Methods for manufacturing oxides and methods for manufacturing Pt / Bi composite catalysts

Abstract

This invention relates to a method for manufacturing oxides and a method for manufacturing Pt / Bi composite catalysts. The method for manufacturing oxides enables the efficient production of oxides of organic compounds in the presence of Pt / Bi composite catalyst feedstocks. The method for manufacturing Pt / Bi composite catalysts enables the production of catalysts exhibiting high activity in the dehydrogenation reaction of organic compounds, even in the presence of organic compounds that serve as feedstocks for oxides. One method for manufacturing oxides involves subjecting an organic compound having one primary hydroxyl group to a dehydrogenation reaction in the presence of a Pt and Bi ion source supported on a support and water, under conditions where the minimum pH value in the reaction is less than 7, to obtain an oxide of the organic compound.

Description

Technical Field

[0001] This invention relates to a method for manufacturing oxides and a method for manufacturing Pt / Bi composite catalysts. Background Technology

[0002] It has long been known to combine Bi as a co-catalyst with Pt as a noble metal catalyst to perform contact dehydrogenation of hydroxyl and aldehyde compounds, converting them into corresponding carboxyl and ketone compounds.

[0003] Japanese Patent Application Publication No. 2016-120484 (Patent Document 1) discloses a method for preparing a catalyst by adding an aqueous dispersion of a catalyst supported on activated carbon to an aqueous solution containing Bi in an ionic state, and a method for manufacturing an oxide by dehydrogenating an alcohol or the like in the presence of the catalyst obtained by the preparation method.

[0004] In addition, Japanese Patent Application Publication No. 1-146840 (Patent Document 2) discloses a method for manufacturing an ether carboxylic acid by oxidizing a polyalkoxy alcohol or an aliphatic alcohol alkoxylate in an alkaline aqueous phase in the presence of a catalyst containing a noble metal of Group VIII of the Japanese Periodic Table, such as Pd or Pt. Summary of the Invention

[0005] This invention relates to a method for manufacturing an oxide, wherein an organic compound having one primary hydroxyl group is subjected to a dehydrogenation reaction in the presence of a Pt or Bi ion source supported on a carrier and water, under conditions where the minimum pH value in the reaction is less than 7, to obtain an oxide of the organic compound.

[0006] In addition, the present invention relates to a method for manufacturing a Pt / Bi composite catalyst, wherein a Bi ion source and Pt supported on a support are mixed in the presence of water and an organic compound having one primary hydroxyl group, and the reaction is carried out under conditions where the minimum pH value in the reaction is less than 7. Detailed Implementation

[0007] The catalyst preparation method described in Patent Document 1 involves steps other than those used in the manufacture of oxides of alcohols, etc. Therefore, catalyst manufacturing equipment needs to be prepared separately from the equipment used for manufacturing oxides of alcohols, etc. Furthermore, the catalyst preparation process requires steps beyond the preparation of the catalyst raw materials, including separation and purification of the catalyst. The prepared catalyst also needs to be stored under appropriate conditions until it is used in the manufacture of oxides of alcohols, etc. This results in significant costs and labor required for catalyst preparation outside of the manufacture of oxides of alcohols, etc. Additionally, the method for manufacturing ether carboxylic acids described in Patent Document 2 suffers from low yield rates for ether carboxylic acids.

[0008] This invention relates to a method for manufacturing oxides and a method for manufacturing Pt / Bi composite catalysts. In the method for manufacturing oxides, oxides of organic compounds can be obtained efficiently in the presence of raw materials for Pt / Bi composite catalysts. In the method for manufacturing Pt / Bi composite catalysts, a catalyst exhibiting high activity in the dehydrogenation reaction of organic compounds can be produced even in the presence of organic compounds that serve as raw materials for oxides.

[0009] The inventors have discovered that even in the presence of a Pt / Bi composite catalyst, by setting the pH of the reaction to less than 7, oxides of organic compounds can be obtained efficiently. Furthermore, even in the presence of an organic compound that becomes an oxide, by setting the pH of the reaction to less than 7, a catalyst exhibiting high activity in the dehydrogenation reaction of organic compounds can be produced.

[0010] The present invention relates to the following [1] and [2].

[0011] [1] A method for manufacturing an oxide, wherein an organic compound having one primary hydroxyl group is subjected to a dehydrogenation reaction in the presence of a Pt or Bi ion source supported on a support and water, under the condition that the minimum pH value in the reaction is less than 7, to obtain an oxide of the organic compound.

[0012] [2] A method for manufacturing a Pt / Bi composite catalyst, wherein a Bi ion source and Pt supported on a support are mixed in the presence of an organic compound having one primary hydroxyl group and water, and the reaction is carried out under the condition that the minimum pH value in the reaction is less than 7.

[0013] According to the present invention, a method for manufacturing an oxide and a method for manufacturing a Pt / Bi composite catalyst can be provided. In the method for manufacturing the oxide, an oxide of an organic compound can be obtained efficiently in the presence of a raw material for the Pt / Bi composite catalyst. In the method for manufacturing the Pt / Bi composite catalyst, a catalyst exhibiting high activity for the dehydrogenation reaction of organic compounds can be produced even in the presence of an organic compound that serves as a raw material for the oxide.

[0014] The present invention will now be described in detail.

[0015] [Methods for manufacturing oxides]

[0016] The method for manufacturing the oxide of the present invention is a method for manufacturing an oxide of an oxide of an organic compound having one primary hydroxyl group by performing a dehydrogenation reaction on an organic compound (hereinafter also simply referred to as "organic compound") in the presence of a Pt or Bi ion source supported on a carrier and water, under the condition that the minimum pH value in the reaction is less than 7.

[0017] According to the method for manufacturing oxides of the present invention, oxides of organic compounds can be obtained efficiently.

[0018] The reason for achieving the aforementioned effect is uncertain, but it is presumed to be as follows.

[0019] In the method for manufacturing the oxide of the present invention, when a dehydrogenation reaction of an organic compound is to be carried out, the Pt / Bi composite catalyst used in the reaction is added together with the raw material, thereby manufacturing the Pt / Bi composite catalyst in the reaction system while the organic compound undergoes a dehydrogenation reaction.

[0020] In the preparation of Pt / Bi composite catalysts used in the dehydrogenation reaction of organic compounds, a reducing agent is usually added to the Pt ion source and Bi ion source under alkaline conditions, thereby causing Pt and Bi to precipitate and thus preparing a Pt and Bi composite catalyst. However, Bi will segregate in this case, so it is considered to be a catalyst with few effective active structures and low catalyst activity for the dehydrogenation reaction of organic compounds.

[0021] On the other hand, in this invention, if the Pt supported on the support is brought into contact with the Bi ion source under the condition that the minimum pH value in the reaction is less than 7, it is believed that even without a reducing agent, Bi can be uniformly reduced and precipitated on Pt. Therefore, a large number of active structures that are effective for the dehydrogenation reaction of organic compounds can be formed. Therefore, it is believed that a catalyst with high activity can be obtained.

[0022] Furthermore, in the past, in the dehydrogenation reaction of organic compounds with hydroxyl and aldehyde groups, when the catalyst activity was low, there were cases where alkaline conditions were set to improve reactivity. However, in the method for producing oxides of the present invention, in order to improve the catalyst activity as described above under the condition that the minimum pH value in the reaction is less than 7, the formation rate of oxides of organic compounds can be increased without adding an alkaline agent.

[0023] Furthermore, in the conventional dehydrogenation reaction under alkaline conditions described above, the addition of alkali agents to create an alkaline environment generates neutral salts of oxides as byproducts. When neutral salts of oxides are formed in the reaction system, compared to the case where only oxides are present, a higher oxide / water ratio leads to increased viscosity of the reaction solution and gelation. Therefore, in conventional oxidation reactions under alkaline conditions, the reaction must be carried out with a low effective concentration composition that reduces the oxide / water ratio, making it difficult to improve productivity. On the other hand, in the oxide manufacturing method of the present invention, the formation of neutral salts of oxides as byproducts can be suppressed, as well as the increase in viscosity and gelation of the reaction solution. Therefore, the dehydrogenation reaction of organic compounds can be carried out efficiently with a composition that increases the oxide / water ratio and achieves a high effective concentration, thereby improving productivity. Additionally, since the generation of salts produced when removing oxides from the neutral salts of oxides as byproducts can also be suppressed, wastewater generation can be reduced, thus lowering the environmental burden.

[0024] Furthermore, in the method for manufacturing the oxide of the present invention, from the viewpoint of obtaining oxides of organic compounds with a high yield, it is preferable to prepare a Pt / Bi composite catalyst.

[0025] The rationale for favoring the preparation of Pt / Bi composite catalysts is still uncertain, but the following considerations are made.

[0026] By mixing the organic compound in the presence of the Bi ion source and the Pt supported on the support, a dehydrogenation reaction of the organic compound occurs. It is presumed that this generates a small amount of oxide of the organic compound, forming a solution containing the oxide. Therefore, the Bi ion source dissolves to generate Bi ions, which are then reduced and precipitated on the Pt, thereby preparing a Pt / Bi composite catalyst with higher activity than the Pt catalyst in the system. Furthermore, it is presumed that the preparation of the Pt / Bi composite catalyst promotes the dehydrogenation reaction of the organic compound, thereby obtaining the oxide of the organic compound in high yield.

[0027] For the reasons mentioned above, the method for manufacturing oxides of the present invention can simultaneously prepare catalysts within the oxide manufacturing process, thus eliminating the need for additional equipment or processes for manufacturing catalysts. This method can efficiently manufacture oxides of organic compounds, offering significant advantages in terms of production efficiency and cost.

[0028] Unless otherwise specified, Pt represents platinum, Bi represents bismuth, and C represents activated carbon in this specification. Additionally, unless otherwise specified, "%" represents "mass %".

[0029] <Organic compounds with one primary hydroxyl group>

[0030] The method for producing the oxide of the present invention is carried out by subjecting an organic compound having one primary hydroxyl group (hereinafter also referred to as organic compound) to a dehydrogenation reaction.

[0031] Examples of organic compounds having one primary hydroxyl group include aliphatic alcohols, polyoxyalkylene alkyl ethers, amide alcohols, and aromatic alcohols. From the viewpoint of the strength of hydrophilicity, at least one selected from aliphatic alcohols, polyoxyalkylene alkyl ethers, and amide alcohols is preferred, and at least one selected from aliphatic alcohols and polyoxyalkylene alkyl ethers is more preferred.

[0032] Aliphatic alcohols or polyoxyalkylene alkyl ethers are preferably one or more of the following general formulas (1) or (2).

[0033] R 1 OH (1)

[0034] In general formula (1), R 1 It is a monovalent aliphatic hydrocarbon group with 2 or more carbon atoms and less than 40 carbon atoms.

[0035] R 2 O-(AO) n -H (2)

[0036] In general formula (2), R 2 It represents a monovalent aliphatic hydrocarbon group with 2 or more carbon atoms and less than 40 carbon atoms, A represents an alkyldiyl group with 2 or more carbon atoms and less than 4 carbon atoms, AO represents an alkeneoxy group, and n is the average number of moles of alkeneoxy groups added, which is more than 1 and less than 30.

[0037] Regarding R 1 From a reactivity point of view, it is preferred to be a straight-chain or branched monovalent aliphatic primary hydrocarbon group, more preferably a straight-chain or branched primary alkyl or primary alkenyl group, and even more preferably a straight-chain primary alkyl group.

[0038] R 1 There is no particular limitation on the number of carbon atoms, but it can be 6 or more, 8 or more, 10 or more, or 12 or more. From the viewpoint of reactivity, it is preferred to be 36 or less, more preferably 22 or less, further preferably 18 or less, and even more preferably 14 or less.

[0039] Regarding R 2 From a reactivity point of view, it is preferred to be a straight-chain or branched aliphatic primary hydrocarbon group, more preferably a straight-chain or branched primary alkyl or primary alkenyl group, and even more preferably a straight-chain primary alkyl group.

[0040] R 2There is no particular limitation on the number of carbon atoms, but it can be 6 or more, 8 or more, 10 or more, or 12 or more. From the viewpoint of reactivity, it is preferred to be 36 or less, more preferably 22 or less, further preferably 18 or less, and even more preferably 14 or less.

[0041] Regarding A, from a reactivity point of view, ethylene or propylene is preferred, and ethylene is more preferred.

[0042] Similarly, regarding AO, from a reactivity point of view, ethylene oxide (EO) or propylene oxide (PO) is preferred, and ethylene oxide (EO) is more preferred.

[0043] Regarding n, from a reactivity point of view, it is preferably 3 or more, more preferably 25 or less, more preferably 20 or less, even more preferably 16 or less, and even more preferably 12 or less.

[0044] In the method for manufacturing the oxides of the present invention, the strength of the hydrophilicity of the organic compound affects the reactivity; 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 (the balance value between inorganic and organic properties) IV / OV calculated from the organic concept map of the organic compound, the higher the reactivity.

[0045] Therefore, from the viewpoint of high hydrophilicity, polyoxyalkylene alkyl ethers are preferred for organic compounds, and more preferably polyoxyalkylene alkyl ethers represented by the general formula (2).

[0046] Regarding the IOB value of organic compounds based on the organic concept map, from a reactivity point of view, it is preferably 0.3 or more, more preferably 1 or more, and even more preferably 4 or more. The IOB value of organic compounds can be less than 5.

[0047] In the method for manufacturing the oxide of the present invention, the aforementioned organic compound is subjected to a dehydrogenation reaction, thereby obtaining a carboxylic acid compound or a salt of a carboxylic acid compound as an oxide.

[0048] Examples of carboxylic acid compounds or salts of carboxylic acids include carboxylic acid compounds or salts of carboxylic acid compounds obtained by subjecting the aforementioned aliphatic alcohols or polyoxyalkylene alkyl ethers to a dehydrogenation reaction, such as so-called ether carboxylic esters or their salts obtained by subjecting polyoxyalkylene alkyl ethers to an oxidation reaction.

[0049] <Pt carried on a carrier>

[0050] Regarding the carrier used in Pt supported on a carrier, from the viewpoint of carrying out the reaction under conditions where the pH is less than 7, the carrier is preferably selected from titanium dioxide, zirconium oxide, and activated carbon, and more preferably activated carbon.

[0051] There is no particular limitation on the activated carbon, and any type of activated carbon can be used as long as it can adsorb and support Pt. Examples of the activated carbon include vegetable-based activated carbon such as coconut shell activated carbon, mineral-based activated carbon such as coal-based activated carbon, activated carbon from pulp waste liquor, synthetic resin, and organic waste. In addition, the activation method, pore distribution, shape, etc. are not particularly limited. However, the reactivity is different. Compared with vegetable-based activated carbon, coal-based activated carbon is more preferred because of its higher activity. On the other hand, in terms of the strength not to break during filtration, vegetable-based activated carbon is more preferred compared with coal-based activated carbon.

[0052] There is no particular limitation on the particle diameter of Pt supported on the carrier, but from the viewpoint of increasing the loading amount of Pt, it is preferably 1 nm or more, more preferably 3 nm or more, and from the viewpoint of improving the dispersion of Pt on the carrier surface, it is preferably 20 nm or less, more preferably 15 nm or less, and further preferably 10 nm or less.

[0053] Regarding the loading amount of Pt in Pt supported on the carrier, that is, the loading amount of Pt relative to the total amount of the carrier and Pt, from the viewpoint of the reactivity of the dehydrogenation reaction of the organic compound, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, still further preferably 3% by mass or more, and still further preferably 5% by mass or more, and from the viewpoint of improving the dispersion of Pt on the carrier surface, it is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less. In addition, Pt supported on the carrier can be prepared by a known impregnation method or precipitation method, but commercially available products can also be used.

[0054] Regarding the addition amount of Pt supported on the carrier, it can be arbitrarily selected within the range capable of obtaining a practical reaction rate according to the reaction temperature or reaction pressure. However, in the case of carrying out the reaction in a batch manner, from the viewpoint of reactivity, relative to 100 parts by mass of the organic compound, it is preferably 1 part by mass or more, more preferably 3 parts by mass or more, further preferably 4 parts by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and further preferably 6 parts by mass or less.

[0055] <Bi ion source>

[0056] Regarding the Bi ion source, from the viewpoint of improving the catalytic activity of the Pt / Bi composite catalyst produced and efficiently obtaining the oxide, it is preferably water-insoluble.

[0057] The preferred Bi ion source is at least one selected from bismuth nitrate pentahydrate (Bi(NO3)3·5H2O), bismuth oxide (Bi2O3), basic bismuth carbonate ((BiO)2CO3), and bismuth hydroxide (Bi(OH)3).

[0058] Depending on the Bi ion source used, the catalytic activity of the obtained Pt / Bi composite catalyst varies. In this invention, if bismuth oxide is used as the Bi ion source, a Pt / Bi composite catalyst with high catalytic activity can be obtained, which can efficiently produce oxides of organic compounds. Therefore, bismuth oxide is suitable as a Bi ion source.

[0059] Regarding the amount of Bi ion source added, from the viewpoint of catalyst manufacturing efficiency and the viewpoint of organic compound oxide manufacturing efficiency, it is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, even more preferably 0.05 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, even more preferably 0.3 parts by mass or less, relative to 100 parts by mass of the organic compound.

[0060] In the method for manufacturing the oxide of the present invention, the mass ratio (atomic ratio) Bi / Pt of the amount of Bi added relative to Pt is preferably 0.05 or more, more preferably 0.1 or more, and preferably 2.0 or less, more preferably 1.8 or less, further 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.

[0061] When bismuth oxide is added as a Bi ion source, the reactivity of the prepared Pt / Bi composite catalyst varies depending on the amount of bismuth oxide added. Even a small amount of bismuth oxide increases the reactivity of the prepared Pt / Bi composite catalyst. The preferred method for the amount of bismuth oxide added relative to 100 parts by mass of the organic compound is the same as the preferred method for the amount of Bi ion source added mentioned above.

[0062] <Water>

[0063] The method for manufacturing the oxide of the present invention is carried out in the presence of water, preferably ion-exchanged water, distilled water, or pure water.

[0064] Regarding the amount of water used, from the viewpoint of increasing the productivity of the organic compound oxide and suppressing the increase of the viscosity of the liquid phase, it is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and more 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.

[0065] The amount of water used is the sum of the added water, the moisture content of the Pt supported on the carrier, and the moisture content of the Bi ion source.

[0066] <Reaction Conditions>

[0067] (pH during the reaction)

[0068] The minimum pH value in the reaction of the oxide manufacturing method of the present invention is less than 7. By making the minimum pH value in the reaction less than 7, the reaction system can be made acidic, the Bi ion source dissolves and easily generates Bi ions. Since Bi ions can inhibit Bi from precipitating alone onto supports such as activated carbon, Bi can be reduced and precipitated near Pt, thereby forming a highly active structure. Therefore, it is believed that the reactivity of the reaction for manufacturing highly active Pt / Bi composite catalysts and the reactivity of dehydrogenation reactions of organic compounds can be significantly improved.

