Beer Stabilization Technology

-clearly a matter of choice

Seven Steps to a Clear Beer !
Mustafa Rehmanji
Andrew Mola
 Scope of Presentation
• Mechanism of Haze Formation
• Upstream Stabilization : Polyclar Brewbrite
• PVPP
• Silica Gel
• Tannic acid
• Papain
• Admixture : Silica +PVPP
 What is Beer Stability?
Beer stability is the extent to which a beer tastes
and looks as good after aging as it did when it
was first packaged. Stability is assessed by:

• Changes in colloidal stability (HAZE)

• Flavor stability (oxidation and staling)
• Color increase
• Microbial stability

Reference : Jean De Clerck, A Text Book of Brewing

 Beer Stabilization Guidelines
Drinking Life Stabilization
Requirements
CASK BEER (UK) 4 weeks None - Low
KEG BEER 10 weeks Low - Medium
EXPORT KEG 36 weeks Medium
SMALL PACK Bottle up to 52 weeks High
Cans up to 75 weeks High

The extent to which a beer requires colloidal

stabilization depends on the raw materials,
process, required shelf life and storage
conditions
 Non-Biological Haze in Beer
• Protein-Polyphenol complexes - chill &
permanent haze
• Carbohydrates - starch & ß-glucans

• Oxalates

• Other constituents - metal hazes,

collapsed fob, PGA, filter aids, iso-α-
acids etc.
 Structures of Polyphenols, Condensed
Polyphenols and Tannoids
Polyphenol Condensed Polyphenol Tannoids

OH
OH
OH OH

HO O OH HO O
R
OH

OH OH
HO O
OH OH OH
OH
OH
Catechin OH
OH
OH

OH
HO O
HO O R
OH
OH OH
OH n
OH
HO O OH OH
OH OH

OH HO O
Prodelphinidin R
OH
OH

Gallocatechin OH
 Haze Formation in Beer
Simple Flavanoids give haze free beer
Oxidized Flavanoids produce CHILL HAZE
Fully oxidized Flavanoids = TANNOIDS produce PERMANENT HAZE

Oxidized Tannoids
Simple
Flavanoids

Protein
Protein Protein
Oxidized
Flavanoids

Haze free beer

Permanent haze
Chill haze

Ref: O’Rourke et al., 1998

 Model for Protein – Polyphenol
Interaction
Polyphenols are depicted as having two ends that can bind to protein. Proteins
are depicted as having a fixed number of polyphenol binding sites.

polypeptide Proline-rich region

polyphenol

Courtesy : Karl Siebert, Cornell University

Formation of Protein-Polyphenol Haze in Beverages, J. Agric. Food Chem. 1996,44, 1997-2005
 Change in Polyphenols and Flavanoids
During Brewing

Total Polyphenols mg/l Total Flavanoid mg/l

1,600 300
Polyphenols
1,400 250 Flavanoids
1,200
200
1,000
800 150
600 100
400
200 50
0 0
Mash in Last runnings Copper cast Fermenter Polyphenols= EBC 9.9.1
Mash end Copper up Whirlpool Maturation Flavanoids = EBC 9.9.2

Brewing Process
Step 1 – avoid use of very weak wort(<1.5 P)
Chill-Haze Development & Shelf- Life Model
(Forced Aging at 37°C) for a Stabilized
Standard Lager Beer
Total Haze (°EBC)
5

4 Correlation co-efficient r = 0.9915

3
Haze Development
Rate = 0.47°EBC units/week
2
Lag Phase
Shelf life
1 (Time to develop haze = 2°EBC)
Permanent or background haze
0
0 1 2 3 4 5 6 7 8 9 10 11 12
Storage Time (weeks)
 Relative Haze Formation
Beer stabilized with 100 g/hl PVPP to remove
reactive polyphenols

Catechin Haze EBC Tannic Haze EBC

2.4 30
2.2 Catechin
25
2 Oxidized Catechin
1.8 Tannic acid 20
1.6 15
1.4 10
1.2
1 5
0.8 0
0 10 20 30 40 50
Addition rate of reactive polyphenols in g/hl
Step 2 – minimize oxygen pick-up! < 0.1 ppm
 Haze Giving Components in Beer

Proteins Polyphenols

Sensitive Proteins Tannoid precursors

Tannoids
 Haze Development Schedule

Time-scale Activity

1 month on 1. Tannoids complex with proteins to produce haze

2 months on 2. Flavanoids oxidise and react with proteins to form chill-haze

3-6 months 3. Flavanoids converted to tannoids

6 months on 4. Tannoids formed from subsequent POLMERIZATION of the

precursors(Flavanoids). They in turn complex with proteins
to produce permanent haze
 Carbohydrate Hazes
• Prevention - raw material selection
- complete starch conversion
- process effects – identify
sources of ‘shear’ damage
• Remedies - enzymes - ß-glucanase,
amylases
dextrinases
 Oxalate Haze - ‘Green Haze’
• ‘Beer stone’ - calcium oxalate
• Octahedral crystal
• Check oxalic acid levels in malt
• Treated by addition of calcium salts
(CaSO4) to brewing liquor to precipitate
oxalate
 Raw Material & Process Strategies to
Optimize Colloidal Stability
Process Polyphenol Reduction Protein Reduction Process Optimization
Raw material Low proanthocyanidin Low protein Low malt modification
selection malt barley Coarse grind of malt
Hop extract
Brewhouse High adjunct ratio Mashing process Vigorous kettle boil for
Avoid weak worts pH, temperature >60 min.
Avoid excess mineral
salts
Good hot break
Cold wort filtration
Fermentation/ Rapid onset to Early yeast Minimum 7 days
Maturation fermentation removal maturation at -1OC

Filtration Low solids count

Filter at -1OC
Avoid O 2 Pick up

 Step 3 – check & verify cold storage temperatures

 Colloidal Stabilization of Beer
Composition of Chill Haze
Adsorption: Precipitation:
- Silica gel -Tannic acid
PROTEINS
40-75%
Adsorption:
- Polyclar Plus
Carbohydrates 3-13% Degradation:
(PVPP-Si composites) Ash 0.7 - 5% - Papain
- Resins Cu,Fe Traces

POLYPHENOLS
About 17%
Adsorption: Protein-Tannoid
complex:
- Polyclar - Chilling
Other Polyphenol:
(PVPP) - PVP or PVP-silica
 What is Polyclar Brewbrite ?
It is a proprietary composite of a selected
Carrageenan and micronized PVPP

Kappa Carrageenan PVPP

CH OH CH
OSO- 2 O O 2
3 O O N O N O N O
O O

OH OH
n n
ß-D-galactose 4 sulfate 3,6-anhydro-α-D-galactose 2-pyrrolidinone,1-ethenyl-, homopolymer

Marine polysaccharide of Cross-linked

galactose & galactose sulfate polyvinylpyrollidone
monomers
 Function/Purpose of Polyclar Brewbrite

 The addition of Polyclar Brewbrite to the boiling wort has

the following functions:
 To stimulate coagulation of the proteinaceous NMP
 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
 Courtesy of Murphy-Savilles Clarification

Effect of Cold Wort Clarity on Beer Clarity

Bright 3
(<3 EBC)

Hazy 2
Clarity (>4 EBC)
Rating
Cloudy 1
(>8 EBC)

0
0.7 1.4 2.1
Filtered Beer Haze (EBC)

Step 4 – wort clarity is very important and is

related to beer clarity
 Increase in Wort Yield - Commercial Trial

Polyclar Brewbrite gave 3.2% increase in cold

wort collected in FV as compared to untreated wort
Volume of Wort at collection, hl

16.1
16.0
15.9
15.8
15.7
15.6
15.5
15.4
15.3
15.2
Untreated Carrageenan, Polyclar
alone 3.9g/hl Brewbrite 15g/hl
Decrease in Fermentation Time with
Polyclar Brewbrite - Commercial Trial
 Polyclar Brewbrite gave 10 % reduction in
fermentation time as compared to untreated
145

140

135

130

125

120

Untreated Carrageenan alone, Polyclar Brewbrite,

3.9g/hl 15g/hl
Analysis of Packaged Beer - Commercial Trial
Accelerated Forcing Test

3.5
3.0 Polyclar
Total Haze, EBC Units

Brewbrite,
2.5 15g/hl

2.0
1.5
Untreated
1.0
0.5
0.0
Initial Cycle 1 Cycle 2 Cycle 3 Cycle 4 Cycle 5

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
 PVPP - Methods of Use

• Single use
– Added prior to primary filtration and removed
at the filtration stage
• Regeneration
– Used after primary filtration on a horizontal
leaf filter or candle filter and then recovered
for re-use
 Stabilization with PVPP

• Slurried in deaerated water (8 - 10% wt/wt)

• Hydrated for 1 hour (maximum efficacy)
• Added to beer during transfer
• Single use - usually added before DE filter
- 5-10 min. contact time
• Regeneration grade - added after DE
filtration
 Possible Injection Points for
Polyclar Plus and Polyclar PVPP
DE
Stabilizer DE Filter
Inlet Buffer
Buffer Tank
Tank Dosing
Preferred Point Tank

To Bright
Packaging Beer
Tank Trap/Bag
Filter Polish Filter
 Tannoid Reduction with PVPP
50
Tannoids (mg/l PVP K-90 to peak haze)

40

30

20
Detection limit 10 - 12 mg/l

10

0
Untreated 10 g/hl 30 g/hl 50 g/hl

Polyclar 10 (g/hl)

 Step 5 – reduce the tannoids with PVPP

 Increase in Shelf Life of PVPP
- Treated Beer
8

7
Predicted Shelf Life (months)

0
Untreated 10 g/hl 20 g/hl 30 g/hl 50 g/hl

Polyclar 10 (g/hl)
 Hydrogels vs. Xerogels
Hydrogel Xerogel

Contain 30-50% water Contain 5% water

Harder to hydrate & disperse

Easier to disperse
(more dusty)

Used at up to ~150 g/hL Used at up to ~80 g/hL

Greater permeability than xerogel Less Permeability than Hydrogel

Less effective than xerogels More effective than hydrogel

Less microbial stability Greater microbial stability

 Action of Silica gel
Protein adsorption follows three sequential
steps:

• Diffusion of proteins from the beer matrix to

the surface of the silica gel (relatively fast
step)
• Attraction: Surface adsorption of proteins to
the hydrated silica gel (relatively fast step)
• Penetration of the surface adsorbed proteins
into the silica gel (rate determining step)
 Protein Stabilizers - Tannic Acid
• From (Chinese) gallnuts
• Complexes with haze-active proteins
• Used at low dosage rates 4-10g/hL
• Added between FV & MV, or,
• In-line to DE filter
• Minimum contact time 10 min.
• Cannot be used at the same time as PVPP,
but can be used sequentially – tannic first,
then PVPP
 Papain
Substrate
/Protein • Enzyme breaks
down acidic proteins
Papain Enzyme MW 45K to
polypeptides
• Most active pH 6.5
Protein/Substrate and 55o C
Complex
Shorter Polypeptides
Enzyme
 Protein Stabilizers - Papain
• Proteolytic enzyme - from papaya
• Four iso-enzymes
• Degrades proteins - non-specific
• Used at low concentrations 1-6 g/hL
• Added at maturation or beer filtration
• Activated during pasteurisation
• Persists in beer
• Adverse impact on beer foam
• Residual enzyme and degraded protein remain in beer
which is undesirable.
 What is Polyclar® Plus ?

A proprietary composite of
micronized
Polyvinylpolypyrrolidone (PVPP)
and selected Silica Xerogel
 Haze Development in Beer over
12 Months
Lager beer stored for 3 days after stabilization
Combined treatment of PVPP & SHG (silica hydrogel)
PVPP (g/hL)
0 g/hl SHG
100 g/hl SHG
0 g/hl PVPP 200 g/hl SHG

15 g/hl PVPP

30 g/hl PVPP

0 5 10 15 20 25
Final haze EBC after 12 months
Benefits of Combined Stabilization

7
Heat-Forcing Cycles to 2 EBC

Silica Silica + Polyclar

Beer Treatment
 Plant Scale Trial at a Microbrewery with
Polyclar Plus 730
(ml P40/100 ml Beer to 5 EBC Additional Haze)

100 Predicted Shelf-Life in Months

90
5
Increasing Protein Stability ==>

80

70
4
60

50 Stabilized - 10 lb/100 bbl 3

40
2
30

20 1
Unstabilized Region
10

0 0
0 10 20 30 40 50 60 70 80 90 100
Increasing Polyphenol Stability ==> I week @ 370C with total haze @ 2 EBC
(ml T125/100 ml Beer to 2 EBC Additional Haze) is equivalent to I month of shelf-life
 Predicted Shelf Results- Plant Trial with Polyclar
Plus 730
(Composite 70%Si + 30%PVPP)
Cycles to 2 EBC (Warm Days)
60°C/24 hr. - 0°/24 hr. 10
8
6
4
2
0

Si hydrogel Si hydrogel Polyclar®

95 g/hl 95 g/hl Plus 730
+ PVPP 60 g/hl
20 g/hl

 Step 6 – Balanced stabilization is efficient

and cost effective
Brewery Trials – Filter Pressures, Run Lengths
& Beer Stability with Polyclar Plus

Stabilizer Dose rate ∆P/hr* Filter Run Time Total Haze**

g/hl (hr.) (EBC)

Xerogel only 35.8 0.49 6.4 6.9

PVPP only 12.6 0.35 7.4 3.6
Polyclar Plus 730 33.0 0.25 12.0 1.2

*Pressure increase at steady state

**Total haze measured at 0oC after 5 days
incubation at 60oC
 Beer Transport

5 Store 0 C

EBC
Store 40 C
4
Cycled
3

Haze
Shaken 40 C
2

Treatments

 Step 7 – don’t forget the beer after it leaves the

brewery!
 Seven Steps to Colloidal Stability
1. Avoid use of very weak wort(<1.5 P)

2. Minimize O2 pickup throughout the brewing process(<0.1

ppm dissolved O2 in beer ex-fermenter and into package)

3. Cold store, transfer & filter beer at 0oC, or below

4. Wort & beer clarity are important – optimize finings & filter
aid use

5. Ensure that the tannoids are reduced (removed) from fresh

beer – use PVPP
6. Balanced stabilization is efficient and cost effective
– silica + PVPP

7. Consider beer transport & storage

Thank You!