Chemical Engineering Science 54 (1999) 2585}2595

Parametric study of unsteady-state #ow modulation in trickle-bed

reactors
M.R. Khadilkar, M.H. Al-Dahhan*, M.P. DudukovicH
Chemical Reaction Engineering Laboratory (CREL), Department of Chemical Engineering, School of Engineering and Applied Science Washington
University, Campus Box 1198, St. Louis, MO 63130-3899, USA

Abstract

Unsteady-state liquid #ow modulation (periodic operation) was investigated for hydrogenation of alpha-methylstyrene to cumene
in a hexane solvent over 0.5% Pd on alumina spheres. This test reaction was run under both gas and liquid reactant-limited
conditions. It is shown that periodic liquid #ow modulation can alter the supply of liquid and gaseous reactants to the catalyst and
result in reactor performance di!erent from that obtained under steady-state conditions. The e!ect of key parameters such as extent of
gas/liquid limitation, total cycle period, cycle split, and liquid mass velocity were investigated experimentally to demonstrate the
cause}e!ect relationships in periodic operation. Performance enhancement was observed for a wide range of operating conditions
under gas reactant limitation. It was strongly dependent upon the extent of catalyst wetting under liquid-limited conditions. The
feasibility of achieving improved reactor performance is shown to depend on the extent of reactant limitation, the cycle period and
split, mean liquid mass velocity, and the improvement of liquid maldistribution by periodic operation. Moreover, performance
enhancement is dependent upon the induced #ow modulation frequency and this is discussed in relation to the natural frequency of
the governing process.  1999 Elsevier Science Ltd. All rights reserved.

Keywords: Trickle-bed reactors; Periodic operation; Induced #ow modulation; Hydrogenation

1. Introduction mance under di!erent operating conditions. Thorough

Trickle-bed reactors, packed beds of catalysts with
cocurrent down#ow of gas and liquid are used extensive-
ly for hydrotreating and hydrodesulfurization applica-
tions in the re"ning industry, and for hydrogenation,
oxidation, and, hydrodenitrogenation applications in the
chemical, biochemical, and waste treatment industry
(Al-Dahhan et al., 1997; Saroha and Nigam, 1996). High
operating pressures and temperatures are generally em-
ployed to obtain desirable reaction}transport behavior
in these reactors. Traditionally, trickle beds have been
designed through a stepwise empirical approach with the
objective of steady-state operation. The acceptance of
alternative approaches for design and operation of
existing and new reactors depends on an improved un-
derstanding of the phenomena that govern their perfor-
* Corresponding author. Tel.: 001-314-935-7187; fax: 001-314-935-
4832; e-mail: muthanna@wuche.che.wustl.edu.
Present address: GE Plastics, One Lexan Lane, Mt Vernon, IN
47620, USA.
understanding of these reaction}transport interactions is
complicated by the presence of multiple catalyst wetting
conditions induced by two-phase #ow, which can a!ect
performance di!erently depending upon whether the re-
action is gas reactant or liquid reactant limited (Mills and
DudukovicH , 1980). Typically, a high liquid mass velocity
and completely wetted catalyst are desirable for liquid-
limited reactions, whereas a low liquid mass velocity and
partially wetted catalyst are preferable in gas-limited
reactions. Because of the competition between the phases
in supplying reactants to the catalyst, the possibility of
performance enhancement (the increase in the #ow-aver-
aged conversion in comparison with the steady-state
conversion) by operating under unsteady-state condi-
tions exists in these reactors. Unsteady-state (periodic)
operation has been shown to yield better performance in
other multiphase reactors, adsorbers, ion exchangers,
etc., on industrial scale (Silveston, 1990), but has not been
implemented on industrial trickle-bed reactors. Indus-
trial implementation of unsteady (periodic) operation in

0009-2509/99/$ } see front matter  1999 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 9 8 ) 0 0 4 2 6 - 6
2586 M.R. Khadilkar et al. /Chemical Engineering Science 54 (1999) 2585}2595

