CN115181012A - Method for extracting and separating estragole from aniseed - Google Patents
Method for extracting and separating estragole from aniseed Download PDFInfo
- Publication number
- CN115181012A CN115181012A CN202210969707.8A CN202210969707A CN115181012A CN 115181012 A CN115181012 A CN 115181012A CN 202210969707 A CN202210969707 A CN 202210969707A CN 115181012 A CN115181012 A CN 115181012A
- Authority
- CN
- China
- Prior art keywords
- estragole
- terpineol
- temperature
- fraction
- azeotrope
- 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.)
- Granted
Links
- ZFMSMUAANRJZFM-UHFFFAOYSA-N Estragole Chemical compound COC1=CC=C(CC=C)C=C1 ZFMSMUAANRJZFM-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 238000000034 method Methods 0.000 title claims abstract description 33
- 240000004760 Pimpinella anisum Species 0.000 title claims description 5
- 235000012550 Pimpinella anisum Nutrition 0.000 title claims description 5
- WRYLYDPHFGVWKC-UHFFFAOYSA-N 4-terpineol Chemical compound CC(C)C1(O)CCC(C)=CC1 WRYLYDPHFGVWKC-UHFFFAOYSA-N 0.000 claims abstract description 48
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 claims abstract description 46
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229940088601 alpha-terpineol Drugs 0.000 claims abstract description 46
- 239000010676 star anise oil Substances 0.000 claims abstract description 31
- WRYLYDPHFGVWKC-SNVBAGLBSA-N 4-Terpineol Natural products CC(C)[C@]1(O)CCC(C)=CC1 WRYLYDPHFGVWKC-SNVBAGLBSA-N 0.000 claims abstract description 24
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims abstract description 17
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 240000007232 Illicium verum Species 0.000 claims abstract description 10
- 235000008227 Illicium verum Nutrition 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000004821 distillation Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- RUVINXPYWBROJD-ONEGZZNKSA-N trans-anethole Chemical compound COC1=CC=C(\C=C\C)C=C1 RUVINXPYWBROJD-ONEGZZNKSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 12
- 240000001851 Artemisia dracunculus Species 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 9
- RUVINXPYWBROJD-UHFFFAOYSA-N para-methoxyphenyl Natural products COC1=CC=C(C=CC)C=C1 RUVINXPYWBROJD-UHFFFAOYSA-N 0.000 claims description 9
- 229940011037 anethole Drugs 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- 235000013399 edible fruits Nutrition 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 22
- 239000007789 gas Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 238000004817 gas chromatography Methods 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 239000012452 mother liquor Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010606 normalization Methods 0.000 description 6
- 239000010617 anise oil Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- -1 monoterpene compounds Chemical class 0.000 description 4
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 2
- 229930003658 monoterpene Natural products 0.000 description 2
- 235000002577 monoterpenes Nutrition 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019476 oil-water mixture Nutrition 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- NPNUFJAVOOONJE-ZIAGYGMSSA-N β-(E)-Caryophyllene Chemical compound C1CC(C)=CCCC(=C)[C@H]2CC(C)(C)[C@@H]21 NPNUFJAVOOONJE-ZIAGYGMSSA-N 0.000 description 2
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 1
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 240000006927 Foeniculum vulgare Species 0.000 description 1
- 235000004204 Foeniculum vulgare Nutrition 0.000 description 1
- 241000720991 Illicium Species 0.000 description 1
- 241000218377 Magnoliaceae Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 244000203593 Piper nigrum Species 0.000 description 1
- 235000008184 Piper nigrum Nutrition 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- NPNUFJAVOOONJE-UHFFFAOYSA-N beta-cariophyllene Natural products C1CC(C)=CCCC(=C)C2CC(C)(C)C21 NPNUFJAVOOONJE-UHFFFAOYSA-N 0.000 description 1
- 229940088623 biologically active substance Drugs 0.000 description 1
- 235000013614 black pepper Nutrition 0.000 description 1
- 229930006737 car-3-ene Natural products 0.000 description 1
- BQOFWKZOCNGFEC-UHFFFAOYSA-N carene Chemical compound C1C(C)=CCC2C(C)(C)C12 BQOFWKZOCNGFEC-UHFFFAOYSA-N 0.000 description 1
- 229930007796 carene Natural products 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229940117948 caryophyllene Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229930007744 linalool Natural products 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002773 monoterpene derivatives Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229930004725 sesquiterpene Natural products 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000000194 supercritical-fluid extraction Methods 0.000 description 1
- 235000019605 sweet taste sensations Nutrition 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/44—Separation; Purification; Stabilisation; Use of additives by treatments giving rise to a chemical modification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for extracting and separating estragole from star anise, which specifically comprises the steps of taking star anise fruits and/or branches and leaves as raw materials to obtain a star anise oil pre-fraction, and carrying out vacuum rectification to obtain an azeotrope rich in estragole, 4-terpineol and alpha-terpineol; the azeotrope is further subjected to reduced pressure distillation to remove 4-terpineol, the obtained azeotrope rich in estragole and alpha-terpineol is placed in a rectifying tower, potassium bisulfate which is 0.005-0.0058 times of the weight of the azeotrope is added for reaction for a period of time, then the temperature is reduced for reduced pressure distillation, the temperature of a tower kettle is set to be 110-120 ℃, the temperature of the tower top is set to be 80-85 ℃, and the fraction at the tower top is collected, namely the estragole. The method of the invention can obtain the estragole with high purity and high yield.
Description
Technical Field
The invention relates to extraction and separation of active ingredients in plants, in particular to a method for extracting and separating estragole from star anise.
Background
Illicium verum hook.f., the family Magnoliaceae, the genus Illicium. Is a unique aromatic plant in China, and the plant is a beautiful name of homology of medicine and food. Mainly distributed in southern China, guangxi, guangdong, yunnan, fujian and Sichuan, wherein the Baise and Qinzhou in Guangxi have the most output. The star anise is a characteristic commercial crop in Guangxi province, and the effective component of the star anise is mainly star anise oil, and the content of the star anise oil is generally 5-12%. The current research finds that the main volatile flavor components in the star anise oil comprise anethole (anethole), anisaldehyde, monoterpene compounds, monoterpene oxides and sesquiterpene compounds, and also comprise high-content lemon 25627rare earth, carene, isocaryophyllene, linalool, estragole, P-caryophyllene, anisaldehyde and the like.
After the anise oil is used for extracting anethole, the front fraction of the anise oil contains 30-40% of estragole (the application research progress of the resource and the biological activity of the estragole in Liang Zhong, wang Guo smart. The research progress of the estragole resource and the biological activity [ J ] Guangxi forestry science 2010, 39 (1): 49-51). Estragole is one of the important fragrances and is also an important biologically active substance or active intermediate. The estragole is also called estragole, isoanethole and methyl black pepper phenol, and has a chemical name of p-methoxyphenylpropylene, also called p-allyl anisole, and a molecular formula C 10 H 12 O(H 3 COC 6 H 4 CH 2 CH＝CH 2 ) And the relative molecular weight was 148.21. The estragole is colorless to light yellow liquid, has strong fennel fragrance and sweet taste, is one of flavors for preparing daily chemical and edible essence, has the boiling point of 217 ℃, 97-97.5 ℃ (1.6 KPa), 86 ℃ (930 KPa), is dissolved in ethanol and chloroform, and is slightly soluble in water.
The invention patent of the applicant's prior application with publication number CN107098797A discloses a method for extracting estragole, comprising: 1) Extracting oleum Foeniculi from fructus Anisi Stellati and folium Anisi Stellati; 2) Rectifying and separating front distillate (30% estragole) generated in the process of preparing anethole from anise oil to obtain azeotrope of estragole and terpineol; 3) Feeding the azeotrope obtained in the step 2) into a high-efficiency rectifying tower for intermittent feeding and high-efficiency rectifying separation, and adjusting the reflux ratio and the vacuum degree through three kettle temperature stages of 80 ℃, 95 ℃ and 110 ℃, so that about 94% of estragons products can be obtained, but the purity of the obtained estragons is not ideal enough.
The invention with publication number CN110835291A provides another preparation method of estragole, which comprises pulverizing fructus Anisi Stellati, soaking in alcohol, and separating alcohol from filtrateThen heated to 70-85 ℃, and the collected intermediate product is processed by supercritical CO 2 Extracting and purifying by 2 times of vacuum distillation to obtain the finished product of the estragole. The invention relates to the supercritical extraction and decompression rectification processes at the same time, the process is complex, the production cost is high, and no experiment and data show that the obtained estragon has high purity.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for extracting and separating estragole from aniseed, which can obtain the estragole with high purity and high yield.
In order to solve the technical problems, the invention adopts the following technical scheme:
the method for extracting and separating estragole from aniseed comprises the following steps:
1) Using illicium verum and/or branches and leaves as raw materials to obtain star anise oil;
2) Collecting the front fraction of the star anise oil by adopting the process of extracting anethole from the star anise oil;
3) Carrying out reduced pressure distillation on the obtained star anise oil front fraction, removing low-boiling-point impurities, setting the temperature of a tower kettle to be 110-120 ℃ and the temperature of a tower top to be 60-75 ℃, and collecting tower top fraction to obtain an azeotrope rich in estragon, 4-terpineol and alpha-terpineol;
4) Performing reduced pressure rectification on the obtained azeotrope rich in the estragole, the 4-terpineol and the alpha-terpineol to remove the 4-terpineol to obtain the azeotrope rich in the estragole and the alpha-terpineol;
5) Putting the obtained azeotrope rich in the estragole and the alpha-terpineol into a rectifying tower, adding potassium bisulfate which is 0.005-0.0058 times of the weight of the azeotrope in the rectifying tower, heating to 200-230 ℃ under normal pressure for reaction, stopping heating after the reaction is finished, carrying out reduced pressure rectification when the temperature of a tower kettle is reduced to be below 100 ℃, firstly setting the temperature of the tower kettle to be 105-110 ℃, setting the temperature of the tower top to be 70-80 ℃, and collecting fraction which is 4-8 percent of the feeding weight of the azeotrope rich in the estragole and the alpha-terpineol; then setting the temperature of the tower kettle at 110-120 ℃ and the temperature of the tower top at 80-85 ℃, and collecting the fraction at the tower top, namely the estragole.
It is known in the art that estragole and alpha-terpineol have similar boiling points (the boiling point of estragole is 217 ℃ C., the boiling point of alpha-terpineol is 217.5 ℃ C.), and are difficult to separate. According to the invention, potassium hydrogen sulfate is added into the azeotrope rich in the estragole and the alpha-terpineol, so that the alpha-terpineol is subjected to dehydration reaction to generate a substance with a low boiling point, and the rectification separation of the alpha-terpineol and the estragole is better realized, and the estragole product with the purity of over 99% is obtained, and the product yield is high.
In the step 1) of the method, the anise oil is obtained by adopting the conventional method, and the method specifically comprises the following steps: placing the star anise fruits and/or branches and leaves in a steam oil pot, adding water, distilling at the temperature of 30-100 ℃ and under the steam pressure of 0.01-0.03 MPa, collecting an oil-water mixture, and performing oil-water separation to obtain the star anise oil.
In the step 2) of the method, the operation of collecting the front fraction of the star anise oil by adopting the process for extracting the anethole from the star anise oil is the same as that in the prior art. Specifically, the method comprises the steps of placing star anise oil into a rectifying tower, controlling the temperature of a tower bottom to be 50-105 ℃ under the pressure condition of 1-5 mmHg, and collecting star anise oil pre-fraction at the flow rate of 10-50 kg/h of overhead fraction, wherein the collection amount of the star anise oil pre-fraction is usually 13-15% of the weight of fed materials in the step.
In order to increase the content of estragole in the star anise oil, it is preferable to perform a freezing crystallization operation to remove the terpene compounds in the star anise oil by the freezing crystallization operation immediately before the star anise oil is put into the rectifying tower before the step 2). The freezing crystallization operation is the same as the prior art, and specifically comprises the following steps: the star anise oil is frozen for 10 to 16 hours at the temperature of between 3 ℃ below zero and 5 ℃, then the star anise oil is crushed and centrifuged, the centrifuged mother liquor is collected, and the subsequent operation is carried out on the obtained centrifuged mother liquor (namely, the centrifuged mother liquor is used as the raw material, and the star anise oil front fraction is collected by adopting the process of extracting anethole).
In the step 3) of the method, the step of removing the low-boiling impurities firstly refers to the step of removing pinene compounds, and specifically, the method comprises the steps of setting the temperature of a tower kettle to be 50-90 ℃, the temperature of a tower top to be 45-60 ℃, collecting fractions which are 50-60% of the weight of the fed material of the front fraction of the star anise oil, and discarding the collected fractions to achieve the purpose of removing the low-boiling impurities. The low-boiling-point impurities are removed through vacuum rectification in the step to obtain relatively purer anise oil pre-fraction, and then the content of estragole in an azeotrope rich in estragole, 4-terpineol and alpha-terpineol is usually 80-84% (w/w), the content of 4-terpineol is usually 7-10% (w/w) and the content of alpha-terpineol is about 3-5% (w/w) in an azeotrope which is obtained by collecting the crude product at the tower bottom temperature of 110-120 ℃ and the tower top temperature of 60-75 ℃.
In step 4) of the method of the invention, the control of the rectification parameters for removing 4-terpineol is the same as that of the prior art. The following operations are preferably adopted in the present application: dividing the azeotrope obtained in the step 3) into two parts with equal weight, firstly putting one part of the azeotrope into a rectifying tower for carrying out intermittent feeding and high-efficiency rectification separation, heating under the pressure condition of 1-5 mmHg, controlling the temperature of a tower kettle to be 80-95 ℃ and the temperature of a tower top to be 65-70 ℃, and collecting a fraction (mainly 4-terpineol) which is 8-12% of the weight of the first feeding in the step; then adding the other part of the azeotrope into the rectifying tower, continuously raising the temperature under the same pressure condition, controlling the temperature of a tower kettle to be 100-105 ℃ and the temperature of a tower top to be 70-75 ℃, collecting a fraction (the fraction is mainly 4-terpineol) which is 8-12% of the total feeding weight in the step, and then continuously collecting a transition intermediate product which is 4-6% of the total feeding weight in the step by replacing a tank; and finally, continuously raising the temperature of the tower kettle to 110-115 ℃ and the temperature of the tower top to 80-85 ℃ under the same pressure condition, and collecting a fraction which is 70-75% of the total feeding weight in the step, wherein the fraction is an azeotrope which is removed from 4-terpineol and is rich in the estragole and alpha-terpineol, and in the obtained azeotrope, the content of the estragole usually reaches 93-94% (w/w), and the content of the alpha-terpineol is about 4-5% (w/w).
In the step 5) of the method, the addition amount of the potassium bisulfate influences the purity and the yield of the estragole, and the test of the applicant shows that the estragole with the purity of more than 99 percent can be obtained on the premise of ensuring the yield only when the addition amount of the potassium bisulfate is within the limited range. From the viewpoint of cost and effect, it is more preferable that the amount of potassium bisulfate added is controlled to 0.005 to 0.0058 times the weight of the azeotrope containing rich estragole and α -terpineol. In the step, after adding the potassium bisulfate, heating to 200-230 ℃ under normal pressure, and controlling the reaction time to be more than or equal to 4 hours, and further preferably controlling the reaction time to be 4-4.5 hours.
In the step 5) of the method, when the temperature of the tower kettle is 110-120 ℃ and the temperature of the tower top is 80-85 ℃, the amount of the fraction collected on the tower top is 84-88% of the feeding weight of the azeotrope rich in the estragole and the alpha-terpineol.
In steps 3) to 5) of the method of the invention, the vacuum distillation is preferably carried out under the pressure condition of 1-5 mmHg.
Compared with the prior art, the method has the advantages that the potassium hydrogen sulfate is added into the azeotrope rich in the estragole and the alpha-terpineol, so that the alpha-terpineol is subjected to dehydration reaction to generate a substance with low boiling point, the rectification separation of the alpha-terpineol and the estragole is better realized, the estragole product with the purity of more than 99 percent is obtained, and the product yield is high.
Drawings
FIG. 1 is a partial gas chromatogram relating to three components of estragole and 4-terpineol and alpha-terpineol in the gas chromatogram of the azeotrope rich in estragole, 4-terpineol and alpha-terpineol obtained in step 3) of example 1 of the present invention.
FIG. 2 is a gas chromatogram of an azeotrope rich in estragole and alpha-terpineol obtained in step 4) of example 1 according to the present invention.
FIG. 3 is a gas chromatogram of the final product of estragole obtained in step 5) of example 1.
FIG. 4 is a gas chromatogram of a finished estragole product obtained in comparative example 1 of the present invention.
FIG. 5 is a gas chromatogram of a finished estragole product obtained in comparative example 2 of the present invention.
FIG. 6 is a gas chromatogram of a final product of estragole obtained in comparative example 3 according to the present invention.
Detailed Description
In order to better explain the technical solution of the present invention, the present invention is further described in detail with reference to the following examples, but the embodiments of the present invention are not limited thereto.
Example 1
1) Placing the star anise fruits and the branches and leaves in a steam oil pot, adding water, distilling at the temperature of 95-100 ℃ and under the steam pressure of 0.02-0.03 MPa, collecting an oil-water mixture, and performing oil-water separation to obtain star anise oil; the star anise oil is frozen for 16h at-3-0 ℃, then crushed and centrifuged, the centrifuged mother liquor is collected, and the obtained mother liquor is analyzed and detected by gas chromatography (the gas chromatography conditions are that Agilent19091N-136 (60m 250μm 0.25μm) is used as a chromatographic column, the temperature is raised to 220 ℃ for 20min at the initial temperature of 150 ℃ for 1min, the temperature is raised to 240 ℃ at the rate of 4 ℃/min for the sample inlet, the FID detector temperature is 250 ℃, the split sampling is adopted, the split ratio is 100, the carrier gas is high-purity nitrogen (the purity is more than or equal to 99.999%), the flow rate is 4ml/min, and the sampling amount is 0.2 μ L), and the chemical composition is shown in the following table 1.
Table 1:
2) Placing the centrifugal mother liquor into a rectifying tower, controlling the temperature of a tower bottom to be 105 ℃ under the pressure condition of 2mmHg, and collecting the star anise oil front fraction at the flow rate of the tower top fraction of 40kg/h, wherein the collection amount of the star anise oil front fraction is equal to 15% of the weight of the centrifugal mother liquor;
3) Placing the obtained star anise oil front fraction into a rectifying tower, controlling the tower bottom temperature to be 90 ℃ and the tower top temperature to be 45-50 ℃ under the pressure condition of 2mmHg, collecting a fraction (the fraction is a pinene compound) which is equivalent to 60% of the feeding weight of the star anise oil front fraction, and discarding the collected fraction; then, under the same pressure condition, continuously heating to control the temperature of a tower kettle to be 110 ℃ and the temperature of a tower top to be 60-65 ℃, collecting an azeotrope rich in estragon, 4-terpineol and alpha-terpineol, wherein the azeotrope is analyzed and detected by adopting a gas chromatography (the chromatographic condition is the same as the above), the chemical composition of the azeotrope is shown in the following table 2, a partial chromatogram relating to three components of estragon, 4-terpineol and alpha-terpineol is intercepted and shown in figure 1, and the content of estragon is 82.9% (w/w) (the retention time is 9.292 min), the content of 4-terpineol is 9.4% (w/w) (the retention time is 8.232 min) and the content of alpha-terpineol is 4.5% (w/w) (the retention time is 9.382 min) according to an area normalization method;
table 2:
4) Dividing 2 tons of azeotrope which is obtained in the step 3) and is rich in estragon, 4-terpineol and alpha-terpineol into two parts (1 ton of each part) with equal weight, firstly putting one part into a high-efficiency rectifying tower, raising the temperature under the pressure of 1mmHg, controlling the temperature of a tower bottom to be 95 ℃ and the temperature of a tower top to be 67 ℃, and collecting a fraction (mainly 4-terpineol) which is equivalent to 10 percent (namely 100 kg) of the weight of the first feeding in the step; then adding the other part of the azeotrope into the rectifying tower, continuously raising the temperature under the same pressure condition, controlling the temperature of a tower kettle to be 100 ℃ and the temperature of a tower top to be 70 ℃, collecting a fraction (the fraction is mainly 4-terpineol) which is 10 percent (namely 200 kg) of the total feeding weight in the step, and then continuously collecting a transition intermediate product which is 5 percent (namely 100 kg) of the total feeding weight in the step by replacing a collection tank; finally, under the same pressure condition, continuously raising the temperature of the tower kettle to 110 ℃, controlling the temperature of the tower top to 85 ℃, collecting a fraction which is 72.5 percent (namely 1450 kg) of the total input weight in the step, wherein the fraction is an azeotrope which is removed from 4-terpineol and is rich in estragole and alpha-terpineol, and the azeotrope is analyzed and detected by gas chromatography (the chromatographic conditions are the same as the above), and the results show that the chemical composition of the azeotrope is shown in the following table 3, the gas chromatogram thereof is shown in fig. 2, and the content of estragole in the azeotrope is 93.6 percent (w/w) (the retention time is 9.294 min) and the content of alpha-terpineol is 4.3 percent (w/w) (the retention time is 9.382 min) are obtained according to an area normalization method;
table 3:
5) Putting 1 ton of the obtained azeotrope rich in estragole and alpha-terpineol into a rectifying tower, adding 5kg (equivalent to 0.005 time of the weight of the azeotrope) of potassium bisulfate into the rectifying tower, heating to 220 ℃ under normal pressure for total reflux reaction for 4 hours, stopping heating after the reaction is finished, reducing the pressure of the system to 1mmHg when the temperature of a tower kettle is reduced to 90 ℃, adjusting the temperature of the tower kettle to 105 ℃ after the pressure is stable, adjusting the temperature of the tower top to 75 ℃, collecting a fraction equivalent to 5 percent (equivalent to 50 kg) of the feeding weight of the azeotrope rich in estragole and alpha-terpineol, adjusting the temperature of the tower kettle to 110 ℃, adjusting the temperature of the tower top to 80 ℃, and collecting 847kg of the fraction at the tower top (the yield is 84.7 percent), thereby obtaining the finished product of the estragole. The obtained estragole finished product is analyzed and detected by gas chromatography (with the same chromatographic conditions as above), and the results show that the chemical composition is shown in the following table 4, the gas chromatogram is shown in fig. 3, and the content of estragole in the estragole finished product is 99.1% (w/w) (retention time is 9.280 min) according to the area normalization method.
Table 4:
comparative example 1
Example 1 was repeated, except that in step 5), 4kg (corresponding to 0.004 times of the weight thereof) of potassium hydrogensulfate was added.
Finally, 842.5kg of overhead fraction (the yield is 84.3%) is collected, namely the finished product of the estragole. The obtained estragole finished product is analyzed and detected by adopting gas chromatography (the chromatographic conditions are the same as those above), the result shows that the chemical composition is shown in the following table 5, the gas chromatogram is shown in figure 4, and the content of the estragole in the estragole finished product is 95.8% (w/w) (the retention time is 9.282 min) according to the area normalization method.
Table 5:
comparative example 2
Example 1 was repeated, except that in step 5) the amount of potassium bisulfate added was 6kg (corresponding to 0.006 times the weight of the azeotrope rich in estragole and α -terpineol).
Finally, 840.8kg of overhead fraction is collected (the yield is 84.1 percent), and the finished product of the estragole is obtained. The obtained estragole finished product is analyzed and detected by gas chromatography (with the same chromatographic conditions as above), and the results show that the chemical composition is shown in the following table 6, the gas chromatogram is shown in fig. 5, and the content of estragole in the estragole finished product is 99.1% (w/w) (retention time is 9.260 min) according to the area normalization method.
Table 6:
comparative example 3
Example 1 was repeated, except that step 5) was omitted, and step 4) was carried out as follows:
4) Putting 2 tons of azeotrope rich in estragole and alpha-terpineol obtained in the step 3) into a high-efficiency rectifying tower, heating under the pressure condition of 1mmHg, controlling the temperature of a tower bottom to be 105 ℃ and the temperature of a tower top to be 75 ℃, and collecting a fraction (mainly 4-terpineol) which is 10 percent (namely 100 kg) of the weight of the feed in the step; then, under the same pressure condition, the temperature of the tower bottom is continuously increased to control the temperature of the tower bottom to be 110 ℃, the temperature of the tower top to be 85 ℃, and a fraction which is equal to 85 percent (namely 1700 kg) of the total feeding weight in the step is collected. The fraction is a finished product of estragole, and the chemical composition of the fraction is shown in the following table 7 by analyzing and detecting the fraction by using a gas chromatography (the chromatographic conditions are the same as the above), and the gas chromatogram is shown in fig. 6, wherein the content of estragole is 94.9% (w/w) (the retention time is 9.298 min) and the content of alpha-terpineol is 4.0% (w/w) (the retention time is 9.388 min) according to an area normalization method. It can be seen that when potassium bisulfate is not added, high-purity estragole cannot be obtained even if the azeotrope rich in estragole and alpha-terpineol is further rectified under reduced pressure.
Table 7:
example 2
Example 1 was repeated except that, in step 5), potassium bisulfate was added in an amount of 5.5kg (equivalent to 0.0055 times the weight of the azeotrope rich in estragole and α -terpineol), and the mixture was heated to 200 ℃ under normal pressure after the addition of potassium bisulfate and reacted for 4.5 hours; after the reaction is finished, when the temperature of the tower bottom is reduced to 100 ℃, the system is decompressed to 1mmHg, the temperature of the tower bottom is adjusted to 105 ℃ after the pressure is stabilized, the temperature of the tower top is adjusted to 70 ℃, and fraction which is equal to 6 percent (namely 60 kg) of the feeding weight of the azeotrope rich in the estragole and the alpha-terpineol is collected.
Finally, 851kg of overhead fraction (the yield is 85.1%) is collected, namely the finished product of the estragole. The obtained estragole finished product is analyzed and detected by adopting gas chromatography (the chromatographic conditions are the same as those above), and the result shows that the content of the estragole is 99.2 percent (w/w).
Example 3
Example 1 was repeated, except that in step 5), 5.8kg of potassium bisulfate (equivalent to 0.0058 times the weight of the azeotrope rich in estragole and α -terpineol) was added; and finally, when the overhead fraction of the estragole is collected, the temperature of the tower kettle is controlled to be 120 ℃, and the temperature of the tower top is controlled to be 85 ℃.
Finally, 848kg of overhead fraction is collected (the yield is 84.8 percent), and the finished product of the estragole is obtained. The obtained estragole finished product is analyzed and detected by gas chromatography (the chromatographic conditions are the same as the above), and the result shows that the content of the estragole is 99.2 percent (w/w).
Claims (7)
1. The method for extracting and separating estragole from aniseed comprises the following steps:
1) Using star anise and/or branches and leaves as raw materials to obtain star anise oil;
2) Collecting the front fraction of the star anise oil by adopting the process of extracting anethole;
3) Carrying out reduced pressure distillation on the obtained star anise oil front fraction, removing low-boiling-point impurities, setting the temperature of a tower kettle to be 110-120 ℃ and the temperature of a tower top to be 60-75 ℃, and collecting tower top fraction to obtain an azeotrope rich in estragon, 4-terpineol and alpha-terpineol;
4) Performing reduced pressure rectification on the obtained azeotrope rich in estragon, 4-terpineol and alpha-terpineol to remove the 4-terpineol to obtain the azeotrope rich in estragon and alpha-terpineol;
5) Putting the obtained azeotrope rich in the estragole and the alpha-terpineol into a rectifying tower, adding potassium bisulfate which is 0.005-0.0058 times of the weight of the azeotrope in the rectifying tower, heating to 200-230 ℃ under normal pressure for reaction, stopping heating after the reaction is finished, carrying out reduced pressure rectification when the temperature of a tower kettle is reduced to be below 100 ℃, firstly setting the temperature of the tower kettle to be 105-110 ℃, setting the temperature of the tower top to be 70-80 ℃, and collecting fraction which is 4-8 percent of the feeding weight of the azeotrope rich in the estragole and the alpha-terpineol; then setting the temperature of the tower kettle at 110-120 ℃ and the temperature of the tower top at 80-85 ℃, and collecting the fraction at the tower top, namely the estragole.
2. The method as set forth in claim 1, wherein in the step 5), the potassium bisulfate is added in an amount of 0.005 to 0.0055 times by weight of the azeotrope rich in estragole and α -terpineol.
3. The method as set forth in claim 1, wherein in the step 5), the reaction is carried out for more than or equal to 4 hours by heating to 200-230 ℃ under normal pressure.
4. The method as set forth in claim 1, wherein the heating to 200-230 ℃ under normal pressure in the step 5) is carried out for 4-4.5 hours.
5. The method as set forth in claim 1, wherein in the step 5), the amount of the overhead fraction collected when the temperature of the column bottom is 110 to 120 ℃ and the temperature of the column top is 80 to 85 ℃ is 84 to 88% of the weight of the feed of the azeotrope rich in estragole and alpha-terpineol.
6. The method as claimed in claim 1, wherein the vacuum distillation in steps 3) to 5) is carried out under a pressure of 1 to 5 mmHg.
7. The method as set forth in any one of claims 1 to 6, wherein in the step 3), the removing of the low-boiling impurities first means: setting the temperature of the tower kettle at 50-90 ℃ and the temperature of the tower top at 45-60 ℃, collecting the fraction which is 50-60% of the weight of the fed material of the star anise oil front fraction, and discarding the collected fraction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210969707.8A CN115181012B (en) | 2022-08-12 | 2022-08-12 | Method for extracting and separating estragole from star anise |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210969707.8A CN115181012B (en) | 2022-08-12 | 2022-08-12 | Method for extracting and separating estragole from star anise |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115181012A true CN115181012A (en) | 2022-10-14 |
| CN115181012B CN115181012B (en) | 2024-01-05 |
Family
ID=83522576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210969707.8A Active CN115181012B (en) | 2022-08-12 | 2022-08-12 | Method for extracting and separating estragole from star anise |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115181012B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107098797A (en) * | 2017-06-23 | 2017-08-29 | 广西万山香料有限责任公司 | A kind of extracting method of chavicol methyl ether |
| CN107188784A (en) * | 2017-06-23 | 2017-09-22 | 广西万山香料有限责任公司 | A kind of extracting method of linalool |
| CN114516785A (en) * | 2022-02-18 | 2022-05-20 | 黄定峰 | Method and equipment for processing high-purity anethole by using star anise oil |
-
2022
- 2022-08-12 CN CN202210969707.8A patent/CN115181012B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107098797A (en) * | 2017-06-23 | 2017-08-29 | 广西万山香料有限责任公司 | A kind of extracting method of chavicol methyl ether |
| CN107188784A (en) * | 2017-06-23 | 2017-09-22 | 广西万山香料有限责任公司 | A kind of extracting method of linalool |
| CN114516785A (en) * | 2022-02-18 | 2022-05-20 | 黄定峰 | Method and equipment for processing high-purity anethole by using star anise oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115181012B (en) | 2024-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102586018B (en) | Method for extracting grape fragrance components from white grape pomace and application of method | |
| CN106433986B (en) | A kind of Japan pepper essential oil and preparation method thereof | |
| CN107912804B (en) | Application of tincture of aroma component on tobacco surface in perfuming tobacco product | |
| CN106190576B (en) | A kind of cinnamon polyphenol extract and cinnamon essential oil industrialize combined extraction technology | |
| CN102836196A (en) | Maca extract and preparation method thereof | |
| CN110003071A (en) | A kind of industrial method quickly and efficiently extracting lutein and quercetagetin | |
| CN113773184B (en) | Method for extracting curcumin compounds | |
| CN112266321A (en) | Method for preparing cannabidiol by decarboxylation of cannabidiolic acid in industrial cannabis sativa | |
| CN104086467B (en) | A kind of solvent extraction and molecularly distilled is utilized to combine the method preparing raphanin | |
| CN101223995B (en) | Preparing method for garlic and onion compound essential oil | |
| CN108658987B (en) | Process for synthesizing and refining diquat | |
| JPS6289637A (en) | Extraction of straight-chain primary aliphatic higher alcohol | |
| CN115181012B (en) | Method for extracting and separating estragole from star anise | |
| CN111171104B (en) | Method for preparing ursolic acid from rosemary oil paste by-product | |
| CN107098797A (en) | A kind of extracting method of chavicol methyl ether | |
| CN110078610B (en) | Preparation method of 6-gingerol | |
| CN104366332A (en) | Deep processing method of chilli seeds | |
| CN101974581A (en) | Theaflavin extraction and purification method | |
| EP3469917B1 (en) | Production process of soybean meal with high content of soluble proteins and product so obtained | |
| CN114671755A (en) | Preparation method of high-content macaene | |
| CN104232310B (en) | A kind of preparation method of dragon fruit pulp quintessence oil | |
| CN110003352A (en) | A kind of extracting method that moringa seeds selenium active constituent is effectively kept | |
| US20230219872A1 (en) | Industrial extraction method of cannabidiol | |
| CN105420293A (en) | Method for separating and purifying resveratrol from traditional Chinese medicine polygonum cuspidatum extraction solution | |
| CN110835291A (en) | Preparation method of estragole |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |