JP2003080068A - Solid catalyst and method for oxidizing alkanes using the same - Google Patents

Abstract

(57) Abstract: A solid catalyst obtained by allowing a carrier to support a transition metal alkynyl alkoxide obtained by reacting a transition metal alkoxide with an alkynyl alcohol, followed by calcining, and an alkane using the same. Oxidation method. The solid catalyst of the present invention can be easily prepared, and is stable in air, so that it is easy to handle. By using this solid catalyst, a wide range of alkanes can be oxidized, and ketones and alcohols can be efficiently produced. In addition, separation after use is easy, and reuse is possible.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a solid catalyst useful for oxidizing various alkanes with molecular oxygen, and a method for oxidizing alkanes using the same.

[0002]

2. Description of the Related Art Conventionally, when oxidizing alkanes with molecular oxygen to produce oxygen-containing compounds such as alcohols and ketones, soluble cobalt compounds such as cobalt naphthenate and boron-based compounds such as metaboric acid are generally used as catalysts. The compound is used.

However, soluble cobalt compounds such as cobalt naphthenate have the drawback that precipitates are formed during the reaction process and the catalyst is deactivated. Further, the soluble catalyst is generally unsuitable from the viewpoint of recovery and reuse of the catalyst, and it is necessary to support it on a carrier or the like for recovery. On the other hand, when a boron-based compound is used as a catalyst, there is a problem that the amount of the boron-based compound used is large because it passes through an ester type intermediate, and the number of steps is large for recycling and reuse of the catalyst.

Further, a catalyst for oxidizing alkanes with a high conversion rate and a high selectivity under milder conditions has been studied.
No. 2000-319211, JP-A-10-291812, etc.), and a method using an imide compound such as N-hydroxyphthalimide (JP-A-20-29120).
No. 00-239200, JP-A-10-286467, etc.) have been proposed. However, the heteropolyacid-based catalyst requires many steps for its preparation, takes much labor and time, and its catalytic activity is not sufficient. In addition, when an imide compound is used, the initial activity of the catalyst is high, but part of the catalyst decomposes and is consumed; a co-oxidant is needed and is consumed; product and catalyst (and its decomposition product) There was a problem that it was not easy to separate from and, and a process for separation was required.

Further, many catalyst systems other than the above have been proposed, but the raw materials to be subjected to the oxidation reaction are often limited to a narrow range, and few are applicable to various raw materials. For example, in Japanese Unexamined Patent Publication No. 4-9344, the starting material alkane is cyclohexane, and in Japanese Unexamined Patent Publication No. 5-269914, the starting material is limited to a specific benzene derivative.

[0006]

Therefore, an object of the present invention is to use a solid catalyst which is easy to prepare and inexpensive, and which can efficiently oxidize a wide range of alkanes by molecular oxygen, and an oxidation using the same. To provide a method.

[0007]

Under the circumstances, as a result of intensive studies by the present inventors, a wide range of alkanes can be oxidized by using a solid catalyst having a specific transition metal compound supported on a carrier, As a result, ketones and alcohols can be efficiently produced, and the separation of the catalyst,
They have found that they can be reused easily and completed the present invention.

That is, the present invention provides a solid catalyst obtained by supporting a transition metal alkynyl alkoxide obtained by reacting a transition metal alkoxide with an alkynyl alcohol on a carrier and then calcining it.

The present invention also provides a method for oxidizing alkanes, which comprises oxidizing alkanes with molecular oxygen in the presence of the above solid catalyst.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The transition metal alkoxide used in the present invention is preferably a transition metal having titanium, zirconium, vanadium, manganese, cobalt or copper, and an alkoxy group bonded to these transition metals. The alkoxy group bonded to the transition metal has 1 to 8 carbon atoms.
Preferred are, for example, methoxy group, ethoxy group, n
-Propoxy group, isopropoxy group, n-butoxy group,
Examples thereof include an isobutoxy group.

