CN113135822B - Method for efficiently separating shikimic acid from ginkgo leaf extract processing wastewater - Google Patents
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Abstract
The invention relates to a method for efficiently separating shikimic acid from ginkgo leaf extract processing wastewater. Taking waste water generated in the production process of the ginkgo leaf extract as a raw material, firstly filtering and separating by using an ultrafiltration membrane with the molecular weight cutoff of 30-50 kDa, continuously concentrating and enriching the permeate of the ultrafiltration membrane by using a nanofiltration membrane, adding the nanofiltration concentrate into a chromatographic column filled with polymer nano microspheres for adsorption and purification, eluting by using 3-4 times of column volume of water after the sample loading is finished, eluting by using 20-30% ethanol solution, collecting an ethanol elution part, decompressing and recovering ethanol from the eluate for concentration and drying to obtain a shikimic acid product, wherein the purity of the shikimic acid is more than 99%. The technology has the advantages of low energy consumption, simple operation, environmental protection and safety, and the shikimic acid can be recovered in a gingko extract workshop without adding new solvent types, so that the technology is very suitable for popularization and use in industry.
Description
Technical Field
The invention relates to the technical field of plant extracts, in particular to a method for efficiently separating and preparing shikimic acid from ginkgo leaf extract processing wastewater.
Background
Gingko is an important economic forest tree species in China, and the gingko industry chain is 200 hundred million yuan and is an important local agriculture and forestry characteristic industry. The gingko resources in China account for more than 85 percent of the world, the planting area is 40 million hectares, and the annual yield of the dried gingko leaves is more than 4 million tons. At present, ginkgo leaves are mainly used for processing ginkgo extracts which mainly contain flavone and lactone active substances and are widely applied to medicines, functional foods and cosmetics. The traditional ginkgo biloba extract processing process can generate a large amount of byproducts such as waste water, leaf residues and the like, most of the byproducts are discharged or treated as fertilizers, the resource utilization rate is low, and the environment is polluted.
The ginkgo extract processing wastewater contains a large amount of shikimic acid which is an important drug synthesis raw material, the application is wide in drug production, the added value is extremely high, and the price of 1 ton reaches 80 ten thousand yuan at present. The content of shikimic acid in the ginkgo leaves is as high as about 4 percent, which is close to the content of shikimic acid in the star anise. The traditional ginkgo extract processing technology adopts a pharmacopoeia method, ginkgo leaves are extracted by dilute ethanol and then purified by macroporous resin, a large amount of chromatography flow-through liquid and water washing liquid are generated in the technological process and are treated as waste liquid, and shikimic acid is not adsorbed by resin and is greatly lost in the waste liquid, and the content of shikimic acid in the waste liquid is 2-3%. Therefore, the green and efficient technology is adopted to separate high-purity shikimic acid from the ginkgo waste liquid, the utilization rate of ginkgo resources can be improved, a ginkgo resource product with high added value can be obtained, and the development and utilization of shikimic acid resources can be expanded.
The existing method for enriching and purifying shikimic acid mainly comprises a solvent extraction method, silica gel column chromatography, an anion exchange resin adsorption method and the like. The solvent extraction method and the silica gel column chromatography can use a large amount of toxic reagents, have poor safety, and have the defects of complex operation, low separation efficiency, no repeated use of silica gel, high cost, difficult scale production and the like. At present, ion exchange resin adsorption separation methods are more applied, but acid liquor or alkali liquor is needed to carry out column elution in the process, so that the environment is polluted, the product recovery cost is high, the yield is only 60-70%, the resin regeneration operation is complicated, the wastewater amount is large, and the production period is long.
The membrane separation is a new separation technology, has the technical advantages of simple and convenient process, no thermal effect, no pollution, high separation efficiency and the like, and is widely applied to the separation of plant active ingredients. The membrane technology is mainly applied to the combination of an ultrafiltration membrane process and a nanofiltration membrane process, the ultrafiltration can remove macromolecular impurities without influencing target components, the nanofiltration can remove small molecular impurities and realize efficient enrichment and concentration without a thermal effect, in addition, the membrane treatment can prevent column chromatography adsorption materials from being polluted and blocked, and the treatment capacity of an adsorption column is improved. The polymer nano-microsphere is a novel macromolecular adsorption material and has good application effect in separation and purification of natural products. Compared with silica gel and ion exchange resin, the method has the advantages of high selectivity, large loading capacity, strong rigidity, long service life, environment-friendly elution solvent, high product yield and purity, simple and convenient operation and the like.
At present, no relevant research and report of applying membrane separation or polymer nano microsphere purification technology to separation of shikimic acid in ginkgo exists. Therefore, the invention provides a method for efficiently enriching shikimic acid from wastewater by using ginkgo biloba extract processing wastewater as a raw material and adopting technologies such as ultrafiltration-nanofiltration combination, polymer nano microsphere adsorption separation and the like to obtain shikimic acid products with the purity of more than 99%. The technology has low energy consumption, realizes the high-efficiency enrichment of shikimic acid, can use ethanol water solution to carry out column elution, is green and safe, can recover shikimic acid without adding new solvent types in a gingko extract workshop, and is very suitable for popularization and use in industry.
Disclosure of Invention
The invention aims to provide a method for efficiently separating and preparing shikimic acid from ginkgo leaf extract processing wastewater, which has the advantages of simple operation, low production cost and high purity of the obtained shikimic acid product, and is suitable for industrial production.
The invention is realized by the following technical scheme.
A method for efficiently separating shikimic acid from ginkgo leaf extract processing wastewater comprises the following specific steps:
(1) Membrane separation
Taking waste water generated in the production process of the ginkgo leaf extract, filtering and separating the waste water by using an ultrafiltration membrane, wherein the molecular weight cut-off of the ultrafiltration membrane is 30-100 kDa; and (3) concentrating and enriching the permeate of the ultrafiltration membrane by using a nanofiltration membrane, wherein the intercepted relative molecular mass of the nanofiltration membrane is 100-300 Da, the operating temperature is 20-30 ℃, and the operating pressure is 0.5-1.5 MPa, so that the nanofiltration concentrate is obtained for later use.
(2) Purification of polymer nano-microspheres
Adding nanofiltration concentrated solution into a chromatographic column filled with polymer nano microspheres to perform sample loading adsorption, eluting with 3-4 times of column volume of water after sample loading is finished, eluting with 20-40% ethanol solution at the rate of 8-12 mL/min, wherein the amount of the ethanol solution is 2-4 times of the column volume, collecting the ethanol eluted part, recovering ethanol from ethanol eluate under reduced pressure, concentrating and drying to obtain shikimic acid products, and analyzing by HPLC, wherein the shikimic acid purity is more than 99%.
The wastewater generated in the production process of the ginkgo leaf extract in the step (1) is a combined solution of column-loading effluent and water washing liquid generated in the process of purifying the ginkgo leaf extracting solution by macroporous resin; the type of the polymer nano microsphere in the step (2) is one of PS25-300, NM-MM100 and PSA 30-300; the drying in the step (2) is one of vacuum drying, spray drying or freeze drying.
The invention takes the waste water generated in the production process of the ginkgo leaf extract as the raw material, and adopts the technologies of ultrafiltration-nanofiltration combination, polymer nano microsphere adsorption separation and the like to efficiently prepare the high-purity shikimic acid product from the waste water.
Filtering and separating the wastewater by using an ultrafiltration membrane, wherein the molecular weight cut-off of the ultrafiltration membrane is 30-100 kDa, and the preferred molecular weight cut-off of the ultrafiltration membrane is 30-50 kDa; the invention inspects the influence of the relative molecular mass intercepted by the ultrafiltration membrane on the shikimic acid permeability and the protein removal rate, and the result shows that the relative molecular mass intercepted by the ultrafiltration membrane is within the range of 30-50 kDa, the shikimic acid permeability is higher than 99 percent, and the protein removal rate is more than 96 percent, so the ultrafiltration membrane with the relative molecular mass intercepted by the ultrafiltration membrane of 30-50 kDa is preferably selected for purification.
