Chemical Engineering Science 56 (2001) 1587}1595

Thermal N O decomposition in regenerative heat exchanger reactors


M. Galle *, D. W. Agar , O. Watzenberger

Chemical Engineering Department, University of Dortmund, Emil-Figge-Str. 66, 44221 Dortmund, Germany

BASF AG, 67056 Ludwigshafen, Germany

Abstract

The decomposition of nitrous oxide (N O), which may be carried out either catalytically or thermally, is a reaction of considerable

environmental signi"cance. A novel non-catalytic process for the destruction of nitrous oxide emissions is presented. Experimental
studies on a laboratory scale demonstrate that a selective removal of N O can be achieved in a purely thermal conversion step within

the temperature range of 8003C}10003C without adversely a!ecting the NO levels in the gas. The new process is also suitable for the
V
treatment of lean waste gas streams, since the integrated heat recovery, for instance in a regenerative reverse #ow reactor, permits
simple, robust autothermal operation with the recovery of useful heat whilst circumventing the danger of additional NO formation.
V
Further studies deal with the simultaneous occurrence of both homogeneous and heterogeneous reactions in the N O decomposition

process and their interaction. The stability limits in the operation of a #ow reversal reactor could well o!er a useful practical means of
discriminating between the relative contributions of the two types of reaction and of identifying coupling mechanisms, as the
combined system exhibits parametric sensitivities and thermokinetic instabilities, such as ignition}extinction phenomena and
multiple periodic steady states, which depend on the underlying structure of the reactive processes. The concepts involved are
illustrated using the results of preliminary model simulations. The stability structure of the system can be analysed expediently using
a combination of dynamic simulation and an asymptotic countercurrent reactor model.  2001 Elsevier Science Ltd. All rights
reserved.

Keywords: Nitrous oxide; Regenerative heat exchanger; Dynamic simulation; Modelling; Reverse #ow reactor; Stability

1. Introduction The existing thermal decomposition processes for

Nitrous oxide, N O, was long considered to be a rela-

tively harmless pollutant. More recently, however, its
negative environmental impact has been widely recog-
nised. Anthropogenic emissions of nitrous oxide are said
to be responsible for around 4% of the greenhouse e!ect
(Bliefert, 1997). Important anthropogenic sources of
N O formation comprise processes such as combustion

and the industrial production of nitric and adipic acids.
The heterogeneously catalysed decomposition of N O
 
is a well-known and thoroughly researched technology
(Kapteijn, Moulijn, & Rodriguez-Mirasol, 1996). Many
of the catalysts employed, however, undergo extensive
deactivation under severe process conditions and at tem-
peratures above 7003C or so.
* Corresponding author. Fax: #49-231-7552698.
E-mail addresses: galle@chemietechnik.uni-dortmund.de (M. Galle),
agar@chemietechnik.uni-dortmund.de (D. W. Agar).
N O destruction require a supplementary fuel supply

together with precise regulation of the temperature in the
combustion zone to avoid the undesirable decomposition
of accompanying NO in the case of process gases or the
V
formation of NO in waste gas streams. A thermal pro-
V
cess capable of ful"lling these criteria yet permitting facile
control of the temperature conditions without external
energy input for both lean and rich gases could thus o!er
an e!ective reaction engineering solution to the problem
of N O removal without the shortcomings of catalytic
processes.
Such reactors incorporating regenerative or recuper-
ative heat exchange, for example the reverse #ow reactor,
are already employed under similar circumstances for the
treatment of organically contaminated waste air streams
(Nieken, 1993).
In addition, a reverse #ow reactor with a catalytic "xed
bed can provide useful insights when studying hybrid, i.e.
combined thermal}catalytic, reaction processes, and can
yield information on both the extent of the individual

0009-2509/01/$ - see front matter  2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 0 0 ) 0 0 3 8 6 - 9
1588 M. Galle et al. / Chemical Engineering Science 56 (2001) 1587}1595
contributions and their interaction. N O decomposition

o!ers an ideal test system for this purpose, with consider-
able overlap between the temperature ranges for homo-
geneous and heterogeneous reaction, well-studied
chemical mechanisms and comparatively straightfor-
ward experimental requirements. Similar coupled hybrid
reaction systems have already been examined using alter-
native techniques in connection with the catalytically
supported combustion process, an e!ective measure for
suppressing NO formation (Goralski & Schmidt, 1999).
V
Both of these aspects of the N O decomposition pro-
 Fig. 1. N O decomposition paths.
cess are covered in this work. First of all, the new thermal
process for the selective decomposition of N O will be

presented together with pertinent laboratory measure-
ments. The qualitative di!erences between coupled ho-
mogeneous}heterogeneous and purely heterogeneous
N O decomposition in terms of reverse #ow reactor

behaviour at the stability limits will then be described. In
both instances, the main results obtained will be dis-
closed and discussed. Since both thermal and catalytic
N O decomposition are of interest, a brief forward will

be provided on the underlying reaction mechanisms and
on the basics of reverse #ow reactor operation.
2. Existing technologies for N O decomposition

N O decomposition (2N OP2N #O ,
H
(¹"
    0 K
298 K)"!163 kJ/mol) is an exothermic reaction,
which can proceed either catalytically or thermally as
depicted in Fig. 1. The dominant mechanism is dictated
by the operating temperature and the catalyst used, with
both paths being important in the intermediate range.
Much work has been devoted to the catalytic decomposi-
tion and numerous catalyst systems with a variety of
compositions, based on platinum, zinc and copper oxides
or zeolites for example, have been developed (Kapteijn et
al., 1996; Turek, 1996; Winter, 1970). A general disadvan-
tage of catalytic processes is that catalysts are subject to
mechanical, chemical or thermal deactivation in various
degrees, including complete loss of activity, depending on
the prevalent operating conditions. Fluctuations in the
N O content of the gas being treated can give rise to

transitional reaction fronts with pronounced hot spots in
"xed bed reactors due to the exothermicity of the de-
composition reaction, which can result in considerable
local damage to the catalyst.
2N OP2N #O , (1)
   If the N O containing gas to be treated is already at
N O#HPN #OH, (2)
 
N O#OHPN #O #*, (3)
  
2OH & O #2H. (4)
 to cooling su$ces to achieve extensive thermal N O
Generally, the mechanism of the catalytic reaction may
be represented as the adsorption of N O on an active


site, usually consisting of a free transition metal ion on
the catalyst surface, followed by the breakdown of the
adsorbed molecule, resulting in the production of gas-
eous nitrogen molecules and adsorbed oxygen atoms.
The latter can be desorbed in the form of molecular
oxygen through recombination with one another or via
the direct reaction with a further N O molecule

(Kapteijn, Mul, Marban, Rodriguez-Mirasol, & Moulijn,
1996), ((2)}(4)).
Due to the considerably higher value of the activation
energy (E +250 kJ/mol, Bamford & Tipper, 1972),
thermal N O decomposition requires much higher tem-

peratures (¹+800}10003C) than the catalytic route
(E +50}160 kJ/mol, Kapteijn et al., 1996).
The mechanism of the thermal reaction cannot, as
a rule, be de"ned in a universally valid form and must be
considered within the context of the gas composition as
a whole. The following mechanism has been proposed for
the thermal decomposition of pure nitrous oxide ((5)}(7))
(Bamford & Tipper, 1972; Dindi, Tsai, & Branch, 1991;
Miller & Bowman, 1989):
N O#MPN #O#M, (5)
 
N O#OPN #O , (6)
  
N O#OP2NO, (7)

where M is the impingent species. Conventional inciner-
ation processes, in which the N O content of the waste

gas is decomposed thermally through the simultaneous
combustion of a fuel/air mixture in a special burner, have
been available for some time (German Patent DE 41 16
950 A1). For gases containing large amounts of other
nitrogen oxides, i.e. NO , one has to ensure that su$cient
V
excess fuel is provided to completely reduce such addi-
tional pollutants.

