JP2016008164A - Method for producing laminar silicate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a laminar silicate.SOLUTION: The method for producing a laminar silicate catalyst comprises the steps of: (1) mixing a laminar silicate, an acid and a metal element compound; (2) thermally treating the mixture obtained in the step (1) at 70°C-170°C; (3) separating a solid from the thermally treated mixture obtained in the step (2); (4) cleaning the solid separated in the step (3) while maintaining the pH of cleaning fluid at 4 or less; and (5) drying the solid obtained in the step (4).

Description

  The present invention relates to a method for producing a layered silicate.

  Patent Document 1 discloses a method for producing a catalyst in which cobalt is supported on a layered silicate by impregnating a layered silicate with an aqueous solution of a cobalt compound, and further using such a catalyst as a catalyst component. A method for producing cycloalkanol and / or cycloalkanone by oxidizing cycloalkane with oxygen is disclosed.

JP 2006-101690 A

In the production of a catalyst in which a metal species is supported on a layered silicate, the layered silicate such as montmorillonite increases in viscosity due to absorption of water and wets. There is a problem that it becomes difficult. Accordingly, an object of the present invention is to provide a method capable of easily preparing a catalyst in which a metal species is supported on a layered silicate. Furthermore, the present invention provides a method for oxidizing an amine using a layered silicate produced by such a method as a catalyst.

As a result of investigations, the present inventors have found a method for solving the above problems by the following method, and have completed the present invention. That is, the present invention includes the following methods.
1. The following steps (1) to (5),
(1): a step of mixing a layered silicate, an acid and a metal element compound,
(2): a step of heat-treating the mixture obtained in step (1) at 70 ° C. to 170 ° C.,
(3): a step of separating the solid from the heat-treated mixture obtained in step (2) (4): a step of washing the solid separated in step (3) while maintaining the pH of the washing liquid at 4 or less,
(5): a step of drying the solid obtained in step (4),
A method for producing a metal-supported layered silicate characterized by comprising:
2. Said 1 manufacturing method whose layered silicate used at a process (1) is a smectite.
3. The production method according to 1 or 2 above, wherein the acid used in the step (1) is an inorganic acid. 4. The metal element compound used in the step (1) is a compound of a Group 4 metal element, a Group 5 metal element. 5. The production method according to any one of 1 to 4 above, which is at least one compound selected from the group consisting of a compound of group 6 metal elements and a germanium compound.
5. The manufacturing method according to item 4 above, wherein the heat treatment in step (2) is performed for 1 to 20 hours 6. Any of items 1 to 5 above in which the solid obtained in step (2) is separated by filtration in step (3) The manufacturing method as described in.
7. The manufacturing method according to any one of the preceding items 1 to 6, wherein the washing liquid is separated by filtration in the step (4) 8. The drying temperature in the step (5) is any one of the preceding items 1 to 7 wherein the drying temperature is 0 ° C. to 600 ° C. Manufacturing method described

9. A layered silicate is produced by the method according to any one of the above, and in the presence of the layered silicate, the formula (I)

（式中、Ｒ^１およびＲ²は、それぞれ独立に水素原子、置換基を有していてもよい炭化水素基、または置換基を有していてもよい複素環基を表すか、あるいは、Ｒ^１およびＲ²は互いにその末端で結合して、Ｒ^１およびＲ²が結合している炭素原子とともに置換基を有していてもよい環を形成している。ただし、Ｒ^１とＲ²は同時に水素原子を表すことはない。）
で示される第一級アミンを分子状酸素で酸化することを特徴とする式（ＩＩ）

(Wherein R ¹ and R ² each independently represents a hydrogen atom, a hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent, or R 1 ¹ and R ² are bonded to each other at an end thereof to form an optionally substituted ring together with the carbon atom to which R ¹ and R ² are bonded, provided that R ¹ and R ² are It does not represent a hydrogen atom at the same time.)
A primary amine represented by the formula (II) is oxidized with molecular oxygen

（式中、Ｒ^１およびＲ²は、前記と同じ意味を表す。）
で示されるオキシム化合物の製造方法。

(Wherein R ¹ and R ² represent the same meaning as described above.)
The manufacturing method of the oxime compound shown by these.

  According to the present invention, a catalyst in which a metal species is supported on a layered silicate can be easily prepared. Oxidation reactions such as oximation can be efficiently performed using the layered silicate produced by this method as a catalyst.

  Hereinafter, the layered silicate used in the present invention will be described. The layered silicate may be a natural product, a synthetic product synthesized artificially, or a mixture thereof. Examples of the synthetic method include a hydrothermal synthesis reaction method, a solid phase reaction method, and a melt synthesis method. Examples of the layered silicate include smectite such as montmorillonite, saponite, beidellite, nontronite, soconite, stevensite, hectorite, bolconscoreite, and swinoldite; vermiculite; muscovite, phlogopite, iron mica, Mica such as East Knight, Siderophyrite Tetraferri Iron Mica, Polyricionite, Celadon Stone, Iron Ceradon Stone, Iron Alumino Ceradon Stone, Alumino Ceradon Stone, Tobe Mica, Paragonite, etc .; Clintnite, Bite Mica, Pearl Mica, etc. Brittle mica; chlorite, chamosite, penanthite, nimite, bailicroa, kukeite, suedite, etc .; talc; pyrophyllite; kaolinite, dickite, nacrite, halloysite, amesite, bercherin, cron Tedaito, Nupoa stone, Keriaito, Fureiponaito, kaolinite such Brin Doria site; antigorite, chrysotile, serpentine, such as lizardite; and the like, can also be used two or more thereof as needed. Among these, smectite is preferable in terms of selectivity of the oxime compound (II) to be obtained. In the present invention, the layered silicate may be used in the form of a clay mineral containing a layered silicate. Examples of the clay mineral containing a layered silicate include bentonite, acid clay, and activated clay. Clay minerals containing montmorillonite such as The layered silicate may be used after being fired, and the firing temperature is preferably 150 to 600 ° C., and the firing time is preferably 0.1 to 100 hours.

