Method for recovering effective components from ergothioneine crude product mother liquor

Abstract

The invention discloses a method for recovering effective components from a mother solution of an ergothioneine crude product, which belongs to the technical field of chemical industry and pharmacy, and comprises the following specific operation steps: (1) dilution: adding water into the mother solution of the ergothioneine crude product for dilution; (2) adsorption and desorption: injecting the diluted ergothioneine crude product mother liquor into a resin column for adsorption to obtain a desorption solution, treating and recycling the desorption solution, and desorbing the adsorption resin column by using a desorption agent to obtain a desorption solution of ergothioneine, methionine and cysteine; and (3) concentrating, crystallizing and drying: respectively concentrating, crystallizing and drying the desorption solutions of the ergothioneine, the methionine and the cysteine to obtain effective components such as the ergothioneine, the methionine and the cysteine. According to the method, effective components such as ergothioneine, methionine and cysteine can be efficiently recycled from the mother liquor of the ergothioneine crude product, the method is reasonable in design, easy and convenient to operate, good in recycling effect, excellent in product quality and environmentally friendly, waste of amino acid in the crystallization mother liquor is avoided, and new economic benefits are created.

Description

Technical Field

[0001] This invention discloses a method for recovering active ingredients from crude ergothioneine mother liquor, belonging to the fields of chemical and pharmaceutical technology. More specifically, it relates to an industrially applicable method for efficiently recovering active ingredients such as ergothioneine, methionine, and cysteine ​​from crude ergothioneine mother liquor. Background Technology

[0002] Ergothioneine (EGT), scientifically known as 2-mercapto-histidine-trimethylammonium sulfate, was initially discovered in fungi. The pure form is a white crystalline solid. It possesses unique antioxidant properties, offering high protection for cells. It is a non-toxic, natural antioxidant that is not easily oxidized in water. In organ protection, it can replace glutathione to protect transplanted organs. In cosmetics, it can be added as a protective agent to minimize the formation of reactive oxygen species and protect cells from radiation damage. Due to its excellent properties, it is now widely used in pharmaceuticals, food, animal feed, cosmetics, and biotechnology.

[0003] Currently, there are three main methods for preparing ergothioneine: chemical synthesis, extraction, and bio-fermentation synthesis. Chemical synthesis is costly, while extraction suffers from low ergothioneine content in raw materials and issues such as high impurity levels, drug residues, and high costs, both of which limit its application to some extent. Currently, bio-fermentation is the mainstream approach for low-cost, large-scale production of ergothioneine. As a highly bioactive natural antioxidant, the recovery of the crude mother liquor and its active ingredients during the production process of ergothioneine is of great significance.

[0004] Currently, Chinese patent CN119707826 A discloses a method for recovering ergothioneine from its mother liquor. The mother liquor is diluted and passed through a cation exchange resin to adsorb the ergothioneine. The resin is then rinsed with water to remove impurities. Next, a methionine solution is used to wash the ergothioneine off the resin. The ergothioneine-containing eluent is collected, concentrated, and then separated by chromatography to remove methionine. The ergothioneine-containing eluent is collected, concentrated, and crystallized to obtain the recovered product. This method achieves a mother liquor recovery rate of 61.08% and a product purity of 98.63%. However, the method involves methionine washing followed by chromatographic purification, which introduces methionine, complicating the recovery process and increasing processing time. Therefore, simplifying the recovery process, improving the recovery rate, and developing universally applicable technologies are not only cost-saving measures to improve economic efficiency but also crucial for practicing green production and ensuring process compliance. This significance increases significantly with increased production volume, especially in large-scale industrial production. Summary of the Invention

[0005] To solve the above-mentioned technical problems, the present invention provides a method for recovering the active ingredient from crude ergothioneine mother liquor, comprising the following steps: (1) Dilution: Add water to the crude ergothioneine mother liquor for dilution; (2) Adsorption and desorption: The diluted crude ergothioneine mother liquor was injected into an ion exchange resin column for adsorption. After adsorption, a desorbent was used for desorption to obtain desorbed solutions containing ergothioneine, methionine and cysteine ​​respectively. (3) Concentration, crystallization and drying: The three desorption solutions are concentrated, crystallized and dried respectively to obtain ergothioneine, methionine and cysteine ​​products.

[0006] Preferably, the dilution factor in step (1) is 6-10 BV (bed volume).

[0007] Preferably, the ion exchange resin in step (2) is D001 resin or 001X7 resin.

[0008] Preferably, the adsorption flow rate in step (2) is 0.1-1.1 BV / h; the desorption flow rate is 0.1-1.1 BV / h.

[0009] Preferably, the desorbent in step (2) is hydrochloric acid with a mass concentration of 0.2%-0.4%.

[0010] Preferably, in step (2), the desorption solutions of cysteine, ergothioneine and methionine are collected in the order of effluent flow during the desorption process.

[0011] Preferably, the cysteine ​​is enriched in the first 2 BV of the desorption solution, the ergothioneine is enriched in 3-5 BV of the desorption solution, and the methionine is enriched in 6-7 BV of the desorption solution.

[0012] Preferably, in step (3), ergothioneine is crystallized by alcohol precipitation, and methionine and cysteine ​​are crystallized by low-temperature static crystallization.

[0013] Preferably, the drying in step (3) is performed using vacuum drying, wherein the drying temperature of ergothioneine is 50-60℃, the vacuum degree is ≥0.060MPa, and the drying time is 2-5h; the drying temperature of methionine is 60-80℃, the vacuum degree is 0.08-0.1MPa, and the drying time is 4-10h; and the drying temperature of cysteine ​​is 40-60℃, the vacuum degree is 0.08-0.1MPa, and the drying time is 4-8h.

[0014] Preferably, the ion exchange resin column is regenerated after use. The regeneration method is as follows: first rinse with 4-6 BV of dilute acid, and then rinse with 4-6 BV of dilute alkali.

[0015] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. The method provided by this invention can efficiently recover ergothioneine, methionine and cysteine ​​and other active ingredients from crude ergothioneine mother liquor. Through specific dilution, adsorption and desorption, concentration, crystallization and drying steps, high recovery rate of active ingredients is achieved, with a recovery rate of more than 90%.

[0016] 2. The ergothioneine, methionine, and cysteine ​​products recovered by the method of this invention have high purity. The purity of ergothioneine can reach 99.9%, and the purity of methionine and cysteine ​​can reach 99.1% and 98.7% or higher, respectively, ensuring the excellent quality of the recovered products and meeting the market demand for high-quality raw materials.

[0017] 3. The method of the present invention does not introduce harmful substances during the recycling process, and reduces the generation of waste through reasonable process design, which meets the requirements of environmental friendliness.

[0018] 4. Compared with existing technologies, this invention simplifies the recycling process and avoids the complex operations and high time consumption caused by introducing additional substances (such as methionine).

[0019] 5. The ion exchange resin used in this invention can be recycled and reused. The regeneration method is as follows: the resin column is first regenerated with 4-6 BV of dilute acid, and then with 4-6 BV of dilute alkali. The resin column can then be reused. Detailed Implementation

[0020] The present invention will now be described in detail through specific embodiments to facilitate understanding of the invention. However, various modifications can be made to the embodiments of the present invention, and the scope of the invention is not limited to the embodiments described below. Providing embodiments of the present invention makes this disclosure clear and complete, fully illustrating the invention to those skilled in the art.

[0021] Example 1 (1) Take 50 L of crude ergothioneine mother liquor (ergothioneine content 50 g / L, methionine 2.5 g / L, cysteine ​​0.9 g / L), and dilute with water to 6 BV.

[0022] (2) The crude mother liquor was injected into the D001 resin column at a flow rate of 0.25 BV / h for adsorption. After adsorption, it was desorbed with 0.25% hydrochloric acid at a flow rate of 0.25 BV / h. The first 2 BV of desorbed solution was cysteine ​​concentrate, the 3-5 BV of desorbed solution was ergothioneine, and the 6-7 BV of desorbed solution was methionine. After desorption, the resin was regenerated.

[0023] (3) Ergothioneine desorption solution was concentrated, crystallized, and dried to obtain 2283.1 g of ergothioneine, white granules, with a purity of 99.9%; methionine desorption solution was concentrated, crystallized, and dried to obtain 114.2 g of methionine, white powder, with a purity of 99.1%; cysteine ​​desorption solution was concentrated, crystallized, and dried to obtain 41.8 g of cysteine, off-white powder, with a purity of 98.7%.

[0024] Example 2 (1) Take 50 L of crude ergothioneine mother liquor (ergothioneine content 54 g / L, methionine 2.1 g / L, cysteine ​​0.7 g / L), and dilute with water to 8 BV.

[0025] (2) The crude mother liquor was injected into the D001 resin column at a flow rate of 1 BV / h for adsorption. After adsorption, it was desorbed with 0.35% hydrochloric acid at a flow rate of 1 BV / h. The first 2 BV of desorbed solution was cysteine ​​concentrate, the 3-5 BV of desorbed solution was ergothioneine, and the 6-7 BV of desorbed solution was methionine. After desorption, the resin was regenerated.

[0026] (3) Ergothioneine desorption solution was concentrated, crystallized, and dried to obtain 2471.1 g of ergothioneine, white granules, with a purity of 99.9%; methionine desorption solution was concentrated, crystallized, and dried to obtain 95.2 g of methionine, white powder, with a purity of 98.9%; cysteine ​​desorption solution was concentrated, crystallized, and dried to obtain 31.8 g of cysteine, off-white powder, with a purity of 99.2%.

[0027] Example 3 (1) Take 50 L of crude ergothioneine mother liquor (ergothioneine content 47 g / L, methionine 2.6 g / L, cysteine ​​1.1 g / L) and dilute with water to 6 BV.

[0028] (2) The crude mother liquor was injected into the D001 resin column at a flow rate of 0.25 BV / h for adsorption. After adsorption, it was desorbed with 0.25% hydrochloric acid at a flow rate of 0.25 BV / h. The first 2 BV of desorbed solution was cysteine ​​concentrate, the 3-5 BV of desorbed solution was ergothioneine, and the 6-7 BV of desorbed solution was methionine. After desorption, the resin was regenerated.

[0029] (3) Ergothioneine desorption solution was concentrated, crystallized, and dried to obtain 2148.5 g of ergothioneine, white granules, with a purity of 99.8%; methionine desorption solution was concentrated, crystallized, and dried to obtain 118.7 g of methionine, white powder, with a purity of 98.1%; cysteine ​​desorption solution was concentrated, crystallized, and dried to obtain 50.2 g of cysteine, off-white powder, with a purity of 98.5%.

[0030] Example 4 (1) Take 50 L of crude ergothioneine mother liquor (ergothioneine content 49 g / L, methionine 2.1 g / L, cysteine ​​0.6 g / L), and dilute with water to 8 BV.

[0031] (2) The crude mother liquor was injected into the 001X7 resin column at a flow rate of 1 BV / h for adsorption. After adsorption, it was desorbed with 0.35% hydrochloric acid at a flow rate of 1 BV / h. The first 2 BV of desorbed solution was cysteine ​​concentrate, the 3-5 BV of desorbed solution was ergothioneine, and the 6-7 BV of desorbed solution was methionine. After desorption, the resin was regenerated.

[0032] (3) The ergothioneine eluent was concentrated, crystallized, and dried to obtain 2247.7 g of ergothioneine, which was white granules with a purity of 99.9%; the methionine eluent was concentrated, crystallized, and dried to obtain 96.3 g of methionine, which was white powder with a purity of 98.7%; and the cysteine ​​eluent was concentrated, crystallized, and dried to obtain 27.1 g of cysteine, which was off-white powder with a purity of 99.0%.

[0033] Comparative Example 1 The steps in this comparative example are exactly the same as in Example 1, except that the desorbent is replaced by a 1% ammonia solution instead of 0.25% hydrochloric acid.

[0034] Comparative Example 2 Compared with Example 1, this comparative example does not involve dilution; the high-concentration mother liquor is directly loaded onto the column.

[0035] The contents of ergothioneine, methionine and cysteine ​​in the desorption solutions of Examples 1-4 and Comparative Examples 1-2 were detected respectively to obtain the purity of ergothioneine, methionine and cysteine, and the yield of ergothioneine, methionine and cysteine ​​was calculated. The results are shown in Table 1 below.

[0036] Table 1 Test Results

[0037] Note: "-" indicates that the target substance was not detected.

[0038] As shown in Table 1, the recovery method provided by this invention can efficiently recover ergothioneine, methionine, and cysteine, with yields all greater than 90% and high purity. In Comparative Example 1, when ammonia was used as the desorbent, the yields of ergothioneine, methionine, and cysteine ​​were low. Ammonia has a weaker desorption capacity than 0.25% hydrochloric acid, failing to completely elute the target substances adsorbed on the resin. Ammonia may also alter the ionic form of the target substances, affecting their stability in the desorption solution or subsequent crystallization processes. In Comparative Example 2, after loading the column with a high-concentration mother liquor, the residual target substances in the desorption solution were high. This was because the resin's adsorption of the target substances in the high-concentration system was not saturated or the adsorption kinetics were poor, resulting in a large amount of unadsorbed target substances being lost with the waste liquid, leading to a decrease in yield. Furthermore, competitive adsorption or adsorption inhibition may occur at high concentrations, affecting the separation effect.

Claims

1. A method for recovering the active ingredient from crude ergothioneine mother liquor, characterized in that, Includes the following steps: (1) Dilution: Add water to the crude ergothioneine mother liquor for dilution; (2) Adsorption and desorption: The diluted crude ergothioneine mother liquor was injected into an ion exchange resin column for adsorption. After adsorption, a desorbent was used for desorption to obtain desorbed solutions containing ergothioneine, methionine and cysteine ​​respectively. (3) Concentration, crystallization and drying: The three desorption solutions are concentrated, crystallized and dried respectively to obtain ergothioneine, methionine and cysteine ​​products.

2. The method according to claim 1, characterized in that, The dilution factor mentioned in step (1) is 6-10 BV.

3. The method according to claim 1, characterized in that, The ion exchange resin mentioned in step (2) is D001 resin or 001X7 resin.

4. The method according to claim 1, characterized in that, The adsorption flow rate in step (2) is 0.1-1.1 BV / h; the desorption flow rate is 0.1-1.1 BV / h.

5. The method according to claim 1, characterized in that, The desorbent mentioned in step (2) is hydrochloric acid with a mass concentration of 0.2%-0.4%.

6. The method according to claim 1, characterized in that, In step (2), during the desorption process, the desorbed solutions of cysteine, ergothioneine and methionine are collected in the order of effluent flow.

7. The method according to claim 6, characterized in that, The cysteine ​​was enriched in the first 2 BV of the desorption solution, the ergothioneine was enriched in 3-5 BV of the desorption solution, and the methionine was enriched in 6-7 BV of the desorption solution.

8. The method according to claim 1, characterized in that, In step (3), ergothioneine is crystallized by alcohol precipitation, while methionine and cysteine ​​are crystallized by low-temperature static crystallization.

9. The method according to claim 1, characterized in that, The drying process described in step (3) is vacuum drying. The drying temperature for ergothioneine is 50-60℃, the vacuum degree is ≥0.060MPa, and the drying time is 2-5h; the drying temperature for methionine is 60-80℃, the vacuum degree is 0.08-0.1MPa, and the drying time is 4-10h; and the drying temperature for cysteine ​​is 40-60℃, the vacuum degree is 0.08-0.1MPa, and the drying time is 4-8h.

10. The method according to claim 1, characterized in that, The ion exchange resin column is regenerated after use. The regeneration method is as follows: first rinse with 4-6 BV of dilute acid, and then rinse with 4-6 BV of dilute alkali.

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