The Reaction Network for the Oxidation of Propylene

_ _
Over a Bismuth Molybdate Catalyst
H. S. TAN, J . DOWNIE, AND D. W. BACON
Department of Chemical Engineering, Queens University, Kingston, Ontario, K7L 3N6
An initial-rate study was conducted to determine the kinetics of the oxidation of acrolein over a bismuth molybdate
catalyst. The results were combined with results from a previous initial-rate study of propylene oxidation on the same
catalyst to develop a quantitative description of the reaction network for propylene oxidation.
The redox steady-state model with half-order in oxygen which provided the best fit to the propylene oxidation data
also provided the best fit to the acrolein oxidation data. The disappearance of propylene occurs through parallel reactions to acrolein, carbon oxides, and acetaldehyde, with subsequent oxidation of the acrolein to carbon oxides.

Une Ctude de vitesse initiale a it6 effectuCe afin de determiner la cinktique de Ioxydation de IacrolCine sur un catalyseur
de rnolybdate de bismuth. Les rksultats ont CtC combinks h des donnCes antCrieures sur ICtude de vitesse initiale de
Ioxydation du propyltne sur le rn&rnecatalyseur pour rnettre au point une description quantitative du rCseau de rtaction
pour Ioxydation du propyltne.
Le modtle permanent doxydo-rCductiondun demi-ordre en oxygtne qui concorde le mieux avec les donntes doxydation du propykne, est celui qui prCsente Cgalernent la rneiUeure concordance avec les donnks doxydation de Iacroltine.
Le propyltne disparait lors de rCactions paralleles produisant Iacroltine, les oxydes de carbone et IacCtaldChyde,suivies
de Ioxydation de IacrolCine en oxydes de carbone.
Keywords: catalytic oxidation kinetics, reaction networks, statistical design, propylene oxidation, acrolein oxidation.

he overall objective of this research was to develop a

quantitative description of the reaction network for the
oxidation of propylene over a bismuth molybdate catalyst.
An initial-rate study of propylene oxidation was completed
first (Tan et al., 1988), using a joint criterion design for
model discrimination and parameter estimation (Tan et al.,
1989). The present paper reports the results of the final two
stages of the work, namely, an initial-rate study of the oxidation of the intermediate acrolein, and the combination of
propylene and acrolein results to develop a quantitative
description of the reaction network.
The first point to be resolved when modelling a reaction
network is whether the individual steps can be adequately
described by the same kinetic model form. Different model
forms can be used for each step but the network model is
simpler if this is not necessary. In the case of propylene and
acrolein there are reports of different models being required
for each (Cartlidge et al., 1975, using bismuth molybdate,
and Forissier et al., 1979, using iron molybdate).

Experimental
The main features of the apparatus for the acrolein oxidation study were the same as in the earlier work on propylene oxidation (Tan et al., 1988). The only change was in
the feed system for acrolein. Liquid acrolein was fed into
the reactor system using a variable speed syringe pump. The
pump was capable of producing flows to within 2 % and mass
balance checks during the runs were within 2.5 %. Acrolein
was vaporized from the syringe needle by a hot stream of
nitrogen and oxygen. The products from the reactor were
directed to a gas chromatograph for analysis.
Experimental runs were carried out at 325, 350, and
365C.

Results and Discussion

KINETICSOF ACROLEIN OXIDATION
The joint criterion design strategy which was used for the
propylene oxidation study (Tan et al., 1989) was employed
412

to direct the acrolein experimental program at 350C. The

objective was to discriminate among four steady-state models
and improve the precision of the parameters.
The four rival rate models which were tested are as
follows:

Model 1 re = k, k, C, C,l(k, C,
Model 2 re

+ n k, C,) . . . . . . . .

(1)

k, k, C,2C,/(k, COI2 n k, C,) . . . . . (2)

+ n k, Cell2) . . . .
C,l2C,121(kaCo12
+ nk,C,2)

Model 3 re = k, k,C,C,2/(k, C,

(3)

