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Received 28 April 1999; received in revised form 2 August 2000; accepted 3 August 2000
Abstract
A mathematical model and computer program have been developed for the study and the design of Catalytic Flow Reversal
Reactors (CFRR). It combines a transient two-dimensional heterogeneous model with a numerical method allowing the fast
formulation of new reactor configurations during the design phase. The program has been validated with experiments performed
for the oxidation of lean methane emissions. It is shown that the dynamic behaviour of the CFRR can be predicted accurately
for a wide range of conditions including small reactor diameter and low air flow rate if the radial effects related to the thermal
insulation are taken in account. Experiments were also accurately predicted for two different heat removal systems: hot air
withdrawal and an internal heat exchange, both in the mid-section of the reactor. © 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Catalytic Flow Reversal Reactors (CFRR); Forced Unsteady State Conditions (FUSC); Two-dimensional heterogeneous model
0098-1354/00/$ - see front matter © 2000 Elsevier Science Ltd. All rights reserved.
PII: S0098-1354(00)00618-9
2624 F. Aubé, H. Sapoundjie6 / Computers and Chemical Engineering 24 (2000) 2623–2632
CFRR technology applied to the elimination of lean model. Gosiewski (1993) specified that the most im-
methane emissions from underground coal mine venti- portant parameter is the gas–solid heat transfer co-
lation air. efficient and observed that an overall radial heat
Various models were proposed to deal with the dy- transfer coefficient has to be introduced to account
namic behaviour of the CFRR. For example, Eigen- for radial heat losses. Furthermore, Sapundzhiev et
berger and Nieken (1988), Gosiewski and Sztaba al. (1988), van de Beld and Westerterp (1996) added
(1990) used a one-dimensional pseudo-homogeneous a heat balance term for the reactor wall since its heat
model. Gawdzik and Rakowski (1988), Silveston, capacity can be significant. They also suggested that,
Hudgins, Bogdashev, Vernijakovskaja and Matros due to the presence of a thick layer of insulation, a
(1990), Thullie and Burghardt (1990), Bhatia (1991) considerable heat buffer had been created and the
proposed a one-dimensional heterogeneous model to performance of a model might be improved by con-
account for the gas – solid temperature difference but sidering its heat capacity. However, Sapundzhiev and
neglected the axial diffusion terms. On the other his co-workers observed that heat losses could be ne-
hand, Sapundzhiev et al. (1990), Young, Hildebrandt glected for reactors with an inner diameter larger
and Glasser (1992), van de Beld and Westerterp than 1 m. Finally, Khinast, Jeong and Luss (1999)
(1994) and Rehacek, Kubicek and Marek (1998) used concluded that, the safest simulation of cases involv-
a similar model but including the axial diffusion ing large temperature difference between the solid and
terms. At a higher complexity level, Sapundzhiev et the gas phase is by using a two-dimensional model.
al. (1988) developed a two-dimensional heterogeneous Concerning numerical procedures found in the liter-
model including radial diffusions and heat and mass ature to solve mathematical models related to CFRR,
transfer between the phases. Later on, van de Beld lot of work focused on computational time reduction
and Westerterp (1996) concluded that a two-dimen- by using performing numerical methods, by simplify-
sional model must be used to improve the model ac- ing mathematical models to one dimension, or by
curacy at low velocities and for small reactor
fixing the boundary values in time at the beginning
diameters.
and end of the half cycle to avoid the need to solve
Each model was developed according to the specific
over the long transient period before the establish-
needs of the respective study. Several recommenda-
ment of the stationary conditions (Gupta & Bhatia,
tions were made to meet minimal accuracy require-
1991; Sapundzhiev et al., 1993). The last technique
ments to describe satisfactorily the dynamic behaviour
has shown satisfactory results to approximate temper-
of this type of reactor.
ature profiles and is useful for basic parametric stud-
Concerning the mass balance, despite a few excep-
ies. However, in the present case and for the majority
tions using a homogeneous model (Eigenberger &
of the CFRR industrial applications where the final
Nieken, 1988; Gawdzik & Rakowski, 1989;
Gosiewski, 1993), the heterogeneous model is gener- design of large units including testing of the reactor
ally employed where its mass transfer term is repre- behavior under critical situations depend on calcula-
sented by a linear expression (e.g. Sapundzhiev et al., tions, the accuracy of simulations is the main con-
1990; Sapundzhiev et al., 1991; Xiao & Yuan, 1994; cern. Therefore, the computer program must be
Nieken, Kolios & Eigenberger, 1995; van de Beld & written in such a way that it allows the detailed de-
Westerterp, 1996; Salinger & Eigenberger, 1996). The sign of reactors including complex geometries, pieces
latter authors also include convective and diffusion of equipment, and other aspects like automatic con-
terms for energy (both fluid and solid phases) and trol of the process, variations of inlet conditions with
mass balances. Vanden Bussche et al. (1993) specified time and different modes of heat removal.
that the introduction of mass and energy capacity The aim of this paper is to demonstrate the impor-
terms for both the bulk gas and the gas phase con- tance of the detailed modeling of heat processes in
tained inside the pores of the catalyst is also essential the reactor wall and the thermal insulation for the
for an adequate modelling. prediction of the transient behaviour of laboratory-
Concerning specifically the energy balance, Kiselev, scale flow reversal reactors. A two-dimensional het-
Matros and Chumakova (1988) found that heat dissi- erogeneous model has been improved by including
pation should be taken into account and can be complete energy balance for the reactor wall and the
defined by several means such as axial heat conduc- thermal insulation, and mass transfer between bulk
tion, heat transfer between the phases or heat transfer and pore gas phases. The computer program has been
inside the catalyst pellets. Rehacek, Kubicek and developed with a unique combination of existing nu-
Marek (1992) and Rehacek et al. (1998) found that merical and interfacing techniques characterized by
complicated regimes existing inside the reactors can high flexibility and adaptability. A powerful personal
only be found by introducing both axial dispersion in workstation was used to meet the requirements for
the gas phase and axial heat conduction into the speed and accuracy needed for the simulations.
F. Aubé, H. Sapoundjie6 / Computers and Chemical Engineering 24 (2000) 2623–2632 2625
A schematic of a typical CFRR process is shown in The general form of the conservation equations writ-
Fig. 1. It consists of a reactor, two pairs of valves and ten in axisymmetrical cylindrical coordinates for the
a heat removal system in the central region separating proposed heterogeneous model is
the catalyst bed into two parts. At both ends of the ( ( 1 (
reactor, an inert (chemically not active) material bed is (r f)+ (r u f)+ (r r6f)
(t (x r (r
present and acts as a thermal capacity. The flow rever-
sal is controlled by the sets of valves. When valves 1 are =
(
G
(f
+
1 (
rG
(f
+ S,
opened and valves 2 are closed, the reaction mixture (x (x r (r (r
flows from left to right (direct flow operation). After a where f=1 for the continuity equation, f=Cs Ts
certain period of time, the position of the valves is (solid phase) and f= Ca Ta (fluid phase) for the energy
reversed in order to reverse the flow direction from conservation equations, and S is the source term (e.g.
right to left (reverse flow operation). Before initiation thermal power generated by chemical reaction for the
of the process the inert and catalyst beds are preheated fluid energy equation).
by an external heat source to an appropriate tempera- This general form has been used to describe the fluid
ture. During normal operation, the system is energy phase and the solid parts of the reactor. On the other
autonomous and the preheating system is switched off. hand, the following assumptions have been made to
In direct flow operation the reaction mixture enters the describe the porous media
reactor from the left side. It heats up, going through the heat transfer occurs between the solids (catalyst and
hot left inert bed and enters the catalyst bed at a inert) and the fluid phase,
sufficient temperature to allow the oxidation of meth- Mass transfer only takes place between the fluid
ane to occur and further heat the air. The hot gas heats stream and the porous catalyst. The inert bed is not
the right inert bed before exiting to the atmosphere. porous.
During the direct flow operation, the left inert bed, The energy conservation equation for the solid
which was initially hot, cools down, while the right porous media can be written as
inert bed, which was relatively cool, heats up. The (T ( (Ts
process switches to reversed flow when the gas mixture (1−o)Cs rs s = (1− o)ks
(t (x (x
temperature entering the left catalyst bed nears a low-
temperature set point, below which catalytic oxidation
+ (1− o)ks
1 ( (Ts
r
A
− has (Ts − Ta )
is less efficient. The incoming feed gas now enters from r (r (r V
the right, heats up while rising through the right inert N−1
DHj
bed, reacts in the catalyst section and heats the left inert +(1− o) % hj Wsj (r̄j,Ts )
bed before leaving the reactor. Direct flow is re-estab- j = 1 Mj
lished at the end of the reverse flow. The heat generated where o is the bed voidage and N is the number of
in excess by the exothermic chemical reaction is with- reactives. A/V is the solid–fluid surface area per unit of
drawn by the heat removal system in the mid-section of bed volume. The corresponding energy conservation
the reactor. equation for the fluid phase is
((raTa ) ( u o ( 6
o Ca + o Ca raTa + Ca rraTa
(t (x o (r o
r
( (Ta 1 ( (T A
=o k +o rka a + has (Ts − Ta )
(x a (x r (r (r V
where the velocity field is determined with the two-di-
mensional form of the momentum balance, using the
Brinkman’s equation (Brinkman, 1947) for porous me-
dia. For each one of the N reactives (indexed j) present
in the fluid stream, the continuity equations can be
written as:
(r ( u 1 ( (r A
o j+o rj = o rD j + bj (r̄j − rj )
(t (x o r (r (r V
where bj is the mass transfer coefficient (bj = 0 in the
non-porous inert beds). The radial convection term has
been neglected. Moreover, for each one of theNreac-
tives located inside the volume of the porous catalyst,
Fig. 1. Schematic of a typical CFRR process. the continuity equation is
2626 F. Aubé, H. Sapoundjie6 / Computers and Chemical Engineering 24 (2000) 2623–2632
reactor avoiding concentration and temperature gradi- almost totally converted by the chemical reaction. The
ents, and under the assumption that the reaction is of outlet gas and the extracted hot air in the mid-section
first order according to methane (oxygen is in excess) contain no nitrogen oxides due to the low oxidation
temperature (below 800°C).
Ws = − rs = − Kr̄ = − Koe − Ea /RTsr̄
where Ko is the reaction rate coefficient and Ea is the
activation energy. 7. Model and code validation
Physical and thermodynamic properties of the gas
mixture flowing through the CFRR, like m, ka, D and The process of code validation for transient simula-
ra vary over a wide range of temperature. This temper- tions implies comparisons with data collected over peri-
ature dependence has been taken into account by using ods of time and for a specific range of operations.
polynomial best curve fits based on handbook data. Simulations were compared to results obtained from
For the solid phase, the properties are assumed con- experiments conducted on the lab-scale reactors, often
stant and are shown in Table 1. Moreover, the parame- lasting for over 8 h and during which operating condi-
ter values needed to solve the model and the transfer tions were varied several times.
relations, used in the calculations for the packed beds, During the experiments, the temperature was regis-
are shown in Table 1 for each one of the reactors. tered mainly in the central axis of the reactor. A radial
temperature registration was done at only two other
places in the reactor, both located in the catalyst beds.
6. Experimental setup No temperature registration was done for the reactor
shell and in the thermal insulation. Moreover, since the
The model and simulation software proposed in this reactor and its thermal insulation both have high heat
paper had been validated for the design of CFRR capacities, any significant difference between the esti-
applied to the oxidation of lean methane emissions. The mated and real temperature values in these sections can
simulation results were compared with the experimental lead to large discrepancies between the simulation re-
data from a 200 mm I.D. and a 500 mm I.D. laboratory sults and the experimental data. For these reasons, a
scale reactors operating with two different configura- calculation procedure was developed to estimate the
tions for heat removal (mid-section hot air withdrawal two-dimensional ‘initial’ temperature field values in the
or internal heat exchange). reactor beds and shell, as well as in the thermal insula-
For each reactor, a set of thermocouples was in- tion. This procedure is as follows: temperature data
stalled along the central axis for temperature registra- taken at the central axis of the reactor are selected for
tion. Methane conversion was measured by gas the beginning of the calculations. The temperature data
chromatography, analysing the methane concentration at that time (set to t= 0) are used to calculate the
in the feed gas stream, the mid-section gas withdrawal ‘initial’ temperature profile at any node of the grid
and the gas at the outlet of the reactor. Methane is along the central axis of the reactor. For simplicity, the
Table 1
List of input parameters for the model simulations shown in this paper
Inert material bed Catalyst bed Reactor wall and insulation Inert material bed Catalyst bed Reactor wall and insulation
m m
di = 4.5 mm cd =7.2 mm dt = 0.3 m di =11.7 mm d =7.2 mm
c dt =0.4 m
Re 0.6 Re 0.6
Heat and mass transfer relations: Wakao & Kaguei (1982), Nu =2.0+1.1 Pr1/3 and Sh=2.0+1.1 Sc 1/3
Fig. 7. 500 mm I.D. reactor. 6 =0.65 m/s, 0.3% v/v of methane, hot
air withdrawal. (a) First half-cycle (t =0 – 200 s); (b) Second half-cycle
(t =200 – 400 s); (c) After 15 cyces (t = 6950 s).
conditions are as follows: feed air superficial velocity of concentration of 0.35% v/v. The heat removed through
0.65 m/s, an inlet temperature of 20°C, and a methane the air–oil heat exchanger is 50% of the total amount
concentration of 0.3% v/v. of heat generated by the chemical reaction. The oil
Fig. 7a shows the temperature evolution along the temperature has been kept to a temperature below
reactor length during the first half-cycle. The flow direc- 350°C in order to prevent boiling. In comparison with
tion is from left to right. The initial temperature profile the hot air withdrawal cases, a significant temperature
is shown as a dashed line. The circles and the solid line decrease in the mid-section and the catalyst beds was
represent the temperature distribution and the predicted observed. It was caused by the air cooling. The in-
profile along the reactor length at the end of the first creased temperature gradients greatly influence the rate
half-cycle (200 s). The flow direction is then reversed. constant of the reaction, which is an exponential func-
The evolution of the heat front during the second tion of the temperature and makes reactor behaviour
half-cycle is shown in Fig. 7b (200 – 400 s) as the more sensitive to process variables. It may result in
difference between the solid and hollow circles. Hot air higher discrepancies between predicted and experimen-
extraction in the mid-section implies adjusting opera- tal results as seen on these figures.
Results obtained at the end of the first and the
tions conditions in order to achieve complete methane
second half-cycle are shown in Fig. 8a and Fig. 8b,
combustion in the upstream catalyst bed and thus
respectively. Moreover, results obtained after 9 and 24
avoiding the presence of methane in the withdrawn air.
cycles (4100 and 10800 s respectively) are shown in Fig.
This restriction imposes shorter cycle duration and
8c–d. There is a progressive axial temperature drift
leads to the formation of two peaks on the axial
between predictions and data with time, particularly at
temperature profile, both located at the catalyst beds. the mid-section. Despite the fact that higher discrepan-
Fig. 7(c) shows temperature profiles after 15 cycles cies were expected, good agreement for short and long-
(6950 s). For this case, the reactor operates in stable term simulations was nevertheless found under these
regime and 52% of the heat generated by the chemical conditions and for the whole investigated range of
reaction is removed by air withdrawal in the central operation.
region of the reactor. The flow rate of the extracted hot
air was kept constant, with an average temperature
around 700°C.
Good agreement between simulations and experi- 9. Conclusions
ments is also observed with the internal heat removal
scenario. Typical results are shown in Fig. 8a – d for a The combination of a two-dimensional heteroge-
fluid superficial velocity of 0.65 m/s and a methane neous model and a special numerical procedure allow-
Fig. 8. 500 mm I.D. reactor. 6 = 0.65 m/s, 0.35% v/v of methane, internal heat remo6al. (a) First half-cycle (t =0 – 200 s); (b) Second half-cycle
(t=200 – 430 s); (c) After 9 cyces (t = 4100 s); (d) After 24 cycles (t= 10800 s).
F. Aubé, H. Sapoundjie6 / Computers and Chemical Engineering 24 (2000) 2623–2632 2631
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