JP2012116758A - Method for producing olefin oxide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve a problem with a conventional method for producing olefin oxide wherein hydrogen peroxide can be left without being perfectly consumed depending on reaction conditions.SOLUTION: The method for producing olefin oxide comprises steps of: [1] reacting hydrogen peroxide with olefin in the presence of titanosilicate and a solvent; and [2] bringing a substance containing at least one element selected from the group consisting of manganese and platinum group elements into contact with a reactant obtained in the above step.

Description

  The present invention relates to a method for producing olefin oxide and the like.

  As a method for producing olefin oxide such as propylene oxide, for example, a method of reacting olefin such as propylene with hydrogen peroxide in the presence of titanosilicate and a solvent is known (for example, Non-Patent Document 1).

Hiroaki Abekawa, Masaru Ishino, Direct Propylene Oxide Synthesis Using Modified Titanosilicate Catalyst, 89th Catalysis Conference, Conference A Proceedings, March 20, 2002, p. 65, 2P13

  In the above olefin oxide production method, depending on the reaction conditions, hydrogen peroxide may remain without being completely consumed.

Under such circumstances, the present inventors diligently studied, and as a result, reached the following present invention.
<1> [1] A step of reacting hydrogen peroxide with an olefin in the presence of titanosilicate and a solvent, and
[2] A step of bringing the reactant obtained by the above step into contact with a substance containing at least one element selected from the group consisting of manganese and a platinum group element;
The manufacturing method of the olefin oxide characterized by including.
<2> The method according to <1>, wherein the solvent is a mixed solvent of an organic solvent and water.
<3> The method according to <2>, wherein the organic solvent is acetonitrile.

<4> The production method according to any one of <1> to <3>, wherein the titanosilicate is a layered titanosilicate having pores having an oxygen 12-membered ring or more.
<5> The method according to any one of <1> to <4>, wherein the titanosilicate is a Ti-MWW precursor.

<6> The method according to any one of <1> to <5>, wherein the substance is a compound containing manganese or a platinum group element, or a simple substance containing a platinum group element.
<7> The method according to any one of <1> to <5>, wherein the substance is manganese dioxide.
<8> The method according to any one of <1> to <5>, wherein the substance is a substance containing at least one element selected from the group consisting of rhodium, palladium, iridium, and platinum.
<9> The method according to any one of <1> to <5>, wherein the substance is a substance containing palladium or platinum.

<10> The method according to any one of <1> to <9>, wherein the substance is a substance supported on a carrier.
<11> The method according to <10>, wherein the carrier is activated carbon.

<12> A peroxide comprising a step of bringing a substance containing at least one element selected from the group consisting of manganese and a platinum group element into contact with a solution containing an olefin oxide, hydrogen peroxide, and a solvent. How to remove hydrogen.

  According to the production method of the present invention, it is possible to provide an olefin oxide with little residual hydrogen peroxide.

One embodiment of the olefin oxide manufacturing apparatus of this invention.

  The present invention includes [1] a step of reacting hydrogen peroxide with an olefin in the presence of titanosilicate and a solvent (hereinafter sometimes referred to as a reaction step), and [2] a reaction obtained by the above step. Including a step of bringing a substance into contact with a substance containing at least one element selected from the group consisting of manganese and a platinum group element (hereinafter may be referred to as the present substance) (hereinafter may be referred to as a contact process) It is a manufacturing method of the olefin oxide characterized by the above-mentioned.

The olefin used in the reaction step is an alkene, cycloalkene, a compound in which the hydrogen atom contained in the alkene may be substituted with a substituent, or a hydrogen atom contained in the cycloalkene may be substituted with a substituent. Means a compound.
Examples of the substituent include a hydroxyl group, a halogen atom, a carbonyl group, an alkoxycarbonyl group, a cyano group, and a nitro group.
Specific examples of the olefin 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, 3-hexene, Examples include 4-methyl-1-pentene, 2-heptene, 3-heptene, 2-octene, 3-octene, 2-nonene, 3-nonene, 2-decene and 3-decene.
Examples of the cycloalkene having 4 to 10 carbon atoms include cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, and cyclodecene.
A more preferred olefin is propylene.

Examples of propylene include those produced by pyrolysis, heavy oil catalytic cracking, or methanol catalytic reforming. Examples of the propylene include purified propylene and crude propylene that has not undergone a purification step.
Preferable propylene purity is, for example, 90% by volume or more, and preferably 95% by volume or more. Examples of the impurities contained in propylene include propane, cyclopropane, methylacetylene, propadiene, butadiene, butane, butene, ethylene, ethane, methane, hydrogen, and the like.

  The amount of olefin used in the reaction step varies depending on the type and reaction conditions, but is preferably at least 0.01 parts by weight, more preferably 100 parts by weight of the total amount of solvents used in the reaction step. Is at least 0.1 parts by weight.

  Examples of the shape of the olefin used in the reaction step include gaseous and liquid forms. Here, examples of the liquid include those in which the olefin is liquid alone, for example, a mixed solution in which the olefin is dissolved in an organic solvent or a mixed solvent of an organic solvent and water. Examples of the gaseous state include gaseous olefins such as a mixed gas of gaseous components such as nitrogen gas and hydrogen gas and gaseous olefins.

Examples of the titanosilicate used in the reaction step include those in which a part of Si in the porous silicate (SiO ₂ ) is replaced by Ti. Ti of titanosilicate is entered SiO ₂ in the backbone, that Ti is in the SiO ₂ in the skeleton can be easily confirmed by a peak in 210nm~230nm in ultraviolet-visible absorption spectrum. In addition, Ti in TiO ₂ is usually 6-coordinated, but Ti in titanosilicate is 4-coordinated. Therefore, it can be easily confirmed by measuring the coordination number by titanium K-shell XAFS analysis or the like.

Examples of the titanosilicate include crystalline titanosilicate, layered titanosilicate, mesoporous titanosilicate, and the like.
Examples of the crystalline titanosilicate include a structure code of IZA (International Zeolite Society), TS-2 having an MEL structure, for example, Ti-ZSM-12 having an MTW structure (for example, Zeolites 15, 236-242, (Described in (1995)), for example, Ti-Beta having a BEA structure (for example, described in Journal of Catalysis 199, 41-47, (2001)), for example, Ti-MWW having an MWW structure. (For example, those described in Chemistry Letters 774-775, (2000)), for example, Ti-UTD-1 having a DON structure (for example, those described in Zeolites 15, 519-525, (1995)), etc. Can be mentioned.
Examples of layered titanosilicates include Ti-MWW precursors (for example, those described in Japanese Patent Publication No. 2003-32745), Ti-YNU-1 (for example, Angewandte Chemie International Edition 43, 236-240, (2004)). And titanosilicate having a structure in which the layers of the MWW structure are widened.
Mesoporous titanosilicate means titanosilicate having regular pores of 2 nm to 10 nm, and Ti-MCM-41 (for example, those described in Microporous Materials 10, 259-271, (1997)), Ti -MCM-48 (for example, described in Chemical Communications 145-146, (1996)), Ti-SBA-15 (for example, described in Chemistry of Materials 14, 1657-1664, (2002)), etc. Can be mentioned.
In addition, titanosilicate having characteristics of both mesoporous titanosilicate and titanosilicate zeolite such as Ti-MMM-1 (for example, those described in Microporous and Mesoporous Materials 52, 11-18, (2002)). Are also illustrated.

  As the titanosilicate used in the reaction step, crystalline titanosilicate or lamellar titanosilicate having pores with 12 or more oxygen rings is preferable. Examples of the crystalline titanosilicate having pores with 12 or more oxygen rings include Ti-ZSM-12, Ti-Beta, Ti-MWW, and Ti-UTD-1. Ti-MWW precursor and Ti-YNU-1 are mentioned as the layered titanosilicate having pores with 12 or more oxygen rings. More preferred titanosilicates include Ti-MWW and Ti-MWW precursors.

The titanosilicate used in the reaction process uses a structure-directing agent, hydrolyzes titanium compounds and silicon compounds, and improves crystallization, layering or pore regularity by hydrothermal synthesis etc. as necessary. Thereafter, those prepared by a method of removing the structure directing agent by baking or extraction are preferred.
Specifically, a boron compound, a silicon compound, and a structure directing agent are mixed in a closed container such as an autoclave, and a gauge pressure of 0 to 10 MPa in a temperature range of 0 ° C. to 250 ° C., preferably 50 ° C. to 200 ° C. The Ti-MWW precursor obtained by heating and pressurizing to the extent is separated by filtration, and further washed with water or the like as necessary. Washing may be appropriately adjusted as necessary while observing the amount of the washing liquid or the pH of the washing filtrate. The Ti-MWW precursor obtained by the above preparation method was further calcined at 500 to 800 ° C. to dehydrate and condense the layers to obtain Ti-MWW, and again in the presence of a structure-directing agent and water, 0 ° C. to A method of heating and pressurizing at a gauge pressure of about 0 to 10 MPa in a temperature range of 250 ° C., preferably 50 ° C. to 200 ° C. can be mentioned. The titanosilicate obtained by such a method becomes a Ti-MWW precursor again.

Here, the structure directing agent is capable of forming a zeolite having an MWW structure, such as piperidine, hexamethyleneimine, adamantyltrimethylammonium salt (for example, adamantyltrimethylammonium hydroxide, adamantyltrimethylammonium iodide, etc. ), Octyltrimethylammonium salt (for example, octyltrimethylammonium hydroxide, octyltrimethylammonium bromide, etc.). These compounds may be used singly or in combination of two or more at an arbitrary ratio.
Preferred structure directing agents are piperidine and hexamethyleneimine.
The amount of the structure directing agent to be used is, for example, 0.001 to 100 parts by weight, preferably 0.1 to 10 parts by weight with respect to 1 part by weight of the total of the boron compound and the silicon compound.

  Examples of the titanium compound include titanium alkoxides such as tetra-n-butyl orthotitanate, peroxytitanates such as tetra-n-butylammonium peroxytitanate, titanium halides such as titanium tetrachloride, titanium acetate, titanium nitrate, Titanium compounds such as titanium sulfate, titanium phosphate, titanium perchlorate, and titanium dioxide are exemplified, and titanium alkoxide is preferable. The amount of the titanium compound used may be in the range of 0.001 to 10 parts by weight, preferably 0.01 to 2 parts by weight, with respect to 1 part by weight of the boron compound. Is mentioned.

Examples of the silicon compound include tetraalkyl orthosilicates such as tetraethyl orthosilicate, silica, and the like.
An example of the boron compound is boric acid.
The boron compound and the silicon compound may be used in approximately the same amount.

The titanosilicate used in the reaction step may be silylated using a silylating agent such as 1,1,1,3,3,3-hexamethyldisilazane.
In addition, titanosilicate is preferably mixed with hydrogen peroxide before being subjected to the reaction step.

  The amount of titanosilicate used in the reaction step can be appropriately selected according to the reaction mode. For example, in the case of the slurry complete mixing mode, 0.001 to 50 parts per 100 parts by weight of the solvent in the reaction vessel. The range of weight part can be mentioned, Preferably, the range of 0.1-10 weight part is mentioned.

Examples of the solvent used in the reaction step include water, an organic solvent, or a mixed solvent thereof, and a mixed solvent of water and an organic solvent is preferable.
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.
As an alcohol solvent, C1-C8 aliphatic alcohols, such as methanol, ethanol, isopropanol, and t-butanol; For example, C2-C8 glycols, such as ethylene glycol and propylene glycol, etc. are mentioned. As a preferable alcohol solvent, C1-C4 monohydric alcohol etc. can be mentioned, for example, More preferably, t-butanol etc. are mentioned.
As said aliphatic hydrocarbon solvent, C5-C10 aliphatic hydrocarbon solvents, such as hexane and heptane, are mentioned, for example. As an aromatic hydrocarbon solvent, C6-C15 aromatic hydrocarbon solvents, such as benzene, toluene, xylene, are mentioned, for example.

Examples of the nitrile solvent include C2-C4 alkyl nitriles such as acetonitrile, propionitrile, isobutyronitrile, and butyronitrile, benzonitrile, and the like, and preferably acetonitrile.
The solvent used in the reaction step is preferably a monohydric alcohol having 1 to 4 carbon atoms, acetonitrile or the like from the viewpoints of catalyst activity and selectivity.
Examples of acetonitrile include crude acetonitrile and purified acetonitrile produced as a by-product in the acrylonitrile production process.
Examples of impurities other than acetonitrile contained in the crude acetonitrile include water, acetone, acrylonitrile, oxazole, allyl alcohol, propionitrile, hydrocyanic acid, ammonia, copper, and iron. The amount of copper and iron contained in the crude acetonitrile is preferably a trace amount of 1% by weight or less. Examples of the purity of acetonitrile include 95% by weight or more, preferably 99% by weight or more, and more preferably 99.9% by weight or more of purified acetonitrile.

The weight ratio of water and the organic solvent in the mixed solvent of water and the organic solvent can include, for example, a range of 0: 100 to 50:50, preferably a range of 10:90 to 40:60. It is done.
As a usage-amount of a solvent, the range of 0.02-70 weight part etc. can be mentioned with respect to 1 weight part of olefins, Preferably, it is 0.2-20 weight part, More preferably, it is 1-10. For example, the range of parts by weight.

As the hydrogen peroxide used in the reaction process, a commercially available product may be used, and as will be described later, it is prepared from oxygen and hydrogen in the presence of a noble metal catalyst (hereinafter referred to as a hydrogen peroxide preparation process). It may be. Moreover, hydrogen peroxide may be supplied in the state dissolved in the said solvent, such as water and acetonitrile, for example.
Examples of the content of hydrogen peroxide with respect to 100 parts by weight of the reaction solution in the reaction step include a range of 0.0001 to 90 parts by weight, preferably 0.001 to 5 parts by weight. The range etc. are mentioned. Examples of the amount of hydrogen peroxide relative to the olefin include a range of olefin: hydrogen peroxide = 1000: 1 to 1: 1000 (molar ratio).

  The noble metal catalyst in the hydrogen peroxide preparation step includes, for example, noble metals such as palladium, platinum, ruthenium, rhodium, iridium, osmium, gold, or alloys or mixtures thereof. Preferable noble metals include, for example, palladium, platinum, gold and the like, and an even more preferred noble metal is palladium. Examples of palladium include palladium compounds such as palladium colloid (see, for example, JP-A-2002-294301, Example 1). In addition, when using a palladium compound as this noble metal catalyst, noble metals other than palladium, such as platinum, gold | metal | money, rhodium, iridium, and osmium, may contain further. Preferred noble metals other than palladium include gold and platinum.

  Different 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 trifluoroacete Divalent palladium compounds such as preparative (II).

The noble metal may be used by being supported on a carrier. Examples of the carrier include oxides such as silica, alumina, titania, zirconia, and niobium; hydrates such as niobic acid, zirconium acid, tungstic acid, and titanic acid; carbon; or a mixture thereof. Can include the above-mentioned titanium silicate. When a noble metal is supported in addition to the titanosilicate, a carrier supporting the noble metal can be mixed with the titanosilicate and the mixture can be used as a catalyst.
For supporting the noble metal compound, a conventionally known method such as an impregnation method can be used.

  The noble metal catalyst is preferably reduced, for example, after the noble metal compound is supported on the support. As a reduction method, when a reducing gas is used, a reduction treatment or the like in which an appropriate filling tube is filled with a solid noble metal compound carrier and a reducing gas is injected into the filling tube can be exemplified. Examples of the reducing gas include hydrogen, carbon monoxide, methane, ethane, propane, butane, ethylene, propylene, butene, butadiene, and the like, or a mixed gas of two or more selected from these. Of these, hydrogen is preferable. The reducing gas may be diluted with, for example, nitrogen, helium, argon, water vapor (steam), or the like, or a diluting gas in which two or more selected from these are mixed.

  As content of the noble metal contained in the said noble metal catalyst, the range of 0.01-20 weight% etc. can be mentioned, for example, Preferably the range of 0.1-5 weight% etc. are mentioned. The lower limit of the amount of the precious metal used may be, for example, 0.00001 part by weight, preferably 0.0001 part by weight or more, more preferably 0.001 part by weight with respect to 1 part by weight of titanosilicate in the preparation process. Part. The upper limit of the amount of the precious metal used may be, for example, 100 parts by weight, preferably 20 parts by weight, and more preferably 5 parts by weight with respect to 1 part by weight of titanosilicate.

As a minimum of reaction temperature in a hydrogen peroxide preparation process, 0 ° C can be mentioned, for example, Preferably 40 ° C is mentioned. As an upper limit of reaction temperature in a preparation process, 200 degreeC can be mentioned, for example, Preferably 150 degreeC is mentioned.
The lower limit of the reaction pressure (gauge pressure) in the hydrogen peroxide preparation step may be, for example, under a pressure of 0.1 MPa, preferably under a pressure of 1 MPa, more preferably under a pressure of 20 MPa. And even more preferably, under a pressure of 10 MPa.

  In the hydrogen peroxide preparation step, the partial pressure ratio of oxygen and hydrogen in the mixed gas of oxygen and hydrogen supplied to the reactor can include, for example, a range of oxygen: hydrogen = 1: 50 to 50: 1. Preferably, the range of oxygen: hydrogen = 1: 10 to 10: 1 is used. When the partial pressure of oxygen is higher than oxygen: hydrogen = 1: 50, it is preferable because the production rate of the oxirane compound tends to be improved. When the partial pressure of oxygen is lower than oxygen: hydrogen = 50: 1, carbon of the olefin -It is preferable because the production of by-products in which the carbon double bond is reduced by a hydrogen atom is reduced and the selectivity to olefin oxide tends to be improved.

  Moreover, it is preferable to handle the mixed gas of oxygen and hydrogen in the presence of a diluent gas. Examples of the gas used for dilution include nitrogen, argon, carbon dioxide, methane, ethane, and propane. Nitrogen and propane are preferable, and nitrogen is more preferable.

  When mixing and handling oxygen, hydrogen, olefin and diluent gas, the mixing ratio will be described by taking as an example the case where the olefin is propylene and the diluent gas is nitrogen gas. 100 square parts of oxygen, hydrogen, olefin and diluent gas On the other hand, the total of hydrogen and propylene is 4.9 parts by volume or less, oxygen is 9 parts by volume or less, and the rest is nitrogen gas, or the total of hydrogen and propylene is 50 parts by volume or more and oxygen is 50 parts by volume or less The remaining is preferably nitrogen gas.

As oxygen, oxygen-containing air or oxygen-containing air may be used. Examples of the oxygen gas include oxygen gas produced by an inexpensive pressure swing method, high-purity oxygen gas produced by cryogenic separation, and the like.
The supply amount of oxygen is, for example, in the range of 0.005 to 10 mol, preferably in the range of 0.05 to 5 mol, with respect to 1 mol of supplied propylene.

  Examples of hydrogen include those obtained by steam reforming hydrocarbons. As a purity of hydrogen, 80 volume% or more can be mentioned, for example, Preferably, 90 volume or more is mentioned. The supply amount of hydrogen can be, for example, in the range of 0.05 to 10 mol, preferably in the range of 0.05 to 5 mol, with respect to 1 mol of supplied propylene.

  In the reaction step, the presence of a buffering agent is preferable because it tends to prevent a decrease in catalyst activity, further increase the catalyst activity, and improve the utilization efficiency of oxygen and hydrogen. Here, the buffer salt means a salt that gives a buffering action to the hydrogen ion concentration of the solution.

The buffering agent is preferably dissolved in the reaction solution of the reaction step. Further, in the hydrogen peroxide preparation step, the buffer may be previously contained in a part of the noble metal catalyst. For example, a method in which an ammonium-containing noble metal compound such as Pd tetraammine chloride is supported on a support by an impregnation method or the like and then reduced to leave ammonium ions to generate ammonium ions as a buffer during the reaction process.
The addition amount of the buffering agent is not more than the solubility of the buffering agent in the solvent used in the reaction step, and preferably includes, for example, a range of 0.001 mmol to 100 mmol per 1 kg of the solvent.

Examples of the buffer include 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, nitric acid An anion selected from the group consisting of ions, 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 a buffer comprising a cation selected from the group consisting of alkaline earth metals.
Examples of the carboxylate ion having 1 to 10 carbon atoms include acetate ion, formate ion, acetate ion, propionate ion, butyrate ion, valerate ion, caproate ion, caprylate ion, caprate ion, benzoate ion, etc. Is mentioned.
Examples of alkylammonium include tetramethylammonium, tetraethylammonium, tetra-n-propylammonium, tetra-n-butylammonium, and cetyltrimethylammonium. Examples of alkali metal and alkaline earth metal cations include lithium cation. 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. Examples thereof include ammonium salts of inorganic acids such as ammonium salts of carboxylic acids having 1 to 10 carbon atoms such as ammonium acetate, and preferable ammonium salts include, for example, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and the like. .

（式中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立に、水素原子を表すか、又は、Ｒ^１とＲ^２と、若しくは、Ｒ^３とＲ^４とが、互いに結合して、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４のそれぞれが結合している炭素原子とともに、置換基を有していてもよいベンゼン環若しくは置換基を有していてもよいナフタレン環を形成していてもよい。ＸおよびＹはそれぞれ独立に、酸素原子もしくはＮＨ基を表す。）
で表される化合物が挙げられる。 In the reaction step, the presence of a quinoid compound is preferable because the selectivity to olefin oxide tends to be further increased.
As the quinoid compound, for example, the formula (1)

(Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, or R ¹ and R ² , or R ³ and R ⁴ are bonded to each other) , R ¹ , R ² , R ³ and R ⁴ , together with the carbon atom to which each is bonded, forms an optionally substituted benzene ring or an optionally substituted naphthalene ring. X and Y each independently represents an oxygen atom or an NH group.)
The compound represented by these is mentioned.

Examples of the compound represented by the formula (1) include 1) a quinone compound in which, in the formula (1), R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, and X and Y are both oxygen atoms (1A),
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、それぞれ独立に、水素原子、ヒドロキシル基もしくはアルキル基（例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基等の炭素数１〜５のアルキル基）を表す。）
で表されるアントラキノン化合物等を挙げることができる。 As another example of the compound represented by formula (1), formula (2)

Wherein X and Y are as defined in formula (1), and R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a hydroxyl group or an alkyl group (for example, a methyl group , An alkyl group having 1 to 5 carbon atoms such as an ethyl group, a propyl group, a butyl group and a pentyl group).
The anthraquinone compound etc. which are represented by these can be mentioned.

X and Y in the compound represented by the formula (1) are preferably oxygen atoms.
Examples of the compound represented by the formula (1) include quinone compounds such as benzoquinone and naphthoquinone, for example, anthraquinone such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, 2-methylanthraquinone, 2-alkylanthraquinone compounds such as 2-butylanthraquinone, 2-t-amylanthraquinone, 2-isopropylanthraquinone, 2-s-butylanthraquinone or 2-s-amylanthraquinone, such as 1,3-diethylanthraquinone, 2,3 -Polyalkylanthraquinone compounds such as dimethylanthraquinone, 1,4-dimethylanthraquinone, 2,7-dimethylanthraquinone, for example, polyhydroxyanthraquinone compounds such as 2,6-dihydroxyanthraquinone For example, naphthoquinone, 1,4-phenanthraquinone p- quinoid compound quinone such, for example, 1,2-, 3,4- and 9,10-phenanthraquinone o- quinoid compounds such like.

Preferred examples of the compound represented by the formula (1) include anthraquinone and 2-alkylanthraquinone compounds (in the formula (2), X and Y represent an oxygen atom, R ⁵ represents an alkyl group, and R ⁶ represents hydrogen. And R ⁷ and R ⁸ represent a hydrogen atom.) And the like.

  As usage-amount of the quinoid compound in a reaction process, the range of 0.001 mmol-500 mmol etc. can be mentioned per kg of solvent, Preferably, the range of 0.01 mmol-50 mmol is mentioned, for example.

  In the reaction step, a salt comprising ammonium, alkylammonium or alkylarylammonium can be added during the reaction step.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、ＸおよびＹは、前記と同じ意味を表す。）
で表される化合物、 The quinoid compound can also be prepared by oxidizing a dihydro form of the quinoid compound using oxygen or the like in the reaction step. For example, hydroquinone or a compound in which a quinoid compound such as 9,10-anthracenediol is hydrogenated may be added to the liquid phase and oxidized with oxygen in a reactor to generate the quinoid compound.
Examples of the dihydro form of the quinoid compound include a formula (3) that is a dihydro form of the compound represented by the formula (1).

(Wherein R ¹ , R ² , R ³ , R ⁴ , X and Y represent the same meaning as described above.)
A compound represented by

（式中、Ｘ、Ｙ、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８は前記と同じ意味を表す。）
等を挙げることができる。
式（３）および式（４）における好ましいＸおよびＹとしては、酸素原子である。
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。 For example, Formula (4) which is a dihydro form of the compound represented by Formula (2)

(In the formula, X, Y, R ⁵ , R ⁶ , R ⁷ and R ⁸ represent the same meaning as described above.)
Etc.
Preferable X and Y in Formula (3) and Formula (4) are oxygen atoms.
Preferred dihydro forms of quinoid compounds include dihydro forms corresponding to the above-mentioned preferred quinoid compounds.

The reaction step may be performed continuously. For example, a solvent and titanium silicate, if necessary, a buffering agent, a quinoid compound, etc. are accommodated in a reaction tank, and hydrogen peroxide and olefin are continuously supplied to the reaction tank. The process etc. which make it react and supply the obtained reaction liquid continuously to the decomposition tank mentioned later can be mentioned.
When hydrogen peroxide is produced from oxygen and hydrogen as described above, a noble metal catalyst is further accommodated in the reaction tank, and oxygen and hydrogen are continuously supplied to the reaction tank. While continuously generating hydrogen peroxide, a reaction solution containing hydrogen peroxide and olefin oxide is continuously obtained. Moreover, oxygen, hydrogen, and olefin may be continuously supplied as a mixed gas mixed with a diluent gas as necessary.
The reaction tank is preferably provided with mixing means such as a stirring blade. When the mixing means is provided, hydrogen peroxide and titanium silicate tend to be mixed efficiently.

A plurality of reaction vessels may be used for the reaction step. That is, a specific embodiment of the reaction vessel is, for example, a reaction vessel represented by (1) to (3) in FIG. 1 (reaction vessel (1), reaction vessel (2), reaction vessel (3), respectively). May be mentioned). That is, the reaction tank (1) has a stirring blade such as a paddle blade inside, a pipe (5) for continuously receiving a mixed gas containing oxygen, hydrogen and olefin in the reaction tank (1), and a reaction tank ( A tube (6) for continuously supplying the reaction solution from 1) to the reaction vessel (2) is connected, the reaction step is performed in the reaction vessel (1), and the reaction solution obtained is the reaction vessel (2). It is continuously supplied to the reaction vessel (2) via the pipe (6) connected to.
The reaction vessel (2) has a stirring blade inside, a pipe (5) for continuously receiving a mixed gas containing oxygen, hydrogen and olefin in the reaction vessel (2), and the reaction vessel (2) to the reaction vessel. The tube (7) for continuously supplying the reaction solution to (3) is connected, the reaction step is performed in the reaction vessel (2), and the obtained reaction solution is a tube connected to the reaction vessel (3). Via (7), it is continuously supplied to the reaction vessel (3).
The reactant obtained in the reaction step (in the above example, the reaction solution supplied from the reaction tank to the decomposition tank) is preferably supplied to the decomposition tank after removing the titanosilicate and the noble metal catalyst. Specifically, a method of supplying the supernatant of the reaction solution containing almost no catalyst component in the reaction tank, a tube for continuously supplying the reaction solution from the reaction tank to the decomposition tank, or a filter or the like before and after the tube. Examples of the method include separation methods.
When using a plurality of reaction vessels, when supplying the reaction solution from the reaction vessel to another reaction vessel, similarly, the reaction solution can be supplied to another reaction vessel after removing the titanosilicate catalyst and the noble metal catalyst. .

Next, a contact process is demonstrated.
This substance used in the contacting step is a substance containing at least one element selected from the group consisting of manganese and platinum group elements. Examples of the platinum group element include ruthenium, rhodium, palladium, osmium, iridium or platinum, preferably rhodium, palladium, iridium or platinum, and more preferably include palladium and platinum.

This substance may be a compound or a simple substance.
When the substance is a simple substance, examples of the simple substance include manganese simple substance, ruthenium simple substance, rhodium simple substance, palladium simple substance, osmium simple substance, iridium simple substance and platinum simple substance, preferably rhodium simple substance, palladium simple substance, iridium simple substance and Platinum simple substance etc. are mentioned, More preferably, palladium simple substance, platinum simple substance, etc. are mentioned.
Ruthenium, rhodium, palladium, osmium, iridium and platinum containing a group 11 element (eg, gold, silver, copper, etc.) as long as the effects of the present invention are not impaired. Is also this substance.

When the substance is a compound, examples of the compound include an alloy of the metal and an oxide containing the element. As the compound, for example, oxides such as manganese oxide, manganese dioxide, RuO ₄ , RuO ₂ , Rh ₂ O ₃ , PdO, OsO ₂ , OsO ₄ , IrO ₂ are preferable, and manganese dioxide is more preferable. In addition, manganese dioxide means a non-stoichiometric compound having a composition ratio of MnO _X ( _X = about 1.9 to 2).

The substance may be supported on a carrier. When the substance is a simple substance, the substance is preferably supported on a carrier.
As the carrier, for example, an oxide (for example, silica, alumina, titania, zirconia, niobia, zeolite, etc.) composed of an element inert to the oxiranyl group, a hydrate (for example, niobic acid) composed of an element inert to the oxiranyl group , Zirconium acid, tungstic acid, titanic acid, etc.), carbon (for example, activated carbon, carbon black, graphite, carbon nanotube, etc.). Preferably it is activated carbon.
Examples of the content of the substance with respect to 100 parts by weight of the substance supported on the carrier include 0.0001 to 20 parts by weight, preferably 0.001 to 10 parts by weight. A range of parts by weight is mentioned.

  As the usage-amount of this substance in a contact process, the range of 0.01-1000 weight part can be mentioned with respect to 1 weight part of hydrogen peroxide contained in this solution, for example, Preferably, it is 0.1-1000 weight part. A range of 100 parts by weight is mentioned.

The reactant used in the contacting step is the reactant obtained in the reaction step (hereinafter sometimes referred to as the present reactant). This reaction product contains residual hydrogen peroxide, olefin oxide, and solvent.
Here, the olefin oxide is an oxirane compound in which the carbon-carbon double bond of the olefin is substituted with an oxiranyl group. For example, ethylene oxide (oxirane), propylene oxide (1-methyloxirane), 1-ethyloxirane, Carbons such as 1-propyloxirane, 1-butyloxirane, 1-pentyloxirane, 1-hexyloxirane, 1-heptyloxirane, 1-octyloxirane, 1-methyl-2-ethyloxirane, 1-methyl-2-methyloxirane An oxirane compound having a number of 2 to 10 can be exemplified, and propylene oxide and the like are preferable.

  As content of the olefin oxide contained in this reaction material, the range of 0.1-50 weight part can be mentioned with respect to 100 weight part of this solution, for example, Preferably, it is the range of 1-30 weight part Is mentioned.

Examples of the solvent contained in the reaction product include the same solvents as in the reaction step. Preferably, the solvent used in the reaction step is used as it is.
As a usage-amount of a solvent, the range of 1-1000000 weight part etc. can be mentioned with respect to 1 weight part of this substance, for example, Preferably, it is the range of 10-100,000 weight part, More preferably, it is 100-10000 weight. The range of the part etc. are mentioned.

  The content of hydrogen peroxide contained in the reaction product can be, for example, in the range of 0.001 to 10 parts by weight, preferably 0.005 to 5 parts per 100 parts by weight of the reaction product. A range of parts by weight is mentioned.

Next, the reaction conditions of the contact process will be described.
As a minimum of reaction temperature in a contact process, 0 ° C can be mentioned, for example, Preferably 20 ° C is mentioned. As an upper limit of reaction temperature in a contact process, 200 degreeC can be mentioned, for example, Preferably 150 degreeC is mentioned.
The pressure (gauge pressure) in the contacting step may be the same as the pressure in the reaction step, or may be reduced after the reaction step and under normal pressure or reduced pressure. Preferably, the reaction is performed at the same pressure as in the reaction step.

You may perform a contact process continuously. Specifically, the solvent and the substance are contained in a decomposition tank, and the reaction product from the reaction step is continuously supplied to the decomposition tank, mixed in the decomposition tank, and residual hydrogen peroxide. And the like can be exemplified.
In order to decompose the hydrogen peroxide contained in this reaction product, the residence time of the reaction solution in the decomposition tank is at least 0.01 hour, preferably 0.1 to 5 hours. it can.

