the theory of cleaning with special focus on using hydrogen … · 2020-05-01 · this...

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replication, or distribution of The Vincit Group® company property is strictly prohibited. Oliver Meinhold

The Theory of Cleaning with Special Focus

on Using Hydrogen Peroxide

Oliver Meinhold



Content

• Raw Materials

• Soil

• How to tackle fouling

• Cleaning parameters (Sinner Circle)

• Oxidizers

• Hydrogen Peroxide



Composition of Malting Barley and MaltComparison 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



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



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

Hop Composition



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

Yeast



Brewing Process

Malting

Brewhouse

Fermentation

Maturation Filtration

PackagingStorage

Barley

Water

Hops

Malt

Wort

Green BeerYeast

Bright Beer

Bottles, Cans, KEGs

Additives

Process steps

Intermediate and final products



Process Steps

• Brewhousedegradation of high molecular polysaccharides (starch) and proteins to small molecular and fermentable saccharides and soluble proteins

• Fermentationconversion of fermentable saccharides to ethanol and CO2

• Maturationyeast settles down and beer flavor matures

• Filtrationseparation of yeast and precipitated conglomerates (e.g. proteins, polyphenols)

• Packagingbright beer is packaged into bottles, cans and KEGs



Calandria



Fermenter

Liquid surface

Fouling above liquid level

Deposit (yeast) after emptying fermentation tank



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 foulingIf there is no value it should be prevented, which is not easy.

• Removal by cleaningIf it cannot be prevented, it needs to be removed by cleaning.



How to tackle fouling

What type is it?

Composition analysis

Any value?

Fouling

No

No

Yes

Yes

Collection

Prevention (research) Cure (CIP)Further use (treatment,

storage, etc.)



Solubility of food deposits before and after thermal impact

Deposit Solubility Ease of removal MechanismChange during

heatingEase of removal

Sugar Water soluble Easy Crystallization Caramelization More difficult

FatWater and alkali soluble

Difficult Crystallization Polymerization More difficult

Protein

Water soluble, alkali soluble, slightly acidic soluble

Very difficult Chemical reaction Denaturation More difficult

MineralsWater solubility variable most are acid soluble

Easy to difficult CrystallizationInteraction with other compounds

Generally easier

Grasshoff, 1997



Change of Cleaning Requirements

Malting

Brewhouse

Wort Cooling

Fermentation

Maturation

Filtration

Brewing steps Type of Fouling Cleaning Requirements

Bright Beer Tank

Packaging

Draft Beer Dispensing

Particulates

Proteins and Minerals

Yeast Films, Proteins

Beer and Minerals

Biofilm

Physical / Visual

Visual and Chemical

Chemical and Microbiological



Cleaning RequirementsProcess Plant Soil Type Required How Obtained

Malting Floors, Screens Particulate Physically cleaned Manually

Milling Mill, Rollers Particulate, Starch, Protein Physically and or chemically cleaned

Manually or CIP

Mashing Mash tun Particulate, Starch, Sugar, Protein, Scale, Tannin

Chemically cleaned Manually or CIP

Lautering Mash tun, Lauter- tun, Mash filter, Strainmaster

Particulate, Starch, Sugar, Protein


Boiling Wort kettle, Hop kettle Particulate, Starch, Sugar, Protein, Scale, Tannin


Separation Whirlpool, Settling tank, Hop-Strainer

Hops, Trub, Tannin Microbiologically cleaned CIP + detergent / or sanitizer

Cooling Heat exchanger Protein, Scale, Particulate Microbiologically cleaned CIP + detergent / or sanitizer

Fermentation Fermentation tanks, Open vessel

Yeast, Protein, Oxidation products, Tannin, Sugar, Scale

Microbiologically cleaned CIP + detergent / or sanitizer




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, Container for Transportation

Yeast, Protein, Scale Microbiologically cleaned CIP + detergent / or sanitizer

Pasteurization Flash Pasteurizer, Heat Exchanger

Protein, Scale Microbiologically cleaned CIP + detergent / or sanitizer




Packaging (KEG) KEG, Cask Filler Protein, Scale, Particulate deposits

Microbiologically cleaned CIP + detergent / or 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, ScaleParticulate deposits

Microbiologically cleaned Dosing of biocide, Scale Control



Cleaning Map

Cleaning solution

Soil complexity

Water ambient temperature

Hot Chemical

Cohesive soilNon-viscous fluids

Hot Water

Viscous fluids

Personal product and pharmaceutical lotions

Sanitizing

Remove by rinsing

Product recovery

Soils that dissolve in water (e.g. sugar)

Product changeover: viscous fluids

Type 1:Viscous liquids

removed with hot water

Type 2:Biofilm

Type 3:Cohesive solids removed

with chemical

Fryer and Asteriadou, 2009



Forces Acting on Soil during Cleaning

Tank wall

Soil

Adhesive forces holding soil on surface

Mechanical force Thermal force Chemical force



Sinner Circle

Temperature

Time

Concentration

Mechanics



Temperature

Soil Effect

Proteins Medium

Fats Good

Carbohydrates Good

Minerals Good

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



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



Mechanics

• Assuming a 2mm film thickness (0.002m)

• Assuming a completely wetted surface

• Internal Surface must be determined:

• Dome

• Cylinder

• Cone



Mechanics

TRANSITIONLAMINAR TURBULENT

0~2100 ~4000

v vRe

H H HD D QD

A

= = =

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)).ν is the kinematic viscosity (ν = μ/ρ)(m²/s).ρ is the density of the fluid (kg/m³).

Laminar

Turbulent

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.



Chemical

Soil Water Caustic Acid

Proteins Poor Good Medium

Fats Poor Good Medium

Carbohydrates Good -- --

Minerals medium Medium Good

Effect on cleaning operation

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



Chemical

• Quality of water used for aqueous cleaning:

• Chemical properties (pH, hardness, etc.)

• Biological properties (bioburden, endotoxins)

• Pre-RinsingSolely for removing loose soil prior to chemical cleaning. Usually based on practicality of what type of water is available.

• Chemical cleaningMost critical is water hardness → effects efficiency of cleaning solutions

• RinsingIn general, the final rinse water used should have the same quality as used in the final production step.



Typical CIP Program

Step Operation Cleaning agent

Temperature [°C/°F] Time [min]

Usage

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



Oxidative Cleaning Intensifiers

• These oxidizing compounds are additionally used next toconventional 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 alkalinesolution they split off active oxygen, which can oxidatively cracktough soils.



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



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 cleaningagents.

• In a hot and alkalinic solution a quick decomposition to water and oxygentakes place, thus the dosage of the cleaning intensifier should take placedirectly before cleaning and as close as possible in front of the equipment tobe cleaned.

• Hermetically sealed installations have to be equipped with a ventilation toremove the oxygen produced, otherwise high pressure builds up inside ifthe installation



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 tosodium 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.



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



Application

• Addition to caustic

• Addition to acid

• Additive in acid foam cleaner



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• 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,

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

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.

Oliver Meinhold

Director of Brewery Division

[email protected]

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