EP3116648A1 - Katalysatorprecursormaterial auf TiO2-Basis, dessen Herstellung und dessen Verwendung - Google Patents

Katalysatorprecursormaterial auf TiO2-Basis, dessen Herstellung und dessen Verwendung

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Publication number
EP3116648A1
EP3116648A1 EP15715967.4A EP15715967A EP3116648A1 EP 3116648 A1 EP3116648 A1 EP 3116648A1 EP 15715967 A EP15715967 A EP 15715967A EP 3116648 A1 EP3116648 A1 EP 3116648A1
Authority
EP
European Patent Office
Prior art keywords
catalyst precursor
precursor material
tio
acid
dried
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP15715967.4A
Other languages
German (de)
English (en)
French (fr)
Inventor
Sonja Grothe
Christian Spitzwieser
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Venator Germany GmbH
Original Assignee
Huntsman P&A Germany GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huntsman P&A Germany GmbH filed Critical Huntsman P&A Germany GmbH
Publication of EP3116648A1 publication Critical patent/EP3116648A1/de
Pending legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/92Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404Removing only nitrogen compounds
    • B01D53/9409Nitrogen oxides
    • B01D53/9413Processes characterised by a specific catalyst
    • B01D53/9418Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04Alumina
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063Titanium; Oxides or hydroxides thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08Silica
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12Silica and alumina
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/40Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/50Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61Surface area
    • B01J35/615100-500 m2/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63Pore volume
    • B01J35/633Pore volume less than 0.5 ml/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63Pore volume
    • B01J35/6350.5-1.0 ml/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027Powdering
    • B01J37/0045Drying a slurry, e.g. spray drying
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0215Coating
    • B01J37/0221Coating of particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04Mixing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06Washing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/082Decomposition and pyrolysis
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00Compounds of titanium
    • C01G23/04Oxides; Hydroxides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00Compounds of titanium
    • C01G23/04Oxides; Hydroxides
    • C01G23/047Titanium dioxide
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/61Micrometer sized, i.e. from 1-100 micrometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
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    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/62Submicrometer sized, i.e. from 0.1-1 micrometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/80Particles consisting of a mixture of two or more inorganic phases
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/12Surface area
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2006/14Pore volume
    • CCHEMISTRY; METALLURGY
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    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/21Attrition-index or crushing strength of granulates
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70Catalyst aspects

Definitions

  • TiOg-based catalyst precursor material its preparation and its use
  • the invention relates to a catalyst precursor material, and more particularly to a powdered Ti0 2 -based catalyst precursor material containing at least one molding assistant, to a process for its preparation, to use for the production of moldings and to the use of the moldings as catalyst or catalyst support.
  • a powdered Ti0 2 -based catalyst precursor material containing at least one molding assistant
  • the use of powdered titanium dioxide to produce shaped catalysts or catalyst supports has long been known.
  • the titanium dioxide moldings can be used directly as a catalyst without the addition of other materials.
  • titanium dioxide-containing moldings with active metals such as Cr, Mo, W, Fe, Ru, Os , Co, Ni, Pd, Pt, Cu, Ag, V or Zn or their metal oxides
  • the titania-containing moldings serve as so-called catalyst carriers, as well as the co-processing of titanium dioxide with active materials for the production of titania-containing catalysts
  • catalysts consisting of titanium dioxide, WO3 and V2O5 are used for the selective catalytic reduction of nitrogen oxides in exhaust gases of combustion plants, waste incineration plants, gas turbines, industrial plants and engines
  • Such titanium dioxide shaped bodies serving as catalyst or catalyst support for fixed bed or fluidized bed Systems used must have sufficiently high strengths Otherwise, since the catalyst can break apart when filling the reactor and / or can be crushed by the gas pressure, the heat load and dynamic loads during the reaction or can be subject to severe a
  • US 41 13660 describes a process for the preparation of catalysts and catalyst supports (moldings) with improved mechanical strengths, the consist predominantly of titanium dioxide.
  • the production of these moldings takes place in such a way that titanium dioxide or a precursor thereof in the presence of metatitanic acid sol or gel is subjected to a calcining treatment at temperatures of 200 to 800 ° C.
  • US Pat. No. 4,388,288 describes a process for producing porous titanium dioxide catalysts / catalyst supports in the form of shaped bodies, in which pulverulent, low-crystalline or amorphous titanium dioxides are mixed with water and a shaping assistant. This paste is then molded and annealed at temperatures of typically 200-900 ° C.
  • No. 3,919,119 describes the preparation of abrasion-enhanced catalyst supports which comprise a mixture of a titanium chelate with titanium dioxide and a gelling agent. After gelation of the mixture, it is dried and calcined.
  • the titanium chelate complex used is preferably diethanolamine titanate.
  • EP 0389041 A1 describes a process for the preparation of titania extrudates from a moldable dough, which process comprises mixing and kneading a particulate titanium dioxide with water and an alkanolamine or ammonia or an ammonia releasing compound. Further, the extrusion and calcination of the extruded dough strands is typically described at 450-750 ° C.
  • EP 0389041 describes titanium dioxide moldings having specific surfaces of less than 100 m 2 / g and prepared only with the addition of inorganic additives, such as silica or zeolites.
  • Powdered catalyst materials based on titanium dioxide which have high specific surface areas and are particularly suitable for producing titanium dioxide moldings with high specific surface areas and with good mechanical strengths, are not known in the prior art.
  • the object of the invention is to overcome the disadvantages of the prior art and a catalyst precursor material based on titanium dioxide with high specific surface area, which is particularly suitable for the production of titanium dioxide moldings with high mechanical strength and high specific surface areas.
  • a powdered Katalysatorprecursormaterial on TiO2-based comprising one or more shaping auxiliary and having specific surface areas of at least 150 m 2 / g, suitable for the production of titanium dioxide molded bodies, which, surprisingly, by high mechanical strengths and high specific surface areas.
  • the TiO 2 -based catalyst precursor material of the present invention may contain such particles of titanium dioxide and hydrated forms thereof as described above.
  • one or more shaping aids additionally also S1O2, Al2O3 and / or their hydrated forms such as AIO (OH) or mixtures thereof, for example with a content of 50-99.5 wt.%, preferably 70-99.5 wt.
  • % TiO 2 0.5-30% by weight, especially 4-15% by weight of forming assistant and 0.1-50% by weight, especially 0.1-1 15% by weight of S1O2, Al2O3 and / or their hydrated forms such as AIO (OH) include.
  • these optional components are preferably added to the TiO 2 component before the addition of the shaping aid (s).
  • the pulverulent catalyst precursor material can also, for example, depending on the neutralizing agent used to neutralize sulfuric acid adhering to the TiO 2 particles, additionally contain 0.5 to 30% by weight, especially 5 to 25% by weight, of CaSO 4 , BaSO 4 or mixtures included.
  • the wt .-% in this specification according to the invention relate to the total weight of the catalyst precursor material after drying at 105 ° C for at least 120 minutes and add up to 100 wt .-% of the total weight of the material, wherein the optional components are included.
  • the powdered catalyst precursor material particularly has a specific surface area of at least 150 m 2 / g, especially at least 200 m 2 / g, especially at least 300 m 2 / g.
  • the total pore volume (N 2 -porosimetry) is at least 0.25 cm 3 / g, especially at least 0.3 cm 3 / g, especially at least 0.4 cm 3 / g and very particularly 0.6 cm 3 / g .
  • the crystalline parts of the titanium dioxide are preferably present in the anatase modification. "Powdered" means according to the invention that the particles generally have a size of ⁇ 1 mm (sieving).
  • the TiO 2 particles of the catalyst precursor material according to the invention in the preferred embodiment have an irregular shape which can be described approximately as spherical. These are not tube, stick or platelet materials.
