JP2001178488A - Transesterification of fat and oil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for transesterification of fat/oil that can attain good transesterification reaction by using powdery lipase through the simple step, as the side reaction is suppressed. SOLUTION: This invention relates to the esterifiction reaction through simple steps by enclosing a powdery lipase only or a mixture thereof with a filter aid into the filtration machine so that the lipase or a combination thereof with the filter aids may form layers and the fat/oil is allowed to pass through the filtration mechanism. In a preferred embodiment, the transesterification reaction is carried out, preferably under the non-solvent and anhydrous conditions, as the particle size of more than 90% of the powdery lipase is adjusted to 1-100 μm, preferably a filter aid with an average particle size of 1-1,000 μm is used together. In a preferred embodiment, the ratio of particle size of the powdery lipase to the particle size of the powdery filter aid is 0.1-10. In another preferred embodiment, the filter-passed fat/oil is circulated and the fat/oil is sent out from the circulation system, after the transesterification rate is kept at a prescribed value.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for transesterifying fats and oils using a powdery lipase, and more particularly to a method in which fats and oils are passed through a filter in which powdery lipase is sealed so as to form a layer. The present invention relates to a method for subjecting fats and oils to a transesterification method in a simple process.

[0002]

2. Description of the Related Art Transesterification is an important technique for producing esters of various fatty acids, sugar esters and steroids, including reforming animal and vegetable fats and oils. An enzyme is present as a catalyst for this transesterification reaction. In addition, with regard to fats and oils, in particular, when a lipase which is a fat and oil hydrolyzing lipase is used, the transesterification reaction can be performed under mild conditions at room temperature to about 80 ° C., and the side reaction can be suppressed as compared with conventional chemical reactions. In addition to the reduction in energy and cost, the safety is high because lipase is a natural product as a catalyst. It is also known that the target product can be efficiently produced by its substrate specificity and positional specificity. However, it is difficult to uniformly disperse a water-soluble lipase in an oily raw material even if it is used for transesterification as it is, such as adding powdery lipase to fats and oils, and the activity is not sufficiently expressed, There is a problem that it is difficult to recover the powdery lipase dispersed in fats and oils for reuse. For this reason, conventionally, powdery lipase has been used as a carrier such as an anion exchange resin (Japanese Patent Application Laid-Open No.
0-98984), a phenol-adsorbing resin (Japanese Unexamined Patent Publication No.
No. 202688), a hydrophobic carrier (Japanese Unexamined Patent Publication (Kokai) No. 2-138986).
), A cation exchange resin (JP-A-3-61485), a chelate resin (JP-A-1-262795), and the like, and used for a transesterification reaction. The immobilized lipase obtained by immobilizing powdered lipase or the like on a carrier is excellent in dispersibility in oils and fats and recoverability after the reaction, but immobilized lipase loses lipase activity due to the immobilization treatment. In addition, when a porous carrier is used, there has been a problem that raw materials and products are clogged in pores, resulting in a decrease in transesterification activity. Furthermore, in the conventional transesterification reaction using immobilized lipase, there is a problem that water retained in the carrier is brought into the reaction system, so that a side reaction occurs.

[0003]

DISCLOSURE OF THE INVENTION The present invention uses a powdery lipase and encapsulates the powdery lipase in a filter so as to form a layer in a filter. It is an object of the present invention to provide a method for transesterifying fats and oils, which can achieve a good transesterification reaction, can further suppress a side reaction, and does not require the operation of recovering powdery lipase.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a powdery lipase alone or a filter aid is enclosed in a filter so as to form a layer, and oil and fat are added to the filter. By passing the oil through, it was found that the transesterification reaction could be performed in a simple step and the transesterification reactivity was good, and the present invention was completed. That is, the present invention relates to a transesterification method for fats and oils, wherein a powdery lipase is enclosed in a filter alone or in combination with a filter aid so as to form a layer, and the fat or oil is passed through the filter. Preferably, transesterification is carried out under solvent-free and anhydrous conditions. Preferably powdered lipase 9
A powdery lipase having a particle size of 0% or more maintained in a particle size range of 1 to 100 μm is used, and preferably, a particle size of 90% or more of the filter aid particles is maintained in a particle size range of 1 to 1000 μm. It is preferable that a dripping filter aid is used, and that the ratio of the particle diameter of the powdery lipase to the particle diameter of the filter aid is 1: 0.1-10. The powdery lipase enclosed in the filter is used alone or the filter aid layer is 1 mm thick.
To 500 mm, and the oil pressure at the time of oil passage is 1
The pressure is preferably 0 Pa to 1000 Pa, and the filter preferably has one or more flat filter membranes. The fat or oil to be passed through the filter is preferably a fat or oil containing powdery lipase or / and a filter aid. In addition, the transesterification rate is 30 per oil passing.
% Or more.
The desired transesterification rate can be achieved by passing the oil through the oil more than once or twice, preferably by circulating the oil or fat that has been passed through the oil. In terms of the process, at least a powdery lipase is circulated alone or in a circulation system consisting of a filter and a tank sealed so as to form a layer together with a filter aid, and the passed oil and fat is circulated to a certain degree of transesterification. This is a fat and oil transesterification system that sends fat and oil to the outside of the circulation system after the rate has reached a certain level.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
TECHNICAL FIELD The present invention relates to a method for transesterification of fats and oils, comprising sealing a powdery lipase alone or together with a filter aid in a filter so as to form a layer, and passing the fat or oil through the filter. The powdery lipase is a powdery lipase that is not immobilized, and the powdery lipase is encapsulated alone or together with a filter aid so as to form a layer in a filter. Depending on efficiency,
The order and amount of the powdery lipase and the filter aid to be sealed, the mass ratio of the powdery lipase and the filter aid, and the like can be suitably adjusted. The powdery lipase or the filter aid may be directly encapsulated, or may be encapsulated by being introduced into a liquid such as oil or fat and agitated to pass through. In order to enclose the layer so as to form a layer, it is preferable to insert the powdery lipase or the filter aid into a liquid, in particular, into an oil or fat, and then stir the oil to pass through the oil. Here, a suitable transesterification reaction is performed by using a powdery lipase in which 90% or more of the particles are maintained in a particle size in the range of 1 to 100 μm. 1 to 1000 μm
When the filter aid is used while keeping the particle size in the range described above, the oil passing efficiency is improved. Furthermore, when the ratio of the particle size of the powdery lipase to the particle size of the filter aid is adjusted to 1: 0.1 to 10, a suitable transesterification reaction and a suitable oil passing efficiency are achieved. That is, it can be said that transesterified oil is efficiently produced. Since the present invention relates to a method for transesterifying fats and oils, the lipase is preferably a lipase.In addition, since a powdery lipase not immobilized on a carrier is used, transesterification is performed under substantially solvent-free and anhydrous conditions. Done. In the present invention, the fats and oils refer to liquid fats and oils, and all fats and oils that are liquid at the time of reaction.
The fats and oils include those containing two or more kinds of fats and oils, and those containing one or more kinds of carboxylic acids such as linear fatty acids having 2 to 28 carbon atoms and alcohols such as glycerin. The thickness of the layer formed with the powdered lipase alone or together with the filter aid enclosed in the filter is 1 mm to 500 m
When the value is m, the fat and oil and the lipase are preferably brought into contact with each other, so that a good ester reaction is performed and the oil passing efficiency is also good. It is preferable that the oil pressure at the time of oil passage be 10 Pa to 1000 Pa, since contact and reaction with lipase are promoted. As the filter, a filter having one or more flat filter membranes is particularly preferable, and a layer of powdery lipase or the like is formed on one surface of the filter membrane. Here, when oil is passed through one of the layers formed on the filtration membrane in the filter, or when oil is passed through two or more layers in the same filter, it can be selected according to the desired transesterification rate. In the above embodiment, by passing the oil through a filter in which powdery lipase or the like is enclosed, in a simple process,
This is a method for transesterifying fats and oils, which does not require the recovery of powdery lipase and provides a good transesterification reaction. Here, the fat or oil to be passed through the filter can contain powdered lipase or / and a filter aid, whereby the reactivity and oil permeability can be adjusted, and the lipase can be deactivated or deactivated. It is possible to appropriately cope with a decrease in filtration efficiency due to clogging, and to complement reactivity and oil permeability.
Further, it can be adjusted so that the transesterification rate is 30% or more in one oil passage. Furthermore, the transesterified oil and fat can be further passed once or more times to improve the transesterification rate, and furthermore, the passed fat and oil can be circulated until the target transesterification rate is achieved. Oil can be passed. In other words, in terms of the process, at least the powdered lipase is circulated alone or in a circulation system consisting of a filter and a tank sealed so as to form a layer together with a filter aid, and the passed oil and fat is circulated to a certain ester. After the exchange rate is reached, a system for transesterifying fats and oils in which fats and oils are fed out of the circulation system can be provided.

[0006] In the present invention, fats and oils refer to liquid fats and oils, and all fats and oils which are liquid during transesterification. The fats and oils include those containing two or more kinds of fats and oils, and those containing one or more kinds of carboxylic acids such as linear fatty acids having 2 to 28 carbon atoms and alcohols such as glycerin. Fats and oils are esters of carboxylic acids and alcohols, and can be obtained by extracting from natural products such as animals, plants, fish and shellfish, microorganisms, and minerals, or by synthesizing esters by a conventional method. Examples of the type of fats and oils include those obtained by squeezing and / or extracting plant bodies, plant seeds, plant fruits, and the like, and purifying raw material fats and oils or purifying animal fats. Specifically, soybean oil, rapeseed oil, high oleic rapeseed oil, sesame oil, corn oil, cottonseed oil, safflower oil, high oleic safflower oil, sunflower oil, high oleic sunflower oil, palm oil, palm olein oil, palm kernel oil , Palm stearin, coconut oil, cocoa oil, rice bran oil, peanut oil, olive oil, perilla oil, perilla oil, linseed oil, grape seed oil, macadamia nut oil, hazelnut oil, pumpkin seed oil,
Walnut oil, camellia oil, teaseed oil, borage oil, babassu oil, tsukumu oil, cottonseed oil, wheat germ oil, algal oil, tallow, lard, chicken oil, fish oil, milk fat, egg oil, lard, seal oil, by breeding These fats and oils and hydrogenated fats and oils which have been reduced in saturation can be used.

As the carboxylic acid, for example, those having 2 to 2 carbon atoms
Preferred are 50 saturated or unsaturated, straight-chain or side-chain aliphatic monobasic acids, so-called fatty acids, aliphatic dibasic acids and tribasic acids. Fatty acids include acetic acid, butyric acid, caprylic acid, isooctylic acid, isononanoic acid, capric acid, lauric acid, palmitic acid, palmitooleic acid, heptadecanoic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, and 10-hydroxystearin Acid, 12-hydroxystearic acid, ricinoleic acid, linoleic acid, linolenic acid, erucic acid, behenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, cerotic acid, montanic acid, nonacosanic acid,
Examples thereof include melicic acid, pentatriacontanic acid, hexatriacontanic acid, and hexatetracontanic acid, and examples of the aliphatic dibasic acid include succinic acid, malic acid, fumaric acid, maleic acid, tartaric acid, glutaric acid, azelaic acid, and sebacic acid. Acids and 1,12-dodecadicarboxylic acid can be exemplified, and examples of the aliphatic tribasic acid include citric acid.

Preferred examples of the alcohol include saturated or unsaturated, linear or branched aliphatic monohydric alcohols having 1 to 50 carbon atoms, and dihydric to hexahydric alcohols. . Examples of these alcohols include methanol, ethanol, isopropyl alcohol, hexanol, isooctanol, isononanol, lauryl alcohol, cetanol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, behenyl alcohol, octacosanol, U.S.A. Monohydric alcohols such as 425 (average molecular weight: 510), unilin alcohol 550 (average molecular weight: 660) and unilin alcohol 700 (average molecular weight: 850), ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, , 8-octanediol,
Dihydric alcohols such as 1,10-decanediol, glycerin, diglycerin, triglycerin, polyglycerin, pentaerythritol, neopentyl glycol,
Examples thereof include trihydric or higher alcohols such as trimethylolethane, trimethylolpropane, xylitol, sorbitol, and mannitol. Furthermore, as alcohols, xylose, fructose, galactose,
Glucosamine, glucose, β-methylglucoside,
Saccharides such as maltose and raffinose, cholesterol, lanosterol, testosterone, anthdrostandiodiol, nandrolone, sterols such as ergocalciphenol, cholecalciphenol, 2,2-dihydroergosterol, dimosterol, sphingosine, and lignoceryl sphingosine. Can also be given. In the above carboxylic acids and alcohols, the upper limit of the number of carbon atoms is set as an industrially easily available one.

The powdery lipase is a powdery lipase which is not immobilized with the powdery lipase. The powdery lipase used herein may be of any origin of animals, plants and microorganisms. Pig pancreatic lipase, lipase derived from soybean, rice bran, castor seed, etc., Aspergillus niger, Candida cylindracea, Rhizopus
Rhizopus delemar, Rhizopus javanicus, Alcaligenes sp.
(Alcaligenes sp.), Alcaligenes faecalis (A
lcaligenes faecalis), Mucor Mehai (Mucor)
miehei), Pseudomonas fluorescens (Pseudo
onas fluorescens). Such a lipase can be extracted and purified from the above-mentioned tissue or culture solution by a conventional method, and it is convenient to use a commercially available product.

