci t y, t emper at ur e and s t eam- t o- car bon r at i o al l
have significant i mpact s on this bal ance; t he net effect
coul d be a decrease, no change or an i ncrease in
met hane conversi on.
Fi ft een cases were si mul at ed here t o pr edi ct t he
effect of pressure over t he range 0.3 t o 2.7 MPa at
t hree different membr ane equi val ent per meat i on ca-
paci t i es, 0.4, 3.0 and 7.0 km. Si mul at i on resul t s t o-
get her wi t h t he cor r espondi ng equi l i br i um conver-
sions at t he r eact or - bed condi t i ons for each oper at i ng
pressure ar e pl ot t ed in Fi g. 4. The conversi ons in Fi g.
4 i ndi cat e t he t wo oppos i ng effects whi ch t he r eact or
pressure has on t he overal l conversi on. At l ow pres-
sure, t he met hane conver si on is l ower t han its equi l i b-
ri um val ue due t o t he i nsi gni fi cant ext ent of hydr ogen
separ at i on, as well as due t o st r ong bubbl e by- passi ng
caused by t he high superfi ci al gas velocity. As t he
pressure increases, t he i mpact of t he per meat i on capa-
ci t y becomes mor e i mpor t ant and t he ext ent of t he
equi l i br i um shift is det er mi ned by t he membr ane ca-
paci t y. The cases shown in Fig. 4 wi t h hi gh per-
meat i on capaci t y (Cep = 7.0 km) exhi bi t t he st r ong
pot ent i al of t he FBMR for SMR react i ons. The 0.96
met hane conver si on obt ai ned here at 800C and
2.7 MPa exceeds t he equi l i br i um conver si on by about
25%. Such a hi gh conver si on coul d onl y be obt ai ned
at a much hi gher oper at i ng t emper at ur e, about 130C
higher, in a convent i onal r efor mi ng react or.
0
0
~7
Q
0 Equi l i bri um
~7 Cep=0.4 km
Cep=3.0 km
Cep=7.0 km
o'.5 1'.o 1'.5 21o 2'.5
R e a c t o r p r e s s u r e , M P a
~7
O
3 . 0
Fig. 4. Effect of reactor pressure on the methane conversion
for different permeation capacities: T = 800C, Fc =
60 mol/h, S/C = 3.5, Ps = 0.4 MPa, Fs = 80 mol/h.
C 0.8-
._o
p -
>~ 0.5-
C
8
~
0.4.
-
g
~ 0.2.
0.0
O Equilibrium c o n ve r s i o n
F B M R c o n ve r s i o n
Hydrogen fraction s e p a r a t e d
O
O
4~o 5~o 0~o r~0
R e a c t o r t e m p e r a t u r e , C
0.50 . ~
T
0 . 45 ~ "
C
.2
o . , ~
e.-
0.35
"1-
800 0. 30
Fig. 5. Effect of reactor temperature on the methane conver-
sion and separation by permeation: P = 1.5 MPa, Fc =
60 mol/h S/C=3.5, Ps = 0.3 MPa, Fs = 80 mol/h, Cep = 7.0 km.
4.1.2. Op er at i ng t e mp e r at ur e . Incr easi ng t he oper -
at i ng t emper at ur e has a posi t i ve effect on bot h t he
r eact i on and t he per meat i on processes, since bot h
depend on t emper at ur e in an Ar r heni us fashion. Bot h
t he met hane conver si on and t he hydr ogen fract i on
separ at ed by per meat i on al ways i ncrease wi t h t em-
per at ur e as shown in Fig. 5. The i ncrease in mem-
br ane per meabi l i t y wi t h i ncreasi ng t emper at ur e does
not necessari l y mat ch t he cor r es pondi ng i ncrease in
r eact i on r at e and equi l i br i um const ant . Therefore, t he
ext ent of t he equi l i br i um shift vari es wi t h t emper at ur e
accor di ng t o t he t emper at ur e dependence of t he per-
meabi l i t y r at e const ant . The membr ane capaci t y
agai n cont r i but es t o t he ext ent t o which t he r eact i on is
shifted from t he t her modynami c equi l i bri um. The re-
act or oper at i ng t emper at ur e is l i mi t ed in pr act i ce by
t he membr ane t ube lifetime and depends on t he exi t
gas compos i t i on r equi r ement s for downs t r eam pr o-
cessing.
4.1.3. S t e a m- t o- c a r b on mol ar f e e d r a t i o (S/C). The
s t eam- t o- car bon mol ar feed r at i o is anot her var i abl e
wi t h t wo oppos i ng effects on t he FBMR. Incr easi ng
0 . 8 -
0 . 5-
2
0. 4-
|
0. 3-
0. 2
Modelling of a fluidized-bed membrane reactor
0.6
2 3 4 5
i t
Q
0
~ , ~ , ;
St ea m - t o- ca r b on m ol a r f eed r a t i o
0. 4
0. 3
0. 2
Fig. 6. Effect of steam-to-carbon molar feed ratio at con-
stant methane flow on the reaction conversion and hydrogen
separation: T = 600C, P = 1.5 MPa, Fc = 60 mol/h, Ps =
0.3 MPa, Fs = 80 mol/h, Cep = 3.0 km.
t .oo
0. 95 -
" ~ 0. 9 0-
O~
0. 85-
o m
0. 80-
t -
o . 7s -
0. 70
2'0
1617
l 0
0 Equilibrium
With p e r m e a t i o n
No p e r m e a t i o n
0 0
4'o 6'0 8'0 1~o
M e t ha n e f l ow, m ol / h
Fig. 7. Effect of reactor throughput on methane conversion:
T = 800C, P = 1.5 MPa, Ps = 0.4 MPa, Fs = 80 mol/h,
S/C = 3.5, Cep = 3.0 km.
the S / C rat i o increases the react i on conversi on ther-
modynami cal l y. However, a higher steam concent ra- 04s
t i on i n the reacting mi xt ure reduces the hydrogen
concent r at i on, t hereby di mi ni shi ng the dri vi ng force .~ 0.44-
for permeat i on. The choice of S / C is const rai ned at its
lower and upper limits by car bon format i on and cata- 043.
lyst re-oxidation, respectively. I n addi t i on, pal l adi um
..
has a t endency t o form oxides i n an oxidizing at mo- ~ 0.42-
sphere (Tsotsis e t al., 1993), and high st eam-t o-carbon ,~
ratios may affect the t ube life. 0.41-
In the si mul at i on, the st eam- t o- car bon mol ar feed
ratio was changed from 1.5 to 5.5 by i ncreasi ng the 0.40
flow of steam at a const ant met hane flow. The result-
ing met hane conversi on and hydrogen fraction separ-
ated for these two cases are presented i n Fig. 6. The
net effect is an overall increase i n met hane conversion.
However, a st rong negative effect on the selective
separat i on process is exhibited i n Fig. 6 by the steep
decrease i n the hydrogen fraction separated, from 0.52
at S / C = 1.5 to 0.27 at S / C = 5.5, i ndi cat i ng a reduc-
t i on i n the extent of the equi l i bri um shift.
40 60 80
0
0
100 120
i
o
o
M e t h a n e c o n ve r s i o n
0 H y d r o g e n s e p a r a t i o n
4'0 ;o 8'0 1~o 1~o
Sw e e p g a s fl o w r a t e , m o l /h
0.38
" 0
0.36
a .
0.34
e-
.o_
0.32 ~
m
0.30 4::
r -
0.28 L~
"10
0.26 ' 3"
0.24
Fig. 8. Effect of sweep gas flow on the reaction conversion
and hydrogen separation: T = 600C, P = 1.5 MPa, Fc =
60 mol/h, S/C = 3.5, Ps = 0.3 MPa, Cep = 3.0 km.
i ndi cat i ng t hat the membr ane separat i on is insuffi-
cient to compensat e for bubbl e by-passing.
