Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
  • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
  • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/18—Carbon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
  • B01J23/42—Platinum
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/56—Platinum group metals
  • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/644—Arsenic, antimony or bismuth
  • B01J23/6447—Bismuth
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/90—Regeneration or reactivation
  • B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
  • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
  • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
  • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
  • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
  • C07C2523/42—Platinum

Definitions

• the present invention relates to a method for producing an oxide and a method for producing a Pt/Bi composite catalyst.
• Patent Document 1 describes a method for preparing a catalyst obtained by adding an aqueous dispersion of a catalyst in which Pt is supported on activated carbon to an aqueous solution containing Bi in an ion state, and A method for producing an oxide is disclosed in which an alcohol or the like is dehydrogenated and oxidized in the presence of the catalyst obtained by the above preparation method to obtain an oxide.
• Patent Document 2 describes a catalyst containing a noble metal of Group VIII of the periodic table such as Pd or Pt, in an alkaline aqueous phase, with a polyalkoxy alcohol or an aliphatic alcohol alkoxylate.
• a method for the preparation of ether carboxylic acids is disclosed which is oxidized in the presence.
• an organic compound having one primary hydroxyl group is subjected to a dehydrogenative oxidation reaction in the presence of Pt supported on a carrier, a Bi ion source, and water under conditions where the minimum pH value during the reaction is less than 7. and obtaining an oxide of the organic compound.
• Pt supported on a carrier and a Bi ion source are mixed in the presence of an organic compound having one primary hydroxyl group and water, and the minimum pH value during the reaction is less than 7. It relates to a method for preparing a Pt/Bi composite catalyst, which is reacted under the conditions.
• the catalyst preparation method described in Patent Document 1 is a separate process from the process for producing oxides such as alcohol, it is necessary to prepare a catalyst production facility separately from the production facility for oxides such as alcohol. there were.
• the process of preparing the catalyst requires a process of separating and purifying the catalyst. Since it is necessary to store the catalyst under appropriate storage conditions during this period, there is a problem that a great deal of cost and labor is required for the preparation of the catalyst in addition to the production of oxides such as alcohol.
• the method for producing an ethercarboxylic acid described in Patent Document 2 has a problem that the productivity of the ethercarboxylic acid is low.
• the present invention provides a method for producing an oxide that can efficiently obtain an oxide of an organic compound in the presence of a raw material for a Pt/Bi composite catalyst, and also in the presence of an organic compound as a raw material for the oxide,
• the present invention relates to a method for producing a Pt/Bi composite catalyst capable of producing a catalyst exhibiting high activity in dehydrogenative oxidation reactions of organic compounds.
• the present inventors have found that even in the presence of raw materials for a Pt/Bi composite catalyst, by setting the pH during the reaction to less than 7, an oxide of an organic compound can be efficiently obtained. It has been found that even in the presence of the organic compound, a catalyst exhibiting high activity in the dehydrogenative oxidation reaction of the organic compound can be produced by setting the pH to less than 7 during the reaction.
• the present invention relates to the following [1] and [2]. [1] In the presence of Pt supported on a carrier, a Bi ion source, and water, an organic compound having one primary hydroxyl group is subjected to a dehydrogenative oxidation reaction under the condition that the minimum pH value during the reaction is less than 7.
• a method for producing an oxide that can efficiently obtain an oxide of an organic compound in the presence of a raw material for a Pt/Bi composite catalyst, a method for producing an oxide that can efficiently obtain an oxide of an organic compound, and in the presence of an organic compound as a raw material for the oxide
• an organic A method for producing an oxide in which a compound (hereinafter also simply referred to as an “organic compound”) undergoes a dehydrogenative oxidation reaction to obtain an oxide of the organic compound.
• an oxide of an organic compound can be obtained efficiently.
• the reason why the above effect is obtained is not clear, it is presumed as follows.
• the Pt/Bi composite catalyst used in the reaction is charged together in the state of raw materials, so that the Pt/Bi composite catalyst is produced in the reaction system. is produced, the organic compound is dehydrogenated and oxidized.
• a Pt ion source and a Bi ion source are usually combined under alkaline conditions by adding a reducing agent.
• a composite catalyst of Pt and Bi is prepared by precipitating and depositing Pt and Bi, but since Bi at this time segregates, there are few active structures effective for the dehydrogenative oxidation reaction of organic compounds, and the catalyst It is considered that the activity of
• Bi when the Pt supported on the carrier is brought into contact with the Bi ion source under the condition that the minimum pH value during the reaction is less than 7, Bi is generated even without a reducing agent, although the reason is not clear. Since it can be uniformly reduced and deposited on Pt, many active structures effective for the dehydrogenative oxidation reaction of organic compounds can be formed, so it is thought that the activity of the catalyst was able to be high. .
• the organic compound can be efficiently dehydrogenated and oxidized with a composition having a high active ingredient concentration in which the ratio of is increased, and the productivity can be improved. Furthermore, since the generation of salts generated when the oxides are extracted from the neutralized salts of the by-produced oxides can be suppressed, the generation of waste liquid can be suppressed and the environmental load can be reduced.
• the method for producing an oxide of the present invention preferably involves preparation of a Pt/Bi composite catalyst from the viewpoint of obtaining an organic compound oxide at a high production rate.
• the reason why the Pt/Bi composite catalyst is preferably prepared is not clear, it is considered as follows.
• a dehydrogenative oxidation reaction of the organic compound occurs.
• a small amount of the oxide of the organic compound is generated, resulting in an oxide-containing solution, so that the Bi ion source is dissolved to generate Bi ions, and Bi is reduced and deposited on Pt, so that it is less than the Pt catalyst.
• the method for producing an oxide of the present invention can prepare a catalyst at the same time in the process of producing an oxide, so that it does not require a separate facility or process for producing a catalyst, and can efficiently produce an organic
• the compound oxide can be produced, which has great advantages in production efficiency and production cost.
• Pt means platinum
• Bi means bismuth
• C means activated carbon.
• % indicates “% by mass” unless otherwise specified in this specification.
• Organic compound having one primary hydroxyl group (hereinafter simply referred to as an organic compound) to a dehydrogenative oxidation reaction.
• organic compounds having one primary hydroxyl group include aliphatic alcohols, polyoxyalkylene alkyl ethers, amide alcohols, and aromatic alcohols. From the viewpoint of hydrophilicity, aliphatic alcohols and polyoxy At least one selected from alkylene alkyl ethers and amido alcohols, more preferably at least one selected from aliphatic alcohols and polyoxyalkylene alkyl ethers.
• the aliphatic alcohol or polyoxyalkylene alkyl ether is preferably one or two or more represented by the following general formula (1) or general formula (2).
• R 1 is a monovalent aliphatic hydrocarbon group having 2 to 40 carbon atoms.
• R 2 O—(AO) n —H (2)
• R 2 is a monovalent aliphatic hydrocarbon group having 2 to 40 carbon atoms
• A is an alkanediyl group having 2 to 4 carbon atoms
• AO represents an alkyleneoxy group
• n is alkyleneoxy. It is the average value of the number of added moles of groups, and is 1 or more and 30 or less.
• R 1 is preferably a linear or branched primary monovalent aliphatic hydrocarbon group, more preferably a linear or branched primary alkyl group or alkenyl groups, more preferably linear, primary alkyl groups.
• R 1 Although the number of carbon atoms in R 1 is not particularly limited, it may be 6 or more, 8 or more, 10 or more, or 12 or more, and from the viewpoint of reactivity, it is preferably 36 or less, more preferably 22 or less, and further It is preferably 18 or less, more preferably 14 or less.
• R 2 is preferably a linear or branched primary aliphatic hydrocarbon group, more preferably a linear or branched primary alkyl or alkenyl group, more preferably More preferably, it is a linear, primary alkyl group.
• the number of carbon atoms in R 2 is not particularly limited, but may be 6 or more, 8 or more, 10 or more, or 12 or more, preferably 36 or less, more preferably 22 or less, from the viewpoint of reactivity. More preferably 18 or less, still more preferably 14 or less.
• A is preferably an ethylene group or a propylene group, more preferably an ethylene group.
• AO is preferably an ethyleneoxy group (EO) or a propyleneoxy group (PO), more preferably an ethyleneoxy group (EO), from the viewpoint of reactivity.
• n is preferably 3 or more, and is preferably 25 or less, more preferably 20 or less, still more preferably 16 or less, and even more preferably 12 or less.
• the strength of the hydrophilicity of the organic compound affects reactivity, and the higher the hydrophilicity, the higher the reactivity between the Pt/Bi composite catalyst and the organic compound. That is, the larger the IOB value (balance value between inorganic and organic) IV/OV calculated from the inorganic value (Inorganic Value) IV and the organic value (Organic Value) OV in the organic conceptual diagram of the organic compound, the reaction highly sexual. Therefore, from the viewpoint of high hydrophilicity, the organic compound is preferably a polyoxyalkylene alkyl ether, more preferably a polyoxyalkylene alkyl ether represented by the general formula (2).
• the IOB value based on the organic conceptual diagram of the organic compound is preferably 0.3 or more, more preferably 1 or more, and still more preferably 4 or more from the viewpoint of reactivity.
• the IOB value of the organic compound may be less than 5.
• a carboxylic acid compound or a salt of a carboxylic acid compound can be obtained as an oxide by subjecting the above-described organic compound to a dehydrogenative oxidation reaction.
• Carboxylic acid compounds or salts of carboxylic acids include carboxylic acid compounds or salts of carboxylic acid compounds obtained by dehydrogenative oxidation reaction of the aforementioned aliphatic alcohols or polyoxyalkylene alkyl ethers, for example, polyoxyalkylene So-called ether carboxylates or salts thereof obtained by oxidation reaction of alkyl ethers can be mentioned.
• the carrier used for the Pt supported on the carrier is preferably a carrier selected from titania, zirconia and activated carbon, more preferably activated carbon, from the viewpoint of allowing the reaction to occur under conditions of pH less than 7.
• the activated carbon is not particularly limited, and any type of activated carbon can be used as long as it can adsorb and support Pt.
• Examples of activated carbon include vegetable activated carbon such as coconut shell activated carbon, mineral activated carbon such as coal-based activated carbon, pulp waste liquid, synthetic resin, and organic waste activated carbon.
• Coal-based activated carbon is preferred because of its high activity compared to vegetable-based activated carbon.
• vegetable activated carbon is more preferable than coal-based activated carbon in terms of strength to prevent crushing during filtration.
• the particle size of Pt supported on the carrier is not particularly limited, but from the viewpoint of increasing the amount of Pt supported, it is preferably 1 nm or more, more preferably 3 nm or more. It is preferably 20 nm or less, more preferably 15 nm or less, still more preferably 10 nm or less.
• the supported amount of Pt with respect to the total amount of the carrier and Pt is preferably 0.1% by mass or more, more preferably 1% by mass, from the viewpoint of the reactivity of the dehydrogenative oxidation reaction of the organic compound. % by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 20% by mass or less from the viewpoint of enhancing the dispersibility of Pt on the carrier surface. , more preferably 15% by mass or less, and still more preferably 10% by mass or less.
• Pt supported on a carrier can be prepared by a known impregnation method or precipitation deposition method, but commercially available products can also be used.
• the amount of Pt supported on the carrier can be arbitrarily selected within a range in which a practical reaction rate can be obtained according to the reaction temperature or reaction pressure. , with respect to 100 parts by mass of the organic compound, preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 4 parts by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass Below, more preferably 6 mass parts or less.
• the Bi ion source is preferably water-insoluble from the viewpoint of improving the catalytic activity of the produced Pt/Bi composite catalyst and efficiently obtaining an oxide.
• Bi ion sources include bismuth nitrate pentahydrate ( Bi ( NO3 ) 3.5H2O ) , bismuth oxide (Bi2O3), basic bismuth carbonate ( ( BiO) 2CO3 ) and bismuth hydroxide. It is preferably at least one selected from (Bi(OH) 3 ).
• the catalytic activity of the obtained Pt/Bi composite catalyst varies depending on the Bi ion source used.
• bismuth oxide when used as the Bi ion source, a Pt/Bi composite catalyst with high catalytic activity is obtained, and organic compounds are produced.
• Bismuth oxide is suitable as the Bi ion source because the oxide can be obtained efficiently.
• the amount of the Bi ion source to be charged is preferably 0.01 part by mass or more, more preferably 0.01 part by mass or more per 100 parts by mass of the organic compound, from the viewpoint of catalyst production efficiency and organic compound oxide production efficiency.
