WO2010106146A1 - Procédé de production de matériaux en dioxyde de titane à surfaces de contact et stabilité thermique élevées - Google Patents

Procédé de production de matériaux en dioxyde de titane à surfaces de contact et stabilité thermique élevées Download PDF

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WO2010106146A1
WO2010106146A1 PCT/EP2010/053555 EP2010053555W WO2010106146A1 WO 2010106146 A1 WO2010106146 A1 WO 2010106146A1 EP 2010053555 W EP2010053555 W EP 2010053555W WO 2010106146 A1 WO2010106146 A1 WO 2010106146A1
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transition metal
metal oxide
silicon
particles
present
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PCT/EP2010/053555
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Alexandra Seeber
Cornelia Roeger
Alexander Traut
Roman Zieba
Iris Schneider
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Basf Se
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    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3684—Treatment with organo-silicon compounds
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter

Definitions

  • the present invention relates to a process for the preparation of particles comprising at least one transition metal oxide and silicon dioxide, comprising at least the following steps: (A) contacting at least one precursor of the at least one transition metal oxide and at least one non-ionic surfactant comprising silicon in at least one non-aqueous organic solvent, to obtain a reaction mixture and (B) drying the reaction mixture obtained in step (A) to obtain particles comprising the at least one transition metal oxide and silicon dioxide.
  • the present invention further relates to the use of TiCI 4 and/or Ti(O 1 Pr) 4 in the preparation of particles comprising TiO 2 and SiO 2 and to a particle comprising at least one transition metal oxide and silicon dioxide.
  • EP 0 668 100 A1 discloses a process for preparing a silica-titania catalyst by adding an acidic solution containing a silicon compound such as sodium silicate and a titanium compound such as titanium sulphate dissolved therein to a solution of a compound such as ammoniumbicarbonate to bring about co-precipitation, in which the acidic solution is a highly concentrated nitric acid-acidic or sulphuric acid-acidic solution.
  • EP 0 668 100 A1 does not disclose that silicon comprising surfactants may be used as structure directing agent.
  • the process according to this document is conducted in an aqueous acidic solution.
  • US 3,887,494 discloses a method for preparing a composition comprising silica and titanium, convertible to a catalyst suitable for olefin polymerisation by the addition of chromium and the process performable therewith, wherein the preparation involves the addition of an alkali metal silicate to an acid containing a titanium compound and recovering a dry gel for use as catalyst upon the addition of chromium.
  • the process according to US 3,887,494 is conducted in an aqueous medium.
  • the use of non-ionic silicon surfactants is not disclosed.
  • EP 0 826 410 A2 discloses a catalyst for purifying exhaust gases, which is capable of maintaining the catalytic property and purification performance against particulates, HC, CO and NOx over a long period of time.
  • the catalyst has a catalyst substrate and a heat-resistant inorganic oxide layer containing catalytic components, which is pro- vided on the catalyst substrate.
  • This layer contains silica-doped titania in anatase modification having a structure that 3 to 35% by weight of silica is finely dispersed between and retained by anatase titania particles which is an oxide obtained in the state where a silicon-containing compound and titanium containing compound are mixed in the molecular state.
  • titanium comprising compound is titania sol
  • silica comprising compound is silica sol
  • EP 0 826 410 A2 does not dis- close the process for the preparation of mixed oxides in non-aqueous organic solvents.
  • non-ionic surfactants comprising silicon is not disclosed in this document.
  • JP 2002-348380 A discloses titanium oxide silica composites and a method for the preparation of these composites.
  • titanium oxide organopolysiloxane hybrid granular material is treated in a mixture of water and chloride-isopropyl alcohol. This granular material is heat-treated to obtain porous titanium oxide silica composites having a BET specific surface area of about 100 m 2 /g.
  • JP 2002-348380 A does not disclose a process for the preparation of titanium dioxide materials doped with silicon dioxide, wherein this process is conducted in a non-aqueous organic solvent in the presence of non-ionic surfactants comprising silicon.
  • WO 2006/058254 A1 discloses a process for the preparation of mesoporous metal ox- ides.
  • the mesoporous oxides of titanium, zirconium or hafnium are disclosed.
  • a solvent for the process according to WO 2006/058254 A1 can be chosen from aqueous or organic solvents.
  • emulsifiers can be added to the reaction mixture, for example glyceryl stearate, polyethyleneglycol-100 stearate etc.
  • JP 2003-073585 A relates to a fluid for titania film formation, a method for forming a titania film and the titania film itself.
  • an organic substance is mixed with the anatase crystal/amorphous mixing titania sol solution containing an amorphous type titania, an anatase type crystal titania, or its precursor.
  • the organic substances, which can be added can be chosen from polyalkylene oxide, like polyethylene oxide, polypropylene oxide and further polyethers.
  • compounds comprising siloxane bonds represented by polydimethylsiloxane can be used.
  • the method according to JP 2003-073585 A is conducted in an aqueous solvent.
  • Xu et al., Adv. Mater. 2002, 14 No. 15, pages 1064 to 1068 disclose a method for the preparation of oxide monoliths and films with unusual long range highly ordered lamellar structures.
  • These lamellar metal oxide (Ti ⁇ 2 and Zr ⁇ 2 ) monoliths and films are prepared by a sol-gel method, wherein a mixture of metal alkoxide, cationic silicon surfactant, water and HCI in ethanol is used.
  • Xu et al. do not disclose particles which are obtained from a non-aqueous organic solution.
  • the problem with the processes according to the prior art is that calcination often leads to polystructured or dense or collapsed materials with low surface areas.
  • mesoporous titanium dioxide materials which are obtained by the methods according to the prior art often show a low thermal stability of both the mesoporous structure and the anatase modification of titanium dioxide. After heating the materials of the prior art to high temperatures, the BET surface area often dramatically decreases in addition to an at least gradual structural phase change to the inactive rutil modification. In addition the removal of surfactants which are commonly used as structure directing agents in the preparation of TiC> 2 particles is often difficult.
  • a process for the preparation of these particles should be provided.
  • reaction mixture (A) contacting at least one precursor of the at least one transition metal oxide and at least one non-ionic surfactant comprising silicon and at least one non-aqueous organic solvent, to obtain a reaction mixture and
  • step (B) drying the reaction mixture obtained in step (A) to obtain particles comprising the at least one transition metal oxide and silicon dioxide.
  • the process according to the present invention gives rise to particles comprising at least one transition metal oxide and silicon dioxide.
  • the at least one transition metal oxide is chosen from the group consisting of TiO 2 , ZrO 2 , ZnO, VO x , NbO x , MoO x , WO 3 , HfO 2 and mixtures thereof.
  • the present invention relates to a process, wherein the transition metal oxide is titanium dioxide (TiO 2 ).
  • the present invention therefore further relates to the process as mentioned above, wherein the transition metal oxide is titanium dioxide (TiO 2 ).
  • titanium dioxide is predominantly present in its anatase modification.
  • titanium dioxide is present in the anatase modification in an amount of at least 50%, more preferred at least 60%, particu- larly preferred at least 70% based on the total amount of titanium dioxide in each case.
  • the particles which are prepared by the process according to the present invention further comprise silicon dioxide.
  • the particles which are prepared by the process according to the present in- vention comprise silicon dioxide in an amount of 0.1 to 30 % by weight, preferably 1 to 20 % by weight, and particularly preferred 3 to 12 % by weight.
  • Step (A) of the process according to the present invention comprises contacting at least one precursor of the at least one transition metal oxide and at least one non-ionic surfactant comprising silicon in at least one non-aqueous organic solvent, to obtain a reaction mixture.
  • all precursors of the at least one transition metal oxide can be used in step (A) of the process according to the present invention, which are known to a person skilled in the art to be convertible to at least one transition metal oxide.
  • suitable precursors of the at least one transition metal oxide are compounds comprising the corresponding metal cation in addition to a suitable anion.
  • Suitable anions are for example chosen from the group consisting of halides, for example chloride, bromide, sulphates, phosphates, carbonates, anions of carboxylic acids, alcoxides, for example methoxide, ethoxide, propoxides, for example n-propoxide, iso-propoxide, butoxides, for example n-butoxide, iso-butoxide, tert.-butoxide and mixtures thereof.
  • Particularly preferred precursors are halides, especially chlorides and/or alkoxides, especially iso-propoxides, of the corresponding transition metal.
  • titanium dioxide is the at least one transition metal oxide
  • preferred precursors are chosen from the group consisting of titanium tetrachloride (TiCI 4 ), titanium tetra- alkoxides, for example titanium tetra isopropoxide, and/or mixtures thereof.
  • TiCI 4 titanium tetrachloride
  • TiCI 4 titanium tetra- alkoxides
  • titanium tetra isopropoxide titanium tetra isopropoxide
  • mixtures thereof titanium tetrachloride
  • the use of a combination of at least one halide and at least one alkoxide as precursor of the at least one transition metal oxide gives rise to the advantage that a nonaqueous organic solvent can be used, instead of water as solvent according to the prior art.
  • non-aqueous organic solvents makes it possible that the solvent is in general easily removed from the reaction mixture obtained in step (A) of the process according to the present invention.
  • a further advantage of the use of a non-aqueous ( ⁇ 1 % H 2 O) organic solvent is that no water molecules are present that may accelerate the hydrolysis process or be trapped within the hydrolyzed metal oxide framework, and may disturb the formation of the desired highly ordered structures.
  • a mixture of at least two different precursor compounds of the at least one transition metal oxide is used in step (A) of the process according to the present invention.
  • Preferred mixtures of at least two different precur- sors are for example at least one halide and at least one alkoxide, especially preferred a mixture of the chloride and the isopropoxide of the corresponding transition metal.
  • These two components of the mixture of precursors can be used in any suitable ratio, for example in a weight ratio of halide : alkoxide of 10:1 to 1 :10.
  • titanium dioxide as the at least one transition metal oxide
  • a very preferred mixture of suitable precursor compounds is titanium tetrachloride (TiCI 4 ) and titanium tetra-isopropoxide (Ti(O 1 Pr) 4 ).
  • titanium tetrachloride and titanium tetra-isopropoxide can be used in any ratio, preferably in a weight ratio of TiCI 4 to Ti(O 1 Pr) 4 of 10:0.1 to 0.1 :10, particularly preferred between 6:1 to 1 :6.
  • step (A) of the process according to the present invention is conducted in at least one non-aqueous organic solvent.
  • non-aqueous means that essentially less than 1 % water is present in the organic solvent at the start of the reaction and that any water introduced to the reaction mixture after the mixing of the precursors of at least one transition metal oxides with the at least one non-ionic surfactant comprising silicon in at least one non-aqueous organic solvent is less than 30% by weight of the entire reaction mixture, preferably less than 20% by weight and particularly preferred less than 10% by weight, in each case in respect of the whole reaction mixture.
  • the amount of water present in the reaction mixture can be acquired by titration according to the known Karl-Fischer method.
  • the non-aqueous organic solvent which is used in step (A) of the process according to the present invention can be any organic solvent, which is able to dissolve or at least to disperse the reaction components, particularly the at least one precursor of the at least one transition metal oxide and the at least one non-ionic surfactant.
  • the at least one organic solvent can be chosen from the group consisting of alcohols, esters, ethers, aliphatic hydrocarbons, aromatic hydrocarbons, amines, ketones, diketones, nitrated or chlorinated hydrocarbons and mixtures thereof.
  • the organic solvent comprises an alcohol and/or a cyclic ether.
  • Suitable alcohols can be chosen from aliphatic alcohols having 1 to 10 carbon atoms, like methanol, ethanol, propanols, like n-propanol, iso-propanol, butanols, like n- butanol, iso-butanol, tert-butanol and mixtures thereof.
  • Suitable ethers can be chosen from cyclic or acyclic ethers.
  • suitable acyclic ethers are dialkyl ethers for example chosen from the group consisting of dimethyl ether, diethyl ether, methyl-tert. -butyl ether and mixtures thereof.
  • suitable cyclic ethers can be chosen from the group consisting of tetrahydrofurane (THF), 1 ,2-dioxane, 1 ,3-dioxane and 1 ,4-dioxane and mixtures thereof.
  • THF tetrahydrofurane
  • Suitable ketones or diketones can be chosen from the group consisting of acetone, acetoacetate, 2-propanone, 2-butanone, benzophenone, diacetyl, acetylacetone, hex- ane-2,5-dione and mixtures thereof.
  • an alcohol for example ethanol, or a mixture of at least two non-aqueous organic solvents is used, for example a mixture of at least one alcohol and at least one ether. Suitable alcohols and ethers are mentioned above. Ethanol or a mixture of ethanol and THF is particularly preferred.
  • the volume ratio of the at least two organic solvents in the case where a mixture is used, can be any volume ratio which gives rise to a mixture that is able to dissolve or at least to disperse the reaction components.
  • the volume ratio of at least two solvents is from 1 :10 to 10:1 , preferably from 1 :5 to 5:1 , for example 1 :2 to 2:1.
  • the at least one non-ionic surfactant comprising silicon can in general be chosen from silicon comprising non-ionic surfactants known to a person having ordinary skill in the art. Suitable compounds are described, for example, in Wang et al., Journal of Colloids and Interface Science 242, 337 to 345 (2001 ) and Wang et al., Journal of Colloids and Interface Science 256, 331 to 340 (2002). An overview of syntheses and structures of common silicone surfactants is given in Silicone surfactants, Randal M. Hill, Surfactant science series, Volume 86, 1999, Ed.: Arthur T. Hubbard.
  • Silicone comprising non-ionic surfactants, comprising polyoxyalkylene polyether groups are preferred, for example made of at least one alkylene oxide, for example chosen from the group consisting of ethylene oxide, propylene oxide, butylene oxide and mix- tures thereof.
  • silicon comprising building blocks, for example -SiR 1 R 2 -O-moieties, in which R 1 and R 2 can be identical or different, and can be chosen from d ⁇ o-alkyl radicals and/or polyoxyalkylene polyether building blocks as mentioned above, are present in the surfactants according to the present invention.
  • Polyoxyalkylene polyether building blocks and silicon comprising moieties are in general connected via hydrolytically unstable -Si-O-C- and/or hydrolytically stable -Si-C- groups.
  • the Si-C linkage is usually made by a Pt-catalysed hydrosilylating addition of an Si-H function in the polysiloxane to a terminal olefinic bond in the substituent poly- ether.
  • the Si-O-C linkage can be made by esterification of chloropolysiloxanes with hydroxyl-functionalized polyether.
  • the arrangement of these different blocks within the surfactant can be random or block-wise, linear or branched.
  • Molecular weight of silicon comprising non-ionic surfac- tants is in general 500 to 50000 g/mol, preferably 1000 to 20000 g/mol.
  • the number of branching points of the silicone and the number of connection points to the polyoxyalkylene polyether building blocks can be varied.
  • non-ionic surfactants comprising silicon which are used in the process according to the present invention are chosen from silicon-polyoxy alkylene polyether copolymers, for example according to formulae (1 ), (2), (3) and (4) and mixtures thereof
  • R 1 independently of each other, radical chosen from Ci-C 2 o-alkyl, Ci-C 25 -alicyclic, Ci-C 2 5-aryl, Ci-C 2 5-alkaryl, Ci-C 25 -aralkyl.
  • R 2 independently of each other a polyoxyalkylene polyether radical of formula (5) -(CH 2 ) a -(OCH 2 CH 2 ) b [OCH 2 CH(CH 3 )]c[OCH 2 CH(CH 2 CH 3 )]d-R 4 (5),
  • a, b, c, d, and R 4 have the following meanings: a integer of 0 to 6, preferably 0 to 4, for example 0, 1 , 2, 3 or 4, most preferably 3 b integer of O to 100, preferably 5 to 50, for example 6, 7, 8, 9, 10, 1 1 , 12, 13,
  • R 4 chosen from the group consisting of functional groups like NH 2 , NH, OH, OR 5 , wherein R 5 is Ci-Cio-alkyl, preferably methyl and/or ethyl, C 5 -Ci 6 -aryl, C 5 -Ci6-alkaryl, preferably benzyl, Ci-C 20 -alkoyl, aroyl, preferably benzoyl, wherein arrangement of polyoxyalkylene polyether units may be block-wise, alternating or randomly, x integer of 0 to 200, preferably 0 to 100, y integer of 1 to 50, preferably 1 to 30.
  • the at least one silicon comprising non-ionic surfactant is chosen from the group consisting of silicon-polyoxy alkylene polyether copolymers according to formulae (1 ), (2) or (3).
  • the at least one silicon comprising non-ionic surfactant is chosen from the group consisting of silicon-polyoxy alkylene polyether copolymers according to formulae (1 ) or (2).
  • the at least one silicon comprising non-ionic surfactant is chosen from the group consisting of silicon-polyoxy alkylene polyether copolymers according to formulae (1 ) or (2) wherein R 1 is methyl, a is 3, b is an integer of 0 to 100, preferably 5 to 50, for example 6, 7, 8, 9, 10, 1 1 , 12, 13, 14 or 15, c is an integer of 0 to 50, preferably 0 to 25, for example 0, 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, d is an integer of 0 to 20, preferably 0 to 10, for example 0, 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, wherein b+c+d ⁇ 1 , R 4 is chosen from OH and OR 5 , wherein R 1 is methyl, a is 3, b is an integer of 0 to 100, preferably 5 to 50
  • the at least one silicon comprising non-ionic surfactant is chosen from the group consisting of silicon-polyoxy alkylene polyether copolymers according to formulae (1 ) or (2) wherein R 1 is methyl, a is 3, b is an integer of 0 to 100, preferably 5 to 50, for example 6, 7, 8, 9, 10, 1 1 , 12, 13, 14 or 15, c is an integer of 0 to 50, preferably 0 to 25, for example 0, 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, d equals 0, R 4 is OH, wherein arrangement of polyoxyalkylene polyether units may be block-wise, alternating or randomly, x is an integer of 0 to 200, preferably 0 to 100, and y is an integer of 1 to 50, preferably 1 to 30.
  • the at least one silicon comprising non-ionic surfactant is chosen from the group consisting of silicon-polyoxy alkylene polyether copolymers according to formula (2) wherein R 1 is methyl, a is 3, b is an integer of 5 to 50, preferably 5 to 30, for example 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14 or 15, c is an integer of 0 to 50, preferably 0 to 25, for example 0, 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, d equals 0, R 4 is OH, wherein arrangement of polyoxyalkylene polyether units may be block-wise, alternating or randomly, x is an integer of 3 to 200, preferably 3 to 100, more preferably 3 to 50, more preferably 10 to 30 and most preferred 15 to 25.
  • the at least one silicon comprising non-ionic surfactant is chosen from the group consisting of silicon-polyoxy alkylene polyether copolymers according to formula (1 ), wherein R 1 is methyl, a is 3, b is an integer of 1 to 30, preferably 1 to 20, for example 8, 9, 10, 11 , 12 c is an integer of 0 to 5, preferably 0-2, d equals 0, R 4 is OH, wherein arrangement of polyoxyalkylene polyether units may be block-wise, alternating or randomly, x is an integer of 1 to 50, preferably 15 to 30, for example 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, and y is an integer of 1 to 50, preferably 1 to 20, for example 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15.
  • formula (1 ) silicon-polyoxy alkylene polyether copolymers according to formula (1 ), wherein R 1 is methyl, a is 3, b is an integer of 1 to 30, preferably 1 to 20, for example 8, 9, 10, 11 , 12 c is an integer of
  • the at least one silicon comprising non-ionic surfactant is chosen from the group consisting of silicon-polyoxy alkylene polyether copolymers according to formula (1 ), wherein R 1 is methyl, a is 3, b is an integer of 1 to 50, preferably 5 to 30, for example 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, c is an integer of 0 to 50, preferably 0 to 25, more preferably 1 to 15, for example 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, d equals 0, R 4 is OH, wherein arrangement of polyoxyalkylene polyether units may be block-wise, alternating or randomly, preferably block-wise, x is an integer of 1 to 100, preferably 30 to 80, more preferably 50 to 70, for example 55, 56, 57, 58, 59, 60, 61 , 62, 63, 64, 65, and y is an integer of 1 to 50, preferably 1 to 20, for example 5, 6, 7, 8, 9,
  • the at least one silicon comprising non-ionic surfactant is chosen from the group consisting of silicon-polyoxy alkylene polyether copolymers according to formula (1 ), wherein R 1 is methyl, a is 3, b is an integer of 1 to 50, preferably 10 to 30, for example 18, 19, 20, 21 , 22, 23, 24, 25, c is an integer of 0 to 50, preferably 0 to 25, more preferably 1 to 10, for example 5, 6, 7, 8, 9, 10, d equals 0, R 4 is OH, wherein arrangement of polyoxyalkylene polyether units may be block-wise, alternating or randomly, preferably block- wise, x is an integer of 1 to 50, preferably 20 to 40, for example 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, and y is an integer of 1 to 50, preferably 1 to 20, for example 5, 6, 7, 8,
  • the at least one silicon comprising non-ionic surfactant is chosen from the group consisting of silicon-polyoxy alkylene polyether copolymers according to formula (1 ), wherein R 1 is methyl, a is 3, b is an integer of 1 to 50, preferably 1 to 20, for example 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, c is an integer of 0 to 50, preferably 20 to 40, for example 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, d equals 0, R 4 is OH, wherein arrangement of polyoxyalkylene polyether units may be block-wise, alternating or randomly, x is an integer of 1 to 30, preferably 1 to 10, for example 1 , 2, 3, 4, 5, 6, 7, and y is an integer of 1 to
  • the at least one silicon comprising non-ionic surfactant is chosen from the group consisting of compounds (6), (7), (8), (9) or (10)
  • step (A) of the process according to the present invention can be conducted in all manners known to the skilled artisan.
  • the reaction components being the at least one precursor of the at least one transition metal oxide, the at least one non-ionic surfactant comprising silicon and the at least one nonaqueous organic solvent can be added subsequently into a suitable reactor.
  • suitable reactors are known to the skilled artisan, for example laboratory equipment like flasks, beakers, etc. In an industrial scale, suitable reactors can be used, which are operated continuously or discontinuously. For reasons of efficiency, a continuous process is preferred.
  • the at least one precursor of the at least one transition metal oxide is added to the dispersed polymer either dispersed in an organic solvent or neat.
  • the at least one precursor of the at least one transition metal oxide is added neat, e.g. that it is not dissolved or dispersed in any solvent, to a solution of the at least one non-ionic surfactant comprising silicon in at least one non-aqueous organic solvent.
  • At least one precursor of the at least one transition metal oxide is present in an amount of 1 to 50% by weight, preferably 5 to 40% by weight, particularly preferred in an amount of 10 to 38% by weight, based on the whole reaction mixture in each case.
  • the at least one non-ionic surfactant comprising silicon is present in an amount of 0.1 to 30% by weight, preferably 1.0 to 25% by weight, particularly preferred in an amount of 2 to 20% by weight, based on the whole reaction mixture in each case.
  • the reaction mixture obtained is stirred for a period long enough to obtain the desired particles in high yield, for example 1 minute to 24 hours, preferably 10 minutes to 10 hours, particularly preferred 30 minutes to 6 hours, for example 2 hours.
  • Stirring of the reaction mixture can be conducted by any method known to a person having ordinary skill in the art, for example blade stirrer, stirrer bar, overhead stirrer, milling (ball milling), mechanical agitation.
  • Step (A) of the process according to the present invention can be conducted at any temperature, at which the reaction mixture is in the liquid or dispersed phase.
  • a reaction temperature of 0 to 80 0 C, particularly preferably 10 to 40 0 C, for example room temperature is suitable.
  • Step (A) of the process according to the present invention can be conducted at any pressure, at which the reaction mixture is in the liquid or dispersed phase.
  • a pressure of 0.5 to 10 bar (absolute), preferably 0.8 to 5 bar (absolute), particularly preferably 0.9 to 2 bar (absolute), for example atmospheric pressure is suitable.
  • a reaction mixture is obtained, which is preferably a homogenous reaction mixture.
  • Step (B) of the process according to the present invention comprises drying the reaction mixture obtained in step (A) to obtain particles comprising the at least one transition metal oxide and silicon dioxide.
  • Step (B) of the process according to the present invention can be conducted by all methods that are known to the person having ordinary skill in the art, for example spray-drying, spontaneous evaporation in an open vessel, evaporation by application of direct or indirect heat or evaporation under reduced pressure (for example in a rotary evaporator or on a Schlenk line).
  • step (B) is conducted by evaporating the at least one nonaqueous organic solvent at a temperature depending on the organic solvent and the method of evaporation.
  • a temperature depending on the organic solvent and the method of evaporation for example, in the case where the non-aqueous organic solvent is ethanol and the evaporation method is the application of heat to an open vessel, step (B) is conducted at temperatures of 25 to 60°C, preferably 30 to 50 0 C, for example 40°C.
  • the particles which are obtained after removing of the non-aqueous organic solvent can further be dried at a higher temperature depending on the organic solvent.
  • step (B) is conducted at temperatures for example 60 to 120 0 C, preferably 70 to 100 0 C, and particularly preferred 70 to 90°C.
  • Drying according to step (B) of the process according to the present invention can be conducted for a period which is long enough to obtain dry particles, meaning that no solvent is left. Suitable periods of time depend upon the amount and choice of organic solvent involved and are generally 10 minutes to two days, particularly preferred 30 minutes to 20 hours, for the first drying step, and 30 minutes to 12 hours, preferably 1 to 8 hours, for the second drying step at higher temperature, as mentioned above.
  • the particles comprising at least one transition metal oxide and silicon dioxide are obtained.
  • the primary size of these particles lies at 1 to 40 nm, preferably 3 to 30 nm, even without any further heat treatment.
  • step (C) can optionally be conducted after step (B):
  • step (C) Calcination of the particles obtained from step (B) of the process according to the present invention at a temperature of 200 to 800 0 C in an oxygen comprising atmosphere.
  • Calcination according to step (C) of the present invention can be conducted in any reactor suitable for a calcination reaction, for example laboratory furnace, shaft furnace, multiple hearth furnace, drying oven, microwave oven, cabinet ovens, batch ovens, tunnel ovens, horizontal or vertical conveyor ovens, tray type ovens, fluidized bed reactor or rotary kiln.
  • reactor suitable for a calcination reaction for example laboratory furnace, shaft furnace, multiple hearth furnace, drying oven, microwave oven, cabinet ovens, batch ovens, tunnel ovens, horizontal or vertical conveyor ovens, tray type ovens, fluidized bed reactor or rotary kiln.
  • the calcination temperature can be chosen from 200 to 800°C, preferably 280 to 600°C. In a preferred embodiment, more than one different temperature are used in step (C) depending on the polyethersiloxane used as structure directing agent, wherein in a particularly preferred embodiment, calcination is firstly conducted at a lower temperature of for example 200 to 400 0 C, followed by a second calcination step at a higher temperature of for example 400 to 700°C.
  • Calcination according to step (C) of the present invention can be conducted for a period of time depending on the amount of sample to be calcined and the initial concentration of polyethersiloxane, generally one to 24 hours, preferably 2 to 12 hours.
  • the first calcination step can be conducted at a lower temperature for a period of time of 15 minutes to five hours, preferably 1 to 3 hours, followed by the second calcination step at a higher temperature for a period of time of 1 to 12 hours.
  • any atmosphere comprising oxygen known to the skilled artisan can be used and different atmospheres can be used for the different calcination steps described above.
  • one or more of these atmospheres can be nitrogen, oxygen, air or an artificial ("oxygen poor” or "oxygen rich") atmosphere comprising oxygen, nitrogen and/or other inert gases.
  • the atmosphere comprising oxygen in step (C) of the process according to the present invention is air or an oxygen poor atmosphere.
  • step (C) of the process according to the present invention particles comprising at least one transition metal oxide and silicon dioxide are obtained.
  • the primary size (diameter) of these particles is in general 0.01 to 40 nm, preferably 0,01 to 30 nm, particularly preferred 0,01 to 15 nm, for example 0,01 to 10 nm, calculated using diffraction data from XRD-measurements and confirmed by transmission electron microscopic analysis.
  • more than 70% of all particles lie in the specified range, preferred more than 80% and particularly preferred more than 90%.
  • the process according to the present invention gives rise to particles as mentioned above, having a high BET surface area.
  • the BET surface area of the particles obtained from the process according to the present invention is higher than 150 m 2 /g, preferably higher than 200 m 2 /g.
  • the BET surface area of the particles obtained from the process according to the present invention is in general lower than 600 m 2 /g.
  • the pore size of the material obtained from the process according to the present invention is in general 0.5 to 25 nm, preferably 1 to 20 nm, particularly preferably 2 to 10 nm.
  • the amount of silicon dioxide which is present in the particles according to the present invention is in general 1 to 20 % by weight, preferably 3 to 12 % by weight, in each case based on the whole particle.
  • SiC> 2 is present within the pores of the high surface area TiC> 2 material, preferably small SiO 2 -particles are present on the pore walls of TiO 2 .
  • the presence of SiO 2 at the pore walls Of TiO 2 gives rise to an improved heat stability of these particles, because the anatase modification Of TiO 2 is less easily transferred into the less active rutil modifica- tion; this is a known effect.
  • the present invention further relates to a particle comprising at least one transition metal oxide and silicon dioxide, obtainable, preferably obtained, by the process according to the present invention.
  • the present invention relates to a particle as mentioned above, wherein the size (diameter) of the primary particle de- termined by XRD method for calculating crystallite size is 1 to 40 nm, the BET surface area of the particle measured according to DIN standard 66131 is higher than 200 m 2 /g and the pore size of the particle calculated using the BHJ method for adsorption is 1 to 6 nm. Preferred embodiments of these particles are mentioned above.
  • the present invention relates to the use of at least one halide, preferably at least one chloride, or at least one alkoxide, preferably at least one iso-propoxide, or a mixture of the two, and of at least one transition metal, in a process for the preparation of particles comprising at least one transition metal oxide and silicon dioxide in the presence of at least one non-ionic surfactant comprising silicon, in a non-aqueous or- ganic solvent, preferably the use of a mixture of titanium tetrachloride (TiCI 4 ) and titanium tetraisopropoxide Ti(O 1 Pr) 4 in the preparation of particles comprising titanium dioxide (TiO 2 ) and silicon dioxide (SiO 2 ). Preferred embodiments of the use of this specific mixture have been mentioned above.
  • the present invention further relates to a mixture comprising the particle according to the present invention and at least one other transition metal oxide, activating agent and/or catalytic material, for example the oxides of the elements of Groups III to XII or metallic nanoparticles for example of platinum, palladium, silver or gold.
  • at least one other transition metal oxide, activating agent and/or catalytic material for example the oxides of the elements of Groups III to XII or metallic nanoparticles for example of platinum, palladium, silver or gold.
  • the present invention further relates to the use of the particles according to the present invention as a catalyst or as a catalyst carrier material.
  • step (D) can optionally be conducted after step (C):
  • the present invention further relates to a process for the preparation of a powder film, wherein particles according to the present invention are applied to a substrate such as glass, plastics, textiles, ceramics or metal.
  • the particles obtained from the process according to the present invention can be suspended into transparent or non- transparent solutions with aqueous or non-aqueous solvents with or without the aid of stabilizing acids, bases or surfactants.
  • the suspensions are introduced to the substrate surface by methods generally known to a person having ordinary skill in the art.
  • the present invention further relates to a process for the preparation of a coating of at least one transition metal oxide and silicon oxide, wherein a mixture comprising at least one precursor of the at least one transition metal oxide and at least one non-ionic sur- factant comprising silicon in at least one non-aqueous organic solvent is applied to a substrate.
  • This mixture is the same mixture that is described above, in respect of step (A) of the process for the preparation of particles. Preferred embodiments are mentioned above.
  • the at last one precursor of at least one transition metal oxide is a combination of titanium tetra-chloride (TiCI 4 ) and titanium tetra-isopropoxide (Ti(O 1 Pr) 4 ).
  • Application of the mixture to the substrate is preferably conducted by dip- or spin-coating. These methods are in general known to a person having ordinary skill in the art.
  • Examples 1 to 30 are prepared by mixing TiCI 4 with Ti(iPrO) 4 in amounts as shown in table 1 , and adding this mixture to a stirred ethanolic or mixed ethanol/THF solution containing the respective surfactant.
  • the volume ratio of ethanol and THF is shown in table 1.
  • the reaction mixture is stirred for 2h at room temperature and is then dried for 16 h at 40 0 C and then for 6 h at 80 0 C.
  • the powder formed upon drying is then cal- cined in air. Calcination temperatures and times are detailed in table 1.
  • BET and N 2 -adsorption measurements are carried out according to DI N standard 66131 .
  • the pore diameter is calculated using the BHJ method for adsorption.
  • the modification of the crystalline TiO 2 and the primary particle size are determined by use of XRD (Powder Diffraction).
  • the Si- and Ti-concentrations are determined by elemental analysis and are given in weight percent.
  • the photocatalytic activity is determined via the rate of degradation of the chlorinated hydrocarbon dichloroacetic acid (DCA) in suspension.
  • the total reaction time of the degradation experiments for determining the rate of degradation of DCA in aqueous solution is 24 hours.
  • the UV-light intensity is 1 mW/cm 2 .
  • the pH-value of the suspension is set to 3 with sodium hydroxide.
  • the temperature of the reaction vessel is 20 to 30 0 C.
  • the concentration of DCA is 20 mmol/L and the concentration of the photocata- lyst is 3 g/L.
  • the degradation rate (ppm/h) is determined by measurement of the pH- value before and after 24h irradiation. Degradation rates are normalized to the weight Of TiO 2 in the sample.
  • Blank tests are carried out to degrade DCA under irradiation using the method de- scribed above in the presence of a commercially available standard photocatalyst (De- gussa P25, ,,blank 1 "), comprising no silicon dioxide, as well as to degrade DCA under irradiation without the presence of a photocatalyst ("blank 2").
  • a commercially available standard photocatalyst (De- gussa P25, ,,blank 1 "), comprising no silicon dioxide, as well as to degrade DCA under irradiation without the presence of a photocatalyst (blank 2").
  • the thermal stability of the mesoporous, SiO 2 -stabilized materials was tested by heating the sample to given temperatures over 10h and measurement of the BET surface area and pore size (via nitrogen adsorption), particle size via XRD analysis, and photo- catalytic activity according to the DCA-degradation test described above.
  • Comparative Example 1 (DT52, Millennium Chemicals), being anatase TiC> 2 with WO3 dopant (BET surface area 78-98 m 2 /g, information from Millennium Inorganic Chemicals website) and Comparative Example 2 (DT58, Millennium Chemicals), being anatase TiC> 2 with SiC> 2 and WO3 dopants (BET surface area 95-125 m 2 /g, information from Millennium Inorganic Chemicals website) were also treated in the same manner.
  • Table 3 The results are given in Table 3:
  • Examples 31 to 38 are prepared by mixing 0.6 g TiCI 4 with 2.5 g Ti( 1 PrO) 4 , and adding this mixture to a stirred 20 mL ethanolic solution containing 2.0 g of surfactant 1. Distilled water is added to the reaction mixture in amounts shown in table 4.
  • the reaction mixture is stirred for 2 h at room temperature and is then dried for 16 h at 40 0 C and then for 6 h at 80 0 C.
  • the powder formed upon drying is then calcined in air for 2 h at 300 0 C and then 5 h at 450 0 C.

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Abstract

L'invention concerne un procédé pour préparer des particules comportant au moins un oxyde de métal de transition et un dioxyde de silicium, comprenant les étapes consistant à : (A) mettre en contact au moins un précurseur dudit au moins un oxyde de métal de transition et au moins un tensioactif non ionique comportant du silicium dans au moins un solvant organique non aqueux pour obtenir un mélange de réaction; (B) sécher le mélange de réaction obtenu en (A) pour obtenir des particules comportant ledit au moins un oxyde de métal de transition et le dioxyde de silicium, et (C) soumettre les particules obtenues en (B), du procédé selon l'invention, à une calcination à 800 degrés Celsius dans une atmosphère contenant de l'oxygène. L'oxyde de métal de transition est du dioxyde de titane.
PCT/EP2010/053555 2009-03-20 2010-03-18 Procédé de production de matériaux en dioxyde de titane à surfaces de contact et stabilité thermique élevées WO2010106146A1 (fr)

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US10106657B2 (en) 2014-11-06 2018-10-23 The Chemours Company Fc, Llc Preparation of lacing resistant, titanium dioxide particles for use in photodurable thin film production

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US9080259B2 (en) 2009-06-30 2015-07-14 Basf Se Polyamide fibers with dyeable particles and production thereof
US10106657B2 (en) 2014-11-06 2018-10-23 The Chemours Company Fc, Llc Preparation of lacing resistant, titanium dioxide particles for use in photodurable thin film production
US10745529B2 (en) 2014-11-06 2020-08-18 The Chemours Company Fc, Llc Preparation of lacing resistant, titanium dioxide particles for use in photodurable thin film production
US11279806B2 (en) 2014-11-06 2022-03-22 The Chemours Company Fc, Llc Preparation of lacing resistant, titanium dioxide particles for use in photodurable thin film production

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