Integrated Membrane Operations in Must and Wine Production

Transcription

1 Integrated Membrane Operations in Must and Wine Production Frederico R. Santos Maria Norberta de Pinho Instituto Superior Técnico / IBET

2 Pressure Driven Membrane Processes Microfiltration (MF) Ultrafiltration (UF) Nanofiltration (NF) Reverse Osmosis (RO) 0,1 10 µm m 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 bar pressure Clarification and Sterilization Macromolecules separation Sugar and organic acids fractionation Salts separation

3 Grape Must and Wine Production Production flow-sheet Grapes Crushing Pressing Grape Must Fermentation Wine Botling Complementar Operations Enrichment, Rectification and Acid Correction Clarification Tartaric Stabilization Biological Stabilization Enological Practices Chaptalization - only allowed in the Northern Europe Addition of Concentrated Must (CM) or Rectificated Concentrated Must (RCM) Partial Concentration in the Winery Addition of Acid Tartaric or Electrodialysis with Bipolar Membranes Sedimentation and Racking Protein fining Centrifugation Kieselguhr or Diatomaceous Earth filtration Dead-end end Microfiltration Tangential Micro and Ultrafiltration Cold Crystalization process with or without crystal seeding Ion Exchangers of styrene and vinyl benzene Electrodialysis Pasteurization Use of Sulfur Dioxide Sterile Filtration

4 Grape Must Enrichment

5 Grape Must Enrichment Grape Maturity Great Variability with Geography, Climatic Condition, Type of Wine and Harvesting Calendar Unprecise Physiological State Disrupted Normal Maturation Kinetics Unbalanced Grapes Grape Must Concentration/Rectification Inferior Wine Quality Improved Wine Quality

6 Present Grape Must Enrichment European Market 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 e winemakers of the Southern Countries. Loby Groups are trying to bring pressure on the European Comission on 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 y with grapes or derived products: better position for competition with wines of the New World.

7 Grape Must Concentration and Rectification Processes

8 Grape Must Concentration/Rectification Conventional processes Vacuum evaporation (VE) High Energetic costs. Aromatic depletion and production of off-flavours 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.

9 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

10 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 XIX Gior. Int. Vitivinicola

11 Grape Must Concentration and Rectification by Nanofiltratiom

12 Grape Must Concentration and Rectification by Nanofiltratiom Selection of Membranes Nanofiltration set-up Total Recirculation Mode Membrane hidraulic permeabilities 20 19,2 Flowmeter Lab cell 16 Feed Pump Valve Manomet Lp (kg/h/m2/bar) ,5 9,9 8,6 4 2,1 1,8 Valve Manometer 0 NF270 ETNA NFT50 NF90 NF200 CA27 in Santos, F. et al, Amer.J.Enol.Viti.

13 Grape Must Concentration and Rectification by Nanofiltratiom Rejection coefficients to sugars (glucose and fructose) ), organic acids and salts Selection of Membranes NF ,8 99,7 99,6 99,7 99,7 96, CA ,7 99,7 96,9 98,6 96,4 98,8 98, ,9 94,5 81, NFT50, NF200 and NF270 show a greater potential for the use in the fractionation of sugars/organic acids Na2SO4 MgSO4 Fru. Glu. NaCl T.A. M.A f' NF200 99,9 99,9 99,6 99,7 99,5 99,1 95,6 97,3 92,2 93,0 90,8 75,5 71,8 53,6 Na2SO4 MgSO4 Fru. Glu. NaCl T.A. M.A f' NF ,4 98,8 82,1 76,2 97,7 98,6 99,4 f f Na2SO4 MgSO4 Fru. Glu. NaCl T.A. M.A f' NFT ,8 99,5 97,1 96,1 98,6 98,5 99,3 72,4 52,4 42,4 Na2SO4 MgSO4 Fru. Glu. NaCl T.A. M.A f' ETNA 0.1PP 98,6 99,0 97,7 97,5 67,2 73,7 86,1 92,1 f f f aparent rejection f intrinsic rejection ,9 34,7 24,6 Na2SO4 MgSO4 Fru. Glu. NaCl T.A. M.A f' f ,7 17,1 16,1 12,8 13,9 Na2SO4 MgSO4 Fru. Glu. NaCl T.A. M.A f' 9,5 f in Santos, F. et al, Amer.J.Enol.Viti.

14 Grape Must Concentration and Rectification by Nanofiltratiom Permeation Fluxes of EDM and Model Grape Musts Composition of EDM grape must and grape must model solutions Grape must Model solutions RD 1 RD 2 EDM RD 1 T RD 1 M RD 2 T RD 2 M Tartaric acid (g L -1 ) Malic acid (g L -1 ) Total sugar (g L -1 ) ph Conductivity(µScm -1 ) Flux of the permeate for grape must and model solutions (kg h -1 m -2 ) Model solutions RD 1 RD 2 RD 1 T RD 1 M. RD2T RD 2 M EDM NFT NF NF NF ETNA 0.1PP CA Operational conditions: transmembrane pressure 35 bar, flow rate 130 L h -1, 25ºC, membrane surface area 13.2x10-4 m 2 ; 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 s with higher sugar content in Santos, F. et al, Amer.J.Enol.Viti.

15 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. NF270 presents the highest gap between the rejection coefficients of the two organic acids in Santos, F. et al, Amer.J.Enol.Viti NF270 - RD1T Glu Fru TA MA f' NF270 - RD2T Glu Fru TA MA f' Glu glucose Fru Fructose TA Tartaric Acid MA Malic Acid f f NF270 - RD1M Glu Fru TA MA f' NF270 - RD2M Glu Fru TA MA f' NF270 - EDM Glu Fru TA MA f' f f f

16 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. et al, Amer.J.Enol.Viti.

17 Integration of Nanofiltration and Electrodialysis for Grape Must Concentration / Rectification

18 Integration of Nanofiltration and Electrolialysis for Grape Must Concentation Grape Must ED - Concentration of Electrodialised Grape Must NF Water Memb: NF200 Memb: NF200 Am = 0,648 m2 Mosto Azal (ca. 10 l) Qr = 9 l/min Surf. Area: m 2 Feed flow rate: 9 L min Water + Organic acids Concentrated Grape Must Jv (l/mh2.h) % Jv, mosto desionizado 50% electrodialised must (17.4 ºBrix) (17.4 ºBrix) Jv, mosto must bruto (18.4 ºBrix) (18.4 ºBrix) º Brix Higher permeate fluxes for the 50% deionised grape must The permeate of the 50% deionised grape must has lower Total Solids content DP (bar) ºBrix ºBrix do of permeado the permeate Permeation flux and total solids content (ºBrix Brix) of the permeate vs transmembrane pressure 5

19 Clarification of Wine by Microfiltration and Ultrafiltration

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

21 Clarification of Wine by Microfiltration and Ultrafiltration Microfiltration Red Wine Ultrafiltration 1.0 bar 1.8 bar 2.6 bar Concentration factor Concentration factor Increasing pressure only affects the start of the operation. Permeation fluxes are more dependent on the transmembrane pressure No need for operating at more than 0.6 bar in Gonçalves, F Sep. Purif. Technology

22 Clarification of Wine by Microfiltration and Ultrafiltration White Wine Permeation fluxes of microfiltration and ultrafiltration essays after stabilization Wine White Red Microfiltration P (bar) 0,6 1,0 1,4 0,6 1,0 1,4 Final flux (Lh -1 m -2 ) Ultrafiltration P (bar) 1,0 1,8 2,6 1,0 1,8 2,6 Final flux (Lh -1 m -2 ) 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 Sep. Purif. Technology

23 Clarification of Wine by Microfiltration and Ultrafiltration Wine White Red Polysaccharides and polyphenols remotion during clarification P (bar) 0,6 1,0 1,4 0,6 1,0 1,4 Microfiltration Percentage removal Polysaccharides 11,4 7,6 7,7 24,6 22,8 23,1 Polyphenols 2,1 0,9 2,6 9,6 12,6 10,2 Wine White Red P (bar) 1,0 1,8 2,6 1,0 1,8 2,6 Ultrafiltration Percentage removal Polysaccharides 16,4 16,4 18,7 82,9 83,9 94,5 Polyphenols 0,0 0,8 4,0 31,5 43,4 54,1 Microfiltration Slight decrease of the polysaccharides content from the white wine, but more significant for the red wine. in Gonçalves, F Sep. Purif. Technology Ultrafiltration Very significant removal of Polysaccharides and Polyphenols in the Red Wine, resulting in a flat body wine. No significative removal of these Macromolecules in white wine

24 Clarification of Wine by Microfiltration and Ultrafiltration Clarification Wine White Red P (bar) 0,6 1,0 1,4 0,6 1,0 1,4 White Wine Water flux recuperation following several cleaning steps Microfiltration 1 st step Water 20ºC, 30 min 83% 82% 80% 81% 48% 31% Cleaning procedure 2 nd step Water 50ºC, 30 min 93% 104% 94% 73% 75% 57% 3 rd step Ultrasil11 0,5% 50ºC, 30 min % 97% 98% Clarification Wine White Red Easier cleaning of the Ultrafiltration membrane in relation to the Microfiltration membrane. Red Wine P (bar) Very difficult cleaning of the Ultrafiltration membranes Impossible recovery of the fluxes when the essay was done with the higher working pressure in Gonçalves, F Sep. Purif. Technology 1,0 1,8 2,6 1,0 1,8 2,6 1 st step Water 20ºC, 30 min 93% 95% 92% 27% 18% 15% Ultrafiltration Cleaning procedure 2 nd step Water 50ºC, 60 min % rd step Ultrasil11 1% 50ºC, 60 min % 65% 44% 4 th step Ultrasil11 1% 50ºC, 3 hr % 91% 66% Less Significant Foulling of the Ultrafiltration Membrane Irreversible Membrane Foulling

25 Tartaric Stabilization of Wine

26 Tartaric Stabilization of Wine Cold crystalization process Removal of potassium hydrogen tartarate (KHT), to avoid the formation of precipitates latter in the botle Traditionally this is done by wine cooling followed by diatomaceous earth filtration. 1 Wine cooling 2 - Tartrate crystal seeding 3 - Dynamic crystalization 4 - Fitration

27 Tartaric Stabilization of Wine Cold Crystalization Process vs Electrodialysis Electrodialysis is an alternative method with: No generation of huge amounts of solid wastes (diatomaceous earth filtration media and tartrates) Competitive costs No effect on the organoleptic wine characteristics Energy Costs: Electrodialysis kwh/m 3 Cold 5 10 kwh/m 3

28 Tartaric Stabilization of Wine Conductivity variation of red and white wine during an electrodialysis essay Red wine White wine Conductivity (µs cm -1 ) Time (h) For both wines the conductivity decrease is mostly explained by the decrease of Potassium and Tartrate Significant decrease of the Calcium and Magnesium ions for both wines Slight decrease of the Acid Malic content for both wines Small decrease of the Lactic Acid content for the Red Wine in Gonçalves, F, Sep. Purif. Technology

29 Tartaric Stabilization of Wine Saturation Temperature (Tsat) of a White Wine at Different Deionization ization Rates Conductivity (ms cm -1 ) Conductivity (ms cm -1 ) Conductivity (ms cm -1 ) Conductivity (ms cm -1 ) WW Deionization 0.0% Temperature (ºC) WW Deionization Temperature (ºC) WW Deionization19.2% Temperature (ºC) WW 6.9.ºC Deionization 9.4% 11.4ºC 30.1% 16.8ºC 19.7ºC Temperature (ºC) Conductivity (ms cm -1 ) Conductivity (ms cm -1 ) Conductivity (ms cm -1 ) Conductivity (ms cm -1 ) Wine - Wine + 4 g L -1 KHT in Gonçalves, F, Sep. Purif. Technology Deionization Temperature (ºC) WW Deionization Temperature (ºC) WW Deionization 25.5% 9.1ºC Temperature (ºC) RW WW Deionization 9.2ºC 4.7% 14.5% 14.8ºC 0.0% 18.2ºC Temperature (ºC) % Deionization The correlation between the Tsat and Deionization Rate let us conclude that the stabilization by Electrodialysis is an effective way of control the tartaric stability of a wine

30 Tartaric Stabilization of Wine Hybrid process for wine stabilization: Integration of cold with electrodialysis Intial Wine Cold (9 days) Cold (3days) ED Cold (3days)+ED Tartaric acid (g/l) K+ (mg/l) T saturation (ºC) T. anthocians (mg/dm 3 ) Simultaneous stabilization of color and tartaric acid Easy integration with conventional processes of tartaric stabilization by cold.

31 Other Membrane Applications in the Wine Industry

32 Other Membrane Applications in the Wine Industry Grape Must Acidification Sugar Removal from the Grape Must Partial Dealcoholization of Wine Electrodialysis with Bipolar Membranes Ultrafiltration and Nanofiltration Reverse Osmosis or Nanofiltration and Destilation Removal of Volatile Acidity Removal of Volatile Phenols Reverse Osmosis and Ion Exchange Reverse Osmosis and PVPP resins

33 Grape Must Acidification by Electrodialysis with Bipolar Membranes Acidified wine KOH Applicability in Hot Wine Growing Regions where BP C BP normaly the grapes have low acidity and high ph Reduce the necessity to add Tartaric Acid Increase quantity of the molecular form of SO 2 Increase of the microbiologic stability of the wine H + K OH - Increment of organoleptic qualities, namely colour, freshness and persistance Wine Water BP bipolar membrane C cationic membrane in EURODIA Industrie and INRA

34 Sugar removal by Ultrafiltration and Nanofiltration REDUX Process Applicability in Hot Wine Growing Regions Increasing concerns about the alcoholism Two stages of membrane processes Restitution of the retentate of the Ultrafiltration Restitution of the permeate of the Nanofiltration in Cottereau, F (ITV)

35 Sugar removal by Ultrafiltration and Nanofiltration REDUX Process Exemple: Cabernet Sauvignon Vintage Initial Must Permeate of UF Retentate of UF Permeate of NF Retentate of NF Sugars (g L-1) L ph AT g H2SO4 / L Anthocians (mg L-1) L TPI K (g L-1) L CI in Cottereau, F (ITV)

36 Sugar removal by Ultrafiltration and Nanofiltration REDUX Process Exemple: Final Wine - Cabernet Sauvignon Ethanol (% vol.) ph AT (g H2SO4 / L) AV (g H2SO4 / L) Tartaric Acid (g L-1) L Lactic Acid (g L-1) L K+ (g L-1) L Anthocians (mg L-1) L IPT IC Early Harvest Test REDUX Reduction of the Alcohol Strength of the Final Wine The Total Acidity and ph doesn t change significantly Significant increase of the Colour Concentration and the Total Polyphenols in Cottereau, F (ITV)

37 Partial Dealcoholization by Reverse Osmosis in Fisher, U XIX Gior. Int. Vitivinicola

38 Removal of Volatile Acidity by Reverse Osmosis and Ion Exchange Resin Important Applicability in face of Adverse Climatic Conditions during Maturity, when Acid Rot establishes on the Grapes Could be very important for Sauternes wines, Late harvest wines and Ice wines The Maximum Acetic Acid Content in Wines is Regulated by Law in Fisher, U XIX Gior. Int. Vitivinicola

39 Removal of Volatile Acidity by Reverse Osmosis and Ion Exchange Reduction of the all parameters related to the perception of Acetic Acid in Fisher, U XIX Gior. Int. Vitivinicola

40 Removal of Volatile Phenols by Reverse Osmosis and PVPP resins Growing awareness of consummers to Medicinal, horse sweat and barnyard off-flavours produced by the yeast Brettanomyces, usualy in wines aged in oak barrels Potential use in quality wine that stays long time in oak barrels in Fisher, U XIX Gior. Int. Vitivinicola

41 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.

42 Thank you