WO2016176987A1 - 一种富含1,3-二油酸-2-棕榈酸甘油三酯结构脂的制备方法 - Google Patents

一种富含1,3-二油酸-2-棕榈酸甘油三酯结构脂的制备方法 Download PDF

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WO2016176987A1
WO2016176987A1 PCT/CN2015/096269 CN2015096269W WO2016176987A1 WO 2016176987 A1 WO2016176987 A1 WO 2016176987A1 CN 2015096269 W CN2015096269 W CN 2015096269W WO 2016176987 A1 WO2016176987 A1 WO 2016176987A1
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oil
acid
palmitic acid
free fatty
fatty acid
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French (fr)
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邹孝强
王兴国
金青哲
黄健花
刘睿杰
常明
王小三
潘秋琴
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Jiangnan University
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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C12P7/6445—Glycerides
    • C12P7/6454—Glycerides by esterification
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; PREPARATION THEREOF
    • A23C11/00—Milk substitutes, e.g. coffee whitener compositions
    • A23C11/02—Milk substitutes, e.g. coffee whitener compositions containing at least one non-milk component as source of fats or proteins
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS OR COOKING OILS
    • A23D9/00—Other edible oils or fats, e.g. shortenings or cooking oils
    • A23D9/02—Other edible oils or fats, e.g. shortenings or cooking oils characterised by the production or working-up
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats

Definitions

  • the invention relates to a preparation method of a 1,3-dioleic acid-2-palmitic acid triglyceride structural grease, and belongs to the technical field of oils and fats.
  • Breast milk is the best food for infants and young children. It provides almost all the nutrients needed for infants and young children. Fat accounts for about 3 to 5% of breast milk, but provides about 50% of energy for infants and young children. Among these fats, the content of triglyceride is 98% or more.
  • the content of palmitic acid in breast milk is 20-30%, a large amount of saturated fatty acid (palmitic acid) is in the sn-2 position of triglyceride, and unsaturated fatty acid is in the sn-1, 3 position, thus forming a large amount of sn-2.
  • sn-2 monoglyceride can be directly absorbed by intestinal epithelial cells, esterified into triglycerides, and then converted into chylomicron to transport energy to various parts of the body.
  • the absorption of fatty acids is related to their saturation and chain length. Long-chain saturated fatty acids easily form a high-melting soap with calcium and magnesium ions in the intestine and are excreted from the body.
  • Palmitic acid can avoid these adverse reactions at the sn-2 position.
  • Related studies have shown that the feces of palm-fed fat-fed infants at the sn-2 position are softer by feeding the infant with high sn-2 palmitic acid fat and fat with random distribution of palmitic acid, respectively.
  • OPO-fed infants were more rapidly transferred than OPO's isomer 1,2-dioleate-3-palmitic acid triglyceride (OOP). Therefore, this special structure of triglyceride in palm acid at the sn-2 position is important for the digestion, absorption and metabolism of fat in infants and young children.
  • the method for preparing an OPO product is mainly obtained by transesterification with a fatty acid by using tripalmitin (palm stearin) or lard as a substrate.
  • palm stearin has palmitic acid at the sn-2 position, but it also has the same amount of palmitic acid at the sn-1 and 3 positions, so it is necessary to prepare a OPO product with a larger substrate ratio.
  • some people use palm stearin as raw material to prepare higher purity OPO by alcoholysis and re-esterification, the process is complicated and it is difficult to obtain industrial production.
  • Lard as a cooking oil has religious taboos and cannot be widely used as a raw material for oils and fats. Therefore, it is extremely important to find a method of preparing an OPO product with a high content of palmitic acid at the sn-2 position, a relatively low total palmitic acid content, and a general-purpose fat.
  • An object of the present invention is to provide an economical and feasible method for preparing a salicylic acid triglyceride-rich structural fat by using salmon oil as a raw material, which is a solid fat component and high extracted from salmon oil.
  • the free fatty acid derived from oleic acid vegetable oil is a substrate, and transesterification is carried out under the catalysis of sn-1, 3-position specific lipase, and the free fatty acid is removed to obtain glycerol rich in 1,3-dioleic acid-2-palmitate.
  • Triester products are examples of the free fatty acid derived from oleic acid vegetable oil.
