CN103695156A - Method of extracting microalgae oil by utilizing ultrasound to assist ionic liquid - Google Patents
Method of extracting microalgae oil by utilizing ultrasound to assist ionic liquid Download PDFInfo
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- CN103695156A CN103695156A CN201310618440.9A CN201310618440A CN103695156A CN 103695156 A CN103695156 A CN 103695156A CN 201310618440 A CN201310618440 A CN 201310618440A CN 103695156 A CN103695156 A CN 103695156A
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Abstract
The invention discloses a method of extracting microalgae oil by utilizing ultrasound to assist an ionic liquid. The method comprises the steps: with oil-containing microalgae as raw material, applying the ionic liquid, adding the microalgae into the ionic liquid, after ultrasound-assisted dissolving, adding water and an organic solvent, and carrying out extraction separation. An organic solvent-oil extraction layer is obtained from the upper layer of a liquid phase, and oil is obtained by distilling; the lower layer of the liquid phase is a mixture of the ionic liquid and water, and regeneration of the ionic liquid is achieved by evaporating water. According to the method, on one hand, the ionic liquid dissolves microalgae cell walls, the oil in the microalgae is allowed to be released, and the oil extraction rate can be significantly improved; and on the other hand, ultrasound has a crushing effect on microalgae cells, and in addition, ultrasonic vibration can accelerate movement of the ionic liquid and movement of an algae powder, so as to increase collision chances of the ionic liquid with the algae powder, thereby improving the oil extraction rate. Moreover, the method also has the advantages of mild separation conditions, and green environmental protection of the extraction solvent.
Description
Technical field
The present invention relates to technical field of biochemical industry, relate in particular to a kind of method of utilizing ultrasonic assisting ion liquid extraction microalgae grease.
Technical background
Clean fuel has become the direction of the necessary primary study of China and development.Biofuel is the clean renewable energy product-derived that is expected to obtain large-scale promotion application, is the pioneer field embodying in China's Renewable Energy Law.Due to what current countries in the world adopted, mostly be the raw materials such as oilseed plant, food crop, have that cost is high, growth cycle long and be subject to the features such as environmental restraint, the price that makes biofuel higher than or approach conventional diesel.Though and the recent raw material of China is sewer oil, raw materials cost is corresponding lower, but exist raw material to collect difficulty, supply the shortcomings such as limited, cause the damp production of current enterprise.Therefore, exploitation high yield, raw material is very urgent cheaply.It is high that algae has photosynthetic efficiency, the feature that adaptive capacity to environment is strong, growth cycle is short, biological yield is high, and in the long run, algae is preparation biofuel desirable feedstock.
The exploitation of micro-algae lipid resource mainly comprise cultivation, extraction, esterification and fatty acid compositional analysis etc., and the high efficiency of fat content embodies, and extracting method is crucial.Microalgae grease extracts the main method that adopts cytoclasis to combine with organic solvent extraction at present, often adopts organic solvent as extracting solvent, as methyl alcohol, acetone, ethyl acetate, chloroform etc.These solvents have larger volatility, can produce a large amount of organic vapors, not only cause environmental pollution, also the mankind's health are formed to great threat.The grease extraction yield of low-toxic solvent (ethanol, Virahol, butanols, normal hexane and ethyl acetate), compares with methyl alcohol combination with high toxicity chloroform, and grease extraction yield is relatively low.Therefore, actively find and develop the extensive common recognition that pollution green solvent little, easy recovery becomes vast extraction worker.
Ionic liquid (ionic liquids, ILs) claims again to consist of ionic liquid at room temperature organic cation and negatively charged ion, and yin, yang ion has many may combination, can design according to particular requirement.Different from organic solvent, there is doping region and nonpolar district in ionic liquid simultaneously, thereby organism, inorganics, biomacromolecule, gas etc. are had to better solvability, is widely used as reaction medium in chemical reaction.In extracting and separating field, ionic liquid due to its liquid wide ranges, non-volatile, structure can regulate and control, target compound is had to certain selectivity, being considered to a kind of alternative conventional solvent novel green can design mode solvent, has now become study hotspot.In the ionic liquid of studying at present, positively charged ion mainly be take glyoxaline cation as main, and it is main (Sun etc., 2010 that negatively charged ion mainly be take halide-ions and other inorganic acid ion (as tetrafluoroborate etc.); Pandey, 2006).
Ultrasonic extraction is a kind of physics shattering process, and ultimate principle is that thing effective constituent to be extracted is extracted in the strengthening of using ultrasound ripple.Ultrasonic wave mainly produces unique mechanical vibration and cavatition to medium.When ultrasonic vibration, can produce and propagate powerful energy, cause that medium particle enters vibrational state with fast speed and acceleration, medium structure is changed, impel limited composition to enter in solvent; In liquid, also cavatition can occur, have under suitable havoc stress, liquid internal forms cavitation bubble phenomenon simultaneously.In addition, the many second-order effects of ultrasonic wave as heating, emulsification, spread, smash, chemistry, biology, flocculating effect etc. also can accelerate thing effective constituent to be extracted diffusion dilution in solvent, promote its effective constituent fully and solvent, be conducive to extract.Wang Xueqing etc. have adopted multigelation and ultrasonic fragmentation fragmentation 17 kinds of microalgae cells, are beneficial to intracellular reactive material and extract, and cytoclasis result shows: through the supersound process of 12min, the percentage of damage of all experiment algae kinds is all more than 90%.Ultrasonic wave ancillary technique, as a kind of advanced person's extracting method, has the features such as simple and efficient to handle, extraction temperature is low, extraction yield is high, the structure of extract is not destroyed.
Summary of the invention
The object of the present invention is to provide a kind of green, extract efficiently the novel method of the lubricant component in micro-algae, provide a kind of and utilize ultrasonic assisting ion liquid to extract the method for grease in micro-algae.
The problem of bringing for fear of organic solvent extraction in prior art, the invention provides a kind of ultrasonic wave and ionic liquid and combines and extract the novel method of microalgae grease.Utilize ion liquid dissolving microalgae cell wall on the one hand, make the grease in microalgae cell or on cell walls be released out, can significantly improve the extraction yield of grease; On the other hand, utilize ultrasonic microalgae cell to be had to crushing effect, and ultrasonic vibration speeding-up ion liquid and the motion of algae powder, increase the chance that they collide mutually, thereby improve grease extraction yield.
The inventive method, comprises the following steps:
(1) algae powder is mixed with the mass ratio of ionic liquid by 1: 100～1: 3, then ultrasonic dissolution.
(2) add water and organic solvent extraction: to add the volume ratio of organic solvent and ionic liquid be 1: 1～1: 3, the volume ratio of water and organic solvent is 1: 3, stratification after vibration.
(3) liquid phase upper strata obtains organic solvent oil extraction layer, removes after organic solvent, obtains grease; Liquid phase lower floor is the mixture of ionic liquid and water, by evaporation, removes water, realizes the regeneration of ionic liquid.
Described in step (1), algae powder comes from oil-producing microalgae chlorella or grid algae.The condition of ultrasonic dissolution is is 20KHz in frequency, ultrasonic middle processing 0.5～4h of power 100～300W, and treatment temp is 50～110 ℃.Ionic liquid is selected from 1-ethyl-3-methylimidazole acetate ([Emim] CH
3cOO), or 1-butyl-3-methylimidazolium bromide ([Bmim] Br), chlorination 1-butyl-3-Methylimidazole ([Bmim] Cl), chlorination 1-allyl group-3-Methylimidazole ([Amim] Cl).
Described in step (2), organic solvent is selected from chloroform, normal hexane or sherwood oil.
Organic solvent recoverable described in step (3).
Advantage of the present invention is: the promoter action that the hyperacoustic cytoclasis of the method and oscillating action extract grease, and the stronger solubility property of ionic liquid, extract the grease in micro-algae, and extraction efficiency is high.Ion liquid dissolving microalgae cell wall, makes the grease in micro-algae be released out on the one hand, can significantly improve grease extraction yield; On the other hand, ultrasonic not only have crushing effect to microalgae cell, and ultrasonic vibration can also speeding-up ion liquid and the motion of algae powder, increases the chance that they collide mutually, thereby improve grease extraction yield.Meanwhile, the method also has separation condition gentleness, extracts the advantage of solvent environmental protection.
Accompanying drawing explanation
Fig. 1 is the inventive method process flow sheet
Embodiment
Below in conjunction with embodiment, the present invention will be further described:
Embodiment 1
Get 1g grid algae and join 50g1-ethyl-3-methylimidazole acetate ([Emim] CH
3cOO) in ionic liquid, be warming up to 50 ℃, ultrasonic power 20KHz, dissolve after 4h, add normal hexane and water (normal hexane and ionic liquid volume ratio are 1:1, and the volume ratio of water and organic solvent is 1: 3), solution left standstill layering, the precipitation that produces the compositions such as a small amount of microalgae cell wall, liquid phase upper strata is the normal hexane phase that contains grease, liquid phase lower floor is ionic liquid and water mixed phase.Take out upper solution, normal hexane is removed in distillation, obtains grease 0.43g; Ionic liquid and water mixed phase divide by dephlegmate, realize ionic liquid regeneration.
Embodiment 2
Getting 1g grid algae joins in 100g 1-butyl-3-methylimidazolium bromide (Br[Emim]) ionic liquid, be warming up to 80 ℃, ultrasonic power 20KHz, dissolve after 0.5h, add chloroform and water (chloroform and ionic liquid volume ratio are 1:3, and the volume ratio of water and organic solvent is 1: 3), solution left standstill layering, the precipitation that produces the compositions such as a small amount of microalgae cell wall, liquid phase upper strata is the chloroform phase that contains grease, liquid phase lower floor is ionic liquid and water mixed phase.Take out upper solution, chloroform is removed in distillation, obtains grease 0.28g; Ionic liquid and water mixed phase divide by dephlegmate, realize ionic liquid regeneration.
Embodiment 3
Get 1g chlorella and join 3g1-ethyl-3-methylimidazole acetate ([Emim] CH
3cOO) in ionic liquid, be warming up to 110 ℃, ultrasonic power 20KHz, dissolve after 2h, add a certain amount of normal hexane and water (normal hexane and ionic liquid volume ratio are 1:2, and the volume ratio of water and organic solvent is 1: 3), solution left standstill layering, the precipitation that produces the compositions such as a small amount of microalgae cell wall, liquid phase upper strata is the normal hexane phase that contains grease, liquid phase lower floor is ionic liquid and water mixed phase.Take out upper solution, normal hexane is removed in distillation, obtains grease 0.23g; Ionic liquid and water mixed phase divide by dephlegmate, realize ionic liquid regeneration.
Embodiment 4
Get 1g chlorella and join 60g chlorination 1-allyl group-3-Methylimidazole (in [Amim] Cl ionic liquid, be warming up to 70 ℃, ultrasonic power 20KHz, dissolve after 2h, add a certain amount of sherwood oil and water (sherwood oil and ionic liquid volume ratio are 1:2, and the volume ratio of water and organic solvent is 1: 3), solution left standstill layering, the precipitation that produces the compositions such as a small amount of microalgae cell wall, liquid phase upper strata is the sherwood oil phase that contains grease, liquid phase lower floor is ionic liquid and water mixed phase.Take out upper solution, sherwood oil is removed in distillation, obtains grease 0.41g; Ionic liquid and water mixed phase divide by dephlegmate, realize ionic liquid regeneration.
Embodiment 5
Get 1g grid algae and join 3g chlorination 1-butyl-3-Methylimidazole (in [Bmim] Cl ionic liquid, be warming up to 50 ℃, ultrasonic power 20KHz, dissolve after 0.5h, add a certain amount of sherwood oil and water (sherwood oil and ionic liquid volume ratio are 1:3, and the volume ratio of water and organic solvent is 1: 3), solution left standstill layering, the precipitation that produces the compositions such as a small amount of microalgae cell wall, liquid phase upper strata is the sherwood oil phase that contains grease, liquid phase lower floor is ionic liquid and water mixed phase.Take out upper solution, sherwood oil is removed in distillation, obtains grease 0.15g; Ionic liquid and water mixed phase divide by dephlegmate, realize ionic liquid regeneration.
Claims (5)
1. utilize ultrasonic assisting ion liquid from micro-algae, to extract a method for grease, it is characterized in that, said method comprising the steps of:
(1) algae powder is mixed with the mass ratio of ionic liquid by 1: 100～1: 3, then ultrasonic dissolution;
(2) add water and organic solvent extraction: to add the volume ratio of organic solvent and ionic liquid be 1: 1～1: 3, the volume ratio of water and organic solvent is 1: 3, stratification after vibration;
(3) liquid phase upper strata obtains organic solvent oil extraction layer, removes after organic solvent, obtains grease; Liquid phase lower floor is the mixture of ionic liquid and water, by evaporation, removes water, realizes the regeneration of ionic liquid.
2. according to claim 1ly utilize ultrasonic assisting ion liquid from micro-algae, to extract the method for grease, it is characterized in that, described in step (1), algae powder comes from oil-producing microalgae chlorella or grid algae.
3. according to claim 1ly utilize ultrasonic assisting ion liquid from micro-algae, to extract the method for grease, it is characterized in that, in step (1), the condition of ultrasonic dissolution is to be 20KHz in frequency, ultrasonic middle processing 0.5～4h of power 100～300W, and treatment temp is 50～110 ℃.
4. according to claim 1ly utilize ultrasonic assisting ion liquid from micro-algae, to extract the method for grease, it is characterized in that, the described ionic liquid of step (1) is selected from 1-ethyl-3-methylimidazole acetate, or 1-butyl-3-methylimidazolium bromide, chlorination 1-butyl-3-Methylimidazole, chlorination 1-allyl group-3-Methylimidazole.
5. according to claim 1ly utilize ultrasonic assisting ion liquid from micro-algae, to extract the method for grease, it is characterized in that, the organic solvent described in step (2) is selected from chloroform or normal hexane, sherwood oil.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104531343A (en) * | 2014-12-19 | 2015-04-22 | 中国科学院广州能源研究所 | Method for combined extraction of microalgal oil by employing methanol and ionic liquid |
| CN105132404A (en) * | 2015-10-12 | 2015-12-09 | 山东大学 | Method for fast accumulating grease through ultrasonic stimulation micro algae |
| CN106306118A (en) * | 2015-06-15 | 2017-01-11 | 财团法人食品工业发展研究所 | Preparation method of blend oil containing fat-soluble functional component |
| CN106318619A (en) * | 2015-06-30 | 2017-01-11 | 财团法人工业技术研究院 | Method for extracting grease in algae |
| CN107129860A (en) * | 2017-05-11 | 2017-09-05 | 韶关学院 | A kind of extracting method of microalgae grease |
| CN107266308A (en) * | 2017-07-20 | 2017-10-20 | 广西南宁桂知科技有限公司 | The technique that a kind of utilization longan pericarp prepares protocatechuic acid |
| CN107488501A (en) * | 2017-09-21 | 2017-12-19 | 嘉必优生物技术（武汉）股份有限公司 | Microbe-derived polyunsaturated fatty acid grease and its preparation technology |
| CN107586959A (en) * | 2017-09-11 | 2018-01-16 | 陕西科技大学 | Utilize the method for heavy metal in intensified by ultrasonic wave functional ionic liquids extraction water |
| CN108034499A (en) * | 2017-12-22 | 2018-05-15 | 江南大学 | A kind of method of fragrant camphor tree essential oil using ionic liquid as green medium Extraction and enrichment 1,8- Cineoles |
| CN108485818A (en) * | 2018-05-25 | 2018-09-04 | 西南石油大学 | A kind of method of microwave radiation technology ionic liquid extract kitchen garbage solid phase waste oil |
| CN109321354A (en) * | 2018-11-13 | 2019-02-12 | 天津大学 | A kind of method of aqueous enzymatic extraction microalgae grease |
| CN110408466A (en) * | 2019-08-05 | 2019-11-05 | 福建福瑞康信息技术有限公司 | A kind of method of enzyme assisting ion liquid extraction microalgae grease |
| CN113322186A (en) * | 2021-06-21 | 2021-08-31 | 昆明理工大学 | Method for rapidly harvesting microalgae by using ionic liquid |
| CN116211975A (en) * | 2022-12-14 | 2023-06-06 | 中国热带农业科学院热带作物品种资源研究所 | Preparation method of semen Alpiniae extract and application of semen Alpiniae extract in inhibiting listeria monocytogenes |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104531343A (en) * | 2014-12-19 | 2015-04-22 | 中国科学院广州能源研究所 | Method for combined extraction of microalgal oil by employing methanol and ionic liquid |
| CN106306118A (en) * | 2015-06-15 | 2017-01-11 | 财团法人食品工业发展研究所 | Preparation method of blend oil containing fat-soluble functional component |
| CN106318619B (en) * | 2015-06-30 | 2019-10-11 | 财团法人工业技术研究院 | Method for extracting grease in algae |
| CN106318619A (en) * | 2015-06-30 | 2017-01-11 | 财团法人工业技术研究院 | Method for extracting grease in algae |
| CN105132404A (en) * | 2015-10-12 | 2015-12-09 | 山东大学 | Method for fast accumulating grease through ultrasonic stimulation micro algae |
| CN107129860A (en) * | 2017-05-11 | 2017-09-05 | 韶关学院 | A kind of extracting method of microalgae grease |
| CN107266308A (en) * | 2017-07-20 | 2017-10-20 | 广西南宁桂知科技有限公司 | The technique that a kind of utilization longan pericarp prepares protocatechuic acid |
| CN107586959A (en) * | 2017-09-11 | 2018-01-16 | 陕西科技大学 | Utilize the method for heavy metal in intensified by ultrasonic wave functional ionic liquids extraction water |
| CN107586959B (en) * | 2017-09-11 | 2018-11-30 | 陕西科技大学 | Utilize the method for heavy metal in intensified by ultrasonic wave functional ionic liquids extraction water |
| CN107488501A (en) * | 2017-09-21 | 2017-12-19 | 嘉必优生物技术（武汉）股份有限公司 | Microbe-derived polyunsaturated fatty acid grease and its preparation technology |
| CN108034499A (en) * | 2017-12-22 | 2018-05-15 | 江南大学 | A kind of method of fragrant camphor tree essential oil using ionic liquid as green medium Extraction and enrichment 1,8- Cineoles |
| CN108485818A (en) * | 2018-05-25 | 2018-09-04 | 西南石油大学 | A kind of method of microwave radiation technology ionic liquid extract kitchen garbage solid phase waste oil |
| CN109321354A (en) * | 2018-11-13 | 2019-02-12 | 天津大学 | A kind of method of aqueous enzymatic extraction microalgae grease |
| CN110408466A (en) * | 2019-08-05 | 2019-11-05 | 福建福瑞康信息技术有限公司 | A kind of method of enzyme assisting ion liquid extraction microalgae grease |
| CN113322186A (en) * | 2021-06-21 | 2021-08-31 | 昆明理工大学 | Method for rapidly harvesting microalgae by using ionic liquid |
| CN116211975A (en) * | 2022-12-14 | 2023-06-06 | 中国热带农业科学院热带作物品种资源研究所 | Preparation method of semen Alpiniae extract and application of semen Alpiniae extract in inhibiting listeria monocytogenes |
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Application publication date: 20140402 |