TW201629030A - Recovery of tocopherols/tocotrienols, glycerine, sterols and fatty acid esters from vegetable OIL distillate and the process thereof - Google Patents

Abstract

A process for recovering tocotrienols/tocopherols from vegetable oil distillate comprising the steps of esterifying the vegetable oil distillate with an alcohol in the presence of an acid catalyst to convert the fatty acids contained therein to produce an esterified mixture comprising fatty acid esters, thereby reducing fatty acid content in the oil to less than 3% by weight; distilling the esterified mixture for separating and removing the fatty acid esters therefrom; transesterifying the distilled mixture with an alcohol in the presence of a basic catalyst for converting glycerides present therein to fatty acid esters and glycerine, forming a transesterified mixture comprising glycerine and fatty acid esters; purifying the transesterified mixture to substantially remove glycerine therefrom; and distilling the purified mixture to substantially remove fatty acid esters, producing a composition comprising a predetermined concentration of tocotrienols/tocopherols.

Description

自植物油餾出物中回收生育酚/生育三烯酚、甘油、固醇和脂肪酸酯的回收程序 Recovery procedure for recovery of tocopherol/tocotrienol, glycerol, sterol and fatty acid esters from vegetable oil distillates

本發明係關於自精煉廠回收植物油餾出物之中的有價值成份。進一步而言，本案發明係關於利用酯化、蒸餾及轉酯之多重步驟，並自棕櫚油餾出物中回收高品質的生育三烯酚/生育烯、固醇、及選擇性的回收甘油以及酯類形式呈現的游離脂肪酸。 The present invention relates to valuable components in the recovery of vegetable oil distillates from a refinery. Further, the present invention relates to the use of multiple steps of esterification, distillation and transesterification, and recovery of high quality tocotrienols/tocopherols, sterols, and selective recovery of glycerol from palm oil distillates and Free fatty acids present in the ester form.

過去數年，天然植物油諸如棕櫚、棕櫚核、米麩、大豆、向日葵、油菜、油菜籽、棉籽、紅花及玉米油已被認為含有高含量對人體健康有益的成分。這些有有益成分包括但不限於生育酚、生育三烯酚、類胡蘿蔔素及類固醇類物質。 In the past few years, natural vegetable oils such as palm, palm kernel, rice bran, soybean, sunflower, canola, rapeseed, cottonseed, safflower and corn oil have been considered to contain high levels of ingredients beneficial to human health. These beneficial ingredients include, but are not limited to, tocopherols, tocotrienols, carotenoids, and steroids.

生育酚及生育三烯酚為植物油之中有價值之成分，其原因在於它們具有抗氧化的能力及提供保護並防止在 大腦、腫瘤及各種類型癌症之中的細胞損壞，以及協助修復損壞的細胞。生育三烯酚獨特的分子結構進一步透露出具有降膽固醇的特徵，從而幫助維持健康的心血管系統。具體地，生育三烯酚能藉由清除累積在動脈的膽固醇來幫助降低血管膽固醇的濃度。類胡蘿蔔素為植物合成的天然色素，其顯現出的顏色有黃色、橙色或紅色。在所有的類胡蘿蔔素中，α-胡蘿蔔素、β-胡蘿蔔素、β-玉米黃素均為維生素A(視黃醇)的前驅物或可互換地視為原維生素A，並作為維生素A的來源。其它類胡蘿蔔素諸如葉黃素、茄紅素及玉米黃素無法轉換成維生素A，但由於他們係為良好抗氧化劑，因此仍具有特殊的重要意義。 Tocopherols and tocotrienols are valuable ingredients in vegetable oils because they have antioxidant capacity and provide protection and prevent Cell damage in the brain, tumors, and various types of cancer, as well as assisting in repairing damaged cells. The unique molecular structure of tocotrienols further reveals cholesterol-lowering characteristics that help maintain a healthy cardiovascular system. Specifically, tocotrienols can help lower the concentration of vascular cholesterol by removing cholesterol accumulated in the arteries. Carotenoids are natural pigments synthesized by plants, which appear in yellow, orange or red colors. Among all carotenoids, α-carotene, β-carotene, and β-zeaxanthin are precursors of vitamin A (retinol) or interchangeably regarded as provitamin A, and serve as a source of vitamin A. Other carotenoids such as lutein, lycopene and zeaxanthin cannot be converted to vitamin A, but they are of particular importance because they are good antioxidants.

另一方面，植物性固醇被認為可阻斷膽固醇的吸收及減少血膽固醇的濃度。由於植物性固醇幾乎與膽固醇相同，它們可彼此相互競爭以便被小腸吸收。然而，植物性固醇不易被人體所吸收，且它們似乎可阻斷膳食膽固醇，從而減少血膽固醇濃度，並降低罹患冠狀動脈心臟疾病的風險。一些研究文獻亦指出植物性固醇具有抗癌、抗發炎、抗動脈粥狀硬化及抗氧化之特徵。 On the other hand, phytosterols are thought to block the absorption of cholesterol and reduce the concentration of blood cholesterol. Since phytosterols are almost identical to cholesterol, they compete with each other for absorption by the small intestine. However, phytosterols are not easily absorbed by the body, and they appear to block dietary cholesterol, thereby reducing blood cholesterol levels and reducing the risk of coronary heart disease. Some research literature also pointed out that phytosterols are characterized by anti-cancer, anti-inflammatory, anti-atherosclerosis and anti-oxidation.

