阅读说明：本技术 一种生物酶皂粒 (Biological enzyme soap granules ) 是由 曾君霞 方海洪 赖丽玲 于 2021-10-09 设计创作，主要内容包括：本发明属于日用品技术领域,具体涉及一种生物酶皂粒,该生物酶皂粒原料以质量份计包括以下组分：氢氧化钠10-20份、脂肪酸30-40份、生丝8-13份、棕榈油4-9份、丙二醇3-8份、沸石粉2-7份、螯合剂0.1-0.6份和固定化蛋白酶0.1-0.6份。本发明技术方案中,通过Ru(Ⅱ)介导的光化学方法交联,将蚕丝蛋白-硬脂酸与蚕丝蛋白-蛋白酶之间的络氨酸残基交联成二络氨酸加合物,蚕丝蛋白与蛋白酶之间产生强烈的分子间相互作用,从而增强了蛋白酶对pH的刚性,另外也克服了固定化的蛋白酶在皂粒生产中的逐步释放的问题；相较于传统的通过共价交联固定蛋白酶的技术,本技术方案无需对蛋白质进行复杂且耗时的改性,保留了蛋白酶最好的活性。(The invention belongs to the technical field of daily necessities, and particularly relates to a biological enzyme soap grain, which comprises the following raw materials in parts by mass: 10-20 parts of sodium hydroxide, 30-40 parts of fatty acid, 8-13 parts of raw silk, 4-9 parts of palm oil, 3-8 parts of propylene glycol, 2-7 parts of zeolite powder, 0.1-0.6 part of chelating agent and 0.1-0.6 part of immobilized protease. According to the technical scheme, through Ru (II) -mediated photochemical crosslinking, the complex amino acid residues between fibroin-stearic acid and fibroin-protease are crosslinked into a di-complex amino acid adduct, strong intermolecular interaction is generated between fibroin and protease, so that the rigidity of the protease to pH is enhanced, and the problem of gradual release of immobilized protease in soap grain production is solved; compared with the traditional technology of fixing the protease through covalent crosslinking, the technical scheme does not need to perform complex and time-consuming modification on the protein, and retains the best activity of the protease.)

1. The bio-enzyme soap particles are characterized by comprising the following raw materials in parts by mass: 10-20 parts of sodium hydroxide, 30-40 parts of fatty acid, 8-13 parts of raw silk, 4-9 parts of palm oil, 3-8 parts of propylene glycol, 2-7 parts of zeolite powder, 0.1-0.6 part of chelating agent and 0.1-0.6 part of immobilized protease;

the immobilized protease is prepared by reacting fibroin and stearic acid to generate fibroin-stearic acid, and then carrying out photochemical crosslinking on the fibroin-stearic acid, fibroin and protease mediated by Ru (II).

2. The bio-enzyme soap granule as claimed in claim 1, wherein said chelating agent is one of ethylenediamine-dipolyphosphoric acid sodium acetate, ethylenediamine tetraacetic acid and nitrilotriacetic acid.

3. A process for the preparation of a bio-enzyme soap according to any of claims 1 to 2 comprising the steps of:

(1) weighing the materials according to the components, and premixing the fatty acid, the propylene glycol and the palm oil to obtain a premix;

(2) cutting raw silk into pieces, boiling in 0.05g/L sodium carbonate solution at 90 deg.C for 30min, washing with deionized water, and drying at room temperature for 12 hr to obtain degummed silk;

(3) dissolving degummed silk in Ca (NO)₃)₂Keeping the mixed solution of ethanol and deionized water at 50-70 ℃ for 1-3h, after complete dissolution, centrifuging at 8000rpm at 4 ℃ for 5-15min, dialyzing with a cellulose dialysis membrane for 2-4 days, and replacing deionized water every 6h to obtain a fibroin solution;

(4) dividing the obtained fibroin solution into two parts, one part is fibroin solution A, the other part is fibroin solution B, adding stearic acid into the fibroin solution A, stirring and reacting for 1-2h to obtain fibroin-stearic acid, adding protease into the fibroin solution B, dissolving in phosphate buffer solution, adding ammonium persulfate and [ Ru (bpy)₃]Cl₂Stirring and mixing the solution to obtain fibroin-protease;

(5) mixing the obtained fibroin-stearic acid and fibroin-protease, irradiating for 5-15min by a 100W optical fiber white light source, then uniformly mixing with sodium hydroxide and a chelating agent, adding into the premix, carrying out saponification reaction, adding zeolite powder after the saponification reaction is complete, uniformly mixing to obtain a soap base, and carrying out vacuum spray drying, extrusion, homogenization, refining and grain cutting to obtain a finished product.

4. The method for preparing bio-enzyme soap particles as claimed in claim 3, wherein the mass ratio of the protease, the fibroin solution and the stearic acid is 1: 1-3: 4-8.

5. The process for preparing bio-enzyme soap particles as claimed in claim 3, wherein the temperature of the pre-mixing in step (1) is 60-70 ℃.

6. The method for preparing bio-enzyme soap granules according to claim 3, wherein the mass ratio of raw silk to sodium carbonate solution in the step (2) is 1: 400-500.

7. The process for preparing bio-enzyme soap particles as claimed in claim 3, wherein the deionized water is washed 2-3 times in the step (2).

8. The process for preparing bio-enzyme soap according to claim 3, wherein Ca (NO) in step (3)₃)₂And the mass ratio of the ethanol to the deionized water is 1: 1-3: 7-9.

9. The process for preparing bio-enzyme soap according to claim 3, wherein the fibroin solution in the step (4), phosphate buffer, ammonium persulfate and [ Ru (bpy)₃]Cl₂The mass ratio of (1): 6-8: 10-14: 15-20.

10. The process for preparing bio-enzyme soap particles as claimed in claim 3, wherein the temperature of saponification reaction in step (4) is 80-140 ℃ and the time is 10-60 min.

Technical Field

The invention belongs to the technical field of daily necessities, and particularly relates to a biological enzyme soap grain.

Background

The laundry soap is an indispensable daily chemical in daily life of people. The main function of the current laundry soap is to remove dirt on clothes, and the cleaning principle of the soap is as follows: the soap molecular structure can be divided into two parts, COO with polarity and charge^-(hydrophilic site); the soap can destroy the surface tension of water, when soap molecules enter water, the hydrophilic part with polarity can destroy the attraction among water molecules to reduce the surface tension of water, so that the water molecules are distributed on the surface of clothes or skin to be cleaned almost uniformly, and the lipophilic part can be combined with oil stain on the clothes, so that the oil stain is decomposed into a plurality of small blocks to be washed away with the water.

At present, the laundry soap sold in the market is usually sodium aliphatate, some laundry soaps can achieve the purpose of efficiently removing oil stains by adding various enzymes, in patent document with publication number CN109135971A, an enzyme adjuvant and an enzyme adjuvant stabilizer are added into soap granules, and the purpose of removing the oil stains on clothes is achieved by the enzymatic hydrolysis of the oil stains on the clothes through the enzyme adjuvants, but the following disadvantages exist: 1) the proper pH range of the enzyme auxiliary agent is generally small, and the enzyme auxiliary agent cannot adapt to fluctuation in the soap grain production process, so that enzyme inactivation is caused; 2) the enzyme adjuvant, when mixed with the soap, is not uniformly distributed in the soap.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a bio-enzyme soap grain, which solves the problem that the traditional bio-enzyme soap grain has poor oil stain removal effect.

In order to achieve the purpose, the invention is realized by the following scheme:

the biological enzyme soap grain comprises the following raw materials in parts by mass: 10-22 parts of sodium hydroxide, 30-40 parts of fatty acid, 8-13 parts of raw silk, 4-9 parts of palm oil, 3-8 parts of propylene glycol, 2-7 parts of zeolite powder, 0.1-0.6 part of chelating agent and 0.1-0.6 part of immobilized protease.

Preferably, the chelating agent is one of ethylenediamine-diphenylphosphinic acid sodium, ethylenediamine tetraacetic acid and nitrilotriacetic acid.

The preparation method of the biological enzyme soap particles comprises the following steps:

(1) weighing the materials according to the components, and premixing the fatty acid, the propylene glycol and the palm oil to obtain a premix;

(2) cutting raw silk into pieces, boiling in 0.05g/L sodium carbonate solution at 90 deg.C for 30min, washing with deionized water, and drying at room temperature for 12 hr to obtain degummed silk;

(3) dissolving degummed silk in Ca (NO)₃)₂Keeping the mixed solution of ethanol and deionized water at 50-70 ℃ for 1-3h, after complete dissolution, centrifuging at 8000rpm at 4 ℃ for 5-15min, dialyzing with a cellulose dialysis membrane for 2-4 days, and replacing deionized water every 6h to obtain a fibroin solution;

(4) dividing the obtained fibroin solution into two parts, one part is fibroin solution A, the other part is fibroin solution B, adding stearic acid into the fibroin solution A, stirring and reacting for 1-2h to obtain fibroin-stearic acid, adding protease into the fibroin solution B, dissolving in phosphate buffer solution, adding ammonium persulfate and [ Ru (bpy)₃]Cl₂Stirring and mixing the solution to obtain fibroin-protease;

(5) mixing the obtained fibroin-stearic acid and fibroin-protease, irradiating for 5-15min by a 100W optical fiber white light source, then uniformly mixing with sodium hydroxide and a chelating agent, adding into the premix, carrying out saponification reaction, adding zeolite powder after the saponification reaction is complete, uniformly mixing to obtain a soap base, and carrying out vacuum spray drying, extrusion, homogenization, refining and grain cutting to obtain a finished product.

Preferably, the mass ratio of the protease to the fibroin solution to the stearic acid is 1: 1-3: 4-8.

Preferably, the temperature during the pre-mixing in the step (1) is 60-70 ℃.

Preferably, the mass ratio of the raw silk to the sodium carbonate solution in the step (2) is 1: 400-500.

Preferably, the deionized water is washed for 2 to 3 times in the step (2).

Preferably, Ca (NO) in said step (3)₃)₂And the mass ratio of the ethanol to the deionized water is 1: 1-3: 7-9.

Preferably, the fibroin solution in the step (4), a phosphate buffer solution, ammonium persulfate and [ Ru (bpy)₃]Cl₂The mass ratio of (1): 6-8: 10-14: 15-20.

Preferably, the temperature of the saponification reaction in the step (4) is 80-140 ℃ and the time is 10-60 min. Compared with the prior art, the method has the beneficial effects that:

(1) according to the technical scheme, through Ru (II) -mediated photochemical crosslinking, the complex amino acid residues between fibroin-stearic acid and fibroin-protease are crosslinked into a di-complex amino acid adduct, strong intermolecular interaction is generated between fibroin and protease, so that the rigidity of the protease to pH is enhanced, and the problem of gradual release of immobilized protease in soap grain production is solved; compared with the traditional technology of fixing the protease through covalent crosslinking, the technical scheme does not need to perform complex and time-consuming modification on the protein, and retains the best activity of the protease.

(2) According to the technical scheme, stearic acid and fibroin are combined through amidation reaction between the fibroin and the stearic acid, and the fibroin introduced with the stearic acid has better intermiscibility with fatty acid, so that the fibroin and the fatty acid can be stably dispersed in soap particles, and the fibroin-protease can better exert the enzymolysis effect of the protease in the soap.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The biological enzyme soap grain comprises the following raw materials in parts by mass: 10 parts of sodium hydroxide, 30 parts of fatty acid, 8 parts of raw silk, 4 parts of palm oil, 3 parts of propylene glycol, 2 parts of zeolite powder, 0.1 part of chelating agent and 0.1 part of immobilized protease.

The chelating agent is ethylenediamine-di-o-phenyl sodium acetate.

In this embodiment, the preparation method of the bio-enzyme soap particles includes the following steps:

(1) weighing the materials according to the components, premixing the fatty acid, the propylene glycol and the palm oil at the temperature of 60 ℃ to obtain a premixed solution;

(2) cutting raw silk into blocks, boiling in 0.05g/L sodium carbonate solution at 90 ℃ for 30min, wherein the mass ratio of the raw silk to the sodium carbonate solution is 1: 400, washing with deionized water for 2 times, and drying at room temperature for 12h to obtain degummed silk;

(3) dissolving degummed silk in Ca (NO)₃)₂Ca (NO) in a mixed solution of ethanol and deionized water₃)₂And the mass ratio of the ethanol to the deionized water is 1: 1: 7, keeping the solution at 50 ℃ for 1h, after complete dissolution, centrifuging the solution at 4 ℃ for 5min at 8000rpm, dialyzing the solution for 2 days by using a cellulose dialysis membrane, and replacing deionized water every 6h to obtain a fibroin solution;

(4) dividing the obtained fibroin solution into two parts, wherein one part is fibroin solution A, the other part is fibroin solution B, adding stearic acid into the fibroin solution A, stirring and reacting for 1h to obtain fibroin-stearic acid after the reaction is finished, adding protease into the fibroin solution B, dissolving in phosphate buffer solution, and then adding ammonium persulfate and [ Ru (bpy)₃]Cl₂In solution, fibroin solution, phosphate buffer solution, ammonium persulfate and [ Ru (bpy)₃]Cl₂The mass ratio of (1): 6: 10: and 15, stirring and mixing to obtain fibroin-protease, wherein the mass ratio of the protease to the fibroin solution to the stearic acid is 1: 1: 4;

(5) mixing the obtained fibroin-stearic acid and fibroin-protease, irradiating for 5min by a 100W optical fiber white light source, then uniformly mixing with sodium hydroxide and a chelating agent, adding into the premix, performing saponification reaction at 80 ℃ for 10min, adding zeolite powder after the saponification reaction is complete, uniformly mixing to obtain a soap base, and performing vacuum spray drying, extrusion, homogenization, refining and grain cutting to obtain the finished product.

Example 2

The biological enzyme soap grain comprises the following raw materials in parts by mass: 12 parts of sodium hydroxide, 32 parts of fatty acid, 9 parts of raw silk, 5 parts of palm oil, 4 parts of propylene glycol, 3 parts of zeolite powder, 0.2 part of chelating agent and 0.2 part of immobilized protease.

The chelating agent is ethylenediamine-di-o-phenyl sodium acetate.

In this embodiment, the preparation method of the bio-enzyme soap particles includes the following steps:

(1) weighing the materials according to the components, premixing the fatty acid, the propylene glycol and the palm oil at the temperature of 60 ℃ to obtain a premixed solution;

(2) cutting raw silk into blocks, boiling in 0.05g/L sodium carbonate solution at 90 ℃ for 30min, wherein the mass ratio of the raw silk to the sodium carbonate solution is 1: 450, then washing with deionized water for 3 times, and drying at room temperature for 12h to obtain degummed silk;

(3) dissolving degummed silk in Ca (NO)₃)₂Ca (NO) in a mixed solution of ethanol and deionized water₃)₂And the mass ratio of the ethanol to the deionized water is 1: 2: 8, keeping the solution at 50 ℃ for 1h, after complete dissolution, centrifuging the solution at 4 ℃ for 5min at 8000rpm, dialyzing the solution for 2 days by using a cellulose dialysis membrane, and replacing deionized water every 6h to obtain a fibroin solution;

(4) dividing the obtained fibroin solution into two parts, wherein one part is fibroin solution A, the other part is fibroin solution B, adding stearic acid into the fibroin solution A, stirring and reacting for 1h to obtain fibroin-stearic acid after the reaction is finished, adding protease into the fibroin solution B, dissolving in phosphate buffer solution, and then adding ammonium persulfate and [ Ru (bpy)₃]Cl₂In solution, fibroin solution, phosphate buffer solution, ammonium persulfate and [ Ru (bpy)₃]Cl₂The mass ratio of (1): 7: 12: 17, stirring and mixing to obtain fibroin-protease, fibroin solution and stearic acidThe mass ratio is 1: 2: 6.

(5) mixing the obtained fibroin-stearic acid and fibroin-protease, irradiating for 5min by a 100W optical fiber white light source, then uniformly mixing with sodium hydroxide and a chelating agent, adding into the premix, performing saponification reaction at 110 ℃ for 30min, adding zeolite powder after the saponification reaction is complete, uniformly mixing to obtain a soap base, and performing vacuum spray drying, extrusion, homogenization, refining and grain cutting to obtain the finished product.

Example 3

The biological enzyme soap grain comprises the following raw materials in parts by mass: 14 parts of sodium hydroxide, 34 parts of fatty acid, 10 parts of raw silk, 6 parts of palm oil, 5 parts of propylene glycol, 4 parts of zeolite powder, 0.3 part of chelating agent and 0.3 part of immobilized protease.

The chelating agent is ethylenediamine-di-o-phenyl sodium acetate.

In this embodiment, the preparation method of the bio-enzyme soap particles includes the following steps:

(1) weighing the materials according to the components, premixing the fatty acid, the propylene glycol and the palm oil at the temperature of 60 ℃ to obtain a premixed solution;

(2) cutting raw silk into blocks, boiling in 0.05g/L sodium carbonate solution at 90 ℃ for 30min, wherein the mass ratio of the raw silk to the sodium carbonate solution is 1: 500, washing with deionized water for 3 times, and drying at room temperature for 12h to obtain degummed silk;

(3) dissolving degummed silk in Ca (NO)₃)₂Ca (NO) in a mixed solution of ethanol and deionized water₃)₂And the mass ratio of the ethanol to the deionized water is 1: 3: 9, keeping the solution at 50 ℃ for 1h, after complete dissolution, centrifuging the solution at 4 ℃ for 5min at 8000rpm, dialyzing the solution for 2 days by using a cellulose dialysis membrane, and replacing deionized water every 6h to obtain a fibroin solution;

(4) dividing the obtained fibroin solution into two parts, one part is fibroin solution A, the other part is fibroin solution B, adding stearic acid into fibroin solution A, stirring and reacting for 1h to obtain fibroin-stearic acid, adding protease into fibroin solution B, and dissolving in phosphate bufferTo the solution, ammonium persulfate and [ Ru (bpy) ]were added₃]Cl₂In solution, fibroin solution, phosphate buffer solution, ammonium persulfate and [ Ru (bpy)₃]Cl₂The mass ratio of (1): 8: 14: 20, stirring and mixing to obtain fibroin-protease, wherein the mass ratio of the protease to the fibroin solution to the stearic acid is 1: 3: 8.

(5) mixing the obtained fibroin-stearic acid and fibroin-protease, irradiating for 5min by a 100W optical fiber white light source, then uniformly mixing with sodium hydroxide and a chelating agent, adding into the premix, performing saponification reaction at 140 ℃ for 60min, adding zeolite powder after the saponification reaction is complete, uniformly mixing to obtain a soap base, and performing vacuum spray drying, extrusion, homogenization, refining and grain cutting to obtain the finished product.

Example 4

The biological enzyme soap grain comprises the following raw materials in parts by mass: 16 parts of sodium hydroxide, 36 parts of fatty acid, 11 parts of raw silk, 7 parts of palm oil, 6 parts of propylene glycol, 5 parts of zeolite powder, 0.4 part of chelating agent and 0.4 part of immobilized protease.

The chelating agent is ethylenediamine-di-o-phenyl sodium acetate.

In this embodiment, the preparation method of the bio-enzyme soap particles includes the following steps:

(1) weighing the materials according to the components, premixing the fatty acid, the propylene glycol and the palm oil at the temperature of 60 ℃ to obtain a premixed solution;

(2) cutting raw silk into blocks, boiling in 0.05g/L sodium carbonate solution at 90 ℃ for 30min, wherein the mass ratio of the raw silk to the sodium carbonate solution is 1: 500, washing with deionized water for 3 times, and drying at room temperature for 12h to obtain degummed silk;

(3) dissolving degummed silk in Ca (NO)₃)₂Ca (NO) in a mixed solution of ethanol and deionized water₃)₂And the mass ratio of the ethanol to the deionized water is 1: 3: 9, keeping the solution at 50 ℃ for 1h, after complete dissolution, centrifuging the solution at 4 ℃ for 5min at 8000rpm, dialyzing the solution for 2 days by using a cellulose dialysis membrane, and replacing deionized water every 6h to obtain a fibroin solution;

(4) dividing the obtained fibroin solution into two parts, wherein one part is fibroin solution A, the other part is fibroin solution B, adding stearic acid into the fibroin solution A, stirring and reacting for 1h to obtain fibroin-stearic acid after the reaction is finished, adding protease into the fibroin solution B, dissolving in phosphate buffer solution, and then adding ammonium persulfate and [ Ru (bpy)₃]Cl₂In solution, fibroin solution, phosphate buffer solution, ammonium persulfate and [ Ru (bpy)₃]Cl₂The mass ratio of (1): 8: 14: 20, stirring and mixing to obtain fibroin-protease, wherein the mass ratio of the protease to the fibroin solution to the stearic acid is 1: 3: 8.

(5) mixing the obtained fibroin-stearic acid and fibroin-protease, irradiating for 5min by a 100W optical fiber white light source, then uniformly mixing with sodium hydroxide and a chelating agent, adding into the premix, performing saponification reaction at 140 ℃ for 60min, adding zeolite powder after the saponification reaction is complete, uniformly mixing to obtain a soap base, and performing vacuum spray drying, extrusion, homogenization, refining and grain cutting to obtain the finished product.

Example 5

The biological enzyme soap grain comprises the following raw materials in parts by mass: 18 parts of sodium hydroxide, 38 parts of fatty acid, 12 parts of raw silk, 8 parts of palm oil, 7 parts of propylene glycol, 6 parts of zeolite powder, 0.5 part of chelating agent and 0.5 part of immobilized protease.

The chelating agent is ethylenediamine-di-o-phenyl sodium acetate.

In this embodiment, the preparation method of the bio-enzyme soap particles includes the following steps:

(1) weighing the materials according to the components, premixing the fatty acid, the propylene glycol and the palm oil at the temperature of 60 ℃ to obtain a premixed solution;

(2) cutting raw silk into blocks, boiling in 0.05g/L sodium carbonate solution at 90 ℃ for 30min, wherein the mass ratio of the raw silk to the sodium carbonate solution is 1: 500, washing with deionized water for 3 times, and drying at room temperature for 12h to obtain degummed silk;

(3) dissolving degummed silk in Ca (NO)₃)₂Ethanol and deionizationCa (NO) in the mixed solution of water₃)₂And the mass ratio of the ethanol to the deionized water is 1: 3: 9, keeping the solution at 50 ℃ for 1h, after complete dissolution, centrifuging the solution at 4 ℃ for 5min at 8000rpm, dialyzing the solution for 2 days by using a cellulose dialysis membrane, and replacing deionized water every 6h to obtain a fibroin solution;

(4) dividing the obtained fibroin solution into two parts, wherein one part is fibroin solution A, the other part is fibroin solution B, adding stearic acid into the fibroin solution A, stirring and reacting for 1h to obtain fibroin-stearic acid after the reaction is finished, adding protease into the fibroin solution B, dissolving in phosphate buffer solution, and then adding ammonium persulfate and [ Ru (bpy)₃]Cl₂In solution, fibroin solution, phosphate buffer solution, ammonium persulfate and [ Ru (bpy)₃]Cl₂The mass ratio of (1): 8: 14: 20, stirring and mixing to obtain fibroin-protease, wherein the mass ratio of the protease to the fibroin solution to the stearic acid is 1: 3: 8.

(5) mixing the obtained fibroin-stearic acid and fibroin-protease, irradiating for 5min by a 100W optical fiber white light source, then uniformly mixing with sodium hydroxide and a chelating agent, adding into the premix, performing saponification reaction at 140 ℃ for 60min, adding zeolite powder after the saponification reaction is complete, uniformly mixing to obtain a soap base, and performing vacuum spray drying, extrusion, homogenization, refining and grain cutting to obtain the finished product.

Example 6

The biological enzyme soap grain comprises the following raw materials in parts by mass: 20 parts of sodium hydroxide, 40 parts of fatty acid, 13 parts of palm fiber, 9 parts of palm oil, 8 parts of propylene glycol, 7 parts of zeolite powder, 0.6 part of chelating agent and 0.6 part of immobilized protease.

The chelating agent is ethylenediamine-di-o-phenyl sodium acetate.

In this embodiment, the preparation method of the bio-enzyme soap particles includes the following steps:

(1) weighing the materials according to the components, premixing the fatty acid, the propylene glycol and the palm oil at the temperature of 60 ℃ to obtain a premixed solution;

(2) cutting raw silk into blocks, boiling in 0.05g/L sodium carbonate solution at 90 ℃ for 30min, wherein the mass ratio of the raw silk to the sodium carbonate solution is 1: 500, washing with deionized water for 3 times, and drying at room temperature for 12h to obtain degummed silk;

(3) dissolving degummed silk in Ca (NO)₃)₂Ca (NO) in a mixed solution of ethanol and deionized water₃)₂And the mass ratio of the ethanol to the deionized water is 1: 3: 9, keeping the solution at 50 ℃ for 1h, after complete dissolution, centrifuging the solution at 4 ℃ for 5min at 8000rpm, dialyzing the solution for 2 days by using a cellulose dialysis membrane, and replacing deionized water every 6h to obtain a fibroin solution;

(4) dividing the obtained fibroin solution into two parts, wherein one part is fibroin solution A, the other part is fibroin solution B, adding stearic acid into the fibroin solution A, stirring and reacting for 1h to obtain fibroin-stearic acid after the reaction is finished, adding protease into the fibroin solution B, dissolving in phosphate buffer solution, and then adding ammonium persulfate and [ Ru (bpy)₃]Cl₂In solution, fibroin solution, phosphate buffer solution, ammonium persulfate and [ Ru (bpy)₃]Cl₂The mass ratio of (1): 8: 14: 20, stirring and mixing to obtain fibroin-protease, wherein the mass ratio of the protease to the fibroin solution to the stearic acid is 1: 3: 8.

(5) mixing the obtained fibroin-stearic acid and fibroin-protease, irradiating for 5min by a 100W optical fiber white light source, then uniformly mixing with sodium hydroxide and a chelating agent, adding into the premix, performing saponification reaction at 140 ℃ for 60min, adding zeolite powder after the saponification reaction is complete, uniformly mixing to obtain a soap base, and performing vacuum spray drying, extrusion, homogenization, refining and grain cutting to obtain the finished product.

Comparative example 1

This comparative example is a commercially available compound soap pellet.

The finished products from examples 1 to 6 and comparative examples were tested according to the following test items in Table 1:

TABLE 1

The test results are shown in table 2 below:

TABLE 2

As can be seen from table 2, the bio-enzyme soap particles prepared according to the technical scheme of the present invention have better fluidity, caking property, detergency, solubility and active content compared to the comparative examples by adding immobilized protease.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.