JP2012115742A - Method for manufacturing titanium-containing silicon oxide catalyst, and method for manufacturing oxirane compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a titanium-containing silicon oxide catalyst capable of manufacturing an oxirane compound from an olefin and an organohydroperoxide highly selectively at a high yield, and a method for manufacturing the oxirane compound.SOLUTION: The method for manufacturing the titanium-containing silicon oxide catalyst includes a first step of obtaining a trialkyl silylated solid by treating a solid containing a titanium-containing zeolite laminar precursor in a solution containing a trialkylsilane compound and an acid to trialkyl silylate the solid and a second step of obtaining the titanium-containing silicon oxide catalyst by treating the trialkyl silylated solid obtained in the first step with a silylation reagent without subjecting the same to baking.

Description

  The present invention relates to a method for producing a titanium-containing silicon oxide catalyst and a method for producing an oxirane compound, which can produce an oxirane compound from an olefin and an organic hydroperoxide with high yield and high selectivity.

  A titanosilicate catalyst typified by TS-1 has a zeolite structure and is known to exhibit high activity in epoxidation of olefins using hydrogen peroxide. However, since these titanosilicate catalysts have a small pore size, there is a problem that epoxidation activity is very low when a large olefin or organic hydroperoxide is used. As an approach for reacting larger molecules, for example, Patent Document 1 includes a method of expanding the layer of a layered zeolite typified by MWW-type zeolite by silylation using dialkoxydialkylsilane.

JP 2008-162846 A

However, in order to produce an oxirane compound from an olefin and an organic hydroperoxide, further improvements have been required in terms of yield and selectivity.
Under such circumstances, the problem to be solved by the present invention is a method for producing a titanium-containing silicon oxide catalyst capable of producing an oxirane compound from an olefin and an organic hydroperoxide with high yield and high selectivity, and an oxirane compound. This is in providing a manufacturing method.

That is, this invention relates to the manufacturing method of the titanium containing silicon oxide catalyst which has the following 1st process and the following 2nd process.
First step: A step of obtaining a trialkylsilylated solid by performing a trialkylsilylation by treating a solid containing a titanium-containing zeolite layered precursor in a solution containing a trialkylsilane compound and an acid. Step: A step of obtaining a titanium-containing silicon oxide catalyst by treating the trialkylsilylated solid obtained in the first step with a silylating agent without subjecting to firing.

  The present invention also relates to a method for producing an oxirane compound in which an olefin and an organic hydroperoxide are reacted in the presence of the catalyst obtained by the above production method.

  According to the present invention, an oxirane compound can be produced from olefin and hydroperoxide with high yield and high selectivity.

The manufacturing method of the titanium containing silicon oxide catalyst of this invention has the following 1st process and the following 2nd process.
First step: A step of obtaining a trialkylsilylated solid by performing a trialkylsilylation by treating a solid containing a titanium-containing zeolite layered precursor in a solution containing a trialkylsilane compound and an acid. Step: A step of obtaining a titanium-containing silicon oxide catalyst by treating the trialkylsilylated solid obtained in the first step with a silylating agent without subjecting to firing.

  The titanium-containing zeolite layered precursor used as a raw material in the first step is a zeolite layered precursor into which titanium atoms have been introduced. As the zeolite layered precursor, the Structure Commission of the International Zeolite Association (IZA- SC), MWW type, FER type, RRO type, CDO type and the like. Of these, an MWW-type zeolite layered precursor is preferable. As a method for producing the zeolite layered precursor, for example, it can be produced by the method described in JP-A-2008-162846.

  The introduction of titanium atoms into the zeolite layered precursor is a direct introduction method in which a titanium source is coexisting when forming a zeolite structure by hydrothermal synthesis, etc., after synthesizing a zeolite layered precursor that does not contain titanium atoms, Any of post-introduction methods in which titanium atoms are introduced by methods such as ion exchange, isomorphous substitution, and atom planting may be used, and direct introduction methods are preferred.

  The structure of the zeolite layered precursor can be observed by X-ray diffraction (XRD), and the introduction of titanium atoms into the zeolite layered precursor can be observed by ultraviolet-visible spectroscopy (UV-Vis) or the like.

  Hereinafter, a case where an MWW-type zeolite layered precursor directly introduced with titanium atoms, which is an example of a preferred embodiment of the present invention, will be described in detail, but the present invention is not limited in any way by these descriptions. is not.

  The titanium-containing MWW-type zeolite layered precursor can be obtained by mixing a silicon compound, a titanium compound, a boron compound, water and a structure-directing agent, and then subjecting to a hydrothermal synthesis reaction.

  Examples of the silicon compound include alkoxysilane and amorphous silica. Examples of the alkoxysilane include tetramethylorthosilicate, tetraethylorthosilicate, and tetrapropylorthosilicate. Examples of the amorphous silica include Examples thereof include fumed silica.

  Examples of the titanium compound include alkoxy titanium, peroxy titanate, titanium halide, titanium acetate, titanium nitrate, titanium sulfate, and titanium phosphate. Examples of the alkoxy titanium include tetra-n-propyl ortho. Examples thereof include titanate, tetra-isopropyl orthotitanate, tetra-n-butyl orthotitanate, etc., and examples of peroxytitanate include tetra-n-butylammonium peroxytitanate, and examples of titanium halide include, for example, , Titanium tetrachloride, titanium tetrabromide, titanium tetraiodide and the like.

  Examples of the boron compound include boric acid and anhydrous boric acid.

  Examples of the structure-directing agent include piperidine, hexamethyleneimine, and trimethyladamantaammonium hydroxide, which can be used alone or mixed in a desired ratio. Of these, piperidine is preferably used alone.

  The use ratio of each of the raw materials (silicon compound, titanium compound, boron compound, water and structure directing agent) is 0.01 to 0.2 mol times as a titanium atom based on the silicon atom in the silicon compound. It is preferable that the boron compound is 0.1 to 3 mol times as a boron atom, water is 3 to 50 mol times, and the structure directing agent is 0.1 to 3 mol times.

  The raw materials are preferably mixed at a temperature of 0 to 60 ° C, more preferably 10 to 50 ° C.

  As the method for mixing the raw materials, for example, all raw materials may be mixed at once, or the raw materials may be mixed sequentially. In particular, mixing the raw material that is a liquid after mixing the raw material that is a liquid in advance allows uniform stirring, and thus can suppress the uneven distribution of titanium atoms in the obtained titanium-containing MWW-type zeolite layered precursor. preferable.

  The mixture of each raw material is subjected to a hydrothermal synthesis reaction in order to obtain a titanium-containing MWW-type zeolite layered precursor. Here, the titanium-containing MWW-type zeolite layered precursor indicates a titanium-containing silicate layer having an MWW-type topology and a structure-directing agent included in and between the silicate layers.

  In general, hydrothermal synthesis refers to the synthesis and crystal growth method of substances performed in the presence of high-temperature and high-pressure water (“Iwanami Physical and Chemical Dictionary”, 4th edition, Iwanami Shoten, 1987, p. 647). Specifically, the above-mentioned raw materials are mixed, heated in an autoclave at a temperature of about 100 to 200 ° C. under a self-pressure, and stirred or allowed to stand for several hours to several days. .

  The solid containing the titanium-containing MWW-type zeolite layered precursor produced by hydrothermal synthesis is usually obtained by filtration, and if necessary, washed with an organic solvent such as water or methanol and then dried.

  The drying method is preferably, for example, heated at 10 to 200 ° C. in a reduced pressure atmosphere or a non-reducing gas such as nitrogen, argon or carbon dioxide or an oxygen-containing gas such as a reduced pressure atmosphere, and 50 to 100 ° C. is preferable. Further preferred.

  The solid containing the titanium-containing MWW-type zeolite layered precursor obtained by the above operation is a solid that has been trialkylsilylated by treatment in a solution containing a trialkylsilane compound and an acid in the first step of the present invention. Can be obtained. The structure-directing agent is simultaneously removed from the titanium-containing MWW-type zeolite layered precursor by treatment with an acid-containing solution.

  The trialkylsilane compound used in the first step may be any compound having a reactive functional group capable of reacting with the surface hydroxyl group of the titanium-containing silicate layer. For example, trialkylalkoxysilane, trialkylhalogenosilane, trialkylsilyl Examples thereof include amines and trialkylsilylamides, and trialkylalkoxysilanes are preferable.

  Moreover, as carbon number of the alkyl group of a trialkylsilane compound, Preferably, it is 1-3, More preferably, it is 1-2, More preferably, it is 1.

  Examples of the trialkylsilane compound include trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, and the like.

  Examples of the acid used in the first step include inorganic acids and organic acids. Examples of the inorganic acids include hydrochloric acid, sulfuric acid, and nitric acid. Examples of the organic acids include formic acid and acetic acid. And is preferably an inorganic acid, more preferably nitric acid. The acid concentration is preferably 0.5 to 10 N. As the solvent, an organic solvent such as alcohol or ketone can be used, and water is more preferable.

  The first step is usually performed at 40 to 120 ° C, more preferably 60 to 100 ° C. The treatment time can be appropriately determined from the viewpoint of the removal of the structure-directing agent and the degree of trimethylsilylation.

  The trialkylsilylated solid obtained in the first step can be usually obtained by filtration, washing with an organic solvent such as water or methanol, if necessary, and then drying. What is important here is that the subsequent second step is carried out without firing.

  Firing is performed at 400 to 700 ° C. for the purpose of removing organic substances. When the solid obtained in the first step is calcined, the trialkylsilyl group is detached or burned, and the pore volume of the catalyst is reduced. This is insufficient from the viewpoint of obtaining a high-performance catalyst.

  In the second step of the present invention, a titanium-containing silicon oxide catalyst is obtained by treating the trialkylsilylated solid obtained in the first step with a silylating agent without subjecting to firing as described above.

  Examples of the silylating agent include organic silanes, organic silylamines, organic silylamides and derivatives thereof, organic silazanes, and other silylating agents.

  Examples of the organic silane include chlorotrimethylsilane, nitrotrimethylsilane, chlorotriethylsilane, chlorodimethylphenylsilane, dimethyl-n-propylchlorosilane, dimethylisopropylchlorosilane, t-butyldimethylchlorosilane, tripropylchlorosilane, dimethyloctylchlorosilane, and tributyl. Chlorosilane, trihexylchlorosilane, dimethylethylchlorosilane, dimethyloctadecylchlorosilane, n-butyldimethylchlorosilane, 3-chloropropyldimethylchlorosilane, dimethoxymethylchlorosilane, triethoxychlorosilane, dimethylphenylchlorosilane, benzyldimethylchlorosilane, diphenylmethylchlorosilane, diphenylvinylchlorosilane , Tribenzylchloro Orchids include 3-cyanopropyl dimethylchlorosilane.

  Examples of the organic silylamine include N-trimethylsilylimidazole, Nt-butyldimethylsilylimidazole, N-dimethylethylsilylimidazole, N-dimethyl-n-propylsilylimidazole, N-dimethylisopropylsilylimidazole, N-trimethylsilyldimethylamine. N-trimethylsilyldiethylamine, N-trimethylsilylpyrrole, N-trimethylsilylpyrrolidine, N-trimethylsilylpiperidine, 1-cyanoethyl (diethylamino) dimethylsilane, pentafluorophenyldimethylsilylamine.

  Examples of organic silylamides and derivatives include N, O-bistrimethylsilylacetamide, N, O-bistrimethylsilyltrifluoroacetamide, N-trimethylsilylacetamide, N-methyl-N-trimethylsilylacetamide, N-methyl-N-trimethylsilyltrifluoro Examples include acetamide, N-methyl-N-trimethylsilylheptafluorobutyramide, N- (t-butyldimethylsilyl) -N-trifluoroacetamide, N, O-bis (diethylhydrosilyl) trifluoroacetamide.

  Examples of the organic silazane include hexamethyldisilazane, heptamethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1,3-bis (chloromethyl) tetramethyldisilazane, 1,3-divinyl- Examples include 1,1,3,3-tetramethyldisilazane and 1,3-diphenyltetramethyldisilazane.

Examples of other silylating agents include N-methoxy-N, O-bistrimethylsilyltrifluoroacetamide, N-methoxy-N, O-bistrimethylsilylcarbamate, N, O-bistrimethylsilylsulfamate, trimethylsilyltrifluoromethane. Examples thereof include sulfonate and N, N′-bistrimethylsilylurea.
A preferred silylating agent is hexamethyldisilazane.

  The silylation treatment can be performed either in the gas phase or in the liquid phase. When carried out in the liquid phase, it is usually carried out in a solvent that does not essentially react with the silylating agent, and a hydrocarbon is preferably used as the solvent. Examples of the hydrocarbon solvent include aliphatic hydrocarbons and aromatic hydrocarbons. Examples of the aliphatic hydrocarbons include hexane and heptane. Examples of the aromatic hydrocarbon include benzene, Examples include toluene and xylene. Processing temperature is 0-300 degreeC, Preferably it is 50-150 degreeC.

  The titanium-containing silicon oxide catalyst obtained in the second step can be usually obtained by filtration, washing with an organic solvent, if necessary, and then drying.

  Moreover, the titanium-containing silicon oxide catalyst obtained by this invention can be shape | molded as needed. This molding may be performed before the first step of the present invention, between the first step and the second step, or at any stage after the second step.

  As the molding method, any method such as compression molding represented by roll press molding (briqueting, compacting), hydraulic press molding, tableting molding, and extrusion molding, and extrusion molding may be used, but compression molding is more preferable. In extrusion molding, generally used organic and inorganic binders can be used. In the present invention, it is preferable not to use a binder.

The compression pressure is usually 0.1 to 10 ton / cm ² , preferably 0.2 to 5 ton / cm ² , more preferably 0.5 to 2 ton / cm ² .

  The shape of the molded body may be any shape such as a tablet, a sphere, or a ring. It may be used in the reaction as it is, or may be crushed to an appropriate size.

  In particular, the catalyst of the present invention can be optimally used in a method for producing an oxirane compound in which an olefin and an organic hydroperoxide are reacted.

  The olefin may be an acyclic, monocyclic, bicyclic or polycyclic compound and may be a monoolefin, diolefin or polyolefin. If there are two or more olefinic bonds, this may be a conjugated bond or a non-conjugated bond. Olefins having 2 to 60 carbon atoms are generally preferred. It may have a substituent, and the substituent is preferably a relatively stable group. Examples of the monoolefin include ethylene, propylene, butene-1, isobutylene, hexene-1, hexene-2, hexene-3, octene-1, decene-1, styrene, cyclohexene, and propylene is preferable. Examples of the diolefin include butadiene and isoprene. Examples of the substituent include various substituents containing a halogen atom, oxygen, sulfur, nitrogen atom together with hydrogen and / or carbon atom. Examples of the olefin having a substituent include unsaturated alcohols, Examples of the unsaturated alcohol include allyl alcohol and crotyl alcohol, and examples of the olefin substituted with the halogen atom include allyl chloride.

Organic hydroperoxides have the general formula R—O—O—H
(Where R is a monovalent hydrocarbyl group.)
Which reacts with an olefin to produce an oxirane compound and a compound R—OH. R is preferably a hydrocarbyl group having 3 to 20 carbon atoms, more preferably a hydrocarbyl group having 3 to 10 carbon atoms, and still more preferably a secondary or tertiary alkyl group having 3 to 10 carbon atoms. Group or a secondary or tertiary aralkyl group having 8 to 10 carbon atoms, particularly preferably a tertiary alkyl group having 3 to 10 carbon atoms or a secondary or tertiary aralkyl group having 8 to 10 carbon atoms. It is a group. Examples of the tertiary alkyl group having 3 to 10 carbon atoms include a tertiary butyl group and a third pentyl group. Examples of the secondary alkyl group having 3 to 10 carbon atoms include a cyclopentyl group and the like. Examples of the tertiary aralkyl group having 8 to 10 carbon atoms include a 2-phenylpropyl-2 group. Furthermore, various tetranylyl groups generated by removing a hydrogen atom from the aliphatic side chain of the tetralin molecule are also mentioned.

  The organic hydroperoxide is preferably cumene hydroperoxide, and in that case, it can be suitably used as part of the propylene oxide single production process described in JP-A-2008-266304.

  The production of the oxirane compound can be carried out in the liquid phase using a solvent and / or a diluent. The solvent and diluent are preferably liquid under the temperature and pressure during the reaction, and are substantially inert to the reactants and products. The solvent may consist of substances present in the organic hydroperoxide solution used. For example, when the cumene hydroperoxide solution is a mixture comprising cumene hydroperoxide and its starting material cumene, it can be used as a substitute for the solvent without particularly adding a solvent.

  The reaction temperature is generally 0 to 200 ° C, but a temperature of 25 to 200 ° C is preferred. The pressure may be sufficient to keep the reaction mixture in a liquid state. In general, the pressure is advantageously between 100 and 10000 kPa.

  After completion of the reaction, the liquid mixture containing the oxirane compound can be easily separated from the catalyst. The liquid mixture can then be purified by a suitable method. Purification includes fractional distillation, selective extraction, filtration, washing and the like. The solvent, catalyst, unreacted olefin and unreacted organic hydroperoxide can be recycled and reused.

  The oxirane compound can be produced in the form of a slurry or a fixed bed. In the case of a large-scale industrial operation, it is preferable to use a fixed bed.

  The following examples illustrate the invention.

[Example 1]
(1) Preparation of titanium-containing zeolite layered precursor 342 g of ion-exchanged water and 119 g of piperidine were placed in a 3 liter separable flask and stirred, and 28 g of tetra-n-butyl orthotitanate was added dropwise thereto at room temperature. added. After stirring for 0.5 hour, 84 g of boric acid was added and stirred for another 0.5 hour. Subsequently, 60 g of Cab-O-Sil M-7D (caboted fumed silica) was added, followed by stirring for 1 hour. Thereafter, 342 g of ion-exchanged water was added, and the mixture which was stirred and homogenized was divided into 8 parts and charged into 8 200 ml polytetrafluoroethylene inner cylinder autoclaves. Hydrothermal synthesis was carried out at 170 ° C. for 7 days with stirring. The resulting solid was collected by filtration, washed with a small amount of ion-exchanged water, and dried at 10 mmHg and 70 ° C. for 5 hours. 50 g of the obtained solid was put into a 1 liter flask, and 500 ml of methanol was added. While stirring, the mixture was heated at the reflux temperature for 1.5 hours, allowed to cool, and then the solution was removed by decantation. The same operation was repeated once more using 500 ml of methanol. Finally, the solid collected by filtration was washed with a small amount of methanol and then dried at 70 ° C. and 10 mmHg for 7 hours to obtain 13 g of a solid containing a titanium-containing zeolite layered precursor.

(2) Trialkylsilylation and removal of structure directing agent (piperidine) (first step)
3 g of the solid containing the titanium-containing zeolite layered precursor obtained by the above method was placed in a flask, and 100 ml of 6N aqueous nitric acid and 3 g of trimethylethoxysilane were added. Heated at 80 ° C. for 5 hours with stirring. After allowing to cool, the solid was collected by filtration, washed with 1 liter of ion exchange water, and dried at 70 ° C. and 10 mmHg for 6 hours to obtain 2.6 g of a trialkylsilylated solid.

(3) Silylation (second step)
1 g of the trialkylsilylated solid obtained in the first step, 1 g of hexamethyldisilazane, and 20 g of toluene were mixed and heated under reflux for 1.5 hours. After allowing to cool, the solid was collected by filtration and dried at 120 ° C. and 10 mmHg for 1.5 hours to obtain 1 g of a titanium-containing silicon oxide catalyst.

(4) Propylene oxide (PO) synthesis 0.5 g of the catalyst obtained by the above method, 60 g of 25% cumene hydroperoxide (CHPO) / cumene solution and 33 g of propylene (C3 ′) were charged into an autoclave, and spontaneously produced. The reaction was carried out at 100 ° C. under pressure for 1.5 hours (including the temperature rising time). After cooling and purging with C3 ′, the autoclave was opened, and the post-reaction solution was sampled and analyzed. The reaction results are shown in Table 1.

[Example 2]
Treatment with methanol without performing vacuum drying of the solid obtained after hydrothermal synthesis when preparing the titanium-containing zeolite layered precursor, treatment temperature of the first step was 88 ° C, amount of catalyst used during PO synthesis Was carried out in the same manner as in Example 1 except that 0.25 g was used. The reaction results are shown in Table 1.

Example 3
The same procedure as in Example 1 was performed except that the treatment temperature in the first step was 97 ° C. and the amount of catalyst used during PO synthesis was 0.25 g. The reaction results are shown in Table 1.

[Comparative Example 1]
The same procedure as in Example 1 was performed except that in the first step, trimethylethoxysilane was not used and only 100 ml of 6N nitric acid was used. The reaction results are shown in Table 1.

[Comparative Example 2]
Treatment with methanol without vacuum drying of the solid obtained after hydrothermal synthesis when preparing titanium-containing zeolite layered precursor, treatment with dimethyldiethoxysilane instead of trimethylethoxysilane in the first step The same procedure as in Example 1 was performed except that the temperature was 97 ° C. The reaction results are shown in Table 1.

＊１：ＴＭＳＯＥｔ＝トリメチルエトキシシラン
＊２：ＤＭＳ（ＯＥｔ）_２＝ジメチルジエトキシシラン
＊３：ＰＯ/Ｃ３’選択率＝生成ＰＯモル/反応Ｃ３’モル*１００

* 1: TMSOEt = trimethylethoxysilane * 2: DMS (OEt) ₂ = dimethyldiethoxysilane * 3: PO / C3 ′ selectivity = generated PO mole / reaction C3 ′ mole * 100

Claims (7)

The manufacturing method of the titanium containing silicon oxide catalyst which has the following 1st process and the following 2nd process.
First step: A step of obtaining a trialkylsilylated solid by performing a trialkylsilylation by treating a solid containing a titanium-containing zeolite layered precursor in a solution containing a trialkylsilane compound and an acid. Step: A step of obtaining a titanium-containing silicon oxide catalyst by treating the trialkylsilylated solid obtained in the first step with a silylating agent without subjecting to firing.   The production method according to claim 1, wherein the titanium-containing zeolite layered precursor is a titanium-containing MWW-type zeolite layered precursor.   The production method according to claim 1 or 2, wherein the trialkylsilane compound is a trialkylalkoxysilane.   The production method according to claim 1, wherein the acid is nitric acid.   The manufacturing method of the oxirane compound which makes an olefin and an organic hydroperoxide react in presence of the catalyst obtained by the manufacturing method of Claim 1.   The production method according to claim 5, wherein the olefin is propylene.   The method according to claim 5 or 6, wherein the organic hydroperoxide is cumene hydroperoxide.