[0069] Regarding the minimum pH value in the reaction of the method for producing the oxide of the present invention, since the organic compound undergoes a dehydrogenation reaction to generate the oxide, it can be adjusted to less than 7 by not adding an alkali or the like to the reaction system.

[0070] Regarding the pH in the method for manufacturing the oxide of the present invention, when using Bi oxide as the Bi ion source, even if it is alkaline during the initial stage of adding raw materials, it gradually becomes acidic as the reaction progresses and the oxides of organic compounds increase in the reaction system.

[0071] Regarding the minimum pH value at the end of the reaction, from the viewpoint of improving the manufacturing efficiency of the Pt / Bi composite catalyst and the manufacturing efficiency of the oxide of the organic compound, it is preferably 6 or less, more preferably 5 or less, even more preferably 4 or less, and preferably 1 or more, more preferably 1.5 or more, and even more preferably 2 or more.

[0072] (Reaction temperature)

[0073] Regarding the reaction temperature in the method for manufacturing the oxide of the present invention, from the viewpoint of the reactivity of the reaction for manufacturing the Pt / Bi composite catalyst and the reactivity of the dehydrogenation reaction of the organic compound, it is preferably 50°C or higher, more preferably 60°C or higher, and from the viewpoint of equipment load, it is preferably 100°C or lower, more preferably 90°C or lower, and even more preferably 85°C or lower.

[0074] (Oxygen-containing gas)

[0075] In the method for manufacturing the oxide of the present invention, from the viewpoint of causing the organic compound to undergo a dehydrogenation reaction, it is preferable to supply oxygen into the reaction system.

[0076] Oxygen can be supplied by circulating oxygen-containing gas in a liquid phase. Examples of oxygen-containing gases include oxygen gas and air.

[0077] When using a mixed gas containing oxygen, from the viewpoint of not affecting the activity, the gas used in conjunction with oxygen is preferably an inert gas such as helium, argon, or nitrogen.

[0078] Regarding the oxygen concentration in the oxygen-containing gas, from the viewpoint of the productivity of the oxide, it is preferably 10% by volume or more, more preferably 50% by volume or more, even more preferably 70% by volume or more, even more preferably 90% by volume or more, and even more preferably 100% by volume.

[0079] (Reaction pressure)

[0080] In the method for manufacturing the oxide of the present invention, the reaction can be carried out under normal pressure or under pressure. Regarding the reaction pressure, from the viewpoint of reactivity, it is preferably 0.09 MPa or more, more preferably 0.10 MPa or more using an absolute pressure gauge; from the viewpoint of equipment load, it is preferably 0.5 MPa or less, more preferably 0.2 MPa or less, and even more preferably 0.11 MPa or less. The reaction is preferably carried out under normal pressure.

[0081] <Refining of Oxides>

[0082] The method for manufacturing the oxide of the present invention may further include a step of purifying the obtained oxide after the dehydrogenation reaction of the organic compound is completed.

[0083] In the method for manufacturing the oxide of the present invention, the Pt / Bi composite catalyst can be removed from the reaction solution containing the oxide of the organic compound by performing, for example, pressure filtration or vacuum filtration after the oxidation reaction of the organic compound is completed.

[0084] In the method for manufacturing the oxides of the present invention, oxides of organic compounds can be obtained with a high yield. Therefore, the reaction solution containing the oxides of the organic compounds can be directly used as a raw material for manufacturing detergents, etc. Furthermore, the reaction solution containing the oxides of the organic compounds can be extracted, distilled, or otherwise subjected to other methods as needed to obtain the organic compounds at a high concentration.

[0085] Other methods for manufacturing oxides

[0086] Another method for manufacturing the oxide of the present invention is as follows: an oxide of an organic compound having one primary hydroxyl group is obtained by subjecting an organic compound to a dehydrogenation reaction in the presence of a Pt / Bi composite catalyst, a Bi ion source and water, under conditions where the minimum pH value in the reaction is less than 7.

[0087] Other methods for manufacturing oxides according to the present invention enable the production of oxides of organic compounds with high yields.

[0088] In other methods of manufacturing the oxides of the present invention, the Pt / Bi composite catalyst refers to the same substance as the Pt / Bi composite catalyst obtained by the above-described method of manufacturing the oxides, or the Pt / Bi composite catalyst obtained by the method of manufacturing the Pt / Bi catalyst described later.

[0089] Other methods for producing the oxides of the present invention are preferably accompanied by the regeneration of the Pt / Bi composite catalyst.

[0090] The rationale for favoring the regeneration of the Pt / Bi composite catalyst is still uncertain, but the following considerations are made.

[0091] Regarding Pt / Bi composite catalysts, it is believed that due to their repeated use in the manufacturing process of oxides of organic compounds, Bi gradually dissolves, causing changes in the catalyst structure and a decrease in catalyst activity.

[0092] In other methods of manufacturing the oxides of the present invention, it is speculated that by adding a Bi ion source together with a Pt / Bi composite catalyst, Bi is reduced and precipitated onto the Pt / Bi composite catalyst, thereby replenishing the amount of dissolved Bi and regenerating the Pt / Bi composite catalyst. It is also speculated that, with the regeneration of the Pt / Bi composite catalyst, the dehydrogenation reaction of the organic compound is promoted, thereby obtaining the oxide of the organic compound in a high yield.

[0093] For the reasons stated above, other methods for manufacturing the oxides of the present invention can regenerate the Pt / Bi composite catalyst during the oxide manufacturing process, thus eliminating the need for additional equipment or processes for catalyst regeneration. This allows for the efficient production of oxides of organic compounds, resulting in significant advantages in terms of production efficiency and cost.

[0094] Furthermore, in the method for manufacturing the oxide of the present invention and other methods for manufacturing the oxide, from the viewpoint of efficiently regenerating the Pt / Bi composite catalyst and increasing the yield of the oxide of the organic compound, it is preferable to add a Bi ion source at the start of the dehydrogenation reaction of the organic compound or in the reaction, and more preferably to add a Bi ion source in the reaction.

[0095] By adding a Bi ion source to the system at the start of the reaction, the degradation of the Pt / Bi composite catalyst can be easily suppressed, thereby facilitating the improvement of the yield of the oxide of the organic compound.

[0096] Furthermore, by adding a Bi ion source to the system in the reaction in a manner that matches the deterioration condition of the Pt / Bi composite catalyst, the Pt / Bi composite catalyst can be regenerated. Therefore, the decrease in the efficiency of the dehydrogenation reaction of organic compounds can be suppressed, thereby making it easier to improve the yield of the oxides of organic compounds.

[0097] In addition, this method can address the problem of Bi dissolution and decreased catalyst activity due to catalyst recycling, and can also provide a way to regenerate the catalyst without re-preparing a high-performance Pt / Bi composite catalyst.

[0098] [Preparation method of Pt / Bi composite catalyst]

[0099] The method for manufacturing the Pt / Bi composite catalyst of the present invention is as follows: a method for manufacturing the Pt / Bi composite catalyst by mixing Bi ion source and Pt supported on a support in the presence of water and an organic compound having one primary hydroxyl group, and carrying out the reaction under the condition that the minimum pH value in the reaction is less than 7.

[0100] According to the method for manufacturing the Pt / Bi composite catalyst of the present invention, a catalyst exhibiting high activity in the dehydrogenation reaction of organic compounds can be produced.

[0101] The reasons for achieving the aforementioned effect are uncertain, but are presumed to be as follows.

[0102] In the preparation of conventional Pt / Bi composite catalysts, a reducing agent is typically added to both Pt and Bi ion sources under alkaline conditions, causing Pt and Bi to precipitate and thus preparing the Pt / Bi composite catalyst. However, in this method, Bi segregation occurs, therefore the resulting composite catalyst is considered to have few effective active structures and low activity for the dehydrogenation reactions of organic compounds.

[0103] On the other hand, it is speculated that in the manufacturing method of the Pt / Bi composite catalyst of the present invention, by contacting Pt supported on the support such as Pt / C catalyst with Bi ions under the condition that the minimum pH value in the reaction is less than 7, Bi can be uniformly reduced and precipitated on Pt even without the addition of a reducing agent, and a large amount of active structure effective for the dehydrogenation reaction of organic compounds can be formed, thereby improving the activity of the catalyst.

[0104] Furthermore, in the method for manufacturing the Pt / Bi composite catalyst of the present invention, from the viewpoint of manufacturing a catalyst exhibiting high activity, it is preferable to accompany the dehydrogenation reaction of an organic compound having one primary hydroxyl group in the reaction system, and more preferably to promote the dehydrogenation reaction of said organic compound.

[0105] Preferably, the reaction is accompanied by a dehydrogenation reaction of the organic compound. More preferably, the reason for promoting this reaction is uncertain, but the following is considered.

[0106] By mixing Pt supported on a support with a Bi ion source in the presence of the organic compound, a dehydrogenation reaction of the organic compound is induced. This generates a small amount of oxide of the organic compound, resulting in a solution containing the oxide. Consequently, the Bi ion source dissolves to produce Bi ions, which are then reduced and precipitated on the Pt. This process creates a Pt / Bi composite catalyst with higher activity than the Pt catalyst itself. It is speculated that the dehydrogenation reaction of the organic compound is subsequently promoted, leading to a high yield of the oxide of the organic compound.

