JP2006265227A - METHOD FOR PRODUCING alpha,beta-UNSATURATED ALDEHYDE AND/OR alpha,beta-UNSATURATED CARBOXYLIC ACID - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an α,β-unsaturated aldehyde and/or an α,β-unsaturated carboxylic acid by a simple process. <P>SOLUTION: The method for producing an α,β-unsaturated aldehyde and/or an α,β-unsaturated carboxylic acid comprises dehydrating and oxidizing an alcohol in a liquid phase in the presence of molecular oxygen and a noble metal-containing catalyst at 110-250°C. Otherwise the method for producing an α,β-unsaturated aldehyde and/or an α,β-unsaturated carboxylic acid comprises dehydrating and oxidizing an alcohol in a liquid phase in the presence of molecular oxygen, a noble metal-containing catalyst and an acidic substance. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a process for producing α, β-unsaturated aldehydes and / or α, β-unsaturated carboxylic acids from alcohols in the liquid phase.

  For example, Patent Document 1 discloses a method for producing an α, β-unsaturated carboxylic acid from an olefin or an α, β-unsaturated aldehyde in the presence of molecular oxygen and a palladium-containing catalyst in a liquid phase. Yes. When an olefin is used as a raw material in this production method, an α, β-unsaturated aldehyde is also produced. Therefore, an α, β-unsaturated aldehyde and / or α, β-unsaturated from an olefin depending on the purpose. It is applicable as a method for producing carboxylic acid.

Patent Document 2 discloses a method for producing methacrolein and methacrylic acid from t-butanol in the gas phase in the presence of molecular oxygen and a molybdenum-bismuth-iron-based catalyst.
JP 2004-141863 A JP 2004-130261 A

  According to the method of Patent Document 2, it is considered possible in principle to produce α, β-unsaturated aldehyde and / or α, β-unsaturated carboxylic acid from not only t-butanol but also other alcohols. Since the method described in Patent Document 2 is a gas phase reaction, there are problems such as a large apparatus such as a reactor to be used and a high reaction temperature.

  In general, the apparatus becomes smaller when a liquid phase reaction is used, but the method of Patent Document 1 does not react with alcohol such as t-butanol, and as it is, α, β-unsaturated aldehyde and / or α, β-unsaturated. Carboxylic acid cannot be produced. Therefore, it is necessary to add a dehydration reaction step for producing an olefin from an alcohol such as t-butanol. Since the dehydration reaction for producing olefin from alcohol is an endothermic reaction, energy for heating is required during the reaction. On the other hand, since the oxidation reaction for producing α, β-unsaturated aldehyde and / or α, β-unsaturated carboxylic acid from olefin is an exothermic reaction, heat removal is required. As described above, separately providing the dehydration reaction step and the oxidation reaction step not only increases the number of reaction steps, but is actually difficult to carry out in one container, which is economically disadvantageous.

  Accordingly, an object of the present invention is to provide an α, β-unsaturated aldehyde and / or α, β-unsaturated in which a dehydration reaction and an oxidation reaction of an alcohol can be carried out in a single container and in one stage in the liquid phase. The object is to provide a method for producing a carboxylic acid.

  The present invention relates to a process for producing an α, β-unsaturated aldehyde and / or an α, β-unsaturated carboxylic acid from an alcohol in the presence of molecular oxygen and a noble metal-containing catalyst in the liquid phase. This is a method for producing an α, β-unsaturated aldehyde and / or an α, β-unsaturated carboxylic acid which dehydrates and oxidizes an alcohol at ° C.

  The present invention also relates to a method for producing an α, β-unsaturated aldehyde and / or an α, β-unsaturated carboxylic acid from an alcohol, wherein molecular oxygen, noble metal-containing catalyst, and acidic substance are contained in the liquid phase. It is a method for producing an α, β-unsaturated aldehyde and / or an α, β-unsaturated carboxylic acid which dehydrates and oxidizes an alcohol in the presence.

  According to the present invention, α, β-unsaturated aldehyde and / or α, β-unsaturated carboxylic acid can be produced from alcohol in a liquid phase by a simple process.

  In the present invention, an α, β-unsaturated aldehyde and / or α, β- is reacted with alcohol in the presence of molecular oxygen and a noble metal-containing catalyst (hereinafter also simply referred to as “catalyst”) in the liquid phase. An unsaturated carboxylic acid is produced.

  Hereinafter, a method for producing an α, β-unsaturated aldehyde and / or an α, β-unsaturated carboxylic acid by reacting an alcohol will be described.

  As the raw material alcohol, an α, β-unsaturated aldehyde and / or an α, β-unsaturated carboxylic acid (hereinafter also referred to as target product) produced by intramolecular dehydration gives an olefin having the same carbon skeleton. Can be used, and examples thereof include isopropanol, t-butanol, n-butanol and the like. The present invention is suitable when the alcohol is isopropanol or t-butanol. In this case, the specific target is acrolein and / or acrylic acid having the same carbon skeleton as propylene when the raw material is isopropanol, and methacrochrome having the same carbon skeleton as isobutylene when the raw material is t-butanol. Rain and / or methacrylic acid.

  Although the solvent (reaction solvent) used for reaction is not specifically limited, Water, ketones, organic acid, organic acid ester, hydrocarbons, etc. can be used. Examples of ketones include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, di-n-propyl ketone, and diisopropyl ketone. Examples of organic acids include acetic acid, n-valeric acid, isovaleric acid and the like. Examples of the organic acid esters include ethyl acetate and methyl propionate. Examples of hydrocarbons include hexane, cyclohexane, and toluene. Moreover, alcohol which is a reaction raw material can also be used as a solvent, In this case, it functions as a solvent and a raw material. Among these, ketones having 3 to 6 carbon atoms, t-butanol, and isopropanol are preferable. The solvent may be one type or a mixed solvent of two or more types.

  Moreover, when using at least 1 sort (s) of alcohols, ketones, and organic acid esters, it is preferable to use it as a mixed solvent with water. The amount of water in the mixed solvent is not particularly limited, but is preferably 2% by mass or more and more preferably 5% by mass or more with respect to the mass of the mixed solvent. Moreover, 70 mass% or less is preferable, and 50 mass% or less is more preferable. The mixed solvent is desirably uniform, but may be used in a non-uniform state.

  This reaction may be carried out in either a continuous type or a batch type, but in view of productivity, the continuous type is preferred industrially.

  When a solvent other than alcohol is used, the amount of alcohol as a raw material in the reaction solution is preferably 0.5% by mass or more, and more preferably 2% by mass or more with respect to the solvent present in the reactor.

  As the molecular oxygen source used in the liquid phase oxidation reaction, air is economical, but pure oxygen or a mixed gas of pure oxygen and air can also be used. If necessary, air or pure oxygen is mixed with nitrogen, dioxide. A mixed gas diluted with carbon, water vapor or the like can also be used. The gas such as air is preferably supplied in a pressurized state into a reaction vessel such as an autoclave.

  When a solvent other than alcohol is used, the amount of molecular oxygen is preferably 0.1 mol or more, more preferably 0.3 mol or more, and even more preferably 0.5 mol or more with respect to 1 mol of alcohol. Moreover, 30 mol or less is preferable, 25 mol or less is more preferable, and 20 mol or less is further more preferable. When using alcohol as a solvent, 0.005 mol or more is preferable with respect to 1 mol of alcohol, and 0.01 mol or more is more preferable. Moreover, 10 mol or less is preferable and 5 mol or less is preferable.

  The catalyst is preferably used in a state suspended in the reaction solution, but may be used in a fixed bed. The amount of the catalyst used is preferably 0.1% by mass or more, more preferably 0.5% by mass or more as a catalyst present in the reactor with respect to the solution present in the reactor performing liquid phase oxidation. 1% by mass or more is more preferable. Moreover, 30 mass% or less is preferable, 20 mass% or less is more preferable, and 15 mass% or less is further more preferable.

  The reaction temperature and reaction pressure are appropriately selected depending on the solvent used and the reaction raw materials. The reaction temperature affects the reaction rate and the productivity of the target substance (production amount per unit time). In general, the temperature is preferably 50 ° C or higher, more preferably 70 ° C or higher, and still more preferably 90 ° C or higher. Considering the reaction rate and the productivity of the target substance, 110 ° C. or higher is particularly preferable. Moreover, 250 degrees C or less is preferable and 200 degrees C or less is more preferable. The reaction pressure is preferably 0 MPa or more (gauge pressure; hereinafter, all pressures are expressed as gauge pressures), and more preferably 2 MPa or more. Moreover, 10 MPa or less is preferable and 7 MPa or less is more preferable.

In the present invention, the reaction can be carried out in the presence of an acidic substance. The acidic substance described here is a substance having H ₀ (Hammett's acidity function) of +4.8 or less. H ₀ can be measured using a Hammett indicator (color development indicator). Specifically, methyl red, which is a Hammett indicator, is a substance that exhibits an acidic color.

  As an effect of adding an acidic substance, it can be mentioned that alcohol can be dehydrated to efficiently convert to an olefin, thereby improving the reaction rate of the oxidation reaction step. Examples of the acidic substance used in the present invention include inorganic acids, heteropolyacids and salts thereof, and solid acids. Examples of inorganic acids include sulfuric acid and phosphoric acid. Examples of heteropolyacids and salts thereof (hereinafter also referred to as heteropolyacids (salts)) include heteropolyacids such as phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, and silicotungstic acid, and salts of these heteropolyacids. It is done. Examples of the solid acid include metal oxides such as silica, alumina, silica alumina, γ-alumina, zirconia, and titania, various zeolites such as HY-type zeolite and mordenite, and strongly acidic ion exchange resins. Among these, when considering the material of the apparatus, separation, and treatment of waste acid, a solid acid is preferable, and γ-alumina, zirconia, titania, various zeolites, and strongly acidic ion exchange resins are more preferable. The acidic substance can be used alone or in combination of two or more. The solid acid can also be present in the reaction system as a support for the noble metal-containing catalyst described later. As the carrier in this case, HY type zeolite, silica, silica alumina, zirconia, titania, strongly acidic ion exchange resin and the like are preferable. The solid acid may be modified with a metal ion or the like.

  In a preferred embodiment of the present invention, the reaction temperature is set to 50 to 250 ° C. in the presence of an acidic substance. The presence of an acidic substance in this way allows the reaction to be performed even at a relatively low temperature. The reaction temperature in this case is preferably 50 to 200 ° C, more preferably 70 to 150 ° C. In the absence of an acidic substance, the reaction temperature is set to 110 to 250 ° C. Thus, even when no acidic substance is present, the reaction can proceed at a temperature of 110 ° C. or higher. In this case, the reaction temperature is preferably 110 to 230 ° C, more preferably 120 to 200 ° C.

  The concentration of the acidic substance is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and particularly preferably 0.5% by mass or more with respect to the reaction solvent. Moreover, 50 mass% or less is preferable, 40 mass% or less is more preferable, and 30 mass% or less is especially preferable.

  The catalyst used in the present invention is a noble metal-containing catalyst. The noble metal contained in the catalyst is palladium, platinum, rhodium, ruthenium, iridium, gold, silver, or osmium. Among them, palladium, platinum, rhodium, ruthenium, iridium, and gold are preferable, and palladium is particularly preferable. The catalyst may contain two or more kinds of noble metals, and may contain elements other than noble metals.

  The catalyst used in the present invention may contain a metal component other than the noble metal. Examples of the metal component other than the noble metal include copper, antimony, tellurium, lead, and bismuth. From the viewpoint of developing high catalytic activity, it is preferable that 50% by mass or more of the metals contained in the catalyst is a noble metal.

  The catalyst may be either a supported catalyst in which a noble metal is supported on a support, or a non-supported catalyst that does not use a support, but a supported catalyst is preferred because the catalyst and the reaction liquid can be easily separated. In the case of a supported catalyst, the loading ratio of the metal component containing the noble metal with respect to the carrier is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more with respect to the carrier before loading. . Moreover, 40 mass% or less is preferable, 30 mass% or less is more preferable, and 20 mass% or less is further more preferable.

  As the catalyst, for example, a commercially available catalyst, a catalyst produced by reducing a compound containing a noble metal element in an oxidized state (hereinafter also referred to as a noble metal compound), or the like can be used. When using a commercially available catalyst, it is preferable to use what was activated by making a catalyst and a reducing agent contact.

  Hereinafter, a method for producing a catalyst by reducing a noble metal compound will be described.

  The noble metal compound to be used is not particularly limited, but noble metal chlorides, oxides, acetates, nitrates, sulfates, tetraammine complexes and acetylacetonato complexes are preferred, and noble metal chlorides, acetates and nitrates are more preferred. . When producing a catalyst containing a metal component other than a noble metal, a metal compound such as a corresponding metal salt or oxide is used in combination.

  The reduction treatment is performed by bringing the noble metal compound into contact with a reducing agent. The reduction treatment may be performed either in the liquid phase or in the gas phase, and is not particularly limited. Below, the reduction process in a liquid phase is mainly demonstrated.

  First, a solution in which a noble metal compound is dissolved in a solvent is prepared. The concentration of the noble metal compound in the solution is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and particularly preferably 0.5% by mass or more. Moreover, 20 mass% or less is preferable, 10 mass% or less is more preferable, and 7 mass% or less is especially preferable.

  When producing a catalyst supported on a carrier, the carrier is immersed in this solution or impregnated with this solution (pore filling), and a reducing agent is added to reduce the noble metal compound. And a method of preparing a catalyst precursor in which a noble metal salt is dispersed on a support and then reducing with a reducing agent, heat treating the catalyst precursor to make at least a part of the noble metal salt an oxide of a noble metal, and The catalyst can be produced by a method of reducing with a reducing agent.

  Among these methods, the method of reducing the oxide after heat treatment is preferable. When the heat treatment is performed, the heat treatment temperature is preferably equal to or higher than the thermal decomposition temperature of the noble metal salt. Moreover, 800 degrees C or less is preferable and 700 degrees C or less is more preferable. The rate of temperature rise to a predetermined heat treatment temperature is not particularly limited, but in order to obtain a good dispersion state of noble metal atoms in the finally obtained noble metal-containing catalyst, the rate of temperature rise is preferably 1 ° C./min or more, and 10 ° C. / Min or less is preferable. The holding time after reaching the predetermined heat treatment temperature is not particularly limited as long as it is a time during which the noble metal salt is decomposed, but is preferably 1 hour or longer, and preferably 12 hours or shorter.

  In addition, the loading method of the metal compound used when producing a catalyst containing a metal component other than the noble metal is not particularly limited, but it can be performed in the same manner as the method of loading the noble metal compound. Further, the metal compound can be supported before the noble metal compound is supported, can be supported after the noble metal compound is supported, or can be supported simultaneously with the noble metal compound.

  The carrier is not particularly limited as long as it can carry a noble metal. For example, activated carbon, carbon black, silica, alumina, silica alumina, magnesia, calcia, titania, zirconia, various zeolites and the like can be mentioned. In the present invention, as described above, a method of heat-treating the support after supporting the noble metal salt on the support is mentioned as a preferred embodiment, and an inorganic oxide support that does not easily burn or deteriorate under the heat-treatment conditions is preferable. For example, silica, alumina, silica alumina, magnesia, calcia, titania, zirconia, and various zeolites are preferable. Of these, silica, titania, zirconia, and various zeolites are more preferable. One type of carrier can be used, or two or more types can be used in combination. Further, as described above, a carrier that functions as a solid acid can also be used.

The specific surface area of the carrier cannot be generally described because the preferred range varies depending on the type of carrier and the like, but in the case of activated carbon, 100 m ² / g or more is preferable, and 300 m ² / g or more is more preferable. Moreover, 5000 m < ² > / g or less is preferable and 4000 m < ² > / g or less is more preferable. Moreover, in the case of zeolite, 100 m < ² > / g or more is preferable and 200 m < ² > / g or more is more preferable. Moreover, 4000 m < ² > / g or less is preferable and 3000 m < ² > / g or less is more preferable. The smaller the specific surface area of the carrier, the more the catalyst with the useful component supported on the surface can be produced, and the larger the specific surface area, the more the catalyst with the useful component supported.

  The solvent used for dissolving the noble metal compound is preferably water. However, depending on the solubility of the noble metal compound and the dispersibility of the carrier when the carrier is used, ethanol, 1-propanol, 2-propanol, n-butanol, t Alcohols such as butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; organic acids such as acetic acid, n-valeric acid and isovaleric acid; and solvents such as hydrocarbons such as heptane, hexane and cyclohexane It can be used alone or in combination. A mixed solvent of these and water can also be used.

  The reducing agent to be used is not particularly limited. For example, hydrazine, formaldehyde, sodium borohydride, hydrogen, formic acid, formic acid salt, ethylene, propylene, 1-butene, 2-butene, isobutylene, 1,3-butadiene, 1- Examples include heptene, 2-heptene, 1-hexene, 2-hexene, cyclohexene, allyl alcohol, methallyl alcohol, acrolein, and methacrolein. The reducing agent can be used alone or in combination of two or more. For reduction in the gas phase, hydrogen is preferred as the reducing agent. In the reduction in the liquid phase, hydrazine, formaldehyde, formic acid, and a salt of formic acid are preferable as the reducing agent.

  The solvent used in the reduction in the liquid phase is preferably water, but depending on the solubility of the reducing agent and the dispersibility of the carrier, ethanol, 1-propanol, 2-propanol, n-butanol, t-butanol Alcohols such as acetone, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; organic acids such as acetic acid, n-valeric acid and isovaleric acid; solvents such as hydrocarbons such as heptane, hexane and cyclohexane alone or Multiple combinations can be used. A mixed solvent of these and water can also be used.

  When a gas is used as a reducing agent in the reduction in the liquid phase, it is preferably carried out in a pressure device such as an autoclave in order to increase the solubility in the solution. In that case, it is preferable to pressurize the inside of a pressurization apparatus with a reducing agent. The pressure is preferably 0.1 MPa or more. Moreover, it is preferable to set it as 1.0 Mpa or less.

  When the reducing agent is a liquid, there is no limitation on the apparatus for reducing the noble metal compound or the noble metal oxide, and the reduction can be performed by adding the reducing agent to the solution. The amount of the reducing agent used at this time is not particularly limited, but it is preferably 1 mol or more and 1 mol or less with respect to 1 mol of the noble metal atom.

  Although the reduction temperature and reduction time vary depending on the reducing agent and the like, the reduction temperature is preferably −5 ° C. or higher, more preferably 15 ° C. or higher. Moreover, 150 degrees C or less is preferable and 80 degrees C or less is more preferable. The reduction time is preferably 0.1 hour or longer, more preferably 0.25 hour or longer, and further preferably 0.5 hour or longer. Moreover, 4 hours or less are preferable, 3 hours or less are more preferable, and 2 hours or less are more preferable.

  After reduction, the catalyst is separated. Although the method for separating the catalyst is not particularly limited, for example, methods such as filtration and centrifugation can be used. The presence or absence of a noble metal in the separated solvent can be easily confirmed by adding a reducing agent such as hydrazine. The amount of noble metal in the solvent can be quantified by elemental analysis such as ICP. The separated catalyst is preferably washed with water or a solvent used in the reaction. The cleaning method is not particularly limited, and can be performed by various methods. The separated and washed catalyst is appropriately dried. It does not specifically limit about the drying method, It can carry out by various methods.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to an Example. Analysis of raw materials and products in the following Examples and Comparative Examples was performed using gas chromatography.

[Example 1]
(Catalyst preparation)
An acetic acid solution in which 1.1 g of palladium acetate was added to 60 g of acetic acid and dissolved by heating at 80 ° C. was prepared. 10 g of zirconia powder (specific surface area 24 m ² / g, average particle size 1 μm, +4.8 <H ₀ ) as a carrier was added to the acetic acid solution and evaporated. Thereafter, as a heat treatment, the temperature was raised from room temperature to 450 ° C. at a rate of 2.5 ° C./min, held at 450 ° C. for 3 hours, and then lowered to room temperature. It added to 50 g of 37 mass% formaldehyde aqueous solution to the heat-processed powder. The mixture was heated to 70 ° C., stirred and held for 2 hours, filtered with suction and filtered and washed with 1000 g of pure water. Furthermore, it dried at 100 degreeC under nitrogen circulation for 2 hours, and obtained 10.5 g of zirconia carrying | support palladium containing catalysts (Palladium metal carrying | support rate: 5 mass%).

(Reaction evaluation)
In an autoclave with a gas inlet (hereinafter referred to as a reactor), 100 g of a 75% by mass aqueous t-butanol solution, 10.5 g of the catalyst prepared above, and 200 ppm of p-methoxyphenol as a radical trapping agent were added to the reaction solvent to react. The vessel was sealed.

  Next, stirring was started at 1000 rpm, and the temperature was raised to 130 ° C. After completion of the temperature increase, nitrogen was introduced into the reactor up to an internal pressure of 2.4 MPa, and then further pressurized with compressed air to an internal pressure of 4.8 MPa to initiate the reaction. At this point, about 35 mmol oxygen (about 65 mmol) was introduced. Although the internal pressure decreased as the reaction proceeded, pure oxygen was added to an internal pressure of 4.8 MPa when the internal pressure decreased by 0.1 MPa. The added pure oxygen was 0.9 MPa in total. The reaction was terminated by stirring for 60 minutes in this state.

  After completion of the reaction, the liquid in the reactor was cooled to about 10 ° C. in an ice bath. A gas collection bag was attached to the gas outlet of the reactor, and the gas outlet was opened to collect all gas components. 1 g of the reaction solution was collected from the reactor, and the catalyst and the reaction solution were separated using a membrane filter (pore size: 0.5 μm). Each component contained in the collected reaction liquid and gas was quantified by gas chromatography. The evaluation results are shown in Table 1.

[Example 2]
(Catalyst preparation)
The same operation as in Example 1 was performed except that silica powder (specific surface area of 528 m ² / g, average particle size of 58 μm, +3.3 <H ₀ ≦ + 4.0) was used as the carrier. It was. As a result, 10.5 g of a silica-supported palladium-containing catalyst (palladium metal support: 5.0% by mass) was obtained.

(Reaction evaluation)
The reaction was evaluated in the same manner as in Example 1 except that 10.5 g of the catalyst was used. The added pure oxygen was 1.6 MPa (about 115 mmol) in total. The results are shown in Table 1.

[Comparative Example 1]
(Reaction evaluation)
Except for using 10.0 g of silica powder (specific surface area 528 m ² / g, average particle size 58 μm, +3.3 <H ₀ ≦ + 4.0) on which palladium is not supported, the same as Example 1 was used. The reaction was evaluated. Since the reaction did not proceed, pure oxygen was not added. The results are shown in Table 1.

[Example 3]
(Catalyst preparation)
HY-type zeolite carrier (SiO ₂ / Al ₂ O ₃ (mol ratio) = 110, specific surface area 736 m ² / g, average particle size 3.3 μm, −8.2 <H ₀ ≦ −5. The same operation as in Example 1 was performed except that 6) was used. As a result, 10.5 g of a HY-type zeolite-supported palladium-containing catalyst (palladium metal support rate: 5% by mass) was obtained.

(Reaction evaluation)
The reaction was evaluated in the same manner as in Example 1 except that 10.5 g of the catalyst was used and the reaction temperature was 90 ° C. The added pure oxygen was 0.8 MPa (about 58 mmol) in total. The results are shown in Table 1.

[Example 4]
(Catalyst preparation)
HY-type zeolite carrier (SiO ₂ / Al ₂ O ₃ (mol ratio) = 70, specific surface area 757 m ² / g, average particle size 2.8 μm, −8.2 <H ₀ ≦ −5. The same operation as in Example 1 was performed except that 6) was used. As a result, 10.5 g of a HY-type zeolite-supported palladium-containing catalyst (palladium metal support rate: 5.0% by mass) was obtained.

(Reaction evaluation)
The reaction was evaluated in the same manner as in Example 1 except that 10.5 g of the catalyst was used and the reaction was completed in 50 minutes. The added pure oxygen was 0.8 MPa (about 58 mmol) in total. The results are shown in Table 1.

[Example 5]
(Catalyst preparation)
1.1 g of palladium acetate and 60 g of an 88% by mass aqueous acetic acid solution were dissolved by heating at 80 ° C. This solution was charged into an autoclave together with 5.0 g of activated carbon powder (specific surface area 780 m ² / g, average particle size 30 μm) and sealed. Agitation was started at 500 rpm, and the system was purged with nitrogen with nitrogen gas. Then, after cooling the temperature of the internal liquid to 10 ° C. or lower, propylene was introduced to an internal pressure of 0.5 MPa and held at 70 ° C. for 1 hour. After 1 hour, the temperature of the internal liquid was cooled to 20 ° C. or lower to release the internal pressure. The obtained slurry was subjected to suction filtration under a nitrogen stream, and then filtered and washed with 1000 g of pure water. Furthermore, it dried at 100 degreeC under nitrogen circulation for 2 hours, and obtained the activated carbon carrying | support palladium containing catalyst (palladium metal carrying | support rate: 10 mass%) 5.5g.

(Reaction evaluation)
100 g of 75 mass% acetone aqueous solution, 6 g of t-butanol, 3 g of Amberlyst-15 dried product (trade name, strongly acidic ion exchange resin, functional group; -SO ₃ H, H ₀ ≦ -8.2) manufactured by Organo, 5.5 g of the prepared catalyst and 200 ppm of p-methoxyphenol as a radical trapping agent were added to the reaction solvent, and the reactor was sealed. The subsequent operation was the same as that of Example 1 except that the reaction temperature was 90 ° C. and the reaction was completed in 50 minutes. The added pure oxygen was 0.6 MPa (about 43 mmol) in total. The results are shown in Table 1.

[Example 6]
(Reaction evaluation)
Reaction evaluation was performed in the same manner as in Example 5 except that 100 g of the 75 mass% acetone aqueous solution and 6 g of t-butanol used in Example 5 were changed to 100 g of 75 mass% t-butanol aqueous solution. The added pure oxygen was 1.4 MPa (about 100 mmol) in total. The results are shown in Table 1.

[Comparative Example 2]
(Reaction evaluation)
Reaction evaluation was performed in the same manner as in Example 6 except that the Amberlyst-15 dried product (trade name of Organo Corporation) was not used. Pure oxygen was not added because the reaction did not proceed. The results are shown in Table 1.

Claims (2)

  A method for producing an α, β-unsaturated aldehyde and / or an α, β-unsaturated carboxylic acid from an alcohol in the presence of molecular oxygen and a noble metal-containing catalyst in a liquid phase at 110 to 250 ° C. A process for producing an α, β-unsaturated aldehyde and / or an α, β-unsaturated carboxylic acid wherein   A method for producing an α, β-unsaturated aldehyde and / or an α, β-unsaturated carboxylic acid from an alcohol, wherein the alcohol is reacted in the liquid phase in the presence of molecular oxygen, a noble metal-containing catalyst, and an acidic substance. A method for producing an α, β-unsaturated aldehyde and / or an α, β-unsaturated carboxylic acid to be dehydrated and oxidized.