CN113443982A - Method for purifying milk lactone crude product - Google Patents
Method for purifying milk lactone crude product Download PDFInfo
- Publication number
- CN113443982A CN113443982A CN202011423160.9A CN202011423160A CN113443982A CN 113443982 A CN113443982 A CN 113443982A CN 202011423160 A CN202011423160 A CN 202011423160A CN 113443982 A CN113443982 A CN 113443982A
- Authority
- CN
- China
- Prior art keywords
- milk lactone
- product
- filter cake
- milk
- crude
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 235000013336 milk Nutrition 0.000 title claims abstract description 65
- 239000008267 milk Substances 0.000 title claims abstract description 65
- 210000004080 milk Anatomy 0.000 title claims abstract description 65
- 150000002596 lactones Chemical class 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000012043 crude product Substances 0.000 title claims abstract description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000012065 filter cake Substances 0.000 claims abstract description 29
- 239000000047 product Substances 0.000 claims abstract description 25
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000012074 organic phase Substances 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000012267 brine Substances 0.000 claims description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 2
- 238000000746 purification Methods 0.000 abstract description 8
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000002253 acid Substances 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 150000002978 peroxides Chemical group 0.000 description 1
- 238000006049 ring expansion reaction Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- WXBXVVIUZANZAU-CMDGGOBGSA-N trans-2-decenoic acid Chemical compound CCCCCCC\C=C\C(O)=O WXBXVVIUZANZAU-CMDGGOBGSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a purification method of a milk lactone crude product, which comprises the following steps: s1, sequentially adding the milk lactone crude product and dicyclohexylamine into an organic solvent, carrying out a salt forming reaction under a stirring condition, separating out crystals from a mixed solution after the reaction is finished, and filtering to obtain a filter cake; and S2, adjusting the pH value of the filter cake obtained in the step S1 to 2-3 by adopting a neutralizing agent, extracting by ethyl acetate, combining organic phases, washing and concentrating to obtain the pure milk lactone. The purification method of the milk lactone crude product has the advantages of simple process, safety and environmental protection, and the purity of the obtained milk lactone pure product can reach more than 98 percent, so the purification method is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of milk lactone purification methods, in particular to a purification method of a milk lactone crude product.
Background
Lactol is a mixture of 5(6) -decenoic acids, english name: milk, 5(6) -decenoic acids mix, is a Milk-flavored flavor product. The unsaturated fatty acid is actually an unsaturated fatty acid, and the extremely small amount of unsaturated fatty acid can generate milk fragrance, has strong fragrance and lasting fragrance, and can be widely applied to foods such as milk, cream, cheese essence, chocolate and the like as spices. In addition, the milk lactone has high boiling point, can be used in baked food, is not easy to be damaged like compound milk essence, and has very wide application prospect.
Chinese patent publication No. CN1266841 discloses a method for synthesizing milk lactone, using cyclohexanone and butyraldehyde as starting materials, performing alkaline condensation, selective hydrogenation, peroxide ring expansion to obtain lactone, and finally dehydrating under acidic condition to obtain 5- (6) -decenoic acid mixture, as shown in fig. 1 specifically; the purity of the milk lactone obtained in the patent is 70-75%, and the purity can only reach 90-94% after once rectification, wherein the purity contains 5-10% of decalactone impurities.
Many domestic and foreign documents also describe that the purity of the milk lactone crude product can be improved to more than 98% by rectification, but the applicant repeatedly adopts the rectification method to purify the milk lactone crude product for many times, and finds that the purity of the milk lactone by the rectification purification method can hardly reach more than 98%, and generally can only reach 90% -94%.
Disclosure of Invention
The invention aims to overcome the defects, provides a method for purifying the crude milk lactone product, has simple, safe and environment-friendly process, ensures that the purity of the obtained pure milk lactone product can reach more than 98 percent, and is suitable for industrial production.
In order to realize the purpose, the invention provides the following technical scheme that the method for purifying the milk lactone crude product comprises the following steps:
s1, sequentially adding the milk lactone crude product and dicyclohexylamine into an organic solvent, carrying out a salt forming reaction under a stirring condition, separating out crystals from a mixed solution after the reaction is finished, and filtering to obtain a filter cake;
and S2, adjusting the pH value of the filter cake obtained in the step S1 to 2-3 by adopting a neutralizing agent, extracting by ethyl acetate, combining organic phases, washing and concentrating to obtain the pure milk lactone.
Preferably, the purity of the crude milk lactone product in the step S1 is 90-94%, and the purity of the pure milk lactone product obtained in the step S2 is more than or equal to 98%.
Preferably, the mass ratio of the crude milk lactone product to the dicyclohexylamine in the step S1 is 1: 0.95 to 1.15.
Preferably, the organic solvent in step S1 is ethyl acetate or acetonitrile.
Preferably, in the step S1, the crude milk lactone is dissolved in an organic solvent, cooled to 0-5 ℃, and then dicyclohexylamine is added.
Preferably, in the step S2, the pH of the filter cake is adjusted to 2-3 by using a neutralizing agent after the filter cake is washed.
Preferably, in the step S2, the filter cake is washed with ethyl acetate, and then the pH of the filter cake is adjusted to 2-3 with a neutralizing agent.
Preferably, in the step S2, the neutralizing agent is 1mol/L hydrochloric acid.
Preferably, in the step S2, extraction is performed 3 times by ethyl acetate.
Preferably, the combined organic phases are washed 1 time with brine.
Compared with the prior art, the invention has the beneficial effects that: the purification method of the milk lactone crude product has the advantages of simple process, safety and environmental protection, and the purity of the obtained milk lactone pure product can reach more than 98 percent, so the purification method is suitable for industrial production.
Drawings
FIG. 1 is a schematic diagram of a method for synthesizing lactonic acid in the Chinese patent publication No. CN 1266841;
FIG. 2 is a schematic diagram of the method for purifying the crude milk lactone product of the present invention.
Detailed Description
In order to make the technical means of the implementation of the present invention, and the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments.
In the following examples, the purity of the product was qualitatively and quantitatively analyzed by gas chromatography. The gas chromatography comprises a chromatographic column (30m × 0.25mm) and a hydrogen ion flame detector, and the detection sample volume is 0.2 μ L, wherein the sample is the obtained pure milk lactone. The injector temperature was 280 ℃, the column box temperature was 60 ℃ and the detector temperature was 280 ℃. The pressure before the column was 150kpa, the split flow was 20ml/min, and the tail blow was 20 ml/min. The temperature programming for the gas chromatograph was: holding at 60 deg.C for 3min, heating to 280 deg.C at 15 deg.C/min, and holding at 280 deg.C for 3 min. The components are calculated according to an area normalization method.
Example 1
Referring to fig. 2, this embodiment discloses a method for purifying a crude milk lactone product, which includes the following steps:
s1, dissolving 200.0g of a milk lactone crude product (with the purity of 92%) in 800ml of ethyl acetate, cooling to 0-5 ℃, adding 218.5g of dicyclohexylamine, stirring at room temperature, carrying out salt forming reaction for 1 hour, and filtering to obtain a filter cake;
s2, washing the filter cake obtained in the step S1 with 50ml of ethyl acetate, then placing the filter cake into a 1L three-necked bottle, adding 1mol/L hydrochloric acid to neutralize until the pH value is 2-3, adding ethyl acetate to extract for 3 times (100ml multiplied by 3), combining organic layers, washing with saturated salt water for 1 time (400ml), drying with anhydrous sodium sulfate, filtering, and concentrating to obtain pure 163.0g of pure milk lactone, wherein the purity of the pure milk lactone is 98.8%.
Example 2
Referring to fig. 2, this embodiment discloses a method for purifying a crude milk lactone product, which includes the following steps:
s1, dissolving 1100.0g of a milk lactone crude product (with the purity of 90%) in 4.8L of ethyl acetate, cooling to 0-5 ℃, adding 1200g of dicyclohexylamine, stirring at room temperature, carrying out a salt forming reaction for 2 hours, and filtering to obtain a filter cake;
s2, washing the filter cake obtained in the step S1 with 200ml of ethyl acetate, then placing the filter cake into a 5L three-necked bottle, adding 1mol/L hydrochloric acid to neutralize until the pH value is 2-3, adding ethyl acetate to extract for 3 times (1.0L multiplied by 3), combining organic layers, washing with saturated salt for 1 time (1L), drying with anhydrous sodium sulfate, filtering, and concentrating to obtain 872g of a pure milk lactone; wherein the purity of the obtained pure milk lactone product is 98.6%.
Example 3
Referring to fig. 2, this embodiment discloses a method for purifying a crude milk lactone product, which includes the following steps:
s1, dissolving 1100.0g of a milk lactone crude product (with the purity of 90%) in 4.8L of acetonitrile, cooling to 0-5 ℃, adding 1200g of dicyclohexylamine, stirring at room temperature, carrying out a salt forming reaction for 2 hours, and filtering to obtain a filter cake;
s2, washing the filter cake obtained in the step S1 with 200ml of ethyl acetate, then placing the filter cake into a 5L three-necked bottle, adding 1mol/L hydrochloric acid to neutralize until the pH value is 2-3, adding ethyl acetate to extract for 3 times (1.0L multiplied by 3), combining organic layers, washing with saturated salt for 1 time (1L), drying with anhydrous sodium sulfate, filtering, and concentrating to obtain 872g of a pure milk lactone; wherein the purity of the obtained pure milk lactone product is 98.6%.
Example 4
Referring to fig. 2, this embodiment discloses a method for purifying a crude milk lactone product, which includes the following steps:
s1, dissolving 1100.0g of a milk lactone crude product (with the purity of 90%) in 4.8L of ethyl acetate, cooling to 0-5 ℃, adding 1045g of dicyclohexylamine, carrying out salt forming reaction for 2 hours under stirring at room temperature, and filtering to obtain a filter cake;
s2, washing the filter cake obtained in the step S1 with 200ml of ethyl acetate, then placing the filter cake into a 5L three-necked bottle, adding 1mol/L hydrochloric acid to neutralize until the pH value is 2-3, adding ethyl acetate to extract for 3 times (1.0L multiplied by 3), combining organic layers, washing with saturated salt for 1 time (1L), drying with anhydrous sodium sulfate, filtering, and concentrating to obtain 757g of a pure milk lactone product; wherein the purity of the obtained pure milk lactone product is 98.8%.
Example 5
Referring to fig. 2, this embodiment discloses a method for purifying a crude milk lactone product, which includes the following steps:
s1, dissolving 1100.0g of a milk lactone crude product (with the purity of 90%) in 4.8L of ethyl acetate, cooling to 0-5 ℃, adding 1265g of dicyclohexylamine, stirring at room temperature, carrying out a salt forming reaction for 2 hours, and filtering to obtain a filter cake;
s2, washing the filter cake obtained in the step S1 with 200ml of ethyl acetate, then placing the filter cake into a 5L three-necked bottle, adding 1mol/L hydrochloric acid to neutralize until the pH value is 2-3, adding ethyl acetate to extract for 3 times (1.0L multiplied by 3), combining organic layers, washing with saturated salt for 1 time (1L), drying with anhydrous sodium sulfate, filtering, and concentrating to obtain 936g of a pure milk lactone; wherein the purity of the obtained pure milk lactone product is 98.8%.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The method for purifying the milk lactone crude product is characterized by comprising the following steps:
s1, sequentially adding the milk lactone crude product and dicyclohexylamine into an organic solvent, carrying out a salt forming reaction under a stirring condition, separating out crystals from a mixed solution after the reaction is finished, and filtering to obtain a filter cake;
and S2, adjusting the pH value of the filter cake obtained in the step S1 to 2-3 by adopting a neutralizing agent, extracting by ethyl acetate, combining organic phases, washing and concentrating to obtain the pure milk lactone.
2. The method for purifying the crude milk lactone product of claim 1, wherein the purity of the crude milk lactone product in the step S1 is 90-94%, and the purity of the pure milk lactone product obtained in the step S2 is not less than 98%.
3. The method for purifying a crude milk lactone product of claim 1, wherein the mass ratio of the crude milk lactone product to the dicyclohexylamine in the step S1 is 1: 0.95 to 1.15.
4. The method of claim 1, wherein the organic solvent in step S1 is ethyl acetate or acetonitrile.
5. The method for purifying a milk lactone crude product as claimed in claim 1, wherein in the step S1, the milk lactone crude product is dissolved in an organic solvent, cooled to 0-5 ℃, and then dicyclohexylamine is added.