4.1.4. R e a c t or throughput. Increasi ng the reactor
t hr oughput (i.e. overall gas flow rate) affects the per-
formance of the FBMR negatively: (a) by i ncreasi ng
bubbl e by-passi ng and (b) by reduci ng the magni t ude
of the equi l i bri um shift due to a reduct i on i n the
fraction of hydrogen separated by permeat i on at the
same membr ane capacity. The effect of this vari abl e
was exami ned by performi ng five si mul at i ons where
the met hane feed rate was increased from 20 to
100 mol / h at a const ant st eam- t o- car bon ratio. Re-
sults are shown i n Fig. 7 confi rmi ng the ant i ci pat ed
negative effect. The predicted met hane conversi on
wi t hout membr ane separat i on is pl ot t ed on the same
graph for compari son. The gap between the conver-
sion with and wi t hout permeat i on is di mi ni shed as the
met hane flow rate increases, due to the decline i n the
role played by membr ane separat i on i n shifting the
equi l i bri um. At the highest met hane flow the FBMR
gives a lower conversi on t han the equi l i bri um value,
4.2. Ef f ect o f membrane-si de design p ar amet er s
The effect of the sweep gas flow rate was studied by
changi ng its value from 40 to 120 mol/h. The pre-
dicted met hane conversi ons and hydrogen fractions
separated are pl ot t ed agai nst sweep gas flow i n Fig. 8.
The increase i n sweep gas flow reduces the hydrogen
part i al pressure on the separat i on side, thereby in-
creasing the permeat i on dri vi ng force and leading to
higher rates of hydrogen removal from the reaction
domai n. The extent of the increase i n conversi on is,
however, relatively small, with a t ri pl i ng of the sweep
gas flow onl y i ncreasi ng the conversi on from about
0.415 to 0.434.
The separat i on side pressure was varied from 0.1 to
0.9 MPa to explore its influence. The predictions are
pl ot t ed i n Fig. 9 showing t hat an increase i n the
separat i on side pressure causes a decrease i n conver-
sion. This is because an increase i n the hydrogen
part i al pressure on the separat i on side reduces the
1618
0.91
0.9
" ) 0.89
!
8 o . ~
I 0 . 8 7
0. 86
0. 85
o
o
D
[]
0
o12 o14 o18 o i .
Separation side p r e s s u r e , M P a
A . M .
0.8
0.5~
0.4
r - I ~ 0.3 }
0.2
Fig. 9. Effect of separation side pressure on the reaction
conversion and hydrogen separation: T = 800C, P =
1.5 MPa, Fc = 60 mol/h, SIC = 3.5, Fs = 80 mol/h, Cev =
3.0 km.
2 4 6
i i i
O
o
0
O Methane conversion
0 Hydrogen sepamlJon
0
1.0
O.S ~
0. 6 e-.
0.4 ~
0.2 ~
"r
1.1111
0.95.
t-
O
' ~ 0 . 80 .
0.85-
O.SO.
t -
~ o.rs-
070 ~ ; 6 o o
Equival ent permeation capacity, Cop, km
Fig. 10. Effect ofmembranecapacity on the reaction conver-
sion and hydrogen separation: T = 800C, P = 1.5 MPa,
Fc = 60 mol/h, SIC = 3.5, Ps = 0.3 MPa, Fs = 80 mol/h.
permeat i on dri vi ng force. The extent of this negative
effect is agai n limited, with the ninefold increase i n the
separat i on side pressure onl y reduci ng the met hane
conversi on by about 4%. It shoul d be remembered,
however, t hat higher membr ane side pressures enabl e
the use of t hi nner membr ane t ube walls, thereby en-
hanci ng permeat i on.
The effect of the capacity of the membr ane tubes,
expressed as the equi val ent permeat i on capacity, Cep,
Adris et al.
was also examined. As expected, the overall conver-
sion increases significantly as the membr ane capacity
increases. The effect is not limited by ot her factors in
the model. Results are plotted i n Fig. 10. However, in
practice tubes must be separated by a distance of at
least 20 dp to 30 dp to mai nt ai n good fluidization
(Grace, 1982), and this puts an upper limit on the
number of tubes. Also the wall thickness must be
sufficient to allow the tubes to wi t hst and mechani cal
forces and erosi on i n the bed. Like the other two
separat i on side paramet ers discussed above, Ce~ must
be optimized on an economic basis, consi deri ng the
cost of the membr ane material together with the cost
of generat i ng and recovering the sweep gas, most
likely steam.
