The Theory of Cleaning with Special Focus

on Using Hydrogen Peroxide

Oliver Meinhold

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 Content
• Raw Materials
• Soil
• How to tackle fouling
• Cleaning parameters (Sinner Circle)
• Oxidizers
• Hydrogen Peroxide

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 Composition of Malting Barley and Malt
Comparison Barley Malt
Starch [%] d.m. 63 – 65 58 – 60
Saccharose [%] d.m. 1–2 3–5
Reducing sugars [%] d.m. 0.1 – 0.2 3–4
Other sugars [%] d.m. 1 2
Soluble gums [%] d.m. 1 – 1.5 2–4
Hemicellulose [%] d.m. 8 – 10 6–8
Cellulose [%] d.m. 4–5 5
Lipids [%] d.m. 2–3 2–3
Raw proteins [%] d.m. 8 – 11 8 – 11
Albumins [%] d.m. 0.5 2
Globulins [%] d.m. 3 -
Hordein [%] d.m. 3–4 2
Glutelin [%] d.m. 3–4 3–4
Amino acids and peptides [%] d.m. 0.5 1–2
Nucleic acids [%] d.m. 0.2 – 0.3 0.2 – 0.3
Minerals [%] d.m. 2 2.2
Other compounds [%] d.m. 5-6 6-7

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 Different Types of Brewing Liquor
Origin Pilsen Munich Vienna Dortmund Burton

Total hardness [mg/L] 28.48 263.44 384.48 747.6 923.82

Carbonate hardness [mg/L] 23.14 252.76 291.92 299.04 234.96

Non-carbonate hardness [mg/L] 5.34 10.68 92.56 448.56 688.86

SO3 [ppm] 4.0 8.0 82.0 241.0 -

Cl [ppm] 5.0 2.0 7.0 107.0 -

Ca [°dH] 17.8 188.68 249.2 653.26 667.5

Mg [°dH] 10.68 74.76 133.5 94.34 256.32

Compensated alkalinity [°dH] 7.12 64.08 90.78 201.14 227.84

Residual alkalinity [°dH] 16.02 188.68 201.14 97.9 7.12

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 Hop Composition
Compound [%] as is
Water 10.0 – 12.0
Total resins 12.0 – 21.0
▪ Humulones 4.0 – 10.0
▪ Lupulones 3.0 – 6.0
▪ Hard resins 2.0 – 3.0
Protein 11.5 – 20.0
Cellulose 10.0 – 17.0
Polyphenols 4.0 – 14.0
Mineral salts 7.0 – 11.0
Carbohydrates 4.0 – 9.0
Fats and waxes <3
Oils 0.5 – 2.5
Fatty acids 0.05 – 0.2
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 Yeast
Compound [%]
Thick pulpy yeast 85 - 90
Pressed yeast 65 - 85
Intracellular water content 55 - 65
Commercial dried yeast 5 - 10 8%
Dry matter:
Nitrogen compounds 45 - 60
Carbohydrates 15 - 37 (10 % Yeast gums and glycogen)
Fat 2 - 12
Ash 6 - 12
Vitamins, etc traces

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 Brewing Process
Barley Malting Malt Process steps
Intermediate and final products
Water Brewhouse Wort

Yeast Fermentation Green Beer

Hops Maturation Filtration

Bright Beer
Additives

Storage Bottles, Cans, KEGs Packaging

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 Process Steps

• Brewhouse
degradation of high molecular polysaccharides (starch) and proteins to small
molecular and fermentable saccharides and soluble proteins
• Fermentation
conversion of fermentable saccharides to ethanol and CO2
• Maturation
yeast settles down and beer flavor matures
• Filtration
separation of yeast and precipitated conglomerates (e.g. proteins, polyphenols)
• Packaging
bright beer is packaged into bottles, cans and KEGs

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 Calandria

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 Fermenter

Fouling above liquid level

Liquid surface

Deposit (yeast) after emptying

fermentation tank

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 Fouling

• What is the fouling (by-product) consist of?

The composition of the fouling material needs to be defined to determine
further processes.
• Product value?
If there is value it should be collected and sold.
• Prevention of fouling
If there is no value it should be prevented, which is not easy.
• Removal by cleaning
If it cannot be prevented, it needs to be removed by cleaning.

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 How to tackle fouling

No
What type is Composition
Fouling
it? analysis

Yes

Yes
Collection Any value?

No

Further use (treatment,

Prevention (research) Cure (CIP)
storage, etc.)

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 Solubility of food deposits before and after thermal impact
Change during
Deposit Solubility Ease of removal Mechanism Ease of removal
heating

Sugar Water soluble Easy Crystallization Caramelization More difficult

Water and alkali

Fat Difficult Crystallization Polymerization More difficult
soluble

Water soluble,
alkali soluble,
Protein Very difficult Chemical reaction Denaturation More difficult
slightly acidic
soluble

Water solubility
Interaction with
Minerals variable most are Easy to difficult Crystallization Generally easier
other compounds
acid soluble

Grasshoff, 1997
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 Change of Cleaning Requirements
Brewing steps Type of Fouling Cleaning Requirements
Malting Particulates Physical / Visual
Brewhouse
Proteins and Minerals Visual and Chemical
Wort Cooling
Fermentation Chemical and Microbiological
Yeast Films, Proteins
Maturation
Filtration
Beer and Minerals
Bright Beer Tank
Packaging
Draft Beer Dispensing Biofilm
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 Cleaning Requirements
Process Plant Soil Type Required How Obtained

Malting Floors, Screens Particulate Physically cleaned Manually

Milling Mill, Rollers Particulate, Starch, Protein Physically and or Manually or CIP
chemically cleaned
Mashing Mash tun Particulate, Starch, Sugar, Chemically cleaned Manually or CIP
Protein, Scale, Tannin
Lautering Mash tun, Lauter- tun, Particulate, Starch, Sugar, Chemically cleaned Manually or CIP
Mash filter, Strainmaster Protein
Boiling Wort kettle, Hop kettle Particulate, Starch, Sugar, Chemically cleaned Manually or CIP
Protein, Scale, Tannin
Separation Whirlpool, Settling tank, Hops, Trub, Tannin Microbiologically cleaned CIP + detergent / or
Hop-Strainer sanitizer
Cooling Heat exchanger Protein, Scale, Particulate Microbiologically cleaned CIP + detergent / or
sanitizer
Fermentation Fermentation tanks, Open Yeast, Protein, Oxidation Microbiologically cleaned CIP + detergent / or
vessel products, Tannin, Sugar, sanitizer
Scale

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 Cleaning Requirements
Process Plant Soil Type Required How Obtained

Yeast Harvest (Separation) Centrifuge, Yeast press Yeast, Protein Microbiologically cleaned CIP + detergent / or
sanitizer manually
followed by a sanitizing
step
Conditioning Closed Vessel Yeast, Protein, Scale Microbiologically cleaned CIP + detergent / or
sanitizer
Filtration Filter, Centrifuge Yeast, Protein Microbiologically cleaned CIP + detergent / or
sanitizer
Storage, Transport Bright Beer Tanks, Yeast, Protein, Scale Microbiologically cleaned CIP + detergent / or
Container for sanitizer
Transportation
Pasteurization Flash Pasteurizer, Heat Protein, Scale Microbiologically cleaned CIP + detergent / or
Exchanger sanitizer

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 Cleaning Requirements
Process Plant Soil Type Required How Obtained

