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Desalination 146 (2002) 393–398

Interest of electrodialysis to reduce potassium level in vinasses.


Preliminary experiments

Martine Declouxa*, André Boriesb, Richard Lewandowskia, Claire Farguesa,


Amel Mersada, Marie Laure Lameloisea, Frédéric Bonneta, Bertrand Dherbecourta,
Leandro Nieto Osunaa
a
ENSIA, UMR Genial, 1 ave des Olympiades, 91744 Massy Cedex, France
Tel. +33 (1) 69 93 50 92; Fax +33 (1) 69 93 50 44; email: decloux@ensia.inra.fr
b
INRA – Equipe bio-procédés et agro-dérivés MIGM, 11430 Gruissan, France
Tel. +33 (4) 68 49 44 06; Fax +33 (4) 68 49 44 02; email: bories@ensam.inra.fr

Received 8 February 2002; accepted 26 March 2002

Abstract

Nowadays, treatment of vinasse from the alcohol fermentation is a major cost centre which decides the economic
viability of this traditional industry. Increasingly stringent environment norms in France have put enormous pressure
on manufacturers of alcohol from traditional feedstock like beet molasses. Nowadays, the most industrial treatment
is the vinasse valorisation as fertiliser in the field after concentration. Nevertheless, the final solids are limited
because of the sulphate potassium crystallisation and precipitation in evaporator tubes, storage tanks and fertiliser
sprayers. The paper gives some figures of beet molasses vinasse composition, details the most widely used treatment
schemes and presents the first results obtained with an electrodialysis treatment to reduce the potassium concentration
in view to prevent the crystallisation and even increase the final dissolved solids of the concentrated vinasse.

Keywords: Stillage; Vinasse; Beet molasses; Potassium; Membrane; Electrodialysis

1. Introduction industry: modification of production procedures,


treatment of effluent at the source” and INRA’s
In April 2000, as part of a joint INRA-CNRS
commitment to conducting cross-disciplinary
project “Minimising wastewater in the food
projects, we undertook a study on the treatment
and utilisation schemes for stillage from distilleries.
*Corresponding author.
Presented at the International Congress on Membranes and Membrane Processes (ICOM), Toulouse, France,
July 7–12, 2002.

0011-9164/02/$– See front matter © 2002 Elsevier Science B.V. All rights reserved
394 M. Decloux et al. / Desalination 146 (2002) 393–398

For each litre of ethanol produced, 10–15 L of Table 1


stillage (vinasse) are evacuated form distillery Typical composition of beet molasses stillage in Greece
units. This vinasse, of varying composition, repre- (mean over 3 years) [4]
sents considerable volumes and must be treated
pH 4.3±0.5
in all cases. To further our research, we carried
Solids, g/L 95±25
out a bibliographic review listing the studies made
Organics, g/L 55±15
in this field and interviewed the main people
Volatile acids, g/L 1.95±0.185
involved in the sector. The aim was to determine
Total nitrogen (N), g/L 4.75±0.15
whether the treatment of vinasse requires studies
Total phosphorus (P), g/L ND
for resolving environmental problems and/or
Sulphate, g/L 3.5±1.05
improving how they can be put to optimum use.
Potash (K2O), g/L 6.7±3.5
This article, first presents the main problems
BOD, g/L 27.5±9.5
underlined in the literature survey on beet
COD, g/L 55.5±25
molasses vinasse treatment [1] then presents the
first laboratory results on membrane treatments
to reduce the potassium concentration. Table 2
Typical composition of stillage in USA [2,3]
2. Composition and valorisation of vinasse
Beet Cane
from beet molasses fermentation
pH 4.6–4.9 4.6–4.9
1.1. Composition Solids, g/L 70–95 70–90
Sugar beet distilleries produce the equivalent Glycerol, g/L 6.5–9.0 24–30
of 4,500,000 hL PA (pure alcohol) mainly from Betaine, g/L 15–20 —
molasses (600,000 t/y), sugar beet syrups and Succinic acid, g/L 0.8–0.9 1.5–2.0
juice. Since January 2001, there is no longer in Inositol, g/L 0.4–0.9 0.9–2.8
France any sugar beet juice distillery which does Aconitic acid, g/L — 0.9–1.3
not adjoin a sugar plant. If the must is constituted Itaconic acid, g/L — 0.7–1.1
only of beet juice, the stillage is recycled in the BOD5 (in O2), g/L 30–40 28–38
diffuser of the sugar plant. This recycling resolves
the problem of treating stillage but increases the
proportion of non-sugars in raw juice hence the
by Table 3 which provides the distribution of the
difficulties in obtaining good quality sugar.
dry matter of several concentrated stillages produced
Outside the sugar harvest period, distilleries
in France.
produce alcohol principally from molasses or green
syrups (intermediary crystallisation products). The
2.2. Most widely used methods of treatment
stillage from the fermentation of sugar beet molasses
has an acid pH, a dry matter content of about In France, concentrated beet vinasse is used
100 g/L including 60% of organic matter, a chemical as fertiliser by all the distilleries. The research
oxygen demand (COD) of around 60 g/L and a bio- conducted by the ITB in close collaboration with
logical oxygen demand (BOD) of about 30 g/L INRA, ITCF and the Water Agencies [5,6] has
(Table 1). The potassium content (K2O) is high demonstrated the fertiliser value of stillage which
(8 g/100 gDM). As specified by [2,3], the stillage is classified as a NPK fertiliser by the AFNOR
of sugar beet molasses is rich in glycerol (6 g/L) NF U 42-001 [7]. These fertilisers must contain
and betaine (15–20 g/L) (Table 2). This is confirmed more than 10% of (N+P2O5+K2O) with a minimum
M. Decloux et al. / Desalination 146 (2002) 393–398 395

