JP2687337B2 - Liquid oil manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention uses a lipase to produce a liquid oil from a solid fat (a fat-and-oil containing a solid fat is also referred to as a solid fat in the present invention) and a liquid oil. It relates to a method of manufacturing. More specifically, it relates to a method for producing a liquid oil, which is obtained by efficiently changing a solid fat into a liquid oil by allowing a lipase having a 1.3-position selectivity to act on a mixture of the solid fat and the liquid oil. (Prior Art) Various studies have been conventionally made on a method for producing a liquid oil containing a solid fat component. The representative ones are as follows. (A) Mixing 50% or less of soft oil (abbreviated as SPO) obtained by fractionating palm oil with liquid oil such as soybean and rapeseed, transesterification using a chemical catalyst, and liquid at room temperature Method for producing oil (JP-A-49-107304). (B) A method in which liquid oil is mixed with palm oil and then the liquid portion is separated after aging at 15 to 20 ° C. for 4 hours or more (JP-A-56-1095).
9). (C) A solid-fat-containing oil or fat is allowed to undergo a transesterification reaction in the absence of a solvent using lipase as a catalyst, and n-
A method for increasing the amount of liquid oil eluted with hexane (JP-A-60-78586). (D) A method for producing a salad oil containing 20 to 50% by weight of palm unfractionated fraction by mixing vegetable liquid oil in the low melting point portion of palm and fractionating at a final temperature of 0 to 10 ° C (JP-A-60-110246). However, these known methods have drawbacks, respectively, and none of them are sufficiently satisfactory methods. The specific drawbacks of the above method are as follows. The method (a) is characterized by using a soft oil / fat having a melting point of 15 to 25 ° C. obtained by fractionating palm oil as a solid oil / fat containing fat and performing chemical transesterification. However, there is a problem that the solid fat that can be used can be applied only to soft palm oil, which is almost similar to liquid oil. Furthermore, since it is necessary to add water to remove the catalyst used for chemical transesterification, hydrolysis of fats and oils is inevitable, and diglyceride produced is mixed into the product, resulting in deterioration of quality. Further, there is a problem that the effect of improving cold resistance is low. The method (b) is characterized in that palm oil is mixed and dissolved in a liquid oil such as rapeseed oil so as to be 20 to 50%, and then fractionated at 15 to 20 ° C to obtain a liquid oil. However, only 30 to 70% of the solid fat palm oil is transferred to the product, which is low in productivity, the process is complicated and energy is required because the fractionation operation is required, and the use of the solid fat that is the fractionation residue produced at the same time There are many drawbacks, such as having to consider both at the same time. With regard to the method (c), the solid fat is reduced by causing a transesterification reaction in the solid fat itself with a lipase as a catalyst in the absence of a solvent (in the present publication, water is also contained in the solvent, and therefore, water does not exist). It is characterized by increasing the liquid oil and improving the liquidity. However, in this method, as disclosed in the examples of the publication, improvement in liquidity (reduction in melting point) is very slight, and as it is, it does not become liquid oil and remains solid fat. Therefore, in order to obtain the liquid oil, a fractionation operation is required, and there are the same drawbacks as the method (b). Further, there are drawbacks such as a long transesterification reaction time of one day, a low rotation rate of the apparatus, poor efficiency, and a low effect of improving cold resistance. Further, in the method (c), the lipase acts on the solid fat itself, whereas the present invention has a fundamental difference in that the lipase acts on the mixture of the solid fat and the liquid oil. The method (d) is a method for producing a salad oil, which comprises mixing a low-melting-point portion of palm