JPH022867B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to an improved method for producing cyclic ketones. More specifically, the present invention utilizes cyclic ketones that are extremely useful as intermediate raw materials for polymer compounds such as nylon and polyester, plasticizers, synthetic lubricating oils, and other organic chemicals, or as solvents. The present invention relates to a method for producing olefins in good yield by liquid phase oxidation. [Prior art] Conventionally, cyclic ketones, especially those with a ring carbon number of 5 to
12 cycloalkenes are known to be important compounds as intermediate raw materials and solvents for various uses. For example, ε-caprolactam and lauryllactam derived from cyclohexanone and cyclododecanone, respectively, are important as raw material monomers for nylon 6 and nylon 12, respectively, and various dicarboxylic acids obtained by oxidizing cycloalkanone, such as cyclo Glutaric acid obtained from pentanone, adipic acid obtained from cyclohexanone, azelaic acid obtained from cyclononanone, sebacic acid obtained from oxidative duplexing of cyclopentanone or cyclodecanone, dodecanedioic acid obtained from oxidative duplexing of cyclohexanone or cyclododecanone. These are important raw materials for various nylons, polyesters, plasticizers, synthetic lubricants, and other organic chemicals. moreover,
Cyclohexanone is used in large quantities as a general-purpose solvent, and high-purity cyclopentanone has recently been in the spotlight as a special solvent in the electronics field. By the way, it is well known that the corresponding aldehydes and ketones can be obtained by oxidizing aliphatic olefins, such as the worker method, and also for cyclic olefins,
Various attempts have been made to produce corresponding cyclic olefins by oxidation. For example, an example of a method for producing cyclopentanone by oxidizing cyclopentene as a cyclic olefin is a rhodium-based catalyst [J.Am.Chem.Soc. .)” Volume 100,
No. 5437 (1978)] and palladium-heteropolyacid catalysts [Catalysis Society of Japan Small Discussion Group ``Catalysis of Heteropolyacids and Related Compounds'' 2nd Lecture Proceedings (December 4, 1980)]. A method of oxidizing with molecular oxygen has been reported. However, in the former method, ether compounds are mainly produced, and in the latter method, the reaction rate is extremely low, which makes it impractical. In addition, a method of liquid phase oxidation using molecular oxygen in the coexistence of alcohol using a composite catalyst of palladium compounds and copper compounds or iron compounds (Japanese Patent Publication No. 1983-330), Method of liquid phase oxidation using oxides (Japanese Unexamined Patent Publication No. 1981-81139)
is proposed. However, these methods are not necessarily satisfactory in terms of conversion rate and selectivity, and the latter method also has drawbacks such as the need to use expensive peroxides. Furthermore, a method of liquid phase oxidation with molecular oxygen using a composite catalyst of a palladium compound and a bismuth compound is also disclosed. (Unexamined Japanese Patent Publication 1986-
Publication No. 92234). However, this method has a problem of low selectivity. [Problems to be Solved by the Invention] The present invention improves the drawbacks of the conventional method of oxidizing cyclic olefins to produce corresponding cyclic ketones, and makes it easy to separate and recover the catalyst. Another object of the present invention is to provide a practical method for producing cyclic ketones from cyclic olefins with high conversion and selectivity. [Means for solving the problem] As a result of intensive research to achieve the above object, the present inventors used a composite catalyst consisting of a palladium compound and a certain metal compound as a catalyst,
Furthermore, the inventors have discovered that the object can be achieved by liquid-phase oxidation of cyclic olefins in the presence of alcohol, and have completed the present invention based on this knowledge. That is, the present invention provides for producing cyclic ketones by liquid-phase oxidation of cyclic olefins, using (A) palladium compounds, (B) gold compounds, platinum compounds, iridium compounds, ruthenium compounds, and rhodium compounds as catalysts. at least one selected from
Provided is a method for producing cyclic ketones, characterized in that the cyclic olefins are subjected to liquid phase oxidation in the presence of an alcohol using at least one selected from seeds and (C) a copper compound and an iron compound. It is something. In the method of the present invention, the cyclic olefin used as a raw material is unsubstituted or has a substituent having at least one unsaturated bond, and is preferably one having 5 to 12 ring carbon atoms and 1 unsaturated bond. Examples include cycloalkenes which are unsubstituted or have a lower alkyl group on the ring. Examples of such substances include cyclopentene, methylcyclopentene isomers, cyclohexene,
Particularly preferred are methylcyclohexene isomers, ethylcyclohexene isomers, cyclooctene, cyclododecene, etc. from the viewpoint of easy availability of raw materials and usefulness of the resulting cycloalkanones. The cyclopentene accounts for 4 to 40% of the ethylene production.
