KR101374630B1 - Method for manufacturing dimer acid methylester using fatty acid derived from animal and vegetable oils or waste oils - Google Patents

Abstract

The present invention facilitates conjugation of unsaturated fatty acid methyl esters in a component by conducting conjugation reaction of animal or vegetable oils derived from fatty acid methyl esters to increase the reactivity and distills and removes unreacted saturated fatty acid methyl esters. It relates to a method capable of producing dimer acid methyl ester.

Description

Production method of dimer acid methyl ester using animal or vegetable oils fatty acid methyl ester {METHOD FOR MANUFACTURING DIMER ACID METHYLESTER USING FATTY ACID DERIVED FROM ANIMAL AND VEGETABLE OILS OR WASTE OILS}

The present invention relates to a process for preparing dimer acid methyl ester using animal or vegetable oils derived from animal or vegetable oils, and more particularly to the conjugation reaction of animal or vegetable oils derived from fatty acid methyl esters of unsaturated fatty acid methyl esters. The present invention relates to a method for producing a high-purity dimer acid methyl ester with high yield by facilitating conjugation to increase reactivity and distilling off unreacted saturated fatty acid methyl ester.

In general, dimer acid using plant oil-derived tall oil, soybean oil, rapeseed oil, olive oil, rice bran oil, etc. is produced by the diels-Alder condensation of unsaturated fatty acids. It is widely known to use the tendency to be more stable cyclic.

U.S. Patent Nos. 3,422,124 and 3,632,822 disclose methods using a catalyst of strong acid under acidic clay. U.S. Patent No. 3,507,890 discloses a method for reacting unsaturated fatty acids at 270 DEG C. and 500 atm in the presence of an acidic or neutral clay catalyst such as montmorillonite, and Japanese Patent Application Laid-Open No. 40-8427 to the presence of acidic or neutral clays. The method of reacting by adding water and lithium carbonate is disclosed below. US Patent No. 3,157, 681 discloses a method of reacting a high concentration of unsaturated fatty acids at 180 to 260 ° C using acidic clay. All of these methods have a problem in that the reaction yield is lowered when using a raw material having a high content of unsaturated fatty acids using a raw material having a high content of unsaturated fatty acids. US Patent No. 6,835,324 discloses a method for synthesizing a dimer acid after a conjugation reaction using tall oil fatty acid, but has a problem of low reactivity. In addition, the foregoing prior arts all disclose methods for synthesizing dimer acid using vegetable oil fatty acids, and there is no mention of fatty acid methyl esters.

US Pat. No. 6,281,373 discloses a method for producing dimer acid in the presence of montmorillonite clay by synthesizing soybean oil with C1-C4 alkanols to synthesize fatty acid C1-C4 alkylmethyl esters, and separating unsaturated fatty acid C1-C4 alkyl esters therefrom. Is disclosed, but there is no mention of reactivity and yield.

It is an object of the present invention to prepare a high-purity dimer acid methyl ester in high yield by increasing the diels-Alder condensation reactivity by using conjugation reaction using animal or vegetable oils or waste oil-derived fatty acid methyl esters, unlike conventional vegetable oils. To provide a way to do it.

For the purposes of the present invention described above, the present inventors proceed with a conjugation (conjugation) reaction of a vegetable or waste oil-derived fatty acid methyl ester to increase the diels-Alder condensation reactivity of the conjugated unsaturated fatty acid methyl ester in the component and After distilling the reaction saturated fatty acid methyl ester, it was successful to prepare high purity dimer acid methyl ester in high yield, and as a result, the present invention was completed.

The present invention comprises the steps of adding a plant or waste oil-derived fatty acid methyl ester to the reactor to perform a conjugation reaction in the presence of an alkali catalyst; After the conjugation reaction, adding and reacting montmorillonite acid clay or lithium stabilized montmorillonite acid clay and water to the reactor; And removing the unreacted saturated fatty acid methyl ester after terminating the reaction.

In one embodiment of the present invention, fatty acid methyl esters of animal or vegetable oils may include palm oil, safflower seed oil, tall oil, fish oil, rapeseed oil, olive oil, and the like. Can be used, but is not necessarily limited thereto.

In one embodiment of the present invention, the conjugation reaction carried out in the presence of an alkali catalyst by adding animal or oil derived fatty acid methyl ester to the reactor is preferably carried out for 3 to 8 hours at 100 ~ 150 ℃.

In addition, in one embodiment of the present invention, the reaction carried out by adding montmorillonite acid clay or lithium stabilized montmorillonite acid clay and water to the reactor is carried out at a reaction pressure of 5 ~ 10 bar at a reaction temperature of 200 ~ 250 ℃ It is preferably carried out for 6 to 12 hours.

In addition, in one embodiment of the present invention, the step of removing the unreacted saturated fatty acid methyl ester is maintained for 3 to 5 hours under a vacuum pressure of 1 to 0.5 torr by maintaining the reactor temperature at 180 ~ 250 ℃ after the completion of the reaction Is preferably carried out during the process.

According to the present invention, a conjugation reaction is carried out on a fatty acid methyl ester derived from a plant or a waste oil to facilitate the conjugation of an unsaturated fatty acid methyl ester in a component, thereby increasing the reactivity and distilling and removing the unreacted saturated fatty acid methyl ester. Acid methyl esters can be obtained in high yield.

1 is a graph showing the results of measurement of NMR (nuclear magnetic resonance) spectrum through sampling in the middle after the progress of the conjugation reaction in Example 1 of the present invention.
Figure 2 is prepared by the dimer acid methyl ester according to Example 1 of the present invention through gel permeation chromatograph (GPC) unreacted saturated fatty acid methyl ester, unsaturated fatty acid methyl ester, dimer acid methyl ester, trimer / oligomeric methyl ester It is a graph showing the results of the analysis.

Hereinafter, the manufacturing method of the dimer acid methyl ester which concerns on this invention is demonstrated concretely.

First, animal or plant oil-derived fatty acid methyl esters are introduced into a reactor to perform a conjugation reaction in the presence of an alkali catalyst.

In the present invention, the animal and vegetable oil-derived fatty acid methyl ester may be palm oil, safflower seed oil, tall oil, fish oil, rapeseed oil, olive oil, and the like. It is not necessarily limited.

As the alkali catalyst used in the present invention, for example, potassium hydroxide, potassium methoxide, sodium hydroxide, etc. may be used, and methoxide potassium is preferably used.

The alkali catalyst may be used in an amount of 1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of a vegetable or waste oil-derived fatty acid methyl ester.

When the alkali catalyst is added less than 1 part by weight, the conjugation reaction yield is lowered. When the alkali catalyst is added more than 10 parts by weight, the hydrogenation reaction proceeds a lot by the catalyst, which may cause a problem that the composition of the fatty acid methyl ester is changed.

Conjugation reactions carried out in the presence of the alkali catalysts by adding animal or waste oil-derived fatty acid methyl esters to the reactor are preferably performed at 100 to 150 ° C. for 3 to 8 hours.

After the completion of the conjugation reaction, montmorillonite acid clay or lithium stabilized montmorillonite acid clay and water are added to the reactor and reacted.

In the present invention, after completion of the conjugation reaction, montmorillonite acid clay or lithium stabilized montmorillonite acid clay is added to the reactor to enhance the conjugation of the unsaturated fatty acid methyl ester after the completion of the reaction to induce a complete reaction of the unsaturated fatty acid methyl ester. Can be.

The montmorillonite-based acidic clay or lithium stabilized montmorillonite-based acidic clay is added in an amount of 1 to 10 parts by weight, preferably 4 to 8 parts by weight, based on 100 parts by weight of a fatty acid methyl ester derived from animal or vegetable oil or waste oil.

When the montmorillonite-based acidic clay or lithium stabilized montmorillonite-based acidic clay is added out of the range of 1 to 10 parts by weight based on 100 parts by weight of fatty acid methyl ester derived from animal or vegetable oil or waste oil, the yield of conjugated unsaturated fatty acid methyl ester is reduced, This can lead to an increase in production costs.

In the present invention, after the completion of the conjugation reaction, the conversion of oligomers in which dimerization proceeds in various forms can be suppressed by adding water to react with montmorillonite acid clay or lithium stabilized montmorillonite acid clay.

The water introduced together with montmorillonite acid clay or lithium stabilized montmorillonite acid clay is introduced into the reactor in an amount of 1 to 5 parts by weight, preferably 1 to 2 parts by weight, based on 100 parts by weight of a fatty acid methyl ester derived from animal or vegetable oil or waste oil.

After adding montmorillonite-based acidic clay or lithium stabilized montmorillonite-based acidic clay and water to the reactor as described above, the reaction pressure was maintained at 5 to 10 bar at a reaction temperature of 200 to 250 ° C. for 6 to 12 hours. Do this.

In the present invention, after the montmorillonite-based acidic clay or lithium stabilized montmorillonite-based acidic clay and water in the reactor as described above, and performing the step of reacting, the step of cooling and adding the phosphoric acid to the reactor, stirred and filtered further Can be done.

By adding hypophosphorous acid to the reactor, it is possible to minimize the color change of the final product that can occur in the subsequent process of distillation for the removal of catalyst and the removal of saturated fatty acid methyl ester.

Finally, after completion of the reaction, the unreacted saturated fatty acid methyl ester is removed.

The step of removing the unreacted saturated fatty acid methyl ester is performed for 3 to 5 hours under a vacuum pressure of 1 to 0.5 torr by maintaining the reactor temperature at 180 to 250 ℃ after the completion of the reaction to obtain an unreacted saturated fatty acid methyl ester Distill out to remove.

When the reaction is carried out according to the above-described process, the unsaturated fatty acid methyl ester in the raw material can be completely reacted by facilitating the conjugation of the unsaturated fatty acid methyl ester, and thereafter, by removing the unreacted saturated fatty acid methyl ester, high purity dimer acid methyl ester is obtained. Can be prepared (see Table 2 below).

The saponification value (SV) of the dimer acid methyl ester described in Table 2 means a fat content, and the dimer acid methyl ester prepared according to the present invention should be 190 or more, and the viscosity is 600 to 1,000 at 25 ° C. cps or less is preferred.

Hereinafter, preferred embodiments and test examples of the present invention will be described in detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary meanings and should be construed in accordance with the technical meanings and concepts of the present invention.

The embodiments and test examples described in the present specification are preferred embodiments of the present invention and are not intended to represent all of the technical ideas of the present invention and thus various equivalents and modifications may be substituted for them at the time of application .

Example 1

After adding 8 g of potassium hydroxide as an alkali catalyst to 400 g of the general waste cooking oil-derived fatty acid methyl ester of the composition shown in Table 1, the conjugation reaction was carried out at a reaction temperature of about 130 ° C. for about 4 hours, and the temperature was lowered to room temperature, followed by montmorillonite. 30 g of acidic clay and 8 g of water were added to the reactor, and the reaction temperature was raised to 250 ° C. for 8 to 12 hours. At this time, the reactor pressure was maintained at about 10 bar. After the completion of the reaction, the reaction mixture was cooled to 130 ° C., added about 8 g of 75% phosphoric acid, stirred for about 30 minutes or more, filtered, and saturated fatty acid was distilled off under vacuum pressure of 0.5 torr and 250 ° C. to prepare dimer acid methyl ester. . The ratios of saturated fatty acids and unsaturated fatty acids, dimers and trimers, viscosity and yield of the prepared dimer acid methyl ester were measured and shown in Table 2. In Example 1, the peaks of the isomers of the double bonds located in Nos. 9 and 12 of the unsaturated fatty acid methyl ester were confirmed by sampling NMR spectra in the middle of the conjugation reaction (see FIG. 1). After the preparation, the unreacted saturated fatty acid methyl ester, unsaturated fatty acid methyl ester, dimer acid methyl ester, and trimer / oligomeric methyl ester were analyzed through GPC (see FIG. 2).

[Example 2]

Dimer acid methyl ester was prepared in the same manner as in Example 1, except that fatty acid methyl ester of safflower seed having the composition shown in Table 1 was used. All conditions were carried out in the same manner as in Example 1 to prepare a dimer acid methyl ester. The ratios of saturated fatty acids and unsaturated fatty acids, dimers and trimers, viscosity and yield of the prepared dimer acid methyl ester were measured and shown in Table 2.

[Example 3]

Dimer acid methyl ester was prepared in the same manner as in Example 1 except that 8 g of methoxide potassium was added to the reactor as an alkali catalyst. The ratios of saturated fatty acids and unsaturated fatty acids, dimers and trimers, viscosity and yield of the prepared dimer acid methyl ester were measured and shown in Table 2.

Example 4

400 g of safflower seed-derived fatty acid methyl ester of the composition shown in Table 1 was added to the reactor as an alkali catalyst, and then the conjugation reaction was carried out at a reaction temperature of about 130 ° C. for about 4 hours. It carried out to prepare dimer acid methyl ester. The ratios of saturated fatty acids and unsaturated fatty acids, dimers and trimers, viscosity and yield of the prepared dimer acid methyl ester were measured and shown in Table 2.

Comparative Example 1

Dimer acid methyl ester was prepared under the same conditions as in Example 1 using the waste cooking oil-derived fatty acid methyl ester of the composition shown in Table 1 without the conjugation reaction process. The ratios of saturated fatty acids and unsaturated fatty acids, dimers and trimers, viscosity and yield of the prepared dimer acid methyl ester were measured and shown in Table 2.

[Comparative Example 2]

Dimer acid methyl ester was prepared under the same conditions as in Example 1 using safflower seed fatty acid methyl ester having the composition shown in Table 1 without the conjugation reaction process. The ratios of saturated fatty acids and unsaturated fatty acids, dimers and trimers, viscosity and yield of the prepared dimer acid methyl ester were measured and shown in Table 2.

[Table 1]

[Table 2]

Referring to Table 2, in Examples 1 to 4 carried out according to the present invention when compared to Comparative Examples 1 and 2 performed without the conjugation reaction process, the conversion to dimer acid methyl ester is improved to obtain a high purity dimer acid methyl ester. It can be seen that it could be obtained in high yield.

Claims (14)

Adding a plant or waste oil-derived fatty acid methyl ester to the reactor to perform a conjugation reaction in the presence of an alkali catalyst;
After the conjugation reaction, adding and reacting montmorillonite acid clay or lithium stabilized montmorillonite acid clay and water to the reactor; And
Removing the unreacted saturated fatty acid methyl ester after terminating the reaction;
As a manufacturing method of dimer acid methyl ester containing
The above-mentioned montmorillonite acid clay or lithium stabilized montmorillonite acid clay is introduced in an amount of 1 to 10 parts by weight based on 100 parts by weight of fatty acid methyl esters derived from animal or plant oils or waste oils.
The water added together with the above-described montmorillonite acid clay or lithium stabilized montmorillonite acid clay is introduced in an amount of 1 to 5 parts by weight based on 100 parts by weight of fatty acid methyl esters derived from animal or vegetable oils or waste oils.
After adding the above-mentioned montmorillonite acid clay or lithium stabilized montmorillonite acid clay and water, the reaction is carried out for 6 to 12 hours while maintaining a reaction pressure of 5 to 10 bar at a reaction temperature of 200 to 250 ° C. The manufacturing method of the dimer acid methyl ester to be.
The method of claim 1, wherein the animal or vegetable oil-derived fatty acid methyl ester is selected from the group consisting of palm oil, safflower seed oil, tall oil, fish oil, rapeseed oil and olive oil.
The method of claim 1, wherein the waste oil-derived fatty acid methyl ester is a waste cooking oil-derived fatty acid methyl ester.
The method according to claim 1, wherein the alkali catalyst is potassium hydroxide, potassium methoxide or sodium hydroxide.
The method of claim 1, wherein the alkali catalyst is used in an amount of 1 to 10 parts by weight based on 100 parts by weight of a fatty acid methyl ester derived from animal or plant oil or waste oil.
The method of claim 5, wherein the alkali catalyst is used in an amount of 1 to 5 parts by weight based on 100 parts by weight of a fatty acid methyl ester derived from animal or plant oil or waste oil.
The methylation of dimer acid according to claim 1, wherein the conjugation reaction carried out in the presence of an alkali catalyst by adding animal or waste oil-derived fatty acid methyl esters to the reactor is performed at 100 to 150 ° C. for 3 to 8 hours. Process for the preparation of esters.
delete The method of claim 1, wherein the montmorillonite acid clay or lithium stabilized montmorillonite acid clay is added to 4 to 8 parts by weight based on 100 parts by weight of the fatty acid methyl ester derived from animal or vegetable oil or waste oil. .
delete According to claim 1, wherein the montmorillonite-based acidic clay or lithium stabilized montmorillonite-based acidic clay is added to the reactor in 1 to 2 parts by weight based on 100 parts by weight of fatty acid methyl ester derived from animal or plant oil or waste oil. Method for producing dimer acid methyl ester.
delete The method of claim 1, wherein after the conjugation reaction is finished, montmorillonite-based acidic clay or lithium stabilized montmorillonite-based acidic clay and water are added and reacted, followed by adding phosphoric acid to the reactor, stirring and filtering. The manufacturing method of the dimer acid methyl ester containing.
The method of claim 1, wherein the step of removing the unreacted saturated fatty acid methyl ester is carried out for 3 to 5 hours under a vacuum pressure of 1 to 0.5 torr by maintaining the reactor temperature at 180 ~ 250 ℃ after the completion of the reaction The manufacturing method of dimer acid methyl ester which is used.

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