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

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

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TW201546263A
TW201546263A TW103119645A TW103119645A TW201546263A TW 201546263 A TW201546263 A TW 201546263A TW 103119645 A TW103119645 A TW 103119645A TW 103119645 A TW103119645 A TW 103119645A TW 201546263 A TW201546263 A TW 201546263A
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oil
microalgae
water
ionic liquid
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TWI513813B (en
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Ya-Hsiu Tseng
Ming-Yu Huang
Jung-Chung Wu
Chin-Yen Chou
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Cpc Corp Taiwan
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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

以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法 Method for simultaneously esterifying algae oil by microalgae breaking and extracting oil with water-resistant acidic ionic liquid

本發明係有關一種以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,尤指一種採用耐水酸性離子液體將微藻進行破壁,並催化微藻油脂酯化成酯肪酸甲酯;此酸性離子液體為親水性,可自動與微藻油脂及脂肪酸甲酯之油相分層,藉以達到破壁、萃油、酯化、油水相分離之目的。 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.

生質燃料是最有希望在未來替代化石能源並發揮重要作用的可再生能源;生質柴油是最常用的生質燃料之一,其主要成分是脂肪酸甲酯(FAME,Fatty Acid Methyl Ester),是以生物質(脂質)為原料,經過酯化或轉酯化製備而成。微藻是生產生質柴油的良好原料,微藻能利用陽光、水、CO2合成自身所需要的生物質(醣類、脂質、蛋白質),許多微藻含油量極高,在適合的培養條件下,一些含油率高達乾藻重50~70%,且微藻油脂中的脂肪酸碳數適合製備生質柴油。藻類相較於植物還具有光合作用效率高、環境適應能力強、生長週期短、生物產量高的特點。據保守估計,每年每公頃微藻可生產8,200~34,000L油脂,而富油植物如棕櫚和麻瘋樹等 每年每公頃的油脂產量僅為1,300~2,700L。 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.

由於微藻油脂大多存在於藻體細胞內,而且部分油脂以與蛋 白質或醣類結合的脂蛋白或脂多醣的形式存在,藻體細胞被較為堅韌的細胞壁所包裹,較難直接將油脂萃取出來。因此,在油脂萃取前需要對藻體進行破壁處理。常見的方法主要分為物理、化學和生物破壁法。微藻細胞採用某些破壁方法預處理後,大部分油脂仍貯留在細胞內,需採用合適的方法將微藻細胞內的油脂進一步萃取出來。目前常用的微藻油脂萃取方法主要有:有機溶劑萃取法、超臨界萃取法、亞臨界溶劑法以及耦合萃取技術等。 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.

離子液體(ionic liquids)係指結構上是由一有機陽離子與一 陰離子耦合之鹽類,此鹽類在室溫下為液態。離子液體的有機陽離子常見為有機氮化合物,如烷基胺型(alkylamine)、烷基咪唑型(Alkylimidazole)、烷基吡啶型(Alkylpyridine)有機氮化合物,陰離子則可為各種帶負電之分子,如BF4 -、PF6 -、Cl-、Br-、NO3 -、H2PO4 -、HSO4 -等;離子液體因為具有下列特性:(1)無蒸氣壓;(2)高沸點;(3)低毒性;(4)溶解度可調整;(5)具有極性及導電性,而被認為是一種綠色溶劑(green solvent)。離子液體已應用於自兩相水溶液中萃取蛋白質、自尿液中萃取賀爾蒙、油脂之酯化及作為生物可分解共聚物(copolymers)之溶劑等。在中華民國專利I325862公報中提到在磷醯化反應、矽烷化反應、硫化反應、醯化反應(光氣化除外)時,使用輔助鹼(含吡啶及其衍生物)可自反應混合物中移除酸,該方法使用輔助鹼與酸(可為鹽酸、乙酸、對-甲苯磺酸、甲烷磺酸或三氟甲烷磺酸)結合形成鹽,該鹽在反應溫度下為液態離子液,且在適當溶劑中之溶液下可 與有價值之產物或有價值產物酸為形成二不互溶之液相。 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.

