Cyclic operation of trickle bed reactors: A review

Arnab Atta
a,b
, Shantanu Roy
a
, Faal Larachi
a,c
, Krishna Deo Prasad Nigam
a,n
a
Department of Chemical Engineering, Indian Institute of Technology Delhi, New Delhi 110 016, India
b
Department of Chemical Engineering, Indian Institute of Technology Kharagpur, Kharagpur 721302, India
c
Department of Chemical Engineering, Universit Laval, Qubec, Canada G1V 0A6
H I G H L I G H T S

We present a concise review on cyclic operation of Trickle Bed Reactors.

Potential applications of its various modes of operation are discussed.

We emphasis on shock wave attenuation that originates during ow modulation.

Scopes for future research are outlined considering process intensication of TBR.
a r t i c l e i n f o
Article history:
Received 16 April 2013
Received in revised form
16 July 2013
Accepted 17 August 2013
Keywords:
Trickle bed reactor
Cyclic operation
Onoff
Minmax
Process intensication
Shock wave attenuation
a b s t r a c t
Familiarized with the steady state behavior and advantages of the trickle bed reactors (TBR), for the past
two decades, researchers and process engineers are continuously exploring the unsteady state hydro-
dynamics of periodically (or cyclic) operated trickle bed reactors to extract even more from its efciency
and performance. Despite its complicated nonlinear behavior that attributes to the process control safety
at the commercial scale, cyclic operation of TBR is a promising process intensication technology that has
immense potential for implementation on industrial TBR. In this paper, we have summarized and
reviewed the research and progresses made in recent years on cyclic operation of TBR and potential
applications of various mode of its operation. Several issues associated with its hydrodynamics scale-up
and designs have been discussed with an emphasis on shock wave attenuation that arises during ow
modulation.
& 2013 Elsevier Ltd. All rights reserved.
1. Introduction
Trickle bed reactor (TBR) is one of the classical multiphase packed
bed reactor congurations that nds extensive application in petro-
leum industries for the purpose of hydrocracking, hydrotreating, and
alkylation (Saroha and Nigam, 1996). TBRs are also commercially
utilized in the petrochemical, and chemical industries for hydrogena-
tion of aldehydes, reactive amination, liquid-phase oxidation, etc.
Recognizing several benets of using TBR, including simplicity in
construction and large production volumes, there is signicant
amount of incentive and motivation involved for further improvement
of its performance from the economic as well as environmental
perspective (Nigam and Larachi, 2005; Charpentier, 2007). Optimiza-
tion of the performance can be accomplished by (a) evolving
process intensifying novel operational methods/techniques, and/or
(b) designing efcient equipment/reactor internals that are potentially
compact, safe, energy-efcient, as well as eco-friendly sustainable
(Stankiewicz and Moulijn, 2000). Cyclic (or periodic/unsteady state)
operation of TBR belongs to the rst category and has gained
considerable attention due to its substantial effect on improved
reaction rate and reactor operational life.
Most of the reactions, encountered in chemical process indus-
tries that are carried out in TBRs, can be broadly categorized as
either limited by liquid phase or by gas phase reactants. In any
case, gaseous reactants must dissolve into and then pass through
the liquid phase to reach the catalyst surface. For sparingly soluble
gaseous reactants, this transport resistance is one of the vital
parameters in inuencing the rector performance. During cyclic
mode of operation, a continuous ow of certain uid phase
contacts other uid stream that is forced to toggle periodically at
the reactor inlet between a low-level (base) and a high-level
(pulse) ow rate. Considerable decrease in transport resistance,
that is desirable for the gas phase limited reactions, can be
achieved by temporal variation of catalyst wetting due to such
liquid feed cycling operation (Boelhouwer et al., 2002b). For liquid
phase limited reactions, the operation of TBR in natural pulsing
Contents lists available at ScienceDirect
journal homepage: www.elsevier.com/locate/ces
Chemical Engineering Science
0009-2509/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ces.2013.08.038
n
Corresponding author. Tel./fax: 91 11 2659 1020.
E-mail addresses: drkdpn@gmail.com, nigamkdp@gmail.com (K.D.P. Nigam).
Please cite this article as: Atta, A., et al., Cyclic operation of trickle bed reactors: A review. Chem. Eng. Sci. (2013), http://dx.doi.org/
10.1016/j.ces.2013.08.038i
Chemical Engineering Science ()
ow regime is most appropriate since complete catalyst wetting
and high solidliquid mass transfer can be achieved; however,
relatively higher supercial liquid/gas velocities (than trickle ow
regime) are associated with higher energy expenses and lesser
conversion due to shorter contact time between phases. As a
trade-off, forced cycling of gas phase feed can be a viable solution
(Xiao et al., 2001).
Despite potential advantages, cyclic operation in TBR at the
commercial scale is seldom exercised, mainly due to its compli-
cated nonlinear hydrodynamic behavior that endangers the pro-
cess control safety. However, advances in meticulous research
including rigorous experiments and comprehensive modeling are
capable of attaining further reliable predictions. Haure et al. (1989)
pioneered the concept of periodic ushing of the bed for the
removal of SO
2
in a TBR, packed with activated carbon. This
process intensication technique eventually resulted in increasing
oxidation rates up to 45%. Since then, several research groups have
mentioned the performance enhancement by practicing different
reactions with various modulation schemes (Silveston and Hanika,
2002; Tuka et al., 2007; Liu et al., 2008). The hydrogenation of
-methyl styrene (AMS) studied by researchers (Lange et al., 1994;
Castellari and Haure, 1995; Gabarain et al., 1997; Lange et al., 1999;
Banchero et al., 2004) has reported an increase in reaction rates
even up to 400% under appropriate condition. An increase in pilot
reactor productivity of styrene hydrogenation by 30% for periodic
operation in comparison with steady state operation has been
reported (Tuka et al., 2007) that can be considered as signicant
achievement for potential industrial applications of cyclic opera-
tion. A summary of few contemporary research works on periodic
operation of TBR is listed in Table 1.
Observing the plausible wide spread use and popularity of cyclic
operation as process intensication technique, this effort is to
summarize the characteristic studies contributed in understanding
this promising area and its present research status. There is a review
article available on periodic operation of all three-phase catalytic
reactors by Silveston and Hanika (2004), and therefore, this study has
been mainly focused on the efforts made in case of only TBR with a
special importance on the hydrodynamic features and applications
thereafter.
2. Flow modulation strategy
During liquid feed cyclic operation, a continuous ow of gas
phase interacts with a liquid stream which is enforced to toggle
periodically at the reactor inlet between a low-level (base) and a
high-level (pulse) liquid ow rate. Similarly, for gas feed cyclic
operation, the liquid phase feed is kept constant while the gas ow
rate is switched. In general, this mode of operation is called as
minmax or basepulse mode. However, when the base or mini-
mum ow rate value is set to zero then it is especially assigned as
onoff mode.
It has been observed that in almost all studies published on
periodically fed TBRs, the specic liquid feed rate is varied in a
square waved pattern and the feed cycle is characterized by four
feed parameters (Fig. 1). The low or base specic liquid feed rate,
u
Lb
, is applied for a duration t
b
, followed by a high or pulse specic
liquid feed rate, u
Lp
, applied for a duration t
p
. There are three key
parameters that are derived as: (i) the feed cycle period (p), (ii) the
split (S), and (iii) the average specic liquid feed rate (u
Lm
) which
can be dened by
p t
b
t
p
1a
S
t
p
t
b
t
p