Specific examples of titanium alkoxides include titanium alkoxides such as titanium methoxide, titanium ethoxide, titanium n-propoxide, titanium isopropoxide, titanium n-butoxide and titanium isobutoxide; titanium diisopropoxy. Examples thereof include titanium dialkoxy dialkanate such as dobis acetylacetonate. Examples of zirconium alkoxides, vanadium alkoxides, manganese alkoxides, cobalt alkoxides, and copper alkoxides include compounds in which each central metal is bonded with various alkoxy groups similar to the above titanium alkoxide. In the case of pentavalent vanadium, vanadium oxyalkoxide may be used, and examples thereof include vanadium oxymethoxide, vanadium oxyethoxide, vanadium oxyn-propoxide, vanadium oxyisopropoxide, vanadium oxyn-butoxide, vanadium oxyisode. Butoxide and the like can be mentioned.

The alkynyl alcohol used in the present invention is not particularly limited as long as it is an aliphatic alcohol having 1 or 2 or more carbon-carbon triple bonds, and may be linear or branched and may be 1 or 2 or more. It may have a hydroxy group. In particular, 3-alkynyl alcohol having 3 to 16 carbon atoms is preferable in terms of handling because the transition metal alkynyl alkoxide produced by reacting with the transition metal alkoxide has higher stability. Specific examples include propargyl alcohol, 1-butyn-3-ol, 2-butyne-1,4-diol, 3,5-dimethyl-1-hexyne-3-ol, and the like, with propargyl alcohol being particularly preferred. .

The alkynyl alcohol is preferably used in excess of the stoichiometrically necessary amount, and is generally used in an amount of 4 mol or more, particularly 10 mol or more, preferably a pentavalent vanadium oxyalkoxide, based on the transition metal alkoxide. In general, it is preferable to use 3 mol or more, particularly 10 mol or more.

When each of the above transition metal alkoxides reacts with an alkynyl alcohol, it generally undergoes easy alcohol exchange with the alkynyl alcohol to form a transition metal alkynyl alkoxide, and dissociates the alcohol from the transition metal alkoxide.

A solvent can be used for the reaction between the transition metal alkoxide and the alkynyl alcohol. As the solvent, an alkynyl alcohol that is the same as or different from the alkynyl alcohol used in the reaction may be used in excess of the number of moles required for the reaction to act as the solvent, or a solvent other than this may be used. Examples of the solvent other than the alkynyl alcohol include aromatic hydrocarbons such as toluene and xylene; ethers such as diethyl ether and dipropyl ether.

The produced transition metal alkynyl alkoxide is generally stable even in the air, and even when the one in contact with the air is used for the catalyst preparation, the performance is hardly deteriorated.
This stability is presumably because the alkynylalkoxy group is strongly bonded to the transition metal due to the resonance stabilization of the alkynylalkoxy group.

The carrier supporting the obtained transition metal alkynyl alkoxide is insoluble in the reaction mixture under the reaction conditions and capable of physically and / or chemically adsorbing a catalytically effective amount of the transition metal alkynyl alkoxide. In addition, it is necessary that the material and the form are such that the adsorbed transition metal alkynyl alkoxide can be retained during handling. Specific examples include silica, silica gel, silica-alumina, zeolite, and the like, and silica gel is particularly preferable.

The method of supporting the transition metal alkynyl alkoxide on the carrier is not particularly limited, and a method generally used for preparing a catalyst can be used. For example, a method of once recovering the produced transition metal alkynyl alkoxide, re-dissolving or suspending this in a solvent, and then impregnating with a carrier; adding the carrier as it is without recovering the produced transition metal alkynyl alkoxide. A method of impregnating; a method of adding a carrier to a transition metal alkoxide and an alkynyl alcohol and allowing three components to react at the same time.

As the solvent used for re-dissolving, for example, aromatic hydrocarbons such as toluene and xylene; ethers such as diethyl ether and dipropyl ether can be used. Further, the same or different alkynyl alcohol as the alkynyl alcohol used for the reaction between the transition metal alkoxide and the alkynyl alcohol can also be used. The impregnation is generally carried out at 60 to 150 ° C, preferably 80 to 130 ° C for 1 to 5 hours.