  The layered silicate preferably contains a cation between layers, and the cation includes a hydrogen ion, an ammonium ion, a quaternary ammonium ion, a cation of an alkali metal element, a cation of an alkaline earth metal element. Ions, cations of Group 3 metal elements, cations of Group 4 metal elements, cations of Group 5 metal elements, cations of Group 6 metal elements, cations of Group 7 metal elements, Group 8 Metal element cation, Group 9 metal element cation, Group 10 metal element cation, Group 11 metal element cation, Group 12 metal element cation, Aluminum ion, Gallium ion, Indium ion , Thallium ion, tin ion, lead ion, germanium ion, positively charged Group 4 metal element oxide, positively charged Group 5 metal element oxide, positively charged Group 6 metal oxide Metal element oxides, positively charged Group 7 metal element oxides, positively charged Group 8 metal element oxides, positively charged Group 9 metal element oxides, positively charged Group 7 metal element oxides Group 10 metal element oxide, positively charged Group 11 metal element oxide, positively charged Group 12 metal element oxide, positively charged aluminum oxide, positively charged gallium oxide Materials, positively charged indium oxide, positively charged thallium oxide, positively charged tin oxide, positively charged lead oxide, positively charged germanium oxide, and the like.

  The smectite used preferably in the present invention is a tetrahedral sheet composed of a cation and oxygen, and an octahedral sheet composed of a cation and oxygen or a hydroxide. It is a layered compound formed and having cations between the unit layers, and generally has the following formula (A)

^{_{X 0.2~0.6 (Y 1, Y 2}} ) 2~3 Z 4 O 10 (OH) 2 · nH 2 O (A)

[Wherein, X represents at least one selected from the group consisting of K ⁺ , Na ⁺ , 1 / 2Ca ²⁺ and 1 / 2Mg ²⁺ , and Y ¹ represents Mg ²⁺ , Fe ²⁺ , Mn ²⁺ , Ni ²⁺ and Zn Y ² represents at least one selected from the group consisting of ²⁺ , Y ² represents at least one selected from the group consisting of Al ³⁺ , Li +, Fe ³⁺ , Mn ³⁺ and Cr ³⁺ , and Z represents from the group consisting of Si and Al It represents at least one selected (except when Z is only Al), and n ≧ 0. ]
Is a layered silicate. X represents a cation between layers, Y ¹ and Y ² represent a cation of an octahedral sheet, and Z represents a cation of a tetrahedral sheet.

  In the present invention, montmorillonite, saponite, stevensite, and hectorite are preferable among smectites in terms of selectivity of the oxime compound (II) to be obtained.

  The montmorillonite preferably used in the present invention has a 2: 1 type structure of silicate sheet / aluminate sheet / silicate sheet as a basic layer structure, and a part of aluminum of the aluminate sheet is replaced with magnesium. Is a layered silicate in which the layer is negatively charged and exchangeable cations are present between the layers.

_{X m (Al 2-m Mg} m) Si 4 O 10 (OH) 2 · nH 2 O (B)

[Wherein, X represents at least one selected from the group consisting of K ⁺ , Na ⁺ , 1 / 2Ca ²⁺ and 1 / 2Mg ²⁺ , and 0.2 ≦ m ≦ 0.6 and n ≧ 0. ]
Is a layered silicate. X represents a cation between layers, and a cation having at least one selected from the group consisting of sodium ion, potassium ion and calcium ion is preferably used.

  In the present invention, a layered silicate catalyst is prepared by mixing the layered silicate together with an acid and a metal element compound.

  Examples of the metal element compound include at least one metal element compound selected from the group consisting of Group 4 metal element compounds, Group 5 metal element compounds, Group 6 metal element compounds, and germanium compounds.

Examples of Group 4 metal element compounds include inorganic compounds of Group 4 metal elements and organic compounds of Group 4 metal elements. Examples of inorganic compounds of Group 4 metal elements include titanium trichloride (TiCl ₃ ), titanium tetrachloride (TiCl ₄ ), titanium tetrabromide (TiBr ₄ ), titanium tetrafluoride (TiF ₄ ), and tetraiodide. Titanium (TiI ₄ ), zirconium trichloride (ZrCl ₃ ), zirconium tetrachloride (ZrCl ₄ ), zirconium tribromide (ZrBr ₃ ), zirconium tetrabromide (ZrBr ₄ ), zirconium tetrafluoride (ZrF ₄ ), four Group 4 metal element halides such as zirconium iodide (ZrI ₄ ); Group 4 metal element nitrates such as titanium tetranitrate (Ti (NO ₃ ) ₄ ) and zirconium tetranitrate (Zr (NO ₃ ) ₄ ) ; zirconyl nitrate (ZrO _{(NO 3) 2)} a group 4 metal elements oxy nitrates such as; disulfate titanium _{(Ti (SO 4) 2)} , disulfate zirconium (Zr _{(SO 4) 2)} sulfate group 4 metal elements such as; titanium phosphate _{(Ti 3 (PO 4) 4} ), zirconium phosphate _{(Zr 3 (PO 4) 4} ) Group 4 metal, such as Elemental phosphates; and the like. Examples of organic compounds of Group 4 metal elements include Group 4 metals such as Ti (OR ³ ) ₄ (hereinafter, R ³ represents an alkyl group having 1 to 4 carbon atoms), Zr (OR ³ ) _{4, and the} like. Elemental alkoxide compounds; TiCl (OR ³ ) ₃ , TiCl ₂ (OR ³ ) ₂ , TiCl ₃ (OR ³ ), ZrCl (OR ³ ) ₃ , ZrCl ₂ (OR ³ ) ₂ , ZrCl ₃ (OR ³ ), etc. Halogenated alkoxide compounds of Group 4 metal elements; acetates of Group 4 metal elements such as titanium tetraacetate (Ti (CH ₃ COO) ₄ ) and zirconium tetraacetate (Zr (CH ₃ COO) ₄ ); It is done. Moreover, the hydrate of the compound of a group 4 metal element may be used as needed, and 2 or more types thereof may be used. The group 4 metal element compound is preferably a halide other than the halide in consideration of the corrosion of the production apparatus. Among them, the sulfate of the group 4 metal element, the alkoxide compound of the group 4 metal element, the group 4 metal element Oxynitrates are preferred, and sulfates of Group 4 metal elements are more preferred.

