CN101678352A - 蜂窝结构体 - Google Patents
蜂窝结构体 Download PDFInfo
- Publication number
- CN101678352A CN101678352A CN200880019932A CN200880019932A CN101678352A CN 101678352 A CN101678352 A CN 101678352A CN 200880019932 A CN200880019932 A CN 200880019932A CN 200880019932 A CN200880019932 A CN 200880019932A CN 101678352 A CN101678352 A CN 101678352A
- Authority
- CN
- China
- Prior art keywords
- honeycomb structured
- structured body
- zeolite
- cellular unit
- cell walls
- 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
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 73
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000010457 zeolite Substances 0.000 claims abstract description 73
- 210000002421 cell wall Anatomy 0.000 claims abstract description 61
- 230000003746 surface roughness Effects 0.000 claims abstract description 43
- 239000011230 binding agent Substances 0.000 claims abstract description 31
- 230000001413 cellular effect Effects 0.000 claims description 118
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 8
- 239000000499 gel Substances 0.000 claims description 7
- 238000005342 ion exchange Methods 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000004113 Sepiolite Substances 0.000 claims description 4
- 229960000892 attapulgite Drugs 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000006193 liquid solution Substances 0.000 claims description 4
- -1 modenite Substances 0.000 claims description 4
- 229910052625 palygorskite Inorganic materials 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- 229910052624 sepiolite Inorganic materials 0.000 claims description 4
- 235000019355 sepiolite Nutrition 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims description 3
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 3
- 239000012013 faujasite Substances 0.000 claims description 3
- 229910001657 ferrierite group Inorganic materials 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 210000004027 cell Anatomy 0.000 abstract description 25
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 23
- 239000000203 mixture Substances 0.000 description 18
- 238000001125 extrusion Methods 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- 239000002912 waste gas Substances 0.000 description 13
- 239000010954 inorganic particle Substances 0.000 description 12
- 239000002002 slurry Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000005238 degreasing Methods 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229920000609 methyl cellulose Polymers 0.000 description 5
- 239000001923 methylcellulose Substances 0.000 description 5
- 235000010981 methylcellulose Nutrition 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000002093 peripheral effect Effects 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 238000010304 firing Methods 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 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 description 1
- 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 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- WTHDKMILWLGDKL-UHFFFAOYSA-N urea;hydrate Chemical compound O.NC(N)=O WTHDKMILWLGDKL-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- 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
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
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- 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
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- 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
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
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Abstract
本发明提供一种蜂窝结构体,其由包含沸石以及无机粘结剂的蜂窝单元构成,该蜂窝单元具有沿长度方向从第一端面延伸至第二端面的多个孔道被孔道壁分隔的柱状形状,所述蜂窝结构体的特征在于:所述沸石在所述蜂窝单元的单位表观体积中的含量为230g/L以上;所述蜂窝单元的开口率P在50~65%的范围;所述蜂窝单元具有31~93个/cm2的孔道密度ρ;所述孔道壁的表面粗糙度Ra在1μm~30μm的范围。
Description
技术领域
本发明涉及一种用于处理废气的蜂窝结构体。
背景技术
关于汽车废气的净化,已经开发了很多技术,但是,由于交通量也在增加,所以还很难说已经采取了完善的废气应对方法。无论在日本国内还是在世界范围内,都在进一步加强对汽车废气的控制。其中,对于柴油废气中的NOX的控制要求正在变得非常严格。目前为止,一般通过控制发动机的燃烧系统来谋求减少NOX,但是,仅使用该方法并不能百分之百地减少NOX。作为应对该问题的柴油NOX净化系统,已经提出了一种将氨作为还原剂来使用的NOX还原系统(被称为SCR(选择性催化还原)系统)。作为应用于这种系统中的催化剂载体,众所周知的有蜂窝结构体。
上述蜂窝结构体具有例如沿长度方向从该蜂窝结构体的一个端面延伸至另一个端面的多个孔道(贯穿孔),这些孔道被担载了催化剂的孔道壁相互分隔。因此,当使废气在这样的蜂窝结构体中流通时,废气中含有的NOx被孔道壁中担载的催化剂所改质,所以,就能够对废气进行处理。
一般来说,上述蜂窝结构体的孔道壁由堇青石构成;在该孔道壁中,作为催化剂,例如可担载沸石(用铁或铜等进行了离子交换的沸石)。另外,还有在孔道壁中使用沸石并形成蜂窝结构体的提议(例如,专利文献1——“国际公开第2005/063653号小册子”)。
在上述蜂窝结构体中,还需要进一步提高NOx净化率。一般来说,为了提高蜂窝结构体的NOx净化率,通过减小蜂窝结构体的开口率来增大用于反应的孔道壁的表面面积的方法较为有效。但是,如果减小蜂窝结构体的开口率,则会产生压力损失过大的问题。因此,一般情况下,并不能使蜂窝结构体的开口率发生变化。
发明内容
本发明是鉴于上述问题而提出的,其目的在于提供一种蜂窝结构体,该蜂窝结构体与现有的蜂窝结构体相比,可以不使蜂窝结构体的开口率发生显著的变化,并具有良好的NOx净化率。
在本发明中,蜂窝结构体由包含沸石和无机粘结剂的蜂窝单元构成,该蜂窝单元具有沿长度方向从第一端面延伸至第二端面的多个孔道被孔道壁分隔的柱状形状,所述蜂窝结构体的特征在于:所述沸石在所述蜂窝单元的单位表观体积中的含量为230g/L以上;所述蜂窝单元的开口率P在50%~65%的范围;所述蜂窝单元具有31~93个/cm2的孔道密度ρ;所述孔道壁的表面粗度Ra在1μm~30μm的范围。
优选的,所述沸石在所述蜂窝单元的单位表观体积中的含量为270g/L以下。
这里,所述蜂窝单元中包含的沸石可为β型沸石、Y型沸石、镁碱沸石、ZSM-5型沸石、丝光沸石、八面沸石、A型沸石或者L型沸石。
另外,在所述沸石中,二氧化硅与氧化铝的重量比可在30~50的范围。
另外,所述沸石可用Fe、Cu、Ni、Co、Zn、Mn、Ti、Ag或者V进行了离子交换。
另外,所述蜂窝单元可包含从由氧化铝颗粒、二氧化钛颗粒、二氧化硅颗粒、氧化锆颗粒以及这些颗粒的前驱体构成的组中选定的至少一种。
另外,所述蜂窝单元中包含的无机粘结剂可包含从由氧化铝胶体溶液、二氧化硅胶体溶液、二氧化钛胶体溶液、水玻璃、海泡石以及绿坡缕石构成的组中选定的至少一种材料。
另外,所述蜂窝单元还可包含无机纤维。
所述无机纤维可为从由氧化铝、二氧化硅、碳化硅、硅铝、玻璃、钛酸钾以及硼酸铝构成的组中选定的至少一种纤维。
所述蜂窝结构体是通过粘结层将多个所述蜂窝单元结合在一起而构成的。
根据本发明,其效果在于可提供一种蜂窝结构体,该蜂窝结构体与现有的蜂窝结构体相比,可以不使蜂窝结构体的开口率发生显著的变化,并具有良好的NOx净化率。
附图说明
图1是本发明的蜂窝结构体的一个例子的立体示意图。
图2是构成图1的蜂窝结构体的蜂窝单元的一个例子的立体示意图。
图3是本发明的蜂窝结构体的其他例子的立体图。
图4是实施例和比较例的表面粗度Ra与NOx净化率之间的关系图。
主要符号说明:
100、200:蜂窝结构体;110:第一端面;115:第二端面;120:涂层;121、122:孔道;123、124:孔道壁;130:蜂窝单元;150:粘结层。
具体实施方式
以下参考附图说明本发明的实施方式。
图1是本发明的蜂窝结构体的示意图。另外,图2是图1所示的蜂窝结构体的基本单位的蜂窝单元的一个例子的示意图。
如图1所示,本发明的蜂窝结构体100具有两个端面110和115。另外,蜂窝结构体100的除了两个端面之外的外周面上形成了涂层120。
蜂窝结构体100例如可由如下方法制成,即:首先通过粘结层150将多个(图1的例中,纵横各4列共16个)图2所示的柱状的陶瓷制蜂窝单元130结合在一起,然后依照预定的形状(图1的例中为圆柱形状)对外周侧进行切削加工。
如图2所示,蜂窝单元130具有沿蜂窝单元长度方向从一端延伸至另一端并在两个端面开口的多个孔道(贯穿孔)121以及用于分隔该孔道的孔道壁123。这里,需要说明的是,蜂窝单元130作为SCR系统,包含有助于NOx净化反应的沸石。因此,将本发明的蜂窝结构体作为NOx净化用催化剂载体来使用时,不一定非得在孔道壁上担载贵金属催化剂。但是,当然也可以在孔道壁上担载贵金属催化剂。沸石在蜂窝单元中的含量较好为230g/L以上,更好为270g/L以下。
