Novel Options for Stabilization of Beer

Mustafa Rehmanji

Ashland Inc.

1005 Route 202/206

Bridgewater, NJ 08807

Scope of Presentation

• Why should you Stabilize your Beer ?

• Implications of Colloidal Stability

• Mechanism of Haze Formation

• Option for Upstream Stabilization with Polyclar Brewbrite

• Combined Stabilization with Polyclar Plus 730

• Consumer expectations for better quality and product

consistency

• Expanded distribution areas: Beer travelling farther from the

brewery

• Challenge of producing quality products in developing markets

to compete with imports

• Need to reduce costs – production, return of beers

Drivers for Beer Stabilization

• Development of Haze in Beer – The colloidal stability of beer is a function of time and temperature.

• The end of useful shelf life of beer is defined in terms of haze.

• Total Haze of 2.0 EBC units is usually taken as the end of shelf life

Beer Haze Stability Definition

Beer Storage and Transport

Treatments

0

1

2

3

4

5

6

7

8

Haz

e E

BC

Store 0 C

Store 40 C

Cycled

Shaken 40 C

Data courtesy Brewing Research Institute, UK.

SimpleFlavanoids

Protein

ProteinOxidizedFlavanoids

Tannoids

Protein

No haze formation Chill haze Permanent haze

Model of Haze Formation

polypeptide Proline-rich region

polyphenol

Polyphenols are depicted as having two ends that can bind to protein. Proteins are depicted as having a fixed number of polyphenol binding sites.

Courtesy : Karl Siebert, Cornell University

Formation of Protein-Polyphenol Haze in Beverages, J. Agric. Food Chem. 1996,44, 1997-2005

Model for Protein – Polyphenol Interaction

Relative Haze FormationBeer stabilized with 100 g/hl PVPP to remove

reactive polyphenols

Catechin Haze EBCOxidized Catechin Tannic Haze EBC

0 10 20 30 40 500.8

1

1.2

1.4

1.6

1.8

2

2.2

2.4

0

5

10

15

20

25

30

Addition rate of reactive polyphenols in g/hl

CatechinOxidized CatechinTannic acid

Flavanoids & Tannoids in Beer

Shelf Life ModelCompare with PRIOR SLIDE

3 months

Haze-active Polyphenols & ProteinsBeer Model

9-12months

5-9months

Flavanols

TannoidsSensitiveProteins

Non-hazeactive

polyphenols

Non-hazeactive

proteins

Proteins Polyphenols

Balanced “As Needed” Stabilization

Raw Material & Process Strategies to Optimize Colloidal Stability

Process Polyphenol Reduction Protein Reduction Process Optimization

Raw materialselection

Low proanthocyanidinmalt

Hop extract

Low protein barley

Low malt modification

Coarse grind of malt

Brewhouse High adjunct ratio

Avoid weak worts

Mashing process pH, temperature

Good hot break

Vigorous kettle boil for>60 min.

Avoid excess mineralsalts

Cold wort filtration

Fermentation/

Maturation

Rapid onset tofermentation

Early yeast removal

Minimum 7 days maturation at -1OC

Filtration Low solids count

Filter at -1OC

Avoid O 2 Pick up

Admixture of Kappa-Carrageenan and micronized PVPP- Polyclar Brewbrite

Marine polysaccharide of galactose & galactose sulfate monomers

OCH

2O

OH

OO

CH2OH

OSO-3O

OH

O

n

ß-D-galactose 4 sulfate 3,6-anhydro-α-D-galactose

ONON N O

Cross-linked polyvinylpyrollidone

n

2-pyrrolidinone,1-ethenyl-, homopolymer

Kappa Carrageenan PVPP

Function/Purpose

The addition of Admixture of Carrageenan/PVPP to the boiling wort has the following functions:

• To stimulate coagulation of the proteinaceous particulates

• To promote the cohesion of the coagulated protein particles and of other protein-carbohydrate complexes into bigger flocs which can settle to the bottom of the tank faster (whirlpool), or are more effectively removed by a mash filter

• To facilitate upstream adsorption of polyphenols, particularly, TANNOIDS from the wort

Effect of Cold Wort Clarity on Beer Clarity

Courtesy of Murphy-Savilles Clarification

wort clarity is very important and is related to beer clarity

Bright(<3 EBC)

Hazy(>4 EBC)

Cloudy(>8 EBC)

ClarityRating

Filtered Beer Haze (EBC)

0.7 1.4 2.1

0

1

2

3

Increase in Wort Yield - Commercial TrialBrewbrite gave 3.2% increase in cold wort collected in FV as compared to untreated wort

Also, Brewbrite gave a higher throughput on the centrifuge and longer filter run lengths

Vo

lum

e o

f W

ort

at

colle

ctio

n,

hl

15.2

15.3

15.415.5

15.6

15.715.8

15.916.0

16.1

Untreated Carrageenan,alone 3.9g/hl

Brewbrite15g/hl

Fer

men

tat i

on

Tim

e , h

ou

rs

Decrease in Fermentation Time –

Commercial Trial Brewbrite gave 10 % reduction in

fermentation time as compared to untreated

120

125

130

135

140

145

Carrageenan alone,

3.9g/hl

Untreated Admixture

15g/hl

Analysis of Packaged Beer - Commercial TrialAccelerated Forcing Test

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Initial Cycle 1 Cycle 2 Cycle 3 Cycle 4 Cycle 5

Admixture

15g/hl

Untreated

Cycle = 24 hours at 600C followed by 24 hours at 00C

No. of Cycles (to reach 2.0 EBC Units) = month of predicted shelf life

To

tal

Ha

ze,

EB

C U

nit

s

Trial AMalt- Adjunct Lager

Control Beers• Average cold wort

collection = 501 hl

• Wort clarity = 4.3 EBC• Total haze at end of

shelf life = 7.1 EBC

Brewbrite Trial Beers• Average cold wort

collection = 506 hl (+1% volume)

• Wort clarity = 1.2 EBC

• Total haze at end of shelf life = 4.5 EBC

Trial B – All Malt LagerDosage Evaluation

0

20

40

60

80

100

120

0 5 10 15 20 25 30

Brewbrite Addition Rate (g/hl)

Tannoid

s (m

g/l)

0

5

10

15

20

25

30

35

Wort C

larity

(E

BC

)

Tannoids (mg/l) Wort Clarity (EBC)

OptimumAddition Range

Dosage Evaluation-Trial B

Dosage Evaluation

0

20

40

60

80

100

120

0 10 15 20 25

Brewbrite Addition Rate (g/hl)

Tannoid

s (

mg/l)

Tannoids (mg/l) Wort Clarity (EBC)

OptimumAddition Range

Trial-B 100% Malt Lager

Polyphenol Reduction

0

50

100

150

200

250

300

350

400

Pre-addition Post addition

Sample Stage

mg

/l

Tannoids Total Polyphenols

Tannoid reduction = 49%

Total Polyphenol reduction = 21%

South America Brewery TrialsBrewery Wort Yield

(%)Beer Stability

A +2 Slight increase

B +2 Similar to 40 g/hl SHG + wort stabiliser

C 0 Similar to 60 g/hl SHG + papain

0

10

20

30

40

50

60

70

80

90

100

110

0 25 50 75 100 125 150

Sample as is

Segregation BEGIN

Segregation MIDDLE

Segregation END

Will the Materials Segregate?

Particle Size in m

% T

ota

l Par

ticl

es

The potential for Polyclar Brewbrite to segregate due to a sifting mechanism is low

Enhances clarity of wort & beer

Increases wort production

Decreases fermentation time

Improves total productivity of plant

Extends shelf life of packaged beer

Longer shelf life requires PVPP treatment at filtration

PVPP helps reduce astringency in beer** Measuring Astringency of Beverages using a Quartz-Crystal Microbalance

J.Am.Soc. Brew. Chem. 61(3):119-124, 2003

Summary of Trial Results

A composite of micronized

Polyvinylpolypyrrolidone (PVPP) and

selected Silica Xerogel- Polyclar® Plus 730

Optimized ratio for preventing chill and permanent haze High adsorptive capacity for haze- forming precursors Improved handling and performance characteristics

Key Features

Inversions required to re-disperse 10% slurries after 24 hours of sedimentation

Improved dispersion results in a more homogeneous dosing into the beer

Greater than 2000

PVPP Xerogel PVPP/Silica Admixture

8057

Re-dispersion PVPP/Silica Admixture

Polish FilterTrap/Bag

Filter

Dosing Tank

InletBufferTank

DE Filter

ToPackaging

DEStabilizer

Buffer Tank

Bright BeerTank

Possible Injection Points

0

2

4

6

8

10

Si hydrogel95 g/hl

Si hydrogel95 g/hl

+ PVPP20 g/hl

AdmixturePVPP/Silica

xerogel40 g/hl

Cyc

les

to 2

EB

C (

War

m D

ays)

60°C

/24

hr.

- 0

°/24

hr.

Forced Haze Development in Packaged Beer - Trial A

AdmixturePVPP/Silica

xerogel60 g/hl

AdmixturePVPP/Silica

xerogel80 g/hl

200 bbl of American lager treated Stabilizer dosed in-line, before buffer tank Dosage rate of PVPP/silica xerogel

admixture - 10 lb/100 bbl (38.5 g/hl)

US Microbrewery Trial B

0

1

2

3

4

5

Untreated Admixture

Predicted Shelf-Life in Months

I week @ 370C with total haze @ 2 EBCis equivalent to I month of shelf-life

0

10

20

30

40

50

60

70

80

90

100

0 10 20 30 40 50 60 70 80 90 100

Increasing Polyphenol Stability ==>(ml T125/100 ml Beer to 2 EBC Additional Haze

Incr

easi

ng

Pro

tein

Sta

bil

ity

==

>(m

l P

40/1

00 m

l B

eer

to

5 E

BC

Ad

dit

ion

al H

aze

Stabilized - 10 lb/100 bbl

Unstabilized Region

Trial B Stabilization ResultsPVPP/Silica Xerogel Admixture

Objective to increase product shelf life Normal regime - silica hydrogel on transfer to MV &

PVPP at filtration Admixture of PVPP/Silica Xerogel (40 g/hl) dosed

on transfer from FV to MV (900 hl) Beer cold stored for 7 days PVPP (20 g/hl) added with DE body-feed - very

short contact time ~3 min.

Ale Stabilization- 2 Stage : Trial C

• Stage 1 - complete tannoid removal & substantial protein and flavanoid reduction •Stage 2 - further flavanoid reduction

BBT FV MV

Tannoids 35.0 <12 <12 (mg/l) T125 Polyphenols 11.9 55.0 123.0 (ml/100ml) P 40 Proteins 21.2 49.4 51.6 (ml/100ml) Admixture PVPP/Silica Xerogel (40 g/hl) PVPP (20 g/hl)

T125 & P40 - high values indicate better stabilization

Ale Stabilization- 2 Stage : Trial C

Brewery Trials – Filter Pressures, Run Lengths & Beer Stability

Admixture PVPP/Silica Xerogel

PVPP only

Xerogel only

Stabilizer

33.0

12.6

35.8

Dose rate

g/hl

12.0

7.4

6.4

Filter Run Time (hr.)

1.2

3.6

6.9

Total Haze**

(EBC)

0.25

0.35

0.49

P/hr*

*Pressure increase at steady state**Total haze measured at 0oC after 5 days incubation at 60oC