[0107] For the reasons stated above, it is preferable that the catalyst can be manufactured simultaneously in the oxide manufacturing process, thus eliminating the need for additional equipment and processes for catalyst manufacturing. This allows for the efficient production of oxides of organic compounds, resulting in significant advantages in terms of production efficiency and cost.

[0108] According to the method for manufacturing the Pt / Bi composite catalyst of the present invention, along with the manufacturing of the Pt / Bi composite catalyst, an oxide, a carboxylic acid compound, or a salt of the carboxylic acid compound of the organic compound can be obtained.

[0109] Examples of carboxylic acid compounds or salts of carboxylic acid compounds include carboxylic acid compounds or salts of carboxylic acid compounds obtained by subjecting the aforementioned aliphatic alcohols or polyoxyalkylene alkyl ethers to a dehydrogenation reaction.

[0110] Examples of carboxylic acid compounds include fatty acids obtained by dehydrogenation of aliphatic alcohols and ether carboxylic esters obtained by dehydrogenation of polyoxyalkylene ethers.

[0111] Salts of carboxylic acid compounds include, for example, the neutralized salts of the fatty acid or ether carboxylic acid esters with alkali metal hydroxides such as sodium and potassium.

[0112] As an organic compound having one primary hydroxyl group in the method for manufacturing the Pt / Bi composite catalyst of the present invention, aliphatic alcohols and polyoxyalkylene alkyl ethers are preferred examples. The substances shown in the organic compounds having one primary hydroxyl group in the method for manufacturing the oxide of the present invention described above can be used appropriately.

[0113] From the viewpoint of oxide formation rate, organic compounds having one primary hydroxyl group are preferred organic compounds with high hydrophilicity. Furthermore, organic compounds having one primary hydroxyl group are preferably polyoxyalkylene ethers, and more preferably polyoxyalkylene ethers represented by the general formula (2).

[0114] Furthermore, the method for manufacturing the Pt / Bi composite catalyst of the present invention can also be carried out in the presence of an oxide of the organic compound. Examples of oxides of the organic compound include carboxylic acid compounds or salts of carboxylic acid compounds obtained by oxidizing the hydroxyl groups of the organic compound, as exemplified in the method for manufacturing the oxides of the present invention.

[0115] The Pt supported on the support used in the method for manufacturing the Pt / Bi composite catalyst of the present invention can be the same material as the Pt supported on the support used in the method for manufacturing the oxide of the present invention, and the preferred range is also the same.

[0116] In the method for manufacturing the Pt / Bi composite catalyst of the present invention, the support for the Pt supported on the carrier is preferably activated carbon. Examples of activated carbon include the same material used in the method for manufacturing the oxides of the present invention, and the preferred range is also the same.

[0117] From the viewpoint of improving the catalytic activity of the manufactured Pt / Bi composite catalyst, the Bi ion source in the method for manufacturing the Pt / Bi composite catalyst of the present invention is preferably non-water-soluble.

[0118] As a Bi ion source, the same substance as the Bi ion source used in the method for manufacturing the oxide of the present invention can be exemplified.

[0119] The method for manufacturing the Pt / Bi composite catalyst of the present invention is carried out in the presence of water. Examples of water include the same substances used in the method for manufacturing the oxides of the present invention, and the preferred range is also the same.

[0120] The minimum pH value in the reaction of the method for manufacturing the Pt / Bi composite catalyst of the present invention is less than 7. By making the minimum pH value in the reaction less than 7, the reaction system can be made acidic, the Bi ion source dissolves and easily generates Bi ions. Since it is possible to suppress the precipitation of Bi ions onto supports such as activated carbon, Bi is reduced and precipitated near Pt, thereby producing a highly active structure. Therefore, it is believed that the reactivity of the reaction for manufacturing highly active Pt / Bi composite catalysts and the reactivity of dehydrogenation reactions of organic compounds can be significantly improved. The preferred pH range for the reaction is the same as that for the reaction in the method for manufacturing the oxides of the present invention.

[0121] The reaction temperature in the method for manufacturing the Pt / Bi composite catalyst of the present invention is the same as the reaction temperature in the method for manufacturing the oxide of the present invention.

[0122] From the viewpoint of enabling organic compounds to undergo dehydrogenation reactions, it is preferable to supply oxygen into the reaction system in the method for manufacturing the Pt / Bi composite catalyst of the present invention.

[0123] Oxygen supply can be implemented by circulating oxygen-containing gas in the liquid phase. Examples of oxygen-containing gases include the same substances used in the method for manufacturing the oxides of the present invention, and the preferred range is also the same.

[0124] The reaction pressure in the method for manufacturing the Pt / Bi composite catalyst of the present invention is the same as the reaction pressure in the method for manufacturing the oxide of the present invention.

[0125] <Catalyst Recovery>

[0126] The catalyst produced in the method for manufacturing the Pt / Bi composite catalyst of the present invention can be recovered by separating it from the reaction liquid. As a recovery method, for example, pressure filtration or vacuum filtration can be used.

[0127] The recovered Pt / Bi composite catalyst can be cleaned, or it can be used directly as a catalyst for the dehydrogenation reaction of organic compounds without cleaning.

[0128] The catalyst produced by the method for manufacturing the Pt / Bi composite catalyst of the present invention can be recycled and used again as a catalyst for the dehydrogenation reaction of the aforementioned organic compounds.

[0129] Other methods for manufacturing Pt / Bi composite catalysts

[0130] Another method for manufacturing the Pt / Bi composite catalyst of the present invention is a method for manufacturing the Pt / Bi composite catalyst by mixing the Pt / Bi composite catalyst and the Bi ion source in the presence of water and an organic compound having one primary hydroxyl group and reacting under conditions where the minimum pH value in the reaction is less than 7.

[0131] According to other methods of manufacturing the Pt / Bi composite catalyst of the present invention, it is possible to produce a catalyst that exhibits high activity in the dehydrogenation reaction of organic compounds.

[0132] In other methods of manufacturing the Pt / Bi composite catalyst of the present invention, the Pt / Bi composite catalyst refers to the same substance as the Pt / Bi composite catalyst obtained by the manufacturing methods of the above-described Pt / Bi composite catalyst or the oxide described later.

[0133] Other methods for manufacturing the Pt / Bi composite catalyst of the present invention preferably involve adding a Bi ion source at the start of the reaction or during the reaction to regenerate the Pt / Bi composite catalyst, and more preferably involve adding a Bi ion source during the reaction to regenerate the Pt / Bi composite catalyst.

[0134] By adding a Bi ion source to the system at the start of the reaction, the degradation of the Pt / Bi composite catalyst can be suppressed, and the yield of the oxide of the organic compound can be improved.

[0135] In addition, by adding a Bi ion source to the system during the reaction, the Pt / Bi composite catalyst can be regenerated, thus suppressing the decrease in the efficiency of the dehydrogenation reaction of organic compounds and improving the yield of the oxides of organic compounds.

[0136] The rationale for regenerating the Pt / Bi composite catalyst by adding a Bi ion source at the start of the reaction or during the reaction is uncertain, but the following is considered.

[0137] Regarding Pt / Bi composite catalysts, it is believed that due to their repeated use in the manufacturing process of oxides of organic compounds, Bi gradually dissolves, causing changes in the catalyst structure and a decrease in catalyst activity.

[0138] In other methods of manufacturing the Pt / Bi composite catalyst of the present invention, it is speculated that by adding a Bi ion source together with the Pt / Bi composite catalyst, Bi is reduced and precipitated onto the Pt / Bi composite catalyst, thereby replenishing the amount of dissolved Bi and regenerating the Pt / Bi composite catalyst. It is also speculated that, with the regeneration of the Pt / Bi composite catalyst, the dehydrogenation reaction of the organic compound is promoted, thereby obtaining the oxide of the organic compound in a high yield.

[0139] For the reasons stated above, other methods for manufacturing the Pt / Bi composite catalyst of the present invention can regenerate the Pt / Bi composite catalyst during the oxide manufacturing process, thus eliminating the need for additional equipment or processes for catalyst regeneration. This allows for the efficient manufacture of Pt / Bi composite catalysts, resulting in significant advantages in terms of production efficiency and cost.

[0140] [Oxides of organic compounds]

[0141] The oxides of organic compounds obtained in the methods for manufacturing the oxides of the present invention and the methods for manufacturing the Pt / Bi composite catalyst can be used in a wide range of fields as detergents, softeners, humectants, dyeing auxiliaries, etc. Furthermore, due to their excellent foaming and cleaning power and low skin irritation, they can also be suitable for use in products that come into prolonged contact with human skin, such as shampoos, shower gels, dishwashing liquids, cosmetic compositions, and fragrances.

[0142] According to the method for manufacturing oxides and the method for manufacturing Pt / Bi composite catalysts of the present invention, oxides of organic compounds can be obtained with high yield.

[0143] In the method for manufacturing the oxide and the method for manufacturing the Pt / Bi composite catalyst of the present invention, the rate of formation of the oxide of the organic compound at the 24th hour of reaction is preferably 75% or more, more preferably 77% or more, further preferably 80% or more, and even more preferably 83% or more.

[0144] Furthermore, the rate of formation of oxides of the organic compound in the third hour of reaction is preferably 20% or more, more preferably 25% or more, and even more preferably 30% or more.

[0145] In this invention, the rate of formation of oxides of organic compounds can be calculated in the same way as the rate of formation of carboxylic acid compounds in the examples described later.

[0146] [Pt / Bi composite catalyst]

[0147] The Pt / Bi composite catalyst of the present invention can be obtained using the methods for manufacturing the oxides and the Pt / Bi composite catalysts of the present invention described above.

[0148] The Pt / Bi composite catalyst of the present invention is suitable for use in reactions to produce oxides of organic compounds by dehydrogenating an organic compound having one primary hydroxyl group. That is, the present invention also relates to a method for producing oxides of organic compounds by dehydrogenating an organic compound having one primary hydroxyl group in the presence of the Pt / Bi composite catalyst. In the method for producing oxides of the present invention, it is preferable to supply oxygen to a composition containing an organic compound having one primary hydroxyl group in the presence of the Pt / Bi composite catalyst, using water as a solvent, to dehydrogenate the organic compound having one primary hydroxyl group.

[0149] Regarding the Bi loading in the Pt / Bi composite catalyst, from the viewpoint of improving the productivity of the oxidation reaction products, it is preferably 0.01% by mass or more, more preferably 0.5% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3.5% by mass or less, and even more preferably 2.5% by mass or less.

[0150] Regarding the mass ratio (atomic ratio) Bi / Pt of Bi to Pt in the Pt / Bi composite catalyst of the present invention, from the viewpoint of improving the productivity of the oxidation reaction products, it is preferably 0.05 or more, more preferably 0.1 or more, more preferably 2.0 or less, more preferably 1.5 or less, further preferably 1.0 or less, and even more preferably 0.5 or less.

[0151] Regarding the above embodiments, the present invention further discloses the following methods for manufacturing oxides and methods for manufacturing Pt / Bi composite catalysts.

[0152] <1> A method for producing an oxide, wherein an organic compound having one primary hydroxyl group is subjected to a dehydrogenation reaction in the presence of a Pt or Bi ion source supported on a support and water, under conditions where the minimum pH value in the reaction is less than 7, to obtain an oxide of the organic compound.

[0153] <2> A method for producing an oxide, wherein an organic compound having one primary hydroxyl group is subjected to a dehydrogenation reaction in the presence of a Pt / Bi composite catalyst, a Bi ion source, and water, under conditions where the minimum pH value in the reaction is less than 7, to obtain an oxide of the organic compound.

[0154] <3> according to <1> or <2> The method for manufacturing oxides described herein includes the preparation of a Pt / Bi composite catalyst.

[0155] <4> according to <1> ~ <3> The method for manufacturing an oxide as described in any one of the present invention, wherein the Bi ion source is non-water-soluble.

[0156] <5> according to <1> ~ <4> The method for manufacturing an oxide as described in any one of the present inventions, wherein the Bi ion source is bismuth oxide.

[0157] <6> according to <1> ~ <5> The method for manufacturing an oxide as described in any one of the present invention, wherein the amount of the Bi ion source added is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, even more preferably 0.05 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, and even more preferably 0.3 parts by mass or less, relative to 100 parts by mass of the organic compound.

[0158] <7> according to <1> ~ <6> In any of the methods for manufacturing oxides, the mass ratio (atomic ratio) of Bi to Pt, Bi / Pt, is preferably 0.05 or more, more preferably 0.1 or more, and 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, even more preferably 1.2 or less, and even more preferably 1.0 or less.

[0159] <8> according to <1> ~ <7> The method for manufacturing an oxide as described in any one of the present inventions, wherein the organic compound is an aliphatic alcohol or a polyoxyalkylene alkyl ether.

[0160] <9> according to <8> The method for manufacturing oxides described herein preferably includes one or more of the following general formulas (1) or (2).

[0161] R 1 OH (1)

[0162] In general formula (1), R 1 It is a monovalent aliphatic hydrocarbon group with 2 or more carbon atoms and less than 40 carbon atoms.

[0163] R 2 O-(AO) n -H (2)

[0164] In general formula (2), R 2 It represents a monovalent aliphatic hydrocarbon group with 2 or more carbon atoms and less than 40 carbon atoms, A represents an alkyldiyl group with 2 or more carbon atoms and less than 4 carbon atoms, AO represents an alkeneoxy group, and n is the average number of moles of alkeneoxy groups added, which is more than 1 and less than 30.

[0165] <10> according to <9> The method for manufacturing oxides described herein, wherein R of general formula (1) 1 Preferably, it is a straight-chain or branched monovalent aliphatic primary hydrocarbon group, more preferably a straight-chain or branched primary alkyl or primary alkenyl group, and even more preferably a straight-chain primary alkyl group.

[0166] <11> according to <9> or <10> The method for manufacturing oxides described herein, wherein R of general formula (1) 1 The carbon number is preferably 6 or more, more preferably 8 or more, further preferably 10 or more, even more preferably 12 or more, and preferably 36 or less, more preferably 22 or less, even more preferably 18 or less, and even more preferably 14 or less.

[0167] <12> according to <9> ~ <11> The method for manufacturing an oxide as described in any one of the formulas, wherein R of the general formula (2) 2 Preferably, it is a straight-chain or branched aliphatic primary hydrocarbon group, more preferably a straight-chain or branched primary alkyl or primary alkenyl group, and even more preferably a straight-chain primary alkyl group.

[0168] <13> according to <9> ~ <12> The method for manufacturing an oxide as described in any one of the formulas, wherein R of the general formula (2) 2 The carbon number is preferably 6 or more, more preferably 8 or more, further preferably 10 or more, even more preferably 12 or more, and preferably 36 or less, more preferably 22 or less, even more preferably 18 or less, and even more preferably 14 or less.

[0169] <14> according to <9> ~ <13> The method for manufacturing an oxide as described in any one of the formulas, wherein A in the general formula (2) is preferably ethylidene or propyleneide, more preferably ethylidene.

[0170] <15> according to <9> ~ <14> The method for manufacturing an oxide as described in any one of the general formulas (2), wherein AO in the general formula (2) is preferably ethyleneoxy (EO) or propyleneoxy (PO), more preferably ethyleneoxy (EO).

[0171] <16> according to <9> ~ <15> The method for manufacturing an oxide as described in any one of the general formulas (2) is preferably 3 or more, and preferably 25 or less, more preferably 20 or less, further preferably 16 or less, and even more preferably 12 or less.

[0172] <17> according to <9> ~ <16> The method for manufacturing an oxide as described in any one of the formulas, wherein the organic compound is preferably a polyoxyalkylene alkyl ether, more preferably a polyoxyalkylene alkyl ether represented by the general formula (2).

[0173] <18> according to <1> ~ <17> A method for manufacturing an oxide as described in any one of the present invention, wherein the oxide of the organic compound is a carboxylic acid compound or a salt of a carboxylic acid compound.

[0174] <19> according to <18> The method for manufacturing oxides described herein, wherein the carboxylic acid compound or the salt of the carboxylic acid is an ether carboxylic acid ester or a salt thereof obtained by oxidizing a polyoxyalkylene alkyl ether.

[0175] <20> according to <1> ~ <19> The method for manufacturing an oxide as described in any one of the present inventions, wherein the carrier is activated carbon.

[0176] <21> according to <1> ~ <20> The method for manufacturing an oxide as described in any one of the present inventions, wherein the particle size of the Pt supported on the carrier is preferably 1 nm or more, more preferably 3 nm or more, and preferably 20 nm or less, more preferably 15 nm or less, and even more preferably 10 nm or less.

[0177] <22> according to <1> ~ <21> In any of the methods for manufacturing oxides, the loading of Pt supported on the carrier, i.e., the loading amount of Pt relative to the total mass of the carrier and Pt, is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, even 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, and even more preferably 10% by mass or less.

[0178] <23> according to <1> ~ <22> In any of the methods for manufacturing oxides, the amount of Pt supported on the carrier added relative to 100 parts by mass of the organic compound is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 4 parts by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 6 parts by mass or less.

[0179] <24> according to <1> ~ <23> In any of the methods for manufacturing oxides, the amount of water is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and more 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.

[0180] <25> according to <1> ~ <24> Any of the methods for producing oxides described herein, wherein no alkali or similar agent is added to the reaction system.

[0181] <26> according to <1> ~ <25> In any of the methods for manufacturing an oxide, the minimum pH value at the end of the reaction in the method for manufacturing an oxide is preferably 6 or less, more preferably 5 or less, even more preferably 4 or less, and preferably 1 or more, more preferably 1.5 or more, and even more preferably 2 or more.

[0182] <27> according to <1> ~ <26> The method for manufacturing an oxide as described in any one of the claims, wherein the reaction temperature in the method for manufacturing the oxide is preferably 50°C or higher, more preferably 60°C or higher, and preferably 100°C or lower, more preferably 90°C or lower, and even more preferably 85°C or lower.

[0183] <28> according to <1> ~ <27> The method for producing an oxide as described in any one of the present invention, wherein, in the method for producing an oxide, oxygen is preferably supplied to the reaction system.

[0184] <29> according to <28> The method for manufacturing oxides described herein involves supplying oxygen by circulating oxygen-containing gas in a liquid phase.

[0185] <30> according to <29> The method for manufacturing oxides described herein, wherein the oxygen-containing gas is oxygen or air.

[0186] <31> according to <30> or <31> The method for manufacturing oxides described herein, wherein 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, even more preferably 90% by volume or more, and even more preferably 100% by volume.

[0187] <32> according to <1> ~ <31> The method for manufacturing an oxide as described in any one of the claims, wherein the reaction pressure, measured in an absolute pressure gauge, is preferably 0.09 MPa or more, more preferably 0.10 MPa or more, and more preferably 0.5 MPa or less, more preferably 0.2 MPa or less, and even more preferably 0.11 MPa or less.

[0188] <33> according to <1> ~ <32> The method for manufacturing an oxide as described in any one of the claims, wherein the reaction is preferably carried out under normal pressure in the method for manufacturing the oxide.

[0189] <34> according to <1> ~ <33> A method for producing an oxide as described in any of the present invention, wherein a Bi ion source is added at the start of the dehydrogenation reaction or during the reaction.

[0190] <35> according to <1> ~ <34> The method for manufacturing an oxide as described in any one of the methods further includes a step of purifying the obtained oxide after the dehydrogenation reaction of the organic compound is completed.

[0191] <36> according to <35> The method for manufacturing oxides described herein includes a step of refining the obtained oxides, wherein after the oxidation reaction of the organic compounds is completed, the Pt / Bi composite catalyst is removed from the reaction solution containing the oxides of the organic compounds by pressure filtration or vacuum filtration.

[0192] <37> A method for manufacturing a Pt / Bi composite catalyst, wherein a Bi ion source and Pt supported on a support are mixed in the presence of water and an organic compound having one primary hydroxyl group, and the reaction is carried out under conditions where the minimum pH value in the reaction is less than 7.

[0193] <38> A method for manufacturing a Pt / Bi composite catalyst, wherein the Pt / Bi composite catalyst and a Bi ion source are mixed in the presence of water and an organic compound having one primary hydroxyl group, and the reaction is carried out under conditions where the minimum pH value in the reaction is less than 7.

[0194] <39> according to <38> The method for manufacturing a Pt / Bi composite catalyst described herein involves adding a Bi ion source at the start of the reaction or during the reaction to regenerate the Pt / Bi composite catalyst.

[0195] <40> according to <37> ~ <39> The method for manufacturing a Pt / Bi composite catalyst described herein includes a dehydrogenation reaction of the organic compound.

[0196] <41> according to <37> ~ <40> The method for manufacturing a Pt / Bi composite catalyst as described in any one of the following: wherein the organic compound is an aliphatic alcohol or a polyoxyalkylene alkyl ether.

[0197] <42> according to <37> ~ <41> The method for manufacturing a Pt / Bi composite catalyst as described in any one of the following methods, wherein the aliphatic alcohol or polyoxyalkylene alkyl ether is preferably one or more of the following general formula (1) or general formula (2).

[0198] R 1 OH (1)

[0199] In general formula (1), R 1 It is a monovalent aliphatic hydrocarbon group with 2 or more carbon atoms and less than 40 carbon atoms.

[0200] R 2 O-(AO) n -H (2)

[0201] In general formula (2), R 2 It represents a monovalent aliphatic hydrocarbon group with 2 or more carbon atoms and less than 40 carbon atoms, A represents an alkyldiyl group with 2 or more carbon atoms and less than 4 carbon atoms, AO represents an alkeneoxy group, and n is the average number of moles of alkeneoxy groups added, which is more than 1 and less than 30.

[0202] <43> according to <42> The method for manufacturing a Pt / Bi composite catalyst of oxides described herein, wherein R of general formula (1) 1 Preferably, it is a straight-chain or branched monovalent aliphatic primary hydrocarbon group, more preferably a straight-chain or branched primary alkyl or primary alkenyl group, and even more preferably a straight-chain primary alkyl group.

[0203] <44> according to <42> or <43> The method for manufacturing a Pt / Bi composite catalyst described herein, wherein R of the general formula (1) 1 The carbon number is preferably 6 or more, more preferably 8 or more, further preferably 10 or more, even more preferably 12 or more, and preferably 36 or less, more preferably 22 or less, even more preferably 18 or less, and even more preferably 14 or less.

[0204] <45> according to <42> ~ <44> The method for manufacturing a Pt / Bi composite catalyst as described in any one of the following methods, wherein R of general formula (2) 2 Preferably, it is a straight-chain or branched aliphatic primary hydrocarbon group, more preferably a straight-chain or branched primary alkyl or primary alkenyl group, and even more preferably a straight-chain primary alkyl group.

[0205] <46> according to <42> ~ <45> The method for manufacturing a Pt / Bi composite catalyst described herein, wherein R of the general formula (2) 2The carbon number is preferably 6 or more, more preferably 8 or more, further preferably 10 or more, even more preferably 12 or more, and preferably 36 or less, more preferably 22 or less, even more preferably 18 or less, and even more preferably 14 or less.

[0206] <47> according to <42> ~ <46> The method for manufacturing a Pt / Bi composite catalyst as described in any one of the above, wherein A in the general formula (2) is preferably ethylene or propylene, more preferably ethylene.

[0207] <48> according to <42> ~ <47> The method for manufacturing a Pt / Bi composite catalyst as described in any one of the following, wherein the AO of the general formula (2) is preferably ethyleneoxy (EO) or propyleneoxy (PO), more preferably ethyleneoxy (EO).

[0208] <49> according to <42> ~ <48> The method for manufacturing a Pt / Bi composite catalyst as described in any one of the general formulas (2) is preferably 3 or more, and preferably 25 or less, more preferably 20 or less, further preferably 16 or less, and even more preferably 12 or less.

[0209] <50> according to <42> ~ <49> The method for manufacturing a Pt / Bi composite catalyst as described in any one of the following, wherein the organic compound is preferably a polyoxyalkylene ether, more preferably a polyoxyalkylene ether represented by general formula (2).

[0210] <51> according to <37> ~ <50> The method for manufacturing a Pt / Bi composite catalyst as described in any one of the present inventions, wherein the reaction is further carried out in the presence of an oxide of the organic compound.

[0211] <52> according to <51> The method for manufacturing a Pt / Bi composite catalyst described herein, wherein the oxide of the organic compound is a carboxylic acid compound or a salt of a carboxylic acid compound.

[0212] <53> according to <52> The method for manufacturing a Pt / Bi composite catalyst described herein includes a carboxylic acid compound or a salt thereof, which is any one of the following: a fatty acid obtained by dehydrogenation of an aliphatic alcohol, an ether carboxylic acid ester obtained by dehydrogenation of a polyoxyalkylene alkyl ether, and a neutral salt thereof with an alkali metal hydroxide such as sodium or potassium.

[0213] <54> according to <37> ~ <53> The method for manufacturing a Pt / Bi composite catalyst as described in any one of the following: wherein the Bi ion source is non-water-soluble.

[0214] <55> according to <37> ~ <54> The method for manufacturing a Pt / Bi composite catalyst as described in any one of the present inventions, wherein the Bi ion source is bismuth oxide.

[0215] <56> according to <37> ~ <55> The method for manufacturing a Pt / Bi composite catalyst as described in any one of the following is preferred to be 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, even more preferably 0.05 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, and even more preferably 0.3 parts by mass or less, relative to 100 parts by mass of the organic compound.

[0216] <57> according to <37> ~ <56> In any one of the methods for manufacturing a Pt / Bi composite catalyst, the mass ratio (atomic ratio) of Bi to Pt is preferably 0.05 or more, more preferably 0.1 or more, and 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, even more preferably 1.2 or less, and even more preferably 1.0 or less.

[0217] <58> according to <37> ~ <57> The method for manufacturing a Pt / Bi composite catalyst as described in any one of the following: wherein the support is activated carbon.

[0218] <59> according to <37> ~ <58> The method for manufacturing a Pt / Bi composite catalyst as described in any one of the following methods, wherein the particle size of the Pt supported on the support is preferably 1 nm or more, more preferably 3 nm or more, and more preferably 20 nm or less, more preferably 15 nm or less, and even more preferably 10 nm or less.

[0219] <60> according to <37> ~ <59> The method for manufacturing a Pt / Bi composite catalyst as described in any one of the claims, wherein the amount of Pt supported on the support, i.e., the amount of Pt supported relative to the total amount of the support and Pt, is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, even 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, and even more preferably 10% by mass or less.

[0220] <61> according to <37> ~ <60> The method for manufacturing a Pt / Bi composite catalyst as described in any one of the claims, wherein the amount of Pt supported on the support added is preferably 1 part by mass or more, more preferably 3 parts by mass or more, further preferably 4 parts by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and further preferably 6 parts by mass or less, relative to 100 parts by mass of the organic compound.

[0221] <62> according to <37> ~ <61> In any of the methods for manufacturing a Pt / Bi composite catalyst, the amount of water is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and more 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.

[0222] <63> according to <37> ~ <62> The method for manufacturing a Pt / Bi composite catalyst as described in any one of the claims, wherein the minimum pH value at the end of the reaction in the method for manufacturing the Pt / Bi composite catalyst is preferably 6 or less, more preferably 5 or less, even more preferably 4 or less, and preferably 1 or more, more preferably 1.5 or more, and even more preferably 2 or more.

[0223] <64> according to <37> ~ <63> Any of the methods described herein for manufacturing a Pt / Bi composite catalyst in which no alkali agent or the like is added to the reaction system.

[0224] <65> according to <37> ~ <64> The method for manufacturing a Pt / Bi composite catalyst as described in any one of the claims, wherein the reaction temperature in the method for manufacturing the Pt / Bi composite catalyst is preferably 50°C or higher, more preferably 60°C or higher, and more preferably 100°C or lower, more preferably 90°C or lower, and even more preferably 85°C or lower.

[0225] <66> according to <37> ~ <65> The method for manufacturing a Pt / Bi composite catalyst as described in any one of the present inventions, wherein oxygen is preferably supplied to the reaction system in the method for manufacturing the Pt / Bi composite catalyst.

[0226] <67> according to <66> The method for manufacturing a Pt / Bi composite catalyst described herein involves supplying oxygen by circulating oxygen-containing gas in a liquid phase.