  • the method comprises: melting the salmon oil at 50 to 60 ° C, holding for 30 to 60 minutes, and cooling to a temperature of 15 to 30 ° C at a temperature decreasing rate of 1 to 5 ° C / min, the salmon After the oil is kept at this temperature for 5 to 48 hours, the liquid oil is removed by filtration to obtain a solid fat component of the palm oil rich in palmitic acid at the sn-2 position; and the sn-1, 3-position specific lipase is used as a catalyst.
  • the free fatty acid derived from the high oleic vegetable oil is used as an acyl donor, and the fat component of the salmon oil is acid-lyzed to remove the free fatty acid to obtain a product rich in 1,3-dioleic acid-2-palmitic acid triglyceride.
  • the catalyst is Lipozyme RM IM and/or Lipozyme TL IM.
  • the high oleic vegetable oil is one or more of high oleic rapeseed oil, high oleic sunflower oil, and olive oil.
  • the reaction temperature of the acid hydrolysis is from 40 ° C to 70 ° C.
  • the molar ratio of the fat component of the salmon oil to the free fatty acid is 1:1 to 10.
  • the acid hydrolysis is a batch reaction
  • the amount of enzyme added is 3% to 15% by weight
  • the reaction time is 1 h to 5 h
  • the stirring rate is 300 r/min to 800 r/min.
  • the acid hydrolysis is a continuous reaction with a substrate residence time of from 0.5 h to 3 h.
  • the removal of free fatty acids is by centrifugation to remove free fatty acids.
  • the free fatty acid is removed by molecular distillation at a temperature of from 180 ° C to 190 ° C, a rotational speed of from 110 to 130 rpm, and an absolute pressure of from 2 to 3 Pa.
  • the removal of free fatty acids is vacuum distillation.
  • the raw material of the raw carp oil used in the invention has the advantages of low price and wide source, and the solid fat component of the squid oil with high sn6 palmitic acid content and sn-1 and 3 palmitic acid content is obtained by fractionation. It can reduce the proportion of free fatty acids used in the acid hydrolysis reaction, and on the other hand, through the conversion, a product rich in 1,3-dioleic acid-2-palmitic acid triglyceride structural grease is obtained, and the product is derived from fish oil and is not religious. Restricted, so it can be widely used in the infant formula market.
  • the refined freshwater squid oil was melted at 60 ° C for 30 min, and then the squid oil was cooled to 30 ° C at a cooling rate of 5 ° C / min, and crystallized for 8 hours, and the solid fat in the squid oil was analyzed.
  • the salmon oil is filtered under vacuum to obtain a fat component of the salmon oil.
  • the squid oil solid fat component contains higher sn-2 palmitic acid and total palmitic acid than salmon oil.
  • the fatty acid composition and distribution of the used salmon oil and its fractionated solid fat are shown in the following table:
  • FA fatty acid content
  • sn-2FA fatty acid content at sn-2;
  • %sn-2FA the relative content of fatty acids in the sn-2 position in total fatty acids
  • Sn-1, 3FA sn-1, 3 fatty acid content.
  • the solid fat component of the squid is acid-decomposed, and the 1,3-position specific lipase Lipozyme RM IM is used as a catalyst.
  • the free fatty acid derived from high oleic sunflower oil is used as the acyl donor, and the molar of the squid oil and fatty acid. The ratio was 1:6, the reaction temperature was 50 ° C, the amount of enzyme added was 10 wt%, and the stirring rate was 500 rpm.
  • the lipase in the reaction mixture was removed by centrifugation.
  • the free fatty acid was removed by molecular distillation.
  • the molecular distillation conditions were: evaporation temperature 185 ° C; heat exchanger temperature 60 ° C; rotation speed 120 rpm; absolute pressure 2 Pa.
  • the fatty acid composition and distribution of the obtained hydrolyzed product are shown in Table 2 below.
  • the product prepared in this example has a palmitic acid content of 57.8%, a sn-1,3 oleic acid content of 60.1%, and a relative content of palmitic acid at the sn-2 position of 86.05%. .
  • the refined freshwater squid oil was melted at 50 ° C for 60 min, and then the squid oil was lowered to 20 ° C at a cooling rate of 3 ° C / min, and crystallized for 7 hours, and the fat was analyzed in the squid oil.