the high temperatures required for thermal decomposi-
tion, as is the case for the exit gas from a catalytic
ammonia oxidation reactor for example, simply prolong-
ing the residence time of the gas at this temperature prior

degradation. The industrial application of such a process
has been described in the patent literature (European
 M. Galle et al. / Chemical Engineering Science 56 (2001) 1587}1595
Patent EP 0 359 286 B1). This option is, however, a speci-
"c solution tailored to a single process and only becomes
economically feasible if appropriate temperature levels
are intrinsic to the process and need not be attained by
additional costly measures. The precise control of tem-
perature in the decomposition zone is essential to prevent
undesirable degradation (with process gases) or forma-
tion (with waste gases) of NO . There still exists a need
V
for an economic process with minimal supplementary
fuel requirements that is capable of treating industrial
gases contaminated with N O whilst leaving utililisable

components intact.
3. Thermal N O decomposition in regenerative reverse

6ow reactors
A complete conversion of N O via thermal decompo-

sition requires high temperature levels. As a rule, values
in the range of 800}12003C are necessary. The generation
of such temperatures can be achieved most expediently
by employing highly e$cient regenerative or recuper-
ative heat exchangers incorporated in "xed bed reactors
to recover and amplify the heat of reaction. For gases,
regenerative heat exchange usually o!ers a superior per-
formance in comparison to similarly sized recuperative
exchangers. Either catalytically active or inert packing
material may be used in the "xed bed. For the case in
hand, the excellent thermal e$ciencies of regenerative
heat exchange within the "xed bed itself are exploited in
the form of the so-called reverse #ow reactor to achieve
non-catalytic N O conversion.

Fixed-bed reactors with periodic #ow reversal have
proved to be a particularly e!ective technology for the
total oxidation of organic contaminants in waste air
streams. Their primary advantages lie in the autothermal,
i.e. thermally self-su$cient, operation at low con-
taminant concentrations and the synergetic integration
of heat regeneration into the reactor. A further advantage
is the reduced sensitivity to operational #uctuations com-
pared to conventional alternatives. The principle is de-
picted schematically in Fig. 2. Initially, the inert packing
in the reaction zone is heated up to 800}10003C. The cool
N O containing gas is then introduced into the bed,

raised to the reaction temperature and the exothermic
decomposition reaction commences. A detailed descrip-
tion of reverse #ow reactor operation can be found in
Nieken (1993) and Matros (1989). Due to the high ther-
mal e$ciency of heat recovery no supplementary energy
need be provided for N O concentrations in excess of

about 1500 ppmV apart from that required for the start-
up process, since the heat of reaction is adequate to
compensate for the unavoidable losses in the system,
i.e. autothermal conditions can be realised. The temper-
ature rise in the reactor is in#uenced by a variety of
parameters, such as N O concentration and switching
 
1589
Fig. 2. Reverse #ow reactor for thermal N O decomposition.

time, which can be used to regulate the values obtained
to the levels desired. Operation at N O concentrations

below 1500 ppmV, i.e. at levels encountered in nitric acid
plant tail gases, necessitates the introduction of small
amounts of fuel gas to maintain the temperatures re-
quired in the reaction zone. The limitations of heat recov-
ery mean that such an additional energy supply, however,
is also unavoidable for alternative catalytic N O de-

composition processes operating at lower temperatures
(&200}6003C) with feed streams at ambient temper-
atures.
The removal of a small hot gas sidestream from the
middle of the reactor has been shown to be a very
e!ective means of regulating temperatures in the reaction
zone Nieken (1993), especially relevant when N O-rich

gases are being treated. Such a hot gas purge prevents
excessive heat retention within the reactor and also per-
mits a convenient recovery of useful heat, e.g. for high
pressure steam generation.
3.1. Selective thermal N O decomposition

Many of the industrial process gases of interest, e.g.
those from the adipic acid production, may have high
concentrations of both NO und N O (Riley & Rich-
V 
mond, 1993; Patent application BASF Aktiengesellschaft
NAE 19980613, 20 January 1999). Since NO can be
V
utilised as raw material in the chemical industry, e.g. for
the production of nitric acid, it is often economically
attractive to recover NO from the N O-containing
V 
gases at integrated production sites.
Depending on the plant available, it may well be more
expedient to remove N O prior to NO recovery.
 V
For this reason, experimental laboratory studies were
carried out in an isothermal reactor on the selective
thermal decomposition of N O in N O/NO/air mix-
 
tures. A selection of the results obtained is presented in
Tables 1 and 2.
In the "rst case, an empty metal tubular reactor was
externally heated up to 850}10003C and a constant #ow
of air containing various amounts of N O und NO was
1590 M. Galle et al. / Chemical Engineering Science 56 (2001) 1587}1595