oil with a vegetable liquid oil and then separating the mixture at a final temperature of 0 to 10 ° C. However, this method has a drawback that only soft palm oil, which is originally a liquid oil and is obtained by fractionation, can be used. Further, as shown in the examples of the publication, even if palm soft oil is used, only at most about 75% of the liquid oil is produced, and therefore, it is necessary to perform a fractionation operation during production, and it is necessary to utilize the residue. After all, there are many drawbacks. (Problems to be Solved by the Present Invention) Problems of the prior art to be solved by the present invention are as follows. The raw materials that can be used when producing liquid oil using solid fat are limited. The transfer rate of solid fats to liquid oil is low and there is a limit. Low improvement in cold resistance. Separation operation is required to obtain liquid oil, the process is complicated, and the separation residue must be used in parallel. Therefore, a brief description of the object of the present invention is to improve all kinds of solid fats into almost all liquid oils without fractionation operation. (Means for Solving Problems) The present inventors separate all solid fats that are normally used for food or industry (in the present invention, fats and oils containing solid fats are also referred to as solid fats) Without, that is, as a result of diligent examination of the method of making all solid fats into liquid oil except for being removed by a usual refining method, a production method effective in achieving the object was found, and the present invention was completed. I made it. That is, the present invention is a liquid oil and 5 to 400 wt% per liquid oil
Is a method for producing a liquid oil, which comprises causing a transesterification reaction with a lipase having a 1.3-position selectivity coefficient of 0.1 or less as a catalyst in a mixture of solid fats. Briefly, the present invention is a method of directly producing liquid oil from a mixture of solid fat and liquid oil. The key points of the present invention are as follows. Mixing solid oil and liquid oil does not produce liquid oil. The reason for the high melting point of solid fat is that there are many saturated fatty acids.
This is because there are many triglycerides containing three or more. However, it has been found that even naturally occurring solid fats such as palm oil contain unsaturated fatty acids that have the action of lowering the melting point, and that they are unevenly distributed in two positions. If it is possible to selectively transesterify only at the 1.3-position by mixing liquid oil containing a large amount of unsaturated fatty acids that lower the melting point not only at the 2-position such as various solid fats and rapeseed oil but also at the 1.3-position. It should be expected that the triglyceride containing two or more saturated fatty acids is reduced and the melting point is significantly reduced (see Table 1). That is, as in the model of Table 1, selective transesterification using an enzyme should reduce the triglyceride in the combination of (S-S-S) and (S-S-U) and improve cold resistance. The present invention will be described in more detail below. The solid fat used in the present invention may be naturally occurring or synthetically produced. Specifically, palm oil, vegetable oil and fat such as palm fractionated solid oil (palm olein, palm stearin, etc.), animal oil and fat such as beef seasoning oil, kennel oil, lard, and milk tallow may be used. Of course, solid fats other than these may be used. One of these solid fats may be used alone, or two or more of them may be used in combination. As the liquid oil used in the present invention, a naturally occurring oil may be used, or a synthetic oil may be used. Specifically, rapeseed oil, soybean oil, corn oil,
Safflower oil, safflower oil, palm fractionated liquid oil may be used. Of course, liquid oils other than these may be used. One of these liquid oils may be used alone, or two or more of them may be used in combination. Next, regarding the mixing ratio of the solid fat and the liquid oil, the solid fat is usually 5 to 400% by weight, preferably 5 to the liquid oil.
It may be blended up to 100% by weight. This mixture of solid fat 2 and liquid oil is subjected to enzymatic transesterification using a lipase having 1.3 selectivity as a catalyst to convert solid fat into liquid oil. As a lipase having 1.3-position selectivity, , Rhizop
us genus), Aspergillus genus (Aspergillus genus), Mucor genus (Mucor genus), Penicillium genus (Penicillium genus)
Is used. Further, in the present invention, it is particularly preferable to use a lipase having a 1.3 selectivity coefficient γ of 0.1 or less among lipases having 1.3 selectivity. Incidentally, γ is defined as follows. That is, when the transesterification of the fatty acid at the 1.3-position reaches 100% in the system of rapeseed oil and palm olein (1: 1), the rate of introduction of palmitic acid at the 1.3-position to the 2-position is random transesterified. Expressed as 1. That is, the purpose is to ensure that the selective transesterification reaction is carried out by using such a lipase having a high 1.3-position selectivity. The lipase of the present invention may be used in a free state, but in order to improve efficiency, it is preferable to use an immobilized lipase agent immobilized on an inert carrier by a usual method. As the carrier, Celite, alumina, activated clay, quartz sand, molecular sieves, porous silica, etc., which are unnecessary or do not adversely affect the enzyme activity in the reaction system of the present invention, are used alone or in combination. . Further, the addition amount of the lipase or the immobilized lipase agent may be appropriately determined. The enzymatic transesterification reaction of the present invention may be carried out in a system in which a nonpolar organic solvent such as hexane or petroleum ether is present, but is preferably carried out in a system in which such a nonpolar solvent is not present. Further, in the present invention, it is necessary to adjust the water concentration of the mixture of solid fat and liquid oil to 2000 ppm or less, preferably 2 to 500 ppm or less. Because 2000ppm in the reaction system
This is because, in the presence of the above water, the lipase undergoes a hydrolysis reaction and the efficient selective transesterification reaction aimed at by the present invention does not occur. The water concentration is a value measured by the Karl Fischer method. Further, if necessary, glycerin having an action of activating lipase may be added to the reaction system in an amount of 0.1 to 2.0% by weight in the entire reaction system. The transesterification reaction may be carried out at 30 to 80 ° C., preferably 40 to 60 ° C. for 5 minutes to 6 hours and 10 minutes to 60 minutes. The reaction may be carried out in a batch system, but it is preferable to carry out a continuous reaction. Specifically, describing the continuous reaction,
It is as follows. Down flow of raw material oil in which the enzyme agent in which the enzyme is appropriately immobilized is packed in a column and the water concentration is adjusted to 2000 ppm or less,
Alternatively, the flow may be up flow. The continuous reaction may be performed in a fluidized tank without using a column. When the enzymatic transesterification reaction as described above is performed, any kind of solid fat can be used as a raw material when producing a liquid oil from the solid fat, and the solid fat can be almost completely used in a shorter time than the conventional one (98%). % Or more) can be converted to liquid oil. Therefore, it is possible to obtain an oil and fat which not only does not require an extra step such as a sorting operation but also has a remarkable cold resistance. (Effect) The present invention, which converts a solid fat into a liquid oil by a selective transesterification reaction using oxygen, has the following advantages that have not been obtained conventionally. That is, any type and amount of solid fat can be transferred to the liquid oil. Almost all the fixed fat (90% or more) can be converted to liquid oil. The transition rate of 90% or more is 75% of the conventional level
It is an excellent achievement that far surpasses. It corresponds to 95% or more. The cold resistance is remarkably improved. Since almost all solid fat (90% or more) is converted to liquid oil, the fractionation operation that was conventionally required is almost unnecessary, resulting in a simpler process and considering the reuse of fractionation residue. It is no longer necessary. Hereinafter, the present invention will be specifically described according to examples. <Example 1> 30 g of RBD palm oil and 70 g of rapeseed white oil were mixed at 60 ° C,
The raw material oil was dried under reduced pressure and the water content was adjusted to 300 ppm. Next, 0.2 g of each lipase (Rhizopus javanicas, Rhizopus delemar, mucor miehei, mucor jabanicas and lipase derived from Candida cyrindrasse) 0.2 g was dissolved in 2 g of water, respectively, and then well dispersed in 2 g of Celite (535), Immobilized lipase agent (water content 1.0%) by drying the water under reduced pressure at a rate of 60% / 1 hour at 40 ° C
Was prepared. 2.0 g of each immobilized lipase thus prepared was packed in each column (diameter 10 mmφ × 100 mm). Next, the above-mentioned raw material oil was supplied to each column and reacted at 60 ° C. for each hour.
In addition to the continuous reaction, a batch reaction was also performed. In the case of batch reaction, 2.0 g of immobilized lipase (lipase derived from Rhizopus dermer) was added to 20 g of the above-mentioned raw material oil (RBD palm oil: rapeseed white squeezing oil = 3: 7) and reacted at 60 ° C for 6 hours. Let As a comparative example, 100 g of the above-mentioned raw material oil was subjected to chemical transesterification (addition of 0.2% Na methylate, reaction at 80 ° C. for 3 hours). Table 2 shows the results. <Example 2> Palm olein oil was used as the solid fat, and rapeseed oil was used as the liquid oil, and blended in the respective proportions as shown in Table 3 below.
Heated to 60 ° C. and mixed. The homogenized mixed oils were dried under reduced pressure to adjust the water concentration to 100 ppm. Then, the lipase derived from Rhizopus delemar was immobilized on Celite by the same method as in Example 1. After 2.0 g of this immobilized lipase agent was packed in each of three columns (10 mmφ × 100 mm), the above-mentioned mixed oil was supplied to each column to carry out a reaction. The reaction conditions were 60 ° C. for 30 minutes, and the lipase derived from Rhizopus dermer used in the reaction had a 1.3 selectivity coefficient of 0.01. The results are shown in Table 3. <Example 3> 210 g of solid fat palm oil and 490 g of liquid corn oil were blended and kept at 40 ° C to completely dissolve the palm oil to obtain a uniform mixed oil. 100g of this homogeneous oil mixture
Divide into 7 equal parts and dry each fraction under reduced pressure to obtain water concentration of 5000ppm, 2000ppm, 500ppm, 200ppm, 100pp.
m, 50 ppm and 10 ppm. Next, using the same method as in Example 1, the lipase derived from Rhizopus javanicus was immobilized on Celite. 5 g of this immobilized lipase agent was added to each of 7 columns (15
(mmφ × 150 mm), the mixed oil was applied to each column to carry out the reaction. The reaction conditions were 60 ° C. and 60 minutes, and the 1.3 selectivity coefficient of Rhizopus javanicus was 0.01. The results are shown in Table 4. It is considered that when the water concentration is 50 ppm or less, the transesterification is somewhat insufficient because the reaction rate decreases. <Example 4> Solid fat and liquid oil were blended as shown in Table 5 and then heated at 60 ° C to be mixed. The homogenized mixed oils were dried under reduced pressure to adjust the water concentration to 200 ppm. Next, the lipase derived from Rhizopus dermer was immobilized on Celite in the same manner as in Example 1. 2.0 g of this solidified lipase was applied to each column (10 mmφ x 100 m
After filling m), each mixed oil was applied to each column to carry out the reaction. The reaction conditions were 60 ° C. and 40 minutes, and the selectivity of the lipase derived from Rhizopus dermer used in the reaction was 1.3. The results are shown in Table 5. <Example 5> 40 g of solid fat palm oil was mixed with 60 g of liquid oil of safflower oil, and the mixture was kept at 40 ° C to completely dissolve the palm oil to obtain a uniform mixed oil. . The mixed oil thus obtained was dried under reduced pressure to adjust the water concentration to 100 ppm or less to obtain a raw material oil. 20 g of the raw material oil thus obtained, 4 g of celite, 1.0 g of a commercial lipase agent (Rhizops, Derema lipase manufactured by Seikagaku Corporation), and glycerin
0.04 g was put in a closed container and shaken to react. At this time, the reaction conditions were 60 ° C. and 6 hours. Also,
The Rhizopus dermer used has a selectivity factor of 0.02 of 1.3.
Met. The migration rate of palm oil at this time was 91%.

Claims (1)

(57) [Claims] A method for producing a liquid oil, which comprises causing an enzymatic transesterification reaction with a lipase having a selectivity coefficient of 1.3 or less as a catalyst in a mixture of liquid oil and 5 to 400% by weight of solid fat per liquid oil. 2. The method according to claim (1), wherein the enzymatic transesterification reaction is carried out in the absence of a nonpolar organic solvent. 3. The method according to claim (1), wherein the enzymatic transesterification reaction is carried out in the presence of 0.1 to 2% by weight of glycerin per reaction. 4. The method according to claim (1), wherein the enzymatic transesterification reaction is carried out under the condition that the water concentration of the mixture of solid fat and liquid oil is 2000 ppm or less. 5. The production method according to claim (1), wherein the enzymatic transesterification reaction is carried out in a continuous reaction.