  • the surface of the powdered catalyst precursor material is coated with the forming aid. This surface coverage of the catalyst percursor material with one or more shaping auxiliaries can be achieved particularly well by the process according to the invention, whereas a pure physical mixture of pulverulent catalyst precursor materials with shaping aids generally does not lead to a comparable surface coverage and formability.
  • the pulverulent catalyst precursor material is obtained by mixing a suspension of TiO 2 particles of the formula TiO (2-x) (OH) 2 x (0 ⁇ x ⁇ 1) with the shaping assistant or mixtures of several shaping aids as such, in solution or suspension is treated and thereby the surface of said TiO2 particles with the (n) forming aid (s) is occupied.
  • the suspension of TiO 2 particles having the formula TiO (2 -X ) (OH) 2 X (0 ⁇ x ⁇ 1) may in one embodiment be metatitanic acid of the formula TiO (OH) 2 , which is used to prepare TiO 2 applied sulfate process is obtained as an intermediate.
  • the suspension of TiO 2 particles with the formula TiO (2 -X ) (OH) 2 X (0 ⁇ x ⁇ 1) can also be prepared by precipitation, hydrolysis or sol-gel processes from Ti-containing solutions, in particular from hydrolysable compounds such as TiOSO 4 or T1OCl 2 -containing solutions.
  • occupying the surface of the particles is also an occupancy within the pores to understand, if possible.
  • the inventors have found that one or more compounds for covering the surface of the TiO (2-X) (OH) 2x (0 ⁇ x ⁇ 1) / TiO 2 particles can be used as shaping aids, which are at temperatures below the transition temperature of Anatase in rutile (915 ° C), preferably to below 600 ° C, more preferably below 400 ° C, preferably as far as possible residue-free, evaporate, sublime or decompose.
  • the forming aid aids shaping and may be left between and / or on the particles of the powdered catalyst precursor material and assist in kneading, as well as helping to singulate the particles of the powdered catalyst precursor material.
  • shaping aids it is possible to add substances which primarily promote the formation of a plastic mass during kneading and, moreover, the mechanical stability of the shaped body during shaping. These shaping aids are removed on calcination of the molding, with complete removal preferred.
  • the shaping assistant may preferably be an organic hydrocarbon compound which may contain at least one functional group selected from hydroxy, carboxy, amino, imino, amido, ester, sulfonyl, keto, and their thio analogues, or several different thereof; at temperatures below the transition temperature of anatase in rutile (915 ° C), preferably below 600 ° C, more preferably below 400 ° C, for example in the preparation of the titanium dioxide molded body according to the invention, evaporated, decomposed or sublimed.
  • Preferred is a low molecular weight organic hydrocarbon compound having at least one functional group containing one or more oxygen atoms, such as hydroxy, carboxy.
  • a low molecular weight organic hydrocarbon compound is understood to mean a hydrocarbon compound having one to twelve carbon atoms which is at least one of the substituent groups selected from hydroxy, carboxy, amino, imino, amido, imido, ester, sulfonyl, keto, and their thio analogues, especially hydroxy, carboxy , having.
  • the shaping aid may be an acid, a base, an alkanolamine or another substance which, when calcined, the titanium dioxide molded body according to the invention at temperatures below the transition temperature of anatase in rutile (915 ° C), preferably below 600 ° C, more preferably vaporizes below 400 ° C, decomposes or sublimates.
  • the shaping assistant is preferably an organic acid, particularly preferably a carboxylic acid, in particular having one to six carbon atoms, including a di- and tricarboxylic acid, particularly preferably acetic acid, oxalic acid, tartaric acid, maleic acid, or citric acid, in particular oxalic acid.
  • Nitrogenic acid, ammonia, alkanolamine or an ammonia-releasing compound may also preferably be used as the shaping assistant.
  • Carbohydrates such as cellulose, cellulose ethers, tyloses, glucose, polyacrylamines, polyvinyl alcohol, stearic acid, polyethylene glycol or mixtures thereof can likewise be used as shaping aids.
  • the molding according to the invention has a residual carbon content of less than 2% by weight, preferably less than 1% by weight, based on the weight of the molding after calcining.
  • the invention thus relates to - wherein the wt .-% in each case based on the total weight of the dried catalyst precursor material:
  • a shaping aid at temperatures below the transition temperature of anatase in rutile (915 ° C), preferably below 600 ° C, more preferably below 400 ° C, for example in the preparation of the inventive Titanium dioxide shaped body, evaporated, decomposed or sublimed, or mixtures thereof; a powdered Ti0 2 -based catalyst precursor material as defined above containing:
  • an organic hydrocarbon compound which may contain at least one functional group selected from hydroxy, carboxy, amino, imino, amido, esters, sulphonyl, keto and their thio analogues, or several of which are different, at temperatures below the transformation temperature of anatase in Rutile (915 ° C), preferably below 600 ° C, especially below 400 ° C, for example in the preparation of the titanium dioxide molded body according to the invention, evaporated, decomposed or sublim tion, for example, an organic acid, preferably a carboxylic acid, particularly preferably acetic acid , Oxalic, tartaric, maleic or citric acid, most preferably oxalic acid,
  • Ammonia alkanolamine or an ammonia-releasing compound
  • - Carbohydrates such as cellulose, cellulose ethers, glucose, polyacrylamines, polyvinyl alcohol, stearic acid, polyethylene glycol or mixtures thereof.
  • a powdered catalyst precursor material based on TiO 2 as defined above with a pore volume (N 2 desorption, total) of at least 0.25 cm 3 / g, preferably at least 0.30 cm 3 / g, particularly preferably at least 0.4 cm3 / g most preferably 0.6 cm 3 / g.
  • hydrated preforms of TiO 2 , SiO 2 and / or Al 2 O 3 are included.
  • This dispersion of titanium dioxide may also contain further constituents such as SiO 2 and / or Al 2 O 3 and / or CaSO 4 and their hydrated forms thereof such as AIO (OH), sulfate ions, phosphate ions and, depending on the preparation of the titanium dioxide dispersion, further typical accompanying substances such as Na , K, etc. included.
  • the sulphate content of the powdered catalyst precursor material according to the invention is less than 2.0% by weight, especially less than 1.5% by weight, based on the total weight of the dried catalyst precursor material.
  • the invention also relates to a process for the preparation of the powdery catalyst precursor material based on TiO 2 , in which:
  • titanium oxide hydrate and / or hydrated titanium dioxide of the general formula TiO (2-X) (OH) 2x (0 ⁇ x ⁇ 1) or mixtures thereof (referred to herein as “titanium dioxide suspension") with the shaping aid or mixtures thereof is mixed and
  • the resulting suspension is dried at a temperature of below 150 ° C and, if necessary, subjected to a grinding step.
  • the forming aid or mixture thereof may be added in dry form, in suspension or in solution.
  • nm-5 pm preferably 10 nm-2000 nm, especially 10 nm-1000 nm, preferably 50 nm-1000 nm, particularly preferably 20 nm-800 nm, very particularly preferably 30-200 nm, and
  • the anatase phase preferably the crystalline phases of the particles consist of anatase.
  • Another embodiment relates to the process for the preparation of the powdery catalyst precursor material based on TiO 2, in which:
  • the washed metatitanic acid preferably as a filter cake, is taken up again in an aqueous phase,
  • a preferably aqueous solution of the shaping assistant is added to the resulting suspension,
  • the suspension obtained is dried at a temperature below 150 ° C and, if necessary, subjected to a grinding step.
  • the metatitanic acid used contains titanium-oxygen compounds and may contain free and bound sulfuric acid, wherein the crystalline components of the titanium-oxygen compounds contained present in anatase modification and have a typical crystallite size of about 5-10 nm.
  • the titanium-oxygen compounds can be defined by the general formula TiO (2 -X ) (OH) 2 ⁇ , where (0 ⁇ x ⁇ 1).
  • the metatitanic acid is produced in the production of Ti0 2 by the sulfate process as an intermediate. In the sulphate process llmenit and / or slag is digested with 90% H 2 S0 4 , the resulting digestion cake dissolved in water and the solution clarified.
  • the neutralization of the (sulfuric) metatitanic according to the invention especially with an alkali, preferably selected from NaOH, ammonia, calcium carbonate, calcium hydroxide or Ba (OH) 2 , particularly preferably with NaOH, take place.
  • an alkali preferably selected from NaOH, ammonia, calcium carbonate, calcium hydroxide or Ba (OH) 2 , particularly preferably with NaOH, take place.
  • the resulting neutralized metatitanic acid is washed with water to a conductivity of at most 500 pS / cm, followed by slurry or dispersion of the washed filter cake, preferably with a stirrer, more preferably a dissolver.
  • the suspension obtained after the ripening step is dried according to the invention at a temperature of below 150 ° C, in order to prevent evaporation or decomposition of the forming aid, preferably in a temperature range of 90-140 ° C, in particular by means of spray-drying or mill-drying, and, if required to undergo a milling step to comminute any agglomerates formed.
  • the Hot gas temperatures in the mill drying usually at 250 ° to 300 ° C, in the spray drying at 250 ° to 500 °, sometimes even up to 600 ° C, product flow and product temperature must be carefully monitored to prevent evaporation or decomposition of the forming aid to Accordingly, during spray-drying, the product outlet temperatures are in the range of 90-140.degree. C., in the case of mill-drying, the product outlet temperatures are approximately 120.degree. to 130.degree. C., in particular 125.degree.
  • the auf2-based powdered catalyst precursor materials according to the invention thus obtained can be used according to the invention for the production of moldings according to the invention using the following method:
  • Peptizing agent preferably hydrochloric acid, sulfuric acid, nitric acid,
  • Plasticizer such. Cellulose, clay, polyvinyl alcohols,
  • Binders such as TiO 2 sols, TiOSO 4 solution, alumina, SiO 2 sols or clays, preferably TiO 2 sol, TiOSO 4 solution or AIO (OH) (boehmite or pseudoboehmite)
  • Bases preferably ammonia or amine-containing compounds iv. Lubricants such.
  • the water content of the paste is preferably chosen so that the paste by means of an extruder (twin screw) with pressures of 1 to 100 bar, or, if necessary, up to 200 bar by a 1-5 mm diameter
  • Nozzle can be pressed
  • the molded articles produced from the catalyst precursor materials according to the invention usually have the following properties:
  • the moldings produced from the catalyst precursor materials according to the invention can be used as catalyst or catalyst support for catalytically active metals such as V, W, Co, Mo, Ni, Fe, Cu, Cr, Ru, Pd, Pt, Ag, Zn for applications in the field of catalytically active metals such as V, W, Co, Mo, Ni, Fe, Cu, Cr, Ru, Pd, Pt, Ag, Zn for applications in the field of catalytically active metals such as V, W, Co, Mo, Ni, Fe, Cu, Cr, Ru, Pd, Pt, Ag, Zn for applications in the field of
  • the sample is burned at 1300 ° C in an oxygen stream.
  • the resulting carbon dioxide is detected by infrared analysis.
  • the sample is burned at 1400 ° C in an oxygen stream.
  • the resulting sulfur dioxide is detected by infrared analysis. Thereafter, the determined S content is converted to S0 4 .
  • the specific surface and the pore structure are carried out by means of N 2 -orosimetry with the device Autosorb 6 or 6B from Quantachrome GmbH.
  • the BET surface area (Brunnauer, Emmet and Teller) is determined according to DIN ISO 9277, the pore distribution according to DIN 66134.
  • the sample weighed into the measuring cell is pre-dried at the baking station for 16 h under vacuum. Subsequently, the heating is carried out under vacuum to 180 ° C in about 30 min. The temperature is then maintained for one hour while maintaining the vacuum. The sample is considered sufficiently degassed if a pressure of 20-30 millitorr is set on the degasser and after disconnecting the vacuum pump the needle of the vacuum gauge remains stable for approx. 2 minutes. Measurement / Evaluation (Ng porosimetry)
  • the entire N 2 isotherm is measured with 20 adsorption points and 25 desorption points.
  • the evaluation of the measurements was carried out as follows:
  • the determination of the total pore volume is carried out according to DIN 66134 according to the Gurvich rule. After the s.g. Gurvich's rule determines the total pore volume of a sample from the last pressure point in the adsorption measurement: p. Pressure of the sorptive
  • the calculation uses the relationship 4Vp / A B ET, which corresponds to the "average pore diameter" A B ET specific surface according to ISO 9277.
  • the measurement of the strength of the extrudates is carried out by applying a pneumatic pressure on an extrudate specimen between two horizontally mounted flat metal plates.
  • a pneumatic pressure on an extrudate specimen between two horizontally mounted flat metal plates.
  • a 4-5 mm long extrudate specimen is placed centrally on a lower, stationary plate.
  • the upper, pneumatically controlled counterplate is slowly driven down to the slight touch of the extrudate specimen.
  • the pressure is now up for destruction (cracking, breaking or splitting) of the extrudate sample body continuously increased.
  • the pressure necessary to destroy the extrudate sample is read on a digital display in kg.
  • the strength of the extrudates is calculated from the average of 30 measurements.
  • phase identification an X-ray diffractogram is taken. For this purpose, the intensities of the x-rays diffracted by the Bragg condition at the lattice planes of a crystal are measured against the diffraction angle 2 theta.
  • the X-ray diffraction pattern is typical for one phase.
  • the material to be examined is brushed onto the preparation carrier with the aid of a slide.
  • the evaluation of the powder diffractometry data is carried out using the JCPDS powder diffractometry database.
  • the phase is identified when the measured diffraction pattern corresponds to the stored bar pattern.
  • D crystallite crystallite size [nm]
  • Theta angular position of the measurement reflex 2 theta / 2
  • Hombikat MTSA (metatitanic acid, commercial product of Sachtleben Chemie GmbH.) Is neutralized with sodium hydroxide solution to a pH of 6.5 and washed with water until the conductivity in the filtrate is less than 200 pS / cm.
  • the properties of this powder are listed in Tab. 1.
  • Hombikat MTSA commercial product of Sachtleben Chemie GmbH. Is neutralized with sodium hydroxide solution to a pH of 6.5 and washed with water until the conductivity in the filtrate is less than 200 pS / cm.
  • the filter cake is redisperigert and treated with an aqueous oxalic acid solution (corresponding to 8 g of oxalic acid dihydrate to 92g ⁇ 2).
  • T 50 ° C
  • T 1 10 +/- 5 ° C.
  • the properties of this spray-dried TiO 2 or titanium oxide hydrate powder are listed in Tab.
  • Example 4 The properties of this spray-dried ⁇ 2 or titanium oxide hydrate powder are listed in Tab. 1.
  • the starting material used is a commercially available titanium oxide hydrate suspension (TiO.sub.x ) (OH) 2 ⁇ (0 ⁇ x ⁇ 1)), with a Ti content calculated as titanium dioxide of about 200 g of T1O.sub.2 / I, an average particle size of 48 nm (measured by PCS measurement after ultrasonic finger dispersion and with a specific surface area of 350 m 2 / g (N 2 -5-Pt-BET, measured after drying at 105 ° C.).
  • the putty is then discharged by extrusion, at a pressure of 140-180 bar, over a 3 mm die and cut to the desired length (about 15 - 20 mm).
  • the extrudates thus produced are first dried in air and then tempered as in Example 1.
  • TiO (2x) (OH) 2x (0 ⁇ x ⁇ 1) a commercially available titanium oxide hydrate suspension (TiO (2x) (OH) 2x (0 ⁇ x ⁇ 1)) is calculated with a Ti content as titanium dioxide of approximately 300 g of T1O2 / l, a mean particle size of 950 nm (measured by PCS measurement after ultrasonic finger dispersion and with a specific surface area of 350 m 2 / g (N 2 -5-Pt-BET, measured after drying at 105 ° C.).
  • the putty is then discharged by extrusion over a 3 mm die and cut to the desired length (about 15 - 20 mm).
  • the extrudates thus prepared are first dried in air and then heated for 60 min at 90 ° C, then for several hours to the calcination temperature of 350 ° C and held for 120 min at this temperature, and then cooled to room temperature.
  • Hombikat MTSA commercial product of Sachtleben Chemie GmbH.
  • T 1 10 +/- 5 ° C.
  • T 1 10 +/- 5 ° C.
  • the properties of this spray-dried Ti0 2 or titanium oxide hydrate powder are listed in Tab. 1. 400 g of this powder and 64 g of an aqueous 2.5% Tyloseains are introduced into the mixing trough of the double Z-kneader and mixed for about 1 min.
  • the putty is then discharged by extrusion over a 3 mm die and cut to the desired length (about 15 - 20 mm).
  • the extrudates thus prepared are first dried in air and then heated for 60 min at 90 ° C, then for several hours to the Caicin réellestemperatur of 350 ° C and held for 120 min at this temperature, and then cooled to room temperature.
  • the putty is then discharged by extrusion, at a pressure of 120-150 bar, over a 3 mm die and cut to the desired length (about 15 - 20 mm).
  • the extrudates thus prepared are first dried in air and then heated for 60 min at 90 ° C, then for several hours to the calcination temperature of 350 ° C and held for 120 min at this temperature, and then cooled to room temperature. Comparative Example 1
  • the kneading material is then discharged by means of extrusion, at a pressure of 40-70 bar, over a 3 mm die and cut to the desired length (about 15-20 mm).
  • the extrudates thus obtained are first dried in air and then tempered as in Example 1.
  • Hombikat MTSA (commercial product from Sachtleben) is neutralized with sodium hydroxide solution to a pH of 6.5 and washed with water to a filtrate conductivity of ⁇ 200 pS / cm.
  • the filter cake is redisperigert and spray dried.
  • the properties of this spray-dried TiO 2 or titanium oxide hydrate powder are listed in Tab. 400 g of this powder are introduced with 100 g of oxalic acid (9, 1%) and 64 g of an aqueous 2.5% Tyloseaims in the mixing trough of the double Z-kneader and mixed for about 1 min. Then 27 g of a 10 wt .-% hydrochloric acid are added. This mixture is then kneaded for 30 minutes.
  • Hombikat M31 1 powder titanium dioxide, commercial product from Sachtleben
  • the surface-modified powders according to the invention with high specific surface areas can be used to produce extrudates with high strength with simultaneously high specific surface areas and high pore volumes. Comparable TiO 2 -based powders with high specific surface areas are not known in the prior art.
  • Example 3 320 0.30 85.2 2.3 n.d. n.d. anatase
  • Example 4 316 0.28 86.4 1, 8 n.d. n.d. anatase
  • Example 5 328 0.30 84.9 1, 8 n.d. n.d. anatase
  • Example 6 344 0.32 88.4 0.55 n.d. n.d. anatase
  • Example 8 349 0.31 87.7 n.d. 0.3 n.d. anatase
  • Example 9 352 0.33 85.1 n.d. 0.31 n.d. anatase
  • Example 1 28 107 0.27 10 anatase
  • Example 8 25 156 0.27 n.d. anatase
  • Example 9 20 232 0.25 n.d. anatase
  • Example 10 20 209 0.24 n.d. anatase
  • Example 12 19 109 0.26 anatase
  • Example 13 37 260 0.27 anatase

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CN109126755B (zh) * 2018-08-04 2021-07-23 山东迅达化工集团有限公司 二氧化钛基硫磺回收催化剂的制备方法
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CN114042445A (zh) * 2021-11-30 2022-02-15 西安向阳航天材料股份有限公司 一种二氧化钛基催化剂载体及其制备方法
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