CN101670010B - Method for extracting flavonoid glycoside substance - Google Patents
Method for extracting flavonoid glycoside substance Download PDFInfo
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- CN101670010B CN101670010B CN200910308171XA CN200910308171A CN101670010B CN 101670010 B CN101670010 B CN 101670010B CN 200910308171X A CN200910308171X A CN 200910308171XA CN 200910308171 A CN200910308171 A CN 200910308171A CN 101670010 B CN101670010 B CN 101670010B
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Abstract
The invention provides a method for extracting flavonoid glycoside substance, comprising the following steps of: taking orange pericarp removed with impurities and dry powder of persimmon leaf as raw materials, and extracting with 20-80% alcohol; setting aside, precipitating, taking supernatant, adding diatomite that is 1-5% of supernatant in terms of mass, fully stirring, pressing and filtering by a plate filter, membrane-filtering the filtrate B with PES membrane material, and taking the micro-molecular solution passing through the membrane; putting the obtained micro-molecular solution into a film evaporator to remove impurities by molecular distillation, collecting the required distillate, performing spray drying, and making into powder to obtain the flavonoid glycoside substance. The method for extracting flavonoid glycoside substance has quite simple and convenient operation and low cost, and can save a large amount of solvent, reduce the requirements on the device, also reduce pollution on the environment and well guarantee the natural quality of the flavonoid glycoside substance; the content of flavonoid glycoside component in the produced flavonoid extract is high with a total content of more than 70%, and the transfer rate of general flavone can reach more than 95% with less residual pigment.
Description
Technical field
The invention belongs to the extraction separation purification process of natural medicinal ingredients bioflavonoids; Be particularly related to the new technology of separation and Extraction flavonoid glycoside substance a kind of peel of drying and ripening of leaf and rutaceae orange (Citrus reticulataBlanco) and the variety thereof from plant Ebenaceae Diospyros plant persimmon (Diospyros kaki Thunb), the present invention not only relates to water-ethanol extraction, also relate to the new process of separating the purification flavonoid glycoside substance with kieselguhr filtering, ultrafiltration, with molecular distillation technique.
Background technology
Bioflavonoids (bioflavonoids) is the aldehydes matter that occurring in nature extensively exists, and also claims Citrin, and normal and vitamin C companion deposits, and is the secondary metabolite of plant.Flavonoid is the derivant of chromanane or chromone, and its basic framework has C
6-C
3-C
6Characteristics, promptly by two aromatic rings A and B, a series of chemical compounds that link each other through central three carbochains.Whether degree of oxidation, link position and three carbochains of B ring on the C ring according to central three carbochains constitute characteristics such as ring-type; Flavonoid is divided into flavone and flavonoid glycoside, flavonol and flavonol glycoside, chalcone derivative, aurone aurones class, anthocyanidin and anthocyanin, flavonol, flavanone, flavanonol, carbon-glycoside flavone, bisflavone and dimeric flavones, isoflavone, isoflavanone, mouthful diphenylene ketone oxide class or claims the benzo chromone and neoflavone 14 big classes, and sum has more than 2700 approximately.Flavonoid distributes very general in plant kingdom, in algae, mushroom, seldom find.
Flavonoid has the various biological function; Be mainly: (1) is to the antioxidative regulating action; Reported through antioxidation in vitro experiment like single poplar (2007) five kinds of monomeric anti-oxidation functions of polymethoxyflavone in the peel of Citrus reticulata Blanco have been studied; Show that five kinds of flavone monomers all have certain anti-linoleic acid oxidability in the peel of Citrus reticulata Blanco, and all be better than rutin; The flavonoid monomer suppresses the liposome oxidability and all shows certain concentration dependence, removes OH free radical ability and respective concentration and also has positive correlation.(2) to the regulating action of lipid metabolism, like woods Depositum urinae preparatum (2000) report, crataegutt can make the mRNA of rat low density lipoprotein receptor (LDLR) transcribe enhancing, and LDLR expresses also and strengthens simultaneously, thereby increases the degraded of low density lipoprotein, LDL (LDL).Lichtenstein (1998) thinks that the soybean prod prevention of arterial is atherosis, the effect of coronary heart disease is owing to Semen sojae atricolor flavonoid etc.(3) inhibitory anti-virus effect; Reported the flavonoid material that has bacteriostasis in the citrus peel residue crude extract like Zhang Lijie (2009); Staphylococcus aureus, escherichia coli and bacillus subtilis are had good bacteriostasis, and the diameter of inhibition zone is 5.9,5.7 respectively, 6.0mm.Propose among the Yan Fenghai (application number 98113018.6), from leaf of Diospyros kaki L.f., extract flavonoid glycoside and make pharmacology and bacteriostatic test, the result shows it with Armeniaca mume Sieb. element and metronidazole effect basically identical, and it has certain curative effect to hematoblastic minimizing and nerve insomnia simultaneously.(4) to endocrine influence; Can promote the recovery of beta Cell of islet like Nielsen (1998), Shen (1993) report flavonoid; Blood sugar lowering and serum cholesterol improve carbohydrate tolerance, to adrenolytic blood glucose increasing effect; It can also suppress aldose reductase simultaneously, can treat diabetes and complication thereof.Rbards and Antolovich (1997) research points out that flavonoid can be used for treating diseases such as osteopathia and osteoporosis; Its mechanism of action is that it both can suppress the collagen protein synthesis increase of PGE2 (PGE2); The synthetic minimizing of NCP that can suppress PGE2 again; And when low concentration PGE2, mainly act on the synthetic of NCP, and mainly act on collagen protein synthesis during high concentration PGE2, can be used to treat osteopathia; And can improve thyroid to estrogenic sensitivity, the effect of parafollicular cells of thyroid gland secretion calcitonin is strengthened, finally suppress bone resorption and treat osteoporosis.(5) to the influence of breeding performonce fo animals; Give rat skin lower injection daidzein 16 days like (1995) such as the outstanding persons of kingdom; RNA/DNA ratio improves 18.7%; The short muscle growth effect that shows daidzein mainly is the loose and protein anabolism reinforcement of myofibrillar trophism, rather than quickens the result of satellite cell breeding.(6) antitumaous effect has reported that like M Noroozi (1998) the hexa methoxy flavone in the peel of Citrus reticulata Blanco has the platelet aggregation of inhibition, antithrombotic effect, and Heptamethoxyflavone all has stronger tumor-suppression activity etc. to stomach cancer cell and leukaemia.
Although the flavonoid in the natural plants has the various biological function, also there is potential side effect.In plant and plant eater's common evolution, plant has been set up Chemical Defence System to resist plant eater's infringement.In the chemoresistance factor of plant, secondary metabolites confrontation plant eater's resistance mainly contains antixenosis (even host plant has non preference or hinders feeding effect) and antibiosis (promptly digest and assimilate the plant eater and then play the endotoxin lethality effect or the effect that physiological activity suppresses its growth promoter such as digest and assimilate through the reduction) effect aspect two.The antixenosis of flavonoid and antibiosis confirm by many research work and practical application, result of study show the intravital low-molecular-weight flavonoid of plant because of with the combination of proteins ability a little less than, do not show tangible anti-oxidant action.The flavonoid that molecular weight is too big (mainly refer to the flavanol compound flavone that the degree of polymerization is higher, its molecular weight is more than 3000) is because poorly soluble; Be difficult for degraded in animal body; Can the nutritive value of plant not exerted an influence yet, can produce remarkable influence (Bravo etc., 1993).
Based on above these effects, the separation and purification of flavone compound is particularly important.The isolation and purification method of flavone compound is a lot; Column chromatography, thin layer chromatography, lead salt deposition, boric acid complexation, the extraction of pH gradient, solvent extraction and the HPLC of using in recent years (HPLC), droplet countercurrent chromatography (DCCC), gas chromatography etc. are arranged; But all there is shortcoming in various degree and limited its suitability for industrialized production, can be used for industrialized supercritical CO
2Extraction is suitable for the last stage of separation process, and adsorption resin method will reach refining to product, and the step that needs is numerous, is used for the purification of flavonoid, and is all undesirable.Molecular distillation (molecular distillation) technology is the non-equilibrium distillation of under high vacuum condition, carrying out; Can solve the problem that the wide variety of conventional distillation technique cann't be solved; Be suitable for separating the composition of the high added value in the thick product and purify; And this separation and purification are that other separation means commonly used are difficult to accomplish; The extraction that is particularly suitable for natural materials with separate, be successfully applied to industries such as petrochemical industry, food, plastics, medicine at present, but also be only limited to the use of liposoluble substance.
Molecular distillation is compared with conventional distillation technique in the application of actual industrialization has following remarkable advantages: operate under the temperature far below the material boiling point (1); And residence time of material is short; Separation for high boiling point, temperature-sensitive and readily oxidizable substance material provides the optimal separation method.(2) but the utmost point removes material such as organic solvent, the stink etc. in the liquid effectively, be unusual effective method for adopting behind the solvent extraction precipitation of liquid; (3) molecular distillation can steam the purpose product selectively, removes other impurity, can separate the material more than 2 kinds simultaneously through multiple stage separation; (4) fractional distillation process of molecular distillation is a physical process, thereby can protect the not contaminated and infringement of separated material well.
Separation of pure dissolves flavone compound from natural plants, not only will have broad application prospects in medicine, food processing industry, has made certain contribution at aspects such as environmental conservation, and is also significant to its physiologic function of further research.
Summary of the invention
The object of the invention be to seek a kind of more economical, from natural product, extract the method for flavones ingredient efficiently.