Model 4 re

(4)

k,k,

Model 1 is the basic Redox Steady-State Model. Model

2 is the Redox Steady-State Model with half-order in oxygen
which was found in the previous study to be the best model
for the oxidation of propylene (Tan et al., 1988). Model 3
was included since a half-order dependency on acrolein was
reported by Cartlidge et al. (1975). Model 4 was included
to examine half-order in oxygen with half-order in acrolein.
Seven runs were carried out at 350C to obtain preliminary estimates of the rate parameters and model probabilities. Then the joint design criterion proposed by Hill et al.
(1968), and discussed by Tan et al. (1989), was used to select
the conditions for each successive run.
The procedure was continued until Run 13. After Run 13,
sufficient model discrimination had been achieved to regard
Model 2 as the best model, and considerable improvement
in the precision of the parameter estimates in Model 2 had
also been accomplished.
Table 1 summarizes the results of the application of the
joint criterion design strategy. It shows that following the
initial run stage, model discrimination was accomplished by
six further designed runs with Model 2 emerging as the best
model. At the same time the precision of the parameter estimates in Model 2, as measured by E;In, was progressively
improved as more designed runs were performed. Compared
with the results from the seven initial runs, the overall
parameter precision showed an improvement of 11% after
Run 8 and an improvement of 60% by Run 13.

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 67,JUNE, 1989

TABLE1
Summary of Results of Joint Criterion Design for Acrolein Oxidation
Run No.

PI

p2

p3

p4

E;X lo7

7
8
9
10
11
12
13

0.005
0.001
O.OO0
O.OO0
O.OO0
O.OO0
O.OO0

0.229
0.330
0.346
0.934
0.959
0.918
0.995

0.341
0.419
0.428
0.052
0.034
0.064
0.003

0.425
0.251
0.225
0.014
0.008
0.018
0.002

2.16
1.92
1.73
1.10
0.97
0.92
0.86

At the end of the design program, fifteen additional

undesigned runs were performed. The objectives of these
runs were: (i) to monitor the catalyst activity for the next
set of experiments (an investigation of the effect of temperature), (ii) to test the adequacy of the fitted model by performing runs in unexplored portions of the design region,
and (iii) to replicate some of the previous runs so that an
estimate of pure error variance could be obtained. The actual
experimental conditions at which these runs were carried out
at 350C are shown in Figure 1 .
Model 2 was fitted to the total data set of 28 runs at 350C
with percentage conversion of acrolein as the measured
response variable. The least squares estimates of k, and k,
in Model 2 are given in Table 2 along with their associated
approximate 95 % confidence intervals. The point estimate
and the associated 95% confidence limits of k, at 350C are
( 1 . 6 7 f 0 . 2 0 ) ~ 1 0 -(mmol
~
L)*/(g . s). Since the same
model form has been found to provide an adequate fit for
both the propylene and the acrolein reactions, and the same
catalyst was used in both studies, the common parameter k,
should have the same value at the same temperature (350C).
The estimate of k, obtained in the propylene oxidation study
~ et al., 1988), which agrees
was ( 1 . 6 5 * 0 . 1 3 ) ~ 1 0 -(Tan
very closely with the value obtained in this study and provides further support for Model 2.
The predicted and measured rates of acrolein oxidation as
functions of oxygen and acrolein concentrations are shown
in Figures 2 and 3. The solid lines in these figures represent
the predicted rates.
The adequacy of the fitted model was checked by examination of residual plots and no significant patterns were found
in these plots, indicating an acceptable fitted model. An
approximate lack of fit test (Draper and Smith, 1981) was
also carried out. The results of analysis of variance show
that the ratio of the mean square due to lack of fit to that
due to pure error (with the associated degrees of freedom
of 19 and 7, respectively) was 1.98. This is substantially
which is
lower than the corresponding value for F19,7,0,05,
3.45. Thus the fitted model does not show significant lack
of fit at the 5 % level of significance.

2.3
25

15, 17,
26, 27,23,

14
18

1131

16

28

20

19,21,24

22

0.2

I
0.4

0.6

0.8

1.o

1.2

ACROLEIN CONCENTRATION (mmollL)

Figure 1 - Experimental runs for acrolein oxidation at 350C

o Statistically designed runs.

Twenty-three additional runs were carried out at 325 and

365 C to study the temperature effects on the kinetics of
acrolein oxidation. Thus a total of 5 1 experiments were performed for acrolein oxidation. These data were used to check
the model by verifying that the rate constants in Model 2
follow an Arrhenius-type temperature dependence.
Model fitting for the 23 additional runs was done by
analyzing the isothermal data sets at 325 and 365 Cindividually. The results are also shown in Table 2, where the point
estimates of k, and k, along with their corresponding
individual 95 % confidence intervals are listed. The residuals
obtained from the fitted model were plotted against the
predicted response and the operating variables. No systematic
patterns in the residual plots were found, thus indicating the
model is adequate. An Arrhenius plot of the estimated values

TABLE2
Estimates of Rate Constants for Acrolein Oxidation
Temperature (C)
No.
325
350
365
[ k , ] = (mmol . L)Z/(g . s)
[k,I = L4g * s)

of runs
13
28
10

k
(7.44+1.61)~10-~
(1.67k0.20)x
(2.50*0.66)X

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 67, JUNE, 1989

(6.77*1.21)X10-4
(1.29f0.11)x10-3
( 1.95*0.49) x 10 - 3

413

-5.1

-0- k, acrolein

-A-

-5.4

k, acrolein

-5.7
-6.0
x

z -6.3
4

-6.6
CONCENTRATION
0 0.3 mmoliL

-6.9

-7.2
0.0

1.5

3.0

4.5

6.0

'1

..
z

-7.5

OXYGEN CONCENTRATION (mmollL)

Figure 2 - Rate of acrolein oxidation as a function of oxygen concentration at 350C.

0.6

.X

\
4

-7.8

1.50

1.53

1.56

1.59

1.62

1.65

1.68

in ( ~ - 1x) 103
Figure 4 - Arrhenius plots of rate constants for acrolein oxidation.

a, Ea

= (2.76f 11.9) X lo5

E, = 97.9f11.3
A, = (9.67f35.2)x103
!a

ke = 82.0k9.6

0 0.5 mmoWL

A
0

0.0

0.2

0.4

0.6

1.2rnmol/L
2.9 mmol/L

0.8

1.0

1.2

1.4

ACROLEIN CONCENTRATION (mmollL)

Figure 3 - Rate of acrolein oxidation as a function of acrolein concentration at 350C.

of k, and k, is shown in Figure 4. The bars shown in the
figure represent the approximate 95 % confidence intervals
for the rate constants. The rate constants follow the Arrhenius
relationship closely. The estimates of rate constants k, and
k, from the propylene oxidation study (Tan et al., 1988) are
also shown in Figure 4 for comparison. The estimates of k,
from the two oxidation studies lie on the same straight line
on the Arrhenius plot. This extends the argument made above
on the basis of k, values at 350C and provides further support for Model 2.
The data were then re-analyzed using the direct procedure
(Pritchard and Bacon, 1975) which involves simultaneous
fitting of all the nonisothermal data with Arrhenius temperature dependence incorporated in the model. The parameter
estimates, their associated individual 95 % confidence
intervals, and their pairwise correlations are as follows:
414

a,

Ee
1 0.9998 -0.896 -0.894
1
-0.893 -0.892
1
0.9998
1

The 95% confidence intervals for both A, and A, include

zero. As discussed in the previous paper (Tan et al. 1988),
the poor precision of the estimates of A, and A, is due to
the high correlations between the Arrhenius parameter
estimates.
The Arrhenius parameter estimates were used to generate
the straight lines in Figure 4. The plot shows close agreement between the results from the isothermal analyses and
those from the direct procedure. The plot also shows the
agreement between the value of E, (97.9f11.3 kJ/mol)
from this study and that from the propylene oxidation study
(92.0f9.2 kJ/mol) (Tan et al., 1988). Examination of
weighted residual plots did not show any evidence of systematic behavior among residuals, and therefore there is no
reason to doubt the adequacy of the fitted model.

REACTIONNETWORK FOR PROPYLENE OXIDATION

The products obtained from propylene oxidation were:
acrolein, acetaldehyde, carbon dioxide, and carbon
monoxide, (Tan et al., 1988). The ratio of carbon dioxide
to carbon monoxide was found to be the same for all experiments at the same temperature (50:l at 350C), and the
carbon oxides were combined and treated as a single product.
The selectivity to each product was plotted against propylene conversion. The product distribution was constant over
the range of experimental conditions, suggesting that the
products were formed in parallel reactions from propylene.
The products from acrolein oxidation were carbon dioxide
and carbon monoxide. The absence of acetaldehyde in the
products of acrolein oxidation indicates that acetaldehyde

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 67, JUNE, 1989

was formed directly from propylene. On the basis of the

above qualitative interpretations, the following reaction network is suggested for the initial stage of the oxidation of
propylene:

kK
- 1

intermediate (acrolein) is involved in the rate expressions.

The approach used here is to assume the reaction step 2 3
is insignificant in the initial rate study of propylene oxidation. This simplifies the reaction network, and the .network
model becomes:

acrolein
k23

propylene

carbon oxides

acetaldehyde
Using the extended form of steady-state model with halforder in oxygen, the rates of formation of the products in
the network can be expressed as:

(kI2C1- kZ3C2)S . . . . . . . . . . . . . . . . . . . . . . .

r2

r3

= (k13CI

+ k23C2)S

.......................

(6)

r4 = k14CIS. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

(7)

where

+ n23k23C21

..............................

+n,,k,,)C,] . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

(5)

(8)

r2, r3 and r4 are the rates of formation of acrolein, carbon

oxides, and acetaldehyde respectively; and C, Cl and C2
are the concentrations of oxygen, propylene, and acrolein
respectively. Also, nI2 and k12 are the stoichiometric
number and rate constant associated with the reaction of
propylene to acrolein. Similar notation applies to the other
three reactions: 13 for reaction of propylene to carbon oxides,
14 for propylene to acetaldehyde, and 23 for acrolein to
carbon oxides.
To describe the reaction network quantitatively, we need
the estimates of the five rate constants in the model: k,, kI2,
k I 3 ,k14, and k 2 3 . The value of k, has been estimated for the
oxidation of propylene at 350, 375, and 390C, (Tan et al.
1988), and for the oxidation of acrolein at 325, 350, and
365C, from the data given above. Estimates of k23,
denoted as k, in Equation 2, have also been obtained from
the acrolein oxidation study at 325, 350, and 365C. The
problem now is to obtain the estimates of the rate constants
for the three parallel reactions from propylene: kI2, k13, and
k14. In the initial-rate study of propylene oxidation described
in the previous paper (Tan et al., 1988), these three rate constants were lumped into a single rate parameter, k,.
The initial rate data from the propylene oxidation study
are not suitable for fitting the network model represented
by Equations 5 to 8 because the concentration C2 of

(1 1)

Parameter estimation was performed by fitting the parallel

reaction model (Equations 9 to 11) to the multiresponse data
for propylene oxidation using the Box-Draper determinant
criterion (Box and Draper, 1965).
The results from the parallel reaction model fitting are summarized in Table 3 where the estimates of the rate constants
and their associated individual 95 % confidence intervals are
shown. The results of an approximate lack-of-fit test on each
response indicate that there is no serious concern about model
inadequacy. Figures 5, 6, and 7 show the plot of observed
versus predicted conversions for the fitted model. Arrhenius
plots of the parameter estimates are shown in Figure 8. The

-8
2

2
rn

1.5

1.4

1.3

1.2

1.1

1.0

K 0.9
W

0.8

8 0.7
fi

>
~e
w
m

0.6 0.5

0.4

0.3

0.0

PROPYLENE CONVERSION
0

lo acmlein

to carbon oxides

d
0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

PREDICTED CONVERSION (h)

Figure 5 - Observed versus predicted conversions for the parallel

reaction model at 350C.

TABLE3
Estimates of Rate Constants for the Parallel Reaction Model
350
(1.67 k0.13) x
fl2
(2.19+0.14) x
1 3
(2.70k0.18)~10-~
4 4
(2.73k0.21)~
[ k , ] = (mmol . L)2/(g. s)
where i j = 12, 13 and 14
[ k O ] = L/(g . s)

Temp^ (C)
k

375
(3.16k0.42) X
(3.86k0.37) X
(2.94k0.31)X
(4.5250.55)X lo-

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 67, JUNE, 1989

390
(4.62k0.46) x
(5.38k0.35) x
(2.70k0.27) x
(6.28k0.71) x

415

-5
1.8
1.6

-6

1.4

&

-7
1.2

P
v)

g
>

1.0

0
0 0.8

-8

8
>
fi 0.6

-9

v)

0.4

o'2

0.0

to acrolein

A
0

to carbon oxides

0.3

0.6

1.2

0.9

1.5

PREDICTED CONVERSION

1.8

1.45

("Yo)

Figure 6 - Observed versus predicted conversions for the parallel

reaction model at 375C.

z
0

7n r

0 1.2

I
I

10

OOai

fi 0.9

v)

0.0

oxides

2ot

1.5

0.3

1.60

0 0.6

1.55

in (K-1) x 103
Figure 8 - Arrhenius plots of rate constants for parallel reactions.
A carbon

2.4

1.50

z 2.1'
v
p
1.8
W
>

l o acetaldehyde
-1 1

0.0

3.0
2.7

x
x'

-10

1
,
0.0

B
/

000

001

003

004

005

006

007

ACROLEIN CONCENTRATION (rnmol/L)

lo acrolein

A
0

002

Figure 9 - Selectivity as a function of acrolein concentration at

350C. Propylene concentration = 1.5 mmollL.

to carbon oxides
to acetaldehyde
I

0.5

1.o

1.5

2.0

2.5

3.0

PREDICTED CONVERSION (X)

Figure 7 - Observed versus predicted conversions for the parallel

reaction model at 390C.

Conclusions

straight lines in Figure 8 were again obtained using the direct

procedure (Pritchard and Bacon, 1975) in which the parallel
reaction model was fitted to all of the nonisothennal data
simultaneously.
A further test of this network was made by carrying out
a number of propylene oxidation runs at 35OoC, and at higher
conversions (9-1 1%) where the consecutive oxidation of
acrolein to carbon oxides was expected to become significant. The selectivity data from these runs were compared
with those predicted using the rate constant estimates given
in Tables 2 and 3. The results indicated that the agreement
between the measured data and the predictions is good.
Figure 9 shows these results. The lines shown in Figure 9
are the predictions. The data on the left of the broken vertical line are the initial-rate data from the earlier study of
propylene oxidation (Tan et al., 1988) and those on the right
are the network checking runs.

The kinetics of acrolein oxidation over silica-supported bismuth molybdate can be described satisfactorily by the
steady-state model with one-half order in oxygen. The estimates of the rate constant for re-oxidation of the catalyst,
k,, and the corresponding activation energy, E,, were found
to agree with those obtained from the propylene oxidation
study (Tan et al., 1988). This study again demonstrated the
effectiveness of the joint criterion design strategy in achieving
the dual objectives of model discrimination and precise
parameter estimation.
Using a model fitting approach, it was shown that the initial disappearance of propylene occurs through parallel reactions to acrolein, carbon oxides and acetaldehyde. An
extended steady-state model satisfactorily described the three
parallel reactions. Based on the results from the analysis of
the parallel reaction data and the study of acrolein oxidation, a quantitative description of the reaction network for
propylene oxidation was developed.

416

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 67, JUNE, 1989

Acknowledgement

Superscript

The financial support of the Natural Sciences and Engineering

Research Council of Canada is gratefully acknowledged.

References

Nomenclature
A,

= Arrhenius pre-exponential factor for oxygen incorpo-

A,

c,
c,
ci
E,
E,
E2-1/2

= estimated value

ration, (mmo~. L)//(g . s)

Arrhenius pre-exponential factor for acrolein reaction, L/(g . s)
= concentration of acrolein, mmol/L
= concentration of oxygen, mmol/L
= concentration of species i, mmol/L
= activation energy for oxygen incorporation, kJ/mol
= activation energy for acrolein reaction, kJ/mol
= size of joint confidence region for k, and k, in
Model 2
value of the F distribution
rate constant for oxygen incorporation,
(mmol . L)/2/(g s)
rate constant for acrolein reaction, L/(g . s)
rate constant for the reaction of species i to speciesj,
L/(g * s)
rate constant for propylene reaction, L/(g . s)
stoichiometric number, moles oxygen required/mole
acrolein reacted
number of moles of oxygen which react with one
mole of species i to produce speciesj
posterior probability associated with model i
rate of disappearance of acrolein, mmol/(g * s)
net rate of formation of product i, mmol/(g * s)
temperature, K
f

Box, G. E. P. and N. R. Draper, The Bayesian Estimation of

Common Parameters from Several Responses, Biometrika 52,
355-365 (1965).
Cartlidge, J., L. McGrath and S. H.Wilson, Mathematical Modelling of Olefin Oxidation over Oxide Catalysts: Part I1 - Propene to Acrolein and Carbon Oxides over Bismuth Molybdate,
Trans. Instn. Chem. Engrs. 53, 117-124 (1975).
Draper, N. R. and H. Smith, Applied Regression Analysis
(Second Edition), John Wiley & Sons, New York (1981).
Forissier, M., J. B. Gros and C. Pralus, Modtles Cinetiques et
Mecanisme de IOxidation Catalytique du Propene en Presence
de Molybdate de Fer, Can. J. Chem. Eng. 57,707-715 (1979).
Hill, W. J., W. G. Hunter and D. W. Wichern, A Joint Design
Criterion for the Dual Problem of Model Discrimination and
Parameter Estimation, Technometrics 10, 145-160 (1968).
Pritchard, D. J. and D. W. Bacon, Statistical Assessment of Chemical Kinetic Models, Chem. Eng. Sci. 30, 567-574 (1975).
Tan, H. S., J. Downie and D. W. Bacon, The Kinetics of the
Oxidation of Propylene over a Bismuth Molybdate Catalyst,
Can. J. Chem. Eng. 66, 611-618 (August, 1988).
Tan, H. S., D. W. Bacon and J. Downie, Sequential Statistical
Design Strategy in a Kinetic Study of Propylene Oxidation, Can.
J. Chem. Eng., in press (1989).
Manuscript received April 18, 1988; revised manuscript received
August 15, 1988; accepted for publication September 22, 1988.

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417