Haze Formation in Beer

Mustafa Rehmanji
Andrew Mola
 Beer Haze Definitions

• Biological Haze - microbial origin

• Non-Biological Haze - presence of
colloidal matter makes beer appear
hazy
• Chill Haze - formed when beer is
cooled to 0oC; re-dissolves on warming
to 20oC. (Increases during storage)
• Permanent Haze - irreversible haze,
remains in beer at 20oC
 Non-Biological Haze in Beer
• Protein-Tannin complexes - chill &
permanent haze
• Carbohydrates - starch & ß-glucans
• Proteins
• Oxalates
• Other constituents - metal hazes,
collapsed fob, PGA, filter aids, iso-α-
acids etc.
 Carbohydrate Hazes
Prevention
• raw material selection
• complete starch conversion
• minimise process effects
Remedies
Use of enzymes:
• ß-glucanase
• amylases
• dextrinases
Oxalate Haze - ‘Green Haze’

• ‘Beer stone’ - calcium oxalate

• Check oxalic acid levels in malt
• Treated by addition of calcium salts
to brewing liquor to precipitate
oxalate
 Mechanism of Non-
Biological Haze Formation
Fresh beer: HAZE <0.6EBC

Flavanoids + Oxygen + Polyphenoloxidase:

• Flavanoids oxidize & become more haze-active,
complexing with proteins to form
CHILL HAZE

• Flavanoids fully oxidize & form Tannoids; these

complex with Protein to form
PERMANENT HAZE
 Formation of Haze in Beer
Simple Flavanoids give haze free beer
Oxidised Flavanoids produce CHILL HAZE
Fully oxidised Flavanoids = TANNOIDS produce PERMANENT HAZE

Oxidised Tannoids
Simple
Flavanoids

Protein
Protein Protein
Oxidised
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
 (Reactive) Polyphenols & Proteins
Model

6-9months

3-5months 9-12months
 Haze Giving Components in Beer

Proteins Polyphenols

Sensitive Proteins Tannoid precursors

Tannoids
 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
 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
 Oxidation of Polyphenols

in a mode l s olution of oxidis e d ca te chin

Ta nnoid conce ntra tion in mg/l Flava nol conce ntra tion mg/l
20 35 Ta nnoids

Flava noids
15 30

10 25

5 20

0 15
0 1 2 3 4 5 6 7
Time of oxida tion in days
process needs polyphenol oxidase
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
00 1 2 3 4 5 6 7 8 9 10 11 12
Storage Time (weeks)
 Haze Formation
Haze (°EBC)

Haze formation
3
Slope = 0.47°EBC / Week
2
Lag Phase
1 Stability
(time until haze of 2°EBC developed)

0
0 1 2 3 4 5 6 7 8 9 10 11 12

Storage at 37°C (weeks)

PT-Formula by Chapon

P + T ↔ PT
 Effects of Chapon´s Law
Polyphenol protein complexes can re-dissolve:
• when beer warms up
• when one of the components is removed
thus -
• beer should be kept cold (0oC, or below)
until addition of stabilizers
• stabilized beer should not flow through a
filter cake of polyphenol-protein
complexes
 Factors Affecting
Haze Development
• Haze-forming Polyphenols
• Haze-forming Proteins
• Oxygen
• Heat
• Movement
• Particulates, Carbohydrates
• Heavy metals (Cu, Fe)
• Light, pH, iso-Alpha-acids + others
 Material & Processes
Strategies to Optimise
Colloidal Stability
PROCESS POLYPHENOL PROTEIN PROCESS
REDUCTION REDUCTION OPTIMIZATION
Raw material Low Low protein (N) barley Low malt modification
selection proanthocyanidin Coarse grind of malt
malt
Hop extract
Brew house High adjunct ratio Mashing process, pH Vigorous kettle boil for >60
Avoid weak worts and temperature min.
Good hot break Avoid excess mineral salts
Cold wort filtration
Fermentation Rapid onset to Early yeast removal Minimum 7 days maturation
and Maturation fermentation at -1°C
Filtration Low solids count
Filter at -1°C
Avoid O2 pick-up
 Stabilization Techniques

COMPOSITION
Adsorption: OF CHILL HAZE Precipitation:
- Silica xerogel or - Tannic acid
hydrogel PROTEINS
40 - 75%
Degradation:
Simultaneous Carbohydrates 3 - 13% - Papain
Adsorption: Ash 0.7 - 5%
- Polyclar® Plus Cu, Fe, Traces

POLYPHENOLS Protein-Tannoid
Adsorption: About 17% Complex Removal:
- Polyclar® (PVPP) - Chilling

Complexation:
Formaldehyde
 Options for Achieving
Beer Stability

• Remove haze-forming Polyphenols

• Remove haze-forming Proteins
• Remove both haze-forming polyphenols
& proteins - combined stabilization

 combined stabilization is the best

option for a good physical stability