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Chemical Engineering Science 59 (2004) 4125 – 4135

www.elsevier.com/locate/ces

Simulation of reverse flow operation for manipulation of catalyst surface


coverage in the selective oxidation of ammonia
Y.W. Budhi, A. Jaree1 , J.H.B.J. Hoebink∗ , J.C. Schouten
Laboratory of Chemical Reactor Engineering, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands

Received 15 December 2003; received in revised form 19 March 2004; accepted 1 April 2004
Available online 10 August 2004

Abstract
A mathematical model has been developed for the simulation of the ammonia oxidation in a reverse flow reactor. Computer simulations
were carried out with a kinetic scheme, based upon elementary reaction steps. Aim was to explore the potential of a reverse flow reactor
for selective oxidation of NH3 to produce either N2 , NO, or N2 O via a dedicated operation procedure. Therefore, the conversion of NH3
and the selectivity toward N2 , NO, or N2 O, were compared for a reverse flow operation and a steady state, once-through operation.
A new operation concept of reverse flow operation in combination with a periodically lower feed concentration is proposed. The novel
reactor concept shows a better performance compared to normal reverse flow operation and to steady state, once-through operation.
The results indicate that reverse flow operation can be applied for manipulation of conversion and selectivity. A periodically lower feed
concentration may increase the conversion, even up to levels that exceed the steady state value.
䉷 2004 Elsevier Ltd. All rights reserved.

Keywords: Reverse flow reactor; Feed concentration programming; Transient response; Selectivity; Modeling; Simulation

1. Introduction Among the various options for transient operation, peri-


odic operation offers the combined benefits of a permanent
Transient operations currently open new ways in process unsteady-state regime and a constant time-averaged regime.
intensification, which may offer considerable advantages for Periodically changing the flow direction through the re-
the performance of a process if a dedicated procedure can be actor, better known as reverse flow operation (hereinafter
developed. In this way, a continuous reactor may be inten- referred to as RFO), has not yet been widely applied for
tionally maintained under forced unsteady state conditions, improvement of conversion or selectivity, but was shown
as contrary to the traditional operation of continuous pro- beneficial for exothermic reactions from a viewpoint of en-
cesses, which focus on steady state. In the case of heteroge- ergy saving (Matros and Bunimovich, 1996). The use of the
neously catalyzed gas reactions in a fixed bed reactor, such reverse flow principle as transient operation procedure for
artificially invoked transient behaviour provides opportuni- a catalytic reactor becomes interesting by the combination
ties to create dynamic changes of the catalyst surface cov- of dynamic properties at a microscale (catalyst) and at a
erage, which affect the rates of the catalytic reactions. This macroscale (reactor). It may produce more favourable con-
principle has been widely explored by applying cycling of centration and temperature profiles for the catalytic process
the feed for improvement of reactor conversion or selectiv- (Ferreira et al., 1999).
ity (Silveston, 1998). In particular, periodic flow reversals provide a way to
∗ Corresponding author. Tel.: +31-40-247-2850; fax: +31-40-2446653.
affect the surface coverage of catalytic sites. In the case
of non-linear kinetics, changes in conversion or selectivity
E-mail address: j.h.b.j.hoebink@tue.nl (J.H.B.J. Hoebink).
1 Current address: Department of Chemical Engineering, Kasetsart Uni- could be expected when compared to once-through opera-
versity, POB 1032, Kasetsart Post Office, Jatujak, Bangkok 10903, Thai- tion. In principle, it could be possible to eliminate an unde-
land. sired intermediate product by reversing the flow when that

0009-2509/$ - see front matter 䉷 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2004.04.040
4126 Y.W. Budhi et al. / Chemical Engineering Science 59 (2004) 4125 – 4135

