CN109160878A - A kind of method of molecular distillation purification carnosic acid - Google Patents
A kind of method of molecular distillation purification carnosic acid Download PDFInfo
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- CN109160878A CN109160878A CN201711117531.9A CN201711117531A CN109160878A CN 109160878 A CN109160878 A CN 109160878A CN 201711117531 A CN201711117531 A CN 201711117531A CN 109160878 A CN109160878 A CN 109160878A
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- carnosic acid
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/12—Molecular distillation
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- 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
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
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- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of method of molecular distillation purification carnosic acid, includes the following steps: (1) carnosic acid hydrotropy: taking the carnosic acid product of low content, cosolvent is added to dissolve；(2) level-one thin-film distillation dehydration degassing: level-one thin-film distillation column is added in the carnosic acid for having added cosolvent and carries out level-one thin-film distillation dehydration degassing；(3) secondary molecules distillation separation: dehydration degassing liquid pump is entered into secondary molecules distiller and carries out secondary molecules distillation separation, obtains weight component, light component is the position containing part carnosic acid；(4) three-level molecular distillation separates: secondary molecules distillation heavy constituent being pumped into three-level molecular still and carries out three-level molecular distillation separation, obtains weight component, light component is carnosic acid.The present invention has the characteristics that the operating time is short, production intensity is low, low energy consumption, production cost is low, while product purity is high, easily realizes serialization industrial production.
Description
Technical field
The present invention relates to a kind of methods of molecular distillation purification carnosic acid.
Background technique
Rosemary (Classification system: Rosmarinus officinalis), Labiatae shrub.Property happiness temperature climate, originate in
The northern Mediterranean of European Region and Africa.China is just once introduced a fine variety in period far away from Caowei Kingdom.It can be extracted from the leaf of rosemary
Antioxidant (carnosic acid and Rosmarinic acid) and Rosemary Oil with excellent anti-oxidation characteristics.Rosemary antioxidant is extensive
It guarantees the quality for medicine, fried food, rich oil food and the fresh-keeping of each quasi-grease；And to be then used for fragrance, air clear for rosemary essence
The daily-use chemical industries industry such as new agent, driving ants and sterilization, desinsection.Wherein there is carboxylic hydroxyl in antioxidant carnosic acid structure, encounters
The condition of light and alkali is easy to oxidize, easily decomposes or aoxidizes at high temperature.Industrial production is mainly mentioned with organic reagent at present
It takes and separates, but since this method heated time is long, oxidation, polymerization reaction easily occurs, therefore product recovery rate is not high, production cost
It is high.
Summary of the invention
The technical problem to be solved by the invention is to provide a kind of product purities, and molecular distillation high, that production cost is low is smart
The method of carnosic acid processed.
Molecular distillation technique is a kind of novel fine isolation technics of liquid-liquid.Since molecular distillation is in hypoxemia inert conditions
Lower distillation, material heated time is short, and operating pressure is low (vacuum degree is high), therefore separation degree, yield and product quality are high, and purify
Ingredient before it is distilled after do not have too big variation.Therefore molecular distillation be particularly adapted to the higher boilings such as carnosic acid, thermal sensitivity with
And oxidizable material isolates and purifies.
The technical solution adopted by the present invention to solve the technical problems is: a kind of side of molecular distillation purification carnosic acid
Method includes the following steps:
(1) carnosic acid hydrotropy: the carnosic acid product of low content is taken, cosolvent is added to dissolve；
(2) level-one thin-film distillation dehydration degassing: level-one thin-film distillation column is added in the carnosic acid for having added cosolvent and carries out level-one
Thin-film distillation dehydration degassing；
(3) secondary molecules distillation separation: dehydration degassing liquid pump is entered into secondary molecules distiller and carries out secondary molecules distillation separation, is obtained
To weight component, light component is the material containing part carnosic acid；
(4) three-level molecular distillation separates: secondary molecules distillation heavy constituent being pumped into three-level molecular still and carries out the steaming of three-level molecule
Fraction is from obtaining weight component, light component is carnosic acid.
