CN103772457A - Method for preparing geniposidic acid in eucommia leaf - Google Patents
Method for preparing geniposidic acid in eucommia leaf Download PDFInfo
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- CN103772457A CN103772457A CN201210404302.6A CN201210404302A CN103772457A CN 103772457 A CN103772457 A CN 103772457A CN 201210404302 A CN201210404302 A CN 201210404302A CN 103772457 A CN103772457 A CN 103772457A
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- geniposidic acid
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- folium eucommiae
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Abstract
The invention discloses a method for preparing geniposidic acid in eucommia leaf. The method is as below: crushing the eucommia leaves, extracting with warm water under assistance of cellulase, carrying out conventional filtration, removing impurities by an ultrafiltration membrane, concentrating by nanofiltration, separating and purifying by macroporous resin, concentrating and drying to obtain a geniposidic acid powder. The method uses cellulose-assisted warm water extraction of geniposidic acid in eucommia leaf, reaches an extraction rate of 95%, and has low water extraction temperature and short extraction time; ultrafiltration membrane is adopted to purification of the extract and separation of other by-products, and has the advantages of simple membrane operation process, stable membrane flux for a long time, easiness for cleaning, long service life and realization of industrialization; nanofiltration membrane is employed for concentrating the extract with impurities removed, so as to reduce the load of subsequent process and lengthen the service life of resins; the nanofiltration filtrate has a COD value of no more than 100, can be reused in the production process, and has no waste water discharge; and macroporous adsorption resin can effectively purify the geniposidic acid, so that the prepared powder contains geniposidic acid with purity greater than 60% and extraction rate of higher than 2.5%.
Description
Technical field
The present invention relates to a kind of method of producing Geniposidic acid in Folium Eucommiae, particularly relate to a kind of method that adopts warm water extraction in enzyme process, membrane separation technique binding resin technique to prepare Geniposidic acid.
Background technology
Geniposidic acid is a kind of important biologically active substance, has the multiple pharmacological effect such as hepatic cholagogic, hypertension, neuroprotective cell, anti-inflammatory, antitumor, antithrombotic, inhibition osteoporosis, is widely used in medical treatment, field of health care products.Geniposidic acid is mainly present in the natural phant such as the bark of eucommia, cape jasmine.The bark of eucommia is the distinctive economical seeds of China, distributed areas are large, aboundresources, in Folium Eucommiae, the content of Geniposidic acid is 1～4%, it is the desirable feedstock of extracting Geniposidic acid, domestic existing carry in process program, exist that extraction yield is not high, product purity is low, energy consumption greatly, in a large number with an organic solvent, the problem such as wastewater flow rate is large, seriously restricted the development of bark of eucommia industry.
Chinese patent: CN101260131A " extracts the method for iridoid active site and monomer " and discloses a kind of technique of preparing Geniposidic acid from the bark of eucommia (skin, leaf or seed) from the bark of eucommia, this technique comprises the steps such as high temperature extraction, the extraction of organic molten profit, preparative chromatography separation, it is high that this scheme exists high temperature extraction energy consumption, when extraction, consumption of organic solvent is large, adopt preparative chromatography to separate and be difficult to realize scale operation, and the problem such as cost is higher.Chinese patent: CN1241560A " by super method of facing outer carbonic acid gas extracting effective components from Folium Eucommiae " discloses a kind of method of extracting Geniposidic acid with supercritical co from Folium Eucommiae, the method gained Geniposidic acid purity higher (reaching more than 90%), but equipment investment is higher.
Summary of the invention
In order to overcome above-mentioned problems of the prior art and shortcoming, the invention provides a kind of method of producing Geniposidic acid in Folium Eucommiae, the method is in the Folium Eucommiae powder after pulverizing, adopt the Geniposidic acid adding in cellulase and middle warm water extraction Folium Eucommiae, by two-stage membrane separation technique binding resin absorb-elute technique, the Geniposidic acid extracting is carried out to separation and purification again, collect ethanol eluate concentrating under reduced pressure, after vacuum-drying, obtain product Geniposidic acid, efficiently solve original Geniposidic acid produce in extraction yield low, large and the low problem of product purity of wastewater flow rate.
The technical solution adopted for the present invention to solve the technical problems is: in the Folium Eucommiae powder after pulverizing, adopt the Geniposidic acid adding in a certain amount of cellulase and middle warm water extraction Folium Eucommiae, by two-stage membrane separation technique binding resin absorb-elute technique, the Geniposidic acid extracting is carried out to separation and purification, after collection ethanol eluate concentrating under reduced pressure, vacuum-drying, obtain product Geniposidic acid powder.