4.3. Ef f e c t o f memb r ane se p ar at i on on f r e e b oa r d r eac-
t i ons
One of the i mpor t ant advant ages of the FBMR
system for reversible reactions is its ability to suppress
undesi rabl e reactions i n the freeboard region by shift-
ing the t her modynami c equi l i bri um by product re-
moval mai nl y in the dense bed. This propert y of the
FBMR is demonst rat ed here by four si mul at i on runs
where, for i l l ust rat i on purposes, the freeboard was
assumed to be cooler t han the average bed temper-
at ure by 75C, while the mass of ent r ai ned catalyst
was assumed to be 4 times t hat estimated for our
r eact i on- per meat i on experiments. The first r un was
performed wi t hout hydrogen separation; in the sec-
ond and third, hydrogen was selectively removed us-
i ng two different membr ane capacities, while the
fourth had membr ane tubes ext endi ng i nt o the free-
boar d region. Tabl e 7 gives the condi t i ons and pre-
dicted results.
Tabl e 7 shows t hat freeboard reactions reduce the
met hane conversi on i n the first case by about 4%,
with the resulting exit conversi on falling between the
equi l i bri um conversi on at bed condi t i ons and t hat
correspondi ng to the freeboard conditions. In the
second case, met hane conversi on at the bed surface
approaches equi l i bri um by virtue of membr ane separ-
ation, with freeboard reactions affecting the conver-
sion in a negative way, but to a lesser extent t han for
the first case. When the membr ane capacity is in-
creased in the t hi rd col umn, the reaction conversi on
exceeds the equi l i bri um limits i n the bed and very
Table 7. Predicted effect of membrane separation on limiting reaction reversal in the freeboard:
P = 1.5 MPa, TR = 800C, T1b = 725C, Fc = 80 mol/h, S/C = 3.5, Fs = 80 mol/h, Ps = 0.4 MPa,
mass of catalyst entrained in the freeboard = 0.03 kg
Permeation capacity in dense bed, km 0 2.80 6.73 2.80
Permeation capacity in dilute phase, km 0 0 0 1.2
Methane conversion at bed surface 0.774 0.822 0.857 0.822
Equilibrium conversion at bed conditions 0.831 0.831 0.831 0.831
Methane conversion at reactor exit 0.735 0.798 0.848 0.819
Equilibrium conversion at freeboard 0.647 0.647 0.647 0.647
conditions
Modelling of a fluidized-bed membrane reactor
little reverse react i on is predicted in the freeboard
region. Indeed, the overall conversi on remained
higher t han the equilibrium conversion for the bed
conditions and much higher t han the equilibrium
conversi on at the freeboard conditions.
It is clear t hat removal of pr oduct hydr ogen from
the dense bed by means of permeable membranes can
significantly reduce adverse freeboard effects. Fur t her
membr ane separat i on in the freeboard region coul d
also be helpful. I n the final case, the membr ane capa-
city in the dense catalyst bed is the same as in the
second case, but Cep is augment ed by a further 1.2 km
of membr ane in the freeboard. This addi t i on leads t o
al most no reduct i on in met hane conversi on in the
freeboard, despite the reduced t emperat ure there. For
the condi t i ons explored here, membr ane surfaces in
the freeboard zone do not cont ri but e t o the net ther-
modynami c equilibrium shift and therefore cannot
lead t o met hane conversions higher t han at the bed
surface. They do, however, cause a reduct i on in the
reverse reaction. The distribution of membr ane capa-
city between the bed and the freeboard is i mpor t ant in
designing a fluidized-bed membr ane reactor, with the
opt i mum distribution depending on operat i ng condi -
tions and catalyst properties, as well as on what is
downst ream of the reforming process.
5. CONCLUSIONS
A comprehensive mat hemat i cal model has been
developed for the fluidized-bed membr ane react or
(FBMR) system and successfully validated against
pilot-plant dat a for steam met hane reforming (SMR).
The model is utilized t o examine the effect of operat -
ing variables beyond those which coul d be realized
experimentally. The predictions demonst rat e the role
played by membr ane separat i on in exceeding equilib-
ri um conversions and in suppressing freeboard reac-
tions. The membr ane capaci t y and their distribution
between the dense catalyst bed and the freeboard
region are i mpor t ant design paramet ers in FBMR
systems.
Hydr odynami c paramet ers have onl y a limited ef-
fect on the model predictions for the condi t i ons ex-
plored because of the domi nance of reaction t hermo-
dynami cs and selective permeat i on as the t wo maj or
phenomena influencing conversi on within the FBMR
system. Mor e experimental measurements are re-
quired t o discriminate between t wo rival assumpt i ons
explored in this work regardi ng the distribution of gas
flow generated by the increase in the number of moles
due t o reaction, p~
NOTATION Pi
ab specific surface area of gas bubbles, R
m2/ m 3 RR1, RR2, RR3
ac overall ent rai nment decay const ant ,
m - 1 Ri
A react or cross-sectional area, m 2
Ci concent rat i on of component i, mol / S/C
m 3
Cep
Cepl
db
db,,,
dbo
dp
D
DeN
Die
Eo
Ez
FBMR
Fc
Fs
#
G
h
H
Ho
AH298
k l , ka
k2
K1, K3
K2
kcH,, kco, kH2
kmo
klq
Mn
ni
Nor
P
Pl-lb, Pna, P m
1619
equivalent permeation capacity: mem-
brane surface/wall thickness, m2/m
equivalent permeat i on capacity per
unit length, m2/ m 2
bubble size, a function of height de-
fined by eq. (B1), m
maxi mum bubble diameter, m
initial bubble size produced at the dis-
t ri but or level, m
mean particle diameter, m
react or diameter, m
denomi nat or of the kinetic rate ex-
pression defined by eq. (A8)
effective molecular diffusivity of com-
ponent i, m2/s
ent rai nment flux of solids at the bed
surface, kg/ m 2 s
ent rai nment flux of solids at distance
z above the bed surface, kg/ m 2 s
fluidized-bed membr ane react or
mol ar feed rate of met hane equiva-
lent, mol/s
mol ar flow rate of sweep gas, mol/s
acceleration of gravity, m/s 2
volumetric flow, m3/s
vertical coordi nat e measured from
di st ri but or plate, m
expanded bed height, m
static bed height, m
heat of reaction at 298 K, J / mol
rate coefficients of reactions (A1) and
(A3), respectively, mol MPaS/ kgc, t s
rate coefficient of reaction (A2),
mol/kgc,t s MPa
equilibrium const ant for reactions
(A1) and (A3), MPa 2
equilibrium const ant for reaction (A2)
dimensionless
adsorpt i on const ant s for CH4, CO
and H2, respectively, MPa - 1
dissociative adsorpt i on const ant for
H20, dimensionless
interphase mass exchange coefficient
for component i, m/s
mol ecul ar weight of hydrogen, kg/ mol
mol ar flow rate of component i, mol/s
number of orifices in the grid
react or t ot al pressure, MPa
partial pressure of hydr ogen in the
bubble, dense and separation phase,
respectively, MPa
total pressure on the separation side,
MPa
partial pressure of component i, MPa
ideal gas constant, 8.314 J / mol K
rates of reactions (A1), (A2) and (A3)
respectively, mol/kgca t s
rate of format i on of component i,
mol/kg~,t s
st eam-t o-carbon mol ar feed ratio, di-
mensionless
1620
SMR
T
TDH
Ub
Ud
uo
U~s
steam met hane reforming
temperature, C
t ransport disengaging height, m
bubble rising velocity, m/s
superficial gas velocity t hr ough the
dense phase, m/s
superficial gas velocity, m/s
superficial gas velocity at mi ni mum
fluidization, m/s
freeboard zone vertical coordinate, m
Greek letters
~mf
~b
~)b, ~)d
( I ) e
Pn
Ps
bed voidage at mi ni mum fluidization
volume fraction of bed occupied by
bubbles
volume fraction of bed occupied by
solids in bubble and dense phases, re-
spectively
effective permeat i on rate constant,
m2/s MPa -5
hydrogen density, kg/ m 3
particle density, kg/ m 3
solids concent rat i on in the freeboard
zone, kg/ m 3
Subscripts
b bubble phase
d dense phase
f feed
f b freeboard
i integer (1-5) denot i ng gaseous com-
ponent s
m maxi mum
m f mi ni mum fluidization
o at di st ri but or plate
R reaction side
s separation side
z at height z in freeboard zone
RE F E RE NCE S
Adris, A. M. (1994) A fluidized bed membrane react or
for steam met hane reforming: experimental verifi-
cat i on and model validation. Ph. D. dissertation,
Univ. of British Columbia, Vancouver, Canada.
Adris, A. M., Elnashaie, S. S. E. H. and Hughes, R.
(1991) A fluidized bed membr ane react or for the
steam reforming of methane. Canad. J. Chem.
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effect and implications of gas vol ume increase
due t o reaction on bed expansion, bubbling and
overall conversion in a fluidized bed reactor.
A.I.Ch.E. Annual Meeting, St. Louis, Novem-
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Adris, A. M., Grace, J . R., Lim, C. J . and Elnashaie,
S. S. E. H. (1994a) Fluidized bed reaction system for
st eam/ hydr ocar bon gas reforming t o produce hy-
drogen. U.S. Pat ent No. 5,326,550.
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fluidized bed membrane react or (FBMR) system:
a pilot scale experimental study. Chem. Engng Sci.
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(1980) Analysis of fluid bed reactors for reaction
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Kai, T. and Furusaki, S. (1987) Met hanat i on of car-
bon dioxide and fiuidization quality in a fluid bed
react or - - the influence of decrease in gas volume.
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gineering, 2nd Ed. But t erwort h-Hei nmann, MA,
U.S.A.
Miwa, K., Mori, S., Kat o, T. and Muchi, I. (1972)
Behaviour of bubbles in gaseous fluidized beds. Int.
Chem. Engng 12, 187-194.
Mori, S. and Wen, C. Y. (1975) Estimation of bubble
diameter in gaseous fluidized beds. A. 1. Ch. E. J. 21,
109-115.
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Reaction time distributions in fluidized catalytic
reactors. Chem. Engng Prog. Syrup. Ser. 85, 1-15.
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ing. In Catalysis Science and Technology, eds. J . R.
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Germany.
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A1-Ubaid, A. S. (1992) Intrinsic kinetics of
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131-138.
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Modelling of a fluidized-bed membrane reactor
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di ffusi on coeffi ci ent s for gases a n d vapor s . I n d .
E n g n # C h e m . 47, 1253- 1257.
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A P P E ND I X A: R E A C T I O N R A T E E Q U A T I O NS A ND
P A R A ME T E R S
The three main reactions taking place in steam reforming
are as follows:
CH4 + H20 = CO + 3H2;
-AH298 = - 206.0 kJ /mol CH4 (A1)
CO + H2 0 = C O 2 + H2;
- AH298 = 41.0 kJ /mol CO (A2)
CH4 + 2H20 = CO2 + 4H2;
--AH298 = -- 164.9 kJ /mol CH 4. (A3)
The net rate of formation of the various components are
R cH, = - (RR1 + Ra3)
Rn2o = -- (RR1 + RR2 + 2RR3)
Rco = RR1 -- RR2
Rco2 = RR2 + RR3
Rn: = 3RR1 + RR2 + 4 RR3 (A4)
where RR1, RR2 and RR3 are the intrinsic rates for reactions
(AI), (A2) and (A3), respectively. The reaction rate expres-
sions developed by Xu and Froment (1989) are used to
estimate the individual reaction rates. The functional forms
of these expressions are
{~ocH.PHzo p O. S p \ /
R R I = k l l p 2. 5 H - ~ l CO) / D 2N (AS)
\ H2
( P c oP H 2o Pco2\ / 2
RR2 = k2 \ Pn2 ~ ' ) / D E N (A6)
I "[Pcu'P22 p O. S p \ /
H2 CO2 2
R R 3 : k 3 ~ . - ~ 2 K1K- - - - - - 2- ) /DEN ( i 7)
where
[ P n ~ o \
DEu = 1 + kcoPco + kn2Pu2 + ken, Pert, + kn2o - z - - - | .