And (3) concentrating and enriching the permeate of the ultrafiltration membrane by using a nanofiltration membrane, wherein the intercepted relative molecular mass of the nanofiltration membrane is 100-300 Da, the operating temperature is 20-30 ℃, the operating pressure is 0.5-1.5 MPa, and the preferred operating pressure is 1.0-1.5 MPa, so that the nanofiltration concentrate is obtained. The invention inspects the influence on the shikimic acid retention rate under different operating pressure conditions, and the result shows that when the operating pressure is in the range of 1.0-1.5 MPa, the shikimic acid retention rate is over 95 percent, so the nanofiltration operating pressure is preferably 1.0-1.5 MPa.
The method adopts a polymer nano microsphere adsorption technology to purify shikimic acid, nano-filtration concentrated solution is added into a chromatographic column filled with polymer nano microspheres to carry out sample loading adsorption, water with 3-4 times of column volume is firstly used for eluting after sample loading is finished, then 20-40% ethanol solution is used for eluting, preferably, the ethanol concentration is 20-30%, the elution speed is 8-12 mL/min, preferably, the elution speed is 10-12 mL/min, the using amount of the ethanol solution is 2-4 times of column volume, an ethanol elution part is collected, ethanol eluent is decompressed, recovered and concentrated and dried to obtain a shikimic acid product, and the purity of the shikimic acid is more than 99% through HPLC analysis.
The invention inspects the influence of different types of polymer nano microspheres on the adsorption and elution performance and the product purity of shikimic acid, and the results show that the adsorption rate of the polymer nano microspheres of NM-MM100 and PSA30-300 is the maximum and reaches more than 95%, and in a desorption test, the desorption rate is more than 90%, and the purity of shikimic acid is higher than 99%, so that the shikimic acid is preferably separated and purified by using the polymer nano microspheres of NM-MM100 and PSA 30-300.
The invention examines the concentration of the ethanol as the elution solvent, and the result shows that the ethanol with the concentration of 20-30 percent can remove more than 90 percent of shikimic acid by acid washing, the purity of the shikimic acid can reach more than 99 percent, so the ethanol with the concentration of 20-30 percent is preferably used as the elution solvent.
The invention examines the elution speed, and the result shows that when the elution speed is 10-12 mL/min, more than 90% of shikimic acid can be washed off by acid, the purity of shikimic acid can reach more than 99%, so the preferred elution speed is 10-12 mL/min.
The shikimic acid drying mode is one of vacuum drying, spray drying or freeze drying; the vacuum drying is ordinary vacuum drying or microwave vacuum drying, the ordinary vacuum drying condition is that the temperature is 60-90 ℃, the vacuum degree is 90-100 KPa, the microwave vacuum drying condition is that the temperature is 30-60 ℃, the vacuum degree is 80-100 KPa, and the microwave power is 800-1600 w; the spray drying conditions are that the air inlet temperature is 160-200 ℃, the feeding flow is 200-400 ml/h, and the air outlet temperature is 60-100 ℃; the freeze drying condition is that the temperature is minus 30 to minus 50 ℃ and the time is 12 to 24 hours.
The invention has the beneficial effects that:
(1) The invention adopts ultrafiltration-nanofiltration membrane combined separation technology to pretreat the ginkgo wastewater, thereby not only effectively removing macromolecular impurities such as protein, polysaccharide and the like in the wastewater and enriching shikimic acid, but also being capable of carrying out non-thermal dehydration concentration, and greatly reducing energy consumption and production cost; the wastewater can also prevent the pollution and blockage of subsequent column chromatography materials after being processed by the membrane.
(2) The method adopts the polymer nano microspheres to separate and purify the shikimic acid, replaces the traditional ion exchange resin separation, has the advantages of strong selectivity, large loading capacity, strong rigidity, high product yield, simple operation, long service life and the like, can use ethanol water solution for elution, is green and safe, can recover the shikimic acid without adding new solvent types in a ginkgo extract workshop, and is very suitable for popularization and use in industry.
(3) The method effectively separates and prepares the shikimic acid from the ginkgo leaf extract processing wastewater, the obtained shikimic acid product has the purity of more than 99 percent, reaches the medicinal grade, has extremely high additional value, not only realizes the high-valued utilization of ginkgo leaf processing waste resources, but also develops new shikimic acid resources.
Detailed Description
The following examples further illustrate the present invention in detail, but the present invention is not limited thereto.
