Article

pubs.acs.org/IECR

Non-Adiabatic Multitubular Fixed-Bed Catalytic Reactor Model

Coupled with Shell-Side Coolant CFD Model
Eric J. Hukkanen,* Michael J. Rangitsch, and Paul M. Witt
The Dow Chemical Company, Midland, Michigan 48674, United States

ABSTRACT: An overall fixed-bed reactor model that combines a one-dimensional plug flow reactor model with a
computational fluid dynamics (CFD) model of the shell-side coolant fluid over a series of individual reactor tubes is presented.
The model chemistry is the partial oxidation of o-xylene to phthalic anhydride, a well-studied system for reactor performance.
The model is used to investigate the effect of variation in cooling temperature on overall reactor performance: temperature
profiles at the wall and centerline and o-xylene conversion. Non-isothermal shell-side cooling temperature profiles are calculated
using computational fluid dynamics and heat flux profiles along the reactor tube length. This analysis demonstrates that, with
faster coolant flow rates, the coupled fixed-bed reactor and CFD model process outputs approach the nominal case. Alternative
shell-side baffle configurations are examined. The calculated coolant velocity profiles, though different between evaluated
configurations, result in similar overall reactor performance. However, it should be noted that none of the simulations observe
isothermal shell-side coolant temperatures, as is commonly assumed in fixed-bed and plug flow reactor models. This coupled
model enables opportunity for further reactor optimization on both the shell-side CFD model and the fixed-bed reactor model, as
it can be applied to pilot- and commercial-scale reactors for existing or new chemistries. This model provides a more realistic
estimation of the reactor performance, when considering isothermal coolant profiles. Specifically, for the fixed-bed reactor model,
alternative catalyst packing schedules (i.e., activity profiles) or feed rates can be considered. Additionally, conditions or individual
reactor tubes can be identified that are more prone to runaway.

■ INTRODUCTION
The multitubular fixed-bed reactor system is used for strongly
exothermic reactions, such as partial oxidation reactions.
A typical multitubular reactor system can contain several
thousand tubes, sometimes up to 20 000 tubes. In these reactor
systems, a circulating heat-transfer fluid is used to remove the
large heat of reaction and maintain the fixed-bed temperature
within a narrow range.1 Proper design, loading, and operation
of fixed-bed reactors requires a combination of reactor
modeling, pilot plant trials, and catalyst bed grading to achieve
desired reactor performance.
Fixed-bed reactor models can be classified into two types of
models: pseudo-homogeneous or heterogeneous.2 Both model
classifications can be modeled in one or two dimensions. The
pseudo-homogeneous one-dimensional models assumes con-
centration and temperature gradients only in the axial direction.
Axial mixing and diffusion can also be incorporated into the
one-dimensional model. The pseudo-homogeneous two-
dimensional model incorporates heat and mass transfer in the
axial and radial direction. Heterogeneous reaction models are
used when it is necessary to distinguish between the fluid phase
and catalyst surface (i.e., concentration and temperature of fluid
are different than those at the catalyst surface). Computational
fluid dynamics (CFD) are more commonly used to investigate
the flow patterns within the fixed-bed reactor tube to better
understand heat and mass transfer and its influence on reaction
kinetics.1,3
As in most cases with fixed-bed reactor models, fixed-bed
reactors and reactor performance are evaluated assuming a
constant shell-side coolant temperature. Recent advances allow
for computational tools that enable more accurate modeling
of multitubular fixed-bed reactors. Hybrid gPROMS-CFD
Multitubular software is one such commercial software package
that enables modeling of fixed-bed reactors and shell-side tem-
perature profiles using CFD.4 This commercial package was
used to evaluate and optimize reactor performance of terephth-
aldehyde production.5
This paper presents a fixed-bed reactor model that combines
a one-dimensional plug flow reactor model with a CFD model
of the shell-side coolant fluid over a series of individual reactor
tubes. The model chemistry is the partial oxidation of o-xylene
to phthalic anhydride. Partial oxidation of o-xylene has been
studied extensively by several researchers.2,6−12 Primary
research topics focused on reaction kinetics, reactor perfor
mance, graded catalyst beds and catalyst activity, and evaluation
of hot spots or runaway conditions. Reactor performance
resulting from non-isothermal shell-side coolant temperature
has not been investigated.
In this analysis, the shell-side temperature of the fixed-bed
reactor is not isothermal. The fixed-bed reactor model presented
is a one-dimensional model based on the work of Hagen et al.13
that accounts for heat generation distribution along the radial
direction. The Hagen method is comparable to two-dimensional
conservation equations, though other appropriate models can
be used.
The shell-side coolant temperature is addressed using computa-
tional fluid dynamics (CFD). While CFD is well suited to
Special Issue: NASCRE 3
Received: March 2, 2013
Revised: May 3, 2013
Accepted: May 6, 2013

© XXXX American Chemical Society A dx.doi.org/10.1021/ie4006832 | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research Article

modeling heat and mass transfer in a tubular packed bed reactor, Table 1. Reactor and Reaction Constants
industrial scale reactors tend to have many individual reactor
constants description value units
tubes (reactors with more than 50 000 tubes are not unknown). It
is possible to model the detailed flow around each tube, but the ΔHrxn,1 heat of reaction 1 −264 kcal/mol
size of the problem thus generated would consume vast amounts ΔHrxn,2 heat of reaction 2 −781 kcal/mol
of computational resources. In cases with large numbers of tubes, ΔHrxn,3 heat of reaction 3 −1045 kcal/mol
it is possible to approximate the shell-side flow domain as a A1 pre-exponential 1.632 × 10−2 mol/(kgcat s atm2)
reaction 1
porous medium. Non-isotropic momentum losses are used to add A2 pre-exponential 1.583 × 10−3 mol/(kgcat s atm2)
the directional nature of pressure drops in a tube bundle. With reaction 2
this treatment it is possible to achieve fairly good agreement with A3 pre-exponential 1.789 × 10−3 mol/(kgcat s atm2)
observed flow distribution and pressure drop.14 The fixed-bed reaction 3
reactor model and CFD model are coupled by the shell-side Bi Biot number, (hwdt/2kr,e) 0.802
coolant temperature and reactor heat flux along each tube. dt reactor tube diam. 0.0254 m
Figure 1 illustrates a schematic of a common multitubular Ea,1 activation energy 27.14 kcal/mol
reaction 1
Ea,2 activation energy 31.00 kcal/mol
reaction 2
Ea,3 activation energy 28.60 kcal/mol
reaction 3
hw heat transfer coefficient 30.93 cal/(m2 s K)
at the wall
kr,e effective radial thermal 0.49 cal/(m s K)
conductivity
l reactor length 9.0 m
P pressure 1.7 atm
Ftot,i initial reactor feed 0.120 mol/s
yox mole fraction of o-xylene 1.12 mol %
in air
ρb bulk catalyst density 1240 kgcat/m3

for the partial oxidation of o-xylene reported by Calverley et al.15

The kinetic parameter values are reported in Table 1. The rate
equations are
r1 = k1PoxPO2
r2 = k 2PphPO2

r3 = k 3PoxPO2
Figure 1. Multitubuluar fixed bed catalytic reactor modeling
schematic. ⎛ E ⎛1 1 ⎟⎞⎞⎟
ki = Ai exp⎜⎜−
a, i
⎜ − for i = 1, 2, 3
⎝ Rg ⎝ T 600 ⎠⎟⎠
fixed-bed catalytic reactor system. The model is used to
investigate impact of coolant flow rate and baffle configuration where ri is the reaction rate for reaction i, Ai is the pre-
on the resulting variation in shell-side cooling temperature. exponential constant for reaction i, Ea,i is the activation energy
The resulting non-isothermal cooling temperature impacts the for reaction i, ki is the reaction rate constant for reaction i, Pox
overall reactor performance: temperature profiles at the wall and is the partial pressure of o-xylene, PO2 is the partial pressure of
centerline and o-xylene conversion. The reactor performance is oxygen, and Pph is the partial pressure of phthalic anhydride.
evaluated for each case.

■
Reactor Model. The conservation equations for mass and
energy define the fixed-bed reactor model. The mole balance
REACTOR MODELING for species i over all reactions j is defined by
Chemistry. The gas-phase partial oxidation of o-xylene n
reaction network is defined by the following reactions: dFi
= Vrρb ∑ νi , jrj for i = 1, ..., m
C8H10 + 3O2 → C8H4O3 + 3H 2O dz j=1 (1)

15 where Vr is the fixed-bed reactor volume and νi,j is the reaction

C8H4O3 + O2 → 8CO2 + 2H 2O stoichiometric coefficient for species i and reaction j. For
2
simplicity, we assume that the fixed-bed reactor is isobaric. It is
21 recognized that this assumption is unrealistic. Alternative pressure
C8H10 + O2 → 8CO2 + 5H 2O
2 drop correlations may be substituted. The energy balance equation
m
Direct conversion of o-xylene to phthalic anhydride is the dĤ 8αk r,eπl
primary reaction. Complete combustion of both o-xylene and ∑ Fi =−
i=1
dz A (2)
phthalic anhydride constitute non-selective competing reactions.
13
Partial oxidation of o-xylene has been studied extensively by is defined using the method developed by Hagan et al. The
several researchers.2,6−10,12 This paper uses kinetic information Hagan method estimates the heat transfer between the process
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Figure 2. (a) Nominal reactor wall temperature and centerline temperature for base case analysis, as calculated from eqs 12 and 13. (b) Nominal
heat flux at reactor tube wall for base case analysis, as calculated from eq 16.

and the shell coolant. The reactor model is a one-dimensional

model that accurately simulates the two-dimensional conserva-
tion equations by accounting for the heat generation distribution
along the radial direction. The energy balance equation, eq 2, is
developed by applying a Taylor’s series expansion of ln f(T)
around the radial mean temperature, Tm, where f(T) is of the
Arrhenius form and Tc is the coolant temperature
⎛ E ⎞
f (T ) = exp⎜⎜ − a ⎟⎟
⎝ R gT ⎠ (3)

Ea
ln f (T ) ≈ − + A(T − Tm) + B(T − Tm)2 + ... Figure 3. Nominal o-xylene conversion for base case analysis assuming
R gTm constant shell-side wall temperature (600 K).
(4)
Table 2. Nominal Results for Base Case Simulation
where
output description value units
E̅
A= zmax normalized axial position at max. 0.267
R gTm2 (5) temp.
Tw(z = zmax) max. reactor wall temp. 620.8 K

B R gTm 1
n⎛ Ea, i − E ̅ ⎞2 Tw(z = 1) final reactor wall temp. 606.9 K
=− + ∑⎜ ⎟ wi Tcent(z = zmax) max. reactor temp. at centerline 629.8 K
A2 E̅ 2 i= 1 ⎝ E̅ ⎠ (6) Tcent(z = 1) final reactor temp. at centerline 609.8 K
χox(z = 1) final o-xylene conversion 57.7 %
The average activation energy, E̅ , is defined by Q̇ r(z = zmax) max. radial heat flux 2693 W/m2
n
Qr total radial heat release 1242 W
E̅ = ∑ Ea,iwi
i=1 (7)
Hagan et al.13 derive the radial temperature profile along the
where the weighting, wi, of reaction i is defined by reactor length where
riΔHrxn, i
wi = 1 ⎡ 4α ⎛ ⎛ r ⎞ 2 ⎞⎤
n
∑i = 1 riΔHrxn, i T (r , α) = Tc + ⎢ − 2ln⎜1 − α + α⎜ ⎟ ⎟⎥
(8) A ⎢⎣ Bi ⎝ ⎝ R ⎠ ⎠⎥⎦
(11)
Hagan applied Taylor series expansion and the Karman−
Temperature profiles at the reactor wall, Tw, and reactor
Pohlhausen procedure16 resulting in an implicit equation for
centerline, Tcent, are of particular interest in work presented
the α term in eq 2.
here. Evaluation at r = R and r = 0 reduces eq 11 to
Bi ⎡ 1 B 2 ⎤
α= ⎢A(Tm − Tc) + ln(1 − α) − ln (1 − α)⎥ 4α
4⎣ 3 A2 ⎦ Tw = Tc +
BiA r=R (12)
(9)
The reactor heat transfer rate adjusts along the axial direction and
based on the local reaction rate and local temperature. 1 ⎡ 4α ⎤
For simplicity, effective thermal conductivity, kr,e, and the heat Tcent = Tc + ⎢⎣ − 2ln(1 − α)⎥
A Bi ⎦ (13)
transfer coefficient at the wall, hw, are assumed to be constant. r=0
Therefore, the Biot number, Bi, is constant as well: The fixed-bed reactor model is coupled to the shell-side CFD
hw d t model through the heat flux at the reactor tube and the shell-
Bi = side coolant temperature, Tc. The energy flux, Q̇ r, in cylindrical
2k r, e (10) coordinates is defined as17
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Figure 4. CFD coolant velocity profiles on the reactor shell-side. Sections are along the center point of the zones.

Figure 5. CFD coolant temperature profiles on the reactor shell-side. Sections are along the center point of the zones.

∂T 4αhw
Q̇ r = −k r,e Q̇ r =
∂r (14) BiA r=R (16)
The energy flux can also be written as
Equation 16 is used to calculate the energy flux from each fixed-
∂T bed reactor tube model to the CFD model for shell-side coolant
−k r,e = hw (Tw − Tc)
∂r (15) temperature.
where hw is the heat transfer coefficient at the wall and Tcool is The mass and energy balance equations are solved using
the coolant temperature. Equation 14 can be rewritten by Athena Visual Studio, which uses a variant of the DASSL
substituting eqs 12 and 15 to incorporate the Hagan method predictor−corrector algorithm to solve the reactor integration
into the energy flux problem. The specific enthalpy of the system is calculated using
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Table 3. Comparison of Reactor Performance for Disk and Doughnut Baffles and Varying Coolant Flow Ratesa
output description 15 kg/s 30 kg/s 50 kg/s units
zmax normalized axial position at max temp. 0.403 ± 0.028 0.289 ± 0.013 0.286 ± 0.006
T̅ c shell-side wall temp. 609.0 ± 10.3 603.9 ± 4.1 602.3 ± 2.3 K
Tw(z = zmax) max. reactor wall temp. 637.0 ± 3.5 626.3 ± 1.0 623.9 ± 0.5 K
Tw(z = 1) final reactor wall temp. 624.5 ± 0.3 614.5 ± 0.1 611.3 ± 0.1 K
Tcent(z = zmax) max. reactor temp. at centerline 649.6 ± 4.6 636.4 ± 1.2 633.7 ± 0.8 K
Tcent(z = 1) final reactor temp. at centerline 628.1 ± 0.4 617.7 ± 0.1 614.4 ± 0.1 K
χox(z = 1) final o-xylene conversion 76.3 ± 0.8 65.3 ± 0.3 62.2 ± 0.2 %
Q̇ r(z = zmax) max. radial heat flux 3780 ± 363 3071 ± 115 2925 ± 68 W/m2
Qr total radial heat release 1640 ± 29 1354 ± 8 1283 ± 4 W
a
Mean output values are reported at 95% confidence.

Figure 6. Resulting shell-side wall temperature profiles, Tc, for 36 Figure 8. Resulting shell-side wall temperature profiles for 36 zones
zones from CFD modeling. Molten salt flow rate is 15 kg/s. Nominal from CFD modeling. Molten salt flow rate is 30 kg/s. Nominal
(initial) shell-side temperature is 600 K (−·−). (initial) shell-side temperature is 600 K (−·−).

Figure 7. Overall reactor performance for 36 zones from CFD modeling. Resulting heat flux profiles (a), Q̇ r, calculated using eq 16. Reactor
temperature at wall, Tw, (b) and centerline, Tcent, (c), as calculated from eqs 12 and 13. Resulting o-xylene conversion profiles (d). Molten salt flow
rate is 30 kg/s. Nominal reactor heat flux, temperature, and o-xylene conversion profiles (−·−) are reported for comparison.

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Industrial & Engineering Chemistry Research Article

Figure 9. Overall reactor performance for 36 zones from CFD modeling. Resulting heat flux profiles (a), Q̇ r, calculated using eq 16. Reactor
temperature at wall, Tw, (b) and centerline, Tcent, (c), as calculated from eqs 12 and 13. Resulting o-xylene conversion profiles (d). Molten salt flow
rate is 30 kg/s. Nominal reactor heat flux, temperature, and o-xylene conversion profiles (−·−) are reported for comparison.

considered representative of the temperature of the coolant

Figure 10. Resulting shell-side wall temperature profiles for 36 zones
from CFD modeling. Molten salt flow rate is 50 kg/s. Nominal
(initial) shell-side temperature is 600 K (−·−).
the Athena Visual Studio flash calculation and the physical prop-
erty database provided with the Athena Visual Studio installation.
While this model uses the Hagan method13 to calculate an
appropriate radial-mean temperature, it is fundamentally a one-
dimensional model, so only the axial activity distribution is being
investigated with this approach.
Shell-Side Model. The linkage between the CFD code and
the reactor model is through the heat balance equation. The
reactor model is used to set a heat source term in the CFD
model. The CFD model generates a cooling medium temper-
ature for the reactor model, using the reactor models calculated
wall heat flux as a heat source term in the CFD energy equation.
The variations in the local conditions encountered by the
individual tubes are accounted for by dividing the tube bundle
into a number of zones (36 in this case). The 36 zones were
arranged in a 6 × 6 grid. The centroid of each zone is
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experienced by each tube located in the zone. The grid was
constructed with the ANSYS program GAMBIT. It is a fully
hexagonal grid with 2.16 million cells (55 × 55 × 743 cells).
The same sized grid was used for all simulations. It was built
so that interblock faces could be labeled as walls to create the
baffling scheme desired, while keeping the same geometry and
cell count. The inter-baffle spacing is set to the diameter of the
bundle.
The CFD code writes the coolant temperature profile vector
for each zone into a series of files that are then copied to the
correct location for the reactor model computation. The fixed-
bed reactor models executes the simulation with the updated
shell-side coolant temperature. The fixed-bed reactor model
solution is obtained in 10 s. The CFD code then calls the
reactor model for each of the bundle zones, and reads the
resulting data files (radial heat flux vector). Each computational
cell is then identified by tube bundle zone and the distance
along the reactor tube. The heat flux (source term) and several
other parameters are read from the reactor model results file and
stored in user defined memory locations in the ANSYS Fluent
code. The parallel nature of the CFD simulation requires that
these steps be done only from the master process of the
simulation. To avoid numerical instabilities, the computed heat
source term is under-relaxed with the heat source term from the
previous model iteration. This technique is reasonably robust
and converges in approximately 5000 iterations per zone and
coolant profile (approximately 30−40 min). Using 32 parallel
processors, the complete CFD-fixed-bed reactor model
simulation would complete in 18−20 h.
Three molten salt flow rates are evaluated and the resulting
profiles are compared to the base case. Cross-cocurrent flow of
Industrial & Engineering Chemistry Research Article

Figure 11. Overall reactor performance for 36 zones from CFD modeling. Resulting heat flux profiles (a), Q̇ r, calculated using eq 16. Reactor
temperature at wall, Tw, (b) and centerline, Tcent, (c), as calculated from eqs 12 and 13. Resulting o-xylene conversion profiles (d). Molten salt flow
rate is 50 kg/s. Nominal reactor heat flux, temperature, and o-xylene conversion profiles (−·−) are reported for comparison.

the molten salt is implemented. Two baffle configuration are also at 95% confidence. Equation 16 is integrated along the length
considered: segmented baffles and disk and doughnut baffles. of the reactor to calculate the total radial heat released. As is

■
RESULTS
Base Case Analysis. The first simulation completed assumes
a constant, uniform shell-side temperature, 600 K, with no
variance in the axial direction (i.e., perfect mixing and isothermal).
This simulation establishes the nominal profile for reactor
temperature along the reactor wall and centerline, defined by
eqs 12 and 13. The nominal heat flux profile along the length of
the reactor is calculated, defined by eq 16. Temperature profiles
at the wall and centerline and heat flux profile are reported in
Figure 2. A maximum reactor temperature and heat flux is
achieved at the normalized axial position 0.267 (2.406 m). The
maximum wall and centerline temperatures are 620.8 and
629.8 K, respectively. The maximum heat flux is 2693 W/m2.
The nominal o-xylene conversion profile across the reactor
length is reported in Figure 3. The o-xylene conversion is 57.7%.
The complete base case results are summarized in Table 2.
Coolant Flow Rate and Impact on Reactor Performance.
The subsequent simulations evaluate the impact of shell-side
coolant feed rate on reactor performance. Three coolant feed
rates were selected: 15, 30, and 50 kg/s. Figure 4 reports the
simulated shell-side coolant velocity profiles for each case.
Figure 5 reports the simulated shell-side temperature profile
for each coolant feed rate. It is evident that the slowest flow
rate (15 kg/s) has a larger temperature gradient along the
length of the reactor. Conversely, the fastest coolant flow rate
(50 kg/s) has a smaller temperature gradient along the length of
the reactor. Table 3 summarizes key characteristics from each
simulation. For each output, the mean of the 36 zones is reported
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expected with faster coolant flow rates, the mean shell-side
coolant temperature decreases (i.e., approaches the ideal case of
600 K). The slowest flow rate (15 kg/s) yields the highest
reactor centerline temperature further into the reactor bed. As
the coolant feed rate increases, the maximum predicted reactor
temperature and normalized axial position decreases (i.e.,
approaches the nominal case). The next sections analyze the
results for each flow rate.
Case 1: 15 kg/s. Figure 6 reports the resulting shell-side
coolant temperature for the 36 zone compared to the nominal
case, 600 K. The slower feed rate results in a larger increase
in shell-side coolant temperature. The shell-side temperature
at the exit of the reactor is more than 15 K larger than the
base case. The resulting overall increase in shell-side coolant
temperature results in a 32% increase in total radial heat release
compared to the base case. The additional heat release and
higher shell-side coolant temperature results in an increase of
almost 20 K of the maximum reactor temperature along the
centerline. This results in a 32% increase in o-xylene conversion.
See Figure 7.
Case 2: 30 kg/s. Figure 8 reports the resulting shell-side
coolant temperature for the 36 zone compared to the nominal
case, 600 K. The coolant feed rate is twice as fast as Case 1. The
shell-side temperature gradient is reduced due to the increased
coolant flow rate. The shell-side temperature at the exit of the
reactor is more than 7 K larger than the base case. The resulting
overall increase in shell-side coolant temperature results in a
9% increase in total radial heat release compared to the base
case. The additional heat release and higher shell-side coolant
temperature results in an increase of almost 7 K of the
Industrial & Engineering Chemistry Research
Figure 12. CFD coolant velocity profiles on the reactor shell-side. Sections are along the center point of the zones.
maximum reactor temperature along the centerline. This results
in a 13% increase in o-xylene conversion. See Figure 9.
Case 3: 50 kg/s. Figure 10 reports the resulting shell-side
coolant temperature for the 36 zone compared to the nominal
case, 600 K. The shell-side temperature gradient is reduced due
to the increased coolant flow rate. The shell-side temperature at
the exit of the reactor is more than 4 K larger than the base case.
The resulting overall increase in shell-side coolant temperature
results in a 3% increase in total radial heat release compared to
the base case. The additional heat release and higher shell-side
coolant temperature results in an increase of almost 7 K of the
maximum reactor temperature along the centerline. This results
in an 8% increase in o-xylene conversion. See Figure 11.
This analysis, as expected, demonstrates that with faster
coolant flow rates, the coupled fixed-bed reactor and CFD model
approach the nominal case. Variance in reactor performance
outputs (i.e., temperature, heat flux, and conversion) for each
tube is reduced with increasing coolant flow rate. There is a
substantial improvement in overall reactor performance when
the flow rate is increased from 15 kg/s to 30 kg/s. The distance
in the reactor bed, zmax, where the peak temperature and heat flux
is observed is reduced 28%. The resulting o-xylene conversion is
reduced 14%. Increasing the coolant flow rate from 30 kg/s to
50 kg/s reduces zmax and χox 1% and 5%, respectively. There may
be physical limitations that must be considered and accounted
for when considering adjusting flow rates.
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Article
Shell-Side Baffle Configuration. Simulations in this
section evaluate the impact of shell-side baffle configuration
on reactor performance. Two shell-side baffle configurations
were selected: segmented and disk and doughnut. There are
alternative baffles, in addition to no baffles, that can be evaluated
but are not addressed in this current work. The shell-side
coolant (molten salt) flow rate was kept constant (50 kg/s) for
each simulation. Figure 12 reports the simulated shell-side
coolant velocity profiles for each case. CFD simulations report
different coolant velocity profiles for the segmented and disk
and doughnut baffled systems, for the same coolant flow rate.
Figure 13 reports the simulated shell-side temperature profile
for each shell-side configuration. The resulting shell-side coolant
temperature profiles for both cases appear to be similar
qualitatively. For either case, the resulting shell-side temperature
is non-isothermal, as is assumed for the base case. In fact, the
shell-side temperature follows an almost linear profile
approaching 604−605 K at the reactor outlet (z = 1), with
the mean shell-side temperature of 602.3 K. Figure 10 reports
the shell-side coolant temperature for the disk and doughnut
baffle case; simulations from the segmented baffle case are
similar. Table 4 reports the reactor model process outputs for
both cases. The reactor performance for both configurations are
statistically similar.
This analysis illustrates that similar reactor performance
is achieved with different external shell-side baffling systems.
Industrial & Engineering Chemistry Research Article

Figure 13. CFD coolant temperature profiles on the reactor shell-side. Sections are along the center point of the zones.

Table 4. Comparison of Reactor Performance for Segmented Baffles and Disk and Doughnut Baffles
output description segmented baffles disk/doughnut baffles units
zmax normalized axial position at max temp. 0.287 ± 0.001 0.286 ± 0.006
T̅ c shell-side wall temperature 602.3 ± 2.3 602.3 ± 2.3 K
Tw(z = zmax) max. reactor wall temp. 623.8 ± 0.4 623.9 ± 0.5 K
Tw(z = 1) final reactor wall temp. 611.2 ± 0.1 611.3 ± 0.1 K
Tcent(z = zmax) max. reactor temp. at centerline 633.5 ± 0.5 633.7 ± 0.8 K
Tcent(z = 1) final reactor temp. at centerline 614.3 ± 0.1 614.4 ± 0.1 K
χox(z = 1) final o-xylene conversion 62.1 ± 0.2 62.2 ± 0.2 %
Q̇ r(z = zmax) max. radial heat flux 2903 ± 36 2925 ± 68 W/m2
Qr total radial heat release 1281 ± 4 1283 ± 4 W

The CFD models calculated significantly different coolant
velocity profiles based on the baffle configuration. The resulting
shell-side coolant temperatures were comparable. The fixed-bed
reactor model confirms that the overall reactor performance are
statistically similar.
reactor performance: temperature profiles at the wall and
centerline and o-xylene conversion.
This analysis demonstrates that with faster coolant flow
rates, the coupled fixed-bed reactor and CFD model process
outputs approach the nominal case. Alternative shell-side baffle

■
CONCLUSIONS
This paper presents an overall fixed-bed reactor model that
combines a one-dimensional plug flow reactor model with a
CFD model of the shell-side coolant fluid over a series of
individual reactor tubes. The model chemistry is the partial
oxidation of o-xylene to phthalic anhydride. The model is used
to investigate the variation in cooling temperature on overall
I dx.doi.org/10.1021/ie4006832 | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
configurations are examined. The calculated coolant velocity
profiles, though different between evaluated configurations,
result in similar overall reactor performance. However, it should
be noted that none of the simulations observe isothermal
shell-side coolant temperatures, as is commonly assumed in
fixed-bed and plug flow reactor models.
This provides opportunity for further reactor optimization on
both the shell-side CFD model and the fixed-bed reactor
model, as it can be applied to pilot- and commercial-scale
Industrial & Engineering Chemistry Research
reactors for existing or new chemistries. This model provides a
more realistic estimation of the reactor performance, when
considering isothermal coolant profiles. Specifically, for the fixed-
bed reactor model, alternative catalyst packing schedules (i.e.,
activity profiles) or feed rates can be considered. Additionally,
conditions or individual reactor tubes can be identified that are
more prone to runaway. The coupled model does provide
flexibility in that such future optimizations are possible.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: ejhukkanen@dow.com.
Notes
The authors declare no competing financial interest.
■
NOMENCLATURE
A, B = Hagan terms (K−1, K−2)
Ai = pre-exponentional factor of reaction i (mol kgcat−1 atm−2 s−1)
Bi = Biot number
dt = reactor tube diameter (m)
Ea,i = activation energy for reaction i (kcal mol−1)
E̅ = average activation energy (kcal mol−1)
Fi = molar flow rate of component i (mol s−1)
Ftot,i = initial reactor feed (mol s−1)
hw = heat transfer coefficient at wall (cal m−2 s−1 K−1)
Ĥ = specific enthalpy (cal mol−1)
ΔHrxn,i = heat of reaction for reaction i (kcal mol−1)
ki = rate constant of reaction i (mol kgcat−1 atm−2 s−1)
kr,e = effective radial thermal conductivity (cal m−1 s−1 K−1)
l = reactor length (m)
m = number of components
n = number of reactions
P = pressure (atm)
Px = partial pressure of component x (atm)
Q̇ r = energy flux in radial direction (W m−2)
Q r = total radial heat release (W)
R = reactor tube radius (m)
Rg = ideal gas constant (cal mol−1 K−1)
ri = rate of reaction i (mol kgcat−1 s−1)
T = temperature (K)
Tc = shell-side temperature (K)
Tcent = reactor centerline temperature (K)
Tm = radial mean temperature (K)
T̅ c = mean shell-side temperature (K)
Tw = reactor wall temperature (K)
Vr = fixed-bed reactor volume (m3)
wi = weighting of reaction i
yox = mole fraction of o-xylene in air
z = dimensionless axial position
zmax = dimensionless axial position at maximum temperature
α = Hagan alpha term
ν = stoichiometric coefficient
ρb = bulk catalyst density (kgcat m−3)
χox = o-xylene conversion (%)
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