6. The method for purifying a milk lactone crude product as claimed in claim 1, wherein the pH of the filter cake is adjusted to 2-3 by using a neutralizing agent after the filter cake is washed in the step S2.
7. The method for purifying the crude milk lactone according to claim 4, wherein in the step S2, the filter cake is washed by ethyl acetate, and then the pH of the filter cake is adjusted to 2-3 by a neutralizing agent.
8. The method of claim 1, wherein in step S2, the neutralizing agent is 1mol/L hydrochloric acid.
9. The method of claim 1, wherein in step S2, the crude milk lactone is extracted 3 times with ethyl acetate.
10. The method of claim 1, wherein the combined organic phases are washed with brine 1 time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011423160.9A CN113443982A (en) | 2020-12-08 | 2020-12-08 | Method for purifying milk lactone crude product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011423160.9A CN113443982A (en) | 2020-12-08 | 2020-12-08 | Method for purifying milk lactone crude product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113443982A true CN113443982A (en) | 2021-09-28 |
Family
ID=77808656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011423160.9A Pending CN113443982A (en) | 2020-12-08 | 2020-12-08 | Method for purifying milk lactone crude product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113443982A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004043942A1 (en) * | 2002-11-14 | 2004-05-27 | Hokko Chemical Industry Co., Ltd. | Process for producing ϝ-jasmolactone |
| CN110156592A (en) * | 2019-06-12 | 2019-08-23 | 广东广益科技实业有限公司 | 5 (6)-decylenic acid method of purification |
-
2020
- 2020-12-08 CN CN202011423160.9A patent/CN113443982A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004043942A1 (en) * | 2002-11-14 | 2004-05-27 | Hokko Chemical Industry Co., Ltd. | Process for producing ϝ-jasmolactone |
| CN110156592A (en) * | 2019-06-12 | 2019-08-23 | 广东广益科技实业有限公司 | 5 (6)-decylenic acid method of purification |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Usuki et al. | Extraction and isolation of shikimic acid from Ginkgo biloba leaves utilizing an ionic liquid that dissolves cellulose | |
| JP6207522B2 (en) | Purification of vanillin by liquid-liquid extraction | |
| CN111249321B (en) | Method for simultaneously preparing black currant polyphenol and polysaccharide | |
| CN110003071B (en) | Industrial method for quickly and efficiently extracting lutein and quercetagetin | |
| CN111072449B (en) | A method for preparing natural ferulic acid from nigre containing oryzanol | |
| CN111620851A (en) | Method for extracting nicotine from tobacco based on tertiary extraction method | |
| CN108558623B (en) | Preparation process of alpha-damascenone | |
| CN113443982A (en) | Method for purifying milk lactone crude product | |
| CN103275151B (en) | A kind of process for purification of Matachrom | |
| CN110835185B (en) | Method for separating acid and ester from mixed solution | |
| CN101041631B (en) | Improved synthesizing technique for beta-carotene | |
| CN113501771B (en) | Preparation method of N- (2-aminoethyl) glycine derivative | |
| CN105294474A (en) | Method for preparing menthane diacetyl amide from p-menthadiene | |
| CN101781175A (en) | Method for separating 2,4-Dichlorophenol and 2,6-Dichlorophenol | |
| CN115819382A (en) | Method for synthesizing 2, 5-dimethyl-4-hydroxy-3 (2H) -furanone perfume by one-pot method | |
| CN112094237B (en) | Synthesis method of fluorobenzene imidazole | |
| CN105801474B (en) | A kind of method of refined 3,6 lontrel | |
| CN103588855B (en) | A kind of method of plant sterol of purifying from deodorization distillate | |
| CN106632163A (en) | Preparation method of gamma-caprolactone | |
| CN102180781B (en) | Method for extracting and producing high-purity xanthohumol from residues generated by extracting hops by carbon dioxide | |
| CN107011254B (en) | Synthesis and purification method of 2-amino-4-methylpyridine | |
| CN107686492A (en) | A kind of method of rhodioside in extraction purification zymotic fluid using macroporous absorbent resin | |
| CN113200917A (en) | Purification method of 4-aminoantipyrine | |
| CN110559347A (en) | Method for extracting and purifying peony pollen flavonoid | |
| CN110917235A (en) | Method for extracting natural components from plants |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210928 |