The present invention produces the method steps of Geniposidic acid in Folium Eucommiae and comprises:
1, the pulverizing of raw material leaf: dry Folium Eucommiae, its water content≤14%, crosses 80 mesh sieves after pulverizing by ordinary method;
2, the auxiliary middle warm water extraction of enzyme process: will add a certain amount of water in the raw material leaf of pulverizing, regulating pH is 4.5, and constant temperature to 50 ℃～60 ℃, add appropriate cellulase to extract under the following conditions: cellulase addition is concentration of substrate 0.2%, every kg feed material leaf need consume cellulase, the Folium Eucommiae of 0.002 kilogram: mass ratio=1 of water: 12, extract 2 times, each 60～80min;
3, filter: merge after extracted twice liquid, remove the impurity such as suspended substance by conventional filtration method;
4, ultra-filtration membrane removal of impurities: it is the ultrafiltration membrane treatment Folium Eucommiae water extraction liquid of 0.02～0.0.06 μ m that the present invention adopts pore size filter, this film can be held back the impurity such as most macro-molecular protein and polysaccharide, and Geniposidic acid molecular weight is can to see through completely about 400Dal, the operational condition of this film is: P=0.2～0.6Mpa, T=30～50 ℃, PH=4～5, Q=60～70L/min;
5, nanofiltration is concentrated: the present invention adopts the nanofiltration membrane that interception molecular weight is 200～400Dal to concentrate one-level membrane filtration liquid, and can be partially desalted.This grade of membrane concentration multiple can reach more than 15 times, and inorganic ion clearance can reach 60%.The operational condition of this film is: P=1.0～1.5Mpa, T=30～60 ℃, PH=4～5, Q=20L/min.
6, the separation and purification of macroporous resin: nanofiltration membrane concentrated solution carries out absorb-elute by macroporous resin, first wash away impurity with the pure water of 2 times of resin column volumes, then be 30% ethanol elution with the concentration of volume percent of 2.5 times of resin column volumes, collect ethanol eluate.
7, concentrated and dry: the ethanol eluate of collection can be obtained to Geniposidic acid powder art after by conventional concentrating under reduced pressure and vacuum-drying.
In above-mentioned steps 2, the extraction yield of Folium Eucommiae Geniposidic acid can reach 95%.
In above-mentioned steps 4,5, two-stage membrane concentration all can concentrate material more than 10 times, and nanofiltration membrane ratio of desalinization can reach 60%, and its liquor C OD value can be reduced to below 100.
In above-mentioned steps 6, macroporous resin is H103 type resin.
Concentrating under reduced pressure in above-mentioned steps 7 and vacuum-drying temperature be not all higher than 60 ℃.
The present invention has following beneficial effect:
1, the Geniposidic acid in warm water extraction Folium Eucommiae in enzyme process, adding of cellulase contributes to break leaf wall, the Geniposidic acid in release cells, extraction yield can reach 95%, and water extraction temperature is lower, extraction time shortening, energy efficient.
2, adopt ultra-filtration membrane to carry out separation and purification to extracting solution, can effectively separate other by products, membrane operations process is simple, and membrane flux can be stablized for a long time, is easy to cleaning, long service life, is easy to realize industrialization.
3, adopt the extracting solution of nanofiltration membrane after to removal of impurities to concentrate, ratio of desalinization can reach 60%, can alleviate the load of subsequent technique, extends work-ing life and the energy efficient of resin, and nanofiltration liquor C OD value≤100 can reuse production process, substantially non-wastewater discharge.
4, adopt effectively purifying Geniposidic acid of macroporous adsorbent resin, the selected resin of this technique is polar macroporous adsorption resin, its, good separating effect large to Geniposidic acid adsorptive capacity, only concentrate wash-out Fractional Collections with a small amount of solvent, just can make higher degree Geniposidic acid.In the powder making through this technique, Geniposide acid content is greater than 65%, and extraction yield is greater than 2.5%.
Accompanying drawing explanation
Fig. 1 is technical process route schematic diagram of the present invention.
