WO2012006934A1 - 湄公河三角洲鲶鱼油脂及应用及制备母乳脂肪替代物的方法 - Google Patents

湄公河三角洲鲶鱼油脂及应用及制备母乳脂肪替代物的方法 Download PDF

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WO2012006934A1
WO2012006934A1 PCT/CN2011/077001 CN2011077001W WO2012006934A1 WO 2012006934 A1 WO2012006934 A1 WO 2012006934A1 CN 2011077001 W CN2011077001 W CN 2011077001W WO 2012006934 A1 WO2012006934 A1 WO 2012006934A1
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fat
oil
squid
fatty acid
mixed
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PCT/CN2011/077001
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English (en)
French (fr)
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伍翔飞
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深圳精益油脂技术有限公司
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B1/00Production of fats or fatty oils from raw materials
    • C11B1/06Production of fats or fatty oils from raw materials by pressing
    • C11B1/08Production of fats or fatty oils from raw materials by pressing by hot pressing
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11CFATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10Ester interchange

Definitions

  • the invention belongs to the field of edible oils and fats, and particularly relates to a fat derived from a salmon of the Mekong Delta and its application in preparing a fat substitute for breast milk.
  • Breast milk is the perfect food for the baby's growth and development. Therefore, WHO advocates breastfeeding for at least 6 months after the baby is born to ensure the baby's growth and development, improve immunity and prevent infectious diseases.
  • Breast milk contains about 4 to 4.5% fat, 98% of which is triglyceride.
  • the types of fatty acids in breast milk are complex. Saturated fatty acids include medium, medium and long chain and long chain saturated fatty acids such as lauric acid ( 5-7%), palmitic acid (20-24%), stearic acid (7.1-9%).
  • Monounsaturated fatty acids include oleic acid (31-38%), palmitoleic acid (2.5-3.8%), n-3 polyunsaturated fatty acids in addition to linoleic acid; n-3 polyunsaturated fatty acids contain ⁇ - In addition to linolenic acid, it also contains docosahexaenoic acid (DHA, 0.3-1.9%).
  • DHA docosahexaenoic acid
  • the fat in the initial infant formula is mainly cow's milk fat in whole milk powder, but the fat composition of milk and fat structure are significantly different from breast milk fat.
  • the content of saturated fatty acids (C4-C10) in low-carbon chains in cow's milk fat is higher, while the content of polyunsaturated fatty acids such as C18:2 is lower, and other polyunsaturated fatty acids such as C18:3, C20:4 and C22:6 are almost No.
  • the saturated fatty acids in the milk are mainly concentrated in the Sn-1, 3 position, while the saturated fatty acids in the breast milk (mainly C16:0) are mostly in the Sn-2 position.
  • the content of saturated fatty acids (SFA) in breast milk fat is significantly lower than that of cow's milk fat.
  • Fat, unsaturated fatty acid (TUFA) and polyunsaturated fatty acids (PUFA) were significantly higher than cow's milk fat.
  • TUFA unsaturated fatty acid
  • PUFA polyunsaturated fatty acids
  • the sources of fats contained in domestic infant formula are: 1. Mixing a single variety of first-grade refined vegetable oil with milk fat; 2. Mixing various refined vegetable oils with cow's milk fat; 3. Using vegetable oils all , where palmitic acid is provided by palm oil.
  • the vegetable oils involved are: high oleic sunflower oil, canola oil, soybean oil, palm oil, palm kernel oil, coconut oil, sunflower oil, safflower oil and other oils.
  • a mixture of several vegetable oils and fats can give a product with a fatty acid composition close to that of breast milk, but because breast milk fat has a special fat structure (the type of triglyceride is mainly USU type, and palmitic acid is mainly present in the Sn-2 position) Therefore, the mixed vegetable oil with palm oil as the main source of palmitic acid can only reach the fatty acid composition close to the breast milk fat, but can not reach the level close to the fat structure of the breast milk.
  • This mixed fat is hydrolyzed by pancreatic lipase into free fatty acids and monoglycerides. Free palmitic acid in the small intestine easily forms insoluble calcium soap with metal ions, resulting in double loss of calcium ions and energy.
  • the oil at the Sn-2 position is superior to the mixed vegetable oil with palm oil as the main source of palmitic acid. That is, the palmitic acid similar to the fat structure of breast milk is mainly located in the Sn-2 position, which is beneficial to increase the absorption rate of fat, enhance the absorption of calcium, increase bone density and reduce the hard stool of infants and young children, and prevent constipation.
  • lard is a religious taboo as a cooking oil and cannot be widely used as a raw material for oils and fats.
  • Saturated fatty acids mainly stearic acid and palmitic acid
  • the palmitic acid fatty acid composition has a palmitic acid ratio of more than 40%, but most palmitic acid is distributed at the Sn-1 or Sn-3 position, and the palmitic acid content at the Sn-2 position is less than 10%.
  • Transesterification Palm oil is subjected to random transesterification under the action of a chemical catalyst (sodium methoxide or sodium ethoxide) to distribute palmitic acid evenly at the Sn-1, Sn-3 and Sn-3 positions of the glyceride. Above, the content of palmitic acid at the Sn-2 position reaches a level of more than 40% of palmitic acid in the total fatty acid composition.
  • a chemical catalyst sodium methoxide or sodium ethoxide
  • Oil and fat fractionation The palm oil is divided into two parts, solid and liquid, by using the difference in melting point and solubility of various triglycerides constituting palm oil at a certain temperature, so that PPP in the solid part (tripy palmitate) The content of the oil ester) is increased, so that the palmitic acid content at the Sn-2 position is raised to the desired level.
  • the palmitic acid content at the Sn-2 position in the fat or oil raw material obtained by the two methods does not exceed 33.3%.
  • a reasonable mixture of mixed fatty acid or fatty acid lower alcohol ester mixture is selected, and the ester is catalyzed by Sn-1,3 specific lipase.
  • the reactant is deodorized under vacuum, and the mixed fatty acid or the fatty acid lower alcohol ester mixture which is replaced by the reaction is removed to obtain a fat which is close to the fat structure of the breast milk.
  • the content of palmitic acid in the Sn-2 position in the final product obtained by this method is not high.
  • the above preparation methods have various defects, such as the palmitic acid at the Sn-2 position of the breast milk fat substitute prepared by transesterification of mixed fats and oils, which accounts for only about 40% of the total palmitic acid.
  • palmitic acid on the actual Sn-2 position of breast milk
  • the palmitic acid is over 67% apart.
  • the transesterification reaction of fats and oils and fatty acids in lipase is used. Since the raw materials mainly use palm oil, the proportion of palmitic acid in the Sn-2 position in palm oil is lower than that of total palmitic acid (not higher than 33.3). %), the content of palmitic acid at the Sn-2 position in the final product after enzymatic transesterification is not high.
  • the object of the present invention is to provide a breast milk fat substitute derived from the mekong milk delta which can be used for preparing a breast milk fat substitute which is close to the fat composition of the breast milk, in view of the above problems existing in the existing breast milk fat substitute for infant formula and its preparation method.
  • the grease is applied to the preparation of a breast milk fat substitute.
  • the oil derived from the Mekong delta squid of the present invention is extracted from whole fish of the Mekong Delta ⁇ Panga ⁇ odon gigas or extracted from the rest of the fish fillet or the fractionated liquid component of the squid fat .
  • the Mekong delta squid refers to basa catf i sh and tra cat f i sh. One or both of them may be employed.
  • the method for extracting the fat of the carp is: washing the raw materials of the carp in the Mekong Delta, pulverizing the whole fish or pulverizing the remaining raw materials after removing the fish pieces, and then continuously retorting, pressure filtration, and heating the filtrate with steam. 20-60 minutes, then centrifuge, The obtained crude fat is dehydrated and then refined to obtain salmon fat.
  • the method for extracting the liquid component of the salmon fat is: heating the fat of the carp of the Mekong Delta to 60 ° C, and after cooling for 20 minutes, cooling to 30 ° C at a rate of 10 ° C / hour, Then, the temperature is lowered to 15 ° C at a rate of 1.5-2.5 ⁇ / hr, and the temperature is crystallized for 3-5 hours. All the above processes are stirred, and the solid crystal portion to be precipitated reaches 10-50% of the total weight, and the temperature is 15 °. Filtration separation was started at C, and after filtration, a liquid component was obtained.
  • a method for preparing a breast milk fat substitute using the oil derived from the Mekong delta carp of the present invention comprises the following steps:
  • step (3) Enzymatic transesterification of the oil obtained in step (1) or step (2) with a mixed fatty acid or a mixed fatty acid lower alcohol ester by lipase catalysis, or a step
  • the mixed fat obtained by mixing the oil and fat obtained in the step (2) with other vegetable oils and enzymatic transesterification reaction with the mixed fatty acid or the mixed fatty acid lower alcohol ester under lipase catalysis, the fat or the mixed fat and the mixed
  • the weight ratio of the fatty acid or the mixed fatty acid lower alcohol ester is (2:1) - (1:2), and after the transesterification reaction, the oil obtained by the reaction is separated by distillation under reduced pressure and refined to obtain a breast milk fat substitute.
  • the extraction method of the (1) ⁇ is to clean the squid raw material of the Mekong Delta, pulverize the whole fish or pulverize the remaining raw materials after removing the fish pieces, and then continuously cook, press-filter, and heat the filtrate with steam. 20-60 minutes, then centrifuge to obtain the crude fat The fat is dehydrated and then refined to obtain salmon fat.
  • the temperature at which the (2) hydrazine is extracted is preferably 15 to 25 °C.
  • the fatty acid lower alcohol ester is preferably a fatty acid ethyl ester.
  • the mixed fatty acid in the (3) hydrazine is derived from a hydrolysis product of any mixed fat of soybean oil, canola oil, sunflower oil, corn oil, coconut oil, palm kernel oil; the mixed fatty acid lower alcohol
  • the ester is derived from the alcoholysis product of any mixed oil of soybean oil, canola oil, sunflower oil, corn oil, coconut oil, palm kernel oil.
  • the lipase is S n-1, a specific lipase of 3, preferably LIPOZYME RLIM.
  • a lipase is directly added to the reactant to carry out a batch reaction, or the reactant is filled in the reaction column by an enzyme.
