Full Paper

Modeling of the Residence Time Distribution and Application

of the Continuous Two Impinging Streams Reactor
in Liquid-Liquid Reactions
By Morteza Sohrabi* and Behrooz Zareikar

The two-phase monosulfonation of toluene, as an example of liquid-liquid reactions, has been conducted in a continuous
two impinging stream reactor (TISR). The extent of reaction under different operating conditions has been determined.
A comparison has been made between the performance capability of the TISR and that of continuous stirred tank reac-
tors (CSTR). Under identical conditions, including mean residence time, temperature, feed compositions and phase ratio,
the impinging stream reactor has shown a higher efficiency. Finally, a stochastic model, based on Markov chain processes
has been developed for the TISR, which describes the flow pattern and the residence time distribution (RTD) within the
reaction system. The RTD model, combined with the kinetic expression, has been applied to calculate the conversion of
toluene in the reactor. The predicted values for toluene conversion have been compared with those determined experi-
mentally.

1 Introduction 2 Experimental

One of the important operations in chemical engineering 2.1 Chemicals

is the mass transfer between immiscible phases. In an im-
pinging stream apparatus, a unique flow behavior is utilized The chemicals used in this study were of analytical grade.
by which the transfer processes in heterogeneous systems is Sulfuric acid (98 %) and toluene (99.8 %) were supplied by
intensified [1]. In such systems two feed streams, flowing Merck KGaA, Germany. Nitrogen was provided by Roham
parallel or counter-currently collide with each other at a Gas Company, Iran. Potassium dichromate (99.9 %) was ob-
zone in which the two streams impinge. tained from Sigma-Aldrich Chemie GmbH, Germany.
The application of two impinging stream systems as
chemical reactors, was first reported by Elperin in 1982
[2]. Some of the multiphase reactions carried out in two 2.2 Reactor System
impinging streams reactors include chemical absorption of
CO2 gas in sodium hydroxide [3] and monoethanolamine The experimental apparatus used in the current work is
solutions [1], and isomerization of glucose to fructose by shown in Fig. 1. The reactor consists of a cylindrical vessel
an immobilized enzyme [4]. Impinging stream systems made of pyrex glass, length 60 cm and internal diameter
have been successfully applied to other chemical processes 14 cm. The reactor is equipped with two circular plates made
such as dissolution, mixing as well as mass and heat trans- of ªTeflonº placed at the two ends of the reactor. Thus, the
fer operations [5±8]. length of the reaction compartment can be varied, by mov-
In the present study, the monosulfonation of toluene by ing the plates away from, or towards each other.
concentrated sulfuric acid, as a typical example of liquid-liq-
uid reactions, has been conducted in TISR. In addition, mea-
surement and modeling of the residence time distribution
(RTD) of the aqueous phase within the two impinging
stream reactors (TISR) has been carried out. Finally, a com-
parison has been made between the experimentally deter-
mined conversion of toluene and the predictions made using
a model developed from a combination of RTD formulation
and the kinetic expression.

±
[*] M. Sohrabi (author to whom correspondence should be addressed, Figure 1. Schematic diagram of the experimental rig: 1, 2 ± feed reservoirs; 3,
sohrabi@aut.ac.ir), B. Zareikar, Amirkabir University of Technology, 4 ± metering pumps; 5, 6, 7 ± needle valves; 8 ± nitrogen cylinder; 9 ± gas flow
Department of Chemical Engineering, Tehran 15914, Iran. meter; 10 ± spray nozzles; 11 ± reactor; 12 ± circular plates.

Chem. Eng. Technol. 2005, 28, No. 1 DOI: 10.1002/ceat.200407016  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 61
 Full Paper
The reactants (toluene and sulfuric acid) were kept in sep-
arate glass containers and fed to the reactor via four identi-
cal feed nozzles made of glass, situated at the two ends of
the vessel. Reactants were transported to the nozzles using
metering pumps. The liquid reactants were sprayed into the
reactor by applying pressurized nitrogen via special ducts
placed behind the feed nozzles.
In order to determine the suitable positions and angles of
the feed nozzles at which stable jets of liquids would be es-
tablished, a number of experiments were performed, using
water and toluene.
These included allowing droplets of reactants to leave the
feed nozzles, and collide at the impingement zone before
being dropped into a funnel connected to the sampling
tubes. A second outlet was also considered for the bulk of
liquid which was collected at the bottom of the vessel.
This experimental set up, allows consideration of the ef-
fects of changing certain pertinent parameters of the system
on the extent of reaction.
2.3 Start-up and Analytical Technique
For each run, the experimental system was first tested
using distilled water. The flow of driving nitrogen gas was
then adjusted and the reactants were fed to the reactor. The
reaction temperature was measured by an iron constantan
thermocouple housed adjacent to the impinging zone. Con-
trol and variation of the temperature, was achieved by heat
transfer to the driving nitrogen from a copper coil equipped
with an automatic temperature regulator. Certain dimen-
sions of the reactor and the shape of the feed nozzles, are
demonstrated in Fig. 2.
When steady state conditions were established, samples
were drawn to the calibrated sampling bottles containing
ice-cold water. The collected samples were allowed to sepa-
rate into two distinct layers. The volumes of each phase were
noted. The dissolved toluene in the acid phase was thor-
oughly extracted by using cyclohexane. Finally, the aqueous
solutions were centrifuged and filtered. A 3 cm3 quantity of
each solution was then diluted to 10 cm3 with deionized
water and the absorbance at 262 nm was measured by a UV-
Figure 2. Dimensions of the reactor (figures are in mm).
62  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
VIS spectrophotometer (Shimadzu UV-3150). Results were
reproducible with a mean absolute deviation of 4±6 %.
3 Results and Discussion
3.1 Two Phase Sulfonation of Toluene in Impinging Stream
Reactors
Heterogeneous sulfonation of toluene occurs in the acid
phase and the extent of reaction in the organic phase is insig-
nificant [9, 10].
A number of experiments were conducted under a variety
of operating conditions to investigate the performance of
the TISR for two liquid phase reactions. It was observed that
increasing the driving nitrogen flow rate and decreasing the
distance between the two feed nozzles enhanced the extent
of the reaction. This could be due to the increase in the im-
pact force of inter droplet collision and multiple circulation
of the drops. The results are summarized in Tab. 1.
As can be observed from this table, at lower concentra-
tions of sulfuric acid, (less than 15.8 mol dm±3) the perfor-
mance capability of TISR and CSTR are approximately the
same. This may be explained by the fact that at lower ranges
of sulfuric acid concentrations and with proper mixing, the
overall rate of two-phase sulfonation is controlled solely by
the kinetics of the reaction [9]. Therefore, enhancing the rate
of mass transfer beyond a critical value should not affect the
overall rate of reaction.
3.2 Stochastic Model for the Residence Time Distribution
of the Aqueous Phase in TISR
A model for the residence time distribution of the aque-
ous phase within the reactor was developed based on the
types first proposed by van de Vusse [11]. Since the collision
of droplets in the impingement zone is a random process, a
suitable mathematical technique to handle the latter, is the
Markov chains model [1].
According to discrete-time Markov chains, the probability
of an event at time t + 1 (t = 0, 1, 2, ...), given only the out-
http://www.cet-journal.de Chem. Eng. Technol. 2005, 28, No. 1
 Full Paper

Table 1. Two phase sulfonation of toluene in a continuous two impinging streams reactor.

Run No. Temperature/C Distance Flow rate toluene Acid flow Concentration Conversion Extent of reaction
between the of nitrogen flow rate rate of acid of toluene in TISR relative to
two feed nozzles that
(L/cm) (cm3/h) (cm3/h) (cm3/h) (mol/dm3) (%) in CSTR

TS1 19.4 25 1200 330 335 14.6 2.2 1.2

TS2 19.4 25 1200 320 315 15.0 4.8 1.1

TS3 19.5 25 1200 335 328 15.4 8.2 1.2

TS4 19.4 25 1200 330 334 15.8 29.2 3.8

TS5 19.4 25 1200 325 332 16.8 95.4 5.4

TS6 20.4 20 1800 220 450 14.6 3.6 1.4

TS7 20.2 20 1800 215 440 15.4 10.1 1.3

TS8 20.1 20 1800 225 450 16.8 90.3 3.7

TS9 20.1 25 1800 700 345 15.0 3.8 1.3

TS10 20.1 25 1800 680 330 16.8 34.5 6.2

TS11 25.2 20 1200 330 335 15.8 44.8 5.6

TS12 25.1 20 1800 220 435 16.8 96.5 7.4

TS13 19.4 25 1800 322 331 15.8 33.2 4.3

come at time t is equal to the probability of the event at time
t + 1, given the entire history of the system. In other words,
the probability of the event at t + 1 is not dependent upon
the state history, prior to time t. Thus, the values of the pro-
cess at the given time t, determines the conditional proper-
ties for future values of the process. These values are called
the state of the process, and the conditional properties are
viewed as transition probabilities between the states i and j,
pij. These values may be displayed in a matrix (P = [pij])
called the one step transition matrix.
The matrix P has N rows and N columns, where N is the
number of possible states for the transition of the system.
The rows of matrix P consist of the probabilities of all possi-
ble transitions from a given state and thus sum to 1:
N
P the Markov process and the transition probability, pij, is the
pij = 1
jˆ1
This matrix completely describes the Markov process.
Some other definitions and equations related to Markov
processes include:
± si(n), the state probability, defined as the probability that
the system will be in state i after n transitions from a given
starting point;
± S(n), the state probability vector, a line vector composed
of elements si(n); S(n) = [s1(n), s2(n), ..., sN(n)].
The equation which governs the Markov processes is:
N
P through the exit port (region 4).
si(n) = 1
iˆ1
Eq. (2) implies that the total probability of the system
reaching one of all possible N states, which can be occupied
after n transitions is equal to unity:
N
P indicates the probability that a droplet entering the system at
sj(n+1) = si(n)pij n = 0, 1, 2, ...
iˆ1
Eq. (3) states that the probability that the system will be
in state j after n + 1 transitions is equal to the sum of the
probabilities of it being in any state i after n transitions, mul-
tiplied by the probability of transferring from state i to state
j in one transition step. This definition is also valid for all the
states expressed by the following:
S(n + 1) = S(n) P (4)
Further details of Markov process may be found else-
where [12, 13].
By considering the pattern of liquid flow within the reac-
tor, the reaction system was divided into four regions with
equal volumes, see Fig. 3. Each region represents a state in
(1) probability of a liquid droplet leaving region i and entering
region j. A recycle stream (r), is also assumed due to the
counter current flows. In Fig. 3(b), it may be observed that
the transfer of fluids to region 4 is only possible from regions
1 and 2. This assumption has been made only to emphasize
the effect of penetration of droplets in opposite regions. In
other words, after collision in the impingement zone, the
droplets within the two opposite streams, are thrown or
dragged into either region 1 or 2, depending upon the rela-
tive forces exerted by them, and from here, drop instantly
down to the bottom of the vessel and leave the latter
(2)
It is worth considering region 4 in Fig. 3(b). Whenever a
droplet reaches this region, it leaves the system to go to state
5, where it then remains. Therefore state 5 is known as a
ªtrapping stateº.
The fourth element of the state probability vector, s4(n)
(3)
n = 0 will leave the system after n Dt (n = 1, 2, ...). The numeri-

Chem. Eng. Technol. 2005, 28, No. 1 http://www.cet-journal.de  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 63
 Full Paper

Figure 3. Model of the reactor: (a) The flow regions proposed for the reaction system: 1, 2, 3 ± perfect mixing regions; 4 ± plug flow region; (b) the resulting model.

cal value of s4(n) for n = 0, 1, 2, ..., represents the impulse
response of the system after n intervals of time length Dt.
It is possible to define the appropriate probabilities along
the path of a droplet from the inlet of the system through to
the exit. The probability of a droplet remaining in regions 1,
2 or 3 during a time interval Dt is given as follows:
In this matrix, the elements located on the diagonal are
the probabilities of remaining in the same region. Those on
the vertical columns are the probabilities of entering region
j, and the elements on the horizontal rows correspond to the
probabilities of leaving region j. The initial state probability
vector is also known:

p11 = p22 = e±2(Q +r)Dt/V; p33 = e±rDt/V (5) S(0) = [s1(0) s2(0) s3(0) s4(0) s5(0)] = [0.5 0.5 0 0 0] (9)

where, Q is the total volumetric flow rate of liquids enter- The two parameters of this model, R and Dh, can be evalu-
ing the reactor, and V, is the volume of each region. ated by considering that the variance (r2) of the experimental
By noting that the probability of leaving any region i (i = 1, RTD data and the measured mean residence time (t) must be
2, 3, 4) is 1 ± pij , the probabilities of a droplet passing from identical with those calculated from the stochastic model.
region 1 to region 3, from region 3 to region 2 or from region To determine the residence time distribution of the aque-
1 to region 4, may be calculated by: ous phase within the reactor, the following experiment was
performed. Toluene and distilled water were fed to the reac-
r …r‡Q†Dt=V
p13 ˆ p23 ˆ …1 e † tor via spray nozzles. At a time, a change from the water
r‡Q
stream to one of water containing a mineral salt (potassium
1 rDt=V
p32 ˆ p31 ˆ …1 e † dichromate) with known concentration and colour intensity
2
(C0) was rapidly performed (step input). Samples at the out-
Q …Q‡r†Dt=V
p14 ˆ p24 ˆ …1 e † (6) let of the reactor were collected, using a circular vessel di-
r‡Q
vided into 24 segments with equal volumes, placed under the
The transition probabilities were rearranged, using two exit port and rotated at a preset speed using an electric mo-
dimensionless parameters, i.e., tor. Successive samples were obtained at equal time intervals
by this method. Changes in the rotating speed altered the
Dt r
Dh ˆ ; Rˆ (7) time intervals between the sample collections. The content
t Q
of each segment was transferred to a separating funnel. The
Thus, the complete transition probabilities matrix, P, may aqueous phase was separated from the organic layer and the
be presented as follows: concentration (colour intensity) of the former was measured
2…1‡R†Dh R 2…1‡R†Dh 1 2…1‡R†Dh
(C), using a UV spectrophotometer. From a plot of C/C0 ver-
e 0 …1 e † …1 e † 0
R‡1 R‡1 sus time, the RTD data were obtained.
2…1‡R†Dh R 2…1‡R†Dh 1 2…1‡R†Dh
The following procedure was applied to determine the pa-
0 e …1 e † …1 e † 0
R‡1 R‡1 rameters of the stochastic RTD model, using the experimen-
1 1 tal data. From the RTD data found experimentally, the mean
…1 e 4RDh
† …1 e 4RDh
† e 4RDh
0 0 2
2 2 residence time, texp , and the variance, rexp , were determined,
applying the following relations:
0 0 0 0 1
n
P
ti Ci Dti
0 0 0 0 1 texp ˆ iˆ1
(10)
Pn
Ci Dti
(8) iˆ1

64  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.cet-journal.de Chem. Eng. Technol. 2005, 28, No. 1
 Full Paper

n
P 2 0.6
…ti t† Ci Dti Model Prediction + Experimental Data
r2exp ˆ iˆ1 n (11)
P 0.5 +
Ci Dti
iˆ1 +
0.4
where, Dt is an arbitrary time incre-
ment and may be taken as equal to

E
0.3
the time intervals between successive
sample collections.
To determine the parameters of 0.2 +
the RTD model, it was assumed that
the experimental mean residence 0.1 + +
time and variance have to be identi- + + + + + + + + +
cal to those of the theoretical model. 0 + + +
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
The variance of the theoretical mod-
Time (s)
el was calculated from the following
equation: Figure 4. An example of the residence time distribution data for the continuous two impinging streams reac-
tor. Nitrogen flow rate = 1800 cm3 h±1, toluene flow rate = 320 cm3 h±1; water flow rate = 325 cm3 h±1, mean
n 2
P 2 residence time 2.2 s, L = 25 cm, parameters of the stochastic RTD model: Dh = 0.62; R = 0.45, r exp = 6.43.
r2mod ˆ S4 …j†…R; Dh†‰t…jDh 1†Š
jˆ1 (12)

S4(j) has been determined by means of successive calcula- tion of toluene was considered [14]. This is based on a fast
tions using Eq. (4) and by taking S(0) as the starting point, reaction in a narrow zone in the aqueous phase, adjacent to
Eq. (9). Since it is generated by means of parametric matrix the interface and takes the form:
multiplication, its elements are functions of R and Dh. p A p

By considering the implication of the equality of the two R = ACTa DkCs ˆ CTo DkCs (14)
u
residence times of the experimental and theoretical RTD
curves, the following relation is obtained: where R, is the overall rate of sulfonation, j, is the toluene
n distribution coefficient, A, is the interfacial area per unit vol-
P
1 ˆ Dh jS4 …j†…R† (13) ume of the acid phase, C*Ta, is the saturation concentration
jˆ1 of toluene in the aqueous phase, D, is the diffusivity of tolu-
In the above equation, S4(j), which is initially a function of ene, CTo and Cs, are the molar concentrations of toluene in
both R and Dh, becomes solely a function of R after replac- the organic phase and sulfuric acid in the aqueous phase re-
ing the Dh values. Therefore, the latter can be solved for R. spectively, and k, is the rate constant.
2
Knowing R and Dh, r mod can be then calculated using Values for the above parameters may be obtained from
2
Eq. (12) and may be compared with rexp . the literature [9, 10, 14, 15]. Some of these data are collected
The operating conditions in one of the experimental runs in Tab. 2. Eq. (14), combined with the performance expres-
were as follows: sion for the CSTR, was applied to calculate the extent of re-
± Distance between the feed nozzles = 25 cm; Nitrogen flow action in the latter reactor. These data were then compared
rate = 1800 cm3 h±1 with those determined experimentally in TISR. Under iden-
± Toluene flow rate = 320 cm3 h±1; Water flow rate = tical conditions, including mean residence time, temperature,
325 cm3 h±1 feed composition and phase ratio, the impinging streams re-
By applying such a procedure, with Dh equal to 0.62, the actor has shown a higher efficiency, see Tab. 1.
value for R was determined as 0.45, while, the two variances
2 2
were rmod = 6.35 and rexp = 6.43.
The residence time distribution data (E) for this case is Table 2. Values of some pertinent parameters of toluene sulfonation in CSTR at
shown in Fig. 4. All calculations were carried out by apply- 20 C.
ing Mathematica version 2.2 software.
[H2SO4] k2 (1) D C*Ta (2) A (3)
mol dm±3 dm3 mol±1 min±1 cm2 s±1 Mol dm±3 cm2 cm±3

14 2.88´10±6 2.2´10±5 1.60´10±3 480

3.3 Two Phase Sulfonation of Toluene 15 5.55´10 ±5
1.8´10 ±5
1.65´10 ±3
500
±4 ±5 ±3
16 8.12´10 1.6´10 1.75´10 520
The performance capability of the two impinging streams
reactor for heterogeneous sulfonation of toluene has been 17 9.78´10±2 1.5´10±5 1.95´10±3 540

compared with that of the CSTR. To perform such a compar- (1) Data extracted from references 9 and 10; (2) Extrapolated data, extracted
ison, a model for the overall rate of the two-phase sulfona- from reference 15; (3) Data extracted from reference 14.

Chem. Eng. Technol. 2005, 28, No. 1 http://www.cet-journal.de  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 65
 Full Paper

A rough comparison has been made be- 70

+
tween the conversions of toluene in the +

Conversion of Toluene (predicted), (%)

impinging reactor and the predicted val- 60

ues, using the RTD model together with +

+
50
the following relation:
R¥ 40
…CTSA † ˆ …CTSA †droplet Edt (15)
0 30
+
where (CTSA) and (CTSA)droplet, are the +
20
toluene sulfonic acid concentration in the +
effluent and that within the droplets, re- 10
spectively. ++ +
++
An expression for (CTSA)droplet may be 0
0 10 20 30 40 50 60 70
found from the rate equation for toluene
Conversion of Toluene (observed), (%)
sulfonation by considering that each aque-
Figure 5. Comparison between predicted and observed toluene conversion.
ous droplet behaves as a batch reactor
and the sulfuric acid concentration in the
latter is in excess in comparison with that of toluene. A pseu- of reaction, presumably due to the increase in impact forces
do first order reaction with respect to toluene was, therefore, of collision. In certain cases, the efficiency of TISR may be
assumed to occur in the aqueous droplets. The results are improved continuous recycling of the unconverted reactants
shown in Fig. 5. to the impingement zone, in order to increase the contact
There is a broad agreement between the observed and cal- time between the phases within the reaction compartment.
culated data. However, the discrepancies may be attributed Received: July 12, 2004 [CET 7016]
to the limitations imposed by mass transfer processes be-
tween the impinging droplets. In addition, deformation and
coalescence of the latter may have serious effects on the ex- References
tent of reaction, which have been neglected in the present
[1] M. Sohrabi, A. M. Jamshidi, J. Chem. Tech. Biotechnol. 1997, 69, 415.
calculation. [2] I. Elperin, A. Tamir, Israeli Patent Appl. No. 66162; 29±6, 1982.
[3] A. Tamir, D. Herskovitz, Chem. Eng. Sci. 1985, 40, 2149.
[4] M. Sohrabi, M. Ahmadi Marvast, Ind. Eng. Chem. Res. 2000, 39, 1903.
[5] A. Tamir, Y. Kirton, Chem. Eng. Comm. 1987, 50, 241.
4 Conclusion [6] A. Tamir, Y. Kirton, Drying Technol. 1989, 7, 183.
[7] A. Tamir, K. Luzzatto, J. Powder Bulk Solids Technol. 1985, 9, 15.
A general conclusion may be drawn from the present [8] A. Tamir, Chem. Eng. Prog. 1989, 85, 53.
[9] M. Sohrabi, T. Kaghazchi, C. Hanson, J. Appl. Chem. Biotechnol. 1977,
study that the performance capability of the TISR is nor- 27, 453.
mally higher than that of the CSTR for two liquid phase re- [10] M. Sohrabi, T. Kaghazchi, J. Chem. Tech. Biotechnol. 1981, 31, 409.
[11] J. G. van de Vusse, Chem. Eng. Sci. 1962, 17, 507.
actions. This may be related to the breakup of droplets as [12] A. Papoulis, Probability, Random Variables and Stochastic Processes, 3rd
the result of shear forces exerted between the phases, lead- ed., McGraw-Hill Inc., New York 1991.
ing to the enhancement of surface area, rejuvenation of the [13] R. A. Howard, Dynamic Programming and Markov Processes, John
Wiley & Sons Inc., New York 1960.
interface, and therefore, an increase in mass transfer rates. [14] M. Sohrabi, Afinidad 1983, 50, 181.
Increasing the driving nitrogen flow rate enhances the extent [15] H. Cerfontain, A. Telder, Rec. Trav. Chim. 1965, 84, 545.

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