JP2001198464A - Catalyst for oxidation of methylbenzenes and method for preparation of aromatic aldehyde - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a novel catalyst for preparing a corresponding aromatic aldehyde in a high yield by conducting a vapor-phase oxidation of methylbenzenes in the presence of molecular oxygen, and provide a method for preparation of an aromatic aldehyde by using the catalyst, and further a method for preparation of cyclohexane dimethanol by hydrogenation of phthalaldehydes obtained by the above method. SOLUTION: The catalyst for oxidation of methylbenzenes has a composition expressed by general formula 1, WaXbYcOx, (wherein W represents a tungsten atom; X represents at least one element selected from the group consisting of P, Sb, Bi, and Si; Y represents at least one element selected from the group consisting of Fe, Co, Ni, Mn, Re, Cr, V, Nb, Ti, Zr, Zn, Cd, Y, La, Ce, B, Al, Tl, Sn, Mg, Ca, Sr, Ba, Li, Na, K, Rb, and Cs; and O represents an oxygen atom).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst for oxidizing methylbenzenes, a method for producing aromatic aldehydes using the catalyst, and a method for producing cyclohexanedimethanol from phthalaldehydes obtained thereby. More specifically, the present invention provides a catalyst suitable for producing a corresponding aromatic aldehyde in high yield by subjecting methylbenzenes to gas phase oxidation in the presence of molecular oxygen, A method in which benzenes are vapor-phase oxidized in the presence of molecular oxygen to produce the corresponding aromatic aldehyde in high yield, and furthermore, the resulting phthalaldehydes are hydrogenated to produce cyclohexanedimethanol On how to do it.

[0002]

2. Description of the Related Art Aromatic aldehydes have highly reactive aldehyde groups and have a wide range of uses among aromatic compounds. Above all, terephthalaldehyde (TPAL) having two aldehyde groups at the para position is used in medicine, pesticides,
It is expected to be used for dyes, liquid crystal polymers, conductive polymers, heat-resistant plastics and the like, and an inexpensive industrial production method is required.

[0003] Attempts to produce terephthalaldehyde by vapor phase oxidation of p-xylene have been made for quite some time. Japanese Patent Publication No. 47-2086 discloses W
An oxide catalyst having a composition in which the ratio of Mo to Mo is in the range of 1: 1 to 20: 1 is disclosed. JP-A-48-47830 discloses a catalyst containing V and Rb or Cs. U.S. Pat. No. 3,845,137 describes W
And Mo, Ca, Ba, Ti, Zr, Hf,
A catalyst comprising an oxide to which at least one element selected from the group consisting of Tl, Nb, Zn and Sn is added is disclosed. U.S. Pat. No. 4,017,547 discloses that
Mo oxide and W oxide or silicotungstic acid, and
A catalyst comprising a Bi oxide is disclosed. U.S. Pat. No. 5,324,702 discloses a special catalyst in which Fe, Zn, etc. and V, Mo, W, etc. are supported by chemical vapor deposition (CVD) on a deborated borosilicate crystal molecular sieve. Have been.

[0004] However, all of these catalysts have low yields of the desired terephthalaldehyde, and have not been commercialized industrially. Furthermore, according to the findings of the present inventors, these catalysts not only have low activity, but also have low selectivity for the target substance. Therefore, when hydrogenating the obtained terephthalaldehyde, 1,4-cyclohexanedimethanol It has been found that there is a tendency for impurities to decrease the yield.

[0005] Cyclohexanedimethanol is an industrially extremely useful compound as a raw material for polyester-based paints, synthetic fibers, synthetic resins and the like. As a method for producing 1,4-cyclohexanedimethanol, a dialkyl terephthalate is used as a starting material, and after the benzene ring of the dialkyl terephthalate is hydrogenated, the resulting 1,4-cyclohexanedicarboxylic acid dialkyl ester is further obtained. Hydrogenation method, using terephthalic acid as a starting material, hydrogenating the benzene ring in the same manner as described above, and further hydrogenating the resulting 1,4-cyclohexanedicarboxylic acid, hydrogenating the benzene ring of xylylene glycol A method and a method of hydrogenating terephthalaldehyde are known.

[0006] Among these production methods, a typical one is the following one. The dialkyl terephthalate as a starting material is obtained by further esterifying terephthalic acid obtained by oxidizing p-xylene with an alcohol. In order to obtain the desired product, a two-stage hydrogenation reaction must be performed thereafter, and a multi-stage reaction is required. In the above method, terephthalic acid obtained by oxidizing p-xylene is used as a starting material, so that an esterification reaction is unnecessary. For example, according to JP-A-52-242, a large amount of Alcohol must be used as a solvent, which causes a problem that productivity is reduced. Furthermore, in these methods, high-temperature and high-pressure are required as conditions for the hydrogenation reaction of the benzene ring and the carboxylic acid or its ester, so that special reaction equipment is required. Further, since the copper chromite catalyst used in the subsequent reaction contains toxic chromium, there is a problem in performing disposal treatment.

[0007] In these reactions, stoichiometrically, 7 moles of hydrogen are required for 1 mole of the raw material, and therefore the reactions consume a large amount of hydrogen. Furthermore, in the method, 2 mol of alcohol is used, and in the method, 2 mol of water is produced as a by-product.
It was not always the preferred method from an economic point of view.

On the other hand, in the above-mentioned method, for example, Example 7 of JP-A-8-187432, a benzene ring of xylylene glycol is prepared under mild conditions using a novel hydrogenation catalyst, a Raneyruthenium catalyst. A method for obtaining cyclohexanedimethanol as a target product by hydrogenation under the following conditions is disclosed. However, in this production method, xylylene glycol as a raw material is very expensive, and an inexpensive industrial production method has not yet been established.

Further, Japanese Patent Application Laid-Open No. 11-3353 recently disclosed
No. 11 proposes a production method based on the above. In this production method, a one-stage hydrogenation reaction for simultaneously hydrogenating an aldehyde group and a benzene ring from terephthalaldehyde under a specific relatively mild reaction condition using a catalyst containing a Group VIII metal of the Long Periodic Table. It has been disclosed. This method requires hydrogenation of the aldehyde group and the benzene ring, but stoichiometrically requires only 5 moles of hydrogen for 1 mole of the raw material, has no alcohol or water by-product, and is a toxic substance. This method does not require the use of a catalyst containing.

However, even in this production method, an industrial production method of terephthalaldehyde as a raw material has not been established at present, and this publication does not specifically describe a production method of terephthalaldehyde.

[0011]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and provides a high yield of a corresponding aromatic aldehyde by subjecting methylbenzenes to gas phase oxidation in the presence of molecular oxygen. And a method for producing the corresponding aromatic aldehyde from methylbenzenes in high yield using this catalyst, and hydrogenation of phthalaldehydes among the aromatic aldehydes obtained by this method To provide a method for producing cyclohexanedimethanol.

[0012]

Means for Solving the Problems The present inventors have intensively studied a novel catalyst capable of producing a corresponding aromatic aldehyde in a high yield by gas-phase oxidation of methylbenzenes in the presence of molecular oxygen. As a result, a catalyst having the composition described below, or a catalyst in which this catalytically active component is supported on a refractory inorganic carrier material shows excellent partial oxidation performance, and by using this catalyst, aromatic aldehyde can be produced in high yield. It was found that it can be manufactured. Furthermore, they have found that cyclohexanedimethanol can be produced with high efficiency by hydrogenating phthalaldehydes among the aromatic aldehydes obtained here, and have completed the present invention. Hereinafter, the present invention will be described in detail.

The methylbenzenes in the present invention are 1
A compound in which one or more methyl groups are directly bonded to a benzene ring, typical examples of which are p-xylene, o
-Xylene, m-xylene, pseudocumene, mesitylene, and durene having 8 to 10 carbon atoms such as methylbenzenes.

The catalyst of the present invention is to produce the corresponding aldehyde by subjecting these methylbenzenes to gas phase oxidation in the presence of molecular oxygen. Specifically, for example, p-
Xylene to terephthalaldehyde and p-tolualdehyde, o-xylene to phthalaldehyde and o-tolualdehyde, m-xylene to isophthalaldehyde and m-tolualdehyde, pseudocumene to 2-methylterephthalaldehyde, 2,4-dimethylbenzaldehyde, 2 , 5-dimethylbenzaldehyde and 3,4
Dimethylbenzaldehyde, 3,5-from mesitylene
Dimethylbenzaldehyde, 5-methylisophthalaldehyde and 1,3,5-triformylbenzene, from durene to 2,5-dimethylterephthalaldehyde, 4,5
-Dimethylphthalaldehyde, 2,4,5-trimethylbenzaldehyde, 2,4,5-triformyltoluene and 1,2,4,5-tetraformylbenzene, respectively. Among them, the oxidation catalyst of the present invention is particularly suitably used for producing terephthalaldehyde from p-xylene.

The catalyst for oxidizing methylbenzenes of the present invention comprises:
It has a composition represented by the following general formula (1): WaXbYcOx (1). In the general formula (1),
W represents a tungsten atom. X is P, Sb, Bi
And at least one element selected from the group consisting of Si and Si. Y is Fe, Co, Ni, Mn, Re, C
r, V, Nb, Ti, Zr, Zn, Cd, Y, La, C
e, B, Al, Tl, Sn, Mg, Ca, Sr, Ba,
It represents at least one element selected from the group consisting of Li, Na, K, Rb and Cs. O represents an oxygen atom. In the above general formula (1), P and S as X components
Among b, Bi and Si, Sb and / or Bi are preferable, and Sb is particularly preferable. In addition, Fe, Co, Ni, Mn, Re, Cr as a Y component,
V, Nb, Ti, Zr, Zn, Cd, Y, La, Ce,
B, Al, Tl, Sn, Mg, Ca, Sr, Ba, L
Fe, Co, N among i, Na, K, Rb and Cs
i, Mn, Zn, Cd, Cr, V, Nb, Ti, Zr,
It is preferably at least one element selected from the group consisting of Ce, Sr and Cs, particularly Fe, Ni,
It is preferably at least one element selected from the group consisting of Co, Zn, Cd and Mn.

In the general formula (1), a, b, c
And x represent the number of W, X, Y and oxygen atoms, respectively. However, the ratio of a, b and c is, when a = 12,
b = 0.5 to 10, c = 0 to 15, and x is a numerical value determined by the oxidation state of an element other than an oxygen atom.
The ratio of a, b and c is preferably when a = 12,
b = 1-6, c = 0-8. Note that the case of a = 12 is used to indicate the ratio of a, b, and c. However, when a is any other numerical value, b and c are determined according to the above ratio.
Will be set.

The oxidation catalyst represented by the general formula (1) of the present invention can be used by being supported on a refractory inorganic carrier for the purpose of improving the activity and the physical durability. As the refractory inorganic carrier, a refractory inorganic carrier generally used for the preparation of this type of catalyst can be used. Typical examples thereof include alumina such as α-alumina, silica, titania, zirconia, and silicon carbide. Among them, a specific surface area of 1 m ² / g or less, preferably 0.1 m ²
Α-alumina and silicon carbide having a low specific surface area of / g or less are preferred because they have few side reactions and can obtain the target product in high yield.
The amount of the catalytically active component to be supported is usually 5 to 5 of the refractory inorganic carrier.
90% by mass.

The method for preparing the oxidation catalyst of the present invention is not particularly limited, and it can be prepared by a method generally used for preparing this kind of catalyst. For example, an aqueous solution of antimony tartrate or antimony trioxide powder, and an aqueous solution of iron nitrate are prepared by adding an aqueous solution of antimony tartrate or an aqueous solution of iron nitrate to an aqueous solution of ammonium metatungstate. Drying with 300 ~
Used after firing at 700 ° C. When the carrier is not used, the homogeneous solution or suspension is heated and stirred as it is to evaporate to dryness, dried at the same temperature as above, pulverized, molded,
It is used after firing at the same temperature as above. There is no particular limitation on the atmosphere at the time of performing the drying and firing, even in the air, in a high oxygen concentration or low oxygen concentration atmosphere, or in a reducing atmosphere, in an atmosphere of an inert gas such as nitrogen, helium, or argon, and further. It can be performed even in a vacuum. These can be appropriately selected according to the characteristics of the raw materials used for preparing the catalyst. In the firing in a low oxygen concentration atmosphere, the catalytic activity tends to be lower than in the air firing, but the selectivity is improved and the yield may be improved in some cases. When an oxide solid powder raw material is used, firing in an inert gas atmosphere is particularly preferred. The raw materials used for preparing the catalyst are not particularly limited, and nitrates, sulfates, oxides, hydroxides, chlorides, carbonates, organic acid salts, oxyacids, ammonium oxyacid salts, heteropolyacids of the elements used can be used. Acids and the like can be used.

The form of use of the refractory inorganic carrier raw material in preparing the catalyst is not particularly limited.
It can be used in various ways depending on the conditions of use of the catalyst, such as powders of oxides and hydroxides, or gels and sols. The shape of the catalyst is not particularly limited, and it can be used in a spherical shape, a pellet shape, a ring shape, or a honeycomb shape.

A method for producing a corresponding aromatic aldehyde by subjecting methylbenzenes to gas phase oxidation in the presence of molecular oxygen, and a method for producing an aromatic aldehyde using the above-mentioned catalyst for oxidizing methylbenzenes is also provided. The present invention is one of the present invention, and can produce a corresponding aromatic aldehyde from methylbenzenes in high yield.

In the method for producing an aromatic aldehyde, methylbenzenes used as a raw material are not particularly limited, and for example, methylbenzenes having 8 to 10 carbon atoms are preferable. Examples of the above-mentioned methylbenzenes having 8 to 10 carbon atoms include the same ones as described above. Among these, the method for producing an aromatic aldehyde of the present invention is suitably applied when producing the corresponding terephthalaldehyde by vapor-phase oxidation of p-xylene.

As a raw material for carrying out the gas phase oxidation reaction of the present invention, a diluent gas can be used, if necessary, in addition to methylbenzenes and molecular oxygen. Air or pure oxygen is used as the molecular oxygen source. The molecular oxygen is usually from 5 to 100 per mole of methylbenzenes.
Used in molar proportions. As the diluent gas, an inert gas such as nitrogen, helium, carbon dioxide, or water vapor is preferably used.

The reaction conditions for carrying out the gas-phase oxidation reaction of the present invention are not particularly limited.
The raw material gas may be brought into contact with the oxidation catalyst of the present invention under the conditions of 100,000 hr ^-1 and a reaction temperature of 350 to 650 ° C. Preferably space velocity 2000-50,000h
r ⁻¹ , the reaction temperature is 450 to 600 ° C. The above reaction is usually carried out at normal pressure or slightly elevated pressure, but can be carried out under either high pressure or reduced pressure. The reaction system is not particularly limited, and may be any of a fixed bed system, a moving bed system, and a fluidized bed system. Further, a single-flow system or a recycling system may be used.

A method for producing cyclohexanedimethanol by hydrogenating phthalaldehyde, wherein the phthalaldehyde is obtained by the above-mentioned method for producing aromatic aldehyde using methylbenzene as xylene. The production method is also one of the present invention, and cyclohexane dimethanol can be produced from xylene at low cost and industrially.

By hydrogenating terephthalaldehyde, 1,
A method for producing 4-cyclohexane dimethanol, wherein the terephthalaldehyde is obtained by the method for producing an aromatic aldehyde, is also a method for producing 1,4-cyclohexane dimethanol according to a preferred embodiment of the present invention. That is, 1,4-cyclohexanedimethanol can be inexpensively and industrially produced from p-xylene.

