JP2012031010A - Titanosilicate, and method for producing olefin oxide using the same as catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst which can produce an olefin oxide in a high yield from an oxidizing agent such as hydrogen peroxide and an olefin compound such as propylene.SOLUTION: A titanosilicate has an X-ray diffraction pattern exhibiting the following values of lattice spacings d/:Å of 12.4±0.8, 10.8±0.5, 9.0±0.3, 6.0±0.3, 3.9±0.1 and 3.4±0.1, and has a bulk density of 0.05 to 0.15 g/ml.

Description

  The present invention relates to titanosilicate, a method for producing olefin oxide using the titanosilicate as a catalyst, and the like.

  In the method for producing olefin oxide such as propylene oxide, titanosilicate is used as a catalyst. As such a catalyst, for example, in Patent Document 1, a boron-containing compound, tetrabutyl orthotitanate, fumed silica and piperidine are hydrothermally synthesized at a temperature of 170 ° C., and the obtained layered compound (also referred to as an as-synthesized sample) is used. Is obtained by contacting with a nitric acid aqueous solution under reflux conditions. Patent Document 1 also describes a method for producing propylene oxide from hydrogen peroxide and propylene by using the titanosilicate as a catalyst.

JP-A-2005-262164 (Example)

A conventional method for producing propylene oxide using titanosilicate as a catalyst is, for example, the yield of olefin compound per oxidant such as the yield of propylene oxide per hydrogen peroxide (hereinafter simply referred to as “yield”). But it was not always enough.
The objective of this invention is providing the catalyst which can manufacture an olefin oxide with the outstanding yield from an oxidizing agent and an olefin compound.

In order to solve such problems, the present inventors have intensively studied. As a result, they have found that bulky titanosilicate is a catalyst capable of producing olefin oxide in an excellent yield, and have reached the following present invention.
<1> A titanosilicate having an X-ray diffraction pattern having a value shown below, wherein the titanosilicate has a bulk density of 0.05 to 0.15 g / ml.
X-ray diffraction pattern lattice spacing d / ｄ (angstrom)
12.4 ± 0.8
10.8 ± 0.5
9.0 ± 0.3
6.0 ± 0.3
3.9 ± 0.1
3.4 ± 0.1
<2> The titanosilicate according to claim 1, wherein the bulk density is 0.08 to 0.11 g / ml.

<3> A method for producing a titanosilicate comprising the following first step and second step.
First step: A step of obtaining a solid by heating a mixture containing a structure-directing agent, a compound containing a group 13 element of the periodic table, a titanium-containing compound, a silicon-containing compound and water to a maximum temperature of less than 155 ° C.
Second step: A step of bringing at least one selected from the group consisting of an inorganic acid and a titanium-containing compound into contact with the solid obtained in the first step.
<4> The method for producing a titanosilicate according to <3>, wherein the compound containing a Group 13 element in the periodic table is a boron-containing compound.
<5> The method for producing a titanosilicate according to <3> or <4>, wherein the structure directing agent is piperidine or hexamethyleneimine.

<6> The method according to any one of <3> to <5>, further comprising a third step of heating the titanosilicate obtained in the second step in a temperature range of 250 to 1000 ° C.
<7> The method according to any one of <3> to <6>, further comprising a fourth step of contacting the titanosilicate obtained in the second step or the third step with the structure directing agent.
<8> The method according to any one of <3> to <7>, further comprising a fifth step of silylating the titanosilicate obtained in the second step, the third step or the fourth step with a silylating agent.
<9> The method according to any one of <3> to <8>, further including a sixth step of contacting the titanosilicate obtained in the second step, the third step, the fourth step, or the fifth step with hydrogen peroxide. Production method.
<10> A titanosilicate obtained by the production method according to any one of <3> to <9>.

<11> A catalyst for producing olefin oxide, comprising the titanosilicate according to <1>, <2> or <10>.
<12> A method for producing an olefin oxide comprising a step of oxidizing an olefin compound with an oxidizing agent in the presence of the catalyst according to <11>.
<13> The method for producing an olefin oxide according to <12>, wherein the olefin compound is propylene and the oxidizing agent is hydrogen peroxide.

  According to the present invention, a novel titanosilicate can be provided as an olefin oxide catalyst having a better yield per oxidant.

Electron micrograph of the titanosilicate obtained in Example 1 Electron micrograph of titanosilicate obtained in Reference Example 1

  The titanosilicate of the present invention has an X-ray diffraction pattern having the value shown above, and its bulk density is 0.05 to 0.15 g / ml, preferably 0.08 to 0.11 g / ml. is there. Titanosilicate having such characteristics is a catalyst capable of producing olefin oxide in an excellent yield. Hereinafter, a catalyst composed of titanosilicate having the above characteristics may be referred to as the present catalyst. As will be described later, this catalyst is extremely useful as a catalyst used in a method for producing olefin oxide.

Here, the titanosilicate is a substance in which a part of silicon atoms in the silicon dioxide skeleton is replaced with titanium atoms.
The replacement of a part of silicon atoms of the silicon dioxide skeleton with titanium atoms means that the UV-visible absorption spectrum of the titanosilicate in the wavelength region of 200 nm to 400 nm shows the maximum absorption peak in the wavelength region of 210 nm to 230 nm. (See, for example, Chemical Communications 1026-1027, (2002) FIGS. 2D and 2E). The ultraviolet-visible absorption spectrum can be measured by a diffuse reflection method using an ultraviolet-visible spectrophotometer equipped with a diffuse reflection device.

The present catalyst has the following X-ray diffraction pattern among titanosilicates.
X-ray diffraction pattern (lattice spacing d / Å)
12.4 ± 0.8
10.8 ± 0.5
9.0 ± 0.3
6.0 ± 0.3
3.9 ± 0.1
3.4 ± 0.1
The X-ray diffraction pattern is obtained using an X-ray diffraction apparatus using copper K-alpha radiation. Detailed analysis conditions will be described in the [Example] section below.

  The bulk density of the catalyst is determined by a tap density method. That is, the catalyst is put in a graduated cylinder and its weight is measured. Subsequently, the graduated cylinder is tapped until tapping is performed until the capacity of the catalyst is not reduced, and the capacity of the catalyst after tapping is measured. The bulk density (g / ml) is calculated from the weight and the volume thus obtained.

In conventional titanosilicate, primary particles aggregate to form secondary particles. On the other hand, the present catalyst has a low bulk density because secondary particles (for example, about 2 to 4 μm) in which the primary particles of titanosilicate aggregate to form the outer shell portion have a space inside. it is conceivable that.
Examples of the primary particles of the catalyst include titanosilicate having a hexagonal flat plate shape. One side of the hexagonal flat plate is, for example, about 0.05 to 0.2 μm, and the thickness thereof is, for example, about 10 to 50 nm. As a representative example, an electron micrograph of titanosilicate obtained in Example 1 described later is shown in FIG.

This catalyst can be manufactured by the manufacturing method which has the following 1st process and 2nd process, for example.
First step: a step of obtaining a solid by heating a mixture containing a structure-directing agent, a compound containing a group 13 element of the periodic table, a titanium-containing compound, a silicon-containing compound and water to a temperature condition of less than 155 ° C. .
Second step: A step of bringing at least one selected from the group consisting of an inorganic acid and a titanium-containing compound into contact with the solid obtained in the first step.