Examples of the Group 5 metal element compound include inorganic compounds of Group 5 metal elements and organic compounds of Group 5 metal elements. Examples of inorganic compounds of Group 5 metal elements include vanadium trichloride (VCl ₃ ), vanadium tetrachloride (VCl ₄ ), vanadium tribromide (VBr ₃ ), vanadium trifluoride (VF ₃ ), and tetrafluoride. Vanadium (VF ₄ ), vanadium triiodide (VI ₃ ), niobium trichloride (NbCl ₃ ), niobium pentachloride (NbCl ₅ ), niobium tribromide (NbBr ₃ ), niobium pentabromide (NbBr ₅ ), five Niobium fluoride (NbF ₅ ), niobium pentaiodide (NbI ₅ ), tantalum trichloride (TaCl ₃ ), tantalum pentachloride (TaCl ₅ ), tantalum pentabromide (TaBr ₅ ), tantalum pentafluoride (TaF ₅ ) And halides of Group 5 metal elements such as tantalum pentaiodide (TaI ₅ ). Examples of organic compounds of Group 5 metal elements include alkoxide compounds of Group 5 metal elements such as Nb (OR ³ ) ₅ and Ta (OR ³ ) ₅ . Moreover, the hydrate of the compound of a Group 5 metal element may be used as needed, and 2 or more types thereof may be used.

Examples of the Group 6 metal element compound include inorganic compounds of Group 6 metal elements and organic compounds of Group 6 metal elements. Examples of inorganic compounds of Group 6 metal elements include chromium dichloride (CrCl ₂ ), chromium trichloride (CrCl ₃ ), chromium dibromide (CrBr ₂ ), chromium tribromide (CrBr ₃ ), and difluoride. Chromium (CrF ₂ ), chromium trifluoride (CrF ₃ ), chromium diiodide (CrI ₂ ), chromium triiodide (CrI ₃ ), molybdenum trichloride (MoCl ₃ ), molybdenum pentachloride (MoCl ₅ ), three Molybdenum bromide (MoBr ₃ ), molybdenum tetrafluoride (MoF ₄ ), molybdenum hexafluoride (MoF ₆ ), tungsten tetrachloride (WCl ₄ ), tungsten hexachloride (WCl ₆ ), tungsten pentabromide (WBr ₅ ) , halides of the group 6 metal element such as tungsten hexafluoride (WF _6); trinitrate chromium (Cr _{(NO 3) 3)} of the group 6 metal elements such as Salt; Chromium sulfate _{(III) (Cr 2 (SO} 4) 3), sulfates of Group 6 metal element and the like; and the like. Examples of organic compounds of Group 6 metal elements include alkoxide compounds of Group 6 metal elements such as Mo (OR ³ ) ₅ , W (OR ³ ) ₅ , and W (OR ³ ) ₆ ; chromium triacetate (Cr ( CH ₃ COO) ₃ ) group 6 metal element acetates; and the like. Moreover, the hydrate of the compound of a Group 6 metal element may be used as needed, and 2 or more types thereof may be used.

Examples of the germanium compound include an inorganic compound of germanium and an organic compound of germanium. Examples of germanium inorganic compounds include germanium halides such as germanium tetrachloride (GeCl ₄ ), germanium tetrabromide (GeBr ₄ ), germanium tetrafluoride (GeF ₄ ), and germanium tetraiodide (GeI ₄ ); And germanium sulfides such as germanium sulfide (GeS). Examples of germanium organic compounds include germanium alkoxide compounds such as Ge (OR ³ ) ₄ ; germanium halogenated alkoxides such as GeCl (OR ³ ) ₃ , GeCl ₂ (OR ³ ) ₂ , and GeCl ₃ (OR ³ ). Compound; and the like. Moreover, the hydrate of a germanium compound may be used as needed, and those 2 or more types may be used. Of these, germanium halides and germanium alkoxide compounds are preferred as the germanium compound.

  The amount of at least one compound selected from the group consisting of a Group 4 metal element compound, a Group 5 metal element compound, a Group 6 metal element compound, and a germanium compound is the Group 4 metal element compound, In terms of a metal element contained in at least one compound selected from the group consisting of a group 5 metal element compound, a group 6 metal element compound and a germanium compound, 0. 01-100 weight part is preferable and 0.05-50 weight part is more preferable. When using two or more kinds of compounds selected from the group consisting of compounds of Group 4 metal elements, compounds of Group 5 metal elements, compounds of Group 6 metal elements, and germanium compounds, the total amount used is within the above range. It only has to be.

  Examples of the acid mixed with the layered silicate and the metal element compound include organic acids and inorganic acids, and among them, inorganic acids are preferable. Examples of the inorganic acid include aqueous solutions of hydrogen chloride, sulfuric acid, phosphoric acid, nitric acid, and the like. In consideration of corrosion of the production apparatus, acids other than hydrogen chloride are preferable, and aqueous solutions of nitric acid and sulfuric acid are particularly preferable. The pH of the acidic aqueous solution is preferably 4 or less. The acidic aqueous solution may contain a polar organic solvent such as methanol, ethanol, acetone, 1,2-dimethoxyethane. In the preparation of the acidic aqueous solution, at least one compound selected from the group consisting of Group 4 metal element compounds, Group 5 metal element compounds, Group 6 metal element compounds, and germanium compounds, hydrolyzable halides, alkoxides When a compound that is hydrolyzed under acidic conditions such as a compound or oxynitrate is used, the compound is hydrolyzed to become an oxide, and the cation between layers is a positively charged group 4 metal element oxide, and is positively charged. Preparing a layered silicate ion-exchanged with at least one selected from the group consisting of Group 5 metal element oxides, positively charged Group 6 metal element oxides and positively charged germanium oxide. it can. In addition, as a Group 4 metal element compound, a Group 5 metal element compound, or a Group 6 metal element compound, two types that are hydrolyzed under acidic conditions such as hydrolyzable halides, alkoxide compounds, oxynitrates, etc. The above Group 4 metal element compound, 2 or more Group 5 metal element compounds, or 2 or more Group 6 metal element compounds, and Group 4 metals contained in these 2 or more compounds When the element, Group 5 metal element or Group 6 metal element are not the same among the compounds, two or more Group 4 metal elements, two or more Group 5 metal elements, or two or more Group 6 elements Since complex oxides containing metal elements can also be generated, two or more Group 4 metal elements, two or more Group 5 metal elements, or two or more Group 6 metals can be used as interlayer cations. Positively charged complex oxides with elements as constituent elements were introduced. That. When using two or more compounds selected from the group consisting of a Group 4 metal element compound, a Group 5 metal element compound, a Group 6 metal element compound and a germanium compound, A positively charged composite oxide having two or more metal elements selected from the group consisting of Group 4 metal elements, Group 5 metal elements, Group 6 metal elements, and germanium as constituent elements may be introduced.

