2316 Ind. Eng. Chem. Res.

2002, 41, 2316-2319

A Contactor for Liquid-Liquid and Liquid-Solid Extraction of

Vanillin
F. G. Zhu* and S. H. Zhou
Petrochemical Institute, East China University Of Chemical Technology, 1166 Songjing Road,
Shanghai 201512, China

A special reciprocating plate extraction contactor using vibration of high frequency and low
amplitude and the component materials, which are oil-attractive, water-repellent, and corrosion-
resisting, and the method of reverse phase extraction have been studied for extracting vanillin
from acidified solution containing sticky particles. The experimental results show that it has
considerable characteristics, that is, better extraction efficiency, higher throughput, less time
of phase separation, more effective prevention of solids accumulating in the column, and longer
service life in corrosion. The extraction of liquid-liquid and liquid-solid can be performed
continuously in the same column when the vanillin transfers from the drops phase, in which
the particles adsorb some vanillin, to the continuous phase. Extraction efficiency of 95% and
crude vanillin of 88.6% can be obtained, resulting in a total yield of the purification processes
from 66.5% up to 86.5%.

Introduction
In a new process of manufacturing vanillin, it is
required to extract vanillin solved in the acidic feed
stream in which there are some particles of resin, gum,
lignin, and so forth. These particles are separated out
when the mass transfer proceeds.The particles adsorb
solute vanillin, thus reducing the extraction efficiency,
and accumulate on the plates to clog the passageway of
the two fluids so that the operation has to be stopped
and the extraction efficiency reduces.
Until now,the extractions of liquid-liquid and liquid-
solid are usually performed in different contactors, such
as RDC,1-3 and RPC4-6 for the former, in which only a
modicum of solids are allowed, and several kinds of
leachers7,8 for the latter. Because the solids are sticky
substances, the liquid-solid extraction will become even
more complicated. Some research9-11 described modified
contactors that could be used for the feed containing the
solids but not for sticky solids yet.
Moreover, the process conditions of temperature 60
C, H2SO4 10% or HCl 5% in extraction, and tempera-
ture 60 C, NaOH 10% in cleaning, are selected so that
the materials would withstand corrosion of both acid
and alkali solution12-14. Figure 1. Structure of extractor.

Experimental Section phase extraction. There were three outlets for extract
overflow, raffinate, and resinous solids, which were
Apparatus Structure. The special reciprocating heated to about 105 C by steam passing through a
plate contactor as shown in Figure 1 was constructed conical jacket, and two inlets for solvent, toluene, and
from an extraction section of 50 mm diameter, 870 mm feed, acidified solution. The structure of this column is
height, two settling sections of 90-mm diameter at the different from conventional RPC.
top and the bottom, and total 160-mm height, in which Experimental Flow Chart. The setup is illustrated
35 plates with 60% opening were fixed on the shaft, with in Figure 2. A measuring pump drew acid liquid from a
frequency and amplitude of vibration varied according feed tank, in which a stirrer was used for dispersing
to the experimental requirement. Epoxy resin, Teflon, sticky solids, and transported them into the tower
and stainless steel were used as vibrating plates for passing a heater at 60 C. Solvent toluene was pumped
different tests. An interface meter was set at the bottom to the column by another measuring pump flowing
settling section instead of at the top for the reverse through a heater at 60 C also. The vibration frequency
of the shaft could be regulated by controlling the input
* To whom correspondence should be addressed. E-mail: voltage of a direct current motor. The interface position
sfercffb@online.sh.cn. Fax: 021-57971075. was adjusted by using an electromagnetic valve that
10.1021/ie010258d CCC: $22.00 2002 American Chemical Society
Published on Web 03/27/2002

Figure 2. Experiment setup.
Figure 3. Accumulation in different transfer directions.
could control the outflow of the raffinate. The resin
heated to temperature 105 C was drained away inter-
mittently twice a day.
When operating, the column was first filled up with
solvent toluene, and then the solvent and feed were
simultaneously set according to the flow rate desired.
After replacing the column volume three times, it could
be considered to have attained a steady state, and
samples of inlet and outlet solutions were collected for
analysis.
Results and Discussions
Effect of Mass-Transfer Directions. Accumulation.
The accumulation of particles in different mass-transfer
directions was plotted versus time in Figure 3. When
the feed containing vanillin and solids acted as dis-
persed phase d and the solvent as continuous phase c
in RPC (i.e., the solute vanillin transferred from d to c
direction), the precipitate of solids on the plates was
<50% of that from c to d at any time after 8 h. If using
RDC, the accumulation quantity was much more, as
much as 5-6 times larger. Because in the mass-transfer
direction from d to c the solids were included within the
dispersed drops and did not make contact with plates,
only a small amount of precipitate accumulated on
them. In RDC, the stator rings and rotating disks were
placed horizontally, so the settling particles accumu-
lated more and more in any mass-transfer directions.
The precipitate quantity in the special RPC can be
expressed by our own experimental model:
j )]0.5(d/c)0.1A-0.08f -0.9
Qp ) 1.16Cs exp(- t)[F/(
(1)
Throughput. From d to c mass-transfer direction, the
increase of total throughput was over 30% (Figure 4)
Ind. Eng. Chem. Res., Vol. 41, No. 9, 2002 2317
Figure 4. Throughput in different transfer directions.
Figure 5. Comparison of throughput.
and the time of phase separation was cut by about 20%
in comparison with the opposite direction. This phe-
nomenon can be explained by the Marangoni effect.15
When the solute vanillin transfers from the dispersed
phase to the continuous phase, coalescence between
drops occurs spontaneously because the liquid films
break easily, in which the vanillin concentration is
higher, but for the opposite case, the films are more
stable, and the drops tend to separate from each other.
The total throughput can be compared with the
correlation given by Baird:16
1.5Ud + Uc ) 0.0224[3/(R2Fj)]1/5[g2F2/(Fcc)]1/3 (2)
R ) (22/3)Fj[(1 - A02)/(A0)2][(2Af)3/Hs] (3)
The calculated values from Bairds equation are lower
than our experimental values because of sticky particles
in the dispersed phase and larger average diameter of
drops in this mass-transfer direction (Figure 5).
The average diameter of drops d32 in this column can
still be calculated by modified Hafezs formula:17
d32 ) 0.44[3/(R2Fj)]1/5 (4)
Efficiency. When mass transfers in the d to c direction
and the /C is less than zero as for the toluene-
vanillin-water system, the coalescence of drops can
enhance the mass-transfer rate and the vibration fre-
quency may be raised by about 30%. Figure 6 shows the
extraction stages in different vanillin transfer direc-
tions. Because of the joint action of stronger coalescence
and higher vibration frequency for dispersing, the tower
efficiency can reach 0.9 extraction stages/m and in-
creases 50% in comparison with the c to d direction
where it is only 0.6 stages/m.
Effect of Vibration Frequency and Amplitude.
Generally, the extraction efficiency increases with fre-
quency (Figure 7). To disperse sticky solids within drops,
2318 Ind. Eng. Chem. Res., Vol. 41, No. 9, 2002

