CN107235949B - Method for extracting anthocyanin extract without plasticizer - Google Patents
Method for extracting anthocyanin extract without plasticizer Download PDFInfo
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- CN107235949B CN107235949B CN201710455843.4A CN201710455843A CN107235949B CN 107235949 B CN107235949 B CN 107235949B CN 201710455843 A CN201710455843 A CN 201710455843A CN 107235949 B CN107235949 B CN 107235949B
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- 239000004014 plasticizer Substances 0.000 title claims abstract description 90
- 150000004636 anthocyanins Chemical class 0.000 title claims abstract description 72
- 229930002877 anthocyanin Natural products 0.000 title claims abstract description 71
- 235000010208 anthocyanin Nutrition 0.000 title claims abstract description 71
- 239000004410 anthocyanin Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000000284 extract Substances 0.000 title claims abstract description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000011347 resin Substances 0.000 claims abstract description 87
- 229920005989 resin Polymers 0.000 claims abstract description 87
- 238000000605 extraction Methods 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000012530 fluid Substances 0.000 claims abstract description 27
- 238000001914 filtration Methods 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 14
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- 230000006837 decompression Effects 0.000 claims abstract description 3
- 238000011068 loading method Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 44
- 238000001179 sorption measurement Methods 0.000 claims description 32
- 239000003480 eluent Substances 0.000 claims description 28
- 239000012528 membrane Substances 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 21
- 238000001728 nano-filtration Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 240000004153 Hibiscus sabdariffa Species 0.000 claims description 9
- 235000001018 Hibiscus sabdariffa Nutrition 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 235000013399 edible fruits Nutrition 0.000 claims description 9
- 235000016357 Mirtillo rosso Nutrition 0.000 claims description 8
- 244000078534 Vaccinium myrtillus Species 0.000 claims description 8
- 244000077923 Vaccinium vitis idaea Species 0.000 claims description 8
- 235000017606 Vaccinium vitis idaea Nutrition 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 235000017537 Vaccinium myrtillus Nutrition 0.000 claims description 6
- 238000000502 dialysis Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 235000003095 Vaccinium corymbosum Nutrition 0.000 claims description 5
- 235000021014 blueberries Nutrition 0.000 claims description 5
- 240000000249 Morus alba Species 0.000 claims description 4
- 235000008708 Morus alba Nutrition 0.000 claims description 4
- 230000009965 odorless effect Effects 0.000 claims description 4
- 238000010828 elution Methods 0.000 claims description 3
- 241000371652 Curvularia clavata Species 0.000 claims description 2
- 244000017020 Ipomoea batatas Species 0.000 claims description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 2
- 235000017848 Rubus fruticosus Nutrition 0.000 claims description 2
- 240000007651 Rubus glaucus Species 0.000 claims description 2
- 235000011034 Rubus glaucus Nutrition 0.000 claims description 2
- 235000009122 Rubus idaeus Nutrition 0.000 claims description 2
- 235000021029 blackberry Nutrition 0.000 claims description 2
- 239000011368 organic material Substances 0.000 claims description 2
- 239000003463 adsorbent Substances 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 description 15
- 229940055416 blueberry extract Drugs 0.000 description 12
- 235000019216 blueberry extract Nutrition 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000447 pesticide residue Substances 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 238000000825 ultraviolet detection Methods 0.000 description 3
- 235000009815 Momordica Nutrition 0.000 description 2
- 241000218984 Momordica Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 235000021022 fresh fruits Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- 235000004101 Gaylussacia dumosa Nutrition 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 244000185386 Thladiantha grosvenorii Species 0.000 description 1
- 235000011171 Thladiantha grosvenorii Nutrition 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229930014669 anthocyanidin Natural products 0.000 description 1
- 150000001453 anthocyanidins Chemical class 0.000 description 1
- 235000008758 anthocyanidins Nutrition 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 230000007665 chronic toxicity Effects 0.000 description 1
- 231100000160 chronic toxicity Toxicity 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000011278 co-treatment Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
- C07D311/60—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with aryl radicals attached in position 2
- C07D311/62—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with aryl radicals attached in position 2 with oxygen atoms directly attached in position 3, e.g. anthocyanidins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Seasonings (AREA)
- Medicines Containing Plant Substances (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Extraction Or Liquid Replacement (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
Abstract
A method for extracting anthocyanin extract without plasticizer comprises the following stepsThe method comprises the following steps: (1) crushing an anthocyanin raw material, adding an extraction solvent to perform continuous countercurrent flash extraction, cooling, filtering, and concentrating under reduced pressure to obtain an anthocyanin extracting solution; (2) filtering to remove impurities, dialyzing the filtrate, and concentrating under reduced pressure to obtain concentrated solution; (3) loading onto macroporous adsorbent resin column, washing with water to colorless, discarding, eluting with ethanol water solution to colorless, and collecting ethanol eluate; (4) removing plasticizer resin column from the ethanol eluate, and concentrating under reduced pressure to obtain anthocyanin extract; (5) by supercritical CO2Fluid extraction, decompression concentration and drying to obtain anthocyanin extract without plasticizer. The plasticizer removal rate of the extract obtained by the method is more than or equal to 99.95 percent; the total yield of the obtained anthocyanin is more than or equal to 90 percent; compared with the prior art, the method has stronger stability and good selectivity, and is suitable for industrial production.
Description
Technical Field
The invention relates to an extraction method of an anthocyanin extract, and particularly relates to an extraction method of a plasticizer-free anthocyanin extract.
Background
The plasticizer (plasticizer) is a high polymer material auxiliary agent, is various, is the most common DEHP, and is colorless and odorless liquid. The plasticizer is used as an industrial polymer material auxiliary agent, is generally applied to materials such as plastic products, concrete, cosmetics, cleaning agents and the like, and is particularly applied to polyvinyl chloride plastic products. In addition, the phthalic lactone can be slowly released in the processes of plastic industrial production, plastic products and plastic waste treatment, food is polluted by various ways, such as atmosphere, water, soil, food packaging and transportation materials and the like, and particularly in white waste polluted soil and water, the plasticizer content is higher.
The plasticizer belongs to persistent organic pollutants, is difficult to degrade, is easy to enrich in human bodies, is difficult to metabolize by the human bodies, has chronic toxicity, and can cause the abnormality of reproductive systems, even carcinogenesis, teratogenesis, mutagenesis and the like if being taken for a long time and enriched to a certain degree.
The anthocyanin extract is used as a natural haematochrome, is a food additive approved by pharmacopoeia, and is widely applied to beverages, cakes and the like. However, many of the anthocyanin extracts on the market have plasticizer indexes exceeding international standards. The existing plasticizer removing mode is single, the plasticizer removing rate is low, and the quality stability is poor.
CN105198942A discloses a process for removing plasticizer from mulberry anthocyanin, which comprises the steps of extracting mulberry with 40-95% ethanol, concentrating an extracting solution, applying the concentrated extracting solution to D-101 macroporous adsorption resin, firstly washing with water until an effluent liquid is clear, then eluting with 30-75% ethanol, collecting an eluent, concentrating until the sugar degree is 15 ℃, extracting with ethyl acetate, wherein the extracting ratio of an extracting agent to a crude extracting solution is 1: 1-5, and extracting for 1-3 times. However, although the ethyl acetate extraction method has a certain effect on removing the plasticizer according to the property that the plasticizer is easily soluble in an organic solvent, the method is single, the operation is complicated, the plasticizer removing effect is limited, and the solvent loss is large.
CN106306991A discloses a method for simultaneously removing pesticide residue and plasticizer in fructus Siraitiae Grosvenorii extract, which is to use supercritical CO containing entrainer for fructus Siraitiae Grosvenorii extract2Extracting to obtain a primary extract of the grosvenor momordica fruit extract, dissolving the primary extract in water, nano-filtering, and spray-drying to obtain the grosvenor momordica fruit extract with pesticide residues and plasticizer removed. The method mainly adopts supercritical CO2Removing fat-soluble plasticizer by extraction, and supercritical CO2The fat-soluble pesticide residue and the water-soluble pesticide residue in the momordica grosvenori extract are respectively removed by combining the extraction and the nanofiltration, although the content of the pesticide residue and the plasticizer is reduced and most of the plasticizer is removed to a certain degree, the quality stability of the product obtained by the method is poor, and the supercritical CO is adopted2The fluid has weak permeability to solid dry powder and only passes through the supercritical CO once2The extraction method cannot effectively and completely remove the plasticizer.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provide the method for extracting the anthocyanin extract without the plasticizer, which has the advantages of simple process, low cost, good selectivity, high purity and recovery rate of the obtained product, stable quality and suitability for industrial production.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for extracting anthocyanin extract without plasticizer comprises the following steps:
(1) pretreatment and flash extraction: crushing an anthocyanin raw material, adding an extraction solvent to perform continuous countercurrent flash extraction, cooling, filtering, and concentrating an extracting solution under reduced pressure to obtain an anthocyanin extracting solution;
(2) filtering and dialyzing: filtering the anthocyanin extracting solution obtained in the step (1) to remove impurities, dialyzing the filtrate, and concentrating the trapped fluid under reduced pressure to obtain concentrated solution;
(3) purifying with macroporous adsorption resin: adsorbing the concentrated solution obtained in the step (2) by using macroporous adsorption resin columns which are continuously connected in series, washing with water until water eluent is colorless, discarding water eluent, eluting the resin columns which are connected in series by using ethanol aqueous solution until the ethanol eluent is colorless, and collecting ethanol eluent;
(4) removing plasticizer from resin: loading the ethanol eluent obtained in the step (3) on a plasticizer resin removing column, and concentrating the effluent under reduced pressure to obtain an anthocyanin extract;
(5) supercritical CO2And (3) extraction: respectively using supercritical CO to the anthocyanin extract obtained in the step (4)2Fluid extraction, decompression concentration and drying to obtain anthocyanin extract without plasticizer.