  • the present invention comprises a mixture of a triglyceride obtained by reacting a fatty acid or a mixed fatty acid lower alcohol ester with a Mekong Delta salmon fat or a liquid component thereof by a specific lipase catalyzed by 1, 3 positions. Due to the relatively high content of palmitic acid at the Sn-2 position in the Mekong Delta salmon fat or its fractionated liquid component, in the final reaction product
  • the palmitic acid content at the Sn-2 position is also relatively high, which is consistent with the palmitic acid content at the Sn-2 position in the breast milk fat, that is, more than 60%.
  • this breast milk fat substitute does not require additional AA and DHA or only a small amount of AA or DHA.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • Basha carp Basa catfish
  • squid tra catfish
  • the refining in the embodiment of the present invention adopts mature technology, and the specific steps include: degumming, deacidification, decolorization and deodorization.
  • the deodorization stage was carried out at a temperature of 240 ° C, a residence time of 65 minutes, and a vacuum of 2. 3 mbar.
  • the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the squid The speed is lowered to 15 ° C, and the temperature is crystallized for 3-5 hours. All the above processes are stirred, and after the solid crystal portion to be precipitated reaches 10-50% of the total weight, the filtration separation starts at a temperature of 15 ° C. The initial filtration pressure is 3 bar and the pressure is reduced to 12 bar. After filtration, the fractionated liquid component is obtained.
  • Enzymatic transesterification The liquid component of the Mekong delta carp obtained from the above second enthalpy is mixed with the mixed fatty acid ethyl ester obtained in the above third step by a ratio of 1:1, and the mixture is passed through a reaction column packed with a lipase LIPOZYME.
  • the reaction temperature was 55 ° C, and the flow rate was a reaction of the same weight as the enzyme per hour.
  • the reaction product is further subjected to molecular distillation at 120-150 Torr for refining to obtain a breast milk fat substitute.
  • Lipase LIPOZYME RMIM was purchased from Novozymes of Denmark.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • the canola oil, soybean oil and coconut oil were mixed in a weight ratio of 6:2:2, heated to 100 ° C while stirring, kept for 20 minutes, and dehydrated.
  • the lye is first added to the saponification to separate the glycerin, and then hydrochloric acid is added for acidification to obtain a mixed fatty acid.
  • the weight ratio of squid fat to mixed fatty acid in the Mekong Delta is 1:1.
  • the lipase LIPOZYME RMIM is added in an amount of 5% by weight of the fat, the reaction temperature is 55 ° C, and the transesterification reaction time is 4 hours. After the reaction is completed, molecular distillation is carried out at 150-18 (TC) to refine, and a breast milk fat substitute is obtained.
  • TC 150-18
  • Corn oil, linseed oil and coconut oil were mixed in a weight ratio of 6:2:2, heated to 100 ° C, stirred, kept for 20 min, and dehydrated.
  • the oil 1% catalyst K0H was added to ethanol (the molar ratio of ethanol to fat was 6:1) and dissolved by stirring. After the grease was cooled to 60 ° C, a catalyst-added ethanol solution was added to start the reaction for 3 hours.
  • a citric acid solution (1:1 molar ratio of citric acid to K0H) was added and washed with water. Vacuum evacuation at 60 ° C for 1-2 hours. The final product is mixed with fatty acid ethyl ester.
  • the weight ratio of the fractionated liquid component of the Mekong delta carp to the mixed fatty acid ethyl ester obtained in the above step is 1 : 1, and the lipase LIPOZYME is added in an amount of 5% by weight of the fat and the reaction temperature is 55. C, reaction time 4 hours. After the end of the transesterification reaction, molecular distillation is carried out at 120-15 CTC, followed by refining to obtain a breast milk fat substitute.
  • the Mekong Delta carp fat is mixed with the palm oil after random transesterification in a weight ratio of 5:5, and the weight ratio of the mixed fat to the mixed fatty acid ethyl ester obtained in the above step 2 is 1:1, and the mixed fat and mixed oil are mixed.
  • the mixture of fatty acid ethyl esters was passed through a reaction column packed with lipase LIPOZYME RMIM at a reaction temperature of 55 ° C and a flow rate of the same amount of reactant per hour as the enzyme.
  • the reaction product is further subjected to molecular distillation at 120-15 CTC, and refined to obtain a breast milk fat substitute.

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Abstract

本发明为一种湄公河三角洲鲶鱼油脂及应用及制备母乳脂肪替代物的方法。本发明的来源于湄公河三角洲鲶鱼的油脂,是从湄公河三角洲鲶鱼(Pangasianodongigas)的全鱼中提取或从去除鱼片以后的其余部位提取的鲶鱼脂肪或其分提液体组分。所述鲶鱼油脂应用于制备母乳脂肪替代物。湄公河三角洲鲶鱼油脂制备的母乳脂肪替代物中的Sn-2位上的棕榈酸含量相对较高,可以达到与母乳脂肪中Sn-2位上棕榈酸含量一致,即达到60%以上。同时,由于湄公河三角洲鲶鱼脂肪或其分提液体组分存在AA和DHA,这种母乳脂肪替代物不需要额外添加AA和DHA或者只需要添加少量的AA或DHA。

Description

湄公河三角洲鲶鱼油脂及应用及制备母乳脂肪替代物的方法
技术领域
本发明属于食用油脂领域,尤其涉及一种来源于湄公河三角洲鲶 鱼的油脂及其在制备母乳脂肪替代物中的应用。
背景技术
母乳是适合婴儿生长发育的最完美的食物。 因此 WHO提倡在婴儿 出生后母乳哺育至少 6个月, 以保证婴儿生长发育、 提高免疫力和预 防传染疾病。 母乳中含有约 4~4.5%的脂肪, 其中 98%是甘油三酯。 母 乳中脂肪酸的种类复杂, 饱和脂肪酸包括, 中链、 中长链及长链饱和 脂肪酸, 如月桂酸 ( 5-7%) 、 棕榈酸 (20-24%) , 硬脂酸 (7.1-9%) ; 单不饱和脂肪酸包括油酸 (31-38%) 、 棕榈油酸 (2.5-3.8%) 、 n-3 多不饱和脂肪酸除含有亚油酸; n-3 多不饱和脂肪酸除含有 α-亚麻 酸外, 还含有二十二碳六烯酸 (DHA, 0.3-1.9%) 。
最初婴儿配方奶粉中的脂肪主要是全脂奶粉中的牛乳脂肪,但是 牛乳脂肪中无论是脂肪酸组成还是脂肪结构,都与母乳脂肪有着显著 的差异。 牛乳脂肪中低碳链的饱和脂肪酸 (C4-C10 ) 含量较高, 而 多不饱和脂肪酸如 C18:2含量较低, 其它的多不饱和脂肪酸 C18:3、 C20:4和 C22:6等几乎没有。 另外, 牛乳中的饱和脂肪酸主要集中在 Sn-1,3位上,而母乳中的饱和脂肪酸(主要是 C16:0 )则大部分在 Sn-2 位上。
如前所述, 母乳脂肪中饱和脂肪酸 (SFA ) 含量显著低于牛乳脂 肪, 不饱和脂肪酸(TUFA)和多不饱和脂肪酸(PUFA)含量显著高于 牛乳脂肪。在婴儿配方食品中通过添加植物油能消除这些差异。目前, 在国内婴儿配方奶粉中所含的油脂来源主要有: 1. 使用单一品种的 一级精炼植物油与牛乳脂肪混合; 2. 使用的多种精炼植物油与牛乳 脂肪混合; 3. 全部采用植物油脂, 其中的棕榈酸由棕榈油提供。 涉 及的植物油种类有: 高油酸葵花籽油, 低芥酸菜籽油、 大豆油、 棕榈 油、 棕仁油、 椰子油、 葵花籽油、 红花油等多种油料。
国际上已经有不少专利, 如 US5,601,860等, 是以植物油直接调 和的方法。 主要用富含 C 16 : 0的油(如棕榈油等)与其它的含必需脂肪 酸的油 (如大豆油等)调和所得。 以牛奶直接代替人乳脂, 如前所述, 其中的甘三酯脂肪酸与人乳脂有差别。如再配以植物油, 也会使甘三 酯结构很难符合要求。 以植物油为原料, 用化学催化剂如甲醇钠进行 随机酯交换, 如专利 EP0376628。
通过几种植物油脂的混合可以得到脂肪酸组成与母乳脂肪相接 近的产品, 但是由于母乳脂肪具有特殊的脂肪结构(甘三酯类型主要 为 USU型, 且棕榈酸主要存在于 Sn-2位上) , 所以以棕榈油为棕榈酸 主要来源的混合植物油只能达到脂肪酸组成与母乳脂肪接近,但不能 达到与母乳脂肪结构相接近的水平。这种混合油脂经胰脂肪酶水解成 游离脂肪酸和单甘酯。而小肠内的游离棕榈酸易与金属离子形成不溶 性的钙皂, 从而导致钙离子和能量的双重流失。近二十年来, 一些营 养学和临床医学研究者对比了这两类结构的油脂 (棕榈酸主要位于 Sn-2位置和 Sn-1, 3位置) 对婴儿营养吸收的影响, 发现棕榈酸主要 位于 Sn-2位的油脂优于以棕榈油为主要棕榈酸来源的混合植物油脂。 即与母乳脂肪结构类似的棕榈酸主位于 Sn-2 位的油脂, 有利于提高 脂肪的吸收率、 增强钙的吸收、 提高骨密度及减少婴幼儿硬便, 防止 便秘。