这样构成的蜂窝结构体100例如可作为具有尿素罐的尿素SCR系统的催化剂单体来使用。在这种尿素SCR系统中,废气流通时,收容在尿素罐中的尿素与废气中的水发生反应,生成氨。
CO(NH2)2+H2O→2NH3+CO2 式(1)
当生成的氨与含有NOx的废气一起从蜂窝结构体100的一个端面(例如,端面110)流入各孔道时,在孔道壁中含有的沸石上,该混合气体之间发生如下反应。
4NH3+4NO+O2→4N2+6H2O 式(2-1)
8NH3+6NO2→7N2+12H2O 式(2-2)
2NH3+NO+NO2→2N2+3H2O 式(2-3)
之后,被净化了的废气从蜂窝结构体100的另一端面(例如,端面115)被排出。这样,通过使废气在蜂窝结构体100内流通,就可以处理废气中的NOx。另外,这里尽管揭示了通过对尿素水进行加水分解来提供NH3的方法,但是也可以采用其他方法来提供NH3。
在这样的蜂窝结构体中,还需要进一步提高NOx的净化率。
一般来说,为了提高NOx净化率,减小蜂窝单元的开口率P,增加沸石的单位体积含量的方法较为有效。但是,如果蜂窝单元的开口率P降低,则会发生压力损失增大等的问题。因此,实际上,蜂窝单元的开口率P由于受到蜂窝结构体的特性上的制约,不能对其进行较大的变动。一般情况下,蜂窝单元的开口率P在50~65%的范围。
因此,在本发明中,对蜂窝单元的孔道密度ρ和孔道壁表面粗度Ra这两个特性进行控制。
蜂窝单元的孔道密度ρ和孔道壁表面粗度Ra对孔道壁的表面面积的影响很大。例如,通过使蜂窝单元的孔道密度ρ增加(ρ≥31个/cm2),可以增加孔道壁的表面面积,这样,就可以增加产生上述式(2-1)、式(2-2)和式(2-3)那样的NOx净化反应的区域。但是,如果极端地增加孔道密度ρ(ρ≥94个/cm2),则在具有那样的蜂窝单元的蜂窝结构体中,会发生压力损失极端地增大,同时孔道壁变得过薄,导致强度降低的问题。因此,在本发明中,孔道密度ρ被控制在31个/cm2≤ρ≤93个/cm2的范围。特别地,孔道密度ρ优选为在47个/cm2≤ρ≤78个/cm2的范围。
同样,通过增加孔道壁的表面粗度Ra(Ra≥1μm),可以增加孔道壁的表面面积,这样,就可以增加产生上述式(2-1)、式(2-2)和式(2-3)那样的NOx净化反应的区域。但是,如果极端地增大孔道壁的表面粗度Ra(Ra≥40μm),则在具有那样的蜂窝单元的蜂窝结构体中,会发生NOx净化率降低的问题。其原因可被推测为,废气很难浸透至孔道壁的内部。因此,在本发明中,孔道壁的表面粗度Ra被控制在1μm≤Ra ≤30μm的范围。特别地,孔道壁的表面粗度Ra优选为在20μm≤Ra≤30μm的范围。
这里,需要说明的是,在本发明中,表面粗度Ra是指JISB0601(第4.2.1章)规定的所谓“算术平均高度”,即:标准长度的Z(x)(任意位置x的轮廓线的高度)的绝对值的平均值。在本发明中,表面粗度Ra是通过如下方法算出的,即:首先从对象样品的表面任意切出5个部分,在这5个部分上分别测定孔道壁的表面粗度Ra,然后计算其平均值。表面粗度计使用了SV-C3100(Mitutoyo公司制)。
这样,在本发明中,蜂窝单元的孔道密度ρ和孔道壁的表面粗度Ra就被控制在适当的范围。因此,在本发明中,蜂窝单元的开口率与现有蜂窝单元的开口率相比几乎没有变化(50%≤P≤65%),并且可以使具有那样的蜂窝单元的蜂窝结构体的NOx净化率显著提高。
这里,蜂窝单元130除了沸石之外还包含无机粘结剂。
沸石例如为β型沸石、Y型沸石、镁碱沸石、ZSM-5型沸石、丝光沸石、八面沸石、A型沸石或者L型沸石。另外,沸石可为由Fe、Cu、Ni、Co、Zn或者Mn进行了离子交换的沸石。另外,沸石中的二氧化硅与氧化铝的重量比最好在30~50的范围。
作为无机粘结剂可以使用无机胶体溶液或粘土系列粘结剂等,作为上述无机胶体溶液的具体实例,例如可以是氧化铝胶体溶液、二氧化硅胶体溶液、二氧化钛胶体溶液、水玻璃等;另外,作为粘土系列粘结剂,例如可以是白土、高岭土、蒙脱土、海泡石以及绿坡缕石等多链结构型粘土等。这些物质可以单独使用,也可以2种以上混合使用。
在这些物质中,最好使用由氧化铝胶体溶液、二氧化硅胶体溶液、二氧化钛胶体溶液、水玻璃、海泡石以及绿坡缕石所构成的组中选定的至少一种物质。
为了提高蜂窝单元的强度,还可以包含除了沸石之外的无机颗粒和/或无机纤维。作为除了沸石之外的无机颗粒,最好是氧化铝颗粒、二氧化硅颗粒、氧化锆颗粒、二氧化钛颗粒、二氧化铈颗粒、莫来石颗粒等,也可以是这些颗粒的前躯体。这些颗粒可以单独使用,也可以2种以上混合使用。另外,特别地,在这些颗粒中,优选为氧化铝颗粒和氧化锆颗粒。
另外,如果向蜂窝单元添加无机纤维,则作为无机纤维的材料,最好是氧化铝、二氧化硅、碳化硅、硅铝、玻璃、钛酸钾或者硼酸铝等。这些材料可以单独使用,也可以2种以上混合使用。在上述材料中,优选为氧化铝。无机纤维也包含须晶。
另外,关于蜂窝单元内含有的无机颗粒(沸石和除了沸石之外的无机颗粒)的总量(相对于蜂窝单元的重量比),其下限较好为30重量%,更好为40重量%,最好为50重量%;另外,其上限较好为90重量%,更好为80重量%,最好为75重量%。如果无机颗粒(沸石和除了沸石之外的无机颗粒)的含量小于30重量%,则有助于NOx净化的沸石的含量相对地变少;另外,如果超过90重量%,则蜂窝单元的强度可能降低。
无机粘结剂的含量以固体成分计较好为5重量%以上,更好为10重量%以上,最好为15重量%以上;另外,无机粘结剂的含量以固体成分计较好为50重量%以下,更好为40重量%以下,最好为35重量%以下。如果无机粘结剂的含量小于5重量%,则制成的蜂窝单元的强度有可能变低;另外,如果无机粘结剂的含量大于50重量%,则原料组合物的成型性有可能下降。
蜂窝单元内含有无机纤维时,关于无机纤维的总量,其下限较好为3重量%,更好为5重量%,最好为8重量%;另外,其上限较好为50重量%,更好为40重量%,最好为30重量%。如果无机纤维的含有量小于3重量%,则对提高蜂窝单元的强度的作用变小;如果大于50重量%,则有助于NOx净化的沸石量相对地变少。
对与上述蜂窝单元130的长度方向垂直的截面形状并无特别限定,只要可以通过粘结层将蜂窝单元结合在一起,可为任何形状。蜂窝单元130的形状可为正方形、长方形、六边形、扇形等。
另外,对与蜂窝单元130的孔道121的长度方向垂直的截面形状并无特别限定,除了正方形之外,例如可为三角形、多边形。
对蜂窝单元130的孔道壁123的厚度并无特别限定,从强度的角度来看,其下限最好为0.1mm;从NOx净化性能的观点来看,其上限最好为0.4mm。
本发明的蜂窝结构体100的形状可为任何形状。例如,蜂窝结构体100的形状除了图1所示的圆柱形之外,还可为椭圆柱形、四棱柱形、多棱柱形等。
蜂窝结构体100的粘结层150通过将粘结层用浆体作为原料来形成。作为粘结层用浆体,对其并无特别限定,例如可使用无机颗粒和无机粘结剂的混合物、无机粘结剂和无机纤维的混合物、无机颗粒、无机粘结剂以及无机纤维的混合物等。另外,还可以在这些混合物中添加有机粘结剂。
作为无机颗粒、无机粘结剂以及无机纤维,可以使用与构成上述蜂窝单元的材料同样的材料。另外,作为有机粘结剂,对其并无特别限定,例如可以是从聚乙烯醇、甲基纤维素、乙基纤维素以及羧甲基纤维素等选出的一种以上的有机粘结剂。在这些有机粘结剂中,优选为羧甲基纤维素。
粘结层的厚度最好在0.3~2mm的范围。如果粘结层的厚度小于0.3mm,则有可能不能得到足够的结合强度;另外,如果粘结层的厚度大于2mm,则压力损失有可能变大。这里,需要说明的是,对结合的蜂窝单元的数量可参考蜂窝结构体的大小进行适当的选定。
蜂窝结构体100的外周涂层120是通过将包含与构成上述蜂窝单元的材料相同的无机颗粒、无机粘结剂以及无机纤维,另外还包含有机粘结剂的浆体作为原料来形成的。外周涂层120可以是与粘结层150相同的材料,也可以是不同的材料,但最好是相同的材料。其原因在于,如果与粘结层一样,就不容易发生剥离或断裂等。在作为原料的浆体中,根据实际要求,可以添加造孔剂;该造孔剂可以是以氧化物系列陶瓷为成分的微小中空球体(即空心球)、球状丙烯酸树脂颗粒、石墨等。外周涂层的最终厚度最好为0.1mm~2.0mm。
在上述记载中,以图1所示的、通过粘结层150将多个蜂窝单元130结合在一起所构成的蜂窝结构体为例进行了说明。
图3所示为本发明的蜂窝结构体的另一例子。这里,需要说明的是,蜂窝结构体200除了是由多个孔道122隔着孔道壁124沿长度方向并排设置的一个蜂窝单元所构成的之外,与蜂窝结构体100相同。另外,需要说明的是,在图3的例子中,蜂窝结构体200的外周面上形成了外周涂层120,但是,可以形成该外周涂层,也可以不形成该外周涂层。
(蜂窝结构体的制作方法)
下面,对本发明的蜂窝结构体的制造方法进行说明。另外,需要说明的是,这里以上述图1所示的、由多个蜂窝单元所构成的蜂窝结构体100的制造方法为例进行说明。
首先,使用以包含沸石的无机颗粒、无机粘结剂为主成分,再根据实际要求添加了无机纤维的原料浆,通过实行使用模具的挤压成型等,制成蜂窝单元的成型体。
在原料浆中,除了上述物质之外,考虑成型性,还可以适当地添加有机粘结剂、分散介质以及成型助剂。作为有机粘结剂,对其并无特别限定,例如可以是从甲基纤维素、羧甲基纤维素、羟乙基纤维素、聚乙二醇、酚醛树脂以及环氧树脂等中选出的一种以上的有机粘结剂。无机颗粒、无机粘结剂以及无机纤维的合计为100重量份时,有机粘结剂的混合量最好为1~10重量份。
作为分散介质,对其并无特别限定,例如可以是水、有机溶剂(甲苯等)以及醇(甲醇等)等。作为成型助剂,对其并无特别限定,例如可以是乙二醇、糊精、脂肪酸、脂肪酸皂以及多元醇等。
对原料浆并无特别限定,最好对其进行混合和混炼,例如,可以使用搅拌机或磨碎机等来混合,也可以使用捏合机等来进行充分的混炼。对原料浆的成型方法并无特别限定,例如,最好使用挤压成型等,将其成型为具有孔道的形状。
其次,最好对得到的成型体进行干燥。对用来进行干燥的干燥机并无特别限定,可以是微波干燥机、热风干燥机、高频干燥机、减压干燥机、真空干燥机以及冷冻干燥机等。另外,最好对干燥后的成型体进行脱脂。对脱脂条件并无特别限定,可以根据成型体中含有的有机物的种类或含量进行适当的选择,最好为大约400℃、2个小时。然后,最好对得到的成型体进行烧成。对烧成条件并无特别限定,较好为600~1200℃,最好为600~1000℃。其理由在于,如果烧成温度小于600℃,则不能进行烧结,蜂窝单元的强度下降;如果大于1200℃,则烧结过度进行,沸石的反应点减少。
另外,需要说明的是,在通过上述的挤压成型制作蜂窝单元成型体的工序中,可以通过事先设计模具以使成型体的孔道尺寸、孔道壁厚度变为适当值的方式,容易地对蜂窝单元的孔道密度ρ进行控制。另外,可以通过事先调整上述模具的、用于对蜂窝单元的孔道壁进行定形的部分的表面粗度的方式,容易地对蜂窝单元的孔道壁的表面粗度Ra进行控制。
接下来,在由上述工序所得到的蜂窝单元的侧面,厚度均匀地涂敷粘结层用浆体,该粘结层用浆体随后将变为粘结层;之后,通过该粘结层用浆体,顺序地将其他蜂窝单元层叠在一起。重复该工序,制成具有想要的尺寸(例如,蜂窝单元被排列成纵横各4列)的蜂窝结构体。
接下来,对上述蜂窝结构体进行加热,在通过使粘结层用浆体干燥、固化以形成粘结层的同时,使蜂窝单元相互粘结固定在一起。
接下来,使用金刚石刀具等,将蜂窝结构体切削加工成例如圆柱状,制成具有想要的外周形状的蜂窝结构体。也可以制作多个不同形状的蜂窝单元(外周具有孔道壁),然后通过粘结层来形成蜂窝结构体。此时,可省略切削工序。
接下来,在蜂窝结构体的外周面(侧面)涂敷外周涂层用浆体,之后,将其干燥、固化,形成外周涂层。
通过粘结层使多个蜂窝单元结合后(但是,如果设有外周涂层,则使外周涂层形成后),最好对该蜂窝结构体进行脱脂。通过该处理,如果粘结层用浆体以及涂层用浆体中含有有机粘结剂,则可以脱脂除去这些有机粘结剂。脱脂条件可以根据含有的有机物的种类或含量进行适当的选择,一般情况下,可为700℃、2个小时左右。
通过上述工序就可以制成如图1所示的蜂窝结构体。
实施例
下面通过实施例对本发明进行详细的说明。
(实施例1)
首先,将2600重量份的Fe沸石颗粒(平均粒径为2μm)、2600重量份的氧化铝胶体溶液、780重量份的氧化铝纤维(平均纤维长度为100μm、平均纤维直径为6μm)、410重量份的甲基纤维素混合(下面,将该混合比称为“混合比A”)。其次,在此混合物中再混合可塑剂和润滑剂(unilub),通过混炼得到混合组成物。Fe沸石颗粒是沸石重量的3wt%被Fe进行了离子交换的Fe沸石颗粒。Fe离子交换是通过将沸石颗粒含浸在硝酸铁铵溶液中进行的。硝酸铁铵溶液的浓度被调整为可以使沸石含有3wt%的铁。另外,沸石使用β型沸石。离子交换量使用ICPS~8100(岛津制作所制)装置通过IPC发光分析法来求得。
其次,使用挤压成型机对上述混合组合物进行挤压成型,得到蜂窝单元成型体。
接下来,使用微波干燥机和热风干燥机对得到的这些成型体进行充分干燥,并在400℃下保持2个小时进行脱脂。之后,在700℃下保持2小时进行烧成,制成实施例1的蜂窝单元(纵35mm×横35mm,全长为150mm)。孔道壁的厚度为0.33mm(13mil),孔道密度ρ为34个/cm2(220cpsi),孔道壁的表面粗度Ra为1μm。另外,开口率为65%。蜂窝单元中含有的单位表观体积的沸石含量为250g/L。
接下来,将得到的蜂窝单元切断成直径30mmφ×长度50mm的大小,作为评价用样品,进行下面的实验。
(实施例2)
通过与实施例1同样的方法制得蜂窝单元。但是,在实施例2中,通过使用表面粗度等与实施例1的模具不同的模具进行挤压成型来制成蜂窝单元。孔道壁厚度为0.33mm(13mil),孔道密度ρ为34个/cm2(220cpsi),孔道壁的表面粗度Ra为10μm。另外,开口率为65%。蜂窝单元中含有的单位表观体积的沸石含量为250g/L。
(实施例3)
首先,将1900重量份的Fe沸石颗粒(平均粒径为2μm)、1100重量份的氧化铝颗粒(平均粒径为2μm)、2600重量份的氧化铝胶体溶液、780重量份的氧化铝纤维(平均纤维长度为100μm、平均纤维直径为6μm)、410重量份的甲基纤维素混合(下面,将该混合比称为“混合比B”)。其次,在此混合物中再混合可塑剂和润滑剂(unilub),通过混合、混炼得到混合组成物。之后,通过与实施例1同样的方法得到蜂窝单元。但是,在实施例3中,通过使用表面粗度等与实施例1的模具不同的模具进行挤压成型来制成蜂窝单元。孔道壁厚度为0.33mm(13mil),孔道密度ρ为62个/cm2(400cpsi),孔道壁的表面粗度Ra为20μm。另外,开口率为55%。蜂窝单元中含有的单位表观体积的沸石含量为250g/L。
(实施例4)
首先,将2250重量份的Fe沸石颗粒(平均粒径为2μm)、550重量份的氧化铝颗粒(平均粒径为2μm)、2600重量份的氧化铝胶体溶液、780重量份的氧化铝纤维(平均纤维长度为100μm、平均纤维直径为6μm)、410重量份的甲基纤维素混合(下面,将该混合比称为“混合比C”)。其次,在此混合物中再混合增塑剂和润滑剂(unilub),通过混合、混炼得到混合组合物。之后,通过与实施例1同样的方法得到蜂窝单元。但是,在实施例4中,通过使用表面粗度等与实施例1的模具不同的模具进行挤压成型来制成蜂窝单元。孔道壁厚度为0.33mm(13mil),孔道密度ρ为47个/cm2(300cpsi),孔道壁的表面粗度Ra为20μm。另外,开口率为60%。蜂窝单元中含有的单位表观体积的沸石含量为250g/L。
(实施例5)
通过与实施例1同样的方法制得蜂窝单元。但是,在实施例5中,通过使用表面粗度等与实施例1的模具不同的模具进行挤压成型来制成蜂窝单元。孔道壁厚度为0.20mm(8mil),孔道密度ρ为93个/cm2(600cpsi),孔道壁的表面粗度Ra为20μm。另外,开口率为65%。蜂窝单元中含有的单位表观体积的沸石含量为250g/L。
(实施例6)
通过与实施例1同样的方法制得蜂窝单元。但是,在实施例6中,通过使用表面粗度等与实施例1的模具不同的模具进行挤压成型来制成蜂窝单元。孔道壁厚度为0.25mm(10mil),孔道密度ρ为62个/cm2(400cpsi),孔道壁的表面粗度Ra为20μm。另外,开口率为65%。蜂窝单元中含有的单位表观体积的沸石含量为250g/L。
(实施例7)
通过与实施例1同样的方法制得蜂窝单元。但是,在实施例7中,通过使用表面粗度等与实施例1的模具不同的模具进行挤压成型来制成蜂窝单元。孔道壁厚度为0.28mm(11mil),孔道密度ρ为47个/cm2(300cpsi),孔道壁的表面粗度Ra为20μm。另外,开口率为65%。蜂窝单元中含有的单位表观体积的沸石含量为250g/L。
(实施例8)
通过与实施例1同样的方法制得蜂窝单元。但是,在实施例8中,通过使用表面粗度等与实施例1的模具不同的模具进行挤压成型来制成蜂窝单元。孔道壁厚度为0.30mm(12mil),孔道密度ρ为42个/cm2(270cpsi),孔道壁的表面粗度Ra为20μm。另外,开口率为65%。蜂窝单元中含有的单位表观体积的沸石含量为250g/L。
(实施例9)
通过与实施例1同样的方法制得蜂窝单元。但是,在实施例9中,通过使用表面粗度等与实施例1的模具不同的模具进行挤压成型来制成蜂窝单元。孔道壁厚度为0.33mm(13mil),孔道密度ρ为34个/cm2(220cpsi),孔道壁的表面粗度Ra为20μm。另外,开口率为65%。蜂窝单元中含有的单位表观体积的沸石含量为250g/L。
(实施例10)
通过与实施例1同样的方法制得蜂窝单元。但是,在实施例10中,通过使用表面粗度等与实施例1的模具不同的模具进行挤压成型来制成蜂窝单元。孔道壁厚度为0.33mm(13mil),孔道密度ρ为34个/cm2(220cpsi),孔道壁的表面粗度Ra为30μm。另外,开口率为65%。蜂窝单元中含有的单位表观体积的沸石含量为250g/L。
(比较例1)
通过与实施例1同样的方法制得蜂窝单元。但是,在比较例1中,通过使用表面粗度等与实施例1的模具不同的模具进行挤压成型来制成蜂窝单元。孔道壁厚度为0.33mm(13mil),孔道密度ρ为34个/cm2(220cpsi),孔道壁的表面粗度Ra为0.5μm。另外,开口率为65%。蜂窝单元中含有的单位表观体积的沸石含量为250g/L。
(比较例2)
通过与实施例1同样的方法制得蜂窝单元。但是,在比较例2中,通过使用表面粗度与实施例1的模具不同的模具进行挤压成型来制成蜂窝单元。孔道壁厚度为0.33mm(13mil),孔道密度ρ为34个/cm2(220cpsi),孔道壁的表面粗度Ra为40μm。另外,开口率为65%。蜂窝单元中含有的、单位表观体积的沸石含量为250g/L。
表1
表1中汇总地列出了实施例1~10和比较例1~2的蜂窝单元的孔道壁厚度、孔道密度ρ、孔道壁的表面粗度Ra、开口率以及混合比的值。
(NOx处理性能的评价)
使用由上述方法制成的实施例1~10和比较例1~2的蜂窝单元(评价用样品)进行NOx处理性能的评价。
NOx处理性能的评价是通过如下方法来实施的,即:使模拟了车辆用柴油发动机的运行条件的实验气体流通蜂窝单元并对其进行NOx处理,然后测定从蜂窝单元(评价用样品)中排出的气体中含有的NO(一氧化氮)的含量。
表2中列出了实验气体的组成。
表2
实验是从向蜂窝单元(评价用样品)导入实验气体开始,一直持续到排出的气体中所包含的NO的浓度几乎不再发生变化为止。NO浓度的测定使用了HORIBA公司制的装置(MEXA-7100D)。该装置的NO的检测极限是0.1ppm。实验温度(蜂窝单元和实验气体温度)设为400℃,并在实验期间保持不变。
根据得到的测定结果算出NOx净化率N。这里,NOx净化率N由以下公式算出。
N(%)={(导入至蜂窝结构体之前的混合气体中的NO浓度-
从蜂窝结构体排出的废气中的NO浓度)}/
(导入至蜂窝结构体之前的混合气体中的NO浓度)×100 (1)
结果被示于表1的最右栏。另外,在图4中,示出了实施例和比较例的表面粗度Ra与NOx净化率之间的关系。由这些结果可知,本发明的蜂窝单元(实施例1~10的评价用样品)与比较例1、2的蜂窝单元(评价用样品)相比,具有较高的NOx净化率。特别地,由图4可知,表面粗度Ra在20μm~30μm的范围内时,可以得到极好的NOx净化率。
Claims (10)
1、一种蜂窝结构体,其由包含沸石以及无机粘结剂的蜂窝单元构成,该蜂窝单元具有沿长度方向从第一端面延伸至第二端面的多个孔道被孔道壁分隔的柱状形状,所述蜂窝结构体的特征在于,
所述沸石在所述蜂窝单元的单位表观体积中的含量为230g/L以上,
所述蜂窝单元的开口率P在50~65%的范围,
所述蜂窝单元具有31~93个/cm2的孔道密度ρ,
所述孔道壁的表面粗度Ra在1μm~30μm的范围。
2、根据权利要求1所述的蜂窝结构体,其特征在于,
所述沸石在所述蜂窝单元的单位表观体积中的含量为270g/L以下。
3、根据权利要求1或2所述的蜂窝结构体,其特征在于,
所述沸石为β型沸石、Y型沸石、镁碱沸石、ZSM-5型沸石、丝光沸石、八面沸石、A型沸石或者L型沸石。
4、根据权利要求1或2中任一项所述的蜂窝结构体,其特征在于,
在所述沸石中,二氧化硅与氧化铝的重量比在30~50的范围。
5、根据权利要求1或2中任一项所述的蜂窝结构体,其特征在于,
所述沸石用Fe、Cu、Ni、Co、Zn、Mn、Ti、Ag或者V进行了离子交换。
6、根据权利要求1或2中任一项所述的蜂窝结构体,其特征在于,
所述蜂窝单元包含从由氧化铝颗粒、二氧化钛颗粒、二氧化硅颗粒、氧化锆颗粒以及这些颗粒的前驱体构成的组中选定的至少一种颗粒。
7、根据权利要求1或2中任一项所述的蜂窝结构体,其特征在于,
所述无机粘结剂包含从由氧化铝胶体溶液、二氧化硅胶体溶液、二氧化钛胶体溶液、水玻璃、海泡石以及绿坡缕石构成的组中选定的至少一种材料。
8、根据权利要求1或2中任一项所述的蜂窝结构体,其特征在于,
所述蜂窝单元还包含无机纤维。
9、根据权利要求8所述的蜂窝结构体,其特征在于,
所述无机纤维为从由氧化铝、二氧化硅、碳化硅、硅铝、玻璃、钛酸钾以及硼酸铝构成的组中选定的至少一种纤维。
10、根据权利要求1或2中任一项所述的蜂窝结构体,其特征在于,
所述蜂窝结构体是通过粘结层将多个所述蜂窝单元结合在一起而构成的。
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US9670809B2 (en) | 2011-11-29 | 2017-06-06 | Corning Incorporated | Apparatus and method for skinning articles |
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US10611051B2 (en) | 2013-10-15 | 2020-04-07 | Corning Incorporated | Systems and methods for skinning articles |
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US8202601B2 (en) | 2012-06-19 |
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