CN102395429A - 蜂窝状催化剂载体及其生产方法 - Google Patents
蜂窝状催化剂载体及其生产方法 Download PDFInfo
- Publication number
- CN102395429A CN102395429A CN2010800169560A CN201080016956A CN102395429A CN 102395429 A CN102395429 A CN 102395429A CN 2010800169560 A CN2010800169560 A CN 2010800169560A CN 201080016956 A CN201080016956 A CN 201080016956A CN 102395429 A CN102395429 A CN 102395429A
- Authority
- CN
- China
- Prior art keywords
- carrier
- aforementioned
- copolymer
- vinyl pyrrolidone
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 239000000758 substrate Substances 0.000 title abstract description 4
- 238000004519 manufacturing process Methods 0.000 title description 2
- 229920000642 polymer Polymers 0.000 claims abstract description 37
- 229920001577 copolymer Polymers 0.000 claims abstract description 27
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 11
- 239000011147 inorganic material Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 27
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 239000002912 waste gas Substances 0.000 claims description 14
- 239000004411 aluminium Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052863 mullite Inorganic materials 0.000 claims description 6
- 230000000269 nucleophilic effect Effects 0.000 claims description 5
- 241001466460 Alveolata Species 0.000 claims description 4
- 229910052878 cordierite Inorganic materials 0.000 claims description 4
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000004756 silanes Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000004071 soot Substances 0.000 claims description 3
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N Caprolactam Natural products O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002161 passivation Methods 0.000 description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 229910000077 silane Inorganic materials 0.000 description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 4
