A novel method for purifying menaquinone-7 using degradable straw stalk resin

Abstract

The invention discloses a method for purifying menadione 7 by a novel degradable straw resin, and a menadione 7 product with high purity is obtained by making a degradable straw resin, extracting and purifying menadione. The purification method is as follows: first, a flocculant is added to the fermentation liquid, and the mixture is stirred and mixed evenly, and plate-frame filtration is performed after standing flocculation precipitation, and the filtered fungus residue is dried, crushed, and fungus residue dry powder is obtained; the obtained fungus residue dry powder is extracted with acetone, and the extract is collected and concentrated under reduced pressure to obtain an extract concentrate; the obtained extract concentrate is transferred to a saponification reactor, sodium hydroxide solid is added for saponification reaction, sodium hydroxide is added dropwise until no solid is precipitated, and filtered to obtain a saponified liquid; the obtained saponified liquid is chromatographed with a straw resin, and washed with an acetone aqueous solution after adsorption is completed, and then eluted with acetone, etc. The method has good purification effect, high yield, and the straw resin can be reused; the organic solvents used for adsorption and desorption are all acetone, which has little impact on the environment and is easy to recycle.

Description

Technical Field

[0001] The invention relates to the purification of menaquinone-7, and in particular to a method for purifying menaquinone-7 using a novel degradable straw stalk resin. Background Art

[0002] Vitamin K2, commonly known as menaquinone, is composed of menaquinone-4 and menaquinone-7. Currently, menaquinone-7 is known to be the most active form of vitamin K2.

[0003] Menaquinone-7 is a series of compounds composed of a methyl menaquinone mother ring and varying numbers of isoprene units. MK-n represents the number of isoprene units on the side chain, and MK-7 contains 7 isoprene units on the side chain. VK2 can enhance the carboxylation of osteocalcin in human serum, thereby increasing bone density and preventing and treating osteoporosis. It can also be used to treat mitochondrial diseases such as Parkinson's syndrome. Among VK2 homologues, MK-7 has the best biological activity due to its longer half-life, can be stably present in the blood, and can be more effectively utilized by the human body.

[0004] The invention patent with patent publication number CN104262129A discloses a method for purifying vitamin menaquinone-7 from Bacillus subtilis natto. The method spray-dries the fermented liquid of Bacillus natto, extracts with a solvent or soaks the spray-dried powder of the fermented liquid of Bacillus natto to obtain an immersion solution. The immersion solution is concentrated to obtain an extract, which is passed through column chromatography and gradient or isocratic elution is performed, and the collected liquid is concentrated to obtain vitamin menaquinone-7. Finally, the crude product of vitamin menaquinone-7 is crystallized and purified to obtain a pure product of vitamin menaquinone-7 (MK-7). Its disadvantage is that a wet column is used for chromatography, the filler cannot be reused, the amount of solid waste is large, the process is cumbersome, and the cost is high.

[0005] The invention patent with the patent publication number CN110041184A discloses a method for purifying vitamin menaquinone-7 from Bacillus subtilis natto. The method adds a flocculant to the fermentation broth of Bacillus subtilis natto, and obtains dry thalli after filter pressing, drying and crushing. The first organic solvent is used to extract to obtain an immersion solution, which is adsorbed with straw resin, washed with a second organic solvent, and eluted with a third organic solvent. After collecting a suitable eluent, it is concentrated, dissolved with a fourth organic solvent, chromatographically filled with a chromatographic filler, eluted with a fifth organic solvent, concentrated after collection, and then crystallized and purified with a sixth solvent to obtain a pure product of vitamin menaquinone-7 (MK-7). Its disadvantage is that a total of 6 solvents are used in the chromatography purification process, which will bring impurities, and there will be a certain amount of residues, and the subsequent process is inconvenient to remove impurities, difficult to separate, and not conducive to recovery. Summary of the invention

[0006] Purpose of the invention: The purpose of the present invention is to provide a method for purifying menaquinone-7 using a novel degradable straw stalk resin.

[0007] Technical solution: A novel method for purifying menaquinone-7 using degradable straw stalk resin, comprising the following steps:

[0008] S1. Making degradable straw resin:

[0009] S11, drying, crushing and sieving plants with high natural plant fiber such as straw and rice husk to obtain fine fiber powder;

[0010] S12, add the fiber powder obtained in step S11 into a reaction kettle, add water to heat, and then add polyhydroxyalkanoate and polylactic acid in sequence under mechanical stirring, and stir at a low speed to fully mix;

[0011] S13, slowly add a binder to the mixed system in step S12, so that all solids are agglomerated and the surface is clear without obvious powder;

[0012] S14, let it stand and settle naturally, filter, clean and dry;

[0013] S15, pass through 200 mesh and 100 mesh sieves to select straw resin of appropriate size, load into column, and rinse with acetone for later use;

[0014] S2. Extraction and purification of menadione:

[0015] S21, adding a flocculant to the fermentation liquid and stirring to mix evenly, allowing it to stand for flocculation and precipitation, and then performing plate-and-frame filtration, and drying and crushing the filtered fungus residue to obtain fungus residue dry powder;

[0016] S22, extracting the mushroom residue dry powder obtained in step S21 with acetone, collecting the extract and concentrating it under reduced pressure to obtain an extract concentrate;

[0017] S23, transferring the leaching concentrate obtained in step S22 to a saponification reaction kettle, adding solid sodium hydroxide to carry out a saponification reaction, adding sodium hydroxide dropwise until no solid precipitates, filtering, and obtaining a saponified solution;

[0018] S24, the saponified liquid obtained in step S23 is chromatographed with straw resin, washed with acetone aqueous solution after adsorption, and then eluted with acetone. The eluate of menaquinone-7 with a purity greater than 90% is collected;

[0019] S25, concentrating the eluate obtained in step S24 by vacuum rotary evaporation, cooling and crystallizing, filtering and drying until there is no moisture, and obtaining menaquinone-7 crystalline powder.

[0020] Preferably, in step S11, the plant with high natural plant fiber content is dried at 115° C. with air blast until the moisture content is ≤2%, crushed by an ultrafine grinder, and sieved through a 3000-mesh sieve.

[0021] Preferably, in step S12, the volume of water is 6 times the weight of the fiber powder obtained in step S11, the heating and stirring temperature is 40-50°C, the weight of polyhydroxyalkanoate is 15%-18% of the weight of the fiber powder, the weight of polylactic acid is 17.5%-21% of the weight of the fiber powder, the low-speed stirring speed is 50-80r / min, and the low-speed stirring time is 2-4h.

[0022] Preferably, in step S13, the weight of the adhesive is 17.5%-21% of the weight of the fiber powder.

[0023] Preferably, in step S14, the natural sedimentation time is 2-3 hours, the filtering method is centrifuge filtration, and the drying is vacuum double cone drying at 80°C.

[0024] Preferably, in step S21, the flocculant is any one of polyaluminium chloride and polyferric sulfate, and the amount of flocculant added is 0.01%-0.5% of the weight of the fermentation liquid; the static flocculation precipitation time is 12 hours; the drying is vacuum double cone drying at 50-60°C; and the pulverization is pulverized by an ultrafine pulverizer.

[0025] Preferably, in step S22, the acetone extraction is performed four times, the volume of acetone used is 10 times the weight of the dry powder of the mushroom residue, the extraction is performed by heating at 60°C with mechanical stirring, the extraction time for each time is 1 hour, and the reduced pressure concentration temperature is 40°C.

[0026] Preferably, in step S23, the weight of the solid sodium hydroxide added is 3% of the volume of the filtrate, the saponification reaction temperature is 90° C., the saponification reaction time is 3 h, and the sodium hydroxide added dropwise is 20% sodium hydroxide aqueous solution.

[0027] Preferably, in step S24, the straw resin chromatography is kept at 60°C throughout the whole process, the volume of the straw resin is 10 times the weight of the saponified liquid obtained in step S23, the acetone aqueous solution used is a 50%-70% acetone aqueous solution, and the volume of the acetone aqueous solution is 5-10 times the volume of the chromatography column until menadione-7 starts to flow out.

[0028] Preferably, in step S25, the eluent is concentrated under vacuum at 60°C to a concentration of 5-6 mg / ml of menadione-7, the crystallization temperature is 10°C, the crystallization time is 5-6 h, and the drying condition is vacuum double cone drying at 40°C.

[0029] Beneficial effects:

[0030] (1) The resin used in the chromatography of the present invention does not need to be disassembled after being loaded into the column, and can be used again after being regenerated. When the separation effect of the straw resin does not meet the use standard after multiple uses, various treatment methods such as microbial degradation can be adopted to reduce the amount of solid waste and reduce environmental protection expenses.

[0031] (2) The present invention uses only acetone as a single organic solvent. Compared with other methods using mixed solvents, a single solvent has great advantages in terms of personnel safety, environmental toxicity and cost reduction through recycling.

