TW201546263A - A method for microalgae cell walls lysis and one-step process of algal lipid extraction and esterification by a water-tolerable acidic ionic liquid - Google Patents

Abstract

The present invention provides a method for microalgae cell walls lysis and one-step process of algal lipid extraction and esterification by a water-tolerable acidic ionic liquid, and when the acidic ionic liquid in the solvent of methanol and hexane is utilized for the extraction of algal lipids, the esterification of the algal lipids is performed simultaneously; the acidic ionic liquid and the solvent of methanol and hexane can both be recycled for repeated use.

Description

Method for simultaneously esterifying algae oil by microalgae breaking and extracting oil with water-resistant acidic ionic liquid

The invention relates to a method for simultaneously esterifying algae oil with microalgae breaking and extracting oil by water-resistant acidic ionic liquid, in particular to using a water-resistant acidic ionic liquid to break the microalgae and catalyzing the esterification of the microalgae oil into an ester. Acid methyl ester; the acidic ionic liquid is hydrophilic, and can be automatically stratified with the oil phase of microalgae oil and fatty acid methyl ester, thereby achieving the purpose of wall breaking, oil extraction, esterification, oil-water phase separation.

Biomass fuel is the most promising renewable energy source to replace fossil energy in the future; biodiesel is one of the most commonly used biofuels, and its main component is fatty acid methyl ester (FAME, Fatty Acid Methyl Ester). It is prepared by esterification or transesterification of biomass (lipid). Microalgae is a good raw material for the production of quality diesel. Microalgae can synthesize the biomass (sugar, lipid, protein) required by sunlight, water and CO ₂ . Many microalgae have extremely high oil content in suitable culture conditions. Below, some oil content is as high as 50~70% of dry algae, and the fatty acid carbon number in microalgae oil is suitable for preparing biodiesel. Compared with plants, algae have the characteristics of high photosynthesis efficiency, strong environmental adaptability, short growth cycle and high biological yield. According to conservative estimates, micro-algae can produce 8,200-34,000 L of fat per hectare per year, while oil-rich plants such as palm and jatropha produce only 1,300-2,700 L of oil per hectare per year.

Because microalgae oil is mostly found in algal cells, and some oils are used with eggs. The form of lipoprotein or lipopolysaccharide bound by white matter or sugar exists, and algae cells are wrapped by relatively tough cell walls, making it difficult to extract the oil directly. Therefore, the algae body needs to be broken before the oil is extracted. Common methods are mainly divided into physical, chemical and biological breaking methods. After the microalgae cells are pretreated by some methods of breaking the wall, most of the oil is still stored in the cells, and the oil in the microalgae cells needs to be further extracted by a suitable method. At present, the commonly used methods for extracting microalgae oil are: organic solvent extraction method, supercritical extraction method, subcritical solvent method and coupled extraction technology.

Ionic liquids are salts which are structurally coupled by an organic cation to an anion which is liquid at room temperature. The organic cations of ionic liquids are usually organic nitrogen compounds, such as alkylamines, Alkylimidazoles, and Alkylpyridine organic nitrogen compounds. The anions can be various negatively charged molecules, such as BF ₄ ^- , PF ₆ ^- , Cl ^- , Br ^- , NO ₃ ^- , H ₂ PO ₄ ^- , HSO ₄ ^- etc.; ionic liquids have the following characteristics: (1) no vapor pressure; (2) high boiling point; 3) low toxicity; (4) solubility can be adjusted; (5) has polarity and conductivity, and is considered to be a green solvent. Ionic liquids have been used for extracting proteins from two-phase aqueous solutions, extracting hormones from urine, esterification of oils and fats, and solvents as biodegradable copolymers. In the Republic of China Patent No. I325862, it is mentioned that in the phosphorus oximation reaction, the oximation reaction, the sulfation reaction, the oximation reaction (except phosgenation), the use of an auxiliary base (containing pyridine and its derivatives) can be removed from the reaction mixture. In addition to the acid, the method uses an auxiliary base in combination with an acid (which may be hydrochloric acid, acetic acid, p-toluenesulfonic acid, methanesulfonic acid or trifluoromethanesulfonic acid) to form a salt which is a liquid ionic liquid at the reaction temperature and The solution in a suitable solvent may form a liquid phase which is immiscible with the valuable product or the valuable product acid.

