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Industrial Engineering Department, University of LAquila, 18 via G. Gronchi, 67100 LAquila, Italy
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:
which performs n-butane partial oxidation to maleic anhydride (MA) catalyzed by (VO)2 P2 O7
solid particles, is proposed. Main assumptions are: gas plug-flow in the dense bed because
gas back-mixing is minimized by internals; perfectly mixed particulate phase in the dense
bed due to high recirculation rate of entrained particles at the bottom of the reactor, after
separation by cyclones; plug-flow of both gas and solids in the freeboard. Literature kinetic
Keywords:
models are considered to simulate reactions, slightly modified to allow careful prediction of
industrial performance. The model is organized in ordinary differential and algebraic equa-
tions describing mass and energy balances and constitutive expressions for reaction rates,
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 flow rate
and n-butane/air feeding ratio are varied within a 10% range around industrial operating 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
lower cost compared to olefins (Hutchenson et al., 2010). Since the 80s,
processes based on this reaction have been replacing the more traditional production of MA from benzene (Reaction 1a) on commercial
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
On the other hand, gas back-mixing reaches a maximum in correspondence of the transition velocity between bubbling and turbulent
regimes and decreases with increasing velocity (Li and Wu, 1991; Bai
et al., 1992). A number of the fluid-dynamic features of the turbulent
regime, such as good gassolid contact, restrained gas back-mixing,
also due to the presence of several internals in the reactor (Zhang et al.,
2008), and uniform temperature in the dense bed are of paramount
importance to switch selectivity to MA production (heterogeneous catalytic reaction) from gas-phase combustion of n-butane, increasing the
reactor yield and reducing the risk of local temperature runaways. In
particular, the temperature control of the bed reduces MA and n-butane
combustion risks that are favored by an increase of temperature.
As far as chemical reaction models are concerned, some literature
studies address the kinetics for MA production process (Centi et al.,
1985; Schneider et al., 1987; Bej and Rao, 1991; Mills et al., 1999; Sharma
et al., 1991). Most of them assume a simplified triangular reaction
network and obtain the pre-exponential factor and activation energy
values for the relevant reaction kinetic expressions under fixed bed
operating conditions, involving low n-butane partial pressure in air
(1.82.7% n-butane volume percentage (Sharma et al., 1991)). Additional
Air/n-butane mixtures can be flammable in relation to their composition ratios, so in principle it is risky to operate simultaneously inside
the flammability limits and above the ignition temperature (Sharma
below (see Table 2), specifically that described by Sharma et al. (1991);
the values of the overall kinetic parameters have been properly tuned,
were also developed, with interchange of gas between dilute and dense
phase regions (Krambeck et al., 1987; Foka et al., 1996); nevertheless,
the representation of the transient and fuzzy nature of voids in turbulent regime is not satisfactory (Thompson et al., 1999). In order to
model typical at low superficial velocities (bubbling fluidization), passing through an axially dispersed plug-flow reactor model (turbulent
fluidization), arriving to a core-annulus model at higher velocities (fast
operated in the turbulent fluidization regime (Du et al., 2002). This flow
regime is commonly considered to take place between bubbling and
fast fluidization regimes (Bi et al., 2000). When fine particle beds are
fluidized at a sufficiently high gas flow rate, instead of bubbles, one
observes a turbulent motion of solid clusters and voids of gas of various
sizes and shapes (Kunii and Levenspiel, 1991). This regime offers distinct operational advantages over different fluidization regimes, such
as vigorous gassolids contact, over the bubbling regime, high solid
fluidization).
The model proposed in this paper adopts a two-regions approach
similar to GFBR (Abba et al., 2003), focusing on correspondence between
simulation results and actual industrial measurements and on representation of turbulent fluidization, with a proper deployment of
calculation resources. In fact, the aim of our model is to faithfully
simulate performances of an actual industrial turbulent fluidized bed
holdup, over the fast fluidization regime, and altogether intense solid
mixing determining a prevailing emulsion phase with relative spatial
uniformity in flow properties (Du et al., 2002).
2.
Model description
81
dFi
= b ri S; i = 1, . . ., 7
dZ
(1)
Fw cp ,w (Tw,in Tw,out ) =
(2)
Ldb
dP
= b g
dZ
(3)
Ldb
Fg,in cp,g Tg,in Tdb + Fw cp,w (Tw,in Tw,out ) + Fs cp,s (Ts,in Tdb )
(4)
j
0
(5)
Tfb Tw
dTw
= hAS
Fw cp,w
dZ
(6)
Table 2 Activation energy values proposed in this work compared to literature studies.
Kinetic model
EA1 [kJ/mol]
45.1
125
72
93
71
79
60
EA2 [kJ/mol]
110
145
7472a
93
1367a
n. p.
45
EA3 [kJ/mol]
57.4
180
n.a.
155
n.a.
243
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.
2.1.