Table3 To limit this spontaneous formation of potassium


Composition of several concentrated beet molasses stillages sulphate crystals during the concentration stage
from French factories or during the storage of the concentrated stillage,
Factory 1 2 3
more and more distilleries acidify the fermentation
must with hydrochloric acid instead of sulphuric
g/100 g solids acid, potassium chloride being much more soluble
Ash 30.5 27.6 21.1 than potassium sulphate.
Organics 69.5 72.4 78.9 It is also possible to promote and control the
Glycerol 9.0 13.6 26.0 crystallisation of potassium sulphate. Moreover,
Betaine 14.4 14.2 12.8 this must be done obligatorily when using con-
Sodium 2.0 2.4 0.9 centrated vinasse for cattle feed. It must in this
Potash (K2O) 7.7 10.7 8.8 case contain less than 2–3% of potassium compared
Sulphate 1.2 1.0 1.5 to the dry matter (less than 9.3 g K2SO4/100 g of
Chloride 1.0 4.5 3.8 concentrated vinasse) and have a total nitrogen
Calcium 0.08 0.3 0.2 content (measured by mineralisation and multiplied
Magnesium 0.03 0.02 0.03 by 6.25) at least equal to 39%. But to crystallise
Nitrogen 4.2 4.04 2.9 potassium sulphate, sufficient sulphate ions are
Total nitrogen (6.25) 26.3 25.23 18.4 necessary to react first with the calcium then with
TOC 37.0 36.88 42.4 the potassium. But beet vinasse is relatively poor
in sulphate ions (Tables 1 and 3), even if the
fermentation medium is acidified with sulphuric
of 3% nitrogen and 6% potash (K2O) and not acid. Sulphate ions therefore need to be added so
contain more than 2% of chlorine. According to that the reaction can occur. Ammonium sulphate
the study conducted by SNPAA [5], the nitrogen (NH4)2SO4 or sodium sulphate Na2SO4 can be
of stillage is almost totally in organic form: amino used. Considering that all the sulphate ions are
acids, glutamic acid salts, betaine (2–4%). The brought by the ammonium sulphate, there needs
average quantity of concentrated stillage applied to be a quantity almost equivalent to that of the
to the land is 3 t/ha, that is 225 kg/ha of K2O and potassium sulphate produced. The ammonium
90 kg/ha of total nitrogen (50–60% of which are sulphate is more interesting because it makes it
available the first year of application). Fertilising possible to limit the sodium sulphate concentration
sugar beet with concentrated stillage improves which must not crystallise and the addition of
the yield per hectare by 2–2.5 t/ha. Molasses vinasse nitrogen can increase the total nitrogen content
enjoys a particular status since it is a natural of the concentrated vinasse. The cost of the
fertiliser produced on a large scale and whose ammonium sulphate is thus in part compensated
quality is acknowledged unanimously. Concen- for by a better utilisation of the vinasse. Potassium
trated vinasse can also be used in organic farming sulphate is used as fertiliser and corresponds to
in conformity with the European directive CEE the norm NF44-001. But, since the cattle feed
2092/91. market is not economically worthwhile, only one
The vinasse at the output of the distillation distillery in France went as far in crystallising
column (light vinasse) is concentrated in multiple potassium sulphate. Nevertheless, several distilleries
effect evaporators to 55% solids. But the final extract crystals from the concentrated vinasse,
solids content is limited by the risks of spontaneous only to limit the deposit in the evaporator and
crystallisation of the potassium sulphate and the the storage reservoirs.
deposit at the bottom of the storage reservoirs. Whatever the concentration, with or without
396 M. Decloux et al. / Desalination 146 (2002) 393–398

potassium crystallisation control, the concentration prevent any crystallisation during the vinasse
phase is accompanied by a production of con- concentration and storage.
densates with a COD (1–5 g/L) above the discharge
norm. These condensates are most often treated 3.1. Materials and methods
in lagooning or in aeration basins. To limit the 3.1.1. Vinasse
cost of this treatment and the water consumption
The vinasse sent by Lillers was repartited in
of the plant, it is possible to filtrate the condensate
five 200-L tanks and stored at 4°C.
with a reverse osmosis unit. The permeate (80%
of the volume of the condensates) is recycled in
3.1.2. Analysis of the potassium
fermentation and the retentate is treated in aerated
lagooning. But that solution is not optimal and Attention was first focused on potassium
only one distillery in France is equipped with such concentration. Three methods were tested:
system since 1997. colorimetric test (Hach 2000), atomic spectro-
metry and capillary electrophoresis (Quanta 4000,
2.3. Conclusion Waters).
According to these results, we decided, in The capillary electrophoresis was selected as
march 2001, to conduct two research projects in it was possible to measure three cations (potassium,
parallel: sodium and calcium) at a time. Furthermore, the
sample dilution level was ten fold smaller than
• A study on the way to recycle condensates in
for atomic spectrometry.
fermentation. A project was submitted to
obtain government founds and a thesis started
3.1.3. Clarification of the vinasse
last October.
• An experimental study started in the ENSIA Tests were performed with a laboratory pilot
pilot plant to test the interest to decrease the equipped with Kerasep mineral membranes (Orelis,
vinasse potassium concentration by electro- France). 0.12 m2 membrane area with 0.1 µm and
dialysis before concentration. The results 15 kg/mol pore sizes were tested using in each
obtained until now are detailed here. case a total recycling mode first, then a concentration
mode up to a VRR (Volumetric Reduction Ratio)
of 3 [8]. All the tests were performed at a cross-
3. Electrodialysis of beet vinasse to reduce flow velocity of 5 m/s and a temperature of 80°C.
potassium concentration The clarification efficiency was checked by
The distillery of Lillers (in the north of France) turbidity measurements with a Hach 2000 AN
sent 1 m3 of light beet vinasse, sampled at the turbiditimeter.
exit of the distillation column. The vinasse was
quite turbid because this plant does centrifuge 3.1.4. Electrodialysis
the wine before distillation. A laboratory electrodialysis pilot (EUR 2B
As the laboratory had not any practice on such 10P30) was purchased from Eurodia (Wissous,
product, it was decided: France). The module contents ten cells with 2
• to set the analysis method to measure the compartments of one anion (AMXsb) and one
potassium concentration, cation (CMXbs) exchange membranes. The
• to test the necessity of a clarifying pre-treatment whole area was 0.2 m2.
before electrodialysis, After some preliminary trials, the following
• then to check that the electrodialysis decreases conditions were chosen:
sufficiently the potassium concentration to • Constant voltage: 17 V
M. Decloux et al. / Desalination 146 (2002) 393–398 397

• Concentrated solution (brine): 2 L of 5 g NaCL/ of vinasse:


L (dilution with tap water) • ultrafiltred vinasse,
• Electrolyte solution: 2 L of 21 g KNO3/L (dilu- • raw vinasse sampled directly from the top of
tion with tap water) the 200-L tank,
During each experiment, current density (A), • raw vinasse taken after agitation of the tank.
conductivity (mS/cm), pH and temperature (°C) One last set of two experiments was performed
were recorded every minute. In each set, four with extraction of samples for analysis.
experiments where consecutively performed with In all the sets, evolution of the parameters were
new vinasse and brine solutions but without any similar (Fig. 1). The current density decreased from
change of the electrolyte solution or membrane 5.5 to 1 A, the pH from 4.5 to 2.9, the conductivity
cleaning. The objective was to check the repro- from 21 to 2 mS/cm and the temperature increased
ducibility. Each solution (diluate and brine) were from 20 to 27°C in 45 min (Fig. 2).
sampled at the beginning and at the end of the
run for analysis. After each set, the pilot was 6
cleaned following five steps (water rinsing,
5
circulation of 4 g/L soda solution at room temp- batch 1
erature during 20 min, water rinsing again, 4 batch 2
circulation of 4 g/L hydrochloric acid during batch 3
3 batch 4
20 min, final water rinsing). The cleaning
efficiency was then controlled measuring the 2
Faraday coefficient recovery.
1

