CN117567420A - Method for extracting and separating hop flavone and hop acid from hop - Google Patents
Method for extracting and separating hop flavone and hop acid from hop Download PDFInfo
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- CN117567420A CN117567420A CN202311518631.8A CN202311518631A CN117567420A CN 117567420 A CN117567420 A CN 117567420A CN 202311518631 A CN202311518631 A CN 202311518631A CN 117567420 A CN117567420 A CN 117567420A
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- 238000000034 method Methods 0.000 title claims abstract description 33
- 229930003944 flavone Natural products 0.000 title claims abstract description 28
- 235000011949 flavones Nutrition 0.000 title claims abstract description 28
- GAMYVSCDDLXAQW-AOIWZFSPSA-N Thermopsosid Natural products O(C)c1c(O)ccc(C=2Oc3c(c(O)cc(O[C@H]4[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O4)c3)C(=O)C=2)c1 GAMYVSCDDLXAQW-AOIWZFSPSA-N 0.000 title claims abstract description 26
- VHBFFQKBGNRLFZ-UHFFFAOYSA-N vitamin p Natural products O1C2=CC=CC=C2C(=O)C=C1C1=CC=CC=C1 VHBFFQKBGNRLFZ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 150000002212 flavone derivatives Chemical class 0.000 title claims abstract description 24
- 239000002253 acid Substances 0.000 title claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 93
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 43
- 238000000605 extraction Methods 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 31
- 235000008694 Humulus lupulus Nutrition 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 23
- 229930003935 flavonoid Natural products 0.000 claims description 14
- 235000017173 flavonoids Nutrition 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 150000002215 flavonoids Chemical class 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000284 extract Substances 0.000 claims description 7
- 150000007513 acids Chemical class 0.000 claims description 6
- 239000007900 aqueous suspension Substances 0.000 claims description 5
- 229930002875 chlorophyll Natural products 0.000 claims description 5
- 235000019804 chlorophyll Nutrition 0.000 claims description 5
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000175 humulus lupulus l. cone oil Substances 0.000 claims description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 239000002075 main ingredient Substances 0.000 claims description 3
- YKGCBLWILMDSAV-GOSISDBHSA-N Isoxanthohumol Natural products O(C)c1c2C(=O)C[C@H](c3ccc(O)cc3)Oc2c(C/C=C(\C)/C)c(O)c1 YKGCBLWILMDSAV-GOSISDBHSA-N 0.000 abstract description 25
- FUSADYLVRMROPL-UHFFFAOYSA-N demethylxanthohumol Natural products CC(C)=CCC1=C(O)C=C(O)C(C(=O)C=CC=2C=CC(O)=CC=2)=C1O FUSADYLVRMROPL-UHFFFAOYSA-N 0.000 abstract description 16
- ORXQGKIUCDPEAJ-YRNVUSSQSA-N xanthohumol Chemical compound COC1=CC(O)=C(CC=C(C)C)C(O)=C1C(=O)\C=C\C1=CC=C(O)C=C1 ORXQGKIUCDPEAJ-YRNVUSSQSA-N 0.000 abstract description 16
- UVBDKJHYMQEAQV-UHFFFAOYSA-N xanthohumol Natural products OC1=C(CC=C(C)C)C(OC)=CC(OC)=C1C(=O)C=CC1=CC=C(O)C=C1 UVBDKJHYMQEAQV-UHFFFAOYSA-N 0.000 abstract description 16
- 235000008209 xanthohumol Nutrition 0.000 abstract description 16
- 238000011084 recovery Methods 0.000 abstract description 15
- -1 flavone compounds Chemical class 0.000 abstract description 11
- YKGCBLWILMDSAV-SFHVURJKSA-N isoxanthohumol Chemical compound C1([C@H]2OC=3C(CC=C(C)C)=C(O)C=C(C=3C(=O)C2)OC)=CC=C(O)C=C1 YKGCBLWILMDSAV-SFHVURJKSA-N 0.000 abstract description 9
- FTVWIRXFELQLPI-ZDUSSCGKSA-N (S)-naringenin Chemical compound C1=CC(O)=CC=C1[C@H]1OC2=CC(O)=CC(O)=C2C(=O)C1 FTVWIRXFELQLPI-ZDUSSCGKSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- WGEYAGZBLYNDFV-UHFFFAOYSA-N naringenin Natural products C1(=O)C2=C(O)C=C(O)C=C2OC(C1)C1=CC=C(CC1)O WGEYAGZBLYNDFV-UHFFFAOYSA-N 0.000 abstract description 8
- 229940117954 naringenin Drugs 0.000 abstract description 8
- 235000007625 naringenin Nutrition 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 150000002213 flavones Chemical class 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 1
- 238000010298 pulverizing process Methods 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- VMSLCPKYRPDHLN-UHFFFAOYSA-N (R)-Humulone Chemical compound CC(C)CC(=O)C1=C(O)C(CC=C(C)C)=C(O)C(O)(CC=C(C)C)C1=O VMSLCPKYRPDHLN-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QRDZSRWEULKVNW-UHFFFAOYSA-N 6-hydroxy-2-oxo-1h-quinoline-4-carboxylic acid Chemical compound C1=C(O)C=C2C(C(=O)O)=CC(=O)NC2=C1 QRDZSRWEULKVNW-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000194 supercritical-fluid extraction Methods 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 235000013373 food additive Nutrition 0.000 description 2
- 239000002778 food additive Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- LSDULPZJLTZEFD-UHFFFAOYSA-N lupulone Chemical compound CC(C)CC(=O)C1=C(O)C(CC=C(C)C)=C(O)C(CC=C(C)C)(CC=C(C)C)C1=O LSDULPZJLTZEFD-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- 239000001606 7-[(2S,3R,4S,5S,6R)-4,5-dihydroxy-6-(hydroxymethyl)-3-[(2S,3R,4R,5R,6S)-3,4,5-trihydroxy-6-methyloxan-2-yl]oxyoxan-2-yl]oxy-5-hydroxy-2-(4-hydroxyphenyl)chroman-4-one Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DFPMSGMNTNDNHN-ZPHOTFPESA-N naringin Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1O[C@H]1[C@H](OC=2C=C3O[C@@H](CC(=O)C3=C(O)C=2)C=2C=CC(O)=CC=2)O[C@H](CO)[C@@H](O)[C@@H]1O DFPMSGMNTNDNHN-ZPHOTFPESA-N 0.000 description 1
- 229930019673 naringin Natural products 0.000 description 1
- 229940052490 naringin Drugs 0.000 description 1
- 125000004971 nitroalkyl group Chemical group 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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- 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
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/28—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only
- C07D311/30—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only not hydrogenated in the hetero ring, e.g. flavones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- 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
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/28—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only
- C07D311/32—2,3-Dihydro derivatives, e.g. flavanones
-
- 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
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/40—Separation, e.g. from natural material; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
Abstract
A method for extracting hop flavone and hop acid from hop includes such steps as extracting hop with alcohol, concentrating, extracting in liquid separator, filtering, concentrating to obtain hop flavone solid, drying, vacuum drying and pulverizing. The process of the present invention is concerned not only with xanthohumol in the hop flavones, but also with other flavone compounds such as isoxanthohumol, 6-isopentenyl naringenin. Can effectively reduce the production cost, achieve the effects of production safety and environmental protection, and realize the recovery with high yield.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and relates to extraction and separation of active ingredients in hops.
Background
Hops are important commercial crops, are widely used for beer production, and have wide application in industries such as medicine, health care, cosmetics and the like. The granular hops in the hop product account for a significant proportion, and hops are not much used for further processing. The domestic mature deep processing scheme is that hops are extracted by carbon dioxide to obtain hop extracts, the quality of the carbon dioxide hop extracts is good, and the main active ingredients are hop acids (including alpha acid and beta acid) and hop oil, so that the method has wide application and is accepted by a plurality of industries. Treating the hop residue after carbon dioxide extraction with alcohol, extracting flavonoid compounds therein, and further refining to obtain various hop flavonoid products. A series of patents filed by the inventors include: an enrichment method of xanthohumol in hop residues extracted by carbon dioxide in China patent 200910117234.3, an industrialized production method of high-purity xanthohumol in China patent 201010167119.X, a method for producing high-purity xanthohumol by extracting hop residues from carbon dioxide in China patent 201110063773.0, and a method for comprehensively extracting flavonoid compounds from hops in China patent 201711429554.3; various technical schemes are provided for extracting, separating and utilizing the hop flavonoids, and products are sold in the market.
Supercritical extraction technology and equipment are increasingly perfect and mature in recent years, but the application equipment investment of the technology is undeniably larger and the operation cost is higher. There are also some deep-processing schemes of hops which do not adopt supercritical extraction technology in China, such as an industrialized method for extracting resin acid and xanthohumol from hops in China patent 202011210988.6, a method for extracting flavonoids and flavonoid substances from hops in China patent 202011287315.0, and the like. The above solutions have certain drawbacks and disadvantages. The Chinese patent 202011210988.6 proposes an industrialized method for extracting resin acid and xanthohumol from hops, and the proposal has the disadvantages of too large consumption of various solvents, adverse reduction of production cost, and adverse production safety and environmental protection. Chinese patent 202011287315.0 is a method for extracting hop flavonoids and flavonoids, which has high alcohol consumption and uses supercritical extraction in the later stage of the process.
Disclosure of Invention
The invention aims to provide a method for extracting and separating hop flavonoids and hop acids from hops with low production cost.
The method for solving the technical problem comprises the following steps:
1. extracting: extracting crushed hops with 90% -95% ethanol by volume;
2. and (3) early-stage concentration: distilling the extract under reduced pressure at-0.06-0.09 MPa to recover ethanol;
3. and (3) extraction and separation: transferring the paste obtained after concentration into a knockout, adding a light phase solvent and an ethanol aqueous solution, and extracting the light solvent phase by using the ethanol aqueous solution;
4. and (3) filtering: filtering the upper light solvent phase, and recovering substances insoluble in two phases;
5. and (3) post concentration: vacuum concentrating the upper layer light solvent phase to obtain paste containing hops acid, part of hops oil and chlorophyll as main ingredients;
vacuum concentrating the lower alcohol solution after extraction, and recovering hop flavone solid;
6. and (3) drying: and (5) vacuum drying and crushing the hop flavone solid obtained in the step (5) to obtain the hop flavone product.
In the step 1, theoretically, solvents such as small molecule alcohols, ketones, esters, halogenated hydrocarbons, acetonitrile and the like can be used for treating hops to extract hops acid and flavonoid compounds, but due to factors such as solvent price, toxicity, use safety and the like, only methanol and ethanol (alcohol) are actually selected optimally. Methanol is low in price, but since methanol is also toxic and has a lower flash point than ethanol, the invention uses 90% -95% ethanol by volume to extract crushed hops. The common extraction method can be fractional heating extraction, ultrasonic or microwave auxiliary extraction, and the invention adopts the production mode of percolation extraction at room temperature to completely extract in consideration of material properties and production efficiency, so that the input amount of alcohol is small. The mass volume ratio (kg: L) of hops to ethanol as an extraction solvent is 1: 3-8, preferably 1:5, the extraction effect can be observed by the color of the effluent, and the initial effluent has a dark color and can be stopped when the effluent has a light color. The optimal proportion of the factory production is determined by workshop benefit analysis and is influenced by the prices of hop raw materials and solvent alcohol and the alcohol consumption.
And (2) distilling the percolate in the step (2) under reduced pressure at-0.06 to-0.09 MPa to recover ethanol, wherein the heating temperature is controlled to be lower than 70 ℃ and preferably lower than 65 ℃ in order to ensure the product quality.
In step 3, the paste obtained after concentration is transferred to a knockout, and a light phase (upper layer) solvent and a heavy phase (lower layer) solvent are added. The light phase (upper layer) solvent adopts a nonpolar or low-polar low-density organic solvent, the density of the solvent is less than 0.8g/ml, and the solvent can be a single solvent or a mixed solvent, for example, butyl acetate and n-hexane which are used by the inventor in China patent 201110063773.0. For environmental protection and cost reduction, the solvent is recovered, so that a single solvent is preferable. The single solvents available from the object property are of a large variety, and in view of cost and toxicity, the available solvents mainly include petroleum ether, n-hexane and cyclohexane. The cyclohexane polarity is slightly stronger than that of petroleum ether and normal hexane, and the effect is good, but considering the requirements of the GB2760 food additive using standard, only petroleum ether and normal hexane can be selected. In the two, the polarity of the n-hexane is slightly stronger than that of petroleum ether, and the effect is slightly better, so that the n-hexane is selected as a light phase (upper layer) solvent. The ratio of the n-hexane dosage to the hop input raw material is 0.8-1.5:1, generally 1.2:1, the n-hexane dosage is large, the solvent recovery burden is increased, the upper layer and the lower layer of the n-hexane dosage are less, the density is similar, the extraction layering is time-consuming and the effect is poor. The heavy phase (lower) solvent is a water miscible organic solvent, which may be small molecule alcohols, ketones, sulfoxides, organic acid amides, aqueous nitroalkanes in terms of physical properties, preferably methanol or aqueous ethanol, more preferably aqueous ethanol, again for reasons of cost, toxicity, source control (e.g., acetone is a regulatory chemical). The concentration of the aqueous ethanol solution is 50% to 70%, preferably 60%. The concentration of ethanol is low, the flavonoid compound is poorly dissolved, the concentration of ethanol is high, and the amount of hops acid and n-hexane dissolved in the lower layer is increased. The ratio of the ethanol water solution to the hop raw material is 0.4-0.7:1, generally 0.5:1. Too little amount can affect the extraction effect, and the amount greatly increases the recovery burden of the solvent. Extracting n-hexane phase with ethanol aqueous solution for 3-6 times, typically 4 times, and the color of the lower layer becomes lighter after each extraction. The recovery rate of xanthohumol, isoxanthohumol and 6-isopentenyl naringenin in the hop flavone can reach more than 95 percent after the hop flavone is extracted for 4 times. During the extraction separation process, a small amount of substances are not dissolved in the upper layer or the lower layer, and the substances are concentrated at the interface of two phases, so that the substances are left in the upper layer for treatment.
The upper n-hexane phase in step 4 is filtered and the materials insoluble in both phases are recovered.
In the step 5, the upper normal hexane phase is concentrated in vacuum, and all normal hexane is recovered by reduced pressure distillation under the pressure of-0.06 to-0.09 MPa, and the heating temperature is controlled to be lower than 65 ℃ and preferably lower than 60 ℃ in order to ensure the product quality. Concentrating to obtain paste containing hops acids, part of hops oil and chlorophyll as main ingredients.
Vacuum concentrating the combined lower alcohol solution, distilling under reduced pressure at-0.06-0.09 MPa to recover all ethanol, and controlling heating temperature below 70deg.C, preferably below 65deg.C to ensure product quality. Concentrating to obtain turbid water suspension, cooling, settling, filtering or centrifuging to recover hop flavone solid.
And (5) vacuum drying and crushing the hop flavone solid obtained in the step (5) to obtain the hop flavone product. The xanthohumol content in the product is generally more than 10%, which is related to the quality of the hop type and the raw material. Wherein the content of isoxanthohumol and 6-isopentenyl naringin is also related to the quality of hops.
The above-mentioned invention is similar to the method for extracting high purity xanthohumol from the residue of carbon dioxide extraction hop in chinese patent 201110063773.0 filed by the present inventor, but the separation principle is improved and greatly simplified according to the difference of raw materials.
The process of the present invention is concerned not only with xanthohumol in the hop flavones, but also with other flavone compounds such as isoxanthohumol, 6-isopentenyl naringenin. Can effectively reduce the production cost, achieve the effects of production safety and environmental protection, and realize the recovery with high yield.
Drawings
FIG. 1 shows a yellow humic acid detection chromatogram of hop flavonoids obtained in example 1;
FIG. 2 shows a chromatogram of detection of isoxanthohumol and 6-isopentenyl naringenin in hop flavonoids obtained in example 1.
Detailed Description
The technical scheme and the implementation steps of the invention are further described in detail through specific examples: example 1
(1) Extracting: 10 kg of crushed dried hops (hop alpha acid 11%, beta acid 6% and xanthohumol 0.6%) are filled into a percolating tank, 90% ethanol is used for percolating and extracting, the color of the initial effluent is very dark, and when 50 liters of percolate flows out, the color is light yellow green, and the extracting process is finished.
(2) And (3) early-stage concentration: and (3) placing 50L of the percolate extract in a concentration tank, carrying out reduced pressure distillation and recovery under the pressure of-0.06 to-0.09 MPa to obtain 47L of 92% ethanol, wherein the ethanol is distilled slowly, and the heating temperature is controlled to be lower than 65 ℃ in the concentration process. After the concentration was stopped, the mixture was cooled naturally, and 4.5 kg of a paste was discharged.
(3) And (3) extraction and separation: transferring the paste obtained after concentration into a knockout, adding 12 liters of normal hexane, adding 5 liters of 60% ethanol, fully stirring, standing and layering. The lower clear alcoholic solution was discharged. Then adding 60% ethanol to 5 liter to a knockout, fully stirring, standing and layering. The lower clear alcoholic solution was discharged. The extraction was repeated 4 times in total. The lower alcohol solution after the 4 th extraction is much lighter in color and is a lighter yellow solution. In the extraction and separation process, a small amount of substances are insoluble in the upper layer and the lower layer, and the substances are concentrated at the interface of two phases and are flocculent. These materials are left in the upper layer for treatment during the separation.
(4) And (3) filtering: the upper n-hexane phase was filtered, and a small amount of the two-phase-insoluble matter was recovered, and after drying, 22 g was weighed, and its composition was yet to be analyzed.
(5) And (3) post concentration: the upper normal hexane phase solution is concentrated in 14 liters of vacuum, and all normal hexane is recovered by reduced pressure distillation under the pressure of-0.06 to-0.09 MPa, and the heating temperature is controlled to be lower than 60 ℃ in the concentration process in order to ensure the product quality. The distilled n-hexane was entrained with a small amount of water and was removed by a knockout. 9.5 liters of n-hexane was recovered. Concentrating to obtain dark green paste 2 kg containing hops acids, part of hops oil, chlorophyll, etc. The recovery rate of hop alpha acid is 90 percent and the recovery rate of hop beta acid is 92 percent through analysis and calculation.
The lower alcohol solution 21L (alcohol and water in the percolate are brought in by the concentrated paste) is concentrated in a concentrating tank under vacuum, and the ethanol is recovered by reduced pressure distillation under the pressure of-0.06 to-0.09 MPa, so as to ensure the product quality, and the heating temperature is controlled to be lower than 70 ℃. 12.3 liters of 80% alcohol was recovered. Concentrating to obtain turbid water suspension, cooling, settling, filtering or centrifuging to recover hop flavone solid, and making its appearance be similar to that of semi-solid at room temperature, and hardening at low temperature.
(6) And (3) drying: and (5) carrying out vacuum drying and crushing on the hop flavone solid obtained in the step (5) to obtain 0.55 kg of hop flavone product. The xanthohumol content is 10.7 percent, and the xanthohumol recovery rate is 98 percent.
And (3) comparing and analyzing peak areas of detection chromatograms of the isoxanthohumol and the 6-isopentenyl naringenin in the raw materials and the products, wherein the recovery rate of the isoxanthohumol and the 6-isopentenyl naringenin is also more than 98%.
Example 2
(1) Extracting: 10 kg of crushed dried hops (hop alpha acid 11%, beta acid 6% and xanthohumol 0.6%) are filled into a percolating tank, 90% ethanol is used for percolating and extracting, the color of the initial effluent is very dark, and when 50 liters of percolate flows out, the color is light yellow green, and the extracting process is finished.
(2) And (3) early-stage concentration: and (3) placing 50L of the percolate extract in a concentration tank, carrying out reduced pressure distillation and recovery under the pressure of-0.06 to-0.09 MPa to obtain 46.5L of 92% ethanol, wherein the ethanol is distilled slowly, and the heating temperature is controlled to be lower than 65 ℃ in the concentration process. After the concentration was stopped, the mixture was cooled naturally, and 4.6 kg of a paste was discharged.
(3) And (3) extraction and separation: transferring the paste obtained after concentration into a knockout, adding 12 liters of cyclohexane, adding 5 liters of 60% ethanol, fully stirring, standing and layering. The lower clear alcoholic solution was discharged. Then adding 60% ethanol to 5 liter to a knockout, fully stirring, standing and layering. The lower clear alcoholic solution was discharged. The extraction was repeated 6 times in total. The color of the lower alcohol solution is much lighter after the 4 th extraction, and the lower alcohol solution is lighter yellow solution after the 6 th extraction. In the extraction and separation process, a small amount of substances are insoluble in the upper layer and the lower layer, and the substances are concentrated at the interface of two phases and are flocculent. These materials are left in the upper layer for treatment during the separation.
(4) And (3) filtering: the upper cyclohexane phase was filtered, and a small amount of the two-phase-insoluble matter was recovered, and after drying, it weighed 20 g, and its composition was yet to be analyzed.
(5) And (3) post concentration: and (3) concentrating 14.5 liters of the upper cyclohexane phase solution in vacuum, and distilling under reduced pressure at-0.06 to-0.09 MPa to recover all cyclohexane, wherein the heating temperature is controlled to be lower than 65 ℃ in the concentration process so as to ensure the product quality. The distilled cyclohexane was entrained with a small amount of water and was removed by a knockout. Cyclohexane was recovered in an amount of 10 liters. Concentrating to obtain dark green paste 2.2 kg containing hops acids, part of hops oil, chlorophyll, etc. The recovery rate of hop alpha acid is 92% and the recovery rate of hop beta acid is 94% through analysis and calculation.
Extracting and mixing the lower alcohol solution 32L (alcohol and water in the percolate are brought in by the concentrated paste), vacuum concentrating in a concentrating tank, distilling under reduced pressure under-0.06-0.09 MPa to recover ethanol, and controlling heating temperature below 70deg.C to ensure product quality. 21.2 liters of 81% alcohol was recovered. Concentrating to obtain turbid water suspension, cooling, settling, filtering or centrifuging to recover hop flavone solid, and making its appearance be similar to that of semi-solid at room temperature, and hardening at low temperature.
(6) And (3) drying: and (3) vacuum drying and crushing the hop flavone solid obtained in the step (5) to obtain 0.42 kg of hop flavone product. The xanthohumol content is 14 percent, and the xanthohumol recovery rate is 98 percent.
And (3) comparing and analyzing peak areas of detection chromatograms of the isoxanthohumol and the 6-isopentenyl naringenin in the raw materials and the products, wherein the recovery rate of the isoxanthohumol and the 6-isopentenyl naringenin is also more than 98%.
Comparing example 1 with example 2, it can be seen that the hop flavone product obtained in example 2 has a higher content and better effect. However, n-hexane should be used in the production process in view of compliance with the requirements of the use standard of the GB2760 food additive.
The foregoing is merely illustrative of the present invention and not restrictive, and other modifications and equivalents thereof may occur to those skilled in the art without departing from the spirit and scope of the present invention.
Claims (9)
1. A method for extracting and separating hop flavonoids and hop acids from hops, which is characterized by comprising the following steps:
(1) Extracting: extracting crushed hops with 90% -95% ethanol by volume;
(2) And (3) early-stage concentration: distilling the extract under reduced pressure at-0.06-0.09 MPa to recover ethanol;
(3) And (3) extraction and separation: transferring the paste obtained after concentration into a knockout, adding a light phase solvent and an ethanol aqueous solution, and extracting the light solvent phase by using the ethanol aqueous solution;
(4) And (3) filtering: filtering the upper light solvent phase, and recovering substances insoluble in two phases;
(5) And (3) post concentration: vacuum concentrating the upper layer light solvent phase to obtain paste containing hops acid, part of hops oil and chlorophyll as main ingredients;
vacuum concentrating the lower alcohol solution after extraction, and recovering hop flavone solid;
(6) And (3) drying: and (3) carrying out vacuum drying and crushing on the hop flavone solid obtained in the step (5) to obtain a hop flavone product.
2. The method according to claim 1, characterized in that: in the step (1), a production mode of diacolation and extraction at room temperature is adopted, and the mass volume ratio of hops to ethanol serving as an extraction solvent is 1:3 to 8, the unit is kg: l.
3. The method according to claim 1, characterized in that: the concentration process in the step (2) is carried out under reduced pressure of-0.06 to-0.09 MPa, and the temperature is lower than 70 ℃.
4. The method according to claim 1, characterized in that: the light phase solvent in the extraction and separation process of the step (3) adopts normal hexane; the ratio of the dosage of the normal hexane to the dosage of the raw material hops is 0.8-1.5:1 by volume and mass, and the unit is L/kg; the concentration of the ethanol aqueous solution is 50% -70%, and the extraction times of the n-hexane phase extracted by the ethanol aqueous solution are 3-6 times.
5. The method according to claim 1, characterized in that: concentrating the upper normal hexane phase in vacuum at the temperature of minus 0.06 to minus 0.09MPa, wherein the temperature is lower than 65 ℃; vacuum concentrating the combined lower alcohol solution at-0.06-0.09 MPa to below 70deg.C to obtain turbid water suspension, cooling, settling, filtering or centrifuging to recover hop flavone solid.
6. The method according to claim 2, characterized in that: the mass volume ratio of the hops to the ethanol serving as the extraction solvent is 1:5, and the units are kg: l.
7. A method according to claim 3, characterized in that: the concentration process temperature is lower than 60 ℃.
8. The method according to claim 4, wherein: the ratio of the n-hexane dosage to the hop input raw material is 1.2:1 by volume and mass; the heavy phase solvent adopts an ethanol water solution, and the concentration of the ethanol water solution is 60 percent.
9. The method according to claim 5, wherein: vacuum concentrating the upper normal hexane phase at-0.06-0.09 MPa and temperature below 60deg.C; the combined lower alcohol solution after extraction is concentrated in vacuum and is carried out under the pressure of minus 0.06 to minus 0.09MPa, and the temperature is lower than 65 ℃. Concentrating to obtain turbid water suspension, cooling, settling, filtering or centrifuging to recover hop flavone solid.
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