Example 1:
membrane purification process
Taking waste water generated in the production process of the ginkgo leaf extract, filtering and separating the waste water by using an ultrafiltration membrane, wherein the molecular weight cut-off of the ultrafiltration membrane is 30-100 kDa, and the relative molecular weight cut-off of the ultrafiltration membrane is preferably 30-50 kDa; concentrating and enriching the permeate of the ultrafiltration membrane by using a nanofiltration membrane, wherein the intercepted relative molecular mass of the nanofiltration membrane is 100-300 Da, the operating temperature is 20-30 ℃, the operating pressure is 0.5-1.5 MPa, and the preferred operating pressure is 1.0-1.5 MPa, so as to obtain the nanofiltration concentrate for later use.
The invention selects ultrafiltration membranes with the retention relative molecular mass of 30, 50, 60 and 100kDa respectively, inspects the influence of the pore size of the ultrafiltration membrane on the shikimic acid permeability and the protein removal rate, and the result is shown in table 1. The table shows that the ultrafiltration membrane has the intercepted relative molecular mass of 30-100 kDa, the shikimic acid permeability is higher than 99 percent, almost no loss exists, but the protein removal effect is reduced along with the increase of the intercepted molecular mass of the ultrafiltration membrane, and the protein removal rate reaches more than 96 percent when the ultrafiltration membrane has the intercepted relative molecular mass of 30-50 kDa, so the ultrafiltration membrane preferably intercepts the ultrafiltration membrane with the intercepted relative molecular mass of 30-50 kDa for purification.
The invention concentrates and enriches the permeate of the ultrafiltration membrane by using a nanofiltration membrane, inspects the influence on the shikimic acid retention rate under different operating pressures (0.5 MPa, 1.0MPa and 1.5 MPa), and has the result shown in table 2. It can be seen from the table that the shikimic acid retention rate increases with the increase of the nanofiltration operation pressure, and when the operation pressure is in the range of 1.0-1.5 MPa, the shikimic acid retention rate is all above 95%, so the nanofiltration operation pressure is preferably 1.0-1.5 MPa.
TABLE 1 separation of shikimic acid and protein by ultrafiltration membranes with different cut-off molecular weights
TABLE 2 Effect of different operating pressures on shikimic acid rejection
Example 2:
adsorption and purification process for polymer nano-microspheres
Adding the nanofiltration concentrated solution into a chromatographic column filled with polymer nano microspheres for sample loading adsorption, eluting with 3-4 times of column volume of water after sample loading is finished, and then eluting with 20-40% ethanol solution, preferably with the ethanol concentration of 20-30%. The elution speed is 8-12 mL/min, preferably 10-12 mL/min. The using amount of the ethanol solution is 2-4 times of the column volume, the ethanol elution part is collected, the ethanol elution is recovered under reduced pressure and concentrated and dried to obtain shikimic acid products, and the purity of the shikimic acid is more than 99 percent through HPLC analysis.
The polymer nano-microsphere is one of PS25-300, NM-MM100 and PSA30-300, the static adsorption capacity test and the static adsorption-elution performance test of different types of polymer nano-microspheres on shikimic acid are considered, and the results are shown in Table 3. The results show that NM-MM100 and PSA30-300 have the largest adsorption rate, both reaching more than 95%, and in the desorption test, the desorption rate is more than 90%, and the purity of shikimic acid is higher than 99%, so that it is preferable to use NM-MM100 and PSA30-300 polymer nanospheres to separate and purify shikimic acid.
TABLE 3 static adsorption-elution Performance test of different Polymer nanospheres on shikimic acid
According to the invention, the concentration of an elution solvent ethanol is considered, 100mL of polymer nano microspheres which fully adsorb shikimic acid are filled into a column, the polymer nano microspheres are eluted with 20%, 30% and 40% ethanol solutions at constant speed respectively, 1 fraction is collected for each concentration, the elution rate and the purity of shikimic acid in each eluent fraction are respectively measured, the result is shown in table 4, the result shows that ethanol with the concentration of 20% -30% can be used for pickling and removing more than 90% of shikimic acid, and the purity of shikimic acid can reach more than 99%. Therefore, 20 to 30 percent of ethanol is preferably used as an elution solvent.
TABLE 4 selection of ethanol concentration of elution solvent
The invention examines the elution speed, takes 100mL polymer nanometer microsphere which fully absorbs shikimic acid to load the column, uses 20% ethanol solution to elute with the speed of 8 mL, 10mL, 12mL/min respectively with 400mL, collects the eluent of each speed respectively, determines the elution rate and purity of shikimic acid in each eluent respectively, the result is shown in Table 5, the result shows that when the elution speed is 10-12 mL/min, more than 90% shikimic acid can be eluted, the shikimic acid purity can reach more than 99%. Therefore, the elution rate is preferably 10 to 12mL/min.
TABLE 5 selection of elution rates
Example 3:
preparation of high purity shikimic acid
(1) Membrane separation
Taking 10L of wastewater generated in the production process of the ginkgo leaf extract, filtering and separating the wastewater by using an ultrafiltration membrane, wherein the relative molecular mass intercepted by the ultrafiltration membrane is 30kDa; and (3) concentrating and enriching the permeate of the ultrafiltration membrane by using a nanofiltration membrane, wherein the intercepted relative molecular mass of the nanofiltration membrane is 100Da, the operating temperature is 20 ℃, and the operating pressure is 1.0MPa, so as to obtain a nanofiltration concentrate.
(2) Adsorption and purification of polymer nano-microsphere
a. And (3) filling the column by a wet method, wherein the diameter of the column is 10cm, the height of the column is 80cm, and the filling amount of the PSA30-300 polymer nano microspheres is 2L.
b. And adsorbing the nanofiltration membrane concentrated solution by using a polymer nano microsphere column, washing the nanofiltration membrane concentrated solution by using 3 times of column volume until the nanofiltration membrane concentrated solution is colorless, eluting the nanofiltration membrane concentrated solution by using 3 times of column volume of 20% ethanol, wherein the elution speed is 10mL/min, collecting an ethanol elution part, recovering ethanol from the ethanol eluate under reduced pressure, concentrating the ethanol, and drying the ethanol eluate in vacuum to obtain 191.3g of shikimic acid product, wherein the shikimic acid purity is 99.15% by HPLC analysis.
Example 4:
(1) Membrane separation
Taking 10L of wastewater generated in the production process of the ginkgo biloba extract, filtering and separating the wastewater by using an ultrafiltration membrane, wherein the relative molecular mass intercepted by the ultrafiltration membrane is 40kDa; and (3) concentrating and enriching the permeate of the ultrafiltration membrane by using a nanofiltration membrane, wherein the intercepted relative molecular mass of the nanofiltration membrane is 100Da, the operation temperature is 30 ℃, and the operation pressure is 1.2MPa, so that the nanofiltration concentrate is obtained.
(2) Adsorption and purification of polymer nano-microsphere
a. And (3) filling the column by a wet method, wherein the diameter of the column is 10cm, the height of the column is 80cm, and the filling amount of the NM-MM100 polymer nano microspheres is 2L.
b. And adsorbing the nanofiltration membrane concentrated solution by using a polymer nano microsphere column, washing with water of 4 times of column volume until the solution is colorless, eluting with 30% ethanol of 4 times of column volume at an elution speed of 12mL/min, collecting an ethanol elution part, recovering ethanol from the ethanol eluate under reduced pressure, concentrating, and freeze-drying to obtain 190.8g of shikimic acid product, wherein the shikimic acid purity is 99.08% through HPLC analysis.
Example 5:
(1) Membrane separation
Taking 10L of wastewater generated in the production process of the ginkgo leaf extract, filtering and separating the wastewater by using an ultrafiltration membrane, wherein the relative molecular mass intercepted by the ultrafiltration membrane is 50kDa; and (3) concentrating and enriching the permeate of the ultrafiltration membrane by using a nanofiltration membrane, wherein the intercepted relative molecular mass of the nanofiltration membrane is 200Da, the operation temperature is 25 ℃, and the operation pressure is 1.5MPa, so that the nanofiltration concentrate is obtained.
(2) Adsorption and purification of polymer nano-microsphere
a. And (3) filling the column by a wet method, wherein the diameter of the column is 10cm, the height of the column is 80cm, and the filling amount of the PSA30-300 polymer nano microspheres is 2L.
b. Adsorbing the nanofiltration membrane concentrated solution by using a polymer nano microsphere column, washing with water of 3 times of column volume until the solution is colorless, eluting with 20% ethanol of 3 times of column volume at an elution speed of 10mL/min, collecting an ethanol elution part, recovering ethanol from the ethanol eluate under reduced pressure, concentrating, and spray drying to obtain 192.5g shikimic acid product, wherein the shikimic acid purity is 99.37% by HPLC analysis.
Example 6:
(1) Membrane separation
Taking 10L of wastewater generated in the production process of the ginkgo leaf extract, filtering and separating the wastewater by using an ultrafiltration membrane, wherein the relative molecular mass intercepted by the ultrafiltration membrane is 30kDa; and (3) concentrating and enriching the permeate of the ultrafiltration membrane by using a nanofiltration membrane, wherein the intercepted relative molecular mass of the nanofiltration membrane is 300Da, the operating temperature is 25 ℃, and the operating pressure is 1.5MPa, so as to obtain a nanofiltration concentrate.
(2) Adsorption and purification of polymer nano-microsphere
a. And (3) filling the column by a wet method, wherein the diameter of the column is 10cm, the height of the column is 80cm, and the filling amount of the NM-MM100 polymer nano microspheres is 2L.
b. And adsorbing the nanofiltration membrane concentrated solution by using a polymer nano microsphere column, washing with water of 4 times of column volume until the solution is colorless, eluting with 30% ethanol of 4 times of column volume at an elution speed of 12mL/min, collecting an ethanol elution part, recovering ethanol from the ethanol eluate under reduced pressure, concentrating, and spray-drying to obtain 193.4g of shikimic acid product, wherein the shikimic acid purity is 99.29% by HPLC analysis.
Claims (3)
1. A method for efficiently separating shikimic acid from ginkgo leaf extract processing wastewater is characterized by comprising the following steps:
(1) Membrane separation
Taking waste water generated in the production process of the ginkgo leaf extract, and filtering and separating the waste water by using an ultrafiltration membrane, wherein the molecular weight cutoff of the ultrafiltration membrane is 30-100 kDa; concentrating and enriching the permeate of the ultrafiltration membrane by using a nanofiltration membrane, wherein the intercepted relative molecular mass of the nanofiltration membrane is 100-300 Da, the operating temperature is 20-30 ℃, and the operating pressure is 0.5-1.5 MPa, so as to obtain a nanofiltration concentrate for later use;
(2) Purification of polymer nano-microspheres
Adding nanofiltration concentrated solution into a chromatographic column filled with polymer nano microspheres, carrying out sample loading adsorption, eluting with 3-4 times of column volume of water after sample loading is finished, eluting with 20-40% ethanol solution at the rate of 8-12 mL/min at the amount of 2-4 times of column volume, collecting ethanol elution part, recovering ethanol from ethanol eluate under reduced pressure, concentrating and drying to obtain shikimic acid product, and analyzing by HPLC, wherein the shikimic acid purity is more than 99%;
the polymer nano microsphere type is one of PS25-300, NM-MM100 and PSA 30-300.
2. The method for efficiently separating shikimic acid from ginkgo biloba leaf extract processing wastewater as claimed in claim 1, wherein the method comprises the following steps: the wastewater generated in the production process of the ginkgo leaf extract in the step (1) refers to a combined solution of column-loading effluent and water washing liquid generated in the process of purifying the ginkgo leaf extracting solution by macroporous resin.
3. The method for efficiently separating shikimic acid from ginkgo biloba leaf extract processing wastewater as claimed in claim 1, wherein: the drying in the step (2) is one of vacuum drying, spray drying or freeze drying.
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| JP2005104921A (en) * | 2003-09-30 | 2005-04-21 | Tama Seikagaku Kk | New extract of ginkgo leaf and method for producing the same |
| JP2006111617A (en) * | 2004-09-15 | 2006-04-27 | Toyo Shinyaku:Kk | Composition containing ginkgo leaf extract |
| JP5737751B2 (en) * | 2011-03-09 | 2015-06-17 | 学校法人上智学院 | Shikimic acid acquisition method and shikimic acid production method |
| CN109593034B (en) * | 2018-11-22 | 2022-02-11 | 桂林莱茵生物科技股份有限公司 | Method for preparing shikimic acid from ginkgo leaf extraction waste liquid |
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