WO2004108873A1

WO2004108873A1 - Process for production of fatty acid ester compositions

Info

Publication number: WO2004108873A1
Application number: PCT/JP2004/007835
Authority: WO
Inventors: Shiro Saka; Toshihiko Fukuzono
Original assignee: Asahi Kasei Kabushiki Kaisha
Priority date: 2003-06-06
Filing date: 2004-06-04
Publication date: 2004-12-16
Also published as: JPWO2004108873A1; JP4530992B2

Abstract

The invention aims at providing a process for producing a fatty acid ester composition having a total glycerin content (Gs) meeting the biodiesel fuel standards under relatively mild reaction conditions in a shorter time in a high yield; and equipment for the production of the composition. The aim is attained by a process for producing a fatty acid ester composition by reacting fats and oils with an alcohol which is characterized by comprising the first step of reacting fats and oils containing fatty acid glycerides with water in a subcritical or supercritical state to form fatty acids, the dehydration step of removing water nearly completely from the reaction mixture obtained in the first step, and the second step of adding an alcohol to the residue obtained in the dehydration step and reacting the alcohol with the residue in a subcritical or supercritical state to form fatty acid esters.

Description

Specification

Method for producing fatty acid ester composition

Technical field

The present invention relates to a method and an apparatus for producing a fatty acid ester composition by reacting a fat or oil with an alcohol.

[0002] This application claims the benefit of foreign priority from the foreign patent applications of Japanese Patent Application No. 2003-16221 and Japanese Patent Application No. 2003-162212, filed on June 6, 003, in Japan. Background art

[0003] Conventional methods for obtaining a fatty acid ester composition from fats and oils containing fatty acid glyceride include, for example, transesterification of fatty acid glyceride with fatty acid ester by an ester exchange reaction with an alcohol using an alkali catalyst or an acid catalyst. There is a method by converting to. However, in the method using an alkali catalyst, the free fatty acid contained in fats and oils reacts with the alkali catalyst to produce alkali stones.In the method using an acid catalyst, the reaction time is long, There are practical problems such as a decrease in the yield of the fatty acid ester when water is contained in the class (for example, when the water content is 5%, the yield is about 5 to 10%). Furthermore, in these methods, since water acts as a reaction inhibitor, it is necessary to remove water contained in oils and fats in advance. The energy such as electric power required for operating the processing equipment and the like required for the water removal processing is enormous.

[0004] On the other hand, as a conventional method for obtaining a fatty acid ester composition from fats and oils containing fatty acid glyceride, there is a supercritical alcohol method. This is because, in the supercritical state of alcohol, the transesterification reaction of fatty acid glycerides contained in fats and oils and the esterification reaction of free fatty acids contained in fats and oils progress, and the fatty acid ester is also deviated from V and deviation. How to get. (See, for example, Patent Document 1).

[0005] Further, in the supercritical alcohol method, even when a large amount of water coexists in a reaction system between fatty acid glyceride contained in fats and oils, free fatty acid and alcohol, an ester of fatty acid glyceride and alcohol is used. In addition to the exchange reaction, a fatty acid is produced by a hydrolysis reaction of the fatty acid glyceride with water. It is known that the oxidation reaction proceeds and fatty acids are obtained. This is called a water-added supercritical alcohol method. On the other hand, in contrast to this, the above-mentioned supercritical alcohol method is called an anhydrous supercritical alcohol method.

[0006] In the reaction system in the water-added supercritical alcohol method in which water coexists, water acts as an acid catalyst for the alcohol in a supercritical state. And, even if the coexistence ratio of water in the reaction system is 100% or more, it does not significantly affect the yield of the fatty acid ester.

Patent Document 1: Japanese Patent Application Laid-Open No. 2000-204392

Disclosure of the invention

Problems the invention is trying to solve

[0008] However, although the supercritical alcohol method has an advantage that the problem of the method using an alkali catalyst or an acid catalyst can be solved, the fatty acid glyceride is converted into a fatty acid ester. The transesterification reaction of monoglyceride, an intermediate product formed in the process, is a rate-determining step, and has a disadvantage that the reaction rate is not high. Specifically, fatty acid glycerides contained in fats and oils are mainly triglycerides, and diglycerides and monoglycerides are produced as intermediate products during the transesterification reaction with alcohols.The transesterification reaction of monoglycerides is the rate-determining step. It becomes. And the reaction rate of the transesterification reaction between tridali ceride and alcohol is smaller than the reaction rate of the esterification reaction between fatty acid and alcohol, and there are considerable problems in practical use. Furthermore, in the conventional supercritical alcohol method, particularly in the anhydrous supercritical alcohol method in which water is removed from oils and fats as much as possible, monoesterification often remains unreacted because the transesterification reaction is the main reaction.

[0009] Further, since the transesterification reaction of monoglyceride is a rate-determining step, a reaction condition of high temperature and high pressure (for example, about 350 ° C, about 40 MPa) is required to reduce the residual amount of monoglyceride.

[0010] By the way, when the fatty acid ester composition is used as a diesel fuel, particularly as a biodiesel fuel, the amount of total glycerin contained therein must be considered as an important factor influencing the quality of the biodiesel fuel. Must. In practice, increasing the total glycerin content should not produce gels or gums that could clog filters in internal combustion engines. This is because any problems arise.

[0011] The total glycerin amount Gs is defined as Gs = 0.2591MG + 0.1488DG + 0.10444TG + G (MG represents monoglyceride, DG represents diglyceride, TG represents triglyceride, and G represents free glycerin). Due to practical issues, the proposed EU standard specifies Gs 0.25% and the United States Gs 0.24% Gs.

[0012] In the conventional anhydrous supercritical alcohol method described above, since the transesterification reaction is the main reaction, the residual amount of monoglyceride is large, and biodiesel fuel standards in EU and US (total glycerin amount (Gs) (0.25% and 0.24%) are difficult to meet. In other words, a reaction conforming to this fuel standard requires the conditions of 350 ° C, 40 MPa, and 10 minutes at a fat / methanol molar ratio of 1Z42, under which the unsaturated fatty acid ester is thermally denatured. In addition, it is clear that high-grade biodiesel fuel cannot be obtained.

[0013] On the other hand, in the above-described water-added supercritical alcohol method coexisting with water, a hydrolysis reaction between water and fatty acid dalyceride is performed, so that the residual amount of monoglyceride is reduced, and the above-mentioned biodiesel fuel standard is not used. (Total glycerin amount (Gs)-0.25% and 0.24%), which is close enough (Gs = 0.29%), but still far from meeting the biodiesel standard. In order to satisfy the fuel specifications, it is necessary to perform the treatment for a longer time, and at this time, as described above, the thermal denaturation of the unsaturated fatty acid ester is caused.

[0014] Further, as a water-added supercritical alcohol method, for example, there is a method such as WO 03/106604 brochure.

