CA2312249A1 - Granules based on pyrogenic titanium dioxide, a process for preparing them and their use - Google Patents
Granules based on pyrogenic titanium dioxide, a process for preparing them and their use Download PDFInfo
- Publication number
- CA2312249A1 CA2312249A1 CA002312249A CA2312249A CA2312249A1 CA 2312249 A1 CA2312249 A1 CA 2312249A1 CA 002312249 A CA002312249 A CA 002312249A CA 2312249 A CA2312249 A CA 2312249A CA 2312249 A1 CA2312249 A1 CA 2312249A1
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- Canada
- Prior art keywords
- titanium dioxide
- granules
- chz
- pyrogenic titanium
- spray
- 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.)
- Abandoned
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 33
- 239000008187 granular material Substances 0.000 title claims abstract description 30
- 230000001698 pyrogenic effect Effects 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000002245 particle Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 4
- 239000000919 ceramic Substances 0.000 claims abstract description 3
- 239000003086 colorant Substances 0.000 claims abstract description 3
- 239000002537 cosmetic Substances 0.000 claims abstract description 3
- 239000011521 glass Substances 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 239000004922 lacquer Substances 0.000 claims abstract description 3
- 238000005498 polishing Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 3
- 239000004945 silicone rubber Substances 0.000 claims abstract description 3
- 230000000475 sunscreen effect Effects 0.000 claims abstract description 3
- 239000000516 sunscreening agent Substances 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 18
- 238000001694 spray drying Methods 0.000 abstract description 5
- 235000010215 titanium dioxide Nutrition 0.000 description 28
- 150000001282 organosilanes Chemical class 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 9
- -1 siloxanes Chemical class 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 2
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
-
- 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
- C01G23/07—Producing by vapour phase processes, e.g. halide oxidation
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/29—Titanium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
- A61K8/645—Proteins of vegetable origin; Derivatives or degradation products thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- 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
- B01J35/31—Density
-
- 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
- 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
- B01J35/613—10-100 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- 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
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
-
- 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
-
- 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
- C09C1/3615—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C1/3638—Agglomeration, granulation, pelleting
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- 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
- C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/69—Particle size larger than 1000 nm
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1409—Abrasive particles per se
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09708—Inorganic compounds
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Glanulating (AREA)
- Silicon Compounds (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
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Abstract
Granules based on titanium dioxide with the characteristics:
Average particle diameter: 10 to 150µm BET surface area: 25 to 100 m2/g PH 3 to 6 Compacted density: 400 to 1,200 g/1 They are prepared by dispersing titanium dioxide in water and spray-drying and silanisin.
In the silanised form, the granules have the following characteristics:
Average particle diameter: 10 to 160µm BET surface area: 15 to 100 m2/g pH: 3.0 to 9.0 Compacted density: 400 to 1,200g/l Carbon content: 0.3 to 12.0 wt.%
The granules are used, inter alia, as catalyst supports, in cosmetics, as sun screens, in silicone rubber, in toning powder, in lacquers and colorants, as grinding and polishing agents and as a raw material for producing glass and ceramics.
Average particle diameter: 10 to 150µm BET surface area: 25 to 100 m2/g PH 3 to 6 Compacted density: 400 to 1,200 g/1 They are prepared by dispersing titanium dioxide in water and spray-drying and silanisin.
In the silanised form, the granules have the following characteristics:
Average particle diameter: 10 to 160µm BET surface area: 15 to 100 m2/g pH: 3.0 to 9.0 Compacted density: 400 to 1,200g/l Carbon content: 0.3 to 12.0 wt.%
The granules are used, inter alia, as catalyst supports, in cosmetics, as sun screens, in silicone rubber, in toning powder, in lacquers and colorants, as grinding and polishing agents and as a raw material for producing glass and ceramics.
Description
Granules based on pyrogenic titanium dioxide, a process for preparing them and their use The invention provides granules based on pyrogenic titanium dioxide, the process for preparing them and the use thereof.
It is known that pyrogenic titanium dioxide can be prepared from TiCl4 by high temperature or flame hydrolysis (Ullmanns Enzyklopadie der technischen Chemie, 4th edition, vol. 21, page 464 (1982)).
Pyrogenic titanium dioxide is characterised by extremely finely divided particles, a high surface area (BET), very high purity, spherically shaped particles and a lack of pores. As a result of these properties, pyrogenic titanium dioxide is increasingly being considered as a support for catalysts (Dr. Koth et al., Chem. Ing. Techn. 52, 628 (1980)). For this application, pyrogenic titanium dioxide is shaped in a mechanical manner using, for example, tabletting machines.
Thus, there is the object of producing spray-dried granules of pyrogenic titanium dioxide which can be used as a catalyst support.
The invention provides granules based on pyrogenic titanium dioxide with the following physico-chemical characteristics:
Average particle diameter: 10 to 150 ~m BET surface area: 25 to 100 m2/g pH: 3 to 6 Compacted density: 400 to 1,200 g/1 ' ~ 980194 FH / AL
It is known that pyrogenic titanium dioxide can be prepared from TiCl4 by high temperature or flame hydrolysis (Ullmanns Enzyklopadie der technischen Chemie, 4th edition, vol. 21, page 464 (1982)).
Pyrogenic titanium dioxide is characterised by extremely finely divided particles, a high surface area (BET), very high purity, spherically shaped particles and a lack of pores. As a result of these properties, pyrogenic titanium dioxide is increasingly being considered as a support for catalysts (Dr. Koth et al., Chem. Ing. Techn. 52, 628 (1980)). For this application, pyrogenic titanium dioxide is shaped in a mechanical manner using, for example, tabletting machines.
Thus, there is the object of producing spray-dried granules of pyrogenic titanium dioxide which can be used as a catalyst support.
The invention provides granules based on pyrogenic titanium dioxide with the following physico-chemical characteristics:
Average particle diameter: 10 to 150 ~m BET surface area: 25 to 100 m2/g pH: 3 to 6 Compacted density: 400 to 1,200 g/1 ' ~ 980194 FH / AL
Granules according to the invention can be prepared by dispersing pyrogenic titanium dioxide in water, spray-drying.
The invention also provides granules based on pyrogenic titanium dioxide with the following physico-chemical characteristics:
Average particle diameter: 10 to 160 ~m BET surface area: 15 to 100 m2/g pH: 3.0 to 9.0 Compacted density: 400 to 1,200 g/1 Carbon content: 0.3 to 12.0 wt.o Granules according to the invention can be prepared by dispersing pyrogenic titanium dioxide in water, spray-drying then silanising the product. Halogenated silanes, alkoxysilanes, silazanes and/or siloxanes are used for silanising.
The following substances may be used in particular as halogenated silanes:
Halogenated organosilanes of the type X3Si (CnH2n+i) X = C1, Br n = 1 - 20 Halogenated organosilanes of the type XZ (R' ) Si (C~HZn+i) X = C1, Br R' - alkyl n = 1 - 20 Halogenated organosilanes of the type X (R' ) 2Si (C~Hz~+O
X = Cl, Br R' - alkyl ' ~ 980194 FH / AI, n = 1 - 20 Halogenated organosilanes of the type X3Si(CHz)m-R' X = Cl, Br m = 0, 1 - 20 R' - alkyl, aryl (e.g. -C6H5) -CqF9, -OCFZ-CHF-CF3, -C6F13, -O-CF2-CHF2 -NH2, -N3, -SCN, -CH=CH2, -OOC ( CH3 ) C=CHZ
-OCH2-CH ( O ) CHz -NH-CO-N-CO- ( CHZ ) 5 -NH-COO-CH3, -NH-COO-CHz-CH3, -NH- (CH2) 3Si (OR) 3 -Sx- (CH2) 3Si (OR) 3 Halogenated organosilanes of the type (R) X2Si (CHZ) m-R' X = Cl, Br R = alkyl m = 0, 1 - 20 R' - alkyl, aryl (e. g. -C6H5) -C9F9, -OCFZ-CHF-CF3, -C6F13, -O-CFZ-CHFz -NH2, -N3, -SCN, -CH=CHZ, -OOC ( CH3 ) C=CHZ
-OCHZ-CH (0) CHZ
-NH-CO-N-CO-(CHZ)s -NH-COO-CH3, -NH-COO-CHZ-CH3, -NH- (CHZ) 3Si (OR) 3 -Sx- (CH2) 3Si (OR) 3 Halogenated organosilanes of the type (R)ZXSi(CH2)m-R' X = C1, Br R = alkyl m = 0, 1 - 20 R' - alkyl, aryl (e. g. -C6H5) -CqF9, -OCFz-CHF-CF3, -C6F13, -O-CF2-CHF2 -NH2, -N3, -SCN, -CH=CHz, 3 5 -OOC ( CH3 ) C=CHz -OCHZ-CH (O) CHZ
' ~ 980194 FH / AL
-NH-CO-N-CO- (CHZ) 5 -NH-COO-CH3, -NH-COO-CH2-CH3, -NH- (CH2) 3Si (OR) 3 -sx- (CH2) 3Si (OR) 3 The following substances may be used in particular as alkoxysilanes:
Organosilanes of the type (RO) 3Si (CnH2~+i) R = alkyl n = 1 - 20 Organosilanes of the type R' x (RO) ySi (CnHZn+i) R = alkyl R' - alkyl n = 1 - 20 x+y = 3 x = l, 2 y = 1, 2 Organosilanes of the type (RO) 3Si (CH2) m-R' R = alkyl m = 0, 1 - 20 R' - alkyl, aryl (e.g. -C6H5) -C4F9, -OCF2-CHF-CF3, -C6Fls, -0-CFZ-CHFZ
-NH2, -N3, -SCN, -CH=CH2, -OOC ( CH3 ) C=CHZ
-OCHZ-CH ( O ) CH2 -NH-CO-N-CO- ( CHz ) s -NH-COO-CH3, -NH-COO-CH2-CH3, -NH- (CHZ) 3Si (OR) 3 -Sx- (CH2) 3S1 (OR) 3 Organosilanes of the type (R")x(RO)ySi(CHZ)m-R' R" - alkyl x+y = 3 x - l, 2 y - l, 2 R' - alkyl, aryl (e. g. -C6H5) ' ' 980194 FH / AI, J
-CqF9, -OCFz-CHF-CF3, -C6F13, -O-CFz-CHFz -NHz, -N3, -SCN, -CH=CHz, -OOC ( CH3 ) C=CHz -OCHz-CH (O) CHz -NH-CO-N-CO-(CHz)s -NH-COO-CH3, -NH-COO-CHz-CH3, -NH- (CHz) 3Si (OR) 3 -SX- (CHz) sSi (OR) 3 The silane Si 108 [(CH30)3-Si-CgHl~] trimethoxyoctylsilane may preferably be used as the silanising agent.
The following substances may be used in particular as silazanes:
Silazanes of the type R'RZSi-N-SiR2R' H
R = alkyl R' - alkyl, vinyl and also, for example, hexamethyldisilazane.
The following substances may be used in particular as siloxanes:
Cyclic polysiloxanes of the types D 3, D 4, D 5, e.g. octamethylcyclotetrasiloxane = D 4 ' ' 980194 FH / AL
CH3 \ /CH3 Si / \
H3C / O O \ CH3 /S i\ / S i H3C O \ ~ CH3 Si / \
Polysiloxanes or silicone oils of the type R R~~ m = 0, 1, 2, 3, . . . o0 n = 0, l, 2, 3, ... co Y-O- Si-O Si-O -Y a = 0, 1, 2, 3, ... o0 Ri in Y = CH3, H, CnH2n+lr n = 1 - 20 Y = Si (CH3) 3, Si (CH3) 2H
Si (CH3) 20H, Si (CH3) 2 (OCH3) Si (CH3) z (CnH2n+1) , n = 1 - 20 R - alkyl, aryl, (CHZ) n-NHZ, H
R' - alkyl, aryl, (CH2) n-NH2, H
R" - alkyl, aryl, (CH2) n-NHZ, H
R' ' ' - alkyl, aryl, (CHZ) n-NH2, H
The carbon content of granules according to the invention may be 0.3 to 12.0 wt. o.
The dispersion in water may have a titanium dioxide concentration of 3 to 25 wt. o.
Organic auxiliary substances may be added to the dispersion in order to increase the stability of the dispersion and to improve the particle morphology after spray-drying.
The following auxiliary substances may be used, for example:
polyalcohols, polyethers, surfactants based on fluorinated hydrocarbons, alcohols.
Spray-drying may be performed at a temperature of 200 to 600°C. Spinning disc atomisers or nozzle atomisers may be used.
Silanising may be performed using the halogenated silanes, alkoxysilanes, silazanes and/or siloxanes described above, wherein the silanising agent may optionally be dissolved in an organic solvent such as, for example, ethanol.
The silane Si 108 [ (CH30) 3-Si-C8H1~] trimethoxyoctylsilane may preferably be used as the silanising agent.
Silanising may be performed by spraying the granules with silanising agent at room temperature and then thermally treating the mixture at a temperature of 105 to 400°C for a period of 1 to 6 h.
An alternative method of silanising the granules may be performed by treating the granules with the silanising agent in vapour form and then thermally treating the mixture at a temperature of 200 to 800°C for a period of 0.5 to 6 h.
Thermal treatment may be performed under a protective gas such as, for example, nitrogen.
Silanising may be performed continuously or batchwise in heatable mixers and dryers with spray devices. Suitable " 980194 FH / AL
devices may be, for example: plough bar mixers, disc dryers, fluidised bed dryers or moving bed dryers.
The physico-chemical parameters of the granules, such as the specific surface area, particle size distribution, compacted density and pH, may be modified within the limits given above by varying the substances used and the conditions used during spraying, heating at constant temperature and silanising.
Titanium dioxide granules according to the invention have the following advantages:
The flow behaviour is better than non-spray-dried titanium dioxide.
Incorporation into organic systems is easier.
Dispersion is simpler.
No additional auxiliary substances are required for granulation.
Titanium dioxide granules according to the invention have a defined particle size, unlike non-spray-dried titanium dioxide which does not have a defined agglomerate size.
Titanium dioxide granules according to the invention can be handled in a dust-free manner.
Lower packaging costs are required for transportation due to the high compacted density.
Titanium dioxide granules according to the invention can be used as a catalyst support.
Non-spray-dried titanium dioxide is not suitable for this purpose because, for example, it is carried out of a fluidised bed.
Granules according to the invention may be used as a support for catalysts, and also in cosmetics, as a sunscreen, in silicone rubber, in toning powder, in lacquers and colorants, as a grinding and polishing agent and as a raw material for producing glass and ceramics.
Examples A titanium dioxide P25 with the following physico-chemical characteristics is used as a pyrogenic titanium dioxide.
It is disclosed in the series of documents called Pigments, no. 56 "Hochdisperse Metalloxide nach dem Aerosilverfahren", 4th edition, February 1989, Degussa AG.