The solution containing at least one compound selected from the group consisting of Group 4 metal element compounds, Group 5 metal element compounds, Group 6 metal element compounds, and germanium compounds includes Group 4 metal element compounds and Group 5 metals. In addition to the elemental compound, the Group 6 metal elemental compound, and the germanium compound, compounds of other elements may be included. Moreover, you may perform the contact with the solution containing the compound of another element before and / or after making it contact with this solution. Examples of other element compounds include compounds of alkali metal elements, compounds of alkaline earth metal elements, compounds of Group 3 metal elements, compounds of Group 7 metal elements, compounds of Group 8 metal elements, Group metal element compounds, Group 10 metal element compounds, Group 11 metal element compounds, Group 12 metal element compounds, aluminum compounds, gallium compounds, indium compounds, thallium compounds, tin compounds, lead compounds, silicon compounds , Arsenic compounds, antimony compounds, bismuth compounds, selenium compounds, tellurium compounds and the like, and two or more of them can be used as necessary. Of these, compounds of Group 8 metal elements, compounds of Group 9 metal elements, compounds of Group 10 metal elements, compounds of Group 11 metal elements, aluminum compounds, and silicon compounds are preferred. As a compound of another element, a compound hydrolyzed under an acidic condition such as an alkoxide compound is used, and is composed of a Group 4 metal element compound, a Group 5 metal element compound, a Group 6 metal element compound, and a germanium compound. When the solution containing at least one compound selected from the group and the compound of the other element is an acidic aqueous solution, the cations between the layers are represented by the following i), ii) and / or iii):
i) A mixture of a cation of at least one metal element selected from the group consisting of Group 4 metal elements, Group 5 metal elements, Group 6 metal elements and germanium, and positively charged oxides of other elements ii) When at least one compound selected from the group consisting of Group 4 metal element compounds, Group 5 metal element compounds, Group 6 metal element compounds and germanium compounds is a compound that is hydrolyzed under acidic conditions. A positively charged Group 4 metal element oxide, a positively charged Group 5 metal element oxide, a positively charged Group 6 metal element oxide, and a positively charged germanium oxide. A mixture of at least one selected with a positively charged oxide of another element iii) at least selected from the group consisting of Group 4 metal elements, Group 5 metal elements, Group 6 metal elements and germanium And one metal element, the other composite oxide and positively charged to a constituent element element ion-exchanged layered silicate can be prepared. Examples of compounds containing other elements that are hydrolyzed under acidic conditions include silicon alkoxide compounds. Examples of silicon alkoxide compounds include tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, and tetrabutyl orthosilicate. And tetraalkyl orthosilicate. By using a silicon alkoxide compound, a layered silicate containing a positively charged silicon oxide can be prepared.

  The mixing of the layered silicate, the metal element compound and the acid may be performed batchwise or continuously. Examples of the batch method include a layered silicate having cations exchangeable between layers in a stirring tank, a group 4 metal element compound, a group 5 metal element compound, and a group 6 metal element. And a method in which the mixture is immersed in a solution containing at least one compound selected from the group consisting of the above compound and a germanium compound and stirred and mixed. Examples of the continuous method include, for example, a group 4 metal element compound, a group 5 metal element compound, and a group 6 metal element in a tubular container filled with layered silicate having cations exchangeable between layers. Group 4 metal elements in a method of circulating a solution containing at least one compound selected from the group consisting of elemental compounds and germanium compounds, and a stirring tank containing layered silicates having exchangeable cations between layers And a method of withdrawing the liquid phase of the mixture while supplying a solution containing at least one compound selected from the group consisting of compounds of Group 5, Group 5 metal elements, Group 6 metal elements, and germanium compounds. .

  The mixture obtained by mixing the layered silicate, the metal element compound and the acid is subjected to heat treatment. The heat processing temperature is 70-170 degreeC normally, Preferably it is 70-120 degreeC, More preferably, it is 70-90 degreeC. The time is usually 0.1 to 240 hours, preferably 0.5 to 120 hours. The pressure is usually 0.1 to 1 MPa in absolute pressure, preferably atmospheric pressure. In addition, the heat treatment is started by mixing one or two of the components in advance and mixing other components so that the heat treatment can be started from the time when the layered silicate, the metal element compound, and the acid are mixed. May be. The amount of the solution containing at least one compound selected from the group consisting of a Group 4 metal element compound, a Group 5 metal element compound, a Group 6 metal element compound and a germanium compound is a layered silicate. Is appropriately set. The heat treatment performed by mixing the layered silicate, the metal element compound and the acid may be performed a plurality of times as necessary, or may be performed by changing the metal element compound and the acid to different compounds.

The slurry of the mixture obtained by mixing the layered silicate, the metal element compound and the acid, the amount of the layered silicate is usually 2% by weight or more, preferably 5% by weight or more based on the moisture in the slurry. It is. The amount of the layered silicate is preferably 20% by weight or less based on the moisture in the slurry.

  The solid of the layered silicate catalyst obtained by heat treatment after the mixing of the layered silicate, metal element compound and acid is usually washed after being separated by solvent evaporation, filtration, decantation or the like. Examples of the method for evaporating the solvent include those using a drying device such as a spray dryer, a disk dryer, an air dryer, and a box dryer. Examples of the filtration method include pressure filtration, vacuum filtration, and centrifugal filtration. Examples of the cleaning liquid include water, an aqueous acidic solution, and a solvent miscible with water (for example, lower alcohol). These may be used in any order or as a mixture thereof. The washing may be performed by bringing the washing liquid into contact with the separated solid, and is typically performed by rinsing or repulping. As the cleaning liquid, water is preferable. At the time of washing, it is preferable to maintain the pH of the washing liquid mixed with the separated solid and the filtrate obtained by filtering the washing liquid at 4 or less. When water is used as the cleaning liquid, it is particularly effective to maintain the pH of the cleaning liquid in the above range because the viscosity of the layered silicate catalyst tends to increase due to the wetness and the handling property tends to deteriorate.

After washing, the produced layered silicate is dried, whereby the layered silicate can be recovered and used as a catalyst.
Drying can be performed under normal pressure or reduced pressure, the drying temperature is preferably 0 to 600 ° C., and the drying time is preferably 0.5 to 100 hours. The drying may be performed in an atmosphere of an oxygen-containing gas such as air, or may be performed in an atmosphere of an inert gas such as nitrogen, helium, argon, or oxygen dioxide.

After drying, you may bake as needed. The firing temperature is preferably 150 to 600 ° C., and the firing time is preferably 0.1 to 100 hours.

Firing may be performed in an atmosphere of an oxygen-containing gas such as air, or may be performed in an atmosphere of an inert gas such as nitrogen, helium, argon, or oxygen dioxide. Water vapor may be contained in the oxygen-containing gas or the inert gas. Firing may be performed in multiple stages under an atmosphere containing an oxygen-containing gas or an inert gas. Firing may be performed by a fluidized bed type or a fixed bed type. The apparatus used for the firing is not particularly limited as long as it can be heated. For example, a hot-air circulating firing furnace, a stationary firing furnace, a tunnel furnace, a rotary kiln, a far infrared furnace, a microwave heating furnace, or the like is used. can do.

The layered silicate obtained by the method of the present invention may be used as a catalyst for an oxidation reaction after being molded using a binder as necessary, or may be used by being supported on a carrier. Such forming treatment or supporting treatment may be performed before mixing the layered silicate, the metal element compound and the acid, or may be performed after the heat treatment of the mixed solution of the layered silicate, the metal element compound and the acid. The cleaning may be performed after the heat treatment of the mixed solution of the layered silicate, the metal element compound, and the acid. The molding process can be performed by a method such as extrusion, compression, tableting, flow, rolling, spraying, etc., and a desired shape, for example, granular, pellet, spherical, cylindrical, plate, ring, clover It can be formed into a shape or the like.

In formulas (I) and (II) and (III), a hydrocarbon group which may have a substituent represented by R ¹ and R ² or a heterocyclic group which may have a substituent In the group, a hydrocarbon group (for example, a linear or cyclic, saturated or unsaturated aliphatic group, aromatic group (aryl group) or aralkyl group) and a heterocyclic group are each independently part or all of The hydrogen atom of may be substituted with other substituents. In R ¹ and R ² , examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and an aryl group.

  As the alkyl group, an alkyl group having 1 to 24 carbon atoms is preferable. For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group, Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, eicosyl, heicosyl , Heneicosyl group, docosyl group, tricosyl group, tetracosyl group and the like.

  The alkenyl group is preferably an alkenyl group having 2 to 24 carbon atoms, for example, vinyl group, allyl group, 2-methylallyl group, isopropenyl group, 1-propenyl group, 1-butenyl group, 2-butenyl group, 3 -Butenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-1-butenyl group, 2-methyl-1-butenyl group, 3-methyl-1-butenyl group, 1-methyl-2-butenyl group, 2-methyl- 2-butenyl group, 3-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pen Nyl group, 2-methyl-1-pentenyl group, 4-methyl-3-pentenyl group, 2-ethyl-1-butenyl group, 2-heptenyl group, 2-octenyl group, 2-nonenyl group, 2-decenyl group, 2-undecenyl group, 2-dodecenyl group, 2-tridecenyl group, 2-tetradecenyl group, 2-pentadecenyl group, 2-hexadecenyl group, 2-heptadecenyl group, 2-octadecenyl group, 2-nonadecenyl group, 2-icosenyl group, A 2-eicosenyl group, a 2-henecocenyl group, a 2-henecocenyl group, a 2-docosenyl group, a 2-tricocenyl group, a 2-tetracocenyl group, and the like can be given.

  The alkynyl group is preferably an alkynyl group having 2 to 24 carbon atoms. For example, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl 2-propynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-methyl-3-butynyl group, 2-methyl-3-butynyl group, 1-hexynyl group, 2 -Hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group, 2-heptynyl group, 2-octynyl group, 2-noninyl group, 2-decynyl group, 2-undecynyl group, 2-dodecynyl group, 2 -Tridecynyl group, 2-tetradecynyl group, 2-pentadecynyl group, 2-hexadecynyl group, 2-heptadecynyl group, 2-octadecynyl group, 2-nonadecini Group, 2-Ikoshiniru group, 2-Eikoshiniru group, 2-Hen'ikoshiniru group, 2-Hen'eikoshiniru group, 2-Dokoshiniru group, 2-Torikoshiniru group, 2-Tetorakoshiniru group and the like.

  The cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

  As a cycloalkenyl group, a C3-C8 cycloalkenyl group is preferable, for example, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group etc. are mentioned.

  Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a tolyl group, and a xylyl group.

In R ¹ and R ² , examples of the substituent that the hydrocarbon group may have include the following substituents. When the hydrocarbon group is an alkyl group, alkenyl group or alkynyl group, examples of the substituent include halogen atoms such as fluorine, chlorine and bromine; cyclopropyl group, 1-methylcyclopropyl group, cyclobutyl group, cyclopentyl group, A cycloalkyl group having 3 to 6 carbon atoms such as 1-methylcyclopentyl group and cyclohexyl group; methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, s-butoxy group, isobutoxy group, t-butoxy group and the like An alkoxy group having 1 to 4 carbon atoms; a thioalkoxy group having 1 to 4 carbon atoms such as a thiomethoxy group, a thioethoxy group, a thiopropoxy group, or a thiobutoxy group; an allyloxy group, a 2-propenyloxy group, a 2-butenyloxy group, Alkenyloxy having 3 to 4 carbon atoms such as 2-methyl-3-propenyloxy group An aralkyloxy group having 7 to 20 carbon atoms; an aryl group having 6 to 18 carbon atoms such as a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthryl group; an aryloxy group such as a phenyloxy group and a naphthyloxy group; An alkanoyl group having 2 to 7 carbon atoms; an aryloyl group having 7 to 19 carbon atoms; an alkoxycarbonyl group having 1 to 6 carbon atoms; When the hydrocarbon group is an alkyl group, examples of the alkyl group substituted with an aryl group having 6 to 18 carbon atoms include benzyl group, phenethyl group, 3-phenylpropyl group, benzhydryl group, trityl group, and triphenylethyl. And aralkyl groups such as a group, (1-naphthyl) methyl group, (2-naphthyl) methyl group and the like.

In R ¹ and R ² , when the hydrocarbon group is a cycloalkyl group, a cycloalkenyl group or an aryl group, examples of the substituent include the halogen atom described above, a cycloalkyl group having 3 to 6 carbon atoms, and a carbon number. Is an alkoxy group having 1 to 4 carbon atoms, a thioalkoxy group having 1 to 4 carbon atoms, an alkenyloxy group having 3 to 4 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, and an aryl group having 6 to 18 carbon atoms , Aryloxy group, alkanoyl group having 2 to 7 carbon atoms, allyloyl group having 7 to 19 carbon atoms, alkoxycarbonyl group having 1 to 6 carbon atoms, methyl group, ethyl group, propyl group, isopropyl group, butyl Group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group and other alkyl groups having 1 to 6 carbon atoms, vinyl group, 1-propenyl group, 2-propenyl 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4 Carbon number such as -pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, etc. Are alkenyl groups having 2 to 6 carbon atoms, aralkyl groups having 7 to 20 carbon atoms such as benzyl, phenethyl, and naphthylmethyl groups.

In R ¹ and R ² , examples of the heterocyclic group include a heteroaryl group and a heteroaralkyl group. The heteroaryl group is preferably a heteroaryl group having 3 to 9 carbon atoms, and examples thereof include a pyridyl group, a quinonyl group, a pyrrolyl group, an imidazolyl group, a furyl group, an indolyl group, a thienyl group, and an oxazolyl group. The heteroaralkyl group is preferably a heteroaralkyl group having 5 to 10 carbon atoms, and examples thereof include a pyridylmethyl group, a quinolylmethyl group, an indolylmethyl group, a furylmethyl group, and a pyrrolylmethyl group.

In R ¹ and R ² , the heterocyclic group may have a substituent. In that case, examples of the substituent of the heterocyclic group include the above-described halogen atom, a cycloalkyl group having 3 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a thioalkoxy group having 1 to 4 carbon atoms. Group, alkenyloxy group having 3 to 4 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, aryl group having 6 to 18 carbon atoms, aryloxy group, alkanoyl group having 2 to 7 carbon atoms, carbon number Is an allyloxy group having 7 to 19 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an aralkyl having 7 to 20 carbon atoms. Groups and the like.

In the formula (I), when R ¹ and R ² each independently represent a hydrogen atom or an optionally substituted hydrocarbon group, examples of the amine compound (I) include methylamine, ethylamine, n -Propylamine, isopropylamine, n-butylamine, isobutylamine, s-butylamine, t-butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetra Decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, icosylamine, eicosylamine, heicosylamine, heneicosylamine, docosylamine, tricosylamine, tetracosyl Amine, 1-methylbutylamine, 2-methylbutylamine, cyclopropylmethylamine, cyclohexylmethylamine, benzylamine, 2-methylbenzylamine, 4-methylbenzylamine, 1-phenylethylamine, 2-phenylethylamine, 3-aminomethyl Pyridine, 1- (4-chlorophenyl) ethylamine, 2- (2-chlorophenyl) ethylamine, 1- (3-methoxyphenyl) ethylamine, 1- (4-methoxyphenyl) ethylamine, 2- (2-methoxyphenyl) ethylamine, 2- (3-methoxyphenyl) ethylamine, 2- (4-methoxyphenyl) ethylamine, 1- [3- (trifluoromethyl) phenyl] ethylamine, 1- (1-naphthyl) ethylamine, 1- (2-naphthyl) Ethyla Min, 1-phenylpropylamine, 3-phenylpropylamine and the like.

In the above formulas (I) and (II), R ¹ and R ² are bonded at their ends, and the C 3-12 fat which may have substitution with the carbon atom to which R ¹ and R ² are bonded. A cyclic hydrocarbon group may be formed, and in that case, the number of carbon atoms is preferably 6 to 12. Here, a C3-C12 alicyclic hydrocarbon group means a 3-12 membered alicyclic hydrocarbon group, and "having a substituent" means in this alicyclic hydrocarbon group This means an alicyclic hydrocarbon group in which part or all of the hydrogen atoms in the methylene group may be substituted with other substituents. When it is substituted with another substituent, the carbon number of the substituent is not included in the above carbon number. When R ¹ and R ² together form an alicyclic hydrocarbon group having 3 to 12 carbon atoms which may be substituted with the carbon atom to which R ¹ and R ² are bonded, the amine compound (I) Examples thereof include cyclohexylamine, cyclooctylamine, cyclopentylamine, cycloheptylamine, cyclododecylamine, 2-methylcyclohexylamine, 4-methylcyclohexylamine and the like.

  Among the amine compounds (I), when cyclohexylamine is used as a raw material, the method of the present invention is advantageously employed in that cyclohexanone oxime can be obtained with high selectivity. The cyclohexylamine may be obtained, for example, by hydrogenating aniline, nitrobenzene, nitrocyclohexane, or the like, or obtained by amination reaction of cyclohexene or cyclohexanol with ammonia. May be.

