T. Colin*, A. Bories**, Y. Sire** and R.

Perrin*
* Evatex SAS, 26 rue Gay Lussac, 59147, Gondecourt, France
** I.N.R.A., Unite Experimentale de Pech Rouge, 11430, Gruissan, France
(E-mail: bories@ensam.inra.fr)
Abstract Taking account of the high specificity of the organic load of winery effluents, a new
biophysical treatment using the stripping of ethanol combined with a final concentration by
evaporation has been studied. Two options are proposed: full treatment and pre-treatment. The study
of the composition of winery wastewater has shown the large, dominant part of ethanol in the organic
load (75 to 99% of the COD). According to a linear correlation between COD and ethanol concentration,
the determination of ethanol concentration can be used to estimate the organic load of winery
wastewater. Full treatment by stripping and concentration at a pilot plant allows the separation of the
wastewater into highly purified water (COD elimination>99%), a concentrated alcoholic solution
usable as bio-fuel and a concentrated by-product. Stripping alone represents an advantageous
pre-treatment of winery wastewater. The purification rate reaches 78 to 85% and ethanol is
recovered. The process facilitates discharge into a sewage system in view of treatment with
domestic effluents and can also improve the efficiency of overloaded or old purification
plants. The economical approach of this method demonstrates its competitiveness in comparison
with biological treatments: low energy consumed, no sludge.
Keywords Winery wastewater treatment; valorisation; ethanol

Water Science and Technology Vol 51 No 1 pp 99106 IWA Publishing 2005

Treatment and valorisation of winery wastewater by a new

biophysical process (ECCF
)

Introduction

Measurements of the organic load of winery wastewater have been increasingly reported for
many years (Mourgues and Maugenet, 1972; Maugenet, 1978) and particularly in recent
times (Rochard, 1993; Racault and Lenoir, 1994). The evaluation criteria of the organic load
such as COD and BOD are global parameters that quantify the organic load but do not
provide the composition of the pollutants. At this time, winery wastewaters are equated with
industrial or urban effluents and, as a result, they are treated with the same technologies:
spreading (Tournier, 1992; Laurens, 1996), natural or forced evaporation, aerobic degradation, activated sludge (Forgeat et al., 1992; Racault, 1998) and methanisation (Bories,
1992a,b; Bories and Moulon, 1995).
Detailed studies of the composition of winery wastewater have revealed that ethanol and,
to a smaller extent and on a temporary basis, sugars (fructose, glucose) represent more than
90% of the organic load of winery effluent (Bories et al., 1998a,b; Bories, 2000). These
results prove that it is worthwhile to recover the organic load of winery wastewater rather
than dissipating it into sludge and CO2. Moreover, ethanol is a compound that is easy to
extract (stripping).
The purpose of this study concerns a new approach to the treatment of the organic load of
winery wastewater using a biophysical process known as ECCF1 (Evapo-concentration
with fractioned distillation). The first stage, when required, is the fermentation of the
sugars to ethanol. The second stage is physical. It involves the stripping of ethanol in
order to obtain a final separation of the wastewater into three phases: highly purified

99

T. Colin et al.

Figure 1 ECCF
process diagram

water, an alcoholic product with at least 40% ethanol and a residual concentrated
by-product.
The aim of this study was to examine the detailed composition and the flows of winery
wastewater over a one-year period. We then report some of the results obtained, on the one
hand, by the treatment of winery effluent using stripping and concentration to carry out a full
treatment and, on the other hand, by stripping alone (pre-treatment). The treatment
performances and economical and technical data are discussed.
Methods

100

The wastewater came from two French wineries: a large winery in the Languedoc
(200,000 hl) and a medium-size winery in Provence (40,000 hl).
Stripping and concentration were carried out with an industrial prototype (Evatex SAS,
Gondecourt, France) consisting of a steam-stripping column (14 plates, flow: 1,000 l/h)
combined with an evaporator (Falling film evaporator, flow: 500 l/h) equipped with
mechanical vapour recompression (Figure 1). Stripping and concentration were conducted at
atmospheric pressure, with additional steam supply.
Alcoholic fermentation took place on a laboratory scale using a 2-litre LSL Biolafitte
reactor, under anaerobic conditions (N2 bubbling) with mechanical agitation (100 rpm)
at room temperature (22 C). Yeast inoculum was made from dehydrated active yeast
(Saccharomyces cerevisiae).
The chemical oxygen demand (COD) was determined by chromic oxidation (French
AFNOR standard 90103). The composition of wastewater and organic compounds (glycerol,
organic acids, ethanol) was determined by HPLC. The apparatus included: an isocratic
pump, an in-line degasser, an automatic injector, a refractive index detector (Waters,
Milford, USA), an Aminex HPX-87H organic acid analysis column (Bio-Rad, USA) and
Millennium chromatography manager software (Waters). Carbohydrates were determined
by HPLC using a Waters carbohydrate column and identical Waters apparatus. Total
suspended solids (TSS) were determined by centrifugation and drying of the bottom at
105 C. Conductivity was measured with a WTW conductivity detector (Weilheim,
Germany).
The ratio of the organic load of a compound on COD was calculated using the theoretical
yield of total oxidation: (in g O2/g of compound) ethanol (2.06), sugars (1.07), malic acid
(0.72), tartaric acid (0.53), lactic acid (1.07), succinic acid (0.95), acetic acid (1.07) and
glycerol (1.22).

10

20
15

10

06

05

03

01

12

10

09

0
Month

T. Colin et al.

Ethanol - Sugars (g/l)

CODd (g O2 /l)

25

Figure 2 Evolution of the dissolved COD (+), of the ethanol (m) concentration and of the sugars,
glucose+fructose (&), of winery wastewater over a one-year period

Results and discussion

Composition of wastewater from wineries

The dissolved organic load (CODd) and the concentrations of ethanol and sugars, during one
season, are presented in Figure 2. The total organic load fluctuated between 7 to 22 g O2/l
during the year. The CODd was not connected with active periods: effluents produced during
racking polluted as much or more than effluents from harvesting or wine production. The
fluctuations of the CODd concentrations are the result of water consumption (washing) that
effects the dilution of the effluents to varying degrees. The ethanol concentration fluctuated
between 2.5 to 8 g/l (0.3 to 1 % vol/vol). Sugars were only present during the harvest phase.
They reached a maximum of 6 g/l at the beginning of the season.
As illustrated in Figure 2, the behaviour of ethanol concentration was close to the CODd.
A linear correlation can be obtained between ethanol and CODd (Figure 3). A very good
estimation of the CODd can be obtained by measuring the ethanol concentration.
In spite of wide variations of the organic load during the year, ethanol always represented
more than 75% (up to 99%) of the total CODd during the year, except during the harvest
(>55%) (Figure 4). Sugar ratios reached 40% of COD during the harvest but rapidly
decreased in October. Addition of ethanol and sugars always represented at least 75% of
the COD.
Averages of detailed analyses of winery wastewater (Table 1) over two seasons
confirmed that ethanol was the main part (80%) of the dissolved organic load. Glucose and
fructose were the main sugars encountered and represented an average of 7% of the CODd
for the year. The organic load of organic acids was lower than 10% (including tartaric acid:
5.3%) of the CODd. Acetic acid concentration was low: 0.3 g/l (2.6% of the CODd).
Glycerol represented 3% of the CODd. The organic load and compound concentrations of the

R2 = 0.9517

CODd = 2.7144 x [ethanol]

CODd (g O2 /l)

40
30
20
10
0
0

10

15

Ethanol (g/l)

Figure 3 Correlation between ethanol concentration and CODd of winery wastewater

101

COD rate (%)

100
80
60
40
20

06

05

03

01

12

10

09

T. Colin et al.

Month
Figure 4 Ethanol COD (m) and sugar COD (&) rates of the CODd over a one-year period

winery wastewater varied from one year to the next. However, no significant difference
could be observed in the distribution of the CODd between the compounds.
In view of the overall results, winery wastewater can be considered to be like a hydroalcoholic solution (12% vol/vol) containing secondary products (glycerol, organic acids)
and sugars from time to time.
Evapo-concentration with fractioned condensation

A treatment process using fractional distillation of the components based on the separation of
ethanol and secondary products was tested and validated. If necessary, sugars contained in
the effluent can be converted to ethanol.
Fractional distillation of winery effluents using stripping and concentration (full treatment)

The stripping of the ethanol and the concentration of the stripped wastewater was directly
carried out from winery waste. Table 2 shows the analytical data of the raw and treated water.
The treatment process produced highly purified wastewater (CODd: 88224 mg O2/l),
corresponding to a global COD elimination of 99%. Many process tests have demonstrated
that the organic load of the purified effluent was between 80 and 240 mg O2/l (Figure 5).
This final condensate was highly demineralised (conductivity: 3139 mS/cm) and free of
suspended matter and microorganisms. It can therefore be recycled as industrial water or be
discharged into a natural environment. A concentrated by-product can simultaneously be
recovered from the concentration stage. The volume of the concentrated by-products
represents about 5% of the initial wastewater. It was previously shown (Bories et al., 1999;
Table 1 Mean composition of winery wastewater in 20012002 and 20022003
20012002
Values

102

pH
TSS (g/l)
COD raw (g O2/l)
COD dissolved (g O2/l)
Ethanol (g/l)
Glucose (g/l)
Fructose (g/l)
Tartaric acid (g/l)
Malic acid (g/l)
Lactic acid (g/l)
Succinic acid (g/l)
Glycerol (g/l)
Acetic acid (g/l)

4.99
3.32
14.6
12.7
4.9
0.35
0.52
1.3
0.07
0.16
0.08
0.32
0.30

20022003
% CODd

Values

% CODd

100
79.5
2.9
4.4
5.3
0.4
1.3
0.6
3.1
2.6

6.11
0.70
10.9
10.1
3.9
0.30
0.44
0.48
0.06
0.20
0.04
0.27
0.19

100
78.5
3.2
4.6
2.5
0.4
2.1
0.4
3.3
2.1

Table 2 Analytical data of treatment of winery wastewater using the ECCF
process
Parameter

pH
CODd (mg O2/l)
Ethanol (g/l)
Conductivity (mS/cm)

Before treatment

After treatment

Removal rate (%)

3.653.82
23,37621,204
7.917.28
2,9801,650

4.033.88
22488
0.060.02
3931

99.2
99.5
98.4

Parameter

pH
Conductivity (mS/cm)
CODd (mg O2/l)
Ethanol (g/l)

Before treatment

After treatment

Removal rate (%)

3.82
1,5071,650
28,72821,204
12.07.28

3.80
1,8131,400
5,1454,318
00.77

80
93

T. Colin et al.

Table 3 Analytical data of pre-treatment of winery wastewater by stripping

Bories, 2000) that the concentrated residues can be used for composting or spreading, and
animal feed is being considered. The recovery of an alcoholic phase (ethanol 3050%) was
obtained at the same time.
Treatment performances are optimal as soon as treatment begins and are not sensitive to
the variations of the organic load or the shutdown or start-up of plant operations.

Stripping (pre-treatment)

40 000

1000

35 000

875

30 000

750

25 000

625

20 000

500

15 000

375

10 000

250

5 000

125

COD after treatment

(mg O2 /l)

COD before treatment

(mg O2 /l)

Stripping alone of the ethanol from winery wastewater resulted in the elimination of about
80% of the CODd (Table 3) represented by alcohol.
Many wineries are equipped with biological treatment plants. Most of these plants have a
small treatment capacity and it is for this reason that treatment is often not effective. In this
case stripping could improve the treatment. In fact, ethanol stripping could be considered as a
pre-treatment. The stripped effluent that consists of partially purified wastewater can be
more easily treated in a biological purification plant than crude effluent. It can also be
discharged and treated by an urban purification plant. Moreover, this system makes it
possible to highly reduce sludge production. The alcohol (3050% vol/vol) is recovered
under the same conditions as those used in the ECCF1 process.

0
1

5
6
Test

10

Figure 5 COD before (^) and after (&) treatment during several tests of the ECCF
process on
winery wastewater

103

1000

16

800

12

600

400

200

Glycerol - Acetic acid

(mg/l)

Sugars - Ethanol
(g/l)

T. Colin et al.

20

0
0

20

40

60

80

100

Time (h)

Figure 6 Kinetics of the fermentation of winery wastewater. m Ethanol, & sugars

(glucose+fructose), * acetic acid, glycerol
Fermentation of wastewater

When sugars are present, the effluent can be fermented for optimal alcohol recovery. For
example (Figure 6), the kinetics of fermentation of wastewater containing 10.3 g/l of sugars
and 11.6 g/l of ethanol showed that sugars were totally fermented to ethanol (yield: 0.4 g
ethanol/g sugars). Glycerol (0.8 g/l) was produced whereas there was no production of
acetic acid.
Alcoholic fermentation of winery wastewater is different from the fermentation of the
must that involves low sugar and ethanol concentrations and variable pH. Effluent
fermentation conditions are favourable. There are no inhibitory effects like those produced
by ethanol.
Technical and economical considerations

The energy required for the stripping and concentration by mechanical vapour recompression is provided by a power input of 20 kWh/m3 of wastewater treated and a steam supply of
about 80 kg/m3. Total energy consumption (fermentation, stripping and concentration) is
estimated at 25 kWh/m3 (about 1.7 kWh/kg CODd for average winery wastewater) and is
independent of the organic load of the wastewater. The operating costs can be valued at
1.5 euro/m3 (0.06 euro/kWh). In comparison, biological treatment of winery effluents
requires a power supply, proportional to the organic load, of at least 45 kWh/m3 (3 kWh/kg
CODd) (ITV, 2000) and generates sludge (0.3 kg/kg BOD).
The ethanol recovered from the wastewater can be sold or used as fuel in steam generators
or boilers. In all cases, the recovery of ethanol (0.3 euro/L) can cover the costs of the ECCF1
process. Moreover, considerable savings can be made when treated water is recovered for
industrial uses (washing, boiler water, etc.) rather than discharged. For these reasons, the
ECCF1 process can be considered within the framework of sustainable development.
Concerning the investment costs for ECCF1 , estimates for industrial plants have shown
levels similar to those of conventional biological treatments. The non-production of sludge,
which is difficult and expensive to separate and eliminate from the effluent, is a great
advantage of the biophysical process compared to biological treatments.
Conclusions

104

Results of the treatment of winery wastewater by the new biophysical process that involves
fermentation and stripping/concentration, obtained on an industrial scale at the winery site,
validated the technical and economical feasibility of the process. These results demonstrated
the high degree of water purification obtained and the valorisation potential of the
co-products (ethanol, concentrated fraction).

T. Colin et al.

The study confirmed the high specificity of the composition of winery wastewater.
Ethanol is always the main component (2.5 to 8 g/l) and represents, on the average, about
80% of the organic load. Secondary compounds include residual sugars, glycerol and organic
acids. These data showed the uniqueness of winery wastewater compared to industrial and
urban effluents and led to new considerations concerning the treatments. First, they underscored the limits of characterising the organic load with only global parameters such COD,
BOD or TOC. Secondly, the prevalence of ethanol in the organic load made it possible
to propose new technologies and improved treatments and technical and economical
performances.
The physical separation of ethanol (stripping) and water (concentration) offers two
possibilities for the treatment of winery wastewater: full treatment and pre-treatment.
Full treatment of effluents by ethanol stripping and concentration results in a total
de-alcoholisation and produces highly purified water: COD<240 mg O2/l. Purified water is
demineralised, free of solids in suspension as well as odours and germs. This water can be
recycled for industrial applications, resulting in considerable savings. The purification rate
can be as high as 99 to 99.7% of the raw DCO and no additional treatment is necessary
for discharge into a natural environment. Stripping and evaporation are well-established,
reliable and efficient processes used in various industries. The third fraction, a rich
concentrated organic and mineral by-product can be used for agricultural applications.
Stripping alone can be considered to be an advantageous pre-treatment of winery
wastewater. Ethanol recovery by stripping reduces the organic load by 78 to 85% and
produces an alcoholic solution (9 to 20 l pure ethanol/m3 effluent). This alcoholic solution
can be sold or used, without treatment, as fuel. The pre-treatment appears to be very
competitive as a result of its technical simplicity and its easy adaptation to variations in
volume and load.
In the case of overload at the biological treatment plant, the stripping stage can be used to
reduce the organic load before treatment and to recover alcohol.
The economic evaluation of the biophysical process has shown it competitiveness in
comparison to conventional biological treatments, particularly for winery wastewater (high
organic load): lower energy input and recovery of valuable compounds (ethanol, water,
concentrated by-product).
The ECCF1 process constitutes a new concept for the treatment of winery effluents and
opens the way to a new generation of treatments, within the framework of sustainable
development, through the valorisation of the compounds present and the purification and
reuse of water.

Acknowledgements

This study was supported by INRA (French Institute of Agricultural Research) and Evatex.
Wastewater was supplied by the Roy Rene, Lambesc and Anne de Joyeuse wineries, Limoux
(France).

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