  • the salmon oil was vacuum filtered to obtain a solid fat component.
  • the squid oil solid fat component contains higher sn-2 palmitic acid and total palmitic acid than salmon oil.
  • the fatty acid composition and distribution of the obtained salmon oil fractionated fat are shown in Table 3 below:
  • Acid-decomposed squid solid fat component in a packed bed continuous reactor using the 1,3-position specific lipase Lipozyme TL IM as a catalyst, using free fatty acids derived from high oleic rapeseed oil as acyl donor, salmon oil and fatty acid
  • the molar ratio was 1:5, the reaction temperature was 40 ° C, and the substrate residence time was 2 hours. After the reaction, mechanical impurities which may be present in the reaction mixture are removed by centrifugation.
  • the obtained reaction mixture was subjected to molecular distillation to remove free fatty acids using the molecular distillation conditions: evaporation temperature, 180 ° C; heat exchanger temperature, 60 ° C; rotation speed, 130 rpm; absolute pressure, 3 Pa.
  • the fatty acid composition and distribution of the resulting product are shown in Table 4 below:
  • the product prepared by the present example has a palmitic acid content of 57.1%, a sn-1,3 oleic acid content of 59.6%, and a relative content of palmitic acid of the sn-2 position of 81.37%. .
  • the refined freshwater salmon oil was melted at 55 ° C for 50 min, and then the salmon oil was cooled to 25 ° C at a cooling rate of 2 ° C / min, and crystallized for 10 hours, and the solid fat in the salmon oil was analyzed.
  • the salmon oil is filtered under vacuum to obtain a solid fat component.
  • the split fat has a higher sn-2 palmitic acid and total palmitic acid than the salmon oil.
  • the fatty acid composition and distribution of the obtained salmon oil fractionated fat are shown in Table 5 below:
  • Acid-decomposition of cod oil in the packed bed continuous reactor using the 1,3 specific lipase Lipozyme TL IM as a catalyst, using fatty acids derived from high oleic rapeseed oil as acyl donor, salmon oil and fatty acid
  • the molar ratio was 1:4
  • the reaction temperature was 60 ° C
  • the substrate residence time was 0.5 hours.
  • mechanical impurities which may be present in the reaction mixture are removed by centrifugation.
  • the obtained reaction mixture was subjected to molecular distillation to remove free fatty acids using the molecular distillation conditions: evaporation temperature, 185 ° C; heat exchanger temperature, 60 ° C; rotation speed, 120 rpm; absolute pressure, 2 Pa.
  • the fatty acid composition and distribution of the obtained product are shown in Table 6 below:
  • the product prepared in this example has a palmitic acid content of 57.3%, a sn-1,3 oleic acid content of 58.33%, and a relative content of 7-29% palmitic acid at the sn-2 position. .
  • the total palmitic acid content of squid oil is about 30%, and about 40% of palmitic acid is in the sn-2 position, which is a good raw material for preparing OPO.
  • the portion rich in sn-2 palmitic acid in salmon oil is extracted and the fatty acid derived from high oleic vegetable oil is used as catalyst with sn-1, 3 selective lipase.
  • the acid solution is divided into salmon oil to obtain a product with a high OPO content.
  • the invention firstly uses the squid oil as a raw material, and combines the enzymatic acid hydrolysis to obtain a 1,3-dioleic acid-2-palmitic acid triglyceride structural ester product, and extracts the enriched squid oil containing sn -2 triglyceride component of palmitic acid, and then a free fatty acid derived from high oleic vegetable oil is used as an acyl donor, and a structural fat product rich in 1,3-dioleic acid-2-palmitic acid triglyceride is obtained by acid hydrolysis. .
  • the raw materials used in the invention are low in price, and the obtained product, the sn-2 bit palmitic acid, can be widely used as an additive in infant formula milk fat.

