JP2001072641A - Method for producing aliphatic aldehyde acid and catalyst for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an advantageous method for producing an aliphatic aldehyde acid (for example, adipaldehyde acid) by oxidizing a cyclic ketone (for example, cyclohexanone) and a catalyst for the production thereof. SOLUTION: The composite comprises a complex in which at least one metal element belonging to Groups 4 to 11 of the periodic table is supported in a liquid phase. And an immobilized catalyst for the production of an aliphatic aldehyde acid prepared in the presence of a basic compound in an amount of from 0.01 to 50 times (molar ratio), and a cyclic ketone using the catalyst, preferably in the presence of water. A method for producing an aliphatic aldehyde acid by oxidizing with oxygen.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an aliphatic aldehyde acid, particularly adipaldehyde acid (5-formylpentanoic acid), and a catalyst useful for the production thereof. Specifically, a catalyst for producing an aliphatic aldehyde acid by oxidizing a cyclic ketone in which a metal element belonging to Groups 4 to 11 of the periodic table, for example, iron is immobilized on a zeolite carrier in a liquid phase in the presence of a basic compound. The present invention relates to a method for producing adipaldehyde acid from, for example, cyclohexanone using the catalyst, and a method for deriving adipaldehyde acid to ε-caprolactam. Is also provided.

[0002]

2. Description of the Related Art Adipaldehyde acid is a compound useful as a synthetic intermediate.
A method of oxidizing cyclohexanone with molecular oxygen in the presence of water and a copper compound (Japanese Patent Publication No. 47-26768), oxidizing cyclohexanone with molecular oxygen in the presence of water and an iron or iridium compound soluble in the reaction system (Japanese Patent Publication No. 4-2583) and the like.

[0003]

However, the catalysts used in these methods are all iron compounds, iridium compounds or copper compounds which are soluble in the liquid phase. There are three problems as follows. First of all, in the oxidation reaction system of cyclohexanone with oxygen, when a homogeneous catalyst containing iron is used, iron atoms are polymerized through oxygen atoms by using for a long time, inert iron hydroxide, It produces basic iron hydroxide, iron oxide, etc., and its activity decreases with time. Second, a homogeneous catalyst containing copper or iridium has a low reaction rate and is inferior in productivity. Third, when a compound in which a metal counter ion is a halogen is used as a catalyst, the activity is generally high. In that case, however, since a halogen is present in the system, a reactor or a pipe made of a material having high corrosion resistance is used. Equipment is required, which increases manufacturing costs. The present inventors have previously proposed an immobilized catalyst composed of a complex in which iron is supported on a water-insoluble carrier having a solid acidity in order to solve the problems of these homogeneous catalysts (Japanese Patent Application No. Hei 10-284,197). No. 10-365682), this immobilized catalyst overcomes these disadvantages, but has the disadvantage that the activity is slightly lower.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, the zeolite was loaded with a metal element belonging to Groups 4 to 11 of the periodic table in an appropriate amount of a base. The complex prepared by being supported in the liquid phase in the presence of a neutral compound is a reaction that oxidizes aliphatic aldehyde acids, especially cyclohexanone, by oxidation of cyclic ketones in a heterogeneous reaction system to form adipaldehyde acid. The present inventors have found that they exhibit high activity as a catalyst for the present invention, and have reached the present invention.

That is, an object of the present invention is to provide an advantageous method for producing an aliphatic aldehyde acid by oxidizing a cyclic ketone, particularly an adipaldehyde acid by oxidizing cyclohexanone. The gist of the present invention is to provide a method for producing a cyclic ketone (cyclohexanone). In producing an aliphatic aldehyde acid (adipaldehyde acid) by oxidation with molecular oxygen in the presence of an immobilized catalyst,
The immobilized catalyst comprises a composite in which at least one metal element belonging to Group 4 to Group 11 of the periodic table is supported on a solid acidic zeolite in a liquid phase, and the composite is used for loading. 0.01 to the total number of moles of the metal element
The present invention resides in a production method characterized by using a catalyst prepared in the presence of a 50-fold amount (molar ratio) of a basic compound.

Another object of the present invention is to provide a composite comprising a solid acidic zeolite having at least one metal element belonging to Groups 4 to 11 of the periodic table supported in a liquid phase, and
The complex is an aliphatic aldehyde acid (adzide) comprising an immobilized catalyst prepared in the presence of a basic compound in an amount of 0.01 to 50 times (molar ratio) based on the total number of moles of the metal element used during loading. In the catalyst for the production of polyaldehyde acid), a further gist is that cyclohexanone is supported in water and at least one metal element belonging to groups 4 to 11 of the periodic table on water and a solid acidic zeolite in a liquid phase. Immobilized catalyst comprising a complex which has been prepared in the presence of a basic compound in an amount of 0.01 to 50 times (molar ratio) the total number of moles of the metal element used during loading. Is oxidized by molecular oxygen in the presence of to produce an oxidation reactant containing adipaldehyde acid, and then reacts adipaldehyde acid obtained from the oxidation reactant with ammonia and hydrogen in the presence of a hydrogenation catalyst. Let me 6-ami To generate a caproic acid, to produce 6
-A method for producing ε-caprolactam, characterized in that aminocaproic acid is heated and converted into ε-caprolactam by a ring closure reaction.

In a preferred embodiment of the present invention, the oxidation of the cyclic ketone (cyclohexanone) is carried out in the coexistence of water, the basic compound is ammonia, a linear alkylamine or a cyclic alkylamine. At least one metal element belonging to Group 4 to Group 11 is iron.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The immobilized catalyst suitable for the oxidation reaction of the cyclic ketone of the present invention,
The solid acidic carrier is composed of a composite in which at least one metal element belonging to Groups 4 to 11 of the periodic table is supported in a liquid phase on a zeolite as a solid acidic carrier. 0.01 to 50 based on the total number of moles of metal elements
It is necessary to make the basic compound twice as much (molar ratio), and if this condition is not satisfied, sufficient catalytic activity cannot be obtained.

As the zeolite used as a carrier,
Although there is no particular limitation on the crystal structure, it is preferable that the channels constituting the zeolite structure have a size exceeding at least one oxygen eight-membered ring in at least one direction. More preferably, a zeolite having two or more channels, and most preferably three or more channels, satisfying the same conditions is suitable as a carrier. Specifically, IZA (Internationa
l Zeolite Association), the skeletal structure type is expressed as FAU, ERI, FER, BEA, M
OR, MWW, MTW, MFI, MEL and the like are preferable.

In the oxidation reaction of the present invention, it is essential that the zeolite has solid acidity. Therefore, in addition to silicon and oxygen as elements forming the skeleton, aluminum, gallium, indium, boron, iron, titanium, zinc, It must contain at least one of the elements that form acid sites, such as manganese, chromium, cobalt, vanadium, and zirconium. Two or more of these elements may be present in the zeolite framework at the same time. In addition, germanium and tin (hereinafter, silicon, germanium and tin are referred to as T elements) as isomorphous elements of silicon
And the like may be used, and two or more of these elements may be used simultaneously. Of the above-mentioned elements, Al, Ga, In, B
Is the element M, the molar ratio of the elements in the zeolite skeleton T / 2M (however, T and M are the total of each element group) in order to realize a sufficient acid amount and acid strength necessary for this reaction. Is preferably 9 or more and 300 or less.

The specific surface area of the zeolite serving as a carrier is preferably 50 to 1500 m ² / g, more preferably 100 to 1500 m ² / g.
1300 m ² / g, and most preferably from 150~1200m ² / g. Similarly, the average particle size of the zeolite is preferably 0, because if the particle size is too small, the catalyst separation property deteriorates, and if it is too large, the outer surface area becomes small and the diffusion rate of the reaction substrate and the target product becomes large. .05μ
m to 10 μm, more preferably 0.08 μm to 8 μm,
Most preferably, it is 0.1 μm to 6 μm. The average particle diameter in this case refers to the number average value of the diameter of the circle when the area projected on the observation surface of the crystal observed by the scanning electron microscope is converted into an equal area circle.

The immobilized catalyst used in the present invention must contain at least one metal element belonging to Groups 4 to 11 of the periodic table in addition to the elements forming the zeolite skeleton. Specifically, as the metal element, titanium, chromium, manganese, iron, cobalt, nickel,
Copper, iridium and the like, among which iron,
Copper and iridium are preferred, and iron is most preferred.
Further, two or more of these elements may be simultaneously contained.

Further, in the immobilized catalyst of the present invention, in the form used for the reaction, in addition to the metal elements belonging to Groups 4 to 11 of the periodic table, a part of zeolite serves as a counter cation to form protons, lithium, sodium, potassium, Group 1 elements such as rubidium, Group 2 elements such as magnesium, calcium and strontium; Group 12 elements such as zinc; Group 13 elements such as boron, aluminum and gallium;
Alternatively, it may be substituted by an ammonium ion, a tetraethylammonium ion, or the like. Of these elements other than the metal elements of Groups 4 to 11, protons and aluminum are preferred, and protons are most preferred.

Group 4 to 11 supported on zeolite
The optimal value of the amount of the metal element belonging to the group differs depending on the element. For example, when iron is taken as an example, 0.001% to 60%, preferably 0.005% to 50% by weight of zeolite as the iron element is used. %, More preferably 0.01 to
A range of 40% is good. If the supported amount is less than this range, sufficient reaction activity may not be obtained, and if the amount is too large, inactive by-products such as low-dispersion hydroxides and oxides may be generated in addition to the catalytic action. Is not preferred.

The immobilized catalyst of the present invention comprises a composite in which zeolite supports at least one metal element belonging to groups 4 to 11 of the periodic table. Must be done inside. The type of the supporting method is preferably carried out in a batch system due to the nature of the present invention. As a solvent, zeolite is dispersed and
There is no particular limitation as long as it can dissolve a required amount of a compound containing a metal element belonging to Group 11 to Group 11. For example,
Examples include water, methanol, and ethanol. These solvents may be used as a mixture of two or more kinds.

The compound containing a metal element belonging to Groups 4 to 11 to be dissolved in the liquid phase is preferably a compound which is soluble in the solvent to be used, and includes nitrates, sulfates, phosphates, and chlorides of the element. , Inorganic salts such as bromide, acetate,
Organic salts such as oxalate and citrate, organic ligands such as 1,2-ethylenediamine and acetylacetone, and / or
Or a complex having an inorganic ligand, a complex salt, and the like. Among these, a nitrate, a sulfate, a chloride, and a bromide are preferable. The preferred concentration of each element in the solution used for loading varies depending on the type of element. For example, when iron is loaded in an aqueous solvent, the volume concentration of iron is usually from 0.001 mol / l (liter) to the molar concentration of iron. It is 10 mol / l, preferably 0.01 mol / l to 5 mol / l. Furthermore, if the concentration of the slurry containing the element-containing solution and zeolite is too low, the efficiency of the catalyst treatment is reduced, so that the concentration in terms of weight percent is usually 0.1% or more, preferably 1% or more. There is no particular limitation on the upper limit of the slurry concentration as long as the mixture of the solution containing the element and the zeolite shows normal fluidity.

In supporting the metal elements belonging to Groups 4 to 11 on the zeolite by supporting them in the liquid phase,
Although three types of zeolite, a solvent, and a compound containing the metal element (hereinafter sometimes collectively referred to as a substance required to be supported) are required, the order of adding these is not particularly limited. There is no particular limitation on the temperature at the initial stage of loading these necessary substances into the container for supporting, but it is preferable that each substance is in a temperature range from room temperature to the temperature at the time of supporting. The temperature at the time of loading varies depending on the scale of loading operation, the type of each substance, and the like, but is usually at room temperature to 100 ° C. When the temperature at the time of loading exceeds room temperature, for loading, heating may be started at an arbitrary stage from a state in which at least one component of the substance required for loading is supplied to the container to just before the start of loading.
The start of loading in this case refers to the point in time when all the substances necessary for loading have been mixed and the temperature required for loading has been reached.
Therefore, when the support is at room temperature, it can be said that the stage at which all the substances necessary for the support are added to the container is the start of the support.

The atmosphere at the time of loading is not particularly limited. An inert gas such as nitrogen, argon, helium or carbon dioxide, or an inert gas such as air mixed with oxygen,
Alternatively, pure oxygen or the like can be used. At the time of loading, stirring may or may not be performed. When performing stirring, it is preferable to perform the stirring with a stirring power of ³ kW / m ³ or less.
For loading, stirring may be started at any stage after the initial filling in which at least one component of the substance required for loading is supplied to the container. The optional step in this case also includes after the start of loading. In order to carry the metal element more efficiently, the system is depressurized and degassed after all the substances necessary for the loading are added, or the ultrasonic wave is irradiated to improve the contact between the solution and the zeolite. May be performed.

[0019] The immobilized catalyst of the present invention comprises a group 4 to 11 group.
A complex in which a metal element belonging to group III is supported on zeolite in a liquid phase. At the time of preparation, it is necessary that a specific amount of a basic compound be present for the metal element used at the time of support. As the basic compound used in the present invention, a compound having a property that a required amount is dissolved in a solvent used at the time of loading and that can be easily removed from the catalyst by a subsequent heat treatment step is preferable. The compounds having the above properties include the following compounds.

(1) Ammonia, hydrazine (2) Chain alkylamines or polyamines having 1 to 12 total carbon atoms containing 1 to 4 nitrogen atoms, or 1 to 12 total carbon atoms excluding substituents Open-chain alkylamines or polyamines having 1 to 4 arbitrary substituents in the following substituent group (A) at any place containing a nitrogen atom (3) One or two nitrogen atoms are placed on the ring 5 to 6-membered cyclic alkylamines or alkylamines having 1 to 3 optional substituents in the following substituent group (B) at any position including a nitrogen atom (4 A) a 5- to 6-membered lactam containing one or two nitrogen atoms on the ring, or one to three of the following substituent groups (B) at any place containing a nitrogen atom in the lactam (5) aromatic having one benzene ring Aromatic amines (6) A 5- to 10-membered heteroaromatic ring compound having 1 to 3 nitrogen atoms on the ring, or 1 to 3 substitutions at any place containing a nitrogen atom in the heteroaromatic ring compound Base group (B)
(7) Quaternary ammonium salts having a hydroxide ion as a counter ion

Substituent group (A) hydroxyl group, methoxy group, ethoxy group, carboxyl group, formyl group, nitro group, cyano group, trifluoromethyl group, chlorine atom, fluorine atom, thiol group, methylthiol group, sulfonic acid Group Substituent group (B) methyl group, ethyl group, 1-propyl group, 2-propyl group,
Hydroxyl, methoxy, ethoxy, carboxyl, formyl, hydroxymethyl, amino, aminomethyl, nitro, cyano, trifluoromethyl, chlorine, fluorine, thiol, methylthiol, Sulfonic acid group

More specifically, ammonia, hydrazine; methylamine, diethylamine, triethylamine, 1,2-ethylenediamine, 1,4-diazabicyclo [2,2,
2] octane, triethanolamine; pyrrolidine, N-
Methylpiperidine; N-methylpyrrolidinone, 2-piperidinone; aniline, hydroxyaniline; pyridine, pyrazine, pyramidine, pyrrole, imidazole, picoline, quinoline, 4-dimethylaminopyridine, 2,6-dimethylpyridine, 1,4-pyridinium water Oxides: hydroxides such as tetrabutylammonium; Among them, ammonia, methylamine, diethylamine, 1,2-ethylenediamine; pyridine, 4-dimethylaminopyridine,
2,6-dimethylpyridine is preferred, and ammonia is particularly preferred.

The amount of the basic compound to be present at the time of preparing the composite is usually 0.01 to 50 times (molar ratio), preferably 0.05 to 50 times the total number of moles of the metal element used at the time of loading. 20 times (molar ratio), more preferably 0.1 times.
The amount is 1 to 10 times (molar ratio), particularly 0.2 to 5 times (molar ratio). Here, the term “at the time of loading” means a series of processes from the initial stage of filling the container with the required substance into the step of carrying out the loading.

The basic compound can be added at any stage as long as the metal element is supported.
(D). That is, (a) "the basic compound is added to the solution containing the metal element and then the zeolite is added", and (b) "the zeolite is brought into contact with the solvent and then the basic compound is added. Then, a substance containing the metal element or a solution in which the substance containing the metal element is dissolved is added ”, (c)“ After adding all the substances necessary for carrying, a basic compound is added thereto ”(d ) "Adding all the substances necessary for supporting, adding a basic compound after reaching a temperature necessary for supporting and treating for a certain time". In either case, there is an effect of improving the catalytic activity, but among them, the method (c) or (d), in which the structure of zeolite is small and the metal element can be efficiently supported, is preferable.

The temperature at which the basic compound is added may be any temperature from room temperature to the temperature at which it is supported, and may or may not be under stirring. In adding the basic compound, the time required for adding the whole amount varies depending on the scale of the support and the like, but is usually 5 seconds to 2 hours, more preferably 1 second to 2 hours.
0 seconds to 1 hour. At this time, the basic compound may be diluted with an appropriate solvent, and when the basic compound is a gas at normal temperature, the solvent may be diluted with another gas. The operation of supporting the metal element in the presence of the basic compound may be repeated a plurality of times. In addition, a zeolite supporting a metal element in advance without using a basic compound may be further subjected to a supporting operation in the presence of a basic compound, and on the other hand, a supporting operation in the presence of the basic compound. After that, a normal supporting operation may be further performed. When the loading operation is performed a plurality of times, a heat treatment described later may be further performed between the loading operations. When the heat treatment is not performed in the middle, the drying step between the loading operations can be omitted.

It is desirable that the complex (sample) after the loading operation is usually separated by a method such as filtration and washed with water, methanol, ethanol or the like. Then, it is subjected to a drying step and a pulverizing step under normal pressure or reduced pressure conditions.
Drying here refers to losing the solvent until the sample after washing shows properties as a powder, and depending on the type of zeolite used, is generally less than or equal to the dry weight of the zeolite. Refers to the state containing a solvent. It is desirable to subject the obtained dried composite to a heat treatment in order to ensure an improvement in the catalytic activity. The temperature in the heat treatment step is usually from 200 ° C. to 1100 ° C., preferably from 300 ° C. to 1 ° C.
000 ° C, most preferably from 400 ° C to 900 ° C. At 200 ° C or lower, the effect of improving the catalyst activity is small, and 1
If the temperature is higher than 100 ° C., the structure of zeolite itself may be irreversibly destroyed. The heat treatment time of the composite after loading is usually 0.5 minutes to 12 hours,
Preferably, it is 1 minute to 6 hours. The heat treatment time refers to the time during which the catalyst is substantially at the processing temperature, and differs from the actual processing time in the apparatus, even if the processing time is apparently the same, depending on the equipment used and the amount of catalyst. There is also.

The atmosphere during the heat treatment may be an inert gas such as nitrogen, argon, helium, carbon dioxide, a mixed gas of an inert gas such as air and oxygen, or oxygen. Of these, nitrogen or air is preferred. Further, these gases may be mixed with water vapor, nitrogen oxides, sulfur oxides and hydrogen chloride up to 10% by volume. The gas used as the atmosphere may or may not flow during the heat treatment. In the case of circulation, the circulation speed is determined by the weight space velocity (WH) for zeolite or a composite of zeolite and a metal element (iron).
SV) is usually 20 / h or less, preferably 10 / h or less. The heat treatment is generally performed under normal pressure, but may be performed under increased or reduced pressure. The treatment is performed in a fixed bed or fluidized bed using any heating device such as a tubular furnace or a muffle furnace.

[0028] The immobilized catalyst of the present invention comprises a group 4 to 11 group.
An organic compound may be further used in combination with the complex of the metal element belonging to the group and zeolite. The organic compound to be used is not particularly limited as long as the metal element is supported on the zeolite. Specifically, triethylamine, 1,2-ethylenediamine, 1,4-diazabicyclo [2,2,
2] octane, pyridine, 4-picoline, quinoline,
2,2′-bipyridyl, 1,10-phenanthroline,
Compounds having a nitrogen-containing functional group such as dimethylglyoxime, 1,2-cyclohexanedione dioxime, acetohydroxamic acid, dimethylformamide, N-methylpyrrolidone, ethylenediaminetetraacetic acid, porphyrin, or 2,2′-biphenyldiol; Compounds having an oxygen-containing functional group, such as 2,3-butanediol, acetylacetone, and 2-hydroxyacetophenone, or compounds having a nitrogen-containing functional group and an oxygen-containing functional group are preferable. Among them, 2,2′-dipyridyl and 2,2 ′
-Biphenyldiol, 1,10-phenanthroline,
Acetyl acetone is preferred, and these can be used in combination.

By adding these organic compounds, it is possible to suppress the formation of by-products such as a cyclic ketone dimer as a raw material, and to suppress the elution of metal elements into the liquid phase during the reaction. It is. This is a purpose essentially different from that of the basic compound used at the time of the above-described loading, and in order to achieve the purpose, the introduction of these organic compounds must be performed after the heat treatment of the composite after the operation of loading the metal element. The amount of the organic compound to be added is 0.001 to 20, more preferably 0.01 to 1 in a molar ratio with respect to the amount of the metal element belonging to Groups 4 to 11 in the zeolite.
0 is good. There is no particular limitation on the method of adding the organic compound, but usually, any metal element from Group 4 to Group 11 is supported on the zeolite in the liquid phase, and if necessary, further heat treatment is performed. Will be As an addition method, an organic compound is added as it is, and the method is introduced under reduced pressure and heating conditions of room temperature or higher, and is introduced into the surface and / or inside of the carrier, or the organic compound is dissolved in a liquid phase such as methanol, A method of contacting with zeolite can be used.

In the immobilized catalyst of the present invention, the metal elements belonging to Groups 4 to 11 supported on the zeolite can take various states in the pores of the zeolite and / or on the outer surface of the zeolite. For example, there are the following states (1) and (2), and both of these states may exist. (1) Present as iron ions. When iron has a ligand, in addition to the above-mentioned added organic compound, water, hydroxide ion, chloride ion, bromide ion, and iron in the process of supporting iron such as 1,2-ethylenediamine on zeolite together with iron Molecules or ions originally introduced into the pores of the zeolite or originally present in the pores of the zeolite may be coordinated. Further, the ligand of one organic compound may coordinate two or more iron atoms. (2) Iron metal clusters or iron oxide clusters. Also in this case, it may be possible to have a ligand similar to (1). The charge in the entire cluster is preferably from 0 to 3. Further, the number of iron atoms contained in one cluster is not limited, but is preferably 2 to 11.

In the method of the present invention, at least one metal element belonging to Group 4 to Group 11 is supported on the zeolite in the liquid phase in the presence of a specific amount of a basic compound. Using an immobilized catalyst prepared through the above, an oxidative cleavage reaction of a cyclic ketone is performed to produce an aliphatic aldehyde acid. The cyclic ketone used as a raw material is a saturated alicyclic monoketone having 4 to 7 carbon atoms, and specific examples thereof include cyclopentanone, cyclohexanone, and cycloheptanone. Of these, cyclohexanone is particularly preferred. Useful. The reaction conditions in the method of the present invention are as follows if an example of production of adipaldehyde acid from cyclohexanone is shown.

In the case of producing adipaldehyde acid by oxidative cleavage of cyclohexanone using the above-mentioned immobilized catalyst according to the method of the present invention, the reaction conditions are as follows. In the production of adipaldehyde acid in the method of the present invention, the presence of water is not always essential, but it is preferable to carry out the reaction in the presence of water. The amount of water to be used is preferably 0.01 to 1000 times, more preferably about 0.05 to 100 times, more preferably 0.1 to 50 times the weight of cyclohexanone. Depending on the amount of water used, the liquid phase of cyclohexanone and water in the reaction system becomes a homogeneous phase or a suspended phase at the reaction temperature, and any of them may be used to carry out the method of the present invention. Here, water refers not only to water supplied externally as a reaction substrate, but also to water including water produced by the intended reaction and side reactions, and the total amount of water is the above-mentioned fixed amount. I just need to be in.

The amount of the immobilized catalyst to be used is preferably 0.005 or more by weight with respect to water. The upper limit may be within a range where the slurry of the immobilized catalyst and the liquid phase maintains fluidity at least under the reaction conditions. The reaction temperature at the time of carrying out the method of the present invention can be selected from a considerably wide range, for example, 0 ° C to 200 ° C, more preferably 20 ° C to 200 ° C.
160 ° C, most preferably 40 ° C to 140 ° C. The reaction can be sufficiently carried out at normal pressure, but the pressure may be increased to normal pressure or higher. The combination of these temperatures and pressures is desirably such that water and cyclohexanone can be kept in a liquid state.

As the molecular oxygen source used in the reaction, pure oxygen may be used, or it may be used in a diluted form such as air. In order to carry out the reaction at a lower pressure, an oxygen concentration exceeding 10% is preferable, and when considering the explosion limit of the gas phase, the oxygen concentration in the diluent gas is preferably 1% to 10%. Examples of the gas for diluting oxygen include nitrogen, argon, carbon dioxide, neon, helium, hydrogen, butane, propane, ethane, and methane.

Further, an aliphatic hydrocarbon, an aromatic hydrocarbon, an oxygen-containing organic compound, a nitrogen-containing organic compound, a sulfur-containing organic compound, a halogen-containing organic compound, and the like may be present in the reaction system. Examples of these compounds include benzene, cyclohexene, 1,3-cyclohexadiene, hexane, pentane, 1,1′-bicyclohexylidene, 3-cyclohexylidenecyclohexene, 1,1′-bicyclohexenyl, and 1-cyclohexylcyclohexene , Hydrocarbons such as dicyclohexyl, methanol, ethanol,
-Propanol, 2-propanol, 1-butanol,
2-butanol, 1,1-dimethylethanol, 1,2
-Ethanediol, cyclohexanol, cis and t
trans-1,2-cyclohexanediol, cis and trans-1,3-cyclohexanediol, ci
s and trans-1,4-cyclohexanediol,
2-cyclohexen-1-ol, 1,6-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 2- (1-cyclohexenyl) -cyclohexanol, 2-cyclohexylidenecyclohexanol, -Cyclohexylcyclohexanol, 1- (1
-Cyclohexenyl) -cyclohexanol.

Also, acetone, 2-hydroxycyclohexanone, 3-hydroxycyclohexanone, 1,2-cyclohexanedione, 2-cyclohexen-1-one,
3-cyclohexen-1-one, 1,2-epoxycyclohexane, 3,4-epoxycyclohexene, 2,3
-Epoxycyclohexane-1-one, caprolactone, 6-hydroxyhexanal, 5-hydroxyhexanal, 5-hexenal, 1,6-hexanedial, 2- (1-hydroxycyclohexyl) -cyclohexanone, 2- (2-hydroxycyclohexyl) ) -Cyclohexanone, 2- (1-cyclohexenyl) -cyclohexanone, 2-cyclohexylidenecyclohexanone, 2-cyclohexylcyclohexanone, dicyclohexyl ether, and other oxygen-containing organic compounds, hydroperoxycyclohexane, 3-hydroperoxycyclohexene, 4-hydro Peroxycyclohexene, 2-hydroperoxycyclohexanone, 3-hydroperoxycyclohexanone, 4-hydroperoxycyclohexanone, 2-hydro Le oxy cyclohexanol, 3
Organic peroxides such as -hydroperoxycyclohexanol and 4-hydroperoxycyclohexanol can also be mentioned.

Further, adipic acid, monomethyl adipate, dimethyl adipate, pentanedioic acid, monomethyl pentanedioate, dimethyl pentanedioate, butanedioic acid, monomethyl butanedioate, dimethyl butanedioate, 6-hydroxyhexanoic acid, Methyl 6-hydroxyhexanoate, 5-
Formyl-6-hydroxyundecandioic acid, 5-formyl-5-undecenedioic acid, 6- (2-oxocyclohexyl) -6-hydroxyhexanoic acid, 6- (2-oxocyclohexylidene) -hexanoic acid, 5- (1-hydroxycyclohexyl) -5-formylpentanoic acid, 5-
Cyclohexylidene-5-formylpentanoic acid, 5-
Carboxylic acids or carboxylic acid derivatives such as (1-cyclohexenyl) -5-formylpentanoic acid; halogen-containing organic compounds such as 2-chlorocyclohexanone;
2,2′-bipyridyl, 2,2′-biphenyldiol, 1,10-phenanthroline, acetylacetone,
Examples include compounds derived from organic compounds added to a catalyst such as dibenzo [b, d] furan.

Among these compounds, compounds corresponding to arbitrary aldehydes and ketones include arbitrary alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1,1- It may be present as an acetal and / or ketal, or a hemiacetal and / or hemiketal with a compound such as dimethylethanol, cyclohexanol, 2-cyclohexenol, or 2-hydroxycyclohexanone. Further, the compound corresponding to an arbitrary aldehyde or ketone may be present together with a compound corresponding to an arbitrary aldehyde or ketone, in the presence of an aldol condensation or a compound formed by an aldol condensation followed by a dehydration reaction. In this case, the compounds corresponding to the two aldehydes and ketones may be different from each other, or may be two molecules of the same type. Further, a compound formed by dehydration reaction after aldol condensation or aldol condensation due to two carbonyl groups present in one molecule may be present. Further, a compound produced by esterification of any of the above-mentioned carboxylic acids and any of the above-mentioned alcohols may be present. Any alcohol may be present during the reaction with the compound formed by the ether bond. When the above-mentioned compounds are present in a large amount in the reaction system, side reactions are likely to occur and adversely affect the activity of the catalyst. Therefore, the amount of each compound in the reaction solution is usually 20 wt.
%, Preferably 10 wt% or less, more preferably 5 wt% or less.
% Or less.

Further, in the aqueous phase and / or the organic phase,
Up to 15% by weight concentration of ions, complexes, clusters, ionic clusters, oxides, ionic metal oxide clusters, hydroxides, metal oxide colloids, etc., derived from the metal elements of Group 11 to Group 11; More preferably it may be present up to 10%. At this time, there is no particular limitation on the ligand coordinated to the metal element and the valence of the metal element. Similarly, in the aqueous phase and / or the organic phase, cations of Group 1 elements such as sodium ion and potassium ion, cations of Group 2 elements such as magnesium ion and calcium ion, and Group 13 cations such as aluminum ion Elemental cations and the like may be contained up to 15%, more preferably up to 10% by weight based on the immobilized catalyst.

The reaction time or residence time of the oxidation reaction of the present invention varies depending on the reaction conditions, reaction type and the like, but is usually 0.1 to 10 hours, preferably 0.2 to 5 hours.
The type of the reaction may be any of a batch type and a continuous type, and the type of the reactor may be any type such as a stirred suspension bed type, a fixed bed type and a fluidized bed type. Usually, it is industrially advantageous to carry out the reaction continuously using a stirred suspension bed. Hereinafter, an example of a continuous oxidation reaction of cyclohexanone using a stirred suspension bed will be specifically described.

[Outline of Reaction Format] The reaction format is arbitrary, and for example, the following reaction format can be used. A reactor containing the immobilized catalyst of the present invention, water,
Cyclohexanone and an oxygen-containing gas that can serve as a molecular oxygen source are continuously supplied to the reactor, and a reaction mixture containing adipoaldehyde acid and unreacted cyclohexanone is simultaneously removed at the same time. The removed reaction mixture is separated into gases in a gas separation tower, and the separated gases are recycled to the reactor. On the other hand, the aqueous layer containing the immobilized catalyst contained in the removed reaction mixture is separated from the organic layer and then recirculated to the reactor. The organic layer containing the target product is led to a distillation column, where it is separated by distillation into unreacted cyclohexanone, the target product adipaldehyde acid, and other by-product compounds. The recovered cyclohexanone may be recycled to the reactor, and unnecessary by-products may be purged. At this time, when a useful compound is contained in the by-product group, the compound can be taken out in this distillation step. Incidentally, if the separation of the organic layer and the aqueous layer of the reaction mixture containing water taken out of the reactor is insufficient and the organic layer contains an insoluble immobilized catalyst, it is separated,
After extracting the remaining organic layer with an organic solvent,
The organic solvent layer may be led to a distillation column to separate a target product or the like.

[Raw Material Supply Method] At the start of the reaction At least a gas containing an immobilized catalyst, cyclohexanone, and oxygen is present in the reactor after the start of the reaction, and there is no particular limitation on the order in which these reaction materials and the like are added at the stage of initial charging to the reactor. . However, in order to reduce the generation of by-products, it is preferable to coexist water in the reaction system and to avoid contact of cyclohexanone with the immobilized catalyst in the absence of water. As a specific order of addition when water is used, it is preferable to use a mixing and filling method in the following manner. (1-1): After putting the immobilized catalyst into the reactor, water is added, and then cyclohexanone is added. (1-2): Cyclohexanone is charged into a reactor, water is further added, and then an immobilized catalyst is added. (1-3): Cyclohexanone is charged into a reactor, and an aqueous dispersion of an immobilized catalyst which has been brought into contact with water and made into a slurry in advance is added. (1-4): An aqueous dispersion of the immobilized catalyst previously brought into contact with water and made into a slurry is added to the reactor, and cyclohexanone is further added. (1-5): (1-1) to (1) in another container for initial filling.
A suspension is prepared by mixing the immobilized catalyst, water and cyclohexanone using the method of -4), and the suspension is transferred to the reactor in the form of a suspended slurry.

The immobilized catalyst may contain an appropriate amount of water as long as the properties of the powder are maintained. For example, in the case of a catalyst using a FAU-type zeolite as a carrier, the catalyst may contain water up to the dry weight of the composite of zeolite and a metal element. When the reaction temperature exceeds room temperature, (1-1) to (1-5)
The heating may be started at an arbitrary stage of each method.

As for the gas containing oxygen, it is preferable that the immobilized catalyst, water and cyclohexanone are charged to the reactor before being added to the reactor. Further, it is preferable that the immobilized catalyst before filling the reactor, water, and cyclohexanone are separately contacted with a gas containing oxygen in advance,
The oxygen concentration in this case does not necessarily have to be the same as the reaction conditions. Further, the stirring of the reaction mixture and the flow of the gas containing oxygen may be carried out in each of the immobilized catalyst, water and cyclohexanone filling steps, or, if the reaction temperature is higher than room temperature, after the heating step of the reactor and after completion of the heating. You may start from. Further, the stirring and the circulation of the gas containing oxygen do not always need to be started at the same time.

2. Supply of Raw Material (Oxygen) During Continuation of Reaction As the oxidation reaction proceeds, cyclohexanone and oxygen in the reactor decrease. Therefore, it is preferable to continuously react while supplementing these. As a method of supplying oxygen,
Any of the following embodiments can be used. (2-1): A cooling device for refluxing cyclohexanone, water, etc. is installed at the top of the reactor, and a gas containing oxygen is maintained at a certain flow rate or a certain pressure at the top of the cooling device. A method of circulating and supplying oxygen continuously. (2-2): A cooling device for refluxing cyclohexanone, water, etc. is installed at the upper part of the reactor, and a gas containing oxygen is passed at the top of the cooling device. The oxygen concentration in the reactor is measured, A method of continuously supplying oxygen by changing the flow rate or oxygen partial pressure of a gas containing oxygen according to the indicated value. (2-3): An oxygen supply port was installed in the reaction solution.
A method according to 1) or (2-2). (2-4): Keep the pressure in the reactor constant, compensate for the decrease in pressure due to the progress of the reaction by adding pure oxygen, or measure the oxygen concentration in the reactor and adjust the indicated value to A method in which pure oxygen or pure oxygen and a diluent gas are supplied, and the total pressure and the oxygen partial pressure in the reactor are kept constant.

When a gas containing oxygen is allowed to flow, the value of “oxygen supply amount (mol / h) / cyclohexanone supply amount (mol / h)” is 0.01 to 200;
Preferably, it is performed between 0.05 and 100. When the gas containing oxygen is directly supplied into the reaction mixture, the shape and size of the supply port are not particularly limited.
The supply port may be attached to a stirring shaft or a stirring blade, or may be separately provided independently of them.

Supply of Raw Material (Cyclohexanone) The method for supplying cyclohexanone to the reactor may be any of the following embodiments, but it is preferable to use the method (3-1) for stabilizing the reaction. . (3-1): A method of continuously supplying to the reactor without interruption (3-2): A method of intermittently supplying after a certain interval time

[Reaction Method] The present reaction may be carried out with or without stirring, but it is preferable to carry out stirring. In that case, the stirring power is usually 4 W / liter or less, more preferably 3 W / liter or less, per volume of the reaction mixture containing the immobilized catalyst. If the stirring power is too large, crushing of the immobilized catalyst is liable to occur, and as a result, the separability of the immobilized catalyst and the catalytic activity are lowered, which is not preferable. The number of stirring shafts may be one, two or more for the tank. The insertion of the stirring shaft into the liquid may be at the top, at the side, at the bottom, or at an intermediate angle. For example, center stirring, center stirring in which a stirring shaft is inserted from the bottom of the tank, eccentric stirring, side stirring, and the like can be cited, but of course, the method is not particularly limited to these methods.

The number of blades of the stirring blade is not particularly limited.
One to ten sheets or the like can be used as appropriate. Any type of stirring blade can be used. For example, propeller wings,
Angled flat blades, pitched flat blades, flat blade disk turbines, flat blades (turbines), paddles, curved blades, faudler type, bull margin type, helical blades, anchor blades, paddle blades with appropriate holes, etc. . Further, a baffle, a baffle plate, a draft tube and the like may be installed in the reactor in order to increase the mixing efficiency of the liquid phases and the contact efficiency with the gas phase. If necessary, the metal (iron) compound may be continuously supplied to the reactor in a form soluble in water or cyclohexanone.

[Method of Separating Reaction Mixture] There is no particular limitation on the method of separating the reaction mixture. For example, the following embodiments are employed. Among them, (4-) is used in order to reduce the burden such as filter clogging. 1) and (4-2) are more preferred. (4-1): A stationary tank for the reaction mixture is provided inside or outside the reactor, and only the liquid phase (organic layer) portion is taken out while avoiding mixing of the immobilized catalyst. (4-2): A stationary tank for the reaction mixture is provided inside or outside of the reactor, and only the liquid phase (organic layer) is taken out while avoiding mixing of the immobilized catalyst. The liquid phase (organic layer) is taken out through a filter for the purpose of removal. (4-3) A filter is installed inside or outside the reactor, the immobilized catalyst is removed, and the liquid phase is taken out. In addition, a plurality of stationary tanks and filters may be used, and in that case, they may be used in parallel or in series, or in a form in which they are mixed. In order to enhance the separation between the organic layer and the aqueous layer, the organic layer may be naturally cooled or forcedly cooled to a temperature lower than the reaction temperature in the standing tank.

[Recycling Method] The reaction mixture taken out of the reactor is allowed to stand, and furthermore, a liquid phase (aqueous layer) containing the immobilized catalyst obtained by passing through a filter is recycled into the reactor. When the cyclohexanone recovered by the distillation operation described below is recycled to the reactor, the temperature of the liquid phase containing the immobilized catalyst or the temperature of the recovered cyclohexanone exceeds (reaction temperature −60 ° C.) More preferably, it is preferable to recycle into the reactor at a temperature exceeding (reaction temperature −50 ° C.). At this time, compressed gas may be used for transfer, and there is no particular restriction on the type of gas, but a gas similar to the gas used in the reaction and a gas used in the reaction are diluted with another inert gas. It is preferable to use a purified gas or an inert gas. In this case, the inert gas refers to nitrogen, argon, carbon dioxide, neon, helium, or the like. When the oxygen-containing gas is recirculated into the reactor, the temperature is arbitrary, but it is preferably between room temperature and the reaction temperature. When the recirculated gas is higher than room temperature, it can be used as a heating medium for the reactor.

[Extraction method] When the reaction mixture is allowed to stand and separated into an organic layer and an aqueous layer, the immobilized catalyst accompanying the organic layer is separated by filtration, and then the liquid phase (organic layer) is extracted with an organic solvent. In this case, various extraction solvents can be used, but among them, cyclohexanone is preferably used. The temperature at the time of extraction is arbitrary, but it is preferably carried out between room temperature and the reaction temperature.

[Distillation method] In order to finally remove adipaldehyde acid which is a target product, it is preferable to use a distillation step. For example, the following method can be used. A mixture mainly composed of an organic compound and / or an extraction solution separated from the reaction mixture is first distilled in the first column,
Cyclohexanone, unreacted or used as extraction solvent, and low-boiling compounds are separated from the reaction mixture. The mixture obtained from the bottom is further distilled in a second column, and the desired product, adipoaldehyde acid, is removed from the top. At this time, high value-added by-products such as adipic acid may be further removed from the mixture obtained from the bottom of the column.

[Catalyst activity stabilization method and catalyst activation method] When the catalyst activity deteriorates with time and the reaction becomes unstable, a part of the reaction solution is continuously taken out and the reaction solution Recycle after applying the activation treatment to the immobilized catalyst, or continuously supply a new immobilized catalyst, a compound containing a metal element supported on zeolite, or a necessary organic compound to the reactor. , It is desirable to keep the catalyst activity in the reactor at a constant level, and may be performed in combination.

As a method for activating the immobilized catalyst, any of the following methods can be used, and these methods may be used in combination as needed. (5-1): a method of treating with an acidic aqueous solution, (5-2): a method of treating with an alkaline aqueous solution, (5-3): a method of treating with an oxidizing agent, (5-4): a method of treating with a reducing agent Method, (5-5): method of removing adhering components on the immobilized catalyst with a solvent, (5-6): method of treating with a supercritical fluid, (5-7): temperature of 100 ° C. or more (5-8): a method of replenishing metal elements, organic compounds, and the like eluted from the immobilized catalyst in a liquid phase or a gas phase, (5-9): a low boiling point compound by reducing the pressure to 50 kPa or less. How to remove

The immobilized catalyst after the activation treatment is recirculated to the reactor in any of a dry state, a slurry state containing water, cyclohexanone, etc., and a cake state containing water, cyclohexanone, etc. May be.
At this time, the dry state refers to a state in which the immobilized catalyst maintains its properties as a powder, and may contain an appropriate amount of water. The temperature at the time of recirculation is from room temperature (reaction temperature + 30 ° C), more preferably,
The temperature is preferably from room temperature (reaction temperature + 20 ° C).

The adipoaldehyde acid obtained by the oxidation reaction of a cyclic ketone, particularly cyclohexanone, according to the present invention is useful as an intermediate material for various synthetic products. It can be reacted with hydrogen to produce 6-aminocaproic acid, which is further heat-treated to give nylon-
6 can be converted to ε-caprolactam.

6-Aminocaproic acid is obtained by adding adipaldehyde acid and / or an adipaldehyde acid derivative, usually 3
Reacting with excess amounts of ammonia and hydrogen in the presence of a hydrogenation catalyst at a temperature of 0 to 300 ° C. under pressure or after amidating adipoaldehyde acid and / or adipoaldehyde acid derivative with ammonia Produced by reacting with hydrogen. In this case, the adipaldehyde acid derivative is mainly derived from the production of the adipaldehyde acid, and may be a mixture containing two or more different types of derivatives. The acetal form of aldehyde acid ester, adipaldehyde acid acetal, and adipaldehyde ester is shown. The alcohol for the ester precursor and the alcohol for the acetal precursor are usually alcohols having 1 to 4 carbon atoms, preferably methanol, ethanol n-propanol, i-propanol, n-butanol, t-butanol, , 4-butanediol. The hydrogenation catalyst can be appropriately selected from known catalysts used for the hydrogenation reaction, and examples thereof include a catalyst mainly containing cobalt, nickel, palladium, platinum, ruthenium, and rhodium. When a solvent is used in these reactions, an alkanol having 1 to 6 carbon atoms, water, a tertiary amine, or an ether having 2 to 10 carbon atoms can be usually used. Further, if necessary, the step of hydrolyzing the ester and the step of hydrolyzing the acetal using an acid catalyst may be carried out at any stage.

After separating the catalyst and ammonia from the product obtained by the reduction and amination reaction, if necessary,
-The aminocaproic acid can be separated, further purified and recovered as a product. On the other hand, when the purpose is to produce ε-caprolactam, the aminocaproic acid-containing solution after separation of the catalyst and ammonia or the aminocaproic acid that has been further subjected to separation and purification is usually used in an amount of 100 to 370.
The mixture is heated to ℃ to cause a condensation ring-closing reaction to convert to the target compound.
[epsilon] -caprolactam is separated and recovered from the reaction solution by a usual method such as distillation.

[0060]

Next, the method of the present invention will be described in more detail with reference to examples and examples, but the present invention is not limited to the following examples and examples unless it exceeds the gist. In the following examples, NH ₃ / Fe [molar ratio] indicates the ratio to the iron element used.

Preparation Example 1 of Immobilized Catalyst (Immobilized Catalyst-1) FAU type zeolite CBV-760 (Si / 2) manufactured by PQ
Al = 55.0 [molar ratio], H-type) was added to a solution in which 4.05 g of iron (III) nitrate nonahydrate was dissolved in 100 ml of demineralized water, and 1 minute at room temperature under an air atmosphere for 1 minute. Stirred. While maintaining this slurry at room temperature, 1.82 ml of concentrated ammonia water (28 to 30% by weight) (NH ₃ / Fe [molar ratio]:
2.79) was added dropwise over 5 minutes. The resulting yellow-brown slurry was heated to 60 ° C. and stirred for 1 hour while maintaining the temperature. The sample was separated by filtration, washed with demineralized water until the pH of the filtrate became 7.5 or less, and then dried under reduced pressure using an evaporator. The dried sample is further subjected to a stream of nitrogen,
The treatment was performed at 750 ° C. for 3 hours using a tube furnace. The obtained sample is referred to as (immobilized catalyst-1). After the obtained solid (sample) was washed and dried with water, the iron content was measured by X-ray fluorescence spectroscopy (hereinafter, referred to as XRF). . The Si / 2Al (molar ratio) after Fe loading was 68.

Example 2 (Immobilized Catalyst-2) In Example 1 (Immobilized Catalyst-1), the volume of concentrated aqueous ammonia added during Fe loading was 3.04 ml (NH ₃ / Fe [molar ratio]: 4.66). (Immobilized catalyst-2) was prepared in exactly the same manner except for the change. According to XRF, the iron content was 4.84%.

Example 3 (Immobilized catalyst-3) 4.05 g of iron (III) nitrate 9 hydrate in 100 ml of demineralized water
1.82 ml of concentrated aqueous ammonia (28 to 30% by weight) was added dropwise over 5 minutes while stirring the solution in which was dissolved at room temperature. The resulting reddish-brown reaction mixture was stirred at room temperature for another 30 minutes, and then PQ FAU zeolite CBV-
760 (Si / 2Al = 55.0 [molar ratio], H type) 1
0.00 g, and the temperature was raised to 60 ° C.
Stirred for hours. The sample was filtered off and the pH of the filtrate was 7.5.
Washing was performed using demineralized water until the temperature became below, and then dried under reduced pressure using an evaporator. The dried sample was further treated at 750 ° C. for 3 hours using a tubular furnace under a nitrogen stream. The obtained sample is referred to as (immobilized catalyst-3). After the obtained solid (sample) was washed and dried with water, the iron content was measured by XRF and found to be 0.91% in terms of weight percent concentration.

Example 4 (Immobilized catalyst-4) FAU type zeolite CBV-760 (Si / 2) manufactured by PQ
Al = 55.0 [molar ratio, H type], a solution of 4.05 g of iron (III) nitrate nonahydrate in 100 ml of demineralized water was added to 10.00 g of the solution, and the temperature was raised to 60 ° C. in an air atmosphere. And stirred for 30 minutes. The reaction mixture was maintained at 60 ° C., and stirred while stirring.
1 was added dropwise over 5 minutes. The resulting tan slurry was stirred at 60 ° C. for another 30 minutes. Thereafter, the sample was separated by filtration, washed with demineralized water until the pH of the filtrate became 7.5 or less, and then dried under reduced pressure using an evaporator. The dried sample is further subjected to a tube furnace under nitrogen stream for 75 minutes.
Treated at 0 ° C. for 3 hours. The obtained sample is referred to as (immobilized catalyst-4). After the obtained solid (sample) was washed and dried with water, the iron content was measured by XRF. As a result, the iron content was 1.55% in terms of weight percent concentration.

Example 5 (Immobilized catalyst-5) FAU type zeolite CBV-760 (Si / 2) manufactured by PQ
Al = 55.0 [molar ratio, H type], a solution of 4.04 g of iron (III) nitrate nonahydrate in 100 ml of demineralized water was added to 10.00 g of the solution, and the temperature was raised to 60 ° C. in an air atmosphere. And stirred for 55 minutes. The reaction mixture was maintained at 60 ° C., and stirred while stirring.
1 was added dropwise over 5 minutes. The resulting tan slurry was stirred at 60 ° C. for a further 5 minutes. Thereafter, the sample was separated by filtration, washed with demineralized water until the pH of the filtrate became 7.5 or less, and then dried under reduced pressure using an evaporator. The dried sample was further subjected to 750 in a tube furnace under a nitrogen stream.
Treated at ℃ for 3 hours. The obtained sample is referred to as (immobilized catalyst-5). After the obtained solid (sample) was washed and dried with water, the iron content was measured by XRF. As a result, the iron content was 1.49% in terms of weight percent concentration.

Example 6 (Immobilized catalyst-6) Zaulyst International FAU type zeolite CBV
-760 (Si / 2Al = 55.0 [molar ratio], H type)
600 ml of a 1 mol / l (liter) aqueous ammonium nitrate solution was added to 30.0 g, and the mixture was stirred at 80 ° C. for 1 hour. Thereafter, the sample was filtered and washed with deionized water. Further, a 1 mol / l (liter) ammonium nitrate aqueous solution 60
After adding 0 ml, the mixture was stirred at 80 ° C. for 1 hour, filtered, washed and dried to obtain ammonium-type FAU zeolite. Among the obtained ammonium-type FAU zeolites, 10.
A solution prepared by dissolving 4.05 g of iron (III) nitrate nonahydrate in 100 ml of demineralized water was added to 00 g of the solution, and the solution was added under an air atmosphere.
The temperature was raised to ° C., and the mixture was stirred for 30 minutes. 60 reaction mixture
C. and 1.82 ml of concentrated aqueous ammonia (28 to 30% by weight) was added dropwise over 5 minutes with stirring. The resulting tan slurry was stirred at 60 ° C. for another 30 minutes. Thereafter, the sample was separated by filtration, washed with demineralized water until the pH of the filtrate became 7.5 or less, and then dried under reduced pressure using an evaporator. The dried sample was further treated at 750 ° C. for 3 hours using a tubular furnace under a nitrogen stream. The obtained sample is referred to as (immobilized catalyst-6). After washing and drying the obtained solid (sample) with water, the iron content was measured by XRF.
3%.

Example 7 (Immobilized catalyst-7) FAU type zeolite CBV-760 (Si / 2) manufactured by PQ
Al = 55.0 [molar ratio, H type], a solution in which 4.05 g of iron (III) nitrate nonahydrate was dissolved in 100 ml of deionized water was added to 10.00 g of the solution, and the temperature was raised to 60 ° C. The mixture was stirred for 1 hour while maintaining the temperature. The sample is filtered off and the pH of the filtrate
Was reduced to 6.5 or less using deionized water, and then dried under reduced pressure using an evaporator. The dried sample was further treated at 750 ° C. for 3 hours in a tubular furnace under a nitrogen stream. The obtained sample is referred to as (immobilized catalyst-7). After washing and drying the obtained solid (sample) with water, X
The iron content was determined by RF to be 0.77% by weight percent. The Si / 2Al (molar ratio) after Fe ion exchange was 70.

Example 1 A glass reactor having an inner diameter of 50 mm and an inner height of 25 mm was charged with 2.00 g of (immobilized catalyst-1), and 15 ml of water was added.
1.5 g of cyclohexanone was added, and under a slight pressurization of molecular oxygen (approximately 1 kPa against normal pressure), using a Teflon-coated nearly cylindrical stirrer bar having a total length of 30 mm and a maximum diameter of 8 mm, using a magnetic stirrer to reduce the molecular weight from 1200 The reaction was carried out at 85 ° C. for 1.5 hours while stirring at 1500 rpm. The immobilized catalyst was centrifuged from the obtained reaction mixture, extracted with a solvent (methanol), and analyzed by gas chromatography using an internal standard. The yield of the target product, adipoaldehyde acid, was found to be 7.
4%.

Examples 2 to 6 and Comparative Examples (Immobilized catalyst-2) to (Immobilized catalyst-7)
Oxidative cleavage of cyclohexanone was carried out under the same reaction conditions as in Example 1 except that 0 g was used, and an adipaldehyde acid as a target product was obtained. Table 1 summarizes the results.

[Table 1]

[0070]

According to the present invention, the activity of an oxidative cleavage catalyst supported on a water-insoluble acidic solid zeolite for the production of aliphatic aldehyde acids, particularly adipaldehyde acid, by oxidizing cyclic ketones is improved. In addition, it is possible to simplify the process of separating and purifying the catalyst, and also to construct a system that does not contain halogen as a counter ion and to reduce the material of the reactor and the like. Can be manufactured.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H006 AA02 BA02 BA05 BA06 BA10 BA14 BA16 BA19 BA20 BA21 BA22 BA34 BA51 BA71 BE30 BE60 BQ10 BS10 DA25 DA35 4H039 CA62 CA65 CH70

Claims (10)

[Claims] (1) In producing an aliphatic aldehyde acid by oxidizing a cyclic ketone with molecular oxygen in the presence of an immobilized catalyst, a solid acidic zeolite belonging to Groups 4 to 11 of the periodic table is used as an immobilized catalyst. It is composed of a composite in which at least one metal element is supported in a liquid phase, and the composite has a content of 0.0 with respect to the total number of moles of the metal element used in the support.
A process for producing an aliphatic aldehyde acid, comprising using a catalyst prepared in the presence of a basic compound in an amount of 1 to 50 times (molar ratio). 2. A method according to claim 1, wherein cyclohexanone is immobilized in the presence of an immobilized catalyst.
A composite comprising at least one metal element belonging to Groups 4 to 11 of the periodic table supported on a solid acidic zeolite in a liquid phase as an immobilization catalyst in producing adipaldehyde acid by oxidation with molecular oxygen. And a catalyst prepared in the presence of a basic compound in an amount of 0.01 to 50 times (molar ratio) with respect to the total number of moles of the metal element used at the time of loading. A method for producing adipaldehyde acid, which is characterized by: 3. The method according to claim 1, wherein the oxidation is carried out in the presence of water. 4. The method according to claim 1, wherein the basic compound is ammonia, a linear alkylamine or an alicyclic alkylamine. 5. The method according to claim 1, wherein at least one metal element belonging to Groups 4 to 11 of the periodic table is iron. 6. A composite in which at least one metal element belonging to Groups 4 to 11 of the Periodic Table is supported in a liquid phase on a solid acidic zeolite, and the composite is used for loading. A catalyst for producing an aliphatic aldehyde acid, comprising an immobilized catalyst prepared in the presence of a basic compound in an amount of 0.01 to 50 times (molar ratio) the total number of moles of a metal element. 7. A composite in which at least one metal element belonging to Groups 4 to 11 of the periodic table is supported on a solid acidic zeolite in a liquid phase, and the composite is used for loading. A catalyst for producing adipoaldehyde acid, comprising an immobilized catalyst prepared in the presence of a basic compound in an amount of 0.01 to 50 times (molar ratio) the total number of moles of a metal element. 8. The catalyst according to claim 6, wherein the basic compound is ammonia, linear alkylamines or alicyclic alkylamines. 9. The catalyst according to claim 6, wherein at least one metal element belonging to Groups 4 to 11 of the periodic table is iron. 10. A complex comprising cyclohexanone supported on water and a solid acidic zeolite in a liquid phase with at least one metal element belonging to groups 4 to 11 of the periodic table, and the complex Is oxidized by molecular oxygen in the presence of an immobilized catalyst prepared in the presence of a basic compound in an amount of 0.01 to 50 times (molar ratio) based on the total number of moles of the metal element used at the time of loading. Forming an oxidation reactant containing adipaldehyde acid, and then reacting the adipaldehyde acid obtained from the oxidation reactant with ammonia and hydrogen in the presence of a hydrogenation catalyst to form 6-aminocaproic acid; The 6-aminocaproic acid thus obtained is heated and a
-A method for producing [epsilon] -caprolactam, which comprises converting into caprolactam.