Packaging (KEG) KEG, Cask Filler Protein, Scale, Particulate Microbiologically cleaned CIP + detergent / or
deposits sanitizer
Inside equipment with
temperature and
causticity
Packaging (Bottle, Can) Bottle / Can Filler Protein, Scale, Paper, Glue Microbiologically cleaned CIP + detergent / or
sanitizer
Inside equipment with
temperature and
causticity
Pasteurization Tunnel Pasteurizer Algae, Scale Microbiologically cleaned Dosing of biocide, Scale
Control
Can/Bottle Warming Can/Bottle Warmer Algae, Scale Microbiologically cleaned Dosing of biocide, Scale
Particulate deposits Control

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 Cleaning Map
Cleaning solution
Hot Chemical Type 3:
Personal product and
pharmaceutical lotions Cohesive solids removed
with chemical
Sanitizing
Type 2:
Biofilm

Non-viscous fluids Viscous fluids Cohesive soil

Type 1:
Viscous liquids Hot Water
Remove by rinsing Soil complexity
removed with hot
water

Soils that dissolve in

water (e.g. sugar)

Product changeover:
Product recovery viscous fluids Water ambient
temperature
Fryer and Asteriadou, 2009
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 Forces Acting on Soil during Cleaning

Mechanical force Thermal force Chemical force

Soil

Tank wall

Adhesive forces holding soil on surface

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 Sinner Circle

Concentration Temperature

Mechanics Time

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 Temperature

Soil Effect
Proteins Medium
Fats Good
Carbohydrates Good
Minerals Good

A temperature increase by 10 °C (18 °F) doubles the speed of reaction

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 Time

• Each CIP cycle step is optimized according to the following parameters

• Type of process equipment
• Type of process
• Duration of process step
• Temperature of cleaning solution
• Concentration of cleaning solution

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 Mechanics
• Assuming a 2mm film thickness (0.002m)
• Assuming a completely wetted surface
• Internal Surface must be determined:
• Dome
• Cylinder
• Cone

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 Mechanics

Laminar

DH is the hydraulic diameter of the pipe; its characteristic travelled length, L, (m).
Q is the volumetric flow rate (m3/s). A is the pipe cross-sectional area (m²).
v is the mean velocity of the object relative to the fluid (SI units: m/s).
μ is the dynamic viscosity of the fluid (Pa·s or N·s/m² or kg/(m·s)).
Turbulent ν is the kinematic viscosity (ν = μ/ρ)(m²/s).
ρ is the density of the fluid (kg/m³).

LAMINAR TRANSITION TURBULENT

0
~2100 ~4000

If a pipe diameter is increased from DN80 to DN100 and the flow volume is maintained, the flow velocity will
drop from to 2 m/sec to 1,25 m/sec.
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 Chemical
Effect on cleaning operation

Soil Water Caustic Acid

Proteins Poor Good Medium
Fats Poor Good Medium
Carbohydrates Good -- --
Minerals medium Medium Good

Required concentrations depend on soil level, processes used, time, temperature, etc.

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 Chemical

• Quality of water used for aqueous cleaning:

• Chemical properties (pH, hardness, etc.)
• Biological properties (bioburden, endotoxins)
• Pre-Rinsing
Solely for removing loose soil prior to chemical cleaning. Usually based on
practicality of what type of water is available.
• Chemical cleaning
Most critical is water hardness → effects efficiency of cleaning solutions
• Rinsing
In general, the final rinse water used should have the same quality as used in
the final production step.

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 Typical CIP Program

Step Operation Cleaning Temperature [°C/°F] Time Usage

agent [min]
1 Pre-Rinse Water 20 – 30 / 68 – 86 2–5 To drain
2 Caustic 2 % Caustic 70 – 80 / 158 – 176 5 – 30 Re-circulated
3 Rinse Water 20 – 30 / 68 – 86 1–5 To drain
4 Acid 1 % Acid 20 – 30 / 68 – 86 3 – 15 Re-circulated
5 Rinse Water 20 – 30 / 68 – 86 4 – 10 To drain
6 Sanitation Sanitizer 20 – 30 / 68 – 86 5 – 15 To drain

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 Oxidative Cleaning Intensifiers
• These oxidizing compounds are additionally used next to
conventional detergents to remove tough soils.
• The following compounds are commonly used:
• Sodium hypochlorite solution ("Chlorine Bleach")
• Hydrogen peroxide
• Perborate
• Percarbonate
• All these compounds have one effect in common. In a hot alkaline
solution they split off active oxygen, which can oxidatively crack
tough soils.

