JPH07149685A - Production of carbonyl compound - Google Patents

Abstract

PURPOSE:To easily, stably obtain in high yield a carbonyl compound useful as a solvent or chemical feedstock by reacting an olefin with an oxidative gas under specified conditions. CONSTITUTION:An olefin is reacted with an oxidative gas in the presence of a palladium compound (e.g. PdSO4.2H2O), polyoxoanionic compound [e.g. (PV3Mo9O40)<6->] and iron-contg. compound [e.g. Fe2(SO4)3] in a solvent consisting of at least one kind of compound selected from oxygen-contg. compounds (e.g. 1,4-dioxane) and sulfur-contg. compounds (e.g. dimethylsulfoxide) or a mixed solvent compound of the compound (s) and water to obtain the objective carbonyl compound useful as a solve or chemical feedstock such as methyl ethyl ketone, methyl isobutyl ketone, acetone, cyclopentanone or cyclohexanone, or as a precursor for higher alcohols such as a ketone or aldehyde. For this reaction, catalytic activity deterioration can be prevented and reaction rate can be maintained stably at high levels without the need for separating reaction process from catalyst regeneration process.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a carbonyl compound, more specifically, it is not necessary to separate the reaction step and the catalyst regeneration step from each other, and the catalyst activity is prevented from deteriorating due to sedimentation or aggregation of catalyst components. Dodecanone, which is a precursor of methyl ethyl ketone, methyl isobutyl ketone, acetone, cyclopentanone, cyclohexanone, or higher alcohol, which is useful as a solvent or a chemical raw material, while maintaining a substantially high level of catalytic activity and reaction rate stably.
The present invention relates to a method for producing a carbonyl compound, which can easily and conveniently produce a carbonyl compound such as a ketone such as tetradecanone or hexadecanone or an aldehyde such as acetaldehyde and at a high yield.

[0002]

2. Description of the Related Art Conventionally, there has been a method of directly oxidizing olefins as a method for producing a carbonyl compound, and a typical example thereof is PdCl _2-.
A Wacker method using a CuCl ₂ catalyst is known. However, in this Wacker method, the reaction rate significantly decreases as the carbon number of the raw material olefin increases,
There are drawbacks such as low reactivity of internal olefins. Moreover, it is necessary to use a relatively large amount of chlorine compounds,
Because of problems such as equipment corrosion and chlorinated by-products, it is industrially used only for the production of lower carbonyl compounds such as acetaldehyde and acetone.

Recently, several improved examples of the Wacker method have been proposed in which a catalyst system or a solvent is devised. For example, Patent Publication No. 63-500923 proposes a method using a catalyst system in which a redox metal such as Cu, Fe and Mn and / or a ligand (acetonitrile etc.) is added to a Pd-polyoxoanion system. Has been done. However, in this case, the addition of either the redox metal or the ligand has a small effect of improving the catalytic activity, and the effect of the synergistic effect of the two is large. Further, even if the initial reactivity is relatively good, there is a serious problem that the catalyst component precipitates as the reaction progresses and the reaction rate significantly decreases.

Also, Journal of American Chemical Society No. 112, pages 5160 to 5166 (1990) describes a method for producing a carbonyl compound using a catalyst containing palladium, a polycyclic metal and quinone. It is disclosed. However, in this case, isomerization of a terminal olefin to an internal olefin occurs due to the presence of an acid, and the reactivity is low. Moreover, there is a problem that the palladium compound rapidly precipitates in the absence of acid.

Further, International Patent Publication No. WO91 / 138
51, WO91 / 13852, WO91 / 13853,
In each publication relating to WO91 / 13854, palladium-
Polyoxoanion-based catalysts such as HCl, MCl
A method for producing a carbonyl compound from an olefin using a chlorine compound such as (M means an alkali metal) is disclosed. The chlorine compound is added to the reaction system in order to make the chloride ion concentration in the reaction system sufficient. This is because the chloride ion concentration of the reaction system cannot be made to a sufficient degree only by the chloride ion generated from the compound such as PdCl ₂ used as the palladium source. However, in this method, since the rate of catalyst regeneration is very slow with respect to the rate of the reaction process, the catalyst regeneration step and the reaction step must be separated, and the catalyst liquid is regenerated by oxygen in another step. The process is complicated as it is used again for the reaction.
Further, in order to prevent the precipitation of the palladium compound, a large amount of polyoxoanion compound and chlorine ion are used to make the residence time in the reaction step very short. as a result,
In addition to being economical, the product concentration after the reaction is extremely low and S
There is also a problem that TY (unit capacity, production amount per unit time) is also low.

The present invention solves the above problems and eliminates the need to separate the reaction step and the catalyst regeneration step, prevents deterioration of the catalytic activity due to sedimentation or agglomeration of the catalytic components, and achieves a substantial catalytic activity and Ketones such as methylethylketone, methylisobutylketone, acetone, cyclopentanone, cyclohexanone, or precursors of higher alcohols, such as dodecanone, tetradecanone, and hexadecanone, which keep the reaction rate stable at a high level for a long time and are useful as solvents and chemical raw materials. An object of the present invention is to provide a method for producing a carbonyl compound, which can easily and conveniently produce a carbonyl compound such as aldehydes such as acetaldehyde and the like and stably in a high yield.

[0007]

The aspects of the present invention for solving the above-mentioned problems will be listed below.

