2652

Ind. Eng. Chem. Res. 1992,31, 2652-2660

Modeling the Catalytic Oxidation of n-Butane to Maleic Anhydride in a

Circulating Fluidized Bed Reactor
Todd S. Pugsley,t Gregory S. Patience,*?*
Franco Bermti,* and Jamal Chaoukif
Department of Chemical and Petroleum Engineering, University of- Calgary, 2500 University Dr. NW,Calgary,
Alberta, Canada T2N lN4, and Departement de Genie Chimique, Ecole Polytechnique de Montreal, C.P. 6079,
Succursale A, Montreal, Quebec, Canada H3C 3A7
A circulating fluidized bed (CFB) is a gas-solid contactor in which solids are transported vertically
in a riser by a high-velocity gas stream. CFB reactors are becoming increasingly attractive for
conducting specific catalytic reactions. The catalytic oxidation of n-butane to maleic anhydride
(MAN) has been simulated for a ao-m-high, 30-cm-diameter CFB to investigate the reactor performance under various operating conditions. The comprehensive simulation combines a core-annular
hydrodynamic model of the CFB with a fixed bed reaction kinetics model. Reactor performance
is evaluated in terms of n-butane conversions, product yields, and selectivity. The simulation can
easily accommodate different reaction kinetics and therefore can be used to predict the performance
of a CFB reactor for any catalytic process.
1. Introduction
Circulating fluidized bed (CFB) reactors are typified by
riser superficial gas velocities normally in the range of 2-10
m/s, compared with less than 1 m/s in conventional
bubbling beds. At these gas velocities, solids throughput
is very large while reactor diameter is minimized and gas
residence time is short. Solids carried out of the riser are
separated from the gas by cyclones and are returned to the
bottom of the riser by a vertical standpipe.
The traditional uses of a CFB have been mainly in
noncatalytic proteases, such as the combustion of low-grade
fossil fuels. However, the unique design of a CFB also
makes it attractive as a catalytic reactor. Figure 1 is a
schematic of a CFB catalytic reactor for the partial oxidation of n-butane to maleic anhydride. Solid catalyst
particles are injected from the standpipe and are transported vertically in the high-velocity gas stream containing
n-butane. The reaction occurs along the riser length, and
the catalyst is rapidly deactivated. The solids and gas exit
from the riser via a smooth elbow and are separated in the
cyclone. The product stream containing maleic anhydride
and other gases is sent downstream for purification. The
deactivated catalyst particles are stripped of any carbonaceous material by an inert such as nitrogen or steam and
sent on to the regenerator section where contact with air
oxidizes the catalyst surface once again. The regenerated
catalyst is gravity fed to the standpipe where it moves to
the base of the riser for reinjection into the riser reaction
zone.
Contractor and Sleight (1987) discussed the inherent
advantages of a CFB in the catalytic partial oxidation of
n-butane to maleic anhydride (MAN). These include
separate catalyst reduction and oxidation zones in the riser
and standpipe, respectively, low catalyst inventory, and
uniform temperature throughout the riser (elimination of
hot spots). Since the catalyst may be regenerated in a
separate vessel, oxygen requirements in the feed are
minimal, thus leading to high selectivity to MAN and a
more concentrated product stream. Contractor and
Chaouki (1990) reviewed other potential uses for the CFB
as a catalytic reactor.

* To whom correspondence should be addressed.

University of Calgary.
t Ecole Polytechnique de Montreal.
*Presentaddress: E. I. du Pont de Nemours & Co.,Wilmington,

DE.

The interest in the partial oxidation of n-butane to

maleic anhydride is due to the importance of the reaction
on an industrial scale. For the first 40 years of maleic
anhydride production, the feedstock was benzene (DeMaio,
19801, but due to increasing environmental concerns over
the use of benzene and escalating benzene costa, almost
all US.plants have switched to n-butane. Annual MAN
production in the United States is approaching 19OOOO
metric tons and is increasing by approximately 6% per
year to meet increasing demand (Irving-Monshaw and
Kislin, 1989). MAN is used primarily in the production
of unsaturated polyester resins, alkyd resins, and specialty
copolymers. It is also used in the manufacture of agricultural chemicals, as an additive in lubricating oils, and
as a building block for L-aspartic acid, used in making
NutraSweet. The high demand for MAN combined with
the interest in the circulating fluidized bed technology for
its production makes a comprehensive simulation for
predicing reactor performance a valuable tool for industry.
2. Kinetics
2.1. Reaction Kinetics Rate Equations. Intrinsic rate
equations and reaction pathways for the partial oxidation
of n-butane to maleic anhydride (MAN) on a vanadium
phosphorus oxide (VPO) catalyst utilizing a packed bed
experimental reactor have been proposed by Centi et al.
(1985). These expressions were later cited in the work by
Contractor and Sleight (1987) and Patience and Chaouki
(1990). The complete reaction pathway involves both
series and parallel reaction steps:

n-C4Hio

- MAN

COZ

(1)

n-C4Hlo C 0 2
(2)
The rate equations proposed by Centi et al. (1985) are
(3)
r2 = rCOs= kZc,B
r3

= -rMAN =

k$MAN(CoY/CB6)

(4)
(5)

where rMAN
is the rate of MAN formation from n-butane,
is the rate of C02formation from n-butane, and -rm
? & e rate of maleic anhydride decomposition to C02and
water. The kinetic parameters determined by Centi et al.
(1985) are summarized in Table I.

0888-5885/92/2631-2652$03.00/00 1992 American Chemical Society

Ind. Eng. Chem. Res., Vol. 91, No. 12,1992 2653

/-MALEIC

ANHYDRIDE

7
OFTGAS

proportional to the number of catalytic sites still active.

If q(t) corresponds to the number of deactivated sites at
solids residence time t., and qo to the maximum number
of sites for a totally deactivated catalyst, then the rate of
maleic anhydride (MAN) formation, for example, h o m e s

REGENERATOR

This parallel deactivation is repreaentsd by Smith (1981)

as a simple fmt-order reaction at the catalyst surfam, and
thus the rate of catalyst deactivation, rd, is writtan as

AIR

Integration of eq 7 gives
RISER

STANDPIPE

Subetitution of eq 8 into eq 6 provides the rate of reaction

incorporating catalyst deactivation:

BUTANE

Figure 1. Schematic of a eirculatiag fluidized bed an a catalytic

reactur.

Table I. ginetia Param&-

340

6.230

KB= 2616 mol/L;

(1

for Itate Quntions of Centi et

9.040
@ = 0.2298; 7

0.966

= 0.6345; 6 = 1.151.

Unlike the resulta of other studies (Wohlfaiut and

Hoffman, 1980, Sharma et al, 1991),the catalyst employed
by Centi and mworkera was very selective toward maleic
anhydride. The vanadium present in the VPO catalyst is
the main oxygen carrier, and during the reaction with the
hydrocarbon in the gas phase, certain crystalline phases
in the solid catalyst are transformed via a reduction proceea. This is written in terms of the valence change as V+5
V+. Contractor (1988) found the average oxidation
state of the catalyst to he about 4.1, with a difference of
0.2 in the average oxidation state between the oxidized and
reduced state of the catalyst. This indicates that most of
the active catalyst exists in the V4oxidation state and that
the catalyst surface provides most of the oxygen needed
for the reaction. As discussed by Centi et al. (1988). the
kinetic model of Centi et al. (1985) is indicative of a fresh
catalyst poeaessing large amounts of surface oxygen and
readily forming the V+ crystalline phase. Therefore, the
model of Centi et al. (1985) is appropriate to use for the
modeling of the CFB reador because of the continuous
reiniection of reeenerated &e.. fresh) catalvst from the
vertical standpiie.
22. Catalyst Deactivation Model. The reduction of
the VPO catalvst is an examole of oarallel deactivation.
where the rea&& form prdrxta &d, at the same time;
deactivate the catalyst. The rate of reaction then becomes

b ( t 3 = MAN exp[-at.l
(9)
The solids residence time used in the catalyst deactivation
model is calculated on the basis of the upward solids v e
locity in the core region. Aa a result, it is assumed that
the catalyst deactivation in the core and annular regions
is the same. This is a large simplifying assumption because
the solids present in the annular region will have been in
the riser for a longer period of time due to solids recirculation down the riser walL Furthermore, the solids present
at any point in the riser will have a varied history due to
solids crossflow between the core and annular regions. A
more rigorous formulation would incorporate the solids
residence time distribution (RTD),and more work is required in this area to improve the simulation. The purpose
of this simplified deactivation model was to acknowledge
the deactivation, which is known to be very fast, and to
investigate the importance of the deactivation on reactor
performance.
3. Riser Hydrodynamics
3.1. Riser Flow Structure. The flow pattam of the
solids in the riser of a CFB is extremely complex and is
dependent on many variables. The column diameter,
height, and exit configuration,particle properties, and gas
characteristics all affect the flow structure in the riser.
Visual observation in a riser of circular cross section indicates the existence of a lean suspension of solids in gas
flowing upward in the center of the riser, with a denser
downilow of solids next to the wall. Weinsteii et aL (1986)
and Bader et al. (1988) both observed decreasing radial
voidage profdes in their experimental units,with the most
dramatic decrease occurring very close to the wall. The
radial location of this sudden change in voidage indicates
the interface between the dilute upward flowingregion and
the dense downward flowing region. The CFB riser is also
characterized by a dense, turbulent portion at ita base
where the solids are introduced into the riser from the
standpipe, which becomes leaner as the flow of solids d e
velops and the particles are accelerated to their steadystate upward velocity in the riser.
3.2. Berruti-Kalogerakis Model. Bermti and Kalcgerakis (1989) modeled the CFB riser as behg characterized by a ooreannular type of flow stmctwe, with solids
moving upward in the lean core region and downward in
the dense annular regior.. The model assumes that the
solids move dmnward ii the dense annular region at the

2654 Ind. Eng. Chem. Res., Vol. 31, No. 12,1992

terminal velocity of a single particle, and that the voidage

in the dense annular region is the same as that of a bubbling bed of the solids at minimum fluidization. This
model requires the solids circulation rate, the axial superficial gas velocity, and the average axial riser voidage
profile as inputs.
The average axial voidage profile can be obtained from
an experimentally determined pressure drop profile according to
1dP
eaVg = 1 - P& dx
Equation 10 assumes that the axial pressure drop profile
is due solely to the weight of solids present at any axial
location, ignoring frictional effects at the wall. Arena et
al. (1986) compared the average axial voidage profile
predicted from pressure drop measurement with the profile
obtained from trapped solids weighing along the riser
length. Pressure drop measurements were found to underpredict the average voidage in the riser, and this discrepancy was attributed to the frictional effects of the wall.
They indicated that the small diameter column used
(4.1-cm i.d.) may have enhanced the frictional effects.
Berruti and Kalogerakis (1989) derived the following
expression for the voidage in the core region of the riser:

this acceleration component is not separated from the

pressure drop data, erroneous voidages will be predicted
in the acceleration zone. The voidage predicted from
pressure drop data if the acceleration component is not
separated is referred to aa the apparent voidage, ewp The
voidage predicted once the acceleration component is
separated is called the actual voidage. The acceleration
zone is modeled assuming a predominantly upward flowing
gas-solids suspension. Wong et al. (1992) derived the
following expression for the aparent solids holdup in the
acceleration zone:

where

r = 1 - -1 - e,

The first term on the right-hand side of eq 13 representa

the effect of the acceleration of particles on the observed
preaeure drop, while the gecond term on the rightrhand side
represents the effect of the weight of solids.
In order to evaluate the constant r, the apparent voidage
at the bottom of the riser, q,, must be known. Wong and
co-workers proposed an empirical correlation for eb developed from a regression analysis on a large pool of
published experimental data. For Geldart group A solids
the correlation is
eb

A solids balance over a volume element of the riser resulted

in the following expression for the core radius, r,:

Equations 11 and 12 may be solved simultaneously to

obtain the values of core voidage and core radius at any
axial position along the riser. The limitation of the Berruti
and Kalogerakis model is the requirement of an experimentally determined axial pressure drop profile. Therefore, the model can only be applied to experimental unita
for which the pressure drop profile has been obtained.
3.3. Predictive Model of Wong et al. (1992). Wong
et al. (1992) have recently developed a predictive model
for the average axial riser voidage profile which is used in
conjunction with the Berruti-Kalogerakis model to describe the internal flow structure of a CFB. Given riser
geometry, solids and gas physical properties, solids circulation rate, and superficial gas velocity, the average axial
voidage profile may be calculated along with the core
voidage and core radius, core gas and solids velocity, and
solids interchange coefficienta between the core and annular regions, all functions of axial location along the riser.
This model considers the CFB riser divided into three
sections: an acceleration zone corresponding to the dense
region at the base of the riser, a fully developed flow zone
immediately above the acceleration zone, and a deceleration zone for risers equipped with an abrupt exit geometry.
If the riser has a smooth exit to the cyclone, the fully
developed zone is assumed to extend all the way to the
outlet.
3.3.1. Acceleration Zone. In the dense region at the
base of the riser of a CFB, a fraction of the total measured
pressure drop between the entrance and the start of the
fully developed flow zone can be attributed to the acceleration of the particles to their steady-state velocity. If

(14)

1 - 0

).' uo

= 0.714(

Ps

-0.02628
~ ~ - 0 . 0 7 9 4-0.12016
R~

(15)

This value is substituted into eq 13 with x = 0. The solids

velocity gradient in the acceleration zone is assumed to be
proportional to the difference between the steady-state
solids velocity in the fully developed flow zone, U,,, and
the average solids velocity in the acceleration zone, U,:
(16)
Assuming U, is zero at the riser inlet ( x = 0), and taking
U, as 0.99U8, at the end of the acceleration zone (where
x = LA,
then the proportionality constant k is determined
from the integrated form of eq 16 with the substituted
limits:
k = -h(O.Ol/Lacc)
(17)
Thus,if the length of the acceleration zone, Lam,is known,
a value of the proportionality constant, k, may be determined. Wong et al. (1992) used a modified version of the
correlation of Enick et al. (1987) to calculate the length
of the acceleration zone:

(18)
3.36. Developed Flow Zone. Immediately above the
acceleration zone, a fully developed flow zone is assumed
where the solids and gas have been accelerated to their
steady-etate velocity, and the average solids holdup remains essentially constant.
Patience et al. (1993) have found that in the fully developed flow regions of circulating fluidized beds, the slip
factor, defined as the ratio of the interstitial gas velocity
to the solids velocity, is approximately equal to 2:

Ind. Eng. Chem. Res., Vol. 31, No. 12, 1992 2655

Knowing that the average solids velocity in the fully developed zone is given by
(20)
eq 19 may be rearranged to solve for the average voidage
in the fully developed flow zone:

Equations 13 and 21 will fully describe the average axial

voidage profdes in CFB risers equipped with a smooth exit
configuration. Typically, average voidage values in the
range of 0.85-0.98 are observed in CFB risers. As shown
in Figure 1, the CFB catalytic reactor for the partial oxidation of n-butane is equipped with a smooth exit, and
therefore this simulation of the CFB catalytic reactor does
not incorporate the deceleration zone.
3.3.3. Solids Interchange Coefficients. The model
of Wong et al. (1992) uses the empirical expression of
Bolton and Davidson (1988), based on a turbulent diffusion
mechanism, to calculate the solids interchange coefficient
between the core and the annular region:
1 - 2.0Re-lI8
K, = 0.1a1/2Uo1 s / 1 2

The determination of the annulus-to-core solids interchange coefficient is based on an analogy with gas-liquid
countercurrent annular flow. It has been suggested (Senior
and Brereton, 1990; Takeuchi and Hirama, 1990)that the
diffuse interface between the core and annular regions of
a CFB is comparable to that of a gas-liquid annular flow
reported in the literature. The expression for the solids
annulus-to-core solids interchange coefficient is

where pmmand Ucomare the combined phase core density

and the combined phase core velocity, respectively, and
defined by Wong et al. (1992). The quantity fi, is the
smooth pipe friction factor. The proportionality constant,
4, is determined for the case of a negligible solids wall layer
thickness such that r, = R and the net solids interchange
is mro. The detailed procedure for calculating 4 is outlined
by Senior and Brereton (1990).
The simulation presented here predicts core-to-annulus
solids interchange coefficients in the range of 1-3 m/s,
while the predicted annulus-to-core solids interchange
coefficients vary between 0.2 and 1 m/s. The largest values
of the solids interchange coefficients occur in the dense,
turbulent bed a t the riser base and then decrease as the
fully developed flow zone forms.
3.3.4. Gas Interchange Coefficients. In this work,
the Higbie penetration theory (Higbie, 1935) is used to
calculate the gas interchange coefficient. The theory was
originaUy developed to describe contact between liquid and
gas occurring for a short period of time. Thus a steadystate concentration gradient would not have time to develop as the gas moves into the liquid. This results in the
following expression for the gas mass-transfer coefficient:
k, = (4Dmt/~t)'/~
(24)
Eaending this to the CFB, the crossflow of gas is assumed
to occur in the coreteannulus direction only. The voidage
in eq 24 is the annular voidage, and the diffusivity D m is

Table 11. Summary of the Major Assumptions Used for the

Computer Simulation
the CFB catalytic reactor operates isothermally
chemical reaction occura in both the core and annular regions
catalyst deactivation i a the same in both core and annular
regions at the same riser axial location
gas input to the annular region is due solely to crossflow of gas
from the core
the chemical reaction is kinetically controlled
rieer diameter = 0.3 m; riser height = 20 m
riser is equipped with a smooth exit to the cyclone
operating conditions
G, = -800
kg/(m2 8)
Uo= 4-6 m/s
CB = 1-50 mol %
T = 573 K
W O catalyst physical properties (Geldart A)
D, = 75 pm
p, = 1500 kg/m3
e d = 0.5
Ut= 0.05 m/s

that of n-butane in air. The predicted values of the gas

interchange coefficients are of the order of
m/s, while
data supplied by G. S. Patience calculated from an experimental gas RTD indicate values for the core-bannulus
gas interchange coefficient in the range of 0.015-0.094 m/s.
Thus there is agreement between the simulation and the
experimental data.
4. Computer Simulation
The major assumptions incorporated into the computer
simulation are outlined in Table 11. The CFB catalytic
reactor is assumed to operate isothermally at T = 573 K.
Solution of the riser energy balance assuming a typical
value of the solids-to-wall heat-transfer coefficient of 150
W/(m2 K)indicates a maximum temperature variation of
3 "C. Contractor and Sleight (1987) listed isothermal
operation as one of the inherent advantages of the CFB
catalytic reactor for the production of maleic anhydride.
The reaction occurs in both the core and annular regions,
the proportion of which is dependent on the local solid
catalyst concentration as calculated by the hydrodynamic
model. The simulation of the reaction requires solution
of the mam balance for each species, i, reacted or formed.
In the core region, where the gas is flowing, the steady-state
mass balance includes a net convective input term plus the
reaction term which is equal to the gas crossflow to the
annulus. The reaction term ri in eqs 25 and 26, is positive
for products formed and negative for reactants consumed.
The core mass balance is written as follows (Patience,
1990):

In the annular region, there is no convective input term.

The gas input to the annulus is due to crossflow from the
core. The annular region mass balance is thus
~s(1 cann)ri

2kgrc

+ (R2- r:)

(Ci,c

- Ci,a) = 0

(26)

The units of the rate of reaction term, ri, in eqs 25 and 26

are mol/ (gcat.s). In order to incorporate the reaction rate
expression into the mass balance equations, the pseudohomogeneous system was assumed. Such a reactor assumes no concentration gradients within a volume element
and is valid for reactions which are kinetically controlled.
The half-life of this reaction waa estimated assuming that
the reaction occurs in a constant-volume batch reactor.
This calculation results in a half-life of approximately 50

2656 Ind. Eng. Chem. Res., Vol. 31, No. 12, 1992

ms, indicative of an extremely fast reaction which would

not normally be kinetically controlled. However, for a
mean particle diameter of 75 fim, typical of the VPO
catalyst used in the reactor, the Thiele modulus is of the
and the effectiveness factor is 1. Thus, inorder of
traparticle resistance is negligible. Furthermore, the high
slip velocities typical of circulating fluidized bed operation
result in excellent mass transfer between the gas phase and
the catalyst surface. Fbh (1986) indicated, in a qualitative
manner, that the slip velocity is at a maximum in the
circulating fluidized bed regime. Therefore, mass transfer
or interparticle resistance will also be negligible. The
negligible intraparticle and interparticle resistances indicate the reaction is kinetically controlled even though
it is very fast, and thus the pseudohomogeneous assumption is valid for the reactor.
In this work, the simulation was run for a 20-m-high riser
of 30-cm diameter. The riser is divided into 100 equal
elements of 20 cm each. The length of the acceleration
zone is calculated, and the hydrodynamic model is invoked
to obtain the average axial voidage profile. From the
Berruti-Kalogerakis model, the core voidage and core radius are obtained for each element. Forward finite differentiation is used to solve the core and annulus mass
balances of eqs 25 and 26. For a given inlet concentration
of reactants to the first volume element, the reaction rates
may be calculated from eqs 3-5 using the kinetic data of
Table 1. From the stoichiometry of the chemical reactions,
the rates of water formation and oxygen depletion are
calculated. It should be noted that since the majority of
gas flows in the core region, the reactant concentration in
the annular region in the first element is taken to be 0.
This sets up the concentration gradient required for the
mass transfer of gas from the core to the annulus.
Taking the gas velocity in the core (Vo in eq 25) as
constant with height within each of the volume elements,
then the axial concentration gradient of species i in the
element dci/dx may be determined. If the partial derivative is put in discrete form, and with the inlet concentrations to the first element known, the outlet concentration of species i from each element may be found. This
concentration becomes the input to the next element where
the mass balances of eqs 25 and 26 are performed again.
These results then become the input to the next element,
and the procedure is continued to the reactor exit,
By keeping track of the molar flows of each species
reacted or formed, the moles of gas generated by the reaction will be known. This is converted to a volumetric
flow of gas via the molar volume at reaction conditions.
In this way, the increase in gas velocity in the riser due
to gas generation may be calculated and the hydrodynamic
model updated at the end of each interval, in order to
evaluate the new flow structure corresponding to increasing
values of the gas superficial velocity.
The n-butane conversion, yields of maleic anhydride and
COP, and maleic anhydride selectivity are calculated a t
each 20-cm interval. The conversion, X,is defined as
moles of butane converted
X=
(27)
moles of butane fed
Maleic anhydride selectivity, S, is defined here as
moles of maleic anhydride formed
S=
(28)
moles of butane converted
Finally, the product yield of MAN or COz, Y, is defined
as
moles of product formed
Y=
= SX
(29)
moles of butane fed

5.0

5.0 mol% c g
20.0 mol% cB

3.5

m
I. 3.0

C, = 800 kg/m s Uoi = 6 m/s

T = 573 K

>
2.5

b?

10

12

14

16

18

20

Riser Height. m

Figure 2. Single pasa butane conversion for various butane in air

mixtures.

5. Simulation Results and Discussion

5.1. Effect of Feed Concentration. A mixture of

n-butane in air can form a potentially explosive mixture.
The experiments of Wohlfahrt and Hoffman (1980) used
a 1 mol % n-butane concentration while Sharma et al.
(1991) limited their n-butane concentrations to less than
3 mol %. However, since the majority of the oxygen required for the reaction to proceed is supplied by the catalyst surface oxygen, and because catalyst regeneration
occurs in a separate section, the CFB reactor may be
operated in the absence of, or with small amounts of,
gas-phase oxygen. As indicated by Contractor et al. (1988),
this allows for operation with higher n-butane feed concentrations. The simulation was performed for feed concentrations of up to 50 mol % n-butane in air, and as
indicated in Figure 2, conversion decreased with increasing
n-butane feed concentration. Figure 2 also indicates that
a limit is reached whereby an increase in the n-butane feed
concentration has only a marginal effect on the conversion.
Repeated runs of the simulation have indicated that for
n-butane feed concentrations greater than 25 mol % ,the
riser conversion profile is essentially unchanged.
Figure 3 presents the rate of n-butane consumption to
form both maleic anhydride and COP Although the nbutane concentration increases by a factor of 20, the reaction rate for 20 mol % n-butane is only 1.5 times the
reaction rate at 1mol % The expected increase in reaction rate at higher n-butane feed concentrations is lessened
by the inhibition term found in the denominator of eq 3.
Conversion is defined in eq 27 as the moles of n-butane
converted per mole of n-butane fed. For an increase in
n-butane feed concentration, the rate of reaction does not
increase proportionally, and thus conversion is decreased.
With the competing series and parallel reactions, the
conversion includes formation of both desired and undesired products. Figures 4 and 5 compare the yields of
maleic anhydride and COPalong the riser length for two
different &/butane mixtures. Figure 4 indicates that for
1mol % n-butane in the feed, the yield of C02is actually
greater than the yield of maleic anhydride. When the feed
concentration is increased to 5 mol % as shown in Figure
5, the yields of both maleic anhydride and COadecrease,
but the yield of the desired product, maleic anhydride, is
now greater than the yield of COO.This is obviously a more

Ind. Eng. Chem. Res., Vol. 31, No. 12, 1992 2657
0.100

I
1.0 mol% c B

G. = 800 kg/m2s
UOi = 6 m / s
T = 573 K

20'o molX c B

0.080

1.2
1.4

.
e

GI = 800 kg/m2 s Uoi = 6 m/s

cg = 5.0 mol%
T = 573 K

0.070

nv)

E 0.060

.-;0.8 c

.-6

0.050

MAN Yield

0.6

0.040

YI

0.030

/-

0.4

0.020

0.2
/

0.010

0.0
0

10

12

14

16

18

20

Riser Height. m

Figure 5. Single pass product yields for 5 mol % butane in air

mixture.
100.0

G, = 800 kg/m2s

Uoi = 6 m/s

90.0

cg = 1.0 mol%

T = 573 K

2.4

80.0
70.0

&

_ _ _ _ _ _ _...
_ _.._..................
_ _ _ _ _ _ _ _......
_ _..._.............
_ _ _ _ _ _,....,
_ _ _,.- - ......... ..........................._._.._.._._ _ _ _ .._...............
.___.__--------__________-----.

2
bp

__----

---_--

'x-

30.0

1.0 mol% c B

---

5.0 mol% cB
.__-20.0 mol% cg
..... .... 50.0 mol% cg

10.0

0.0

10

12

14

16

18

20

Riser Height. m

n
-.-o

G, = 800

kg/m2s
Uo, = 6 m/s

T = 573 K

10

12

14

16

18

20

Riser Height, m

Figure 4. Single pass product yields for 1 mol % butane in air

mixture.

Figure 6. Maleic anhydride selectivity for various butane in air

mixtures.

profitable situation. These results indicate that although

higher conversions are attained at relatively lower feed
concentrations of n-butane, such an operating condition
is not advantageous as the C02yield exceeds that of the
maleic anhydride. The ability to operate a CFB reactor
in the absence of gas-phase oxygen now becomes important, as the resulting higher n-butane concentrations will
result in improved yields of maleic anhydride.
Figure 6 shows the selectivity ,to maleic anhydride
(MAN) along the riser defined in this work as the moles
of MAN produced per mole of n-butane converted. Lower
concentrations of n-butane in the feed result in lower selectivity. At concentrations of 20 mol % or greater, selectivities of 80% are realized. Experimental graphical
data at 360 "C presented by Contractor et al. (1988) indicate selectivites of 75-80% for n-butane concentrations
in the range of 12-50%. Thus the results of this work at
300 OC agree favorably with that data. The initial drop
in selectivity seen a t the lower concentrations in Figure
6 may be attributed to the relatively greater initial oxygen

concentration in the feed. For a 1 mol % n-butane concentration in an air/butane mixture, the corresponding
oxygen concentration is 20.8 mol %. Therefore, the initial
reaction rate for COz formation is favored, and a drop in
selectivity is observed. For 20 mol % n-butane in the feed,
the initial oxygen concentration is 16.8 mol % and a flatter
selectivity profile is seen. Once again, the advantage of
operating the CFB reactor in the absence of gas-phase
oxygen and increased n-butane concentrations is reinforced
as the higher feed concentrations result in significantly
improved selectivities. These selectivity results agree with
the previous results of the product yields. Low yields at
low n-butane concentrations correspond to low maleic
anhydride selectivities.
The yield is defined in eq 29 as the product of the selectivity and the conversion. It has been shown in Figures
2 and 6 that, at high n-butane feed concentrations, conversion and selectivity profiles are constant. Therefore,
the yield will also be constant. It was previously mentioned
that approximately 25 mol % n-butane in the feed is the

2658 Ind. Eng. Chem. Res., Vol. 31, No. 12, 1992

.-r

.........

3.0

0.40
W

0.30

0.20

0.00

k$.

\*..'.
\

'

10

12

14

16

18

20

0.00

10

12

14

16

18

Riser Height, m

Figure 7. Effect of solids circulation rate on butane conversion and

solids holdup.

critical concentration. Operation above this concentration

will not significantly improve product yields or selectivity.
Though the conversions and yields are very low,
throughput from CFB reactors is very large and maleic
anhydride production can be significantly higher than that
from a fixed bed operation. Furthermore, there is the
potential for enhanced reaction rates due to the cyclic
operation between the riser and the regenerator (Matros,
1989; Lang et al., 1989). The cyclic operation has not been
included in the simulation at this time due to lack of reaction kinetics for the process. Contractor et al. (1988)
state that it is possible to improve this conversion by addition of small amounts of gas phase oxygen in the riser.
The potential for secondary air injection along the CFB
riser would be valuable for this purpose.
5.2. Effect of CFB Operating Conditions on Reactor
Performance. The use of the predictive hydrodynamic
model in this simulation allows the effect of operating
parameters such as solids circulation rate and superficial
gas velocity to be carefully studied. These variables will
affect the local solids catalyst holdup in the riser and hence
the conversions and yields.
The n-butane conversion for solids circulation rates of
400,600, and 800 kg/(m2.s) is presented along with the
corresponding actual solids holdup for each circulation rate
in Figure 7. The inlet gas superficial velocity is maintained at 6 m/s, and n-butane concentration in the feed
is 5 mol % . An increased solids circulation rate results in
a greater solids holdup. This improves the contact between
gas and solids, and therefore a higher conversion is
achieved. It should be observed that, at the inlet of the
riser, solids holdup is increased from about 28% solids at
the low solids circulation rate to roughly 35% solids at the
highest solids circulation rate. This increase in solids
holdup is important because the catalyst will be moat
active when it reenters the riser after regeneration in the
standpipe.
In Figure 8, the n-butane conversion along the riser is
presented for inlet superficial gas velocities of 4,5, and 6
m/s along with the corresponding solids holdups. The
solids circulation rate and n-butane feed concentration are
800 kg/ (m2-s)and 5 mol % , respectively. The effect of
increased superficial gas velocity is a dilution of the bed
and thus a decrease in solids holdup. As a result, a de-

20

Riser Height. m

Figure 8. Effect of inlet superficial gas velocity on butane conversion and solids holdup.

50% deactivation
70% deoctivotion

2.0
C

.0

G, = 800 k g / m s Uo, = 6 m/s

cg = 5.0 mol%

T = 573 K

0.0
0

10

12

14

16

18

20

Riser Height, m

Figure 9. Effect of catalyst deactivation on single pass butane

conversion.

crease in the conversion of n-butane is seen at higher gas

velocities. Again, the dense bed at the base of the riser
exhibita the greatest solids holdup.
Figures 7 and 8 confirm that it is beneficial to operate
at the highest possible solids loadings and low gas velocities. The high initial reaction rates and the resulting gas
generation in the dense bed will tend to increase the gas
superficial velocity.
5.3. Results of Catalyst Deactivation Model. The
preceding results were obtained assuming a catalyst
deactivation corresponding to a value of 20% at the outlet
of the riser. This section investigates the importance of
catalyst deactivation as it is modeled here. Values of the
decay constant a in eq 9 were chosen such that the catalyat
was 20%) 50%, and 70% deactivated upon exiting to the
cyclone. Feed concentration and riser operating conditions
were held constant. As shown in Figure 9, increased
catalyst deactivation reduces conversion along the riser.
For approximately the first 3 m of riser length, the conversion is unaffected,but beyond this point the conversion

Ind. Eng. Chem. Res., Vol. 31, No. 12, 1992 2659
0.050 r

G, = 800 kg/m2s
c

Uoi = 6 m/s

0.045
cg = 5.0 mol%

E 0.040

a rapid initial rise in reaction rate in the annular region.

After 8-10 m, the rate of reaction levels off as reactants
are depleted and mass transfer between the core and the
annulus is lessened.

T = 573 K

0.000
0

10

12

14

16

18

20

Riser Height. m

Figure 10. Contribution to reaction by the core and annular regions

for a 5 mol % butane in air mixture.

profiles begin to separate. At the riser inlet, the catalyst

has just been regenerated and exposure to reaction conditions does not show a noticeable effect. Reaction occurs
rapidly at this level, however, and after 3 m the transformation of the catalyst crystalline phases at the expense
of the surface oxygen layers becomes significant. The
higher degree of deactivation, resulting in reduced conversion, will consequently reduce the yields of both maleic
anhydride and COP The results of this simple catalyst
deactivation model indicate that reduction of the catalyst
activity as the reaction proceeds has only a slight effect
on the reactor performance. However, the results will
underpredict the effect of deactivation on conversion due
to the assumptions involved in the deactivation model.
Further work to include the solids RTD in the simulation
will produce more realistic results.
5.4. Influence of the Core and Annular Regions. It
is interesting to investigate the separate contributions of
the core and the annulus to the reaction. While the majority of the gas flows upward in the solids-lean core region,
the annular region will have a higher concentration of
catalyst. Furthermore, although the annulus is very dense,
it is also very thin, which will affect the reaction rate per
unit volume of bed.
Figure 10 separates the contribution to the reaction by
the core and the annular regions. The model assumes that,
initially, all of the gas fed to the riser is in the core region.
The high initial concentration of reactants combined with
the large solids holdup in the core at the base of the riser
results in a high initial reaction rate in the core and essentially zero reaction rate in the annulus. The solids
holdup in the core quickly decreases however, as illustrated
earlier in Figures 7 and 8, and some of the upward flowing
gas is transferred to the annulus. Also, the rapid initial
reaction rate depletes a large portion of the reactants.
These fadors combine to give the steep decline in reaction
rate in the core seen in Figure 10. The gas concentration
gradient between the core and the annulus is initially very
large because all of the gas is concentrated in the core.
Thus, with crossflow of gas modeled by a mass-transfer
mechanism, the annulus gas concentration rises quickly.
This fact, combined with the constant solids holdup corresponding to minimum fluidization voidage as assumed
in the development of the hydrodynamic model, leads to

6. Conclusions
The hydrodynamics of a circulating fluidized bed and
a fixed bed intrinsic kinetics model have been combined
to form a comprehensive computer simulation of the
partial oxidation of n-butane to maleic anhydride. The
model allows investigation of the effect of changes in operating conditions or reactor geometry, important in reactor design and process control. Key results presented
indicate decreased conversion with increased n-butane feed
concentration, but improved selectivity at the higher nbutane concentrations. For high solids circulation rates,
conversion is increased due to increased solids holdup, and
thus better gasaolids contacting. Increasing the gas superficial velocity decreased conversion due to the dilution
of the bed or decreased solids holdup. Catalyst deactivation had a only a slight effect on reactor performance,
however; more work is needed to make the deactivation
model more rigorous.

Acknowledgment
The work reported in this paper has been supported by
a Natural Sciences and Engineering Research Council of
Canada operating grant and scholarship.

Nomenclature
a = deactivation parameter (8-l)
cB = n-butane concentration (mol/L)
c, = oxygen concentration (mol/L)
cMAN = maleic anhydride concentration (mol/L)
q C = concentration of the ith species in the core (mol/L)
ci,, = concentration of the ith species in the annulus (mol/L)
Dm = molecular diffusivity of n-butane in air (m2/s)
D, = mean particle diameter (m)
D,= riser diameter (m)
fi0= smooth pipe interfacial friction factor
g = gravitational acceleration constant (m/s2)
G, = overall solids circulation rate (kg/(m28 ) )
k = proportionality constant in the acceleration zone (m-l)
kl = kinetic constant for maleic anhydride formation (mol'-*
L"/(g 5 ) )
k z = kinetic constant for COz formation (moll-8 LB/(g a))
k3 = kinetic constant for MAN decomposition (mol" L1+/(g
8))

kd = kinetic constant for catalyst surface deactivation (s-l)

k, = gas mass-transfer coefficient from core to annulus (m/s)

K,, = annulus-to-core solids interchange coefficient (m/s)

K,, = core-to-annulus solids interchange coefficient (m/s)
KB = equilibrium constant in Centi kinetics (mol/L)
Lac,= length of the acceleration zone (m)
P = total pressure (Pa)
qo = number of deactivated catalytic sites for a totally
deactivated catalyst
q ( t ) = number of deactivated catalytic sites at any time t
rl, r m = rate of maleic anhydride formation from n-butane
(mol/(g 9))
r2, rCOl = rate of C02 formation from n-butane (mol/(g a))
r,, -rmN = rate of maleic anhydride decomposition (mol/(g
8))

r, = rate of the ith reaction, where i = 1, 2, 3 (mol/(g 8))

r, = core radius (m)
rd = rate of catalyst deactivation (mol/(g 8 ) )
R = riser radius (m)
Re = Reynolds number = U o p p p / p
Re, = particle Reynolds number = fJ$gDp/bg

2660 Ind. Eng. Chem. Res., Vol. 31, No. 12, 1992

S = product selectivity, moles of product formed per moles

converted
S = Stokes number = pJl,2Uo/18pgUt
t , = solids residence time (s)
T = temperature (K)
U,,, = combined phase core velocity (m/s)
Uo = riser superficial gas velocity (m/s)
Ua = average solids velocity (m/s)
U,, = core solids velocity (m/s)
U,, = solids velocity at the end of the acceleration zone (m/s)
Ut = terminal settling velocity of a single solids particle (m/s)
x = axial location in the riser (m)
X = n-butane conversion, moles converted per moles fed
Y = product yield, moles of product formed per moles fed
Greek Letters
a, 8, 6 , = kinetic constants, exponents in Centi rate expressions
r = constant in acceleration zone
tan = annular voidage
fapp = apparent axial voidage in the acceleration zone
taVg= average axial voidage
t b = apparent voidage at riser bottom
tC= core voidage
emf = voidage at minimum fluidization conditions
to = actual voidage at riser bottom
t, = voidage at the end of the acceleration zone
{ = constant in K,,expression
pb = bulk density of solids (kg/m3)
pcom = combined phase core density (kg/m3)
pg = gas density (kg/m3)
pa = solid particle density (kg/m3)
cp = slip factor
4(t) = fraction of the total number of catalytic sites deactivated
Registry No. Butane, 106-97-8;maleic anhydride, 108-31-6;
vanadium phosphorus oxide, 65506-75-4.

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Revised manuscript received August 10, 1992
Accepted September 4,1992