TW200829331A - Rhodium-tellurium intermetallic compound particle, method for producing the same, and use of the same - Google Patents

Abstract

For the purpose of efficiently producing a high-purity rhodium-tellurium intermetallic compound particle, a solution containing a rhodium salt, a tellurium salt and a complexing agent is brought into contact with a reducing agent and an organic compound containing a sulfur atom and/or a nitrogen atom is used as the complexing agent.

Description

200829331 IX. Description of the invention: [Technical field to which the invention pertains] It::::: A method for producing ruthenium-iridium intermetallic compound particles; and a ruthenium-based metallographic compound particle, which is produced by using a secret-ruthenium metal: And: an oxidation catalyst, and a method for producing an oxidative addition product using the oxidation catalyst. [Prior Art]

In order to promote the oxidative ethoxylation reaction of decadiene, the industry mainly uses PdTe-based catalyst. ‘, : The two phases are more selective than the PdTe-based catalysts. RhTe-based catalysts can be used. In terms of economic superiority, the development of RhTe = media will be of great significance. However, since the Rh (10) medium is largely dissolved in the acetic acid belonging to the solvent in the reaction, the activity is reduced in the active phase, so that it has not yet reached industrialization. As a general technique for producing alloy particles, it is known to mix a solution containing a gold salt and a solution containing a reducing agent, and at this time, a reduction reaction is carried out to obtain alloy particles. Specifically, a method L of dropping a metal salt solution into a heated reducing solvent as described in Non-Patent Document 1 or a method of dropping a solution of a prolonged agent in a heated metal salt solution as described in Patent Document 1 is employed. Method, etc. However, according to these methods, the reduction reaction is carried out while mixing and diffusing the reducing agent and the genus salt, so that the reduction method of the metal salt is different, and as a result, only the alloy particles having the unevenness can be obtained to improve the problem. In order to increase the reduction reaction rate and reduce the influence of the mixing/diffusion 312XP/invention specification (supplement)/97-01/96135322 5 200829331, it is proposed in Patent Document 2 that the metal salt solution is previously mixed and reduced. The solution of the first reducing agent having a weaker force is dropped to a method of heating the solution containing the second reducing agent having a strong reducing power, but the effect is not sufficient. Λ In addition, in the non-specialized 2, EDTA is described as a wronging agent, which is contacted with a reducing agent according to neutral conditions, but in this method, the mismatched Rh salt is precipitated. Even after the reduction operation, it is difficult to synthesize an intermetallic compound. ' (Non-Patent Document 1) J0urnal of the American Chewed Society, 83, 4916, 1962 (Non-Patent Document 2) Pre-collection of the 96th Catalyst Workshop, 3E12, 3El3. (Patent Document 1) Japanese Patent Laid-Open Japanese Patent Publication No. 4294608 (Patent Document 2) SUMMARY OF THE INVENTION (Problems to be Solved by the Invention) The present invention has been made in view of the above circumstances. That is, the object of the present invention is to provide a method for efficiently producing high-purity ruthenium-intermetallic compound particles, and a scorpion intermetallic compound scorpion manufactured by the method and a long one for one kind of money - an oxidizing catalyst in which the ruthenium intermetallic compound particles are supported on a carrier, and the ruthenium is added to the oxidized addition V of the (4) oxidation catalyst. (Means for Solving the Problem) The inventors of the present invention have intensively studied in view of the above problems, and as a result, found that 312 ΧΡ / invention specification (supplement) / 97_〇1/96135322 200829331 measures the use of a sulfur atom and/or a nitrogen atom. The organic compound, and the solution containing the cerium salt and the hoof salt and the complexing agent, can be efficiently produced to produce a high-purity ruthenium ruthenium metal bond, and the obtained hoof-homometallic compound When the oxidized catalyst is used as the oxidizing catalyst, it is classified as the active species. 'Yes, i.e., the present invention is intended to be an intermetallic compound particle having a ruthenium and a ruthenium, and its specific 仫 is 6 to 16 nm, and the atomic ratio of ruthenium to osmium is 3 Å. Qiao 2 3. 4 (Shenzhen patents are here, the atom of 锗 and 碲 is better than 3: 2, 3: 4 or 丨:! (applicable to the scope of patent application 2). Other aspects of the invention are intended to An oxidizing catalyst characterized in that the ruthenium-iridium intermetallic compound particles of the present invention are carried on the carrier patent claim 3 (3). Mat Ming; b $ ^ ^ Oxidation catalyst is preferably a catalyst for the ifoxylation reaction (article 4 of the patent application). The other method of the present invention is to provide a method for contacting a solution containing a cerium salt and a cerium salt and a complexing agent with a reducing agent, at least the coating method of the cerium-cerium intermetallic compound particles. The mixture is an organic compound containing a sulfur atom and/or a U group (application patent item 5). In this case, the above-mentioned cerium salt and cerium salt and the complexing agent are dissolved in an aqueous alkali solution, and then contacted with a reducing agent (Patent Patent No. 6). Further, the above-mentioned salt is preferably ruthenium chloride (item 7 of the patent application). 312XP/Invention Manual (Supplement)/97·〇1/96135322 ? 200829331 In addition, the above-mentioned cerium salt is preferably selected from the group consisting of citric acid and its salts, and linoleic acid and its salts (application patent scope) 8 items). Further, other aspects of the present invention are directed to a ruthenium-iridium intermetallic compound particle 'the feature 4 which is obtained by the above-described production method, item 9).

Further, the other aspect of the present invention is directed to an oxidation catalyst which is characterized in that the above-mentioned ruthenium-iridium metallographic compound particles are supported (claim No. 1 of the patent application). Further, the other method of the present invention is directed to an oxidative addition product, which is characterized in that, in the presence of the above-mentioned oxidative contact molecular oxygen, the milk nucleophile is oxidatively added to the rare Smoke or (application for patent scope 11). The chemical substance (the effect of the invention) According to the present invention, the ruthenium-iridium intermetallic compound particles can be efficiently obtained by a simple method. ,. The second ’ 使 所得 所得 碲 碲 碲 碲 碲 碲 碲 碲 碲 , 碲 , , 碲 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The present invention will be described in detail below, but the present invention is not limited thereto, and various modifications can be made without departing from the spirit and scope of the invention. The method of producing the 铭-碌 intermetallic compound particles of the present invention is abbreviated as "the manufacturing method of the present invention". The solution of the mixture and the reducing agent are contacted with the two-person aging salt and the sand-day mixture is an organic compound having a sulfur atom and/or a nitrogen atom in the 312XP/invention specification (supplement)/97-01/96135322 8 200829331. In the present invention, by controlling the metal salt, the type of the complexing agent and the reducing agent, and the pH at the time of the reduction reaction, the reducing degree of the metal salt can be controlled to synthesize a homogeneous nano-metal compound. [1 -1·铑 salt] The onium salt used in the production method of the present invention may, for example, be an inorganic compound (such as an oxide of cerium, a nitrate or a sulfate), a halide (such as a chloride of cerium), or an organic compound. An acid salt (such as an acetate of hydrazine), a mixed salt (such as an ammonia complex of hydrazine), an acetylamine complex of an organometallic compound (10), and the like. Further, it is also possible to dissolve the genus itself in the reaction solution to make it, as a cerium salt, preferably an inorganic compound containing cerium, a dentate of a cerium, or an organometallic compound containing cerium, more specifically using cerium chloride. Compound. Ma Shanghe's money can be used alone or in combination of two or more kinds in any combination and in any ratio. [1 -2·碲 salt] The onium salt used in the production method of the present invention may, for example, be a capped a substance (an oxide of lanthanum, a mechanical acid and a salt thereof, a phthalic acid, and a pot: Such as the wide-toothed compound (the gasification of bismuth, desertification, etc.), the organic bismuth compound, the anti-Ben Λ 碑 碑 、, etc.). Further, the hoof metal itself may be dissolved in the reaction liquid to be used. ^中二 as a bismuth salt 'better' contains an inorganic compound, a dentate, a ruthenium-organic compound _ ' 更 无机 无机 无机 无机 无机 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明9 200829331 Chloride of matter or bismuth. The salts and the perindic acid and salts thereof are preferred as the onium salts, especially those selected from the group consisting of decanoic acid and succinic acid. In addition, the onium salt may be used alone or in combination of two or more. [1 - 3 · Wrong agent] The species may be in any combination and ratio. In the production method of the present invention, the complexing agent is a very important factor. The manufacturing method of the present invention is characterized in that an organic compound containing a sulfur atom and/or a nitrogen atom is used as a blocking agent. Examples of the complexing agent containing a sulfur atom or a nitrogen atom include organic acids, phosphorus compounds, hydrazines, guanamines, amines, and alcohols. Specific examples of the organic acid include the compounds listed below. D-2-Amino-3-mercapto-3-mercaptobutyric acid (D-2-Amino-3-Mercapto-3 ie1:hylbutanoic acid) (penicillamine: molecular formula CsHnOAS), _imino group Iminodiacetic acid (IDA: C4Hr〇4N), (N-(Cyclohexyl) iminodiacetic acid) (Molecular formula:

Ci〇Hi7〇4N) ^ Nitrilotriacetic acid (NTA: molecular formula C6H9〇6N), N-(2-tetrahydropyranyl) imidodiacetic acid (N-(2-TetrahydropyranyImethy1) Iminodiacetic acid) (CuHLN), 312XP/invention specification (supplement)/97·01/96135322 10 200829331 N-(2-hydroxyethyl)-extended ethyldiazepine-anthracene, Ν', Ν'-three Acetic acid (N-(2-Hydroxyethyl)ethylenedinitrilo-N, Ν', Ν'-tr. iacetic acid) (HEDTA for short: molecular formula CioHuOD, Ethylenedinitrilotetraacetic acid (EDTA: molecular formula GLN2) , DL-(Methylethylene) dinitrilotetraacetic acid (PDTA: molecular formula CllHl8〇8N2), 10 trans-1,2-cyclohexyldiazide tetraacetic acid (trans -1,2-Cyclohexylene dinitrilotetraacetic acid) (CDTA: molecular formula C14H22O8N2), Ethylenebis (oxyethylenenitrilo) tetraacetic acid (referred to as EGTA · · molecular formula, di-ethyl Triazatetraacetic acid • (Diethylenetrini Trilotetraacetic acid) (referred to as DTPA: molecular formula C14H23O1DN3), Triethylenetetranitrilohexaacetic acid (TTHA: molecular formula CuHsoOuNO, . 6-mercaptopurine _2-acidic acid (6-Methlpyridine-2) -carboxy 1 ic ^ acid) (N-(2-Pyridylmethyl)iminodiacetic acid) (Molecular Formula 312XP/Invention Manual (Repair) )/97-01/96135322 11 200829331 C10H12O4N2), (substituted thio)acetic acid represented by the formula Z-SCH2CO2H (in the above formula, z represents a thiol group, an ethyl group, a propyl group, An alkyl group having 1 to 30 carbon atoms such as butyl, 1-mercaptopropyl, pentyl or hexyl; 2-propenyl (卩1*(^-2-61^1), 3-butenyl ( 6111:-3-61^1), 4-pentenyl (Pent-4-enyl) or the like having 2 to 30 carbon atoms; benzyl group or the like having 6 to 30 carbon atoms. ), DL-Mercaptobutanedioic acid (thiomalic acid: molecular formula C4H6O4S), (Ethylenedithio) diacetic acid (molecular formula C6Hi) 〇〇4S2), Oxybis (ethylenethioacetic acid) (Molecular Formula C8Hu〇5S2), Thiobis (ethylenethioacetic acid) (Molecular Formula) C8Hn〇4S3), 0 Carboxymethylthiobutanedioic acid (CeEUOeS), 2,2-bis(hydroxyindenyl)-3-mercaptopropanol (2,2-Bis(hydroxymethyl)-3 -mercaptopropanol) (monothiopentaerythtitol: molecular formula. C5H12O3S), Thiosalicylic acid (TS: molecular formula C^HsChS) 〇 As a specific example of the phosphorus compound, for example, 3-(II) Phenylphosphino)benzene 312XP/Invention Manual (supplement)/97-01/96135322 12 200829331 3-(Diphenylphosphino)benzenesulfonic acid (3-sulfotriphenylphosphine) : Molecular formula C18H15O3SP), etc.Specific examples of the anthraquinone include, for example, butyl-2,3-dione dioxime

V (Butane-2, 3-diondioxime) (dimethylglyoxime: molecular formula C4H8O2N2), 1,2-diphenylethene-1,2-di(1,2-Diphenylethane-1, 2-dione dioxime) (M^*a-¥*:^(a-benzildioxiine): * 10 subform C-2N2) and the like. Specific examples of the guanamines include the following compounds. Sulfurylamine carbonate (111丨0031^31111(16) (thiourea urea (1:1^01^68): molecular formula CH4N2S), monothiooxamide (molecular formula GfhONzS), N-N' - N, Ν'-Bis(2-hydroxyethyl)monothiooxamide (Molecular Formula • C6H12O3N2S), N-N' _bis(3_hydroxypropyl)monosulfide N,Ν'-Bis(3-hydroxypropy1)monothiooxamide (Molecular Formula C8H16O3N2S), N-N'-bis(4-carbylbutyl)monothiooxydecylamine. (1^, ^-618(4-1^(11"〇71)11士71)111〇11〇1:111〇〇31111(16)(Molecular Formula C10H20O3N2S) 'N-N'-Bis(5-Hydroxypentyl) ) N, Ν'-Bis (5-hydroxypentyl) monothiooxamide (Molecule 312XP / invention specification (supplement) / 97-01/96135322 13 200829331 Formula CuI^Os-S), N- Ν'-Bis(2-sulfoethyl)dithiooxamide (Molecular Formula C6H12O6N2S4) 〇 As a specific example of the amine, for example The following compounds: methylamine (pour 61:1^1311^116) (molecular formula (:115?0, ethyl (Ethylamine) (Molecular Formula C2H7N), Propylamine (Molecular Formula C3H9N), Butylamine (Molecular Formula C4H11N), Pentylamine (CsHuN), Hexylamine (CiHisN) ), Isobutylamine (Molecular Formula C4H11N), 2-Aminoethanol (ethanolamine: Molecular Formula C2H7ON), Ethylenediamine (Molecular Formula C2IM2), φ Triterpenoid II Trimethylenediamine (Molecular Formula C3Hi〇N2), Tetraethylenediamine (Molecular Formula C4H12N2), Pentamethylenediamine (Molecular Formula), 1,3-Diamino-2-propanol (1,3-Diamino-2-propanol) (2-hydroxytrimethylenediamine: molecular formula. C3H10ON2) > Oxy-bis(2-ethylamine) (0xybis(2-ethyl) Amine)) (17-Diaza-4-oxaheptane): Molecular Formula 312XP/Invention Manual (Supplement)/97-01/96135322 14 200829331 C4H12ON2), Extension Ethyl bis(oxy-2-ethethylamine) (Ethy 1 enebis (oxy-2-ethy 1 am) Ine)) 0,10-diaza-4,7-dioxadecane (1,10-diaza-4, 7-dioxadecane): molecular formula C6H16O2N2), thiobis(2-ethylamine) Thi〇bis(2-ethylamine)) (l,7-diaza-4-thiaheptane: molecular formula C4H12N2S), 1,2,3-triaminopropane (1,2, 3-Triaminopropane) Molecular Formula • CH), Tr is (ami nomethyl) met hane (Molecular Formula C4H13N3), Dimethylamine (Molecular Formula C2H7N), 1,4, 1,4,7-Triazaheptane (Molecular Formula C4H13N3) 〇 As a specific example of the alcohol, for example, 1,3-dihydroxy-4-(2-pyridine-ylazo) Benzene (1,3-dihydroxy-4-(2_pyridylazo)benzene) (abbreviated as PAR: molecular formula CnH9〇2N3). Among them, as the complexing agent, an organic acid or an alcohol is preferable, and specifically, the compounds listed below are preferable. Oxy bis (ethylenethioacetic acid) (molecular formula CsHhOA), .N-(2-hydroxyethyl) extended ethyldiazide-N,N,,N,- N-(2-Hydroxyethyl)ethylenedinitrilo-N, hydrazine, N,-tr iacetic acid (HEDTA: composition formula Ci〇Hi8〇7N2), 312xp/invention specification (supplement)/97-01/ 96135322 15 200829331 Ethylenedinitrilotetraacetic acid (EDTA: composition formula CbH-), 3-(Diphenylphosphino)benzenesulfonic acid (3-sulfonate) 3-sulfotriphenylphosphine · · molecular formula CisHi5 〇 3SP), DL-Mercaptobutanedioic acid (thiomalic acid: composition CdHeChS), thiosalicylic acid (Thiosal icy 1 ic acid) (TS _·composed formula • CMO2S) '1,3-dihydroxy-4-(2-pyridylazo)benzene (1,3-dihydroxy-4-(2-pyridylazo) Benzene) (abbreviated as PAR · · composition C11H9O2N3). Among them, as a complexing agent, Ethylenedinitrilotetraacetic acid (EDTA: composition formula Ci〇Hi6〇8N2) and Thiosal icy 1 ic acid (referred to as 10TS · Composition C7H6O2S), 1,3-dipyridyl-4-(2-σ ratio azo azo)benzene (1,3-(111^(11:〇父7-4-(2-07]:1) (171&2〇)56112 6116) (referred to as? Bamin: composition formula CnH9〇2N3). Particularly good is Thiosalicylic acid (TS: composition formula C7H6O2S), 1, dipyridyl _4 -(2-dihydroxy-4-(2-pyridylazo)benzene) (abbreviated as PAR: , composition formula CnH9〇2N3). Further, the various exemplified agents described above may be Any one of them may be used alone or in combination of two or more types in any combination and ratio. 312XP/Invention Manual (Repair y97-〇l/96135322 16 200829331 In addition, a second wrong sword listed in τ may be used as needed. In particular, when tannic acid is used as the onium salt, it is preferred to use a second crosslinking agent. As the second crosslinking agent, for example, a compound having a « and/or a trans group and being soluble in water can be used. Specific examples include, for example, citric acid, malonic acid, frequency acid, succinic acid, tartaric acid, maleic acid, citric acid, acidic amino acid, neutral amino acid, basic neck, and Lack #田基&Special. Among them, 'preferably citric acid, / vermiculite I, frequency fruit acid, preferably citric acid. : and the second wrong agent exemplified above can be used alone or in combination. Two or more types can be used in combination according to any combination and ratio. Π-4·Metal salt solution], 容ΐ:::! In the method of making 'use a solution of money salt and strontium salt and a wrong agent (hereinafter referred to as " The metal salt solution "), and the reduction reaction described later is carried out. If the type of the agent is used to solve the problem of the present invention, then: =: = If water or an organic solvent is usually used, for example, For example, alcohols such as methanol and ethanol. Water = media, from the viewpoint of easy pH control, water is preferred, and distilled water is particularly preferred. q Also, the solvent can be used alone or in any of the two. It can be used in combination with the above. It can also be used according to the combination and proportion of the above-mentioned solvents. Mp; van Gogh salt and the wrong agent, so that the strontium salt and the 意 仃 仃 , , , , 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲 碲Further, in the production method of the present invention, the straw is reduced by the original agent, anti-π χ ρ / @ Η _ ^ (supplement) / 97 613 ying 17 200829331, and the complexing agent is completely dissolved in the gold solution.

In the case of the strontium salt and the cerium salt solution, it is important to make the metal salt (the cerium salt and the cerium salt) and the complexing agent two: There are no special restrictions. Each of the metal salts and the impurities may be dissolved in a solvent to be mixed, or the metal salt and the mixed salt may be mixed and dissolved in the solvent. σ II and I prevent the precipitation of the metal salt solution, preferably the phase is selected appropriately

The concentration of the metal salt (onium salt and sulfonium salt) and the complexing agent on the solvent, and the temperature at the time of mixing and dissolution. Also, the concentration of each metal salt (salt salt and strontium salt) and the wrong agent in the salt, the liquid solution is set to be equal to or less than the saturation degree of each metal salt (antimony salt and barium salt) and the wrong agent. concentration. The saturation solubility varies depending on the type of the metal salt and the complexing agent, the type of the solvent, the temperature at the time of dissolution, and the like, and the concentration of each of the metal salts (onium salt and onium salt) and the complexing agent can be selected. In general, the degree of each metal salt (onium salt and sulfonium salt) of the metal salt solution is generally 0.001% by weight or more, preferably 0.005% by weight or more, based on the weight of the metal. The amount is preferably 1% by weight or more, and is usually 10% by weight or less, preferably 5% by weight or less, more preferably 2% by weight or less. In addition, the ratio of each of the metal atoms (铑 and 碲) in the metal salt (yttrium salt and yttrium salt) is set to be a metal atom feed which is almost identical to the composition of the target 锗_碲 intermetallic compound. proportion. The ratio of the amount of the metal atom (铑 and 碲) to the metal salt (铑 and 碲) may be the stoichiometric mixture of the metal 312ΧΡ/invention specification (supplement)/97-01 /96135322 18 200829331 (stoichiometric mixture ratio) or more, if the ratio of the cross-linking agent is too high, the metal concentration is lowered due to the solubility relationship, and the amount of metal that can be carried in one operation is reduced. And in terms of economy, it is not good. In general, the stoichiometric mixing ratio is usually 1.0 or more, and usually 10 or less, preferably 5 or less, more preferably 2 or less, and particularly preferably 1.5 or less. Further, the metal salt solution may contain other components in addition to the above-mentioned onium salt, onium salt, a complexing agent and a solvent, within a range not inhibiting the reduction reaction described later. As an example of other components, for example, a metal salt having a metal atom other than ruthenium and osmium may be mentioned. Further, these may be used alone or in combination of two or more kinds in any combination and in any ratio. [1 - 5·Reduction reaction] The production method of the present invention has a step of bringing a solution (metal salt solution) containing a cerium salt and a cerium salt and a reducing agent into contact with a reducing agent to carry out a reduction reaction. , Lu Reducing agent used in the manufacturing method of the invention is not limited as long as it is a solvent soluble in metal salt/gluten. Specific examples of the reduction form include a nitrogen compound such as a nitrogen compound, a boron compound such as vaporized sulfonate, a carboxylic acid such as formic acid or a salt thereof, an alcohol such as decyl alcohol, or the like. Among them, as the reducing agent, sodium hydride and hydrazine are preferred. - Still the 'reducing agent exemplified above. If you use one of them in advance, you can use them in combination of two or more types depending on the combination and ratio. As the amount of the carrier, the amount of all metal complexes contained in the above metal salt solution 312XP/invention specification (supplement)/97-〇1/96135322 200829331 can be sufficiently reduced to the amount of metal. . In general, it is usually i times equivalent or more with respect to 1 equivalent of the metal, and is preferably 12 equivalents or more, more preferably 1.5 equivalents or more, still more preferably 2 equivalents or more, in consideration of the efficiency of the reduction reaction. In addition, in consideration of the post-treatment of the unreacted material, the upper limit is usually 5 〇〇 equivalent or less, preferably 100 equivalents or less, more preferably 40 equivalents or less. Also, 'have (4) when using hydrazine as a reducing agent' because the original reaction carried out by hydrazine differs depending on the type of metal salt to be reduced and the pH, and the reduction reaction cannot be expected. Therefore, in the present invention, it is assumed to be 2 equivalents per 1 mole. There is no method for making the metal salt solution "different". (IV) Usually, a reducing agent is added to the above metal salt solution and mixed to carry out a reduction reaction. The reducing agent may be directly added to the mixture of the genus salt and mixed. However, it is easy to mix and dissolve the solution, so it is possible to mix and mix the salt solution in advance. The agent solution is added to the golden blood:: ': is the solvent'. If the reducing agent can be dissolved, the type And: 2 recording the use of a single solvent, can also be used in any combination and ratio of two or more solvents. The same solvent as the solvent. The amount of reduction in the reducing agent solution using the metal salt solution is not particularly limited. In the case of using ^=f and the solution of the original agent, the amount of the agent can be added to the metal salt solution, and the amount of the agent in the above range is "reduction of the metal in the liquid 312XP / invention manual ( Supplement) /97-01/96135322 20 200829331 The temperature at the time of the reduction reaction is usually 55t: or more, preferably 7〇. 〇 above, : 'usually below the boiling point, preferably 9 (rc or less, better 8 (dry circumference of rc or less. If the temperature during the reduction reaction is too high, the reduction reaction is fast = row, so there is a target metal On the other hand, if the temperature is too low, the reducing power is too weak and the target compound of gold f cannot be obtained. In the following description, the above-mentioned predetermined temperature range is referred to as "regulation. In the order of the start of the de-reaction reaction, for example, the following two methods can be used, and any one of the steps can be used. • A low temperature (not exceeding the above-mentioned regulations) to the extent that the reduction reaction is not carried out even if a reducing agent is added. The temperature in the range of the reduction temperature is usually below normal temperature, preferably 1 (TC or less, more preferably 5 aC), and a reducing agent (reducing agent solution) is added to the metal salt solution and mixed, and then the temperature is raised until the reduction reaction can be sufficiently performed. The temperature at which the temperature is carried out (the temperature within the above specified temperature range). • The metal salt solution is heated in advance to allow the reduction reaction of the metal salt to be sufficiently carried out at a temperature (in the above specified temperature range). Temperature), a method of adding a reducing agent to start the reduction reaction in this state. Further, in the case of the reduction reaction, it is preferred to adjust the reaction liquid (liquid in which the reducing agent is added to the metal salt solution) to be inspective. In other words, it is preferable that the pH of the reaction liquid is usually 1 or more, preferably 12 or more, and more preferably 13 or more. If the pH of the reaction liquid is too low (that is, the alkalinity is too weak), Rh may not be formed. The condition of the reaction solution is not limited, and the pjj modifier is usually used. As a pH adjuster, if it is not metal with a metal salt (铑 or hoof), the 312XP/invention specification (supplement)/97 -01/96135322 21 200829331 Compounds that coordinate or do not hinder the degree of mismatch, the metal #合(四) is generally low-shelled and has a helmet limitation. As a pH adjuster, it can be... Cattle such as hydrochloric acid, nitric acid, sulfuric acid, ammonia water, sodium, etc., in the middle of the hydrazine is hydrochloric acid, nitric acid, hydrogen and oxygen

Further, the pH adjuster may be used alone or in combination of two or more. Any one of the steps of adjusting the pH by using a pH adjuster in any combination may be adjusted to the above-mentioned predetermined range while keeping the metal salt from being precipitated. Specific one can be. There are no restrictions. In the state in which the reduction of the reaction liquid can be carried out, the following steps can be exemplified, and before the solution of the metal salt solution is prepared by dissolving the strontium salt, the sulfonium salt and the cleavage agent in the solvent, respectively. The pH of each solution was individually adjusted by a Qiu adjuster. • After the = metal salt solution containing (4), cerium salt and the wrong agent is prepared, the metal salt solution of the metal salt solution is adjusted by the pH adjusting agent before the reduction reaction, and the reduction reaction is not carried out. After adding a reducing agent under temperature conditions (temperature conditions not exceeding the above-mentioned predetermined temperature range), the pH adjusting agent is adjusted by heating the reaction liquid to a temperature condition (temperature condition within the above-mentioned predetermined temperature range) during which the reduction reaction is carried out. The pH of the reaction solution. Further, the pH adjustment by the pH adjuster can be carried out once or in two or more steps. [1 -6· Post-treatment] By the above reduction reaction, ruthenium-iridium intermetallic compound particles 312 ΧΡ / invention specification (supplement) / 97-〇 1/96135322 22 200829331 can be obtained. The obtained ruthenium-iridium intermetallic compound particles can be used as they are, and can be subjected to separation, washing, drying, heat treatment, etc., as needed. The method of separating the obtained ruthenium-iridium intermetallic compound particles from the reaction liquid, and the soaking &' can be, for example, an over-concentration method using crepe paper or crepe paper, separation, precipitation separation (decantation method, etc.), and the like. Among them, filtration and methods are generally used. These methods may be used singly or in combination of two or more kinds in any combination. The solvent (washing solvent) in the case where the ruthenium-ruthenium intermetallic compound particles are removed from the knives is not the same as the ruthenium-iridium intermetallic compound granules: the reactants or the two-way intermetallic compound particles. There is no limitation on the adverse effect, and for example, a solvent of the same kind as the solvent which can be used is usually used. Further, the "washing solvent" may be used alone or in combination according to any combination and ratio. Drying and drying the hoof's hoof intermetallic compound particles after the second gentleman or washing) can be dried under normal pressure and reduced pressure (or vacuum). The conditions of the vicinity (Μ or how many additions and subtractions) are as a drying method, for example, a rotary drying like a stationary rotary evaporator such as a furnace, a fixed bed gas, a moving = two, a spray drying such as a dryer, In the case of a belt-type furnace or a dry type, it is possible to use a 帛 ace ace = = , , , , , , , , 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 As a gas that flows during drying, • (4), by _ 312XP/^H^W(M#)/97-〇l/96135322 23 200829331 =,: Air, nitrogen, etc. are often used. Further, in the case of performing enthalpy, intermetallicization: in the case of air treatment of the particles, hydrazine can be added to the gas to be circulated during drying. The === is used for the desired use of the carbon-hoof metallization without the hydrogen treatment after drying, and is preferably gas from the viewpoint of economy. And /: ^ soil phantom moon gas 2 with any kind, the village recorded combination and ratio (4) 2 like the combination of t, quick drying, from the point of view, 'preferably in the circulation of the water . There is no special restriction on the temperature during drying. == The agent is dried for two times. :: Two drying or dry-welding with the pressure increase of the 诏 诏 ^. ^r... ffl Dry. In the case of heat drying, dry fresh is dried by heating. . The following range. In the case of (9)t / usually 40 c or more, the outline, the brother, the anti-ducking machine is used for the prevention of the heart, the drama of the Buddha, and the temperature below the net solvent. deal with. ^The public media or washing in the dry 锗 碲 碲 碲 _ _ _ 作为 作为 作为 作为 作为 作为 作为 作为 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ , kiln or rotating..., knowing the % conversion, fixed, ancient ^, etc., can be used. The selection of the transfer drying method of the machine wood, the belt-type furnace, etc. is determined depending on the amount of processing, etc., regardless of the use of any - 312XP / invention manual (supplement) machine _6135322 ^ 200829331 drying method, it is preferable to let the gas flow Dry on one side. As a gas to be circulated, it is preferably a gas containing no oxygen. Specific examples thereof include an inert gas such as nitrogen, argon or helium; hydrogen or the like. These gases may be used singly or in combination of two or more kinds in any combination and in any ratio. Preferably, nitrogen or hydrogen is used alone or as a mixture. The lower limit of the temperature of the heat treatment is usually 100 ° C or more, preferably 丨 5 (rc or more, more preferably 200 ° C or more, still more preferably 3 ° C or more. The upper limit of the heat treatment temperature is usually 锗-碲When the melting point of the intermetallic compound particles is not higher than the melting point of the intermetallic compound particles, the ruthenium-iridium intermetallic compound particles are doubled due to sintering, and the surface area of the metal is lowered. Therefore, when the obtained ruthenium-iridium intermetallic compound particles are used for catalyst use, The activity of the catalyst is lowered. Therefore, from the viewpoint of enhancing the activity of the catalyst, the upper limit of the heat treatment temperature is usually not more than °c, preferably 60 (src or less, more preferably 5 〇 (rc or less. [2 · money-碲Intermetallic compound particles] The ruthenium-iridium intermetallic compound particles obtained by the production method of the present invention (hereinafter referred to as "the ruthenium-iridium intermetallic compound particles of the present invention" or simply referred to as "X-month particles") are usually High-purity intermetallic compounds formed by ruthenium and osmium. Here, it should be noted that the particles of the present invention are intermetallic compounds, not amorphous alloys or colloidal particles. The particles of the present invention are intermetallic compounds, as in the examples. verification In general, it can be confirmed by the results of the powder 1 ray diffraction measurement. In the present specification, the term "intermetallic compound" means a compound in which two or more metal elements are bonded in a simple integer ratio, and 312XP/invention Instruction manual (supplement) /97·01/96Β5322 200829331 A compound of physical and chemical properties that is not unique to the constituent metal elements. ^ According to J〇urnal of Phase Equilibria, 12(1), 199 The intermetallic compound formed by ruthenium exhibits the presence of, for example, Rh3Te2, RhTeu, RhlTei, Rh3Te4, and Rh3Te8#. Thus, the ruthenium-iridium intermetallic compound particles of the present invention preferably have an atom of ruthenium and osmium of 3: 2~ 3: 4, more preferably 3: 2, 3: 4 or 1 : 1. Any shape of the 锗-碲 intermetallic compound particles of the present invention is not limited, and the average particle diameter of the hanging system is 1 nm or more, 1 The primary particles of about 〇〇 nm or less are collected to form agglomerates of secondary particles, which are completely different from the colloidal particles whose surface is covered by the protective group. Further, the ruthenium-iridium metal of the present invention Chemical The particle diameter of the particles is preferably 6 nm or more and 16 nm or less. The use of the ruthenium-iridium intermetallic compound particles of the present invention is not limited, and as described in the following example, α can be widely used as a contact for oxidation reaction. Medium _ (oxidation catalyst), which is suitably used as a catalyst for the oximation reaction. [3. Oxidation catalyst] The sensible money-ruthenium intermetallic compound particles are used as the oxidation catalyst%, and may also be used. The ruthenium intermetallic compound particles obtained by the reduction reaction are directly used. In this case, an oxidation reaction can be carried out by adding a reaction substrate of the oxidation reaction to the reaction liquid after the reduction reaction. • In addition, the ruthenium-iridium intermetallic compound particles obtained by the reduction reaction can be used as an oxidation catalyst in addition to any of the above-mentioned subsequent treatments (separation, washing, drying, heat treatment, etc.). 312ΧΡ/Invention Manual (Supplement)/97-01/96135322 26 200829331 'From the viewpoint of improving the dispersibility of primary particles, it is preferred: the 锗-锗 intermetallic compound particles are carried on the second, : , Ueda H 4 and U.S. sinensis are used as an oxidation catalyst. Porous 载::::Inventory of the invention, the intermetallic compound particles are carried on the _ butterfly, which is simply referred to as "the oxidation of the present invention.

As a carrier, there is no limitation. Usually, an example of using an inorganic porous body machine porous body can be used, and it can be used to solve the problem. (_, oxidation = oxidative emulsification (Ah〇3), titanium dioxide (Ti〇2) ), 舻 坊 坊, 氮化 夕 夕 si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si. After that, for example, the surface of the oxidized stone (Si〇2) is coated with carbon and then used.

Mixing the metal salt solution with the square/, 'sub-m defined' of the carbon-ruthenium intermetallic compound particles supported on the carrier, for example, at a temperature at which the temperature of the reduction reaction is not carried out After the reducing agent, the obtained mixed solution is impregnated into the pores of the carrier, and the ruthenium of the present invention is synthesized by adding to the temperature at which the original reaction is carried out (the temperature within the above-mentioned predetermined temperature range). The intermetallic compound particles are carried in the pores of the carrier. The catalyst of the present invention is preferably used in the liquid phase reaction. That is, it is preferred that at least one of the substrate and the oxygen nucleophile at the time of the reaction is in a liquid state: it is in contact with the oxidation catalyst of the present invention. 312XP/Invention Manual (Supplement)/97-01/90135322 27 200829331 fj-1, the oxidation catalyst of the present invention, if applied to oxidizing an oxygen nucleophile: addition to an olefin or an aromatic compound In the method for producing the oxidative addition product of the second reaction, it is preferred to use the method of the second embodiment. In this case, the oxygen nucleophile is subjected to an oxidative addition reaction to, for example, an unsaturated binding site of an olefinic t-fragrance compound or an aromatic side chain. Examples of the oxidative addition reaction using the oxidation catalyst of the present invention include, for example, aldehyde synthesis by oxidation of an olefin; oxychlorination (j) xyChiQrinati()n) or an oxidative oxy-oxyl group. Oxidation (oxyanionizatior O; coupling reaction of olefin and/or aromatic; oxidative carboxylation; etc.), such as oxidative cyanation or mono-alkoxylation, as a specific example of oxychlorination, for example Such as the synthesis of ethylene chloride from ethylene, the synthesis of allyl gasification from propylene, the synthesis of dichloromethylbutene from isobutadiene, the synthesis of chlorobenzene from benzene, The side chain of toluene or xylene is chlorinated, etc. _ As a specific example of oxylation, for example, a decyloxy group represented by ethylene and represented by vinyl acetate, and a dimethoxy olefin butene derived from butadiene t, synthesis of dimethoxymethylbutene from isoprene, synthesis of benzylbenzene from benzene, side chain oximation of fluorene or diphenyl, etc. As a specific example of cyanation For example, the synthesis of acrylonitrile from ethylene to dicyanobutane from butadiene Synthesis of ene, synthesis of dicyanylmethylbutene from isoprene, synthesis of cyanobenzene from benzene, side chain cyanation of toluene or xylene, etc. As a specific example of the alkoxylation, an example is exemplified. Such as thiol ethyl 312XP from ethylene / invention instructions (supplement) / 97-01/96135322 28 200829331 ether synthesis, synthesis of butadiene from butadiene, alkoxylate from isoindole Synthesis of mercaptobutene, synthesis of alkoxybenzene derived from benzene, side chain alkoxylation of toluene or dinonylbenzene, etc. Specific examples of the coupling reaction include, for example, biphenyl synthesis from benzene, from Sakamoto Synthesis of methylbenzene dimer, synthesis of ethylene oxide from vinyl acetate, synthesis of styrene and benzene diphenylethylene, benzene, styrene and benzene triphenylbenzene Tetraphenylbenzene synthesis, etc. Specific examples of the oxidative silking include, for example, acrylic acid synthesis from ethylene disk carbon monoxide, oxalic acid diester synthesis from carbon monoxide and alcohol, and aromatic acid derived from olefin and carbon monoxide and alcohol. Synergistic synthesis, from dibutyl sulphate and cerium oxide and alcohol The synthesis of the adipate esters, etc. As a specific example of the acid synthesis, for example, acetic acid synthesis derived from a woman, etc., can be used as the oxidation catalyst of the present invention. Or the catalyst for the alkoxylation reaction is extremely active and preferably. If the oxidation catalyst of the present invention is applied to an aromatic compound which oxidizes an oxygen nucleophile with a side chain group. Moreover, the effect is also high in the production method using the ruthenium addition product. In this case, the adjacent carbon is added to the aromatic ring of the side chain alkyl group. [4. Manufacture of oxidative addition product Method 312XP/Invention Manual for Producing Oxidative Addition Products by Using the Reaction of the Oxidation Catalyst to the Olefin or Fragrance Compound (or Has a Side Chain Alkyl Group B Compound) (Supplement) / 97-01/96135322 29 200829331 ^ Method i Hereinafter, the "manufacturing method of the oxidative additive product of the present invention" will be described. The method for producing an oxidative addition product of the present invention is produced by oxidizing an oxo-oxidative olefin or an aromatic compound in the presence of a catalyst and molecular oxygen of the present invention. Addition product The method for producing an oxidative addition product of the present invention is used as a raw material.

(4) Hydrocarbons (hereinafter referred to as "raw materials") are not restricted to the reaction, and their types are thermally restricted, preferably linear or branched, or monocyclic or polycyclic. Or a condensed cyclic cycloolefin, more preferably a linear or branched chain olefin or a monocyclic cycloolefin. The raw material olefin may have a substituent in a range which does not adversely affect the oxidation reaction of the present invention. Examples of the substituent include an allyl group, an aryl group, a halogen group, a nitrico-7-cyano group, an amine group, a decylamino group, an alkoxy group, a decyl group, a carboxyl group, a decyl group, a decyloxy group, a hydroxyl group, and the like. Hydroxy thiol and the like. The number of the above substituents in the raw material flue gas is 0 or more per molecule of the olefin fire passing system, and is usually 3 or less, preferably 2 or less, more preferably 1 or less. In the case where the raw material olefin has two or more substituents, the mutually different phases may be the same or different. The linear or branched linear olefin has a carbon number of usually 2 or more, and is usually 30 or less, preferably 12 or less, more preferably 1 or less. The carbon number of the mono-, poly- or condensed cyclic cycloolefin is usually 4 or more, preferably 5 or more, more preferably 6 or more, and usually 3 or less, compared to 隹 312XP / invention specification (supplement) / 97 -01/96135322 30 200829331 12 or less, preferably 1 〇 or less. Further, the total carbon number of the substituent such as the substituent of the raw material olefin is in the above range. The system also includes, for example, propylene, hexamethylene dibutyl, cyclohexanthene, cyclohexylene, cyclopentylene, butadiene, and a ring thereof as a raw material olefin, preferably a conjugated diene. Diterpenoids, s - π / , 』 - cloth), 2,3-monomethylbutadiene ') pentylene (1,3-pentadiene), pentane diene, cyclohexadiene, etc. [ a fine, conjugated diene (cycloalkyl group, medium 'as a total of a diene, preferably butadiene, pentadiene butadiene) is preferably a butadiene or alkyl substituted butadiene In particular, 'as a raw material olefin, preferably a cycloolefin. A specific example of a cyclic olefin' may, for example, be a hexene olefin, etc. Further, 'the raw materials olefins may be singly and in combination. In the above method, the oxidizing addition product of any group is used, and the Japanese compound (hereinafter referred to as "raw material aromatic compound") is used as the original method. = It is not necessary for the reaction to be good. It can be a fragrant compound. In the case of a condensed ring, the ring f is entangled to 2 or more, and usually 10 or less, preferably 6 or less, more preferably the following. As a raw material aromatic compound, it is preferably a single ring 312XP / invention specification (supplement) / 97·01/96135322 200829331 more preferably a single ring aromaticization The aromatic compound of the condensed ring of the 2-ring. The compound of the == group may have a substituent in the case of not causing the oxidation reaction of the present invention to be unfavorable to 曰. ^ As an example of the substituent, for example, from the prefecture , allyl, aryl, dentate, schlossyl, cyano, amine, amide, alkoxy, aryl, enantiomer, sulfhydryl, ethoxylate, ##虱基, 经基, At least one selected from the group consisting of hydroxy fluorenyl groups

The number of the above substituents which the aryl 3 has no compound is, usually, a subaromatic compound. The above is usually 3 or more, more preferably 2 or less, still more preferably 1 or less. In the case where the raw material aromatic compound has two, Um (tetra) may be the same or different from each other. Specific examples of the starting material aromatic compound include, for example, anthracene, ethyl 4, anthracene, m-diphenyl, p-diphenyl, diethylbenzene, o-chloro; p-Chlorotoluene, Dichlorotoluene, O-Shishatoluene, m-Nitro: Benzene, Molybdenum toluene, o-methoxytoluene, m-methoxytoluene, p-:toluene toluene, o-phenoxytoluene, m-phenoxy Toluene, p-phenoxymethyl, 4-toluene, toluic acid, p-toluic acid, o-quinone furfural, m-toluic acid, toluene-formaldehyde, o-cresol, m-cresol, p-cresol, o-methyl benzyl Alcohol, m-methylbenzyl alcohol, p-methylbenzyl alcohol, and the like. In addition, any of the raw material aromatic compounds may be used singly or in combination of two or more kinds in any combination and in any ratio. The milk nucleating agent is subjected to an oxidative addition reaction to the above-exemplified raw material olefin or raw material aromatized human, for example, at its unsaturated bonding site. ° 312XP/Invention Manual (Supplement)/97·〇1/96135322 32 200829331 As the production of the oxidative addition product of the present invention =, the domain (4) diene and the unsaturated oxygen ester of the molecular oxygen should be exemplified. Time method; method for preparing second-acting alcohol and ==: reaction to produce corresponding unsaturated ethylene glycol diether; reacting cyclohexene', carboxy oxime and knife-shaped oxygen to produce corresponding oxirane ring A method for producing alkene benzene by reacting a calcined acid with an acid and a molecular oxygen. n 乳 丞 X In the above specific example, the conjugated diene is preferably selected from the above-mentioned butadiene, pentadiene and the tert-substituted butadiene. Further, the formic acid is preferably an acid. According to the following description, in the above specific example, the corresponding unsaturated diethylene glycol diester is produced by reacting a conjugated diene with a carboxylic acid and a molecular oxygen and performing oximation. The method for producing the oxygenated additive product of the present invention will be described in detail. As the total of the diene which is a reaction raw material, the above-mentioned butadiene, alkyl substituted butadiene (isoprene (2-methyl-l 3-butadiene), 102, 3-anthracene can be used. Butadiene, etc.), pentadiene (1,3-decadiene), iota, 4-hexadiene, cyclic conjugated diene (cyclopentadiene, cyclohexadiene, etc.). Among them, butadiene, pentadiene, and alkyl-substituted butadiene are preferred. The conjugated diene belonging to the reaction raw material is not necessarily pure, and may contain an inert gas such as nitrogen; a saturated hydrocarbon such as decane, ethane or butane; or an unsaturated hydrocarbon such as butane-ene. ingredient. Specifically, the ratio of the conjugated diene to the conjugated hexene and other components is usually 1% by weight or more, preferably 50% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more. . 312XP/Inventive Manual (Supplement)/97-01/96135322 33 200829331 • As the money for other reaction materials, any of aliphatic acid, sulphuric acid, aromatic carboxylic acid, and the like can be used. 1 曰 / 八 丄 万 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Specific examples thereof include acetic acid, propionic acid, citric acid, and isonic acid. From the viewpoint of reactivity and price, acetic acid is preferred. ° is a reaction raw material line acid, and the system is used as a solvent. If necessary, an inert organic solvent can be used for the reaction, for example, saturated smoke solution = wherein 5% by weight or more of the preferred reaction solvent is a reaction product: a carboxylic acid. The amount of citric acid used is in the range of 100 m or less relative to the total amount of diene. In the method for producing an oxidative addition product of the present invention, a gas of molecular oxygen is used. It is preferred to contact the raw material (common vehicle and carboxylic acid) with a solid catalyst in a liquid phase. The gas system of oxidizing oxygen refers to the chylomicron of pure oxygen or oxygen and an inert gas. Examples of the inert gas include nitrogen, argon, and helium, and the mixed gas also includes air. x. Molecular oxygen may be supplied to the reaction system in an arbitrary state according to an arbitrary mixing ratio of the inert gas, but it is preferable that the oxygen concentration is not in the range of the explosive phase in the gas phase portion of the reaction system. - Generally speaking, the oxidation reaction is higher in oxygen and the more favorable the reaction rate, so it is better to be within the limits of the range of 6 n people (4). Light supply. However, with regard to higher oxygen concentrations than air, it is necessary to promote combustion reactions and oxygen concentration, and due to the high concentration of oxygen gas 312XP / invention manual (supplement) / 97-01/96135322 200829331 itself is dangerous Sex also increases, so it is generally not used except for the case where the reaction speed is specifically required. Further, the oxygen partial pressure is determined depending on the oxygen concentration supplied, the composition in the reaction system, the reaction force, and the temperature. The method for producing the oxidative addition product of the present invention can be carried out by any of a fractional method and a continuous method. Further, as the reaction method, any method such as a fixed bed type, a flow type, or a (four) tank type may be employed, and the industrial type is preferably a fixed bed type. The reaction temperature can usually be carried out according to the above temperature. When considering the reaction rate and the formation of by-products, it is preferably 4 (rc or more, 12 (cm or less). / Alternatively, the reaction pressure may be normal pressure or pressure. In order to increase the internal reaction rate, it is preferred to pressurize, but the reaction equipment (4) tends to be high. If these factors are considered, the suitable reaction pressure is normal pressure (the range of lOOkgf/cm2 or less.) In the above step, in the above step, decylcyclohexene can be produced by using cyclohexene instead. In this case, the cyclohexene used as a raw material has a ring-burning, benzene, etc., and It is also possible to use a trace amount of water, for example, more than 90 parts by weight, and the purity is usually 5% by weight. In addition, in the above step, a decyloxyalkyl group can be produced. ^ ^ (III) Conjugated埽, 312XP/Inventive Manual (Supplement)/97-01/96135322 35 200829331 In this case, 'burning benzene used as a raw material, benzene, etc., may contain traces of water. & Among them, in this case, the purity of the raw material benzene is relatively high. In terms of body, the original Μ γ = eh 丄 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 杲 杲 杲 杲 杲 杲 杲The type of the alcohol is not particularly limited, and a lower alcohol having a carbon number of 4 or less such as an alcohol, propanol or isopropanol can be used industrially. [Examples] The present invention will be described in more detail, but the present invention is not limited to the following examples. Λ [Example 1] To a distilled water, ruthenium chloride of 0·15ιη〇ι and 0 30 mm〇1 were added. Thereafter, 1,3-dihydroxy-4-(2-pyridylazo)benzene (abbreviated as pAR ·· molecular formula CuH9〇2N3), Sodium hydroxide was added to adjust the pH to 13, whereby ruthenium chloride and PAR were dissolved to prepare 1 〇ml of a ruthenium-containing solution. This was used as the solution A. Further, 0.40 mmol of citric acid was added to the distilled water to dissolve it. After that, O.lOminol was added to make it dissolved, and it was prepared into a 碲ml solution containing hydrazine. This was used as the B solution. It-human, mixed A solution and B Liquid, after adding steam and sodium hydroxide to adjust to PH13 and make a total amount of 48ml, mix 312XP / invention manual (supplement) / 97-01/96135322 36 200829331 for a sufficient time, then add 80% 2 ml of a saturated hydrazine solution was subjected to reduction at 70X for 3 hours. The black powder obtained by the reduction was filtered in a nitrogen atmosphere, washed with water, and dried at 90 ° C for 1 hour under a nitrogen stream, and then heated to 150X: After maintaining for 1 hour, it was cooled to room temperature to obtain a compound powder (the compound powder of Example 1). 0. 015 g of the compound powder of Example 1 was added to a 100 ml four-necked flask containing 5Og of acetic acid, and the temperature was raised to 90 °C under nitrogen blowing of the acetic acid layer. Nitrogen blowing was stopped, and instead of 1,3-butadiene, a flow rate of 1010 ml/min was applied, and a 10% oxygen/nitrogen mixed gas was blown in with a flow rate of 25 ml/min to start the reaction. After reacting for 3 hours, the blown gas was again switched to nitrogen, cooled to room temperature, and the compound powder was filtered off. The reaction solution was analyzed by gas chromatography to give 1,4-diethoxycarbonyl-2-butene of 2.9 匪. In addition, the concentration of ruthenium dissolved in the reaction liquid was measured by Inductively Coupled Plasma Mass Spectrometry (hereinafter referred to as φ "ICP-MS"), and it was 21 ppm. Compared with Comparative Example 3 described later, it was found that the elution of ruthenium was suppressed. [Example 2] After the compound powder of Example 1 was heated to 150 ° C in a nitrogen gas stream, the gas to be passed was switched from nitrogen to hydrogen, and the temperature was raised to 400 ° C and kept at 2 hours. Thereafter, the gas to be passed was again switched to nitrogen and cooled to room temperature to obtain a compound powder (the compound powder of Example 2). The powder of the compound of Example 2 was subjected to powder X-ray diffraction measurement. The obtained powder X-ray diffraction pattern is shown together with the standard peak of RhsTe2 in 312XP/Invention Manual (supplement)/97-01/96135322 37 200829331

figure 1. As is apparent from Fig. 1, the powder X-ray diffraction pattern of the compound powder of Example 2 was almost identical to the standard peak, so that the compound powder of Example 2 was an intermetallic compound and was of high purity Rh3Te2. [Example 3] After the hydrazine hydrate of 〇·15ra〇1 and the thiosalicyloside of 〇·45_〇1 were knocked and dissolved, the pH was adjusted to 13, Thereby, 10 ml of a cerium-containing solution was prepared. Use this as the A solution. Further, after adding the sodium citrate of 〇.15 mm〇i to the hydrolyzed water to dissolve it, the pH was adjusted to 13 by adding sodium oxychloride to prepare a hydrazine-containing solution. This is used as the b solution. Further, after adding 2 mmol of sodium borohydride to the distilled water to dissolve it, the pH was adjusted to 13 by adding sodium oxynitride, thereby preparing a sodium borohydride-containing solution 1 〇m 1 . Use this as a c solution. Next, the mixture of the A solution and the B solution was mixed, and distilled water and sodium hydroxide were added thereto to adjust the pH to 3, and a total amount of 48 ml was prepared. After mixing for a sufficient period of time, the solution C was further added, and reduction was carried out at 7 ° C for 3 hours. The black powder obtained by the reduction was filtered in a nitrogen atmosphere, and washed with water. After drying at 9 ° C for 1 hour under a nitrogen stream, the temperature was raised to 151 TC, and the circulating gas was switched from nitrogen to hydrogen and then raised to 4 Torr ( The rc was kept for 2 hours, and then switched to nitrogen and cooled to room temperature to obtain a compound powder (the compound powder of Example 3).

The powder of the compound of Example 3 was subjected to powder X-ray diffraction measurement. The resulting powder X-ray diffraction pattern is shown in Fig. 2 together with the standard peak of RhlTei. As is apparent from Fig. 2, the powder of the compound of Example 3, powder X 312XP / invention specification (supplement) / 97-01/96135322 38 200829331, is almost identical, so that the compound of Example 3 is a high purity RhiTei. The ray diffraction pattern and the standard peak powder are intermetallic compounds, [Example 4] - The amount of citric acid used is set to 1 with respect to the steaming water, and the rest depends on the examples! The synthesis of the compound powder was carried out under the same conditions, and heat treatment was carried out under the same conditions as in Example 2 to obtain a compound powder (the compound powder of Example 4). The powder of the compound of Example 4 was subjected to powder X-ray diffraction measurement. The resulting powder X-ray diffraction pattern is shown in Fig. 3 together with the rib 3 at a standard peak of 4. As is apparent from Fig. 3, the powder X-ray diffraction pattern of the compound powder of Example 4 was almost identical to the standard peak, so that the compound powder of Example 4 was an intermetallic compound and was of high purity Rh3Te4. [Comparative Example 1] To the steamed water, 0. 15 mmol of chlorinated chloride, 〇·45 mmol of thiosalicylic acid was added, and then sodium hydroxide was added to adjust the pH to 3, 5, 9, 1 and _, respectively. , 12. In either case, the sulfur-based salicylic acid was not dissolved, and the Rh complex of the target precursor was not formed. [Comparative Example 2] To a distilled water, 0.15 mmol of ruthenium chloride and 1,3-30ππηο1 of 1,3-dihydroxy-4-(2-nl-pyridylazo)benzene (1,3-dihydroxy-4-(2) was added. -pyridylazo)benzene) (abbreviated as PAR: . molecular formula CuHgChN3), and then added sodium hydroxide to adjust the pH to 3, 5, 9, 10, 11, and 12, respectively. In either case, the PAR did not dissolve and could not form the Rh complex of the target precursor. 312XP/Invention Manual (Supplement)/97-01/96135322 39 200829331 [Comparative Example 3] To a distilled water, 0·15 mmol of cerium chloride and cerium·10 mm 〇1 of citric acid were added and dissolved. Use this as the D solution. 0.2 g of an 80% saturated hydrazine solution was added to 10 g of distilled water and heated to 85 C. The D solution was slowly dropped on this, and heated for further 2 hours to carry out reduction. The black powder obtained by the reduction was filtered in a nitrogen atmosphere, washed with water, and heated at 90 ° C for 1 hour under air atmosphere and dried. After raising the temperature to 15 ° C for 1 hour, it was cooled to room temperature to obtain a compound powder (Comparative Compound Powder of Example 3). 15 g of the compound powder of Comparative Example 3 was added to a 100 ml four-necked flask containing 5 liters of vinegar, and the temperature was raised to 90 ° C under nitrogen blowing of the acetic acid layer. Nitrogen blowing was stopped, instead of argon, 3-butadiene, respectively, at a flow rate of 10 ml per minute, and a 1% oxygen/nitrogen mixed gas was blown in a flow of 25 ml per minute to start the reaction. After the reaction for 3 hours, the blowing gas was changed to nitrogen and cooled to room temperature to filter and release the alloy powder. The concentration of hydrazine dissolved in the reaction liquid was measured by I Cp-MS and found to be 6 〇 ppm. [Comparative Example 4] After the compound powder of Comparative Example 3 was heated to 15 Torr in a nitrogen stream, the gas to be circulated was switched from nitrogen to hydrogen, and the temperature was raised to 400 ° C for 2 hours to carry out heat treatment. Thereafter, the gas to be circulated was switched to nitrogen again. • The mixture was cooled to room temperature to obtain a compound powder (the compound powder of Comparative Example 4). The alloy powder of Comparative Example 4 was subjected to powder X-ray diffraction measurement. The obtained powder X-ray diffraction pattern is shown in Fig. 1 together with the standard peak of RhsTe2. As is apparent from Fig. 1, the powder X-ray 312XP/invention specification (supplement)/97-01/96135322 40 200829331 of the compound powder of Comparative Example 4 is different from that of the embodiment 2, and is not related to the standard peak [ Comparative Example 5] - The compound powder was subjected to the same conditions as in Comparative Example 3 except that the amount of citric acid used was set to be the same as that of Comparative Example 3 except for "A △ , 苟 U · 15 mm 〇 l - The resultant was subjected to heat treatment under the same conditions as in Comparative Example 4, whereby a dimer powder (the compound powder of Comparative Example 5) was obtained. f The powder of the compound of Comparative Example 5 was subjected to powder enthalpy diffraction measurement. The X-ray diffraction pattern and the standard peak of RhlTei are shown in Fig. 2. It is apparent from Fig. 2 that the powder ray diffraction pattern of the compound powder of Comparative Example 5 is different from that of Example 3 except for the standard peak of RhlTei' A peak which is considered to be an impurity is also mixed. [Comparative Example 6] The compound powder was subjected to the same conditions as in Comparative Example 3 except that the amount of citric acid used was changed to 〇.2〇mm〇l with respect to distilled water. Synthetic The heat treatment was carried out under the same conditions as in Comparative Example 4, whereby a clarified conjugate powder (the compound powder of Comparative Example 6) was obtained. The powder of the compound of Comparative Example 6 was subjected to powder X-ray diffraction measurement. The obtained powder X-ray diffraction pattern was obtained. It is shown in Fig. 3 together with the standard peak of the rib 3164. It is apparent from Fig. 3 that the powder X-ray diffraction pattern of the alloy powder of Comparative Example β is different from that of Example 4 except that the standard peak of RhsTe4 is mixed with * It is considered to be a peak of impurities. [Example 5] After adding 0.97 mol of cerium chloride and 2.92 mmol of thiohydric salicylic acid to distilled water and dissolving it, sodium hydroxide was added to adjust the pH to 13, by 41 312XP/Inventive Manual (Replenishment)/97·〇ι/96135322 200829331 This is a 5 锗 solution containing 锗 solution for 5 weeks. This is used as a solution. In addition, after adding 1.94 mmol of sodium citrate to distilled water to dissolve it, * Adding sodium hydroxide to adjust the pH to 13, thereby preparing a cerium-containing solution • l 〇 ml. This is used as the F solution. The corpse and the hydrazine water are added to the hydride of sodium hydride, and then dissolved. Sodium oxide adjusts the pH to 13, thereby modulating it into 10 ml of sodium borohydride solution was used as a bismuth solution. • Add 4 parts of steamed water to 6 g of granule-formed carbon (10)m company, 6 〇g = 60% of nitrate: 60 g of acid was heat-treated for 3 hours, and then cooled to room.乂 乂 知 乂 乂 乂 乂 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 After mixing and mixing for a sufficient period of time, the mixed solution was cooled to hydrazine. To this end, G solution 〇·5mi was added, and then the carrier η of 〇g was added to impregnate the solution, and the mixture was heated to a stage for reduction, and then cooled to a temperature. The obtained activated carbon containing ruthenium and ruthenium was transferred to a tube for sintering in a nitrogen stream according to 9 (rc 3 hours, followed by drying for 15 hours and 2 hours, and the obtained carrier was supported by activated carbon). Oxidation catalyst of ruthenium intermetallic compound particles (oxidation catalyst of Example 5) ^Oxidation catalyst of Bellows Example 5 was observed by a transmission electron microscope - The obtained oxidation catalyst of Example 5 was obtained. A penetrating electron microscope photograph (photograph of a substitute image) is shown in Fig. 4. From the photograph of Fig. 4, the particle diameter of the ruthenium-iridium intermetallic compound particle on the activated carbon carrier and (4) ship, and 312XP/invention specification (Supplement) /97-01/96135322 200829331 is carried with high dispersion. (Industrial Applicability) ^ The 铑-碲 intermetallic compound of the present invention can be widely used, for example, from "t σ particles". • a catalyst (oxidation catalyst) for emulsification reaction, etc. Further, the oxidation catalyst of the present invention can be used, for example, by oxidatively adding an oxygen nucleophile to a rare hydrocarbon or an aromatic compound. Method for producing an oxidative addition product (manufactured by an oxidative addition product) In the above, the present invention will be described in detail with reference to the specific embodiments thereof, and it is understood by those skilled in the art that the invention can be modified without departing from the spirit and scope of the invention. According to Japanese Patent Application No. 2006-258836 filed on Sep. 25, 2006, the entire disclosure of which is incorporated herein by reference in its entirety. A powder X-ray diffraction pattern, which is shown together with a standard peak of RhsTe2. φ Fig. 2 is a diagram showing a powder X-ray diffraction pattern of the compound powder of Example 3 and Comparative Example 5 together with a standard peak of RhiTei. Fig. 3 is a view showing a powder X-ray diffraction pattern of the compound powder of Example 4 and Comparative Example 6 together with a standard peak of RhsTe4. Fig. 4 is a transmission electron micrograph of the oxidation catalyst of Example 5. (Photograph replaced by photo) 312XP/Invention Manual (supplement)/97-〇1/96135322 43

Claims (1)

200829331 X. Patent application garden: 1. A particle of a ruthenium-iridium intermetallic compound, characterized in that the metal particle diameter of the j and 碲 is 6~16nm; the atomic ratio of 姥 to 碲 is 3: 2~3: 4. In the first item of the range, the intermetallic compound particles, the ratio of % in the atom to the atom of 碲 are 3:2, 3:4 and 1:1.姥-hoof:: Catalyst, which is characterized in that the first or second item of the patent application is carried on the carrier. Application::: Oxidation catalyst of the third item of the patent range' is a method for producing 醯oxylated anti-5 kinds of ruthenium-iridium intermetallic compound particles, and the contact agent of the pot characterization agent will contain (4) salt and strontium salt. And the solution of the wronging agent and the reducing agent = the organic compound containing a sulfur atom and/or a nitrogen atom. In the fifth item of the range of the application 2, the 'eight in the intermetallic compound particles' is dissolved in the aqueous solution and then contacted with the reducing agent. Solution to the base 7. The method for producing 碡_碡 intermetallic compound particles according to item 5 of the patent application scope wherein the above-mentioned salt is ruthenium chloride. A method of coating an intermetallic compound particle as described in the patent application pp. 535, wherein the above-mentioned onium salt is selected from the group consisting of citric acid and a salt thereof, and a hydrazine acid and a salt thereof. 9. A bismuth-tellurium intermetallic compound particle characterized by a β 10.-oxidation obtained by the manufacturing method of the 312XP/invention specification (supplement)/97-01/96135322 44 200829331 The catalyst is characterized in that the 锗-碲 intermetallic compound particles of the ninth application patent range are carried on a carrier. A method for producing an oxidative addition product of η', characterized in that an oxygen nucleophile is oxidatively added to an olefin or in the presence of an oxidation catalyst and molecular oxygen of claim 10 Aromatic compound. 312ΧΡ/Invention Manual (supplement)/97-01/96135322 45