Easy-to-wash low 1, 4-dioxane two-component food detergent, preparation method and application

Abstract

The invention discloses an easy-to-wash low 1, 4-dioxane bi-component food detergent, a preparation method and application, the detergent comprises alkyl glycoside, cocamidopropyl betaine, sodium citrate, lipase, a bacteriostatic agent, ethanol, beta-cyclodextrin, a pH regulator, edible essence and deionized water, and the detergent is applied to food cleaning or preparation of other detergents. The preparation process comprises the steps of enzyme stabilization pretreatment, staged temperature control mixing, ultrasonic dispersion and sterile filling. The APG and the CAPB are adopted to replace traditional SLES, ethylene oxide by-products are avoided, 1, 4-dioxane control is achieved, lipase and beta-cyclodextrin form a compound, the enzyme activity is prolonged, the grease decomposition efficiency is improved, flushing is easy, the combination of ethyl alcohol and beta-cyclodextrin aims at worm eggs and pesticide residues, and the preparation method has the advantages of being simple in process, convenient to operate and low in cost. The composite system improves the denaturation efficiency of egg surface protein by 3 times, and has significant application potential in the field of household fruit and vegetable, tableware cleaning or food processing equipment cleaning.

Description

Technical Field

[0001] The present invention belongs to the field of food detergents, and relates to a two-component food detergent, specifically an easily rinsed two-component food detergent with low 1,4-dioxane, a preparation method and an application thereof. Background Art

[0002] Common harmful components in food detergents include methanol and formaldehyde. The newly released GB 14930.1-2022 "National Food Safety Standard Detergents" has added restrictions on the safety item of 1,4-dioxane in food detergents. And in the highly efficient analytical technique of gas chromatography-mass spectrometry (GC-MS), the detection of harmful components in food detergents is quite accurate.

[0004] In relevant formulation experimental studies, we have conducted sufficient research and experiments on 1,4-dioxane. The structural formula of 1,4-dioxane is 1,4-dioxane, which is a cyclic ether compound with high water solubility (infinitely miscible with water), low volatility (boiling point 101.3 °C) and chemical stability. It is widely used in fields such as medicine, pesticides, and fragrances, for example as a solvent, a precursor of anesthetic, etc. And due to its excellent solvent properties, it was once widely used in the synthesis of surfactants and the production of cleaning agents. In the field of food detergents, 1,4-dioxane mainly comes from the surfactants in food detergents and is a by-product during the ethoxylation production of surfactants.

[0005] Research shows that 1,4-dioxane has the following toxicities: (1) relatively strong toxicity, being a carcinogen, irritating to the skin, eyes and respiratory system; (2) may cause damage to the liver, kidneys and nervous system, and may lead to death in acute poisoning; (3) having weak genotoxicity, and although the impact on human reproduction is not yet clear, a developmental study on rats shows that 1,4-dioxane has slight toxicity to developing rat fetuses.

[0006] Although 1,4-dioxane can be microencapsulated, microencapsulation is usually used to encapsulate functional components such as flavors and probiotics for the purpose of controlled release, protecting activity or masking bad properties. However, 1,4-dioxane is neither a functional component of the detergent (such as surface activity, detergency, etc.) nor a "beneficial activity" that needs to be protected. If forced to encapsulate: (1) release risk: the mechanical force, temperature or acid-base environment during the washing process may damage the capsule wall, resulting in the leakage of 1,4-dioxane into the washing system; (2) residue hazard: even if the capsule is not broken, the microcapsules remaining on the tableware itself may become a new source of pollution.

[0007] The use of alkylphenol polyoxyethylene ether in the preparation of detergents is common in detergent formulations. The drawback is that it may produce dioxane by-products. If the content of 1,4-dioxane in food detergents is to be controlled below the standard, it is necessary to innovate and research the formulation, replace the components that are prone to generate 1,4-dioxane, and optimize the formulation ratio and process flow to achieve good washing effects during washing while reducing the formation of 1,4-dioxane. Summary of the Invention

[0008] The purpose of the present invention is to solve the drawbacks existing in the prior art, and a two-component food detergent with easy rinsing and low 1,4-dioxane, a preparation method and an application are proposed. By adopting the combination of APG and CAPB two components, the control of 1,4-dioxane is achieved. By forming a complex of lipase and β-cyclodextrin, the enzyme activity can be prolonged and the oil decomposition efficiency can be improved to achieve easy rinsing.

[0009] To achieve the above purpose, the present invention adopts the following technical scheme: A two-component food detergent with easy rinsing and low 1,4-dioxane, comprising alkyl polyglycoside, cocamidopropyl betaine, sodium citrate, lipase, bacteriostatic agent, pH regulator, food-grade ethanol, β-cyclodextrin and deionized water in parts by weight.

[0010] A two-component food detergent with easy rinsing and low 1,4-dioxane, calculated by mass percentage, the food detergent comprises the following components: 20-25% of alkyl polyglycoside, 8-12% of cocamidopropyl betaine, 10-15% of sodium lauryl ether sulfate, 5-8% of sodium citrate, 1-2% of lipase, 0.5-1% of natural bacteriostatic agent, 0.5-1% of pH regulator, 3-5% of food-grade ethanol, 2-3% of β-cyclodextrin, 0.5% of biodegradation promoter, 0.5-1% of edible essence, and the balance is deionized water.

[0011] A two-component food detergent with easy rinsing and low 1,4-dioxane, calculated by mass percentage, the food detergent comprises the following components: 10-15% of alkyl polyglycoside, 5-8% of cocamidopropyl betaine, 2-3% of amine oxide, 5-8% of sodium citrate, 0.5-1% of lipase, 3.1-5.5% of bacteriostatic agent, 5-10% of food-grade ethanol, 2-3% of β-cyclodextrin, 2-4% of pH regulator, 0.5-1% of edible essence, and the balance is deionized water.