Titanium dioxide P25 CAS no. 13463-67-7 Behaviour in water hydrophilic Appearance loose white powder BET surface area ' m'/g 50 15 Average size of primary 21 particles nm Compacted density ' g/1 about 100 Specific weight g/1 about 3.7 Loss on drying ' on leaving < 1.5 supplier (2 h at 105C) o Loss on ignition ' " (2 h < 2 1000C ) at pH ' (in 4a aqueous 3-4 dispersion) Si02 ' < 0.2 A12p3 ~J < 0 . 3 _ -< 0 . 01 Fe203 Ti02 > >99. 5 Z r02 -Hf02 ' -HC1 < 0.3 Sieve residue ' (Mocker's method, 45 ~.m)o < 0.05 1) according to DIN 66131 2) according to DIN ISO 787/XI, JIS K 5101/18 (not sieved) 5 3) according to DIN ISO 787/II, ASTM D 280, JIS K 5101/21 4) according to DIN 55921, ASTM D 1208, JIS K 5101/23 5) according to DIN ISO 787/IX; ASTM D 1208; JIS K 5101/29 6) according to DIN ISO 787/XVIII; ~JIS K 5101/20 7) with respect to substance dried for 2 h at 105°C
10 8) with respect to substance ignited for 2 h at 1000°C
9) HC1 content is component of loss on ignition 10) determined with an air comparison density bottle '' 980194 FH / AL
The titanium dioxides are prepared by spraying a volatile titanium compound into an oxyhydrogen flame formed from hydrogen and air. In most cases, titanium tetrachloride is used. This substance hydrolyses under the effect of the water being produced during the oxyhydrogen gas reaction to give titanium dioxide and hydrochloric acid. After leaving the flame, the titanium dioxide enters a so-called coagulation zone in which the titanium dioxide primary particles and primary aggregates agglomerate. The product, present at this stage as a kind of aerosol, is separated from the gaseous accompanying substances in cyclones and is then post-treated with moist hot air.
The particle sizes of the titanium dioxides may be varied by varying the reaction conditions such as, for example, temperature of the flame, proportion of hydrogen or oxygen, amount of titanium tetrachloride, residence time in the flame or the length of the coagulation zone.
The BET surface area is determined using nitrogen in accordance with DIN 66 131.
The compacted volume is determined in a similar way to that described in ASTM D 4164-88.
Equipment: Compacted volume meter STA V 2003 from the Engelsmann Co., in accordance with DIN 53194, para. 5.2 b-f 250 ml measuring cylinder, graduation mark every 2 ml Balance with max. error limit of ~ 0.1 g Performing the determination Set the counter on the compact=ed volume meter to 1000 strokes.
Tare the measuring cylinder.
Fill measuring cylinder with granules up to the 250 ml mark.
Note down the weight (~ 0.1 g).
Clamp the measuring cylinder in the compacted volume meter and switch the instrument on.
End of compacting -~ instrument automatically stops after 1000 strokes.
Read the compacted bulk volume accurately, to 1 ml.
Calculation E: weight of granules in g V: volume read off in ml W: water content in wt.°s (determined in accordance with test instructions P001) E x (100 - W) Compacted density = - -----V x 100 The pH is determined in 4 % strength aqueous dispersion, in the case of hydrophobic catalyst supports in water: ethanol 1:1.
Preparing granules accordin to the invention The pyrogenic titanium dioxide is dispersed in fully deionised water. A dispersing apparatus is used which operates on the rotor/stator principle. The dispersions being produced are spray-dried. Deposition of the final product is achieved using a filter or a cyclone.
The spray-dried and optionally heated granules are initially introduced into a mixer to be silanised and are sprayed optionally first with water and then with the silanising agent, under intense mixing. After completion of the spraying procedure, mixing is continued for 15 to 30 min and then the mixture is heated at a constant temperature of 100 to 400°C for 1 to 4 h.
The water used may be acidified with an acid, for example hydrochloric acid, until the pH is 7 to 1. The silanising agent used may be dissolved in a solvent such as, for example, ethanol.
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The invention also provides granules based on pyrogenic titanium dioxide with the following physico-chemical characteristics:
Average particle diameter: 10 to 160 ~m BET surface area: 15 to 100 m2/g pH: 3.0 to 9.0 Compacted density: 400 to 1,200 g/1 Carbon content: 0.3 to 12.0 wt.o Granules according to the invention can be prepared by dispersing pyrogenic titanium dioxide in water, spray-drying then silanising the product. Halogenated silanes, alkoxysilanes, silazanes and/or siloxanes are used for silanising.
The following substances may be used in particular as halogenated silanes:
Halogenated organosilanes of the type X3Si (CnH2n+i) X = C1, Br n = 1 - 20 Halogenated organosilanes of the type XZ (R' ) Si (C~HZn+i) X = C1, Br R' - alkyl n = 1 - 20 Halogenated organosilanes of the type X (R' ) 2Si (C~Hz~+O
X = Cl, Br R' - alkyl ' ~ 980194 FH / AI, n = 1 - 20 Halogenated organosilanes of the type X3Si(CHz)m-R' X = Cl, Br m = 0, 1 - 20 R' - alkyl, aryl (e.g. -C6H5) -CqF9, -OCFZ-CHF-CF3, -C6F13, -O-CF2-CHF2 -NH2, -N3, -SCN, -CH=CH2, -OOC ( CH3 ) C=CHZ
-OCH2-CH ( O ) CHz -NH-CO-N-CO- ( CHZ ) 5 -NH-COO-CH3, -NH-COO-CHz-CH3, -NH- (CH2) 3Si (OR) 3 -Sx- (CH2) 3Si (OR) 3 Halogenated organosilanes of the type (R) X2Si (CHZ) m-R' X = Cl, Br R = alkyl m = 0, 1 - 20 R' - alkyl, aryl (e. g. -C6H5) -C9F9, -OCFZ-CHF-CF3, -C6F13, -O-CFZ-CHFz -NH2, -N3, -SCN, -CH=CHZ, -OOC ( CH3 ) C=CHZ
-OCHZ-CH (0) CHZ
-NH-CO-N-CO-(CHZ)s -NH-COO-CH3, -NH-COO-CHZ-CH3, -NH- (CHZ) 3Si (OR) 3 -Sx- (CH2) 3Si (OR) 3 Halogenated organosilanes of the type (R)ZXSi(CH2)m-R' X = C1, Br R = alkyl m = 0, 1 - 20 R' - alkyl, aryl (e. g. -C6H5) -CqF9, -OCFz-CHF-CF3, -C6F13, -O-CF2-CHF2 -NH2, -N3, -SCN, -CH=CHz, 3 5 -OOC ( CH3 ) C=CHz -OCHZ-CH (O) CHZ
' ~ 980194 FH / AL
-NH-CO-N-CO- (CHZ) 5 -NH-COO-CH3, -NH-COO-CH2-CH3, -NH- (CH2) 3Si (OR) 3 -sx- (CH2) 3Si (OR) 3 The following substances may be used in particular as alkoxysilanes:
Organosilanes of the type (RO) 3Si (CnH2~+i) R = alkyl n = 1 - 20 Organosilanes of the type R' x (RO) ySi (CnHZn+i) R = alkyl R' - alkyl n = 1 - 20 x+y = 3 x = l, 2 y = 1, 2 Organosilanes of the type (RO) 3Si (CH2) m-R' R = alkyl m = 0, 1 - 20 R' - alkyl, aryl (e.g. -C6H5) -C4F9, -OCF2-CHF-CF3, -C6Fls, -0-CFZ-CHFZ
-NH2, -N3, -SCN, -CH=CH2, -OOC ( CH3 ) C=CHZ
-OCHZ-CH ( O ) CH2 -NH-CO-N-CO- ( CHz ) s -NH-COO-CH3, -NH-COO-CH2-CH3, -NH- (CHZ) 3Si (OR) 3 -Sx- (CH2) 3S1 (OR) 3 Organosilanes of the type (R")x(RO)ySi(CHZ)m-R' R" - alkyl x+y = 3 x - l, 2 y - l, 2 R' - alkyl, aryl (e. g. -C6H5) ' ' 980194 FH / AI, J
-CqF9, -OCFz-CHF-CF3, -C6F13, -O-CFz-CHFz -NHz, -N3, -SCN, -CH=CHz, -OOC ( CH3 ) C=CHz -OCHz-CH (O) CHz -NH-CO-N-CO-(CHz)s -NH-COO-CH3, -NH-COO-CHz-CH3, -NH- (CHz) 3Si (OR) 3 -SX- (CHz) sSi (OR) 3 The silane Si 108 [(CH30)3-Si-CgHl~] trimethoxyoctylsilane may preferably be used as the silanising agent.
The following substances may be used in particular as silazanes:
Silazanes of the type R'RZSi-N-SiR2R' H
R = alkyl R' - alkyl, vinyl and also, for example, hexamethyldisilazane.
The following substances may be used in particular as siloxanes:
Cyclic polysiloxanes of the types D 3, D 4, D 5, e.g. octamethylcyclotetrasiloxane = D 4 ' ' 980194 FH / AL
CH3 \ /CH3 Si / \
H3C / O O \ CH3 /S i\ / S i H3C O \ ~ CH3 Si / \
Polysiloxanes or silicone oils of the type R R~~ m = 0, 1, 2, 3, . . . o0 n = 0, l, 2, 3, ... co Y-O- Si-O Si-O -Y a = 0, 1, 2, 3, ... o0 Ri in Y = CH3, H, CnH2n+lr n = 1 - 20 Y = Si (CH3) 3, Si (CH3) 2H
Si (CH3) 20H, Si (CH3) 2 (OCH3) Si (CH3) z (CnH2n+1) , n = 1 - 20 R - alkyl, aryl, (CHZ) n-NHZ, H
R' - alkyl, aryl, (CH2) n-NH2, H
R" - alkyl, aryl, (CH2) n-NHZ, H
R' ' ' - alkyl, aryl, (CHZ) n-NH2, H
The carbon content of granules according to the invention may be 0.3 to 12.0 wt. o.
The dispersion in water may have a titanium dioxide concentration of 3 to 25 wt. o.
Organic auxiliary substances may be added to the dispersion in order to increase the stability of the dispersion and to improve the particle morphology after spray-drying.
The following auxiliary substances may be used, for example:
polyalcohols, polyethers, surfactants based on fluorinated hydrocarbons, alcohols.
Spray-drying may be performed at a temperature of 200 to 600°C. Spinning disc atomisers or nozzle atomisers may be used.
Silanising may be performed using the halogenated silanes, alkoxysilanes, silazanes and/or siloxanes described above, wherein the silanising agent may optionally be dissolved in an organic solvent such as, for example, ethanol.
The silane Si 108 [ (CH30) 3-Si-C8H1~] trimethoxyoctylsilane may preferably be used as the silanising agent.
Silanising may be performed by spraying the granules with silanising agent at room temperature and then thermally treating the mixture at a temperature of 105 to 400°C for a period of 1 to 6 h.
An alternative method of silanising the granules may be performed by treating the granules with the silanising agent in vapour form and then thermally treating the mixture at a temperature of 200 to 800°C for a period of 0.5 to 6 h.
Thermal treatment may be performed under a protective gas such as, for example, nitrogen.
Silanising may be performed continuously or batchwise in heatable mixers and dryers with spray devices. Suitable " 980194 FH / AL
devices may be, for example: plough bar mixers, disc dryers, fluidised bed dryers or moving bed dryers.
The physico-chemical parameters of the granules, such as the specific surface area, particle size distribution, compacted density and pH, may be modified within the limits given above by varying the substances used and the conditions used during spraying, heating at constant temperature and silanising.
Titanium dioxide granules according to the invention have the following advantages:
The flow behaviour is better than non-spray-dried titanium dioxide.
Incorporation into organic systems is easier.
Dispersion is simpler.
No additional auxiliary substances are required for granulation.
Titanium dioxide granules according to the invention have a defined particle size, unlike non-spray-dried titanium dioxide which does not have a defined agglomerate size.
Titanium dioxide granules according to the invention can be handled in a dust-free manner.
Lower packaging costs are required for transportation due to the high compacted density.
Titanium dioxide granules according to the invention can be used as a catalyst support.
Non-spray-dried titanium dioxide is not suitable for this purpose because, for example, it is carried out of a fluidised bed.
Granules according to the invention may be used as a support for catalysts, and also in cosmetics, as a sunscreen, in silicone rubber, in toning powder, in lacquers and colorants, as a grinding and polishing agent and as a raw material for producing glass and ceramics.
Examples A titanium dioxide P25 with the following physico-chemical characteristics is used as a pyrogenic titanium dioxide.
It is disclosed in the series of documents called Pigments, no. 56 "Hochdisperse Metalloxide nach dem Aerosilverfahren", 4th edition, February 1989, Degussa AG.
Titanium dioxide P25 CAS no. 13463-67-7 Behaviour in water hydrophilic Appearance loose white powder BET surface area ' m'/g 50 15 Average size of primary 21 particles nm Compacted density ' g/1 about 100 Specific weight g/1 about 3.7 Loss on drying ' on leaving < 1.5 supplier (2 h at 105C) o Loss on ignition ' " (2 h < 2 1000C ) at pH ' (in 4a aqueous 3-4 dispersion) Si02 ' < 0.2 A12p3 ~J < 0 . 3 _ -< 0 . 01 Fe203 Ti02 > >99. 5 Z r02 -Hf02 ' -HC1 < 0.3 Sieve residue ' (Mocker's method, 45 ~.m)o < 0.05 1) according to DIN 66131 2) according to DIN ISO 787/XI, JIS K 5101/18 (not sieved) 5 3) according to DIN ISO 787/II, ASTM D 280, JIS K 5101/21 4) according to DIN 55921, ASTM D 1208, JIS K 5101/23 5) according to DIN ISO 787/IX; ASTM D 1208; JIS K 5101/29 6) according to DIN ISO 787/XVIII; ~JIS K 5101/20 7) with respect to substance dried for 2 h at 105°C
10 8) with respect to substance ignited for 2 h at 1000°C
9) HC1 content is component of loss on ignition 10) determined with an air comparison density bottle '' 980194 FH / AL
The titanium dioxides are prepared by spraying a volatile titanium compound into an oxyhydrogen flame formed from hydrogen and air. In most cases, titanium tetrachloride is used. This substance hydrolyses under the effect of the water being produced during the oxyhydrogen gas reaction to give titanium dioxide and hydrochloric acid. After leaving the flame, the titanium dioxide enters a so-called coagulation zone in which the titanium dioxide primary particles and primary aggregates agglomerate. The product, present at this stage as a kind of aerosol, is separated from the gaseous accompanying substances in cyclones and is then post-treated with moist hot air.
The particle sizes of the titanium dioxides may be varied by varying the reaction conditions such as, for example, temperature of the flame, proportion of hydrogen or oxygen, amount of titanium tetrachloride, residence time in the flame or the length of the coagulation zone.
The BET surface area is determined using nitrogen in accordance with DIN 66 131.
The compacted volume is determined in a similar way to that described in ASTM D 4164-88.
Equipment: Compacted volume meter STA V 2003 from the Engelsmann Co., in accordance with DIN 53194, para. 5.2 b-f 250 ml measuring cylinder, graduation mark every 2 ml Balance with max. error limit of ~ 0.1 g Performing the determination Set the counter on the compact=ed volume meter to 1000 strokes.
Tare the measuring cylinder.
Fill measuring cylinder with granules up to the 250 ml mark.
Note down the weight (~ 0.1 g).
Clamp the measuring cylinder in the compacted volume meter and switch the instrument on.
End of compacting -~ instrument automatically stops after 1000 strokes.
Read the compacted bulk volume accurately, to 1 ml.
Calculation E: weight of granules in g V: volume read off in ml W: water content in wt.°s (determined in accordance with test instructions P001) E x (100 - W) Compacted density = - -----V x 100 The pH is determined in 4 % strength aqueous dispersion, in the case of hydrophobic catalyst supports in water: ethanol 1:1.
Preparing granules accordin to the invention The pyrogenic titanium dioxide is dispersed in fully deionised water. A dispersing apparatus is used which operates on the rotor/stator principle. The dispersions being produced are spray-dried. Deposition of the final product is achieved using a filter or a cyclone.
The spray-dried and optionally heated granules are initially introduced into a mixer to be silanised and are sprayed optionally first with water and then with the silanising agent, under intense mixing. After completion of the spraying procedure, mixing is continued for 15 to 30 min and then the mixture is heated at a constant temperature of 100 to 400°C for 1 to 4 h.
The water used may be acidified with an acid, for example hydrochloric acid, until the pH is 7 to 1. The silanising agent used may be dissolved in a solvent such as, for example, ethanol.
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Claims (5)
1. Granules based on pyrogenic titanium dioxide with the following physico-chemical characteristics:
Average particle diameter: 10 to 150µm BET surface area: 25 to 100 m2/g pH 3 to 6 Compacted density: 400 to 1,200 g/1
Average particle diameter: 10 to 150µm BET surface area: 25 to 100 m2/g pH 3 to 6 Compacted density: 400 to 1,200 g/1
2. A process for preparing granules according to Claim 1, characterised in that pyrogenic titanium dioxide is dispersed in water and spray-dried.
3. Granules based on pyrogenic titanium dioxide with the following physico-chemical characteristics:
Average particle diameter: 10 to 160 µm BET surface area: 15 to 100 m2/g pH: 3.0 to 9.0 Compacted density: 400 to 1,200 g/1 Carbon content: 0.3 to 12.0 wt.%
Average particle diameter: 10 to 160 µm BET surface area: 15 to 100 m2/g pH: 3.0 to 9.0 Compacted density: 400 to 1,200 g/1 Carbon content: 0.3 to 12.0 wt.%
4. A process for preparing granules according to Claim 3, characterised in that pyrogenic titanium dioxide is dispersed in water and spray-dried and then silanised.
5. Use of granules according to Claims 1 and 3 as catalyst supports, and also in cosmetics, as sun screens, in silicone rubber, in toning powder, in lacquers and colorants, as grinding and polishing agents and as a raw material for producing glass and ceramics.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19928851A DE19928851A1 (en) | 1999-06-24 | 1999-06-24 | Granulates useful as catalyst support, abrasive, polish and raw material for glass and ceramics, in silicone rubber, toner, lacquer, paint and cosmetics and for sun protection are based on pyrogenic titanium dioxide |
| DE19928851.8 | 1999-06-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2312249A1 true CA2312249A1 (en) | 2000-12-24 |
Family
ID=7912317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002312249A Abandoned CA2312249A1 (en) | 1999-06-24 | 2000-06-23 | Granules based on pyrogenic titanium dioxide, a process for preparing them and their use |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP1078883B1 (en) |
| JP (1) | JP3581079B2 (en) |
| KR (1) | KR100413930B1 (en) |
| AT (1) | ATE214034T1 (en) |
| CA (1) | CA2312249A1 (en) |
| DE (2) | DE19928851A1 (en) |
| ES (1) | ES2173063T3 (en) |
| PT (1) | PT1078883E (en) |
| SG (1) | SG85194A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090280309A1 (en) * | 2006-08-30 | 2009-11-12 | Evonik Degussa Gmbh | Pyrogenic titanium dioxide compressed to slugs |
| US7897256B2 (en) | 2001-02-28 | 2011-03-01 | Evonik Degussa Gmbh | Surface-modified, doped, pyrogenically produced oxides |
| US10010489B2 (en) | 2011-11-03 | 2018-07-03 | Beiersdorf Ag | Cosmetic preparation comprising pulverized hydrophilic substances |
| US10610464B2 (en) | 2011-11-03 | 2020-04-07 | Beiersdorf Ag | Cosmetic preparation comprising pulverized hydrophobic substances |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10059002A1 (en) * | 2000-11-28 | 2002-07-11 | Degussa | Improving stability of polymers, e.g. silicones, to heat and flames, involves addition of pyrogenic, hydrophobic titanium dioxide |
| DE10122269A1 (en) | 2001-05-08 | 2002-11-21 | Degussa | Silane-modified biopolymer, bio-oligomeric, oxidic or silicate filler, process for its production and its use |
| DE10146871A1 (en) * | 2001-09-24 | 2003-04-24 | Sachtleben Chemie Gmbh | Tap hole mass with fine TiO¶2¶, process for its production and its use |
| DE10151478C1 (en) | 2001-10-18 | 2003-03-13 | Wacker Chemie Gmbh | Production of aminoalkylsilyl-modified solid, used in powder system, as thickener or in toner, developer or charge transfer ancillary, involves reacting surface hydroxyl groups with cyclic silazane |
| EP1308422A1 (en) | 2001-10-30 | 2003-05-07 | Degussa AG | A method of producing glass of optical qualitiy |
| DE10213364B4 (en) * | 2002-03-26 | 2006-12-21 | Degussa Ag | Process for the heat stabilization of silicone rubber |
| DE10218350A1 (en) * | 2002-04-25 | 2003-11-20 | Degussa | Silane-modified oxidic or silicate filler, process for its production and its use |
| DE102004014020A1 (en) * | 2004-03-19 | 2005-10-06 | Eckart Gmbh & Co. Kg | Cosmetic preparation with UV protection and use of effect pigments |
| SI1896253T1 (en) * | 2005-06-06 | 2014-08-29 | Tioxide Group Services Limited | Methods for forming pigment pseudoparticles |
| DE102011085685A1 (en) * | 2011-11-03 | 2013-05-08 | Beiersdorf Ag | Cosmetic preparation with powdered substances to improve the perfume adhesion |
| DE102011087385A1 (en) | 2011-11-30 | 2013-06-06 | Evonik Degussa Gmbh | Granules based on titanium dioxide particles with high mechanical stability |
| JP5927226B2 (en) * | 2013-04-04 | 2016-06-01 | 石原産業株式会社 | Abrasive particles and method of using the same |
| EP2881367A1 (en) | 2013-12-09 | 2015-06-10 | Evonik Industries AG | Method for reducing the dust component of metal oxide granules |
| EP3153549A1 (en) | 2015-10-30 | 2017-04-12 | Kronos International, Inc. | The preparation of matt paints and printing inks |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3611449A1 (en) * | 1986-04-05 | 1987-10-15 | Degussa | BASIC MATERIAL FOR THE PRODUCTION OF CERAMIC MATERIALS |
| DE4202695C2 (en) * | 1992-01-31 | 1993-12-09 | Degussa | Surface-modified, pyrogenic titanium dioxide |
| DE19500674A1 (en) * | 1995-01-12 | 1996-07-18 | Degussa | Surface modified pyrogenic mixed oxides, process for their production and use |
| ES2154748T3 (en) * | 1995-02-04 | 2001-04-16 | Degussa | GRANULATES BASED ON SILICON DIOXIDE PREPARED BY VIA PIROGENA, PROCEDURE FOR PREPARATION AND EMPLOYMENT. |
| DZ2304A1 (en) * | 1996-09-10 | 2002-12-28 | Shell Int Research | Fischer-tropsch catalyst and process for the preparation of hydrocarbons. |
-
1999
- 1999-06-24 DE DE19928851A patent/DE19928851A1/en not_active Ceased
-
2000
- 2000-06-20 PT PT00112944T patent/PT1078883E/en unknown
- 2000-06-20 DE DE50000118T patent/DE50000118D1/en not_active Expired - Lifetime
- 2000-06-20 AT AT00112944T patent/ATE214034T1/en not_active IP Right Cessation
- 2000-06-20 ES ES00112944T patent/ES2173063T3/en not_active Expired - Lifetime
- 2000-06-20 EP EP00112944A patent/EP1078883B1/en not_active Expired - Lifetime
- 2000-06-20 SG SG200003483A patent/SG85194A1/en unknown
- 2000-06-21 JP JP2000186693A patent/JP3581079B2/en not_active Expired - Lifetime
- 2000-06-23 CA CA002312249A patent/CA2312249A1/en not_active Abandoned
- 2000-06-23 KR KR10-2000-0034804A patent/KR100413930B1/en active IP Right Grant
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7897256B2 (en) | 2001-02-28 | 2011-03-01 | Evonik Degussa Gmbh | Surface-modified, doped, pyrogenically produced oxides |
| US20090280309A1 (en) * | 2006-08-30 | 2009-11-12 | Evonik Degussa Gmbh | Pyrogenic titanium dioxide compressed to slugs |
| US8349441B2 (en) * | 2006-08-30 | 2013-01-08 | Evonik Degussa Gmbh | Pyrogenic titanium dioxide compressed to slugs |
| US10010489B2 (en) | 2011-11-03 | 2018-07-03 | Beiersdorf Ag | Cosmetic preparation comprising pulverized hydrophilic substances |
| US10610464B2 (en) | 2011-11-03 | 2020-04-07 | Beiersdorf Ag | Cosmetic preparation comprising pulverized hydrophobic substances |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3581079B2 (en) | 2004-10-27 |
| SG85194A1 (en) | 2001-12-19 |
| KR20010049615A (en) | 2001-06-15 |
| DE50000118D1 (en) | 2002-04-11 |
| PT1078883E (en) | 2002-07-31 |
| ATE214034T1 (en) | 2002-03-15 |
| EP1078883B1 (en) | 2002-03-06 |
| DE19928851A1 (en) | 2000-12-28 |
| EP1078883A1 (en) | 2001-02-28 |
| ES2173063T3 (en) | 2002-10-16 |
| KR100413930B1 (en) | 2004-01-13 |
| JP2001039714A (en) | 2001-02-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |