JPWO2008133189A1 - Process for producing fatty acid alkyl ester and / or glycerin from fats and oils - Google Patents

Abstract

When producing fatty acid alkyl esters and / or glycerol by reacting fats and oils with alcohol, active metal components do not elute even if the catalyst is used repeatedly, and excellent catalytic activity is maintained for a long time even in the presence of water. High activity in both transesterification of glycerides contained in fats and oils and esterification of free fatty acids, and high catalytic activity even in the presence of impurities such as free fatty acids (FFA) contained in fats and oils And a method for producing fatty acid alkyl esters and / or glycerin suitable for use in foods, fuels, etc. with high efficiency, by simplifying or eliminating complicated steps such as catalyst recovery steps, etc. An object is to provide a catalyst. A method for producing a fatty acid alkyl ester and / or glycerin comprising the step of bringing an oil and fat into contact with an alcohol in the presence of a catalyst, the catalyst comprising a manganese compound and a tetravalent metal element and / or a tetravalent metal A method for producing a fatty acid alkyl ester and / or glycerin having a compound of a metalloid element.

Description

The present invention relates to a method for producing a fatty acid alkyl ester and / or glycerin. More specifically, the present invention relates to a method for producing a fatty acid alkyl ester and / or glycerin useful for uses such as fuel, food, cosmetics and pharmaceuticals, and a catalyst used therefor.

As fatty acid alkyl esters, those obtained from vegetable oils and fats are used as edible oils, and are also used in the fields of cosmetics, pharmaceuticals and the like. In recent years, it has been attracting attention as a fuel added to light oil and the like. For example, for the purpose of reducing CO ₂ emission, several percent of light oil is added to light oil as a plant-derived biodiesel fuel. Glycerin is mainly used as a raw material for producing nitroglycerin, and is also used in various fields such as raw materials such as alkyd resins, pharmaceuticals, foodstuffs, printing inks and cosmetics. As a method for producing such fatty acid alkyl ester or glycerin, a method is known in which triglyceride, which is the main component of fats and oils, is transesterified with alcohol.
In such a production method, a method using a homogeneous alkali catalyst is generally used industrially, but a complicated catalyst separation and removal step is required. Moreover, since free fatty acids contained in fats and oils are saponified by the alkali catalyst, soap is produced as a by-product, and not only a washing process with a large amount of water is required, but also the fatty acid alkyl ester is not allowed to be washed by the emulsifying action of the soap. The yield may decrease, and the subsequent purification process of glycerin may be complicated.

As a conventional technique for producing glycerin and / or fatty acid alkyl ester from natural fats and oils, a method for producing glycerin and alkyl ester in the presence of a catalyst comprising zinc and aluminum is disclosed (for example, Patent Document 1). reference.). However, when the water content in the raw material is higher than 1500 ppm, there is a problem that soap is generated and the catalytic activity is significantly reduced. Therefore, there is room for improvement such as reducing the decrease in activity even when water is further contained.

Regarding the technology for producing glycerin and / or fatty acid alkyl ester from natural fats and oils, for example, an oxide containing zinc and titanium, an oxide containing zinc, titanium and aluminum, an oxide containing bismuth and titanium, or bismuth And an oxide containing titanium and aluminum are disclosed (for example, refer to Patent Document 2). Also disclosed are a solid catalyst for transesterification reaction containing zirconium oxide and titanium oxide, and a method for producing a fatty acid ester, in which a raw fatty acid ester and a raw alcohol or raw fatty acid are transesterified in the presence of this catalyst. (For example, refer to Patent Document 3).

And a method for producing a fatty acid alkyl ester and / or glycerin comprising a step of bringing an oil and an alcohol into contact with each other in the presence of a catalyst, wherein the catalyst is a metal oxide having an ilmenite structure and / or a srilankite structure. A method for producing a fatty acid alkyl ester and / or glycerin is disclosed (for example, see Patent Document 4).

Furthermore, it is a method for producing glycerin and / or fatty acid alkyl ester, comprising the step of bringing oils and alcohols into contact with each other in the presence of a catalyst, wherein the catalyst comprises zirconium, groups 4, 5, and 8. A method for producing glycerol and / or a fatty acid alkyl ester, which is a metal oxide containing at least one metal element selected from the group as an essential component, and a catalyst thereof are disclosed (for example, see Patent Document 5).
However, in these techniques, for example, there is room for improvement such as further improving the reaction activity and catalyst life and suppressing the decrease in activity even in the presence of free fatty acid (FFA) and / or water contained in the raw material. .

Examples of the technology for producing glycerin and / or fatty acid alkyl ester from natural fats and oils include, for example, a method for producing fatty acid alkyl ester and / or glycerin comprising a step of contacting fats and oils with alcohol in the presence of a catalyst. The catalyst is a single or complex oxide containing at least one metal element selected from the group consisting of group 5 metal elements as an essential component, and crystallized to have the essential component elements in the crystal lattice A method for producing a fatty acid alkyl ester and / or glycerin is disclosed (for example, see Patent Document 6).
In addition, animal and vegetable oils and fats and 2 to 40 times (molar ratio) of alcohol in the presence of a metal oxide catalyst that is 0.1 to 10% by weight of magnesium oxide (MgO) or manganese oxide (MnO). A method for producing a fatty acid ester comprising a step of reacting at 60 to 200 ° C. for 0.5 to 18 hours to obtain a mixture of a fatty acid ester and glycerin and a step of separating the mixture is disclosed (for example, see Patent Document 7). .)
Furthermore, a method of transesterifying a plant or animal-derived triglyceride with a monohydric or polyhydric alcohol in the presence of a heterogeneous solid catalyst, wherein the heterogeneous solid catalyst includes aluminum, chromium, magnesium, zinc, calcium, A method using copper, manganese, or a mixed oxide derived therefrom is disclosed (for example, see Patent Document 8).
However, these techniques further improve the catalyst life, and there is room for contrivance such as suppressing the decrease in activity due to elution of active ingredients even in the presence of free fatty acid (FFA) and / or water contained in the raw material. was there.

As a conventional method for solving the above-mentioned problems, for example, it is conceivable to frequently exchange a catalyst having a decreased activity with a new catalyst in order to avoid a decrease in yield and a decrease in product purity. If the replacement frequency of the catalyst is increased, it is not desirable for industrial production because of a decrease in productivity caused by stopping the apparatus and an increase in catalyst cost. In addition, it is conceivable to prevent reduction in the activity of the catalyst by removing impurities such as free fatty acid (FFA) in advance in water and fat contained in the raw oil and fat, but the impurities are completely removed from a large amount of raw oil and fat. This is very difficult, and it is necessary to add a new process. Therefore, a very complicated operation is required. Therefore, the above catalyst has room for contrivance for making the catalyst difficult to elute active components and maintaining excellent catalytic activity for a long time in the presence of impurities such as water and free fatty acid (FFA). there were.
US Pat. No. 6,878,837 (paragraphs 1 and 6) European Patent No. 1593732 Japanese Patent Laying-Open No. 2005-177722 (page 1-2) JP 2006-225352 A (page 1-2) JP 2006-225578 A (page 1-2) Japanese Patent No. 3941876 (page 1-2) Korean Patent No. 415396 Specification International Publication No. 1998/56747 Pamphlet

The present invention has been made in view of the above situation, and when a fatty acid alkyl ester and / or glycerin is produced by reacting fats and oils with alcohol, elution of the active metal component occurs even if the catalyst is repeatedly used. In addition, excellent catalytic activity can be maintained for a long time even in the presence of water, and high activity can be exhibited in both the transesterification of glycerides contained in fats and oils and the esterification of free fatty acids. Free fatty acids contained in fats and oils Using a catalyst that can exhibit high catalytic activity even in the presence of impurities such as (FFA), complicated processes such as a catalyst recovery process are simplified or unnecessary, and can be used efficiently for edible and fuel applications. It is an object to provide a method for producing a suitable fatty acid alkyl ester and / or glycerin and a catalyst thereof.

The present inventors have made various studies on methods for producing fatty acid alkyl esters and / or glycerin. As a result, there is a method for producing fatty acid alkyl esters and / or glycerin by contacting oils and fats with alcohol in the presence of a solid catalyst. Focusing on the fact that it is industrially useful, various studies have been conducted on the catalyst used in such a process. When a catalyst having a manganese compound and a compound of a tetravalent metal element and / or a tetravalent metalloid element is used, It was found that elution of the active metal component was more sufficiently suppressed, the catalyst life was sufficiently long, high activity could be maintained even in the presence of water, and the starting alcohol was not decomposed. I came up with the idea that the problem could be solved wonderfully. Further, the present inventors have made the effect of extending the catalyst life and the presence of water by using a compound of a tetravalent metal element and / or a tetravalent metalloid element contained in the catalyst as a silicon compound and / or a zirconium compound. It was also found that the effect of maintaining high activity is remarkably exhibited. Achieving both of these simultaneously at a high level is a problem that a person skilled in the art has not been able to achieve for a long time, and is a problem that only the present invention has successfully solved.

That is, the present invention is a method for producing a fatty acid alkyl ester and / or glycerin comprising a step of contacting fats and oils in the presence of a catalyst, wherein the catalyst comprises a manganese compound and a tetravalent metal element. And / or a method for producing a fatty acid alkyl ester and / or glycerin having a compound of a tetravalent metalloid element.
The present invention is also a catalyst for producing a fatty acid alkyl ester and / or glycerin used in the method for producing the fatty acid alkyl ester and / or glycerin.
The present invention is described in detail below.

In the method for producing a fatty acid alkyl ester and / or glycerin of the present invention, fats and oils are brought into contact with alcohol in the presence of a manganese compound and a catalyst having a tetravalent metal element and / or a tetravalent metalloid compound. It will be. The production method of the present invention can not only perform an esterification reaction and a transesterification reaction simultaneously by using a catalyst having a manganese compound and a compound of a tetravalent metal element and / or a tetravalent metalloid element. It is possible to produce a fatty acid alkyl ester and / or glycerin with high catalytic activity and high yield and high selectivity. In addition, the elution of the catalytically active component is sufficiently suppressed and the catalyst life is improved, so that the catalyst recovery process can be remarkably simplified or unnecessary, and is repeatedly used in the reaction. As a result, the recyclability of the catalyst is improved, utility costs and equipment costs can be significantly reduced, catalyst-related costs can be reduced, and stable and long-term production can be achieved. In particular, even in the presence of free fatty acids (FFA), mineral acids, metal components and water contained in fats and oils, soap is not produced as a by-product, and high catalytic activity can be exhibited without being affected by these impurities.

The catalyst in the present invention may be used alone or in combination of two or more, and may contain impurities and other components produced in the catalyst preparation step as long as the effects of the present invention are exhibited. However, it is preferable that the manganese compound and the tetravalent metal element and / or tetravalent metalloid compound are the main components of the catalyst. When the total mass of the catalyst (the catalyst component excluding the support) is 100 parts by mass, the total mass of the manganese compound and the tetravalent metal element and / or tetravalent metalloid element compound is 50 parts by mass or more. It is preferable. More preferably, it is 80 mass parts or more, More preferably, it is 85 mass parts or more, Most preferably, it is 90 mass parts or more, Most preferably, it is 95 mass parts or more.
In the above catalyst, the manganese compound and the tetravalent metal element and / or the tetravalent metalloid compound constitute a component having catalytic activity. Therefore, when the catalyst satisfies the above-described mass ratio and the like, the effect of the present invention can be achieved more remarkably.

Normally, free fatty acids (FFA) and / or water will be present in the fats and oils, and mineral acids, metal components and sterols derived from natural fats and oils used to remove impurities derived from natural fats and oils. And so on. Therefore, in the embodiments of the present invention, mineral acids, metal components, sterols, phospholipids, water, and free fatty acids (FFA) are usually included. In such embodiments, manganese and tetravalent are also included. A form using a complex oxide and / or mixed oxide of a metal element and / or a tetravalent metalloid element is a preferred form.
Of course, since this catalyst can keep the catalytic activity high even under various reaction conditions, for example, when the free fatty acid (FFA) and / or water is not substantially present in the reaction system, or the free fatty acid ( FFA) and / or even when it is not substantially affected by water, it can be suitably used.

Examples of the existence form of the manganese compound in the catalyst include simple substances, alloys, complexes, organic metals, salts, halides, sulfides, cyanides, and oxides. Among these, oxidation is also possible. It is preferable that it is a thing. The presence of manganese as an oxide is advantageous in terms of catalyst stability.
Thus, it is one of the preferred embodiments of the present invention that the catalyst contains a manganese oxide as a manganese compound.
In addition, as a form of an oxide, the form of a single oxide, a complex oxide, and a mixed oxide is mentioned. A single oxide is an oxide in which one atom other than oxygen is present in the same crystal structure, and a composite oxide is an oxide in which two or more atoms other than oxygen are present in the same crystal structure. The mixed oxide is a mixture of two or more single oxides and / or composite oxides.
Note that in this specification, the simple term “composite oxide” means one type of composite oxide that is not a mixed oxide. A mixed oxide of manganese and a single oxide of a tetravalent metal element and / or a tetravalent metalloid element are mixed oxides in this specification.

The manganese oxide is in the form of a single oxide, that is, a single oxide represented by MnO _x (wherein x is a number of 1 or more and 7/2 or less). is there. The manganese single oxide is preferably MnO, MnO _4/3 , MnO _3/2 , MnO ₂ , or MnO _7/2 . More preferred are MnO, MnO _4/3 , MnO _3/2 and MnO ₂ . MnO _4/3 here is synonymous with Mn ₃ O ₄ , MnO _3/2 is synonymous with Mn ₂ O ₃ , and MnO _7/2 is synonymous with Mn ₂ O ₇ .

The manganese oxide in the form of a composite oxide may be crystallized or amorphous, but it is preferable to use a crystallized form. Those having manganese and other metal elements in the crystal lattice are preferred. As the other metal element, for example, one or more of aluminum element, titanium element, chromium element, iron element, cobalt element, nickel element, copper element, zinc element, niobium element, lanthanoid element and the like are preferable.

Examples of the presence form of the tetravalent metal element and / or tetravalent metalloid element compound in the catalyst include, for example, simple substance, alloy, complex, organic metal, salt, halide, sulfide, cyanide, and oxidation. Among these, an oxide is preferable. The presence of a tetravalent metal element and / or a tetravalent metalloid compound as an oxide is advantageous in terms of catalyst stability.

Examples of the tetravalent metal element and / or the tetravalent metalloid element include zirconium, hafnium, tin, lead, silicon, germanium, and titanium. Among these, silicon or zirconium is preferable. .
That is, it is one of preferred embodiments of the present invention that the compound of the tetravalent metal element and / or the tetravalent metalloid element is a silicon compound and / or a zirconium compound.
In the catalyst of the present invention, when the tetravalent metal element and / or the tetravalent metalloid element is silicon and / or zirconium, the catalyst is made difficult to elute the active ingredient, and water and free fatty acid (FFA) are used. In the presence of impurities such as), the effect of maintaining excellent catalytic activity for a long time is remarkably exhibited. In particular, when silicon is used, a catalyst having more excellent catalytic activity in the presence of impurities such as water and free fatty acid (FFA) can be obtained.

It is one of the preferred embodiments of the present invention that the catalyst is in the form of mixed oxide or composite oxide.
Examples of the catalyst in the form of a mixed oxide or composite oxide include, for example, a single oxide and / or composite oxide of manganese and a single element of the above tetravalent metal element and / or tetravalent metalloid element. The form which is a mixed oxide which comprises a monoxide and / or complex oxide is mentioned.

When the tetravalent metal element and / or the tetravalent metalloid element constituting the catalyst is zirconium, it is preferable to combine a manganese compound with a single oxide and / or composite oxide of zirconium. More preferably, it is preferable to combine a single oxide and / or complex oxide of manganese with a single oxide and / or complex oxide of zirconium. More preferably, it is a combination of a single oxide and / or complex oxide of manganese and a single oxide of zirconium. Particularly preferred is MnOx or a combination of MnTiO ₃ and ZrO ₂ . Most preferably, it is a combination of MnTiO ₃ and ZrO ₂ when firing at 950 ° C. or higher, and a combination of MnOx and ZrO ₂ when firing at less than 950 ° C.
Further, in the catalyst having the manganese compound and the zirconium compound, the ratio of the manganese element in the total mass of the manganese element and the zirconium element is preferably 1% or more and 99% or less, and more preferably 3% or more and 95% or less. Preferably, it is 5% or more and 90% or less. The ratio of manganese element and zirconium element in the catalyst can be determined by measuring the catalyst by fluorescent X-ray analysis (XRF) or powder X-ray diffraction (XRD).

When the tetravalent metal element and / or the tetravalent metalloid element constituting the catalyst is zirconium, the oxide of the tetravalent metal element and / or the tetravalent metalloid element is a single oxide of zirconium. It is preferable that A single oxide of zirconium is a compound represented by ZrO ₂ . The zirconium oxide may have any of tetragonal, cubic, and monoclinic structures, but preferably has a monoclinic structure. When the zirconium oxide has such a form, the catalyst is further stabilized.

When the tetravalent metal element and / or the tetravalent metalloid element constituting the catalyst is zirconium, examples of the complex oxide containing manganese and zirconium include Mn _0.2 Zr _0.8 O _1.8 Etc. The composite oxide containing manganese and zirconium is preferably obtained using metal alkoxide as a raw material.

A mixed oxide comprising the above manganese oxide and zirconium oxide, wherein the manganese oxide contains a composite oxide, for example, a co-precipitated solution in which manganese and zirconium are dissolved, It is preferable that the raw material is prepared by supporting a manganese compound with zirconium oxide as a carrier. More preferably, it is obtained by firing the raw material obtained by the above method. More preferably, it is obtained by setting the firing temperature to 280 ° C. or higher and lower than 950 ° C. This is because elution may not be sufficiently suppressed when it is lower than 280 ° C. Most preferably, the calcination temperature is 400 ° C or higher and lower than 950 ° C.
A mixed oxide comprising the above manganese oxide and zirconium oxide, wherein the manganese oxide is a composite oxide, for example, a powder comprising manganese and a powder comprising zirconium It is preferable that the powder is prepared from a raw material. More preferably, the powder mixture is obtained by atomizing and firing. More preferably, the calcination temperature is 950 ° C. or higher and 1300 ° C. or lower. This is because if the temperature exceeds 1300 ° C., a sufficient catalyst surface area cannot be obtained and the fatty acid alkyl ester and / or glycerin may not be produced with high efficiency. This is because the oxide may not be prepared. Most preferably, the calcination temperature is 950 ° C. or more and 1200 ° C. or less. In addition, it is suitable to perform atomization of mixed powder by, for example, extruding and drying with a wet extrusion granulator and shearing with a fine grinding device.
The firing time is preferably 30 minutes or longer and within 24 hours. More preferably, it is 1 hour or more and 12 hours or less. The gas phase atmosphere during firing is preferably air, nitrogen, argon, oxygen or the like. More preferably, the firing is performed in air.

When the tetravalent metal element and / or the tetravalent metalloid element constituting the catalyst is silicon, the catalyst may be a combination of a manganese compound and a single oxide and / or composite oxide of silicon, A compound having manganese and silicon is preferable. More preferably, it is a combination of manganese oxide and silicon single oxide and / or composite oxide, or a composite oxide containing manganese and silicon. More preferably, when firing at 850 ° C. or higher, manganese and silicon composite oxides MnSiO ₃ , MnSi ₂ O ₅ , Mn ₂ SiO ₄ , Mn ₄ SiO ₇ , Mn ₅ Si ₃ O ₁₂ , Mn ₇ SiO ₁₂ and Mn ₇ Si ₇ O ₂₁ are included, and when firing at less than 850 ° C., a combination of MnOx and SiO ₂ . Most preferably, when firing at 850 ° C. or higher, Mn ₇ SiO ₁₂ is included, and when firing at less than 850 ° C., a combination of MnOx and amorphous SiO ₂ . This further stabilizes the catalyst. Incidentally, _Mn 7 _{SiO 12} here has the same meaning as _{Mn 7 O 8 (SiO 4)} .

Further, in the catalyst having the manganese compound and the silicon compound, the ratio of the manganese element in the total mass of the manganese element and silicon is preferably 1% or more and 99% or less, and more preferably 5% or more and 95% or less. More preferably, it is 10% or more and 90% or less. The ratio of the manganese element and the silicon in the catalyst can be determined by measuring the catalyst by fluorescent X-ray analysis (XRF) or powder X-ray diffraction (XRD).

When the mixed oxide comprises the manganese oxide and the silicon oxide and does not include the composite oxide having manganese and silicon, the catalyst contains silicon in a solution containing manganese. It is preferable that the raw material is one obtained by adding to the compound. More preferably, a material obtained by impregnating and supporting manganese by adding an acidic solution dissolving manganese to a solid containing silicon is used as a raw material. More preferably, the mixture is obtained by firing. Even more preferably, the firing temperature is 280 ° C or higher and lower than 850 ° C. This is because elution may not be sufficiently suppressed when it is lower than 280 ° C. It is particularly preferable that the firing temperature is 400 ° C or higher and lower than 850 ° C.
When the composite oxide containing manganese oxide and silicon is included, the catalyst is preferably prepared using a material obtained by adding a solution containing manganese to a compound containing silicon. More preferably, a material obtained by impregnating and supporting manganese by adding an acidic solution dissolving manganese to a solid containing silicon is used as a raw material. More preferably, the mixture is obtained by firing. Even more preferably, the firing temperature is 850 ° C. or higher and 1300 ° C. or lower. This is because if the temperature exceeds 1300 ° C., a sufficient catalyst surface area cannot be obtained and the fatty acid alkyl ester and / or glycerin may not be produced with high efficiency. This is because there is a possibility that a composite oxide having the above cannot be prepared. Most preferably, the calcination temperature is 850 ° C. or more and 1200 ° C. or less.
The firing time is preferably 30 minutes or longer and within 24 hours. More preferably, it is 1 hour or more and 12 hours or less. The gas phase atmosphere during firing is preferably air, nitrogen, argon, oxygen or the like. More preferably, the firing is performed in air.

The production method of the present invention is insoluble (hereinafter also referred to as “insoluble catalyst”) to any of fats and alcohols and products (fatty acid alkyl ester, glycerin, etc.) under reaction conditions. Is preferred. In the reaction in which fats and oils are contacted in the presence of a catalyst, after the reaction is completed, when the alcohol is distilled off in the absence of the catalyst, an upper layer mainly containing fatty acid alkyl ester and a lower layer mainly containing glycerin As a result, the separation between the fatty acid alkyl ester and glycerin can be improved, and the recovery rate can be improved. If the active metal component of the catalyst is eluted, the reverse reaction proceeds in the above steps due to the fact that the transesterification reaction is a reversible reaction, and the yield of the fatty acid alkyl ester decreases. Thus, by performing phase separation after distilling off alcohol from the reaction solution in the absence of a catalyst, purification in the method for producing fatty acid alkyl ester and / or glycerin is facilitated, and the yield can be improved. it can. That is, the production method comprises a step of bringing oils and alcohols into contact with each other in the presence of a catalyst, and the catalyst comprises oils and alcohols and products (fatty acid alkyl ester, glycerin, etc.) under the reaction conditions. A form in which alcohol is distilled off in the absence of a catalyst prior to phase separation of an ester phase and a glycerin phase, which are reaction products, is one of the preferred forms of the present invention. One. In addition, it becomes possible to further improve the separation and purification of fatty acid alkyl ester and glycerin by adding a small amount of water.

The absence of the catalyst means that it contains almost no insoluble solid catalyst and the total concentration of active metal components eluted from the catalyst in the solution after the reaction is 1000 ppm or less. The eluted active metal component refers to a metal component derived from an insoluble solid catalyst dissolved in a reaction solution that can act as a homogeneous catalyst having activity in the transesterification reaction and / or esterification reaction under operating conditions. means. If the concentration of the eluted active metal component exceeds 1000 ppm, the reverse reaction cannot be sufficiently suppressed in the above-described alcohol distillation step, and the utility load in the production cannot be sufficiently reduced. Preferably it is 800 ppm or less, More preferably, it is 600 ppm or less, More preferably, it is 300 ppm or less. Particularly preferably, the active metal component is not substantially contained.
The elution amount of the active metal component of the catalyst in the reaction solution can be measured by fluorescent X-ray analysis (XRF) while the reaction solution after the reaction is in a solution state. Moreover, when measuring a very small amount of elution, it is preferable to measure by a high frequency induction plasma (ICP) emission analysis method.

In the production method of the present invention, as the metal oxide, as described above, the metal oxide has a performance capable of performing an esterification reaction and a transesterification reaction at the same time, and influences of mineral acids and metal components contained in the oil and fat. Therefore, the fatty acid alkyl ester and / or glycerin can be produced with high efficiency in the production method of the present invention.

The method for producing a fatty acid alkyl ester and / or glycerin of the present invention comprises a step of bringing oils and alcohols into contact with each other in the presence of a catalyst.
In the contact step, for example, as shown in the following formula, fatty acid methyl ester and glycerin are generated by transesterification of triglyceride and methanol.

In the formula, R is the same or different and represents an alkyl group having 6 to 24 carbon atoms or an alkenyl group having 6 to 24 carbon atoms having one or more unsaturated bonds. As these carbon number, More preferably, it is C10-22, More preferably, it is C12-22.
In the above production method, since the transesterification reaction and the esterification reaction can be performed simultaneously by using the above-described catalyst, even if the fats and oils as raw materials contain free fatty acids, in the transesterification reaction step At the same time, since the esterification reaction of free fatty acid proceeds, the yield of fatty acid alkyl ester can be improved without providing an esterification reaction step separately from the ester exchange reaction step.
In the production method, as shown in the above formula, glycerin is obtained together with the fatty acid alkyl ester by transesterification. In the present invention, purified glycerin can be easily obtained industrially, but such glycerin can be suitably used for various applications as a chemical raw material.

In the above contact step, the fats and oils contain fatty acid esters of glycerin and may be used as raw materials for fatty acid alkyl esters and / or glycerin together with alcohol, and are generally referred to as “fats and fats”. Can be used. Oils and fats usually contain triglycerides (triesters of glycerin and higher fatty acids) as the main component and contain a small amount of diglycerides, monoglycerides and other subcomponents. Tripalmitin or the like may be used as long as any of triglyceride, diglyceride and monoglyceride is contained in a small amount.
Specific examples of the fats and oils include rapeseed oil, sesame oil, soybean oil, corn oil, sunflower oil, palm oil, palm kernel oil, coconut oil, safflower oil, linseed oil, cottonseed oil, tung oil, castor oil, and coconut oil. Vegetable oils and fats; animal fats and oils such as beef tallow, pork oil, fish oil and whale fat; used oils (waste cooking oils) of various edible oils, etc. are suitable, and these may be used alone or in combination of two or more. it can. Furthermore, these oils and fats may contain organic acids, may contain fatty acid alkyl esters and / or glycerin obtained by the reaction, and may have been subjected to pretreatment such as deoxidation.

When the fats and oils contain phospholipids, proteins, and the like as impurities, it is preferable to use a product obtained by adding a mineral acid such as sulfuric acid, nitric acid, phosphoric acid, boric acid, etc. and performing a degumming step for removing the impurities. Since the method for producing a fatty acid alkyl ester and / or glycerin of the present invention is such that the catalyst is less susceptible to reaction inhibition by mineral acid, after performing the degumming step, the fats and oils contain mineral acid, A fatty acid alkyl ester and / or glycerin can be produced efficiently.

In the above contact step, the alcohol is preferably an alcohol having 1 to 6 carbon atoms, more preferably an alcohol having 1 to 3 carbon atoms, for the purpose of producing biodiesel fuel. Examples of the alcohol having 1 to 6 carbon atoms include methanol, ethanol, propanol, isopropyl alcohol, 1-butanol, 2-butanol, t-butyl alcohol, 1-pentanol, 3-pentanol, 1-hexanol, 2- Examples include hexanol. In particular, methanol or ethanol is preferable. You may use these 1 type or in mixture of 2 or more types.
The alcohol is preferably a polyol for the purpose of producing edible oils, cosmetics, medicines and the like. As the polyol, ethylene glycol, propylene glycol, glycerin, pentaerythritol, sorbitol and the like are suitable. Among these, glycerin is preferable. You may use these 1 type or in mixture of 2 or more types. Thus, when using a polyol as said alcohol, the manufacturing method of the fatty-acid alkylester of this invention can be used suitably in the method of obtaining glycerides.
In the manufacturing method of the said fatty-acid alkylester and / or glycerol, other components other than fats and oils, alcohol, and a catalyst may exist.

As the usage-amount of the said alcohol, it is preferable that it is 1-30 times the theoretical required amount in reaction of fats and oils and alcohol. If it is less than 1 time, the fats and alcohols may not react sufficiently, and the conversion rate may not be sufficiently improved. If it exceeds 30 times, the amount of excess alcohol recovered and recycled increases, which may increase costs. It is more preferably 1.2 to 20 times, further preferably 1.5 to 15 times, and more preferably 2 to 10 times.
The theoretical required amount of alcohol referred to in the present invention means the number of moles of alcohol corresponding to the saponification value of fats and oils, and can be calculated by the following formula.
Theoretical required amount of alcohol (kg) = molecular weight of alcohol × [amount of used fat (kg) × saponification value (g-KOH / kg-fat) / 56100]

When a polyol is used as the alcohol, diglycerides can be suitably obtained by the method for producing a fatty acid alkyl ester of the present invention as described above, and such a form is one of the preferred embodiments of the present invention. It is. The diglycerides thus obtained can be suitably used in the food field and the like as additives for improving the plasticity of fats and oils. In addition, when diglycerides are used as edible oils and blended in various foods, they exhibit obesity prevention, weight gain inhibitory action, etc., so the form using the diglycerides obtained by the present invention as edible oils is also present. It is one of the preferred embodiments of the invention.
In the form of obtaining the above diglycerides, for example, when glycerin is used as a polyol, a reaction as shown in the following formula proceeds.

In the formula, R is the same or different and represents an alkyl group having 6 to 22 carbon atoms or an alkenyl group having 6 to 22 carbon atoms having one or more unsaturated bonds.

In the method for producing a fatty acid alkyl ester and / or glycerin of the present invention, the reaction temperature is preferably 100 ° C. at the lower limit and 300 ° C. at the upper limit. If it is less than 100 ° C, the reaction rate may not be sufficiently improved, and if it exceeds 300 ° C, side reactions such as alcohol decomposition may not be sufficiently suppressed. More preferably, the lower limit is 120 ° C. and the upper limit is 270 ° C., and more preferably the lower limit is 150 ° C. and the upper limit is 235 ° C.
In addition, as a catalyst used for the manufacturing method of the said fatty-acid alkylester and / or glycerol, when using at the reaction temperature within the said range, it is preferable that an active metal component does not elute. By using such a catalyst, the activity of the catalyst can be sufficiently maintained even when the reaction temperature is high, and the reaction can be carried out satisfactorily.

In the method for producing the fatty acid alkyl ester and / or glycerin, the reaction pressure is preferably a lower limit of 0.1 MPa and an upper limit of 10 MPa. If it is less than 0.1 MPa, the reaction rate may not be sufficiently improved, and if it exceeds 10 MPa, the side reaction may easily proceed. In addition, a special device that can withstand high pressure is required, and utility costs and facility costs may not be sufficiently reduced. More preferably, the lower limit is 0.2 MPa and the upper limit is 9 MPa, and more preferably the lower limit is 0.3 MPa and the upper limit is 8 MPa.

Even when such reaction temperature and pressure are set, in the method for producing a fatty acid alkyl ester and / or glycerin according to the present invention, since a highly active catalyst is used as described above, the reaction can be carried out satisfactorily. It becomes possible.
In addition, the said catalyst (catalyst which has a manganese compound and a zirconium compound) can also be used on the supercritical conditions of the alcohol to be used. The supercritical condition refers to a region exceeding the critical temperature and critical pressure inherent to the substance. When methanol is used as the alcohol, the temperature is 239 ° C. or higher and the pressure is 8.0 MPa or higher. By using the catalyst, fatty acid alkyl ester and / or glycerin can be efficiently produced even under supercritical conditions.

Moreover, in the manufacturing method of the said fatty-acid alkylester and / or glycerol, as a catalyst amount used for reaction, in the case of a batch type, a minimum is 0.5 mass% and an upper limit is 20 with respect to the total preparation mass of fats and oils, alcohol, and a catalyst. It is preferable that it is mass%. If it is less than 0.5% by mass, the reaction rate may not be sufficiently improved, and if it exceeds 20% by mass, the catalyst cost may not be sufficiently reduced. More preferably, the lower limit is 1.5% by mass and the upper limit is 10% by mass. In addition, in the case of a fixed bed flow system, the contact liquid amount relative to the catalyst per unit time calculated by the following equation (LHSV) is a lower limit of 0.1 hr ^-1, it is preferable upper limit is 10 hr ^-1. More preferably, the lower limit is 0.3 hr ⁻¹ and the upper limit is 5 hr ⁻¹ .
LHSV (hr ⁻¹ ) = {flow rate of fat / oil per hour (L · hr ⁻¹ ) +1 flow rate of alcohol per hour (L · hr ⁻¹ )} / catalyst capacity (L)

A preferable form of the contact step is a batch type (batch type) or a continuous flow type, and among them, a fixed bed flow type is preferable because a catalyst separation step is unnecessary. That is, the contact step is preferably performed using a fixed bed flow reactor. Moreover, as a preferable form of the batch type, the catalyst is put into a mixed system of fats and oils and alcohol.

In the production method of the present invention, since a recycling process can be easily established by using the above catalyst, unreacted raw materials, intermediate glycerides and the like may be included after the reaction is completed. In this case, for example, after distilling off light-boiling components such as alcohol and water in the absence of a catalyst from the mixed solution after completion of the reaction, unreacted glycerides and free fatty acids are separated and recovered to obtain raw materials. A process of mixing and reacting again is preferred. Thereby, it becomes possible to obtain a high-purity fatty acid alkyl ester and glycerin with higher yield, and the purification cost can be further reduced.

In the production method of the present invention, in order to obtain a higher purity fatty acid alkyl ester or glycerin, it is preferable to construct a multistage reaction process. In particular, when a fatty acid alkyl ester is used for fuel added to light oil or the like, it is necessary to produce a higher purity fatty acid alkyl ester. When the above catalyst is used, a small amount of intermediate glyceride can also be efficiently converted into a fatty acid alkyl ester. Therefore, a high-purity fatty acid alkyl ester or glycerin can be produced by using a multistage reaction process. In this case, for example, after removing light boiling components such as alcohol in the absence of a catalyst from the reaction solution after completion of the reaction, the solution after separating and removing glycerin by a method such as phase separation is mixed with alcohol, A process of reacting again is preferred. Thereby, it becomes possible to obtain a high-purity fatty acid alkyl ester and glycerin with higher yield, and the purification cost can be further reduced.

The fatty acid alkyl ester obtained by the production method of the present invention is suitably used for various uses as a raw material for industrial raw materials and pharmaceuticals, a fuel and the like. Among these, diesel fuel using fatty acid alkyl esters obtained from vegetable oils and waste cooking oils by the above production method can sufficiently reduce utility costs and equipment costs in the production process, and does not require a catalyst recovery process. Since the catalyst can be repeatedly used, the environmental conservation effect can be sufficiently exerted from the manufacturing stage, and can be suitably used as various fuels. The diesel fuel containing the fatty acid alkyl ester obtained by the above production method is also one aspect of the present invention.

The preferable form of the manufacturing process in the manufacturing method of the fatty-acid alkylester and / or glycerol of this invention is shown to FIG. Note that the present invention is not limited to these forms.
In FIG. 1, the process of making these contact in presence of a catalyst is shown by fats and oils and alcohol by batch type. In such a form, fats and alcohol and alcohol are mixed with a catalyst, and reaction is performed. This reaction solution is allowed to stand to separate into an ester phase mainly containing fatty acid alkyl esters and glycerides and a glycerin phase mainly containing glycerol and alcohol. Alcohol and a catalyst are added to the ester phase obtained by separating the glycerin phase, and the reaction is further performed. The ester phase and the glycerin phase are separated to obtain a fatty acid alkyl ester and glycerin. In such a form, before the reaction solution is phase-separated and after the solid catalyst is separated and removed from the liquid phase by a process such as filtration, the alcohol is distilled off to obtain the fatty acid alkyl esters and glycerin. It is preferable at the point which can improve isolation | separation. The fatty acid alkyl ester and / or glycerin thus obtained may be further purified by operations such as distillation, adsorption removal, and water washing, depending on the purpose.

In FIG. 2, the process of making these contact with a catalyst in the filling reaction tube which made the solid catalyst the stationary phase using fats and oils and alcohol by the fixed bed continuous flow-type reaction apparatus is shown. The post-reaction solution reacted in the catalyst-filled reaction tube is allowed to stand in a settler and separated into an ester phase and a glycerin phase. The ester phase obtained by separating the glycerin phase is further reacted with alcohol in a catalyst-packed reaction tower to distill off the alcohol from the post-reaction solution, and then left in a settler to leave the ester phase and glycerin. Separated into phases to obtain fatty acid alkyl ester and glycerin. The fatty acid alkyl ester and / or glycerin thus obtained may be further purified by operations such as distillation, adsorption removal, and water washing, depending on the purpose.

The present invention is also a catalyst for producing a fatty acid alkyl ester and / or glycerin used in the method for producing the fatty acid alkyl ester and / or glycerin.
As for the form, structure, production method, and specific examples of the catalyst, those described above are suitable.
By using such a catalyst in the above production method, there is no leaching (elution) even if it is used repeatedly, it can be used for a long time, and the process for separating and purifying the catalyst should be simplified. Can be made economically. In addition, the manufacturing method of this invention may include other processes, such as a separation process and a refinement | purification process, as mentioned above.
Furthermore, as a preferred embodiment of the present invention, there is also a method of using the above oxide as a catalyst in a fatty acid alkyl ester and / or glycerin comprising a step of contacting fats and oils with an alcohol in the presence of a catalyst.
The details in the method of use are the same as in the manufacturing method.

Since the method for producing a fatty acid alkyl ester and / or glycerin according to the present invention has the above-described configuration, the following effects can be achieved.
In terms of simplifying the reaction process,
(1) The catalyst separation and removal step can be simplified or made unnecessary.
(2) The process of removing moisture in the raw material can be simplified or made unnecessary.
(3) Not only transesterification of fats and oils, but also esterification of free fatty acids in fats and oils proceeds simultaneously.
(4) Since the activity can be maintained for a long period of time, a complicated process such as a catalyst regeneration step can be eliminated.
In terms of simplifying the purification process,
(1) Since the elution of the active ingredient is not observed even when the catalyst is repeatedly used for a long time, the catalytic reverse reaction does not occur after the catalyst separation, so that the alcohol can be sufficiently distilled off, and the liquid-liquid two-phase The distribution equilibrium is improved (the mutual solubility is lowered), and the separation process other than the phase separation process can be simplified or made unnecessary.
(2) Since the catalyst is highly active and has a long life, a highly pure fatty acid alkyl ester and / or glycerin can be produced by a simple purification process.

FIG. 1 is a schematic diagram showing one of the preferred forms of the production process in the method for producing a fatty acid alkyl ester and / or glycerin of the present invention. FIG. 2 is a schematic diagram showing one of the preferred forms of the production process in the method for producing a fatty acid alkyl ester and / or glycerin of the present invention. FIG. 3-1 is a chart showing an XRD pattern of the catalyst prepared in Catalyst Preparation Example 1. FIG. 3-2 is a chart showing the content calculated from the XRD pattern of the catalyst prepared in Catalyst Preparation Example 1. FIG. 4-1 is a chart showing an XRD pattern of the catalyst prepared in Catalyst Preparation Example 2. FIG. 4-2 is a chart showing the content calculated from the XRD pattern of the catalyst prepared in Catalyst Preparation Example 2. FIG. 5-1 is a chart showing an XRD pattern of the catalyst prepared in Catalyst Preparation Example 3. FIG. 5-2 is a chart showing the content calculated from the XRD pattern of the catalyst prepared in Catalyst Preparation Example 3. FIG. 6 is a chart showing the XRD pattern of the catalyst prepared in Catalyst Preparation Example 5. FIG. 7 is a chart showing changes in palm oil conversion, methyl ester yield, and glycerin yield in Examples 5 and 6. FIG. 8 is a chart showing changes in palm oil conversion, methyl ester yield, and glycerin yield in Examples 7 and 8. FIG. 9-1 is a chart showing an XRD pattern of the catalyst prepared in Catalyst Preparation Example 6. FIG. 9-2 is a chart showing the content calculated from the XRD pattern of the catalyst prepared in Catalyst Preparation Example 6. FIG. 10-1 is a chart showing an XRD pattern of the catalyst prepared in Catalyst Preparation Example 7. FIG. 10-2 is a chart showing the content calculated from the XRD pattern of the catalyst prepared in Catalyst Preparation Example 7. FIG. 11-1 is a chart showing an XRD pattern of the catalyst prepared in Catalyst Preparation Example 8. FIG. 11-2 is a chart showing the content calculated from the XRD pattern of the catalyst prepared in Catalyst Preparation Example 8. FIG. 12 is a chart showing the XRD pattern of the catalyst prepared in Catalyst Preparation Example 9. FIG. 13 is a chart showing changes in conversion rate of palm oil, yield of methyl ester, and yield of glycerin in Example 9. FIG. 14 is a chart showing changes in the conversion rate of palm oil, the yield of methyl ester, and the yield of glycerin in Example 10. FIG. 15 is a chart showing changes in the conversion rate of palm oil, the yield of methyl ester, and the yield of glycerin in Example 11. FIG. 16 is a chart showing an XRD pattern of the catalyst prepared in Comparative Catalyst Preparation Example 1.

Explanation of symbols

1: Alcohol, oil and fat, catalyst 2: Glycerin phase (glycerin)
3: First separation 4: Ester phase (fatty acid alkyl ester, glycerides)
5: Distill off alcohol 6: Alcohol, catalyst 7: Second separation 8: Glycerin phase (glycerin)
9: Ester phase (fatty acid alkyl ester)
10: Distill off alcohol 11: Oil, alcohol 12: Catalyst 13: Glycerin phase (glycerin)
14: Settler 15: Ester phase (fatty acid alkyl ester, glycerides)
16: Distill off the alcohol 17: Alcohol 18: Catalyst 19: Settler 20: Glycerin phase (Glycerin)
21: Ester phase (fatty acid alkyl ester)
22: Distilling off alcohol 23: ZrO ₂ peak 24: MnO _4/3 peak 25: Mn _0.2 Zr _0.8 O _1.8 peak 26: ZrO ₂ peak 27: MnTiO ₃ peak 28: Mn ₇ O ₈ (SiO ₄ ) peak 29: Mn ₂ O ₃ peak 30: ZrO ₂ peak 31: Mn ₂ O ₃ peak 32: TiO ₂ peak 33: Mn ₂ O ₃ peak 34: Mn ₇ Peak of O ₈ (SiO ₄ )

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.
The conversion and yield in the examples were calculated by the following formula.
Conversion rate (%) = (Mole number of fat or fatty acid consumed at the end of reaction) / (Mole number of fat or fatty acid charged) × 100 (%)
Methyl ester yield (mol%) = (number of moles of methyl ester formed at the end of reaction) / (number of moles of effective fatty acids at the time of charging) × 100 (%)
Yield of glycerin (mol%) = (number of moles of free glycerin produced at the end of reaction) / (number of moles of effective glycerin component at the time of preparation) × 100 (%)

Effective fatty acids refer to triglycerides, diglycerides, monoglycerides and free fatty acids of fatty acids contained in oils and fats. That is, the number of moles of effective fatty acids at the time of preparation is calculated by the following formula.
Number of moles of effective fatty acids at the time of charging (mol) = [Feed amount of fats and oils (g) × Saponification value of fats and oils (mg-KOH / g-oil and fat) / 56100] + Number of moles of charged fatty acids (mol)
In addition, the effective glycerin component refers to a component capable of producing glycerin by the method of the present invention, and specifically refers to triglycerides, diglycerides, and monoglycerides of fatty acids contained in fats and oils. The content of the effective glycerin component is calculated by quantifying the amount of glycerin liberated by saponifying fats and oils (reaction raw materials) by gas chromatography.

Catalyst preparation example 1 (MnO _x / ZrO ₂ )
145 g of a 50% aqueous solution of manganese nitrate and 200 g of a 25% aqueous solution of zirconium oxynitrate were mixed, and 1000 mL of pure water was added. To this aqueous solution, 4 mol / L aqueous ammonia was added until the pH reached 7. The precipitate was filtered, washed with water, and calcined at 1000 ° C. for 5 hours in an air atmosphere. Further, the XRD pattern of the catalyst obtained in Catalyst Preparation Example 1 and the contents calculated from the XRD pattern are shown in FIGS. 3-1 and 3-2, respectively. The XRD pattern was measured as follows.
Apparatus: X'pert PRO made by PANalytical
Measurement condition X-ray output setting: 40 mA, 45 kV
Tube: Cu tube measurement range: 20-80 or 5-80 (° 2 Theta)
Scanning speed: 1 (° 2 Theta / min)
Step size: 0.001 (° 2 Theta / min)
In FIG. 3-1, FIG. 4-1, FIG. 5-1, FIG. 6, FIG. 9-1, FIG. 10-1, FIG. 11-1, FIG. Represents the diffraction angle (°), and “Counts” represents the intensity of the diffracted X-ray.

Catalyst preparation example 2 (Mn _0.2 Zr _0.8 O _1.8 )
A solution obtained by mixing 23.4 g of a 70% propanol solution of zirconium tetrapropoxide and 100 mL of isopropanol was refluxed at normal pressure. While refluxing, a solution prepared by dissolving 12.26 g of manganese acetate tetrahydrate in 100 mL of water was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred for 3 hours under reflux conditions. The obtained precipitate was filtered, washed with water, and calcined at 700 ° C. for 5 hours in an air atmosphere. Further, the XRD pattern of the catalyst obtained in Catalyst Preparation Example 2 and the contents calculated from the XRD pattern are shown in FIGS. 4-1 and 4-2, respectively.

Catalyst preparation example 3 (MnTiO ₃ / ZrO ₂ )
99.5 g of manganese carbonate, 55.5 g of anatase-type titanium oxide, 36 g of zirconium oxide, and 3.91 g of alkyl cellulose (Metroze 90SH-15000 manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed well. To the mixed powder, 73 g of water was added in several portions uniformly and mixed well. This was extruded from a hole having a diameter of 0.4 mm by a wet extrusion granulator (Dome Gran DG-L1 manufactured by Fuji Paudal Co., Ltd.). The extruded product was dried at 120 ° C. for one day and night, and was sheared to a length of about 5 mm with a fine pulverizer (a sample mill manufactured by Fuji Powder Co., Ltd.). The sheared product was fired at 1000 ° C. for 5 hours in an air atmosphere. Further, the XRD pattern of the catalyst obtained in Catalyst Preparation Example 3 and the contents calculated from the XRD pattern are shown in FIGS. 5-1 and 5-2, respectively.

Catalyst preparation example 4 (MnTiO ₃ )
353 g of manganese carbonate, 196 g of anatase-type titanium oxide, and 8 g of alkyl cellulose (Metrozu 90SH-15000 manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed well. To the mixed powder, 150 g of water was added in several portions uniformly and mixed well. This was extruded from a hole having a diameter of 0.4 mm by a wet extrusion granulator (Dome Gran DG-L1 manufactured by Fuji Paudal Co., Ltd.). The extruded product was dried at 120 ° C. for one day and night, and was sheared to a length of about 5 mm with a fine pulverizer (a sample mill manufactured by Fuji Powder Co., Ltd.). The sheared product was fired at 1000 ° C. for 5 hours in an air atmosphere.

Example 1 (MnO _x / ZrO ₂ )
Palm oil (55.35 g), palmitic acid (6.15 g), methanol (20 g) and 2.5 g of the catalyst synthesized in Catalyst Preparation Example 1 were charged into an autoclave having a capacity of 200 mL. After the nitrogen substitution, the reaction was carried out for 6 hours at 200 ° C. with stirring inside. As a result, the conversion of palm oil was 100%, and the conversion of palmitic acid was 93%.

Example 2 (Mn _0.2 Zr _0.8 O _1.8 )
The reaction was performed in the same manner as in Example 1 except that palm oil (58.42 g), palmitic acid (3.08 g), the catalyst was synthesized in Catalyst Preparation Example 2, and the reaction time was 3 hours. However, the conversion rate of palm oil was 98%, and the conversion rate of palmitic acid was 89%.

Example 3 (MnTiO ₃ / ZrO ₂ )
It carried out on the following reaction conditions using the fixed bed pipe | tube type | mold flow reactor.
Reaction conditions: reaction temperature 200 ° C., reaction pressure 5 MPa, catalyst: catalyst synthesized in Catalyst Preparation Example 3 (MnTiO ₃ / ZrO ₂ ), catalyst amount: 15 mL, LHSV = 1 hr ⁻¹
Reactants: Purified Palm Oil 6.3 g · ^{hr -1} and methanol 6.3 g · ^{hr -1,} the supply amount of methanol to palm oil, it was 9 times the stoichiometric required amount.
From 4 hours after the stabilization of the reaction, water was added to the raw material so that the water content in the reaction system was 1% by mass, and the reaction was allowed to proceed for 24 hours. Then, the activity change of the catalyst was measured by returning to the raw material without moisture (<300 ppm). The results are shown in Table 1 below.

Example 4 (MnTiO ₃ )
The reaction was performed in the same manner as in Example 3 except that LHSV was set to 2 hr ⁻¹ and the catalyst obtained in Catalyst Preparation Example 4 (MnTiO ₃ ) was used. The results are shown in Table 1 below.

The results shown in Table 1 are examined as follows.
The catalyst (MnTiO ₃ / ZrO ₂ ) used in Example 3 did not change greatly in activity even under conditions of 1% water for 24 hours, whereas the catalyst (MnTiO ₃ ) used in Example 4 did not change. ₃ ) It can be seen that the catalyst has a high activity in the absence of water, but the activity decreases when exposed to conditions containing 1% of water for 24 hours.

Catalyst preparation example 5 Mn ₇ O ₈ (SiO ₄ )
20 g of Caractect Q50 (trade name, manufactured by Fuji Silysia, particle size: 180 to 500 μm) was impregnated and supported with 40 g of a 50% aqueous solution of manganese nitrate. After drying at 100 ° C. for a whole day and night, baking was performed at 1000 ° C. for 5 hours in an air stream. The catalyst after calcination had a structure of Mn ₇ O ₈ (SiO ₄ ) as a result of XRD measurement, and the content was 100%. The XRD pattern of the catalyst obtained in Catalyst Preparation Example 5 is shown in FIG.

Example 5 Mn ₇ O ₈ (SiO ₄ )
It carried out on the following reaction conditions using the fixed bed pipe | tube type | mold flow reactor.
Reaction conditions: reaction temperature 200 ° C., reaction pressure 5 MPa, catalyst: catalyst Mn ₇ O ₈ (SiO ₄ ) synthesized in Catalyst Preparation Example 5, catalyst amount: 15 mL, LHSV = 1 hr ⁻¹
Reactants: Purified Palm Oil 6.3 g · ^{hr -1} and methanol 6.3 g · ^{hr -1,} the supply amount of methanol to palm oil, it was 9 times the stoichiometric required amount.
As a result, even after 700 hours, the conversion rate of palm oil, the yield of methyl ester, and the yield of glycerin were not reduced. FIG. 7 shows changes in the conversion rate of palm oil, the yield of methyl ester, and the yield of glycerin until 700 hours elapse.

Example 6
The reaction was performed in the same manner as in Example 5 except that the catalyst obtained in Catalyst Preparation Example 4 (MnTiO ₃ ) was used. The result is shown in FIG.

The results shown in FIG. 7 are examined as follows.
The catalyst (MnTiO ₃ ) used in Example 6 is highly active with a conversion rate of palm oil of 95% even after 200 hours from the start of the reaction. However, when 700 hours have elapsed after the start of the reaction, the conversion rate of palm oil is 90% or more, and although the activity is high, the activity tends to decrease. However, the catalyst (Mn ₇ O ₈ (SiO ₄ )) used in Example 5 is more active than the highly active MnTiO 3 in 200 hours after the reaction, and the conversion rate of palm oil is almost 100%. Furthermore, even after 700 hours from the start of the reaction, no significant decrease in activity was observed, indicating that high activity was maintained for a long time. That is, it was found that the catalyst used in Example 5 had a higher activity and a longer life than the catalyst used in Example 6.

Example 7 Mn ₇ O ₈ (SiO ₄ )
Reaction conditions: reaction temperature 200 ° C., reaction pressure 5 MPa, catalyst: catalyst Mn ₇ O ₈ (SiO ₄ ) synthesized in Catalyst Preparation Example 5, catalyst amount: 15 mL, LHSV = 1 hr ⁻¹
Reactants: Purified Palm Oil 6.3 g · ^{hr -1} and methanol 6.3 g · ^{hr -1,} the supply amount of methanol to palm oil, it was 9 times the stoichiometric required amount.
After the reaction was stabilized, water was added to the raw material so that the water content in the reaction system was 1500 ppm. Even after 350 hours from the addition of water, no reduction in the conversion of palm oil, the yield of methyl ester, and the yield of glycerin was observed. FIG. 8 shows changes in the conversion rate of palm oil, the yield of methyl ester, and the yield of glycerin until 350 hours have elapsed after the addition of water.

Example 8
The reaction was performed in the same manner as in Example 7 except that the catalyst obtained in Catalyst Preparation Example 4 (MnTiO ₃ ) was used. The result is shown in FIG.

The results shown in FIG. 8 are examined as follows.
The catalyst (MnTiO ₃ ) used in Example 8 has a conversion rate of palm oil of 95% or more even when 70 hours have passed since the water in the system was kept at 1500 ppm, and high even if moisture was present in the system. Maintains activity. When this catalyst was also kept at 1500 ppm of water for 350 hours, the conversion rate of palm oil was as high as about 95%, but the methyl ester yield and glycerin yield tended to decrease. However, the catalyst used in Example 7 ((Mn ₇ O ₈ (SiO ₄ )) had a conversion rate of palm oil of 97% or more even after 70 hours had passed since the water in the system was kept at 1500 ppm. Even if this state is maintained, there is no change in the conversion rate of palm oil, the yield of methyl ester, and the yield of glycerin, and no decrease in activity is observed. It was found that even in the presence of water, the activity is high and the activity is maintained for a long time.

Catalyst preparation example 6 (MnOx / SiO ₂ )
The synthesis was performed in the same manner as in Catalyst Preparation Example 5, except that the calcination temperature was 800 ° C. As a result of XRD measurement, it had a structure of Mn ₂ O ₃ . The XRD pattern of the catalyst obtained in Catalyst Preparation Example 6 and the contents calculated from the XRD pattern are shown in FIGS. 9-1 and 9-2, respectively.

Catalyst preparation example 7 (MnOx / ZrO ₂ )
Zirconium oxide (BOP-3M) manufactured by Daiichi Rare Element Chemical Co., Ltd. was crushed and sieved to 125 to 500 μm. The sieved zirconium oxide was dried well. 80.0 g of the zirconium oxide thus obtained was impregnated with 25.3 g of a 50% aqueous solution of manganese nitrate. After drying at 120 ° C. for a whole day and night, baking was performed at 800 ° C. for 5 hours in an air stream. As a result of XRD measurement, the catalyst after calcination had a structure of ZrO ₂ and Mn ₂ O ₃ . The XRD pattern of the catalyst obtained in Catalyst Preparation Example 7 and the contents calculated from the XRD pattern are shown in FIGS. 10-1 and 10-2, respectively.

Catalyst preparation example 8 (MnOx / TiO ₂ )
Titanium oxide (ST-31119) manufactured by Norton was crushed to 125 to 500 μm and sieved. The screened titanium oxide was thoroughly dried. The titanium oxide thus obtained was impregnated and supported on 31.5 g of a 50% aqueous solution of manganese nitrate. After drying at 120 ° C. for a whole day and night, baking was performed at 800 ° C. for 5 hours in an air stream. The catalyst after calcination had a structure of TiO ₂ and Mn ₂ O ₃ as a result of XRD measurement. The XRD pattern of the catalyst obtained in Catalyst Preparation Example 8 and the contents calculated from the XRD pattern are shown in FIGS. 11-1 and 11-2, respectively.

Catalyst preparation example 9 (Mn ₇ O ₈ (SiO ₄ ))
The synthesis was performed in the same manner as in Catalyst Preparation Example 5 except that the calcination temperature was 900 ° C. As a result of XRD measurement, the calcined catalyst had a structure of Mn ₇ O ₈ (SiO ₄ ), and its content was 100%. The XRD pattern of the catalyst obtained in Catalyst Preparation Example 9 is shown in FIG.

Catalyst preparation example 10 (Mn ₇ O ₈ (SiO ₄ ))
The synthesis was performed in the same manner as in Catalyst Preparation Example 5 except that the calcination temperature was 900 ° C. and the amount of 50% manganese nitrate aqueous solution was 10 g. The catalyst after calcination results of XRD measurement _had a structure of _{Mn 7 O 8 (SiO 4)} . As a result of XRF measurement, the ratio of manganese element to the total mass of manganese element and silicon in the entire catalyst was 10%.

Example 9
The reaction was carried out under the same conditions as in Example 5 except that the catalyst was synthesized in Catalyst Preparation Example 6, the catalyst amount was 7.5 mL, and LHSV was 2 hr ⁻¹ .
As a result, even after 270 hours, the conversion rate of palm oil, the yield of methyl ester, and the yield of glycerin were not reduced. Changes in palm oil conversion, methyl ester yield, and glycerin yield until 270 hours elapse are shown in FIG.

Example 10
The experiment was performed in the same manner as in Example 5 except that the catalyst synthesized in Catalyst Preparation Example 7 was used as the catalyst. As a result, even if 500 hours passed, the conversion rate of palm oil, the yield of methyl ester, and the yield of glycerin were not reduced. FIG. 14 shows changes in the conversion rate of palm oil, the yield of methyl ester, and the yield of glycerin until 500 hours elapse.

Example 11
The experiment was performed in the same manner as in Example 5 except that the catalyst synthesized in Catalyst Preparation Example 8 was used as the catalyst. As a result, even if 300 hours passed, the conversion rate of palm oil, the yield of methyl ester, and the yield of glycerin were not reduced. Changes in the conversion rate of palm oil, the yield of methyl ester, and the yield of glycerin until 300 hours elapse are shown in FIG.

The results of FIGS. 7, 13, 14, and 15 are examined as follows.
The catalyst (MnTiO ₃ ) used in Example 6 is highly active with a conversion rate of palm oil of 95% even after 200 hours from the start of the reaction. However, the catalyst used in Example 9 (MnOx / SiO ₂ ), the catalyst used in Example 10 (MnOx / ZrO ₂ ), and the catalyst used in Example 11 (MnOx / TiO ₂ ) The conversion rate of oil is 98% or more, and no further decrease in activity is observed. Among them, the catalyst used in Example 9 has a high activity even when LHSV is set to 2 hr ⁻¹ , and is found to be significantly higher than that of MnTiO ₃ , which has been highly active until now. The fact that LHSV is highly active even at 2 hr ⁻¹ means that the amount of the catalyst can be halved, and the reduction of the catalyst cost and the equipment cost can be greatly reduced, which is very advantageous industrially.

Example 12
An experiment was conducted in the same manner as in Example 5 except that the catalyst synthesized in Catalyst Preparation Example 9 was used as the catalyst. When 100 hours passed, the conversion rate of palm oil, the yield of methyl ester, and the yield of glycerin were 99%, 97%, and 93%, respectively.

Example 13
The experiment was performed in the same manner as in Example 5 except that the catalyst synthesized in Catalyst Preparation Example 10 was used as the catalyst. When 100 hours passed, the conversion rate of palm oil, the yield of methyl ester, and the yield of glycerin were 92%, 89%, and 84%, respectively.

Comparative Example 1
Triolein (61.5 g), methanol (20 g) and 2.5 g of manganese dioxide manufactured by Wako Pure Chemical Industries, Ltd. as a catalyst were charged into an autoclave having a capacity of 200 mL. After nitrogen substitution, the reaction was carried out for 24 hours at a reaction temperature of 150 ° C. with stirring inside. The conversion of triolein was 100%, but manganese dioxide was eluted in the reaction solution by 80% of the charged amount. It was.

Catalyst preparation comparative example 1 (Mn-P)
50 g of manganese phosphate (III) (monobasic) (tetrahydrate) manufactured by Sanei Chemical Industry Co., Ltd. was fired at 600 ° C. for 5 hours in an air atmosphere, and 20 t using a molding compressor (manufactured by Maekawa Tester). Molded for 3 minutes. The molded sample was crushed and sieved to 250 μm to 850 μm.

Comparative Example 2
An experiment was conducted in the same manner as in Example 5 except that the catalyst synthesized in Catalyst Preparation Comparative Example 1 was used as the catalyst. The conversion rate of palm oil, the yield of methyl ester, and the yield of glycerin after 100 hours were 25%, 2%, and 0%, respectively.

The results of Comparative Example 1 and Comparative Example 2 are examined as follows.
Since the catalyst (MnO ₂ ) used in Comparative Example 1 was only a manganese compound, it was found that there was much elution and it was not suitable for use as a solid catalyst. Moreover, although the catalyst (Mn-P) used in Comparative Example 2 is a complex oxide and / or mixed oxide of a manganese compound and a pentavalent nonmetal, this reaction hardly proceeds with this catalyst. all right.

Catalyst preparation comparative example 2 (Co-Si)
Synthesis was performed in the same manner as in Catalyst Preparation Example 5, except that a 50% aqueous solution of cobalt nitrate was used instead of the 50% aqueous solution of manganese nitrate. As a result of XRD measurement, the calcined catalyst had a structure of Co ₂ SiO ₄ and its content was 100%. The XRD pattern of the catalyst obtained in Catalyst Preparation Example C is shown in FIG.

Comparative Example 3
An experiment was conducted in the same manner as in Example 5 except that the catalyst synthesized in Catalyst Preparation Comparative Example 2 was used as the catalyst. When 100 hours passed, the conversion rate of palm oil, the yield of methyl ester, and the yield of glycerin were 35%, 4%, and 1%, respectively.

The results of Comparative Example 3 are examined as follows.
The catalyst (Co-Si) used in Comparative Example 3 is a composite oxide of cobalt and silicon, which is a tetravalent metalloid element. However, if a manganese compound is not included as a catalyst, the activity is a manganese compound. It was found to be significantly lower than that included.

From the examples and comparative examples described above, it was found that the following can be said. That is, in the method for producing a fatty acid alkyl ester and / or glycerin comprising the step of bringing an oil and fat into contact with an alcohol in the presence of a catalyst, a manganese compound and a tetravalent metal element and / or a tetravalent metalloid element. It was found that the activity was very high by using a catalyst having a compound. It was also found that high activity was maintained for a long time without elution of active metal. Furthermore, even in the presence of free fatty acid (FFA) and water contained in fats and oils, it is possible to maintain the catalytic activity for a long time, thereby increasing the yield of fatty acid alkyl ester and / or glycerin. It has been found that the advantageous effect of being obtained at a rate is exerted and is remarkable.

Claims (4)

A method for producing a fatty acid alkyl ester and / or glycerin comprising a step of bringing an oil and fat into contact with an alcohol in the presence of a catalyst,
The method for producing a fatty acid alkyl ester and / or glycerin, characterized in that the catalyst has a manganese compound and a compound of a tetravalent metal element and / or a tetravalent metalloid element. The method for producing a fatty acid alkyl ester and / or glycerin according to claim 1, wherein the compound of the tetravalent metal element and / or the tetravalent metalloid element is a silicon compound and / or a zirconium compound. The method for producing a fatty acid alkyl ester and / or glycerin according to claim 1 or 2, wherein the catalyst is in the form of a mixed oxide or a complex oxide. A catalyst for producing a fatty acid alkyl ester and / or glycerin, which is used in the method for producing a fatty acid alkyl ester and / or glycerin according to any one of claims 1 to 3.