Further, in step (1), the carnosic acid product of the low content refers to that content is lower than the carnosic acid of 40wt%
Product.Rosemary extraction is separated with conventional method, conventional method includes means of supercritical extraction, sub-critical extraction, with organic
The methods of reagent extraction.
Further, in step (1), add cosolvent in 65 ± 2 DEG C of stirring and dissolvings.
Further, in step (1), the cosolvent is propylene glycol, glycerine, vegetable oil (such as soybean oil) or poly- second two
It is one or more of in alcohol 300~600 etc..
Further, in step (2), the heating temperature of the level-one thin-film distillation is 60~120 DEG C, vacuum degree is 20~
500Pa, knifing rotating speed are 100~300rpm, and discharging condensation temperature is 40~80 DEG C.
Further, in step (3), 120~200 DEG C of heating temperature of secondary molecules distillation, discharging condensation temperature is
40~80 DEG C, knifing rotating speed is 100~300rpm, and vacuum degree is 20~100Pa.
Further, in step (4), 160~210 DEG C of the heating temperature of the three-level molecular distillation, discharging condensation temperature be
40~80 DEG C, knifing rotating speed is 100~300rpm, and vacuum degree is 3~10Pa.
Compared with prior art, the present invention has the advantage that
1, the present invention provides a kind of optimal separation method-for higher boilings, temperature-sensitive and oxidizable materials such as separation carnosic acids
Molecular distillation because molecular distillation far below material boiling point at a temperature of operate, and residence time of material is short, therefore to object
Material destroys small；
2, the present invention can effectively remove the substances such as organic solvent, stink in material using molecular distillation, this is for Salvia japonica
Acid is very effective；
3, the present invention uses multiple-grade molecular distillation, and degassing, dehydration, precipitation and the purpose for refining target product can be achieved at the same time；
4, fractional distillation process of the invention is pure physical process, thus can protect separated object matter not contaminated well and encroach on；
5, the avoidable rectifying column technological operation of the present invention, more other conventional distil-lations are short with the operating time, production intensity is low, energy consumption
Low, the features such as production cost is low, while product purity is high, easily realizes serialization industrial production.
Detailed description of the invention
Fig. 1 is that carnosic acid liquid phase test map is made in the embodiment of the present invention 1；
Fig. 2 is that carnosic acid liquid phase test map is made in the embodiment of the present invention 2；
Fig. 3 is that carnosic acid liquid phase test map is made in the embodiment of the present invention 3；
Fig. 4 is that carnosic acid liquid phase test map is made in the embodiment of the present invention 4.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and embodiments.
Embodiment 1
A kind of method of molecular distillation purification carnosic acid, includes the following steps
(1) carnosic acid hydrotropy: the carnosic acid product for taking 1kg to be 15% with the content that conventional method is tentatively extracted adds 2kg poly-
Ethylene glycol 400 is in 65 ± 2 DEG C of stirring and dissolvings；
(2) level-one thin-film distillation dehydration degassing: the carnosic acid of cosolvent will have been added steadily to be pumped into one with the flow velocity of 40ml/min
Level-one thin-film distillation dehydration degassing is carried out in grade thin-film distillation column, wherein the heating temperature of level-one thin-film distillation is 90 DEG C, vacuum
Degree is 100~200Pa, knifing rotating speed 100rpm, and discharging condensation temperature is 65 DEG C；
(3) secondary molecules distillation separation: dehydration degassing liquid is pumped into secondary molecules distiller with the flow velocity of 40ml/min and carries out two
Grade molecular distillation separation, obtains light component 0.05kg and heavy constituent 2.45kg, and wherein the heating temperature of secondary molecules distillation is 180
DEG C, discharging condensation temperature is 75 DEG C, knifing rotating speed 100rpm, and vacuum degree is 20~50Pa；