[0015] In view of the above problems, the present invention provides a fatty acid ester composition in a relatively short reaction time under a relatively mild reaction condition, in which the total glycerin amount Gs conforms to the biodiesel fuel standard and in a shorter time and with a higher yield. It is an object to provide a manufacturing method 'apparatus.

Means for solving the problem

[0016] A representative configuration according to the present invention for solving the above-mentioned problem is a method for producing a fatty acid ester composition by reacting an oil or fat with an alcohol, wherein the oil or fat containing fatty acid glyceride is mixed with water. A first step of producing fatty acids by co-existing and reacting in a subcritical state or a supercritical state, a water removal step of roughly removing water from the first step reaction product after the first step, and a residual step in the water removal step. To the residue of the draining process A second step of producing a fatty acid ester by reacting in a subcritical state or a supercritical state.

[0017] Further, the present invention relates to a method for producing a fatty acid ester composition by reacting fats and oils with alcohols, wherein fats and oils containing fatty acid glycerides coexist with water, and fatty acids are reacted by reaction in a subcritical state or a supercritical state. A first step of producing, and a second step of adding an alcohol to a reaction product of the first step after the first step to produce a fatty acid ester by a reaction in a subcritical state or a supercritical state. I do.

Further, the temperature condition and the pressure condition in the first step are substantially the same as the temperature condition and the pressure condition in the second step.

The invention's effect

[0019] According to the production method of the present invention, for example, as compared with the reaction conditions of the supercritical alcohol method mainly involving transesterification (for example, about 350 ° C and about 40 MPa as described above), Under relatively low temperature conditions of 50 ° C to 100 ° C and pressure conditions of about 20MPa to 30MPa, these are used to promote the hydrolysis and esterification reactions. Requires very little energy. In particular, when the temperature and / or pressure is maintained in the second step, the temperature is not lowered to room temperature or normal pressure, so that the production method is more economical. Furthermore, it was confirmed that under the relatively mild reaction conditions, the above-mentioned thermal denaturation of the unsaturated fatty acid ester did not occur.

[0020] In addition, since the reaction can be performed in a state in which water is present in fats and oils, a dehydration treatment that requires energy such as enormous electric power required for operation of a treatment device or the like that removes water from fats and oils is called. Since no pretreatment is required, this viewpoint is an economical manufacturing method.

[0021] Further, according to the production method 'apparatus of the present invention, since the transesterification reaction is not the main reaction, it is possible to sufficiently suppress the residual amount of monoglyceride' diglyceride unreacted fatty acid glyceride, which is an intermediate product. It is possible and therefore it is possible to adapt the total glycerin content to the biodiesel fuel standard.

[0022] Regarding the yield, the fatty acid glyceride is positively converted to a fatty acid by a hydrolysis reaction, and further, the fatty acid is obtained by esterification reaction between the fatty acid and a free fatty acid in fats and oils with an alcohol. Therefore, compared to the conventional supercritical alcohol method, Very high yield, equal to or higher.

[0023] Furthermore, since the hydrolysis reaction and the esterification reaction have a higher reaction rate than the transesterification reaction, the fatty acid ester can be prepared in a shorter time under milder reaction conditions than the conventional supercritical alcohol method. It is possible to obtain a composition.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a reaction formula in a method for producing a fatty acid ester composition of the present invention.

FIG. 2 is a flowchart of a manufacturing method according to the first embodiment.

FIG. 3 is an example of an apparatus configuration of a manufacturing apparatus according to the first embodiment.

FIG. 4 is a flowchart of a manufacturing method according to a second embodiment.

FIG. 5 is a device configuration example of a manufacturing device in a second embodiment.

FIG. 6 is an explanatory diagram of a reference example in which the compositions of organic media are compared.

Explanation of reference numerals

[0025] a Supply device

b Supply device

c Supply device

1 First processing unit

2 Second processing unit

4 Flasher

5 Decanter

6 Distillation equipment

7 Enokuku Poreta

11 First processing unit

12 Drainage treatment equipment

13 Second processing unit

14 Purification equipment

15 Enoch Porator

BEST MODE FOR CARRYING OUT THE INVENTION

[0026] The fats and oils in the present invention widely refer to fats and oils such as animal oils and fats, vegetable oils and fats. And waste oils and fats after their use. It should be noted that oils are liquid at room temperature and oils are solid at room temperature, and oils and fats are a generic term for these. Animal fats and vegetable fats include sardine oil, sword oil, tuna oil, tallow, lard, sunflower oil, safflower oil, tung oil, linseed oil, soybean oil, rapeseed oil, cottonseed oil, olive oil, camellia oil, coconut oil, palm oil , Palm kernel oil, sesame oil and the like. Examples of waste fats and oils include waste oils obtained after the exemplified animal fats and vegetable fats and oils have been used as trape oil. Further, a mixture of two or more of these forces, butter, margarine and the like may be used.

[0027] Fats and oils are rich in fatty acid glycerides. For example, natural fats and oils are mixtures of esters (fatty acid glycerides) of glycerin, a trihydric alcohol, and fatty acids, various monocarboxylic acids. In addition, fatty acid glycerides are classified into the above-mentioned monoglycerides (MG), diglycerides (DG), and triglycerides (TG) according to the number of the three hydroxyl groups of glycerin substituted by the same or different functional groups.

[0028] Examples of the fatty acid include unsaturated fatty acids such as oleic acid, linoleic acid, and linoleic acid, such as saturated fatty acids such as capryprilic acid, lauric acid, norremitic acid, and stearic acid. The type of fatty acid ester-linked to glycerin differs depending on the fat or oil.

[0029] The alcohol used in the present invention is not particularly limited, and may be any of a monohydric alcohol, a dihydric alcohol, and a trihydric alcohol. In general, it is preferable to use a monohydric alcohol from the viewpoint of the reaction rate, the yield of the fatty acid ester, and the like, while the alcohol having a small number of carbon atoms is more preferable. Examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and 1-octanol. The lower alcohol exemplified here is, of course, not a saturated monohydric alcohol, and is not intended to be limited to a saturated alcohol. Unsaturated monohydric or unsaturated polyhydric alcohols are acceptable.

[First Embodiment]

Hereinafter, a first embodiment of the present invention will be described with reference to the drawings. However, the following embodiments do not limit the present invention. The embodiments can be appropriately modified without departing from the spirit of the present invention. FIG. 1 shows a reaction formula in the method for producing a fatty acid ester composition of the present invention, FIG. 2 shows a flowchart of the production method in the present embodiment, and FIG. 1 shows an example of an apparatus configuration of a manufacturing apparatus in a state.

Hereinafter, the manufacturing method of the first embodiment will be specifically described.

