Journal of Chemical Engineering of Japan, Vol. 43, No. 5, pp.

429–434, 2010 Short Research

Communication
RegularPaper
Issue

Mass Transfer Performance of a Capillary Microreactor during Ultrasound-

Assisted Phase Transfer Catalysis
Salah ALJBOUR, Hiroshi YAMADA and Tomohiko TAGAWA
Department of Chemical Engineering, Nagoya University,
Furo-cho, Chikusa-ku, Nagoya-shi, Aichi 464-8603, Japan

Keywords: Microreactor, Ultrasound, Phase Transfer Catalysis, Process Intensification

In this study, the liquid–liquid catalytic phase transfer reaction between benzyl chloride and sodium sulfide
was investigated in an ultrasound-based capillary microreactor. The mass transfer performance in the multi-
phase reaction was evaluated in terms of the mass transfer coefficient and was compared to the performance of
other systems namely, a capillary microreactor under silent conditions, a batch reactor with different speeds of
agitation, an ultrasound-assisted batch reactor, and an ultrasound-assisted batch reactor with mechanical agita-
tion.
In the batch reactor system, the mass transfer coefficient increased by a large factor when mechanical agita-
tion was accompanied by ultrasound irradiation. However, the capillary microreactor was superior to the batch
reactor system under different operation conditions.
In the case of the capillary microreactor, it was found that the mass transfer performance was enhanced by a
greater degree under sonication conditions than under silent conditions. Under sonication conditions, the mass
transfer performance was further enhanced by increasing the aqueous-to-organic phase flow rate ratio.

malonic esters. The results revealed that altering the

Introduction
Phase transfer catalysis (PTC) is a technique for
carrying out reactions between two of more partially
miscible or immiscible reagents in a multiphase system.
A phase transfer catalyst is added to the system to trans-
fer a functional reactant ion or group from one phase to
another phase in which it can rapidly react with another
reactant (Starks et al., 1994). The mass transfer step is
considered as one of the basic steps during the PTC
cycle. For some PTC reactions, the mass transfer is con-
sidered as the limiting step in the whole PTC process.
In the past few years, the emergence of microreac-
tors has provided a potentially new platform for per-
forming PTC reactions. The focus in the studies respon-
sible for this development was enhancement mass trans-
fer by utilizing the high surface area-to-volume ratio of-
fered by these devices. Ueno et al. (2003) investigated
the catalytic phase transfer alkylation reactions of β -keto
esters in a microreactor in a two-phase segmented flow
system. They reported that reducing the width of the mi-
croreactor promoted higher reaction rates as a result of
an extended interfacial area. Okamoto (2006) studied the
effect of alternate pumping of two reactants into a mi-
crochannel on the catalytic phase transfer alkylation of
Received on December 24, 2009; accepted on February 1, 2010
Correspondence concerning this article should be addressed to
S. Aljbour (E-mail address: saljbour@yahoo.com).
Presented at the 2009 AIChE Annual Meeting, at Nashville,
November, 2009.
pumping technique resulted in the development of a seg-
mented flow pattern inside the microchannel, promoting
an efficient mixing and high product yield compared to
those in batch processes.
These investigations suggest that dispersing one
phase into the other in a so-called “slug flow” or “seg-
mented flow” will enhance the mass transfer perform-
ance. The dimension of these slugs depends on the chan-
nel diameter, the mixer type, and the flow rates of the
immiscible phases (Onal et al., 2005).
In the present study, we investigate the mass trans-
fer performance in a liquid–liquid PTC reaction by uti-
lizing the slug flow in a capillary microreactor assisted
by ultrasound irradiation. As a model reaction (Aljbour
et al., 2009), we studied the reaction between benzyl
chloride (RCl) and sodium sulfide (Na2S) to produce
dibenzyl sulfide (RSR) in the presence of tetrahexylam-
monium bromide (THAB) as a phase transfer catalyst
(Figure 1).
1. Experimental
Figure 2 shows a schematic diagram of the ultra-
sound-assisted capillary-microreactor apparatus. The
aqueous and organic fluids were fed via two separate
lines and brought together in a T-shaped connector (U-
428, SUS T). The capillary tubing (ICT-55P, Institute of
Microchemical Technology Co., Ltd.) was attached di-
rectly downstream of the T-shaped connector. The capil-

Copyright © 2010 The Society of Chemical Engineers, Japan 429

 RSR. The catalyst salt (QCl) is then transferred back to
the interfacial region for regeneration.

Fig. 1 Model reaction: The phase transfer catalysis of benzyl 3. Mass Transfer Model
chloride
To compare the mass transfer performance of the
slug flow in the ultrasound-assisted capillary microreac-
lary tubing was made of PEEK resin; the diameter of the tor with those of other systems, the active catalyst
tubing was 0.26 mm and its length was 100 cm. The cap- (QSQ) mass transfer coefficient (kL) was estimated. The
illary-microreactor was spirally immersed in the ultra- rate at which the benzyl chloride (RCl) reactant was
sound bath with the help of a stainless steel holder with consumed is given by
rings attached on it. The frequency and the total output dCRCl,org
power of the ultrasound device (Fine, FU-10C) were k1CRCl,orgCQSQ,org  k2CRCl,orgCQSR,org (1)
28 kHz and 60 W, respectively. dt
External heat was supplied to the ultrasound bath where k1 and k2 are second order reaction rate constants.
via a coil-heat exchanger. The temperature rise in the ul- The rate at which the second active catalyst (QSR)
trasound bath caused by the heat generated by the ultra- was produced is given by
sound was measured using thermocouples. It is expected dCQSR,org
that power generation, can result in considerable heating  k1CRCl,orgCQSQ,org  k2CQSR,orgCRCl,org (2)
after minutes of continuous operation. In these experi- dt
ments, for each flow rate, the apparatus was stopped The initial conditions of the species are
when appropriate amounts of each phase could be col-
CQSQ,org,0  CQSR,org,0  0 and CRCl,org  CRCl,org,0
lected. Under the lowest feed flow rates, a temperature
rise of 2–3°C occurred before the amount appropriate QSR is characterized by high activity (Ido et al., 2000;
for analysis was collected. This is the maximum temper- Wang and Tseng, 2003). In experiments, QSR was not
ature rise that has been observed during the experiments. detectable in the organic phase solution. Thus, the
Two HPLC pumps were used to pump the aqueous pseudo-steady-state hypothesis (PSTH) is adopted:
and organic feeds. The reaction products were analyzed dCQSR,org
by GC. 0 (3)
The organic phase feed comprised a solution of dt
benzyl chloride (0.4 mol/L RCl, 0.04 mol/L THAB, This implies
0.1 mol/L n-docane as an internal standard, toluene as a
k1CQSQ,org  k2CQSR,org  kapp,1 (4)
solvent). The aqueous phase feed comprised sodium sul-
fide (1 mol/L Na2S · 9H2O) and water. where kapp,1 is the rate coefficient of the pseudo-first
The batch reactor experiments were carried out in a order reaction. Equation (4) suggests that the pseudo-
three-neck glass reactor (capacity: 500 mL) that included first-order constant is a linear function of the active cata-
a thermocouple and was capable of sampling. The batch lyst concentration. This observation has been made by
reactor was immersed in the ultrasound bath to a level at many authors for a variety of phase transfer reactions
which the aqueous phase and the organic phase volumes (Starks et al., 1994). Accordingly, Eq. (1) can be rewrit-
were completely irradiated by ultrasound. A mechanical ten as
agitator (six blades, flat blade made of glass) with auto- dCRCl,org
mated speed control was used. 2 kapp,1CRCl,org (5)
dt
The conversion fraction of RCl is defined as X:
2. Reaction Mechanism
CRCl,org
THAB is a phase transfer catalyst with a large qua- X  1 (6)
CRCl,org,0
ternary cation size (Q) associated with a bromide anion
(X). The quaternary ammonium cation reacts with the Thus, Eq. (5) is expressed as
sulfide anion to form the first active catalyst (QSQ).
ln(1  X )  2kapp,1t (7)
Similar to the depiction by Wang and Tseng (2003)
for a similar system, the mechanism of the reaction Equation (7) is valid under kinetics limitations. In this
might be formulated as depicted in Figure 3. phase transfer reaction, the concentration of RCl is
This mechanistic model reveals that the organic re- higher than the concentration of the phase transfer cata-
action step involves a displacement reaction between the lyst. In addition, RCl is highly soluble in the organic
first transferred active catalyst QSQ and benzyl chloride phase. Therefore, the mass transfer limitaions for RCl
(RCl) to produce the second active catalyst (QSR). The can be neglected.
second active catalyst QSR reacts with RCl to produce To estimate the rate of delivery of QSQ into the or-

