JPH0412710B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for producing mono- and diglycerides using oils and fats as raw materials and utilizing glycerolysis reaction using lipase as a catalyst. More specifically, the present invention relates to a method for producing mono- and diglycerides that can be produced industrially by reacting with a specific lipase at a specific amount of water without producing free fatty acids as a by-product and rapidly obtaining mono- and diglycerides. [Prior Art and Problems] Mono- and diglycerides are highly safe and have been used as surfactants with excellent performance in fields such as foods, pharmaceuticals and cosmetics, feeds, and synthetic resins. There are several methods for producing mono- and diglycerides depending on the reaction type. Namely, there are methods using partial hydrolysis of fats and oils, methods using esterification reaction between fatty acids and glycerin, methods using glycerolysis reaction of fats and oils, and there are also special methods such as addition reaction of fatty acids to glycidol. Each of these methods has its own characteristics, which serve as criteria when selecting a model, but the most important industrial method for producing mono- and diglycerides is the glycerolysis reaction of fats and oils. That is, according to the glycerolysis reaction, fats and oils can be used as they are as a source of fatty acids, and the reaction process can be made continuous because there is no generation of water due to the reaction. Therefore, it can be said that industrial production of mono- and diglycerides is substantially carried out by glycerolysis reaction of fats and oils. [Problems to be Solved by the Invention] However, in the glycerolysis reaction of fats and oils in this industrial production, metals, metal oxides, metal chlorides, metal hydroxides, metal hydroxide salts, etc. are added to the fats and oils and glycerin as catalysts. In addition, 220-250℃
It is generally carried out at high temperatures. For this reason, there have been disadvantages such as inevitable deterioration of fats and oils and glycerin due to high temperatures and high energy costs. Incidentally, there is a method in which a metal alcoholate is used as a catalyst to carry out glycerolysis of fats and oils at low temperatures, but this method is not practical as an industrial production method because of deactivation and alcohol by-products. On the other hand, there is also a method in which the glycerolysis reaction of fats and oils is carried out using a lipase catalyst. These reactions are carried out at low temperatures and can be said to be an excellent method in that there is no thermal deterioration of fats and oils and glycerin. However, these lipase-catalyzed reactions involve the by-product of undesirable free fatty acids, and the uses of the produced mono- and diglycerides are limited, or purification operations are required in the next step. . The by-product of free fatty acids is thought to be based on the hydrolysis reaction of fats and oils by water used to activate lipase. Therefore, a method has been devised in which a glycerolysis reaction of fats and oils is carried out using a lipase catalyst in the absence of water, but this method has not always been sufficient as an industrial production method due to the reaction rate. [Means for Solving the Problem] In view of the above circumstances, the present inventors have conducted intensive research and have determined the amount of water in the reaction system using a specific lipase as a catalyst in the production of mono- and diglycerides through the glycerolysis reaction of fats and oils. By adjusting the reaction within the range, the reaction progresses at a practical rate and the desired mono- and diglycerides can be obtained without by-product of free fatty acids, leading to the completion of the present invention. Ivy. The method of the present invention will be described in detail below. The glycerolysis reaction of fats and oils in the method of the present invention involves adding glycerin to fats and oils and then causing transfer of fatty acid residues. Applicable oils and fats are not limited, and may be oils and fats produced by microorganisms, but edible oils and fats of common animal and plant origin are usually used. Examples include olive oil, soybean oil, rapeseed oil, safflower oil, cottonseed oil, palm oil, coconut oil, corn oil, lard, beef tallow, and fish oil. Furthermore, these fractionated oils and fats, processed oils and fats, and hardened oils and fats can also be used. If the melting point of the fat or oil is higher than the reaction temperature, the fat or oil needs to be dissolved in a solvent before use. Solvents that can be used in the method of the present invention include normal hexane, normal heptane, octane, petroleum ether, diethyl ether, acetone, etc. It is suitable because it has little inhibition on lipase. The ratio of raw materials oil and glycerin is not limited, but is preferably 1:2 to 1:5 by weight.
That's about it. If the amount of glycerin is small, the amount of mono- and diglycerides produced will be small, and if the amount of glycerin is too large, there will be an increase in glycerin which has virtually no effect, which is not efficient. In the method of the present invention, the type of lipase used is limited. In other words, the glycerolysis reaction proceeds at a specific water content and free fatty acids are not produced, such as Pseudomonas fluorescens and Chromobacterium
viscosum), Arthrobacter ureafaciens, or Rhizopus delemer, and only when these lipases are used can the desired mono- and diglycerides be obtained by glycerolysis of oil and glycerin. I can do things. The lipase may be used in its free state, but it can also be used in a fixed form for the purpose of recovery, reuse, or continuous use. Immobilization methods are generally classified into three types, including adsorption to a carrier, chemical bonding to a carrier, and inclusion in a gel. In the method of the present invention, the amount of water in the reaction system is further limited. That is, the amount of water blended is 0.3 to 5% with respect to the amount of glycerin used as a reaction raw material, and preferably
It is 0.5-3%. If it is less than 0.3%, free fatty acids may be produced as by-products, but the reaction rate is slow and it is not practical.
Moreover, if it exceeds 5%, the reaction is fast, but free fatty acids are produced as by-products, which is inappropriate. The water used can be distilled water, ion-exchanged water, tap water, etc., and is not limited to any particular water. There is no need to use a buffer because there are no by-product fatty acids and there is no decrease in the pH of the reaction solution. However, if necessary, cofactors such as Ca ions may be added to promote enzyme activity. There are no particular limitations on the equipment used for the reaction, such as a container, but the stirring must be strong enough to cope with the high viscosity of the reaction liquid, which is mainly composed of glycerin.
A method using multi-stage propeller stirring is suitable. The reaction temperature in the method of the present invention is suitably in the range of 25 to 70°C in view of the activation and deactivation characteristics of the lipase. The oil composition at the end of the glycerolysis reaction, that is, when the reaction reaches equilibrium, is approximately constant regardless of the enzyme concentration or reaction temperature. This oil component is used as the target mono- and diglyceride, but it is also possible to use the oil component in the middle of the reaction as the target mono- and diglyceride. The obtained oil can be used as it is, but it can also be used after being treated with diatomaceous earth or activated clay, filtered, and subjected to a purification process to remove protein and water. [Examples] The present invention will be further explained below with reference to Examples and Comparative Examples, but the present invention is not limited to these unless the gist thereof is exceeded. Example 1 4 g of Pseudomonas fluorescens-producing lipase was dissolved in 90 g of ion-exchanged water, and this was added to 3 kg of glycerin. 1 kg of corn oil was added to this and charged into a reactor with a jacket. under stirring
After reacting at 60°C for 4 hours, the oil was extracted with chloroform 5, and the chloroform was distilled off under reduced pressure to obtain the desired product. Composition analysis values by Iatroskyan are 34% triglycerides, 41% diglycerides, 25% monoglycerides, 0% glycerin, and 0% free fatty acids.
It was hot. The Iatroskian analysis method was performed as follows. Chromarod was soaked in a 3% boric acid solution for 5 minutes, dried and baked in Iatroskiyan TH-10 (manufactured by Yatron Co., Ltd.), and then the sample was spotted.
The developing solvent was benzene:chloroform:acetic acid (70:
30:2v/v/v) was used. After development, dry and FID
The weight composition (%) was determined based on the peak area ratio of the integrator. Example 2 2 g of Pseudomonas fluorescens-producing lipase was dissolved in 8 g of ion-exchanged water, and this was added to 2000 g of glycerin. Add 500 g of rapeseed oil to this and react at 40°C for 24 hours to obtain the desired product under the same conditions as in Example 1. The analytical values were 58% triglyceride, 27% diglyceride, 15% monoglyceride, 0% glycerin, and 0% free fatty acid. Example 3 In the same manner as in Example 2, 2 g of Pseudomonas fluorescens-producing lipase was dissolved in 45 g of ion-exchanged water, and this was added to 1000 g of glycerin. 500g of rapeseed oil was added to this and reacted at 40℃ for 4 hours under the same conditions as in Example 1. Analysis values of the target product were 16% for triglyceride, 66% for diglyceride, and 18% for monoglyceride.
%, glycerin 0%, free fatty acid 0%. Comparative Example 1.2 4 g of the same lipase as in Example 1, ie, Pseudomonas fluorescens-producing lipase, was dissolved in 7.5 g or 180 g of ion-exchanged water. 3 kg of glycerin was added to each, and then 1 kg of corn oil was added to each, and the reaction, extraction and analysis were carried out in the same manner as in Example 1. The composition of the obtained oil is 95% triglycerides, 3% diglycerides, 2% monoglycerides, 0% glycerin, and 0% free fatty acids when using 7.5 g of ion-exchanged water (0.25% by weight based on glycerin).
The reaction virtually did not proceed. Also ion exchange water
In the case of 180 g (6% by weight based on glycerin), the composition is 29% triglycerides, 48% diglycerides, 19% monoglycerides, 0% glycerin, and 3% free fatty acids, and the reaction is fast, but with the undesirable by-product of free fatty acids. Ta. Comparative example 3.4 Rhizopus japanicus (Rhizopus
japanicus) produced in the same manner as in Example 1, the reaction hardly proceeded with 90 g of ion-exchanged water (3% based on glycerin), and the composition of the obtained oil was 93% triglycerides and 6% diglycerides.
%, monoglyceride 1%, glycerin 0%, free fatty acid 0%. Also 150g of ion exchange water
(5% based on glycerin), the obtained oil composition,
62% triglycerides, 28% diglycerides, 4% monoglycerides, 0% glycerin, 6% free fatty acids
gave. Although the reaction proceeded somewhat, the by-product of undesirable free fatty acids was promoted. Examples 4 to 7 Various oils and fats were subjected to glycerolysis reaction using the lipase used in the method of the present invention as a catalyst to obtain mono- and diglycerides. The operating method was the same as in Example 1, and the details and results are shown in Table 1. A variety of mono- and diglycerides were obtained by the method of the invention.

[Table] [Effects of the Invention] Table 2 shows a list of the results of Examples 1 to 7 and Comparative Examples 1 to 4.

【table】

[Table] As shown in Table 2, when the lipase claimed in the present invention is produced by Pseudomonas fluorescens, Chromobacterium viscozam, Arthrobacter ureafaciens or Rhizopus deremer, free fatty acids are produced less. , the production rate of mono- and diglycerides is high, but the glycerolysis reaction does not proceed with other lipases, and the desired mono- and di-glycerides are not produced, or free fatty acids are produced as by-products. or,
Even if the claimed lipase is used, if the water content of the reaction system is in a range other than 0.3 to 5% based on glycerin, that is, less than 0.3%, free fatty acids will not be produced by-product, but the reaction rate will be slow and impractical. If 5% or more is used, free fatty acids will be produced as a by-product, making it unsuitable. Therefore, the invention can be said to be a more ideal method for producing industrial mono- and diglycerides, and a more innovative method than other production methods.

Claims (1)

[Claims] 1. In the glycerolysis reaction of fats and oils, the water content in the system is adjusted to 0.3 to 5% by weight based on glycerin, and the reaction is carried out using a specific lipase as a catalyst. Production method. 2 Lipases that allow the glycerolysis reaction to proceed with adjusted water content and do not produce free fatty acids are found in Pseudomonas fluorescens and Chromobacterium viscozam.
2. A process for producing mono- and diglycerides according to claim 1, comprising the production of Arthrobacter ureafaciens (Viscosum), Arthrobacter ureafaciens and Rhizopus delemer.