[0032] First, the above-mentioned fats and oils and water are coexistently accommodated in a reactor. Here, fats and oils must be made into a single kind, not fats. In other words, taking sardine oil as an example of the above-mentioned animal oil as an example, sardine oil may be a mixture of rapeseed oil, beef tallow, etc., which is not a single kind of sardine oil. Coexisting with water implies both active and passive coexistence. Here, the active coexistence means that water is actively added separately from fats and oils. On the other hand, passive coexistence means that water contained in fats and oils is not removed. In general, fats and oils, particularly natural fats and oils, contain moisture, and for example, used sesame oil after use, which is waste fats and oils, contains water contained in the foodstuffs used as the material for the sesame. As can be understood from the fact, waste oils and fats contain a considerable amount of water.

[0033] Note that "water" and "water" are used synonymously unless otherwise specified. Strictly speaking, "water" is still water as a substance, and "moisture" is still water, which is the water contained in an object.

[0034] By heating and pressurizing the reactor in which oils and fats coexist with water, the state of the reactor is changed from the housed state to the subcritical state or the supercritical state. Here, the subcritical state or supercritical state refers to a state for water. Preferably, it transitions to a subcritical state for water. Although the temperature and pressure in the subcritical state are not clearly defined, high temperature and high pressure near the critical point (critical temperature of water is about 374 ° C and critical pressure is about 22. IMPa) Means the state. Therefore, for example, heating and pressing are performed at about 300 ° C. and about 17 MPa.

[0035] Here, the procedure in which oils and fats and water are first stored in the reactor and then heating and pressurization are described has been described, but this is not necessarily the case. For example, as a pretreatment for storing oils and fats and water in the reactor, they may be heated and pressurized to a subcritical state or a supercritical state or a state close to these, and then stored in the reactor. Particularly in plants that continuously produce fatty acid ester compositions, rather than heat and pressurize oils and fats in a reactor one by one, instead of heating and pressurizing, If it is sent to the reactor, the production efficiency is significantly improved. [0036] In the first step as described above, the hydrolysis reaction of the fatty acid glyceride contained in the fats and oils with water proceeds, and the fatty acid is generated. Specifically, the reaction shown in FIG. 1 (a) proceeds. In addition, in the reaction formula, R attached with a number represents a hydrocarbon group. This reaction has a significantly higher reaction rate than the transesterification reaction under the same conditions.

[0037] In the subsequent water removal step, the temperature of the first-step reactant that has passed through the first step (the first-step reactant mainly contains a fatty acid according to the reaction formula shown) is lowered.

[0038] The temperature condition does not need to be lowered to room temperature. Rather, it is preferable not to lower the temperature to room temperature. Because it is necessary to change the state to the supercritical state (or subcritical state) in the subsequent second step described later, the first step is to heat to the subcritical state, and in the water removal step, it is cooled to room temperature, Furthermore, in the second step, the reheating to the supercritical state is because it is uneconomic from the viewpoint of energy economy such as electric power supplied to the operation of the devices in each step.

[0039] Then, in the water removal step, water is removed at a lower temperature than in the first step. That is, the liquid is separated into a light liquid containing fatty acids and a heavy liquid containing water by decantation, for example, and the aqueous phase, which is a heavy liquid, is removed. This aqueous phase contains glycerin dissolved in water. Therefore, by removing the aqueous phase, the residual phase (light liquid), which is the residue of the water removal step, mainly contains high fatty acids. Here, the decantation is used, but there is no particular limitation as long as the method can separate the fatty acid and water generated in the first step.

[0040] In this draining step, it is not necessary to change the pressure conditions. Of course, this does not preclude lowering the pressure to, for example, normal pressure, but it is necessary to transition the state to a supercritical state (or subcritical state) in the second step described below. Pressurizing to a subcritical state, depressurizing to normal pressure in the water draining step, and repressurizing to the supercritical state in the second step is the energy economy such as electric power input to the operation of equipment in each step Because it is uneconomical from the viewpoint of

[0041] As described above, in the water removal step, the temperature condition is preferably 50 350 ° C and the pressure condition is preferably 0.2 MPa 45 MPa. More preferably, the temperature condition is 100 ° C 300 ° C, the pressure condition is 5MPa 30MPa, and still more preferably, the temperature condition is 120 ° C 200 ° C, pressure condition is about lOMPa-22MPa.

[0042] In the subsequent second step, alcohol is added to the residue of the water removal step remaining in the water removal step, and the state is further transited to a subcritical state or a supercritical state to progress the reaction. Here, the subcritical state or supercritical state refers to a state for alcohol. Preferably, the transition is made to a supercritical state for the alcohol. For example, in the case of methanol, the critical temperature is about 239 ° C and the critical pressure is about 8. IMPa. Therefore, heating and pressurizing are performed at about 270 ° C to 300 ° C and about 1 OMPa-17MPa.

In the second step, the esterification reaction of the alcohol added with the fatty acid highly contained in the residue of the water removal step and the esterification of the free fatty acid contained in the fats and oils with the added alcohol are carried out. The reaction proceeds to produce fatty acid esters. Specifically, the reaction shown in FIG. 1 (b) proceeds. Furthermore, even if diglyceride-monoglyceride is contained in trace amounts in the residue of the water removal step as an intermediate product, they are converted into fatty acid esters by the esterification reaction with methanol.

[0044] The quantitative ratio of the fats and oils to water and alcohol is preferably 1 to 1000 moles of water per 1 mole of the fatty acid glyceride contained in the fats and oils in the first step. In order to sufficiently promote the hydrolysis reaction in the first step, the amount of water is preferably as large as possible. And since most of this water is removed in the draining process, there is no particular effect on the second process due to the large amount of water. However, it is not advisable to increase the amount of water unnecessarily from the viewpoint of miniaturization and cost performance of the apparatus for implementing the manufacturing method of the present invention. Therefore, the amount of water is preferably about 3 to 1000 mol per mol of the fatty acid glyceride. The amount of alcohol in the second step is preferably 3200 mol per 1 mol of fatty acid glyceride contained in fats and oils.

[0045] In order to sufficiently promote the esterification reaction of the fatty acid in the second step, it is preferable to use a larger amount of alcohol. However, the apparatus for performing the production method of the present embodiment is also reduced in size and cost performance. It is not wise to increase alcohol unnecessarily from the point of view. In the production method of the present invention, about 3 to 200 mol of alcohol is required and sufficient for 1 mol of fatty acid dalyceride.

[0046] Further, the reaction treatment time in the first step and / or the second step is the above-mentioned temperature- Under pressure conditions, between about 1 minute and about 10 hours is preferred. More preferably, it is about 1 minute to 3 hours, and still more preferably, about 1 minute to 1 hour. Of course, the reaction time usually varies depending on the type of fats and oils and alcohols and the temperature and pressure conditions, and therefore can be changed as appropriate. Exclude the case where the reaction time is 10 hours or more. Not something.

[0047] Further, the reaction product in the second step after the second step is purified (removal of dalyserin generated as shown in the above reaction formula, water remaining in the water removal step, alcohol added in the second step, and the like). And a fatty acid ester composition containing a high content of fatty acid ester. There is no particular limitation on the purification method, for example, a method such as decantation or distillation.

[0048] While the fatty acid ester composition produced by the production method of the present embodiment contains a high content of fatty acid ester, the total glycerin amount is set to be equal to or less than the upper limit of the biodiesel fuel standard in the EU and the United States. It is possible to use it as a biodiesel fuel.

[0049] As shown in Fig. 3, the apparatus for producing a fatty acid ester composition by the above-described production method produces fatty acids by a reaction in a subcritical state or a supercritical state in which oils and fats containing fatty acid glycerides coexist with water. A first treatment device 11 for removing water, a water removal treatment device 12 for substantially removing water from the reaction product generated in the first treatment device 11, and a second treatment device residual phase remaining in the water removal treatment device 12. A second processing apparatus 13 is provided that obtains a fatty acid ester by adding alcohol and reacting in a subcritical state or a supercritical state.

[0050] The first treatment device 11, the water removal treatment device 12, and the second treatment device 13 are not particularly limited, and may be, for example, a heat-resistant pressure-resistant tank, a tubular reactor, or the like. In particular, since the first treatment device 11 and the second treatment device 13 are used in a subcritical state or a supercritical state of water and Z or an alcohol, it is preferable that they have appropriate resistance.

[0051] As the drainage treatment device 12, there is no particular limitation, for example, a flasher, a decanter, an evaporator, or the like can be used. Further, for example, by providing a separation device such as the evaporator 15, the water removed by the water removal treatment device 12 may be separated into water and glycerin. [0052] Further, a purification device 14 for purifying the fatty acid ester composition by roughly removing alcohol and / or moisture from the reaction product generated in the second treatment device 13 may be provided. . Although there is no particular limitation for such a purification device 14, for example, a flasher, a distillation device, or the like can be used.

[0053] Further, it is preferable to provide a heating device that can heat and pressurize the first processing device 11 and the second processing device 13 to a subcritical state or a supercritical state of water and / or alcohol. ,. Needless to say, it is preferable to provide a temperature control device and / or a pressure control device capable of performing appropriate temperature control and pressure control as well as heating and pressing. Such a temperature control device and a pressure control device may be additionally provided in the drainage treatment device 12.

[0054] Further, the apparatus may be provided with a preheating apparatus capable of heating oils and fats, water, and alcohol to a temperature equal to or close to the temperature condition of the first processing apparatus 11 and / or the second processing apparatus 13 in advance. Les ,. This is economical because it is possible to eliminate waste such as lowering the temperature of the reactant and reheating. Further, a precompression device capable of pressurizing oils and fats, water, and alcohol to a pressure equal to or close to the pressure condition of the first treatment device 11 and / or the second treatment device 13 in advance may be provided. By providing such a preheating / precompression device, the raw materials such as fats and oils, water, and alcohol are heated and pressurized in advance to a subcritical state or a supercritical state or a state close to them, and then continuously subjected to the first pressure. By sending the fatty acid ester composition to the treatment device 11 and the second treatment device 13, the fatty acid ester composition is suitable for efficient production.

[0055] Of course, it is also possible to process the reactant generated in the first processing apparatus 11 with a preheating / preloading apparatus. That is, for example, even when each of the first treatment device 11, the water removal treatment device 12, and the second treatment device 13 is provided with a temperature control device and a pressure control device, in the case of the oils and fats, water, alcohol, and the first treatment device 11, The device configuration may be such that the generated reactant is heated and pressurized by a preheating / preloading device.

When the fatty acid ester composition is continuously produced, it is preferable to provide supply devices a, b, and c capable of continuously supplying fats and oils, water, and alcohol. Fatty acids, water, and alcohol are appropriately preheated from the supply devices _a , b, and c to the precompression device, the first treatment device 11, and the second treatment device 13, so that a fatty acid ester composition is continuously obtained. It becomes possible. In addition, the supply devices a, b, and c are provided with adjusting valves such as valves that can adjust the amount of supply from the supply devices a, b, and c. It may be provided with a supply amount control device capable of controlling the supply amount separately from the supply devices a, b, and c.

Hereinafter, an example of obtaining a fatty acid ester composition of oils and fats, water, and alcohol will be described with reference to FIG.

First, oils and fats and water are continuously supplied from the supply devices b and c, respectively, to a preheating device (not shown). The fats and oils and water are heated and pressurized by the preheating / preloading device until the temperature and pressure conditions in the first processing device 11, respectively, and then sent to the first processing device 11. In the first treatment device 11, the hydrolysis reaction between oils and fats and water proceeds, and fatty acids and dalyserin are obtained. The reactant generated in the first treatment device 11 is sent to a water removal treatment device 12 to remove water. At this time, glycerin is also removed as described above. Then, the reaction product that has passed through the water removal treatment device 12 is fed into the second treatment device 13 after being heated and pressurized as necessary.

On the other hand, the alcohol is continuously sent to a preheating / preloading device (not shown) by the supply device a, and heated and pressurized to the temperature and pressure conditions in the second processing device 13. Sent to. In the second treatment device 13, the esterification reaction between the fatty acid and the alcohol proceeds, and a fatty acid ester is obtained. The reaction product containing the obtained fatty acid ester and passing through the second treatment device 13 is appropriately fed to a purification device 14 such as a distillation device to remove alcohol, moisture, etc., so that the fatty acid ester is highly contained. The resulting fatty acid ester composition is obtained.

The present embodiment will be described in more detail by giving numerical values according to Example 1 described later.

[Second Embodiment]

Hereinafter, a second embodiment of the present invention will be described with reference to the drawings. However, the following embodiments do not limit the present invention. The description of the same configuration as that of the first embodiment is omitted, and the same reference numerals are given in the drawings. The embodiments can be appropriately modified without departing from the gist of the present invention. FIG. 1 shows a reaction formula in the method for producing a fatty acid ester composition of the present invention, FIG. 4 shows a flowchart of the production method in the present embodiment, and FIG. 5 shows an example of an apparatus configuration of a production apparatus in the present embodiment. Hereinafter, the manufacturing method of the present embodiment will be specifically described.

[0063] First, in the first step, the above-mentioned fats and oils and water are coexistently accommodated in a reactor. Then, by heating and pressurizing the reactor in which oils and fats coexist with water, the state of the reactor is changed from the state in which it is contained to the subcritical state or the supercritical state. In the first step, the hydrolysis reaction between the fatty acid glyceride contained in the fats and oils and water proceeds under such conditions to produce fatty acids. Specifically, the reaction shown in FIG. 1 (a) proceeds.

[0064] In the subsequent second step, the reaction product of the first step after the first step (as shown in the reaction formula shown in the figure, the reaction product of the first step mainly contains fatty acid glycerin, and further contains water, intermediate product The product contains a small amount of monoglyceride, etc.) and alcohol.

