CN111714953A - Method for removing phthalate plasticizer in extract - Google Patents
Method for removing phthalate plasticizer in extract Download PDFInfo
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- CN111714953A CN111714953A CN202010563681.8A CN202010563681A CN111714953A CN 111714953 A CN111714953 A CN 111714953A CN 202010563681 A CN202010563681 A CN 202010563681A CN 111714953 A CN111714953 A CN 111714953A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D36/00—Filter circuits or combinations of filters with other separating devices
- B01D36/003—Filters in combination with devices for the removal of liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D36/00—Filter circuits or combinations of filters with other separating devices
- B01D36/003—Filters in combination with devices for the removal of liquids
- B01D36/008—Means to filter or treat the separated liquid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a method for removing phthalate plasticizer from extract, which comprises the following steps: a. taking an extract with an excessive plasticizer, dissolving the extract with dilute ethanol, and carrying out solid-liquid separation to obtain a clear extract solution; b. adsorbing the extract solution by plasticizer-removing resin, collecting effluent liquid, then carrying out deep resolution on the resin by using high-concentration ethanol solution, and collecting eluent; c. concentrating and drying the resin effluent to obtain a plasticizer-free extract A; d. concentrating the eluate, removing ethanol, and adding appropriate amount of purified water to obtain concentrated solution I; e. extracting the concentrated solution I by using an organic solvent, and collecting an organic phase; f. concentrating the organic phase, and removing the organic solvent to obtain extract; g. dissolving the extract with ethanol solution, performing solid-liquid separation to obtain a solution to be crystallized, and performing crystallization and recrystallization to obtain the plasticizer-free extract B with high content. According to the method, the plasticizer-free extracts with different specifications are prepared, so that the loss of functional components is effectively avoided, and the cost of the plasticizer removal process is favorably controlled.
Description
Technical Field
The application relates to the technical field of extraction and separation, in particular to a method for removing a plasticizer from an extract.
Background
The molecular structure of the plasticizer is similar to hormone, which is called as 'environmental hormone', and toxic chemical substances in Taiwan environmental protection agency of China can cause the abnormal reproductive system and even cause the risk of teratogenesis and cancer if the plasticizer is eaten for a long time.
Plasticizer compounds are present in some plant materials due to pollution of soil resources, lack of knowledge of reasonable use of plastic films by crop growers, and stricter management of plastic films for planting. Meanwhile, as the plasticizer is not well known by part of extract manufacturers, the plasticizer may be transferred from the plastic products to the extract during the transportation, transfer, storage and the like of the materials by the plastic products in the production process. The extract is mainly used as a raw material to be applied to the industries of food, beverage and health food, and the problem of the plasticizer in the extract product is not only related to the future of the product but also related to the development of the industry at present when food safety is concerned day by day.
The existing method for removing the plasticizer in the extract mainly comprises the following steps: CO 22Supercritical process, resin and CO2Supercritical combined process, CO2Supercritical and nanofiltration combined method, mesoporous material adsorption method, etc. The supercritical method for removing the plasticizer has high operation requirement and small treatment capacity, and the methods cannot fully recover the effective components, so that the effective components are lost to a certain extent.
Disclosure of Invention
The invention aims to provide a method capable of effectively removing plasticizer from an extract, which has the characteristics of simple operation, stability, reliability, economy, practicability, industrial production and the like.
The scheme adopted by the invention for solving the technical problems is as follows: a method for removing phthalate plasticizers from an extract comprises the following steps:
(1) preparing an extract solution: dissolving the extract with diluted ethanol solution, filtering to remove impurities to obtain extract solution;
(2) removing plasticizer from resin: passing the solution obtained in the step (1) through plasticizer removing resin, collecting effluent liquid, eluting the resin by using high-concentration ethanol solution, and collecting ethanol eluent;
(3) concentrating and drying: concentrating the effluent obtained in the step (2) under reduced pressure, and drying to obtain a plasticizer-free extract A;
(4) concentration: concentrating the ethanol eluate obtained in the step (2) under reduced pressure, removing ethanol, and adding a proper amount of purified water to obtain a concentrated solution I;
(5) organic solvent extraction: extracting the concentrated solution I obtained in the step (4) by using an organic solvent, and collecting an organic phase;
(6) concentration: concentrating the organic phase obtained in the step (5) under reduced pressure, and removing the organic solvent to obtain an extract;
(7) dissolving and filtering: and (4) dissolving the extract obtained in the step (6) by using an ethanol solution, and carrying out solid-liquid separation to obtain uniform liquid to be crystallized.
(8) And (3) crystallization and recrystallization: and (4) crystallizing and recrystallizing the liquid to be crystallized obtained in the step (7) to obtain the plasticizer-free extract B with high content.
Preferably, in the step (1), the concentration of the dilute ethanol solution for dissolving the extract is 10-70%; the concentration of the high-concentration ethanol solution for eluting the resin is 90-100 percent; the dissolving amount of the extract in a diluted ethanol solution is 1g/100 mL-10 g/100 mL; and filtering and removing impurities from the ethanol solution by using a filter or a centrifuge.
Preferably, in the step (2), the plasticizer removing resin is strong polar adsorption resin such as LX-1T, LX-3020, XDA-8D and the like; the ratio of the diameter to the height of the plasticizer removing resin in the column is 1: 5-1: 10; the mass ratio of the plasticizer removing resin to the extract is 10: 1-1: 1; the sample loading flow rate of the extract solution is 0.5 BV-3 BV;
preferably, in the step (3) and the step (4), the reduced pressure concentration temperature of the resin effluent is 50-75 ℃, and the pressure is-0.05-0.1 MPa.
Preferably, in the step (3), the resin effluent is concentrated under reduced pressure until the solid content is 40-70%, and the drying mode is reduced pressure drying or spray drying.
Preferably, in the step (4), the resin eluate is concentrated under reduced pressure until the recovered solution does not contain ethanol.
Preferably, in the step (5), the organic solvent is a solvent which is not completely miscible with water, such as n-butanol, ethyl acetate, dichloromethane and the like; the volume ratio of the organic solvent to the concentrated solution I is 0.2: 1-5: 1; and (3) collecting an organic phase, wherein the extraction temperature is 20-50 ℃, the extraction times are 2-3 times.
Preferably, in the step (6), the organic phase is concentrated under reduced pressure until the recovered solution does not contain an organic solvent.
Preferably, in the step (7), the dissolving step is to add 30% -95% ethanol in an amount 5-30 times that of the extract, heat, stir, dissolve, and separate solid and liquid to obtain a clear solution, and obtain a solution to be crystallized.
Preferably, in the step (8), the crystallization step is: and (3) refrigerating the liquid to be crystallized at a low temperature for crystallization, then carrying out solid-liquid separation, and collecting the solid.
Preferably, in the step (8), the recrystallization step is: heating and dissolving the solid obtained by crystallization by using 15-50 times of 30-95% ethanol, carrying out solid-liquid separation, removing insoluble substances, then cooling and crystallizing, carrying out solid-liquid separation, and then dispersing and washing the solid by using 2-5 times of 30-95% ethanol.
Preferably, in the step (8), the number of recrystallization operations may be increased or decreased according to the content requirement and the plasticizer residue.
It is to be noted that all reagents used in the method of the present invention are plasticizer-free reagents; in the method, equipment, pipelines and storage tanks which are in contact with the materials are all made of stainless steel materials.
The invention has the following beneficial effects: by preparing plasticizer-free extracts with different specifications, loss of functional components is effectively avoided, cost control in the plasticizer removal process is facilitated, and the method is suitable for industrial production.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
(1) Preparing an extract solution: dissolving 5kg of herba Epimedii extract (icariin 20%) containing plasticizer in 250L 50% ethanol solution, centrifuging, and removing impurities to obtain herba Epimedii extract solution.
(2) Removing plasticizer from resin: enabling the epimedium extract solution obtained in the step (1) to pass through 50L of pretreated LX-1T adsorption resin, and collecting effluent liquid; then eluting with 100L 95% ethanol solution, and collecting 95% ethanol eluate.
