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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.
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 2 Activation energy values proposed in this work compared to literature studies.
Kinetic model EA1 [kJ/mol] EA2 [kJ/mol] EA3 [kJ/mol]
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
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
3 1 2
0 0 0
[%]
-3 -1 -2
-6 -2 -4
-10 0 10 -10 0 10 -10 0 10
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.
3 Notations
Variaon of dense bed temperature [%]
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