WO2015184629A1

WO2015184629A1 - Method for breaking microalgal walls and extracting oil while simultaneously esterfying algal oil with water-tolerant acidic ionic liquid

Info

Publication number: WO2015184629A1
Application number: PCT/CN2014/079324
Authority: WO
Inventors: 曾雅秀; 黄铭郁; 吴荣宗; 周金言
Original assignee: 台湾中油股份有限公司
Priority date: 2014-06-06
Filing date: 2014-06-06
Publication date: 2015-12-10

Abstract

Disclosed is a method for breaking microalgal walls while extracting oil and simultaneously esterfying algal oil with a water-tolerant acidic ionic liquid. This acidic ionic liquid is utilized to extract an algal oil in a methanol-hexane solvent, and at the same time, to perform a process for esterfying the algal oil; and the acidic ionic liquid and the methanol-hexane solvent in the process can both be recycled and re-used.

Description

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

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

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. 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 (saccharides, lipids, proteins) required by sunlight, water and C0 ₂ . Many microalgae have high oil content, suitable for cultivation. Under the conditions, 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 has 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 oil per hectare per year, while oil-rich plants such as palm and jatropha produce only 1,300-2,700 L per hectare.

Since microalgae oil is mostly present in algal cells, and some oils are present in the form of lipoproteins or lipopolysaccharides bound to proteins or sugars, 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 wall 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 is extracted by a suitable method. At present, the commonly used microalgae oil extraction methods include: organic solvent extraction method, supercritical extraction method, subcritical solvent method and coupled extraction technology.

Ionic liquids are structurally composed of an organic cation and an anion Coupled salts, which are liquid at room temperature. The organic cations of ionic liquids are usually organic nitrogen compounds, such as alkylamine, Alkylimidazole, Alkylpyridine organic nitrogen compounds, and anions can be various negatively charged molecules. Such as BF ₄ —, PF ₆ —, CI—, Br—, N0 ₃ —, H ₂ P0 ₄ —, HS0 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) polarity and conductivity, and is considered to be a green solvent. Ionic liquids have been used to extract proteins from two-phase aqueous solutions, from urine. Extracting hormones from liquids, esterification of oils and fats, and solvents as biodegradable copolymers. In the Republic of China Patent No. 1325862, it is mentioned that in the phosphorylation reaction, the silicon oximation reaction, the sulfurization reaction, and the acylation reaction (except phosgenation), an auxiliary base (containing pyridine and its derivative) can be used in the self-reactive mixture. The acid is removed. The method uses an auxiliary base in combination with an acid (which may be hydrochloric acid, acetic acid, p-toluenesulfonic acid, formamidinesulfonic acid or trifluoromethanesulfonic acid) to form a salt which is a liquid ionic liquid at the reaction temperature. And in a solution in a suitable solvent, a valuable product or a valuable product acid can be formed into a liquid phase which is immiscible.

Ionic liquids have been used in the extraction of microalgae algae oil. It has been studied that l-ethyl-3-methyl imidazolium methyl sulfate ([EMIM]S0 ₃ ) and methanol can be co-solvent at 65°. After 18 hours of C reaction, 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 permeability The algae oil 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 pointed out that the algae oil extraction of chlorella (C. vulgaris) was carried out by using l-butyl-3-methylimidazolium methyl sulfate ([BMIM]S0 ₃ ) ionic liquid and [EMIM]S0 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]P0 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 the ionic liquid can be reused up to 4 times. the above.

In foreign patents, it is mentioned that when the ionic liquid [EMIM]CI is added by 25~100%, the single-cell or multi-cellular algae with partial dehydration (water content 0~25%) can be broken at 15CTC. Algae oil and ionic liquids can be separated by automatic separation due to differences in hydrophobicity and hydrophilicity. The [EMIM]CI ionic liquid is added to the cell wall microcellulose component of the Chlorella pyreniodosa algae at 1-20%, and the algal oil (triglyceride) is separated at 105-140 °C. And the ionic liquid of the imidazole derivative [EMIM]Ac, l-methyl-3-octylimidazolium chloride [0MIM]CI, l-Hexyl-3-methylimidazolium chloride [HMIM]CI, l-Hexyl-3-methylimidazolium iodide [HMIM ]I and [EMIM]CF3 for various microalgae Tetraselmis sp., Chlorella pyrenoidosa, Chlorella ellipsoidea, Chlorella vulgaris, Laminaria digitata, Nannochloropsis oculata, jellyfish The low temperature (below 50 °C) wall-breaking oil extraction process of Sargassum muticum and Scenedesmus dimorphus is also covered by patent protection. Summary of the invention

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 methanol-hexane solvent in the algae oil, using the cable type The extraction device can effectively extract the algae oil and esterify the free fatty acid in the algae oil into a fatty acid methyl ester, and can effectively remove the algal residue in the oil or ionic liquid, and the obtained low acid algae oil can be directly applied to the rotation. Esterification process to produce fatty acid methyl ester (FAME, Fatty Acid Methyl Ester).

A method for simultaneously esterifying algae oil with a water-resistant acidic ionic liquid for microalgae breaking and oil extraction, and the steps are as follows:

The microalgae is broken by a water-resistant acidic ionic liquid to form a first microalgae wall-breaking 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 oil extraction and homo-esterification reaction, followed by filtration to form an upper layer liquid and a lower layer liquid;

The supernatant liquid and the lower layer liquid are separately distilled under reduced pressure, and the algae oil and the first organic solvent are obtained from the supernatant liquid, and the methanol and the water-resistant acidic ionic liquid are obtained from the lower layer liquid. The water-resistant acidic ionic liquid is obtained by using a sulfonate-containing organic nitrogen-containing compound and a Bronsted strong acid at 60 to 90 ° C for 1 hour to obtain a transparent viscous state. A water-resistant acidic ionic liquid, wherein the sulfonate-containing organic nitrogen-containing compound and the Bronsted strong acid molar ratio are between 1.0 and 2.5.

The first microalgae wall-breaking mixture is a mixture of the water-resistant acidic ionic liquid in a wet algae body, the mass ratio is 5 to 100%, the heating temperature is between 50 and 180 ° C, and the stirring time is between 5 and 300. Minutes, the microalgae broke.

Wherein the refluxing oil extraction and the homologous esterification reaction and filtration are carried out by moving the first microalgae broken wall mixture into a glass fiber material of a cable fat extractor filter paper to add 1 to 50 times the first microalgae to be broken. The volume of the wall mixture and the first organic solvent in a volume of 1 to 50 times the algae solution are refluxed at 50-90 ° C for 2 to 5 hours; the reflux oil extraction and the same The second microalgae wall-breaking mixture after esterification is left to be layered, the upper layer liquid is the first organic solvent of algae oil, and the lower layer liquid is dissolved in the methanol and water by the water-resistant acidic ionic liquid; After the upper liquid and the lower liquid are separated, respectively, vacuum distillation is performed, 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 resistant acidic ionic liquid.

The organic nitrogen-containing compound in the sulfonic acid lactone-containing organic nitrogen-containing compound is a nitrogen compound of Alkylimidazole, Alkylpyridine and Alkylamine.

Wherein the strong acid of Brunstr is sulfoxide (Thionyl chloride, S0C1 ₂ ), sulfuric acid (H ₂ S0 ₄ ) or monoterpene sulfonic acid (R-S0 ₃ H) Bronsted acid.

The sulfhydryl group of the Alkylimidazole, Alkylpyridine and Alkylamine nitrogen compounds of the organic nitrogen-containing compound in the sulfonic acid lactone-containing organic nitrogen-containing compound is C _m H _2m+1 , where m is from 1 to 18.

The sulfonate group of the sulfonate-containing organic nitrogen-containing compound has a sulfonate group of C _n H _2n , wherein _n is from 3 to 6.

Wherein the sulfonic acid (R-S0 ₃ H) Bronsted acid is fluorosulfonic acid (FS0 ₃ H), trifluoromethanesulfonic acid (CF ₃ S0 ₃ H) and p-toluenesulfonic acid (p-CH) ₃ -C ₆ H ₄ -S0 ₃ H).

Preferably, the wet algae body is mixed with the water-resistant acidic ionic liquid by a mass ratio of 20 to 70%. The wet algae body is mixed with the water-resistant acidic ionic liquid, and a second organic solvent is further added.

The second organic solvent is an anthracene hydrocarbon solvent (C _n H _2n+2 ), a cyclic anthraquinone hydrocarbon solvent (C _n H _2n ), or a mixed organic solvent containing an anthracene hydrocarbon or a cyclic anthracene hydrocarbon.

Wherein the hydrocarbon solvent embankment _{(211 + 2} ^ 0) and the ring embankment hydrocarbon solvent (C _n H _2n) where n is -5 to

20.

The amount of the terpene hydrocarbon solvent (0^ ₂ . ₊₂ ) in the second organic solvent is between 10% and 100%.

The amount of the cyclic anthraquinone solvent (C _n H _2n ) in the second organic solvent is between 10% and 100%.

The heating temperature is preferably further between 80 and 130 ° C.

The stirring time is preferably between 5 and 60 minutes.

The volume ratio of the methanol to the first microalgae wall-breaking mixture is preferably between 5 and 30. The first organic solvent is a hydrazine hydrocarbon solvent (C _n H _2n+2 ), a cyclic hydrazine hydrocarbon solvent (C _n H _2n ), or a mixed organic solvent containing an anthracene hydrocarbon or a cyclic hydrazine hydrocarbon.

12.

The amount of the terpene hydrocarbon solvent (0^ ₂ . ₊₂ ) in the first organic solvent is between 10% and 100%.

The amount of the cyclic hydrazine hydrocarbon solvent (0^ ₂ ) in the first organic solvent is between 10% and 100%.

Wherein the volume ratio of the first organic solvent to the first microalgae wall-breaking mixture is

5-30 is preferred.

The wet algae body is a single-cell freshwater or seawater algae whose cell walls are cellulose, pectin and glycoprotein, and is a Chlorella, Chlamydomonas, and a grid. Algae (Scendesmus), Nannochloropsis and Ettlia.

The wet algae body is a microalgae cultured in a photoreactor, an open cell or a fermentation tank for self-operating, multi-battalion or mixed culture.

The wet algae body is a microalgae obtained by cultivating sea water, fresh water or waste water. The wet algae body is used to remove part of the water for the cultured microalgae by centrifugation, filtration or natural sedimentation, and the wet algae body having a concentration of the algae of 250-1000 g/L is obtained.

The invention provides a method for esterifying algae oil by microalgae breaking and oil extraction 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 S0 ₄ , SA), thionyl chloride (S0CI ₂ ) or sulfonic acid (R-S0 ₃ H a class of trifluoromethanesulfonic acid (CF ₃ S0 ₃ H, TFMSA) and p-toluenesulfonic acid (p-CH ₃ -C ₆ H ₄ -S0 ₃ H, P-TSA) and other strong acids, at 60~90° The mixture is stirred for 0.5 to 1 hour to obtain a transparent viscous water-resistant acidic ionic liquid, wherein the molar ratio of the strong acid to the amphoteric compound is from 1.0 to 0.5.

(2) Mix 5~100% (w/w) acidic ionic liquid with wet algae, stir and heat at room temperature ~ 10CTC 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 carry out the reflux algal oil extraction at 70~90 °C with a volume of 5-12 times algae solution of methanol-hexane solvent (1:1 v/v). And 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 recovers methanol and acidic ionic liquids.

(5) The microalgae of the present invention refers to single-cell freshwater or seawater algae _whose cell walls are cellulose (cell _U | _0Se ), pectin and glycoprotein, such as Chlorella, Chlamydomonas (Chlamydomonas), Scenedesmus, Nannochloropsis, and Ettlia.

The wet algae body 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 algal 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; 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 is only interfered by the accumulation of chlorophyll of the microalgae when used repeatedly, and the rate of broken wall oil is reduced by 7-10% when recycled.

The above detailed description is a specific description of a possible embodiment of the present invention, but the actual The examples are not intended to limit the scope of the invention, and equivalents or modifications of the invention are intended to be included in the scope of the invention.

In summary, this case is not only innovative in terms of space type, but also can enhance the above-mentioned multiple functions compared with commonly used items. It should have fully complied with the statutory invention patent requirements of novelty and enthusiasm, so the application is made according to law. The bureau approved the application for the invention patent, in order to invent the invention, to the sense of virtue. DRAWINGS

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. detailed description

In order to facilitate the review of the technical features, the contents and the advantages of the present invention and the efficacies thereof, the present invention will be described in conjunction with the accompanying drawings, and the description of the embodiments will be described in detail below. The subject matter is only for the purpose of illustration and supplementary description. It is not necessarily the 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. , combined with the first description.

As shown in Fig. 1, a flow chart of a method for simultaneously esterifying algae oil by microalgae breaking and extracting with a water-resistant acidic ionic liquid according to the present invention is as follows:

S11: Microalgae cultivation is a microalgae cultivated in a photoreactor, open pond, fermenter seawater, fresh water or wastewater for self-operated, hetero-barrier, mixed operation, and the concentration of microalgae at this time is l~3 g/L. ;

S12: collecting algae, collecting microalgae, centrifuging, filtering or sedimenting, wherein the concentration of microalgae is 250~1000 g/L;

S13: The microalgae is broken, add 5~100% PPS acidic ionic liquid, and stir at room temperature ~100 °C for 5~30 minutes;

S14: The algae oil is extracted with the same oxime ester, and the oil is refluxed at 70-90 ° C with a so-called fat extractor at a volume of 5 to 12 times of methanol-hexane (1:1) at room temperature and homogenized 2~ After 5 hours, the algae residue is separated (in the filter paper tube);

S15: separation of algae oil, the above liquid is allowed to stand layered, the upper layer is dissolved in hexane by the algae oil, and the ionic liquid is dissolved in methanol and water in the lower layer; S16: Solvent and ionic liquid recovery, respectively, the algae oil solution and the ionic solution are distilled under reduced pressure, and the algae oil [FAME] and triglyceride (TG) are recovered, and methanol, hexane, water and ionic liquid are recovered. reusable.

Example 1: Water-resistant acidic ionic liquid on the dewatering and refining rate of freshwater algae:

Experimental group (1):

Following the procedure outlined in the examples, 2.02 g (0.01 mole) of PPS white solid was placed in a round bottom flask and 0.98 g (0.01 mole) of H ₂ S0 ₄ (SA) was added dropwise at 60. Stir in a C water bath for 30 minutes to form a transparent viscous ionic liquid.

The freshwater aquaculture Chlorella sorokiniana was collected by centrifugation, and 10 _{g of} wet algae (dry weight about 0.8~ll g) was weighed. The acidic ionic liquid prepared above was added and heated at 60 ° C for 250 min at 250 rpm. , the microalgae broke. Then transfer all the mixture (including acidic ionic liquid) after the microalgae is broken to the soxon extractor filter paper, add 400 mL of extraction esterification solvent (methanol: hexane = 1:1), oil at 70~75 °C The bath is subjected to reflux extraction of algae oil and esterification reaction, 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 (algae) is separated by a separatory funnel. The oil is dissolved in the hexane and the lower layer (acid ionic liquid and water). After the upper and lower layers are separated, the solvent and water are separately concentrated under reduced pressure, and the upper layer liquid can obtain the algal oil product, and the lower layer can recover the acidic ionic liquid. The algae oil product was weighed, and its composition was analyzed by a 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) χ 100%

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

Control group (1):

Weigh 10 g of wet algae (dry weight about 0.8~1.1 g), add 5 g of quartz sand (particle size 0.7 mm), shake the cell wall with a cell homogenizer at a speed of 6.5 m/s for 15 seconds, and then crush the cell wall 10 times. The algal oil extraction and esterification reaction was carried out in the same manner as in the experimental group (1), 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), and finally the esterification reaction was followed. 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 S0 ₃ H, TFMSA) 1.50 g ( 0.01 mole), the results of 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 -S0. ₃ H, PTSA) 1.72 g (0.01 mole). The results of 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 extraction and esterification were carried out. However, the strong ionic liquid in the ionic liquid was changed to thionyl chloride (SOCI ₂ ) 1.19 g (O.Olmole). 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 9 CTC for 30 minutes. The final esterification reaction was shown in Table 1. in.