(3) Concentrating and drying: concentrating the effluent obtained in step (2) at 70 deg.C and-0.09 MPa under reduced pressure, and spray drying to obtain 3.2kg herba Epimedii extract A with icariin content of 18.1% and no phthalate.
(4) Concentration: concentrating the 95% ethanol eluate obtained in step (2) under reduced pressure to remove ethanol to obtain about 5L concentrated solution; then adding purified water to the volume of about 35L to obtain herba Epimedii concentrated solution I.
(5) And (3) ethyl acetate extraction: extracting the epimedium concentrated solution I obtained in the step (4) with 35L ethyl acetate for 2 times at the temperature of 50 ℃, collecting and combining ethyl acetate phases.
(6) Concentration: and (4) concentrating the ethyl acetate phase obtained in the step (5) under reduced pressure to dryness, and then adding 15L of 80% ethanol into the dried product for dissolving to obtain a crystalline liquid.
(7) And (3) crystallization: and (4) standing the liquid to be crystallized obtained in the step (6) at the temperature of 5 ℃ for 24h for crystallization, carrying out solid-liquid separation, and collecting crystals.
(8) And (3) recrystallization: adding the crystal obtained in the step (7) into 6L of 50% ethanol, heating to 60 ℃ for dissolving, then cooling to about 10 ℃ for crystallization, and carrying out solid-liquid separation to obtain 0.38kg of epimedium extract B, wherein the icariin content is 93.5% by detection, and no phthalate ester substances are detected.
Example 2
(1) Preparing an extract solution: dissolving 5kg of plasticizer-containing Ginseng radix extract (total saponin 40%) in 250L 50% ethanol solution, filtering, and removing impurities to obtain Ginseng radix extract solution.
(2) Removing plasticizer from resin: enabling the solution obtained in the step (1) to pass through 50L of pretreated XDA-8D adsorption resin, and collecting effluent liquid; then eluting with 100L 95% ethanol solution, and collecting 95% ethanol eluate.
(3) Concentrating and drying: concentrating the effluent obtained in step (2) at 65 deg.C and-0.1 MPa under reduced pressure, and drying to obtain 3.7kg of Ginseng radix extract A, which has been detected to have total saponin content of 35% and no phthalate.
(4) Concentration: and (3) concentrating the 95% ethanol eluate obtained in the step (2) under reduced pressure, removing ethanol, and adding a proper amount of purified water until the concentration is about 20L to obtain a ginseng concentrated solution I.
(5) N-butanol extraction: and (4) extracting the concentrated solution I obtained in the step (4) for 2 times by using 40L of n-butanol, and collecting an n-butanol phase.
(6) Concentration: and (3) concentrating the n-butanol phase obtained in the step (5) under reduced pressure to dryness, and then adding 10L 60% ethanol into the dried product for dissolving to obtain a liquid to be crystallized.
(7) And (3) crystallization: and (4) standing the liquid to be crystallized obtained in the step (6) at the temperature of 5 ℃ for 24h for crystallization, carrying out solid-liquid separation, and collecting crystals.
(8) And (3) recrystallization: and (3) adding the crystals obtained in the step (7) into 15L of 30% ethanol, heating to 65 ℃ for dissolving, then cooling to about 10 ℃ for crystallization, and carrying out solid-liquid separation to obtain 0.4kg of a ginseng extract B, wherein the content of total saponins is detected to be 90%, and no phthalate ester substances are detected.
The above description is only an example of the present application and is not intended to limit the scope of the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A method for removing phthalate plasticizers from an extract is characterized by comprising the following steps:
(1) preparing an extract solution: dissolving the extract with diluted ethanol solution, filtering, and removing impurities to obtain extract solution.
(2) Removing plasticizer from resin: passing the solution obtained in the step (1) through plasticizer removing resin, collecting effluent liquid, eluting the resin by using high-concentration ethanol solution, and collecting ethanol eluent;
(3) concentrating and drying: and (3) concentrating the effluent obtained in the step (2) under reduced pressure, and drying to obtain the plasticizer-free extract A.
(4) Concentration: concentrating the ethanol eluate obtained in the step (2) under reduced pressure, removing ethanol, and adding a proper amount of purified water to obtain a concentrated solution I;
(5) organic solvent extraction: extracting the concentrated solution I obtained in the step (4) by using an organic solvent, and collecting an organic phase;
(6) concentration: concentrating the organic phase obtained in the step (5) under reduced pressure, and removing the organic solvent to obtain an extract;
(7) dissolving and filtering: and (4) dissolving the extract obtained in the step (6) by using an ethanol solution, and carrying out solid-liquid separation to obtain uniform liquid to be crystallized.
(8) And (3) crystallization and recrystallization: and (4) crystallizing and recrystallizing the liquid to be crystallized obtained in the step (7) to obtain the plasticizer-free extract B with high content.
2. The method according to claim 1, wherein in the step (1), the concentration of the dilute ethanol solution for dissolving the extract is 10-70%; the concentration of the high-concentration ethanol solution for eluting the resin is 80-100 percent; the dissolving amount of the extract in a diluted ethanol solution is 1g/100 mL-10 g/100 mL; and filtering and removing impurities from the ethanol solution by using a filter or a centrifuge.
3. The method as claimed in claim 1, wherein in step (2), the deplasticizer resin is strong polar adsorption resin such as LX-1T, LX-3020 and XDA-8D.
4. The method according to claim 1, wherein in the step (3), the resin effluent is concentrated under reduced pressure to a solid content of 20-70%, and the drying mode is reduced pressure drying or spray drying.
5. The method according to claim 1, wherein in the step (4), the resin eluate is concentrated under reduced pressure until the recovered solution does not contain ethanol.
6. The method according to claim 1, wherein in the step (5), the organic solvent is a solvent which is not completely miscible with water, such as n-butanol, ethyl acetate, dichloromethane and the like; the volume ratio of the organic solvent to the concentrated solution I is 0.2: 1-5: 1; the extraction temperature is 5-70 ℃, and the extraction times are 1-5.
7. The method according to claim 1, wherein in the step (6), the organic phase is concentrated under reduced pressure until the recovered solution contains no organic solvent.
8. The method according to claim 1, wherein in the step (7), the dissolving step is: adding 30-95% ethanol of 5-30 times into the extract, heating, stirring, dissolving, and performing solid-liquid separation to obtain a clear liquid to be crystallized.
9. The method according to claim 1, wherein in the step (8), the crystallization step is: and (3) refrigerating the liquid to be crystallized at a low temperature for crystallization, then carrying out solid-liquid separation, and collecting the solid.
10. The method according to claim 1, wherein in the step (8), the recrystallization step is: heating and dissolving the solid obtained by crystallization by using 15-50 times of 30-95% ethanol, carrying out solid-liquid separation, removing insoluble substances, then cooling and crystallizing, carrying out solid-liquid separation, and then dispersing and washing the solid by using 2-5 times of 30-95% ethanol; furthermore, the number of recrystallization operations can be increased or decreased according to the content requirement and the residual situation of the plasticizer.
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| CN202010563681.8A CN111714953B (en) | 2020-06-18 | 2020-06-18 | Method for removing phthalate plasticizer in extract |
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| CN202010563681.8A CN111714953B (en) | 2020-06-18 | 2020-06-18 | Method for removing phthalate plasticizer in extract |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112546665A (en) * | 2020-12-01 | 2021-03-26 | 晨光生物科技集团股份有限公司 | Method for removing plasticizer from pepper, preparation method of pepper oleoresin and pepper oleoresin |
| CN113956322A (en) * | 2021-11-17 | 2022-01-21 | 湖南华诚生物资源股份有限公司 | Method for removing harmful substances in momordica grosvenori extract |
| CN117065453A (en) * | 2023-08-17 | 2023-11-17 | 广东青云山药业有限公司 | Device and process for removing phthalate plasticizers in ganoderma lucidum triterpene extract |
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| CN112546665A (en) * | 2020-12-01 | 2021-03-26 | 晨光生物科技集团股份有限公司 | Method for removing plasticizer from pepper, preparation method of pepper oleoresin and pepper oleoresin |
| CN113956322A (en) * | 2021-11-17 | 2022-01-21 | 湖南华诚生物资源股份有限公司 | Method for removing harmful substances in momordica grosvenori extract |
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