- 239000013047 polymeric layer Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- 241000264877 Hippospongia communis Species 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000784 Nomex Polymers 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000002152 aqueous-organic solution Substances 0.000 description 1
- 238000009924 canning Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007571 dilatometry Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000004763 nomex Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- -1 siloxanes Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
- C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
- C04B35/185—Mullite 3Al2O3-2SiO2
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
- C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
- C04B35/195—Alkaline earth aluminosilicates, e.g. cordierite or anorthite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/478—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on aluminium titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0006—Honeycomb structures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/48—Macromolecular compounds
- C04B41/4857—Other macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/82—Coating or impregnation with organic materials
- C04B41/83—Macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
本发明的主题是由多孔无机材料制成的催化剂载体,用于处理废气的,具有蜂窝状结构,该结构的面之一用于吸入待处理的废气并且另一个面用于排出处理过的废气,所述结构包括,在这些吸入和排出面之间,被多孔壁分开的互相平行轴的相邻管或通道的阵列,所述载体被在至少部分的它的内表面上涂布以至少一种乙烯基吡咯烷酮聚合物或共聚物。
Description
本发明涉及的领域是由多孔无机材料制成的催化剂载体(substrat de catalyseur),其用于处理排出废气(gaz d’échappement),特别地来自内燃机,尤其是来自汽车,例如来自柴油发动机的废气。这些载体具有蜂窝状结构,该结构的面之一用于吸入待处理的废气并且另一个面用于排出处理过的废气,所述结构包括,在这些吸入和排出面之间,被多孔壁分开的互相平行轴的相邻管或通道的阵列。通道可以在该结构的末端中的一个或其它处(l’une ou l’autre des extrémités)交替地被密封以便滤出废气中所含的颗粒物或灰粒。这样,获得了通常称为颗粒过滤器的过滤器结构。
某些无机材料,例如钛酸铝(Al2TiO5)或堇青石,具有非常低的热膨胀,直到约800℃的温度。这种有利的特征应归于陶瓷颗粒中微裂纹的存在。在加热期间,材料的固有扩张首先引起微裂纹闭合,但没有载体的宏观扩张。由于这种低热膨胀,有可能使用单块的载体或过滤器,即由单个陶瓷块制成。
然而,在蜂窝状物的多孔壁的表面上沉积催化涂层通常导致这些微裂纹被密封,使得基材或过滤器的热膨胀由此增加。催化剂的存在将实际上防止微裂纹闭合。
已经建议针对这个问题的若干方法,但是它们都不是没有缺点的。这些方法在于将聚合化合物沉积在载体的表面上,然后是催化涂层,一种被称为"钝化"的技术。