Table 1. Comparison of Material Characteristics

materials corrosion (5% HCl or 10% H2SO4) corrosion (10% NaOH) capacity of H2O-attract rigidity cost
Teflon best best weakest weak expensive
epoxy resin good good weaker stronger cheap
stainless steel corrosion good strong strongest middle

tation of sticky particles on the plates. The comparison

of materials corrosion in alkali or acid solution is shown
in Table 1, in which it can be seen that Teflon is the
best, but in rigidity and economy, epoxy resin is excel-
lent. Stainless steel cannot be used because it attracts
water strongly.
The rate equations (7) and (8) of resin corrosion in
NaOH, H2SO4 solution have been offered by Hojo
et al.:18

Figure 6. Column efficiency. w ) k1(t - t0)1/2 (7)

y ) k2(t - t0)1/2 (8)

The service life of epoxy resin is more than 5 years

according to the calculations and our own experiment.

Conclusions
This investigation has shown that the special RPC
can be used for liquid-liquid and liquid-solid extraction
process in which there are sticky particles suspended
in the feed, and optimum process conditions have been
Figure 7. Extraction efficiency under different vibration condi-
tions. obtained. Reverse phase extraction, vibration of high
frequency and low amplitude, and the oil-attractive and
water-repellent materials are three important factors
which prevent sticky particles accumulating in the
column. For industrial design and calculation, math-
ematical models have been selected and some have been
Figure 8. Effect of different materials on the wetting of water. found by experiment. Epoxy resin and Teflon are the
best materials for reverse phase extraction, resisting
increase vanillin yield, and reduce particles accumula- both acid and alkali corrosion.
tion, a higher vibration frequency is necessary. At
amplitude 2.5 mm, frequency over 300 rpm, the extrac- Acknowledgment
tion efficiency increases. When A ) 7.5 mm and f ) 150
rpm, the extraction efficiency increases slowly, and at The authors are very grateful to Professor Teh C. Lo
this amplitude, f above 300 rpm, the extraction ef- of T. C. Lo & Associates who gave the guidance and
ficiency falls because the mass-transfer coefficient de- offered useful materials and data. Thanks are due to
creases as the drops become rigid. Ms. Hai-Yan Fei, Zhen-Ping Ye, and Mr. Zhen-Xun
Simultaneously, the throughput will decrease signifi- Gong for the experimental work.
cantly. The best process conditions are amplitude 5 mm
and frequency 250 rpm. Thus, the extraction efficiency Nomenclature
is over 95%, the throughput is more than 6.62 m3/m2h,
A0 ) fractional open area
the purity of vanillin in extract-removed solvent reaches
A ) amplitude of vibration, mm
88.6% as the phase ratio reduces to 0.8, and it makes a Cs ) solids concentration, gL-1
total yield of purification processes from 66.5% up to d32 ) average drop diameter, mm
86.5%. D ) column diameter, mm
The results of measuring input power P of vibration f ) frequency of vibration, rmin-1
are close to the equation proposed by Hafez:17 g ) gravity acceleration, ms-2
Hs ) distance between plates, cm
P ) 2AfnNmaxD2/(4) (5) k1, k2 ) coefficient
n ) plate numbers
Nmax ) (9.7 103)Af + (1.8 106)A2f2 (6) P ) input power, W
Qp ) precipitate quantity on the plates of RDC or RPC,
gm-2
The consumption power in A ) 7.5 mm is larger than t0, t ) incubation period, time, h
in A ) 5 mm. Ud, Uc ) flow velocity of dispersed and continuous phases,
Effect of Material Characteristics. Figure 8 rep- ms-1
resents the repellent action between water and three w ) amount of dissolution, mgm-2
kinds of materials which are Teflon (photo A), epoxy y ) penetration depth of solution, m
resin (photo B), and stainless steel (photo C). The less ) coefficient
the wetting of the plates, the more difficult the precipi- ) interfacial tension, Nm-1

) mechanical efficiency of vibration
Fj, Fc, F ) average and continuous phase density, density
difference, kgm-3
j , c, d ) average, continuous, and dispersed phase
viscosity, Pas
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Received for review March 22, 2001
Revised manuscript received November 30, 2001
Accepted November 30, 2001
IE010258D