JP2013072071A - Method for producing fatty acid alkyl ester and/or glycerol from oil and fat - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of fatty acid alkyl ester and/or glycerol, and a catalyst for the production method which sufficiently suppress structural changes of main catalytically-active metal component or the like even when using the catalyst repeatedly or using the catalyst for a long period, on the production of fatty acid alkyl ester and/or glycerol according to reaction of a fatty or oily material and alcohol, moreover, which can maintain superior catalytic activity even in the presence of water, can exhibit high catalytic activity in both reactions of interesterification of glycerides contained in oils and fats, and esterification of free fatty acid, can exhibit high catalytic activity even in the presence of impurities of the free fatty acid (FFA) or the like contained in oils and fats, therefore, can maintain the high activity over a long term, further elongating the life of the catalyst, further stabilizing the reaction system and improving productivity, qualities, etc., of products, and simplifies or makes elaborate step such as recovery step of catalyst unnecessary and is efficiently suited for applications of food, fuel, etc.SOLUTION: The production method of fatty acid alkyl ester and/or glycerol includes a step of bringing oils and fats into contact with alcohol in the presence of a catalyst, wherein the catalyst contains oxides which comprises manganese element, aluminum element and a third component element, and the third component element is at least one element selected from elements belonging to eighth to twelfth groups of the periodic table.

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.

Under such circumstances, studies on heterogeneous catalysts are underway with respect to methods for producing fatty acid esters and the like by transesterification. For example, a method for producing a fatty acid monoester and a polyhydric alcohol by transesterifying a polyhydric alcohol with a compound selected from the group consisting of animal-derived oils and fats, plant-derived oils and fats, and fatty acid methyl esters, A technique for performing a transesterification reaction in the presence of a basic solid catalyst that is an oxide selected from the following group is disclosed (for example, see Patent Document 1).
(1) Mixed oxide of one or more kinds of monovalent metals and one or more kinds of trivalent metals (2) Mixture of one or more kinds of divalent metals and one or more kinds of trivalent metals Oxide (3) Arbitrary mixture of these mixed oxides This technique is intended to produce fatty acid monoesters and polyhydric alcohols using solid base catalysts containing specific elements. The calcination temperature in the catalyst preparation is 750 ° C. or less, and in the examples, a catalyst made of Li—Al and Mg—Al at a calcination temperature of 450 ° C. is used.

Further, a technique using a manganese compound and a trivalent metal element oxide as a catalyst is disclosed (for example, see Patent Document 2). This technique is a method for producing a fatty acid alkyl ester and / or glycerin, which comprises a step of bringing an oil and fat into contact with an alcohol in the presence of a catalyst, the catalyst comprising oxidizing a manganese compound and a trivalent metal element. It is characterized by having a thing. The calcination temperature in the catalyst preparation is preferably 500 ° C. or higher and 1500 ° C. or lower when preparing a mixed oxide and / or composite oxide comprising a manganese oxide and an aluminum oxide. A catalyst made of Mn—Al, Mn—Zr—Al, Mn—Si—Al is used at a firing temperature of 600 to 1500 ° C.

Furthermore, a technique using a catalyst containing zinc aluminate is disclosed (for example, see Patent Document 3). This technique is a method for producing a fatty acid ester and glycerin, and uses a catalyst containing ZnAl ₂ O ₄ , xZnO, and yAl ₂ O ₃ (x and y are 0 to 2). The calcination temperature in the catalyst preparation is 400 ° C. or higher. In the examples, a catalyst made of Zn—Al at a calcination temperature of 600 ° C. is used.

International Publication No. 2005/35479 Pamphlet International Publication No. 2009/66539 Pamphlet French Patent Application Publication No. 2752242

However, the technique described in Patent Document 1 has a problem that the catalyst component is eluted during the reaction and has a short life, and there is room for devising such as suppressing a decrease in activity due to the elution of the active component.
As a conventional method for solving such a problem, for example, in order to avoid a decrease in yield and a decrease in product purity, it is considered to frequently exchange a catalyst having a decreased activity with a new catalyst. However, 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. Moreover, in order to remove the active ingredient eluted from the product, a complicated purification step such as washing with water or distillation is necessary, and it is desirable for industrial production in that a new step needs to be added to the production apparatus. Absent. Therefore, in the catalyst described in Patent Document 1, the active component is difficult to elute, and excellent catalytic activity can be maintained for a long time in the presence of impurities such as water and free fatty acid (FFA). There was room for ingenuity to do.
In the technique described in Patent Document 3, it cannot be said that the activity of the catalyst is sufficient, and it is necessary to increase the amount of the catalyst used and thereby increase the size of the reactor, and to avoid them in industrial production. There was room for ingenuity.

On the other hand, in the technique described in Patent Document 2, by using a catalyst having a manganese element and a trivalent metal element, the elution of the active metal component is further suppressed, the catalyst life is long, High activity can be maintained even in the presence of contained free fatty acid (FFA), mineral acid, metal component, and water, and the raw material alcohol is not decomposed. Furthermore, when the trivalent metal element is in the form of an oxide, the effect of maintaining a high activity for a long period of time regardless of whether water is contained in the raw material is more exhibited, and the trivalent contained in the catalyst. This effect is further exhibited by using an oxide of aluminum as the metal element oxide.
Thus, in the method for producing a fatty acid alkyl ester and / or glycerin from oils and alcohols in the presence of a catalyst by the technique described in Patent Document 2, in terms of extending the life of the catalyst and maintaining high activity. This has improved problems that those skilled in the art have not previously achieved over the long term.

However, there is still room for further improvement. For example, the conversion rate of fats and oils and the longer life of the catalyst have been considerably improved compared to the conventional case, but if the reaction system is further stabilized. As a result, productivity of the product is improved and quality is improved. By achieving such further improvement, it is expected to greatly increase the industrial utility as an additive of plant-derived biodiesel fuel, which has been attracting attention to achieve CO ₂ emission reduction. It is a place.

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 an oil and fat with an alcohol, the catalyst may be used repeatedly or for a long time. In addition, structural changes of the main catalytically active metal components, etc. are sufficiently suppressed, and excellent catalytic activity can be maintained for a long time even in the presence of water. Both transesterification of glycerides contained in fats and oils and esterification of free fatty acids Simplifies or eliminates complicated processes such as the catalyst recovery process that can exhibit high activity in the reaction and can exhibit high catalytic activity even in the presence of impurities such as free fatty acids (FFA) contained in fats and oils. It is an object of the present invention to provide a method for producing a fatty acid alkyl ester and / or glycerin suitable for uses such as food and fuel with high efficiency and a catalyst thereof. This aims at maintaining high activity over a long period of time, further extending the life of the catalyst, achieving further stabilization of the reaction system, and improving product productivity, quality, and the like.

The present inventors have made various studies on methods for producing fatty acid alkyl esters and / or glycerin by bringing oils and alcohols into contact with each other in the presence of a solid catalyst. As a result, a catalyst having a manganese element and a trivalent metal element is obtained. By using it, compared to other solid catalysts, an improvement effect is recognized in terms of extending the life of the catalyst and maintaining high activity. However, if the number of reactions increases by reusing the catalyst, the valence of Mn It has been found that a new problem arises that the catalyst structure gradually changes and causes destabilization of the catalyst structure.
In addition to the manganese element, an aluminum element is selected as a trivalent metal element to be a catalyst component, and in addition to these, as a third component element, at least one of the elements belonging to Groups 8 to 12 of the periodic table is selected. When one element is selected and the catalyst is in the form of an oxide, in addition to the advantageous effect of using a catalyst having a manganese element and a trivalent metal element, high activity can be maintained for a longer period of time. It has been found that the product life, quality, and the like can be improved because the lifetime can be extended and the conversion rate in the reaction system can be further stabilized. By adding the third component, it is surmised that the stability of the main active species, manganese element (Mn), in the catalyst was increased, particularly by combining the third component. Thereby, for example, the oil / fat conversion rate can be stabilized at a high value, and the fatty acid alkyl ester and / or the glycerin product can be supplied more stably.

That is, the present invention is a method for producing a fatty acid alkyl ester and / or glycerin comprising a step of bringing oils and alcohols into contact with each other in the presence of a catalyst, wherein the catalyst comprises a manganese element, an aluminum element, and In the method for producing a fatty acid alkyl ester and / or glycerin, which includes an oxide composed of a third component element, and the third component element is at least one element selected from elements belonging to Groups 8 to 12 of the periodic table is there.
The present invention is also a catalyst for use in a method for producing a fatty acid alkyl ester and / or glycerin comprising a step of bringing oils and alcohols into contact with each other in the presence of a catalyst, wherein the catalyst has the following composition formula: Formula (1);
_{X a Mn b Al c O d} (1)
(In the formula, X represents at least one element selected from elements belonging to Groups 8 to 12 of the periodic table. A, b, c, and d are the number of X atoms, the number of Mn atoms, and Al, respectively. And the valence of X, the valence of Mn, and the valence of Al are represented by α, β, and γ, respectively, and d = (aα + bβ + cγ) / 2). It is also a catalyst for the production of fatty acid alkyl ester and / or glycerin containing a compound.
The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

In the production method of the present invention, a step of bringing oils and alcohols into contact with each other in the presence of a catalyst is essential, and both or at least one of a fatty acid alkyl ester and glycerin is produced. Preferably, it is set as the manufacturing method which produces both fatty-acid alkylester and glycerol.
In one aspect of the production method of the present invention, an oxide comprising a manganese element, an aluminum element, and a third component element (in the present specification, these are also referred to as essential elements) is used as a catalyst in the production method. In addition, the third component element essentially uses a catalyst that is at least one element selected from elements belonging to Groups 8 to 12 of the periodic table.
In one aspect of the catalyst for production of fatty acid alkyl ester and / or glycerin of the present invention, the compound represented by the general formula (1) is essential. In the above production method, the catalyst can maintain high activity, further extend the life of the catalyst, and further stabilize the conversion rate in the reaction system as compared with the conventional catalyst. The catalyst can be suitably applied as the most advantageous catalyst for the production method.
In the present invention, the catalyst contains Mn in Group 7 of the periodic table and Al in Group 13 and at least one element belonging to Groups 8-12, which is a group between them.

In the above catalyst, the inclusion of an aluminum element may include one or more trivalent metal elements other than the aluminum element and the third component element in place of or together with the aluminum element. Is possible. That is, it is also possible to use a catalyst containing an oxide composed of a manganese element, a trivalent metal element, and a third component element.
However, in the present invention, if an oxide of an aluminum element is included, it is advantageous in terms of catalyst stability. Therefore, an aluminum element is selected as a trivalent metal element, and this is essential. Examples of the trivalent metal element include gallium, indium, thallium, scandium, yttrium, vanadium, chromium, iron, cobalt, and a lanthanoid element.

As a composition ratio of the essential elements constituting the catalyst, a preferable range can be specified by a molar ratio based on manganese elements. The composition ratio can be calculated by the number of moles of essential elements in the product.
That is, the above catalyst preferably has 0.01 <Al / Mn (mol) <300, where (number of moles of aluminum element) / (number of moles of manganese element) is expressed as Al / Mn (mol). More preferably, 0.15 <Al / Mn (mol) <150, and still more preferably 0.5 <Al / Mn (mol) <75. If it is out of these ranges, the effect of the present invention by combining the manganese element and the aluminum element may not be sufficiently exhibited. The above molar ratio can be applied to the manganese element and the trivalent metal element. In the present invention, since aluminum is selected as the trivalent metal element, the above molar ratio is set between the manganese element and the aluminum element. This is applied in combination.

Moreover, it is preferable that the said catalyst is 0.01 <X / Mn (mol) <100, when (number of moles of the third component element / number of moles of manganese element) is expressed as X / Mn (mol). More preferably, 0.1 <X / Mn (mol) <10, and more preferably 0.2 <X / Mn (mol) <5. If it is out of these ranges, there is a possibility that the effect of increasing the stability in the catalyst of manganese element, which is the main active species, by adding the third component may not be sufficiently exhibited.
Moreover, as said molar ratio, it is preferable to satisfy | fill said Al / Mn (mol) and said X / Mn (mol) simultaneously. That is, it is preferable to satisfy one of the preferable ranges of Al / Mn (mol) and to satisfy one of the preferable ranges of X / Mn (mol).

In the compound represented by the general formula (1) in the fatty acid alkyl ester and / or glycerin production catalyst of the present invention, a is the number of X atoms, b is the number of Mn atoms, and c is the number of Al atoms. Yes, X corresponds to the third component element. About the preferable ratio of these a, b, and c, it can set on the basis of the atomic number b of a manganese element similarly to having mentioned above. The ratio can be calculated by the number of moles of essential elements in the product, similar to the above composition ratio.
That is, in the general formula (1), a / b is preferably 0.01 <a / b <100. More preferably, 0.1 <a / b <10, and still more preferably 0.2 <a / b <5. Further, c / b is preferably 0.01 <c / b <300. More preferably, 0.15 <c / b <150, and still more preferably 0.5 <c / b <75.
Moreover, as said molar ratio, it is preferable to satisfy said a / b and said c / b simultaneously. That is, it is preferable to satisfy one of the preferable ranges of a / b and to satisfy one of the preferable ranges of c / b.
The element ratio in the catalyst can be measured by X-ray diffraction (XRD) or X-ray fluorescence analysis (XRF) that can analyze the crystal structure.

In the catalyst of the present invention, the third component element is preferably at least one element selected from elements belonging to the fourth period of Groups 8 to 12. The elements belonging to the fourth period of Group 8-12 are iron element (Fe), cobalt element (Co), nickel element (Ni), copper element (Cu), and zinc element (Zn).
According to such a preferred embodiment, in the fourth period of the periodic table, together with manganese element (Mn), which is an element of group 7, the same fourth period, groups 8 to 12 which are groups subsequent to group 7 By including at least one element among these elements, the interaction between the manganese element and the aluminum element becomes stronger through the third component element, and the change in the valence of the manganese element is further suppressed. As a result, the effect of increasing the stability of the manganese element, which is the main active species, in the catalyst by adding the third component is more fully exhibited.
More preferably, among the elements belonging to the fourth period of the 8th to 12th groups, at least one of a cobalt element, a nickel element, and a zinc element is selected. More preferably, the cobalt element and / or Zinc element is selected, and most preferably, cobalt element is selected.
In the present invention, it is preferable that the manganese element, the aluminum element, and the third component element are in the form of a composite oxide. More preferably, a manganese oxide, an aluminum element, and at least one element selected from elements belonging to the fourth period of Group 8 to 12 are in the form of a composite oxide. Thereby, the interaction between the three elements of the manganese element, the aluminum element, and the third component element is more effectively exhibited, and the change in the valence of the manganese element is further suppressed.

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, in order to sufficiently exhibit the effects of the present invention, an oxide composed of the manganese element, the aluminum element, and the third component element is the main component of the catalyst in the present invention. It is preferable that When the total mass of the catalyst in the present invention is 100 mass%, it is preferable that the mass% of the oxide composed of the manganese element, the aluminum element, and the third component element is 50 mass% or more. More preferably, it is 80 mass% or more, More preferably, it is 85 mass% or more, Most preferably, it is 90 mass% or more, Most preferably, it is 95 mass% or more.

Examples of the existence form of the essential element in the catalyst include simple substances, alloys, complexes, organic metals, salts, halides, sulfides, cyanides, and oxides, but in the present invention, Since it is advantageous in the stability of the catalyst, it contains an oxide. In addition, it is preferable that it is a catalyst which mainly contains the oxide, and it does not exclude including another form.
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.

In the present invention, the oxide may be a mixed oxide or a complex oxide.
In other words, the catalyst used in the production method of the present invention is a catalyst made of a mixed oxide and / or composite oxide in which a manganese element, an aluminum element, and a third component element are essential components.
The fatty acid alkyl ester and / or glycerin production catalyst of the present invention is a catalyst comprising a mixed oxide and / or a composite oxide in which the compound represented by the general formula (1) is an essential component.

The mixed oxide is a mixture of two or more oxides as described above, and each oxide includes an element selected from the group consisting of a manganese element, an aluminum element, and a third component element. It is preferable to contain at least one kind. The composite oxide contains two or more elements selected from the group consisting of manganese element, aluminum element and third component element, manganese element, aluminum element and third component element. It is preferable.
Therefore, as the mixed oxide and / or composite oxide, for example, (1) a form in which a single oxide of a manganese element, a single oxide of an aluminum element, and a single oxide of a third component element are mixed, (2) A composite oxide containing two elements selected from the group consisting of a manganese element, an aluminum element, and a third component element, and a group selected from the group consisting of a manganese element, an aluminum element, and a third component element A mixed form of single oxides of one or more elements, (3) a composite oxide containing two elements of manganese element, aluminum element and third component element, and the two kinds (4) Complex oxides containing three types of elements, manganese element, aluminum element and third component element, and manganese element, aluminum Element, and it can include forms like a mixture of single oxides of one or more elements selected from the group consisting of the third component element. Regarding (4) above, the carrier component usually remains as a single oxide even when the three components are complex oxides.
Thus, the essential elements may be contained in separate compounds (crystal structure) or in the same compound (crystal structure). That is, in the present invention, when it is described that the catalyst includes an oxide composed of a manganese element, an aluminum element, and a third component element, the element is also included in a separate compound (crystal structure) in the catalyst. It may be included in the same compound (crystal structure).
Moreover, in the oxide which consists of the said manganese element, aluminum element, and a 3rd component element, elements other than the said essential element may be contained, In that case, even if it is contained in the said complex oxide In addition, an oxide of an element other than the essential elements may be included. The single oxide may be a complex oxide by containing an element other than the essential element.
Preferably, the mixed oxide and / or the composite oxide include a manganese element, an aluminum element, and a third component element as elements other than oxygen.

Other components that can be included in the catalyst of the present invention, that is, elements other than the essential elements are not particularly limited as long as they do not hinder the action of the catalyst, zirconium, hafnium, tin, lead, silicon, A tetravalent metal element such as germanium or titanium, a divalent metal element, or a metalloid element can be used.

The single oxide of manganese element is a single oxide represented by MnO _x (wherein x is a number of 1 or more and 7/2 or less). 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 oxide of the manganese element is in the form of a complex oxide, which may be crystallized or amorphous, but use a crystallized form. Are preferred, and those having a manganese element and other metal elements in the crystal lattice are preferred. More preferably, it is a complex oxide having a manganese element and the third component element in the crystal lattice. More preferably, it is a complex oxide having a manganese element, the third component element and an aluminum element in the crystal lattice.
That is, as the other metal element, one or more elements belonging to Group 8 to 12 of the periodic table are preferable, and iron element which is an element belonging to Group 8 to 12 of Period 4 of the Periodic Table More preferably, one or more of cobalt element, nickel element, copper element, and zinc element are used. As other metal elements other than these, for example, one or more of titanium element, niobium element, lanthanoid element and the like are suitable.

The oxide of aluminum element may be a single oxide of aluminum element or a complex oxide with other metal elements. The single oxide of aluminum element is a compound represented by Al ₂ O ₃ . This oxide may be a single oxide of crystalline aluminum element such as α, γ, δ, η, θ, κ, or a single oxide of amorphous aluminum element, but it is stable. From the viewpoint of properties, crystalline α, γ-Al ₂ O ₃ or amorphous aluminum single oxide is preferable. More preferably, it is γ-Al ₂ O ₃ .
When the oxide of the aluminum element is a complex oxide with other elements, examples of the element that forms the complex oxide with the aluminum element include manganese and third component elements. Other than that, zirconium, hafnium And tetravalent metal elements such as tin, lead, silicon, germanium, and titanium, divalent metal elements, metalloid elements, and the like. Among these, zirconium, silicon, and titanium are preferably used.

If the catalyst is in the form of mixed oxide and / or composite oxide, the active component of the catalyst is difficult to elute, and excellent catalytic activity in the presence of impurities such as water and free fatty acid (FFA) is long. The effect of maintaining time will be exhibited more remarkably. Due to this effect, when this catalyst is used in a fixed bed flow type reaction apparatus, a continuous and long-term reaction can be performed, which is extremely advantageous industrially.

Examples of the catalyst include a single oxide of manganese, a single oxide of aluminum and a single oxide of a third component element, or a composite oxide of manganese and a third component element and a single oxide of aluminum. It is preferably a mixed oxide of monoxide, or a mixed oxide of manganese, a third component element, and aluminum and a single oxide of aluminum. More preferably, a mixed oxide of a complex oxide of manganese and a third component element and a single oxide of aluminum, or a complex oxide of manganese, a third component element and aluminum, and a single oxide of aluminum It is a mixed oxide. More preferably, it is a mixed oxide of manganese, a third component element, and aluminum and a single oxide of aluminum. Thereby, the interaction between the manganese element and the aluminum element becomes stronger through the third component element. In particular, when a composite oxide composed of the three components of the manganese element, the third component element, and the aluminum element is included, 3 It is considered that the destabilization of the catalyst structure caused by the complexation of elements and the gradual change of manganese valence is further suppressed.
In the case of the mixed oxide, the manganese compound is supported on the aluminum compound, the third component element compound (compound having the third component element) is mixed and fired, or the manganese compound and the third component element are mixed. It can be obtained by carrying it on an aluminum compound and firing it. The catalyst thus obtained is a preferred embodiment of the present invention.

In preparation of the mixed oxide, the manganese compound can be supported on the aluminum compound by impregnating the aluminum compound with an aqueous solution of the manganese compound.
In addition, the manganese compound and the third component element compound can be supported on the aluminum compound by impregnating the aluminum compound with an aqueous solution of the manganese compound and the third component element compound.
In these cases, the aluminum compound is usually supplied as an oxide or hydroxide powder or particles, and impregnated with and supported by an aqueous solution of a manganese compound or an aqueous solution containing a manganese compound and a third component element compound. become. When an aqueous solution containing a manganese compound and a third component element compound is impregnated and supported on an aluminum compound, in addition to a single oxide of manganese element and third component element, a complex oxide of manganese element and third component element And / or a composite oxide of a manganese element, a third component element, and an aluminum element is also generated.

In addition, manganese nitrate, manganese sulfate, manganese chloride, manganese acetate, etc. can be used as a manganese compound used as a raw material for the catalyst preparation. As the third component element compound, nitrate, sulfate, chloride, acetate, etc. of the third component element can be used.
In the preparation of the mixed oxide, when the aluminum compound is supported, the manganese compound and the third component element compound may be any compound that can be impregnated in the aluminum compound as described above. After impregnating and supporting using such a compound, it is preferable to perform a baking treatment after drying. After performing the firing treatment, mixed oxide containing manganese oxide, aluminum oxide and third component element oxide, and / or the above-described composite oxide, or the above-described composite oxide It becomes a thing. A method for preparing such a mixed oxide and / or composite oxide catalyst is also a preferred embodiment of the present invention.

In the preparation of the above mixed oxide, a preferred form when it is supported on an aluminum compound is as follows.
As carrier composition is represented by _Al 2 _{O 3,} crystalline _{α, γ-Al 2 O 3} , or a single oxide of amorphous aluminum element, preferably _γ-Al 2 _{O 3} It is.
The carrier shape is preferably powder or particulate.
After impregnating the above aqueous solution into an aluminum compound, it is preferable to dry and perform a firing step, and the drying temperature is preferably 40 ° C. or higher and 200 ° C. or lower. More preferably, it is 40 degreeC or more and 120 degrees C or less.

In the firing step, for example, it is preferably performed as follows.
For example, the firing temperature is preferably 300 ° C. or higher and 1500 ° C. or lower. If the temperature is lower than 300 ° C, the composite oxide may not be sufficiently obtained. If the temperature exceeds 1500 ° C, a sufficient catalyst surface area may not be obtained and the fatty acid alkyl ester and / or glycerin may not be produced with high efficiency. is there. A more preferable lower limit temperature is 600 ° C., and a more preferable upper limit temperature is 1300 ° C., 900 ° C., and 850 ° C. in a preferable order. For example, it is more preferably 300 ° C. or higher and 900 ° C. or lower, still more preferably 300 ° C. or higher and 850 ° C. or lower, and still more preferably 600 ° C. or higher and 850 ° C. or lower.
The firing time is preferably 30 minutes or longer and within 24 hours. The more preferred lower limit time is 1 hour, 2 hours, and 3 hours in the preferred order, and the more preferred upper limit time is 15 hours and 12 hours in the preferred order. For example, it is more preferably 1 hour or more and 15 hours or less, and still more preferably 3 hours or more and 12 hours or less.
The gas phase atmosphere during firing can be an atmosphere of air, nitrogen, argon, oxygen or the like.
Preferably, it is a gas phase atmosphere of 10% by mass or less of oxygen or an inert gas atmosphere. By firing in an atmosphere with reduced oxygen, a composite oxide can be easily prepared.

The production method of the present invention is a catalyst (hereinafter also referred to as “insoluble catalyst”) insoluble in any of fats and oils and alcohol and products (fatty acid alkyl ester, glycerin, etc.) under reaction conditions. Is preferred. After the reaction of bringing oils and alcohols into contact with each other in the presence of a catalyst, when the alcohol is distilled off in the absence of the catalyst, a phase mainly containing a fatty acid alkyl ester (ester phase) and a by-product glycerin are obtained. In this case, the phase is separated into mainly containing phases (glycerin phase). In this case, both phases contain alcohol, resulting in insufficient phase separation. At this time, when the alcohol is distilled off in the absence of the catalyst, the mutual solubility between the upper layer mainly containing the fatty acid alkyl ester and the lower layer mainly containing glycerin is reduced, and the separation of the fatty acid alkyl ester and glycerin is improved. The product, fatty acid alkyl ester and glycerin can be obtained with high purity. At this time, 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 fatty acid alkyl ester decreases. Become. 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.

When the catalyst in the present invention is used as the catalyst, the catalyst is suitable as the insoluble catalyst, and has the capability of performing an esterification reaction and a transesterification reaction at the same time. Since it is not affected by acids or metal components, and exhibits effects such as that alcohol does not decompose, it is possible to produce fatty acid alkyl esters and / or glycerin with high efficiency in the production method of the present invention. It is what.

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 embodiment of the present invention, usually, mineral acid, metal component, sterol, phospholipid, water, free fatty acid (FFA) and the like are included. In such embodiment, the catalyst in the present invention is also included. A form using 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.

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 7 to 23 carbon atoms or an alkenyl group having 7 to 23 carbon atoms having one or more unsaturated bonds. As these carbon number, More preferably, it is C9-21, More preferably, it is C11-21.
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. Usually, it is preferable to use a fat or oil containing triglyceride (triester of glycerin and higher fatty acid) as a main component and a small amount of diglyceride, monoglyceride and other subcomponents, but triolein, tripalmitin or the like may be used. .
Examples of the oils and fats include vegetable oils such as rapeseed oil, sesame oil, soybean oil, corn oil, sunflower oil, palm oil, palm kernel oil, safflower oil, linseed oil, cottonseed oil, tung oil, castor oil, coconut oil; Animal oils and fats such as oil, fish oil and whale fat; used oils (waste cooking oils) of various edible oils and the like are suitable, and these can be used alone or in combination of two or more. Further, these oils and fats may contain an organic acid, or may be subjected to a pretreatment such as deoxidation or degumming.

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 a glyceride.
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 particularly 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 7 to 23 carbon atoms or an alkenyl group having 7 to 23 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 it at the reaction temperature within the said range, an active metal component is a thing which does not elute substantially, and the main catalytically active metal It is preferable that structural changes of components and the like are sufficiently suppressed. 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. Therefore, the catalyst in the present invention is suitably applied.

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 (The catalyst containing the oxide which consists of a manganese element, an aluminum element, and a 3rd component element, the catalyst containing the compound represented by General formula (1)) may be used on the supercritical conditions of the alcohol to be used. it can. 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.

In the method for producing the fatty acid alkyl ester and / or glycerin, as a catalyst amount used for the reaction, in the case of a batch type, the lower limit is 0.5% by mass and the upper limit is 20% with respect to the total charged mass of fat, alcohol and catalyst. % Is preferred. 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 ^{5 hr -1.} More preferably, the lower limit is 0.2 hr ⁻¹ and the upper limit is 3 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)

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 from the mixed solution after completion of the reaction in the absence of a catalyst, an ester phase containing unreacted glycerides and free fatty acid (FFA) is added. It is preferable that the glycerin phase is separated and recovered by phase separation and used as a raw material for the second and subsequent reactions. 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 step. 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 oils and alcohol are mixed with a catalyst to carry out the reaction. After the solid catalyst is separated and removed from the liquid phase by a process such as filtration from this reaction solution, the alcohol is distilled off, and the ester phase mainly containing fatty acid alkyl ester and glycerides, and glycerin and alcohol are left standing. Separated into mainly containing glycerin phase. 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. The fatty acid alkyl ester and / or glycerin thus obtained may be further purified by an operation such as distillation 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. At this time, it is preferable to distill off the alcohol before allowing the post-reaction solution to stand in the settler in terms of increasing the separation efficiency of the ester phase and the 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 an operation such as distillation depending on the purpose.

In the method for producing a fatty acid alkyl ester and / or glycerin according to the present invention, the contact step in which the catalyst and the reaction solution are brought into contact includes a batch type (batch type) or a continuous flow type. Is a mode in which the catalyst is introduced into a mixed system of oils and fats and alcohol.
Among these, in the method for producing a fatty acid alkyl ester and / or glycerin of the present invention, it is preferable that the contact step is performed in a fixed bed flow type because the step of catalyst separation is unnecessary. That is, the contact step is preferably performed using a fixed bed flow reactor. If the catalyst and the reaction raw material are brought into contact in a reaction tube having a solid catalyst as a stationary phase, the reaction yield can be increased compared to the case of performing a batch reaction, and it can be used for repeated reactions. However, there is no leaching (elution) of the catalyst, the structural change of the main catalytically active metal component and the like is sufficiently suppressed, and the catalyst can be used for a longer period of time, so the life of the catalyst is extended.
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.

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) Both the neutralization and removal step of free fatty acid and the esterification step with an acid catalyst can be made unnecessary.
(3) Saponification of free fatty acids does not occur.
(4) Not only transesterification of fats and oils, but also esterification of free fatty acids in fats and oils proceeds simultaneously.
In terms of simplifying the purification process, i.e. easily obtaining purified glycerin,
(1) Since the catalytic reverse reaction does not occur after the catalyst separation, the alcohol can be distilled off sufficiently, the liquid-liquid two-phase distribution equilibrium is improved (the mutual solubility is reduced), and the product separation is good. Can be done.
(2) Since there is no strong acid or base point on the catalyst surface, there is little alcohol decomposition (dehydration, coking, etc.), and fatty acid alkyl esters can be obtained with high selectivity, and the trace amount contained in fats and oils The point which is hard to receive to the influence of a metal component and the mineral acid used for pre-processing is mentioned.
In addition to the advantageous effects described above, it is possible to maintain high activity for a longer period of time, further extend the life of the catalyst, and further stabilize the conversion rate in the reaction system, thereby improving product productivity, quality, etc. Can be improved.

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 is a chart showing the XRD pattern of the catalyst prepared in Catalyst Preparation Example 1. FIG. 4 is a chart showing an XRD pattern of the catalyst prepared in Catalyst Preparation Example 2. FIG. 5 is a chart showing 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 4. FIG. 7 is a chart showing the XRD pattern of the catalyst prepared in Catalyst Preparation Example 5. FIG. 8 is a chart showing the XRD pattern of the catalyst prepared in Catalyst Preparation Comparative Example 1. FIG. 9 is a chart showing the palm oil conversion rate in each batch of Example 6 and Comparative Example 2.

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. Note that “%” means “mass%” unless otherwise specified.

(Catalyst Preparation Example 1)
To 23.6 g of 50% aqueous manganese (II) nitrate solution, 19.3 g of cobalt nitrate (II) hexahydrate was added, and 7.1 g of pure water was further added to prepare an aqueous solution. The prepared aqueous solution was impregnated with 100 g of activated alumina. After drying on a hot water bath, it was calcined at 800 ° C. for 5 hours. The XRD pattern of the catalyst obtained in Catalyst Preparation Example 1 is shown in FIG. Moreover, as a result of measuring this catalyst by the fluorescent X ray analysis method (XRF), the molar ratio of each element was Al / Mn = 29 and Co / Mn = 1.0.

(Catalyst preparation example 2)
24.3 g of iron (III) nitrate nonahydrate was added to 21.4 g of 50% manganese (II) nitrate aqueous solution, and 4.3 g of pure water was further added to prepare an aqueous solution. The prepared aqueous solution was impregnated with 100 g of activated alumina. After drying on a hot water bath, it was calcined at 800 ° C. for 5 hours. The XRD pattern of the catalyst obtained in Catalyst Preparation Example 2 is shown in FIG. Moreover, as a result of measuring this catalyst by the fluorescent X ray analysis method (XRF), the molar ratio of each element was Al / Mn = 33 and Fe / Mn = 0.8.

(Catalyst Preparation Example 3)
19.2 g of nickel nitrate (II) hexahydrate was added to 23.7 g of 50% aqueous manganese (II) nitrate solution, and 7.1 g of pure water was further added to prepare an aqueous solution. The prepared aqueous solution was impregnated with 100 g of activated alumina. After drying on a hot water bath, it was calcined at 800 ° C. for 5 hours. The XRD pattern of the catalyst obtained in Catalyst Preparation Example 3 is shown in FIG. Moreover, as a result of measuring this catalyst by the fluorescent X ray analysis method (XRF), the molar ratio of each element was Al / Mn = 28 and Ni / Mn = 0.9.

(Catalyst Preparation Example 4)
Copper (II) nitrate trihydrate (17.1) was added to 25.3 g of 50% aqueous manganese (II) nitrate solution, and 7.6 g of pure water was further added to prepare an aqueous solution. The prepared aqueous solution was impregnated with 100 g of activated alumina. After drying on a hot water bath, it was calcined at 800 ° C. for 5 hours. The XRD pattern of the catalyst obtained in Catalyst Preparation Example 4 is shown in FIG. Moreover, as a result of measuring this catalyst by the fluorescent X ray analysis method (XRF), the molar ratio of each element was Al / Mn = 27 and Cu / Mn = 0.8.

(Catalyst Preparation Example 5)
20.4 g of zinc nitrate (II) hexahydrate was added to 24.6 g of 50% aqueous manganese (II) nitrate solution, and 5.0 g of pure water was further added to prepare an aqueous solution. The prepared aqueous solution was impregnated with 100 g of activated alumina. After drying on a hot water bath, it was calcined at 800 ° C. for 5 hours. The XRD pattern of the catalyst obtained in Catalyst Preparation Example 5 is shown in FIG. Moreover, as a result of measuring this catalyst by the fluorescent X ray analysis method (XRF), the molar ratio of each element was Al / Mn = 28 and Zn / Mn = 1.1.

(Catalyst Preparation Example 6)
To 10.0 g of 50% aqueous manganese (II) nitrate solution, 8.2 g of cobalt nitrate (II) hexahydrate was added, and 31.8 g of pure water was further added to prepare an aqueous solution. The prepared aqueous solution was impregnated with 100 g of activated alumina. After drying on a hot water bath, it was calcined at 800 ° C. for 5 hours. As a result of measuring this catalyst by fluorescent X-ray analysis (XRF), the molar ratio of each element was Al / Mn = 60 and Co / Mn = 0.9.

(Catalyst preparation comparative example 1)
100 g of activated alumina was impregnated with 50 g of a 23.6% aqueous manganese (II) nitrate solution. FIG. 8 shows the XRD pattern of the catalyst obtained in Catalyst Preparation Comparative Example 1 after drying on a hot water bath and calcining at 800 ° C. for 5 hours. Moreover, as a result of measuring this catalyst by fluorescent X-ray analysis (XRF), the molar ratio of each element was Al / Mn = 27.

(Catalyst preparation comparative example 2)
100 g of activated alumina was impregnated with 50.0 g of a 10% manganese nitrate (II) aqueous solution. After drying on a hot water bath, it was calcined at 800 ° C. for 5 hours. As a result of measuring this catalyst by fluorescent X-ray analysis (XRF), the molar ratio of each element was Al / Mn = 61.
In these catalyst preparation examples and catalyst preparation comparative examples, as shown in FIG. 8, in the catalyst preparation comparative example, a peak attributed to Mn ₂ O ₃ can be confirmed, but in the catalyst preparation comparative example, Mn ₂ O _It can be confirmed that the peak belonging to ₃ has disappeared. Further, in the catalyst preparation examples, it is expected that Mn is in a form of being compounded with other elements.

(Definitions in the examples, reaction conditions)
(1) The 1st stage reaction liquid fatty acid methyl phase represents the fatty acid methyl phase obtained by phase-separating the reaction liquid when palm oil and methanol are reacted under the following reaction conditions in a fixed bed tubular flow reactor. .
(2) Reaction conditions: reaction temperature 200 ° C., reaction pressure 5 MPa, LHSV = 1 hr ⁻¹ , catalyst synthesized in catalyst preparation examples and catalyst preparation comparative examples, and the amount of methanol supplied to palm oil is 4. 5 times.
(3) Conversions and yields in the examples were calculated by the following formulas.
Conversion rate (mol%) = (mol number of fats or fatty acids consumed at the end of the reaction) / (number of moles of fats or fatty acids charged) × 100 (%)
Fatty acid methyl yield (mol%) = (mol number of fatty acid methyl produced at the end of reaction) / (mol number of charged effective fatty acids) × 100 (%)
-Glycerol yield (mol%) = (number of moles of free glycerin produced at the end of the reaction) / (number of moles of charged effective glycerin component) x 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 material) by gas chromatography.

Example 1
Palm oil (30 g), methanol (30 g) and 3 g of the catalyst synthesized in Catalyst Preparation Example 1 were charged into an autoclave having a capacity of 200 mL. After nitrogen substitution, the reaction was carried out at 190 ° C. for 3 hours while stirring the interior. As a result, the conversion was 88.1%, the yield of fatty acid methyl was 66.8%, and the yield of glycerin was 57.5. %Met.

(Example 2)
The reaction was carried out under the same conditions as in Example 1 except that the catalyst was changed to Catalyst Preparation Example 2. The conversion was 77.8%, the yield of fatty acid methyl was 55.2%, and the yield of glycerin was 39.2%.

(Example 3)
The reaction was conducted under the same conditions as in Example 1 except that the catalyst was changed to Catalyst Preparation Example 3. The conversion was 92.8%, the yield of fatty acid methyl was 78.0%, and the yield of glycerin was 66.9%.

Example 4
The reaction was carried out under the same conditions as in Example 1 except that the catalyst was changed to Catalyst Preparation Comparative Example 4. The conversion was 78.1%, the yield of fatty acid methyl was 54.3%, and the yield of glycerin was 26.9%.

(Example 5)
The reaction was conducted under the same conditions as in Example 1 except that the catalyst was changed to Catalyst Preparation Comparative Example 5. The conversion was 85.7%, the yield of fatty acid methyl was 64.6%, and the yield of glycerin was 49.8%.

(Example 6)
1B (batch): Palm oil (30 g), methanol (30 g), and 3 g of the catalyst synthesized in Catalyst Preparation Example 6 were charged into an autoclave having a capacity of 200 mL. After substitution with nitrogen, the reaction was carried out at 200 ° C. for 3 hours while stirring the interior. As a result, the conversion was 74.1%, the yield of fatty acid methyl was 46.4%, and the yield of glycerol was 29.7. %Met. After the reaction, 3 g of the washed and dried catalyst, the first stage reaction liquid fatty acid methyl phase (60 g), and methanol (30 g) were charged into an autoclave having a capacity of 200 mL. After purging with nitrogen, the mixture was reacted for 15 hours at a reaction temperature of 200 ° C. with stirring, washed and dried.

2B: 3 g of the catalyst after drying the 1B above, palm oil (30 g), and methanol (30 g) were charged into an autoclave having a capacity of 200 mL. After nitrogen substitution, the reaction was carried out at 200 ° C. for 3 hours while stirring the interior. The conversion was 71.6%, the yield of fatty acid methyl was 46.1%, and the yield of glycerin was 29.9. %Met. After the reaction, 3 g of the washed and dried catalyst, the first stage reaction liquid fatty acid methyl phase (60 g), and methanol (30 g) were charged into an autoclave having a capacity of 200 mL. After purging with nitrogen, the reaction was performed at a reaction temperature of 200 ° C. for 15 hours while stirring the interior, and the catalyst was washed and dried.

3B: 3 g of the catalyst after drying the 2B, palm oil (30 g), and methanol (30 g) were charged into an autoclave having a capacity of 200 mL. After the nitrogen substitution, the reaction was carried out at 200 ° C. for 3 hours while stirring the interior. As a result, the conversion was 65.9%, the yield of fatty acid methyl was 39.1%, and the yield of glycerin was 23.9. %Met.
After the reaction, 3 g of the washed and dried catalyst, the first stage reaction liquid fatty acid methyl phase (60 g), and methanol (30 g) were charged into an autoclave having a capacity of 200 mL. After purging with nitrogen, the reaction was carried out at a reaction temperature of 200 ° C. for 15 hours while stirring the interior, and the catalyst was washed and dried.

4B: 3 g of the catalyst after drying the 3B, palm oil (30 g), and methanol (30 g) were charged into an autoclave having a capacity of 200 mL. After substitution with nitrogen, the reaction was carried out at 200 ° C. for 3 hours while stirring the interior. As a result, the conversion was 61.8%, the yield of fatty acid methyl was 39.6%, and the yield of glycerin was 23.2. %Met.

5B: 3 g of the catalyst after drying the 4th B, palm oil (30 g), and methanol (30 g) were charged into an autoclave having a capacity of 200 mL. After the nitrogen substitution, the reaction was carried out at 200 ° C. for 3 hours while stirring the interior. As a result, the conversion was 60.1%, the yield of fatty acid methyl was 40.5%, and the yield of glycerin was 23.7. %Met.

6B: 3 g of the catalyst after drying the 5th B, palm oil (30 g), and methanol (30 g) were charged into an autoclave having a capacity of 200 mL. After substitution with nitrogen, the reaction was carried out at 200 ° C. for 3 hours while stirring the interior. As a result, the conversion was 54.5%, the yield of fatty acid methyl was 34.9%, and the yield of glycerin was 19.2. %Met.

7B: 3 g of the catalyst after drying the 6B, palm oil (30 g), and methanol (30 g) were charged into an autoclave having a capacity of 200 mL. After substitution with nitrogen, the reaction was carried out at 200 ° C. for 3 hours while stirring the interior. As a result, the conversion was 53.1%, the yield of fatty acid methyl was 34.8%, and the yield of glycerin was 18.5. %Met.

8B: 3 g of the catalyst after drying the 7B, palm oil (30 g), and methanol (30 g) were charged into an autoclave having a capacity of 200 mL. After the nitrogen substitution, the reaction was carried out at 200 ° C. for 3 hours while stirring the interior. As a result, the conversion was 49.9%, the yield of fatty acid methyl was 33.5%, and the yield of glycerin was 18.0. %Met.
The palm oil conversion rate in each batch in Example 6 is shown in FIG.

(Comparative Example 1)
The reaction was carried out under the same conditions as in Example 1 except that the catalyst was changed to Catalyst Preparation Comparative Example 1. The conversion was 90.9%, the yield of fatty acid methyl was 67.4%, and the yield of glycerin was 54.2%.

(Comparative Example 2)
The reaction was performed under the same conditions as in Example 6 except that the catalyst was changed to Catalyst Preparation Comparative Example 2.
1B: Conversion was 82.3%, fatty acid methyl yield was 54.2%, and glycerin yield was 38.5%.
2B: Conversion was 73.4%, the yield of fatty acid methyl was 45.1%, and the yield of glycerin was 31.4%.
3B: The conversion was 69.9%, the yield of fatty acid methyl was 38.5%, and the yield of glycerin was 25.3%.
4B: The conversion was 57.7%, the yield of fatty acid methyl was 32.8%, and the yield of glycerin was 17.5%.
5B: The conversion was 56.3%, the yield of fatty acid methyl was 34.2%, and the yield of glycerin was 19.0%.
6B: Conversion was 49.9%, fatty acid methyl yield was 31.1%, and glycerin yield was 16.2%.
7B: The conversion was 45.5%, the yield of fatty acid methyl was 28.9%, and the yield of glycerin was 13.0%.
8B: Conversion rate was 41.3%, fatty acid methyl yield was 25.6%, and glycerin yield was 10.9%.
The palm oil conversion rate in each batch in Comparative Example 2 is shown in FIG.

FIG. 9 shows that the following can be said. That is, by adding a third component element other than Mn and Al to the Mn-Al catalyst to make a catalyst composed of three components, the initial palm oil conversion is lower than that of the Mn-Al catalyst, but the batch reaction is repeated. As the batch reaction continues, the palm oil conversion rate reverses with respect to the Mn-Al catalyst, resulting in a higher activity over a longer period than the Mn-Al catalyst. It is possible to carry out the reaction while maintaining The same applies to the yields of fatty acid methyl and glycerin.
For Example 6 and Comparative Example 2, a catalyst prepared by reducing the amount of manganese and cobalt elements (catalyst preparation) in order to confirm a decrease in catalyst activity in a short-term evaluation as compared with an actual long-term production process. The catalyst of Example 6 and Catalyst Preparation Comparative Example 2) is evaluated, but it is considered that the same tendency is observed in the actual long-term production process.
Thus, in addition to the advantageous effect of using aluminum element as a catalyst having manganese element and trivalent metal element, the addition of the third component element can maintain high activity for a long period of time, and the long life of the catalyst. And further stabilization of the reaction system, further improving the productivity of the product and contributing to the improvement of quality.

In addition, compared with Comparative Example 1 using a catalyst having a manganese element and an aluminum element, even in Example 2-5 using a catalyst having a third component element, the initial conversion rate and the like may be slightly lower. The performance of maintaining the catalytic activity over a long period of time when the batch reaction is continued is similarly excellent as demonstrated by the Co—Mn—Al based catalyst. That is, by using an oxide including an element belonging to Group 8 to 12 as a third component element together with Mn of Group 7 of the periodic table and Al of Group 13 as a third component element, By including the compound represented by the formula (1), in particular, as the third component element, it is the same fourth period as Mn, and at least one of the elements of Groups 8 to 12 which is a group following Group 7. By including two elements, the mechanism of action that the stability in the catalyst of manganese element, which is the main active species, is increased by the interaction between Mn, Al and the third component element is the same. Conceivable.
Therefore, from the results of the above catalyst preparation examples and examples, the present invention can be applied in the entire technical scope of the present invention and in various forms disclosed in this specification, and can exhibit advantageous effects. It can be said.

1-a: fats and oils, alcohol, catalyst 1-b: glycerin phase (glycerin)
1-c: First separation 1-d: Distilling off alcohol 1-e: Ester phase (fatty acid alkyl ester, glycerides)
1-f: alcohol, catalyst 1-g: second separation 1-h: ester phase (fatty acid alkyl ester)
1-i: Glycerin phase (glycerin)
1-j: Distilling off alcohol 2-a: Fat and oil, alcohol 2-b: Catalyst 2-c: Glycerin phase (glycerin)
2-d: Settler 2-e: Distilling off alcohol 2-f: Ester phase (fatty acid alkyl ester, glycerides)
2-g: alcohol 2-h: catalyst 2-i: settler 2-j: ester phase (fatty acid alkyl ester)
2-k: glycerin phase (glycerin)
2-m: Distill off alcohol

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 catalyst includes an oxide composed of a manganese element, an aluminum element, and a third component element,
The method for producing a fatty acid alkyl ester and / or glycerin, wherein the third component element is at least one element selected from elements belonging to Groups 8 to 12 of the periodic table. In the catalyst, the molar ratio of the manganese element to the third component element is 0.01 <Al / Mn, where (mol number of aluminum element) / (mol number of manganese element) is expressed as Al / Mn (mol). The process for producing a fatty acid alkyl ester and / or glycerin according to claim 1, wherein (mol) <300. A catalyst used in a method for producing a fatty acid alkyl ester and / or glycerin, comprising a step of bringing a fat and an alcohol into contact with each other in the presence of a catalyst,
The catalyst has a composition formula of the following general formula (1);
_{X a Mn b Al c O d} (1)
(In the formula, X represents at least one element selected from elements belonging to Groups 8 to 12 of the periodic table. A, b, c, and d are the number of X atoms, the number of Mn atoms, and Al, respectively. And the valence of X, the valence of Mn, and the valence of Al are represented by α, β, and γ, respectively, and d = (aα + bβ + cγ) / 2). A fatty acid alkyl ester and / or a catalyst for production of glycerin, characterized in that In the said General formula (1), a / b is 0.01-100, and c / b is 0.01-300, The fatty-acid alkylester of Claim 3 characterized by the above-mentioned // Catalyst for production of glycerin.

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