JP3941876B2 - Process for producing fatty acid alkyl ester and / or glycerin - Google Patents

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.

A method of performing a transesterification reaction using a solid catalyst as a catalyst other than a homogeneous catalyst is known. Among solid catalysts, basic ion exchange resins have been proposed for solid base catalysts (see, for example, Patent Document 1). When such a basic ion exchange resin is used, the mineral acid used in the pretreatment to remove fatty acids mixed as impurities in the fat and oil, glycerin as one product, and phospholipids and proteins contained in the fat and oil And the like act as catalyst poisons, it is necessary to use a large excess of alcohol in order to maintain the catalytic activity. For this reason, a great cost is required for alcohol recovery. In addition, since it does not have esterification activity of free fatty acids contained in fats and oils, a step of removing free fatty acids or a step of esterifying free fatty acids with an acid catalyst is required before the transesterification step, and the reaction process becomes complicated. . Therefore, in order to use the basic ion exchange resin as an industrial catalyst, there is room for improvement in these respects.

As for the inorganic solid base catalyst, for example, a heterogeneous solid catalyst composed of sodium carbonate and / or sodium hydrogen carbonate (see, for example, Patent Document 2), a solid catalyst containing at least one of calcium hydroxide and calcium oxide (for example, Patent Document 3), hydrotalcite catalyst (for example, see Patent Document 4), solid basic catalyst (for example, see Patent Document 5) composed of potassium compound and iron oxide, or potassium compound and zirconium oxide. Proposed. However, these inorganic solid base catalysts require catalytic active components such as alkali metals and alkaline earth metals to reach and elute into the reaction solution, so that a catalyst life point and a complicated removal process of the eluted components are required. Therefore, there was room for contrivance for industrial use.

Furthermore, with respect to other solid acid catalysts, a method using a cation exchange resin, montmorillonite, or the like (see, for example, Patent Document 6), after contacting a metal oxide and / or metal hydroxide with a solution containing phosphate ions A method using a transesterification catalyst obtained by calcination (for example, see Patent Document 7) has been proposed. However, when such a general solid acid is used as a catalyst, an acid site that is an active site may be poisoned by a trace amount of metal components contained in the oil or fat. In general, an acid catalyst has a lower transesterification activity than a base catalyst. Therefore, it is necessary to increase the reaction temperature. However, when these solid acid catalysts are used at a high temperature in the presence of alcohol, In order to use industrially satisfactorily, byproducts such as etherified products and glycerin condensates are generated, and alcohol is decomposed to cause coking, resulting in a shortened catalyst life. was there.

Further disclosed is a method of using a catalyst comprising a composite metal oxide having a perovskite structure when a lower alkyl ester is produced by performing a transesterification reaction between an oil and fat and a lower alcohol in the presence of a catalyst. (For example, refer to Patent Document 8). The composite metal oxide having a perovskite structure has strong basicity, and preferably contains a cesium (Cs) compound. As what contains a cesium (Cs) compound, what has Ca, Sr, and Ba is mentioned. However, when using a composite metal oxide having such a perovskite structure, pure perovskite has a low activity and requires a high reaction temperature. When the reaction temperature becomes high, the catalytically active component is eluted. In addition, when calcium oxide or cesium components are present outside the perovskite crystal lattice, the activity becomes high and the reaction can be performed even at normal pressure, but a large amount of active metal components such as Ca and Cs are present in the reaction solution. Elution.
JP 62-218495 A (first page) JP 61-254255 A (first page) JP 2001-271090 A (page 1-2) International Publication No. 98/56747 Pamphlet (Summary) JP 2000-44984 A (page 2) JP-A-6-313188 (page 2-3) JP 2001-17862 A (page 1-3) JP 2002-294277 A (2nd page)

The present invention has been made in view of the above situation, and when producing fatty acid alkyl esters and / or glycerin by reacting fats and alcohols with alcohol, there is almost no elution of active metal components and it is contained in fats and oils. By using a catalyst that can exhibit high activity in both the transesterification of glycerides and the esterification of free fatty acids, it is possible to simplify or eliminate complicated processes such as the catalyst recovery process and to achieve high efficiency. Another object of the present invention is to provide a method for producing a fatty acid alkyl ester and / or glycerin suitable for edible and fuel applications, and a catalyst used therefor.

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, in such a process, a catalyst having at least one metal element selected from the group consisting of Group 4 and Group 5 metal elements as an essential component is esterified and transesterified. It has been found that the catalyst has a performance capable of simultaneously carrying out the above, is not affected by mineral acids and metal components contained in fats and oils, and exhibits a working effect such as alcohol does not decompose. In addition, since there is almost no elution of the active metal component and the catalyst life is long, the catalyst recovery process can be remarkably simplified or unnecessary as compared with the homogeneous catalyst used in the conventional method. It was found that it can be used repeatedly for the reaction, and it was conceived that the above problems could be solved brilliantly. And in such a catalyst, it is further selected from the group consisting of the elements of Group 3, Group 6, Group 8, Group 9, Group 10, Group 11, Group 12, Group 14, Group 15, Group 16 and Lanthanoid Use of an element containing at least one element further improves the reaction activity and / or catalyst life, sufficiently suppresses the elution of the active metal component, and exhibits the effects of the present invention more fully. I found that I could do it.

That is, the present invention is 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, wherein the catalyst is composed of a Group 4 and Group 5 metal element. This is a method for producing a fatty acid alkyl ester and / or glycerin which contains at least one metal element selected from the group consisting of essential components. In the present invention, the catalyst is further selected from the group consisting of elements of Group 3, Group 6, Group 8, Group 9, Group 10, Group 11, Group 12, Group 14, Group 15, Group 16 and Lanthanoid It is also a method for producing a fatty acid alkyl ester and / or glycerin containing at least one element.
The present invention is described in detail below.

In the method for producing a fatty acid alkyl ester and / or glycerin according to the present invention, a catalyst comprising oils and fats and alcohol as essential components at least one metal element selected from the group consisting of Group 4 and Group 5 metal elements. Will be contacted in the presence of.
As a catalyst in the present invention, by using the above metal element as an essential component, elution of the active metal component is sufficiently suppressed, and since it has a high catalytic activity, it is possible to carry out the reaction more efficiently. It becomes.

The catalyst having at least one metal element selected from the group consisting of the group 4 and group 5 metal elements as an essential component is not particularly limited as long as it has the above essential component. For example, a single or composite oxide , Sulfates, phosphates, complexes and the like are preferable, and among these, single or composite oxides are preferable. More preferably, at least one metal element selected from the group consisting of Ti, Zr, V, Nb and Ta is preferably an essential component, and particularly preferably from the group consisting of Ti, V, Nb and Ta. It is preferable that at least one selected metal element is an essential component. For example, titanium oxide, zirconium oxide, vanadium oxide, niobium oxide, tantalum oxide, titanium vanadium composite oxide, titanium niobium composite oxide, titanium vanadium zirconium ternary composite oxide, composite with other group metals An oxide etc. are mentioned. In addition, these forms may be supported or fixed on a support, and examples of the support include silica, alumina, silica / alumina, various zeolites, activated carbon, diatomaceous earth, zirconium oxide, and rutile type. Examples include titanium oxide, tin oxide, lead oxide and the like.

The catalyst is further at least one selected from the group consisting of elements of Group 3, Group 6, Group 8, Group 9, Group 10, Group 11, Group 12, Group 14, Group 15, Group 16 and Lanthanoid It is preferable that the element contains, specifically, Si, Fe, Co, Ce, Zn, Mo, W, Ni, Cu, Sc, Y, La, Sn, Pb, Sb, Bi, Se, and Te. It is preferable that it contains at least one element selected from the group consisting of elements of Group 8, 9, 14, and lanthanoids. . Specifically, Si, Fe, Co, and Ce are particularly preferable because the catalyst performance is improved. Such an element is preferably used as the second component of the catalyst having essential components. The “second component” in this case means an additional component for the essential component, and the essential component and the second component include a plurality of cases. Note that a metal element selected from the group consisting of Group 4 and Group 5 metal elements is also referred to as “essential component atom”, which is Group 3, Group 6, Group 8, Group 9, Group 11, Group 12, Group 14, An element selected from the group consisting of elements of group 15, group 15, group 16 and lanthanoid is also referred to as “second component atom”.
Although content of the said 2nd component is not specifically limited, Usually, the abundance ratio of the 2nd component atom with respect to an essential component atom is 0.05 or more, and is 10 or less. If it is 0.05 or less, the effect of improving the catalyst activity may not be sufficiently exhibited. If it is 10 or more, the active metal component (essential component and / or second component) of the catalyst is eluted into the reaction solution. May not be sufficiently suppressed. As a lower limit, More preferably, it is 0.1, More preferably, it is 0.2. Moreover, as an upper limit, More preferably, it is 5, More preferably, it is 3. As a preferable range, it is 0.1-5, More preferably, it is 0.2-3.

In the catalyst having at least one metal element selected from the group consisting of the group 4 and group 5 metal elements as the essential component, the form having the essential component atom and the second component atom may be, for example, a composite An oxide, a mixture of single oxides, and the like are preferable, and among them, a composite oxide including the essential component atom and the second component atom is preferable. Such a complex oxide may be crystallized or amorphous, but it is preferable to use a crystallized form, which is an essential component in the crystal lattice. A structure having an atom and a second component atom is preferred. By being crystallized, the catalytic activity is further improved, and the elution of the essential component element and the second component element which are active metal components can be sufficiently suppressed.
The form for forming the composite oxide is not particularly limited. For example, the form in which the essential component atom and the second component atom are covalently bonded through an oxygen atom; the form in which the essential component atom and the second component atom are bonded. And a form in which an oxygen atom is covalently bonded; a composite of an oxide of an essential component atom and an oxide of a second component atom, a solid solution thereof, and the like. Moreover, the form which carry | supported or fix | immobilized complex oxide, the complex, etc. on the support | carrier may be sufficient.

Examples of the composite oxide include titanium silicon composite oxide, titanium vanadium composite oxide, titanium niobium composite oxide, titanium tantalum composite oxide, iron vanadium composite oxide, cobalt vanadium composite oxide, cerium vanadium composite oxide, Molybdenum niobium composite oxide, molybdenum tantalum composite oxide, tungsten niobium composite oxide, tungsten tantalum composite oxide, zinc vanadium composite oxide, nickel vanadium composite oxide, copper vanadium composite oxide, scandium vanadium composite oxide, yttrium vanadium Composite oxide, lanthanum vanadium composite oxide, tin vanadium composite oxide, lead vanadium composite oxide, antimony vanadium composite oxide, bismuth vanadium composite oxide, selenium vanadium composite oxide, tellurbana Complex oxide: silicon niobium complex oxide, iron niobium complex oxide, cobalt niobium complex oxide, cerium niobium complex oxide, zinc niobium complex oxide, nickel niobium complex oxide, copper niobium complex oxide, scandium niobium complex oxide Oxide, yttrium niobium composite oxide, lanthanum niobium composite oxide, tin niobium composite oxide, lead niobium composite oxide, antimony niobium composite oxide, bismuth niobium composite oxide, selenium niobium composite oxide, tellurium niobium composite oxide; silicon tantalum Composite oxide, Iron tantalum composite oxide, Cobalt tantalum composite oxide, Cerium tantalum composite oxide, Zinc tantalum composite oxide, Nickel tantalum composite oxide, Copper tantalum composite oxide, Scandium tantalum composite oxide, Yttrium tantalum composite oxide Lantern In addition to the forms including tin complex oxide, tin tantalum complex oxide, lead tantalum complex oxide, antimony tantalum complex oxide, bismuth tantalum complex oxide, selenium tantalum complex oxide, tellurium tantalum complex oxide, etc. It is preferable to include a form supported or immobilized on the carrier described above.
Among them, titanium silicon composite oxide, titanium vanadium composite oxide such as TiVO _4, iron vanadium composite oxide such FeVO _4, cobalt vanadium composite oxide such as Co ₂ V _{2 O 7,} cerium vanadium composite oxide such as CEVO ₄ It is preferable that the material contains molybdenum niobium composite oxide, molybdenum tantalum composite oxide, tungsten niobium composite oxide, and tungsten tantalum composite oxide. In addition, these may be used independently and may use 2 or more types together.

Examples of the catalyst include (1) a form of a titanium-containing oxide catalyst having a Hammett acidity function of −3.0 ≦ H ₀ ≦ + 12.2, and (2) a crystalline titanium composite oxide catalyst having a crystal lattice A crystalline microporous material catalyst containing titanium in the interior and / or a crystalline mesoporous material catalyst containing titanium in the crystal lattice, (3) an oxide having a triclinic crystal structure More preferably, it is a form in which one or more of the forms are combined.

In the form (1), a titanium-containing oxide catalyst having a Hammett acidity function of −3.0 ≦ H ₀ ≦ + 12.2 is used. If the reaction temperature is less than −3.0, condensation of glycerin or decomposition of alcohol may proceed when the reaction temperature becomes high, or the catalyst life may be shortened by coking. If it exceeds +12.2, the active component of the catalyst may be eluted when the reaction temperature becomes high, and a separation or removal step of the catalyst becomes necessary, and the activity as a catalyst cannot be sufficiently maintained. There is a risk of As a lower limit, Preferably, it is -1, More preferably, it is +1.5, More preferably, it is +3.3. Moreover, as an upper limit, Preferably, it is +10, More preferably, it is +9, More preferably, it is +7. Such a titanium-containing oxide catalyst may be a titanium-containing composite oxide catalyst and the above-described crystalline titanium composite oxide catalyst, and if it is a crystalline titanium composite oxide catalyst, Hammett's acidity function Is preferably -3.0 or more and +12.2 or less. More preferably, they are +1.5 or more and +10 or less, More preferably, they are +3.3 or more and +7 or less.
Examples of the titanium-containing oxide catalyst include anatase TiO ₂ , rutile TiO ₂ , titania silica, titania zirconia, titania magnesia, titania calcia, titania yttria, titania boria, titania-tin oxide, and the like. Among them, anatase type TiO ₂ , rutile type TiO ₂ , and titania silica are preferable.

In the form of (2), a crystalline microporous material containing titanium in the crystal lattice and / or a crystalline titanium composite oxide catalyst which is a crystalline mesoporous material containing titanium in the crystal lattice is used. It will be.
The crystalline titanium composite oxide is a crystallized composite oxide and means that it exhibits catalytic activity that requires titanium atoms. Since it is crystallized in this way and has a large surface area, the activity as a catalyst is improved. Such crystalline titanium composite oxides preferably include those in which titanium atoms and other metal atoms are covalently bonded via oxygen atoms. Further, a structure having a titanium atom in the crystal lattice is preferable. As a result, the elution of the active metal component can be sufficiently suppressed, so that the process of separating the active metal component can be omitted and the manufacturing process can be simplified, and the catalyst can be used for a long time. Become.
The crystalline titanium composite oxide is particularly preferably crystalline titanosilicate. Crystalline titanosilicate has a structure in which a titanium atom is incorporated into a silicon skeleton through an oxygen atom. Titanium atoms are difficult to elute and less leaching, thus simplifying the separation and removal process of the catalyst. Or can be kept active as a catalyst over a long period of time.

The above-mentioned crystalline microporous material containing titanium in the crystal lattice has a titanium atom as an essential component in the crystal lattice constituting the crystallizing catalyst, and is a crystalline composite classified by the size of the crystal pores. It belongs to the smallest classification among oxides. A preferred form is one having pores with a diameter of less than 2 nm.
Examples of the titanium-containing crystalline microporous material in the crystal lattice include titanosilicate (TS-1), MFI type titanoaluminosilicate having an MFI type zeolite structure, MEL type titanosilicate (TS-2), and MEL. Type titanoaluminosilicate, BEA type titanosilicate, BEA type titanoaluminosilicate, RUT type titanosilicate, RUT type titanoaluminosilicate, MWW type titanosilicate, MWW type titanoaluminosilicate, ETS-4 type tita Crystalline microporous materials with zeolite structure such as nosilicate, ETS-10 type titanosilicate; crystalline microporous materials with titanoaluminophosphates such as TAPO-5, TAPO-11, TAPO-34, etc. T -1 type titanosilicate is preferred.

The titanium-containing crystalline mesoporous material in the crystal lattice has a titanium atom as an essential component in the crystal lattice constituting the crystallizing catalyst, and is a crystalline composite oxidation classified by the size of the crystal pores. Among the materials, it belongs to the next largest category after the above-mentioned titanium-containing crystalline microporous material in the crystal lattice. A preferred form is one having regular pores having a diameter of 2 nm or more and 20 nm or less. Examples of such a titanium-containing crystalline mesoporous material in the crystal lattice include Ti-containing MCM-41, Ti-containing SBA-1, Ti-containing SBA-15, and the like.

In the form of (3), the triclinic system is a crystal system in which all three crystal axes are obliquely crossed and the lengths of the crystal axes are different from each other, and have a triclinic lattice. Among them, those containing triclinic FeVO ₄ are preferable.

In the above catalyst, it is also preferable that (4) an oxide in which crystals are constituted by an octahedral skeleton formed by binding an essential metal component to an oxygen atom in a hexacoordinate configuration. Among them, (5) a form in which the crystal structure is a rutile structure, (6) a layered oxide in which a crystal is constituted by an octahedral skeleton, and at least one pair of the octahedrons is bonded side by side. A form is more preferable and it is also preferable that it is a form which combined these 1 or 2 or more.

In the form (4), in the essential metal component, six oxygen atoms are coordinated as a ligand, and an octahedral skeleton having the oxygen atom as a vertex is formed. Preferably, it is a form in which the essential metal component is located in the octahedral skeleton. Since the metal component is six-coordinated, it is difficult for the metal component to elute. Examples of the crystal structure of such a catalyst include a rutile structure, a corundum structure, and an ilmenite structure, and a rutile structure is preferable. Examples of such a catalyst include a rutile type TiVO ₄ composite oxide (or solid solution).
In the form of (5) above, the rutile structure is a crystal structure that belongs to a tetragonal system and is formed by a compound represented by AB ₂ (A: positive atom, B: negative atom). In such a crystal structure, A atoms are octahedrally coordinated by B atoms, and each octahedron shares a vertex or a ridge with an adjacent octahedron to form a skeleton structure. Note that a compound having a rutile structure can be obtained by baking a compound having an anatase structure.

The side-shared octahedral layered oxide in the form (6) is in a state where essential metal components are confined in the octahedron. Therefore, it is possible to obtain an oxide.
The layered oxide is a layered structure formed by laminating a plurality of sheet-like oxides. Preferably, a plurality of complex oxides containing at least one metal element selected from the group consisting of Group 4 and Group 5 metal elements are stacked to form a layered structure.
Moreover, for example, a composite oxide having a so-called nanosheet structure obtained by peeling off a sheet-like titanium-containing layered composite oxide using a quaternary ammonium salt can also be suitably used.

The catalyst also includes the following general formula (1);
ATi _X MO _{(2X + 3)} (1)
(A represents a hydrogen atom or an alkali metal atom. M represents a niobium atom or a tantalum atom. X is a natural number of 7 or less.)
A is a hydrogen atom or an alkali metal atom, and among them, a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, and a cesium atom are preferable, and a hydrogen atom is more preferable. Such a layered oxide is preferably a titanium-containing layered complex oxide, and among them, a titanium-containing layered complex oxide catalyst can be suitably used.
As the layered oxide, for _{example, HTiNbO 5, KTiNbO 5, CsTiNbO} 5, HTi 2 NbO 7, CsTi 2 NbO 7, HTi 3 NbO 9, KTi 3 NbO 9, CsTi 3 NbO 9, HNb 3 O 8, KNb 3 _{O 8, CsNb 3 O 8,} HTiTaO 5, KTiTaO 5, CsTiTaO 5, HNbMoO 6, KNbMoO 6, CsNbMoO 6, HNbWO 6, KNbWO 6, CsNbWO 6, HTaMoO 6, KTaMoO 6, CsTaMoO 6, HTaWO 6, KTaWO 6, CsTaWO ₆ , titanium phosphate and the like are preferable. These may be used alone or in combination of two or more. Among these, HTiNbO ₅ , HTi ₂ NbO ₇ , HNb ₃ O ₈ , HNbMoO ₆ , and HNbWO ₆ are preferable.

As the catalyst in the present invention, a baked product may be used, whereby the elution of the active metal component can be further suppressed. The firing temperature is preferably set in consideration of the surface area of the catalyst. For example, the firing temperature is preferably 280 ° C. or higher and 1300 ° C. or lower. If it is lower than 280 ° C., elution may not be sufficiently suppressed, and if it exceeds 1300 ° C., a sufficient catalyst surface area cannot be obtained and fatty acid alkyl ester and / or glycerin may not be produced with high efficiency. . More preferably, it is 400 degreeC or more and 1200 degrees 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 present invention is also a composition obtained by reacting fats and oils with alcohol using a catalyst, and the composition contains 98.00% by mass or more and 99.92% by mass or less of a fatty acid alkyl ester. In addition, it is a composition containing 800 ppm or more and 4500 ppm or less of free fatty acid. By having said composition, it becomes a thing suitable for using for a biodiesel fuel use or surfactant intermediate raw material use, and using for a biodiesel fuel among these is preferable.
If the content of the free fatty acid is less than 800 ppm, the steps such as purification and washing cannot be simplified, so that it cannot be sufficiently advantageous in terms of energy, and if it exceeds 4500 ppm, corrosion of the diesel engine is prevented. This is not preferable because it cannot be sufficiently suppressed or the cetane number decreases. The lower limit is preferably 900 ppm, and more preferably 1000 ppm. Moreover, as an upper limit, Preferably it is 3000 ppm, More preferably, it is 2500 ppm.
When the content of the fatty acid alkyl ester is less than 98.00% by mass, the fatty acid alkyl ester cannot be sufficiently suitably used for various applications, and when it exceeds 99.92% by mass, the energy is sufficiently advantageous. It will not be possible. The lower limit is preferably 98.50% by mass, and the upper limit is preferably 99.90% by mass.

In the method for producing a fatty acid alkyl ester and / or glycerin of the present invention, the method comprises a step of bringing oils and alcohols into contact with each other in the presence of a catalyst. The product is insoluble in any of the products (fatty acid alkyl ester, glycerin, etc.), and the alcohol is distilled off in the absence of a catalyst prior to phase separation of the ester phase and the glycerin phase, which are reaction products. Is also one of the preferred forms.

In the method for producing the fatty acid alkyl ester and / or glycerin, the catalyst is preferably insoluble in oils and fats and alcohol and products such as the fatty acid alkyl ester and glycerin (hereinafter also referred to as insoluble catalyst). In the reaction in which fats and oils are brought into contact with each other, when the reaction proceeds, the phase is mainly separated into a phase mainly containing a fatty acid alkyl ester (ester phase) and a phase mainly containing glycerin as a byproduct (glycerin phase). Become. In this case, alcohol will be contained in both phases, and as a result, fatty acid alkyl ester and glycerol will mutually partition. At this time, when the alcohol is distilled off in the absence of a 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 separation of the fatty acid alkyl ester and glycerin can be improved. Thus, 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. 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 alcohol distillation step, and the utility load in the production cannot be reduced sufficiently. 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 is measured by fluorescent X-ray analysis (XRF) while the reaction solution after the reaction is in a solution state. Moreover, when measuring a more minute elution amount, it measures by a high frequency induction plasma (ICP) emission analysis method.

The present invention is also a catalyst used in the production method of the present invention as described above. The catalyst of the present invention has a performance capable of simultaneously performing esterification and transesterification, and exhibits effects such as that it is not affected by mineral acids and metal components contained in fats and oils and alcohol is not decomposed. In the production method of the present invention, the fatty acid alkyl ester and / or glycerin can be produced with high efficiency.

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 above 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 22 carbon atoms or an alkenyl group having 6 to 22 carbon atoms having one or more unsaturated bonds.
In the above production method, since the transesterification reaction and the esterification reaction can be performed by using the catalyst, the free fatty acid can be simultaneously used in the transesterification reaction step even if the raw oil / fat contains a free fatty acid. Since the esterification reaction proceeds, the yield of the fatty acid alkyl ester can be improved without providing an esterification reaction step separately from the ester exchange reaction step.
In the said manufacturing method, as shown to the said formula, glycerol is obtained with a fatty-acid alkylester by transesterification. In the present invention, purified glycerin can be easily obtained industrially. Such glycerin is useful for various applications as a chemical raw material.

As said fats and oils, what contains fatty acid ester of glycerin and should just become a raw material of fatty acid alkyl ester and / or glycerin with alcohol, and what is generally called "fat" is used. it can. Usually, it is preferable to use oils and fats containing triglyceride (triester of glycerin and higher fatty acid) as a main component and a small amount of diglyceride, monoglyceride and other subcomponents, but using fatty acid ester of glycerin such as triolein Also good.
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, palm oil, safflower oil, linseed oil, cottonseed oil, gill oil, castor oil; beef fat, pig Animal oils and fats such as oil, fish oil and whale fat; used oils (waste cooking oils) of various edible oils are suitable, and these may be used alone or in combination of two or more. Also good.

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.

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 is preferable. You may use these 1 type or in mixture of 2 or more types.
The alcohol is also 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. The method for producing a fatty acid alkyl ester of the present invention can be suitably used in a method for obtaining diglycerides as described later when a polyol is used as the alcohol.
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 to 5 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 five times, the amount of excess alcohol recovered and recycled increases, which may increase costs. The lower limit is more preferably 1.1 times, still more preferably 1.3 times, and particularly preferably 1.5 times. The upper limit is more preferably 4.8 times, still more preferably 4.5 times, and particularly preferably 4.0 times. Moreover, as a more preferable range, it is 1.1 to 4.8 times, More preferably, it is 1.3 to 4.5 times, Especially preferably, it is 1.5 to 4.0 times.
The theoretical required amount of alcohol 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 the alcohol is a polyol, diglycerides can be obtained by the method for producing a fatty acid alkyl ester of the present invention. Such a form is one of the preferred embodiments of the present invention. Diglycerides 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.
According to the method of the present invention, it is preferable to obtain a mixture having monoglyceride and diglyceride as main components, add a free fatty acid or an alkyl ester thereof, and react in the presence of lipase, thereby achieving high selectivity. Diglycerides can be obtained.

The lipase is preferably an immobilized lipase or a bacterial lipase. More preferred is an immobilized lipase or intracellular lipase that selectively acts at positions 1 and 3. As the immobilized lipase, those obtained by immobilizing a 1,3-position selective lipase on an ion exchange resin are preferable. Examples of the 1,3-position selective lipase include the genus Rhizopus, the genus Aspergillus, the genus Mucor, the genus Rhizomucor, the genus Candida, and the genus Thermomyces. Lipases derived from microorganisms such as genera are preferred.
The conditions for causing the lipase to act can be appropriately selected as long as the conditions for obtaining good lipase activity are obtained, but the reaction temperature is preferably 10 to 100 ° C, more preferably 20 ° C or higher and 80 ° C or lower. is there.

Examples of the method for obtaining diglycerides include a method in which a first reaction in which fats and oils are reacted with a polyol using a catalyst, and a second reaction in which lipase is allowed to act on the obtained mixture. In such a method, when alkali is used as a catalyst in the first reaction, it is necessary to adjust the pH after the completion of the first reaction in order to bring the pH in the second reaction to an optimum range for the activity of the lipase. However, by using the method for producing a fatty acid alkyl ester of the present invention as the first reaction, the necessity for adjusting the pH in the second reaction is reduced, and the reaction process can be simplified. Thus, it is one of preferred embodiments to use the method for producing a fatty acid alkyl ester of the present invention in a method for obtaining diglycerides.

As reaction temperature in the manufacturing method of the fatty-acid alkylester of this invention and / or glycerol, it is preferable that it is 50-300 degreeC. If it is less than 50 ° 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, it is 70 degreeC or more and 290 degrees C or less, More preferably, it is 100 degreeC or more and 280 degrees C or less.
It is preferable that the catalyst used for the manufacturing method of the said fatty-acid alkylester and / or glycerol does not elute an active metal component, when using it at the reaction temperature within the said range. 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.

The reaction pressure in the method for producing the fatty acid alkyl ester and / or glycerin of the present invention is preferably 0.1 to 10 MPa. If the pressure 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, it is 0.2 MPa or more and 9 MPa or less, More preferably, it is 0.3 MPa or more and 6 MPa or less.

Even when the reaction temperature and pressure are sufficiently reduced in this way, the method for producing a fatty acid alkyl ester and / or glycerin according to the present invention uses a highly active catalyst as described above, so that the reaction is carried out satisfactorily. It becomes possible to do.
The catalyst having at least one metal element selected from the group consisting of Group 4 and Group 5 metal elements as an essential component can also be used in the supercritical state of the alcohol used. The supercritical state 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.

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 the reaction can be repeatedly carried out by using the catalyst, unreacted raw materials, intermediate glycerides and the like may be contained after the reaction is completed. In this case, for example, after distilling off light boiling components such as alcohol and water from the mixture after the reaction in the absence of a catalyst, unreacted glycerides and free fatty acids are separated and recovered from the effluent. In addition, it is preferably reused together with raw material fats and oils. 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 contacting these in presence of a catalyst is shown by batch type using palm oil as fats and oils and using methanol as alcohol. In such a form, palm oil and methanol are mixed together with a catalyst to carry out the reaction. The reaction solution is allowed to stand to separate into an ester phase mainly containing fatty acid methyl esters and glycerides and a glycerin phase mainly containing glycerol and methanol. Methanol and a catalyst are added to the ester phase obtained by separating the glycerin phase, and the reaction is further performed to separate the ester phase and the glycerin phase to obtain fatty acid methyl ester and glycerin. In such a form, before phase separation of the reaction solution, after separating and removing the solid catalyst from the liquid phase by a process such as filtration, the alcohol is distilled off to obtain the fatty acid methyl esters and glycerin. It is preferable in that the separation can be improved.
The fatty acid methyl ester and / or glycerin thus obtained is preferably further purified by operation of a distillation column depending on the purpose.

FIG. 2 shows a process of contacting a catalyst in a packed reaction tower using a solid catalyst as a stationary phase, using palm oil as fats and methanol as alcohol, using a fixed bed continuous flow reactor. Has been. The post-reaction liquid reacted in the catalyst-packed reaction tower 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 was further reacted with methanol in a catalyst-packed reaction tower to distill off methanol 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 methyl ester and glycerin. The fatty acid methyl ester and / or glycerin thus obtained is preferably further purified by operation of a distillation column depending on the purpose.

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 neutralization removal process of a free fatty acid or the esterification process by an acid catalyst can be made unnecessary.
(3) Saponification of free fatty acids does not occur.
(4) 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 alcohol can be distilled off after the catalyst separation and no reverse reaction occurs, the liquid-liquid two-phase distribution equilibrium is improved (the mutual solubility is lowered) and the product can be separated well. it can.
(2) Further, a crystalline oxide catalyst having at least one metal element selected from the group consisting of Group 4 and Group 5 metal elements as an essential component uses the essential metal component in the crystal skeleton as an active species. Therefore, there is no leaching, the catalyst can have a long life, and 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 is highly selective. The point which can obtain ester and the point which is hard to be influenced by the trace metal component contained in fats and oils and the mineral acid used for pre-processing are mentioned.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “% by mass”.
The conversion and yield in the examples were calculated by the following formula.
Conversion rate (%) = (moles consumed of fats and oils at the end of reaction) / (number of moles of fats and oils 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 diglyceride (mol%) = (number of moles of diglyceride generated at the end of reaction × 2) / (number of moles of effective fatty acids at the time of charging) × 100 (%)
Monoglyceride yield (mol%) = (mol number of monoglyceride produced at the end of reaction) / (mol number 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]
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: Preparation of Titanium Vanadium Oxide Catalyst (Catalyst A) In a solution obtained by dissolving 25.74 g of ammonium metavanadate in 700 g of distilled water at 90 ° C., 169.66 g of a 20% aqueous solution of titanium (III) trichloride was added. It was dripped. After evaporating to dryness, pre-calcination was performed at 350 ° C. for 2 hours in an air stream, followed by calcination at 750 ° C. for 5 hours to obtain a titanium vanadium oxide catalyst (Catalyst A). As a result of the X-ray diffraction measurement of the catalyst A, it was mainly a mixture of a complex oxide having a rutile type TiVO ₄ structure and vanadium pentoxide.

Catalyst Preparation Example 2: Preparation of Iron Vanadium Oxide Catalyst (Catalyst B) 14.04 g of ammonium metavanadate was dissolved in 700 g of distilled water at 90 ° C. (Solution A). A solution prepared by dissolving 48.48 g of iron (III) nitrate nonahydrate in 40 g of distilled water was added dropwise to Solution A and evaporated to dryness. An iron vanadium oxide catalyst (Catalyst B) was obtained by pre-calcining at 350 ° C. for 2 hours under an air stream and subsequently calcining at 750 ° C. for 5 hours. As a result of the X-ray diffraction measurement of the catalyst B, it was a composite oxide mainly having a triclinic FeVO ₄ structure.

Catalyst Preparation Example 3: Preparation of Silica-Supported Iron Vanadium Oxide Catalyst (Catalyst C) In a solution in which 7.49 g of vanadyl oxyoxalate and 13.45 g of iron (III) nitrate nonahydrate were uniformly dissolved in methanol Then, 10 g of silica powder was kneaded and evaporated to dryness with stirring. A silica-supported iron vanadium oxide catalyst (Catalyst C) was obtained by pre-calcining at 350 ° C. for 2 hours under an air stream and subsequently calcining at 750 ° C. for 5 hours.

Catalyst Preparation Example 4: Preparation of Cerium Vanadium Oxide Catalyst (Catalyst D) Same as Catalyst Preparation Example 2 (Catalyst B), except that 53.17 g of cerium (III) nitrate hexahydrate was used instead of iron nitrate. Thus, a cerium vanadium oxide catalyst (catalyst D) was obtained. According to the X-ray diffraction measurement of the catalyst D, it was mainly an oxide having a structure of cerium (IV) dioxide and CeVO ₄ .

Catalyst Preparation Example 5: Preparation of Cobalt Vanadium Oxide Catalyst (Catalyst E) Same as Catalyst Preparation Example 2 (Catalyst B), except that 35.64 g of cobalt (II) nitrate hexahydrate was used instead of iron nitrate. Thus, a cobalt vanadium oxide catalyst (catalyst E) was obtained. As a result of the X-ray diffraction measurement of the catalyst E, it was a complex oxide mainly having a Co ₂ V ₂ O ₇ structure.

Catalyst Preparation Example 6: Preparation of vanadium oxide catalyst (catalyst F) 21.06 g of ammonium metavanadate powder was calcined at 500 ° C. for 3 hours in an air stream to obtain a vanadium oxide catalyst (catalyst F). As a result of the X-ray diffraction measurement of the catalyst F, it was mainly vanadium pentoxide.

Catalyst preparation examples 7 to 8 (catalysts G and H)
Niobium oxide (Nb ₂ O ₅ ) manufactured by Wako Pure Chemicals was used as the catalyst G, and tantalum oxide (Ta ₂ O ₅ ) manufactured by the same company was used as the catalyst H.

Catalyst Preparation Example 9: Synthesis of Titanium Vanadium Zirconium Ternary Complex Oxide (Catalyst I) 80.99 g of zirconyl nitrate (IV) dihydrate was dissolved in 1000 g of distilled water (solution B). 9.21 g of titanium oxysulfate (IV) was dissolved in 23 g of distilled water and added dropwise to Solution B, and a solution obtained by diluting 48.07 g of 25% aqueous ammonia solution with 100 g of distilled water was added dropwise to precipitate a solid. The obtained solid was washed 6 times with 500 mL of distilled water and then dried at 120 ° C. overnight (solid A). 8.46 g of vanadyl sulfate (IV) tetrahydrate was dissolved in 25 g of distilled water, kneaded with the previously obtained solid A, and evaporated to dryness with stirring. Titanium vanadium-zirconium ternary composite oxide (catalyst I) was obtained by preheating at 350 ° C. for 2 hours in an air stream and subsequently firing at 750 ° C. for 5 hours.

Catalyst Preparation Example 10: Preparation of H-type niobate (Catalyst J) 3.47 g of potassium carbonate and 19.96 g of niobium oxide (Nb ₂ O ₅ ) were mixed well in a mortar, and a small amount of water was added and kneaded well. After drying at 120 ° C. for 4 hours, the layered KNb ₃ O ₈ was obtained by firing at 1100 ° C. for 3 hours. This was repeated ion exchange twice with 1N nitric acid aqueous solution (1 L), then washed with water and calcined at 500 ° C. for 2 hours to obtain HNb ₃ O ₈ (catalyst J) ion-exchanged into H-type.

Catalyst Preparation Example 11 Preparation of H-type Titanoniobate (Catalyst K) Potassium carbonate (13.9 g) was dissolved in distilled water (30 g). Anatase-type titanium oxide (16.0 g) and niobium oxide (Nb ₂ O ₅ ) (26.6 g) were mixed well in a mortar, and the potassium carbonate solution was added and kneaded to be homogeneous. After drying at 120 ° C. for a whole day and night, baking was performed at 1100 ° C. for 3 hours to obtain K-type titanoniobate (KTiNbO ₅ ). This was repeated ion exchange twice with 6N nitric acid aqueous solution (150 mL), then washed with water and calcined at 500 ° C. for 2 hours to obtain HTiNbO ₅ (catalyst K) ion-exchanged to H type. The acid strength (H ₀ ) of the thus obtained HTiNbO ₅ catalyst was measured by the Hammett indicator method and found to be between +3.3 and +6.3.

Catalyst Preparation Example 12: Preparation of MFI Titanosilicate (TS-1) (Catalyst L) Under a nitrogen atmosphere, 96.8 g of tetramethyl orthosilicate and 4.8 g of tetraethyl orthotitanate were mixed. To this solution, 400 g of a 10% tetrapropylammonium hydroxide aqueous solution was added dropwise. The mixture was refluxed at 90 ° C. for 3 hours, then transferred to an autoclave and hydrothermally synthesized at 175 ° C. for 48 hours. The obtained white slurry was centrifuged, washed with water, and calcined at 550 ° C. for 3 hours in an air stream to obtain an MFI type titanosilicate (TS-1) catalyst (catalyst L). The obtained titanosilicate had a Ti / Si atomic ratio of 1/22. As a result of measuring the acid strength (H ₀ ) of the TS-1 catalyst thus obtained by the Hammett indicator method, it was between +6.3 and +8.3.

Catalyst Preparation Example 13: Preparation of silica-supported titanium oxide catalyst (catalyst M) 20 g of silica powder was kneaded in a solution in which 3.56 g of titanium tetraisopropoxide was uniformly dissolved in isopropanol, and evaporated to dryness while stirring. did. The silica-supported titanium oxide catalyst (Catalyst M) was obtained by calcination at 500 ° C. for 5 hours in an air stream. The acid strength (H ₀ ) of the titania silica catalyst thus obtained was measured by the Hammett indicator method and found to be between +6.3 and +8.3.

In Examples 1 to 13 and Comparative Example 1, in order to simplify the analysis, triolein or oleic acid-containing triolein was used as a reaction raw material as a reaction raw material.
Example 1
Triolein (60 g), methanol (20 g) and catalyst A (Ti-V) (2.5 g) were charged into an autoclave having a capacity of 200 mL. After substitution with nitrogen, the reaction was carried out for 24 hours at a reaction temperature of 150 ° C. while stirring the interior. It was confirmed by XRF analysis that the total concentration of Ti and V as active elution components was 1000 ppm or less, and further ICP analysis was performed. As a result, elution of Ti and V was not observed.

Comparative Example 1
In Example 1, the reaction was performed in the same manner as in Example 1 except that hydrotalcite was used as a catalyst. The yield of methyl oleate was 77% and the yield of glycerin was 63%. As a result of XRF analysis of the ester phase, as shown in Table 1, almost all of magnesium constituting hydrotalcite and about half of aluminum were eluted.

Examples 2-13
In Examples 2 to 10, the reaction was performed in the same manner as in Example 1 except that catalysts B to J were used instead of catalyst A. In Examples 11 to 13, the reaction was performed in the same manner as in Example 1 except that the catalysts K to M were used instead of the catalyst A and the reaction temperature was changed from 150 ° C to 200 ° C.

Example 14
In Example 1, instead of triolein, a saponification value of 195.9, an effective fatty acid content of 96.5%, a free fatty acid content of 5.1%, and a water content of 0.06% were used. The reaction was carried out in the same manner as in Example 1. The yield of fatty acid methyl ester was 72%, the yield of glycerin was 41%, and the conversion rate of free fatty acid was 64%.

Example 15
In Example 14, except that catalyst K was used instead of catalyst A, the amounts of palm oil, methanol, and catalyst were changed to 70 g, 14 g, and 7.8 g, respectively, and the reaction concentration was changed from 150 ° C. to 200 ° C. Reaction was carried out in the same manner as in Example 14. The yield of fatty acid methyl ester was 65%, the yield of glycerin was 29%, and the conversion rate of free fatty acid was 49%. Further, elution of Ti was not observed.

Example 16
The reaction was conducted in the same manner as in Example 1 except that 2.5 g of oleic acid was further added as a reaction raw material in Example 1. The yield of oleic acid methyl ester was 77%, and the yield of glycerin was 45%. Moreover, elution of Ti and V was not recognized.

Example 17
In Example 16, the reaction was performed in the same manner as in Example 16 except that the catalyst K was used instead of the catalyst A and the reaction temperature was changed from 150 ° C to 200 ° C. The yield of oleic acid methyl ester was 78%, and the yield of glycerin was 71%. Moreover, elution of Ti was not confirmed.

Example 18
The reaction was conducted in the same manner as in Example 17 except that the catalyst L was used instead of the catalyst K in Example 17. The yield of oleic acid methyl ester was 81%, and the yield of glycerin was 74%. Moreover, elution of Ti was not confirmed.

Example 19
Catalyst A was compression molded and then crushed to a particle size of 300 to 850 μm.
Into a SUS-316 straight tube reaction tube having an inner diameter of 10 mm and a length of 210 mm, 15 mL (25 g) of the molded catalyst A was charged. At the outlet of the reactor, a filter and a back pressure valve were attached via an air-cooled cooling pipe so that the pressure could be controlled.
Using a precision high-pressure metering pump, triolein and methanol were circulated downward from the top of the reactor at a flow rate of 0.192 mL / min and 0.040 mL / min (molar ratio = 1/5), respectively. The pressure in the reaction tube was set to 2.5 MPa with a pressure valve.
The reaction tube portion was heated from the outside using a GC oven, and the temperature was set to 150 ° C. The yield of methyl oleate at the outlet of the reactor 3.5 hours after the temperature and pressure were stabilized was 50%.

Example 20
In Example 19, catalyst K was used instead of catalyst A, the flow rates of triolein and methanol were changed to 0.170 mL / min and 0.065 mL / min (molar ratio = 1/9), respectively, and the reaction temperature was 2 The reaction was performed in the same manner as in Example 19 except that the reaction temperature was changed from 0.5 MPa to 3.7 MPa and the reaction temperature was changed from 150 ° C to 200 ° C. The conversion rate of triolein 1.5 hours after stabilization of temperature and pressure was 84%, the yield of oleic acid methyl ester was 50%, and the yield of glycerin was 15%.

Example 21
Saponification value 195.9, effective fatty acid content 96.5%, free fatty acid content 5.1%, water content 0.06% palm oil (28 g), glycerin (9.6 g) and catalyst L (1.25 g) ) In an autoclave having a volume of 100 mL. After nitrogen substitution, the reaction was carried out at a reaction temperature of 250 ° C. for 6 hours while stirring the interior. The conversion was 75%, the diglyceride yield was 20%, and the monoglyceride yield was 55%. There was no byproduct of glycerin condensate or etherified product, and Ti was not eluted.

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.

Claims (9)

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 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, characterized in that: The catalyst is vanadium oxide, niobium oxide, tantalum oxide, titanium vanadium composite oxide, titanium niobium composite oxide, titanium vanadium zirconium ternary composite oxide, or a composite oxide of these and other group metals. is there
The method for producing a fatty acid alkyl ester and / or glycerin according to claim 1. The catalyst may be at least one selected from the group consisting of Group 3, Group 6, Group 8, Group 9, Group 10, Group 11, Group 12, Group 14, Group 15, Group 16 and Lanthanoid elements. The method for producing a fatty acid alkyl ester and / or glycerin according to claim 1 or 2 , which comprises an element and has the element in a crystal lattice . The fatty acid alkyl ester and / or glycerin according to claim 1 , wherein the catalyst is a titanium-containing oxide catalyst having a Hammett acidity function of −3.0 ≦ H ₀ ≦ + 12.2. Production method. 5. The catalyst according to claim 1, wherein the catalyst is an oxide in which a crystal is composed of an octahedral skeleton formed by binding an essential metal component to an oxygen atom in a hexacoordinate configuration. A method for producing a fatty acid alkyl ester and / or glycerin. 6. The method for producing a fatty acid alkyl ester and / or glycerin according to claim 1, 2 , 3, or 5, wherein the catalyst is a vanadium composite oxide having a triclinic crystal structure. The method for producing a fatty acid alkyl ester and / or glycerin according to claim 1, 2 , 3 , 4, or 5, wherein the catalyst is a titanium vanadium composite oxide having a crystal structure of a rutile structure. . The catalyst is a layered oxide in which a crystal is constituted by an octahedral skeleton, and at least one set of the octahedrons is bonded side by side . A method for producing a fatty acid alkyl ester and / or glycerin according to 4 or 5. The layered oxide has the following general formula (1):
ATi _X MO _{(2X + 3)} (1)
9. The compound represented by (A represents a hydrogen atom or an alkali metal atom. M represents a niobium atom or a tantalum atom. X is a natural number of 7 or less.) The manufacturing method of fatty-acid alkylester and / or glycerol of description.

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