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Chemical Engineering Research and Design

journal homepage: www.elsevier.com/locate/cherd

Simulation of an industrial turbulent uidized bed


reactor for n-butane partial oxidation to maleic
anhydride

A. Romano a , A. Di Giuliano a, , K. Gallucci a , P.U. Foscolo a , C. Cortelli b ,


S. Gori b , M. Novelli b
a Industrial Engineering Department, University of LAquila, 18 via G. Gronchi, 67100 LAquila, Italy
b Polynt S.p.A, 51 via E. Fermi, 24020 Scanzorosciate, Bergamo, Italy

a r t i c l e i n f o a b s t r a c t

Article history: A uid-dynamic and chemical model of an industrial-scale turbulent uidized-bed reactor,
Received 11 April 2016 which performs n-butane partial oxidation to maleic anhydride (MA) catalyzed by (VO)2 P2 O7
Received in revised form 4 July 2016 solid particles, is proposed. Main assumptions are: gas plug-ow in the dense bed because
Accepted 1 August 2016 gas back-mixing is minimized by internals; perfectly mixed particulate phase in the dense
Available online 9 August 2016 bed due to high recirculation rate of entrained particles at the bottom of the reactor, after
separation by cyclones; plug-ow of both gas and solids in the freeboard. Literature kinetic
Keywords: models are considered to simulate reactions, slightly modied to allow careful prediction of
Maleic anhydride production industrial performance. The model is organized in ordinary differential and algebraic equa-
Turbulent uidized bed tions describing mass and energy balances and constitutive expressions for reaction rates,
Fluid dynamic-kinetic model heat and mass transport phenomena, and implemented in MATLAB . Numerical results
simulate accurately temperature along the reactor, MA yield and by-products selectivity
in the outlet stream, and allow to estimate the solid circulation rate. Inlet gas ow rate
and n-butane/air feeding ratio are varied within a 10% range around industrial operat-
ing conditions, to test the parametric sensitivity of the model: corresponding dense bed
height, n-butane conversion, products selectivity in the outlet stream vary within 5% of
the experimental performances, depicting stable conditions.
2016 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction scale (Ballarini et al., 2006).

The partial oxidation of n-butane to maleic anhydride (MA) catalyzed by C4 H10 + 3.5O2 C4 H2 O3 + 4H2 O H0 298K = 1268 kJ/mol
vanadyl pyrophosphate (VO)2 P2 O7 (Reaction 1) is a successful example
(Reaction 1)
of light alkanes conversion to valuable chemicals by high-temperature
contact with a redox catalyst (Ballarini et al., 2006; Hutchings, 1993).
C6 H6 + 4.5O2 C4 H2 O3 + 2CO2 + 2H2 O H0 298K = 1880 kJ/mol
Hydrocarbon selective oxidation processes are quite popular in indus-
try, specically in the context of alkane functionalization due to their (Reaction 1a)
lower cost compared to olens (Hutchenson et al., 2010). Since the 80s,
processes based on this reaction have been replacing the more tradi- It is worth mentioning here that Reaction 1 has a higher chemical
tional production of MA from benzene (Reaction 1a) on commercial efciency: all carbon atoms in n-butane molecule are converted to the


Corresponding author.
E-mail address: andrea.digiuliano@graduate.univaq.it (A. Di Giuliano).
http://dx.doi.org/10.1016/j.cherd.2016.08.001
0263-8762/ 2016 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
80 chemical engineering research and design 1 1 4 ( 2 0 1 6 ) 7988

desired product, with evident economic and environmental advantages On the other hand, gas back-mixing reaches a maximum in corre-
in comparison to Reaction 1a, where two carbon atoms are wasted in spondence of the transition velocity between bubbling and turbulent
the formation of CO2 for each reacting benzene molecule. regimes and decreases with increasing velocity (Li and Wu, 1991; Bai
ALMA (Alusuisse Italia-Lummus Crest) process, jointly developed et al., 1992). A number of the uid-dynamic features of the turbulent
and licensed by Lummus Technology Inc. and Polynt SpA, operates in regime, such as good gassolid contact, restrained gas back-mixing,
turbulent uidized bed conditions; Polynt reactor is located in Ravenna also due to the presence of several internals in the reactor (Zhang et al.,
(Italy), with a nominal MA capacity of 65,000 tons per year (Tecnon 2008), and uniform temperature in the dense bed are of paramount
OrbiChem, 2014, 2015). importance to switch selectivity to MA production (heterogeneous cat-
n-Butane partial oxidation to MA occurs in xed-, uidized- or alytic reaction) from gas-phase combustion of n-butane, increasing the
transport bed reactors (Lohbeck et al., 2000). The ALMA process is reactor yield and reducing the risk of local temperature runaways. In
heterogeneously catalyzed by vanadyl pyrophosphate (VO)2 P2 O7 ne particular, the temperature control of the bed reduces MA and n-butane
particles and uses uidized bed technology for producing high purity combustion risks that are favored by an increase of temperature.
MA (>99.9%w , downstream the plant purication section) (Stefani et al., As far as chemical reaction models are concerned, some literature
1990). This reactor choice is dictated by the noticeable heat of reaction, studies address the kinetics for MA production process (Centi et al.,
to limit temperature and concentration gradients within the catalyst 1985; Schneider et al., 1987; Bej and Rao, 1991; Mills et al., 1999; Sharma
and among different bed regions; the uid dynamic behavior of these et al., 1991). Most of them assume a simplied triangular reaction
systems is characterized as Geldart Group A (Gibilaro, 2001). Polynt SpA network and obtain the pre-exponential factor and activation energy
have been operating ALMA plant since 1994. In the ALMA reactor unit values for the relevant reaction kinetic expressions under xed bed
in Ravenna the supercial uidization velocity allows to obtain a tur- operating conditions, involving low n-butane partial pressure in air
bulent uidization regime. The dense bed temperature is below 723 K; (1.82.7% n-butane volume percentage (Sharma et al., 1991)). Additional
the reactor pressure is about 24 bar (Dente et al., 2003). An alternative, studies are performed under high n-butane concentration in aerobic
Circulating Fluidized Bed (CFB) technology, including catalyst reduc- (ALMA process) and anaerobic (DuPont process (Lohbeck et al., 2000))
ing and oxidizing reactors linked together by a solid circulation loop, conditions and more detailed kinetic schemes are considered (Gascn
was also developed by E.I. du Pont de Nemours, for partial oxidation et al., 2006; Lorences et al., 2004). In this paper, to keep reasonable the
of n-butane to MA (Patience and Bockrath, 2010), however commercial burden of calculations, it has been chosen to use the simplied tri-
exploitation of this process has been stopped. angular reaction network proposed in different kinetic studies quoted
Air/n-butane mixtures can be ammable in relation to their compo- below (see Table 2), specically that described by Sharma et al. (1991);
sition ratios, so in principle it is risky to operate simultaneously inside the values of the overall kinetic parameters have been properly tuned,
the ammability limits and above the ignition temperature (Sharma taking into account the industrial reactor operating performance and
et al., 1991). At room temperature, this mixture is characterized by low compared with literature estimates of the corresponding activation
and high ammability limits equal to 1.8%v and 8.5%v of n-butane, energies.
respectively (Centi et al., 2012). The spontaneous ignition tempera- As regards simulation of turbulent uidized beds, a quite large num-
ture at the stoichiometric concentration ratio is 704 K (Sharma et al., ber of uid dynamic models were developed to describe the reactor
1991). In a turbulent uidized bed reactor, the presence of a well dis- behavior. Turbulent-uidized-bed reactor models often assume single
persed particulate solid phase inhibits the mechanisms leading to an phase, either one dimensional plug ow (Van Swaaij, 1978; Fane and
explosive reaction; this has been clearly demonstrated in a study on Wen, 1982), or a continuous stirred tank reactor (CSTR) (Wen, 1984) or
methane homogeneous combustion (Van der Vaart, 1992). The ability axially dispersed plug ow (ADPF) (Wen, 1984; Edwards and Avidan,
of the granular phase to suppress non-selective homogeneous com- 1986). Two-phase models, adapted from bubbling uidization regime,
bustion and at the same time to promote the selective heterogeneous were also developed, with interchange of gas between dilute and dense
reactions is documented in the literature also for n-butane catalytic phase regions (Krambeck et al., 1987; Foka et al., 1996); nevertheless,
oxidation (Hutchenson et al., 2010). In such conditions, it is possible the representation of the transient and fuzzy nature of voids in tur-
to operate safely with n-butane/air ratios higher (about 45% n-butane bulent regime is not satisfactory (Thompson et al., 1999). In order to
volume percentage) than in a xed bed where more severe explosion overcome this a Generic Fluidized Bed Reactor model (GFBR) (Abba
problems exist, together with more stringent limitations to dissipate et al., 2002, 2003) was developed: different uidization regimes (bub-
the reaction heat. bling, turbulent, fast) are simulated for a two-regions (i.e. dense bed
A number of commercial gassolid uidized-bed reactors aimed at and freeboard) uidized bed, by transitions from a two-phase bubble
different processes, such as FischerTropsch synthesis, acrylonitrile model typical at low supercial velocities (bubbling uidization), pass-
production, FCC regeneration and silicon chlorination, are routinely ing through an axially dispersed plug-ow reactor model (turbulent
operated in the turbulent uidization regime (Du et al., 2002). This ow uidization), arriving to a core-annulus model at higher velocities (fast
regime is commonly considered to take place between bubbling and uidization).
fast uidization regimes (Bi et al., 2000). When ne particle beds are The model proposed in this paper adopts a two-regions approach
uidized at a sufciently high gas ow rate, instead of bubbles, one similar to GFBR (Abba et al., 2003), focusing on correspondence between
observes a turbulent motion of solid clusters and voids of gas of various simulation results and actual industrial measurements and on rep-
sizes and shapes (Kunii and Levenspiel, 1991). This regime offers dis- resentation of turbulent uidization, with a proper deployment of
tinct operational advantages over different uidization regimes, such calculation resources. In fact, the aim of our model is to faithfully
as vigorous gassolids contact, over the bubbling regime, high solid simulate performances of an actual industrial turbulent uidized bed
holdup, over the fast uidization regime, and altogether intense solid reactor, strictly designed to operate in this uid dynamic condition.
mixing determining a prevailing emulsion phase with relative spatial
uniformity in ow properties (Du et al., 2002).
In turbulent uidization conditions, the gas volume fraction is 2. Model description
greater compared to the bubbling regime (Bi et al., 2000), assuring a
better expansion of the bed. One of the most attractive features, partic-
In the case examined here, the industrial reactor conguration
ularly with highly exothermic or endothermic reactions, is an uniform
suggests to assume plug ow behavior for the gas phase, due
temperature eld, due to intense solids back-mixing, greater than in
to the presence of distributed reactor internals (heat transfer
bubbling and fast uidization regimes (Du et al., 2002). In a mixing
study on a commercial scale unit, it was suggested that the solids axial
tube bundles and bafes), and perfect mixing for the par-
dispersion coefcient is proportional to the square root of the bed diam- ticulate phase, according to uniform dense bed temperature
eter (Wei et al., 1993). From the above ndings follows that the particle measured in all production campaigns. On the other hand, in
bed closely approaches perfect mixing conditions in a large industrial the reactor freeboard above the bed, both gas and entrained
reactor like that considered here (ID > 5 m). solid phases are described by the plug-ow assumption. Actu-
chemical engineering research and design 1 1 4 ( 2 0 1 6 ) 7988 81

Table 1 Model equations.


dFi
Mole balances = b ri S; i = 1, . . ., 7 (1)
dZ

Ldb

Energy balance for Fw cp ,w (Tw,in Tw,out ) = hAS (Tw Tdb ) dZ (2)


the pressurized
0
cooling water in
the dense bed
dP
Pressure drop along = b g (3)
dZ
the reactor

Ldb
 
Global energy Fg,in cp,g Tg,in Tdb + Fw cp,w (Tw,in Tw,out ) + Fs cp,s (Ts,in Tdb )  |rij (Z) |b (Z) SdZHij = 0; j = 1, . . . , 3 (4)
j
balance in the
0
dense bed (Fogler,
2005)
dTfb hAS (Tw Tfb ) Sb 3j=1 |rij (Z) |Hij
Energy balance in = (5)
dZ Fg cpg + Fs cps
the freeboard
dTw Tfb Tw
Energy balance for = hAS (6)
dZ Fw cp,w
the pressurized
cooling water in
the freeboard

Table 2 Activation energy values proposed in this work compared to literature studies.
Kinetic model EA1 [kJ/mol] EA2 [kJ/mol] EA3 [kJ/mol]

Centi et al. (1985) 45.1 110 57.4


Buchanan and Sundaresan (1986) 125 145 180
Schneider et al. (1987) 72 7472a n.a.
Sharma et al. (1991) 93 93 155
Mills et al. (1999) 71 1367a n.a.
Dente et al. (2003) 79 n. p. 243
This work 60 45 190

n.a.: In these studies, a parallel reaction model is considered, which does not include MA oxidation, so that this activation energy is not available.
n.p.: Not published.
a
Two different reactions and corresponding activation energy values are considered for n-butane oxidation to CO2 and CO, respectively.

ally, recent studies are focusing on CFD simulation of the plug-ow of the gas phase and complete mixing of the solid
hydrodynamic behavior in the turbulent uidized bed using phase in the dense bed;
the standard EulerianEulerian two-uid model and in this uniform temperature in the dense bed;
frame the kinetic theory of granular ow (Gidaspow, 1994; negligible temperature differences between solid and gas
Wang, 2009, 2010; Xu et al., 2012; Yao et al., 2014; Chen et al., phases;
2015). This approach would be too expensive and time con- pressure gradients are entirely due to the weight of the cat-
suming when applied to the simulation of the MA industrial alyst holdup per unit reactor height, while inertial and wall
reactor, due to its dimensions and the presence of distributed effects are negligible;
internals (a complex geometry). Only a very ne grid, in fact, complete separation of catalyst particles from the product
could identify such complicated structures, while a loose grid gas in the cyclone, according to plant data showing negligi-
would distort the computational results (Wang, 2009). ble catalyst recovery in the subsequent lter unit;
In the model, the industrial reactor layout is schematized progressive temperature decrease with reactor length in the
as in Fig. 1. The air grid is located at the bottom of the reactor, freeboard, due to heat transfer to pressurized water owing
while a sparger is used to feed n-butane. The gaseous phase in tube bundles located along the reactor.
products and the elutriated solid particles leave the reactor
at the top and enter a cyclone, where solids are separated
and then recycled to the bottom of the bed. There are two The model equations are the following ones:
distinct zones inside the reactor, dense bed and freeboard, in
which reactions occur and the heat of reactions is transferred dense bed region: a system of nine differential conserva-
to pressurized water owing in the tube bundles. tion equations (seven molar balances for chemical species,
including nitrogenthe inert component, the energy bal-
2.1. Conservation equations ance for the cooling water owing in the tube bundles,
the momentum balance along the reactor to determine the
The following modeling assumptions are employed: pressure prole), plus a global energy balance referred to the
whole dense bed volume to calculate its temperature level;
reactor freeboard region: ten differential equations to
reactor layout, bed inventory and inlet conditions are xed describe concentrations, temperature, heat transfer and
according to plant data; pressure along the reactor length.
82 chemical engineering research and design 1 1 4 ( 2 0 1 6 ) 7988

is considered constant above the TDH (Total Disengagement


Product Height); TDH is evaluated by means of empirical relations pro-
Cyclone gas posed by Zenz and Wei (1958), Amitin et al. (1968) and Horio
et al. (1980). In this case, TDH resulted always lower than the
Water In freeboard height.
Evaluations for the elutriated catalyst ux, Gs , are available
from the plant data and have been utilized in the model equa-
Freeboard

tions; they are in fairly good agreement with values calculated


Water Out from literature correlations (Choi et al., 1999):
The knowledge of the overall catalyst inventory in the reac-
Gas and tor volume, Ms , allows to determine the dense bed height by
entrained
catalyst recycle
a trial and error procedure addressed to match the particulate
catalyst
Dip leg for
solid mass balance:
(PFR)
Water Out 
Ldb Lfd
b (Z) SdZ + b (Z) SdZ = Ms (11)
0 Ldb
Water In
Dense bed

The heat transfer coefcient for immersed horizontal tubes


Gas Solids in the dense bed is evaluated according to Vreedenberg (1958):
(PFR) (CSTR)
kg   0.44
hw = 0.66Prg0.3 g (1 ) /g ReD (12)
n-butane Dt

ReD = Dt Ug /g (13)


Air

Fig. 1 Simplied model representation of the industrial In the freeboard, the outer heat transfer coefcient from
n-butane partial oxidation reactor (nominal MA the uidized bed to the tube surface is evaluated as suggested
capacity = 65,000 tons per year). in the literature (Kunii and Levenspiel, 1991), using the same
decay constant as in Eq. (9):
The corresponding mathematical expressions are summa-
rized in Table 1. hfb = (hwdb hw ) exp (aZfb /2) + hw (14)
In the equations in Table 1, the index i denotes a gas com-
ponent, reactant or product, while j denotes the chemical where hwdb is evaluated by Eq. (12) at the top of the dense bed
reaction. The gas ow rate Fg includes also the inert com- while hw is that evaluated at the reactor head.
ponent, nitrogen. In the energy balances i is the reference The tube side convective heat transfer contribution is eval-
component for the heat of reaction, Hij . uated by means of the correlation:
To estimate the dense bed height, a modied
RichardsonZaki equation is applied to correlate the aver- Nu = 0.023Re0.8 Pr0.33 (15)
age voidage with the supercial gas velocity (Avidan and
Yerushalmi, 1982; Bi et al., 2000): 2.2. Reaction kinetics

U/Ut = ndb (7) Catalyst ne particles and a rather vigorous gas velocity are
adopted so that intra-phase and inter-phase mass transfer
where expressions to estimate Ut and n are provided by limitations are negligible and consequently there is not a mass
Venderbosch (1998) and the supercial gas velocity is evalu- transfer control on the reaction process. As mentioned above,
ated as a function of bed height, assuming ideal gas law: a simplied triangular reaction network is adopted: together
with the desired heterogeneous reaction of n-butane to maleic
U = Ftot RT/ (SP) (8) anhydride (Reaction 1), an undesired homogeneous oxidation
reaction is assumed to occur in parallel (Reaction 2). Finally,
The catalyst volume fraction in the freeboard is assumed to the catalytic partial combustion of maleic anhydride closes
decay exponentially with reactor length, from the value at the the network (Reaction 3). The stoichiometry of secondary reac-
top surface of the dense bed, db (Z = Ldb ) = 1 db (Z = Ldb ) tions and their rate Eqs. (16) and (17) are:
(Kunii and Levenspiel, 1991):
C4 H10 + 5.5O2 2CO + 2CO2 + 5H2 O H0 298K = 2092 kJ/mol
 =  + (db  ) exp (aZfb ) (9)
(Reaction 2)
where:

r2 = k2 p0.54 (16)
 = Gs / ((U Ut ) p ) (10) n-but

and a is given by (Abba et al., 2003). Gs = Fs /S is the elu-


C4 H2 O3 + O2 4CO + H2 O H0 298K = 258 kJ/mol
triated catalyst ux at the reactor head and Ut is the particle
terminal velocity. Gs corresponds to the elutriation rate, which (Reaction 3)
chemical engineering research and design 1 1 4 ( 2 0 1 6 ) 7988 83

Table 3 Pre-exponential factor for the three relevant


reaction kinetics, this work and Sharma et al. (1991).
Parameter This work Sharma et al.

k1 673 [mol kg1 s1 atm0.54 ] 2.20 103 0.96 103


k2 673 [mol kg1 s1 atm0.54 ] 0.30 103 0.15 103
k3 673 [mol kg1 s1 atm1 ] 0.22 102 0.29 102
KMA [atm1 ] 185 310

r3 = k3 pMA /(1 + KMA pMA )2 (17)

The rate equation for Reaction 1 is:

r1 = k1 p0.54 / + KMA pMA )


nbut (1
(18)

The above kinetic expressions are those proposed by


Fig. 2 Catalyst bulk density prole along reactor height
Sharma et al. (1991). The oxygen partial pressure does not
(normalized by overall reactor height, L).
appear explicitly: as the matter of fact, the plant data show
that the reactor always operates with an oxygen excess.
The rate constants are given by an Arrhenius type temper- SCO = (Fg out xout CO )/(4(Fg in xin n-but Fg out xoutn-but )) (22)
ature dependency:
Then a sensitivity parametric study is carried out to check
 E 
Ai the ability of simulations to comply with control strategies
ki = ki673 exp (1 673/T) (19)
673R usually adopted at the plant site and to help investigating
process optimization measures.
Values for activation energies and pre-exponential factors
found in the literature mainly depend on the range of experi-
3.1. Comparison between numerical calculations and
mental conditions, as already mentioned.
experimental results
Finally, the reaction rate expressions for each reactant and
product species, to be used in the equations of Table 1, fol-
3.1.1. Kinetic constants
low immediately from stoichiometric relations of Reactions
The pre-exponential factor and activation energy for Reac-
(1)(3), together with the corresponding constitutive kinetic
tions (1)(3) were obtained starting from the corresponding
expressions given by Eqs. (16)(18) and the kinetic parameters
values proposed by Sharma et al. (1991) and optimizing them
reported in Tables 2 and 3, in Section 3.1.1.
to allow a good tting of the industrial performance. The
activation energy values, nally identied as a result of this
2.3. Numerical procedure to integrate model equations procedure, are compared with literature results in Table 2.
As shown in Table 2, the activation energy values xed in
The numerical integration was implemented in MATLAB
this study are well inside the range of values proposed in the
using the integration routine ode45, based on an explicit
literature. This result provides a general indication that the
RungeKutta numerical scheme of 4th order. The input data
reactor model proposed here is able to combine correctly the
include: reactor geometry; overall catalyst inventory; parti-
uid-dynamic and chemical aspects of the reacting system
cle density, equivalent diameter and specic heat capacity;
under consideration.
inlet gas ow rate, air/n-butane ratio, temperature and pres-
As far as the pre-exponential factor is concerned, a direct
sure; cooling water ow rate and heat transfer surface per unit
comparison is possible only with Sharma et al. (1991), as
reactor volume. Before the integration, dense bed temperature
reported in Table 3. It should be considered that in Sharma
and height, together with solids recirculation rate, need to be
et al. (1991) the experimental concentration ratio n-butane/air
assumed and iteratively adjusted until reactor steady condi-
was different from that adopted in the industrial reactor.
tions are reached: this preliminary step completes the input
data set to nally solve the system of model equations.
3.1.2. Catalyst bulk density and pressure prole along the
reactor height
3. Results and discussion In this section, simulation results are presented, in dimen-
sionless form, for the catalyst bulk density and pressure drop
In order to validate the predictive capabilities of the pro-
prole along the reactor height and catalyst recirculation rate.
posed model, simulations were carried out at typical operating
Fig. 2 shows the catalyst bulk density, b , as a function of reac-
conditions of the MA reactor. The numerical calculations are
tor height. The corresponding pressure drop along the reactor
compared with experimental results in terms of pressure drop
height is calculated as shown in Fig. 3. Numerical results in
and temperature prole, n-butane conversion (20), MA selec-
Fig. 2 are in very good agreement with the pressure drop trend
tivity (21), CO selectivity (22) and the ratio CO/CO2 .
recorded at the plant site (measured values in Fig. 3) and allow
to determine the dense bed height inside the reactor.
Xn-but = (Fg in xin n-but Fg out xout n-but )/(Fg in xin n-but ) (20) As mentioned above, the catalyst recirculation rate pre-
dicted by model equations is close to that one evaluated at
SMA = (Fg out xout MA )/(Fg in xin n-but Fg out xout n-but ) (21) the plant site. The renewal time of the solid reactor hold up is
84 chemical engineering research and design 1 1 4 ( 2 0 1 6 ) 7988

Fig. 3 Dimensionless pressure prole as a function of


dimensionless reactor height: comparison of numerical
results () with experimental data (). Measured pressures
oscillate between 5% of the respective average values.

Fig. 5 (a) Normalized n-butane conversion predicted by the


model as a function of the dimensionless reactor height: (b)
MA and CO selectivity, and CO/CO2 ratio predicted by the
model as functions of the normalized n-butane conversion,
Fig. 4 Dimensionless temperature prole as a function of compared with corresponding experimental data recorded
the dimensionless reactor height: comparison of numerical at the exit of the reactor. Measured selectivities and CO/CO2
results () with experimental data (). Measured ratio oscillate between 2% of the respective average value.
temperatures oscillate between 1% of the respective
average value.
The catalyst inlet temperature, Ts,in , at the bottom of the
estimated to be of the order of ten minutes. The consequent reactor is chosen to be 20 K below the exit temperature from
considerable ux of solid from cyclones enters the reactor at the top of reactor. Ts,out , according to plant estimates:
its bottom section at signicantly lower temperature than the
dense bed temperature: this contributes to avoid hot-spots in T s,in = T s,out 20 (23)
the reactor region where the reactant concentrations are max-
imum (i.e. the bottom) and to keep the dense bed temperature 3.1.4. MA yield and selectivities
reasonably constant, as shown in the next section. In Fig. 5a, the n-butane conversion is shown as a function of
the reactor height, while in Fig. 5b MA and CO selectivity and
3.1.3. Temperature prole CO/CO2 ratio are reported as functions of the n-butane conver-
Very good agreement is found between calculated and mea- sion; activation energy and pre-exponential factor values are
sured temperature in the dense bed and for most of the those reported in Tables 2 and 3, respectively. Model predic-
freeboard region. The highest heat exchange tube bundle is tions are compared to the experimental data recorded at the
located just below 80% of the overall reactor height. The exit of the reactor.
reaction rate is also quite small there, so that the model pre-
dicts substantially constant temperature above 80% of reactor 3.2. Parametric sensitivity analysis of the simulation
height. On the other hand, the temperature measured in the model
cyclone inlet pipe is somehow lower (Fig. 4, Z/L = 1); this dif-
ference is mainly ascribable to local gas cooling at the exit of The simulation model is now applied to examine the inuence
the reactor due to an increase of heat losses to the ambient, of small perturbations in inlet parameters on the reactor per-
close to the reactor ceiling and in the exit pipe. formance; perturbed parameters are inlet gas ow rate and
chemical engineering research and design 1 1 4 ( 2 0 1 6 ) 7988 85

n-BUTANE CONVERSION MA SELECTIVITY DENSE BED HEIGHT

Variaon calculated by the model


6 2 4

3 1 2

0 0 0
[%]

-3 -1 -2

-6 -2 -4
-10 0 10 -10 0 10 -10 0 10

Imposed perturbaon of the input variable [%]

CATALYST RECIRCULATION RATE CO/CO2 RATIO OUTLET O2 MOLAR FRACTION


40 2 30
Variaon calculated by the

20 1 15
model [%]

0 0 0

-20 -1 -15

-40 -2 -30
-10 0 10 -10 0 10 -10 0 10
Imposed perturbaon of the input variable [%]

Fig. 6 Parametric sensitivity analysis of the simulation model: predicted percentage variation of n-butane conversion, MA
selectivity, dense bed height, catalyst recirculation rate, CO/CO2 ratio and outlet O2 molar fraction as functions of 10%
change of input variables: actual gas inlet ow rate () and n-butane/air ratio (), respectively.

n-butane/air feeding ratio. In real circumstances, its impor- 10


Variaon of steam producon [%]

tant to keep the temperature of the dense bed at its steady


state level because of catalyst sensitivity to this quantity:
5
the catalyst may change its constitutive phases and its activ-
ity (Gabriele et al., 1988), so that kinetic parameters utilized
in model equations would become less reliable. As a conse- 0
quence, in each simulation the heat transfer surface in the
reactor is appropriately increased or reduced, in such a way
-5
as to keep the temperature prole almost constant: this corre-
sponds closely to the real operative procedure at the plant site
to control the reactor temperature: opening or closing valves -10
-10 -5 0 5 10
regulating the ow of pressurized water through internal tube
Imposed variaons of the input variable [%]
bundles, so controlling the number of tubes actually operating
for heat removal. Fig. 7 Parametric sensitivity analysis of the simulation
Fig. 6 shows effects on n-butane conversion, MA selectivity, model: predicted percentage variation of steam production
dense bed height, catalyst recirculation rate, CO/CO2 ratio and required to keep constant the dense bed temperature level
oxygen molar fraction at reactor exit, due to a variation within at each simulated condition, as a function of 10% change
a 10% range of the above mentioned inlet parameters. Fig. 7 of input variables: actual gas inlet ow rate () and
reports the corresponding effects on the steam production n-butane/air ratio (), respectively.
(proportional to the heat subtracted from the reactor by the
pressurized water ow) required to keep constant the dense above. It is worth stressing here that simulations take into
bed temperature level at each operating condition. consideration variations in the reactor hydrodynamic behav-
The reactor results to operate at quite stable conditions: ior brought about by each perturbed state: parameter values
variations in quantities (except for oxygen molar fraction and are properly adjusted to different operating conditions (Eqs.
catalyst recirculation rate) at reactor exit (about 5% maximum (7)(15)) and the constraint of turbulent uidization regime is
relative deviation) are smaller than the amplitude of uctu- always satised, so that model predictions are expected to be
ation imposed to inlet parameters. On the other hand, the reliable, also because of previous validation with the reactor
corresponding variation of steam production required to keep real outputs.
the dense bed temperature (Fig. 7) shows that the reactor In the reactor energy balance, an additional operating
behavior is quite sensitive to this quantity: the model conrms parameter is represented by the heat ow associated to the
the appropriateness and reliability of the temperature control particulate catalyst recirculated to the bottom section (Fig. 1):
strategy implemented in the actual reactor and mentioned the exothermic reactions extent is particularly relevant in the
86 chemical engineering research and design 1 1 4 ( 2 0 1 6 ) 7988

3 Notations
Variaon of dense bed temperature [%]

A Heat-transfer surface area per unit reactor volume


1.5 [m1 ]
a Decay constant [m1 ]
Ar Archimedes number [dimensionless]
0
CD Particle drag coefcient based on the supercial gas
Reference operating conditions velocity [dimensionless]
-1.5 cp Heat capacity [kJ mol1 K1 ] [kJ kg1 K1 ]
Dt Cooling tube diameter [m]
-3 dp Particle equivalent diameter [m]
-1 0 1 2 fd Drag force on the particle per projection area [Pa]
Variaon of catalyst inlet temperature [%]
fg Gravity force minus buoyancy force per projection
area of particle [Pa]
Fig. 8 Model prediction of dense bed temperature as a Fg Gas ow rate [mol s1 ]
function of the temperature variation of catalyst Fs Solid ow rate [kg s1 ]
recirculated to the bottom of the reactor. Fw Water ow rate [kg s1 ]
g Acceleration of gravity [m s2 ]
reactants inlet region, so that solid recirculation rate is very Gs Solids ux [kg m2 s1 ]
important to assure reactor thermal stability (making avail- h Overall bed-to-surface heat-transfer coefcient
able its heat capacity in that region), in addition to a proper [kJ s1 m2 K1 ]
recovery of the elutriated catalyst. Simulations have been per- hw Outer heat transfer coefcient [kJ s1 m2 K1 ]
formed keeping constant the catalyst recirculation rate, found KMA Maleic anhydride adsorption rate constant [atm1 ]
in Section 3.1, and assuming small deviations of its inlet tem- kg Gas thermal conductivity [kJ s1 m1 K1 ]
perature. With relation to the reference operating conditions, kw Water thermal conductivity [kJ s1 m1 K1 ]
small perturbations of the catalyst recirculation temperature L Overall reactor height [m]
determine an appreciable variation in dense bed temperature, Ldb Dense bed height [m]
as reported in Fig. 8, showing the important role of the catalyst Lfb Freeboard height [m]
heat capacity to control the reactor temperature in the feeding Ms Overall catalyst inventory [kg]
zone, in addition to the heat transfer system, the inuence of Nu Nusselt number Nu = hwin Dt /kw , dimensionless
which is already examined in Fig. 7. P Pressure [atm]
Pr Prandtl number Pr = cpw w /kw , dimensionless
4. Conclusions r Reaction rate [mol kg1 s1 ]
Re Reynolds number, Re = Dt U/ [dimensionless]
The focus of this paper is on uid-dynamic and chemi- ReD Reynolds number based on tube diameter [dimen-
cal simulation of an industrial scale, turbulent uidized-bed sionless]
reactor for n-butane catalytic partial oxidation with air to Rep Particle Reynolds number Rep =
maleic anhydride: model equations and constitutive expres- p dp U/, [dimensionless]
sions were fully described, assumptions and input variables S Bed cross-sectional area [m2 ]
were carefully identied so that numerical solutions can be SCO CO selectivity [dimensionless]
obtained for diversied operating conditions of interest. SMA MA selectivity [dimensionless]
The model assumes reasonable gas and solid dispersion T Temperature [K]
conditions in the dense bed and in the freeboard, literature U Supercial velocity [m s1 ]
correlations to estimate turbulent uidization quality and a Ut Particle terminal velocity [m s1 ]
simplied reaction kinetic model, in which activation ener- Ut Effective terminal cluster velocity [m s1 ]
gies and pre-exponential factors are adjusted to match the Xn-bu n-Butane conversion [dimensionless]
real plant operating data. x Component molar fraction [dimensionless]
The model can simulate faithfully the industrial reactor Z Axial coordinate [m]
behavior and highlight the role of major variables, such as the
heat exchange system or the heat capacity and temperature Greek letters
of catalyst recirculated at the bottom of the reactor. H Heat of reaction [kJ mol1 ]
A parametric sensitivity analysis was also performed, con- Bed voidage [dimensionless]
sidering the inuence of inlet ow rate and n-butane/air ratio  Viscosity [Pa s]
on n-butane conversion, MA selectivity, dense bed height, b Bulk density, b = p (1 ), [kg m3 ]
catalyst recirculation rate, CO/CO2 ratio, outlet reactor tem- g Gas density [kg m3 ]
perature and steam production by the heat transfer system. p Particle density [kg m3 ]
This analysis depicts a reactor operating in stable conditions,  Catalyst volume fraction [dimensionless]
with relatively small changes of these quantities in presence
of inlet parameter perturbations. This result agrees with the Subscripts
evidences emerged from actual MA production campaigns in db Dense bed
the real plant. fb Freeboard
In force of these experimental proofs and despite its sim- g Gas
ple, however not simplistic, approach, the model developed h Particle size index
in this work is proposed as a useful tool to design and apply i Component index
appropriate reactor control strategies. in Inlet
chemical engineering research and design 1 1 4 ( 2 0 1 6 ) 7988 87

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