CN1073867C - Separation method for material composition by supercritical fluid crystallization - Google Patents
Separation method for material composition by supercritical fluid crystallization Download PDFInfo
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- CN1073867C CN1073867C CN98111546A CN98111546A CN1073867C CN 1073867 C CN1073867 C CN 1073867C CN 98111546 A CN98111546 A CN 98111546A CN 98111546 A CN98111546 A CN 98111546A CN 1073867 C CN1073867 C CN 1073867C
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Abstract
The present invention relates to a method for crystallizing and separating supercritical fluids with substance components. A supercritical fluid extraction technique and a traditional separation method are combined, and the method comprises the preparation of multiple-liquid phase mix material and a system which is composed of a booster pump, a heat exchanger, a crystallization kettle, a separator and a buffer tank. When the system maintains certain temperature and pressure, the processes of extraction, adsorption, crystallization and dryness are carried out in a crystallization kettle under the combined action of supercritical fluid, organic solvent and a crystallizer, and the active ingredients of the mix material carries out one-step gradient crystallization and separation. The method has the advantages of high separation efficiency and high product purity, and greatly simplifies the substance purification technique.
Description
The present invention relates to the separation process in the chemical process, exactly is a kind of crystalization in supercritical fluid separation method of material composition.
For the homogeneous phase system, separate the operating process that is absolutely necessary, the difference according to mass transfer feature between the phase border mainly contains unit operations such as absorption, extraction, lixiviate, crystallization, absorption and rectifying.To the separation of liquid phase system again based on extraction, crystallization, absorption and rectifying.Above separation method is used very extensive in fields such as chemical, medicine, food.
Particularly the active component of natural materials is very complicated mostly, and wherein some have thermal sensitivity, if use above-mentioned separation method, exists mostly then that separative efficiency is low, energy consumption big, the residual drawback such as exceed standard of Toxic in the active ingredient destructible, product.Some product qualities are required very strict with medicine, the food service industry, its application is difficult to satisfy production requirement.
Supercritical fluid extraction (Supercritical Fluid Extraction. is called for short SFE) is a kind of novel separation method of rising in recent years, treasury is got and is distilled in one, have extraction efficiency height, no solvent residue toxicity, active skull cap components and thermal sensitivity composition be difficult for being decomposed destruction, can keep to greatest extent extract natural feature, can realize plurality of advantages such as Selective Separation, in the trend that current people thirst for going back to nature, the SFE method gains great popularity.In developed country, existing application SFE technology extracting hop active ingredient, high-grade natural essence and pigment, and coffee bean removes the suitability for industrialized production report of caffeine.Limitation such as but that supercritical liquid extraction technique still exists is big such as extraction component narrow range, extraction equipment specification requirement height, construction investment, be difficult to accomplish continuous operation, production efficiency is low.
The objective of the invention is to provide a kind of method of efficient separate substance composition, this method can once realize the isolation and purification of composition in the polynary mixed system.
The present invention is on the basis of summing up existing separation method technical characterstic, utilize the dissolution extraction characteristic of supercritical fluid to solvent and solute, the SFE process is introduced in extraction, absorption and crystallization, constitute a system, utilize the compound action of extraction, distillation, absorption and crystallization, thereby realize purpose of the present invention.
This method is utilized organic solvent and the solute in the polynary mixed stocker of supercritical fluid extraction, changes the dissolution characteristics of material composition in organic solvent and supercritical fluid, and the solute crystallization is separated out; Also utilize simultaneously the crystallizer surface physical characteristic to the absorption of different material, block, gather performance difference, make the solute composition of separating out form the orderly gradient crystallization that is similar to the chromatography effect and distribute.Thereby realize effective separation of disposable multiple material, obtain high purity product.
Accompanying drawing is depicted as the process principle figure of this method.
Shown in the figure, form supercritical fluid after the treated supercharging of working media. Working media can CO2, alkane, alkene etc.
Raw material is exactly object to be separated, can be to live through the biology that contains that solvent extraction and separation obtains The polynary liquid phase mixture material of property composition; Also can be such as lixiviate, squeeze, calcine, synthesize etc. Other method Diversity material that make or natural. The solvent that extraction is used is by hydro carbons, alcohol One pack system or many groups such as class, aldehydes, ester class, ketone, ethers, acids, bases, salt and water Branch consists of. Raw material can directly or drop into after filtering in the crystallization kettle, also can be with entrainer together through heat Enter crystallization kettle behind the interchanger. Employed mixed solvent should have bigger in supercritical fluid Dissolubility.
Dismountable crystallizer is set in the crystallization kettle. Crystallizer is by one group or some groups of crystallization plates or knot Wafer consists of. Thin plate (sheet), net with processing such as pottery, glass, metal, macromolecular materials The various shapes such as lattice plate (sheet), corrugated plating (sheet), cavity slab (sheet). According to separate object Difference, for improving separative efficiency, except the shape that changes crystallization plates (sheet), its surface can Apply silica gel, aluminium oxide, magnesia, glass microballoon, active carbon, macrolattice polymeric adsorbent, poly-Acid amides, magnetic material etc. change crystallization plates (sheet) surface physical properties, strengthen the suction to solute Attached property and selective. In addition, can also be in crystallizer the filling filler to improve separative efficiency.
For improving separative efficiency, in supercritical fluid, can also add entrainer (claiming polarity modifier again), entrainer also is a kind of solvent, its effect is the solubility property that improves supercritical fluid.If working media is selected appropriate, also can not use entrainer.
Separating still is used to the solute that separates solvent, working media and extract.
When system works, crystallization kettle and separating still all are under separately the temperature and pressure condition, the crystallization control time, supercritical fluid and polynary liquid phase mixture material are finished extraction, absorption, crystallization, distillation (drying) in crystallization kettle, under the effect of crystallizer, make single or one step of composite parts realization Crystallization Separation or gradient crystallization separation in the multicomponent system.After treating system's cooling, release, on crystallizer, collect highly purified product.
In the method, the employed solvent of Crystallization Separation is a supercritical fluid, the abstraction technique of supercritical fluid and traditional separation method are united, treasury is got, absorption, crystallization, dry in one, under the acting in conjunction of solvent, supercritical fluid and crystallizer, to polynary liquid phase mixture is to realize that a step selectivity gradient crystallization separates the separative efficiency height.Product is separated out with crystallization, so purity is also high, this has just simplified enrichment, the purifying process of material greatly.
This method is applicable under the normal temperature to be the isolation and purification that is crystalline material under crystalline solid matter or the specified conditions, is not only applicable to separation, the purifying of biomaterial active material, also is applicable to separation, the purifying of non-biological material material.
Non-limiting examples: 1. with the 50g ginkgo biloba crude extract (total lactone 6%, poisonous phenolic content 〉=500ppm) are raw material,
It is dissolved in (mass ratio is in the mixed solvent of being made up of low mass molecule alcohol, ester, ketone, ether
1: 4-1: 20), get solution after the filtration, input high pressure crystal still, and with the 0.3mm rectangle not
Rust steel corrugated plating places crystallization kettle, at crystallization kettle operating pressure 15-25MPa, temperature 35-
55 ℃, separating still operating pressure 3.5-9.0MPa, temperature 20-45 ℃, crystallization time 0.5
Under the condition of-2.5h, use supercritical CO
2One step of extractive crystallization is isolated 65% ginkgolides
With 15% Bilobalide, the rate of recovery of Total Terpene Lactones reaches 80%.2. ether (5 times of cold carrying 3 times of the amount) extract with 50g chrysanthemum mugwort powder is a raw material, distills back
After receiving ether, be dissolved in (mass ratio in the mixed solvent of forming by low molecule ketone, alcohol and ester
1: 5-1: 30), after the filtration, filtrate is gone into the high pressure crystal still, presets 5mm in the still and scribbles silica gel
The rectangular ceramic plate organize more.At crystallization kettle operating pressure 26-32MPa, temperature 45-60 ℃,
Separating still operating pressure 3.5-9.0MPa, temperature 20-50 ℃, crystallization time 0.5-2h's
Under the condition, use supercritical CO
2Extractive crystallization is prepared the product of 1g artemislnin content 80%.3. be raw material with 20g hypericum perforatum crude extract, it be dissolved in formed by low molecule ether and alcohol
(mass ratio is 1: 5-1: 20), fully stirring and dissolving is filtered filtrate in the hot mixed solvent
Go into the high pressure crystal still, and the many groups of rectangular metal plate that 0.5mm scribbles aluminium oxide are placed crystallization kettle
In.At crystallization kettle operating pressure 8-32MPa, temperature 35-60 ℃, separating still operating pressure 3.5
-15.0MPa, temperature 20-50 ℃, under the condition of crystallization time 0.5-3.5h, face with super
The CO of boundary
2Extractive crystallization is prepared the product of 3.1g hypericin content 60%.4. get 2-amino-phenol and 2-pyridine carboxaldehyde by 1: 1 weight, be dissolved in the ethanol, stir,
After adding hydration one-tenth, drop into crystallization kettle, under 8-32MPa, temperature 40-50 ℃, face with super
The CO of boundary
2Crystallization Separation gets high-purity 2-pyridine carboxaldehyde and contracts-the 2-hydroxyanilines.This product can be used
As the photometering developer.
Claims (4)
1. the crystalization in supercritical fluid separation method of a material composition, comprise the preparation of polynary liquid phase mixture material and the system that constitutes by booster pump, heat exchanger, crystallization kettle, separator and surge tank, it is characterized in that: when crystallization kettle in the system and separating still are kept certain temperature and pressure separately, supercritical fluid and polynary liquid phase mixture material in crystallization kettle under the effect of crystallizer, finish extraction, absorption, crystallization and drying in the certain hour, make the active ingredient in the mixed material realize that a step gradient crystallization separates.
2. crystalization in supercritical fluid separation method according to claim 1 is characterized in that: crystallizer is made of one group or some groups of crystallization plates or crystalline wafer.
3. crystalization in supercritical fluid separation method according to claim 1 and 2 is characterized in that: the surface-coated of crystallization plates or crystalline wafer has silica gel, aluminium oxide, magnesia, glass microballoon, active carbon, macrolattice polymeric adsorbent, polyamide, magnetic material.
4. crystalization in supercritical fluid separation method according to claim 1 is characterized in that: add entrainer in supercritical fluid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98111546A CN1073867C (en) | 1998-10-23 | 1998-10-23 | Separation method for material composition by supercritical fluid crystallization |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98111546A CN1073867C (en) | 1998-10-23 | 1998-10-23 | Separation method for material composition by supercritical fluid crystallization |
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| CN1220906A CN1220906A (en) | 1999-06-30 |
| CN1073867C true CN1073867C (en) | 2001-10-31 |
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| CN98111546A Expired - Fee Related CN1073867C (en) | 1998-10-23 | 1998-10-23 | Separation method for material composition by supercritical fluid crystallization |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1634925B (en) * | 2004-10-21 | 2010-04-28 | 潘见 | Separation and purification method for ginkgolide monomer |
| CN102058996A (en) * | 2010-10-29 | 2011-05-18 | 华侨大学 | Method for preparing ultrafine drug particles in process of improving supercritical anti-solvent by nonsolvent method |
| CN102329367A (en) * | 2011-07-26 | 2012-01-25 | 苏州宝泽堂医药科技有限公司 | Method for preparing pristimerin |
| CN111606488A (en) * | 2020-05-28 | 2020-09-01 | 陕西煤业化工技术研究院有限责任公司 | Critical desalting method and system for high-salinity wastewater |
| CN114288945A (en) * | 2021-12-29 | 2022-04-08 | 陕西巨子生物技术有限公司 | Extraction crystallization kettle and supercritical CO2Extraction device and extraction method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994013377A1 (en) * | 1992-12-11 | 1994-06-23 | Geert Feye Woerlee | Process and device for separating a mixture or extracting a material |
| JPH08154689A (en) * | 1994-12-06 | 1996-06-18 | Shin Nippon Kagaku Kogyo Kk | Method for purifying natural type abscisic acid |
| CN1124591A (en) * | 1995-10-10 | 1996-06-19 | 金绍黑 | Supercritical CO2 extracting process for bad-smell-less garlicin |
| CN1125215A (en) * | 1995-05-30 | 1996-06-26 | 华东理工大学 | Process for making high explosive microgranula by using supercritical fluid devitrification method |
| US5584989A (en) * | 1990-07-13 | 1996-12-17 | Isco, Inc. | Apparatus for supercritical fluid extraction having means for removing extraction from collection solvent |
| JPH0952866A (en) * | 1995-08-09 | 1997-02-25 | Chlorine Eng Corp Ltd | Concentrated separation of fatty acid ester |
-
1998
- 1998-10-23 CN CN98111546A patent/CN1073867C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5584989A (en) * | 1990-07-13 | 1996-12-17 | Isco, Inc. | Apparatus for supercritical fluid extraction having means for removing extraction from collection solvent |
| WO1994013377A1 (en) * | 1992-12-11 | 1994-06-23 | Geert Feye Woerlee | Process and device for separating a mixture or extracting a material |
| JPH08154689A (en) * | 1994-12-06 | 1996-06-18 | Shin Nippon Kagaku Kogyo Kk | Method for purifying natural type abscisic acid |
| CN1125215A (en) * | 1995-05-30 | 1996-06-26 | 华东理工大学 | Process for making high explosive microgranula by using supercritical fluid devitrification method |
| JPH0952866A (en) * | 1995-08-09 | 1997-02-25 | Chlorine Eng Corp Ltd | Concentrated separation of fatty acid ester |
| CN1124591A (en) * | 1995-10-10 | 1996-06-19 | 金绍黑 | Supercritical CO2 extracting process for bad-smell-less garlicin |
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