JP2001271090A - Method for producing fatty acid ester and fuel containing fatty acid ester - Google Patents

Abstract

(57) [Summary] [Problem] From oils and fats and alcohol, using a solid catalyst,
Provided are a method for producing a fatty acid ester and glycerin in a low-temperature and low-pressure system which is relatively advantageous in production, and a fuel containing the fatty acid ester. A method for producing a fatty acid ester from fats and oils and an alcohol, comprising the steps of: producing a fatty acid ester containing at least one of calcium hydroxide and calcium oxide;
A method for producing a fatty acid ester and glycerin, characterized in that the reaction is carried out in a temperature range of from 0 ° C. to 240 ° C., and a fuel, a diesel fuel, and a lubricating base oil containing the fatty acid ester and glycerin produced by the method. Or fuel oil additives.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing fatty acid esters and glycerin by reacting fats and oils and alcohols, and to a fuel containing fatty acid esters obtained by the production method.

[0002]

BACKGROUND OF THE INVENTION Fats and oils are mainly composed of esters of fatty acids and glycerin called triglycerides, and fatty acid esters obtained by transesterification using fats and oils and alcohols are widely used in industrial raw materials and pharmaceuticals.

[0003] There has been reported a method for producing a diesel fuel or a lubricating base oil containing a fatty acid ester, which replaces the conventional mineral oil by transesterifying the oil or fat with an alcohol to cause transesterification. For example, in JP-A-9-235573 and JP-A-7-197047, diesel fuel is produced by reacting waste edible oil with methanol in the presence of caustic soda. JP-A-7-197047 discloses that the transesterification reaction is usually carried out at 50 ° C. to 70 ° C. under atmospheric pressure using an alkali catalyst such as caustic soda.

[0004] On the other hand, sodium carbonate as a heterogeneous solid catalyst
To normal pressure or normal pressure using
Under close conditions, the boiling point of the alcohol used or a temperature close to it
(Japanese Patent Laid-Open No. 61-2 / 1986)
No. 54255). Fats and alcohols are ZnO,
Or 170-250 ° C under a composite oxide catalyst of Zn and Al
In the range of 10 MPa (100 bar) or less
Technology for producing fatty acid esters (US Pat. No. 5,090,894)
No. 6 is also known. Also, alkaline earth metals
Using a solid catalyst or the like containing an oxide,
Range: 1 atm (0.1 MPa) to 100 atm (1
Under a pressure of 0.1 MPa), oils and fats react with alcohol
To selectively produce monoglyceride (Spain)
Japanese Patent No. 2124166) has been proposed,
How to make fatty acid alkyl esters and glycerin
Not disclosed. Further, Romanian Patent No. 1093
In the specification No. 28, from a temperature of 65 ° C. using a CaO catalyst,
85 ° C, pressure 1atm (0.1MPa) to 2atm
(0.2 MPa), reaction time 1 hour to 3 hours, etc.
A method for reacting fats and oils with methanol has been proposed.
However, the reaction is slow and inefficient.

[0005]

DISCLOSURE OF THE INVENTION The inventors of the present invention have developed a method for producing a fatty acid ester and glycerin by reacting a fat and an alcohol with an alcohol and a fuel containing the fatty acid ester by adding a solid base catalyst to the fat and / or glycerin. Alternatively, a method has been proposed in which the reaction is carried out under conditions in which the alcohol is in a supercritical state exceeding 260 ° C.
No. 6), but this method requires high-temperature and high-pressure equipment. An object of the present invention is to provide a method for producing fatty acid esters and glycerin in a low-temperature and low-pressure system which is relatively advantageous in production from fats and oils and alcohols using a solid catalyst, and to provide a fuel containing the fatty acid esters and the like. is there.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, if the reaction is carried out under an appropriate temperature condition in the presence of a solid catalyst containing calcium,
The inventors have found that the reaction proceeds efficiently, and have completed the present invention.

That is, the present invention provides the following [1] to [5]
I will provide a. [1] A method for producing a fatty acid ester from fats and oils and alcohols, the method comprising the steps of:
A method for producing a fatty acid ester and glycerin, characterized in that the reaction is carried out in a temperature range of 40 ° C. [2] A fuel containing the fatty acid ester and glycerin produced by the production method according to the above [1]. [3] A diesel fuel containing the fatty acid ester and glycerin produced by the production method according to [1]. [4] A lubricating base oil containing a fatty acid ester and glycerin produced by the production method according to [1]. [5] A fuel oil additive containing the fatty acid ester and glycerin produced by the production method according to [1].

