WO2005063388A1

WO2005063388A1 - Method for preparing solid acid catalyst and method for producing lactam compound using such catalyst

Info

Publication number: WO2005063388A1
Application number: PCT/JP2004/019298
Authority: WO
Inventors: Yasushi Yamamoto; Jun Haruta; Yukimasa Fukuta
Original assignee: Ube Industries, Ltd.
Priority date: 2003-12-25
Filing date: 2004-12-24
Publication date: 2005-07-14
Also published as: JPWO2005063388A1; JP2009131847A; JP4760917B2; JP4297115B2

Abstract

A method for preparing a solid acid catalyst is characterized in that at least one compound selected from oxides and hydroxides is brought into contact with a gas containing a sulfur trioxide. A method for producing a lactam compound is characterized in that a corresponding lactam compound is produced by Beckmann rearrangement of a cycloalkanone oxime compound in the presence of a solid acid catalyst prepared by the above-described method.

Description

Specification

TECHNICAL FIELD The present invention relates to a method for preparing a solid acid catalyst and a method for producing a ratatum compound using the catalyst.

The present invention relates to a method for preparing an environment-friendly solid acid catalyst having a high activity in an acid-catalyzed reaction, and a method for producing a corresponding ratatum compound from a cycloalkanone oxime compound by Beckmann rearrangement using the same. Things. The obtained ratatum compound is an important compound as a raw material for nylon.

Background art

Conventionally, acid catalysts such as sulfuric acid, aluminum chloride, hydrogen fluoride, and phosphoric acid have been used for acid catalyst reactions such as alkylation reaction, esterification reaction, and Beckmann rearrangement reaction. However, these acid catalysts are difficult to separate and recover, and there are problems of equipment corrosion and waste acid treatment.

[0003] Acid catalysts that solve these problems include, for example, single metal oxides such as alumina and titania, composite oxides such as silica-alumina, silica-titania, and alumina-boria, ZSM_5, / 3-zeolite, and the like. Many solid acid catalysts such as zeolite and clay minerals such as montmorillonite are known (for example, see Non-Patent Document 1). However, since these solid acid catalysts have a relatively weak acid strength, depending on the reaction system, they may not show sufficient activity as a solid acid catalyst.

[0004] On the other hand, as a solid acid catalyst having a strong acidity, a solution containing a Group IV metal hydroxide or oxide of 5 to 20 times by weight of a 0.01 to 5 molar concentration of a sulfate group-containing solution is used as a solid acid catalyst having strong acidity. Sintered by calcining in the temperature range of 350-800 ° C after contact with acid, acid strength (H) is stronger than -10.

0

A solid acid catalyst has been proposed (for example, see Patent Document 1). However, this treatment method in which the solution is brought into contact with the sulfate group-containing solution also causes problems such that the acid sites are poisoned by water in the solution, and that water remaining in the catalyst causes side reactions in the solid acid catalyst reaction. It is also known that when this treatment method is applied to, for example, a mesoporous body having low acid resistance, the skeletal structure of the mesoporous body is destroyed (for example, see Non-Patent Document 2). Destruction of the skeletal structure causes a decrease in the pore diameter, pore volume, and surface area of the solid catalyst, and reduces the catalytic activity. It is not preferable because it has an adverse effect.

[0005] In industrial production of ε-force prolatatam by rearrangement of cyclohexanone oxime, fuming sulfuric acid is used as an acid catalyst. However, in this method, it is necessary to neutralize a strong acid such as sulfuric acid with ammonia in order to separate and recover ε-force prolatatam, and a large amount of ammonium sulfate is by-produced. In addition, as described above, development of an efficient catalyst for rearrangement, which has many process problems such as equipment corrosion, is expected.

[0006] Therefore, various studies have been made on a homogeneous catalyst or a heterogeneous catalyst with respect to a Beckmann rearrangement reaction in a liquid phase without using a sulfuric acid catalyst. However, since a homogeneous catalyst makes the separation of the catalyst complicated, a heterogeneous catalyst which is easy to separate the catalyst is more preferable industrially.

[0007] Regarding heterogeneous catalysts, a method using a rhenium compound as a catalyst, a method using a β-zeolite containing zinc as a catalyst, and a method using a group IV metal or a group III metal such as zirconium oxide, titanium oxide, or aluminum oxide. A method using a catalyst that supports a Group VIII metal such as palladium, platinum, rhodium and ruthenium on an oxide carrier, a method using a zeolite supporting iminium ion as a catalyst, and a method using a catalyst having a dielectric constant of 6-60 in the presence of a solid catalyst. A method of performing a reaction in the presence of a compound in the range has been proposed.

[0008] In a method using a rhenium compound as a catalyst (for example, see Non-Patent Document 2), the selectivity of force prolatatam is extremely low. Furthermore, the reaction temperature is as high as 200 ° C or higher. A similar method using a renium compound as a catalyst (see, for example, Patent Document 3) has a high conversion rate of 100% and a yield of force product of 81.4 mol%, but it uses a nitrogen-containing heterocyclic compound such as pyridine in combination. However, the reaction system is complicated.

[0009] beta containing zinc - zeolite in the method of the catalyst (for example, see Patent Document 4), the conversion in the anti応温of 130 ° C 47 mole ^_0/0, the power Puroratatamu selectivity 72 mole ^_0/0 (yield The rate is 34 mol%), and if the deviation is low, there is a problem.

[0010] A method using a catalyst in which an oxide of a Group IV metal or a Group III metal such as zirconium oxide, titanium oxide, or aluminum oxide is supported as a carrier and supports a Group VIII metal such as palladium, platinum, rhodium, or ruthenium (for example, see Patent Document 1) 5) is high in both conversion and yield, but precious metals such as palladium, platinum, rhodium and ruthenium are expensive and have large price fluctuations. Is not satisfactory.

[0011] The method using a zeolite supporting iminium ion as a catalyst (for example, see Patent Document 6) has a problem that the method for preparing the catalyst is complicated and the conversion of cyclohexanone oxime is as low as 34%.

[0012] In a method in which a reaction is performed in the presence of a solid acid catalyst in the presence of a compound having a dielectric constant in the range of 6-60 (for example, see Patent Document 7), a compound having a dielectric constant in the range of 6-60 is present. Despite the effects, the catalytic activity of the solid acid catalyst used is insufficient, and the yield of hydroprolatam is low. For example, when dehydrated benzonitrile is used as a compound having a dielectric constant in the range of 6-60, when the solid acid catalyst is 3-zeolite, the yield is 53%, and when the solid acid catalyst is Zn-containing; 3-zeolite is the same. 33%, Y-type zeolite 61%, Si〇-supported heteropolyacid 36%, A1-containing mesoporous catalyst 26%

2

There is a problem that the yield cannot be obtained.

[0013] Non-patent document 1: Catalyst dictionary (Asakura Shoten) 236 pages

Non-Patent Document 2 Journal of Molecular Catalysis A: Chemical 192 (2003) 1 53-170

Patent Document 1: Japanese Patent Publication No. 59-006181

Patent Document 2: JP 08-151362 A

Patent Document 3: JP-A-09-301952

Patent Document 4: JP 2001-19670 A

Patent Document 5: JP-A-62-169769

Patent Document 6: Japanese Patent Application Laid-Open No. 09-040641

Patent Document 7: Japanese Patent Application Laid-Open No. 2001-072657

Disclosure of the invention

Problems to be solved by the invention

An object of the present invention is to provide a method for preparing a solid acid catalyst effective for an acid catalyzed reaction. Particularly, when producing a corresponding ratatum compound from a cycloalkanone oxime compound by a Beckmann rearrangement reaction, Ratatam compounds in high yields under mild reaction conditions It is an object of the present invention to provide a method for preparing a catalyst for producing a catalyst.

Means for solving the problem

[0015] The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that at least one compound selected from the group consisting of oxides and hydroxides is brought into contact with a gas containing sulfur trioxide. The inventors have found that the above object can be achieved by a method for preparing a solid acid catalyst, which is a feature of the present invention, and have completed the present invention.

Further, according to the present invention, there is provided a method for producing a corresponding ratatum compound by a Beckmann rearrangement reaction of a cycloalkanone oxime compound in the presence of the solid acid catalyst.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

The sulfur trioxide used in the present invention is not particularly limited as long as it is produced from a substance containing sulfur. Examples of sulfur compounds used for producing sulfur trioxide include sulfur, SO, SO (n = 5-8), H SO, fuming sulfuric acid, (NH 2) SO, H SO, and H SO.

2 n n 2 4 4 2 4 2 3 2 2 n

(n = 3-7), gold such as FSO H, CF SO H, C1SO H, SOC1, SO CI, and TiSO

3 3 3 2 2 2 4 group sulfate. These may be used alone or in combination.

Of these compounds, those that are gaseous at room temperature are used as sulfur trioxide by oxidation or thermal decomposition as it is or after dilution with an inert gas. Those which are liquid or solid at room temperature can be used as sulfur trioxide by oxidizing, pyrolyzing, or pyrolyzing it and then oxidizing it.

Preferably, sulfur trioxide (SO 2) obtained by oxidizing gaseous sulfur dioxide (SO 2) at room temperature is used.

In the case of SO, for example, those diluted with an inert gas or the like can be used.

2

[0019] The oxidation of sulfur dioxide (SO 2) is usually carried out using oxygen in the presence or absence of an oxidation catalyst.

2

In the presence of an oxidation reaction, an oxidizing agent such as ozone or peroxide can be used.

There is no particular limitation on the oxygen oxidation, and those diluted with pure oxygen, air, or an inert gas can be used. However, it is preferable that the water content is small. Specifically, the amount of water in the gas to be introduced is preferably 100 ppm or less, more preferably 1 ppm or less. The content is controlled to 00 ppm, more preferably 10 ppm or less, and most preferably the water content is controlled to 10 ppm or less.

[0020] The oxidation catalyst used in the oxidation reaction performed in the presence of the oxidation catalyst is not particularly limited as long as it has a capability of oxidizing sulfur dioxide, and examples thereof include vanadium, copper, iron, and cobalt. A catalyst containing at least one of nickel and nickel can be preferably used. Preference is given to vanadium, copper and iron.

Due to their role, these oxidation catalysts are usually charged upstream of oxides or hydroxides against flowing gas.

As the at least one compound selected from the oxides and hydroxides used in the present invention, any compound can be used as long as it is surface-modified with sulfur trioxide. For example, porous oxides such as HMS and MCM41 and those in which metals are supported or introduced, zeolites such as ZSM-5 and β-zeolite and those in which metals are supported or introduced, silica alumina

And oxides such as silica, alumina, zirconia, and titania, and hydroxides serving as precursors of these, such as silica-zirconia and silica-titania.

[0022] Specific examples of at least one compound selected from oxides and hydroxides include Group 414 of the Periodic Table (using a serial number of 1-18 for the group number, according to the IUPAC inorganic chemical nomenclature revised in 1989). ), Oxides and hydroxides containing one or more elements (excluding carbon) selected from the group consisting of group numbers according to (1). The specific surface area of these oxides and hydroxides is not particularly limited, but is preferably at least 300 m ² / g, more preferably at least 700 m ² Zg, and even more preferably <700-1200 m ² / g. is there.

[0023] Specific examples of the elements selected from Group 414 of the Periodic Table include titanium, zirconium, hafnium, group 5 vanadium, neodymium, tantalum, group 6 chromium, molybdenum, and tungsten. , Group 7 manganese, rhenium, group 8 iron, ruthenium, osmium, group 9 cono-noreth, rhodium, iridium, group 10 nickel, noradium, platinum, group 1 copper, silver, gold, group 12 Zinc, cadmium, mercury, group 13 boron, anoremium, gallium, indium, thallium, group 14 silicon, germanium, tin, and lead. Preferred are titanium, zirconia, zinc, boron, anoremium, gallium, indium, thallium, germanium, tin, lead and silicon. More preferably, dinoconium, aluminum, gallium and silicon Is prime.

There is no problem if two or more of these elements are used as a mixture.

[0024] The treatment mode of at least one compound selected from oxides and hydroxides with sulfur trioxide is not particularly limited. For example, sulfur trioxide can be directly contacted in the gas phase, and can be contacted in the gas phase in the presence of sulfur dioxide (or a sulfur-containing compound), oxygen and an oxidation catalyst. As an example of the method of contacting in the gas phase in the presence of oxygen and an oxidation catalyst, an oxide and a hydroxide are filled in a lower part of a glass tube, and an oxidation catalyst is filled in an upper part thereof, and sulfur dioxide (or a sulfur-containing compound) is charged. ) And an oxygen-containing gas in the gas phase at a temperature of 100-800 ° C, preferably 200-700 ° C, for a period of 10 minutes to 1000 hours. In this case, it is preferable to allow the gas to flow from the upper layer toward the lower layer. The concentration of sulfur trioxide generated in the gas is not particularly limited, but the total supply amount of the sulfur-containing compound is preferably 0.1 mmol to 100 mol with respect to oxide and hydroxide lg. The oxygen concentration is not particularly limited, either, but is preferably 0.1 to 1000 times the molar amount of the gaseous sulfur-containing compound.

[0025] Oxides and / or hydroxides before being subjected to contact treatment with sulfur trioxide in the gas phase may have water or organic substances attached thereto. It is preferable to perform calcination in an atmosphere (preferably while flowing air or an inert gas). In order to remove the sulfur-containing compound which is weakly physically adsorbed on the surface of the catalyst, it is also preferable to carry out the post-treatment by calcination in air or under an inert gas atmosphere (preferably while flowing air or an inert gas). The firing temperature and the firing time for the pre-treatment and the post-treatment are not particularly limited, and the force that can be selected depending on the case is preferably 100 to 800 ° C, and one minute to one hundred hours.

[0026] The solid acid catalyst thus obtained can be effectively used as a catalyst in the production of a corresponding ratata compound by an acid catalysis reaction, particularly a Beckmann rearrangement reaction from a cycloalkanone oxime compound. Is done.

[0027] The cycloalkanone oxime compound used for producing the ratatum compound in the present invention is preferably a cycloaliphatic hydrocarbon oxime compound having 5 to 12 carbon atoms. Specifically, cyclopentanone oxime, cyclohexanone oxime, cycloheptanone oxime, cyclooctanone oxime, cyclononanonoxime, cyclodecanone oxime, cycloundecanone oxime, cyclododecanone oxime No. Preferably , Cyclohexanone oxime and cyclododecanone oxime.

[0028] These cycloalkanone oximes can also be used in the form of a salt. As the salt, it is used as a hydrochloride or a sulfate.

These cycloalkanone oxime compounds can be used alone or in combination of two or more without any problem.

[0029] Specific examples of the corresponding ratatam compound obtained in the present invention include valerolatatum from cyclopentanone oxime, force prolatatam from cyclohexanone oxime, enantholactam and cyclododecanone oxime from cycloheptanone oxime. Is lau mouth ratatum.

[0030] The reaction conditions of the Beckmann rearrangement reaction of the present invention are not particularly limited, and the reaction is carried out by a gas phase reaction, a trickle reaction, and a liquid phase reaction, and preferably a liquid phase reaction.

[0031] In the liquid phase reaction, it is not always necessary to use a solvent. Specific examples of the use of a solvent include nitrile compounds such as benzonitrile, acetonitrile, propionitrile, butyronitrile, forcepronitrile, adiponitrile, and tolunitrile; and benzene, toluene, xylene, mesitylene, and methoxybenzene. Aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds such as n-hexane, n-heptane, n-octane, n-dodecane, ester compounds such as dimethyl phthalate, dibutyl phthalate and dimethyl malonate, benzyl alcohol, cyclo Hexanol compounds, hexane compounds such as isopropyl alcohol, isopropyl alcohol compounds, aldehyde compounds such as acetoaldehyde, benzaldehyde, ketone compounds such as acetyl ketone, methyl ethyl ketone, cyclohexanone, and diethyl. Examples thereof include ether compounds such as lenglycol dimethylethanol ether, and halogen-containing hydrocarbon compounds such as chlorobenzene. These can be used alone or in combination. Preferably, it is a nitrile compound.

[0032] The amount of these solvents to be used is not particularly limited, but is 0.1 to 10,000 times by weight, preferably 1 to 1000 times by weight, more preferably 2 to 100 times by weight, based on the cycloalkanone oxime compound. It is by weight, more preferably 3 to 50 times by weight.

[0033] The amount of the solid acid catalyst produced by the above-mentioned method is not particularly limited. However, the amount of the solid acid catalyst to be used is 0.00000001-10 times by weight based on the cycloalkanone oxime compound. preferable.

[0034] The Beckmann rearrangement reaction in a liquid phase, which is a preferred embodiment of the present invention, is usually carried out by introducing a cycloanolecanone oxime compound and a solid acid catalyst into an appropriate solvent and then heating. The reaction is usually carried out in the presence of air or a gas inert to the rearrangement reaction, preferably in the presence of a gas inert to the rearrangement reaction. Examples of the gas inert to the rearrangement reaction include nitrogen, helium, and argon. The reaction is usually carried out at a temperature of 30 to 350 ° C, preferably 50 to 250 ° C, more preferably 60 to 200 ° C. The reaction pressure is not particularly limited, and the reaction is carried out under normal pressure or under pressure.

If the rearrangement reaction temperature is lower than the above range, the reaction may hardly proceed. On the other hand, if the reaction temperature is higher than the above range, a side reaction proceeds, and the yield of the desired product, ratatum, decreases, which is not preferable.

[0036] The reaction may be carried out in any of a batch reaction and a continuous flow reaction, and may be carried out in any of a suspended bed, a fixed bed and a fluidized bed. The reaction time or residence time varies depending on the reaction conditions, but is carried out for 1 minute to 24 hours.

[0037] The obtained ratatum compound is separated and purified by a commonly used crystallization, distillation operation or the like.

(Example of oxide synthesis)

Next, a method for synthesizing the oxide used in the present invention will be described.

[0039] The atomic ratio of the constituents of the oxide was determined by ICP analysis using an ICP-AES measuring device (ICAP-575II; manufactured by Nippon Jarrell's Ash Co.). BET specific surface area measurement (pretreatment under vacuum at 120 ° C for 30 minutes) by nitrogen adsorption using (NOVA-1200; manufactured by urea ionitas) and X-ray diffraction pattern (Cu-K α ray ) Were measured using a powder X-ray diffractometer (RAD-RX: manufactured by Rigaku Corporation).

[0040] (Synthesis example 1 of oxide)

200 mmol of tetraethyl orthosilicate and 10 mmol of a 70 wt% zirconium propoxide / pronol solution were mixed and stirred at room temperature for 1 minute. The obtained solution (1) is added to a mixture (2) of dodecinoleamine (60 mmol), ethanol (1.3 mol) and water (7.2 mol), and the mixture is stirred at room temperature for 1 hour. Stir vigorously for a while. After the formed white gel was aged at room temperature for 113 hours, the white solid was collected by filtration, washed with water and ethanol, and dried at 105 ° C for 24 hours. Next, the temperature was raised from room temperature to 600 ° C. in 5 ° C.Z in the air, and calcined at 600 ° C. for 1 hour. X-ray diffraction measurement (Cu-Ka line) and nitrogen adsorption isotherm by nitrogen adsorption measurement confirmed that the obtained composite oxide was a mesoporous material. The specific surface area was 993 m ² / g. An ICP analysis of this composite oxide revealed that Si / Zr (atomic ratio) was 16. Hereinafter, this is abbreviated as Zr_MS-16.

(Oxide Synthesis Example 2)

A composite oxide was prepared in the same manner as in Solid Oxide Production Example 1, except that the 70 wt% zirconium propoxide / propanol solution was changed to 2 mmol. X-ray diffraction measurement confirmed that the obtained composite oxide was a mesoporous material. Si / Zr (atomic ratio) = 87. Hereinafter, this is abbreviated as Zr-MS-87.

(Oxide Synthesis Example 3)

200 mmol of tetraethylorthosilicate, 1.3 mol of ethanol and 20 Ommol of isopropanol were mixed, and 4.O mmol of gallium nitrate was added thereto, followed by stirring at room temperature for 20 minutes. The obtained mixture (1) was added to a mixture (2) of dodecylamine 60 mmol and water 7.2 mol, and the mixture was vigorously stirred at room temperature for 1 hour. After the resulting white gel was aged at room temperature for 113 hours, the white solid was collected by filtration, washed with water and ethanol, and dried at 105 ° C for 24 hours. Then, the temperature was raised from room temperature to 600 ° C. in air at 5 ° C. for 5 minutes and calcined at 600 ° C. for 1 hour. X-ray diffraction measurement confirmed that the obtained composite oxide was a mesoporous material. SiZGa (atomic ratio) = 50. Hereinafter, this is abbreviated as Ga_MS_50.

(Oxide Synthesis Example 4)

200 mmol of tetraethyl orthosilicate, 1.3 mol of ethanol and 20 Ommol of isopropanol were mixed, and 4.O mmol of aluminum isopropoxide was added thereto, followed by stirring at 70 ° C. for 20 minutes. The obtained mixture (1) was added to a mixture (2) of dodecinoleamine (60 mmol) and water (7.2 mol), and the mixture was vigorously stirred at room temperature for 1 hour. The resulting white gel was aged at room temperature for 113 hours, then the white solid was collected by filtration, washed with water and ethanol, and dried at 105 ° C for 24 hours. Next, the temperature is raised from room temperature to 600 ° C in air at 5 ° C / min and baked at 600 ° C for 1 hour did. X-ray diffraction measurement confirmed that the obtained composite oxide was a mesoporous material. Si / Al (atomic ratio) = 50. Hereinafter, this is abbreviated as A1-MS-50.

(Oxide Synthesis Example 5)

70wt. /. Zirconium propoxide An oxide was prepared in the same manner as in Production example 1 of the solid oxide except that the Z-propanol solution was not added. X-ray diffraction measurement confirmed that the obtained oxide was a mesoporous material. Hereinafter, this is abbreviated as MS.

(Oxide Synthesis Example 6)

Sodium silicate solution (27% Si〇, 14% NaOH) 23. Og and 25% cetyltrimethinolean

2

20 g of the monium chloride solution was mixed with vigorous stirring, and 1N hydrochloric acid was added to adjust the pH of the mixture to 8.5. This was stirred at room temperature for 3 hours, then charged in an autoclave, and kept at 100 ° C for 16 hours. After cooling, the solid was collected by filtration, washed with water, and dried in air at 85 ° C. The dried product was calcined at 200 ° C for 2 hours and further at 540 ° C for 6 hours under an air stream. The obtained oxide showed a diffraction pattern similar to that of MCM41 in X-ray diffraction measurement. Hereinafter, this is abbreviated as MCM41.

Example

Next, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0047] The sulfur content of the solid acid catalyst was determined by a fully automatic X-ray fluorescence spectrometer (PW-2400: PHI

(Manufactured by LIPS). The conversion of the cycloalkanone oxime compound and the yield of the lactam compound were calculated by analyzing the reaction solution by liquid chromatography.

In addition, sulfur trioxide was confirmed by installing a water bubbler at the outlet of the reactor, using sulfuric acid as the reaction gas, and using an ion chromatograph analyzer (IC7000S: manufactured by Yoko J11 Denki Co., Ltd.).

Example 1

0.6g of Zr-MS-16 (oxide) in the lower layer of quartz glass tube and 8g of 7wt% vanadium pentoxide / silica catalyst (oxidation catalyst) in the upper layer, nitrogen-based 5000ppm sulfur dioxide gas at 40ml / min And mixed gas of 100ml / min G2 grade pure air CJFP product standard) and 420 ° C

2

Contact for 18 hours. As a pre-treatment, it is recommended Firing was performed at 420 ° C. for 1 hour in a stream of air (100 ml / min) as a post-treatment for 1 hour. The resulting catalyst had a sulfur content of 2.2% by weight. The specific surface area was 828 m ² / g.

[0049] At this time, the mixed gas (exhaust gas) after contact with the oxide was brought into contact with water for 1 hour, and ion chromatography analysis of sulfate ions and sulfite ions contained in the water was performed. The ions were detected at 0.058 mmol and 0.019 mmol, respectively.

[0050] Cyclododecanone oxime treated with 0.05 g of this catalyst and dried under reduced pressure at 50 ° C for 12 hours 2.

A 50 ml glass flask was charged with 5 mmol and benzonitrile 5 · Og, and a Beckmann rearrangement reaction was performed at 90 ° C. for 4 hours. As a result, the conversion of cyclododecanone oxime was 89.6 mol%, and the yield of lauguchi ratatum was 83.0 monole%.

[0051] Comparative Example 1

2 g of Zr—MS-16 was immersed in 10 ml of 1N H 2 SO 4 aqueous solution, filtered, and then filtered at 105 ° C for 24 hours.

twenty four

Dried for hours. The dried product was heated in the air to a room temperature power of 400 ° C at a rate of 5 ° C / min and calcined at 400 ° C for 3 hours. The specific surface area of the obtained catalyst was 579 m ² / g.

[0052] Using this catalyst, a reaction was carried out in the same manner as in Example 1. As a result, the conversion of cyclododecanone O oxime is 66.8 Monore ^_0/0, the yield of Lau port Ratatamu is 60.2 mol ⁰ /. Met.

Comparative Example 2

A Beckmann rearrangement reaction was carried out in the same manner as in Example 1, except that the catalyst was changed to untreated Zr-MS-16. As a result, the conversion of cyclododecanone O oxime is 26.1 mole ^_0/0, Lau port rata Tam yield was 19.3 mol ^_0/0.

Example 2

A catalyst was prepared in the same manner as in Example 1 except that the 7 wt% vanadium pentoxide Z silica catalyst was changed to lOwf / o copper oxide / silica catalyst, and a Beckmann rearrangement reaction was performed using the prepared catalyst. As a result, the conversion of cyclododecanone O oxime is 87.2 mol ^_0/0, the yield of Lau port Ratatamu was 79.8 Monore%.

Example 3

A catalyst was prepared in the same manner as in Example 1 except that the 7 wt% vanadium pentoxide Z silica catalyst was changed to lOwf / o iron oxide / silica catalyst, and a Beckmann rearrangement reaction was performed using the prepared catalyst. It was. As a result, the conversion of cyclododecanone O oxime is 75.2 mol ^_0/0, the yield of Lau port Ratatamu was 72.0 Monore%.

Example 4

A catalyst was prepared in the same manner as in Example 1 except that the 7 wt% vanadium pentoxide Z silica catalyst was changed to an lOwf / o cobalt oxide Z silica catalyst, and a Beckmann rearrangement reaction was performed using the prepared catalyst. As a result, the conversion of cyclododecanone O oxime is 39.4 mol ^_0/0, the yield of Lau port rata Tam was 36.7 mol ^_0/0.

Example 5

A catalyst was prepared in the same manner as in Example 1 except that the 7 wt% vanadium pentoxide / silica catalyst was changed to a 10 wt% nickel oxide / silica catalyst, and a Beckmann rearrangement reaction was performed using the prepared catalyst. As a result, the conversion of cyclododecanone O oxime is 25.4 mol ^_0/0, Lau port rata Tam yield 23-4 mole ⁰ /. Met.

Comparative Example 3

A catalyst was prepared in the same manner as in Example 1 except that the catalyst was not charged with 7 wt% of vanadium pentoxide / silica, and a Beckmann rearrangement reaction was performed using the prepared catalyst. As a result, the conversion of cyclododecanone O oxime is 18, 5 mole ^_0/0, the yield of Lau port Ratatamu was 14.8 mol ^_0/0.

[0059] From the above results, without an oxidation catalyst, SO could not be oxidized to S 酸化, and the solid acid catalyst

twenty three

Function was not expressed.

Example 6

7 wt% Vanadium pentoxide Z silica catalyst to 16 g, 5000 ppm SO gas flow rate 100

2

The catalyst was prepared in the same manner as in Example 1 except that the flow rate of G2 grade pure air (JFP product standard) was changed to 250 mlZ, and the contact time was changed to 9 hours. A rearrangement reaction was performed. As a result, the conversion of cyclododecanone O oxime 9 4.0 Monore ^_0/0, the yield of Lau port Ratatamu was 86.6 mol ^_0/0.

Example 7

A catalyst was prepared in the same manner as in Example 6 except that the amount of the 7 wt% vanadium pentoxide Z silica catalyst was changed to 8 g, and a Beckmann rearrangement reaction was performed using the prepared catalyst. As a result, the cyclod Conversion of Dekanonokishimu is 61.7 mol ^_0/0, the yield of Lau port Ratatamu is 56.9 mole ^_0/0 der ivy.

Example 8

A catalyst was prepared in the same manner as in Example 1 except that the oxide was changed to Zr-MS-87, and a Beckmann rearrangement reaction was performed using the prepared catalyst. As a result, the conversion of cyclododecanone O oxime is 76.1 mole ^_0/0, the yield of Lau port Ratatamu is 71.4 mol ⁰ /. Met. The catalyst had a sulfur content of 2.1% by weight.

[0063] Comparative Example 4

A Beckmann rearrangement reaction was performed in the same manner as in Example 1 except that the catalyst was changed to untreated Zr-MS-87. As a result, the conversion of cyclododecanone O oxime is 5.3 mol ^_0/0, Lau port rata Tam yield 2 2.0 mol ⁰ /. Met.

Example 9

A catalyst was prepared in the same manner as in Example 1 except that the oxide was changed to Ga-MS-50, and a Beckmann rearrangement reaction was performed using the prepared catalyst. As a result, the conversion of cyclododecanone O oxime is 97.8 Monore ^_0/0, the yield of Lau port Ratatamu is 93.3 mol ⁰ /. Met. The catalyst had a sulfur content of 2.1% by weight.

Comparative Example 5

A catalyst was prepared in the same manner as in Comparative Example 1 except that the oxide was changed to Ga-MS-50, and a Beckmann rearrangement reaction was performed using the prepared catalyst. As a result, the conversion of cyclododecanone O oxime is 55.3 Monore ^_0/0, the yield of Lau port Ratatamu was 48.2 Monore ^_0/0.

Comparative Example 6

A Beckmann rearrangement reaction was performed in the same manner as in Example 1 except that the catalyst was changed to untreated Ga-MS-50. As a result, the conversion of cyclododecanone O oxime is 18.7 mol ^_0/0, Lau port rata Tam yield was 12.3 mol ^_0/0.

Example 10

A catalyst was prepared in the same manner as in Example 1 except that the oxide was changed to A1-MS-50, and a Beckmann rearrangement reaction was performed using the prepared catalyst. As a result, the conversion of cyclododecanone O oxime is 90.9 Monore ^_0/0, the yield of Lau port Ratatamu is 86.4 mol ⁰ /. Met. The catalyst sulfur The content was 2.0% by weight.

[0068] Comparative Example 7

A catalyst was prepared in the same manner as in Comparative Example 1 except that the oxide was changed to A1-MS-50, and a Beckmann rearrangement reaction was performed using the prepared catalyst. As a result, the conversion of cyclododecanone O oxime is 33.4 Monore ^_0/0, the yield of Lau port Ratatamu was 32.0 Monore ^_0/0.

[0069] Comparative Example 8

A Beckmann rearrangement reaction was carried out in the same manner as in Example 1 except that the catalyst was changed to untreated A1-MS-50. As a result, the conversion of cyclododecanone O oxime is 27.9 mole ^_0/0, Lau port rata Tam yield 27-3 mole ⁰ /. Met.

Example 11

A catalyst was prepared in the same manner as in Example 1 except that the oxide was changed to β-zeolite (manufactured by UOP) which had been calcined in air at 600 ° C for 2 hours, and a Beckmann rearrangement reaction was performed using the prepared catalyst. Was. As a result, cyclododecanone O conversion of oxime is 92.4 Monore ^_0/0, the yield of Lau port Ratatamu was 89.1 mol%. The catalyst had a sulfur content of 3.0% by weight.

[0071] Comparative Example 9

A catalyst was prepared in the same manner as in Comparative Example 1, except that the oxide was changed to β-zeolite (manufactured by UOP) which had been calcined in air at 600 ° C for 2 hours, and a Beckmann rearrangement reaction was performed using the prepared catalyst. Was. As a result, the conversion of cyclododecanone O oxime is 23.1 mole ^_0/0, the yield of Lau port Ratatamu was 5 mol% 19..

[0072] Comparative Example 10

A Beckmann rearrangement reaction was carried out in the same manner as in Example 1, except that the catalyst was changed to untreated / 3-zeolite (manufactured by UOP) which had been calcined in air at 600 ° C for 2 hours in advance. As a result, the conversion of Shikurodode Kanonokishimu is 26.5 Monore ^_0/0, the yield of Lau port Ratatamu was filed with 23.8 mole ^_0/0.

Example 12

A catalyst was prepared in the same manner as in Example 1 except that the oxide was changed to MS, and a Beckmann rearrangement reaction was performed using the prepared catalyst. As a result, the conversion of cyclododecanone O oxime 49. 4 mol ^_0/0, the yield of Lau port Ratatamu is 45.8 mol ⁰ /. Met. The sulfur content of the catalyst Was 1.3% by weight.

[0074] Comparative Example 11

A catalyst was prepared in the same manner as in Comparative Example 1 except that the oxide was changed to MS, and a Beckmann rearrangement reaction was performed using the prepared catalyst. As a result, the conversion of cyclododecanone O oxime 17. 9 moles ^_0/0, the yield of Lau port Ratatamu was 7.3 mol%. Sulfur was not detected in the catalyst.

[0075] Comparative Example 12

A Beckmann rearrangement reaction was performed in the same manner as in Example 1, except that the catalyst was changed to untreated MS. As a result, the conversion of cyclododecanone O oxime is 10.2 mol ^_0/0, the yield of Lau port Ratatamu was 1.7 Monore%.

Example 13

A catalyst was prepared in the same manner as in Example 1 except that the oxide was changed to MCM41, 0.7 g, and a Beckmann rearrangement reaction was performed using the prepared catalyst. As a result, the conversion of cyclododecanone O oxime is 83.4 Monore ^_0/0, the yield of Lau port Ratatamu is 76.3 mol ⁰ /. Met. The catalyst had a sulfur content of 1.8% by weight.

Example 14

A catalyst was prepared in the same manner as in Example 1 except that the oxide was changed to AEROSIL 200 (manufactured by Nippon AEROSIL) and 0.7 g, and a Beckmann rearrangement reaction was performed using the prepared catalyst. As a result, the conversion of cyclododecanone O oxime is 21.7 mol ^_0/0, the yield of Lau port Ratatamu was 18.7 mol%. The catalyst had a sulfur content of 0.5% by weight.

Example 15

A catalyst was prepared in the same manner as in Example 1 except that the oxide was changed to CARIACT Q_30 (manufactured by Fuji Silicon Chemicals) and 1.2 g, and a Beckmann rearrangement reaction was performed using the prepared catalyst. As a result, the conversion of cyclododecanone O oxime is 12.8 Monore ^_0/0, the yield of Lau port Ratatamu was 9. 9 mole percent. The catalyst had a sulfur content of 0.4% by weight.

Example 16

The catalyst was prepared in the same manner as in Example 1 except that the oxide was changed to 1.6 g of aluminum hydroxide, which is a hydroxide, and the pretreatment was not performed, and the Beckmann rearrangement reaction was performed using the prepared catalyst. Responded. As a result, the conversion of cyclododecanone O oxime is 12.5 mole ^_0/0, Lau port rata Tam yield was 0 mol% 8.. The catalyst had a sulfur content of 9.8% by weight.

Example 17

The catalyst was prepared in the same manner as in Example 1 except that the oxide was changed to zirconium hydroxide, which is a hydroxide, and 3.Og, and the pretreatment was not performed, and the Beckmann rearrangement reaction was performed using the prepared catalyst. went. As a result, the conversion of cyclododecanone O oxime is 37.2 mol ^_0/0, Lau port rata Tam yield was 32.3 mol%. The sulfur content of the catalyst was 0.8% by weight.

Table 1 summarizes the above Examples 117 and Comparative Examples 112.

[0082] [Table 1]

Industrial applicability

According to the present invention, at least one compound selected from the group consisting of oxides and hydroxides By using, it is possible to produce a solid acid catalyst having a high activity for an acid catalyst reaction. In addition, by using this catalyst, even in the absence of a strong acid, the Beckmann rearrangement reaction of a cycloalkanone oxime compound proceeds efficiently, and the corresponding ratatam compound with a small amount of by-product oligomers can be advantageously produced in high yield. Can be.

Claims

The scope of the claims

[I] A method for preparing a solid acid catalyst, comprising contacting at least one compound selected from the group consisting of oxides and hydroxides with a gas containing sulfur trioxide.

[2] The method for preparing a solid acid catalyst according to claim 1, wherein the gas containing sulfur trioxide is obtained by oxidizing sulfur dioxide.

[3] The method for preparing a solid acid catalyst according to claim 2, wherein the oxidation of sulfur dioxide is carried out in the presence of an oxidation catalyst.

4. The method for preparing a solid acid catalyst according to claim 3, wherein the oxidation catalyst is a catalyst containing at least one element selected from the group consisting of vanadium, copper, iron, cobalt, and nickel.

5. The method for preparing a solid acid catalyst according to claim 4, wherein the oxidation catalyst is a catalyst containing at least one element selected from the group consisting of vanadium, copper, and iron.

[6] The compound is characterized in that one compound selected from the group consisting of oxides and hydroxides contains one or more elements selected from the group consisting of Groups 414 of the Periodic Table, except for carbon. 6. The method for preparing a solid acid catalyst according to any one of claims 1 to 5, wherein

[7] The method for preparing a solid acid catalyst according to claim 6, wherein the oxide is a composite oxide containing silicon.

[8] A method for producing a corresponding ratatam compound from a cycloalkanone oxime compound by a Beckmann rearrangement reaction in the presence of a solid acid catalyst obtained by the preparation method according to any one of claims 17 to 17. A method for producing a ratatam compound, which is characterized in that:

[9] Reaction

(1) In the liquid phase,

(2) At a reaction temperature of 30-350 ° C,

9. The method for producing a ratatum compound according to claim 8, wherein the method is carried out.

[10] The method for producing a ratatum compound according to claim 8 or 9, wherein the compound is cyclododecanone oxime and / or cyclohexanone oxime.

[II] A solid acid catalyst obtained by the preparation method according to any one of claims 17 to 17.