The first aspect of the present invention is to provide at least one selected from the group consisting of an oxygen-containing compound and a sulfur-containing compound, or these and water in the presence of a palladium compound, a polyoxoanion compound and an iron-containing compound. A method for producing a carbonyl compound, which comprises reacting an olefin and an oxidizing gas in a solvent of a mixture with a carbonyl compound. The second aspect of the present invention is the method for producing a carbonyl compound according to the first aspect. In the method of producing the carbonyl compound according to claim 1, wherein the content of the water in the solvent is 50% by volume or less, the third aspect of the present invention is the first aspect or the In the method for producing a carbonyl compound according to the second aspect, the olefin comprises a chain internal olefin, a chain terminal olefin and a cyclic olefin. The fourth aspect of the present invention is at least one selected from the group, and in the method for producing a carbonyl compound according to any one of the first to third aspects, the oxidizing gas is selected from the group consisting of oxygen and an oxygen-containing gas. At least one selected.

The method for producing the carbonyl compound according to the present invention will be described in more detail below.

In the method of the present invention, by reacting a raw material in a specific solvent in the presence of a specific catalyst,
A carbonyl compound is produced.

-Catalyst- The catalyst in the present invention is a) a palladium compound,
Obtained from b) polyoxoanion compounds and c) iron-containing compounds.

A) Palladium Compound The palladium compound is not particularly limited as long as it is a compound containing palladium (Pd) as a metal component, and various compounds known per se can be mentioned.
For example, various inorganic systems such as palladium sulfate, palladium nitrate, palladium chloride, palladium bromide, sodium tetrachloropalladate, sodium tetrabromopalladate, potassium tetrachloropalladate, potassium tetrabromopalladate, palladium hydroxide, and palladium oxide. palladium _{compound; Pd (NH 3) 4 Cl} 2,
Ammine complex compounds such as Pd (NH ₃ ) ₂ Cl ₄ ; Palladium organic acid salts such as palladium acetate; Palladium acetylacetonate (abbreviation: Pd (acac) ₂ ); Organic palladium compounds such as alkylpalladium compounds;
Pd (CH ₃ CN) ₂ Cl ₂ , Pd (PhCN) ₂ Cl
₂ {however, Ph represents a phenyl group. same as below. } Palladium nitrile complex such as Pd (PPh ₃ ) ₄ Palladium phosphine complex such as Pd (edta) {however,
edta represents ethylenediaminetetraacetic acid. }, Pd ₂
(Dba) ₃ CHCl ₃ (where dba represents dibenzylideneacetone). }, Pd (cod) Cl ₂ {where cod represents cyclooctadiene. }, Various organic complexes; palladium-containing polyoxoanion compounds such as heteropolyacid palladium salt and isopolyacid palladium salt; active metal palladium such as palladium colloid and highly dispersed palladium metal.

Of these, inorganic palladium compounds are preferable from the viewpoint of the activity of the oxidation reaction, and among them, inorganic palladium compounds having divalent (oxidation number +2) palladium are preferable, and PdSO ₄ .2H _{2 is} particularly preferable. O is preferred.

The palladium compound may be an anhydride or a water of crystallization content, and may be used alone or in combination of two or more as a mixture, a complex compound or a composition. Good. The palladium compound can be used in various forms such as various solutions such as an aqueous solution and an organic solvent solution, a suspension state, or a state of being supported on a carrier such as activated carbon.

B) Polyoxoanion compound As the polyoxoanion compound, in the catalytic cycle, reduced Pd is converted into oxidized Pd, especially Pd ^2+.
There is no particular limitation as long as it is a polyoxoanion compound that can be easily oxidized and the reduced polyoxoanion itself generated thereby can be easily reoxidized by an oxidizing agent such as oxygen, and various known publicly known compounds can be used. Mention may be made of polyoxoanion compounds. For example, V, Mo, W,
Examples thereof include polyoxoanions containing one kind or two or more kinds of metal components such as Nb and Ta. The polyoxoanion may be either a heteropolyoxoanion or an isopolyoxoanion. The heteropolyoxoanion may include, for example, P, Si, As, Ge, B, Se, in the skeletal structure of the polyoxoanion.
It is a compound having various heteroatoms such as Te. P is preferable as the hetero atom.

Among these polyoxoanions, in the case where the metal component is one, those containing Mo or V are preferable, and in the case of the mixed coordination type containing two or more metal components, Mo, V and Mo. Those containing W or two kinds of V and W, and those containing three kinds of Mo, W and V are preferable.

Specific preferred examples of the polyoxoanion include (PV ₃ Mo ₉ O ₄₀ ) ^6- and (PV ₄ Mo ₈ O
₄₀ ) ^7- , (PV ₆ Mo ₆ O ₄₀ ) ^9- , (PV ₂ Mo
₁₀ O ₄₀ ) ^5- , (PV ₈ Mo ₄ O ₄₀ ) ^11- , (PMo ₆ W
₆ O ₄₀ ) ^3- , (P ₂ VMo ₂ W ₁₅ O ₆₂ ) ^7- , (P ₂ VM
^{_{o 5 W 12 O 62) 7-}} , (PMo 12 O 40) heteropolyoxometalate anion of ^3-like, and _{(V 3 Mo 3 O 19)} 5-, (V 2
Mo ₆ O ₂₆ ) ^6- , (V ₄ Mo ₈ O ₃₆ ) ^4- , (V ₆ Mo ₆
O ₃₆ ) ^6- , (V ₈ Mo ₄ O ₃₆ ) ^8- , (V ₂ Mo ₃ W ₇ O
₃₆ ) ^{Isopolyoxoanions} such as ^2- can be mentioned.