鑒於上述，期望自天然植物油之中萃取或回收這些有益成分。通常在回收這些成分的過程中，有很大一部分的生育三烯酚及生育酚在各種蒸餾氣流之中損失。這些蒸餾氣流典型地包含高於0.1%重量百分比(或1000ppm)的生育 三烯酚/生育酚。然而這些蒸餾氣流亦包含高於10%重量百分比之高游離脂肪酸濃度。不僅僅是游離脂肪酸，其它成分諸如固醇酯類、單酸甘油脂、雙三甘油脂、三酸甘油脂、甘油等亦可出現在蒸餾氣流之中。因此，為了獲得具有濃縮的生育三烯酚/生育酚之組成物，必須自油餾出物之中去除這些不想要的雜質。 In view of the above, it is desirable to extract or recover these beneficial ingredients from natural vegetable oils. A large proportion of tocotrienols and tocopherols are typically lost in various distillation streams during the recovery of these components. These distilled gas streams typically contain more than 0.1% by weight (or 1000 ppm) of fertility Trienol/tocopherol. However, these distilled gas streams also contain high free fatty acid concentrations above 10% by weight. Not only free fatty acids, other ingredients such as sterol esters, monoglycerides, ditriglycerides, triglycerides, glycerol, etc. can also be present in the distillation gas stream. Therefore, in order to obtain a composition having concentrated tocotrienol/tocopherol, these undesired impurities must be removed from the oil distillate.

過去已出現許多回收技術，諸如溶劑抽取、溶劑部分分離法、離子交換樹脂處理及色層分析法。然而這些技術擁有許多缺點，包含低產量、整個過程中欲抽取的成分顯著衰解及使用有機致癌溶劑等。因此，需要一種改良方法來回收生育三烯酚/生育酚。 Many recycling techniques have appeared in the past, such as solvent extraction, solvent partial separation, ion exchange resin treatment, and chromatography. However, these techniques have a number of disadvantages, including low yields, significant degradation of the components to be extracted throughout the process, and the use of organic carcinogenic solvents. Therefore, there is a need for an improved method for recovering tocotrienols/tocopherols.

本發明提供一種自棕櫚油餾出物之中分離生育三烯酚/生育酚的改良方法，且同時回收甘油及酯類形式呈現的游離脂肪酸。為了進一步提升經回收組成分的品質，在回收生育三稀酚/生育酚之前，本發明的前處理步驟中進行酸性酯化反應，接著進行轉酯化反應，以去除其中出現的脂肪酸。 The present invention provides an improved process for isolating tocotrienols/tocopherols from palm oil distillates while recovering free fatty acids in the form of glycerol and esters. In order to further improve the quality of the recovered component, an acidic esterification reaction is carried out in the pretreatment step of the present invention before the recovery of the tocotrienol/tocopherol, followed by a transesterification reaction to remove the fatty acid present therein.

本發明的目的之一為提供一種自棕櫚油餾出物之中分離生育三烯酚、生育酚及固醇類的方法，且同時回收甘油及酯類形式呈現的游離脂肪酸。 One of the objects of the present invention is to provide a process for separating tocotrienols, tocopherols and sterols from palm oil distillates, and simultaneously recovering free fatty acids in the form of glycerol and esters.

本發明又一目的為提供一種進一步進行轉酯化 反應之前利用酸性酯化反應作為前處理步驟以減少天然油中的脂肪酸含量的方法，進而提高自天然油中所回收或分離之組成物的品質。 Another object of the present invention is to provide a further transesterification The method of using an acidic esterification reaction as a pretreatment step to reduce the fatty acid content in the natural oil prior to the reaction, thereby improving the quality of the composition recovered or separated from the natural oil.

本發另一目的為提供一種分離及回收生育三烯酚/生育酚及視選擇性其它組成分的方法，諸如甘油及固醇類，其在整個過程中不會被降解或修飾。 Another object of the present invention is to provide a method for separating and recovering tocotrienol/tocopherol and optionally other components, such as glycerol and sterols, which are not degraded or modified throughout the process.

本發明還有一目的為提供一種多重蒸餾步驟以作為後處理，進而提高所想到之組成物的純度。 Still another object of the present invention is to provide a multiple distillation step for post-treatment to increase the purity of the contemplated composition.

本發明所提供之至少一種實施例，其全部或部分描述一種自植物油餾出物中回收生育三烯酚/生育酚的方法，其步驟包含：在酸性催化劑存在下，使用醇類對植物油餾出物進行酯化反應，轉換植物油餾出物之中的脂肪酸，產生含有脂肪酸酯類的酯化混合物，從而減少植物油餾出物之中的脂肪酸的含量至低於3%重量百分比；對酯化混合物進行蒸餾，從而分離且去除酯化混合物中的脂肪酸酯類，以形成蒸餾混合物；在鹼性催化劑的存在下，使用醇類對蒸餾混合物進行轉酯交換反應，使蒸餾混合物之中的甘油酯轉換成脂肪酸酯類和甘油，形成含有甘油及脂肪酸酯類之轉酯混合物；純化轉酯混合物，實質上去除轉酯混合物中的甘油，以形成純化混合物；以及對純化混合物進行蒸餾，實質上去除純化混合物之中的脂肪酸酯類，產生含有預定濃度之生育三烯酚/生育酚的組成物。 At least one embodiment of the present invention, which wholly or partially describes a process for recovering tocotrienol/tocopherol from a vegetable oil distillate, the process comprising: distilling the vegetable oil with an alcohol in the presence of an acidic catalyst The esterification reaction converts the fatty acid in the vegetable oil distillate to produce an esterified mixture containing the fatty acid ester, thereby reducing the fatty acid content in the vegetable oil distillate to less than 3% by weight; Distilling to separate and remove fatty acid esters in the esterification mixture to form a distillation mixture; transesterification of the distillation mixture with an alcohol in the presence of a basic catalyst to convert the glyceride in the distillation mixture Forming fatty acid esters and glycerol to form a transesterified mixture containing glycerol and fatty acid esters; purifying the transesterified mixture to substantially remove glycerol from the transesterified mixture to form a purified mixture; and subjecting the purified mixture to distillation, substantially removing and purifying Fatty acid esters in the mixture, producing tocotrienol/sheng containing a predetermined concentration The composition of the tocopherol.

在本發明之較佳實施例中，該植物油餾出物為棕櫚脂肪酸餾出物或任意之在總組成分中含有脂肪酸高於10%重量百分比的植物油餾出物。 In a preferred embodiment of the invention, the vegetable oil distillate is a palmitic fatty acid distillate or any vegetable oil distillate containing more than 10% by weight of the fatty acid in the total composition.

根據先前之實施例，在進一步進行蒸餾之前，將植物油餾出物進行酯化、蒸餾、轉酯化反應及純化。較佳地，在酸性催化劑存在下進行酯化反應，酸性催化劑可以為氫氯酸、乙酸、硫酸或檸檬酸，同時在鹼性催化劑存在下，進行轉酯化反應，鹼性催化劑可以為甲醇鈉或甲醇鉀。 According to the previous examples, the vegetable oil distillate is subjected to esterification, distillation, transesterification and purification prior to further distillation. Preferably, the esterification reaction is carried out in the presence of an acidic catalyst, and the acidic catalyst may be hydrochloric acid, acetic acid, sulfuric acid or citric acid, and the transesterification reaction is carried out in the presence of a basic catalyst, and the basic catalyst may be sodium methoxide. Or potassium methoxide.

前述所提及的純化步驟指的是離心或重力沉降，以自轉酯混合物中移除甘油。 The aforementioned purification step refers to centrifugation or gravity settling to remove glycerol from the autorotation ester mixture.

在本發明之另一較佳實施例中，本發明所提供的方法進一步包含對酯化混合物或純化混合物進行洗滌的步驟，以去除催化劑、未反應之醇類及其它雜質，接著對經洗滌的酯化混合物進行加熱，以減少混合物中殘餘的水氣含量至低於0.07%重量百分比。 In another preferred embodiment of the present invention, the method provided by the present invention further comprises the step of washing the esterification mixture or the purified mixture to remove the catalyst, unreacted alcohols and other impurities, followed by washing. The esterification mixture is heated to reduce the residual moisture content of the mixture to less than 0.07% by weight.

本發明又一較佳實施例提供自植物油餾出物中回收生育三稀酚/生育酚，其進一步包還自組成物中回收固醇類的步驟。組成物經過醇類處理及將形成的混合物進行冷卻，最後使回收的固醇類以結晶形式呈現。 A further preferred embodiment of the present invention provides for the recovery of tocotrienol/tocopherol from a vegetable oil distillate, which further comprises the step of recovering sterols from the composition. The composition is subjected to alcohol treatment and the resulting mixture is cooled, and finally the recovered sterols are presented in crystalline form.

較佳地，在酯化、轉酯化反應或固醇回收步驟中所使用的醇類可以為甲醇、乙醇、丙醇及丁醇任一種或其組合。 Preferably, the alcohol used in the esterification, transesterification or sterol recovery step may be any one of methanol, ethanol, propanol and butanol or a combination thereof.

本發明所屬技術領域中具有一般技藝者應清楚明瞭本發明係以最佳實施例來達成前述所提及的各項優點及說明書中提及的所有特徵。值得注意的是，下述本發明之較佳實施例的敘述並非用以窮盡或限縮本發明之技術揭露。 It is to be understood by those skilled in the art that the present invention <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; It is noted that the following description of the preferred embodiments of the invention is not intended to be exhaustive or limiting.

本發明所屬技術領域中具有一般技藝者應清楚明瞭本發明係以最佳實施例來達成前述所提及的各項優點及說明書中提及的所有特徵，本發明將參照下述實施例，作更詳細的敘述。值得注意的是，下述本發明之較佳實施例的敘述，僅用以解釋及說明，而非用以窮盡或限縮本發明之技術揭露。 It will be apparent to those skilled in the art that the present invention, in the <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; A more detailed description. It is noted that the following description of the preferred embodiments of the invention is intended to be illustrative and not restrictive.

說明書中出現的用語「生育三烯酚/生育酚」或「生育酚/生育三烯酚」係指生育三烯酚及生育酚任何其中之一或其組合。 The term "tocotrienol/tocopherol" or "tocopherol/tocotrienol" as used in the specification refers to any one or a combination of tocotrienol and tocopherol.

本發明係關於自精煉廠從植物油餾出物中回收生育三烯酚/生育酚之一種多重步驟的方法，此多重步驟涉及酯化、蒸餾、轉酯化以及進一步蒸餾。本發明所提供的方法選擇性地回收固醇、甘油以及以酯類形式呈現的游離脂肪酸。 The present invention relates to a process for recovering tocotrienol/tocopherol from a vegetable oil distillate from a refinery which involves esterification, distillation, transesterification and further distillation. The method provided by the present invention selectively recovers sterols, glycerol, and free fatty acids in the form of esters.

本發明技術領域中具有一般技藝者應清楚明瞭 本說明書中所指的植物油餾出物較佳為含有生育三烯酚/生育酚、固醇酯類、脂肪酸、單酸甘油酯、雙酸甘油酯、及三酸甘油酯的組成分，其中生育三烯酚/生育酚佔總組成分的0.1%至0.5%重量百分比，同時在總組成分中脂肪酸的含量高於10%重量百分比。 It should be clear to those of ordinary skill in the art of the present invention. The vegetable oil distillate referred to in the present specification preferably contains a component of tocotrienol/tocopherol, sterol ester, fatty acid, monoglyceride, diglyceride, and triglyceride, wherein fertility The trienol/tocopherol accounts for 0.1% to 0.5% by weight of the total composition, while the content of the fatty acid in the total composition is more than 10% by weight.

根據本發明之較佳實施例，本發明自植物油餾出物回收生育三烯酚/生育酚，其步驟包含在酸性催化劑的存在下，使用醇類對植物油餾出物進行酯化反應，轉換植物油餾出物之中的脂肪酸，產生含有脂肪酸酯類的酯化混合物，從而減少該植物油餾出物之中的脂肪酸含量至低於3%重量百分比；對酯化混合物進行蒸餾，從而分離且去除酯化混合物中的脂肪酸酯類，最後形成蒸餾混合物；在鹼性催化劑的存在下，使用醇類對蒸餾混合物進行轉酯交換反應，使蒸餾混合物中的甘油酯轉換成脂肪酸酯類和甘油，以形成含有甘油及脂肪酸酯類之轉酯混合物；純化轉酯混合物，實質上去除轉酯混合物中的甘油，以形成一純化的混合物；以及對純化的混合物進行蒸餾，實質上去除純化混合物之中的脂肪酸酯類，最後製造出含有預定濃度之生育三烯酚/生育酚的組成物。 According to a preferred embodiment of the present invention, the present invention recovers tocotrienol/tocopherol from a vegetable oil distillate, the step comprising: esterifying the vegetable oil distillate with an alcohol in the presence of an acidic catalyst, converting the vegetable oil The fatty acid in the distillate produces an esterified mixture containing fatty acid esters to reduce the fatty acid content in the vegetable oil distillate to less than 3% by weight; the esterification mixture is distilled to separate and remove the ester The fatty acid esters in the mixture, finally forming a distillation mixture; in the presence of a basic catalyst, the transesterification reaction is carried out on the distillation mixture using an alcohol to convert the glyceride in the distillation mixture into fatty acid esters and glycerol to form a transesterified mixture comprising glycerol and a fatty acid ester; purifying the transesterified mixture to substantially remove glycerol from the transesterified mixture to form a purified mixture; and subjecting the purified mixture to distillation to substantially remove fatty acids from the purified mixture The ester is finally produced into a composition containing a predetermined concentration of tocotrienol/tocopherol.

本發明之較佳實施例揭示，當醇類及酸性催化劑的存在下，對含有生育三烯酚/生育酚之植物油餾出物進行酯化反應，進而將存在油之中的脂肪酸轉換成脂肪酸烷基酯，進而形成含有甘油酯、脂肪酸烷基酯、固醇酯及生育酚/生育 三烯酚的酯化混合物，從而減少脂肪酸的含量至低於1%。較佳地，在酯化反應中所使用的醇類係為低級烷基醇類，例如甲醇、乙醇、異丙醇及丁醇，同時氫氯酸、磷酸、檸檬酸或其它適合的酸類可被作為酸性催化劑。應清楚明瞭，在酯化溶液(亦即酸性催化劑與醇類的混合溶液)中的酸性催化劑與低級烷基醇類的比例為0.005~5：1。 A preferred embodiment of the present invention discloses esterification of a vegetable oil distillate containing tocotrienol/tocopherol in the presence of an alcohol and an acidic catalyst, thereby converting a fatty acid present in the oil to a fatty acid alkane a base ester, which in turn forms a glyceride, a fatty acid alkyl ester, a sterol ester, and a tocopherol/fertility The esterification mixture of the triene phenol reduces the fatty acid content to less than 1%. Preferably, the alcohol used in the esterification reaction is a lower alkyl alcohol such as methanol, ethanol, isopropanol and butanol, while hydrochloric acid, phosphoric acid, citric acid or other suitable acid can be As an acidic catalyst. It should be clearly understood that the ratio of the acidic catalyst to the lower alkyl alcohol in the esterification solution (that is, the mixed solution of the acidic catalyst and the alcohol) is from 0.005 to 5:1.

在本發明較佳實施例中，酸性酯化反應係在溫度5℃至90℃下進行0.5小時至6小時，在進行此反應時，可以攪拌或不攪拌，但以攪拌為較佳。 In a preferred embodiment of the invention, the acidic esterification reaction is carried out at a temperature of from 5 ° C to 90 ° C for from 0.5 hours to 6 hours, and may be stirred or not stirred during the reaction, but stirring is preferred.

較佳地，進行完酸性酯化反應之後，將整個酯化混合物進行加熱，較佳以真空蒸發的方式或本技術領域中的降膜式蒸發器來實質上去除混合物中多餘的甲醇。此蒸發步驟在溫度30℃至60℃範圍內進行1小時至6小時。去除的甲醇與酯化混合物(亦即酸性催化劑、醇類及油餾出物)的比例為0.05~0.166：1。 Preferably, after the acidic esterification reaction has been carried out, the entire esterification mixture is heated, preferably by vacuum evaporation or by a falling film evaporator in the art to substantially remove excess methanol from the mixture. This evaporation step is carried out at a temperature of from 30 ° C to 60 ° C for from 1 hour to 6 hours. The ratio of methanol removed to the esterified mixture (ie, acidic catalyst, alcohol and oil distillate) is 0.05 to 0.166:1.

接著，將得到的酯化混合物以直流水或逆流水的方式進行洗滌，從而實質上去除多餘的酸性催化劑、可能出現的未反應的醇類及其它諸如固醇酯類的雜質。在此步驟中可使用熱水或冷水，但較佳使用溫度從40℃至80℃的水。為了確保自酯化混合物之中移除催化劑、醇類及其它雜質的效果可達到最佳，洗滌步驟需重複地進行直到酯化混合物的pH值達到6至8的範圍內。 Next, the resulting esterified mixture is washed with direct current water or countercurrent water to substantially remove excess acidic catalyst, unreacted alcohols that may be present, and other impurities such as sterol esters. Hot water or cold water can be used in this step, but water having a temperature of from 40 ° C to 80 ° C is preferably used. In order to ensure that the effect of removing catalysts, alcohols and other impurities from the esterification mixture is optimized, the washing step is repeated until the pH of the esterification mixture reaches a range of 6 to 8.

由於洗滌步驟的關係，酯化混合物中的水氣含量會因此增加。因此，為了進行後續的反應步驟，需特地將酯化混合物中的水氣含量減少至低於0.07%重量百分比。較佳地，以乾燥的方式來去除經洗滌之酯類混合物中的水氣，因而在一般大氣壓力下將經洗滌的酯類混合物在35℃至80℃的溫度下加熱0.5小時至10小時，從而酯類混合物中的水氣蒸發掉。 Due to the washing step, the moisture content in the esterification mixture will therefore increase. Therefore, in order to carry out the subsequent reaction steps, it is necessary to specifically reduce the moisture content in the esterification mixture to less than 0.07% by weight. Preferably, the moisture in the washed ester mixture is removed in a dry manner, whereby the washed ester mixture is heated at a temperature of from 35 ° C to 80 ° C for 0.5 to 10 hours under normal atmospheric pressure. Thereby the moisture in the ester mixture evaporates.

接著，將經乾燥的酯類混合物進行蒸餾，其中蒸餾步驟較佳在低於一般大氣壓力下進行(也被稱作為真空蒸餾)。此蒸餾步驟牽涉一個以上蒸餾管，產生含有脂肪酸烷基酯之第一濃縮餾出物與含有生育三烯酚/生育酚之第二濃縮餾出物。在本發明之較佳實施例中，在兩個依序排列的蒸餾管內進行蒸餾，此兩個依序排列的蒸餾管在大氣壓力0.01至1kPa及溫度120℃至180℃下進行反應。自酯化混合物之中分離大部分的脂肪酸烷基酯、未反應的脂肪酸及低沸點物質，這些所分離出的餾出物以第一分餾管之頂部流的形式呈現。剩餘的物質接著以剩餘流的形式從第一分餾管送入後續的蒸餾管之中，以進一步分離酯化混合物之中的脂肪酸烷基酯。自後續的蒸餾管中，實質上分離脂肪酸烷基酯及可能出現的脂肪酸，進而產生底部流，或是分離前述說明所提及的經蒸餾的酯化混合物，其中底部流包含佔總組成分中1%至5%的生育三烯酚/生育酚。 Next, the dried ester mixture is subjected to distillation, wherein the distillation step is preferably carried out at a lower than normal atmospheric pressure (also referred to as vacuum distillation). This distillation step involves more than one distillation tube to produce a first concentrated distillate containing fatty acid alkyl esters and a second concentrated distillate containing tocotrienol/tocopherol. In a preferred embodiment of the invention, the distillation is carried out in two successively arranged distillation tubes which are reacted at an atmospheric pressure of 0.01 to 1 kPa and at a temperature of 120 to 180 °C. Most of the fatty acid alkyl esters, unreacted fatty acids, and low boiling materials are separated from the esterification mixture, and the separated distillate is presented as a top stream of the first fractionator. The remaining material is then passed from the first fractionator to the subsequent distillation tube in the form of a residual stream to further separate the fatty acid alkyl esters in the esterification mixture. From the subsequent distillation tube, the fatty acid alkyl ester and the fatty acid that may be present are substantially separated, thereby producing a bottoms stream, or separating the distilled esterification mixture mentioned in the above description, wherein the bottom stream contains the total composition 1% to 5% tocotrienol/tocopherol.

在本發明之更佳的實施例中，在進行蒸餾之前，將酯化混合物送入管中進行烘乾，以進一步將水氣減少至低於0.01%重量百分比。 In a more preferred embodiment of the invention, the esterification mixture is sent to a tube for drying prior to distillation to further reduce moisture to less than 0.01% by weight.

根據本發明之較佳的實施例，在醇類及鹼性催化劑的存在下，將經蒸餾之酯化混合物進行轉酯反應，以使酯化混合物中的甘油酯轉換成脂肪酸酯類及甘油，進而形成轉酯混合物，此轉酯混合物含有甘油、脂肪酸酯類、生育三烯酚/生育酚及其它諸如固醇酯及甘油酯的雜質。在轉酯反應中所使用的醇類較佳為低級烷基醇，諸如甲醇、乙醇、異丙醇及丁醇，同時鹼性催化劑可以為甲醇鈉或甲醇鉀。本發明所屬技術領域中具有通常技藝者可以理解經蒸餾的酯化混合物與轉酯化溶液(鹼性催化劑與醇類的混合物)的比例為0.5-10：1。 According to a preferred embodiment of the present invention, the distilled esterified mixture is subjected to a transesterification reaction in the presence of an alcohol and a basic catalyst to convert the glyceride in the esterified mixture into fatty acid esters and glycerin. Further, a transesterified mixture is formed which contains glycerin, fatty acid esters, tocotrienol/tocopherol, and other impurities such as sterol esters and glycerides. The alcohol used in the transesterification reaction is preferably a lower alkyl alcohol such as methanol, ethanol, isopropanol or butanol, and the basic catalyst may be sodium methoxide or potassium methoxide. It will be understood by those of ordinary skill in the art that the ratio of the distilled esterified mixture to the transesterification solution (mixture of basic catalyst and alcohol) is from 0.5 to 10:1.

較佳地，轉酯化反應在溫度5℃至90℃下進行0.5至6小時，反應進行時可以攪拌或不攪拌，但以攪拌為佳。更佳地，在進行轉酯化反應前，藉由加熱來去除其中的水氣，以使水氣蒸發，進而減少第一餾出物中的水氣至低於0.20%重量百分比的程度。 Preferably, the transesterification reaction is carried out at a temperature of from 5 ° C to 90 ° C for from 0.5 to 6 hours, and the reaction may be carried out with or without stirring, but stirring is preferred. More preferably, the water vapor is removed by heating before the transesterification reaction to evaporate the water vapor, thereby reducing the moisture in the first distillate to less than 0.20% by weight.

進一步根據本發明之較佳實施例，藉由分離轉酯混合物中的甘油，來對轉酯混合物進行純化。可將轉酯混合物進行離心或重力沉降，以生產出富含酯部分(或稱為”純化化合物”)及富含甘油部分，富含甘油部分具有20%至40%重量百 分比的甘油。 Further in accordance with a preferred embodiment of the invention, the transesterified mixture is purified by isolating the glycerol in the transesterified mixture. The transesterified mixture can be subjected to centrifugation or gravity sedimentation to produce an ester-rich portion (or "purified compound") and a glycerin-rich portion having a glycerol-rich portion of 20% to 40% by weight. Fractional glycerin.

富含甘油部分以諸如氫氯酸、乙酸或硫酸進行中和，使其中多餘的鹼性催化劑轉換成鹽類，而此鹽類可輕易從甘油中分離，進而產生75%至90%重量百分比的甘油。 The glycerin-rich portion is neutralized with, for example, hydrochloric acid, acetic acid or sulfuric acid to convert excess alkaline catalyst into salts, which can be easily separated from the glycerol to produce 75% to 90% by weight. glycerin.

從前述步驟中所獲得的經純化的混合物較佳以直流水或逆流水進行洗滌，以去除多餘催化劑及可能出現未反應醇類及其它諸如固醇類的雜質。在此步驟中可使用熱水或冷水，但較佳將水從溫度40℃加熱至80℃，再來進行洗滌步驟。如同前述之洗滌步驟，較佳將富含酯部分重複進行洗滌直到富含酯部分的pH值降至6至8的範圍。 The purified mixture obtained from the foregoing step is preferably washed with direct current water or countercurrent water to remove excess catalyst and possibly unreacted alcohols and other impurities such as sterols. Hot water or cold water can be used in this step, but it is preferred to heat the water from a temperature of 40 ° C to 80 ° C to carry out a washing step. As with the aforementioned washing step, it is preferred to repeat the washing of the ester-rich portion until the pH of the ester-rich portion is lowered to the range of 6 to 8.

洗滌步驟進行完之後，經純化的混合物之中的水氣會因此增加，為了進一步進行後續的流程，需要使其中的水氣含量減少至低於0.07%重量百分比。藉由將經純化的混合物加熱0.5至10小時，使其溫度從35℃提高至80℃進而實質上移除其中的水氣。 After the washing step is completed, the moisture in the purified mixture is thus increased, and in order to further carry out the subsequent process, it is necessary to reduce the moisture content therein to less than 0.07% by weight. By heating the purified mixture for 0.5 to 10 hours, the temperature is raised from 35 ° C to 80 ° C to substantially remove the moisture therein.

隨著水氣減少或去除步驟之後，對所獲得經純化的混合物進行蒸餾以回收生育三烯酚/生育酚。值得注意的是，此處所提及的蒸餾類似於本說明書前述提及的蒸餾。具體地，經純化的混合物在兩個依序排列的蒸餾管以真空蒸餾方式進行，第一蒸餾管在大氣壓力0.01至1kPa及溫度120℃至180℃下進行反應，另一蒸餾管則在大氣壓力0.01至3kPa及溫度120℃至180℃下進行反應。在第一蒸餾管中，脂肪酸 酯類及其它低沸點成分主要以餾出物的形式進行回收，同時尚未回收的成分則以剩餘流的形式排出，此剩餘流再被送入下一個蒸餾管中，以進一步分離剩餘流中的脂肪酸酯類。大部分的脂肪酸酯類再次以餾出物自下一個蒸餾管中分離。在此同時，產生富含生育三烯酚/生育酚的剩餘流，其中生育三烯酚/生育酚占5%至35%重量百分比。值得注意，此剩餘流也可被稱為「經蒸餾的轉酯混合物」。 Following the water gas reduction or removal step, the purified mixture obtained is subjected to distillation to recover tocotrienol/tocopherol. It is worth noting that the distillation referred to herein is similar to the distillation mentioned above in this specification. Specifically, the purified mixture is subjected to vacuum distillation in two successively arranged distillation tubes, the first distillation tube is reacted at an atmospheric pressure of 0.01 to 1 kPa and at a temperature of 120 to 180 ° C, and the other distillation tube is at atmospheric pressure. The reaction is carried out at a pressure of 0.01 to 3 kPa and at a temperature of 120 ° C to 180 ° C. Fatty acid in the first distillation tube The esters and other low-boiling components are mainly recovered in the form of distillates, while the unrecovered components are discharged as residual streams, which are then sent to the next distillation tube to further separate the remaining streams. Fatty acid esters. Most of the fatty acid esters are again separated from the next distillation tube as a distillate. At the same time, a residual stream rich in tocotrienol/tocopherol is produced, wherein the tocotrienol/tocopherol comprises from 5% to 35% by weight. It is worth noting that this residual stream can also be referred to as a "distilled transesterified mixture."

在本發明之較佳實施例中，在進行蒸餾前，可將經純化的混合物進行加熱或將經純化的混合物送入乾燥器，以進一步減少水氣含量至低於0.01%重量百分比。 In a preferred embodiment of the invention, the purified mixture can be heated or the purified mixture can be sent to a dryer to further reduce the moisture content to less than 0.01% by weight prior to distillation.

