by Ph.D. Student: Fernando Salazar G. Supervisor: Dr. Francisco López

1. WHITE WINE CLARIFICATION BY A NEW HYBRID PROCESS by Ph.D. Student: Fernando Salazar G. Supervisor: Dr. Francisco López February 3th, 2005, Tarragona, Spain

2. CONTENT • Introduction • Objectives • Materials & Methods • Preliminary Results • Preliminary Conclusions DEA Project: White wine clarification by a new hybrid process 2/20

3. INTRODUCTION WHITE WINE MAKING CRUSH PRESS CLARIFICATION RAW MATERIAL FERMENTATION SETTLING CLARIFICATION STABILIZATION IN THIS POINT IS FOCUS OUR RESEARCH AGING STERILIZATION FILTRATION PAUSTERIZATION WINE INDUSTRY • Proteins and polysaccharides, the colloidal fraction of wine, have a considerable influence on the basic operation carried out during winemaking (e.g clarification, filtration and cold stabilization) BOTTLED 3/20

4. CLARIFICATION TECHNIQUES • Settling • Centrifugation • Filtration • Cross-flow microfiltration DEA Project: White wine clarification by a new hybrid process 4/20

5. CROSS-FLOW MICROFILTRATION Polarization concentration Cake Pore blocking Internal adsorption FOULING PHENOMENA CROSS-FLOW CONFIGURATION Pressure Concentrate Feed Membrane Permeate Fig.1 Configuration cross-flow microfiltration and fouling phenomena 5/20

6. CROSS-FLOW MICROFILTRATION PROBLEMS • Flux decline during the microfiltration process due to fouling on the membrane DEA Project: White wine clarification by a new hybrid process 6/20

7. HOW TO SOLVE THE PROBLEM? • Using Bentonite followed by microfiltration Retentate Permeate Microfiltration Feed Addition bentonite • Applying a new hybrid process using zirconium oxide as adsorbent material: continuous process Retentate Permeate Packed column Hybrid process batch (used actually) Hybrid process using the packed column as a filter (continuous process) Feed 7/20

8. OBJECTIVE The main goal of this work is to increase the yield of the white wine cross-flow microfiltration using a new hybrid process DEA Project: White wine clarification by a new hybrid process 8/20

9. SUB-OBJECTIVES • To design a new hybrid process using a packed column with zirconium oxide and cross-flow microfiltration. • To evaluate the yield of the cross-flow microfiltration with or without previous adsorption process. • To evaluate the effect of the proteins and polyphenols content on the permeate flux. • To evaluate the wine protein stabilization considering the cross-flow microfiltration and the new hybrid process. DEA Project: White wine clarification by a new hybrid process 9/20

10. MATERIALS & METHODS WHITE WINE SAMPLES • Pinot Noir • Sauvignon Blanc • Chardonnay • Malvasia These samples were obtained from Mas dels Frares Winery, harvests 2003 and 2004. Tarragona, Spain. DEA Project: White wine clarification by a new hybrid process 10/20

11. MATERIALS & METHODS 3 7 2 8 4 6 9 12 5 13 14 1 10 CROSS-FLOW MICROFILTRATION 11 1. FEED 2. PUMP 3. TRANSMEMBRANE PRESSURE (MANOMETER) 4. VALVULE 5. VALVULE 6. PURGE 7. INPUT PRESSURE (MANOMETER) 8. TUBULAR MODULE MEMBRANE 9. PERMEATE STREAM 10. DIGITAL BALANCE 11. DATA ACQUISITION SYSTEM 12. OUTPUT PRESSURE (MANOMETER) 13. VALVULE 14. RETENTATE STREAM • Operation conditions: • Tubular module membrane: ceramic ZrO2, length 25 cm, area 0.0094 m2, pore size 0.2 mm • Transmembrane pressure: 1.5 bar • Cross-flow velocity: 2 • Volumetric flow rate retentate: 3.7 • Room temperature25 ºC 11/20

12. MATERIALS & METHODS ADSORPTION WITH ZIRCONIUM OXIDE IN PACKED COLUMN 3 2 Packed column 4 White wine without treatment previous White wine after of the adsorption 1 1. FEED 2. PERISTALTIC PUMP 3. ZIRCONIUM PACKED COLUMN 4. WHITE AFTER OF THE ADSORPTION WITH ZIRCONIUM OXIDE Peristaltic pump • Operation conditions: • Zirconium oxide pellet • The packed column is of 19 cm high and internal diameter of 5.1 cm, 200-250 g of ZrO2 • The wine is pumped up-flow mode by a Watson Marlow 101 U/R peristaltic pump at a constant volumetric flow rate of 2 ml/min (1 h of residence time ). 12/20

13. MATERIALS & METHODS PROTEIN ANALYSIS • TOTAL PROTEIN • Bradford’s Method • PROTEIN FRACTIONS • HPLC • Molecular Weight (MW) • Proteins standards: • Bovine serum albumin (BSA) • Ovalbumin (OV) • Lysozyme (LY) • PROTEIN HEAT STABILITY TEST • 2 h at 80ºC and after for 2 h at 4ºC • Nephelometric turbidity units (NTU) DEA Project: White wine clarification by a new hybrid process 13/20

14. MATERIALS & METHODS POLYPHENOLS ANALYSIS • TOTAL POLYPHENOLS • Folin’s Method • POLYPHENOLIC PROFILE • HPLC • Polyphenols standards: • Gallic acid • Benzoic acid • Furfural acid, etc. DEA Project: White wine clarification by a new hybrid process 14/20

15. MATERIALS & METHODS PHYSICOCHEMICAL PROPERTIES • pH • Total acidity, g/L tartaric acid • Volatile acidity, g/L acetic acid • Fixed acidity, g/L tartaric acid • Sugar reducer, g/L • Volumetric alcoholic degree, %vol • Total dry extract, g/L • Ash, g/L • Chloride, g/L NaCl • Sulphates, g/L K2SO4 • Chromatic characteristics (absorbance at 420, 520 and 620nm) DEA Project: White wine clarification by a new hybrid process 15/20

16. PRELIMINARY RESULTS THE PERMEATE FLUX • The permeate flux increased a 13% using the new hybrid process. Fig.2 Pinot Noir wine microfiltration with and without adsorption process DEA Project: White wine clarification by a new hybrid process 16/20

17. PRELIMINARY RESULTS PNWT PNB PNC PNBC The protein and polyphenols content or both? Pinot Noir Without treatment Bentonite 2 g/l Activated carbon 10 m/l Bentonite 2 g/l and Activated Carbon 10 ml/l DEA Project: White wine clarification by a new hybrid process 17/20

18. PRELIMINARY RESULTS The protein content Wine protein stabilisation The polyphenol content PNWT: wine without treatment PNAA: wine after adsorption process PNAHP: wine after hybrid process PNAM: wine after microfiltration PNB: wine after bentonite treatment PNC: wine after activated carbon treatment PNBC: wine after bentonite&carbon treatment 18/20

19. PRELIMINARY RESULTS PERMEATE FLUX • Moreover to decrease the amount of proteins and polyphenols increasing the permeate flux. Fig.3 Permeate flux of Pinot Noir wine during the microfiltration process considering the bentonite&active carbon treatment DEA Project: White wine clarification by a new hybrid process 19/20

20. PRELIMINARY RESULTS PERMEATE FLUX • The proteins content has the highest effect on the permeate flux decline Fig.4 Permeate flux of Pinot Noir wine during the microfiltration process considering different treatments DEA Project: White wine clarification by a new hybrid process 19/20

21. PRELIMINARYCONCLUSIONS • Necessary to increase the residence time during the adsorption process. • According to preliminary results of Pinot Noir, the hybrid process allowed to increase the permeate flux during the microfiltration process. • Necessary to use another adsorbent material more selective with the total polyphenols. • Very important to know the behaviour of the other wines and the results by HPLC DEA Project: White wine clarification by a new hybrid process 20/20

22. Thanks for your attention!! Any questions? DEA Project: White wine clarification by a new hybrid process