Chemical Engineering Science 58 (2003) 643 – 648

www.elsevier.com/locate/ces

Selective oxidation of n-butane to maleic anhydride in &uid bed reactors:

detailed kinetic investigation and reactor modelling
Mario Dentea;∗ , Sauro Pieruccia , Enrico Tronconia , Marco Cecchinib , Federico Ghel0b
a Dipartimento “G. Natta”, Politecnico di Milano, P.zza L. da Vinci 32, 20133 Milano, Italy
b Lonza Polymers & Intermediates, Scanzorosciate (BG), Italy

Abstract

The kinetics of n-butane oxidation to maleic anhydride over a commercial V-P-O catalyst for &uid bed reactors was investigated
systematically and modelled according to a scheme of eight reactions, involving also the combustion of both n-butane and maleic anhydride
to CO and CO2 , as well as the formation and the combustion of acetic and acrylic acids. A one-dimensional, heterogeneous (two-phase)
&uid bed reactor model incorporating the independently derived kinetic scheme was successfully validated on a predictive basis against
conversion, selectivity and steam production data collected in a full-scale MA production plant.
? 2003 Elsevier Science Ltd. All rights reserved.

Keywords: Fluid bed; Multiphase reactors; Selective oxidation; Maleic anhydride; Kinetics; Simulation

1. Introduction from reaction engineering considerations. Nevertheless,

Maleic anhydride (MA) is an important intermediate in
the industrial production of unsaturated resins, chemicals
for agriculture and food additives. Modern commercial pro-
cesses for MA are based on the selective gas-phase oxida-
tion of n-butane over V-P-O catalysts either in 0xed- or in
&uidized-bed reactors. Fixed bed is a well-known technol-
ogy where the main contribution to improved performances
currently relies on modi0cations of the catalysts rather than
on reactor design. Fluidized-bed reactors, a solution pre-
ferred for large-scale plants (Arnold, Suciu, Verde, & Neri,
1985; Contractor & Sleight, 1987), represent a newer tech-
nology: they are used by BP and Mitsubishi in their own
plants, whereas ABB Lummus/Lonza, under the brand
name ALMA, have licensed 9 units all over the world in a 7
year period. Under typical conditions (T 6 450◦ C, P =
2–4 bar a, n-butane feed concentration 4–5% v=v) the
nC4 H10 conversion in a &uidized-bed reactor exceeds 80%,
but the MA molar yield is limited to ≈ 50–55%. In the past
most of the eDorts aimed at improving the overall MA yields
have been focused on catalyst development, at the present
stage, however, signi0cant progress can also be expected
∗ Corresponding author. Fax: +39-2-7063-8173.
E-mail address: mario.dente@polimi.it (M. Dente).
publications addressing the kinetics and the reactor de-
sign for this process are scarce in the literature (Centi,
Fornasari, & Tri0rGo, 1985; Schneider, Emig, & Hofmann,
1987; Sharma, Cresswell, & Newson, 1991; Bej & Rao,
1991; Mills, Randall, & McCracken, 1999). Also, all of the
kinetic studies available in the literature assume a simpli-
0ed triangular reaction scheme accounting for the parasitic
combustion of both the reactant and the desired product
to COx , but neglect the formation of other by-products.
Furthermore, the investigated ranges of the reaction vari-
ables are often limited to atmospheric pressure and/or low
butane concentrations, which are not representative of the
industrial process conditions.
In this work, we present 0rst an extensive, systematic
kinetic study of the n-butane oxidation to MA over a com-
mercial V-P-O catalyst designed for &uid bed reactors,
which addresses also the formation of acrylic and acetic
acid, the two most signi0cant by-products in addition to
COx . In fact their concentration in the eJuent stream from
the reactor is relevant to the design of the downstream sep-
aration/puri0cation sections of the plant. The ranges of the
investigated kinetic variables, including total pressure and
n-butane concentration, fully cover the operating conditions
prevailing in industrial &uid bed reactors. Experiments with
addition of the main reaction products to the test reactor
feed were also performed in order to assess their kinetic

0009-2509/03/$ - see front matter ? 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0009-2509(02)00590-0
644 M. Dente et al. / Chemical Engineering Science 58 (2003) 643 – 648
role in the reaction network. Next we present the develop-
ment of a two-phase model of the industrial &uidized-bed
reactor, fully accounting for &uid dynamics, mass and heat
transfer eDects, as well as detailed internal geometry. The
reactor model, which incorporates the independently de-
rived kinetic scheme with no further adaptation, is eventu-
ally validated on a predictive basis against industrial plant
data.
2. Experimental
Apparatus and procedures—Kinetic experiments of
nC4 H10 oxidation were carried out in a stainless steel tubu-
lar micro&ow reactor (inner diameter = 12 mm) loaded
with a commercial &uid bed V-P-O catalyst supplied
by Lonza Polymers & Intermediates (average particle
diameter = 62 m) diluted with inert quartz (1:2 w/w). A
1=16 tube was inserted coaxially into the reactor tube to
act as a thermowell for a sliding thermocouple, allowing
to measure the axial temperature pro0le. The feed section
of the test rig included three distinct lines for nC4 H10 =N2
mixtures, O2 and N2 , respectively, in order to vary indepen-
dently the feed contents of the two reactants as well as the
total &ow rate. Furthermore, a saturator placed prior to the
reactor was used to enrich the feed stream with liquid com-
pounds in dedicated experiments. The feed line was also
equipped with a safety valve as well as a rupture disk set
at 5 bar a. A crystallizer, normally kept at r.t., was placed
immediately downstream from the reactor outlet and used
to collect part of the maleic anhydride formed during the
kinetic runs. The outlet line from the crystallizer, heated at
75◦ C, proceeded through a backpressure regulator and led
to two glass absorbers in series, the former being 0lled with
water at r.t. to collect the residual fraction of maleic anhy-
dride and the acidic by-products, the latter being immersed
in an ice bath to condense most of the steam. Before being
vented, the uncondensed gases were sampled and analysed
on line by an HP 5890 GC equipped with a Porapak col-
umn (for analysis of CO2 and nC4 H10 ), a molecular sieve
column (for analysis of O2 , N2 and CO), and two TC de-
tectors. Each kinetic run lasted between 4 and 7 h. At the
end, the contents of the absorbers and of the crystallizer
were accurately collected and combined to obtain a single
aqueous solution, which was then added with an internal
standard (phenol) and analysed by a second oD line HP
5890 GC equipped with a &ame ionization detector and
an HP5 capillary column: the only products detected were
acetic acid, acrylic acid and maleic anhydride. Since repro-
ducibility of the GC analysis of MA was not satisfactory,
however, the standard evaluation of the produced MA was
obtained by titration of the total acidity in the solution, upon
subtracting the acetic and the acrylic acid. This analytical
procedure was found reproducible and consistent, yielding
typical overall C-balances in the range 98–99%: no runs
with C-balances in error of 3% or more were accepted.
Preliminary experiments—Preliminary blank runs
demonstrated signi0cant conversions of n-butane in the
empty reactor tube already at atmospheric pressure at tem-
peratures in excess of 400◦ C; the conversion was greater
when the pressure was raised to a few bars. However, the
homogeneous reactions became practically negligible at
the same conditions when the reactor was packed with 0ne
quartz particles. Accordingly, in all the kinetic runs the
voids upstream and downstream from the catalyst bed were
accurately 0lled with quartz. Diagnostic calculations proved
that the kinetic runs were performed in a genuine chemical
regime, even under the most severe investigated conditions.
Gas–solid (external) diDusional limitations were ruled out
also by classical experiments which involved the same
space velocity but a threefold variation of the linear gas
velocity.
3. Kinetic study
Chemical enrichment experiments—A complete series
of runs was carried out where each relevant product of the
reaction, namely H2 O, CO, CO2 , MA, acrylic acid and acetic
acid, was individually added to the test reactor feed stream
(n-butane/air) in growing concentrations. Most of the same
products (CO, MA, acrylic acid and acetic acid) were also
fed to the reactor in the absence of n-butane. Comparison
with the results of reference runs provided uncorrelated and
uncontroversial information concerning the kinetic eDects as
well as the evolution of reaction products. For instance, it
was clearly apparent that MA, acrylic acid and acetic acid
were more or less readily oxidized to COx . On the other
hand, the conversion of CO was found almost negligible over
the tested V-P-O catalyst. As shown in Fig. 1, steam added
to the feed stream inhibited the conversion of n-butane but
promoted slightly the MA selectivity, and more signi0cantly
the selectivities of the two acid by-products. The addition
of even large amounts of either CO or CO2 to the feed
stream, however, did not modify the reaction performances
to any signi0cant extent. Notably, in the case of CO2 addition
the present results are at variance with recent reports by
Xue et al. (2001) who claimed drastic increments of MA
selectivity upon feeding n-butane/air mixtures rich in CO2
over a Dupont V-P-O catalyst.
Kinetic runs—The kinetic study was executed according
to a sequential, three-step experimental strategy. A 0rst ex-
ploratory design was carried out in order to investigate over
a suitable range of space velocities the individual eDects of
the following process variables: reaction temperature (360
–480◦ C), pressure (1–4:5 bar a), n-butane and oxygen feed
contents (0.8–7 and 4.4 –23% v/v, respectively). A second,
extensive set of kinetic runs was later organized according to
a four-factor centralized composite design in order to grant
a uniform coverage of the experimental space. Eventually, a
0nal set of runs was added to cover the experimental space at
the highest butane conversions and to complement the study
 M. Dente et al. / Chemical Engineering Science 58 (2003) 643 – 648 645

Fig. 1. EDect of steam addition at T = 440◦ C, P = 2:5 bar a, YnC

◦
4 H10
= 4% in air.

MA 2 CO + CO2 45

1 40
Acrylic Acid 4 CO + CO2
3 35
n-C4H10 5 Acetic Acid 6
CO + CO2 MA
Yield (%) 30 CO
7 CO2
CO 25
8
20
CO2
15
Fig. 2. Reaction network assumed for the kinetic analysis.
10

0
of the reaction variables. A total of 71 kinetic runs were thus 0 1 2 3 4 5 6 7

collected for the purpose of kinetic parameter estimation. Y˚n-C4H10 (%)

The overall conversion—selectivity correlation emerging

from our data showed that the MA selectivity remains
virtually independent of conversion (and constant around
70 –75%) as long as the nC4 H10 conversion is limited,
6 70%.
Analysis of kinetic data—The kinetic data were analysed
on the basis of a reaction scheme (see Fig. 2) comprising
8 parallel and consecutive reactions, namely the oxidation
of n-butane to MA, acrylic and acetic acid, CO and CO2 ,
as well as the successive total combustions of MA, acrylic
and acetic acid. In view of the 0nal scope of this work, i.e.
the construction of a &uidized-bed reactor model, simple
LHHW-type empirical rate expressions were assumed for
each pseudo-reaction. In line with the preliminary eval-
uations, a simple ideal plug-&ow reactor model could be
adopted for the kinetic analysis; however, since the tem-
perature pro0les observed in our test reactor exhibited sig-
ni0cant gradients at the highest investigated conversions,
non-isothermal PFR model equations had to be integrated
for each run, interpolating the measured T-distributions. On
such a basis, the 5 molar yields of MA, acrylic and acetic
acid, CO and CO2 measured in the 71 runs were 0tted suc-
cessfully by multiresponse non-linear regression using 21
adaptive kinetic parameters, which left 334 residual degrees
of freedom. The objective function for the least-squares pro-
cedure was the sum of the sum of squared residuals of each
Fig. 3. Experimental and 0tted molar yields in microreactor: eDect of
◦
nC4 H10 feed concentration YnC at T = 410◦ C, P = 2:5 bar a.
4 H10
response over all runs, weighted by the corresponding re-
sponse variance determined from replicated runs. The good-
ness of 0t is illustrated in Figs. 3–5. The average percentage
error of the 0t was about 8% for MA, CO and CO2 , and
about 20% for acetic and acrylic acids: these 0gures com-
pare fairly well with the corresponding experimental errors,
which are obviously greater for the small yields of the two
acids. Concerning the parameter estimates, all of them were
found statistically signi0cant at the 95% con0dence level.
On a more physico-chemical basis, it is worth mentioning
that the estimated activation energy for the main reaction
(formation of MA from n-butane, 79:2 ± 3:6 kJ=mol)
resembles the estimates reported in previously published
kinetic studies over similar V-P-O catalysts, which range
between 71 (Mills et al., 1999) and 103 kJ=mol (Bej & Rao,
1991). Likewise, the higher estimated activation energy for
the MA combustion reaction (243 ± 48:1 kJ=mol) is also in
line with other published estimates: e.g. 162 kJ=mol (Bej &
Rao, 1991), 180 kJ=mol (Buchan & Sundaresan, 1986),
and is consistent with the well-known detrimental eDect of
high reaction temperatures on the MA selectivity.
646 M. Dente et al. / Chemical Engineering Science 58 (2003) 643 – 648

55
1.4
50 MA Acetic Acid
45 CO 1.2
Acrylic Acid
CO2
40
1.0
% Yield

35

% Yield
30 0.8

25
0.6
20

15 0.4

10 0.2
5
0.0
0 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
Pressure, bar a
Pressure, bar a

Fig. 4. Experimental and 0tted molar yields in microreactor: eDect of total pressure at T = 430◦ C, YnC
◦
4 H10
= 1:6% v=v.

60

50
Calculated MA yield, %

40

30

20

10

0
0 10 20 30 40 50 60
Experimental MA yield, %
Fig. 6. Fluidized-bed reactor (diameter=7 m): discretization into sections.
Fig. 5. Parity plot for MA in microreactor.

@Tb Abe fb
=
NC
@z b b
1 Wi Cp; i
4. Fluidized-bed reactor model
 NC


b b
An industrial &uidized-bed reactor (diameter over 5 m) lo- × Tb Cp; i Kx; i (!i − !ie ) − Hbe (Tb − Te ) (2)
cated in Italy was modelled and the model was validated with 1
experimental data. Fig. 6 provides a representative sketch
while the emulsion phase is described by
of the reactor layout, and also the model concept. Air is
 Z
fed to the reactor bottom, &uidizing the catalyst. n-Butane
is vaporized and injected directly into the &uidized catalyst Wie = Wie; in + Ri i Ve + Abe fb Kx; i (!ib − !ie ) d z
0
bed. The heat of reaction is removed by direct steam gen-
eration in cooling coils immersed in the catalyst bed. The (i = 1; NC): (3)
speci0cs of the reactor design, catalyst properties (including
Eqs. (1) and (2) are the material and energy balances, re-
particle size distribution) and operating conditions (super-
spectively, for the bubble phase under the assumption of a PF
0cial velocity etc.) were found to make the reactor operate
behavior, while Eq. (3) is the material balances for the CSTR
like a series of N successive sections (see Fig. 6). Each of
reactor describing the emulsion phase. The sub/super-scripts
them may be modelled following the approach proposed by
b and e refer to bubble and emulsion phase, respectively,
Davidson and Harrison (1963). Therefore, the equations for
while be indicates values at the interfacial area. Wi and !i
the bubble phase are:
are, respectively, the mass &ow rate and fraction of the ith
component, T is the temperature value and z is the current
@Wib axial length. For a greater detail on the meaning of the cited
= −Abe fb Kx; i (!ib − !ie ) (i = 1; NC) (1)
@z variables, see the appended Notation.
 M. Dente et al. / Chemical Engineering Science 58 (2003) 643 – 648 647

The gas fraction fb in the bubble phase is calculated N-Butane Conversion

from bubble sizes and spatial velocity as reported by Kunii (100 = Design Value)
and Levenspiel (1969). Mass transfer coeQcients Kx; i are 105
estimated by assuming, for each component, two contribu-
tions: bubble-cloud and cloud-emulsion evaluated by the fol-
lowing expressions (Kunii & Levenspiel, 1969): 100

Calculated
 
1=2 1=4
umf Dbc g
Kbc = 4:5 + 5:85 95
db db5=4

1=2
Dce ub !mf 90
Kce = 6:78 :
d3b 90 95 100 105
Experimental
The heat transfer coeQcient Hbe neglects the emulsion-cloud
resistance, taking therefore into account only the two con- Fig. 7. Parity plot: n-Butane conversion.
tributions of bubble-cloud and gas-particles to the bubbles.

umf "g Cpgas (kg "g Cpgas )1=2 g1=4

Hbc = 4:5 + 5:85 Maleic Selectivity
db db5=4 (100 = Design Value)
Nup kg 115
hgp = ······ (Nup = 2 + 0:6Pr 1=3 Re1=2 ):
dp
110
The production rate Ri of each component is adjusted with Calculated
a decay factor which takes into account the catalyst decay
105
along the run time. The dependence on time-on-stream t is
expressed by the relation:
100
1 + at
i =
1 + bt
95
which enables the description of the catalyst decay as a re- 95 100 105 110 115
duction of the active surface due, for example, to synter-
Experimental
ing of adjacent crystals. The constant values a and b are
evaluated from experimental plant data. The heat of reac- Fig. 8. Parity plot: MA Selectivity.
tion is removed at practically constant Te by cooling coils
immersed into the &uidized bed. The heat transfer coeQ-
cient for immersed horizontal tubes is evaluated according
The system of Eqs. (1)–(3) is solved with its initial val-
to Vreedenberg (1958):
ues conditions including the emulsion temperature Te . The

0:3
kg Cpgas )g diDerential portion of the system (Eqs. (1) and (2)) may be
hw = 0:66 disjointly solved from Eq. (3) once the !ie mass fractions
dt kg
are known; this fact suggests that the whole system may be



0:4
d t "g u 0 1 − !f "s reduced to an algebraic one formed by Eq. (3) in the un-
× (Re ¡ 2000) knowns Wie : each function evaluation, so far, implies the
)g !f "g
solution of the diDerential portion . Standard ODE and Al-

0:3
kg Cpgas )g gebraic Systems solvers have been used for the numerical
hw = 420 solution.
dtubi kg
On site experimental data, daily averaged and covering

 2 
0:3
dti "g u0 )g "s a period of about two years, have been collected from the
× 3
(Re ¿ 2000) plant DCS. The reactor performances have been then eval-
)g d p "s g "g
uated in terms of n-butane conversion and MA selectivity.
dp " g u 0 Figs. 7 and 8 report the comparison between experimental
Re = : and predicted values for a signi0cant set of available in-
)g
dustrial scale data. Although the model overestimates both
The internal convective contribution due to water &owing values on the average, the discrepancies can be regarded as
inside the tubes is evaluated with the standard correlation: acceptable and the model rated suitable for the engineering
Nu = 0:023 Re0:8 Pr 0:33 . purposes of the present work.
648 M. Dente et al. / Chemical Engineering Science 58 (2003) 643 – 648

5. Conclusions )g gas viscosity

!ib mass fraction in bubble phase
The combination of intrinsic kinetics for n-butane oxida- !ie mass fraction in emulsion phase
tion to maleic anhydride over a V-P-O catalyst, determined "g gas density
on the basis of about one-hundred overall test runs in a ded- "s solid density
icated lab-scale rig, and a fully deterministic model of com- i catalyst decay factor
mercial &uid bed reactors has proven successful in repro-
ducing the most signi0cant features of the operation of an
industrial unit. It is expected that 0ne tuning of this com- Acknowledgements
bined kinetic-modelling approach will provide an eQcient
tool for guiding process development aimed at exploiting at The contribution of C. Trecciola, L. Sobacchi, A. Bram-
best the intrinsic catalyst performances, involving also ex- billa, F. Ravandoni, A. Vele and A. Venci is gratefully
perimentation in a semi-commercial &uidized-bed reactor. acknowledged.

Notation References

Abe interfacial area bubble-emulsion Arnold, S. C., Suciu, G. D., Verde, L., & Neri, A. (1985). Use &uid bed
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September, pp. 123–126.
Cpgas gas heat capacity
Bej, S. K., & Rao, M. S. (1991). Selective Oxidation of n-Butane to
db bubble diameter Maleic Anhydride. 1. Optimization Studies. Industrial Engineering
dp catalyst particle diameter and Chemical Research, 30, 1819–1824.
dt cooling coil diameter Buchan, J. S., & Sundaresan, S. (1986). Kinetics and redox properties of
Dbc diDusion coeQcient, bubble-cloud vanadium phosphate catalysts for butane oxidation. Applied Catalysis,
26, 211–226.
Dce diDusion coeQcient, cloud-emulsion
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ub bubble velocity
Chemical Engineering Science, 54, 3709.
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