Ionic liquids have been used in the extraction of microalgae oil. It has been studied to react with 1-ethyl-3-methyl imidazolium methyl sulfate ([EMIM]SO ₃ ) and methanol to form a co-solvent at 65 ° C. After 18 hours, the algae oil extract of freeze-dried Chlorella was raised from 11.23% to 38%; the ionic liquid against Duniella: a seawater algae without cell wall resistance and high osmotic pressure, algae oil The extraction rate decreased from 11.1% to 8.6% compared to the conventional rope extraction method (extracted with hexane). In this study, the effect of the type of EMIM co-solution on the extraction rate was also compared. The results were better with methanol and isopropanol.

Another study indicated that the algae oil extraction of chlorella (C. vulgaris) was carried out by using 1-butyl-3-methylimidazolium methyl sulfate ([BMIM]SO ₃ ) ionic liquid and [EMIM]SO ₃ -methanol co-solution. The 10.6% extraction rate of the Bligh and Dyer method (extracted with chloroform and methanol) was increased to 12.5% and 11.9%, respectively.

Recent studies using [EMIM]PO ₂ for 3% marine aquaculture wet algae (water content 95% w/w) can be used for wall-breaking oil extraction without heating at room temperature with the addition of chloroform, and ionic liquids can be reused up to 4 More than once.

When adding 25~100% of ionic liquid [EMIM]Cl in foreign patents Single-cell or multi-cellular algae with partial dehydration (water content 0~25%) can be broken at 150 °C. Algae oil and ionic liquid can be separated by automatic layering due to different hydrophobicity and hydrophilicity. Adding [EMIM]Cl ionic liquid to the cell wall microcellulose component of Chlorella pyreniodosa 1-20% can break the algae oil (triglyceride) at 105~140 °C. And the various ionic liquids of the imidazole derivative [EMIM]Ac, 1-methyl-3-octylimidazolium chloride[OMIM]Cl, 1-Hexyl-3-methylimidazolium chloride[HMIM]Cl, 1-Hexyl-3-methylimidazolium iodide[HMIM]I and [EMIM]CF3 against various microalgae (Tetraselmis sp.), Chlorella pyrenoidosa (Chlorella ellipsoidea, Chlorella vulgaris), brown algae (Laminaria digitata), The low temperature (below 50 ° C) broken wall extraction process of Nannochloropsis oculata, Sargassum muticum, and Scenedesmus dimorphus is also covered by patent protection.

The invention provides a method for simultaneously esterifying algae oil by microalgae breaking and extracting oil with water-resistant acidic ionic liquid, and the acidic ionic liquid can catalyze the esterification reaction of algae oil in the methanol-hexane solvent system, using the cable extraction device It can effectively extract algae oil and simultaneously esterify free fatty acids in algae oil into fatty acid methyl esters, and can effectively remove algal residue in oil or ionic liquid. The obtained low acid algae oil can be directly applied to the transesterification process. , production of fatty acid methyl ester (FAME, Fatty Acid Methyl Ester) biodiesel.

The invention provides a method for simultaneously esterifying algae oil by microalgae breaking and extracting oil with water-resistant acidic ionic liquid, and the steps are as follows:

(1) PPS (pyridinium propyl sulfobetaine) and Bronsted strong acid, such as sulfuric acid (H ₂ SO ₄ , SA), thionyl chloride (SOCl ₂ ) or alkanesulfonic acid (R-SO ₃ H a strong acid such as trifluoromethanesulfonic acid (CF ₃ SO ₃ H, TFMSA) and p-toluenesulfonic acid (p-CH ₃ -C ₆ H ₄ -SO ₃ H, P-TSA) at 60-90 ° C After stirring for 0.5 to 1 hour, a transparent and viscous water-resistant acidic ionic liquid is obtained, wherein the strong acid and the amphiphilic compound molar ratio are between 1.0 and 1.5.

(2) Mix 5~100% (w/w) acidic ionic liquid with wet algae, stir and heat at room temperature ~100 °C for 5~30 minutes, and break the wall of microalgae, which is the broken algae liquid.

(3) Transfer the broken algae liquid into the filter tube of the cable fat extractor, and extract and synchronize the reflux algal oil at 70~90 °C with 5~12 times the volume of algae solution in methanol-hexane solvent (1:1v/v). Esterification for 2 to 5 hours.