Specific embodiments of the decomposition tank include, for example, a decomposition tank represented by (4) in FIG. 1 (hereinafter may be referred to as a decomposition tank (4)). That is, the decomposition tank (4) has a paddle blade inside, and has a pipe (8) for continuously receiving the reaction solution from the reaction tank (3). Hydrogen peroxide is removed from the decomposition tank (4). A pipe (9) or the like for continuously discharging the solution containing the olefin oxide with reduced hydrogen peroxide obtained by decomposition is connected, and the pipe containing the solution containing the olefin oxide with reduced hydrogen peroxide from (9). It can be obtained from (9). In the decomposition tank, the remaining hydrogen peroxide is decomposed, but the olefin oxide is hardly decomposed.
When the residual hydrogen peroxide is decomposed from the decomposition tank to obtain a solution containing olefin oxide, it is preferable that the substance stays in the decomposition tank. Specifically, a method of supplying the supernatant of the reaction solution containing almost no substance in the decomposition tank, a tube (9) for continuously obtaining a solution containing olefin oxide from the decomposition tank, or a filter before and after the above catalyst component The method etc. which isolate | separate can be mentioned.

Examples of the reaction tank used in the reaction process and the decomposition tank used in the contact process include a flow-type fixed bed reaction apparatus and a flow-type slurry complete mixing apparatus.
When a flow-type slurry complete mixing device is used, a titanosilicate and a noble metal catalyst, or this substance (hereinafter sometimes collectively referred to as a catalyst) is a filter installed inside or outside the reaction vessel. It is preferable to filter by using and again to be used in the reaction vessel. Specifically, for example, a part of the catalyst in the reaction tank or the decomposition tank is withdrawn continuously or intermittently, the catalyst is regenerated as necessary, and then the catalyst is put into the reaction tank or the decomposition tank. For example, a part of the catalyst in the reaction tank or the decomposition tank is discharged continuously or intermittently, and the amount of new titanosilicate corresponding to the discharged catalyst reacts with the noble metal catalyst or this substance. Examples include a method of adding to the apparatus.
When a flow-type fixed bed reactor is used, for example, a reaction vessel containing a catalyst with reduced productivity of olefin oxide performs a catalyst regeneration process as a reaction vessel for regenerating the catalyst, and performs reaction and regeneration. Examples include a method that is repeated alternately, and a decomposition tank that is used when the activity of the substance is reduced can similarly include a method that is performed by alternately repeating decomposition and regeneration of hydrogen peroxide. . In that case, it is preferable to use what was shape | molded by the type | mold agent etc. as a catalyst.

  The product of the contact step can be obtained olefin oxide by performing a separation operation such as distillation. For example, in the case of obtaining propylene oxide, after the contacting step, a gas consisting of crude propylene oxide, mainly hydrogen / oxygen / nitrogen, passes through a gas-liquid separation tower, a solvent separation tower, a crude propylene oxide separation tower, a propane separation tower, and a solvent purification tower Examples of the method include separation into components, recovered propylene, recovered solvent, and recovered quinone compound. The recovered propylene, the recovered solvent and the recovered quinone compound are desirably supplied again to the reaction tank and recycled. If the recovered propylene contains impurities such as propane, cyclopropane, methylacetylene, propadiene, butadiene, butanes, butenes, ethylene, ethane, methane, or hydrogen, they can be separated and purified if necessary and recycled. Good.

  A solution containing olefin oxide, hydrogen peroxide, and a solvent other than the reaction product, for example, a mixture of olefin oxide, hydrogen peroxide, and a solvent prepared separately, is brought into contact with the substance, Hydrogen peroxide can be removed.

  According to the present invention, almost no impurities such as glycol are generated from a solution containing olefin oxide in which hydrogen peroxide remains (for example, almost propylene glycol is generated from a solution containing propylene oxide in which hydrogen peroxide remains). Not) and can decompose hydrogen peroxide.

  Hereinafter, the present invention will be described in more detail with reference to examples.

(Preparation example 1 of titanosilicate)
At room temperature (about 25 ° C.), in an Air atmosphere, 899 g of piperidine, 2402 g of pure water, 112 g of TBOT (tetra-n-butyl orthotitanate), 565 g of boric acid, 410 g of fumed silica (cab-o-sil M7D) A gel was prepared by dissolving with stirring, aged for 1.5 hours, and then sealed. The mixture was further heated for 8 hours with stirring, and then kept at 160 ° C. for 120 hours to obtain a suspension. The obtained suspension solution was filtered, and then washed with water until the filtrate reached about pH 10. Next, the cake was dried at 50 ° C. to obtain a white powder still containing water. To 15 g of the obtained powder, 750 mL of 2N nitric acid was added and heated under reflux for 20 hours. Next, the mixture was filtered, washed with water to near neutral, and sufficiently dried at 50 ° C. to obtain 11 g of white powder. As a result of measuring the X-ray diffraction pattern of this white powder using an X-ray diffractometer using copper K-alpha radiation, it was confirmed that it was a Ti-MWW precursor, and the titanium content by ICP emission analysis was 1.65. % By weight.
Next, 2.28 g of the powder was stirred for 1 hour at room temperature in about 80 ml of a water / acetonitrile = 20/80 (weight ratio) solution containing 0.1% by weight of hydrogen peroxide and filtered. The titanosilicate was obtained.

(Production Example 1 of this reaction product obtained by the reaction step)
A reaction process for obtaining propylene oxide from hydrogen peroxide and propylene separately prepared in the presence of titanosilicate and a solvent in the reaction tank (1) is shown below.
After charging 131 g of acetonitrile water having a weight ratio of water / acetonitrile = 30/70 and 2.28 g of the titanosilicate in an internal volume 300 cc autoclave equipped with a jacket, the pressure was adjusted to 4 MPa with nitrogen, The temperature in the autoclave was adjusted to 50 ° C. by circulating hot water through the jacket. Acetonitrile water (water / acetonitrile) containing 143 L (standard state) / Hr of nitrogen gas, 0.7 mmol / kg of anthraquinone, 0.7 mmol / kg of ammonium dihydrogen phosphate, 3.3% by weight of hydrogen peroxide in the autoclave The weight ratio was 30/70) and the propylene liquid was continuously fed at 36 g / Hr. During the reaction process, the reaction temperature was controlled to 50 ° C. and the reaction pressure to 4 MPa. The titanosilicate, which is a solid component, was filtered through a sintered filter, returned to normal pressure, then separated into gas and liquid, and a liquid component and a gas component were continuously extracted. After 6.5 hours, the liquid component and gas were sampled simultaneously, and the liquid component and gas were analyzed for propylene oxide (PO) and propylene glycol (PG) by gas chromatography, respectively, and hydrogen peroxide by titration with potassium permanganate. The concentration of was analyzed. The increase in PO, including the liquid component and the PO entrained with the gas, was 177 mmol / hr. The liquid component contained 4.2 wt% PO, 0.2 wt% PG, and 4530 wt ppm hydrogen peroxide.

(Production Example 2 of this reaction product obtained by the reaction step)
A reaction process for obtaining propylene oxide from hydrogen peroxide and propylene while preparing hydrogen peroxide from oxygen and hydrogen in the presence of titanosilicate and a solvent in the reaction tank (1) is shown below.
A 300 cc autoclave equipped with a jacket was charged with 131 g of acetonitrile water having a weight ratio of water / acetonitrile = 30/70, 2.28 g of the titanosilicate, and 0.20 g of activated carbon catalyst supporting 1% by weight of palladium, followed by pressure. Was adjusted to an absolute pressure of 4 MPa with nitrogen, and the temperature in the autoclave was adjusted to 50 ° C. by circulating hot water through the jacket. 146 L (standard state) / Hr, anthraquinone 0.7 mmol / kg, diammonium hydrogen phosphate, a mixed gas having a composition of 3.6 vol% hydrogen, 2.1 vol% oxygen, and 94.3 vol% nitrogen was added to the autoclave. Acetonitrile water containing 3.0 mmol / kg (the weight ratio of water / acetonitrile is 30/70) was continuously supplied at 90 g / Hr and a propylene solution at 36 g / Hr. During the reaction, the reaction temperature was controlled to 50 ° C. and the reaction pressure to 4 MPa. Titanosilicate and palladium-supported activated carbon catalyst, which are solid components, were filtered through a sintered filter, returned to normal pressure, and then separated into gas and liquid, and the liquid component and gas component were continuously extracted. After 6 hours, the liquid component and gas were sampled simultaneously, and the liquid component and gas were analyzed for propylene oxide (PO) and propylene glycol (PG) by gas chromatography, respectively, and the concentration of hydrogen peroxide was determined by potassium permanganate titration. Was analyzed. The increase in PO, including the liquid component and the PO entrained with the gas, was 50 mmol / hr. The liquid component contained 3.1 wt% PO, 0.2 wt% PG, and 760 wt ppm hydrogen peroxide.

(Production Example 3 of this reaction product obtained by the reaction step)
As a reaction step in the reaction vessel (2) or (3), while preparing hydrogen peroxide from oxygen and hydrogen in the presence of titanosilicate and a solvent, propylene is produced from the hydrogen peroxide and propylene contained in acetonitrile water. The reaction process for obtaining oxide is shown below.
A 300 cc autoclave equipped with a jacket was charged with 131 g of acetonitrile water having a weight ratio of water / acetonitrile = 30/70, 2.28 g of the titanosilicate, and 1.198 g of 1 wt% palladium-supported activated carbon catalyst. The absolute pressure was adjusted to 4 MPa with nitrogen, and the temperature in the autoclave was adjusted to 50 ° C. by circulating hot water through the jacket. In the autoclave, 146 L (standard state) / Hr, anthraquinone 0.7 mmol / kg, ammonium dihydrogen phosphate was mixed with 3.6 vol% hydrogen, 2.1 vol% oxygen, and 94.3 vol% nitrogen. Acetonitrile water containing 0.7 mmol / kg and 10.0% by weight of propylene oxide (water / acetonitrile weight ratio is 30/70) was continuously supplied at 90 g / Hr and propylene liquid at 36 g / Hr. . During the reaction, the reaction temperature was controlled to 50 ° C. and the reaction pressure to 4 MPa. The titanosilicate and palladium-supported activated carbon catalyst, which are solid components, were filtered through a sintered filter, separated into gas and liquid, then returned to normal pressure, and the liquid component and gas component were continuously extracted. After 6 hours, the liquid component and gas were sampled simultaneously, and the liquid component and gas were analyzed for propylene oxide (PO) and propylene glycol (PG) by gas chromatography, respectively, and the concentration of hydrogen peroxide was determined by potassium permanganate titration. Was analyzed. The increase in PO, including the liquid component and the PO entrained with the gas, was 36 mmol / hr. The liquid component contained 11.6 wt% PO, 0.3 wt% PG, and 980 wt ppm hydrogen peroxide.

Example 1
(Preparation of solution containing olefin oxide, hydrogen peroxide and solvent)
10.8% by weight of propylene oxide, 0.002% by weight of propylene glycol, 1.1% by weight of hydrogen peroxide, anthraquinone as a quinone compound, 0.7 mmol / kg (based on an acetonitrile aqueous solution), ammonium dihydrogen phosphate (( These were mixed so as to contain NH ₄ ) ₂ HPO ₄ ) 3 mmol / kg (based on acetonitrile aqueous solution) to prepare 200 g of Solution 1 (acetonitrile / water = 7/3).

(Contact process)
Nitrogen gas at 800 mL / min was passed through the decomposition tank filled with the solution 1, and then 2.0 g of manganese dioxide was added and stirred at 50 ° C.
Immediately after adding manganese dioxide, the content of hydrogen peroxide (H ₂ O ₂ ) and propylene oxide (PO) in the decomposition tank was measured together with the stirring time shown in Table 1, and manganese dioxide was added. Table 1 shows the retention when each content immediately after is set to 100. In addition,-means unmeasured.
Table 1 also shows the case of stirring without mixing manganese dioxide.
As apparent from Table 1, H ₂ O ₂ was reduced to a retention rate of 0.1% in 40 minutes. Although the amount of evaporation due to the nitrogen gas flow decreased, PO was maintained at the same level as when manganese dioxide was not mixed.
The concentration of propylene glycol (PG) in the solution 1 is also shown in Table 1. It can be seen that PG hardly increases even when manganese dioxide is added.

(Example 2)
(Preparation of solution containing olefin oxide, hydrogen peroxide and solvent)
Propylene oxide 10.1 wt%, propylene glycol 0.003% wt, hydrogen peroxide 1.2 wt%, anthraquinone 0.7 mmol / kg (based on acetonitrile solution) as a quinone compound, diammonium hydrogen phosphate ((NH ₄ ) ₂ HPO ₄ ) These were mixed so as to contain 3 mmol / kg (based on acetonitrile aqueous solution) to prepare 200 g of solution 2 (acetonitrile / water = 7/3).

(Contact process)
1. Nitrogen gas 800 mL / min was circulated through the decomposition tank filled with the solution 2, and then 5% by weight of ruthenium simple substance was supported on the activated carbon (hereinafter sometimes referred to as Ru-supported activated carbon). 1 g was added and stirred at 50 ° C.
Immediately after the addition of Ru-supported activated carbon, the content of hydrogen peroxide (H ₂ O ₂ ) and propylene oxide (PO) in the decomposition tank was measured together with the stirring time shown in Table 2, and Ru-supported activated carbon Table 2 shows the retention when each content immediately after the addition is 100. In addition,-means unmeasured.
Table 2 also shows the case of stirring without mixing the Ru-supported activated carbon.
As is apparent from Table 2, H ₂ O ₂ was reduced to a retention rate of 2.5% in 120 minutes. Although the amount of evaporation due to the nitrogen gas flow decreased, PO was maintained at the same level as when Ru-supported activated carbon was not mixed.
The concentration of propylene glycol (PG) in the solution 2 is also shown in Table 2. It can be seen that PG hardly increases even when Ru-supported activated carbon is added.

(Example 3)
(Preparation of solution containing olefin oxide, hydrogen peroxide and solvent)
Propylene oxide 10.3 wt%, propylene glycol 0.005 wt%, hydrogen peroxide 1.2 wt%, anthraquinone 0.7 mmol / kg (based on acetonitrile aqueous solution) as a quinone compound, diammonium hydrogen phosphate ((NH ₄ ) ₂ HPO ₄ ) These were mixed so as to contain 3 mmol / kg (based on acetonitrile aqueous solution) to prepare 200 g of solution 3 (acetonitrile / water = 7/3).

(Contact process)
1. Nitrogen gas 800 mL / min was circulated through the decomposition tank filled with the solution 3, and then 5% by weight of palladium alone was supported on the activated carbon (hereinafter sometimes referred to as Pd-supported activated carbon). 2 g was added and stirred at 50 ° C.
Immediately after the addition of Pd-supported activated carbon, the content of hydrogen peroxide (H ₂ O ₂ ) and propylene oxide (PO) in the decomposition tank was measured together with the stirring time described in Table 3, Table 3 shows the retention when each content immediately after the addition was taken as 100. In addition,-means unmeasured.
Table 3 also shows the case of stirring without mixing the Pd-supported activated carbon.
As is apparent from Table 3, H ₂ O ₂ was reduced to a retention rate of 0.01% in 20 minutes. Although the amount of evaporation due to the nitrogen gas flow decreased, PO was maintained at the same level as when Pd-supported activated carbon was not mixed.
The concentration of propylene glycol (PG) in the solution 3 is also shown in Table 3. It can be seen that PG hardly increases even when Pd-supported activated carbon is added.

Example 4
(Preparation of solution containing olefin oxide, hydrogen peroxide and solvent)
Propylene oxide 10.0 wt%, propylene glycol 0.004 wt%, hydrogen peroxide 1.2 wt%, anthraquinone 0.7 mmol / kg (based on acetonitrile solution) as a quinone compound, diammonium hydrogen phosphate ((NH ₄ ) ₂ HPO ₄ ) These were mixed so as to contain 3 mmol / kg (based on acetonitrile aqueous solution) to prepare 200 g of Solution 4 (acetonitrile / water = 7/3).

(Contact process)
Nitrogen gas 800 mL / min is circulated through the decomposition tank filled with the solution 4, and 5% by weight of platinum alone is supported on the activated carbon (hereinafter sometimes referred to as Pt-supported activated carbon) 0 .2g was added and stirred at 50 ° C.
Immediately after the addition of Pt-supported activated carbon, the content of hydrogen peroxide (H ₂ O ₂ ) and propylene oxide (PO) in the decomposition tank was measured together with the stirring time described in Table 4, Table 4 shows the retention when each content immediately after the addition is 100. In addition,-means unmeasured.
Table 4 also shows the case of stirring without mixing the Pt-supported activated carbon.
As is apparent from Table 4, H ₂ O ₂ was reduced to a retention rate of 0.3% in 30 minutes. Although the amount of evaporation due to the nitrogen gas flow decreased, PO was maintained at the same level as when Pt-supported activated carbon was not mixed.
The concentration of propylene glycol (PG) in this solution 4 is also shown in Table 4. It can be seen that PG hardly increases even when Pt-supported activated carbon is added.

(Example 5)
The contact step is performed in the same manner as in Example 1, using the liquid component obtained in (Preparation Example 1 of the present reaction product obtained by the reaction step) as this solution.

(Example 6)
The contact step is performed in the same manner as in Example 3 using the liquid component obtained in (Preparation Example 2 of the present reaction product obtained by the reaction step) as this solution.

(Example 7)
The contact step is carried out in the same manner as in Example 4 using the liquid component obtained in (Preparation Example 3 of the present reaction product obtained by the reaction step) as this solution.

  According to the present invention, olefin oxide with reduced hydrogen peroxide can be obtained from a solution containing olefin oxide and hydrogen peroxide.

(1) to (3): Reaction tank (4): Decomposition tank (5): Mixed gas supply pipes of hydrogen peroxide, oxygen, hydrogen, olefin and diluent gas (6) to (8): (unreacted excess (Including hydrogen oxide and olefin oxide)
Reaction solution discharge pipe and reaction solution supply pipe (9): (including olefin oxide with reduced unreacted hydrogen peroxide)
Reaction solution discharge pipe

Claims (12)

[1] A step of reacting hydrogen peroxide with an olefin in the presence of titanosilicate and a solvent, and
[2] A step of bringing the reactant obtained by the above step into contact with a substance containing at least one element selected from the group consisting of manganese and a platinum group element;
The manufacturing method of the olefin oxide characterized by including. The method according to claim 1, wherein the solvent is a mixed solvent of an organic solvent and water. The method according to claim 2, wherein the organic solvent is acetonitrile. The manufacturing method according to any one of claims 1 to 3, wherein the titanosilicate is a layered titanosilicate having pores having 12 or more oxygen rings. The manufacturing method according to claim 1, wherein the titanosilicate is a Ti-MWW precursor. The manufacturing method according to claim 1, wherein the substance is a compound containing manganese or a platinum group element, or a simple substance containing a platinum group element. The manufacturing method according to claim 1, wherein the substance is manganese dioxide. The method according to claim 1, wherein the substance is a substance containing at least one element selected from the group consisting of rhodium, palladium, iridium, and platinum. The method according to claim 1, wherein the substance is a substance containing palladium or platinum. The manufacturing method according to claim 1, wherein the substance is a substance supported on a carrier. The method according to claim 10, wherein the carrier is activated carbon. Removal of hydrogen peroxide, comprising a step of bringing a substance containing at least one element selected from the group consisting of manganese and a platinum group element into contact with a solution containing an olefin oxide, hydrogen peroxide, and a solvent. Method.

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