JP2006342328A - Method for producing fatty acid ester and method for producing glycerol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a simple method for production with which a high-purity product (a fatty acid ester or glycerol) is obtained at a low cost/high reaction efficiency without requiring a step of separating a catalyst. <P>SOLUTION: The method for producing the fatty acid ester from oils and fats and a monohydric alcohol comprises using a chemical catalyst. In the method, the excessive monohydric alcohol in a state of superheated vapor is continuously fed to a reaction system and subjected to a transesterification with the oils and fats. The resultant reaction product containing the fatty acid ester in a state of a vapor phase or a mixed phase accompanying a droplet-like phase thereof is continuously taken out together with the superheated vapor of the monohydric alcohol. Thereby, the fatty acid ester is separated and recovered. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a useful method for producing a fatty acid ester or glycerin by reacting a triglyceride contained in fats and oils with an alcohol and transesterifying it, and an ester exchange reaction apparatus used therefor.

  Attempts to use plant-derived fuels in place of fossil fuels have been actively conducted as one of the efforts to meet carbon dioxide emission regulations. Palm oil, rapeseed oil, etc., usually obtained from plants are mainly composed of triglycerides, so the viscosity is higher than that of light oil, and it solidifies in cold districts due to the melting point. Not always appropriate. For this reason, attempts have been made to produce a diesel fuel equivalent to light oil by carrying out an ester exchange reaction with triglycerides using an alkyl alcohol to obtain a fatty acid alkyl ester, and various methods have been proposed.

  For example, as a method using a chemical catalyst, Patent Document 1 proposes a method using an alkali catalyst such as a caustic potash catalyst, a potash carbonate catalyst, and a calcium hydroxide catalyst, and there are scattered examples of practical use on a small scale. The methods specifically disclosed in these documents are substantially low in productivity because of batch processing, and it is difficult to recover the catalyst from the mixture with by-product glycerin. . Therefore, even if these methods are used, there are many examples in which they must be treated as hazardous waste together with glycerin. In addition, this type of method is applicable to small-scale production, but is not suitable for mass production that can contribute to environmental problems.

On the other hand, in order to improve the production speed, a continuous production method is disclosed in Patent Document 2, but the productivity is still not sufficient even when this method is used, and the catalyst recovery is the same as above. There's a problem.
JP 2003-96473 A Japanese Patent Laid-Open No. 10-182518

  In the present invention, it is an object to develop a simple production method that solves the problems of the production method described above and obtains a product (fatty acid ester and glycerin) with low cost, high reaction efficiency, and high purity without a catalyst separation step. .

  The inventors of the present invention have made the following invention by combining the above-mentioned chemical catalyst method with simple and high reaction efficiency and the collection of a high-purity product by gas phase collection of reaction products.

  (1) A method for producing a fatty acid ester from fats and oils and a monohydric alcohol using a chemical catalyst, wherein excess monohydric alcohol is continuously supplied to the reaction system in the form of superheated steam. The reaction product containing the fatty acid ester is continuously withdrawn together with the superheated vapor of the monohydric alcohol in the gas phase or in the mixed phase with the droplet phase, and the fatty acid ester is separated and recovered. A method for producing a fatty acid ester.

  (2) The method for producing a fatty acid ester according to (1), wherein the chemical catalyst is an alkali metal compound or / and an alkaline earth metal compound.

  (3) The method for producing a fatty acid ester according to the above (1) or (2), wherein the chemical catalyst is sodium hydroxide or / and potassium hydroxide.

  (4) The amount of the chemical catalyst to be used is 0.0002 mol to 0.2 mol with respect to 1 kg of the raw material oil stored in the reaction vessel, according to any one of the above (1) to (3) A method for producing a fatty acid ester.

  (5) The reaction is caused to occur at a reaction vessel pressure of about normal pressure, the temperature of alcohol in the state of superheated steam is 250 ° C to 350 ° C, and the temperature of fats and oils is 250 ° C to 350 ° C. The manufacturing method of the fatty acid ester in any one of said (1)-(4).

  (6) A method for producing glycerin from fats and oils and monohydric alcohols using a chemical catalyst, wherein excess monohydric alcohols are continuously supplied to the reaction system in the form of superheated steam, A transesterification reaction is performed, and a reaction product containing glycerin is continuously withdrawn together with superheated steam of monohydric alcohol in a gas phase or a mixed phase with a droplet phase therein, and glycerin is separated and recovered. A method for producing glycerin.

  (7) A reaction vessel equipped with a heating / heat-retaining device, an oil / fat supply port, a nozzle for supplying alcohol in the form of superheated steam below the reaction vessel, a gas phase or a droplet phase above the reaction vessel The method for producing a fatty acid ester according to any one of (1) to (5) or a glycerin according to (6), wherein an outlet for extracting the reaction product in a mixed phase state together with superheated steam of a monohydric alcohol is provided. For transesterification used in the production method.

  (8) A draft tube, an impeller, and a static mixer are installed in a reaction vessel equipped with a heating and heat insulation device, a supply port for supplying fats and oils, and a nozzle for supplying alcohol in the form of superheated steam (1) to (5) provided with an outlet for extracting a reaction product in a gas phase or a mixed phase accompanied by a droplet-like phase together with superheated steam of monohydric alcohol at the upper part of the reaction vessel. ) Or a transesterification reaction apparatus for use in the method for producing glycerin according to (6) above, wherein the fats and oils containing bubbles of alcohol in the form of superheated steam and the chemical catalyst are used. The mixture descends inside the draft tube by the impeller, forms a circulating flow that rises outside the tube, and passes through the static mixer on the way to facilitate gas-liquid contact. Transesterification reactor was so that.

  (9) The transesterification reactor according to (7) or (8), further comprising a temperature control device for superheated steam of monohydric alcohol supplied to the reaction vessel and / or a temperature control device for fats and oils supplied to the reaction vessel .

  (10) The transesterification reaction apparatus according to any one of (7) to (9), wherein a nozzle for supplying superheated steam of monohydric alcohol is installed so as to discharge the superheated steam toward the lower side of the reaction vessel.

  (11) The transesterification reaction device according to any one of (7) to (10), wherein a perforated plate is provided at the nozzle tip.

  According to the present invention, fatty acid esters and glycerin can be produced with high purity and low cost by a simple apparatus and operation.

  In addition, since the chemical catalyst remains in the reaction system, the method of the present invention can be operated without additional supply of the chemical catalyst over a long period of time.

  Furthermore, in this invention, fatty acid ester and glycerol can be manufactured continuously.

  The present invention is a method for producing a fatty acid ester and glycerin using a chemical catalyst from fats and oils (including waste fats and oils) and a monohydric alcohol (hereinafter simply referred to as alcohol). In the present invention, Excess alcohol is continuously supplied to the reaction system in the form of superheated steam to react with fats and oils, and the reaction product containing the fatty acid ester and glycerin is in a gas phase or a mixed phase with a droplet phase. Along with alcohol superheated steam, it is continuously extracted to separate fatty acid ester and glycerin, respectively.

  In the present invention, “alcohol in the state of superheated steam” refers to an alcohol maintained at a temperature higher than the boiling point corresponding to the pressure of the alcohol.

  Examples of the fats and oils used in the present invention include fats and oils having esters of glycerin, preferably triglycerides. Natural oils such as palm oil, rapeseed oil, soybean oil, olive oil, corn oil, peanut oil, coconut oil, safflower oil, sesame oil, linseed oil, castor oil, tung oil, sunflower oil, Animal oils such as pig oil, beef tallow, horse oil, sardine oil, shark oil, whale oil, synthetic fats and oils, and the like, and these may be waste oils and fats, edible oils, and mixtures thereof. Also good.

  When using the above fats and oils, especially waste fats and oils and waste cooking oils, components other than fats and oils may be mixed in, but there is a possibility of causing clogging in the manufacturing process or reaction inhibition. It is preferable to remove in advance by a method such as distillation or filtration.

  As alcohol used by this invention, C1-C3 monohydric alcohol is mentioned preferably, Specifically, methanol and ethanol are mentioned, However, Methanol is especially preferable.

  The chemical catalyst used in the present invention means a compound having a catalytic activity for transesterification by bringing oils and fats into contact with alcohol, and is a concept that excludes simple metals. Preferred examples of the chemical catalyst used in the present invention include alkali metal compounds and alkaline earth metal compounds, and these can be used alone or in combination of two or more.

  The alkali metal is preferably at least one selected from potassium and sodium, and the alkaline earth metal is preferably at least one selected from barium, calcium and magnesium.

  Moreover, as a form of the said metal compound, it is preferable that it is any 1 type of an oxide, a hydroxide, an inorganic acid salt, and an organic acid salt, or a thing containing 2 or more types of multiple compounds.

  The inorganic acid salt is preferably a carbonate group or a group to which a hydroxyl group is further added. Specific examples of such compounds include sodium hydroxide (caustic soda), potassium hydroxide (caustic potash), sodium carbonate, potassium carbonate, and the like. Among these, caustic soda, caustic potash and the like are preferable.

  The organic acid salt preferably contains a carboxylic acid group or is further added with a hydroxyl group. Specific examples include potassium palmitate.

  The amount of the chemical catalyst used in the present invention is 0.0002 mol to 0.2 mol, preferably 0.002 mol to 0.05 mol, relative to 1 kg of the raw oil stored in the reaction vessel.

  The basic reaction in the production method of the present invention involves contacting an alcohol and fats and oils in the presence of a chemical catalyst to cause a transesterification reaction to produce a fatty acid ester and glycerin. At that time, after excessive alcohol is continuously supplied to the reaction system in the form of superheated steam and reacted in the reaction system, the reaction product containing the fatty acid ester and glycerin is converted into a gas phase or a droplet phase. It is characterized by being continuously extracted together with the alcohol superheated steam in the accompanying mixed phase state.

  In the above, supplying “excess alcohol” does not necessarily need to be in excess of the theoretical chemical equivalent required for transesterification of the total amount of glycerin ester in the raw oil and fat. It is sufficient that the amount of the reaction product is excessive, and when the reaction product obtained by the reaction is withdrawn out of the system, a phenomenon in which alcohol in the superheated steam state is also withdrawn is observed. Especially, it is preferable to control the supply amount so that the amount of alcohol in the superheated steam state is about 30 to 80% by weight in the mixture of alcohol and reaction product in the superheated steam state to be extracted.

  Moreover, it is preferable that the reaction container internal pressure at the time of reaction shall be near normal pressure, and it is more preferable to set it as 0.101-0.150 MPa.

  The temperature of the alcohol in the state of superheated steam to be supplied is 250 ° C to 350 ° C (more preferably 270 ° C to 300 ° C), and the temperature of the fats and oils is 250 ° C to 350 ° C (more preferably 270 ° C to 300 ° C). Is preferably caused to occur.

  Furthermore, the temperature of the mixture of the reaction product containing fatty acid ester and glycerin when extracted from the reaction system (gas phase or a mixed phase with a droplet phase) and alcohol superheated steam is 250 ° C to 350 ° C. It is preferable that

In the present invention, the reaction apparatus for supplying the fats and oils in the superheated steam state to cause the ester exchange reaction in the presence of the chemical catalyst and extracting the resulting reaction mixture together with the superheated steam state alcohol is various forms. Can be carried out in the reactor or the manufacturing process described in Japanese Patent Application No. 2004-40566, PCT / JP2004 / 010349, and Japanese Patent Application No. 2004-231676. Implementation is possible.

First embodiment:
In the first embodiment, a reaction vessel equipped with a heating / heat-retaining device, a stirring device, an oil / fat supply port, a nozzle for supplying alcohol in the form of superheated steam below the reaction vessel, and a gas phase above the reaction vessel Alternatively, a transesterification apparatus used in a method for producing glycerin is provided with an outlet for extracting the reaction product in a mixed phase state accompanied by a droplet phase together with the superheated alcohol vapor.

  A preferred embodiment of the above method will be described with reference to FIG. 1, but is not limited thereto.

  As shown in FIG. 1a, a stainless steel cylindrical reaction vessel 1 equipped with a heating / heat-retaining device stores a mixture of raw oils and fats 5 heated to a predetermined temperature and a chemical catalyst (for example, caustic potash) 6; The alcohol 7 in the superheated steam state heated to a predetermined temperature by the heating device 2a from 3 is blown, and the reaction product (fatty acid ester and glycerin) 8 is collected together with the excessive alcohol 7 in the superheated steam state from the upper part of the reaction vessel. To do. As the reaction proceeds, the raw oils and fats corresponding to the consumed amount are heated to a predetermined temperature by the heating device 2 b and supplied from the supply pipe 4. Stirring is performed by the stirrer 9 as necessary. The nozzle tip has a shape to which a perforated plate 10 is added if necessary. An example of such a shape is shown in FIG.

  The amount of the chemical catalyst (caustic potash) to be used is 0.001 Wt% to 1 Wt% (preferably 0.01 Wt% to 0.3 Wt%) with respect to the raw material oil stored in the reaction vessel, and the temperature of the fats and oils as the raw material is The temperature of the vaporized alcohol in the state of 250 ° C to 350 ° C (preferably 270 ° C to 290 ° C) and superheated steam is 250 ° C to 350 ° C (preferably 270 ° C to 290 ° C).

Second embodiment:
In the second embodiment, a draft tube, an impeller, and a static mixer are installed in a reaction vessel equipped with a heating / heat-retaining device, a supply port for supplying fats and oils, and an alcohol in a superheated steam state. Provided with an outlet for extracting the reaction product in a gas phase or a mixed phase with a droplet-like phase together with alcohol superheated steam at the top of the reaction vessel. A mixture of fats and oils containing alcohol bubbles in a state and a chemical catalyst descends the inside of the draft tube by the impeller, forms a circulating flow that rises outside the tube, and passes through the static mixer on the way to the gas-liquid contact This is a method using a transesterification reaction apparatus in which is promoted.

  A preferred embodiment of the above method will be described with reference to FIG. 2, but is not limited thereto.

  As shown in FIG. 2, a draft tube 11, an impeller 12, and a static mixer 13 are installed in a reaction vessel 1 equipped with a heating / warming device, and the state of superheated steam heated to a predetermined temperature by a heating device 2a The alcohol 7 is blown into a mixture of the raw material fats and oils 5 and the chemical catalyst (for example, caustic potash) 6 at a predetermined temperature stored from the nozzle 3, together with the alcohol 7 that is in the state of excess superheated steam from the upper part of the reaction vessel The reaction product (fatty acid ester and glycerin) 8 is collected. The mixture of raw oils and fats containing alcohol bubbles in the form of superheated steam and the chemical catalyst descends the inside of the draft tube by the impeller, forms a circulating flow that rises outside the tube, and passes through the static mixer on the way This promotes gas-liquid contact.

  The amount of the chemical catalyst, the temperature of the raw material fats and oils, and the temperature of the alcohol in the superheated steam state are the same as in the first embodiment. The nozzle tip has a shape (for example, FIG. 1b) with a perforated plate added as necessary.

  The static mixer may be an appropriate one that is usually used in a chemical apparatus, for example, a proper type of sulzer type, and more simply a plurality of porous plates laminated at appropriate intervals.

  In the above preferred embodiment, the continuous or sequential supply of fats and oils during the transesterification reaction can be omitted unless particularly inconvenient, and such an embodiment is also included in the production method of the present invention.

  In the present invention, a mixture of a reaction product containing a fatty acid ester and glycerin in a gas phase or a mixed phase accompanied by a droplet phase extracted from the reaction system and an alcohol superheated steam is obtained by an ordinary method. It can be separated and recovered. That is, alcohol can be distilled off in the gas phase, and then the fatty acid ester and glycerin can be recovered by phase separation by a method such as standing or centrifugation.

  It is preferable to control the temperature to be higher than the boiling point of alcohol (for example, methanol has a boiling point of 65 ° C.) and lower than the boiling point of fatty acid ester or glycerol (290 ° C.), preferably about 150 ° C. ± 50 ° C. As a result, the alcohol in the mixture is mainly in a gas phase, and the fatty acid ester and glycerin are condensed into a liquid phase, so that the gas phase alcohol can be easily separated. The liquid phase fatty acid ester and glycerin can be recovered by phase separation by the above method.

  Furthermore, when there is a certain difference in the boiling points of the fatty acid ester and glycerin, the following method can also be adopted, that is, the above mixture extracted from the reaction system is once between the boiling point of glycerin and the boiling point of the fatty acid ester. By controlling the temperature, the condensate A mainly containing the compound having the higher boiling point can be separated. Thereafter, by controlling the temperature of the remaining gas phase mixture below the boiling point of the low boiling point compound and above the boiling point of methanol, the condensate B mainly containing the compound having the lower boiling point can be separated. The remaining gas phase is a gas mainly containing alcohol. The condensates A and B can be further purified as necessary to obtain desired products.

  The separated vapor-phase alcohol can be heated again to be in the form of superheated steam and used for the next reaction.

  The production method of the present invention has the following advantages by adopting the above method.

  That is, the reaction of bringing oils and alcohols into contact with each other and transesterifying them to produce fatty acid esters and glycerin is generally an equilibrium reaction, and conventional batch methods and the like have limitations on the amount of fatty acid ester and glycerin produced. However, in the present invention, since the fatty acid ester and glycerin, which are reaction products, are continuously extracted from the reaction system, the fatty acid ester and glycerin are efficiently generated without reaching an equilibrium state.

  In addition, since the reaction product obtained is extracted from the reaction system in the gas phase together with the vapor phase flow of the alcohol in the form of superheated steam, it contains little or no catalyst. Therefore, it is not necessary to remove the catalyst from the reaction product, the fatty acid ester after separation, or glycerin. In addition, high-purity glycerin and fatty acid esters can be obtained.

  Furthermore, since the chemical catalyst remains in the reaction system, the operation can be performed without additional supply of the chemical catalyst for a long time.

  In general, since the boiling point of alcohol and fatty acid ester or glycerin are greatly different from each other, the reaction product in a gas phase extracted from the reaction system or a mixed phase with a droplet-like phase and an alcohol in a superheated steam state are used. By using the difference between the boiling points of the reaction product and the alcohol, the gas phase alcohol can be easily separated from the gas phase alcohol with a relatively small cooling. Furthermore, the alcohol can be used for the next reaction by heating it slightly to form an alcohol in the form of superheated steam.

The ICP analysis and gas chromatographic analysis evaluated in the examples were performed under the following conditions.
ICP analysis: ICP emission spectrometer OPTIMA300DV manufactured by PerkinElmer, detection limit 1 μg / g
Gas chromatographic analysis:
Body: GC-380 manufactured by GL Sciences
Column: J & W DB-1, length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm
Carrier gas: Helium 90KPa
Column temperature chamber: 50 ° C. held for 1 minute, raised to 100 ° C. at 30 ° C./minute, raised to 325 ° C. at 3 ° C./minute, held for 163 minutes Detector: FID; Sample injection amount: diluted normal hexane 10 times 2 μl of liquid

Example 1
150 g of rapeseed oil (purity 92%) is stored in a sample cylinder made of SUS316L (inner diameter 46 mm, filled with 100 ml of SUS304 McMahon packing) having a capacity of 300 ml, and 0.075 g of chemical catalyst (caustic potash, purity 85.5%) (Equal to 0089 mol) was added in a hot-air circulating thermostat at 270 ° C., and methanol in the form of superheated steam at 270 ° C. under atmospheric pressure was blown from the bottom at a rate of 50 g per hour. Both reaction products (fatty acid ester and glycerin) were taken out from above with methanol in an excess of superheated steam and cooled and liquefied. The obtained reaction product was concentrated under reduced pressure (3 KPa, 70 ° C.) with a rotary evaporator to remove excess methanol, and then the upper fatty acid ester and the lower glycerin were separately obtained by standing separation and weighed. The collected amounts of fatty acid ester and glycerin were 30.6 g and 3.1 g, respectively, in the 1 hour interval from the first hour to the second hour from the start of the experiment. In the ICP analysis of the reaction product, potassium was not detected from the fatty acid ester and glycerin. In the gas chromatographic analysis of the reaction product, the content of the raw material fat contained in the fatty acid ester was less than 0.1% (relative area).

Example 2
The same operation as in Example 1 was carried out except that the chemical catalyst was changed from caustic potash to 0.10 g of caustic soda (purity 96%) (corresponding to 0.017 mol per kg of rapeseed oil). The collected amounts of fatty acid ester and glycerin were 31.1 g and 3.2 g in the 1 hour interval from the first hour to the second hour, respectively. In the ICP analysis of the reaction product, sodium was not detected from the fatty acid ester and glycerin. In the gas chromatographic analysis of the reaction product, the content of the raw material fat contained in the fatty acid ester was less than 0.1% (relative area).

Example 3
The same operation as in Example 1 was carried out except that the addition amount of the chemical catalyst was changed to 0.15 g of caustic potash (corresponding to 0.018 mol per kg of rapeseed oil). The collected amounts of fatty acid ester and glycerin were 51.6 g and 5.3 g in the 1 hour interval from the first hour to the second hour, respectively. In the ICP analysis of the reaction product, potassium was not detected from the fatty acid ester and glycerin. In the gas chromatographic analysis of the reaction product, the content of the raw material fat contained in the fatty acid ester was less than 0.1% (relative area).

Example 4
The same operation as in Example 1 was conducted except that the addition amount of the chemical catalyst was changed to 0.02 g of caustic potash (corresponding to 0.0024 mol per kg of rapeseed oil). The collected amounts of fatty acid ester and glycerin were 23.4 g and 2.3 g in the 1 hour interval from the first hour to the second hour, respectively. In the ICP analysis of the reaction product, potassium was not detected from the fatty acid ester and glycerin. In the gas chromatographic analysis of the reaction product, the content of the raw material fat contained in the fatty acid ester was less than 0.1% (relative area).

Comparative Example 1
The same operation as in Example 1 was carried out under the condition that no chemical catalyst was added. The collected amounts of fatty acid ester and glycerin were 7.2 g and 0.7 g in the 1-hour interval from the first hour to the second hour, respectively. In the gas chromatographic analysis of the reaction product, the content of the raw material fat contained in the fatty acid ester was less than 0.1% (relative area).

Comparative Example 2
In a 300 ml three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 150 g of rapeseed oil (purity 92%) and 30 g of methanol (boiling point 65 ° C.) are taken and heated and stirred until the temperature reaches 65 ° C. After the internal liquid reaches a predetermined temperature, 0.075 g of a chemical catalyst (caustic potash, purity: 85.5%) (corresponding to 0.018 mol per kg of rapeseed oil) is added and heated for 1 hour while maintaining the temperature at 65 ° C. Stir. The reaction solution was concentrated under reduced pressure (3 KPa, 70 ° C.) with a rotary evaporator to remove excess methanol, and then distilled under reduced pressure (1.3 Kpa, 250 ° C.). As a result, 1.8 g of distillate (fatty acid ester and glycerin) was obtained. Obtained.

Example 5
1500 g of rapeseed oil (purity 92%) is stored in the apparatus shown in FIG. 1 (a stainless steel cylindrical container having a diameter of 100 mm and a height of 500 mm, a propeller type stirring apparatus), and caustic potash (purity 85.5%) 0.75 g as a chemical catalyst. (Equivalent to 0.0089 mol per kg of rapeseed oil) was added and stirred and heated to 290 ° C. A porous plate (hole diameter 3 mm, hole number 20) was added to the tip of a stainless steel tube with an inner diameter of 5 mm at a height of 50 mm from the bottom of the container. Then, 290 ° C. superheated methanol vapor was blown at a rate of 1000 g per hour. During the experiment, raw oils and fats were replenished in small amounts so that the liquid level was kept at the original height. The reaction product (fatty acid ester and glycerin) is taken out together with excess superheated vapor of methanol from above, cooled to 150 ° C, the reaction product (fatty acid ester and glycerin) is selectively condensed, and is allowed to stand, separate and weigh. . The collected amounts of fatty acid ester and glycerin per hour in an almost stable state after 1 hour from the start of the experiment were 1000 g to 1100 g and 90 g to 110 g, respectively. In the ICP analysis of the product, no potassium was detected from the fatty acid ester and glycerin. In the gas chromatographic analysis of the reaction product, the content of the raw material fat contained in the fatty acid ester was less than 0.1% (relative area).

Example 6
The experiment was performed in the same manner as in Example 5 except that the propeller type stirring device was stopped. The collected amounts of fatty acid ester and glycerin per hour in an almost stable state after 1 hour from the start of the experiment were 950 g to 1100 g and 90 g to 100 g, respectively. In the ICP analysis of the product, no potassium was detected from the fatty acid ester and glycerin. In the gas chromatographic analysis of the reaction product, the content of the raw material fat contained in the fatty acid ester was less than 0.1% (relative area).

Comparative Example 3
The experiment was performed in the same manner as in Example 5 with no chemical catalyst added. The collected amounts of fatty acid ester and glycerin per hour in an almost stable state after 1 hour from the start of the experiment were 200 g to 220 g and 20 g to 22 g, respectively. In the gas chromatographic analysis of the reaction product, the content of the raw material fat contained in the fatty acid ester was less than 0.1% (relative area).

  According to the present invention, high-purity fatty acid esters and by-product glycerin are produced at a low cost, and the replacement of fossil diesel fuels with plants is promoted.

FIG. 1a is an example of a reaction apparatus according to the present invention, and FIG. 1b is an example of a nozzle tip in the reaction apparatus. 1 is an example of a reaction apparatus according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Reaction container 2a Heating apparatus 2b Heating apparatus 3 Nozzle 4 Oils and fats supply pipe 5 Oils and fats 6 Chemical catalyst 7 Alcohol in the state of superheated steam 8 Reaction product 9 Stirrer 10 Perforated plate 11 Draft tube 12 Impeller 13 Static mixer

Claims (11)

A method for producing fatty acid esters from fats and oils and monohydric alcohols using a chemical catalyst, wherein excess monohydric alcohols are continuously supplied to the reaction system in the form of superheated steam and transesterified with fats and oils. The reaction product containing the fatty acid ester is continuously withdrawn together with the superheated vapor of the monohydric alcohol in a gas phase or a mixed phase with a droplet-like phase, and the fatty acid ester is separated and recovered. A method for producing a fatty acid ester. 2. The method for producing a fatty acid ester according to claim 1, wherein the chemical catalyst is an alkali metal compound or / and an alkaline earth metal compound. 3. The method for producing a fatty acid ester according to claim 1, wherein the chemical catalyst is sodium hydroxide or / and potassium hydroxide. The method for producing a fatty acid ester according to any one of claims 1 to 3, wherein the amount of the chemical catalyst used is 0.0002 mol to 0.2 mol based on 1 kg of the raw material oil stored in the reaction vessel. The reaction is caused to occur at a reaction vessel internal pressure of about normal pressure, a temperature of alcohol in a superheated steam state of 250 ° C to 350 ° C, and a temperature of oils and fats of 250 ° C to 350 ° C. The manufacturing method of the fatty acid ester in any one of -4. This is a method for producing glycerin from fats and oils and monohydric alcohols using a chemical catalyst, and the excess monohydric alcohol is continuously supplied to the reaction system in the form of superheated steam to transesterify with fats and oils. Production of glycerin, wherein the reaction product containing glycerin is continuously extracted together with superheated steam of monohydric alcohol in a gas phase or mixed phase with a droplet-like phase, and glycerin is separated and recovered Method. Reaction vessel equipped with heating and heat retention device, oil and fat supply port, nozzle for supplying alcohol in the form of superheated steam below the reaction vessel, mixed phase with gas phase or droplet phase above the reaction vessel The ester used for the manufacturing method of the fatty acid ester in any one of Claims 1-5 or the manufacturing method of the glycerol of Claim 6 which provided the outlet for extracting the reaction product of the state of this with the superheated steam of monohydric alcohol Exchange reaction equipment. A draft tube, an impeller, and a static mixer are installed in a reaction vessel equipped with a heating and heat insulation device, and a supply port for supplying fats and oils and a nozzle for supplying alcohol in the state of superheated steam are provided. The outlet according to any one of claims 1 to 5, wherein an outlet for extracting a reaction product in a gas phase or a mixed phase accompanied by a droplet-like phase together with a superheated vapor of monohydric alcohol is provided at an upper part of the reaction vessel. An apparatus for transesterification used in a method for producing a fatty acid ester or a method for producing glycerin according to claim 6, wherein a mixture of fats and oils containing alcohol bubbles in the form of superheated steam and a chemical catalyst is placed inside a draft tube by an impeller. The gas-liquid contact is promoted by forming a circulating flow that rises outside the tube and passing through a static mixer on the way. Ester exchange reaction apparatus. The transesterification apparatus according to claim 7 or 8, further comprising a temperature control device for superheated steam of monohydric alcohol supplied to the reaction vessel and / or a temperature control device for fats and oils supplied to the reaction vessel. The transesterification apparatus according to any one of claims 7 to 9, wherein a nozzle for supplying superheated steam of monohydric alcohol is installed so as to discharge the superheated steam toward the bottom of the reaction vessel. The transesterification apparatus according to any one of claims 7 to 10, wherein a perforated plate is provided at a nozzle tip.

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