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WO2025074199A1 - Neutral enzyme-based cip detergent for dairy and livestock facilities - Google Patents

Neutral enzyme-based cip detergent for dairy and livestock facilities Download PDF

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Publication number
WO2025074199A1
WO2025074199A1 PCT/IB2024/059312 IB2024059312W WO2025074199A1 WO 2025074199 A1 WO2025074199 A1 WO 2025074199A1 IB 2024059312 W IB2024059312 W IB 2024059312W WO 2025074199 A1 WO2025074199 A1 WO 2025074199A1
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weight
concentrations
detergent
percent
rpm
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French (fr)
Inventor
Nadia MEHRABI
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Tavakolian Alireza
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Tavakolian Alireza
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Priority to PCT/IB2024/059312 priority Critical patent/WO2025074199A1/en
Publication of WO2025074199A1 publication Critical patent/WO2025074199A1/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0026Low foaming or foam regulating compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2093Esters; Carbonates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/28Heterocyclic compounds containing nitrogen in the ring
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10Objects to be cleaned
    • C11D2111/14Hard surfaces
    • C11D2111/20Industrial or commercial equipment, e.g. reactors, tubes or engines

Definitions

  • the present invention is in the field of chemistry and especially the production of detergents and cleaners.
  • the PCT.App. NO. W02005015996 discloses antimicrobial compositions, which include carboxylic acids, such as fatty acid antimicrobial agents, and alkoxylated amines. These compositions form stable and clear solutions while retaining antimicrobial activity and providing effective soil removal.
  • the alkoxylated amines which can be primary, secondary, or tertiary, are used to couple carboxylic acids into aqueous or acidic solutions without complexing or reacting with them. They include alkoxylate or ether moieties, such as ethoxylate and propoxylate.
  • the composition offers the advantages of forming clear and stable solutions, retaining antimicrobial activity, and effectively removing soil. It can be said that the above invention contains isopropyl alcohol solvent with antimicrobial properties and a mixture of acids and ethoxylated amines.
  • the PCT.App. NO. W02009118714 describes an invention related to compositions used as cleaning agents, antimicrobials, and bleaching agents with improved storage stability and effectiveness at lower concentrations.
  • the liquid, storage-stable composition includes a mixture of sulfoperoxycarboxylic acid, C1 to C4 percarboxylic acid, C5 to C10 percarboxylic acid, a peroxide agent, a hydrotrope, an acidulant, and a liquid. These compositions contain free sulfocarboxylic acid, free C1 to C4 carboxylic acid, and free C5 to C10 carboxylic acid.
  • the invention also covers methods for making these compositions and their use as low or no-foaming cleaning, bleaching, and antimicrobial agents. They are phase stable, have low or no odor, are effective at lower temperatures, and are water-soluble.
  • the compositions are suitable for cleaning in place (CIP) and clean out of place (COP) applications, such as cleaning tanks, lines, pumps, and various surfaces. They are also effective as low-temperature bleaches and pH- optimized peroxygen bleaches in detergents, particularly in the food, beverage, and meat processing industries.
  • the product disclosed in present document combines enzymes, surfactants, and emulsifiers to dissolve fats, mineral deposits, and proteins. Additionally, this detergent reduces the accumulation of pacifier sealant residue on surfaces and lines of diary factory. With strong germicidal properties, including enzymes such as protease and lipase, it is particularly effective for removing stains from the steel surfaces of devices, pipes, and glass. According to the present document, milk stone washing in the dairy industry is performed on-site in a single step with a neutral pH of 7. This method does not cause corrosion, is odorless and colorless, and has an efficiency of 2 to 5 mm/m 2 .This product is ideal for use on both steel and glass, materials commonly found in dairy industry equipment.
  • the neutral and eco-friendly detergent offers optimal cleaning conditions for dairy factory production lines and livestock farm milking systems.
  • This detergent solution loosens all types of dairy stains, making them easy to remove from various surfaces, whether horizontal or vertical. Additionally, its enzyme formula reduces bacterial adhesion to tank and milking system surfaces.
  • Biodetergents non-soap cleaners
  • biological cleaners are effective in breaking down the extracellular polymers that form the biofilm matrix, thereby aiding in biofilm removal.
  • the specific enzymes required vary depending on the type of microflora forming the biofilm.
  • the main components of the detergent solution introduced in the present document comprise the following:
  • 2-Amino (alpha-amino) carboxylic acids are organic molecules, consisting of an amino group (-NH2), a carboxyl group (-COOH), and an organic chain (R). These molecules can attach to metals through their carboxylate and amine groups. Due to their molecular structure, amino carboxylic acids can bond with metal ions such as iron and nickel. This property is utilized in various industries to remove metal ions or alter their properties.
  • Protease Enzyme are enzymes that break the peptide bonds of proteins. They are categorized into three types: acidic, neutral, and alkaline proteases. In the main embodiment of invention, the properties of neutral protease are utilized. These enzymes can be sourced from plants, animals, and microorganisms under various conditions, such as high salt concentrations.
  • Biodetergents and biological cleaners have been explored for biofilm control.
  • Biodetergents (non-soap cleaners) and biological cleaners are effective in breaking down the extracellular polymers that form the biofilm matrix, thereby aiding in biofilm removal.
  • the specific enzymes required vary depending on the type of microflora forming the biofilm.
  • enzyme-based detergents such as biodetergents and biological cleaners
  • the formation of biofilms in dairy and food processing equipment and lines can be prevented, as demonstrated in the present document.
  • Significant cleaning is achieved with 0.1 mg of enzyme.
  • increasing the enzyme content within the range of 0.1 -1 mg% w/v and approaching 100% in the range of 1 -2 mg% w/v significantly enhances cleaning efficiency. Beyond this, with enzyme content varying between 2 to 100 mg wt%, the cleaning efficiency remains almost constant at around 100%. Therefore, an enzyme concentration of 20 mg weight percent by volume is preferred according to the practice of the present invention.
  • lipase and protease enzymes are used in concentrations ranging from 0.001 % to 2% by weight of the total composition to effectively remove protein and fat stains.
  • the amino acids used in the present document for producing the introduced CIP detergent can include amide amino acids and hydroxyl amino acids.
  • Amino acid surfactants derived from natural amino acids, serve as cleaners and emulsifiers in various industrial and consumer applications. These surfactants are biodegradable and environmentally friendly alternatives to traditional surfactants. Their unique structure allows them to perform a wide range of functions, making them suitable for various applications.
  • amino acid surfactants include alkyl-L- amino acids, alkyl di-amino acids, alkyl amino acids, and alkyl-L-glutamate.
  • the detergent solution incorporates amino acids in concentrations ranging from 1% to 5% by weight of the total composition.
  • Water is an excellent solvent due to its polar nature and its ability to dissolve a wide range of substances.
  • a solvent water can dissolve various minerals, salts, gases, and other organic and inorganic compounds. Its polarity makes it particularly effective for dissolving polar or ionic (hydrophilic) solutes.
  • polar or ionic hydrophilic
  • water is used as the main solvent, comprising between 65% and 95% by weight of the total composition.
  • Table 1 specifies the main ingredients of the composition, which are crucial for the final product and provide its primary advantages.
  • the prepared soluble secondary materials comprise:
  • Eucalyptus globulus essential oil This oil is a potential source of bioactive compounds with significant biological activity. Its chemical composition has been identified using gas chromatography (GC) and gas chromatography/mass spectrometry (GC/MS).
  • GC gas chromatography
  • GC/MS gas chromatography/mass spectrometry
  • the main components of EGEO are monoterpenes, including 1 ,8-cineole, p-cimene, beta-pinene, alpha-pinene, and a-limonene.
  • the essential oil can neutralize 55.44 ⁇ 0.99% of ABTS*+ with just 10 microliters, equivalent to 3.22 ⁇ 0.01 TEAC.
  • Eucalyptus oil possesses antibacterial, antimicrobial, antifungal, and overall disinfectant properties. It dissolves greasy and sticky substances and is also used as a deodorizer in this invention.
  • Hydrogenated soybean oil (hydrogenated oil contains a lot of solid fat that forms by hydrogenating liquid oil, increasing its resistance to oxidation and enhancing the absorption of soybean oil) and hydrogenated castor oil are used as emulsions. They are also used as fat dissolvers. PEG-40 hydrogenated castor oil is used as a softener, emulsifier, solvent, surfactant, and cleaning agent.
  • Isothiazolin tetra-compound an antimicrobial substance used to control fungi, bacteria, or algae
  • secondary materials that provide additional benefits to the product are specified.
  • Antifoams are based on silicone, mineral oils, fatty alcohol, poly-glycol as well as non-silicone organic antifoams.
  • raw materials are placed in two separate parts, A and B, in the reactor as the first part and second part. Under specific temperature and pressure conditions, these parts are combined in a particular order to produce the final material.
  • Composition A [0051]
  • Carboxymethyl Cellulose (CMC) substance comprising 1 to 9 percent by weight of the total composition, is gradually added to deionized water (65 to 95 percent by weight of the total composition) inside the reactor.
  • the reactor is operated at a stirring speed of 450 to 650 revolutions per minute (RPM) and at an initial temperature between 25°C and 65°C. The stirring process continues until the CMC is fully dissolved, as indicated by the clarity of the solution.
  • RPM revolutions per minute
  • Sorbitol comprising 0.1 to 2 percent by weight of the total composition, is added to deionized water (65 to 95 percent by weight of the total composition) inside another reactor. This is done at a stirring speed of 450 to 650 rpm and at a temperature between 25°C and 35°C.
  • eucalyptus oil or hydrogenated castor oil comprising 0.01 to 3 percent by weight of the total composition, is slowly added at a temperature between 25°C and 65°C, with a stirring speed of 450 to 650 RPM.
  • the stirring speed is set between 450 and 650 RPM, and the production temperature is maintained between 55 and 65 °C.
  • the temperature is adjusted to between 35 and 45 °C, and the stirring speed is reduced to between 150 and 250 RPM. This decrease in temperature and stirring speed is due to the characteristics of the raw materials used.
  • part B of the material is added to the initial solution of part A in the next step, the temperature is lowered to stabilize the newly added material.
  • Citric Acid Used as a pH adjuster to maintain the acidity and stability of the solution.
  • Sodium Benzoate (0.3%): Acts as a preservative to prevent microbial growth.
  • D-Panthenol Provides skin-conditioning benefits, making it suitable for personal care products.
  • Tea Tree Oil Provides natural antibacterial and antifungal properties.
  • coconut Oil A natural emollient that enhances skin softness and hydration
  • This invention relates to an on-site method and product for cleaning milk processing equipment. It is designed for use in milk processing factories and can also be applied to other food or beverage processing equipment where feasible. Additionally, it is suitable for cleaning milking lines, other equipment, and milk storage tanks on livestock farms.
  • the primary goal of this invention is to offer an easy-to-use cleaning solution for dairy factories. Another objective is to provide a cleaning method specifically adapted to remove milk scale and other milk deposits from the interior surfaces of dairy equipment

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Molecular Biology (AREA)
  • Detergent Compositions (AREA)

Abstract

A single-stage, enzyme-based, neutral, and environmentally friendly milk stone detergent (CIP) designed for dairy industries. The formulation includes enzymes such as lipase and protease to effectively remove protein and fat stains. Surfactants and emulsifiers, including amino acid surfactants, enhance cleaning efficiency. CMC or Modified Carboxymethyl Cellulose serves multiple roles, including thickening and stabilizing. Amino carboxylic acids act as chelating agents, while water is the primary solvent. Eucalyptus globulus essential oil provides disinfection, and aloe vera oil offers cleansing and anti-inflammatory benefits. Hydrogenated oils function as emulsifiers and fat dissolvers, and isothiazolin tetra-compound acts as a biocide- preservative. Antifoams are included to control foam. This detergent is optimized for effective and sustainable cleaning in dairy processing environments.

Description

Description
Title of Invention : Neutral Enzyme-Based CIP Detergent for Dairy and Livestock Facilities
Technical Field
[0001] The present invention is in the field of chemistry and especially the production of detergents and cleaners.
Background Art
[0002] Today, there are many methods for descaling milk stone in the dairy industry, including acidic and alkaline detergents. These acidic and alkaline detergents, in turn, have harmful effects on the polluting environment as well as by producing some toxic gases and industrial wastes. These detergents clean the equipment of the milking machine in several stages. Some acidic and alkaline detergents are in the market recently that reduce the washing process from 5-7 steps to 3-4 steps.
[0003] The PCT.App. NO. W02005015996 discloses antimicrobial compositions, which include carboxylic acids, such as fatty acid antimicrobial agents, and alkoxylated amines. These compositions form stable and clear solutions while retaining antimicrobial activity and providing effective soil removal. The alkoxylated amines, which can be primary, secondary, or tertiary, are used to couple carboxylic acids into aqueous or acidic solutions without complexing or reacting with them. They include alkoxylate or ether moieties, such as ethoxylate and propoxylate. Overall, the composition offers the advantages of forming clear and stable solutions, retaining antimicrobial activity, and effectively removing soil. It can be said that the above invention contains isopropyl alcohol solvent with antimicrobial properties and a mixture of acids and ethoxylated amines.
[0004] The PCT.App. NO. W02009118714 describes an invention related to compositions used as cleaning agents, antimicrobials, and bleaching agents with improved storage stability and effectiveness at lower concentrations. The liquid, storage-stable composition includes a mixture of sulfoperoxycarboxylic acid, C1 to C4 percarboxylic acid, C5 to C10 percarboxylic acid, a peroxide agent, a hydrotrope, an acidulant, and a liquid. These compositions contain free sulfocarboxylic acid, free C1 to C4 carboxylic acid, and free C5 to C10 carboxylic acid. The invention also covers methods for making these compositions and their use as low or no-foaming cleaning, bleaching, and antimicrobial agents. They are phase stable, have low or no odor, are effective at lower temperatures, and are water-soluble. The compositions are suitable for cleaning in place (CIP) and clean out of place (COP) applications, such as cleaning tanks, lines, pumps, and various surfaces. They are also effective as low-temperature bleaches and pH- optimized peroxygen bleaches in detergents, particularly in the food, beverage, and meat processing industries.
[0005] US.App.NO 20180187129 discloses an acid detergent compositions, concentrates, and use solutions, particularly suited for removing soils, especially milk soils, from clean-in-place (CIP) systems in the dairy and food processing industries. These compositions include an acidic component (inorganic or alkanesulfonic acid) and a blend of surfactants to provide high cleaning efficiency and low foam generation. They may also contain an antimicrobial agent for sanitization. The compositions are effective in cleaning and optionally sanitizing CIP equipment. The concentrated detergent composition comprises an acidic component (inorganic or alkanesulfonic acid, optionally combined with an organic acid), a first surfactant (non-ionic), and a second surfactant, with specific weight ratios. The compositions achieve excellent cleaning efficiency, especially for milk soils, and can include a sanitizing component that provides significant bacterial reduction. Depending on the acid selection, the compositions can be biodegradable and sustainable.
Summary of Invention
[0006] The CIP detergent disclosed in the present document is neutral, has controlled foam, very thick, free of odor and heavy vapors, non-burning, non- corrosive, non-flammable and environmentally friendly and has zero waste and only during One step of the process of cleaning the entire milking system is done in a way that it is prepared by diluting two percent in drinking water or well water. This product does not produce industrial waste water, and as a result, it does not require the process of wastewater treatment, thus saving energy, time, and water.
[0007] The formulation of the present detergent comprises enzymes such as lipase and protease, to effectively remove protein and fat stains. Surfactants and emulsifiers, including amino acid surfactants, enhancing cleaning efficiency. CMC or Modified Carboxymethyl Cellulose, serves multiple roles, including thickening and stabilizing. Amino carboxylic acids, act as chelating agents, while water, is the primary solvent. Eucalyptus globulus essential oil, provides disinfection, and aloe vera oil, offers cleansing and anti-inflammatory benefits. Hydrogenated oils, function as emulsifiers and fat dissolvers, and isothiazolin tetra-compound, acts as a biocide-preservative. Antifoams, are included to control foam. This detergent is optimized for effective and sustainable cleaning in dairy processing environments.
[0008] Using this detergent offers several benefits for dairy industries. It effectively removes protein and fat stains with enzymes like lipase and protease, while surfactants and emulsifiers enhance cleaning efficiency. CMC or Modified Carboxymethyl Cellulose thickens and stabilizes the detergent, and amino carboxylic acids act as chelating agents to bind and remove metal ions. Eucalyptus globulus essential oil provides natural disinfection, and aloe vera oil offers cleansing and anti-inflammatory benefits. Hydrogenated oils function as emulsifiers and fat dissolvers, and isothiazolin tetra-compound acts as a biocidepreservative. Antifoams control foam, making the cleaning process more manageable. Overall, this neutral and environmentally friendly detergent is optimized for effective and sustainable cleaning in dairy processing environments.
Technical Problem
[0009] In nature and food systems, microorganisms are attracted to the surfaces of solids that provide sufficient nutrients for their survival and growth. These microorganisms initially deposit on surfaces, then attach, grow, and actively reproduce to form colonies. These cell masses grow large enough to trap organic and inorganic debris, nutrients, and other small organisms, leading to the formation of microbial biofilms. In dairy and food processing equipment, food or milk residues can deposit on surfaces, allowing microorganisms to form biofilms.
[0010] The global CIP(Cleaning in Place) standard for washing dairy industry equipment involves 5 to 7 steps, typically using acidic and alkaline detergents. These traditional detergents have a pungent smell, cause pollution, release toxic gases into the environment, and produce industrial waste. [0011 ] In the first stage of this process, devices and equipment contaminated with scale in the dairy industry are pre-washed and soaked with water at 60-70°C. In the next stage, they are washed with water at 45°C. Following this, they undergo a caustic wash with an alkaline solution, such as 1 -2% baking soda. As a general rule, cleaning with alkaline detergents should be performed at the same temperature to which the product is exposed, at least 70°C. After the caustic wash, the equipment is rinsed with water at 45-60°C to remove any traces of soda. Finally, acidic substances, including chlorine or nitric acid, are applied to disinfect the system and remove milk stone, which is a very hard type of fat.
[0012] In the next step, the device is washed again with water at 45 or 60 degrees Celsius to remove the effects of acid washing. In the final stage, after this solution enters the wastewater, the wastewater treatment process is performed. It should be noted that a significant amount of water is used in the wastewater treatment process. Even Clean-ln-Place (CIP) methods cannot entirely prevent the accumulation of microorganisms on equipment surfaces.
Advantageous Effects of Invention
[0013] The neutral and one-step enzyme-based CIP detergent product with strong germicide offers several advantages. It serves as an alternative to the traditional multi-step washing process in dairy industries, providing high efficiency in a single step. This neutral detergent with a pH of 7 can replace both alkaline and acidic detergents, increasing production efficiency and extending the time for dairy processing operations. It reduces energy costs and the time needed to wash equipment, significantly cuts down on waste production, and shortens the washing process duration. Additionally, it saves water consumption due to its powerful water-based formulation. The product is non-corrosive, non-burning, has low reactivity, and is non-flammable. It does not release dangerous gases or heavy vapors, reducing COD and BOD treatment costs of wastewater. Environmentally friendly and zero waste, it contains enzymes with strong germicidal properties. It is suitable for low-temperature storage and fully automatic systems, and the enzymatic detergent solution reduces the adhesion of bacteria to the surfaces of tanks and milking systems.
Description of Embodiments [0014] A single-stage, enzyme-based, neutral, and environmentally friendly milk stone detergent for dairy industries is disclosed in the present document. The CIP detergent disclosed in the present document, which consists of a combination of enzymes, surfactants, and emulsifiers, has a pH of 7 and is neutral, with controlled foam, very thick, free of odor and heavy vapors, and non-burning. It is non-corrosive, non-flammable, and environmentally friendly. It produces few waste and requires only one step in the cleaning process of the entire shower system. By diluting two percent of this product in drinking water or well water, the CIP detergent is prepared. It can be mixed with any type of water, even heavy water, and maintains its characteristics for single-step washing of equipment. The temperature range of water required for diluting the product is between 25°C and 65°.
[0015] The product disclosed in present document combines enzymes, surfactants, and emulsifiers to dissolve fats, mineral deposits, and proteins. Additionally, this detergent reduces the accumulation of pacifier sealant residue on surfaces and lines of diary factory. With strong germicidal properties, including enzymes such as protease and lipase, it is particularly effective for removing stains from the steel surfaces of devices, pipes, and glass. According to the present document, milk stone washing in the dairy industry is performed on-site in a single step with a neutral pH of 7. This method does not cause corrosion, is odorless and colorless, and has an efficiency of 2 to 5 mm/m2.This product is ideal for use on both steel and glass, materials commonly found in dairy industry equipment. Unlike acidic and alkaline detergents, the neutral and eco-friendly detergent offers optimal cleaning conditions for dairy factory production lines and livestock farm milking systems. This detergent solution loosens all types of dairy stains, making them easy to remove from various surfaces, whether horizontal or vertical. Additionally, its enzyme formula reduces bacterial adhesion to tank and milking system surfaces.
[0016] Currently, the use of biodetergents and biological cleaners is being investigated for biofilm control. Biodetergents (non-soap cleaners) and biological cleaners are effective in breaking down the extracellular polymers that form the biofilm matrix, thereby aiding in biofilm removal. The specific enzymes required vary depending on the type of microflora forming the biofilm. By using enzyme detergents such as biodetergents and biological cleaners, the formation of biofilms in dairy and food processing equipment and lines can be prevented, as described in the present document.
[0017] The main components of the detergent solution introduced in the present document comprise the following:
[0018] The primary ingredients of the prepared solution are:
[0019] 1 -CMC or Modified Carboxymethyl Cellulose: This polymer compound serves as a multi-purpose additive and food additive. It easily dissolves in water and disperses completely, leading to the suspension and stabilization of particles and the regulation of rheology. In the final formulation, it acts as a thickener, stabilizer, strength enhancer, water retention agent, dispersing agent, suspension agent, and water purifier. For water purification, the detergent solution contains between 1 -9 percent by weight of carboxymethyl cellulos.
[0020] 2-Amino (alpha-amino) carboxylic acids (R-CH(NH2)-COOH) are organic molecules, consisting of an amino group (-NH2), a carboxyl group (-COOH), and an organic chain (R). These molecules can attach to metals through their carboxylate and amine groups. Due to their molecular structure, amino carboxylic acids can bond with metal ions such as iron and nickel. This property is utilized in various industries to remove metal ions or alter their properties.
[0021 ] These ligands can bond to metal atoms using more than two pairs of electrons. Hexadentate ligands form very stable complexes, usually octahedral structures, with most transition metals. This polyamino carboxylic acid material is used to trap small amounts of transition metals that can potentially catalyze product decomposition. It is a colorless, odorless, non-flammable, non-corrosive, non-burning substance, soluble in water, and is used to improve cleaning performance as a chelating agent. In the preparation of the detergent solution, aminocarboxylic acid is used in concentrations of 5-15% by weight of the total composition to enhance cleaning properties.
[0022] Polysorbate (with the chemical formula C64H124026) is an emulsifier with a long polyoxyethylene chain, allowing it to dissolve in water and various organic solvents such as ethanol, methanol, ethyl acetate, and toluene. It is used as a softener, moisturizer, and to enhance cleaning properties. This surfactant is a completely biological composition based on natural fatty acids and the sugar alcohol sorbitol.
[0023] 3-Polysorbate is a polymeric surfactant derived from sorbitol (a type of sugar alcohol with the chemical formula C6H14O6) used in detergents. Polymeric surfactants help to suspend soil, remove soil, and reduce surface tension. New compounds selected from polymers have been used as active ingredients in detergent formulations. Petroleum-based active materials such as soft acid slurry and alpha olefin sulfonate can be partially replaced with these new polymers. As petroleum resources become scarcer and more expensive, replacing them with new plant-based polymers will contribute to environmental sustainability.
[0024] Polysorbate is used to stabilize water-in-oil emulsion systems as an emulsifier and oil-in-water systems as an auxiliary emulsifier. It is also used for the uniform distribution of non-polar pigments and in industrial coating processes as a stabilizing material. The presence of the sorbitan ester part in polysorbate is very effective as a stabilizing factor in water-in-oil emulsion systems, especially when used together with ethoxylated derivatives. In the preparation of the detergent solution, polysorbate is used in concentrations of 1 -7% by weight of the total composition to serve as an emulsifier, softener, and moisturizer, thereby improving the cleaning properties.
[0025] 4. Enzymes (lipase and protease) are used to remove protein and fat stains.
[0026] A. Lipase enzyme: Microbial lipases are a valuable group of biotechnological enzymes due to their versatile functional properties and ease of mass production. Lipases of microbial origin exhibit a wide diversity in enzyme properties and substrate specificity, making them highly attractive for industrial applications. This document describes the applications of microbial lipases in detergents. Enzymes can reduce the environmental burden of detergent products by decreasing the need for conventional chemicals. They are biodegradable, non-toxic, and do not leave any harmful residues. Enzymes are used to remove protein and fat stains effectively.
[0027] B. Protease Enzyme Proteases are enzymes that break the peptide bonds of proteins. They are categorized into three types: acidic, neutral, and alkaline proteases. In the main embodiment of invention, the properties of neutral protease are utilized. These enzymes can be sourced from plants, animals, and microorganisms under various conditions, such as high salt concentrations.
[0028] In nature and food systems, microorganisms are attracted to the surfaces of solids that provide sufficient nutrients for their survival and growth. These microorganisms initially deposit on surfaces, then attach, grow, and actively reproduce to form colonies. These cell masses grow large enough to trap organic and inorganic debris, nutrients, and other small organisms, leading to the formation of microbial biofilms. In dairy and food processing equipment, when food or milk residues remain, they deposit on surfaces, allowing microorganisms to begin forming biofilms. Even clean-in-place (CIP) methods cannot completely prevent the accumulation of microorganisms on the equipment surfaces.
[0029] The use of biodetergents and biological cleaners has been explored for biofilm control. Biodetergents (non-soap cleaners) and biological cleaners are effective in breaking down the extracellular polymers that form the biofilm matrix, thereby aiding in biofilm removal. The specific enzymes required vary depending on the type of microflora forming the biofilm. By using enzyme-based detergents such as biodetergents and biological cleaners, the formation of biofilms in dairy and food processing equipment and lines can be prevented, as demonstrated in the present document. Significant cleaning is achieved with 0.1 mg of enzyme. However, increasing the enzyme content within the range of 0.1 -1 mg% w/v and approaching 100% in the range of 1 -2 mg% w/v significantly enhances cleaning efficiency. Beyond this, with enzyme content varying between 2 to 100 mg wt%, the cleaning efficiency remains almost constant at around 100%. Therefore, an enzyme concentration of 20 mg weight percent by volume is preferred according to the practice of the present invention.
[0030] In the preparation of the present detergent solution, lipase and protease enzymes are used in concentrations ranging from 0.001 % to 2% by weight of the total composition to effectively remove protein and fat stains. The amino acids used in the present document for producing the introduced CIP detergent can include amide amino acids and hydroxyl amino acids. Amino acid surfactants, derived from natural amino acids, serve as cleaners and emulsifiers in various industrial and consumer applications. These surfactants are biodegradable and environmentally friendly alternatives to traditional surfactants. Their unique structure allows them to perform a wide range of functions, making them suitable for various applications. Examples of amino acid surfactants include alkyl-L- amino acids, alkyl di-amino acids, alkyl amino acids, and alkyl-L-glutamate. To enhance cleaning performance, the detergent solution incorporates amino acids in concentrations ranging from 1% to 5% by weight of the total composition.
[0031] Water is an excellent solvent due to its polar nature and its ability to dissolve a wide range of substances. As a solvent, water can dissolve various minerals, salts, gases, and other organic and inorganic compounds. Its polarity makes it particularly effective for dissolving polar or ionic (hydrophilic) solutes. When an ionic or polar compound enters water, it is surrounded by water molecules. The relatively small size of water molecules allows many of them to surround a single solute molecule. The semi-negative dipoles of water are attracted to the positively charged components of solutes. In this CIP detergent solution, water is used as the main solvent, comprising between 65% and 95% by weight of the total composition.
[0032] Table 1 specifies the main ingredients of the composition, which are crucial for the final product and provide its primary advantages.
[0033] Table 1 .
Figure imgf000010_0001
[0034] The prepared soluble secondary materials comprise:
[0035] Eucalyptus globulus essential oil (EGEO): This oil is a potential source of bioactive compounds with significant biological activity. Its chemical composition has been identified using gas chromatography (GC) and gas chromatography/mass spectrometry (GC/MS). The main components of EGEO are monoterpenes, including 1 ,8-cineole, p-cimene, beta-pinene, alpha-pinene, and a-limonene.
[0036] Antioxidant Potential:
[0037] The essential oil can neutralize 55.44 ± 0.99% of ABTS*+ with just 10 microliters, equivalent to 3.22 ± 0.01 TEAC.
[0038] Antimicrobial Activity:
[0039] Determined through disc diffusion and minimum inhibitory concentration methods, the best antimicrobial activity was observed against C. albicans (14.00 ± 1 .00 mm) and microscopic fungi (11 .00 ± 0.00 mm - 12.33 ± 0.58 mm). The minimum inhibitory concentration showed the best results against C. tropicalis (MIC 50: 2.93 pL/mL, MIC 90: 3.17 pL/mL).
[0040] Anti-Biofilm Activity:
[0041] EGEO’s effectiveness against biofilm-forming P. fluorescens has been confirmed in scientific studies.
[0042] Eucalyptus oil possesses antibacterial, antimicrobial, antifungal, and overall disinfectant properties. It dissolves greasy and sticky substances and is also used as a deodorizer in this invention.
[0043] Aloe vera contains many active ingredients, including vitamins, enzymes, minerals, sugars, lignin, saponins, salicylic acids, and amino acids. Aloe vera oil includes at least six antiseptic agents: lupeol, salicylic acid, urea nitrogen, cinnamic acid, phenols, and sulfur. All of these agents have inhibitory effects on fungi, bacteria, and viruses.
[0044] Hydrogenated soybean oil (hydrogenated oil contains a lot of solid fat that forms by hydrogenating liquid oil, increasing its resistance to oxidation and enhancing the absorption of soybean oil) and hydrogenated castor oil are used as emulsions. They are also used as fat dissolvers. PEG-40 hydrogenated castor oil is used as a softener, emulsifier, solvent, surfactant, and cleaning agent.
[0045] Isothiazolin tetra-compound (an antimicrobial substance used to control fungi, bacteria, or algae) acts as a biocide with a very high efficacy in removing and destroying aerobic and anaerobic microorganisms. It is used in water and disinfectants with antimicrobial properties. [0046] In Table 2, secondary materials that provide additional benefits to the product are specified.
[0047] Table 2.
Figure imgf000012_0001
[0048] Antifoams are based on silicone, mineral oils, fatty alcohol, poly-glycol as well as non-silicone organic antifoams.
[0049] Production process of single-step CIP detergent with enzyme:
[0050] In this process, raw materials are placed in two separate parts, A and B, in the reactor as the first part and second part. Under specific temperature and pressure conditions, these parts are combined in a particular order to produce the final material.
[0051] Composition A:
[0052] Carboxymethyl Cellulose (CMC) substance, comprising 1 to 9 percent by weight of the total composition, is gradually added to deionized water (65 to 95 percent by weight of the total composition) inside the reactor. The reactor is operated at a stirring speed of 450 to 650 revolutions per minute (RPM) and at an initial temperature between 25°C and 65°C. The stirring process continues until the CMC is fully dissolved, as indicated by the clarity of the solution.
[0053] Once a stable mixture of water and CMC is formed, with no visible suspended particles, amino carboxylic acid (5 to 15 percent by weight of the total composition) is gradually introduced into the reactor. This step is carried out at a temperature between 35°C and 45°C, with the stirring speed maintained at 450 to 650 RPM. When properly executed, this results in a clear and colorless solution, referred to as compound A. [0054] Composition B:
[0055] Sorbitol, comprising 0.1 to 2 percent by weight of the total composition, is added to deionized water (65 to 95 percent by weight of the total composition) inside another reactor. This is done at a stirring speed of 450 to 650 rpm and at a temperature between 25°C and 35°C.
[0056] Next, eucalyptus oil or hydrogenated castor oil, comprising 0.01 to 3 percent by weight of the total composition, is slowly added at a temperature between 25°C and 65°C, with a stirring speed of 450 to 650 RPM.
[0057] Finally, the amino acid composition, comprising 1 to 5 percent by weight of the total composition, is added to the reactor at a temperature between 25°C and 65°C, with a stirring speed of 450 to 650 RPM.
[0058] Then part B is slowly added to part A at a temperature between 25°C and 35°C, with a stirring speed between 150 and 650 RPM. After creating a stable and uniform mixture from compounds A and B, lipase and protease enzymes, comprising 0.001 to 2 percent by weight of the total compound, are added to the existing concentrate, respectively.
[0059] During production, it is preferable to use antifoam agents (such as those based on silicone, mineral oils, fatty alcohol, polyglycol, and non-silicone organic antifoams) in water, comprising 0.001 to 1 percent by weight of the total composition, to control possible foam.
[0060] Finally, it is preferable to use a mixture of isothiazoline, comprising 0.001 to 2 percent by weight of the total composition, as a preservative. One of the signs of completing this process correctly is achieving a clear, colorless, and neutral solution.
[0061] If the composition and order of use of materials are changed, the pH of the final product will not be neutralized. This is due to the interactions between raw materials and the formation of process intermediates. Experimentally and practically, this specific combination and order of use of raw materials lead to the production of a neutral and efficient final product. The production time for this solution ranges between 4 and 8 hours. [0062] The production of this product involves an alternating formulation process of raw materials, utilizing a high-speed reactor equipped with a mechanical stirrer and precise temperature control capabilities ranging from 25°C to 85°C. The production process is conducted in multiple stages within the reactor, operating at stirring speeds from 55 to 650 RPM. These parameters ensure efficient mixing and formulation, enabling precise control over environmental conditions and production temperatures, which are critical for the optimal preparation of the detergent solution.
[0063] At the beginning of the process, the stirring speed is set between 450 and 650 RPM, and the production temperature is maintained at 55 to 65 degrees Celsius. Gradually, the temperature is adjusted to 35 to 45 degrees Celsius, and the mixer speed is reduced to 150 to 250 RPM. This decrease in temperature and reactor speed is due to the properties of the raw materials used. When part B of the material is added to the initial solution of part A in the next step, the temperature is lowered to ensure the stability of the subsequent added material, as high temperatures may cause the degradation of secondary materials added to the composition.
[0064] In the production process of a single-step CIP detergent solution containing enzymes, raw materials are placed in two separate parts, A and B, in the reactor. Under a series of specific temperature and pressure conditions, these two parts are combined in a specific order to produce the final material.
[0065] If the composition and order of the materials are changed, the pH of the final product will not be neutral. This is due to the interactions between the raw materials and the formation of process intermediates. Experimentally and practically, this specific combination and order of raw materials result in a neutral and efficient final product. The production time for this solution ranges between 4 and 8 hours.
[0066] The production of this product is based on the alternating formulation process of raw materials using a high-speed reactor equipped with a mechanical stirrer and the ability to control the temperature within the range of 25 to 85 °C. The multi-stage production process in a mechanical reactor operates at speeds varying from 55 to 650 RPM. These features facilitate the production process of the proposed detergent solution by allowing the environmental conditions and temperature of the production environment to be adjusted and controlled.
[0067] At the beginning of the process, the stirring speed is set between 450 and 650 RPM, and the production temperature is maintained between 55 and 65 °C.
Gradually, the temperature is adjusted to between 35 and 45 °C, and the stirring speed is reduced to between 150 and 250 RPM. This decrease in temperature and stirring speed is due to the characteristics of the raw materials used. When part B of the material is added to the initial solution of part A in the next step, the temperature is lowered to stabilize the newly added material.
Examples
Figure imgf000015_0001
Figure imgf000016_0001
[0068] Additional Additives:
[0069] Glycerin (2%): Adds moisturizing properties to the solution.
[0070] Citric Acid (0.5%) : Used as a pH adjuster to maintain the acidity and stability of the solution.
[0071] Sodium Benzoate (0.3%): Acts as a preservative to prevent microbial growth.
[0072] Fragrance (0.2%): Optional additive to give the product a pleasant smell.
[0073] D-Panthenol (Provitamin B5) (0.1 %): Provides skin-conditioning benefits, making it suitable for personal care products.
Figure imgf000017_0001
Figure imgf000018_0001
[0074] Tea Tree Oil: Provides natural antibacterial and antifungal properties.
[0075] Coconut Oil: A natural emollient that enhances skin softness and hydration
Industrial Applicability
[0076] This invention relates to an on-site method and product for cleaning milk processing equipment. It is designed for use in milk processing factories and can also be applied to other food or beverage processing equipment where feasible. Additionally, it is suitable for cleaning milking lines, other equipment, and milk storage tanks on livestock farms. The primary goal of this invention is to offer an easy-to-use cleaning solution for dairy factories. Another objective is to provide a cleaning method specifically adapted to remove milk scale and other milk deposits from the interior surfaces of dairy equipment

Claims

Claims
[Claim 1] Neutral Enzyme-Based CIP Detergent for Dairy and Livestock Facilities, comprising:
Enzymes, including lipase and protease, in concentrations ranging from 0.001% to 2% by weight, for removing protein and fat stains;
Surfactants and emulsifiers, including amino acid surfactants in concentrations ranging from 1% to 5% by weight;
Modified Carboxymethyl Cellulose in concentrations of 1 -9% by weight, acting as a thickener, stabilizer, strength enhancer, water retention agent, dispersing agent, suspension agent, and water purifier; polysorbate is used at 1 -7% by weight to act as an emulsifier, softener, and moisturizer;
Amino (alpha-amino) carboxylic acids in concentrations of 5-15% by weight, acting as chelating agents;
Water, comprising 65% to 95% by weight, as the main solvent;
Eucalyptus globulus essential oil (EGEO) in concentrations of 0.001% to 2% by weight, acting as a disinfectant;
Aloe vera oil in concentrations of 0.001% to 2% by weight, acting as a cleanser and anti-inflammatory agent;
Hydrogenated oils, including hydrogenated soybean oil and hydrogenated castor oil, in concentrations of 0.001% to 3% by weight, acting as emulsifiers and fat dissolvers;
Isothiazolin tetra-compound in concentrations of 0.001% to 2% by weight, acting as a biocide-preservative;and
Antifoams in concentrations of 0.001% to 1% by weight.
[Claim 2] The detergent solution of claim 1 , wherein the enzymes are microbial lipases and neutral proteases.
[Claim 3] The detergent solution of claim 1 , wherein the amino acid surfactants include alkyl-L-amino acids, alkyl di-amino acids, alkyl amino acids, and alkyl-L-glutamate.
[Claim 4] The detergent solution of claim 1 , wherein the eucalyptus globulus essential oil contains monoterpenes such as 1 ,8-cineole, p-cimene, betapinene, alpha-pinene, and a-limonene.
[Claim 5] The detergent solution of claim 1 , wherein the hydrogenated oils include PEG-40 hydrogenated castor oil, which serves as a softener, emulsifier, solvent, surfactant, and cleaning agent.
[Claim 6] The detergent solution of claim 1 , wherein the isothiazolin tetra-compound acts as a biocide with high efficacy in removing aerobic and anaerobic microorganisms.
[Claim 7] The detergent solution of claim 1 , wherein the antifoams are based on silicone, mineral oils, fatty alcohol, poly-glycol, and non-silicone organic compounds.
[Claim 8] A method for producing a detergent solution, comprising:
Preparing raw materials in two separate parts to make the final solution;
For making the first part, gradually adding Carboxymethyl Cellulose in concentrations of 1 to 9 percent by weight to deionized water, with stirring at 450 to 650 RPM and an initial temperature between 25°C and 65°C until fully dissolved;
Introducing amino carboxylic acid in concentrations of 5 to 15 percent by weight, with stirring at 450 to 650 RPM to form a clear and colorless solution and making the first part of final solution;
- For preparation of second part, adding sorbitol in concentrations of 0.1 to 2 percent by weight to deionized water, with stirring at 450 to 650 RPM;
- Adding eucalyptus oil or hydrogenated castor oil in concentrations of 0.01 to 3 percent by weight, with stirring at 450 to 650 RPM;
- Adding amino acid composition in concentrations of 1 to 5 percent by weight to the second part, with stirring at 450 to 650 RPM; - Combining the second part with first part of solution with stirring at 150 to 650 RPM to form a stable mixture;
- Adding lipase and protease enzymes in concentrations of 0.001 to 2 percent by weight to the final mixture;
- Using antifoam agents in concentrations of 0.001 to 1 percent by weight during production to control foam;
- Adding a mixture of isothiazoline in concentrations of 0.001 to 2 percent by weight to final mixture as a preservative.
[Claim 9] The method of claim 8 , wherein the production process involves an alternating formulation process of raw materials, utilizing a high-speed reactor equipped with a mechanical stirrer and precise temperature control capabilities ranging from 25°C to 85°C, with stirring speeds from 55 to 650 RPM.
[Claim 10] The method of claim 8, wherein the amino carboxylic acid is introduced into the first part at a temperature between 35°C and 45°C.
[Claim 11 ] The method of claim 8, wherein sorbitol is added to deionized water in the second part at a temperature between 25°C and 35°C.
[Claim 12] The method of claim 8, wherein eucalyptus oil or hydrogenated castor oil is added to part B at a temperature between 25°C and 65°C.
[Claim 13] The method of claim 8, wherein the amino acid composition is added to the second part at a temperature between 25°C and 65°C.
[Claim 14] The method of claim 8, wherein the second part is combined with the first part at a temperature between 25°C and 35°C
PCT/IB2024/059312 2024-09-25 2024-09-25 Neutral enzyme-based cip detergent for dairy and livestock facilities Pending WO2025074199A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996006910A2 (en) * 1994-08-31 1996-03-07 Ecolab Inc. Improved proteolytic enzyme cleaner
WO2018136693A1 (en) * 2017-01-19 2018-07-26 Diversey, Inc. Formulations and method for low temperature cleaning of dairy equipment
WO2023275191A1 (en) * 2021-06-29 2023-01-05 Christeyns Improved enzyme-containing additive and detergent liquor formulations

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996006910A2 (en) * 1994-08-31 1996-03-07 Ecolab Inc. Improved proteolytic enzyme cleaner
WO2018136693A1 (en) * 2017-01-19 2018-07-26 Diversey, Inc. Formulations and method for low temperature cleaning of dairy equipment
WO2023275191A1 (en) * 2021-06-29 2023-01-05 Christeyns Improved enzyme-containing additive and detergent liquor formulations

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PANT KARAN J., COTTER PAUL D., WILKINSON MARTIN G., SHEEHAN JEREMIAH J.: "Towards sustainable Cleaning‐in‐Place (CIP) in dairy processing: Exploring enzyme‐based approaches to cleaning in the Cheese industry", COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY, vol. 22, no. 5, 1 September 2023 (2023-09-01), US , pages 3602 - 3619, XP093301799, ISSN: 1541-4337, DOI: 10.1111/1541-4337.13206 *

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