  An oxygen-containing gas is preferably used as an oxygen source for oxygen used for oxidation. The oxygen-containing gas may be, for example, air, pure oxygen, or air or pure oxygen diluted with an inert gas such as nitrogen, argon, or helium. Good. Further, oxygen-enriched air obtained by adding pure oxygen to air can also be used. When an oxygen-containing gas is used, the oxygen concentration is preferably 1 to 30% by volume.

  In the oxidation, it is preferable to use a solvent. Examples of the solvent include an organic solvent, water, and a mixed solvent of an organic solvent and water. Among them, an organic solvent or a mixed solvent of an organic solvent and water is preferable, and an organic solvent is more preferable. Examples of organic solvents include methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol, n-hexanol, 2-ethylhexanol, n-dodecanol and other alcohols; pentane, hexane, heptane, octane, petroleum ether, Aliphatic hydrocarbons such as ligroin; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, o-xylene, m-xylene, and p-xylene; dichloromethane, chloroform, 1 Halogenated hydrocarbons such as 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethylene, 1,1,2,2-tetrachloroethylene, chlorobenzene, o-dichlorobenzene; acetonitrile, benzonitrile, etc. Nitrile; nitro compounds such as nitrobenzene; ethyl acetate, isopropyl acetate, butyl acetate, ester compounds such as ethyl benzoate and the like, can also be used two or more of them as required. Of these, alcohol, aromatic hydrocarbon, and nitrile are preferable. Among alcohols, methanol, ethanol, and t-butanol are preferable. Among aromatic hydrocarbons, toluene, o-xylene, m-xylene, and p-xylene are preferable. Among nitrites, acetonitrile is preferable.

  When using a solvent, the quantity is 0.1-300 weight part normally with respect to 1 weight part of amine compound (I), Preferably it is 0.5-100 weight part.

  The oxidation may be performed in a batch system, a semi-batch system, a continuous system, or a combination of a batch system, a semi-batch system, and a continuous system. For continuous operation, fixed bed method, fluidized bed method, moving bed method, suspension bed method, and the method of extracting the liquid phase of the reaction mixture while supplying the reaction raw material into the stirring / mixing type or loop type reactor. It can implement by various methods, such as.

  The reaction temperature in the oxidation is preferably 50 to 200 ° C, more preferably 70 to 150 ° C. The reaction pressure is usually 0.1 to 10 MPa, preferably 0.2 to 7.0 MPa in absolute pressure. The oxidation is preferably performed under pressure. In this case, the pressure may be adjusted using an inert gas such as nitrogen or helium. When the oxidation is carried out batchwise or continuously using an oxygen-containing gas under a liquid phase condition in a stirring and mixing reactor, an oxygen-containing gas is supplied to the gas phase part of the reactor. Alternatively, the oxygen-containing gas may be supplied into the liquid phase, or the oxygen-containing gas may be supplied into the gas phase portion and the liquid phase of the reactor.

  In the oxidation, a radical initiator, a phenol chain transfer agent or the like may coexist. From the viewpoint of improving the selectivity of the oxime compound (II), it is preferable to coexist a radical initiator. Examples of the radical initiator include hydrazyl radicals and hydrazine compounds disclosed in International Publication No. 2005/009613, azo compounds and peroxides disclosed in JP-A No. 2005-15381. If necessary, two or more kinds of radical initiators may be used. As the hydrazyl radical, 2,2-diphenyl-1-picrylhydrazyl and 2,2-di (4-tert-octylphenyl) -1-picrylhydrazyl are preferable. As the hydrazine compound, 1,1-diphenyl-2-picrylhydrazine is preferable. In the present invention, at least one selected from the group consisting of 2,2-diphenyl-1-picrylhydrazyl and 1,1-diphenyl-2-picrylhydrazine is preferably used as the radical initiator. As said phenol type chain transfer agent, the compound etc. which are disclosed by Unexamined-Japanese-Patent No. 2005-15382 are mentioned, for example.

  The post-treatment operation of the reaction mixture containing the oxime compound (II) obtained by oxidation can be selected as appropriate, and may be combined with treatments such as filtration, washing, distillation, crystallization, extraction, recrystallization, and chromatography as necessary. The oxime compound (II) can be purified and used for various purposes. The catalyst recovered after the oxidation can be reused after being subjected to treatments such as washing, calcination and ion exchange treatment as necessary. Moreover, when a solvent and an unreacted raw material are contained in the reaction mixture, the recovered solvent and unreacted raw material can be reused.

（式中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、置換基を有していてもよい炭化水素基又は置換基を有していてもよい複素環基を表す（但し、Ｒ^１及びＲ^２が共に水素原子であることはない。）か、あるいは
Ｒ^１及びＲ^２は一緒になって、Ｒ^１が結合する窒素原子と、Ｒ^２が結合する炭素原子と共に置換基を有していてもよい複素環を形成する。）
で表されるアミド化合物を製造するための原料として好適に使用される。 The obtained oxime compound (II) is subjected to, for example, a Beckmann rearrangement reaction to obtain a compound represented by the formula (III):

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent (provided that R ¹ and R ² are not both hydrogen atoms), or R ¹ and R ² together have a nitrogen atom to which R ¹ is bonded and a carbon atom to which R ² is bonded. A heterocyclic ring which may be
It is used suitably as a raw material for manufacturing the amide compound represented by these.

In formula (III), R ¹ and R ² together represent a nitrogen atom to which R ¹ is bonded and a C 3-12 fat optionally having substitution with the carbon atom to which R ² is bonded. amide compound to form the group heterocyclic ring, in the formula (II), R ¹ and R ² together, R ¹ and R ² is which may be the number 3 to 12 carbon substituted together with the carbon atom bonded It is obtained by subjecting an oxime compound forming an alicyclic hydrocarbon group to a Beckmann rearrangement reaction.

  Examples of such Beckmann rearrangement include a method performed under liquid phase conditions and a method performed under gas phase conditions. The Beckmann rearrangement reaction under liquid phase conditions includes, for example, a method performed in the presence of a strong acid such as fuming sulfuric acid, and can be performed according to the method described in Japanese Patent Publication No. 48-4791. The Beckmann rearrangement reaction under gas phase conditions includes, for example, a method performed in the presence of a solid catalyst such as zeolite, and can be performed according to the method described in JP-A-5-170732. For example, when cyclohexylamine is used as the amine compound (I), ε-caprolactam can be produced by subjecting cyclohexanone oxime obtained by the oxidation to Beckmann rearrangement reaction.

  Examples of the present invention and comparative examples are shown below, but the present invention is not limited thereby.

Example 1
In a 2 L flask, 444 g of 1N nitric acid (manufactured by Wako Pure Chemical Industries, Ltd.) and montmorillonite (Kunipia F, manufactured by Kunimine Kogyo Co., Ltd., montmorillonite containing sodium ion, potassium ion and calcium ion as cations between layers) 25 g was added and stirred. Next, using a water bath, the temperature was raised to 90 ° C. with stirring, and 31 g of a 35 wt% titanium sulfate solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour. Heat treatment was performed while stirring the mixed solution at 6 ° C. for 6 hours. After the elapse of 6 hours, the heat treatment was completed, the mixture was cooled to room temperature, and stirring was stopped. When the solid was separated by pressure filtration of the obtained mixture, the filtration time was within 10 minutes. Moreover, when this solid was washed with 1 L of water and the solid was separated again by pressure filtration, the pH of the filtrate was 1 or less and the filtration time was within 15 minutes. After washing, the obtained solid was dried at 110 ° C. overnight to obtain catalyst A (montmorillonite containing titanium ions between layers).

Comparative Example 1
In Example 1, a mixture of 1N nitric acid and montmorillonite was heated to 50 ° C. while stirring, and after the completion of dropwise addition of 35% titanium sulfate, the same operation as in Example 1 was performed except that the heat treatment was performed at 50 ° C. for 6 hours. The filtration time when pressure-filtering the mixture was within 15 minutes, and the pH of the filtrate after washing with 1 L of water was 1 or less, and the filtration time was 1 hour or more.

Example 2
In a 1 L poly beaker, 266 g of 1N nitric acid (manufactured by Wako Pure Chemical Industries, Ltd.), montmorillonite (Kunipia F, manufactured by Kunimine Kogyo Co., Ltd.), montmorillonite containing sodium ion, potassium ion and calcium ion as cations between layers ) 15 g was added and stirred. Next, using a water bath, the temperature was raised to 50 ° C. while stirring, and 19 g of 35 wt% titanium sulfate solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour. The liquid was transferred to a SUS autoclave and heated to 110 ° C. Thereafter, heat treatment was performed while stirring the mixed solution at 110 ° C. for 4 hours. After the elapse of 4 hours, the heat treatment was completed, the mixture was cooled to room temperature, and stirring was stopped. The obtained mixture was filtered under pressure to separate the solid, and the filtration time was within 5 minutes. Moreover, when this solid was washed with 500 mL of water and the solid was separated again by pressure filtration, the pH of the filtrate was 1 or less and the filtration time was within 10 minutes. After washing, the obtained solid was dried at 110 ° C. overnight to obtain catalyst B (montmorillonite containing titanium ions between layers).

Example 3
In a reactor made of SUS316 (capacity: 200 mL) equipped with a thermocouple, a magnetic stirrer, a gas supply line, and a gas discharge line, 0.30 g of the catalyst A obtained in Example 1 and cyclohexylamine (Wako Pure Chemical Industries, Ltd. ( Co., Ltd.) and 1.99 g of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) were added, and the gas phase in the reactor was replaced with nitrogen gas, then sealed, and the gas in the reactor was sealed. A gas mixture of oxygen and nitrogen (oxygen concentration: 7% by volume) was introduced into the phase part to adjust the pressure in the reactor to 0.95 MPa (gauge pressure). Next, the temperature in the reactor was raised to 86 ° C. while stirring. The pressure in the reactor at this time was 1.15 MPa (gauge pressure). Next, the mixture was kept at 86 ° C. for 4 hours while continuing stirring, and then cooled. The obtained reaction mixture was diluted with methanol and then filtered, and the obtained filtrate was analyzed. The conversion of cyclohexylamine was 1.3% and the selectivity of cyclohexanone oxime was 75.1%. there were.

Claims (9)

The following steps (1) to (5),
(1): a step of mixing a layered silicate, an acid, and a metal element compound,
(2): a step of heat-treating the mixture obtained in step (1) at 70 ° C. to 170 ° C.,
(3): a step of separating the solid from the heat-treated mixture obtained in step (2),
(4): a step of washing the solid separated in step (3) while keeping the pH of the washing liquid at 4 or less,
(5): a step of drying the solid obtained in step (4),
A process for producing a layered silicate catalyst comprising: The production method according to claim 1, wherein the layered silicate used in the step (1) is smectite. The production method according to claim 1 or 2, wherein the acid used in step (1) is an inorganic acid. The metal element compound used in step (1) is at least one compound selected from the group consisting of compounds of Group 4 metal elements, compounds of Group 5 metal elements, compounds of Group 6 metal elements, and germanium compounds. The manufacturing method of claim | item 1-3. The method according to any one of claims 1 to 4, wherein the heat treatment in the step (2) is performed for 1 to 20 hours. The method according to any one of claims 1 to 5, wherein in step (3), the solid obtained in step (2) is separated by filtration. The method according to claim 1, wherein in step (4), the cleaning liquid is separated by filtration. The method according to any one of claims 1 to 7, wherein the drying temperature in step (5) is from 0C to 600C.
A layered silicate catalyst is produced by the method according to any one of claims 1 to 8, and in the presence of this layered silicate catalyst, the compound of formula (I)

(Wherein R ¹ and R ² each independently represents a hydrogen atom, a hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent, or R 1 ¹ and R ² are bonded to each other at their ends to form a ring together with the carbon atom to which R ¹ and R ² are bonded, provided that R ¹ and R ² do not represent a hydrogen atom at the same time. )
A primary amine represented by the formula (II) is oxidized with molecular oxygen

(Wherein R ¹ and R ² represent the same meaning as described above.)
The manufacturing method of the oxime compound shown by these.