離子液體曾被應用在微藻藻油萃取上,有研究以 1-ethyl-3-methyl imidazolium methyl sulfate([EMIM]SO3)與甲醇配製成共溶液(co-solvent)可在65℃反應18小時後,對冷凍乾燥之小球藻(Chlorella)之藻油萃從11.23%提升至38%;該離子液體對杜莎藻(Duniella):一種不具細胞壁耐高透壓的海水藻,藻油萃取率則相較於傳統索式萃取法(以己烷萃取)從11.1%下降至8.6%。該研究中也比較了EMIM共溶液之種類對萃油率之影響,結果以甲醇及異丙醇效果較佳。 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.

另有研究指出分別利用1-butyl-3-methylimidazolium methyl sulfate([BMIM]SO3)離子液體及[EMIM]SO3-甲醇共溶液對小球藻(C.vulgaris)進行藻油萃取時相較於Bligh and Dyer法(以氯仿及甲醇萃取)的10.6%萃油率分別提高至12.5%及11.9%。 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.

近期研究以[EMIM]PO2針對3%海水養殖之濕藻體(含水量 95% w/w)可無需加熱於室溫下配合添加氯仿進行破壁萃油,而且離子液體可重複使用達4次以上。 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.

在國外專利中提到以離子液體[EMIM]Cl添加25~100%時 可對部分脫水(含水量0~25%)之單細胞或多細胞藻類於150℃下進行破壁,藻油及離子液體則因疏水及親水性不同則可自動分層分離。針對細胞壁微纖維素成分之小球藻(Chlorella pyreniodosa)藻種添加[EMIM]Cl離子液體1~20%可時於105~140℃下破壁分離藻油(三酸甘油酯)。而咪唑衍生物之多種離子液體[EMIM]Ac,1-methyl-3-octylimidazolium chloride[OMIM]Cl,1-Hexyl-3-methylimidazolium chloride[HMIM]Cl, 1-Hexyl-3-methylimidazolium iodide[HMIM]I及[EMIM]CF3對各種微藻扁藻(Tetraselmis sp.),小球藻(Chlorella pyrenoidosa,Chlorella ellipsoidea,Chlorella vulgaris),褐藻(Laminaria digitata),擬球藻(Nannochloropsis oculata),海黍子馬尾藻(Sargassum muticum),二形柵藻(Scenedesmus dimorphus)之低溫(50℃以下)破壁萃油製程也被列入專利保護範圍。 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.

本發明提供一種以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,同時酸性離子液體可以催化甲醇-己烷溶劑系統中藻油的酯化反應,利用索式萃取設備既可有效萃取藻油並同步酯化藻油中的游離脂肪酸成脂肪酸甲酯,而且可有效移除油或離子液體中之藻體殘渣,所得之低酸藻油可直接應用於轉酯化製程,產製脂肪酸甲酯(FAME,Fatty Acid Methyl Ester)生質柴油。 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.

本發明提供一種以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,步驟如下: 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)將PPS(pyridinium propyl sulfobetaine)與布倫斯特強酸作用,如硫酸(H2SO4,SA)、氯化亞碸(Thionyl chloride,SOCl2)或烷磺酸(R-SO3H)類之三氟甲磺酸(CF3SO3H,TFMSA)及對-甲苯磺酸(p-CH3-C6H4-SO3H,P-TSA)等強酸,於60~90℃下攪拌0.5~1小時,即得到透明黏稠狀之耐水酸性離子液體,其中,該強酸與該兩性化合物莫耳比係介於1.0~1.5。 (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)以濕藻體混合5~100%(w/w)酸性離子液體,於室溫~100℃攪拌加熱5~30分鐘,進行微藻破壁,即為破壁藻液。 (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)將破壁藻液移入索式脂肪抽出器濾紙筒中,以5~12倍藻液體積之甲醇-己烷溶劑(1:1v/v)於70~90℃進行迴流藻油萃取及同步酯化2~5小時。 (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)迴流後溶液靜置分層,上層為藻油溶於己烷中,下層為酸性離子液體溶於甲醇及水中;分別收集上層及下層進行減壓蒸餾,上層可回收藻油、己烷;下層可回收甲醇及酸性離子液體。 (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)本發明之微藻係指細胞壁為纖維素(cellulose)、果膠(pectin)及醣蛋白(glycoprotein)之單細胞淡水或海水藻類,例如小球藻(Chlorella)、衣藻(Chlamydomonas)、柵藻(Scendesmus)、擬球藻(Nannochloropsis)及艾氏藻屬(Ettlia)。 (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.