In the above method for producing cyclohexanedimethanol, any known method may be employed for the hydrogenation of phthalaldehyde. Specifically, for example, (I) a noble metal (platinum group) such as palladium, platinum, ruthenium, rhodium, and iridium is converted into activated carbon, alumina,
Noble metal supported catalyst supported on a carrier such as diatomaceous earth; (I
I) Noble metal oxides such as palladium oxide, platinum oxide, ruthenium oxide, rhodium oxide and iridium oxide; (III)
Noble metals such as palladium black, platinum black, ruthenium black, and rhodium black; (IV) Raney-based catalysts such as Raney nickel, Raney cobalt, and Raney ruthenium; (V) Reduction of base metal-supported catalysts having a base metal supported on a carrier Hydrogenation can be carried out using a general method such as a method of reacting with hydrogen using as a catalyst.

In the present invention, phthalaldehydes of high purity are obtained by the oxidation in the first stage, and these can be used without purification. Of course, it may be used after purification.
Reaction conditions The reaction conditions such as temperature and hydrogen partial pressure may be set according to the type and amount of the reduction catalyst, and are not particularly limited, but the reaction temperature is in the range of room temperature to 250 ° C, preferably. Is a temperature of 50 to 200C. If the reaction temperature is outside these ranges, the reaction rate may be significantly reduced, or a side reaction such as a elimination reaction of a functional group may occur to significantly lower the selectivity.

The hydrogen partial pressure is preferably at least 1 MPa. If it is less than 1 MPa, a large amount of xylylene glycol in which only the unreacted aldehyde group has been reduced may remain in a large amount. The hydrogenation can be carried out by suspending phthalaldehyde in an inert medium, but is preferably carried out by dissolving in a suitable solvent such as alcohol or ether. As an embodiment of hydrogenation, any of a batch system, a semi-batch system, and a continuous flow system may be used.

[0029]

The present invention will be described more specifically with reference to the following examples. The conversion, selectivity and single-stream yield in the reaction are defined as follows, including by-products. Conversion (mol%) = (mol number of reacted raw material / mol number of supplied raw material) × 100 Selectivity (mol%) = (mol number of each compound generated / mol number of reacted raw material) × (production Number of carbons of each compound obtained / number of carbons of raw material supplied) × 100 Single stream yield (mol%) = (moles of each compound generated / moles of raw material supplied) × (carbon number of each compound generated) /
Carbon number of supplied raw material) x 100

Example 1 An antimony tartrate aqueous solution was first prepared as an antimony raw material.
Made. Dissolve 150.0 g of L-tartaric acid in 310 ml of water
To the antimony trioxide (99.9% purity) powder
36.5 g was added, and the mixture was dissolved by heating under reflux. this
, Add a small amount of water, adjust the total mass to 500 g,
b. An antimony tartrate aqueous solution having a concentration of 0.5 mmol / g
Obtained. Further, an aqueous solution of iron nitrate was prepared as an Fe raw material.
Dissolve 40.4 g of iron nitrate nonahydrate in water and adjust the quality of the whole solution.
Amount of iron is 100 g, and aqueous solution of iron nitrate with Fe concentration of 1 mmol / g
A solution was obtained. 6.00 g of the above antimony tartrate aqueous solution
2.00 g of an aqueous solution of iron nitrate was added to
Ammonium formate aqueous solution (WO_Three 50% by mass
Yes) 5.56 g was added to obtain a uniform impregnation liquid. 1 in advance
Α-alumina support SA5218 preheated to 00 ° C
(Norton, 3/8 inch sphere) 20 g of the above impregnating liquid
And heat and stir on a water bath.
Hardened. This is dried at 120 ° C. for 16 hours, and
Was calcined at 650 ° C. for 2 hours in the atmosphere. Shake the powder
The catalyst finally dropped and obtained (the same applies to the following examples)
E) is 14.3% by mass W₁₂Sb_Three Fe_Two Ox / S
A5218. 20 g of this catalyst is used in a normal flow
The reactor was charged and reacted under the following conditions. Table of results
It is shown in FIG. Reaction pressure: normal pressure Reaction gas composition: p-xylene / Air = 0.8 / 99.
2 (p-xylene / O_Two= 1 / 25.8) Reaction gas supply rate: 1.25 L (liter) (standard condition)
State; gas 0 ° C, 1.013 × 10^-1MPa volume))
/ Min SV: 5680 hr^-1  Reaction temperature: 550 ° C. Even in the following Examples, except for the reaction temperature, unless otherwise specified.
The reaction was performed under the same reaction conditions. However, SV means that the catalyst
It varies slightly depending on the difference in packing specific gravity. Reaction temperature and reaction result
Are shown in Table 1.

Example 2 A catalyst was prepared in the same manner as in Example 1 except that the amount of the aqueous solution of antimony tartrate was changed to 8.00 g. The composition of the obtained catalyst was 14.6% by mass W ₁₂ Sb ₄ Fe ₂ Ox / SA5
218.

Example 3 A catalyst was prepared in the same manner as in Example 1 except that the amount of the aqueous solution of antimony tartrate was changed to 4.00 g. The composition of the obtained catalyst was 13.6% by mass W ₁₂ Sb ₂ Fe ₂ Ox / SA5
218.

Example 4 A catalyst was prepared in the same manner as in Example 1 except that the amount of the aqueous solution of iron nitrate was changed to 3.00 g. The composition of the obtained catalyst was 1
It was 4.6% by mass W ₁₂ Sb ₃ Fe ₃ Ox / SA5218.

Example 5 A catalyst was prepared in the same manner as in Example 1 except that the amount of antimony tartrate was changed to 2.00 g and the amount of aqueous iron nitrate solution was changed to 1.00 g. The composition of the obtained catalyst was 12.9% by mass W
₁₂ Sb ₁ Fe ₁ Ox / SA5218.

Example 6 An aqueous solution of zirconyl nitrate was prepared as a raw material for Zr. 13.50 g of zirconyl nitrate dihydrate is dissolved in water to make the total weight of the solution 100 g, and the Zr concentration is 0.5 mmol.
/ G aqueous solution of zirconyl nitrate. A catalyst was prepared in the same manner as in Example 1, except that 1.00 g of the aqueous solution of zirconyl nitrate was added to the impregnating liquid of Example 1. The composition of the obtained catalyst was 14.4% by mass W ₁₂ Sb ₃ Fe ₂ Z.
r _0.5 Ox / SA5218.

Example 7 An aqueous cesium nitrate solution was prepared as a raw material for Cs. 9.75 g of cesium nitrate was dissolved in water, and the total weight of the solution was reduced to 5%.
The amount was adjusted to 0 g to obtain a cesium nitrate aqueous solution having a Cs concentration of 1 mmol / g. A catalyst was prepared in the same manner as in Example 1 except that the impregnating liquid obtained by adding 0.5 g of the cesium nitrate aqueous solution to the impregnating liquid of Example 1 was used. The composition of the obtained catalyst is 14.
4% by mass W ₁₂ Sb ₃ Fe ₂ Cs _0.5 Ox / SA5218
Met.

Example 8 A niobium oxalate aqueous solution was prepared as a raw material of Nb. 12.97 niobium oxalate (containing 20.5% in terms of Nb ₂ O ₅ )
g was dissolved in water, the total weight of the solution was adjusted to 100 g,
An aqueous niobium oxalate solution having an Nb concentration of 0.1 mmol / g was obtained. A catalyst was prepared in the same manner as in Example 1, except that 5.0 g of this aqueous solution was added to the impregnating liquid of Example 1. The composition of the obtained catalyst was 14.4% by mass W ₁₂ Sb ₃ F.
e ₂ Nb _0.5 Ox / SA5218.

Example 9 An aqueous solution of bismuth nitrate and nitric acid was prepared as a Bi raw material. Bismuth nitrate (24.26 g) was dissolved in a solution prepared by diluting 20 g of 60% nitric acid with 50 g of water, and water was added to adjust the total weight of the solution to 100 g to obtain a nitric acid aqueous solution having a Bi concentration of 0.5 mmol / g. First, this bismuth nitrate aqueous solution of nitric acid 6.
Using only 0 g as the impregnating liquid, impregnation and evaporation to dryness were performed in the same manner as in Example 1. Further, an impregnation operation is performed using a solution obtained by adding an aqueous solution of ammonium metatungstate and an aqueous solution of iron nitrate in the same amount as in Example 1, and drying and drying are performed in the same manner as in Example 1.
The firing was performed. The composition of the obtained catalyst was 14.9% by mass W
₁₂ Bi ₃ Fe ₂ Ox / SA5218.

Example 10 Phosphotungstic acid (H ₃ (PW ₁₂ O ₄₀ ) .nH ₂ O)
A solution prepared by dissolving 3.42 g in 5 ml of water was used as an impregnating liquid, and was prepared in the same manner as in Example 1. The composition of the obtained catalyst was 12.8% by mass W ₁₂ P ₁ Ox / SA5218.

Example 11 Silicotungstic acid (SiO ₂ .12WO ₃ .26H ₂₎
O) A solution prepared by dissolving 2.84 g in 5 ml of water was used as an impregnating liquid, and was prepared in the same manner as in Example 1. The composition of the obtained catalyst was 12.1% by mass W ₁₂ Si ₁ Ox / SA5218.

Example 12 A potassium nitrate aqueous solution was prepared as a K raw material. 5.06 g of potassium nitrate was dissolved in water, and the total weight of the solution was reduced to 50.
g, and an aqueous solution of potassium nitrate having a K concentration of 1 mmol / g was obtained. This potassium nitrate aqueous solution was added to the impregnating solution of Example 8 in an amount of 0.1%.
A catalyst was prepared in the same manner as in Example 1 except that the impregnating solution to which 5 g was added was used. The composition of the obtained catalyst was 14.5% by mass.
It was W ₁₂ Sb ₃ Fe ₂ Nb _0.5 K _0.5 Ox / SA5218.

Example 13 An aqueous cobalt nitrate solution was prepared as a Co raw material. 14.64 g of cobalt nitrate hexahydrate was dissolved in water to make the total weight of the solution 50 g, and a cobalt nitrate aqueous solution having a Co concentration of 1 mmol / g was obtained. This aqueous cobalt nitrate solution 3.00
g in place of the aqueous iron nitrate solution, the amount of the antimony tartrate aqueous solution was increased to 9.00 g, the aqueous solution of ammonium metatungstate was increased to 8.34 g, and the calcination temperature was set to 600 ° C., and the catalyst was the same as in Example 1. Preparation was performed. The composition of the obtained catalyst was 17.1% by mass W ₁₂ Sb ₃ C
o ₂ Ox / SA5218.

Example 14 A catalyst was prepared in the same manner as in Example 13 except that the amount of the aqueous solution of cobalt nitrate was increased to 9.00 g. The composition of the obtained catalyst was 16.7% by mass W ₁₂ Sb ₃ Co ₆ Ox / SA5218.
Met.

Example 15 A nickel nitrate aqueous solution was prepared as a Ni raw material. 14.55 g of nickel nitrate hexahydrate was dissolved in water to make the total weight of the solution 50 g, and a nickel nitrate aqueous solution having a Ni concentration of 1 mmol / g was obtained. This nickel nitrate aqueous solution 9.00
A catalyst was prepared in the same manner as in Example 13, except that g was used instead of the aqueous cobalt nitrate solution. The composition of the obtained catalyst was 15.4% by mass W ₁₂ Sb ₃ Ni ₆ Ox / SA5218.
Met.

Example 16 An aqueous zinc nitrate solution was prepared as a Zn raw material. 14.89 g of zinc nitrate hexahydrate was dissolved in water to make the total weight of the solution 50 g, and a zinc nitrate aqueous solution having a Zn concentration of 1 mmol / g was obtained. A catalyst was prepared in the same manner as in Example 13, except that 9.00 g of the aqueous zinc nitrate solution was used in place of the aqueous cobalt nitrate solution. The composition of the obtained catalyst was 16.3% by mass.
It was W ₁₂ Sb ₃ Zn ₆ Ox / SA5218.

Example 17 A cadmium nitrate aqueous solution was prepared as a Cd raw material. 15.44 g of cadmium nitrate tetrahydrate was dissolved in water to make the total weight of the solution 50 g, and an aqueous solution of cadmium nitrate having a Cd concentration of 1 mmol / g was obtained. A catalyst was prepared in the same manner as in Example 13, except that 9.00 g of the cadmium nitrate aqueous solution was used instead of the cobalt nitrate aqueous solution. The composition of the obtained catalyst was 15.8% by mass W ₁₂ Sb ₃ Cd ₆ Ox / SA.
5218.

Example 18 A manganese nitrate aqueous solution was prepared as a Mn raw material. 14.37 g of manganese nitrate hexahydrate was dissolved in water to make the total weight of the solution 50 g, and a manganese nitrate aqueous solution having a Mn concentration of 1 mmol / g was obtained. This manganese nitrate aqueous solution 9.00
A catalyst was prepared in the same manner as in Example 13, except that g was used instead of the aqueous cobalt nitrate solution. The composition of the obtained catalyst was 12.7% by mass W ₁₂ Sb ₃ Mn ₆ Ox / SA5218.
Met.

Example 19 A calcium nitrate aqueous solution was prepared as a Ca raw material. 14.37 g of calcium nitrate tetrahydrate was dissolved in water to make the total weight of the solution 50 g, and a calcium nitrate aqueous solution having a Ca concentration of 1 mmol / g was obtained. A catalyst was prepared in the same manner as in Example 13 except that 3.00 g of the aqueous calcium nitrate solution was used instead of the aqueous cobalt nitrate solution. The composition of the obtained catalyst was 14.6% by mass W ₁₂ Sb ₃ Ca ₂ Ox / SA.
5218.

Example 20 A strontium nitrate aqueous solution was prepared as a Sr raw material.
10.69 g of strontium nitrate was dissolved in water to make the total weight of the solution 50 g, and an aqueous solution of strontium nitrate having an Sr concentration of 1 mmol / g was obtained. A catalyst was prepared in the same manner as in Example 13 except that 3.00 g of this aqueous strontium nitrate solution was used instead of the aqueous cobalt nitrate solution. The composition of the obtained catalyst was 14.3 mass% W ₁₂ Sb ₃ Sr ₂ O
x / SA5218.

Example 21 A lanthanum nitrate aqueous solution was prepared as a La raw material. 21.67 g of lanthanum nitrate hexahydrate was dissolved in water to make the total weight of the solution 100 g, and an aqueous lanthanum nitrate solution having a La concentration of 0.5 mmol / g was obtained. A catalyst was prepared in the same manner as in Example 13, except that 6.00 g of this lanthanum nitrate aqueous solution was used instead of the cobalt nitrate aqueous solution. The composition of the obtained catalyst was 15.5% by mass W ₁₂ Sb ₃ La ₂ Ox / SA.
5218.

Example 22 An aqueous solution of chromium nitrate was prepared as a Cr raw material. 20.03 g of chromium nitrate nonahydrate was dissolved in water to make the total weight of the solution 50 g, and a chromium nitrate aqueous solution having a Cr concentration of 1 mmol / g was obtained. A catalyst was prepared in the same manner as in Example 16 except that 0.45 g of this chromium nitrate aqueous solution was added to the impregnating solution of Example 16. The composition of the obtained catalyst was 16.9% by mass W
₁₂ Sb ₃ Zn ₆ Cr _0.3 Ox / SA5218.

Example 23 Except that the same catalyst as in Example 22 was used, the reaction gas supply rate was changed to 1.95 L (liter) (standard state) / min, and the reaction temperature was changed to 570 ° C. The reaction was performed under the same conditions. Table 1 shows the obtained results.

Example 24 An aqueous solution of ammonium metavanadate was prepared as a V raw material. 5.91 g of ammonium metavanadate is dissolved in water to make the total weight of the solution 50 g, and the V concentration is 1 mmo.
An aqueous solution of 1 / g ammonium metavanadate was obtained. A catalyst was prepared in the same manner as in Example 16 except that 0.15 g of this aqueous solution was added to the impregnating solution of Example 16. The composition of the obtained catalyst was 17.2% by mass W ₁₂ Sb ₃ Zn ₆ V _0.1 Ox /
SA5218.

Example 25 Titanium tetrachloride aqueous solution (containing 16.0 to 17.0% of Ti)
A catalyst was prepared in the same manner as in Example 16, except that 0.44 g was added to the impregnating solution of Example 16. The composition of the obtained catalyst was 16.8% by mass W ₁₂ Sb ₃ Zn ₆ Ti ₁ Ox / SA52.
It was 18.

Example 26 Instead of the carrier SA5218, a silicon carbide self-sintering carrier (5 m
A catalyst was prepared in the same manner as in Example 1 except that 20 g of m-sphere) was used. The composition of the obtained catalyst was 13.6% by mass W ₁₂
It was Sb ₃ Fe ₂ Ox / SiC.

Example 27 The amount of the antimony tartrate aqueous solution was changed to 12.00 g, the amount of the iron nitrate aqueous solution was changed to 4.00 g, and the amount of the ammonium metatungstate aqueous solution was changed to 11.12 g. A catalyst was prepared in the same manner as in Example 1 except that the reaction was performed under a gas flow of (nitrogen). The composition of the obtained catalyst was 18.0% by mass W ₁₂ Sb ₃ Fe ₂ Ox / SA5218.
Met.

Example 28 In place of the aqueous solution of antimony tartrate, 1.166 g of antimony trioxide powder (purity: 99.999%) was used, and the mixture obtained by mixing and stirring was used as an impregnating liquid. A catalyst was prepared in the same manner as in Example 27 except that the catalyst was changed to. The composition of the obtained catalyst was 25.0% by mass W ₁₂ Sb.
₄ Fe ₂ Ox / SA5218.

Example 29 Example 2 was repeated except that 4.00 g of a bismuth nitrate aqueous solution having a Bi concentration of 0.5 mmol / g was added to the impregnating solution of Example 28.
Catalyst preparation was carried out in the same manner as in No. 8. The composition of the resulting catalyst was 2
3.0% by mass W ₁₂ Sb ₄ Bi ₁ Fe ₂ Ox / SA521
It was 8.

Example 30 A cerium nitrate aqueous solution was prepared as a Ce raw material. 21.73 g of cerium nitrate hexahydrate was dissolved in water to make the total weight of the solution 100 g, and a cerium nitrate aqueous solution having a Ce concentration of 0.5 mmol / g was obtained. A catalyst was prepared in the same manner as in Example 28 except that 2.00 g of the cerium nitrate aqueous solution was added to the impregnating solution of Example 28. The composition of the obtained catalyst was 25.4% by mass W ₁₂ Sb ₄ Fe ₂ Ce _0.5 Ox / SA5
218.

Example 31 A catalyst was prepared in the same manner as in Example 1 except that the aqueous iron nitrate solution was not used. The composition of the obtained catalyst was 13.8% by mass W ₁₂ Sb ₃ Ox / SA5218.

Comparative Example 1 A catalyst was prepared in the same manner as in Example 1 except that only 5.56 g of an aqueous solution of ammonium metatungstate was diluted with 8 ml of water. The composition of the resulting catalyst was 12.0
wt% WOx / SA5218.

[0062]

[Table 1]

Example 32 The same liquid as the impregnating liquid used in Example 1 was used, and the mixture was heated, stirred, concentrated and evaporated to dryness on a water bath without using a carrier, and dried at 120 ° C. for 16 hours. After crushing this, pellets (diameter 5 mm, length 5 mm)
The mold was tableted and fired at 650 ° C. for 2 hours in the atmosphere. The composition of the obtained catalyst was W ₁₂ Sb ₃ Fe ₂ Ox. Using 10 g of this catalyst, the reaction gas supply rate was 6.0.
0 L (standard state) / min (SV42600 hr ^-1 ),
The reaction was carried out under exactly the same conditions as in Example 1 except that the reaction temperature was 510 ° C. The reaction results were as follows: p-xylene conversion 93.1%, terephthalaldehyde selectivity 57.7%,
The p-tolualdehyde selectivity was 5.4%, the terephthalaldehyde single-stream yield was 53.7%, and the p-tolualdehyde single-stream yield was 5.0%.

Example 33 The outlet gas from 8 hours to 10 hours after the start of the reaction in Example 1 was collected with cooled methanol. After collection, the solution was concentrated using an evaporator to prepare a 75 g methanol solution. 4.06 g of terephthalaldehyde, p
It contained 0.44 g of tolualdehyde. This solution and ruthenium on activated carbon (ruthenium content 5% by mass)
1 g was charged and sealed. Next, after the inside of the autoclave was replaced with nitrogen, hydrogen gas was charged, the inside of the autoclave was pressurized to 5 MPa, and then heated to 80 ° C. The reaction was continued while stirring until hydrogen gas was no longer absorbed (until the internal pressure did not decrease). After the completion of the reaction, the content was taken out and filtered, and the reaction solution was analyzed using gas chromatography. As a result, the reaction solution contained 3.85 g of 1,4-cyclohexanedimethanol, and the conversion of terephthalaldehyde was 100%. Therefore, the yield of 1,4-cyclohexanedimethanol was 89 mol% based on terephthalaldehyde. Incidentally, 4% of p-xylylene glycol was produced.

Example 34 The outlet gas from 8 hours to 10 hours after the start of the reaction in Example 6 was collected with cooled methanol and concentrated by an evaporator to prepare a 75 g methanol solution. This solution contained 4.25 g of terephthalaldehyde and 0.32 g of p-tolualdehyde. This solution and 1 g of Raney nickel (nickel content 93 to 95% by mass, aluminum 5 to 7% by mass) were charged and sealed. Next, after the inside of the autoclave was replaced with nitrogen, hydrogen gas was charged, the inside of the autoclave was pressurized to 4 MPa, and then heated to 60 ° C. The reaction was continued while stirring until hydrogen gas was no longer absorbed (until the internal pressure did not decrease). After the completion of the reaction, the content was taken out and filtered, and the reaction solution was analyzed using gas chromatography. As a result, the reaction solution contained 3.97 g of 1,4-cyclohexanedimethanol, and the conversion of terephthalaldehyde was 100%. Therefore, 1,
The yield of 4-cyclohexanedimethanol was 87 mol% based on terephthalaldehyde. 5% of p-xylylene glycol was produced.

Comparative Example 2 The reaction gas in Comparative Example 1 was collected in the same manner as in Example 1 to prepare a 75 g methanol solution. This solution contained 0.56 g of terephthalaldehyde and 0.14 g of p-tolualdehyde. As a result of performing a hydrogenation reaction under the same conditions as in Example 1, the yield of 1,4-cyclohexanedimethanol was 56% based on terephthalaldehyde charged.

[0067]

The catalyst for oxidizing methylbenzenes of the present invention is excellent in partial oxidation performance and can produce the corresponding aromatic aldehyde from methylbenzenes in high yield. Further, according to the method for producing cyclohexanedimethanol according to the present invention, industrially very easy to obtain, using inexpensive xylene as a starting material, extremely useful as a raw material for polyester-based paints, synthetic fibers, synthetic resins, and the like. Cyclohexanedimethanol can be produced inexpensively and industrially.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C07C 29/50 C07C 29/50 33/14 33/14 45/36 45/36 47/542 47/542 / / C07B 61/00 300 C07B 61/00 300 (72) Inventor Hiroki Nagamura 4-1-1 Koraibashi, Chuo-ku, Osaka-shi, Osaka Japan Inside Nippon Shokubai Co., Ltd. (72) Inventor Akino Nakajima Koyohama, Himeji-shi, Hyogo 992 Nishioki 1 Inside Nippon Shokubai Co., Ltd. (72) Inventor Masashi Hashimoto 992 Nishioki Hyogo Prefecture, Amebashi-ku Kohinhama 1-Nishioki 992 Nishioki Co., Ltd. (72) Inventor 992 Nishioki 1 Nippon Shokubai Co., Ltd.

Claims (4)

[Claims] 1. A catalyst for oxidizing methylbenzenes in the gas phase in the presence of molecular oxygen to produce the corresponding aromatic aldehydes, comprising the following general formula (1): WaXbYcOx (1) 1) (where W represents a tungsten atom; X represents P, S
represents at least one element selected from the group consisting of b, Bi and Si. Y is Fe, Co, Ni, Mn, R
e, Cr, V, Nb, Ti, Zr, Zn, Cd, Y, L
a, Ce, B, Al, Tl, Sn, Mg, Ca, Sr,
It represents at least one element selected from the group consisting of Ba, Li, Na, K, Rb and Cs. O represents an oxygen atom. a, b, c and x represent the number of atoms of W, X, Y and oxygen atoms, respectively. However, the ratio of a, b and c is such that when a = 12, b = 0.5 to 10 and c = 0 to 15
Where x is a numerical value determined by the oxidation state of elements other than oxygen atoms. A catalyst for oxidizing methylbenzenes, which has a composition represented by the following formula: 2. The catalyst for oxidizing methylbenzenes according to claim 1, wherein the catalyst is supported on a refractory inorganic carrier. 3. A method for producing a corresponding aromatic aldehyde by subjecting methylbenzenes to gas-phase oxidation in the presence of molecular oxygen, which is used for oxidizing methylbenzenes according to claim 1 or 2. A method for producing an aromatic aldehyde, comprising using a catalyst. 4. A method for producing cyclohexanedimethanol by hydrogenating phthalaldehyde, wherein the phthalaldehyde is obtained by the method for producing aromatic aldehyde according to claim 3, wherein methylbenzenes are used as xylene. A process for producing cyclohexane dimethanol, characterized in that: