WO1999043616A1 - A modified titanium dioxide and a method for its preparation - Google Patents
A modified titanium dioxide and a method for its preparation Download PDFInfo
- Publication number
- WO1999043616A1 WO1999043616A1 PCT/IL1998/000090 IL9800090W WO9943616A1 WO 1999043616 A1 WO1999043616 A1 WO 1999043616A1 IL 9800090 W IL9800090 W IL 9800090W WO 9943616 A1 WO9943616 A1 WO 9943616A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- titanium dioxide
- hydroxide
- dioxide according
- novel modified
- silica sol
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 42
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims description 35
- 238000002360 preparation method Methods 0.000 title description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 194
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims abstract description 72
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 53
- 239000004202 carbamide Substances 0.000 claims abstract description 31
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 238000001556 precipitation Methods 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 11
- 239000012452 mother liquor Substances 0.000 claims abstract description 11
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 7
- 230000003247 decreasing effect Effects 0.000 claims abstract description 5
- -1 titanyl sulfate Chemical class 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims abstract description 4
- 238000012986 modification Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 85
- 239000000243 solution Substances 0.000 claims description 67
- 239000000377 silicon dioxide Substances 0.000 claims description 35
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 31
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000000725 suspension Substances 0.000 claims description 19
- 229910052681 coesite Inorganic materials 0.000 claims description 18
- 229910052906 cristobalite Inorganic materials 0.000 claims description 18
- 229910052682 stishovite Inorganic materials 0.000 claims description 18
- 229910052905 tridymite Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 230000003993 interaction Effects 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical class [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000007900 aqueous suspension Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000000413 hydrolysate Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- 235000011132 calcium sulphate Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000001038 titanium pigment Substances 0.000 claims description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims 1
- 239000000920 calcium hydroxide Substances 0.000 claims 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims 1
- 235000011116 calcium hydroxide Nutrition 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- 238000010979 pH adjustment Methods 0.000 claims 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims 1
- 235000010215 titanium dioxide Nutrition 0.000 description 69
- 239000007858 starting material Substances 0.000 description 16
- 239000002253 acid Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 238000011282 treatment Methods 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 239000003607 modifier Substances 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000011021 bench scale process Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229940043430 calcium compound Drugs 0.000 description 2
- 150000001674 calcium compounds Chemical class 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 230000000051 modifying effect Effects 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910019982 (NH4)2TiO Inorganic materials 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241001572615 Amorphus Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 206010026749 Mania Diseases 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910004028 SiCU Inorganic materials 0.000 description 1
- 239000004965 Silica aerogel Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000002571 modificatory effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 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
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
-
- 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
- C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
- C01P2006/12—Surface area
- C01P2006/13—Surface area thermal stability thereof at high temperatures
-
- 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
-
- 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
- C01P2006/17—Pore diameter distribution
Definitions
- the present invention relates to Titanium dioxide. More particularly, the invention relates to a novel modified Titanium dioxide and method for its preparation.
- Titanium dioxide has been known to be produced by drying or calcining of Titanium hydroxide. There are various methods of producing Titanium hydroxide from different types of Titanium compounds. Three crystalline forms of Titanium dioxide are known in the art: Anatase, Rutile and Brookite. Anatase or amorphus Titanium dioxide partially crystallized into Anatase, are commonly used as catalysts (for example see US Patent No. 4,388,288 and US Pat. No.4,422,958).
- Mesopore structure is determined by the method of the active material precipitation from a solution and its subsequent treatment. Macropore structure is determined mainly by the process of granulation or shaping. Many catalytic processes are carried out under increased temperatures where Titanium dioxide undergoes shrinkage. Its active surface area is reduced and its activity is also decreased. Since the heat treatment will take a long period of time, the Titanium dioxide aging process leads to its structure transformation from Anatase to Rutile crystalline form, and these alterations cause a significant decrease in its catalytic activity. Since Titanium dioxide is quite an expensive material it is most desirable that such catalyst should possess a prolonged effective period of use.
- Titania/Silica mixed oxides preparation Several investigations were performed in the field of Titania/Silica mixed oxides preparation. The idea of this approach is a coprecipitation of titanium hydroxide and silicic acid, Titania/Silica mixed oxides preparation and their use as supports for Nickel catalyst were described (Journal of Catalysis 105, p. 511-520 1987). As mentioned therein, a mixed oxide was precipitated from a mixture of TiC and SiCU .
- titania-silica aerogels obtained by an alkoxide-sol-gel route, were prepared and tested in the reaction of epoxidation of olefins (Journal of Catalysis 153, 177-189, 1995), Crystalline titanium silicates having specific adsorption and catalytic properties were described in literature (Advances in Catalysis, Vol. 41 , 253-327, 1996).
- Modified titanium dioxide is prepared from two types of starting materials.
- the first one is an aqueous solution containing a mixture of dissolved sulfate salts including titanium sulfate, having a pH up to 1.7.
- the second one is titanium hydroxide or titanium dioxide prepared by any known method.
- titanium dioxide is prepared from titanium hydroxide precipitated and hydrothermally treated in its mother liquor in the presence of urea and further modified with basic silica sol.
- titanium hydroxide or titanium dioxide in the form of dough, paste, or suspension is brought to a pH in the range of 6.0-11 with urea or ammonia and then interacted with a basic silica sol.
- the first type of starting materials includes solutions of a double salt ammonium titanyl sulfate (NH 4 )2TiO(S ⁇ 4)2nH 2 0, commercially produced as acid titanyl sulfate solution, for example UNITi 992 or a similar acid titanyl sulfate solution prepared with different titanium dioxides, or titanium hydroxides dissolved in sulfuric acid.
- acid titanyl sulfate solution for example UNITi 992 or a similar acid titanyl sulfate solution prepared with different titanium dioxides, or titanium hydroxides dissolved in sulfuric acid.
- the dried titanium hydrolysates commercially produced (UNITi
- These partially neutralized solutions can be used as starting materials for the modified titanium dioxide preparation.
- the solution of the above mentioned ammonium titanyl sulfate salt may be used as a starting material in its aqueous solution containing besides titanyl sulfate, ammonium sulfate, the pH of this solution being in the range of 0.7 to 0.9.
- the modified titanium dioxide produced from the first type of starting materials as mentioned above is characterized by a specific combination of high surface area, an enhanced thermal and hydrothermal stability of the pore, a crystalline structure, a decreased sulfur content and a high catalytic activity.
- Typical examples of the second type of starting materials are the intermediate products of titanium pigment UNITi 902TM and final materials produced by FINNTi S-140TM and FINNTi-150TM.
- Titanium Hydroxide cake precipitated according to the European Patent Application No. EP 0722905 A1 (after washing but without adding potassium hydroxide and phosphoric acid) as well as Titanium Hydroxide or Titanium Dioxide precipitated according to U.S. Patent No. 4,929,586 (before vanadyl oxalate addition) can be also used as a starting material of the second type.
- the thermal stability of modified titanium dioxide produced from the second type of starting material is similar to that of modified titanium dioxides produced on the basis of the first type of starting material.
- the modified titanium dioxides produced on the basis of the second type of starting materials are characterized by a decrease in the sulfur content compared with the starting materials.
- Titanium dioxide possessing the above improved properties are unknown up to the present invention.
- two modifiers can be used during a particular procedure for producing the novel modified titanium dioxide.
- These modifiers are urea and basic silica sol i.e. a colloidal solution of silica having a pH of above 7.0 .
- Urea is a known commercial product, which can be used either in a solid form or in an aqueous solution.
- silica sols colloids which contain particles of silica with a diameter in the range of 2-100 nm.
- the inner part of each particle consists almost of dehydroxylated silica, while silicon atoms located on the outer part of each particle, are hydroxylated.
- Silica sols can be stable, if some cations compensate the negative charge of silica particles.
- sodium, potassium and ammonium it should be mentioned sodium, potassium and ammonium.
- Commercial silica sols, prepared with any known procedure, usually with a cation exchange method, can be used as modifiers.
- Such sols can also be prepared during the process of modified titanium dioxide preparation with any other known procedure.
- Basic silica sol is used as a modifying agent for the formed titanium hydroxide or for the dry titanium dioxide.
- the titanium hydroxide is separated from the mother liquor and washed.
- the titanium hydroxide obtained in the form of a suspension, wet cake, or dried material is treated with basic silica sol under conditions which exclude the coagulation of a sol. However, these conditions promote the reaction between hydroxylated silica particles of the sol and the hydroxylated surface of titanium hydroxide or titanium dioxide.
- the second type of starting materials in the form of an aqueous suspension, wet cake or dough, it is mixed with an alkali constituent selected from urea, ammonia, sodium or potassium hydroxide, leading a titanium hydroxide or titanium dioxide having a pH in the range of 6.0 to 11.0.
- an alkali constituent selected from urea, ammonia, sodium or potassium hydroxide, leading a titanium hydroxide or titanium dioxide having a pH in the range of 6.0 to 11.0.
- a basic silica sol is introduced and a reaction occurs between the hydroxylated surface of silica particles and the hydroxylated surface of titanium hydroxide or titanium dioxide.
- the process of the modified titanium dioxide preparation from the first type of starting material consists of the following steps:
- preparing the initial sulfate solution b. precipitation of Titanium hydroxide from the above mentioned sulfate solution in the presence of urea followed by a hydrothermal treatment of the formed Titanium hydroxide in its mother liquor, also in the presence of urea as modifier; c. separation of the formed precipitated Titanium hydroxide and its washing; . the dough, wet cake, or dried material, or the resulted water suspension of the formed precipitated Titanium hydroxide treatment with basic silica sol as the modificating agent; e. filtration of Titanium hydroxide and washing with water; and f. transformation of Titanium hydroxide into Titanium dioxide by a heating treatment.
- stage (a) an aqueous acid solution comprising titanyl sulfate is partially neutralized, thus producing a mixture of sulfate salts having a pH up to + 1.7 and preferably in the range of between 0.02 to 1,2.
- This neutralization is carried out with various alkali compounds such as sodium hydroxide, sodium carbonate, potassium carbonate or bicarbonate, an aqueous solution of ammonia, calcium compounds, etc.
- an insoluble calcium sulfate is produced and preferably it has to be separated from the neutralized solution.
- the solution obtained can be used for titanium hydroxide precipitation, following a hydrothermal treatment (stage b) containing a mixture of titanyl sulfate and another dissolved sulfate salt.
- the solution has a concentration in the range of between 20 to 250 g/l titanium and preferably between 40-150 g/l (calculated as Ti ⁇ 2).
- the above solution can be used directly in stage “b" in the presence of urea as modifier, or it can be maintained at a temperature in the range of between 20° to 70° C for a period between 0.3 - 300 hours.
- the weight ratio between the quantity of urea added to the solution to the quantity of titanium dioxide present in the solution has to be in the range of between 0.3 to 11.0. Titanium dioxide precipitation takes place either during the urea addition, or during heating the solution to about 80°to 100°C. Although the duration of stage “b" is generally in the range of between 0.5 to 5 hours, the precipitation of titanium hydroxide is quicker. The main part of the above mentioned period is required for the hydrothermal treatment of the precipitated titanium hydroxide.
- the urea introduced into the sulfate solution reacts in the step of precipitation as well as in the process of hydrothermal treatment of the precipitated titanium hydroxide in its mother liquor.
- stage “b” The duration of stage “b” depends on the titanyl sulfate content in the solution, the pH of the solution before urea addition, the amount of urea added and the temperature which prevails in the mixture.
- stage "c" The precipitated titanium hydroxide after being subjected to a hydrothermal treatment is separated from the mother liquor and washed.
- titanium hydroxide produced after a thermal treatment at a temperature in the range of between 100° -250° C is characterized by a high surface area, a developed mesopore structure and a decreased sulfur content.
- a second modifier stage u d"
- titanium hydroxide in the form of a dough, wet cake, suspension or dried material has to possess a pH in the range of 6.0 to 11.0 and preferably between 8 to 10. This adjustment may be carried out with urea, ammonia or their mixture introduced into the above mentioned dough, wet cake or suspension of the titanium hydroxide.
- this titanium hydroxide is mixed with basic silica sol having a concentration of between 1% to 40% and preferably in the range of between 3% to 20% by weight calculated as Si0 2 .
- the required quantity of silica sol has to be as a weight ratio of Si02 to TiO2, in the range of between 0.01 to 0.30 and preferably between 0.05 to 0.15.
- the temperature during this stage of modification may be between the ambient one and the boiling point of the liquid phase.
- an intensive chemical interaction of silica sol with titanium hydroxide takes place.
- the coagulation of silica sol into silica gel is avoided due to the high pH.
- the rate of interaction between the basic sol and hydroxylated surface of titanium hydroxide or titanium dioxide at ambient temperature is low, but increases when the temperature is also increased. It may be assumed that as a result of this interaction, some chemical bonds Ti - O - Si are formed and as a result, a reinforcement in the structure of the network occurred.
- the modified titanium hydroxide can be used either in the form of a wet cake, or a suspension in the catalyst manufacture, or can be dried at a temperature between 100°C-250°C and after that calcined at about 500 °C.
- the modified titanium hydroxide obtained was analyzed by the following tests for the dry samples as well as for samples calcined at a temperature between 500 °C to 900°C: - determination of the specific surface area, using the so called "1 point method"
- the titanium dioxide was also tested as a carrier of a catalyst used in the oxidation of organic impurities present in air.
- the resulted solution contained 80 g/l titanyl sulfate (calculated as Ti02) which corresponds to the formula of the respective double salt (NH4)Ti02(SO4) and an amount of ammonium sulfate.
- Titanium hydroxide was separated from the mother liquor and washed with demineralized water. The resulted wet cake of titanium hydroxide was suspended in a basic silica sol, prepared from a commercial sodium
- the titanium dioxide was prepared as in Examplel, but the amount of the basic silica sol used corresponded to a weight ratio SiO2 :Ti ⁇ 2 to 0.05 (as in Table 1).
- the data on the specific surface areas of the prepared sample and the respective thermal stability, compared with typical commercial titanium dioxide, are given in Table 1.
- the first stage of titanium dioxide preparation was based on a titanyl sulfate solution, having a composition similar to a commercial titanyl sulfate and sulfuric acid solution, known as "UNITi 992" produced by Kemira Pigments Inc.
- the solution (A) contained 9.5% by weight Ti02 and 37% by weight sulfuric acid was prepared as follows: An amount of 9.8 kg of a commercial titanium dioxide (hydrolysate) UNITi 908, having a loss on ignition of 19.6 by weight (at 1000°C), was dissolved in an amount of 43.8 kg of boiling sulfuric acid having a concentration of 70% by weight). After cooling, an amount of 1 I of this solution was diluted with an equal volume of demineralized water. The resulted solution having a concentration of 123 g/l Ti ⁇ 2, was used in the
- the precipitated titanium hydroxide was separated from the mother liquor and washed with demineralized water.
- the resulted wet cake was divided in three portions, used in the Examples 3, 4 and 5.
- Each wet cake sample was diluted with demineralized water, obtaining a suspension which had a concentration of 10% (calculated as Ti02).
- a basic silica sol was prepared as known in the art, but different cations were used for the sol stabilization; in Example 3: sodium, in Example 4: potassium and in Example 5: ammonium.
- the amount of basic sol used calculated as % of SiO2 to Ti ⁇ 2 was 10% (by weight).
- the three different basic silica sols were mixed separately with the above mentioned three samples of suspension and the resulted mixtures were heated to about 90° C and maintained at this temperature for about 1 hour. In each case, substantially all the quantities of silica were consumed by the titanium hydroxide.
- the resulted precipitates were separated from the liquid phase by filtration and converted into titanium dioxides by a thermal treatment at four different temperatures: 110°C, 500° C, 700°C and 900°C.
- the conditions for the interaction of precipitated titanium hydroxides with basic sols are described in Table 3 and the values of specific surface
- Example 6 the neutralized solution was maintained at 50°C for 5 hours and 30 minutes before urea addition; in Example 15 the neutralized solution was maintained at 55°C for 8 hours after urea addition.
- Example 17 the acid titanyl sulfate solution was first neutralized with calcium carbonate reaching a pH of 0.09, then the formed calcium sulfate was filtered out. The final neutralization of the solution was carried out with ammonium bicarbonate, reaching a pH of 0.69 as shown Table 2.
- the conditions of the precipitated titanium hydroxides in the interaction with the basic sols are given in Table 3. As can be noticed, titanium hydroxide was treated with silica sol, both in suspension and also in a wet cake.
- modified titanium hydroxides are given in Tables 4, 8, 9, 10 , 11, 12, 13, 14 and X-Ray diagrams for samples 6 and UNITi 908. As can be noticed from these Tables and X-Ray diagrams, modified titanium dioxides are characterized by a significant higher thermal and hydrothermal stability than the known titania and titania/silica mixed oxides.
- Example 12 The sample prepared in Example 12 was investigated with the EDAX method and the data regarding the respective compositions by weight at different points are presented below:
- sample 6 contains only anatase, at the same time commercial titanium dioxide UNITi 908 was converted only partially into rutile (about 60%).
- a definite stabilizing effect can be detected also in this case, although it is less than with the same amount (10%) of the basic silica sol added to the titanium hydroxide under the conditions as described above (compare Examples 5 and 18 in the Tables 2 and 4.)
- titanium hydrolysates (S-1 0 and S-150) as produced by
- KEMIRA PIGMENT OY Finland
- a hydrolysate (UNITi 908) produced by KEMIRA PIGMENT (U.S.A.) was used.
- the beneficial effects of the method according to the present invention are evident from the Tables 6, 7, 8 and 13.
- the modified titanium dioxide contains only initial crystaline anatase phase, once about 60% of the commercial titanium dioxide had been converted into rutile.
- Example 2 The modified titanium dioxide as obtained in Example 1 , was mixed with powdery silica N60 (produced by PPG) and an acid silica sol.
- the powdery silica was used as an inert filler and the silica sol was used as a binder component.
- the composition of this mixture, in weight percentage was as follows:
- This Example shows that the modified titanium dioxide can be used also as a carrier for catalysts which is effective in the oxidation of organic compounds in a gas phase.
- Two samples were prepared and tested in a laboratory unit for the catalytic oxidation of propane (3 mol.%) in air at 400°C, In the two cases titanium dioxide was doped with vanadium oxide.
- compositions of the catalysts and the results of the respective tests are given in Table 14.
- the titanium dioxide as prepared by the present invention is useful as a catalyst carrier for organic impurities in air oxidation.
- the titanium dioxide according to the present invention can be successfully used as a photocatalyst for detecting organic impurities in water oxidation.
- the titanium hydroxide precipitated from a sulfate solution in the presence of urea and after washing was separated in the form of a wet cake containing 25% by weight TiO2 before the treatment with basic silica sol (as in Example 7).
- the procedure of the testing consists in the use of a suspension of 0.15 - 0.30 grams, calculated as TiO2 placed in a bottle of 2 I.
- a quartz tube (internal diameter 1 cm and length 1 m) was used as a sun radiation reactor.
- titanium dioxides modified with urea in the process of titanium hydroxides precipitation from a solution of ammonium titanyl sulfate. following a hydrothermal treatment in its mother li ⁇ uor and then modified with basic silica sol.
- x the steaming stream contained 90% by volume water vapors and 10% by volume air.
- Example 6 A 0.63 180 0.49 233 0.54 235
- Example 6 Example 10 [Example 1 Example Q
- Titanium hydroxide from Example 7 35 28 23 17
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PCT/IL1998/000090 WO1999043616A1 (en) | 1998-02-24 | 1998-02-24 | A modified titanium dioxide and a method for its preparation |
EP98904358A EP1060128A4 (en) | 1998-02-24 | 1998-02-24 | A modified titanium dioxide and a method for its preparation |
AU62283/98A AU6228398A (en) | 1998-02-24 | 1998-02-24 | A modified titanium dioxide and a method for its preparation |
US09/623,007 US6956006B1 (en) | 1998-02-24 | 1998-02-24 | Modified titanium dioxide and a method for its preparation |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4081510A (en) * | 1975-10-15 | 1978-03-28 | Hitachi, Ltd. | Process for catalytically treating an exhaust gas containing ammonia gas and oxygen gas to reduce said ammonia gas to nitrogen |
US4176089A (en) * | 1978-08-03 | 1979-11-27 | Exxon Research & Engineering Co. | Process for the preparation of silica-titania and catalysts comprising the same |
US4537873A (en) * | 1982-11-29 | 1985-08-27 | Hitachi, Ltd. | Catalyst for catalytic combustion |
US4977127A (en) * | 1986-09-13 | 1990-12-11 | Sakai Chemical Industry Co., Ltd. | Catalyst for denitrizing nitrogen oxides contained in waste gases |
US5120701A (en) * | 1990-04-19 | 1992-06-09 | Degussa | Titanium dioxide compacts, method of their production and a catalyst coated on a carrier of titanium dioxide |
US5718878A (en) * | 1996-07-12 | 1998-02-17 | Akzo Nobel N.V. | Mesoporous titania and process for its preparation |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3887494A (en) | 1970-11-12 | 1975-06-03 | Phillips Petroleum Co | Olefin polymerization catalyst |
DE2555901A1 (en) * | 1974-12-19 | 1976-06-24 | Mitsubishi Chem Ind | PROCESS FOR THE PRODUCTION OF METHACRYLIC ACID ESTERS |
DE2710630A1 (en) * | 1977-03-11 | 1978-09-21 | Mitsubishi Chem Ind | Esterification, transesterification and ester hydrolysis - over solid titanium and silicon catalysts, pref. prepd. using polymeric pptn. aids |
JPS601056B2 (en) | 1980-02-19 | 1985-01-11 | 千代田化工建設株式会社 | Hydrotreatment of heavy hydrocarbon oils containing asphaltenes |
FR2481145A1 (en) | 1980-04-23 | 1981-10-30 | Rhone Poulenc Ind | PROCESS FOR PRODUCING CATALYSTS OR TITANIUM OXIDE-BASED CATALYST SURFACE SUPPORTS AND THEIR CATALYSIS CLAUS APPLICATIONS |
FR2501532B1 (en) | 1981-03-13 | 1985-12-13 | Rhone Poulenc Spec Chim | CATALYST AND METHOD FOR THE TREATMENT OF INDUSTRIAL WASTE GASES CONTAINING SULFUR COMPOUNDS |
US4388149A (en) | 1981-10-13 | 1983-06-14 | Societe Nationale De L'amiante | Titanium coated asbestos fiber |
JPS6425770A (en) | 1987-04-16 | 1989-01-27 | Mitsui Toatsu Chemicals | Production of epichlorohydrins |
FR2621577B1 (en) | 1987-10-09 | 1990-01-12 | Rhone Poulenc Chimie | TITANIUM OXIDE WITH STABILIZED PROPERTIES |
US4929586A (en) * | 1988-06-09 | 1990-05-29 | W. R. Grace & Co.-Conn. | Catalysts for selective catalytic reduction DeNOx technology |
US5175136A (en) | 1990-05-31 | 1992-12-29 | Monsanto Company | Monolithic catalysts for conversion of sulfur dioxide to sulfur trioxide |
US5124303A (en) * | 1990-08-27 | 1992-06-23 | Nippon Shokubai Co., Ltd. | Reinforced catalyst for treatment of waste gas |
US5389309A (en) | 1990-12-21 | 1995-02-14 | Lopez; Richard A. | Composition and method for making fire-retardant materials |
US5162283A (en) | 1991-01-22 | 1992-11-10 | Mobil Oil Corporation | Highly porous amorphous titania and titania/silica phases |
DE4213018C1 (en) | 1992-04-21 | 1993-12-09 | Degussa | Catalyst for the oxidative purification of exhaust gases from diesel engines |
DE4235996A1 (en) | 1992-10-24 | 1994-04-28 | Degussa | Titanium dioxide mixed oxide produced by flame hydrolysis, process for its preparation and use |
US5587349A (en) | 1994-02-15 | 1996-12-24 | Mitsubishi Gas Chemical Company, Inc. | Process for preparing silica-titania catalyst |
US5935895A (en) | 1994-09-22 | 1999-08-10 | Roche Vitamins Inc. | Heterogeneous catalysts |
GB9501086D0 (en) | 1995-01-20 | 1995-03-08 | Tioxide Group Services Ltd | Preparation of anatase titanium dioxide |
JP3379627B2 (en) | 1996-08-30 | 2003-02-24 | 株式会社キャタラー | Exhaust gas purification catalyst |
US6117814A (en) | 1998-02-10 | 2000-09-12 | Exxon Research And Engineering Co. | Titania catalysts their preparation and use in fischer-tropsch synthesis |
-
1998
- 1998-02-24 US US09/623,007 patent/US6956006B1/en not_active Expired - Fee Related
- 1998-02-24 AU AU62283/98A patent/AU6228398A/en not_active Abandoned
- 1998-02-24 EP EP98904358A patent/EP1060128A4/en not_active Withdrawn
- 1998-02-24 WO PCT/IL1998/000090 patent/WO1999043616A1/en not_active Application Discontinuation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4081510A (en) * | 1975-10-15 | 1978-03-28 | Hitachi, Ltd. | Process for catalytically treating an exhaust gas containing ammonia gas and oxygen gas to reduce said ammonia gas to nitrogen |
US4176089A (en) * | 1978-08-03 | 1979-11-27 | Exxon Research & Engineering Co. | Process for the preparation of silica-titania and catalysts comprising the same |
US4537873A (en) * | 1982-11-29 | 1985-08-27 | Hitachi, Ltd. | Catalyst for catalytic combustion |
US4977127A (en) * | 1986-09-13 | 1990-12-11 | Sakai Chemical Industry Co., Ltd. | Catalyst for denitrizing nitrogen oxides contained in waste gases |
US5120701A (en) * | 1990-04-19 | 1992-06-09 | Degussa | Titanium dioxide compacts, method of their production and a catalyst coated on a carrier of titanium dioxide |
US5718878A (en) * | 1996-07-12 | 1998-02-17 | Akzo Nobel N.V. | Mesoporous titania and process for its preparation |
Non-Patent Citations (1)
Title |
---|
See also references of EP1060128A4 * |
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Also Published As
Publication number | Publication date |
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US6956006B1 (en) | 2005-10-18 |
EP1060128A1 (en) | 2000-12-20 |
EP1060128A4 (en) | 2005-08-03 |
AU6228398A (en) | 1999-09-15 |
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