JP2012201627A - Method for producing oxime - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an oxime from a ketone, an organic peroxide and ammonia in a good yield, while reducing the production of by-products obtained by the reaction of the ketone with ammonia.SOLUTION: The method for producing the oxime from the ketone, the organic peroxide and ammonia is characterized by placing the ammonia on one side of the diaphragm and reacting the ammonia penetrated the diaphragm, the organic peroxide and the ketone in the presence of a catalyst on the other side of the diaphragm. The catalyst is preferably supported on the surface of the diaphragm on the other side of the diaphragm.

Description

  The present invention relates to a process for producing oximes from ketones, organic peroxides and ammonia. Oxime is useful as a raw material for amides and lactams.

  As a method for producing an oxime from a ketone, an organic peroxide and ammonia, Patent Documents 1 and 2 describe that an oxime is produced by mixing a ketone, an organic peroxide and ammonia in the presence of a catalyst in a reactor. How to do is described.

JP 2010-24144 A JP 2011-21006 A

  However, in the above conventional method, in addition to the target oxime, the amount of by-products obtained by the reaction of ketone and ammonia may increase, which is in terms of oxime quality and yield. It was not always satisfactory. Accordingly, an object of the present invention is to provide a method for producing oximes from ketones, organic peroxides and ammonia in a good yield by reducing the production of by-products obtained by the reaction of ketones with ammonia. is there.

  As a result of intensive studies, the present inventors have completed the present invention that can achieve the above-mentioned object.

  That is, the present invention is characterized in that ammonia is present on one side of the diaphragm, and ammonia permeated through the diaphragm, organic peroxide, and ketone are reacted in the presence of a catalyst on the other side of the diaphragm. An oxime production method is provided.

  According to the present invention, it is possible to reduce the production of a by-product obtained by the reaction between a ketone and ammonia, and to produce an oxime from the ketone, the organic peroxide and ammonia with a good yield.

It is a schematic explanatory drawing which shows typically one Embodiment of the manufacturing method of the oxime which concerns on this invention.

  Hereinafter, the present invention will be described in detail. In the present invention, ammonia is present on one side of the diaphragm, and on the other side of the diaphragm, ammonia that has permeated through the diaphragm, an organic peroxide, and a ketone are reacted in the presence of a catalyst. 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 preferably adjusted so that the ammonia concentration in the liquid phase of the reaction mixture is 0.01% by weight or more after the reaction with the organic peroxide and the ketone. Thus, by setting the ammonia concentration in the liquid phase to a predetermined value or more, the conversion rate of the ketone and the selectivity of the target oxime can be increased, and as a result, the yield of the target oxime can be increased. Can do. This ammonia concentration is preferably 0.1% by weight or more, and is usually 10% by weight or less, preferably 5% by weight or less. In addition, the standard of the amount of ammonia used is usually 0.1 mol or more, further 0.5 mol or more with respect to 1 mol of the ketone, and usually 0.1 mol or more with respect to 1 mol of the organic peroxide. Furthermore, it is 0.5 mol or more.

  Organic peroxides include hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, cyclohexyl hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide. T-butyl cumyl peroxide, di-t-butyl peroxide, di-t-hexyl peroxide, dicumyl peroxide, α, α'-di (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5; Dialkyl peroxides such as di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3; cumylperoxyneodecanoate, 1,1,3 3-tetramethylbutyl per Oxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxyneoheptanoate, t-hexylperoxyvalate, t-butylperoxypivalate, 2,5- Dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t -Butylperoxy-2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxy-3,5,5-trimethylhexanoate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxy-2- Ethylhexyl monocarbonate, 2,5-dimethyl Peroxyesters such as -2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, t-hexylperoxybenzoate, t-butylperoxybenzoate; diisobutyryl peroxide, di (3,5,5-trimethylhexa Noyl) peroxides, dilauroyl peroxides, disuccinic acid peroxides, dibenzoyl peroxides, diacyl peroxides such as di (4-methylbenzoyl) peroxides; diisopropylperoxydicarbonates, di-n-propylperoxydicarbonates, bis (4-t Peroxydicarbonates such as -butylcyclohexyl) peroxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-sec-butylperoxydicarbonate Ruboneto, and the like. Of these, hydroperoxide is preferable.