430 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

 Fig. 2 Ultrasound-assisted capillary microreactor apparatus
Fig. 3 Mechanism of the catalytic phase transfer reaction
ganic phase (RA), the theory of mass transfer when ac-
companied with chemical reaction can be employed.
Assuming that the rate of reaction between RCl and
QSQ in the organic phase is relatively greater than the
mass transport rate of QSQ into the organic phase, then
the rate of extraction of QSQ is given by (Nanda and
Sharma, 1967)
RA  CQSQ,org DQSQ,org k1CRCl,org  kLCQSQ,org (8)
where, kL  DQSQ,org k1CRCl,org is the mass transfer co-
efficient for mass transfer accompanied by fast chemical
reaction. This assumption of mass transfer limitations
which are associated with the transport of the phase
transfer catalyst seems to be valid since this type of reac-
tion proceeds so readily when using alkali metal sulfides
(Starks et al., 1994).
Experimentally, kapp,1 is determined from the slope
of the straight line obtained by plotting ln(1  X ) versus
time. Then, the intrinsic rate constant is obtained from
Eq. (4). The diffusion coefficient of QSQ in toluene at
T  303 K was calculated to be 5.34  1010 m2/s by
using the Wilke–Chang equation (Wilke and Chang,
1955).
VOL. 43 NO. 5 2010
4. Results and Discussion
4.1 Mass transfer performance in the batch reactor
system
As suggested by the reaction mechanism shown in
Figure 3, the overall PTC process is greatly affected by
the mass transfer steps; the steps involve the mass trans-
fer of the first active catalyst (QSQ) from the interfacial
region to the bulk of the organic phase and the mass
transfer of the catalyst salt (QCl) from the bulk of the or-
ganic phase back to the interfacial region for regenera-
tion. Thus, it is anticipated that an enhancement in the
mass transfer of QSQ and QCl will enhance the rate in
the overall PTC cycle, and as a result, the rate of cat-
alytic conversion of RCl will increase.
Table 1 shows the apparent reaction rate constants
(kapp,1) in the batch reactor under different operational
conditions.
Figure 4 shows the estimated mass transfer coeffi-
cient (kL) for different operation conditions.
Under silent conditions, increasing the speed of ag-
itation resulted in an increase in the apparent reaction
rate constant and mass transfer coefficient. This indi-
cates clearly that the reaction is influenced by mass
transfer limitations. Under agitation, the organic phase
was dispersed in the aqueous phase in the form of
smaller droplets. This increased the contact area between
phases. Therefore, the mass transfer was enhanced.
Under conditions involving only sonication, the re-
action was initiated and proceeded as a good speed; 15%
conversion was achieved 8 min after the reaction was ini-
tiated. The effect of ultrasound on chemical reactions is
attributed to the implosive collapse of microbubbles that
formed during the rarefaction, or negative pressure pe-
riod, of sound waves. The implosive collapse of mi-
crobubbles, typically referred to as cavitation, generates
energy, and this energy is believed to be responsible for
the chemical or/and the mechanical effects in the system
involved (Mason and Lorimer, 1988; Hagenson and
Doraiswamy, 1998). The collapse of cavitation bubbles
at or near the interface of immiscible liquids causes dis-
431
Table 1 PTC reaction performance in the batch reactor
under different operation conditions
Operational conditions kapp,1 [min1]
0 rpm 0.00195
100 rpm 0.00565
250 rpm 0.102
500 rpm 0.1625
1000 rpm 0.1915
Sonication only 0.0105
500 rpm  sonication 0.615
Fig. 4 The mass transfer performance in the batch reactor