然而，發明所屬技術領域中具有一般技藝者應理解要製造較高純度的氣流或欲得之重量百分比之含有生育三烯酚/生育酚的氣流，可將經蒸餾之轉酯混合物進行另一蒸餾步驟或更多的蒸餾步驟。經蒸餾的轉酯混合物可選擇性地被回收至蒸餾管內。 However, one of ordinary skill in the art will appreciate that to produce a higher purity gas stream or a desired percentage by weight of a tocotrienol/tocopherol-containing gas stream, the distilled transesterified mixture can be subjected to another distillation. Step or more distillation steps. The distilled transesterified mixture can be selectively recovered into the distillation tube.

本發明之另一較佳實施例揭示在蒸餾步驟中可獲得蒸餾氣流，此蒸餾氣流主要包含脂肪酸酯類，其可進一步加工或直接銷售以供應全球市場的需求。 Another preferred embodiment of the invention discloses that a distillation gas stream can be obtained in the distillation step, the distillation gas stream comprising primarily fatty acid esters which can be further processed or sold directly to supply the needs of the global market.

進一步根據本發明之較佳實施例，富含生育三烯酚/生育酚之經蒸餾的轉酯混合物可進一步進行加工步驟。較佳地，在此經蒸餾的轉酯混合物中添加低級烷基醇類，諸如甲醇、乙醇、丙醇及丁醇中之任一種或其組合，以分離呈現 晶體形式的固醇類。將得到的混合物連續攪拌且在溫度-30℃至0℃內進行12小時至3天的冷卻，最後形成結晶固醇。接下來將此混合物進行固液分離，以移除結晶固醇。較佳地，將此混合物進行離心，產生上層液及底層液。 Further in accordance with a preferred embodiment of the present invention, the tocotrienol/tocopherol-rich distilled transesterified mixture can be further subjected to processing steps. Preferably, a lower alkyl alcohol such as any one or a combination of methanol, ethanol, propanol and butanol is added to the distilled transesterified mixture to separate and present Sterols in crystalline form. The resulting mixture was continuously stirred and cooled at a temperature of -30 ° C to 0 ° C for 12 hours to 3 days to finally form a crystalline sterol. This mixture is then subjected to solid-liquid separation to remove the crystalline sterol. Preferably, the mixture is centrifuged to produce an upper layer liquid and a bottom layer liquid.

將含有固醇結晶體之底層液進一步以加熱或其它乾燥方式將其中的溶劑進行蒸發。 The bottom liquid containing the sterol crystals is further subjected to evaporation by heating or other drying means.

應清楚明瞭自離心所獲得的上層液包含30%至90%重量百分比之生育三烯酚/生育酚。上層液可進一步加熱，以蒸發或去除部分出現在上層液中的醇類，形成所需濃度之含有生育三烯酚/生育酚之組成物。發明所屬技術領域中具有一般技藝者亦可清楚明瞭此組成物也可包含其它化合物，諸如鯊烯(squalne)、固醇及CoQ10。 It should be clearly understood that the supernatant obtained from centrifugation contains 30% to 90% by weight of tocotrienol/tocopherol. The supernatant liquid may be further heated to evaporate or remove some of the alcohol present in the supernatant liquid to form a composition containing tocotrienol/tocopherol at a desired concentration. It will also be apparent to those skilled in the art that the composition may also include other compounds such as squalene, sterol, and CoQ10.

雖然本發明已以實施例揭露如上，然其並非用以限定本發明。任何該領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作些許之更動與潤飾。因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。 Although the present invention has been disclosed above by way of example, it is not intended to limit the invention. Anyone having ordinary knowledge in the field can make some changes and refinements without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims.

Claims (18)

一種自植物油餾出物回收生育三烯酚/生育酚的方法，其步驟包含：在酸性催化劑存在下，使用醇類對該植物油餾出物進行酯化反應，轉換該植物油餾出物之中的脂肪酸，產生一含有脂肪酸酯類的酯化混合物，從而減少該植物油餾出物之中的脂肪酸的含量至低於3%重量百分比；對該酯化混合物進行蒸餾，從而分離且去除該酯化混合物中的該脂肪酸酯類，以形成一蒸餾混合物；在鹼性催化劑的存在下，使用醇類對該蒸餾混合物進行轉酯交換反應，使該蒸餾混合物中的甘油酯轉換成脂肪酸酯類和甘油，形成含有甘油及脂肪酸酯類之轉酯混合物；純化該轉酯混合物，實質上去除該轉酯混合物中的甘油，以形成一純化混合物；以及對該純化混合物進行蒸餾，實質上去除該純化混合物之中的脂肪酸酯類，產生含有預定濃度之生育三烯酚/生育酚的組成物。 A method for recovering tocotrienol/tocopherol from a vegetable oil distillate, the method comprising: esterifying the vegetable oil distillate with an alcohol in the presence of an acidic catalyst, and converting the vegetable oil distillate a fatty acid, producing an esterified mixture containing fatty acid esters, thereby reducing the content of fatty acids in the vegetable oil distillate to less than 3% by weight; distilling the esterified mixture to separate and remove the esterified mixture The fatty acid esters to form a distillation mixture; the transesterification reaction is carried out on the distillation mixture using an alcohol in the presence of a basic catalyst to convert the glyceride in the distillation mixture into fatty acid esters and glycerin, Forming a transesterified mixture comprising glycerol and a fatty acid ester; purifying the transesterified mixture to substantially remove glycerol from the transesterified mixture to form a purified mixture; and subjecting the purified mixture to distillation to substantially remove the purified mixture The fatty acid esters in the form produce a composition containing a predetermined concentration of tocotrienol/tocopherol. 如申請專利範圍第1項之方法，其進一步包含對該酯化混合物進行洗滌的步驟，以去除催化劑、未反應之醇類及其它雜質，接著對已洗滌的酯化混合物進行加熱，以減少該混合物中殘餘的水氣含量至低於0.07%重量百分比。 The method of claim 1, further comprising the step of washing the esterification mixture to remove the catalyst, unreacted alcohols and other impurities, and then heating the washed esterification mixture to reduce the The residual moisture content of the mixture is less than 0.07% by weight. 如申請專利範圍第1項之方法，其進一步包含對該純化混合物進行洗滌的步驟，以去除催化劑、未反 應之醇類及其它雜質，接著對經洗滌的轉酯混合物進行加熱，以減少該混合物中殘餘的水氣含量至低於0.07%重量百分比。 The method of claim 1, further comprising the step of washing the purified mixture to remove the catalyst, not The alcohol and other impurities are then applied, and the washed transesterified mixture is then heated to reduce the residual moisture content of the mixture to less than 0.07% by weight. 如申請專利範圍第1項之方法，其中執行該純化步驟過程中，藉由離心或重力沉降去除該轉酯混合物中的甘油。 The method of claim 1, wherein the glycerin in the transesterified mixture is removed by centrifugation or gravity settling during the purification step. 如申請專利範圍第1項之方法，其進一步包含從該組成物中回收固醇類。 The method of claim 1, further comprising recovering sterols from the composition. 如申請專利範圍第1或5項之方法，其中該固醇類的回收係藉由醇類處理該組成物並冷卻處理後續形成之混合物，進而製造出結晶的固醇類。 The method of claim 1 or 5, wherein the recovery of the sterols is carried out by treating the composition with an alcohol and cooling the subsequently formed mixture to produce crystalline sterols. 如申請專利範圍第2或3項之方法，其中該洗滌步驟係為直流水或逆流水之洗滌步驟。 The method of claim 2, wherein the washing step is a washing step of direct current water or countercurrent water. 如申請專利範圍第2或3項之方法，其中該洗滌步驟係利用加熱至40℃到80℃的水來進行。 The method of claim 2, wherein the washing step is carried out using water heated to 40 ° C to 80 ° C. 如申請專利範圍第2或3項之方法，其中該洗滌的混合物係被加熱0.5至10小時，且溫度在35℃至80℃。 The method of claim 2, wherein the washed mixture is heated for 0.5 to 10 hours and the temperature is between 35 ° C and 80 ° C. 如申請專利範圍第9項之方法，其中該洗滌的混合物係被加熱0.5至10小時。 The method of claim 9, wherein the washed mixture is heated for 0.5 to 10 hours. 如申請專利範圍第1項之方法，其中對該酯化混合物進行蒸餾的步驟係在溫度120℃至180℃且壓力在0.01至1kPa下之兩個依序排列的蒸餾管內進行。 The method of claim 1, wherein the step of subjecting the esterification mixture to distillation is carried out in two sequentially arranged distillation tubes at a temperature of from 120 ° C to 180 ° C and a pressure of from 0.01 to 1 kPa. 如申請專利範圍第1項之方法，其中對該純化混合物進行蒸餾的步驟係在兩個依序排列的蒸餾管內進行，其中一個蒸餾管係在溫度120℃至180℃且壓力在0.01至1kPa下操作，另一個蒸餾管係在溫 度120℃至180℃且壓力在0.01至3Pa下操作。 The method of claim 1, wherein the step of distilling the purified mixture is carried out in two successively arranged distillation tubes, wherein one of the distillation tubes is at a temperature of from 120 ° C to 180 ° C and a pressure of from 0.01 to 1 kPa. Under the operation, another distillation tube is in the temperature The temperature is from 120 ° C to 180 ° C and the pressure is operated at 0.01 to 3 Pa. 如申請專利範圍第1項之方法，其進一步包含加熱該酯類混合物，或將該酯類混合物放入乾燥器的步驟，以進一步減少水氣含量至低於0.01%重量百分比。 The method of claim 1, further comprising the step of heating the mixture of esters or placing the mixture of the esters in a dryer to further reduce the moisture content to less than 0.01% by weight. 如申請專利範圍第1項之方法，其進一步包含加熱該純化混合物，或將該純化混合物放入乾燥器的步驟，以進一步減少水氣含量低於0.01%重量百分比。 The method of claim 1, further comprising the step of heating the purified mixture or placing the purified mixture in a dryer to further reduce the moisture content to less than 0.01% by weight. 如申請專利範圍第1項之方法，其中該鹼性催化劑係為甲醇鈉或甲醇鉀。 The method of claim 1, wherein the basic catalyst is sodium methoxide or potassium methoxide. 如前述任一項申請專利範圍之方法，其中該醇類係為甲醇、乙醇、丙醇及丁醇之其中任一種或組合。 A method according to any one of the preceding claims, wherein the alcohol is any one or combination of methanol, ethanol, propanol and butanol. 如申請專利範圍第1項之方法，其中該酸性催化劑係為氫氯酸、乙酸、硫酸或檸檬酸。 The method of claim 1, wherein the acidic catalyst is hydrochloric acid, acetic acid, sulfuric acid or citric acid. 如申請專利範圍第1項之方法，其中該植物油餾出物係棕櫚脂肪酸餾出物或任意之在總組成分中含有脂肪酸高於10%重量百分比的植物油餾出物。 The method of claim 1, wherein the vegetable oil distillate is a palmitic fatty acid distillate or any vegetable oil distillate having a fatty acid content greater than 10% by weight in the total composition.