[0065] In the second step, the reaction proceeds in a subcritical state or a supercritical state. Here, the subcritical state or supercritical state refers to the state of the added alcohol. Preferably, a supercritical state is established for the added alcohol.

[0066] As the temperature condition and the pressure condition in the first step and / or the second step, it is preferable that the temperature condition is 200 ° C to 400 ° C and the pressure condition is 2MPa to 45MPa. More preferably, the temperature condition is 240 ° C to 380 ° C, and the pressure condition is 7MPa to 30MPa. More preferably, the temperature condition is 250 ° C to 300 ° C, and the pressure condition is about 8MPa to 22MPa.

Here, in the first step and the second step, it is preferable that the reaction conditions are approximately the same. This is because the manufacturing method of the present embodiment does not perform the dehydration treatment between the first step and the second step.Furthermore, there is a difference in the critical temperature and critical pressure between water and alcohol. Focusing on this, the temperature condition and the pressure condition in the first step and the second step can be set more preferably. In other words, the temperature and pressure conditions in the first and second steps are approximately the same as the temperature and pressure conditions under which the water becomes a subcritical state and the alcohol becomes a supercritical state.

[0068] Specifically, for example, when methanol is used as the alcohol, the critical temperature of methanol is about 239 ° C and the critical pressure is about 8. IMPa, while the critical temperature of water is about 374 ° C. Since the pressure is about 22. IMPa, set the temperature condition in the first and second steps between about 239 ° C and about 374 ° C, and the pressure condition from about 8 MPa to about 22 MPa. Is preferred.

[0069] Regarding the quantitative ratio of fats and oils, water and alcohol, in the first step, it is preferable that water is 3-200 moles with respect to 1 mole of fatty acid glyceride contained in the fats and oils. In order to sufficiently promote the hydrolysis reaction in the first step, the amount of water is preferably as large as possible. However, it is not advisable to increase the amount of water unnecessarily from the viewpoint of miniaturization and cost performance of the apparatus for performing the manufacturing method of the present embodiment. In addition, since the process proceeds to the second step after the first step without removing water from the reaction product of the first step, if there is too much water, the hydrolysis reaction of the fatty acid ester generated in the second step will occur at the same time, and It is not preferable because the esterification reaction is slightly inhibited. Therefore, the amount of water is preferably about 3 to 200 mol per 1 mol of the fatty acid dalyceride.

[0070] The amount of alcohol in the second step is preferably 3200 mol per 1 mol of fatty acid glyceride contained in fats and oils. In order to sufficiently promote the esterification reaction of fatty acids in the second step, it is preferable that the amount of alcohol is larger, but from the viewpoint of reducing the size of the apparatus for performing the production method of the present embodiment and reducing cost performance. It is not wise to use alcohol unnecessarily. In the production method of the present embodiment, about 3-200 mol of alcohol is necessary and sufficient for 1 mol of fatty acid glyceride.

[0071] The reaction treatment time in the first step and / or the second step is preferably between about 1 minute and about 10 hours under the above-described temperature and pressure conditions. More preferably, it is about 1 minute to 3 hours, and still more preferably, about 1 minute to 1 hour. Of course, this reaction treatment time usually varies depending on the type of fats and oils, alcohols, and temperature and pressure conditions, and thus can be changed as appropriate, and does not exclude the case where the reaction treatment time is 10 hours or more. Nare,

[0072] In the production method of the present embodiment, since no dehydration treatment is performed between the first step and the second step, it is not necessary to make the reaction conditions different between the first step and the second step. In other words, there is no need for the operation of heating / cooling, pressurization * decompression, and thus energy required for the operation, that is, energy such as electric power for operating the heating / cooling device or pressurization / decompression device, is unnecessary. . [0073] In the second step, the Esterich reaction between the fatty acid generated in the first step and the added alcohol and the Esterich reaction between the free fatty acid contained in the fats and oils and the added alcohol proceed, and the fatty acid ester Is generated.

[0074] Specifically, the reaction shown in FIG. 1 (b) proceeds. This reaction is much faster than the transesterification reaction under approximately the same conditions. In the reaction formulas, R and a number-added R represent a hydrocarbon group, and ROH may be a monohydric alcohol or an unsaturated and saturated polyhydric alcohol.

Further, by purifying the reaction product of the second step after the second step (removal of added water, alcohol, and glycerin generated as in the above reaction formula), the fatty acid ester can be increased. The resulting fatty acid ester composition is obtained.

[0076] There is no particular limitation on the purification method, such as decantation or distillation. The alcohol can be separated by evaporation by distillation. Since glycerin has any solubility in water, decantation can separate glycerin together with water in the second step reaction.

[0077] While the fatty acid ester composition produced by the production method of the present embodiment contains a high content of fatty acid ester, it is possible to make the total glycerin amount equal to or less than the upper limit of the biodiesel fuel standard. Useful as a diesel fuel.

[0078] When the fatty acid ester composition produced by the production method of the present embodiment is used as a diesel fuel, it is required to be practically suitable for use in cold regions. This is because, in a low temperature condition such as a cold region, if the diesel fuel solidifies or loses its fluidity, clogging of an internal combustion engine system filter and malfunction of ignition occur.

[0079] In fatty acid esters, the freezing point generally tends to decrease as the length of the hydrocarbon group derived from alcohol becomes longer. That is, the alcohol added in the second step is preferably an alcohol having a large number of carbon atoms. However, when an alcohol having a large number of carbon atoms is used, it is generally known that the reaction rate of the transesterification reaction is reduced, and the method using a conventional alkali catalyst or an acid catalyst or the conventional method described above is used. A practical problem arises in a typical (critical transesterification) supercritical alcohol method. As described above, the production method according to the present embodiment obtains a fatty acid ester (composition) through the hydrolysis reaction and the esterification reaction, as described above. Since the reaction rate is higher than the reaction, it is particularly effective when an alcohol having a large number of carbon atoms is used.

[0081] The production method of the present embodiment is characterized in that the reaction proceeds without using a catalyst under the condition of a subcritical or supercritical state, but it is not necessary to exclude the use of a catalyst. Depending on the reaction, an alkali catalyst or an acid catalyst, or an enzyme catalyst such as lipase phosphpholipase A2, which is an enzyme for decomposing fats and oils, may be used.

[0082] As shown in Fig. 5, an apparatus for producing a fatty acid ester composition by the above-described production method causes fatty acids containing fatty acid glycerides to coexist with water and to produce fatty acids by a reaction in a subcritical state or a supercritical state. A first processing apparatus 1 that performs the reaction in a subcritical state or a supercritical state by adding an alcohol to a reaction product generated in the first processing apparatus 1 to generate a fatty acid ester. It is. Between the first processing device 1 and the second processing device 2, there is no need to perform a step of substantially removing water from the reactant generated in the first processing device 1, so that the first processing device 1 and the second processing device 2 There is no need to install a moisture removal device between them.

[0083] The first processing apparatus 1 and the second processing apparatus 2 are not particularly limited, and may be, for example, a heat-resistant pressure-resistant tank, a tubular reactor, or the like. Since the first treatment device 1 and the second treatment device 2 are used in a subcritical state or a supercritical state of water and / or alcohol, it is preferable that they have appropriate resistance.

[0084] Further, a purification device for purifying the fatty acid ester composition by removing alcohol and / or moisture from the reaction product generated in the second treatment device 2 may be provided. Although there is no particular limitation on such a purification device, for example, a flasher, a decanter, an evaporator, or the like can be used.

[0085] Specifically, for example, alcohol and water are volatilized from the reaction product generated in the second processing apparatus 2 by the flasher 4, and then water containing glycerin is removed by the decanter 5. Furthermore, the alcohol / water remaining in the distillation device 6 is sufficiently removed to obtain a fatty acid ester composition. The water removed in the decanter 5 is separated into water and glycerin. A separate separation device, for example, an evaporator 7 may be provided.

[0086] It is preferable to provide a heating device and a pressurizing device that can heat and pressurize the first processing device 1 and the second processing device 2 to a subcritical state or a supercritical state of water and / or alcohol. Of course, it is preferable to provide a temperature control device and / or a pressure control device capable of performing appropriate temperature control and pressure control as well as heating and pressing.

[0087] Further, for example, when alcohol is added to the reaction product generated by the first processing apparatus 1, the alcohol to be added is heated in advance to the temperature condition in the second processing apparatus 2. Since it is possible to eliminate waste such as lowering the temperature of the reactants and reheating, oils, fats, water, and alcohol are heated in advance to a temperature similar to or close to the temperature conditions of the first processing unit 1 and the second processing unit 2. It may be provided with a possible preheating device. Further, a pre-pressurizing device may be provided which can pressurize oils, fats, water and alcohol to a pressure equal to or close to the pressure condition of the first processing device 1 and the second processing device 2 in advance. By providing such a preheating * preloading device, the raw materials such as fats, oils, water, and alcohol are heated and pressurized in advance to a subcritical state or supercritical state or a state close to them, and then the first By feeding into the processing apparatus 1 and the second processing apparatus 2, it becomes suitable for efficient production of the fatty acid ester composition.

Incidentally, the first processing apparatus 1 and the second processing apparatus 2 may be the same reactor. As described in the above-mentioned manufacturing method, the reaction conditions of the first processing apparatus 1 and the second processing apparatus 2 are almost the same, and between the first step and the second step, the reaction conditions are generated in the first step. Since alcohol is added to the reaction product, an operation such as transferring the reaction product generated in the first step to another device is not required. Therefore, as a manufacturing apparatus, the first process is performed in this reactor as a reactor which is the same device without distinguishing the first processing device 1 and the second processing device 2, and subsequently, the reactor is subjected to the first process. The second step may be performed by adding alcohol.

Further, the processing apparatus may be a single reactor including a first processing section corresponding to the first processing apparatus and a second processing section corresponding to the second processing apparatus. In other words, the same reactor is not only a physical entity whose function is to perform batch processing, but also has the same reactor as the physical entity but has the first process processing unit and the The function may be to perform a flow process approximately by having a two-step processing unit. In particular, a processing apparatus as the same reactor including a first processing section corresponding to the first processing apparatus and a second processing section corresponding to the second processing apparatus is suitable for continuous production of the fatty acid ester composition. It is. This makes it possible to reduce the number of devices and reduce the size of the fatty acid ester composition manufacturing device.

[0090] When the fatty acid ester composition is continuously produced, it is preferable to provide supply devices a, b, and c capable of continuously supplying fats and oils, water, and alcohol. Fatty acids, water, and alcohol are appropriately preheated from the supply devices _a , b, and c to the precompression device, the first treatment device 1, and the second treatment device 2 to continuously obtain a fatty acid ester composition. It becomes possible. In addition, the supply devices a, b, and c may be provided with an adjusting valve such as a valve capable of adjusting the supply amount from the supply devices a, b, and c, or the supply devices a, b, and c Separately, a device provided with a supply amount control device capable of controlling the supply amount may be used.

[0091] Hereinafter, an example of obtaining a fatty acid ester composition of oils and fats, water, and alcohol will be described with reference to FIG.

[0092] First, oils and fats and water are continuously supplied from supply devices b and c, respectively, to a preheating device (not shown). The fats and oils and water are sent to the first treatment device 1 after being preheated * heated by the preload device * pressurized until the temperature and pressure conditions in the first treatment device 1 respectively.

[0093] In the first treatment apparatus 1, the hydrolysis reaction between oils and fats and water proceeds, and fatty acids and glycerin are obtained (see Fig. 1 (a)).

[0094] The reactant generated in the first processing device 1 is sent to the second processing device 2. On the other hand, the alcohol is continuously sent to the preheating / preloading device (not shown) by the supply device _a , and is heated to the temperature and pressure conditions in the second processing device 2 and then sent to the second processing device 2 after being pressurized. .

[0095] In the second processing apparatus 2, the esterification reaction between the fatty acid and the alcohol proceeds, and a fatty acid ester is obtained (see Fig. 1 (b)). Then, the reaction product containing the obtained fatty acid ester through the second treatment device 2 is appropriately fed to a purification device such as a distillation device 6 to remove alcohol, moisture and the like, thereby containing a high content of fatty acid ester. A fatty acid ester composition is obtained. [0096] According to the production method 'apparatus of the present embodiment, compared to the reaction conditions (for example, about 350 ° C and about 40MPa, as described above) of the supercritical alcohol method in which the transesterification reaction is the main reaction. For example, a relatively mild reaction condition, such as a temperature condition of about 50-100 ° C and a pressure condition of about 20MPa-30MPa, may be used to promote the hydrolysis reaction and the esterification reaction. Energy, ie, power for operating the preheating device, the device that heats and cools the first and / or second treatment device, and the device that pressurizes and decompresses it, is considerably less. Do it. In particular, in the second step, the temperature is not lowered to room temperature and / or normal pressure, so that the production method is more economical. In addition, since the reaction can be carried out in the presence of water in fats and oils, the pre-treatment of dehydration, which requires enormous electricity and other energy required for the operation of processing equipment that removes water from fats and oils, is not possible. This perspective is also an economical manufacturing method because it is not necessary.

[0097] Further, according to the production method 'apparatus of the present embodiment, since the transesterification reaction is not the main reaction, it is possible to sufficiently suppress the residual amount of monoglyceride' diglyceride, an unreacted fatty acid glyceride, which is an intermediate product. It is therefore possible to adapt the total glycerin level to the biodiesel standards in the EU and the United States. In addition, regarding the yield, fatty acid glycerides are positively converted into fatty acids by a hydrolysis reaction, and furthermore, the fatty acids and the free fatty acids in the fats and oils undergo an esterification reaction with alcohol to obtain fatty acid esters. The yield is very high, equivalent to or better than the conventional supercritical alcohol method.

[0098] Furthermore, since the hydrolysis reaction and the esterification reaction progress at a higher reaction rate than the transesterification reaction, the fatty acid can be prepared in a shorter time under milder reaction conditions than the conventional supercritical alcohol method. It is possible to obtain an ester composition.

[0099] This embodiment will be described in further detail by giving numerical values according to Example 2 described later.

[Example 1]

Example 1 As Example 1, an example using a method (two-step method) corresponding to the above-described first embodiment will be described.

[0101] In the production apparatus shown in Fig. 3, rapeseed oil: 1. Okg and water: 4.4 kg {water / Triglyceride = 217/1 (molar ratio) is fed into the first treatment apparatus 11 and is subjected to a hydrolysis reaction at a temperature of 270 ° C and a pressure of 17 MPa for about 30 minutes (first step). ).

[0102] The reaction product obtained in the first step is cooled to a temperature of 150 ° C and transferred to a decanter (water drainage treatment device 12). The liquid is separated into a heavy liquid mainly containing water, and a light liquid mainly containing fatty acids is transferred to the next second treatment device 13.

[0103] Next, the pre-heated and pressurized methanol: 4.7 kg (methanol / fatty acid = 42) in the reactant (fatty acid-containing composition) transferred to the second processing apparatus 13 for performing the esterification reaction. / 1 (molar ratio), and the esterification reaction is carried out for about 30 minutes at a temperature of 270 ° C and a pressure of 17 MPa (second step).

[0104] Next, the fatty acid ester-containing composition obtained in the second step is separated into a fatty acid ester composition and a water-methanol-glycerin-containing composition by, for example, a purifying apparatus 14 in a purification step. The yield of the resulting fatty acid ester composition (fatty acid ester composition / triglyceride in the raw material) is 93%, and the total glycerin (Gs) is 0.18%, which satisfies biodiesel fuel standards in the EU and the United States. Was something.

[Comparative Example 1]

As Comparative Example 1, an example in which a conventional method (one-step method) is performed at a reaction temperature of 350 ° C is shown. As raw materials, 1. Okg of rapeseed oil and 4.7 kg of methanol were reacted at 350 ° C and 20 MPa for about 10 minutes. The yield of the resulting fatty acid ester composition (fatty acid ester composition / triglyceride in the raw material) is 96%, the total glycerin content (Gs) is 0.25%, and the biodiesel fuel standards in the EU and the United States are met. It was at last fulfilling.

[Comparative Example 2]

As Comparative Example 2, an example in which a conventional method (one-step method) is performed at a reaction temperature of 270 ° C. is shown. Rapeseed as raw material 1. Okg and 4.7 kg of methanol were reacted at 270 ° C and 17MPa for 60 minutes. The yield of the resulting fatty acid ester composition (triglyceride in the fatty acid ester composition Z raw material) was very low at 70%.

[Example 2]

Example 2 is an example using a method (two-step method) corresponding to the above-described second embodiment. Show. In the production apparatus shown in FIG. 5, rapeseed oil: 1. Okg and water: 4.4 kg {water / triglyceride = 217/1 (molar ratio)} are fed into the first treatment apparatus 1 as raw materials, and the temperature is: The hydrolysis reaction was carried out for about 30 minutes under the conditions of 270 ° C. and pressure: 17 MPa (first step).

[0108] The reactant obtained in the first step is then transferred into the second processing apparatus 2, and the transferred reactant is preliminarily heated and pressurized with methanol: 5.5 kg (methanol / fatty acid). = 50/1 (molar ratio), and the esterification reaction is carried out for about 30 minutes at a temperature of 270 ° C and a pressure of 17 MPa (second step).

Next, the fatty acid ester-containing composition obtained in the second step is passed through the flasher 4 and transferred to the decanter 5 from the bottom of the flasher 4. Alternatively, transfer directly to decanter 5 without passing through flasher 4. The decanter 5 separates the light liquid mainly containing fatty acid ester and the heavy liquid mainly containing water-glycerin, and the light liquid mainly containing fatty acid ester is subjected to, for example, distillation in the next purification step. By the device 6, the fatty acid ester composition and the water-containing methanol composition were separated. The yield of the resulting fatty acid ester composition (fatty acid ester composition / triglyceride in the raw material) is 93% and the total glycerin content (Gs) is 0.22%, which meets the biodiesel fuel standards in the EU and the United States. It was a fulfillment.

[0110] The water-containing methanol composition generated in this purification step is mixed with the water-containing methanol composition discharged from the upper portion of the flasher 4, and after removing water, the methanol is returned to the second step. May be reused.

[0111] The water 'glycerin-containing composition discharged from the bottom of the decanter 5 is separated into water and glycerin in the next evaporator 7, and the water is converted into water for the first step (hydrolysis reaction) as follows. It may be used for the reaction.

[Comparison of Example and Comparative Example 1]

Comparing Example of the present invention with Comparative Example 1, the yield of the obtained fatty acid ester composition was both high. It is also possible to obtain biodiesel fuels that meet the EU and US biodiesel fuel standards (total dalyserine (Gs), 0.25% and 0.24%).

However, since the reaction is performed at a high temperature of 350 ° C., the processing apparatus has a higher heat resistance and resistance to heat than the processing apparatus of the embodiment which can perform the reaction at a low temperature of 270 ° C. Expensive materials with excellent corrosiveness must be used. There is a problem that it is inferior.

[0114] Importantly, fatty acid esters obtained at high temperatures are highly likely to undergo thermal denaturation. When a three-dimensional crosslinked structure is formed by heat denaturation, the fluidity of the fatty acid ester decreases. Furthermore, fatty acid esters obtained at high temperatures are highly likely to undergo structural transformation due to thermal denaturation as shown in Reference Example (FIG. 6). When the structural transition (isomerization) due to thermal denaturation as shown in the reference example (Fig. 6) occurs, the melting point of the fatty acid ester increases. Therefore, when a fatty acid ester obtained at a high temperature is used as a fuel, the fluidity of the fuel may be insufficient particularly in a low temperature situation such as in winter. That is, when the fatty acid ester obtained by such a high-temperature reaction is used as a fuel, the fuel filter and the fuel nozzle are easily clogged, and unburned carbon adheres to the combustion chamber immediately, and fine particles are also contained in the exhaust gas. And problems such as clogging and reduction in catalytic activity in the exhaust gas treatment device are likely to occur.

[0115] In order to avoid such a problem in the high-temperature reaction, it is preferable to obtain the fatty acid ester by reacting at a lower temperature condition. For reference, an example is shown in which methyl linolenate was produced under high and low temperature conditions. Figure 6 (a) is the FT-IR spectrum when methyl linolenate was obtained at 270 ° C, and Figure 6 (b) is the FT-IR spectrum when methyl linolenate was obtained at 350 ° C. It is. In Fig. 6, when comparing the spectral amount of the trans-form and the cis-form of the double bond, the transition from the cis-form to the trans-form was hardly observed in the one obtained under the reaction conditions of 270 ° C. However, those obtained under the reaction conditions of 350 ° C show much more transition to the trans form (isomerization) than those obtained under the reaction conditions of 270 ° C. Fatty acid chains having many trans-type double bonds have a higher melting point than those having many cis-type double bonds, and are easily solidified in a low temperature region. Thus, at 270 ° C., where it is preferred to obtain the fatty acid ester at lower temperatures to reduce the trans-transformation, such isomerization does not occur.

[Comparison between Example and Comparative Example 2]

Comparing the Example of the present invention with Comparative Example 2, the yield of the fatty acid ester composition obtained at the same temperature and the same time in the same time was 93% in this example, and 70% in Comparative Example 2, which was very low. And the total glycerin level (Gs) is very high. Therefore, it can be said that the embodiment of the present invention is superior. [0117] Considering these facts, according to the present invention, a high yield can be achieved even when the fatty acid ester composition is performed under a low-temperature reaction condition of 270 ° C. In addition, the resulting fatty acid ester composition has low thermal denaturation and good fluidity, so that biodiesel fuel with high fluidity under low temperature conditions can be obtained, and the factors that clog nozzles and fuel filters can be reduced. Power S can.

Industrial applicability

[0118] The present invention can be used for a method and an apparatus for producing a fatty acid ester composition by reacting an oil or fat with an alcohol.

Claims

The scope of the claims

[1] A method for producing a fatty acid ester composition by reacting an oil or fat with an alcohol,

A first step of causing fatty acids containing fatty acid glycerides to coexist with water and producing fatty acids by a reaction in a subcritical or supercritical state;

A water removal step of approximately removing water from the first step reaction product after the first step; and alcohol in a water removal step residue remaining in the water removal step, and a reaction in a subcritical state or a supercritical state. And a second step of producing a fatty acid ester by the method.

[2] The temperature condition and the pressure condition in the first step and / or the second step are as follows:

Pressure condition: 2.0—45MPa

Temperature condition: 200—400 ° C

And in the water removal step temperature conditions' pressure conditions,

Pressure condition: 0.2—45MPa

Temperature condition: 50-350 ° C

2. The method for producing a fatty acid ester composition according to claim 1, wherein the method is characterized in that:

[3] The production of the fatty acid ester composition according to claim 1, wherein water is 31,000 mol and alcohol is 3200 mol per 1 mol of the fatty acid glyceride contained in the fats and oils. Method.

[4] A method for producing a fatty acid ester composition by reacting an oil or fat with an alcohol,

A second step in which alcohol is added to the reaction product of the first step after the first step and a fatty acid ester is produced by a reaction in a subcritical state or a supercritical state;

A method for producing a fatty acid ester composition, comprising:

[5] The temperature condition and the pressure condition in the first step and / or the second step are as follows: Pressure condition: 2.0-45MPa

Temperature condition: 200—400 ° C

5. The method for producing a fatty acid ester composition according to claim 4, wherein the method is in the range of:

[6] The temperature and pressure conditions in the first step and the second step are approximately the same as the temperature and pressure conditions in which the water is in a subcritical state and the alcohol is in a supercritical state. The method for producing a fatty acid ester composition according to claim 4, wherein

[7] The fatty acid ester composition according to claim 4, wherein water is 3200 moles and alcohol power is 200 moles per mole of fatty acid glyceride contained in fats and oils. Production method.

[8] The fatty acid according to claim 1, wherein the temperature condition and the pressure condition in the first step and the temperature condition * pressure condition in the second step are substantially the same. A method for producing an ester composition.

[9] The method according to claim 2, further comprising, following the second step, a purification step of purifying the fatty acid ester composition by substantially removing alcohol and / or water contained in the reaction product of the second step. Item 5. The method for producing a fatty acid ester composition according to Item 1 or 4.

[10] The method according to claim 1, wherein the alcohol is a monohydric alcohol.

Item 5. The method for producing a fatty acid ester composition according to Item 4.

[11] The fat according to claim 1 or 4, wherein the reaction treatment time in the first step and / or the second step is between about 1 minute and about 10 hours. A method for producing an acid ester composition.

12. The method for producing a fatty acid ester composition according to claim 1, wherein the fat or oil contains a fatty acid.

[13] The method for producing a fatty acid ester composition according to claim 1, wherein the fats and oils are animal fats or vegetable fats or waste fats and oils.

[14] The first aspect of the present invention, wherein the fatty acid ester is a component of a diesel fuel. Item 5. The method for producing a fatty acid ester composition according to item 4 or 4.

[15] A diesel fuel containing the fatty acid ester composition produced by the production method according to claim 1 or 4.

[16] An apparatus for producing a fatty acid ester composition by a reaction between fats and oils and alcohol,

A first treatment device that causes fatty acids containing fatty acid glycerides to coexist with water and generates fatty acids by a reaction in a subcritical or supercritical state;

A fatty acid ester composition, characterized by comprising: a second processing device that adds an alcohol to a reaction product generated in the first processing device and generates a fatty acid ester by a reaction in a subcritical state or a supercritical state. Manufacturing equipment.

[17] An apparatus for producing a fatty acid ester composition by a reaction between a fat or oil and an alcohol,

A water removal treatment device for approximately removing water from the reaction product generated in the first treatment device;

A second treatment device that adds an alcohol to a residue of the water removal treatment device remaining in the water removal treatment device and generates a fatty acid ester by a reaction in a subcritical state or a supercritical state. An apparatus for producing a fatty acid ester composition.

18. The method according to claim 16, wherein at least one of the processing devices includes a temperature control device capable of controlling a temperature and / or a pressure control device capable of controlling a pressure. For producing a fatty acid ester composition.

[19] The second treatment apparatus further includes a purifying apparatus for purifying the fatty acid ester composition by removing alcohol and / or water from the reaction product generated in the second processing apparatus. Item 18. An apparatus for producing a fatty acid ester composition according to Item 16 or 17.

20. The apparatus for producing a fatty acid ester composition according to claim 16, wherein the first processing apparatus and the second processing apparatus are the same reactor. A supply device capable of continuously supplying oils and fats, water, and alcohol, respectively,

Heating fats and oils, water and alcohol to a temperature and pressure close to or near the subcritical or supercritical state of water and / or alcohol.Preheating that can be pressurized. Any or all of the alcohol and the reactants generated in the first processing apparatus are processed in a preheating / preloading apparatus before being processed in the first processing apparatus and / or the second processing apparatus. 18. The apparatus for producing a fatty acid ester composition according to claim 16 or 17, wherein: