NL1039702C2 - METHOD FOR PRODUCING ALKEEN OXIDE AND PALLADIUM-CONTAINING CATALYST TO WHICH THIS IS USED - Google Patents

Abstract

An object of the present invention is to provide a production method and a novel catalyst and the like used for the same that result in providing a high production amount of an alkylene oxide in a reaction for producing an alkylene oxide from oxygen, hydrogen and an olefin by using together with a titanosilicate-containing catalyst. This object can be achieved by a method for producing an alkylene oxide, comprising the step of reacting oxygen, hydrogen and an olefin, in the presence of a carbon-containing gas-treated palladium-containing catalyst which is obtained by contacting a palladium-containing composition comprising palladium and a carrier with a compound selected from the group consisting of acetylene, ethylene and carbon monoxide and a titanosilicate-containing catalyst, and a carbon-containing gas-treated palladium-containing catalyst and the like used for the same.

Description

Process for producing olefin oxide and palladium-containing catalyst in which it is used 5

Technical area

The present invention relates to a process for producing an olefin oxide and a palladium-containing catalyst and the like in which they are used.

Background of the Prior Art A method for producing an olefin oxide such as propylene oxide by obtaining hydrogen peroxide from hydrogen and oxygen using a noble metal support as a first catalyst and converting the resulting hydrogen peroxide with an olefin such as propylene in the same reaction vessel using a titanium silicate as a second catalyst is known. In particular, patent document 1 describes, for example, as a noble metal support which is a first catalyst, a catalyst in which palladium tetraamine chloride is supported on activated carbon. A process for producing propylene oxide from oxygen, hydrogen, and propylene using a titanium silicate that is a second catalyst is also described.

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Citation list 1039702 2

Patent document

Patent document 1: JP-A 2008-201776 Summary of the invention Technical problem

An object to be accomplished by the present invention is to provide a production process and a new catalyst and the like, using these, which result in providing a high production amount of an olefin oxide at a reaction for producing an olefin oxide from oxygen, hydrogen, and an olefin by co-using a titanium silicate-containing catalyst.

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Solution of the problem

Under these circumstances, the present inventors have studied intensively, and therefore completed the present invention below.

More particularly, the present invention provides: 1. A process for producing an olefin oxide comprising the step of converting oxygen, hydrogen and an olefin, in the presence of a carbon-containing, gas-treated, palladium-containing catalyst which is obtained by contacting a palladium-containing composition, comprising palladium and a support with a compound selected from the group consisting of acetylene, ethylene and carbon monoxide and a titanium silicate-containing catalyst (hereinafter referred to as the production process for olefin oxide according to the the present invention); 2. A process for producing an olefin oxide according to item 1, wherein the olefin is propylene; 3. Method for producing an olefin oxide according to points 1 or 2, wherein the titanium silicate-containing catalyst comprises titanium silicate particles with an X-ray diffraction pattern with peaks at the positions below which are represented as spacing from the grid surface; <Positions of the peaks in an X-ray diffraction pattern displayed as distance from the grid surface (distance 10 from the grid surface d / A)> 12.4 ± 0.8, 10.8 ± 0.5, 9.0 ± 0.3 , 6.0 ± 0.3, 3.9 ± 0.3 and 3.4 ± 0.1 4. A process for producing an olefin oxide according to any of points 1-3, wherein the step is a step of converting oxygen, hydrogen and an alkene in the presence of a solvent; The method for producing an olefin oxide according to item 4, wherein the solvent is an organic solvent; 6. Process for producing an olefin oxide according to point 4, wherein the solvent is a solvent mixture of an organic solvent and water; A process for producing an olefin oxide according to item 5 or 6, wherein the organic solvent is acetonitrile; 8. A process for producing an olefin oxide according to any of the points 1-7, wherein the palladium-containing catalyst is a palladium-containing catalyst, the catalytic activity of which has been recovered or regenerated by previously contacting with a carbon-providing compound with 4 or fewer carbon atoms that is gaseous under normal temperature and pressure conditions; 9. A process for producing an olefin oxide according to item 8, wherein the carbon-providing compound with 4 or fewer carbon atoms that is gaseous under normal temperature and pressure conditions is propylene; 10. Carbon-containing, gas-treated, palladium-containing catalyst obtained by contacting a palladium-containing composition, comprising palladium and a support with a compound selected from the group consisting of acetylene, ethylene and carbon monoxide (hereinafter referred to as the palladium-containing catalyst of the present invention); A carbon-containing, gas-treated, palladium-containing catalyst according to item 10, wherein the support 15 is a support selected from the group consisting of activated carbon, Al 2 O 3 and ZrC> 2; 12. Carbon-containing, gas-treated, palladium-containing catalyst according to points 10 or 11, wherein the value of the distance of the crystal plane of a (111) - 20 plane of a palladium metal, calculated from a diffraction angle determined by means of an X-ray diffraction analysis is 2,270A or more; and such.

Advantageous effects of the invention

[0006] According to the present invention, it is possible to provide a production method and a new catalyst used for this, which result in providing a high production amount of an olefin oxide in a reaction for producing propylene oxide from oxygen. , hydrogen and propylene by using a titanium silicate-containing catalyst together.

BRIEF DESCRIPTION OF THE DRAWINGS [FIG. 1] Figure 1 is a graph showing X-ray diffraction spectra of "palladium-containing catalyst B", which is the palladium-containing catalyst of the present invention and the "palladium-containing composition B".

Description of the embodiments

The process for producing olefin oxide according to the present invention comprises the step of converting oxygen, hydrogen, and an olefin in the presence of a carbon-containing, gas-treated, palladium-containing catalyst obtained by contacting a palladium-containing composition comprising palladium and a support with a compound selected from the group consisting of acetylene, ethylene and carbon monoxide and a titanium silicate-containing catalyst.

The carbon-containing, gas-treated, palladium-containing catalyst (ie, the palladium-containing catalyst of the present invention) used for the production process for olefin oxide of the present invention is obtained by contacting a palladium-containing composition comprising palladium and a carrier with a compound selected from the group consisting of acetylene, ethylene and carbon monoxide (hereinafter a carbon-containing gas) as described above.

In this document, examples of the "carrier" include oxides such as silica, alumina, titanium oxide, zirconia, niobium oxide and the like, hydroxides such as niobic acid, zirconic acid, tungstic acid, titanium acid and the like, carbon materials such as activated carbon, carbon black, graphite , carbon nanotubes and the like, and mixtures thereof. Preferred examples thereof include zirconia, alumina, titania and activated carbon. More preferred examples thereof include zirconium oxide. In addition, the titanium silicate-containing catalyst of the present invention can be used as a carrier.

In this document, the "palladium-containing composition comprising palladium and a carrier" can be obtained, for example, by using a method for carrying colloidal palladium or a palladium compound by a known method or the like and then a heat treatment of the result. Examples of the preferred palladium-containing composition include a palladium-containing composition which essentially comprises palladium and a carrier. In addition, examples of impurities present in minute amounts in the palladium-containing composition include noble metals such as gold, platinum, osmium, iridium, silver, rhenium and the like, alkali metals such as lithium, sodium, potassium, rubidium, cesium and the like, alkaline earth metals such as magnesium, calcium, strontium, barium and the like, rare earth metals such as scandium, yttrium, lanthanum, cerium, praseodymium, neodymium and the like, iron, titanium, manganese, molybdenum and tin.

In the following, a typical method for preparing the "palladium-containing composition comprising palladium and a carrier" is described.

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Examples of the "colloidal palladium" include the colloidal palladium and the like described in, for example, JP-A 2002-294301, Example 1.

In addition, examples of the "palladium-5 compound" include tetravalent palladium compounds such as sodium hexachloro palladate (IV) tetrahydrate, potassium hexachloro palladate (IV) and the like; and divalent palladium compounds such as palladium (II) chloride, palladium (II) bromide, palladium (II) acetate, palladium (11) acetyl acetonate, dichlorobis (benzonitrile) palladium (II), dichloro-bis (acetonitrile) palladium (II) dichloro (bis (diphenylphosphino) ethane) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichlorotetraamine palladium (II), dibromotetraamine palladium (II), dichloro (cycloocta-1.5) -15 diene) palladium (II), palladium (11) trifluoroacetate and the like.

Examples of the support method include ordinary wet support methods such as the impregnation method, immersion method, wet adsorption method, ion exchange method and the solvent evaporation method, and methods in which these methods are combined.

Examples of the solvent used in the above wet carrier processes include aqueous solvents, non-aqueous solvents, and solvent mixtures of these.

Typical examples of the solvent include water such as pure water, ion-exchanged water, tap water, industrial water and the like; alcohols such as methanol, ethanol, isopropanol, hexanol, octanol and the like; hydrocarbon solvents such as pentane, petroleum ether, hexane, cyclohexane, benzene, toluene, xylene, and the like; ketones such as acetone, ethyl methyl ketone, cyclohexanone, acetophenone and the like; halogenated hydrocarbon solvents such as methyl chloride, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, tetrachloroethane, propyl chloride, chlorobenzene, dichlorobenzene, methyl fluoride and the like; esters such as methyl acetate, ethyl acetate, propyl acetate and the like; ethers such as diethyl ether, dipropyl ether, tetrahydrofuran, dioxane and the like; nitriles such as acetonitrile, propionitrile and the like; organic acids such as acetic acid, propionic acid and the like; amines such as dimethylamine, trimethylamine, triethylamine, propylamine, aniline and the like; and amides such as dimethylformamide, diethylformamide, dimethylacetamide and the like. Preferred examples of the solvent include water. In addition, these solvents can be used individually and can be used in combination of two or more types.

The amount of the solvent used is not particularly limited, but is preferably an amount sufficient to come into contact with the whole of the carrier used. In addition, when the amount of the solvent used is present in large excess for the above suitable amount, a drying treatment takes a long time. Also, if the amount of the solvent used is too low for the above suitable amount, homogeneous dispersion on the support will not be easy.

Examples of the processing system when supported by the above wet carrier method 30 include stationary method, stirring method, flowing solution method, method in which the solvent is refluxed and a method in which these methods are combined.

A palladium-containing composition can be obtained using the above carrier method. Moreover, when the solvent or the palladium-containing solution remains excessive together with the resulting palladium-containing composition, the palladium-containing composition can usually be recovered by separating and removing an excess solvent or the noble metal-containing solution, or by evaporating of an excess of the solvent or the palladium-containing solution.

Examples of the method for separating and removing an excess of the solvent or the palladium-containing solution include common solid / liquid separation methods such as filtration, centrifugation, decantation and the like. In addition, examples of the methods of evaporating an excess of the solvent or the palladium-containing solution include natural evaporation method, evaporation method under reduced pressure, evaporation method by blowing, and evaporation method by bubbling gas distribution.

The palladium-containing composition obtained as described above can further be subjected to conventional drying by means of a heating treatment in an oven or the like, or be subjected to a known suitable pre-treatment or activation treatment. such as a heating treatment by means of an inert gas, a reduction treatment by means of a reducing gas such as hydrogen, an oxidation treatment by means of air or the like, or a treatment in which these treatments are directly and if necessary combined.

The palladium content present in the palladium-containing composition is, for example, 0.00001 part by weight or more, preferably 0.01 part by weight or more, more preferably, for example 0.1 part by weight or more, furthermore preferably, for example, in the range of 0.01 to 20 parts by weight, and especially preferably, for example, in the range of 0.1 to 5 parts by weight, calculated on 100 parts by weight of the palladium-containing composition.

The palladium-containing catalyst of the present invention may contain impurities that are present in small amounts in the "palladium-containing composition comprising palladium and a carrier" which is the raw material. In this document, examples of the impurities as described above include noble metals such as gold, platinum, osmium, iridium, silver, renium and the like, alkali metals such as lithium, sodium, potassium, rubidium, cesium and the like, alkaline earth metals such as magnesium, calcium, strontium, barium and the like, rare earth metals such as scandium, yttrium, lanthanum, cerium, praseodymium, neodymium and the like, iron, titanium, manganese, molybdenum and tin.

Any method can be used to contact the palladium-containing composition, comprising palladium and a carrier with the compound selected from the group consisting of acetylene, ethylene and carbon monoxide, and include examples thereof (1) a dry process, wherein the palladium-containing composition, including palladium and a support, is introduced into a reactor, then the compound is circulated while 11 keeps the heat, and (2) a wet process, wherein the palladium-containing composition, including palladium and a carrier in a solvent or the like are suspended in a sealed container such as an autoclave, mixed together with the compound and kept at the same temperature, or the compound is circulated by bubbling or the like.

The temperature of the contacting step is for example in the range of 25 ° C to 500 ° C, preferably for example in the range of 50 ° C to 300 ° C and more preferably for example in the range of 100 ° C to 200 ° C. The pressure of the contacting step by means of an overpressure is also in the range of 0 to 10 MPa, for example.

The lower limit of the contact time of the contacting step 15 is, for example, 10 minutes, preferably for example 2 hours, more preferably for example 10 hours, and further preferably for example 12 hours. Also, the upper limit of the contact time of the contact step is, for example, 120 hours, preferably for example 72 hours, more preferably for example 30 hours, and further preferably for example 24 hours.

In the contacting step, the palladium-containing composition, including palladium and a support, may be in the state in which they are mixed together with the titanium-silicate-containing catalyst described below.

The palladium catalyst according to the present invention can further be subjected to conventional drying by means of a heating treatment in an oven or the like, or subjected to a known suitable pre-treatment or activation treatment such as a heat treatment by means of an inert gas, a reduction treatment by means of reducing gas such as hydrogen, an oxidation treatment by means of air or the like or a treatment in which these treatments are combined, directly and if necessary, and can be used as a catalyst in the reaction .

Examples of the palladium catalyst of the present invention include those in which the value of the distance of the crystal plane of a (111) plane of a palladium metal calculated from a diffraction angle determined by means of an X-ray diffraction analysis is 2,270A or more. This is a physical value for confirming that, by subjecting the palladium-containing composition comprising palladium and a support for the step of contacting the compound consisting of the group consisting of acetylene, ethylene and carbon monoxide, the carbon obtained from the above is introduced into the palladium-containing composition. There may be a case in which only the above physical value is not enough for the attachment due to the effect of the background value or the like in the determination, depending on the type of carrier present in the palladium-containing composition, but the above physical value is especially suitable when the carrier is carbon such as activated carbon, carbon black, graphite, carbon nanotubes or the like, or a mixture thereof.

An X-ray diffraction pattern can be determined using a commercially available general X-ray diffraction device using a copper K alpha radiation as a radiation source. In particular, for example using the palladium catalyst of the present invention or the palladium-containing composition as a sample, the determination can be performed using an X-ray diffraction device such as RINT 2500 V manufactured by Rigaku Corporation under the conditions below .

5 (Determination conditions) - Output: 40 kV - 300 mA - Scan area: 29 = 30 - 90 ° - Scan speed: 1 ° / minute

The palladium-containing catalyst of the present invention can be used as a catalyst to produce an olefin oxide from hydrogen, oxygen, and an olefin. Moreover, the palladium-containing catalyst of the present invention is used in conjunction with a titanium silicate-containing catalyst (more particularly used together in the form, wherein both the titanium silicate-containing catalyst and the palladium-containing catalyst of the present invention are integrated or in the form, each of which is independently independent) and results in providing a high production amount of an olefin oxide in a reaction to produce propylene oxide from oxygen, hydrogen, and propylene.

Examples of the "titanium silicate-containing catalyst" used in the olefin oxide production process of the present invention include a catalyst referred to as titanium silicate particles. The titanium silicate particles with predominantly tetra-coordinated Ti, with the maximum absorption peak appearing within a wavelength range of 210-230 nm for an ultra-violet / visible light absorption spectrum within a wavelength range of 200-400 nm, are preferred (see, for example, Chemical Communications 1026-1027 (2002), fig.

14 2 (d) and (e)). In addition, the ultraviolet / visible light absorption spectrum can be determined based on a diffuse reflection method using an ultra-violet / visible light spectrophotometer equipped with a diffuse reflection device.

When the titanium silicate particles are used as a catalyst in, for example, a process for producing hydrogen peroxide such that oxygen and hydrogen are reacted in the presence of the palladium-containing catalyst of the present invention, titanium silicate particles that are previously in contact with hydrogen peroxide become been used preferably. The concentration of hydrogen peroxide that is subjected to the contact is, for example, in the range of 0.0001% by weight to 50% by weight.

Typical examples of the titanium silicate particles include those described in 1-7 below.

1. Small pore crystalline titanium silicates of a 10-membered oxygen ring:

In the IZA (International Zeolite Association) structure code, TS-1 with an MFI structure (e.g., U.S. Patent No. 4,410,501), TS-2 with an MEL structure (e.g., Journal of Catalysis 130, 440-446 , 25 (1991)), Ti-ZSM-48 with an MRE structure (e.g. Zeolites 15, 164-170, (1995)), Ti-FER with an FER structure (e.g. Journal of Materials Chemistry 8, 1685-1686 (1998)) and the like.

2. Small pore crystalline titanium silicates from a 12-membered oxygen ring:

Ti-beta with a BEA structure (e.g. Journal of Catalysis 199, 41-47, (2001)), Ti-ZSM-12 with an MTW structure (e.g. Zeolites 15, 236-242, (1995)), Ti - MOR with an MOR structure (e.g. The Journal of Physical Chemistry B 102, 9297-9303, (1998)), Ti-ITQ-7 with an ISV structure (e.g. Chemical Communications 761-5 762, (2000)), Ti-MCM-68 with an MSE structure (e.g.

Chemical Communications 6224-6226, (2008), Ti-MWW with an MWW structure (e.g., Chemistry Letters 774-775, (2000)), and the like.

3. Small pore crystalline titanium silicates from a 14-membered oxygen ring:

Ti-UTD-1 with a DON structure (e.g., Studies in Surface Science and Catalysis 15, 519-525, (1995)), and the like.

4. Small pore layered titanium silicates of a 10-membered oxygen ring:

Ti-ITQ-6 (e.g., Angewandte Chemie International Edition 39, 1499-1501, (2000)), and the like.

5. Small pore layered titanium silicates of a 12-membered oxygen ring: A Ti-MWW precursor (e.g. European patent application 1 731 515 A1), Ti-YNU-1 (e.g. Angewandte Chemie International Edition 43, 236 -240, (2004)), Ti-MCM-36 (e.g., Catalysis Letters 113, 160-164, (2007)),

Ti-MCM-56 (e.g., Microporous and Mesoporous Materi-25 as 113, 435-444, (2008)), and the like.

6. Mesoporous titanium silicates:

Ti-MCM-41 (e.g. Microporous Materials 10, 259-271, (1997)), Ti-MCM-48 (e.g., Chemical Communications 145-146, (1996)), Ti-SBA-15 (e.g., Chemistry of Materials 14 , '1657-1664, (2002)), and the like.

7. Silylated titanium silicates: 16

Compounds obtained by silylating the titanium silicates 1-6 described above, such as silylated Ti-MWW and the like.

In this document, "small pore" means a small pore composed of an Si-O bond or a Ti-O bond. Examples of the small pore include a small half-cup pore, called a side pocket (namely, it is not necessary to penetrate primary particles of the titanium silicate).

Also, the phrase "no less than X-membered oxygen ring" means that the number of oxygen atoms is no less than X at (a) a cross-section of the narrowest portion of a small pore, or (b) a ring structure at the entrance of the small pore. Moreover, the fact that the titanium silicate particles have small pores of no less than an X-membered oxygen ring is confirmed by, for example, an analysis of an X-ray diffraction pattern, and when the titanium silicate particles have a known structure, it can be easily confirmed by comparison with a X-ray diffraction pattern of the known compound.

In this document, the "layered titanium silicate" is a generic name for titanium silicates with a layered structure, such as layered precursors of a crystalline

Titanium silicate, and a titanium silicate, wherein the distances between the layers are expanded in a crystalline titanium silicate. Whether or not a titanium silicate has a layered structure can be confirmed by means of an electron microscope or an X-ray diffraction pattern.

30. In addition, the "layered precursor" indicates a titanium silicate that forms a crystalline titanium silicate by performing a treatment such as dehydration condensation and the like. It can easily be determined that a layered titanium silicate has small pores of a not less than 12-membered oxygen ring from the structure of a corresponding crystalline titanium silicate.

In addition, the "mesoporous titanium silicate" is a generic name of titanium silicates with regular mesopores. The regular mesopore indicates a structure in which the mesopores are arranged regularly and repeatedly. In addition, the "mesopore" indicates a small pore with a small pore diameter of 2-10 nm.

[0041] Also, the "silylated titanium silicate" refers to a compound obtainable by treating the titanium silicates 1-4 as described above with a silylating agent. Examples of the silylating agent include 1,1,1,3,3,3-hexamethyldisilazane and trimethylchlorosilane (e.g. European Patent Application 1 488 853 A1). Furthermore, a compound can be used which is obtained by mixing the silylated titanium silicate with a hydrogen peroxide solution (hereinafter referred to as the hydrogen peroxide treatment). The concentration of the hydrogen peroxide solution in the hydrogen peroxide treatment is, for example, in the range of 0.0001% by weight to 50% by weight. Examples of the solvent of the hydrogen peroxide solution water and the solvents used in the production process for olefin oxide according to the present invention. The temperature in the treatment with hydrogen peroxide is, for example, in the range of 0 ° C to 100 ° C and preferably in the range of 0 ° C to 60 ° C. The treatment time (mixing time) of the hydrogen peroxide treatment depends on the concentration of the hydrogen peroxide, and 18 is, for example, in the range of 10 minutes to 10 hours, and preferably, for example, in the range of 1 hour to 3 hours.

Among the above titanium silicate particles, preferred examples thereof include the small-pore titanium silicate of a not less than 12-membered oxygen ring. Such a titanium silicate can be a crystalline titanium silicate or a layered titanium silicate. Typical examples of the small pore titanium silicate of a not less than 12-membered oxygen ring include T-MWW and a Ti-MWW precursor.

Among the small-pore titanium silicate particles of a not less than 12-membered oxygen ring, preference is given to titanium silicate particles with an X-ray diffraction pattern with peaks at the positions shown below as lattice surface distances.

<Positions of the peaks in an X-ray diffraction pattern shown as distance from the grid surface (distance 20 from the grid surface d / A)> 12.4 ± 0.8, 10.8 ± 0.5, 9, 0 ± 0.3 , 6.0 ± 0.3, 3.9 ± 0.3 and 3.4 ± 0.1

A method for determining an X-ray diffraction pattern is described below.

An X-ray diffraction pattern can be determined using a commercially available general X-ray diffraction device using a copper K alpha radiation as a radiation source. In particular, for example using the titanium silicate particles as a sample, the determination can be made using an X-ray diffraction device such as RINT 2500 V, manufactured by Rigaku Corporation under the conditions below.

19 (Determination conditions) - Output: 40 kV - 300 mA - Scan area: 20 = 0.75 - 30 ° - Scan speed: 1 ° / minute 5 Typical examples of the titanium silicate particles with the X-ray diffraction pattern as described above (which with an X-ray diffraction pattern with peaks at the above positions shown as spacing from the grid surface include a Ti-MWW precursor 10 (e.g., titanium silicate particles described in JP-A 2005-262164), Ti-YNU-1 (e.g. titanium silicate particles described in Angewandte Chemie International Edition, 43, 236-240, (2004)), crystalline titanium silicates, Ti-MWW which is a crystalline titanium silicate with an MWW structure in the IZA (International Zeolite Association) structure code (e.g. titanium silicate particles described in JP-A 2003-327425) and Ti-MCM-68 which is a crystalline titanium silicate with an MSE structure in the IZA structure code (e.g. titanium silicate particles-20 described in JP-A 2008-50186).

The Ti-MWW precursor is a titanium silicate with a layered structure and indicates a substance that forms Ti-MWW by dehydration condensation of the Ti-MWW precursor. The dehydration condensation is usually carried out by heating the Ti-MWW precursor at a temperature higher than 200 ° C and not higher than 1000 ° C, and preferably in the range of 300 ° C to 650 ° C. In addition, the Ti-MWW precursor can be treated with a structure-directing agent, as described below in the production process. Furthermore, the Ti-MWW precursor obtained as described above can be treated again with a structure directing agent, as described below. These are also referred to as the "Ti-MWW precursor" in the present invention.

The Ti-MWW precursor can be used as a catalyst in various oxidation reactions and the like.

The silicon to nitrogen molar ratio (Si / N ratio) of the Ti-MWW precursor is, for example, in the range of 5 to 100 and preferably, for example, in the range of 10 to 20.

Examples of the process for preparing a Ti-MWW precursor include the various processes below.

(1) First method: a method comprising the step of heating a mixture comprising a structure-directing agent, a connection to an element 15 from group 13 of the periodic table of the elements (hereinafter referred to as a "group 13") element-containing compound "designated), a silicon-containing compound, a titanium-containing compound and water (hereinafter referred to as" Step (1-1) ") and the step of mixing a layered compound associated with Step (1-1) ) is obtained and an acid.

(2) Second method: a method comprising the step of heating a mixture comprising a structure directing agent, a group 13 element-containing compound, a silicon-containing compound and water (hereinafter referred to as "Step (2-1)") and the step of mixing a layered compound obtained in Step (2-1), a titanium-containing compound and an acid.

(3) Third method: a method comprising the step of heating a mixture comprising a structure directing agent, a group 13 element-containing compound, a silicon-containing compound, a titanium-containing compound and water (hereinafter as "Step (3-) 1) "21) and the step of mixing a layered compound obtained in Step (3-1), a titanium-containing compound and an acid.

(4) Fourth method: a method comprising the 5 steps of baking a layered borosilicate obtainable by heating a mixture comprising a structure directing agent, a group 13 element-containing compound, a silicon-containing compound and water (at preferably after contacting with an acid, the structure directing agent being removed, whereby B-MWW is obtained, removing boron by means of an acid or the like from the resulting B-MWW, then adding a structure-directing agent, a titanium-containing compound and water thereto, heating the resulting mixture, thereby obtaining a layered compound, and contacting the resulting compound with about 6 M nitric acid (see, for example, Chemical Communications, 1026-1027, (2002 )).

The T-MWW precursor obtained by means of the first to the fourth method is preferably further treated with a structure-directing agent for adjusting the molar ratio of silicon to nitrogen (Si / N ratio) up to a predetermined value 25 (e.g. in the range of 10 to 20).

For example, a titanium silicate-containing catalyst is mixed with a structure-directing agent and water in a sealable pressure-resistant container such as an autoclave, and the sealable pressure-resistant container is sealed, then immovable or stirred and then heated and mixed under pressure to obtain a liquid mixture, and a solid product can be obtained 22 by separating the resulting liquid mixture using a method such as filtration or centrifugation. In addition, they are mixed in a glass bottom in the atmosphere by stirring, or without stirring, thereby obtaining a liquid mixture, and a solid product can be separated by separating the resulting liquid mixture using a method such as filtration or centrifugation obtained from the resulting liquid mixture.

Moreover, the obtained titanium silicate-containing catalyst can be washed using water or the like. The washing can be suitably carried out, while the amount of a washing liquid or the pH value of a washing filtrate, if circumstances so require, is observed.

Furthermore, the washed product obtained can be dried, for example in the range of 0 ° C to 200 ° C, for example drying by means of an air stream, drying under reduced pressure or freeze-drying under vacuum, to an extent that weight reduction is no longer observed.

The temperature used in the above mixing operation is, for example, in the range of 0 ° C to 250 ° C, preferably in the range of 20 ° C to 200 ° C and more preferably in the range of 50 ° C to 180 ° C.

The mixing time used in the above mixing operation is, for example, in the range of 1 hour to 720 hours, preferably in the range of 2 hours to 720 hours, more preferably in the range of 4 hours to 720 hours and especially with preferably in the range of 8 hours to 720 hours.

The pressure used in the above mixing operation is not particularly limited, and is, for example, in the range of 0-10 MPa excess pressure.

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The amount of titanium-containing compound used in the above various processes is, for example, in the range of 0.001 to 1 part by weight and preferably, for example, in the range of 0.01 to 0.5 part by weight, as the weight of titanium atoms in the titanium-containing compound, calculated on 1 part by weight of the resulting layered compound.

Examples of the acid used in the above various processes include inorganic acids such as nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, boric acid, fluorosulfonic acid and the like, organic acids such as formic acid, acetic acid, propionic acid, tartaric acid and the like, and combinations of two or more thereof. Preferred examples thereof include acids containing at least one inorganic acid with a redox potential higher than that of tetravalent titanium. In this document, examples of the "inorganic acid with a redox potential higher than that of tetravalent titanium" include nitric acid, perchloric acid, fluorosulfonic acid, a combination of nitric acid and sulfuric acid, and a combination of nitric acid and boric acid.

The acid used in the above various processes is usually used in the state of a solution prepared by dissolving in a solvent. In this document, examples of the "solvent" include water, alcohol solvents, ether solvents, ester solvents, ketone solvents, and mixtures thereof. Preferred examples thereof include water.

The concentration of the acid present in the solution is, for example, in the range of 0.01 to 20 mol / l. When an inorganic acid is used as the acid, the concentration of the inorganic acid is preferably in the range of 1 to 5 mol / l, for example.

Examples of the "Group 13 Element of the Periodic Table of the Elements" used in the process for preparing a Ti-MWW precursor include a boron-containing compound, an aluminum-containing compound and a gallium-containing compound . Preferred examples thereof include a boron-containing compound.

Examples of the boron-containing compound include boric acid, borates, boron oxide, boron halide, and a trialkyl boron compound having an alkyl group of 1-4 carbon atoms. Preferred examples thereof include boron.

Examples of the aluminum-containing compound include sodium aluminate.

Examples of the gallium-containing compound include gallium oxide.

The amount of the group 13 element-containing compound used in the process for preparing a Ti-MWW precursor is, for example, in the range of 0.01 to 10 moles and preferably in the range of 0. 1 to 5 moles, calculated on 1 mole of silicon contained in the silicon-containing compound.

Examples of the "silicon-containing compound" used in the process for preparing a Ti-MWW precursor include silica, silicates, silica, silicon halide, tetraalkyl orthosilicate, and colloidal silicon. Preferred examples thereof include orthosilicic acid, meta-silica and meta-silica.

Examples of the silicate include alkali metal silicates such as sodium silicate, potassium silicate and the like, and alkaline earth metal silicates such as calcium silicate, magnesium silicate and the like.

Examples of the silica include crystalline silica such as quartz and amorphous silica such as high disperse silica. Preferred examples thereof include highly dispersed silica. In this document, as the "highly dispersed silica", generally commercially available high dispers silica can be used with a specific BET surface area of 50-380 m 2 / g. Among these, highly dispersed silica with a specific BET surface area of 50-200 mm 2 / g is preferred for ease of processing. In addition, dispersed silica with a specific BET surface area of 100 - 380 mm 2 / g is preferred, since it easily dissolves in an aqueous solution.

Examples of the silicon halide include silicon tetrachloride and silicon tetrafluoride.

Examples of the tetraalkyl orthosilicate include tetramethyl orthosilicate and tetraethyl orthosilicate.

Examples of the "titanium-containing compound" used in the process for preparing a Ti-MWW precursor include titanium alkoxide, titaniumates, titanium oxide, titanium halide, inorganic acid salts of titanium and organic acid salts of titanium.

Examples of the titanium alkoxide include titanium alkoxides that have an alkoxy group of 1-4 carbon atoms, for example tetramethyl orthotitanate, tetraethyl orthotitanate, tetraisopropyl orthotitanate and tetra-n-butyl orthotitanate. Preferred examples thereof include titanium alkoxides. More preferred examples thereof include tetra-n-butyl orthotitanate.

26

Examples of the organic acid salts of titanium include titanium acetate.

Examples of the inorganic acid salts of titanium include titanium nitrate, titanium sulfate, titanium phosphate and titanium perchlorate.

Examples of the titanium halide include titanium tetrachloride.

Examples of the titanium oxide include titanium dioxide.

Examples of the "water" used in the process for preparing a Ti-MWW precursor include purified water such as distilled water, ion-exchanged water and the like.

The amount of water used in the process for preparing a Ti-MWW precursor is, for example, in the range of 5 to 20 moles and preferably in the range of 10 to 50 moles, calculated on 1 mole of silicon that is present in the silicon-containing compound.

Examples of the "structure-directing agent" used in the process for preparing a Ti-MWW precursor (namely, a structure-directing agent that can form zeolite with an MWW structure) include piperidine, hexamethyleneimine, N, N, N-trimethyl-1-adamantane ammonium salts (e.g., N, N, N-trimethyl-1-adamantane ammonium hydroxide, N, N, N-trimethyl-1-adamantane-ammonium iodide, etc.) and octyltrimethylammonium salts (e.g., octyltrimethylammonium hydroxide, octyltrimethylammonium ammonium .) (see, for example, Chemistry Letters 916-917 (2007)). Preferred examples thereof include piperidine and hexamethylene imine. These compounds can be used individually or can be used as a mixture of two or more of them in any ratio.

27

The amount of the structure-directing agent used in the process for preparing a Ti-MWW precursor is, for example, in the range of 0.1 to 5 moles and preferably, for example, in the range of 0 , 5 to 3 moles, calculated on 1 mole of silicon present in the silicon-containing compound.

Also, the amount of the structure-directing agent used in the treatment of a Ti-MWW precursor with a structure-directing agent is, for example, in the range of 0.001 to 100 parts by weight and preferably, for example, in the range of 0.1 to 10 parts by weight, calculated on 1 part by weight of the titanium silicate.

The amount of the titanium silicate-containing catalyst used that is used for the reaction in the olefin oxide production process according to the present invention varies depending on the type, reaction conditions and the like, and is, for example, in the range of 0, 01 to 20 parts by weight, preferably in the range of 0.1 to 10 parts by weight and more preferably in the range of 0.5 to 8 parts by weight, calculated on 100 parts by weight of the mixture of an acetonitrile-containing solvent, the palladium-containing catalyst according to the present invention, the titanium silicate-containing catalyst and the raw materials present in the reaction system.

The amount of the palladium-containing catalyst according to the present invention used for the reaction in the production process for olefin oxide according to the present invention varies depending on the type, reaction conditions and the like, and is, for example, in the range from 0.01 to 20 parts by weight, preferably in the range of 0.1 to 10 parts by weight and more preferably in the range of 0.5 to 8 parts by weight, calculated on 100 parts by weight of the mixture of an acetonitrile-containing solvent, the palladium-containing catalyst of the present invention, the titanium silicate-containing catalyst, and the raw materials present in the reaction system.

The "acetonitrile-containing solvent" refers to a solvent containing acetonitrile, and the acetonitrile-containing solvent may contain a solvent other than acetonitrile. Examples of the solvent other than acetonitrile include organic solvents other than acetonitrile and water. Preferably, the weight ratio of the acetonitrile present in the acetonitrile-containing solvent is, for example, 50% or more and is preferably in the range of 60% to 100%.

Examples of the "olefin" which is one of the raw materials used for the reaction in the olefin oxide production process of the present invention include a hydrocarbon group with optionally a substituent, and compounds wherein hydrogen is on a carbon atom bonded, which forms an olefin bond.

In this document, examples of the "hydrocarbon group" substituent include a hydroxyl group, a halogen atom, a carbonyl group, an alkoxycarbonyl group, a cyano group, and a nitro group. Also, examples of the "hydrocarbon group" include saturated hydrocarbon groups such as an alkyl group and the like.

Typical examples of the "olefin" which is one of the raw materials used for the reaction in the olefin oxide production process of the present invention include olefins with 2-10 carbon atoms and cycloalkenes with 4- 10 carbon atoms.

29

Examples of the "olefins" with 2-10 carbon atoms "include ethylene, propylene, butene, pentene, hexene, heptene, octene, noneen, decene, 2-butene, isobutene, 2-pentene, 3-pentene, 2-hexene, 3 -hexene, 4-methyl-1-pentene, 2-heptene, 3-heptene, 2-octene, 3-octene, 2-nonene, 3-nonene, 2-decene and 3-decene. In addition, examples of the "include cycloalkenes with 4-10 carbon atoms "cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene and cyclodecene.

The preferred examples among the "olefins" include alkenes having 2 to 10 carbon atoms. More preferred examples thereof include olefins with 2-5 carbon atoms. Particularly preferred examples thereof include propylene.

When the "olefin" which is one of the raw materials used for the reaction in the production process for olefin oxide according to the present invention is "propylene", examples of the propylene include those which, by pyrolysis, catalytic cracking of heavy oil or catalytic reforming of methanol are produced.

The propylene can be purified propylene or can be crude propylene obtained without undergoing a purification process or the like. Preferred examples of propylene include propylene with a purity of 90 vol% or more and preferably a purity of 95 vol% or more.

In addition, examples of impurities present in propylene include propane, cyclopropane, methylacetylene, propadiene, butadiene, butanes, butenes, ethylene, ethane, methane, and hydrogen.

30

The form of the propylene is, for example, gaseous or a liquid form. In this document, examples of the "liquid form" include (i) propylene in liquid form of itself and (ii) a liquid mixture obtained by dissolving propylene in an organic solvent or a solvent mixture of an organic solvent and water . Also examples of the "gas form" include (i) propylene in gas form of itself and (ii) a gas mixture of gaseous propylene and other gas components such as nitrogen gas and hydrogen gas.

The amount of the olefin such as the propylene varies depending on the type, the reaction conditions and the like, and is for example 0.01 part by weight or more and preferably 0.1 part by weight or more, calculated on 100 parts by weight of the mixture of the acetonitrile-containing solvent, the titanium silicate-containing catalyst and the raw materials present in the reaction system.

The content of titanium atoms in the titanium silicate present in the titanium silicate-containing catalyst used in the production process for olefin oxide according to the present invention is, for example, in the range of 0.001 to 0.1 mol and preferably in the range of 0.005 to 0.05 mole, calculated on 1 mole of the content of silicon atoms.

The weight ratio of a noble metal to a titanium silicate (weight of noble metal / weight of titanium silicate) is, for example, in the range of 0.01% to 100% by weight and preferably, for example, in the range of 0.1% to 30% by weight to 20% by weight.

Examples of the solvent used in the olefin oxide production process of the present invention include the same solvents as those used in the hydrogen peroxide production process of the present invention. Preferred examples thereof include a nitrile solvent and a solvent mixture of a nitrile solvent and water. More preferred examples thereof include a solvent mixture of acetonitrile and water.

The ratio (weight ratio) of water to an organic solvent when a mixture of water and an organic solvent is used is, for example, in the range of 90: 10 to 0.01: 99.99 and preferably in the range of 50: 50 to 0.1: 99.9.

It may be advantageous to carry out the olefin oxide production method according to the present invention in the presence of a buffer.

In this document, the "buffer" refers to a compound comprising an anion and a cation that provide a pH buffering action. The buffer is preferably dissolved in a reaction solution, but the buffer may rather be present in the palladium-containing catalyst of the present invention.

The amount of the buffer used is, for example, in the range of 0.001 to 100 mmol / kg, calculated on 1 kg of the solvent.

The reaction temperature in the production process for olefin oxide according to the present invention is, for example, in the range of 0 ° C to 200 ° C and preferably, for example, in the range of 40 ° C to 150 ° C. Moreover, the reaction pressure (excess pressure) is, for example, a pressure of 0.1 MPa or more, preferably for example a pressure of 1 MPa or more, more preferably for example a 32 pressure of 10 MPa or more, and furthermore more preferably for example a pressure of 20 MPa or more.

For the reaction in the production process for olefin oxide according to the present invention, an ammonium salt, an alkyl ammonium salt, an alkylarylammonium salt and the like may be present in the reaction system.

A buffer tends to prevent the reduction of the catalytic activity, further to increase the catalytic activity, to improve the efficiency of using oxygen and hydrogen and the like, and can thus be present in the reaction system. In this document, the "buffer" refers to a compound such as a salt that provides a buffering action to the hydrogen ion concentration of a solution.

The amount of the buffer is, for example, an amount not less than the solubility of the buffer in the mixture of an acetonitrile-containing solvent, the palladium-containing catalyst according to the present invention and the raw materials present in the reaction system, and is in the range of preferably in the range of 0.001 to 100 mmol, calculated on 1 kg of the mixture.

Examples of the buffer include buffers comprising (1) an anion from the group consisting of a sulfate ion, a hydrogen sulfate ion, a carbonate ion, a hydrogen carbonate ion, a phosphate ion, a hydrogen phosphate ion, a dihydrogen phosphate ion, a hydrogen ion pyrophosphate ion, a pyrophosphate ion, a halogen ion, a nitrate ion, a hydroxide ion and a carboxylate ion with 1-10 carbon atoms is selected; and (2) a cation selected from the group consisting of ammonium, alkylammonium with 1-20 carbon atoms, alkylarylammonium with 7-20 carbon atoms, 33 alkali metal cations and alkaline earth metal cations.

Examples of the "carboxylate ion with 1-10 carbon atoms" include an acetate ion, formate ion, an acetate ion, a propionate ion, a butylate ion, a valerate ion, a caproate ion, a caprylaation ion, a capraate ion and a benzoate ion .

Examples of the "alkylammonium ion with 1-20 carbon atoms" include tetramethylammonium, tetraethylammonium, tetra-n-propylammonium, tetra-n-butylammonium, and trimethyl trimethyl ammonium.

Examples of the cation selected from the group consisting of alkali metal cations and alkaline earth metal cations include a lithium, a sodium, a potassium, a rubidium, a cesium, a magnesium, a calcium, a strontium and a barium cation.

Examples of the preferred buffer include ammonium salts of carboxylic acids with 1-10 carbon atoms such as ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, ammonium bicarbonate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, ammonium hydrogen pyro phosphate, ammonium pyrophosphate ammonium ammonium such, ammonium salts of inorganic acids such as ammonium chloride, ammonium nitrate and the like, and ammonium salts of carboxylic acids such as ammonium acetate and the like, and preferred examples of ammonium salts include ammonium benzoate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate.

The reaction in the olefin oxide production process according to the present invention is preferably carried out continuously. For example, the raw materials are continuously fed to an epoxidation reaction tank containing the acetonitrile-containing solvent and a catalyst whereby the reaction in the olefin oxide production process of the present invention proceeds in the epoxidation reaction tank.

[0079] When "hydrogen peroxide" is generated from "oxygen and hydrogen" in the reaction in the olefin oxide production process according to the present process, the partial pressure ratio of oxygen to hydrogen in the gas mixture of oxygen and hydrogen is at the reactor. for example oxygen: hydrogen = 1: 50 to 50: 1 and preferably oxygen: hydrogen = 1: 10 to 10: 1. It is preferred that the partial pressure of oxygen is higher than oxygen: hydrogen = 1: 50, since the production rate of propylene oxide tends to increase. It is preferable that the oxygen partial pressure is lower than oxygen: hydrogen = 50: 1, since the production of by-products, whereby the carbon-carbon double bond of the propylene with hydrogen atoms is reduced, is reduced and the selectivity to propylene oxide tends to be increased.

In addition, the gas mixture of oxygen and hydrogen is preferably processed in the coexistence of a dilution gas. In this document, "dilution gas" examples include nitrogen, argon, carbon dioxide, methane, ethane, and propane, preferably nitrogen and propane, and more preferably nitrogen.

In order to describe the mixing ratio, when oxygen, hydrogen, propylene and a dilution gas are processed in the form of a mixture, with a case where the dilution gas serves as an example, the mixing ratio with a total concentration of water is added. 35 terrogen and propylene of 4.9 volume% or less, an oxygen concentration of 9 volume% or less and the remainder nitrogen gas, or with a total concentration of hydrogen and propylene of 50 volume% or more, an oxygen concentration of 50 vol. % or 5 less and the remainder nitrogen gas is preferred.

As the oxygen, other than oxygen gas, air containing oxygen can be used. As the oxygen gas, an inexpensive oxygen gas can be used, which is produced by a pressure swing method, and high-purity oxygen gas, which is produced by cryogenic separation or the like.

The feed amount of oxygen is, for example, in the range of 0.005 to 10 moles and preferably in the range of 0.05 to 5 moles, calculated on 1 mole of the propylene fed.

Examples of the hydrogen include those obtained by means of the steam-reformed hydrocarbons. The purity of hydrogen is, for example, 80% by volume or more and preferably 90% by volume or more. The feed amount of hydrogen is, for example, in the range of 0.05 to 10 moles and preferably in the range of 0.05 to 5 moles, calculated on 1 mole of the fed propene.

[0084] When "hydrogen peroxide" is generated from "oxygen and hydrogen" in the reaction in the production process for olefin oxide according to the present process, it is preferable to prepare a quinoid compound present in the reaction system, since the selectivity to an oxirane compound tends to be further increased.

Examples of the quinoid compound include compounds represented by formula (1): 36, 1 r-M '

Y

wherein R1, R2, R3 and R4 each independently represent a hydrogen atom, or R1 and R2, or R3 and R4 are bonded to each other and form a benzene ring with optionally a substituent or a naphthalene ring with optionally a substituent together with the carbon atoms, to which R1, R2, R3 and R4 are each attached, and X and Y represent an oxygen atom or an NH group independently of each other.

Examples of the compound represented by formula (1) include: 1) a quinone compound (IA), wherein in formula (1), R1, R2, R4 and R4 are a hydrogen atom and both X and Y are a Are oxygen atom; 2) a quinone-imine compound (1B), wherein in formula (1), R 1, R 2, R 4 and R 4 are a hydrogen atom, X is an oxygen atom and Y is an NH group; and 3) a quinone diimide compound (1C), wherein in formula (1), R 1, R 2, R 4 and R 4 are a hydrogen atom and X and Y are an NH group.

[0087] Other examples of the compound represented by the formula (1) include an anthraquinone compound represented by the formula (2): 37

V

R7 II R5

DuC5 R8 II R6

Y

wherein X and Y are as defined in formula (1) and R5, R6, R7 and R8 are each independently a hydrogen atom, a hydroxyl group or an alkyl group (e.g. an alkyl group with 1-5 carbon atoms such as a methyl group , an ethyl group, a propyl group, a butyl group, a pentyl group or the like).

Preferred examples of X and Y in the compound 10 represented by the formula (1) include an oxygen atom.

Examples of the compound represented by formula (1) include quinone compounds such as benzoquinone, naphthoquinone and the like; anthraquinone; 2-15 alkylanthraquinone compounds such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, 2-methylanthraquinone, 2-butylanthraquinone, 2-t-amylanthraquinone, 2-isopropylanthraquinone, 2-s-butylanthraquinone, 2-s-amylanthraquinone and such; polyalkylanthraquinone compounds such as 1,3-diethylanthraquinone, 2,3-dimethylanthraquinone, 1,4-dimethylanthraquinone, 2,7-dimethylanthraquinone and the like; polyhydroxy anthraquinone compounds such as 2,6-dihydroxy anthraquinone and the like; p-quinoid compounds such as naphthoquinone, 1,4-phenanthraquinone and the like; and o-quinoid compounds such as 1,2-phenanthraquinone, 3,4-phenanthraquinone, 9,10-phenanthraquinone and the like. Preferred examples thereof include anthraquinone and 2-alkyl anthraquinone compounds (in formula (2), X and Y represent an oxygen atom, R 5 represents an alkyl group, 38 R 6 represents a hydrogen and R 7 and R 8 represent a hydrogen atom).

The amount of the quinoid compound used in the reaction in the production process for olefin oxide according to the present invention is, for example, in the range of 0.001 to 500 mmol and preferably in the range of 0.01 to 50 mmol per 1 kg of the solvent.

The quinoid compound can be prepared by oxidizing and dihydroforming the quinoid compound in the reaction system using oxygen or the like. For example, a compound obtained by hydrogenating a quinoid compound such as 9,10-anthracendiol or hydroquinone can be added to a liquid phase, whereby it is oxidized by oxygen in the reaction system, thereby generating and using a quinoid compound.

Examples of the "dihydro form of the quinoid compound" include a compound represented by the formula (3), which is a dihydro form of the compound represented by the formula (1):

XH

r3v ^ \ / r1 r2

YH

Wherein R1, R2, R3, R4, X and Y represent the same as defined above and a compound represented by formula (4), which is a dihydro form of the compound, represented by formula (2) shown: 39

XH

R7 | Rs ncpj • RS I R «

YH

wherein X, Y, R5, R6, R7 and R8 represent the same as defined above.

Among the compounds represented by formula (3) and the compounds represented by formula (4), preferred compounds include dihydroforms corresponding to the preferred quinoid compounds. In addition, preferred examples of X and Y in the compounds represented by formula (3) and the compounds represented by formula (4) include an oxygen atom.

[0091] Next, in order to regain or regain the catalytic activity of the palladium-containing catalyst of the present invention, the catalytic activity of which is reduced as a result of use in the production of olefin oxide or the like for a long time, regenerating, the palladium-containing catalyst of the present invention is previously contacted with a carbon-providing compound having 4 or fewer carbon atoms that is gaseous under conditions of ordinary pressure and temperature.

Any method can be used to contact the palladium-containing catalyst of the present invention with a carbon-providing compound having 4 or fewer carbon atoms that is gaseous under conditions of ordinary temperature and pressure, and include 40 examples thereof (1) a dry process in which the palladium-containing catalyst of the present invention is introduced into a reactor, then the compound is circulated while being kept warm, and (2) a wet process in which the palladium-containing catalyst of the present invention is is suspended in a solvent or the like in a sealed container such as an autoclave together with the compound and kept at the same temperature, or the compound is circulated by bubbling or the like.

Examples of the "carbon-providing compound with 4 or fewer carbon atoms that is gaseous under normal temperature and pressure conditions" used in the catalytic activity recovery and regeneration step include carbon monoxide, methane, ethane, propane , butane, ethylene, propylene, butene and butadiene. Preferred examples thereof include propylene and the like.

The temperature of the catalytic activity recovery and regeneration step is, for example, in the range of 25 ° C to 500 ° C, preferably, for example, in the range of 50 ° C to 300 ° C, and more preferably, for example, in the range from 100 ° C to 200 ° C. Also, the pressure of the catalytic activity recovery and regeneration step is, for example, in the range of 0 to 10 MPa overpressure.

The lower limit of the contact time of the catalytic activity recovery and regeneration step is for example 10 minutes, preferably for example 2 hours, more preferably for example 10 hours and further preferably for example 12 hours. Also, the upper limit of 41 the contact time of the catalytic activity recovery and regeneration step is, for example, 120 hours, preferably for example 72 hours, more preferably for example 30 hours and further preferably for example 24 hours.

In the contacting step, the palladium-containing composition, including palladium and a support, may be in the state in which it is mixed together with the titanium silicate-containing catalyst described below.

Furthermore, the palladium-containing catalyst of the present invention can be used as a catalyst for producing hydrogen peroxide from oxygen and hydrogen. The process for producing hydrogen peroxide is described below.

The process for producing hydrogen peroxide using the palladium-containing catalyst of the present invention comprises the step of converting oxygen and hydrogen in the presence of the palladium-containing catalyst of the present invention.

Oxygen and hydrogen are necessary in the above step. Any source of oxygen and hydrogen can be used, and examples of the source of oxygen include a high purity oxygen gas produced by cryogenic separation or the like, an inexpensive oxygen gas produced by a pressure swing method and sky.

The molar ratio of hydrogen to oxygen (¾: O2) used in the above step is, for example, in the range of 1: 50 to 50: 1, preferably in the range of 1: 10 to 10: 1 and more preferably in the range of 1: 5 to 5: 1.

42

In addition to oxygen and hydrogen, an inert gas can be used for the dilution in the above step. Examples of a suitable inert gas include helium, argon, nitrogen, and carbon dioxide. Preferred examples thereof include nitrogen. The inert gas is prepared in the reaction system, whereby the levels of oxygen and hydrogen in the reaction mixture can advantageously be kept outside the explosion limit.

[0100] The above step can be carried out in the presence of a solvent.

Examples of the solvent used in the above step include water, organic solvents, and mixtures thereof. Examples of the organic solvent include alcohol solvents with 1-12 carbon atoms such as methanol, ethanol, isopropyl alcohol, t-butyl alcohol, glycerol and the like, ketone solvents with 3-12 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and the like , nitrile solvents with 2-12 carbon atoms such as acetonitrile, propionitrile, isobutyronitrile, butyronitrile, benzitrile and the like, ether solvents such as diethyl ether, tetrahydrofuran, propylene glycol dimethyl ether and the like, aliphatic hydrocarbon solvents with 5-12 carbon atoms such as pentane, cyclopentane, cyclopentane , cyclohexane, ethylene dichloride, chloroform and the like, aromatic hydrocarbon solvents with 6-12 carbon atoms such as benzene, toluene, xylene, chlorobenzene and the like, ester solvents such as ethyl acetate, butyl acetate, propylene glycol diacetate and the like, and mixtures thereof. Preferred examples thereof include a nitrile solvent alone or an alcohol solvent separately, and solvent mixtures of a nitrile solvent or an alcohol solvent and water. More preferred examples include solvent mixtures of acetonitrile or methanol and water.

The ratio (weight ratio) of water to an organic solvent when a mixture of water and an organic solvent is used is, for example, in the range of 90: 10 to 0.01: 99.99 and preferably in the range of 50 : 50 to 0.1: 99.9.

The process for producing hydrogen peroxide can be carried out in various ways such as continuous flow, semi-batch and batch, and is preferably carried out in a continuous flow method. The palladium-containing catalyst of the present invention can be used in a slurry or fixed bed.

[0102] The reaction temperature in the process for producing hydrogen peroxide is, for example, in the range of 0 ° C to 100 ° C and preferably, for example, in the range of 20 ° C to 60 ° C.

The lower limit of the reaction pressure in the hydrogen peroxide production process is, for example, 0.1 MPa and preferably, for example, 1 MPa. On the other hand, the upper limit is, for example, 20 MPa and preferably, for example, 10 MPa.

[0103] It may be advantageous to carry out the process for producing hydrogen peroxide in the presence of an acid.

Examples of the acid used in the process for producing hydrogen peroxide include inorganic acids such as nitric acid, sulfuric acid, phosphoric acid, hydrochloric acid, hydrobromic acid and the like, and organic acids such as pyrophosphoric acid, acetic acid and the like.

44

The amount of the acid used in the hydrogen peroxide production process is, for example, in the range of 0.1 to 1000 parts per million by weight, preferably in the range of 0.1 to 100 parts per million per weight weight and more preferably in the range of 1 to 10 parts per million by weight, calculated on 1 part by weight of the reaction mixture.

Examples [0104] The present invention is further described below with reference to the examples.

[0105] <Various analytical devices used in the examples> (Method for elemental analysis) The levels of Pd (palladium), Ti (titanium) and Si (silicon) in the palladium-containing catalyst of the present invention, containing a palladium composition and a titanium silicate-containing catalyst were determined by means of an alkaline melt-nitric acid solution -20 emission spectrometry with ICP. More specifically, 20 mg of a sample was weighed in a platinum crucible and sodium carbonate was passed onto the sample, followed by a melting operation by means of a gas burner. After melting, the contents of the platinum after crucible were dissolved in pure water and nitric acid with heating, and then their volume was adjusted with pure water. The resulting assay solution was then analyzed with an ICP emission spectrometer (ICPS-8000, manufactured by Shimadzu Corporation), quantitative determination of the amount of each element.

In addition, the content of N (nitrogen) in the titanium silicate-containing catalyst was determined by means of a sample weighing 10 - 20 mg, calculated on circulating combustion with oxygen and TCD detection systems using SUMIGRAPH (manufactured by Sumika Chemical Analysis Service. Ltd.) (reaction temperature of 850 ° C, reduction temperature of 600 ° C). A column packed with porous polymer beads was used as the separation column and acetanilide was used as the standard sample.

[0106] (X-ray diffraction (XRD)) An X-ray diffraction pattern of the titanium silicate-containing catalyst of the present invention was determined using the device below under the following assay conditions.

- Device: RINT 2500 V, manufactured by Rigaku Corpo-15 ration - X-ray (source): Cu-Ka - Output: 40 kV - 300 mA - Scan area: 29 = 0.75 - 30 ° - Scan speed: 1 ° / minute 20 X-ray diffraction patterns of the palladium-containing catalyst of the present invention and the palladium-containing composition were determined using the device below under the following assay conditions.

25 - Device: RINT 2500 V, manufactured by Rigaku Corpo ration

- X-ray (source): Cu-Ka - Output: 40 kV - 300 mA

- Scan area: 20 = 30 - 90 ° 30 - Scan speed: 1 ° / minute

(Ultraviolet visible absorption spectrum (UV-Vis)) 46

The titanium silicate-containing catalyst of the present invention was thoroughly pulverized in an agate mortar and further formed into pellets (7 mm ¢), whereby a sample was prepared for determination. An ultraviolet visible absorption spectrum of the resulting sample for the assay was determined using the device below under the following assay conditions.

- Device: diffuse reflector (Praying Mantis, manufactured by HARRICK) - Accessory: ultraviolet-visible spectrophotometer (V-7100, manufactured by JASCO Corporation) - Pressure: atmospheric pressure - Measured value: reflection 15 - Data acquisition time: 0.1 second - Bandwidth: 2 nm - Wavelength of the determination: 200 - 900 nm - Gap height: half open - Data acquisition interval: 1 nm 20 - Baseline correction (reference): BaSO ^ pellets (7 mm <t)

(Reference control example 1: preparation of palladium-containing composition A)

A regeneration round bottom of 11 was loaded with 20 g of zirconia-25 µmoxide (DAIICHI KIGENSO KAGAKU KOGYO CO., LTD., Trade name: RSC-100) and 300 ml of water and the substances were stirred under air at 20 °. To this suspension was slowly added dropwise 100 ml of an aqueous solution with 1.90 mmol of colloidal Pd (produced by JGC Catalysts 30 and Chemicals Ltd., see JP-A 2002-294301, Example 1 and the like) at room temperature under air. After the dropwise addition, the suspension was further stirred for 47 hours at room temperature under air. After completion of the stirring, water was removed using a rotary evaporator and the resulting substance was dried under vacuum at 80 ° for 6 hours, whereby a palladium-containing composition A was obtained. The concentration of palladium present in the palladium-containing composition was 1.14% by weight with respect to the palladium metal (analysis value based on analysis by ICP emission).

(Example 1: preparation of palladium-containing composition A according to the present invention)

A glass flame tube was filled with 10 g of the palladium-containing composition A obtained in reference control example 1 and 100% ethylene gas was passed over the solid at 25 ° 15 at a rate of 10 ml / minute. Furthermore, the temperature of the contents was raised to 200 ° under a stream of ethylene gas for 2 hours, and the contents were further kept at the same temperature for 6 hours. After completion, the gas was immediately replaced with nitrogen gas at 100 ml / minute and the contents allowed to cool to room temperature, thereby obtaining the palladium-containing catalyst A of the present invention. The concentration of the palladium present in the palladium-containing catalyst A was 1.14% by weight with respect to the palladium metal (analysis value based on an analysis by ICP emission).

[0110] (Reference Control Example 2: Preparation of Palladium-containing Composition B) A regeneration round bottom of 1 liter was prepared with 3 g of activated carbon (produced by Wako Pure Chemical Industries, Ltd., trade name: activated carbon powder) and 48 225 ml of acetonitrile (produced by NACALAI TESQUE, INC.), and the substances were stirred at 20 ° C in air. To the resulting suspension was slowly added dropwise 35 ml of acetonitrile with 0.0647 g of palladium acetate (produced by Aldrich) at room temperature under air. After the dropwise addition, the resulting suspension was stirred under air at room temperature for 8 hours. After completing the stirring, water was removed using a rotary evaporator and then the resulting residue was dried under vacuum for 6 hours at 80 ° C, whereby a palladium-containing composition B was obtained. The concentration of palladium present in the palladium-containing composition B was 1.01% by weight with respect to the palladium metal (analysis value based on an analysis by ICP emission).

(Example 2: preparation of palladium-containing catalyst B according to the present invention)

A glass flame tube was filled with 1.43 g of the palladium-containing composition B obtained in reference control example 2 and 100% ethylene gas was passed over the solid at 25 ° at a rate of 10 ml / minute. Furthermore, the temperature of the contents was raised to 200 ° under a stream of ethylene gas for 2 hours, and the contents were further kept at the same temperature for 6 hours. After completion, the gas was immediately replaced with nitrogen gas at 100 ml / minute and the contents were allowed to cool to room temperature, whereby the palladium-containing catalyst B of the present invention was obtained. The concentration of the palladium present in the palladium-containing catalyst B was 1.01% by weight with respect to the palladium metal (analysis value based on an analysis by ICP emission).

In this document, the X-ray diffraction patterns of the palladium-containing catalyst B according to the present invention obtained above and the palladium-containing composition B obtained in reference control example 2 are shown in FIG. It is clear that the palladium-containing catalyst B according to the present invention has a value of the distance of the grating surface 10 of a (111) surface of a palladium metal of 2,270 Å or more.

(Example 3: production of titanium silicate-containing catalyst)

Under an air atmosphere, 899 g of piperidine and 2402 g of ion-exchanged water were mixed and stirred at room temperature (22 °). To the resulting mixture was added dropwise 46 g of TBOT (tetra-n-butyl orthotitanate) and the substance was dissolved with stirring. After TBOT was dissolved, 565 g of boric acid was added to the mixture and dissolved with stirring.

Then 410 g of high-dispersion silica (cab-o-sil M7D, produced by Cabot Corporation) was added to the resulting mixture and dissolved with stirring under an air atmosphere, and then the mixture was allowed to stand for 1.5 hours. The solution was transferred to a 5-liter autoclave equipped with two anchor-type stirring blades and then the autoclave was sealed. An airtightness test was conducted at 1.5 MPa (excess pressure) using argon gas, then the pressure of the autoclave was lowered and the autoclave was resealed.

50

Subsequently, the temperature of the contents in the autoclave was raised to 150 ° C for 8 hours while the anchor-type stirring blades rotated. The temperature was kept at the same temperature for 120 hours and the contents in the autoclave were cooled, thereby obtaining a suspended solution as a reactant.

The resulting suspended solution was filtered, then the product on the filter was washed with ion-exchanged water until the washed filtrate 10 had a pH of about 10.

The product was then dried on the filter after washing (drying temperature: 50 ° C) until the mass decrease was no longer observed. The resulting dry matter was washed with ion-exchanged water and dried, yielding about 520 g of a layered compound. The above processes were repeated six times, yielding a total of 3120 layered compound.

Under an air atmosphere, at an outside temperature of 20-30 ° C, a metal container with glass lining (200 l, 20 coated with a reflux tube) with 3 kg of the resulting layered compound, 158 kg of a 2 M aqueous nitric acid solution and 0.38 kg of TBOT loaded. The jacket temperature of the container was raised to 115 ° C, kept at the same temperature for 9 hours and further raised to a jacket temperature of 124 ° C, and the contents were refluxed for 7 hours at the same temperature. After refluxing, heating of the jacket was terminated, the contents being cooled to room temperature.

The resulting content was filtered, then the product on the filter was washed with ion-exchanged water 51 until the washed filtrate had a pH of about 5.

The product was then dried on the filter after washing (drying temperature: 80 ° C) until no more reduction of the mass was observed, whereby a white solid was obtained, and furthermore the white solid was pulverized, whereby a white powder was obtained. A portion of the resulting white powder was introduced into a glass tube, and the temperature was raised from a room temperature to 530 ° C for 2 hours under a nitrogen gas stream of 6 1 (0 ° C with respect to 1 atm.) / Hour 2 hours at the same temperature. The nitrogen gas stream was then replaced with an air stream of 6 1 (0 ° C, relative to 1 atm.) / Hour, and the temperature was kept at 530 ° C for 4 hours.

A 1.5 L autoclave was charged with 150 g of the white powder fired as described above, 300 g of piperidine and 600 g of ion-exchanged water under an air atmosphere at room temperature. The charged contents were dissolved under the same atmosphere at the same temperature with stirring and then the mixture was allowed to stand for 1.5 hours. The solution was transferred to a 1.51 autoclave equipped with one anchor type rudder blade, and then the autoclave was sealed. An airtightness test was conducted at 1.0 MPa (excess pressure) using argon gas, then the pressure of the autoclave was lowered and the autoclave was closed again.

Subsequently, the temperature of the contents in the autoclave was raised to 150 ° C for 4 hours while the anchor type rudder blade rotated. The contents were then heated for 1 day to maintain a temperature in the range of 52 from 150 ° C to 170 ° C with 160 ° C as a guide. After heating, the contents in the autoclave were cooled, whereby a suspended solution was obtained as a reactant.

The resulting suspended solution was filtered, then the product on the filter was washed with ion-exchanged water heated to about 100 ° C. until the washed filtrate had a pH value of about 9, with a white solid substance was obtained.

The resulting white solid was sufficiently dried at 150 ° C using a vacuum drier and then pulverized to yield a white powder. As a result of the elemental analysis, the white powder had a Ti content of 2.06% by weight, an Si content of 36.3% by weight and an N content of 0.91% by weight. It was also confirmed that the X-ray diffraction pattern of the white powder peaks at 12.4 d / A, 11.2 d / A, 9.0 d / A, 6.2 d / A, 3.9 d / A and 3.4 d / A. Furthermore, it was found that the white powder exhibited the maximum absorption peak at 213 nm for an ultraviolet visible absorption spectrum in a wavelength range of 200-400 nm, and it was confirmed to be a Ti-MWW precursor.

[0113] (Example 4: method 1 for producing olefin oxide according to the present invention)

An 0.5 L autoclave was added with 1.14 g of the titanium-silicate-containing catalyst obtained in Example 3, 0.53 g of the palladium-containing catalyst A of the present invention obtained in Example 1 and 117 g of a 30/70 (weight ratio) water / acetonitrile solution was charged, and then the autoclave was sealed.

53

Subsequently, a raw material gas with an oxygen / hydrogen / nitrogen / propylene volume ratio of 3.8 / 3, 1 / 93.0 / 86.9 / 6.3 was introduced into the autoclave at a speed of 107 NL / hour and 0.7 mmol / kg of anthraquinone and a solution of water with 3.0 mmol / kg of diammonium hydrogen phosphate / acetonitrile with a ratio of 30/70 (weight ratio) were introduced into the autoclave at a rate of 117 g / h and then reaction mixture was taken out of the autoclave through a filter, a continuous reaction being carried out. In this document, the conditions of the continuous reaction were a temperature of 60 ° C, a pressure of 0.8 MPa (excess pressure) and a residence time of 60 minutes.

A sampling was performed at 2 hours and 5 hours after the start of the reaction, and the liquid sample and gas phases were analyzed using gas chromatography. The results showed that the production amount of propylene oxide was 87.4 mmol / g (palladium support) / hour (average of the results after 3 and 5 hours).

(Reference control example 3: method 1 for producing olefin oxide for the reference control)

The same processes as in Example 4 were performed, except that the palladium-containing composition obtained in Reference Control Example 1 was used instead of the palladium-containing catalyst A of the present invention to produce propylene oxide. A sampling was performed at 2 hours and 5 hours after the start of the reaction, and the liquid sample and gas phases were analyzed using gas chromatography. The results showed that the production amount of propylene oxide was 77.5 mmol / g 54 (palladium support) / hour (average of the results after 3 and 5 hours).

(Example 5: Process 2 for producing olefin oxide according to the present invention) The same processes as in Example 4 were carried out, except that the palladium-containing composition B obtained in Example 2 instead of the palladium-containing catalyst A according to the present invention was used to produce propylene oxide. A sampling was performed at 2 hours and 5 hours after the start of the reaction, and the liquid sample and gas phases were analyzed using gas chromatography. The results showed that the production amount of propylene oxide was 60.4 mmol / g (palladium carrier) / hour (average of the results after 3 and 5 hours).

(Reference control example 4: method 2 for producing olefin oxide for the reference control)

The same processes as in Example 4 were performed, except that the palladium-containing composition B 20 obtained in Reference Control Example 2 was used instead of the palladium-containing catalyst A of the present invention to produce propylene oxide. A sampling was performed at 2 hours and 5 hours after the start of the reaction, and the liquid sample and gas phases were analyzed using gas chromatography. The results showed that the production amount of propylene oxide was 56.8 mmol / g (palladium support) / hour (average of the results after 3 and 5 hours).

[0117] (Example 6: method 3 for producing olefin oxide according to the present invention) 55

An 0.5 L autoclave was added with 1.14 g of the titanium-silicate-containing catalyst obtained in Example 3, 0.53 g of the palladium-containing catalyst A of the present invention obtained in Example 1 or the palladium-containing composition A obtained with reference control example and 117 g of a 30/70 (weight ratio) solution of water / acetonitrile was charged, and then the autoclave was sealed.

Subsequently, a raw material gas with an oxygen / hydrogen / nitrogen / propylene volume ratio of 3.8 / 3.1 / 93.0 / 86.9 / 6.3 was introduced into the autoclave at a speed of 107 NL / hour and 0.7 mmol / kg of anthraquinone and a solution of water with 3.0 mmol / kg of diammonium hydrogen phosphate / acetonitrile with a ratio of 30/70 (weight ratio) were introduced into the autoclave at a rate of 117 g / hour and then the reaction mixture was taken out of the autoclave through a filter, whereby a continuous reaction was performed. In this document, the conditions of the continuous reaction were a temperature of 60 ° C, a pressure of 0.8 MPa (excess pressure) and a residence time of 60 minutes.

After the predetermined reaction time was over and the catalytic activity was reduced, only propylene feeding was continued in the state where feeding of (a) only hydrogen, (b) oxygen only or (c) both in the gas of the raw material material was terminated (a state where the reaction for the production of olefin oxide was terminated). The temperature at that time point was the reaction temperature or higher. The activity of the palladium-containing catalyst, the catalytic activity of which was reduced due to the predetermined treatment time, was recovered or regenerated, and the reaction for the production of olefin oxide can be carried out again with a favorable catalytic activity.

[0118] (Example 7: use of palladium-containing catalyst according to the present invention: process for producing hydrogen peroxide)

A 0.5 L autoclave was charged with 0.06 g of the palladium-containing catalyst A of the present invention, and then a raw material gas with a nitrogen / hydrogen / oxygen volume ratio of 90.0 / 4.7 / 4, 4 was introduced into the autoclave at a rate of 18 L / hour and a solvent (water / methanol) = 20/80 (weight ratio) was introduced into the autoclave at a rate of 171 g / hour, then the reaction mixture was passed through a filter from the autoclave, with a continuous reaction being carried out. In this document, the conditions of the continuous reaction were a temperature of 40 ° C, a pressure of 0.8 MPa (excess pressure) and a residence time of 45 minutes to produce hydrogen peroxide.

20

Industrial applicability

[0119] According to the present invention, it is possible, by using a titanium silicate-containing catalyst together, to provide a catalyst that results in providing a high production amount of an olefin oxide in a reaction for producing an olefin oxide. from oxygen, hydrogen and an olefin.

30 1039702

Claims (12)

Method for producing an olefin oxide comprising the step of converting oxygen, hydrogen and an olefin, in the presence of a carbon-containing, gas-treated, palladium-containing catalyst obtained by contacting bringing a palladium-containing composition comprising palladium and a support with a compound selected from the group consisting of acetylene, ethylene and carbon monoxide and a titanium silicate-containing catalyst. 2. Method for producing an olefin oxide according to claim 1, wherein the olefin is propylene. 3. A method for producing an olefin oxide according to claim 1 or 2, wherein the titanium silicate-containing catalyst comprises titanium silicate particles with an X-ray diffraction pattern with peaks at the positions shown below as the distance from the grid surface. <Positions of the peaks in an X-ray diffraction pattern represented as distance from the grid surface (distance from the grid surface d / A)> 12.4 ± 0.8, 10.8 ± 0.5, 9.0 ± 0.3 , 6.0 ± 0.3, 3.9 ± 0.3 and 3.4 ± 0.1 4. A process for producing an olefin oxide according to any of claims 1-3, wherein the step is a step of converting oxygen, hydrogen and an olefin in the presence of a solvent. 1039702 The method for producing an olefin oxide according to claim 4, wherein the solvent is an organic solvent. The method for producing an olefin oxide according to claim 4, wherein the solvent is a solvent mixture of an organic solvent and water. 7. Method for producing an olefin oxide according to claim 5 or 6, wherein the organic solvent is acetonitrile. 8. A method for producing an olefin oxide according to any of claims 1-7, wherein the palladium-containing catalyst is a palladium-containing catalyst, the catalytic activity of which has been recovered or regenerated by previously contacting a carbon-providing agent compound having 4 or fewer carbon atoms that is gaseous under conditions of ordinary temperature and pressure. 9. A method for producing an olefin oxide according to claim 8, wherein the carbon-providing compound with 4 or fewer carbon atoms that is gaseous under normal temperature and pressure conditions is propylene. 10. A carbon-containing, gas-treated, palladium-containing catalyst obtained by contacting a palladium-containing composition comprising palladium and a support having a compound selected from the group consisting of acetylene, ethylene and carbon monoxide. A carbon-containing, gas-treated, palladium-containing catalyst according to claim 10, wherein the carrier is a carrier selected from the group consisting of activated carbon, Al 2 O 3 and ZrO 2. 12. A carbon-containing, gas-treated, palladium-containing catalyst according to claim 10 or 11, wherein the value of the distance of the crystal surface of a (111) surface of a palladium metal, calculated from a diffraction angle that is X-rayed diffraction analysis has been determined to be 2.270A or more. 15 20 25 30 1039702