JP2013189414A - Method for producing oxime - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an oxime in high yield by ammoximation reaction of a ketone with an organic peroxide and ammonia.SOLUTION: There is provided a method for producing an oxime characterized by ammoximation reaction of a ketone with an organic peroxide and ammonia in the presence of a catalyst produced by contacting, with a titanium compound, a smectite having at least one kind selected from hydrogen ion, ammonium ion and quaternary ammonium ion as an interlayer cation.

Description

  The present invention relates to a method for producing an oxime by ammoximation reaction of a ketone. Oxime is useful as a raw material for amides and lactams.

  As a method for producing an oxime by ammoximation reaction of a ketone, for example, Patent Documents 1 to 3 disclose that a ketone is contained in the presence of MFI type (including TS-1) or MWW type microporous titanosilicate. A method for ammoximation reaction with hydrogen oxide and ammonia is described. However, since hydrogen peroxide is a relatively expensive raw material, and becomes water after the reaction and is difficult to reuse as hydrogen peroxide, the method using hydrogen peroxide is not always sufficient from the cost aspect, A method using an organic peroxide as a recyclable peroxide has been desired. As such a method, for example, Patent Document 4 describes a method of ammoximation reaction of a ketone with an organic peroxide and ammonia in the presence of MWW type microporous titanosilicate. A method for ammoximation reaction of a ketone with an organic peroxide and ammonia in the presence of MCM-41 type or HMS type mesoporous titanosilicate is described.

JP 2006-169168 A JP 2007-1952 A JP 2007-238541 A JP 2010-24144 A JP 2011-21006 A

  However, the above method may not always be sufficient in terms of oxime yield. Accordingly, an object of the present invention is to provide a method for producing an oxime with a good yield by an ammoximation reaction of a ketone with an organic peroxide and ammonia.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.

That is, this invention consists of the following structures.
(1) In the presence of a catalyst obtained by contact-treating smectite having at least one selected from the group consisting of hydrogen ions, ammonium ions and quaternary ammonium ions as an interlayer cation with a titanium compound, a ketone is organically treated. A method for producing an oxime, characterized by causing an ammoximation reaction with an oxide and ammonia.
(2) The production method according to (1), wherein the smectite has hydrogen ions as cations between layers.
(3) The production method according to (2) above, wherein the smectite having hydrogen ions as a cation between layers is obtained by acid treatment of smectite.
(4) The manufacturing method in any one of said (1)-(3) whose smectite is a montmorillonite.
(5) The manufacturing method in any one of said (1)-(4) whose organic peroxide is a hydroperoxide.
(6) The production method according to (5), wherein the hydroperoxide is t-butyl hydroperoxide, cumene hydroperoxide, or 1,1-dimethylpropyl hydroperoxide.
(7) The production method according to any one of (1) to (6), wherein the ketone is a cycloalkanone.

  According to the present invention, an oxime can be produced in good yield by an ammoximation reaction of a ketone with an organic peroxide and ammonia.

  Hereinafter, the present invention will be described in detail. In the present invention, a catalyst obtained by using a ketone as a raw material and contact-treating smectite having at least one selected from the group consisting of hydrogen ion, ammonium ion and quaternary ammonium ion as a cation between layers with a titanium compound. In the presence of oxime, an oxime is produced by an ammoximation reaction with an organic peroxide and ammonia.

  The raw material ketone may be an aliphatic ketone, an alicyclic ketone, an aromatic ketone, or two or more of them as necessary. Specific examples of ketones include dialkyl ketones such as acetone, ethyl methyl ketone, and isobutyl methyl ketone; alkyl alkenyl ketones such as mesityl oxide; alkyl aryl ketones such as acetophenone; diaryl ketones such as benzophenone; cyclopentanone And cycloalkanones such as cyclohexanone, cyclooctanone and cyclododecanone; cycloalkenones such as cyclopentenone and cyclohexenone. Among them, cycloalkanone is a suitable subject of the present invention.

  The raw material ketone may be, for example, one obtained by oxidation of alkane, one obtained by oxidation (dehydrogenation) of secondary alcohol, or hydration and oxidation of alkene ( It may be obtained by dehydrogenation.

  Ammonia may be used in a gaseous form, in a liquid form, or as a solution in an organic solvent. When gaseous ammonia is used, it is diluted with an inert gas as necessary. Examples of the inert gas include nitrogen, carbon dioxide, helium, and argon. The amount of ammonia used is usually 1 mol or more, preferably 1.5 mol or more, per 1 mol of ketone.

  In the present invention, an organic peroxide is used for the ammoximation reaction. When an organic peroxide is used, the organic peroxide is converted into an alcohol or carboxylic acid, but these can be recovered by distillation, extraction, etc., which is advantageous in terms of cost. For example, when cumene hydroperoxide is used as the organic peroxide, 2-phenyl-2-propanol obtained after the ammoximation reaction can be recovered and reused as cumene hydroperoxide by hydrogenation and oxidation. . For example, when t-butyl hydroperoxide is used as the organic peroxide, 2-methyl-2-propanol obtained after the ammoximation reaction is recovered and reused as a t-butyl hydroperoxide by hydrogenation and oxidation. can do. For example, when 1,1-dimethylpropyl hydroperoxide is used as the organic peroxide, 2-methyl-2-butanol obtained after the ammoximation reaction is hydrogenated and oxidized to produce 1,1-dimethylpropyl hydroperoxide. It can be recovered as a peroxide and reused.

  Organic peroxides include t-butyl hydroperoxide, cumene hydroperoxide, 1,1-dimethylpropyl hydroperoxide, cyclohexyl hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetra Hydroperoxides such as methylbutyl hydroperoxide; t-butylcumyl peroxide, di-t-butyl peroxide, di-t-hexyl peroxide, dicumyl peroxide, α, α′-di (t-butylperoxy) diisopropylbenzene, Dialkyl peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3; cumylperoxyneodeca Noe 1,1,3,3-tetramethylbutylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxyneoheptanoate, t-hexyl Peroxypivalate, t-butylperoxypivalate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexano Ate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxy-3,5,5-trimethylhexanoate, t -Hexylperoxyisopropyl monocarbonate, t-butylperoxy-2- Peroxyesters such as tilhexyl monocarbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, t-hexylperoxybenzoate, t-butylperoxybenzoate; diisobutyryl peroxide; Diacyl peroxides such as di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, disuccinic acid peroxide, dibenzoyl peroxide, di (4-methylbenzoyl) peroxide; diisopropyl peroxydicarbonate, di-n- Propyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-sec-butyl Peroxydicarbonate, such as peroxydicarbonates and the like. Of these, hydroperoxide is preferable. Among the hydroperoxides, t-butyl hydroperoxide, cumene hydroperoxide, and 1,1-dimethylpropyl hydroperoxide are preferable.

  The amount of the organic peroxide to be used is preferably 0.5 to 3.0 mol, more preferably 0.7 to 2.0 mol, per 1 mol of ketone.

  In the ammoximation reaction of the present invention, a solvent is usually used. Examples of solvents include hydrocarbons such as butane, pentane, hexane, cyclohexane, benzene, cumene, toluene, xylene, acetonitrile, propionitrile, butyronitrile, isobutyronitrile, trimethylacetonitrile, valeronitrile, Nitriles such as isovaleronitrile and benzonitrile, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 2-methyl-1-propanol, 1-pentanol, 2-pentanol, 2-methyl-2-butanol, 3-methyl-1-butanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-2-butanol, neopentyl alcohol 1-hexanol 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 2-methyl-2-pentanol, 3-methyl-2- Pentanol, 4-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol, 2,2-dimethyl-1-butanol, 2,3-dimethyl-1-butanol, 3,3-dimethyl-1-butanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, Alcohols such as 1-octanol, 2-octanol, isooctyl alcohol, 2-ethylhexanol, and ethylene glycol monomethyl alcohol Le, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, and ethers such as ethylene glycol diethyl ether, water and the like, optionally may be used two or more thereof. Among these, alcohol, ether, a mixed solvent of alcohol and water, a mixed solvent of ether and water, or a mixed solvent of alcohol, ether and water are preferable.

  When a solvent is used, the amount is usually 2 to 300 parts by weight, preferably 3 to 100 parts by weight with respect to 1 part by weight of the ketone.

  Smectite is a tetrahedral sheet composed of a cation and oxygen, and an octahedral sheet composed of a cation and oxygen or hydroxide to form a negatively charged unit layer. Is a layered compound in which a cation is present, and generally has the following formula (I)

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

[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 ^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⁺ , Fe ³⁺ , Mn ³⁺ and Cr ³⁺ , and Z is selected from the group consisting of Si and Al It represents at least one (except when Z is only Al), and n ≧ 0. ]
It is a layered compound shown by these. 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.

  Examples of the smectite include montmorillonite, saponite, beidellite, nontronite, hectorite, soconite, and stevensite, and two or more of them can be used as necessary. Among these, montmorillonite and saponite are preferable, and montmorillonite is more preferable. The smectite to be used may be a natural product, an artificially synthesized product, 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.

  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 compound in which a layer is negatively charged and an exchangeable cation is present between the layers, and is generally represented by the following formula (II)

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

[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. ]
It is a layered compound shown by these. X represents a cation between layers.

  Since the cations X between layers can be exchanged with other cations, the cations X between layers can be exchanged with other cations by subjecting smectite to ion exchange treatment.

  In the present invention, as a smectite having at least one selected from the group consisting of hydrogen ion, ammonium ion and quaternary ammonium ion as a cation between layers used for the preparation of the catalyst, for example, by subjecting smectite to ion exchange treatment What is obtained can be suitably used. As the smectite to be subjected to the ion exchange treatment, those having at least one selected from the group consisting of sodium ion, potassium ion and calcium ion as the cation between layers are preferably used. The respective contents of sodium ion, potassium ion and calcium ion in smectite can be determined by, for example, inductively coupled plasma (ICP) emission analysis. Among smectites having at least one selected from the group consisting of hydrogen ions, ammonium ions and quaternary ammonium ions as interlayer cations, it is preferable to use smectites having hydrogen ions as interlayer cations.

  Examples of the method for preparing smectite having hydrogen ions as interlayer cations include (A) a method of acid-treating smectite, and (B) a method of baking smectite having ammonium ions as cations between layers. Of these, the method (A) is preferred. Examples of the acid used for the acid treatment include inorganic acids such as hydrogen chloride, nitric acid, phosphoric acid, sulfuric acid, and nitrous acid, and organic acids such as acetic acid and trifluoromethanesulfonic acid. Among these, inorganic acids are preferable and inorganic acids are preferred. Of the acids, hydrogen chloride, nitric acid, and phosphoric acid are preferred. The acid treatment is preferably performed by bringing smectite into contact with a solution containing an acid. By the acid treatment, interlayer cations X are ion-exchanged, and smectite having hydrogen ions as interlayer cations can be prepared.

  A smectite having an ammonium ion as a cation between layers can be prepared, for example, by subjecting smectite to an ion exchange treatment with at least one selected from the group consisting of ammonia and an ammonium salt. Examples of the ammonium salt include ammonium chloride, ammonium nitrate, ammonium phosphate, ammonium sulfate, and ammonium acetate, and two or more of them can be used as necessary. The ion exchange treatment is preferably performed by bringing smectite into contact with a solution containing at least one selected from the group consisting of ammonia and ammonium salts. By the ion exchange treatment, cations X between layers are ion-exchanged, and smectites having ammonium ions as cations between layers can be prepared.

  A smectite having a quaternary ammonium ion as a cation between layers can be prepared, for example, by subjecting smectite to an ion exchange treatment with a quaternary ammonium compound. Examples of the quaternary ammonium compound include tetramethylammonium, tetraethylammonium, n-propyltrimethylammonium, tetra-n-propylammonium, tetra-n-butylammonium, triethylmethylammonium, tri-n-propylmethylammonium, Examples include hydroxides and halides of various quaternary ammoniums such as tri-n-butylmethylammonium, benzyltrimethylammonium, and dibenzyldimethylammonium, and two or more of them can be used as necessary. . The ion exchange treatment is preferably performed by bringing smectite into contact with a solution containing a quaternary ammonium compound. By the ion exchange treatment, the cation X between layers is ion-exchanged, and a smectite having a quaternary ammonium ion as a cation between layers can be prepared.

  In the preparation of a solution containing the above acid, a solution containing at least one selected from the group consisting of ammonia and an ammonium salt, or a solution containing a quaternary ammonium compound, solvents used include water, methanol, ethanol, and acetone. Polar solvents such as the above, and two or more of them can be used as necessary. Of these, water is preferred. The usage-amount of a solvent is set suitably. When the acid treatment is performed, the pH of the solution containing the acid is preferably 3 or less.

  The acid treatment, the ion exchange treatment with at least one selected from the group consisting of ammonia and ammonium salts, or the ion exchange treatment with a quaternary ammonium compound may be carried out batchwise or continuously. Also good. As a batch method, for example, in a stirred tank, smectite is converted into a solution containing the above acid, a solution containing at least one selected from the group consisting of ammonia and an ammonium salt, or a solution containing a quaternary ammonium compound. Examples of the method include soaking and stirring and mixing. Examples of the continuous method include a solution containing at least one selected from the group consisting of the above-mentioned acid, ammonia and an ammonium salt in a tubular container filled with smectite, or a solution containing a quaternary ammonium compound. While supplying a solution containing at least one selected from the group consisting of the above acid, ammonia and an ammonium salt, or a solution containing a quaternary ammonium compound to a stirring tank containing smectite. And a method of extracting the liquid phase of the mixture.

  The temperature in the acid treatment, at least one ion exchange treatment selected from the group consisting of ammonia and ammonium salts, or the ion exchange treatment with a quaternary ammonium compound is usually 0 to 150 ° C., preferably 20 to 100 ° C. The time in these treatments is usually 0.1 to 240 hours, preferably 0.5 to 120 hours. The pressure in these treatments is usually 0.1 to 1 MPa in absolute pressure, preferably atmospheric pressure. Moreover, the usage-amount with respect to the smectite of the solution containing at least 1 type chosen from the solution containing said acid, the group which consists of ammonia and ammonium salt, or the solution containing a quaternary ammonium compound is set suitably. The acid treatment, the ion exchange treatment with at least one selected from the group consisting of ammonia and an ammonium salt, or the ion exchange treatment with a quaternary ammonium compound may be performed a plurality of times as necessary.

  In the catalyst, the contact treatment between smectite and titanium compound having at least one selected from the group consisting of hydrogen ion, ammonium ion and quaternary ammonium ion as a cation between layers is performed by contacting the smectite with a solution containing a titanium compound. It may be an ion exchange treatment by allowing the smectite to be impregnated with a solution containing a titanium compound and then dried, but in terms of the catalytic activity of the resulting catalyst, Ion exchange treatment is preferred. By this contact treatment, smectite containing titanium is obtained as a catalyst. Further, when the contact treatment is performed by ion exchange treatment, at least one selected from the group consisting of hydrogen ions, ammonium ions and quaternary ammonium ions present as interlayer cations is ion-exchanged, and interlayer cations are used. A smectite having a titanium cation can be prepared. In the catalyst, the content of titanium contained in the catalyst is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight.

  The ion exchange treatment by contacting with the solution containing the above-described titanium compound may be carried out batchwise or continuously. As a batch method, for example, a smectite having at least one selected from the group consisting of hydrogen ions, ammonium ions, and quaternary ammonium ions as a cation between layers in a stirring tank is immersed in a solution containing a titanium compound. Examples thereof include a method of stirring and mixing. For example, the continuous method may include a solution containing a titanium compound in a tubular container filled with smectite having at least one selected from the group consisting of hydrogen ions, ammonium ions, and quaternary ammonium ions as cations between layers. While supplying a solution containing a titanium compound to a stirring tank containing smectite having at least one selected from the group consisting of hydrogen ions, ammonium ions and quaternary ammonium ions as a cation between layers, Examples include a method of extracting the liquid phase.

Examples of the titanium compound used for the ion exchange treatment include inorganic titanium compounds and organic titanium compounds. Examples of the inorganic titanium compound include titanium trichloride (TiCl ₃ ), titanium tetrachloride (TiCl ₄ ), titanium tetrabromide (TiBr ₄ ), titanium tetrafluoride (TiF ₄ ), and titanium tetraiodide (TiI ₄ ). Titanium tetranitrate (Ti (NO ₃ ) ₄ ); titanium disulfate (Ti (SO ₄ ) ₂ ); titanium phosphate (Ti ₃ (PO ₄ ) ₄ ); Examples of the organic titanium compound include titanium alkoxide compounds such as Ti (OR) ₄ (hereinafter, R represents an alkyl group having 1 to 4 carbon atoms); TiCl (OR) ₃ , TiCl ₂ (OR) ₂ , TiCl ₃ (OR) and other halogenated titanium alkoxide compounds; titanium tetraacetate (Ti (CH ₃ COO) ₄ ); Moreover, the hydrate may be used as needed and 2 or more types thereof may be used. In the present invention, among these, titanium halide, titanium disulfate, and titanium alkoxide compounds are preferable, and titanium halide is more preferable. The amount of the titanium compound used is preferably 0.01 to 100 parts by weight and more preferably 0.05 to 50 parts by weight with respect to 100 parts by weight of smectite in terms of titanium.

  In the preparation of the solution containing a titanium compound, examples of the solvent used include polar solvents such as water, methanol, ethanol, and acetone, and two or more of them can be used as necessary. As a solution containing a titanium compound, an acidic aqueous solution containing a titanium compound is preferably used. As the acidic aqueous solution, when the pH when the titanium compound is mixed with water to form an aqueous solution is acidic, it may be used as it is, or may be further mixed with an acid. If the pH when the titanium compound is mixed with water to form an aqueous solution is not acidic, an acidic aqueous solution obtained by mixing an acid may be used. Examples of the acid used as necessary for the preparation of the acidic aqueous solution include organic acids and inorganic acids. Among these, inorganic acids are preferable. Examples of the inorganic acid include hydrogen chloride, sulfuric acid, phosphoric acid, nitric acid, etc. Among them, hydrogen chloride is preferable. The pH of the acidic aqueous solution is preferably 4 or less, and a base may be added to adjust the pH. The acidic aqueous solution may contain a polar organic solvent such as methanol, ethanol, and acetone. In the preparation of the acidic aqueous solution, when a titanium compound that is hydrolyzed under acidic conditions such as titanium alkoxide compound or titanium tetrachloride is used, the titanium compound is hydrolyzed to titanium oxide, and hydrogen ions, ammonium ions, and quaternary ions between layers. A smectite in which at least one selected from the group consisting of ammonium ions is ion-exchanged with positively charged titanium oxide can be prepared.

  Moreover, the solution containing a titanium compound may contain a compound containing a metal element other than titanium. Examples of compounds containing metal elements other than titanium include silicon compounds, germanium compounds, zirconium compounds, tin compounds, hafnium compounds, aluminum compounds, scandium compounds, gallium compounds, vanadium compounds, niobium compounds, molybdenum compounds, tungsten compounds. Etc., and two or more of them can be used as necessary. When using an acidic aqueous solution containing a titanium compound hydrolyzed under acidic conditions such as a titanium alkoxide compound or titanium tetrachloride as a solution containing a titanium compound, other than titanium hydrolyzed under acidic conditions such as a silicon alkoxide compound When a compound containing a metal element is added, a titanium compound and a compound containing a metal element other than titanium are hydrolyzed to become oxides of metal elements other than titanium oxide and titanium, or other than titanium and titanium. It becomes a composite oxide having other metal elements as constituent elements, and at least one selected from the group consisting of hydrogen ions, ammonium ions and quaternary ammonium ions between layers is positively charged titanium oxide and positively charged titanium Oxides of other metal elements other than titanium, titanium and other metal elements other than titanium Charged composite oxide or ion-exchanged smectite mixtures thereof can be prepared. When two or more compounds containing metal elements other than titanium that are hydrolyzed under acidic conditions are used, positively charged complex oxidation using titanium and two or more metal elements other than titanium as constituent elements A smectite ion-exchanged with a product can be prepared. Examples of the silicon alkoxide compound include tetraalkyl orthosilicates such as tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, and tetrabutyl orthosilicate.

  As a smectite containing titanium by the above-described ion exchange treatment, ion exchange is performed with titanium, titanium oxide, a composite oxide containing titanium or one or more metal elements other than titanium as a constituent element, or a mixture thereof. Smectite prepared can be prepared. Among them, in terms of catalytic activity, it is possible to obtain smectite ion-exchanged with titanium, and smectite ion-exchanged with a composite oxide containing titanium and one or more metal elements other than titanium as constituent elements. Is preferred. Examples of the other metal elements include silicon, germanium, zirconium, tin, hafnium, aluminum, scandium, gallium, vanadium, niobium, molybdenum, tungsten, and the like.

  The temperature in the ion exchange treatment by contacting with the solution containing the above titanium compound is usually 0 to 150 ° C., and at least one selected from the group consisting of hydrogen ions, ammonium ions and quaternary ammonium ions between layers and titanium. It is preferably 10 to 100 ° C., more preferably 30 to 70 ° C. in that ion exchange with can be performed more efficiently. The ion exchange time is usually 0.1 to 240 hours, preferably 0.5 to 120 hours. The pressure during the ion exchange treatment is usually 0.1 to 1 MPa in absolute pressure, preferably atmospheric pressure. Moreover, the usage-amount with respect to the smectite of the solution containing a titanium compound is set suitably. In addition, you may perform the above-mentioned ion exchange process in multiple times as needed.

  The smectite containing titanium obtained after the ion exchange treatment by contacting with the solution containing the above-described titanium compound is subjected to treatment such as washing and drying as necessary. When the smectite containing titanium obtained after the ion exchange treatment is in a slurry state, the smectite containing titanium may be recovered by drying the slurry, or the obtained smectite containing titanium is filtered or decanted. After separating by, for example, the smectite containing titanium may be recovered by washing and drying as necessary. If the anion contained in the titanium compound used during the ion exchange treatment or the anion derived from the acid used as necessary remains in the smectite containing titanium, the catalytic activity of the resulting smectite containing titanium may be reduced. Therefore, it is preferable to wash the smectite containing titanium obtained after the ion exchange treatment. The drying can be performed under normal pressure or reduced pressure, the drying temperature is preferably 20 to 150 ° 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 the drying, it may be fired as necessary. The firing temperature is preferably 150 to 600 ° C., and the firing time is preferably 0.1 to 100 hours.

  The 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. Further, the calcination may be performed in multiple stages in an atmosphere of an oxygen-containing gas or an inert gas. The firing may be performed by a fluidized bed method or a fixed bed method.

  The catalyst may be used after being formed into a granular or pellet shape 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 the ion exchange treatment or after the ion exchange treatment.

  The ammoximation reaction 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. Among these, it is preferable to carry out continuously. In the case of continuous operation, the liquid phase of the reaction mixture is supplied while the reaction raw material is supplied into a fixed bed flow method in which a reaction raw material is passed through a fixed bed reactor filled with a catalyst, or in a stirring and mixing type reactor. It is desirable from the viewpoint of productivity and operability to carry out the above reaction in an extracting manner. From the viewpoint of preventing decomposition of the organic peroxide, the reactor is preferably glass-lined or stainless steel.

  The reaction in the fixed bed flow system is, for example, up-flowing or down-loading the reaction materials such as ketone, organic peroxide and ammonia together with a solvent to a fixed-bed reactor filled with smectite containing titanium. The reaction can be carried out by passing through a flow. When gaseous ammonia is used as ammonia, the gaseous ammonia is diluted with an inert gas as necessary, and the supply direction thereof is parallel or countercurrent to the supply direction of raw materials other than ammonia. Either of these may be used. The reaction is preferably carried out under pressurized conditions. The contact time between the catalyst and the reaction raw material can be adjusted by controlling the pressurizing condition.

  As the fixed bed reactor, various flow-type fixed bed reactors in which a raw material supply port and a reaction liquid outlet port are provided in the reactor can be used. The number of reaction tubes is not particularly limited, and either a single tube fixed bed reactor or a multi-tube fixed bed reactor can be used. Moreover, a fixed bed reactor of an adiabatic system or a heat exchange system can be used.

  The reaction temperature of the ammoximation reaction is usually 50 to 150 ° C, preferably 70 to 120 ° C. The reaction pressure is usually 0.1 to 1.5 MPa in absolute pressure, preferably 0.2 to 1.2 MPa. The ammoximation reaction is preferably performed under pressure in order to facilitate the dissolution of ammonia in the liquid phase of the reaction mixture. In this case, the pressure is adjusted using an inert gas such as nitrogen or helium. Also good.

  The post-treatment operation of the obtained reaction mixture is appropriately selected. For example, the oxime can be separated by subjecting the reaction mixture to distillation. When a catalyst is contained in the reaction mixture, the oxime can be separated by subjecting the liquid phase to distillation after separating the catalyst by filtration, decantation, or the like. The catalyst recovered after the reaction 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 solvent and the unreacted raw material recovered by distillation of the liquid phase can be reused. The obtained oxime is suitably used as a raw material for producing the corresponding amide compound by Beckmann rearrangement reaction.

  Hereinafter, although the Example and comparative example of this invention are shown, this invention is not limited by this. In the examples, the reaction mixture was analyzed by gas chromatography, and the conversion of cyclohexanone, the selectivity of cyclohexanone oxime and the yield were calculated.

Reference example 1
[Acid treatment of montmorillonite]
In a 1 L separable flask, 600 g of hydrochloric acid (concentration: 2 mol / L) was added, and montmorillonite (Kunipia F manufactured by Kunimine Kogyo Co., Ltd., montmorillonite having sodium ions, potassium ions and calcium ions as cations between layers) 60 g And stirred at room temperature for 5 minutes. Then, stirring the obtained mixture, it heated up at 90 degreeC using the oil bath, and stirring was continued at 90 degreeC for 12 hours. After 12 hours, the mixture was cooled to room temperature and stirring was stopped. The obtained mixture was subjected to pressure filtration to separate a solid, and this solid was washed and filtered with water by pressure filtration, and washed repeatedly until the pH of the washing filtrate became 5 or more. After washing, the resulting solid was dried at 110 ° C. overnight to obtain montmorillonite (A) having hydrogen ions as interlayer cations.

[Preparation of catalyst]
In a 2 L poly beaker, 700 g of ion-exchanged water and 17.9 g of a 20 wt% titanium trichloride solution (TiCl ₃ dilute hydrochloric acid solution, manufactured by Wako Pure Chemical Industries, Ltd.) were stirred for 5 minutes at room temperature. 15 g of the montmorillonite (A) obtained above was added to the obtained liquid mixture and stirred at room temperature for 5 minutes, and then the gas phase part in the poly beaker was replaced with nitrogen. Next, using a water bath, the mixture in the poly beaker was heated to 50 ° C. while stirring, and stirring was continued at 50 ° C. for 12 hours. After 12 hours, the mixture was cooled to room temperature and stirring was stopped. The obtained mixture was subjected to pressure filtration to separate a solid, and this solid was washed and filtered with water by pressure filtration, and washed repeatedly until the pH of the washing filtrate became 5 or more. After washing, the resulting solid was dried at 110 ° C. overnight to prepare Catalyst A.

Reference example 2
[Acid treatment of montmorillonite]
The same procedure as in Reference Example 1 [Acid treatment of montmorillonite] was carried out except that an aqueous nitric acid solution (concentration: 2 mol / L) was used instead of hydrochloric acid (concentration: 2 mol / L). As a result, montmorillonite (B) having hydrogen ions was obtained.

[Preparation of catalyst]
Catalyst B was prepared in the same manner as in Reference Example 1 [Preparation of catalyst] except that montmorillonite (B) was used instead of montmorillonite (A).

Reference example 3
[Acid treatment of montmorillonite]
Except for using a phosphoric acid aqueous solution (concentration: 2 mol / L) instead of hydrochloric acid (concentration: 2 mol / L), the same operation as in Reference Example 1 [Acid treatment of montmorillonite] was carried out, Montmorillonite (C) having hydrogen ions as ions was obtained.

[Preparation of catalyst]
Catalyst C was prepared in the same manner as in Reference Example 1 [Preparation of catalyst] except that montmorillonite (C) was used instead of montmorillonite (A).

Example 1
7.0 g of catalyst A is filled into a SUS reaction tube having an inner diameter of 1 cm to form a catalyst layer. Under a helium flow, the pressure in the reaction tube is maintained at 1.0 MPa (absolute pressure), and the temperature of the catalyst layer is increased. After the temperature was raised to 90 ° C., an ethylene glycol dimethyl ether solution of ammonia (ammonia content: 0.69 wt%) was added to an ethylene glycol dimethyl ether solution (cyclohexanone content: 2) containing 5.6 g / h, cyclohexanone, cumene hydroperoxide and water. 0.0% by weight, cumene hydroperoxide content: 4.7% by weight, water content: 1.5% by weight) is supplied to the reaction tube at a flow rate of 5.6 g / h, and is circulated in an up-flow. Started. The molar ratio of supplied ammonia / cumene hydroperoxide / water / cyclohexanone was 2.0 / 1.5 / 4.0 / 1.0 (molar ratio).

  When the reaction mixture derived from the reaction tube outlet was analyzed by gas chromatography after 9 hours had elapsed from the start of the reaction, the conversion of cyclohexanone was 79.3%, and the selectivity for cyclohexanone oxime was 99.4. %, And the yield of cyclohexanone oxime was 78.8%. The production rate of cyclohexanone imine (a compound in which cyclohexanone was iminized) and cyclohexanone supplied with impurities derived from the imine was 0.5%.

Example 2
The same operation as in Example 1 was performed except that catalyst B was used instead of catalyst A. When 9 hours passed from the start of the reaction, the reaction mixture derived from the outlet of the reaction tube was analyzed by gas chromatography. The conversion of cyclohexanone was 83.5% and the selectivity for cyclohexanone oxime was 80.2. %, And the yield of cyclohexanone oxime was 67.0%. The production rate of cyclohexanone imine (a compound in which cyclohexanone was iminized) and cyclohexanone supplied with impurities derived from the imine was 16.5%.

Example 3
The same operation as in Example 1 was performed except that the catalyst C was used instead of the catalyst A. When 9 hours passed from the start of the reaction, the reaction mixture derived from the outlet of the reaction tube was analyzed by gas chromatography. The conversion of cyclohexanone was 87.0% and the selectivity for cyclohexanone oxime was 82.0. %, And the yield of cyclohexanone oxime was 71.3%. The production rate of cyclohexanone imine (a compound obtained by iminating cyclohexanone) and cyclohexanone supplied with impurities derived from the imine was 15.7%.

Comparative Example 1
It replaced with the catalyst A and performed operation similar to Example 1 except having used montmorillonite (Kunimine F Co., Ltd. product Kunipia F). When the reaction mixture derived from the outlet of the reaction tube was analyzed by gas chromatography after 6 hours from the start of the reaction, the conversion of cyclohexanone was 13.2% and the selectivity of cyclohexanone oxime was 0%. Yes, the yield of cyclohexanone oxime was 0%. The production rate of cyclohexanone imine (a compound obtained by iminating cyclohexanone) and cyclohexanone supplied with impurities derived from the imine was 13.2%.

Comparative Example 2
The same operation as in Example 1 was performed except that Ti-MCM-41 was used in place of the catalyst A. When the reaction mixture derived from the reaction tube outlet was analyzed by gas chromatography when 12 hours had elapsed from the start of the reaction, the conversion of cyclohexanone was 7.7% and the selectivity for cyclohexanone oxime was 46.7. %, And the yield of cyclohexanone oxime was 3.6%. In addition, the yield of cyclohexanone imine (a compound in which cyclohexanone was iminized) and cyclohexanone supplied with impurities derived from the imine was 4.1%.

Comparative Example 3
The same operation as in Example 1 was performed except that Ti-HMS was used in place of the catalyst A. When 12 hours passed from the start of the reaction, the reaction mixture derived from the outlet of the reaction tube was analyzed by gas chromatography. The conversion of cyclohexanone was 22.5% and the selectivity for cyclohexanone oxime was 16.3. %, And the yield of cyclohexanone oxime was 3.7%. Moreover, the production rate with respect to cyclohexanone supplied with cyclohexanone imine (a compound obtained by iminating cyclohexanone) and impurities derived from the imine was 18.8%.

Comparative Example 4
It replaced with the catalyst A and performed operation similar to Example 1 except having used TS-1. When the reaction mixture derived from the reaction tube outlet was analyzed by gas chromatography when 12 hours had elapsed from the start of the reaction, the conversion of cyclohexanone was 11.0% and the selectivity for cyclohexanone oxime was 4.6. %, And the yield of cyclohexanone oxime was 0.5%. Moreover, the production rate with respect to cyclohexanone supplied with cyclohexanone imine (a compound in which cyclohexanone was iminized) and impurities derived from the imine was 10.5%.

Example 4
7.0 g of catalyst A is filled into a SUS reaction tube having an inner diameter of 1 cm to form a catalyst layer. Under a helium flow, the pressure in the reaction tube is maintained at 1.0 MPa (absolute pressure), and the temperature of the catalyst layer is increased. After raising the temperature to 90 ° C., 4-methyl-2-pentanol solution of ammonia (ammonia content: 2.1 wt%) was added to 5.3 g / h of 4-methyl-2 containing cyclohexanone, cumene hydroperoxide and water. -A pentanol solution (cyclohexanone content: 6.0 wt%, cumene hydroperoxide content: 14.0 wt%, water content: 4.4 wt%) is supplied to the reaction tube at a flow rate of 5.3 g / h. Then, the reaction was started by distributing it in an up flow. The molar ratio of supplied ammonia / cumene hydroperoxide / water / cyclohexanone was 2.0 / 1.5 / 4.0 / 1.0 (molar ratio).

  When the reaction mixture derived from the reaction tube outlet was analyzed by gas chromatography after 6 hours from the start of the reaction, the conversion of cyclohexanone was 46.4% and the selectivity of cyclohexanone oxime was 57.3. %, And the yield of cyclohexanone oxime was 26.6%. The production rate of cyclohexanone imine (a compound obtained by iminating cyclohexanone) and cyclohexanone supplied with impurities derived from the imine was 19.8%.

Example 5
The same operation as in Example 4 was performed except that catalyst B was used instead of catalyst A. When the reaction mixture derived from the reaction tube outlet was analyzed by gas chromatography at the time when 6 hours passed from the start of the reaction, the conversion of cyclohexanone was 38.5% and the selectivity of cyclohexanone oxime was 57.6. %, And the yield of cyclohexanone oxime was 22.2%. The production rate of cyclohexanone imine (a compound obtained by iminating cyclohexanone) and cyclohexanone supplied with impurities derived from the imine was 16.3%.

Example 6
The same operation as in Example 4 was performed except that the catalyst C was used instead of the catalyst A. When the reaction mixture derived from the reaction tube outlet was analyzed by gas chromatography at the time when 6 hours passed from the start of the reaction, the conversion of cyclohexanone was 50.6%, and the selectivity of cyclohexanone oxime was 58.0. %, And the yield of cyclohexanone oxime was 29.3%. Moreover, the production rate with respect to cyclohexanone supplied with cyclohexanone imine (a compound in which cyclohexanone was iminized) and impurities derived from the imine was 21.2%.

Example 7
7.0 g of catalyst A is filled into a SUS reaction tube having an inner diameter of 1 cm to form a catalyst layer. Under a helium flow, the pressure in the reaction tube is maintained at 1.0 MPa (absolute pressure), and the temperature of the catalyst layer is increased. After raising the temperature to 90 ° C., 5.1 g / h of a 2-methyl-2-propanol solution containing ammonia and water (ammonia content: 3.5 wt%, water content: 7.3 wt%), cyclohexanone, A flow rate of 5.1 g / h of a 2-methyl-2-propanol solution containing t-butyl hydroperoxide and water (cyclohexanone content: 10.0 wt%, t-butyl hydroperoxide content: 13.8 wt%) Was supplied to the reaction tube and circulated in an up flow to start the reaction. The molar ratio of supplied ammonia / t-butyl hydroperoxide / water / cyclohexanone was 2.0 / 1.5 / 4.0 / 1.0 (molar ratio).

  When the reaction mixture derived from the reaction tube outlet was analyzed by gas chromatography after 6 hours from the start of the reaction, the conversion of cyclohexanone was 48.2% and the selectivity for cyclohexanone oxime was 66.5. %, And the yield of cyclohexanone oxime was 32.1%. The production rate of cyclohexanone imine (a compound obtained by iminating cyclohexanone) and cyclohexanone supplied with impurities derived from the imine was 16.2%.

Claims (7)

  In the presence of a catalyst obtained by contact-treating smectite having at least one selected from the group consisting of hydrogen ion, ammonium ion and quaternary ammonium ion as a cation between layers with a titanium compound, a ketone is converted into an organic peroxide and A process for producing an oxime, which comprises ammoximation reaction with ammonia.   The manufacturing method according to claim 1, wherein the smectite has hydrogen ions as cations between layers.   The production method according to claim 2, wherein the smectite having hydrogen ions as cations between layers is obtained by acid treatment of smectite.   The method according to any one of claims 1 to 3, wherein the smectite is montmorillonite.   The method according to any one of claims 1 to 4, wherein the organic peroxide is a hydroperoxide.   The production method according to claim 5, wherein the hydroperoxide is t-butyl hydroperoxide, cumene hydroperoxide or 1,1-dimethylpropyl hydroperoxide.   The production method according to claim 1, wherein the ketone is a cycloalkanone.