[rH~ /
(A8)
1621
Values of the various constants are given in Table A1.
Equilibrium constants:
K1 = exp ( - 26, 830/ T + 30.114)
K2 = exp (4,400/T -- 4.036)
K3 = K1K2
A P P E ND I X B: HY D R O D Y NA MI C P A R A ME T E R S
The model uses the Mori and Wen (1975) correlation
which accounts for bubble growth due to coalescence to
estimate bubble size as a function of height, i.e.
d b = dbm - - (db,, - - dbo)e - ' 3h / (B1)
where db,, is the maximum bubble diameter at the given gas
flow rate given by
d b , , = 1.64[A(Uo -- U,,I)] '4 (B2)
and dbo is the initial bubble size produced at the distributor
level which can be estimated (Miwa e t al., 1972) as
1.38 FA ( Uo - - U, s ) l ' 4
d b o = ~ L ~ j . (B3)
Here Nor is the number of orifices in the grid, with No~ = 116
in the pilot-scale reactor used in the present study. The above
relations for estimating the bubble size were developed for
freely bubbling beds, i.e. without internals. The presence of
vertical internals in the bed may significantly affect the
bubble size. The sensitivity of the model predictions to
bubble size estimations is explored in this paper.
Because of the net increase in the total number of moles
due to reaction, the superficial gas velocity, Uo, changes with
height. Equations (B1) and (B2) are therefore re-used at each
step in height to recalculate db. The model uses experi-
mentally measured values for the expanded bed height, H, as
discussed in an earlier paper (Adris e t al., 1993). Because the
bubble diameter increases with height, the ratio, ab, of
bubble surface area per volume, given by the relation,
ab = 6/db, decreases with height.
A mean value is used for the volume fraction of bed
occupied by solids dispersed in the bubble phase, ~b. Kunii
and Levenspiel (1969) found t hat 0.001eb < ~b <0.01eb,
where eb is the volume fraction of the bed occupied by
bubbles, which can be estimated by
eb = (Uo - U, . f ) / Ub . (B4)
Table A1. Rate expression parameters and equilibrium constants due
to Xu and Froment (1989) used in this work
Activation energies and
Const ant s Pre-exponential factors heats of absorption*
kl 9.49 1015 240.1
k 2 4.39 106 67.13
k3 2.29 x 1015 243.9
kco 8.23 x 10- 5 70.65
kcm 6.65 x 10- s - 38.28
kn2o 1.77 x 105 88.68
ka2 6.12 10 -9 -- 82.9
* Units are given in the Notation.
1622 A. M. Adris e t al.
Here the bubble rising velocity is calculated by the com-
monly used relation (Davidson and Harrison, 1963):
Ub = Uo - - Umf + 0. 711( g. db ) 1/2. (B5)
The volume fraction occupied by the dense phase solids, Od,
is approximated by including all of the solids in the clouds,
wakes and emulsion in the dense phase and assuming the
dense-phase voidage to be constant and equal to emI" Thus,
O~ can be estimated (Grace, 1986) as
Od = (1 - eb)(1 -- t~I)' (B6)
The interphase mass exchange coefficient for component i,
ki~, is calculated using the semi-empirical equation of Sit and
Grace (1981):
Umy ['4Diee, mIVb ~ 1/2
k,q = ~ + ~ - - ) (B7)
where D~e, the effective molecular diffusivity of component
i in the gas mixture, is estimated based on the average
composition of the bubble phase and dense phase [i.e.
(Cib + Cid)/2] using a relation given by Wilke and Lee (1995).