• the mass ratio (atomic ratio) Bi/Pt of the charged amount of Bi to Pt is preferably 0.05 or more, more preferably 0.05 or more, from the viewpoint of improving the productivity of oxidation reaction products. is 0.1 or more, and is preferably 2.0 or less, more preferably 1.8 or less, even more preferably 1.5 or less, even more preferably 1.4 or less, still more preferably 1.2 or less , and more preferably 1.0 or less.
• the reactivity for preparing the Pt/Bi composite catalyst varies depending on the amount of bismuth oxide charged. Addition of even a small amount of bismuth oxide improves the reactivity for preparing a Pt/Bi composite catalyst.
• a preferred embodiment of the amount of bismuth oxide to be charged with respect to 100 parts by mass of the organic compound is the same as the preferred embodiment of the amount of the Bi ion source to be charged.
• the method for producing an oxide of the present invention is carried out in the presence of water, and water preferably includes ion-exchanged water, distilled water, pure water, and the like.
• the amount of water used is preferably 15 parts by mass or more, more preferably 20 parts by mass or more with respect to 100 parts by mass of the organic compound, from the viewpoint of improving the productivity of the organic compound oxide and suppressing the increase in the viscosity of the liquid phase. , preferably 35 parts by mass or less, more preferably 30 parts by mass or less.
• the amount of water used is the sum of the water to be charged, the water content of Pt supported on the carrier, and the water content of the Bi ion source.
• the minimum value of pH during the reaction is less than 7.
• the inside of the reaction system can be made acidic, the Bi ion source is easily dissolved and Bi ions are easily generated, and Bi can be generated from Bi ions alone by activated carbon or the like. Since precipitation on the carrier can be suppressed and Bi can be reduced and precipitated in the vicinity of Pt to create a highly active structure, a highly active Pt/Bi composite catalyst can be produced, and dehydrogenative oxidation of organic compounds. It is considered that the reactivity of the reaction is greatly improved.
• the minimum value of the pH during the reaction is less than 7 by not adding an alkaline agent or the like to the reaction system because the organic compound undergoes a dehydrogenative oxidation reaction to produce an oxide. can be adjusted.
• the organic compound is added to the reaction system. As the amount of oxides increases, it becomes acidic.
• the minimum value of the pH at the end of the reaction is preferably 6 or less, more preferably 5 or less, still more preferably 5 or less, from the viewpoint of improving the production efficiency of the Pt/Bi composite catalyst and improving the production efficiency of the organic compound oxide. 4 or less, and preferably 1 or more, more preferably 1.5 or more, and still more preferably 2 or more.
• reaction temperature The reaction temperature in the oxide production method of the present invention is preferably 50° C. or higher, more preferably 60° C., from the viewpoint of the reaction for producing the Pt/Bi composite catalyst and the reactivity of the dehydrogenative oxidation reaction of the organic compound. From the viewpoint of equipment load, the temperature is preferably 100° C. or lower, more preferably 90° C. or lower, and even more preferably 85° C. or lower.
• oxygen-containing gas In the method for producing an oxide of the present invention, it is preferable to supply oxygen to the reaction system from the viewpoint of dehydrogenating and oxidizing the organic compound.
• the supply of oxygen can be carried out by passing an oxygen-containing gas through the liquid phase.
• the oxygen-containing gas include gases containing oxygen such as oxygen gas and air.
• the gas used in combination with oxygen is preferably an inert gas such as helium, argon, or nitrogen from the viewpoint of not affecting activity.
• the oxygen concentration in the oxygen-containing gas is preferably 10% by volume or more, more preferably 50% by volume or more, even more preferably 70% by volume or more, and even more preferably 90% by volume or more. , and more preferably 100% by volume.
• reaction pressure In the method for producing an oxide of the present invention, the reaction may be carried out under normal pressure or under pressure. From the viewpoint of reactivity, the absolute pressure of the reaction is preferably 0.09 MPa or higher, more preferably 0.10 MPa or higher, and from the viewpoint of equipment load, preferably 0.5 MPa or lower, more preferably 0.2 MPa. 0.11 MPa or less, more preferably 0.11 MPa or less. The reaction is preferably carried out under normal pressure.
• the method for producing an oxide of the present invention may further include a step of purifying the obtained oxide after completion of the dehydrogenative oxidation reaction of the organic compound.
• the Pt/Bi composite catalyst is removed from the reaction solution containing the oxide of the organic compound by performing, for example, filtration under pressure, filtration under reduced pressure, etc. after the completion of the oxidation reaction of the organic compound. can be done.
• an oxide of an organic compound can be obtained at a high production rate, so that the reaction solution containing the oxide of the organic compound can be used as it is as a raw material for producing a detergent or the like. can. Further, if necessary, the organic compound can be obtained at a high concentration by extracting, distilling, or the like from the reaction liquid containing the oxide of the organic compound.
• Another method for producing the oxide of the present invention has one primary hydroxyl group in the presence of a Pt/Bi composite catalyst, a Bi ion source, and water under the condition that the minimum pH value during the reaction is less than 7.
• a method for producing an oxide comprising subjecting an organic compound to a dehydrogenative oxidation reaction to obtain an oxide of the organic compound.
• an oxide of an organic compound can be obtained at a high production rate.
• the Pt/Bi composite catalyst is a Pt/Bi composite catalyst obtained by the above-described method for producing an oxide or a Pt/Bi composite catalyst obtained by a method for producing a Pt/Bi catalyst described later. It is similar to the Bi composite catalyst.
• Another method of producing the oxides of the invention preferably involves regeneration of the Pt/Bi composite catalyst.
• regeneration of the Pt/Bi composite catalyst is preferably accompanied is not clear, it is considered as follows. It is thought that when the Pt/Bi composite catalyst is repeatedly used in a method for producing oxides of organic compounds, Bi is gradually eluted, the structure of the catalyst changes, and the catalytic activity decreases.
• Bi is reduced and precipitated on the Pt/Bi composite catalyst, thereby replenishing the eluted Bi content. It is presumed that the Pt/Bi composite catalyst is regenerated.
• the dehydrogenative oxidation reaction of the organic compound is promoted as the Pt/Bi composite catalyst is regenerated, and the oxide of the organic compound is obtained in high yield.
• the other method for producing an oxide of the present invention can accompany regeneration of the Pt/Bi composite catalyst in the oxide production process, and therefore does not require separate equipment and processes for catalyst regeneration. Therefore, it is possible to efficiently produce an oxide of an organic compound, which has great advantages in terms of production efficiency and production cost.
• the method for producing an oxide of the present invention and other methods for producing an oxide from the viewpoint of efficiently regenerating the Pt/Bi composite catalyst and improving the yield of the oxide of the organic compound, dehydration of the organic compound It is preferable to add the Bi ion source at the start of the oxygen oxidation reaction or during the reaction, and it is more preferable to add the Bi ion source during the reaction. By adding the Bi ion source to the system at the start of the reaction, deterioration of the Pt/Bi composite catalyst can be easily suppressed, and the yield of organic compound oxides can be easily improved.
• the Pt/Bi composite catalyst can be regenerated by adding a Bi ion source to the system during the reaction in accordance with the deterioration state of the Pt/Bi composite catalyst, the dehydrogenative oxidation reaction of the organic compound can be performed. A decrease in efficiency can be suppressed, and the yield of the oxide of the organic compound can be easily improved.
• the catalyst in order to solve the problem that Bi is eluted due to the recycling of the catalyst and the catalytic activity is lowered, the catalyst can be regenerated without re-preparing a high-performance Pt/Bi composite catalyst.
• Method for producing Pt/Bi composite catalyst In the method for producing a Pt/Bi composite catalyst of the present invention, Pt supported on a carrier and a Bi ion source are mixed in the presence of an organic compound having one primary hydroxyl group and water, and the pH during the reaction is adjusted to A method for producing a Pt/Bi composite catalyst in which the minimum value is less than 7.
• a catalyst exhibiting high activity in the dehydrogenative oxidation reaction of organic compounds.
• Pt and Bi are usually precipitated by adding a reducing agent to a Pt ion source and a Bi ion source under alkaline conditions.
• a composite catalyst was prepared with However, since Bi segregates in such a method, the obtained composite catalyst has few active structures effective for the dehydrogenative oxidation reaction of organic compounds, and the catalytic activity is considered to be low.
• the reaction system preferably involves a dehydrogenative oxidation reaction of an organic compound having one primary hydroxyl group. More preferably, the dehydrogenative oxidation reaction of the organic compound is promoted.
• the dehydrogenative oxidation reaction of the organic compound is preferably accompanied, and more preferably the reaction is accelerated, it is considered as follows.
• a dehydrogenative oxidation reaction of the organic compound is accompanied by mixing the carrier-supported Pt and the Bi ion source in the presence of the organic compound.
• a carboxylic acid compound or a salt of a carboxylic acid compound which is an oxide of the organic compound, can be obtained along with the production of the Pt/Bi composite catalyst.
• the carboxylic acid compound or the salt of the carboxylic acid compound include the carboxylic acid compound or the salt of the carboxylic acid compound obtained by subjecting the above-described aliphatic alcohol or polyoxyalkylene alkyl ether to a dehydrogenative oxidation reaction.
• carboxylic acid compounds include fatty acids obtained by dehydrogenative oxidation reaction of aliphatic alcohols, ether carboxylates obtained by dehydrogenative oxidation reaction of polyoxyalkylene alkyl ethers, and the like.
• Salts of carboxylic acid compounds include, for example, neutralized salts of the above fatty acid or ether carboxylates and alkali metal hydroxides such as sodium and potassium.
• Preferred examples of the organic compound having one primary hydroxyl group in the method for producing a Pt/Bi composite catalyst of the present invention include aliphatic alcohols and polyoxyalkylene alkyl ethers.
• the organic compounds having one primary hydroxyl group can be preferably used.
• the organic compound having one primary hydroxyl group is preferably a highly hydrophilic organic compound from the viewpoint of oxide production rate.
• the organic compound having one primary hydroxyl group is preferably a polyoxyalkylene alkyl ether, more preferably a polyoxyalkylene alkyl ether represented by the general formula (2).
• the reaction may be further carried out in the presence of the oxide of the organic compound.
• the oxide of the organic compound include a carboxylic acid compound or a salt of the carboxylic acid compound in which the hydroxy group of the organic compound is oxidized, as exemplified in the method for producing an oxide of the present invention.
• Examples of Pt supported on a carrier used in the method for producing a Pt/Bi composite catalyst of the present invention include the same Pt supported on a carrier used in the method for producing an oxide of the present invention. , and the preferred ranges are also the same.
• the carrier of Pt supported on a carrier used in the method for producing the Pt/Bi composite catalyst of the present invention is preferably activated carbon. Examples of the activated carbon include those similar to those used in the method for producing an oxide of the present invention, and the preferred range is also the same.
• the Bi ion source is preferably water-insoluble from the viewpoint of improving the catalytic activity of the produced Pt/Bi composite catalyst.
• the Bi ion source include those similar to the Bi ion source used in the oxide production method of the present invention.
• the method for producing the Pt/Bi composite catalyst of the present invention is carried out in the presence of water.
• water the same water as used in the method for producing an oxide of the present invention is exemplified, and the preferred range is also the same.
• the minimum value of pH during the reaction is less than 7.
• the inside of the reaction system can be made acidic, the Bi ion source is easily dissolved and Bi ions are easily generated, and Bi can be generated from Bi ions alone by activated carbon or the like. Since precipitation on the carrier can be suppressed and Bi can be reduced and precipitated in the vicinity of Pt to create a highly active structure, a reaction that produces a highly active Pt/Bi composite catalyst and dehydrogenation of organic compounds It is considered that the reactivity of the oxidation reaction is greatly improved.
• the pH condition during the reaction is the same as the preferred pH range during the reaction in the method for producing an oxide of the present invention.
• the reaction temperature in the Pt/Bi composite catalyst production method of the present invention is the same as the reaction temperature in the oxide production method of the present invention.
• oxygen-containing gas As the oxygen-containing gas, the same oxygen-containing gas as used in the method for producing an oxide of the present invention is exemplified, and the preferred range is also the same.
• the reaction pressure in the method for producing the Pt/Bi composite catalyst of the present invention is the same as the reaction pressure in the method for producing oxides of the present invention.
• the catalyst produced in the method for producing a Pt/Bi composite catalyst of the present invention can be recovered by separating it from the reaction solution.
• a recovery method for example, filtration under pressure, filtration under reduced pressure, or the like can be performed.
• the recovered Pt/Bi composite catalyst may be washed, but can be used as a dehydrogenative oxidation reaction catalyst for organic compounds without washing.
• the catalyst produced by the method for producing a Pt/Bi composite catalyst of the present invention can be reused as a dehydrogenative oxidation reaction catalyst for the aforementioned organic compounds.
• Another method for producing the Pt/Bi composite catalyst of the present invention is to mix the Pt/Bi composite catalyst and the Bi ion source in the presence of an organic compound having one primary hydroxyl group and water, and adjust the pH during the reaction.
• the Pt/Bi composite catalyst is the same as the Pt/Bi composite catalyst described above or the Pt/Bi composite catalyst obtained by the method for producing oxides described later. is.
• Another method for producing the Pt/Bi composite catalyst of the present invention preferably includes adding a Bi ion source at the start of the reaction or during the reaction to regenerate the Pt/Bi composite catalyst. is added to regenerate the Pt/Bi composite catalyst.
• a Bi ion source By adding the Bi ion source to the system at the start of the reaction, deterioration of the Pt/Bi composite catalyst can be suppressed and the yield of organic compound oxides can be improved.
• the Pt/Bi composite catalyst can be regenerated, so that a decrease in the efficiency of the dehydrogenative oxidation reaction of the organic compound can be suppressed, and the oxide of the organic compound yield can be improved.
• the Pt/Bi composite catalyst is regenerated by adding the Bi ion source at the start of the reaction or during the reaction. It is thought that when the Pt/Bi composite catalyst is repeatedly used in a method for producing oxides of organic compounds, Bi is gradually eluted, the structure of the catalyst changes, and the catalytic activity decreases. In another method for producing the Pt/Bi composite catalyst of the present invention, by adding a Bi ion source together with the Pt/Bi composite catalyst, Bi is reduced and precipitated on the Pt/Bi composite catalyst, so that the eluted Bi It is presumed that the Pt/Bi composite catalyst is regenerated by replenishing the required amount.
• the other method for producing the Pt/Bi composite catalyst of the present invention can involve regeneration of the Pt/Bi composite catalyst within the oxide production process.
• a Pt/Bi composite catalyst can be produced efficiently without the need for a
• the oxide of an organic compound obtained by the method for producing an oxide and the method for producing a Pt/Bi composite catalyst of the present invention can be used in a wide range of fields as a cleaning agent, a softening agent, a wetting agent, a dyeing aid, and the like. .
• a cleaning agent e.g., a cleaning agent for producing an oxide
• a softening agent e.g., a wetting agent
• a dyeing aid e.g., a dyeing aid, and the like.
• it has excellent foaming power and detergency and low skin irritation, it is suitable for products such as shampoos, body soaps, kitchen detergents, cosmetic compositions, cosmetics, etc., which come into contact with the human skin for a long time. can be used.
• an oxide of an organic compound can be obtained at a high production rate.
• the production rate of the organic compound oxide after 24 hours of reaction is preferably 75% or more, more preferably 77% or more, and still more preferably. 80% or more, more preferably 83% or more.
• the production rate of the oxide of the organic compound after 3 hours of reaction is preferably 20% or more, more preferably 25% or more, and still more preferably 30% or more.
• the production rate of the oxide of the organic compound can be determined in the same manner as the calculation method of the carboxylic acid compound production rate in Examples described later.
• the Pt/Bi composite catalyst of the present invention can be obtained by the method for producing an oxide and the method for producing a Pt/Bi composite catalyst of the present invention described above.
• the Pt/Bi composite catalyst of the present invention is suitably used in the reaction of dehydrogenating and oxidizing the above-described organic compound having one primary hydroxyl group to produce an oxide of the organic compound. That is, the present invention also relates to a method for producing an oxide, comprising dehydrogenating and oxidizing the organic compound having one primary hydroxyl group in the presence of the Pt/Bi composite catalyst to obtain an oxide of the organic compound. .
• the method for producing an oxide of the present invention contains water as a solvent, supplies oxygen to a composition containing an organic compound having one primary hydroxyl group in the presence of the Pt/Bi composite catalyst, It is preferable to dehydrogenate the organic compound having one primary hydroxyl group.
• the amount of Bi supported in the Pt/Bi composite catalyst is preferably 0.01% by mass or more, more preferably 0.5% by mass or more, and preferably 10% by mass, from the viewpoint of improving the productivity of the oxidation reaction product. % by mass or less, more preferably 5% by mass or less, even more preferably 3.5% by mass or less, and even more preferably 2.5% by mass or less.
• the mass ratio (atomic ratio) Bi/Pt of Bi to Pt is preferably 0.05 or more, more preferably 0.05 or more, from the viewpoint of improving productivity of oxidation reaction products. It is 1 or more, preferably 2.0 or less, more preferably 1.5 or less, even more preferably 1.0 or less, and even more preferably 0.5 or less.
• the present invention further discloses the following oxide production method and Pt/Bi composite catalyst production method.
• oxide production method In the presence of Pt supported on a carrier, a Bi ion source, and water, an organic compound having one primary hydroxyl group is dehydrogenated and oxidized under conditions where the minimum pH value during the reaction is less than 7. and a method for producing an oxide, wherein the oxide of the organic compound is obtained.
• ⁇ 2> In the presence of a Pt/Bi composite catalyst, a Bi ion source, and water, an organic compound having one primary hydroxyl group is subjected to a dehydrogenative oxidation reaction under conditions where the minimum pH value during the reaction is less than 7, A method for producing an oxide, wherein the oxide of the organic compound is obtained.
• ⁇ 3> The method for producing an oxide according to ⁇ 1> or ⁇ 2>, which involves preparing a Pt/Bi composite catalyst.
• ⁇ 4> The method for producing an oxide according to any one of ⁇ 1> to ⁇ 3>, wherein the Bi ion source is water-insoluble.
• ⁇ 5> The method for producing an oxide according to any one of ⁇ 1> to ⁇ 4>, wherein the Bi ion source is bismuth oxide.
• the charge amount of the Bi ion source is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and still more preferably 0.05 parts by mass or more with respect to 100 parts by mass of the organic compound. and preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, and still more preferably 0.3 parts by mass or less, production of the oxide according to any one of ⁇ 1> to ⁇ 5> Method.
• the mass ratio (atomic ratio) Bi/Pt of the charged amount of Bi to Pt is preferably 0.05 or more, more preferably 0.1 or more, and preferably 2.0 or less, more preferably of ⁇ 1> to ⁇ 6>, which is 1.8 or less, more preferably 1.5 or less, even more preferably 1.4 or less, even more preferably 1.2 or less, and even more preferably 1.0 or less
• R 2 O—(AO) n —H (2)
• R 2 is a monovalent aliphatic hydrocarbon group having 2 to 40 carbon atoms
• A is an alkanediyl group having 2 to 4 carbon atoms
• AO represents an alkyleneoxy group
• n is alkyleneoxy. It is the average value of the number of added moles of groups, and is 1 or more and 30 or less.
