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Desalination 231 (2008) 283–289

Nanofiltration and reverse osmosis in winemaking

A. Massota, M. Mietton-Peuchota*, C. Peuchotb, V. Milisica


a
Equipe Génie des Procédés et Environnement, UMR Œnologie INRA), Université Bordeaux 2, France
Tel. +33 (5) 5684 6495; Fax +33 5 5684 6468, -97; email: mmp@genproc.u-bordeaux.fr
b
Institut de la Filtration et Techniques Séparatives, Agen, France

Received 9 June 2007; accepted revised 20 October 2007

Abstract
The paper is an overview of the application of membrane processes to winemaking. The aim is to present both
the application of membrane processes in winemaking and a general philosophy of their development from a
process engineering point of view. Several examples illustrate this approach, in particular applications of nanofiltration
and reverse osmosis membranes, but the other techniques such as microfiltration, ultrafiltration and electrodialysis
are also mentioned. The principal condition for further development of membrane processes in winemaking is a
good understanding of membrane techniques, separation techniques and characterisation of the membrane itself
and the product (must or wine) to be filtered. The last constrain, given the complexity and variability of must and
wine composition, is not trivial and needs a considerable effort at both industrial and research levels. For the same
reasons, the coupling of the membrane and other physico-chemical treatments appears to be a promising research
domain.
Keywords: Wine; Membrane filtration; Alcohol content control; Nanofiltration

1. Introduction past, the membrane material was not adapted to


the wine filtration, but at present, the clarifica-
Membrane filtration has been applied to wine
tion cartridges suit perfectly and are integrated in
for a long time. It should be noted that 0.65 μm
all bottling units.
and 0.45 μm filtration cartridges very often used
Subsequently, in a cross-flow filtration mode,
in oenology, are made from membranes. In the
microfiltration membranes were the first to be
applied for wine clarification. The main advan-
*Corresponding author. tage of membranes over cartridges was their ca-

Presented at International Workshop on Membranes and Solid–Liquid Separation Processes, INSA-Toulouse, France
11 July 2007

0011-9164/08/$– See front matter © 2008 Elsevier B.V. All rights reserved
284 A. Massot et al. / Desalination 231 (2008) 283–289

pacity to accept a higher solid concentration in membranes and the large choice of the membranes
the retentate. Initially, the mineral and organic should facilitate their application and increase the
membranes were proposed with 0.2 μm cut-off possibilities for coupling with other membrane
and were used in the final clarification of wines. techniques (reverse osmosis–nanofiltration, ultra-
That application was first developed for the treat- filtration–nanofiltration) with the objective of
ment of large volumes, and afterwards spread to performing corrections to must or wine by reduc-
other domains, for example, to noble-rotted sweet ing or increasing the concentration of a given sol-
wines. Today, microfiltration is largely used in ute. So, for must it is possible to apply the combi-
oenology for must, lees and wine filtration at dif- nation of RO–NF instead of a sole reverse osmo-
ferent membrane cut-off, from 0.1 to 1.2 μm. sis stage as it can treat a smaller quantity of must
The development of reverse osmosis applica- and obtain a higher sugar concentration in must
tion in must concentration was practically done (up to 45°Brix, [7]).
in parallel with that of microfiltration in clarifi- These corrections aim to provide a better equi-
cation [1,2]. However, in both cases two prob- librium and to improve the stability of wine. Mem-
lems slowed their developments; one was tech- brane processes could also be coupled with ion
nological and the second was legislative. The first exchange treatment or with vacuum evaporation.
rose from the fact that the classical RO modules At present, that kind of application is being tested
were designed essentially for water treatment ap- experimentally or is already practised in some
plications where suspended solid concentrations countries for:
are low and particle sizes are small [3]. New de- • Alcohol content control by its partial removal
sign (double spacer for spiral modules), more ef- from wines or by partial sugar removal from
ficient pre-treatment before concentration and musts;
better knowledge of the product to be filtered en- • Volatile acidity reduction in wines;
abled the development of that technique. The RO • Acidification of wines;
membranes being very selective, let through only • Flaw (defect) elimination.
very small molecules or ions. For example, RO
wine permeate contains water, alcohol, acetic acid
2. Control of alcohol content
(60% of the initial concentration), ethylic acetate
(40% of the initial concentration) and lactic acid The studies on control of alcohol content of
(15% of the initial concentration) [4,5]. The re- wines by partial removal of alcohol or sugar from
tention rates are a function of the selected mem- must are initiated by the problems of over con-
brane characteristics. The level of concentration centration of sugar and alcohol that some coun-
is limited by osmotic pressure generated by the tries frequently face, or by the new social trends
process itself and by the applied pressure. of limiting alcohol consumption [8–10]. The pro-
With recent advances in nanofiltration mem- duction of over alcoholised wine concerns the
brane processing different new applications in main part of Mediterranean wine regions in
oenology can be foreseen. The complex separa- France, Spain or Italy, as well as Californian and
tion mechanisms that occur in nanofiltration South American vineyards [11]. The problem
(physical, chemical and electrical interaction be- originates from commendable wine-grower and
tween the solvent, solutes and membrane) make oenological practice. It is widely known that the
the number of the operating parameters that con- quality of red wines depends essentially on the
trol separation efficiency long and give different maturity of phenolic components contained in
results for the same feed and the same membrane grape berries. Phenolic maturity is directly linked
[6]. The specific performance of nanofiltration to a high sugar concentration. Thus the grapes are
A. Massot et al. / Desalination 231 (2008) 283–289 285

picked having high potential alcohol content, up partial sugar reduction combines an ultrafiltration
to 17% vol., with low acidity. This over maturity membrane that allows the sugar to pass through
leads to difficulties in wine making: difficulties and a nanofiltration membrane that retains the
in alcoholic fermentation, in microbiological sugar. The maximum degree of concentration is
stabilisation, as well as gustatory disequilibrium limited by the resistance of the nanofiltration
(strengthening of warm sensation in wine). These membrane under applied pressure (around 75 bar),
problems are augmented by other administrative noting that the osmotic pressure of the concen-
constraint: in some countries, as USA, a supple- trate rises constantly during filtration. An example
mentary tax is added where the alcohol content is given in Table 1 shows that the maximum sugar
over 14.5% vol. Meanwhile, consumers show concentration obtained is approximately 400 g/L.
preference for wines with less alcohol content A second stage of treatment by evaporation
(between 9 and 13% vol.), a tendency reinforced could help to continue the concentration, in par-
by anti-alcohol campaigns. So, Institut de Recher- ticular in partial alcohol removal from wine by
che Agronomique of Pech Rouge was granted by means of two membranes with different selectivi-
Agence Nationale de Recherche a research project ties against alcohol. Here the selectivity of the
on “quality wines with reduced alcohol content”. second membrane decreases strongly and so im-
The aim of the study is to produce wine by taking pedes the final concentration. Table 2 shows such
into account both aspects and other wine by-prod- example.
ucts with an alcohol content of less than 6% vol. The system for partial alcohol removal pro-
Several French companies as IMECA, Bucher posed by the Australian company Memstar in-
Vaslin, Michael Paetzold, InterRhône have the volves a reverse osmosis membrane followed by
same objective and are developing processes that a membrane contactor (Liquid Cel by Membrana).
integrate systematically at least one membrane Two such plants are installed in Chile and Aus-
technique. tralia. A Californian company, Vinovation also
This technology is already implemented in proposes membranes for partial alcohol removal
countries where the regulation permits this kind and claims that at present 10% of premium wines
of experiments. All systems proposed at present in USA undergo a small correction of alcohol con-
induce to a certain extent the reduction of must or tent.
wine volumes due to the elimination of a concen-
trate of sugar or alcohol. This decrease in volume
3. Volatile acidity or malic acid reduction
is related to the desired reduction in sugar or al-
cohol content and involves a slight concentration The same company markets a system for vola-
of other components. For example, the process of tile acidity reduction by coupling reverse osmo-

Table 1
Results of must concentration analyses at different stages of treatment

Sugar pH Total acidity Tartaric acid Malic acid IPT


(g.L–1) (gH2SO4.L–1) (g.L–1) (g.L–1)
Raw juice 271 3.60 2.66 3.93 0.79 19.2
CUF 311 3.50 4.00 5.84 0.65 118.0
PUF 249 3.55 2.53 3.34 0.91 3.8
CNF 428 3.60 3.0 4.23 0.92 6.9
PNF 40 3.40 1.93 2.19 0.89 0.8
286 A. Massot et al. / Desalination 231 (2008) 283–289

Table 2
Evolution of alcohol content (DAV) at the second stage
membrane MEMBRANES

Time Permeate DAV permeate DAV concentrate 1 2 4


(min) rate (l/h) (%. vol) (%. vol)
RAW WINE
0 180 n.d 6.2
25 150 1.40 8.2 PERMEATE 5
3
50 90 2.1 13.0 TREATMENT
70 60 5.5 17.0
95 40 7.1 19.1 FINAL WINE
120 20 10.3 21.8
140 20 n.d 23.8
Wi Aft R l

Fig. 1. Coupling of a membrane technique and a perme-


sis and ion exchange resins (weak anionic res- ate treatment (adsorption, ion exchange resins) — gen-
ins). This process is interesting in that it is a case eral scheme.
where the fermentation is stopped [12,13]. The
trials of volatile acidity reduction with some hun-
dred lots enabled rapid resumption of alcoholic The analyses of the wine so treated show an
fermentation in 75% of lots. VA Filtration, a com- increase of alcohol (+0.1), of phenolic content and
pany from USA, proposes a technique for vola- of colour intensity. The increase is due to a por-
tile acidity reduction based on one stage of tion of neutralised permeate which corresponds
nanofiltration followed by selective adsorption of to the “dead” volume of the second reverse os-
volatile acidity (Fig. 1). mosis plant not mixed with the treated wine (3%
The volatile acidity or malic acid reduction in the present case). The result is a slight rise of
could also be done by coupling two stages of re- wine component concentration. The results pre-
verse osmosis (membrane DESAL, NaCl reten- sented in Table 3 show the decrease of volatile
tion rate >99%). Since the free acids are poorly and total acidity of the treated wine and a small
retained by the membrane, the permeate after the increase of pH (+0.02).The potassium concentra-
first stage filtration (“permeate 1”, Fig. 2) con- tion remains stable because of the equilibrium
tains free acids, salts, esters and other small mol- between the resulting demineralisation and the
ecules. Once the permeate is neutralised with pH concentration of wine due to the loss of volume.
of the targeted acid, it will be retained by the sec- The equipment for volatile acidity reduction
ond stage membrane in a salty form. The other is proposed by the Italian company VELO and
components passing through (“permeate 2”, that for malic acid — by the company Bucher
Fig. 2) are re-injected in the initial wine. The po- Vaslin. The parameters that control the process
tassium hydroxide is used for neutralisation. and help to optimise it are an adequate choice of
During the treatment, the decrease of the ace- membrane characteristics and neutralisation con-
tic acid concentration in wine is progressive ditions.
(Fig. 2). The rejection rate of acetic acid in first
reverse osmosis varies between 40 and 50%. Af-
4. Others applications
ter the neutralisation, the rejection rate of potas-
sium acetate in second reverse osmosis is higher The elimination of wine “bad taste” appears
than 90%. to be a promising research subject. Chilean re-
A. Massot et al. / Desalination 231 (2008) 283–289 287

Volatile Acidity of wine Permeate 1 Permeate 2


0,9

0,8
Volatile Acidity (g H 2 SO 4 /L)

0,7

0,6

0,5

0,4

0,3

0,2

0,1

0
0 200 400 600 800 1000 1200 1400 1600

Permeate volume (litres)


Fig. 2. Evolution of wine volatile acidity and of permeates of two reverse osmosis stages.

Table 3
Results of physico-chimical analyses of wines before and after treatment

Red wine sample Red wine treated White wine sample White wine treated
Alcohol content (% v/v) 11.5 11.5 9.20 9.30
Total acidity (gH2SO4/l) 3.92 3.72 7.84 7.35
Volatile acidity (gH2SO4/l) 0.71 0.37 0.86 0.63
pH 3.56 3.58 3.75 3.77
Potassium (mg/l) 1500 1500 1386 1320
Total phenol index (TPI) 24.1 27.3 / /
Colour intensity 0.43 0.49 / /

searchers [14] explored the methods for 4- cient. In principal, it should be possible to isolate
ethylphenol and 4-ethylguaiacol reduction in red the “bad taste” by using nanofiltration membranes,
wines by combining nanofiltration and adsorp- but for this elimination it would be necessary to
tion. The permeate obtained by nanofiltration is improve the post-treatment (e.g. by adsorption,
treated by hydrophobic adsorbent resins (XAD- fining, etc.).
16HP) and recycled up to the level of desired con- The tartaric acid stabilisation of wines is usu-
centration. They claim that the same process could ally done by cold treatment. It is progressively
also be used for herby taste elimination. The re- replaced by electrodialysis. A Californian study
sults show that the resin selectivity is not suffi- [15] suggests the use of nanofiltration and
288 A. Massot et al. / Desalination 231 (2008) 283–289

Table 4
Synthesis of proposed membrane processes

Objective Processes
Concentration of must Reverse osmosis
Reduction of the sugar content in must Ultrafiltration + nanofiltration
Ultrafiltration + evaporation
Partial alcohol removal Reverse osmosis 1 + reverse osmosis 2
Reverse osmosis + distillation
Reverse osmosis + membrane contactor
Reduction of volatile acidity Reverse osmosis + anionic resins
Reverse osmosis + reverse osmosis
Reverse osmosis + adsorption
Tartaric stabilisation Electrodialysis
Nanofiltration + microfiltration
Bad taste reduction Nanofiltration + resins adsorption
Nanofiltration + PVPP
Reduction of malic acid Nanofiltration+ nanofiltration
pH control Electrodialysis

microfiltration for tartaric acid stabilisation. At • The volume loss induced by the process pro-
first, the wine is concentrated by a nano-mem- vokes an enrichment of wine in phenolic com-
brane until the precipitation of the tartar. The crys- ponents and macromolecules.
tals are then eliminated by microfiltration and the • Finally, compared to alcohol, the management
two permeates are gathered. The process clarifies of sugar concentrate, from a regulatory point
the wine at the same time. of view, is less problematic.
The electrodialysis experiments have been
carried out by the company Eurodia with the ob- The destination and denomination of the con-
jective of acidifing the wine by potassium reten- centrate at present are discussed: “concentrated
tion (Table 4). must for enrichment in sugar” or “concentrated
and rectified must”. As far as alcohol is concerned,
the legislation problems are certainly those that
5. Conclusion
limit the development of a double stage membrane
The possibility of coupling several membrane alcohol removal. The handling and destination of
techniques enables numerous new applications. alcohol is an administrative problem. The mem-
It cannot be realised without a good knowledge branes enabling 80% ethanol retention do exist,
of the membranes themselves, the transfer phe- but the maximum concentration extent is limited
nomena and the separation mechanisms. The re- to 25% vol., beyond which the retention rate de-
duction of sugar content in the must is a good creases rapidly.
example: that process represents an innovative Numerous other applications could be intended
solution, applying a well known technology. The with the aim of bringing some corrections to must
treatment has the following advantages: or wine, as, for example, reduction of malic acid
• The risk of stuck fermentation is limited and it content in must, pH control, or bad taste elimina-
helps the winemaker have better control of tion. In all these cases, must or wine are fractioned
extraction phenomena during vatting. by the membranes selected and tasted with care.
A. Massot et al. / Desalination 231 (2008) 283–289 289

So, the solutes to be retained are separated and [5] M. Mietton-Peuchot, V. Milisic and P. Noilet,
the initial wine is reconstructed free of rogue com- Desalination, 148 (2002) 125–129.
ponents that veil its optimum quality. [6] V. Milisic and M. Hamachi, Proc. 3rd Nanofiltration
and Applications Workshop, 2001, pp. 26–28.
[7] I. Kiss, G. Vatay and E. Bekassy-Molnar,
Acknowledgements Desalination, 162 (2004) 295–300.
[8] J. Regan, Fermentation, 3(4) (1990) 235–237.
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25(4) (1993) 245–250.
[11] J.L. Escudier, Rev. fr. œno., 119 (1989) 56–61.
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