专利申请US 2006/183632由此建议使用明胶或乙烯醇/乙烯胺共聚物或乙烯醇/乙烯基甲酰胺共聚物来钝化载体的表面。通常添加交联剂。钝化层然后与催化涂层同时被煅烧。然而,这种方法导致催化涂层对载体的低亲合力,并且因此降低了可以被固定到载体上的催化剂的量。此外,煅烧交联剂常常形成有毒的废气,后者必须被再处理。
专利申请DE 10 2007 023120建议沉积硅烷(silanes),通过交联将转变为硅氧烷。然而,在煅烧期间硅酮的分解形成大量废气并且产生二氧化硅,其密封微裂纹,因此增加热膨胀系数。
本发明的一个目标是通过提供对环境更友好的钝化(passivation)方法消除这些各种各样的缺点。本发明的另一目标是在载体或钝化层和催化涂层之间获得较好的亲合力(煅烧前后),所述催化涂层是在钝化步骤后沉积的。本发明的另一目标是限制具有其催化涂层的载体的宏观膨胀系数的增加。
为此,本发明的一个主题是由多孔无机材料制成的催化剂载体,用于处理废气的,具有蜂窝状结构,该结构的面之一用于吸入待处理的废气并且另一个面用于排出处理过的废气,所述结构包括,在这些吸入和排出面之间,被多孔壁分开的互相平行轴的相邻管或通道的阵列,所述载体被在至少部分的它的内表面上涂布以至少一种乙烯基吡咯烷酮聚合物或共聚物。
本发明的另一主题是一种用于获得根据本发明的由多孔无机材料制成的催化剂载体的方法,包括其中在所述载体上沉积乙烯基吡咯烷酮聚合物或共聚物的步骤,随后干燥步骤。
使用基于聚乙烯吡咯烷酮(PVP)的聚合物作为钝化材料具有若干优点。
不需要交联剂或固化剂,因为这些聚合物在干燥期间自交联。该方法因此更快速和成本更低,也对环境更友好,因为它包括使用无毒物质并且减小了煅烧期间废气的问题。
相对于现有技术的方法,催化涂层和载体之间的化学亲合力也进一步被改善。这种更好的亲合力使以下成为可能:随后每一单位面积固定更大量的催化剂,和获得更均匀的催化涂层(或修补基面涂层(washcoat))即在表面上更好地分布,和因此对于相同的载体的表面面积更大的催化效率。
基于聚乙烯吡咯烷酮的聚合物特别适合于钝化载体,其上随后沉积催化涂层,所述催化涂层在煅烧后具有非常小的微晶,特别地尺寸小于20nm,以便增加涂层的催化性能。这种类型的涂层,例如以勃姆石形式沉积的,然而具有容易渗透到载体的微裂纹中的缺点。
相比于从现有技术中已知的那些,基于聚乙烯吡咯烷酮的聚合物也被证明是更好的钝化材料。当在沉积任何催化涂层前在载体上沉积时,它们使以下成为可能:限制由于催化剂渗透到载体的陶瓷颗粒的微裂纹中造成的热膨胀系数的增加。
优选地,通道在末端中的一个或其它处交替地被密封以便滤出废气中所含的颗粒物或灰粒。于是,所获得的载体是颗粒过滤器,其具有催化组分,例如,使以下成为可能:消除以下类型的污染气体:NOx,一氧化碳(CO)或未烧尽烃(HC)。
优选地,多孔无机材料选自钛酸铝,堇青石(cordierite)和富铝红柱石(mullite)。也可使用其它材料,例如碳化硅或烧结金属。短语"钛酸铝"被理解为是指不仅式Al2TiO5的钛酸铝本身,而且也指基于钛酸铝的任何材料,特别地包括至少70%,或80%并且甚至90%的钛酸铝相的任何材料,任选地,对于钛和铝原子,有可能部分地被置换,尤其被硅,镁或锆原子置换。作为实例,钛酸铝可以包含如专利申请WO
2004/011124中教导的富铝红柱石(mullite)型,或如专利申请EP 1 559696中教导的长石(feldspar)型的再生相。材料的实例也在专利申请WO 2009/156652,WO 2010/001062,WO
2010/001064,WO 2010/001065和WO 2010/001066中给出。
乙烯基吡咯烷酮聚合物或共聚物优选地选自聚乙烯基吡咯烷酮,乙烯基吡咯烷酮(vinylpyrrolidole)/乙酸乙烯酯共聚物,乙烯基吡咯烷酮/乙烯基咪唑(vinylimidazone)共聚物和乙烯基吡咯烷酮(vinylypyrrolidone)/乙烯基己内酰胺共聚物,或它们的混合物中的任一种。优选地,不添加交联剂。
根据本发明的载体也可被在至少部分的它的内表面上涂布以至少一种硅烷型(type silane)化合物,尤其具有至少一个具有至少一种亲核基团的碳链的硅烷型化合物。这种化合物通常与乙烯基吡咯烷酮聚合物或共聚物同时沉积。这允许将乙烯基吡咯烷酮聚合物或共聚物更好地接枝到多孔陶瓷载体上。当添加硅烷后,硅烷的醇盐被载体表面上存在的羟基水解并且结合到这个表面。具有至少一个具有至少一种亲核基团的碳链的硅烷可以将被接枝的硅烷的另一端连接到乙烯基吡咯烷酮聚合物或共聚物,这是通过与后者的羰基反应实现的。
具有至少一个具有至少一种亲核基团的碳链的硅烷尤其是Nu-R1-Si-(OR2)3类型的,其中R1和R2是烷基,和亲核基团Nu可以选自NH2,SH和OH。可以将硅烷添加到聚合物或共聚物水溶液或水/醇混合物使得分散变得更容易和限制了其的水解。
优选地,通过液体,尤其水性溶液或分散体的浸渍,沉积了乙烯基吡咯烷酮聚合物或共聚物。在溶液或分散体中乙烯基吡咯烷酮聚合物或共聚物的重量含量有利地是1-30%,优选地5-15%。乙烯基吡咯烷酮聚合物或共聚物的平均分子量,尤其在沉积时,优选地是10000-1000000g/mol,尤其15000-500000g/mol,或15000-400000g/mol,或15000-300000g/mol或甚至20000-100000g/mol。这些各种的参数--溶液或分散体中的重量含量和平均分子量--用来调节溶液或分散体的粘度,和因此聚合物到载体的微裂纹中的穿透率。已经注意到,对于高分子量,典型地1000000或更高,可以随后被固定到载体上的催化涂层的量显著地降低。乙烯基吡咯烷酮聚合物或共聚物的平均分子量因此优选地小于1000000g/mol。
浸渍可以特别地通过浸渍基材和/或真空浸渍来进行。在后者情况中,基材可以在25毫巴或更低的压力下被置于干燥器中并且将聚合物溶液或分散体倒在载体上。
在浸渍后,过量的溶剂,尤其水,可以被除去,例如通过在载体的一端用气体如空气吹扫(blast),或者通过施加降低的压力,例如,在小于100毫巴的压力。
为优化催化涂层对载体的粘合,在至少100℃,尤其130-170℃或甚至130-160℃的温度下优选地进行干燥步骤。对于较低的温度,聚合物对载体的粘合是较弱的。聚合物更可溶于水中并且冒在催化涂层的沉积期间被溶解的风险。过高的温度,尤其高于180℃或甚至190℃,冒使聚合物变硬和在载体中产生机械应力的风险,特别地在催化涂层的沉积期间。还已经注意到这些高干燥温度具有降低可以随后被固定到载体上的催化涂层的量的作用。
根据本发明的载体优选地被在至少部分的它的表面上涂布以催化涂层。这钝化步骤后,这种涂层被沉积在载体或过滤器的壁的表面上。优选地,它包括基础材料和催化剂。基础材料通常是高比表面积(典型地大约10-100m2/g)的无机材料,这确保催化剂的分散和稳定。有利地,基础材料选自氧化铝,氧化锆,氧化钛,稀土氧化物,如二氧化铈,和碱金属或碱土金属氧化物。优选地,催化剂是基于贵金属,如铂,钯或铑,或基于过渡金属。
其中催化剂颗粒被置于其上的基础材料的颗粒尺寸通常为大约数纳米至数十纳米,或例外地数百纳米。
本发明的方法因此优选地随后是以下的步骤:沉积催化涂层并且然后煅烧步骤,典型地在空气中和在300-900℃,优选地400-600℃进行。
本发明的主题还是可以通过这种优选方法获得的催化剂载体。
在煅烧前,根据本发明的载体在其表面上具有聚合物层(乙烯基吡咯烷酮聚合物或共聚物)。这种聚合物层在煅烧期间被除去。然而,它的存在使获得煅烧的载体成为可能,而所述煅烧的载体不同于现有技术的已知的载体。
使用以下两种方法,在煅烧前,可以尤其确定聚合物层:
-通过与质谱相连的热重分析以便确定沉积的聚合物的分解产物;
-通过提取,例如通过浸出,随后色谱法分析,任选地与质谱相连。
催化涂层典型地通过浸渍含基础材料或它的前体和催化剂,或这种催化剂的前体来进行沉积。通常,所使用的前体采取有机或无机盐或溶解或悬浮在水溶液或有机溶液中的化合物的形式。浸渍之后是煅烧热处理以便最终涂层包含在载体或过滤器的孔中的催化活性固相。
这样的方法以及用于进行它们的设备例如描述于以下专利申请或专利中:US 2003/044520, WO 2004/091786,
US 6 149 973, US 6 627 257, US 6 478 874,, US 5 866 210, US 4 609 563, US 4 550
034, US 6 599 570, US 4 208,454 和 US 5
422 138。
根据本发明的催化剂载体或催化过滤器可以用于内燃机,典型地柴油发动机的废气管线中。为此,催化剂载体或催化过滤器可以被封装在纤维垫中然后被插入金属罐(metal
can),通常被称为"罐体(canning)"。纤维垫优选地由无机纤维形成以便给予应用的必需的热绝缘性能。无机纤维优选地是陶瓷纤维,如氧化铝,富铝红柱石,氧化锆,氧化钛,二氧化硅,碳化硅或氮化硅纤维,或玻璃纤维,如R-玻璃纤维。这些纤维可以通过纤维化获得,从熔融氧化物的浴开始,或者从有机金属前体的溶液开始(溶胶-凝胶过程)。优选地,纤维垫是非泡沸的并且有利地采取针刺毡的形式。
本发明非限制性地通过以下实施例说明,其中全部百分比是重量百分比。
使用上述方法,获得多孔的钛酸铝载体。
在预备步骤中,由以下原材料制备钛酸铝:
-约40wt%氧化铝,Al2O3纯度水平大于99.5%和中值直径d50为90μm,在标注AR75®下由Pechiney销售;
-约50wt%氧化钛,金红石形式的,包含多于95%
TiO2和约1%氧化锆,中值直径d50约120μm,由Europe Minerals销售;
-约5wt%二氧化硅,SiO2纯度水平大于99.5%和中值直径d50约210μm,由SIFRACO销售;和
-约4wt%的氧化镁粉,MgO纯度水平大于98%,大于80%的其的颗粒的直径为0.25-1mm,由Nedmag销售。
在电弧炉中,在空气中,在氧化电操作下将反应性氧化物的初始混合物熔化。熔融混合物然后浇铸到CS模具中以便实现快速冷却。研磨并且筛分所获得的产物以便获得各种颗粒尺寸分数的粉末。更确切地说,研磨和筛分操作在用于最终获得以下两种颗粒尺寸分数的条件下进行:
-一种颗粒尺寸分数特征为中值直径d50基本上等于50微米,由术语"粗"表示;和
-一种颗粒尺寸分数特征为中值直径d50基本上等于1.5微米,由术语"细"表示。
在本说明书的范围中,中值直径d50表示这样的颗粒直径,其通过沉降法测量,群体中50体积%处于该颗粒直径以下。
微探针分析显示这样获得的融合相的全部颗粒具有以下表1中再现的组成,以氧化物的重量百分比计:
表
1
Al2O3 | TiO2 | MgO | SiO2 | CaO | Na2O | K2O | Fe2O3 | ZrO2 | TOTAL |
40.5 | 48.5 | 3.98 | 4.81 | 0.17 | 0.15 | 0.47 | 0.55 | 0.85 | 100.00 |
然后使用这样获得的颗粒来制造生整料(基材(substrats))。
在混合器中混合根据以下组成的粉末:
-100%的两种钛酸铝粉末的共混物,其是预先通过下述方式生产的:熔融(fuse)浇铸,即约75%的中值直径50μm的第一粉末和25%的中值直径1.5μm的第二粉末。
接下来,添加以下:相对于混合物的总质量:
-4wt%的纤维素型的有机粘合剂;
-15%wt的造孔剂;
-5%的衍生自乙二醇的增塑剂;
-2%的润滑剂(油);
-0.1%的表面活性剂;和
-约20%的水,以便使用技术工艺,在混合后获得均质浆料,其的可塑性使得能够通过模具挤出蜂窝状结构,该结构在过火后具有如表2中的尺寸特征。
接下来,通过微波干燥来干燥所获得的生整料足够的时间以便使化学非结合水含量小于1wt%。
使用众所周知的技术,例如专利US 4557773中所述的那些,用满足以下配方的混合物塞住整料的两端的通道:
-100%的两种钛酸铝粉末的共混物,其是预先通过下述方式生产的:熔融(fuse)浇铸,即约66%的中值直径50μm的第一粉末和34%的中值直径1.5μm的第二粉末;
-1.5%的纤维素型的有机粘合剂;
-21.4%的造孔剂;
-0.8%的基于羧酸的分散剂;和
-约55%的水以便获得能在每隔一个通道(every
other channel)上密封整料的混合物。
在空气中渐进地过火直到到达1450℃的温度,该温度被维持4小时后的整料(载体)的特性以下在表2中给出:
表
2
整料形状 | 正方形 |
宽度 | 33mm |
长度 | 152.4mm |
胞腔截面 | 正方形 |
胞腔浓度 | 33个胞腔/cm2 |
壁厚 | 350μm |
过滤壁和塞的组成材料 | 基本上钛酸铝相 |
孔隙度 | 44% |
中值孔径 | 13μm |
在65和1000℃之间的平均热膨胀系数 | 1.3×10-6/℃ |
通过使用Micromeritics 9500孔率计进行高压水银孔率法分析,测量孔隙度特性。
然后,通过将整料浸渍在含聚合物的溶液中并且然后干燥,进行整料浸渍。
在对比例C1-C5的情况下,使用的聚合物是聚乙烯醇,由Celanese
Corporation在标注Celvol 205下销售。它的水解度大于88%。在对比例C4和C5的情况下,使用柠檬酸将聚合物交联。
对比例C6相应于未钝化的整料(因此没有沉积聚合物)。
在实施例1和2的情况下,聚合物是聚乙烯基吡咯烷酮,平均分子量58000g/mol。
在实施例3至7的情况下,聚合物是聚乙烯基吡咯烷酮,平均分子量30000g/mol。所使用的溶液是由BASF在标注Luvitec K30下销售。对于实施例4,通过添加NaOH,使溶液达到pH值为10。
以下表3表明:
-干燥时间和干燥温度,分别地由t和T表示;
-浸渍溶液的浓度,由C表示并且以相对于溶液量的聚合物的重量百分比表示;
-实际沉积的聚合物(钝化材料)的量,以重量百分比计,由Q表示;
-钝化后的水吸收,由P表示,以重量百分比表示;
-氧化铝吸收,由A表示,以重量百分比表示;和
-具有其催化涂层的载体的平均热膨胀系数,由TEC表示并且以10-6/℃表示。
使用钝化后的水吸收来估算可以被固定到载体上的催化剂的量,和因此载体和未来催化涂层之间的亲合力。测量方法在于将钝化的载体浸渍在水中并且然后使其末端之一经受突然的抽吸操作以便仅仅将水膜留在壁的表面上。高剩余水量的特征在于在未来催化涂层和载体之间的强化学亲合力,并且因此固定更多催化涂层的可能性。这样的方法描述于专利申请EP
1462171中。
氧化铝吸收(A)是按以下方式测量的:通过下述方式制备20wt%勃姆石溶液:将200g的勃姆石(Dispersal®,由Sasol提供)悬浮在1升的蒸馏水中,添加浓(52%)硝酸来酸化溶液直到达到pH=2,和通过强烈搅拌2小时获得分散体。然后,通过将整料浸渍在该溶液中1分钟,来浸渍整料,在整料上存在的过量的溶液通过用压缩空气将其吹扫(blast)而除去。该部分然后在空气中在120℃干燥2小时,然后在500℃在空气中煅烧2小时以便形成氧化铝涂层。氧化铝吸收相应于相当于氧化铝涂层的质量的增加。
根据NF B40-308标准,以5℃/分钟的温度升高,通过差示热膨胀测量法在65℃和1000℃之间测量平均热膨胀系数(TEC)。通过从与整料的挤出方向平行的平面中的蜂窝状物中切出材料样本而获得所测试的材料样本。它的维度是大约5mm×5mm×15mm。在勃姆石沉积和煅烧后进行测量以便模拟在煅烧后催化涂层具有非常小尺寸(即,约10nm)的微晶的效果。
重量增加或重量损失(Q,P,A,L)以相对于浸渍前的干燥载体的重量的重量百分比表示。
表
3
t(小时) | T(℃) | C | Q | P | A | TEC | |
C1 | 3 | 105 | 10 | 2.3 | 11 | ||
C2 | 3 | 105 | 5 | 1.4 | 14 | ||
C3 | 3 | 105 | 2 | 0.5 | 16 | 2.0 | 4.5 |
C4 | 3 | 105 | 5 | 1.5 | 7 | ||
C5 | 3 | 105 | 2 | 0.7 | 8 | ||
C6 | - | - | - | 0 | 23 | 2.8 | 5.3 |
1 | 3 | 105 | 5 | 0.9 | 25 | ||
2 | 3 | 105 | 2 | 0.3 | 25 | ||
3 | 3 | 105 | 10 | 2.6 | 23 | ||
4 | 3 | 105 | 10 | 2.7 | 23 | ||
5 | 1 | 130 | 10 | 2.7 | 25 | ||
6 | 1 | 150 | 10 | 4 | 26 | ||
7 | 1 | 160 | 10 | 2.3 | 25 | 2.9 | 3.1 |
这些结果表明使用聚乙烯基吡咯烷酮代替聚乙烯醇显著地改善了载体和钝化后沉积的催化涂层之间的亲合性。其原因在于根据本发明的实施例的水吸收的水平比实施例C1-C5高很多并且非常类似于未钝化结构。
聚乙烯基吡咯烷酮的钝化效果,以实施例7举例说明,是特别有利的,因为钝化并且然后具有其催化涂层的载体的热膨胀系数相比于在沉积催化涂层前的未钝化载体(实施例C6)来说,降低了达多于40%。聚乙烯基吡咯烷酮的钝化效果也超过聚乙烯醇(实施例C3)。
以下表4举例说明干燥温度对聚合物粘合到载体的影响。
不同于实施例7,实施例9和11分别地在170℃和190℃进行干燥。
不同于实施例7和9,分别地在实施例8和10中,以相对于聚乙烯基吡咯烷酮的重量5%wt的数量,将3-氨基丙基三甲氧基甲硅烷(99%纯度,由Sigma Aldrich提供)添加到该溶液。
除已经描述的参数外,表4包括由L表示的参数,其相应于在室温下将干燥载体浸在水里1分钟并且然后在105℃在空气中干燥后的重量损失。
表
4
t(小时) | T(℃) | C(wt%) | Q(wt%) | P(wt%) | L(wt%) | |
3 | 3 | 105 | 10 | 2.6 | 23 | 2.5 |
5 | 1 | 130 | 10 | 2.7 | 25 | 1.2 |
7 | 1 | 160 | 10 | 2.3 | 25 | 0.6 |
8 | 1 | 160 | 10 | 2.4 | 26 | 0.3 |
9 | 1 | 170 | 10 | 2.5 | 22 | 0.6 |
10 | 1 | 170 | 10 | 2.7 | 21 | 0.2 |
11 | 1 | 190 | 10 | 2.8 | 17 | 0.2 |
这些结果表明较高的干燥温度导致钝化聚合物层对载体的更好的粘合,因为当干燥温度增加后,在载体浸渍后的重量损失(L)降低。然而,对于最高的干燥温度,这也导致与未来催化涂层的亲合性降低,因为当干燥温度增加时,钝化后的水吸收(P)也降低。因此,130-170℃,或实际上130-160℃的干燥温度构成最佳方案。
实施例8-10与实施例7-9的比较分别地表明添加少量的甲硅烷进一步改进了聚合物层与载体的粘合性。
Claims (15)
1.
由多孔无机材料制成的催化剂载体,其用于处理废气,具有蜂窝状结构,该结构的面之一用于吸入待处理的废气并且另一个面用于排出处理过的废气,所述结构包括,在这些吸入和排出面之间,被多孔壁分开的互相平行轴的相邻管或通道的阵列,所述载体被在至少部分的它的内表面上涂布以至少一种乙烯基吡咯烷酮聚合物或共聚物。
2.
前述权利要求的载体,其中通道在末端中的一个或其它处交替地被密封以便滤出废气中所含的颗粒物或灰粒。
3.
前述权利要求中一项的载体,使得多孔无机材料选自钛酸铝,堇青石和富铝红柱石。
4.
前述权利要求中一项的载体,使得乙烯基吡咯烷酮聚合物或共聚物选自聚乙烯基吡咯烷酮,乙烯基吡咯烷酮/乙酸乙烯酯共聚物,乙烯基吡咯烷酮/乙烯基咪唑共聚物和乙烯基吡咯烷酮/乙烯基己内酰胺共聚物,或它们的混合物中的任一种。
5.
前述权利要求中一项的载体,被在至少部分的它的内表面上涂布以至少一种硅烷型化合物,尤其具有至少一个具有至少一种亲核基团的碳链的硅烷型化合物。
6.
前述权利要求中一项的载体,被在至少部分的其表面上涂布以催化涂层。
7.
前述权利要求的载体,使得催化涂层包括基础材料和催化剂。
8.
前述权利要求的载体,使得基础材料是比表面积为约10-100m2/g的无机材料。
9.
一种用于获得前述权利要求中一项的由多孔无机材料制成的催化剂载体的方法,包括其中在所述载体上沉积乙烯基吡咯烷酮聚合物或共聚物的步骤,随后干燥步骤。
10.前述权利要求的方法,其中通过液体,尤其水性溶液或分散体的浸渍,沉积了乙烯基吡咯烷酮聚合物或共聚物。
11.前述权利要求的方法,使得在溶液或分散体中乙烯基吡咯烷酮聚合物或共聚物的重量含量为1-30%,优选地5-15%。
12.前述方法权利要求中任一项的方法,使得乙烯基吡咯烷酮聚合物或共聚物的平均分子量为10000-1000000g/mol,尤其20000-100000g/mol。
13.前述方法权利要求中任一项的方法,使得干燥步骤在至少100℃,尤其130-170℃的温度下进行。
14.前述方法权利要求中任一项的方法,随后沉积催化涂层的步骤,和然后煅烧步骤。
15.通过前述权利要求的方法可以获得的催化剂载体。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0952493 | 2009-04-16 | ||
FR0952493 | 2009-04-16 | ||
PCT/FR2010/050720 WO2010119226A1 (fr) | 2009-04-16 | 2010-04-14 | Substrat de catalyseur en nid d'abeilles et son procédé d'obtention |
Publications (1)
Publication Number | Publication Date |
---|---|
CN102395429A true CN102395429A (zh) | 2012-03-28 |
Family
ID=41136803
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2010800169560A Pending CN102395429A (zh) | 2009-04-16 | 2010-04-14 | 蜂窝状催化剂载体及其生产方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US20120021895A1 (zh) |
EP (1) | EP2419211A1 (zh) |
JP (1) | JP2012523954A (zh) |
KR (1) | KR20110138241A (zh) |
CN (1) | CN102395429A (zh) |
MX (1) | MX2011010797A (zh) |
WO (1) | WO2010119226A1 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102584186A (zh) * | 2012-01-12 | 2012-07-18 | 刘光文 | 一种红柱石蜂窝废气净化催化剂载体的制备方法 |
CN109414691A (zh) * | 2016-07-14 | 2019-03-01 | 揖斐电株式会社 | 蜂窝结构体和该蜂窝结构体的制造方法 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013126491A1 (en) * | 2012-02-21 | 2013-08-29 | Georgetown University | Polyvinylpyrrolidone (pvp) for enhancing the activity and stability of platinum-based electrocatalysts |
JP2018027508A (ja) * | 2015-01-07 | 2018-02-22 | 住友化学株式会社 | ハニカムフィルタの製造方法 |
KR102498089B1 (ko) * | 2022-11-08 | 2023-02-10 | 에널텍티엠에스(주) | Toc 수질측정기에 사용되는 백금 코팅 허니컴 촉매 제조방법 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU1614000A (en) * | 1998-11-12 | 2000-06-05 | Abb Lummus Global Inc. | Attrition resistant thin film catalyst and method of preparation |
JP2003175307A (ja) * | 1999-12-24 | 2003-06-24 | Asahi Glass Co Ltd | 窒化ケイ素フィルタおよびその製造法 |
DE10322182A1 (de) * | 2003-05-16 | 2004-12-02 | Blue Membranes Gmbh | Verfahren zur Herstellung von porösem, kohlenstoffbasiertem Material |
US7166555B2 (en) * | 2005-02-14 | 2007-01-23 | Corning Incorporated | Coated ceramic catalyst supports and method |
KR100871898B1 (ko) * | 2005-10-28 | 2008-12-05 | 에스케이에너지 주식회사 | 디젤 엔진의 배기가스 정화 장치 |
DE102007023120A1 (de) * | 2007-05-16 | 2008-11-20 | Robert Bosch Gmbh | Verfahren zur Herstellung eines Filters sowie Filter |
-
2010
- 2010-04-14 US US13/259,273 patent/US20120021895A1/en not_active Abandoned
- 2010-04-14 KR KR1020117024191A patent/KR20110138241A/ko not_active Application Discontinuation
- 2010-04-14 MX MX2011010797A patent/MX2011010797A/es not_active Application Discontinuation
- 2010-04-14 WO PCT/FR2010/050720 patent/WO2010119226A1/fr active Application Filing
- 2010-04-14 JP JP2012505208A patent/JP2012523954A/ja active Pending
- 2010-04-14 EP EP10723674A patent/EP2419211A1/fr not_active Withdrawn
- 2010-04-14 CN CN2010800169560A patent/CN102395429A/zh active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102584186A (zh) * | 2012-01-12 | 2012-07-18 | 刘光文 | 一种红柱石蜂窝废气净化催化剂载体的制备方法 |
CN109414691A (zh) * | 2016-07-14 | 2019-03-01 | 揖斐电株式会社 | 蜂窝结构体和该蜂窝结构体的制造方法 |
Also Published As
Publication number | Publication date |
---|---|
WO2010119226A1 (fr) | 2010-10-21 |
JP2012523954A (ja) | 2012-10-11 |
KR20110138241A (ko) | 2011-12-26 |
EP2419211A1 (fr) | 2012-02-22 |
MX2011010797A (es) | 2011-10-28 |
US20120021895A1 (en) | 2012-01-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9321694B2 (en) | Method for applying discriminating layer onto porous ceramic filters via gas-borne prefabricated porous assemblies | |
US9745227B2 (en) | Method for applying discriminating layer onto porous ceramic filters | |
EP1982767B1 (en) | Honeycomb segment, honeycomb structure and process for producing the same | |
US6939825B1 (en) | Carrier for catalyst and method for preparing the same | |
EP3505244B1 (en) | Honeycomb structure, honeycomb structure type catalyst, and production methods therefor | |
EP1679109B1 (en) | Ceramic honeycomb filter and method for production thereof, and sealing material for ceramic honeycomb filter | |
EP1243335A1 (en) | Catalyst and method for preparation thereof | |
JP5455637B2 (ja) | ハニカム構造体の製造方法およびハニカム構造体 | |
EP1550494A1 (en) | Honeycomb structure | |
EP2364200A1 (en) | Coated particulate filter and method | |
CN102395429A (zh) | 蜂窝状催化剂载体及其生产方法 | |
EP2143694B1 (en) | Honeycomb structure | |
JP2010513206A (ja) | 炭化珪素基材の多孔構造を得る方法 | |
JP3414445B2 (ja) | パティキュレートフィルタとその製造方法 | |
JP2011527938A (ja) | 触媒用途のためのテクスチャが形成された微粒子フィルター | |
JP2024503481A (ja) | 触媒活性微粒子フィルタ本体及びその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120328 |