under different operation conditions
ruption and mixing, resulting in the formation of very
fine emulsions. This is essentially a mechanical effect,
and it has been exploited to realize highly efficient emul-
sification (Mason and Lorimer, 1988; Mason, 1997).
Thus, in the presence of ultrasound in the system, a cavi-
tational collapse near the liquid–liquid interface dis-
rupted the interface; this led to the formation of fine
emulsions and an increase in the interfacial contact area
across which mass transfer of species can take place.
Interestingly, the reaction conversion was intensi-
fied up to a complete conversion within a short time
(around 5 min) when mechanical agitation (500 rpm)
was carried out with ultrasound irradiation. As shown in
Figure 4, the mass transfer coefficient was of the order
of 103 when mechanical agitation was carried out at a
speed of 500 rpm, whereas it was of the order of 104
when sonication was applied without mechanical agita-
tion. However, the mass transfer coefficient was in-
creased by a large factor when mechanical agitation (500
rpm) and ultrasound irradiation were simultaneously
carried out. As shown in Figure 5, such a combination
produces very fine dispersions, thereby increasing the
interfacial area.
4.2 Mass transfer performance of the capillary mi-
croreactor
Table 2 lists the profile of the mass transfer per-
formance of the capillary microreactor under silent and
sonication conditions.
432
Table 2 The mass transfer performance of the capillary mi-
croreactor under silent and sonication conditions
kapp,1 [min1] kL [m/s]  104
Silent 1.3 35
Sonication 1.8 41
Fig. 5 Dispersion of the two-phase system: a) two-phase
system under static conditions; b) the two-phase sys-
tem after being subjected to ultrasound irradiation
A comparison of the mass transfer performance of
the capillary microreactor with that of the batch reactor
system under the different operational conditions shows
that the microreactor is superior to the batch reactor sys-
tem. Under the operation conditions of this study, the
mass transfer coefficient of the capillary microreactor is
greater than that for the batch reactor. Introducing aque-
ous-organic two-phase immiscible fluids into a capillary
microreactor generates a two-phase slug-flow pattern in-
side the capillary. This flow pattern is characterized by a
uniform area of the interface between the slugs
(Dummann et al., 2003).
Figure 6 shows a typical slug flow pattern in the
capillary microreactor.
Assuming that only the ends of the slugs participate
in mass transfer, the surface area per unit slug volume
can be approximated as 2/L, where L is the slug length.
Under the operation conditions in this study, the slug
sizes under silent conditions ranged from 0.5  103 to
1  103 m. In this case, the surface area per unit slug
volume can be calculated as 2,000–4,000 m1. This spe-
cific interfacial area is greater than those reported for
conventional laboratory and production vessels (typi-
cally around 100 m1 and seldom above 1,000 m1,
Kiwi-Minsker and Renken, 2005).
During the transport of these slugs through the cap-
illary, internal circulations are generated within the
slugs. The internal circulation is believed to be a result
of the shear between the wall surface and the slug axis
(Kashid et al., 2005). This circulation pattern enhances
mixing within the slugs and reduces the thickness of
boundary layer at the liquid–liquid interface. Thus, two
mechanisms are responsible for the mass transfer be-
tween the two phases: convection within the individual
slugs and interfacial diffusion between the adjacent
JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

Fig. 6 Slug flow pattern in a capillary microreactor under
silent and sonication conditions
slugs. Thus, the rate of mass transfer is enhanced.
However, the mass transfer performance in the cap-
illary microreactor under sonication conditions is supe-
rior to that under silent conditions. The presence of ul-
trasound affected the length of the organic phase slugs.
The slug sizes under sonication condition were irregular
and depended strongly on the flow rate. The irregularity
in slug sizes is attributed to the continuous deformation
of phase boundaries of the formed slugs in under ultra-
sound irradiation.
Optical observations clearly indicate that the phase
boundary of each slug is affected by interfacial instabil-
ity caused by the continuous exposure to the ultrasound
irradiation. Under ultrasound irradiation, the organic
slugs undergo continuous break-up and coalescence.
This behavior is important from a mass transfer stand-
point since it enhances mixing within the slugs and
helps to establish a new gradient of the driving force for
mass transfer at the slug interface. This results in in-
creased mass transfer rates.
4.3 Effect of flow rate ratio on the mass transfer
performance
The mass transfer performance in the ultrasound-
assisted capillary microreactor was studied at different
flow rate ratios (q).
Qaq
q (9)
Qorg
Figure 7 shows the effect of changing the q value on the
mass transfer coefficient. The organic phase flow rate
was fixed at 0.1 mL/min while changing the aqueous
phase flow rate.
It is obvious from Figure 7 that increasing the flow
rate ratio resulted in an increase in the mass transfer co-
efficient. This is because the organic phase becomes
more segmented in the continuous aqueous phase at high
aqueous-to-organic flow rate ratios. For many microflu-
idic liquid–liquid applications, such segmentation re-
VOL. 43 NO. 5 2010
Fig. 7 Effect of changing the flow rate ratio on the mass
transfer performance in the capillary microreactor
quires relatively high velocities of the carrier fluid and
low superficial velocities of the dispersed phase (Zhao et
al., 2006). The segmentation of the organic phase re-
sulted in an increase in the overall interfacial area.
In addition, increasing the aqueous-to-organic
phase flow ratio increases the total phase flow rate. This
resulted in an increase in the mass transfer rate because
of the increased disruption of the concentration gradi-
ents at higher phase velocities.
Conclusions
An ultrasound-based capillary-microreactor was
designed. The use of this reactor to carry out the phase
transfer catalysis reaction of benzyl chloride with
sodium sulfide in a two-phase slug flow system was
demonstrated. The mass transfer performance was evalu-
ated in terms of the mass transfer coefficient. Ultrasound
irradiation enhanced the mass transfer performance by
increasing the overall interfacial area over which mass
transfer and the reaction occured.
The combination of ultrasound irradiation and me-
chanical agitation promoted almost complete conversion
within a few minutes. The combination of the ultrasound
irradiation with microreactor technology will eliminate
the mass transfer limitations in phase transfer reactions,
and this will result in an increase in the overall reaction
rate.
The green aspect of this prototype is the rate en-
hancement and the continuous mode of operation.
Nomenclature
CQSQ,org  concentration of the first active catalyst [mol/m3]
CQSR,org  concentration of the second active catalyst [mol/m3]
CRCl,org  concentration of benzyl chloride [mol/m3]
CQSQ,org,0  initial concentration of the first active catalyst
[mol/m3]
CQSR,org,0  initial concentration of the second active catalyst
[mol/m3]
CRCl,org,0  initial concentration of benzyl chloride [mol/m3]
DQSQ,org  diffusion coefficient of QSQ [m2/s]
433
 Eng. Chem. Res., 44, 5003–5010 (2005)
k1  second order reaction rate constant [m3/(mol · s)]
Kiwi-Minsker, L. and A. Renken; “Microstructured Reactors for Cat-
k2  second order reaction rate constant [m3/(mol · s)]
alytic Reactions,” Catal. Today, 110, 2–14 (2005)
kapp,1  apparent reaction rate constant [s1]
Mason, T. J.; “Ultrasound in Synthetic Organic Chemistry,” Chem. Soc.
kL  the mass transfer coefficient for mass transfer accom-
Rev., 26, 443–451 (1997)
panied by fast chemical reaction [m/s]
Mason, T. J. and J. P. Lorimer; Sonochemistry: Theory, Applications
L  slug length [m]
and Uses of Ultrasound in Chemistry, Ellis Horwood Publishers,
QA  organic phase volumetric flow rate [m3/s]
Chichester, U.K. (1988)
QB  aqueous phase volumetric flow rate [m3/s]
Nanda, A. K. and M. M. Sharma; “Kinetics of Fast Alkaline Hydroly-
q  aqueous-to-organic flow rate ratio [—]
sis of Esters,” Chem. Eng. Sci., 22, 769–775 (1967)
RA  rate of delivery of QSQ into the organic phase
Okamoto, H.; “Effect of Alternating Pumping of Two Reactants into
[mol/(m2 · s)]
a Microchannel on a Phase Transfer Reaction,” Chem. Eng. Tech-
t  reaction time [s]
nol., 29, 504–506 (2006)
X  conversion [—]
Onal, Y., M. Lucas and P. Claus; “Application of a Capillary Microre-
actor for Selective Hydrogenation of α ,β -Aldehyde in Aqueous
Literature Cited
Multiphase Catalysis,” Chem. Eng. Technol., 28, 972–978 (2005)
Aljbour, S., H. Yamada and T. Tagawa; “Ultrasound-Assisted Phase
Starks, C. M., C. L. Liotta and M. Halpern; Phase Transfer Catalysis:
Transfer Catalysis in a Capillary Microreactor,” Chem. Eng.
Fundamentals, Application and Industrial Perspectives, Chapman
Process., 48, 1167–1172 (2009)
& Hall, New York, U.S.A. (1994)
Dummann, G., U. Quittmann, L. Groschel, D. W. Agar, O. Worz and K.
Ueno, M., H. Hisamoto, T. Kitamori and S. Kobayashi; “Phase-Trans-
Morgenschweis; “The Capillary-Microreactor: A New Reactor
fer Alkylation Reactions Using Microreactors,” Chem. Commun.,
Concept for the Intensification of Heat and Mass Transfer in Liq-
936–937 (2003)
uid–Liquid Reactions,” Catal. Today, 79-80, 433–439 (2003)
Wang, M.-L. and Y.-H. Tseng; “Phase Transfer Catalytic Reaction of
Hagenson, L. C. and L. K. Doraiswamy; “Comparison of the Effects of
n-Bromobutane and Sodium Sulfide in a Two-Phase Solution and
Ultrasound and Mechanical Agitation on a Reacting Solid–Liquid
Its Kinetics,” J. Mol. Catal. A: Chem., 203, 79–93 (2003)
System,” Chem. Eng. Sci., 53, 131–148 (1998)
Wilke, C. R. and P. Chang; “Correlation of Diffusion Coefficients in.
Ido, T., T. Susaki, G. Jin and G. Goto; “Characteristics of Third Phase
Dilute Solutions,” AIChE J., 1, 264–270 (1955)
for Reaction of Benzyl Chloride with Sodium Sulfide in Phase
Zhao, Y., G. Chen and Q. Yuan; “Liquid–Liquid Two-Phase Flow Pat-
Transfer Catalytic System,” Appl. Catal., A, 201, 139–143 (2000)
terns in a Rectangular Microchannel,” AIChE J., 52, 4052–4060
Kashid, M. N., I. Gerlach, S. Goetz, J. Franzke, J. F. Acker, F. Platte, D.
(2006)
W. Agar and S. Turek; “Internal Circulation within the Liquid
Slugs of a Liquid–Liquid Slug-Flow Capillary Microreactor,” Ind.

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