CN101547734B - 排气净化装置 - Google Patents
排气净化装置 Download PDFInfo
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- CN101547734B CN101547734B CN2007800444496A CN200780044449A CN101547734B CN 101547734 B CN101547734 B CN 101547734B CN 2007800444496 A CN2007800444496 A CN 2007800444496A CN 200780044449 A CN200780044449 A CN 200780044449A CN 101547734 B CN101547734 B CN 101547734B
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- occlusion
- catalyst
- emission
- zeolite
- control equipment
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- 239000003054 catalyst Substances 0.000 claims abstract description 83
- 239000000758 substrate Substances 0.000 claims abstract description 54
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 23
- 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 23
- 239000010457 zeolite Substances 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 21
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 18
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 63
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 16
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims description 15
- 150000001340 alkali metals Chemical class 0.000 claims description 15
- 239000002585 base Substances 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 abstract description 12
- 238000011144 upstream manufacturing Methods 0.000 abstract description 11
- 239000011232 storage material Substances 0.000 abstract 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 abstract 2
- 238000011068 loading method Methods 0.000 description 18
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
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- 238000006243 chemical reaction Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
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- 230000009467 reduction Effects 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 231100000572 poisoning Toxicity 0.000 description 5
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- 229920006395 saturated elastomer Polymers 0.000 description 5
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- 239000003599 detergent Substances 0.000 description 4
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- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
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- 150000003624 transition metals Chemical class 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- 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 3
- 239000000446 fuel Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 230000010718 Oxidation Activity Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
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- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
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- Toxicology (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Exhaust Gas After Treatment (AREA)
Abstract
由载体基材(30)和涂层(31)构成了吸藏催化剂(3),所述载体基材(30)由选自Al2O3、CeO2、ZrO2、TiO2和沸石中的至少一种形成,且比表面积为30m2/g以上,所述涂层(31)是在包含选自Al2O3、CeO2、ZrO2、TiO2和沸石中的至少一种的载体粉末上担载吸藏NOx和SOx的吸藏材料和贵金属而成的。由于载体基材(30)的比表面积大,因此吸藏NOx和SOx的吸藏材料的担载量格外地增大。因此,配置在NOx吸藏还原催化剂的上游侧的吸藏催化剂的SOx吸藏量增大,在低温区中的NOx吸藏量增大。
Description
技术领域
本发明涉及净化从汽车等的内燃机中排出的排气的排气净化装置,详细地讲,涉及最适合于对来自稀燃发动机的排气进行净化的NOx吸藏还原型的排气净化装置。
背景技术
近年来,二氧化碳所造成的地球温室化现象已成为问题,降低二氧化碳排出量已成为课题,对于汽车,降低排气中的二氧化碳量也成为课题,已使用在氧过剩气氛下使燃料稀薄燃烧的稀燃发动机。利用这种稀燃发动机,可减少燃料的使用量,因此能够抑制二氧化碳的排出量。
另外,作为对来自稀燃发动机的排气中的有害成分进行净化的催化剂,已知在担载贵金属的同时还担载选自碱金属、碱土类金属和稀土类元素中的NOx吸藏材料的NOx吸藏还原催化剂。如果使用该NOx吸藏还原催化剂,在稀薄气氛的中途脉冲状地控制混合气组成使之成为理论配比气氛~浓气氛,则能够高效地进行HC以及CO的氧化和NOx的还原,能够得到高的净化性能。
然而,一般的NOx吸藏还原催化剂,存在在低温区的NOx吸藏量不充分的问题。
另外,在排气中含有在燃料中所含的硫(S)燃烧而生成的SOx,该SOx在氧过剩气氛中被催化剂金属氧化,变成SO3。并且,该SO3还由于排气中含有的水蒸气的作用而容易地变成亚硫酸或硫酸,由于这些酸与NOx吸藏材料反应,生成亚硫酸盐、硫酸盐,因此,NOx吸藏材料中毒劣化。另外,氧化铝等的多孔质载体具有容易吸藏SOx的性质,因此也有促进上述硫中毒的问题。
并且,当NOx吸藏材料这样地变成亚硫酸盐、硫酸盐时,已经难以吸藏NOx,存在耐久后的对NOx的净化性能降低的不良情况。
因此,日本特开2002-011347号公报记载了含有包含稀土类元素和铝氧化物的复合氧化物的SOx吸藏材料,并记载了将该SOx吸藏材料配置在NOx吸藏还原催化剂的上游侧。
另外,日本特开2001-113172号公报提出了在NOx吸藏还原催化剂层的上层设置抑制SOx扩散的阻挡层的排气净化用催化剂。阻挡层由担载了贵金属和过渡金属的无机氧化物构成。根据该排气净化用催化剂,在阻挡层中在稀薄气氛下贵金属将S氧化,生成的SOx被过渡金属牢固地捕捉,因此可抑制SOx向下层的NOx吸藏还原催化层扩散。并且,阻挡层的贵金属在理论配比气氛~浓气氛中将SOx还原,切断过渡金属与SOx的结合,从阻挡层中放出SOx。所以阻挡层的SOx吸藏能力不会饱和。
因此,可考虑将日本特开2001-116172号公报所述的只形成阻挡层的催化剂配置在NOx吸藏还原催化剂的上游侧。
这样,根据在NOx吸藏还原催化剂的上游侧配置了担载有能够吸藏SOx的SOx吸藏材料的吸藏催化剂的排气净化装置,能够抑制下游侧的NOx吸藏还原催化剂的硫中毒。另外,吸藏SOx意味着也吸藏NOx,因此有时可得到在低温区中的NOx吸藏量增加的优点。
然而,现有的吸藏催化剂,SOx吸藏材料的担载量存在极限,SOx的吸藏性能不充分,具有不能够充分地防止配置在下游侧的NOx吸藏还原催化剂的硫中毒的问题。另外,大量地担载SOx吸藏材料的场合,SOx吸藏材料与载体基材反应,存在载体基材的强度大幅度地降低的问题。
专利文献1:日本特开2001-113172号
专利文献2:日本特开2002-011347号
发明内容
本发明是鉴于上述状况而完成的研究,其要解决的课题是使配置在NOx吸藏还原催化剂的上游侧的吸藏催化剂的SOx吸藏量增大,并使低温区下的NOx吸藏量也增大。
解决上述课题的本发明的排气净化装置的特征在于,该排气净化装置包含吸藏NOx和SOx的吸藏催化剂、和配置在吸藏催化剂的排气下游侧的NOx吸藏还原催化剂,吸藏催化剂包含载体基材和涂层,所述载体基材由选自Al2O3、CeO2、ZrO2、TiO2和沸石中的至少一种形成,且比表面积为30m2/g以上,所述涂层在该载体基材的表面形成,是在包含选自Al2O3、CeO2、ZrO2、TiO2和沸石中的至少一种的载体粉末上担载吸藏NOx和SOx的吸藏材料和贵金属而成的。