早在上世纪八十年代随着婴儿营养吸收的研究的深入,关于棕榈酸主 要位于 Sn-2位的结构油脂的制备研究已经展开。制备母乳脂肪替代物 的关键是要找到 Sn-2位高棕榈酸含量的油脂。 目前报道的高 Sn-2位 高棕榈酸含量油脂原料有两类: 棕榈油硬脂和酯交换的棕榈油。猪油 也是一种 Sn-2棕榈酸含量较高的油脂,脂肪酸组成中棕榈酸的比例为 20-30%, 而 Sn-2位上的棕榈酸含量则高达 60%以上。 但猪油作为食 用油存在宗教禁忌, 不能作为油脂原料被广泛使用。植物油中饱和脂 肪酸 (主要是硬脂酸和棕榈酸) 天然分布于 Sn-1 或 Sn-3 位上, Sn-2 位上的棕榈酸含量很少。棕榈油的脂肪酸组成中棕榈酸比例高达 40% 以上, 但绝大部分棕榈酸分布于 Sn-1或 Sn-3位上, Sn-2位上的棕榈 酸含量不到 10%。
为了得到 Sn-2位高棕榈酸含量的植物油脂, 可以采用油脂改性 的方法: 酯交换和分提。 (1 )酯交换: 将棕榈油在化学催化剂(甲醇 钠或乙醇钠) 的作用下, 进行随机酯交换反应, 将棕榈酸平均分布于 甘油酯的 Sn-1、 Sn-3和 Sn-3位上, 从而使得 Sn-2位上棕榈酸的含量 达到总的脂肪酸组成中棕榈酸 40%以上的水平。 (2 )油脂分提:在一 定温度下利用构成棕榈油的各种甘三酯的熔点差异及溶解度的不同, 把棕榈油分成固、 液两部分, 使得固体部分中的 PPP (三棕榈酸甘 油酯) 的含量提高, 从而 Sn-2位上的棕榈酸含量提高到预期水平。 但这两种方法所得到的油脂原料中 Sn-2位上的棕榈酸含量不会超过 33.3%。
根据上述的 Sn-2 位高棕榈酸含量的油脂与母乳之间的脂肪酸差 异, 选择合理配比的混合脂肪酸或脂肪酸低级醇酯混合物, 在 Sn-1,3 特异性脂肪酶的催化下进行酯交换反应, 反应物在真空条件下脱臭, 去除多余及反应置换出来的混合脂肪酸或脂肪酸低级醇酯混合物,即 可得到与母乳脂肪结构接近的油脂。 但是由于原料中 Sn-2 位上的棕 榈酸含量的局限, 采用这种方法得到的最终产品中的 Sn-2 位上的棕 榈酸含量也不高。
目前母乳脂肪替代物的制备, 主要有两种方法: 混合油脂在脂肪 酶催化下的酯交换反应和油脂与混合脂肪酸在脂肪酶催化下的酯交 换反应。
混合油脂在脂肪酶催化下的酯交换反应制备: Unilever 公司专 利 W01994/268551中报道,将一定比例的棕榈油与棕榈仁油在 1, 3位 选择性脂肪酶催化下进行酯交换, 酯交换产物与高油酸葵花籽油、葵 花籽油以及椰子油按一定比例进行调配, 得到饱和脂肪酸占 30%的甘 三酯混合物, 其中 Sn-2位上的饱和脂肪酸占总的饱和脂肪酸的 40% 以上, 与母乳脂肪接近。
油脂与混合脂肪酸在脂肪酶催化下的酯交换反应制备: 美国专利 US 4876107中将棕榈油高熔点分提组分(成分为 80%PPP 和 20%P0P) 与油酸以重量比 3 : 1混合, 溶解到正已垸中, 40°C下在 来源于毛霉的脂肪酶作用下发生油脂重排反应。过滤去除酶, 再通过 蒸馏脱除正已垸, 真空条件下脱臭除去游离脂肪酸, 产物再与乳脂、 葵花籽油、 大豆油和椰子油等调配, 得到母乳脂肪替代物。
美国专利 US 5658768中将棕榈油硬脂与高油酸葵花籽油脂肪酸 按重量比 1 : 0. 75混合, 在固定化 Novo SP-392脂肪酶催化下反应, 再通过蒸馏除去多余的脂肪酸, 产物在二甘酯特异性脂肪酶 Amano lipase G作用下与脂肪酸反应, 减少生成物中二甘酯的含量。 50%该 产物与 30%液体植物油、 20椰子油混合后在脂肪酶 Novo SP-392催化 下酯交换反应, 降低油脂中的三饱和甘油酯的含量, 从而得到母乳脂 肪替代物。
欧洲专利 EP 0496456中将 Sn_2位高棕榈酸含量( 90%)的甘三 酯与卡诺拉油脂肪酸以重量比 1: 1混合,通过装有固定化脂肪酶 Novo SP-392的填充柱反应, 反应温度 70°C, 不添加溶剂。 反应结束, 93% 的脂肪酸转移到甘三酯中, 同时产生了 5%的甘二酯。 多余的脂肪酸 通过蒸馏除去, 并经过中和去除痕量的游离脂肪酸。甘二酯则经过硅 胶填充柱吸附去除。上述产物再溶解在丙酮中, _5 °C低温下溶剂分提, 得到的液体部分精炼后即为母乳脂肪替代物。
另外, 与上述专利类似, 也有将高纯度三棕榈酸甘三酯 (PPP) 与油酸或油酸甲酯在脂肪酶催化下进行酸解反应的报道。
但上述制备方法都有各种各样的缺陷,如混合油脂在脂肪酶催化 下的酯交换反应制备的母乳脂肪替代物 Sn-2位上的棕榈酸占总的棕 榈酸只能达到 40%左右, 与母乳脂肪实际的 Sn-2位上的棕榈酸占总 的棕榈酸达到 67%以上相距甚远。 而采用油脂与混合脂肪酸在脂肪酶 催化下的酯交换反应, 由于原料主要采用棕榈油, 棕榈油中 Sn-2位 上的棕榈酸占总的棕榈酸的比例较低 (不高于 33. 3% ) ,酶法酯交换 后终产物中的 Sn-2位上的棕榈酸含量也不高。
还有报道使用中国廉价易得的猪油原料 (甘三酯主要为 USU型) 在 Lipozyme IM脂肪酶催化下与大豆油脂肪酸进行酸解反应, 酶添加 量 13. 6%, 猪油与脂肪酸的摩尔比为 1 : 2. 4, 反应温度 61 °C, 可得到 成本低廉的母乳脂肪替代产物。但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。
发明内容
本发明的目的在于针对现有用于婴儿配方食品的母乳脂肪替代 物及其制备方法存在的以上所述问题, 提供一种可用于制备与母乳 脂肪组成接近的母乳脂肪替代物的来源于湄公河三角洲鲶鱼的油脂 并将该油脂应用于制备母乳脂肪替代物。
本发明的来源于湄公河三角洲鲶鱼的油脂,是从湄公河三角洲鲶 Panga匪 odon gigas)的全鱼中提取或从去除鱼片以后的其余部位 提取的鲶鱼脂肪或所述鲶鱼脂肪的分提液体组分。
所述湄公河三角洲鲶鱼 (Pcmgasicmodcm gigas)是指巴沙鲶鱼 ( basa catf i sh )和楂鲶鱼( tra catf i sh)。可采用其中一种或两种。
作为优选方案, 所述鲶鱼脂肪的提取方法是: 将湄公河三角洲鲶 鱼原料清洗, 将全鱼进行粉碎或将去除鱼片后余下的原料进行粉碎, 然后经过连续蒸煮,压滤,将滤液用蒸汽加热 20-60分钟,然后离心, 得到的粗脂肪进行脱水, 然后精炼, 即得鲶鱼脂肪。
作为优选方案, 所述鲶鱼脂肪的分提液体组分的分提方法是: 将 湄公河三角洲鲶鱼脂肪加热到 60°C, 稳定 20分钟后, 以 10°C/小时 的速度降温至 30°C, 再以 1.5-2.5Ό/小时的速度降温至 15°C,恒温 结晶 3-5 小时,前述所有过程加带搅拌,待析出的固体结晶部分达到 总重量的 10-50%后,在温度 15°C下开始进行过滤分离,经过过滤后得 到分提液体组分。
一种采用本发明的来源于湄公河三角洲鲶鱼的油脂制备母乳脂 肪替代物的方法, 包括如下歩骤:
(1) 提取来源于湄公河三角洲鲶鱼 (¾«giww«oio« gzgfl^)的脂 肪;
(2) 将上一歩骤得到的鲶鱼脂肪在 10-3CTC温度条件下进行油 脂分提得到其分提液体组分;
(3) 将歩骤 (1) 或歩骤 (2) 得到的油脂在脂肪酶催化下与混 合脂肪酸或混合脂肪酸低级醇酯进行酶法酯交换反应,或者是将步骤
(1)或歩骤(2)得到的油脂与其它植物油混合所得到的混合油脂在 脂肪酶催化下与混合脂肪酸或混合脂肪酸低级醇酯进行酶法酯交换 反应,所述油脂或混合油脂与混合脂肪酸或混合脂肪酸低级醇酯的重 量比为 (2:1) - (1:2), 酯交换反应后经减压蒸馏分离出反应所得到 的油脂并精炼, 即得母乳脂肪替代物。
所述第 (1) 歩的提取方法是, 将湄公河三角洲鲶鱼原料清洗, 将全鱼进行粉碎或将去除鱼片后余下的原料进行粉碎,然后经进连续 蒸煮, 压滤, 将滤液用蒸汽加热 20-60分钟, 然后离心, 得到的粗脂 肪进行脱水, 然后精炼, 即得鲶鱼脂肪。
所述第 (2 ) 歩油脂分提的温度优选为 15-25°C。
所述脂肪酸低级醇酯优选为脂肪酸乙酯。
所述第 (3 ) 歩中的混合脂肪酸来源于大豆油、 低芥酸菜籽油、 葵花籽油、 玉米油、 椰子油、 棕榈仁油的任意混合油脂的水解产物; 所述混合脂肪酸低级醇酯来源于大豆油、 低芥酸菜籽油、 葵花籽油、 玉米油、 椰子油、 棕榈仁油的任意混合油脂的醇解产物。
所述脂肪酶为 S n-1, 3位专一性脂肪酶, 优选 LIPOZYME RLIM。 所述酶法酯交换反应中, 直接向反应物中添加脂肪酶进行间歇 式反应, 或将反应物通过酶填充反应柱进行。
本发明的技术效果在于: 本发明通过在 1,3位特异脂肪酶催化下 混合脂肪酸或混合脂肪酸低级醇酯与湄公河三角洲鲶鱼脂肪或其分 提液体组分反应得到的甘三酯混合物。由于湄公河三角洲鲶鱼脂肪或 其分提液体组分 Sn-2位上的棕榈酸含量相对较高, 反应终产物中的
Sn-2位上的棕榈酸含量也相对较高, 可以达到与母乳脂肪中 Sn-2位 上棕榈酸含量一致, 即达到 60%以上。 同时, 由于湄公河三角洲鲶鱼 脂肪或其分提液体组分存在 AA和 DHA, 这种母乳脂肪替代物不需 要额外添加 AA和 DHA或者只需要添加少量的 AA或 DHA。 具体实施方式
实施例一:
1、 提取湄公河三角洲鲶鱼脂肪:
将湄公河三角洲巴沙鲶鱼 (basa catfish ) 和楂鲶鱼 ( tra catfish) 清洗, 然后去掉鱼片, 将余下的原料进行粉碎, 然后经过 在连续蒸煮机内进行连续蒸煮,压滤,除渣后用蒸汽加热 20-60分钟, 然后将得到的粗脂肪离心, 再经过闪蒸工序脱水, 最后精炼, 得到湄 公河三角洲鲶鱼脂肪成品。
本发明实施例中所述精炼采用成熟技术, 具体歩骤包括: 脱胶、 脱酸、 脱色和脱臭。 其中的脱臭阶段按温度 240°C、 停留时间 65分 钟、 真空度 2. 3mbar条件下进行。
2、 油脂分提:
将上述歩骤得到的湄公河三角洲鲶鱼脂肪加热到 55-60°C, 稳定 20分钟后, 以 10°C/小时的速度降温至 30°C, 再以 1. 5-2. 5°C/小时 的速度降温至 15°C,恒温结晶 3-5小时,前述所有过程加带搅拌, 待 析出的固体结晶部分达到总重量的 10-50%后, 在温度 15°C下开始进 行过滤分离,起始过滤压力为 3bar, 加压至 12bar停止。 经过过滤后 得到分提液体组分。
3、 制备混合脂肪酸乙酯:
将葵花籽油、 紫苏油和椰子油按 6: 2: 2的重量比混合, 加热升 温到 100°C, 同时搅拌, 保持 20分钟, 然后脱水。 将脱水后油重的 1%催化剂 K0H加入到乙醇中,乙醇与油脂的摩尔比为 6 : 1,搅拌溶解。 待油脂冷却到 60°C, 加入上述含有催化剂的乙醇溶液, 开始反应, 时间 3小时。反应后加入浓度为 8%的柠檬酸溶液水洗, 柠檬酸与 K0H 的摩尔比为 1 : 1, 再第二次水洗。 60°C下真空抽气 1-2小时。 得终产 物混合脂肪酸乙酯。
4、 酶法酯交换: 将上述第 2歩所得的湄公河三角洲鲶鱼分提液体组分与上述第 3 歩骤得到的混合脂肪酸乙酯按重量比为 1 : 1混合,将混合物通过充填 有脂肪酶 LIPOZYME 履 IM的反应柱, 反应温度 55°C, 流速为每小时 通过与酶同等重量的反应物。 反应产物再在 120-150Ό下分子蒸馏, 精炼, 得到母乳脂肪替代物。
脂肪酶 LIPOZYME RMIM购自丹麦的诺维信公司。
实施例二:
1、 湄公河三角洲鲶鱼脂肪的提取:
将湄公河三角洲巴沙鲶鱼 (basa catfish ) 和楂鲶鱼 ( tra catfish) 清洗, 经过连续蒸煮, 压滤, 除渣后用蒸汽加热 20-60分 钟, 然后将得到的粗脂肪离心, 再经过闪蒸工序脱水, 最后精炼, 得 到湄公河三角洲鲶鱼脂肪成品。
2、 混合脂肪酸的制备:
将低芥酸菜油、 大豆油和椰子油按 6: 2: 2的重量比混合, 加热 升温到 100°C, 同时搅拌, 保持 20min, 脱水。 先加入碱液进行皂化, 分离出甘油, 再加入盐酸进行酸化, 得到混合脂肪酸。
3、 酶法酯交换:
湄公河三角洲鲶鱼脂肪与混合脂肪酸的重量比为 1 : 1, 脂肪酶 LIPOZYME RMIM的添加量为油脂重量的 5%, 反应温度 55°C, 酯交换 反应时间 4小时。 反应结束后再在 150-18(TC下分子蒸馏, 精炼, 得 到母乳脂肪替代物。 实施例三:
1、 提取湄公河三角洲鲶鱼脂肪:
具体提取歩骤见实施例一。
2、 油脂分提:
具体分提歩骤见实施例一。
3、 混合脂肪酸乙酯的制备:
将玉米油、 亚麻籽油和椰子油按 6: 2: 2的重量比混合, 加热升 温到 100°C, 同时搅拌, 保持 20min, 脱水。 油重的 1%催化剂 K0H加 入到乙醇中(乙醇与油脂的摩尔比为 6 : 1), 搅拌溶解。 待油脂冷却到 60°C, 加入加有催化剂的乙醇溶液, 开始反应, 时间 3小时。 加入柠 檬酸溶液 (柠檬酸与 K0H的摩尔比为 1 : 1)水洗。 60°C下真空抽气 1-2 小时。 得终产物混合脂肪酸乙酯。
4、 酶法酯交换:
湄公河三角洲鲶鱼的分提液体组分与上述歩骤得到的混合脂肪 酸乙酯的重量比为 1 : 1, 脂肪酶 LIPOZYME履 IM的添加量为油脂重量 的 5%, 反应温度 55。C, 反应时间 4 小时。 酯交换反应结束后再在 120-15CTC下分子蒸馏, 精炼, 得到母乳脂肪替代物。 实施例四:
1、 湄公河三角洲鯰鱼脂肪的提取:
具体提取歩骤见实施例一。 2、 混合脂肪酸乙酯的制备:
将葵花籽油、 亚麻籽油和棕榈仁油按 6: 1: 2重量比混合, 加热 升温到 100°C, 同时搅拌, 保持 20min, 脱水。 油重的 1%催化剂 K0H 加入到乙醇巾(乙醇与油脂的摩尔比为 6 : 1), 搅拌溶解。 待油脂冷却 到 60°C, 加入加有催化剂的乙醇溶液, 开始反应, 时间 3小时。 加 入柠檬酸溶液 (柠檬酸与 K0H的摩尔比为 1 : 1)水洗。 60°C下真空抽气 1-2小时。 得终产物混合脂肪酸乙酯。
3、 酶法酯交换:
将湄公河三角洲鲶鱼脂肪按 5 : 5的重量比例与随机酯交换后的 棕榈油混合,混合油脂与上述歩骤 2中得到的混合脂肪酸乙酯的重量 比为 1 : 1, 将混合油脂与混合油脂肪酸乙酯的混合物通过充填有脂肪 酶 LIPOZYME RMIM的反应柱, 反应温度 55°C, 流速为每小时通过与 酶同等重量的反应物。 反应产物再在 120-15CTC下分子蒸馏, 精炼, 得到母乳脂肪替代物。

Claims

权 利 要 求 书
1. 一种来源于湄公河三角洲鲶鱼的油脂, 其特征在于: 是从湄 公河三角洲鲶鱼 gzgo^的全鱼巾提取或从去除鱼片以 后的其余部位提取的鲶鱼脂肪或所述鲶鱼脂肪的分提液体组分。
2. 根据权利要求 1所述的来源于湄公河三角洲鲶鱼的油脂, 其 特征在于: 所述鲶鱼脂肪的提取方法是, 将湄公河三角洲鲶鱼原料清 洗, 将全鱼进行粉碎或将去除鱼片后余下的原料进行粉碎, 然后经过 连续蒸煮, 压滤, 将滤液用蒸汽加热 20-60分钟, 然后离心, 得到的 粗脂肪进行脱水, 然后精炼, 即得鲶鱼脂肪。
3.根据权利要求 1或 2所述的来源于湄公河三角洲鲶鱼的油脂, 其特征在于: 所述鲶鱼脂肪的分提液体组分的分提方法是, 将湄公河 三角洲鲶鱼脂肪加热到 55-60°C, 稳定 20分钟后, 以 10°C/小时的速 度降温至 30°C, 再以 1. 5-2. 5 °C/小时的速度降温至 10-30°C,恒温结 晶 3-5 小时,前述所有过程加带搅拌,待析出的固体结晶部分达到总 重量的 10-50%后, 在温度 10-3CTC下开始进行过滤分离,经过过滤后 得到分提液体组分。
4. 根据权利要求 1所述的来源于湄公河三角洲鲶鱼的油脂, 其 特征在于: 所述湄公河三角洲鲶鱼 ( ¾«go w«oi o« gzgo^是巴沙鲶鱼
(basa catfish ) 禾口楂 It鱼 ( tra catfi sh)。
5. 一种权利要求 1至 4任一权利要求所述的来源于湄公河三角 洲鲶鱼的油脂在制备母乳脂肪替代物中的应用。
6. 一种采用权利要求 1至 4任一权利要求所述的来源于湄公河 (1) 提取来源于湄公河三角洲鲶鱼 (¾«giww«oio« gzgfl^)的脂 肪;
(2) 将上一歩骤得到的鲶鱼脂肪在 10-3CTC温度条件下进行油 脂分提得到其分提液体组分;
(3) 将歩骤 (1) 或歩骤 (2) 得到的油脂在脂肪酶催化下与 混合脂肪酸或混合脂肪酸低级醇酯进行酶法酯交换反应,或者是将歩 骤(1)或歩骤(2)得到的油脂与其它植物油混合所得到的混合油脂 在脂肪酶催化下与混合脂肪酸或混合脂肪酸低级醇酯进行酶法酯交 换反应,所述油脂或混合油脂与混合脂肪酸或混合脂肪酸低级醇酯的 重量比为 (2:1) - (1:2), 酯交换反应后经减压蒸馏分离出反应所得 到的油脂并精炼, 即得母乳脂肪替代物。
7. 根据权利要求 6所述的采用来源于湄公河三角洲鲶鱼的油脂 制备母乳脂肪替代物的方法, 其特征在于: 所述第 (1) 歩的提取方 法是, 将湄公河三角洲鲶鱼原料清洗, 将全鱼进行粉碎或将去除鱼片 后余下的原料进行粉碎, 然后经进连续蒸煮, 压滤, 将滤液用蒸汽加 热 20-60分钟, 然后离心, 得到的粗脂肪进行脱水, 然后精炼, 即得 鲶鱼脂肪。
8. 根据权利要求 6或 7所述的采用来源于湄公河三角洲鲶鱼的 油脂制备母乳脂肪替代物的方法, 其特征在于: 所述第 (2) 歩油脂 分提的温度优选为 15-25°C。
9. 根据权利要求 6或 7所述的采用来源于湄公河三角洲鲶鱼的 油脂制备母乳脂肪替代物的方法, 其特征在于: 所述脂肪酸低级醇酯 优选为脂肪酸乙酯。
10. 根据权利要求 6或 7所述的采用来源于湄公河三角洲鲶鱼 的油脂制备母乳脂肪替代物的方法, 其特征在于: 所述第 (3 ) 歩中 的混合脂肪酸来源于大豆油、 低芥酸菜籽油、 葵花籽油、 玉米油、 椰 子油、棕榈仁油的任意混合油脂的水解产物; 所述混合脂肪酸低级醇 酯来源于大豆油、 低芥酸菜籽油、 葵花籽油、 玉米油、 椰子油、 棕榈 仁油的任意混合油脂的醇解产物。
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