Hereinafter, the compound containing the group 13 element of the periodic table, the silicon-containing compound, the titanium-containing compound, and the structure directing agent used in the first step will be described.
Examples of the compound containing a group 13 element in the periodic table (hereinafter sometimes referred to as a group 13 element-containing compound) include a boron-containing compound, an aluminum-containing compound, and a gallium-containing compound.
Examples of the boron-containing compound include boric acid; borate salt; boron oxide; boron halide; trialkyl boron-containing compound having an alkyl group having 1 to 4 carbon atoms, and the aluminum-containing compound includes, for example, Examples of the gallium-containing compound include gallium oxide.
Preferable group 13 element-containing compounds include, for example, boron-containing compounds, and more preferably boric acid.

  Examples of the silicon-containing compound include silicic acid, silicate, silicon oxide, silicon halide, fumed silica, tetraalkylorthosilicate, colloidal silica, and the like, and fumed silica is preferable.

Examples of the titanium-containing compound include titanium alkoxide, titanium organic acid salt, titanium inorganic acid salt, titanium halide, and titanium oxide.
Titanium alkoxide is a compound having an alkoxyl group having 1 to 4 carbon atoms, and examples thereof include tetramethyl orthotitanate, tetraethyl orthotitanate, tetraisopropyl orthotitanate, and tetra-n-butyl orthotitanate.
Examples of the organic acid salt of titanium include titanium acetate. Examples of the inorganic acid salt of titanium include titanium nitrate, titanium sulfate, titanium phosphate, titanium perchlorate, and the like. Examples of the titanium oxide include titanium tetrachloride. Examples of the titanium oxide include titanium dioxide.
As the titanium-containing compound, titanium alkoxide is preferable, and tetra-n-butyl orthotitanate is particularly preferable.
The titanium atom content of this catalyst can mention the range of 0.005-0.05 mol etc. with respect to 1 mol of silicon atoms contained in this catalyst, Preferably 0.01-0.05. The range of moles.
As a method for adjusting the titanium atom content contained in the present catalyst, for example, the respective usage amounts of the titanium-containing compound and the silicon-containing compound used in the first step are set to a predetermined titanium atom content within the above range. It may be adjusted as appropriate.

A structure directing agent means a nitrogen-containing organic compound that contributes to the formation of a zeolite structure. Such a structure-directing agent can form a precursor of a zeolite structure by organizing polysilicate ions or polymetallosilicate ions around it (see Zeolite Science and Engineering on pages 33-34, 2000, Kodansha Scientific). .
Examples of the structure-directing agent include organic amines such as piperidine and hexamethyleneimine; N, N, N-trimethyl-1-adamantanammonium salt (N, N, N-trimethyl-1-adamantanammonium hydroxide, N, N Quaternary ammonium salts such as octyltrimethylammonium salts (octyltrimethylammonium hydroxide, octyltrimethylammonium bromide, etc.) described in Chemistry Letters 916-917 (2007), and the like. . One type of structure directing agent may be used, or two or more types of structure directing agents may be mixed and used in an arbitrary ratio.
Preferred structure directing agents are piperidine, hexamethyleneimine and mixtures thereof.

Next, the first step will be described.
The amount of water used in the first step may be adjusted to a range of 5 to 200 mol, preferably 10 to 50 mol, based on 1 mol of silicon in the silicon-containing compound used in the first step. .
The first step will be described in more detail. A mixture containing a structure-directing agent, a group 13 element-containing compound, a titanium-containing compound, a silicon-containing compound and water is placed in a closed container such as an autoclave, and the temperature range is less than 155 ° C. at the maximum. Heat. Preferably, it heats within the temperature range of 100 degreeC or more and less than 155 degreeC, Preferably, it is within the temperature range of 130 to 150 degreeC. When the temperature is 100 ° C or higher, the crystallinity of the present catalyst tends to be excellent, and when the temperature is lower than 155 ° C, the present catalyst having a bulk density of 0.15 g / ml or less can be provided.
Here, the temperature range means not the temperature of the outer surface of the sealed container but the temperature displayed by a thermometer that is directly or indirectly contacted with the mixture using a sheath tube or the like.

  The heating time in the first step is the time until the solid obtained in the first step gives the X-ray diffraction pattern, and varies depending on the heating temperature and the amount of raw material used. Within the range, for example, the range of 10 to 200 hours can be mentioned.

The mixture obtained in the first step can be solid-liquid separated by, for example, filtration to obtain a solid.
The obtained solid is further washed with water or the like to remove unreacted raw materials such as a structure-directing agent, a group 13 element-containing compound, a titanium-containing compound, and a silicon-containing compound before being subjected to the second step. It is preferable. Here, the washing is preferably performed until the pH of the washed liquid becomes 10 to 11.
It is preferable to dry the washed solid by, for example, ventilation drying, reduced pressure drying, vacuum freeze drying, or the like until there is no weight loss of the solid.

The second step is a step of contacting at least one selected from the group consisting of inorganic acids and titanium-containing compounds with the solid obtained in the first step.
Here, examples of the inorganic acid include sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, fluorosulfonic acid, and a mixture thereof. Preferably, for example, nitric acid, perchloric acid, fluorosulfonic acid, or these And the like.
The inorganic acid is preferably a solution mixed with a solvent, and examples of such a solvent include water, alcohol solvents, ether solvents, ester solvents, ketone solvents, and mixtures thereof. It is.
Examples of the concentration of the inorganic acid include a range of 0.01M to 20M (M: number of moles of inorganic acid / volume of inorganic acid solution (L)), preferably a range of 1M to 5M.

Examples of the titanium-containing compound used in the second step are the same as the titanium-containing compound used in the first step.
As usage-amount of the titanium containing compound used for a 2nd process, 10 weight part or less can be mentioned with respect to 1 weight part of solid, for example, Preferably it is 0.01-2 weight part.

As a contact temperature in a 2nd process, the temperature range of 20-150 degreeC can be mentioned, for example, Preferably, the temperature range of 50-104 degreeC is mentioned.
The second step may be performed under reduced pressure, normal pressure, or increased pressure, but is preferably performed under slight pressure in the range of about 0 to 10 MPa as a gauge pressure.
Moreover, it is preferable to perform a 2nd process in solvent presence. As a solvent, the solvent illustrated above as a solvent mixed with an inorganic acid is preferable.

  The present catalyst obtained in the second step has a layered structure, and the present dehydrated and condensed catalyst forms Ti-MWW. Here, Ti-MWW means having an MWW structure in the structure code of IZA (International Zeolite Society).

The titanosilicate obtained in the second step is the present catalyst, and further obtained by heating the titanosilicate obtained in the third step, ie, the second step, in a temperature range of 250 to 1000 ° C. The titanosilicate produced is also the present catalyst.
The third step will be specifically described. For example, the product obtained in the second step is placed in a heating furnace such as electricity, and the temperature is within a temperature range of 250 to 1000 ° C. over 1 to 24 hours, preferably 300 to Examples include a step of raising the temperature to a temperature range of 600 ° C., further keeping the temperature for 1 to 24 hours, and naturally cooling in the furnace.
The third step is, for example, in a heating furnace under an atmosphere of an inert gas such as nitrogen, argon or helium; an oxidizing gas such as air, oxygen or carbon dioxide; or a reducing gas such as hydrogen, carbon monoxide or propylene. Preferably it is done.
By the third step, the titanosilicate obtained in the second step is dehydrated and condensed.

The titanosilicate obtained through the step of contacting the titanosilicate obtained in the second step or the third step with the structure directing agent (hereinafter sometimes referred to as the fourth step) is also the present catalyst.
The operation of the fourth step will be specifically described. For example, the titanosilicate obtained in the second step or the titanosilicate obtained in the third step, a structure directing agent, and a solvent as necessary are autoclaved. In an airtight container such as a glass flask or the like, for example, in the atmosphere, in a container such as a glass flask, the titanosilicate obtained in the second step or the titanosilicate obtained in the third step The operation of stirring and mixing the structure directing agent and the solvent as necessary, for example, in the atmosphere, in a container such as a glass flask, the titanosilicate obtained in the second step or obtained in the third step Examples of the operation include static mixing of titanosilicate, a structure-directing agent, and, if necessary, a solvent.
Examples of the solvent used in the fourth step include water, an alcohol solvent, an ether solvent, an ester solvent, a ketone solvent, a mixture thereof, and the like, preferably water.
Examples of the structure-directing agent include those similar to the structure-directing agent used in the first step.

The lower limit of the temperature at the time of contact between the titanosilicate and the structure directing agent in the fourth step can be, for example, 0 ° C., preferably 20 ° C., more preferably 50 ° C., and particularly preferably 100 ° C. be able to. The upper limit of the temperature at the time of contact of the titanosilicate and the structure directing agent in the fourth step can be, for example, 250 ° C., preferably 200 ° C., more preferably 180 ° C.
The pressure at the time of contact between the titanosilicate and the structure directing agent in the fourth step can be under normal pressure, under reduced pressure or under pressure, and preferably under normal pressure from 0 to 10 MPa in terms of gauge pressure. . The titanosilicate obtained through the fourth step is separated by, for example, filtration. If necessary, the separated solid may be further subjected to post-treatment such as washing and drying.

The titanosilicate obtained through the step of silylating the titanosilicate obtained in the second step, the third step or the fourth step with a silylating agent (hereinafter sometimes referred to as the fifth step) is also the present catalyst. It is.
The fifth step will be specifically described. For example, the titanosilicate obtained in the second step using a silylating agent such as 1,1,1,3,3,3-hexamethyldisilazane, the third step Examples thereof include a step of silylating the titanosilicate obtained in step 4 or the titanosilicate obtained in the fourth step according to the method described in European Patent Publication No. EP1488853A1.

Also obtained through the step of contacting the titanosilicate obtained in the second step, the third step, the fourth step or the fifth step with hydrogen peroxide (hereinafter sometimes referred to as the sixth step) This catalyst.
The concentration of hydrogen peroxide used in the sixth step is, for example, in the range of 0.0001 wt% to 50 wt%.
Here, as a solvent of a hydrogen peroxide solution, the solvent illustrated at the 4th process can be mentioned, Preferably, water, acetonitrile, these mixed solvents, etc. can be mentioned, for example.
As temperature in a 6th process, the range of 0 degreeC-100 degreeC, for example, Preferably the range of 0 degreeC-60 degreeC can be mentioned.

The method for producing olefin oxide of the present invention is a method using the present catalyst. That is, the method for producing olefin oxide of the present invention includes a step of oxidizing an olefin compound with an oxidizing agent in the presence of the present catalyst (hereinafter sometimes referred to as an oxidation reaction).
An oxidizing agent means the compound which gives an oxygen atom to an olefin compound. Examples of the oxidizing agent include oxygen and peroxide. Examples of the peroxide include hydrogen peroxide and organic peroxide.
Examples of the organic peroxide include t-butyl hydroperoxide, di-t-butyl peroxide, t-amyl hydroperoxide, cumene hydroperoxide, methylcyclohexyl hydroperoxide, tetralin hydroperoxide, isobutylbenzene hydroperoxide, ethyl naphthalene hydroperoxide. And peracetic acid. As the oxidizing agent, a mixture of two or more of the above-exemplified peroxides can be used.
Hydrogen peroxide may be commercially available, or may be produced from oxygen and hydrogen in the presence of a noble metal in the same reaction system as the oxidation reaction.
Preferable oxidizing agents include peroxides, more preferably hydrogen peroxide, and particularly preferably hydrogen peroxide aqueous solution having a concentration in the range of 0.0001% by weight or more and less than 100% by weight. It is done.

  The amount of the oxidizing agent used can be arbitrarily selected according to the type of olefin compound, reaction conditions, and the like. For example, 0.01 part by weight or more, more preferably 0.1 parts by weight with respect to 100 parts by weight of the olefin compound. It is more than part by weight. The upper limit of the amount of the oxidizing agent used can be, for example, 1000 parts by weight with respect to 100 parts by weight of the olefin compound, and a preferable upper limit is, for example, 100 parts by weight.

The olefin compound used in the oxidation reaction is a compound in which an optionally substituted hydrocarbyl group or hydrogen is bonded to a carbon atom constituting an olefin double bond.
Examples of the substituent of the hydrocarbyl group include a hydroxyl group, a halogen atom, a carbonyl group, an alkoxycarbonyl group, a cyano group, and a nitro group. Examples of the hydrocarbyl group include saturated hydrocarbyl groups, and examples of the saturated hydrocarbyl group include alkyl groups.
Specific examples of the olefin compound include alkene having 2 to 10 carbon atoms and cycloalkene having 4 to 10 carbon atoms.
Examples of the alkene having 2 to 10 carbon atoms include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, 2-butene, isobutene, 2-pentene, 3-pentene, 2-hexene and 3-hexene. 4-methyl-1-pentene, 2-heptene, 3-heptene, 2-octene, 3-octene, 2-nonene, 3-nonene, 2-decene, 3-decene and the like.
Examples of the cycloalkene having 4 to 10 carbon atoms include cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, and cyclodecene.
In the present invention, the olefin compound is preferably an alkene having 2 to 10 carbon atoms, more preferably an alkene having 2 to 5 carbon atoms, and particularly preferably propylene.

  In the oxidation reaction, the amount of the olefin compound can be arbitrarily selected according to the type, reaction conditions, etc., for example, 0.01 parts by weight or more with respect to 100 parts by weight of the total amount of the reaction solution for the oxidation reaction. More preferably, it is 0.1 parts by weight or more. The upper limit of the amount of the olefin compound can be 1000 parts by weight, preferably 100 parts by weight, with respect to 100 parts by weight of the total amount of the reaction solution.

It is preferable to use a solvent for the oxidation reaction. Examples of the solvent include water, an organic solvent, a mixture of both, and the like.
Examples of the organic solvent include alcohol solvents, ketone solvents, nitrile solvents, ether solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, ester solvents, and mixtures thereof.
Examples of the aliphatic hydrocarbon solvent include aliphatic hydrocarbons having 5 to 10 carbon atoms such as hexane and heptane. As an aromatic hydrocarbon solvent, C6-C15 aromatic hydrocarbon solvents, such as benzene, toluene, xylene, are mentioned, for example.
As an alcohol solvent, C1-C6 monohydric alcohol, C2-C8 glycol, etc. are mentioned, for example. The alcohol solvent is preferably an aliphatic alcohol having 1 to 8 carbon atoms, more preferably a monohydric alcohol having 1 to 4 carbon atoms such as methanol, ethanol, isopropanol and t-butanol, and further preferably t-butanol.
Examples of the nitrile solvent include C2-C4 alkyl nitriles such as acetonitrile, propionitrile, isobutyronitrile, butyronitrile, benzonitrile, and the like, and acetonitrile is preferable.
As the solvent used in the oxidation reaction, water, an alcohol solvent, a nitrile solvent, and a mixed solvent thereof are preferable from the viewpoint of catalytic activity and selectivity.

  In the oxidation reaction, the amount of the catalyst can be appropriately selected according to the type of the olefin compound. For example, the lower limit is 0.01 parts by weight, preferably 0 with respect to 100 parts by weight of the total amount of the solvent. 0.1 part by weight, more preferably 0.5 part by weight, and the upper limit may be, for example, 20 parts by weight, preferably 10 parts by weight, more preferably 8 parts by weight.

As a minimum of reaction temperature in an oxidation reaction, 0 ° C can be mentioned, for example, Preferably 40 ° C can be mentioned. As an upper limit, 200 degreeC can be mentioned, for example, Preferably 150 degreeC can be mentioned.
The lower limit of the reaction pressure of the oxidation reaction can be, for example, 0.1 MPa, preferably 1 MPa, and the upper limit can be, for example, 20 MPa, preferably 10 MPa. it can.

In the oxidation reaction, when the oxidizing agent is hydrogen peroxide, the hydrogen peroxide may be supplied by producing in the same reaction system as the oxidation reaction.
When the hydrogen peroxide is produced in the same reaction system as the oxidation reaction, it can be produced, for example, from oxygen and hydrogen in the presence of a noble metal catalyst.
Examples of the noble metal catalyst include noble metals such as palladium, platinum, ruthenium, rhodium, iridium, osmium and gold, or alloys or mixtures thereof. Preferable noble metals include palladium, platinum, and gold. A more preferred noble metal is palladium. As palladium, for example, a palladium colloid may be used (see, for example, JP-A-2002-294301, Example 1). As the noble metal catalyst, a noble metal compound that is converted into a noble metal by reduction in an oxidation reaction system may be used.

When palladium is used as the noble metal catalyst, metals other than palladium such as platinum, gold, rhodium, iridium, and osmium can be further mixed with palladium. Preferred metals other than palladium include gold and platinum.
Examples of the palladium compound include tetravalent palladium compounds such as sodium hexachloropalladium (IV) tetrahydrate and potassium hexachloropalladium (IV); palladium (II) chloride, palladium (II) bromide, palladium acetate (II), palladium acetylacetonate (II), dichlorobis (benzonitrile) palladium (II), dichlorobis (acetonitrile) palladium (II), dichloro (bis (diphenylphosphino) ethane) palladium (II), dichlorobis (triphenyl) Phosphine) palladium (II), dichlorotetraammine palladium (II), dibromotetraammine palladium (II), dichloro (cycloocta-1,5-diene) palladium (II), palladium trifluoroacetate (II) 2-valent palladium compounds such as are exemplified.

The noble metal is usually used by being supported on a carrier. The noble metal can be used by being supported on the catalyst, oxides such as silica, alumina, titania, zirconia, and niobium, hydrates such as niobic acid, zirconium acid, tungstic acid, titanic acid, carbon, and the like. It can also be used by being supported on a mixture. When a noble metal is supported in addition to the present catalyst, a carrier supporting the noble metal can be mixed with the present catalyst, and the mixture can be used as a catalyst.
When a catalyst other than the present catalyst is used as a support, carbon is a preferable support. Known carbon carriers include activated carbon, carbon black, graphite, carbon nanotubes and the like.

As a method for preparing a noble metal catalyst, for example, a method in which a noble metal compound is supported on a support and then reduced is known. For supporting the noble metal compound, a conventionally known method such as an impregnation method can be used.
As a reduction method, reduction may be performed using a reducing agent such as hydrogen, or reduction may be performed with ammonia gas generated during thermal decomposition in an inert gas atmosphere. The reduction temperature varies depending on the kind of the noble metal compound, but is preferably in the range of 100 to 500 ° C, more preferably in the range of 200 to 350 ° C.
The noble metal catalyst contains a noble metal, for example, in the range of 0.01 to 20% by weight, preferably in the range of 0.1 to 5% by weight.
The weight ratio of the noble metal to the catalyst (the weight of the noble metal / the weight of the catalyst) is preferably 0.01 to 100% by weight, more preferably 0.1 to 20% by weight.

In the oxidation reaction, when a buffering agent is present in the reaction system of the oxidation reaction, it is preferable because the conversion rate and yield of the olefin oxide per oxidizing agent tend to be further improved. Here, the buffering agent means a compound composed of an anion and a cation giving a pH buffering action.
The buffering agent is generally dissolved in the reaction system of the oxidation reaction. However, when hydrogen peroxide produced in the same reaction system is used as the oxidizing agent, a buffering agent is added to the precious metal catalyst in advance. Good. For example, there may be mentioned a method in which an ammine complex such as Pd tetraammine chloride is supported on a support by an impregnation method or the like and then reduced to leave ammonium ions and generate a buffer during the oxidation reaction.
Examples of the addition amount of the buffering agent include a range of 0.001 mmol / kg to 100 mmol / kg per 1 kg of the solvent.

As buffering agents, 1) sulfate ion, hydrogen sulfate ion, carbonate ion, hydrogen carbonate ion, phosphate ion, hydrogen phosphate ion, dihydrogen phosphate ion, hydrogen pyrophosphate ion, pyrophosphate ion, halogen ion, nitrate ion An anion selected from the group consisting of hydroxide ions and carboxylate ions having 1 to 10 carbon atoms, 2) ammonium, alkyl ammonium having 1 to 20 carbon atoms, alkylaryl ammonium having 7 to 20 carbon atoms, alkali metal, and Examples thereof include a buffer comprising a cation selected from the group consisting of alkaline earth metals.
Examples of the carboxylate ion include acetate ion, formate ion, acetate ion, propionate ion, butyrate ion, valerate ion, caproate ion, caprylate ion, caprate ion, and benzoate ion.
Examples of the alkylammonium include tetramethylammonium, tetraethylammonium, tetra-n-propylammonium, tetra-n-butylammonium, and cetyltrimethylammonium. Examples of alkali metal and alkaline earth metal cations are lithium cations. Sodium cation, potassium cation, rubidium cation, cesium cation, magnesium cation, calcium cation, strontium cation, barium cation and the like.
Preferable buffering agents include, for example, ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, ammonium hydrogen carbonate, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, ammonium hydrogen pyrophosphate, ammonium pyrophosphate, ammonium chloride, ammonium nitrate. An ammonium salt of inorganic acid such as ammonium salt and an ammonium salt of carboxylic acid such as ammonium acetate are preferable, and a preferable ammonium salt is ammonium dihydrogen phosphate.

（式中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、水素原子を表すかあるいは、Ｒ^１とＲ^２、あるいはＲ^３とＲ^４は、それぞれ独立に、その末端で結合し、それぞれが結合している炭素原子とともに、置換されていてもよいナフタレン環を表し、ＸおよびＹは同一または互いに相異なり、酸素原子もしくはＮＨ基を表す。）
のρ−キノイド化合物およびο−キノイド化合物が例示される。 When the oxidation reaction uses hydrogen peroxide synthesized from oxygen and hydrogen in the reaction system as an oxidizing agent, the selectivity of olefin oxide tends to increase by the presence of the quinoid compound in the reaction system of the oxidation reaction. This is preferable.
As a quinoid compound, following formula (1)

(Wherein R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom, or R ¹ and R ² , or R ³ and R ⁴ are each independently bonded at their ends, Along with the bonded carbon atom, it represents an optionally substituted naphthalene ring, and X and Y are the same or different from each other and represent an oxygen atom or an NH group.)
The ρ-quinoid compound and the o-quinoid compound are exemplified.

As a compound of Formula (1),
1) A quinone compound (1A) in which in formula (1), R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, and X and Y are both oxygen atoms,
2) In formula (1), R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, X is an oxygen atom, and Y is an NH group, a quinoneimine compound (1B),
3) In Formula (1), R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, and quinonediimine compound (1C) in which X and Y are NH groups is exemplified.

（式中、ＸおよびＹは式（１）において定義されたとおりであり、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８は、同一または互いに相異なり、水素原子、ヒドロキシル基もしくはアルキル基（例えば、メチル、エチル、プロピル、ブチル、ペンチル等のＣ_１−Ｃ_５アルキル基）を表す。） The quinoid compound of the formula (1) includes the following anthraquinone compound (2).