The technical scheme that the present invention adopts is:
A kind of method for distilling of flavonoid glycoside substance; Described method is that the dry fragment of getting peel of Citrus reticulata Blanco, leaf of Diospyros kaki L.f. is that raw material carries out as follows: the peel of Citrus reticulata Blanco of impurity is removed in (1), the dried powder of leaf of Diospyros kaki L.f. is a raw material, and (2) add 20～80% ethanol that quality is 10～20 times of peel of Citrus reticulata Blanco, the dry fragment quality of leaf of Diospyros kaki L.f. summation, and 2～4h are extracted in 30～70 ℃ of insulations; Centrifugal, filtration; The A that must filtrate, filtering residue repeats to extract 1～5 time again, merges each filtrating A that extracts and gets extracting solution; (3) step (2) gained extracting solution is staticly settled, get supernatant, adding quality is the kieselguhr of said supernatant 1～5%, after fully stirring, with the flame filter press filter pressing, uses the filter pressing of 3～10 layers of DANFU silk filter cloth usually, gets liquor B; DANFU silk filter cloth is called for short filter cloth in the present invention; (4) liquor B is carried out membrane filtration with the poly (ether sulfone) film material, molecular cut off 5kD gets the micromolecule solution of filter membrane; (5) get the micromolecule solution that step (4) obtains; Feeding membrane evaporator separates; Described membrane evaporator comprises the level Four distillator, control material flow 1～3ml/min, and knifing rotating speed at different levels is 100-300rpm; Preferred knifing rotating speed at different levels is 100-200rpm, and circulating water temperatures at different levels are respectively done for oneself 30～70 ℃; The vacuum of controlling first distillator is that 600～900Pa, vapo(u)rizing temperature are that 40 ℃～60 ℃, cryosurface temperature are to carry out thin film evaporation under 15～25 ℃ the condition; Must heat up in a steamer excess A and directly get into the after-fractionating device; The vacuum of control after-fractionating device is that 100～300Pa, vapo(u)rizing temperature are that 60 ℃～80 ℃, cryosurface temperature are to carry out thin film evaporation under 15～25 ℃ the condition; Must heat up in a steamer excess B and directly get into the 3rd distillator; The vacuum of controlling the 3rd distillator is that 10～50Pa, vapo(u)rizing temperature are that 80 ℃～110 ℃, cryosurface temperature are to carry out thin film evaporation under 15～25 ℃ the condition, must heat up in a steamer excess C and directly get into the 4th distillator, and the vacuum of controlling the 4th distillator is 0.01～2Pa; Vapo(u)rizing temperature is that 150 ℃～300 ℃, cryosurface temperature are to carry out thin film evaporation under 15～40 ℃ the condition, collects distillate; (6) distillate of collecting carries out spray drying and processes powdery, promptly described flavonoid glycoside substance.More than said filtrating A, liquor B be meant the filtrating in different process stage in the technical process; Distinguish with A, B, the filtrating of repeating to extract gained in the step (2) also all is defined as filtrating A, though the filtrating A that repeats to obtain is inequality at every turn; But belong to same processing step, be extracting solution after the merging.Membrane evaporator knifing rotating speed at different levels is roughly the same, preferably is controlled between 100～200rpm, and circulating water temperatures at different levels are respectively done for oneself 30～70 ℃; The preferred first distillator circulating water temperature is 30 ℃, and after-fractionating device circulating water temperature is 30 ℃, and the 3rd distillator circulating water temperature is 40 ℃, and the 4th distillator circulating water temperature is 70 ℃.
The present invention filters out from natural plants through external bacteriostatic experiment that to help extracting the leaf of Diospyros kaki L.f. and the peel of Citrus reticulata Blanco that obtain flavonoid glycoside substance be compound; The total extract that obtains through water-alcohol extraction; After adopting kieselguhr filtering, hyperfiltration technique to remove materials such as float class impurity, starch, half soluble cellulose, pectin, protein, chlorophyll, glycoprotein, lipid, adopt molecular distillation technology to obtain flavonoid glycoside substance again.The main points of invention are to adopt molecular distillation technology, and find suitable technological parameter to obtain to adopt small-molecular weight, high, the stay-in-grade flavonoid glycoside substance of purity.
The method for distilling of further flavonoid glycoside substance of the present invention, the dry fragment of said peel of Citrus reticulata Blanco, leaf of Diospyros kaki L.f. was preferably the dried powder of 20 mesh sieves.
The mass ratio of said peel of Citrus reticulata Blanco, leaf of Diospyros kaki L.f. can be an arbitrary proportion; Arbitrarily the peel of Citrus reticulata Blanco of mass ratio, leaf of Diospyros kaki L.f. extract with method of the present invention and prepare flavonoid glycoside substance and all reasonable effect can be arranged, but the present invention more preferably the mass ratio of peel of Citrus reticulata Blanco, leaf of Diospyros kaki L.f. be 2: 3.
The method for distilling of flavonoid glycoside substance of the present invention, the described sedimentation time is for precipitating 12～48 hours, preferred 12～24 hours.Described filter press has been adopted 3～10 metafiltration cloth filter pressings.
The vacuum that further step of the present invention (5) is preferably controlled first distillator is that 750～850Pa, vapo(u)rizing temperature are 40 ℃～50 ℃, and the cryosurface temperature is to carry out thin film evaporation under 15～25 ℃ the condition, and this step separates and removes gas and part ethanol; The vacuum of control after-fractionating device is that 150～250Pa, vapo(u)rizing temperature are 65 ℃～75 ℃, and the condition that the cryosurface temperature is 15～25 ℃ is carried out thin film evaporation, separates and removes ethanol and part water; The vacuum of controlling the 3rd distillator is that 20～40Pa, vapo(u)rizing temperature are 80 ℃～100 ℃, and the condition that the cryosurface temperature is 15～25 ℃ is carried out thin film evaporation, separates and removes most of water; The vacuum of controlling the 4th distillator is 0.01～0.5Pa; More preferably 0.01～0.1Pa, vapo(u)rizing temperature is 200 ℃～300 ℃, the cryosurface temperature is to carry out thin film evaporation under 20～30 ℃ the condition; Collect distillate, stay excess this moment is high boiling point and the involatile constituent that is removed.
The distillate that spray drying described in the step of the present invention (6) recommends to get step (5) collection directly is used for carrying out spray drying powder process.
Concrete, the method for distilling of flavonoid glycoside substance of the present invention carries out as follows: the mass ratio that impurity is removed in (1) is that 2: 3 peel of Citrus reticulata Blanco, the dry powder of leaf of Diospyros kaki L.f. are raw material; (2) add 55%～60% the ethanol that quality is 10～15 times of peel of Citrus reticulata Blanco, leaf of Diospyros kaki L.f. dry powder quality summation, 2.5～3h are extracted in 50 ℃ of insulations, and are centrifugal, filter, and the A that must filtrate, filtering residue repeat to extract 2～3 times again, merge each filtrating A and get extracting solution; (3) step (2) gained extracting solution was left standstill 12～24 hours, deposition is got supernatant, and adding quality is the kieselguhr of said supernatant 2%, after fully stirring, with 6～8 metafiltration cloth filter pressings, gets liquor B with flame filter press; (4) liquor B is carried out membrane filtration with the poly (ether sulfone) film material, molecular cut off 5kD gets the micromolecule solution of filter membrane; (5) get the micromolecule solution that step (4) obtains, feed membrane evaporator and separate, described membrane evaporator comprises the level Four distillator; Control material flow 2～3ml/min, the vacuum of controlling first distillator is that 750～850Pa, vapo(u)rizing temperature are that 40 ℃～50 ℃, cryosurface temperature are that 15～25 ℃, circulating water temperature are 30～70 ℃, carries out thin film evaporation under the condition that the preferred cycle coolant-temperature gage is 30 ℃; Must heat up in a steamer excess A and directly get into the after-fractionating device; The vacuum of control after-fractionating device is that 150～250Pa, vapo(u)rizing temperature are that 65 ℃～75 ℃, cryosurface temperature are that 15～25 ℃, circulating water temperature are 30～70 ℃, carries out thin film evaporation under the condition that the preferred cycle coolant-temperature gage is 30 ℃, must heat up in a steamer excess B and directly get into the 3rd distillator; The vacuum of controlling the 3rd distillator is that 20～40Pa, vapo(u)rizing temperature are that 80 ℃～90 ℃, 15～25 ℃ of cryosurface temperature, circulating water temperature are 30～70 ℃; Carry out thin film evaporation under the condition that the preferred cycle coolant-temperature gage is 40 ℃, must heat up in a steamer excess C and directly get into the 4th distillator, the vacuum of controlling the 4th distillator is 0.01～0.05Pa; Vapo(u)rizing temperature is 250 ℃～280 ℃; 30 ℃ of cryosurface temperature, knifing rotating speed 300rpm, circulating water temperature are 30～70 ℃; Carry out thin film evaporation under 70 ℃ of conditions of preferred cycle coolant-temperature gage, collect distillate; (6) getting distillate that step (5) collects carries out spray drying and processes powdery, promptly described flavonoid glycoside substance.
Beneficial effect of the present invention is mainly reflected in:
1. the diatomite filtration clarification and the ultrafiltration technology that are adopted among the present invention have been removed materials such as the protein in the extracting solution, half soluble fiber, pectin, starch, chlorophyll, glycoprotein, lipid, have saved organic solvent extraction, and polyamide is refining; And the membrane material physical and chemical stability is high, and mechanical strength is good, can repeatedly use; Technological operation is very easy, with low cost.
2. the molecular distillation method that the present invention adopted is pure physical separating process; Can save high amounts of solvents, reduce requirement, reduce pollution simultaneously environment to equipment; And can not bring new impurity and noxious substance into, can guarantee the natural quality of flavonoid glycoside substance well; Though the initial stage one-time investment is bigger, follow-up production cost (comprising material, water power, labour force etc.) is smaller; Be applicable to large-scale industrial production.
3. the flavonoid glycoside component content is high in the flavone extract that is gone out by explained hereafter of the present invention, and total content is more than 70%, and the total flavones rate of transform can reach more than 95%, and color and luster is good.After existing skill is stated common employing alcohol extraction or supersound extraction, the flavonoid glycoside substance that acid-alkali treatment or multiple-stage solvent extraction are extracted from plant, but content is very low usually; Generally have only about 40%; Also have and adopt adsorption resin method to carry out purification, but will reach refining to product, the step that needs is cumbersome.
The specific embodiment
Below in conjunction with specific embodiment the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1
(1). the preparation of raw material: clean Zhejiang Province respectively and produce exsiccant peel of Citrus reticulata Blanco, exsiccant leaf of Diospyros kaki L.f., remove impurity wherein, after the pulverizing, cross 20 mesh sieves, respectively peel of Citrus reticulata Blanco dry powder, leaf of Diospyros kaki L.f. powder are for use;
(2). the processing of raw material: in peel of Citrus reticulata Blanco dry powder and leaf of Diospyros kaki L.f. dry powder quality ratio is that 2: 3 ratios were got peel of Citrus reticulata Blanco dried powder 0.2kg, leaf of Diospyros kaki L.f. dried powder 0.3kg, adds quality and be 60% ethanol water of 10 times of peel of Citrus reticulata Blanco dry powder and leaf of Diospyros kaki L.f. dry powder quality summations, and temperature control is at 50 ℃～60 ℃; Extract 3h; Centrifugal, filtration, the A that must filtrate, filtering residue extracts 2 times by above method again; Merging filtrate A gets extracting solution 7.2L;
(3). filter: step (2) gained extracting solution is staticly settled, and the kieselguhr 0.14kg with the supernatant 7.0L after staticly settling adds supernatant quality 2% to adsorb most of colloid, chlorophyll etc., uses the flame filter press filter pressing with its filtering then; (3) step (2) gained extracting solution is staticly settled, get supernatant, adding quality is the kieselguhr of said supernatant 2%, after fully stirring, with the flame filter press filter pressing, gets 8 layers of DANFU silk filter cloth during filter pressing, gets liquor B 6.2L;
(4). liquor B is carried out membrane filtration with poly (ether sulfone) film material (molecular weight 5kD, 95%), molecular cut off 5kD, and further remove tannin, peptide class etc., get the micromolecule solution 3.6L of filter membrane;
(5). get the micromolecule solution 3.6L that step (4) obtains, feed membrane evaporator and separate, described membrane evaporator comprises the level Four distillator; Control material flow 2ml/min, knifing rotating speed 100rpm at different levels, the vacuum of controlling first distillator is that 800Pa, vapo(u)rizing temperature are that 45 ℃, cryosurface temperature are to carry out thin film evaporation under the condition of 30 ℃ of 25 ℃, circulating water temperature; Separate and remove gas and part ethanol; Must heat up in a steamer excess A and directly get into the after-fractionating device, the vacuum of control after-fractionating device is that 200Pa, vapo(u)rizing temperature are that 70 ℃, cryosurface temperature are to carry out thin film evaporation under the condition of 30 ℃ of 25 ℃, circulating water temperature, separates and removes ethanol and part water; Must heat up in a steamer excess B and directly get into the 3rd distillator; The vacuum of controlling the 3rd distillator is that 30Pa, vapo(u)rizing temperature are to carry out thin film evaporation under 90 ℃, the condition of 25 ℃ of cryosurface temperature, 40 ℃ of circulating water temperatures, separates and removes most of water, must heat up in a steamer excess C and directly get into the 4th distillator; The vacuum of controlling the 4th distillator is 0.02Pa; Vapo(u)rizing temperature is 260 ℃, and the cryosurface temperature is to carry out thin film evaporation under the condition of 70 ℃ of 30 ℃, circulating water temperature, collects distillate 0.26L; Stay excess this moment is high boiling point and the involatile constituent that is removed.
(6). the distillate 0.26L that gets step (5) collection processes powdery with spray drying tower, and promptly flavonoid glycoside substance 0.00603kg is a standard specimen with the rutin, and use determined by ultraviolet spectrophotometry wherein general flavone content is 77.4%.
Embodiment 2
(1). the preparation of raw material: clean Zhejiang Province respectively and produce exsiccant peel of Citrus reticulata Blanco, exsiccant leaf of Diospyros kaki L.f., remove impurity wherein, after the pulverizing, cross 20 mesh sieves, respectively peel of Citrus reticulata Blanco dry powder, leaf of Diospyros kaki L.f. powder are for use;
(2). the processing of raw material: in peel of Citrus reticulata Blanco dry powder and leaf of Diospyros kaki L.f. dry powder quality ratio is that 2: 3 ratios were got peel of Citrus reticulata Blanco dried powder 0.3kg, leaf of Diospyros kaki L.f. dried powder 0.45kg, adds quality and be 40% ethanol of 10 times of peel of Citrus reticulata Blanco dry powder and leaf of Diospyros kaki L.f. dry powder quality summations, and temperature control is at 40 ℃～50 ℃; Extract 3h; Centrifugal, filtration, the A that must filtrate, filtering residue extracts 2 times by above method again; Merging filtrate A gets extracting solution 10.6L;
(3). step (2) gained extracting solution is staticly settled, and the kieselguhr 0.204kg with the supernatant 10.2L after staticly settling adds supernatant quality 2% to adsorb most of colloid, chlorophyll etc., uses the flame filter press filter pressing with its filtering then; After fully stirring,, get 8 metafiltration cloth during filter pressing, get liquor B 8.7L with the flame filter press filter pressing;
(4). liquor B is carried out membrane filtration with poly (ether sulfone) film material (molecular weight 5kD, 95%), molecular cut off 5kD, and further remove tannin, peptide class etc., get the micromolecule solution 4.9L of filter membrane;
(5). get the micromolecule solution 4.9L that step (4) obtains, feed membrane evaporator and separate, described membrane evaporator comprises the level Four distillator; Control material flow 2ml/min, knifing rotating speed 200rpm at different levels, the vacuum of controlling first distillator is that 750Pa, vapo(u)rizing temperature are that 40 ℃, cryosurface temperature are to carry out thin film evaporation under the condition of 30 ℃ of 25 ℃, circulating water temperature; Separate and remove gas and part ethanol; Must heat up in a steamer excess A and directly get into the after-fractionating device, the vacuum of control after-fractionating device is that 150Pa, vapo(u)rizing temperature are that 60 ℃, cryosurface temperature are to carry out thin film evaporation under the condition of 30 ℃ of 25 ℃, circulating water temperature, separates and removes ethanol and part water; Must heat up in a steamer excess B and directly get into the 3rd distillator; The vacuum of controlling the 3rd distillator is that 40Pa, vapo(u)rizing temperature are to carry out thin film evaporation under 100 ℃, the condition of 25 ℃ of cryosurface temperature, 40 ℃ of circulating water temperatures, separates and removes most of water, must heat up in a steamer excess C and directly get into the 4th distillator; The vacuum of controlling the 4th distillator is 0.05Pa; Vapo(u)rizing temperature is 270 ℃, and the cryosurface temperature is to carry out thin film evaporation under the condition of 70 ℃ of 25 ℃, circulating water temperature, collects distillate 0.42L; Stay excess this moment is high boiling point and the involatile constituent that is removed.
(6) the distillate 0.42L that gets step (5) collection processes powdery with spray drying tower, and promptly flavonoid glycoside substance 0.00915kg is a standard specimen with the rutin, and use determined by ultraviolet spectrophotometry wherein general flavone content is 74.1%.
Embodiment 3
(1). the preparation of raw material: clean Zhejiang Province respectively and produce exsiccant peel of Citrus reticulata Blanco, exsiccant leaf of Diospyros kaki L.f., remove impurity wherein, after the pulverizing, cross 20 mesh sieves, respectively peel of Citrus reticulata Blanco dry powder, leaf of Diospyros kaki L.f. powder are for use;
(2). the processing of raw material: in peel of Citrus reticulata Blanco dry powder and leaf of Diospyros kaki L.f. dry powder quality ratio is that 2: 3 ratios were got peel of Citrus reticulata Blanco dried powder 0.2kg, leaf of Diospyros kaki L.f. dried powder 0.3kg, adds quality and be 50% ethanol of 12 times of peel of Citrus reticulata Blanco dry powder and leaf of Diospyros kaki L.f. dry powder quality summations, and temperature control is at 35 ℃～45 ℃; Extract 2.5h; Centrifugal, filtration, the A that must filtrate, filtering residue extracts 2 times by above method again; Merging filtrate A gets extracting solution 8.3L;
(3). step (2) gained extracting solution is staticly settled, and the kieselguhr 0.16kg with the supernatant 8.0L after staticly settling adds supernatant quality 2% to adsorb most of colloid, chlorophyll etc., uses the flame filter press filter pressing with its filtering then; After fully stirring,, get 6 metafiltration cloth during filter pressing, get liquor B 7.1L with the flame filter press filter pressing;
(4). liquor B is carried out membrane filtration with poly (ether sulfone) film material (molecular weight 5kD, 95%), molecular cut off 5kD, and further remove tannin, peptide class etc., get the micromolecule solution 3.9L of filter membrane;
(5). get the micromolecule solution 3.9L that step (4) obtains, feed membrane evaporator and separate, described membrane evaporator comprises the level Four distillator; Control material flow 2ml/min, knifing rotating speed 150rpm at different levels, the vacuum of controlling first distillator is that 850Pa, vapo(u)rizing temperature are that 50 ℃, cryosurface temperature are to carry out thin film evaporation under the condition of 30 ℃ of 25 ℃, circulating water temperature; Separate and remove gas and part ethanol; Must heat up in a steamer excess A and directly get into the after-fractionating device, the vacuum of control after-fractionating device is that 150Pa, vapo(u)rizing temperature are that 75 ℃, cryosurface temperature are to carry out thin film evaporation under the condition of 30 ℃ of 25 ℃, circulating water temperature, separates and removes ethanol and part water; Must heat up in a steamer excess B and directly get into the 3rd distillator; The vacuum of controlling the 3rd distillator is that 40Pa, vapo(u)rizing temperature are to carry out thin film evaporation under 100 ℃, the condition of 25 ℃ of cryosurface temperature, 40 ℃ of circulating water temperatures, separates and removes most of water, must heat up in a steamer excess C and directly get into the 4th distillator; The vacuum of controlling the 4th distillator is 0.08Pa; Vapo(u)rizing temperature is 280 ℃, and the cryosurface temperature is to carry out thin film evaporation under the condition of 70 ℃ of 25 ℃, circulating water temperature, collects distillate 0.31L; Stay excess this moment is high boiling point and the involatile constituent that is removed.
(6). the distillate 0.31L that gets step (5) collection processes powdery with spray drying tower, and promptly flavonoid glycoside substance 0.00583kg is a standard specimen with the rutin, and use determined by ultraviolet spectrophotometry wherein general flavone content is 72.6%.
Embodiment 4
Step (1)～(4) are with the step among the embodiment 1 (1)～(4), the micromolecule solution 3.5L of final filter membrane;
Step (5): get micromolecule solution 3.5L, extracted the micromolecule solution behind the ultrafilter membrane successively with petroleum ether, carbon tetrachloride, chloroform, ethyl acetate, each water intaking layer of each extraction carries out next step extraction; When using ethyl acetate extraction at last, get ethyl acetate layer, the consumption of every kind of reagent is 1/3 of mother solution at that time at every turn; Every kind of reagent all extracts 3 times, obtain ethyl acetate layer 3.9L after, concentrate to remove ethyl acetate with Rotary Evaporators; Obtain solution 0.33L, adopt boulton process to carry out drying, obtain flavonoid glycoside substance 0.00947kg; With the rutin is standard specimen, and use determined by ultraviolet spectrophotometry wherein general flavone content is 38.6%.