Preferably, in the step (1), the mass-to-volume ratio (kg/L) of the anthocyanin raw material to the extraction solvent is 1: 10-20.
Preferably, in the step (1), the anthocyanin raw material is one or more of blueberry, blackberry, raspberry, huckleberry, black rice, mulberry, purple sweet potato or roselle. The mass content of the anthocyanin in the anthocyanin raw material is 0.5-1.0%, and the content of the total plasticizer is 1.0-3.0 mg/kg. Plasticizers are mainly used in soil, water and plastic materials that come into contact during picking, packaging and transportation.
Preferably, in the step (1), the extraction solvent is an ethanol aqueous solution with a volume concentration of 40-95% (more preferably 70-80%).
Preferably, in the step (1), the temperature of the continuous countercurrent flash extraction is 30-60 ℃, the extraction time is 50-120 s, and the extraction frequency is more than or equal to 2 times. The extraction apparatus is a continuous countercurrent flash extractor. Because the property of anthocyanin in the raw material is unstable, and the anthocyanin structure can be damaged after long-time or high-temperature extraction, the continuous countercurrent flash extraction is adopted, so that the extraction time can be shortened, the continuity of industrial production can be ensured, and the extraction yield of anthocyanin is improved under stirring.
Preferably, in step (1), the cooling is performed by a plate heat exchanger. And filtering the solution subjected to continuous countercurrent flash extraction by using a filter screen of 100-400 meshes.
Preferably, in the step (1), the temperature of the reduced pressure concentration is 40-70 ℃, the pressure is-0.10-0.07 MPa, and the concentration is carried out until the solid content is 5-10%.
Preferably, in the step (2), the membrane pressure of the filtration is 1-4 MPa, and the temperature is 5-30 ℃. The anthocyanin raw material is extracted by ethanol, after the ethanol is recovered under reduced pressure and concentrated, part of alcohol-soluble water-insoluble impurities can be separated out in the process of low-temperature placement, and can be effectively removed by using membrane filtration.
Preferably, in the step (2), the ceramic membrane is used for filtration, and the pore diameter of the ceramic membrane is 0.2-1.0 μm.
Preferably, in the step (2), the membrane pressure of the dialysis is 1-3 MPa, and the temperature is 5-20 ℃. The dialysis can effectively get rid of small molecule impurity, promotes product purity, simultaneously because the molecular weight of plasticizing agent is less, also can get rid of by most through the mode of dialysis.
Preferably, in the step (2), a nanofiltration membrane made of a high molecular organic material is used for dialysis, and the molecular weight of the nanofiltration membrane is 500-5000 kilodaltons (more preferably 600-2000 kilodaltons).
Preferably, in the step (2), the temperature of the reduced pressure concentration is 30-70 ℃, the pressure is-0.10-0.07 MPa, and the concentration is carried out until the solid content is 5-20%.
Preferably, in the step (3), the diameter-height ratio of the macroporous adsorption resin column is 1: 1-8 (more preferably 1: 5-7). The macroporous adsorption resin is mainly used for adsorbing, separating and purifying the effective component anthocyanin in the anthocyanin raw material.
Preferably, in the step (3), the volume-to-mass ratio (L/kg) of the macroporous adsorption resin to the anthocyanin raw material is 1: 8-40 (more preferably 1: 10-20).
Preferably, in the step (3), the number of the macroporous adsorption resin columns connected in series is more than or equal to 2, and more preferably 3 resins are connected in series.
Preferably, in the step (3), the model of the macroporous absorption resin is one or more of HP-20, HPD-100, XDA-6 or HP2MGL and the like. The XDA-6 type macroporous adsorbent resin is preferably obtained from New science and technology materials, Inc. of Xian blue, Xiao, Inc., the HP-20 and HPD-100 type macroporous adsorbent resins are preferably obtained from Aikojian (China) biological medicine, Inc., and the HP2MGL type macroporous adsorbent resin is preferably obtained from Mitsubishi resin corporation.
Preferably, in the step (3), the flow rate of the upper column is 0.5-3.0 BV/h (more preferably 1-2 BV/h).
Preferably, in the step (3), the flow rate of the water washing is 1.0-4.0 BV/h.
Preferably, in the step (3), the volume-to-mass ratio (L/kg) of the ethanol aqueous solution to the anthocyanin raw material is 1: 2-5.
Preferably, in the step (3), the flow rate of the ethanol elution is 0.4-0.8 BV/h. The ethanol elution is mainly used for eluting the anthocyanin adsorbed by the macroporous adsorption resin.
Preferably, in the step (3), the volume concentration of the ethanol aqueous solution is 50-80%.
Preferably, in the step (4), the de-plasticizer resin column has a column diameter-height ratio of 1: 4-12.
Preferably, in the step (4), the volume ratio (L/L) of the resin for deplasticizing agent to the eluent is 1: 40-60.
Preferably, in the step (4), the flow rate of the upper column is 0.5-2.0 BV/h.
Preferably, in the step (4), the resin for deplasticizing agent is a special macroporous adsorption resin, the resin type is one or more of XDA-8G, XDA-8D, HPD-500, HPD-950 or D4020, and the like, and XDA-8G and/or XDA-8D are/is more preferable. The XDA-8G, XDA-8D type deplasticizer resin is preferably obtained from New science and technology materials, Inc. of Xian blue, Xiao, Xian, the HPD-500 and HPD-950 type deplasticizer resins are preferably obtained from Aimejian (China) biomedical, Inc., and the D4020 type deplasticizer resin is preferably obtained from Tianjin Nankai and ChengTechni, Inc. The inventor researches and discovers that although the deplasticizing agent resin is mainly used in the white spirit industry and is less applied to natural products, the resin has firmer adsorption effect on the plasticizing agent and less adsorption effect on anthocyanin in a certain concentration of alcohol phase.
Preferably, in the step (4), the temperature of the reduced pressure concentration is 40-70 ℃, the pressure is-0.10-0.07 MPa, and the reduced pressure concentration is carried out until the solid content is 30-50%.
Preferably, in the steps (3) and (4), before use, the resin is soaked in 1.5-2.5 BV of 90-99% ethanol by volume concentration for 20-30 h, then washed with 90-99% ethanol by volume concentration until the effluent is colorless and odorless and no plasticizer can be detected, then washed with 3-5 BV of 3-5% sodium hydroxide solution by mass concentration, then washed with water until the effluent is neutral, finally washed with 3-5 BV of 3-5% hydrochloric acid by mass concentration, and then washed with water until the effluent is neutral and no plasticizer can be detected.
Preferably, in step (5), the supercritical CO2The pressure of fluid extraction is 20-40 MPa, the extraction temperature is 20-30 ℃, the extraction time is 1-2 h, and the extraction time is more than or equal to 2 times. The supercritical CO2The fluid is mainly used for extracting and removing the plasticizer.
Preferably, in the step (5), the anthocyanin extract is mixed with CO2The mass-to-volume ratio (kg/L) of the fluid is 1: 10-25.
Preferably, in step (5), the supercritical CO2The entrainer used in the fluid extraction is used for extracting CO210-30% of the volume of the fluid, wherein the entrainer is 70-95% of methanol or ethanol water solution (more preferably ethanol water solution) by volume fraction.
Preferably, in the step (5), the temperature of the reduced pressure concentration is 40-70 ℃, the pressure is-0.10-0.07 MPa, and the concentration is carried out until the solid content is 40-60%.
Preferably, in the step (5), the drying mode is microwave drying, the temperature of the microwave drying is 10-40 ℃, the pressure is-0.10-0.07 MPa, and the drying is carried out until the water content is less than or equal to 3%.
The equipment used for concentration in the method is a single-effect concentrator, a double-effect concentrator or a triple-effect concentrator.
The reagents used in the method are food-grade plasticizer-free reagents.
The equipment, the pipeline and the storage tank which are used in the method and are in contact with the materials are all made of acid and alkali resistant stainless steel materials.
The principle of the method of the invention is as follows: because the anthocyanin raw material is inevitably contacted with the material containing the plasticizer in the processes of picking, packaging, transporting, producing and packaging, especially when a high-content anthocyanin product is prepared, macroporous adsorption resin is traditionally used for purifying, and although the macroporous adsorption resin has an enrichment effect on the plasticizer, the plasticizer is eluted along with the product when a high-concentration organic solvent is used for eluting. The invention adopts nanofiltration technology, macroporous adsorption resin purification, resin plasticizer removal and supercritical CO2The anthocyanin extract without the plasticizer is prepared by the fluid extraction technology combined in sequence. Firstly, a nanofiltration technology is adopted for dialysis and plasticizer removal, the main plasticizer is a fat-soluble component which is easily soluble in ethanol, the molecular weight is 300-500, most of the plasticizer can be dialyzed, most of the ethanol can be removed, and part of small molecular impurities can be removed through a nanofiltration membrane with the molecular weight cut-off of 600-5000 kilodaltons, so that the time for recovering the solvent is shortened, the loss of anthocyanin is reduced, and the purity of the anthocyanin is improved. However, the method has certain limitations on plasticizer removal and anthocyanin purity improvement by only using nanofiltration membrane separation and purification, so that macroporous adsorption resin is adopted to be connected in series for separation and purification, which is mainly used for purifying anthocyanin, and anthocyanin extracts with different specifications can be obtained, but the obtained extract still contains a small amount of plasticizer due to the enrichment effect of the macroporous adsorption resin on the plasticizer, so that the plasticizer can be effectively removed and simultaneously the plasticizer can be removed by adopting a specific resinReduce the adsorption loss of the resin to the anthocyanin. Finally adopting supercritical CO2The extraction technique synergistically removes the plasticizer, although fat-soluble supercritical CO2The fluid has strong plasticizer extraction capacity, but the inventor researches and discovers that if the technology is singly adopted, the technology has certain limitation, and the problems of incomplete removal, unstable quality and the like exist. In the specific large-scale production process, due to the factors of wide raw material production area sources, large production solvent and the like, the plasticizer content of each batch of products is different, and the plasticizer content is high or low, so that the plasticizer is removed by using a single mode, and the final removal effect is large in difference and limited in function due to the same process. Therefore, the method adopts a nanofiltration technology, a macroporous adsorption resin purification technology, a resin plasticizer removal technology and supercritical CO2The extraction technology is combined in sequence, and most of the plasticizer is removed in the processes of nanofiltration and resin deplasticizing agent removal, and then supercritical CO is used2The stability of the product quality can be ensured by the extraction technology.
The method has the following beneficial effects:
(1) the method adopts a nanofiltration technology, a resin plasticizer removing technology and supercritical CO2The plasticizer removal rate of the composite technology of the extraction technology is more than or equal to 99.95 percent, and the plasticizer content after plasticizer removal meets the international standard; the plasticizer of the anthocyanin extract obtained by the method reaches the anthocyanin product of the international standard, the anthocyanin content is more than or equal to 40 percent, and the total yield of the obtained anthocyanin is more than or equal to 90 percent;
(2) the solvent dosage for extraction in the method is reduced from 30-40 times of the raw material dosage to 10-20 times of the raw material dosage when the extraction tank is used for extraction originally, so that the energy consumption and the cost are reduced;
(3) the method uses nanofiltration technology, resin plasticizer removal technology and supercritical CO2The plasticizer is removed by combining the extraction technologies in sequence, compared with single supercritical CO2The extraction technology or the solvent extraction technology has better effect, stronger stability and good selectivity, and is suitable for industrial production.
Detailed Description
The present invention will be further described with reference to the following examples.
The blueberry fresh fruits, the cowberry fresh fruits and the roselle are sold in the market, the mass contents of the anthocyanidin are respectively 0.67%, 0.65% and 0.75%, and the total plasticizer contents are respectively 1.8mg/kg, 1.2mg/kg and 2.5 mg/kg; the reagents used in the examples of the invention were all food grade plasticizer-free reagents; the equipment, the pipelines and the storage tank which are used in the embodiment of the invention and are in contact with the materials are made of acid and alkali resistant stainless steel;
the XDA-6 type macroporous adsorbent resin used in the examples of the present invention was purchased from New scientific and technological materials, Inc. of Xian blue, Xiao, West, the HPD-100 type macroporous adsorbent resin was purchased from Ai's Kejian (China) biological medicine, Inc., and the HP2MGL type macroporous adsorbent resin was purchased from Mitsubishi resin corporation; the XDA-8G, XDA-8D type plasticizer-removing resin used in the examples of the present invention was purchased from New scientific and technical materials, Inc., Xian blue, and the HPD-500 type plasticizer-removing resin was purchased from Aimejian (China) biomedical Inc.;
before the macroporous adsorption resin or the plasticizer removing resin in the embodiment of the invention is used, the macroporous adsorption resin or the plasticizer removing resin is soaked in 2BV of 95% ethanol by volume for 24 hours, then washed by 95% ethanol by volume until effluent liquid is colorless and odorless and no plasticizer can be detected, washed by alkaline by 4BV of 5% sodium hydroxide by mass concentration, washed by water until the effluent liquid is neutral, finally washed by 4BV of 5% hydrochloric acid by mass concentration and washed by water until the effluent liquid is neutral and no plasticizer can be detected.
The starting materials or chemicals used in the examples of the present invention are, unless otherwise specified, commercially available in a conventional manner.
Example 1
(1) Pretreatment and flash extraction: crushing 1000kg of fresh blueberry fruits, adding 10000L of ethanol aqueous solution with volume fraction of 70%, continuously performing countercurrent flash extraction for 60s at 40 ℃ by using continuous countercurrent flash extraction equipment, extracting for 2 times, cooling by using a plate heat exchanger, filtering by using a 200-mesh filter screen, performing reduced pressure concentration on an extracting solution by using a single-effect concentrator at 50 ℃ and under the vacuum degree of-0.08 MPa, and recovering ethanol until the solid content of the concentrated solution is 8% to obtain a blueberry extracting solution;
(2) filtering and dialyzing: filtering and removing impurities from the blueberry extract obtained in the step (1) by using a ceramic membrane with the aperture of 0.5 mu m at the membrane pressure of 2MPa and the temperature of 10 ℃, dialyzing filtrate by using a nanofiltration membrane with the molecular weight of 600 ten thousand daltons at the membrane pressure of 1MPa and the temperature of 10 ℃, and concentrating trapped fluid by using a single-effect concentrator under the reduced pressure at the temperature of 40 ℃ and the vacuum degree of-0.08 MPa until the solid content of the concentrated solution is 10 percent to obtain 423kg of concentrated solution;
(3) purifying with macroporous adsorption resin: adsorbing 423kg of the concentrated solution obtained in the step (2) by using 3 XDA-6 type macroporous adsorption resin columns (the diameter-height ratio is 1:5, the dosage of the macroporous resin is 80L) which are continuously connected in series at the column flow rate of 1BV/h, then firstly washing with water at the flow rate of 2BV/h until the water eluent is colorless, discarding the water eluent, then eluting the resin columns which are connected in series at the flow rate of 0.4BV/h until the ethanol eluent is colorless by using 200L of 60% ethanol aqueous solution, and collecting the ethanol eluent with the volume of 200L;
(4) removing plasticizer from resin: feeding 200L of ethanol eluent obtained in the step (3) to an HPD-500 type plasticizer removal resin column (the diameter-height ratio is 1:4, the using amount of the resin is 5L) at the column flow rate of 0.8BV/h, and concentrating the effluent liquid under reduced pressure to 35% of solid content at 50 ℃ and-0.08 MPa by using a single-effect concentrator to obtain 30.8kg of blueberry extract;
(5) supercritical CO2And (3) extraction: subjecting 30.8kg of blueberry extract obtained in step (4) to 400L of supercritical CO2Extracting the fluid for 1h at 20MPa and 20 ℃ for 3 times, then concentrating the fluid under reduced pressure by using a single-effect concentrator at 50 ℃ and-0.08 MPa until the solid content is 40%, and finally drying the fluid by using microwaves at 20 ℃ and-0.08 MPa until the water content is 3% to obtain 15.13kg of plasticizer-free blueberry extract; wherein the entrainer is ethanol water solution with volume fraction of 70%, and the amount of the entrainer is 80L.
The total plasticizer content of the plasticizer-free blueberry extract obtained in the embodiment is 0.03mg/kg and the removal rate is 99.98% according to the detection of a gas chromatography-mass spectrometry (GC-MS) method, and the international standard is met.
Through ultraviolet detection, the anthocyanin content of the plasticizer-free blueberry extract obtained in the embodiment is 40.6%, and the total yield is 91.5%.
Example 2
(1) Pretreatment and flash extraction: crushing 1000kg of fresh cowberry fruits, adding into 15000L ethanol aqueous solution with volume fraction of 80%, performing continuous countercurrent flash extraction for 3 times at 50 deg.C for 100s by continuous countercurrent flash extraction equipment, cooling by plate heat exchanger, filtering with 300 mesh filter screen, concentrating the extractive solution with double-effect concentrator at 60 deg.C under vacuum degree of-0.095 MPa, and recovering ethanol under reduced pressure until the solid content of the concentrated solution is 5% to obtain cowberry extractive solution;
(2) filtering and dialyzing: filtering and removing impurities from the cowberry fruit extracting solution obtained in the step (1) by using a ceramic membrane with the aperture of 0.3 mu m at the membrane pressure of 3MPa and the temperature of 20 ℃, dialyzing the filtrate by using a nanofiltration membrane with the molecular weight of 1000 ten thousand daltons at the membrane pressure of 2MPa and the temperature of 15 ℃, and concentrating the trapped fluid by using a double-effect concentrator under the reduced pressure at the temperature of 60 ℃ and the vacuum degree of-0.095 MPa until the solid content of the concentrated solution is 15 percent to obtain 300kg of concentrated solution;
(3) purifying with macroporous adsorption resin: adsorbing 300kg of the concentrated solution obtained in the step (2) by using 3 HP2MGL type macroporous adsorption resin columns (the diameter-height ratio is 1:6, the dosage of the macroporous resin is 100L) which are continuously connected in series at the column flow rate of 2BV/h, then washing with water at the flow rate of 1BV/h until the eluent is colorless, discarding the water eluent, then eluting the resin columns connected in series by using 300L of ethanol aqueous solution with the volume concentration of 70% at the flow rate of 0.5BV/h until the ethanol eluent is colorless, and collecting the ethanol eluent, wherein the volume of the ethanol eluent is 300L;
(4) removing plasticizer from resin: feeding 300L ethanol eluate obtained in step (3) into XDA-8D type deplasticizing agent resin column (diameter-height ratio is 1:6, dosage of resin is 5L) at column flow rate of 1BV/h, concentrating the effluent liquid under reduced pressure at 60 deg.C and-0.095 MPa to solid content of 40% in a double-effect concentrator to obtain 35.5kg cowberry fruit extract;
(5) supercritical CO2And (3) extraction: subjecting 35.5kg of cowberry fruit extract obtained in step (4) to 800L of supercritical CO2Extracting fluid at 30 deg.C under 30MPa for 2 hr for 2 times, and concentrating with double-effect concentrator at-0.095 MPa at 60 deg.CConcentrating under reduced pressure to solid content of 45%, and microwave drying at-0.095 MPa at 20 deg.C to water content of 2% to obtain 13.68kg of plasticizer-free cowberry fruit extract; wherein the entrainer is 80% ethanol water solution by volume fraction, and the amount of the entrainer is 80L.
The total plasticizer content of the plasticizer-free blueberry extract obtained in the embodiment is 0.01mg/kg, the removal rate is 99.99%, and the plasticizer-free blueberry extract meets the international standard through detection of a gas chromatography-mass spectrometry (GC-MS) method.
Through ultraviolet detection, the anthocyanin content of the plasticizer-free blueberry extract obtained in the embodiment is 43.2%, and the total yield is 90.5%.
Example 3
(1) Pretreatment and flash extraction: crushing 1000kg roselle, adding into 20000L ethanol water solution with volume fraction of 70%, continuously countercurrent flash extracting for 60s at 60 deg.C for 3 times by continuous countercurrent flash extraction equipment, cooling with plate heat exchanger, filtering with 200 mesh filter screen, concentrating the extractive solution with single-effect concentrator at 60 deg.C under vacuum degree of-0.095 MPa, and recovering ethanol under reduced pressure until the solid content of the concentrated solution is 5% to obtain roselle extractive solution;
(2) filtering and dialyzing: filtering and removing impurities from the roselle extract obtained in the step (1) by using a ceramic membrane with the aperture of 0.8 mu m at the membrane pressure of 4MPa and the temperature of 30 ℃, dialyzing filtrate by using a nanofiltration membrane with the molecular weight of 2000 ten thousand daltons at the membrane pressure of 3MPa and the temperature of 20 ℃, and concentrating trapped fluid by using a single-effect concentrator under reduced pressure at the temperature of 70 ℃ and the vacuum degree of-0.95 MPa until the solid content of the concentrate is 10 percent to obtain 532kg of concentrate;
(3) purifying with macroporous adsorption resin: adsorbing 532kg of the concentrated solution obtained in the step (2) by using 3 HPD-100 type macroporous adsorption resin columns (the diameter-height ratio is 1:7, and the dosage of the macroporous resin is 60L) which are continuously connected in series at the column flow rate of 2BV/h, then washing with water at the flow rate of 3BV/h until the water eluent is colorless, discarding the water eluent, then eluting the resin columns which are connected in series at the flow rate of 0.6BV/h until the ethanol eluent is colorless by using 500L of 80% ethanol water solution, and collecting the ethanol eluent, wherein the volume of the ethanol eluent is 500L;
(4) removing plasticizer from resin: feeding the 500L ethanol eluate obtained in the step (3) into an XDA-8G type plasticizer removal resin column (the diameter-height ratio is 1:10, the dosage of the resin is 10L) at the column flow rate of 1.5BV/h, and concentrating the effluent liquid under reduced pressure to 45% of solid content at 70 ℃ and-0.095 MPa by using a single-effect concentrator to obtain 40.5kg of a roselle extract;
(5) supercritical CO2And (3) extraction: subjecting 40.5kg of the extract of Hibiscus sabdariffa obtained in step (4) to supercritical CO treatment with 800L2Extracting fluid for 2 hours at the temperature of 30 ℃ under 40MPa for 2 times, then concentrating the fluid under reduced pressure by using a single-effect concentrator at the temperature of 70 ℃ and under the pressure of-0.095 MPa until the solid content is 50 percent, and finally drying the fluid by using microwaves at the temperature of 30 ℃ and under the pressure of-0.095 MPa until the water content is 2 percent to obtain 15.13kg of plasticizer-free roselle extract; wherein the entrainer is ethanol water solution with volume fraction of 90%, and the amount of the entrainer is 80L.
The total plasticizer content of the plasticizer-free blueberry extract obtained in the embodiment is 0.05mg/kg, the removal rate is 99.97% and the plasticizer-free blueberry extract meets the international standard through detection of a gas chromatography-mass spectrometry (GC-MS) method.
Through ultraviolet detection, the anthocyanin content of the plasticizer-free blueberry extract obtained in the embodiment is 45.6%, and the total yield is 92.5%.
Claims (9)
1. The extraction method of the anthocyanin extract without the plasticizer is characterized by comprising the following steps of:
(1) pretreatment and flash extraction: crushing an anthocyanin raw material, adding an extraction solvent to perform continuous countercurrent flash extraction, cooling, filtering, and concentrating an extracting solution under reduced pressure to obtain an anthocyanin extracting solution;
(2) filtering and dialyzing: filtering the anthocyanin extracting solution obtained in the step (1) to remove impurities, dialyzing the filtrate, and concentrating the trapped fluid under reduced pressure to obtain concentrated solution;
(3) purifying with macroporous adsorption resin: adsorbing the concentrated solution obtained in the step (2) by using macroporous adsorption resin columns which are continuously connected in series, washing with water until water eluent is colorless, discarding water eluent, eluting the resin columns which are connected in series by using ethanol aqueous solution until the ethanol eluent is colorless, and collecting ethanol eluent;
(4) removing plasticizer from resin: loading the ethanol eluent obtained in the step (3) on a plasticizer resin removing column, and concentrating the effluent under reduced pressure to obtain an anthocyanin extract;
(5) supercritical CO2And (3) extraction: respectively using supercritical CO to the anthocyanin extract obtained in the step (4)2Fluid extraction, decompression concentration and drying to obtain anthocyanin extract without plasticizer;
in the step (1), the extraction solvent is an ethanol water solution with volume concentration of 40-95%;
in the step (2), the membrane pressure of the filtration is 1-4 MPa, and the temperature is 5-30 ℃; filtering with a ceramic membrane, wherein the aperture of the ceramic membrane is 0.2-1.0 mu m; the membrane pressure of dialysis is 1-3 MPa, and the temperature is 5-20 ℃; dialyzing by using a high molecular organic material nanofiltration membrane, wherein the molecular weight of the nanofiltration membrane is 500-5000 ten thousand daltons; the temperature of the reduced pressure concentration is 30-70 ℃, the pressure is-0.10 to-0.07 MPa, and the concentration is carried out until the solid content is 5-20%;
in the step (3), the model of the macroporous adsorption resin is one or more of HP-20, HPD-100, XDA-6 or HP2 MGL;
in the step (4), the type of the resin for removing the plasticizer is one or more of XDA-8G, XDA-8D, HPD-500, HPD-950 or D4020.
2. The method for extracting anthocyanin extract without plasticizer according to claim 1, wherein the method comprises the following steps: in the step (1), the mass-to-volume ratio of the anthocyanin raw material to the extraction solvent is 1: 10-20 kg/L; the anthocyanin raw material is one or more of blueberry, blackberry, raspberry, cowberry fruit, black rice, mulberry, purple sweet potato or roselle; the temperature of the continuous countercurrent flash extraction is 30-60 ℃, the extraction time is 50-120 s, and the extraction frequency is more than or equal to 2 times; the temperature of the reduced pressure concentration is 40-70 ℃, the pressure is-0.10 to-0.07 MPa, and the concentration is carried out until the solid content is 5-10%.
3. The method for extracting anthocyanin extract without plasticizer according to claim 2, wherein the method comprises the following steps: in the step (3), the diameter-height ratio of the macroporous adsorption resin column is 1: 1-8; the volume-mass ratio of the macroporous adsorption resin to the anthocyanin raw material is 1: 8-40L/kg; the number of the macroporous adsorption resin columns connected in series is more than or equal to 2.
4. The method for extracting anthocyanin extract without plasticizer according to claim 3, wherein the method comprises the following steps: in the step (3), the flow rate of the upper column is 0.5-3.0 BV/h; the flow rate of the water washing is 1.0-4.0 BV/h; the volume-mass ratio of the ethanol water solution to the anthocyanin raw material is 1: 2-5L/kg; the flow rate of the ethanol water solution elution is 0.4-0.8 BV/h; the volume concentration of the ethanol water solution is 50-80%.
5. The method for extracting anthocyanin extract without plasticizer according to claim 4, wherein the method comprises the following steps: in the step (4), the ratio of the diameter to the height of the plasticizer-removed resin column is 1: 4-12; the volume ratio of the resin for deplasticizing agent to the eluent is 1: 40-60; the flow rate of the upper column is 0.5-2.0 BV/h; the temperature of the reduced pressure concentration is 40-70 ℃, the pressure is-0.10 to-0.07 MPa, and the reduced pressure concentration is carried out until the solid content is 30-50%.
6. The method for extracting anthocyanin extract without plasticizer according to claim 5, wherein the method comprises the following steps: in the steps (3) and (4), before the resin is used, the resin is soaked in 1.5-2.5 BV of 90-99% ethanol by volume concentration for 20-30 h, then washed by 90-99% ethanol by volume concentration until the effluent is colorless and odorless and no plasticizer is detected, then washed by 3-5 BV of 3-5% sodium hydroxide solution by mass concentration, washed by water until the effluent is neutral, finally washed by 3-5 BV of 3-5% hydrochloric acid by mass concentration, and washed by water until the effluent is neutral and no plasticizer is detected.
7. The method for extracting anthocyanin extract without plasticizer according to claim 6, wherein: in the step (5), the supercritical CO2The pressure of fluid extraction is 20-40 MPa, the extraction temperature is 20-30 ℃, the extraction time is 1-2 h, and the extraction time is more than or equal to 2 times.
8. The method for extracting anthocyanin extract without plasticizer according to claim 7, wherein: in the step (5), the anthocyanin extract extractum is mixed with CO2The mass-to-volume ratio of the fluid is 1: 10-25 kg/L; the supercritical CO2The entrainer used in the fluid extraction is used for extracting CO210-30% of the volume of the fluid, wherein the entrainer is a methanol or ethanol aqueous solution with the volume fraction of 70-95%.
9. The method for extracting anthocyanin extract without plasticizer according to claim 8, wherein: in the step (5), the temperature of the reduced pressure concentration is 40-70 ℃, the pressure is-0.10-0.07 MPa, and the concentration is carried out until the solid content is 40-60%; the drying mode is microwave drying, the temperature of the microwave drying is 10-40 ℃, the pressure is-0.10 to-0.07 MPa, and the drying is carried out until the water content is less than or equal to 3 percent.
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