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Abstract

提供一种制备富含1,3-二油酸-2-棕榈酸甘油三酯结构脂的方法，属于油脂技术领域；将鲶鱼油在50～60℃熔化，保持30～60min，并以1～5℃/min的降温速率降温至15～30℃，将鲶鱼油在此温度下保持5～48h后，采用过滤的方式除去液态油，得到在sn-2位富含棕榈酸的鲶鱼油固脂成分；以sn-1,3位特异性脂肪酶为催化剂，以高油酸植物油来源的游离脂肪酸为酰基供体，酸解所述鲶鱼油固脂成分，除去游离脂肪酸后得到富含1,3-二油酸-2-棕榈酸甘油三酯的产品；原料价格低廉，所得产品1,3-二油酸-2-棕榈酸甘油三酯含量高，可作为添加剂广泛应用于婴幼儿配方奶粉脂肪中。

Description

一种富含1,3-二油酸-2-棕榈酸甘油三酯结构脂的制备方法 技术领域
本发明涉及一种富含1,3-二油酸-2-棕榈酸甘油三酯结构脂的制备方法，属于油脂技术领域。
背景技术
母乳是婴幼儿最佳的食物，提供包括婴幼儿所需的几乎所有的营养物质，其中脂肪占据母乳的3～5％左右，却为婴幼儿提供大约50％以上的能量。这些脂肪中，甘油三酯的含量在98％以上。母乳中棕榈酸的含量为20～30％，大量的饱和脂肪酸(棕榈酸)在甘油三酯的sn-2位，而不饱和脂肪酸在sn-1,3位，因此形成了大量的sn-2位饱和脂肪酸，sn-1,3位不饱和脂肪酸的甘油三酯，如1,3-二油酸-2-棕榈酸甘油三酯(OPO)。
脂肪经过婴幼儿摄入之后，大约有10～30％会首先通过舌脂酶及胃脂肪酶水解成为sn-2,3甘油二酯，然后再通过胰脂酶以及胆盐的作用水解成为sn-2单甘脂和脂肪酸，sn-2单甘脂可以直接通过小肠上皮细胞吸收，酯化为甘油三酯，再转化为乳糜乳粒运送到身体的各部位提供能量。脂肪酸的吸收同其饱和度及链长有重要关系。长链饱和脂肪酸容易同肠道内的钙镁离子形成高熔点的皂，排出体外。对于婴幼儿来说，这样会导致能量的损失，同时还可能导致便秘或者肠烂等后果。棕榈酸在sn-2位则可避免这些不良反应。相关研究表明，通过分别采用高sn-2棕榈酸的脂肪和随机分布棕榈酸的脂肪来喂养婴儿，以棕榈酸在sn-2位的脂肪喂养的婴儿的粪便更加柔软。同时，相关报道也显示，采用OPO喂养婴儿，相比采用OPO的同分异构体1,2-二油酸-3-棕榈酸甘油三酯(OOP)喂养，OPO的转移速度更快。因此，棕榈酸在sn-2位的这种特殊结构的甘油三酯，对脂肪在婴幼儿体内的消化、吸收以及代谢都有重要意义。
目前，制备OPO产品的方法主要是以三棕榈酸甘油酯(棕榈硬脂)或猪油为底物，通过与脂肪酸进行酯交换得到。其中，棕榈硬脂虽然在sn-2位上有棕榈酸，但是其在sn-1,3位也有相同量的棕榈酸，因此需要采用较大的底物比来制备OPO产品。虽有人采用棕榈硬脂为原料，以醇解及再酯化的方法来制备得到较高纯度的OPO，但是工艺比较复杂，难以得到工业化生产。而猪油作为食用油存在宗教禁忌，不能作为油脂原料被广泛使用。因此，找到一种sn-2位棕榈酸含量高，总棕榈酸含量相对低，同时又能够得到通用的油脂，并开发出制备OPO产品的方法就具有极为重要的意义。
发明内容
本发明的一个目的在于提供一种经济可行的以鲶鱼油为原料的制备sn-2位富含棕榈酸甘油三酯结构脂的方法，是以从鲇鱼油中分提得到的固脂成分和高油酸植物油来源的游离脂肪酸为底物，在sn-1,3位特异性脂肪酶的催化下发生酯交换反应，除去游离脂肪酸后得到富含1,3-二油酸-2-棕榈酸甘油三酯的产品。
在本发明的一种实施方式中，所述方法包括：将鲶鱼油在50～60℃熔化，保温30～60min，并以1～5℃/min的降温速率降温至15～30℃，将鲶鱼油在此温度下保持5～48h后，采用过滤的方式除去液态油，得到在sn-2位富含棕榈酸的鲶鱼油固脂成分；以sn-1,3位特异性脂肪酶为催化剂，以高油酸植物油来源的游离脂肪酸为酰基供体，酸解所述鲶鱼油固脂成分，除去游离脂肪酸后得到富含1,3-二油酸-2-棕榈酸甘油三酯的产品。
在本发明的一种实施方式中，所述催化剂为Lipozyme RM IM和/或Lipozyme TL IM。
在本发明的一种实施方式中，所述高油酸植物油为高油酸菜籽油、高油酸葵花籽油以及橄榄油中的一种或几种。
在本发明的一种实施方式中，所述酸解的反应温度为40℃～70℃。
在本发明的一种实施方式中，所述鲶鱼油固脂成分与游离脂肪酸的摩尔比为1：1～10。
在本发明的一种实施方式中，所述酸解为批次反应，其加酶量为3％～15wt％，反应时间为1h～5h，搅拌速率为300r/min～800r/min。
在本发明的一种实施方式中，所述酸解为连续反应，其底物停留时间在0.5h～3h。
在本发明的一种实施方式中，所述除去游离脂肪酸为离心分离除去游离脂肪酸。
在本发明的一种实施方式中，所述除去游离脂肪酸为分子蒸馏，温度为180℃～190℃，转速为110～130rpm，绝对压力为2～3Pa。
在本发明的一种实施方式中，所述除去游离脂肪酸为减压蒸馏。
本发明的有益效果：本发明所用原料鲶鱼油价格低廉，来源广泛，通过分提得到了sn-2棕榈酸含量高同时sn-1,3位棕榈酸含量低的鲇鱼油固脂成分，一方面能够降低酸解反应中所用游离脂肪酸比例，另一方面通过转化得到了富含1,3-二油酸-2-棕榈酸甘油三酯结构脂的产品，同时本产品来源于鱼油，不受宗教限制，因而可广泛应用于婴幼儿配方奶粉市场。
具体实施方式
在下面的描述中阐述了很多具体细节以便于充分理解本发明，但是本发明还可以采用其他不同于在此描述的其它方式来实施，本领域技术人员可以在不违背本发明内涵的情况下做 类似推广，因此本发明不受下面公开的具体实施例的限制。除另有说明，本发明涉及的测定脂肪酸、脂肪含量的方法为本领域常规采用的方法。
实施例1：
将精制淡水鲶鱼油在60℃下熔化，并保持30min，再将鲶鱼油以5℃/min的降温速率降温至30℃下，并结晶8小时，鲶鱼油中的固脂成分析出。将鲶鱼油通过真空过滤，得到鲶鱼油固脂成分。鲶鱼油固脂成分含有较鲶鱼油更高的sn-2棕榈酸及总棕榈酸。所用鲶鱼油及其分提固脂的脂肪酸组成及分布如下表所示：
表1.鲶鱼油及其分提固脂的脂肪酸组成及分布
Figure PCTCN2015096269-appb-000001
FA：脂肪酸含量；
sn-2FA：sn-2位脂肪酸含量；
％sn-2FA：sn-2位脂肪酸占总脂肪酸的相对含量；
sn-1,3FA：sn-1,3位脂肪酸含量。
从表1可以看出，通过分提得到的鲇鱼油固脂成分，相比鲇鱼油，sn-2棕榈酸的含量由49.34％提高到60.42％。
在间歇反应器中酸解鲶鱼固脂成分，以1,3位特异性脂肪酶Lipozyme RM IM为催化剂，采用源于高油酸葵花籽油的游离脂肪酸为酰基供体，鲶鱼油与脂肪酸的摩尔比为1:6，反应温度为50℃，加酶量为10wt％，搅拌速率为500转/min。反应后，通过离心去除反应混合物中的脂肪酶。并通过分子蒸馏的方式去除游离脂肪酸，所用分子蒸馏条件为：蒸发温度185℃；热交换器温度60℃；转速120rpm；绝对压力2Pa。所得酶解产物的脂肪酸组成及分布如下表2所示。
表2.酶解产物的脂肪酸组成及分布
FA种类 FA sn-2FA ％sn-2FA sn-1,3FA
C14:0 3.59 4.10 38.07 3.34
C16:0 22.39 57.80 86.05 4.69
C18:0 5.62 5.30 31.44 5.78
C18:1 60.10 21.88 12.14 79.21
C18:2 7.03 8.40 39.83 6.35
C18:3 0.30 0.40 44.44 0.25
由表2的数据可知，本实施例制备的产品sn-2棕榈酸含量可达57.8％，sn-1,3油酸的含量达60.1％，同时sn-2位棕榈酸的相对含量为86.05％。
实施例2：
将精制淡水鲶鱼油在50℃下熔化，保持60min，再将鲶鱼油以3℃/min的降温速率降至20℃，结晶7小时，鲶鱼油中固脂成分析出。将鲶鱼油真空过滤，得到固脂成分。鲶鱼油固脂成分含有较鲶鱼油更高的sn-2棕榈酸及总棕榈酸。所得鲶鱼油分提固脂的脂肪酸组成及分布如下表3所示：
表3.  20℃鲶鱼油分提固脂的脂肪酸组成及分布
Figure PCTCN2015096269-appb-000002
Figure PCTCN2015096269-appb-000003
在填充床连续反应器中酸解鲶鱼固脂成分，以1,3位特异性脂肪酶Lipozyme TL IM为催化剂，采用源于高油酸菜籽油的游离脂肪酸为酰基供体，鲶鱼油与脂肪酸的摩尔比为1:5，反应温度为40℃，底物停留时间为2小时。反应之后，通过离心去除反应混合物中可能有的机械杂质。
将所得反应混合物通过分子蒸馏的方式去除游离脂肪酸，所用分子蒸馏条件为：蒸发温度，180℃；热交换器温度，60℃；转速，130rpm；绝对压力，3Pa。所得产品的脂肪酸组成及分布如下表4所示：
表4.酶解产物的脂肪酸组成及分布
FA种类 FA sn-2FA ％sn-2FA sn-1,3FA
C14:0 3.42 4.15 40.45 3.06
C16:0 23.39 57.10 81.37 6.54
C18:0 5.67 5.51 32.39 5.75
C18:1 59.60 21.17 11.84 78.82
C18:2 7.22 8.86 40.90 6.40
C18:3 0.30 0.40 44.44 0.25
由表4的数据可知，本实施例制备的产品sn-2棕榈酸含量可达57.1％，sn-1,3油酸的含量达59.6％，同时sn-2位棕榈酸的相对含量为81.37％。
实施例3：
将精制淡水鲶鱼油在55℃下熔化，并保持50min，再将鲶鱼油以2℃/min的降温速率降温至25℃，并结晶10小时，鲶鱼油中的固脂成分析出。将鲶鱼油通过真空过滤，得到固脂成分。分提固脂含有较鲶鱼油更高的sn-2棕榈酸及总棕榈酸。所得鲶鱼油分提固脂的脂肪酸组成及分布如下表5所示：
表5. 25℃鲶鱼油分提固脂的脂肪酸组成及分布
FA种类 FA sn-2FA ％sn-2FA sn-1,3FA
C12:0 0.33 0.59 59.60 0.20
C14:0 4.72 4.38 30.93 4.89
C16:0 34.88 58.89 56.28 22.88
C16:1 0.49 0.62 42.18 0.43
C18:0 9.22 4.88 17.64 11.39
C18:1 37.57 18.93 16.80 46.89
C18:2 8.62 8.74 33.80 8.56
C18:3 0.52 0.41 26.28 0.58
C20:0 0.51 0.39 25.49 0.57
C20:1 1.28 0.35 9.11 1.75
C20:2 0.23 0.12 17.39 0.29
C20:3 0.32 0.21 21.88 0.38
C20:4 0.17 0.10 19.61 0.21
C22:0 0.35 0.15 14.29 0.45
C22:1 0.31 0.08 8.60 0.43
C22:2 0.08 0.06 25.00 0.09
C24:1 0.11 0.05 15.15 0.14
C22:4 0.05 0.07 46.67 0.04
C22:5 0.09 0.10 37.04 0.09
C22:6 0.08 0.08 33.33 0.08
在填充床连续反应器中酸解鲶鱼油固脂成分，以1,3位特异性脂肪酶Lipozyme TL IM为催化剂，采用源于高油酸菜籽油的脂肪酸为酰基供体，鲶鱼油与脂肪酸的摩尔比为1:4，反应温度为60℃，底物停留时间为0.5小时。反应之后，通过离心去除反应混合物中可能有的机械杂质。
将所得反应混合物通过分子蒸馏的方式去除游离脂肪酸，所用分子蒸馏条件为：蒸发温度，185℃；热交换器温度，60℃；转速，120rpm；绝对压力，2Pa。所得产品的脂肪酸组成及分布如下表6所示：
表6.酶解产物的脂肪酸组成及分布
FA种类 FA sn-2FA ％sn-2FA sn-1,3FA
C14:0 3.48 4.01 38.41 3.22
C16:0 24.49 57.3 77.99 8.09
C18:0 5.43 5.62 34.50 5.34
C18:1 58.33 21.07 12.04 76.96
C18:2 7.42 9.02 40.52 6.62
C18:3 0.2 0.4 66.67 0.10
由表8的数据可知，本实施例制备的产品sn-2棕榈酸含量可达57.3％，sn-1,3油酸的含量达58.33％，同时sn-2位棕榈酸的相对含量为77.99％。
从表1可以看出鲶鱼油总棕榈酸含量在30％左右，大约有40％以上的棕榈酸在sn-2位，是制备OPO的良好原料。根据鲶鱼油的脂肪酸组成及分布，通过分提富集鲶鱼油中富含sn-2棕榈酸的部分，再以sn-1,3位选择性脂肪酶为催化剂，以高油酸植物油来源的脂肪酸为酰基供体，酸解分提鲶鱼油，可得到高OPO含量的产品。
本发明首次以鲶鱼油为原料，结合分提及酶法酸解制备得到富含1,3-二油酸-2-棕榈酸甘油三酯结构脂产品，通过分提富集鲶鱼油中含有sn-2棕榈酸的甘油三酯成分，再以高油酸植物油来源的游离脂肪酸为酰基供体，通过酸解得到富含1,3-二油酸-2-棕榈酸甘油三酯的结构脂产品。本发明所用原料价格低廉，所得产品sn-2位棕榈酸及可作为添加剂广泛应用于婴幼儿配方奶粉脂肪中。
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。

Claims (9)

  1. 一种富含1,3-二油酸-2-棕榈酸甘油三酯结构脂的制备方法，其特征在于：包括，
    将鲶鱼油在50～60℃熔化，保持30～60min，并以1～5℃/min的降温速率降温至15～30℃，将鲶鱼油在此温度下保持5～48h后，采用过滤的方式除去液态油，得到在sn-2位富含棕榈酸的鲶鱼油固脂成分；
    以sn-1,3位特异性脂肪酶为催化剂，以高油酸植物油来源的游离脂肪酸为酰基供体，酸解所述鲶鱼油固脂成分，除去游离脂肪酸后得到富含1,3-二油酸-2-棕榈酸甘油三酯的结构脂。
  2. 根据权利要求1所述的方法，其特征在于：所述催化剂为对甘油三酯的1,位和3位具有选择性的脂肪酶。
  3. 根据权利要求1所述的方法，其特征在于：所述高油酸植物油为高油酸菜籽油、高油酸葵花籽油以及橄榄油中的一种或几种。
  4. 根据权利要求1所述的方法，其特征在于：所述酸解，其反应温度为40℃～70℃。
  5. 根据权利要求1所述的方法，其特征在于：所述鲶鱼油固脂成分与游离脂肪酸的摩尔比为1：1～10。
  6. 根据权利要求1、4或5所述的方法，其特征在于：所述酸解为批次反应，其加酶量为3％～15wt％，反应时间为1h～5h，搅拌速率为300r/min～800r/min。
  7. 根据权利要求1、4或5所述的方法，其特征在于：所述酸解为连续反应，其底物停留时间在0.5h～3h。
  8. 根据权利要求1所述的方法，其特征在于：所述除去游离脂肪酸为离心分离或过滤。
  9. 根据权利要求1所述的方法，其特征在于：所述除去游离脂肪酸为分子蒸馏或者减压蒸馏。
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