CN106554845A - A kind of method for extracting microalgae grease - Google Patents

A kind of method for extracting microalgae grease Download PDF

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CN106554845A
CN106554845A CN201510635029.1A CN201510635029A CN106554845A CN 106554845 A CN106554845 A CN 106554845A CN 201510635029 A CN201510635029 A CN 201510635029A CN 106554845 A CN106554845 A CN 106554845A
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microalgae
solution
inorganic salt
added
soap
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CN106554845B (en
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李晓姝
高大成
师文静
廖莎
孙启梅
王鹏翔
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Abstract

The invention discloses a kind of method for extracting microalgae grease, including(1)A certain amount of inorganic salt solution and aqueous slkali are added in the microalgae collected, radiant heating in microwave generator after mixing, is placed in, cell wall lysis is made, is crushed using the synergism of alkali, salt and microwave;(2)The fatty acid ester discharged from intracellular continues that saponification occurs with alkali, generates soap;(3)It is filtered to remove frustule fragment;(4)Inorganic salt solution is continuously added in system, is separated out soap, solid is collected by filtration;(5)Mineral acid is added in soap, is acidified, obtain free fatty, collect product fatty acid.The present invention extracts microalgae grease using Aqueous phase, with operating process is simple, microalgae grease high income, advantages of environment protection.

Description

A kind of method for extracting microalgae grease
Technical field
The present invention relates to a kind of method for extracting microalgae grease, relates in particular to a kind of method that employing Aqueous phase extracts microalgae grease.
Background technology
Microalgae is that a class is grown in water, and species is various and is distributed extremely extensive rudimentary plant.It is this kind of biological with efficient photosynthesis response system, CO can be passed through2Fixation, convert light energy into chemical energy, and be stored in somatic cell in the form of the Organic substance such as oils and fatss or starch.As the pressure and environmental problem of human society shortage of resources are increasingly serious, the exploitation of biodiesel and its part fossil energy substitute products is carried out using microalgae, it has also become the focus studied at present.
It is a complicated system engineering that production of biodiesel is carried out using microalgae, covers multiple sport technique segments, including several aspects such as the screening and cultivation of microalgae algae kind, the scale evaluation of microalgae and induction Lipid-producing, the collection of oils and fatss and processing.Microalgae starts from the sixties in 20th century as the research of biodiesel raw material, in recent years, with the development of biotechnology, by the biogenic reworking to algae kind, the abundant microalgae resource with high oil productive capacity is obtained, therefore this new production of biodiesel pattern has had application prospect very much.
Microalgae is used as a kind of novel biomass energy, but its advantage is it will be apparent that in its utilization, from the point of view of current progress, also in the starting stage.Current research is concentrated mainly on screening advantage algae kind, improve oily algae growth pressure, increase fat content in terms of, and the research to improving oils and fatss yield, setting up the aspects such as industrialized process for extracting is also little.However, for the research of microalgae, its final purpose is will to solve the problems, such as alternative energy source towards petrochemical industry, so the research for exploring efficient, to be suitable to large-scale production and application grease extraction should become the direction of a period research from now on.
The fat content difference of microalgae is very big; in variety classes; even bigger difference is there is also between same kind of different lines; some are easy to the algae kind of pilot scale culture; its fat content typically constitutes from the 20%~50% of dry cell weight; well below conventional oil crop, therefore some classical grease extractions are not suitable for the extraction of microalgae grease.CN200810240949.3 discloses one kind from microalgae while extracting oils and fatss and method of protein, and the method is adjusted pH value to alkalescence or alkalescence, the dissolution of breaking cellular wall, oils and fatss and the protein of microalgae cell is carried out by steam with wet algae mud as a raw material.The molten slurry of gained microalgae obtains oils and fatss and protein mixture after filtering off except cell residue, then carries out oil-water separation using cyclone hydraulic separators, obtains microalgae grease.Because the specific surface area of microalgae cell is very big, and the phospholipid composition content on cell membrane is very high, although therefore the method preparation process is simple, as a result of filter pretreatment mode, increased the loss rate of lubricant component.CN200910060589.3 discloses the extracting method of a kind of microbial grease and its short-link alcohol fatty acid ester, including:Adjust moisture:To obtain including the wet culture that the water content containing grease microorganism is 20~90%;Microwave treatment:The broken born of the same parents of microwave radiation are carried out to wet culture and makes water content be down to 5%~40%;Short chain alcohol process:The oils and fatss in partial alcoholysis microbial body in the presence of base catalyst, while oil and grease extracting;Recycling design:Make solid-liquid separation, and the mixture of microbial grease and short-link alcohol fatty acid ester is obtained Jing after short chain alcohol is reclaimed in evaporation.The method adds short chain alcoholic solvent to be processed after microalgae carries out the broken born of the same parents of microwave treatment, although the short chain alcoholic solvent has certain dissolution to breaking the cell membrane phospholipid layer after born of the same parents, but the effect of its alcohol dissolving is limited, and short chain alcohol mainly participates in base catalyzed reactions.
The content of the invention
For the deficiencies in the prior art, the invention provides a kind of method for extracting microalgae grease.The present invention extracts microalgae grease using Aqueous phase, with operating process is simple, microalgae grease high income, advantages of environment protection.
The method that the present invention extracts microalgae grease, including following content:
(1)A certain amount of inorganic salt solution and aqueous slkali are added in the microalgae collected, radiant heating in microwave generator after mixing, is placed in, cell wall lysis is made, is crushed using the synergism of alkali, salt and microwave;
(2)The fatty acid ester discharged from intracellular continues that saponification occurs with alkali, generates soap;
(3)It is filtered to remove frustule fragment;
(4)Inorganic salt solution is continuously added in system, is separated out soap, solid is collected by filtration;
(5)Mineral acid is added in soap, is acidified, obtain free fatty, collect product fatty acid.
Microalgae of the present invention may come from any oil-producing microalgae with accumulation oils and fatss, fatty acid ability, can such as be chlorella, diatom, red algae etc., especially chlorella or Wild Vitis species.It can also be microalgae mud that the microalgae of collection can be microalgae powder.
Step(1)Described in inorganic salt can be NaNO3、Na2CO3、NaHCO3, sodium ascorbyl phosphate, one or more in potassium phosphate etc., concentration is 0.01~0.03mol/L.Inorganic salt solution can be prepared using culture fluid detached with frustule after microalgae is collected.Described aqueous slkali can be the NaOH solution or KOH solution that mass concentration is 10%~30%.The microalgae of collection(Quality is in terms of dry weight)With the mass volume ratio (g of inorganic salt solution and aqueous slkali:Ml it is) 1:5~1:10, wherein inorganic salt solution and the volume ratio of aqueous slkali are 5:1~1:1.
Step(1)The power of described microwave generator be 5~20kW, microwave frequency may be selected 2450MHz or 915 MHz in one kind, 50~70 DEG C of radiant heating temperature, heat time heating time be 15~60min.
Step(3)The removing frustule fragment can adopt membrane filtration or centrifugal filtration.
Step(4)The inorganic salt and step(1)Middle addition it is consistent, can be unsaturated solution or saturated solution that concentration is 0.8~3mol/L, preferably inorganic salt saturated solution, addition and the microalgae collected(Quality is in terms of dry weight)Volume mass ratio (ml:G) it is 10:1~5:1.
Step(5)Described in mineral acid can be one or more in sulphuric acid, hydrochloric acid, nitric acid etc., be acidified to pH 1~4.Described to collect the method that fatty acid adopt centrifugation, after centrifugation, fatty acid is mutually preferably separated with water, phase product in collection.
Compared with prior art, the inventive method has the advantage that:
(1)Break process is carried out to microalgae cell by the way of saline solution and aqueous slkali combine, the addition of one side saline solution has autolysises to microalgae cell, the saponification of the opposing party's flour base can be such that frustule wall quickly dissolves, and salt can significantly improve frustule crushing effect with the synergism of alkali.
(2)The mixed system of microalgae, saline solution and aqueous slkali is heated using microwave radiation, as the presence of salt and alkali enhances the ability that system absorbs microwave, compared to traditional heating mode, the broken more thorough of cell can be caused, while oils and fatss yield is improved, shorten the response time, improve the utilization ratio of energy.
(3)By oils and fatss are transformed into salt and then the process for separating out first, oils and fatss are separated with other water-soluble macromolecule Organic substances and other impurities in frustule well, the extraction of oils and fatss is carried out with one step of purification, significantly reduce the load that early stage is processed when prepared by biodiesel.
(4)The inorganic salt that salting-out process is used is a kind of nutritive salt in micro-algae culture medium, and after saltouing, detached liquid is rich in inorganic nutrient salt, can continue reuse as the component of micro-algae culture medium.
The inventive method extracts microalgae grease using Aqueous phase, belongs to low energy consumption, environmentally friendly technology path, while having process is simple, it is easy to the characteristics of amplifying with oils and fatss high income.
Specific embodiment
The detailed process and effect that method is sent out to the present invention with reference to embodiment is illustrated, but is not limited to following examples.
In the present invention, oils and fatss yield=(product fatty acid quality/initial frustule dry weight) × 100%.Mass volume ratio of the present invention or volume mass are g than the unit of middle quality, and the unit of volume is ml.
Embodiment 1
Microalgae is chlorella(chlorella vulgaris), Jing 10L bioreactors culture 10 days, analyze at the end of culture frustule concentration be 1.82g/L(Dry weight meter).Take 5L microalgae liquid to be centrifuged, control centrifuge RPMs 4000rpm, centrifugation time 3min, obtain microalgae mud.The Na of 0.03mol/L is added in microalgae mud2CO3The sodium hydroxide solution 45ml of solution 45ml and 10%.Above-mentioned system is placed in microwave generator after mixing, microwave generator power 5kW is set, microwave frequency 2450MHz, 50 DEG C of heating-up temperature heat 20min, carry out the saponification of cell breakage and oils and fatss.Membrane aperture is used to be 10 afterwards-1μm micro-filtrate membrane filtration, remove frond cell, fragment.1mol/L is continuously added in liquid system Na2CO3Solution 90ml, separates out soap, solid is collected by filtration;Fatty acid salt solid is dissolved in a small amount of water, is added hydrochloric acid solution to be acidified to pH2.0, is obtained free fatty;By the system centrifugal treating, phase in collection, the acid of 3.17g product fatties is obtained, oils and fatss yield is 34.8%.
Embodiment 2
Microalgae is Wild Vitis species, Jing 10L bioreactors culture 10 days, analyze at the end of culture frustule concentration is 1.78g/L(Dry weight meter).Take 5L microalgae liquid to be centrifuged, control centrifuge RPMs 4000rpm, centrifugation time 5min, obtain microalgae mud, by microalgae mud drying, milled processed, obtain the micro- algae powders of 8.9g.The NaNO of 0.02mol/L is added in micro- algae powder3The sodium hydroxide solution 29ml of solution 58ml and 30%.Above-mentioned system is placed in microwave generator after mixing, microwave generator power 10kW is set, microwave frequency 915MHz, 55 DEG C of heating-up temperature heat 30min, carry out the saponification of cell breakage and oils and fatss.Membrane aperture is used to be 10 afterwards-1μm micro-filtrate membrane filtration, remove frond cell, fragment.The NaNO of 1.5mol/L is continuously added in liquid system3Solution 45ml, separates out soap, solid is collected by filtration;Fatty acid salt solid is dissolved in a small amount of water, is added hydrochloric acid solution to be acidified to pH 3.0, is obtained free fatty;By the system centrifugal treating, phase in collection, the acid of 3.34g product fatties is obtained, oils and fatss yield is 37.5%.
Embodiment 3
Microalgae is Wild Vitis species, Jing 10L bioreactors culture 10 days, analyze at the end of culture frustule concentration is 1.92g/L(Dry weight meter).Take 5L microalgae liquid to be centrifuged, control centrifuge RPMs 4000rpm, centrifugation time 5min, obtain microalgae mud, by microalgae mud drying, milled processed, obtain the micro- algae powders of 9.6g.The KH of 0.03mol/L is added in micro- algae powder2PO4The potassium hydroxide solution 40ml of solution 40ml and 10%.Above-mentioned system is placed in microwave generator after mixing, microwave generator power 15kW is set, microwave frequency 915MHz, 65 DEG C of heating-up temperature heat 40min, carry out the saponification of cell breakage and oils and fatss.Membrane aperture is used to be 10 afterwards-1μm micro-filtrate membrane filtration, remove frond cell, fragment.The KH of 1.5mol/L is continuously added in liquid system2PO4Solution 48ml, separates out soap, solid is collected by filtration;Fatty acid salt solid is dissolved in a small amount of water, adds hydrochloric acid solution to be acidified to pH 3.0, obtain free fatty;By the system centrifugal treating, phase in collection, the acid of 3.70g product fatties is obtained, oils and fatss yield is 38.5%.
Embodiment 4
Microalgae is chlorella, Jing 10L bioreactors culture 10 days, analyze at the end of culture frustule concentration is 1.93g/L(Dry weight meter).Take 5L microalgae liquid to be centrifuged, control centrifuge RPMs 4000rpm, centrifugation time 5min, obtain microalgae mud, by microalgae mud drying, milled processed, obtain the micro- algae powders of 9.65g.The K of 0.01mol/L is added in micro- algae powder2HPO4•3H2The potassium hydroxide solution 20ml of O solution 50ml and 20%.
Above-mentioned system is placed in microwave generator after mixing, microwave generator power 20kW is set, microwave frequency 915MHz, 70 DEG C of heating-up temperature heat 50min, carry out the saponification of cell breakage and oils and fatss.Membrane aperture is used to be 10 afterwards-1μm micro-filtrate membrane filtration, remove frond cell, fragment.The K of 1mol/L is continuously added in liquid system2HPO4••3H2O solution 60ml, separate out soap, solid are collected by filtration;Fatty acid salt solid is dissolved in a small amount of water, is added hydrochloric acid solution to be acidified to pH4.0, is obtained free fatty;By the system centrifugal treating, phase in collection, the acid of 3.52g product fatties is obtained, oils and fatss yield is 36.5%.
Embodiment 5
Microalgae chlorella, Jing 10L bioreactors culture 10 days, analyze at the end of culture frustule concentration be 1.82g/L(Dry weight meter).Take 5L microalgae liquid to be centrifuged, control centrifuge RPMs 4000rpm, centrifugation time 4min, obtain microalgae mud, by microalgae mud drying, milled processed, obtain the micro- algae powders of 9.1g.The NaH of 0.02mol/L is added in micro- algae powder2PO4The potassium hydroxide solution 20ml of solution 60ml and 25%.Above-mentioned system is placed in microwave generator after mixing, microwave generator power 20kW is set, microwave frequency 2450MHz, 60 DEG C of heating-up temperature heat 60min, carry out the saponification of cell breakage and oils and fatss.Membrane aperture is used to be 10 afterwards-1μm micro-filtrate membrane filtration, remove frond cell, fragment.The NaH of 3mol/L is continuously added in liquid system2PO4Solution 50ml, separates out soap, solid is collected by filtration;Fatty acid salt solid is dissolved in a small amount of water, is added hydrochloric acid solution to be acidified to pH2.5, is obtained free fatty;By the system centrifugal treating, phase in collection, the acid of 3.59g product fatties is obtained, oils and fatss yield is 39.4%.
Embodiment 6
Microalgae is diatom, Jing 10L bioreactors culture 10 days, analyze at the end of culture frustule concentration is 1.66g/L(Dry weight meter).Take 5L microalgae liquid to be centrifuged, control centrifuge RPMs 4000rpm, centrifugation time 3min, obtain 8.3g microalgae muds.The Na of 0.03 mol/L is added in microalgae mud2CO3The sodium hydroxide solution 10ml of solution 40ml and 10%.Above-mentioned system is placed in microwave generator after mixing, microwave generator power 18kW is set, microwave frequency 2450MHz, 55 DEG C of heating-up temperature heat 45min, carry out the saponification of cell breakage and oils and fatss.Membrane aperture is used to be 10 afterwards-1μm micro-filtrate membrane filtration, remove frond cell, fragment.The Na of 1.5mol/L is continuously added in liquid system2CO3Solution 83ml, separates out soap, solid is collected by filtration;Fatty acid salt solid is dissolved in a small amount of water, is added hydrochloric acid solution to be acidified to pH2.0, is obtained free fatty;By the system centrifugal treating, phase in collection, the acid of 2.89g product fatties is obtained, oils and fatss yield is 34.8%.
Embodiment 7
Microalgae is Wild Vitis species, Jing 10L bioreactors culture 10 days, analyze at the end of culture frustule concentration is 2.08g/L(Dry weight meter).Take 5L microalgae liquid to be centrifuged, control centrifuge RPMs 4000rpm, centrifugation time 3min, obtain microalgae mud.0.02 is added in microalgae mud The NaHCO of mol/L3The sodium hydroxide solution 25ml of solution 75ml and 15%.Above-mentioned system is placed in microwave generator after mixing, microwave generator power 14kW is set, microwave frequency 2450MHz, 45 DEG C of heating-up temperature heat 55min, carry out the saponification of cell breakage and oils and fatss.Membrane aperture is used to be 10 afterwards-1μm micro-filtrate membrane filtration, remove frond cell, fragment.The NaHCO of 0.8mol/L is continuously added in liquid system3Solution 100ml, separates out soap, solid is collected by filtration;Fatty acid salt solid is dissolved in a small amount of water, is added hydrochloric acid solution to be acidified to pH2.0, is obtained free fatty;By the system centrifugal treating, phase in collection, the acid of 3.33g product fatties is obtained, oils and fatss yield is 32.0%.
Embodiment 8
Na is added in liquid system after membrane filtration2CO3Saturated solution 90ml, separates out soap.Other conditions are with embodiment 1.The acid of 3.50g product fatties is obtained, oils and fatss yield is 38.5%.
Embodiment 9
NaNO is added in liquid system after membrane filtration3Saturated solution 45ml, separates out soap.Other conditions are with embodiment 2.The acid of 3.40g product fatties is obtained, oils and fatss yield is 38.7%.
Comparative example 1
In microalgae cell shattering process, after adding saline solution and aqueous slkali, do not adopt microwave radiation to heat, above-mentioned system is heated to into 50 DEG C, while stirring, keeps 20min, remaining is with embodiment 1.2.74g fatty acids are obtained, oils and fatss yield is 30.1%.
Comparative example 2
10% sodium hydroxide solution 90ml in microalgae cell shattering process, is only added in microalgae mud, saline solution is added without, remaining is with embodiment 1.2.38g fatty acids are obtained, oils and fatss yield is 26.2%.
Comparative example 3
With embodiment 1, but in microalgae cell shattering process, the Na of 0.03mol/L is only added in microalgae mud2CO3Solution 90ml, is not added with sodium hydroxide solution, above-mentioned system is placed in microwave generator after mixing, microwave generator power 5kW, microwave frequency 2450MHz, 50 DEG C of heating-up temperature are set, heating 20min, afterwards with the micro-filtrate membrane filtration that membrane aperture is 10-1 μm, removes frond cell, fragment.To in system, add hydrochloric acid solution to be acidified to pH 2.0, by the system centrifugal treating, phase in collection.Due to fatty acid ester, a part can occur hydrolysis generation fatty acid in acid condition, but hydrolysis is incomplete, so being the mixed phase of fatty acid ester and fatty acid in last upper phase, be not separated by, it is impossible to extract fatty acid.

Claims (11)

1. it is a kind of extract microalgae grease method, it is characterised in that including following content:
(1)A certain amount of inorganic salt solution and aqueous slkali are added in the microalgae collected, radiant heating in microwave generator after mixing, is placed in, cell wall lysis is made, is crushed using the synergism of alkali, salt and microwave;
(2)The fatty acid ester discharged from intracellular continues that saponification occurs with alkali, generates soap;
(3)It is filtered to remove frustule fragment;
(4)Inorganic salt solution is continuously added in system, is separated out soap, solid is collected by filtration;
(5)Mineral acid is added in soap, is acidified, obtain free fatty, collect product fatty acid.
2. method according to claim 1, it is characterised in that:Described microalgae comes from any with accumulation oils and fatss, the chlorella of fatty acid ability, diatom or red algae, and the microalgae of collection is microalgae powder or microalgae mud.
3. method according to claim 2, it is characterised in that:Described microalgae is chlorella or Wild Vitis species.
4. method according to claim 1, it is characterised in that:Step(1)Described in inorganic salt be NaNO3、Na2CO3、NaHCO3, sodium ascorbyl phosphate, one or more in potassium phosphate, concentration is 0.01~0.03mol/L.
5. method according to claim 1, it is characterised in that:Step(1)Described in aqueous slkali be NaOH solution or KOH solution that mass concentration is 10%~30%.
6. the method according to claim 1,4 or 5, it is characterised in that:Step(1)The microalgae of middle collection(Quality is in terms of dry weight)With inorganic salt solution and the mass volume ratio of aqueous slkali(g:ml)For 1:5~1:10, wherein inorganic salt solution and the volume ratio of aqueous slkali are 5:1~1:1.
7. method according to claim 1, it is characterised in that:Step(1)The power of described microwave generator is 5~20kW, and microwave frequency is 2450MHz or 915 MHz, and 50~70 DEG C of radiant heating temperature, heat time heating time are 15~60min.
8. method according to claim 1, it is characterised in that:Step(3)The removing frustule fragment can adopt membrane filtration or centrifugal filtration.
9. method according to claim 1, it is characterised in that:Step(4)The inorganic salt and step(1)Middle addition it is consistent, concentration is the unsaturated solution or saturated solution of 0.8~3mol/L, addition and the microalgae collected(Quality is in terms of dry weight)Volume mass ratio(ml:g)For 10:1~5:1.
10. method according to claim 1, it is characterised in that:Step(4)The inorganic salt solution adopts inorganic salt saturated solution.
11. methods according to claim 1, it is characterised in that:Step(5)Described in mineral acid be sulphuric acid, hydrochloric acid, one or more in nitric acid, be acidified to pH 1~4.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109499472A (en) * 2018-12-19 2019-03-22 浙江工业大学 A kind of Surface active biological material and preparation method thereof

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CN101586078A (en) * 2009-06-18 2009-11-25 南京工业大学 Scalization harvesting method and device for microalgae producing biological diesel oil
CN103045352A (en) * 2011-10-17 2013-04-17 中国石油化工股份有限公司 Extraction method of microalga grease
CN103396303A (en) * 2013-07-25 2013-11-20 浙江大学 Method for separating and purifying eicosapentaenoic acid and docosahexaenoic acid from micro-algal oil or fish oil

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Publication number Priority date Publication date Assignee Title
CN101586078A (en) * 2009-06-18 2009-11-25 南京工业大学 Scalization harvesting method and device for microalgae producing biological diesel oil
CN103045352A (en) * 2011-10-17 2013-04-17 中国石油化工股份有限公司 Extraction method of microalga grease
CN103396303A (en) * 2013-07-25 2013-11-20 浙江大学 Method for separating and purifying eicosapentaenoic acid and docosahexaenoic acid from micro-algal oil or fish oil

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109499472A (en) * 2018-12-19 2019-03-22 浙江工业大学 A kind of Surface active biological material and preparation method thereof

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