JP2007320878A - Method for producing cycloalkanol and cycloalkanone - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an industrially suitable method for producing a cycloalkanol and cycloalkanone, exhibiting high decomposition activity and high selectivity of objective materials. <P>SOLUTION: This method for producing the cycloalkanol and cycloalkanone is provided by performing the decomposition reaction of a cycloalkyl hydroperoxide in the presence of a metal chloride loaded on activated charcoal, silica gel or alumina. Here, as the metal chloride, e.g. the chloride of an element in the 11th group (such as cupric chloride, etc.), molybdenum chloride, ruthenium chloride, etc. are cited. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing cycloalkanol and cycloalkanone by decomposing cycloalkyl hydroperoxide obtained by oxidation reaction of cycloalkane. Cycloalkanol and cycloalkanone are extremely useful compounds as raw materials for producing polyamide-based polymer monomers such as nylon, synthetic raw materials for chemicals, and organic solvents.

As a method for producing cycloalkanol and cycloalkanone by decomposing cycloalkyl hydroperoxide, a method using a cobalt salt of a carboxylic acid and a cobalt complex having porphyrin as a ligand as a catalyst (Patent Document 1). And a method using a cobalt compound such as cobalt octylate and a ruthenium compound such as ruthenium octylate as a catalyst (Patent Document 2) are known. Although these methods show high decomposition activity and high selectivity of the target product, a high reaction temperature (120 ° C. or higher) is necessary to increase the reaction rate. Moreover, since the amount of the catalyst used is small, it is difficult to separate and recover and reuse it, and therefore, there remains a problem as an industrial production method.
JP 2006-36642 A JP 2006-56814 A

  An object of the present invention is to provide an industrially suitable process for producing cycloalkanol and cycloalkanone which solves the above problems, exhibits high decomposition activity and high selectivity of the target product, and facilitates catalyst recovery and reuse. It is to provide.

  The object of the present invention is solved by a process for producing cycloalkanol and cycloalkanone characterized by decomposing cycloalkyl hydroperoxide in the presence of a metal chloride supported on activated carbon, silica gel or alumina.

  The present invention does not require a high reaction temperature (120 ° C. or higher), exhibits a high decomposition activity for cycloalkyl hydroperoxide, and a high selectivity for the target cycloalkanol and cycloalkanone, thereby recovering the catalyst. Provide an industrially suitable process for producing cycloalkanol and cycloalkanone that can be easily reused.

Examples of the metal chloride supported on activated carbon, silica gel, or alumina used in the decomposition reaction of the cycloalkyl hydroperoxide of the present invention include group 11 element chlorides (such as cupric chloride), molybdenum chloride, ruthenium chloride, and the like. The chlorides of group 11 elements and ruthenium chloride are preferred, and cupric chloride and ruthenium chloride are more preferred.
The periodic table used in the present invention is based on the group 18 element periodic table, IUPAC, inorganic chemical nomenclature, and the 1990 rules.
The metal chloride supported on activated carbon, silica gel or alumina can be prepared by, for example, a pore filling method, but a commercially available product can also be used.
Here, the loading amount of the metal chloride on the activated carbon, silica gel or alumina is 0.0001 to 0.5 g, preferably 0.001 to 0.3 g, with respect to 1 g of the activated carbon, silica gel or alumina.

  The amount of metal chloride supported on activated carbon, silica gel, or alumina is preferably 0.001 to 5000 ppm by mass, more preferably 0.01 as a metal atom with respect to the mixed liquid containing cycloalkyl hydroperoxide. It is -1000 mass ppm.

  Specific examples of the cycloalkyl hydroperoxide include, for example, cyclopentyl hydroperoxide, cyclohexyl hydroperoxide, cycloheptyl hydroperoxide, cyclooctyl hydroperoxide, cyclononyl hydroperoxide, cyclodecyl hydroperoxide, and cyclododecyl. Examples thereof include cycloalkyl hydroperoxide having 5 to 20 carbon atoms, such as hydroperoxide, cyclopentadecyl hydroperoxide, and cyclohexadecyl hydroperoxide.

The cycloalkyl hydroperoxide is usually used in the presence or absence of a metal catalyst such as cobalt in the presence or absence of a cycloalkane and molecular oxygen such as air under a reaction temperature of 120 to 180 ° C. and a reaction pressure of 1 to 20 atmospheres. It can be obtained by a liquid phase contact reaction.
In the present invention, the crude cycloalkyl hydroperoxide thus obtained (that is, the above oxidation reaction solution) is used as it is or after being concentrated, so that the cycloalkyl hydroperoxide in these mixed solutions can be efficiently used. Cycloalkanol and cycloalkanone can be produced by being well decomposed, but the cycloalkyl hydroperoxide separated from the above oxidation reaction solution by distillation or extraction is diluted with a raw material cycloalkane or a solvent such as benzene or toluene, or It may be used after being dissolved. In addition, the cycloalkyl hydroperoxide contained in a liquid mixture is 0.1-20 mass% normally, Preferably it is 0.5-10 mass%.

  In the case of using a cycloalkane oxidation reaction solution, it is preferable to remove the contained acid by washing the oxidation reaction solution with water, if necessary, before decomposing the cycloalkyl hydroperoxide. Note that a weak alkaline aqueous solution (for example, an aqueous solution of an alkali metal or alkaline earth metal carbonate) can be used instead of water.

  The decomposition of the cycloalkyl hydroperoxide is carried out in the presence of the metal chloride supported on activated carbon, silica gel or alumina in the mixed solution containing the cycloalkyl hydroperoxide, and the reaction temperature is 25 to 180 ° C., preferably The reaction is performed at 50 to 160 ° C., more preferably 70 to 120 ° C., and a reaction pressure of 1 to 30 atm. When the reaction temperature is lower than 25 ° C., the reaction rate is slow, and when the reaction temperature is higher than 180 ° C., the yield of the target product decreases, which is not preferable. Further, there is no particular problem even if the concentration of the catalyst is high, but the above range is preferable from an industrial point of view.

  The decomposition reaction is performed, for example, in a pressure resistant or non-pressure resistant reactor equipped with a reflux condenser and a stirring device in order to release reaction heat generated during the reaction and appropriately control the reaction temperature.

  As described above, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclononanone, cyclodecanone, cyclododecanone, cyclopentadecanone, cyclohexanone, and other cycloalkanones, and cyclopentanol, cyclohexanol, Cycloheptanol, cyclooctanol, cyclononanol, cyclodecanol, cyclododecanol, cyclopentadecanol, cyclohexadecanol and other cycloalkyl hydroperoxide-containing decomposition reaction liquids can be obtained. If necessary, the canon and cycloalkanol are separated and purified by distillation or the like after washing the decomposition reaction solution with water or an alkaline aqueous solution to remove the acid. In addition, when the oxidation reaction liquid of cycloalkane is used for the reaction, unreacted cycloalkane is distilled and separated and recycled for the oxidation reaction.

Reference Example 1 (Synthesis of cyclohexyl hydroperoxide)
A pressure-resistant glass autoclave having an internal volume of 500 ml equipped with a reflux condenser, a thermometer, a gas introduction pipe and a stirring device was charged with 0.8 g of cyclohexane and cobalt octylate as a Co metal concentration under stirring (600 rpm) and a pressure of 0. The temperature was raised while venting nitrogen gas at 95 MPaG and a flow rate of 40 L / hr. After the temperature reached 160 ° C., the nitrogen gas was switched to air (pressure 1.0 MPaG, flow rate 45 L / hr) to start the oxidation reaction. After the reaction for 25 minutes, the reaction solution was cooled to obtain an oxidation reaction solution of cyclohexane containing 0.1399 mmol of cyclohexyl hydroperoxide, 0.1655 mmol of cyclohexanol, and 0.0992 mmol of cyclohexanone per 1 g of the oxidation reaction solution.
In addition, in the decomposition reaction of cyclohexyl hydroperoxide, what increased the density | concentration of cyclohexyl hydroperoxide by concentrating the oxidation reaction liquid prepared by the said method was used as needed.

Reference Example 2 (Preparation of activated carbon-supported copper (II) chloride catalyst (CuCl ₂ / C))
2.68 g of cupric chloride (CuCl ₂ .2H ₂ O) was put into a 100 mL beaker, and 15 mL of water was added and dissolved. The solution was added to 9 g of powdered activated carbon (manufactured by NE Chemcat) and allowed to stand for 2 hours. Thereafter, dehydration drying was performed with an evaporator to prepare a 10 wt% CuCl ₂ / C catalyst.

Reference Example 3 (Preparation of silica-supported ruthenium chloride catalyst (RuCl ₃ / SiO ₂ ))
Ruthenium chloride (RuCl ₃ .3H ₂ O) 0.517 g was dissolved in 10 ml of concentrated hydrochloric acid and evaporated to dryness in an evaporating dish, and then redissolved in 15 ml of water. The solution was added to 10 g of SiO ₂ (Fuji Silysia Chemical Co., Ltd. CARIACT Q-50) and left for 2 hours. Thereafter, dehydration drying was performed with an evaporator to prepare a 2 wt% RuCl ₃ / SiO ₂ catalyst.

Reference Example 4 (Preparation of alumina-supported copper chloride catalyst (CuCl ₂ / Al ₂ O ₃ ))
2.68 g of cupric chloride (CuCl ₂ .2H ₂ O) was put into a 100 mL beaker, and 15 mL of water was added and dissolved. The solution was added to 9 g of alumina (CS-33) and allowed to stand for 2 hours. Thereafter, dehydration and drying were performed with an evaporator to prepare a 10 wt% CuCl ₂ / Al ₂ O ₃ catalyst.

Example 1 (Decomposition reaction of cyclohexyl hydroperoxide with activated carbon-supported copper chloride (II) (CuCl ₂ / C))
An oxidation reaction solution of cyclohexane prepared by the method shown in Reference Example 1 (cyclohexyl hydroperoxide per gram of the oxidation reaction solution) was added to a 300 mL pressure-resistant glass autoclave equipped with a reflux condenser, a thermometer, a gas introduction tube, and a stirring device. 160 g) (including 0.3508 mmol, cyclohexanol 0.1811 mmol, and cyclohexanone 0.0903 mmol) and 10 wt% CuCl ₂ / C catalyst prepared by the method shown in Reference Example 2 were charged so that the Cu metal concentration was 1000 ppm by mass. While stirring (300 rpm), the temperature was increased while aeration of nitrogen gas at a pressure of 1.0 MPaG and a flow rate of 20 L / hr. After the temperature reached 80 ° C., reaction was performed for 30 minutes, and the reaction solution was cooled. When the obtained reaction liquid was analyzed by gas chromatography, cyclohexyl hydroperoxide was completely decomposed (decomposition rate 100%), and the total yield of cyclohexanol and cyclohexanone was 92.9%.

Example 2 (Decomposition reaction of cyclohexyl hydroperoxide with activated carbon-supported ruthenium chloride (RuCl ₃ / SiO ₂ ))
20 g of cyclohexane oxidation reaction solution prepared by the method shown in Reference Example 1 and 2 wt% RuCl ₃ / SiO ₂ catalyst prepared by the method shown in Reference Example 3 in a pressure-resistant glass reactor having an internal volume of 50 ml and a Ru metal concentration of 500 It added so that it might become mass ppm, and it was made to decompose-react for 30 minutes at 90 degreeC, stirring under nitrogen atmosphere. The reaction solution was cooled and the obtained reaction solution was analyzed by gas chromatography. As a result, the decomposition rate of cyclohexyl hydroperoxide was 98.5%, and the total yield of cyclohexanol and cyclohexanone was 97.7%.

Comparative Example 1 (Decomposition reaction of cyclohexyl hydroperoxide with cobalt octylate)
Add 20 g of cyclohexane oxidation reaction solution and cobalt octylate catalyst prepared in the manner shown in Reference Example 1 to a pressure resistant glass reactor with an internal volume of 50 ml so that the Co metal concentration is 5 ppm by mass, and stir in a nitrogen atmosphere. The decomposition reaction was carried out at 80 ° C. for 30 minutes. The reaction solution was cooled and the obtained reaction solution was analyzed by gas chromatography. As a result, the decomposition ratio of cyclohexyl peroxide was 20.5%. The same reaction was performed when the reaction temperature was 120 ° C. and 140 ° C., and the decomposition rates of cyclohexyl hydroperoxide were 30.9% and 78.9%, respectively.

Example 3 (Recycling experiment of silica-supported ruthenium chloride catalyst (RuCl ₃ / SiO ₂ ))
20 g of cyclohexane oxidation reaction solution prepared by the method shown in Reference Example 1 and 2 wt% RuCl ₃ / SiO ₂ catalyst prepared by the method shown in Reference Example 3 in a pressure-resistant glass reactor having an internal volume of 50 ml and a Ru metal concentration of 500 It added so that it might become mass ppm, and it was made to decompose-react for 30 minutes at 90 degreeC, stirring under nitrogen atmosphere. The reaction solution was cooled and the obtained reaction solution was analyzed by gas chromatography. As a result, the decomposition ratio of cyclohexyl hydroperoxide was 98.74%.
The reaction solution was filtered through a membrane filter, and the recovered silica-supported ruthenium chloride catalyst (RuCl ₃ / SiO ₂ ) was used again for the same reaction to decompose cyclohexyl hydroperoxide, which was repeated 12 times. . Table 1 shows the number of uses of the silica-supported ruthenium chloride catalyst (RuCl ₃ / SiO ₂ ) and the decomposition rate of cyclohexyl hydroperoxide.

Claims (2)

A process for producing a cycloalkanol and a cycloalkanone, characterized in that a cycloalkyl hydroperoxide is decomposed in the presence of a metal chloride supported on activated carbon, silica gel or alumina. The process for producing cycloalkanol and cycloalkanone according to claim 1, wherein the metal chloride is cupric chloride or ruthenium chloride.