CN106076356A - A kind of titanium tungsten powder and its production and use - Google Patents
A kind of titanium tungsten powder and its production and use Download PDFInfo
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- CN106076356A CN106076356A CN201610428439.3A CN201610428439A CN106076356A CN 106076356 A CN106076356 A CN 106076356A CN 201610428439 A CN201610428439 A CN 201610428439A CN 106076356 A CN106076356 A CN 106076356A
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- catalyst
- tungsten powder
- tungsten
- titanium
- titanium tungsten
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- 239000000843 powder Substances 0.000 title abstract description 39
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 title abstract description 38
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 76
- 238000000034 method Methods 0.000 abstract description 45
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 29
- 238000002360 preparation method Methods 0.000 abstract description 25
- 239000002253 acid Substances 0.000 abstract description 20
- 230000008569 process Effects 0.000 abstract description 18
- 229910052721 tungsten Inorganic materials 0.000 abstract description 15
- 239000010937 tungsten Substances 0.000 abstract description 15
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 abstract description 14
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 14
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- 239000002243 precursor Substances 0.000 abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 239000002270 dispersing agent Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 150000003657 tungsten Chemical class 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 62
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 28
- 238000000576 coating method Methods 0.000 description 27
- 239000011248 coating agent Substances 0.000 description 26
- 239000000084 colloidal system Substances 0.000 description 25
- 239000007789 gas Substances 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 20
- 238000001354 calcination Methods 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 15
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 15
- 241000264877 Hippospongia communis Species 0.000 description 14
- 239000000919 ceramic Substances 0.000 description 14
- 238000004506 ultrasonic cleaning Methods 0.000 description 12
- 229910052720 vanadium Inorganic materials 0.000 description 12
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 description 11
- 230000032683 aging Effects 0.000 description 10
- 239000004411 aluminium Substances 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000003292 glue Substances 0.000 description 10
- 238000009955 starching Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 description 9
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical group [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
- 230000033228 biological regulation Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- PAVDBIKKZYPKDI-UHFFFAOYSA-N molybdenum;oxalic acid Chemical compound [Mo].OC(=O)C(O)=O PAVDBIKKZYPKDI-UHFFFAOYSA-N 0.000 description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 230000002269 spontaneous effect Effects 0.000 description 5
- 150000003608 titanium Chemical class 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000029087 digestion Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 150000002751 molybdenum Chemical class 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- MVZPCNRERCVJMS-UHFFFAOYSA-N cerium copper titanium Chemical compound [Ti][Cu][Ce] MVZPCNRERCVJMS-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000029219 regulation of pH Effects 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical class [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 229910015189 FeOx Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- -1 Tungsten salt Chemical class 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- DBRMBYFUMAFZOB-UHFFFAOYSA-N molybdenum nitric acid Chemical compound [Mo].[N+](=O)(O)[O-] DBRMBYFUMAFZOB-UHFFFAOYSA-N 0.000 description 1
- BQBYSLAFGRVJME-UHFFFAOYSA-L molybdenum(2+);dichloride Chemical compound Cl[Mo]Cl BQBYSLAFGRVJME-UHFFFAOYSA-L 0.000 description 1
- 230000008450 motivation Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- BBJSDUUHGVDNKL-UHFFFAOYSA-J oxalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BBJSDUUHGVDNKL-UHFFFAOYSA-J 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WTHDKMILWLGDKL-UHFFFAOYSA-N urea;hydrate Chemical compound O.NC(N)=O WTHDKMILWLGDKL-UHFFFAOYSA-N 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- 239000002912 waste gas Substances 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/012—Diesel engines and lean burn gasoline engines
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
Abstract
The invention provides a kind of titanium tungsten powder and its production and use, it is to be prepared via a method which: configuration tungsten precursor water solution, ferric nitrate is added in above-mentioned solution, the metatitanic acid prepared sulfuric acid process again and surface dispersant join in above-mentioned solution and are stirred, it is finally dried and calcines, obtaining required titanium tungsten powder；Described tungsten presoma is solvable tungsten salt.The metatitanic acid that the present invention uses sulfuric acid process to prepare is precursor synthesis titanium tungsten powder, the problem that in tradition titanium tungsten powder preparation process, tungsten load is uneven and production efficiency is low can be avoided, during for preparing catalyst, add the selectivity of catalytic reaction, and the lifting of the sulfur resistance of catalyst is greatly improved.
Description
Technical field
The present invention relates to diesel engine vent gas process field, specifically, relate to a kind of titanium tungsten powder and preparation method thereof and use
On the way.
Background technology
Over nearly 20 years, in the face of the increasingly exhausted pressure bringing to social development of world petroleum resource, in the face of automobile pollution
The impact on environment for the sharp increase, world car ceaselessly realizes the solution of auto industry sustainable development in searching,
In continuous technology development, people diesel engine for automobile and diesel vehicle have been had renewal, deeper into understanding, diesel engine and gasoline engine
Compare on the premise of economical, dynamic property is superior, the pollution of environment is brought certain negative, with environmental quality
Deterioration, the limit value also increasingly stringent to moving source pollution emissions such as vehicles, especially as integrated environment quality evaluation
Nitrogen oxides (the NO of one of indexX).Having research display, it not only can cause acid rain, photochemical fog etc. to destroy earth ecology
The series of problems of environment, but also the health of human body in serious harm.Therefore, denitrification how is effectively gone to become
An important topic attracting people's attention in current field of Environment Protection.Ammonia selective catalytic reduction (selective catalytic
Reduction, SCR) due to ripe and efficiently become the denitration technology of main flow, and its key problem is that grinding of catalyst
System and the adaptability of catalyst and various operating modes.Many catalyst systems have been carried out going deep into systematic research by Chinese scholars,
Such as V2O5-WO3/TiO2,MnO2/TiO2,FeOx/TiO2,CuO/TiO2,Cr2O3/TiO2And CeO2/TiO2Deng.At present, industrialization should
NH3-SCR catalyst, how with TiO2For carrier, then upload a certain amount of V2O5、WO3、MoO3Deng.To this end, people are to denitration
The research of catalysis technique is deepening constantly, and to seek the wider array of denitrating catalyst of range, adapts to various operating mode with this.
CN201110389934 mono-kind is used for the preparation method of the SCR vanadium catalyst series of exhaust gas from diesel vehicle denitration, this
The bright preparation method disclosing a kind of SCR vanadium catalyst series for exhaust gas from diesel vehicle denitration.Catalyst uses simple leaching
Stain method introduces active component, then by carrying out different temperature calcination process to catalyst carrier or catalyst, so obtains
SCR vanadium catalyst series there is prominent catalytic performance improve, considerably increase catalysis activity, catalyst strength also increases
Add.The vanadium series denitrating catalyst that the present invention provides has higher denitration efficiency and wider temperature window, it is adaptable to diesel oil
The removing field of tail gas nitrogen oxides.Laboratory simulation exhaust gas from diesel vehicle evaluation is used to show, when air speed is 30000h-1, NO
Content is 500ppm, H2Under conditions of O content is 4%, the temperature range of 170-460 DEG C, the inventive method is used to prepare
SCR vanadium catalyst series to the removal efficiency of NOx more than 90%.There is the life-span in SCR catalyst prepared by this employing infusion process
Short defect, has an impact to the durability band of catalyst.
CN201210055163.0 mono-kind is used for low-temperature SCR catalyst of diesel car tail gas refining and preparation method thereof, should
Invention relates to a kind of low-temperature SCR catalyst for diesel car tail gas refining and preparation method thereof, it is therefore an objective to have higher thermal steady
Qualitative and preferable low-temperature catalytic activity；This catalyst components content is by weight percentage: silica alumina ratio Si/Al is 38～50
Molecular sieve HZSM-5:40～80%；Ammonium molybdate (NH4)6Mo7O24·4H2O:0～12.1%；Anhydrous FeCl3: 0.1～
10.7%；Manganese acetate: 0.1～19.9%；Cerous nitrate: 0.1～17.0%；The purity of each component is pure for analyzing；Its preparation method
It is to add ammonium molybdate (NH in deionized water4)6Mo7O24·4H2O and anhydrous FeCl3, after stirring and dissolving, add molecular sieve
HZSM-5, keeps homogeneous temperature stirring, until moisture distilled-to-dryness；It is dried 12h at a temperature of 110～130 DEG C, then 500～
700 DEG C of temperature lower calcination 3～6h, obtain intermediate products；Manganese acetate and cerous nitrate are mixed with this intermediate products, adds deionization
Water stirs, and with ammoniacal liquor regulation pH value to 12～13, continues stirring 2h, vacuum filtration, washing；Freeze-day with constant temperature 12h at 110 DEG C,
Roasting 5h at 350～550 DEG C again.There is life-span short defect in SCR catalyst prepared by this method, durable to catalyst
Property band has an impact.
CN201110425117 electrospray SCR diesel engine tail gas catalyst, this disclosure of the invention is a kind of EFI
SCR diesel motor exhaust catalyst.The present invention starts with in nature from Diesel engine, in conjunction with diesel engine emissions tail gas
Each composition CO/HC/NOX/NH3The character of gas, carries out catalytic purification to the pernicious gas in exhaust emissions, and has taken pin
Measure to property, has been respectively coated with modified RE oxide catalyst coatings, catalyst activity component coating and catalysis to carrier
Agent active component solution is coated.The present invention needs to combine urea water when being used in Diesel engine tail gas catalyzed and makees reducing agent,
By urea pyrolysis, hydrolysis of urea, the series reaction such as NOx reduces, ammonia oxidation, could tail gas catalytic purification the most at last.This
Invention is experimentally confirmed, the tail gas catalytic purification effect to Diesel engine, and preparation cost is cheap, effective.
CN1101584992A urea scr catalyst and manufacture method thereof, this invention relates to a kind of selective reduction catalysis
Agent: wherein substantially along the longitudinal, half catalyst (entrance) scribbles Mn/TiO2, and second half catalyst (outlet) scribbles Fe-boiling
Stone/ZSM, and prepare finishing coat by adding cerous carbonate, thus in finishing coat, form hole by the decomposition in roasting process,
And increase active surface area and the effectiveness of performance of catalyst.This aspect is characterised by the preparation side of this selective reduction catalyst
Method.The defect of denitration catalyst agent material prepared by this employing impregnation method is that service life is short, it is impossible to fit with various operating mode phases
Should.
CN101954281A is used for cerium copper titanium compound oxide catalyst and preparation method, this disclosure of the invention of denitrating flue gas
A kind of cerium copper titanium compound oxide catalyst for denitrating flue gas and preparation method, the component of this catalyst includes CeO2、
CuO and TiO2.Catalyst preparation uses coprecipitation, can reach preferable denitration effect.The advantage of this catalyst is: 1) to cigarette
The catalysis reduction of nitrogen oxides in gas has higher activity；2) the adaptive temperature window of catalyst is wider, at 150～450 DEG C
In whole temperature range, all there is certain activity；3) catalyst can be effectively improved at SO2And H2Runnability under the conditions of O, right
Bad working environments in the presence of sulfur dioxide and water etc. has stronger adaptability, exercisable wider；4) raw material is prepared easy
, preparation technology simple, catalyst cost is relatively low, and the defect of denitration catalyst agent material prepared by this employing coprecipitation is to make
Short with the life-span, it is impossible to adapt with various operating modes.
SCR technology is as removing diesel engine NOXMainstream technology, especially vanadium titanium series selectivity
Catalytic reduction catalysts, has higher NOXRemoval efficiency, preferable sulfur resistance, longer service life, in addition China's oil
The national condition of product, SCR is Chinese Diesel machine NOXDischarge optimal a kind of technology path.But due in traditional catalyst
Using middle discovery, selectivity during reaction is not strong, the defects such as service life is short.In addition, perovskite type catalyst can not only reduce
The use of noble metal, makes catalyst keep excellent low temperature active simultaneously.Therefore, these catalyst become numerous research work
The target that person pursues.
Content of the invention
In order to overcome defect of the prior art, it is an object of the invention to provide a kind of perovskite structure material, its system
Preparation Method and purposes.For realizing the purpose of the present invention, technical scheme is as follows:
The invention provides the method preparing perovskite structure material, it is prepared via a method which to obtain:
1) titanium salt is added in deionized water, is configured to the colloid that weight percent concentration is 5～35%, add pH regulation
Agent regulates pH value 7～8, is washed with deionized gained colloidal material；
2) it is added to molybdenum salt in deionized water, is configured to the colloid that weight percent concentration is 1～25%, add pH regulation
Agent regulates pH value 7～8, is washed with deionized gained colloidal material；
3) by the material after above-mentioned washing and V2O5Mixing, heat preservation and dryness and precalcining.
In the preferred embodiment of the present invention, titanium, molybdenum and the ratio of the amount of the material of vanadium are 1～10: 0.5～2: 1-10.
In the preferred embodiment of the present invention, described titanium salt be the one in titanium tetrachloride, Titanium Nitrate or titanium oxalate or
Multiple.
In the preferred embodiment of the present invention, described molybdenum salt be the one in molybdenum dichloride, oxalic acid molybdenum or nitric acid molybdenum or
Multiple.
In the preferred embodiment of the present invention, described pH adjusting agent is in ammoniacal liquor, ammonium carbonate, ammonium hydrogen carbonate or urea
One or more.
In the preferred embodiment of the present invention, by the material mixing after washing, heat preservation and dryness 15-25h, holding temperature is
110-150℃。
In the preferred embodiment of the present invention, it is placed in the material of gained after insulation in Muffle furnace, under air atmosphere, with
The heating rate of 5-15 DEG C/min is warming up to 300-450 DEG C, is cooled to room temperature through spontaneous combustion, after grinding after carrying out constant temperature 2-4 hour
Obtain perovskite structure material.
Prepared according to the methods of the invention perovskite structure material.
Prepared according to the methods of the invention perovskite structure material is used for processing diesel engine vent gas NO in preparationXSCR
Application in catalyst
Present invention also offers the preparation method of a kind of titanium tungsten powder, described method includes following: configuration tungsten presoma is water-soluble
Liquid, adds ferric nitrate (as coagent) in above-mentioned solution, then metatitanic acid and the surface dispersant of preparing sulfuric acid process add
Enter and be stirred in above-mentioned solution, be finally dried and calcine, obtain required titanium tungsten powder；Described tungsten presoma is solvable
Tungsten salt
Described metatitanic acid is that ilmenite concentrate, low-grade titaniferous ore deposit or slag prepare TiO through sulfuric acid process2Intermediate product, or
Its mixture.