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 Oxidative Cleaning Boosters

• Better soil wetting and penetration

• Better soil removal
• Less corrosion to metal
• Can be used at hot temperatures (160 – 180 °F)
• Less manual scrubbing

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 Hydrogen Peroxide
Mode of action:
H2O2 → H2O + O
Hydrogen peroxide is not as effective as sodium hypochlorite (oxidation potential),
however, it is an efficient cleaning intensifier in combination with alkaline cleaning
agents.
• In a hot and alkalinic solution a quick decomposition to water and oxygen
takes place, thus the dosage of the cleaning intensifier should take place
directly before cleaning and as close as possible in front of the equipment to
be cleaned.
• Hermetically sealed installations have to be equipped with a ventilation to
remove the oxygen produced, otherwise high pressure builds up inside if
the installation

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 Hydrogen Peroxide - Advantages
• Less or no manual scrubbing
• Reduced chemical usage
• Time saving, shorter CIP cleaning cycles
• Improves removal of protein compared to only caustic
• Less active alkalinity (caustic) required to get the same cleaning result
• The metal compatibility (steel, gaskets, etc.) is definitely better compared to
sodium hypochlorite.
• Hydrogen peroxide is relatively inexpensive
• Due to the bleaching effect they are well suited to remove discolorations
caused by pigments.
• Hydrogen peroxide is also able to remove flavor compounds.

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 Hydrogen Peroxide - Disadvantages

• Hydrogen peroxide is instable. Stabilized versions for about 30 minutes

• Hydrogen peroxide and caustic reacts very violently if blended as
concentrates
• Extra step necessary to add the hydrogen peroxide at point of use
• Lower quality grade stainless steel could potentially from rust

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 Application

• Addition to caustic
• Addition to acid
• Additive in acid foam cleaner

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 Thank you
• Block, S.S. (1977) Disinfection, Sterilisation and Preservation Lea & Febigal
• Brewing Microbiology Third Edition, edited by Fergus G. Prest and Iain
Campbell, 2003 Oliver Meinhold
• Briggs, D.E., Boulton, C.A., Brookes, P.A., Stevens, R., 2004, Chapter 13 –
15, Woodhead Publishing, Cambridge, England.
• Characterising the cleaning behaviour of brewery foulants, Kylee Rebecca

•
Goode, August 2012
Elmore, D.G (1980) Proceedings of the Brewing Technology Conference,
Director of Brewery Division
Harrogate, 8.
• Felgentraeger, W., Ricketts, N., 2003, Save energy and reduce operating

•
costs, The Brewer International, 3: 22-23.
Fryer, P.J., Asteriadou, K., 2009. A Prototype cleaning map: a classification
[email protected]
of industrial cleaning processes. Trends in Food Science & Technology 20,
225–262.
• Fryer, P J., Robbins, P T., Cole, P A, Goode, K R., Zhang, Z., Asteriadou, K.,
2011, Populating the cleaning map: can data for cleaning be relevant
across different length scales? Procedia Food science, 1: 1761 – 1767.
• Goode, K.R, Asteriadou, K., Fryer, P.J., Picksley, M., Robbins, P.T., 2010,
Characterising the cleaning mechanisms of yeast and the implications for
Cleaning In Place (CIP), Food and Bioproducts Processing 88: 365-374
• Hobbs, G. and Wilson, G.S. (1942) Journal of Hygiene, 42, 436
• O’Rourke, 2003, CIP – Cleaning In Place, The Brewer International, 3: 30-
34.

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