Cyclohexene can be easily obtained by partial hydrogenation of 5% by weight cyclopentadiene, cyclohexene can be easily obtained by partial dehydrogenation of cyclohexane, dehydrochlorination of chlorocyclohexane, etc., and various isomers of methylcyclohexene and each isomer of ethylcyclohexene can be obtained. can be easily obtained by partially dehydrogenating methylcyclohexane and ethylcyclohexane obtained by hydrogenating toluene and ethylbenzene, respectively. Additionally, cyclooctene can be obtained by partially hydrogenating cyclooctatetraene obtained by tetramerizing acetylene, while cyclododecene can be easily obtained by partially hydrogenating cyclododecatriene obtained by trimerizing butadiene. . These cyclic olefins may contain saturated cyclic alkanes as long as the oxidation reaction is not inhibited. In the method of the present invention, as a catalyst, at least one selected from (A) a palladium compound, (B) a gold compound, a platinum compound, an iridium compound, a ruthenium compound, and a rhodium compound, and (C) a copper compound and an iron compound. A composite catalyst consisting of at least one selected from the following is used. Examples of the palladium compound used as component (A) of the catalyst include halides, inorganic acid salts, organic acid salts, and organic complex salts, among which palladium chloride is particularly preferred. The amount of component (A) added is usually selected within the range of 0.001 to 10% by weight, preferably 0.01 to 1% by weight, based on the cyclic olefin. Examples of the gold compound, platinum compound, iridium compound, ruthenium compound, and rhodium compound used as component (B) include halides,
Examples include inorganic acid salts, organic acid salts, and organic complex salts, with halides being particularly preferred. These compounds may be used alone or in combination of two or more, and the amount added is usually 0.001 to 10% by weight, preferably 0.01% by weight, based on the cyclic olefin.
-1% by weight. Further, examples of copper compounds and iron compounds used as component (C) include halides, inorganic acid salts,
Examples include organic acid salts and organic complex salts, and among these, chlorides such as cuprous chloride, cupric chloride, ferrous chloride, and ferric chloride are preferred. These compounds may be used alone or in combination of two or more, and the amount added is usually 0.01 to 20% by weight, preferably 0.01 to 20% by weight, based on the cyclic olefin.
It is selected in the range of 0.1 to 10% by weight. In the present invention, at least one of the catalyst components described above can be supported on a desired carrier and used. In particular, the use of activated carbon as a carrier on which palladium (component (A)) and precious metal element (component (B)) are supported not only improves the conversion rate and selectivity but also allows the separation and recovery of expensive precious metal catalysts. This is preferable because it makes it easier. There are no particular restrictions on the method for supporting palladium and the noble metal element (B) on activated carbon, and conventional methods can be used. For example, a predetermined amount of activated carbon is added to an acidic aqueous solution of hydrochloric acid containing a predetermined concentration of at least one noble metal chloride selected from palladium dichloride and component (B), and the temperature is preferably 60 to 100°C. The activated carbon is heated to evaporate to dryness, and then calcined under air circulation at a temperature preferably in the range of 50 to 300°C for usually about 2 to 8 hours to add palladium to the activated carbon.
A catalyst supporting the noble metal element (B) is obtained. Of course, the metal elements supported on the activated carbon are not limited to the above combinations, for example, a combination of palladium and the metal element of the (C) component, or a combination of the metal element of the (B) component and the metal element of the (C) component. It may be a combination with The amount of metal elements supported in the catalyst thus obtained is usually 0.01
It is desirable that the amount is in the range of ~10% by weight, preferably 0.1-3% by weight. In the method of the present invention, it is necessary to carry out the oxidation in the presence of alcohol. As the alcohol, aliphatic alcohols having 1 to 20 carbon atoms, alicyclic alcohols, and aromatic ring-substituted alcohols thereof are preferable, and they may be linear or branched, and primary or secondary alcohols may be used. It may be of either class or tertiary class. Examples of such alcohol include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, - Aliphatic alcohols such as octyl alcohol, 2-ethylhexyl alcohol, and nonyl alcohol, alicyclic alcohols such as cyclopentyl alcohol and cyclohexyl alcohol, and aromatic ring-substituted alcohols such as benzyl alcohol, phenylethyl alcohol, and phenylpropyl alcohol. be able to. These alcohols may be used alone or in combination of two or more, and may also be used in solvents that are compatible with the alcohol, such as water, dioxane, and tetrahydrofuran, as long as the purpose of the present invention is not impaired. ethers such as acetone, ketones such as methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene and toluene, etc. good. In the method of the present invention, it is preferable to use molecular oxygen as the oxidizing agent, such as pure oxygen gas, a mixed gas of oxygen gas diluted with a diluent inert to the reaction, such as nitrogen, helium, argon, etc. Air etc. are used. Next, to explain one preferred example of the embodiment of the present invention, first, to 100 parts by weight of the cyclic olefin, alcohol is preferably added in the range of 10 to 1,000 parts by weight, and to this, preferably activated carbon is added as a catalyst. Components (A) and (B) are supported on
Predetermined amounts of each component (C) are added, and then the cyclic olefin is subjected to liquid phase oxidation using an oxidizing agent such as molecular oxygen, usually at room temperature to 200°C, preferably in the range of 30 to 100°C. There is no particular restriction on the reaction pressure as long as it is at least the pressure necessary to maintain the liquid phase of the reaction system, but it is usually between normal pressure and 20 kg/kg.
Oxidation takes place in the cm ² ·G range. If the reaction temperature is too low, the reaction rate will be slow and impractical, while if it exceeds 200°C, side reactions and solvent loss will increase and equipment will become expensive. The reaction time varies depending on the reaction temperature, the type of catalyst, the amount added, etc., but is usually in the range of 10 minutes to 24 hours. The cyclic ketones thus obtained are isolated by distillation or other means according to commonly used methods. Further, when using a catalyst supported on activated carbon, it can be easily separated and recovered by means such as filtration, centrifugation, and sedimentation. [Examples] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. Note that gas chromatography was used to analyze the reaction products. Example 1 Palladium dichloride (PdCl ₂ ) equivalent to 1 mg atom of palladium and platinum chloride (PtCl ₄ 5H ₂ O) equivalent to 0.5 mg atom of platinum were dissolved in 10 ml of concentrated hydrochloric acid, and diluted by adding 10 ml of pure water to this. did. After adding 8 g of granular activated carbon to this solution and evaporating it to dryness at 80°C on a hot water bath, this was calcined at 250°C for 4 hours under air circulation.
An activated carbon-supported catalyst on which 1.3% by weight of palladium and 1.2% by weight of platinum was supported was obtained. Next, in a stainless steel autoclave with an internal volume of 200 ml, 3.5 g of the activated carbon-supported catalyst, 40 ml of ethanol, 6.8 g (100 mmol) of cyclopentene, and an amount of cupric chloride (CuCl _{2 2} H _{2 )} equivalent to 0.8 mg of copper were added. After adding O), add 9.0Kg of oxygen/
The oxidation reaction was carried out under pressure at ⁵⁰ ° C. and stirred for 6 hours. As a result, the conversion rate of cyclopentene was 90%, the selectivity of cyclopentanone was 84%, and therefore the yield of cyclopentanone was 76%. Example 2 The oxidation reaction of cyclopentene was carried out in exactly the same manner as in Example 1, except that the amount of platinum chloride was changed to 0.25 mg atom equivalent. As a result, the conversion rate of cyclopentene was 92%, the selectivity of cyclopentanone was 83%, and therefore the yield of cyclopentanone was 76%. Example 3 In Example 1, gold was used instead of platinum chloride.
Chloroauric acid (HAuCl ₄ .
The oxidation reaction of cyclopentene was carried out in the same manner as in Example 1 except that 4H ₂ O)) was used. The results are shown in the attached table. Examples 4 to 7 In Example 1, instead of platinum chloride, iridium chloride (IrCl ₄ ) was used in an amount equivalent to 0.6 mg atom of iridium and 0.3 mg atom, and rhodium chloride (RhCl ₃ . The oxidation reaction of cyclopentene was carried out in the same manner as in Example 1, except that ruthenium chloride (RuCl ₄ .5H ₂ O) in an amount equivalent to 1.0 mg of ruthenium atoms was used. The results are shown in the attached table. Example 8 The same procedure was carried out as in Example 1, except that ferric chloride (FeCl ₃ 6H ₂ O) equivalent to 0.8 mg of iron atoms and 40 ml of n-propanol were used instead of cupric chloride and ethanol. The oxidation reaction of cyclopentene was carried out in exactly the same manner as in Example 1. The results are shown in the attached table. Comparative Example 1 The oxidation reaction of cyclopentene was carried out in exactly the same manner as in Example 1, except that platinum chloride was not used. The results are shown in the attached table. Comparative Example 2 The oxidation reaction of cyclopentene was carried out in exactly the same manner as in Example 1, except that 40 ml of cyclohexane was used instead of ethanol. The results are shown in the attached table. Comparative Example 3 An oxidation reaction was carried out in the same manner as in Example 8 except that platinum chloride was not used. The results are shown in the attached table.

〔Effect of the invention〕

According to the method for producing cyclic ketones of the present invention, corresponding cyclic ketones can be obtained from cyclic olefins with high conversion and selectivity, and the expensive palladium and other noble metals used as catalysts can be used on activated carbon, etc. The cyclic ketones obtained can be easily separated and recovered, and the obtained cyclic ketones can be used, for example, as intermediate raw materials for polymer compounds such as nylon and polyester, plasticizers, synthetic lubricating oils, and other organic chemicals. It is a very useful compound as a solvent, and the method of the present invention can be said to be of high practical value.

Claims (1)

[Claims] 1. In producing cyclic ketones by liquid-phase oxidation of cyclic olefins, (A) palladium compounds, (B) gold compounds, platinum compounds, iridium compounds, ruthenium compounds, and rhodium compounds are used as catalysts. at least one selected from among (C) at least one selected from copper compounds and iron compounds;
1. A method for producing cyclic ketones, comprising liquid-phase oxidation of the cyclic olefins in the presence of an alcohol using seeds. 2. The method for producing cyclic ketones according to claim 1, wherein the cyclic olefin is a cycloalkene having 5 to 12 ring carbon atoms and having one unsaturated bond. 3. The method for producing cyclic ketones according to claim 2, wherein the cycloalkene is cyclopentene. 4. The method for producing cyclic ketones according to claim 1, 2, or 3, wherein at least one catalyst component is supported on a carrier. 5. The method for producing cyclic ketones according to claim 1, 2, 3, or 4, wherein the oxidizing agent is molecular oxygen.