JP3764793B2 - Method for producing diglycerides - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention produces diglycerides or polyglycerin difatty acid esters (hereinafter referred to as “diglycerides”) in a short time and in a high yield and high purity from fats and oils and glycerin or polyglycene (hereinafter referred to as “glycerin”). On how to do.
[0002]
[Prior art]
Diglycerides are used as a base in the fields of cosmetics and pharmaceuticals. It is also used in the food field as an additive for improving plasticity of fats and oils.
[0003]
Such diglycerides are usually produced by a method such as esterification of glycerin or the like with a fatty acid, or alcohol group exchange reaction of glycerin or the like with an oil or fat. These methods are roughly classified into a chemical reaction method using an alkali catalyst and the like and a biochemical reaction method using an oil and fat hydrolase such as lipase.
[0004]
The chemical reaction method includes, for example, vegetable oils such as olive oil and coconut oil, animal fats such as lard and head, or a predetermined fatty acid and glycerin in the presence of, for example, sodium hydroxide, for example, at a high temperature of about 120 to 190 ° C. ("New surfactant", Hiroshi Horiguchi, Sankyo Publishing, October 10, 1975, pages 631-634). Diglycerides are produced in a short time because of the reaction at such a high temperature.
[0005]
The biochemical reaction is, for example, a method of reacting a predetermined fatty acid or the like with glycerin or the like using lipase as a catalyst. For example, the following techniques are known.
[0006]
A process for producing a diglyceride characterized by reacting a predetermined fatty acid and the like with glycerin in the presence of a 1,3-position selective lipase while removing the reaction product water etc. from the system (Japanese Patent Laid-Open No. 64-71495) Publication). In the synthesis reaction of a predetermined fatty acid and glycerin, adding glycerin at an equimolar amount or more of the fatty acid and reacting, stopping the reaction in a state where the diglyceride concentration is high, separating insoluble glycerin, and then performing further reaction while dehydrating A method for producing diglyceride, which is characterized (Japanese Patent Laid-Open No. 4-330289).
[0007]
[Problems to be solved by the invention]
However, the above chemical reaction method has a drawback that a large amount of by-products such as monoglyceride and triglyceride are produced, and it is difficult to separate and remove the diglycerides with high yield and high purity. In addition, the biochemical reaction method uses an enzyme reaction at room temperature, and the reaction time is generally long because glycerin and fatty acids have a low mutual solubility and become a heterogeneous reaction in which a fatty acid phase and a glycerin phase exist. , Has the disadvantage of poor efficiency.
[0008]
Accordingly, an object of the present invention is to provide a method for producing high-purity diglycerides in a high yield in a short time with a high reaction rate.
[0009]
[Means for Solving the Problems]
As a result of diligent research in view of the actual situation, the present inventors have first made diglycerides (hereinafter referred to as “reaction mixture”) containing a large amount of by-products such as monoglycerides by reacting fats and oils with glycerin and the like at high temperature in the presence of a catalyst. ”) In a short time, and a saturated or unsaturated fatty acid having 2 to 24 carbon atoms or a lower alkyl ester thereof is added to the resulting reaction mixture, and the reaction is further carried out using an enzyme catalyst. The present invention was completed by finding that diglycerides can be obtained in a short yield and a high yield.
[0010]
That is, in the present invention, glycerin or the like and fats and oils are reacted at 120 ° C. or higher in the presence of a catalyst (reaction 1), and a saturated or unsaturated fatty acid having 2 to 24 carbon atoms or a lower alkyl ester thereof is added to the obtained reaction mixture. Furthermore, the present invention provides a method for producing diglycerides characterized by further reacting in the presence of immobilized lipase or intracellular lipase (Reaction 2).
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The fats and oils used in the present invention may be animal fats and oils such as beef tallow, pork tallow, fish oil and whale fat, vegetable oils such as rapeseed oil, olive oil, soybean oil, coconut oil, palm oil, linseed oil and safflower oil. . In general, fats and oils are mainly composed of triglycerides, but monoglycerides, diglycerides, complex lipids (for example, phospholipids such as lecithin and kephalin), free fatty acids, long chain alcohols, sterols, hydrocarbons (for example, squalene), It may contain fat-soluble vitamins, pigments and the like. Further, the extraction method may be any of the squeezing method, the frying method, the cooking method, and the like.
[0012]
The fatty acid used in the present invention is a saturated or unsaturated fatty acid having 2 to 24 carbon atoms, such as butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid. Palmitic acid, zomarinic acid, stearic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, arachidonic acid, gadrenic acid, arachidic acid, behenic acid, erucic acid, eicosapentaenoic acid, docosahexaenoic acid and the like can be used. Moreover, the said fatty acid may form ester with C1-C3 lower alcohol. Examples of the lower alcohol having 1 to 3 carbon atoms include methanol, ethanol, propanol, and isopropanol. These fatty acids or fatty acid esters can be used alone or in a mixed state.
[0013]
About the polyglycerol used for this invention, although there is no restriction | limiting in particular in the polymerization degree of glycerol, For example, it is 2-10, Preferably it is 2-5. Commercially available products can be used for glycerin and polyglycerin. In addition, components other than fats and oils, glycerol, etc. may exist in the raw material of reaction 1. In Reaction 2, components other than the reaction mixture of Reaction 1 and a saturated or unsaturated fatty acid having 2 to 24 carbon atoms or a lower alkyl ester thereof may be present.
[0014]
The catalyst used in the reaction 1 of the present invention is not particularly limited. For example, an alkali such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, or an alkoxide such as sodium methylate or sodium ethylate. Etc. can be used.
[0015]
Further, the immobilized lipase or intracellular lipase used in the present invention is an immobilized lipase or intracellular lipase that selectively acts on positions 1 and 3 (hereinafter referred to as “immobilized or intracellular 1- and 3-position selective lipase”). Preferably there is. The immobilized 1,3-selective lipase can be obtained by immobilizing the 1,3-position selective lipase by a known method. Known methods for immobilization are described, for example, in “Immobilization Enzyme” edited by Ichiro Chibata, published by Kodansha, pages 9-85 and “Immobilized Biocatalyst” edited by Ichiro Chibata, published by Kodansha, pages 12-101. However, a method of immobilizing on an ion exchange resin is exemplified as a preferable one. Examples of the 1,3-position selective lipase used for immobilization include lipases derived from microorganisms such as Rhizopus, Aspergillus, and Mucor, and spleen lipase. For example, Rhizopus delemer, Rhizopus japonicus, Rhizopus niveus, Aspergillus niger, Mucor javanic, Mucor or hei Lipases originating from such as can be used. Examples of commercially available immobilized 1,3-position selective lipase include “Lipozyme IM” manufactured by Novo Nordisk Bioindustry. As the 1,3-position selective lipase in the microbial cell, a 1,3-position selective lipase is adsorbed or bound to the microbial cell, and a commercially available product is “Olipase” manufactured by Osaka Bacteria Institute. These immobilized or intracellular lipases need to exhibit water retention capacity in order to maintain their characteristics even under reduced pressure conditions. For this purpose, a lipase immobilized with an ion exchange resin is particularly preferred.
[0016]
In reaction 1, since it is preferable that the fats and oils are reacted almost completely and unreacted fats and oils are not left, the number of moles of fats x 3 / (number of moles of fats and fats + number of moles of glycerin, etc.) is 0.3-2. In particular, the reaction 1 is preferably performed in the range of 0.5 to 1. Here, the number of moles of fats and oils × 3 represents the number of moles of all fatty acid groups (FA ′) in Reaction 1, and the number of moles of fats and oils + the number of moles of glycerin and the like represents the number of moles of molecules having a glyceryl group (GLY).
[0017]
In Reaction 2, since it is preferable that two fatty acids are bonded to glycerin or polyglycerin (number of moles of oil and fat × 3 + number of moles of saturated or unsaturated fatty acid having 2 to 24 carbon atoms or lower alkyl ester thereof). It is preferable to carry out the reaction 2 in a range of / (number of moles of fats and oils + number of moles of glycerin, etc.) of 1 to 3.5, particularly 1.6 to 2.8, and more particularly about 2. The number of moles of fats and oils × 3 + the number of moles of saturated or unsaturated fatty acid having 2 to 24 carbon atoms or a lower alkyl ester thereof represents the number of moles of all fatty acid groups (FA) in Reaction 2.
[0018]
Reaction 1 of this invention can be performed in accordance with a conventional method. That is, for example, the oil and fat can be obtained by stirring while heating to a predetermined temperature, and adding a catalyst, glycerin, and the like to react. In order to improve the reaction rate, the reaction temperature in the reaction 1 of the present invention is reacted at 120 ° C. or higher, preferably 200 ° C. or higher, under reduced pressure or a nitrogen stream. Further, the reaction time of reaction 1 is not particularly limited, but if it is a long time, a polymer or the like is generated, and from the viewpoint of economy, it is generally 5 hours or less, preferably 3 hours or less.
[0019]
Reaction 2 of this invention can be performed by the following methods, for example. A saturated or unsaturated fatty acid having 2 to 24 carbon atoms or a lower alkyl ester thereof is added to the reaction mixture obtained by the reaction 1 (the resultant is hereinafter referred to as “the raw material mixture of the reaction 2”). The raw material mixture of reaction 2 is reacted in the presence of the above-described immobilized lipase or intracellular lipase. Although reaction temperature does not have a restriction | limiting in particular, For example, it is 20-100 degreeC, Preferably it is 35-80 degreeC.
[0020]
In this reaction, a solvent of hexane, octane or petroleum ether may be used, but it is preferable not to add a solvent in consideration of removal and purification. Moreover, in order to suppress hydrolysis, it is preferable not to add water to the reaction system other than the lipase preparation and the water dissolved in the reaction raw material.
[0021]
In order to increase the ester synthesis rate, it is preferable to carry out the reaction while removing water or lower alcohol produced by the reaction out of the system. Examples of methods for removing water and the like out of the system include dehydration and dealcoholization methods such as dehydration by depressurization and dealcoholization, ventilation of a dry inert gas, or use of a water absorbent such as molecular sieves. Can be used. However, a method using a reduced pressure that can be performed at a low temperature and that does not require collection of an inert gas or a dehydrating agent is preferable. These dehydration and dealcoholization may be performed in the enzyme reactor, or may be performed in the dehydration unit and the dealcoholization unit outside the reactor, and may be circulated with the enzyme reactor.
[0022]
The reaction may be batch, semi-batch or continuous.
[0023]
The lipase preparation is filtered from the reaction product, and unreacted glycerin, fatty acids or lower alkyl esters of fatty acids, and monoglycerides are easily removed by using conventional well-known separation and purification means such as molecular distillation alone or in combination as appropriate. be able to. Thus, purified diglycerides can be obtained with high purity and good yield in a short time. According to the present invention, all diglycerides can be produced.
[0024]
【Example】
EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited to a following example.
[0025]
Example 1
750 g of purified olive oil, 250 g of glycerin, and 1 g of sodium hydroxide were mixed and reacted for 1 hour with stirring at a temperature of 230 ° C. under a nitrogen stream (reaction 1). In Reaction 1, FA ′ was 2.55 mol, GLY was 3.57 mol, and FA ′ / GLY was 0.71. The resulting reaction mixture was 12% by weight of glycerin, 56% by weight of monoglyceride, 28% by weight of diglyceride, and 4% by weight of triglyceride. To the reaction mixture, 1290 g of oleic acid and 200 g of immobilized enzyme (Lipozyme IM, manufactured by Novo) were added and reacted with stirring while dehydrating under reduced pressure at 40 ° C. and 5 Torr, and the fatty acid concentration was 15% by weight. At this point, the reaction was terminated. The reaction time was 2.5 hours (Reaction 2). That is, the sum of the reaction times of Reaction 1 and Reaction 2 was 3.5 hours. The diglyceride in the filtrate after the lipase was filtered off from the reaction product was 62%. In Reaction 2, FA was 7.12 mol, GLY was 3.57 mol, and FA / GLY was 1.99.
[0026]
Comparative Example 1
Same as Example 1, 2010 g of oleic acid (same as the number of moles of all fatty acid groups in Reaction 2 of Example 1) and 330 g of glycerin (same as the number of moles of molecules having a glyceryl group in Reaction 2 of Example 1) 200 g of the immobilized enzyme was mixed and reacted under the same temperature and reduced pressure as in Example 1. The reaction was terminated when the fatty acid concentration reached 15% by weight. The reaction time was 5 hours. The diglyceride in the filtrate after the lipase was filtered off from the reaction product was 63%.
[0027]
According to the method of Example 1, it was possible to shorten the reaction time for 1.5 hours compared with the case of Comparative Example 1 in order to obtain diglycerides having almost the same yield.
[0028]
【The invention's effect】
According to the method of the present invention, high yield and high purity diglycerides can be obtained in a short time. That is, a reaction mixture can be obtained in a short time by first reacting at a high temperature in the presence of a catalyst, and then a high-yield and highly pure diglyceride can be obtained by subsequent enzymatic reaction.

Claims (5)

Glycerin or polyglycerin and fats and oils are reacted at 120 ° C. or higher in the presence of a catalyst (reaction 1), and a saturated or unsaturated fatty acid having 2 to 24 carbon atoms or a lower alkyl ester thereof is added to the obtained reaction liquid, and further immobilized. A method for producing glycerin or polyglycerin difatty acid ester, characterized by reacting in the presence of lipase or intracellular lipase (Reaction 2). The production method according to claim 1, wherein the immobilized lipase or intracellular lipase specifically acts at positions 1 and 3 of glycerin. The production method according to claim 1 or 2, wherein water or lower alcohol produced by the reaction is removed from the system. The manufacturing method of any one of Claims 1-3 which perform the said reaction 1 by 0.3-2 of the number-of-moles of fats and oils x3 / (number of moles of fats + mole number of glycerol or polyglycerol). The reaction 2 is carried out by the following formula: (number of moles of fat and oil × 3 + number of moles of saturated or unsaturated fatty acid having 2 to 24 carbon atoms or lower alkyl ester thereof) / (number of moles of fat and oil + number of moles of glycerin or polyglycerin) The manufacturing method of any one of Claims 1-4 performed by 3.5.