In the present invention, it is preferable to use a powdery lipase in which 90% or more of the particles have a particle size of 1 to 100 μm, preferably 5 to 70 μm, more preferably 10 to 60 μm. A transesterification reaction takes place. If the particle size of the powdered lipase is too large, the efficiency of contact with oils and fats deteriorates, and the reactivity decreases. Conversely, if the particle size is too small, liquid permeability deteriorates. The particle size of the powdery lipase can be adjusted, for example, by sonication, pulverization, microfiltration, centrifugal sedimentation, or the like.

[0011] Examples of the filter aid include cellulose-based and celite-based aids, but are not limited thereto, and any filter aid can be used. Particularly, a cellulose-based filter aid is preferable. If the particles of the filter aid are too large or too small, the liquid passing speed cannot be increased. When powder lipase is used, the particle size of 90% or more of the particles is 1 to 100.
By using the filter aid kept in the range of 0 μm, the oil passing efficiency is improved.

Further, the ratio of the particle size of the powdery lipase to the particle size of the filter aid is 1: 0.1 to 10, preferably 1: 0.5 to 5, and more preferably 1: 1 to 3. When adjusted, a suitable transesterification reaction and a suitable oil passing efficiency are achieved. That is, it can be said that transesterified oil is efficiently produced.

In addition, since the powdery lipase which is not immobilized on the carrier is used, there is no mixing of water or the like from the carrier, so that transesterification is carried out under substantially solvent-free and anhydrous conditions. Side reactions are suppressed, generation of impurities is suppressed, reactivity is improved, and quality and production efficiency are improved.

The powdery lipase is enclosed alone or together with a filter aid so as to form a layer in a filter. In this case, the powdery lipase,
It is possible to suitably adjust the order and amount of the filter aid to be enclosed, the mass ratio of the powdery lipase to the filter aid, and the like. In order to control the liquid passing speed, a filter aid is used as necessary, but there is a method in which the filter aid is used as a bed in advance on a filtration membrane or the like, or a method in which a layer is formed together with powdered lipase, but is not limited thereto. It does not make it. Also, powder lipase or filter aid can be directly enclosed,
It may be sealed by introducing the mixture into a liquid such as oil and fat, stirring and dispersing the mixture, and then passing the mixture. In the present invention, it is preferable that a powdery lipase or a filter aid is charged into a liquid, in particular, an oil or fat, and the oil is passed through and stirred to form a layer so as to form a layer. The stirring time required for dispersion is not particularly limited, but about 30 to 60 minutes is sufficient.

The layer to be formed is formed on one surface of a filter membrane or the like together with the powdered lipase alone or together with a filter aid, and transesterification is performed by passing oil and fat through the layer. The degree of transesterification is affected by the conditions under which the fats and oils pass through the layer, ie, the conditions under which the fats and oils come into contact with the powdered lipase.
The amount of the powdery lipase, the particle size of the powdery lipase which is related to the contact efficiency, the contact time between the powdery lipase and the fats and oils, etc., have an effect.From this, the thickness of this layer depends on the degree of transesterification. Will have an impact. In addition, the thickness of this layer also affects the oil permeability. In the present invention, when the thickness of the layer formed with the powdery lipase alone or together with the filter aid is 1 mm to 500 mm, a good ester reaction is performed because the fat and oil and the lipase are preferably in contact, and the oil permeability is also good. It is. Here, the thickness of the layer is not limited to the above range.

The thickness of the layer formed of powdery lipase or the like depends on the particle size ratio, mass ratio of the powdery lipase and the filtering agent,
It also depends on whether or not the layer to be formed contains a filter aid and the method of passing oil. For example, when forming a layer in which the powdery lipase and the filter aid are present from the beginning, the ratio of the particle size of the powdery lipase to the filter aid is 1: 1 and the mass ratio is 1:
1, and the thickness of the layer is preferably formed to be 20 to 100 mm. Further, for example, in the case where the filter aid is used before being bedded with a filter aid, the filter aid having a particle size ratio to the powdery lipase of 1: 5 is 100 to 400 mm.
And then 10 to 5 more days with powdered lipase
It is preferable to add a 0 mm layer. The above is only an example, and the present invention is not limited to these.

Transesterification refers to, for example, one or more esters selected from esters of a carboxylic acid and an alcohol, or a carboxylic acid or an alcohol coexisting with the ester and a carboxylic acid residue or an alcohol residue of the ester. The exchange of groups. The transesterification of fats and oils refers to, for example, one or two or more esters selected from esters of glycerin and fatty acids, or a carboxylic acid or an alcohol coexisting therewith, and a carboxylic acid residue or an alcohol residue of the ester. Is to exchange.