(4) After refluxing, the solution is allowed to stand layering. The upper layer is dissolved in hexane, and the lower layer is acidic ionic liquid dissolved in methanol and water. The upper layer and the lower layer are separately collected for vacuum distillation, and the upper layer can recover algae oil and hexane. The lower layer can recover methanol and acidic ionic liquid.

(5) The microalgae of the present invention refers to single-cell fresh water or seawater algae whose cell walls are cellulose, pectin and glycoprotein, such as Chlorella and Chlamydomonas. , Scenedesmus, Nannochloropsis, and Ettlia.

The wet algae system of the present invention refers to the microalgae after being cultured to 1-3 g/L, and then removing part of the water by centrifugation, filtration or natural sedimentation to reach an algae body having a concentration of 250-1000 g/L. The algae oil of the present invention means a mixture of oil-soluble components such as fatty acid methyl ester (FAME) and triglyceride (TAG). The water-resistant acidic ionic liquid of the invention has a wall-breaking oil extraction rate which is 1.1 to 3.8 times higher than that of the same concentration of Brunsten acid under the same conditions; and the esterification rate of the algae oil can reach 98.9%. The ionic liquid of the invention can be reused for more than four times, and only suffers from the accumulation of chlorophyll accumulation of microalgae when used repeatedly, and the rate of broken wall oil extraction decreases by 7-10% when recycled.

The detailed description of the preferred embodiments of the present invention is intended to be limited to the scope of the invention, and is not intended to limit the scope of the invention. The patent scope of this case.

In summary, this case is not only innovative in terms of space type, but also can enhance the above-mentioned multiple functions compared with the customary items. It should fully meet the statutory invention patent requirements of novelty and progressiveness, and apply for it according to law. This invention patent application, in order to invent, To the sense of virtue.

S11~S16‧‧‧Step process

Fig. 1 is a flow chart showing the method for simultaneously esterifying algae oil by microalgae breaking and oil extraction with water-resistant acidic ionic liquid according to the present invention.

The technical features, contents, and advantages of the present invention, as well as the advantages thereof, can be understood by the reviewing committee, and the present invention will be described in detail with reference to the accompanying drawings. The subject matter is only for the purpose of illustration and description. It is not intended to be a true proportion and precise configuration after the implementation of the present invention. Therefore, the scope and configuration relationship of the attached drawings should not be interpreted or limited. First described.

As shown in Fig. 1, a flow chart of a method for simultaneously esterifying algae oil by microalgae breaking and extracting oil with water-resistant acidic ionic liquid according to the present invention is as follows: S11: microalgae cultivation, which is self-operated and operated. Mixing and cultivating microalgae in the photoreactor, open pond, fermenter seawater, fresh water or wastewater. The concentration of microalgae at this time is 1~3g/L; S12: collecting algae, collecting microalgae, After centrifugation, filtration or sedimentation, the concentration of microalgae is 250~1000g/L; S13: microalgae breaks the wall, adding 5~100% PPS acidic ionic liquid, stirring at room temperature ~100 °C for 5~30 minutes; S14: Simultaneous esterification of algae oil extraction, refluxing with 70-90 times of methanol-hexane (1:1) in a volume of 5-12 times with a cable fat extractor and simultaneous esterification for 2-5 hours , separating algae residue (filter paper tube) S15: Separation of algae oil, the above liquid is allowed to stand layered, the upper layer is dissolved in hexane, the lower layer is ionic liquid dissolved in methanol and water; S16: solvent and ionic liquid are recovered, respectively, algae oil solution The ionic solution is subjected to vacuum distillation, and there are algal oils [FAMEs and triglycerides (TG), and methanol, hexane, water, and ionic liquids can be recycled.

Example 1: Comparison of water-resistant acidic ionic liquids on the wall-breaking oil extraction and simultaneous esterification rate of freshwater algae:

Experimental group (1):

According to the procedure mentioned in the embodiment, 2.02 g (0.01 mole) of PPS white solid was first placed in a round bottom bottle, 0.98 g (0.01 mole) of H ₂ SO ₄ (SA) was added dropwise, and stirred in a 60 ° C water bath. In minutes, a transparent, viscous ionic liquid is formed.

