JP2005225821A - Method for producing cyclic amide compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a cyclic amide compound in high yield and facilitating the separation and the recovery of a catalyst without requiring complicated operation such as a previous dehydrating and drying treatment of a solvent or the like, and the coexistence of a dehydrating agent in the reaction system when carrying out a liquid-phase Beckmann's rearrangement reaction. <P>SOLUTION: The method for producing the cyclic amide compound uses a crystalline aluminosilicate as the catalyst and water as the solvent in the reaction when producing the cyclic amide compound by the liquid-phase rearrangement of an oxime of a cyclic ketone compound. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a cyclic amide compound by carrying out a Beckmann rearrangement reaction of an oxime of a cyclic ketone compound in a liquid phase.

It is widely known that an amide compound is produced by a Beckmann rearrangement reaction of a corresponding oxime compound. In particular, when the oxime compound is cyclohexanone oxime, ε-caprolactam useful as a raw material for nylon-6 is produced. . As the Beckmann rearrangement reaction, a liquid phase reaction using concentrated sulfuric acid or fuming sulfuric acid is widely used industrially. However, it is known that such a method has a problem that a large amount of ammonium sulfate is produced as a by-product and the corrosion of the apparatus due to the use of a strong acid. Thus, various studies have been made on the Beckmann rearrangement reaction without using sulfuric acid.
For example, as a Beckmann rearrangement reaction in a gas phase, a boric acid catalyst (see Patent Document 1), a phosphoric acid catalyst (see Patent Document 2), a silica-alumina catalyst (see Patent Document 3), or a zeolite catalyst (patent) A method using the literature 4) has been proposed. However, when these solid catalysts are used for the rearrangement reaction, high temperature gas phase reaction conditions are required, and thus there are problems such as a decrease in yield of the produced amide compound, for example, ε-caprolactam, and catalyst deterioration due to coking.

On the other hand, as a Beckmann rearrangement reaction in a liquid phase with relatively mild reaction conditions, a method of rearranging an oxime compound using a perrhenate as a catalyst in the presence of a strong acid (see Patent Document 5), an oxime compound in the presence of a rhenium compound There has been proposed a method of translocating (see Patent Document 6). However, since a homogeneous catalyst is used in such a liquid phase reaction, a special technique is required for the catalyst separation operation, which is complicated. Therefore, a heterogeneous liquid phase reaction using a solid acid catalyst is more preferable.
As the heterogeneous liquid phase Beckmann rearrangement reaction, a solid acid catalyst is used and a oxime compound is rearranged using a solvent having a dielectric constant of 6 to 60 at 20 to 25 ° C., more preferably a nitrile solvent (see Patent Document 7). ) Has been proposed. Further, a method of rearranging an oxime compound using a zeolite catalyst supporting iminium ions (see Patent Document 8) has been proposed. In such a reaction, the reaction solvent is an organic solvent inert to the reaction, preferably N, N-dimethylformamide is used.

  However, in the above heterogeneous liquid phase Beckmann rearrangement reaction, a nitrile solvent (see Patent Document 7) and an amide solvent (see Patent Document 8), which are proposed as preferable solvents, are contained in trace amounts under the rearrangement reaction conditions. It is easily hydrolyzed by water. The presence of the decomposition product of the solvent complicates the separation of the target amide product and causes a decrease in purity. Therefore, the solvent used, the raw material oxime compound and the solid catalyst need to be dehydrated and dried in advance. Alternatively, it is necessary to allow a dehydrating agent to coexist in the reaction system, and these operations have a problem of making the process more complicated.

Japanese Patent Publication No. 48-12754 Japanese Examined Patent Publication No. 45-23549 Japanese Patent Publication No. 48-39952 JP-A-62-123167 JP-A-5-51366 JP-A-8-143544 JP 2001-72657 A JP-A-9-40641

  An object of the present invention is to produce a cyclic amide compound by a rearrangement reaction from an oxime of a cyclic ketone compound, without using fuming sulfuric acid or concentrated sulfuric acid, or performing a reaction under gas phase conditions, under liquid phase conditions, To provide a method for producing a cyclic amide compound in a high yield and easily separating and recovering a catalyst without requiring a complicated operation such as a dehydrating and drying treatment of a solvent or the like or a dehydrating agent in the reaction system in advance. It is.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have surprisingly achieved a liquid phase Beckmann rearrangement reaction using a crystalline aluminosilicate catalyst and using water as a solvent. Based on this finding, the present inventors have made the present invention.
That is, the present invention is (1) when a cyclic amide compound is produced from an oxime of a cyclic ketone compound by liquid phase rearrangement, the reaction is carried out using crystalline aluminosilicate as a catalyst and further using water as a solvent. A method for producing an amide compound.
(2) The method for producing a cyclic amide compound according to the above (1), wherein the crystalline aluminosilicate of the catalyst is 5 to 500 in terms of Si / Al molar ratio.

(3) The method for producing a cyclic amide compound according to the above (1) to (2), wherein the crystalline aluminosilicate of the catalyst has an oxygen-containing 10-membered ring structure.
(4) The method for producing a cyclic amide compound according to any one of (1) to (3) above, wherein the crystalline aluminosilicate of the catalyst is ZSM-5 zeolite, ZSM-5-like zeolite or ZSM-11 zeolite.
(5) The method according to (1) to (4) above, wherein the oxime of the cyclic ketone compound is cyclohexanone oxime and the cyclic amide compound is ε-caprolactam.

  In the present invention, water is used as a solvent, and a complicated operation for preventing hydrolysis of the solvent in the liquid phase Beckmann rearrangement reaction is not required. Furthermore, the cyclic amide compound can be produced with high yield, and the catalyst can be easily separated and recovered.

Hereinafter, the present invention will be specifically described.
Examples of the oxime of the raw material cyclic ketone compound used in the liquid phase Beckmann rearrangement reaction of the present invention include cyclopentanone oxime, cyclohexanone oxime, cyclododecanone oxime and the like, and in particular, a cyclic ketone compound having 5 to 13 carbon atoms. Are preferred, and cyclohexanone oxime is more preferred.
In the present invention, crystalline aluminosilicate is used as a catalyst, but the Si / Al molar ratio having high activity for this rearrangement reaction is 5 to 500. Preferably, a crystalline aluminosilicate having a Si / Al molar ratio of 5 to 200 is used, and a crystalline aluminosilicate having a Si / Al molar ratio of 5 to 100 is more active for the rearrangement reaction. preferable. In addition, a catalyst in which a part of Al atoms is skeleton-substituted by atoms selected from B, Ga, Ti, Cr, Zn, Zr, V, Nb, Fe, Sn and the like can be used.

  The crystalline aluminosilicate in the present invention has an oxygen-containing 10-membered ring pore structure or more in its crystal structure, preferably an oxygen-containing 10-membered ring pore structure, more preferably ZSM- 5 zeolite or ZSM-5 similar zeolite or ZSM-11 zeolite. The term “oxygen-containing 10-membered ring structure” as used herein refers to a zeolite containing 10 oxygen atoms in the ring structure of the zeolite pore cross section, and the classification of the pore structure of the zeolite includes, for example, zeolite science and engineering (2000). Published by Kodansha Scientific, edited by Yoshio Ono and Kenaki Yashima), pages 4-5.

  The structure of crystalline zeolite can be attributed by a powder X-ray diffraction pattern, and powder X-ray diffraction data of a known zeolite having an oxygen-containing 10-membered ring pore structure is, for example, Collection of Simulated XRD Powder Patterns for Zeolites ( 1996, Elsevier). ZSM-5 zeolite, ZSM-5-like zeolite, and ZSM-11 zeolite are all zeolites having an oxygen-containing 10-membered ring structure. ZSM-5 similar zeolite includes ZSM-5 similar zeolite described in Studies in Surface Science and Catalysis 33 (1987) pp. 167 to 215, TSZ (see European Patent No. 101232), TSZ-III (see European Patent No. 1707551), FZ-1 (see European Patent No. 31255), LZ-105 (see US Pat. No. 4,257,885), USI-108 (US Pat. No. 4,432,020) ZBM-30 (see European Patent No. 46504), ZSM-5 / ZSM-11 (see US Pat. No. 4,289,607), and the like.

The crystalline aluminosilicate used in the present invention is synthesized by ordinary hydrothermal synthesis. The silica source used in that case is not particularly limited, and water glass, silica sol, silica gel and the like can be used. As the alumina source, various inorganic compounds such as nitrates, chlorides, oxides, and organometallic compounds can be used.
In the synthesis of the crystalline aluminosilicate used in the present invention, an organic template may coexist if necessary. In that case, preferred are urea compounds such as dimethylurea, quaternary ammonium salts such as tetrapropylammonium, diamines such as hexamethylenediamine, and alcohols. However, when an organic template is used, it is necessary to remove organic substances from the crystals after hydrothermal synthesis. As a method for removing the organic substance in that case, firing in the air at a temperature of 400 ° C. or higher, a liquid phase oxidation method using an oxidizing agent such as hydrogen peroxide, or the like is used.

In order to make the crystalline aluminosilicate from which organic substances have been removed in this way into a desired cation type, a normal ion exchange operation is performed to introduce the desired cation into the crystal. The cation to be introduced is preferably a proton and is usually obtained by treatment with an aqueous solution such as hydrochloric acid or nitric acid. Further, the crystalline aluminosilicate used for the reaction may be formed into a powdery, crushed, particulate or columnar shape according to the reaction system to be carried out.
In the present invention, the reaction temperature is appropriately set depending on the productivity of the process, the oxime of the cyclic ketone compound as a raw material, the stability of the cyclic amide compound to be produced, etc., but it is in the range of 100 to 220 ° C, preferably 120 to 210 ° C. The reaction is carried out in the range of 150 to 200 ° C. A reaction temperature of 100 ° C. or higher is preferable because the reaction rate is improved, and a reaction temperature of 220 ° C. or lower is preferable because side reactions are suppressed.

There is no restriction | limiting in particular in reaction pressure, What is necessary is just the range which can keep a reaction system in a liquid phase. This reaction can be carried out in the presence of an inert gas such as nitrogen, hydrogen, helium or argon.
The liquid phase reaction type is not particularly limited, and any of batch type, semi-batch type and continuous type can be carried out. Also, the residence time and the like are not particularly specified. For example, when the reaction is carried out by suspending the powdered catalyst in a batch reactor, it is usually 0.2 to 4 hours. Since the amount of the catalyst used varies depending on the reaction mode and usage, it cannot be specified unconditionally. For example, in the case of a batch system, 0.01 to 20 times by mass, preferably 0.05 to What is necessary is just to add 10 mass times, more preferably 0.1-5 mass times a catalyst, and to make it react. When a continuous reaction mode is used, the catalyst concentration can be further increased.

  In the present invention, water is used as a solvent. Regarding the solvent effect of the liquid phase rearrangement reaction of an oxime compound using a zeolite catalyst, for example, Journal of Molecular Catalysis A: Chemical 159 (2000), page 391, the following description is given as the effect of organic solvents including water. is there. “The liquid phase Beckmann rearrangement does not proceed in polar protic solvents, but proceeds in polar aprotic solvents.” Patent Document 7 states that “in the method of producing an amide compound from an oxime compound in the presence of a solid acid catalyst in the liquid phase, the reaction is performed in the presence of a compound having a dielectric constant of 6 to 60 at 20 to 25 ° C.” It is disclosed. According to Chemical Handbook, Basic Revision, 3rd Edition (published in 1984, edited by the Chemical Society of Japan) Page 501, the dielectric constant of water is 80.1 at 20 ° C, which means that water has traditionally been used as a solvent for the liquid phase Beckmann rearrangement reaction It was considered undesirable. Furthermore, there has been concern about the hydrolysis reaction of the cyclic amide compound produced by using water as a solvent. Surprisingly, by using water as the solvent, a cyclic amide compound can be obtained in a high yield. When the cyclic amide compound to be produced is ε-caprolactam, it has been found that the hydrolysis which is concerned does not proceed.

The amount of water used in the present invention is not particularly limited and is appropriately set depending on the productivity of the process, the solubility of the oxime of the cyclic ketone compound in water, etc., but is usually 1 to 10,000 with respect to the oxime of the charged cyclic ketone compound. An amount of mass times, preferably 5 to 5000 times mass, more preferably 10 to 500 times mass is used. When using 1 mass times or more of water, since thermal decomposition of the oxime of a cyclic ketone compound can be suppressed, it is preferable. In addition, when water of 10,000 times by mass or less is used, the productivity of the cyclic amide compound per reaction volume can be increased, which is advantageous in industrial implementation.
According to the method of the present invention, a cyclic amide compound can be obtained in a high yield without requiring a complicated operation for preventing hydrolysis of the solvent. The resulting cyclic amide compound is recovered from the mixture in the reactor by conventional means such as distillation or extraction operations. Separation of the solid catalyst and the reaction solution after the reaction is extremely easy, and complicated operations relating to the separation and recovery of the catalyst components that are essential in the liquid phase rearrangement reaction using a homogeneous catalyst are not required.
Next, the present invention will be described with reference to examples and reference examples.

The conversion of cyclohexanone oxime and the yield of ε-caprolactam used in the following examples and comparative examples are respectively defined by the following formulae.
Cyclohexanone oxime conversion (%) = 100 × (O—R) / O
ε-caprolactam yield (%) = 100 × L / O
O = Preparation cyclohexanenon oxime (mol)
R = unreacted cyclohexanone oxime (mol)
L = generated ε-caprolactam (mol)

[Example 1]
1) Preparation of ZSM-5 128 g of sodium silicate solution (water glass No. 3) was dissolved in 120 g of water (solution A). 3.9 g of aluminum sulfate 18 hydrate and 4 g of concentrated sulfuric acid were dissolved in 40 g of water (Liquid B). 20 g of 1,3-dimethylurea was dissolved in 80 g of water (solution C). Using a homogenizer, liquid A was mixed with liquids B and C while stirring vigorously, and stirring was continued for 1 hour. The mixed solution was transferred to an autoclave and crystallized by heating at 150 ° C. for 40 hours. The obtained product was filtered, washed with water, dried at 120 ° C. for 5 hours, and further baked in air at 500 ° C. for 5 hours to remove organic substances. Thereafter, the product was subjected to ion exchange using 1 mol / L nitric acid, filtered, washed with water, and then dried at 120 ° C. for 6 hours to obtain a proton-type crystalline aluminosilicate. As a result of powder X-ray diffraction analysis, it was identified as zeolite ZSM-5. Further, the Si / Al molar ratio of this zeolite was measured as follows. First, 0.2 g of this zeolite and 50 g of a 5 mol / L sodium hydroxide aqueous solution were charged into a 100 ml microbomb and kept at 150 ° C. for 12 hours to completely dissolve the zeolite. When this solution was diluted so as to be suitable for analysis and the Si and Al contents were measured by ICP emission analysis, the Si / Al molar ratio was 15.

2) Beckmann rearrangement reaction of cyclohexanone oxime A 100 ml microbomb was charged with 20 ml of distilled water, 0.20 g (1.767 mmol) of cyclohexanone oxime, and 0.50 g of the catalyst obtained in 1). The inside of the system was replaced with nitrogen gas, and the total pressure in the system was further set to 0.5 MPa with nitrogen gas, and then reacted at 190 ° C. for 1 hour. After the reaction, the entire reaction solution was recovered using ethanol, and the catalyst was filtered off, followed by analysis by gas chromatography. As a result, the conversion of cyclohexanone oxime was 100%, and the yield of ε-caprolactam was 72%.

[Example 2]
A 100 ml microbomb is charged with 20 ml of distilled water, 0.20 g (1.767 mmol) of cyclohexanone oxime, and 0.50 g of ZSM-5 type zeolite (manufactured by NE Chemcat, Si / Al molar ratio = 65, proton type). The reaction was carried out in the same manner as in Example 1. As a result of analyzing the reaction solution by gas chromatography, the conversion of cyclohexanone oxime was 99%, and the yield of ε-caprolactam was 69%.

[Example 3]
1) Preparation of ZSM-11 Synthesis was performed based on the method described in Japanese Patent Publication No. 53-23280. That is, 90 g of sodium silicate and 1 g of sodium aluminate were dissolved in 168 g of water (A solution). 11 g of tetrabutylphosphonium chloride was dissolved in 152 g of water (Liquid B). Using a homogenizer, 10 g of sulfuric acid was added while vigorously stirring the solution A to adjust the pH to 10 or less, and then the solution B was gradually added. The mixture was transferred to an autoclave and crystallized by heating at 150 ° C. for 90 hours. The obtained product was filtered, washed with water, and dried at 120 ° C. for 5 hours. Thereafter, this product was subjected to ion exchange using a 1 mol / L aqueous ammonium chloride solution, filtered, washed with water, dried at 120 ° C. for 6 hours, and further calcined in air at 500 ° C. for 5 hours to obtain proton type crystalline alumino Obtained silicate. As a result of powder X-ray diffraction analysis, it was identified as zeolite ZSM-11. Moreover, when the Si / Al molar ratio of this zeolite was measured using the same method as in Example 1, the Si / Al molar ratio was 24.

2) Beckmann rearrangement reaction of cyclohexanone oxime 100 ml microbomb was charged with 20 ml of distilled water, 0.20 g (1.767 mmol) of cyclohexanone oxime, and 0.50 g of the catalyst obtained in 1), and the same procedure as in Example 1 was conducted. Reaction was performed. As a result of analyzing the reaction solution by gas chromatography, the conversion of cyclohexanone oxime was 99%, and the yield of ε-caprolactam was 67%.

[Example 4]
A 100 ml micro bomb was charged with 20 ml of distilled water, 0.20 g (1.767 mmol) of cyclohexanone oxime, and 0.50 g of the catalyst obtained in Example 1, and the reaction temperature was changed to 160 ° C. The reaction was performed. As a result of analyzing the reaction solution by gas chromatography, the conversion of cyclohexanone oxime was 93% and the yield of ε-caprolactam was 65%.

[Example 5]
As in Example 1, 20 ml of distilled water, 0.10 g (0.884 mmol) of cyclohexanone oxime, and 0.50 g of mordenite zeolite (manufactured by Tosoh, Si / Al molar ratio = 9, proton type) were charged into a 100 ml microcylinder. The reaction was carried out. As a result of analyzing the reaction liquid by gas chromatography, the conversion of cyclohexanone oxime was 85% and the yield of ε-caprolactam was 21%.

[Example 6]
As in Example 1, 20 ml of distilled water, 0.10 g (0.884 mmol) of cyclohexanone oxime, and 0.50 g of beta zeolite (manufactured by ZEOLYST, Si / Al molar ratio = 13, proton type) were charged into a 100 ml microcylinder. The reaction was carried out. As a result of analyzing the reaction solution by gas chromatography, the conversion of cyclohexanone oxime was 100%, and the yield of ε-caprolactam was 18%.

[Comparative Example 1]
A 100 ml microbomb was charged with 15 ml of benzonitrile, 0.10 g (0.884 mmol) of cyclohexanone oxime, and 0.10 g of the catalyst obtained in Example 1, and reacted in the same manner as in Example 1. At this time, the solvent, the raw material cyclohexanone oxime, and the catalyst obtained in Example 1 were not dehydrated and dried. As a result of analyzing the reaction solution by gas chromatography, the yield of ε-caprolactam was 9%. In the gas chromatograph, a component considered to be a hydrolyzate of the solvent was detected, and when the reaction liquid was further analyzed by gas chromatography-mass spectrometry, the component considered to be a hydrolyzate of the solvent was benzamide. Was confirmed.

[Comparative Example 2]
1) Preparation of Silicalite-1 After adding 278 g of ethanol to 130 g of tetraethyl orthosilicate, 291 g of 10% tetrapropylammonium hydroxide aqueous solution was added and dissolved. The solution was stirred vigorously for 30 minutes using a homogenizer. The mixed solution was transferred to an autoclave and crystallized by heating at 110 ° C. for 150 hours. The obtained product was filtered, washed with water, dried at 120 ° C. for 12 hours, and further baked in air at 550 ° C. for 6 hours to remove organic substances. As a result of powder X-ray diffraction analysis, the obtained zeolite was identified as Silicalite-1.
2) Beckmann rearrangement reaction of cyclohexanone oxime In a 100 ml micro bomb, 20 ml of distilled water, 0.10 g (0.884 mmol) of cyclohexanone oxime, and 0.50 g of the catalyst obtained in 1) were charged in the same manner as in Example 1. Reaction was performed. As a result of analyzing the reaction solution by gas chromatography, the conversion of cyclohexanone oxime was 40% and the yield of ε-caprolactam was 0%.

  In particular, ε-caprolactam obtained by rearrangement of cyclohexanone oxime has high industrial utility value. In the present invention, in a liquid phase where the reaction conditions are milder than those in the gas phase reaction, there is no need for complicated operations such as dehydration drying treatment with a solvent or the like, or coexistence of a dehydrating agent in the reaction system, and a high yield of ε It is very significant that caprolactam was obtained and that it was possible to provide a method in which the catalyst can be easily separated and recovered.

Claims (5)

A method for producing a cyclic amide compound, characterized in that when a cyclic amide compound is produced from an oxime of a cyclic ketone compound by liquid phase rearrangement, the reaction is carried out using crystalline aluminosilicate as a catalyst and water as a solvent. The method for producing a cyclic amide compound according to claim 1, wherein the crystalline aluminosilicate of the catalyst is 5 to 500 in terms of Si / Al molar ratio. The method for producing a cyclic amide compound according to claim 1 or 2, wherein the crystalline aluminosilicate of the catalyst has an oxygen-containing 10-membered ring structure. 4. The method for producing a cyclic amide compound according to claim 1, wherein the crystalline aluminosilicate of the catalyst is ZSM-5 zeolite, ZSM-5-like zeolite or ZSM-11 zeolite. The oxime of the cyclic ketone compound is cyclohexanone oxime, and the cyclic amide compound is ε-caprolactam.