(4) three-level molecular distillation separates: secondary molecules distillation heavy constituent is pumped into three-level molecular distillation with the flow velocity of 40ml/min
Device carries out three-level molecular distillation separation, obtains light component 0.12kg and heavy constituent 1.72kg, and light component is 85% Salvia japonica of purity
Acid, wherein the heating temperature of three-level molecular distillation is 200 DEG C, and discharging condensation temperature is 65 DEG C, knifing rotating speed 100rpm, vacuum
Degree is 3~10Pa.(map is shown in Fig. 1)
Embodiment 2
A kind of method of molecular distillation purification carnosic acid, comprising the following steps:
(1) carnosic acid hydrotropy: the carnosic acid product for taking 1.2kg to be 23% with the content that conventional method is tentatively extracted adds 2kg
Propylene glycol is in 65 ± 2 DEG C of stirring and dissolvings；
(2) level-one thin-film distillation dehydration degassing: the carnosic acid of cosolvent will have been added steadily to be pumped into one with the flow velocity of 40ml/min
Level-one thin-film distillation dehydration degassing is carried out in grade thin-film distillation column, wherein the heating temperature of level-one thin-film distillation is 90 DEG C, vacuum
Degree is 100~200Pa, knifing rotating speed 100rpm, and discharging condensation temperature is 60 DEG C；
(3) secondary molecules distillation separation: dehydration degassing liquid is pumped into secondary molecules distiller with the flow velocity of 40ml/min and carries out two
Grade molecular distillation separation, obtains light component 0.18kg and heavy constituent 2.85kg, and wherein the heating temperature of secondary molecules distillation is 180
DEG C, discharging condensation temperature is 75 DEG C, knifing rotating speed 100rpm, and vacuum degree is 20~50Pa；
(4) three-level molecular distillation separates: secondary molecules distillation heavy constituent is pumped into three-level molecular distillation with the flow velocity of 40ml/min
Device carries out three-level molecular distillation separation, and obtaining light component is 0.51kg and heavy constituent 2.20kg, and light component is 91% rat-tail of purity
Oxalic acid, wherein the heating temperature of three-level molecular distillation is 200 DEG C, and discharging condensation temperature is 75 DEG C, knifing rotating speed 100rpm, very
Reciprocal of duty cycle is 3~5Pa.(map is shown in Fig. 2)
Embodiment 3
A kind of method of molecular distillation purification carnosic acid, comprising the following steps:
(1) carnosic acid hydrotropy: the carnosic acid product for taking 1kg to be 28% with the content that conventional method is tentatively extracted adds 2kg third
Triol is in 65 ± 2 DEG C of stirring and dissolvings；
(2) level-one thin-film distillation dehydration degassing: the carnosic acid of cosolvent will have been added steadily to be pumped into one with the flow velocity of 40ml/min
Level-one thin-film distillation dehydration degassing is carried out in grade thin-film distillation column, wherein the heating temperature of level-one thin-film distillation is 90 DEG C, vacuum
Degree is 100~200Pa, knifing rotating speed 100rpm, and discharging condensation temperature is 60 DEG C；
(3) secondary molecules distillation separation: dehydration degassing liquid is pumped into secondary molecules distiller with the flow velocity of 40ml/min and carries out two
Grade molecular distillation separation, obtains light component 0.11kg and heavy constituent 2.48kg, and wherein the heating temperature of secondary molecules distillation is 180
DEG C, discharging condensation temperature is 75 DEG C, knifing rotating speed 100rpm, and vacuum degree is 20~50Pa；
(4) three-level molecular distillation separates: secondary molecules distillation heavy constituent is pumped into three-level molecular distillation with the flow velocity of 40ml/min
Device carries out three-level molecular distillation separation, and obtaining light component is 0.33kg and heavy constituent 2.02kg, and light component is 80% rat-tail of purity
Oxalic acid, wherein the heating temperature of three-level molecular distillation is 200 DEG C, and discharging condensation temperature is 75 DEG C, knifing rotating speed 100rpm, very
Reciprocal of duty cycle is 3~5Pa.(map is shown in Fig. 3)
Embodiment 4
A kind of method of molecular distillation purification carnosic acid, comprising the following steps:
(1) carnosic acid hydrotropy: the carnosic acid product for taking 1kg to be 28% with the content that conventional method is tentatively extracted adds 2kg olive
Olive oil is in 65 ± 2 DEG C of stirring and dissolvings；
(2) level-one thin-film distillation dehydration degassing: the carnosic acid of cosolvent will have been added steadily to be pumped into one with the flow velocity of 40ml/min
Level-one thin-film distillation dehydration degassing is carried out in grade thin-film distillation column, wherein the heating temperature of level-one thin-film distillation is 90 DEG C, vacuum
Degree is 100~200Pa, knifing rotating speed 100rpm, and discharging condensation temperature is 60 DEG C；
(3) secondary molecules distillation separation: dehydration degassing liquid is pumped into secondary molecules distiller with the flow velocity of 40ml/min and carries out two
Grade molecular distillation separation, obtains light component 0.17kg and heavy constituent 2.48kg, and wherein the heating temperature of secondary molecules distillation is 180
DEG C, discharging condensation temperature is 70 DEG C, knifing rotating speed 100rpm, and vacuum degree is 20~50Pa；
(4) three-level molecular distillation separates: secondary molecules distillation heavy constituent is pumped into three-level molecular distillation with the flow velocity of 40ml/min
Device carries out three-level molecular distillation separation, and obtaining light component is 0.32kg and heavy constituent 2.13kg, and light component is 87% rat-tail of purity
Oxalic acid, wherein the heating temperature of three-level molecular distillation is 200 DEG C, and discharging condensation temperature is 70 DEG C, knifing rotating speed 100rpm, very
Reciprocal of duty cycle is that 3~5Pa(map is shown in Fig. 4).
Claims (10)
1. a kind of method of molecular distillation purification carnosic acid, which comprises the steps of:
(1) carnosic acid hydrotropy: the carnosic acid product of low content is taken, cosolvent is added to dissolve；
(2) level-one thin-film distillation dehydration degassing: level-one thin-film distillation column is added in the carnosic acid for having added cosolvent and carries out level-one
Thin-film distillation dehydration degassing；
(3) secondary molecules distillation separation: dehydration degassing liquid pump is entered into secondary molecules distiller and carries out secondary molecules distillation separation, is obtained
To weight component, light component is the material containing part carnosic acid；
(4) three-level molecular distillation separates: secondary molecules distillation heavy constituent being pumped into three-level molecular still and carries out the steaming of three-level molecule
Fraction is from obtaining weight component, light component is carnosic acid.
2. the method for molecular distillation purification carnosic acid according to claim 1, which is characterized in that described in step (1)
The carnosic acid product of low content refers to that content is lower than the carnosic acid product of 40wt%.
3. the method for molecular distillation purification carnosic acid according to claim 1 or 2, which is characterized in that in step (1),
Add cosolvent in 65 ± 2 DEG C of stirring and dissolvings.
4. the method for molecular distillation purification carnosic acid according to claim 1 or 2, which is characterized in that in step (1),
The cosolvent is one or more of in propylene glycol, glycerine, vegetable oil or Liquid Macrogol~600.
5. the method for molecular distillation purification carnosic acid according to claim 3, which is characterized in that described in step (1)
Cosolvent is one or more of in propylene glycol, glycerine, vegetable oil or Liquid Macrogol~600.
6. the method for molecular distillation purification carnosic acid according to claim 1 or 2, which is characterized in that in step (2),
The heating temperature of the level-one thin-film distillation be 60~120 DEG C, vacuum degree be 20~500Pa, knifing rotating speed be 100~
300rpm, discharging condensation temperature are 40~80 DEG C.
7. the method for molecular distillation purification carnosic acid according to claim 1 or 2, which is characterized in that in step (3),
120~200 DEG C of heating temperature of secondary molecules distillation, discharging condensation temperature are 40~80 DEG C, knifing rotating speed is 100~
300rpm, vacuum degree are 20~100Pa.
8. the method for molecular distillation purification carnosic acid according to claim 6, which is characterized in that described in step (3)
Secondary molecules distillation 120~200 DEG C of heating temperature, discharging condensation temperature be 40~80 DEG C, knifing rotating speed be 100~
300rpm, vacuum degree are 20~100Pa.
9. the method for molecular distillation purification carnosic acid according to claim 1 or 2, which is characterized in that in step (4),
160~210 DEG C of the heating temperature of the three-level molecular distillation, discharging condensation temperature be 40~80 DEG C, knifing rotating speed be 100~
300rpm, vacuum degree are 3~10Pa.
10. the method for molecular distillation purification carnosic acid according to claim 8, which is characterized in that in step (4), institute
160~210 DEG C of heating temperature for stating three-level molecular distillation, discharging condensation temperature be 40~80 DEG C, knifing rotating speed be 100~
300rpm, vacuum degree are 3~10Pa.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711117531.9A CN109160878A (en) | 2017-11-13 | 2017-11-13 | A kind of method of molecular distillation purification carnosic acid |
| PCT/CN2018/103157 WO2019091194A1 (en) | 2017-11-13 | 2018-08-30 | Method for refining carnosic acid by means of molecular distillation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711117531.9A CN109160878A (en) | 2017-11-13 | 2017-11-13 | A kind of method of molecular distillation purification carnosic acid |
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| WO (1) | WO2019091194A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171104A (en) * | 2020-01-09 | 2020-05-19 | 湖南德诺健康产业有限公司 | Method for preparing ursolic acid from rosemary oil paste by-product |
| CN111544922A (en) * | 2020-04-03 | 2020-08-18 | 广州正明生物科技有限公司 | Preparation method of rosemary extract and application of rosemary extract in antioxidation of edible oil |
| CN112426739A (en) * | 2020-10-16 | 2021-03-02 | 安庆缘启医药科技有限公司 | Preparation process for extracting anticancer medicine by molecular distillation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417447A (en) * | 2011-10-31 | 2012-04-18 | 广西亿康药业股份有限公司 | Production method of undecylenic acid |
| CN102617315A (en) * | 2012-02-29 | 2012-08-01 | 华南理工大学 | Method for refining pseudoionone through molecular distillation |
| CN105601477A (en) * | 2016-01-29 | 2016-05-25 | 广东嘉博制药有限公司 | Method for producing high-purity propofol |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102286059A (en) * | 2011-09-08 | 2011-12-21 | 南京泽朗医药科技有限公司 | Method for extracting ursolic acid, carnosic acid and rosmarinic acid from rosmarinus officinalis |
-
2017
- 2017-11-13 CN CN201711117531.9A patent/CN109160878A/en active Pending
-
2018
- 2018-08-30 WO PCT/CN2018/103157 patent/WO2019091194A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417447A (en) * | 2011-10-31 | 2012-04-18 | 广西亿康药业股份有限公司 | Production method of undecylenic acid |
| CN102617315A (en) * | 2012-02-29 | 2012-08-01 | 华南理工大学 | Method for refining pseudoionone through molecular distillation |
| CN105601477A (en) * | 2016-01-29 | 2016-05-25 | 广东嘉博制药有限公司 | Method for producing high-purity propofol |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171104A (en) * | 2020-01-09 | 2020-05-19 | 湖南德诺健康产业有限公司 | Method for preparing ursolic acid from rosemary oil paste by-product |
| CN111544922A (en) * | 2020-04-03 | 2020-08-18 | 广州正明生物科技有限公司 | Preparation method of rosemary extract and application of rosemary extract in antioxidation of edible oil |
| CN112426739A (en) * | 2020-10-16 | 2021-03-02 | 安庆缘启医药科技有限公司 | Preparation process for extracting anticancer medicine by molecular distillation |
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| WO2019091194A1 (en) | 2019-05-16 |
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