JP2005105336A - Method of coprecipitating chalcogen compound, method of producing platinum group-chalcogen alloy, method of producing platinum group-chalcogen alloy/inorganic porous carried product, and method of producing oxide reaction product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of producing a platinum group-chalcogen alloy useful as a highly functional material and a catalyst, and to provide a method of producing an oxide reaction product where olefine or the like and carboxylic acid or the like are brought into reaction with molecular oxygen using a platinum group-chalcogen alloy/inorganic porous carried catalyst. <P>SOLUTION: A 1.6N-NaOH aqueous solution is added to a spherical silica carrier impregnated with a palladium chloride-containing hydrochloric acid solution and a telluric acid aqueous solution, and alkali treatment is performed. Thus, a palladium compound and a telluric compound are coprecipitated, and are adsorbed and carried on the surface of the spherical silica simple substance. Next, the palladium compound and telluric compound sucked and carried on the spherical silica carrier are subjected to washing with distilled water, drying with gaseous nitrogen, and reduction treatment with hydrogen at 1N1/min to prepare a palladium-tellurium/silica-carried catalyst. The palladium-tellurium/silica-carried catalyst acts as the catalyst with high activity in the case the converting reaction of butadiene into diacetoxy-butadiene is performed in the presence of molecular oxygen. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for coprecipitation of chalcogen compounds, and more particularly to a method for producing a platinum group-chalcogen alloy / inorganic porous material support using a coprecipitate of a platinum group-chalcogen compound.

  Chalcogens are known to form compounds with many metals, especially transition metals, and are known to form alloys, and many intermetallic compounds are also known. These alloys are considered to be extremely useful as highly functional materials, and are put into practical use for applications such as catalysts and semiconductors.

  For example, as a catalyst application, a solid catalyst in which palladium and tellurium are supported on a solid support such as silica is used as a catalyst for producing an unsaturated glycol ester by reacting a conjugated diene with a carboxylic acid and molecular oxygen. (See Patent Document 1).

Japanese Patent Laid-Open No. 08-003110

  By the way, many methods have been proposed as a method for producing an alloy catalyst of such a chalcogen and a transition metal, and a method of immobilizing and dissolving the porous metal after impregnating the dissolved metal is a basic method. In this case, in the method using the principle of adsorbing and fixing metal ions on the porous carrier by the interaction between the metal ions in the metal raw material solution and the surface functional group of the porous carrier, the interaction of the metal ion species The alloy form synthesized varies depending on the difference. For example, when a platinum group metal and tellurium dissolved in mineral acid is adsorbed to activated carbon, the adsorption capacity for activated carbon is generally higher than that of chalcogen, so the composition ratio of alloy particles is It is difficult to carry evenly. As described above, it is extremely difficult for the platinum group and the chalcogen to be uniformly loaded in a multi-component system having greatly different ion characteristics.

  In addition, a method in which metal ions are forcibly deposited on the support by drying or the like in a state where there is almost no interaction between the metal ions in the metal raw material solution and the surface functional groups of the porous support is industrially adopted. However, in this method, since the deposition rate of each metal salt is governed by the solubility, it is difficult to carry alloy particles having a uniform composition ratio on the porous carrier.

  Furthermore, a precipitation method in which a metal salt is precipitated using a chemical reaction is also known. For example, in the case of the platinum group, the platinum group is removed by adding an alkali component to the solution of the platinum group compound. The technique of depositing as an oxide is widely used. However, in the case of chalcogen, since a compound of chalcogen and an alkali metal or alkaline earth metal is generally water-soluble, a method for precipitating a metal salt of chalcogen has not been adopted.

  Thus, in the prior art, a production method that industrially satisfies the platinum group-chalcogen alloy has not been obtained. On the other hand, since platinum group metals are extremely expensive, development of a catalyst with high activity per unit metal amount is required. Development of a method for industrially producing a highly active platinum group-chalcogen alloy is extremely important. is there.

The present invention has been made to solve such technical problems, and an object of the present invention is to provide a method for coprecipitation of a platinum group compound and a chalcogen compound.
Another object of the present invention is to provide a method for producing a platinum group-chalcogen alloy useful as a highly functional material or a catalyst.
Furthermore, another object of the present invention is to provide a method for producing a platinum group-chalcogen alloy / inorganic porous support that can be applied to applications such as catalysts or semiconductors under industrially satisfactory conditions.
Another object of the present invention is to provide a method for producing an oxidation reaction product in which a highly active platinum group-chalcogen alloy / inorganic porous supported catalyst is used to react olefin and carboxylic acid with molecular oxygen. It is to provide.

  As a result of intensive investigations by the present inventors to solve such problems, a palladium compound-tellurium containing a tellurium compound that does not precipitate alone is added by adding an aqueous solution in which a palladium compound and a tellurium compound are dissolved in an aqueous sodium silicate solution. The inventors have found that a coprecipitate of the compound can be obtained, and have completed the present invention based on this finding.

  Thus, the gist of the present invention is a coprecipitation method of a chalcogen compound, wherein the chalcogen compound solution is brought into contact with an alkali component in the presence of the platinum group compound to precipitate the platinum group compound and the chalcogen compound.

  The gist of the present invention is characterized in that a chalcogen compound solution is brought into contact with an alkali component in the presence of a platinum group compound, a coprecipitate of the platinum group compound and the chalcogen compound is precipitated, and the coprecipitate is reduced. The platinum group-chalcogen alloy is produced.

  Furthermore, the present invention provides a platinum group compound and chalcogen compound solution in contact with an alkali component in the presence of an inorganic porous material, and deposits a coprecipitate of the platinum group compound and chalcogen compound on the inorganic porous material. It can be understood as a method for producing a platinum group-chalcogen alloy / inorganic porous material carrier characterized by subjecting a product to reduction treatment.

  The platinum group-chalcogen alloy / inorganic porous material carrier produced by such a production method can be used as a catalyst for various synthetic reactions. The platinum group compound is preferably a compound of palladium, rhodium or ruthenium. The chalcogen compound is preferably a tellurium compound. Furthermore, the inorganic porous body is preferably silica.

  Next, the present invention relates to a platinum group-chalcogen alloy / inorganic porous material-supported catalyst and molecular oxygen obtained by reducing a coprecipitate of a platinum group compound and a chalcogen compound adsorbed and supported on an inorganic porous material. In the presence of olefin, an oxidative addition of a nucleophile to at least one reaction substrate selected from olefins and aromatic compounds can be considered as a method for producing an oxidation reaction product.

  In the method for producing an oxidation reaction product to which the present invention is applied, if the reaction substrate is a conjugated diene and the nucleophile is a carboxylic acid or an alcohol, an unsaturated glycol diester is produced by a highly active solid catalyst. Can be manufactured.

  In general, since a compound of a chalcogen such as tellurium and an alkali metal or an alkaline earth metal is water-soluble, the metal salt of the chalcogen is not insolubilized alone. However, in the present invention, it is considered that a complex salt formed of a platinum group such as palladium and a chalcogen such as tellurium is simultaneously insolubilized in the common solution, so that the platinum group compound-chalcogen compound is coprecipitated.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a platinum group-chalcogen alloy useful as a highly functional material or a catalyst is provided.

Hereinafter, the best mode for carrying out the present invention (hereinafter referred to as an embodiment of the present invention) will be described in detail.
Examples of the platinum group element used in this embodiment include ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold. The platinum group used as a raw material for alloy production in the present embodiment includes compounds with inorganic acids such as halides, sulfates, nitrates, acetates, cyanides, thiocyanates, acetylacetyls. Organic compounds such as sodium salts may be used.