Embodiment 5
Step (1)～(4) are with the step among the embodiment 1 (1)～(4) method, the micromolecule solution 4.9L that obtains;
(5). get the micromolecule solution 4.9L that step (4) obtains, feed membrane evaporator and separate, described membrane evaporator comprises the level Four distillator; Control material flow 2ml/min, the vacuum of controlling first distillator is that 850Pa, vapo(u)rizing temperature are that 45 ℃, cryosurface temperature are to carry out thin film evaporation under the condition of 30 ℃ of 25 ℃, circulating water temperature, separates and removes gas and part ethanol; Must heat up in a steamer excess A and directly get into the after-fractionating device; The vacuum of control after-fractionating device is that 350Pa, vapo(u)rizing temperature are 70 ℃, knifing rotating speed 300rpm, and 30 ℃ of cryosurface temperature of circulating water temperature are to carry out thin film evaporation under 25 ℃ the condition, separate and remove ethanol and part water; Must heat up in a steamer excess B and directly get into the 3rd distillator; The vacuum of controlling the 3rd distillator is that 30Pa, vapo(u)rizing temperature are to carry out thin film evaporation under 100 ℃, the condition of 25 ℃ of cryosurface temperature, 40 ℃ of circulating water temperatures, separates and removes most of water, must heat up in a steamer excess C and directly get into the 4th distillator; The vacuum of controlling the 4th distillator is 0.5Pa; Vapo(u)rizing temperature is 280 ℃, and the cryosurface temperature is to carry out thin film evaporation under the condition of 70 ℃ of 25 ℃, circulating water temperature, collects distillate 0.46L; Stay excess this moment is high boiling point and the involatile constituent that is removed;
(6). the distillate 0.46L that gets step (5) collection processes powdery with spray drying tower, and promptly flavonoid glycoside substance 0.00518kg is a standard specimen with the rutin, and use determined by ultraviolet spectrophotometry wherein general flavone content is 52.4%.
Embodiment 6
Step (1)～(4) are with the step among the embodiment 1 (1)～(4) method, the micromolecule solution 3.6L that obtains;
(5). get the micromolecule solution 3.6L that step (4) obtains, feed membrane evaporator and separate, described membrane evaporator comprises the level Four distillator; Control material flow 1ml/min, knifing rotating speed 100rpm, the vacuum of controlling first distillator is that 800Pa, vapo(u)rizing temperature are that 45 ℃, cryosurface temperature are to carry out thin film evaporation under the condition of 30 ℃ of 25 ℃, circulating water temperature; Separate and remove gas and part ethanol; Must heat up in a steamer excess A and directly get into the after-fractionating device, the vacuum of control after-fractionating device is that 200Pa, vapo(u)rizing temperature are that 70 ℃, cryosurface temperature are to carry out thin film evaporation under the condition of 30 ℃ of 25 ℃, circulating water temperature, separates and removes ethanol and part water; Must heat up in a steamer excess B and directly get into the 3rd distillator; The vacuum of controlling the 3rd distillator is that 30Pa, vapo(u)rizing temperature are to carry out thin film evaporation under 90 ℃, the condition of 25 ℃ of cryosurface temperature, 40 ℃ of circulating water temperatures, separates and removes most of water, must heat up in a steamer excess C and directly get into the 4th distillator; The vacuum of controlling the 4th distillator is 2Pa; Vapo(u)rizing temperature is 260 ℃, carries out thin film evaporation under the condition of 25 ℃ of cryosurface temperature, 70 ℃ of circulating water temperatures, collects distillate 0.25L; Stay excess this moment is high boiling point and the involatile constituent that is removed;
(6). the distillate 0.25L that gets step (8) collection processes powdery with spray drying tower, and promptly flavonoid glycoside substance 0.00203kg is a standard specimen with the rutin, and use determined by ultraviolet spectrophotometry wherein general flavone content is 40.6%.
The vacuum that the present invention preferably controls the 4th distillator is 0.01～0.5Pa; Vapo(u)rizing temperature is 200 ℃～300 ℃, and the cryosurface temperature is 20～30 ℃, and the knifing rotating speed is 250-350rpm; Carry out thin film evaporation under 30～70 ℃ of conditions of circulating water temperature, collect distillate.In the 5th step of embodiment 6 vacuum of the 4th distillator be 2Pa more excessive relatively, though also can isolate flavonoid glycoside substance, the total flavones yield is less relatively.
Claims (10)
1. the method for distilling of a flavonoid glycoside substance; It is characterized in that described method is that the dry fragment of getting peel of Citrus reticulata Blanco, leaf of Diospyros kaki L.f. is that raw material carries out as follows: the peel of Citrus reticulata Blanco of impurity is removed in (1), the dry fragment of leaf of Diospyros kaki L.f. is a raw material; (2) add 20～80% ethanol that quality is 10～20 times of peel of Citrus reticulata Blanco, the dry fragment quality of leaf of Diospyros kaki L.f. summation; 2～4h is extracted in 30～70 ℃ of insulations, centrifugal, filtration, and A must filtrate; Filtering residue repeats to extract 1～5 time again, merges each filtrating A that extracts and gets extracting solution; (3) step (2) gained extracting solution is staticly settled, get supernatant, adding quality is the kieselguhr of said supernatant 1～5%, after fully stirring, with the flame filter press filter pressing, gets liquor B; (4) liquor B is carried out membrane filtration with the poly (ether sulfone) film material, molecular cut off 5kD gets the micromolecule solution of filter membrane; (5) getting micromolecule solution that step (4) obtains feeds membrane evaporator and separates; Described membrane evaporator comprises the level Four distillator; Control material flow 1～3ml/min; Knifing rotating speed at different levels is 100-300rpm, and circulating water temperatures at different levels are respectively done for oneself 30～70 ℃, and the vacuum of controlling first distillator is that 600～900Pa, vapo(u)rizing temperature are that 40 ℃～60 ℃, cryosurface temperature are to carry out thin film evaporation under 15～25 ℃ the condition; Must heat up in a steamer excess A and directly get into the after-fractionating device; The vacuum of control after-fractionating device is that 100～300Pa, vapo(u)rizing temperature are that 60 ℃～80 ℃, cryosurface temperature are to carry out thin film evaporation under 15～25 ℃ the condition, must heat up in a steamer excess B and directly get into the 3rd distillator, and the vacuum of controlling the 3rd distillator is that 10～50Pa, vapo(u)rizing temperature are that 80 ℃～110 ℃, cryosurface temperature are to carry out thin film evaporation under 15～25 ℃ the condition; Must heat up in a steamer excess C and directly get into the 4th distillator; The vacuum of controlling the 4th distillator is 0.01～2Pa, and vapo(u)rizing temperature is that 150 ℃～300 ℃, cryosurface temperature are to carry out thin film evaporation under 15～40 ℃ of conditions, collects distillate; (6) getting distillate that step (5) collects carries out spray drying and processes powdery, promptly described flavonoid glycoside substance.
2. the method for distilling of flavonoid glycoside substance as claimed in claim 1, the dry fragment that it is characterized in that said peel of Citrus reticulata Blanco, leaf of Diospyros kaki L.f. was the dried powder of 20 mesh sieves.
3. the method for distilling of flavonoid glycoside substance as claimed in claim 1, it is characterized in that said peel of Citrus reticulata Blanco, leaf of Diospyros kaki L.f. dry fragment mass ratio be 2: 3.
4. the method for distilling of flavonoid glycoside substance as claimed in claim 1 is characterized in that the described sedimentation time is for precipitating 12～48 hours.
5. the method for distilling of flavonoid glycoside substance as claimed in claim 1 is characterized in that described flame filter press is with the filter pressing of 3～10 layers of DANFU silk filter cloth.
6. the method for distilling of flavonoid glycoside substance as claimed in claim 1; The vacuum that it is characterized in that described step (5) control first distillator is that 750～850Pa, vapo(u)rizing temperature are 40 ℃～50 ℃, and the cryosurface temperature is to carry out thin film evaporation under 15～25 ℃ the condition.
7. the method for distilling of flavonoid glycoside substance as claimed in claim 1; The vacuum that it is characterized in that described step (5) control after-fractionating device is that 150～250Pa, vapo(u)rizing temperature are 65 ℃～75 ℃, and the condition that the cryosurface temperature is 15～25 ℃ is carried out thin film evaporation.
8. the method for distilling of flavonoid glycoside substance as claimed in claim 1 is characterized in that the vacuum of described step (5) control the 3rd distillator is that 20～40Pa, vapo(u)rizing temperature are 80 ℃～100 ℃, and the condition that the cryosurface temperature is 15～25 ℃ is carried out thin film evaporation.
9. the method for distilling of flavonoid glycoside substance as claimed in claim 1; The vacuum that it is characterized in that described step (5) control the 4th distillator is 0.01～0.5Pa; Vapo(u)rizing temperature is 200 ℃～300 ℃, and the cryosurface temperature is to carry out thin film evaporation under 20～30 ℃ the condition, collects distillate.
10. the method for distilling of the described flavonoid glycoside substance of claim 1, it is characterized in that described method is for as follows: the mass ratio that impurity is removed in (1) is that 2: 3 peel of Citrus reticulata Blanco, the dried powder of leaf of Diospyros kaki L.f. are raw material; (2) add 55%～60% the ethanol that quality is 10～15 times of peel of Citrus reticulata Blanco, leaf of Diospyros kaki L.f. dried powder quality summation, 2.5～3h are extracted in 50 ℃ of insulations, and are centrifugal, filter, and the A that must filtrate, filtering residue repeat to extract 2～3 times again, merge each filtrating A and get extracting solution; (3) step (2) gained extracting solution was left standstill 12～24 hours, deposition is got supernatant, and adding quality is the kieselguhr of said supernatant 2%, after fully stirring, with 6～8 metafiltration cloth filter pressings, gets liquor B with flame filter press; (4) liquor B is carried out membrane filtration with the poly (ether sulfone) film material, molecular cut off 5kD gets the micromolecule solution of filter membrane; (5) getting micromolecule solution that step (4) obtains feeds membrane evaporator and separates; Described membrane evaporator comprises the level Four distillator; Control material flow 1～3ml/min, knifing rotating speed at different levels is 100-200rpm, circulating water temperature is respectively done for oneself 30～70 ℃; The vacuum of controlling first distillator is that 750～850Pa, vapo(u)rizing temperature are that 40 ℃～50 ℃, cryosurface temperature are to carry out thin film evaporation under 15～25 ℃ the condition; Must heat up in a steamer excess A and directly get into the after-fractionating device, the vacuum of control after-fractionating device is that 150～250Pa, vapo(u)rizing temperature are that 65 ℃～75 ℃, cryosurface temperature are to carry out thin film evaporation under 15～25 ℃ the condition, must heat up in a steamer excess B and directly get into the 3rd distillator; The vacuum of controlling the 3rd distillator is that 20～40Pa, vapo(u)rizing temperature are to carry out thin film evaporation under the condition of 15～25 ℃ of 80 ℃～90 ℃, cryosurface temperature; Must heat up in a steamer excess C and directly get into the 4th distillator, the vacuum of controlling the 4th distillator is 0.01～0.05Pa, and vapo(u)rizing temperature is 250 ℃～280 ℃; Carry out thin film evaporation under the condition that the cryosurface temperature is 30 ℃, collect distillate; (6) getting distillate that step (5) collects carries out spray drying and processes powdery, promptly described flavonoid glycoside substance.
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