Preparation method of chlorophyllin copper potassium salt

Abstract

The invention discloses a preparation method of chlorophyllin copper potassium salt, which comprises the following steps: (1) pretreatment of coarse silkworm excrement: screening, winnowing, crushing and screening the coarse silkworm excrement to obtain purified silkworm excrement powder; (2) impurity removal by a water method and acidic copper substitution: adjusting the pH value of the silkworm excrement powder, heating, carrying out copperization, carrying out water extraction and separating to obtain a precipitate; (3) drying and organic solvent extraction: performing vacuum drying on the precipitate, and extracting and separating with an organic solvent to obtain an organic solvent extracting solution; (4) saponification and precipitation: carrying out vacuum concentration on the extracting solution, heating and saponifying with potassium hydroxide, cooling and separating to obtain a chlorophyll copper potassium salt crude product; and (5) washing and drying the crude product: carrying out low-temperature washing, separation and vacuum drying on the crude product by using an organic solvent to obtain the chlorophyllin copper potassium salt product. The method is easy to implement, convenient to operate, outstanding in product characteristic, easy in equipment type selection and matching, high in product additional value and good in economic benefit, and the prepared potassium copper chlorophyllin is high in yield, high in purity, high in sanitary safety, good in solubility and low in cost and can be used for mechanically preparing the potassium copper chlorophyllin.

Description

Technical Field

[0001] The present invention relates to the technical field of deep processing of natural pigments, and more specifically to a method for manufacturing potassium copper chlorophyllin, which is applicable to manufacturing potassium copper chlorophyllin or sodium copper chlorophyllin by using silkworm excrement and processing waste of agricultural and sideline products rich in chlorophyll or waste Chinese medicinal herb residues as raw materials. Background Art

[0002] Silkworm excrement is the dried feces discharged by the larvae of Bombycidae insects, presenting a granular shape. Silkworm excrement contains rich active substances and medicinal components. According to statistics, in 2021 alone, the mulberry field area in Guangxi reached as high as 191,800 hectares, the output of silkworm cocoons was 407,400 tons, and the output of silkworm excrement was over 1.5 million tons, with extremely rich silkworm excrement resources. However, the current utilization rate of silkworm excrement is low, and most of the silkworm excrement is treated as fertilizer, and its own value has not been fully reflected. The resulting waste of resources and environmental pollution are problems that need to be solved urgently. The chemical compositions of silkworm excrement at different instars and from different producing areas have certain differences. According to analysis and determination, the contents of nitrogen-free extractives soluble in water, fat, protein, ash, crude fiber, total flavonoids, and β-carotene in silkworm excrement from the 3rd to 5th instars produced in Guangxi are 40.0% - 42.3%, 4.4% - 7.3%, 12.2% - 14.4%, 14.4% - 15.7%, 16.1% - 17.5%, 1.13% - 2.21%, and 9.5 - 14.8 mg / 100 g respectively. Using silkworm excrement as raw material, chlorophyll and its derivatives, phytol (phytyl alcohol, leaf alcohol or chlorophyllol), pectin, folic acid, 1-deoxynojirimycin (DNJ), 1-tritriacontanol, alkaloids, flavonoids and other substances can be extracted.

[0003] Silkworms feed on fresh mulberry leaves, producing silkworm cocoons (silk) and excreting feces (silkworm excrement). Fresh mulberry leaves contain chlorophyll and chloroplasts distributed with chlorophyllase. Chlorophyll is a magnesium porphyrin compound, including chlorophyll a, b, c, d, and f, with chlorophyll a being the main component. Chemically speaking, chlorophyll is a diester of chlorophyllic acid. Chlorophyllic acid is a dicarboxylic acid containing a lactone bond, one of the carboxyl groups is esterified with methanol, and the other is esterified with phytol (or called leaf alcohol, phytyl alcohol, chlorophyllol) (see Figure 1 left). The research by Zheng Tianyao on extracting chlorophyll from silkworm excrement with organic solvents proves that for the same batch of silkworms fed with the same kind of mulberry leaves, the chlorophyll content in the produced silkworm excrement is closely related to the instar of the silkworms, and the chlorophyll content in the silkworm excrement of the 3rd instar is the highest. Different researchers use different methods, and there are significant differences in the extraction rate of chlorophyll and the yield of preparing sodium copper chlorophyllin from silkworm excrement. Summary of the Invention

[0004] Aiming at the deficiencies existing in the existing technologies for producing sodium copper chlorophyllin and potassium copper chlorophyllin from silkworm excrement, the purpose of the present invention is to provide a method for manufacturing potassium copper chlorophyllin. This method is easy to implement, convenient to operate, with prominent product features, easy equipment selection and matching, less equipment investment, high product added value, good economic benefits, and can be mechanized. The present invention uses dried silkworm excrement that has been purified, copperized, and has removed water-soluble impurities under acidic heating conditions as raw materials, and adopts the methods of organic solvent extraction and potassium hydroxide saponification to manufacture potassium copper chlorophyllin. The technical solution is reasonable, extracting both chlorophyll and dephytylated chlorophyll from silkworm excrement. The extraction rate of total chlorophyll is high, and the potassium copper chlorophyllin manufactured has a high yield, high purity, high hygienic safety, good solubility, and low cost, and potassium copper chlorophyllin can be mechanized manufactured.

[0005] In order to achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0006] The applicant of this application, through a large number of repeated experimental studies, first discovered that: during the process of digesting fresh mulberry leaves and forming wet silkworm excrement (feces), due to the destruction of the cell structure of fresh mulberry leaves, chlorophyllase (EC 3.1.1.14) in chloroplasts is released, hydrolyzing chlorophyll to generate dephytylated chlorophyll (i.e., dephytylated chlorophyll monoacid or dechlorophyllized chlorophyll monoacid, see Figure 1 lower right) and phytol (phytyl alcohol, phytol, chlorophyllol, see Figure 1 upper right); (wet) silkworm excrement contains both more than 3.32% calcium ions and relatively high contents of divalent or higher-valent metal ions such as magnesium ions, iron ions, and zinc ions. Dephytylated chlorophyll monoacid reacts with divalent and higher-valent metal ions such as calcium ions in silkworm excrement to form calcium salts of dephytylated chlorophyll monoacid that are insoluble in both water and organic solvents. The longer the silkworm age, the more chlorophyll in silkworm excrement is hydrolyzed by chlorophyllase to form calcium salts of dephytylated chlorophyll monoacid, resulting in a lower extraction rate of chlorophyll in silkworm excrement and a lower yield of sodium copper chlorophyllin prepared.

[0007] The applicant of this application also, through a large number of repeated experimental studies, first discovered that: due to the presence of calcium carbonate (CaCO3) in the cystoliths of fresh mulberry leaves, silkworm excrement contains a large amount of carbonates such as calcium carbonate. Depending on the origin and silkworm age differences, silkworm excrement usually contains 0.8 - 2.0% chlorophyll and is the preferred raw material for preparing chlorophyll and chlorophyll derivatives such as sodium copper chlorophyllin. The magnesium in chlorophyll can be replaced by copper to form copper chlorophyll. Copper chlorophyll contains a phytol ester bond, a methanol ester bond, and a lactone bond, and can be saponified by potassium hydroxide to form dipotassium copper chlorophyllate ( Figure 2 left, or dipotassium copper chlorophyllin) and tripotassium copper chlorophyllate ( Figure 2Right, or tripotassium copper chlorophyllin), potassium copper chlorophyllin is a mixture of dipotassium copper chlorophyllide and tripotassium copper chlorophyllide. Potassium copper chlorophyllin is a similar product to sodium copper chlorophyllin and is also an upgraded and replacement product of sodium copper chlorophyllin. It has various application prospects such as coloring, health care, and treatment in the fields of food, health products, medicine, and agriculture.

