Chemical Engineering Science 57 (2002) 34393451

www.elsevier.com/locate/ces
Modelling the catalytic steam reforming of methane: discrimination
between kinetic expressions using sequentially designed experiments

K. Jarosch, T. El Solh, H. I. de Lasa

Faculty of Engineering Science, Chemical Reactor Engineering Centre, University of Western Ontario, London, Ont., Canada N6A 5B9
Received 26 March 2001; received in revised form 3 September 2001; accepted 4 September 2001
Abstract
The kinetics of steam reforming of methane on a uidizable Ni}:-alumina catalyst is studied in a novel CREC riser simulator reactor.
The BoxHill discrimination function is used to design sequential experiments for discrimination between six candidate models for the
rate of steam reforming of methane carried out over a uidized bed of catalyst. Proposed models include one model in which the rate of
reforming is dependent only on the partial pressure of methane (rst order), a model in which the rate is dependent on the partial pressures
of the products and of the reactants (power law) and four models with various adsorption eects. Models are expressed in a form such that
the parameters are close-to-linear. Discrimination results indicate that the rate of methane reforming has a rst order dependency on the
partial pressure of methane in the numerator and the adsorption of methane in the denominator. Estimates of the close-to-linear parameters
in the most probable model are made using 85 observations of the conversion of methane made over a 20 wt% Ni}:-alumina catalyst. All
parameters are found to be signicant at the 95% condence level and correlation between the parameters is found to be moderate (0.84).
? 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Discrimination; Fluidization; Kinetics; Modelling; Parameter identication; Statistics
1. Introduction
Steam reforming of hydrocarbons is the primary indus-
trial process for the production of hydrogen and synthesis
gas. The reforming reaction is both endothermic and equi-
librium limited. The feedstock for the reforming process,
usually natural gas or light distillates, is mixed with steam
and brought into contact with a catalyst consisting primar-
ily of nickel dispersed on :-alumina. If the temperature is
suciently high, the hydrocarbons react with the steam pro-
ducing a mixture of partially reacted hydrocarbons, carbon
monoxide and hydrogen. Carbon dioxide is also present in
the product gas mixture as the watergas shift reaction si-
multaneously takes place.
On the industrial scale, reforming is carried out over a
xed bed of monolithic catalyst packed into tubes. The large

Manuscript prepared for the special issue of Chemical Engineering

Science in honour of Dr. J. C. Charpentier.

Corresponding author. Tel.: +1-519-661-2144;

fax: +1-519-661-3498.
E-mail address: hdelasa@eng.uwo.ca (H. I. de Lasa).
quantity of heat required by the reforming reaction is pro-
vided by locating the tubes in a furnace. Operating condi-
tions depend on the end use of the synthesis gas but outlet
temperatures range from 700900

C. Operating pressures
are in the region of 23 MPa. Molar steam-to-carbon ratios
employed are in the range 3:15:1.
A novel multifunctional reactor concept for steam reform-
ing, called CATFORMING that combines high-temperature
hydrogen-permeable membranes with a circulating u-
idized bed, (CFB) has been under study in the Chemical
Reactor Engineering Centre (CREC) at the University of
Western Ontario (UWO) (Jarosch, 1995, 2000). In the
CATFORMER reactor concept (Fig. 1), the reactant
gas meets with catalyst and the resulting gassolid
suspension enters the riser}downer section of the re-
actor. The suspension ows down the reactor tube
and the reforming and watergas shift reactions take
place. After a certain distance, hydrogen is continu-
ously removed from the mixture via diusion through
a membrane. Hydrogen removal shifts the conversion
of methane to values above those attainable at equilib-
rium as well as favorably aecting the selectivity. After
0009-2509/02/$ - see front matter ? 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0009- 2509( 02) 00214- 2
3440 K. Jarosch et al. / Chemical Engineering Science 57 (2002) 34393451
Fig. 1. Schematic ow diagram of the CATFORMER concept shown as
in the downow conguration.
exiting the reactor, the synthesis gas product is separated
from the catalyst and sent for further processing or direct
use in the synthesis of alcohols.
During steam reforming, coke may be formed by two
mechanisms. When the reactant gas is far from the composi-
tion at chemical equilibrium, coke may be formed via kinetic
processes. When the reactant gas composition is close to the
composition at chemical equilibrium, coke will be formed
if graphitic carbon formation is predicted at chemical equi-
librium. In conventional tubular reforming, the formation
of coke by either mechanism is strictly avoided by ensur-
ing the equilibrated gas principle applies. This means that
conditions are maintained such that the formation of carbon
is not favored at equilibrium and the rate of reforming is
controlled by the rate of heat transfer such that the reactant
gas composition is very close to its equilibrium value at any
given point in the reformer. In this process, coke formation
is expected via kinetic processes and as a result, some frac-
tion of the catalyst will need to be regenerated. After regen-
eration, hot catalyst is recirculated to the downow section
thus relieving a portion of the heat duty required in the pri-
mary section of the reactor.
Studies have been carried out on aspects of this process
including:
(a) the development of suitable catalysts (El Solh, Jarosch,
& de Lasa, 2001),
(b) the development of suitable membranes (Jarosch & de
Lasa, 2001),
(c) the collection of data on catalyst coking,
(d) the study of the eect of time-on-stream on catalyst ac-
tivity,
(e) the collection of reaction rate data for kinetic modelling
(Jarosch, 2000).
Emphasis was also placed on the evaluation of catalysts and
membranes under reactor conditions of temperature (750
850

C) and total pressure (2.03.0 MPa) closely approxi-

mating industrial conditions.
2. Steam reforming of methane
Natural gas is the primary feedstock for the steam re-
forming process. As the main component of natural gas
is methane, methane was used as analog for natural gas.
The chemical processes involved in the steam reform-
ing of methane can be expressed using two independent
equilibrium-limited reactions. These are the endothermic
reforming reaction (Eq. (1)) and the exothermic watergas
shift reaction (Eq. (2)).
CH
4
+ H
2
O CO + 3H
2
, (1)
CO + H
2
O CO
2
+ H
2
. (2)
A wide variety of rate expressions for the steam reform-
ing of methane have been proposed. These models range in
complexity from simple rst order dependency on methane
such as those proposed by Munster and Grabke (1981) and
Prokopiev, Aristov, Parmon, and Giordano (1992) involving
two parameters to complex LangmuirHinshelwood mod-
els with over ten parameters (Xu & Froment, 1989). It is
generally agreed, with the exception of Al-Ubaid and Wolf
(1987, 1988), that the rate of methane reforming has a rst
order dependency on methane. Furthermore, it is also agreed
that the rate-determining step in the reforming process is the
formation of adsorbed carbon species (Munster & Grabke,
1981):
CH
4
+Metal site C
Ads
+2H
2
. (3)
The formation of adsorbed carbon from methane is a step-
wise process that requires that a CH bond be broken while
methane is in the gas phase. The resultant CH
3
species must
then come into contact with an open site on the surface of
the metal crystal. After being adsorbed to the surface of the
metal crystal, the CH
3
is transformed into adsorbed carbon
by stepwise dehydrogenation (Rostrup-Nielsen, 1993):
CH
gas
4
CH
gas
3
CH
3
CH
2
-
CH
1
C
Ads
. (4)
This mechanism leads to the formulation of rate equations
of the following form (Munster & Grabke, 1981):
r
CH
4
k
CH
4

:
H
2
. (5)
In Eq. (5), the value of : is found to depend on temperature,
having a value close to 1 at low temperatures (700

C)
and approaching 0 at high temperatures (700

C).
Kinetic rate expressions for the steam reforming of
methane found in the literature use the steady state
K. Jarosch et al. / Chemical Engineering Science 57 (2002) 34393451 3441
Fig. 2. Two models each possessing one independent variable and having
multiple parameters.
approximation and take the form (Rostrup-Nielsen, 1993):
r
CH
4
=k
CH
4
[(
H
2
O
,
H
2
)
(1 + [(
CH
4
,
H
2
O
,
H
2
,
CO
,
CO
2
))

_
1

CO

3
H
2

CH
4

H
2
O
K
1
_
. (6)
Most kinetic data reported in the literature have been col-
lected using packed bed reactors at temperatures and pres-
sures signicantly lower than those employed in industrial
reforming using catalyst designed for xed bed use. Given
that the data CATFORMER is a uidized reactor, operated
at both high temperature and pressure and that a number of
competing mechanisms are reported in the literature, an ef-
cient experimental strategy needed to be devised for the
selection of an appropriate kinetic expression.
3. Sequential design for the model discrimination
It is often desirable to encapsulate the behavior of a sys-
tem in a mathematical model and just as often there may be
more than one plausible model available. The question is as
to how does one select between plausible kinetic models.
This is the motivation for the model discrimination. There
are two possible approaches. The rst approach involves col-
lecting experimental data estimating the model parameters
and then comparing the models based on such criteria such
as residual sum, lack-of-t and signicance of the parame-
ters. The second approach involves the use of a statistical
criterion to select settings of the independent variables (ex-
perimental conditions) such that dierences between models
are emphasized.
Fig. 2, representing two multiparameter models of one
independent variable, illustrates the hazards involved when
the rst method is employed for model discrimination. If
all the experimental data were collected with settings of the
independent variable in the shaded region, then it will be
dicult to judge which is the better model as the predicted
values are very close. For simple models, it may be easy
to select unaided a set of experimental conditions that al-
low discrimination, but for systems that are more complex
this may be dicult or impossible. It is under these circum-
stances that the second technique, true model discrimina-
tion, becomes necessary. The use of a statistical criterion to
guide the selection of experimental conditions ensures that
the experimental conditions are moved into the unshaded
region of Fig. 2 so that the dierences between the models
become clear.
Model discrimination can be thought of as an iterative
process. Starting with a hypothesis, for example the selection
of a set of candidate models, an initial set of experiments
is designed and performed so that the parameters present in
each model can be estimated. With this information and a
statistically based criterion, an experimental condition can
be selected that will improve our knowledge of which model
best describes the behavior. This process continues until the
experimenter is satised that one model is superior to the
others proposed.
4. Criterion for model discrimination
In the section above, it was suggested that a criterion
could be used to design sequential experiments, the con-
ditions of which would allow for maximum discrimination
between the proposed models. One criterion that could be
used would be the experimental conditions (levels of the in-
dependent variables) that maximizes the dierence between
the model outputs. This criterion would be satisfactory for
the case depicted in Fig. 2. However, this criterion proves
to be less satisfactory if the models are of similar mathe-
matical form. In the case of models of similar mathemati-
cal form, a desirable criterion would not only maximize the
dierence in the model outputs but would also employ the
variance of the experimental response to maximize the like-
lihood of discrimination. An example of such a criterion is
the Kullback discrimination function (Kullback, 1978).
The Kullback discrimination function can be formulated
if we have two models, with outputs,

Y
1
and

Y
2
, each out-
put being a random variable, that is to say having statistical
properties such as a mean and variance. If we wish to deter-
mine which of the two models is more likely, we can say that
if model 1 is correct

Y
1
will be distributed as the probabil-
ity density function
1
(,). If model 2 is correct

Y
2
will be
distributed as
2
(,). For example, imagine an observation
of the output lies at ,

as in Fig. 3. One could ask the ques-

tion, what are the odds that this observation is from
1
(,)
as opposed to
2
(,)? Kullback suggests that the following
ratio can be taken as a measure (Kullback, 1978, p. 4):
ln
_

1
(,)

2
(,)
_
. (7)
3442 K. Jarosch et al. / Chemical Engineering Science 57 (2002) 34393451
Fig. 3. If the observation ,

made at x is normally distributed, what are

the odds that it is from either
1
(,) or
2
(,).
Using the ratio suggested by Kullback (Eq. (7)), the ex-
pected value of the odds in favor of selecting model 1 can
be found by integrating
I (1:2) =
_

1
(,) ln
_

1
(,)

2
(,)
_
d,. (8)
Similarly, the expectation in favor of selecting model 2 can
be found as follows:
I (2:1) =
_

2
(,) ln
_

2
(,)

1
(,)
_
d,. (9)
Eqs. (8) and (9) can be regarded as the weight of information
in favor of choosing model 1 or 2. For independent random
events I (1:2) and I (2:1) are additive by the principle of
divergence (Kullback, 1978, p. 12) so the integral form of
the Kullback discrimination function can be written as
J(1, 2) = I (1:2) + I (2:1) =
_

(
1
(,)

2
(,)) ln
_

1
(,)

2
(,)
_
d,. (10)
The Kullback discrimination function (Eq. (10)) is a mea-
sure of the total information available when discriminating
between two hypotheses. When the function (Eq. (10)) is
maximized, discrimination between the models may become
possible. To accomplish this, the nature of the distributions
needs to be known.
Given that model r is the correct model, it will have an
expected value (E[Y
r
(X, x
(n+1)
)]) when evaluated at x
(n+1)
and this can be written as

Y
(n+1)
r
. When the (n + 1)th ex-
perimental response, Y
(n+1)
, is measured, we nd that due
to the experimental error, c
EXP
, it diers from the expected
value

Y
(n+1)
r
. We can assume that Y
(n+1)
is normally dis-
tributed around the expected value of each model,

Y
(n+1)
r
,
with a variance of o
2
Y
and that

Y
(n+1)
r
is distributed in a lin-
earized region around the predicted value,

Y
(n+1)
r
, with a
variance of o
2
r
. When this is the case we can say that Y
(n+1)
is distributed around

Y
(n+1)
r
with a variance of o
2
Y
+o
2
r
. Af-
ter taking this into account, the probability density function
of Y
(n+1)
for the rth model can be written as

r
(Y
(n+1)
) =
1
_
2(o
2
Y
+ o
2
r
)
exp
_

1
2
(Y
(n+1)

Y
(n+1)
r
)
2
o
2
Y
+ o
2
r
_
. (11)
If the appropriate substitution of Eq. (11) into Eqs. (8)
and (9) is made and integrated, the followings result:
I (1:2) =
1
2
ln
_
o
2
Y
+ o
2
2
o
2
Y
+ o
2
1
_
+
1
2
o
2
Y
+ o
2
1
o
2
Y
+ o
2
2

1
2
+
1
2
(

Y
(n+1)
1


Y
(n+1)
2
)
2
o
2
Y
+ o
2
2
, (12)
I (2:1) =
1
2
ln
_
o
2
Y
+ o
2
1
o
2
Y
+ o
2
2
_
+
1
2
o
2
Y
+ o
2
2
o
2
Y
+ o
2
1

1
2
+
1
2
(

Y
(n+1)
1


Y
(n+1)
2
)
2
o
2
Y
+ o
2
1
. (13)
Eqs. (12) and (13) can be added as per Eq. (10) to give
J(1, 2) =
1
2
(o
2
1
o
2
2
)
_
1
o
2
Y
+ o
2
2

1
o
2
Y
+ o
2
1
_
+
1
2

_
1
o
2
Y
+ o
2
2
+
1
o
2
Y
+ o
2
1
_
(

Y
(n+1)
1


Y
(n+1)
2
)
2
.
(14)
Now we can nd the vector of independent variables, x
(n+1)
,
that maximizes J(1, 2). The development given above is
valid for two models but it can be extended for any number
of models.
As neither o
2
Y
nor o
2
r
s are known they need to be esti-
mated. The variance o
2
Y
can be estimated by using s
2
e
, mea-
sured by doing repeat experiments. The variances of the
models, o
2
r
s, can be estimated from the variance of the
residuals when the models are t to n observations.
5. The BoxHill discrimination function
Box and Hill (1967) proposed an improvement to the
Kullback discrimination function that takes into account
what is called the prior probability,

P
(n)
r
of the models or
in other words, the probability that model r of a set of t
models is the correct model after n experiments. Box and
Hill suggest that by weighting Kullbacks information func-
tions, I (i:)), with the prior probabilities, we will be able to
increase the eciency of the discrimination. The BoxHill
K. Jarosch et al. / Chemical Engineering Science 57 (2002) 34393451 3443
discrimination function can be developed as follows:
K
J
= [

P
(n)
1


P
(n)
t
]
_

_
I (1:1) I (1:2) I (1:t)
I (2:1) I (2:2) I (2:t)
.
.
.
.
.
.
.
.
.
I (t:1) I (t:2) I (t:t)
_

P
(n)
1
.
.
.
.
.
.

P
(n)
t
_

_
. (15)
If we note that the diagonal of the I matrix is zero, then we
nd
K
J
=

P
(n)
1

P
(n)
2
J(1, 2) +

P
(n)
1

P
(n)
3
J(1, 3) +
+

P
(n)
1

P
(n)
t
J(1, t) +

P
(n)
2

P
(n)
t
J(2, t)
+ +

P
(n)
t1

P
(n)
t
J(t 1, t), (16)
K
J
=
1
2
t

i=1
t

)=i+1

P
(n)
i

P
(n)
)
_
(o
2
i
o
2
)
)
2
(o
2
Y
+ o
2
i
)(o
2
Y
+ o
2
)
)
+ (

Y
(n+1)
i

Y
(n+1)
)
)
2
_
1
o
2
Y
+ o
2
i
+
1
o
2
Y
+ o
2
)
__
. (17)
The variances required to calculate K
J
(Eq. (17)) can be
estimated as described above. After n experiments,

P
(n)
r
can
be evaluated using Bayes theorem with

P
(n1)
r
, the proba-
bility that any given model is correct prior to evaluating the
experimental data, set to 1}t and
r
(Y
(n)
) evaluated with
Eq. (11) (with n replacing n + 1). This is to say that be-
fore having any information on the behavior in question, if
t plausible models for the behavior are proposed, the prob-
ability that any one of them is the correct model is 1}t. The
result is as follows:

P
(n)
r
=

P
(n1)
r

r
(Y
(n)
)

t
r=1

P
(n1)
r

r
(Y
(n)
)
. (18)
This method can be extended to accommodate multiple
outputs. The advantage of discrimination on more than one
output is that the rate of discrimination is increased signi-
cantly. The BoxHill criterion also allows for discrimination
between models of similar mathematical form as it accounts
for the variance of the prediction, a function of the number
of parameters, as well as the value of the sum of the squared
residuals.
6. Procedure for sequential experimentation
The procedure for a sequential design using the BoxHill
discrimination function can be summarized as follows:
(a) Using the best information possible, design an experi-
ment to collect n observations with repeats for the esti-
mation of o
2
Y
.
(b) Estimate the parameters of the models in question and
calculate o
2
r
for each model.
(c) Calculate

P
(n)
r
.
(d) Find the vector of experimental conditions (x
(n+1)
)
which maximizes K
J
.
(e) Run the conditions x
(n+1)
, return to step (b).
A number of approaches are available for nding the ex-
perimental conditions x
(n+1)
that maximize K
J
; however, in
most cases the problem is restated as a minimization prob-
lem. This restatement is accomplished by simply searching
for values of x
(n+1)
that minimize K
J
. In this case, a nu-
merical tool for nding constrained minima of multivariate
functions from the MATLAB
TM
optimization toolbox called
CONSTR.M was used. The numerical approach employed
in this work to nd values of x
(n+1)
that minimize K
J
is reported in detail by Jarosch (2000). MATLAB
TM
is a
trademark of the MathWorks Inc.
7. Assumptions and limitations
No statistical technique should be considered as a
panacea. These techniques only provide guidelines and the
judgment and experience of the experimenter are still re-
quired. This is particularly evident when model discrimina-
tion techniques are employed. The input of the experimenter
is critical in determining which models will be considered,
the number of models considered and the level at which the
discrimination will be terminated. The experimenter must
always keep in mind that no discrimination technique will
be able to identify the best model if it is not included in
the set being discriminated. The experimenter must also
keep in mind that if none of the models are adequate, no
discrimination may be possible.
In addition to the limitations inherent in the technique,
a number of assumptions are used. The most important as-
sumptions are that the error associated with the lack-of-t is
additive and that it follows the probability density function
expressed in Eq. (11). This will only be strictly correct if
the model in question is the true model and behaves in a
linear manner. This deviation from the assumption is com-
pounded by the fact that the variances o
2
Y
and o
2
r
must be
estimated using experimentally determined values.
In the work presented here, three steps were taken to en-
sure that the models behaved in a linear or close-to-linear
manner. The rst step, which also underlines the judgment
of the experimenter as mentioned above was that, models
3444 K. Jarosch et al. / Chemical Engineering Science 57 (2002) 34393451
Fig. 4. Cross-sectional view of a Riser Simulator unit modied for use
in the CATFORMING process.
were selected such that the initial LangmuirHinshelwood
model forms possessed only low order polynomials in the
denominator. Models with high order polynomials, such as
those suggested by Agnelli, Ponzi, and Yeramian (1987),
with orders as high as 7, given their essentially empiri-
cal character, were not considered. The second step was to
ensure that the LangmuirHinshelwood models were repa-
rameterized such that parameters behave in a close-to-linear
manner (Ratkowsky, 1990). The third step was to employ
the technique of temperature centering to reduce the cor-
relation between the activation energy and pre-exponential
factor for each parameter.
8. Experimental setup and materials
Experimental trials were carried out in a modied Riser
Simulator (de Lasa, 1991) specically manufactured for
the current project (Jarosch, 2000). The Riser Simulator
(Fig. 4) is a bench scale reactor used to simulate the behav-
ior of riser}downer reactors operating in the fast uidization
regime. This is achieved by trapping a sample of catalyst
between two porous metal disks in a basket that is inserted
into the body of the reactor and, when seated, lies beneath a
turbine impeller. When the impeller is spun, reactant gas is
drawn through the basket causing the sample of catalyst to
become fully uidized. As the internal recirculation rate is
high, the Riser Simulator can be used to follow the progress
of a well-mixed plug as it ows up a riser or down a down-
ow reactor.
The unit used in this study was modied to allow for
the insertion of a high-temperature hydrogen membrane
by lengthening the upper shell (to allow the basket to be
Fig. 5. Schematic ow diagram of the experimental setup.
inserted) and truncating the lower shell. The membrane
(when present) is welded into a plate which is inserted
between the upper and lower shells. The lower shell has a
pocket located directly below the membrane. Inlet and out-
let ports on the lower shell allow sweep gas to remove the
permeate gas. Runs without the membrane can be carried
out using a blank plate.
In addition to the Riser Simulator, several other major
pieces of equipment were required to complete the experi-
mental setup; the methane and steaminjector, the blowdown
and GC sampling system, and the data acquisition system
(Fig. 5). Injections of methane were made using an auto-
mated injection system (AIS). The injector consists of a bar-
rel tted with a plunger actuated by a double-action pneu-
matic piston. The volume injected was controlled by restrict-
ing the stroke of the actuator. The ow through the injector
was controlled by a slider valve. In the ll position, feed
gas is allowed to ow from the supply cylinder into the bar-
rel and out to the vent via a needle valve. The pressure in the
injector was controlled by adjusting the needle valve. When
the slider valve is in the inject position, the inlet and out-
let ports are closed and a third port is open such that when
the plunger moves forward, the contents of the barrel are
injected into the reactor through H2OV and HPV1. The si-
multaneous generation and injection of the required amount
of steam was also necessary. This was accomplished by us-
ing a peristaltic pump to circulate heated distilled water at
a rate of 50 ml min
1
from a reservoir and through a loop
connected to the six-port valve (H2OV). To make an injec-
tion of steam and methane, H2OV was rotated to allow the
methane from the AIS to travel through the loop prior to
entering the reactor thus carrying the water along before it.
In order to speed the vaporization of the water, the section
of tubing (which lies outside the reactors insulating shell)
between HPV1 and the reactor was heated independently
using a heating tape.
Reaction runs were terminated by opening valves, HPV2
and LPV2, and allowing the pressure to equalize. The ratio
of volume between the blow down bottle and the reactor is
K. Jarosch et al. / Chemical Engineering Science 57 (2002) 34393451 3445
approximately 6:1, as the bottle is kept at room temperature.
This provided a pressure reduction of about 18:1 (depending
on the initial reactor temperature). Product gas would then
be allowed to ow through a sample loop attached to the
valve GCV. Samples of product gas could then be injected
in the GC for TCD analysis.
Pressure, temperature and GC output data from each trial
were collected using a PC-based data acquisition system.
The pressures in both the reactor and blow down bottle were
recorded for each trial along with their respective tempera-
tures. The system was also used to record the response of
the GC TCD.
9. Methodology for parameter estimation=discrimination
As mentioned above, the measured experimental response
was the conversion of methane, that is to say, the extent of
the reforming reaction (Eq. (1)). As the bench scale CAT-
FORMER (Riser Simulator) operates in batch mode, the
material balance must be integrated in order to calculate the
reaction extent. This was done in the following manner, rst
the extent of the reforming reaction (c
REF
) based on the ini-
tial number of moles of methane injected (N
0
CH
4
) and the
number of moles consumed is expressed as a function of
contact time:
dc
REF
dt
=
dN
CH
4
}dt
N
0
CH
4
. (19)
The number of moles of methane consumed as a function
of contact time was expressed as
dN
CH
4
dt
=r
CH
4
w, (20)
where r
CH
4
is a function of the partial pressure of the reac-
tants and has a form similar to Eq. (6), and w the mass of
catalyst.
Based on the initial number of moles of methane and
water (N
0
H
2
O
) injected, the partial pressures of each species
present were calculated as

CH
4
=
_
N
0
CH
4
c
REF
N
0
1
+ 2c
REF
_
P
1
; (21a)

H
2
O
=
_
N
0
H
2
O
c
REF
c
WGS
N
0
1
+ 2c
REF
_
P
1
, (21b)

CO
=
_
c
REF
c
WGS
N
0
1
+ 2c
REF
_
P
1
; (22a)

H
2
=
_
3c
REF
+ c
WGS
N
0
1
+ 2c
REF
_
P
1
, (22b)

CO
2
=
_
c
WGS
N
0
1
+ 2c
REF
_
P
1
; (23a)
P
1
=
N
1
R1
J
R
. (23b)
Under the conditions used, the watergas shift reaction was
found to be at chemical equilibriumwith the conditions in the
reactor at any given time (Jarosch & de Lasa, 1999). The
extent of the watergas shift reaction (c
WGS
) could, therefore,
be estimated using the chemical equilibrium relationship:
K
2
=

CO
2

H
2

CO

H
2
O
. (24)
If Eqs. (21b), (22a), (22b) and (23a) are substituted into Eq.
(24) the extent c
WGS
can be calculated from the quadratic
form:
c
WGS
=
b

b
2
4ac
2a
(25)
with
a = K
2
1, (26a)
b =(K
2
N
0
H
2
O
+ 3c
REF
), (26b)
c = K
2
c
REF
(N
0
H
2
O
c
REF
). (26c)
Once a model form was selected for the rate of methane
consumption, r
CH
4
, and given a set of parameter values, the
predicted extent of the reforming reaction could be calcu-
lated. The parameter estimation procedure was executed
using the non-linear least-squares regression routine,
CURVEFIT.M, available in the Optimization Toolbox (ver-
sion 2.0) of MATLAB
TM
release 11 version 5.3.0.10183.
The integration required in the parameter estimation was
performed numerically using the MATLAB
TM
m-le
ODE45.M available in the MATLAB
TM
Toolbox version
5.3 (Jarosch, 2000).
10. The models
Six models were proposed as candidates to represent the
rate of consumption of methane. The model forms were
selected such that they would represent a broad range of
possible mechanisms while at the same time maintaining a
low degree of parameterization.
MODEL I: Being the First Order model, it represents
the rate of consumption of methane as having a rst or-
der dependence on the partial pressure of methane. This be-
havior was reported by Munster and Grabke (1981) when
nickel foil was used as a catalyst for the steam reforming of
methane in the temperature range 700900

C. This can be
represented as follows:
r
CH
4
1
= 0

CH
4
_
1

CO

3
H
2

CH
4

H
2
O
K
1
_
. (27)
3446 K. Jarosch et al. / Chemical Engineering Science 57 (2002) 34393451
MODEL II: In Model 1, adsorption is assumed to play
a minimal role in determining the rate; while in Model II,
the First Order Adsorption model, adsorption of methane
is assumed to play a role in determining the apparent rate
of methane consumption.
r
CH
4
2
=

CH
4
(0

1
+ 0

CH
4
)
_
1

CO

3
H
2

CH
4

H
2
O
K
1
_
. (28)
In addition, the formation of an adsorbed carbon species
(Eq. (3)) is assumed to be the direct result of methane ad-
sorption to the nickel crystal surface. The products, hydro-
gen and carbon monoxide, are not adsorbed. Water reacts
directly with the adsorbed carbon species.
Model III: In the rst two models proposed, the rate
was assumed to depend only on the partial pressure of
methane. In Model III, it is assumed that two adjacent sites
on the surface of the nickel crystal are required. One for
the non-dissociate adsorption of water and a second for the
adsorbed carbon species. Although not technically of sec-
ond order, this model was referred to as the Second Order
Adsorption model.
r
CH
4
3
=

CH
4

H
2
O
(0

1
+ 0

CH
4
+ 0

H
2
O
)
2
_
1

CO

3
H
2

CH
4

H
2
O
K
1
_
.
(29)
Model IV: It was suggested by Agnelli et al. (1987) as
one of the ve possible mechanistically based rate equations
for the steam reforming of methane. Of the ve rate mod-
els suggested by Agnelli et al. (1987), the models selected
(Models IV and V) were chosen as they include the basic
adsorption eects suggested in the other proposed models
while at the same time preserving a low order in the denom-
inator.
r
CH
4
4
=

CH
4
(0

1
+ 0

H
2
O
+ 0

CO
)
_
1

CO

3
H
2

CH
4

H
2
O
K
1
_
.
(30)
As with Model III, adsorbed water in Model IV (Eq. (30))
is assumed not to dissociate into hydrogen and an adsorbed
oxygen species. Model IV diers from Model III in that the
carbon monoxide product is expected to be adsorbed.
Model V: It was also suggested by Agnelli et al. (1987)
as one of the ve possible mechanistically based rate equa-
tions for the steam reforming of methane. Model V diers
from Models III and IV in that, in this case, water is assumed
to dissociate and form an adsorbed oxygen species. Reac-
tion between adjacent adsorbed carbon and oxygen species
results in the production of carbon monoxide.
r
CH
4
5
=

CH
4
(0

1
+ 0

2
(
H
2
O
}
H
2
) + 0

CO
+ 0

CO
2
)

_
1

CO

3
H
2

CH
4

H
2
O
K
1
_
. (31)
Signicant product adsorption is assumed in Model V
(Eq. (31)) and as adsorbed carbon monoxide can react with
adsorbed oxygen, carbon dioxide is produced. This leads to
the contribution of both carbon dioxide and carbon monox-
ide partial pressures to the apparent reforming rate.
Model VI: The sixth model, unlike the others, presup-
poses that the rate of consumption of methane can be corre-
lated to the respective partial pressures of the reactants and
products. Model VI, the Power Law model, was selected
as such forms are often able to describe chemical kinetic
behaviors without having a rm mechanistic foundation.
r
CH
4
6
= 0

CH
4

0
2
H
2
O

0
3
H
2

0
4
CO

0
5
CO
2
_
1

CO

3
H
2

CH
4

H
2
O
K
1
_
.
(32)
In each model the parameters, 0

i
, were allowed to vary
with temperature (with the exception of the exponents in
Eq. (32)). This behavior was represented using the Arrhe-
nius relationship centered on temperature:
0

i
= 0
1, i
exp
_
0
2, i
R
_
1
1

1
1
c
__
. (33)
This centered form reduces the correlation between the
pre-exponential factor 0
1, i
and the activation energy 0
2.i
thereby improving the statistical properties of the estimate
for the pre-exponential factor.
Typical LangmuirHinshelwood-type rate expressions, in
which the adsorption constants appear in both the numerator
and the denominator of the expression, lead to mathemati-
cal models that are highly non-linear with respect to their
parameters. This non-linearity in the parameters results in a
high degree of parameter correlation. The rate expressions
used here (Eqs. (28)(31)) have been reparameterized as
suggested by Ratkowsky (1990) to provide models that are
close-to-linear with respect to their parameters.
11. Results and discussion
In order to start the process of model discrimination, ini-
tial estimates of the parameters for each of the six candi-
date models were made using 29 observations collected over
20 wt% Ni}:-alumina catalyst (Jarosch, 2000). Settings for
the independent variables likely to allow discrimination be-
tween the models were then identied using MATLAB
TM
via the procedure described above. A trial was then carried
out using the conditions identied and a new set of condi-
tions was identied. This sequence was repeated until one
model was considered to be more probable than the oth-
ers. The experimental conditions identied in this manner
are reported in Table 1. A total of six sets of experimental
conditions were identied and carried out.
As all six models are reasonable, prior to collecting any
data the probability that any one of the models would best de-
scribe the data was presumed to be the same. The probability
K. Jarosch et al. / Chemical Engineering Science 57 (2002) 34393451 3447
Table 1
Sequentially designed experimental conditions
Experiment
a
Temperature Pressure Steam-to-methane ratio Mass of catalyst Contact time
(

C) (MPa g) (g mol g mol

1
) (g) (s)
1 773 2.406 1 0.700 100
2 730 1.393 2.6 0.700 100
3 800 0.352 1 0.304 60
4 750 0.524 2.1 0.700 90
5 750 1.227 6.3 0.303 60
6 750 1.262 6.5 0.275 60
a
Experiments 16 represent the experimental conditions used to obtain observations 3035 in Fig. 7.
Fig. 6. Posterior probability of the six candidate models after each of the
discrimination trials. The observation at 32.5 represents the redistribution
of probability after dropping Models I and III.
that any one of the models would best describe the data was
0.167. After 29 experiments, information is available once
the parameters have been estimated and therefore the pos-
terior probability for each model was to be calculated (Fig.
6). Of the six models, Models II and III had accumulated
approximately half of the probability, 0.23 and 0.26, respec-
tively. The other four models shared the remaining proba-
bility equally.
After the rst discrimination experiment (observation 30,
Fig. 6), Model II had accumulated a probability of 0.38 and
Model III a probability of 0.19. At this point, discrimina-
tion was also made between Models I and V and Models
IV and VI. The results of the second discrimination experi-
ment brought the probabilities of Models II and III together.
Discrimination continued between the remaining four other
models. After the third discrimination experiment, Model II
accumulated a posterior probability of 0.46. The probability
of Model III fell sharply to 0.006 and further dis-
crimination between the four remaining models was
observed.
At this point in the discrimination procedure, two mod-
els were removed from consideration, Models I and III. Of
the models with signicant probability, Model I consistently
had the lowest probability and as the remaining models con-
tained a rst order dependency it was removed in order to
speed the discrimination process. Model III was removed
from the process as its posterior probability was so low as
to have no measurable inuence on the selection of subse-
quent experimental conditions. The posterior probabilities
of the remaining models (II and IVVI) were then adjusted
such that the sum was equal to 1.0. The adjusted prior prob-
abilities for each model were plotted as observation 32.5 in
Fig. 6.
The subsequent three discrimination experiments (obser-
vations 3335, Fig. 6) demonstrated the increasing proba-
bility of Model II at the expense of Model VI, the power law
model. Models IVand Vmaintained approximately the same
probabilities. The nal probabilities were 0.74 for Model II,
the rst order adsorption model, 0.15 for Model IV and 0.11
for Model V.
Once the mathematical form of the model was estab-
lished, the parameters for Model II were estimated using 85
observations collected over 20 wt% Ni}:-alumina catalyst
over a wide range of temperatures, molar SMRs and total
reactor pressures. The parameter estimates with their corre-
sponding 95% condence intervals and correlation matrix
are presented in Table 2. Aplot of the reconciliation between
the experimentally observed conversion of methane and
those predicted using the least-squares parameter estimates
(Table 2) can be found in Fig. 7.
In addition, the parameters for Model II were es-
timated using 52 observations collected over 4 wt%
Ni}:-alumina catalyst collected over a range of temper-
atures, molar SMRs and total reactor pressures similar
to those employed in for the data collected over the
20 wt% Ni}:-alumina catalyst. The parameter estimates
with their corresponding 95% condence intervals and
correlation matrix are presented in Table 3. A plot of
the reconciliation between the experimentally observed
3448 K. Jarosch et al. / Chemical Engineering Science 57 (2002) 34393451
Table 2
Estimates for the parameters in Model II for data collected over 20 wt% Ni}:-alumina catalyst including linearized 95% condence intervals and parameter
correlation
0
1, 1
0
2, 1
0
1, 2
0
2, 2
(kPa g
cat
s mol
1
) (J mol
1
) (g
cat
s mol
1
) (J mol
1
)
Estimate 7.20 10
6
1.25 10
5
5.04 10
3
2.50 10
5
Interval 1.19 10
6
0.33 10
5
3.66 10
3
1.70 10
5
o
2
r
= 0.00658 n = 85 1
c
= 1041 K
Parameter correlation matrix
0
1, 1
0
2, 1
0
1, 2
0
2, 2
0
1, 1
1
0
2, 1
0.0348 1
0
1, 2
0.8362 0.1826 1
0
2, 2
0.4862 0.6029 0.8392 1
Fig. 7. Reconciliation plot for model II (Eq. (28)) when t to 85 exper-
imental observations collected over 20 wt% Ni}:-alumina catalyst. Data
were collected over a temperature range of 727855

C, a molar SMR
range of 1.36.8 and reaction pressure range of 20002700 kPa.
conversion of methane and those predicted using the
least-squares parameter estimates (Table 3) can be found
in Fig. 8.
When the results of the parameter estimation for the
20 wt% Ni/:-alumina catalyst are inspected (Table 2), it
can be seen that the four parameters of Model II are all sig-
nicant at the 95% condence level. In addition, the repa-
rameterization and temperature centering were successful
in reducing the overall correlation between the parameters
to very moderate levels. Only the pre-exponential factor,
0
1, 2
, shows some degree of correlation with its associated
activation energy, 0
2, 2
, and the pre-exponential factor 0
1, 1
both at the level 0.84. From this it can be concluded that
the model is not overparameterized as would be the case if
one or more parameters were not signicant and/or highly
correlated (i.e. correlation near 1.0).
Inspecting the results of the parameter estimation for the
4 wt% Ni}:-alumina catalyst (Table 3), it can be seen that
three of the four parameters of Model II are signicant at
the 95% condence level. As with the 20 wt% Ni}:-alumina
catalyst, the reparameterization and temperature centering
were successful in reducing the overall correlation be-
tween the parameters to very moderate levels. However, the
pre-exponential factor, 0
1, 2
, once again demonstrated the
highest degree of correlation but in this case the correlation
is primarily with the pre-exponential factor 0
1, 1
. The level
of the correlation was estimated to be at the level 0.99. It is
this high degree of correlation that leads to the large 95%
condence interval on parameter 0
1, 2
.
Previously, it was noted that no statistical dierence could
be found in the behavior of 4 and 20 wt% Ni}:-alumina
catalysts in terms of catalytic activity, stability of activity
with time-on-stream and coking activity (Jarosch, 2000; El
Solh et al., 2001). At the root of this similarity in behavior
was the fact that the relationship between bulk metal load-
ing on the catalyst and metal dispersion led to both cata-
lysts having similar available metal surface areas, 0.416 and
0.406 m
2
}g
cat
for the 4 and 20 wt% Ni}:-alumina catalysts,
respectively. Once again, this similarity is reected in the
parameter values.
In describing the data collected, Model II was not overpa-
rameterized, however, the possibility exists that the model
is underparameterized. This is to say that the experimental
system is displaying a behavior not accounted for in the
model. Specically, Model II did not accumulate all the
probability but Models IV and V retained a relatively stable
residual probability throughout the discrimination process.
Such a result indicates one or more of the adsorption terms in
Models IV and V may contribute signicantly to the model.
If this is correct, Model II may be underparameterized
K. Jarosch et al. / Chemical Engineering Science 57 (2002) 34393451 3449
Table 3
Estimates for the parameters in Model II for data collected over 4 wt% Ni}:-alumina catalyst including linearized 95% condence intervals and parameter
correlation
0
1, 1
0
2, 1
0
1, 2
0
2, 2
(kPa g
cat
s mol
1
) (J mol
1
) (g
cat
s mol
1
) (J mol
1
)
Estimate 8.06 10
6
1.41 10
5
6.61 10
3
2.57 10
5
Interval 3.66 10
6
0.51 10
5
7.75 10
3
1.33 10
5
o
2
r
= 0.00518 n = 52 1
c
= 1036 K
Parameter correlation matrix
0
1, 1
0
2, 1
0
1, 2
0
2, 2
0
1, 1
1
0
2, 1
0.3565 1
0
1, 2
0.9857 0.3229 1
0
2, 2
0.7085 0.3028 0.7750 1
Fig. 8. Reconciliation plot for model II (Eq. (28)) when t to 52 ex-
perimental observations collected over 4 wt% Ni}:-alumina catalyst. Data
were collected over a temperature range of 718850

C, a molar SMR
range of 1.23.8 and reaction pressure range of 20002700 kPa.
resulting in residuals that are not randomly distributed and
a residual sum that is inated.
Lack-of-t due to underparameterization can be observed
in a number of manners. A qualitative assessment can be
made by inspecting a residual or reconciliation plot such
as that presented in Figs. 7 and 8. If a signicant eect
is not included in the model, data points may cluster in
horizontal bands. This banding is a result of changes in the
observed conversion caused by an independent variable not
included in the model. Vertical banding can be symptomatic
of overparameterization. Neither of these eects can be seen
in the reconciliation plots (Figs. 7 and 8).
A quantitative assessment of underparameterization can
be made by inspecting the information content of the resid-
uals. If the model ts the data, that is to say, there is no
information left in the residuals, they should be normally
distributed with an expected value of zero. This assumption
can be tested by comparing the sum of the squared values
of the normalized residual, Q, to the value of the cumula-
tive ,
2
distribution with the same degree of freedom as the
residuals. If the model is underparameterized, the sum of the
squared residual will be inated and Q will be greater than
,
2
. If this is the case, the null hypothesis, that the model
has the correct number of parameters, can be rejected and
the alternative hypothesis, that the residuals are not nor-
mally distributed (i.e. the model is underparameterized) can
be accepted. The sum of the squared normalized residuals
for Model II when it was t to the data acquired over the
20 wt% Ni}:-alumina catalyst, Q, ( 5.15) was found to be
less than the value of the inverse cumulative ,
2
distribu-
tion ( 103) evaluated at 0.95 with 81 degrees of freedom
(number of observations less than the number of parame-
ters). Thus, the null hypothesis can be accepted, the Model
II adequately describes the data acquired over the 20 wt%
Ni}:-alumina catalyst and the residuals are not inated due
to underparameterization.
When the same test was performed for the residuals from
Model II t to the data acquired over the 4 wt% acquired
over the 20 wt% Ni}:-alumina catalyst the value of Q was
found to be 2.92. The value of the inverse cumulative
,
2
distribution evaluated at 0.95 with 48 degrees of free-
dom was found to be 65.2. From this it was concluded
that Model II was not under parameterized when t to the
observations made over the 4 wt% Ni}:-alumina catalyst.
Model II was parameterized based on the assumption
that the adsorption of methane would follow a Langmuir
isotherm as follows:
r
CH
4
=
kK
A

CH
4
1 + K
A

CH
4
=

CH
4
[
1
kK
A
+
1
k

CH
4
]
=

CH
4
0

1
+ 0

CH
4
. (34)
3450 K. Jarosch et al. / Chemical Engineering Science 57 (2002) 34393451
Based on this form (Eq. (34)), the sign of 0
1, 2
, the inverse
of the rate constant for methane consumption, is expected to
be negative. The sign of 0
1, 1
is also expected to be negative.
If Tables 2 and 3 are consulted, it can be seen that the sign
of 0
1, 2
was found to be negative but that the sign of 0
1, 1
was
found to be positive.
A negative apparent adsorption constant can be explained
if the following isotherm is considered:
[ =
K
A

CH
4
1 + (K
A
o)
CH
4
. (35)
In Eq. (35), when the value of K
A
is much larger than the
value o, a typical concave Langmuir chemisorption isotherm
is the result. When the value of K
A
is close to the value of
o the isotherm approaches a straight line. When the value
of K
A
is much less than the value of o a convex isotherm of
type III, is the result. Type III isotherms are found in cases
where physisorption, the adsorption of multiple species per
site, occurs below the saturation vapor pressure. Given the
parameterization used here (Eq. (34)), a negative apparent
adsorption constant would result if K
A
o.
In general, to have physical meaning, the value of o should
be taken as the inverse of the saturation vapor pressure for
the species under consideration. In this case the value of o
appears to be substantially larger than that if calculated from
the saturation vapor pressure. This is likely due to the fact
that, under the conditions of temperature and pressure used
in this study, methane readily reacts with the surface of the
nickel crystal (Eqs. (3) and (4)) producing active carbon.
This active carbon is free to participate in the steam reform-
ing reaction but may also form reactive coke. Clustering of
active carbon species as coke can explain high surface cov-
erage at pressures removed from saturation.
12. Conclusions
Based on the results gathered during the present study,
the following conclusions can be drawn:
(a) The use of a statistical criterion such as the BoxHill
function is a powerful tool for the design of experiments
that optimizes eort expended to information acquired,
in this case allowing for the discrimination between six
dierent plausible models with as few as six sequential
experiments in addition to those used to make initial the
parameter estimates.
(b) Results of the model discrimination indicate that the ad-
sorption of methane plays an important role in determin-
ing the observed rate of methane consumption during
the steam reforming of methane in the CATFORMER
reactor.
(c) Previous observations (Jarosch, 2000; El Solh et
al., 2001) on the behavior of the 4 and 20 wt%
Ni}:-alumina catalysts led to the conclusion that they
should possess similar kinetic parameters. This was con-
rmed when kinetic parameters of Model II were eval-
uated using large data sets collected over both catalysts.
(d) Based on the estimated value of the parameters, the
adsorption behavior of methane appears to follow an
isotherm of type III. This is indicative of physisorption
stemming from the presence of more than one active
carbon species per site at pressures well below the sat-
uration vapor pressure for methane.
Notation
I (i:)) expected value of odds in favor of i over )
J(i, )) I (i:)) +I ():i), Kullbacks discrimination function
k rate constant for the reforming reaction,
mol g
1
cat
kPa
1
s
1
k
a
, k
d
adsorption/desorption rate constants for hydrogen
k
e
, k
dis
emergence/dissolution rate constants for atomic
hydrogen
K
A
adsorption constant for methane, kPa
1
K
J
value of the BoxHill discrimination function, di-
mensionless
K
1
equilibrium constant for steam reforming, kPa
2
K
2
equilibrium constant for water gas shift, dimen-
sionless
N number of moles, mol

i
partial pressure of species i, kPa
(,) probability density function for ,
P pressure, kPa
P
Sat
saturation vapor pressure, kPa
P

relative pressure, P
1
Sat

P
(n)
r
prior probability of model r after n experiments
Q sum of squared normalized residuals
r rate of consumption, mol g
1
cat
s
1
R universal gas constant, J mol
1
or kPa cm
3
mol
1
K
1
s
2
e
experimental variance measured by performing re-
peat experiments
SMR molar steam-to-methane ratio, dimensionless
1 temperature, K
t total number of models proposed, dimensionless
J
R
reactor volume, ml
w mass of catalyst, g
x
(n)
matrix containing settings of the independent vari-
ables for model/experiment
x
(n+1)
vector containing the settings of the independent
variables of model Y
r
(X, x) selected by discrimi-
nation criterion after n observations
,

value of an observed response

Y
(n)
value of experimental observation made using
settings of the independent variables in x
(n)

Y
(n)
r
expected value of nth response model Y
r
(X, x
(n)
)

Y
(n)
r
predicted value of nth response of model Y
r
(X, x
(n)
)
K. Jarosch et al. / Chemical Engineering Science 57 (2002) 34393451 3451
Greek letters
o Asymptote in generalized isotherm, kPa
1
c
REF
Extent of the methane reforming reaction, mol
c
WGS
extent of the water gas shift reaction, mol
c
EXP
experimental error, Y
(n)

Y
(n)
, dierence between
the observed value (experimental observation) and
the expected value of the model
X vector of parameters for model estimated using n
observations
0
i
parameter in power law rate model, dimensionless
0

i
generalized parameter following an Arrhenius tem-
perature relationship
0
1, i
pre-exponential factor for generalized parameter 0

i
0
2, i
activation energy for generalized parameter
0

i
, J mol
1
o
2
r
variance of model prediction

Y
(n)
r
o
2
Y
variance of observed response, Y
(n)
, estimated us-
ing s
2
e
as measured by performing experimental re-
peats
[ surface coverage, dimensionless
,
2
Chi-squared value of cumulative distribution
Subscripts/superscripts
C center value
(n) evaluated after n number of experiments
r model number
1 total
t total number of models
CH
4
methane
H
2
O water/steam
H
2
hydrogen
CO carbon monoxide
CO
2
carbon dioxide
0 initial
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