  The usage-amount of an organic peroxide is 0.05-20 mol normally with respect to 1 mol of ketones, Preferably it is 0.1-15 mol.

  In the present invention, the organic peroxide is converted into alcohol or carboxylic acid after the reaction, but these can be recovered by distillation, extraction or the like, and thus are advantageous in terms of cost. For example, when cumene hydroperoxide is used as the organic peroxide, 2-phenyl-2-propanol obtained after the reaction can be recovered and reused as cumene hydroperoxide by hydrogenation and oxidation.

  As the catalyst in the present invention, a catalyst containing a transition metal and an oxide is preferable. Examples of the transition metal include titanium, zirconium, hafnium, and the like, and these may include one or more. Of these, titanium is preferable. Examples of the oxide include silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, and the like, and these may include one or more kinds, and when two or more kinds are included. These composite oxides may also be used. Of these, silicon oxide is preferable. As a catalyst containing a transition metal and an oxide, a catalyst containing titanium and a silicon oxide is preferable.

  Examples of the catalyst containing titanium and silicon oxide include silicate containing titanium, silica containing titanium, and the like.

  Examples of the silicate containing titanium include mesoporous silicate containing titanium, crystalline silicate containing titanium, and the like. Examples of the mesoporous silicate include MCM-41, MCM-48, HMS, SBA-15, FSM-16, MSU-H, MSU-F and the like. Examples of the crystalline silicate include silicalite-1 (MFI type), silicalite-2 (MEL type), ITQ-1 (MWW type), YNU-2 (MSE type), and the like. Among silicates containing titanium, mesoporous silicates containing titanium are preferable, MCM-41 containing titanium, and HMS containing titanium are more preferable (hereinafter referred to as MCM-41 containing titanium and HMS containing titanium). These may be referred to as Ti-MCM-41 and Ti-HMS, respectively). The mesoporous silicate means a mesoporous silicate having a pore diameter of about 2 to 50 nm. The presence or absence of a mesoporous structure can be confirmed by the presence or absence of a peak at 2θ = 0.2 to 4.0 ° in XRD (X-ray diffraction) measurement using copper Kα rays. Titanium in the silicate containing titanium may be incorporated into the silicate skeleton, may be incorporated into the pores, or may be supported on the surface of the silicate skeleton. In the silicate containing titanium, the mesoporous silicate containing titanium, the crystalline silicate containing titanium, the MCM-41 containing titanium, and the HMS containing titanium, each contains titanium in the silicate skeleton. Is preferred.

  Examples of the silica containing titanium include those in which titanium is supported on a silica carrier, titania-silica composite oxide, and the like.

  Examples of elements other than titanium, silicon, and oxygen that can be included in the catalyst containing titanium and silicon oxide include boron, aluminum, gallium, iron, and chromium. When the catalyst is a silicate containing titanium, elements other than titanium, silicon and oxygen may be incorporated into the silicate skeleton, may be incorporated into the pores, and may be incorporated into the surface of the silicate skeleton. It may be supported. When the catalyst is a silicate containing titanium in a silicate skeleton (titanosilicate), the silicate contains titanium, silicon and oxygen as elements constituting the skeleton, and substantially includes titanium, silicon and oxygen. The skeleton may be composed of only the skeleton, and the element forming the skeleton may further contain elements other than titanium, silicon, and oxygen, such as boron, aluminum, gallium, iron, and chromium. When the catalyst is titanium-containing silica, elements that can be contained in addition to titanium, silicon, and oxygen may be incorporated in the silica skeleton or may be supported on the silica surface.

  The titanium content in the catalyst containing titanium and silicon oxide is usually 0.0001 or more, preferably 0.005 or more, and usually 1.0 or more, expressed as an atomic ratio (Ti / Si) to silicon. Hereinafter, it is preferably 0.5 or less. When the catalyst containing titanium and silicon oxide contains an element other than titanium, silicon and oxygen, the content of the element is usually 1.0 or less, preferably 0.5 in terms of atomic ratio relative to silicon. It is as follows. Oxygen can be present corresponding to the content and oxidation number of each element other than oxygen. A typical composition of such a catalyst containing titanium and silicon oxide can be represented by the following formula with silicon as the reference (= 1).

SiO ₂ · xTiO ₂ · yM ⁿ O _{n / 2}

(In the formula, M represents at least one element other than silicon, titanium and oxygen, n is the oxidation number of the element, x is 0.0001 to 1.0, and y is 0 to 1.0. .)

  In the above formula, M is an element other than titanium, silicon, and oxygen, and examples thereof include boron, aluminum, gallium, iron, and chromium.

  The catalyst containing titanium and silicon oxide is prepared by a hydrothermal synthesis method, a sol-gel method, or the like. For example, in the case of mesoporous silicate containing titanium, after mixing a raw material titanium compound, a raw material silicon compound, and a structure directing agent (template) in an aqueous solvent in the presence of an acidic compound or a basic compound, a constant temperature and pressure are mixed. The titanium-containing silicate in which the structure-directing agent is incorporated is obtained by aging under the conditions or under the conditions of changing the temperature and / or pressure within the range of the temperature and pressure described later, and the structure-directing agent is obtained from the titanium-containing silicate. Is removed to prepare mesoporous silicate containing titanium. In the case of a titania-silica composite oxide, after mixing the raw material titanium compound and the raw material silicon compound in an aqueous solvent in the presence of an acidic compound or a basic compound, conditions of constant temperature and pressure, or the temperature and pressure described later Is prepared by aging under conditions that vary the temperature and / or pressure within the range of

  The structure of the mesoporous silicate containing titanium can be adjusted depending on the type and amount of the structure-directing agent used. For example, when preparing Ti-MCM-41, a structure such as cetyltrimethylammonium bromide is used. When a quaternary ammonium salt or the like is used and Ti-HMS is prepared, a primary amine such as n-dodecylamine is used. On the other hand, examples of the raw material titanium compound include tetraalkyl orthotitanates such as tetra-n-butyl orthotitanate, peroxytitanates such as tetra-n-butylammonium peroxytitanate, and titanium halides. Examples of the silicon compound include tetraalkyl orthosilicates such as tetraethyl orthosilicate, silica and the like. Examples of the acidic compound include inorganic acids such as hydrogen chloride and organic acids such as acetic acid. Examples of the basic compound include inorganic bases such as alkali hydroxide and ammonia and organic bases such as pyridine. Furthermore, examples of the aqueous solvent include water, a water-soluble organic solvent such as methanol, ethanol, propanol, and 2-propanol, or a mixed solvent of water and a water-soluble organic solvent.

  The temperature for aging during preparation of the mesoporous silicate or titania-silica composite oxide containing titanium is usually -20 to 200 ° C, preferably 20 to 170 ° C, and the pressure is usually 0.1 to absolute pressure. 1.0 MPa, preferably 0.1 to 0.8 MPa. The aging time is usually 0.5 to 170 hours, preferably 4 to 72 hours.

  When preparing a mesoporous silicate containing titanium, the above aging yields a titanium-containing silicate in which a structure-directing agent is incorporated, and then the structure-directing agent is removed from the titanium-containing silicate. Examples of such a removal method include a method of washing with an organic solvent such as methanol, acetone, and toluene, a method of washing with hydrochloric acid (aqueous hydrogen chloride solution), an aqueous solution of sulfuric acid, an aqueous nitric acid solution, a method of heat treatment at 200 to 800 ° C., and the like. It is done. Any one of the removal methods may be employed, or two or more may be employed in combination.

  Ti-MCM-41 can be prepared, for example, in accordance with the method described in Microporous and Mesoporous Materials, 2007, P312-321. Ti-HMS is, for example, Nature, 1994, can be prepared according to the method described in P321-323.

  The catalyst containing titanium and silicon oxide may be contact-treated with a silicon compound. Examples of such silicon compounds include organic silicon compounds and inorganic silicon compounds, and among them, organic silicon compounds are preferable. The organosilicon compound is preferably one that can react with a catalyst containing titanium and silicon oxide and bond to the surface thereof. Among them, an alkoxysilane compound, an organic disilazane compound, and a halogenated organosilane compound are preferred. More preferred are silane compounds and organic disilazane compounds. Each of the alkoxysilane compound, organic disilazane compound, and halogenated organic silane compound may be used alone or in combination of two or more. Examples of the alkoxysilane compound include tetraalkoxysilane, alkyltrialkoxysilane, dialkyldialkoxysilane, and trialkylalkoxysilane, among which trialkylalkoxysilane is preferable. Examples of the tetraalkoxysilane include tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetrabutyl orthosilicate, and the like. Examples of the alkyltrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, and the like. Examples of the dialkyl dialkoxysilane include dimethyldiethoxysilane, and examples of the trialkylalkoxysilane include trimethylethoxysilane and trimethylmethoxysilane. Examples of the organic disilazane compound include hexaalkyldisilazane such as hexamethyldisilazane and di-n-butyltetramethyldisilazane, divinyltetramethyldisilazane, diphenyltetramethyldisilazane, and tetraphenyldimethyldisilazane. Of these, hexaalkyldisilazane is preferable. Examples of the halogenated organic silane compound include chlorotrimethylsilane, dichlorodimethylsilane, trichloromethylsilane, chlorobromodimethylsilane, and iododimethylbutylsilane. It is preferable to use at least one selected from the group consisting of trialkylalkoxysilane and hexaalkyldisilazane as the organosilicon compound in that the hydroxyl group on the catalyst surface can be converted into a trialkylsilyl group.

  Examples of the inorganic silicon compound include silicic acid, silica gel, fumed silica, colloidal silica, and the like.

  Examples of the contact treatment method using a silicon compound include a method in which a catalyst containing titanium and silicon oxide is immersed in a liquid or slurry containing a silicon compound, or a gas containing a silicon compound is brought into contact with the catalyst containing titanium and the silicon oxide. Methods and the like. The contact treatment can be performed under an acidic condition, a basic condition or a neutral condition by appropriately adding an acid or a base, and the acidic, basic or neutral conditions are changed during the contact treatment. You may go while. The immersion is preferably performed while stirring. In the immersion, after the immersion, for example, by drying the mixture after immersion as it is, or after separating the obtained catalyst containing titanium and silicon oxide from the mixture after immersion by filtration, decantation, or the like. The catalyst containing titanium and silicon oxide obtained by contact treatment with a silicon compound is obtained by washing and drying as necessary. 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 usage-amount of a silicon compound is 1-10000 weight part normally with respect to 100 weight part of catalysts containing titanium and a silicon oxide, Preferably it is 5-2000 weight part, More preferably, it is 10-1500 weight part. In addition, as above-mentioned, when using 2 or more types together among an alkoxysilane compound, an organic disilazane compound, and a halogenated organosilane compound as a silicon compound, what is necessary is just to make it the total usage-amount become the said range. Further, as described above, when trialkylalkoxysilane and hexaalkyldisilazane are used as the silicon compound, the total amount used may be within the above range.

  The temperature of the contact treatment with the silicon compound is preferably 0 to 200 ° C., more preferably 30 to 100 ° C. when immersed in a liquid or slurry, and preferably 0 to 800 ° C., more preferably when contacting the gas. 100-500 ° C. The time for the contact treatment is preferably 0.5 to 50 hours, more preferably 1 to 20 hours when immersed in a liquid or slurry, and 0.5 to 100 hours, preferably 1 when contacting the gas. ~ 50 hours.

  In the preparation of the liquid or slurry containing the silicon compound, a solvent may be used in order to allow the silicon compound to exist stably. Alternatively, a liquid containing a silicon compound and a solvent may be vaporized and used as a gas containing a silicon compound. Examples of the solvent include water, methanol, ethanol, acetonitryl, toluene, xylene, cumene, tetrahydrofuran, carbon tetrachloride, N, N-dimethylacetamide and the like. Any one or two or more of the solvents may be employed.

  The treatment for bringing the gas containing the silicon compound into contact with the catalyst containing titanium and silicon oxide may be performed in the presence of an inert gas together with the gas containing the silicon compound. Examples of the inert gas include nitrogen, carbon dioxide, helium, and argon.

  The catalyst used in the production method of the present invention may be used after being formed into a granular shape or a pellet shape, if necessary, using a binder, or supported on a carrier different from the diaphragm. May be used by being supported on a diaphragm, or may be used as a diaphragm by forming itself, but is preferably supported by being supported on a diaphragm.

  Examples of the material of the diaphragm (excluding the diaphragm obtained by forming a catalyst) include, for example, porous bodies such as oxides and sintered metals. Among these, oxide porous bodies are preferable. Examples of the oxide include alumina, silica, zirconia, etc., and use a mixture of two or more of them, a composite oxide of two or more of them, ceramics mainly composed of oxide, glass, or the like. Of these, alumina is preferred.

  Examples of the shape of the diaphragm include a flat membrane shape, a tube shape, a monolith shape, and a honeycomb shape.

  In the case of using the catalyst supported on a diaphragm, the supporting method includes (A) a method in which a catalyst raw material is subjected to hydrothermal synthesis together with the diaphragm to form a catalyst layer on the diaphragm, and (B) the catalyst is applied to the diaphragm. A method of impregnating a solution or slurry containing, (C) a method of immersing a diaphragm in a solution or slurry containing a catalyst, (D) a method of dropping a solution or slurry containing a catalyst on the diaphragm while rotating the diaphragm, (E ) A method of removing a solvent from a solution or slurry containing a catalyst through a diaphragm and forming a catalyst layer on the diaphragm is preferable, and the method (E) is preferable. The amount of the catalyst supported on the diaphragm is appropriately set depending on the amount of the catalyst used relative to the raw material, etc., and is 0.1 to 10 parts by weight with respect to 100 parts by weight of the diaphragm.

  In the production method of the present invention, it is preferable to use a solvent. 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, alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, s-butyl alcohol, t-butyl alcohol, and t-amyl alcohol Is mentioned. Of these, hydrocarbons and nitriles are preferred. Moreover, those 2 or more types can also be used as needed.

  When a solvent is used, the amount is usually 1 to 500 parts by weight, preferably 2 to 300 parts by weight per 1 part by weight of the ketone, and usually 1 to 500 parts per 1 part by weight of the organic peroxide. Part by weight, preferably 2 to 300 parts by weight.

  Next, the reaction mode in the method for producing oxime according to the present invention will be described. In the present invention, first, reaction conditions such as temperature and pressure are appropriately adjusted on one side of the diaphragm, and ammonia is present (however, organic peroxide and ketone are present on one side of the diaphragm. Shall not be allowed). Ammonia permeates the diaphragm and moves to the other side of the diaphragm. Therefore, the ammonia that has moved is subjected to organic peroxidation by appropriately adjusting the reaction conditions such as temperature and pressure in the presence of a catalyst on the other side of the diaphragm. By reacting with a product and a ketone, an oxime reaction of the ketone occurs, and an oxime that is a target product is generated. The transferred ammonia may be reacted with an organic peroxide in the presence of a catalyst, and then the resulting reaction product containing hydroxylamine may be contacted with a ketone to perform an oximation reaction of the ketone. . Adopting this reaction mode makes it easier for the supplied ammonia to come into contact with the catalytically active species formed from the catalyst and the organic peroxide, so that hydroxylamine and ketone produced from the reaction of the catalytically active species and ammonia Can be efficiently reacted, and as a result, the amount of by-products produced by the contact of unreacted ammonia and ketone can be reduced, and oxime can be produced in good yield. The catalyst present on the other side of the diaphragm may be present as a catalyst packed layer separately from the diaphragm, may be added to the reaction system, or may be supported on the diaphragm surface. Although it is good, it is preferable to make it exist on the surface of the diaphragm. A catalyst may also be present on one side of the diaphragm. When using a solvent, the solvent may be present on the other side of the diaphragm by allowing the solvent to be present on one side of the diaphragm and passing through the diaphragm, or only on the other side of the diaphragm. A solvent may be present.

  In the method for producing oxime according to the present invention, a specific example of the reactor to be used includes a reactor having two chambers separated by the diaphragm, a so-called membrane reactor. Examples of the membrane reactor include a catalyst membrane reactor in which catalytic activity is imparted to the diaphragm, and a packed bed membrane reactor having a catalyst as a packed layer separately from the diaphragm, but a catalyst membrane reactor is preferred. The reactor is preferably glass-lined or stainless steel from the viewpoint of preventing the decomposition of the organic peroxide.

  The reaction temperature of the oximation reaction is usually 50 to 200 ° C, preferably 80 to 150 ° C. The reaction pressure is usually 0.1 to 1.0 MPa in absolute pressure, preferably 0.2 to 0.9 MPa. In order to make ammonia easily dissolve in the liquid phase of the reaction mixture, the reaction is preferably performed under pressure. In this case, the pressure may be adjusted using an inert gas such as nitrogen or helium.

  The post-treatment operation of the obtained reaction mixture after the oximation reaction is appropriately selected. For example, the oxime can be separated by subjecting the mixture after the oximation reaction to distillation. When the mixture after the oximation reaction is a slurry containing a solid catalyst, for example, after separating the solid catalyst by filtration, decantation, or the like, the oxime can be separated by subjecting the liquid phase to distillation. The separated catalyst can be reused after being subjected to treatments such as washing, calcination, and recontact with a silicon compound as necessary. Moreover, when a solvent and an unreacted raw material are contained in the mixture after oximation reaction, the solvent and unreacted raw material which were collect | recovered by distillation of the said liquid phase can be reused. The obtained oxime is suitably used as a raw material for producing a corresponding amide compound such as lactam by, for example, Beckmann rearrangement reaction.

  Next, with reference to FIG. 1, one Embodiment of the manufacturing method of the oxime concerning this invention is described. FIG. 1 is a schematic view showing the internal structure of a membrane reactor used for carrying out the oxime production method of the present embodiment.

  In FIG. 1, a membrane reactor 10 includes an organic peroxide and ketone supply port 1 for supplying organic peroxide and ketone, a reaction mixture outlet 2 for deriving a mixture after the oximation reaction, and ammonia. An ammonia supply port 3, a gas outlet 4, a diaphragm 5, an oximation reaction part 6, an ammonia retention part 7, an inner cylinder 8, and an outer cylinder 9 are provided. A space between the inner cylinder 8 and the outer cylinder 9 forms an ammonia retention part 7 as a first chamber. The inner cylinder 8 is composed of a diaphragm 5 and an oximation reaction portion 6, and the oximation reaction portion 6 is formed as a second chamber. The catalyst is present at least on the second chamber side.

  From the viewpoint of increasing the surface area of the diaphragm, increasing the contact efficiency, and increasing the reaction efficiency, the diaphragm 5 is preferably monolithic or honeycomb-shaped, and its outer shape is preferably cylindrical. Moreover, the thing to which the catalyst activity was provided is preferable at the point which a post-processing operation becomes easy, without a catalyst mixing in the reaction mixture obtained after oximation reaction. Examples of the diaphragm to which catalytic activity is imparted include a diaphragm on which a catalyst is supported and a diaphragm on which the catalyst itself is formed. From the viewpoint of mechanical strength, a diaphragm on which a catalyst is supported is preferable. When using a diaphragm carrying a catalyst, at least the one carrying the catalyst on the diaphragm surface on the second chamber side is used.

  Ammonia is supplied from an ammonia supply port 3 to an ammonia retention part 7 formed outside the diaphragm 5, and ammonia passes through the diaphragm 5. At this time, the ammonia retention part 7 is adjusted to a predetermined reaction pressure and reaction temperature. The ammonia that has permeated through the diaphragm 5 is formed in the oximation reaction unit 6 from the catalyst present inside the diaphragm 5 and the organic peroxide supplied from the organic peroxide and ketone supply port 1. Contact with the catalytically active species, and further contact with the ketone supplied from the supply port 1 of the organic peroxide and the ketone causes an oximation reaction to produce the desired oxime. At this time, the oximation reaction unit 6 is adjusted to a predetermined reaction pressure and reaction temperature. The gas outlet 4 may be closed or may be sealed with nitrogen, but is preferably closed. In the case of nitrogen sealing, unreacted ammonia is discharged from the gas outlet 4 along with nitrogen as a gas. The reaction mixture containing the produced oxime is led out from the reaction mixture outlet 2. In addition, it is preferable that ammonia supply, organic peroxide and ketone supply, and reaction mixture derivation are continuously performed from the viewpoint of productivity and operability. The reaction is preferably carried out under pressurized conditions.

  The organic peroxide and ketone may be supplied alone (so-called co-feed) or a mixture thereof.

  In the continuous reaction, the supply amount of ammonia is preferably 0.1 mol or more, more preferably 0.5 mol or more, and more preferably 0.5 mol or more, with respect to 1 mol of ketone. 1 mol or more is preferable, More preferably, it is 0.5 mol or more. In the continuous reaction, the supply amount of the organic peroxide is preferably 0.05 to 20 mol, more preferably 0.1 to 15 mol, per 1 mol of the ketone.

  Moreover, when using a solvent for reaction, a solvent may be supplied with ammonia, may be supplied with an organic peroxide and a ketone, is supplied with ammonia, and is supplied with an organic peroxide and a ketone. Alternatively, another supply port may be provided for supply.

  As the membrane reactor 10, a plurality of inner cylinders 8 composed of the diaphragm 5 and the oximation reaction unit 6 are installed in the outer cylinder 9 from the viewpoint of increasing the surface area of the diaphragm and increasing the reaction efficiency. What has the tubular diaphragm 5 is preferable.

  The supply of ketone, organic peroxide, and ammonia as raw materials may be performed by supplying the organic peroxide and ketone to the first chamber and supplying ammonia to the second chamber. In this case, the catalyst is present at least on the first chamber side.

  The reaction apparatus that can be used in the production method of the present invention is not limited to these, and the design can be arbitrarily changed within a range not impairing the effects of the present invention. Although illustration in FIG. 1 is omitted, a commonly used heating device, cooling device, thermometer, pressure gauge, pressure regulating valve, and the like can be appropriately installed.

10: Membrane reactor, 1: Organic peroxide and ketone supply port, 2: Reaction mixture outlet, 3: Ammonia supply port, 4: Gas outlet, 5: Membrane, 6: Oxidation reaction part, 7: Ammonia retention part , 8: inner cylinder, 9: outer cylinder

Claims (9)

  A method for producing an oxime, characterized in that ammonia is present on one side of a diaphragm, and ammonia permeated through the diaphragm, an organic peroxide, and a ketone are reacted in the presence of a catalyst on the other side of the diaphragm. .   The manufacturing method according to claim 1, wherein the catalyst is supported on a diaphragm surface on the other side of the diaphragm.   The production method according to claim 2, wherein the organic peroxide is hydroperoxide.   The manufacturing method according to claim 1, wherein the catalyst is a catalyst containing titanium and silicon oxide.   The production method according to claim 4, wherein the catalyst is a silicate containing titanium or a silica containing titanium.   The manufacturing method according to claim 5, wherein the silicate is a mesoporous silicate.   The production method according to claim 4, wherein the catalyst is contact-treated with a silicon compound.   The production method according to claim 7, wherein the silicon compound is at least one selected from the group consisting of an alkoxysilane compound, an organic disilazane compound, and a halogenated organic silane compound.   The production method according to any one of claims 1 to 8, wherein the ketone is a cycloalkanone.

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