The freshwater cultured Chlorella sorokiniana was collected by centrifugation, and 10 g of wet algae (dry weight: about 0.8 to 1.1 g) was weighed, and the acidic ionic liquid prepared above was added thereto, and heated at 60 ° C for 250 min at 250 rpm to carry out microalgae. Broken wall. Then, all the mixture (including acidic ionic liquid) after the microalgae is broken is transferred to the cable extractor of the cable extractor, and 400 mL of the extracted esterification solvent (methanol: hexane = 1:1) is added, and the oil bath is 70-75 ° C. The algae oil and the esterification reaction are carried out by reflux extraction, and the esterification is carried out until the filter paper tube extract is colorless (about 2 to 5 hours), the heating extraction is stopped, and after cooling to room temperature, the upper layer liquid is separated by the separatory funnel (algae oil solution). In the hexane) and the lower layer (acid ionic liquid and water), the upper and lower layers are separated, and the solvent and water are separately concentrated under reduced pressure. The upper layer liquid can obtain the algal oil product, and the lower layer liquid can recover the acidic ionic liquid. The algae oil product was weighed and analyzed by gas chromatograph, and the oil extraction rate and esterification rate were calculated. The extraction rate and esterification rate are calculated as follows:

Oil extraction rate = (algal oil weight / dry algae weight) × 100%

Esterification rate = (FAME total weight / extraction oil weight) × 100%

Control group (1):

Weighing 10g of wet algae (dry weight about 0.8~1.1g), adding 5g of quartz sand (particle size 0.7mm) to the cell homogenizer at a speed of 6.5m / s for 15 seconds, a total of 10 times broken cell wall, using the experimental group (1) Algin oil extraction and esterification reaction was carried out in the same manner, and the results of the esterification reaction are shown in Table 1.

Control group (2):

In the same way as the experimental group (1), the algae breaking and extracting esterification reaction was carried out. However, the acidic ionic liquid was changed to concentrated sulfuric acid (98%) 0.98 g (0.01 mole). The final esterification reaction was shown in Table 1. in.

Experimental group (2)

In the same way as the experimental group (1), the algae breaking and extracting esterification reaction was carried out. However, the strong ionic liquid in the ionic liquid was changed to trifluoromethanesulfonic acid (CF ₃ SO ₃ H, TFMSA) 1.50 g ( 0.01 mole)). The results after the final esterification reaction are shown in Table 1.

Experimental group (3)

In the same way as the experimental group (1), the algae breaking and extraction and esterification were carried out. However, the strong ionic liquid in the ionic liquid was changed to p-CH ₃ -C ₆ H ₄ -SO. ₃ H, PTSA) 1.72 g (0.01 mole), and the results after the final esterification reaction are shown in Table 1.

Experimental group (4)

In the same way as the experimental group (1), the algae breaking and extracting esterification reaction were carried out. However, the strong acid in the acidic ionic liquid was changed to Thionyl chloride (SOCl ₂ ) 1.19 g (0.01 mole). The results of the final esterification reaction are shown in Table 1.

Experimental group (5)

In the same way as the experimental group (1), the algae breaking and extracting esterification reaction was carried out. However, after the acidic ionic liquid was added to the wet algae body, the mixture was heated and stirred at 90 ° C for 30 minutes, and the result of the esterification reaction was shown in the table. One.

Experimental group (6)

In the same manner as in the experimental group (1), the weight of the acidic ionic liquid was changed to 50% (w/w) of the wet algae weight, and the mixture was heated and stirred at 60 ° C for 30 minutes. The result of the esterification reaction was shown in the table. One.

According to the results of Table 1,

(1) Comparing the experimental group (1) with the control group (2), under the sulfuric acid containing the same molar number, the sulfated ionic liquid has a higher extraction rate and a catalytic esterification rate than sulfuric acid.

(2) Comparing experimental groups (1), (2), (3), (4), the oil extraction rate of the acidic ionic liquid containing the same molar number is TFMSA>SA>SOCl ₂ >PTSA; catalytic esterification rate For TFMSA>SOCl ₂ >SA>PTSA.

(3) Comparing the experimental group (1) and the experimental group (5), under the same concentration of sulfated ionic liquid, increasing the reaction temperature from 60 ° C to 90 ° C, can significantly improve the oil extraction rate and esterification rate of 98.9%.

(4) Comparing the experimental group (1) and the experimental group (6), at the same reaction temperature, increasing the addition amount of the sulfated ionic liquid from 20% (w/w) to 50% (w/w) can significantly increase the oil extraction rate. It reached 28.43% and the esterification rate reached 95.98%.

(5) Comparing the control group (1) and the experimental group (5), using 20% sulfuric acid ionic liquid for the microalgae wall-breaking oil extraction, the oil extraction rate is only 21.16%, which is slightly worse than the conventional homogenizer broken cell wall. However, the effect of the ionic liquid catalyzing the esterification reaction can increase the esterification rate by 98.9%.

Example 2: Comparison of the breakwater extraction and simultaneous esterification rate of seawater algae by different acidic ionic liquids: According to the reaction test procedure mentioned in the embodiment, centrifugation of seawater (containing 3% NaCl) after cultured Nannochloropsis sp.), weighed 10g of wet algae (dry weight about 1.9~2.1g), added 20% (w/w) of acidic ionic liquid, heated and stirred at 90°C for 250min, 30min, and moved to the cable extractor of the cable extractor. Add 300mL of extraction esterification solvent (methanol: hexane = 1:1), carry out reflux extraction and esterification to the filter paper tube colorless (about 2~5 hours), use the separatory funnel to divide the upper layer liquid (algae oil dissolved in The alkane and the lower liquid (acid ionic liquid and water) were respectively concentrated under reduced pressure to remove the solvent, and then the algae oil and the acidic ionic liquid were recovered; the results of the final esterification reaction are shown in Table 2. The oil extraction rate of different acidic ionic liquids containing the same molar number at 90 °C was PTSA>TFMSA>SA>SOCl ₂ ; the catalytic esterification rate was PTSA>SOCl ₂ >SA>TFMSA. This trend is different from the result of Example 1 freshwater algae. The extraction rate of algae oil and the esterification rate of algae oil are affected by the difference in cell wall composition of microalgae and the salt concentration of algae.

Example 3: Effect of repeated use of sulfuric acid ionic liquid on the oil extraction rate and esterification rate of freshwater algae: According to the reaction test procedure mentioned in the embodiment, collecting the oil and esterification of Chlorella sorokiniana After use, the lower layer of sulfuric acid ionic liquid is recovered, extracted by adding equal weight of hexane three times to remove residual algal oil, and concentrated under reduced pressure to remove methanol solvent and water, that is, recovery of sulfuric acid ionic liquid. According to the method of Example 1, 20% (w/w) sulfuric acid ionic liquid was added per 10 g of wet algae to carry out algae-breaking oil extraction, and the oil extraction rate and esterification rate were evaluated; the results showed that the ionic liquid can be reused four times or more. , When recycling, the efficiency of broken wall extraction can be maintained above 95%, and the esterification efficiency is almost unaffected.

The detailed description of the present invention is intended to be illustrative of a preferred embodiment of the invention, and is not intended to limit the scope of the invention. The patent scope of this case.

To sum up, this case is not only innovative in terms of technical thinking, but also has many of the above-mentioned functions that are not in the traditional methods of the past. It has fully complied with the statutory invention patent requirements of novelty and progressiveness, and applied for it according to law. Approved this invention patent application, in order to invent invention, to the sense of virtue.

S11~S16‧‧‧Step process

Claims (27)

The invention relates to a method for simultaneously esterifying algae oil by microalgae breaking and extracting oil with water-resistant acidic ionic liquid, the steps of which are as follows: microalgae breaking with a water-resistant acidic ionic liquid to form a first microalgae broken wall mixture; The first microalgae wall-breaking mixture is placed in a methanol and a first organic solvent to form a second microalgae wall-breaking mixture; the second microalgae wall-breaking mixture is subjected to reflux extraction and simultaneous esterification. After the reaction, filtration is performed to form an upper layer liquid and a lower layer liquid; and the upper layer liquid and the lower layer liquid are respectively subjected to vacuum distillation, and the algae oil and the first organic solvent are obtained from the upper layer liquid, and the lower layer liquid is obtained from the lower layer liquid. The methanol and the water resistant acidic ionic liquid. The method for esterifying algae oil by microalgae breaking and extracting oil with a water-resistant acidic ionic liquid according to the first aspect of the patent application, wherein the water-resistant acidic ionic liquid system utilizes an organic nitrogen-containing sulfonate-containing compound a compound, which is reacted with a Bronsted strong acid at 60-90 ° C for 1 hour to obtain a transparent viscous water-resistant acidic ionic liquid, wherein the sulfonic acid lactone-containing organic nitrogen-containing compound The Bronsted strong acid molar ratio is between 1.0 and 2.5. The method for esterifying algae oil by microalgae breaking and extracting oil with water-resistant acidic ionic liquid according to claim 1, wherein the first microalgae wall-breaking mixture is mixed with a wet algae body to resist water The ratio of acidic acidic ionic liquid is 5~100% (w/w), the heating temperature is between 50~180 °C, the stirring time is between 5~300 minutes, and the microalgae is broken. The method for esterifying algae oil by microalgae breaking and extracting oil with a water-resistant acidic ionic liquid according to the first aspect of the patent application, wherein the first microalgae is refluxed by oil extraction and simultaneous esterification reaction and filtration The broken wall mixture is transferred into the cable fat extractor filter paper (glass fiber material) to Adding 1 to 50 times the volume of the first microalgae wall mixture and the first organic solvent of 1 to 50 times the volume of the algae solution, refluxing and extracting at 50 to 90 ° C for 2 to 5 hours. The second microalgae wall-breaking mixture after refluxing and oil-removing and simultaneous esterification is left to be layered. The upper layer liquid is algae oil in the first organic solvent, and the lower layer liquid is dissolved in the water-resistant acidic ionic liquid. After separating the upper liquid and the lower liquid, the liquid is distilled under reduced pressure, and the upper liquid can obtain the algal oil and the recovered first organic solvent, and the lower liquid can obtain the methanol and the water resistance. Acidic ionic liquid. The method for esterifying algae oil by microalgae breaking and oil extraction with water-resistant acidic ionic liquid according to the second aspect of the patent application, wherein the organic nitrogen-containing compound in the organic nitrogen-containing compound containing sultone is It is an alkyl imidazole type (Alkylimidazole), an alkylpyridine type (Alkylpyridine) and an alkyl alkyl type (Alkylamine) nitrogen compound. The method for esterifying algae oil by microalgae breaking and extracting oil with a water-resistant acidic ionic liquid according to the second aspect of the patent application, wherein the strong acid of Brensted is thionyl chloride (SOCl _2). ), sulfuric acid (H ₂ SO ₄ ) or monoalkylsulfonic acid (R-SO ₃ H) Bronsted acid. a method for simultaneously esterifying algae oil with microalgae breaking and extracting oil with a water-resistant acidic ionic liquid according to the fifth aspect of the patent application, wherein the organic nitrogen-containing compound in the organic nitrogen-containing compound containing a sultone The alkyl group in the alkyl imidazole type (Alkylimidazole), the alkylpyridine type (Alkylpyridine) and the alkyl alkyl type (Alkylamine) nitrogen compound is C _m H _2m+1 , wherein the m system is from 1 to 18. A method for simultaneously esterifying algae oil with a water-resistant acidic ionic liquid, wherein the microalgae is broken and extracted with oil, as described in claim 5, wherein the sulfonate-containing organic nitrogen-containing compound is sultone The alkyl group is C _n H _2n , wherein n is 3-6. A method for simultaneously esterifying algae oil by microalgae breaking and oil extraction with a water-resistant acidic ionic liquid according to the fifth aspect of the patent application, wherein the alkanesulfonic acid (R-SO ₃ H) Bronsted acid system is Fluorosulfonic acid (FSO ₃ H), trifluoromethanesulfonic acid (CF ₃ SO ₃ H) and p-toluenesulfonic acid (p-CH ₃ -C ₆ H ₄ -SO ₃ H). The method for esterifying algae oil by microalgae breaking and extracting oil with water-resistant acidic ionic liquid according to claim 3, wherein the ratio of the water-resistant acidic ionic liquid mixed with the wet algae is further 20 to 70 %(w/w) is preferred. The method for esterifying algae oil by microalgae breaking and extracting oil with water-resistant acidic ionic liquid according to claim 3, wherein the wet algae body is mixed with the water-resistant acidic ionic liquid, and further added a second Organic solvents. The method for esterifying algae oil by microalgae breaking and oil extraction with a water-resistant acidic ionic liquid according to claim 11, wherein the second organic solvent is an alkane solvent (C _n H _2n+2 ) A cycloalkane solvent (C _n H _2n ) or a mixed organic solvent containing an alkane or a cycloalkane. A method for simultaneously esterifying algae oil by microalgae breaking and oil extraction with a water-resistant acidic ionic liquid as described in claim 12, wherein an alkane solvent (C _n H _2n+2 ) and a naphthenic solvent (C) _{The n in n} H _2n ) is _5-20 . The method for simultaneously esterifying algae oil by microalgae breaking and oil extraction with a water-resistant acidic ionic liquid according to claim 12, wherein the amount of the alkane solvent (C _n H _2n+2 ) in the second organic solvent is as described in claim 12 The system is between 10~100%. The method for esterifying algae oil by microalgae breaking and oil extraction with water-resistant acidic ionic liquid according to claim 12, wherein the amount of naphthenic solvent (C _n H _2n ) in the second organic solvent is Between 10~100%. Microalgae breaking and extraction with water-resistant acidic ionic liquid as described in item 3 of the patent application scope The method for simultaneously esterifying algae oil with oil, wherein the heating temperature is further preferably between 80 and 130 ° C. The method for esterifying algae oil by microalgae breaking and oil extraction with water-resistant acidic ionic liquid as described in claim 3, wherein the stirring time is preferably from 5 to 60 minutes. The method for esterifying algae oil by microalgae breaking and oil extraction with water-resistant acidic ionic liquid according to item 4 of claim 4, wherein the volume ratio of the methanol to the first microalgae wall-breaking mixture is between 5 ~30 is preferred. The method for simultaneously esterifying algae oil with microalgae breaking and extracting oil with water-resistant acidic ionic liquid according to claim 4, wherein the first organic solvent is an alkane solvent (C _n H _2n+2 ) A cycloalkane solvent (C _n H _2n ) or a mixed organic solvent containing an alkane or a cycloalkane. A method for simultaneously esterifying algae oil by microalgae breaking and oil extraction with a water-resistant acidic ionic liquid as described in claim 19, wherein an alkane solvent (C _n H _2n+2 ) and a cycloalkane solvent (C) _{The n in n} H _2n ) is 5 to 12. The method for simultaneously esterifying algae oil by microalgae breaking and oil extraction with a water-resistant acidic ionic liquid according to claim 19, wherein the amount of the alkane solvent (C _n H _2n+2 ) in the first organic solvent is as described in claim 19 The system is between 10~100%. The method for simultaneously esterifying algae oil by microalgae breaking and oil extraction with a water-resistant acidic ionic liquid according to claim 19, wherein the quantity of naphthenic solvent (C _n H _2n ) in the first organic solvent is Between 10~100%. The method for simultaneously esterifying algae oil with microalgae breaking and extracting oil with water-resistant acidic ionic liquid according to claim 4, wherein the first organic solvent and the first microalgae broken wall mixture The volume ratio is preferably between 5 and 30. The method for esterifying algae oil by microalgae breaking and extracting oil with water-resistant acidic ionic liquid according to claim 3, wherein the wet algae system is cellulose (cell) and pectin (cell). And single-cell freshwater or seawater algae of glycoprotein, which are Chlorella, Chlamydomonas, Scenedesmus, Nannochloropsis, and Ettlia. The method for esterifying algae oil by microalgae breaking and extracting oil with water-resistant acidic ionic liquid according to claim 3, wherein the wet algae system is self-operated, operated in a camp or mixed culture in a photoreactor Microalgae cultured in open ponds or fermenters. The method for esterifying algae oil by microalgae breaking and oil extraction with water-resistant acidic ionic liquid according to claim 3, wherein the wet algae system is microalgae obtained by culturing sea water, fresh water or waste water. The method for esterifying algae oil by microalgae breaking and extracting oil with water-resistant acidic ionic liquid according to claim 3, wherein the wet algae system is used for centrifugation, filtration or natural sedimentation of the cultured microalgae Part of the water, the wet algae body having a concentration of algae of 250 to 1000 g/L.