其中,本發明之濕藻體係指微藻經培養至1~3g/L後以離心、過濾或自然沉降法去除部分水分,達到濃度為250~1000g/L之藻體。本發明之藻油係指含有脂肪酸甲酯(FAME)及三酸甘油酯(TAG)等油溶性成分混合物。本發明之耐水型酸性離子液體破壁萃油率較相同條件下相同濃度之布倫斯特強酸可提高1.1~3.8倍;對藻油之酯化率可達98.9%。本發明之離子液體可重複使用達四次以上,唯重複使用時受到微藻葉綠素累積之干擾,回收使用時破壁萃油率會下降7~10%。 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.

上列詳細說明係針對本發明之一可行實施例之具體說明,惟該實施例並非用以限制本發明之專利範圍,凡未脫離本發明技藝精神所為之等效實施或變更,均應包含於本案之專利範圍中。 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.

綜上所述,本案不但在空間型態上確屬創新,並能較習用物品增進上述多項功效,應已充分符合新穎性及進步性之法定發明專利要件,爰依法提出申請,懇請 貴局核准本件發明專利申請案,以勵發明, 至感德便。 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‧‧‧步驟流程 S11~S16‧‧‧Step process

第1圖為本發明之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法流程圖。 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.

為利 貴審查委員了解本發明之技術特徵、內容與優點及其所能達到之功效,茲將本發明配合附圖,並以實施例之表達形式詳細說明如下,而其中所使用之圖式,其主旨僅為示意及輔助說明書之用,未必為本發明實施後之真實比例與精準配置,故不應就所附之圖式的比例與配置關係解讀、侷限本發明於實際實施上的權利範圍,合先敘明。 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.

如第1圖所示,為本發明之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法流程圖,步驟如下:S11:微藻養殖,係為自營、異營、混營培養於光反應器、開放池、發酵槽海水、淡水或廢水之微藻,此時之微藻濃度係為1~3g/L;S12:藻體收集,係將收集之微藻,經過離心、過濾或沉降,此時之微藻濃度係為250~1000g/L;S13:微藻破壁,加入5~100% PPS酸性離子液體,在室溫~100℃攪拌5~30分鐘;S14:藻油萃取同步酯化,用索式脂肪抽出器以5~12倍藻液體積之甲醇-己烷(1:1)於70~90℃迴流萃油及同步酯化2~5小時後,將藻渣分離(濾紙筒 中);S15:藻油分離,將上述之液體靜置分層,上層為藻油溶於己烷,下層為離子液體溶於甲醇及水;S16:溶劑及離子液回收,分別將藻油溶液及離子溶液進行減壓蒸餾,有藻油[脂肪酸甘油酯(FAME)及三酸甘油酯(TG),回收甲醇、己烷、水及離子液體可重複使用。 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.

實施例一:耐水酸性離子液體對淡水藻之破壁萃油及同步酯化率比較: Example 1: Comparison of water-resistant acidic ionic liquids on the wall-breaking oil extraction and simultaneous esterification rate of freshwater algae:

實驗組(一): Experimental group (1):

依實施方式中所提之步驟,先取2.02g(0.01mole)PPS白色固體置於一圓底瓶中,逐滴加入0.98g(0.01mole)H2SO4(SA),在60℃水浴中攪拌30分鐘,形成透明黏稠狀離子液體。 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.

將淡水養殖後之引藻(Chlorella sorokiniana)離心收集,秤取濕藻體10g(乾重約0.8~1.1g),加入上述所製備之酸性離子液體,於60℃攪拌250rpm加熱30min,進行微藻破壁。再將微藻破壁後所有混合物(包括酸性離子液體)移至索式萃取器濾紙筒中,加入400mL之萃取酯化溶劑(甲醇:己烷=1:1),在70~75℃油浴中進行迴流萃取藻油及酯化反應,萃取酯化至濾紙筒萃取液呈無色(約2~5小時),停止加熱萃取,冷卻至室溫後,再利用分液漏斗劃分上層液(藻油溶於己烷)及下層液(酸性離子液體及水),上下層液分離後,分別以減壓濃縮去除溶劑及水,上層液可得藻油產品,下層液可回收酸性離子液體。藻油產品秤重,並利用氣體層析儀分析其組成,再計算萃油率及酯化率。萃油率及酯化率計算方法如下: 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:

萃油率=(藻油重/乾藻重)×100% Oil extraction rate = (algal oil weight / dry algae weight) × 100%

酯化率=(FAME總重/萃油重)×100% Esterification rate = (FAME total weight / extraction oil weight) × 100%

對照組(一): Control group (1):

秤取濕藻體10g(乾重約0.8~1.1g),加入5g石英砂(粒徑0.7mm)以細胞均質機於6.5m/s速度震盪15秒共10次破碎細胞壁後,採用與實驗組(一)相同的方式進行藻油萃取酯化反應,酯化反應後結果示於表一中。 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.

對照組(二): Control group (2):

以與實驗組(一)相同的方式進行薇藻破壁及萃取酯化反應,然而酸性離子液體改以濃硫酸(98%)0.98g(0.01mole),最後酯化反應後結果示於表一中。 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.

實驗組(二) Experimental group (2)

以與實驗組(一)相同的方式進行薇藻破壁及萃取酯化反應,然而酸性離子液體中布倫斯特強酸改為三氟甲磺酸(CF3SO3H,TFMSA)1.50g(0.01mole),最後酯化反應後結果示於表一中。 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.

實驗組(三) Experimental group (3)

以與實驗組(一)相同的方式進行薇藻破壁及萃取酯化反應,然而酸性離子液體中布倫斯特強酸改為對-甲苯磺酸(p-CH3-C6H4-SO3H,PTSA)1.72g(0.01mole),最後酯化反應後結果示於表一中。 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.

實驗組(四) Experimental group (4)

以與實驗組(一)相同的方式進行薇藻破壁及萃取酯化反應,然而酸性離子液體中布倫斯特強酸改為氯化亞碸(Thionyl chloride,SOCl2)1.19g(0.01mole),最後酯化反應後結果示於表一中。 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.

實驗組(五) Experimental group (5)

以與實驗組(一)相同的方式進行薇藻破壁及萃取酯化反應,然而酸性離子液體加入濕藻體後,改為在90℃加熱攪拌30分鐘,最後酯化反應後結果示於表一中。 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.

實驗組(六) Experimental group (6)

以與實驗組(一)相同的方式進,然而改添加酸性離子液體重量為濕藻重之50%(w/w)後,在60℃加熱攪拌30分鐘,最後酯化反應後結果示於表一中。 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.

根據表一結果顯示: According to the results of Table 1,

(1)比較實驗組(一)與對照組(二),含相同莫耳數之硫酸下,硫酸離子液體相較於硫酸會有較高之萃油率及催化酯化率。 (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)比較實驗組(一)、(二)、(三)、(四),含相同莫耳數之酸性離子液體中其萃油率為TFMSA>SA>SOCl2>PTSA;催化酯化率為TFMSA>SOCl2>SA>PTSA。 (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)比較實驗組(一)及實驗組(五),於相同濃度之硫酸離子液體下,提高反應溫度從60℃至90℃,可明顯提高萃油率及酯化率達98.9%。 (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)比較實驗組(一)及實驗組(六),於相同反應溫度下,提高硫酸離子液體添加量從20%(w/w)至50%(w/w)可明顯提高萃油率達28.43%及酯化率達95.98%。 (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)比較對照組(一)及實驗組(五),利用20%硫酸離子液體進行微藻破壁萃油其萃油率僅達21.16%相較傳統以均質機破碎細胞壁之29.5%稍差,但離子液體兼具催化酯化反應之效果可提升酯化率達98.9%。 (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%.