t
p
p
1b
u
Lm

u
Lb
t
b
u
Lp
t
p
t
b
t
p
1c
It is interesting to note from most of the studies that the ow
regimes during both high and low liquid ow rates are in trickle-
ow regime. Based on the time period applied for the pulse/max
mode ow rate, there also exists slow mode operation, where the
Table 1
Summary of some recent studies on cyclic TBR.
Researchers Modulation
strategy
System studied Reactor dia. and packings Observations
Lange et al. (2004) Onoff, slow
mode
Hydrogenation of
-methyl styrene
ID: 0.02 m, 0.7% Pd=-Al
2
O
3
Reactor performance was signicantly improved by feed
liquid ow modulation
Massa et al.
(2005)
Onoff, slow
mode
Oxidation of phenols ID: 0.021 m, cylindrical
pellets of 2.6 mm size CuO/
Al
2
O
3
catalyst
Mild effect on phenol conversion due to liquid ow modulation was detected
but the ow modulation did not affect product distribution, in the range
of operating conditions studied
Fraguio et al.
(2004);
Muzen et al.
(2005)
Onoff, slow
mode
Catalytic oxidation of
ethyl and benzyl
alcohols
ID: 0.04 m, 3 mm spherical
1% Pd=-Al
2
O
3
Conversion was improved for different combinations of cycle period and
split. Depending on liquid reactant and operating variables, both positive
and detrimental effects of the liquid ow modulation were observed
Liu et al. (2005);
Liu and Mi
(2005)
Onoff, slow
and fast mode
Hydrogenation of
2-ethylanthraquinone
ID: 0.021 m, 1.9 mm spherical
0.5% Pd=-Al
2
O
3
Improvement in conversion and selectivity up to 21% and 12%, respectively,
was found. A transient model involving axial dispersion, partial wetting, and
drainage behaviour was developed
Liu et al. (2008) Onoff, min
max, hybrid
mode
Hydrogenation of
dicyclopentadiene
ID: 0.024 m, 1.9 mm 0.3%
Pd=-Al
2
O
3
egg-shell catalyst
A novel operation strategy of trickle bed reactor, hybrid modulation of liquid
ow rate and concentration was proposed. The performance enhancement
under the hybrid modulation was higher (15%) than the minmax
modulation of single parameter
Schubert et al.
(2010)
Onoff, slow
mode
Hydrodynamics of
airwater ow
ID: 0.10 m, 3.24 mm
spherical -alumina particles
Time-averaged liquid saturation decreased in slow mode operation,
particularly at small splits and long period length. Unlike previous studies,
improvement of the liquid distribution was not detected
Ayude et al.
(2012)
Onoff, slow
mode
Catalytic oxidation
of ethanol
ID: 0.0254 m, 2.7 mm 0.5%
Pd=-Al
2
O
3
egg-shell catalyst
Product distribution was signicantly adjusted by frequency tuning. High
frequency liquid ow modulation increased selectivity towards the
intermediate product, however, low frequency led to catalyst deactivation
Wongkia et al.
(2013)
Onoff, slow
and fast mode
Hydrogenation of
styrene
ID: 0.0191 m, 2 mm spherical
0.3 wt% Pd=-Al
2
O
3
Fast mode was found favourable. A maximum improvement of styrene
conversion of 18% was observed
A. Atta et al. / Chemical Engineering Science () 2
Please cite this article as: Atta, A., et al., Cyclic operation of trickle bed reactors: A review. Chem. Eng. Sci. (2013), http://dx.doi.org/
10.1016/j.ces.2013.08.038i
phase feed changes periodically over few-minutes time spans, and
fast mode operation, where the feed pulse incursion lasts for a
few-seconds (Aydin et al., 2006; Hamidipour et al., 2007).
Continuity shock waves may appear as a result of uid
accumulation in a ow channel depending on its ow rate
variation (Wallis, 1969). Boelhouwer et al. (2002a) reported that
liquid feed ow rate modulations result in formation of liquid-rich
continuity shock waves that propagate down the bed. It is
apparent from the experimental analysis (Boelhouwer et al.,
2002a) that these shock waves also diminish by leaving liquid
behind their tail while moving down the reactor. At sufciently
high gas ow rates, inception of pulses may occur within the
liquid-rich shock waves that can be referred as liquid-induced
pulsing ow. The frequency of the pulses during fast mode of
liquid-induced pulsing ow is usually less than 1 Hz. Giakoumakis
et al. (2005) redened a clear demarcation between various mode
of induced pulsing. Based on the measure of the existence of at least
one pulse in the packed bed, at any time, Giakoumakis et al. (2005)
mentioned that when the characteristic time period of a pulse is
bigger than the ratio of reactor height and pulse rapidity, it will be
referred as slow mode operation. Giakoumakis et al. (2005) also
mentioned that at substantially smaller frequencies compared to
limiting case, the bed can operate at a liquid-rich and a gas-rich
state, interchangeably. According to their study, apart from the
temporal and spatial holdup variations, a typical feature of slow
mode operation is noticeable pressure drop uctuations, whereas
in case of fast mode operation, the pressure drop over the bed
remains almost unchanged (Giakoumakis et al., 2005).
2.1. Onoff mode
There are numerous studies on the onoff mode operation to
unveil the transient behavior of cyclic TBR. Giakoumakis et al.
(2005) experimentally characterized several parameters of
induced pulses namely, its evolution, holdup, pressure drop, pulse
intensity and celerity for fast mode cycling operation in a cylind-
rical bed of 0.14 m inner diameter. With the help of conductivity
probes for measuring liquid holdup, they analyzed axial propaga-
tion and attenuation of the induced liquid pulses. In line with the
study of Boelhouwer (2001), their study also recognizes the
varying shape of induced pulses and its decay down the length
of the bed (Fig. 2).
In order to distinguish between slow and fast mode of operations,
Giakoumakis et al. (2005) highlighted that considerably larger
amount of liquid holdup than the static holdup of the packed bed
was found during fast mode. This phenomenon was ascribed to the
greater characteristic time of drainage of the bed compared to the
pulse periodicity at the inlet that results into liquid accumulation in
the bed in between two consecutive pulses. Such fast mode operation
was further examined by Trivizadakis et al. (2006) in an identical
experimental setup to study the particle shape and size effects on
pulse characteristics (Fig. 3). Considering widely used catalyst parti-
cles in TBR applications, Trivizadakis et al. (2006) selected two
different types of porous alumina particles (3 mm spheres and
1.5 mm dia. cylindrical extrudates) along with 6 mm glass beads for
the comparative study.
From Figs. 2 and 3, it can be observed that liquid holdup traces
displayed similar trends for same kind of particle shape (e.g.,
6 mm and 3 mm glass spheres). In the case of cylindrical extru-
dates, the liquid holdup traces completely faded even before
reaching the bottom of the bed. For both spherical and extrudate
particles, Trivizadakis et al. (2006) also indicated that during fast
mode of onoff liquid pulsing, total liquid holdup (i.e. sum of
dynamic and static holdup) was always higher than the static
liquid holdup. This, in turn, implies that chances of liquid dry-out
phenomena can be minimized by fast mode of operation as there
will be always ample liquid in the bed at all the time of pulses.
Time
L
i
q
u
i
d
f
e
e
d
r
a
t
e
t
p
t
b
u
Lp
u
Lb
Fig. 1. Schematic of the cyclic liquid feed. u
Lb
base liquid feed; u
Lp
pulse liquid
feed; t
b
duration of base liquid feed; t
p
duration of pulse liquid feed.
Fig. 2. Typical simultaneous liquid holdup traces (gure reprinted from Giakoumakis et al., 2005 with permission from the publisher, Elsevier). The packing material is glass
spheres of 6 mm diameter and the ow rates are G0.22 kg m
2
s
1
, L3.34 kg m
2
s
1
. Cycle frequency0.167 Hz (3 s on3 s off).
A. Atta et al. / Chemical Engineering Science () 3
Please cite this article as: Atta, A., et al., Cyclic operation of trickle bed reactors: A review. Chem. Eng. Sci. (2013), http://dx.doi.org/
10.1016/j.ces.2013.08.038i
Trivizadakis et al. (2006) further claimed that the trend of liquid
holdup traces is similar for several operating conditions including,
liquid cyclic feed frequency and mean uid ow rates. However,
due to smaller pressure drop and rate of pulse attenuation,
spherical packings can hold signicant advantages over cylindrical
extrudates of comparable size.
To recognize the effect of porous packings on pulse attenuation due
to liquid ow modulation, Ayude et al. (2007b) extensively studied the
temporal variations of the liquid holdup at different axial positions in a
mini-pilot scale TBR (of inner diameter 0.07 m), packed with porous
beads of -Al
2
O
3
. Using a conductometric technique, Ayude et al.
(2007b) analyzed liquid holdup modulation for different supercial
velocities, bed depth and cycling parameters. For a square wave input
of liquid feed, slightly deformed structure of the wave was found
down the bed length during slowmode operation. These structures, as
it moved along the column length, had different trends of decay that
occurred during the dry period of the ow modulation (Ayude et al.,
2007b). Furthermore, a decrease in the width of plateau was also
realized during the wet period of the ow modulation. In case of fast
mode onoff operation, the structure of input pulse deteriorates
severely and eventually becomes at at the lower part of the bed
representing a pseudo steady state (Ayude et al., 2007b). Moreover, it
was realized that the mean liquid velocity determined the pulse
intensity in the bed. In case of lowmean liquid velocity, pulse intensity
can only be realized near the feed inlet and diminishes to zero down
the length of the bed. However, in case of a higher mean velocity,
there is a continuous decrease in pulse intensity along the bed length
and can be appreciated even at the bottomof the column (Ayude et al.,
2007b).
Banchero et al. (2004) experimented the efcacy of onoff fast
mode liquid modulation in a TBR, of 0.04 m inner diameter, packed
with Pd/C catalyst for -methyl styrene hydrogenation (AMS). This
study disclosed that cyclic operation can improve the conversion
rate up to 60% compared to the steady state operation for any
particular operating condition. Because the experiments were
executed in isothermal conditions, this conversion rate improve-
ment clearly advocates the utility of periodic operation that led to
increased mass transfer.
Ayude et al. (2008) discussed the effect of onoff liquid ow
modulation on the oxidation of ethanol in a lab-scale TBR having
internal diameter of 0.0254 m. For a varied set of uid ow rates,
cycle periods and splits, experiments were carried out to compare
the performance with the steady-state experiments. Fig. 4 shows
substantial improvements ( 30%) in catalyst activity with larger
split for any xed period of modulation. This study also revealed
that enhancement in reaction rate was favored during relatively
fast mode of liquid feed cycling (i.e. shorter off period).
It has been observed that experiments to unravel the hydro-
dynamics characteristics were scarcely reported in case of gas feed
modulation. In fact, there are very few literature available dealing
with gas feed modulation. One of the main reasons behind this can
ascribe to the fact that compared to the liquid phase, the inertia
effect due to gas phase modulation is considerably small which
does not help in damping of the oscillation (Banchero et al., 2004).
Nonetheless, with a different feed modulation strategy than the
conventional type operation, Larruy et al. (2007) tested gas feed
modulation instead of liquid ow modulation (Tuka et al., 2003;
Massa et al., 2005) in catalytic wet air oxidation (CWAO) of phenol.
They studied the possibilities of reducing active carbon burn-off
using gas ow and composition modulation in a small TBR of
0.011 m internal diameter. It was demonstrated that modulation of
gas feed composition was essentially advantageous for CWAO of
phenol due to considerable reduction in active carbon burn-off
compared to steady state operation. Larruy et al. (2007) further
showed that gas feed modulation with high splits was very
attractive for preserving catalyst activity in long term.
Later, Ayude et al. (2007a) added to this observation with
extended experimental study in a similar reactor setup to analyze
the impact of gas feed composition and ow rate modulation on
the short time activity of the catalyst through 50 h of operation.
Fig. 5 depicts the signicant result of this study. It shows that
nearly same conversion rates of phenol and total organic carbon
(TOC) can be achieved by either gas feed composition or ow rate
modulation. However, the temperature proles are different in
both cases (Ayude et al., 2007a). From the perspective of
Fig. 3. Typical, simultaneously recorded, liquid holdup traces along the packed bed
(gure reprinted from Trivizadakis et al., 2006 with permission from the publisher,
Elsevier). The ow rates are G0.12 kg m
2
s
1
, L3.34 kg m
2
s
1
. Cycle fre-
quency0.167 Hz (3 s on3 s off). (a) 3 mm spheres, (b) 1.5 mm dia. extrudates.
Fig. 4. Enhancement as a function of split for different periods (9, 6 and 3 min),
(gure reprinted from Ayude et al., 2008 with permission from the publisher,
Elsevier). V
L;ss
70 mL min
1
; V
G
200 mL min
1
.
A. Atta et al. / Chemical Engineering Science () 4
Please cite this article as: Atta, A., et al., Cyclic operation of trickle bed reactors: A review. Chem. Eng. Sci. (2013), http://dx.doi.org/
10.1016/j.ces.2013.08.038i
commercial application, such results are extremely appealing
because consumption of nitrogen can be minimized which in turn
also reduces operating costs.
All these studies proved the effectiveness of periodic gas phase
modulation in CWAO of phenol, compared to steady state oxida-
tion with proper selection of cycling parameters, i.e. split and
period. Higher splits and cycle periods were found to be highly
benecial to the catalyst activity in CWAO of phenol. Ayude et al.
(2007a) disclosed that mean conversion rate in phenol CWAO can
signicantly be enhanced (from 35% to 60%) by gas feed cycling
with suitable split and period of modulation.
Researchers argue that periodic liquid feed modulation can
minimize liquid maldistribution in the TBR which is an inherent
advantage of the cyclic operation of TBR. With a state-of-art
noninvasive multiphase ow visualization technique, Electrical
Capacitance Tomography (ECT), Liu et al. (2009) demonstrated
this fact while analyzing the transient behaviors of the liquid
holdup of airkerosene system in a periodically operated TBR, of
0.14 m internal diameter, packed with spherical glass particles.
They captured instantaneous ECT images at several axial positions
of a TBR modulated with the slow mode onoff operation.
Furthermore, the transient radial liquid distributions and a mal-
distribution factor were computed from those ECT images to
estimate the liquid distribution under periodic modulation. Their
study revealed that liquid maldistribution generally occurred
during the draining period and more appreciable at the top section
of the bed. This study manifests further investigations using
noninvasive process tomography in cyclic TBR considering the
limitations of intrusive measurement techniques such as conduc-
tometric technique for determining local liquid-holdup and radial
distributions that are prevalent for industrial applications.
2.2. Minmax mode
There are relatively limited amount of literature available on
the peakbase or minmax mode of operation than onoff mode
of operation. Urseanu et al. (2004) examined the use of periodic
liquid feed modulation in a high pressure TBR which is very
relevant from the standpoint of industrial application of cyclic TBR.
They studied the effect of minmax periodic operation on the
reaction rate in hydrogenation of -methyl styrene (AMS) to
cumene in a TBR of 0.051 m diameter. Their results showed an
increase of at least 50% in reaction rate for the case of periodic
operation compared to steady state operation. Fig. 6 shows the
temperature prole of the liquid with the corresponding situation
of liquid feed velocity. It can be observed from Fig. 6 that during
the ushing of the bed with liquid, the temperature of liquid
increased as it effectively removed the heat from the catalyst.
In an attempt to compare and quantify the liquid maldistribu-
tion during onoff and minmax operation, Borremans et al.
(2004) came up with the remarks that for the very limited number
of operating conditions, periodic operation was not able to
improve the liquid distribution compared to steady state case in
a TBR with 0.3 m diameter. In these operating conditions, the
maldistribution factors had their minimum values in steady state
operation, signifying best possible distribution that could have
been achieved. They argued that for periodic operation, better
distribution can be achieved in cases of lower mean liquid ow
rates and by setting base liquid ow velocity to zero i.e. by onoff
operation. Borremans et al. (2004) also indicated that cyclic
modulation of liquid feed can ensure better liquid distribution in
the conditions that are close of pulsing regime under steady state
operation.
Considering the advantage of shock wave formation during ow
rate modulation, Hamidipour et al. (2007) applied minmax opera-
tion to reduce nes deposition that helped to prolong reactor
operational life under ltration conditions of a TBR. In order to
examine the efciency of the shock waves in delaying solids
re-deposition, Hamidipour et al. (2007) studied several modes of
operation, namely, slow-, fast- and semi-fast liquid cyclic operation,
fast-mode gas cyclic operation, alternating gas/liquid cyclic opera-
tion including the effects of cycle time, split ratio and bed height in
Fig. 5. Temperature, phenol and total organic carbon (TOC) conversion proles with time for different gas phase modulations. Filled and empty symbols represent phenol
and TOC conversion, respectively. (Figure reprinted from Ayude et al., 2007a with permission from the publisher, Elsevier.)
Fig. 6. Adiabatic temperature rise of the liquid phase and supercial liquid velocity
during periodic operation (period480 s; split0.25). (Figure reprinted from
Urseanu et al., 2004 with permission from the publisher, Elsevier.)
A. Atta et al. / Chemical Engineering Science () 5
Please cite this article as: Atta, A., et al., Cyclic operation of trickle bed reactors: A review. Chem. Eng. Sci. (2013), http://dx.doi.org/
10.1016/j.ces.2013.08.038i
a TBR of 0.057 m internal diameter. They concluded that slow- and
fast-mode liquid cyclic operation strategies were not capable of
minimizing deposition and pressure drop. However, a new scheme,
semi-fast mode liquid cyclic operation, dened as minutes-lasting
pulses and seconds-lasting base velocities, was benecial in reducing
bed deposition. Additionally, alternating gas/liquid cyclic operation
was also found to be efcient in reducing deposition.
In an interesting and industry relevant study, contrary to the
previous investigations focusing on liquid induced pulsing ows
that were performed only at atmospheric pressure and ambient
temperature, Aydin et al. (2006) illustrated the effects of tempera-
ture and pressure on the shock wave characteristics of both
Newtonian and non-Newtonian liquids in slow mode induced
pulsing of minmax operation. In a 0.048 m diameter TBR, they
showed reduced decay process in shock waves for increasing
temperature and pressure (Figs. 7 and 8). Aydin et al. (2006) also
demonstrated that the shock wave breakthrough and decay times
decreased with increasing temperature and pressure. Liquid
holdup was also found to decrease with temperature, especially
at the high liquid feed rates. This phenomenon may lead to
reduced reactor performance during liquid induced pulsing ow
at high temperature and pressure operations.
Most recently, Atta et al. (2010) paid attention on the propaga-
tion of a solitary square-wave liquid feed to visualize its behavior,
effect and attenuation in the bed during the minmax operation.
For analyzing the inherent ow dynamics during wave propaga-
tion in a cyclic TBR, experiments for multiphase ow visualization
and local variable measurements using ECT were carried out in
0.057 m diameter TBR. To unveil the behavior and effect of solitary
liquid-rich square-wave on the continuous mode of minmax
periodic operation, two different types of ow modulation had
been examined (slow mode of 60 s and fast mode of 10 s) for
different gas velocities. The effect of gas velocity on the shape of
solitary wave is shown in Figs. 9 and 10 for fast and slow modes,
respectively. The deformation in shape of solitary liquid rich wave
is apparent from these gures. Figs. 9 and 10 also depict the
propagation characteristics of the wave down the column length.
In both the cases, higher gas velocity restricted the upper limit of
liquid holdup and tries to atten the square shape of the wave.
It was evident from all the experiments that the solitary liquid
wave always restricted within the steady state holdups range of
base and pulse velocities in the bed. It had also been observed that
in case of slow mode minmax operation, the liquid rich wave
plateau upheld the steady state liquid holdup value (correspond-
ing to pulse velocity) for sufciently long period even at the
bottom of the column which in turn helped to envisage the
situation as a pseudo-steady state TBR operation. However, in case
of fast mode operation, this plateau just touched the upper limit of
liquid holdup at the bottom of reactor and then starts to decay
within very short duration. The duration of decaying period was
longer in cases of fast mode operation which got prolonged by the
increase in gas supercial velocity. It was also noticed that the rise
of the solitary wave got delayed with the reduction of the gas
supercial velocity. Therefore, in this scenario, it can be antici-
pated that if continuously short (in duration) pulse or liquid rich
wave comes in the bed then there may be chances of pulsing
inside the bed (even at trickle ow regime) which can be treated
as pseudo-natural pulsing during fast mode minmax cyclic
operation. Henceforth, that study suggested that slow mode
operation tried to keep the shock-wave identity intact thus is
benecial for the cases of exothermic gas phase limited reactions
where partial catalyst wetting is more desirable and simulta-
neously hot spot formation occurs. In case of fast mode operation,
0.20
0.15
0.05
0.10
T = 25C
L

0.00
Time (s)
T = 50C
T = 75C
0 50 100 150
Fig. 7. Effect of temperature on shock wave patterns measured 40 cm from bed top,
P0.3 MPa, u
G
0.2 m s
1
. Air-water system, u
Lb
0.0035 ms
1
, u
Lp
0.0105 m s
1
(Aydin et al., 2006).
0.16
0.08
0.12
0.04
L

L
0
Time (s)
P = 0.3MPa
P = 0.7MPa
0 50 100 150
Fig. 8. Effect of pressure on shock wave patterns measured 40 cm from bed top,
T75 1C, u
G
0.2 m s
1
. Airwater system, u
Lb
0.0035 m s
1
, u
Lp
0.0105 m s
1
(Aydin et al., 2006).
Fig. 9. Experimental visualization of solitary liquid wave propagation with time
along the bed length for (a) u
G
0.062 m s
1
and (b) u
G
0.25 m s
1
during fast
mode (10 s) cyclic operation (Atta et al., 2010).
A. Atta et al. / Chemical Engineering Science () 6
Please cite this article as: Atta, A., et al., Cyclic operation of trickle bed reactors: A review. Chem. Eng. Sci. (2013), http://dx.doi.org/
10.1016/j.ces.2013.08.038i
with shorter pulse ow rate time period and higher liquid ow
rate, pseudo-natural pulsing situation can be achieved at the
bottom of the reactor due to its longer decay time.
3. Modeling and simulation
Despite several advantages, commercial cyclic TBR is far from its
application mainly due to process control safety related with the scale
up issues. Highly non-linear hydrodynamics coupled with poor
understanding of the transport processes and reaction kinetics makes
the situation even more involved for unsteady operation of TBR.
In order to demystify the complex behavior, several modeling studies
have been reported in the literature, dealing with both transient and
pseudo-transient models (Lange et al., 1999; Khadilkar et al., 2005;
Dietrich et al., 2005; Ayude et al., 2005a, 2005b; Liu et al., 2008;
Ayude et al., 2009; Brzi et al., 2010). All models basically stem from
the variation of steady state approach and have corresponding
limitation that restricts their use to real unsteady state or periodic
systems. Khadilkar et al. (2005) had comprehensively pointed out the
general limitations of presented reaction models as follows:

Most of the formulations assume plug ow condition in the

bed, thus neglecting any spatial and temporal change in phase
velocity and holdup.

For simplication, most of the models are based on equilibrium

or pseudo-homogeneous condition between reacting phases.
Accumulation terms for non-limiting species have never been
considered.

Thermodynamically ideal uid conditions are assumed for

calculating single component mass transfer terms.

Several models are based on computing reaction and transport

phenomena of only the limiting species, considering constant
concentrations of other species.

Most of the models do not incorporate multi-component

transport between phases.

In some cases, spatial terms on the catalyst level are disre-

garded to simplify computation.
Furthermore, most of those models take partial wetting of
catalyst pellets into account but neglect the role of static liquid
holdup during off period of a cyclic TBR (Liu et al., 2008). Although
nearly 2030% of the total area of the catalyst may be exposed to
stagnant liquid (Rajashekharam et al., 1998), however during off
period of a cyclic operation such exposed area may rise to 7090%
(Liu et al., 2008). Considering aforementioned limitations in the
previously proposed formulations, Liu et al. (2008) suggested a
model involving vaporliquid equilibrium of a complex exother-
mic reaction under unsteady-state operation. They chose hydro-
genation of dicylcopentadiene (DCPD) in the presence of Pd/Al
2
O
3
catalyst as the sample reaction and proposed an unsteady-state
TBR model with the following improvements over their steady-
state model (Liu et al., 2006):

New model incorporated time dependency of species concen-

tration variation in gas phase.

It also included dynamic exposure of the catalyst surface to

pulsing liquid, and temperature of liquid and solid phases.

To estimate the axial liquid holdup proles during liquid ow

modulation, Liu et al. (2008) utilized a nonlinear approxima-
tion of liquid holdup and time.

Moreover, periodic initial conditions were utilized in the new

unsteady state model.
The model, thus formulated, demanded several parameters to be
approximated from the correlations reported in the literature.
Thereafter, this model was solved by the method of lines for
several operation strategies including modulation of liquid ow
rate and/or concentration, and a hybrid modulation of liquid ow
rate and concentration (Fig. 11). Liu et al. (2008) reported an
improvement in hydrogenation rate up to 1020% by the modula-
tion of liquid ow rate in TBR of 0.024 m internal diameter.
In cases of hybrid modulation of liquid ow rate and concentra-
tion, the performance enhancement was higher than the min
max/peakbase modulation of a single parameter. Despite the fact
that only few typical operating conditions for different modulation
strategies were examined, Liu et al. (2008) showcased a promising
modulation strategy for the exothermic reactions through dynamic
modeling.
Regarding, the cold ow hydrodynamics during max/min and
on/off periodic operation, Brkljac et al. (2007) proposed a model
based on the relative permeability concept for predicting two-
phase pressure drop and dynamic liquid holdup. They utilized the
permeability parameters determined under steady-state condi-
tions to model dynamic operation of a TBR. Brkljac et al. (2007)
demonstrated that two-phase pressure drop and dynamic liquid
holdup during max/min periodical operation were better pre-
dicted by the use of the permeability parameters estimated under
the decreasing liquid ow rate mode (i.e. upper branch of the
hysteresis curve). Similarly, hydrodynamic conditions during on
off periodic operation were more closely predicted by the use of
the permeability parameters corresponding to the lower hysteresis
branch. To exhibit the feasibility of process intensication by
Fig. 10. Experimental visualization of solitary liquid wave propagation with time
along the bed length for (a) u
G
0.062 m s
1
and (b) u
G
0.25 m s
1
during slow
mode (60 s) cyclic operation (Atta et al., 2010).
A. Atta et al. / Chemical Engineering Science () 7
Please cite this article as: Atta, A., et al., Cyclic operation of trickle bed reactors: A review. Chem. Eng. Sci. (2013), http://dx.doi.org/
10.1016/j.ces.2013.08.038i
increased gasliquid mass transfer, Borren et al. (2010) presented
an interesting simulation study on gas-limited reaction in a cyclic
TBR that predicted an enhancement in conversion of about 14%
based on the appropriate selection of the operating mode. With
the help of Magnetic Resonance Imaging (MRI) results, Dietrich
et al. (2011) showed that application of actual local liquid dis-
tribution, measured by NMR-tomography, as input to the simula-
tion studies provided more reliable assessment of a cyclic TBR and
its corresponding benet.
Additionally, despite several successful numerical attempts to
model the multiphase ow in TBR operating under steady state
condition, except the study of Janecki et al. (2008), a CFD based
model to track the shock wave attenuation in a cyclic TBR was
seldom reported (Wang et al., 2013). Giakoumakis et al. (2005) and
Kostoglou and Karabelas (2006) discussed the applicability of the
multi-uid model to correlate pulse decay. They concluded that for
their studies (onoff mode), the lack of temporal stability of the
multi-uid closures makes it incapable for tracking the transient
dynamics of the TBR. Janecki et al. (2008) employed this tradi-
tional three-phase Eulerian model along with the closures devel-
oped by Attou et al. (1999) for their studies on minmax operation.
The results from this study encourage accessing the applicability of
drag force models, developed for steady state situations, in case of
cyclic operation. However, the study was unable to provide the
details of rise and falling (or tail) characteristics of a shock wave
inside the bed. Recently, Atta et al. (2010) singled out a solitary
liquid-rich square-wave and studied its propagation phenomena
inside the bed. A two-phase Eulerian model, based on porous
media concept (Atta et al., 2007b, 2007a) had been successfully
employed to examine the exibility and temporal stability of the
CFD modeling approach in case of unsteady operation. This study
also helped in understanding the underlying physics behind the
pulse attenuation during its propagation across the bed. Considering
catalytic wet oxidation as test cases, few studies (Lopes and
Quinta-Ferreira, 2010, 2011; Lopes et al., 2012a, 2012b) reported
the application of a CFD framework embedded with volume-of-
uid (VOF) model to predict the dynamic behavior of a pilot TBR
and to demonstrate the efcacy of periodic operation over steady
state operation.
4. Summary
With the help of periodic operation in a TBR, the mass transfer
rate of the gaseous reactant can be considerably enhanced which
in turn results into higher solubility of gaseous phase in the liquid.
Therefore, for a desired conversion, cyclic TBR can be operated at
fairly lower pressures. Commercially, low pressure operating
conditions can substantially reduce capital and energy costs
(Boelhouwer, 2001). For gas-limited reactions, partial wetting of
catalysts is generally preferred (Boelhouwer, 2001). However, in a
steady state TBR operation, partial wetting leads to severe liquid
maldistribution. To eliminate the risk of bed scale maldistribution
that strongly affects reactor performance, cyclic liquid feed can
result in temporal variations of the catalyst wetting efciency.
Such modulation also minimizes the possibilities of hot spot
formation.
In cases of consecutive reactions, selectivity is the key para-
meter during periodic operation. During the off/base period of
the feed cycle, there are extreme probabilities of the side chain
reactions to the undesired product. Therefore, a faster mode of
Fig. 11. Parameters characterization of periodic operation of TBR. (a) onoff modulation of liquid ow rate; (b) peakbase modulation of liquid ow rate; (c) peakbase
modulation of concentration; (d) hybrid modulation of liquid ow rate and concentration. (Figure reprinted from Liu et al., 2008 with permission from the publisher,
Elsevier.)
A. Atta et al. / Chemical Engineering Science () 8
Please cite this article as: Atta, A., et al., Cyclic operation of trickle bed reactors: A review. Chem. Eng. Sci. (2013), http://dx.doi.org/
10.1016/j.ces.2013.08.038i
feed modulation can prevent the conversion to undesired products
(Boelhouwer, 2001).
For liquid-limited reactions, the ideal operating condition can
arise when there is complete catalyst wetting and the maximum
possible particleliquid mass transfer. Such optimum scenario can
only be achieved in pulse ow regime of any steady state TBR
operation. However, operating in pulse regime will eventually
demand undesirable energy expenses and lesser conversion due to
shorter contact time between phases. In this regard, fast mode of
liquid-induced pulsing ow can considerably decrease the need of
higher liquid ow rates (Boelhouwer, 2001). Furthermore, without
induction of natural pulsing, a relatively slow mode operation may
reduce the risk of hot-spot formation in the bed. Since liquid feed
modulation induces continuity shock waves which try to retain their
identity as it moves along the bed, can act as ushing of the bed.
The plausible advantages of periodic or cyclic operation have
been established by intense exploitation of onoff mode operation.
In this regard, the exploring potentials of minmax operation need
more extensive attention. Interesting characteristics of this mode
have been disclosed in some recent studies (Urseanu et al., 2004;
Borremans et al., 2004; Aydin et al., 2006; Hamidipour et al., 2007;
Atta et al., 2010). Numerous attempts have been demonstrated
focusing the important aspect of pulse attenuation revelation in
the bed over the past 5 years. Utilization of non-invasive measure-
ment technique, e.g. ECT, has considerably enhanced the knowl-
edge behind fundamental physics of transport during several
different modes of operations (Hamidipour et al., 2008, 2009;
Liu et al., 2009; Atta et al., 2010; Hamidipour et al., 2013).
Several mathematical and few numerical models have been
proposed by researchers. Unsteady state model development
incorporating the possible complicated parameters which were
neglected or assumed for model simplication in earlier years,
have been observed over the years. Few CFD studies have been
reported in recent years for cold ow simulation and tracking of
the shock wave attenuation.
5. Recommendations for future studies

Despite having a notion of reduced liquid maldistribution

during cyclic operation, more ow visualization studies should
be directed to strongly establish this fact for different modes of
operations.

Since purposely used cyclic operation can enhance the reactor

performances, innovative hybrid cycling schemes can be
recommended for specic processes.

Although the effect of particle diameter on modes of cyclic

operation has been studied, the effect of larger scale bed
diameters has to be tested thoroughly with an ambition of
commercial utility of the results or predictions.
To realize the inuence of all key parameters while purposeful
usage and designing of a cyclic TBR only by extensive experiments
is emphatically cumbersome and sometimes exceedingly expen-
sive. With the advent of sophisticated instrumentation, increasing
computational power and development of CFD, a sensible and
effective alternative may be the use of CFD based model validated
by comprehensive experimental data set for further investigations.

Considering the feasibility of numerical modeling in case of

only minmax operation, unsteady state CFD models should be
meticulously developed incorporating all possible parameters
for extensive studies which will essentially lay the foundation
of scale-up and design in industrial scale.

Understanding the model instability limitations in cases of

numerical modeling of onoff operation, the potentials of
minmax operation should be exploited for industrial purpo-
sive use and recommendation should be identied by the
CFD model.

Studies on multidimensional CFD based model, particularly

including reaction kinetics, are necessary for better match with
experimental results reported in the literature and for further
reliable predictions in view of attracting professionals for
industrial applications.
Nomenclature
Roman symbols
C molar concentration (mol L
1
)
G gas phase mass ow rate (kg m
2
s
1
)
L liquid phase mass ow rate (kg m
2
s
1
)
P pressure (MPa)
t time (s)
T temperature (1C)
u velocity (m s
1
)
V ow rate (mL min
1
)
X conversion ()
Greek symbol
holdup
Subscripts
A time averaged value
b base
G gas phase
L liquid phase
p pulse
ss steady state
Acknowledgment
One of the authors (K.D.P. Nigam) thanks AvH Foundation for
the Humboldt Research Award during the preparation of this
manuscript.
References
Atta, A., Hamidipour, M., Roy, S., Nigam, K., Larachi, F., 2010. Propagation of slow/
fast-mode solitary liquid waves in trickle beds via electrical capacitance
tomography and computational uid dynamics. Chemical Engineering Science
65, 11441150.
Atta, A., Roy, S., Nigam, K., 2007a. Investigation of liquid maldistribution in trickle-
bed reactors using porous media concept in CFD. Chemical Engineering Science
62, 70337044.
Atta, A., Roy, S., Nigam, K., 2007b. Prediction of pressure drop and liquid holdup in
trickle bed reactor using relative permeability concept in CFD. Chemical
Engineering Science 62, 58705879.
Attou, A., Boyer, C., Ferschneider, G., 1999. Modelling of the hydrodynamics of the
cocurrent gasliquid trickle ow through a trickle-bed reactor. Chemical
Engineering Science 54, 785802.
Aydin, B., Fries, D., Lange, R., Larachi, F., 2006. Slow-mode induced pulsing in
trickle-bed reactors at elevated temperature. AIChE Journal 52, 38913901.
Ayude, A., Cassanello, M., Martnez, O., Haure, P., 2012. Yield optimization in a
cycled trickle-bed reactor: ethanol catalytic oxidation as a case study. Chemical
Engineering and Technology 35, 899903.
Ayude, A., Cechini, J., Cassanello, M., Martnez, O., Haure, P., 2008. Trickle bed
reactors: effect of liquid ow modulation on catalytic activity. Chemical
Engineering Science 63, 49694973.
Ayude, A., Rodriguez, T., Font, J., Fortuny, A., Bengoa, C., Fabregat, A., Stber, F.,
2007a. Effect of gas feed ow and gas composition modulation on activated
carbon performance in phenol wet air oxidation. Chemical Engineering Science
62, 73517358.
A. Atta et al. / Chemical Engineering Science () 9
Please cite this article as: Atta, A., et al., Cyclic operation of trickle bed reactors: A review. Chem. Eng. Sci. (2013), http://dx.doi.org/
10.1016/j.ces.2013.08.038i
Ayude, M., Cassanello, M., Martnez, O., Haure, P., 2005a. Phenomenological
approach to interpret the effect of liquid ow modulation in trickle bed
reactors at the particle scale. Chemical Engineering Science 60, 62626269.
Ayude, M., Cassanello, M.C., Haure, P.M., Martnez, O.M., 2005b. Periodic operation
of trickle bed reactors: an approach to catalyst design through modeling at the
particle scale. Industrial and Engineering Chemistry Research 44, 95949600.
Ayude, M., Martnez, O., Cassanello, M., 2007b. Modulation of liquid holdup along a
trickle bed reactor with periodic operation. Chemical Engineering Science 62,
60026014.
Ayude, M.A., Haure, P.M., Martnez, O.M., Cassanello, M.C., 2009. Towards a
comprehensive model for liquid ow modulation in trickle bed reactors.
Chemical Engineering Journal 154, 162167.
Banchero, M., Manna, L., Sicardi, S., Ferri, A., 2004. Experimental investigation of
fast-mode liquid modulation in a trickle-bed reactor. Chemical Engineering
Science 59, 41494154.
Boelhouwer, J., 2001. Nonsteady Operation of Trickle-Bed Reactors. Ph.D. Thesis,
Technische Universiteit Eindhoven.
Boelhouwer, J., Piepers, H., Drinkenburg, A., 2002a. Liquid-induced pulsing ow in
trickle-bed reactors. Chemical Engineering Science 57, 33873399.
Boelhouwer, J.G., Piepers, H.W., Drinkenburg, B.A.H., 2002b. Advantages of forced
non-steady operated trickle-bed reactors. Chemical Engineering and Technol-
ogy 25, 647650.
Borremans, D., Rode, S., Wild, G., 2004. Liquid ow distribution and particleuid
heat transfer in trickle-bed reactors: the inuence of periodic operation.
Chemical Engineering and Processing 43, 14031410.
Borren, B., Zeitler, O., Schmaus, C., Agar, D.W., 2010. Gasliquid mass transfer in
periodically operated trickle-bed reactors: inuence of the liquid-phase physi-
cal properties and ow modulation. Chemical Engineering and Processing 49,
923929.
Brkljac, B., Bludowsky, T., Dietrich, W., Grnewald, M., Agar, D.W., 2007. Modelling
of unsteady-state hydrodynamics in periodically operated trickle-bed reactors:
Inuence of the liquid-phase physical properties. Chemical Engineering Science
62, 70117019.
Brzi, D., Schubert, M., Hring, H., Lange, R., Petkovska, M., 2010. Evaluation of
periodic operation of a trickle-bed reactor based on empirical modeling.
Chemical Engineering Science 65, 41604165.
Castellari, A., Haure, P., 1995. Experimental study of the periodic operation of a
trickle-bed reactor. AIChE Journal 41, 15931597.
Charpentier, J.C., 2007. In the frame of globalization and sustainability, process
intensication a path to the future of chemical and process engineering
(molecules into money). Chemical Engineering Journal 134, 8492.
Dietrich, W., Anadon, L., Sederman, A., Gladden, L., Agar, D., 2011. Simulation
studies on the performance enhancement in periodically operated trickle-bed
reactors based on experimental local liquid distribution measurements. Indus-
trial and Engineering Chemistry Research 51, 16721679.
Dietrich, W., Grnewald, M., Agar, D.W., 2005. Dynamic modelling of periodically
wetted catalyst particles. Chemical Engineering Science 60, 62546261.
Fraguio, M., Muzen, A., Martinez, O., Bonelli, P., Cassanello, M., 2004. Catalytic wet
oxidation of ethanol in an integral trickle-bed reactor operated with liquid ow
modulation. Latin American Applied Research 34, 1116.
Gabarain, L., Castellari, A., Cechini, J., Tobolski, A., Haure, P., 1997. Analysis of rate
enhancement in a periodically operated trickle-bed reactor. AIChE Journal 43,
166172.
Giakoumakis, D., Kostoglou, M., Karabelas, A., 2005. Induced pulsing in trickle beds
characteristics and attenuation of pulses. Chemical Engineering Science 60,
51835197.
Hamidipour, M., Chen, J., Larachi, F., 2013. Cfd study and experimental validation of
trickle bed hydrodynamics under gas, liquid and gas/liquid alternating cyclic
operations. Chemical Engineering Science 89, 158170.
Hamidipour, M., Larachi, F., Ring, Z., 2007. Cyclic operation strategy for extending
cycle life of trickle beds under gas-liquid ltration. Chemical Engineering
Science 62, 74267435.
Hamidipour, M., Larachi, F., Ring, Z., 2008. Monitoring ltration in trickle beds using