Table 1
Selective thermal N O decomposition in an empty tubular reactor

In Out
Residence ¹ x(NO) x(N O) x(N ) x(O ) x(NO) x(NO ) x(N O)
    
time (s) (3C) vol% vol% vol% vol% vol% vol% vol%

20 950 20 10 81.7 (0.02 10.96 11.58 0.19

20 1000 20 10 79.7 (0.02 0.78 21.03 (0.02

Table 2
Selective thermal N O decomposition in an inert "xed-bed reactor

Residence In x(NO) x(N O) Out x(O ) x(NO) x(NO ) x(N O)
   
time (s) ¹ vol% vol% x(N ) vol% vol% vol% vol%

(3C) vol%

47.5 814 * 12.45 93.5 5.84 * * (0.02

23.7 847 * 12.45 93.8 6.42 * * (0.02
11.9 832 * 12.45 93.7 5.99 * * (0.02
5.9 773 20 10.08 78.2 6.76 21.41 * (0.02
5.9 795 * 12.45 94.2 5.93 * * (0.02
5.9 827 * 12.45 93.6 5.95 * * (0.02
2 781 10 11.34 87.1 6.28 12.85 * (0.02
2 792 * 12.45 87.2 12.4 * * (0.02

passed through it under atmospheric pressure condit-

ions. In the second set of experiments the reactor was
"lled with inert packing material. The results from
both series of measurements indicate that selective
N O decompostion can be achieved in the presence of

NO. No net losses of NO occur, although some oxidation
of NO to NO was observed. This reversible endother-

mic reaction (Eq. (8)) takes place at intermediate temper-
atures:

NO & NO# O ,
   (8)



H (¹"298 K)"#56.5 kJ/mol.
0 K
Fig. 3. Temperature pro"les prior to switching for simultaneous
It is also obvious that much lower temperatures exothermic/endothermic conversion in a reverse #ow reactor.
(*8003C) and residence times (2 s) are required for the
N O decomposition in the reactor with the &inert' "xed

bed. In the empty tubular reactor complete N O conver- NO in overlapping temperature ranges (Eqs. (5)}(8)) for

sion was only achieved at temperatures of around a feed comprising air, NO and N O. The endothermic
 
10003C with residence times of 20 s or more. degradation of NO to NO simply exerts a moderating

In addition to its role as a heat storage medium for in#uence on the net release of heat at intermediate tem-
regenerative heat exchange, it appears that a quasi-cata- peratures.
lytic phenomenon is occurring, possibly as a result of
local overheating e!ects. The periodically stable temper-
ature and concentration pro"les calculated from the 4. Hybrid catalytic/thermal N O decomposition

model simulations carried out to back-up the experi-
mental work are illustrated in Figs. 3 and 4. Apart from the above-mentioned coupling between
A novelty in these results is the consideration of the exothermic and endothermic reaction, the behaviour
interaction between the exothermic N O decomposition of the reverse #ow reactor can be used to provide

and the reversible endothermic conversion of NO to a novel technique for examining the hybrid thermal

 M. Galle et al. / Chemical Engineering Science 56 (2001) 1587}1595 1591

The energy balance for the catalyst was formulated in an

analogous manner:
¹ ¹
(1!) c Q "(1!) Q !a  (¹ !¹ )
Q NQ t Q x 4 EQ Q E

#r
H . (10)
Q 0
Corresponding to the energy balance, the mass balance
takes the mass transport by convection and dispersion as
well as the transfer between gas and catalyst and reaction
terms for both phases into account. The mass balance for
the gas phase is as follows:
w w w
 E "!GQ E #D E
Fig. 4. Concentration pro"les for simultaneous exothermic/endother- E t V x  x
mic conversion in a reverse #ow reactor.
#a   (w !w )#r M (11)
4 E EQ Q E E G
and for the catalyst surface, neglecting dispersion,
(homogeneous) and catalytic (heterogeneous) contribu-
tions to high temperature reactions, such as the N O w
 (1!) Q "!a   (w !w )#r M . (12)
decomposition, and to yield insights into the mechanisms Q t 4 E EQ Q E Q G
by which they interact with one another. For example,
the homogeneous reaction can be &ignited' by local over- The inlet and outlet boundary conditions applied are
heating e!ects in catalytic "xed-bed reactors, which can
¹
rise due to the high surface temperatures caused by GQ c ¹ "GQ c ¹ ! E
V NE E  V NE E E x
transport limitations. As simulation results will indicate,
qualitative di!erences may be discerned between hybrid w
and purely homogeneous or heterogeneous reaction sys- and GQ w "GQ w ! ) D E, (13)
V E  V E  x
tems with respect to the stability limits for the operation


of a catalytic reverse #ow reactor, which could allow one ¹
to discriminate between the relative importance of the Q "0
x
two routes. The objective of such work is to develop more V

  
reliable models for describing the behaviour of hybrid ¹ ¹ w
and E " Q " E"0. (14)
homogeneous/heterogeneous reaction systems and thus x x x
to design more appropriate reactors for high-temper- V* V* V*
ature &catalytic' processes, the performance of which The balances described represent a one-dimensional
is often in#uenced strongly by homogeneous reaction parabolic system of di!erential equations and were sol-
contributions. ved numerically for the boundary conditions given in (13)
and (14) using an adaptive &method of lines' algorithm
PDEXPACK (Nowak, Frauhammer, & Nieken, 1996).
4.1. Reactor modelling and simulation This numerical algorithm is fully adaptive in space and
time and is especially suitable for the resolution of the
The simulation of reverse #ow reactor operation steep reaction front structures that can arise, for example,
was based on a dynamic one-dimensional, two-phase from the ignition of thermal reaction paths.
model incorporating mass and energy balances for
both the gas and the "xed bed. The energy balance for 4.2. Potential for the discrimination of hybrid interactions
the gas phase includes heat transport via convection
and conduction, the exchange of heat between the gas The inclusion of both reaction paths (homogeneous
and the catalyst phase together with a heat of reaction and heterogeneous) in the model "rst implicitly assumed
term for the homogeneous contribution to N O de-
 that the interaction is of a purely thermal nature. Fig. 5(a)
composition: shows representative temperature pro"les both for the
heterogeneous reaction alone and for a thermally
¹ ¹ ¹
 c E "!GQ c E # E coupled hybrid system. The mechanisms of the decompo-
E NE t V NE x E x sition reactions were taken into account using simple
relationships based on the equations presented earlier
#a  (¹ !¹ )#r
H . (9) (Eqs. (2), (3), (5) and (6)).
4 EQ Q E E 0
1592 M. Galle et al. / Chemical Engineering Science 56 (2001) 1587}1595
Fig. 5. Comparison between purely catalytic and thermally coupled
hybrid decomposition. Pro"les prior to switching: (a) temperature, (b)
normalised mass fraction N O.

The simulations show that a more pronounced gradi-
ent emerges in the temperature pro"le owing to the
ignition of a homogeneous reaction. A distinct di!erence
between the maximal temperatures attained is only ob-
served under conditions where the catalytic reaction
alone is no longer able to maintain complete conversion.
This is apparent in the concentration pro"les depicted in
Fig. 5(b). For high conversions, the discrepancies be-
tween the values for the hybrid and purely heterogeneous
routes become less evident. In addition to the strictly
thermal coupling, a chemical interaction between the two
reaction paths may also be present. For example, reactive
intermediates from the homogeneous reaction (radicals)
can adsorb on the catalytic surface and their withdrawal
from the gas phase can inhibit the homogeneous reac-
tion. Alternatively, it is conceivable that reactive inter-
mediates from the heterogeneous surface reaction can be
passed into the gas phase and promote the homogeneous
reaction. In the case of N O decomposition, it would

appear physically unrealistic from the reaction mecha-
nisms proposed in Eqs. (2)}(4) that the catalytic surface
acts as a source of radicals. The loss of radicals formed in
the homogeneous reaction through reaction with surface
species would seem to be the more likely alternative
(Benz, 1993). In an initial simpli"ed treatment of the
problem, it was thus decided to broaden the model to
incorporate both thermal and chemical reaction coupling
mechanisms, with the latter involving the reaction of
Fig. 6. Comparison between thermally and thermally/chemically
coupled hybrid N O decomposition, switching period"200 s: (a) de-

velopment of max. temperature, (b) temperature pro"le at t"5000 s.
oxygen radicals from the gas phase with a surface species
as given in

OH#OPO
H
#H (kH: reaction rate constant). (15)

The results of the extended model are shown in Fig. 6. As
would be expected, the chemical interaction clearly in-
hibits the contribution of the homogeneous reaction. In
contrast to strictly thermal coupling, the maximum tem-
perature is "rst attained at much larger times. The higher
the value of the reaction rate for the coupling reaction
(15), the greater is the time necessary to reach the maxi-
mal temperature level. In Fig. 6(b) the temperature pro-
"le over the reactor length is illustrated for a "xed point
in time (5000 s, cf. Fig. 6(a)). The pro"les indicate the
inhibitory in#uence of chemical coupling on the hybrid
reaction. The qualitative di!erences between the pro"les
for purely thermal and thermal/chemical interactions
should be re#ected in the stability characteristics of the
reverse #ow reactor and thus enable one to discriminate
between various coupling mechanisms.
It is well-known that multiple &steady states' can be
encountered in the operation of reverse #ow reactors.
Stable periodic solutions almost always include an
extinguished state with reactor temperatures only mar-
ginally higher than the inlet value and minimal conver-
sions and an ignited state with higher conversions. The
coupling mechanism for the hybrid reaction system reac-
tions considered here gives rise to three stable solutions
 M. Galle et al. / Chemical Engineering Science 56 (2001) 1587}1595
Fig. 7. Hysteresis behaviour of thermal/chemically coupled hybrid
N O decomposition.

comprising one extinguished and two ignited reactor
states. One of the ignited states lies in a temperature
range where the reaction takes place exclusively via the
heterogeneous route, while the second involves both het-
erogeneous and homogeneous contributions. A critical
parameter when studying extinction}ignition phe-
nomena in a reverse #ow reactor is switching time. The
variation of the switching period can lead to the familiar
hysteresis e!ects for such systems (Fig. 7).
The hysteresis behaviour can be used to visualise
qualitative di!erences between thermal and thermal/
chemical interactions in the transition region between
ignited and extinguished states.
For chemical coupling between the homogeneous and
heterogeneous reactions, which can also be diagnosed
independently by the deliberate introduction of radical
modifying additives, the shift in the stability behaviour is
evident and o!ers the possibility of quantifying the con-
tribution of each reaction path through the selection of
appropriate switching times. The dynamic simulation of
reactor operation only reveals the stable reactor states, as
the calculation of the ignition}extinction hysteresis just
presented con"rms. Directly ascertaining multiple cyclic
&steady states' is not feasible using this approach, as no
unstable solution branches may be identi"ed. Knowledge
of the unstable solutions is, however, a prerequisite for
establishing the boundaries between the regions of igni-
tion and extinction. It can be assumed that temperature
pro"les above the limiting case for the unstable solution
lead to ignition of the reactor and vice versa (Nieken,
1993). If no information is available as to the location of
the separatrix, one cannot be sure as to whether the
reactor operating state will tend towards the ignited or
the extinguished cyclic steady states from an arbitrary
intermediate initial temperature pro"le.
A "rst approximation for the unstable reactor cyclic
steady states can be obtained by considering a quasi-
homogeneous countercurrent reactor model to describe
1593
Fig. 8. Countercurrent reactor with and without thermal coupling.
Conversion as a function of (a) adiabatic temperature rise, (b) length of
reactor.
the asymptotic behaviour of the reverse #ow reactor at
short switching times (Nieken, 1993). With the help of the
unstable reactor operating states thus located, rough
estimates can be made of the temperature and concentra-
tion conditions required at reactor start-up to reach
either the hybrid or the purely heterogeneous reaction
branch and the stability characteristics of the system can
be investigated more thoroughly. Fig. 8 depicts the con-
version as a function of the inlet concentration expressed
in terms of the associated adiabatic temperature rise for
the feed gas and the concentration pro"les along the
reactor calculated for the asymptotic countercurrent op-
eration. The dashed curves indicate the results for cata-
lytic decomposition alone, while the solid curves describe
the behaviour of the thermally coupled hybrid reaction
system. The ignition of the homogeneous reaction is
apparent in the upper conversion range of both dia-
grams. Furthermore, one can clearly identify both stable
solutions on the ignited state trajectory and the extin-
guished state at X"0.
The qualitative shifts in the stability behaviour
of a hybrid reaction system that would be predicted for
di!erent coupling mechanisms will be veri"ed
shortly in experimental studies. A suitable pilot-scale
(¸"1500 mm, E"120 mm) reverse #ow reactor for
this purpose has already been constructed and is illus-
trated in Fig. 9. Initial tests indicate that the heat losses
can be cut to an acceptable level ((400 W) at which the
1594 M. Galle et al. / Chemical Engineering Science 56 (2001) 1587}1595

Fig. 9. Pilot-scale reverse #ow reactor.

resulting distortions of the adiabatic temperature pro"les D dispersion coe$cient, kg/m s

can be allowed for without introducing extra uncertainty GQ speci"c mass #ow, kg/ms
V
into the interpretation of the results. Furthermore, cata-
H
molar heat of reaction, kJ/mol
0 K
lyst screening has identi"ed a suitable monolithic catalyst M molar weight, kg/kmol
with platinum as the active component that exhibits r reaction rate
adequate thermal stability, i.e. negligible loss of activity t time, s
at 9003C over several days. A detailed examination of the w weight fraction, kg/kg
stability behaviour of hybrid reaction systems with vari- x spatial coordinate, m
ous coupling mechanisms in a reverse #ow reactor using X conversion, dimensionless
direct calculation of the cyclic steady states (Salinger
& Eigenberger, 1996) and the consequences of the hybrid Greek letters
reaction models determined for the design of high-tem-
perature catalytic reactors will be the subject of future  heat transfer coe$cient, W/mK
work.  mass transfer coe$cient, m/s
The in#uence of additional compounds that might be  void fraction, dimensionless
encountered in industrial waste gas systems, such as NO  thermal conductivity, W/m K
V
and H O on heterogeneous and homogeneous reaction  density, kg/m

contributions will also be investigated.
Subscripts and superscripts

Notation * normalised
in inlet
a speci"c surface area, m/m s solid
4
c speci"c heat capacity, J/kg K g gas
N
 M. Galle et al. / Chemical Engineering Science 56 (2001) 1587}1595 1595

e! e!ective German patent DE, 41 16 950 A1.

x spatial coordinate Goralski Jr, C. T., & Schmidt, L. D. (1999). Modelling hetero-
N O nitrous oxide geneous and homogeneous reactions in the high-temperature cata-
 lytic combustion of methane. Chemical Engineering Science, 54,
max maximum 5791}5807.
Kapteijn, F., Moulijn, J. A., & Rodriguez-Mirasol, J. (1996). Heterogen-
Abbreviations eous catalytic decomposition of nitrous oxide. Applied Catalysis B:
Environmental, 9, 25}64.
het heterogeneous Kapteijn, F., Mul, G., Marban, G., Rodriguez-Mirasol, J., & Moulijn, J.
A. (1996). Decomposition of nitrous oxide over ZSM-5 catalysts. In
hom homogeneous J. W. Hightower, W. N. Delgass, E. Iglesia, & A. T. Bell (Eds.),
Studies in surface science and catalysis, Vol. 101 (pp. 641}650).
Amsterdam: Elsevier.
Acknowledgements Matros, Y. S. (1989). Catalytic processes under unsteady-state condi-
tions. Studies of surface science and catalysis, Vol. 43. Amsterdam:
The authors would like to express their gratitude to the Elsevier.
Institute of `Chemische Verfahrenstechnika at the Uni- Miller, J. A., & Bowman, C. T. (1989). Mechanism and modelling of
versity of Stuttgart, Germany, for permission to use the nitrogen chemistry in combustion. Progress in Energy Combustion
Science, 15, 287.
PDEXPACK algorithm. Nowak, U., Frauhammer, J., & Nieken, U. (1996). A fully adaptive
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