JP2011208021A - Process and catalyst for producing fatty acid alkyl ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for readily producing a fatty acid alkyl ester at a high reaction rate with a high yield without using any alkali metal catalyst, and a catalyst for producing the fatty acid alkyl ester.SOLUTION: The method for producing a fatty acid alkyl ester includes reacting triglyceride and alcohol in the presence of a catalyst, wherein the catalyst is a catalyst solution obtained by stirring and mixing a basic calcium compound and a specific quaternary ammonium salt, and removing a solid material from the resulting mixture solution.

Description

  The present invention relates to a raw material for producing soap, a synthetic raw material such as a higher alcohol and a surfactant, a method for producing a fatty acid alkyl ester useful as a fuel, and a catalyst for producing a fatty acid alkyl ester.

  Fatty acid alkyl esters are widely used as raw materials for soap production, synthetic raw materials such as higher alcohols and surfactants, and fuels. Examples of methods for obtaining fatty acid alkyl esters include triglycerides and methanol, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkali metal catalysts such as alkali metal alcoholates such as sodium methylate and sodium ethylate. It can manufacture by making it transesterify below (patent document 1).

  However, when an alkali metal catalyst is used when producing a fatty acid alkyl ester by transesterification of triglyceride and methanol, the alkali metal used as the catalyst is dissolved in the mixture containing the produced fatty acid alkyl ester. When the fatty acid alkyl ester is used as a fuel for a diesel engine, for example, with the alkali metal remaining, the alkali metal accumulates as a deposit in the metal part of the fuel system parts, lowering the fuel flow rate, lowering the output, worsening the exhaust gas Cause. For this reason, several water washing processes for removing an alkali metal are separately required, and there arises a problem of wastewater treatment and a high manufacturing cost.

  Under such circumstances, it has been studied to use a basic calcium compound which is a catalyst having low solubility in a mixed liquid containing a fatty acid alkyl ester. For example, as a method for obtaining a fatty acid alkyl ester from a triglyceride and methanol by transesterification without using an alkali metal catalyst, Patent Document 2 describes that calcium oxide or calcium hydroxide is used as a catalyst for transesterification. Yes. Patent Documents 3 and 4 describe a method in which highly active calcium oxide obtained by firing calcium carbonate or the like under specific conditions is used as a catalyst. Furthermore, Patent Document 5 describes a method using calcium oxide activated in alcohol as a catalyst. Furthermore, Patent Document 6 describes a method using calcium methoxide powder as a catalyst.

JP-A 56-120799 JP 2001-271090 A WO2006 / 134845 WO2008 / 090987 WO2007 / 088702 WO2009 / 107739

  However, in any method, when a basic calcium compound such as calcium oxide is used as a catalyst, there is a problem that the reaction rate of the transesterification reaction is slow and the fatty acid alkyl ester cannot be obtained efficiently. In addition, in the reaction mixture obtained after the transesterification reaction, a large amount of basic calcium compound remains, so when separating glycerol from the reaction mixture, the separability of the fatty acid alkyl ester layer and the glycerol layer is reduced, There is a problem that the extraction of the glycerin layer is also hindered. Furthermore, since a large amount of calcium is contained in the obtained fatty acid alkyl ester product, a calcium removal step using a chelating agent or the like for removing calcium is necessary, and there is a problem that the production process becomes complicated.

  Accordingly, the present invention provides a method for producing a fatty acid alkyl ester and a catalyst for producing a fatty acid alkyl ester, which can easily produce a fatty acid alkyl ester at a high reaction rate and in a high yield using a basic calcium compound as a catalyst. The purpose is to do.

  In order to achieve the above object, the present inventors have conducted extensive research. As a result, in the method for producing a fatty acid alkyl ester by reacting triglyceride and alcohol in the presence of a catalyst, a basic calcium compound and a specific compound are used as a catalyst. By using a catalyst solution obtained by stirring and mixing with a quaternary ammonium salt and removing solids from the obtained mixed solution, it can be easily obtained at a high reaction rate and in a high yield without using an alkali metal catalyst. It has been found that fatty acid alkyl esters can be produced.

  That is, the present invention is a method for producing a fatty acid alkyl ester by reacting triglyceride and alcohol in the presence of a catalyst, wherein the catalyst comprises a basic calcium compound, the following formula (1) or the following formula (2). And a catalyst solution obtained by removing solids from the obtained mixed solution by stirring and mixing with at least one compound represented by the formula:

  The present invention also provides a catalyst for producing a fatty acid alkyl ester used for producing a fatty acid alkyl ester by reacting a triglyceride and an alcohol, wherein the basic calcium compound and the above formula (1) or the above formula (2) A catalyst for producing a fatty acid alkyl ester comprising a catalyst solution obtained by stirring and mixing at least one compound represented to remove solids from the obtained mixed solution.

  As described above, according to the present invention, a fatty acid alkyl ester production method and a fatty acid alkyl ester can be easily produced at a high reaction rate and in a high yield using a basic calcium compound as a catalyst. A production catalyst can be provided.

As the triglyceride used in the method for producing a fatty acid alkyl ester and the catalyst for producing a fatty acid alkyl ester according to the present invention, those represented by the following formula (3) are preferable. In the formula, R ¹ , R ² and R ³ may be aliphatic hydrocarbon groups containing 6 to 24 carbon atoms, and R ¹ , R ² and R ³ are saturated aliphatic hydrocarbon groups. It may be an unsaturated aliphatic hydrocarbon group. Furthermore, R ¹ , R ² and R ³ may contain a hydroxy group.

_{^{CH 2 (OCOR 1) -CH (}} OCOR 2) -CH 2 OCOR 3 ... (3)

  As the triglyceride, various substances such as those contained in natural fats and oils such as vegetable oils and animal oils and chemically synthesized oils can be used, and it is particularly preferable that they are derived from biomass.

  Vegetable oil and animal oil include fish oil, animal oil such as beef tallow and lard, safflower oil, sunflower oil, linseed oil, soybean (soybean) oil, rapeseed (rapeseed) oil, cottonseed oil, olive oil, palm oil, corn And vegetable oils such as oil, sesame oil, castor oil, rice oil, and Jatropha oil. These fats and oils may use only 1 type, and may mix and use 2 or more types. Furthermore, these fats and oils may be waste oil (waste cooking oil) such as tempura oil.

  When waste oil is used, it is preferable to remove impurities using a known filter such as a filter press in advance. At this time, use known filter media such as activated clay, diatomaceous earth, zeolite, activated carbon, acidic clay, bentonite, silica-based adsorbent, silica-alumina compound, calcium carbonate, bone ash, perlite, cellulose, magnesia, alumina, and gypsum. You can also. The amount of the filter medium can be appropriately set according to the type of waste oil, the amount of impurities contained in the waste oil, and the like.

  The alcohol used in the method for producing a fatty acid alkyl ester and the fatty acid alkyl ester production catalyst according to the present invention is preferably one represented by the following formula (4).

R ⁴ OH (4)

In the formula, R ⁴ is preferably a saturated aliphatic hydrocarbon group having 1 to 24 carbon atoms. As such alcohols, primary alcohols such as methanol, ethanol, n-propanol and n-butanol, secondary alcohols such as isopropanol and sec-butanol, and tertiary alcohols such as tert-butanol may be used. it can. In this, methanol and ethanol are preferable and methanol is especially preferable.

  In the method for producing a fatty acid alkyl ester according to the present invention, when the triglyceride represented by the formula (3) is reacted with the alcohol represented by the formula (4), the following formulas (5) to (7) are used. Fatty acid alkyl esters can be obtained.

R ¹ COOR ⁴ (5)

R ² COOR ⁴ (6)

R ³ COOR ⁴ (7)

In the fatty acid alkyl ester represented by the formulas (5) to (7), R ^{1 to} R ⁴ are the same as those in the formulas (3) and (4). In the case where R ⁴ is in the above-described range, the fatty acid alkyl ester represented by the formulas (5) to (7) obtained by the transesterification can be favorably used for various purposes.

  In the method for producing a fatty acid alkyl ester according to the present invention, the temperature condition for the reaction of triglyceride and alcohol is preferably 50 ° C. or higher. When the temperature condition is excessively lower than 50 ° C., the yield of the fatty acid alkyl ester is lowered. A more preferable temperature range is 50 to 100 ° C. when the alcohol is methanol, ethanol, propanol or the like. The proportion of triglyceride and alcohol is preferably 4 to 150 mol of alcohol, more preferably 5 to 60 mol, per 1 mol of triglyceride.

  In the method for producing a fatty acid alkyl ester according to the present invention, the reaction is carried out in the presence of a catalyst solution. The catalyst solution is prepared by first stirring and mixing a basic calcium compound and at least one compound represented by the formula (1) or (2), and then removing solids from the obtained mixed solution. Can be obtained by:

  Examples of the basic calcium compound include calcium alkoxides such as calcium oxide, calcium hydroxide, and calcium methoxide, and hydrates of calcium alkoxide such as hydrates of calcium methoxide. Among these, calcium oxide and calcium alkoxide such as calcium methoxide are preferable, and calcium methoxide is more preferable. The average particle size of the basic calcium compound is preferably 1 to 100 μm, and more preferably 1 to 50 μm. It is preferable that the usage-amount of a basic calcium compound is 0.01-0.3 mol with respect to 1 mol of triglycerides.

  The compound mixed with the basic calcium compound is a bis quaternary ammonium carbonate represented by the formula (1) or a quaternary ammonium monoalkyl carbonate represented by the formula (2).

In Formula (1) and Formula (2), R ^{5 to} R ⁹ are each independently a hydrocarbon group having 1 to 24 carbon atoms, and preferably a hydrocarbon group having 1 to 18 carbon atoms. Any two or three of R ^{5 to} R ⁸ may be bonded to each other to form a heterocycle or condensed ring via a carbon, oxygen, or nitrogen atom. The hydrocarbon group may be a linear, branched, or cyclic aliphatic hydrocarbon group or an aromatic hydrocarbon group, and has a substituent as long as the effects of the present invention are not impaired. It may be.

Examples of the heterocyclic ring formed by any two or three of R ^{5 to} R ⁸ include, for example, pyrrolidine, piperidine, morpholine, pyridine, imidazole, imidazoline, pyrazole, pyrrole, pyrroline, 1,4-diazabicyclo [2.2. .2] various heterocycles such as octane, 1,5-diazabicyclo [4.3.0] non-5-ene, and 1,8-diazabicyclo [5.4.0] undec-7-ene. . Specific examples of three of R ^{5 to} R ⁸ forming a heterocycle via a carbon or nitrogen atom include the carbonates shown in the following formula (8) and the following formula (9). Examples of R in the following formula (8) and the following formula (9) include a hydrocarbon group, an amino group, a halogen group, a nitro group, a cyano group, an alkoxy group, a phenyl group, and a hydroxyl group. Specific examples of R include 4-dimethylamino group. R is bonded to any position of the heterocycle.

  Specific examples of the compound represented by the formula (1) include bistriethylmethylammonium carbonate, bis (1-methyl-4-dimethylaminopyridinium) carbonate, bis (1,1-dimethylpyrrolidinium) carbonate. Bis (4,4-dimethylmorpholidium) carbonate, bis (1-ethyl-1-methylpyrrolidinium) carbonate, and the like.

  Specific examples of the compound represented by the formula (2) include triethylmethylammonium monomethyl carbonate, 1-methyl-4- (N, N-dimethylamino) pyridinium monomethyl carbonate, N, N-dimethylmorpholium monomethyl. Carbonate, N, N-dimethylaminopiperidinium monomethyl carbonate, tetramethylammonium monomethyl carbonate, diethyldimethylammonium monomethyl carbonate, triethylmethylammonium monomethyl carbonate, trioctylmethylammonium monomethyl carbonate, and N- (2 -Hydroxyethyl) -N, N, N-trimethylammonium monomethyl carbonate and the like.

  Specific examples of the compound represented by the formula (8) include bis (1-methyl) pyridinium carbonate and bis (1-methyl, 4-dimethylamino) pyridinium carbonate. Specific examples of the compound represented by the formula (9) include 1-methylpyridinium monomethyl carbonate and (1-methyl, 4-dimethylamino) pyridinium monomethyl carbonate.

About the compound represented by Formula (1) and Formula (2), it can manufacture as follows. The compound represented by Formula (1) is, for example, dialkyl carbonate having R ⁸ in Formula (1) as an alkyl group with respect to 1 mol of tertiary amine having R ^{5 to} R ⁷ as a substituent in Formula (1). 0.5 mol is mixed and reacted. In the reaction, a solvent such as methanol may be used. The reaction temperature is preferably 100 to 180 ° C.

On the other hand, the compound represented by the formula (2) includes, for example, 1 mol of a tertiary amine having R ^{5 to} R ⁷ as a substituent in the formula (2) and R ⁸ in the formula (2) as an alkyl group. A mixture of 1 mol or more of dialkyl is reacted. In the reaction, a solvent such as methanol may be used. The reaction temperature is preferably 100 to 180 ° C. Compounds represented by formula (8) and formula (9) can also be obtained in the same manner as described above. In addition, about the manufacturing method of Formula (1) and Formula (2), it is not limited to the above, According to the kind of tertiary amine and dialkyl carbonate, the molar ratio of tertiary amine and dialkyl carbonate, reaction temperature, a solvent, etc. Set as appropriate.

  When a basic calcium compound and at least one compound represented by formula (1) or formula (2) are mixed, a basic calcium compound, or at least one compound represented by formula (1) or formula (2) The reaction rate of triglyceride and alcohol can be improved as compared with the case where is used alone.

  The mixing ratio of the basic calcium compound and at least one compound represented by the formula (1) or the formula (2) is represented by the formula (1) or the formula (2) with respect to 1 mol of the basic calcium compound. The at least one compound is preferably 1.0 mol or more, more preferably 1.0 to 10 mol, and particularly preferably 1.0 to 5 mol.

  The stirring and mixing of the basic calcium compound and at least one compound represented by the formula (1) or the formula (2) can be performed using a general means, for example, various stirrers such as a magnetic stirrer. Can be mixed with stirring.

  In the stirring and mixing, it is preferable to stir and mix the basic calcium compound and at least one compound represented by the formula (1) or the formula (2) in the presence of a solvent. The solvent is preferably a basic calcium compound, at least one compound represented by formula (1) or formula (2), and a triglyceride and an alcohol that are inactive with the fatty acid alkyl ester. The same alcohol as that used for the production is more preferred, and methanol is particularly preferred.

  The amount of the solvent added is preferably such that the basic calcium compound concentration is 1 to 40% by mass, more preferably 3 to 20% by mass in Formula A below. It is particularly preferable to add so that it becomes 10 mass%.

Basic calcium compound concentration (mass%) = basic calcium compound / (solvent + at least one compound represented by formula (1) or formula (2)) × 100 (formula A)

  In addition to the solvent, an alkali metal salt or alkaline earth metal salt of a fatty acid may be added. By adding these, the reaction rate can be further improved and the fatty acid methyl ester can be produced in a high yield. Examples of the fatty acid include fatty acids containing 6 to 24 carbon atoms, and specific examples include stearic acid. Examples of the alkali metal include sodium and potassium, and examples of the alkaline earth metal include calcium and magnesium.

  The temperature of stirring and mixing may be lower than the decomposition temperature of at least one compound represented by formula (1) or formula (2). When a solvent is used for stirring and the decomposition temperature is higher than the boiling point of the solvent, stirring and mixing may be performed at a temperature from room temperature to less than the boiling point of the solvent. Usually, there is no problem if stirring and mixing are performed at room temperature.

  The time for stirring and mixing is generally 3 minutes or longer and 3 hours or shorter. For example, when the basic calcium compound is calcium methoxide, in a container having an internal volume of 100 mL at room temperature, the concentration of calcium methoxide (average particle size 0.1 to 10 μm) is 3 to 8% by mass, methanol and methyl (methyltriethyl). In the condition of a total amount of ammonium) carbonate of 40 to 50 mL and a stirrer rotation speed of 100 to 300 rpm, the stirring and mixing time is preferably 3 minutes to 3 hours, more preferably 10 minutes to 2 hours, It is particularly preferable that the time be from 1 minute to 1 hour. Stirring for too long is uneconomical and undesirable. In the present invention, it is preferable to carry out stirring and mixing under conditions that give at least a solid-liquid contact effect equivalent to that under these conditions.

  The pressure at the time of stirring and mixing is not particularly limited, and can be performed, for example, under normal pressure. The stirring and mixing is preferably performed in an atmosphere in which moisture absorption and carbonation of the basic calcium compound can be suppressed, for example, in a nitrogen atmosphere, but may be normally performed in the air.

  A preferred specific example of stirring and mixing in the case where the basic calcium compound is calcium methoxide will be described. First, a calcium methoxide suspension is prepared from calcium oxide as described in Patent Document 6. At least one compound represented by formula (1) or formula (2) is added to the obtained calcium methoxide suspension at the above ratio, and under stirring and mixing conditions that give the solid-liquid contact effect as described above. Stir and mix. When preparing calcium methoxide from calcium oxide, at least one compound represented by formula (1) or formula (2) may be added, and calcium methoxide may be prepared and stirred at the same time.

  Examples of means for removing the solid content from the mixed solution obtained by stirring and mixing include filtration and centrifugation. The solid content does not need to be completely removed, but the calcium concentration in the catalyst solution obtained by removing the solid content from the mixed solution is preferably 5000 ppm by mass or less, and more preferably 3000 ppm by mass or less. preferable. In the stirring and mixing of the basic calcium compound and at least one compound represented by the formula (1) or (2), the calcium concentration in the catalyst solution obtained by removing solids from the mixed solution obtained by stirring and mixing is It is preferable to carry out within this range.

  In the method for producing a fatty acid alkyl ester according to the present invention, a fatty acid alkyl ester mixture (reaction mixture) containing a fatty acid alkyl ester is obtained by reacting triglyceride and alcohol in the presence of the catalyst solution. Since the fatty acid alkyl ester mixture contains glycerin as an impurity, the method for producing a fatty acid alkyl ester according to the present invention preferably includes a separation step of separating glycerin from the fatty acid alkyl ester mixture. Examples of the separation step include static separation and centrifugal separation, and static separation is preferable.

  The method for producing a fatty acid alkyl ester according to the present invention comprises, if necessary, an activated clay, diatomaceous earth, zeolite, activated carbon, acidic clay, bentonite, silica-based adsorbent, silica-alumina. It includes a filtration step of filtering using a known filter medium such as a compound, calcium carbonate, bone ash, perlite, cellulose, magnesia, alumina, or gypsum. The amount of the filter medium varies depending on the state of the produced fatty acid alkyl ester mixture, but is 1 to 20% by mass of the fatty acid alkyl ester obtained in the separation step.

  In addition, the method for producing a fatty acid alkyl ester according to the present invention may include a water washing step if necessary, or phosphoric acid, phosphorous acid, hypophosphoric acid, hypophosphorous acid, pyrophosphoric acid, metaphosphoric acid, sulfuric acid, pyro Provided with a neutralization / washing step of adding / mixing one or more acids selected from the group consisting of sulfuric acid, carbon dioxide, hydrochloric acid, acetic acid and oxalic acid and water to the fatty acid alkyl ester obtained in the separation step It may be.

  In the method for producing a fatty acid alkyl ester according to the present invention, the produced fatty acid alkyl ester represented by the formulas (5) to (7) is used for various uses such as fuels, high-quality soaps and higher alcohol raw materials. be able to.

  According to the method for producing a fatty acid alkyl ester and the catalyst for producing a fatty acid alkyl ester according to the present invention, as a catalyst, a basic calcium compound and at least one compound represented by formula (1) or formula (2) are stirred and mixed. Although solids are removed, the reaction rate of triglyceride and alcohol can be remarkably improved compared to conventional methods using a basic calcium compound as a catalyst, and fatty acid alkyl esters are efficiently obtained in high yield. be able to. In the separation step, the fatty acid alkyl ester and glycerin can be easily left and separated, and the glycerin can be extracted without hindrance. Furthermore, the calcium concentration in the fatty acid alkyl ester obtained can satisfy the EN standard without any special calcium removal operation.

  Further, according to the fatty acid alkyl ester production method and fatty acid alkyl ester production catalyst according to the present invention, since an alkali metal catalyst is not used, several separate water washing steps for removing the alkali metal are not required, A fatty acid alkyl ester having a low acid value can be obtained.

  Furthermore, if necessary, the post-treatment process may be a filtration process using activated clay or the like, or a single neutralization / water washing process, and no major problems occur.

  Next, examples of the method for producing a fatty acid alkyl ester according to the present invention will be described. The basic calcium compound used in this example and the compounds represented by formula (1) and formula (2) were produced as follows.

(Production Example 1: Calcium methoxide)
A calcium methoxide dispersion was prepared by pulverizing 2.625 g of calcium oxide produced by burning heavy calcium carbonate in the air in the atmosphere with a rocking mill in 30 g of methanol for 2 hours. The average particle size of the particles in the obtained dispersion was 1.3 μm.

(Production Example 2: Methyl (methyltriethylammonium) carbonate)
In a 200 ml SUS autoclave (manufactured by pressure-resistant glass industry), 67.5 g (0.75 mol) of dimethyl carbonate (manufactured by Ube Industries), 75.0 g (0.74 mol) of triethylamine (manufactured by Wako Pure Chemical), and methanol ( 48 g (1.5 mol) manufactured by Wako Pure Chemical Industries, Ltd.) was charged and reacted at a reaction temperature of 140 ° C. for 3 hours. The pressure at this time was 2.0 MPaG (G represents a gauge pressure). Unreacted dimethyl carbonate, triethylamine, and methanol were distilled off under reduced pressure, and then 30 ml of dimethyl carbonate was added for washing. After removing the upper dimethyl carbonate layer, the lower part dimethyl carbonate was distilled off under reduced pressure to obtain 98.5 g of a viscous liquid. ^{From the result of 1} H-NMR and ¹³ C-NMR analysis, it was confirmed that the viscous liquid was methyl (methyltriethylammonium) carbonate (hereinafter referred to as MMTEAC).
¹ H-NMR: 1.29-1.38 ppm (m, 9H, CH3 CH2N), 2.96 ppm (s, 3H, N CH3 ), 3.30-3.36 ppm (m, 9H, OCOO CH3 , CH3 CH2 N)
¹³ C-NMR (CD3OD, δ): 7.95 ppm (—NCH 2 CH 3 ), 47.05 ppm (—N CH 3 ), 56.98 ppm (—N CH 2 CH 3), 60.14 ppm (OCOO CH 3 ), 163.10 ppm (O C OO)

(Production Example 3: Catalyst solution 1)
To the total amount of the calcium methoxide dispersion prepared in Production Example 1, 10.5 g of MMTEAC obtained in Production Example 2 (1.2 times mol with respect to Ca) was added, and the mixture was added at 30 at normal pressure and room temperature. The mixture was stirred and mixed for a minute (basic calcium compound concentration at the time of stirring and mixing: 6.5% by mass). The obtained mixed solution was subjected to suction filtration using a filter paper (No. 5A filter paper, manufactured by Toyo Filter Paper Co., Ltd.) to remove the solid matter, whereby catalyst solution 1 was obtained. The calcium concentration in this catalyst solution was 1130 mass ppm.

(Production Example 4: Catalyst solution 2)
A catalyst solution 2 was obtained in the same manner as in Production Example 3 except that the amount of MMTEAC added was 17.5 g (2.0 moles relative to Ca) (basic calcium compound concentration during stirring and mixing: 5. 5% by mass). The calcium concentration in the catalyst solution was 279 mass ppm.

(Production Example 5: Catalyst solution 3)
A catalyst solution 3 was obtained in the same manner as in Production Example 3, except that the stirring and mixing time was changed to 5 minutes. The calcium concentration in the catalyst solution was 1022 mass ppm.

(Production Example 6: Catalyst solution 4)
A catalyst solution 4 was obtained in the same manner as in Production Example 3, except that the stirring and mixing time was 3 hours. The calcium concentration in this catalyst solution was 49 mass ppm.

(Production Example 7: Catalyst solution 5)
A catalyst solution 5 was obtained in the same manner as in Production Example 4 except that 0.525 g of calcium stearate was added in addition to MMTEAC. The calcium concentration in this catalyst solution was 407 mass ppm.

[Example 1]
A 1000 mL separable flask equipped with a stirrer and a reflux condenser was charged with 750 g of rapeseed oil (rapeseed white squeezed oil; manufactured by Riken Agricultural Processing) and 103.6 g of methanol, and the temperature was kept at 64 ° C. Thereafter, the whole amount of the catalyst solution 1 was added to start the reaction, and the yield of fatty acid methyl ester was measured by gas chromatography after 0.5 hours. Instead of setting the reaction time to 0.5 hour, the yield of fatty acid methyl ester was similarly measured by gas chromatography with 1.0 hour and 1.5 hour. The results are shown in Table 1.

[Example 2]
The reaction was performed in the same manner as in Example 1 except that the whole amount of the catalyst solution 2 was added instead of the catalyst solution 1. The results are shown in Table 1.

[Comparative Example 1]
Instead of the catalyst solution 1, the reaction was performed in the same manner as in Example 1 except that the total amount of the calcium methoxide dispersion prepared in Production Example 1 was added. The results are shown in Table 1.

[Comparative Example 2]
Instead of the catalyst solution 1, the reaction was performed in the same manner as in Example 1 except that 10.5 g of MMTEAC prepared in Production Example 2 (14.0 kg / kg rapeseed oil) was added. The results are shown in Table 1.

[Comparative Example 3]
The reaction was performed in the same manner as in Example 1 except that 17.5 g of MMTEAC prepared in Production Example 2 (23.3 kg / kg rapeseed oil) was added instead of Catalyst Solution 1. The results are shown in Table 1.

Example 3
The reaction was performed in the same manner as in Example 1 except that the whole amount of the catalyst solution 3 was added instead of the catalyst solution 1. The results are shown in Table 2.

Example 4
The reaction was performed in the same manner as in Example 1 except that the whole amount of the catalyst solution 4 was added instead of the catalyst solution 1. The results are shown in Table 2.

Example 5
The reaction was carried out in the same manner as in Example 1 except that the entire amount of the catalyst solution 5 was added instead of the catalyst solution 1. However, the reaction time was 2 hours and 3 hours. The results are shown in Table 3. In addition, when the reaction mixture after completion | finish of reaction 3 hours was cooled, heavy liquid (glycerin layer) stood and separated, and methanol was depressurizingly distilled from the obtained light liquid (fatty acid methyl ester layer), in fatty acid methyl ester The calcium concentration of was 1.9 ppm by mass.

Example 6
The reaction was carried out in the same manner as in Example 1 except that 218.1 g of methanol was used instead of 103.6 g of methanol, and the entire amount of catalyst solution 2 was added instead of catalyst solution 1. However, the reaction time was 2 hours and 3 hours. The results are shown in Table 3. The reaction mixture after the completion of the reaction for 3 hours was cooled, the heavy liquid was allowed to stand and separated, and methanol was distilled off from the obtained light liquid under reduced pressure. As a result, the calcium concentration in the fatty acid methyl ester was 2.7 ppm by mass. Met.

Example 7
The reaction was performed in the same manner as in Example 1 except that 218.1 g of methanol was used instead of 103.6 g of methanol, and the entire amount of the catalyst solution 5 was added instead of the catalyst solution 1. However, the reaction time was 2 hours and 3 hours. The results are shown in Table 3. The reaction mixture after the completion of the reaction for 3 hours was cooled, the heavy liquid was allowed to stand and separated, and methanol was distilled off from the obtained light liquid under reduced pressure. As a result, the calcium concentration in the fatty acid methyl ester was 0.4 mass ppm. Met.

Claims (8)

A method of producing a fatty acid alkyl ester by reacting triglyceride and alcohol in the presence of a catalyst,
The catalyst is a catalyst solution obtained by stirring and mixing a basic calcium compound and at least one compound represented by the following formula (1) or the following formula (2), and removing solids from the obtained mixed solution. A method for producing a fatty acid alkyl ester, comprising:
  The fatty acid alkyl ester according to claim 1, wherein 1.0 mol or more of at least one compound represented by the formula (1) or the formula (2) is used with respect to 1 mol of the basic calcium compound. Production method.   The method for producing a fatty acid alkyl ester according to claim 1 or 2, wherein the basic calcium compound is calcium oxide or calcium alkoxide.   The method for producing a fatty acid alkyl ester according to any one of claims 1 to 3, wherein the catalyst solution has a calcium concentration of 5000 ppm or less. In the catalyst for fatty acid alkyl ester production used when producing a fatty acid alkyl ester by reacting triglyceride and alcohol,
A catalyst solution obtained by stirring and mixing a basic calcium compound and at least one compound represented by the following formula (1) or the following formula (2) to remove solids from the obtained mixed solution is included. A catalyst for producing a fatty acid alkyl ester.
  6. The fatty acid alkyl ester according to claim 5, wherein at least one compound represented by the formula (1) or the formula (2) is 1.0 mol or more per 1 mol of the basic calcium compound. Catalyst for production.   7. The fatty acid alkyl ester production catalyst according to claim 5, wherein the basic calcium compound is calcium oxide or calcium alkoxide. The catalyst for producing a fatty acid alkyl ester according to any one of claims 5 to 7, wherein the catalyst solution has a calcium concentration of 5000 ppm or less.