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Pressure-Driven Membrane Processes
in Must and Wine Production
Maria Norberta de Pinho
Vítor Geraldes
Instituto Superior Técnico

VINIDEAs – Novas Aplicações Enológicas

Porto – Março, 2009
 Pressure Driven Membrane Processes

Microfiltration (MF) Ultrafiltration (UF) Nanofiltration (NF) Reverse Osmosis (RO)

• 0,1 – 10 μm pores • 1 – 10 nm pores • 0,5 – 5 nm pores • 0,1 – 1 nm pores

• 0,1 – 1 bar pressure • 0,5 – 5 bar pressure • 5 – 60 bar pressure • 20 – 100 bar pressure
• Clarification and • Macromolecules • Sugar and organic • Salts separation
Sterilization separation acids fractionation
 Grape Must and Wine Production
Production flow-sheet Complementar Enological Practices
Operations • Chaptalization - only allowed in the Northern
Europe
Grapes
• Addition of Concentrated Must (CM) or
Rectificated Concentrated Must (RCM)
Crushing • Partial Concentration in the Winery
• Addition of Acid Tartaric or Electrodialysis with
Pressing Bipolar Membranes
Enrichment,
• Sedimentation and Racking
Rectification
Grape Must • Protein fining
and Acid
Correction • Centrifugation
• Kieselguhr or Diatomaceous Earth filtration
Fermentation
• Dead-end Microfiltration
• Tangential Micro and Ultrafiltration
Clarification • Cold Crystalization process with or without
Wine crystal seeding
Tartaric • Ion Exchangers of styrene and vinyl benzene
Stabilization • Electrodialysis
• Pasteurization
Biological • Use of Sulfur Dioxide
Botling
Stabilization
• Sterile Filtration
Partial dealcoholization of wines by
Nanofiltration
 Partial wine dealcoholization by Nanofiltration

Wine
Partial
Nanofiltration Reconstitution
dealcoholized
wine

Wine
Permeate

Distillation
alcohol

Patent: Maria Noberta de Pinho and Gonçalves F.

“Integrated Nanofiltration Process to Reduce the Alcohol Content of Alcoholic Beverages”,
PCT/PT2004/000014/W02004/113489;04737058.0;US10/561,540; 2004250092(Australia); 1521-2004 (Chile);
P040102148(Argentina).
Grape Must Enrichment
 Grape Must Enrichment
Grape Maturity

Great Variability with Geography,

Climatic Condition, Type of Wine and Unprecise
Harvesting Calendar Physiological State

Disrupted Normal
Maturation Kinetics

Grape Must
Unbalanced Grapes
Concentration/Rectification

Inferior Wine Quality Improved Wine Quality

 Grape Must Enrichment
European Market
Present
• The enrichment of the grape must by the addition of saccharose (Chaptalization) can only
be made by the European Northern Countries (historical reasons). For the Southern
Countries the addition of CM, RCM and the partial concentration of must in the winery are
the only pratices allowed.
• Chaptalization is half the price of the other alternative techniques.
• In order to regulate the market and create equal competition conditions between North
and South, the EU pays a subsidy for the use of RCM and CM by the winemakers of the
Southern Countries.
• Loby Groups are trying to bring pressure on the European Comission to make the
Chaptalization an interdicted enological pratice in the EU.

Future
• The interdiction of the Chaptalization would resolve the problem of wine excess in the EU.
• Quality raise of the final product, as it would be processed only with grapes or derived
products: better position for competition with wines of the “New World”.
Grape Must Concentration and
Rectification Processes
Grape Must Concentration/Rectification
Conventional processes
• Vacuum evaporation (VE)
• High Energetic costs.
• Aromatic depletion and production of off-flavours

• Reverse Osmosis (RO)

• Preservation of the aromatic characteristics
• High operating pressure.
• Limitation of the maximum concentration factor.
• Precipitation of Potassium Tartrate.
• Impossibility of simultaneous fractionation

• Ion Exchange Resins for Rectification

• Additional operation to the VE or RO concentration
• Resins regeneration leads to production of waste water and solid
residues.
 Grape Must Concentration/Rectification
Nanofiltration or Nanofiltration/Electrodialysis

• Preservation of the aromatic characteristics of the grape must

• Lower operating presure (related to RO)

• No precipitation of Potassium Tartrate.

• Simultaneous concentration and rectification through tailoring of NF with

the selective permeation of the organic acids in Nanofiltration

• Integration of Electrodialysis for partial removal of salts and organic acids

with NF for concentration
Patent:
Maria Noberta de Pinho, Vitor Geraldes, Isabel Catarino,
‘Method for Simultaneous Concentration and Rectification of Grape Must Using Nanofiltration
and Electrodialysis’,
PCT/PT2007/000045;3026-2007 (Chile); P-070104717(Argentina)
 Grape Must Concentration/Rectification
Nanofiltration or Nanofiltration/Electrodialysis

Concentration using
Membrane Processes

• Preservation and
increment of the
aromatic characteristics
of the grape must

in Fisher, U. 2006. XIX Gior. Int. Vitivinicola

Grape Must Concentration and
Rectification by Nanofiltratiom
 Grape Must Concentration and
Rectification by Nanofiltratiom
Selection of Membranes
Nanofiltration set-up
Membrane hidraulic permeabilities
Total Recirculation Mode

in Santos, F. , Geraldes V. and Norberta de Pinho, 2008. Amer.J.Enol.Viti.

 Grape Must Concentration and
Rectification by Nanofiltratiom
Selection of Membranes
NF90 CA27-87.5
100 100 100 100 99,7 99,7 99,7 96,9 98,6 96,4

Rejection coefficients to sugars 100

99,8 99,7 99,6 99,7 96,5 100 100
100

80
98,8 98,0 100 100
90,9 94,5
80
(glucose and fructose) , organic 60 60
81,1

acids and salts 40 40

20 20

0 0
Na2SO4 MgSO4 Fru. Glu. NaCl T.A. M.A Na2SO4 MgSO4 Fru. Glu. NaCl T.A. M.A
f' f f' f

• NFT50, NF200 and NF270

NF200 NFT50
99,9 99,9 99,6 99,7 100 100 100 100 98,6 98,5 99,3
100 92,2 93,0 90,8 100
99,5 99,1 97,3 99,8 99,5 97,1
95,6 96,1

show a greater potential 80

60
75,5
71,8
80

60
72,4

for the use in the 40

53,6
40
52,4
42,4

20 20

fractionation of 0
Na2SO4 MgSO4 Fru. Glu. NaCl T.A. M.A
0
Na2SO4 MgSO4 Fru. Glu. NaCl T.A. M.A

sugars/organic acids.
f' f f' f

NF270 ETNA 0.1PP

100 100 100 100 97,7 98,6 99,4 98,6 99,0 97,7 97,5
100 100 92,1
86,1
99,4 98,8
80 73,7
80
82,1
f – aparent rejection 60
76,2
60 67,2

f’ – intrinsic rejection 40 45,9 40 50,7

34,7
20 24,6 20
17,1 16,1 12,8 13,9
9,5
0 0
in Santos, F. , Geraldes V. and Norberta de Na2SO4 MgSO4 Fru. Glu. NaCl T.A. M.A Na2SO4 MgSO4 Fru. Glu. NaCl T.A. M.A
Pinho, 2008. Amer.J.Enol.Viti. f' f f' f
 Grape Must Concentration and
Rectification by Nanofiltratiom
Permeation Fluxes of EDM and Model Grape Musts
Composition of EDM grape must and grape Flux of the permeate for grape must and model
must model solutions solutions (kg h-1m-2)
Grape must Model solutions Model solutions

RD1 RD2 EDM

RD1 RD2 EDM
RD1T RD1M. RD2T RD2M
RD1T RD1M RD2T RD2M
NFT50 28 32 13 13 18
-1
Tartaric acid (g L ) 2.0 - 2.6 - 2.0 NF90 23 24 9 8 11

Malic acid (g L-1) - 2.5 - 3.3 5.0 NF200 27 29 12 12 16

NF270 35 35 18 17 24
Total sugar (g L-1) 150 150 200 200 107
ETNA 0.1PP 113 84 80 65 31
pH 2.64 2.41 2.52 2.33 3.19
CA 27-87.5 16 17 9 9 10

Conductivity(μScm-1) 892 700 913 685 2200

Operational conditions: transmembrane pressure 35 bar, flow rate
130 L h-1, 25ºC, membrane surface area 13.2x10-4 m2; for EDM the
transmembrane pressure was 30 bar.

• Permeation fluxes are similar for the NFT50, NF90, NF200, and NF270
• For the model solutions with higher sugar content fluxes are lower

• Permeation fluxes of EDM must are closer to the ones of the model solutions with higher sugar content

in Santos, F. , Geraldes V. and Norberta de Pinho, 2008. Amer.J.Enol.Viti.

 Grape Must Concentration and
Rectification by Nanofiltratiom
Rejection Coefficients to Sugars and Organic Acids

NF270 Membrane
• Rejection coefficients of model solutions:
Sugars > 90%
Organic acids < 35%
• Rejection coefficients of EDM must:
Sugars ~100%
Tartaric acid ~89%
Malic acid ~64%
• The increase of the sugar content
enhances the preferential permeation of
the organic acids.
Glu – glucose
• NF270 presents the highest gap between Fru – Fructose
the rejection coefficients of the two organic TA – Tartaric Acid
acids MA – Malic Acid

in Santos, F. , Geraldes V. and Norberta de Pinho, 2008. Amer.J.Enol.Viti.

 Grape Must Concentration and
Rectification by Nanofiltratiom
Conclusions
• The complex composition of EDM must is the basis for the occurrence of
solute/solute interactions that play an important role on the selective
permeation performance of Nanofiltration

• The low fluxes, of a grape must, can be attributed to the osmotic

pressure of other solutes that are present in its more complex matrix.

• The preferential permeation of the organic acids with respect to the

sugars, verified for the binary solutions is also confirmed in the EDM
grape must and in the grape must model solutions and this is particularly
pronounced for the NF270

• The increase of sugar content enhances the selective permeation of

organic acids with respect to sugars

in Santos, F. , Geraldes V. and Norberta de Pinho, 2008. Amer.J.Enol.Viti.

Integration of Nanofiltration and
Electrodialysis for Grape Must
Concentration / Rectification
 Integration of Nanofiltration and
Electrolialysis for Grape Must Concentation
Concentration of Electrodialised Grape Must
ED
Grape
-
NF Memb: NF200
Must Surf. Area: 0.648 m2
Water Feed flow rate: 9 L min-1

50%

Water electrodialised must

(17.4 ºBrix)

Concentrated
must
Grape Must
+

Organic acids (18.4 ºBrix)

ºBrix of the permeate

• Higher permeate fluxes for the

50% deionised grape must
Permeation flux and total solids content (ºBrix) of the
• The permeate of the 50% permeate vs transmembrane pressure
deionised grape must has lower
Total Solids content
Clarification of Wine by Microfiltration
and Ultrafiltration
Clarification of Wine by Microfiltration and Ultrafiltration
White Wine
Microfiltration Ultrafiltration

Concentration factor Concentration factor

• Significant increase of the fluxes when the • Increasing pressure only affects the start of
pressure is raised from 0.6 bar to 1.0 bar. the operation.
• No need for operating at more than 1.0 bar
in Gonçalves, F. and Norberta de Pinho, 2001. Sep. Purif. Technology
Clarification of Wine by Microfiltration and Ultrafiltration

Red Wine
Microfiltration Ultrafiltration
1.0 bar
1.8 bar
2.6 bar

Concentration factor Concentration factor

• Increasing pressure only affects the start of • Permeation fluxes are more dependent on
the operation. the transmembrane pressure
• No need for operating at more than 0.6 bar
in Gonçalves, F. and Norberta de Pinho, 2001. Sep. Purif. Technology
Clarification of Wine by Microfiltration and Ultrafiltration
Permeation fluxes of microfiltration and
ultrafiltration essays after stabilization
Microfiltration Ultrafiltration
ΔP Final flux ΔP Final flux
Wine
(bar) (Lh-1m-2) (bar) (Lh-1m-2)
0,6 93 1,0 122
White 1,0 118 1,8 129
1,4 140 2,6 135
0,6 35 1,0 16
Red 1,0 34 1,8 18
1,4 39 2,6 23
White Wine
• Significant increment of the microfiltration permeation fluxes when operating pressure is raised from 0.6
to 1.0 bar
• Aproximatly equal values for the ultrafiltration permeation fluxes over any of the three working pressures
Red Wine
• Much lower fluxes than the ones for white wine
• During microfiltration there are no gain of productivity from the raising of the working pressure
• Extremly low permeation fluxes for the ultrafiltration of red wines
in Gonçalves, F. and Norberta de Pinho, 2001. Sep. Purif. Technology
Clarification of Wine by Microfiltration and Ultrafiltration
Polysaccharides and polyphenols remotion during clarification
Microfiltration Ultrafiltration
Percentage removal Percentage removal

ΔP ΔP
Wine Polysaccharides Polyphenols Wine Polysaccharides Polyphenols
(bar) (bar)

0,6 11,4 2,1 1,0 16,4 0,0

White 1,0 7,6 0,9 White 1,8 16,4 0,8

1,4 7,7 2,6 2,6 18,7 4,0

0,6 24,6 9,6 1,0 82,9 31,5

Red 1,0 22,8 12,6 Red 1,8 83,9 43,4
1,4 23,1 10,2 2,6 94,5 54,1

Microfiltration Ultrafiltration
• Slight decrease of the polysaccharides • Very significant removal of Polysaccharides
content from the white wine, but more and Polyphenols in the Red Wine, resulting in
significant for the red wine. a flat body wine.
• No significative removal of these
Macromolecules in white wine
in Gonçalves, F. and Norberta de Pinho, 2001. Sep. Purif. Technology
Clarification of Wine by Microfiltration and Ultrafiltration
Water flux recuperation following several cleaning steps
Microfiltration Ultrafiltration
Clarification Cleaning procedure Clarification Cleaning procedure
1st step 2nd step 3rd step
ΔP ΔP 1st step 2nd step 3rd step 4th step
Wine Water 20ºC, Water 50ºC, Ultrasil11 0,5%
Wine Water 20ºC, Water 50ºC, Ultrasil11 1% Ultrasil11 1%
(bar) 30 min 30 min 50ºC, 30 min (bar) 30 min 60 min 50ºC, 60 min 50ºC, 3 hr
0,6 83% 93% -
1,0 93% - - -
White 1,0 82% 104% -
White 1,8 95% - - -
1,4 80% 94% -
2,6 92% - - -
0,6 81% 73% 97%
1,0 27% 38% 75% 95%
Red 1,0 48% 75% 97%
Red 1,8 18% - 65% 91%
1,4 31% 57% 98%
2,6 15% - 44% 66%

White Wine
Less Significant Foulling
• Easier cleaning of the Ultrafiltration membrane in of the Ultrafiltration
relation to the Microfiltration membrane. Membrane
Red Wine
• Very difficult cleaning of the Ultrafiltration membranes
• Impossible recovery of the fluxes when the essay was Irreversible
done with the higher working pressure Membrane Foulling
in Gonçalves, F. and Norberta de Pinho, 2001. Sep. Purif. Technology
 Acknowledgments
The authors would like to acknowledge the financial support from
NanoMemPro Work Group and from the Foundation for Science and
Technology (FCT) through the project POCI/AGR/58450/2004 and
Frederico Rosa Santos and Isabel Catarino would like to thank FCT for the
scholarship awarded in the framework of the project.
Thank you