(Wherein X and Y are as defined in formula (1), R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different from each other, and are each a hydrogen atom, a hydroxyl group or an alkyl group (for example, C ₁ -C ₅ alkyl groups such as methyl, ethyl, propyl, butyl, pentyl)).

In formula (1) and formula (2), X and Y preferably represent an oxygen atom.
Examples of the quinoid compound include benzoquinone, naphthoquinone, anthraquinone, alkylanthraquinone compound, polyhydroxyanthraquinone, and 9,10-phenanthraquinone.
Examples of the alkylanthraquinone compound include 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, 2-methylanthraquinone, 2-butylanthraquinone, 2-t-amylanthraquinone, 2-isopropylanthraquinone, and 2-s. 2-alkylanthraquinone compounds such as butylanthraquinone or 2-s-amylanthraquinone; polyalkylanthraquinones such as 1,3-diethylanthraquinone, 2,3-dimethylanthraquinone, 1,4-dimethylanthraquinone, 2,7-dimethylanthraquinone Compounds.
Examples of the polyhydroxyanthraquinone include 2,6-dihydroxyanthraquinone.

Preferred quinoid compounds include anthraquinone and 2-alkylanthraquinone compounds (in formula (2), X and Y are oxygen atoms, R ⁵ is an alkyl group substituted at the 2-position, R ⁶ represents hydrogen, R ⁷ and R ⁸ represent a hydrogen atom).
As the usage-amount of the said quinoid compound, the range of 0.001 mmol / kg-500 mmol / kg can be mentioned per 1 kg of solvent.
A preferable amount of the quinoid compound is 0.01 mmol / kg to 50 mmol / kg.
In the olefin oxide production method of the present invention, it is also possible to simultaneously add a salt comprising ammonium, alkylammonium or alkylarylammonium to the reaction system of the oxidation reaction.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、ＸおよびＹは、前記式（１）に関して定義されたとおり。）

（式中、Ｘ、Ｙ、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８は前記式（２）に関して定義されたとおり。）
式（３）および式（４）において、ＸおよびＹは、好ましくは酸素原子を表す。
好ましいキノイド化合物のジヒドロ体としては、上述の好ましいキノイド化合物に対応するジヒドロ体が挙げられる。 The quinoid compound can also be prepared by oxidizing the dihydro form with oxygen or the like in the reaction system of the oxidation reaction. For example, hydroquinone or a compound in which a quinoid compound such as 9,10-anthracenediol is hydrogenated is added to the reaction system of the oxidation reaction, and oxidized with oxygen in the reactor to generate a quinoid compound. Good.
Examples of the dihydro form of the quinoid compound include compounds of the following formulas (3) and (4) which are dihydro forms of the compounds of the formulas (1) and (2).

(Wherein R ¹ , R ² , R ³ , R ⁴ , X and Y are as defined above for formula (1).)

(Wherein X, Y, R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined above for formula (2).)
In formula (3) and formula (4), X and Y preferably represent an oxygen atom.
Preferred dihydro forms of quinoid compounds include dihydro forms corresponding to the above-mentioned preferred quinoid compounds.

  The oxidation reaction can be applied to any chemical reaction process of continuous type, batch type, or semi-batch type, and is preferably performed in a batch type or a semi-batch type.

  In the case of a reaction in which an olefin compound is oxidized using a pre-produced peroxide, the reaction gas atmosphere is not limited.

  When hydrogen peroxide is produced from oxygen and hydrogen in the same reaction as the reaction system of the oxidation reaction, the partial pressure ratio of oxygen and hydrogen supplied into the reaction system is, for example, oxygen: hydrogen = 1: 50. A range of ˜50: 1, preferably a range of 1: 2 to 10: 1 can be mentioned. It is preferable that the partial pressure ratio of oxygen and hydrogen (oxygen / hydrogen) is 50/1 or less because the production rate of olefin oxide tends to be improved. Moreover, when the partial pressure ratio of oxygen and hydrogen (oxygen / hydrogen) is 1/50 or more, the by-product of the alkane compound in which the olefin compound is reduced tends to decrease, and the selectivity of the olefin oxide tends to improve. preferable.

Here, oxygen and hydrogen may be diluted. Examples of the gas used for dilution include nitrogen, argon, carbon dioxide, methane, ethane, and propane. Although there is no restriction | limiting in the density | concentration of the gas for dilution, if necessary, oxygen or hydrogen is diluted and the synthesis reaction of hydrogen peroxide is performed.
As oxygen, oxygen may be used as it is, or a mixed gas of oxygen such as air and the gas used for the dilution. As the oxygen gas, oxygen gas produced by an inexpensive pressure swing method can be used, and high-purity oxygen gas produced by cryogenic separation or the like can be used as necessary.

As reaction temperature in an oxidation reaction, the range of 0 degreeC-200 degreeC etc. can be mentioned, for example, Preferably the range of 40 degreeC-150 degreeC etc. are mentioned.
When the reaction temperature is 0 ° C. or higher, the reaction rate tends to be improved, and when the reaction temperature is 200 ° C. or lower, side reactions are suppressed and the alkylene oxide selectivity tends to be improved. preferable.

  The reaction pressure in the oxidation reaction can be, for example, under pressure in the range of 0.1 MPa to 20 MPa as a gauge pressure, and preferably under pressure in the range of 1 MPa to 10 MPa.

  After the oxidation reaction is completed, the olefin oxide can be extracted by, for example, distillation of the reaction product of the oxidation reaction.

Hereinafter, the present invention will be described with reference to examples.
<Analyzer in Examples>
(Elemental analysis method)
The weight of Ti (titanium atom) and Si (silicon atom) contained in the catalyst was determined by ICP emission analysis. That is, about 20 mg of a sample was weighed in a platinum crucible, and sodium carbonate was put on the sample, and then a melting operation was performed with a gas burner. After melting, the contents in the platinum crucible are heated and dissolved with pure water and nitric acid, and then the volume is adjusted with pure water. Then, this measurement solution is analyzed with an ICP emission analyzer (ICPS-8000 manufactured by Shimadzu Corporation). Quantification of each element was performed.

(Powder X-ray diffraction method (XRD))
The powder X-ray diffraction pattern of this catalyst was measured with the following apparatus and conditions.
Apparatus: RINT2500V manufactured by Rigaku Corporation
Radiation source: Cu Kα ray output 40kV-300mA
Scanning range: 2θ = 0.75-20 °
Scanning speed: 1 ° / min

(Ultraviolet visible absorption spectrum (UV-Vis))
The catalyst was thoroughly pulverized in an agate mortar and further pelletized (7 mmφ) to prepare a measurement sample, and the ultraviolet-visible absorption spectrum of the measurement sample was measured using the following apparatus and conditions.
Device: Diffuse reflection device (Playing Mantis manufactured by HARRICK)
Accessories: UV-visible spectrophotometer (V-7100 manufactured by JASCO)
Pressure: Atmospheric pressure Measured value: Reflectance data acquisition time: 0.1 seconds Band width: 2 nm
Measurement wavelength: 200 to 900 nm
Slit height: Half-open data capture interval: 1 nm
Baseline correction (reference): BaSO ₄ pellet (7mmφ)

(Bulk density measurement of this catalyst)
About 5 ml of the catalyst, which was well ground in a mortar, was accurately weighed and placed in a 10 ml graduated cylinder, and the graduated cylinder was vibrated until the volume of the catalyst remained unchanged. The bulk density (g / ml) of the catalyst was determined from the weighed weight (g) of the catalyst and the volume (ml) of the catalyst measured with the graduated cylinder scale.