electrical capacitance tomography. Industrial and Engineering Chemistry
Research 48, 11401153.
Hamidipour, M., Larachi, F., Ring, Z., 2009. Cyclic operation strategies in trickle beds
and electrical capacitance tomography imaging of ltration dynamics. Indus-
trial and Engineering Chemistry Research 49, 934952.
Haure, P., Hudgins, R., Silveston, P., 1989. Periodic operation of a trickle-bed reactor.
AIChE Journal 35, 14371444.
Janecki, D., Burghardt, A., Bartelmus, G., 2008. Computational simulations of the
hydrodynamic parameters of a trickle-bed reactor operating at periodically
changing feeding the bed with liquid. Chemical and Process Engineering:
Inzynieria Chemiczna i Procesowa 29, 583596.
Khadilkar, M.R., Al-Dahhan, M.H., Dudukovi, M.P., 2005. Multicomponent ow-
transport-reaction modeling of trickle bed reactors: application to unsteady
state liquid ow modulation. Industrial and Engineering Chemistry Research
44, 63546370.
Kostoglou, M., Karabelas, A., 2006. Inadequacy of the two-uid formulation to
model forced periodic ow in trickle beds. Chemical Engineering and Technol-
ogy 29, 303307.
Lange, R., Gutsche, R., Hanika, J., 1999. Forced periodic operation of a trickle-bed
reactor. Chemical Engineering Science 54, 25692573.
Lange, R., Hanika, J., Stradiotto, D., Hudgins, R., Silveston, P., 1994. Investigations of
periodically operated trickle-bed reactors. Chemical Engineering Science 49,
56155621.
Lange, R., Schubert, M., Dietrich, W., Grnewald, M., 2004. Unsteady-state operation
of trickle-bed reactors. Chemical Engineering Science 59, 53555361.
Larruy, B., Ayude, A., Font, J., Fortuny, A., Bengoa, C., Fabregat, A., Stber, F., 2007.
Gas feed composition modulation in phenol CWAO over active carbon.
Chemical Engineering Science 62, 55645566.
Liu, G., Duan, Y., Wang, Y., Wang, L., Mi, Z., 2005. Periodically operated trickle-bed
reactor for EAQs hydrogenation: experiments and modeling. Chemical Engi-
neering Science 60, 62706278.
Liu, G., Lan, J.a., Cao, Y., Huang, Z., Cheng, Z., Mi, Z., 2009. New insights into transient
behaviors of local liquid-holdup in periodically operated trickle-bed reactors
using electrical capacitance tomography (ECT). Chemical Engineering Science
64, 33293343.
Liu, G., Mi, Z., 2005. Hydrogenation of 2-ethylanthraquinones in a periodically
operated trickle-bed reactor. Chemical Engineering and Technology 28,
857862.
Liu, G., Mi, Z., Wang, L., Zhang, X., Zhang, S., 2006. Hydrogenation of dicyclopenta-
diene into endo-tetrahydrodicyclopentadiene in trickle-bed reactor: experi-
ments and modeling. Industrial and Engineering Chemistry Research 45,
88078814.
Liu, G., Zhang, X., Wang, L., Zhang, S., Mi, Z., 2008. Unsteady-state operation of
trickle-bed reactor for dicyclopentadiene hydrogenation. Chemical Engineering
Science 63, 49915002.
Lopes, R.J., Quinta-Ferreira, R.M., 2010. Numerical studies of catalyst wetting and
total organic carbon reaction on environmentally based trickle-bed reactors.
Industrial and Engineering Chemistry Research 49, 1073010743.
Lopes, R.J., Quinta-Ferreira, R.M., 2011. High-pressure modeling of unsteady-state
hydrodynamics in cocurrent gasliquid trickle-bed reactor. Industrial and
Engineering Chemistry Research 50, 27062714.
Lopes, R.J., Quinta-Ferreira, R.M., Larachi, F., 2012a. ECT imaging and CFD simulation
of different cyclic modulation strategies for the catalytic abatement of hazar-
dous liquid pollutants in trickle-bed reactors. Chemical Engineering Journal
211212, 270284.
Lopes, R.J., de Sousa, V.S., Quinta-Ferreira, R.M., 2012b. Numerical simulation of
reactive pulsing ow for the catalytic wet oxidation in TBR using a VOF
technique. AIChE Journal 58, 493504.
Massa, P., Ayude, M., Ivorra, F., Fenoglio, R., Haure, P., 2005. Phenol oxidation in a
periodically operated trickle bed reactor. Catalysis Today 107108, 630636.
Muzen, A., Fraguo, M., Cassanello, M., Ayude, M., Haure, P., Martnez, O., 2005.
Clean oxidation of alcohols in a trickle-bed reactor with liquid ow modulation.
Industrial and Engineering Chemistry Research 44, 52755284.
Nigam, K., Larachi, F., 2005. Process intensication in trickle-bed reactors. Chemical
Engineering Science 60, 58805894.
Rajashekharam, M., Jaganathan, R., Chaudhari, R., 1998. A trickle-bed reactor model
for hydrogenation of 2, 4 dinitrotoluene: experimental verication. Chemical
Engineering Science 53, 787805.
Saroha, A., Nigam, K., 1996. Trickle bed reactors. Reviews in Chemical Engineering
12, 207347.
Schubert, M., Kryk, H., Hampel, U., 2010. Slow-mode gas/liquid-induced periodic
hydrodynamics in trickling packed beds derived from direct measurement of
cross-sectional distributed local capacitances. Chemical Engineering and Pro-
cessing 49, 11071121.
Silveston, P., Hanika, J., 2002. Challenges for the periodic operation of trickle-bed
catalytic reactors. Chemical Engineering Science 57, 33733385.
Silveston, P., Hanika, J., 2004. Periodic operation of three-phase catalytic reactors.
The Canadian Journal of Chemical Engineering 82, 11051142.
Stankiewicz, A.I., Moulijn, J.A., 2000. Process intensication: transforming chemical
engineering. Chemical Engineering Progress 96, 2234.
Trivizadakis, M., Giakoumakis, D., Karabelas, A., 2006. Induced pulsing in trickle
beds-particle shape and size effects on pulse characteristics. Chemical Engi-
neering Science 61, 74487462.
Tuka, V., Hanika, J., Chyba, V., 2003. Periodic state of wet oxidation in trickle-bed
reactor. Catalysis Today 79, 427431.
Tuka, V., imkov, M., Chyba, V., Lederer, J., Kolena, J., Hanika, J., Jiin, V., Stank, V.,
Stavrek, P., 2007. The behavior of pilot trickle-bed reactor under periodic
operation. Chemical Engineering Science 62, 48914895.
Urseanu, M., Boelhouwer, J., Bosman, H., Schroijen, J., 2004. Induced pulse
operation of high-pressure trickle bed reactors with organic liquids: hydro-
dynamics and reaction study. Chemical Engineering and Processing 43,
14111416.
Wallis, G., 1969. One-Dimensional Two-Phase Flow. McGraw-Hill.
Wang, Y., Chen, J., Larachi, F., 2013. Modelling and simulation of trickle-bed reactors
using computational uid dynamics: a state-of-the-art review. The Canadian
Journal of Chemical Engineering 91, 136180.
Wongkia, A., Suriye, K., Nonkhamwong, A., Praserthdam, P., Assabumrungrat, S.,
2013. Catalytic performance improvement of styrene hydrogenation in trickle
bed reactor by using periodic operation. Korean Journal of Chemical Engineer-
ing 30, 593597.
Xiao, Q., Cheng, Z.M., Jiang, Z.X., Anter, A.M., Yuan, W.K., 2001. Hydrodynamic
behavior of a trickle bed reactor under forced pulsing ow. Chemical
Engineering Science 56, 11891195.
A. Atta et al. / Chemical Engineering Science () 10
Please cite this article as: Atta, A., et al., Cyclic operation of trickle bed reactors: A review. Chem. Eng. Sci. (2013), http://dx.doi.org/
10.1016/j.ces.2013.08.038i