[0008] The technical concept of the present invention is as follows: The present invention utilizes the fact that the solid impurities in crude silkworm excrement that are not silkworm excrement can be separated by physical methods. The phytyl chlorophyllin monoacid in silkworm excrement can be converted into water-insoluble phytyl chlorophyllin monoacid under acidic conditions. Calcium carbonate, calcium oxalate, and calcium pectate in silkworm excrement can be converted into water-soluble calcium chloride under acidic conditions. Chlorophyll and phytyl chlorophyllin monoacid in silkworm excrement can be demagnesiated and copperated into copper chlorophyll and copper phytyl chlorophyllin monoacid under acidic heating conditions. Copper chlorophyll and copper phytyl chlorophyllin monoacid are insoluble in water, and excessive copper ions can be dissolved in water and separated under acidic conditions. The water-soluble impurities in silkworm excrement that are not chlorophyll can be dissolved in water and separated under acidic heating conditions. Copper chlorophyll and copper phytyl chlorophyllin monoacid can be extracted by organic solvents and saponified with potassium hydroxide under heating conditions into potassium copper chlorophyllin that is insoluble in organic solvents such as isopropanol at low temperature, and the impurity components such as potassium fatty acid, phytol, methanol, glycerol, lutein, carotenoid, sterol, and flavonoid in the saponification solution are soluble in organic solvents such as isopropanol. After the crude silkworm excrement is screened, air-selected, and pulverized and screened, purified silkworm excrement powder is obtained; the purified silkworm excrement powder is subjected to impurity removal by heating with acidic water and acidic copperation, and the precipitate obtained after separating all the water-soluble impurities that are soluble in water under acidic heating conditions is dried to obtain purified and copperated silkworm excrement; the purified and copperated silkworm excrement is extracted with organic solvents to obtain copper chlorophyll and copper phytyl chlorophyllin monoacid, and an organic solvent extract is obtained; the organic solvent extract is concentrated, saponified, cooled and precipitated, washed with organic solvents, and dried to obtain the potassium copper chlorophyllin product.

[0009] A method for manufacturing potassium copper chlorophyllin, comprising the following steps:

[0010] (1) Pretreatment of crude silkworm excrement: Take dry crude silkworm excrement, screen out large particle solid impurities such as residual mulberry branches, mulberry leaves, mulberry leaf stalks, rice straw, and nylon ropes in the crude silkworm excrement with a stainless steel sieve with a diameter of 3.5 - 4.5 mm, and then use an air separator to remove solid impurities such as soil, sediment, lime, small broken mulberry leaves, and mulberry stalks and branches (small broken mulberry leaves, mulberry stalks, and branches refer to the very small particles of broken mulberry leaves, mulberry stalks, and branches, the same below) in the crude silkworm excrement to obtain purified silkworm excrement; pulverize the purified silkworm excrement with a stainless steel pulverizer and screen it through a 2 - 60 mesh standard sieve to obtain purified silkworm excrement powder for standby;

[0011] (2) Acidic aqueous method for impurity removal and acidic copper substitution: Take the purified silkworm excrement powder obtained in step (1), soak it in water with a mass multiple of 10 - 20 times that of the silkworm excrement powder for 0.5 - 3 hours to fully absorb water and expand. Then, under stirring, adjust the pH to 1.5 - 1.9 with dilute hydrochloric acid to convert the phytyl chlorophyll monoacid in the silkworm excrement into water-insoluble phytyl chlorophyll monoacid, decompose and convert the carbonates such as calcium carbonate and magnesium carbonate insoluble in water in the silkworm excrement into water-soluble hydrochlorides such as calcium chloride and magnesium chloride, and convert the oxalates, sulfates, phosphates, pectates, etc. of divalent and higher metal ions such as calcium ions in the silkworm excrement into water-soluble hydrochlorides. After continuing to stir for 0.5 - 1 hour, readjust and maintain the pH at 1.5 - 1.9; add solid copper chloride with a mass fraction of 0.1% - 1.5% of the silkworm excrement powder, stir to dissolve and mix evenly; under stirring, heat to a temperature of 80 - 90 °C and stir for 0.5 - 2 hours to demagnesium and copper-substitute the chlorophyll and phytyl chlorophyll monoacid in the silkworm excrement, converting them into copper-substituted chlorophyll and copper-substituted phytyl chlorophyll monoacid, extract the impurities soluble in water under acidic heating conditions including all ash in the silkworm excrement, and extract the toxic and harmful components in the silkworm excrement (feces); filter or centrifuge to obtain the supernatant and precipitate; discard the supernatant, dissolve and disperse the precipitate evenly in water with a mass multiple of 5 - 10 times that of the silkworm excrement powder, and perform the second and third water extractions under the conditions of a temperature of 80 - 90 °C, a pH of 1.5 - 1.9, and a stirring time of 0.5 - 1 hour to fully separate all water-soluble impurities including calcium ions and copper ions, filter or centrifuge to obtain the supernatant and precipitate; discard the supernatant, and keep the precipitate for later use;

[0012] (3) Precipitate drying and organic solvent extraction: Take the precipitate obtained in step (2), dry it to a water content of less than 4% at a temperature of 40 - 60 °C by vacuum drying (ordinary, the same below) to obtain the purified and copper-substituted silkworm excrement; under the conditions of a mass ratio of purified and copper-substituted dried silkworm excrement: organic solvent = 1:2 - 6, a temperature of 20 - 50 °C, and a stirring extraction time of 0.5 - 2.5 hours, extract the copper-substituted chlorophyll and copper-substituted phytyl chlorophyll monoacid three times with an organic solvent, filter or centrifuge separately, discard the precipitate, reuse the third organic solvent extraction solution, and combine the first two organic solvent extraction solutions to obtain the organic solvent extraction solution of copper-substituted chlorophyll and copper-substituted phytyl chlorophyll monoacid for later use;

[0013] (4) Saponification and precipitation of the organic solvent extract: Take the organic solvent extract obtained in step (3), concentrate it to 1 / 2 to 1 / 4 of its volume by vacuum concentration to obtain a concentrated solution of the organic solvent extract. Add solid potassium hydroxide with a mass fraction of 1.0% - 10% of the concentrated solution, stir to dissolve, heat to 50 - 59 °C and stir for 0.5 - 5.5 hours to saponify copper chlorophyll and copper phytolide monoacid to form dipotassium copper chlorophyllate (or copper chlorophyllin dipotassium) and tripotassium copper chlorophyllate (or copper chlorophyllin tripotassium) that are slightly soluble in organic solvents, namely copper potassium chlorophyllate; after the saponification is completed, under stirring conditions, cool the saponified solution to 0 - 20 °C and continue to stir for 1.0 - 10.0 hours to fully precipitate and separate out copper potassium chlorophyllate; filter or centrifuge to separate, discard the supernatant, and obtain the crude product of copper potassium chlorophyllate for standby;

[0014] (5) Organic solvent washing and drying: Take the crude product of copper potassium chlorophyllate obtained in step (4), use an organic solvent with a multiple of 0.3 - 1.5 times the mass of the crude product of copper potassium chlorophyllate, and stir and wash the crude product of copper potassium chlorophyllate at a temperature of 0 - 20 °C for 0.5 - 1.0 hour to dissolve and separate residual impurity components such as potassium fatty acid, phytol, methanol, glycerol, lutein, carotenoid, sterol, and flavonoid in the crude product of copper potassium chlorophyllate. Wash 1 - 2 times, filter or centrifuge to separate, discard the supernatant, and obtain the wet refined product of copper potassium chlorophyllate. Use vacuum drying (ordinary) at a temperature of 30 - 50 °C to remove the residual organic solvent in the wet refined product of copper potassium chlorophyllate, and thus obtain the product of copper potassium chlorophyllate.

[0015] Preferably: The crude silkworm excrement described in step (1) is non - purified silkworm excrement with a water content percentage ≤ 5%.

[0016] More preferably, the crude silkworm excrement described in step (1) is non - purified silkworm excrement with a water content percentage ≤ 4%.

[0017] Preferably: The copper chloride described in step (2) is copper chloride of analytical purity, chemical purity, and industrial grade.

[0018] More preferably, the copper chloride described in step (2) is copper chloride of analytical purity.

