JP2013542727A - Process for producing diacylglycerol-enriched oil or fat - Google Patents

Abstract

The present invention is a process for producing a diacylglycerol-enriched fat or oil comprising the following:
Adding a fat or oil and an immobilized lipase preparation into a reaction chamber to obtain a reaction mixture; glycerol in the reaction mixture at a rate of 40 parts by weight or less of glycerol per 100 parts by weight of the immobilized lipase preparation per hour A step of removing water in the reaction mixture by dehydration; and separating unreacted materials and by-products from the reaction mixture to obtain a diacylglycerol-enriched fat or oil. About.

Description

  The present invention relates to a process for producing a diacylglycerol enriched fat or oil. More particularly, the present invention relates to a process for producing a diacylglycerol enriched fat or oil with a low impurity content.

  Oils or oils containing diacylglycerol at high concentrations (hereinafter referred to as “diacylglycerol-enriched oils or oils”) are known to have advantageous pharmacological properties such as body fat burning action in the human body. is there. Accordingly, diacylglycerol-enriched fats or oils have been widely used as edible oils.

  It is known that diacylglycerol can be produced by several processes including esterification; transesterification; glycerolysis; and partial hydrolysis. The process can be carried out using a chemical alkali catalyst or the like; or a fatty acid reaction enzyme catalyst such as lipase. Enzymatic processes are more commonly used in terms of product purity, consumer acceptance and energy consumption.

  However, some of the diacylglycerol rich fats or oils produced by the process contain impurities such as free fatty acids, monoacylglycerols and other components. In diacylglycerol-rich fats or oils used as edible oils, it is desirable to reduce the impurities to enhance the flavor.

  Patent Document 1 discloses a partial hydrolysis process in which diacylglycerol is produced by reacting triacylglycerol with water in the presence of 1,3-position-specific immobilized lipase. The process requires precise moisture control to obtain the optimal diacylglycerol yield. However, the process also produces relatively large amounts of free fatty acids of 30-35% by weight as by-products. Removing the large amount of by-products generated from the process is not cost effective.

  U.S. Patent No. 6,057,032 describes a glycerolysis process that produces diacylglycerol from triacylglycerol and glycerol in the presence of water and lipase. The process is carried out under conditions where crystals are partially precipitated in the reaction system during the reaction. The concentration of free fatty acids present in the oil phase is 8-30% by weight. The concentration is relatively lower than the amount disclosed in Patent Document 1. However, the disclosed process needs to be performed at a low temperature of 0-25 ° C. in order to allow free fatty acids and monoacylglycerols to crystallize. Furthermore, the disclosed process has a long reaction time of about 10 to 200 hours. Therefore, the operating cost is even higher.

  Patent Document 3 discloses a glycerol decomposition process in which diacylglycerol is produced by reacting triacylglycerol with glycerol in the presence of potassium acetate as a catalyst. However, the reaction temperature of this process is high and requires 190-240 ° C. Exposure of the reaction mixture to elevated temperatures tends to form other undesirable compounds.

International Publication No. 2007/075079 US Patent Application Publication No. 6,337,414 International Publication No. 03/029392

  The process for producing diacylglycerol-rich fats or oils according to the present invention solves the above and other problems and develops the art. It is an advantage of the process of the present invention to provide a diacylglycerol enriched fat or oil by the process of the present invention with low amounts of free fatty acids and monoacylglycerols. A second advantage of the present invention is that the process allows the glycerolysis reaction to proceed without inactivation of the immobilized lipase preparation with glycerol.

  In an embodiment of the invention, the process involves adding glycerol to a reaction mixture comprising a fat or oil and an immobilized lipase preparation at a rate of 40 parts by weight or less per 100 parts by weight of the immobilized lipase preparation per hour. To produce a diacylglycerol-enriched oil or oil. In this embodiment, the process is performed by the following method. The process begins with a fat or oil and an immobilized lipase preparation in a reaction chamber to obtain a reaction mixture. Glycerol is then added to the reaction mixture at a rate of 40 parts by weight or less per 100 parts by weight of immobilized lipase preparation per hour. Water in the reaction mixture is removed by dehydration. The unreacted material and by-products contained in the reaction mixture after the reaction are then separated from the reaction mixture to obtain the desired diacylglycerol enriched fat or oil.

  In certain embodiments of the invention, water is further added to the reaction mixture. In particular, in one of the embodiments, the glycerol is premixed with additional water to obtain a glycerol / water mixture, and then the glycerol / water mixture is added to the reaction mixture at an immobilized lipase preparation 100 per hour. A glycerol / water mixture is added in an amount of 40 parts by weight or less per part by weight. In another aspect of this embodiment, the additional water is added in an amount of at least 0.2 to 100 parts by weight per immobilized lipase preparation.

  According to an embodiment of the invention, glycerol is added to the reaction mixture to an amount of 15% by weight or less of the fat or oil.

  In certain embodiments of the present invention, by-products generated in the process include free fatty acids and monoacylglycerols. In some of such embodiments, the total concentration of free fatty acids and monoacylglycerol in the reaction mixture after addition of glycerol is preferably no more than 15% by weight of the fat or oil. In another aspect of this embodiment, the concentration of free fatty acid in the reaction mixture after addition of glycerol is more preferably 10% by weight or less of the oil and fat.

According to an embodiment of the invention, the immobilized lipase preparation is prepared by immobilizing the lipase on a hydrophilic carrier.
These and other advantages and features of the present invention are described in the following detailed description and illustrated in the following drawings.

It is a graph which shows the time passage of the diacylglycerol manufacture from Examples 1-5 and Comparative Examples 1-5.

  The present invention is for producing a diacylglycerol-enriched fat or oil with improved purity as an edible oil while retaining the biologically advantageous components of the fat or oil used in the production of the fat or oil product. Providing a cost-effective and environmentally friendly process.

  In the present invention, glycerol is added at a rate of 40 parts by weight or less per 100 parts by weight of the immobilized lipase preparation per hour to the reaction mixture containing the oil or fat and the oil and the immobilized lipase preparation. A process for producing a diacylglycerol-enriched fat or oil is obtained that yields a mixture comprising monoacylglycerol and free fatty acids. In one preferred embodiment, glycerol is added to the reaction mixture in a ratio of 5 to 40 parts by weight per 100 parts by weight of the immobilized lipase preparation. Glycerol is added continuously or semi-continuously to the reaction mixture.

  In one embodiment of the invention, the process includes placing a fat or oil and an immobilized lipase preparation in a reaction chamber to obtain a reaction mixture. Glycerol is then added to the reaction mixture at a rate of not more than 40 parts by weight per 100 parts by weight of immobilized lipase preparation per hour. Glycerol is added to the reaction mixture in a controlled manner so that the glycerol degradation reaction occurs without glycerol inactivating the immobilized lipase preparation.

  The process of embodiments of the present invention further includes removing water in the reaction mixture by a dehydration method. In one embodiment of the invention, water in the reaction mixture is removed from the reaction chamber while glycerol is added to the reaction mixture. In another embodiment of the reaction, water in the reaction mixture is removed after completion of the glycerolysis reaction. The unreacted material and by-products contained in the reaction mixture are then separated from the reaction mixture after completion of the glycerolysis reaction to obtain the desired diacylglycerol enriched fat or oil.

Examples of fats or oils used in the process of the present invention include crude or refined vegetable oils and / or animal oils. Vegetable oils include: canola oil, palm oil, corn oil, cottonseed oil, palm oil, palm kernel oil, peanut oil, rapeseed oil, safflower oil, soybean oil, sunflower oil, olive oil, rice bran oil, corn bran oil, borage Oil, primrose oil, flaxseed oil, grape seed oil, linseed oil, argan oil, alfalfa oil, almond seed oil, apricot oil, avocado oil, babas oil, baobab oil, black currant seed oil, brazil nut oil, cocoa seed oil, Camellia oil, carrot oil, cashew nut oil, hazelnut oil, cannabis seed oil, kiwi seed oil, macadamia nut oil, mango seed oil, melon seed oil, niger seed oil, peach seed oil, egoma oil, pistachio oil, coconut seed oil, pumpkin Seed oil, rambutan seed oil, rosehip oil, sesame oil, shea seed oil, tall oil, walnut oil Any one or mixtures of two or more fine wheat germ oil. Animal oils include beef tallow, lard and / or fish oil. The fat or oil used in the process may further be a fat or oil obtained from the process of curing, hydrogenation, transesterification or randomization, fractionation, distillation; and mixtures thereof. Machining fats or oils according to the present invention comprises a C ₂ -C ₂₄ saturated or unsaturated fatty acids or mixtures thereof. Examples of the fats and oils include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, myristic acid, palmitic acid, Palmitoleic acid, zomarinic acid, stearic acid, oleic acid, elaidic acid, petrothelic acid, linoleic acid, α-linolenic acid, γ-linolenic acid, stearidonic acid, arachidic acid, arachidonic acid, gadoleic acid, arachidic acid, dihomo-γ- Examples thereof include linolenic acid, eicosapentanoic acid, behenic acid, erucic acid, adrenic acid, docosapentaenoic acid, docosahexaenoic acid, and nervonic acid. Furthermore, any isomer of the above acids can be used without departing from the invention.

  The immobilized lipase preparation used in the present invention is preferably a lipase immobilized on a hydrophilic carrier. The hydrophilic carrier is preferably silica gel. However, those skilled in the art will recognize that other suitable hydrophilic carriers may be used without departing from the invention.

  The lipase used in the present invention may be a non-position specific lipase or a 1,3-position specific lipase. Preferable examples of the lipase include lipases derived from microorganisms belonging to the genus Rhizopus, Aspergillus, Mucor, Candida and Pseudomonas, and more particularly, Rhizopus delemar. (Rhizopus delemar), Rhizopus japonicus, Rhizopus niveus, Aspergillus niger, Mucor javanicus, Mucor miehei, Kankor miehei Candida rugosa), Candida antarctica, Pseudomonas cepacia-derived lipase and the like.

  The immobilized lipase preparation is obtained by immobilizing the lipase by a known method for immobilizing an enzyme, preferably by adsorption and / or absorption. Commercially available immobilized lipase preparations used in the present invention include “Lipozyme TL IM” (trade name: product of Novozymes).

  In the present invention, the ratio of the total glycerol added to the reaction mixture is not particularly limited. In one embodiment of the present invention, the glycerolysis reaction is carried out so that the proportion of total glycerol added to the reaction mixture is not more than 15% by weight of the fat or oil used in the process, preferably the fat or oil used in the process. It is carried out by a method such that it is 5 to 10% by weight.

  The process of the present invention may be carried out in the absence or presence of water other than that contained in the immobilized lipase preparation and / or raw material. In a preferred embodiment of the invention, the glycerolysis reaction is carried out in the presence of other water. In this embodiment, glycerol added to the reaction mixture is premixed with water to obtain a glycerol / water mixture. The resulting glycerol / water mixture is then added to the reaction mixture at a rate of not more than 40 parts by weight of glycerol / water mixture per 100 parts by weight of the immobilized lipase preparation per hour, preferably 100 parts of the immobilized lipase preparation per hour. A glycerol / water mixture is added in an amount of 5 to 40 parts by weight or less per part by weight to obtain a mixture containing triacylglycerol, diacylglycerol, monoacylglycerol and free fatty acid.

  In the glycerolysis reaction of the process of the present invention, the amount of water present in the reaction mixture at any point in the reaction is 10-100 parts by weight of the immobilized lipase preparation, more preferably 0.2-0.2% of the immobilized lipase preparation. It is carried out in such a way that the amount is from 2 to 100 parts by weight. During the glycerolysis reaction, the amount of water in the reaction mixture can vary. As the amount of water increases, excess water can be removed from the reaction chamber by any known dehydration method. In one preferred embodiment of the invention, the pressure in the reaction chamber is reduced to remove excess water from the reaction chamber.

  The process of the invention is carried out at a temperature within the operating temperature range of the immobilized lipase preparation. In one preferred embodiment of the invention, the glycerolysis reaction is carried out at a temperature in the range of 50-90 ° C, more preferably 60-80 ° C.

  By-products produced by the process of the present invention include free fatty acids and monoacylglycerols. The by-product can be easily separated from triacylglycerol and diacylglycerol contained in the reaction mixture after completion of the glycerolysis reaction using standard separation techniques. Such techniques include deodorization, steam distillation, molecular distillation, adsorption chromatography, and any combination thereof. However, those skilled in the art will recognize that other separation methods may be used without departing from the invention.

  Preferably, the content of free fatty acid and monoacylglycerol in the reaction mixture after the glycerol decomposition reaction is 15% by weight or less of the fat or oil used in the process. Preferably, the content of free fatty acid in the reaction mixture after the glycerolysis reaction is 10% by weight or less of the fat or oil used in the process.

  The amount of diacylglycerol in the diacylglycerol-enriched fat or oil produced by the process of the present invention preferably comprises 25-60% by weight of the fat or oil used in the process. Higher yields of diacylglycerol are obtained with the process of the present invention. Preferably, the yield of diacylglycerol is 45-55% by weight.

  The process of the present invention reduces the amount of undesirable by-products produced, so that the diacyl has improved refinement as an edible oil while retaining the biologically advantageous components of the oil or oil used. Produces a glycerol rich fat or oil. This further reduces the time and steps required to remove unwanted by-products, and the process of the present invention is cost effective. The process of the present invention is further more cost effective in that it uses relatively inexpensive fats or oils as raw materials and relatively low cost lipase preparations as catalysts. The process of the present invention further controls the amount of glycerol or glycerol / water mixture added to the reaction mixture so that the glycerolysis reaction can occur without the glycerol inactivating the immobilized lipase preparation.

  The following examples are provided to further illustrate and describe certain specific embodiments of the present invention, and are intended for the specific procedures, conditions or compositions described herein. It should not be construed as limiting.

Example 1
A 500 ml flask was charged with 100 g palm olein and 10 g lipozyme TL IM. 8 g of glycerol was then mixed with 0.08 ml of water and the resulting glycerol / water mixture was added at a rate of 1.6 g glycerol / hour. The reaction mixture was reacted at 70 ° C. for 8 hours. In the course of the reaction, samples were taken from the reaction mixture at 1 hour intervals. Sample free fatty acids, monoacylglycerol (MAG), diacylglycerol (DAG) and triacylglycerol (TAG) were then analyzed by high performance liquid chromatography. The results are shown in Table 2.

  As shown in Table 1, the amounts of glycerol and water in the glycerol / water mixture and the rate of addition thereof differ in Examples 1 to 5.

Comparative Example 1
A 500 ml flask was charged with 100 g palm olein and 10 g lipozyme TL IM. 8 g of glycerol was then mixed with 0.08 ml of water and the resulting glycerol / water mixture was added all at once at the start of the reaction. The reaction mixture was reacted at 70 ° C. for 8 hours. In the course of the reaction, samples were taken from the reaction mixture at 1 hour intervals. Sample free fatty acids, monoacylglycerol (MAG), diacylglycerol (DAG) and triacylglycerol (TAG) were then analyzed by high performance liquid chromatography. The results are shown in Table 2.

  As shown in Table 1, the amounts of glycerol and water in the glycerol / water mixture are different in Comparative Examples 1 to 5.

The above is an explanation of what the inventor regards as an invention, and it is believed that others can design another system that includes the present invention based on the above disclosure.

Claims (15)

A process for producing a diacylglycerol-enriched fat or oil comprising the following:
Placing a fat or oil and an immobilized lipase preparation in a reaction chamber to obtain a reaction mixture;
Adding glycerol to the reaction mixture at a rate of not more than 40 parts by weight per 100 parts by weight of the immobilized lipase preparation per hour;
Removing water in the reaction mixture by dehydration; and separating unreacted materials and by-products from the reaction mixture to obtain a diacylglycerol-enriched oil or oil;
Including the process.   The process of claim 1, further comprising adding additional water to the reaction mixture.   The additional water is premixed with glycerol to obtain a glycerol / water mixture, and then the glycerol / water mixture is added to the reaction mixture with the glycerol / water mixture per 100 parts by weight of the immobilized lipase preparation per hour. The process according to claim 2, further comprising a step of adding at a ratio of 40 parts by weight or less.   4. The process of claim 3, wherein the additional water is added in an amount of at least 0.2-100 parts by weight of the immobilized lipase preparation.   The process according to claim 1, wherein the glycerol added to the reaction mixture is in an amount of less than 15% by weight of the fat or oil.   The process of claim 1, wherein the by-products comprise free fatty acids and monoacylglycerols.   The process according to claim 6, wherein the total concentration of the free fatty acid and the monoacylglycerol in the reaction mixture after adding the glycerol is not more than 15% by weight of the fat or oil.   The process according to claim 6, wherein the concentration of the free fatty acid in the reaction mixture after adding the glycerol is not more than 10% by weight of oils and fats.   The process of claim 1, wherein the lipase is immobilized on a hydrophilic carrier to prepare the immobilized lipase preparation.   The process according to claim 9, wherein the hydrophilic support is a silica-based material.   The process of claim 1, wherein the dehydration method comprises dehydrating under reduced pressure.   The process of claim 1, wherein the glycerol is added to the reaction mixture in a continuous manner.   The process of claim 1, wherein the glycerol is added to the reaction mixture in a semi-continuous manner.   The immobilized lipase preparation comprises a lipase derived from microorganisms of Rhizopus, Aspergillus and Mucor, spleen lipase, Rhizopus delemar, Rhizopus japonicus An immobilized 1,3-position selected from the group consisting of lipases from Rhizopus niveus, Aspergillus niger, Mucor javanicus and Mucor miehei The process according to claim 1, comprising a chemical lipase.   The process according to claim 1, wherein the fat or oil is selected from the group consisting of vegetable oil, vegetable fat, animal oil, animal fat, processed oil, processed fat, and mixtures thereof.

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