component is detected at the reactor outlet. In this contribu- is abundant on the surface. In the case of multiple reaction
tion, possible operation procedures for fixed bed reactors in products, the actual surface coverages determine the product
reverse flow mode are explored. distribution.
The advantages of the so-called forced transient opera- Suitable operation procedures for fixed bed reactors in
tion have been highlightened and enumerated some decades reverse flow mode should be developed. Basic idea is that
ago. The concept of RFO was refined and then extended to regular flow reversals result in spatio-temporal patterns of
catalytic reactors by Boreskov et al. (1982). An implementa- both gas phase concentration and catalyst surface coverages.
tion was made for SO2 oxidation (Bunimovich et al., 1995; The time-average behaviour may deviate from the steady
Sapundzhiev et al., 1988, 1990; Xiao et al., 1999), which state result. The aim of this paper is to demonstrate that
was continued by the installation of a successful process reverse flow operation may create dynamic changes of ac-
on an industrial scale (Matros, 1990). Ferreira et al. (1999) tive site coverages, which might form the selectivity to-
proposed reverse flow operation as a way to decrease the ward a desired product. The selective oxidation of ammo-
hot spot temperature and to obtain a more favourable tem- nia is chosen as a model reaction because of its various
perature distribution along the bed for o-xylene oxidation products.
to phthalic anhydride. The reverse flow operation can also If the flow direction is regularly reversed at a low fre-
be successfully applied for NOx reduction (Bobrova et al., quency, it is to be expected that reactor performance will
1988; Jirat et al., 1999; Matros et al., 1999). hardly deviate from the steady state performance. At high
Matros (1989) studied methanol synthesis under reverse frequencies, however, one should expect a considerable drop
flow operation, followed by Thullie and Burghardt (1990), in conversion when compared to the steady state. This is
and Neophytides and Froment (1992). vanden Bussche et al. due to the amount of unreacted gas, which has just entered
(1993) considered a one-dimensional heterogeneous model the reactor, but is driven out immediately after each flow re-
for this application. Various levels of transient modeling versal. Therefore, apart from normal reverse flow operation,
were compared. The most sophisticated model, accounting this paper also addresses situations in which the feed con-
for mass and energy capacities in both solid and gas phase centration is periodically lowered for a short while prior to
was used to assess the influence of a number of operating reversing the flow direction. Such a procedure can prevent
parameters. This model has been applied in a wide range of an obvious decrease of conversion during normal RFO.
process industries. More details on the potential of reverse
flow operation have been reported in an excellent overview
by Matros and Bunimovich (1996). 2. Ammonia oxidation
A transient operation according to the reverse flow princi-
ple gives rise to complicated dynamic behaviour of the fixed The oxidation of ammonia (NH3 ) with oxygen (O2 ) may
bed reactor, as has been reported on several occasions for the yield the products nitrogen (N2 ), nitrous oxide (N2 O), or
classical application of energy saving (e.g. Khinast and Luss, nitric oxide (NO), according to the exothermic global reac-
2000; Salinger and Eigenberger, 1996). The complexity of tions:
the non-linear dynamics of the whole system is caused by the
usually non-linear reaction kinetics on the scale of a catalytic 4NH3 + 3O2 → 2N2 + 6H2 O + 1266 kJ, (1)
active site, in combination with heat transfer aspects on the
4NH3 + 4O2 → 2N2 O + 6H2 O + 1102 kJ, (2)
scale of the reactor. Even a single, first order, exothermic re-
action, carried out in a reverse flow reactor, may show five 4NH3 + 5O2 → 4NO + 6H2 O + 904 kJ. (3)
regions with different bifurcation diagrams, the Damköhler
number being the bifurcation parameter (Khinast and Luss, The industrial production of NO from NH3 over catalytic
2000). The existence of stable periodic states depends on the platinum/rhodium gauzes is known as the Ostwald process.
bifurcation parameter value and on the route that leads to Extremely short contact times and very high temperatures,
the specific position in the bifurcation diagram. Knowledge typically over 1125 K, are applied. One tries to reach 100%
of the bifurcation behaviour is important for reactor design NH3 conversion in order to avoid downstream formation
and reactor control in order to avoid unstable operation. It of NH4 NO3 . The actual NH3 conversion of the process is
is also important to assess a safe reactor start-up procedure, around 96%. The selectivity towards NO is also around 96%
which includes a start-up period as short as possible. if that high reactor temperature is maintained. The selectiv-
Improvements of conversion and/or selectivity by feed ity to N2 O is 1.5–2%, and the remainder is N2 . At temper-
composition cycling or by admittance of pulses in the reactor ature below 773 K, the reactor produces mainly N2 , which
feed were ascribed to temporary changes in the coverage indicates that the reaction selectivity is strongly depending
of the catalyst’s active sites by reacting species (Silveston, on the applied temperature.
1998). The most favourable situation was obtained if the Apart from the selectivity, a high temperature is also re-
surface coverages are in agreement with the stoichiometry quired for activation of new gauzes in the reactor. Depend-
of the desired reaction as it occurs on the catalyst surface. ing on the applied process pressure, the lifetime of gauzes is
The catalyst’s activity drops considerably when one species in the order of 2–8 months. They suffer considerably from
Y.W. Budhi et al. / Chemical Engineering Science 59 (2004) 4125 – 4135 4127

Table 1
Elementary step kinetics for ammonia oxidation over supported Pt (Rebrov et al., 2003): { }= top site, ( )= hollow site, reaction rate parameters in form
k = A exp(−Ea /RT ) exp(j /RT )

rk Elementary step A Ea  Rate expression

1a NH3 +{ } → {NH3 } 2.00 × 108 0.0 0.0 R1 = k1 pNH3 top


2b {NH3 } → NH3 + { } 6.04 × 1015 9.60 × 104 0.0 R2 = k2 NH3
3a O2 +2( )→ 2(O) 4.30 × 106 0.0 0.0 R3 = k3 pO2 2hol
4b 2(O)→ O2 +2( ) 1.00 × 1013 2.13 × 105 6 × 104 R4 = k4 2O
5b {NH3 } + 3(O) + ( ) → (N) + 3(OH) + { } 1.14 × 1014 1.31 × 105 0.0 R5 = k5 NH3 O
6b (N)+(N)→ N2 + 2( ) 2.10 × 1011 9.82 × 104 0.0 R6 = k6 2N
7b (N)+{NO} → N2 O + { } + ( ) 4.10 × 109 8.60 × 104 0.0 R7 = k7 N NO
8b {NO} + 2( ) → (N) + (O) + { } 1.00 × 1013 1.18 × 105 0.0 R8 = k8 NO 2hol
9b (OH)+(OH)→ (O) + ( ) + H2 O 1.00 × 1011 4.82 × 104 0.0 R9 = k9 2OH
10b (N)+(O)+{ } → {NO} + 2( ) 5.65 × 1012 1.21 × 105 0.0 R10 = k10 N O
11a H2 O + ( ) + (O) → (OH) + (OH) 2.00 × 108 6.05 × 104 0.0 R11 = k11 pH2 O O
12b {NO} → NO + { } 1.00 × 1013 1.40 × 105 0.0 R12 = k12 NO
13a N2 O + ( ) → N2 + (O) 2.50 × 108 7.22 × 104 0.0 R13 = k13 pN2 O hol
a Pre-exponential factors are in s−1 atm −1 .
b Pre-exponential factors are in s−1 .

the necessary high temperature because platinum is oxidized steady state data with respect to NH3 and O2 conversions,
into platinum oxide, which evaporates. The rhodium enrich- as well as the selectivities to N2 , N2 O, and NO.
ment of the gauzes causes a slight decrease of the NO se- In general, the transient character of a reverse flow reac-
lectivity from 96% to 92%. As a result, the selectivity to N2 tor implies that steady state kinetics as usually expressed by
increases, while the selectivity to N2 O remains at the level Langmuir–Hinshelwood type of rate equations cannot be ap-
of 1.5–2%. plied. During steady state, rates of adsorption, surface reac-
Over the years, ammonia oxidation has become a highly tion, and desorption are all equal to each other, which is not
optimized and balanced process. Consequently, it is hard to necessarily the case during transient operation. Moreover, a
implement any proposals for improvement in existing plants rate-determining step may vary during a transient, while it is
even proven technology. In this respect, the current research fixed for a steady state operation. Therefore, the application
should be considered as providing a long-term solution that of a reverse flow reactor requires that the reaction kinetics
could be applied for new plants. However, implementation be determined on the level of elementary reaction steps.
in existing processes could become a serious option if the
N2 O and N2 formations would be suppressed in favour of the
NO selectivity. A further investigation of the mechanism and 3. Modeling of reverse flow reactor
kinetics of the ammonia oxidation, notably the formation of
nitrous oxide, would be very useful. Fig. 1 represents a simplified process scheme of the re-
The current work uses the ammonia oxidation kinetics verse flow reactor. During the 1st half of each cycle, the flow
as developed by Rebrov et al. (2003) for Pt/Al2 O3 cata- passes through 1-2-R-3-4, and during the 2nd half of each cy-
lyst, following work of Bradley et al. (1997), who observed cle, the flow passes through 1-2 -R-3 -4. In most RFO cases,
that adsorbed oxygen, up to coverages of 0.35 ML, does not the catalyst acts not only as a chemical reaction booster, but
block the adsorption of ammonia. The experimentally ob- also as a heat sink necessary for accumulating energy from
tained kinetic results were interpreted with a dual site mech- the exothermic reaction due to the fact that the heat capac-
anism. This means that nitrogen-containing species occupy ity of the catalyst bed is much higher compared to that of
one type of sites, so-called top sites, while non-nitrogen the processed gas. In this respect, the catalyst bed eventually
containing species occupy another type, known as hollow provides a periodic heat exchange between the stored energy
sites. and the cooler feed gas (Matros and Bunimovich, 1996).
A new approach in developing the kinetic scheme states From a viewpoint of energy saving, the flow should be
that adsorbed N itself can be considered in the hollow sites reversed as soon as the outlet flow temperature starts to rise
instead of top sites. According to experimental results on after the previous reversal (Bunimovich et al., 1995). As
ammonia synthesis over Ru, adsorbed N residing in hollow such, flow reversal frequencies should be related to the heat
sites was energetically favoured (Zhang et al., 2002). The of reaction, as well as to the reactor’s thermal inertia and
elementary steps of the kinetic scheme and the reaction rate throughput. These effects deal with the dynamic character-
parameters are shown in Table 1 (Rebrov et al., 2003). This istics of the whole reactor system. The bulk gas concentra-
kinetic model provides accurate predictions for experimental tions and catalyst surface coverages change in the direction
4128 Y.W. Budhi et al. / Chemical Engineering Science 59 (2004) 4125 – 4135

as follows:
*pi 1 *pi
2
Def * pi  
=− + 2 +  b RT rk , (4)
2nd half-cycle *t  *z Lr *z2 b
dj 
2' 3
= rk , (5)
dt
Flow in Flow out 
{} = 1 − ts
j , (6a)
1 4 
() = 1 − hs
j . (6b)

1st half-cycle 2 3' In a reverse flow operation, the linear velocity us changes
in sign for every ts seconds, with ts being the time period
between subsequent switches of the flow direction. When
Catalyst the reactor inlet is at coordinate z = 0 (forward flow), the
linear velocity is positive. On the contrary, the linear velocity
Fig. 1. Principle diagram of reverse flow operation. is negative when the reactor inlet is at coordinate z = 1
(backward flow). The linear velocity changes can be written
as follows:

of flow due to reaction, leading to locally different rates and us (t) = (t)u, (7a)

point selectivities. In RFO, the disturbance of such profiles +1 at t ∈ [2(n − 1)ts , 2(n − 0.5)ts ],
(t) = (7b)
along the reactor axis is governed by the dynamic properties −1 at t ∈ [2(n − 0.5)ts , 2nt s ],
of the catalytic processes, notably adsorption, desorption,
and surface reaction rates, as well as the storage capacity where u > 0 is the absolute value of the linear velocity, and
of the catalytic surface and the supply of reactants in the n = 1, 2, . . . is the number of switches (Matros and Buni-
reactor feed. In general, these catalytic processes are much movich, 1996).
faster (a factor one hundred is typical) than the dynamics re- For the dispersed plug flow model, the use of Danckwerts
lated to heat transfer aspects. The question of conversion and boundary conditions is required, which are shown for the gas
selectivity enhancement was earlier addressed (Bunimovich phase components as written in Eqs. (8a) and (8b). Because
et al., 1995), but for a cycle chosen for heat recovery. No the flow direction in the reactor is periodically reversed, the
enhancement was observed at lower inlet concentrations. In reactor inlet and outlet boundary conditions also have to be
the current work, a typical switching time for heat recovery periodically altered to reflect the change in operation mode.
would require dozens of minutes. It means that manipulation 
*pi  1 + (t) us Lr 0
of the reactor selectivity requires considerably more frequent  = (p − pi ), (8a)
flow reversals than would be necessary from a viewpoint of *z z=0 2 Def i

energy saving. Consequently, one can assume that the heat *pi  1 − (t) us Lr 0
=− (p − pi ). (8b)
*z z=1
balance is always in a relaxed steady state regime and that
2 Def i
the benefits of energy saving are maintained if one aims at
improvement of the selectivity. In this study, the purpose of The steady state situation in a reactor without flow rever-
modeling and simulation is to demonstrate the effect of pe- sal was used as the initial condition for the continuity equa-
riodic flow reversal on conversion and product selectivity. tion. The assumption was taken for the sake of computation
A dynamic, pseudo-homogeneous, one-dimensional model in order to save CPU time, because the steady state concen-
of a fixed bed reactor was used to describe the reverse flow tration profile would be a reasonable estimate of the situa-
reactor performance. tion under conditions of flow reversals at low frequency.
Flow reversal leads to transient behaviour, which means
that accumulation should be incorporated in the continuity pi = piss at t = 0, z ∈ [0, 1], (9)
equations. The fixed bed reactor was considered as a plug j = ss
j at t = 0, z ∈ [0, 1]. (10)
flow reactor, but an axial dispersion term was included for
reasons of numerical stability. The dispersion coefficient was The model equations, shown above, were numeri-
set to the value 10−7 m2 s−1 and it was verified that this small cally solved by using the software package, FlexPDE
value did not affect the obtained simulation results. Hayes (PDE Solutions Inc., 2001) which solved partial differen-
and Kolaczkowski (1997) verified that a plug flow model tial equation (PDE’s), coupled with ordinary differential
would not be expected to give significantly different results equations (ODE’s) and algebraic equations. Each con-
compared to the dispersed plug flow model. The continuity tinuity equation in the gas phase gave rise to a PDE
equation for the gas phase and the solid phase can be written (Eq. (4)), while each surface species led to an ODE
Y.W. Budhi et al. / Chemical Engineering Science 59 (2004) 4125 – 4135 4129

(Eq. (5)). Vacant top and hollow sites were written each as Table 2
an algebraic equation (Eqs. (6a) and (6b)). Operating conditions
FlexPDE is a scripted finite element model builder and Reactor
numerical solver (Backstrom, 1999). It means that from a Diameter (m) 15 × 10−3
script written by the user, FlexPDE performs the operations Length (m) 30 × 10−3
necessary to turn a PDE system into a finite element model, Bed bulk density (kg mr−3 ) 1230
solve the system of equations, and present graphical output Void fraction (mg3 mr−3 ) 0.45
Catalyst weight (kg) 6.054 × 10−3
of the results. The FlexPDE calculations also involve au-
Total number of sites (mol) 6.85 × 10−8
tomatic remeshing when stiff profiles prevail. Such events
happen in particular due to discontinuities when the flow Operating conditions
direction is reversed. Inlet temperature (K) 800
As a first step, preliminary simulations were carried out Total pressure (atm) 1
for a reactor with imposed steady temperature profile as typ- Superficial velocity (m s−1 ) 0.135 × 10−2
Residence time (s) 10
ical for a reverse flow reactor, which seems allowed because Switching time (s) Varied
thermal behaviour and kinetic behaviour have completely NH3 in feed (mol%) 1
different time scales. The former can be considered as in a O2 /NH3 ratio in feed 1:1
relaxed steady state regime when compared to the latter. It He (mol%) Balance
points out that there was no need to incorporate heat bal-
ances into the reactor model. It should be sufficient to impose
a symmetrical, steady temperature profile along the reactor involving heat balances, and it was checked that a permanent
axis. At both ends of the reactor, the temperature equals the cyclic regime had been established. Note that the reactor
feed temperature. The maximum temperature in the middle wall temperature and heat loss through the reactor wall are
corresponds to the maximum adiabatic temperature rise, cor- irrelevant if the temperature profile is known.
rected for heat loss. This simplification was made because The conversion and selectivity during reverse flow op-
of the complexity and stiffness of the system of equations eration were calculated as time-average values, obtained
when working with a full elementary-step scheme of am- by integration of the actual values over a complete cycle
monia oxidation. Some justifications of this approach were consisting of two flow reversals. In the case that inlet and
found in the rather frequent switches of the flow direction outlet concentrations change as function of time, both con-
and the great difference in heat capacity of gas and catalyst centrations should be determined by averaging the instan-
phase. taneous concentration over a complete cycle (Eqs. (11a)
Fig. 2 shows the imposed gas phase temperature profile and (11b)):
along the reactor. This profile was calculated for one case,
 tc /2 t
i 0 C(t)|z=Lr dt + tcc/2 C(t)|z=0 dt
C =  tc , (11a)
0 dt
 tc /2  tc
o 0 C(t)|z=0 dt + tc /2 C(t)|z=Lr dt
810 C =  tc . (11b)
0 dt
808
For the special case of a constant density reactor, the
Temperature [K]

cycle-averaged conversion can be easily determined by using


806 the cycle-averaged inlet and outlet concentrations. Similarly,
the selectivity and productivity towards N2 , NO, and N2 O,
804 can also be formulated.
The reactor specification and typical operating conditions
802
used during the reverse flow simulations are shown in Table
2 , unless otherwise indicated. The catalyst data refer to Pt
on alumina catalyst.
800

4. Simulation results
0.0 0.2 0.4 0.6 0.8 1.0
Reactor length [-]
4.1. Once-through operation
Fig. 2. Imposed steady temperature profile as used for reverse flow
simulations. The inlet temperature is 800 K and the maximum temperature First of all, steady state simulations, i.e. without flow re-
is 810 K. versals, were performed at various conditions as mentioned
4130 Y.W. Budhi et al. / Chemical Engineering Science 59 (2004) 4125 – 4135

above. These results should be considered as necessary 4.2. Reverse flow simulation
references in order to judge the potential of reverse flow
operation for improvement of the reactor performance. All simulations were performed with an imposed sym-
Moreover, the steady state results were used as initial metrical temperature profile to assure that thermal behaviour
condition for solving the model equations in the case of is in relaxed steady state regime compared to the dynamics
reverse flow operation. The steady state was obtained by of the mass balance. The concentration profiles as function
solving the transient equations, starting from a reactor of time generally show stable oscillations after three cycles,
completely free from reactants and products, until changes which supports the earlier suggestion that the dynamics of
in the reactor profile became negligible in time. All cal- the mass balance are much faster than those of the energy
culations were carried out using the software package balance. Therefore, a steady temperature profile can always
FlexPDE. be imposed, once the proper function is known. It should be
Fig. 3 shows the conversion and selectivity (a and c) and noted that a temperature profile could be directly measured
surface coverages (b and d) as function of temperature for during experimental work in reverse flow reactors. For low
a residence time of 10 s and two distinct O2 /NH3 feed ra- feed concentrations and/or low conversion, isothermal reac-
tios. A temperature rise at fixed residence time and O2 /NH3 tor operation will be achieved, which means that model val-
feed ratio decreases the selectivity toward N2 and N2 O, and idation can be performed with a relatively uniform reactor
increases the NO selectivity. In general, the conversion in- temperature.
creases at higher temperature, but this is not the case at low The steady state results were inspected with respect to the
O2 /NH3 when O2 becomes the limiting reactant (Fig. 3a). occurrence of pronounced axial profiles of gas phase con-
A feed temperature of 800 K was chosen for simulations of centrations and/or catalyst surface coverages. Conceivably,
reverse flow operation because it appears that at this tem- such behaviour is most likely affected by applying reverse
perature, considerable gradients of surface coverages exist flow operation. Reverse flow simulations were therefore per-
along the reactor axis. Such profiles seem most promising formed at conditions that give rise to pronounced axial pro-
to obtain beneficial effects of RFO when compared to the files.
steady state operation. At lower temperature, the conversion Apart from the three process variables: temperature (T),
of NH3 becomes quite low, although steeper profiles of ad- residence time (), and feed ratio (FR), that characterize
sorbed species appear in this situation. At higher tempera- the steady state, one needs a new parameter , defined as
ture, only vacant sites are present due to large species des- the ratio of switching time (ts ) and residence time in order
orption rates. to clearly define RFO conditions. As mentioned previously,
Fig. 4 shows the conversion and selectivity (a) and sur- the time scale of the switching time for the application of
face coverage (b) as function of the O2 /NH3 feed ratio. An reverse flow operation for selectivity manipulation is com-
increase of the feed ratio stimulates the conversion of NH3 pletely different when compared to the similar operation for
and selectivity to NO considerably. The selectivity to N2 O energy saving. For the latter, the switching time is quite
changes only slightly, while the N2 selectivity decreases sig- large, in the range of several minutes to several hours. In
nificantly. At low feed ratio, mainly vacant sites are present the current application, the time scale of switching has the
on the catalyst surface. Such conditions are less interest- same order of magnitude as the residence time (seconds). It
ing for the issue of selectivity manipulation using RFO. At should be verified if such high switching frequencies could
high feed ratio, the number of vacant hollow site drops sig- be realized in industrial practice.
nificantly as adsorbed O increases up to a fraction of 0.8. Three ranges of the parameter  can be distinguished be-
The availability of adsorbed O drives many reaction steps, cause perturbation may either disturb the steady state of a
which causes the rather small decrease of the number of process or may prevent that a process becomes steady. The
vacant top sites at higher O2 /NH3 ratios. The feed ratio of three regimes are illustrated in Figs. 5a–c, where NH3 partial
O2 /NH3 = 1:1 was applied during the reverse flow simula- pressure responses are plotted versus time. The time-average
tion because the NH3 conversion reaches a high level and value (ptavg ) and the value during steady state once-through
significant profiles of adsorbed species along the reactor axis operation are also shown for comparison.
are clearly present.
A larger residence time at fixed reactor temperature and • A high flow reversal frequency ( < 1), see Fig. 5a, means
feed ratio leads to higher N2 selectivity, but lower NO se- that a central part of the reactor is never refreshed with
lectivity if NH3 is in excess. An increase of the NH3 feed fresh reactants by convection. Apparently, this causes a
fraction at fixed temperature and residence time increases decrease of the conversion, as indicated by the level of
the N2 selectivity, but decreases the NH3 conversion and the ptavg and pss . Depending on the flow direction, this gas
NO and N2 O selectivities. The N2 O selectivity decreases volume moves up- and downwards, which leads to ex-
considerably at higher temperatures; the influence of the res- change between gas phase and catalyst surface. As such,
idence time and NH3 /O2 ratio is minor. However, it should this amount of gas is not to be considered as dead volume.
be kept in mind that high selectivities to N2 O are possible The limiting reactant might be completely converted into
at extremely short residence time (Rebrov et al., 2003). products, which means that a high product concentration
Y.W. Budhi et al. / Chemical Engineering Science 59 (2004) 4125 – 4135 4131

100 1.0
NH3 { }
( )

Conversion, Selectivity [%]


80 0.8

Surface coverage [-]


NO

60 0.6

40 0.4 (O)
N2

20 0.2 {NH3}
{NO}
N2O (OH)
(N)
0 0.0
750 800 850 900 750 800 850 900
(a) Temperature [K] (b) Temperature [K]

100 1.0
NH3 { }
Conversion, Selectivity [%]

0.9
80 NO (O)

Surface coverage [-]


0.8
60
0.7
40 {NO}
0.2 ( )
20 N2 0.1 (N)
{NH3}
N2O (OH)
0 0.0
750 800 850 900 750 800 850 900
(c) Temperature [K] (d) Temperature [K]

Fig. 3. The conversion and selectivity (a and c) and surface coverage (b and d) as a function of temperature. Feed ratios of O2 to NH3 are 1:1
(a and b) and 2:1 (c and d), and residence time is 10 s.

100 1.0 0.06


{ }
(O)
Conversion, Selectivity [%]

NH3 ( ) {NO}
80 0.8
Surface coverage [-]

NO
0.04
60 0.6

40 0.4
N2 (N) (OH) 0.02

20 0.2
N2O
{NH3}
0 0.0 0.00
0.25 0.75 1.25 1.75 2.25 0.25 0.75 1.25 1.75 2.25
(a) Feed ratio of O2 to NH3 (b) Feed ratio of O2 to NH3

Fig. 4. The conversion and selectivity (a) and surface coverage (b) as a function of feed ratio of O2 /NH3 . Temperature and residence time are 800 K and
10 s, respectively.

is always trapped inside the reactor. Therefore, period- •   1 means that flow reversals occur at low frequency,
ically flushing the trapped gas by a short once-through which leads to quasi-steady state behaviour, in fact
operation might be an interesting option to increase the steady state behaviour, because the flow direction hardly
conversion and product selectivity. At extremely frequent affects the time average result. As shown in Fig. 5b,
flow reversals, the reactor outlet will not respond any- the dynamic response completely coincides with the
more to the perturbation, which should be considered as steady state except for a short period after a flow
the relaxed steady state. reversal.
4132 Y.W. Budhi et al. / Chemical Engineering Science 59 (2004) 4125 – 4135

0.01 0.01

Partial pressure of NH3 [atm]

Partial pressure of NH3 [atm]


prss
ptavg

p*tavg pqss

ptavg pss
pss

0.00 0.00
0 1 2 3 4 0 25 50 75 100
(a) Time [s] (b) Time [s]
0.01
Partial pressure of NH3 [atm]

pdyn

ptavg

pss

0.00
0 5 10 15 20
(c) Time [s]

Fig. 5. Different types of flow reversal behaviour at different time scale. The partial pressure response of NH3 at reactor outlet is plotted as a function
of time. pss stands for partial pressure of NH3 in steady state, once-through operation, prss , pqss , and pdyn for relaxed-steady state, quasi-steady state,
and dynamic responses in reverse flow operation, respectively, and ptavg for the time-average value. Switching time: (a) 2 s, (b) 50 s, (c) 10 s. Other
operating conditions as mentioned in Table 2.

Table 3 average conversion of NH3 during reverse flow operation is


Conversion and selectivity compared for SSO and RFO at various switch- always smaller than that of once-through operation, regard-
ing frequencies with operating conditions as mentioned in Table 2
less of . To overcome this effect, one case of an intermit-
RFO SSO tent flushing method was studied (see 2 # in Table 3). After
every 5 semi-cycles of 2 s, the gas content of the bed was
Switching time (s) 2 2# 10 15 50 —
Conversion of NH3 (%) 33.1 54.7 71.2 75.4 80.8 82.7 flushed for a period of 10 s, which is the same as the res-
Selectivity of N2 (%) 32.6 32.0 31.0 30.8 30.7 30.6 idence time. Flushing the reactor after a number of cycles
Selectivity of NO (%) 58.9 61.1 60.9 61.1 61.2 61.3 increases the conversion because reactants are almost fully
Selectivity of N2 O (%) 8.5 6.9 8.1 8.1 8.1 8.1 converted in the centre of the reactor (see the NH3 partial
# 5 times in semi-cycle, then flushed during 10 s. ∗
pressure ptavg in the trapped gas, Fig. 5a). However, the
conversion is still smaller than in the steady state value and
during RFO with higher switching times, while the selec-
• Situations with  ≈ 1, where perturbation and process tivity is hardly affected. Therefore, the flushing strategy is
have comparable time scales, cause real dynamic be- basically not useful for low frequencies of RFO.
haviour with possible involvement of resonance effects As shown in Table 3, RFO affects the product distribu-
due to non-linear behaviour of the whole system as shown tion. Therefore, the relation between conversion and selec-
in Fig. 5c. This region seems most interesting. tivity was considered in order to make certain that selectiv-
ity changes are really caused by reverse flow operation, and
Table 3 shows the comparison of simulation results be- not as an artifact of the change in conversion.
tween the reverse flow operation with various switching time Table 4 compares the simulation results for once-through
and the steady state operation at the same conditions, i.e. and reverse flow operations at the same temperature and feed
temperature, residence time, and feed ratio. At low flow re- ratio, but different residence time in order to maintain the
versal frequency, conversion and selectivities approach the same conversion. At 800 K and O2 to NH3 = 1:1, SSO with
steady state values as expected. Only minor changes in the a residence time of 1.1 s and RFO with a residence time of 10
various selectivities due to RFO are observed. The time- s and switching time of 0.5 s, provide the same conversion
Y.W. Budhi et al. / Chemical Engineering Science 59 (2004) 4125 – 4135 4133

Table 4 100
Comparison of conversion and selectivity for SSO and RFO at the same
conversion with operating conditions as mentioned in Table 2 NH3
NH3SSO
T 800 K, O2 /NH3 1:1 SSO RFO
80
Residence time (s) 1.1 10

Conversion, Selectivity [%]


Switching time (s) — 0.5 NO
Conversion of NH3 (%) 17.3 17.3
60 NOSSO
Selectivity to N2 (%) 34.1 32.6
Selectivity to NO (%) 56.0 59.6
Selectivity to N2 O (%) 9.9 7.8

40
N2
of 17.3%. Note that the product distributions are different.
This example clearly shows that the differences in product N2SSO

distributions are really caused by reverse flow operation. 20


The effect of RFO on the selectivity may be positive or not, N2O
N2OSSO
depending on the chosen process conditions and the actually
desired product. 0
0 2 4 6 8 10
Time period [s]
4.3. Reverse flow operation in combination with periodic
lower feed concentration Fig. 6. Conversion and selectivity as a function of the time period of
lower feed concentration. The steady state values (SSO) are indicated
In the normal RFO, the feed concentration is kept con- on the right axis. Switching time is 10 s. Other operating conditions as
mentioned in Table 2.
stant. The time-average conversion of a reverse flow reac-
tor is always smaller than that of the steady state operation.
A major reason for a lower conversion under RFO when of the NH3 concentration for both inlet and outlet. The latter
compared to SSO at the same conditions deals with the fact is alternating between 152 and 1.52 mmol m−3 during each
that the gas, which has just entered the reactor, is driven half-cycle.
out again at very low conversion shortly after a flow rever- Fig. 6 shows that if the time period of a low feed concen-
sal. This rather inefficient way of working could be avoided tration of NH3 increases, the reactor conversion increases
by periodically lowering the feed concentration for a short as well up to a maximum. Further increase in this time
period before the flow direction is reversed. In this way, a period decreases the conversion. The maximum conversion
waste of raw material in the feed is avoided, which could of NH3 is reached when the time period of low feed con-
be considered as feed stock saving. As a result, the reactor centration is 7.1 s. The conversion may even exceed the
performance is improved when compared to SSO and the steady state value in a certain range of this parameter. The
normal RFO, i.e. without lowering feed concentration. The selectivities to N2 and N2 O decrease, while the selectiv-
feed stock saving depends on the time period of low feed ity for NO increases. Considering the reactor productivity,
concentration (tL ). Table 5 and Fig. 6 show typical simu- defined as conversion times selectivity, Table 5 shows that
lation results. The conditions are mentioned in Table 2, but the productivity of notably NO can be largely improved by
a constant switching time ts of 10 s is chosen for compar- RFO with periodical low feed concentration when com-
ison with the normal RFO mode. Conversion and selectiv- pared to the steady state performance. Operating a reverse
ities are again expressed as time-average values over one flow reactor in this mode can offer more benefits than reg-
complete cycle with incorporation of the time-dependence ular flow reversals. This seems analogous to energy saving

Table 5
Productivity and production rate with periodically lowering feed concentration; operating conditions as mentioned in Table 2

Switching time 10 s RFO SSO

Time period of lower feed concentration (s) 9.5 8 5 3 1 0 —


Productivity of N2 10.5 17.7 23.8 24.5 23.3 22.1 25.3
Productivity of NO 72.8 69.4 60.0 55.2 48.5 43.4 50.7
Productivity of N2 O 4.6 5.6 7.4 6.4 6.2 5.8 6.7
Production of N2 (mol s−1 × 106 ) 0.11 0.62 2.02 2.91 3.54 3.73 4.27
Production of NO (mol s−1 × 106 ) 1.46 4.87 10.22 13.09 14.75 14.64 17.11
Production of N2 O (mol s−1 × 106 ) 0.05 0.20 0.63 0.76 0.94 0.98 1.13
4134 Y.W. Budhi et al. / Chemical Engineering Science 59 (2004) 4125 – 4135

1 1

Adsorbed O [-]

Adsorbed O [-]
z = 0.4 z = 0.6
z = 0.4 z = 0.6
z = 0.2 z = 0.8
z = 0.2 z = 0.8
z=0 z=1
z=0 z=1

0 0
140 145 150 155 160 140 145 150 155 160
(a) Time [s] (b) Time [s]

Fig. 7. Adsorbed O as a function of time after starting flow reversals at 140 s: (a) reverse flow operation without periodically lower feed concentration,
(b) reverse flow operation with periodically lower feed concentration. Other process conditions as mentioned in Table 2.

application, where the feed temperature can be lowered on scale compared to the conventional application for energy
account of the availability of the heat trapped inside the re- saving. Such an operation leads to a different reactor per-
actor, so reducing the preheater duty. If the feed concentra- formance in comparison to the steady state performance.
tion is kept constant at a high level, the catalyst layer at the At low flow reversal frequency, the time-average conversion
outer ends of the reactor does not contribute much to the re- and selectivities approach the steady state values. Only mi-
action, so the amount of unconverted ammonia flowing out nor changes in the various selectivities due to RFO are ob-
of the reactor is larger. served. On the other hand, the conversion drops consider-
It should be noted that the higher NO productivity is ac- ably if RFO is carried out at a high flow reversal frequency.
companied by a lower production of all components (see It was clearly demonstrated that the differences in product
Table 5), meaning that a larger reactor or reactors in parallel distribution are really caused by reversing the flow direc-
are required to maintain the production level. It was verified tion. The effect of RFO on the selectivity may be positive
by comparing two cases with and without programmed feed or not, depending on the chosen conditions.
concentration, but at the same time-average feed concentra- A new concept is proposed to overcome the decrease of
tion that the improved conversion in RFO with periodically conversion during reverse flow operation. In this concept, a
lower feed concentration was indeed caused by the concen- periodically lower feed concentration is programmed before
tration programming. As an example, the conversion of NH3 the flow direction is reversed. Such a procedure increases the
in RFO with periodic lower feed concentration ( = 10 s, conversion, which may even exceed the steady state value.
ts = 10, tL = 5 s) is 15% higher than in normal RFO at the The selectivities are also changed.
same time-average inlet concentration.
Fig. 7 shows the adsorbed oxygen coverage as function of
time during one cycle for the case without (Fig. 7a) and with Notation
(Fig. 7b) periodically lower feed concentration. The param-
eter in the figure refers to the dimensionless length along A pre-exponential factor, s−1 atm−1 or s−1
the reactor axis. It is apparent that a lower feed concentra- C gas concentration, mol m−3
tion induces locally and temporarily high levels of adsorbed Def axial dispersion coefficient, m2 s−1
oxygen species, which favour NH3 conversion and NO se- Ea activation energy, J mol−1
lectivity. At larger time periods of lower feed concentration, FR feed ratio of O2 /NH3
the availability of ammonia becomes smaller, which limits k reaction rate coefficient, s−1 atm−1 or s−1
the conversion of NH3 . The selectivity to N2 is lower with Lr reactor length, m
increasing time period of lower feed concentration. On the p partial pressure of gas, atm
contrary, the selectivity to NO becomes larger due to the fact r reaction rate, s−1
that the reaction rate to produce NO is now strongly driven R ideal gas constant, m3 atm mol−1 K −1
by a better availability of adsorbed O. S selectivity, %
t time, s
5. Conclusion tc cycling time (double of switching time when sym-
metric operation), s
A cyclic operation of reversing the flow direction for ma- tL time period of low feed concentration, s
nipulation of conversion and selectivity has a different time ts switching time, s
Y.W. Budhi et al. / Chemical Engineering Science 59 (2004) 4125 – 4135 4135

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G.F., 1993. Modeling and simulation of the reversed-flow operation
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