pilot- and commercial-scale trickle-bed reactors will fol-
low rigorous modeling, simulation, and laboratory-scale
experimental investigation on test reaction systems. Ob-
serving reactor performance under unsteady-state opera-
tion can also yield an insight into the reaction}transport
interactions occurring in a trickle bed, which can be used
to improve steady-state operation. Performance im-
provement in existing trickle-bed reactors can have
signi"cant economic impact due to high capital costs
and large capacity involved, particularly in the re"ning
industry.
2. Background and modulation strategies
The literature dealing with unsteady-state behavior in
chemical systems was reviewed by Silveston (1990) and
classi"ed into two categories: (i) parameter forcing,
and (ii) #ow reversal. Most of the investigations sum-
marized in his review were parameter forcing studies on
stirred tanks, heat exchangers, ion exchangers, and a few
#ow reversal studies on gas}solid "xed beds, adsorbers
and fractionators. On the basis of the observations on
these systems, several strategies were suggested for pos-
sible performance enhancement in trickle-bed reactors
(Silveston, 1990), such as modulation of (i) #ow, (ii) com-
position, or (iii) catalyst activity. Some of these have been
considered in the few studies that have appeared in the
past decade (as summarized in Table 1). However, none
of these strategies has been implemented commercially as
a result of a number of factors: (i) lack of knowledge of
the transport-kinetic parameters in processes of interest
under dynamic conditions, (ii) lack of an established
methodology and sets of operating parameters for imple-
mentation of periodic operation, and (iii) apprehensions
about operation and control of large-scale continuous
reactors under transient conditions. Rigorous experi-
mental and modeling e!ort is necessary to understand
the phenomena underlying unsteady-state operation in
order to establish guidance for commercial implementa-
tion. This study is a step in that direction and represents
an attempt to expand the knowledge and understanding
of unsteady-state behavior of trickle-bed reactors.
The results reported in the literature on unsteady-state
operation of trickle-bed reactors are summarized in
Table 1 and only the key observations are brie#y dis-
cussed here. Haure et al. (1990) and Lee et al. (1995)
studied periodic #ow modulation (also referred to as
induced pulsing or induced #ow modulation) of water
(referred to as ON}OFF #ow modulation) for SO oxi-

dation to obtain concentrated sulfuric acid. They ob-
served an enhancement in supply of SO and O to the
 
catalyst during the liquid OFF cycle, resulting in higher
performance and a temperature rise of up to 153C. They
also attempted to model unsteady-state operation based
on the Institute of Catalysis approach (Stegasov et al.,
1994) and were able to predict the rate enhancement and
the temperature rise with limited success. Lange et al.
(1994) experimentally investigated (1) hydrogenation of
cyclohexene, and (2) hydrogenation of alpha-methyl-
styrene on a palladium catalyst by modulation of liquid
feed concentration and feed rate, respectively. They used
the non-isothermal composition modulation of cyclo-
hexene to control the conversion and temperature. Their
total cycle period was based on the time at which a switch
occurs from a three-phase to a two-phase system due to
complete evaporation of the liquid phase. For the case of
hydrogenation of alpha-methylstyrene under isothermal

Table 1
Literature studies on unsteady-state operation in trickle beds

Author(s) System studied Modulation strategy L and G #ow rates Cycle period (q) Performance
and split (p) enhancement
(%) (temperature
rise (3C))

Haure et al. (1990) SO oxidation Flow (non-isothermal) < "0.03}1.75 mm/s q"10}80 min 30}50%
 *
< "1}2 cm/s (p"0.1, 0}0.5)
%
Lange et al. (1994) Cyclohexene Composition Q "80}250 ml/h q"up to 30 min 2}15% (Temp.
*
hydrogenation (non-isothermal) Conc"5}100% (p"0.2}0.5) rise"303C)
a-MS Liquid #ow Q "0}300 ml/h, q"1}10 min
*
hydrogenation (isothermal) Q "20 l/h (p"0.25}0.5)
%
Stegasov et al. (1994) SO oxidation Model < "0.1}0.5 cm/s, q"10}30 min Max"80%
 *
< "1.7}2.5 cm/s (p"0.1}0.5)
%
Lee et al. (1995) SO oxidation Adiabatic #ow modulation < "0.085}0.212 cm/s, q"up to 60 min
 *
S< "1000 h\ (p"0.02}0.1)
%
Castellari a-MS hydrogenation Non-isothermal Q "2.27 ml/s q"5}45 min 400% (Temp.
*
and Haure (1996) Q "900 ml/s (p"0.3}0.5) rise"453C)
%
Conv. (US)!Conv. (SS)
Performance enhancement, %" ;100.
Conv. (SS)
 M.R. Khadilkar et al. /Chemical Engineering Science 54 (1999) 2585}2595
conditions, the authors observed the maximum improve-
ment in performance (#ow-averaged conversion) at
a cycle period of 8 min and a cycle split of 0.5. The
observed improvement in conversion (between 2 and
15%) was attributed to better wetting due to the liquid
pulse and presumably removal of the stagnant liquid
upon passage of the pulse. The present study extends the
work on this system to look at the performance govern-
ing factors for a wider range of operating and reaction
conditions. Castellari and Haure (1995) investigated the
performance enhancement (in conversion) by #ow modu-
lation of pure alpha-methylstyrene under semi-runaway
conditions (complete catalyst dryout) and demonstrated
signi"cant enhancement resulting from high gas-phase
reaction rates. The large temperature rise (&453C) dur-
ing the liquid OFF part of the cycle was quenched by the
liquid reactant in the ON part of the cycle.
All of the above-mentioned studies on periodic opera-
tion of trickle-bed reactors are restricted to gaseous reac-
tant limited conditions. Periodic operation under gas
reactant limited conditions can ensure periodic dryout of
catalyst particle and direct access of gaseous reactant to
the catalyst sites, replenishment of catalyst with liquid
reactant, periodic removal of products by fresh liquid,
and quenching of a predetermined rise in temperature.
On the other hand, under liquid-limited conditions, cata-
lyst wetting and liquid supply to the particles is crucial,
and periodic operation can reduce and eliminate liquid
maldistribution, ensure a completely irrigated bed, and,
quench developing hotspots. Several industrial reactors
are operated under liquid-limited conditions at high
pressure and su!er from maldistribution of the liquid
reactants, which can cause externally dry or even inter-
nally completely dry catalyst pellets. One of the options
to overcome this is to operate at high liquid and gas mass
velocities, under pulsing #ow regime, where a signi"cant
improvement in catalyst wetting and e!ective removal of
hot spots has been reported (Blok and Drinkenburg,
1982). However, operation in the pulsing regime is not
always practical in industrial reactors due to a large
pressure drop and little control over the slugging process.
Periodic #ow modulation with a low base #ow and
a periodic slug of very high liquid #ow (referred to as
BASE}PEAK #ow modulation) can improve catalyst
utilization even at low mean liquid #ows (lower pressure
drop) and still achieve temperature and #ow control due
to arti"cially induced pulses (or slugs). No study has been
reported in the open literature on periodic operation
using liquid-limited reactions in laboratory reactors.
Some industrial processes do employ periodic localized
quenching of hot spots by injection of cold #uids at
multiple axial locations into the reactor (Yan, 1980).
It is evident from the discussion of the studies available
in the literature and their limited range of reaction condi-
tions (summarized in Table 1) that a comprehensive
study of unsteady-state operation of trickle beds over
2587
a wide range of parameters and operating conditions is
not yet available. This study focuses on establishing the
e!ect of key parameters, such as extent of gas and liquid
limitation, total cycle period, cycle split (fraction of the
cycle period with liquid ON), and liquid mass velocity on
the performance of trickle-bed reactors operated under
liquid #ow modulation.
3. Experimental
The reaction system chosen for this study is the hydro-
genation of alpha-methylstyrene to iso-propyl benzene
(cumene). This reaction has been used widely as a bench-
mark in trickle-bed reactor studies at atmospheric as well
as elevated pressures (Satter"eld and Roberts, 1968; El-
Hisnawi et al., 1982; Khadilkar et al., 1996). The advant-
age is that a single product is formed with well-known
kinetics. The high-pressure packed-bed reactor facility
used in this study consists of four main components, the
reactor section, the gas and liquid delivery system, the
gas}liquid separator, and the #ow modulation system
(Fig. 1a). The liquid delivery and periodic #ow modula-
tion were obtained by using a set of solenoid valves and
timers connected to a pressurized liquid delivery tank
(Fig. 1b). A detailed description of the setup can be found
elsewhere (Al-Dahhan and Dudukovic, 1995; Khadilkar
et al., 1996). The catalyst (0.5% Pd on alumina spheres)
was packed to a height of 26 cm (with glass beads on both
sides to a total height of 59 cm) and reduced in situ (to
avoid contact with moisture and oxygen). The bed was
prewetted and operated for several hours until a constant
activity was achieved. Since the activity varied slightly
between runs, steady-state test runs were performed be-
fore and after each set of unsteady-state runs to ensure
reproducibility of the catalyst activity in each set. a-
methylstyrene (99.9% purity) in hexane (ACS grade,
99.9% purity) was used as the liquid phase. Pure hydro-
gen (prepuri"ed, industrial grade) was used as the gas
phase. The reactor was operated under adiabatic condi-
tions. Liquid samples were drawn from the gas}liquid
separator after steady state was reached at each liquid
#ow rate. The samples were analyzed by gas chromatog-
raphy (Gow Mac Series 550, with a thermal conductivity
detector) from which the steady-state conversion of
a-methylstyrene was determined. Unsteady-state conver-
sion was determined by evaluating the concentration of
a liquid sample collected over multiple cycles to get the
#ow average concentration. The reproducibility of the
data was observed to be within 3%. The ranges of operat-
ing conditions investigated are presented in Table 2. The
feed concentrations and operating pressures were chosen
so as to examine both gas- and liquid-limited conditions
(as evaluated by the availability of the reactants at the
catalyst sites determined by the c parameter (c "D C /
C
D C* )). This criterion evaluates reactant limitation in
C 
2588 M.R. Khadilkar et al. /Chemical Engineering Science 54 (1999) 2585}2595

Fig. 1. (a) Experimental setup for unsteady-state #ow modulation experiments. (b) Flow arrangement and operating sequence for ON}OFF and
BASE}PEAK operation.

the absence of external transport e!ects, implying liquid et al., 1996). The liquid mass velocities were chosen so as
reactant limitation when c(1, and gaseous reactant to cover partial-to-complete external wetting of the cata-
limitation when c'1 (Beaudry et al., 1987; Khadilkar lyst. Both liquid ON}OFF and BASE}PEAK #ow
 M.R. Khadilkar et al. /Chemical Engineering Science 54 (1999) 2585}2595 2589

Table 2
Reactor and operating conditions

Reactor properties Super"cial liquid mass velocity 0.05}2.5 kg/m s

Total length 59 cm Super"cial gas mass velocity 3.3;10\}15;10\ kg/m s
Diameter 2.2 cm
Active catalyst length 26 cm Operating pressure 30}200 psig (3}15 atm)
Feed concentration 2.5}30% (200}2400 mol/m)
Catalyst properties
Active metal 0.5% Pd Feed temperature 20}253C
Catalyst support Alumina Cycle time, q (total period) 5}500 s
Packing shape Sphere Cycle split, p (ON #ow fraction) 0.1}0.6
Packing dimensions 3.1 mm Max. allowed temperature rise 253C

modulation (illustrated in Fig. 1b) were studied over

a range of liquid mass velocities for each set of experi-
ments.

4. Results and discussion

4.1. Performance comparison for liquid yow modulation

under gas- and liquid-limited conditions

Performance comparison experiments were conducted

for the two cases of interest: (i) gas reactant limitation,
and (ii) liquid reactant limitation, obtained by changing
operating pressure and feed concentration (Wu et al.,
1996). Performance under unsteady-state operation was
obtained by evaluating the #ow-averaged conversion
over several cycles of operation according to the proced-
ure outlined in the previous section. Based on several
trial runs, a total cycle time of 60 s and a cycle split of 0.5
was chosen for this set of experiments with liquid
ON}OFF #ow (see Fig. 8 for liquid mass velocities cor-
responding to the space times investigated). Under near
liquid-limited conditions (i.e., high pressure and low feed
concentrations, c(4) no enhancement is observed with
this modulation strategy (as shown in Fig. 2a), except at
very low liquid mass velocities (high mean space times
("< /Q (mean)). At low space times (high mass velocity,
0 *
Fig. 2a), conversion enhancement is not seen under la-
boratory conditions as a result of several factors such as
small reactor diameter and good distribution which
yields good catalyst wetting (as seen in Fig. 8). The
conditions investigated in the present experiments cor- Fig. 2. (a) Comparison of steady- and unsteady-state performance
respond to fairly high liquid hourly space velocities under near-liquid-limited conditions (c(4). (b) Comparison of steady-
(LHSV"3600*Q (mean)/< ) in comparison with in- and unsteady-state performance under gas-limited conditions (c"25).
* 0
dustrial trickle beds, where maldistribution may be more
pronounced. LHSV varied from 3 to 15 in our experi-
ments as compared to 1.5 to 5 used in industrial reactors. combination of the ON and OFF #ows which lies below
This can be qualitatively seen by examining the shape of the contacting e$ciency curve. Hence, theoretically bet-
the catalyst wetting e$ciency (contacting e$ciency) ter performance is expected under steady-state condi-
curve (Fig. 8) obtained by correlation (El-Hisnawi, 1982). tions. This analysis can not however be applied at low
The concavity of this curve to the abscissa indicates liquid mass velocity where the unsteady-state wetting
better catalyst wetting at the mean #ow than at any linear and replenishment of stagnant liquid pockets with fresh
2590 M.R. Khadilkar et al. /Chemical Engineering Science 54 (1999) 2585}2595

liquid reactants can make enhancement possible. Under

these conditions, the bed is poorly irrigated and the
disadvantage due to reactor-scale liquid maldistribution
(the e!ect of which is not included in steady-state con-
tacting e$ciency plot as shown in Fig. 8) can be
overcome by the high #ow rate liquid pulse in periodic
operation (high space time in Fig. 2a, c(4).
In case of gas-limited conditions (i.e., at low operating
pressures and high liquid reactant feed concentration), it
can be seen that unsteady-state performance (#ow-aver-
aged conversion) is signi"cantly higher than that under
steady-state conditions at all space times (Fig. 2b,
c&25). This case illustrates the conditions of a liquid-full
catalyst and enhanced supply of the gaseous reactant (in
the liquid OFF cycle) leading to better performance. This
enhancement improves as the extent of partial wetting is
increased, as seen at higher space times (lower liquid
mass velocities). This also corroborates the "ndings of
Lange et al. (1994) and Castellari and Haure (1995) that
enhancement is feasible under mild-to-severe gas reac-
tant limitation (50% (v/v) and 100% pure liquid react-
ants respectively were used in their studies). Castellari
and Haure (1995) explored this enhancement further by
increasing the total cycle time to allow complete internal
drying, gas-phase reaction and corresponding large tem-
perature rise resulting in semirunaway conditions. This
was not feasible in the present study whereby further
enhancement is possible due to higher gaseous reactant
supply and lower liquid ON times. It must be noted that
a small exothermic contribution was also observed
during unsteady-state operation with maximum bed tem-
peratures reaching &63C higher than steady-state tem-
peratures.

Fig. 3. (a) E!ect of cycle split (p) on unsteady-state performance under

4.2. Ewect of modulation parameters (cycle split and cycle gas-limited conditions (c"25). (b) E!ect of total cycle period (q) on
unsteady-state performance under gas-limited conditions (c"25).
period) on unsteady-state performance

To explore whether further performance enhancement
(the increase in the #ow-averaged conversion in compari-
son with the steady state) is achievable (for the gas
reactant limited case) by increasing gaseous reactant sup-
ply to the catalyst, the cycle split (r) was varied to vary
the ratio of the gas-to-liquid access times at a constant
mean liquid mass velocity (space time"660 s,
¸"0.24 kg/m s). It can be seen (in Fig. 3a) that further
enhancement was indeed possible as cycle split was
lowered from steady state (p"1) to a value of p"0.25,
the performance improved by as much as 60% over
steady state at the same mean liquid mass velocity
(Fig. 3a). This improvement continues up to the point
where liquid limitation sets in at very low cycle split
(indicating that the liquid is completely consumed in
a time interval less than the OFF time of the cycle),
beyond which the performance will be controlled by
liquid reactant supply. This implies that performance can
be maximized by choosing an appropriate cycle split
(at a given liquid mass velocity and total cycle period).
The e!ect of the total cycle period was investigated at
the cycle split (p) value of 0.33, where performance en-
hancement was observed to be signi"cant (&47%,
Fig. 3a). The performance enhancement is seen to in-
crease with total cycle period up to a maximum, after
which it drops to near (or below) steady-state values
(Fig. 3b). Similar behavior was observed both by Lange
et al. (1994) and Haure et al. (1990) in their reaction
systems. A qualitative explanation for this phenomenon
can be deduced on the basis of their observations and the
present data. At low cycle periods the liquid reactants are
supplied at shorter time intervals than needed for their
consumption by the gaseous reactants leading to aggra-
vation of the gas limitation (or gas reactant starvation).
At large cycle periods (for the same cycle split), opposite
behavior is seen due to longer gas access time than is
 M.R. Khadilkar et al. /Chemical Engineering Science 54 (1999) 2585}2595
necessary to consume liquid reactants (liquid reactant
starvation). Castellari and Haure (1995) have examined
the e!ect of very large cycle times (up to 40 min) and seen
that the temperature rise initially observed due to large
reaction rates drops o! as liquid starvation sets in at the
end of the long cycle. They have attempted to "nd an
optimum total cycle period based on this maximum
temperature rise (maximum rate due to gas-phase reac-
tion on completely externally and then internally dry
catalyst). Because of the competition between gas reac-
tant starvation at the low cycle periods and liquid reac-
tant starvation at the high ones, a feasibility envelope can
be determined (Fig. 3b) based on which the performance
enhancement can be optimized. The location of max-
imum enhancement depends on the liquid reactant con-
centration as seen from the much higher values of the
maximum enhancement in the experiments of Lange
et al. (1994) (cycle period for maximum enhancement
&7.5 min for &50% v/v of alpha-methylstyrene) under
conditions similar to the present case. This maximum
may be correlated to the c parameter (as de"ned earlier)
evaluated under dynamic conditions whereby the e!ect
of cycle split and liquid mass velocity can be incorpor-
ated. This would be possible if transient variation of
concentration is known via continuous measurements or
using a model to simulate the dynamics. The above
e!ects of cycle split and total cycle period were examined
at a constant liquid mass velocity. Because of the strong
dependence of catalyst wetting and reaction rate (both
steady and unsteady), the dependence of liquid mass
velocity (which can be referred to as the amplitude of #ow
modulation) is important from the point of view of com-
mercial-scale application and is examined next.
4.3. Ewect of amplitude ( liquid mass velocity) on unsteady-
state TBR performance
The feasibility envelope (region where performance
enhancement is possible, Fig. 3b) is strongly dependent
on the relative supply of gaseous and liquid reactants as
discussed in the previous section and observed in litera-
ture (Lange et al., 1994; Haure et al., 1990). Gaseous
reactant access is governed by the extent of wetting
(depending on liquid #ow) and the formation of dry areas
(depending on evaporation). Castellari and Haure (1995)
examined catalyst drying in their experiments, which was
attributed to complete external and internal evaporation
of liquid (until liquid reactant is completely consumed).
However, all of their experiments were conducted at the
same mean liquid mass velocity (&10 times higher than
in the present study) at which the steady-state catalyst
wetting is complete. Since the change in catalyst wetting
due to evaporation in the present study is not large
(compared to Castellari and Haure, 1995) as compared to
that caused by the change in liquid #ow rate with time, it
is important to explore whether the feasibility region can
2591
Fig. 4. E!ect of liquid mass velocity on unsteady-state performance
under gas-limited conditions (c"25).
be altered by changing liquid mass velocity. Two mean
liquid mass velocities were examined, under the condi-
tions when wetting would have the most e!ect (lowest
mass velocity possible, see Fig. 8), at a cycle split of 0.25
by varying the total cycle periods as done previously. The
results presented in Fig. 4 compare normalized enhance-
ment (conversion at unsteady state over that at steady
state). A signi"cantly higher enhancement is observed at
lower mean liquid mass velocity. At a mass velocity of
0.137 kg/m s, a similar feasibility envelope is seen (as in
Fig. 3b) which ends in degradation of performance to
below steady-state values at higher cycle periods due to
depletion of the liquid reactant (liquid starvation as dis-
cussed in the previous section). Lower liquid mass velo-
city allows more time for the liquid reactant supply
(higher mean space times) to the catalyst. This is re#ected
in the shift in the onset of liquid starvation to even higher
total cycle periods (Fig. 4), while the gas starvation side
remains unchanged (compared to that observed in Fig.
3b). The higher maximum enhancement at lower mass
velocity (Fig. 4) clearly indicates the trend towards a pos-
sible limit of maximum enhancement (the limiting case of
zero #ow of liquid reactant and complete conversion).
4.4. Ewect of liquid reactant concentration and pressure on
performance
Two key parameters, which decide the extent of gas or
liquid reactant limitation are liquid reactant feed concen-
tration and operating pressure (Wu et al., 1996). The
combined e!ect of these was discussed earlier for two sets
of steady- and unsteady-state performance data corres-
ponding to the gas-limited and liquid-limited extremes. It
was shown that with the ON}OFF liquid #ow modula-
tion strategy, performance enhancement was possible
under gas-limited conditions (Fig. 2a). The e!ect of
2592 M.R. Khadilkar et al. /Chemical Engineering Science 54 (1999) 2585}2595
Fig. 5. (a) E!ect of liquid reactant feed concentration on unsteady-
state performance under gas-limited conditions. (b) E!ect of operating
pressure on unsteady-state performance under gas-limited conditions.
individual contributions of pressure and liquid reactant
feed concentration under gas-limited conditions needs to
be carefully examined to determine the exact cause}e!ect
relationship in performance enhancement. The e!ect of
liquid reactant feed concentration was examined under
gas-limited conditions by evaluating enhancement at two
feed concentrations (1484 and 2082 mol/m) at di!erent
cycle splits. With increase in gas limitation at higher
liquid reactant feed concentration, we would expect high-
er enhancement as a result of #ow modulation at such
conditions. This was however not observed in the present
case (as shown in Fig. 5a). Since the absolute value of
conversion at higher liquid reactant feed concentrations
is lower (due to gas reactant limitation), the enhancement
seen was not as high, even at lower mean liquid mass
velocity (mass velocity used at the higher liquid reactant
feed concentration was 0.1 kg/m s as compared to
0.24 kg/m s at the lower feed concentration).
The e!ect of operating pressure was examined at con-
stant gas velocity of 5.4;10\ m/s and liquid mass velo-
city of 0.085 kg/m s. Under gas-limited conditions, both
Fig. 6. (a) E!ect of IFM frequency on unsteady-state performance
under gas-limited conditions (p"0.5). (b) E!ect of IFM frequency on
unsteady-state performance under gas-limited conditions (p"0.2, 0.5).
steady and unsteady performance improves with increase
in pressure as expected (due to enhanced solubility at
elevated pressures). This enhancement diminishes as
liquid-limited conditions are approached at further in-
creased pressures, especially at liquid mass velocities at
which the bed irrigation is complete (under laboratory
conditions). The liquid mass velocity used was fairly low
in this particular case, hence the performance enhance-
ment was seen even at the highest pressure studied
(Fig. 5b).
4.5. Ewect of induced yow modulation (IFM) frequency on
unsteady-state performance
Liquid ON}OFF #ow modulation can be considered
as square wave cycling about the mean #ow for the case
with a cycle split of 0.5. Conversion under periodic condi-
tions can then be used to examine the dominant time
scales a!ected by (induced) #ow modulation (IFM)
by examining the frequency (u) dependence of #ow-
averaged conversion. The use of the term induced #ow
 M.R. Khadilkar et al. /Chemical Engineering Science 54 (1999) 2585}2595 2593

modulation is done so as to di!erentiate it from natural

#ow modulation (natural pulsing) and the frequency ef-
fects associated with it, which is not the subject of this
study. Fig. 6a and b shows performance enhancement as
a function of the IFM frequency for a di!erent set of feed
conditions with similar trends of the frequency depend-
ence seen at di!erent pressures, feed concentrations, and
even for a case of non-square wave pulsing (p"0.2). The
performance in both cases shows degeneration of the
enhancement at low frequencies tending to the steady-
state operation at zero frequency. But as frequency is
increased, the conversion reaches a clear maximum im-
provement point. Ritter and Douglas (1970) observed
similar frequency dependence (in dynamic experiments
on stirred tanks) and attributed the maximum to the
resonance frequency of the rate controlling process. All
transport processes typically have a natural frequency
corresponding to their characteristic time scale.
Gas}liquid transport in trickle beds corresponds to Fig. 7. Unsteady-state performance with BASE}PEAK #ow modula-
0.2}0.8 Hz (at low pressures), liquid}solid transport cor- tion under liquid-limited conditions (c(1.2).
responds to 0.5}2 Hz, whereas catalyst level reaction-
di!usion processes correspond typically to much lower
frequency (larger time scale) depending upon intrinsic
rates in pellets. Typical hydrogenation reactions in indus-
trial trickle-bed reactors have been reported to corres-
pond to a frequency range of 0.01}0.1 Hz (Wu et al.,
1995). Natural pulsing occurs in trickle beds at high
liquid #ows and displays frequencies of 1}10 Hz, at which
external transport is signi"cantly enhanced (Blok and
Drinkenberg, 1982; Wu et al., 1995). The present IFM
frequencies are much lower than those corresponding to
natural pulsing. The frequency dependence of the reactor
performance (Fig. 6a and b) shows that the highest e!ect
of IFM can be observed at low frequencies (u&0.1 Hz)
at which catalyst-level processes could be predominantly
a!ected resulting in the observed enhancement. Some
e!ect on external transport processes can also be seen (in
Fig. 6a and b) with some enhancement observed corres-
Fig. 8. E!ect of liquid mass velocity on steady-state liquid}solid con-
ponding to their natural frequencies. This opens up the
tacting e$ciency.
possibility of selectivity enhancement and control for
complex reaction schemes by controlling reactant supply
by the proper choice of the IFM frequency for the desired 4.6. Ewect of BASE}PEAK yow modulation on perfor-
reactant (Wu et al., 1995). The low enhancement seen at mance
both ends (uP0 and uPR) can be explained on the
basis of the frequency analysis done by Lee and Bailey For the case of liquid-limited conditions (i.e., at high
(1974). The low IFM frequency limit (uP0) corresponds pressure and low feed concentrations) complete absence
to an equilibrium state or pseudosteady state, where of liquid during the OFF part of the cycle (as done in
the reaction transport processes have time to catch up ON}OFF #ow modulation) is not bene"cial, as this
with the modulated variable (#ow in this case) and the would worsen the liquid limitation. This was con"rmed
overall system behaves as a combination of discrete in the present study (in Fig. 2a) and in experiments of
steady states. On the other hand, at the high IFM Lange et al. (1994). Instead of the conventional ON}OFF
frequency limit (uPR), the input #uctuations are so liquid #ow, a low base #ow of magnitude similar to the
rapid that none of the reaction}transport processes in mean operating #ow with a periodic high #ow slug is
the system can respond fast enough to the IFM, and, no introduced (Gupta, 1985; Lange et al., 1994). This high
gain in performance due to the modulated variable is #ow rate liquid can improve liquid distribution and open
feasible. up multiple #ow pathways for the liquid to #ow during
2594 M.R. Khadilkar et al. /Chemical Engineering Science 54 (1999) 2585}2595
the rest of the cycle. The cycle split (p) here is the fraction
of the cycle period for which the high #ow rate slug is on
(typically chosen to be very short, p"0.01}0.2). Tests
were conducted at a cycle split of 0.1 and cycle times
varying from 30 to 200 s at an operating pressure of
150 psig and low liquid reactant feed concentration
(C "784 mol/m) to ensure (near) liquid-limited
+1 
conditions. This strategy is shown to yield some improve-
ment over steady-state performance (Fig. 7, c(1.2), al-
though this enhancement is not as high as observed
under gas limitation. The maximum enhancement ob-
served here was 12% as compared to 60% under gas-
limited conditions. This limited enhancement is primarily
due to good #ow distribution in a small diameter labor-
atory reactor, which would not be the case in typical pilot
or industrial reactors where much higher enhancement
can be anticipated.
5. Conclusions
Unsteady-state liquid #ow modulation (periodic op-
eration) was investigated for a hydrogenation test
reaction under gas- and liquid-limited conditions. Perfor-
mance enhancement under gas-limited conditions (with
ON}OFF #ow modulation) was observed to be greater
when gas supply is enhanced, i.e., at lower space time and
lower cycle split. Maximum enhancement of about 60%
was possible with a cycle split of 0.25 at the lowest liquid
mass velocity (0.068 kg/m s) under gas-limited condi-
tions. The enhancement-cycle period data showed a max-
imum at all the liquid #ow rates examined, indicating
competition between the gas- and liquid-phase reactants
on either side of the maximum. Performance enhance-
ment under liquid-limited conditions was observed only
with BASE}PEAK #ow modulation and seen to be pos-
sible only under poorly irrigated conditions (low mean
liquid mass velocity) in the trickle bed. Performance en-
hancement was shown to be a strong function of
the induced #ow modulation (IFM) frequency and in-
dicative of the natural frequency of the governing pro-
cess. Further experiments are necessary to investigate
this e!ect to obtain insight into the cause of enhancement
under a wide range of operating conditions, particularly
when the rate controlling processes are di!erent. Test
simulation results are underway to demonstrate the dy-
namic access of gaseous and liquid reactants in a typical
cycle period. Quantitative comparisons of the model
predictions with the experimental data will facilitate bet-
ter understanding of the underlying phenomena, and are
being pursued in our laboratory.
Acknowledgements
The authors acknowledge the "nancial support of the
industrial sponsors of the Chemical Reaction Engineer-
ing Laboratory (CREL) and Engelhard Corporation for
the palladium catalyst used in this study.
Notation
C alpha-methylstyrene concentration
+1
C*(H ) saturation concentration of hydrogen

D e!ective di!usivity, m/s
C
G mass velocity of gas, kg/m s
¸ mass velocity of liquid, kg/m s
P operating pressure, psig
Q ,Q volumetric #ow rate of liquid, gas
* %
<,< super"cial velocity of liquid, gas
* %
< reactor volume, m
0
X(ss) steady-state conversion
X(us) unsteady-state conversion
Greek letters
c reactant limitation criterion
("D C /D C* )
C+1 +1  e (H ) (H )
q total cycle period, s
p cycle split (see Fig. 1b for de"nition)
u #ow modulation frequency, Hz
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