by

Ph.D. Student: Fernando Salazar G.

Supervisor: Dr. Francisco López

February 3th, 2005, Tarragona, Spain

WHITE WINE CLARIFICATION BY A NEW HYBRID PROCESS

CONTENT

DEA Project: White wine clarification by a new hybrid process

Introduction

Objectives

Materials & Methods

Preliminary Results

Preliminary Conclusions

2/20

INTRODUCTION

WHITE WINE MAKING

CRUSH

RAW MATERIAL

PRESS

FERMENTATION

CLARIFICATION

SETTLING

CLARIFICATION

STABILIZATION

AGING

STERILIZATION FILTRATION

PAUSTERIZATION

BOTTLED

IN THIS POINT IS FOCUS OUR RESEARCH

WINE INDUSTRYProteins 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)

3/20

Settling

Centrifugation

Filtration

Cross-flow microfiltration

CLARIFICATION TECHNIQUES

DEA Project: White wine clarification by a new hybrid process4/20

CROSS-FLOW MICROFILTRATION

Pressure

Feed

Permeate

Concentrate

Membrane

Pore blocking

Cake

Polarization concentration

Internal adsorption

Fig.1 Configuration cross-flow microfiltration and fouling phenomena

FOULING PHENOMENACROSS-FLOW CONFIGURATION

5/20

Flux decline during the microfiltration process due to fouling on the membrane

CROSS-FLOW MICROFILTRATION

PROBLEMS

DEA Project: White wine clarification by a new hybrid process6/20

Using Bentonite followed by microfiltration

HOW TO SOLVE THE PROBLEM?

Applying a new hybrid process using zirconium oxide as adsorbent material: continuous process

Addition bentonite

Retentate

Retentate

Permeate

Permeate

Feed

Feed

Packed column Hybrid process batch (used actually)

Hybrid process using the packed column as a filter (continuous process)

Microfiltration

7/20

OBJECTIVE

DEA Project: White wine clarification by a new hybrid process

The main goal of this work is to increase the yield of the white wine cross-flow microfiltration

using a new hybrid process

8/20

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 process9/20

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 process10/20

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

11

3 7

6

28

10

14

1

4

5 12

9

13

CROSS-FLOW MICROFILTRATION

MATERIALS & METHODS

Operation conditions:

Tubular module membrane: ceramic ZrO2, length 25 cm, area 0.0094 m2, pore size 0.2 m

Transmembrane pressure: 1.5 bar

Cross-flow velocity: 2

Volumetric flow rate retentate: 3.7

Room temperature 25 ºC

min

L

s

m

11/20

ADSORPTION WITH ZIRCONIUM OXIDE IN PACKED COLUMN

Packed column

White wine after of the adsorption

Peristaltic pump

White wine without

treatment previous

1

4

3

2

1. FEED

2. PERISTALTIC PUMP

MATERIALS & METHODS

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 ).

3. ZIRCONIUM PACKED COLUMN

4. WHITE AFTER OF THE ADSORPTION WITH ZIRCONIUM OXIDE

12/20

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 process13/20

MATERIALS & METHODS

POLYPHENOLS ANALYSIS

TOTAL POLYPHENOLS

Folin’s Method

POLYPHENOLIC PROFILE

HPLC

Polyphenols standards: Gallic acidBenzoic acidFurfural acid, etc.

DEA Project: White wine clarification by a new hybrid process14/20

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 process15/20

PRELIMINARY RESULTS

Fig.2 Pinot Noir wine microfiltration with and without adsorption process

0.0

0.2

0.4

0.6

0.8

1.0

0 5 10 15 20 25 30

Time (min)

Pe

rme

ate

Flu

x N

orm

aliz

ed

(J

/J 0

)

Microfiltration

Hybrid process

The permeate flux increased a 13 % using the new hybrid process.

THE PERMEATE FLUX

DEA Project: White wine clarification by a new hybrid process16/20

The protein and polyphenols content or both?

PNWT PNB PNC PNBC

Bentonite 2 g/l Activated carbon 10 m/l

Bentonite 2 g/l and Activated Carbon 10 ml/l

Pinot Noir Without treatment

DEA Project: White wine clarification by a new hybrid process17/20

PRELIMINARY RESULTS

The protein content

The polyphenol content

0

5

10

15

20

25

To

tal P

rote

in (

BS

A,

mg

/l)

PNWT PNAA PNAHP PNAM PNB PNC PNBC

Treatment

0

1

2

3

4

5

6

To

tal p

oly

ph

en

ols

(IP

)

PNWT PNAA PNAHP PNAM PNB PNC PNBC

Treatment

Wine protein stabilisation

0

5

10

15

20

25

Ne

ph

elo

me

tric

Tu

rbid

ity u

nits

(N

TU

)

PNWT PNAA PNAHP PNAM

Treatment

18/20

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

PRELIMINARY RESULTS

0.0

0.2

0.4

0.6

0.8

1.0

0 5 10 15 20 25 30

Time (min)

Pe

rme

ate

Flu

x N

orm

aliz

ed

(J

/J

0)

Microfiltration

Hybrid process

Bentonite & activated carbon

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

Moreover to decrease the amount of proteins and polyphenols increasing the permeate flux.

19/20

PRELIMINARY RESULTS

PERMEATE FLUX

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

The proteins content has the highest effect on the permeate flux decline

19/20

PRELIMINARY RESULTS

0.0

0.2

0.4

0.6

0.8

1.0

0 5 10 15 20 25 30

Time (min)

Pe

rme

ate

Flu

x N

orm

aliz

ed

(J

/J 0

)

Microfiltration

Hybrid process

Bentonite & Activated Carbon

Activated Carbon

Bentonite

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

20/20

PRELIMINARY CONCLUSIONS

DEA Project: White wine clarification by a new hybrid process

Thanks for your attention!!Any questions?

DEA Project: White wine clarification by a new hybrid process