The transesterification rate is an index for measuring the degree of progress of the transesterification reaction.
%, It is possible to set the transesterification rate according to the target quality, stop the reaction at the transesterification rate, and use the present exchange rate as an index. The content of the transesterification rate is defined as 100, where the difference between the specific triglyceride component of the fat and oil before the start of the reaction and the specific triglyceride component after the complete transesterification is 100, and the specific triglyceride component of any transesterified fat and oil before the reaction starts. The degree of change in comparison with is expressed as a percentage, which is described in detail in Tokuhyo Hei 10-508497. Specifically, it is calculated by the following equation. Ester exchange rate (%) = (Xt-XO) / (Xeq-XO)
× 100 X: a measurable property that depends on the molecular composition of the triglyceride mixture and is a composition before the start of transesterification,
Properties of the composition after complete transesterification have the extreme values thereof. XO: Value of X before transesterification Xeq: Value of X after complete transesterification Xt: Transesterification is measured X value of the composition to be determined

As a filter for enclosing a powdery lipase or the like and passing oil or fat, a single plate type, a multi-stage type, a cylindrical type, a filter press type and the like can be used, but not limited thereto, any filter can be used. . The types of filtration membrane include fibers such as cotton cloth, linen cloth and filter paper, animal fibers such as wool cloth, silk cloth and felt, various filter papers made of synthetic fibers such as nylon, saran, krehalon, and vinylon cloth, vinyl sponge, rubber, and sintered metal. A flat membrane, a plate-like membrane, a hollow membrane, or the like made of a material such as unglazed, ceramic, porous material such as porous porcelain, glass wool, or glassfight can be used. The filtration method can be a method by mechanical pressurization, a method of suction by vacuum or decompression, etc., and a cross-flow method in which oil is passed through the membrane in parallel with a method in which oil is passed vertically through the filtration membrane. The effect of the present invention can also be obtained by the method.

The filter is preferably a filter having one or more flat filtration membranes, and a layer of powdery lipase or the like is formed on one surface of the filtration membrane. When a layer is formed on a flat filtration membrane, the thickness of the layer is generally uniform, and there is no possibility that the reactivity or the like will be deviated or a certain portion will not be easily clogged. Here, the oil may be passed through one of the layers formed on the filtration membrane in the filter, or may be passed through two or more layers in the same filter,
It can be suitably selected depending on the desired transesterification rate and the like.

Further, the oil pressure at the time of oil passage to the filter is 10 Pa-
A pressure of 1000 Pa is preferred because contact and reaction with lipase are promoted. Flow rate is 0.01kg / min ~ 1
It is preferably adjusted at 000 kg / min, and although there is a relationship with the thickness of the layer, the time of staying in the layer formed by powdery lipase or the like is preferably 10 seconds to 10 hours. The reaction temperature can be any temperature as long as it is a temperature at which lipase reaction can be performed at -50 to 150 ° C. When edible oils and fats are reacted, 40 to 80 ° C. is preferable from the viewpoint of flavor and quality.

The present invention is characterized in that powder lipase is sealed in a filter, and the reaction is carried out by passing oil and fat through the powder lipase sealed so as to form a layer. As in the case of powdered lipase, it is not necessary to disperse in fats and oils, stir for a long time to make contact with the fats and oils to advance the reaction, collect used lipase, and add it to fats and oils again for reuse . Recovery of lipase used, addition to fats and oils for reuse,
No agitation for dispersion or reaction promotion is required. The powdered lipase encapsulated in the filter is continuously used until the powdered lipase is deactivated to such an extent that the expected reaction cannot be achieved, and then discharged. During this time, a new powdery lipase and a filter aid may be added while observing the transesterification rate and oil permeability, but the powdery lipase enclosed in the filter is collected at regular intervals and converted to oils and fats. There is no need to re-add. Here, the above description does not mean that lipase which has been discharged due to poor oil permeability and not inactivated cannot be added again. In addition, since a filter is usually provided with an automatic or manual discharge mechanism, it is very easy to discharge powder lipase or the like after use. It can be said that it is excellent in workability, cost reduction of the entire process, suppression of side reactions, and the like.

According to the present invention, the fats and oils can be transesterified by passing the fats and oils through the filter in which the powdery lipase or the like is sealed in the above-described embodiment. In addition, it is naturally possible not only to pass a new raw material fat and oil through the filter in which the powdery lipase is sealed, but also to pass the fat and oil used for sealing the powdery lipase again. Is also preferred. The present invention is a method for transesterifying fats and oils, which does not require the recovery of powdery lipase in a simple step and can provide a good transesterification reaction.

The fat or oil to be passed through the filter can contain powdery lipase or / and a filter aid, and the transesterification method of the present invention can be carried out by passing the oil. A powdery enzyme or a filter aid can be added to the fat or oil to be passed. Thus, during the production of a continuous transesterification oil, the reactivity and oil permeability can be adjusted without stopping the continuous production, and the lipase is inactivated and the filtration efficiency is reduced due to clogging. It can cope with the decrease, and can complement the reactivity and oil permeability in a timely manner.

According to the present invention, the reaction can be carried out at a transesterification rate of 1% to 99% by one pass of oil, and the transesterification rate can be adjusted preferably to 30% or more. Further, the transesterified oil can be further re-passed or passed twice more to improve the transesterification rate. Further, the trans-passed fat is circulated until the target transesterification rate is achieved. Can be passed through a filter.

That is, in terms of the process, at least a powdered lipase is used alone or in a circulation system consisting of a filter and a tank sealed so as to form a layer together with a filter aid.
It is possible to provide a system for transesterifying fats and oils in which the passed fats and oils are circulated and after a certain transesterification rate is reached, the fats and oils are sent out of the circulation. More specifically, after enclosing the powdery lipase in the filter, the oil and fat are circulated and passed, and when the transesterification rate at the outlet of the filter reaches a predetermined value, the filter is not circulated any further. The reaction solution is drawn out of the system. After completion of the reaction, the reaction can be carried out simply by operating the valve at the outlet of the filter. After that, while the powdered lipase is sealed in the filter, the new raw material oil is passed through the filter, and circulated through the filter in the same manner as above, and when the transesterification rate at the filter outlet reaches a predetermined value, The reaction liquid is drawn out of the system from the filter without circulation. This can be repeated until the transesterification reaction does not proceed to the target condition due to inactivation of lipase or the like. Thereafter, the transesterification method of the present invention can be carried out again by enclosing the powdery lipase in the above-described manner, and passing and circulating the fat and oil. The transesterification reaction can be simply and repeatedly performed.

According to the present invention, since the lipase to be used is in a powder form, the contact with fats and oils is good, and the transesterification reactivity is good. Further, by using a filter aid, The oil passing efficiency is also good. In other words, reactivity,
This means that the oil passage is good and the production efficiency of the target transesterified fat is good. Further, by adding lipase and an auxiliary agent to the raw material fat and passing the oil through a filter, it is possible to adjust the ester exchange rate and the oil passing rate and to supplement the decrease in the ester exchange rate. As described above, the transesterification rate in one oil pass can be adjusted, and the ester exchange rate can also be adjusted by repeating circulation and oil passing, that is, by the number of times of oil passing. In addition, powder lipase is used, but according to the present invention, since there is no lipase recovery operation, lipase loss due to recovery, activity reduction due to moisture absorption can be avoided, and it is also preferable from the viewpoint of workability on site. . Since the immobilized lipase immobilized on the carrier is not used, and since there is no lipase recovery operation, there is little possibility that water is mixed into the system, and side reactions hardly occur. Further, as a matter of course, the filtration step can also be performed. According to the present invention, transesterification can be easily and repeatedly performed.

[0028]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited by the examples. The method for measuring the particle size of the powdery lipase and the filter aid and the method for measuring the transesterification rate are shown below. <Method for Measuring Particle Size of Powdered Lipase and Filter Aid> The powdered lipase is dispersed in purified fat and oil, and the particle size is measured using a laser diffraction type particle size distribution analyzer LA500 (manufactured by HORIBA, Ltd.). Was measured. <Ester exchange ratio> The composition of the transesterified fat was measured by a capillary gas chromatograph, and the relative change of a specific molecular species was calculated as a ratio. In particular,

According to the method described above.

Example 1 To a mixed oil of 5 kg of palm olein and 5 kg of rapeseed oil was added 200 g of a lipase derived from the genus Alcaligenes (“Lipase PL” manufactured by Meito Sangyo Co., Ltd.). After dispersing the above particles having a particle diameter of 1 μm to 100 μm and an average particle diameter of 40 μm), 200 g (90%) of cellulose powder is used as a filter aid.
% Of particles having a particle diameter of 10 μm to 80 μm and an average particle diameter of 40 μm). This dispersion is transferred to a tank and
While maintaining the temperature at ° C., the oil was passed through a pressure filter having a total filtration area of about 0.1 square meter to form a layer of powder lipase or the like (layer thickness: about 50 mm). Thereafter, the oils and fats were passed through a filter and circulated through a tank to perform a transesterification reaction. The oil pressure sent to the circulating filter is 30
0 Pa. Immediately after starting oil passing and 16 hours after starting oil passing
Later, the transesterification rate of the reaction oil at the outlet of the filter was measured, and the change in triglycerides having a total of 52 carbon atoms of the constituent fatty acids was measured by capillary gas chromatography (GC17A manufactured by Shimadzu Corporation).
It was analyzed and calculated. The transesterification rate was 30% immediately after the start of oil passage and 94% after 16 hours from the start of oil passage. After 16 hours from the start of oil passage, the route at the outlet of the filter was switched to feed oil outside the circulation system, and the reaction oil was recovered. Here, the transesterification rate of the reaction oil at the outlet of the filter immediately after the start of collection and immediately before the end of the recovery,
All were 94%. This filtrate was subjected to ordinary alkali deoxidation, decolorization and deodorization treatment.

Example 2 A mixed oil of palm oil and rapeseed oil was transesterified. As a method for introducing into a filter, first, a cellulose powder (9
A mixture of 400 g of 0% or more of particles having a particle diameter of 100 μm to 400 μm and an average particle diameter of 150 μm) mixed with 5 kg of a mixed oil is passed to form a filter aid layer (10 mm) on the filtration surface, followed by lipase ("Lipase QL" manufactured by Meito Sangyo, 9
A dispersion of 3 kg of 0% or more particles having a particle diameter of 1 μm to 100 μm and an average particle diameter of 30 μm) dispersed in 5 kg of a mixed oil was passed through to form a layer (layer thickness of lipase: 25 mm). Thereafter, the oils and fats were circulated in the same manner as in Example 1. The pressure during circulation was 200 Pa. Immediately after starting oil passing and 16h after starting oil passing
After r, the transesterification rate of the reaction oil at the outlet of the filter was calculated by analyzing the change in triglycerides having a total of 52 carbon atoms of the constituent fatty acids by capillary gas chromatography. The transesterification rate is 20% immediately after the start of oil passage, and 16 hours after the start of oil passage
After r was 95%. After 16 hours from the start of oil passage, the route at the outlet of the filter was switched to feed oil outside the circulation system, and the reaction oil was recovered. Here, the transesterification rate of the reaction oil at the outlet of the filter immediately before and immediately after the start of the recovery was 95%. This filtrate was subjected to ordinary alkali deoxidation, decolorization and deodorization treatment.

Example 3 Transesterification of palm stearin and palm kernel oil was carried out in the same manner as in Example 1. The transesterification rate immediately after passing through the oil was 35%. The rate was 98% after 16 hours from the start of oil passage. After 16 hours from the start of oil passage, the route at the outlet of the filter was switched to feed oil outside the circulation system, and the reaction oil was recovered. Here, the transesterification rate of the reaction oil at the outlet of the filter immediately after the start of collection and immediately before the end of the recovery,
All were 98%.

Example 4 The transesterification was carried out on ultra-hard rapeseed oil and triacetin in the same manner as in Example 1. However, the enzyme was lipase ("Lipase QL" manufactured by Meito Sangyo Co., Ltd., and the particle diameter of 90% or more particles was 1 μm to 1 μm).
The filter aid is Celite powder (90% or more particles having a particle diameter of 30 μm).
m-100 μm, average particle size 60 μm).
The transesterification rate immediately after the oil passing was 30%. The ratio was 99% after 16 hours from the start of oil passage. After 16 hours from the start of oil passage, the route at the outlet of the filter was switched to feed oil outside the circulation system, and the reaction oil was recovered. Here, the transesterification rate of the reaction oil at the outlet of the filter immediately after the start of collection and immediately before the end thereof was 99%.

Table 1 summarizes the types of oils and fats, the types and particle sizes of lipases, the types and particle sizes of filter aids, and the transesterification rates in Examples 1 to 4.

[0034]

[Table 1]

Example 5 Using a mixed oil of 5 kg of palm stearin and 5 kg of palm kernel oil, the reaction was carried out in the same procedure and under the same conditions as in Example 1. However, 10 g of alkaligenes lipase ("Lipase QL" manufactured by Meito Sangyo Co., Ltd.) was used as the lipase, and the cellulose powder was also 10 g. The reaction temperature was 50 ° C. 16h
After the reaction oil was recovered after r, a new mixed oil was put into the tank, and the oil was passed through and circulated again through the filter. The reaction was carried out, and the reaction oil was circulated for 16 hours. This operation was repeated, and circulation was performed once for 16 hours, and a total of 50 reactions were performed. The transesterification rates of the reaction fats and oils in the first, 25th and 50th reactions were 99% and 92%, respectively.
% And 85%. The acid value after the second time is 0.6 ~
0.8.

Example 6 Using a mixed oil of 5 kg of palm stearin and 5 kg of palm kernel oil, the reaction was carried out in the same manner and in the same manner as in Example 5. However, every 10 times 1 g of lipase and 1 g of cellulose powder
Was added. The transesterification rates of the reaction fats and oils of the first, 25th and 50th reactions were 99%, 98%, respectively.
It was 99%. The acid value after the second time is 0.6-0.8
Met.

Comparative Example 1 The same fats and oils, powdered lipase, and filter aid as in Example 5 were used.
A batch-type transesterification reaction was carried out using a powder whose particle size and the like were adjusted to the same conditions. After transferring the mixed oil to which the powdery lipase was added to the tank, the mixture was stirred and uniformly dispersed with a propeller stirrer, and further stirred for transesterification. After 16 hours, cellulose powder was added, and the powdery enzyme was added. By filtering the contained reaction fat, the reaction fat and powdery lipase were recovered. Here, the mixture of the recovered powdery lipase and cellulose powder was added again to a new fat and oil, and stirred in the same procedure,
The reaction was performed, and a total of 50 transesterification reactions were performed. The transesterification rates of the filtrates of the first, 25th and 50th reactions were 99%, 70% and 50%, respectively. The acid value of the filtrate after the second time was 1.1 to 1.9.

Tables 2 and 3 summarize the types of oils and fats, the types and particle sizes of lipases, the types and particle sizes of filter aids, the ester exchange rates and the acid values of Examples 5 and 6 and Comparative Example 1.

[0039]

[Table 2]

Examples 1 to 4 show that the method of the present invention can provide a suitable and uniform transesterification oil with a simple process and labor. From Examples 5 and 6 and Comparative Example 1, according to the method of the present invention, it is possible to maintain a suitable transesterification rate for a long period of time as compared with the ordinary batch-type method, and further to recover enzymes and the like. It has been found that since there is no compound, the contamination of impurities and moisture is suppressed, and thus the deterioration of the reaction oil is suppressed. The above means that it is possible to use the enzyme for a long time, which is also cost-effective. In addition, it can be seen that high quality fats and oils can be obtained in combination with the fact that deterioration is suppressed. In addition, the ordinary batch method requires a collection operation every time the circulation is completed, and thus the work load is very large. In the case of the method of the present invention, the recovery operation may be performed mainly at the time of disposal because the enzyme has been inactivated, and the work load is very light. According to the method of the present invention, continuous reaction for a long time is possible, so that workability is further improved.

[0041]

According to the present invention, it is possible to avoid the loss of lipase due to the recovery and the decrease in the activity due to moisture absorption without the need for the recovery of lipase, and it is possible to reduce the labor of the recovery. In addition, since the reactivity and oil permeability are good, the production efficiency of the target transesterified fat is good, and the transesterification rate in one oil pass can be adjusted and circulated, The transesterification rate can be adjusted by repeating oil passing, that is, by the number of oil passing. According to the present invention, transesterification can be easily and repeatedly performed.

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 4B064 AD87 CA21 CA35 CB26 CC03 CC05 CD21 CD22 DA16 4H059 BA12 BA26 BA30 BB02 BB03 BC03 BC13 BC45 BC48 CA05 CA35 CA96 DA16

Claims (11)

[Claims] 1. A transesterification method for fats and oils, wherein powdery lipase is enclosed in a filter alone or together with a filter aid so as to form a layer, and the fat or oil is passed through the filter. 2. The transesterification method according to claim 1, which is carried out without solvent and under anhydrous conditions. 3. A powdery lipase having a particle size of at least 90%
3. The transesterification method according to claim 1, wherein the particle size is maintained in a range of 100 [mu] m. 4. A particle size of 90% or more of the particles of the filter aid is 1 to 4.
The transesterification method according to any one of claims 1 to 3, wherein the particle size is maintained in a range of 1000 µm. 5. The transesterification method according to claim 1, wherein the ratio of the particle size of the powdery lipase to the particle size of the filter aid is 1: 0.1 to 10. 6. The transesterification method according to claim 1, wherein the filter has one or more flat filtration membranes. 7. The transesterification method according to any one of claims 1 to 6, wherein an oil or fat containing a powdery lipase and / or a filter aid is passed through. 8. The transesterification method according to claim 1, wherein the transesterification rate is 30% or more in one pass of oil. 9. The transesterification method according to any one of claims 1 to 8, wherein the passed oil is further passed once or twice. 10. The method according to claim 1, wherein the passed oil is circulated.
10. The transesterification method according to any one of 9 above. 11. A circulating system comprising a filter and a tank in which at least powdered lipase is used alone or together with a filter aid to form a layer. The oil and fat transesterification system that sends oil and fat to the outside of the circulation system after it becomes