實施例二:不同酸性離子液體對海水藻之破壁萃油及同步酯化率比較:依實施方式中所提之反應測試步驟,離心收集海水(含3% NaCl)養殖後之擬球藻(Nannochloropsis sp.),秤取濕藻體10g(乾重約1.9~2.1g),加入酸性離子液體20%(w/w),於90℃加熱攪拌250rpm,30min,移至索式萃取器濾紙筒中,加入300mL之萃取酯化溶劑(甲醇:己烷=1:1),進行迴流萃取及酯化至濾紙筒無色(約2~5小時),利用分液漏斗劃分上層液(藻油溶於己烷)及下層液(酸性離子液體及水),分別以減壓濃縮去除溶劑後回收藻油及酸性離子液體;最後酯化反應後結果示於表二中。比較含相同莫耳數之不同酸性離子液體於90℃其萃油率為PTSA>TFMSA>SA>SOCl2;催化酯化率為PTSA>SOCl2>SA>TFMSA。此趨勢與實施例一淡水藻之結果不同,係因不同酸性離子液之萃油率及藻油酯化率會受到微藻細胞壁組成份不同及藻體含鹽濃度不同之影響。 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.

實施例三、硫酸離子液體回收重複使用對淡水藻破壁萃油率及酯化率之影響:依實施方式中所提之反應測試步驟,收集引藻(Chlorella sorokiniana)破壁萃油及酯化使用後回收之下層硫酸離子液體,加入等重之己烷萃取三次以去除殘留藻油,以減壓濃縮去除甲醇溶劑及水,即為回收硫酸離子液體。根據實施例一之方法,每10g濕藻添加20%(w/w)硫酸離子液體進行引藻破壁萃油,並評估萃油率及酯化率;結果顯示離子液可重複使用四次以上, 回收使用時破壁萃油效率可維持在95%以上,其酯化效率幾乎不受影響。 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.

上列詳細說明乃針對本發明之一可行實施例進行具體說明,惟該實施例並非用以限制本發明之專利範圍,凡未脫離本發明技藝精神所為之等效實施或變更,均應包含於本案之專利範圍中。 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.

綜上所述,本案不僅於技術思想上確屬創新,並具備習用之傳統方法所不及之上述多項功效,已充分符合新穎性及進步性之法定發明專利要件,爰依法提出申請,懇請 貴局核准本件發明專利申請案,以勵發明,至感德便。 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‧‧‧步驟流程 S11~S16‧‧‧Step process

Claims (27)