Example 1
Piperidine (Wako Pure Chemical Industries, Ltd.) 899 g, ion-exchanged water 2402 g, TBOT (tetra-n-butyl orthotitanate, Wako Pure Chemical Industries, Ltd.) 46.4 g, boric acid (Wako Pure Chemical Industries, Ltd.) 565 g and fume A gel was obtained by dissolving 410 g of dosilica (cab-o-sil M7D, Cabot) in an autoclave while stirring at 25 ° C. The gel was further stirred for 1.5 hours and then the autoclave was sealed. Subsequently, the temperature of the gel was raised to 150 ° C. over 8 hours while stirring the gel, and then the suspension was obtained by maintaining the temperature at the same temperature for 120 hours. The obtained suspension solution was filtered, and then washed with water until the pH of the filtrate reached 10.3. The obtained solid was dried at 50 ° C. until no weight loss was observed, and 524 g of solid 1 was obtained.
After adding 3750 mL of 2M nitric acid and 9.5 g of TBOT (manufactured by Wako Pure Chemical Industries, Ltd.) to 75 g of the solid 1, the mixture was heated and refluxed for 20 hours. The resulting solid product is then filtered, washed with water until the pH of the filtrate is 5 or higher, and then the solid product is heated at 150 ° C. until no weight loss of the washed solid product is observed. While drying under vacuum, 59 g of white powder was obtained (Catalyst A). The X-ray diffraction pattern of this catalyst A has peaks of 12.3d / Å, 11.0d / Å, 9.0d / Å, 6.1d / Å, 3.9d / Å, and 3.4d / Å. Was confirmed, and the UV-visible absorption spectrum revealed that it was titanosilicate. The titanium content was 1.99% by weight by elemental analysis. Furthermore, the bulk density of the catalyst A was 0.10 g / ml.

(Example 2)
50 g of the catalyst A obtained in Example 1 was heated at 530 ° C. for 6 hours to obtain 45 g of a powdery catalyst B. The X-ray diffraction pattern of the obtained catalyst B has peaks of 12.3d / Å, 11.0d / Å, 9.0d / Å, 6.1d / Å, 3.9d / Å, and 3.4d / Å. Confirmed to have. The UV-visible absorption spectrum measurement result revealed that it was titanosilicate. Furthermore, the bulk density of the catalyst B was 0.11 g / ml.

(Example 3)
Piperidine (manufactured by Wako Pure Chemical Industries, Ltd.) 899 g, ion-exchanged water 2402 g, TBOT (manufactured by Wako Pure Chemical Industries, Ltd.) 46 g, boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) 565 g, fumed silica (cab-o-sil M7D, A gel was obtained by dissolving 410 g (manufactured by Cabot Corporation) in an autoclave while stirring at 25 ° C. The gel was further stirred for 1.5 hours, and then the autoclave was sealed. Subsequently, the temperature of the gel was raised to 145 ° C. over 8 hours while stirring the gel, and then held at the temperature for 120 hours to obtain a suspension solution. The obtained suspension solution was filtered, and then washed with water until the pH of the filtrate reached 10.5. The obtained solid was dried at 50 ° C. until no weight loss was observed, and 508 g of solid 2 was obtained.
After adding 750 mL of 2M nitric acid and 1.9 g of TBOT (manufactured by Wako Pure Chemical Industries, Ltd.) to 15 g of the solid 2, the mixture was heated and refluxed for 20 hours. The resulting solid product is then filtered, washed with water until the pH of the filtrate is 5 or higher, and then the solid product is heated at 150 ° C. until no weight loss of the washed solid product is observed. While being vacuum dried, 11.3 g of white powder was obtained (Catalyst C). The X-ray diffraction pattern of this catalyst C has peaks of 12.3d / Å, 11.0d / Å, 9.0d / Å, 6.1d / Å, 3.9d / Å, and 3.4d / Å. Was confirmed, and the UV-visible absorption spectrum revealed that it was titanosilicate. Moreover, the titanium content was 1.89% by weight by elemental analysis. Furthermore, the bulk density of the catalyst C was 0.09 g / ml.

Example 4
A gel was obtained by dissolving 300 g of piperidine (manufactured by Guangei Chemical Industry Co., Ltd.), 600 g of ion-exchanged water, and 80 g of catalyst B obtained in Example 2 while stirring at 25 ° C. in an autoclave. The gel was further stirred for 1.5 hours, and then the autoclave was sealed. Subsequently, the temperature of the gel was raised to 160 ° C. over 4 hours while stirring the gel, and then kept at the temperature for 24 hours to obtain a suspension solution. The obtained suspension solution is filtered, then washed with water until the pH of the filtrate reaches 10.5, and then the solid product is heated at 150 ° C. until no weight loss of the washed solid product is observed. While drying under vacuum, 79 g of white powder was obtained (Catalyst D). The X-ray diffraction pattern of the catalyst D has peaks of 12.3d / Å, 11.1d / Å, 9.0d / Å, 6.1d / Å, 3.9d / Å, and 3.4d / Å. Was confirmed, and the UV-visible absorption spectrum revealed that it was titanosilicate. Moreover, the titanium content was 2.08% by weight by elemental analysis. Furthermore, the bulk density of the catalyst D was 0.09 g / ml.

(Example 5)
The silylation of the catalyst D was carried out with reference to the method of JP-A No. 2003-326171. That is, 1.0 g of 1,1,1,3,3,3-hexamethyldisilazane (manufactured by Wako Pure Chemical Industries, Ltd.), 100 mL of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.5 g of catalyst D were mixed and heated. The silylation was performed by refluxing for 3 hours. Furthermore, after filtering the obtained reaction mixture, the obtained solid was washed with 500 mL of acetone and 1 L of a water / acetonitrile (= 1/4, mass ratio) mixed solvent in this order, and the solid after washing was reduced in mass. The mixture was vacuum-dried at 150 ° C. until disappearance gave 0.50 g of white powder (Catalyst E). The X-ray diffraction pattern of this catalyst E has peaks of 12.5 d / Å, 11.2 d / Å, 9.1 d / Å, 6.2 d / Å, 3.9 d / Å, 3.4 d / Å. Was confirmed, and the UV-visible absorption spectrum revealed that it was titanosilicate. Further, the bulk density of the catalyst E was 0.08 g / ml.

(Reference Example 1)
The Ti-MWW precursor was synthesized by the same method as Chemistry Letters 774-775 (2000). Specifically, 200 g of piperidine (manufactured by Wako Pure Chemical Industries, Ltd.) and 564 g of ion-exchanged water were mixed in a 2 L resin beaker under an air atmosphere at 25 ° C. to obtain an aqueous piperidine solution. The aqueous solution was divided into two portions of 382 g to prepare a piperidine aqueous solution (1) and a piperidine aqueous solution (2).
The gel was obtained by stirring piperidine aqueous solution (1), TBOT (manufactured by Wako Pure Chemical Industries, Ltd.) 5.6 g, fumed silica (cab-o-sil M7D, manufactured by Cabot) 49.5 g at 25 ° C. in an air atmosphere. (1) was obtained. The gel was allowed to stir for 1 hour.
On the other hand, an aqueous piperidine solution (2), 136.5 g of boric acid (manufactured by Wako Pure Chemical Industries, Ltd.), and 49.5 g of fumed silica (cab-o-sil M7D, manufactured by Cabot Corporation) are stirred in an Air atmosphere at 25 ° C. This gave a gel (2). The gel was allowed to stir for 1 hour.
Gel (1) and gel (2) were mixed in an autoclave under an Air atmosphere at 25 ° C., and further stirred for 1.5 hours to obtain gel (3). The composition (molar) ratio of the mixture in the gel (3) was SiO ₂ : TiO ₂ : B ₂ O ₃ : piperidine: H ₂ O = 1: 0.01: 0.67: 1.4: 19. . The autoclave was sealed, heated up to a temperature of 130 ° C. over 5.5 hours with stirring at a rotational speed of 100 rpm, and then kept at that temperature for 24 hours. After maintaining at 130 ° C., the temperature of the contents was increased to 150 ° C. over 1 hour, and then maintained at that temperature for 24 hours. After maintaining at 150 ° C., the temperature of the contents was raised to 170 ° C. over 1 hour, and then maintained at that temperature for 120 hours to obtain a suspension solution. The obtained suspension solution was filtered, and then washed with water until the pH of the filtrate reached 10.0. The obtained solid was dried at 50 ° C. until no weight loss was observed, and 117 g of solid 3 was obtained.
60 mL of 2M nitric acid was added to 33 g of the solid 33, and the mixture was kept at 100 ° C. for 20 hours with stirring. Next, the obtained solid product was filtered, washed with water until the pH of the filtrate reached 5 or more, and dried at 150 ° C. until no weight loss was observed, and 2.3 g of white powder was obtained (catalyst) 1). The X-ray diffraction pattern of the catalyst 1 has peaks of 12.3 d / Å, 11.0 d / Å, 8.8 d / Å, 6.1 d / Å, 3.9 d / Å, and 3.4 d / Å. Was confirmed, and the UV-visible absorption spectrum revealed that it was titanosilicate. Moreover, the titanium content was 0.76% by weight by elemental analysis. Furthermore, the bulk density of the catalyst 1 was 0.18 g / ml.

(Reference Example 2)
Piperidine (manufactured by Wako Pure Chemical Industries, Ltd.) 899 g, ion-exchanged water 2402 g, TBOT (manufactured by Wako Pure Chemical Industries, Ltd.) 47 g, boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) 565 g, fumed silica (cab-o-sil M7D, A gel was obtained by dissolving 410 g (manufactured by Cabot Corporation) in an autoclave while stirring at 25 ° C. The gel was further stirred for 1.5 hours, and then the autoclave was sealed. Subsequently, the temperature of the gel was raised to 160 ° C. over 8 hours while stirring the gel, and then held at the temperature for 120 hours to obtain a suspension solution. The obtained suspension solution was filtered, and then washed with water until the pH of the filtrate was 10.4. The obtained solid content was dried at 50 ° C. until no weight loss was observed, and 508 g of solid 4 was obtained.
3750 mL of 2M nitric acid and 9.5 g of TBOT (manufactured by Wako Pure Chemical Industries, Ltd.) were added to 75 g of the solid 4 and then heated and refluxed for 20 hours. The resulting solid product is then filtered, washed with water until the pH of the filtrate is 5 or higher, and then the solid product is heated to 150 ° C. until no weight loss of the washed solid product is observed. While drying under vacuum, 56 g of white powder was obtained (Catalyst 2). The X-ray diffraction pattern of the catalyst 2 has peaks of 12.3d / Å, 11.0d / Å, 9.0d / Å, 6.1d / Å, 3.9d / Å, and 3.4d / Å. Was confirmed, and the UV-visible absorption spectrum revealed that it was titanosilicate. Moreover, the titanium content was 1.89% by weight by elemental analysis. Furthermore, the bulk density of the catalyst 2 was 0.35 g / ml.

(Reference Example 3)
50 g of Catalyst 1 obtained in Reference Example 1 was heated at 530 ° C. for 6 hours to obtain 45 g of Catalyst 3. The X-ray diffraction pattern of the catalyst 3 has peaks of 12.3d / Å, 11.0d / Å, 8.9d / Å, 6.1d / Å, 3.9d / Å, and 3.4d / Å. Was confirmed, and the UV-visible absorption spectrum revealed that it was titanosilicate. The UV-visible absorption spectrum measurement result showed that it was titanosilicate. Furthermore, the bulk density of the catalyst 3 was 0.35 g / ml.

(Reference Example 4)
Piperidine (manufactured by Wako Pure Chemical Industries, Ltd.) 899 g, ion-exchanged water 2402 g, TBOT (manufactured by Guangei Chemical Industry Co., Ltd.) 899 g, boric acid (manufactured by Yoneyama Chemical Co., Ltd.) 565 g, fumed silica (cab-o-sil M7D, A gel was obtained by dissolving 410 g (manufactured by Cabot Corporation) in an autoclave while stirring at 25 ° C. The gel was further stirred for 1.5 hours, and then the autoclave was sealed. Subsequently, the temperature of the gel was raised to 160 ° C. over 8 hours while stirring the gel, and then held at the temperature for 120 hours to obtain a suspension solution. The obtained suspension solution was filtered, and then washed with water until the pH of the filtrate reached 10.5. The obtained solid was dried at 50 ° C. until no weight loss was observed, and 508 g of solid 5 was obtained.
After adding 3750 mL of 2M nitric acid to 75 g of the solid 5, the mixture was heated and refluxed for 20 hours. The resulting solid product is then filtered, washed with water until the pH of the filtrate is 5 or higher, and then the solid product is heated to 150 ° C. until no weight loss of the washed solid product is observed. While being vacuum-dried, 52 g of white powder was obtained (Catalyst 4). The X-ray diffraction pattern of the catalyst 4 has peaks of 12.3 d / Å, 11.0 d / Å, 8.9 d / Å, 6.1 d / Å, 3.9 d / Å, and 3.4 d / Å. Was confirmed, and the UV-visible absorption spectrum revealed that it was titanosilicate. Moreover, the titanium content was 1.80% by weight by elemental analysis. Furthermore, the bulk density of the catalyst 4 was 0.40 g / ml.

(Reference Example 5)
50 g of the catalyst 4 obtained in Reference Example 4 was heated at 530 ° C. for 6 hours to obtain 45 g of solid 6. When the X-ray diffraction pattern of the obtained solid 6 was measured, it was confirmed that the solid had an MWW structure by comparing with FIG. 2 in JP-A-2005-262164. The UV-visible absorption spectrum measurement result revealed that it was titanosilicate.
A gel was obtained by dissolving 45 g of piperidine (manufactured by Wako Pure Chemical Industries, Ltd.), 90 g of ion-exchanged water, and 15 g of solid 615 in an autoclave while stirring at 25 ° C. The gel was further stirred for 1.5 hours, and then the autoclave was sealed. Subsequently, the temperature of the gel was raised to 160 ° C. over 4 hours while stirring the gel, and then kept at the temperature for 16 hours to obtain a suspension solution. The obtained suspension solution was filtered and washed with water until the pH of the filtrate reached 9.3. The obtained solid was dried at 50 ° C. until no weight loss was observed, and 13.5 g of catalyst 5 was obtained. The X-ray diffraction pattern of the catalyst 5 has peaks of 12.3d / Å, 11.1d / Å, 9.0d / Å, 6.1d / Å, 3.9d / Å, and 3.4d / Å. Was confirmed, and the UV-visible absorption spectrum revealed that it was titanosilicate. Moreover, the titanium content was 1.80% by weight by elemental analysis. Furthermore, the bulk density of the catalyst 5 was 0.39 g / ml.

(Hydrogen peroxide treatment)
The titanosilicate obtained in Examples and Reference Examples of the present invention was contacted with hydrogen peroxide according to the following method.
A mixture of 0.1 g of titanosilicate and 100 g of a solution of water / acetonitrile = 1/4 (weight ratio) containing 0.1% by weight of hydrogen peroxide was stirred at room temperature (about 20 ° C.) for 1 hour. Thereafter, the mixture was filtered, and the obtained cake was washed with 500 mL of water to obtain a titanosilicate treated with hydrogen peroxide.

(Propylene oxide production example 1: Example 6)
Aqueous solution containing 30% by weight of hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.), acetonitrile (manufactured by Nacalai Tesque) and ion-exchanged water are mixed, and an acetonitrile / water mixture containing 0.5% by weight of hydrogen peroxide is mixed. A solvent (acetonitol / water = 4/1 (weight ratio)) solution was prepared. Separately, 60 g of the prepared solution and 0.010 g of the catalyst A ′ obtained by treating the catalyst A obtained in Example 1 with the hydrogen peroxide were charged into a 100 mL stainless steel autoclave. The autoclave was then transferred to an ice bath and charged with 1.2 g of propylene. Further, the pressure in the autoclave was increased to 2 MPa (gauge pressure) with argon. While stirring the mixed solution in the autoclave, the temperature was raised to 60 ° C. over 15 minutes, and the mixture was stirred at the same temperature for 1 hour. Next, stirring was stopped and the autoclave was cooled with ice.
After cooling with ice, the resulting mixture was analyzed by gas chromatography. The yield of propylene oxide per hydrogen peroxide amount was 49%.

(Propylene oxide production example 2: Example 7)
Propylene oxide was produced in the same manner as in Example 6 except that the catalyst B ′ obtained by treating the catalyst B obtained in Example 2 with hydrogen peroxide instead of the catalyst A ′ was used. As a result, the yield of propylene oxide per amount of hydrogen peroxide was 54%.

(Propylene oxide production example 3: Example 8)
The same procedure as in Example 6 was performed except that the catalyst C ′ obtained by treating the catalyst C obtained in Example 3 with hydrogen peroxide instead of the catalyst A ′ was used. As a result, the yield of propylene oxide per amount of hydrogen peroxide was 51%.

(Propylene oxide production example 4: Example 9)
Propylene oxide was produced in the same manner as in Example 6 except that the catalyst D ′ obtained by treating the catalyst D obtained in Example 4 with hydrogen peroxide instead of the catalyst A ′ was used. As a result, the yield of propylene oxide per amount of hydrogen peroxide was 63%.

(Propylene oxide production example 5: Example 10)
Propylene oxide was produced in the same manner as in Example 6 except that the catalyst E ′ obtained by treating the catalyst E obtained in Example 5 with hydrogen peroxide instead of the catalyst A ′ was used. As a result, the yield of propylene oxide per amount of hydrogen peroxide was 77%.

(Reference Production Example 1 of Propylene Oxide 1: Use of Catalyst 1 of Reference Example 1)
Propylene oxide was produced in the same manner as in Example 6 except that 0.020 g of catalyst 1 obtained in Reference Example 1 was used instead of 0.010 g of catalyst A ′. As a result, the yield of propylene oxide per amount of hydrogen peroxide was 20%.

(Reference Production Example 2 of Propylene Oxide: Use of Catalyst Treated with Hydrogen Peroxide from Catalyst 1 of Reference Example 1)
Propylene oxide was produced in the same manner as in Example 6 except that the catalyst 1 ′ obtained by treating the catalyst 1 obtained in Reference Example 1 with hydrogen peroxide instead of the catalyst A ′ was used. As a result, the yield of propylene oxide per amount of hydrogen peroxide was 29%.

(Reference Production Example 3 of Propylene Oxide: Use of Catalyst Treated with Hydrogen Peroxide from Catalyst 2 of Reference Example 2)
Propylene oxide was produced in the same manner as in Example 6 except that the catalyst 2 ′ obtained by treating the catalyst 2 obtained in Reference Example 2 with hydrogen peroxide instead of the catalyst A ′ was used. As a result, the yield of propylene oxide per amount of hydrogen peroxide was 42%.

(Reference Production Example 4 of Propylene Oxide: Use of Catalyst Treated with Hydrogen Peroxide from Catalyst 3 of Reference Example 3)
Propylene oxide was produced in the same manner as in Example 6 except that the catalyst 3 ′ obtained by hydrogen peroxide treatment of the catalyst 3 obtained in Reference Example 3 was used instead of the catalyst A ′. As a result, the yield of propylene oxide per amount of hydrogen peroxide was 38%.

(Reference Production Example 5 of Propylene Oxide: Use of Catalyst Treated with Hydrogen Peroxide of Catalyst 4 of Reference Example 4)
Propylene oxide was produced in the same manner as in Example 6 except that the catalyst 4 ′ obtained by treating the catalyst 4 obtained in Reference Example 4 with hydrogen peroxide instead of the catalyst A ′ was used. As a result, the yield of propylene oxide per amount of hydrogen peroxide was 43%.

(FE-SEM observation of catalyst A and catalyst 1)
Electron micrographs of the catalyst A obtained in Example 1 and the catalyst 1 obtained in Reference Example 1 were taken under the following measurement conditions. FIG. 1 shows that the catalyst A is hollow secondary particles, and FIG. 2 shows that the secondary particles of the catalyst 1 are simply aggregated primary particles.
(Measurement condition)
Measuring device: Field Emission Scanning Electron Microscope (FE-SEM) S-5500 manufactured by Hitachi High-Technologies Corporation
Observation conditions: A dark field scanning transmission image (STEM-DF image) is observed at an acceleration voltage of 30 kV.
Pretreatment method: The sample is mixed and deaerated in room temperature curing type epoxy resin (epocure) and embedded. A section with a film thickness of 80 to 100 nm was prepared with a microtome (LEICA ultramicrotome EMUC6) (room temperature wet) and collected on a Cu mesh for observation.

  According to the present invention, a novel titanosilicate can be provided as an olefin oxide catalyst having a better yield per oxidant.

Claims (13)

A titanosilicate having an X-ray diffraction pattern having the following value and a bulk density of 0.05 to 0.15 g / ml.
X-ray diffraction pattern lattice spacing d / ｄ (angstrom)
12.4 ± 0.8
10.8 ± 0.5
9.0 ± 0.3
6.0 ± 0.3
3.9 ± 0.1
3.4 ± 0.1   The titanosilicate according to claim 1, which has a bulk density of 0.08 to 0.11 g / ml. It has the following 1st process and 2nd process, The manufacturing method of the titanosilicate characterized by the above-mentioned.
First step: A step of obtaining a solid by heating a mixture containing a structure-directing agent, a compound containing a group 13 element of the periodic table, a titanium-containing compound, a silicon-containing compound and water under a temperature condition of less than 155 ° C.
Second step: A step of bringing at least one selected from the group consisting of an inorganic acid and a titanium-containing compound into contact with the solid obtained in the first step.   The method for producing a titanosilicate according to claim 3, wherein the compound containing a Group 13 element in the periodic table is a boron-containing compound.   5. The method for producing titanosilicate according to claim 3 or 4, wherein the structure directing agent is piperidine or hexamethyleneimine.   The manufacturing method according to any one of claims 3 to 5, further comprising a third step of heating the titanosilicate obtained in the second step in a temperature range of 250 to 1000 ° C.   The manufacturing method according to any one of claims 3 to 6, further comprising a fourth step of contacting the titanosilicate obtained in the second step or the third step with the structure directing agent.   The production method according to any one of claims 3 to 7, further comprising a fifth step of silylating the titanosilicate obtained in the second step, the third step or the fourth step with a silylating agent.   The manufacturing method according to any one of claims 3 to 8, further comprising a sixth step of contacting the titanosilicate obtained in the second step, the third step, the fourth step or the fifth step with hydrogen peroxide.   The titanosilicate obtained with the manufacturing method in any one of Claims 3-9.   A catalyst for producing olefin oxide comprising the titanosilicate according to claim 1, 2 or 10.   The manufacturing method of the olefin oxide including the process of oxidizing an olefin compound with an oxidizing agent in presence of the catalyst of Claim 11.   The method for producing an olefin oxide according to claim 12, wherein the olefin compound is propylene and the oxidizing agent is hydrogen peroxide.

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