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WO2012015056A1 - Titanosilicate et procédé de production d'oxyde d'oléfine à l'aide du titanosilicate comme catalyseur - Google Patents

Titanosilicate et procédé de production d'oxyde d'oléfine à l'aide du titanosilicate comme catalyseur Download PDF

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Publication number
WO2012015056A1
WO2012015056A1 PCT/JP2011/067567 JP2011067567W WO2012015056A1 WO 2012015056 A1 WO2012015056 A1 WO 2012015056A1 JP 2011067567 W JP2011067567 W JP 2011067567W WO 2012015056 A1 WO2012015056 A1 WO 2012015056A1
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Prior art keywords
titanosilicate
catalyst
compound
producing
hydrogen peroxide
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Tomonori Kawabata
Yuka Kawashita
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/12—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation
    • B01J2229/123—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation in order to deactivate outer surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy

Definitions

  • the present invention relates to a titanosilicate, a process for producing thereof and a process for producing an olefin oxide using the titanosilicate as a catalyst.
  • JP 2005-262164 A describes a titanosilicate obtained by hydrothermally synthesizing of a boron-containing compound, tetrabutyl orthotitanate, fumed silica and piperidine at a temperature of 170°C, and bringing the obtained layered compound (also referred to as an as-synthesized sample) into contact with an aqueous nitric acid solution under reflux conditions.
  • JP 2005-262164 A also describes a process for producing a propylene oxide from hydrogen peroxide and propylene by using the titanosilicate as a catalyst.
  • a yield of an olefin compound based on the amount of an oxidizing agent (hereinafter sometimes simply referred to as a "yield"), such as a yield of propylene oxide based on the amount of hydrogen peroxide, is not necessarily satisfactory.
  • An object of the present invention is to provide a catalyst capable of producing an olefin oxide from an oxidizing agent and an olefin compound in a high yield.
  • a titanosilicate with low bulk density is a catalyst capable of producing an olefin oxide in a high yield, and accomplished the present invention.
  • the present invention provides the followings:
  • a titanosilicate having a bulk density of 0.05 g/ml to 0.15 g/ml, and having an X-ray diffraction pattern with the following values :
  • a process for producing a titanosilicate comprising a first step of heating a mixture containing a structure-directing agent, a compound containing an element belonging to Group 13 of the periodic table, a titanium-containing compound, a silicon-containing compound and water under a temperature condition of lower than 155°C to obtain a solid; and a second step of bringing at least one selected from the group consisting of inorganic acids and titanium-containing compounds into contact with the solid obtained in the first step.
  • a catalyst for producing an olefin oxide comprising the titanosilicate according to the above item [1], [2] or [10].
  • a process for producing an olefin oxide comprising a step of oxidizing an olefin compound with an oxidizing agent in the presence of the catalyst according to the above item [11] .
  • Fig. 2 is an electron micrograph showing the
  • the titanosilicate of the present invention has an X-ray diffraction pattern with values described above, and has a bulk density of 0.05 g/ml to 0.15 g/ml, preferably 0.08 g/ml to 0.11 g/ml.
  • the titanosilicate having such properties is a catalyst capable of producing an olefin oxide in a high yield.
  • the catalyst containing the titanosilicate having the properties described above sometimes referred to as the "present catalyst".
  • the present catalyst is very useful as a catalyst used in process for producing an olefin oxide, as described below.
  • the titanosilicate has the following X-ray diffraction pattern.
  • the bulk density of the present catalyst can be determined in accordance with a tap density method. That is, the present catalyst is put in a graduated cylinder, and its weight is measured. Subsequently, the graduated cylinder is tapped until the volume of the present catalyst does not decrease any more. After tapping, the volume of the present catalyst is measured. From the weight and volume thus obtained, the bulk density (g/ml) is calculated.
  • the primary particle of the present catalyst may be a titanosilicate in a hexagonal plate shape.
  • One side of the hexagonal plate is, for example, about 0.05 ⁇ to about 0. 2 urn, and the thickness of the hexagonal plate is, for example, about 10 nm to about 50 nm.
  • An electron micrograph of the titanosilicate obtained in Example 1 described below is shown in Fig. 1 as a typical example.
  • the present catalyst can be produced by, for example, a production method comprising the following first step and second step:
  • the first step a step of heating a mixture containing a structure-directing agent, a compound containing an element belonging to Group 13 of the periodic table, a
  • silicon-containing compound, the titanium-containing compound and the structure-directing agent, which are used in the first step, will be described.
  • Group 13 element-containing compound examples include boron-containing compounds, aluminum-containing compounds and gallium-containing compounds.
  • gallium-containing compound include gallium oxide.
  • the boron-containing compounds is preferable, and boric acid is more preferable.
  • titanium-containing compound examples include titanium alkoxides, organic acid salts of titanium, inorganic acid salts of titanium, halogenated titanium and titanium oxide .
  • Examples of the organic acid salt of titanium include titanium acetate; examples of the inorganic acid salt of titanium include titanium nitrate, titanium sulfate, titanium phosphate, and titanium perchlorate; examples of halogenated titanium include titanium tetrachloride; and examples of titanium oxide include titanium dioxide.
  • the titanium alkoxides are preferable, and tetra-n-butyl orthotitanate is more preferable.
  • the structure-directing agent means a
  • Such a structure-directing agent can form a precursor of the zeolite structure by organizing polysilicate ions or polymetallosilicate ions around the agent (see “Zeoraito no Kagaku” (Science and Technology of Zeolites) , pp.33-34, 2000, Kodansha Scientific) .
  • the amount of water used in the first step may be adjusted to a range of 5 mol to 200 mol, preferably 10 mol to 50 mol per mol of silicon in the silicon-containing compound used in the first step.
  • silicon-containing compound and water is put in a closed vessel such as an autoclave, and heated to a temperature in the range of at most lower than 155°C.
  • the mixture is heated at a temperature in the range of preferably 100°C or higher and lower than 155°C, more preferably in the range of 130°C to 150°C.
  • the temperature is 100°C or higher, the crystallinity of the present catalyst tends to be excellent, and when it is lower than 155°C, the present catalyst having a bulk density of 0.15 g/ml or less can be obtained.
  • the temperature range described above does not mean a temperature of an external surface of the closed vessel, it means a temperature indicated by a thermometer which is brought into contact with the mixture directly, or indirectly using a sheath tube or the like.
  • the second step is a step in which at least one selected from the group consisting of inorganic acids and
  • titanium-containing compounds is brought into contact with the solid obtained in the first step.
  • inorganic acid examples include sulfuric acid, hydrochloric acid, nitric acid, perchloric acid,
  • fluorosulfonic acid and mixtures thereof are preferred.
  • preferred are nitric acid, perchloric acid, fluorosulfonic acid and mixtures thereof.
  • the inorganic acid it is preferable to use it in the form of a solution in which the acid is mixed with a solvent.
  • a solvent examples include water, alcohol solvents, ether solvents, ester solvents, ketone solvents and mixtures thereof, and among them, preferred is water.
  • the concentration of the inorganic acid in the solution may be in a range of 0.01 M to 20 M (M: the number of moles of the inorganic acid/the volume of the inorganic acid solution (L) ) , preferably 1 M to 5 M.
  • the second step is preferably carried out in the presence of a solvent.
  • a solvent the solvents which are listed above as the solvents to be mixed with the inorganic acid are preferable.
  • the third step will be specifically described.
  • the third step may be a step in which the product obtained in the second step is put in a heating furnace such as an electric furnace, the temperature is elevated to from 250°C to 1000°C, preferably from 300°C to 600°C over 1 to 24 hours, the temperature is kept for 1 hour to 24 hours, and the product is allowed to cool naturally in the furnace.
  • the titanosilicate obtained in the second step is subjected to dehydration condensation.
  • the operation of the fourth step will be specifically described.
  • Examples of the operation include an operation in which the titanosilicate obtained in the second step or the titanosilicate obtained in the third step, the
  • structure-directing agent and optionally a solvent are put in a closed vessel such as an autoclave, and the mixture is pressurized with heating; an operation in which the
  • structure-directing agent and optionally a solvent are stirred and mixed in a container such as a glass flask under the atmosphere; and an operation in which the titanosilicate obtained in the second step or the titanosilicate obtained in the third step, the structure-directing agent and optionally a solvent are statically mixed in a container such as a glass flask under the atmosphere.
  • Examples of the solvent used in the fourth step include water, alcohol solvents, ether solvents, ester solvents, ketone solvents and mixtures thereof, among them, preferred is water.
  • the lower limit of the temperature at which the titanosilicate and the structure-directing agent are brought into contact with each other in the fourth step may be 0°C, preferably 20°C, more preferably 50°C, further more preferably 100°C.
  • the upper limit of the temperature at which the titanosilicate and the structure-directing agent are brought into contact with each other in the fourth step may be 250°C, preferably 200°C, more preferably 180°C.
  • the titanosilicate and the structure-directing agent may be brought into contact with each other in the fourth step under normal pressure, reduced pressure or increased pressure. Preferably, they are brought into contact with each other under normal pressure or increased pressure such as a gauge pressure of from 0 Pa to 10 Pa.
  • the titanosilicate obtained through the fourth step is separated through, for example, filtration.
  • the separated solid may be further subj ected to a post-treatment such as washing or drying, if necessary.
  • the fifth step will be specifically described.
  • the fifth step may be a step in which the titanosilicate obtained in the second step, the titanosilicate obtained in the third step, or the titanosilicate obtained in the fourth step is silylated with a silylating agent such as 1,1,1,3,3, 3-hexamethyldisilazane in accordance with the process described in EP 1488853 Al.
  • a titanosilicate obtained through a step in which the titanosilicate obtained in the second step, the third step, the fourth step or the fifth step is brought into contact with hydrogen peroxide (hereinafter sometimes referred to as a "sixth step") is also the present catalyst.
  • the concentration of hydrogen peroxide used in the sixth step may be in a range of 0.0001% by weight to 50% by weight.
  • the temperature of the sixth step may be from 0°C to 100°C, preferably from 0°C to 60°C.
  • the process for producing an olefin oxide of the present invention is a process using the present catalyst. That is, the process for producing an olefin oxide of the present invention comprises a step in which an olefin compound is oxidized with an oxidizing agent in the presence of the present catalyst (hereinafter sometimes refereed to as an "oxidation reaction" ) .
  • the oxidizing agent means a compound capable of giving oxygen atoms to the olefin compound.
  • Examples of the oxidizing agent include oxygen and peroxides.
  • Examples of the peroxide include hydrogen peroxide and organic peroxides.
  • the hydrogen peroxide a commercially available product may be used. And also the hydrogen peroxide may be prepared from oxygen and hydrogen in the presence of a noble metal in the same reaction system as that of the oxidation reaction.
  • the amount of the oxidizing agent used in the oxidation reaction can be properly selected according to the kind of the olefin compound and the reaction conditions, and it is, for example, 0.01 part by weight or more, more preferably 0.1 part by weight or more per 100 parts by weight of the olefin compound.
  • the upper limit of the amount of the oxidizing agent used may be 1000 parts by weight, preferably 100 parts by weight per 100 parts by weight of the olefin compound.
  • the olefin compound used in the oxidation reaction refers to a compound in which a hydrocarbyl group optionally having a substituent or hydrogen is bonded to a carbon atom which forms an olefin double bond.
  • olefin compound examples include alkenes having 2 to 10 carbon atoms, and cycloalkenes having 4 to 10 carbon atoms.
  • alkene having 2 to 10 carbon atoms examples include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, 2-butene, isobutene, 2-pentene, 3-pentene, 2-hexene, 3-hexene, 4-methyl-l-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.
  • alkenes having 2 to 10 carbon atoms are preferable, alkenes having 2 to 5 carbon atoms are more preferable, and propylene is further more preferable.
  • the amount of the olefin compound used can be properly selected according to the kind thereof and the reaction conditions.
  • the amount of the olefin compound may be 0.01 part by weight or more, more preferably 0.1 part by weight or more per 100 parts by weight of the total amount of the reaction solution in the oxidation reaction.
  • the upper limit of the amount of the olefin compound may be 1000 parts by weight, preferably 100 parts by weight per 100 parts by weight of the total amount of the reaction solution.
  • organic solvent examples include alcohol solvents, ketone solvents, nitrile solvents, ether solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, ester solvents and mixtures thereof .
  • Examples of the aliphatic hydrocarbon solvent include aliphatic hydrocarbons having 5 to 10 carbon atoms such as hexane and heptane.
  • Examples of the aromatic hydrocarbon solvent include aromatic hydrocarbon solvents having 6 to 15 carbon atoms such as benzene, toluene and xylene.
  • the alcohol solvent examples include monohydric alcohols having 1 to 6 carbon atoms and glycols having 2 to 8 carbon atoms.
  • the alcohol solvent aliphatic alcohols having 1 to 8 carbon atoms are preferable, monohydric alcohols having 1 to 4 carbon atoms such as methanol, ethanol, isopropanol and t-butanol are more preferable, and t-butanol is further more preferable.
  • nitrile solvent examples include alkyl nitriles having 2 to 4 carbon atoms such as acetonitrile, propionitrile, isobutyronitrile and butyronitrile, and benzonitrile . Among them, preferred is acetonitrile.
  • solvent used in the oxidation reaction water, alcohol solvents, nitrile solvents and mixed solvents thereof are preferable from a viewpoint of the catalyst activity and selectivity.
  • the amount of the present catalyst may be properly selected according to the kind of the olefin compound.
  • the lower limit of the amount may be 0.01 part by weight, preferably 0.1 part by weight, more preferably 0.5 part by weight per 100 parts by weight of the total amount of the solvent.
  • the upper limit thereof may be 20 parts by weight, preferably 10 parts by weight, more preferably 8 parts by weight per 100 parts by weight of the total amount of the solvent.
  • the lower limit of the reaction temperature in the oxidation reaction may be 0°C, preferably 40°C.
  • the upper limit thereof may be 200°C, preferably 150°C.
  • the lower limit of the reaction pressure in the oxidation reaction may be 0.1 MPa, preferably 1 MPa.
  • the upper limit thereof may be 20 MPa, preferably 10 MPa.
  • hydrogen peroxide When hydrogen peroxide is produced in the same reaction system as that of the oxidation reaction, hydrogen peroxide can be synthesized, for example, from oxygen and hydrogen in the presence of a noble metal catalyst.
  • the noble metal catalyst examples include noble metals such as palladium, platinum, ruthenium, rhodium, iridium, osmium and gold, and alloys and mixtures thereof.
  • Preferable noble metals are palladium, platinum and gold.
  • Palladium is a more preferable noble metal.
  • palladium for example, palladium colloid may be used (see, for example, JP 2002-294301 A, Example 1, etc. ) .
  • a noble metal compound capable of being converted into a noble metal by reduction in the oxidation reaction system may be used.
  • palladium When palladium is used as the noble metal catalyst, it is possible to use a mixture of palladium and a metal other than palladium, such as platinum, gold, rhodium, iridium or osmium. Preferable metals other than palladium are gold and platinum.
  • the palladium compound examples include tetravalent palladium compounds such as sodium hexachloropalladate ( IV) -tetrahydrate, and potassium hexachloropalladate (IV); and divalent palladium compounds such as palladium (II) chloride, palladium (II) bromide, palladium (II) acetate, palladium acetylacetonate (II), dichlorobis (benzonitrile) palladium (II), dichlorobis (acetonitrile) palladium (II),
  • the noble metal is usually used in the state where it is supported on a support.
  • the noble metal may be supported on the present catalyst and the resulting product may be used, or the noble metal may be supported on an oxide such as silica, alumina, titania, zirconia or niobia, a hydrate of niobic acid, zirconic acid, tungstic acid, titanic acid or the like, carbon, or a mixture thereof, and the resulting product may be used.
  • the support which supports the noble metal may be mixed with the present catalyst, and the resulting mixture may be used as the catalyst.
  • carbon is preferably used as a support.
  • the carbon support for example, activated carbon, carbon black, graphite and carbon nanotube are known.
  • a process for preparing the noble metal catalyst for example, a process in which the noble metal compound is supported on the support and then the product is reduced, is known.
  • conventionally known methods such as an impregnation method may be used.
  • the reduction may be carried out using a reducing agent such as hydrogen, or using an ammonia gas which is generated upon thermal decomposition in an inert gas atmosphere.
  • the reduction temperature may vary depending on the kind of the noble metal compound, and is preferably from 100°C to 500°C, more preferably from 200°C to 350°C.
  • the noble metal catalyst contains the noble metal in an amount in a range of, for example, 0.01% by weight to 20% by weight, preferably 0.1% by weight to 5% by weight.
  • the weight ratio of the noble metal to the present catalyst is preferably from 0.01% by weight to 100% by weight, more preferably from 0.1% by weight to 20% by weight .
  • the buffer refers to a compound comprising anions and cations which are capable of providing a pH buffer action.
  • the buffer is dissolved in the oxidation reaction system, but when hydrogen peroxide produced in the same reaction system is used as the oxidizing agent, the buffer may be previously contained in the noble metal catalyst.
  • a method for example, a method in which after an ammine complex such as Pd-tetraammine chloride is supported on the support by impregnation or the like, the resulting product is reduced and ammonium ions are left, and the buffer is generated during the oxidation reaction, is exemplified.
  • the amount of the buffer added may be in the range of 0.001 mmol/kg to 100 mmol/kg per kg of the solvent.
  • buffers comprising 1) an anion selected 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 pyrophosphate ion, a pyrophosphate ion, a halogen ion, a nitrate ion, a hydroxide ion and a carboxylate ion having 1 to 10 carbon atoms, and 2) a cation selected from the group consisting of an ammonium, an alkyl ammonium having 1 to 20 carbon atoms, an alkyl aryl ammonium having 7 to 20 carbon atoms, an alkali metal and an alkaline earth metal.
  • carboxylate ion examples include an acetate ion, a formate ion, a propionate ion, a butyrate ion, a valerate ion, a caproate ion, a caprylate ion, a caprate ion and a benzoate ion.
  • alkyl ammonium examples include tetramethyl ammonium, tetraethyl ammonium, tetra-n-propyl ammonium, tetra-n-butyl ammonium, and cetyl trimethyl ammonium;
  • examples of the alkali metal and the alkaline earth metal cation include a lithium cation, a sodium cation, a potassium cation, a rubidium cation, a cesium cation, a magnesium cation, a calcium cation, a strontium cation and a barium cation.
  • the buffer include ammonium salts of inorganic acids such as ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, ammonium hydrogen carbonate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, ammonium hydrogen pyrophosphate, ammonium pyrophosphate, ammonium chloride and ammonium nitrate; and ammonium salts of carboxylic acids such as ammonium acetate.
  • ammonium dihydrogen phosphate is preferable.
  • the quinoid compound may be a p-quinoid compound and an o-quinoid compound represented by the following formula (1) :
  • R 1 , R 2 , R 3 and R 4 are each a hydrogen atom; or R 1 and R 2 , or R 3 and R 4 , are bonded to each other at the ends thereof to form an optionally substituted naphthalene ring together with carbon atoms to which they attach; and X and Y are the same or different and represent an oxygen atom or a NH group.
  • Examples of the compound of the formula (1) include 1) a quinone compound (1A) represented by the formula (1) in which R 1 , R 2 , R 3 and R 4 are each a hydrogen atom, and both X and Y are each an oxygen atom;
  • the quinoid compound represented by the formula (1) includes the following anthraquinone compound (2) :
  • X and Y are each preferably an oxygen atom.
  • quinoid compound examples include benzoquinone, naphthoquinone, anthraquinone, alkyl anthraquinone compounds, polyhydroxyanthraquinone and 9, 10-phenanthraquinone .
  • alkyl anthraquinone compound examples include 2-alkyl anthraquinone compounds such as 2-ethyl anthraquinone, 2-t-butyl anthraquinone, 2-amyl anthraquinone, 2-methyl anthraquinone, 2-butyl anthraquinone, 2-t-amyl anthraquinone, 2-isopropyl anthraquinone, 2-s-butyl anthraquinone and
  • polyhydroxyanthraquinone examples include
  • R 5 is an alkyl group which is substituted at the 2-position
  • R 6 is a hydrogen atom
  • R 7 and R 8 are each a hydrogen atom.
  • the quinoid compound can also be prepared by oxidizing a dihydro form of the quinoid compound in the oxidation reaction system using oxygen or the like.
  • a quinoid compound such as hydroquinone or 9, 10-anthracene diol which has been hydrogenated may be added to the oxidation reaction system and oxidized with oxygen in the reaction vessel to generate a quinoid compound, and the resulting quinoid compound may be used .
  • dihydro form of the quinoid compound examples include compounds represented by the following formulae (3) and (4), which are the dihydro forms of the compounds represented by the formulae (1) and (2) :
  • R 1 , R 2 , R 3 , R 4 , X and Y mean the same as defined in the formula (1) :
  • X and Y are each preferably an oxygen atom.
  • dihydro form of the quinoid compound examples include dihydro forms corresponding to the preferable quinoid compounds described above.
  • oxygen and hydrogen may be diluted.
  • the gas used for dilution include nitrogen, argon, carbon dioxide, methane, ethane and propane .
  • the concentration of the dilution gas is not limited, and, if necessary, the synthesis reaction of hydrogen peroxide is carried out after diluting oxygen or hydrogen.
  • Oxygen may be used as it is, or a mixed gas such as air or a mixed gas of oxygen and the gas used for dilution described above may be used.
  • An oxygen gas which is produced by an inexpensive pressure swing method may be used, or, if necessary, a high purity oxygen gas which is produced by cryogenic separation may also be used as the oxygen gas.
  • reaction temperature When the reaction temperature is 0°C or more, the reaction speed tends to increase. When the reaction temperature is 200°C or less, side reactions are inhibited and the selectivity of the alkylene oxide tends to increase.
  • the oxidation reaction may be carried out under increased pressure, for example, under a gauge pressure of 0.1 Pa to 20 MPa, preferably 1 MPa to 10 MPa.
  • the olefin oxide can be taken out by distillation of the reaction product of the oxidation reaction.
  • Weights of Ti (titanium atoms) and Si (silicon atoms) contained in the present catalyst were measured by the ICP emission spectrometry. That is, about 20 mg of a sample was measured into a platinum crucible, and the sample was covered with sodium carbonate. After that, melting operation was carried out by using a gas burner. After melting, the content in the platinum crucible was dissolved in pure water and nitric acid with heating. Subsequently, the volume thereof was fixed with pure water. Then, this solution was analyzed with the ICP emission spectrometer (ICPS-8000 manufactured by Shimadzu Corporation) , and an amount of each element was quantified.
  • ICPS-8000 manufactured by Shimadzu Corporation
  • a powder X-ray diffraction pattern of the present catalyst was determined by using the following device under the following conditions.
  • UV-Vis Ultraviolet and Visible Absorption Spectrum
  • the present catalyst was thoroughly pulverized in an agate mortar, and formed into pellets (7mm ⁇ j) ) to prepare a sample for measurement.
  • An ultraviolet and visible absorption spectrum of the sample was determined by using the following device under the following conditions.
  • a diffusion reflector (Praying Mantis manufactured by HARRICK)
  • V-7100 ultraviolet and visible spectrophotometer
  • Catalyst A had peaks at 12.3 d/A, 11.0 d/A, 9.0 d/A, 6.1 d/A, 3.9 d/A and 3.4 d/A, and it was found that the product was titanosilicate from the ultraviolet and visible absorption spectrum.
  • the titanium content measured by elemental analysis was 1.99% by weight .
  • Catalyst A had a bulk density of 0.10 g/ml.
  • Catalyst C had peaks at 12.3 d/A, 11.0 d/A, 9.0 d/A, 6.1 d/A, 3.9 d/A and 3.4 d/A, and it was found that Catalyst C was titanosilicate from the ultraviolet and visible absorption spectrum.
  • the titanium content measured by elemental analysis was 1.89% by weight .
  • Catalyst C had a bulk density of 0.09 g/ml .
  • Catalyst D had peaks at 12.3 d/A, 11.1 d/A, 9.0 d/A, 6.1 d/A, 3.9 d/A and 3.4 d/A, and it was found that Catalyst D was titanosilicate from the ultraviolet and visible absorption spectrum.
  • the titanium content measured by elemental analysis was 2.08% by weight.
  • Catalyst D had a bulk density of 0.09 g/ml.
  • Catalyst D was silylated with reference to the method described in JP 2003-326171 A. That is, the silylation was carried out by mixing 1.0 g of 1, 1, 1, 3, 3, 3-hexamethyl disilazane (manufactured by Wako Pure Chemical Industries, Ltd.), 100 mL of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.5 g of Catalyst D, and refluxing the mixture for 3 hours with heating.
  • Catalyst E a white powder
  • Catalyst E a white powder
  • the X-ray diffraction pattern of Catalyst E had peaks at 12.5 d/A, 11.2 d/A, 9.1 d/A, 6.2 d/A, 3.9 d/A and 3.4 d/A, and it was found that Catalyst E was titanosilicate from the ultraviolet and visible absorption spectrum.
  • Catalyst E had a bulk density of 0.08 g/ml .
  • a Ti-MWW precursor was synthesized in the same manner as described in Chemistry Letters 774-775 (2000) . That is, 200 g of piperidine (manufactured by Wako Pure Chemical Industries, Ltd. ) and 564 g of ion-exchanged water were mixed in a 2-L resin beaker at 25°C under an air atmosphere to obtain an aqueous piperidine solution. The aqueous solution was divided into two portions 382 g each, whereby an aqueous piperidine solution (1) and an aqueous piperidine solution (2) were prepared.
  • the aqueous piperidine solution (1), 5.6 g of TBOT (manufactured by Wako Pure Chemical Industries, Ltd.), and 49.5 g of fumed silica (cab-o-sil M7D manufactured by Cabot Corporation) were stirred at 25°C under an air atmosphere to obtain Gel (1) .
  • Gel (1) was stirred for 1 hour.
  • aqueous piperidine solution (2) 136.5 g of boric acid (manufactured by Wako Pure Chemical Industries, Ltd. ) , and 49.5 g of fumed silica (cab-o-sil M7D, manufactured by Cabot Corporation) were stirred at 25°C under an air atmosphere to obtain Gel (2) .
  • Gel (2) was stirred for 1 hour.
  • Gel (1) and Gel (2) were mixed in an autoclave at 25°C under an air atmosphere, and the mixture was stirred for another 1.5 hours to obtain Gel (3) .
  • the autoclave was sealed, the temperature of the content was elevated to 130°C over 5.5 hours while the mixture was stirred at a rotating speed of 100 rpm, and the content was kept at that temperature for 24 hours . After the content was kept at 130°C, the temperature of the content was elevated to 150°C over 1 hour, and the content was kept at that temperature for 24 hours.
  • Catalyst 1 had peaks at 12.3 d/A, 11.0 d/A, 8.8 d/A, 6.1 d/A, 3.9 d/A and 3.4 d/A, and it was found that the product was titanosilicate from the ultraviolet and visible absorption spectrum.
  • the titanium content measured by elemental analysis was 0.76% by weight.
  • Catalyst 1 had a bulk density of 0.18 g/ml.
  • Catalyst 1 50 g of Catalyst 1 obtained in Reference Example 1 was heated at 530°C for 6 hours to obtain 45 g of Catalyst 3. It was confirmed that the X-ray diffraction pattern of Catalyst
  • Catalyst 3 had peaks at 12.3 d/A, 11.0 d/A, 8.9 d/A, 6.1 d/A, 3.9 d/A and 3.4 d/A, and it was found that the product was titanosilicate from the ultraviolet and visible absorption spectrum. In addition, Catalyst 3 had a bulk density of 0.35 g/ml. [0076]
  • the temperature of the gel was elevated to 160°C over 8 hours with stirring, and the gel was kept at that temperature for 120 hours to obtain a suspension.
  • the filtrate was washed with water until its pH reached 10.5.
  • the obtained solid was dried at 50°C until weight loss thereof was no longer observed to obtain 508 g of Solid 5.
  • Catalyst 4 had peaks at 12.3 d/A, 11.0 d/A, 8.9 d/A, 6.1 d/A, 3.9 d/A and 3.4 d/A, and it was found that the product was titanosilicate from the ultraviolet and visible absorption spectrum.
  • the titanium content measured by elemental analysis was 1.80% by weight .
  • Catalyst 4 had a bulk density of 0.40 g/ml.
  • Catalyst 5 had peaks at 12.3 d/A, 11.1 d/A, 9.0 d/A, 6.1 d/A, 3.9 d/A and 3.4 d/A, and it was found that the product was titanosilicate from the ultraviolet and visible absorption spectrum.
  • the titanium content measured by elemental analysis was 1.80% by weight .
  • Catalyst 5 had a bulk density of 0.39 g/ml.
  • titanosilicates obtained in examples of the present invention and reference examples were brought into contact with hydrogen peroxide in accordance with the following method.
  • a mixture of 100 g of a solution of water/acetonitrile 1/4 (weight ratio) containing 0.1 g of titanosilicate and 0.1% by weight of hydrogen peroxide was stirred at room temperature (about 20°C) for 1 hour, filtered, and the obtained cake was washed with 500 mL of water to obtain a titanosilicate treated with hydrogen peroxide.
  • a 100 mL-stainless steel autoclave was filled with 60 g of the prepared solution, and 0.010 g of Catalyst A', which was separately obtained by treating Catalyst A from Example 1 with hydrogen peroxide as described above.
  • the autoclave was put in an ice bath, to which 1.2 g of propylene was added.
  • the pressure inside the autoclave was increased to 2 MPa (gauge pressure) with argon.
  • the temperature thereof was elevated to 60°C over 15 minutes while the mixed liquid in the autoclave was stirred, and the mixed liquid was stirred at that temperature for 1 hour. Then, the stirring was stopped, and the autoclave was cooled with ice.
  • the obtained mixed liquid was analyzed by gas chromatography.
  • the yield of propylene oxide was 49% based on the amount of hydrogen peroxide.
  • Propylene oxide was produced in the same manner as in Example 6 except that Catalyst B', which was obtained by treating Catalyst B from Example 2 with hydrogen peroxide, was used instead of Catalyst A' .
  • the yield of propylene oxide was 54% based on the amount of hydrogen peroxide.
  • Propylene oxide was produced in the same manner as in Example 6 except that Catalyst C, which was obtained by treating Catalyst C from Example 3 with hydrogen peroxide, was used instead of Catalyst A' . As a result, the yield of propylene oxide was 51% based on the amount of hydrogen peroxide.
  • Propylene oxide was produced in the same manner as in Example 6 except that Catalyst D', which was obtained by treating Catalyst D from Example 4 with hydrogen peroxide, was used instead of Catalyst A' . As a result, the yield of propylene oxide was 63% based on the amount of hydrogen peroxide.
  • Propylene oxide was produced in the same manner as in Example 6 except that Catalyst E', which was obtained by treating Catalyst E from Example 5 with hydrogen peroxide, was used instead of Catalyst A' . As a result, the yield of propylene oxide was 77% based on the amount of hydrogen peroxide.
  • Propylene oxide was produced in the same manner as in Example 6 except that 0.020 g of Catalyst 1, which was obtained in Reference Example 1, was used instead of 0.010 g of Catalyst A' . As a result, the yield of propylene oxide was 20% based on the amount of hydrogen peroxide.
  • Propylene oxide was produced in the same manner as in Example 6 except that Catalyst 1', which was obtained by treating Catalyst 1 from Reference Example 1 with hydrogen peroxide, was used instead of Catalyst A' . As a result, the yield of propylene oxide was 29% based on the amount of hydrogen peroxide .
  • Propylene oxide was produced in the same manner as in Example 6 except that Catalyst 2 1 , which was obtained by treating Catalyst 2 from Reference Example 2 with hydrogen peroxide, was used instead of Catalyst A' . As a result, the yield of propylene oxide was 42% based on the amount of hydrogen peroxide .
  • Propylene oxide was produced in the same manner as in Example 6 except that Catalyst 4 ' , which was obtained by treating Catalyst 4 from Reference Example 4 with hydrogen peroxide, was used instead of Catalyst A' . As a result, the yield of propylene oxide was 43% based on the amount of hydrogen peroxide .
  • a dark-field scanning transmission image (STEM-DF image) was observed at an acceleration voltage of 30 kV.
  • Pre-treatment method A sample was mixed with a cold setting epoxy resin (Epocure) , and the mixture was degassed and thus the sample was embedded.
  • a specimen having a film thickness of 80 to 100 nm was prepared by using Microtome (Ultramicrotome EMUC 6 manufactured by LEICA) (normal temperature and wet type) , and the sample was collected on a Cu mesh for observation.
  • the present invention can provide a novel titanosilicate as a catalyst for producing an olefin oxide capable of giving a higher yield based on the amount of an oxidizing agent.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Epoxy Compounds (AREA)
  • Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

La présente invention concerne un titanosilicate ayant une masse volumique apparente allant de 0,05 g/ml à 0,15 g/ml, et ayant un diffractogramme de rayons X ayant les valeurs suivantes : distance interréticulaire d/Angström 12,4 +/- 0,8, 10,8 +/- 0,5, 9,0 +/- 0,3, 6,0 +/- 0,3, 3,9 +/- 0,1, 3,4 +/- 0,1. La présente invention concerne également un procédé de production du titanosilicate et un procédé de production d'un oxyde d'oléfine à l'aide du titanosilicate comme catalyseur.
PCT/JP2011/067567 2010-07-30 2011-07-25 Titanosilicate et procédé de production d'oxyde d'oléfine à l'aide du titanosilicate comme catalyseur Ceased WO2012015056A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030040649A1 (en) * 2000-09-29 2003-02-27 Wataru Oguchi Crystalline mww-type titanosilicate catalyst for producing oxidized compound, production process for the catalyst, and process for producing oxidized compound by using the catalyst
WO2003074421A1 (fr) * 2002-03-07 2003-09-12 Showa Denko K. K. Silicate de titane, procede de production et utilisation de celui-ci dans la production d'un compose oxyde
US20060105903A1 (en) * 2003-02-03 2006-05-18 Takashi Tatsumi Modified layered metallosilicate material and production process thereof
US20080026938A1 (en) * 2004-03-22 2008-01-31 Sumitomo Chemical Compamy, Limited Method for Producing Propylene Oxide
WO2010032879A2 (fr) * 2008-09-19 2010-03-25 Sumitomo Chemical Company, Limited Procédé de production de composé oxydé

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030040649A1 (en) * 2000-09-29 2003-02-27 Wataru Oguchi Crystalline mww-type titanosilicate catalyst for producing oxidized compound, production process for the catalyst, and process for producing oxidized compound by using the catalyst
WO2003074421A1 (fr) * 2002-03-07 2003-09-12 Showa Denko K. K. Silicate de titane, procede de production et utilisation de celui-ci dans la production d'un compose oxyde
EP1490300B1 (fr) * 2002-03-07 2009-04-08 Showa Denko K.K. Silicate de titane, procede de production et utilisation de celui-ci dans la production d'un compose oxyde
US20060105903A1 (en) * 2003-02-03 2006-05-18 Takashi Tatsumi Modified layered metallosilicate material and production process thereof
US20080026938A1 (en) * 2004-03-22 2008-01-31 Sumitomo Chemical Compamy, Limited Method for Producing Propylene Oxide
WO2010032879A2 (fr) * 2008-09-19 2010-03-25 Sumitomo Chemical Company, Limited Procédé de production de composé oxydé

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