Embodiment
Example 1, referring to Figure of description 1, get dry Folium Eucommiae 10Kg, pulverize after cross 80 mesh sieves, add 120Kg water, regulate 55 ℃ of temperature, constant temperature also regulates pH value to 4.5, then adds 10g cellulase, extract with this understanding 60min, filter, filter residue extracts for the second time by aforementioned extraction conditions again, merges twice filtrate, conventional filtration, Geniposidic acid extraction yield is 95.8%; Be P=0.3Mpa in operational condition, T=45 ℃, PH=4.5, Q=70L/min filtrate is crossed 0.03 μ m ultra-filtration membrane, and extracting solution has concentrated 11.2 times under this condition, and this ultra-filtration membrane average flux is 226.3L/m
2h; At operational condition P=1.5Mpa, T=50 ℃, PH=4.5, Q=20L/min is by ultrafiltrate after 200 molecular weight nanofiltration membrane, and ultrafiltrate has concentrated 16.6 times under this condition, and inorganic ion clearance is 63%, and this nanofiltration membrane average flux is 18.7L/m
2h, nanofiltration liquor C OD is 94; Nanofiltration concentrated solution is passed through to H103 resin purification, first use 2 times of resin column volume pure water wash-out impurity, then be 30% ethanol elution with the concentration of volume percent of 2.5 times of resin column volumes, after collecting ethanol eluate concentrating under reduced pressure, vacuum-drying (the dry temperature of its concentrating under reduced pressure and vacuum is not all higher than 60 ℃), can obtain Geniposidic acid powder, detecting Geniposidic acid purity through HPLC is 68.5%, and yield is 2.62%.
Example 2, referring to washing bright book accompanying drawing 1, get dry Folium Eucommiae 10Kg, pulverize after cross 80 mesh sieves, add 120Kg water, regulate temperature 50 C, constant temperature also regulates pH value to 4.5, then adds 10g cellulase, extract with this understanding 80min, filter, filter residue extracts for the second time by aforementioned extraction conditions again, merges twice filtrate, conventional filtration, Geniposidic acid extraction yield is 95.3%; Be P=0.3Mpa in operational condition, T=45 ℃, PH=4.5, Q=70L/min filtrate is crossed 0.02 μ m ultra-filtration membrane, and extracting solution has concentrated 12.8 times under this condition, and this ultra-filtration membrane average flux is 221.3L/m
2h; At operational condition P=1.5Mpa, T=50 ℃, PH=4.5, Q=20L/min is concentrated after 400 molecular weight nanofiltration membrane by ultrafiltrate, ultra-filtration membrane filtrate has concentrated 15.2 times under this condition, and inorganic ion clearance is 60%, and this nanofiltration membrane average flux is 19.5L/m
2h, nanofiltration liquor C OD is 91; Nanofiltration concentrated solution is passed through to H103 resin purification, first use 2 times of resin column volume pure water wash-out impurity, then be 30% ethanol elution with the concentration of volume percent of 2.5 times of resin column volumes, after collecting ethanol eluate concentrating under reduced pressure, vacuum-drying (the dry temperature of its concentrating under reduced pressure and vacuum is not all higher than 60 ℃), can obtain Geniposidic acid powder, detecting Geniposidic acid purity through HPLC is 68.4%, and yield is 2.85%.
Claims (3)
1. produce the method for Geniposidic acid in Folium Eucommiae for one kind, comprise the Geniposidic acid in waste Folium Eucommiae take Folium Eucommiae powder, it is characterized in that: in the Folium Eucommiae powder of pulverizing, add the Geniposidic acid in cellulase and middle warm water extraction Folium Eucommiae, by two-stage membrane separation technique binding resin absorb-elute technique, the Geniposidic acid extracting is carried out to separation and purification, collection ethanol eluate concentrating under reduced pressure, vacuum-drying obtain product Geniposidic acid powder.
2. a kind of method of producing Geniposidic acid in Folium Eucommiae according to claim 1, is characterized in that: the method for Geniposidic acid in Folium Eucommiae of producing comprises the following steps:
(1), the pulverizing of raw material leaf: by water content≤14% Folium Eucommiae, cross 80 mesh sieves after pulverizing by ordinary method;
(2), the auxiliary middle warm water extraction of enzyme process: will add a certain amount of water in the raw material leaf of pulverizing, regulating pH is 4.5, and constant temperature to 50 ℃-60 ℃, add appropriate cellulase to extract under the following conditions: cellulase addition is concentration of substrate 0.2%, every kg feed material leaf need consume cellulase, the Folium Eucommiae powder of 0.002 kilogram: mass ratio=1 of water: 12, extract 2 times, each 60-80min;
(3), filter: merge after extracted twice liquid, remove the impurity such as suspended substance by conventional filtration method;
(4), ultra-filtration membrane removal of impurities: adopting pore size filter is the ultrafiltration membrane treatment Folium Eucommiae water extraction liquid of 0.02-0.0.06 μ m, hold back the impurity such as macro-molecular protein and polysaccharide with ultra-filtration membrane, and Geniposidic acid molecular weight can see through completely in 400Dal left and right, the operational condition of this film is: P=0.2-0.6Mpa, T=30-50 ℃, PH=4-5, Q=60-70L/min;
(5), nanofiltration is concentrated: adopt the nanofiltration membrane that interception molecular weight is 200-400Dal to concentrate one-level membrane filtration liquid, partially desalted, this grade of membrane concentration multiple can reach more than 15 times, and inorganic ion clearance can reach 60%; The operational condition of this film is: P=1.0-1.5Mpa, T=30-60 ℃, PH=4-5, Q=20L/min;
(6), the separation and purification of macroporous resin: nanofiltration membrane concentrated solution carries out absorb-elute by macroporous resin, first wash away impurity with the pure water of 2 times of resin column volumes, then be 30% ethanol elution with the concentration of volume percent of 2.5 times of resin column volumes, collect ethanol eluate;
(7), concentrated and dry: the ethanol eluate of collection can be obtained to Geniposidic acid powder after by conventional concentrating under reduced pressure and vacuum-drying.
3. according to claim 1 and a kind of method of producing Geniposidic acid in Folium Eucommiae claimed in claim 2, it is characterized in that: concentrating under reduced pressure and vacuum-drying temperature be not all higher than 60 ℃.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017356A (en) * | 2015-08-31 | 2015-11-04 | 桂林茗兴生物科技有限公司 | Method for extracting geniposide from gardenia jasminoides ellis |
| CN105131060A (en) * | 2015-08-31 | 2015-12-09 | 桂林茗兴生物科技有限公司 | Method for extracting geniposide acid from folium cortex eucommiae |
| CN106317140A (en) * | 2015-06-29 | 2017-01-11 | 上海中医药大学 | Novel crystal form of geniposidic acid, and preparation method and application thereof |
| CN113861253A (en) * | 2021-10-20 | 2021-12-31 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Preparation method and application of genipin nucleotide monomer |
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| CN1241560A (en) * | 1999-06-25 | 2000-01-19 | 遵义古特杜仲开发有限公司 | Method of extracting the effective components from gettama leaf by using supercritical carbon dioxide |
| CN1785954A (en) * | 2005-11-08 | 2006-06-14 | 湘西自治州和益生物科技有限公司 | Technological method of continuous extracting effective components in eucommia ulmoides kernel by super critical carbon dioxide |
| CN101260131A (en) * | 2008-04-19 | 2008-09-10 | 吉首大学 | Method for extracting iridoid active site and monomer from eucommia bark |
| CN102040519A (en) * | 2009-10-22 | 2011-05-04 | 湖北老龙洞杜仲开发有限公司 | Method for preparing chlorogenic acid in Eucommia ulmoides leaves |
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2012
- 2012-10-17 CN CN201210404302.6A patent/CN103772457B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1241560A (en) * | 1999-06-25 | 2000-01-19 | 遵义古特杜仲开发有限公司 | Method of extracting the effective components from gettama leaf by using supercritical carbon dioxide |
| CN1785954A (en) * | 2005-11-08 | 2006-06-14 | 湘西自治州和益生物科技有限公司 | Technological method of continuous extracting effective components in eucommia ulmoides kernel by super critical carbon dioxide |
| CN101260131A (en) * | 2008-04-19 | 2008-09-10 | 吉首大学 | Method for extracting iridoid active site and monomer from eucommia bark |
| CN102040519A (en) * | 2009-10-22 | 2011-05-04 | 湖北老龙洞杜仲开发有限公司 | Method for preparing chlorogenic acid in Eucommia ulmoides leaves |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317140A (en) * | 2015-06-29 | 2017-01-11 | 上海中医药大学 | Novel crystal form of geniposidic acid, and preparation method and application thereof |
| CN106317140B (en) * | 2015-06-29 | 2020-12-04 | 上海中医药大学 | Novel crystal form of geniposide and preparation method and application thereof |
| CN105017356A (en) * | 2015-08-31 | 2015-11-04 | 桂林茗兴生物科技有限公司 | Method for extracting geniposide from gardenia jasminoides ellis |
| CN105131060A (en) * | 2015-08-31 | 2015-12-09 | 桂林茗兴生物科技有限公司 | Method for extracting geniposide acid from folium cortex eucommiae |
| CN113861253A (en) * | 2021-10-20 | 2021-12-31 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Preparation method and application of genipin nucleotide monomer |
| CN113861253B (en) * | 2021-10-20 | 2024-06-21 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Preparation method and application of geniposide acid monomer |
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