In the preferred embodiment of the present invention, the weight percent concentration of tungsten presoma is 5～20%, the weight of ferric nitrate
Amount percent concentration is 5～10%.
In the preferred embodiment of the present invention, the addition of described surface dispersant is tungsten precursor water solution weight
1～15%.
In the preferred embodiment of the present invention, described surface dispersant is ammonium citrate, ammonium oxalate, ammonium fluoride or inclined phosphorus
One or more in acid ammonium.
In the preferred embodiment of the present invention, the metatitanic acid that prepared by described sulfuric acid process and the weight of tungsten precursor water solution
Ratio is 30～65: 50～80.
In the preferred embodiment of the present invention, baking temperature be 150～300 DEG C, drying time be 5～30h, calcining temperature
Degree is 350～700 DEG C, calcination time is 1～25h.
Prepared according to the methods of the invention titanium tungsten powder.
Prepared according to the methods of the invention titanium tungsten powder is being used for processing diesel engine vent gas NOXSCR catalyst in should
With.
The metatitanic acid that the present invention uses sulfuric acid process to prepare is precursor synthesis titanium tungsten powder, and tradition titanium tungsten powder can be avoided to prepare
The problem that in journey, tungsten load is uneven and production efficiency is low, can improve power production efficiency simultaneously, it is ensured that the high of catalyst is lived
Property and sintering strength.Use the titanium tungsten powder prepared of the method, it is possible to decrease existing power production cost and achieve environmental friendliness, open up
Wide application in denitrating catalyst for the powder.In addition, titanium tungsten powder of the present invention is uniformly dispersed, specific surface area is high, is used for preparing catalysis
During agent, add the selectivity of catalytic reaction, and the lifting of the sulfur resistance of catalyst is greatly improved.
Present invention also offers preparation for processing diesel engine vent gas NOXThe method of SCR catalyst, described method includes
Following steps:
1) perovskite structure material, titanium tungsten powder and aluminium glue are mixed, add polyvinyl alcohol to be stirred with deionized water,
It is prepared coating colloid under high speed shear emulsification condition；
Described perovskite structure material, titanium tungsten powder, aluminium glue, polyvinyl alcohol, the weight ratio of deionized water be 5～35: 50～
90: 1.5～10: 0.05～2: 80～200；
2) adding ammonium humate to be aged to above-mentioned coating adhesive body, the addition of ammonium humate is colloidal materials weight
0.05～2%；
3) the coating colloid after the ceramic honey comb that ultrasonic cleaning is good being placed in ageing carries out dip loading starching, coating
Load thickness is at 0.01～0.1mm；
4) it is respectively put into the ceramic honeycomb carrier of starching in baking oven and Muffle furnace and is dried and roasting, obtain SCR and urge
Agent.
Wherein, described perovskite structure material is to be prepared by following methods:
A) titanium salt is added in deionized water, is configured to the colloid that weight percent concentration is 5～35%, add ammoniacal liquor to adjust
Gained colloidal material is washed with deionized by joint pH value 7～8；
B) it is added to molybdenum salt in deionized water, is configured to the colloid that weight percent concentration is 1～25%, add ammoniacal liquor to adjust
Gained colloidal material is washed with deionized by joint pH value 7～8；
C) by the material after above-mentioned washing and V2O5Mixing, titanium, molybdenum are 1～10: 0.5～2 with the ratio of the amount of the material of vanadium:
1-10, heat preservation and dryness 15-25h, holding temperature is 110-150 DEG C, finally, is placed in Muffle furnace the material of gained after insulation in advance
Calcining, under air atmosphere, is warming up to 300-450 DEG C with the heating rate of 5-15 DEG C/min, carries out after constant temperature 2-4 hour through spontaneous combustion
It is cooled to room temperature, after grinding, obtain perovskite structure material.
In the preferred embodiment of the present invention, described titanium tungsten powder is to be prepared by following methods: configuration percentage by weight is dense
Degree is 5～20% tungsten precursor water solution, in above-mentioned solution add weight percent concentration be 5～10% ferric nitrates (as
Coagent), then metatitanic acid and the ammonium citrate of preparing sulfuric acid process be added to be stirred in above-mentioned solution, finally does
Dry, baking temperature is 150～300 DEG C, drying time is 5～30h and calcining, and calcining heat is 350～700 DEG C, calcination time
Being 1～25h, obtaining required titanium tungsten powder, wherein said tungsten presoma is solvable tungsten salt.
In the preferred embodiment of the present invention, the addition of ammonium citrate be tungsten precursor water solution weight 1～
15%.
In the preferred embodiment of the present invention, the metatitanic acid that prepared by described sulfuric acid process and the weight of tungsten precursor water solution
Ratio is 30～65: 50～80.