[0227] <68> according to <67> The method for manufacturing a Pt / Bi composite catalyst described herein, wherein the oxygen-containing gas is oxygen or air.

[0228] <69> according to <67> or <68> The method for manufacturing a Pt / Bi composite catalyst described herein, wherein the oxygen concentration in the oxygen-containing gas is preferably 10% by volume or more, more preferably 50% by volume or more, further preferably 70% by volume or more, even more preferably 90% by volume or more, and even more preferably 100% by volume.

[0229] <70> according to <37> ~ <69> The method for manufacturing a Pt / Bi composite catalyst as described in any one of the claims, wherein the reaction pressure, measured in absolute pressure gauge, is preferably 0.09 MPa or more, more preferably 0.10 MPa or more, and more preferably 0.5 MPa or less, more preferably 0.2 MPa or less, and even more preferably 0.11 MPa or less.

[0230] <71> according to <37> ~ <70> The method for manufacturing a Pt / Bi composite catalyst as described in any one of the claims, wherein the reaction is preferably carried out under normal pressure in the method for manufacturing the Pt / Bi composite catalyst.

[0231] <72> A method for manufacturing an oxide, wherein, in utilizing <37> ~ <71> In the presence of a Pt / Bi composite catalyst obtained by any of the methods described in the present invention, the organic compound is subjected to a dehydrogenation reaction to obtain an oxide of the organic compound.

[0232] Example

[0233] The present invention will be specifically described below through examples, but the present invention is not limited to these examples in any way. The values ​​of each property were measured and evaluated using the methods described below.

[0234] [Preparation of Pt / Bi composite catalysts and carboxylic acid compounds]

[0235] <Example 1>

[0236] The raw materials are added as shown below to a 500 mL 5-necked flask equipped with a reflux tube, a dissolved oxygen meter (METTLER TOLEDO), a mechanical stirrer (IWAKI, with a glass stirring rod fitted with crescent-shaped stirring blades (blade width 7.5 cm × height 2.2 cm × thickness 0.4 cm), a glass temperature regulator, and a glass tube for gas blowing.

[0237] (Added ingredients, etc.)

[0238] • Organic compound: AE1 (a polyoxyalkylene alkyl ether with an average of 3.6 mol of ethylene oxide added to 1 mol of lauryl alcohol): 100 parts by weight (200 g).

[0239] • Pt supported on the carrier: 5% Pt / C (manufactured by Evonik, C: charcoal, moisture content: 59.9% by mass): 4.90 parts by mass (24.45 g) were added based on the solid components after removing the moisture content.

[0240] • Bi ion source: Bismuth oxide (manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.): 0.11 parts by weight (0.219 g).

[0241] • Water: Add (35.35g) of ion-exchanged water to bring the total water content (5% Pt / C) to 25 parts by mass.

[0242] Next, under nitrogen flow conditions, the five-necked flask was immersed in a water bath, and the added raw materials were stirred at 600 rpm while the temperature was raised to 80°C. After reaching 80°C, the nitrogen flow was stopped, and oxygen was bubbled into the added raw materials at 60 mL / min, and the reaction was carried out at atmospheric pressure for 24 hours.

[0243] The reaction was divided into several parts, with each part carried out every few hours. When temporarily stopping the reaction, the reaction temperature was lowered to room temperature, oxygen bubbling was stopped, and nitrogen was allowed to flow through, maintaining a dissolved oxygen concentration of 0 ppm for 1 hour to stop the reaction. To restart the reaction, stirring was performed at 600 rpm under nitrogen flow conditions, while the temperature was raised to 80°C. Then, nitrogen flow was stopped, and oxygen was bubbled at 60 mL / min to initiate the reaction.

[0244] After 24 hours of reaction, oxygen bubbling was stopped and nitrogen was introduced. The dissolved oxygen concentration was maintained at 0 ppm for 1 hour. Then, using a pressure filter, nitrogen was introduced at 80°C at a rate of 4 kgf / cm³. 2 Nitrogen is injected, thereby pressurizing and filtering the reaction solution to separate the reaction solution from the catalyst.

[0245] During the reaction, the reaction solution was sampled every hour, and the formation rate of carboxylic acid compounds was determined using the method described later. The formation rates of carboxylic acid compounds are summarized in Tables 1-4.

[0246] (Calculation of the formation rate of carboxylic acid compounds)

[0247] Add a mixture of 60 mL acetone and 10 mL deionized water to 0.3 g of the sampled reaction solution and stir to prepare the test sample. Titrate the test sample with a 0.05 mol / L ethanolic potassium hydroxide aqueous solution to determine the neutralization point. Calculate the measured acid value of the reaction solution from the determined neutralization point, and use the following formula to calculate the rate of formation of the carboxylic acid compound.

[0248] Carboxylic acid compound formation rate (%) = (Measured acid value / Theoretical acid value) × 100

[0249] The theoretical acid value and the measured acid value are shown below.

[0250] (1) Calculation of theoretical acid value: The OHV (hydroxyl value) of the organic compound (AE1) was calculated and the result was 162 mg KOH / g. In addition, based on the molecular weight of the carboxylic acid compound obtained by oxidation of the organic compound (AE1), the acid value (theoretical acid value) when 100% of the carboxylic acid compound is generated in the reaction was calculated and the result was 156 mg KOH / g.

[0251] (2) Calculation of measured acid value: The measured acid value is calculated using the following formula based on the neutralization point.

[0252] Measured acid value (mgKOH / g) = Titration volume of potassium hydroxide aqueous solution (mL) × 56.11 (g / mol) × 0.05 (mol / L) / Sample volume (g) / 0.7692 (mass ratio of raw materials in the reaction solution)

[0253] <Examples 2 and 3>

[0254] The amount of bismuth oxide added was varied as shown in Table 1, and the reactions of Examples 2 and 3 were performed in the same manner as in Example 1. The formation rates of carboxylic acid compounds at the 24th hour of the reaction are summarized in Table 1.

[0255] <Example 4>

[0256] The Bi ion source was changed to 0.23 parts by mass of bismuth nitrate pentahydrate (manufactured by Fujifilm and Koimitsu Chemical Co., Ltd.) as shown in Table 1, and the reaction of Example 4 was carried out in the same manner as in Example 1. The formation rate of carboxylic acid compounds at the 24th hour of reaction is summarized in Table 1.

[0257] <Example 5>

[0258] The type of organic compound was changed to K2098 (Kalcohol 2098, manufactured by Kao Corporation) as shown in Table 2, and the reaction of Example 5 was carried out in the same manner as in Example 1. Furthermore, the OHV of K2098 is 301 mg KOH / g, and the theoretical acid value of its oxidation product (carboxylic acid compound) is 280 mg KOH / g. The formation rate of the carboxylic acid compound at the 7th hour of reaction is summarized in Table 2.

[0259] <Example 6>

[0260] The organic compound was changed to AE2 (a polyoxyalkylene alkyl ether with an average of 9 mol of ethylene oxide added to 1 mol of 1-octanol) as shown in Table 2, and the reaction time was set to 7 hours. Otherwise, the reaction of Example 6 was carried out in the same manner as in Example 1. Furthermore, the OHV of AE2 was 107 mg KOH / g, and the theoretical acid value of its oxidation product (carboxylic acid compound) was 104 mg KOH / g. The formation rate of the carboxylic acid compound at the 7th hour of reaction is summarized in Table 2.

[0261] <Comparative Example 1>

[0262] Bi ion source was added as shown in Table 1, and the reaction of Comparative Example 1 was otherwise performed in the same manner as in Example 1. The formation rates of carboxylic acid compounds at the 24th hour of the reaction are summarized in Table 1.

[0263] <Comparative Example 2>

[0264] A pH meter (Nisshin Rika Co., Ltd.) was installed in the reaction vessel, and a 48% sodium hydroxide aqueous solution (Kanto Chemical Co., Ltd.) was added as an alkali to maintain a constant pH of 7.0 during the reaction. The reaction time was set to 9 hours, and the reaction was carried out. Otherwise, the reaction of Comparative Example 2 was carried out in the same manner as in Example 1. The rate of formation of carboxylic acid compounds was calculated using the following method, and the rate of formation of carboxylic acid compounds at the third hour of reaction is summarized in Table 3.

[0265] (Calculation of the formation rate of carboxylic acid compounds when an alkali agent is added)

[0266] Add 0.5 g of 6M hydrochloric acid (manufactured by Fujifilm and Koichi Chemical Co., Ltd.) to 1 g of the sampled reaction solution, mix thoroughly, and filter using a syringe. Then add 1 mL of methylation reagent (reagent name "TMSI-H", manufactured by GL Science) to the substance that has undergone oil-water separation after standing, react at 70°C for 10 minutes, filter using a syringe, and perform GC (gas chromatography) analysis.

[0267] (GC assay conditions)

[0268] • GC device: Agilent Technologies 6850 (Model: Agilent19091A-102E, manufactured by Agilent Technologies)

[0269] ·Column: Ultra1 Methyl Siloxane (25.0m×200μm×0.33μm)

[0270] Injection temperature: 300℃

[0271] • Detector temperature: 300℃

[0272] Temperature program:

[0273] Hold at 100°C for 5 minutes, then increase the temperature to 300°C at a rate of 5°C / min (total 45 minutes), and then hold at 300°C for 40 minutes (total 90 minutes program).

[0274] Injection volume: 1.0 μL

[0275] • Shift ratio: 25.0:1

[0276] Total flow rate: 28.2 mL / min (Gas: He)

[0277] <Comparative Example 3>

[0278] A 48% sodium hydroxide aqueous solution (manufactured by Kanto Chemical Co., Ltd.) was added as an alkaline agent to maintain a constant pH of 12.0 during the reaction. The reaction was carried out for 9 hours, otherwise, the reaction was carried out in the same manner as Comparative Example 2. The rate of formation of carboxylic acid compounds was calculated using the method described in Comparative Example 2, and the rate of formation of carboxylic acid compounds at the third hour of reaction is summarized in Table 3.

[0279] <Reference Example 1>

[0280] In Example 1, the catalyst was separated and recovered from the reaction solution after the reaction was completed. The recovered catalyst was then added in place of the Bi ion source and the Pt supported on the support. The reaction time was set to 17 hours, and the reaction was carried out in the same manner as in Example 1. It should be noted that the total amount of catalyst recovered in Example 1 was 17.80 g. The composition of the recovered catalyst, calculated based on the amount added in Example 1, was as follows: 10 g of 5% Pt / C and bismuth oxide, 1.56 g of water, and 6.24 g of organic compounds (unreacted AE1 and carboxylic acid compounds). The formation rate of carboxylic acid compounds at the 17th hour of reaction is summarized in Table 4.

[0281] [Table 1]

[0282] Table 1

[0283]

[0284] *1: Total amount of ion-exchanged water and water-containing water from platinum catalyst.

[0285] *2: Total amount of ion-exchanged water, water content from platinum catalyst, and water content from bismuth ion source.

[0286] [Table 2]

[0287] Table 2

[0288]

[0289] *1: Total amount of ion-exchanged water and water-containing water from platinum catalyst.

[0290] [Table 3]

[0291] Table 3

[0292]

[0293] *1: Total amount of ion-exchanged water and water-containing water from platinum catalyst.

[0294] *2: Total amount of water from ion-exchanged water, water from the platinum catalyst, and water from the alkali agent.

[0295] [Table 4]

[0296] Table 4

[0297]

[0298] *1: The total amount of catalyst recovered from Example 1 (17.80 g) will be added.

[0299] (Except for the catalyst, it contains 1.56g of water and 6.24g of organic compounds (unreacted AE1 and EC))

[0300] *2: Total amount of ion-exchanged water and water-containing water from platinum catalyst.

[0301] *3: Total amount of water containing moisture from ion-exchanged water and the catalyst recovered from Example 1.

[0302] According to Tables 1-4, the Pt / Bi composite catalyst obtained by mixing Pt and Bi ion sources supported on a support and reacting in the presence of an organic compound having one primary hydroxyl group, under conditions where the minimum pH value during the reaction is less than 7, exhibits a high rate of carboxylic acid compound formation at any reaction time, thus efficiently yielding oxides of the target organic compound. Furthermore, in Reference Example 1, where the catalyst from Example 1 was separated, recovered, and reused for the oxidation reaction of an organic compound, a high rate of carboxylic acid compound formation was also observed.

[0303] On the other hand, regarding the Pt / Bi composite catalyst of Comparative Example 1 without the addition of a Bi ion source, the carboxylic acid compound content was about 74% at 24 hours, which could not efficiently yield the oxide of the target organic compound.

[0304] Furthermore, regarding the Pt / Bi composite catalysts of Comparative Examples 2 and 3, which were prepared under conditions where an alkaline agent was added to the reaction and the minimum pH value of the reaction was set to 7 or higher, the carboxylic acid compound formation rates at the third hour of the reaction were 16.7% and 5.4%, respectively, which were lower than the carboxylic acid compound formation rate of 37.9% at the third hour of the reaction in Example 1. This is a result of the poor reaction efficiency of the oxidation reaction of organic compounds.

[0305] Furthermore, the formation rate of carboxylic acid compounds at the 17th hour of the reaction in Reference Example 1 was 91.3%, which was higher than the 81.6% formation rate of carboxylic acid compounds at the 17th hour of the reaction in Example 1. This is believed to be because the catalyst in Reference Example 1 was a catalyst obtained by separating and recovering the catalyst from Example 1. Therefore, it was a case of using a highly active Pt-Bi / C catalyst that was presumably already formed in the system, thus eliminating the time for catalyst formation in the system and starting the oxidation reaction of organic compounds immediately after the start of the reaction in Reference Example 1.

[0306] Industrial availability

[0307] The method for producing oxides of the present invention can efficiently produce oxides of organic compounds in the presence of a Bi ion source and Pt supported on a carrier, and can be used in conjunction with the production of a Pt / Bi composite catalyst. Therefore, without the need for additional equipment or processes for producing catalysts, oxides of organic compounds can be produced efficiently, and the resulting oxides of organic compounds can be used in a wide range of fields as detergents, softeners, wetting agents, dyeing auxiliaries, etc.

[0308] Furthermore, the method for manufacturing the Pt / Bi composite catalyst of the present invention can also produce a catalyst exhibiting high activity for the dehydrogenation reaction of organic compounds in the presence of organic compounds as raw materials for oxides, and can be used in conjunction with the oxidative dehydrogenation reaction of organic compounds. Therefore, without the need for additional equipment or processes for manufacturing catalysts, oxides of organic compounds can be produced efficiently, and the obtained Pt / Bi composite catalyst can be suitably used in reactions that cause the dehydrogenation of organic compounds to produce oxides of said organic compounds.

Claims

1. A method for manufacturing an oxide, wherein, In the presence of a Pt or Bi ion source supported on a carrier and water, an organic compound having one primary hydroxyl group undergoes a dehydrogenation reaction under conditions where the minimum pH reached during the reaction is less than 7 and no alkali is added, to obtain an oxide of the organic compound. Among them, the preparation of Pt / Bi composite catalysts, A Bi ion source is added at the beginning of the dehydrogenation reaction or during the reaction. The Bi ion source is selected from at least one of bismuth nitrate pentahydrate, bismuth oxide, basic bismuth carbonate, and bismuth hydroxide. The oxide of the organic compound is a carboxylic acid compound. The organic compound is an aliphatic alcohol or a polyoxyalkylene alkyl ether. The aliphatic alcohol or polyoxyalkylene alkyl ether is one or more of the following general formula (1) or general formula (2). R 1 O-H (1) In general formula (1), R 1 It is a monovalent aliphatic hydrocarbon group with 2 or more carbon atoms and less than 40 carbon atoms. R 2 O-(AO) n -H (2) In general formula (2), R 2 It represents a monovalent aliphatic hydrocarbon group with 2 or more carbon atoms and less than 40 carbon atoms, A represents an alkyldiyl group with 2 or more carbon atoms and less than 4 carbon atoms, AO represents an alkeneoxy group, and n is the average number of moles of alkeneoxy groups added, which is more than 1 and less than 30.

2. The method for manufacturing the oxide according to claim 1, wherein, The Bi ion source is selected from at least one of bismuth nitrate pentahydrate and bismuth oxide.

3. The method for manufacturing the oxide according to claim 1 or 2, wherein, The amount of the Bi ion source added is more than 0.01 parts by mass and less than 0.3 parts by mass relative to 100 parts by mass of the organic compound.

4. The method for manufacturing the oxide according to claim 1 or 2, wherein, The mass ratio of Bi to Pt, expressed as an atomic ratio, is 0.1 or more and 1.2 or less.

5. The method for manufacturing the oxide according to claim 1 or 2, wherein, R in the general formula (1) 1 It is a straight-chain primary alkyl group.

6. The method for manufacturing the oxide according to claim 1 or 2, wherein, R in general formula (2) 2 It is a straight-chain primary alkyl group.

7. The method for manufacturing the oxide according to claim 1 or 2, wherein, In the general formula (2), A is ethylidene or propylidene.

8. The method for manufacturing the oxide according to claim 1 or 2, wherein, In the general formula (2), n is 12 or less.

9. The method for manufacturing the oxide according to claim 1 or 2, wherein, The carboxylic acid compound is an ether carboxylic acid obtained by oxidizing a polyoxyalkylene alkyl ether.

10. The method for manufacturing the oxide according to claim 1 or 2, wherein, The carrier is activated carbon.

11. A method for manufacturing an oxide, wherein, In the presence of a Pt / Bi composite catalyst supported on a Pt support, a Bi ion source, and water, an organic compound with one primary hydroxyl group undergoes a dehydrogenation reaction under conditions where the minimum pH reached during the reaction is less than 7 and no alkali is added, to obtain an oxide of the organic compound. Among them, the regeneration of the Pt / Bi composite catalyst, A Bi ion source is added at the beginning of the dehydrogenation reaction or during the reaction. The Bi ion source is selected from at least one of bismuth nitrate pentahydrate, bismuth oxide, basic bismuth carbonate, and bismuth hydroxide. The oxide of the organic compound is a carboxylic acid compound. The organic compound is an aliphatic alcohol or a polyoxyalkylene alkyl ether. The aliphatic alcohol or polyoxyalkylene alkyl ether is one or more of the following general formula (1) or general formula (2). R 1 O-H (1) In general formula (1), R 1 It is a monovalent aliphatic hydrocarbon group with 2 or more carbon atoms and less than 40 carbon atoms. R 2 O-(AO) n -H (2) In general formula (2), R 2 It represents a monovalent aliphatic hydrocarbon group with 2 or more carbon atoms and less than 40 carbon atoms, A represents an alkyldiyl group with 2 or more carbon atoms and less than 4 carbon atoms, AO represents an alkeneoxy group, and n is the average number of moles of alkeneoxy groups added, which is more than 1 and less than 30.

Images