JPS63243051A - Production of cycloalkanone - Google Patents

Abstract

PURPOSE:To facilitate separation and generation of a catalyst, improve catalyst activity and obtain the titled compound in high conversion and selectivity, by subjecting a cycloalkene to liquid oxidation in the coexistence of a specific catalyst, an active carbon and alcohol further in the presence of a specific amount of water. CONSTITUTION:A cycloalkene is subjected to liquid oxidation using at least one kind of compound selected from a palladium compound, copper compound and iron compound in the coexistence of an active carbon treated with H2O2 and alcohol and the presence of water of 10-1,000mmol. per 1mmol. palladium compound to efficiently provide the aimed compound useful as an intermediate, solvent, etc., for a high polymer compound such as nylon and polyester, plasticizer, synthetic lubricant and organic chemicals. The used catalyst can repeatedly be used because of having reduced lowering of catalyst activity when the catalyst is recovered and reused.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an improved method for producing cycloalkanones. More specifically, the present invention relates to polymer compounds such as nylon and polyester, plasticizers,
Cycloalkanones are extremely useful as intermediate raw materials for synthetic lubricants and other organic chemicals, and as solvents.
The present invention relates to a method for efficiently producing the corresponding cycloalkene by liquid phase oxidation.

[Conventional technology]

Conventionally, cycloalkanones having 5 to 12 ring carbon atoms are
It is known to be an important compound as an intermediate raw material or solvent for various uses.

For example, ε-caprolactam and lauryllactam, which are 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 penquinone, adipic acid obtained from cyclohexanone, azelaic acid obtained from cyclononanone, sebacic acid obtained from oxidative trimerization of cyclopentanone or cyclodecanone, dodecanni obtained from oxidative trimerization of cyclohexanone or cyclododecanone. Acids are important as raw materials for various nylons, polyesters, plasticizers, synthetic lubricants, and other organic chemicals. Furthermore, 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, various attempts have been made to oxidize cycloalkenes to produce corresponding cyclic ketones.

For example, as a method for producing cycloalkanones by liquid-phase oxidation of cycloalkenes, a method has been proposed in which liquid-phase oxidation is carried out with molecular oxygen in alcohol using a palladium compound and a copper or iron compound as a catalyst (Tokuko Showa). 6
0-330, Japanese Patent Publication No. 60-332).

However, this method has the disadvantage that palladium mirrors are produced, which may make it difficult to separate and regenerate the spent catalyst.

[Problem that the invention seeks to solve]

The present invention improves the drawbacks of the conventional method of oxidizing a cycloalkene to produce a corresponding cycloalkanone, facilitates the separation and regeneration of the catalyst, improves the catalyst activity, and improves the efficiency of the catalyst. The object of the present invention is to provide a practical method for producing cycloalkanones from cycloalkenes with high conversion and selectivity while suppressing a decrease in activity.

[Means for solving problems]

As a result of extensive research to achieve the above object, the present inventors have discovered that the presence of a specific amount of water in the reaction system improves catalytic activity and suppresses the decrease in catalytic activity. The present invention was completed based on the findings.

That is, the present invention uses (A) as a catalyst when producing a cycloalkanone by liquid phase oxidation of a cycloalkene.
The cycloalkene is prepared by using a palladium compound and (B) at least one compound selected from copper compounds and iron compounds, in the presence of activated carbon and alcohol, and in the presence of 10 to 1000 mmol of water per 1 mmol of the palladium compound. The present invention provides a method for producing a cycloalkanone, which is characterized by carrying out liquid phase oxidation of a cycloalkanone.

In the method of the present invention, the cycloalkene used as a raw material is unsubstituted or has a substituent having at least one unsaturated bond, and preferably one having 5 to 12 ring carbon atoms and one 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 5% by weight of the ethylene production amount.
Cyclohexene can be easily obtained by partial hydrogenation of the by-produced cyclopentadiene, cyclohexene can be easily obtained by partial dehydrogenation of cyclohexane, dehydrochlorination of chlorocyclohexane, etc., and each isomer of methylcyclohexene and each isomer of ethylcyclohexene can be obtained, respectively. It can be easily obtained by partially dehydrogenating methylcyclohexane and ethylcyclohexane obtained by hydrogenating toluene and ethylbenzene. 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 cycloalkanes as long as the oxidation reaction is not inhibited.

In the method of the present invention, a composite catalyst comprising (A) a palladium compound and (B) at least one compound selected from copper compounds and iron compounds is used.

Examples of the palladium compound used as component (A) of the catalyst include halides, inorganic acid salts, organic acid salts, organic complex salts, etc. Among these, palladium chloride, particularly palladium dichloride, is preferred. . This (A
) component is usually added in an amount of 0.
The amount of fluorite is selected in the range of 0.01 to 10% by weight, and the amount of fluorite is selected in the range of 0.01 to 4% by weight.

In addition, examples of the copper compound and iron compound used as component (B) include halides, inorganic acid salts, organic acid salts,
Examples include organic complex salts, among which chlorides such as cupric 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 0.1% by weight, based on the cyclic olefin.
-10% by weight.

In the present invention, it is necessary to coexist activated carbon. Activated carbon may be present as a carrier for the catalyst, or may be present separately from the catalyst.

The presence of activated carbon improves conversion and selectivity and facilitates separation and regeneration of the catalyst.

There is no particular restriction on the method of supporting the palladium compound or the copper or iron compound on activated carbon, and any conventionally used method can be used. For example, a predetermined amount of activated carbon is added to a hydrochloric acid aqueous solution containing palladium dichloride and copper or iron chloride at a predetermined concentration, and the activated carbon is heated to a temperature of preferably 60 to 100°C to evaporate to dryness. A catalyst in which a palladium compound and copper or iron compound points are supported on activated carbon can be obtained by calcining the mixture under air circulation at a temperature preferably in the range of 50 to 300° C. for usually about 2 to 8 hours. The amount of metal elements supported in the catalyst thus obtained is usually 0.01 to 10% by weight.
, preferably in the range of 0.1 to 3% by weight.

There are various types of activated carbon used here, but for example, those made by carbonizing wood, coconut shell, lignin, cow bone, lignite, coal, etc. as raw materials, activating this, and granulating it if necessary are used. Particularly preferably, activated carbon treated with hydrogen peroxide is used. The method for treating hydrogen peroxide may be any method in which hydrogen peroxide is brought into contact with activated carbon, and this can be carried out by bringing hydrogen peroxide into contact with activated carbon in a liquid phase or a gas phase. The amount of activated carbon to be added is not particularly limited, but is usually 5 to 50 g per mmol of palladium compound.
Preferably it is 7 to 25 g.

In the method of the present invention, it is necessary to carry out oxidation in the presence of water in the presence of alcohol.

As the alcohol, aliphatic alcohols, alicyclic alcohols, and aromatic ring-substituted alcohols having 1 to 2 carbon atoms are preferable, and they may be linear or branched, and may be primary or secondary. It may be either grade 3 or grade 3. Examples of such alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 5ec-butyl alcohol,
Aliphatic alcohols such as tert-butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, alicyclic alcohols such as cyclopentyl alcohol and cyclohexyl alcohol, benzyl alcohol, phenylethyl alcohol and aromatic ring-substituted alcohols such as phenylpropyl alcohol.

Each of these alcohols may be used alone, or
Two or more types may be used in combination, and solvents that are compatible with the alcohol, such as ethers such as dioxane and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, as long as the object of the present invention is not impaired.
It may contain esters such as methyl acetate and ethyl acetate, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene and toluene, and the like.

Water is 10 to 100 per mmol of palladium compound.
Q, mmol, preferably 30 to 600, particularly preferably 40 to 400 mmol, is added to the reaction system. If the amount of water is less than 10 mmol, the activity of the catalyst will not improve;
When the amount exceeds millimole, the activity of the catalyst decreases.

In the method of the present invention, hydrogen peroxide, te
Peroxides such as rt-butyl peroxide, oxygen, etc. can be used, but it is preferable to use molecular oxygen. For example, pure oxygen gas or a diluent inert to the reaction of oxygen gas, such as nitrogen, A mixed gas diluted with helium, argon, etc., or air is used.

Next, to explain one preferred example of the embodiment of the present invention, first, alcohol is preferably added in a range of 10 to 1000 parts by weight to 100 parts by weight of cycloalkene,
To this, a predetermined amount of activated carbon supported with component (A) and/or component (B) is added as a catalyst,
Next, the cycloalkene is heated using an oxidizing agent such as molecular oxygen, usually at 20-200°C, preferably at 30-100°C.
Liquid phase oxidation is carried out in the 'C range. 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/cal-
Oxidation is carried out in the 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 loss of solvent will increase, and the 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 cycloalkanone thus obtained is isolated by distillation or other means according to commonly used methods. Furthermore, it can be easily separated and recovered by means such as filtration, centrifugation, and sedimentation. and,
Even if the catalyst recovered by filtering the reaction solution is reused, its activity will not decrease much.

〔Example〕

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.

Example 1 Palladium dichloride (PdC1z) Immo 1 manufactured by Senkohun Co., Ltd. was dissolved in 10 ml of concentrated hydrochloric acid, and 10 ml of pure water was added to dilute the solution. 8 g of granular activated carbon was added to this solution and evaporated to dryness at 80°C on a hot water bath.
It was calcined at ℃ for 4 hours to obtain an activated carbon-supported catalyst in which 1.3% by weight of palladium was supported.

Reaction method internal volume 200 mj! in a stainless steel autoclave,
3.5 g of the above activated carbon supported catalyst, 40 mA of ethanol,
6.8 g of cyclopentene and cupric chloride (CuC12
・2H20) 0.8 mg atom, water 56 mmol (1
I added mjiri. Add 9k of oxygen to this autoclave.
g/CIJG was injected under pressure, and the mixture was reacted at 50° C. for 6 hours with stirring. After the reaction, the reaction solution and catalyst were separated by filtration, and the filtrate was analyzed, and the results showed that the conversion rate of cyclopentene was 85%, the selectivity of cyclopentanone was 87%, and the yield of cyclopentanone was 74%. .

Next, the filtered catalyst was placed in a stainless steel autoclave with an internal volume of 200 mJ, and the same reaction method as described above was carried out. The catalyst was repeatedly used in this manner five times, and the fifth reaction solution was analyzed. As a result, the conversion rate of cyclopentene was 82%, and the selectivity of cyclopentanone was 83%.
The yield of cyclopentanone was 68%.

Example 2 In Example 1, the amount of water added was 112 mmol (
The same reaction method as in Example 1 was performed except that the current was changed to 2 mA). As a result, the conversion rate of cyclopentene was 8
7%, the selectivity for cyclopentanone was 86%, and the yield of cyclopentanone was 75%. Furthermore, as a result of repeating the use of the catalyst 5 times and analyzing the reaction solution at the 5th time, the conversion rate of cyclopentene was 81%, the selectivity of cyclopentanone was 89%, and the yield of cyclopentanone was 7.
It was 2%.

Example 3 In Example 1, the amount of water added was 224 mmo I
(Other than changing the reaction rate to 4 m/liter, the same operation as in the reaction method of Example 1 was performed. As a result, the conversion rate of cyclopentene was 82%, the selectivity of cyclopentanone was 86%, and cyclopentanone The yield of cyclopentene was 70%.The catalyst was used 5 times and the reaction solution of the 5th time was analyzed, and the conversion rate of cyclopentene was 72%, and the selectivity of cyclopentanone was 90%. , the yield of cyclopentanone was 65%.

Comparative example 1 Made by Senokusato.

1 mmol of palladium dichloride (PdC1z) was dissolved in 10 ml of concentrated hydrochloric acid, and 10 mβ of pure water was added thereto for dilution. 8 g of granular activated carbon was added to this solution and evaporated to dryness at 80°C on a hot water bath.
It was calcined at ℃ for 4 hours to obtain an activated carbon-supported catalyst in which 1.3% by weight of palladium was supported.

Reaction method In a stainless steel autoclave with an internal volume of 200 mβ, 3.5 g of the above activated carbon-supported catalyst, 40 mβ of ethanol, 6.8 g of cyclopentene, and cupric chloride (CuC12.
2H20) 0.8nw atoms were added.

Oxygen was pressurized at 9 kg/cJG into this autoclave,
The reaction was carried out at 50° C. for 6 hours with stirring. After the reaction, the reaction solution and catalyst were separated by filtration, and the filtrate was analyzed. As a result, the conversion rate of cyclopentene was 80%, and the selectivity of cyclopentanone was 8.
1%, and the yield of cyclopentanone was 65%.

Next, the filtered catalyst was placed in a stainless steel autoclave having an internal volume of 200 m It, and the same reaction method as described above was carried out. The catalyst was repeatedly used in this manner five times, and the fifth reaction solution was analyzed. As a result, the conversion rate of cyclopentene was 52%, the selectivity of cyclopentanone was 76%, and the yield of cyclopentanone was 39%. %Met.

Example 4 Preparation of catalyst 16 g of granular activated carbon was immersed in an aqueous solution of 1 mL of 35% hydrogen peroxide solution and 100 mA of pure water.
After stirring for an hour, the mixture was evaporated to dryness at 80°C on a hot water bath.

On the other hand, 1 mmol of palladium dichloride (PdCI2) was dissolved in 10 ml of concentrated hydrochloric acid, and 10 ml of pure water was added to dilute the solution. To this solution, 8 g of the granular activated carbon treated with hydrogen peroxide was added, and the mixture was evaporated to dryness at 80°C on a hot water bath. This was then calcined at 250°C for 4 hours under air circulation, resulting in a palladium content of 1.3 An activated carbon-supported catalyst having a weight percent support was obtained.

In a stainless steel autoclave with an internal volume of 200 m1, 3.5 g of the above activated carbon-supported catalyst and 40 m1 of ethanol were placed.
4. 6.8 g of cyclopentene and cupric chloride (CuC
1z ・2Hz O) 0.8ntr atom, water 112m
Mo 1 (2 ml) was added to this autoclave, and 9 kg/cdG of oxygen was added to the autoclave, and the reaction was carried out at 50°C for 6 hours with stirring. After the reaction, the reaction solution and catalyst were separated by filtration.
As a result of analyzing the filtrate, the conversion rate of cyclopentene was 91%.
The M loss rate of cyclopentanone was 88%, and the yield of cyclopentanone was 80%.

Next, the filtered catalyst has an internal volume of 200mj! The mixture was placed in a stainless steel autoclave, and the same reaction method as described above was performed. Repeated use of catalyst using this method
As a result of analyzing the reaction solution of the fifth time, the conversion rate of cyclopentene was 82%, and the selectivity of cyclopentanone was 90%.
%, and the yield of cyclopentanone was 74%.

Example 5 In Example 4, cupric chloride (CuCI2
The same reaction method as in Example 4 was carried out except that the amount of 2HzO) was changed to 166 ■ atoms.

As a result, the conversion rate of cyclopentene was 95%, the selectivity of cyclopentanone was 88%, and the yield of cyclopentanone was 83%.

In addition, the catalyst was repeatedly used 5 times and the reaction solution of the 5th time was analyzed. As a result, the conversion rate of cyclopentene was 94%, the selectivity of cyclopentanone was 85%, and the yield of cyclopentanone was 80%. Met.

Example 6 In a stainless steel autoclave with an internal volume of 200 mβ, P
dC1z O,4, mmo 1, ethanol 40ml 1l
, cyclopentene 6.8 g, cupric chloride (Cuc
12-2H20) 0.8w atom, water 112mm.

] (Added 2rr+j and 6g of powdered activated carbon.

Into this autoclave, pressurize 9 kg of oxygen at 10 JG.
The reaction was carried out at 50° C. for 6 hours with stirring. After the reaction, the reaction solution and catalyst were separated by filtration, and the filtrate was analyzed, and the conversion rate of cyclopentene was 84%, and the selectivity of cyclopentanone was 8.
The yield of cyclopentanone was 74%.

Furthermore, as a result of repeating the use of the catalyst five times and analyzing the reaction solution for the fifth time, the conversion rate of cyclopentene was 85%, the selectivity of cyclopentanone was 86%, and the yield of cyclopentanone was 73%. Met.

〔Effect of the invention〕

According to the method for producing a cycloalkanone of the present invention, the corresponding cycloalkanone can be obtained from a cycloalkene with high conversion rate and selectivity, and the expensive palladium used as a catalyst can be used in the coexistence of activated carbon. It can be easily separated and recovered. In addition, even if the catalyst used in the present invention is recovered and reused, there is little decrease in catalytic activity, and repeated use is possible, so the method of the present invention can be said to be a method of high practical value.

Claims (1)

[Claims] 1. In producing a cycloalkanone by liquid phase oxidation of a cycloalkene, at least one selected from (A) a palladium compound and (B) a copper compound and an iron compound is used as a catalyst. 1. A method for producing a cycloalkanone, which comprises oxidizing the cycloalkanone in a liquid phase using a compound in the presence of activated carbon and an alcohol in the presence of 10 to 1000 mmol of water per 1 mmol of the palladium compound. 2. The method for producing a cycloalkanone according to claim 1, wherein the activated carbon is treated with hydrogen peroxide.