In the preferred embodiment of the present invention, step 1) in, described high-speed shearing machine is prepared colloid, cutter
Rotating speed is 150～300r/min, and preparation time is 1～10h；Perovskite structure material, titanium tungsten powder, aluminium glue, polyvinyl alcohol and go
The weight ratio of ionized water is 20: 65: 2.5: 0.5: 150.
In the preferred embodiment of the present invention, step 2) in, described coating colloid adds the corruption of 0.05～2.0% to plant
Acid ammonium is aged, and digestion time is 5～30 days；Purity >=99.9% of described ammonium humate.
In the preferred embodiment of the present invention, step 3) in, after the ceramic honeycomb that ultrasonic cleaning is good is placed in ageing
Carrying out in coating colloid soaking load starching, the load thickness of coating is at 0.03～0.1mm.
In the preferred embodiment of the present invention, step 4) in, baking temperature controls at 90～200 DEG C, and drying time is 1
～10h, sintering temperature controls at 450～550 DEG C, roasting time 1～10h.
Being used for of prepared in accordance with the method for the present invention processes diesel engine vent gas NOXSCR catalyst.
The above-mentioned perovskite structure material containing molybdenum and vanadium, has the effect of high degree of dispersion between vanadium titanium, the conduct of titanium own
The matrix material of SCR catalyst, is partly introduced in this step, is also V2O5The matrix material of whole catalyst is carried out
Pre-dispersed.
The present invention sets up a kind of for diesel engine vent gas process NOXSCR catalyst and preparation method, in the system of catalyst
Synthesize during Bei and be prepared for the material containing molybdenum and the perovskite structure of vanadium, synthesize and be prepared for titanium tungsten powder, making catalyst
Active component be dispersed in respectively in respective matrix material, add the selectivity of catalytic reaction, also improve catalyst
Sulfur resistance and extend catalyst benefit from the life-span, the SCR catalyst performance adaptation condition model preparing through this technique
Enclose width, service life the advantage such as length.
The invention have the advantage that (1) this technique uses titanium salt presoma to synthesize the perovskite structure material containing molybdenum and vanadium,
Titanium salt will be added drop-wise in deionized water, add ammoniacal liquor regulation pH value, gained colloidal materials is washed with deionized chlorion
Mix with the colloidal materials of gained after molybdenum salt hydrolysis afterwards, after mixing, after heat preservation and dryness and calcining at a certain temperature, obtain calcium titanium
Ore deposit structural material, this perovskite structure material improves V2O5And MoO3The selectivity of the uniformity and catalytic reaction, by inclined tungsten
The metatitanic acid prepared by sulfuric acid process is modified obtaining titanium tungsten powder by acid ammonium；Use ferric nitrate as the activity in synthesis titanium tungsten powder
Auxiliary agent, obtains titanium tungsten powder through being dried and calcining, improves the sulfur resistance of catalyst and the service life of catalyst；(2) calcium
Perovskite like structure material, titanium tungsten powder, aluminium glue, polyethylene glycol are stirred with water, are prepared painting under high speed shear emulsification condition
Layer colloid, this active component adds selectivity during catalyst reaction with the scattered mode of respective matrix；(3) humic is used
Coating colloid is aged by acid ammonium, improves the consistency of coating, reduces the thickness of coating；(4) rational coating design
Scheme, makes catalyst have low temperature active.The catalyst treated application 8L co-rail diesel that drying of the present invention and roasting obtain
Machine frame cleaning test shows, gas reaction temperature at 180～420 DEG C of transformation efficiencies still keeping nitrogen oxides to have 97%,
Product is after stand quick aging, and gas reaction temperature is 180～420 DEG C of conversion effects still keeping nitrogen oxides to have 89%
Rate, can meet Europe IV/V and above Abgasgesetz；(5) it is placed in the ceramic honeycomb that ultrasonic cleaning is good in coating colloid and soaks
Bubble load coating；(6) ceramic honeycomb carrier of starching is respectively put into baking oven and Muffle furnace is dried and roasting；(7) this
Bright prepare metatitanic acid by sulfuric acid process and prepare titanium tungsten powder, greatly reduce its production cost.
Detailed description of the invention
Embodiment 1
(1) perovskite structure material is prepared
A) titanium tetrachloride is added in deionized water, is configured to the colloid that weight percent concentration is 20%, add ammoniacal liquor
Gained colloidal material is washed with deionized by regulation pH value 7～8；
B) it is added to oxalic acid molybdenum in deionized water, is configured to the colloid that weight percent concentration is 25%, add ammoniacal liquor to adjust
Gained colloidal material is washed with deionized by joint pH value 7～8；
C) by the material after above-mentioned washing and V2O5Mixing, titanium, molybdenum are 1: 0.5: 1 with the ratio of the amount of the material of vanadium, and insulation is dry
Dry 25h, holding temperature is 130 DEG C, finally, the material of gained after insulation is placed in precalcining in Muffle furnace, under air atmosphere, with
The heating rate of 10 DEG C/min is warming up to 400 DEG C, carries out constant temperature and is cooled to room temperature through spontaneous combustion after 4 hours, obtains calcium titanium after grinding
Ore deposit structural material.
Wherein purity >=99.9% of titanium tetrachloride；Purity >=99.9% of oxalic acid molybdenum.
(2) titanium tungsten powder is prepared
Configuration weight percent concentration is 15% ammonium metatungstate aqueous solution, adds weight percent concentration in above-mentioned solution
It is 5% ferric nitrate (as coagent), then metatitanic acid (TiO prepared by sulfuric acid process2Content 50%, sulfate radical content
10wt.%) and ammonium citrate is added to be stirred in above-mentioned solution, being finally dried, baking temperature is 250 DEG C, when being dried
Between be 15h and calcining, calcining heat is 450 DEG C, calcination time is 15h, obtains required titanium tungsten powder；
Wherein the addition of ammonium citrate is the 10% of ammonium metatungstate aqueous solution weight；Metatitanic acid prepared by above-mentioned sulfuric acid process
Weight ratio with ammonium metatungstate aqueous solution is 45: 60
Purity >=99.9% of wherein said ammonium metatungstate.
(3) preparation of catalyst
A) perovskite structure material, titanium tungsten powder and aluminium glue are mixed, add polyvinyl alcohol to be stirred with deionized water,
Being prepared coating colloid under high speed shear emulsification condition, cutter rotating speed is 200r/min, and preparation time is 5h；
Described perovskite structure material, titanium tungsten powder, aluminium glue, polyvinyl alcohol, the weight ratio of deionized water are 20: 65: 2.5:
0.5∶150；
B) being aged above-mentioned coating colloid addition ammonium humate, the addition of ammonium humate is colloidal materials weight
0.5%, digestion time is 15 days；Purity >=99.9% of described ammonium humate；
C) by a size of Φ 267mm × 152mm, hole count is 62/cm2Cordierite ceramic honeycomb to be placed in ultrasonic wave clear
Wash and instrument carry out ultrasonic cleaning, and add hydrofluoric acid regulation cleaning fluid pH=2, wherein the frequency of ultrasonic washing instrument be 50HZ,
Power is 100W, and the ultrasonic cleaning time is 120min.In coating colloid after the ceramic honey comb that ultrasonic cleaning is good is placed in ageing
Carrying out dip loading starching, the load thickness of coating is at 0.05mm；
D) it is respectively put into the ceramic honeycomb carrier of starching in baking oven and Muffle furnace and is dried and roasting, baking temperature control
System is at 150 DEG C, and drying time is 10h, and sintering temperature controls at 500 DEG C, and roasting time 5h obtains SCR catalyst.
Embodiment 2
(1) perovskite structure material is prepared
A) titanium tetrachloride is added in deionized water, is configured to the colloid that weight percent concentration is 30%, add ammoniacal liquor
Gained colloidal material is washed with deionized by regulation pH value 7～8；
B) it is added to oxalic acid molybdenum in deionized water, is configured to the colloid that weight percent concentration is 25%, add ammoniacal liquor to adjust
Gained colloidal material is washed with deionized by joint pH value 7～8；
C) by the material after above-mentioned washing and V2O5Mixing, titanium, molybdenum are 1.5: 0.8: 1.5 with the ratio of the amount of the material of vanadium, protect
Temperature is dried 25h, and holding temperature is 140 DEG C, finally, the material of gained after insulation is placed in precalcining in Muffle furnace, air atmosphere
Under, it is warming up to 450 DEG C with the heating rate of 15 DEG C/min, carry out constant temperature and be cooled to room temperature through spontaneous combustion after 4 hours, obtain after grinding
Perovskite structure material.
Wherein purity >=99.9% of titanium tetrachloride；Purity >=99.9% of oxalic acid molybdenum.
(2) titanium tungsten powder is prepared
Configuration weight percent concentration is 20% ammonium metatungstate aqueous solution, adds weight percent concentration in above-mentioned solution
It is 8% ferric nitrate (as coagent), then metatitanic acid (TiO prepared by sulfuric acid process2Content 50%, sulfate radical content
10wt.%) and ammonium citrate is added to be stirred in above-mentioned solution, being finally dried, baking temperature is 300 DEG C, when being dried
Between be 15h and calcining, calcining heat is 500 DEG C, calcination time is 15h, obtains required titanium tungsten powder；
Wherein the addition of ammonium citrate is the 12% of ammonium metatungstate aqueous solution weight；Metatitanic acid prepared by above-mentioned sulfuric acid process
Weight ratio with ammonium metatungstate aqueous solution is 55: 75
Purity >=99.9% of wherein said ammonium metatungstate.
(3) preparation of catalyst
A) perovskite structure material, titanium tungsten powder and aluminium glue are mixed, add polyvinyl alcohol to be stirred with deionized water,
Being prepared coating colloid under high speed shear emulsification condition, cutter rotating speed is 250r/min, and preparation time is 7h；
Described perovskite structure material, titanium tungsten powder, aluminium glue, polyvinyl alcohol, the weight ratio of deionized water are 26: 70: 5: 0.9
∶175；
B) adding ammonium humate to be aged to above-mentioned coating adhesive body, the addition of ammonium humate is colloidal materials weight
2%, digestion time is 25 days；Purity >=99.9% of described ammonium humate；
C) by a size of Φ 267mm × 152mm, hole count is 62/cm2Cordierite ceramic honeycomb to be placed in ultrasonic wave clear
Wash and instrument carry out ultrasonic cleaning, and add hydrofluoric acid regulation cleaning fluid pH=2, wherein the frequency of ultrasonic washing instrument be 50HZ,
Power is 100W, and the ultrasonic cleaning time is 120min.In coating colloid after the ceramic honey comb that ultrasonic cleaning is good is placed in ageing
Carrying out dip loading starching, the load thickness of coating is at 0.08mm；
D) it is respectively put into the ceramic honeycomb carrier of starching in baking oven and Muffle furnace and is dried and roasting, baking temperature control
System is at 200 DEG C, and drying time is 10h, and sintering temperature controls at 550 DEG C, and roasting time 5h obtains SCR catalyst.
Embodiment 3
(1) perovskite structure material is prepared
A) titanium tetrachloride is added in deionized water, is configured to the colloid that weight percent concentration is 35%, add ammoniacal liquor
Gained colloidal material is washed with deionized by regulation pH value 7～8；
B) it is added to oxalic acid molybdenum in deionized water, is configured to the colloid that weight percent concentration is 25%, add ammoniacal liquor to adjust
Gained colloidal material is washed with deionized by joint pH value 7～8；
C) by the material after above-mentioned washing and V2O5Mixing, titanium, molybdenum are 2.5: 1: 2.5 with the ratio of the amount of the material of vanadium, insulation
Being dried 25h, holding temperature is 150 DEG C, finally, the material of gained after insulation is placed in precalcining in Muffle furnace, under air atmosphere,
It is warming up to 450 DEG C with the heating rate of 15 DEG C/min, carry out constant temperature and be cooled to room temperature through spontaneous combustion after 4 hours, after grinding, obtain calcium
Perovskite like structure material.
Wherein purity >=99.9% of titanium tetrachloride；Purity >=99.9% of oxalic acid molybdenum.
(2) titanium tungsten powder is prepared
Configuration weight percent concentration is 20% ammonium metatungstate aqueous solution, adds weight percent concentration in above-mentioned solution
It is 10% ferric nitrate (as coagent), then metatitanic acid (TiO prepared by sulfuric acid process2Content 50%, sulfate radical content
10wt.%) and ammonium citrate is added to be stirred in above-mentioned solution, being finally dried, baking temperature is 300 DEG C, when being dried
Between be 20h and calcining, calcining heat is 550 DEG C, calcination time is 20h, obtains required titanium tungsten powder；
Wherein the addition of ammonium citrate is the 15% of ammonium metatungstate aqueous solution weight；Metatitanic acid prepared by above-mentioned sulfuric acid process
Weight ratio with ammonium metatungstate aqueous solution is 60: 80
Purity >=99.9% of wherein said ammonium metatungstate.
(3) preparation of catalyst
A) perovskite structure material, titanium tungsten powder and aluminium glue are mixed, add polyvinyl alcohol to be stirred with deionized water,
Being prepared coating colloid under high speed shear emulsification condition, cutter rotating speed is 300r/min, and preparation time is 10h；
Described perovskite structure material, titanium tungsten powder, aluminium glue, polyvinyl alcohol, the weight ratio of deionized water are 35: 80: 6.5: 2
∶200；
B) adding ammonium humate to be aged to above-mentioned coating adhesive body, the addition of ammonium humate is colloidal materials weight
2%, digestion time is 30 days；Purity >=99.9% of described ammonium humate；
C) by a size of Φ 267mm × 152mm, hole count is 62/cm2Cordierite ceramic honeycomb to be placed in ultrasonic wave clear
Wash and instrument carry out ultrasonic cleaning, and add hydrofluoric acid regulation cleaning fluid pH=2, wherein the frequency of ultrasonic washing instrument be 50HZ,
Power is 100W, and the ultrasonic cleaning time is 120min.In coating colloid after the ceramic honey comb that ultrasonic cleaning is good is placed in ageing
Carrying out dip loading starching, the load thickness of coating is at 0.1mm；
D) it is respectively put into the ceramic honeycomb carrier of starching in baking oven and Muffle furnace and is dried and roasting, baking temperature control
System is at 200 DEG C, and drying time is 10h, and sintering temperature controls at 550 DEG C, and roasting time 10h obtains SCR catalyst.
The SCR catalyst preparing according to embodiment 2, product size is 267mm × 152mm, and quantity is 2, catalyst pores
Number is 62 holes/cm2, inwall wall thickness is 0.15mm, and the density of product is 560g/l.Catalyst cascade is carried out install and carry out to send out
Motivation bench test, diesel fuel injection system is high-pressure common rail, and waste gas purification technology path is DOC+SCR, fresh state and
Aging state emission result is shown in Table the 1st, table 2 respectively, and stand aging 100h experimental condition is carried out.Remarks: (aging condition: HJ451-
2008 People's Republic of China's state environment protecting standards " environmental protection product technology requirement-diesel engine truck exhaust post processing dress
Put ".)
Table 1 fresh state testing result
| Project | CO | HC | NO<sub>X</sub> | PM |
| ESC limit value IV (g/kWh) | 1.5 | 0.46 | 3.5 | 0.02 |
| ESC limit value V (g/kWh) | 0.25 | 0.25 | 2.0 | 0.02 |
| Former car discharges (g/kWh) | / | / | 8.6 | / |
| Purify discharge (g/kWh) | / | / | 0.2 | / |
| Selective % | / | / | 97.7 | / |
The durable state testing result of table 2 stand 100h quick aging
| Project | CO | HC | NO<sub>X</sub> | PM |
| ESC limit value IV (g/kWh) | 1.5 | 0.46 | 3.5 | 0.02 |
| ESC limit value V (g/kWh) | 0.25 | 0.25 | 2.0 | 0.02 |
| Former car discharges (g/kWh) | / | / | 8.6 | / |
| Purify discharge (g/kWh) | / | / | 0.9 | / |
| Selective % | / | / | 89.5 | / |
Claims (8)
1. the method preparing titanium tungsten powder, it is characterised in that described method includes following: configuration tungsten precursor water solution,
Above-mentioned solution adds ferric nitrate, then metatitanic acid and the surface dispersant of preparing sulfuric acid process join in above-mentioned solution and stir
Mix, be finally dried and calcine, obtain required titanium tungsten powder；Described tungsten presoma is solvable tungsten salt；
Described metatitanic acid is that ilmenite concentrate, low-grade titaniferous ore deposit or slag prepare TiO through sulfuric acid process2Intermediate product, or its mixing
Thing.
2. method according to claim 1, it is characterised in that the weight percent concentration of tungsten presoma is 5～20%, nitre
The weight percent concentration of acid iron is 5～10%.
3. method according to claim 1, it is characterised in that the addition of described surface dispersant is that tungsten presoma is water-soluble
The 1～15% of liquid weight.
4. method according to claim 1, it is characterised in that described surface dispersant is ammonium citrate, ammonium oxalate, fluorination
One or more in ammonium or ammonium metaphosphate.
5. method according to claim 1, it is characterised in that metatitanic acid prepared by described sulfuric acid process is water-soluble with tungsten presoma
The weight ratio of liquid is 30～65:50～80.
6. method according to claim 1, it is characterised in that baking temperature is 150～300 DEG C, drying time be 5～
30h, calcining heat is 350～700 DEG C, calcination time is 1～25h.
7. the titanium tungsten powder that prepared by the method according to any one of claim 1-6.
8. the titanium tungsten powder that prepared by the method according to any one of claim 1-6 is for processing diesel engine vent gas NOXSCR
Application in catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610428439.3A CN106076356A (en) | 2016-06-16 | 2016-06-16 | A kind of titanium tungsten powder and its production and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610428439.3A CN106076356A (en) | 2016-06-16 | 2016-06-16 | A kind of titanium tungsten powder and its production and use |
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| JP2009255057A (en) * | 2008-03-24 | 2009-11-05 | Kumamoto Univ | Particulate material combustion catalyst, its manufacturing method, and filter for purifying exhaust gas |
| CN103608090A (en) * | 2011-05-11 | 2014-02-26 | 莎哈利本颜料有限公司 | Raw material for vanadium-free or vanadium-less denitration catalyst and preparation method thereof |
| CN104415745A (en) * | 2013-08-22 | 2015-03-18 | 上海郎特汽车净化器有限公司 | Perovskite structure substance and preparation method thereof |
| CN104415747A (en) * | 2013-08-22 | 2015-03-18 | 上海郎特汽车净化器有限公司 | Titanium tungsten powder and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009255057A (en) * | 2008-03-24 | 2009-11-05 | Kumamoto Univ | Particulate material combustion catalyst, its manufacturing method, and filter for purifying exhaust gas |
| CN103608090A (en) * | 2011-05-11 | 2014-02-26 | 莎哈利本颜料有限公司 | Raw material for vanadium-free or vanadium-less denitration catalyst and preparation method thereof |
| CN104415745A (en) * | 2013-08-22 | 2015-03-18 | 上海郎特汽车净化器有限公司 | Perovskite structure substance and preparation method thereof |
| CN104415747A (en) * | 2013-08-22 | 2015-03-18 | 上海郎特汽车净化器有限公司 | Titanium tungsten powder and preparation method thereof |
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