[0032] (3) The extract extracted after fermentation must contain a lot of oil. The subsequent process, whether through chromatography or crystallization, is not completely processed and may be brought into the final product. The present invention can remove most of the oil through saponification, thereby increasing the content. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 Schematic diagram of the liquid phase purity of the extraction mixture in Example 1 of the present invention;

[0034] Figure 2 Schematic diagram of the purity of the liquid phase after saponification in Example 1 of the present invention;

[0035] Figure 3 Schematic diagram of the purity of the liquid phase after chromatography in Example 1 of the present invention;

[0036] Figure 4 Schematic diagram of the purity of the liquid phase after crystallization of Example 1 of the present invention;

[0037] Figure 5 Schematic diagram of the liquid phase purity of the extraction mixture in Example 2 of the present invention;

[0038] Figure 6 Schematic diagram of the purity of the liquid phase after saponification in Example 2 of the present invention;

[0039] Figure 7 Schematic diagram of the purity of the liquid phase after chromatography in Example 2 of the present invention;

[0040] Figure 8 Schematic diagram of the purity of the liquid phase after crystallization of Example 2 of the present invention;

[0041] Fig. 9 Schematic diagram of the liquid phase purity of the extraction mixture in Example 3 of the present invention;

[0042] Fig.10 Schematic diagram of the purity of the liquid phase after saponification in Example 3 of the present invention;

[0043] Fig.11 Schematic diagram of the purity of the liquid phase after chromatography in Example 3 of the present invention;

[0044] Fig.12 Schematic diagram of the purity of the liquid phase after crystallization of Example 3 of the present invention;

[0045] Fig.13 It is a schematic diagram of the liquid phase purity of the extraction mixed solution of Comparative Example 1 of the present invention;

[0046] Fig.14It is a schematic diagram of the purity of the liquid phase after chromatography of Comparative Example 1 of the present invention;

[0047] Fig.15 It is a schematic diagram of the purity of the liquid phase after crystallization of Comparative Example 1 of the present invention. DETAILED DESCRIPTION

[0048] In order to make the technical solution of the present invention clearer, the present invention is further described in detail below with reference to the accompanying drawings and specific embodiments.

[0049] Example 1

[0050] Degradable straw resin production:

[0051] 1) Dry 1kg of straw at 115℃ with air blast until the moisture content is ≤2%, crush it with an ultra-fine grinder, pass it through a 3000-mesh sieve, and obtain 0.95kg of fiber fine powder;

[0052] 2) Add the fiber fine powder obtained in step 1) into the reaction kettle, add 5.7 kg of water, heat to 40°C, add 142.5 g of polyhydroxyalkanoate and 166.25 g of polylactic acid in sequence under mechanical stirring, stir at a low speed of 50 r / min for 2 h to fully mix;

[0053] 3) Slowly add 166.25 g of binder to the mixed system obtained in step 2) until all solids are agglomerated and the surface is clear without obvious powder;

[0054] 4) Allow to settle naturally for 2 hours, filter, clean, and dry at 80℃ under vacuum;

[0055] 5) Pass through 200-mesh and 100-mesh sieves to select straw resin of appropriate size, load it into the column according to the weight of the saponified liquid, and rinse it with acetone for later use.

[0056] Menadione extraction and purification:

[0057] 1) Add 1% polyaluminium chloride (based on the weight of the fermentation liquid) to the fermentation liquid and stir to mix evenly. After standing for flocculation and precipitation for 12 hours, perform plate and frame filtration. Dry and crush the filtered fungus residue at 50°C to obtain fungus residue dry powder.

[0058] 2) Take 100g of dried mushroom residue powder, add 400mL of acetone, heat to 60℃ and stir for 1h. After the first extraction, filter and collect the filtrate. Add 300mL of acetone to the mushroom residue and stir for 1h. Filter and collect the filtrate. After the second extraction, add 200mL of acetone to the extraction tank and stir for 1h. Filter and collect the filtrate. After the third extraction, add 100mL of acetone to the extraction tank and stir for 1h. Filter, collect and mix all the filtrates.

[0059] 3) The filtrate was concentrated to 100 mL under reduced pressure and transferred to a saponification reactor. Sodium hydroxide solid was added at 3% of the filtrate volume. After reacting under pressure at 90°C for 3 hours, sodium hydroxide was added dropwise until no white solid precipitated. The saponified liquid was filtered and used for chromatography.

[0060] 4) Keep the temperature at 60℃ during the whole chromatography process. After loading, wash with 50%-70% acetone. After washing to 5-10 times the volume of the column, menaquinone-7 begins to flow out, and then switch to 100% acetone to start elution. When switching to elution, start collecting.

[0061] 5) The effluent mixture was concentrated under reduced pressure at 60°C to a concentration of 5-6 mg / mL, cooled to 10°C while stirring, and kept warm for more than 3 hours. After refrigeration, menaquinone-7 was completely precipitated and filtered.

[0062] 6) Dry at room temperature under reduced pressure until there is no moisture.

[0063] Example 2

[0064] Degradable straw resin production:

[0065] 1) Dry 1kg of straw at 115℃ with air blast until the moisture content is ≤2%, crush it with an ultra-fine grinder, pass it through a 3000-mesh sieve, and obtain 0.96kg of fiber fine powder;

[0066] 2) Add the fiber powder obtained in step 1) into the reaction kettle, add 5.76 kg of water, heat to 45 ° C, add 158.4 g of polyhydroxyalkanoate and 187.2 g of polylactic acid in sequence under mechanical stirring, stir at a low speed of 65 r / min for 3 hours to fully mix;

[0067] 3) Slowly add 187.2 g of binder to the mixed system obtained in step 2) until all solids are agglomerated and the surface is clear without obvious powder;

[0068] 4) Allow to settle naturally for 2.5 hours, filter, clean, and dry at 80℃ under vacuum;

[0069] 5) Pass through 200-mesh and 100-mesh sieves to select straw resin of appropriate size, load it into the column according to the weight of the saponified liquid, and rinse it with acetone for later use.

[0070] Menadione extraction and purification:

[0071] 1) Add 3% polyaluminium chloride (based on the weight of the fermentation liquid) to the fermentation liquid and stir to mix evenly. After standing for flocculation and precipitation for 12 hours, perform plate and frame filtration. Dry and crush the filtered fungus residue at 55°C to obtain fungus residue dry powder.

[0072] 2) Take 100g of dried mushroom residue powder, add 400mL of acetone, heat to 60℃ and stir for 1h. After the first extraction, filter and collect the filtrate. Add 300mL of acetone to the mushroom residue and stir for 1h. Filter and collect the filtrate. After the second extraction, add 200mL of acetone to the extraction tank and stir for 1h. Filter and collect the filtrate. After the third extraction, add 100mL of acetone to the extraction tank and stir for 1h. Filter, collect and mix all the filtrates.

[0073] 3) The filtrate was concentrated to 100 mL under reduced pressure and transferred to a saponification reactor. Sodium hydroxide solid was added at 3% of the filtrate volume. After reacting under pressure at 90°C for 3 hours, sodium hydroxide was added dropwise until no white solid precipitated. The saponified liquid was filtered and used for chromatography.

[0074] 4) Keep the temperature at 60℃ during the whole chromatography process. After loading, wash with 60% acetone. After washing to 5-10 times the volume of the column, menaquinone-7 begins to flow out, and then switch to 100% acetone to start elution. When switching to elution, start collecting.

[0075] 5) The effluent mixture was concentrated under reduced pressure at 60°C to a concentration of 5-6 mg / mL, cooled to 10°C while stirring, and kept warm for more than 3 hours. After refrigeration, menaquinone-7 was completely precipitated and filtered.

[0076] 6) Dry at room temperature under reduced pressure until there is no moisture.

[0077] Example 3

[0078] Production of degradable straw resin:

[0079] 1) Dry 1kg of straw at 115℃ with air blast until the moisture content is ≤2%, crush it with an ultra-fine grinder, pass it through a 3000-mesh sieve, and obtain 0.95kg of fiber fine powder;

[0080] 2) Add the fiber powder obtained in step 1) into the reaction kettle, add 5.7 kg of water, heat to 40°C, add 171 g of polyhydroxyalkanoate and 199.5 g of polylactic acid in sequence under mechanical stirring, stir at a low speed of 80 r / min for 4 hours to fully mix;

[0081] 3) Slowly add 199.5 g of binder to the mixed system obtained in step 2) until all solids are agglomerated and the surface is clear without obvious powder;

[0082] 4) Allow to settle naturally for 3 hours, filter, clean, and dry at 80℃ under vacuum;

[0083] 5) Pass through 200-mesh and 100-mesh sieves to select straw resin of appropriate size, load it into the column according to the weight of the saponified liquid, and rinse it with acetone for later use.

[0084] Menadione extraction and purification:

[0085] 1) Add 5% polyaluminium chloride (based on the weight of the fermentation liquid) to the fermentation liquid and stir to mix evenly. After standing for flocculation and precipitation for 12 hours, perform plate and frame filtration. Dry and crush the filtered fungus residue at 60°C to obtain fungus residue dry powder.

[0086] 2) Take 100g of dried mushroom residue powder, add 400mL of acetone, heat to 60℃ and stir for 1h. After the first extraction, filter and collect the filtrate. Add 300mL of acetone to the mushroom residue and stir for 1h. Filter and collect the filtrate. After the second extraction, add 200mL of acetone to the extraction tank and stir for 1h. Filter and collect the filtrate. After the third extraction, add 100mL of acetone to the extraction tank and stir for 1h. Filter, collect and mix all the filtrates.

[0087] 3) The filtrate was concentrated to 100 mL under reduced pressure and transferred to a saponification reactor. Sodium hydroxide solid was added at 3% of the filtrate volume. After reacting under pressure at 90°C for 3 hours, sodium hydroxide was added dropwise until no white solid precipitated. The saponified liquid was filtered and used for chromatography.

[0088] 4) Keep the temperature at 60℃ during the whole chromatography process. After loading, wash with 70% acetone. After washing to 5-10 times the volume of the column, menaquinone-7 begins to flow out, and then switch to 100% acetone to start elution. When switching to elution, start collecting.

[0089] 5) The effluent mixture was concentrated under reduced pressure at 60°C to a concentration of 5-6 mg / mL, cooled to 10°C while stirring, and kept warm for more than 3 hours. After refrigeration, menaquinone-7 was completely precipitated and filtered.

[0090] 6) Dry at room temperature under reduced pressure until there is no moisture.

[0091] Comparative Example 1

[0092] Same as Example 1, except that no saponification treatment was performed.

[0093] Liquid phase method: Determine according to high performance liquid chromatography (General Rule 0512). Operate in a dark environment.

[0094] Internal standard solution: Take about 37.5 mg of cholesteryl benzoate, place it in a 25 ml volumetric flask, dissolve it with mobile phase and dilute to the scale, and shake well.

[0095] Test solution: Take about 20 mg of this product, accurately weigh it, place it in a 50 ml volumetric flask, add mobile phase to dissolve and dilute to the scale, shake well, accurately measure 5 ml and 1 ml of internal standard solution, place it in a 10 ml volumetric flask, dilute to the scale with mobile phase, and shake well.

[0096] Reference solution: Take about 20 mg of menadione-7 reference substance, accurately weigh it, place it in a 50 ml volumetric flask, add mobile phase to dissolve and dilute to the scale, shake well, accurately measure 5 ml and 1 ml of internal standard solution, place it in a 10 ml volumetric flask, dilute to the scale with mobile phase, and shake well.

[0097] Chromatographic conditions: silica gel as filler; petroleum ether (60-90°C)-n-pentanol (2000:2.5) as mobile phase; detection wavelength at 254nm; injection volume 10μl.

[0098] System suitability requirements: The separation between the peak of menadione-7 and the peak of the internal standard substance should meet the requirements.

[0099] Determination method: Accurately measure the test solution and the reference solution, inject them into the liquid chromatograph respectively, record the chromatogram, and calculate by the sum of the peak areas according to the internal standard method.

[0100] Table 1 Liquid phase test results of examples and comparative examples

[0101]

[0102] As shown in Table 1, it can be seen from the data of Example 1, Example 2 and Example 3 that the quality of the menaquinone-7 product purified by the method of the present invention is relatively stable, and it can be seen from the data of Example 1 and Comparative Example 1 that adding a saponification step can effectively improve the purity of the product.

