J. Chem. T echnol. Biotechnol.

1997, 70, 247252

Recovery and Concentration by Electrodialysis of

Tartaric Acid from Fruit Juice Industries Waste
Waters
Luis J. Andre s,1* Francisco A. Riera2 & Ricardo Alvarez2
1 Technological Institute of Materials (ITMA), Parque Tecnologico de Asturias, 33428 Llanera, Asturias,
Spain
2 Department of Chemical Engineering, University of Oviedo, 33071 Oviedo, Spain
(Received 10 December 1996 ; revised version received 3 June 1997 ; accepted 12 June 1997)

Abstract : Electrodialysis (ED) has been used as a membrane technique to con-

centrate tartaric acid from ion exchange regeneration waters obtained in grape
juice treatment. The initial ion tartrate concentration in these streams varies
between 1 and 10 kg m~3 and can be concentrated more than 60% (532 kg m~3
after 13 300 s). Permeate ux of other common ionic components has been
shown. Optimum intensities and current efficiency have been calculated with syn-
thetic solutions. A mathematical approach has been used to predict nal tartaric
acid concentration and electro-osmotic eects.

J. Chem. T echnol. Biotechnol. 70, 247252 (1997)

No. of Figures : 5. No. of Tables : 4. No. of Refs : 15

Key words : tartaric acid, electrodialysis, waste waters, recovery, fruit juice

NOTATION Superscript
0 At time 0
A Membrane area per cell-pair (m2)
C Solute concentration (mol m~3)
F Faradays constant (A s eq~1) 1 INTRODUCTION
i Current density (A m~2)
J Massic solute ux (kg m~2 s~1) Tartaric acid is present in almost all fruits, but it is
J Volumetric water ux (m s~1) especially common in grapes. This organic compound
w
m Anion mass (kg) can be synthesized in the laboratory but, due to eco-
n Number of cell-pairs (dimensionless) nomic reasons, it is usually obtained from fruit wastes,
N Normality (eq m~3) grapes spirit, crude argols, lees, etc. Many well-
S Electrode surface (m2) established processes are in use all over the world.
t Time (s) In the classic process, tartaric acid is precipitated as
V Batch or solution volume (m3) calcium tartrate so that it can be isolated from the rest
of the raw material compounds. Then, it is put into an
a Constant in eqn (2) (m~3 g~1)
acidic medium (sulphuric acid) and is regenerated as
b Constant in eqn (2) (s m~3 g~1)
tartaric acid. A subsequent concentration step is carried
g Current efficiency (dimensionless)
out by means of evaporation and, nally, it is blended
Subscripts by means of crystallization.
c Related to the concentrated stream Special attention must be paid during the tartaric
w Related to water transport acid purication process if the nal product is to be
used as an acidulant compound in soft drinks or as in
* To whom correspondence should be addressed. an additive in medicines, cosmetics, etc.
247
( 1997 SCI. J. Chem. T echnol. Biotechnol. 0268-2575/97/$17.50. Printed in Great Britain
248
Other sub-products are being used nowadays as a
source of tartaric compounds ; among these, the most
important are by-products from the wine industries.
Two dierent aspects must be taken into account when
these materials are to be processed. Firstly, they are
important pollutants and hence must be pretreated
before disposal. Secondly, the tartaric content in these
kinds of materials is very low and it has been demon-
strated that production of tartaric acid from these
sources is only protable if its content is above 20% wt
in the raw material.1
During industrial production of fruit juices, tartaric
acid must be partially removed from the juice in order
to be stabilized prior to consumption. Ion exchange
techniques are widely used in this step. In this process,
tartrate ions are removed from the juice in order to
avoid later precipitations of tartrate crystals when the
temperature of the juice decreases. In ionic exchange,
tartrate ions are then substituted by chloride ions.
During ion exchange processes huge amounts of
regeneration solutions from the resins are produced.
These solutions contain between 1 and 10 kg m~3 of
equivalent tartaric acid. These streams are usually not
re-used. Preconcentration of these streams is necessary
in order to recover residual tartaric acid.
Some dierent techniques such as electrodialysis
(ED), evaporation, ionic exchange, reverse osmosis, etc.
could be useful to preconcentrate the tartaric acid from
these streams. ED has some advantages related to the
ease with which the process can be developed at an
industrial scale (modular processes), and in addition it
does not add any external compound to the solution.2h4
Consequently, tartaric acid recovered by ED can be
used in food and medicines without any other kind of
treatment.
During the ED process, tartrate can be recovered
mainly as potassium tartrate, and then it can undergo a
methatesis reaction with conventional or bipolar mem-
branes.5 After this purication, a nal concentration
can be made by thermal processes.
Fig. 1. Schematic diagram of the ED stack.
L . J. Andre s, F. A. Riera, R. Alvarez
The aim of this work was to study the ED process as
an alternative method for purifying and concentrating
tartaric acid from regeneration waters of an ion
exchange treatment. Two synthetic solutions have been
tested in order to know the maximum tartaric concen-
tration and purity achieved.
2 MATERIALS AND METHODS
Runs were carried out in an Stantech stack (LT-1)
(Hamburg, Germany) used in its standard congu-
ration. Cationic and anionic membranes were separated
either by a diluting or a concentrating spacer. Two
guard channels were incorporated near each electrode.
The complete unit consists of 10 cell pairs sand-
wiched between two electrodes made of non-corrosive
materials (the cathode of 316 stainless steel and the
anode of platinized titanium). The eective membrane
surface of the unit was 02 m2.
The membrane used were of the SC-1 (cation
exchange, t ` \ 091) and SA-1 (anion exchange,
Na
t ~ \ 093) type which present low electrical resistance
Cl
and good mechanical and thermal properties.
Most of the microorganisms aecting tartaric acid
solutions show optimum growth at temperatures
between 28 and 37C.6 Thus, the experiments were per-
formed at 25C and 40C to limit this growth. The unit
is batch designed and concentrated and diluted streams
are totally recycled. Figure 1 shows a schematic
diagram of the ED unit.
2.1 Raw materials
The streams from ion exchange regeneration dier in
composition, depending on the kind of fruit used even
on the season.
In order to study the ED behaviour when other com-
pounds (mainly sugars) are present in the feed, synthetic
solutions were prepared and electrodialysed.
Electrodialysis of tartaric acid from waste waters 249

TABLE 1 The tartrate concentration throughout the experi-

Composition of Regeneration Waters from Ionic Exchange ment was measured by colorimetric determination at
535 nm of a pervanadyltartrate complex formed.10
Compounds Concentration (kg m~3) Other ionic compounds were measured by means of
high resolution ionic chromatography and atomic
Cations
Na` 0102 absorption.11,12
K` 117 Maximum tartaric concentration is limited by
NH` 803 ] 10~3 electro-osmotic and diusion eects. In general, the con-
4 centration of each ion in the concentrated stream can be
Ca2` 6070 ] 10~3
Mg2` 360 ] 10~3 written as :13
Acids
Tartaric 47 m0 ] JAt
Malic 40950 ] 10~3 C \ c (1)
c V 0 ] J At
Acetic 4147 ] 10~3 c w
Citric 5220 ] 10~3 where m0 is the tartaric anion mass at t \ 0 in the con-
Siquimic 328 ] 10~3 c
centrated stream, V 0 is the solution volume at t \ 0 in
Others c
the concentrated stream, A is the membrane area, t is
Sugars \ 01 ] 10~3
pH 46 the operating time, J is the ionic ux across the mem-
branes and J is the water permeate ux.
w
Equation (1) can be linearized as follows :
2.1.1 First synthetic feed
The inuence of glucose in tartrate electrodialysis is not 1 1
yet well understood. Glucose can cause membrane \a]b (2)
*C t
fouling or even pass through the membrane. This eect c
can be important from the point of view of nal tartaric where *C is the ion concentration dierence at time t,
acid purity in the concentrated stream. c
and a, b are parameters related to the process.
A solution (45 dm3) containing 10 kg m~3 of equiva- In order to check the validity of eqn (2), synthetic
lent tartaric acid and 60 kg m~3 of glucose was electro- solutions (numbers 1 and 2) were tested under the same
dialysed at 40C (outlet temperature in real plants). Two conditions. In both cases a good agreement between
dm3 of tartaric acid, 10 kg m~3, was used as concen- eqn (2) and the experimental results was found.
trated solution and 10 dm3 of 20 kg m~3 sodium sul- Table 2 shows the experimental values of a and b.
phate (pH 2) was used as electrode washer. These two parameters can be related to permeate ux
and to the maximum concentration of tartrate ion.
2.1.2 Second synthetic feed
Real regeneration waters from ionic exchange columns
have some ionic compounds apart from tartrate ion J\
a V0 1
c
A] C0
B (3)
b A a c
that can compete during the electrodialysis process.
A sample from a real stream was analysed in order to a V0
prepare a synthetic solution which includes all the ionic J \ c (4)
w b A
compounds. Table 1 shows the composition of the real
solution. J 1
One dm3 potassium tartrate (5 kg m~3 analytical (C ) \ \ ] C0 (5)
c Max J a c
grade) was used as the concentrated stream. The elec- w
trode washer was sodium sulphate (20 kg m~3) and the Permeate ux of both tartaric acid and water, and
solution was adjusted to pH 2 by adding sulphuric acid maximum tartrate ion concentration reached can be
(980 kg m~3). calculated from eqns (3), (4) and (5). Figures 2 and 3
TABLE 2
3 EXPERIMENTAL RESULTS AND Experimental Values of a and b Parameters from eqn (2)
DISCUSSION
i a b r
Critical current densities were measured according to (A m~2) (m3 kg~1) (s m3 kg~1)
previous procedures.7 The values obtained between 135
157 523 ] 10~3 19228 0999
and 145 A m~2, are in good agreement with results
135 489 ] 10~3 25141 0999
from previous work.8,9 It was found that temperature 60 612 ] 10~3 45813 0974
and ow across the stack, in the experimental range 100 600 ] 10~3 27698 0997
used, have no important inuence on critical current 122 492 ] 10~3 18121 0991
densities.
250
Fig. 2. Permeate ux of tartrate ion and water versus current
density. , Tartrate ion ; L, water.
show permeate ux and maximum ion tartrate concen-
tration, respectively.
Maximum tartrate ion concentration can be obtained
near to the critical current density. Higher intensities do
not improve the permeate ux. On the other hand,
electro-osmotic eects that oppose the ion concentra-
tion are enhanced at high intensities. With respect to
the optimum intensity, maximum tartrate ion concen-
Fig. 3. Maximum tartrate ion concentration, current effi-
ciency and energy consumption versus current density.
L . J. Andre s, F. A. Riera, R. Alvarez
tration can be easily obtained from Fig. 3 However, it is
necessary to take into account current efficiency (g) and
energy consumption. These two aspects are included in
Fig. 3.
Current efficiency has been dened as the current
carried by ion tartaric and the total current across ED
stack ratio, i.e. :
*N V F
g\ c c 100 (6)
inSt
where N is the tartrate ion concentration in the con-
c
centrated stream at time t expressed as normality, V is
c
the volume of concentrated stream at t, n is the cell-pair
number in the stack, S is the electrode surface and F is
Faradays constant.
As can be seen, maximum current efficiency (nearly
65%) corresponds to the same intensity at which the
energy consumption is at a minimum. The current effi-
ciency obtained in this work is close to others found in
similar processes.14 The presence of other ionic com-
pounds (that compete with the tartrate ion), the Joule
eect and local short-circuits can explain this percent-
age.
From these results, optimum current density is about
120 A m~2. This value corresponds to an initial voltage
of 244 volts between electrodes.
In order to check the validity of the developed mathe-
matical approach a run was carried out at 25C for
37 h. From eqn (2) the concentration evolution of tar-
trate ion in the concentrated stream can be estimated.
This dependence is shown in Fig. 4. Final tartrate con-
centration was 532 kg m~3, very near to the concentra-
tion obtained from eqn (2). Thus, a good agreement is
obtained.
With respect to the rest of the ionic species con-
sidered in the raw material, Table 3 shows the nal con-
centration and the average permeate ow in each case.
The absence of glucose in the concentrated stream
was veried. From Table 3, the degree of purication of
tartrate ion in the nal concentrated stream can be cal-
culated. The high value obtained, more than 60%, must
be considered as a good result, since the concentration
factor was very high at the end of the process.
Fig. 4. Evolution of tartrate ion concentration with time. L,
Experimental results ; line, mathematical approach (eqn (2)).
Electrodialysis of tartaric acid from waste waters 251

TABLE 3 considerations it is possible to make an estimation of

Final Concentrations and Average Permeate Flux of Other membrane area.
Ions Basis
Ion Final concentration Ionic mass ux Labour time 2000 h
(kg m~3) (kg m~2 s~1) Waste water treated 1300 m3
Feed tartaric concentration 10 kg m~3
K` 51 425 ] 10~6 Tartaric acid production 13 000 kg
Na` 94 635 ] 10~6 Current efciency (overall) 65%
NO~ 07 527 ] 10~7 Tartrate ux (average) 4 ] 10~5 kg m~2 s~1
3
Acetate 12 917 ] 10~7
Power consumption 5 ] 103 kJ kg~1
Malate 14 106 ] 10~6
Citrate \03
tartaric acid
The membrane area required is given by :
Membrane area
From eqn (4), the volume of water transferred from
diluted to concentrated streams (electro-osmotic eects) tartaric acid production
\ \ 45 m2 (7)
can be predicted. These eects contribute to the dilution labour time ] tartaric ux
of tartrate ion and must be minimized as much as pos-
sible. Figure 5 shows the good agreement between the There are commercial ED stacks available that are
mathematical model (eqn (4)) and the experimental being used in wine demineralization. Data relative to
results. costs and economic aspects have been reported.15 Table
The key process parameters governing the design and 4 summarizes the costs estimation. It should be empha-
economy of the ED process are the membrane area, sized that the operating costs in Table 4 take as refer-
power consumption, membrane life and costs. The eco- ence a concentrated solution of tartaric acid of about
nomic estimations presented in this work assume a sea- 20% (w/w). Additional costs must be included in further
sonal production of waste water. Thus, 2000 h of labour concentrating steps (e.g. evaporation processes), if neces-
per operation has been considered. According to these sary.

4 CONCLUSIONS

Tartaric acid is a valuable by-product from regener-

ation waters of ionic exchange towers. In order to
obtain an economic benet, a concentration/
purication step until 20% (w/w) is necessary. However,
it would be desirable to recover the tartaric acid in
higher concentration with a minimum amount of impu-
rities. On the other hand the exhausted waters would
represent an environmental problem if they are wasted.
Fig. 5. Prediction of electro-osmotics eects. L, Experimental In this work the technical feasibility of tartaric acid
results ; line, theoretical data from eqn (4). concentration with conventional electrodialysis has
been shown. The initial tartaric concentration (between
TABLE 4 1 and 10 kg m~3) can be increased ve times after 37 h
Capital Costs and Operating Cost Estimation of the ED- at 25C. Data extrapolation allows a maximum concen-
Tartaric Acid Operation tration of about 200 kg m~3 to be predicted.
Limit current density is about 135145 A m~2 and
T otal capital (thousands $) optimal current density has been estimated at
Stacks and auxiliaries. Total direct
120 A m~2. This parameter is slightly dependent on
costs (DC) 319.0
Indirect costs (45% DC) 143.6
temperature and ow rate but it seems not to be
Contingency (20% DC) 63.8 aected by other variables. Current efficiency is about
Total capital costs (TC) 526.4 65% and the energy consumption is around
50 ] 103 kJ kg~1 tartaric acid. All these data are in
Operating costs (thousands $) reasonable agreement with those reported in the liter-
Membrane life (years) 3
ature.13
Membrane replacement 16.6
Direct power consumption (kW h) 1.8 ] 104
Because ED separation processes do not need the
Power consumption addition of chemicals and the technique is a simulta-
(0.1 $ per kW h) 2.8 neous concentrationpurication process, the tartaric
acid obtained is quite pure ( B 60%) and thus useful for
252
further transformations in the food or pharmaceutical
industries.
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