Experimental group (6)

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

According to the results of Table 1,

(1) Comparing the experimental group (1) with the control group (2), the sulfuric acid ionic liquid has a higher oil recovery rate and a catalytic esterification rate than the sulfuric acid in the same molar number of sulfuric acid.

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

(3) Comparing the experimental group (1) and the experimental group (5), under the same concentration of sulfuric acid 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. Up to 24.43% and esterification rate of 95.98%

(5) Comparing the control group (1) with the experimental group (5), using 20% sulfated ionic liquid for microalgae wall-breaking oil extraction, the oil extraction rate is only 21.16% compared with 29.5% of the cell wall broken by the homogenizer. Poor, but the effect of ionic liquids catalyzing the esterification reaction can increase the esterification rate by 98.9%.

Table 1

Example 2: Comparison of the breakwater extraction and homogenization rate of seawater algae by different acidic ionic liquids: According to the reaction test procedure mentioned in the embodiment, the cultured seawater (containing 3% NaCI) is cultured with Nannochloropsis sp., and the wet algae body is 10 g (dry weight about 1.9-2.1 g). Add 20% (w/w) of acidic ionic liquid and heat and stir at rpm at 90 °C.

After 30 min, move to the cable extractor of the cable extractor and add 300 mL of extraction esterification solvent (methanol: hexane = 1:1), carry out reflux extraction and esterification until the filter paper tube is colorless (about 2~5 hours). The upper layer liquid (algae oil dissolved in hexane) and the lower layer liquid (acid ionic liquid and water) are separated by a separating funnel, and the algae oil and the acidic ionic liquid are recovered after concentration and removal of the solvent respectively under reduced pressure; the result of the esterification reaction is shown in In Table 2. The oil extraction rates of different acidic ionic liquids containing the same number of moles at 9CTC were PTSA>TFMSA>SA>SOCI ₂ ; the catalytic esterification rate was PTSA>SOCI ₂ >SA>TFMSA. This trend is different from the results of Example 1 freshwater algae because the oil extraction rate and algal oil esterification rate of different acidic ionic liquids are affected by the difference in cell wall composition of the microalgae and the salt concentration of the algae.

C18:0 acid 0.35 0.47 - -

C18: l acid 20.98 4.55 9.43 17.74 Example 3: Effect of repeated use of sulfuric acid ionic liquid on the extraction rate and esterification rate of freshwater algae:

According to the reaction test procedure mentioned in the embodiment, the ground leaching oil of Chlorella somkiniana and the lower layer of sulfated ionic liquid recovered after esterification are collected, and the equal weight of hexane is extracted three times to remove residual algal oil. The methanol solvent and water are removed by concentration under reduced pressure, that is, the sulfuric acid ionic liquid is recovered. 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. As described above, the efficiency of the wall-breaking oil recovery can be maintained at 95% or more, and the esterification efficiency is hardly affected.

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

In summary, 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 usual traditional methods. It has fully complied with the statutory invention patent requirements of novelty and enthusiasm, so the application is made according to law. You have approved this invention patent application, in order to invent invention, to the sense of virtue.

Claims

Claim

A method for simultaneously esterifying algae oil with a water-resistant acidic ionic liquid for microalgae breaking and oil extraction, wherein the steps are as follows:

The supernatant liquid and the lower layer liquid were separately distilled under reduced pressure, and the first layer liquid was obtained from the supernatant liquid and the first organic solvent, and the methanol and the water-resistant acidic ionic liquid were obtained from the lower layer liquid.

2. The method for simultaneously esterifying algae oil by microalgae breaking and oil extraction with a water-resistant acidic ionic liquid according to claim 1, wherein the water-resistant acidic ionic liquid utilizes a sultone-containing solvate. An organic nitrogen-containing compound, which is reacted with a Bronsted strong acid at 60 to 90 ° C for 1 hour to obtain a transparent viscous, water-resistant acidic ionic liquid, wherein the sultone-containing organic compound The molar ratio of the nitrogen-containing compound to the Bronsted strong acid is between 1.0 and 2.5.

The method for simultaneously esterifying algae oil by microalgae breaking and oil extraction with water-resistant acidic ionic liquid according to claim 1, wherein the first microalgae wall-breaking mixture is a wet algae body The mass ratio of the water-resistant acidic ionic liquid is 5 to 100%, the heating temperature is between 50 and 180 ° C, and the stirring time is between 5 and 300 minutes to break the microalgae.

4. The method according to claim 1, wherein the microalgae breaking and extracting oil simultaneously esterifies the algal oil with the water-resistant acidic ionic liquid, wherein the refluxing oil extraction and the homologous esterification reaction and filtration are The first microalgae broken wall mixture is transferred into a cable fat filter paper tube, that is, a glass fiber material, to add 1 to 50 times the volume of the first microalgae broken wall mixture of the methanol and 1 to 50 times the volume of the algae liquid. The first organic solvent is subjected to reflux extraction and oil extraction at 50 to 90 ° C for 2 to 5 hours; the second microalgae broken wall mixture after refluxing and oil extraction and homogenization is allowed to stand still. a layer, wherein the upper layer liquid is algae oil in the first organic solvent, the lower layer liquid is dissolved in the methanol and water by the water resistant acidic ionic liquid; and the upper layer liquid and the lower layer liquid are separated, and then subjected to vacuum distillation, respectively. The upper layer can obtain algae oil and the first one to be recovered The solvent of the claim, the lower layer liquid can obtain the methanol and the water resistant acidic ionic liquid.

The method according to claim 2, wherein the microalgae breaking and extracting oil simultaneously esterifies the algal oil with the water-resistant acidic ionic liquid, wherein the organic content of the sulfonic acid lactone-containing organic nitrogen-containing compound The nitrogen compound is a mercapto imidazole type, a mercaptopyridine type, and a mercapto ammonia type nitrogen compound.

6. The method according to claim 2, wherein the microalgae breaking and extracting oil simultaneously esterifies the algal oil with the water-resistant acidic ionic liquid, wherein the Bronsted strong acid is thionyl chloride, sulfuric acid or A sulfonate Bronsted acid.

The method according to claim 5, wherein the microalgae breaking and extracting oil simultaneously esterifies the algal oil with the water-resistant acidic ionic liquid, wherein the organic content of the sulfonic acid lactone-containing organic nitrogen-containing compound The mercapto group in the mercapto imidazole type, the mercaptopyridine type, and the mercapto ammonia type nitrogen compound of the nitrogen compound is C _m H _2m+1 , wherein _m is from 1 to 18.

The method according to claim 5, wherein the microalgae breaking and extracting oil simultaneously esterifies the algal oil with the water-resistant acidic ionic liquid, wherein the sulfonic acid lactone-containing sulfonic acid in the organic nitrogen-containing compound The thiol group of the lactone is C _n H _2n , where n is from 3 to 6.

The method for simultaneously esterifying algae oil with microalgae breaking and extracting oil with water-resistant acidic ionic liquid according to claim 5, wherein the sulfonate sulfonate acid is fluorosulfonic acid, Trifluoromethanesulfonic acid and p-toluenesulfonic acid.

The method for simultaneously esterifying algae oil by microalgae breaking and oil extraction with water-resistant acidic ionic liquid according to claim 3, wherein the wet algae body is mixed with the water-resistant acidic ionic liquid. A twist of 20 to 70% is preferred.

The method for simultaneously esterifying algae oil by microalgae breaking and oil extraction 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 A second organic solvent is added.

12 . The method according to claim 11 , wherein the second organic solvent is an anthraquinone solvent or a cyclonon hydrocarbon, wherein the microalgae is broken and oiled by the water-resistant acidic ionic liquid, and the algae oil is simultaneously esterified. Solvent-like, or a mixed organic solvent containing anthracene hydrocarbons or cyclic hydrocarbons.

The method for simultaneously esterifying algae oil by microalgae breaking and oil extraction with water-resistant acidic ionic liquid according to claim 12, wherein the hydrazine hydrocarbon solvent and the hydrazine hydrocarbon The n in the solvent of the claims is 5 to 20.

The method according to claim 12, wherein the microalgae breaking and extracting oil simultaneously esterifies the algal oil with the water-resistant acidic ionic liquid, wherein the amount of the terpene hydrocarbon solvent in the second organic solvent is between 10 ~100% between.

The method according to claim 12, wherein the microalgae breaking and extracting oil simultaneously esterifies the algal oil with the water-resistant acidic ionic liquid, wherein the amount of the cyclic hydrazine hydrocarbon solvent in the second organic solvent is between 10 ~100% between.

The method according to claim 3, wherein the microalgae breaking and extracting oil simultaneously esterifies the algal oil with the water-resistant acidic ionic liquid, wherein the heating temperature is further increased to between 80 and 130 ° C. Better between.

The method according to claim 3, wherein the microalgae breaking and extracting oil simultaneously esterifies the algal oil with the water-resistant acidic ionic liquid, wherein the stirring time is preferably from 5 to 60 minutes.

The method according to claim 4, wherein the microalgae breaking and extracting oil simultaneously esterifies the algal oil with the water-resistant acidic ionic liquid, wherein the volume ratio of the methanol to the first microalgae wall-breaking mixture is It is preferably between 5 and 30.

The method according to claim 4, wherein the first organic solvent is an anthraquinone hydrocarbon solvent or a cyclic anthracene hydrocarbon, wherein the microalgae is broken and the oil is simultaneously esterified with the water-resistant acidic ionic liquid. Solvent-like, or a mixed organic solvent containing anthracene hydrocarbons or cyclic hydrocarbons.

The method according to claim 19, wherein the microalgae breaking and extracting oil simultaneously esterifies the algal oil with the water-resistant acidic ionic liquid, wherein n of the anthraquinone solvent and the cyclic hydrocarbon solvent is 5 to 12.

The method according to claim 19, wherein the microalgae breaking and extracting oil simultaneously esterifies the algal oil with the water-resistant acidic ionic liquid, wherein the amount of the terpene hydrocarbon solvent in the first organic solvent is between 10 ~100% between.

The method according to claim 19, wherein the microalgae breaking and extracting oil simultaneously esterifies the algal oil with the water-resistant acidic ionic liquid, wherein the amount of the cyclic hydrazine hydrocarbon solvent in the first organic solvent is between 10 ~100% between.

The method according to claim 4, wherein the microalgae breaking and extracting oil simultaneously esterifies the algal oil with the water-resistant acidic ionic liquid, wherein the first organic solvent and the first The volume ratio of the microalgae to the wall mixture is preferably between 5 and 30.

The method according to claim 3, wherein the microalgae breaking and extracting oil simultaneously esterifies the algal oil with the water-resistant acidic ionic liquid, wherein the wet algae body is a cell wall made of cellulose, pectin and sugar. The single-cell freshwater or seawater algae of the protein are Chlorella, Chlamydomonas, Scenedesmus, Chlorella, and Erigeron.

The method according to claim 3, wherein the microalgae breaking and extracting oil simultaneously esterifies the algal oil with the water-resistant acidic ionic liquid, wherein the wet algae body is self-operated, multi-operated or mixed culture Microalgae cultured in a photoreactor, open cell or fermentation tank.

The method for simultaneously esterifying algae oil by microalgae breaking and oil extraction with water-resistant acidic ionic liquid according to claim 3, wherein the wet algae body is obtained by cultivating seawater, fresh water or waste water. Microalgae.

The method for simultaneously esterifying algae oil by microalgae breaking and oil extraction with water-resistant acidic ionic liquid according to claim 3, wherein the wet algae is centrifuged, filtered or cultured for the cultured microalgae. The natural sedimentation method removes part of the water and reaches the wet algae body with a concentration of algae of 250-1000 g/L.