CN102553295A - Novel supercritical carbon dioxide extraction technology for continuously carrying out fine extraction on liquid raw materials - Google Patents
Novel supercritical carbon dioxide extraction technology for continuously carrying out fine extraction on liquid raw materials Download PDFInfo
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Abstract
The invention relates to a novel supercritical carbon dioxide extraction technology for continuously carrying out fine extraction on liquid raw materials. The liquid raw materials are filtered, have slag removed, and then are added into a container communicated to an extraction kettle; a random pressure and a random temperature are set in the range that the extraction pressure is higher than or equal to 7.3 MPa and the extraction temperature is higher than or equal to 3.2 DEG C; the flow of the liquid raw materials pumped into the extraction kettle from the container communicated to the extraction kettle is controlled and the flow rate of supercritical carbon dioxide pumped into the extraction kettle is regulated so as to change the ratio of supercritical liquid to a liquid sample to reach the optimal separation efficiency of different liquid samples and implement the continuous dynamic extraction; and fraction in a separation kettle is collected at regular time or continuously, so that corresponding extraction phases can be obtained; the extraction phases are absorbed by column chromatography fillers; and the extraction phases can be extracted by methods of changing the extraction pressure and the extraction temperature or changing the flow rate of the supercritical liquid or pumping a cosolvent and the like. According to the invention, the continuous supercritical carbon dioxide extraction of the liquid raw materials is implemented; the novel supercritical carbon dioxide extraction technology has the advantages of simple process flow, high repeatability, short process flow and wide application range, is convenient to operate, is green and has no pollution.
Description
Technical field
The present invention relates to a kind of supercritical CO 2 extraction technology, be meant a kind of supercritical carbon dioxide extraction method of new type of continuous quintessence liquid material especially.
Background technology
Supercritical liquid extraction technique is a kind of novel extraction and separation technology that rises the sixties in 20th century; Supercritical extraction technique (Supercritical Fluid Extraction; SFE) generally adopt carbon dioxide as extractant, have advantages such as technology is simple, organic solvent-free is residual, operating condition is gentle, survivable active ingredient.Its principle is to utilize unique solvability and the solubility of material in supercritical fluid of supercritical fluid to pressure, the highstrung characteristic of variation of temperature; Through intensification, step-down means (or both dual-purposes) institute's dissolved substances in the supercritical fluid is separated, reached and separate the purpose of purifying.
Conventional supercritical carbon dioxide extraction process flow cooperates shown in Figure 1, and it is specially:
Carbon dioxide comes out from carbon dioxide steel cylinder 1, removes by filter the impurity in the carbon dioxide through filter 2, through refrigerator 3; Temperature dropped to guarantee below 0 ℃ that carbon dioxide is liquid, through carbon dioxide membrane pump 4, constantly pumps into extraction kettle 6 with liquid carbon dioxide; Make liquid carbon dioxide pressure reach setting pressure (more than the 7.3MPa); This moment, the heating liquid carbon dioxide made its temperature reach design temperature (more than 31 ℃) through hot water machine 5; This moment, carbon dioxide reached supercriticality in extraction kettle 6; Become supercritical fluid---neither also on-gaseous of liquid state, under supercriticality, supercritical carbon dioxide had not only had the high osmosis of gas but also had had the highly dissoluble of liquid.Sample to be extracted in the extraction kettle 6 (solid or liquid), under the extraction of supercritical carbon dioxide, the active ingredient in the sample gets in the separating still 7 with supercritical carbon dioxide; Set the pressure and temperature of separating still 7; Make carbon dioxide not be in supercriticality, then dissolving active ingredient wherein just parses, and lodges in the separating still 7; Collect through valve 8; Carbon dioxide is then recycled again, and the active ingredient of treating sample in the extraction kettle 6 extracts when complete, need vary operation.
This shows this supercritical CO 2 extraction technology, exist the extraction kettle can't continued operation, cause the space-time yield of device lower, good solution is not arranged at present as yet; Mostly the cut that simultaneously traditional supercritical extract equipment extraction obtains is mixture, is more difficult to get the higher problems such as high value added product of purity, has seriously restricted the development of supercritical extraction technique.
Summary of the invention
The supercritical carbon dioxide extraction method that the purpose of this invention is to provide a kind of new type of continuous quintessence liquid material is realized continuous quintessence liquid charging stock, and this technology has production efficiency height, continous way production, simple, the also suitable large-scale production of environmental protection of technology.
For realizing above-mentioned purpose, solution of the present invention is:
A kind of supercritical carbon dioxide extraction method of new type of continuous quintessence liquid material, its concrete steps are:
Liquid charging stock in the said step 1 comprises various liquid natural extracts, industrial chemicals and goods, medical material and goods, raw-food material and goods and produces waste liquid.
Filler in the said step 2 is to realize that the chromatography that different chemical composition separates uses filler, comprises one or more mixing of adsorption chromatography filler, ion-exchange chromatography filler, hydrophobic interaction chromatography filler, immobilized metal ion afinity chromatography filler or affinity chromatograph filling.
Be after earlier the certain amount of fluid raw material being adsorbed with the column chromatography filler fully, to insert in the extraction kettle in the said step 2.
Be earlier the certain quantity of fluid raw material to be adsorbed with the column chromatography filler fully in the said step 2, insert in the extraction kettle, add an amount of column chromatography filler again.
Advantage of the present invention is: can realize continuous production, shorten the production cycle, reduce production costs; Green non-pollution; Technological process is simple, reliable; Can realize that efficient, selectivity obtains or remove the purpose of some composition.
The present invention is directed to this market status, column chromatographic technique on traditional supercritical extract appearance basis is developed a kind of novel continuous supercritical extraction technique.This technology combines the high efficiency and the column chromatography filler selection property fractionated of supercritical carbon dioxide extracting; Reach the purpose of quintessence, and have that extraction efficiency height, production efficiency are high, flow process is simple, characteristics such as no solvent residue, pollution-free, environmental protection.
Description of drawings
Fig. 1 is a supercritical carbon dioxide extracting equipment sketch map.
The specific embodiment
What the present invention disclosed is a kind of supercritical carbon dioxide extraction method of new type of continuous quintessence liquid material, cooperates shown in Figure 1ly, and specifically technology is:
After earlier the certain amount of fluid raw material being adsorbed with the column chromatography filler fully; Insert in the extraction kettle 6; Perhaps earlier the certain quantity of fluid raw material is adsorbed with the column chromatography filler fully; Insert in the extraction kettle 6, add an amount of column chromatography filler again, make the liquid charging stock and the amount of total column chromatography filler reach certain ratio; The liquid charging stock of in the container that leads to extraction kettle 9, packing into.
Carbon dioxide comes out from carbon dioxide steel cylinder 1, removes by filter the impurity in the carbon dioxide through filter 2, through refrigerator 3; Temperature dropped to guarantee below 0 ℃ that carbon dioxide is liquid; Through carbon dioxide membrane pump 4, liquid carbon dioxide is constantly pumped into extraction kettle 6, make liquid carbon dioxide pressure reach setting pressure (more than the 7.3MPa); This moment is through hot water machine 5; The heating liquid carbon dioxide makes its temperature reach design temperature (more than 31 ℃), and this moment, carbon dioxide reached supercriticality in extraction kettle 6.Simultaneously under the effect of high-pressure pump 10; The liquid charging stock that will lead in the container 9 of extraction kettle pumps into extraction kettle 6; Under the centrifugation of the extraction of supercritical carbon dioxide and column chromatography filler, the active ingredient in the sample gets in the separating still 7 with supercritical carbon dioxide, sets the pressure and temperature of separating still 7; Make carbon dioxide not be in supercriticality; Then dissolving active ingredient wherein just parses, and lodges in the separating still 7 and can collect in real time through valve 8, and carbon dioxide is then recycled again.So just can realize continuous extraction to fluid sample.
Concrete performing step of the present invention is: with the liquid charging stock filter cleaner, add and lead in the container of extraction kettle, liquid charging stock comprises various liquid natural extracts, industrial chemicals and goods, medical material and goods, raw-food material and goods and produces waste liquid; In extraction kettle, fill up the column chromatography filler; Filler is to realize that the chromatography that different chemical composition separates uses filler, comprises one or more mixing of adsorption chromatography filler, ion-exchange chromatography filler, hydrophobic interaction chromatography filler, immobilized metal ion afinity chromatography filler or affinity chromatograph filling.According to actual conditions, setting extracting pressure is >=7.3MPa that extraction temperature is any pressure and temperature of >=32 ℃.From the container that leads to extraction kettle, pump into the flow of extraction kettle through the control liquid charging stock; And the adjusting supercritical carbon dioxide pumps into the flow velocity of extraction kettle; Thereby change the ratio of supercritical fluid and fluid sample,, realize continuous dynamic extraction to reach optimal separation efficiency to the different liquids sample.Regularly or continuously collect the cut in the separating still, can obtain corresponding extraction phase, raffinate phase is then by the column chromatography filling adsorption.Through changing extracting pressure, temperature or supercritical fluid flow velocity or pumping into method such as entrainer, can raffinate phase be come together.
Free fatty in the rice bran oil and wax have a strong impact on the quality of rice bran oil, therefore need rice bran oil is dewaxed and the free-fat acid treatment.With slightly pressing in the container that rice bran oil is packed into extraction kettle communicates, in extraction kettle, fill up zeolite and compacting.Supercritical fluid is a carbon dioxide, and the setting extracting pressure is 50MPa, and extraction temperature is 70 ℃; Separating still pressure is 4.5 ~ 7MPa, and the separating still temperature is 75 ℃, carries out continuous extraction; Can be dewaxed and the rice bran oil of low free fatty, improved the applying value of rice bran oil.
Use the extraction of technology of the present invention and n-hexane method technology to compare about rice bran oil.
The wax that contains 2-4% in the rough rice bran oil, the free fatty of 1-2% phosphatide and 5-25%, pigment etc., this makes rough rice bran oil be difficult to purifying.And contain the large number of biological active component in the rough on the other hand rice bran oil, and like the characteristic component gamma oryzanol of rice bran oil, phytosterol, vitamin E, and in traditional subtractive process, these active components receive heavy damage.
| Project | Supercritical carbon dioxide extracting | The n-hexane method |
| Wax | 0.5~1% | 1.8~2.3% |
| Free fatty (FFA) | 1.0~4.0% | 5.0~8.0% |
| Oryzanol | 2.0~2.5% | 0.5~1.5% |
| Phytosterol | 1.5~2.0% | 1.0~1.6% |
| Vitamin E | 0.15~0.2% | 0.05~0.1% |
| Dissolvent residual | Do not have | Have |
Contain a large amount of terpenes compositions in the thick lemon that presses, it is prone to oxidized, influences the stability of lemon as food additives, and the lemon that therefore takes off terpene has better stability and market value.Pack into and can lead in the container of extraction kettle slightly pressing lemon, 40 ~ 60 purpose microsphere silica gel and the compactings of packing in the 2L extraction kettle.Supercritical fluid is a carbon dioxide, and the setting extracting pressure is 9MPa, and extraction temperature is 40 ℃, and the separating still temperature is that 45 ℃, pressure are 4.5MPa.Control essential oil raw material pumps into the flow of extraction kettle from the container that leads to extraction kettle, regulate the flow velocity that liquid carbon dioxide pump is gone into extraction kettle, and the velocity ratio that makes both is 4:1.Collect in the separating still this moment is mainly the terpenes composition in the lemon.After treating that silica gel absorption is saturated, changing extraction conditions is 20MPa, and extraction temperature is 40 ℃, under this technology, collect in the separating still obtain for taking off the terpene lemon, realize making with extra care to lemon.
Use the extraction of technology of the present invention and way of distillation technology to compare about taking off the terpene lemon:
| Project | Supercritical carbon dioxide | The way of distillation |
| The ratio of oxygenatedchemicals/hydrocarbon compound | 8-15 | 0.07-3 |
| Flavor component destroys | Seldom | More |
Contain the furocoumarin composition in the Bergamot, it can cause allergic even canceration, therefore will furocoumarin constituents wherein be removed.With furocoumarin content is that the thick Bergamot of 4541ppm is packed into and led in the container of extraction kettle, 60 ~ 80 purpose diatomite of packing in the 2L extraction kettle.Supercritical fluid is that carbon dioxide setting extracting pressure is 20MPa; Extraction temperature is 40 ℃; The separating still temperature is that 45 ℃, pressure are 4.5MPa; Control essential oil raw material pumps into the flow of extraction kettle from the container that leads to extraction kettle, regulate the flow velocity that liquid carbon dioxide pump is gone into extraction kettle, and the velocity ratio that makes both is 6:1.Under this technology, can obtain taking off the Bergamot of furocoumarin.
Taking off furocoumarin uses the extraction of technology of the present invention and solvent extraction technology to compare:
| Project | Supercritical carbon dioxide | Solvent extraction |
| Furocoumarin content | <200ppm | 200~1000ppm |
| Dissolvent residual | Do not have | Have |
Claims (5)
1. the supercritical carbon dioxide extraction method of a new type of continuous quintessence liquid material, its concrete steps are:
Step 1 places liquid charging stock in the container that can lead to extraction kettle;
Step 2, packed column chromatographic stuffing in extraction kettle;
Step 3 is set extraction conditions: extracting pressure >=7.3Mpa, and the carbon dioxide that makes of extraction temperature >=32 ℃ is in the condition of supercriticality;
Step 4; Through pump with being continuously pumped into extraction kettle in the container of liquid charging stock from step 1; In extraction kettle, liquid charging stock is under the effect of column chromatography filler and supercritical carbon dioxide, and the composition in the liquid sample is realized fractionated; The composition that is soluble in the supercritical carbon dioxide is preferentially flowed out from the extraction kettle top get into the separating still, the composition that is not soluble in the carbon dioxide then residues in the extraction kettle; Regularly or continuously collect extraction phase, thereby realize the continuous quintessence of fluid sample.
2. the supercritical carbon dioxide extraction method of a kind of new type of continuous quintessence liquid material according to claim 1 is characterized in that: the liquid charging stock in the said step 1 comprises various liquid natural extracts, industrial chemicals and goods, medical material and goods, raw-food material and goods and produces waste liquid.
3. the supercritical carbon dioxide extraction method of a kind of new type of continuous quintessence liquid material according to claim 1; It is characterized in that: the filler in the said step 2 is to realize that the chromatography that different chemical composition separates uses filler, comprises one or more mixing of adsorption chromatography filler, ion-exchange chromatography filler, hydrophobic interaction chromatography filler, immobilized metal ion afinity chromatography filler or affinity chromatograph filling.
4. according to the supercritical carbon dioxide extraction method of claim 1,2 or 3 described a kind of new type of continuous quintessence liquid materials, it is characterized in that: be after earlier the certain amount of fluid raw material being adsorbed with the column chromatography filler fully, to insert in the extraction kettle in the said step 2.
5. according to the supercritical carbon dioxide extraction method of claim 1,2 or 3 described a kind of new type of continuous quintessence liquid materials; It is characterized in that: be earlier the certain quantity of fluid raw material to be adsorbed with the column chromatography filler fully in the said step 2; Insert in the extraction kettle, add an amount of column chromatography filler again.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305343A (en) * | 2013-06-07 | 2013-09-18 | 佰香汇生物科技（厦门）有限公司 | Method for removing pesticide residue in citrus essential oil |
| CN106457064A (en) * | 2014-01-07 | 2017-02-22 | 科慕埃弗西有限公司 | Perfluoropolyether extraction processes |
| CN107400563A (en) * | 2017-09-20 | 2017-11-28 | 江苏福美景点开发有限公司 | For extracting the process units and its production method of fragrant plant composition |
| CN110055130A (en) * | 2019-03-06 | 2019-07-26 | 中国热带农业科学院农产品加工研究所 | A kind of preparation method and application of natural plants hydrosol |
| CN112764329A (en) * | 2019-10-21 | 2021-05-07 | 昆山晶科微电子材料有限公司 | Supercritical CO2Photoresist removing liquid and method for removing photoresist |
| CN113350827A (en) * | 2021-07-05 | 2021-09-07 | 广州市名花香料有限公司 | Fissistigma Oldhamii extractive solution and its preparation method |
| CN114717051A (en) * | 2022-03-28 | 2022-07-08 | 河北中烟工业有限责任公司 | Extraction method and analysis method of aroma components in coke flavor extract type tobacco flavor |
| CN117185596A (en) * | 2023-08-01 | 2023-12-08 | 河北工业大学 | Method for extracting nitrogen and phosphorus elements in sludge by supercritical carbon dioxide |
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| CN1665576A (en) * | 2002-07-03 | 2005-09-07 | 费罗公司 | Particles from supercritical fluid extraction of emulsion |
| CN102093321A (en) * | 2010-12-16 | 2011-06-15 | 厦门大学 | Device and method for separating orange oil from honey pomelo essential oil by supercritical fluid chromatography |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1665576A (en) * | 2002-07-03 | 2005-09-07 | 费罗公司 | Particles from supercritical fluid extraction of emulsion |
| CN102093321A (en) * | 2010-12-16 | 2011-06-15 | 厦门大学 | Device and method for separating orange oil from honey pomelo essential oil by supercritical fluid chromatography |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305343A (en) * | 2013-06-07 | 2013-09-18 | 佰香汇生物科技（厦门）有限公司 | Method for removing pesticide residue in citrus essential oil |
| CN103305343B (en) * | 2013-06-07 | 2015-02-18 | 佰香汇生物科技（厦门）有限公司 | Method for removing pesticide residue in citrus essential oil |
| CN106457064A (en) * | 2014-01-07 | 2017-02-22 | 科慕埃弗西有限公司 | Perfluoropolyether extraction processes |
| CN106457064B (en) * | 2014-01-07 | 2019-12-13 | 科慕埃弗西有限公司 | Perfluoropolyether extraction method |
| CN107400563A (en) * | 2017-09-20 | 2017-11-28 | 江苏福美景点开发有限公司 | For extracting the process units and its production method of fragrant plant composition |
| CN110055130A (en) * | 2019-03-06 | 2019-07-26 | 中国热带农业科学院农产品加工研究所 | A kind of preparation method and application of natural plants hydrosol |
| CN112764329A (en) * | 2019-10-21 | 2021-05-07 | 昆山晶科微电子材料有限公司 | Supercritical CO2Photoresist removing liquid and method for removing photoresist |
| CN113350827A (en) * | 2021-07-05 | 2021-09-07 | 广州市名花香料有限公司 | Fissistigma Oldhamii extractive solution and its preparation method |
| CN114717051A (en) * | 2022-03-28 | 2022-07-08 | 河北中烟工业有限责任公司 | Extraction method and analysis method of aroma components in coke flavor extract type tobacco flavor |
| CN114717051B (en) * | 2022-03-28 | 2023-09-08 | 河北中烟工业有限责任公司 | Extraction method and analysis method of aroma components in scorched aroma type extract tobacco flavor |
| CN117185596A (en) * | 2023-08-01 | 2023-12-08 | 河北工业大学 | Method for extracting nitrogen and phosphorus elements in sludge by supercritical carbon dioxide |
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Application publication date: 20120711 |