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-

Transient operations currently open new ways in process
intensification, which may offer considerable advantages for
the performance of a process if a dedicated procedure can be
developed. In this way, a continuous reactor may be inten-
tionally maintained under forced unsteady state conditions,
as contrary to the traditional operation of continuous pro-
cesses, which focus on steady state. In the case of heteroge-
neously catalyzed gas reactions in a fixed bed reactor, such
artificially invoked transient behaviour provides opportuni-
ties to create dynamic changes of the catalyst surface cov-
erage, which affect the rates of the catalytic reactions. This
principle has been widely explored by applying cycling of
the feed for improvement of reactor conversion or selectiv-
ity (Silveston, 1998).
∗ Corresponding author. Tel.: +31-40-247-2850; fax: +31-40-2446653.
E-mail address: j.h.b.j.hoebink@tue.nl (J.H.B.J. Hoebink).
1 Current address: Department of Chemical Engineering, Kasetsart Uni-
versity, POB 1032, Kasetsart Post Office, Jatujak, Bangkok 10903, Thai-
land.
odic operation offers the combined benefits of a permanent
unsteady-state regime and a constant time-averaged regime.
Periodically changing the flow direction through the re-
actor, better known as reverse flow operation (hereinafter
referred to as RFO), has not yet been widely applied for
improvement of conversion or selectivity, but was shown
beneficial for exothermic reactions from a viewpoint of en-
ergy saving (Matros and Bunimovich, 1996). The use of the
reverse flow principle as transient operation procedure for
a catalytic reactor becomes interesting by the combination
of dynamic properties at a microscale (catalyst) and at a
macroscale (reactor). It may produce more favourable con-
centration and temperature profiles for the catalytic process
(Ferreira et al., 1999).
In particular, periodic flow reversals provide a way to
affect the surface coverage of catalytic sites. In the case
of non-linear kinetics, changes in conversion or selectivity
could be expected when compared to once-through opera-
tion. In principle, it could be possible to eliminate an unde-
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-
tion, possible operation procedures for fixed bed reactors in
reverse flow mode are explored.
The advantages of the so-called forced transient opera-
tion have been highlightened and enumerated some decades
ago. The concept of RFO was refined and then extended to
catalytic reactors by Boreskov et al. (1982). An implementa-
tion was made for SO2 oxidation (Bunimovich et al., 1995;
Sapundzhiev et al., 1988, 1990; Xiao et al., 1999), which
was continued by the installation of a successful process
on an industrial scale (Matros, 1990). Ferreira et al. (1999)
proposed reverse flow operation as a way to decrease the
hot spot temperature and to obtain a more favourable tem-
perature distribution along the bed for o-xylene oxidation
to phthalic anhydride. The reverse flow operation can also
be successfully applied for NOx reduction (Bobrova et al.,
1988; Jirat et al., 1999; Matros et al., 1999).
Matros (1989) studied methanol synthesis under reverse
flow operation, followed by Thullie and Burghardt (1990),
and Neophytides and Froment (1992). vanden Bussche et al.
(1993) considered a one-dimensional heterogeneous model
for this application. Various levels of transient modeling
were compared. The most sophisticated model, accounting
for mass and energy capacities in both solid and gas phase
was used to assess the influence of a number of operating
parameters. This model has been applied in a wide range of
process industries. More details on the potential of reverse
flow operation have been reported in an excellent overview
by Matros and Bunimovich (1996).
A transient operation according to the reverse flow princi-
ple gives rise to complicated dynamic behaviour of the fixed
bed reactor, as has been reported on several occasions for the
classical application of energy saving (e.g. Khinast and Luss,
2000; Salinger and Eigenberger, 1996). The complexity of
the non-linear dynamics of the whole system is caused by the
usually non-linear reaction kinetics on the scale of a catalytic
active site, in combination with heat transfer aspects on the
scale of the reactor. Even a single, first order, exothermic re-
action, carried out in a reverse flow reactor, may show five
regions with different bifurcation diagrams, the Damköhler
number being the bifurcation parameter (Khinast and Luss,
2000). The existence of stable periodic states depends on the
bifurcation parameter value and on the route that leads to
the specific position in the bifurcation diagram. Knowledge
of the bifurcation behaviour is important for reactor design
and reactor control in order to avoid unstable operation. It
is also important to assess a safe reactor start-up procedure,
which includes a start-up period as short as possible.
Improvements of conversion and/or selectivity by feed
composition cycling or by admittance of pulses in the reactor
feed were ascribed to temporary changes in the coverage
of the catalyst’s active sites by reacting species (Silveston,
1998). The most favourable situation was obtained if the
surface coverages are in agreement with the stoichiometry
of the desired reaction as it occurs on the catalyst surface.
The catalyst’s activity drops considerably when one species
is abundant on the surface. In the case of multiple reaction
products, the actual surface coverages determine the product
distribution.
Suitable operation procedures for fixed bed reactors in
reverse flow mode should be developed. Basic idea is that
regular flow reversals result in spatio-temporal patterns of
both gas phase concentration and catalyst surface coverages.
The time-average behaviour may deviate from the steady
state result. The aim of this paper is to demonstrate that
reverse flow operation may create dynamic changes of ac-
tive site coverages, which might form the selectivity to-
ward a desired product. The selective oxidation of ammo-
nia is chosen as a model reaction because of its various
products.
If the flow direction is regularly reversed at a low fre-
quency, it is to be expected that reactor performance will
hardly deviate from the steady state performance. At high
frequencies, however, one should expect a considerable drop
in conversion when compared to the steady state. This is
due to the amount of unreacted gas, which has just entered
the reactor, but is driven out immediately after each flow re-
versal. Therefore, apart from normal reverse flow operation,
this paper also addresses situations in which the feed con-
centration is periodically lowered for a short while prior to
reversing the flow direction. Such a procedure can prevent
an obvious decrease of conversion during normal RFO.
2. Ammonia oxidation
The oxidation of ammonia (NH3 ) with oxygen (O2 ) may
yield the products nitrogen (N2 ), nitrous oxide (N2 O), or
nitric oxide (NO), according to the exothermic global reac-
tions:
4NH3 + 3O2 → 2N2 + 6H2 O + 1266 kJ, (1)
4NH3 + 4O2 → 2N2 O + 6H2 O + 1102 kJ, (2)
4NH3 + 5O2 → 4NO + 6H2 O + 904 kJ. (3)
The industrial production of NO from NH3 over catalytic
platinum/rhodium gauzes is known as the Ostwald process.
Extremely short contact times and very high temperatures,
typically over 1125 K, are applied. One tries to reach 100%
NH3 conversion in order to avoid downstream formation
of NH4 NO3 . The actual NH3 conversion of the process is
around 96%. The selectivity towards NO is also around 96%
if that high reactor temperature is maintained. The selectiv-
ity to N2 O is 1.5–2%, and the remainder is N2 . At temper-
ature below 773 K, the reactor produces mainly N2 , which
indicates that the reaction selectivity is strongly depending
on the applied temperature.
Apart from the selectivity, a high temperature is also re-
quired for activation of new gauzes in the reactor. Depend-
ing on the applied process pressure, the lifetime of gauzes is
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
into platinum oxide, which evaporates. The rhodium enrich-
ment of the gauzes causes a slight decrease of the NO se-
lectivity from 96% to 92%. As a result, the selectivity to N2
increases, while the selectivity to N2 O remains at the level
of 1.5–2%.
Over the years, ammonia oxidation has become a highly
optimized and balanced process. Consequently, it is hard to
implement any proposals for improvement in existing plants
even proven technology. In this respect, the current research
should be considered as providing a long-term solution that
could be applied for new plants. However, implementation
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
kinetics of the ammonia oxidation, notably the formation of
nitrous oxide, would be very useful.
The current work uses the ammonia oxidation kinetics
as developed by Rebrov et al. (2003) for Pt/Al2 O3 cata-
lyst, following work of Bradley et al. (1997), who observed
that adsorbed oxygen, up to coverages of 0.35 ML, does not
block the adsorption of ammonia. The experimentally ob-
tained kinetic results were interpreted with a dual site mech-
anism. This means that nitrogen-containing species occupy
one type of sites, so-called top sites, while non-nitrogen
containing species occupy another type, known as hollow
sites.
A new approach in developing the kinetic scheme states
that adsorbed N itself can be considered in the hollow sites
instead of top sites. According to experimental results on
ammonia synthesis over Ru, adsorbed N residing in hollow
sites was energetically favoured (Zhang et al., 2002). The
elementary steps of the kinetic scheme and the reaction rate
parameters are shown in Table 1 (Rebrov et al., 2003). This
kinetic model provides accurate predictions for experimental
steady state data with respect to NH3 and O2 conversions,
as well as the selectivities to N2 , N2 O, and NO.
In general, the transient character of a reverse flow reac-
tor implies that steady state kinetics as usually expressed by
Langmuir–Hinshelwood type of rate equations cannot be ap-
plied. During steady state, rates of adsorption, surface reac-
tion, and desorption are all equal to each other, which is not
necessarily the case during transient operation. Moreover, a
rate-determining step may vary during a transient, while it is
fixed for a steady state operation. Therefore, the application
of a reverse flow reactor requires that the reaction kinetics
be determined on the level of elementary reaction steps.
3. Modeling of reverse flow reactor
Fig. 1 represents a simplified process scheme of the re-
verse flow reactor. During the 1st half of each cycle, the flow
passes through 1-2-R-3-4, and during the 2nd half of each cy-
cle, the flow passes through 1-2 -R-3 -4. In most RFO cases,
the catalyst acts not only as a chemical reaction booster, but
also as a heat sink necessary for accumulating energy from
the exothermic reaction due to the fact that the heat capac-
ity of the catalyst bed is much higher compared to that of
the processed gas. In this respect, the catalyst bed eventually
provides a periodic heat exchange between the stored energy
and the cooler feed gas (Matros and Bunimovich, 1996).
From a viewpoint of energy saving, the flow should be
reversed as soon as the outlet flow temperature starts to rise
after the previous reversal (Bunimovich et al., 1995). As
such, flow reversal frequencies should be related to the heat
of reaction, as well as to the reactor’s thermal inertia and
throughput. These effects deal with the dynamic character-
istics of the whole reactor system. The bulk gas concentra-
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
references in order to judge the potential of reverse flow
operation for improvement of the reactor performance.
Moreover, the steady state results were used as initial
condition for solving the model equations in the case of
reverse flow operation. The steady state was obtained by
solving the transient equations, starting from a reactor
completely free from reactants and products, until changes
in the reactor profile became negligible in time. All cal-
culations were carried out using the software package
FlexPDE.
Fig. 3 shows the conversion and selectivity (a and c) and
surface coverages (b and d) as function of temperature for
a residence time of 10 s and two distinct O2 /NH3 feed ra-
tios. A temperature rise at fixed residence time and O2 /NH3
feed ratio decreases the selectivity toward N2 and N2 O, and
increases the NO selectivity. In general, the conversion in-
creases at higher temperature, but this is not the case at low
O2 /NH3 when O2 becomes the limiting reactant (Fig. 3a).
A feed temperature of 800 K was chosen for simulations of
reverse flow operation because it appears that at this tem-
perature, considerable gradients of surface coverages exist
along the reactor axis. Such profiles seem most promising
to obtain beneficial effects of RFO when compared to the
steady state operation. At lower temperature, the conversion
of NH3 becomes quite low, although steeper profiles of ad-
sorbed species appear in this situation. At higher tempera-
ture, only vacant sites are present due to large species des-
orption rates.
Fig. 4 shows the conversion and selectivity (a) and sur-
face coverage (b) as function of the O2 /NH3 feed ratio. An
increase of the feed ratio stimulates the conversion of NH3
and selectivity to NO considerably. The selectivity to N2 O
changes only slightly, while the N2 selectivity decreases sig-
nificantly. At low feed ratio, mainly vacant sites are present
on the catalyst surface. Such conditions are less interest-
ing for the issue of selectivity manipulation using RFO. At
high feed ratio, the number of vacant hollow site drops sig-
nificantly as adsorbed O increases up to a fraction of 0.8.
The availability of adsorbed O drives many reaction steps,
which causes the rather small decrease of the number of
vacant top sites at higher O2 /NH3 ratios. The feed ratio of
O2 /NH3 = 1:1 was applied during the reverse flow simula-
tion because the NH3 conversion reaches a high level and
significant profiles of adsorbed species along the reactor axis
are clearly present.
A larger residence time at fixed reactor temperature and
feed ratio leads to higher N2 selectivity, but lower NO se-
lectivity if NH3 is in excess. An increase of the NH3 feed
fraction at fixed temperature and residence time increases
the N2 selectivity, but decreases the NH3 conversion and the
NO and N2 O selectivities. The N2 O selectivity decreases
considerably at higher temperatures; the influence of the res-
idence time and NH3 /O2 ratio is minor. However, it should
be kept in mind that high selectivities to N2 O are possible
at extremely short residence time (Rebrov et al., 2003).
4.2. Reverse flow simulation
All simulations were performed with an imposed sym-
metrical temperature profile to assure that thermal behaviour
is in relaxed steady state regime compared to the dynamics
of the mass balance. The concentration profiles as function
of time generally show stable oscillations after three cycles,
which supports the earlier suggestion that the dynamics of
the mass balance are much faster than those of the energy
balance. Therefore, a steady temperature profile can always
be imposed, once the proper function is known. It should be
noted that a temperature profile could be directly measured
during experimental work in reverse flow reactors. For low
feed concentrations and/or low conversion, isothermal reac-
tor operation will be achieved, which means that model val-
idation can be performed with a relatively uniform reactor
temperature.
The steady state results were inspected with respect to the
occurrence of pronounced axial profiles of gas phase con-
centrations and/or catalyst surface coverages. Conceivably,
such behaviour is most likely affected by applying reverse
flow operation. Reverse flow simulations were therefore per-
formed at conditions that give rise to pronounced axial pro-
files.
Apart from the three process variables: temperature (T),
residence time (), and feed ratio (FR), that characterize
the steady state, one needs a new parameter , defined as
the ratio of switching time (ts ) and residence time in order
to clearly define RFO conditions. As mentioned previously,
the time scale of the switching time for the application of
reverse flow operation for selectivity manipulation is com-
pletely different when compared to the similar operation for
energy saving. For the latter, the switching time is quite
large, in the range of several minutes to several hours. In
the current application, the time scale of switching has the
same order of magnitude as the residence time (seconds). It
should be verified if such high switching frequencies could
be realized in industrial practice.
Three ranges of the parameter  can be distinguished be-
cause perturbation may either disturb the steady state of a
process or may prevent that a process becomes steady. The
three regimes are illustrated in Figs. 5a–c, where NH3 partial
pressure responses are plotted versus time. The time-average
value (ptavg ) and the value during steady state once-through
operation are also shown for comparison.
• A high flow reversal frequency ( < 1), see Fig. 5a, means
that a central part of the reactor is never refreshed with
fresh reactants by convection. Apparently, this causes a
decrease of the conversion, as indicated by the level of
ptavg and pss . Depending on the flow direction, this gas
volume moves up- and downwards, which leads to ex-
change between gas phase and catalyst surface. As such,
this amount of gas is not to be considered as dead volume.
The limiting reactant might be completely converted into
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,
depending on the chosen process conditions and the actually
desired product.
4.3. Reverse flow operation in combination with periodic
lower feed concentration
In the normal RFO, the feed concentration is kept con-
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
compared to SSO at the same conditions deals with the fact
that the gas, which has just entered the reactor, is driven
out again at very low conversion shortly after a flow rever-
sal. This rather inefficient way of working could be avoided
by periodically lowering the feed concentration for a short
period before the flow direction is reversed. In this way, a
waste of raw material in the feed is avoided, which could
be considered as feed stock saving. As a result, the reactor
performance is improved when compared to SSO and the
normal RFO, i.e. without lowering feed concentration. The
feed stock saving depends on the time period of low feed
concentration (tL ). Table 5 and Fig. 6 show typical simu-
lation results. The conditions are mentioned in Table 2, but
a constant switching time ts of 10 s is chosen for compar-
ison with the normal RFO mode. Conversion and selectiv-
ities are again expressed as time-average values over one
complete cycle with incorporation of the time-dependence
N2O
N2OSSO
0
0 2 4 6 8 10
Time period [s]
Fig. 6. Conversion and selectivity as a function of the time period of
lower feed concentration. The steady state values (SSO) are indicated
on the right axis. Switching time is 10 s. Other operating conditions as
mentioned in Table 2.
of the NH3 concentration for both inlet and outlet. The latter
is alternating between 152 and 1.52 mmol m−3 during each
half-cycle.
Fig. 6 shows that if the time period of a low feed concen-
tration of NH3 increases, the reactor conversion increases
as well up to a maximum. Further increase in this time
period decreases the conversion. The maximum conversion
of NH3 is reached when the time period of low feed con-
centration is 7.1 s. The conversion may even exceed the
steady state value in a certain range of this parameter. The
selectivities to N2 and N2 O decrease, while the selectiv-
ity for NO increases. Considering the reactor productivity,
defined as conversion times selectivity, Table 5 shows that
the productivity of notably NO can be largely improved by
RFO with periodical low feed concentration when com-
pared to the steady state performance. Operating a reverse
flow reactor in this mode can offer more benefits than reg-
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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