Next, the solid component thus produced is filtered, dried and calcined to obtain the solid catalyst of the present invention. Firing is generally 300 to 900 ° C., preferably 400 to 600 ° C. for 1 to 18 hours, preferably 2
It takes 10 hours.

In the obtained solid catalyst, the amount of the transition metal supported is an amount effective for the activity as a catalyst. For example, when silica gel is used as a carrier, the silicon atom and the transition metal in the solid catalyst are used. The ratio with the atoms (silicon / transition metal ratio (gram atomic ratio)) is preferably 40 to 600. If the silicon / transition metal ratio is less than 40, the amount of transition metal relative to silicon becomes too large, and as a result, it is difficult to uniformly disperse the transition metal and the activity decreases. When the silicon / transition metal ratio exceeds 600, the amount of the transition metal with respect to silicon is too small and the activity is lowered.

The solid catalyst of the present invention thus obtained is particularly useful as a catalyst for the oxidation reaction of alkanes. That is, the alkanes can be efficiently oxidized by oxidizing the alkanes with molecular oxygen in the presence of the solid catalyst of the present invention.

Examples of alkanes applicable to the oxidation reaction include cyclic or chain alkanes. As the cyclic alkane, a monocyclic cyclic alkane (cycloalkane),
Examples thereof include polycyclic cyclic alkanes and aromatic ring-containing cyclic compounds. The aromatic ring-containing cyclic compound refers to a compound in which the alkane moiety of the compound is bonded or shared with a part of the aromatic ring to form a ring.

More specifically, examples of the monocyclic cyclic alkane include cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane and cyclooctane; examples of the polycyclic cyclic alkane include decalin, norbornane and adamantane. And so on;
Examples of the aromatic ring-containing cyclic compound include indane, tetrahydronaphthalene, fluorene and the like. Further, the chain alkane has 4 to 12 carbon atoms,
Examples thereof include butane, pentane, hexane, octane and the like. Of these, monocyclic cyclic alkanes, polycyclic cyclic alkanes, and cyclic alkanes of aromatic ring-containing cyclic compounds are preferable because of their higher oxidation reactivity.

The amount of the solid catalyst of the present invention used with respect to the alkane is 2 × 10 ^{−4 to} 1.0, particularly 5 × 10 ⁻⁴ to 1.0, based on the molar ratio of the transition metal in the solid catalyst to 1 mol of the alkane.
It is preferably 0.2.

The oxidation reaction using the solid catalyst of the present invention can be carried out without solvent. For example, alkanes such as hexane, octane and decane; ethers such as diethyl ether and dibutyl ether; isopropyl alcohol,
Alcohols such as tert-butyl alcohol; benzene,
It is also possible to use a solvent such as toluene.

Examples of the molecular oxygen include high-purity oxygen gas and air, as well as mixed gas obtained by diluting these with nitrogen, helium, argon, methane and the like.

The oxidation reaction using the solid catalyst of the present invention can be carried out by a slurry method or a fixed bed method, a batch method, a semi-continuous method, a continuous method or the like. The reaction conditions are appropriately set depending on the raw material alkane, but generally 20 to 250
C., preferably 60 to 200.degree. C., for 0.5 to 48 hours,
It can be preferably carried out under the condition of 1 to 24 hours.
The reaction pressure is preferably 0.01 to 5 MPa, particularly preferably 0.05 to 3 MPa in terms of oxygen partial pressure.

Since the catalyst of the present invention is in a solid state, it can be easily separated from the liquid phase containing the target product after completion of the reaction, and the target product is recovered from the liquid phase by separation / purification. can do. The recovered catalyst, solvent and unreacted raw material alkanes can be circulated and reused.

[0030]

EXAMPLES Next, the present invention will be further described with reference to examples, but the present invention is not limited to these examples.
The analysis in the examples was carried out by the following method. (1) Identification of transition metal alkynyl alkoxide: ¹³ C-
NMR and FT-IR (2) Analysis of transition metal atoms and silicon atoms: X-ray fluorescence method (3) Conversion and selectivity (molar basis): Gas chromatographic method

Reference Example 1 (Reaction of Titanium Alkoxide with Alkynyl Alcohol) A mixture of 1.06 g of titanium tetraisopropoxide and 200 g of propargyl alcohol was reacted by stirring at 80 ° C. for 30 minutes. Using part of the reaction product as it is
^{The 13} C-NMR was measured, and the FT-IR was measured using a product obtained by distilling off the solvent and alcohol components from the reaction product and further evaporating to dryness. And got ¹³
C-NMR spectrum (FIGS. 1 and 2) and FT-IR
Formation of titanium propargyl alkoxide was confirmed by analysis of the spectrum (FIG. 3).

That is, the peak (A ') derived from the carbon of the methylene group of 52 ppm seen in the spectrum of propargyl alcohol of FIG. 2 is greatly reduced in FIG. 1 after the reaction, and is a broad peak (A) at 56 ppm. Is appearing. The ppm shifts to the higher side and becomes broad because propargyl alcohol undergoes an alcohol exchange reaction with titanium tetraisopropoxide and the hydroxyl group of propargyl alcohol is bonded to titanium, which affects the methylene group adjacent to oxygen. it is conceivable that.

Further, when the spectrum of FT-IR (FIG. 3) was analyzed, each absorption could be specified as follows, and it was confirmed that titanium propargyl alkoxide was produced. 3290~3275cm ^-1 C-H bonds 2120～2105Cm ^-1 carbons of C-H bonds 2915～2862Cm ^-1 methylene group alkyne group - carbon triple bond 1620,1575,1112cm ^-1 Ti-O bond

Example 1 (Preparation of solid catalyst (A)) In the same manner as in Reference Example 1, titanium tetraisopropoxide 1.
8g of a mixture of 06g and 200g of propargyl alcohol
After stirring for 30 minutes at 0 ° C., silica gel 100 (specific surface area (BET method) 270 to 370 m ² / g, pore volume 0.9 to
14 mL of 1.2 mL / g and a particle size of 0.063 to 0.2 mm) was added and refluxed for 2 hours. After cooling, the solid content was collected by filtration and dried. Then, the obtained solid content is crushed to 50
The solid catalyst (A) was obtained by baking at 0 ° C. for 5 hours. The obtained solid catalyst (A) was analyzed to find that silicon /
The titanium ratio was 75.4.

Example 2 (Preparation of solid catalyst (B)) A mixture of 1.43 g of zirconium tetra-n-butoxide and 200 g of propargyl alcohol was stirred at 80 ° C. for 30 minutes, and then 14 g of the same silica gel as in Example 1 was added. And refluxed for 2 hours. Then, the same treatment as in Example 1 was carried out to obtain a solid catalyst (B). Obtained solid catalyst (B)
Has a silicon / zirconium ratio of 100.0 as a result of analysis.
Met.

Example 3 (Preparation of Solid Catalyst (C)) A mixture of 0.91 g of vanadium oxytriisopropoxide and 100 g of propargyl alcohol was added at 80 ° C. for 30 minutes.
After stirring for 1 minute, 7 g of the same silica gel as in Example 1 was added and refluxed for 2 hours. Then, the same treatment as in Example 1 was carried out to obtain a solid catalyst (C). Obtained solid catalyst (C)
As a result of analysis, the silicon / vanadium ratio was 53.8.

Example 4 (Preparation of solid catalyst (D)) The solid catalyst (D) was prepared in the same manner as in Example 1 except that silica gel (MCM-41 type) prepared by a conventional method was used as the carrier instead of silica gel. ) Got.

Example 5 In a reactor, 0.1 g of the solid catalyst (B) and 5.0 g (16.9 mmol) of cyclohexane were collected, and then air was added to 2.
Introduce up to 0MPa and keep the pressure of air constant 15
The reaction was carried out at 0 ° C for 4 hours. When the reaction product was analyzed, the conversion rate of cyclohexane as a raw material was 6.9%,
The selectivity of the product is 27.1 mol of cyclohexanol
% And cyclohexanone 71.5 mol%.

Example 6 After the reaction of Example 5, the oxidation reaction of cyclohexane was carried out in the same manner as in Example 5 except that the solid catalyst (B) used in the reaction was separated by filtration and recovered. . The conversion of cyclohexane was 6.5%, and the selectivity of the product was 30.4 mol% of cyclohexanol and 6 of cyclohexanone.
It was 3.3 mol%. Therefore, even if the solid catalyst (B) recovered by filtration was reused, the conversion rate and the selectivity were not decreased.

Example 7 0.1 g of solid catalyst (B) and 5.0 g of cyclopentane
(7.1 mmol) using air 2.0MPa,
The reaction was carried out at 0 ° C for 3 hours. The conversion of cyclopentane was 0.78%, and the selectivities of products were 22.4 mol% of cyclopentanol and 48.9 mol% of cyclopentanone.

Example 8 0.1 g of solid catalyst (A) and 0.5 g of adamantane (3.
6 mmol) and 5.0 g of benzene, air pressure 2.0MP
Under the conditions of a, the reaction was carried out at 190 ° C. for 7 hours. The conversion rate of adamantane was 56.3%, and the selectivities of the products were 1-adamantanol 67.4 mol%, 2-adamantanol 12.4 mol%, and 2-adamantanone 6.0 mol%.

Example 9 0.1 g of solid catalyst (B) and 0.5 g of adamantane (3.
6 mmol) and 5.0 g of benzene were used and reacted in the same manner as in Example 8. The conversion rate of adamantane is 24.9%,
The selectivity of the product is 1-adamantanol 70.3mol
%, 2-adamantanol 20.2 mol%, and 2-adamantanone 2.8 mol%.

Example 10 1.4 g of solid catalyst (A) and 0.48 g of fluorene (2.
9 mmol) and 5.6 g of benzene were used and reacted in the same manner as in Example 8. The conversion of fluorene was 41.2% and the selectivity of the product was 9-fluorenone 74.0 mol%.

Example 11 0.22 g of solid catalyst (C) and 0.5 g of fluorene (3.
0 mmol) and 5.0 g of benzene were used and reacted in the same manner as in Example 8. The conversion of fluorene was 78.9% and the selectivity of the product was 9-fluorenone 87.9 mol%.

Example 12 Solid catalyst (D) 0.18 g, fluorene 0.49 g
Example 8 using (3.0 mmol) and 2.1 g of benzene.
The reaction was performed in the same manner as in. Conversion of fluorene is 70.8%
The product selectivity is 9-fluorenone 96.0 mol.
%Met.

Example 13 0.1 g of solid catalyst (A) and 2.0 g of indane (16.
9 mmol) and an air pressure of 1.4 MPa at 100 ° C.
And reacted for 3 hours. Indan conversion rate is 43.1%
And the selectivity of the product is 11.6 mol of 1-indanol
%, 1-indanone 56.0 mol%.

Example 14 0.1 g of solid catalyst (C) and 2.0 g of indane (16.
9 mmol) and an air pressure of 1.4 MPa at 100 ° C.
And reacted for 8 hours. Indan conversion rate is 69.2%
Then, the selectivity of the product is 15.2 mol of 1-indanol.
%, 1-indanone 75.3 mol%.

Example 15 Solid catalyst (D) 0.05 g and indane 2.0 g (1
6.9 mmol) and an air pressure of 1.4 MPa under the conditions of 15
The reaction was carried out at 0 ° C for 3 hours. Indan conversion rate is 70.3
%, The product selectivity is 2.4 mol of 1-indanol
%, 1-indanone 52.8 mol%.

Example 16 (Preparation of solid catalyst (E)) 10 g of manganese n-butoxide / ethanol solution (containing 10 mmol of manganese), 10 g of propargyl alcohol.
After stirring a mixture of toluene and 95 g of toluene at 80 ° C. for 30 minutes, silica gel 100 (specific surface area (BET method) 27
0-370 m ² / g, pore volume 0.9-1.2 mL / g, particle size 0.063-0.2 mm) 14 g were added and refluxed for 2 hours. After cooling, the solid content was collected by filtration and dried. Then, the obtained solid content was calcined at 500 ° C. for 5 hours to obtain a solid catalyst (E). As a result of analysis, the obtained solid catalyst (E) had a silicon / manganese ratio of 78.

Example 17 (Preparation of solid catalyst (F)) 1.4 g of cobalt n-butoxide / ethanol solution (containing 9.8 mmol of cobalt), propargyl alcohol 1
A mixture of 0 g and 90 g of toluene was stirred at 80 ° C. for 30 minutes, 14 g of the same silica gel as in Example 16 was added, and the mixture was refluxed for 2 hours. Then, the same treatment as in Example 16 was carried out to obtain a solid catalyst (F). Obtained solid catalyst (F)
As a result of analysis, the silicon / cobalt ratio was 251.

Example 18 (Preparation of solid catalyst (G)) 7 g of copper n-butoxide / ethanol solution (6.2 mmol of copper)
And 100 g of propargyl alcohol were stirred at 80 ° C. for 30 minutes, 7 g of the same silica gel as in Example 16 was added, and the mixture was refluxed for 2 hours. Then, the same treatment as in Example 16 was carried out to obtain a solid catalyst (G). The solid catalyst (G) thus obtained was analyzed and found to have a silicon / copper ratio of 52.
It was 0.

Example 19 In a reactor, 0.1 g of the solid catalyst (E) and 5.0 g (16.9 mmol) of cyclohexane were collected, and then air was added to 2.
Fill up to 0MPa and keep the air pressure at 150 ℃
And reacted for 3 hours. When the reaction product was analyzed, the conversion of cyclohexane was 3.8%, and the selectivities of the product were 26.6 mol% of cyclohexanol and 33.8 mol% of cyclohexanone.

Example 20 In the same manner as in Example 19, 0.1 g of the solid catalyst (F) and 5.0 g (16.9 mmol) of cyclohexane were used and the reaction was carried out at 140 ° C. for 2.5 hours at an air pressure of 2.0 MPa. When the reaction product was analyzed, the conversion of cyclohexane was 4.
At 7%, the product selectivity is cyclohexanol 32.
The contents were 5 mol% and 57.6 mol% cyclohexanone.

Example 21 In the same manner as in Example 19, 0.1 g of the solid catalyst (G) and 5.0 g (16.9 mmol) of cyclohexane were used and the reaction was carried out at an air pressure of 2.0 MPa and 150 ° C. for 2 hours. When the reaction product was analyzed, the conversion of cyclohexane was 10.4.
% Product selectivity is 24.3% cyclohexanol
% and cyclohexanone 45.1 mol%.

Example 22 0.1 g of solid catalyst (E) and 5.0 g of adamantane (3.
6 mmol) and 5.0 g of benzene, air pressure 2.0MP
a, reacted at 190 ° C. for 7 hours. When the reaction product was analyzed, the conversion of adamantane was 79.4%, the selectivity of the product was 1-adamantanol 72.3 mol%,
The content of 2-adamantanol was 2.8 mol% and the content of 2-adamantanone was 4.0 mol%.

Example 23 0.1 g of solid catalyst (F) and 5.0 g of adamantane (3.
6 mmol) and 5.0 g of benzene, air pressure 2.0MP
a, reacted at 190 ° C. for 7 hours. When the reaction product was analyzed, the conversion of adamantane was 10.7%, the selectivity of the product was 1-adamantanol 69.1 mol%,
The content of 2-adamantanol was 5.4 mol% and that of 2-adamantanone was 22.3 mol%.

Example 24 0.1 g of solid catalyst (G) and 5.0 g of adamantane (3.
6 mmol) and 5.0 g of benzene, air pressure 2.0MP
a, reacted at 190 ° C. for 7 hours. When the reaction product was analyzed, the conversion of adamantane was 24.9%, the selectivity of the product was 1-adamantanol 74.8 mol%,
The content of 2-adamantanol was 2.8 mol% and that of 2-adamantanone was 19.5 mol%.

Example 25 0.5 g of solid catalyst (E), 0.5 g of fluorene (0.3
0 mmol) and 5.0 g of benzene, and an air pressure of 2.0 MP
a, reacted at 190 ° C. for 15 hours. When the reaction product was analyzed, the conversion rate of fluorene was 82.6% and the selectivity of the product was 9-fluorenone 81.3 mol%.

Example 26 0.5 g of solid catalyst (F), 0.5 g of fluorene (0.3
mmol) and 5.0 g of benzene, and an air pressure of 2.0 MP
a, reacted at 190 ° C. for 7 hours. When the reaction product was analyzed, the conversion of fluorene was 32.8% and the selectivity of the product was 9-fluorenone 79.8 mol%.

Example 27 0.5 g of solid catalyst (G), 0.5 g of fluorene (0.3
mmol) and 5.0 g of benzene, and an air pressure of 2.0 MP
a, reacted at 190 ° C. for 7 hours. When the reaction product was analyzed, the conversion rate of fluorene was 54.3% and the selectivity of the product was 9-fluorenone 83.0 mol%.

Comparative Example 1 (Preparation of solid catalyst (H)) Ethanol was used in place of propargyl alcohol,
The same treatment as in Example 16 was carried out to obtain a solid catalyst (H).

Comparative Example 2 (Preparation of Solid Catalyst (I)) Ethanol was used in place of propargyl alcohol,
The same treatment as in Example 17 was carried out to obtain a solid catalyst (I).

Comparative Example 3 0.25 g of solid catalyst (H) and 0.5 g of fluorene (0.
3 mmol) and 5.0 g of benzene, and an air pressure of 2.0 MP
a, reacted at 190 ° C. for 7 hours. When the reaction product was analyzed, the conversion rate of fluorene was 64.8% and the selectivity of the product was 9-fluorenone 66.1 mol%.

Comparative Example 4 0.5 g of solid catalyst (I), 0.5 g of fluorene (0.3
mmol) and 5.0 g of benzene, and an air pressure of 2.0 MP
a, reacted at 190 ° C. for 7 hours. When the reaction product was analyzed, the conversion of fluorene was 34.2% and the selectivity of the product was 90.0-fluorenone 30.0 mol%.

Comparative Example 5 (Preparation of Solid Catalyst (J)) Ethanol was used in place of propargyl alcohol, and manganese (II) chloride was used in place of manganese n-butoxide / ethanol solution. To obtain a solid catalyst (J).

Comparative Example 6 (Preparation of Solid Catalyst (K)) Ethanol was used in place of propargyl alcohol, and cobalt (II) chloride was used in place of cobalt n-butoxide / ethanol solution, and treated in the same manner as in Example 17. To obtain a solid catalyst (K).

Comparative Example 7 (Preparation of Solid Catalyst (L)) Ethanol was used instead of propargyl alcohol and copper n
-Copper (II) chloride instead of butoxide / ethanol solution
Was treated in the same manner as in Example 18 to obtain a solid catalyst (L).

Comparative Example 8 0.5 g of solid catalyst (J), 0.5 g of fluorene (0.3
mmol) and 5.0 g of benzene, and an air pressure of 2.0 MP
a, reacted at 190 ° C. for 7 hours. When the reaction product was analyzed, the conversion of fluorene was 55.6% and the selectivity of the product was 9-fluorenone 55.3 mol%.

Comparative Example 9 0.5 g of solid catalyst (K), 0.5 g of fluorene (0.3
mmol) and 5.0 g of benzene, and an air pressure of 2.0 MP
a, reacted at 190 ° C. for 7 hours. When the reaction product was analyzed, the conversion rate of fluorene was 37.4% and the selectivity of the product was 91.0 fluorenone 31.0 mol%.

Comparative Example 10 0.5 g of solid catalyst (L), 0.5 g of fluorene (0.3
mmol) and 5.0 g of benzene, and an air pressure of 2.0 MP
a, reacted at 190 ° C. for 7 hours. When the reaction product was analyzed, the conversion of fluorene was 65.1% and the selectivity of the product was 9-fluorenone 59.8 mol%.

Examples 25 to 27, Comparative Examples 3 to 4 and 8 to
The results of 10 are shown in Table 1.

[0072]

[Table 1]

From the results shown in Table 1, when the metal is manganese,
When carrying an n-butoxide compound (Comparative Example 3),
The conversion rate and selectivity decreased, and when chloride was used (Comparative Example 8), the conversion rate and selectivity further decreased. Also,
In the case of cobalt and copper, although the conversion rate is similar,
The selectivity is greatly reduced. Therefore, it was confirmed that the solid catalyst of the present invention has high activity and is particularly excellent in selectivity.

[0074]

INDUSTRIAL APPLICABILITY The solid catalyst of the present invention can be easily prepared by supporting a transition metal alkynyl alkoxide on a carrier, and since it is stable in air, it is easy to handle. By using this solid catalyst, a wide range of alkanes can be oxidized, and ketones and alcohols can be efficiently produced. In addition, it can be easily separated after use and can be reused.

[Brief description of drawings]

FIG. 1 Product obtained by reacting titanium tetraisopropoxide with propargyl alcohol (reaction mixture)
It is a figure which shows the ¹³ C-NMR spectrum of.

FIG. 2 is a diagram showing a ¹³ C-NMR spectrum of propargyl alcohol.

FIG. 3 is a diagram showing an FT-IR spectrum of a product (titanium propargyl alkoxide) obtained by reacting titanium tetraisopropoxide with propargyl alcohol.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B01J 29/70 B01J 37/02 101Z 37/02 101 C07C 27/12 310 C07C 27/12 310 35/06 35 / 06 35/08 35/08 35/32 35/32 35/37 35/37 35/38 35/38 45/33 45/33 49/395 49/395 49/403 A 49/403 49/453 49 / 453 49/67 49/67 49/675 49/675 C07B 61/00 300 // C07B 61/00 300 B01J 23/74 311Z (72) Inventor Makoto Irie 5-10-15 F-term, Maebaru Nishi, Funabashi City, Chiba Prefecture (Reference) 4G069 AA03 AA08 BA01A BA02A BA02B BA07A BA07B BA38 BC29A BC31A BC31B BC50A BC50B BC51A BC51B BC54A BC54B BC62A BC62B BC67A BC67B BE06C CB07 DA45 BA30 BA60 BA81 BA60 BA20 BA60 BA60 BA20 BA60 BA20 BA60 BA20 BA60 BA02 BA60 BA02 BA60 BA02 AC08 AZA44A02H0808ZA32B02H0808ZA32A02B08A16A02BA08BA16BA02 BA08BA16 BA02 BA08 BA16 BA02 BA08 BA16 BA02 BA08 BA16 BA02 BA08 BA16 BA02 AC08 AZABAA4 FC22 FC56 4H039 CA60 CA62 CC30

Claims (10)

[Claims] 1. A solid catalyst obtained by supporting a transition metal alkynyl alkoxide obtained by reacting a transition metal alkoxide with an alkynyl alcohol on a carrier and then calcining the carrier. 2. The solid catalyst according to claim 1, wherein the transition metal is zirconium, vanadium, manganese, cobalt or copper. 3. The solid catalyst according to claim 1, wherein the carrier is silica-alumina or zeolite. 4. The solid catalyst according to claim 1, which is a catalyst for the oxidation reaction of alkanes. 5. The solid catalyst according to claim 4, wherein the transition metal is titanium, zirconium, vanadium, manganese, cobalt or copper. 6. The alkynyl alcohol is propargyl alcohol, 1-butyn-3-ol, 2-butyne-.
The solid catalyst according to claim 1, which is 1,4-diol or 3,5-dimethyl-1-hexyn-3-ol. 7. The solid catalyst according to claim 4, wherein the carrier is silica gel. 8. The solid catalyst according to claim 7, wherein the silicon / transition metal ratio (gram atomic ratio) in the solid catalyst is 40 to 600. 9. The solid catalyst according to claim 4, wherein the alkane is a monocyclic cyclic alkane, a polycyclic cyclic alkane, or an aromatic ring-containing cyclic compound. 10. A method for oxidizing alkanes, which comprises oxidizing alkanes with molecular oxygen in the presence of the solid catalyst according to any one of claims 1 to 9.