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CN-118005703-B - Method for recovering hesperidin and rutin from hesperidin crystallization mother liquor

CN118005703BCN 118005703 BCN118005703 BCN 118005703BCN-118005703-B

Abstract

A method for recovering hesperidin and rutin from hesperidin crystallization mother liquor belongs to the technical field of plant extraction, and comprises the steps of S1, membrane filtration, ceramic membrane filtration and nanofiltration membrane filtration of the hesperidin crystallization mother liquor in sequence, S2, chromatographic separation, namely, chromatographic separation of nanofiltration membrane filtrate, and collection of eluent of 1-2BV and eluent of 3-4BV respectively by using 50-95% of methanol aqueous solution as gradient elution solvent, S3, concentration of eluent of 1-2BV of rutin crystallization, cooling crystallization by adding crystallization solvent, and S4, concentration of eluent of 3-4BV to a certain solid content, cooling crystallization by adding crystallization solvent, and obtaining the product of hesperidin. The method for recovering the hesperidin and the rutin has the advantages of simple and convenient operation, high recovery yield and high content of the products of the hesperidin and the rutin.

Inventors

  • LI GUOLEI
  • WANG HAO
  • GAO WEI
  • AN XIAODONG

Assignees

  • 晨光生物科技集团股份有限公司

Dates

Publication Date
20260512
Application Date
20240221

Claims (5)

  1. 1. A method for recovering hesperidin and rutin from hesperidin crystallization mother liquor, which is characterized by comprising the following steps: Step S1, membrane filtration, namely sequentially carrying out ceramic membrane filtration and nanofiltration membrane filtration on the hesperidin crystallization mother liquor; step S2, chromatographic separation, namely performing chromatographic separation on nanofiltration membrane filtrate, adopting 50-95% methanol water solution as a gradient elution solvent, and respectively collecting eluent of 1-2BV and eluent of 3-4 BV; Step S3, crystallizing the naringin, namely concentrating the eluent of 1-2BV to a certain solid content, adding a crystallization solvent for cooling crystallization to obtain the naringin product; Step S4, hesperidin crystallization, namely concentrating the eluent of 3-4BV to a certain solid content, adding a crystallization solvent for cooling crystallization to obtain a product hesperidin; the hesperidin crystallization mother liquor in the step S1 is a filtrate obtained by soaking, crushing, preprocessing, impurity removing, extracting, pH adjusting, crystallizing and filtering the hesperidin raw material, the steps of preprocessing the hesperidin raw material are carried out by adding water into the mixture for 1 to 12 hours, the water adding amount is 0.5 to 4 times of the raw material, and the crushing mesh number of wet materials is 2 to 40 meshes; the chromatographic separation in the step S2 is a silica gel chromatographic column, and gradient elution is that firstly, methanol aqueous solution with the volume fraction of 75-85% is adopted for eluting, and eluent with the volume fraction of 1-2BV is collected, and then methanol aqueous solution with the volume fraction of 90-95% is adopted for eluting, and eluent with the volume fraction of 3-4BV is collected; In the step S3, the temperature is reduced from 50 ℃ to 5-7 ℃ per hour to 15-30 ℃ by adopting the vacuum concentration until the solid content of the concentrated solution is 30-60%, 5-10% petroleum ether is added, the temperature is kept for 2 hours at 15-30 ℃, the temperature is reduced to 0-10 ℃ at 5-7 ℃ per hour, and the temperature is kept for 6-10 hours; In the step S4, the concentrated solution is concentrated to 25-50% of solid content in vacuum at 50 ℃, the temperature reduction curve is cooled from 50 ℃ to 20-30 ℃ at 4-8 ℃ per hour, 3-12% petroleum ether is added, the temperature is kept for 2 hours at 20-30 ℃, the temperature is reduced to 0-10 ℃ at 4-8 ℃ per hour, and the temperature is kept for 8-15 hours.
  2. 2. The method for recovering hesperidin and naringin from hesperidin crystallization mother liquor according to claim 1, wherein the impurity removing liquid used in the impurity removing step is one or more selected from sodium citrate solution, sodium carbonate solution and calcium chloride solution, the concentration of the impurity removing liquid is 0.1% -2.0%, the impurity removing temperature is 10-40 ℃, and the impurity removing time is 0.5-4 h.
  3. 3. The method for recovering hesperidin and naringin from hesperidin crystallization mother liquor according to claim 1, wherein the extraction solvent in the extraction step is sodium hydroxide aqueous solution, the extraction temperature is 10-40 ℃, the extraction time is 0.5-4 h, the extraction times are 3-6, the use amount of each extraction solvent is 2-20 times of that of the raw material, and the secondary extraction solution or the tertiary extraction solution is used as the extraction solvent for the next extraction.
  4. 4. The method for recovering hesperidin and naringin from hesperidin crystallization mother liquor according to claim 1, wherein the pH value of the hesperidin extract is adjusted to 7-8, the acid used for adjusting the pH is any one of hydrochloric acid, phosphoric acid and sulfuric acid, and then the mixture is kept stand for 6-10 hours at 20-35 ℃.
  5. 5. The method for recovering hesperidin and naringin from hesperidin crystallization mother liquor according to claim 1, wherein the pore diameter of the ceramic membrane in the step S1 is 5nm-50nm, the filtration temperature is 20-35 ℃, the filtration pressure is 0.30+ -0.10 MPa, the molecular weight of the nanofiltration membrane is 700-900, the filtration temperature is 20-35 ℃, and the filtration pressure is 0.60+ -0.10 MPa.

Description

Method for recovering hesperidin and rutin from hesperidin crystallization mother liquor Technical Field The invention belongs to the technical field of plant extraction, and particularly relates to a method for recovering hesperidin and rutin from hesperidin crystallization mother liquor. Background The hesperidin is used as a pharmaceutical intermediate, has the function of protecting blood vessels, is used for treating cardiovascular diseases, or is used as an intermediate for synthesizing diosmin or other raw materials, and is one of main components of Chinese patent medicine Maitong. The rutin naringin can be used as natural pigment, flavor modifier and bittering agent for food and beverage production, can be used as raw material for synthesizing novel sweeteners naringin dihydrochalcone and neohesperidin dihydrochalcone, can be used for producing medicaments for preventing and treating cardiovascular and cerebrovascular diseases, easing pain, clearing heat and diminishing inflammation in the pharmaceutical industry, and can also be used for preparing various high-added-value organic matters such as rhamnose, lemon-rope acidic azo dyes and semisynthetic flavonoid compounds with higher biological activity and medicinal value. The existing production process for extracting the hesperidin is an alkali extraction and acid precipitation method, namely, the hesperidin is extracted by ring-opening dissolution under an alkali condition, and closed-loop precipitation is carried out under an acid condition for separation, a large amount of waste water (the amount of waste water processed by each ton of raw materials is 10-20 tons) is generated in the process, and 0.18-0.30% of hesperidin and 0.25-0.35% of rutin are not effectively developed and utilized, so that the resource waste is caused. The patent CN111423476A discloses a process for extracting and purifying the rutin from the bitter orange processing waste liquid, which is mainly characterized in that the rutin is filtered by a ceramic membrane and purified by a macroporous adsorption resin column for 2 times, 3 examples of which are described in the specification, and the content of the rutin in the obtained extract rutin product is only 26.1%, 35.4% and 33.7% respectively. The recycling of the hesperidin and the rutin in the hesperidin wastewater has extremely important significance for the comprehensive utilization and development of young fruits of oranges. Disclosure of Invention The invention aims to provide a method for recovering hesperidin and naringin from hesperidin crystallization mother liquor, which overcomes the defects in the prior art, is convenient to operate, and has high yield and high content of hesperidin and naringin. In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a method for recovering hesperidin and naringin from hesperidin crystallization mother liquor, comprising the following steps: step S1, membrane filtration, namely sequentially carrying out ceramic membrane filtration and nanofiltration membrane filtration on the hesperidin crystallization mother liquor; step S2, chromatographic separation, namely performing chromatographic separation on nanofiltration membrane filtrate, adopting 50-95% methanol water solution as a gradient elution solvent, and respectively collecting eluent of 1-2BV and eluent of 3-4 BV; Step S3, crystallizing the naringin, namely concentrating the eluent of 1-2BV to a certain solid content, adding a crystallization solvent for cooling crystallization to obtain the naringin product; And S4, crystallizing the hesperidin, namely concentrating the eluent of 3-4BV to a certain solid content, adding a crystallization solvent, and cooling and crystallizing to obtain the hesperidin product. The invention further improves the technical scheme that the source of the hesperidin crystallization mother liquor in the step S1 is a filtrate obtained by soaking, crushing, preprocessing, impurity removing, extracting, pH adjusting, crystallizing and filtering the hesperidin raw material, wherein the water is added into the hesperidin raw material preprocessing procedure for soaking for 1-12h, the water addition amount is 0.5-4 times of that of the raw material, and the wet material crushing mesh number is 2-40 mesh. The technical scheme of the invention is further improved in that the impurity removing liquid used in the impurity removing step is one or more selected from sodium citrate solution, sodium carbonate solution and calcium chloride solution, the concentration of the impurity removing liquid is 0.1% -2%, the mass ratio of feed liquid is 1:2-1:8, the impurity removing temperature is 10-40 ℃, and the impurity removing time is 0.5-4 h. The technical scheme of the invention is further improved in that the extraction solvent in the extraction step is sodium hydroxide aqueous solution, the extraction temperature is 10-40 ℃, the extraction time is 0.5-4 h, the extract