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The main reaction of the production method of the present invention is represented by the following reaction formula (2)
Indicated by

[0009]

Embedded image

(Wherein R ₁ , R ₂ and R ₃ are each independently
Shows the carbon chain of the fatty acid. The carbon number of R _{1 to} R ₃ varies depending on the type of fat. R ₄ represents a hydrocarbyl group which may be substituted with a hydrocarboxyl group.) The fat or oil used in the present invention is mainly composed of triglyceride which is an ester of fatty acid and glycerin. Here, "mainly containing triglyceride" means that triglyceride is contained in 50% by weight or more of the fat or oil.

The fats and oils used in the present invention are represented by the reaction formula (2)
Containing mainly triglyceride 1 of the fatty acids shown
Quality, and may be a natural fat or a synthetic fat. For fats and oils,
Typical are lard fat, chicken fat, butter
Fat, tallow, cocoa butter fat, corn oil, peanut
A oil, cottonseed oil, soybean oil, coconut oil, olive oil, safra
Wheat oil, linseed oil, coconut oil, oak oil, almond
Oil, apricot kernel oil, beef bone fat, black walnut oil, castor oil,
Daifuko oil, Chinese fat, cod liver oil, cottonseed stearin, sesame
Oil, tallow, dolphin, sardine, mackerel, horse fat, lard,
Bone oil, linseed oil, sheep fat, beef leg oil, palm oil, palm kernel
Oil, porpoise oil, shark oil, sperm whale oil, paulownia
Oil, whale oil, etc., but are not limited to these.
No. A mixture of a plurality of these fats and oils, diglyceride
Fats and oils including lido and monoglyceride, some, oxidation, reduction, etc.
Fats and oils that have been denatured may be used. Unrefined fats and oils
In, what may contain free fatty acids and water,
Waste from restaurants, food factories, households, etc.
Cooking oil may be used, but perform appropriate pretreatment as necessary
Is preferred. For example, the present invention is applied to waste oil such as waste cooking oil.
When insoluble solids are mixed in fats and oils
Blockage of the pump and pressure control valve, hindering stable operation
Wire mesh, filter before feeding to the preheater as it may
It is preferable to remove insoluble solids from fats and oils, etc.
No.

The fats and oils may contain components other than fats and oils. Specifically, crude oil, heavy oil, light oil, mineral oil, essential oil, coal, fatty acid, saccharide, metal powder, metal salt, protein, amino acid, hydrocarbon, cholesterol, flavor, coloring compound, enzyme, fragrance, alcohol, fiber, Resin, rubber,
Paints, cements, detergents, aromatics, aliphatics,
Examples include, but are not limited to, soot, glass, earth and sand, nitrogen-containing compounds, sulfur-containing compounds, phosphorus-containing compounds, and halogen-containing compounds.

The above-mentioned substances contained in fats and oils may be involved in the reaction, for example, when they may inhibit the reaction, or when they are solid and may be clogged in the production process. Is preferably removed using a technique such as filtration or distillation before the reaction. As a method of distillation,
Examples thereof include, but are not limited to, vacuum distillation, steam distillation, molecular distillation, and extractive distillation. In the present invention, waste fats and oils, waste edible oils, and the like can be used as the fats and oils.

The alcohol (2 in the reaction formula (2)) used in the present invention is not particularly limited,

An alcohol represented by the formula: R-OH (1) wherein R represents a hydrocarbyl group having 1 to 10 carbon atoms or a hydrocarbyl group having 2 to 10 carbon atoms and substituted by a hydrocarbyloxyl group. preferable.

Examples of the hydrocarbyl group having 1 to 10 carbon atoms in R include an alkyl group, an aralkyl group, an alkenyl group and an alkynyl group.

Examples of the alcohol in which R is an alkyl group include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-
Butanol, pentanol, hexanol, cyclohexanol, heptanol and the like are exemplified.

Examples of the alcohol in which R is an aralkyl group include benzyl alcohol, α-phenethyl alcohol, β
-Phenethyl alcohol, with benzyl alcohol being preferred.

Examples of the alcohol in which R is an alkenyl group include allyl alcohol, 1-methylallyl alcohol,
2-methylallyl alcohol, 3-butene-1-o-
And allyl alcohol is preferred.

Examples of the alcohol in which R is an alkynyl group include 2-propyn-1-ol and 2-butyn-1-o-.
And 3-butyn-1-ol, 3-butyn-2-ol and the like.

Examples of the alcohol in which R is a hydrocarbyl group substituted with a hydrocarboxyl group having 2 to 10 carbon atoms include 2-methoxyethanol, 2-methoxypropanol and 3-methoxybutanol.

Among these, as the alcohol, R is preferably an alkyl group having 1 to 4 carbon atoms. Specifically, methanol in which R is a methyl group, ethanol in which R is an ethyl group, propanol in which R is a propyl group,
Isopropanol wherein R is an isopropyl group, R is n-
Preferred are n-butanol which is a butyl group, isobutanol where R is an isobutyl group, and t-butanol where R is a t-butyl group, more preferably methanol and ethanol, and even more preferably methanol. The purity of the alcohol is not particularly limited, but is preferably 9
It is at least 5%, more preferably at least 98%. One type of alcohol may be used, or two or more types may be mixed and used. In addition, the alcohol also includes an optical isomer when an optical isomer is present.

The supply weight of alcohol is preferably 1 to 100 times (reaction equivalent ratio) the theoretical supply weight of alcohol calculated according to the following equation.

[0023]

## EQU1 ## Theoretical supply weight of alcohol = (supply weight of fat / oil × saponification value of fat / oil × molecular weight of alcohol) ÷ 56100

(Here, the saponification value of fats and oils means 1 g of fats and oils.
The amount of potassium hydroxide required to completely saponify is expressed in mg.) When the ratio is smaller than 1, the reaction yield decreases, which is not preferable. If it is larger than 100, the apparatus may be too large, which is not preferable.

Typical examples of the fatty acid ester 3 produced by the reaction of the formula (2) include valeric acid, caproic acid, enantonic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid and tridecyl. Acid, myristic acid, pentadecylic acid, palmitic acid, heptedylic acid, stearic acid, nonadecanoic acid, arachiic acid, penic acid, lignoceric acid, serotinic acid, heptacosanoic acid, montanic acid, melisic acid, lacceric acid, crotonic acid, isocrotonic acid , Undecylenic acid, oleic acid, elaidic acid, setleic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, propiolic acid, stearolic acid, nervonic acid, ricinoleic acid,
Examples include, but are not limited to, esters such as (+)-hydronocarbic acid and (+)-chaurum-grulinic acid. The alcohol residue of the ester is determined by the alcohol used. For example, when methyl alcohol is used as the alcohol, a methyl ester is obtained, and when ethyl alcohol is used, an ethyl ester is obtained. When the fatty acid residue has an optical isomer, the fatty acid residue also includes the optical isomer. Further, in the present manufacturing method,
In addition to fatty acid esters, the main product is glycerin 4
Is generated.

Next, the solid catalyst used in the present invention will be described.
I will tell. The solid catalyst used in the present invention is calcium hydroxide.
And a catalyst comprising at least one of calcium oxide
preferable. The form of the solid catalyst may be, for example, a powder form.
Then, it may be formed into granules. Also carried on inorganic surfaces
May be done.

The amount of the catalyst used is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, based on calcium, based on 100 parts by weight of the fat or oil.

The temperature at which the oil or fat of the present invention is reacted with alcohol.
The temperature condition is preferably in a temperature range of 90C to 240C. Book
Pressure in the reaction vessel for reacting the oil and fat of the invention with alcohol
The condition is in the range of 0.2 MPa to 8 MPa.
Is preferred. Reacting the oil and fat of the present invention with alcohol
The duration is preferably between 1 minute and 180 minutes
The range is more preferably from 2 minutes to 120 minutes. Even better
More preferably, it ranges from 3 minutes to 60 minutes. Reaction temperature, anti
The reaction time and the amount of catalyst added should be within the above ranges as necessary.
You can choose more freely, but if the reaction temperature is low,
The reaction time and the amount of catalyst added are higher than when the temperature is high.
Tend to add.

This reaction can be carried out in various reaction modes. For example, it may be performed by a batch method or a distribution method. In the present invention, the fats and oils and the alcohol may be uniformly mixed during the reaction, or may be separated into two layers as long as they can react. In the case of separation into two layers, for example, the reaction can be further efficiently performed by increasing the contact area between the two layers by performing the reaction under stirring.

After completion of the reaction, the reaction mixture contains fatty acid esters, glycerin, excess unreacted alcohol, and may further contain unreacted raw materials and other impurities. From this reaction mixture to the purity required for each application,
Purify the fatty acid ester. The method for purification is not particularly limited, and general methods such as distillation and extraction can be applied according to the properties of the fatty acid ester to be produced. For example, in the case where methanol is used as the alcohol, an excess (or unreacted) methanol component is vaporized, separated and collected, and then allowed to stand still to be separated into a light liquid and a heavy liquid.

The solid catalyst used in the present invention is relatively easy to separate from the reaction solution as compared with a caustic soda catalyst or the like, and the post-treatment of the reaction solution is simple. The light liquid is mainly composed of a fatty acid methyl ester and can be used as a raw material for diesel fuel or a raw material for natural higher alcohols. Further, the heavy liquid of glycerin main component can be used as a raw material of industrial glycerin. Separation of unreacted alcohol, other than distillation such as vacuum distillation, may be exemplified by mixer-settler extraction, liquid-liquid extraction, extraction using a pulse column, jet extraction, Bodovierniak rotary extraction, etc. However, it is not limited to this.
Further, the alcohol may be completely separated, and only the fatty acid ester may be taken out, or the alcohol may be recovered in a state where the alcohol remains.

The fatty acid ester produced by the method of the present invention depends on the structure of the raw material fat, but when a natural fat or oil is used, it is generally a mixture of several fatty acid esters. In this case, the mixture can be used as it is depending on the application, or if necessary, only a specific fatty acid ester can be separated and used by a general method such as distillation or extraction.

The fatty acid ester produced as described above may be used alone or in a fuel such as a diesel fuel, a lubricating base oil, a fuel oil additive, etc., depending on the requirements of its use.
It can be used by mixing with other components.

New Edition Automobile Engineering Handbook (Corporation
According to the Society of Automotive Engineers of Japan), when used as diesel fuel, ignitability and viscosity are important. If a fatty acid ester having a relatively low viscosity is used, it causes abrasion or burning, so that it is necessary to use a fatty acid ester having a viscosity suitable for a diesel engine. On the other hand, if the molecular weight is too high, it causes odor and smoke emission, so such fatty acid esters are not preferred. For example, fatty acid methyl ester, fatty acid ethyl ester, fatty acid isopropyl ester, fatty acid isobutyl ester and the like are preferably used as diesel fuel. Among them, fatty acid isopropyl ester,
Fatty acid isobutyl ester becomes a diesel fuel with high properties at low temperatures. Even when used as a lubricating base oil, viscosity is important. For summer use, a relatively high viscosity is desired in order to provide high lubricity, but when used in winter or at a low temperature, a relatively low viscosity, high fluidity fatty acid ester is desired. Therefore, a wide range of fatty acid esters can be used as the lubricating base oil. As a fuel oil additive, a fatty acid ester is added to fuel mainly for the purpose of reducing friction. It plays almost the same role as the lubricating oil, and the same properties as the lubricating base oil are desired.

The produced fatty acid ester is
As long as there is no problem in use, glycerin, excess unreacted alcohol, unreacted fats and oils, and other impurities contained in the reaction mixture after the reaction may be contained within the range. Further, if necessary for the application, the yield can be further improved by repeating the reaction under the conditions of the present invention.

[0036]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Embodiment 1  As a fat mainly composed of triglycerides, a solid catalyst
0.03% of calcium hydroxide powder (calcium
Soybean oil 0.751 dispersed
g, weigh 1.085 g of methanol as alcohol
And a stainless steel reaction tube (about 4.5 cm^Three) Filled densely
Closed. This reaction tube is a fluidized bed temperature-controlled to 240 ° C.
30 minutes after putting into a sand bath and raising the temperature and reacting
And immediately put in water to cool. Used for this reaction
The amount of methanol used was such that soybean oil was completely methyl ester
About 13 times the theoretical amount necessary for
About 13 times). Next, the reaction solution in the reaction tube is
After collection, the THF washing was repeated three times to collect the collected solution.
Chromatographic analysis of methyl ester and glycerin components
Evaluate reactivity by quantitative analysis by torography (GC method)
As a result, the yield of fatty acid methyl ester (MES) was about
96%, glycerin (GL) yield was about 94%
(Shown in Table 1). Here, the yield refers to 1 mol of soybean oil.
3 moles of fatty acid methyl ester and 1 mole of glycerin
It is a value calculated based on the reaction to be performed. Also the reaction
A size exclusion tool that separates and analyzes components in the liquid based on differences in molecular weight
As a result of analysis by chromatography (SEC method),
97% methyl ester component (MES)
Ceride component (MG) is 2%, diglyceride component (DG)
Was 1% and the triglyceride component (TG) was 0%
(Shown in Table 1).

Comparative Example 1 A test was conducted in the same manner as in Example 1 except that soybean oil in which zinc oxide powder was dispersed in 1.2% was used as a solid catalyst, and the recovered liquid was analyzed. Is about 68
%, GL yield was about 47%. The MES component in the reaction solution by the SEC method was 65%, the MG component was 12%, and D
The G component was 13% and the TG component was 10% (shown in Table 1).

Examples 2 to 9 and Comparative Example 2  Using a hot air circulation type electric furnace as the temperature control method,
Table 1 shows the amount of the solvent, the reaction temperature, the reaction time, and the reaction equivalent ratio.
The test was carried out in the same manner as in Example 1 except that the test was performed by changing
gave. These reaction liquids are separated by the GC method and the SEC method.
The results of the analysis are as shown in Table 1.

Examples 10 to 12 and Comparative Example 3  Large dispersion of calcium oxide powder in advance as a solid catalyst
The test was performed in the same manner as in Examples 2 to 9 except that soybean oil was used.
did. The reaction solution was analyzed by GC and SEC methods.
The results were as shown in Table 1.

[0041]

[Table 1]

In the table, MES is a fatty acid methyl ester, MG
Is fatty acid monoglyceride, DG is fatty acid diglyceride,
TG is fatty acid triglyceride and GL is glycerin.

[0043]

According to the present invention, it is possible to provide a method for efficiently producing a fatty acid ester from fats and oils and alcohol under relatively low temperature and low pressure conditions, and a fuel containing the fatty acid ester, and the like. Its industrial value is great. It is also useful from the viewpoint of resource reuse and pollution prevention.

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Claims (11)

[Claims] 1. A process for producing a fatty acid ester from fats and oils and alcohols, the method comprising the steps of:
A method for producing a fatty acid ester and glycerin, wherein the reaction is carried out under a temperature range of 40 ° C. 2. The method for producing fatty acid esters and glycerin according to claim 1, wherein the alcohol is represented by the following general formula (1). Embedded image R—OH (1) (R represents a hydrocarbyl group having 1 to 10 carbon atoms or a hydrocarbyl group having 2 to 10 carbon atoms and substituted by a hydrocarboxyl group.) 3. The method for producing a fatty acid ester and glycerin according to claim 2, wherein R in the general formula (1) is an alkyl group having 1 to 4 carbon atoms. 4. The method for producing a fatty acid ester and glycerin according to claim 3, wherein R in the general formula (1) is a methyl group or an ethyl group. 5. The method for producing a fatty acid ester and glycerin according to claim 4, wherein R in the general formula (1) is a methyl group. 6. The method for producing a fatty acid ester and glycerin according to claim 1, wherein the fat is a waste fat. 7. The method for producing a fatty acid ester and glycerin according to claim 1, wherein the fat or oil is a waste cooking oil. 8. A fuel containing a fatty acid ester produced by the production method according to claim 1. 9. A diesel fuel containing a fatty acid ester produced by the production method according to claim 1. 10. A lubricating base oil containing a fatty acid ester produced by the production method according to claim 1. 11. A fuel oil additive containing a fatty acid ester produced by the production method according to claim 1.