• R 1 in the general formula (1) is preferably a linear or branched primary monovalent aliphatic hydrocarbon group, more preferably a linear or branched primary alkyl group
• the method for producing an oxide according to ⁇ 9> which is an alkenyl group, more preferably a linear primary alkyl group.
• R 1 in the general formula (1) The number of carbon atoms in R 1 in the general formula (1) is preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, still more preferably 12 or more, and preferably 36 or less,
• the method for producing an oxide according to ⁇ 9> or ⁇ 10> which is more preferably 22 or less, still more preferably 18 or less, and even more preferably 14 or less.
• R 2 in the general formula (2) is preferably a linear or branched primary aliphatic hydrocarbon group, more preferably a linear or branched primary alkyl group or alkenyl group , and more preferably a linear primary alkyl group, the method for producing an oxide according to any one of ⁇ 9> to ⁇ 11>.
• the number of carbon atoms in R 2 in the general formula (2) is preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, still more preferably 12 or more, and preferably 36 or less,
• a in the general formula (2) is preferably an ethylene group or a propylene group, more preferably an ethylene group.
• AO in the general formula (2) is preferably an ethyleneoxy group (EO) or a propyleneoxy group (PO), more preferably an ethyleneoxy group (EO)
• EO in the general formula (2) is preferably an ethyleneoxy group (EO) or a propyleneoxy group (PO), more preferably an ethyleneoxy group (EO)
• EO in the general formula (2) is preferably 3 or more, and is preferably 25 or less, more preferably 20 or less, still more preferably 16 or less, and still more preferably 12 or less
• ⁇ 17> Any one of ⁇ 9> to ⁇ 16>, wherein the organic compound is preferably a polyoxyalkylene alkyl ether, more preferably a polyoxyalkylene alkyl ether represented by the general formula (2).
• a method for producing an oxide is preferably a polyoxyalkylene alkyl ether, more preferably a polyoxyalkylene alkyl ether represented by the general formula (2).
• ⁇ 18> The method for producing an oxide according to any one of ⁇ 1> to ⁇ 17>, wherein the oxide of the organic compound is a carboxylic acid compound or a salt of a carboxylic acid compound.
• the carboxylic acid compound or the carboxylic acid salt is an ether carboxylate or a salt thereof obtained by an oxidation reaction of a polyoxyalkylene alkyl ether.
• the support is activated carbon.
• the particle size of the Pt supported on the carrier is preferably 1 nm or more, more preferably 3 nm or more, and is preferably 20 nm or less, more preferably 15 nm or less, and still more preferably 10 nm or less.
• the amount of Pt supported relative to the total amount of the carrier and Pt is preferably 0.1% by mass or more, more preferably 1% by mass or more, and still more preferably 2% by mass or more.
• the charge amount of Pt supported on the carrier is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 4 parts by mass or more with respect to 100 parts by mass of the organic compound, and
• the method for producing an oxide according to any one of ⁇ 1> to ⁇ 22> which is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and still more preferably 6 parts by mass or less.
• the amount of water is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and preferably 35 parts by mass or less, more preferably 30 parts by mass or less, relative to 100 parts by mass of the organic compound.
• the minimum pH value at the end of the reaction in the method for producing an oxide is preferably 6 or less, more preferably 5 or less, still more preferably 4 or less, and is preferably 1 or more, more preferably 1.
• the reaction temperature in the method for producing the oxide is preferably 50°C or higher, more preferably 60°C or higher, and is preferably 100°C or lower, more preferably 90°C or lower, and still more preferably 85°C or lower.
• ⁇ 28> The method for producing an oxide according to any one of ⁇ 1> to ⁇ 27>, wherein oxygen is preferably supplied into the reaction system.
• ⁇ 29> The method for producing an oxide according to ⁇ 28>, wherein oxygen is supplied by circulating an oxygen-containing gas in a liquid phase.
• the oxygen-containing gas is oxygen gas or air.
• the oxygen concentration in the oxygen-containing gas is preferably 10% by volume or more, more preferably 50% by volume or more, still more preferably 70% by volume or more, even more preferably 90% by volume or more, and even more preferably 100% by volume. % by volume.
• the reaction pressure in terms of absolute pressure, is preferably 0.09 MPa or higher, more preferably 0.10 MPa or higher, and preferably 0.5 MPa or lower, more preferably 0.2 MPa.
• ⁇ 34> The method for producing an oxide according to any one of ⁇ 1> to ⁇ 33>, wherein a Bi ion source is added at the start of the dehydrogenative oxidation reaction or during the reaction.
• ⁇ 35> The method for producing an oxide according to any one of ⁇ 1> to ⁇ 34>, further comprising a step of purifying the obtained oxide after the completion of the dehydrogenative oxidation reaction of the organic compound.
• the Pt/Bi composite catalyst is removed from the reaction solution containing the oxide of the organic compound by pressure filtration or vacuum filtration, ⁇ 35>.
• ⁇ 41> The method for producing a Pt/Bi composite catalyst according to any one of ⁇ 37> to ⁇ 40>, wherein the organic compound is an aliphatic alcohol or a polyoxyalkylene alkyl ether.
• the organic compound is an aliphatic alcohol or a polyoxyalkylene alkyl ether.
• ⁇ 42> Any one of ⁇ 37> to ⁇ 41>, wherein the aliphatic alcohol or polyoxyalkylene alkyl ether is preferably one or more represented by the following general formula (1) or general formula (2)
• a method for preparing the described Pt/Bi composite catalyst R 1 OH (1)
• R 1 is a monovalent aliphatic hydrocarbon group having 2 to 40 carbon atoms.
• R 2 O—(AO) n —H (2)
• R 2 is a monovalent aliphatic hydrocarbon group having 2 to 40 carbon atoms
• A is an alkanediyl group having 2 to 4 carbon atoms
• AO represents an alkyleneoxy group
• n is alkyleneoxy. It is the average value of the number of added moles of groups, and is 1 or more and 30 or less.
• R 1 in the above general formula (1) is preferably a linear or branched primary monovalent aliphatic hydrocarbon group, more preferably a linear or branched primary alkyl group or an alkenyl group, more preferably a linear primary alkyl group.
• the number of carbon atoms in R 1 in the general formula (1) is preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, still more preferably 12 or more, and preferably 36 or less,
• the method for producing a Pt/Bi composite catalyst according to ⁇ 42> or ⁇ 43> which is more preferably 22 or less, still more preferably 18 or less, and even more preferably 14 or less.
• R 2 in the general formula (2) is preferably a linear or branched primary aliphatic hydrocarbon group, more preferably a linear or branched primary alkyl group or alkenyl group , and more preferably a linear primary alkyl group, the method for producing a Pt/Bi composite catalyst according to any one of ⁇ 42> to ⁇ 44>.
• the number of carbon atoms in R 2 in the general formula (2) is preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, still more preferably 12 or more, and preferably 36 or less,
• the method for producing a Pt/Bi composite catalyst according to ⁇ 42> to ⁇ 45> which is more preferably 22 or less, still more preferably 18 or less, and even more preferably 14 or less.
• a in the general formula (2) is preferably an ethylene group or a propylene group, more preferably an ethylene group. .
• AO in the general formula (2) is preferably an ethyleneoxy group (EO) or a propyleneoxy group (PO), more preferably an ethyleneoxy group (EO)
• EO in the general formula (2) is preferably an ethyleneoxy group (EO) or a propyleneoxy group (PO), more preferably an ethyleneoxy group (EO)
• EO in the general formula (2) is preferably 3 or more, and is preferably 25 or less, more preferably 20 or less, still more preferably 16 or less, and still more preferably 12 or less, ⁇ 42 > to the method for producing a Pt/Bi composite catalyst according to any one of ⁇ 48>.
• ⁇ 50> Any one of ⁇ 42> to ⁇ 49>, wherein the organic compound is preferably a polyoxyalkylene alkyl ether, more preferably a polyoxyalkylene alkyl ether represented by the general formula (2).
• a method for producing a Pt/Bi composite catalyst is preferably a polyoxyalkylene alkyl ether, more preferably a polyoxyalkylene alkyl ether represented by the general formula (2).
• ⁇ 51> The method for producing a Pt/Bi composite catalyst according to any one of ⁇ 37> to ⁇ 50>, wherein the reaction is further performed in the presence of an oxide of the organic compound.
• ⁇ 52> The method for producing a Pt/Bi composite catalyst according to ⁇ 51>, wherein the oxide of the organic compound is a carboxylic acid compound or a salt of a carboxylic acid compound.
• the carboxylic acid compound or the salt of the carboxylic acid compound is a fatty acid obtained by a dehydrogenative oxidation reaction of an aliphatic alcohol, an ether carboxylate obtained by a dehydrogenative oxidation reaction of a polyoxyalkylene alkyl ether, and
• the method for producing a Pt/Bi composite catalyst according to ⁇ 52> which is any one of neutralized salts of these and alkali metal hydroxides such as sodium and potassium.
• ⁇ 54> The method for producing a Pt/Bi composite catalyst according to any one of ⁇ 37> to ⁇ 53>, wherein the Bi ion source is water-insoluble.
• the Bi ion source is bismuth oxide.
• the charge amount of the Bi ion source is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and still more preferably 0.05 parts by mass or more with respect to 100 parts by mass of the organic compound.
• the mass ratio (atomic ratio) Bi/Pt of the charged amount of Bi to Pt is preferably 0.05 or more, more preferably 0.1 or more, and preferably 2.0 or less, more preferably ⁇ 37> to ⁇ 56>, which is 1.8 or less, more preferably 1.5 or less, even more preferably 1.4 or less, even more preferably 1.2 or less, and even more preferably 1.0 or less
• ⁇ 58> The method for producing a Pt/Bi composite catalyst according to any one of ⁇ 37> to ⁇ 57>, wherein the carrier is activated carbon.
• the particle size of the Pt supported on the carrier is preferably 1 nm or more, more preferably 3 nm or more, and is preferably 20 nm or less, more preferably 15 nm or less, and still more preferably 10 nm or less.
• the amount of Pt supported relative to the total amount of the carrier and Pt is preferably 0.1% by mass or more, more preferably 1% by mass or more, and still more preferably 2% by mass or more. , more preferably 3% by mass or more, even more preferably 5% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, ⁇ 37 > to the method for producing a Pt/Bi composite catalyst according to any one of ⁇ 59>.
• the charge amount of Pt supported on the carrier is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 4 parts by mass or more with respect to 100 parts by mass of the organic compound, and
• the amount of water is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and preferably 35 parts by mass or less, more preferably 30 parts by mass or less, relative to 100 parts by mass of the organic compound.
• the minimum value of the pH at the end of the reaction in the method for producing a Pt/Bi composite catalyst is preferably 6 or less, more preferably 5 or less, still more preferably 4 or less, and preferably 1 or more, more preferably is 1.5 or more, more preferably 2 or more.
• the reaction temperature in the method for producing the Pt/Bi composite catalyst is preferably 50°C or higher, more preferably 60°C or higher, and is preferably 100°C or lower, more preferably 90°C or lower, and still more preferably 85°C.
• the method for producing a Pt/Bi composite catalyst according to any one of ⁇ 37> to ⁇ 64> the method for producing a Pt/Bi composite catalyst according to any one of ⁇ 37> to ⁇ 64>.
• ⁇ 66> The method for producing a Pt/Bi composite catalyst according to any one of ⁇ 37> to ⁇ 65>, wherein oxygen is preferably supplied into the reaction system.
• ⁇ 67> The method for producing a Pt/Bi composite catalyst according to ⁇ 66>, wherein oxygen is supplied by circulating an oxygen-containing gas in a liquid phase.
• the oxygen-containing gas is oxygen gas or air.
• the oxygen concentration in the oxygen-containing gas is preferably 10% by volume or more, more preferably 50% by volume or more, still more preferably 70% by volume or more, even more preferably 90% by volume or more, and even more preferably 100% by volume. % by volume.
• the reaction pressure in absolute pressure, is preferably 0.09 MPa or more, more preferably 0.10 MPa or more, and preferably 0.5 MPa or less, more preferably The method for producing a Pt/Bi composite catalyst according to any one of ⁇ 37> to ⁇ 69>, wherein the pressure is 0.2 MPa or less, more preferably 0.11 MPa or less.
• the reaction is preferably carried out under normal pressure.
• the organic compound is subjected to a dehydrogenative oxidation reaction, and the organic A method for producing an oxide, which obtains an oxide of a compound.
• Example 1 A glass stirring rod equipped with a reflux tube, a dissolved oxygen concentration meter (manufactured by METTLER TOLEDO), and a mechanical stirrer (manufactured by IWAKI, a crescent-shaped stirring blade (blade width 7.5 cm ⁇ height 2.2 cm ⁇ thickness 0.4 cm). Attached), a glass temperature control holder, and a glass tube for blowing gas into a 500 mL five-necked flask were charged with raw materials and the like as follows.
• the five-necked flask was immersed in a water bath under nitrogen flow, and the temperature was raised to 80°C while stirring the charged raw materials at 600 rpm. After the temperature reached 80°C, the flow of nitrogen was stopped, oxygen was bubbled through the charged raw materials at 60 mL/min, and the reaction was carried out under normal pressure for 24 hours.
• the reaction was divided and carried out every few hours.
• oxygen bubbling was stopped and nitrogen was circulated, and the dissolved oxygen concentration was kept at 0 ppm for 1 hour to stop the reaction.
• the temperature was raised to 80° C. while stirring at 600 rpm under nitrogen flow, then the nitrogen flow was stopped and oxygen was bubbled at 60 mL/min to initiate the reaction.
• reaction liquid was filtered under pressure to separate the reaction liquid and the catalyst.
• Carboxylic acid compound production rate (%) (measured acid value/theoretical acid value) x 100
• the theoretical acid value and the actually measured acid value were as follows.
• (2) Calculation of measured acid value The measured acid value was obtained from the obtained neutralization point by the following formula.
• Measured acid value titration amount of potassium hydroxide aqueous solution (mL) x 56.11 (g/mol) x 0.05 (mol/L)/sampling amount (g)/0.7692 (reaction solution mass ratio of raw materials inside)
• Example 2 and 3> The reactions of Examples 2 and 3 were carried out in the same manner as in Example 1, except that the amount of bismuth oxide charged as the Bi ion source was changed as shown in Table 1. Table 1 summarizes the carboxylic acid compound production rate after 24 hours of reaction.
• Example 4> Example 4 reaction was carried out in the same manner as in Example 1 except that the Bi ion source was changed to 0.23 parts by mass of bismuth nitrate pentahydrate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) as shown in Table 1. did Table 1 summarizes the carboxylic acid compound production rate after 24 hours of reaction.
• Example 5 The reaction of Example 5 was carried out in the same manner as in Example 1, except that the type of organic compound was changed to K2098 (Kalcol 2098 (lauryl alcohol), manufactured by Kao Corporation) as shown in Table 2.
• the OHV of K2098 is 301 mgKOH/g, and the theoretical acid value of its oxidation product (carboxylic acid compound) is 280 mgKOH/g.
• Table 2 summarizes the carboxylic acid compound formation rate after 7 hours of reaction.
• Example 6> As shown in Table 2, the type of organic compound was changed to AE2 (polyoxyalkylene alkyl ether obtained by adding an average of 9 mol of ethylene oxide to 1 mol of 1-octanol), and the reaction time was set to 7 hours. The reaction of Example 6 was carried out in the same manner. The OHV of AE2 is 107 mgKOH/g, and the theoretical acid value of its oxidation product (carboxylic acid compound) is 104 mgKOH/g. Table 2 summarizes the carboxylic acid compound formation rate after 7 hours of reaction. ⁇ Comparative Example 1> As shown in Table 1, the reaction of Comparative Example 1 was carried out in the same manner as in Example 1, except that the Bi ion source was not charged.
• Table 1 summarizes the carboxylic acid compound production rate after 24 hours of reaction.
• Comparative Example 2 A pH meter (manufactured by Nisshin Rika Co., Ltd.) was attached to the reaction vessel, and a 48% sodium hydroxide aqueous solution (manufactured by Kanto Kagaku Co., Ltd.) was added as an alkaline agent so that the pH during the reaction was constant at 7.0. However, the reaction of Comparative Example 2 was carried out in the same manner as in Example 1, except that the reaction was carried out for 9 hours. The carboxylic acid compound production rate was calculated by the following method, and Table 3 summarizes the carboxylic acid compound production rate after 3 hours of reaction.
• Example 1 The total amount of catalyst recovered in Example 1 was 17.80 g.
• the breakdown of the composition contained in the recovered catalyst is, from the amount charged in Example 1, a total of 10 g of 5% Pt/C and bismuth oxide, 1.56 g of water content, and 6 organic compounds (unreacted AE1 and carboxylic acid compound). .24 g.
• Table 4 summarizes the carboxylic acid compound production rate after 17 hours of reaction.
• Pt and Bi ion sources supported on a carrier are mixed in the presence of an organic compound having one primary hydroxyl group, and the minimum pH value during the reaction is less than 7.
• the resulting Pt/Bi composite catalyst showed a high production rate of carboxylic acid compounds in any reaction time, and the target organic compound oxide was efficiently obtained. Further, in Reference Example 1, in which the catalyst of Example 1 was separated and recovered and used again in the oxidation reaction of organic compounds, a high carboxylic acid compound production rate was exhibited.
• the Pt/Bi composite catalyst of Comparative Example 1 to which no Bi ion source was added, had a carboxylic acid compound content of about 74% after 24 hours, and the oxide of the target organic compound could not be obtained efficiently.
• the production rate of the carboxylic acid compound after 17 hours of reaction in Reference Example 1 was 91.3%, which was higher than the production rate of carboxylic acid compound after 17 hours of reaction in Example 1 (81.6%).
• the method for producing an oxide of the present invention can efficiently obtain an oxide of an organic compound in the presence of a Pt and Bi ion source supported on a carrier, and further involves the production of a Pt/Bi composite catalyst. can be done. Therefore, it is possible to efficiently produce oxides of organic compounds without requiring separate equipment or processes for catalyst production, and the resulting oxides of organic compounds can be used as cleaning agents, softening agents, wetting agents, dyeing agents, It can be used in a wide range of fields as an adjuvant or the like.
• the method for producing a Pt/Bi composite catalyst of the present invention can produce a catalyst that exhibits high activity in the dehydrogenative oxidation reaction of an organic compound even in the presence of an organic compound that is a raw material of an oxide. It can involve an oxidative dehydrogenation reaction of the compound. Therefore, it is possible to efficiently produce an oxide of an organic compound without requiring a separate facility or process for catalyst production, and the resulting Pt/Bi composite catalyst is obtained by dehydrogenating and oxidizing the organic compound. It can be suitably used in reactions for producing oxides of organic compounds.

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