Specifically, for example, when palladium is taken as an example, any of fluoride, chloride, bromide, and iodide can be used as a halide, and more specifically, for example, as a chloride. , PdCl ₂ , Na ₂ PdCl ₄ , K ₂ PdCl ₄ , Cs ₂ PdCl ₄ , inorganic halides; allyl palladium chloride dimer, C ₆ H ₁₀ Cl ₂ Pd ₂ , bisethylenediamine palladium chloride [Pd (C ₂ H Organic halides such as ₈ N ₂ ) ₂ ] Cl ₂ and dichlorobistriethylphosphine palladium [PdCl ₂ {P (C ₆ H ₅ ) ₃ } ₂ ]. Moreover, you may use what melt | dissolved metallic palladium with the acid containing a halogen as needed. As the kind of halogen, chloride most industrially used is preferable because of its availability.

Furthermore, sulfates such as PdSO ₄ ; nitrates such as Pd (NO ₃ ) ₂ ; acetates such as Pd (COOCH ₃ ) ₂ ; cyanides such as Pd (CN) ₂ ; thiocyanides such as Pd (SCN) ₂ ; Complex salts such as bis (acetylacetonato) palladium may also be used.

As described above, various platinum group compounds can be used. Inorganic chlorides are available in terms of easy availability and price, solubility of raw material compounds, and dissolution of reactive organisms with alkali metals or alkaline earth metals. The product is most preferred. _{Specifically, RuCl 3, H 2 RuCl 6} , Na 2 RuCl ruthenium chloride such as _{6; RhCl 3, H 2 RhCl} 6, Na 2 RhCl rhodium chloride such as _{6; PdCl 2, H 2 PdCl} 4, Li Palladium chloride such as ₂ PdCl ₄ , Na ₂ PdCl ₄ , K ₂ PdCl ₄ ; Silver chloride; Rhenium chloride such as ReCl ₃ , ReClO ₃ , ReCl ₄ O; Osmium chloride such as OsCl ₄ , Os (OH) Cl ₃ Iridium chlorides such as IrCl ₃ , IrCl ₄ , H ₂ IrCl ₆ , Na ₂ IrCl ₆ and IrCl ₂ (OH); platinum chlorides such as H ₂ PtCl ₆ and Na ₂ PtCl ₆ ; HAuCl ₄ and NaAuCl ₄ The gold chloride is preferred.

  These platinum groups are used in a dissolved state. The method for preparing the solution is not particularly limited as long as the platinum group is dissolved in the solvent. As the solvent, water is generally used, but an organic solvent such as acetone, alcohol, organic carboxylic acid, ether, ester or the like may be used as necessary, and a mixture thereof may also be used. Since the concentration of the solution in which the platinum group is dissolved is limited depending on the application of the alloy to be manufactured, it cannot be generally limited, but is usually used in the range of 0.05% by weight to the maximum solubility.

Examples of chalcogens used in this embodiment include sulfur, selenium, and tellurium. More specifically, examples of the sulfur compound used as a raw material in the present embodiment include sulfides such as Na ₂ S, NaSH, and K ₂ S; sulfates such as NaHSO ₄ and Na ₂ SO ₄ ; Na ₂ S Examples include pyrogenic sulfates such as ₂ O ₇ ; thiosulfates such as K ₂ S ₂ O ₃ and Na ₂ S ₂ O ₃ .

Selenium used as a raw material in the present embodiment includes selenides such as Na ₂ Se and NaHSe; halides such as SeCl ₄ ; oxides such as SeO ₂ ; selenite such as selenite and Na ₂ SeO _3. Acid salt; Selenate, selenate such as Na ₂ SeO _{4 and the} like. Moreover, you may use what melt | dissolved the selenium metal in the acid or the alkali as needed.

Tellurium used as a raw material in the present embodiment includes telluride such as Na ₂ Te, chloride such as TeCl ₄ ; oxide such as TeO ₂ ; telluric acid, Na ₂ TeO ₃ , K ₂ TeO _{3 and the} like. And telluric acid salts such as telluric acid, telluric acid, telluric acid salts such as Na ₂ TeO ₄ and K ₂ TeO ₄ . If necessary, a tellurium metal dissolved in an acid or alkali may be used. For example, organic tellurium such as diphenyl ditelluride may be used, but telluric acid is easy to obtain and easy to handle. And its salts are most preferred.

  These chalcogens are used in a dissolved state. The method for preparing the solution is not particularly limited as long as the chalcogen is dissolved in the solvent. As the solvent, water is generally used, but an organic solvent such as acetone, alcohol, organic carboxylic acid, ether, ester or the like may be used as necessary, or a mixture thereof. The concentration is limited depending on the application of the alloy to be manufactured, and thus cannot be generally limited, but is usually used in the range of 0.05% by weight to the maximum solubility.

  According to the present embodiment, the platinum group and the chalcogen are used after being prepared as a metal raw material liquid in which both coexist in the solution. The concentration ratio between the platinum group and the chalcogen in the metal raw material liquid is usually 0.05 mol or more, preferably 0.1 mol or more, more preferably 0.15 mol or more with respect to 1 mol of the platinum group. It is. However, it is usually 5 mol or less, preferably 2 mol or less, more preferably 0.5 mol or less. This metal raw material solution may be mixed after each metal raw material is dissolved individually, or may be used by dissolving at the same time.

Examples of the alkali component used in the present embodiment include hydroxides such as KOH and NaOH; carbonates such as K ₂ CO ₃ and Na ₂ CO ₃ ; acetates such as CH ₃ COOK and CH ₃ COONa; K ₂ Alkali metal compounds such as silicates such as SiO ₃ and Na ₂ SiO ₃ can be widely used. Furthermore, organic alkalis typified by amines such as diethylamine and diisopropylamine may be used.

  The amount of the alkali component used in the present embodiment is not particularly limited. When the amount of the alkali component is small, a part of the platinum group and chalcogen does not precipitate, but they can be used (recovered) as a part of the metal raw material liquid after separating the precipitate. However, if the recovery rate is excessively high, loss of the metal component increases, which is not preferable in handling expensive noble metals. Therefore, industrially, the amount of the alkali component is usually 0.2 times or more, preferably 0.5 times or more, more preferably 1 times of Ma (unit: mol) obtained by the following formula (1). The amount is more than double.

  On the other hand, the excess alkali component can be recycled as a part of the alkali component after separating the precipitate, so the upper limit of the amount used is not particularly limited, but from the viewpoint of productivity, 500 times or less of Ma (unit: mol) calculated | required by Formula (1) is preferable. However, if the porous body is in charge and there are special circumstances such as the porous body is dissolved by alkali or the pore structure is changed, the amount of alkali component used is A smaller amount is preferable, and specifically, an amount 20 times or less of Ma (unit: mol) obtained by the following formula (1) is preferable.

(In the formula (1), Mp is the number of moles of platinum group contained in the metal raw material liquid, A is a constant and is usually 2, however, in the case of gold, Mc is 1 in the metal raw material liquid. The number of moles of chalcogen contained, and Z is the alkali valence of the alkali component (for example, Z = 1 in the case of NaOH, Z = 2 in the case of Na ₂ SiO ₃ ))

  The method of bringing the chalcogen compound solution into contact with the alkali component in the presence of the platinum group compound is not particularly limited. Usually, however, a solution containing the platinum group and the chalcogen (hereinafter referred to as “metal raw material liquid”) and the alkali component are used. Contact. For example, a solution containing an alkali component (hereinafter referred to as “alkali solution”) may be prepared in advance, and the alkali solution may be mixed with the metal raw material solution, or the metal solution may be mixed with the alkali solution. The mixing method is not particularly limited, and may be any of dropping, showering, spraying, and the like. If necessary, the alkali component itself may be added to the metal raw material liquid. The mixing temperature is usually room temperature, and may be cooled or heated as necessary. If a temperature equal to or higher than the boiling point is necessary, the mixing may be performed in a pressurized system.

  The concentration of the alkali component of the alkaline solution used in the present embodiment is usually selected from the range of 0.1 wt% to the maximum solubility, preferably 0.5 wt% to the maximum solubility, and more Preferably, it ranges from 2% by weight to maximum solubility. If the concentration of the alkali component in the alkaline solution is excessively low, the coprecipitate of the platinum group compound-chalcogen compound does not precipitate sufficiently and is not preferable.

  Examples of the inorganic porous material used in the present embodiment include activated carbon, silica, alumina, titania, zirconia, and other oxide carriers, and mixed oxides thereof. Among these, silica is particularly preferable. The carrier physical properties are required to be porous, and those having an average pore diameter of 10 nm to 50 nm are preferable. The carrier shape is not particularly limited. However, when the platinum group-chalcogen alloy / inorganic porous material support obtained by the production method to which the present embodiment is applied is used as a catalyst, as described later, when using a fixed bed catalytic reaction mode, Industrially, the carrier particle diameter is preferably 1 mm or more. However, the carrier particle diameter is preferably 8 mm or less. If the carrier particle diameter is too large, the outer surface area of the catalyst particles becomes relatively small. On the other hand, if it is too small, the pressure loss of the catalyst packed bed increases. Further, when a fluidized bed catalytic reaction format or a suspension phase catalytic reaction format is adopted, the carrier particle diameter is preferably 5 μm or more industrially, more preferably 10 μm or more. However, the carrier particle diameter is preferably 2000 μm or less, and more preferably 1000 μm. If the carrier particle diameter is excessively large, the fluidity of the catalyst is lowered. If the carrier particle size is too small, it becomes difficult to separate the catalyst.

  The method for precipitating a coprecipitate of a platinum group compound and a chalcogen compound (hereinafter sometimes simply referred to as “coprecipitate”) on the inorganic porous body is, for example, as follows: After impregnating the porous material, contact the alkali solution, (2) Impregnate the inorganic porous material with the alkaline solution and then contact the metal raw material liquid, (3) Impregnate the inorganic porous material with the alkaline solution After drying, the alkali component is precipitated in the pores of the inorganic porous body, and then the metal raw material liquid is brought into contact with the inorganic porous body. Among these, (1) a method in which an inorganic porous body is impregnated with a metal raw material solution and then contacted with an alkali solution is preferable.

  Specifically, in the method (1) or (2) described above, first, an inorganic porous material is impregnated with a metal raw material solution or an alkali solution. The method is not particularly limited. For example, a method of adding an inorganic porous material to a metal raw material solution or an alkali solution, a method of bringing a metal raw material solution or an alkali solution into contact with an inorganic porous material, a method of spraying a metal raw material solution or an alkali solution onto an inorganic porous material, etc. Either is fine. The amount of the metal raw material liquid or the alkali solution when impregnating the inorganic raw material with the metal raw material liquid or the alkali solution is not particularly limited, and an excess of the metal raw material liquid or the alkali solution is used than the pore volume of the inorganic porous material. If so, the excess can be recycled. In addition, when it is not desired to impregnate the metal raw material liquid or the alkali solution up to the center of the particles of the inorganic porous body, the metal raw material liquid or the alkali solution may be used in an amount smaller than the pore volume of the inorganic porous body. .

  Furthermore, the method of bringing the other solution into contact with the inorganic porous material impregnated with either the metal raw material solution or the alkali solution is not particularly limited, and any of dripping, showering, spraying, and the like may be used. The temperature to be contacted is usually room temperature, and may be in a cooled or heated state as necessary, and may be carried out in a pressurized system if a temperature higher than the boiling point is necessary.

  Next, in the method (3) described above, the inorganic porous body is impregnated with an alkaline solution and then dried in the method (2). The drying method in this case is not particularly limited. For example, fluidized bed vacuum drying using a rotary evaporator or a conical blender; static drying such as a vacuum dryer or shelf drying device; fluidized bed drying such as a kiln drying device; a method of drying under reduced pressure in a cooled and frozen state; Any drying method such as a method of heating and drying in an air current may be used. Among these, industrially, a method of heating and drying in an air stream is preferable.

  The method for drying the alkaline solution impregnated in the inorganic porous material in an air stream may be any of fixed bed drying, fluidized bed drying, and kiln type drying, for example. Kiln-type drying is not limited by the particle size of the inorganic porous material, but industrially, when the particle size of the inorganic porous material is 1 mm or more, fixed bed drying is preferable, and the particles of the inorganic porous material are When the diameter is 0.2 mm or less, fluid bed drying is preferred. The gas component in the case of airflow drying may be air, an inert gas such as nitrogen, or a mixture thereof, and a dehumidified gas may be used as necessary. The gas flow rate used in this case is usually selected in the range of 20 (l / l · hour) or more in space velocity (SV) with respect to the catalyst, and more preferably 1000 (l / l · hour) to 8000 ( l / l · hour). If the value of space velocity (SV) is too low, the drying time becomes long, and if it is too high, the amount of gas used becomes large, which is uneconomical.

  Next, in this manner, in the presence or absence of the inorganic porous body, the coprecipitate of the platinum group compound and the chalcogen compound obtained by bringing the metal raw material solution into contact with the alkali component is precipitated, By reducing the coprecipitate, a platinum group-chalcogen alloy can be produced. The method for reducing the coprecipitate is not particularly limited. For example, the reducing agent may be brought into contact with a solution containing the coprecipitate obtained by supporting the metal raw material liquid and the alkali component, or the metal raw material. After the coprecipitate is separated from the solution containing the coprecipitate obtained by bringing the liquid and the alkali component into contact with each other, the reduction treatment may be performed. Further, if necessary, the coprecipitate may be washed and / or dried or calcined before the reduction treatment, and if necessary, these may be repeated. The reduction method is not particularly limited as long as the coprecipitate of the platinum group compound and the chalcogen compound is reduced to obtain a platinum group-chalcogen alloy. For example, gas phase reduction with hydrogen gas, methanol gas, etc .; hydrazine, formalin, Any of liquid phase reduction represented by formic acid and its salts may be used.

  In this Embodiment, the method of isolate | separating the inorganic porous body containing the coprecipitate containing a platinum group and a chalcogen or a coprecipitate before a reduction process as needed is not specifically limited. For example, any of decantation, filtration, centrifugation and the like may be used. Moreover, what is necessary is just to isolate | separate with the inorganic porous body, when carrying out the coprecipitation precipitation in the pore of an inorganic porous body.

  In this Embodiment, the method of wash | cleaning the inorganic porous body containing a coprecipitate or a coprecipitate before a reduction process as needed is not specifically limited. In general, washing with water is used, but several types of chemicals that can remove impurities may be used as necessary.

  In this Embodiment, the method of drying the inorganic porous body containing a coprecipitate or a coprecipitate before a reduction process as needed is not specifically limited. For example, fluidized bed vacuum drying using a rotary evaporator, conical blender, etc .; static drying such as vacuum dryers, shelf dryers, etc .; fluidized bed drying such as kiln dryers; Any drying method such as heating and drying in an air stream may be used.

  Especially, as a method of drying and / or firing in an air stream, for example, any of fixed bed drying, fluidized bed drying, and kiln type drying may be used. Kiln type drying is not limited by the particle size of the target product, but industrially, fixed bed drying is preferred when the particle size is 1 mm or more, and fluidized bed drying is preferred when the particle size is 0.2 mm or less. As a gas component in the case of airflow drying, an inert gas such as air or nitrogen or a mixture thereof may be used, and a dehumidified gas may be used as necessary. It is preferable to use hydrogen as the gas because drying and reduction can be performed simultaneously. The gas flow rate is usually selected in the range where the space velocity (SV) is 20 (l / l · hour) or more with respect to the coprecipitate, more preferably 1000 (l / l · hour) to 10,000 (l / l).・ Time) range. If the value of space velocity (SV) is too low, the drying time becomes long, and if it is too high, the amount of gas used becomes large, which is uneconomical.

  One application of the platinum group-chalcogen alloy of this embodiment is a catalyst, which can be widely used for catalytic reactions. The platinum group-chalcogen alloy obtained by the reduction treatment can be used as a catalyst as it is, but it may be used after removing alkali metals, halogens and the like remaining in the alloy. As the removal method, a method of washing with a liquid that does not essentially dissolve the platinum group-chalcogen alloy is usually used. As the cleaning liquid, for example, water or warm water may be used, and a weak acid such as acetic acid or oxalic acid and a weak base such as sodium carbonate adjusted to an arbitrary concentration may be used.

  Among these, water or warm water is more preferable in terms of price and safety. In addition, since it is difficult to completely remove the alkali metal component with water or warm water, it is generally industrially removed to such an extent that it does not cause a problem in the reaction system. The amount that does not cause this problem varies depending on the reaction substrate, conditions, process flow, etc., and therefore cannot be generally stated, but is generally less than 0.5%, preferably less than 0.2%. However, depending on the process, it may be desired to remove alkali metals and halogens as completely as possible. When it is desired to remove the alkali in particular, the removal efficiency is good by washing with a weak acid such as acetic acid or oxalic acid. If it is desired to remove the halogen component in particular, the cleaning efficiency is good by washing with a weak base such as sodium carbonate. The washing method is not particularly limited, but industrially, it is general to fill a washing tank with a catalyst and distribute the washing liquid.

  Hereinafter, the usage method as a catalyst is demonstrated in detail. The platinum group-chalcogen alloy / inorganic porous material support obtained by the production method to which the present embodiment is applied can be widely used as an oxidation catalyst for oxidation catalyst reaction, but it can be used in a liquid phase reaction. preferable. That is, at the time of reaction, it is preferable that at least one of the substrate and the oxygen nucleophile is in a liquid state and contacts the catalyst. In particular, it is highly effective when applied to an oxidative addition reaction method in which an oxygen nucleophile is oxidatively added to an olefin or an aromatic compound and a method for producing an oxidative addition product using the oxidative addition reaction method. For example, aldehyde synthesis by oxidation of olefins; oxychlorination and oxidative acyloxylation; oxidative cyanation; oxyanionization such as oxidative alkoxylation; olefin and / or aromatic coupling reaction; oxidative carboxylation, etc. Reaction.

  More specifically, examples of aldehyde synthesis include acetaldehyde synthesis from ethylene. As oxychlorination, synthesis of vinyl chloride from ethylene; synthesis of allyl chloride from propylene; synthesis of dichlorobutene from butadiene; synthesis of dichloromethylbutene from isoprene; synthesis of chlorobenzene from benzene; side chain chlorination such as toluene or xylene Is mentioned. As acyloxylation, acyloxyvinyl synthesis represented by vinyl acetate synthesis from ethylene; diacyloxybutene synthesis from butadiene; diacyloxymethylbutene synthesis from isoprene; acyloxybenzene synthesis from benzene; toluene or xylene, etc. Side chain acyloxylation and the like. Examples of the cyanation include acrylonitrile synthesis from ethylene; dicyanobutene synthesis from butadiene; dicyanomethylbutene synthesis from isoprene; cyanobenzene synthesis from benzene; side chain cyanation such as toluene or xylene. Alkoxylation includes methyl ethyl ether synthesis from ethylene; dialkoxybutene synthesis from butadiene; dialkoxymethyl butene synthesis from isoprene; alkoxybenzene synthesis from benzene; side chain alkoxylation such as toluene or xylene. It is done. Coupling reactions include biphenyl synthesis from benzene; methylbenzene dimer synthesis from toluene; diacetoxybutadiene synthesis from vinyl acetate; stilbene synthesis from styrene and benzene; triphenylbenzene from styrene or styrene and benzene and Examples include tetraphenylbenzene synthesis. In oxidative carboxylation, acrylic acid synthesis from ethylene and carbon monoxide; oxalic acid diester synthesis from carbon monoxide and alcohol; succinic acid diester synthesis from ethylene, carbon monoxide and alcohol; butadiene and carbon monoxide and alcohol Synthesis of adipic acid esters from

  Most preferably, it is highly active when used as a catalyst for liquid phase oxidative acyloxylation and / or alkoxylation reactions. In particular, it is highly effective when applied to an oxidative addition reaction method in which an oxygen nucleophile is oxidatively added to an olefin or an aromatic compound and a method for producing an oxidative addition product using the oxidative addition reaction method. In this case, the oxygen nucleophile performs an oxidative addition reaction on, for example, an unsaturated bond site of the olefin or aromatic compound. Alternatively, it is highly effective when applied to an oxidative addition reaction method in which an oxygen nucleophile is oxidatively added to an aromatic compound having a side chain alkyl group and a method for producing an oxidative addition product using the oxidative addition reaction method. In this case, the oxygen nucleophile performs an oxidative addition reaction, for example, on the carbon adjacent to the aromatic ring of the side chain alkyl group.

  The raw material olefin used in the present embodiment is not particularly limited as long as it does not adversely influence the reaction, but it is a straight chain or branched olefin, or a monocyclic, polycyclic or condensed cyclic olefin. Olefin is preferable, and linear or branched olefin or monocyclic cycloolefin is particularly preferable. These olefins or cycloolefins may be substituted with a substituent that does not adversely affect the oxidation reaction of the present invention. Examples of the substituent include allyl group, aryl group, halogen group, nitro group, cyano group, amino group, amide group, alkoxy group, acyl group, carboxyl group, formyl group, acyloxy group, hydroxyl group, and hydroxymethyl group. However, the present invention is not limited to this.

  The carbon number of the linear or branched olefin is usually 2 or more, and usually 30 or less, preferably 12 or less, more preferably 10 or less. The carbon number of the monocyclic, polycyclic or condensed cyclic cycloolefin is usually 4 or more, preferably 5 or more, more preferably 6 or more, and usually 30 or less, preferably 12 or less, more preferably 10 or less. It is. Examples of the olefin include ethylene, propylene, butene, 2,3-dimethylbutene, cyclopentene, cyclohexene, cycloheptene, butadiene, and cyclohexadiene. Of these, conjugated dienes are preferable. Specific examples of the conjugated diene include butadiene, piperylene (1,3-pentadiene), 1,4-hexadiene, and isoprene (2-methyl-1,3-butadiene), alkyls such as 2,3-dimethylbutadiene. Substituted butadiene (a kind of branched olefin), and cyclic dienes such as cyclopentadiene and cyclohexadiene can be used. Preferably, it is butadiene, piperylene, or alkyl-substituted butadiene, and most preferably is either butadiene or alkyl-substituted butadiene. Further, cycloolefin is also preferable, and examples thereof include cyclopentene, cyclohexene, cycloheptene and the like. Particularly preferred is cyclohexene.

The aromatic compound used in the present embodiment is not particularly limited as long as it does not adversely affect the reaction, but a monocyclic or condensed aromatic compound is used, and the number of condensed rings is usually 2 to 10, preferably 2 to 6, more preferably 2 or 3. Among these, a monocyclic or bicyclic condensed ring aromatic compound is preferable, and a monocyclic aromatic compound is more preferable. These aromatic compounds may be substituted with a substituent that does not adversely affect the oxidation reaction of the present invention. Examples of substituents include alkyl groups, allyl groups, aryl groups, halogen groups, nitro groups, cyano groups, amino groups, amide groups, alkoxy groups, acyl groups, carboxyl groups, formyl groups, acyloxy groups, hydroxyl groups, and hydroxymethyls. Although at least 1 substituent chosen from group is mentioned, It is not limited to this.
For the olefin or aromatic compound as described above, the oxygen nucleophile performs, for example, an oxidative addition reaction at the unsaturated bond site.

  The aromatic compound having a side chain alkyl group used in this embodiment is not particularly limited as long as it does not adversely affect the reaction, but the above aromatic compound is substituted with one alkyl group. Or an alkyl group, allyl group, aryl group, halogen group, nitro group, cyano group, amino group, amide group, alkoxy group, acyl group, carboxyl group, formyl group, acyloxy group, hydroxyl group, Examples include aromatic compounds in which at least one substituent selected from hydroxymethyl groups is directly bonded.

A specific example is as follows. Toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, diethylbenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, dichlorotoluene, o-nitrotoluene, m-nitrotoluene, p-nitrotoluene, o- Methoxytoluene, m-methoxytoluene, p-methoxytoluene, o-phenoxytoluene, m-phenoxytoluene, p-phenoxytoluene, o-toluic acid, m-toluic acid, p-toluic acid, o-tolualdehyde, m- Examples include tolualdehyde, p-tolualdehyde, o-cresol, m-cresol, p-cresol, o-methylbenzyl alcohol, m-methylbenzyl alcohol, p-methylbenzyl alcohol and the like.
For the aromatic compound having a side chain alkyl group as described above, the oxygen nucleophile performs, for example, an oxidative addition reaction to carbon adjacent to the aromatic ring of the side chain alkyl group.

Specific production methods using these reactions include, for example, a method of producing a corresponding unsaturated glycol diester by reacting a conjugated diene with carboxylic acid and molecular oxygen, and reacting a conjugated diene with alcohol and molecular oxygen. A corresponding unsaturated glycol diether, a method of reacting cyclohexene with carboxylic acid and molecular oxygen to produce the corresponding acyloxycyclohexene, a reaction of alkylbenzene with carboxylic acid and molecular oxygen And a method for producing siloxyalkylbenzene.
In these production methods, the conjugated diene is preferably selected from butadiene, piperylene, and alkyl-substituted butadiene. Preferably, the carboxylic acid is acetic acid.

  When the platinum group-chalcogen alloy of the present embodiment is used as a catalyst for these reactions, palladium is preferable as the platinum group, and tellurium is preferable as the chalcogen. The catalyst is preferably a platinum group-chalcogen alloy / inorganic porous material-supported catalyst in which a platinum group-chalcogen alloy is supported on an inorganic porous material. In the method for producing an oxidation reaction product in which nucleophile is oxidatively added to at least one reaction substrate selected from olefin, phenyl group or side chain alkyl group in the presence of molecular oxygen, a platinum group-chalcogen alloy / When an inorganic porous material-supported catalyst is used, the amount of platinum group-chalcogen alloy supported on the inorganic porous material is not particularly limited as long as an oxidation reaction product can be obtained. It is platinum group 1 mg or more and 100 mg or less, and chalcogen 1 mg or more and 100 mg or less per 1 g. The ratio of the platinum group to the chalcogen is usually 0.1 mol or more, usually 5 mol or less, preferably 2 mol or less with respect to 1 mol of the platinum group.

As an example of a method for producing an oxidation reaction product in which nucleophilic agent is oxidatively added to at least one reaction substrate selected from olefin, phenyl group or side chain alkyl group in the presence of molecular oxygen, The production of unsaturated glycol diester by acyloxylation will be described in detail below.
The conjugated diene used as a reaction raw material when producing an unsaturated glycol diester using a platinum group-chalcogen alloy / inorganic porous material supported catalyst to which the present embodiment is applied is, for example, butadiene; isoprene, 2, An alkyl-substituted butadiene such as 3-dimethylbutadiene; piperylene; and a cyclic diene such as cyclopentadiene can be used. Preferably, the conjugated diene is selected from butadiene, alkyl-substituted butadiene, and piperylene. The conjugated diene is not necessarily pure, and may include an inert gas such as nitrogen gas, a saturated hydrocarbon such as methane, ethane, and butane, and an unsaturated hydrocarbon such as butene.

  Next, as the carboxylic acid as the other reaction raw material, any of aliphatic, alicyclic, aromatic and the like can be used, but industrially, acetic acid, propionic acid, butyric acid, isobutyric acid And lower aliphatic monocarboxylic acids (having 4 or less carbon atoms). In particular, acetic acid is more preferable in terms of reactivity and price. In addition, the carboxylic acid is a reaction raw material and may also serve as a reaction solvent. Further, if necessary, an organic solvent such as a saturated hydrocarbon or an ester that is inert to the oxidation reaction may be present. good. However, 50% by weight or more of the reaction solvent is preferably a raw material carboxylic acid. The amount of carboxylic acid used is preferably in the range of not less than the stoichiometric amount and not more than 60 mol per mol of the conjugated diene.

  In the method for producing an oxidation reaction product to which the present embodiment is applied, the above-described raw material is contacted with a solid catalyst, preferably in a liquid phase, using molecular oxygen, usually a gas containing molecular oxygen. Here, the gas containing molecular oxygen refers to pure oxygen or a mixed gas of oxygen and inert gas. The inert gas is nitrogen, argon, helium or the like, and the mixed gas includes air. Molecular oxygen can be supplied to the reaction system as an atmospheric pressure to pressurized state at any mixing ratio with an inert gas, but the oxygen concentration is preferably within the range where the gas phase portion in the reaction system does not become an explosive composition. . In general, since the oxidation reaction is more advantageous in terms of the reaction rate as the oxygen partial pressure is higher, it is more preferable to supply the maximum concentration in consideration of the safety factor within the limited range. However, for oxygen concentrations higher than air, it is necessary to provide equipment for promoting the combustion reaction and increasing the oxygen concentration, as well as increasing the danger of the high-concentration oxygen gas itself. It is not generally used except in special cases. The oxygen partial pressure is determined by the oxygen concentration supplied, the composition in the reaction system, the reaction pressure, and the temperature.

Using a platinum group-chalcogen alloy / inorganic porous material-supported catalyst to which this embodiment is applied, a conjugated diene is reacted with a carboxylic acid and molecular oxygen to produce an oxidation-reactive carboxylic acid diester of an unsaturated glycol. The method for producing can be carried out by either a batch method or a continuous method. Moreover, as a reaction system, arbitrary systems, such as a fixed bed system, a fluid bed system, a suspension tank system, can be employ | adopted, and a fixed bed system is more preferable industrially. The reaction temperature is usually 20 ° C. or higher, and considering the reaction rate and by-product formation, the preferred reaction temperature range is 40 ° C. to 120 ° C. The reaction pressure can be normal pressure or pressurization. In order to increase the reaction rate, pressurization is preferable, but the cost of the reaction equipment increases, and considering these factors, a suitable reaction pressure is in the range of normal pressure to 100 kgf / cm ² .

In the above reaction example, acyloxycyclohexene can be produced by using cyclohexene instead of conjugated diene. At this time, the purity of cyclohexene to be used is not particularly limited. For example, even if it contains some cyclohexane and benzene, and even if it contains a trace amount of water, there is no particular problem. Moreover, an acyloxyalkylbenzene can be manufactured by using alkylbenzene instead of conjugated diene. At this time, the purity of the alkylbenzene used is not particularly limited. For example, even if it contains a small amount of benzene or a small amount of water, there is no particular problem.
Furthermore, in the above reaction example, an unsaturated glycol diether can be produced by using alcohol instead of carboxylic acid. The alcohol that can be used in the present invention is not particularly limited, but industrially, for example, lower alcohols having 4 or less carbon atoms such as methanol, ethanol, propanol, and isopropanol are used.

Hereinafter, the present embodiment will be described in more detail based on examples, but the present embodiment is not limited to the following examples unless it exceeds the gist.
(Example 1)
Add 9.7 g of H ₆ TeO ₆ solution containing 15.3% by weight of tellurium to 34.6 g of Na ₂ PdCl ₄ solution containing 14.3% by weight of palladium, and then add 51.6 g of distilled water. Thus, a metal raw material liquid was prepared. This solution contained 5.2 wt% palladium and 1.5 wt% tellurium, and the tellurium / palladium atomic ratio was 0.25. 0.54 g of this metal raw material solution was added dropwise to 5.02 g of an alkaline solution containing 10% by weight of Na ₂ SiO ₃ with stirring, and then allowed to stand overnight, and the precipitate was filtered off. 20 g of distilled water was added to the precipitate, washed with water, and then filtered again.

Next, the precipitate was placed in a Pyrex (registered trademark) glass tube having an inner diameter of 2.5 cm (effective cross-sectional area 4.9 cm ² ) covered with glass wool, and 90 ° C. while flowing 1.0 Nl / min of nitrogen gas. And then heated to 150 ° C. and dried for 1 hour. Next, it was switched to hydrogen at 0.5 Nl / min, heated at a rate of 50 ° C. per hour, held at 400 ° C. for 2 hours, then cooled in a nitrogen stream and reduced, and the precipitate turned black. . The whole amount of this was taken out together with glass wool, extracted with aqua regia, and quantified by ICP. As a result, it contained 24.1 mg of palladium and 7.4 mg of tellurium, and the tellurium / palladium atomic ratio was 0.25.

(Example 2)
An alloy was synthesized in the same manner as in Example 1 except that 0.56 g of the metal raw material solution used in Example 1 was dropped into 5.04 g of an alkaline solution containing 18% by weight of Na ₂ CO _3. As a result of quantifying the palladium and tellurium contents of the catalyst, it contained 19.7 mg of palladium and 5.6 mg of tellurium, and the tellurium / palladium atomic ratio was 0.24.

(Example 3)
16.7 g of H ₆ TeO ₆ solution containing 15.3 wt% tellurium is added to 20.2 g of RhCl ₃ solution containing 10.1 wt% rhodium, and then 3.24 g of distilled water is added. Thus, a metal raw material liquid was prepared. This solution contained 5.1 wt% rhodium and 6.4 wt% tellurium, and the tellurium / rhodium atomic ratio was 1.0. An alloy was synthesized in the same manner as in Example 1 except that 0.56 g of this metal raw material solution was dropped into 5.11 g of an alkaline solution containing 10 wt% Na ₂ SiO _3, and contained rhodium and tellurium in the alloy. As a result of quantitative determination, it contained rhodium 23.1 mg and tellurium 29.3 mg, and the tellurium / rhodium atomic ratio was 1.0.

Example 4
An alloy was synthesized in the same manner as in Example 1 except that 0.65 g of the metal raw material solution used in Example 3 was dropped into 5.13 g of an alkaline solution containing 16% by weight of NaOH, and rhodium in the alloy and As a result of quantifying the tellurium content, it contained 25.6 mg of rhodium and 33.0 mg of tellurium, and the tellurium / rhodium atomic ratio was 1.0.

(Example 5)
An alloy was synthesized in the same manner as in Example 1 except that 0.65 g of the metal raw material solution used in Example 3 was dropped into 5.12 g of an alkaline solution containing 18% by weight of Na ₂ CO _3. As a result of quantifying the rhodium and tellurium contents, it contained 26.9 mg of rhodium and 35.4 mg of tellurium, and the tellurium / rhodium atomic ratio was 1.1.

(Example 6)
A metal raw material solution was prepared by adding 10.6 g of a H ₆ TeO ₆ solution containing 15.3% by weight of tellurium to 15.3 g of a RuCl ₃ solution containing 8.4% by weight of ruthenium. This solution contained 5.0 wt% ruthenium and 6.3 wt% tellurium, and the tellurium / ruthenium atomic ratio was 1.0. An alloy was synthesized in the same manner as in Example 1 except that 0.56 g of this metal raw material solution was dropped into 5.05 g of an alkaline solution containing 10% by weight of Na ₂ SiO _3, and contained ruthenium and tellurium in the alloy. As a result of quantitative determination, it contained 22.8 mg of ruthenium and 29.0 mg of tellurium, and the tellurium / ruthenium atomic ratio was 1.0.

(Example 7)
An alloy was synthesized in the same manner as in Example 1 except that 0.56 g of the metal raw material solution used in Example 6 was dropped into 5.05 g of an alkaline solution containing 16% by weight of NaOH, and ruthenium and As a result of quantifying the tellurium content, 22.3 mg of ruthenium and 27.6 mg of tellurium were contained, and the tellurium / ruthenium atomic ratio was 1.0.

(Example 8)
An alloy was synthesized in the same manner as in Example 1 except that 0.52 g of the metal raw material solution used in Example 6 was dropped into 5.08 g of an alkaline solution containing 22 wt% KOH, and ruthenium and As a result of quantifying the tellurium content, it contained 20.4 mg of ruthenium and 26.6 mg of tellurium, and the tellurium / ruthenium atomic ratio was 1.0.

(Comparative Example 1)
Although 1.52 g of a H ₆ TeO ₆ solution containing 15.3% by weight of tellurium was added dropwise to 5.09 g of an alkaline solution containing 10% by weight of Na ₂ SiO ₃ with stirring, no precipitate was observed. There wasn't.

(Comparative Example 2)
Although 1.55 g of a H ₆ TeO ₆ solution containing 15.3% by weight of tellurium was added dropwise to 5.22 g of an alkaline solution containing 16% by weight of NaOH with stirring, no precipitate was observed.

Example 9
A 50 ml volumetric flask is charged with 3.8 g of a telluric acid aqueous solution containing 13.7% by weight of Te, and 18.6 g of a palladium chloride hydrochloric acid solution containing 9.34% by weight of palladium is added thereto. Was added to 50 ml. To this solution, 26.0 g of a spherical silica carrier (CariACT-15 manufactured by Fuji Silysia Chemical Ltd., particle diameter 1.7 mm to 3.4 mm) was added and immersed for 2 hours at room temperature. Then, the solution was removed by filtration. Furthermore, by removing the liquid with a centrifugal separator, 52.4 g of a spherical silica carrier impregnated with a palladium chloride hydrochloric acid solution and an aqueous telluric acid solution was obtained. To 50.0 g of this spherical silica carrier, 52.6 g of 1.6N-NaOH aqueous solution was added, stirred at room temperature for 4 h, and left overnight. Next, the spherical silica support was filtered off, transferred to a Pyrex (registered trademark) glass tube having an inner diameter of 3.5 cm (effective cross-sectional area of 9.6 cm ² ), and continuously with distilled water of about 1 liter / h for 8 hours. Washed. This was filtered to remove the solution, placed in a Pyrex (registered trademark) glass tube having an inner diameter of 4.6 cm (effective area 16.6 cm ² ), and flowing nitrogen gas at 8 Nl / min for 3 hours at 90 ° C. Further, the temperature was raised to 150 ° C. and dried for 2 hours. Next, it was switched to hydrogen at 1 Nl / min, heated at a rate of 50 ° C. per hour, maintained at 400 ° C. for 2 hours, cooled in a nitrogen stream and activated, and 24.1 g of palladium chloride and telluric acid / spherical silica supported catalyst. Got. The catalyst contained 3.3% by weight palladium and 1.0% by weight tellurium.

Next, 4 g of this catalyst was filled into a stainless steel reaction tube having an inner diameter of 12 mm (effective cross-sectional area of 1.005 cm ² ), and reaction pressure was 60 kgf / cm ^{2 at a} reaction temperature of 80 ° C., 0.13-mol of 1,3-butadiene, The diacetoxylation reaction of butadiene was carried out continuously for 7 hours with a flow rate of 2.5 mol / hour of acetic acid and 100 Nl / hour of nitrogen containing 6% oxygen. In this reaction, the product was quantified by gas chromatography for the reaction liquid fraction for 4 to 5 hours and the reaction liquid fraction for 6 to 7 hours after the start of the reaction, and the average value was used as the reaction result. . Activity and selectivity are determined from the reaction results, and the results are shown in Table 1.

  In Table 1, the activity (unit: mmol) is 3,4-diacetoxybutene-1, 3-hydroxy-4-acetoxybutene-1, 1-acetoxy which is a product per hour with respect to 1 kg of catalyst. Sum of crotonaldehyde, 1,4-diacetoxybutene-2 (1,4-DABE), 1-hydroxy-4-acetoxybutene-2, 1,4-dihydroxybutene-2, diacetoxyoctatriene and triacetoxybutene Is the production amount. The 1,4-DABE selectivity is 1, 4 to the total amount of products obtained by adding the products of furan, acrolein, monoacetoxybutene, butanol and monoacetoxy-1,3-butadiene to the above products. -The ratio (unit; mol%) of the production amount of diacetoxybutene-2.

(Example 10)
A 50 ml volumetric flask was charged with 3.8 g of an aqueous telluric acid solution containing 13.7% by weight of Te, and a 30% palladium chloride hydrochloric acid solution containing 5.7% by weight of palladium and 6.2% by weight of NaCl. 7 g was added, and the volume was increased to 50 ml by adding demineralized water. To this solution, 25.8 g of a spherical silica carrier (CariACT-15 manufactured by Fuji Silysia Chemical Co., Ltd., particle diameter 1.7 mm to 3.4 mm) was added and immersed for 2 hours at room temperature. Further, 52.4 g of a spherical silica carrier impregnated with a palladium chloride hydrochloric acid solution and an aqueous telluric acid solution was obtained by removing the solution with a centrifugal separator. Palladium chloride and telluric acid / spherical silica-supported catalyst was prepared and activated in the same manner as in Example 9, except that 51.3 g of 1.6N-NaOH aqueous solution was added to 50.1 g of this spherical silica support 24 .3 g was obtained. The catalyst contained 3.3% by weight palladium and 1.0% by weight tellurium. Using this catalyst, a diacetoxylation reaction of butadiene was carried out in the same manner as in Example 9. The results are shown in Table 1.

(Example 11)
Into a 50 ml volumetric flask is placed 3.8 g of an aqueous telluric acid solution containing 13.7 wt% Te, and to this was added 12.1 g of a sodium chloropalladate solution containing 14.3 wt% palladium. It was made up to 50 ml by adding brine. To this solution was added 26.1 g of spherical silica support (CariACT-15 manufactured by Fuji Silysia Chemical Co., Ltd., particle diameter 1.7 mm to 3.4 mm) and immersed for 2 hours at room temperature, and this was filtered to remove the solution. Furthermore, 52.6 g of a spherical silica carrier impregnated with a sodium chloropalladate solution and a telluric acid aqueous solution was obtained by removing the solution with a centrifuge. A catalyst was prepared in the same manner as in Example 9 except that 33.4 g of 1.6N-NaOH aqueous solution was added to 33.4 g of this spherical silica support, and activated sodium chloropalladate and telluric acid / spherical silica supported catalyst. 16.2 g was obtained. The catalyst contained 3.2% by weight palladium and 1.0% by weight tellurium. Using this catalyst, a diacetoxylation reaction of butadiene was carried out in the same manner as in Example 9. The results are shown in Table 1.

(Example 12)
Into a 50 ml volumetric flask is placed 3.6 g of an aqueous telluric acid solution containing 13.7% by weight of Te. To this was added 10.3 g of a sodium chloropalladate solution containing 16.0% by weight of palladium. It was made up to 50 ml by adding brine. 25.5 g of spherical silica support (CariACT-15 manufactured by Fuji Silysia Chemical Co., Ltd., particle diameter 1.7 mm to 3.4 mm) was added to this solution and immersed for 2 hours at room temperature, and this was filtered to remove the solution. Furthermore, 51.0 g of a spherical silica carrier impregnated with a sodium chloropalladate solution and an aqueous telluric acid solution was obtained by draining with a centrifuge. To 25.2 g of this spherical silica support, 31.1 g of an alkaline solution containing 4.8% by weight of diisopropylamine was added, stirred at room temperature for 15 minutes, and then filtered to remove the solution. Next, after filtering this spherical silica support, it was transferred to a Pyrex (registered trademark) glass tube having an inner diameter of 3.5 cm (effective area 9.6 cm ² ), and continuously with distilled water of about 1 liter / hour. Washed for hours. This was filtered to remove the solution, placed in a Pyrex (registered trademark) glass tube having an inner diameter of 4.6 cm (effective area 16.6 cm ² ), and flowing nitrogen gas at 8 Nl / min for 3 hours at 90 ° C. Further, the temperature was raised to 150 ° C. and dried for 2 hours. Next, it was switched to hydrogen at 1 Nl / min, heated at a rate of 50 ° C. per hour, maintained at 400 ° C. for 2 hours, cooled in a nitrogen stream, and activated and treated with sodium chloropalladate and telluric acid / spherical silica 12 .4 g was obtained. The catalyst contained 3.1% by weight palladium and 1.0% by weight tellurium. Using this catalyst, a diacetoxylation reaction of butadiene was carried out in the same manner as in Example 9. The results are shown in Table 1.

(Example 13)
Into a 50 ml volumetric flask is placed 3.6 g of an aqueous telluric acid solution containing 13.7% by weight of Te. To this was added 10.3 g of a sodium chloropalladate solution containing 16.0% by weight of palladium. It was made up to 50 ml by adding brine. 25.5 g of spherical silica support (CariACT-15 manufactured by Fuji Silysia Chemical Co., Ltd., particle diameter 1.7 mm to 3.4 mm) was added to this solution and immersed for 2 hours at room temperature, and this was filtered to remove the solution. Further, 51.0 g of a spherical silica carrier impregnated with a sodium chloropalladate solution and an aqueous telluric acid solution was obtained by removing the solution with a centrifugal separator. A sodium chloropalladate and telluric acid / spherical silica supported catalyst were prepared in the same manner as in Example 9 except that 32.4 g of an alkaline solution containing 10.0 wt% sodium silicate was added to 25.8 g of this spherical silica support. 13.1 g of the prepared and activated catalyst was obtained. The catalyst contained 3.1% by weight palladium and 1.0% by weight tellurium. Using this catalyst, a diacetoxylation reaction of butadiene was carried out in the same manner as in Example 9. The results are shown in Table 1.

(Comparative Example 3)
A 50 ml volumetric flask is charged with 2.7 g of a telluric acid aqueous solution containing 19.7% by weight of tellurium, and 7.4 g of a palladium chloride hydrochloric acid solution containing 24.2% by weight of palladium is added thereto. It was made up to 50 ml by adding brine. To this solution was added 22.8 g of a spherical silica support (CARIACT-15, manufactured by Fuji Silysia Chemical Co., Ltd., particle diameter 1.7 mm to 3.4 mm) and immersed for 1 hour at room temperature, and this was filtered to remove the solution. Further, by removing the solution with a centrifugal separator, 46.0 g of a spherical silica carrier impregnated with a sodium chloropalladate solution and an aqueous telluric acid solution was obtained. This spherical silica support was placed in a Pyrex (registered trademark) glass tube having an inner diameter of 2.5 cm (effective cross-sectional area of 4.9 cm ² ), and at 150 ° C. for 3 hours while flowing 6.7 Nl / min of nitrogen gas, an additional 150 The temperature was raised to ° C. and dried for 2 hours. Next, it was switched to 0.42 Nl / min of hydrogen, heated at a rate of 50 ° C. per hour, held at 400 ° C. for 2 hours, then cooled and activated in a nitrogen stream and activated by sodium chloropalladate and telluric acid / spherical silica. 23.7 g of supported catalyst was obtained. The catalyst contained 3.2% palladium and 0.96% tellurium. Using this catalyst, a diacetoxylation reaction of butadiene was carried out in the same manner as in Example 9. The results are shown in Table 1.

(Comparative Example 4)
16.8 g of an aqueous nitric acid solution containing telluric acid containing 2.8% by weight of tellurium and palladium nitrate containing 9.5% by weight of palladium is added to a 50 ml volumetric flask, and demineralized water is added. As a result, the volume was increased to 50 ml. To this solution was added 21.8 g of a spherical silica support (CariACT-15 manufactured by Fuji Silysia Chemical Ltd., particle diameter 1.7 mm to 3.4 mm) and immersed for 1 hour at room temperature. Then, this was filtered to remove the solution. Further, by removing the liquid with a centrifuge, 44.4 g of a spherical silica carrier impregnated with a sodium chloropalladate solution and an aqueous telluric acid solution was obtained. This spherical silica support was placed in a Pyrex (registered trademark) glass tube having an inner diameter of 2.5 cm (effective cross-sectional area of 4.9 cm ² ), and at 150 ° C. for 3 hours while flowing 6.7 Nl / min of nitrogen gas, an additional 150 The temperature was raised to ° C. and dried for 2 hours. Next, it was switched to 0.42 Nl / min of hydrogen, heated at a rate of 50 ° C. per hour, held at 400 ° C. for 2 hours, cooled in a nitrogen stream and activated, and supported with sodium chloropalladate and telluric acid / spherical silica 22.6 g of catalyst was obtained. The catalyst contained 3.0% by weight palladium and 0.89% by weight tellurium. Using this catalyst, a diacetoxylation reaction of butadiene was carried out in the same manner as in Example 9. The results are shown in Table 1.

(Comparative Example 5)
Into a 50 ml volumetric flask is placed 26.2 g of a solution of 6.3 wt% metal palladium as palladium and 1.9 wt% metal tellurium as tellurium in nitric acid, which contains 8.0 wt% sodium. 13.8 g of an aqueous sodium chloride solution to be added was added, and the volume was increased to 50 ml by adding demineralized water. To this solution was added 21.5 g of a spherical silica carrier (CariACT-15 manufactured by Fuji Silysia Chemical Co., Ltd., particle diameter 1.7 mm to 3.4 mm) and immersed for 1 hour at room temperature. Then, this was filtered to remove the solution. Furthermore, 46.0 g of a spherical silica carrier impregnated with a nitric acid solution of metallic palladium and metallic tellurium was obtained by draining with a centrifugal separator. This spherical silica support was placed in a Pyrex (registered trademark) glass tube having an inner diameter of 2.5 cm (effective cross-sectional area of 4.9 cm ² ), and at 150 ° C. for 3 hours while flowing 6.7 Nl / min of nitrogen gas, an additional 150 The temperature was raised to ° C. and dried for 2 hours. Next, it was switched to 0.42 Nl / min of hydrogen, heated at a rate of 50 ° C. per hour, held at 400 ° C. for 2 hours, cooled in a nitrogen stream and activated, and the metal palladium-metal tellurium / spherical silica supported catalyst 22 was activated. 0.7 g was obtained. This catalyst contained 3.0% by weight palladium, 0.91% by weight tellurium and 2.0% by weight sodium. Using this catalyst, a diacetoxylation reaction of butadiene was carried out in the same manner as in Example 9. The results are shown in Table 1.

From the results of Table 1, when a palladium compound-tellurium / silica supported catalyst to which the present embodiment is applied and diacetoxylation reaction of butadiene is performed in the presence of molecular oxygen (Examples 9 to 13), It can be seen that the catalytic activity is extremely high.
In contrast, when a butadiene diacetoxylation reaction was performed in the presence of molecular oxygen using a palladium compound-tellurium / silica supported catalyst prepared without alkali treatment (Comparative Examples 3 to 5), Compared with Examples 9-13, it turns out that catalyst activity is about 1/2 or less.

(Example 14)
4 g of the catalyst prepared in Example 9 was packed into a stainless steel reaction tube having an inner diameter of 12 mm (effective cross-sectional area of 1.005 cm ² ), acetic acid 2.5 mol / hour, nitrogen 100 Nl / hour at 80 kg at 60 kgf / cm ² . The alkali metal and halogen contained in the catalyst were washed by flowing for 7 hours at a flow rate of 5%. Thereafter, at a reaction pressure of 60 kgf / cm ² , a reaction temperature of 80 ° C., isoprene was 81 mmol / hr, acetic acid was 2.2 mol / hr, and the flow rate was 100 Nl / hr of nitrogen containing 6% by volume of oxygen, and diacetoxylation reaction of isoprene. For 7 hours continuously. In this reaction, 1,4-diacetoxy-2-methylbutene-2 was quantified by gas chromatography on the reaction liquid fraction for 4 to 5 hours and the reaction liquid fraction for 6 to 7 hours after the start of the reaction. The average value was taken as the reaction result. The activity was determined from the reaction results, and the results are shown in Table 2.

(Comparative Example 6)
Using the catalyst prepared in Comparative Example 3, an acetoxylation reaction of isoprene was carried out in the same manner as in Example 14. The results are shown in Table 2.

(Comparative Example 7)
Using the catalyst prepared in Comparative Example 4, the acetoxylation reaction of isoprene was carried out in the same manner as in Example 14. The results are shown in Table 2.

From the results in Table 2, when the palladium compound-tellurium / silica supported catalyst to which the present embodiment is applied is used and the diacetoxylation reaction of isoprene is performed in the presence of molecular oxygen (Example 14), the production rate Is very large.
On the other hand, when a diacetoxylation reaction of isoprene was carried out in the presence of molecular oxygen using a palladium compound-tellurium / silica supported catalyst prepared without performing alkali treatment (Comparative Examples 6 and 7), Compared to Example 13, it can be seen that the generation rate is about ½.

Claims (9)

  A method of coprecipitation of a chalcogen compound, comprising contacting a solution of a chalcogen compound with an alkali component in the presence of a platinum group compound to precipitate the platinum group compound and the chalcogen compound. Contacting a solution of the chalcogen compound with an alkali component in the presence of a platinum group compound to precipitate a coprecipitate of the platinum group compound and the chalcogen compound;
A method for producing a platinum group-chalcogen alloy, comprising reducing the coprecipitate. Contacting a platinum group compound and a chalcogen compound solution with an alkali component in the presence of an inorganic porous material;
Depositing a coprecipitate of the platinum group compound and the chalcogen compound on the inorganic porous body;
A method for producing a platinum group-chalcogen alloy / inorganic porous material carrier, wherein the coprecipitate is reduced.   The method for producing a platinum group-chalcogen alloy / inorganic porous material support according to claim 3, wherein the platinum group-chalcogen alloy / inorganic porous material support is a catalyst.   5. The method for producing a platinum group-chalcogen alloy / inorganic porous material support according to claim 3, wherein the platinum group compound is a compound of palladium, rhodium, or ruthenium.   The method for producing a platinum group-chalcogen alloy / inorganic porous material carrier according to any one of claims 3 to 5, wherein the chalcogen compound is a tellurium compound.   The method for producing a platinum group-chalcogen alloy / inorganic porous material carrier according to any one of claims 3 to 6, wherein the inorganic porous material is silica.   In the presence of platinum group-chalcogen alloy / inorganic porous material supported catalyst and molecular oxygen obtained by reducing the coprecipitate of platinum group compound and chalcogen compound adsorbed and supported on the inorganic porous material, olefins and aromatics A method for producing an oxidation reaction product, wherein a nucleophile is oxidatively added to at least one reaction substrate selected from the group compounds.   The method for producing an oxidation reaction product according to claim 8, wherein the reaction substrate is a conjugated diene, and the nucleophile is a carboxylic acid or an alcohol.