[0019] Preferably: The organic solvent described in steps (3) and (5) is any one of isopropanol, absolute ethanol, and propanol.

[0020] More preferably, the organic solvent described in steps (3) and (5) is isopropanol.

[0021] In addition, the present invention also claims to protect the copper potassium chlorophyllate manufactured by the described manufacturing method.

[0022] Compared with the prior art, the advantages and beneficial effects of the method of the present invention are as follows:

[0023] (1) The crude silkworm excrement contains 10-30% of solid impurities other than silkworm excrement. By screening to remove large particle solid impurities such as residual mulberry branches, residual mulberry leaves, residual mulberry stalks, rice straw and nylon ropes in the crude silkworm excrement, and by pneumatic separation to remove solid impurities with high density such as soil, sediment and lime in the crude silkworm excrement, as well as solid impurities with relatively low density such as fine broken mulberry leaves, mulberry stalks and mulberry branches, the technical problem that it is difficult to separate the crude silkworm excrement from non-silkworm excrement solid impurities such as sediment, residual mulberry stalks, residual mulberry branches and broken leaves is solved, achieving the technical effects of purifying the crude silkworm excrement, reducing the mass of the crude silkworm excrement by 10-30%, reducing the usage amount of subsequent extraction solvents, improving the extraction efficiency of subsequent copperized chlorophyll and copperized monophyllic dephytylated chlorophyll, and reducing the cost of preparing potassium copper chlorophyllin.

[0024] (2) Acidic water method for impurity removal is one of the most critical technical treatments of the present invention. Since fresh mulberry leaves contain chlorophyllase, silkworm excrement contains both chlorophyll and chlorophyllide monoacid and its salts. At the same time, silkworm excrement contains about 60% of impurities that are soluble in water under acidic heating conditions, including non-chlorophyll and chlorophyllide monoacid. The method of the present invention uses dilute hydrochloric acid to adjust the pH to 1.5 - 1.9 for three times of heating water extraction, converts the chlorophyllide monoacid salts in silkworm excrement into water-insoluble chlorophyllide monoacid, decomposes and converts the water-insoluble carbonates such as calcium carbonate and magnesium carbonate in silkworm excrement into water-soluble hydrochlorides such as calcium chloride and magnesium chloride, converts the oxalates, sulfates, phosphates, pectates, etc. of divalent and higher metal ions such as calcium ions in silkworm excrement into water-soluble hydrochlorides, extracts the impurities that are soluble in water under acidic heating conditions including all ash in silkworm excrement and the toxic and harmful components in silkworm excrement (feces), and fully separates all water-soluble impurity components including calcium ions and excess copper ions. This technical treatment solves the technical problems of difficult separation of divalent and higher metal ion salts including calcium salts in silkworm excrement, difficult separation of toxic and harmful components in silkworm excrement (feces), loss of chlorophyllide monoacid salts with water (such as sodium chlorophyllide monoacid or potassium chlorophyllide monoacid dissolved in water) or inability to extract with organic solvents (such as calcium chlorophyllide monoacid, magnesium chlorophyllide monoacid, zinc chlorophyllide monoacid, iron chlorophyllide monoacid, and copper chlorophyllide monoacid insoluble in organic solvents). It achieves the technical effects of fully separating the water-soluble impurities of non-chlorophyll and chlorophyllide monoacid in silkworm excrement, reducing the mass of silkworm excrement by about 60%, significantly reducing the usage amount of subsequent extraction solvents, improving the extraction efficiency of subsequent copperized chlorophyll and copperized chlorophyllide monoacid, avoiding the reaction of residual calcium ions and copper ions with potassium copper chlorophyllin salt during the subsequent saponification process to form calcium copper chlorophyllin salt and copper copper chlorophyllin salt that are insoluble in both water and organic solvents, increasing the yield of potassium copper chlorophyllin salt, reducing the cost of preparing potassium copper chlorophyllin salt, and improving the hygienic safety of potassium copper chlorophyllin salt. Through the technical treatments of acidic water method for impurity removal and acidic copper substitution, the impurities in silkworm excrement are fully removed, the mass of silkworm excrement is reduced by about 60%, the chlorophyll content in silkworm excrement is increased by 2.5 times, and the chlorophyll and chlorophyllide monoacid in silkworm excrement are 100% utilized.

[0025] (3) The acid copper substitution of chlorophyll and chlorophyllide a is one of the most critical technical treatments of the present invention. By means of the method of the present invention, in an aqueous environment heated with dilute hydrochloric acid adjusted to a pH of 1.5 - 1.9, chlorophyll and chlorophyllide a are converted into pheophytin and pheophorbide a. Without using an organic solvent to extract chlorophyll and chlorophyllide a from silkworm excrement, the technical treatment of selectively copper substituting the pheophytin and pheophorbide a that have been demetallized in silkworm excrement with copper chloride to form copper chlorophyll and copper pheophorbide a solves the technical problem that chlorophyll must be extracted with an organic solvent first before copper substitution, achieving the technical effects of copper substituting both chlorophyll and chlorophyllide a, improving the extraction efficiency of subsequent copper chlorophyll and copper pheophorbide a, increasing the yield of subsequent preparation of potassium copper chlorophyllin, and reducing the cost of preparing potassium copper chlorophyllin. The copper substitution rate of chlorophyll and chlorophyllide a is 100%.

[0026] (4) By means of the method of the present invention, through the technical treatment of saponifying copper chlorophyll and copper pheophorbide a in the concentrated organic solvent extract and lowering the temperature to reduce the solubility of potassium copper chlorophyllin, which is slightly soluble in the organic solvent, the technical problems of insufficient precipitation and low yield caused by the slight solubility of potassium copper chlorophyllin in the organic solvent at room temperature are solved, achieving the technical effects of increasing the yield of potassium copper chlorophyllin and reducing the cost of preparing potassium copper chlorophyllin.

[0027] (5) Compared with the prior art, the progress of the present invention lies in that it fully utilizes all the chlorophyll in silkworm excrement, including chlorophyllide (chlorophyllide a), completely prevents the formation of copper calcium chlorophyll and copper copper chlorophyll, reduces the amount of organic solvent used by more than 60%, achieving the innovative effects of 100% utilization rate of chlorophyll and 100% conversion rate of chlorophyll into potassium copper chlorophyllin. The potassium copper chlorophyllin product obtained by the present invention is a dark green to dark black powder, and all indicators are uniformly superior to the requirements of the national food safety standard GB 1886.307 - 2020 "Food Additive Potassium Copper Chlorophyllin". Among them, the mass percentage content of potassium copper chlorophyllin (dry basis) ≥ 98.0%, free copper is not contained, there are no residues of dichloromethane, methanol, n - hexane and n - heptane, and the residual amount of isopropanol ≤ 15 ppm, and the contents of lead (Pb) and arsenic (As) are both ≤ 0.1 ppm. Description of the Drawings

[0028] Figure 1 It is a process flow chart of a manufacturing method of potassium copper chlorophyllin.

[0029] Figure 2 It is a chemical equation for the hydrolysis of chlorophyll by chlorophyllase.

[0030] Figure 3It is the chemical structural formula of potassium copper chlorophyllin. Detailed implementation mode

[0031] Below, the applicant will further elaborate on the method of the present invention in combination with specific embodiments.

[0032] Example 1:

[0033] According to Figure 1 it is known that a manufacturing method of potassium copper chlorophyllin has the following steps:

[0034] (1) Pretreatment of crude silkworm excrement: Take 5 kg of dry crude silkworm excrement, first use a stainless steel sieve with a diameter of 4.5 mm to screen out residual mulberry branches, mulberry leaves, and mulberry leaf stalks and other large solid impurities in the crude silkworm excrement, then use a winnowing machine to remove soil, sediment, lime, and other high-density solid impurities in the crude silkworm excrement, as well as lighter solid impurities such as fine broken mulberry leaves, mulberry stalks, and mulberry branches. Then, pulverize the obtained purified silkworm excrement with a stainless steel pulverizer and sieve it through a 30-mesh standard sieve to obtain 4.25 kg of purified silkworm excrement powder; purification treatment and pulverization;

[0035] (2) Impurity removal by acidic water method and acidic copper substitution: Take the purified silkworm excrement powder obtained in step (1), add 64 kg of water and soak for 1.5 hours. Then, under stirring, adjust the pH to 1.7 with 10% dilute hydrochloric acid. After continuing to stir for 1.0 hour, readjust and maintain the pH at 1.7. Add 34 g of analytical pure solid copper chloride, stir to dissolve and mix evenly, continue to stir and heat the mixture to 85 °C, stir for 1.0 hour, and then centrifuge to obtain a precipitate; dissolve and disperse the precipitate evenly with 32 kg of water, and perform the second and third water extractions under the conditions of a temperature of 85 °C, a pH of 1.7, and a stirring time of 0.5 hour, and then centrifuge to obtain a precipitate;

[0036] (3) Precipitate drying and extraction: Use vacuum drying to dry the precipitate obtained in step (2) at 50 °C until the moisture content is less than 4% to obtain 1.7 kg of purified and copper-substituted silkworm excrement. Add 6.8 kg of analytical pure isopropanol, and under the conditions of a temperature of 35 °C and a stirring extraction time of 1.5 hours, extract copper chlorophyll and copper dephytol chlorophyll monoacid three times, filter and discard the precipitate respectively, and reuse the third isopropanol extract. Combine the first two isopropanol extracts to obtain 13.6 kg of isopropanol extract;

[0037] (4) Saponification and precipitation: Use vacuum concentration to concentrate the isopropanol extract obtained in step (3) to 4.5 kg, add 250 g of analytical pure solid potassium hydroxide, stir to dissolve, and then carry out a saponification reaction under the conditions of a temperature of 55 °C and a stirring time of 3.0 hours; under stirring conditions, cool the saponification solution to 10 °C, continue to stir for 5.5 hours, and then centrifuge to obtain the crude product of potassium copper chlorophyllin;

[0038] (5) Washing and drying: Add isopropanol in an amount 0.9 times the mass of the crude potassium copper chlorophyllin obtained in step (4) to the crude product, control the temperature of the mixture at 10 °C, stir and wash the crude product for 1.0 hour, wash twice, and centrifuge to obtain the wet refined potassium copper chlorophyllin. Use the vacuum drying method to remove the residual isopropanol in the wet refined potassium copper chlorophyllin at a temperature of 40 °C to obtain 47 g of potassium copper chlorophyllin product.

[0039] In the attached drawings, the crude silkworm excrement, purification treatment, pulverization, and purified powdered silkworm excrement are incorporated into the pretreatment of the crude silkworm excrement in step 1; in the attached drawings, the impurity removal by acidic water method and acidic copper substitution, purification, and copper-substituted silkworm excrement are incorporated into the impurity removal by acidic water method and acidic copper substitution in step 2; in the attached drawings, precipitation drying and organic solvent extraction are incorporated into precipitation drying and extraction in step 3; in the attached drawings, the saponification and precipitation of the concentrated organic solvent extract and the crude potassium copper chlorophyllin are incorporated into saponification and precipitation in step 4; in the attached drawings, organic solvent washing and drying and the potassium copper chlorophyllin product are incorporated into washing and drying in step 5.

[0040] Determined by the standard method specified in GB 1886.307-2020, the purity (dry basis) of the obtained potassium copper chlorophyllin product is 98.5%.

[0041] Example 2:

[0042] According to Figure 1 It can be known that a method for manufacturing potassium copper chlorophyllin, the steps are as follows:

[0043] (1) Pretreatment of crude silkworm excrement: Take 300 kg of dry crude silkworm excrement, first screen out the residual mulberry branches, mulberry leaves, and mulberry leaf stalks and other large solid impurities in the crude silkworm excrement with a stainless steel sieve with a diameter of 4.5 mm, and then use an air separator to remove the soil, sediment, lime, and other high-density solid impurities in the crude silkworm excrement, as well as the lighter solid impurities such as small broken mulberry leaves, mulberry stalks, and mulberry branches. Then, pulverize the obtained purified silkworm excrement with a stainless steel pulverizer and sieve it through a 60-mesh standard sieve to obtain 255 kg of purified silkworm excrement powder;

[0044] (2) Impurity removal by acidic water method and acidic copper substitution: Take the purified silkworm excrement powder obtained in step (1), add 5100 kg of water and soak for 3.0 hours. Then, under stirring, adjust the pH to 1.5 with 5% dilute hydrochloric acid, continue stirring for 1.0 hour, readjust and maintain the pH at 1.5, add 3.8 kg of analytical pure solid copper chloride, stir to dissolve and mix evenly, heat the mixture to 90 °C, stir for 2.0 hours, and then centrifuge to obtain a precipitate; Dissolve and disperse the precipitate evenly with 2550 kg of water, and carry out the second and third water extractions under the conditions of a temperature of 90 °C, a pH of 1.5, and a stirring time of 1.0 hour, and then centrifuge to obtain a precipitate;

[0045] (3) Precipitation drying and extraction: The precipitate obtained in step (2) was dried by vacuum drying at 60 °C until the moisture content was less than 4% by weight, obtaining 69 kg of purified and copper-substituted silkworm excrement. 414 kg of analytical pure isopropanol was added, and under the conditions of a temperature of 50 °C and a stirring extraction time of 2.5 hours, copper-substituted chlorophyll and copper-substituted chlorophyllide a were extracted three times. Each time, the mixture was filtered, and the precipitate was discarded. The third isopropanol extract was recycled, and the first two isopropanol extracts were combined to obtain 830 kg of isopropanol extract;

[0046] (4) Saponification and precipitation: After the isopropanol extract obtained in step (3) was concentrated to 208 kg by vacuum concentration, 2.1 kg of analytical pure solid potassium hydroxide was added. After stirring and dissolving, a saponification reaction was carried out at a temperature of 59 °C and a stirring time of 5.5 hours. The saponified solution was cooled to 0 °C, stirred for an additional 10 hours, and then centrifuged to discard the supernatant, obtaining a crude product of potassium copper chlorophyllin;

[0047] (5) Washing and drying: Isopropanol with a mass multiple of 1.5 times that of the crude product of potassium copper chlorophyllin obtained in step (4) was added. The temperature of the mixture was controlled at 0 °C, and the crude product was stirred and washed for 1.0 hour. This washing process was repeated twice, and then centrifuged to discard the supernatant, obtaining a wet high-quality product of potassium copper chlorophyllin. The residual isopropanol in the wet high-quality product of potassium copper chlorophyllin was removed by vacuum drying at 50 °C, obtaining 3.3 kg of potassium copper chlorophyllin product.

[0048] Other implementation steps are the same as those in Example 1.

[0049] Determined by the standard method specified in GB 1886.307-2020, the purity (dry basis) of the obtained potassium copper chlorophyllin product is 99.0%.

[0050] Example 3:

[0051] According to Figure 1 it can be known that a method for manufacturing potassium copper chlorophyllin has the following steps:

[0052] (1) Pretreatment of crude silkworm excrement: 750 kg of dry crude silkworm excrement was taken. First, it was screened through a stainless steel sieve with a diameter of 4.0 mm to remove residual large solid impurities such as mulberry branches, mulberry leaves, and mulberry leaf stalks in the crude silkworm excrement. Then, a pneumatic separator was used to remove solid impurities with a high density such as soil, sediment, and lime in the crude silkworm excrement, as well as lighter solid impurities such as small (as above) broken mulberry leaves, mulberry stalks, and mulberry branches. Then, the obtained purified silkworm excrement was pulverized with a stainless steel pulverizer and sieved through a 10-mesh standard sieve, obtaining 675 kg of purified silkworm excrement powder;

[0053] (2) Acidic aqueous method for impurity removal and acidic copper substitution: Take the purified silkworm excrement powder obtained in step (1), add 6750 kg of water and soak for 3.0 hours. Then, under stirring, adjust the pH to 1.9 with 7% dilute hydrochloric acid. Continue stirring for 0.5 hours, readjust and maintain the pH at 1.9. Add 2.1 kg of analytical pure solid copper chloride, stir to dissolve and mix evenly. Heat the mixture to 80 °C, stir for 1.5 hours, and then centrifuge to obtain a precipitate. Dissolve and disperse the precipitate evenly with 3350 kg of water. Under the conditions of a temperature of 80 °C, a pH of 1.9, and a stirring time of 1.0 hour, perform the second and third water extractions, and then centrifuge to obtain a precipitate;

[0054] (3) Precipitate drying and extraction: Use vacuum drying to dry the precipitate obtained in step (2) at 60 °C until the moisture content is less than 4% by weight, obtaining 290 kg of purified and copper-substituted silkworm excrement; Add 580 kg of analytical pure isopropanol, and under the conditions of a temperature of 40 °C and a stirring extraction time of 0.5 hour, extract copper-substituted chlorophyll and copper-substituted chlorophyllide monoacid three times. Filter and discard the precipitate each time. The third isopropanol extract is recycled. Combine the first two isopropanol extracts to obtain 1162 kg of isopropanol extract;

[0055] (4) Saponification and precipitation: Use vacuum concentration to concentrate the isopropanol extract obtained in step (3) to 581 kg, then add 5.8 kg of analytical pure solid potassium hydroxide, stir to dissolve, and perform a saponification reaction under the conditions of a temperature of 50 °C and a stirring time of 1.5 hours; After the saponification is completed, cool the saponified solution to 20 °C, continue stirring for 1.0 hour, then centrifuge and discard the supernatant to obtain a crude product of potassium copper chlorophyllin;

[0056] (5) Washing and drying: Add isopropanol with a mass multiple of 0.3 times that of the crude product of potassium copper chlorophyllin to the crude product of potassium copper chlorophyllin obtained in step (4), control the temperature of the mixture at 20 °C, stir and wash the crude product for 0.5 hour, wash twice, centrifuge and discard the supernatant to obtain a wet fine product of potassium copper chlorophyllin. Use vacuum drying to remove the residual isopropanol in the wet fine product of potassium copper chlorophyllin at 45 °C, obtaining 6.1 kg of potassium copper chlorophyllin product.

[0057] Other implementation steps are the same as those in Example 1.

[0058] Determined by the standard method specified in GB 1886.307-2020, the purity (on dry basis) of the obtained potassium copper chlorophyllin product is 98.0%.

[0059] Example 4:

[0060] According to Figure 1 It can be known that a method for manufacturing potassium copper chlorophyllin, the steps of which are:

[0061] (1) Pretreatment of crude silkworm excrement: Take 10 kg of dry crude silkworm excrement. First, screen out the residual mulberry branches, mulberry leaves, and solid large particle impurities such as mulberry leaf stalks in the crude silkworm excrement with a stainless steel sieve with a diameter of 4.5 mm. Then, use a pneumatic separator to remove the solid impurities with high density such as soil, sediment, and lime in the crude silkworm excrement, as well as the lighter solid impurities such as fine (the same as above) broken mulberry leaves, mulberry stalks, and mulberry branches. Then, pulverize the obtained purified silkworm excrement with a stainless steel pulverizer and sieve it through a 40-mesh standard sieve to obtain 9.0 kg of purified silkworm excrement powder;

[0062] (2) Impurity removal by acidic water method and copper substitution: Take the purified silkworm excrement powder obtained in step (1), add 98 kg of water and soak for 2.0 hours. Then, under stirring, adjust the pH to 1.6 with 6% dilute hydrochloric acid. After continuing to stir for 0.5 hours, readjust and maintain the pH at 1.6; add 81 g of analytical pure solid copper chloride, stir to dissolve and mix evenly. Heat the mixture to 86 °C, stir for 0.5 hours, and then centrifuge to obtain a precipitate; dissolve and disperse the precipitate evenly with 54 kg of water. Under the conditions of a temperature of 86 °C, a pH of 1.6, and a stirring time of 0.5 hours, perform the second and third water extractions, and then centrifuge to obtain a precipitate;

[0063] (3) Precipitate drying and extraction: Use vacuum drying to dry the precipitate obtained in step (2) at 55 °C until the moisture content is less than 4% to obtain 3.5 kg of purified and copper-substituted silkworm excrement; add 16 kg of analytical pure isopropyl alcohol. Under the conditions of a temperature of 45 °C and a stirring extraction time of 2.0 hours, extract copper-substituted chlorophyll and copper-substituted monophytol chlorophyll acid three times. Filter and discard the precipitate each time. The third isopropyl alcohol extract is recycled. Combine the first two isopropyl alcohol extracts to obtain 32.5 kg of isopropyl alcohol extract;

[0064] (4) Saponification and precipitation: Use vacuum concentration to concentrate the isopropyl alcohol extract obtained in step (3) to 11 kg, then add 0.7 kg of analytical pure solid potassium hydroxide, stir to dissolve, and carry out a saponification reaction under the conditions of a temperature of 55 °C and a stirring time of 3.5 hours; after the saponification is completed, cool the saponified solution to 5 °C, continue to stir for 5.5 hours, and then centrifuge to discard the supernatant to obtain a crude product of potassium copper chlorophyllin;

[0065] (5) Washing and drying: Add isopropyl alcohol with a mass multiple of 1.1 times that of the crude product of potassium copper chlorophyllin obtained in step (4) to the crude product of potassium copper chlorophyllin, control the temperature of the mixture at 5 °C, stir and wash the crude product for 0.5 hours, wash 2 times, centrifuge to discard the supernatant to obtain a wet fine product of potassium copper chlorophyllin. Use vacuum drying to remove the residual isopropyl alcohol in the wet fine product of potassium copper chlorophyllin at 45 °C to obtain 108 g of potassium copper chlorophyllin product.

[0066] Determined by the standard method specified in GB 1886.307-2020, the purity (dry basis) of the obtained potassium copper chlorophyllin product is 98.6%.

[0067] Example 5:

[0068] According to Figure 1 it is known that a method for manufacturing potassium copper chlorophyllin comprises the following steps:

[0069] (1) Pretreatment of crude silkworm excrement: Take 55 kg of dry crude silkworm excrement, first screen out the residual mulberry branches, mulberry leaves and mulberry leaf stalks and other large solid impurities in the crude silkworm excrement with a stainless steel sieve with a diameter of 4.0 mm, and then use a pneumatic separator to remove the soil, sediment, lime and other high-density solid impurities in the crude silkworm excrement, as well as the lighter solid impurities such as fine broken mulberry leaves, mulberry stalks and mulberry branches. Then, pulverize the obtained purified silkworm excrement with a stainless steel pulverizer and sieve it through a 10-mesh standard sieve to obtain 47 kg of purified silkworm excrement powder;

[0070] (2) Impurity removal by acidic water method and copper substitution: Take the purified silkworm excrement powder obtained in step (1), add 660 kg of water and soak for 2.0 hours. Then, under stirring, adjust the pH to 1.8 with 5% dilute hydrochloric acid. After continuing to stir for 0.5 hour, readjust and maintain the pH at 1.8. Add 280 g of analytical pure solid copper chloride, stir to dissolve and mix evenly. Heat the mixture to 85 °C, stir for 1.0 hour and then centrifuge to obtain a precipitate; Dissolve and disperse the precipitate with 282 kg of water evenly. Under the conditions of a temperature of 85 °C, a pH of 1.8 and a stirring time of 0.5 hour, perform the second and third water extractions, and centrifuge to obtain a precipitate;

[0071] (3) Precipitate drying and extraction: Use vacuum drying to dry the precipitate obtained in step (2) at 60 °C until the moisture content is less than 4% to obtain 19.3 kg of purified and copper-substituted silkworm excrement. Add 58 kg of analytical pure isopropanol, and under the conditions of a temperature of 50 °C and a stirring extraction time of 1.0 hour, extract copper-substituted chlorophyll and copper-substituted chlorophyllide monoacid three times. Filter and discard the precipitate respectively. The third isopropanol extract is recycled, and the first two isopropanol extracts are combined to obtain 117 kg of isopropanol extract;

[0072] (4) Saponification and precipitation: Use vacuum concentration to concentrate the isopropanol extract obtained in step (3) to 58 kg, add 3.0 kg of analytical pure solid potassium hydroxide, stir to dissolve, and perform a saponification reaction under the conditions of a temperature of 59 °C and a stirring time of 2.0 hours; After the saponification is completed, cool the saponified solution to 15 °C, continue to stir for 4.5 hours and then centrifuge to discard the supernatant to obtain a crude product of potassium copper chlorophyllin;

[0073] (5) Washing and drying: Add isopropanol in an amount 0.8 times the mass of the crude potassium copper chlorophyll obtained in step (4) to the crude product, control the temperature of the mixture at 15 °C, stir and wash the crude product for 0.5 hours, wash twice, centrifuge to separate and discard the supernatant, and obtain the wet refined potassium copper chlorophyll. Remove the residual isopropanol in the wet refined potassium copper chlorophyll at 45 °C by vacuum drying method to obtain 471 g of potassium copper chlorophyll product.

[0074] Other implementation steps are the same as those in Example 1.

[0075] Determined by the standard method specified in GB 1886.307-2020, the purity (dry basis) of the obtained potassium copper chlorophyll product is 98.3%.

[0076] Example 6:

[0077] According to Figure 1 it can be known that a manufacturing method of potassium copper chlorophyll has the following steps:

[0078] (1) Pretreatment of crude silkworm excrement: Take 20 kg of dry crude silkworm excrement, first screen out the residual large solid impurities such as mulberry branches, mulberry leaves and mulberry leaf stalks in the crude silkworm excrement with a stainless steel sieve with a diameter of 4.5 mm, then use an air separator to remove the solid impurities with high density such as soil, sediment and lime in the crude silkworm excrement, as well as the lighter solid impurities such as small broken mulberry leaves, mulberry stalks and mulberry branches, and then pulverize the obtained purified silkworm excrement with a stainless steel pulverizer and sieve it through a 60-mesh standard sieve to obtain 17 kg of purified silkworm excrement powder;

[0079] (2) Impurity removal by acidic water method and acidic copper substitution: Take the purified silkworm excrement powder obtained in step (1), add 305 kg of water and soak for 3.0 hours, then under stirring, adjust the pH to 1.65 with 4% dilute hydrochloric acid, continue to stir for 0.5 hours and then readjust and maintain the pH at 1.65, add 220 g of analytical pure solid copper chloride, stir to dissolve and mix evenly, heat the mixture to 90 °C, stir for 0.5 hours and then centrifuge to obtain a precipitate; Dissolve and disperse the precipitate evenly with 150 kg of water, and carry out the second and third water extractions under the conditions of a temperature of 90 °C, a pH of 1.65 and a stirring time of 1.0 hour, and centrifuge to obtain a precipitate;

[0080] (3) Precipitate drying and extraction: Dry the precipitate obtained in step (2) to a moisture content of less than 4% at 55 °C by vacuum drying method to obtain 6.3 kg of purified and copper-substituted silkworm excrement, add 35 kg of analytical pure isopropanol, and under the conditions of a temperature of 50 °C and a stirring extraction time of 1.0 hour, extract copper-substituted chlorophyll and copper-substituted dephytylated chlorophyll monoacid three times, filter and discard the precipitate respectively, and reuse the third isopropanol extract, and combine the first two isopropanol extracts to obtain 71 kg of isopropanol extract;

[0081] (4) Saponification and precipitation: After concentrating the isopropanol extract obtained in step (3) to 18 kg by vacuum concentration, 1.7 kg of analytical pure solid potassium hydroxide is added, stirred and dissolved, and then saponification reaction is carried out under the conditions of a temperature of 59 °C and a stirring time of 5.0 hours; after the saponification is completed, the saponified solution is cooled to 5 °C, stirred continuously for 9.0 hours, and then centrifuged to discard the supernatant, obtaining a crude product of potassium copper chlorophyllin;

[0082] (5) Washing and drying: Add isopropanol with a multiple of 0.5 times the mass of the crude product of potassium copper chlorophyllin obtained in step (4), control the temperature of the mixture at 5 °C, stir and wash the crude product for 1.0 hour, wash twice, centrifuge to discard the supernatant, obtaining a wet refined product of potassium copper chlorophyllin. The residual isopropanol in the wet refined product of potassium copper chlorophyllin is removed by vacuum drying at 50 °C, obtaining 222 g of potassium copper chlorophyllin product.

[0083] Other implementation steps are the same as those in Example 1.

[0084] Determined by the standard method specified in GB 1886.307-2020, the purity (dry basis) of the obtained potassium copper chlorophyllin product is 98.9%.

[0085] Example 7:

[0086] According to Figure 1 it can be known that a manufacturing method of potassium copper chlorophyllin, the steps are as follows:

[0087] (1) Pretreatment of crude silkworm excrement: Take 300 kg of dry crude silkworm excrement, first screen out the residual mulberry branches, mulberry leaves and mulberry leaf stalks and other solid large-particle impurities in the crude silkworm excrement with a stainless steel sieve with a diameter of 4.5 mm, and then use a pneumatic separator to remove the solid impurities with a large density such as soil, sediment and lime in the crude silkworm excrement, as well as the lighter solid impurities such as fine broken mulberry leaves, mulberry stalks and mulberry branches. Then, the obtained purified silkworm excrement is pulverized with a stainless steel pulverizer and sieved through a 60-mesh standard sieve, obtaining 370 kg of purified silkworm excrement powder;

[0088] (2) Impurity removal by acidic water method and acidic copper substitution: Take the purified silkworm excrement powder obtained in step (1), add 4800 kg of water and soak for 0.5 hour, then under stirring, adjust the pH to 1.85 with 10% dilute hydrochloric acid, continue to stir for 1.0 hour, readjust and maintain the pH at 1.85, add 3.7 kg of analytical pure solid copper chloride, stir to dissolve and mix evenly, heat the mixture to a temperature of 80 °C and stir for 2.0 hours, and centrifuge to obtain a precipitate; the precipitate is dissolved and dispersed evenly with 2350 kg of water, and under the conditions of a temperature of 80 °C, a pH of 1.85 and a stirring time of 1.0 hour, carry out the second and third water extractions, and centrifuge to obtain a precipitate;

[0089] (3) Precipitation drying and extraction: The precipitate obtained in step (2) was dried by vacuum drying at 60 °C until the moisture content was less than 4% by weight, obtaining 156 kg of purified and copper-substituted silkworm excrement; 312 kg of analytical grade isopropanol was added, and under the conditions of a temperature of 50 °C and a stirring extraction time of 1.0 hour, the copper-substituted chlorophyll and copper-substituted chlorophyllide a were extracted three times. The precipitate was filtered off respectively, and the third isopropanol extract was recycled. The first two isopropanol extracts were combined to obtain 625 kg of isopropanol extract;

[0090] (4) Saponification and precipitation: After the isopropanol extract obtained in step (3) was concentrated to 312 kg by vacuum concentration, 22 kg of analytical grade solid potassium hydroxide was added. After stirring and dissolving, a saponification reaction was carried out under the conditions of a temperature of 59 °C and a stirring time of 1.5 hours; after the saponification was completed, the saponified solution was cooled to 10 °C, and stirring was continued for 3.0 hours, followed by centrifugation to discard the supernatant, obtaining a crude product of potassium copper chlorophyllin;

[0091] (5) Washing and drying: Isopropanol with a mass multiple of 1.5 times that of the crude product of potassium copper chlorophyllin was added to the crude product of potassium copper chlorophyllin obtained in step (4). The temperature of the mixture was controlled at 10 °C, and the crude product was stirred and washed for 0.5 hour, washed twice, and the supernatant was discarded by centrifugation, obtaining a wet refined product of potassium copper chlorophyllin. The residual isopropanol in the wet refined product of potassium copper chlorophyllin was removed by vacuum drying at 50 °C, obtaining 3.35 kg of potassium copper chlorophyllin product.

[0092] Other implementation steps are the same as those in Example 1.

[0093] Determined by the standard method specified in GB 1886.307-2020, the purity (dry basis) of the obtained potassium copper chlorophyllin product is 98.1%.

[0094] Example 8:

[0095] According to Figure 1 It can be known that a method for manufacturing potassium copper chlorophyllin, the steps are:

[0096] (1) Pretreatment of crude silkworm excrement: 125 kg of dry crude silkworm excrement was taken. First, it was screened through a stainless steel sieve with a diameter of 4.0 mm to remove residual large solid impurities such as mulberry branches, mulberry leaves, and mulberry leaf stalks in the crude silkworm excrement. Then, a pneumatic separator was used to remove solid impurities with a large density such as soil, sediment, and lime in the crude silkworm excrement, as well as lighter solid impurities such as fine broken mulberry leaves, mulberry stalks, and mulberry branches. Then, the obtained purified silkworm excrement was pulverized with a stainless steel pulverizer and sieved through a 20-mesh standard sieve, obtaining 113 kg of purified silkworm excrement powder;

[0097] (2) Acidic aqueous method for impurity removal and acidic copper substitution: Take the purified silkworm excrement powder obtained in step (1), add 1582 kg of water and soak for 2.5 hours. Then, under stirring, adjust the pH to 1.55 with 5% dilute hydrochloric acid. After continuing to stir for 1.0 hour, readjust and maintain the pH at 1.55; add 1.15 kg of analytical pure solid copper chloride, stir to dissolve and mix evenly. Heat the mixture to 90 °C, continue to stir for 1.5 hours, and then centrifuge to obtain a precipitate. Dissolve and disperse the precipitate evenly with 1020 kg of water. Under the conditions of a temperature of 90 °C, a pH of 1.55, and a stirring time of 1.0 hour, perform the second and third water extractions, and then centrifuge to obtain a precipitate;

[0098] (3) Precipitate drying and extraction: Use vacuum drying to dry the precipitate obtained in step (2) at 60 °C until the moisture content is less than 4% by weight, obtaining 43 kg of purified and copper-substituted silkworm excrement. Add 236 kg of analytical pure isopropanol, and under the conditions of a temperature of 50 °C and a stirring extraction time of 2.5 hours, extract copper-substituted chlorophyll and copper-substituted monophytol chlorophyll acid three times. Filter and discard the precipitate each time. The third isopropanol extract is recycled. Combine the first two isopropanol extracts to obtain 473 kg of isopropanol extract;

[0099] (4) Saponification and precipitation: Use vacuum concentration to concentrate the isopropanol extract obtained in step (3) to 158 kg, then add 12 kg of analytical pure solid potassium hydroxide, stir to dissolve, and perform a saponification reaction under the conditions of a temperature of 55 °C and a stirring time of 4.0 hours; after the saponification is completed, cool the saponified solution to 0 °C, continue to stir for 8.0 hours, and then centrifuge to discard the supernatant to obtain a crude product of potassium copper chlorophyllin;

[0100] (5) Washing and drying: Add isopropanol with a mass multiple of 1.0 times that of the crude product of potassium copper chlorophyllin obtained in step (4) to the crude product, control the temperature of the mixture at 0 °C, stir and wash the crude product for 1.0 hour, wash 2 times, centrifuge to discard the supernatant to obtain a wet fine product of potassium copper chlorophyllin. Use vacuum drying to remove the residual isopropanol in the wet fine product of potassium copper chlorophyllin at 45 °C, obtaining 1.4 kg of potassium copper chlorophyllin product.

[0101] Other implementation steps are the same as those in Example 1.

[0102] Determined by the standard method specified in GB 1886.307-2020, the purity (dry basis) of the obtained potassium copper chlorophyllin product is 98.8%.

[0103] Example 9:

[0104] According to Figure 1 It can be known that a method for manufacturing potassium copper chlorophyllin, the steps of which are:

[0105] (1) Pretreatment of crude silkworm excrement: Take 80 kg of dry crude silkworm excrement. First, sieve it through a stainless steel sieve with a diameter of 4.5 mm to remove residual mulberry branches, mulberry leaves, and solid large particle impurities such as mulberry leaf stalks in the crude silkworm excrement. Then, use a pneumatic separator to remove solid impurities with high density such as soil, sediment, and lime in the crude silkworm excrement, as well as lighter solid impurities such as fine broken mulberry leaves, mulberry stalks, and mulberry branches. Then, pulverize the obtained purified silkworm excrement with a stainless steel pulverizer and sieve it through a 40-mesh standard sieve to obtain 68 kg of purified silkworm excrement powder;

[0106] (2) Impurity removal by acidic water method and acidic copper substitution: Take the purified silkworm excrement powder obtained in step (1), add 1020 kg of water and soak for 1.5 hours. Then, under stirring, adjust the pH to 1.7 with 8% dilute hydrochloric acid. After continuing to stir for 1.0 hour, readjust and maintain the pH at 1.7. Add 550 g of analytical pure solid copper chloride, stir to dissolve and mix evenly. Heat the mixture to 85 °C, stir for 1.0 hour, and then centrifuge to obtain a precipitate; Dissolve and disperse the precipitate evenly with 510 kg of water, and carry out the second and third water extractions under the conditions of a temperature of 85 °C, a pH of 1.7, and a stirring time of 0.5 hour, and then centrifuge to obtain a precipitate;

[0107] (3) Precipitate drying and extraction: Use vacuum drying to dry the precipitate obtained in step (2) at 60 °C until the moisture content is below 3% to obtain 27.2 kg of purified and copper-substituted silkworm excrement. Add 68 kg of analytical pure anhydrous ethanol, and under the conditions of a temperature of 50 °C and a stirring extraction time of 1.5 hours, extract copper-substituted chlorophyll and copper-substituted monophytol chlorophyll acid three times. Filter and discard the precipitate each time. The third anhydrous ethanol extract is recycled, and the first two anhydrous ethanol extracts are combined to obtain 137 kg of anhydrous ethanol extract;

[0108] (4) Saponification and precipitation: Use vacuum concentration to concentrate the anhydrous ethanol extract obtained in step (3) to 46 kg, then add 2.5 kg of analytical pure solid potassium hydroxide, stir to dissolve, and carry out a saponification reaction under the conditions of a temperature of 55 °C and a stirring time of 3.0 hours; After the saponification is completed, cool the saponified solution to 10 °C, continue to stir for 5.5 hours, and then centrifuge to discard the supernatant to obtain a crude product of potassium copper chlorophyllin;

[0109] (5) Washing and drying: Add anhydrous ethanol with a mass multiple of 0.9 times that of the crude product of potassium copper chlorophyllin obtained in step (4) to the crude product of potassium copper chlorophyllin, control the temperature of the mixture at 10 °C, stir and wash the crude product for 0.5 hour, wash 2 times, centrifuge to discard the supernatant to obtain a wet fine product of potassium copper chlorophyllin. Use vacuum drying to remove the residual anhydrous ethanol in the wet fine product of potassium copper chlorophyllin at 50 °C to obtain 682 g of potassium copper chlorophyllin product.

[0110] Other implementation steps are the same as those in Example 1.

[0111] Determined by the standard method specified in GB 1886.307-2020, the purity of the obtained potassium copper chlorophyllin product (calculated on a dry basis) is 98.8%.

[0112] Example 10:

[0113] According to Figure 1 it is known that a method for manufacturing potassium copper chlorophyllin comprises the following steps:

[0114] (1) Pretreatment of crude silkworm excrement: Take 45 kg of dry crude silkworm excrement, first screen out the residual mulberry branches, mulberry leaves and mulberry leaf stalks and other large solid impurities in the crude silkworm excrement with a stainless steel sieve with a diameter of 4.5 mm, and then use a pneumatic separator to remove the soil, sediment, lime and other high-density solid impurities in the crude silkworm excrement, as well as the lighter solid impurities such as fine broken mulberry leaves, mulberry stalks and mulberry branches. Then, pulverize the obtained purified silkworm excrement with a stainless steel pulverizer and sieve it through a 60-mesh standard sieve to obtain 40 kg of purified silkworm excrement powder;

[0115] (2) Impurity removal by acidic water method and acidic copper substitution: Take the purified silkworm excrement powder obtained in step (1), add 800 kg of water and soak for 3.0 hours. Then, under stirring, adjust the pH to 1.5 with 10% dilute hydrochloric acid. After continuing to stir for 1.0 hour, readjust and maintain the pH at 1.5. Add 600 g of analytical pure solid copper chloride, stir to dissolve and mix evenly. Heat the mixture to 90 °C and stir for 2.0 hours, then centrifuge to obtain a precipitate; Dissolve and disperse the precipitate in 400 kg of water evenly. Under the conditions of a temperature of 90 °C, a pH of 1.5 and a stirring time of 0.5 hour, perform the second and third water extractions, and centrifuge to obtain a precipitate;

[0116] (3) Precipitate drying and extraction: Use vacuum drying method to dry the precipitate obtained in step (2) at 60 °C until the moisture content is below 3% to obtain 14.5 kg of purified and copper-substituted silkworm excrement. Add 87 kg of analytical pure absolute ethanol. Under the conditions of a temperature of 50 °C and a stirring extraction time of 2.5 hours, extract copper-substituted chlorophyll and copper-substituted chlorophyllide monoacid three times. Filter and discard the precipitate respectively. The third absolute ethanol extract is recycled. Combine the first two absolute ethanol extracts to obtain 175 kg of absolute ethanol extract;

[0117] (4) Saponification and precipitation: Use vacuum concentration method to concentrate the absolute ethanol extract obtained in step (3) to 44 kg, then add 4.4 kg of analytical pure solid potassium hydroxide, stir to dissolve, and carry out saponification reaction under the conditions of a temperature of 59 °C and a stirring time of 4.5 hours; After the saponification is completed, cool the saponified solution to 0 °C, continue to stir for 10 hours, then centrifuge to discard the supernatant to obtain the crude product of potassium copper chlorophyllin;

[0118] (5) Washing and drying: Add anhydrous ethanol with a mass multiple of 1.0 times that of the crude product of potassium copper chlorophyllin obtained in step (4) to the crude product, control the temperature of the mixture at 0 °C, stir and wash the crude product for 0.5 hours, wash twice, centrifuge and separate to discard the supernatant, and obtain wet fine product of potassium copper chlorophyllin. Use vacuum drying method to remove the residual anhydrous ethanol in the wet fine product of potassium copper chlorophyllin at 50 °C, and obtain 460 grams of potassium copper chlorophyllin product.

[0119] Other implementation steps are the same as those in Example 1.

[0120] Determined by the standard method specified in GB 1886.307-2020, the purity (dry basis) of the obtained potassium copper chlorophyllin product is 99.1%.

[0121] The specific embodiments described in this specification are merely illustrative of the spirit of the present invention. Those skilled in the technical field to which the present invention pertains can make various modifications or supplements to the described specific embodiments or use similar ways to replace them, but will not deviate from the spirit of the present invention or exceed the scope defined by the appended claims.

Claims

1. A method for producing copper potassium chlorophyll, characterized in that: The steps include: (1) Pretreatment of coarse silkworm excrement: dry coarse silkworm excrement is taken, and after being screened with a stainless steel sieve having a diameter of 3.5 to 4.5 mm to remove the large solid impurities of mulberry branches, mulberry leaves, mulberry leaf stems, straw and nylon rope remaining in the coarse silkworm excrement, a winnowing machine is used to remove the soil, silt, lime, fine broken mulberry leaves, mulberry stems and mulberry branches in the coarse silkworm excrement to obtain purified silkworm excrement; the purified silkworm excrement is crushed with a stainless steel crusher, and sieved with a standard sieve of 2 to 60 meshes to obtain purified silkworm excrement powder for later use; (2) Acidic water method for impurity removal and acid copper substitution: Take the purified silkworm excrement powder obtained in step (1), soak it in water with a mass multiple of 10 to 20 times the silkworm excrement powder for 0.5 to 3 hours to fully absorb water and swell, and then adjust the pH to 1.5 to 1.9 with dilute hydrochloric acid while stirring, and readjust and maintain the pH to 1.5 to 1.9 after continuing stirring for 0.5 to 1 hour; add solid copper chloride with a mass fraction of 0.1% to 1.5% of the silkworm excrement powder, stir to dissolve and mix evenly; heat to a temperature of 80 to 90° C. and stir for 0.5 to 2 hours while stirring, filter or centrifuge to obtain a supernatant and a precipitate; discard the supernatant, dissolve and disperse the precipitate evenly with water with a mass multiple of 5 to 10 times the silkworm excrement powder, perform a second and third water extraction under the conditions of a temperature of 80 to 90° C., a pH of 1.5 to 1.9 and a stirring time of 0.5 to 1 hour, and filter or centrifuge to obtain a supernatant and a precipitate; discard the supernatant and obtain the precipitate for use; (3) Precipitation drying and organic solvent extraction: the precipitate obtained in step (2) is dried by vacuum drying at a temperature of 40-60° C. to a moisture content of less than 4% to obtain purified and copper-substituted silkworm excrement; the copper-substituted chlorophyll and the copper-substituted dephytolated chlorophyll monoacid are extracted three times with an organic solvent at a mass ratio of purified and copper-substituted dry silkworm excrement: organic solvent = 1:2-6, a temperature of 20-50° C. and a stirring extraction time of 0.5-2.5 hours, and the extractions are filtered or centrifuged respectively, the precipitate is discarded, the third organic solvent extraction is reused, and the first two organic solvent extractions are combined to obtain the copper-substituted chlorophyll and the copper-substituted dephytolated chlorophyll monoacid organic solvent extractions for standby use; (4) Saponification and precipitation of the organic solvent extract: The organic solvent extract obtained in step (3) is concentrated to 1 / 2 to 1 / 4 of its volume by vacuum concentration to obtain a concentrated solution of the organic solvent extract, solid potassium hydroxide is added at a mass fraction of 1.0% to 10% of the concentrated solution, and the solution is stirred and dissolved, and the solution is heated to 50 to 59° C. and stirred for 0.5 to 5.5 hours to saponify the copper-substituted chlorophyll and the copper-substituted dephytol chlorophyll monoacid to generate copper-substituted chlorophyllin dipotassium salt and copper-substituted chlorophyllin tripotassium salt, i.e., copper potassium chlorophyll. After the saponification is completed, the saponified solution is cooled to 0 to 20° C. under stirring, and the stirring is continued for 1.0 to 10.0 hours, and the solution is filtered or centrifuged, and the supernatant is discarded to obtain a crude copper potassium chlorophyll for later use; (5) washing and drying with organic solvent: the crude copper potassium chlorophyll salt obtained in step (4) is washed with an organic solvent in an amount 0.3 to 1.5 times the mass of the crude copper potassium chlorophyll salt at a temperature of 0 to 20° C., stirred for 0.5 to 1.0 hour, washed 1 to 2 times, filtered or centrifuged, and the supernatant is discarded to obtain a wet fine copper potassium chlorophyll salt. The residual organic solvent in the wet fine copper potassium chlorophyll salt is removed by vacuum drying at a temperature of 30 to 50° C. to obtain copper potassium chlorophyll salt.

2. The method for producing potassium copper chlorophyll according to claim 1, characterized in that: The coarse silkworm excrement described in step (1) is non-purified silkworm excrement with a moisture content of ≤5%.

3. The method for producing copper potassium chlorophyll according to claim 1, characterized in that: The cupric chloride described in step (2) is analytically pure, chemically pure and technical grade cupric chloride.

4. The method for producing potassium copper chlorophyll according to claim 1, characterized in that: The organic solvent described in step (3) and step (5) is any one of isopropanol, anhydrous ethanol and propanol.

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