3.2. Results and discussion 0


0 10 20 30 40
3.2.1. Vinasse clarification by micro- and time (min)
ultrafiltration
Fig. 1. Current evolution during electrodialysis of light beet
The clarification of the vinasse with 0.1 µm molasses stillage.
pore size membrane was not efficient and the
fouling was important.
With the 15 kg/mol pore size membrane and 32 5
a 0.5 bar average transmembrane pressure, the 28 4.5
flux stabilised around 50 L.h–1.m–2. The VRR 4
24
increase up to 3 was not high enough to detect 3.5
20
any flux decrease. 3

As, the main interest of these experiments, was


pH

16 2.5
conductivity (mS/cm)
to collect clarified vinasse for the electrodialysis 12 temperature (°C) 2
pH
experiments, not any optimisation was carried 8
1.5

out. 1
4 0.5
0 0
3.2.2. Electrodialysis of clarified and raw 0 5 10 15 20 25 30 35 40 45
vinasse Time (min)

Three sets of 4 experiments as explained Fig. 2. Parameters evolution during electrodialysis of light
previously were performed with different kinds beet molasses stillage.
398 M. Decloux et al. / Desalination 146 (2002) 393–398

It was found that the clarification of the vinasse 10.0


before electrodialysis was not compulsory. 8.0
Thanks to the last set, with regular sampling
6.0
of diluate (vinasse), it was possible to link the
conductivity decrease to the cation concentration 4.0
evolution. Regular decreasing of potassium 2.0
(Fig. 3) from 10 to 2.5 g/L and even 0.5 g/L was
0.0
observed while the decreasing of calcium and
0 10 20 30 40
sodium ion levels was very low, from 0.3 to time (min)
0.25 g/L and 2 to 1.5 g/L, respectively. Fig. 3. Potassium concentration evolution during the
Expressed in equivalents, the potassium electrodialysis of light beet molasses vinasse.
concentration decrease was 0.5 equivalent with
0.2 m2 membrane area in nearly 30 min. The from the drained brine has also to be taken in
potassium flux was then of 5 eq.h–1.m–2. account.
It may be considered that the limit of the
potassium sulphate concentration in concentrated References
vinasse is equivalent to 105.59 g K 2SO 4/L
(23.7 g K/L) at 20°C according to [10]. [1] M. Decloux and A. Bories, Traitement et valorisation
des vinasses: problématique et synthèse des voies de
If the potassium concentration of the vinasse valorisation. Industries Alimentaires et Agricoles,
is decreased to 2 g/L by electrodialysis, it will be 118(7/8) (2001) 61–73.
possible to concentrate this electrodialysed vinasse [2] W.H. Kampen and M. Saska. Value-added products
with a factor of 7 (from 10% solids to 70% solids) from stillage of ethanol from molasses and corn to
without any risk of potassium sulphate precipitation. ethanol plants. In: Sugar Industry Technologist. 1999.
[3] W.H. Kampen and M. Saska. Value added products
from stillage of ethanol from molasses plants. Symp.
4. Conclusions on Advanced Technology for Raw Sugar and Cane
These first results are encouraging. They and Beet Refined Sugar Production, New Orleans,
Louisiana, USA, 1999.
proved that the reduction of potassium concen- [4] A. Vlissidis and A.I. Zouboulis, Thermophilic
tration in vinasse using electrodialysis is performant anaeriobic digestion of alcohol distillery wastewaters,
and that it is not necessary to operate a previous Bioresource Technology, 43(2) (1993) 131–140.
clarification step. [5] SNPAA, Vinasse concentrée: aspects agronomiques
Nevertheless, these results must be completed et environnementaux. Syndicat National des Pro-
by bigger pilot tests (at least with 1 m2 membrane ducteurs d’Alcool Agricole, Paris, 1994, p. 25.
area) and longer tests to check the cleaning [6] SNPAA, Vinasse concentrée: étude bibliographique.
recovery. In the same way, experiments have to Syndicat National des Producteurs d’Alcool Agricole,
Paris, 1994, p. 25.
be carried out to measure the real potassium
[7] AFNOR, Amendements organiques: dénominations
sulphate solubility in concentrated vinasse, because et spécifications. Norme NF 44-051, Paris, France, 1981.
it is known [9] that it depends on the vinasse [8] M. Decloux, L. Tatoud and M. Dornier, Essais de
composition which is linked to many factors faisabilité en filtration tangentielle et stratégie de
(molasses composition, must preparation, distilla- dimensionnement d’une unité industrielle. Industries
tion scheme). Furthermore, at an industrial scale, Alimentaires et Agricoles, 7–8 (2000) 59–68.
the brine is not changed after each experiment [9] B. Colin, Cristallisation du sulfate de potassium dans
but regularly drained and diluted with fresh tap les vinasses. Société Messo, 1999.
[10] Mersmann, Crystallization Technology Handbook,
water. The recovery mode of the potassium sulphate
Marcel Dekker, 1995.

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