CN111893000B - Non-phosphorus detergent for dish-washing machine and preparation process thereof - Google Patents

Abstract

The invention provides a phosphorus-free detergent for a dish-washing machine, which comprises the following components in percentage by mass: 40-50% of carbonate, 10-20% of bicarbonate, 30-40% of scale scavenger, 0-10% of filler, 2-6% of enzyme preparation, 0.5-1% of propylene glycol ester emulsifier, 0.5-1% of tween emulsifier and 1-3% of terpenoid. The invention also comprises a preparation process of the detergent. The invention adds the terpenoid substance with the six-membered ring structure into the formula of the detergent, and finds an unexpected effect on removing residual pesticide; according to the invention, the propylene glycol ester emulsifier and the tween emulsifier are used as an emulsifier pair, so that a mixture formed by residual pesticide and terpenoid in fruits and vegetables can be effectively emulsified; according to the invention, the mixture of citrate and sodium gluconate is added as a scale scavenger to replace a phosphorus-containing compound, so that a good scale-resistant effect can be achieved, and the water scale inhibitor is environment-friendly and safe.

Description

Non-phosphorus detergent for dish-washing machine and preparation process thereof

Technical Field

The invention relates to the technical field of detergents, in particular to a phosphorus-free detergent for a dish washer and a preparation process thereof.

Background

Household dishwashers are now quite popular abroad as an important member of modern kitchen appliances. The prevalence rate in economically developed european and american countries such as the united states, germany, france, etc. has reached 70%, while the ownership rate of dishwashers in newly built households is higher, estimated to exceed 90%. In asia, the ownership rate of dishwashers in japan is the highest, and the sales of dishwashers in port, australia, tai, and southeast asia have been rapidly increasing in recent years. The dishwasher can meet the high-level requirements of consumers on living health and leisure time enjoyment, and is more suitable for high-rhythm life of modern families. Automatic dish-washing machines are currently used in major restaurants, hotels and canteens in cities in China. From the analysis of the data, the cumulative retail amount of the dishwasher market is 64 hundred million yuan in 2019, the retail quantity is 134.8 ten thousand, and the total retail amount is respectively increased by 24.5 percent and 23.9 percent.

Due to the limitation of the working principle of the dishwasher, the hand washing detergent and the machine washing detergent cannot be mixed. In hand dishwashing, consumers often determine whether the amount of detergent added is sufficient based on the amount of suds. Therefore, hand dishwashing detergents are foamy or even have a certain foam stabilizing property, and moreover, the surfactant content is high, and the surfactant plays a major role in soil removal. Furthermore, hand dishwashing detergents generally do not require the additional use of builders. However, in the machine washing, in order to protect the water pump, prevent overflow, etc., the detergent for the dish washer must be a low-foaming or even non-foaming product, the surfactant plays a more role in surface wetting, and a large amount of builder is required to improve detergency and to achieve a bright and dry appearance of the dishes. Because the organic matter content in the machine washing detergent is low and the surfactant with the functions of penetration, emulsification and solubilization is lacked, the machine washing detergent has poor effect of removing residual pesticides in fruits and vegetables.

Terpenes are a group of hydrocarbons of natural origin that are widely present in plants and can be obtained from many plants, in particular conifers. Terpenoids with small molecular weights, such as monoterpenes and sesquiterpenes, are volatile oily liquids with a characteristic odor and are therefore widely used in perfumery and flavor. At present, no washing agent for dish washing machines, which is added with terpenoids, is available in the market so as to achieve the effect of removing pesticide residues in fruits and vegetables.

Disclosure of Invention

In order to solve the defects and shortcomings of the prior art, the invention provides a phosphorus-free detergent for a dish washer.

The technical scheme adopted by the invention is as follows:

a non-phosphorus detergent for a dish-washing machine comprises the following components in percentage by mass: 40-50% of carbonate, 10-20% of bicarbonate, 30-40% of scale scavenger, 0-10% of filler, 2-6% of enzyme preparation, 0.5-1% of propylene glycol ester emulsifier, 0.5-1% of tween emulsifier and 1-3% of terpenoid.

Further, the terpenoid is at least one of d-limonene, terpinolene, alpha-pinene, beta-pinene, gamma-terpinolene, alpha-terpinolene and 3-carene, and the terpenoids have six-membered ring structures.

Further, the propylene glycol ester emulsifier is at least one of propylene glycol palmitate, propylene glycol arachinate and propylene glycol behenate.

Further, the tween emulsifier is at least one of tween-20, tween-40, tween-60 and tween-80.

Further, the enzyme preparation is at least one of alpha-amylase, beta-amylase, protease, lipase and cellulase.

Specifically, the source of the alpha-amylase is bacillus licheniformis, aspergillus niger, bacillus amyloliquefaciens, bacillus subtilis, rhizopus oryzae, aspergillus oryzae or geobacillus stearothermophilus, and can also be pancreas secretion of pigs or cattle.

Specifically, the source of the beta-amylase is barley, sweet potato, soybean, wheat or malt, and can also be bacillus subtilis.

Specifically, the protease is derived from endoplasmic reticulum, Bacillus licheniformis, Aspergillus niger, Bacillus amyloliquefaciens, Bacillus subtilis, Rhizomucor miehei, Aspergillus oryzae, Kluyveromyces lactis, Mucor minutissima, Aspergillus melleus, or Geobacillus stearothermophilus.

Specifically, the lipase is derived from Aspergillus niger, Rhizopus oryzae, Rhizomucor miehei, Rhizopus niveus, Aspergillus oryzae or Candida cylindracea, can be salivary gland, forestomach tissue or throat secretion of cattle or sheep, and can be pancreatic secretion of pig or cattle.

Specifically, the cellulase is derived from Aspergillus niger, Trichoderma reesei or Trichoderma viride.

Further, the filler is sodium sulfate.

Further, the scale remover is a mixture of citrate and sodium gluconate.

Furthermore, the mass ratio of the citrate to the sodium gluconate is 99: 1-1: 99.

Further, the cation of the carbonate, bicarbonate, and citrate is potassium or sodium.

The invention also comprises a preparation process of the phosphorus-free detergent for the dish-washing machine, which comprises the following steps:

s1, weighing carbonate, bicarbonate, a scale scavenger and a filler required by the product, and putting into a mixer;

s2, mixing a propylene glycol ester emulsifier and a tween emulsifier, and heating the mixed emulsifier to 40-50 ℃;

s3, starting a mixer, and adding the emulsifier mixture and the terpenoid in a spraying mode while mixing;

s4, adding an enzyme preparation, and uniformly stirring;

and S5, sieving the product and packaging.

The selection of the mixer can be a spiral ribbon mixer, a double-cone mixer, a conical double-spiral mixer and other mixing equipment in the prior art, the mixer is provided with 2 or more nozzles, the emulsifier mixture and the terpenoid can be simultaneously and respectively added through the two nozzles, the addition of the emulsifier and the terpenoid is controlled by a metering pump, the mixing time of the enzyme preparation is controlled in order to ensure that the enzyme preparation is uniformly mixed and a coating layer of the enzyme preparation is not damaged, and the emulsifier, the carbonate, the bicarbonate, the scale scavenger, the filler, the emulsifier and the terpenoid are uniformly mixed and then added.

At present, the commonly used organic pesticides such as propoxur, cypermethrin, pyrethrin, kresoxim-methyl, imidacloprid, thiamethoxam and the like in the market have benzene rings or six-membered rings with other structures. The inventor is inspired by the fact that terpenoids with six-membered ring structures are added into the detergent formula disclosed by the invention, and the terpenoids are found to have unexpected effects on removing residual pesticides.

According to the invention, the propylene glycol ester emulsifier and the tween emulsifier are used as an emulsifier pair, so that a mixture formed by residual pesticide and terpenoid in fruits and vegetables can be effectively emulsified.

The invention does not add phosphorus-containing compounds, does not pollute water and does not burden the environment. According to the invention, a mixture of citrate and sodium gluconate is added as a scale scavenger, so that a good scale-resistant effect can be achieved, and the scale remover is environment-friendly and safe.

All the raw materials adopted by the invention are food additives, and completely meet the national safety standard for food.

Detailed Description

All materials, reagents and equipment selected for use in the present invention are well known in the art, but do not limit the practice of the invention, and other reagents and equipment well known in the art may be suitable for use in the practice of the following embodiments of the invention.

Examples

A non-phosphorus detergent for a dish-washing machine comprises the following components in percentage by mass: 40-50% of carbonate, 10-20% of bicarbonate, 30-40% of (citrate + sodium gluconate), 0-10% of sodium sulfate, 2-6% of an enzyme preparation, 0.5-1% of a propylene glycol ester emulsifier, 0.5-1% of a tween emulsifier and 1-3% of terpenoids.

Wherein the terpenoid is at least one of d-limonene, terpinolene, alpha-pinene, beta-pinene, gamma-terpinolene, alpha-terpinolene and 3-carene; the propylene glycol ester emulsifier is at least one of propylene glycol palmitate, propylene glycol arachidate and propylene glycol behenate; the Tween emulsifier is at least one of Tween-20, Tween-40, Tween-60 and Tween-80; the enzyme preparation is at least one of alpha-amylase, beta-amylase, protease, lipase and cellulase; the mass ratio of the citrate to the sodium gluconate is 99: 1-1: 99; the cation of the carbonate, bicarbonate and citrate is potassium or sodium.

The preparation process of the phosphorus-free detergent for the dish washer comprises the following steps:

s1, weighing carbonate, bicarbonate, citrate, sodium gluconate carbonate and sodium sulfate required by the product, and putting into a mixer;

s2, mixing a propylene glycol ester emulsifier and a tween emulsifier, and heating the mixed emulsifier to 40-50 ℃;

s3, starting a mixer, and adding the emulsifier mixture and the terpenoid in a spraying mode while mixing;

s4, adding an enzyme preparation, and uniformly stirring;

and S5, sieving the product and packaging.

The mixer in this embodiment may be a ribbon mixer, a double cone mixer, a conical double screw mixer, or other mixing devices in the prior art, the mixer has 2 or more nozzles, the emulsifier mixture and the terpenoid may be added through two nozzles, respectively, the emulsifier and the terpenoid may be added through a metering pump, the mixing time of the enzyme preparation may be controlled to ensure the enzyme preparation is uniformly mixed without damaging the enzyme preparation coating, and the mixture may be added after the carbonate, the bicarbonate, the scale scavenger, the filler, the emulsifier and the terpenoid are uniformly mixed.

Experiments on pesticide residue effects are performed in examples 1-6, and the specific steps are performed according to GB/T24691-2009-fruit and vegetable detergent appendix A.

The following tests related to detergency of various soils, namely the actual washing effect test of the dishwasher, were also carried out by examples 1 to 6, specifically:

after a certain amount of artificial soil was applied to tableware and washed with a detergent solution for household tableware at a predetermined concentration in a dishwasher, the performance of the detergent, such as removal of soil, was referenced by visual evaluation. Non-stained tableware can also be used as a standard and compared therewith.

1) Reagents and materials

Unless otherwise stated, only distilled or deionized water or water of comparable purity, lard, tallow, refined vegetable oil, milk powder, wheat flour, fresh eggs, tomato ketchup, mustard, tea, oatmeal, citric acid were used in the analysis.

2) Apparatus and device

Analytical balance, tray balance, dishwasher (controllable temperature, dry, can hold 6 sets of tableware at least), thermometer, pig palm oil paint brush, electromagnetic heating agitator, beaker, stainless steel strainer (1mm mesh), rice bowl (114.3mm), vegetable dish (203.2mm, interior concave surface 140mm), glass cup (60mm 130mm), teacup (70mm 50mm), teacup tray (130mm, interior concave surface 95mm), little oval dish (230mm), condiments dish (70mm), soup basin (200mm), chopsticks, soup spoon, soup ladle, knife, fork.

3) Artificial dirt

The artificial dirt is used for coating the vegetable dish and the small oval dish, and the formula of the artificial dirt comprises the following components in percentage by mass: 10% of mixed oil, 15% of wheat flour, 7.5% of whole milk powder, 30% of fresh whole egg liquid, 4% of tomato sauce, 1% of mustard and 32.5% of distilled water. The lard, the beef tallow and the vegetable oil are placed in a beaker according to the mass ratio of 1:1:2, heated to be melted, and stirred uniformly for later use.

Shelling fresh eggs, placing the eggs in a beaker, and uniformly stirring the eggs for later use; mixing wheat flour and whole milk powder; the mixed oil is put in a beaker and heated to 50-60 ℃ for melting. Transferring the uniformly mixed wheat flour and the whole milk powder into a beaker of melted mixed oil for stirring; adding the fresh egg liquid into a beaker in several times and stirring uniformly; adding tomato sauce and mustard, stirring, adding distilled water into beaker, and stirring to obtain fine artificial dirt.

The dishes were first washed in a dishwasher with a 1% citric acid solution, and even new dishes, were washed in the dishwasher before each use, first with a 1% citric acid solution and then with a detergent at the concentrations recommended by the manufacturer, each of which was subjected to a conventional wash cycle. Deionized or distilled water is used in the rinsing process. When there is any stain on the glass, the drying cycle of the dishwasher is not used. No water mark on the glass indicates that the glass is rinsed well. Taking out, washing with distilled water until water drops are not hung, drying in a drying oven, and cooling for later use.

Dipping the artificial dirt with a pig palm oil paint brush, uniformly coating the artificial dirt on the concave central surface of the plate, and placing the plate at the temperature of (25 +/-1) ℃ for 8h for later use after the artificial dirt is coated.

4) Tea stain

The tea stain is used for coating tea cups and tea holders. The preparation process comprises the following steps: in a suitable container, 1000mL of boiling water [ water hardness (2.5. + -. 0.2) mmol/L ] is added to 16g of tea leaves and soaked for 15min, and the tea water is poured into another container through a sieve while stirring. Adding 100mL of filtered tea water into each cup, adding 10mL into each saucer, standing at (25 + -1) ° C for 8h, and discarding the tea water for later use.

5) Oat stain

187mL of deionized water was mixed with 12.5g of oatmeal, and the mixture was boiled for 10min with constant stirring. Smeared with a brush onto the inner surface of the dish. The inner edge of the upper part of the dish was left 20mm free of coating. After smearing, the mixture is placed at the temperature of (25 +/-1) ℃ for 4 hours for standby. 6) The smearing is as follows with reference to table 1:

TABLE 1 stain watch

7) Test procedure

The stained dishware and other utensils were placed in the dishwasher as per the specifications of the dishwasher. The power was turned on and the program was set to a standard washing state for the test. The dish washer is taken out and aired on the bracket quickly after being automatically stopped, and after being cooled to room temperature, the evaluation is carried out according to the specific evaluation mode shown in the table 2 according to the test purpose, and the performance of the detergent is graded. When the surface of the starchy soil is marked visually, an iodine solution (KI-I) can be used₂) Coloring to make the residue more striking. In order to compare the performance difference of the embodiment conveniently, when the dirt is artificial dirt, the round vegetable dish is uniformly used as an evaluation object; when the dirt is oat stain, uniformly using a rice bowl as an evaluation object; when the dirt is tea stain, tea bowls are uniformly used as evaluation objects.

TABLE 2 Performance evaluation Table

The stain removal effect on certain soils was evaluated as: total number of dishes rated for the total number of dishes rated for performance.

The specific components, the added mass percentages, and the experimental results of examples 1-6 are shown in table 3:

table 3 examples 1-6

As can be seen from the table, the ratio of the removal rate of pesticide residues in the above examples 1-6 ranges from 5.4 to 5.7, which is higher than the requirement (not less than 4) in appendix A of GB/T24691-2009 fruit and vegetable cleaning agent.

Comparative example

A phosphorus-free detergent was prepared in a similar manner to the above examples, except that terpenoids and emulsifier pairs (propylene glycol ester emulsifiers and Tween emulsifiers) were not added.

The preparation process of the phosphorus-free detergent comprises the following steps:

s1, weighing carbonate, bicarbonate, citrate, sodium gluconate carbonate and sodium sulfate required by the product, and putting into a mixer;

s2, adding an enzyme preparation, and uniformly stirring;

and S3, sieving the product and packaging.

The following experiments on the pesticide residue effect are carried out by the comparative examples 1-6, and the specific steps are carried out according to GB/T24691-2009-fruit and vegetable cleaning agent appendix A.

Various soil detergency-related tests of dishwasher actual washing effect tests were also carried out below by comparative examples 1 to 6, in the same manner as in the above examples.

The specific ingredients, the mass percentages of additions, and the experimental results of comparative examples 1-6 are shown in table 4:

TABLE 4 comparative examples 1-6

As can be seen from the table, the ratio of the removal rate of pesticide residues in the comparative examples 1 to 6 ranges from 3.5 to 3.8, and is lower than the requirement (not less than 4) in the appendix A of GB/T24691-2009 fruit and vegetable cleaning agent.

As can be seen from examples 1 to 6 and comparative examples 1 to 6, the detergency of the examples was significantly higher than that of the comparative examples.

In conclusion, the phosphorus-free detergent for the dish-washing machine has a good effect of removing pesticide residues on fruits and vegetables, and all the added raw materials are food additives and completely meet the national safety standard for food.

The present invention is not limited to the above-described embodiments, and various modifications and variations of the present invention are intended to be included within the scope of the claims and the equivalent technology of the present invention if they do not depart from the spirit and scope of the present invention.

Claims (7)

1. The phosphorus-free detergent for the dish washer is characterized by comprising the following components in percentage by mass: 40-50% of carbonate, 10-20% of bicarbonate, 30-40% of scale scavenger, 0-10% of filler, 2-6% of enzyme preparation, 0.5-1% of propylene glycol ester emulsifier, 0.5-1% of tween emulsifier and 1-3% of terpenoid; the terpenoid is at least one of d-limonene, terpinolene, alpha-pinene, beta-pinene, gamma-terpinolene, alpha-terpinolene and 3-carene; the propylene glycol ester emulsifier is at least one of propylene glycol palmitate, propylene glycol arachidate and propylene glycol behenate; the Tween emulsifier is at least one of Tween-20, Tween-40, Tween-60 and Tween-80.

2. The phosphorus-free detergent of claim 1, wherein the enzyme preparation is at least one of an alpha-amylase, a beta-amylase, a protease, a lipase, and a cellulase.

3. The phosphorus-free detergent composition as claimed in claim 1, wherein the filler is sodium sulfate.

4. The phosphorus-free detergent of claim 1, wherein the scale remover is a mixture of citrate and sodium gluconate.

5. The phosphorus-free detergent according to claim 4, wherein the mass ratio of the citrate to the sodium gluconate is 99: 1-1: 99.

6. The phosphorus-free detergent composition of claim 5, wherein the cation of said carbonate, bicarbonate or citrate is potassium or sodium.

7. The process for preparing the phosphorus-free detergent for the dish-washing machine as claimed in any one of claims 1 to 6, which comprises the following steps:

s1, weighing carbonate, bicarbonate, a scale scavenger and a filler required by the product, and putting into a mixer;

s2, mixing a propylene glycol ester emulsifier and a tween emulsifier, and heating the mixed emulsifier to 40-50 ℃;

s3, starting a mixer, and adding the emulsifier mixture and the terpenoid in a spraying mode while mixing;

s4, adding an enzyme preparation, and uniformly stirring;

and S5, sieving the product and packaging.