[0012] An easily rinsable low 1,4-dioxane two-component food detergent. Calculated by mass percentage, the food detergent comprises the following components: alkyl polyglycoside 15-20%, cocamidopropyl betaine 8-12%, sodium carbonate / sodium citrate 5-8%, lipase 1-3%, citric acid 2-4%, natural bacteriostatic agent 0.5-1%, pH regulator 2-4%, food-grade ethanol 5-8%, β-cyclodextrin 2-3%, coconut amide monoethanolamine 1-2%, sodium gluconate 0.5-1%, edible essence 0.5-1%, and the balance being deionized water.

[0013] An easily rinsable low 1,4-dioxane two-component food detergent. Calculated by mass percentage, the food detergent comprises the following components: alkyl polyglycoside 12-18%, cocamidopropyl betaine 8-12%, sodium citrate 4-6%, lipase 0.3-0.7%, food-grade ethanol 5-10%, β-cyclodextrin 2-3%, polyethylene glycol 2-4%, silicone ether defoamer 0.2-0.4%, sodium benzoate 0.2-0.4%, chitosan quaternary ammonium salt 0.5-1.5%, phytic acid 1-3%, edible essence 0.1-0.3%, and the balance being deionized water.

[0014] As a further description of the above technical solution: An easily rinsable low 1,4-dioxane two-component food detergent, the bacteriostatic agent is one of tea tree oil nanoemulsion, tea tree oil, and phenoxyethanol, and the pH regulator is citric acid or citric acid-sodium bicarbonate.

[0015] As a further description of the above technical solution: The bacteriostatic agent includes a natural bacteriostatic agent and a synthetic bacteriostatic agent. The natural bacteriostatic agent is honeysuckle extract, and the synthetic bacteriostatic agent is benzalkonium chloride. Among them, the natural bacteriostatic agent is 3-5%, and the synthetic bacteriostatic agent is 0.1-0.5%. The pH regulator is citric acid or citric acid-sodium bicarbonate.

[0016] A preparation method of an easily rinsable low 1,4-dioxane two-component food detergent for preparing an easily rinsable low 1,4-dioxane two-component food detergent. The preparation method comprises the following operation steps. S1: Enzyme stabilization pretreatment; β-cyclodextrin and lipase are mixed in a mass ratio of 1:4 and added to a stainless steel reaction kettle. The temperature is set at 45°C, and the stirring speed is 50 rpm for 30 minutes to form an inclusion complex.

[0017] S2: Temperature-controlled mixing in stages; SS1: Aqueous phase treatment. Deionized water at 40 - 45 °C was added. Sodium citrate and food - grade ethanol were added to a stainless - steel reactor and stirred for 20 minutes. The deionized water and sodium citrate were cooled to 25 °C, and then alkyl polyglycoside and betaine were added to an ultrasonic homogenizer for ultrasonic dispersion. The rotation speed of the ultrasonic homogenizer was 2000 rpm and the homogenization time was 10 minutes; SS2: Add β - cyclodextrin, lipase, and bacteriostatic agent to a thermostatic magnetic stirrer, and maintain the thermostatic magnetic stirrer at 25 °C to avoid enzyme inactivation; SS3: Adjust the pH in three gradients. The gradient is set as 6.0 → 6.5 → 7.0. Use a pH automatic titrator to add a pH regulator to adjust the pH to 7.0 ± 0.2.

[0018] S3: Ultrasonic dispersion; Add the remaining substances in the formula and perform ultrasonic treatment at 20 kHz for 5 minutes with an energy density of 0.5 W / cm³; S4: Sterile filling; After filtering through a 0.22 - μm filter membrane, it is filled under nitrogen protection.

[0019] As a further description of the above - mentioned technical solution: After SS2, there is a vacuum degassing step. The pressure is set to - 0.08 MPa and the time is 30 minutes to eliminate the bubbles introduced by stirring and prevent foam overflow during filling.

[0020] As a further description of the above - mentioned technical solution: During the sterile filling in step S4, the pH value is monitored in real - time. The detected pH value is 6.5 - 7.5 and the viscosity is 350 ± 50 mPa·s. After passing the inspection, it is filtered through a 0.22 - μm filter membrane and filled under nitrogen protection.

[0021] As a further description of the above - mentioned technical solution: An application of an easy - to - rinse low - 1,4 - dioxane two - component food detergent, which includes the described easy - to - rinse low - 1,4 - dioxane two - component food detergent, and the application of the easy - to - rinse low - 1,4 - dioxane two - component food detergent in the preparation of detergents.

[0022] Due to the adoption of the above - mentioned technical solution, the beneficial effects obtained by the present invention are: (1) The present invention realizes the control of 1,4 - dioxane by adopting the APG and CAPB two - component combination; (2) The present invention forms a complex by lipase and β - cyclodextrin, which can prolong the enzyme activity and improve the oil decomposition efficiency to achieve easy rinsing; (3) The present invention combines ethanol and β - cyclodextrin for egg and pesticide residues, and the complex system improves the denaturation efficiency of the surface protein of eggs by 3 times. Description of the drawings

[0023] Figure 1 This is a flow chart of a preparation method of an easily rinsable food detergent with low 1,4-dioxane proposed by the present invention.

[0024] Figure 2 This is a bar chart of the functional test results of Example 7 of an easily rinsable food detergent with low 1,4-dioxane proposed by the present invention. Detailed implementation manners

[0025] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0026] Please refer to the appendix Figure 1-2 , and the present invention provides the following embodiments to describe the present invention in detail: Example 1

[0027] An easily rinsable food detergent with low 1,4-dioxane, calculated by mass percentage, the food detergent includes the following components: alkyl polyglycoside 23%, cocamidopropyl betaine 10%, sodium laureth sulfate (low dioxane type SLES) 12%, sodium citrate 7%, bioenzyme 1%, nanoemulsion of tea tree oil 0.5%, citric acid-sodium bicarbonate 0.5%, ethanol 3.5%, β-cyclodextrin 2.5%, biodegradation promoter 0.5%, edible essence 0.1%, and the balance is deionized water.

[0028] In this example, the alkyl polyglycoside (APG) is of natural origin, specifically synthesized from glucose and fatty alcohol. The selection of alkyl polyglycoside (APG) avoids the original ethoxylation process, improves the generation of 1,4-dioxane from the source, and at the same time, alkyl polyglycoside (APG) can also achieve low-foaming and easy rinsing, strong wax and dirt removal, and excellent biodegradability.

[0029] Simply adding cocamidopropyl betaine to the food detergent has the effects of increasing foam and stabilizing foam, synergistic decontamination, and mild antibacterial. However, in this formula, we adopt a binary compound design of alkyl polyglycoside (APG) and cocamidopropyl betaine. After compounding, it can reduce the critical micelle concentration (CMC) and improve the emulsifying ability for oils and fats.

[0030] For example, in our experiment, after adding the binary components of alkyl polyglycoside (APG) and cocamidopropyl betaine to a common food detergent (dishwashing liquid) on the market, the removal rate of olive oil increased from 75% when using only alkyl polyglycoside (APG) to 90%, and at the same time, the amount of rinsing water was reduced by 30% to achieve the same cleanliness.

[0031] Sodium Laureth Sulfate (low dioxane type SLES) adopts an optimized process to reduce dioxane to <1 ppm and enhance the degreasing ability.

[0032] β-Cyclodextrin can encapsulate fat-soluble pesticides such as organophosphorus to improve the removal rate. Food-grade ethanol is selected, which can assist in dissolving wax and accelerate volatilization to reduce residues. The composite system of ethanol and β-cyclodextrin is designed for egg residues and pesticide residues. Ethanol dissolves non-polar pollutants such as the wax outer layer, and β-cyclodextrin encapsulates the inner hydrophobic groups. In the test, compared with the addition of β-cyclodextrin or ethanol alone, the removal rate of artificial wax increased from 65% to 92%; and the denaturation efficiency of the protein on the egg surface by the composite system increased by 3 times.

[0033] Sodium citrate is modified sodium citrate, which can effectively chelate calcium and magnesium ions, enhance the ability to remove deposits, and replace traditional phosphates.

[0034] The bio-enzyme lipase and / or protease / lipase complex enzyme can target and decompose protein / fat stains, and directionally decompose oil, starch stains and egg adhesion substances, such as the removal of eggs and wax. Tea tree oil nanoemulsion, as a natural bacteriostatic agent, can damage the microbial cell membrane, thereby inhibiting the generation of bacteria. The bio-enzyme adopts microcapsule embedding technology to extend the shelf life of the enzyme preparation. The edible essence is natural citrus fragrance, and citric acid-sodium bicarbonate maintains the pH at 6.5-7.5 to protect the enzyme activity. The biodegradation promoter can accelerate the mineralization of components, such as the metabolites of Bacillus subtilis.

[0035] In the present invention, the compounding of lipase and sodium citrate improves the oil decomposition efficiency. At the same time, the formation of a complex by lipase and β-cyclodextrin can extend the enzyme activity and improve the oil decomposition efficiency. Example 2

[0036] In this example, alkyl polyglycoside is replaced by sodium N-lauroyl glutamate, and the remaining components and proportions remain the same as in Example 1. Due to the lower cost of sodium N-lauroyl glutamate, this formulation is more convenient for cost control and is suitable for cleaning production equipment such as dairy products and baking equipment. Example 3

[0037] In this example, a concentrated formulation can be formed. The specific method is to increase alkyl polyglycoside (APG) to 30% and add 5% of PEG-600 as a coupling agent to make a 10-fold concentrated solution. The remaining components and proportions remain the same as in Example 1. Example 4

[0038] In this embodiment, a low-temperature adaptable formulation can be formed. Specifically, 2% propylene glycol is added as an antifreeze agent to ensure normal use below 0°C, and the remaining components and proportions remain unchanged compared to Embodiment 1.

[0039] To more clearly illustrate the formulation functions described in Embodiments 1-4, we used a sampling method to verify the performance indicators. Each embodiment provided 100 cleaning samples, and 10 samples were randomly selected from each embodiment for project performance testing. The average value method of sampling was used for various indicators, and the test methods and results are shown in Table 1.

[0040] Table 1: 。

[0041] Therefore, according to Embodiments 1-4, the present invention achieves the following three beneficial effects: (1) Dioxane control: ① Purify SLES using molecular distillation technology to make the 1,4-dioxane residue < 1 ppm (national standard < 30 ppm); ② Partially replace SLES with alkyl polyglycoside (APG) to reduce the dependence on ethoxylates.

[0042] (2) Targeted detergency synergy, the combination of ethanol and β-cyclodextrin for egg and pesticide residues: ① β-cyclodextrin adsorption: Preferentially bind to non-polar pesticide molecules such as pyrethroids; ② Ethanol solubilization: Quickly dissolve wax and promote rinsing;

[0043] (3) By compounding lipase and sodium citrate, the oil decomposition efficiency is improved. At the same time, a complex is formed between lipase and β-cyclodextrin, which can extend the enzyme activity and improve the oil decomposition efficiency. Embodiment 5

[0044] An easily rinsed food detergent with low 1,4-dioxane content, calculated by mass percentage, the food detergent comprises the following components: 12% alkyl polyglycoside, 6% cocamidopropyl betaine, 2.5% cocamine oxide, 6% sodium citrate, 0.8% lipase (alkaline), 4% honeysuckle extract, 8% ethanol (food grade), 2.5% β-cyclodextrin, 3% pH regulator (citric acid), 0.2% benzalkonium chloride, 0.5-1% edible essence, and the balance is deionized water.

[0045] In this embodiment, the synergistic effects of the components are as follows: 1. The combination of alkyl polyglycoside and cocamidopropyl betaine surfactants balances detergency and safety. It can enable APG (the main detergency agent) and CAPB (the auxiliary foaming agent) to form micelles and act synergistically, thereby reducing the critical micelle concentration (CMC) and increasing the detergency efficiency by 30%. Cocamine oxide has bactericidal activity, with an antibacterial rate against Escherichia coli > 99%. After addition, it can also enhance foam stability through charge neutralization. After being compounded with APG, the foam half-life is extended to 15 minutes. The three components of alkyl polyglycoside, cocamidopropyl betaine, and cocamine oxide synergistically constitute the core surfactant system, achieving the characteristics of easy rinsing and low dioxane.

[0046] 2. Lipase and sodium citrate can achieve the synergistic addition of enzyme-chelating agent. Through the compounding of lipase and sodium citrate, the oil decomposition efficiency and the removal efficiency of oil / wax are improved. Among them, sodium citrate chelates Ca²⁺ to prevent lipase inactivation, increasing its activity by 40% at pH 6.5. At the same time, lipase decomposes triglycerides into monoesters, which emulsify oils synergistically with surfactants, increasing the detergency by 50%. At the same time, lipase forms a complex with β-cyclodextrin, which can extend the enzyme activity and improve the oil decomposition efficiency.

[0047] 3. Flos Lonicerae extract is a natural antibacterial agent containing chlorogenic acid and luteoloside, with an inhibition rate against Staphylococcus aureus and Salmonella > 90%. Benzalkonium chloride is a quaternary ammonium salt cationic bactericide with broad-spectrum bactericidal activity, and the killing rate of mold spores > 99.9%. Controlling the concentration at 0.1 - 0.3% can avoid toxicity risks. In the formula of the present invention, the ratio of benzalkonium chloride is set at 0.2%, which not only avoids toxicity but also has good bactericidal effects;

[0048] By the antibacterial circle experiment, the synergistic ratio of Flos Lonicerae extract (3 - 4%) and benzalkonium chloride (0.2%) is optimized to provide double antibacterial protection and inhibit the growth of microorganisms. Chlorogenic acid in Flos Lonicerae destroys the cell membrane of microorganisms, and benzalkonium chloride penetrates and kills them, with an antibacterial rate against Escherichia coli > 99.9%. After compounding, the dosage of the antibacterial agent is reduced by 50%, and still maintains equivalent antibacterial effects.

[0049] 4. Ethanol is selected as a food-grade solvent with a purity > 99.5%, which assists in dissolving oils and enhancing the bactericidal effect. In the actual use process, the synergistic antibacterial rate of ethanol and benzalkonium chloride (0.2%) can be increased by 20%.

[0050] 5. The combination of ethanol and β-cyclodextrin is aimed at eggs and pesticide residues. Ethanol dissolves non-polar pollutants, such as the waxy outer layer, and β-cyclodextrin embeds the inner hydrophobic groups, increasing the artificial wax removal rate from 65% to 92%; the denaturation efficiency of the protein on the surface of eggs by the composite system is increased by 3 times.

[0051] Verified by orthogonal experiments, this formulation can remove 95% of artificial wax and 90% of organophosphorus pesticides after being soaked at 40°C for 10 minutes. The biodegradation rate within 28 days is >92%, and the residue of 1,4-dioxane is <5 ppm, fully meeting the requirements of the food industry for highly efficient, safe, and environmentally friendly detergents.

[0052] In the present invention, the functions of easy rinsing and low 1,4-dioxane can be achieved. To prove this experimental result, the test method adopts a comparative experimental design: Control group: A commercially available detergent containing sodium lauryl sulfate (SLES) (1,4-dioxane content: 20 μg / kg).

[0053] Experimental group: This formulation.

[0054] The test results are shown in Table 2.

[0055] Table 2: 。

[0056] Overall effect test and comparative analysis The test of the formulation effect is as follows: (1) Design the test plan according to GB 14930.1-2022 "National Food Safety Standard Detergent" and AOAC standard: (2) Detergency test: Use an artificially contaminated cloth (a mixture of beef tallow / protein stains), and determine the change value of reflectance ΔR through the method specified in WS / T 211-2015; (3) Antibacterial performance: According to the film method of ISO 20743:2021, test the bactericidal rates against Escherichia coli (ATCC 25922) and Staphylococcus aureus (ATCC 6538); (4) Residue detection: Determine the residue of pesticides (chlorpyrifos) after β-cyclodextrin inclusion by GC-MS method; (5) Enzyme activity retention rate: Detect the change in lipase activity after accelerating storage at 37°C for 30 days; (6) Skin irritation: Use the in vitro reconstructed epidermal model EpiSkin to determine the cell survival rate.

[0057] Through comparative experimental design and result presentation, the present invention designs 3 groups of comparative examples to verify the synergistic effect of key components. Among them, there is no lipase in Comparative Example 1, APG is replaced by SLES in Comparative Example 2, and there is no β-cyclodextrin in Comparative Example 3. The results are shown in Table 3.

[0058] Table 3: 。

[0059] Therefore, through Tables 2-3, we can draw the following conclusions: 1. APG and CAPB are used to replace traditional SLES, avoiding the by-products of ethylene oxide and achieving the control of 1,4-dioxane.

[0060] 2. In the present invention, by forming a complex of lipase and β-cyclodextrin, the enzyme-cyclodextrin synergy can prolong the enzyme activity and improve the oil decomposition efficiency. Removing lipase results in a 16.5% decrease in the protein stain removal rate, and the absence of β-cyclodextrin increases the pesticide residue by 2.34 times.

[0061] 3. After replacing alkyl polyglycoside with sodium lauryl sulfate (SLES), the skin irritation significantly increases, and the enzyme activity retention rate decreases by 14%, showing the biocompatibility advantage of APG; 4. Using a natural antibacterial system, the synergistic effect of honeysuckle extract and benzalkonium chloride reduces the amount of chemical preservatives, making it safer and more protective of human health.

[0062] Example 6 In this example, the natural bacteriostatic agent we selected is the honeysuckle-menthol compound extract, with an addition weight ratio of 4%. The rest is the same as in Example 5. The bacteriostatic rate of the detergent added with the honeysuckle-menthol compound extract > 99%.

[0063] The beneficial effects that can be achieved in Examples 5 - 6 are: easy to rinse, low 1,4-dioxane, bacteriostatic, good foam quality. At the same time, as a food detergent, it can remove attachments, artificial edible wax, and pesticide residues, and biodegradation can effectively remove eggs.

[0064] Example 7 An easy-to-rinse food detergent with low 1,4-dioxane. Calculated by mass percentage, the food detergent includes the following components: alkyl polyglycoside 18%, cocamidopropyl betaine 10%, sodium carbonate 6%, lipase 2%, citric acid 3%, tea tree oil or phenoxyethanol 0.8%, ethanol 7%, β-cyclodextrin 2.5%, pH buffer 3%, coconut monoethanolamide 1.5%, sodium gluconate 0.8%, edible essence 0.5%, and the balance is deionized water.

[0065] In this example, the bacteriostatic agent is configured as tea tree oil or phenoxyethanol, which can achieve a natural bacteriostatic agent without drug resistance. The combined effect of ethanol and β-cyclodextrin and the effect of the formation of a complex of lipase and β-cyclodextrin are the same as those in Example 5.

[0066] The binary combination of alkyl polyglycoside (APG) and cocamidopropyl betaine (CAB) can reduce the mixed micelle particle size from 120 nm to 85 nm, and increase the emulsification efficiency of artificial edible wax by 180%. For example, the measured data shows that the emulsification rate of a 5% waxy stain sample reaches 92% within 30 seconds. At the same time, the combination of alkyl polyglycoside (APG) (non-ionic surfactant) and cocamidopropyl betaine (CAB) (amphoteric surfactant) is used to avoid the ethoxylation process of traditional SLES / ALS surfactants, eliminating the risk of 1,4-dioxane formation from the source.

[0067] The binary combination of alkyl polyglycoside (APG) and cocamidopropyl betaine (CAB) achieves a low interfacial tension, rapidly penetrating wax and sediment; sodium carbonate provides an alkaline environment to decompose stubborn stains, and ethanol enhances the dissolution of hydrophobic components. After synergy, it is easily rinsed away by water.

[0068] The terpene compounds contained in tea tree oil can damage the cell membranes of microorganisms, the enzyme preparation decomposes the protein adhesion layer on the surface of the eggs, and food-grade ethanol assists in penetration and inactivation. The triple effect ensures hygiene and safety.

[0069] Cocamidopropyl betaine (CAB) provides a dense foam, coconut monoethanolamide (CMEA) inhibits the generation of large bubbles and prolongs the foam life, and alkyl polyglycoside (APG) regulates the system viscosity, achieving a balance between low residue and good user experience.

[0070] In the above embodiments, the relevant functional test results are as Figure 2 shown.

[0071] Examples 1-7 of this formulation achieve a balance among functionality, safety, and environmental friendliness through multiple synergistic effects, are applicable to the cleaning scenarios of fruits, vegetables, and tableware, have a high biodegradation rate, and avoid imposing a burden on the aquatic ecosystem.

[0072] Example 8 An easily rinsed food detergent with low 1,4-dioxane content. Calculated by mass percentage, the food detergent includes the following components: 15% alkyl polyglycoside, 10% cocamidopropyl betaine, 5% sodium citrate, 0.5% lipase, 6% ethanol, 2.5% β-cyclodextrin, 3% polyethylene glycol (PEG-1000), 0.3% silicone ether defoamer, 0.3% sodium benzoate, 1% chitosan quaternary ammonium salt, 3% pH regulator, 2% phytic acid, 0.2% edible essence, and the balance is deionized water.

[0073] In this formulation, we still use the binary combination of alkyl polyglycoside (APG) and cocamidopropyl betaine (CAB) to achieve a low interfacial tension, rapidly penetrating wax and sediment. At the same time, lipase (≥100,000 U / g) is used as a wax and sediment degrading enzyme.

[0074] The difference between this embodiment and Embodiments 1-7 is that polyethylene glycol (PEG-1000) is added as a foam stabilizer and solubilizer, sodium benzoate as a preservative, chitosan quaternary ammonium salt as an antibacterial agent and egg hatching agent, phytic acid as a pesticide chelating agent / metal ion blocker, and citric acid or citric acid-sodium bicarbonate as a pH regulator.

[0075] In this formula, we use the combination of ethanol and β-cyclodextrin, the combination of lipase and β-cyclodextrin, and at the same time, polyethylene glycol (PEG-1000), silicone ether defoamer, sodium benzoate, chitosan quaternary ammonium salt, and phytic acid achieve better effects.

[0076] In the method for determining the optimal ratio of each component in the formula, we use orthogonal experiments to confirm the optimal ratio.

[0077] 1. In the single-factor concentration scan, APG concentration gradient: 10%, 15%, 20%.

[0078] Test indicators: critical micelle concentration (CMC), surface tension (25 °C).

[0079] Optimal point: When the concentration is 15%, the CMC drops to 0.012 g / L, and the surface tension is 32 mN / m (balancing detergency and mildness). Betaine concentration gradient: 8%, 10%, 12%.

[0080] Key indicators: mixed micelle particle size, emulsification rate (emulsification time of olive oil).

[0081] Optimal point: When the concentration is 10%, the micelle particle size is 85 nm (30% smaller than that of single APG), and the emulsification time is shortened to 15 seconds.

[0082] Table 4: Orthogonal test design (L9 (3 4 )): Table 4: .

[0083] The synergistic effect of alkyl polyglycoside (APG) and coconut oil amide propyl betaine (CAB) reduces the mixed micelle particle size from 120 nm to 85 nm, and the emulsification efficiency of artificial edible wax is increased by 180%. In a specific implementation process, through measured data, the emulsification rate of 5% waxy dirt sample reaches 92% within 30 seconds.

[0084] By adding chitosan quaternary ammonium salt, the positively charged group destroys the bacterial cell membrane, and the antibacterial rate against Escherichia coli is ≥99.9%, achieving antibacterial effect. It dissolves the chitin layer of the eggshell, and the egg hatching rate is 85%+ within 48 hours, achieving the effect of inhibiting egg hatching.

[0085] By adding lipase, which preferentially decomposes wax esters (C16-C36) and sediment grease, the degradation rate of palm wax is 78%. An enzymatic emulsification system is formed with APG, reducing the need for mechanical friction and achieving synergistic decontamination.

[0086] By adding phytic acid, the metal ion cofactors of organophosphorus / pyrethroid pesticides are complexed, and the desorption efficiency is increased by 60%, achieving the chelation of agricultural residues. At the same time, Fe³⁺ / Ca²⁺ in water is blocked to prevent pigment deposition, achieving anti-redeposition.

[0087] In the specific description of this embodiment, two cases are added for illustration.

[0088] Case 1: All-in-one decontamination combination: APG, betaine, lipase, phytic acid combination.

[0089] Mechanism of action: APG emulsifies wax → lipase hydrolyzes wax ester → phytic acid chelates residual pesticides.

[0090] Measured data: The removal rate of artificial wax on the apple surface is 97.3%, and the chlorpyrifos pesticide residue is reduced from 0.8 mg / kg to 0.02 mg / kg (lower than the national standard of 0.1 mg / kg). Case 2: Antibacterial and antifouling cycle: Chitosan quaternary ammonium salt, sodium citrate, sodium benzoate combination.

[0091] Synergistic effect: Chitosan destroys the bacterial membrane → sodium citrate adjusts pH to inhibit spores → sodium benzoate blocks metabolism.

[0092] Advantages: Form a triple barrier of "lysis, inhibition, and anti-corrosion", and the colony count decreases by 99.99% in 72 hours.

[0093] In this embodiment, the following effects are obtained through inspection of various formulations and the synergistic effects of the formulations: The specific values are shown in Table 5.

[0094] Table 5: 。

[0095] Therefore, the beneficial effects that can be achieved in this embodiment are: (1) Enzyme-surfactant synergistic technology: Lipase and APG form a dual-effect decontamination of "biocatalysis + physical emulsification"; (2) Targeted scavenging system: The specific functions of chitosan to lyse eggs / phytic acid to chelate agricultural residues; (3) Green closed-loop design: Biobased raw materials (APG / chitosan) and high degradability (96.2%).

[0096] This formulation has significant application potential in the field of cleaning food processing equipment, especially suitable for high-standard production lines sensitive to residues, such as dairy and baking equipment, and at the same time provides a technical reference for the development of low-toxic and environmentally friendly detergents.

[0097] The recommended water temperature for the detergents described in Examples 1-8 of the present invention is 30-50 °C to keep the enzyme preparation at an appropriate water temperature. The action principles of lipase at low and high temperatures are different. High temperature will destroy the activity of lipase and make it unable to regain its activity. Low temperature generally only inhibits the activity of lipase and does not damage the molecular structure of lipase. When the temperature returns to normal, the activity of lipase will recover.

[0098] Since most areas in China are hard water areas with a hardness range of 8-25 degrees, and the hardness in North China and Northwest China is generally higher than that in South China, for the hard water areas in the north and northwest, 0.5% of methylglycine diacetic acid (MGDA) can be added to the detergent in the present invention to improve the chelating ability.

[0099] Specific application scenarios of the food detergent provided by the present invention: (1) Fruit and vegetable cleaning: Dilution ratio 1:200 (0.5% concentration), soaking for 5 minutes can remove 90% of pesticide residues.

[0100] (2) Removing fishy smell from meat: Treating with 1% solution for 10 minutes, the fishy smell removal rate > 95%.

[0101] (3) Tableware rinsing: The rinsing time is shortened to 15 seconds (the traditional product requires 30 seconds) because ethyl hydroxyethyl cellulose ether reduces the surface tension.

[0102] (4) Adding active ingredients of other detergents: Due to the innovative composition method of the formulation, it has researchability and can be added as a composition in other detergents that need to control 1,4-dioxane.

[0103] The detergent described in the present invention can produce the food detergent described in the present invention. In the preparation process, equipment such as a stainless steel reaction kettle, an ultrasonic homogenizer, a magnetic stirrer, and a pH automatic titrator are required. The steps are as follows.

[0104] 1. Enzyme stabilization pretreatment step.

[0105] β-cyclodextrin and lipase are mixed in a mass ratio of 1:4 and added to a stainless steel reaction kettle. The temperature is set at 45 °C, and the stirring speed is 50 rpm for 30 minutes to form an inclusion complex.

[0106] In this step, the model of the stainless steel reactor we selected is: a stainless steel reactor with a nominal capacity of 500L - 2000L, such as the 500L model, and a heating power of 4×9kW. Since the production of food detergents usually requires a certain batch scale, the capacity of 500L - 2000L can meet the needs of medium and large-scale production. Stainless steel materials (such as 304 or 316L) have the characteristics of corrosion resistance, hygiene, and no environmental pollution, meeting the hygiene requirements of the food industry. The reactor heats up quickly and is resistant to high temperatures, capable of meeting the heating conditions that may be required during the preparation of detergents. It has various stirring forms. For example, the frame stirring can ensure the uniform mixing of materials in a short time, enabling the substances participating in the reaction to be fully mixed, improving the reaction efficiency and product quality;

[0107] 2. Step of temperature-controlled mixing in stages.

[0108] Step (1): Treatment of the aqueous phase. Add deionized water at 45°C, and add sodium citrate and ethanol to the stainless steel reactor, and stir for 20 minutes.

[0109] Cool the deionized water and sodium citrate to 25°C.

[0110] Add alkyl polyglycoside and betaine to the ultrasonic homogenizer for ultrasonic dispersion.

[0111] For the ultrasonic homogenizer, we use the ultrasonic industrial homogenizer of Nanjing Hanzhou Technology Co., Ltd., a tubular homogenizer with a power of 2000W and a frequency of 20KHz.

[0112] The ultrasonic homogenizer utilizes the cavitation effect to generate huge energy, which can strongly disperse the liquid flowing through the equipment, playing the role of emulsification and homogenization. It can evenly mix various components in the food detergent, improving the stability and quality of the product.

[0113] It can expel tiny bubbles inside the liquid, crush large particle substances, and prevent precipitation, which is very important for the appearance and use performance of the detergent product.

[0114] The tubular homogenizer has a large single-machine power, reaching several kilowatts or more. It has over-current and over-voltage protection functions, as well as soft start and under-voltage protection functions. The frequency is automatically tracked and adjusted, which can ensure stable operation under different working conditions and has a wide range of applications, meeting the needs of batch liquid treatment during the production of food detergents.

[0115] In this step, we set the rotation speed of our ultrasonic homogenizer to 2000 rpm and the homogenization time to 10 minutes.

[0116] Step (2): Add β-cyclodextrin, lipase, and bacteriostatic agent to a thermostatic magnetic stirrer (09A / 09B series magnetic stirrer). Maintain the thermostatic magnetic stirrer at 25°C to avoid enzyme inactivation, and then perform vacuum degassing. Set the pressure to -0.08 MPa and the time to 30 minutes to eliminate the bubbles introduced by stirring and prevent foam overflow during filling.

[0117] We select the 09A / 09B series magnetic stirrer, which has a liquid crystal display screen, a menu-style operation interface, and multiple groups of data displayed on one screen, making the operation simple and convenient. It uses feedback control to heat the temperature of the heating plate and is equipped with a Pt100 sensor, which can accurately control the temperature of the experimental sample. The high temperature can reach 350 degrees, and the accuracy is 0.5 degrees, which can meet the requirements for temperature control in the preparation of food detergents and ensure that the materials react or mix at the appropriate temperature. It has a digital timer function, with a timing range of 99 hours and 59 minutes, and also has temperature, rotation speed, and timer memory storage functions, which are convenient for operators to set and repeat operations according to different process requirements. The speed range is 100 - 1400 revolutions, and the speed control accuracy is 5 revolutions, which can provide different stirring intensities to meet the mixing requirements of different materials.

[0118] Step (3): Adjust the pH in three gradients, with the gradient settings of 6.0 → 6.5 → 7.0. Use a pH automatic titrator to add a pH regulator to adjust the pH to 7.0 ± 0.2.

[0119] The model of the pH automatic titrator is selected as the German Schott TitroLine7000 automatic potentiometric titrator.

[0120] This instrument is simple and practical for potentiometric titration. It has a high-resolution Ph / Mv and dead-stop measurement interface, which can quickly, reliably, and accurately measure a wide range of parameter values. It is suitable for food analysis, water quality analysis, etc., and can also meet the requirements for accurate measurement and control of pH values in the production process of food detergents.

[0121] 3. Ultrasonic dispersion step; Add the remaining substances in the formula and perform ultrasonic treatment at 20 kHz for 5 minutes, with an energy density of 0.5 W / cm³; 4. Aseptic filling; Monitor the pH value in real-time. When the detected pH value is 6.5 - 7.5 and the viscosity is 350 ± 50 mPa·s, after passing through a 0.22 μm filter membrane, fill under nitrogen protection.

[0122] For the equipment used to monitor the pH value in real time, we adopt an online pH meter, which can be directly installed on the detergent production line to continuously monitor the pH value of the solution in real time, and can transmit the measured data to the central control room or other monitoring devices through signal transmission for timely adjustment and control to ensure the stability and dynamic adjustment of the pH value during the production process.

[0123] Traditional detergent production generally adopts the step-by-step mixing method: (1) Heat the aqueous phase (surfactant + chelating agent) to 50°C and stir; (2) Add solid components (enzymes, preservatives) and disperse; (3) Adjust the pH and then fill.

[0124] The pain points in traditional detergent production are: enzymes are easily inactivated (denatured by high temperature), natural extracts are unevenly dispersed, and batch stability is poor.

[0125] During the research process, we compared the traditional process with the process described in the present invention and found that our process has the following advantages, as shown in Table 6.

[0126] Table 6: 。

[0127] Therefore, this process has the following advantages: (1) Improved enzyme stability: Microencapsulation pretreatment and low-temperature mixing reduce the enzyme activity loss rate from 35% in the traditional process to 10.3%.

[0128] (2) Balance of efficiency and quality: Ultrasonic dispersion shortens the mixing time by 40%, and the particle size uniformity (PDI ≤ 0.25) is better than that of the traditional process (PDI ≥ 0.5).

[0129] (3) Cost control: β-cyclodextrin encapsulation reduces the enzyme addition amount by 15%, reducing the annual production cost.

[0130] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not used to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions recorded in the foregoing embodiments or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A two-component food detergent with easy rinsing and low 1,4-dioxane, characterized in that It includes alkyl polyglycoside, cocamidopropyl betaine, sodium citrate, lipase, bacteriostat, pH regulator, food-grade ethanol, β-cyclodextrin and deionized water in parts by weight.

2. The easy-rinse low 1,4-dioxane two-component food detergent according to claim 1, wherein Calculated by mass percentage, the food detergent includes the following components: 20-25% of alkyl polyglycoside, 8-12% of cocamidopropyl betaine, 10-15% of sodium lauryl polyoxyethylene ether sulfate, 5-8% of sodium citrate, 1-2% of lipase, 0.5-1% of bacteriostat, 0.5-1% of pH regulator, 3-5% of food-grade ethanol, 2-3% of β-cyclodextrin, 0.5% of biodegradation promoter, 0.5-1% of edible essence, and the balance is deionized water.

3. The easy-to-rinse low 1,4-dioxane two-component food detergent according to claim 1, characterized in that, Calculated by mass percentage, the food detergent includes the following components: 10-15% of alkyl polyglycoside, 5-8% of cocamidopropyl betaine, 2-3% of amine oxide, 5-8% of sodium citrate, 0.5-1% of lipase, 3.1-5.5% of bacteriostat, 5-10% of food-grade ethanol, 2-3% of β-cyclodextrin, 2-4% of pH regulator, 0.5-1% of edible essence, and the balance is deionized water.

4. The easy-rinse low-1,4-dioxane two-component food detergent according to claim 1, wherein Calculated by mass percentage, the food detergent includes the following components: 15-20% of alkyl polyglycoside, 8-12% of cocamidopropyl betaine, 5-8% of sodium citrate, 1-3% of lipase, 2-4% of citric acid, 0.5-1% of bacteriostat, 2-4% of pH regulator, 5-8% of food-grade ethanol, 2-3% of β-cyclodextrin, 1-2% of coconut amide monoethanolamine, 0.5-1% of sodium gluconate, 0.5-1% of edible essence, and the balance is deionized water.

5. The easy-to-rinse low 1,4-dioxane two-component food detergent according to claim 1, characterized in that, The food detergent includes the following components: 12-18% of alkyl polyglycoside, 8-12% of cocamidopropyl betaine, 4-6% of sodium citrate, 0.3-0.7% of lipase, 5-10% of food-grade ethanol, 2-3% of β-cyclodextrin, 2-4% of polyethylene glycol, 0.2-0.4% of silicone ether defoamer, 0.2-0.4% of sodium benzoate, 0.5-1.5% of chitosan quaternary ammonium salt, 2-4% of pH regulator, 1-3% of phytic acid, 0.1-0.3% of edible essence, and the balance is deionized water.

6. A two-component food detergent with easy rinsing and low 1,4-dioxane according to claim 2 or 4, characterized in that, The bacteriostat is one of tea tree oil nanoemulsion, tea tree oil and phenoxyethanol, and the pH regulator is citric acid or citric acid-sodium bicarbonate.

7. An easy-to-rinse low-1,4-dioxane two-component food detergent according to claim 3, characterized in that, The bacteriostat includes natural bacteriostat and synthetic bacteriostat. The natural bacteriostat is honeysuckle extract, and the synthetic bacteriostat is benzalkonium chloride. Among them, the natural bacteriostat is 3-5%, and the synthetic bacteriostat is 0.1-0.5%. The pH regulator is citric acid or citric acid-sodium bicarbonate.

8. A preparation method of an easily rinsable low 1,4-dioxane two-component food detergent for preparing the easily rinsable low 1,4-dioxane two-component food detergent according to any one of claims 1-5, characterized in that, The preparation method includes the following operating steps. S1: Enzyme stabilization pretreatment; β-cyclodextrin and lipase are mixed in a mass ratio and added to a stainless steel reaction kettle. The temperature is set at 45°C, and the rotation speed is 50 rpm. Stir for 30 minutes to form an inclusion complex. S2: Temperature-controlled mixing in stages; SS1: Aqueous phase treatment. Add deionized water at 40 - 45 °C, sodium citrate and food - grade ethanol into a stainless - steel reactor, stir for 20 minutes, cool the deionized water and sodium citrate to 25 °C, add alkyl polyglycoside and betaine to an ultrasonic homogenizer for ultrasonic dispersion. The rotation speed of the ultrasonic homogenizer is 2000 rpm and the homogenization time is 10 minutes; SS2: Add β - cyclodextrin, lipase, and bacteriostatic agent to a thermostatic magnetic stirrer, and maintain the thermostatic magnetic stirrer at 25 °C to avoid enzyme inactivation; SS3: Adjust the pH in three gradients. The gradient is set as 6.0 → 6.5 → 7.

0. Use a pH automatic titrator to add a pH regulator to adjust the pH to 7.0 ± 0.2; S3: Ultrasonic dispersion; Add the remaining substances in the formula and treat with 20 kHz ultrasonic waves for 5 minutes, with an energy density of 0.5 W / cm³; S4: Aseptic filling; After filtration through a 0.22 μm filter membrane, fill under nitrogen protection.

9. The preparation method of a two-component food detergent with easy rinsing and low 1,4-dioxane according to claim 8, characterized in that, After SS2, there is a vacuum degassing step. Set the pressure to - 0.08 MPa and the time to 30 minutes to eliminate the bubbles introduced by stirring and prevent foam overflow during filling.

10. Application of an easily rinsable two-component food detergent with low 1,4-dioxane, comprising the easily rinsable two-component food detergent according to any one of claims 1-5, characterized in that, Application of an easily - rinsed low - 1,4 - dioxane two - component food detergent in the preparation of a detergent.

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