一種以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其步驟如下:以一耐水性酸性離子液體進行微藻破壁,形成一第一微藻破壁混合液;將該第一微藻破壁混合液置於一甲醇及一第一有機溶劑後形成一第二微藻破壁混合液;將該第二微藻破壁混合液進行迴流萃油及同步酯化反應後,進行過濾,形成一上層液及一下層液;以及將該上層液及該下層液分別進行減壓蒸餾,由該上層液取得一藻油及該第一有機溶劑,由該下層液取得該甲醇及該耐水性酸性離子液體。 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. 如申請專利範圍第1項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中該耐水性酸性離子液體係利用一含磺酸內酯之有機含氮化合物,與一布倫斯特強酸作用,於60~90℃之間,攪拌1小時,取得透明黏稠狀之該耐水性酸性離子液體,其中,該含磺酸內酯之有機含氮化合物與該布倫斯特強酸莫耳比係介於1.0~2.5之間。 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. 如申請專利範圍第1項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中該第一微藻破壁混合液係以一濕藻體混合該耐水性酸性離子液體比例為5~100%(w/w),加熱溫度介於50~180℃之間,攪拌時間介於5~300分鐘,進行微藻破壁。 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. 如申請專利範圍第1項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中迴流萃油及同步酯化反應與過濾之係將該第一微藻破壁混合液移入索式脂肪抽出器濾紙筒(玻璃纖維材質)中,以 加入1~50倍該第一微藻破壁混合液體積之該甲醇及1~50倍藻液體積之該第一有機溶劑,於50~90℃進行迴流萃油及同步酯化2~5小時;將進行迴流萃油及同步酯化後之該第二微藻破壁混合液靜置分層,該上層液為藻油該第一有機溶劑中,該下層液為該耐水性酸性離子液體溶於該甲醇及水中;將該上層液及該下層液分離後,分別進行減壓蒸餾,該上層液可取得藻油及回收之該第一有機溶劑,該下層液可取得該甲醇及該耐水性酸性離子液體。 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. 如申請專利範圍第2項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中該含磺酸內酯之有機含氮化合物中之有機含氮化合物係為烷基咪唑型(Alkylimidazole)、烷基吡啶型(Alkylpyridine)及烷基氨型(Alkylamine)氮化合物。 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. 如申請專利範圍第2項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中該布倫斯特強酸係為氯化亞碸(Thionyl chloride,SOCl2)、硫酸(H2SO4)或一烷磺酸(R-SO3H)布倫斯特酸。 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. 如申請專利範圍第5項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中該含磺酸內酯之有機含氮化合物中之有機含氮化合物的烷基咪唑型(Alkylimidazole)、烷基吡啶型(Alkylpyridine)及烷基氨型(Alkylamine)氮化合物中之烷基為CmH2m+1,其中m係為1~18。 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. 如申請專利範圍第5項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中該含磺酸內酯之有機含氮化合物中之磺酸內酯之烷基為CnH2n,其中n係為3~6。 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. 如申請專利範圍第5項所述之以耐水酸性離子液體進行微藻破壁與萃 油同時酯化藻油之方法,其中該烷磺酸(R-SO3H)布倫斯特酸係為氟磺酸(FSO3H)、三氟甲磺酸(CF3SO3H)及對-甲苯磺酸(p-CH3-C6H4-SO3H)。 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). 如申請專利範圍第3項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中該濕藻體混合該耐水性酸性離子液體比例更進一步為20~70%(w/w)為較佳。 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. 如申請專利範圍第3項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中該濕藻體混合該耐水性酸性離子液體,更進一步添加一第二有機溶劑。 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. 如申請專利範圍第11項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中該第二有機溶劑係為烷烴類溶劑(CnH2n+2)、環烷烴類溶劑(CnH2n),或含有烷烴類、環烷烴類之混合有機溶劑。 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. 如申請專利範圍第12項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中烷烴類溶劑(CnH2n+2)及環烷烴類溶劑(CnH2n)中之n係為5~20。 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 . 如申請專利範圍第12項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中該第二有機溶劑中烷烴類溶劑(CnH2n+2)量係介於10~100%之間。 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%. 如申請專利範圍第12項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中該第二有機溶劑中環烷烴類溶劑(CnH2n)量係介於10~100%之間。 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%. 如申請專利範圍第3項所述之以耐水酸性離子液體進行微藻破壁與萃 油同時酯化藻油之方法,其中加熱溫度係更進一步介於80~130℃之間較佳。 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. 如申請專利範圍第3項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中攪拌時間介於5~60分鐘較佳。 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. 如申請專利範圍第4項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中該甲醇與該第一微藻破壁混合液體積比係介於5~30較佳。 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. 如申請專利範圍第4項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中該第一有機溶劑係為烷烴類溶劑(CnH2n+2)、環烷烴類溶劑(CnH2n),或含有烷烴類、環烷烴類之混合有機溶劑。 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. 如申請專利範圍第19項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中烷烴類溶劑(CnH2n+2)及環烷烴類溶劑(CnH2n)中之n係為5~12。 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. 如申請專利範圍第19項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中該第一有機溶劑中烷烴類溶劑(CnH2n+2)量係介於10~100%之間。 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%. 如申請專利範圍第19項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中該第一有機溶劑中環烷烴類溶劑(CnH2n)量係介於10~100%之間。 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%. 如申請專利範圍第4項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中該第一有機溶劑與該第一微藻破壁混合液 體積比係介於5~30較佳。 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. 如申請專利範圍第3項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中該濕藻體係為細胞壁為纖維素(cellulose)、果膠(pectin)及醣蛋白(glycoprotein)之單細胞淡水或海水藻類,係為小球藻(Chlorella)、衣藻(Chlamydomonas)、柵藻(Scendesmus)、擬球藻(Nannochloropsis)及艾氏藻屬(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 cellulose (cell) and pectin (cell). And single-cell freshwater or seawater algae of glycoprotein, which are Chlorella, Chlamydomonas, Scenedesmus, Nannochloropsis, and Ettlia. 如申請專利範圍第3項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中該濕藻體係為自營、異營或混營培養於光反應器、開放池或發酵槽中培養的微藻。 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. 如申請專利範圍第3項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中該濕藻體係為海水、淡水或廢水經培養而得之微藻。 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. 如申請專利範圍第3項所述之以耐水酸性離子液體進行微藻破壁與萃油同時酯化藻油之方法,其中該濕藻體係為培養之微藻經離心、過濾或自然沉降法去除部分水分,達到藻體濃度為250~1000g/L之該濕藻體。 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.
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