Conservation equations
dense bed region: a system of nine differential conservation equations (seven molar balances for chemical species,
including nitrogenthe inert component, the energy balance for the cooling water flowing in the tube bundles,
the momentum balance along the reactor to determine the
pressure profile), plus a global energy balance referred to the
whole dense bed volume to calculate its temperature level;
reactor freeboard region: ten differential equations to
describe concentrations, temperature, heat transfer and
pressure along the reactor length.
82
Cyclone
Product
gas
Freeboard
Water In
Gas and
entrained
catalyst
(PFR)
Water Out
Water Out
Ldb
Lfd
b (Z) SdZ +
Dense bed
Water In
hw =
n-butane
(12)
Air
(13)
0.44
kg
0.66Prg0.3 g (1 ) /g ReD
Dt
(11)
Gas Solids
(PFR) (CSTR)
U/Ut = ndb
b (Z) SdZ = Ms
Ldb
(9)
(14)
where hwdb is evaluated by Eq. (12) at the top of the dense bed
while hw is that evaluated at the reactor head.
The tube side convective heat transfer contribution is evaluated by means of the correlation:
Nu = 0.023Re0.8 Pr0.33
2.2.
(15)
Reaction kinetics
(Reaction 2)
where:
= Gs / ((U Ut ) p )
(10)
and a is given by (Abba et al., 2003). Gs = Fs /S is the elutriated catalyst flux at the reactor head and Ut is the particle
terminal velocity. Gs corresponds to the elutriation rate, which
r2 = k2 p0.54
n-but
C4 H2 O3 + O2 4CO + H2 O
(16)
83
This work
Sharma et al.
2.20 103
0.30 103
0.22 102
185
0.96 103
0.15 103
0.29 102
310
(17)
(18)
E
Ai
673R
(1 673/T)
(19)
2.3.
3.
In order to validate the predictive capabilities of the proposed model, simulations were carried out at typical operating
conditions of the MA reactor. The numerical calculations are
compared with experimental results in terms of pressure drop
and temperature profile, n-butane conversion (20), MA selectivity (21), CO selectivity (22) and the ratio CO/CO2 .
Xn-but = (Fg in xin n-but Fg out xout n-but )/(Fg in xin n-but )
(20)
SMA = (Fg out xout MA )/(Fg in xin n-but Fg out xout n-but )
(21)
(22)
3.1.
Comparison between numerical calculations and
experimental results
3.1.1.
Kinetic constants
The pre-exponential factor and activation energy for Reactions (1)(3) were obtained starting from the corresponding
values proposed by Sharma et al. (1991) and optimizing them
to allow a good fitting of the industrial performance. The
activation energy values, finally identified as a result of this
procedure, are compared with literature results in Table 2.
As shown in Table 2, the activation energy values fixed in
this study are well inside the range of values proposed in the
literature. This result provides a general indication that the
reactor model proposed here is able to combine correctly the
fluid-dynamic and chemical aspects of the reacting system
under consideration.
As far as the pre-exponential factor is concerned, a direct
comparison is possible only with Sharma et al. (1991), as
reported in Table 3. It should be considered that in Sharma
et al. (1991) the experimental concentration ratio n-butane/air
was different from that adopted in the industrial reactor.
84
3.1.3.
Temperature profile
Very good agreement is found between calculated and measured temperature in the dense bed and for most of the
freeboard region. The highest heat exchange tube bundle is
located just below 80% of the overall reactor height. The
reaction rate is also quite small there, so that the model predicts substantially constant temperature above 80% of reactor
height. On the other hand, the temperature measured in the
cyclone inlet pipe is somehow lower (Fig. 4, Z/L = 1); this difference is mainly ascribable to local gas cooling at the exit of
the reactor due to an increase of heat losses to the ambient,
close to the reactor ceiling and in the exit pipe.
3.1.4.
(23)
3.2.
model
85
n-BUTANE CONVERSION
MA SELECTIVITY
-3
-1
-2
-6
-2
-10
-4
-10
10
-10
10
10
CO/CO2 RATIO
40
30
20
15
-20
-1
-15
-40
-2
-10
10
-30
-10
-10
10
10
n-butane/air feeding ratio. In real circumstances, its important to keep the temperature of the dense bed at its steady
state level because of catalyst sensitivity to this quantity:
the catalyst may change its constitutive phases and its activity (Gabriele et al., 1988), so that kinetic parameters utilized
in model equations would become less reliable. As a consequence, in each simulation the heat transfer surface in the
reactor is appropriately increased or reduced, in such a way
as to keep the temperature profile almost constant: this corresponds closely to the real operative procedure at the plant site
to control the reactor temperature: opening or closing valves
regulating the flow of pressurized water through internal tube
bundles, so controlling the number of tubes actually operating
for heat removal.
Fig. 6 shows effects on n-butane conversion, MA selectivity,
dense bed height, catalyst recirculation rate, CO/CO2 ratio and
oxygen molar fraction at reactor exit, due to a variation within
a 10% range of the above mentioned inlet parameters. Fig. 7
reports the corresponding effects on the steam production
(proportional to the heat subtracted from the reactor by the
pressurized water flow) required to keep constant the dense
bed temperature level at each operating condition.
The reactor results to operate at quite stable conditions:
variations in quantities (except for oxygen molar fraction and
catalyst recirculation rate) at reactor exit (about 5% maximum
relative deviation) are smaller than the amplitude of fluctuation imposed to inlet parameters. On the other hand, the
corresponding variation of steam production required to keep
the dense bed temperature (Fig. 7) shows that the reactor
behavior is quite sensitive to this quantity: the model confirms
the appropriateness and reliability of the temperature control
strategy implemented in the actual reactor and mentioned
-5
-10
-10
-5
0
5
Imposed variaons of the input variable [%]
10
86
1.5
-3
-1
0
1
Variaon of catalyst inlet temperature [%]
4.
Conclusions
The focus of this paper is on fluid-dynamic and chemical simulation of an industrial scale, turbulent fluidized-bed
reactor for n-butane catalytic partial oxidation with air to
maleic anhydride: model equations and constitutive expressions were fully described, assumptions and input variables
were carefully identified so that numerical solutions can be
obtained for diversified operating conditions of interest.
The model assumes reasonable gas and solid dispersion
conditions in the dense bed and in the freeboard, literature
correlations to estimate turbulent fluidization quality and a
simplified reaction kinetic model, in which activation energies and pre-exponential factors are adjusted to match the
real plant operating data.
The model can simulate faithfully the industrial reactor
behavior and highlight the role of major variables, such as the
heat exchange system or the heat capacity and temperature
of catalyst recirculated at the bottom of the reactor.
A parametric sensitivity analysis was also performed, considering the influence of inlet flow rate and n-butane/air ratio
on n-butane conversion, MA selectivity, dense bed height,
catalyst recirculation rate, CO/CO2 ratio, outlet reactor temperature and steam production by the heat transfer system.
This analysis depicts a reactor operating in stable conditions,
with relatively small changes of these quantities in presence
of inlet parameter perturbations. This result agrees with the
evidences emerged from actual MA production campaigns in
the real plant.
In force of these experimental proofs and despite its simple, however not simplistic, approach, the model developed
in this work is proposed as a useful tool to design and apply
appropriate reactor control strategies.
Notations
A
Heat-transfer surface area per unit reactor volume
[m1 ]
Decay constant [m1 ]
a
Archimedes number [dimensionless]
Ar
Particle drag coefficient based on the superficial gas
CD
velocity [dimensionless]
Heat capacity [kJ mol1 K1 ] [kJ kg1 K1 ]
cp
Cooling tube diameter [m]
Dt
Particle equivalent diameter [m]
dp
fd
Drag force on the particle per projection area [Pa]
Gravity force minus buoyancy force per projection
fg
area of particle [Pa]
Fg
Gas flow rate [mol s1 ]
Solid flow rate [kg s1 ]
Fs
Water flow rate [kg s1 ]
Fw
g
Acceleration of gravity [m s2 ]
Gs
Solids flux [kg m2 s1 ]
Overall bed-to-surface heat-transfer coefficient
h
[kJ s1 m2 K1 ]
hw
Outer heat transfer coefficient [kJ s1 m2 K1 ]
KMA
Maleic anhydride adsorption rate constant [atm1 ]
Gas thermal conductivity [kJ s1 m1 K1 ]
kg
Water thermal conductivity [kJ s1 m1 K1 ]
kw
Overall reactor height [m]
L
Ldb
Dense bed height [m]
Freeboard height [m]
Lfb
Ms
Overall catalyst inventory [kg]
Nusselt number Nu = hwin Dt /kw , dimensionless
Nu
Pressure [atm]
P
Pr
Prandtl number Pr = cpw w /kw , dimensionless
Reaction rate [mol kg1 s1 ]
r
Re
Reynolds number, Re = Dt U/ [dimensionless]
ReD
Reynolds number based on tube diameter [dimensionless]
Particle
Rep
Reynolds
number
Rep =
p dp U/, [dimensionless]
S
Bed cross-sectional area [m2 ]
CO selectivity [dimensionless]
SCO
SMA
MA selectivity [dimensionless]
Temperature [K]
T
Superficial velocity [m s1 ]
U
Ut
Particle terminal velocity [m s1 ]
Viscosity [Pa s]
Bulk density, b = p (1 ), [kg m3 ]
b
Gas density [kg m3 ]
g
p
Particle density [kg m3 ]
Catalyst volume fraction [dimensionless]
Subscripts
Dense bed
db
Freeboard
fb
g
Gas
Particle size index
h
i
Component index
Inlet
in
j
out
s
w
Reaction index
Outlet
Solid
Water
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