[0103] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent of the present invention. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A novel method for purifying menaquinone-7 using degradable straw resin, characterized in that: The following steps are involved: S1, preparing degradable straw stalk resin; S11, drying, crushing and sieving the straw stalks and rice husks to obtain fine fiber powder; S12, add the fiber powder obtained in step S11 into a reaction kettle, add water to heat, and then add polyhydroxyalkanoate and polylactic acid in sequence under mechanical stirring, and stir at a low speed to fully mix; S13, slowly add a binder to the mixed system in step S12, so that all solids are agglomerated and the surface is clear without obvious powder; S14, let it stand and settle naturally, filter, clean and dry; S15, pass through 200 mesh and 100 mesh sieves to select straw stalk resin of appropriate size, load into column, and rinse with acetone for later use; S2, extraction and purification of menaquinone-7; S21, adding a flocculant to the fermentation liquid and stirring to mix evenly, allowing it to stand for flocculation and precipitation, and then performing plate-and-frame filtration, and drying and crushing the filtered fungus residue to obtain fungus residue dry powder; S22, extracting the mushroom residue dry powder obtained in step S21 with acetone, collecting the extract and concentrating it under reduced pressure to obtain an extract concentrate; S23, transferring the leaching concentrate obtained in step S22 to a saponification reaction kettle, adding solid sodium hydroxide to carry out a saponification reaction, adding sodium hydroxide dropwise until no solid precipitates, filtering, and obtaining a saponified solution; S24, the saponified solution obtained in step S23 is chromatographed with straw resin, and after adsorption is completed, it is washed with 50%-70% acetone aqueous solution, and then eluted with acetone, and the eluate of menadione-7 with a purity greater than 90% is collected; S25, concentrating the eluate obtained in step S24 by vacuum rotary evaporation, cooling and crystallizing, filtering and drying until there is no moisture, and obtaining menaquinone-7 crystalline powder.

2. The method for purifying menaquinone-7 using a novel degradable straw stalk resin according to claim 1, characterized in that: In the step S11, drying is performed by air drying at 115° C. until the moisture content is ≤2%, pulverizing is performed by using an ultrafine pulverizer, and sieving is performed by passing through a 3000 mesh sieve.

3. The method for purifying menaquinone-7 using a novel degradable straw stalk resin according to claim 1, characterized in that: In the step S12, the water volume is 6 times the weight of the fiber powder obtained in step S11, the heating and stirring temperature is 40-50°C, the weight of the polyhydroxyalkanoate is 15%-18% of the weight of the fiber powder, the weight of the polylactic acid is 17.5%-21% of the weight of the fiber powder, the low-speed stirring speed is 50-80r / min, and the low-speed stirring time is 2-4h.

4. The method for purifying menaquinone-7 using a novel degradable straw stalk resin according to claim 1, characterized in that: In the step S13, the weight of the adhesive is 17.5%-21% of the weight of the fiber fine powder.

5. The method for purifying menaquinone-7 by using a novel degradable straw stalk resin according to claim 1, characterized in that: In the step S14, the natural sedimentation time is 2-3 hours, the filtering method is centrifuge filtering, and the drying method is vacuum double cone drying at 80°C.

6. The method for purifying menaquinone-7 using a novel degradable straw stalk resin according to claim 1, characterized in that: In the step S21, the flocculant is any one of polyaluminium chloride and polyferric sulfate, and the amount of the flocculant added is 0.01%-0.5% of the weight of the fermentation liquid; the static flocculation precipitation time is 12 hours; the drying is vacuum double cone drying at 50-60°C; and the pulverization is pulverized by an ultrafine pulverizer.

7. The method for purifying menaquinone-7 using a novel degradable straw stalk resin according to claim 1, characterized in that: In step S22, the acetone extraction is performed four times, the volume of acetone used is 10 times the weight of the dry powder of the mushroom residue, the extraction is performed by heating at 60°C with mechanical stirring, each extraction time is 1 hour, and the reduced pressure concentration temperature is 40°C.

8. The method for purifying menaquinone-7 using a novel degradable straw stalk resin according to claim 1, characterized in that: In the step S23, the weight of the solid sodium hydroxide added is 3% of the volume of the leaching concentrate, the saponification reaction temperature is 90° C., the saponification reaction time is 3 h, and the sodium hydroxide added dropwise is 20% sodium hydroxide aqueous solution.

9. The method for purifying menaquinone-7 using a novel degradable straw stalk resin according to claim 1, characterized in that: In step S24, the straw resin chromatography is kept at 60°C throughout the whole process, the volume of the straw resin used is 10 times the weight of the saponified solution obtained in step S23, and the volume of the acetone aqueous solution used is 5-10 times the volume of the chromatography column until menadione-7 begins to flow out.

10. The method for purifying menaquinone-7 by using a novel degradable straw stalk resin according to claim 1, characterized in that: In step S25, the eluent is concentrated under vacuum at 60°C to a concentration of 5-6 mg / ml of menaquinone-7, the crystallization temperature is 10°C, the crystallization time is 5-6 h, and the drying condition is vacuum double cone drying at 40°C.

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