JP2008031400A - Method for producing fatty acid ester from fats and oils as raw material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a biodiesel fuel in high efficiency. <P>SOLUTION: This method for producing a fatty acid ester comprises performing an ester interchange reaction in the presence of sea salt or a group 2 element halide such as magnesium chloride. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a useful method for producing a fatty acid ester by transesterification by reacting triglyceride contained in fats and oils with alcohol.

One approach to comply with carbon dioxide emission regulations is to use plant-derived fuels instead of fossil fuels. Alkyl alcohol is used as the main triglyceride such as palm oil and rapeseed oil obtained from plants. Thus, it has been put into practical use to produce a diesel fuel equivalent to light oil by performing a transesterification reaction to obtain a fatty acid alkyl ester. Various methods have been proposed for the transesterification, but at present, most of them use a chemical catalyst, particularly an alkali catalyst such as caustic soda or caustic potash. (For example, Patent Documents 1, 2, and 3) In this method, the alkali compound used as a catalyst is discharged together with glycerin as a by-product, and the cost is too high for recycling. At present, this process is added.

In order to omit such a post-treatment of the catalyst, a method using a solid acid catalyst or a solid alkali catalyst as one direction (for example, Patent Document 4) has been studied, but in terms of the cost of the catalyst or the life of the catalyst. It has not yet been put to practical use.

Similarly, in order to omit the post-treatment of the catalyst, as another direction, it is studied to perform the reaction without using the catalyst. One of them is a method that utilizes the high activity of chemical species in the supercritical state (for example, Patent Documents 5, 6, and 7), and alcohol in the supercritical state (in the case of methanol, a critical temperature of 238 ° C., a critical pressure of 7. Since the pressure is 9 MPa, the target alkyl ester is obtained by performing transesterification by reacting oils and fats without any catalyst under conditions of temperature and pressure higher than this. The reaction rate increases with increasing temperature and pressure, so continuous mass production is considered possible, but because it is a high temperature and high pressure reaction, an increase in capital investment and running costs is unavoidable, and there is considerable operational safety. Consideration is necessary. In addition to the activation of chemical species in a supercritical state, an attempt to obtain economically advantageous reaction conditions using a catalyst (mostly a fixed catalyst) is also proposed (for example, Patent Documents 8, 9, 10, 11). However, it still requires considerable high temperature and high pressure, and the fixed catalyst still has the same difficulties as described above. This kind of method has not yet reached the stage of practical verification.

More recently, it is easier to control the reaction than direct transesterification, and it is suitable for practical industrialization. It is a combination of a two-stage method in which triglyceride is hydrolyzed and the resulting fatty acid is esterified with alcohol and supercritical conditions. Is proposed (Patent Document 12), but difficulties such as the necessity of removing moisture during the process and problems with the apparatus due to high-temperature and high-pressure water are expected.

The present inventors separately carry out the reaction under normal pressure using only a non-catalyst or a solid catalyst, and select gas-liquid contact means, whereby superheated methanol and raw oils and fats are brought to near atmospheric pressure (0.101-0). .150 MPa) · The reaction is conducted under a temperature of 350 ° C. or less, the reaction product is taken out from the reaction vessel as a mixed gas stream together with excess superheated vaporized alcohol, cooled, and the alkyl ester and glycerin are condensed sequentially or simultaneously. A method (Patent Documents 13, 14, 15, 16, and 17) for obtaining an ester fuel with a good yield by sampling is proposed. This method does not use a catalyst and can obtain alkyl esters and glycerin having high purity at normal pressure. However, the temperature of fats and oils is higher for operation with higher reaction efficiency than the alkali catalyst method. It is desirable to keep (around 290 ° C.), and in this case, it is necessary to consider energy costs and deterioration of fats and oils.
JP-A-9-235573 JP-A-10-182518 JP 2000-144172 A JP2000-143586 JP2000-109883 JP 2000-204392 A JP 2001-302584 A JP2002-308825 JP 2001-226694 A JP 2003-55299 A JP 2004-263011 A Japanese Patent Application No. 2003-43641 Japanese Patent Application No. 2004-40565 Japanese Patent Application No. 2004-40566 PCT / JP2004 / 010349 Japanese Patent Application No. 2004-231676

In the present invention, among the above-mentioned production methods, in particular, the problems of those previously proposed by the present inventors are solved, and simple products for obtaining high-purity products (fatty acid esters and glycerin) at low cost, high reaction efficiency, and the like. Develop manufacturing methods.

(1) In the production of fatty acid esters from fats and oils (including waste fats and oils) and monohydric alcohols (hereinafter simply referred to as alcohols), excess alcohol is heated to superheated alcohol (the pressure of the alcohol) above the required theoretical chemical equivalent. The reaction product (fatty acid ester and glycerin) is used in the reaction in the state of an alcohol held at a temperature higher than the boiling point corresponding to In a method for producing a fatty acid ester obtained as a mixture with a superheated vaporized alcohol or a droplet-like reaction product), the reaction between the fats and oils with sea salt (evaporation of seawater moisture) In the presence of residual solids obtained by the above method.
(2) In the production of fatty acid esters from fats and oils (including waste fats and oils) and monohydric alcohols (hereinafter simply referred to as alcohols), excess alcohol is heated to superheated vaporized alcohol (the pressure of the alcohol) beyond the required theoretical chemical equivalent. The reaction product (fatty acid ester and glycerin) is used in the reaction in the state of an alcohol held at a temperature higher than the boiling point corresponding to In a method for producing a fatty acid ester obtained as a mixture with a superheated alcohol or a droplet-like reaction product), the reaction between the fats and oils and the chemical components constituting the sea salt A method for producing a fatty acid ester, wherein the fatty acid ester is produced in the presence of at least one.
(3) In the production of fatty acid esters from fats and oils (including waste fats and oils) and monohydric alcohols (hereinafter simply referred to as alcohols), excess alcohol is heated to superheated vaporized alcohol (pressure of the alcohol) beyond the required theoretical chemical equivalent. The reaction product (fatty acid ester and glycerin) is used in the reaction in the state of an alcohol held at a temperature higher than the boiling point corresponding to In a method for producing a fatty acid ester obtained as a mixture with a superheated vaporized alcohol or a droplet-like reaction product), the reaction between the oil and fat and the alcohol is caused to occur in the presence of magnesium chloride. The manufacturing method of the fatty acid ester characterized by these.
(4) In the production of fatty acid esters from fats and oils (including waste fats and oils) and monohydric alcohols (hereinafter simply referred to as alcohols), excess alcohol is heated to superheated vaporized alcohol (the pressure of the alcohol) above the required theoretical chemical equivalent. The reaction product (fatty acid ester and glycerin) is mixed with a superheated vaporized alcohol (gas phase reaction product) In a method for producing a fatty acid ester obtained as a mixture with a superheated alcohol or a droplet-like reaction product), the reaction between the oil and fat and the alcohol is carried out by subjecting the element long-period periodic table group 2 A method for producing a fatty acid ester, characterized in that it is produced in the presence of at least one kind of halide of an element belonging to 3 to 7 cycles.
(5) In the production method according to (1) to (4), the pressure in the container at the time of reaction is 0.1 Mpa to 10 Mpa, preferably near normal pressure (0.101 to 0.150 MPa), and the temperature of the superheated vaporized alcohol is A method for producing a fatty acid ester, characterized by causing the reaction to occur at 250 ° C. to 350 ° C. and the temperature of the fats and oils at 180 ° C. to 320 ° C., preferably 250 ° C. to 300 ° C.
(6) The manufacturing method of the fatty acid ester whose fats and oils of (1)-(5) are vegetable oils.
(7) A method for producing a fatty acid ester, wherein the fats and oils according to (1) to (5) include at least one of palm oil, rapeseed oil, coconut oil, sunflower oil or Jatroha oil.
(8) A method for producing a fatty acid ester, wherein the alcohol according to (1) to (5) is methanol or / and ethanol.
(9) Fatty acid ester and glycerin produced by any of the methods described in (1) to (8).

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.

The present invention can be carried out in various types of reactors, for example, the reactor described in Japanese Patent Application No. 2004-40566, PCT / JP2004 / 010349, and Japanese Patent Application No. 2004-231676. Due to the high reaction activity, it can be carried out in a simpler form.

First Embodiment: In the first embodiment, as shown in FIG. 1a, raw material fats and oils 5 heated to a predetermined temperature in a cylindrical reaction vessel 1 made of stainless steel equipped with a heating / warming device; Additives (sea salt or at least one of the sea salt components or magnesium chloride or elemental halides belonging to Group 2 to Group 7 of Periodic Periodic Table 2) The superheated vaporized alcohol 7 heated to a predetermined temperature by the heating device 2a is blown from the nozzle 3 and the reaction product (fatty acid ester and glycerin) 8 is collected together with the excess superheated vaporized alcohol 7 from the upper part of the reaction vessel. . As the reaction proceeds, the raw fats and oils corresponding to the consumed amount are heated to a predetermined temperature by the heating device 2b 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 this shape is shown in FIG.

The amount of the additive used is 0.5 Wt% to 3.0 Wt% with respect to the raw material oil stored in the reaction vessel, the temperature of the raw oil and fat is 200 ° C to 320 ° C, preferably 280 ° C to 300 ° C, superheated alcohol The temperature is 250 ° C. to 350 ° C. (preferably 270 ° C. to 290 ° C.).

Although the present invention can be applied in the pressure range of 0.1 Mpa to 10 Mpa, it is preferably performed in the vicinity of normal pressure (0.101 to 0.150 MPa) from the viewpoint of equipment and operation.

Second Embodiment: In the second embodiment, 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 and heat insulation device, and heating is performed. The superheated vaporized alcohol 7 heated to a predetermined temperature by the apparatus 2a is blown into a mixture of the raw material fats and oils 5 and the additive 6 at a predetermined temperature stored from the nozzle 3, and the excess superheated vaporized alcohol 7 from the upper part of the reaction vessel. At the same time, the reaction product (fatty acid ester and glycerin) 8 is collected. The mixture of raw oils and fats containing bubbles of superheated alcohol and additives is lowered by the impeller inside the draft tube, forming a circulating flow that rises outside the tube, and passing through the static mixer on the way to the gas-liquid contact Is promoted.

The amount of sea salt, the temperature of raw material fats and oils, and the temperature of superheated vaporized alcohol 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.

Example 1: Rapeseed oil (purity 92%) is stored from a low part to 300 mm in a glass cylindrical container having a diameter of 50 mm and a height of 500 mm, and 100 g of sea salt added is heated to 290 ° C. A 50 mm height stainless steel tube with an inner diameter of 5 mm, with a perforated plate (hole diameter 3 mm, number of holes 20) added to the tip, was placed upward, and 290 ° C. superheated vaporized methanol was blown at a flow rate of 284 ml / hr. . 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) was taken out together with excess superheated vaporized methanol from above, cooled, separated and weighed to determine the amount of distillation per hour. FIG. 3 shows a comparison with a similar experiment conducted without the addition of sea salt. In the figure, 14 is the amount of distillate of fatty acid ester when sea salt is added, and 15 is the amount of distillate of fatty acid ester when no sea salt is added, indicating that sea salt significantly promotes the reaction. It was.

Example 2: The result of adding 10 g of magnesium chloride (reagent grade 1) under the same conditions as in Example 1 is shown in FIG. In FIG. 14, 15 is the amount of distillate of fatty acid ester when no additive is added as in Example 1, and 17 is the amount of distillate of fatty acid ester when 10 g of sodium methylate (reagent first grade), which is usually used as a catalyst, is added. It was shown that magnesium chloride significantly promoted the reaction. Also, 18 in FIG. 4 is the amount of distillate of fatty acid ester when 100 g of sea salt is added and the experiment is conducted at a temperature of 250 ° C., and the equivalent outflow amount is lower at a lower temperature than when no addition is made. It was shown to be obtained.

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

  It is an example of the reaction apparatus concerning this invention.   It is an example of the reaction apparatus concerning this invention.   It is a result of one Example of this invention.   It is a result of one Example of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Reaction container 2 Heating apparatus 3 Heating apparatus 4 Raw material fats and oils supply pipe 5 Raw material fats and oils 6 Chemical catalyst 7 Superheated alcohol 8 Reaction product 9 Stirrer 10 Porous plate 11 Draft tube 12 Impeller 13 Static mixer 14 Sea salt addition 15 Fatty acid ester distillate without additive 16 Fatty acid ester distillate with magnesium chloride 17 Fatty acid ester distillate with sodium methylate 18 250 ° C, with sea salt added Fatty acid ester distillate

Claims (9)

In the production of fatty acid esters from fats and oils (including waste fats and oils) and monohydric alcohols (hereinafter simply referred to as alcohols), an excess of alcohol exceeding the required theoretical chemical equivalent is superheated vaporized alcohol (corresponding to the pressure of the alcohol). The reaction product (fatty acid ester and glycerin) is used in the reaction in the state of an alcohol kept at a temperature higher than the boiling point), and the reaction product (fatty acid ester and glycerin) is mixed with superheated vaporized gas (gas phase reaction product and superheated vaporized alcohol). In the method for producing a fatty acid ester obtained as a mixture with or a droplet-like reaction product), the reaction between the oil and fat and the alcohol is carried out by using sea salt (residue after the water in the seawater has evaporated). It is caused to occur in the presence of solid matter (including rock salt). In the production of fatty acid esters from fats and oils (including waste fats and oils) and monohydric alcohols (hereinafter simply referred to as alcohols), an excess of alcohol exceeding the required theoretical chemical equivalent is superheated vaporized alcohol (corresponding to the pressure of the alcohol). The reaction product (fatty acid ester and glycerin) is used in the reaction in the state of an alcohol kept at a temperature higher than the boiling point), and the reaction product (fatty acid ester and glycerin) is mixed with superheated vaporized gas (gas phase reaction product and superheated vaporized alcohol). In the method for producing a fatty acid ester obtained as a mixture with a liquid or a droplet-like reaction product), the reaction between the oil and fat and the alcohol is carried out at least one of the chemical components constituting the sea salt. A method for producing a fatty acid ester, characterized in that it occurs in the presence of two. In the production of fatty acid esters from fats and oils (including waste fats and oils) and monohydric alcohols (hereinafter simply referred to as alcohols), an excess of alcohol exceeding the required theoretical chemical equivalent is superheated and vaporized alcohol (corresponding to the pressure of the alcohol). The reaction product (fatty acid ester and glycerin) is used in the reaction in the state of an alcohol kept at a temperature higher than the boiling point), and the reaction product (fatty acid ester and glycerin) is mixed with superheated vaporized gas (gas phase reaction product and superheated vaporized alcohol). In which the reaction between the fats and the alcohol occurs in the presence of magnesium chloride. A method for producing a fatty acid ester. In the production of fatty acid esters from fats and oils (including waste fats and oils) and monohydric alcohols (hereinafter simply referred to as alcohols), an excess of alcohol exceeding the required theoretical chemical equivalent is superheated vaporized alcohol (corresponding to the pressure of the alcohol). The reaction product (fatty acid ester and glycerin) is used in the reaction in the state of an alcohol kept at a temperature higher than the boiling point), and the reaction product (fatty acid ester and glycerin) is mixed with superheated vaporized gas (gas phase reaction product and superheated vaporized alcohol). In the method for producing a fatty acid ester obtained as a mixture with or a droplet-like reaction product), the reaction between the fats and oils and the alcohol is carried out by subjecting the element long-period periodic table group 2 to group 7 to 7 A method for producing a fatty acid ester, characterized in that it is produced in the presence of at least one halide of an element belonging to a cycle. 5. The production method according to claim 1, wherein the pressure in the container during the reaction is 0.1 Mpa to 10 Mpa, preferably near normal pressure (0.101 to 0.150 MPa), and the temperature of the superheated vaporized alcohol is 250 ° C. to 5 ° C. A process for producing a fatty acid ester, characterized in that the reaction is caused to occur at 350 ° C. and the temperature of the fats and oils at 180 ° C. to 320 ° C., preferably 250 ° C. to 300 ° C. The manufacturing method of the fatty acid ester whose fats and oils of Claims 1-5 are vegetable oils. A method for producing a fatty acid ester, wherein the fats and oils according to claims 1 to 5 contain at least one of palm oil, rapeseed oil, coconut oil, sunflower oil or Jatroha oil. The manufacturing method of the fatty acid ester whose alcohol of Claims 1-5 is methanol or / and ethanol. A fatty acid ester and glycerin produced by any of the methods according to claim 1.

Images