As the polyoxoanion compound,
A compound comprising the above-mentioned heteropolyoxoanion or isopolyoxoanion and one or more cation components (counter cations), that is, heteropolyacid or a salt thereof and isopolyacid or a salt thereof can be mentioned. The polyoxoanion compound may contain water of crystallization. Examples of the cation component (counter cation) include H
⁺ , NH ₄ ⁺ , Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ ,
Cu ²⁺ , Ag ⁺ , Pd ²⁺ , Rh ^{3+ and the} like can be mentioned. Of these, H ⁺ is particularly preferable.

There are various polyoxoanion compounds depending on the kind and combination of the polyoxoanion and the cation component, and any of them can be used. In the present invention, among these, a heteropoly acid composed of the heteropolyoxoanion and H ⁺ is preferable from the viewpoint of catalytic activity and the like. In consideration of a combination with the palladium compound, an inorganic palladium compound, particularly an inorganic palladium compound having divalent (oxidation number +2) palladium, particularly PdSO ₄ .2H ₂ O
As the polyoxoanion compound to be combined with, a heteropolyacid composed of the above heteropolyoxoanion and H ⁺ is preferable.

Particularly preferred specific examples of the heteropolyacid include H ₅ (PV ₂ Mo ₁₀ O ₄₀ ), H ₆ (PV ₃ Mo
₉ O ₄₀ ), H ₇ (PV ₄ Mo ₈ O ₄₀ ), H ₉ (PV ₆ M
o ₆ O ₄₀ ), H ₁₁ (PV ₈ Mo ₄ O ₄₀ ), H ₃ (PMo ₆
W ₆ O ₄₀ ), H ₇ (P ₂ VMo ₂ W ₁₅ O ₆₂ ), H _{7
(P 2 VMo 5 W 12 O} 62) , and the like.

Of these, H ₆ is particularly preferable.
It is at least one selected from the group consisting of (PV ₃ Mo ₉ O ₄₀ ), H ₇ (PV ₄ Mo ₈ O ₄₀ ), and H ₃ (PMo ₆ W ₆ O ₄₀ ).

The polyoxoanion compound may be an anhydride or a water of crystallization, and may be used alone or in a mixture of two or more, a complex compound,
You may use together as a composition. Further, the polyoxoanion compound can be used in various forms such as various solutions such as an aqueous solution and an organic solvent solution, a suspension state, or a state of being supported on a carrier such as activated carbon.

The amount of the polyoxoanion compound used can be appropriately selected according to the purpose, but is usually 0.5 to 500 times by mole with respect to the palladium compound.
It is preferably 1 to 300 times mol. The amount used is 0.
If it is less than 5 mol, the reoxidation of the palladium compound in the catalytic cycle may not be sufficiently carried out, or in some cases, a high level of catalyst activity may not be maintained. By-products are likely to be generated, which may be economically disadvantageous.

C) Iron-containing compound As the iron-containing compound, iron (Fe) is used as a metal component.
There is no particular limitation as long as it is a compound containing, and various known compounds can be mentioned. For example, Fe ₂
(SO ₄ ) ₃ , FeSO ₄ , Fe (NO ₃ ) ₃ , Fe
(NO ₃ ) ₂ , Fe (OH) ₂ , Fe (NH ₄ ) ₂ (S
O ₄ ) ₂ , Fe (NH ₄ ) (SO ₄ ) ₂ , FeK (SO
₄ ) ₂ , Fe (ClO ₄ ) ₃ , Fe (ClO ₄ ) _{2 and} other inorganic iron-containing compounds; FeC ₆ H ₅ O ₇ , Fe (CH ₃
CO ₂ ) ₂ , Fe ₂ (C ₂ O ₄ ) ₃ , FeC ₂ O _{4 and} other organic iron-containing compounds; Fe (CO) ₃ , FeCl ₂ (P
Ph ₃ ) ₂ , Na ₃ [Fe (C ₂ O ₄ ) ₃ ], K ₃ [F
e (C ₂ O ₄ ) ₃ ], Na ₄ [Fe (CN) ₆ ], K ₄
[Fe (CN) ₆ ], (NH ₄ ) ₄ [Fe (C
N) ₆ ], Na ₃ [Fe (CN) ₆ ], K ₃ [Fe (C
Complex compounds such as N) ₆ ], (NH ₄ ) ₃ [Fe (CN) ₆ ] and ferrocene can be mentioned.

Of these, inorganic iron-containing compounds and organic iron-containing compounds are preferable as the iron-containing compound,
Further, from the viewpoint of the activity of the oxidation reaction, Fe ₂ (SO ₄ ) ₃ , F
e (ClO ₄ ) ₃ and FeC ₆ H ₅ O ₇ are preferable, and Fe ₂ (SO ₄ ) ₃ is particularly preferable.

Even if the iron-containing compound is an anhydride,
It may be a crystal water-containing material, or may be used alone.
Alternatively, two or more kinds may be used together as a mixture, a complex compound, a composition and the like. Further, the iron-containing compound can be used in various forms such as various solutions such as an aqueous solution and an organic solvent solution, a state of suspension, or a state of being supported on a carrier such as activated carbon. The amount of the iron-containing compound used can be appropriately selected depending on the purpose, but is usually 0.01 to 100 times mol, preferably 0.1 to 50 times mol, of the palladium compound. The amount used is
If it is less than 0.01 mol, it may not be possible to improve the catalytic activity and prevent deactivation of the palladium compound.
If it exceeds 100 times by mole, the reaction rate may decrease.

In the present invention, the iron-containing polyoxoanion compound may be used instead of the iron-containing compound. Specific examples thereof include a polyoxoanion compound having Fe in the polyoxoanion structure and a polyoxoanion compound having Fe as a cation component.

-Solvent- The solvent is a specified solvent and is a solvent of at least one selected from the group consisting of oxygen-containing compounds and sulfur-containing compounds or a mixture thereof with water.

Examples of the oxygen-containing organic compound include ethers, alcohols, ketones, esters and the like. When an oxygen-containing organic compound is used as the solvent, one of the various oxygen-containing organic compounds may be used alone, or two or more thereof may be mixed and used.

Examples of the sulfur-containing organic compound include dimethyl sulfoxide and sulfolane.
When using a sulfur-containing organic compound as a solvent, one of the various sulfur-containing organic compounds may be used alone,
Moreover, you may use it in mixture of 2 or more types.

Further, as the solvent, it is also possible to use a mixture of one or more of the oxygen-containing organic compounds and one or more of the sulfur-containing organic compounds.

In the present invention, the oxygen-containing organic compound is preferable.

Specific preferred examples of the oxygen-containing organic compound are shown below. Examples of the ethers include 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and the like. Of these, cyclic ethers such as 1,4-dioxane and tetrahydrofuran are particularly preferable. The alcohols include methanol,
Ethanol, n-propanol, isopropanol, n
-Butanol, sec-butanol, n-pentanol, n-hexanol and other monohydric alcohols having about 1 to 6 carbon atoms, and ethylene glycol, propylene glycol and other polyhydric alcohols having about 1 to 6 carbon atoms And the like. Examples of the ketones include acetone, methyl ethyl ketone, and diethyl ketone. Examples of the esters include γ-butyrolactone and δ-valerolactone.

The solvent may be a solvent of a mixture of water and at least one selected from the group consisting of the oxygen-containing compound and the sulfur-containing compound.

The ratio of water contained in the solvent is 5
It is preferably 0% by volume or less, particularly preferably 0.5 to 30% by volume. If the above ratio exceeds 50% by volume, the palladium compound may aggregate and precipitate easily, and the catalytic activity may decrease. In addition, since the solubility of olefin in water is low, the contact efficiency between the olefin and the catalyst (catalyst solution) may be lowered, especially in the case of liquid phase reaction, and a sufficient reaction rate may not be obtained. On the contrary, if the ratio is extremely small, the solubility of the catalyst component may be low, or the reaction rate may be slow due to the reaction mechanism.
When alcohols are used as the solvent, the above effects can be obtained without adding water.

The amount of the solvent to be used is sufficient as long as the catalyst is dissolved, and can be appropriately selected according to the purpose. Usually, it is 1 to 10, with respect to 1 mol of the palladium compound. 000 liters, preferably 50
~ 5,000 liters.

-Raw material- The above-mentioned raw materials are d) olefin and e) oxidizing gas.

D) Olefin The olefin is not particularly limited as long as it has at least one olefinic double bond (C = C),
Mention may be made of mono-olefins and olefins having a plurality of olefinic double bonds such as dienes and trienes. The olefin may be a terminal olefin having the C = C bond at the molecular end, or an internal olefin having the C = C bond inside the molecule, or may have C = C bonds at both the molecular end and inside. Further, not only chain olefins such as chain alkenes and chain alkadienes, but also cyclic olefins such as cycloalkenes and cycloalkadienes, and olefins having substituents such as cycloalkyl groups and aromatic groups may be used. The number of carbon atoms of the olefin is not particularly limited as long as the number of carbon atoms is 2 or more, but it is usually 2 to 30 carbon atoms, preferably about 2 to 20 carbon atoms.

The chain olefin may be linear or branched, and specific examples thereof include ethylene, propylene, 1-butene, trans-2-butene, cis-2-butene, Isobutene, 1-pentene,
2-pentene, 3-methyl-1-butene, 2-methyl-
Isopentene such as 2-butene, 1-hexene, 2-hexene, 3-hexene, 3-methyl-1-pentene, 4-
Isohexene such as methyl-1-pentene and 4-methyl-2-pentene, neohexene, 1-heptene, 2-heptene, 3-heptene, isoheptene such as 4-methyl-1-hexene, 1-octene, 2-octene, 3-octene, 4-octene, isooctene, 1-nonene, 2-nonene, isononene, 1-decene, 2-decene, 3-decene, 4-decene, 5-decene, isodecene, undecene, dodecene, tridecene, tetradecene, Examples include monoolefins such as hexadecene, pentadienes, hexadienes, heptadiene, octadiene, and dienes such as decadiene, and further isomers thereof.

Specific examples of the cyclic olefin include cycloalkene such as cyclopentene, cyclohexene, cyclooctene and cyclodecene, cycloalkadiene such as cyclohexadiene and cyclooctadiene, and further substituted with a substituent such as an alkyl group. You can list things like

As the olefin having an aromatic group, various chain olefins and cyclic olefins exemplified above are substituted with aryl groups such as phenyl and alkylphenyl groups, and various aromatic olefins and alkyl groups. The thing which the substituent of was substituted can be mentioned. Examples of typical compounds thereof include styrene hydrocarbons such as styrene, p-methylstyrene and β-methylstyrene. Examples of other olefins having a cyclic structure include vinylcyclohexane,
Examples thereof include vinylcyclohexene and allylcyclohexane. Among these, chain olefins having 2 to 30 carbon atoms, particularly 2 to 20 carbon atoms and 4 to 2 carbon atoms
0, especially a C4-C15 cyclic olefin is preferable.
Specific examples of suitable olefins include ethylene, propylene, 1-butene, trans-2-butene and ci.
s-2-butene, 1-pentene, 2-pentene, isopentene, 1-hexene, 2-hexene, 3-hexene,
Isohexene such as 4-methyl-1-pentene, neohexene, 1-heptene, 2-heptene, 1-octene, 2
-Octene, isooctene, 1-nonene, 2-nonene,
Examples include isononene, 1-decene, 2-decene, isodecene, undecene, dodecene, tridecene, tetradecene, hexadecene, cyclopentene, cyclohexene, cyclooctene, styrene and the like.

In the method of the present invention, high reactivity can be realized not only for α-olefins but also for internal olefins such as 2-butene and cyclic olefins such as cyclopentene. In the method of the present invention, an olefin which is usually a hydrocarbon is used as the olefin, but the olefin is not necessarily limited to this, and unless the object of the present invention is impaired, an olefin containing a hetero atom is used. You may use it as an olefin. The various olefins may be used alone or in combination as a mixture of two or more. Further, the olefin used may contain other components as long as the object of the present invention is not impaired.

The amount of the olefin used cannot be unconditionally specified because it depends on the activity of the catalyst and other reaction conditions, but usually 1 to 1 relative to the palladium compound.
It is 10,000 times the molar amount. If the ratio of the amount used is less than 1 mol, the productivity per catalyst may decrease, which may be economically disadvantageous. On the other hand, if it exceeds 10,000 times by mole, a sufficient conversion rate may not be obtained, or the reaction time may become long, and productivity may decrease.

E) Oxidizing Gas Examples of the oxidizing gas include oxygen gas, oxygen-containing gas such as air, and mixed gas of these oxygen gas or oxygen-containing gas and diluent gas. Nitrogen gas is usually used as the diluent gas, but the diluent gas is not limited to this and, for example, helium, argon, carbon dioxide, or the like can be used. Further, the oxygen gas and the oxygen-containing gas may contain other components, water, a solvent component and the like, if necessary, within a range not hindering the object of the present invention. The proportion of oxygen contained in the oxidizing gas can be appropriately selected according to the explosion range.

-Reaction- The reaction is carried out in the presence of the catalyst in the solvent according to an appropriately selected reaction method and reaction conditions.

In the present invention, the palladium compound, polyoxoanion compound and iron-containing compound are
When used in the solvent, it may be used in any form of a homogeneous state, a heterogeneous state, or a combination state thereof.
For example, the three components may be used as a homogeneous solution dissolved in the solvent, or only a part of the three components may be dissolved in the solvent, or a part of the three components may be dispersed in the solvent. You may use. Further, a part or all of these three components may be supported or immobilized on a suitable carrier such as activated carbon, silica or polymer.

The reaction system is not particularly limited, and various systems such as a batch system, a semi-batch system, a semi-continuous system, a continuous flow system, or a combination thereof can be adopted. Specifically, a mixed liquid obtained by mixing the catalyst and the solvent or a batch method in a liquid phase in which a mixed liquid of the catalyst and the solvent is used as a liquid phase, a gaseous olefin and an oxidizing gas into the mixed liquid. (Oxygen gas or oxygen-containing gas), or a method of circulating an oxidizing gas in a mixed liquid with the catalyst, a method of simultaneously circulating the catalyst liquid, an olefin and an oxidizing gas in the reaction region, Each catalyst component is used in a non-uniform state (solid state) by supporting or immobilizing the catalyst on a carrier or polymer, and a gaseous olefin, an oxidizing gas, and a solvent vapor (a gaseous coexisting substance) are circulated through this. It is possible to appropriately adopt a gas phase distribution method such as the above.

When the batch method is used, the ratio of the olefin to the catalyst used cannot be uniformly defined because it depends on the activity of the catalyst, other reaction conditions, etc. 1 to 1
It is suitable to select it in an amount of 10,000 mol, preferably 10 to 5,000 mol. In the case of the distribution method, the flow rate of the olefin or the oxidizing gas is not particularly limited,
Usually, it is about 1 to 1,000 ml / min.

Examples of the reaction conditions include reaction temperature and reaction pressure.

In the case of liquid phase reaction, the reaction temperature is usually set to a temperature of 0 to 200 ° C., preferably 20 to 100 ° C. In this case, if the reaction temperature is lower than 0 ° C, the reaction rate may decrease, while if it exceeds 200 ° C, a side reaction is likely to occur. In the case of gas phase reaction, the reaction temperature is usually 5
It is appropriate to appropriately select a temperature of 0 to 700 ° C, preferably 100 to 500 ° C. In this case, if the reaction temperature is lower than 50 ° C., the reaction rate may decrease, whereas if it exceeds 700 ° C., a side reaction may easily occur.

The reaction pressure can be appropriately selected from a wide range from normal pressure to high pressure, and economically, it is usually selected appropriately from normal pressure to 100 kg / cm ^2. Good.

-Carbonyl Compound- As described above, carbonyl compounds such as corresponding aldehydes and ketones, and optionally a mixture thereof, can be efficiently and stably obtained from the various olefins. Specifically, acetaldehyde is used when ethylene is used as the olefin, acetone is used when propylene is used, and methyl ethyl ketone is used from 1-butene, 2-butene or a mixture thereof,
It is possible to obtain methyl isobutyl ketone from methyl-1-pentene, dodecane from dodecene, tetradecane from tetradecene, hexadecane from hexadecene, cyclopentanone from cyclopentene, and cyclohexanone from cyclohexene.

The obtained carbonyl compound can be isolated and purified by a conventional method to obtain a single compound or a mixture having a desired purity or composition. When the unreacted raw material remains, the unreacted raw material can be recovered and recycled to the reaction system for use. The used catalyst may be appropriately regenerated or separated if necessary, and may be repeatedly used.

According to the method of the present invention, methyl ethyl ketone, methyl isobutyl ketone, acetone, or ketones such as dodecanone, tetradecanone, hexadecanone, cyclopentanone, cyclohexanone and carbonyl compounds such as aldehydes such as acetaldehyde can be stably obtained in high yield. Can be manufactured. Since there is no sedimentation or agglomeration of the catalyst component during production, deterioration of the catalyst activity can be prevented and the substantial catalyst activity and reaction rate can be stably maintained at a high level. Moreover, since it is not necessary to separately perform the reaction step and the catalyst regeneration step, the operation is easy and simple. The solvent used can be easily separated and recovered according to a conventional method, and can be repeatedly used if necessary.

The methyl ethyl ketone, methyl isobutyl ketone, acetone and the like thus produced can be used as a solvent as they are, and the carbonyl compound formed from a long chain olefin such as dodecanone, tetradecanone and hexadecanone can be hydrogenated to give an alcohol. Therefore, it can be used as a surfactant or the like. Furthermore, various other carbonyl compounds can be suitably used as various chemicals in various fields such as synthetic chemistry.

Therefore, in the method of the present invention, the raw material olefin has 2 to 10 carbon atoms so that the solvent carbonyl compound and the raw material olefin have 10 to 3 carbon atoms.
By setting the value to 0, the carbonyl compound for synthesizing the surfactant can be produced particularly easily and easily, and stably in a high yield.

[0057]

EXAMPLES Examples and comparative examples of the present invention will be described below. The present invention is not limited to the following embodiments.

(Example 1) 25 ml of 1,4-dioxane
And 5 ml of water, 0.1 mmol (0.0239 g) of PdSO ₄ .2H ₂ O, 3.6 mmol (8.1065)
g, water content 24.8% by weight) H ₆ PV ₃ Mo ₉ O ₄₀ and 0.5 mmol (0.2673 g) Fe ₂ (SO
₄₎ were charged ₃ · 7.5 h the mixture was dissolved ₂ O in an autoclave at a 270mmol at 80 ° C. 1-butene, oxygen, and the pressure 9 kg / cm ² (conditions gauge pressure) (holding pressure by the oxygen supply) The reaction was carried out for 1 hour. After the reaction, the liquid component was removed and the above-mentioned solvent was added to the recovered catalyst component for re-reaction, and the same operation was repeated 10 times. As a result, the amounts of methyl ethyl ketone (hereinafter, sometimes referred to as MEK) produced at the third time and the tenth time were 56.4 mmol and 55.7 mmol, respectively, and MEK per unit time based on the palladium compound.
The amount of production (TOF: turnover frequency) is 5 each
64 (mol / mol-Pd · hr), 557 (mol
/ Mol-Pd · hr). These results are shown in Table 1.
It was shown to.

(Example 2) In Example 1, 1,4-
50 ml of dioxane and 10 ml of water respectively
And replace cis-2-butene with 27 instead of 1-butene.
The reaction was performed in the same manner as in Example 1 except that 0 mmol was used. The results are shown in Table 1.

(Example 3) In Example 1, H ₆ PV
The amount of ₃ Mo ₉ O ₄₀ is 0.9 mmol (2.0266 g)
The reaction was performed in the same manner as in Example 1 except that
The results are shown in Table 1.

Example 4 In Example 1, H ₆ PV
The amount of ₃ Mo ₉ O ₄₀ is 0.9 mmol (2.0266 g)
And replace cis-2-butene with 27 instead of 1-butene.
The reaction was performed in the same manner as in Example 1 except that 0 mmol was used. The results are shown in Table 1.

(Example 5) In Example 1, Fe ₂
Instead of (SO ₄ ) ₃ · 7.5H ₂ O, Fe ₂ (C ₂ O
₄ ) The reaction was performed in the same manner as in Example 1 except that 0.05 mmol (0.0188 g) of ₃ was used. The results are shown in Table 1.

(Example 6) In Example 1, Fe ₂
(SO ₄ ) ₃ · 7.5H ₂ O instead of FeC ₆ H ₅ O
_The reaction was performed in the same manner as in Example 1 except that 1.0 mmol (0.2448 g) of ₇ was used. The results are shown in Table 1.

(Embodiment 7) In Embodiment 1, PdSO
₄ · 2H ₂ O in place of Pd (CH ₃ CO _{2) 2} 1.0
The reaction was performed in the same manner as in Example 1 except that mmol (0.1958 g) was used. The results are shown in Table 1.

(Embodiment 8) In Embodiment 1, PdSO
0.1mm _of Pd (PPh _{3) 4} in place of ₄ · 2H ₂ O
The reaction was performed in the same manner as in Example 1 except that ol (0.1154 g) was used. The results are shown in Table 1.

(Example 9) In Example 1, H ₆ PV
H ₇ PV ₄ Mo ₈ O ₄₀ in place of ₃ Mo ₉ O ₄₀ 3.6
The reaction was performed in the same manner as in Example 1 except that mmol (7.7614 g, water content 23.5% by weight) was used. The results are shown in Table 1.

Example 10 In Example 1, H ₆ P
H ₃ PW ₆ Mo ₆ O ₄₀ in place of V ₃ Mo ₉ O ₄₀ 3.
6 mmol (10.023 g, water content 15.5% by weight)
The reaction was carried out in the same manner as in Example 1 except that it was used. The results are shown in Table 1.

(Example 11) 50 m of 1,4-dioxane
l and 25 ml of water, 1.8 mmol of (V ₈ Mo
_In a solution containing ₄ O ₃₆ ) ^8- , 0.1 mmol (0.023
9 g) PdSO ₄ .2H ₂ O and 0.5 mmol
(0.2673 g) of Fe ₂ (SO ₄ ) ₃ · 7.5H ₂
Except for charging the mixture in which O was dissolved into the autoclave,
The reaction was performed in the same manner as in Example 1. The results are shown in Table 1.
It was shown to.

(Embodiment 12) In Embodiment 1, 1, 4
-Amount of dioxane and water of 15 ml and 15 m, respectively
The reaction was performed in the same manner as in Example 1 except that the amount was changed to 1.
The results are shown in Table 1.

(Embodiment 13) In Embodiment 1, 1, 4
-The reaction was performed in the same manner as in Example 1 except that tetrahydrofuran was used instead of dioxane. The results are shown in Table 1.

(Embodiment 14) In Embodiment 1, 1, 4
-Instead of 25 ml of dioxane and 5 ml of water, 30 ml of ethanol was used and the reaction temperature was 50 ° C,
The reaction was performed in the same manner as in Example 1. The results are shown in Table 1.
It was shown to.

(Example 15) In Example 1, 1, 4
The reaction was performed in the same manner as in Example 1 except that γ-butyrolactone was used instead of dioxane. The results are shown in Table 1.

(Example 16) In Example 1, 1, 4
-The reaction was performed in the same manner as in Example 1 except that 20 ml of sulfolane and 10 ml of water were used instead of 25 ml of dioxane and 5 ml of water. The results are shown in Table 1.

(Example 17) 25 m of 1,4-dioxane
0.2 mmol (0.0477 g) in 1 and 5 ml of water
Of PdSO ₄ .2H ₂ O, 1.8 mmol (4.0533
g, water content 24.8% by weight) H ₆ PV ₃ Mo ₉ O ₄₀ and 1.0 mmol (0.5346 g) Fe ₂ (SO
_{4) 3} · 7.5H ₂ O were dissolved mixture was charged into an autoclave, a pressure of 1 cyclopentene 150mmol and an oxygen-containing gas _{(N 2 / O 2 = 84} /16) at 80 ° C.
The reaction was carried out at 0 kg / cm ² (holding pressure by supplying oxygen) for 2 hours. The results are shown in Table 1.

(Example 18) 50 m of 1,4-dioxane
0.4 mmol (0.0956) in 1 and 10 ml of water.
g) PdSO ₄ .2H ₂ O, 4.2 mmol (9.05)
50 g, moisture content 23.5% by weight) H ₇ PV ₄ Mo ₈ O
₄₀ and 2.0 mmol (1.0694 g) Fe ₂
(SO ₄ ) ₃ · 7.5H ₂ O was dissolved in a mixture of propylene and oxygen at 40 ml / min and 20 ml, respectively.
The mixture was blown at a flow rate of / min and reacted at 80 ° C. for 1 hour. The results are shown in Table 1.

(Example 19) 50 m of 1,4-dioxane
1 mmol and water 10 ml, 0.1 mmol (0.0239
g) PdSO ₄ .2H ₂ O, 4.2 mmol (9.05)
50 g, moisture content 23.5% by weight) H ₇ PV ₄ Mo ₈ O
₄₀ and 1.0 mmol (0.5346 g) Fe ₂
Further, 100 mmol of 1-octene was dissolved in a mixture in which (SO ₄ ) ₃ · 7.5H ₂ O was dissolved, and oxygen was added to
It was blown in at 0 ml / min and reacted at 80 ° C. for 1 hour. The results are shown in Table 1.

Example 20 25 m of 1,4-dioxane
0.1 mmol (0.0239 g) in 1 and 5 ml of water
Of PdSO ₄ .2H ₂ O, 1.8 mmol (8.1065)
g, water content 24.8% by weight) H ₆ PV ₃ Mo ₉ O ₄₀ and 0.5 mmol (0.2673 g) Fe ₂ (SO
_{4) 3} · 7.5H the mixture was dissolved ₂ O were charged into an autoclave, at 80 ° C. 1-dodecene 50mmol an oxygen-containing gas _{(N 2 / O 2 = 84} /16) and the pressure 25kg
/ Cm ² (holding pressure by oxygen supply) was reacted for 1 hour.
After the reaction, the unreacted raw material and the product were removed, and the recovered catalyst solution was used for re-reaction, and the same operation was repeated 10 times. The results of the third and tenth reactions are shown in Table 1.

(Example 21) In Example 20, 1-
The reaction was performed in the same manner as in Example 20, except that 50 mmol of 1-tetradecene was used instead of dodecene. The results are shown in Table 1.

(Embodiment 22) In Embodiment 20, 1-
The reaction was performed in the same manner as in Example 20 except that 50 mmol of 1-hexadecene was used instead of dodecene. The results are shown in Table 1.

Comparative Example 1 25 ml of 1,4-dioxane
And 5 ml of water, 0.1 mmol (0.0239 g) of PdSO ₄ .2H ₂ O and 3.6 mmol (8.106 g).
5 g of H ₂ PV ₃ Mo ₉ O ₄₀ (water content: 24.8%) was dissolved, and the mixture was charged into an autoclave.
270 mmol of butene and oxygen were reacted for 1 hour under the condition of pressure 9 kg / cm ² (holding pressure by supplying oxygen). After the reaction, the liquid component was removed and the above-mentioned solvent was added to the recovered catalyst component for re-reaction, and the same operation was repeated 5 times. The results of the third and fifth reaction are shown in Table 1.

(Comparative Example 2) In Comparative Example 1, 1,4-
50 ml of dioxane and 10 ml of water respectively
And replace cis-2-butene with 27 instead of 1-butene.
The reaction was performed in the same manner as in Comparative Example 1 except that 0 mmol was used. The results of the first and third reactions are shown in Table 1.

(Comparative Example 3) 25 ml of 1,4-dioxane
And 5 ml of water, 0.1 mmol (0.0263 g) of PdSO ₄ .2H ₂ O, 3.6 mmol (8.1650)
g, water content 24.8% by weight) H ₆ PV ₃ Mo ₉ O ₄₀ and 1.0 mmol (0.2496 g) CuSO _4.
The mixture in which 5H ₂ O was dissolved was charged into an autoclave,
270 mmol of 1-butene and oxygen at 80 ° C. under a pressure of 9 k
The reaction was performed for 1 hour under the condition of g / cm ² (holding pressure by supplying oxygen). After the reaction, the liquid component is removed and the above-mentioned solvent is added to the recovered catalyst component to re-react.
Repeated times. The results of the second and fourth reactions are shown in Table 1.

(Comparative Example 4) In Comparative Example 3, CuSO
₄ · 5H ₂ O l of MnSO ₄ · 5H ₂ O in place of. 0
The reaction was performed in the same manner as in Comparative Example 3 except that mmol (0.2410 g) was used. The results of the third and fifth reaction are shown in Table 1.

Comparative Example 5 In Comparative Example 3, 1,4-
50 ml of dioxane and 10 ml of water respectively
And replace cis-2-butene with 27 instead of 1-butene.
The reaction was performed in the same manner as in Comparative Example 3 except that 0 mmol was used. The results of the first and second reactions are shown in Table 1.

(Comparative Example 6) In Example 12, 1, 4
-The reaction was performed in the same manner as in Example 12 except that 10 ml of acetonitrile and 30 ml of water were used instead of 15 ml of dioxane and 15 ml of water. The results of the first and second reactions are shown in Table 1.

[0086]

[Table 1]

Next, a specific example of a method for producing an alcohol by hydrogenating a carbonyl compound produced from a long-chain olefin will be shown as a reference example.

-Hydrogenation Reaction of Dodecanone- (Reference Example 1) 5% -Pt was added to a mixed solution of 10.2 mmol (1.8730 g) of 2-dodecanone obtained in Example 20 and 30 ml of 1,4-dioxane. Activated carbon is Pt
The mixture to which 0.1 mmol (0.3903 g) was added was charged into an autoclave, and hydrogen gas was reacted at 80 ° C. at a pressure of 8 kg / cm ² (holding pressure by supplying hydrogen) for 1 hour to obtain 2-dodecanol. The production amount of 2-dodecanol was 5.59 mmol, and the yield was 55.0%. The results are shown in Table 2. Reference Example 2 The reaction was performed in the same manner as in Reference Example 1 except that the reaction time was 3 hours in Reference Example 1. The results are shown in Table 2.

Reference Example 3 In a mixed solution of 9.9 mmol (1.8318 g) of 2-dodecanone obtained in Example 20, 20 ml of methanol and 10 ml of benzene,
0.025 mmol (0.0125 g) of [Rh (CO
D) Cl] ₂ (COD; 1,5-cyclooctadiene), 0.16 mmol (0.0419 g) triphenylphosphine and 0.25 mmol (0.0258).
The mixture to which g) of triethylamine was added was charged into an autoclave, and hydrogen gas at a pressure of 8 kg / cm ² was added at 80 ° C.
The reaction was carried out for 1 hour under (pressure holding by supplying hydrogen) to obtain 2-dodecanol. The results are shown in Table 2.

[0090]

[Table 2]

[0091]

According to the present invention, it is not necessary to separately perform the reaction step and the catalyst regeneration step, and it is possible to prevent the catalyst activity from deteriorating due to the sedimentation and aggregation of the catalyst components, and to achieve a substantial catalyst activity and reaction rate. Stable and stable at high level, useful as solvents and chemical raw materials methyl ethyl ketone, methyl isobutyl ketone, acetone, or carbonyl compounds such as dodecanone, tetradecanone, hexadecanone, cyclopentanone, cyclohexanone, and aldehydes such as acetaldehyde. It is possible to provide a method for producing a carbonyl compound, which can be produced easily and easily and stably in a high yield.

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Claims (2)

[Claims] 1. In a solvent of at least one selected from the group consisting of an oxygen-containing compound and a sulfur-containing compound or a mixture of these and water in the presence of a palladium compound, a polyoxoanion compound and an iron-containing compound. A method for producing a carbonyl compound, which comprises reacting an olefin with an oxidizing gas. 2. The method for producing a carbonyl compound according to claim 1, wherein the content of water in the solvent is 50% by volume or less.