JP2007044602A - Catalyst carrier, metal fixed catalyst, production method thereof, and method for oxidizing alcohol using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metal fixed catalyst excellent in chemical stability, and having a high catalyst activity. <P>SOLUTION: The metal fixed catalyst is provided in which a metal is fixed on a catalyst carrier containing a phosphate represented by the general formula (I): (M<SP>IV</SP>O<SB>2</SB>)(P<SB>2</SB>O<SB>5</SB>)<SB>x</SB>(I), wherein M<SP>IV</SP>represents one or two or more elements selected from the group consisting of titanium, zirconium, hafnium, silicon, germanium and tin, and x represents 0.6 to 1. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a catalyst carrier, a metal-immobilized catalyst, a production method thereof, and a production method of an aldehyde or a ketone using the same.

  The oxidation reaction is one of the most basic reactions in organic chemistry, and more than 60% of chemical industry processes are said to be oxidation reactions or related reactions. Among them, the method of producing aldehydes and ketones by oxidation of alcohol is an industrially important reaction. For the purpose of efficiently performing the oxidation reaction of alcohol, chromic acid, lead compounds, mercury compounds, osmium tetroxide, and the like are used as catalysts. However, these are not only toxic and have to be handled with great care, but also pose a problem in the disposal of used catalysts because of the high environmental load.

  As one of the methods for oxidizing alcohol, a method using a combination of dichlorotris (triphenylphosphine) ruthenium (II), which is a ruthenium complex, and an oxidizing agent such as a peroxide is known (Patent Document 1, Japanese Patent Application Laid-Open No. Hei 9 (1999) 11-226417). However, in addition to the complicated synthesis of the ruthenium complex, this method has a drawback that it is very difficult to separate and recover the ruthenium complex from the reaction solution because it is a homogeneous catalytic reaction system. On the other hand, in the heterogeneous catalytic reaction system, a solid catalyst with a small environmental load using only 1 atmosphere of molecular oxygen as an oxidant has been found. For example, in the above oxidation reaction, a method using a solid catalyst in which ruthenium is immobilized on hydrotalcite, which is a layered double hydroxide (Patent Document 2, JP 2002-274852 A), ruthenium is immobilized on hydroxyapatite. A method using a solid catalyst (Patent Document 3, Japanese Patent Application Laid-Open No. 2001-246262) and a method using a catalyst in which ruthenium is immobilized on alumina (Patent Document 4, Japanese Patent Application Laid-Open No. 2004-894) are proposed.

These solid catalysts are easy to separate and recover the catalyst from the reaction solution after the reaction, but have a problem that the catalytic activity is insufficient and the productivity of aldehyde and ketone is low. In addition, hydrotalcite and hydroxyapatite used as a carrier have the property of dissolving under acidic conditions, so that there is a problem that the use conditions of the catalyst are remarkably restricted.
Japanese Patent Laid-Open No. 11-226417 JP 2002-274852 A JP 2001-246262 A JP 2004-000894 A

  Accordingly, the object of the present invention is to solve the above problems and provide a highly active catalyst composition which can be used for oxidation reactions of alcohols, etc., which are excellent in chemical stability and capable of enhancing catalytic activity. There is to do.

  As a result of intensive studies in view of the above problems, the present inventors have developed a phosphate-containing catalyst carrier containing one or more elements selected from the group consisting of titanium, zirconium, hafnium, silicon, germanium, and tin. By immobilizing a metal such as ruthenium, the above-mentioned problems were solved all at once, and the metal-immobilized catalyst was found to be useful for catalytic reactions such as an oxidation reaction, thereby completing the present invention.

That is, the present invention relates to the general formula (I)
^{_{(M IV O 2) (P}} 2 O 5) x (I)
(Wherein, M ^IV represents titanium, zirconium, hafnium, silicon, one or more elements selected from the group consisting of germanium, and tin, x is representing a 0.6 to 1.) Expressed in The present invention relates to a catalyst support containing a phosphate.

In addition, the general formula (II)
(MO) _y (M ^IV O ₂ ) (P ₂ O ₅ ) _z (II)
(In the formula, M represents one or more elements selected from the group consisting of alkali metals, alkaline earth metals, fourth periodic elements of Groups 6 to 12 of the periodic table, and silver, and M ^IV represents (It represents one or more elements selected from the group consisting of titanium, zirconium, hafnium, silicon, germanium and tin, y represents 0.25 to 1, and z represents 0.75 to 1.) The catalyst carrier containing the phosphate represented by these.

Furthermore, the present invention, M ^IV is zirconium or titanium, to the catalyst support.

  The present invention also relates to the catalyst carrier, wherein M is sodium, potassium, lithium, calcium, magnesium or manganese.

  Furthermore, the present invention relates to a metal-immobilized catalyst in which a metal is immobilized on a catalyst carrier containing a phosphate represented by general formula (I) or general formula (II).

  Moreover, this invention relates to the said metal fixed catalyst whose metal is ruthenium.

  Furthermore, this invention relates to the said metal fixed catalyst whose content of ruthenium is 0.1-20 weight% with respect to the total weight of a metal fixed catalyst.

The present invention also relates to a compound of the general formula (I)
^{_{(M IV O 2) (P}} 2 O 5) x (I)
(Wherein, M ^IV represents titanium, zirconium, hafnium, silicon, one or more elements selected from the group consisting of germanium, and tin, x is representing a 0.6 to 1.) Expressed in The present invention relates to a method for producing a metal-immobilized catalyst, wherein a metal is brought into contact with a phosphate.

Furthermore, the present invention provides a compound of the general formula (II)
(MO) _y (M ^IV O ₂ ) (P ₂ O ₅ ) _z (II)
(In the formula, M represents one or more elements selected from the group consisting of alkali metals, alkaline earth metals, fourth periodic elements of Groups 6 to 12 of the periodic table, and silver, and M ^IV represents (It represents one or more elements selected from the group consisting of titanium, zirconium, hafnium, silicon, germanium and tin, y represents 0.25 to 1, and z represents 0.75 to 1.) It is related with the manufacturing method of the metal fixed catalyst which makes a metal contact the phosphate represented by these.

  Moreover, this invention relates to the manufacturing method of the said metal fixed catalyst which makes a ruthenium contact a phosphate.

  Furthermore, this invention relates to the method of manufacturing an aldehyde or a ketone from alcohol using the said metal fixed catalyst.

  The present invention also relates to the use of the metal immobilization catalyst for alcohol oxidation reactions.

The catalyst carrier of the present invention contains a phosphate having a structure represented by the above general formula (I) or general formula (II), has high chemical stability, and has a conventional hydrotalcite or hydroxyapatite. Unlike in acidic conditions, it does not dissolve. In particular, a phosphate carrier in which M ^IV is zirconium or titanium is excellent in chemical stability and can be used in a wide pH range.

The phosphate represented by the general formula (II) includes an alkali metal (sodium, potassium, lithium, etc.), an alkaline earth metal (calcium, magnesium, etc.), a fourth periodic element of Groups 6-12 of the periodic table, and Since one or more elements selected from the group consisting of silver (hereinafter also referred to as “cationic component”) M has immobilized (MO) _y , phosphate (MO) _y (M ^IV The catalytic activity of the support itself containing O ₂ ) (P ₂ O ₅ ) _z is suppressed. Therefore, a catalyst using such a phosphate as a catalyst carrier can obtain even higher selectivity.

  In the catalyst carrier of the present invention, the phosphate represented by the general formula (I) or the general formula (II) can be used as a catalyst carrier as it is, but it should be used as a composite carrier in combination with other catalyst carriers. You can also.

  When the metal immobilization catalyst of the present invention is ruthenium, an aldehyde or a ketone can be easily produced with high conversion and high selectivity by using it for an oxidation reaction of alcohol or the like. In addition, since the metal-immobilized catalyst has high chemical stability, it can be used repeatedly without reducing its activity as a catalyst even when used under high temperature conditions or high or low pH conditions. Furthermore, even when the catalytic activity is reduced by a catalytic reaction such as an oxidation reaction, the catalytic activity can be easily regenerated by immersing in an aqueous solution containing an acid, an alkali, or sodium chloride.

  In particular, a ruthenium-immobilized catalyst having a ruthenium content of 0.1 to 20% by weight with respect to the total weight of the metal-immobilized catalyst can perform an oxidation reaction of alcohol or the like at a high conversion rate. Moreover, since the metal fixed catalyst of this invention can be manufactured only by making a catalyst support | carrier and a metal contact, a metal fixed catalyst can be manufactured very simply.

(1) Catalyst carrier (i) One form of the catalyst carrier of the present invention is represented by the general formula (I)
^{_{(M IV O 2) (P}} 2 O 5) x (I)
(Wherein, M ^IV represents titanium, zirconium, hafnium, silicon, one or more elements selected from the group consisting of germanium, and tin, x is representing a 0.6 to 1.) Expressed in Containing a phosphate.

Here, from the viewpoint of chemical stability of the phosphate as the catalyst support, ^MIV is preferably titanium or zirconium, more preferably zirconium.

When M ^IV is selected from two or more elements, any combination of the above elements is possible, such as zirconium-titanium, zirconium-hafnium, zirconium-silicon, zirconium-germanium, zirconium-tin, titanium-hafnium. , Titanium / silicon, titanium / germanium, titanium / tin, silicon / hafnium, silicon / germanium, silicon / tin, germanium / hafnium, combination of two elements of germanium / tin and hafnium / tin, titanium / zirconium / hafnium, Titanium, zirconium, silicon, titanium, zirconium, germanium, titanium, zirconium, tin, zirconium, hafnium, silicon, zirconium, hafnium, silicon, zirconium, hafnium, germanium, zirconium A combination of three elements such as mu, hafnium, tin, zirconium, silicon, germanium, zirconium, silicon, and tin, or a combination of four or more of the above elements.

The phosphate carrier need not be a crystallographically pure substance. For example, even if a phosphate carrier is crystallographically a mixture of zirconium pyrophosphate and silicon orthophosphate, each constituent element has the general formula What is necessary is just to satisfy (I). Therefore, as long as general formula (I) is satisfy | filled, the phosphate which 2 or more types of elements couple | bonded with oxygen may be sufficient. For example, when M ^IV is two elements of M ^IV _A and M ^IV _B , the general formula (I) is ((M ^IV _A ) _m (M ^IV _B ) _1-m O ₂ ) (P ₂ O ₅ ) _x (Where m represents an arbitrary numerical value in the range of 0 <m <1). As phosphates in which M ^IV is two kinds of elements, (Zr _0.5 Ti _0.5 O ₂ ) (P ₂ O ₅ ) _x , (Zr _0.5 Si _0.5 O ₂ ) (P ₂ O ₅ ) _{x and the} like.

_X of (P ₂ O ₅ ) _{x in} the general formula (I) represents 0.6 to 1, and in the general formula (I), (M ^IV O ₂ ) and (P ₂ O ₅ ) are (M ^IV O ₂ ): (P ₂ O ₅ ) = 1: The ratio is 0.6 to 1. From the viewpoint of chemical stability under a high temperature region, orthophosphate having x of 0.67 or pyrophosphate having x of 1 is particularly preferable.

Preferred examples of the phosphate represented by the general formula (I) include zirconium orthophosphate (ZrO ₂ ) (P ₂ O ₅ ) _0.67 , zirconium pyrophosphate (ZrO ₂ ) (P ₂ O ₅ ), and ortholine. Titanium oxide (TiO ₂ ) (P ₂ O ₅ ) _0.67 , titanium pyrophosphate (TiO ₂ ) (P ₂ O ₅ ), hafnium orthophosphate (HfO ₂ ) (P ₂ O ₅ ) _0.67 , hafnium pyrophosphate (HfO ₂ ) (P ₂ O ₅ ), silicon orthophosphate (SiO ₂ ) (P ₂ O ₅ ) _0.67 , silicon pyrophosphate (SiO ₂ ) (P ₂ O ₅ ), germanium orthophosphate (GeO ₂ ) (P ₂ O ₅ ) _0.67 , germanium pyrophosphate (GeO ₂ ) (P ₂ O ₅ ), tin orthophosphate (SnO ₂ ) (P ₂ O ₅ ) _0.67 , tin pyrophosphate (SnO ₂ ) (P ₂ O ₅ ) and the like.

  Of the above phosphates, zirconium orthophosphate or zirconium pyrophosphate is more preferable from the viewpoints of chemical stability and heat resistance.

(Ii) Another form of the catalyst support of the present invention is represented by the general formula (II)
(MO) _y (M ^IV O ₂ ) (P ₂ O ₅ ) _z (II)
(In the formula, M represents one or more elements selected from the group consisting of alkali metals, alkaline earth metals, fourth periodic elements of Groups 6 to 12 of the periodic table, and silver, and M ^IV represents (It represents one or more elements selected from the group consisting of titanium, zirconium, hafnium, silicon, germanium and tin, y represents 0.25 to 1, and z represents 0.75 to 1.) It contains a phosphate represented by:

^{(M IV} _{O 2)} ^M IV in is synonymous with ^{M IV} of the general formula (I). M is an alkali metal such as lithium, sodium or potassium, an alkaline earth metal such as magnesium, calcium, strontium or barium, a group 6-12 of the periodic table of chromium, manganese, iron, cobalt, nickel, copper and zinc. The fourth periodic element and one or more metals selected from the group consisting of silver are represented. From the viewpoint of the chemical stability of the phosphate, M is preferably sodium, potassium, calcium or magnesium, more preferably potassium or calcium.

M in (MO) means (M _I ) ₂ when selected from a monovalent element M _I such as an alkali metal, and when selected from a divalent element M _II such as an alkaline earth metal means M _II. Regardless of the valence, these monovalent or divalent elements may contain only one type or two or more types in the phosphate represented by the general formula (II). Good. Accordingly, as long as the general formula (II) is satisfied, even if the structure is such that, for example, (Na ₂ O) (M ^IV O ₂ ) (P ₂ O ₅ ) _x , one element is bonded to oxygen, (NaKO ) (M ^IV O ₂ ) (P ₂ O ₅ ) _z may have a structure in which two or more elements are bonded to oxygen, and (Na ₂ O) (K ₂ O) (M ^IV O ₂ ) (P ₂ O ₅ ) _x may be a phosphate having an oxide of two or more elements.

By containing (MO) _y , the catalytic activity of the phosphate itself represented by the general formula (I) is suppressed, so that the catalyst carrier containing the phosphate represented by the general formula (II) In a solid catalyst in which a metal is immobilized, side reactions due to phosphate are suppressed, and the catalytic reaction can proceed with high selectivity.

  y represents 0.25 to 1, and z represents 0.75 to 1. y and z can be set independently, but from the viewpoint of chemical stability of the phosphate, it is preferable to set y and z so that the phosphate is orthophosphate. It is.

Preferable examples of the phosphate represented by the general formula (II) include (Na ₂ O) (ZrO ₂ ) (P ₂ O ₅ ) (y = 1, Z = 1; ZrNa ₂ (PO ₄ ) ₂ ). , (Na ₂ O) _0.25 (ZrO ₂ ) (P ₂ O ₅ ) _0.75 (y = 0.25, z = 0.75; Zr ₂ Na (PO ₄ ) ₃ ), (K ₂ O) (ZrO ₂ ) (P ₂ O ₅ ) (y = 1, Z = 1; ZrK ₂ (PO ₄ ) ₂ ), (K ₂ O) _0.25 (ZrO ₂ ) (P ₂ O ₅ ) _0.75 ( y = 0.25, z = 0.75; Zr ₂ K (PO ₄ ) ₃ ), (Na ₂ O) (TiO ₂ ) (P ₂ O ₅ ) (y = 1, Z = 1; TiNa ₂ (PO ₄ ) ₂ ), (Na ₂ O) _0.25 (TiO ₂ ) (P ₂ O ₅ ) _0.75 (y = 0.25, z = 0.75; Ti ₂ Na (PO ₄ ) ₃ ), ( CaO) _0.25 (ZrO ₂ ) (P ₂ O ₅ ) _0.75 (y = 0 .25, z = 0.75; Zr ₄ Ca (PO ₄ ) ₆ ), (MnO) _0.25 (ZrO ₂ ) (P ₂ O ₅ ) _0.75 (y = 0.25, z = 0.75) Zr ₄ Mn (PO ₄ ) ₆ ) and the like.

Among these, for example, when ruthenium is immobilized to obtain a ruthenium-immobilized catalyst, the conversion rate and selectivity of the oxidation reaction of alcohol are high, (K ₂ O) (ZrO ₂ ) (P ₂ O ₅ ) (y = 1, Z = 1; ZrK ₂ (PO ₄ ) ₂ ) and (CaO) _0.25 (ZrO ₂ ) (P ₂ O ₅ ) _0.75 (y = 0.25, z = 0.75; Zr ₄ Ca (PO ₄ ) ₆ ) is particularly preferred.

(2) Metal-immobilized catalyst The metal-immobilized catalyst of the present invention is obtained by immobilizing a metal M _{cat on} a catalyst carrier containing a phosphate represented by the above general formula (I) or (II). It is.

The metal M _cat immobilized on the catalyst support is not particularly limited, but is an element included in Groups 3 to 12 of the periodic table, and examples thereof include ruthenium, osmium, rhodium, palladium, platinum, and gold, and particularly ruthenium. Is preferred. The metal M _cat can immobilize one or more metals on the catalyst support. In addition, the metal fixed catalyst of this invention may be used independently in a catalytic reaction, or may be used in combination of 2 or more type.

(3) Production of catalyst carrier and metal-immobilized catalyst The metal-immobilized catalyst of the present invention is obtained by, for example, (a) mixing the raw material components of the phosphate-containing catalyst carrier with the general formula (I) or (II). (B) a catalyst carrier containing a phosphate represented by the general formula (I); A method of immobilizing a metal after immobilizing a valent or divalent cation component to form a catalyst support containing a phosphate represented by the general formula (II), (c) represented by the general formula (I) A method of simultaneously immobilizing a monovalent or divalent cation component and a metal on a catalyst carrier containing phosphate, (d) a raw material component of a catalyst carrier containing a phosphate represented by the general formula (I) Are mixed with a monovalent or divalent cation component and a metal at the same time, And a method for obtaining a metal-immobilized catalyst in which a metal is immobilized on a catalyst carrier containing a phosphate represented by the formula: From the viewpoint of easily obtaining a desired product having good catalytic activity, the methods (a) and (b) are preferred. Hereinafter, a method for producing a catalyst carrier composed of a phosphate and an immobilization method using ruthenium as a metal will be described more specifically. These methods are examples of the production method of the present invention, and the present invention is not limited to these. It is not limited to.

(I) Method for producing a catalyst carrier composed of a phosphate represented by the general formula (I) Titanium, zirconium, hafnium, silicon, germanium or tin oxynitrate, oxychloride, oxyacetate or chloride, A solution in which an alkoxide or the like (hereinafter also referred to as “metal raw material”) is dissolved in water and / or an organic solvent (alcohol or the like), and phosphoric acid or diammonium hydrogen phosphate, triammonium phosphate, a phosphate ester, or the like Alternatively, a solution dissolved in an organic solvent (alcohol or the like) is mixed to prepare a phosphate slurry, and then the slurry is spray-dried to produce a particulate phosphate catalyst support. The concentration of the metal raw material is preferably 0.01 to 5.0 mol / l, more preferably 0.5 to 2.0 mol / l. Moreover, 0.01-5.0 mol / l is preferable and, as for the density | concentration of phosphoric acid or a phosphate, 0.1-2.0 mol / l is more preferable. The mixing time is preferably 0.01 to 24 hours, and the mixing temperature is preferably 15 to 40 ° C. The obtained phosphate catalyst carrier is preferably subjected to heat treatment at 300 to 800 ° C. for 0.1 to 24 hours in order to increase the catalytic activity after the ruthenium fixation and to increase the mechanical strength of the catalyst carrier.

(Ii) Method for producing a catalyst carrier composed of a phosphate represented by the general formula (II), a solution of the metal raw material, a solution of the phosphoric acid or phosphate, an alkali metal, an alkaline earth metal, Nitrate, chloride, acetate, etc. of one or more elements selected from the group consisting of the fourth periodic element of Groups 6-12 of the periodic table and silver, and water and / or organic solvent (alcohol etc.) And the solution dissolved in (2) is prepared to prepare a phosphate slurry represented by the general formula (II), and then the slurry is spray-dried to produce a particulate phosphate catalyst support.

  The concentration of the salt of one or more elements selected from the group consisting of alkali metals, alkaline earth metals, group 4 to group 12 elements of the periodic table, and silver is 0.01 to 5 0.0 mol / l is preferable, and 0.5 to 2.0 mol / l is more preferable. The concentration of metal raw material, phosphoric acid or phosphate, mixing time, and mixing temperature are the same as those in the method for producing a catalyst carrier composed of the phosphate represented by the above general formula (I).

  The catalyst support composed of the phosphate represented by the general formula (II) obtained by the above method increases the catalytic activity after immobilization of ruthenium and increases the mechanical strength of the catalyst support. Heat treatment is preferably performed at 800 ° C. for 0.1 to 24 hours. Also, a catalyst carrier composed of a phosphate represented by the general formula (I) is prepared in advance, and a catalyst composed of a phosphate represented by the general formula (II) by immobilizing a cation component. When a carrier is used, its components, concentration, mixing time, and temperature are the same as in the above production method.

(Iii) Method for immobilizing ruthenium After bringing the water and / or alcohol solution of the ruthenium compound into contact with the phosphate catalyst carrier, filtration, washing, drying and the like are performed. Examples of the ruthenium compound include ruthenium chloride, ruthenium nitrate, ruthenium acetylacetonate, and the like. The concentration of the solution is preferably 0.001 to 10 g / l, and more preferably 0.1 to 5.0 g / l. The contact method is not particularly limited, and may be any method such as mixing or liquid passing. The contact time is preferably from 0.1 to 24 hours, and more preferably from 0.5 to 4 hours. 5-50 degreeC is preferable and, as for contact temperature, 20-40 degreeC is more preferable. Washing can be performed with water, acetone, methanol, or the like, and drying can be performed by vacuum drying, vacuum drying, heat drying, air drying, or the like. In order to obtain higher catalytic activity, air drying is preferred.

  The amount of ruthenium immobilized is preferably 0.1 to 20% by weight relative to the total weight of the ruthenium-immobilized catalyst, and more preferably 1 to 10% by weight in order to carry out the oxidation reaction at a high conversion rate. Further, the cation component and its concentration in the methods (c) and (d) above, and the ruthenium compound component and its concentration are the same as those in the production method described in (i) or (ii) above, The immobilization time and temperature are the same as in the case of (iii) ruthenium immobilization method.

(4) Oxidation reaction of alcohol or the like The corresponding aldehyde or ketone can be produced by bringing the ruthenium-immobilized catalyst obtained by the above method into contact with an alcohol in the absence of a solvent or in the presence of a solvent. As alcohol used for reaction, C1-C20 aliphatic linear alcohol, C1-C20 aliphatic cyclic alcohol, etc. are mentioned, These may be either saturated and unsaturated, unsubstituted Or may have a substituent, and includes any of primary alcohols, secondary alcohols and tertiary alcohols. Substituents include alkyl groups such as methyl, ethyl, and hexyl groups, alkoxy groups such as methoxy, ethoxy, and butoxy groups, aromatic hydrocarbon groups such as phenyl, and heterocyclic groups such as pyridyl and thienyl. , Nitro group, cyano group, amino group, halogen such as chlorine atom, and the like.

  Specific examples of the alcohol used in the reaction include methanol, ethanol, 1-butanol, 2-butanol, t-butanol, 1-hexanol, 2-hexanol, 1-octanol, 2-octanol, 3-octanol, 1-dodecanol, Aliphatic linear alcohols, cyclohexanol, cyclopentanol, 1-cyclohexenol, 1-cyclopene, which may have a substituent such as benzyl alcohol, phenethyl alcohol, cinnamyl alcohol, 2- (hydroxymethyl) pyridine Examples include aliphatic cyclic alcohols which may have a substituent such as tenol.

  The solvent is not particularly limited as long as it does not adversely affect the oxidation reaction, and may not be used. Examples of the solvent include benzene, toluene, acetonitrile, dichloromethane, cyclohexane, dichloroethane, chloroform and the like. To promote the oxidation reaction efficiently, toluene, benzene and the like are preferable.

  The oxidation reaction temperature is preferably 0 to 150 ° C, more preferably 20 to 100 ° C. The reaction time is preferably 0.01 to 50 hours, more preferably 0.1 to 30 hours. The contact method is not particularly limited, and means such as mixing and liquid passing can be used.

  The ruthenium-immobilized catalyst of the present invention is particularly suitable as an alcohol oxidation catalyst, but is not limited thereto, and can be used for an oxidation reaction of a substrate other than alcohol. For example, aldehydes, amines and thiols can be used as a substrate for the reaction to oxidize to the corresponding carboxylic acid, nitrile and disulfide.

(5) Method for regenerating metal-immobilized catalyst The metal-immobilized catalyst of the present invention may have reduced catalytic activity when used. In such a case, for example, the catalytic activity of the metal-immobilized catalyst used in the oxidation reaction can be regenerated by a treatment such as acid dipping, alkali dipping, or sodium chloride aqueous solution dipping. Examples of the acid used here include hydrochloric acid, sulfuric acid, nitric acid, and the like. The concentration is preferably 0.001 to 1000 mmol / l, and 0.001 to 100 mmol / l is more preferable for obtaining a higher regeneration effect. .

  Examples of the alkali include sodium hydroxide and potassium hydroxide, and the concentration is preferably 0.001 to 100 mmol / l, and more preferably 0.001 to 10 mmol / l in order to obtain a higher regeneration effect. Sodium chloride is preferably 0.001 to 1000 mol / l, and more preferably 0.01 to 100 mol / l in order to obtain a higher regeneration effect. In any immersion liquid, the immersion time is preferably 0.5 to 24 hours, and the immersion temperature is preferably 15 to 70 ° C.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

Example 1
(1) Production of zirconium phosphate carrier 1 liter of 0.5 mol / l zirconium oxynitrate aqueous solution and 1 liter of 1.0 mol / l ammonium dihydrogen phosphate aqueous solution were dropped and mixed to prepare a zirconium phosphate slurry. The slurry was spray-dried to produce zirconium phosphate particles. The obtained zirconium phosphate particles were heat-treated at 650 ° C. for 4 hours, and X-ray diffraction measurement was performed.

The diffraction lines observed in the powder X-ray diffraction profile were in good agreement with the Powder Diffraction File (PDF) No. 85-0896 ZrP ₂ O ₇ (International Center for Diffraction Data).

Diffraction line No .; Diffraction index; Lattice spacing (actual value / PDF value), 1; 111; 0.47665 nm / 0.47631 nm, 2; 200; 0.41297 nm / 0.41250 nm, 3; 210; 0.36957 nm / 0.36895 nm, 4 211; 0.33707 nm / 0.33681 nm, 5; 220; 0.29191 nm / 0.29168 nm, 6; 311; 0.24887 nm / 0.24875 nm

  The measurement conditions for X-ray diffraction (RINT2100 / PC manufactured by Rigaku Corporation) are: target Cu, tube voltage 40 kV, tube current 40 mA, divergence slit 1/2 °, divergence longitudinal restriction slit 10.00 mm, scattering slit 1/2 °. The light receiving slit was set to 0.30 mm.

(2) Immobilization of ruthenium After putting 10 g of zirconium phosphate support in 1 liter of ruthenium chloride aqueous solution (containing 0.5 g of Ru in 1 liter) and adding sodium hydroxide aqueous solution to adjust the pH to 4.5, Stir for 4 hours at room temperature using a magnetic stirrer. Thereafter, it was filtered and washed with water, washed with acetone and then air-dried. The amount of Ru immobilized was quantified by fluorescent X-ray analysis and confirmed to be 5% by weight based on the total weight of the ruthenium immobilized catalyst. The fluorescent X-ray uses a ZSX100e wavelength dispersion type fluorescent X-ray analyzer (manufactured by Rigaku Corporation). The conditions are: analytical line Ru-Lα, target Rh, tube voltage-tube current 50 kV-70 mA, detector PC, Spectral crystal Ge was set.

Example 2
(1) Production of zirconium phosphate support 1 liter of a 0.75 mol / l zirconium oxynitrate aqueous solution and 1 liter of a 1.0 mol / l ammonium dihydrogen phosphate aqueous solution were dropped and mixed to prepare a zirconium phosphate slurry. The slurry was spray pyrolyzed to produce zirconium phosphate particles. The obtained zirconium phosphate particles were heat-treated at 700 ° C. for 4 hours, and X-ray diffraction measurement was performed in the same manner as in Example 1. The powder X-ray diffraction profile showed a halo pattern showing an amorphous phase.

(2) Immobilization of ruthenium After putting 10 g of zirconium phosphate support in 1 liter of aqueous ruthenium chloride solution (containing 1.0 g of Ru in 1 liter) and adjusting the pH to 5.0 by adding aqueous sodium hydroxide solution, Stir for 4 hours at room temperature using a magnetic stirrer. Thereafter, it was filtered and washed with water, washed with acetone and then air-dried. The amount of Ru immobilized was determined by fluorescent X-ray analysis in the same manner as in Example 1 and confirmed to be 10% by weight based on the total weight of the ruthenium immobilized catalyst.

Example 3
(1) Production of Titanium Phosphate Carrier One liter of 0.5 mol / l titanium tetraisopropoxide in isopropanol and 1 liter of 1.0 mol / l phosphoric acid in isopropanol were added dropwise and mixed to form white titanium phosphate. A precipitate was obtained. The white precipitate was filtered off, washed with water, dried at 150 ° C. for 8 hours, and then heat treated at 600 ° C. for 4 hours, and X-ray diffraction measurement was performed in the same manner as in Example 1 (TiP ₂ O ₇ ). The powder X-ray diffraction profile showed a halo pattern showing an amorphous phase.

(2) Immobilization of ruthenium After adding 10 g of titanium phosphate carrier (1) to an aqueous ruthenium chloride solution (containing 0.5 g of Ru in 1 liter) and adjusting the pH to 4.5 by adding an aqueous potassium hydroxide solution The mixture was stirred for 4 hours at room temperature using a magnetic stirrer. Thereafter, it was filtered and washed with water, washed with acetone and then air-dried. The amount of Ru immobilized was determined by fluorescent X-ray analysis in the same manner as in Example 1 and confirmed to be 5% by weight based on the total weight of the ruthenium immobilized catalyst.

Example 4
(1) Manufacture of titanium phosphate carrier 1 liter of an isopropanol solution of 0.75 mol / l titanium tetraisopropoxide and 1 liter of an isopropanol solution of 1.0 mol / l phosphoric acid are dropped and mixed to form a slurry of titanium phosphate Got. The slurry was spray dried and then heat treated at 650 ° C. for 4 hours, and X-ray diffraction measurement was performed in the same manner as in Example 1. The powder X-ray diffraction profile showed a halo pattern showing an amorphous phase.

(2) Immobilization of ruthenium After putting 10 g of titanium phosphate carrier in 1 liter of ruthenium nitrate aqueous solution (containing 0.5 g of Ru in 1 liter) and adjusting the pH to 4.5 by adding aqueous sodium hydroxide, Stir for 4 hours at room temperature using a magnetic stirrer. Thereafter, it was filtered and washed with water, washed with acetone and then air-dried. The amount of Ru immobilized was determined by fluorescent X-ray analysis in the same manner as in Example 1 and confirmed to be 5% by weight based on the total weight of the ruthenium immobilized catalyst.

Example 5
(1) Production of potassium zirconium phosphate carrier 1 liter of 0.5 mol / l zirconium oxynitrate aqueous solution, 1 liter of 1 mol / l phosphoric acid aqueous solution, and 0.5 liter of 2 mol / l potassium hydroxide aqueous solution are dropped. Mixing to prepare a potassium zirconium phosphate slurry. The slurry was spray-dried to produce potassium zirconium phosphate particles. The obtained potassium zirconium phosphate particles were heat treated at 650 ° C. for 4 hours to obtain a catalyst carrier. When X-ray diffraction measurement was performed in the same manner as in Example 1, a halo pattern showing an amorphous phase was obtained in the powder X-ray diffraction profile. Furthermore, the diffraction line observed in the powder X-ray diffraction profile of potassium zirconium phosphate obtained by heat treatment at 1000 ° C. was in good agreement with PDF No. 76-0242 K ₂ Zr (PO ₄ ) ₂ .

Diffraction line No .; Diffraction index; Lattice plane spacing (actual value / PDF value), 1; 001; 0.90190 nm / 0.90110 nm, 2; 011; 0.40157 nm / 0.40134 nm, 3; 012; 0.31794 nm / 0.31777 nm, 4 110; 0.25902 nm / 0.25880 nm, 5; 104; 0.20127 nm / 0.20129 nm, 6; 11-3; 0.19609 nm / 0.19606 nm

(2) Immobilization of ruthenium 10 g of zirconium phosphate potassium support (1) was put into a ruthenium chloride aqueous solution (containing 0.5 g of Ru in 1 liter), and stirred with a magnetic stirrer at room temperature for 4 hours. Thereafter, it was filtered and washed with water, washed with acetone and then air-dried. The amount of ruthenium immobilized was quantified by fluorescent X-ray analysis in the same manner as in Example 1, and it was confirmed that the amount was 5% by weight based on the total weight of the ruthenium immobilized catalyst.

Example 6
(1) Production of sodium zirconium phosphate carrier 1 liter of 0.5 mol / l zirconium oxynitrate aqueous solution, 1 liter of 0.75 mol / l phosphoric acid aqueous solution, and 0.25 mol / l sodium hydroxide aqueous solution 1.0 The mixture was added dropwise to prepare a sodium zirconium phosphate slurry. The slurry was spray-dried to produce sodium zirconium phosphate particles. The obtained sodium zirconium phosphate particles were heat treated at 650 ° C. for 4 hours to obtain a catalyst carrier. When X-ray diffraction measurement was performed in the same manner as in Example 1, the diffraction line observed in the powder X-ray diffraction profile was in good agreement with PDF No. 70-0233 NaZr ₂ (PO ₄ ) ₃ .

Diffraction line No .; Diffraction index; Lattice plane spacing (actual value / PDF value), 1; 104; 0.45953 nm / 0.45604 nm, 2; 110; 0.44004 nm / 0.44075 nm, 3; 113; 0.38143 nm / 0.38105 nm, 4 024; 0.31625 nm / 0.31692 nm, 5; 116; 0.28810 nm / 0.28741 nm, 6; 300; 0.25364 nm / 0.25447 nm, 7; 324; 0.16720 nm / 0.16738 nm

(2) Immobilization of ruthenium 10 g of sodium zirconium phosphate support (1) was put in a ruthenium chloride aqueous solution (containing 0.5 g of Ru in 1 liter), and stirred at room temperature for 2 hours using a magnetic stirrer. Thereafter, it was filtered and washed with water, washed with acetone and then air-dried. The amount of ruthenium immobilized was quantified by fluorescent X-ray analysis in the same manner as in Example 1, and it was confirmed that the amount was 5% by weight based on the total weight of the ruthenium immobilized catalyst.

Example 7
(1) Production of lithium zirconium phosphate support 1 liter of 0.5 mol / l zirconium oxynitrate aqueous solution, 1 liter of 0.75 mol / l diammonium hydrogen phosphate aqueous solution, and 1 mol / l lithium nitrate aqueous solution 0.25 A lithium zirconium phosphate slurry was prepared by dropwise mixing with 1 liter. The slurry was spray-dried to produce lithium zirconium phosphate particles. The obtained lithium zirconium phosphate particles were heat-treated at 650 ° C. for 4 hours to obtain a catalyst carrier. When X-ray diffraction measurement was performed in the same manner as in Example 1, the diffraction line observed in the powder X-ray diffraction profile was in good agreement with PDF No. 84-0998 LiZr ₂ (PO ₄ ) ₃ .

Diffraction line No .; Diffraction index; Lattice plane spacing (actual value / PDF value), 1; 110; 0.44060 nm / 0.44235 nm, 2; 300; 0.25476 nm / 0.25539 nm, 3; 134; 0.19941 nm / 0.19850 nm

(2) Immobilization of ruthenium 10 g of zirconium phosphate potassium support (1) was put into a ruthenium chloride aqueous solution (containing 0.5 g of Ru in 1 liter), and stirred with a magnetic stirrer at room temperature for 4 hours. Thereafter, it was filtered and washed with water, washed with acetone and then air-dried. The amount of ruthenium immobilized was quantified by fluorescent X-ray analysis in the same manner as in Example 1, and it was confirmed that the amount was 5% by weight based on the total weight of the ruthenium immobilized catalyst.

Example 8
(1) Production of calcium zirconium phosphate carrier 2 liters of a 2 mol / l zirconium oxynitrate aqueous solution, 3 liters of a 2 mol / l diammonium hydrogen phosphate aqueous solution, and 0.5 liters of a 2 mol / l calcium nitrate aqueous solution are dropped. Mixing to prepare a calcium zirconium phosphate slurry. The slurry was spray pyrolyzed to produce zirconium calcium phosphate particles. The obtained zirconium calcium phosphate particles were heat-treated at 650 ° C. for 4 hours to obtain a catalyst carrier (Zr ₄ Ca (PO ₄ ) ₆ ). When X-ray diffraction measurement was performed in the same manner as in Example 1, the diffraction line observed in the powder X-ray diffraction profile was in good agreement with PDF No. 33-0321 CaZr ₄ (PO ₄ ) ₆ .

Diffraction line No .; Diffraction index; Lattice spacing (actual value / PDF value), 1; 012; 0.62224 nm / 0.63160 nm, 2; 110; 0.44225 nm / 0.43920 nm, 3; 113; 0.37635 nm / 0.37980 nm, 4 024; 0.31360 nm / 0.31594 nm, 5; 116; 0.28702 nm / 0.28651 nm, 6; 214; 0.25576 nm / 0.25643 nm, 7; 220; 0.21978 nm / 0.21965 nm, 8; 306; 0.21132 nm / 0.21062 nm, 9 134; 0.19770 nm / 0.19777 nm

(2) Immobilization of ruthenium 10 g of zirconium calcium phosphate support (1) is put into an aqueous ruthenium chloride solution (containing 0.5 g of Ru in 1 liter), and 1 mol / l sodium hydroxide is added so that the pH becomes 4.0. The aqueous solution was added and stirred using a magnetic stirrer at room temperature for 4 hours. Thereafter, it was filtered and washed with water, washed with acetone and then air-dried. The amount of ruthenium immobilized was determined by fluorescent X-ray analysis in the same manner as in Example 1, and it was confirmed that the amount was 5% by weight based on the total weight of the ruthenium immobilized catalyst.

Example 9
(1) Manufacture of magnesium zirconium phosphate support 2 liters of a 2 mol / l zirconium oxynitrate aqueous solution, 3 liters of a 2 mol / l diammonium hydrogen phosphate aqueous solution, and 0.5 liters of a 2 mol / l magnesium nitrate aqueous solution were dropped. Mixing to prepare a magnesium zirconium phosphate slurry. The slurry was spray pyrolyzed to produce magnesium zirconium phosphate particles. The obtained magnesium zirconium phosphate particles were heat treated at 750 ° C. for 4 hours to obtain a catalyst carrier. When X-ray diffraction measurement was performed in the same manner as in Example 1, the diffraction line observed in the powder X-ray diffraction profile was in good agreement with PDF No. 45-0419 MgZr ₄ (PO ₄ ) ₆ .

Diffraction line No .; Diffraction index; Lattice spacing (actual value / PDF value), 1; 011; 0.56116 nm / 0.56015 nm, 2; 111; 0.44270 nm / 0.44171 nm, 3; -121; 0.39554 nm / 0.39553 nm, 4; -221; 0.37788 nm / 0.37670 nm, 5; 012; 0.33472 nm / 0.3352 nm, 6; -222; 0.31341 nm / 0.31349 nm, 7; 400; 0.31042 nm / 0.31069 nm, 8; -213; 0.27450 nm / 0.27462 nm, 9; 202; 0.25545 nm / 0.25511 nm

(2) Immobilization of ruthenium 10 g of zirconium magnesium phosphate support (1) was put in an aqueous ruthenium chloride solution (containing 0.5 g of Ru in 1 liter), and the pH was adjusted to 4.5 by adding an aqueous sodium hydroxide solution. Then, it stirred using the magnetic stirrer at normal temperature for 4 hours. Thereafter, it was filtered and washed with water, washed with acetone and then air-dried. The amount of ruthenium immobilized was quantified by fluorescent X-ray analysis in the same manner as in Example 1, and it was confirmed that the amount was 5% by weight based on the total weight of the ruthenium immobilized catalyst.

Example 10
(1) Manufacture of zirconium phosphate manganese support 2 liters of 2 mol / l zirconium oxynitrate aqueous solution, 3 liters of 2 mol / l diammonium hydrogen phosphate aqueous solution and 0.5 liter of 2 mol / l manganese nitrate aqueous solution were dropped and mixed. Thus, a zirconium manganese phosphate slurry was prepared. The slurry was spray pyrolyzed to produce zirconium manganese phosphate particles. The obtained zirconium manganese phosphate particles were heat-treated at 800 ° C. for 4 hours to obtain a catalyst carrier. When X-ray diffraction measurement was performed in the same manner as in Example 1, the diffraction lines observed in the powder X-ray diffraction profile were in good agreement with PDF No. 45-0015 MnZr ₄ (PO ₄ ) ₆ .

Diffraction line No .; Diffraction index; Lattice spacing (actual value / PDF value), 1; 200; 0.44268 nm / 0.44230 nm, 2; 211; 0.37770 nm / 0.37810 nm, 3; 004; 0.31073 nm / 0.31250 nm, 4 213; 0.28675 nm / 0.28720 nm, 5; 114; 0.28183 nm / 0.27990 nm, 6; 312; 0.25546 nm / 0.25560 nm, 7; 420; 0.19814 nm / 0.19840 nm

(2) Immobilization of ruthenium 10 g of zirconium phosphate manganese support (1) was added to a ruthenium chloride aqueous solution (containing 0.5 g of Ru in 1 liter), and the pH was adjusted to 4.0 by adding an aqueous sodium hydroxide solution. Then, it stirred using the magnetic stirrer at normal temperature for 4 hours. Thereafter, it was filtered and washed with water, washed with acetone and then air-dried. The amount of ruthenium immobilized was determined by fluorescent X-ray analysis in the same manner as in Example 1, and it was confirmed that the amount was 5% by weight based on the total weight of the ruthenium immobilized catalyst.

Example 11
(1) Production of zirconium phosphate silver support 1 liter of 0.5 mol / l zirconium oxynitrate aqueous solution, 1 liter of 0.75 mol / l phosphoric acid aqueous solution, and 1.0 liter of 0.25 mol / l silver nitrate aqueous solution The mixture was added dropwise to prepare a silver zirconium phosphate slurry. The slurry was spray dried to produce silver zirconium phosphate particles. The obtained silver phosphate silver particles were heat treated at 600 ° C. for 4 hours to obtain a catalyst carrier. When X-ray diffraction measurement was performed in the same manner as in Example 1, the diffraction line observed in the powder X-ray diffraction profile was in good agreement with PDF No. 34-1245 AgZr ₂ (PO ₄ ) ₃ .

Diffraction line No .; lattice spacing (actual value / PDF value), 1; 0.44141 nm / 0.43800 nm, 2; 0.38244 nm / 0.38000 nm, 3; 0.28634 nm / 0.28700 nm, 4; 0.25466 nm / 0.25400 nm, 5; 0.19089 nm / 0.19000 nm

(2) Immobilization of ruthenium 10 g of zirconium phosphate silver support (1) was put in a ruthenium chloride aqueous solution (containing 0.5 g of Ru in 1 liter), and stirred at room temperature for 2 hours using a magnetic stirrer. Thereafter, it was filtered and washed with water, washed with acetone and then air-dried. The amount of ruthenium immobilized was determined by fluorescent X-ray analysis in the same manner as in Example 1, and it was confirmed that the amount was 5% by weight based on the total weight of the ruthenium immobilized catalyst.

Example 12
Ruthenium (10% by weight) immobilized zirconium phosphate of Example 2 0.1 g and DL-1-phenylethyl alcohol 2 mmol were added to 10 ml of toluene, and 0.5 hours at 80 ° C. under atmospheric pressure and oxygen atmosphere. Stir. The product was quantified by gas chromatography in the same manner as in Example 12, and acetophenone was obtained in a yield of 96%. The conversion rate at this time was 96%, and the selectivity was 100%. The gas chromatography uses GC-17A (manufactured by Shimadzu Corporation), and the analysis conditions are column: DB-WAX 30 m × 0.25 mm (manufactured by J & W), carrier gas: helium, detector: FID, column temperature. : 180 ° C.

Example 13
Ruthenium (5 wt%)-immobilized titanium phosphate of Example 4 0.1 g and DL-1-phenylethyl alcohol 2 mmol were added to 10 ml of toluene and stirred at 80 ° C. for 1 hour under atmospheric pressure and oxygen atmosphere. . The product was quantified by gas chromatography in the same manner as in Example 12, and acetophenone was obtained in a yield of 99%. The conversion rate at this time was 99%, and the selectivity was 100%.

Example 14
Ruthenium (5 wt%) immobilized potassium potassium phosphate of Example 5 0.1 g and DL-1-phenylethyl alcohol 2 mmol were added to 10 ml of toluene, and the mixture was heated at 80 ° C. under atmospheric pressure, oxygen atmosphere or air atmosphere. It was made to react with. The product was quantified by gas chromatography in the same manner as in Example 12. As a result, acetophenone was obtained in a yield of 100% at a reaction time of 0.5 hour under any atmosphere. The conversion and selectivity under each condition were both 100%.

Example 15
Using 0.5 g of ruthenium (5% by weight) immobilized potassium zirconium phosphate of Example 5 as a catalyst, the conversion and selectivity of the substrates shown in Table 1 were examined. The conversion, selectivity, reaction temperature and reaction time are shown in Table 1. As shown in Table 1, it can be seen that aldehydes or ketones can be obtained with high conversion and high selectivity using any substrate.

Example 16
The ruthenium (5 wt%) immobilized sodium zirconium phosphate of Example 6 and 0.5 mmol of DL-1-phenylethyl alcohol were added to 10 ml of toluene and stirred at 80 ° C. for 1 hour under atmospheric pressure and oxygen atmosphere. did. The product was quantified by gas chromatography in the same manner as in Example 12, and acetophenone was obtained in a yield of 100%. The conversion rate at this time was 100%, and the selectivity was 100%.

Example 17
0.5 g of ruthenium (5 wt%) immobilized lithium zirconium phosphate and 2 mmol of benzyl alcohol in Example 7 were added to 10 ml of toluene and stirred at 80 ° C. for 1 hour under atmospheric pressure and oxygen atmosphere. The product was quantified by gas chromatography in the same manner as in Example 12, and benzaldehyde was obtained in a yield of 100%. The conversion rate at this time was 100%, and the selectivity was 100%.

Example 18
Ruthenium (5 wt%)-immobilized zirconium calcium phosphate of Example 8 0.1 g and DL-1-phenylethyl alcohol 2 mmol were added to 10 ml of toluene and stirred at 80 ° C. for 2 hours under atmospheric pressure and oxygen atmosphere. did. The product was quantified by gas chromatography in the same manner as in Example 12, and acetophenone was obtained in a yield of 98%. The conversion rate at this time was 99%, and the selectivity was 99%.

Example 19
Ruthenium (5 wt%) immobilized magnesium magnesium phosphate of Example 9 0.1 g and DL-1-phenylethyl alcohol 2 mmol were added to 10 ml of toluene and stirred at 80 ° C. for 2 hours under atmospheric pressure and oxygen atmosphere. did. The product was quantified by gas chromatography in the same manner as in Example 12, and acetophenone was obtained in a yield of 98%. The conversion rate at this time was 99%, and the selectivity was 99%.

Example 20
10 g of ruthenium (5 wt%)-immobilized zirconium phosphate of Example 10 and 2 mmol of DL-1-phenylethyl alcohol were added to 10 ml of toluene and stirred at 80 ° C. for 2 hours under atmospheric pressure and oxygen atmosphere. did. The product was quantified by gas chromatography in the same manner as in Example 12, and acetophenone was obtained in a yield of 99%. The conversion rate at this time was 99%, and the selectivity was 100%.

Example 21
0.2 g of ruthenium (5 wt%)-immobilized silver phosphate of Example 11 and 2 mmol of DL-1-phenylethyl alcohol were added to 10 ml of toluene and reacted at 80 ° C. under atmospheric pressure and oxygen atmosphere. The product was quantified by gas chromatography in the same manner as in Example 12. As a result, acetophenone was obtained in a yield of 100% at a reaction time of 4 hours. The conversion and selectivity under the above conditions were both 100%.

Comparative Example 1
As in Example 6, 0.1 g and 1− of ruthenium (9.2% by weight) / hydroxyapatite (HAp, manufactured by Wako Pure Chemical Industries, Ltd.) and ruthenium (5% by weight) / alumina (manufactured by Acros) were used. 2 mmol of phenylethyl alcohol was added to 10 ml of toluene, followed by stirring at 80 ° C. for 1 hour under atmospheric pressure and oxygen atmosphere. The results of quantifying the product by gas chromatography in the same manner as in Example 5 are shown in Table 2. As compared with the ruthenium-immobilized catalyst of the present invention, ruthenium / HAp and ruthenium / alumina had a low conversion rate.

Claims (12)

Formula (I)
^{_{(M IV O 2) (P}} 2 O 5) x (I)
(Wherein, M ^IV represents titanium, zirconium, hafnium, silicon, one or more elements selected from the group consisting of germanium, and tin, x is representing a 0.6 to 1.) Expressed in A catalyst carrier containing a phosphate. Formula (II)
(MO) _y (M ^IV O ₂ ) (P ₂ O ₅ ) _z (II)
(In the formula, M represents one or more elements selected from the group consisting of alkali metals, alkaline earth metals, fourth periodic elements of Groups 6 to 12 of the periodic table, and silver, and M ^IV represents (It represents one or more elements selected from the group consisting of titanium, zirconium, hafnium, silicon, germanium and tin, y represents 0.25 to 1, and z represents 0.75 to 1.) The catalyst support | carrier containing the phosphate represented by these. The catalyst support according to claim 1 or 2, wherein M ^IV is zirconium or titanium. The catalyst carrier according to claim 2 or 3, wherein M is sodium, potassium, lithium, calcium, magnesium or manganese.   A metal-immobilized catalyst, wherein a metal is immobilized on the catalyst carrier according to claim 1.   The metal-immobilized catalyst according to claim 5, wherein the metal is ruthenium.   The metal-immobilized catalyst according to claim 6, wherein the content of ruthenium is 0.1 to 20% by weight based on the total weight of the metal-immobilized catalyst. Formula (I)
^{_{(M IV O 2) (P}} 2 O 5) x (I)
(Wherein, M ^IV represents titanium, zirconium, hafnium, silicon, one or more elements selected from the group consisting of germanium, and tin, x is representing a 0.6 to 1.) Expressed in A method for producing a metal-immobilized catalyst, wherein a metal is brought into contact with a phosphate. Formula (II)
(MO) _y (M ^IV O ₂ ) (P ₂ O ₅ ) _z (II)
(In the formula, M represents one or more elements selected from the group consisting of alkali metals, alkaline earth metals, fourth periodic elements of Groups 6 to 12 of the periodic table, and silver, and M ^IV represents (It represents one or more elements selected from the group consisting of titanium, zirconium, hafnium, silicon, germanium and tin, y represents 0.25 to 1, and z represents 0.75 to 1.) The manufacturing method of the metal fixed catalyst which makes a metal contact the phosphate represented by these.   The method for producing a metal-immobilized catalyst according to claim 8 or 9, wherein ruthenium is brought into contact with the phosphate.   A method for producing an aldehyde or a ketone from an alcohol using the metal immobilization catalyst according to claim 6 or 7.   Use of the metal-immobilized catalyst according to claim 6 or 7 for an alcohol oxidation reaction.