Dynamic Model of an Industrial SteamReformer and Its Use for

Multiobjective Optimization
Anjana D. Nandasana,

Ajay K. Ray,

and Santosh K. Gupta*

,
Department of Chemical Engineering, I ndian I nstituteof Technology, Kanpur 208016, I ndia, and
Department of Chemical and Environmental Engineering, National University of Singapore, 10,
Kent RidgeCrescent, Singapore119260
An i ndustri al si de-fi red steam reformer i n a hydrogen pl ant i s si mul ated under dynami c
condi ti ons. A ri gorous model wi th veri fi ed reacti on ki neti cs i s used. Thi s model i ncorporates
aspects of heat transfer i n the furnace and di ffusi on i nsi de the catal yst pel l et. The dynami c
model i s used to study the effects of a few (pl anned) di sturbances that reduce the producti on of
both hydrogen and steam and adversel y i nfl uence the safety of the pl ant i f correcti ve control
acti on i s not taken i n ti me. The operati on of the steam reformer i s si mul ated i n the presence of
three i deal i zed di sturbances i n (1) the i nl et feed temperature, (2) the i nl et feed rate of natural
gas, and (3) the furnace gas temperature. The model i s then used to obtai n opti mal operati ng
condi ti ons requi red to negate the effects of two di sturbances usi ng several control or deci si on
vari abl es. Two objecti ve functi ons are mi ni mi zed si mul taneousl y: the cumul ati ve (i ntegrated
over ti me) devi ati on of the fl ow rate of hydrogen and the cumul ati ve devi ati on of the steam fl ow
rate. The el i ti st nondomi nated sorti ng geneti c al gori thm NSGA-I I i s used to obtai n sol uti ons of
thi s mul ti objecti ve opti mi zati on probl em. Nondomi nati ng Pareto-opti mal sol uti ons are obtai ned.
Introduction
Steam reformi ng of hydrocarbons i s an economi cal
method of produci ng synthesi s gas and generati ng
hydrogen. The former i s the feedstock for the synthesi s
of ammoni a, methanol , etc., and the l atter i s an envi -
ronmental l y cl ean fuel .
1
Steam reformi ng pl ants al so
produce consi derabl e amounts of exportabl e steam. The
process fl ow sheet of a typi cal pl ant i s shown i n Fi gure
1. A hydrocarbon stream, assumed to be essenti al l y
methane (wi th CO
2
and N
2
i mpuri ti es) i n thi s study, i s
desul furi zed and preheated. Thi s stream i s mi xed wi th
appropri ate quanti ti es of steam and recycl ed hydrogen
(both from the plant) and fed to the fi rst reactor (cal l ed
the reformer). The fol l owi ng catal yti c reacti ons take
pl ace i n thi s reactor
The gas exi ti ng the reformer, ri ch i n CO and H
2
,
exchanges heat wi th the boi l er feedwater to generate
very hi gh pressure (VHP) steam. The cool ed process gas
i s then fed to a two-stage adi abati c shi ft converter,
where CO i s converted i nto CO
2
and addi ti onal hydro-
gen. Hydrogen i s separated from the exi t gas i n a
pressure-swi ng adsorpti on (PSA) uni t.
The reformi ng reacti ons (eqs 1 and 3) are strongl y
endothermi c i n nature and requi re l arge energy i nputs.
I ncreasi ng energy costs and competi ti on requi re that
reformi ng pl ants be operated opti mal l y, both under
steady-state condi ti ons and i n the presence of un-
pl anned di sturbances. The effects of these di sturbances
need to be negated by advanced model -based process
control strategi es. A good dynami c model i s a prereq-
ui si te for thi s. The devel opment and appl i cati on of such
a model -based control strategy i s the mai n focus of the
present study.
Several studi es
2-6
have been reported i n the open
l i terature on the steady-state model i ng, si mul ati on,
ki neti cs, opti mi zati on, and control of steam reformers.
These have been revi ewed by El nashai e and El shi shi ni
2
and Rajesh et al .
6
El nashai e and El shi shi ni
7
al so
presented an el aborate study on the dynami c model i ng
of gas-sol i d catal yti c reactors i n general but di d not
study i ndustri al reformers i n detai l . Al ati qi and co-
workers
8-12
reported some work on the dynami c model -
i ng and si mul ati on of i ndustri al steam reformers under
l oad di sturbances and val i dated thei r si mul ati on resul ts
wi th actual pl ant data. However, they di d not provi de
compl ete i nformati on on thei r approach for propri etary
reasons. They used di fferent control methods to mi ni -
mi ze the effects of di sturbances. Thei r dynami c model
uses a si mpl i fi ed overal l reacti on rate expressi on rather
than eqs 1-3. I n addi ti on, the reacti on-cum-di ffusi on
of the several mol ecul ar speci es present i nsi de the
porous catal yst i s not consi dered separatel y. Kvamsdal
et al .
13
al so carri ed out the dynami c si mul ati on of
i ndustri al steam reformers i n the presence of sudden
stoppages (tri ppi ng) of the feed gas fl ow and of the
steam suppl y. They used the pseudo-homogeneous
ki neti c model of Xu and Froment.
3
Agai n, these workers
di d not provi de compl ete detai l s on the reactor. There
i s, thus, a defi ni te need for the devel opment of a
dynami c model based on fi rst pri nci pl es, wi th compl ete
* To whom correspondence shoul d be addressed. E-mai l :
skgupta@i i tk.ac.i n. Fax: 91-512-590104.

I ndi an I nsti tute of Technol ogy.

Nati onal Uni versi ty of Si ngapore.

Reformi ng: CH
4
+ H
2
O h CO + 3H
2
H
r
) 8.623 10
5
kJ/kmol (1)
Shi ft: CO + H
2
O h CO
2
+ H
2
H
r
) -1.7196 10
5
kJ/kmol (2)
Reformi ng: CH
4
+ 2H
2
O h CO
2
+ 4H
2
H
r
) 6.904 10
5
kJ/kmol (3)
4028 I nd. Eng. Chem. Res. 2003, 42, 4028-4042
10.1021/i e0209576 CCC: $25.00 2003 Ameri can Chemi cal Soci ety
Publ i shed on Web 07/23/2003
detai l s provi ded. Such fundamental model s can al so be
used for off-l i ne opti mi zati on purposes to obtai n opti mal
control strategi es requi red to negate the effects of a
number of i deal i zed di sturbances. A fi l e of such strate-
gi es (a few of whi ch are obtai ned here) woul d be of
i mmense use for the opti mal operati on of these pl ants.
I t shoul d be menti oned here that the detai l ed model
devel oped here for the steam reformer i s somewhat
si mi l ar to that for packed-bed adsorbers,
14
i n whi ch no
reacti ons take pl ace.
Formulation
The steady-state model
6
of the reformer i s modi fi ed
i n thi s study to appl y to transi ent condi ti ons. The
concentrati ons, C
i
(Z,t), and the temperature, T(Z,t), of
the gas phase (outsi de the sol i d) are functi ons of both
the axi al l ocati on, Z, and the ti me, t. I t i s assumed
2,7
that there are no radi al gradi ents i n the gas phase. The
equati on for C
i
(Z,t) can be wri tten,
15
for a semi di ffer-
enti al control vol ume of l ength Z, as
Here, v
l
i s the superfi ci al vel oci ty of the gas;
b
i s the
voi d fracti on i n the catal yst bed (outsi de the porous
sol i ds); F
b
i s the densi ty of the catal yst bed (i ncl udi ng
the voi d i n the bed and the pores i n the catal yst); R
i
i s
the net rate of consumpti on of the ith speci es because
of the three reacti ons, whi ch i s rel ated to r
i
, the (net)
forward rate of the ith reacti on (eqs 1-3), at the
condi ti ons just outsi de the catal yst parti cl e, through the
stoi chi ometri c coeffi ci ents
i,k
; and
i
i s the effecti veness
factor for the ith reacti on.
6
No accumul ati on term
correspondi ng to the sol i d i s necessary i n thi s equati on,
as the bal ance i s on the gas al one.
The most general form of the energy bal ance equa-
ti on
15
woul d make the probl em computati onal l y i ntense
and woul d requi re separate equati ons for the gas and
sol i d phases. I n such a model , the temperature of the
sol i d phase, T
s
(Z,t,l), woul d depend on Z and t as wel l
as the i nternal l ocati on, l. At the sol i d boundary, thi s
temperature woul d be rel ated to the l ocal gas-phase
temperature, T(Z,t), through a gas-fi l m resi stance
model . Si mpl i fyi ng assumpti ons are needed to obtai n a
model that i s useful for opti mi zati on and control . I t i s
known
2,4,16
that the thermal conducti vi ty of the catal yst
pel l et i s qui te hi gh (l ow Prater number). Al so, the
resi stance of the gas fi l m surroundi ng the catal yst
parti cl es i s smal l .
16
Under these condi ti ons, we can
assume that the enti re catal yst parti cl e attai ns the
temperature, T(Z,t), of the gas phase (at axi al posi ti on
Z and ti me t) i nstantl y. Vi l l adsen and Mi chel sen
17
and
El nashai e and El shi shi ni
2
menti on that thi s i s a rea-
sonabl e approxi mati on to make. We can then wri te the
si mpl i fi ed energy bal ance equati on for the semi di ffer-
enti al control vol ume (gas pl us sol i d) of l ength Z as
I n eq 5, G ( F
g
v
l
) i s the mass vel oci ty of the gas;
c
i s
the vol ume fracti on of the pores i nsi de the catal yst
parti cl es, F
s
and F
g
are the densi ti es of the porous
catal yst (ki l ograms of sol i d per cubi c meter of porous
catal yst parti cl es) and of the pure gas, respecti vel y; U
i s the fi l m heat-transfer coeffi ci ent on the i nsi de of the
tube surface (sum of the effects of heat transfer to the
gas and to the sol i d); C
p,g
and C
p,s
are the heat capaci ti es
of the pure gas mi xture (i n the voi ds) and of the sol i d
catal yst (wi thout pores), respecti vel y; T
w,i
i s the tem-
perature at the i nner tube wal l ; and H
i
i s the heat of
reacti on of the ith reacti on. Equati on 5 can easi l y be
deduced from eqs e and f (page 492) of Froment and
Bi schoff,
15
usi ng these assumpti ons. I t woul d be i nter-
esti ng to compare the resul ts obtai ned from the si mpl i -
fi ed model devel oped here wi th those obtai ned usi ng a
more ri gorous model for T
s
(Z,t,l), when the l atter
becomes avai l abl e (work i s i n progress al ong these
l i nes).
The fol l owi ng i ni ti al condi ti ons (I Cs) can be used wi th
eqs 4 and 5
Figure 1. Process fl ow di agram of the steam reformi ng pl ant usi ng natural gas feed.

Z
(v
l
C
i
) )
b
C
i
t
+ F
b

i
R
i
,
i ) CH
4
, H
2
O, CO
2
, CO, H
2
(4)
C
i
(Z,t)0) ) C
i
SS
(Z), 0 e Z e L (6a)
T(Z,t)0) ) T
i
SS
(Z), 0 e Z e L (6b)

Z
(GC
p,g
A
c
T) ) d
i
U(T
w,i
- T) -
({C
p,s
F
b
+ [
b
+ (1 -
b
)
c
]F
g
C
p,g
}A
c
)
T
t
+
A
c
i)I
I I I
(-H
i
)
i
r
i
F
b
(5)
I nd. Eng. Chem. Res., Vol . 42, No. 17, 2003 4029
Here, C
i
SS
and T
SS
are the profi l es that can be obtai ned
usi ng the steady-state (SS) code of Rajesh et al .
6
I t i s
assumed that the reformer i s operati ng at steady state
for t e 0 and that a di sturbance i s i ntroduced at t ) 0.
Because most of the gradi ent i n the catal yst parti cl e
exi sts i n thi n l ayers near the two faces of the Raschi g
ri ng catal yst parti cl e, the l atter can be assumed to have
a sl ab geometry,
6
i .e., i t can be sl i ced al ong the l ength
and opened up to gi ve an equi val ent sl ab geometry
havi ng a cross-secti onal area A
p
[ (r
1
+ r
2
)l
p
] and
thi ckness 2l
c
() r
2
- r
1
) (see Fi gure 2). The si mpl i fi ed
model I I of El nashai e and El shi shi ni
2
gi ves the fol l owi ng
equati ons at ti me t for the i ntrapel l et concentrati ons,
c
i
wi th the fol l owi ng boundary condi ti ons (BCs) at l ) 0
and l ) l
c
I n the above equati ons, N
i
i s the mol ar fl ux of compo-
nent i at any l ocati on l (0 e l e l
c
) i nsi de the catal yst
sl ab, and D
i
e
i s the effecti ve di ffusi vi ty of component i
i n the catal yst.
2
r
k
i s the net forward rate of the kth
reacti on (k ) I -I I I for eqs 1-3, respecti vel y) at any l
and t, and
i,k
i s the stoi chi ometri c coeffi ci ent of the ith
component parti ci pati ng i n the kth reacti on. The con-
centrati ons of CO, CO
2
, and H
2
(and N
2
) i nsi de the
catal yst at any l ocati on l and ti me t are eval uated usi ng
stoi chi ometry.
6
The compl ete set of model equati ons i s
gi ven i n the appendi x. The l i st of model parameters
used, as wel l as the detai l s of the i ndustri al reformer
and the i ni ti al operati ng condi ti ons, are gi ven i n Tabl e
1.
2,4,6,18,19
The correl ati ons for the esti mati on of the
effecti ve di ffusi vi ty are taken from El nashai e and
El shi shi ni ,
2,6
and the correl ati ons for the speci fi c heat,
vi scosi ty, and thermal conducti vi ty are taken from
6
the
HYSYS Process (versi on 1.5) code.
Figure 2. (a) Sketch of the catal yst pel l et (Raschi g ri ng). (b)
Notati on used for the reacti on-di ffusi on probl em.
d
dl
(N
i
A
p
) ) A
p
F
s
k)I
I I I

i,k
r
k
, i ) CH
4
, H
2
O (7a)
N
H
2
) -N
H
2
O
- 2N
CH
4
(7b)
N
CO
) N
H
2
O
- 2N
CH
4
(7c)
N
CO
2
) -N
H
2
O
+ N
CH
4
(7d)
N
i
) -D
i
e
dc
i
dl
, i ) CH
4
, H
2
O, CO, CO
2
, H
2
(7e)
c
i
(l)0,Z,t) ) C
i
(Z,t), i ) CH
4
, H
2
O, CO, CO
2
, H
2
N
i
(l)l
c
,Z,t) ) 0, i ) CH
4
, H
2
O, CO, CO
2
, H
2
(8)
Table 1. Model Parameters for the Industrial Steam
Reformer
2,4,6,17,18
model parameter val ue/speci fi cati on ref
reformer data
heated l ength of reformer
tube, L
11.95 m 2
i nsi de di ameter of reformer
tubes, d
i
0.0795 m 2
outsi de di ameter of
reformer tubes, do
0.102 m 2
rati o of reformer tube pi tch
to di ameter
2.4 2
number of tubes 176 2
refractor surface area, A
ref 1164 m
2
2
number of burners, Nb 112 2
fl ame surface area, Af 0.01 m
2
6
catal yst data
catal yst shape Raschi g ri ng 2
catal yst pel l et di mensi on 16 6 16 mm 2
pel l et porosi ty,
c 0.51963 2
pel l et spheri ci ty, s 0.6563 2
pel l et equi val ent
di ameter, Dp
17.4131 mm 2
pel l et tortuosi ty, 2.74 2
sol i d catal yst densi ty, Fs 2396.965 kg/m
3
cal cd from refs 2, 4
mean pore radi us 80.0 2
pel l et characteri sti c
l ength, l c
1.948 mm 2
catal yst bed densi ty, Fb 946.8 kg/m
3
2
catal yst bed voi d
fracti on, b
0.605 17
other data
carbon di oxi de-to-methane
rati o, D/C
0.091 2
ni trogen-to-methane
rati o, N/C
0.021 2
emi ssi vi ty of fl ames,
f 0.1 2
emi ssi vi ty of furnace
gases, g
0.1 2
emi ssi vi ty of reformer
tubes, t
0.95 18
adi abati c fl ame
temperature, Tf
2200 K 6
tube thermal
conducti vi ty, kw
10.738 +
0.0242Tw
W/(m K)
18
no. of col l ocati on
poi nts, M + 2
10 thi s work
acti ve fracti on, a 0.2 2
k
I , KI , kI I , KI I , kI I I ,
KI I I , Hi
- 2, 6
other properti es - 6
operati ng condi ti ons at SS1
F
CH4,i n 593.564 kmol /h 6
Tg 1625 K 6
S/C 4.8 6
H/C 0.34 6
Pi n 2548.8 kPa 6
Ti n 841.7 K 6
4030 I nd. Eng. Chem. Res., Vol . 42, No. 17, 2003
The profi l es, c
i
(l,Z,t), and the effecti veness factors,
i
,
are eval uated
6
usi ng the method of orthogonal col l oca-
ti on on fi ni te el ements (OCFE).
16,20,21
The regi on 0 e l
e l
c
i s di vi ded i nto two fi ni te el ements
6
extendi ng over
0 e ve 0.2 (outer regi on) and 0.2 e ve 1 (i nner regi on),
where v l/l
c
. I t i s assumed that al l fl uxes are zero at
Figure3. Axi al profi l es of di fferent vari abl es at the i ni ti al and fi nal steady states and the devi ati ons of these vari abl es from thei r i ni ti al
steady-state val ues at di fferent ti mes for the fi rst si mul ati on probl em (step i ncrease i n the i nl et feed temperature).
I nd. Eng. Chem. Res., Vol . 42, No. 17, 2003 4031
v ) 0.2. Thi s i mpl i es that, i n the i nner regi on of the
catal yst sl ab, the reacti ons are at (i nstantaneous l ocal )
equi l i bri um. There are a total of 10 orthogonal col l oca-
ti on (OC) poi nts (i ncl udi ng two at the boundari es of the
el ement) i n the outer fi ni te el ement, where most of the
concentrati on changes take pl ace.
Figure4. Axi al profi l es of di fferent vari abl es at the i ni ti al and fi nal steady states and the devi ati ons of these vari abl es from thei r i ni ti al
steady-state val ues at di fferent ti mes for the second si mul ati on probl em (step decrease i n the i nl et fl ow rate of natural gas). Approach
numbers (1, 2, and 3) are i ndi cated.
4032 I nd. Eng. Chem. Res., Vol . 42, No. 17, 2003
The PDEs characteri zi ng the gas phase are converted
i nto ODEs usi ng the fi ni te di fference method (the
method of l i nes) wi th unequal spaci ng of the gri d poi nts
[the fi ni te di fference equati ons
21
used are accurate to
O(Z
2
)]. The regi on 0 e Z e 0.5 m, whi ch encompasses
sharp changes i n the vari abl es, i s di vi ded i nto si x
equal l y spaced gri d poi nts (two at Z ) 0 and 0.5 m).
The remai ni ng 11.45 m of the reactor
2,6
i s di vi ded i nto
10 equal l y spaced gri d poi nts. The fi rst poi nt i n 0.5 e Z
e 11.95 m i s the same as the l ast poi nt i n 0 e Z e 0.5
m. The resul ti ng set of ODEs (i n t) i s sol ved wi th the
code D02EJF from the NAG l i brary for the i ntegrati on
of sti ff ordi nary di fferenti al equati ons usi ng Gears
techni que.
20,21
We use the C05NCF subrouti ne of the
NAG l i brary to sol ve the nonl i near al gebrai c col l ocati on
equati ons for c
i
(v,Z,t) for any desi red val ues of C
i
(Z,t)
and T(Z,t) i n the gas phase. These sol uti ons are used
to eval uate the effecti veness factors (eqs A21 and A22,
Appendi x) usi ng appropri ate Gauss-Legendre quadra-
tures.
20,21
The pressure at axi al l ocati on Z and ti me t i s
computed from a fl ui d-mechani cs-based equati on (eq
A4b) by the Eul er techni que.
20,21
Results and Discussion
A Fortran 90 program was wri tten to sol ve the
equati ons for di fferent i deal i zed di sturbances. The CPU
ti me requi red for sol vi ng a typi cal dynami c si mul ati on
i s 2 h on a Penti um 4 computer (1.7 GHz). The code
was tested by starti ng from one steady state, SS1
(generated usi ng an SS code,
6
as gi ven i n Tabl e 1),
provi di ng a step change (at t )0) i n one of the operati ng
vari abl es, and sol vi ng unti l the fi nal SS i s attai ned. The
resul ts obtai ned at l arge val ues of t from the dynami c
code, matched the fi nal SS profi l es generated di rectl y.
6
The model i s then used to sol ve two sampl e mul ti ob-
jecti ve opti mi zati on probl ems under dynami c opti mal
control .
Dynamic Simulation. The fi rst probl em studi ed
i nvol ves a step i ncrease of 100 K i n the feed tempera-
ture. Nonl i near effects of the model are exhi bi ted under
such l arge di sturbances. The axi al profi l es of several
i mportant vari abl es are shown i n Fi gure 3a-h, both at
the i ni ti al and the fi nal steady states, as wel l as thei r
vari ati ons wi th ti me (i n terms of devi ati ons from the
i ni ti al SS). The fi nal SS val ues of the temperature
(Fi gure 3a), are observed to be hi gher than the i ni ti al
SS val ues. There i s an undesi rabl e i ncrease (Fi gure 3c,d)
i n the outer wal l temperature, T
w,o
(even smal l i ncreases
i n T
w,o
beyond 1200 K l ead to a si gni fi cant reducti on i n
the l i fe of the reformer tubes). Hi gher process-gas
temperatures, however, l ead to hi gher conversi ons of
methane (Fi gure 3e,f) and hi gher producti ons of CO
(Fi gure 3g,h) and steam.
2
The mol e fracti on of CO
2
i ncreases from i ts i ni ti al SS val ue i n the earl y part of
the reformer, but fal l s beyond some axi al l ocati on. Thi s
i s because of the i nhi bi ti ng effect of the exothermi c
reacti on (eq 2) at hi gher process-gas temperatures. Pl ots
of both the conversi on of methane and the mol e fracti on
of CO
2
are not shown here, but can be suppl i ed on
request.
The second dynami c si mul ati on studi ed here i nvol ves
a step decrease of 30 kmol /h i n the i nl et fl ow rate of
methane i n the natural gas feed (the correspondi ng fl ow
rates of the accompanyi ng CO
2
and N
2
are al so de-
Figure5. Axi al profi l es of di fferent vari abl es at the i ni ti al and fi nal steady states and the devi ati ons of these vari abl es from thei r i ni ti al
steady-state val ues at di fferent ti mes for the thi rd si mul ati on probl em (step decrease i n the furnace gas temperature).
I nd. Eng. Chem. Res., Vol . 42, No. 17, 2003 4033
4034 I nd. Eng. Chem. Res., Vol . 42, No. 17, 2003
creased), whi l e the fl ow rates of recycl e steam and
hydrogen are mai ntai ned at thei r ori gi nal val ues. The
superfi ci al vel oci ty of the process gas at the feed end
decreases (from 3.24 to 3.21 m/s) i mmedi atel y upon the
i ntroducti on of thi s step di sturbance, and a wave front
(wi th a l ower superfi ci al gas vel oci ty upstream and a
hi gher val ue downstream) travel s through the reformer.
Because of vi scous effects, thi s front does not actual l y
remai n sharp, so one shoul d real l y sol ve the equati ons
of moti on (eq A4b shoul d be repl aced by the hi ghl y
nonl i near PDEs of fl ui d mechani cs) si mul taneousl y wi th
the reacti on equati ons. Thi s woul d make the dynami c
model al most i ntractabl e. Three si mpl er, though em-
pi ri cal , approaches were expl ored to model thi s phen-
omenon, whi l e sti l l usi ng eq A4b and keepi ng the CPU
ti me reasonabl e. I n the fi rst approach (approach 1), we
use the l ower mass vel oci ty G
new,i n
, at al l l ocati ons and
ti mes. I n approach 2, the ori gi nal (hi gher) mass vel oci ty
i s used throughout, even after the di sturbance. I n
approach 3, whi ch i s sl i ghtl y more real i sti c, we assume
that the wave front i s sharp and i s travel i ng through
the reformer tube at a constant vel oci ty of u
new
()
G
new,i n
/F
i n
) 3.21 m/s). The val ue of t* () Z/u
new
) i s
computed at each fi ni te-di fference gri d poi nt. Thi s i s the
ti me at whi ch the wave front passes the parti cul ar gri d
poi nt. The new mass vel oci ty i s used at any gri d poi nt
i f t g t*; otherwi se, the ori gi nal mass vel oci ty i s used.
Fi gure 4a-c shows the resul ts. These resul ts do not
di ffer much even at t ) 3.6 s, and i n fact, al l three
approaches gi ve i denti cal resul ts (not shown) for hi gher
val ues of t. Hence, one can use any one of these three
approaches. Fi gure 4a shows some osci l l ati ons i n the
fl ow rates of H
2
at l ow val ues of t. Such behavi or i s
characteri sti c of the numeri cal sol uti on of probl ems wi th
sharp movi ng fronts and can be mi ni mi zed by usi ng
movi ng fi ni te-el ement techni ques, as for the far si mpl er
col or equati on.
20,21
Fi gure 4d-g shows the profi l es of
several vari abl es at di fferent ti mes.
Because of the decrease i n the i nl et feed rate of
natural gas, the concentrati on of methane i n the process
gas decreases. Thi s reduces the extent of the endother-
mi c reacti ons (referred to as the concentrati on effect)
and reduces the fl ow rates of both H
2
and CO (and
steam; see Fi gure 4f,g). However, the hi gher tempera-
tures of the process gas tend to i ncrease the conversi on
to hydrogen and carbon monoxi de by the endothermi c
reacti ons. Thi s can be referred to as the temperature
effect. Fi gure 4f and g i ndi cates that the l atter effect
domi nates. The compl ex i nterpl ay of several opposi ng
physi cal phenomena i s exhi bi ted here qui te wel l . Agai n,
there i s an i ncrease i n the outer wal l temperature.
I n the thi rd dynami c si mul ati on probl em studi ed, a
step decrease of 200 K i s i ntroduced i n the furnace gas
temperature. Such a di sturbance can ari se i n i ndustry
through burner fai l ure or a change i n the feed rate of
the fuel . No changes i n the mass vel oci ty are i nvol ved.
Because l ess heat i s transferred from the furnace after
the di sturbance, the process-gas temperature, as wel l
as T
w,o
, decreases wi th ti me to new SS val ues (Fi gure
5a,b). Thi s l eads to a si mul taneous reducti on i n the
producti on of H
2
and CO (and thus al so steam; see
Fi gure 5c,d). Obvi ousl y, the negati ve effect of such a
fai l ure on the producti on of desi red chemi cal s needs to
be compensated by appropri ate control acti on, e.g., an
i ncrease i n the feed temperature.
Optimization. We now study two sampl e opti mi za-
ti on probl ems (referred to as probl ems 1 and 2) to
i l l ustrate the use of our dynami c model . A step pul se (0
e t e t
T
, t
T
) 0.0245 h) of -20 kmol /h i n the i nl et fl ow
rate of methane i s taken as the di sturbance
There i s a correspondi ng reducti on i n the fl ows of CO
2
and N
2
(i n the natural gas) as wel l . I f the i nput fl ow
rates of (recycl e) hydrogen and steam remai ned un-
changed, there woul d be a decrease i n the i nl et concen-
trati on of methane. Such a decrease woul d l ead to a
decrease i n the outl et conversi ons associ ated wi th the
reformi ng reacti ons and to a decrease i n the heat
consumed by these endothermi c reacti ons. I f, i n addi -
ti on, the suppl y of heat from the furnace i s unchanged,
thi s woul d l ead to an i ncrease i n the temperature, T
w,o
,
of the outer wal l of the reformer tube. I ndeed, Kvamsdal
et al .
13
have shown that a decrease i n the fl ow rate of
methane coul d l ead to thermal runaways i n the re-
former. Thi s can reduce the l i fe of the reformer tubes
or cause thei r rupture. To counter the i l l effects of thi s
di sturbance, we use the fol l owi ng general control acti on
(pul se over 0 e t e t
T
)
Figure 6. Pareto set, deci si on vari abl es, and dynami c vari ati ons of some vari abl es at the outl et for the mul ti objecti ve opti mi zati on
probl em 1 (sol i d l i ne, wi th opti mal control acti on; broken l i ne, wi thout opti mal control acti on). Chromosome numbers 1, 2, and 3 i ndi cated
i n pl ots i and j.
F
CH
4
,i n
) F
CH
4
,i n,SS
() 593.564 kmol /h, SS1),
t e 0 or t g t
T
F
CH
4
,i n
) F
CH
4
,i n,SS
- 20 kmol /h, 0 e t e t
T
(9)
I nd. Eng. Chem. Res., Vol . 42, No. 17, 2003 4035
The deci si on vari abl es are, thus, T
g
, (S/C), and
(H/C).
Two objecti ve functi ons ar e mi ni mi zed si mul ta-
neousl y. They are the total (cumul ati ve over t) devi a-
ti ons
22
of the producti on of (a) hydrogen and (b) steam,
from thei r SS1 val ues, i ntegrated over an appropri atel y
l ong ti me span, 0 e t e t
f
(t
f
) 0.05 h), so that thei r
rates of producti on reattai n thei r i ni ti al steady-state
val ues. The fl ow rate of steam i s rel ated to that of CO,
and we can mi ni mi ze the cumul ati ve devi ati on of the
producti on of CO.
6
The fi nal opti mi zati on probl em
(referred to as probl em 1) i s wri tten mathemati cal l y
(al ong wi th the constrai nts and bounds) as
subject to (s.t.) the constrai nt
and the bounds
I n eqs 11, F
H2,out
(t) and F
CO,out
(t) are the mass fl ow rates
of H
2
and CO, respecti vel y, i n the syngas exi ti ng the
reformer. I t can be noted that we do not use the squares
of the i ntegrands i n eqs 11a and b, because any short-
term i ncreases i n the fl ow rates above the steady-state
val ues need not be penal i zed because they are benefi ci al .
The constrai nt on T
w,o
i s that used by Rajesh et al .
6
I n
these equati ons, the bounds on (S/C) and (H/C) are
taken to be about 5% of the SS val ues and are of the
same order as the devi ati on i n the methane fl ow rate.
The fol l owi ng penal ty
23
i s added to both objecti ve
functi ons
to take care of the constrai nt on T
w,o
. (Al ternati ves
exi st.
23
) The mul ti pl i er (10
4
) was suffi ci entl y l arge, and
the resul ts were found to be i nsensi ti ve to an i ncrease
i n i ts val ue.
The second mul ti objecti ve opti mi zati on probl em (prob-
l em 2) i nvol ves a pul se decrease i n the feed temperature
wi th t
T
taken as 0.023 h (sl i ghtl y di fferent than for
probl em 1). Because of the decrease i n the i nl et feed
temperature, the outl et temperature of the syngas and
the conversi on of methane decrease. Thi s resul ts i n a
decrease i n the producti on of both hydrogen and steam.
The effects of thi s di sturbance are negated once agai n
usi ng step changes i n the furnace gas temperature, T
g
;
the steam-to-methane rati o, S/C; and the hydrogen-to-
methane rati o, H/C, as fol l ows
t
1
and t
2
are addi ti onal deci si on vari abl es used to make
the probl em general . An i ncrease i n the temperature of
the furnace gas i ncreases the heat content of the
reformer gases and hel ps compensate for the effect of
the decrease i n the i nl et feed temperature. Hi gher
steam-to-methane rati os hel p to i ncrease the hydrogen
producti on, whi l e hi gher hydrogen-to-methane rati os
i ncrease the carbon monoxi de (and, therefore, al so the
steam) producti on. Probl em 2 can, thus, be wri tten as
s.t.
wi th t
f
) 0.058 h. The l ower bound on T
g
i s rel ati vel y
uni mportant because, i ntui ti vel y, i t i s expected that T
g
wi l l be posi ti ve. The upper bound on T
g
was deter-
mi ned on the basi s of the normal operati ng condi ti ons
possi bl e i n i ndustri al reformers. The ranges of (S/C)
T
i n
) T
i n,SS
() 841.7 K
6
), t e 0, t g t
T
T
i n
) T
i n,SS
- 50 K, 0 e t e t
T
(13)
T
g
) T
g,SS
() 1625 K
6
), t e t
1
or t g t
2
(14a)
T
g
) T
g,SS
+ T
g
, t
1
e t e t
2
(14b)
S/C ) (S/C)
SS
() 4.8
6
), t e t
1
or t g t
2
(14c)
S/C ) (S/C)
SS
+ (S/C), t
1
e t e t
2
(14d)
H/C ) (H/C)
SS
() 0.34
6
), t e t
1
or t g t
2
(14e)
H/C ) (H/C)
SS
+ (H/C), t
1
e t e t
2
(14f)
Probl em 2
mi n f
1
[T
g
,(S/C),(H/C),t
1
,t
2
]

0
t
f
[F
H
2
,SS,out
-
F
H
2
,out
(t)] dt (15a)
mi n f
2
[T
g
,(S/C),(H/C),t
1
,t
2
]

0
t
f
[F
CO,SS,out
-
F
CO,out
(t)] dt (15b)
T
w,o
e 1200 K (15c)
-15 e T
g
e 25 K (15d)
-0.4 e (S/C) e 0.3 (15e)
-0.03 e (H/C) e 0.03 (15f)
0 e t
1
e 0.023 h (15g)
0.023 e t
2
e 0.058 h (15h)
T
g
) T
g,SS
() 1625 K
6
), t e 0, t g t
T
(10a)
T
g
) T
g,SS
- T
g
, 0 e t e t
T
(10b)
S/C ) (S/C)
SS
() 4.8
6
), t e 0, t g t
T
(10c)
S/C ) (S/C)
SS
+ (S/C), 0 e t e t
T
(10d)
H/C ) (H/C)
SS
() 0.34
6
), t e 0, t g t
T
(10e)
H/C ) (H/C)
SS
+ (H/C), 0 e t e t
T
(10f)
Probl em 1
mi n f
1
[T
g
,(S/C),(H/C)]

0
t
f
[F
H
2
,SS,out
-
F
H
2
,out
(t)] dt (11a)
mi n f
2
[T
g
,(S/C),(H/C)]

0
t
f
[F
CO,SS,out
-
F
CO,out
(t)] dt (11b)
T
w,o
e 1200 K (11c)
-25 e T
g
e 5 (11d)
-0.4 e (S/C) e 0.3 (11e)
-0.02 e (H/C) e 0.02 (11f)
P 10
4
[(T
w,o
- 1200) + abs(T
w,o
- 1200)] (12)
4036 I nd. Eng. Chem. Res., Vol . 42, No. 17, 2003
and (H/C) were determi ned on the basi s of the mag-
ni tude of the di sturbance. The l ower bound on t
1
i s the
ti me at whi ch the di sturbance i s i ntroduced (t ) 0),
whi l e the upper bound (and the l ower bound on t
2
) i s
set at a conservati vel y hi gh val ue of t
T
, the ti me at whi ch
the i nput di sturbance ceases (hi gher val ues of t
1
are
nonopti mal ). The upper bound on t
2
i s the ti me corre-
spondi ng to the fi nal steady state, t
f
. The val ue of t
f
i s
sel ected on the basi s of experi ence wi th si mul ati on runs.
The recentl y devel oped robust and effi ci ent techni que
cal l ed the el i ti st nondomi nated sorti ng geneti c al go-
ri thm (NSGA-I I )
23,24
i s used to sol ve these probl ems. The
parameters associ ated
23-25
wi th NSGA-I I for probl ems
1 and 2 are gi ven i n Tabl e 2. The CPU ti mes requi red
to sol ve probl ems 1 (9 generati ons) and 2 (18 genera-
ti ons) on a Si l i con Graphi cs server (SGI ori gi n 270, 400
MHz) are 110 and 144 h, respecti vel y. The hi ghl y
computati onal l y i ntensi ve nature of these probl ems puts
constrai nts on the number of runs (or the si ze of
popul ati ons or the number of generati ons), and we have
to be content wi th the reasonabl e Pareto sol uti ons
obtai ned. Because the mai n focus i n thi s paper was not
opti mi zati on, we di d not expl ore other techni ques (e.g.,
usi ng paral l el computi ng pl atforms or devel opi ng em-
pi ri cal and faster model equati ons) to i mprove the
sol uti ons. Several checks were made on our code, as
di scussed by Kasat et al .,
26
to ensure that the sol uti ons
obtai ned were correct. I n addi ti on, we used the -con-
strai nt techni que
27
(i n whi ch one objecti ve functi on i s
taken as a constant, , to form an addi ti onal constrai nt
and the resul ti ng si ngl e-objecti ve-functi on opti mi zati on
probl em i s sol ved usi ng a di fferent code) and found that
the sol uti ons matched those obtai ned usi ng NSGA-I I ,
confi rmi ng that we di d, i ndeed, attai n opti mal sol uti ons.
The resul ts for probl em 1 are shown i n Fi gure 6. I f
we go from any one poi nt (say, 1) to another (say, 2) i n
Fi gure 6a, we fi nd that f
1
i mproves (decreases) whereas
f
2
worsens (i ncreases). Thi s pl ot, therefore, represents
a Pareto set.
23-25
Cl earl y, the control acti on taken to
negate the effect of thi s di sturbance i s unabl e to i ncrease
the rates of producti on of both hydrogen and steam. A
deci si on maker woul d have to deci de on the preferred
sol uti on (operati ng poi nt) from among these several ,
equal l y good, Pareto poi nts. Fi gure 6b-d shows the
correspondi ng deci si on vari abl es (actual val ues). Hi gh
val ues of T
g
and the S/C rati o are associ ated wi th l ower
f
1
val ues (l arger hydrogen producti on) and hi gher f
2
val ues (l ower CO or steam producti on) under opti mal
condi ti ons. The opti mal val ues of H/C do not appear to
exhi bi t any defi ni te trend, and we bel i eve that there i s
some scatter i n these data. Such scatter i n one or more
deci si on vari abl es seems to be the norm rather than an
excepti on for most real -l i fe probl ems
25
and to refl ect the
rel ati ve i nsensi ti vi ty of the objecti ve functi ons to vari a-
ti ons i n these deci si on vari abl es. As menti oned before,
the resul ts coul d be i mproved but at the cost of excessi ve
computati onal effort. A study of several members of the
i ni ti al (nonopti mal ) sol uti ons reveal s that chromosomes
havi ng hi gh val ues of T
g
and rel ati vel y l ow val ues of
S/C vi ol ate the constrai nt on the outer wal l tempera-
ture, T
w,o
, and are ki l l ed over the generati ons. Tabl e
3 reports the val ues of the deci si on vari abl es for three
di fferent chromosomes, 1-3 (i n Fi gure 6a), i n the Pareto
set.
The vari ati on of several i mportant vari abl es over
ti me, both i n the absence (broken curves) and i n the
presence (conti nuous curves) of opti mal control acti on
for chromosome 1, are shown i n Fi gure 6e-h. I t i s
observed that the outer tube-wal l temperature at the
exi t (the hi ghest val ue i n the reformer) under opti mal
condi ti ons hovers around i ts bound of 1200 K (see Fi gure
6g). I f control acti on were not used, the tube-wal l
temperature woul d vi ol ate thi s constrai nt. Thi s si mul -
taneousl y l eads to the gas temperature at the exi t of
the reformer l yi ng near i ts steady-state val ue of 1076
K. The l ower process-gas temperatures i n the presence
of opti mal control l ead to l ower conversi ons of methane
and l ower producti ons of both hydrogen and carbon
monoxi de/steam. Fi gure 6i and j shows the vari ati ons
of the exi t fl ow rates of both hydrogen and carbon
monoxi de for chromosomes 1-3. Chromosomes havi ng
hi gh val ues of S/C (e.g., chromosome 3) are associ ated
wi th a l ower cumul ati ve devi ati on i n the fl ow rate of
hydrogen but a hi gher devi ati on i n the fl ow rate of
carbon monoxi de.
Fi gure 7a shows the Pareto set at the 18th generati on
for probl em 2. I t can be noted that negati ve val ues (hi gh
total producti on of hydrogen under dynami c control ) of
f
1
are obtai ned here. Thi s, of course, occurs wi th a
worseni ng of f
2
. Fi gure 7b-f shows the correspondi ng
deci si on vari abl es. I t i s observed that the furnace gas
temperature, T
g
, remai ns at sl i ghtl y hi gher val ues (than
the SS val ue) for al l of the Pareto poi nts. I n contrast,
S/C and t
2
decrease as the opti mal val ue of f
1
i ncreases.
The opti mal val ues of t
1
remai n near thei r l ower bounds.
Fi gure 7g-j shows the vari ati ons of some i mportant
vari abl es over ti me for chromosome 2 of the Pareto set.
The hi gh val ue of S/C used for thi s chromosome i n-
creases the producti on of hydrogen (to even better
val ues than i n the absence of the di sturbance; see
Fi gure 7i ) and reduces the producti on of carbon mon-
oxi de and steam. Fi gure 7k and l shows the vari ati ons
of the exi t fl ow rates of both hydrogen and carbon
monoxi de wi th ti me for chromosomes 1-3 i n Fi gure 7a.
I t can be observed from these di agrams that chromo-
somes havi ng hi gher S/C val ues have l ower devi ati ons
i n the exi t fl ow rate of hydrogen and hi gher devi ati ons
i n the exi t fl ow rate of carbon monoxi de. Hi gh val ues of
T
g
i mprove both objecti ve functi ons. Tabl e 4 provi des
val ues of the deci si on vari abl es for the three di fferent
chromosomes, 1-3, shown i n Fi gure 7a.
Conclusions
A dynami c model for the fi rst reactor, the reformer,
i n a steam reformer pl ant i s presented. The effects of a
Table 2. GA Parameters Used for Optimization
parameter probl em 1 probl em 2
total chromosome l ength (Nchr) 22 20
popul ati on si ze (Np) 70 50
number of generati ons (Nga) 9 18
crossover probabi l i ty (pc) 0.95 0.95
mutati on probabi l i ty (pm) 0.01 0.05
random seed number 0.888 76 0.888 76
Table 3. Decision Variables (in Nondeviation Form) and
Objective Functions for Three Chromosomes in
Figure 6a
chromosome
deci si on
vari abl e 1 2 3
Tg 1609.8 1619.2 1620.4
S/C 4.63 5.01 5.09
H/C 0.326 0.358 0.359
f1 3.12 1.50 0.645
f2 7.84 6.69 8.92
I nd. Eng. Chem. Res., Vol . 42, No. 17, 2003 4037
4038 I nd. Eng. Chem. Res., Vol . 42, No. 17, 2003
few i deal i zed di sturbances are studi ed. The model i s
then used to study two sampl e mul ti objecti ve opti mi za-
ti on probl ems for thi s reactor, and Pareto-opti mal
sol uti ons are obtai ned. An extensi ve fi l e of si mi l ar
opti mal control acti ons under a vari ety of di sturbances
can be generated for l ater use.
Acknowledgment
Parti al fi nanci al support from the Department of
Sci ence and Technol ogy, Government of I ndi a, New
Del hi , I ndi a [through grant I I I -5(13)/2001-ET] i s grate-
ful l y acknowl edged.
Nomenclature
a ) fracti onal l ength of the hal f-catal yst sl ab i n whi ch the
concentrati on vari es
A
c
) i nsi de cross-secti onal area of the reformer tube, m
2
A
f
) surface area of the fl ame produced by a si ngl e burner,
m
2
A
p
) cross-secti onal area of the catal yst sl ab, m
2
A
ref
) surface area of the refractor, m
2
A
t,i
) total i nternal surface area of reformer tubes, m
2
c
i
) concentrati on of speci es i i n the catal yst sl ab, kmol
m
-3
C
i
) concentrati on of speci es i i n the gas phase, kmol m
-3
C
p,g
) speci fi c heat of the process gas, kJ kmol
-1
K
-1
C
p,s
) speci fi c heat of the sol i d (catal yst), kJ kmol
-1
K
-1
C
p,t
) speci fi c heat of the bed, kJ kmol
-1
K
-1
C
t
)mol ar concentrati on of the gas mi xture ()P/RT), kmol
m
-3
d
i
, d
o
) i nner and outer di ameters, respecti vel y, of the
reformer tube, m
D
i
e
) effecti ve di ffusi vi ty of speci es i i n the catal yst at
axi al l ocati on Z and ti me t, m
2
h
-1
D
p
) equi val ent di ameter of the catal yst pel l et (Raschi g
ri ng), m
D/C ) rati o of carbon di oxi de to methane i n feed, (kmol /h
of CO
2
)/[kmol /h of methane fed (F
CH4,i n
)]
E ) quanti ty defi ned i n eq A11
f
i
) objecti ve functi on, i ) 1, 2
F ) total feed rate, kmol h
-1
F
CH4
) fl ow rate of methane, kg h
-1
F
CO
) fl ow rate of CO, kg h
-1
F
H2
) fl ow rate of H
2
, kg h
-1
G ) mass vel oci ty of the process gas i n the reformer, kg
m
-2
h
-1
H/C ) rati o of hydrogen to methane i n feed, (kmol /h of
hydrogen recycl ed)/[kmol /h of methane fed (F
CH4,i n
)]
Figure 7. Pareto set, deci si on vari abl es, and dynami c vari ati ons of some vari abl es at the outl et, for the mul ti objecti ve opti mi zati on
probl em 2 (sol i d l i ne, wi th opti mal control acti on; broken l i ne, wi thout opti mal control acti on). Chromosome numbers 1, 2, and 3 i ndi cated
i n pl ots k and l .
Table 4. Decision Variables (in Nondeviation Form) and
Objective Functions for Three Chromosomes in
Figure 7a
chromosome
deci si on
vari abl e 1 2 3
Tg 1633.8 1633.8 1627.1
S/C 4.87 5.03 5.02
H/C 0.367 0.366 0.368
t1 0.0084 0.00726 0.0028
t2 0.0331 0.0383 0.056
f1 -0.0443 -0.679 -0.986
f2 2.79 4.44 8.59
I nd. Eng. Chem. Res., Vol . 42, No. 17, 2003 4039
H
i
) enthal py of the ith reacti on, kJ kmol
-1
k
g
) thermal conducti vi ty of the process gas, kJ h
-1
m
-1
K
-1
k
w
) thermal conducti vi ty of the tube-wal l materi al , kJ h
-1
m
-1
K
-1
k
i
)rate constant of the ith (i )I -I I I ) reacti on, kmol kPa
0.5
kg
cat
-1
h
-1
or kmol kPa
-1
kg
cat
-1
h
-1
K
I
, K
I I
, K
I I I
) equi l i bri um constants of reacti ons I -I I I ,
respecti vel y
K
i
) equi l i bri um adsorpti on constant for speci es i (i ) CH
4
,
H
2
, CO, H
2
O), kPa
-1
l ) axi al l ocati on i n the catal yst sl ab, m
l
c
) thi ckness of the wal l of the Raschi g ri ng, m
l
p
) l ength of the Raschi g ri ng, m
L ) total l ength of the reactor, m
M ) number of i nternal col l ocati on poi nts
N/C ) rati o of carbon di oxi de to methane i n feed, (kmol /h
of ni trogen)/[kmol /h of methane fed (F
CH4,i n
)]
N
b
) number of burners i n the reformer furnace
N
chr
) total chromosome l ength for NSGA-I I
N
ga
) number of generati ons for NSGA-I I
N
i
) fl ux of speci es i at any axi al l ocati on l i nsi de the
catal yst sl ab, kmol m
-2
h
-1
N
p
) popul ati on si ze for NSGA-I I
p
c
) probabi l i ty of crossover
p
m
) probabi l i ty of mutati on
P ) operati ng pressure at axi al l ocati on Z and ti me t, kPa
q
cond
) conducti ve heat fl ux based on the average surface
area of the tube, kJ m
-2
h
-1
q
conv
) convecti ve heat fl ux based on the i nner surface area
of the tube, kJ m
-2
h
-1
q
rad
) radi ati ve heat fl ux based on the outer surface area
of the tube, kJ m
-2
h
-1
r ) radi al posi ti on, m
r
i
) rate of the ith reacti on (i ) I -I I I ) correspondi ng to
condi ti ons at the catal yst surface at axi al l ocati on Z and
ti me t, kmol h
-1
kg
cat
-1
R ) sum of feed mol ar rati os
R
i
) rate of producti on of the ith component at the catal yst
surface at any axi al l ocati on Z and ti me t, kmol h
-1
kg
cat
-1
R
i,n
) rate of producti on of the ith component at the nth
col l ocati on poi nt i nsi de the catal yst sl ab at axi al l ocati on
Z and ti me t, kmol h
-1
kg
cat
-1
S/C ) rati o of carbon di oxi de to methane i n feed, (kmol /h
of steam recycl ed)/[kmol /h of methane fed (F
CH4,i n
)]
t ) ti me, h
T ) process-gas temperature at axi al l ocati on Z and ti me
t, K
T
f
) adi abati c fl ame temperature at any axi al l ocati on i n
the reactor, K
T
g
) temperature of the furnace gas, K
T
w
) tube-wal l temperature, K
U ) fi l m heat-transfer coeffi ci ent on the i nsi de of the tube
(to gas + catal yst), kJ h
-1
m
-2
K
-1
v) di mensi onl ess di stance wi thi n the catal yst sl ab () l/l
c
)
(v ) 0 at catal yst surface)
v
l
) superfi ci al vel oci ty of gas i n the reformer, m h
-1
y
i
) mol e fracti on of speci es i i n the gas phase at axi al
l ocati on Z and ti me t
yj
i,n
) mol e fracti on of component i at the nth col l ocati on
poi nt i nsi de the catal yst sl ab at axi al l ocati on Z and ti me
t
Z ) axi al l ocati on, m
Greek Symbols

b
) voi d fracti on i n the catal yst bed (outsi de the porous
catal yst pel l et)

c
) vol ume fracti on of pores i nsi de a catal yst pel l et

I
,
I I
,
I I I
) effecti veness factors for reacti ons I -I I I , re-
specti vel y, at axi al l ocati on Z and ti me t

i
) effecti veness factor for component i at axi al l ocati on
Z and ti me t
) vi scosi ty of the gas mi xture at axi al l ocati on Z and
ti me t, kg m
-1
h
-1

g
) emi ssi vi ty of the furnace gas

f
) emi ssi vi ty of the fl ames

t
) emi ssi vi ty of the tube materi al
F
b
) densi ty of the catal yst bed (sol i d + voi ds + pores), kg
m
-3
F
g
) densi ty of the gas mi xture, kg m
-3
F
s
) densi ty of the catal yst pel l et (sol i d + pores), kg m
-3
) Stefan-Bol tzmann constant, kJ h
-1
m
-2
K
-4

ik
) stoi chi ometri c coeffi ci ent of the ith component par-
ti ci pati ng i n the kth reacti on
) tortuosi ty of the catal yst pel l et

s
) spheri ci ty of the catal yst pel l et
Subscripts/ Superscripts
i , 1 ) i nner or i ni ti al
i n ) i nl et of the reformer
o, 2 ) outer
out ) outl et of the reformer
SS ) steady state
SS1 ) i ni ti al steady state
w ) wal l
Appendix
Model Equations.
2,6
(a) Gas Phase
F
CH
4
,i n
) 16
F
R
,
where R ) [1 + (S/C) + (H/C) + (D/C) + (N/C)]
(A1)
F
H
2
,out
) 2C
H
2
,out
(v
l ,out
A
c
) (A2)
F
CO,out
) 28C
CO,out
(v
l ,out
A
c
) (A3)
C
i
t
)
1

b
[
(v
l
C
i
)
Z
- F
b

i
R
i]
,
i ) CH
4
, H
2
O, CO, CO
2
, H
2
(A4a)
P
Z
) -
1.75G
2
(1 -
b
)

s
D
p

b
3
F
g
(A4b)
T
t
)
1
C
p,t
[
4U(T
w,i
- T)
d
i
- F
g
C
p,g
v
l
T
Z
+
F
b
i)I
I I I
(-H
i
)
i
r
i
]
(A4c)
C
p,t
) F
b
C
p,s
+ [
b
+ (1 -
b
)
c
]F
g
C
p,g
(A4d)
I ni ti al Condi ti ons
C
i
(Z,t)0) ) C
i
SS
(Z),
0 e Z e L; i ) CH
4
, H
2
O, CO, CO
2
, H
2
(A4e)
4040 I nd. Eng. Chem. Res., Vol . 42, No. 17, 2003
The i nner tube wal l temperature, T
w,i
, i s obtai ned by
equati ng the heat fl uxes due to (i ) radi ati ve transfer
from the furnace gases to the exteri or surface of the
tubes
(i i ) conducti ve transfer through the tube materi al
and (i i i ) convecti ve transfer to the gas mi xture and
catal yst bed from the i nner surface of the tubes
(b) Solid (Catalyst) Phase. The i ntraparti cl e mol e
fracti on, yj
i,n
(v), of speci es i at the nth orthogonal
col l ocati on poi nt for a catal yst sl ab at axi al l ocati on Z
and ti me t i s obtai ned by sol vi ng the coupl ed set of 5M
equati ons (n ) 1 i s the fi rst col l ocati on poi nt at v ) 0;
n ) M + 2 i s the l ast col l ocati on poi nt at v ) 0.2; n ) 2,
3, ..., M + 1 are the i nternal col l ocati on poi nts i n 0 e v
e 0.2): 3M al gebrai c and 2M di fferenti al equati ons
(whi ch are transformed i nto al gebrai c equati ons by the
method of orthogonal col l ocati on on fi ni te el ements)
(where the rates, R
i
, are gi ven i n eqs A7-A11)
Effecti veness factors for the components are eval uated
from those for the reacti ons
2
through the equati on
Literature Cited
(1) Armor, J. N. The Mul ti pl e Rol es for Catal ysi s i n the
Producti on of H2. Appl. Catal. A 1999, 176, 159.
(2) El nashai e, S. S. E. H.; El shi shi ni , S. S. Modeling, Simula-
tion and Optimization of I ndustrial CatalyticFixed Bed Reactors;
Gordon and Breach: Amsterdam, The Netherl ands, 1993.
(3) Xu, J.; Froment, G. F. Methane Steam Reformi ng, Metha-
nati on and Water-Gas Shi ft: I . I ntri nsi c Ki neti cs. AI ChE J . 1989,
35, 88.
(4) Xu, J.; Froment, G. F. Methane Steam Reformi ng: I I .
Di ffusi onal Li mi tati ons and Reactor Si mul ati on. AI ChE J . 1989,
35, 97.
(5) Si ngh, C. P. P.; Saraf, D. N. Si mul ati on of Si de Fi red
Steam-Hydrocarbon Reformers. I nd. Eng. Chem. Process Des.
Dev. 1979, 18, 1.
P(Z,t)0) ) P
SS
(Z), 0 e Z e L (A4f)
T(Z,t)0) ) T
SS
(Z), 0 e Z e L (A4g)
y
i
) C
i
/C
t
, i ) CH
4
, H
2
O, CO, CO
2
, H
2
(A5)
y
N
2
) 1 - (y
CH
4
+ y
H
2
O
+ y
CO
+ y
CO
2
+ y
H
2
) (A6)
R
i
)

k)I
I I I

ik
r
k
, i ) CH
4
, H
2
O, CO, CO
2
, H
2
(A7)
r
I
)
k
I
E
2
y
H
2
2.5
P
(
y
CH
4
y
H
2
O
-
P
2
y
H
2
3
y
CO
K
I
)
(A8)
r
I I
)
k
I I
P
E
2
y
H
2
(
y
CO
y
H
2
O
-
y
H
2
y
CO
2
K
I I I
)
(A9)
r
I I I
)
k
I I I
E
2
y
H
2
3.5
P
(
y
CH
4
y
H
2
O
2
-
P
2
y
H
2
4
y
CO
2
K
I
K
I I
)
(A10)
E )
[
1 + P(K
CO
y
CO
+ K
CH
4
y
CH
4
+ K
H
2
y
H
2
) +
K
H
2
O
y
H
2
O
y
H
2
]
(A11)
q
rad
)
(A
t,o
+ A
ref
)
g

t
(A
t,o
+ A
ref
)
g
+ A
t,o
(1 -
g
)
t
(T
g
4
- T
w,o
4
) +

N
b
A
f

t
(1 -
g
)
A
t,o
T
f
4
(A12)
q
cond
)
2k
w
(T
w,o
- T
w,i
)
l n(d
o
/d
i
)
(A13)
q
conv
) U(T
w,i
- T) (A14)
U ) 0.4
k
g
D
p
[
2.58
(
D
p
G

)
1/3
(
C
p,g

k
g
)
1/3
+
0.094
(
D
p
G

)
0.8
(
C
p,g

k
g
)
0.4
]
(A15)
d
2
yj
CH
4
,n
dv
2
) a
2
l
c
2
[
F
s
(r
I
+ r
I I
+ r
I I I
)
b
(P/RT)D
CH
4
e
]
R
CH
4
,n
R
H
2
O,l
,
n ) 2, 3, ..., M + 1 (A16)
d
2
yj
H
2
O,n
dv
2
) a
2
l
c
2
[
F
s
(r
I
+ r
I I
+ 2r
I I I
)
b
(P/RT)D
H
2
O
e
]
R
H
2
O,n
R
H
2
O,l
,
n ) 2, 3, ..., M + 1 (A17)
yj
CO,n
) y
CO
-
1
D
CO
e
[2D
CH
4
e
(yj
CH
4
,n
- y
CH
4
) -
D
H
2
O
e
(yj
H
2
O,n
- y
H
2
O
)], n ) 2, 3, ..., M + 1 (A18)
yj
CO
2
,n
) y
CO
2
+
1
D
CO
2
e
[D
CH
4
e
(yj
CH
4
,n
- y
CH
4
) -
D
H
2
O
e
(yj
H
2
O,n
- y
H
2
O
)], n ) 2, 3, ..., M + 1 (A19)
yj
H
2
,n
) y
H
2
-
1
D
H
2
e
[2D
CH
4
e
(yj
CH
4
,n
- y
CH
4
) +
D
H
2
O
e
(yj
H
2
O,n
- y
H
2
O
)], n ) 2, 3, ..., M + 1 (A20)
Boundary Condi ti ons
(at Axi al Locati on Z and Ti me t)
yj
i,1
) y
i
(Z,t), i ) CH
4
, H
2
O, CO, CO
2
, H
2
dyj
i,M+2
dv
) 0, i ) CH
4
, H
2
O, CO, CO
2
, H
2

k
)

v)0
v)a
r
k
(yj
i
,T,P) dv
r
k
(y
i
,T,P)l
c
, k ) I , I I , I I I (A21)

i
)

k)I
I I I

ik

k
r
k

k)I
I I I

ik
r
k
, i ) CH
4
, H
2
O, CO, CO
2
, H
2
(A22)
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Received for review December 3, 2002
Revised manuscript received Apri l 15, 2003
Accepted June 14, 2003
I E0209576
4042 I nd. Eng. Chem. Res., Vol . 42, No. 17, 2003