JP5994212B2 - Composition for promoting transesterification of fats and oils - Google Patents

Description

  The present invention relates to a reaction accelerating composition that is added to promote transesterification of fats and oils.

  Transesterification, which is one of the oil and fat modification technologies, is an important technology for producing wax esters, various fatty acid esters, sugar esters, steroids, etc., or for modifying vegetable oils and animal oils. Widely used along with crystallization and fractionation techniques. In addition, the transesterification reaction of fats and oils is classified into two types, while random transesterification reaction performed in a state in which the fats and oils are melted, while crystallizing high melting point fats and oils components such as trisaturated acid glycerides contained in the reaction fats and oils There are direct transesterification reactions to be carried out, and the reaction method is selected depending on the target oil and fat composition.

  As the two types of transesterification catalysts, alkali catalysts such as sodium methylate are widely used because of their low cost and high reactivity. However, fats and oils produced by transesterification reaction using an alkali catalyst are not only colored, but also contain catalyst residues and by-product fatty acid metal salts. Must be removed from inside. Therefore, after completion of the transesterification reaction, decolorization using various adsorbents, removal of fatty acid metal salts by washing with water, and the like are performed. However, when washing with water, in order to increase the number of contact between the transesterification oil and water and water, emulsification occurs when the transesterification oil and water are vigorously mixed, and it becomes difficult to separate the water after that. The yield of will also decrease. On the other hand, when the reaction oil and water are brought into gentle contact with each other so as not to cause emulsification, there is a problem that the efficiency of removing the fatty acid metal salt from the reaction oil and fat deteriorates. Thus, many attempts have been made regarding treatments for removing fatty acid metal salts.

  For example, in Patent Document 1, a plant or oil fat is subjected to a random transesterification reaction, and water is immediately added to inactivate the catalyst. At the same time, the by-product fatty acid metal salts are released as hydrates and centrifuged or separated. A method of removing fatty acid metal salts by filtration and then removing residual fatty acid metal salts in the transesterification oil by washing with water is disclosed.

  In Patent Document 2, 3% of water is added to the transesterification oil and fat to release the fatty acid metal salts as hydrates, and then the fatty acid metal salts are removed by centrifugation, followed by washing with water. After that, a method of performing a decoloring process using an adsorbent is disclosed.

  Although the treatment for removing fatty acid metal salts described in Patent Documents 1 and 2 can effectively prevent the adsorptivity of the adsorbent from being reduced by the fatty acid metal salts, the treatment liquid is centrifuged to remove the fatty acid metal salts. Therefore, there is a disadvantage that the processing cannot be performed in a series of steps and the processing efficiency is extremely low. Furthermore, the fatty acid metal salts in the transesterification reaction fats and oils cannot be completely removed only by centrifugation, and the treatment liquid after centrifugation needs to be washed with water. Moreover, when removing fatty acid metal salts that are liberated only by washing without centrifuging, a large amount of water is required, and the production efficiency is low.

  Further, in Patent Document 3, 0.3 to 5.0 parts by weight of water is added per 100 parts by weight of the transesterified oil, followed by dehydration and decoloring treatment by adding an adsorbent, followed by filtration. Also disclosed is a method for removing fatty acid metal salts, alkali catalysts and adsorbents after decolorization treatment contained in transesterified oil. According to this method, after adding water, the water is dehydrated and removed, whereby fatty acid metal salts contained as a by-product in the transesterified oil are aggregated to grow into large particles. Then, a decrease in the adsorption performance of the adsorbent is effectively prevented, and decolorization with the adsorbent can be performed effectively. However, this method still has low production efficiency because water is added and dehydrated to remove fatty acid metal salts.

  Furthermore, Non-Patent Document 1 also discloses a method of using a mixed reaction liquid of fats and oils to be transesterified and an alkali catalyst as a reaction promoting composition for promoting the transesterification reaction. According to this method, the transesterification reaction can proceed efficiently and continuously by adding the reaction promoting composition to the dehydrated unreacted raw material fat. Since the transesterification starts when the alkali catalyst generates a complex with triacylglyceride, the reaction time can be shortened by preparing the composition for promoting transesterification in advance. However, in this method, although the reaction time can be shortened, a purification step such as a water washing step and a decolorization step is necessary, and the purification step after the transesterification reaction using an alkali catalyst requires time. ing.

  In addition, the direct transesterification reaction is performed at a lower temperature than the ordinary transesterification reaction in order to crystallize high melting point components such as trisaturated acid triacyl glyceride. Therefore, in order to improve the reaction rate, many alkali catalysts are used. Although it is necessary to use it, it is known that the following adverse effects are caused by the fatty acid metal salt produced as a by-product. One problem is that the fatty acid metal salt produced crystallizes and increases the viscosity of the direct transesterification product. On the other hand, when filtration is performed to recover only the liquid triacylglyceride component at the end of the direct transesterification reaction, since the fatty acid metal salt crystals affect the network of triacylglyceride crystals, There was also a problem that the recovery rate of triacylglyceride was significantly reduced.

JP 56-10598 A JP-A-51-61510 JP 2010-31190 A

See Yukagaku, Vol. 28, No. 10, pp. 26-34

  In view of the problems as described above, there is no industrially effective method especially regarding the adverse effect of the fatty acid metal salt during the direct transesterification reaction, and a solution has been desired.

  Therefore, an object of the present invention is to industrially produce transesterified fats and oils having a low content of fatty acid metal salt in a short time without performing a treatment for removing the fatty acid metal salt such as a water washing treatment. And it is providing the composition for accelerating | stimulating the transesterification reaction which does not reduce the transesterification reaction rate, and the method of manufacturing this composition for accelerating | stimulating this reaction.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have mixed and stirred the dehydrated filter aid into the place where the mixture of the alkali catalyst and the triacyl glyceride is in a state where the transesterification reaction has been continued. In addition, the fatty acid metal salt has been removed from the composition obtained by filtration, and when the composition is added to the raw material mixture to be transesterified, it can be transesterified without generating a new fatty acid metal salt. The headline and the present invention were completed.

That is, the first of the present invention is a fatty acid which is a reaction product of a fatty acid in the triacyl glyceride and the alkali catalyst from a reaction product of animal oil or vegetable oil which is a triacyl glyceride and sodium methylate which is an alkali catalyst. The present invention relates to a composition for promoting transesterification of fats and oils from which metal salts have been removed. A preferable embodiment relates to the composition for promoting transesterification of fats and oils as described above, wherein the content of the fatty acid metal salt is 0.9% by weight or less in the entire composition for promoting transesterification. In the second aspect of the present invention, the transesterification reaction time for producing the transesterification reaction promoting composition is 30 minutes or less, and the animal oil or vegetable oil that is triacylglyceride is reacted with sodium methylate that is an alkali catalyst. A method for producing a composition for promoting transesterification of fats and oils, characterized in that a filter aid whose water content is adjusted to 0.3 wt% or less is passed through a filter while stirring and mixed, and the filtrate is recovered. . A preferred embodiment relates to a method for producing a composition for promoting transesterification of fats and oils as described above, wherein the filter aid is at least one selected from activated clay, pearlite, silicon dioxide, and diatomaceous earth. In the third aspect of the present invention, the transesterification reaction accelerating composition according to claim 1 or 2 is added in an amount of 5 to 35 parts by weight with respect to 100 parts by weight of a triacylglyceride as a raw material to be transesterified. It is related with the manufacturing method of the oil-fat composition characterized by performing. A preferred embodiment relates to the method for producing an oil and fat composition as described above, wherein the transesterification reaction is a direct transesterification reaction and the reaction temperature is 20 to 70 ° C.

According to the present invention, it is possible to industrially produce transesterified fats and oils having a low content of fatty acid metal salt in a short time without performing a treatment for removing the fatty acid metal salt such as a washing treatment. Moreover, it is possible to provide a composition for promoting transesterification without lowering the transesterification reaction rate and a method for producing the composition for promoting reaction .

  Hereinafter, the present invention will be described in more detail. The composition for promoting transesterification of the present invention is a fatty acid metal salt by removing the fatty acid metal salt from the reaction product after reacting for a certain period of time after starting the transesterification reaction of triacylglyceride and an alkali catalyst. A transesterification composition for promoting the transesterification reaction having a specific content of not more than a specific amount is obtained. The content of the fatty acid metal salt in the entire transesterification reaction fat is preferably as small as possible, but is preferably 0.9% by weight or less, more preferably 0.6% by weight or less, and even more preferably 0.3% by weight or less. .

  The triacylglyceride used as the raw material of the composition for promoting transesterification of the present invention may be animal oil or vegetable oil. However, when the triacyl glyceride is reacted with the alkali catalyst, the water content in the triacyl glyceride hinders the transesterification reaction, so that the water content in the raw oil / fat may be reduced to 0.1% by weight or less. More preferably, it is 0.05 weight% or less, More preferably, it is 0.03 weight% or less, Most preferably, it is 0.01 weight% or less. Here, in order to dehydrate the raw material fats and oils, heating vacuum dehydration, nitrogen bubbling, or the like may be performed.

  As the alkali catalyst used for preparing the composition for promoting transesterification reaction of the present invention, any substance having transesterification ability may be used. Sodium alloys are preferred, and sodium methylate is preferred from the viewpoint of economy and ease of handling.

  As the filter aid used in the preparation of the composition for promoting transesterification of the present invention, the effect of removing the fatty acid metal salt produced by the reaction of triacylglyceride and an alkali catalyst is obtained, and the ability to promote transesterification is lost. In addition, the fatty acid metal salt is aggregated during filtration and the filtration rate is likely to decrease, so that any fatty acid salt may be used as long as it has an effect of increasing the filtration rate. Specific examples include activated clay, pearlite, silicon dioxide, diatomaceous earth, and activated carbon. In addition, two or more types of filter aids may be used, but it is preferable to use only one type in consideration of economic efficiency and ease of work.

  The filter aid is used to remove the fatty acid metal salt from the reaction product of triacylglyceride and fatty acid metal salt. However, when a normal filter aid is used as it is, it is not preferable because moisture contained in the filter aid deactivates the transesterification promoting ability of the reaction promoting composition. Therefore, it is necessary to dehydrate the filter aid before using the filter aid to remove the fatty acid metal salt, but there is no particular limitation on the method, for example, dry heat dehydration at 120 ° C. or higher, vacuum It is possible to remove water from the filter aid by using dehydration.

  However, in the case of dry heat dehydration, when the filter aid is returned to room temperature, moisture may be absorbed immediately. In the case of vacuum dehydration, if the filter aid is returned to the atmosphere, moisture may be absorbed immediately. For this reason, it is possible to avoid moisture absorption again by setting the entire reaction system to a state where moisture does not exist, such as in a nitrogen atmosphere, but the manufacturing cost increases and it may be difficult to enjoy the effects of the present invention. Therefore, in order to suppress the moisture absorption of the filter aid that occurs after dehydration as much as possible, it is preferable to dehydrate the filter aid as follows.

<Method of dehydrating filter aid>
First, the filter aid is sufficiently stirred and mixed with triacylglyceride. There is no particular limitation on the triacyl glyceride used at this time, but an alkali is used as a raw material for the transesterification reaction promoting composition, considering that the dehydrated filter aid is then brought into contact with the triacyl glyceride mixed with an alkali catalyst. It is preferable to use the same triacylglyceride used for mixing with the catalyst.

  The filter aid mixed with the triacyl glyceride is dehydrated as it is under vacuum. Triacyl glyceride usually does not easily absorb moisture, so if dispersed in triacyl glyceride, it is difficult to absorb the filter aid. Further, even when the filter aid is sufficiently dehydrated, even if it is separated from the triacyl glyceride, the surface is covered with a film of triacyl glyceride, so that it does not absorb more moisture than the triacyl glyceride. For this reason, it becomes possible to easily maintain the low moisture state of the filter aid even after the moisture in the filter aid has been reduced. The lower the water content in the filter aid after dehydration, the better. It is preferably 0.3% by weight or less, more preferably 0.1% by weight or less, still more preferably 0.05% by weight or less, particularly preferably. 0.03% by weight or less.

  It should be noted that the filter aid may be dehydrated as it is after dry heat dehydration or vacuum dehydration as it is, and may be sufficiently stirred and mixed with triacylglyceride, but considering the operability and some water absorption before stirring and mixing, etc. The former is preferred.

  Moreover, what is necessary is just to perform the measuring method of the moisture content of the filter aid dehydrated in a triacyl glyceride as follows.

<Measurement method of water content of filter aid in triacylglyceride>
The water content of the filter aid in the triacyl glyceride can be measured by using a Karl Fischer moisture meter. First, the water content in the mixture of triacylglyceride and dehydrated filter aid is measured using a Karl Fischer. Thereafter, the water content in the triacyl glyceride excluding the filter aid is measured by filter filtration or the like. The difference between these two water amounts is calculated as the water amount of the filter aid.

  In the present invention, the fatty acid metal salt removed during the production of the composition for promoting transesterification is a component generally called soap, the fatty acid in the triacylglyceride in the oil and fat, and the alkali catalyst. Is produced by the reaction. Specific examples include sodium palmitate and potassium stearate.

  The composition for promoting transesterification from which the fatty acid metal salt is removed according to the present invention can be obtained by mixing with a raw material animal or vegetable oil for which the transesterification reaction is to be promoted to obtain a transesterification reaction product having a low fatty acid metal salt content. Therefore, the fewer the fatty acid metal salts in the composition for promoting transesterification, the better. Even if the fatty acid metal salt content in the transesterification reaction promoting composition is high, the transesterification reaction product after mixing the composition with the triacylglyceride as a raw material to be transesterified It does not matter if the content of fatty acid metal salt is small. However, when the content of the fatty acid metal salt in the composition for promoting transesterification reaction is large, the amount of the mixture with the raw animal and vegetable oil is decreased, so that the transesterification reaction promoting ability may be decreased.

  Therefore, the mixing amount of the transesterification reaction promoting composition is such that the content of the fatty acid metal salt in the entire transesterification product when the transesterification reaction is stopped after the addition of the composition is 0.9% by weight or less. It is preferable to mix, it is more preferable to mix so that it may become 0.6 weight% or less, and it is still more preferable to mix so that it may become 0.3 weight% or less. If the fatty acid metal salt content is satisfied, the amount of the fatty acid metal salt in the composition for promoting transesterification reaction is not limited. However, the amount of the fatty acid metal salt in the transesterification reaction promoting composition as a whole is preferably 12% by weight, more preferably 6% by weight or less, and even more preferably 3% by weight or less.

  In addition, the measurement of the fatty acid metal salt in the composition for promoting transesterification reaction of the present invention is performed according to 2.6.2-1996 soap of “Standard Oil Analysis Method” (issue year: 1996) edited by Japan Oil Chemical Association. May be followed.

  The composition for promoting transesterification of the present invention is not particularly limited, but can be suitably produced as follows.

<Method 1 for Producing Transesterification Reaction Promoting Composition 1 (no filter aid mixed)>
The alkali catalyst is preferably 0.04 to 4 parts by weight, more preferably 0.2 parts by weight to 2 parts by weight, and still more preferably 0.8 parts by weight with respect to 100 parts by weight of the triacylglyceride having a reduced water content as described above. 4 parts by weight to 1.6 parts by weight are added, and the mixture is sufficiently stirred and mixed for reaction. When the usage-amount of an alkali catalyst is less than 0.04 weight part, the transesterification reaction promotion ability of the composition for promoting transesterification reaction of this invention may become low. Moreover, when more than 4 weight part, the amount of fatty acid metal salt produced | generated after reaction with a triacyl glyceride may increase.

  The reaction temperature between the triacyl glyceride and the alkali catalyst is not particularly problematic as long as the reaction proceeds. However, a high temperature is preferable in that the reaction proceeds quickly. However, if the temperature is too high, fats and oils are deteriorated. Therefore, the reaction temperature is preferably 50 to 90 ° C, more preferably 70 to 90 ° C, and further preferably 80 to 90 ° C.

  Regarding the reaction time of the triacylglyceride and the alkali catalyst, the time from the start of the transesterification to the removal of the fatty acid metal salt by filtration is important. That is, when the fatty acid metal salt is removed from the transesterification reaction oil or fat, it is utilized that the produced fatty acid metal salt is solidified by forming a network in the transesterification reaction oil or fat. Since the network of fatty acid metal salts in fats and oils increases with time, a longer transesterification reaction time is preferable because many fatty acid metal salts can be removed. The transesterification state continues even after the fatty acid metal salt is removed from the reaction system.

  In the present invention, the time from the start of the transesterification reaction to the start of removal of the fatty acid metal salt by filtration is referred to as the transesterification reaction time for producing the transesterification reaction promoting composition. . In the above, since the network of fatty acid metal salt grows too much and filtration becomes difficult when the transesterification reaction time for producing the transesterification reaction promoting composition is too long, the transesterification reaction promoting composition is When the transesterification reaction time for preparation is short, it is preferable at the point that filtration time becomes quick. Therefore, the transesterification time for producing the transesterification reaction promoting composition is preferably 3 minutes to 1 hour, more preferably 5 minutes to 40 minutes, and even more preferably 10 minutes to 30 minutes.

  In the above, when removing the fatty acid metal salt, the fatty acid metal salt is removed from the reaction mixture by passing the transesterification reaction mixture of the triacyl glyceride and the alkali catalyst through a filter filled with dehydrated filter aid. The obtained filtrate is a composition for promoting transesterification. In addition, what is necessary is just to adjust the timing which passes a filter so that the transesterification time for producing the said composition for transesterification reaction promotion may be satisfy | filled.

  If the amount of the filter aid used in the above is too small, the effect of removing the fatty acid metal salt may be small. If the amount is too large, the processing cost may be increased although the effect of removing the fatty acid metal salt is large. Therefore, the amount of the filter aid used is preferably 0.5 to 10 parts by weight, more preferably 1 to 7 parts by weight, and still more preferably based on 100 parts by weight of the total amount of triacylglyceride and alkali catalyst used as raw materials. Is 2 to 5 parts by weight.

  In addition, since the composition for promoting transesterification reaction of the present invention may inactivate the reaction promoting ability due to contact with moisture in the air, the production method 1 is anhydrous, that is, under a nitrogen atmosphere. It is preferable to carry out under vacuum.

<Method 2 for Producing Transesterification Reaction Acceleration (mixing filter aid before filtration)>
In the production method 1 for the transesterification reaction promoting composition, when removing the fatty acid metal salt from the transesterification reaction mixture, the filter aid after dehydration obtained according to the dehydration method of the filter aid is not separated from the triacylglyceride. The transesterification reaction was promoted in the same manner except that the reaction mixture of the alkali catalyst and triacyl glyceride was added to the remaining mixture, and the mixture of the triacyl glyceride, filter aid, and alkali catalyst was filtered. A filtrate that is a composition is obtained.

  The composition for promoting transesterification reaction of the present invention may be inactivated by contact with moisture in the air, so that the production method 2 is anhydrous, that is, under a nitrogen atmosphere. It is preferable to carry out under vacuum.

<Production Method 3 of Transesterification Reaction Promoting Composition (Batch Mixing)>
An alkali catalyst is added to the mixture of the filter aid after the dehydration obtained in accordance with the method for dehydrating the filter aid without being separated from the triacylglyceride, and the mixture is stirred and mixed. The triacylglyceride, filter aid, alkali By filtering the mixture of the catalyst, a filtrate which is a composition for promoting transesterification is obtained. The transesterification reaction time for preparing the transesterification reaction promoting composition in this production method starts from the time when the alkali catalyst is added and stirred and mixed, and the mixture of triacylglyceride, filter aid, and alkali catalyst is filtered. Similarly, the transesterification time is preferably 3 minutes to 1 hour, more preferably 5 minutes to 40 minutes, and even more preferably 10 minutes to 30 minutes.

  In addition, since the composition for promoting transesterification reaction of the present invention may inactivate the reaction promoting ability due to contact with moisture in the air, the production method 3 is an anhydrous system, that is, in a nitrogen atmosphere. It is preferable to carry out under vacuum.

<Method for producing transesterification oil composition>
A desired triacyl glyceride transesterification reaction is carried out using the transesterification reaction promoting composition. In this case, the transesterification reaction conditions are not particularly limited and may be ordinary conditions, but the transesterification reaction temperature is preferably 20 to 90 ° C, more preferably 30 to 90 ° C, and further preferably 40 to 80 ° C. Especially preferably, it is 50-70 degreeC.

  Furthermore, when the transesterification of triacylglycerides such as animal and vegetable oils using the composition for promoting transesterification reaction is a direct transesterification reaction, the transesterification temperature and the fatty acid metal salt in the composition for promoting transesterification are contained. Conditions other than the amount can be performed under the same conditions as in ordinary transesterification.

  The direct transesterification reaction temperature is preferably 20 to 60 ° C, more preferably 30 to 50 ° C. When the temperature is lower than 20 ° C., components other than trisaturated acid triacylglyceride such as disaturated acid diunsaturated acid triacylglyceride are crystallized at the same time. Therefore, trisaturated acid triacylglyceride and triunsaturated acid triacyl are also crystallized. The purpose of direct transesterification, which is a reaction that increases glyceride, may not be satisfied. If the temperature is higher than 60 ° C., the oil and fat may be deteriorated, and the trisaturated acid triglyceride which is a high melting point component is not crystallized, so that the reaction may not proceed from the randomized state.

  Further, the content of fatty acid metal salt during the direct transesterification reaction is preferably as low as possible, but is preferably 1% by weight or less, more preferably 0.6% by weight or less, and still more preferably in the entire direct ester reaction oil / fat composition. It is 0.3% by weight or less, particularly preferably 0.1% by weight or less. If it exceeds 1% by weight, the viscosity of the reaction fat composition will increase, or the fatty acid metal salt crystals will affect the network of triacylglyceride crystals, and the liquid fats and oils will be separated without dissolving the direct transesterification reaction fat composition. May be difficult.

  Here, when the solid fat content in the direct transesterification reaction oil / fat composition increases, the viscosity may increase at the same time, but in order to obtain the desired triacylglyceride composition, the end point of the direct transesterification reaction is reached. It is not possible to change the solid fat content generated by the time. However, when separating the liquid fat without dissolving the direct transesterification reaction fat composition as described above, the lower the viscosity, the easier the separation, so the viscosity of the direct ester reaction fat composition should be controlled to 10000 cp or less. Is more preferable, and it is more preferably controlled to 7000 cp or less, and further preferably controlled to 4000 cp or less.

  In the above, the viscosity of the direct transesterification oil / fat composition may be controlled as follows. When it is desired to increase the viscosity, the fatty acid metal salt content in the reaction fat composition is increased or the cooling rate of the reaction fat composition is increased. If you want to lower the viscosity, you can do the opposite.

  The timing for adding the transesterification reaction-promoting composition to triacylglycerides such as animal and vegetable oils for transesterification is preferably within 20 minutes after the fatty acid metal salt removal treatment, and within 3 minutes after the treatment. More preferable. If the composition for promoting transesterification is added after 20 minutes have passed from the fatty acid metal salt removal treatment, the transesterification promoting ability of the composition for promoting transesterification may be deactivated.

  In addition, since it is possible to reduce the trouble of generating the composition for promoting transesterification, it is preferable to store it in a tank or the like. It is necessary to keep it at 05% by weight or less, more preferably 0.03% by weight or less, and still more preferably 0.01% by weight or less. Moreover, since it may change color when stored for a long time, the use as a composition for promoting transesterification is preferably within 24 hours, more preferably within 12 hours, further preferably within 6 hours, and particularly preferably within 3 hours. .

  The amount of the transesterification reaction accelerating composition used for the production of the transesterification oil / fat composition is not particularly limited and can be used as it is as the transesterification oil. It is preferable to add 5 to 35 parts by weight with respect to parts. If the amount of the transesterification reaction promoting composition used is less than 5 parts by weight, the ester reaction rate may be low. When adding more than 35 parts by weight, it is necessary to keep the content of the fatty acid metal salt in the transesterification reaction promoting composition to be as small as possible, and a large amount of the composition for promoting transesterification reaction is always stored. It may be necessary and handling may be worse.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the examples, “parts” and “%” are based on weight.

<Analysis of total carbon number of fatty acid bonded to triacylglyceride>
The total carbon number content bound to the triacylglyceride of the present invention was measured using gas chromatography and calculated from the retention time and area ratio of each peak obtained. The analysis conditions are described below.

Column: “DB-1” (about 1 m × 0.25 mm × 0.25 μm) manufactured by Agilent
Inlet temperature: 320 ° C
FID detector temperature: 330 ° C
Oven temperature: Starting from 100 ° C., the temperature is increased to 320 ° C. at a rate of 10 ° C./min, and held at 320 ° C. for 8 minutes.

Inlet pressure: 25 kPa
Analytical sample: Approximately 50 mg of oil and fat was dissolved in 4 mL of isooctane, and 1 μL of the solution was analyzed by gas chromatography.

<Measurement of transesterification rate of transesterification reaction fat>
The transesterification reaction rate is determined by measuring the total carbon number before the reaction, focusing on the triacyl glyceride having a specific total carbon number in the above total carbon number analysis result of the fatty acid bonded to the triacyl glyceride before and after the transesterification reaction. The result was 0%, and the calculated total carbon number after the reaction was calculated with 100% random transesterification. The difference between the measurement results before and after the reaction was expressed as a percentage.

<Measurement of content of fatty acid metal salt in composition for promoting transesterification>
The measurement was carried out according to the method described in 2.6.2-1996 soap of “Reference Oil Analysis Method” (issue year: 1996) edited by Japan Oil Chemical Association.

<Determination of transesterification reaction promoting ability>
Add 100 parts by weight of the composition for promoting transesterification obtained in Examples / Comparative Examples to 100 parts by weight of the same oil and fat as the raw materials used to produce the composition for promoting transesterification, and at 90 ° C. in a vacuum state Stirring (300 rpm) was performed at (3 torr). After stirring for 1 hour, if the transesterification reaction had progressed, it was determined that the composition for promoting transesterification had the ability to promote transesterification, and indicated as “◯”. When there was no promotion ability, it described as "x".

(Example 1) Preparation of transesterification reaction promoting composition 1 According to Table 1, 400 parts by weight of palm olein (iodine value: 60) and 4 parts by weight of activated clay ("NVZ" manufactured by Mizusawa Chemical) were placed in an eggplant flask. While stirring (300 rpm), dehydration in a vacuum state (3 torr) was performed at 90 ° C. for 30 minutes to reduce the water content in the activated clay to 0.08 wt%. After dehydration of the activated clay, 1.6 parts by weight of sodium methylate was added to the mixture of palm olein and activated clay and stirred (300 rpm) in a vacuum state (3 torr) at 90 ° C. for 20 minutes (fatty acid metal salt). Content: 2.4% by weight). Thereafter, the activated clay was separated by filtration at a rate of 400 parts by weight / minute using a Nutsche laid with filter paper (“No. 2” manufactured by Advantech Co., Ltd.) to obtain a composition 1 for promoting transesterification. The content of the fatty acid metal salt in the composition 1 for promoting transesterification was 0.423% by weight.

Example 2 Production of Transesterification Reaction Promoting Composition 2 100 parts by weight of palm olein (iodine value: 60) and 4 parts by weight of activated clay (“NVZ” manufactured by Mizusawa Chemical) were placed in an eggplant flask and stirred (300 rpm). While performing dehydration in a vacuum state (3 torr) at 90 ° C. for 30 minutes, the water content in the activated clay was reduced to 0.075% by weight. The activated clay after dehydration was separated by filtration. In parallel with the dehydration of the activated clay, 400 parts by weight of palm olein (iodine value: 60) was placed in an eggplant flask, and dehydration in a vacuum state (3 torr) was performed at 90 ° C. for 30 minutes while stirring (300 rpm). The amount of water in the fat was adjusted to 0.03% by weight. Thereafter, 1.6 parts by weight of sodium methylate was added and held for 20 minutes to conduct a transesterification reaction. 2 parts by weight of the dehydrated activated clay was added to 100 parts by weight of the transesterification product and stirred (300 rpm) in a vacuum state (3 torr) at 90 ° C. for 10 minutes (content of fatty acid metal salt: 2. 5% by weight). Thereafter, using Nutsche with filter paper (“No. 2” manufactured by Advantech Co., Ltd.), the activated clay was separated by filtration from the transesterification reaction product at a rate of 410 parts by weight / minute, and the transesterification reaction promoting composition 2 was obtained. Obtained. The content of the fatty acid metal salt in the transesterification reaction promoting composition 2 was 0.598% by weight.

Example 3 Production of Transesterification Reaction Promoting Composition 3 400 parts by weight of palm olein (iodine value: 60) and 12 parts by weight of pearlite (“Topcoperlite” manufactured by Toko Perlite Kogyo) were placed in an eggplant flask and stirred (300 rpm). ), Dehydration in a vacuum state (3 torr) was performed at 90 ° C. for 30 minutes, and the water content in the activated clay was reduced to 0.007% by weight. After dehydration of the activated clay, 1.6 parts by weight of sodium methylate was added to the mixture of palm olein and activated clay, and the mixture was stirred (300 rpm) in a vacuum state (3 torr) at 90 ° C. for 20 minutes (fatty acid metal salt). Content: 2.45% by weight). Thereafter, pearlite was separated by filtration at a rate of 140 parts by weight / minute using a Nutsche with filter paper (“No. 2” manufactured by Advantech Co., Ltd.) to obtain a composition 3 for promoting transesterification. In addition, the content of the fatty acid metal salt in the transesterification reaction promoting composition 3 was 0.68% by weight.

(Example 4) Production of transesterification reaction promoting composition 4 400 parts by weight of palm olein (iodine value: 60) and 12 parts by weight of activated clay ("SA1" manufactured by Nippon Activated clay) were placed in an eggplant flask and stirred (300 rpm). ), Dehydration in a vacuum state (3 torr) was performed at 90 ° C. for 30 minutes to reduce the water content in the activated clay to 0.06 wt%. After dehydration of the activated clay, 1.6 parts by weight of sodium methylate was added to the mixture of palm olein and activated clay, and the mixture was stirred (300 rpm) in a vacuum state (3 torr) at 90 ° C. for 20 minutes (fatty acid metal salt). Content: 2.36% by weight). Thereafter, the activated clay was separated by filtration at a rate of 400 parts by weight / minute using a Nutsche laid with filter paper (“No. 2” manufactured by Advantech Co., Ltd.) to obtain a composition 4 for promoting transesterification. In addition, the fatty acid metal salt content in the transesterification reaction promoting composition 4 was 0.319% by weight.

(Example 5) Production of transesterification reaction promoting composition 5 400 parts by weight of beef tallow and 12 parts by weight of activated clay ("Mizuka Life F-2G" manufactured by Mizusawa Chemical) were placed in an eggplant flask and stirred (300 rpm). Dehydration in a vacuum state (3 torr) was performed at 90 ° C. for 30 minutes to reduce the water content in the activated clay to 0.06% by weight. After dehydration of the activated clay, 1.6 parts by weight of sodium methylate was added to the mixture of palm olein and activated clay, and the mixture was stirred (300 rpm) in a vacuum state (3 torr) at 90 ° C. for 20 minutes (fatty acid metal salt). Content: 2.4% by weight). Then, the transmutation reaction promoting composition 5 was obtained by separating the activated clay by filtration at a rate of 160 parts by weight / min using a Nutsche with filter paper (“No. 2” manufactured by Advantech Co., Ltd.). In addition, the content of the fatty acid metal salt in the composition 5 for promoting transesterification was 0.174% by weight.

Example 6 Preparation of Transesterification Reaction Promoting Composition 6 400 parts by weight of palm olein (iodine value: 60) and 6 parts by weight of activated clay (“NVZ” manufactured by Mizusawa Chemical) were placed in an eggplant flask and stirred (300 rpm). However, dehydration in a vacuum state (3 torr) was performed at 90 ° C. for 30 minutes to reduce the water content in the activated clay to 0.07% by weight. After dehydration of the activated clay, 1.6 parts by weight of sodium methylate was added to the mixture of palm olein and activated clay, and the mixture was stirred (300 rpm) in a vacuum state (3 torr) at 90 ° C. for 20 minutes (fatty acid metal salt). Content: 2.42% by weight). At the same time, 100 parts by weight of palm olein (iodine value: 60) and 6 parts by weight of diatomaceous earth (“Radiolite # 700” manufactured by Showa Chemical Co., Ltd.) are placed in an eggplant flask and stirred (300 rpm) in a vacuum state (3 torr). Was dehydrated at 90 ° C. for 30 minutes to reduce the water content in the activated clay to 0.007% by weight. The diatomaceous earth after dehydration was separated by filtration. 150 parts by weight of the separated diatomaceous earth was spread on Nutsche with a filter paper (“No. 2” manufactured by Advantech Co., Ltd.), and 407.6 parts by weight of a mixture of palm olein, activated clay, and sodium methylate was added on top of that. The filtrate was obtained as the transesterification reaction-promoting composition 6 by filtering at a rate of parts by weight / minute. In addition, the content of the fatty acid metal salt in the present transesterification reaction promoting composition 6 was 0.137% by weight.

(Example 7) Preparation of transesterification reaction promoting composition 7 100 parts by weight of rapeseed oil and 3 parts by weight of pearlite (“Topcoperlite” manufactured by Toko Perlite Kogyo) were placed in an eggplant flask and stirred (300 rpm) in a vacuum state ( (3 torr) was dehydrated at 90 ° C. for 30 minutes to reduce the water content in the pearlite to 0.007% by weight. After dehydration of pearlite, 1.6 parts by weight of sodium methylate was added to the mixture of palm olein and pearlite, and the mixture was stirred (300 rpm) in a vacuum state (3 torr) at 90 ° C. for 20 minutes (content of fatty acid metal salt) : 2.4% by weight). Then, perlite was separated by filtration at a rate of 100 parts by weight / minute using a Nutsche laid with filter paper (“No. 2” manufactured by Advantech Co., Ltd.) to obtain a composition 7 for promoting transesterification. The content of the fatty acid metal salt in the transesterification reaction promoting composition 7 was 0.84% by weight.

Example 8 Production of Transesterification Reaction Promoting Composition 8 400 parts by weight of palm olein (iodine value: 60) and 4 parts by weight of pearlite (“Topcoperlite” manufactured by Toko Perlite Kogyo) were placed in an eggplant flask and stirred (300 rpm). ), Dehydration in a vacuum state (3 torr) was performed at 90 ° C. for 30 minutes, and the water content in the pearlite was reduced to 0.005 wt%. After dehydration of pearlite, 1.6 parts by weight of sodium methylate was added to the mixture of palm olein and pearlite, and the mixture was stirred (300 rpm) in a vacuum state (3 torr) at 90 ° C. for 1 hour (content of fatty acid metal salt) : 2.4% by weight). Thereafter, perlite was separated by filtration at a rate of 40 parts by weight using a Nutsche laid with filter paper (“No. 2” manufactured by Advantech Co., Ltd.) to obtain a transesterification reaction promoting composition 8. Moreover, the fatty acid metal salt content in the transesterification reaction promoting composition 8 was 0.186% by weight.

Comparative Example 1 Production of Transesterification Reaction Promoting Composition 9 400 parts by weight of palm olein (iodine value: 60) was placed in an eggplant flask, and dehydration in a vacuum state (3 torr) was performed at 90 ° C. while stirring (300 rpm). After 30 minutes, 1.6 parts by weight of sodium methylate was added, and the mixture was stirred for 20 minutes in a vacuum state (3 torr) to obtain a transesterification reaction promoting composition 9. The fatty acid metal salt content in the composition 9 for promoting transesterification was 2.45% by weight.

(Comparative Example 2) Production of Transesterification Reaction Promoting Composition 10 400 parts by weight of palm olein (iodine value: 60) was placed in an eggplant flask, and dehydration in a vacuum state (3 torr) was performed at 90 ° C while stirring (300 rpm). Then, 1.6 parts by weight of sodium methylate was added, and the mixture was stirred for 20 minutes in a vacuum state (3 torr) to obtain a mixture of triacylglyceride and alkali catalyst. 4 parts by weight of non-dehydrated activated clay (“NVZ” manufactured by Mizusawa Chemical) was added and stirred (300 rpm) in a vacuum state (3 torr) at 90 ° C. for 20 minutes (fatty acid metal salt content: 2.4% by weight). Thereafter, the activated clay was separated by filtration at a rate of 400 parts by weight using a Nutsche with filter paper (“No. 2” manufactured by Advantech Co., Ltd.) to obtain a composition 10 for promoting transesterification. The fatty acid metal salt content in the transesterification reaction promoting composition 10 was reduced to 0.71% by weight.

Comparative Example 3 Preparation of Transesterification Reaction Promoting Composition 11 400 parts by weight of palm olein (iodine value: 60) and 4 parts by weight of perlite (“Topcoperlite” manufactured by Toko Perlite Kogyo) were placed in an eggplant flask and stirred (300 rpm). ), Dehydration in a vacuum state (3 torr) was performed at 90 ° C. for 30 minutes, and the water content in the pearlite activated clay was reduced to 0.008% by weight. After dehydration of pearlite, 1.6 parts by weight of sodium methylate was added to the mixture of palm olein and pearlite, and the mixture was stirred (300 rpm) in a vacuum state (3 torr) at 90 ° C. for 2 hours (content of fatty acid metal salt) : 2.4% by weight). Then, it filtered using the Nutsche which spread the filter paper ("No. 2" by Advantech). However, the filtration could not be completed even after 1 hour, and the amount of the obtained filtrate, that is, the transesterification reaction promoting composition 11 was only 130 parts by weight. The content of the fatty acid metal salt in the transesterification reaction promoting composition 11 was 0.167% by weight.

(Example 9) Transesterification reaction of triacylglyceride using transesterification reaction promoting composition 1200 parts by weight of palm olein (iodine value: 60) in a separable flask in a vacuum state (3 torr) (containing water) (Amount: 0.005% by weight) was maintained at 50 ° C. while stirring at 300 rpm, and 400 parts by weight of the composition 1 for promoting transesterification obtained in Example 1 was added thereto. The transesterification reaction was completed in 53 minutes. Moreover, the fatty acid metal salt content in the transesterification oil after the reaction was 0.106% by weight. The results are summarized in Table 2.

(Example 10) Transesterification of triacylglyceride using composition for promoting transesterification reaction 200 parts by weight of the composition for promoting transesterification prepared in Example 1 was added to palm olein (iodine) in a separable flask. Value 60) 1,400 parts by weight (water content: 0.007% by weight) was added in a state of 70 ° C., 300 rpm, and a vacuum state (3 torr). The transesterification reaction was completed in 30 minutes. Moreover, the fatty acid metal salt content in the transesterification oil after the reaction was 0.051% by weight. The results are summarized in Table 2.

(Example 11) Transesterification of triacylglyceride using composition for promoting transesterification reaction 400 parts by weight of the composition for promoting transesterification prepared in Example 2 was added to palm olein (iodine) in a separable flask. Value 60) To 1200 parts by weight (water content: 0.006% by weight), it was added at 80 ° C., 300 rpm, and in a vacuum state (3 torr). The transesterification reaction was completed in 5 minutes. Further, the content of the fatty acid metal salt in the transesterification oil after the reaction was 0.15% by weight. The results are summarized in Table 2.

(Example 12) Transesterification reaction of triacylglyceride using composition for promoting transesterification reaction 100 parts by weight of the composition for promoting transesterification prepared in Example 5 was 1500 parts by weight of beef tallow contained in a separable flask. It added in the state of 70 degreeC, 300 rpm, and a vacuum state (3 torr) with respect to (water content: 0.009 weight%). The transesterification reaction was completed in 10 minutes. Moreover, fatty acid metal salt content in the transesterification reaction fat after reaction was 0.044 weight%. The results are summarized in Table 2.

(Comparative Example 4) Transesterification reaction of triacylglyceride using composition for promoting transesterification reaction 400 parts by weight of the composition for promoting transesterification prepared in Comparative Example 1 was added to palm olein (iodine iodine) in a separable flask. Value 60) To 1,200 parts by weight (water content: 0.009% by weight), it was added at 50 ° C., 300 rpm, and in a vacuum state (3 torr). The transesterification reaction was completed in 50 minutes. The content of the fatty acid metal salt in the transesterification oil after the reaction was 0.625% by weight. The results are summarized in Table 2.

(Comparative Example 5) Transesterification of Triacyl Glyceride Using Transesterification Reaction Promoting Composition 200 parts by weight of the transesterification reaction promoting composition prepared in Comparative Example 1 was added to palm olein (iodine) in a separable flask. Value 60) 1,400 parts by weight (water content: 0.009% by weight) was added at 70 ° C., 300 rpm, and in a vacuum state (3 torr). The transesterification reaction was completed in 30 minutes. The content of the fatty acid metal salt in the transesterification oil after the reaction was 0.31% by weight. The results are summarized in Table 2.

(Comparative Example 6) Transesterification reaction of triacyl glyceride using transesterification reaction promoting composition 1600 parts by weight of palm olein (iodine value 60) (water content: 0.007% by weight) was put in a separable flask, The temperature was controlled at 50 ° C. while stirring (300 rpm). Thereafter, 1.6 parts by weight of sodium methylate was added in a vacuum state (3 torr). The transesterification reaction was completed in 85 minutes. The content of the fatty acid metal salt in the transesterification oil after the reaction was 0.64% by weight. Moreover, when the obtained transesterification reaction fat was washed with water and the fatty acid metal salt removal process was performed, the fatty acid metal salt in the obtained fat was 0.053 weight%. The results are summarized in Table 2.

(Comparative Example 7)
1600 parts by weight of palm olein (iodine value 60) (water content: 0.01% by weight) was put into a separable flask, and the temperature was controlled at 50 ° C. while stirring (300 rpm). Thereafter, 0.8 parts by weight of sodium methylate was added in a vacuum state (3 torr). The transesterification reaction was completed in 170 minutes. The content of the fatty acid metal salt in the transesterification oil after the reaction was 0.325% by weight. The results are summarized in Table 2.

<Measurement of solid fat content>
Solid fat content in fats and oils is determined by the method described in 2.2.9-2003 solid fat content (NMR method) of “Standard Oil and Fat Analysis Method” (issue year: 1996) edited by Japan Oil Chemical Association. The measurement was performed.

<Measurement of viscosity>
The viscosity of fats and oils is measured by the method described in 2.2.1.5-1996 viscosities (Brookfield method) of “Standard oil and fat analysis method” (issue year: 1996) edited by Japan Oil Chemical Association. went.

Example 13 Direct Transesterification Reaction of Triacyl Glyceride Using Transesterification Reaction Promoting Composition 400 parts by weight of the transesterification reaction promoting composition prepared in Example 1 was added to palm olein in a separable flask ( The iodine value was added to 1,200 parts by weight (water content: 0.005% by weight) at 80 ° C., 100 rpm, and in a vacuum state (3 torr). After holding at 80 ° C. for 20 minutes, the reaction temperature was lowered to 35 ° C. and the reaction was terminated after 24 hours. The solid fat content of the reaction fat was 26.1%, and the viscosity was 3,600 cp. The content of fatty acid metal salt in the reaction fat / oil was 0.106% by weight. Further, 980 parts by weight (yield: 61%) of a liquid oil component was obtained from the reaction oil / fat composition by using pressure filtration (maximum pressure 3 MPa). The results are summarized in Table 3.

(Comparative Example 9) Direct transesterification reaction of triacylglyceride using transesterification reaction promoting composition 400 parts by weight of the transesterification reaction promoting composition prepared in Comparative Example 1 was added to palm olein in a separable flask ( The iodine value was added to 1,200 parts by weight (water content: 0.005% by weight) at 80 ° C., 100 rpm, and in a vacuum state (3 torr). After holding at 80 ° C. for 20 minutes, the reaction temperature was lowered to 35 ° C. and the reaction was terminated after 24 hours. The solid fat content of the reaction fat was 25.9%, and the viscosity was 12400 cp. Moreover, fatty acid metal salt content in reaction fats and oils was 0.625 weight%. Moreover, 850 weight part (yield: 53 weight%) of liquid oil components was obtained from the reaction oil-fat composition using pressure filtration (maximum pressure of 3 MPa). The results are summarized in Table 3.

Claims (4)

  The transesterification time for producing the transesterification reaction promoting composition is 30 minutes or less, and after reacting animal oil or vegetable oil as triacylglyceride with sodium methylate as alkali catalyst, the water content is reduced to 0. A method for producing a composition for promoting transesterification of fats and oils, wherein a filter aid adjusted to 3% by weight or less is passed through a filter while being stirred and mixed, and the filtrate is recovered. The method for producing a composition for promoting transesterification of fats and oils according to claim 1 , wherein the filter aid is at least one selected from activated clay, pearlite, silicon dioxide, and diatomaceous earth. The transesterification reaction promoting composition obtained by the production method according to claim 1 or 2 is added in an amount of 5 to 35 parts by weight with respect to 100 parts by weight of a triacylglyceride serving as a raw material to be transesterified to perform a transesterification reaction. The manufacturing method of the oil-fat composition characterized by the above-mentioned. The method for producing an oil and fat composition according to claim 3 , wherein the transesterification reaction is a direct transesterification reaction, and the reaction temperature is 20 to 70 ° C.