Chemical Engineering Science 55 (2000) 5945}5967

Review
Autothermal "xed-bed reactor concepts
G. Kolios, J. Frauhammer, G. Eigenberger*
Institut fu( r Chemische Verfahrenstechnik, Universita( t Stuttgart, Bo( blinger Str.72, D-70199 Stuttgart, Germany
Received 22 October 1999; accepted 24 March 2000

Abstract

The principles, properties and applications of autothermal "xed-bed reactor concepts are presented. First we focus on di!erent
reactor types for weakly exothermic reactions and discuss their basic behavior, their stability and nonlinear dynamic features. The
second part is devoted to the autothermal coupling of endothermic and exothermic reactions. A systematic classi"cation is proposed
for the process alternatives developed so far and a simpli"ed model is developed from which basic features of an optimal design can be
deduced.  2000 Elsevier Science Ltd. All rights reserved.

Keywords: Autothermal operation; Reverse #ow operation; Circulation loop reactor; Countercurrent reactor stability; Coupling of exothermic and
endothermic reactions

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5946
2. Autothermal operation for weakly exothermic reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5946
2.1. Basic principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5946
2.1.1. The countercurrent "xed-bed reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5946
2.1.2. Periodic #ow reversal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5946
2.1.3. The analogy between fast #ow reversal and countercurrent operation . . . . . . . 5948
2.2. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5950
2.2.1. Autothermal reactors for total oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5950
2.2.2. Autothermal reactors for equilibrium limited reactions. . . . . . . . . . . . . . . . . . . 5951
2.3. Autothermal reactor stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5952
2.3.1. Circulation loop reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5953
2.3.2. The cooled reverse #ow reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5953
2.4. Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5954
3. Autothermal combination of exo- and endothermal reactions . . . . . . . . . . . . . . . . . . . . . . . . 5955
3.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5955
3.2. Simultaneous operation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5957
3.3. Asymmetric operation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5958
3.4. Symmetric operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5960
3.5. A simpli"ed picture of the autothermal coupling of endo- and exothermic reactions . . 5962
3.5.1. Simultaneous operation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5962
3.5.2. Asymmetric operation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5963
3.5.3. Symmetric operation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5963
3.5.4. Regenerative heat transfer. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5964
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5965
Notation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5965
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5965
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5965

* Corresponding author. Tel.: #49-711-641-2229; fax: #49-711-641-2242.

E-mail address: eigenberger@icvt.uni-stuttgart.de (G. Eigenberger).

0009-2509/00/$ - see front matter  2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 0 0 ) 0 0 1 8 3 - 4
5946 G. Kolios et al. / Chemical Engineering Science 55 (2000) 5945}5967

1. Introduction where m is the mass #ux density, (1!e) is the wall

The unit operation concept of Chemical Engineering
requires that chemical processes are set up as a sequence
of separate operations for mixing, heat transfer, reaction,
separation, etc. where each unit operation is usually
represented by a separate device. In contrast, the ex-
tended or multifunctional reactor concept, explicitly for-
mulated by Agar and Ruppel (1988a,b) suggests to take
advantage of the combination of chemical reaction with
selective reactant addition or product removal and the
intended and speci"c addition or removal of heat in one
apparatus. Such concepts have meanwhile attracted con-
siderable attention in our community (Blumenberg, 1992;
Westerterp, 1992; Ho!mann & Sundmacher, 1997). One
of the simplest and most common examples of multifunc-
tional reactors which have been in use in Chemical Reac-
tion Engineering for many decades are autothermal
reactors for weakly to moderately exothermic reactions,
where the cold reactor feed is heated up to the required
reaction temperature by the hot reactor e%uent. This can
be done in a separate heat exchanger or by partial or
total integration of the heat exchange into the reactor.
Typical well-known examples are the integration of
a countercurrent heat exchanger into the high-pressure
housing of a methanol or ammonia synthesis reactor
(Hochgesand et al., 1989; Bakemeier et al., 1985). But it is
not too long ago when it became obvious that the integ-
ration of either regenerative or recuperative heat ex-
change into the catalyst packing of a catalytic "xed-bed
reactor could have some speci"c advantages over
a simple combination of an adiabatic reactor with a sep-
arate heat exchanger. Even more recent is the systematic
exploitation of the autothermal coupling of exo- and
endothermic reactions.
X
volume fraction, h is the heat transfer coe$cient (as-
U
sumed equal for up- and down#ow) and a is the speci"c
T
heat transfer area.
2.1.1. The countercurrent xxed-bed reactor
It is obvious that the countercurrent heat exchange
can be integrated into the catalyst "xed bed or a counter-
current heat exchanger could be "lled with catalyst inside
and outside its tubes (Fig. 1b). If the heat transfer condi-
tions in both designs of Fig. 1 are similar, the temperature
pro"les in the heat exchange sections will be the same
since the temperature slope is given by Eq. (1). In the
following, such a reactor will be called a `countercurrent
"xed-bed reactora. The advantages of the countercurrent
reactor design are twofold: The packing allows for a bet-
ter heat transfer to the walls and hence for a more
compact and possibly less expensive design. The second
advantage is a considerably reduced temperature sensi-
tivity which will be discussed in more detail later.
2.1.2. Periodic yow reversal
A second approach to autothermal operation is closely
connected with the phenomenon of a moving or creeping

2. Autothermal operation for weakly exothermic

reactions

2.1. Basic principles

The standard reactor design for an autothermal "xed-

bed reactor consists of an adiabatic "xed bed of catalyst
which is connected with a heat exchanger so that the hot
reactor e%uent heats up the cold feed. If we consider the
countercurrent heat exchanger of Fig. 1a, the slope of the
temperature pro"le can be approximated by Eq. (1)
(Nieken, Kolios & Eigenberger, 1995).

d¹ m c
" X N *¹
dz 2j  Fig. 1. Two types of autothermal "xed-bed reactors with typical tem-
 perature pro"les. The dotted pro"les correspond to a doubling of the
adiabatic temperature rise. (a) Standard design with adiabatic "xed bed
(m c )
with j "j (1!eU)# X N , (1) and separate countercurrent heat exchange, (b) `countercurrent "xed-
 U h a bed reactora.
U T
 G. Kolios et al. / Chemical Engineering Science 55 (2000) 5945}5967
reaction front, a topic with a long and prominent history
in Chemical Reaction Engineering (Wagner, 1945; Wicke
& Vortmeyer, 1959; Padberg & Wicke, 1967; Gilles, 1974;
Pinjala, Chen & Luss, 1988; Chen & Luss 1989; Bur-
ghardt, Berezowski & Jacosen, 1999). If an adiabatic
reactor is started by heating the catalyst bed above the
ignition temperature of the exothermic reaction con-
sidered, the feed temperature can subsequently be
lowered to ambient. As a consequence a moving reaction
front develops where the bed is cooled by the cold feed
and the feed is heated up by the hot bed (Fig. 2a).
The lateral displacement of the temperature front can
easily be calculated from the well-known formula of the
velocity w of a moving reaction front (Wicke & Vor-
tmeyer, 1959):
(1!(*¹ /*¹)) eoc
w"  N . (2)
(1!(*¹ /*¹)) eoc #(1!e)o c
 N Q Q
As long as the moving front is still inside the catalyst bed,
full conversion will be obtained but if it moves out, the
reactor will extinguish. Several ways have been conceived
Fig. 2. Principles of reverse-#ow operation: (a) Temperature (¹) and
conversion (X) pro"les of a moving reaction front in an adiabatic
"xed-bed reactor; (b) temperature and conversion pro"les at the end of
the two "rst semicycles; (c) transient to the periodic steady state.
5947
of how to prevent the extinction and to perpetuate the
reactor operation. One way would be to reignite the
reaction at the entrance as soon as the front leaves
the reactor. This leads to the circulation loop reactor
discussed in Section 2.3.1. Certainly the best-known way
is to reverse the #ow direction after the front has moved
to a certain position into the bed and to repeat this #ow
reversal periodically until a periodic steady state has
been established. Fig. 2b shows the pro"les of an irrevers-
ible reaction at the end of the "rst and the second semi-
cycle and Fig. 2c shows the evolution to the periodic
steady state for the pro"les at the end of the half-period
where the #ow comes from the left.
Fig. 3 gives a schematic of an adiabatic "xed-bed
reactor with periodic #ow reversal showing the temper-
ature and concentration pro"les in the periodic steady
state and the course of the reactor exit temperature
¹J with time t. In the periodic steady state the temper-
ature (and conversion) pro"les for two successive
semicycles are just mirror images of each other. It follows
from an overall heat balance that the integral mean of the
reactor exit temperature ¹J will exceed the feed temper-
ature ¹ just by *¹ . Under periodic #ow reversal both
 
ends of the "xed bed are obviously used as regenerative
heat exchangers. Since regenerative heat exchange is gen-
erally considered simpler and more e$cient than recu-
perative heat exchange, the reverse #ow reactor has
found considerable industrial application primarily for
the catalytic or homogenous combustion of organic pol-
lutants in exhaust air.
It is not too surprising that the autothermal operation
of "xed-bed reactors with regenerative heat exchange has
a long history of periodic reinventions. Khinast, Jeong
and Luss (1999) report a "rst patent issued to Cottrell
(1938) for exhaust puri"cation, a subsequent mentioning
in Frank-Kamenetski (1955) for selective oxidation,
a patent for SO oxidation issued to Watson (1975) and

a patent for catalytic puri"cation of Wojciechowski
Fig. 3. Adiabatic "xed-bed reactor with periodic #ow reversal: (a)
reactor scheme with switching valves; (b) temperature and concentra-
tion pro"les in the periodic steady state (feed values: ¹, c); (c) exit
temperature ¹J vs. time t.
5948 G. Kolios et al. / Chemical Engineering Science 55 (2000) 5945}5967

(1980). But the credit has certainly to be given to the

Novosibirsk school of Boreskov and Matros and their
colleagues for elaborating the scienti"c understanding,
for demonstrating the potential of reverse #ow reactors
up to the industrial scale and for communicating
this principal all around the world (Matros, 1989; Matros
& Bunimovich, 1996 and references therein).
In the reverse #ow reactor both ends of the packed bed
are used as regenerative heat exchangers in much the
same way as recuperative heat exchange is used in the
countercurrent "xed-bed reactor. And the question may
arise of how the two di!erent concepts of autothermal
operation compare with each other.

2.1.3. The analogy between fast yow reversal and

countercurrent operation
If we consider an adiabatic "xed-bed reactor with very
fast #ow reversals (Fig. 4a) the temperature of the catalyst
bed can hardly follow the gas temperature changes and
stays almost constant (Fig. 4b). If the cold gas comes
from the left it is heated up by the hot packing, if the hot
gas comes from the right out of the hot center part it
delivers its heat to the packing.
The limit of fast #ow reversal leads to a direct corre-
spondence with countercurrent operation (Eigenberger
& Nieken, 1994; Nieken et al., 1995). If we consider similar
operating conditions as above for a countercurrent "xed-
bed reactor where the catalyst is deposited at the separat-
ing wall (Fig. 4c), we get the same temperature and com-
position pro"les in the two channels which we obtain
under fast #ow reversal in successive semicycles, provided
the heat transfer parameters to the catalyst are the same
and the heat resistance of the wall is negligible. As any
limiting case the limit of fast #ow reversal is somewhat
academic since it assumes quasisteady gas balances, which
means that the residence time of the gas has to be con-
siderably shorter than the switching period. Nevertheless
this analogy provides a simple basis for short-cut calcu-
lations since the steady-state pro"le of a countercurrent
reactor can be computed much easier than the periodic
steady state of a reverse #ow reactor. This has been shown
by Matros and co-workers with what they call the `sliding
regimea (Matros (1989) as well as by Bhatia (1991)).
In case of a single irreversible reaction the analogy can
also be used for drawing a simpli"ed plot of the resulting
(periodic) steady state pro"les. This is explained in Fig.
4d. Eq. (1) can be used to calculate the slope of the
temperature pro"le for the part of the bed where only
heat is exchanged. As soon as the ignition temperature
¹  is exceeded, the conversion starts and countercur-
rent heat exchange and reaction take place simulta-
neously. In the reaction zone the temperature rises by at
least *¹ over ¹ . As a lower limit approximation

for the maximum temperature we therefore get
¹
'¹ #*¹ and the temperature and conversion

pro"les as given in Fig. 4d result.
Fig. 4. Analogy between fast #ow reversal and countercurrent opera-
tion: (a) scheme of a reverse-#ow reactor. The catalyst is the shaded
area; (b) temperature pro"les in the gasphase (**) and in the solid
phase (!!!) in the reverse-#ow reactor for short switching periods
(`sliding regimea); (c) scheme of a countercurrent reactor with geometric
and catalytic properties equivalent to (a); (d) temperature and conver-
sion pro"les in the countercurrent reactor.
The simple graphical design of Fig. 4d allows for a very
easy interpretation of the in#uence of design and operat-
ing parameters on the temperature and conversion pro-
"les for countercurrent or reverse #ow conditions (Fig. 5):
If two reactors run under identical operating conditions
but with catalysts of di!erent activity, the slope of the
temperature pro"le remains constant. The ignition tem-
perature of the less active catalyst, ¹  will be higher,

leading to the higher maximum temperature pro"le
2 (Fig. 5a).
Autothermal catalytic reactors are in a certain range
self-adaptive with respect to a slow catalyst deactivation: If
the activity decreases, the ignition temperature rises and as
long as it stays below ¹
(Fig. 5a) a longer portion of the
reactor will be used for heat exchange. This self-regulation
mechanism can however be detrimental if a catalyst with
a low thermal stability is used. Then a vicious circle results
where catalyst decay causes an increased maximum tem-
perature which in turn accelerates decay.
Inert packings at the reactor ends, frequently used for
reducing costs, destroy this self-regulation mechanism
since the minimum length of the heat exchanging part of
 G. Kolios et al. / Chemical Engineering Science 55 (2000) 5945}5967 5949

Fig. 5. Simpli"ed graphical design for an interpretation of the in#uence of design and operating parameters on the temperature and conversion pro"les
for countercurrent or reverse #ow conditions: (a) in#uence of catalyst activity or inert sections; (b) in#uence of feed concentration or adiabatic
temperature rise; (c) in#uence of the period length q .


the reactor is "xed by the extension of the inert zones. In
Fig. 5a the temperature pro"le 2 would also result for
a very active catalyst if inert front and end sections would
extend over a length z .

If the feed concentration (or the adiabatic temperature
rise) is increased, steeper gradients and a higher temper-
ature rise above the ignition temperature result (Fig. 5b).
The extent of the `plateaua of the temperature pro"le is
5950 G. Kolios et al. / Chemical Engineering Science 55 (2000) 5945}5967

therefore a measure for the robustness of the steady state

against extinction.
Compared to the conventional design of Fig. 1a the
integrated autothermal reactor is less sensitive to concen-
tration changes. This can be seen qualitatively from the
dotted temperature pro"les in Fig. 1. They correspond to
a doubling of the feed concentration for a simple irrevers-
ible reaction like the total catalytic combustion of or-
ganic pollutants in exhaust air. The doubling of the feed
concentration corresponds to a doubling of the adiabatic
temperature rise *¹ and, according to Eq. (1) to

a doubling of the temperature gradient. For the conven-
tional design this results in a doubling of the temperature
increase (¹ !¹). In the countercurrent "xed-bed

reactor or the reverse #ow reactor the maximum temper-
ature will be considerably lower since the catalytic reac-
tion will ignite at about the same ignition temperature
¹ . This means that the section of countercurrent heat
exchange without reaction is reduced and so is the sub-
sequent temperature increase.
The lateral displacement of the temperature-front in
a reverse-#ow rector can be calculated from Eq. (2). This
allows for the estimation of the maximum possible dura-
tion q of one semicycle which can be calculated from

the equations given in Fig. 5c as q "*l /w.


The simpli"ed results of Fig. 5 can be readily used for
a "rst short-cut design or an interpretation of experi-
ments. This has been shown for a number of examples by
Nieken (1993), Nieken et al. (1995) van de Beld and
Westerterp (1994) and ZuK #e and Turek (1997). Fig. 6
gives an example for the oxidation of similar amounts
(same *¹ ) of propane and of propene in a reverse #ow

reactor. The temperature gradient in the end section is
the same for both gases but di!erent maximum temper-
atures result because the ignition temperatures of pro-
pane is about 4003C as opposed to 2003C for propene.
2.2. Applications
The application of the reverse #ow reactor concept for
weakly exothermic reactions has been studied in numer-
ous contributions in recent years. Most of them are
mentioned in a comprehensive review by Matros and
Bunimovich (1996).
2.2.1. Autothermal reactors for total oxidation
Total oxidation of combustible components in exhaust
air has so far been the prime industrial application. Both
homogeneous combustion in an inert packing and cata-
lytic oxidation is used. The catalytic oxidation has the
advantage of considerably lower maximum temperature,
resulting in less fuel consumption if fuel has to be added
to sustain the autothermal operation. NO production is
V
generally no problem since the maximum temperature
seldom exceeds 5003C. Catalytic combustion is within
limits adaptive with respect to gradual catalyst decay as
Fig. 6. Periodic steady-state temperature pro"les for the oxidation of
similar amounts (same *¹ ) of propane and of propene under periodic

#ow reversal, experimental results from (Nieken, 1993).
explained in connection with Fig. 5a. Homogeneous
combustion is preferred where catalyst poisoning could
be a problem. Here temperature is often controlled to
above 9003C by co-feeding of natural gas.
One practical problem to be solved in periodic #ow
reversal is the prevention of a back#ush of untreated gas
into the exit line immediately after #ow reversal (see Fig.
3a). The most common solution in o!-gas puri"cation is
the use of a three-bed design where the beds switch from
reverse #ow operation to a purge step and back to
reverse #ow operation (Fig. 7). An elegant possibility of
operating a regenerative "xed-bed reactor in a continu-
ous mode with integrated purge steps without using
valves is to use a LjungstroK m-type rotating regenerator
design (Fig. 8) (Eigenberger & Nieken, 1991, Eigenberger,
1992). Since rotating seals are only necessary on the cold
gas side they present no major problem.
In large-scale operation catalytic combustion with an
adiabatic temperature rise as low as 103C (corresponding
to a feed concentration in the order of 0.025 wt% hydro-
carbons) can be run autothermally in reverse #ow reac-
tors. If the feed concentration is less, combustibles have
to be added to the feed to prevent extinction. Care must
be taken that the added combustibles have a similar
ignition temperature as the exhaust components, other-
wise extinction or only partially ignited steady states may
result (Nieken, Kolios & Eigenberger, 1994). Alterna-
tively hot exhaust gases from an external combustion
chamber can be injected into the center of the reactor
(Nieken, 1993). The more severe problem consists in the
prevention of overheating if the feed is temporarily too
rich in combustibles which can hardly be excluded in
industrial exhaust puri"cation. Due to the e$cient heat
exchange a rapid temperature increase would result
which could deteriorate catalyst activity or even damage
 G. Kolios et al. / Chemical Engineering Science 55 (2000) 5945}5967
Fig. 7. Three-bed design for o!-gas puri"cation with the middle bed
being back#ushed by a clean purge.
Fig. 8. Schematic of a rotating "xed-bed reactor.
the construction. Several methods have been proposed
including internal cooling, cold gas addition, hot gas
withdrawal, and structuring of the packed-bed activity
and heat conductivity but no single measure is able to
solve the problem without reducing the puri"cation e$-
ciency (Nieken, 1993). In addition internal cooling may
give rise to an instability of the periodic steady state
which will be treated in Section 2.3.
A countercurrent "xed-bed reactor requires a very
high speci"c heat exchange surface to compete with the
e$ciency of regenerative packed-bed heat exchange.
A standard shell and multitube design would be insu$-
cient. Possible concepts can be deduced from compact
heat exchangers, e.g. parallel plate heat exchangers where
the catalyst is deposited at the plate walls (Gaiser, 1993).
5951
An alternative solution is shown in Fig. 9 (Friedrich,
Gaiser, Eigenberger, Opferkuch & Kolios, 1997). Here
the in- and outcoming gas #ow is separated by a multiply
folded wall and the catalyst is deposited on an undulated
carrier which is inserted into the folds. This construction
allows for a simple sealing at the cold feed/exit sides and
easy replacement of the catalyst. With a channel width in
the order of 2 mm a countercurrent reactor will reach
a similar thermal e$ciency as a design using regenerative
heat exchange. Fig. 10 shows experimental results ob-
tained for the catalytic combustion of propene. The min-
imum adiabatic temperature rise for autothermal
operation of the pilot plant unit was 20 K. The compact
countercurrent reactor design is particularly suited for
smaller gas #ows up to 2000 m /h.
,
2.2.2. Autothermal reactors for equilibrium limited
reactions
The autothermal oxidation of SO to SO belongs to
 
the "rst reactions with periodic #ow reversal studied and
published by the Novosibirsk group of Boreskov, Matros
and Kiselev (1979), and Boreskov and Matros (1983).
Subsequent examples comprise the methanol and the
ammonia synthesis. These reactions belong to the class of
moderately exothermic equilibrium limited reactions.
Also the countercurrent "xed-bed reactor concept of Fig.
1b has been proposed for this class of reactions (Anony-
mous, 1994). Both the bene"ts and the limitations of
autothermal operation for equilibrium limited exother-
mic reactions have been nicely brought out in a paper by
Young, Hildebrandt and Glasser (1992). An example of
their simulations of the methanol synthesis is given in
Fig. 11. The temperature pro"le resembles the familiar
bell shape of a catalytic combustion, but contrary to the
previous examples the reaction is not completed when
the temperature maximum has been reached. It is only
subdued by approaching equilibrium as can be seen from
the conversion pro"les. With decreasing temperature to-
wards the exit section the conversion exceeds the equilib-
rium conversion of adiabatic operation. This can also be
seen from the temperature/conversion plot of Fig. 11
(bottom) where the equilibrium line and the line of opti-
mal temperature (maximum reaction rate) are given.
Autothermal operation is superior to one adiabatic reac-
tor since its operation line is closer to the optimal tem-
perature, but a two-stage adiabatic reactor with
interstage cooling (thick line) will result in a considerably
better conversion plus the production of process steam.
About the same "ndings can be drawn from the study of
Van den Bussche and Froment (1996) of the so-called
STAR-con"guration of reverse #ow reactors for meth-
anol synthesis. They showed that in order to obtain
reasonable conversion and to avoid excess temperatures
it is necessary to place a separate heat exchanger/steam
generator at the high-temperature node of their STAR
5952 G. Kolios et al. / Chemical Engineering Science 55 (2000) 5945}5967
Fig. 9. Autothermal parallel plate countercurrent reactor: Schematic of the folded plate countercurrent reactor (left) and measured temperature
pro"les for the noncatalytic combustion of traces of propene (right).
Fig. 10. Experimental results obtained for the catalytic combustion of
propene in the parallel plate countercurrent reactor of Fig. 9 (feed
concentration propene: 380 ppm).
arrangement which limits the maximum temperature to
about 2303C.
The general conclusion to be drawn is that autother-
mal operation could be of advantage for the processing of
low concentration feeds like SO containing e%uents

from the metallurgical industry (Xiao, Wang & Yuan,
1999) or of purge gas from a methanol synthesis loop but
that it is of limited value for exothermic equilibrium-
limited synthesis reactions.
2.3. Autothermal reactor stability
It is obvious that autothermal operation always takes
place in the region of multiple steady states. Fig. 12a
shows the region of multiplicity of an autothermal reac-
tor con"guration of Fig. 1a with the feed temperature
¹ as parameter. The ignited steady state is the desired

solution for normal operation. The other stable steady
state lies at the extinguished branch with (almost) no
conversion. The intermediate steady state is the unstable
solution. It separates the temperature region in which the
reactor would ignite from the region in which the reac-
tion will extinguish to the lower steady state. Similar
results can be obtained for the adiabatic "xed-bed reac-
tor with periodic #ow reversal.
Whereas the stability analysis of a countercurrent
"xed-bed reactor is fairly straightforward, special consid-
erations are required for reactors with periodic #ow
reversal. Here the truely stationary steady state of the
countercurrent reactor has its equivalence in the oscillat-
ing `periodic steady statea. Methods are required which
allow for the direct computation of the periodic steady
states and it is not until recently that e$cient methods for
this task have been developed. It has been shown by
several groups that a single exothermic reaction in an
autothermal reactor of the countercurrent or the
adiabatic reverse #ow reactor type has only the above
 G. Kolios et al. / Chemical Engineering Science 55 (2000) 5945}5967
Fig. 11. Reverse #ow reactor for an exothermic equilibrium reaction
(Young et al., 1992). Temperature and conversion pro"les during one
half-period (top and middle) and the course of the reaction in a temper-
ature/conversion plot (bottom). The reverse #ow reactor characteristic
(thin lines) is comapred to a two-stage adiabatic reactor with interstage
cooling (thick line).
three symmetrical solutions (Chumakova & Zolotarskii,
1990; Salinger & Eigenberger, 1996a,b; Khinast & Luss,
1997). If multiple exothermic reactions can take place,
more than three steady states are possible depending on
how many reactions may ignite independently (Nieken,
1993; Salinger & Eigenberger, 1996a,b; Khinast & Luss,
1997) but dynamic instabilities can be excluded as long as
countercurrent or reverse #ow reactors with negligible
heat losses are considered.
5953
This result is not too obvious since it was already
observed by Ruppel (1980), that a conventional autother-
mal reactor of the type shown in Fig. 1a can exhibit
autonomous periodic oscillations. Fig. 13 is a reprint of
the original work from which a physical explanation can
be drawn: The oscillations move through the packed bed
in the form of temperature peaks in which total conver-
sion takes place. As soon as a peak moves from the
adiabatic reactor into the heat exchanger it creates a new
temperature peak which reignites a new combustion
front. The bifurcation diagram (Fig. 13c) shows a similar
hysteresis loop like in Fig. 12a which is marked by their
maximum peak temperature. In addition a branch of
periodic oscillations occurs.
2.3.1. Circulation loop reactor
This dynamic instability of autothermal reactors
has in the sequence been studied in detail by
Gilles and coworkers (Mangold & Gilles, 1996; Hua,
Mangold & Gilles, 1998). They found that the dynamic
instability is most pronounced if a cocurrent heat
exchanger is used, since in this case the leaving temper-
ature front has the longest time to create a new front at
the reactor entrance. A respective reactor has been
named a circulation loop reactor and is shown in
Fig. 14a. The cocurrent heat exchange section and a part
of the reactor loop are "lled with catalyst. The entrance
heater is needed to start the reactor and to support its
operation. The bifurcation diagram (Fig. 14b) shows
a largely instable hysteresis loop and a broad region of
autonomous oscillations, an example of which is given in
Fig. 14c.
2.3.2. The cooled reverse yow reactor
The reverse #ow reactor also can produce dynamic
instabilities but so far this has only been observed if heat
losses from the packed bed are taken into account. This
has "rst been shown in a pioneering paper by R[ ehac\ ek,
Kubic\ ek and Marek (1992) and was later con"rmed
in a "rst detailed stability analysis by Salinger & Eigen-
berger (1996a,b). The most comprehensive analysis so
far has just appeared in two papers by Khinast,
Gurumoorthy and Luss (1998) and Khinast et al. (1999).
Only a few basic points shall be discussed in the following
while the reader is referred to the original sources for
details.
We assume a reverse #ow reactor with one moderately
exothermic reaction which is cooled over its entire length.
Fig. 15 a shows the in#uence of increasing cooling
intensity on the periodic steady-state temperature pro-
"les. The adiabatic pro"le (D"0) exhibits the well-
known shape. If cooling is applied (D'0) a typical
double hump in the temperature plateau develops. It is
caused by the fact that the heat of reaction is only set free
in a small portion of the catalyst bed after the ignition
temperature has been exceeded. With increasing cooling
5954 G. Kolios et al. / Chemical Engineering Science 55 (2000) 5945}5967
Fig. 12. Multiplicity features of an autothermal reactor: Maximum temperature versus inlet temperature (a); and conversion versus inlet temper-
ature (b).
Fig. 13. Autonomous oscillations of adiabatic "xed-bed reactors with
heat recycle (Ruppel, 1980). (a) Reactor con"guration. (b) Periodically
travelling reaction front with reignition inside the heat exchanger. (c)
Branch of stable steady state (**) and branch of stable oscillating
solutions (2).
intensity D the temperatures of the two maxima decrease
and they get closer together until they merge to a single
maximum. This situation is reached immediately before
extinction, which occurs because of a too strong cooling
intensity.
The solutions of Fig. 15a are symmetric since the
pro"le at the end of a period is just a mirror image of the
pro"le one or two or N periods before. It turned out that
in addition there can also be asymmetric solutions, pre-
ferably for short periods where the pro"les move between
two positions which are both shifted either to the left or
the right of the center. The most interesting feature how-
ever is the appearance of aperiodic solutions where the
pro"les never come back exactly into the same position.
This is shown in some detail in Fig. 16. The temperature
and weight fraction pro"les at the end of two successive
semicycles are given in each of the pictures for a sequence
of periods. The solid lines mark a semicycle with #ow
from the left, the dashed lines with #ow from the right.
The sequence of temperature pro"les in successive cycles
is marked by a creation of new temperature maxima,
their subsequent movement and growth and their "nal
shrinkage and disappearance. Conversion will be com-
pleted in the dominating temperature maximum as long
as it stays in the center part of the reactor but as soon as
it approaches one boundary, residence time may be too
short for total conversion and a new maximum develops.
An example is the left temperature maximum which "rst
appears in the 5th period, is dominating between the 31st
and the 35th period while it slowly moves to the left and
is later on replaced by a new maximum created to the
right of it. This right maximum will increase in height and
move to the right in subsequent cycles. In total we have
a slow autonomous movement of subsequent temper-
ature maxima to the left or the right and the periodic
switches of the #ow direction. And since two periodic
processes are in general not synchronized, a
quasiperiodic behavior results. It may even turn into
deterministic chaos as was already observed in R[ ehac\ ek
et al. (1992) and R[ ehac\ ek, Kubic\ ek and Marek (1998) and
recently con"rmed by Khinast et al. (1999). A new publi-
cation of Garg, Khinast and Luss (2000) shows that
a rather similar oscillatory instability can also be ob-
served in a cooled countercurrent reactor.
2.4. Summary
Multifunctional autothermal reactors with integrated
heat recovery are used for weakly exothermic high-tem-
perature reactions. Main applications so far are in the
"eld of waste gas puri"cation. Two alternative designs
exist which are based on di!erent mechanisms for heat
recovery, the countercurrent reactor using recuperative
heat exchange and the reverse #ow reactor using regen-
erative heat exchange. Both designs have comparable
properties with respect to design parameters and operat-
ing conditions. They show a certain adaptivity against
deviations in operating conditions due to the integrated
heat exchange. Autothermal reactors are usually oper-
ated in the region of multiple steady states, where the
ignited branch is the desired one. It has been shown
 G. Kolios et al. / Chemical Engineering Science 55 (2000) 5945}5967 5955

Fig. 14. Circulation loop reactor (Mangold & Gilles, 1996): Schematic of the reactor (a); bifurcation diagram (b); and temperature pro"les at di!erent
times in periodic steady state (c).

through detailed stability analysis that the countercur-
rent "xed-bed reactor and the reverse #ow reactor with
a single reaction have only three steady states if heat
losses are excluded, whereas the autothermal reactor
with separated heat exchanger can also exhibit dynamic
instabilities through autonomous reignitions. In addi-
tion, a variety of instabilities has been discovered for
reverse #ow reactors if heat losses from the packed bed
are taken into account. They include aperiodic front
movement in subsequent cycles and deterministic chaos.
3. Autothermal combination of exo- and endothermal
reactions
3.1. Introduction
Endothermic reactions can only be carried out if the
heat of reaction is supplied at the required reaction
temperature. Since the necessary heat is usually provided
by an auxiliary combustion reaction, many concepts
have been conceived and realized industrially of how the
5956 G. Kolios et al. / Chemical Engineering Science 55 (2000) 5945}5967

Fig. 15. Stability of the symmetric solution in a reverse #ow reactor with heat losses over the wall (Khinast et al., 1998): (a) The in#uence of cooling
intensity D on the shape of the symmetric solution pro"les (dimensionless temperature H over reactor length m); (b) the corresponding stability

diagram.

Fig. 16. Aperiodic oscillations of temperature (¹) and concentration (c) pro"les in a cooled reverse #ow reactor. The solid lines mark the last pro"les
before #ow reversal with #ow from the left, the broken lines the respective pro"les with #ow from the right.

endo- and exothermic reactions can be reasonably com-
bined. Such a combination has often been called
`autothermala if it is realized inside of one reactor, irre-
spective of the fact that the feed and exit temperatures of
this reactor could be pretty high. Well-known examples
are autothermal steam reforming (Hochgesand et al.,
1989), the Cato"n Process (Ercan & Gartside, 1996) or
several propositions for the use of periodic #ow reversal
for endothermic reactions (Haynes, Georgakis & Caram,
1992; Kulkarni & DudukovicH , 1996a).
In the following we will restrict ourselves to the more
narrow de"nition of autothermal operation of Section 1,
where the feed and the exit temperatures are considered
to be close to ambient or slightly above the evaporation
or condensation temperatures of the reactants involved.
This ensures optimal heat recovery in the reactor. Since
this kind of autothermal operation is only possible if the
overall reaction is weakly-to-moderately exothermic it
poses a "rst constraint on the coupling of the two reac-
tions. Again we can in principle use either indirect heat
exchange in an appropriate countercurrent reactor set-
up or regenerative heat exchange under reverse #ow
operation. In both cases the heat from the hot e%uent is
recovered in order to heat up the feed so that the feed
enters and the products leave the reactor with low tem-
perature. In their analysis Kolios and Eigenberger (1997)
 G. Kolios et al. / Chemical Engineering Science 55 (2000) 5945}5967 5957

endothermic reaction comes from both sides as in simul-

taneous operation and the necessary heat of reaction
from the exothermic reaction is supplied directly or in-
directly in the middle of the reactor.

3.2. Simultaneous operation

A pioneering paper on simultaneous operation was

published by Blanks, Wittrig and Peterson (1990). They
studied methane steam reforming together with methane
combustion in a reverse #ow reactor consisting of two
inert end portions and the active center part. Successful
operation of several laboratory and pilot plant reactors
up to 60 cm ID and 4 m length with CO yields up to 90%
has been reported. The periodic steady-state pro"les are
symmetric in the sense that they are mirror images of
each other in successive semicycles (Fig. 18), but they
di!er from the steady-state pro"les discussed in Section
2. The rapid methane combustion results in a distinct
temperature peak which is followed by the temperature
decrease caused by the endothermic steam reforming.
The length of the active catalyst zone and the cycle time
had to be properly adjusted to prevent excess temper-
atures, back reaction with decreasing temperatures or
coke formation at temperatures below 7503C. This

Fig. 17. Simultaneous, symmetric and asymmetric operation for the

coupling of exothermic and endothermic reactions (methane combus-
tion and methane steam reforming).

have found three di!erent ways to achieve this goal,

which we call

E the simultaneous operation,

E the asymmetric operation and,
E the symmetric operation.

The di!erences are shown in Fig. 17 for the example of

methane steam reforming coupled with methane com-
bustion. Under simultaneous operation the reactants for
both (endo- and exothermic) reactions are mixed and all
reactions run more or less in parallel. The simultaneous
mode is thus rather similar to the reactor operation
discussed in Section 2. Under asymmetric and under
symmetric conditions both reactions are separated in
time or in space. Under asymmetric conditions the feed
for the endothermic reaction always comes from one side
(in the regenerative mode during one portion of the
whole period) and the feed for the exothermic reaction
comes from the opposite side (during the rest of the Fig. 18. Syngas generation with simultaneous methane combustion in
period). Under symmetric conditions the feed for the a reverse-#ow reactor (Blanks et al., 1990).
5958 G. Kolios et al. / Chemical Engineering Science 55 (2000) 5945}5967

Fig. 19. Gas temperature (¹ ) and concentration (y) pro"les for asymmetric operation of methane steam reforming (RE-GAS process, Kulkarni and
E
DudukovicH , 1998); (a,b) `wrong way processa; (c,d) `normala process. The odd semicycle denotes methane combustion, the even semicycle methane
steam reforming (reverse reactions excluded).

sensitivity obviously led Amoco to stop the further devel-
opment of this process.
3.3. Asymmetric operation
One of the "rst mentions of autothermal asymmetric
operation can be found in Levenspiels Dankwerts Mem-
orial Lecture in 1988 (Levenspiel, 1988). Among other
integrated reactor concepts he proposed and discussed
the RE-GAS process for coal gasi"cation. Using periodic
#ow reversal as depicted in Fig. 17b he assumed a #ow of
powdered coal in air for one semicycle to heat up an inert
packed bed and an opposite #ow of suspended coal with
steam for coal gasi"cation for the second half-period.
Compared to alternative options with simultaneous feed
of coal, air and steam the RE-GAS process allows to
obtain a nitrogen-free syngas during the steaming period.
This scheme was theoretically studied for catalytic "xed-
bed processes in a series of papers by Kulkarni and
DudukovicH (1996b,1998). They came to the conclusion
that the asymmetric process with `colda feeds and e%u-
ents, which they called the wrong-way process (after the
wrong way behavior of a moving temperature front (Pin-
jala et al., 1988)) was the wrong way to combine exo- and
endothermic reactions. Their "ndings were based on
simulations of methane steam reforming where no reas-
onably concentrated fuel mixtures could be processed
without exceeding peak temperatures of 1500 K. This
was due to the fact that with cold feed from the combus-
tion side a high and moving temperature peak with steep
slopes was formed in which not enough heat for the
subsequent endothermic reaction could be stored
(Fig. 19, left). They proposed a `normal RE-GAS pro-
cessa instead which was fed from the combustion side
with feed temperatures above the ignition temperature of
methane (1000 K). This ensured the establishment of
a broader, not moving temperature zone which accumu-
lated enough heat for the subsequent steam reforming
(Fig. 19, right), but the goal to incorporate the full heat
exchange between feeds and e%uents in the reactor could
not be met.
Independent work of Kolios (1997) and Kolios and
Eigenberger (1997,1999) on asymmetric operation con-
cerned the coupling of dehydrogenation of ethylbenzene
to styrene with the combustion of the hydrogen produc-
ed. One result of these studies was the big in#uence of an
axial structuring of the catalyst bed into front and end
sections and an active center part. Without inert sections
 G. Kolios et al. / Chemical Engineering Science 55 (2000) 5945}5967
Fig. 20. E!ect of inert zones for ethylbenzene dehydrogenation coupled
with hydrogen combustion (asymmetric operation mode) in a reverse
#ow reactor (Kolios, 1997). First line: Temperature pro"les during the
ethylbenzene dehydrogenation (production phase); Second line: Ethyl-
benzene conversion pro"les during the production phase; Third line:
Temperature pro"les during hydrogen combustion (regeneration
phase); Fourth line: Hydrogen mass-fraction pro"les during the regen-
eration phase; Reactor with active catalyst only (left column) and
reactor with inert end sections (right). The heat production through
hydrogen combustion is the same in both cases.
the maximum temperature reached during hydrogen
combustion was too low to start styrene synthesis, Fig. 20
(left column). The reason is the low ignition temperature
of hydrogen combustion on styrene catalyst, the result of
which had been discussed in Fig. 5a. Using inert front
and end sections brought the bed temperature up. Kolios
showed that in this case a larger portion of the "xed bed
could be used for high-temperature heat storage during
the combustion stage (Fig. 20, right column). At the
beginning of the dehydrogenation period surprisingly
high conversions could be obtained because of the favor-
able increasing temperature pro"le. Unfortunately the
heat consumption led to a rapid drop of the temperature
pro"le, causing a drop in conversion so that the mean
5959
conversion over the half-cycle was only moderate. Modi-
"cations e.g. by using latent storage packings in the
reaction zone gave some improvements but since in
asymmetric operation styrene production takes place
only during one semicycle, this mode was considered less
attractive.
Since short cycle times are obviously fortunate for the
asymmetric operation mode it seems interesting to look
at the alternative for fast cycling, countercurrent opera-
tion. This option has been studied in some detail by
Frauhammer, Eigenberger, von Hippel and Arntz (1998)
and Frauhammer, Eigenberger, von Hippel & Arntz
(1999) using again the example of methane steam reform-
ing. They considered asymmetric countercurrent opera-
tion as shown in Fig. 17b (left) in adjacent channels
of a ceramic monolith. Fig. 21 shows simulation results
for temperature and conversion. If active catalyst extends
over the full length of both channels (a) the incoming
fuel gas (methane and air) ignites readily and a temper-
ature maximum develops close to the right border of
the monolith reactor. The process gas coming from
the opposite side is continuously heated up leading to
total conversion before the maximum temperature is
reached. Afterwards, the dropping temperature pro"le
causes a decrease in the equilibrium conversion and some
back-reaction which reduces the exit conversion to about
70%.
An obvious measure to avoid back-reaction is to limit
the reforming catalyst to the part of the reactor where
maximum conversion is obtained (Fig. 21b). Heat recov-
ery could be improved further by providing a larger heat
exchanger zone at the right entrance. This can be done by
reducing the length of the active catalyst section in the
combustion channels (Fig. 21c). Compared to the
two previous examples now the gas streams enter and
leave the monolith at lower temperatures and the energy
e$ciency (the ratio between the actual heat consumption
of the endothermic reaction and the actual heat release
of the combustion) increases from 48% in example (a)
over 69% in (b) to 76% in (c). Obviously the proper
position of the active catalyst inside the reactor is impor-
tant for the optimization of the reactor's performance
and e$ciency. Nevertheless the adjustment of the posi-
tion of the reaction zones is a nontrivial task since
a methane}air mixture tends to ignite homogeneously
above about 7503C.
A second problem of practical realization is the ther-
mal stability of the reactor material. An appropriate
ceramic monolith should be able to generally withstand
the expected maximum temperatures in the combustion
channels of up to 15003C but so far experimental veri"ca-
tion was only possible for diluted feed with maximum
temperatures below 10003C (Fig. 22). Higher temper-
atures caused cracks in the ceramic material which were
attributed to thermal stress in the peak temperature
region.
5960 G. Kolios et al. / Chemical Engineering Science 55 (2000) 5945}5967
Fig. 21. Steam reforming of methane in a countercurrent monolith reactor (asymmetric operation mode) from (Frauhammer et al., 1999). Simulation
results for di!erent positions of active catalyst (black bars).
Fig. 22. Steam reforming of methane in a countercurrent monolith
reactor- experimental results (Frauhammer et al., 1999).
3.4. Symmetric operation
First simulation results on symmetric operation have
been published by Snyder and Subramaniam (1994) for
the reverse #ow operation of styrene synthesis through
ethylbenzene dehydrogenation. Similar to Fig. 17c (right)
ethylbenzene and steam were fed alternatingly from left
to right and vice versa while superheated steam, gener-
ated by the combustion of the produced hydrogen was
continuously fed into the center of the reactor. Several
options with central feed or distributed steam feed were
studied which showed the general applicability of the
concept. Compared to the industrially established multi-
tubular isothermal or the adiabatic multibed process the
simulated results were however not too encouraging
since only conversions below 25% were predicted. In an
independent study Kolios (1997) and Kolios and Eigen-
berger (1997,1999) showed that these moderate predic-
tions had to be attributed to the use of somewhat
outdated kinetics and too conservative estimates about
the maximum temperature allowed.
Fig. 23 shows these simulation results for a base case
con"guration. As in the study of Snyder and Sub-
ramaniam inert front and end portions and an active
catalyst in the center are assumed. Fig. 23a shows tem-
perature pro"les in the periodic steady state. After the
#ow switch the synthesis gas enters from left and is
heated up by the packing according to pro"le 1. In the
center of the reactor superheated steam of 12003C is
added and assumed to mix perfectly with the passing gas.
The favorable increasing temperature pro"le causes an
ethylbenzene conversion of above 50% (Fig. 23b). During
the course of the semicycle the bed temperature of the
reactor decreases in the left part due to endothermic
reaction but it increases in the right part due to the hot
steam feed. This causes the maximum temperature and
the conversion to stay at su$ciently high values over the
whole cycle (Fig. 23c and d). Compared to the asymmet-
ric operation of Fig. 20 which was simulated under com-
parable operating conditions, the reactor behavior is
 G. Kolios et al. / Chemical Engineering Science 55 (2000) 5945}5967 5961

Fig. 23. Symmetric operation mode for ethylbenzene dehydrogenation with hot gas injection in the midle of the reactor: Temperature pro"les (a) and
conversion pro"les (b) during one semicycle in periodic steady state with #ow entrance from the left, maximum and exit temperature (c) and conversion
and selectivity during the cyclic steady state (d).

Fig. 24. Experimental results for the ethylbenzene dehydrogenation in an autothermal reverse #ow reactor. (a) Schematics of the lab-scale reactor and
the catalytic burner (Kolios, 1997; Kolios & Eigenberger, 1999). (b) Temperature pro"les in cyclic steady state at the end of semicycle when #ow comes
from the right: Simulation (**) and experiment (} # }).

much more favorable. It could be further improved by
increasing the amount of side stream. Conversions up to
80% with good selectivities were predicted. In most cases
the hydrogen e$ciency (the amount of hydrogen produc-
ed over the amount of hydrogen used for the generation
of the hot side stream) was above 1, ensuring operation
without external thermal energy consumption.
The predictions could be veri"ed in a sequence of
experiments in a lab scale reactor shown in Fig. 24a.
A catalytic burner for hydrogen and air with steam as
carrier gas was placed in the center of the packed bed.
Fig. 24b shows measured temperature pro"les at the end
of the period where #ow comes from the right. Also
shown are simulation results where axial heat conduction
in the walls and the internals was taken into account.
A reasonable agreement can be observed except for the
center section at and behind the hot side feed. Here
mixing of the two gas streams is obviously incomplete
and the thermocouples are more in#uenced by the hot
side stream than by the colder synthesis gas. Conversions
of about 65% with selectivities corresponding to the best
values obtained with the same catalyst under isothermal
operation could be obtained. The results show that sym-
metric operation seems to be a prospective method for
the e$cient coupling of endo- and exothermic reactions
without the danger of too high maximum temperatures.
This will be further substantiated with the following
considerations.
5962 G. Kolios et al. / Chemical Engineering Science 55 (2000) 5945}5967
3.5. A simplixed picture of the autothermal coupling
of endo- and exothermic reactions
It should be obvious from the preceding discussion
that there are several interesting options for an e$cient
autothermal coupling of endo- and exothermic reactions.
But so far most of the options published still have draw-
backs or problems which need to be solved before an
industrial realization can be considered promising. In
general these problems are related to the temperaure
control of the process, i.e. to the question of how the
exothermic and the endothermic reaction can be e$-
ciently coupled without the occurrence of excessively
high temperatures. To answer this question it seems
reasonable to start with some basic constraints and spec-
ify some general features which need to be incorporated
into an e$cient autothermal coupling.
One starting point is that the feed and exit streams of
the autothermal reactor should be `colda, that means
considerably lower than the required reaction temper-
ature. Since inside the reactor temperatures well above
the ignition temperatures of both the exothermic and the
endothermic reaction are required, one should try to
incorporate the most e$cient heat exchange available
which is countercurrent recuperative heat exchange of
#ows with equal thermal capacity (or a respective regen-
erative heat exchange with short cycle times).
The basic energy constraint is that the heat generation
of the exothermic reaction has to exceed the heat con-
sumption of the endothermic reaction. Assuming #ows of
equal thermal capacity this means that the adiabatic
temperature rise of the exothermic reaction *¹ has to
 
exceed the adiabatic temperature drop of the endother-
mic reaction !*¹ and that the sum of both,

*¹"(*¹#*¹) (3)
 
will be available for countercurrent heat exchange for the
two #ows. The countercurrent heat exchangers must be
big enough to heat the combustion feed both above the
ignition temperature of the combustion reaction ¹  and
the syngas feed to a su$ciently high reactor entrance
temperature. In case that the following reactor is
adiabatic, `su$ciently higha means that the reactor en-
trance temperature has to exceed the required reactor
exit temperature ¹ by the expected adiabatic temper-
ature drop *¹. ¹ is a lower limit temperature

which guarantees that the rate of the endothermic reac-
tion at the required exit conversion is still su$ciently
rapid. *¹, *¹, ¹  and ¹ together with the
 
temperature slope of equal capacity countercurrent heat
exchange are the "ve important quantities which in the
following will be used to de"ne base cases of autothermal
coupling of exo- and endothermic reactions. Note that in
Fig. 5 we needed only *¹, ¹  and d¹/dz (Eq. (1)) to

get a full picture of the autothermal behavior with an
exothermic reaction.
'17503C.
Before discussing integrated reactor concepts it seems
reasonable to "rst go back to the unit operation ap-
proach mentioned in Section 2.1 and to consider combi-
nations of countercurrent heat exchangers with adiabatic
reactors which ful"ll the above requirements. In the fol-
lowing we will do this for each of the three con"gurations
given in Fig. 17a}c.
As a "rst example we will try to combine an exother-
mic reaction with a thermally neutral reaction
(*H "0), such that the reactor feed temperatures well
0
exceed the ignition limits of both reactions ¹ . The
result is given in Fig. 25a. The appropriate sequence of
unit operations consists of two countercurrent heat ex-
changers connecting an adiabatic reactor for the exother-
mic reaction and an adiabatic reactor for the thermally
neutral reaction. Assuming temperature-independent
heat transport parameters as in Fig. 5, a similar graphical
construction can be used for the temperature pro"les of
the heat exchange sections. From Eq. (1) the slope in both
heat exchangers is given. To obtain the highest maximum
temperatures or optimal energy utilization requires equal
temperature di!erences in both countercurrent heat ex-
changers, hence *¹ "*¹ "*¹/2"*¹/2. If the
  
available heat exchange area would have been divided
such that the left heat exchanger gets 4/5 and the
right one 1/5 of it, the temperature pro"les, as shown
in Fig. 25b would result. The position of the new temper-
ature maximum is given by the length of the respective
heat exchangers, hence the temperature slopes in the
respective heat exchange sections (Eq. (1)) correspond
to 1 : 4. This means that *¹ "*¹/5 and
 
*¹ "4*¹/5. This is about the result obtained in

Fig. 21b, where the length of the right heat transfer
section was limited by the rapid ignition of the combus-
tion reaction. It is obvious that this design is inferior to
Fig. 25a if a maximum area of the catalyst bed should
stay above an assumed ignition temperature ¹ in or-

der to obtain maximum conversion with minimum en-
ergy consumption.
3.5.1. Simultaneous operation
A unit operation analogue of the simultaneous opera-
tion concept of Fig. 17a (left) which ful"lls all of the above
requirements is given in Fig. 26. The (simultaneous) exo-
and endothermic reaction is now considered to take
place sequentially in two consecutive adiabatic reactors.
It is obvious that the sequence of exothermic and en-
dothermic reaction requires less heat transfer area to
bring the feed to a required reaction temperature than
the oppposite sequence. In the adiabatic reactor arrange-
ment of Fig. 26 the maximum temperature is given
by ¹#(!*¹), assuming ¹ (¹. Since

*¹'!*¹ an estimate for the steam reforming
 
of methane with undiluted feed (¹ "7003C,
*¹"!10503C) in Fig. 26 would lead to a max-

imum temperature of ¹
 G. Kolios et al. / Chemical Engineering Science 55 (2000) 5945}5967
Fig. 25. Asymetric operation between a thermally neutral and an exothermic reaction. Heat exchangers of equal (a) and of di!erent size (b).
Fig. 26. A unit operation analogue of simultaneous operation.
If, contrary to the assumptions of Fig. 26 the two
reactions could be run in the same catalyst bed with
comparable rates the heat generation and consumption
would compensate and the temperature would remain
almost constant at ¹. In the example of Fig. 18 the
exothermic reaction is obviously considerably faster than
the endothermic one leading to the pronounced temper-
ature peak. A possible remedy in this case would be to
slow down the combustion reaction and * since this
seems impossible * to either use multiple feeds for oxy-
gen or to care for an excellent axial heat transfer in the
reaction zone. Since the behavior of both #ow directions
of the design in Fig. 26 is obviously similar, the reactor
5963
design can be simpli"ed to the part depicted by solid lines
with an internal recycle of the #ow between the exother-
mic and the endothermic stage.
3.5.2. Asymmetric operation
An energetically optimal unit operation analogue for
the asymmetric operation of Fig. 17b is given in Fig. 27
(top). It can be seen that the left heat exchanger has to be
considerably longer than the right one since it has to heat
up the endothermic feed to a maximum temperature
which is again given by ¹#*¹. Since the thermal

capacity of both streams should be equal, a driving
temperature di!erence of (*¹#*¹)/2 is available
 
at each heat exchanger and the temperature slopes are
equal. If heat exchange would be allowed between the
two adiabatic reactors the maximum temperature could
be reduced. If the heat production and the heat consump-
tion rates could be made equal for both reactions, the
maximum temperature would even be limited to about
¹. Since this seems impossible, similar remedies as
discussed for simultaneous operation should be con-
sidered.
3.5.3. Symmetric operation
A unit operation analogue for symmetric operation is
shown in Fig. 28. It is su$cient for countercurrent opera-
tion and could be extended as in Fig. 26 by a symmetric
counterpart at its right-hand side in order to map the
principle of the reverse #ow process in Section 3.4. Sev-
eral con"gurations are possible. Since the necessary heat
of reaction shall be supplied by heat exchange with a fuel
5964 G. Kolios et al. / Chemical Engineering Science 55 (2000) 5945}5967
Fig. 27. A unit operation analogue of asymmetric operation.
combustion circuit or by direct hot gas addition from it,
two interconnected circuits, the (endothermic) syngas
loop and the (exothermic) combustion circuit have to be
considered. As before, optimal energy utilization requires
that both streams have equal thermal capacity and equal
speci"c heat exchange area. This leads to the con"gura-
tions of Fig. 28 where the temperature pro"les in the two
main countercurrent heat exchangers are identical. In
Fig. 28a the heat exchange between the two circuits takes
place via a third countercurrent heat exchanger, whereas
Fig. 28. A unit operation analogue of symetric operation. Con"guration with heat supply by heat exchange (a) and heat supply by hot gas addition (b).
in Fig. 28b the hot gas stream is added to the syngas #ow
before and an equivalent amount is withdrawn after the
active catalyst bed. If this addition is distributed over the
length of the syngas reactor the maximum temperature
on the syngas side can be considerably reduced. As a re-
sult, simple addition of a hot side stream as suggested in
Fig. 17 and utilized in Figs. 23 and 24 turns out to be an
energetically suboptimal solution because the require-
ment of equal heat capacity streams in the heat exchan-
gers is violated.
Comparing Figs. 28a and b it might be surprising that
the countercurrent solution of Fig. 28a is equivalent to
the mixed stream solution Fig. 28b. The reason is simple
that the feed temperature of the (endothermic) syngas
reactor is of no importance as long as its exit temperature
at the required conversion is above ¹. Of course the
design of Fig. 28b will need a bigger syngas reactor
because of the lower feed temperature and the diluted
feed concentration. The latter however can be of advant-
age for equilibrium-limited reactions with volume in-
crease like dehydrogenations.
3.5.4. Regenerative heat transfer
So far an optimized design has primarily been dis-
cussed for countercurrent operation. The easiest transfer
to regenerative operation with periodic #ow reversal is
obviously possible for symmetrical operation. This was
already shown for the examples of Kolios and Eigenber-
ger (1997) and Snyder and Subramaniam (1994). The
only required addition is the above-mentioned provision
 G. Kolios et al. / Chemical Engineering Science 55 (2000) 5945}5967 5965

of a countercurrent heat exchanger for the burner feed sequence substitutes of the integrated process. Detailed
gas. Here it might be of advantage to switch the positions simulation and analysis is necessary for further optimiza-
of the hot gas feed ports from half-period to half-period tion of the structure and of the operating conditions of
as already suggested by Snyder and Subramaniam (1994). these reactor concepts.
Under simultaneous as well as under asymmetric
operation there is always the danger of a high and narrow
temperature maximum if the rate of the exothermic reac- Notation
tion could not be slowed down to that of the endothermic
one. This is well demonstrated by the simulations of Kul- a surface to volume ratio
karni and DudukovicH (1998), where Fig. 19a has a close T
c speci"c heat capacity of the gas mixture
shape similarity with the idealized temperature pro"les of N
c speci"c heat capacity of the solid packing
Fig. 27. For periodic #ow reversal the pro"les are even less Q
c feed concentration
advantageous than for countercurrent operation because h wall or catalyst heat transfer coe!cient
only few thermal energy can be stored in the regenerative U
mR mass #ux density
reaction zone without reaching excessive peak temper- X
¹ temperature
atures. The only remedies recommended are again an ¹ feed temperature
increased axial heat transport, possibly combined with ¹ required reaction zone exit temperature for en-
a latent heat storage (Kolios & Eigenberger, 1997). But in dothermic equilibrium reaction
general it seems that recuperative heat exchange is of ¹  (approximate) ignition temperature of reaction
advantage for the simultaneous or the asymmetric coup- ¹  maximum reactor temperature
ling of endo- and exothermic reactions, if the problem of v e!ective velocity of gas mixture
material stability for high-temperature heat exchange can w front moving velocity (Eq. (2))
be su$ciently solved. w weight fraction
X conversion
> mole fraction
4. Conclusions z axial reactor coordinate

Autothermal multifunctional reactors have gained Greek letters

a considerable interest in the last decades. The integration
of reaction and heat exchange within one piece of equip- *H enthalpy of reaction
0
ment has basic advantages over the conventional unit *¹ total temperature rise (maximum minus feed
operation design: Heat losses can be minimized and the temperature)
reactor is less sensitive to perturbations because of its *¹ adiabatic temperature rise of the reaction

inherent adaptivity. Autothermal reactors are widely spread *¹ driving heat exchange temperature di!erence
in industrial applications in the "eld of waste air puri"ca- (see Eq. (3))
tion. Nevertheless the design of autothermal reactors is e void fraction of catalyst
a nontrivial task because the intrinsic feedback of heat gives j e!ective axial heat conductivity of reactor or
rise to a complex parametric and dynamic behavior. 
heat exchanger
A new and very promissing application of autothermal j heat conductivity of wall
U
multifunctional reactors is the coupling of endothermic o density of the gas mixture
and exothermic reactions where the product of the en- o solid density (of packing)
dothermic reaction is the desired one. Several process Q
schemes have been proposed which can be subdivided in
three categories: the simultaneous, the asymmetric and Acknowledgements
the symmetric operation mode. So far the potential of the
new processes has been demonstrated, but also the need Our results presented in this review have been made
for optimization became obvious. The development of possible through grants of the German Science Founda-
new reactor designs (monolith reactor, folded-plate reac- tion (DFG) and of the German Bundesministerium fu( r
tor) and the application of advanced materials have been Bildung und Forschung (BMBF).
triggered by these studies in order to enhance the process
e$ciency. The distribution of the catalytic activity in
di!erent zones along the axis has been shown to have
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