优选载体基材中也含有上述吸藏材料。
发明效果
根据本发明的排气净化装置,吸藏催化剂使用了由选自Al2O3、CeO2、ZrO2、TiO2和沸石中的至少一种形成,且比表面积为30m2/g以上的载体基材。该载体基材的比表面积大,因此吸藏NOx和SOx的吸藏材料的担载量格外地增大,SOx吸藏量和在低温区中的NOx吸藏量格外地增大。另外,由这样的材质形成的载体基材,难以与吸藏NOx和SOx的吸藏材料反应,因此也没有载体基材的强度降低的问题。
因此,作为排气净化装置整体,NOx净化性能提高,并且能够防止下游侧的NOx吸藏还原催化剂的硫中毒,所以耐久性提高。
附图说明
图1是表示本发明的一个实施例的排气净化装置的说明图。
图2是表示NOx吸藏量的条形图。
图3是表示吸藏硫量的条形图。
附图标号说明
1-发动机、2-催化转化器、3-吸藏催化剂、4-NOx吸藏还原催化剂
具体实施方式
本发明的排气净化装置,包含吸藏NOx和SOx的吸藏催化剂、和配置在吸藏催化剂的排气下游侧的NOx吸藏还原催化剂。其中,NOx吸藏还原催化剂可以使用由多孔质氧化物载体、担载在多孔质氧化物载体上的贵金属、和选自碱金属、碱土类金属和稀土类元素且担载在多孔质氧化物载体上的NOx吸藏材料构成的与以往同样的催化剂。
作为NOx吸藏还原催化剂所使用的多孔质氧化物载体,可以使用氧化铝、二氧化硅、二氧化硅-氧化铝、氧化锆、二氧化钛、沸石等。既可以使用其中的一种,也可以将多种混合或复合化而使用。其中,优选使用活性高的γ-Al2O3。
作为NOx吸藏还原催化剂所使用的贵金属,可例举出Pt、Rh、Pd、Ir等。其中,特别优选活性高的Pt。另外,贵金属的担载量优选为每1升催化剂0.1~10g,比该担载量少时,净化活性不足,即使比该担载量多地担载,效果也饱和,并且成本高。
另外,NOx吸藏还原催化剂中的NOx吸藏材料的担载量,优选为每1升催化剂0.01~2摩尔的范围。担载量比该范围少时,NOx吸藏量降低,因此NOx净化能力降低,比该范围多时,贵金属被NOx吸藏材料覆盖从而活性降低。
作为碱金属,可例举出锂、钠、钾、铯。作为碱土类金属,可例举出周期表2A族元素的钡、铍、镁、钙、锶等。另外,作为稀土类元素。可例举出钪、钇、镧、铈、镨、钕、镝、镱等。
构成本发明特征的吸藏催化剂,包含载体基材和在载体基材的表面形成的涂层。载体基材由选自Al2O3、CeO2、ZrO2、TiO2和沸石中的至少一种形成,且比表面积为30m2/g以上。比表面积低于30m2/g时,吸藏材料的担载量不充分,SOx吸藏量减少,并且在低温区中的NOx吸藏量也减少,因而不优选。特别优选载体基材的比表面积为50m2/g以上。
另外,载体基材的材质,在上述材质中特别优选Al2O3或ZrO2。γ-Al2O3由于比表面积显著地高因而优选。ZrO2由于碱度高因此SOx的吸藏性能进一步提高。另外,由于后述的理由,沸石也是优选的材质。
涂层是在包含选自Al2O3、CeO2、ZrO2、TiO2和沸石中的至少一种的载体粉末上,担载吸藏NOx和SOx的吸藏材料和贵金属而成的涂层。作为载体粉末,由于与上述同样的理由,特别优选Al2O3或ZrO2,由于后述的理由也优选沸石。涂层的形成量优选为每1升吸藏催化剂100g以上,特别优选为150g以上。涂层的形成量少时,NOx和SOx的吸藏量降低。
吸藏NOx和SOx的吸藏材料,优选使用选自碱金属和碱土类金属中的至少一种,其中,优选碱度高且稳定性优异的Mg或Ba。
例如碱金属的氧化物、碱土类金属的氧化物等,虽然吸藏NOx和SOx的能力高,但其另一面,难以放出所吸藏的NOx和SOx。因此放出NOx和SOx的温度变高,在低温至中温区使用的场合,NOx和SOx的吸藏量饱和,具有难以吸藏更多的NOx和SOx的不良情况。然而,如果为在沸石等的载体粉末上离子交换担载了碱金属、碱土类金属的吸藏材料,则放出所吸藏的NOx和SOx的温度变低,即使是低温至中温区的排气温度,也能够重复NOx和SOx的吸藏和放出。
另外,在ZrO2中添加了碱金属、碱土类金属的材料,与其他的吸藏材料相比显示出特别优异的吸藏能力。并且,当在添加了碱金属、碱土类金属的ZrO2上担载Pt、Rh、Pd等贵金属或Co3O4、NiO2、MnO2、Fe2O3等的过渡金属氧化物时,吸藏能力进一步提高。可以认为这是由于,通过Pt、Co3O4、NiO2、MnO2、Fe2O3等呈现氧化活性,排气中的NO或SO2被氧化,吸藏量增加的缘故。
这样,虽然碱金属、碱土类金属发生效果的原因并不清楚,但可以认为是因为,通过碱金属、碱土类金属在ZrO2晶格中固溶,碱金属、碱土类金属与ZrO2复合化,由此ZrO2表面被改质,新生成吸藏区域的缘故。
吸藏材料,根据其种类,吸藏NOx和SOx的温度不同。因此,也优选同时使用显示最大吸藏量的温度不同的多种的吸藏材料。例如,如果在最上游侧配置在低温下高效地吸藏NOx和SOx的低温型吸藏材料,在其下游侧配置在中温~高温下高效地吸藏NOx和SOx的中温型吸藏材料,则NOx和SOx从吸藏温度低的上游侧慢慢地被吸藏,因此能够在从低温区到高温区的较宽温度区中吸藏NOx和SOx。另外,由于由NOx和SOx的吸藏所导致的放热,排气被加热,因此也具有下游侧的吸藏材料或NOx吸藏还原催化剂的活性早期地呈现的效果。
作为例如在室温~100℃显示最大吸藏量的吸藏材料,可举出在沸石上担载了Ce等稀土类元素的材料、在沸石上担载了碱金属、碱土类金属或过渡金属的材料等。作为在100~200℃显示最大吸藏量的吸藏材料,可举出在ZrO2上担载了贵金属的材料、担载了Co3O4等过渡金属的材料等,作为在300℃以上显示最大吸藏量的吸藏材料,可举出在ZrO2、Al2O3等上担载了贵金属、与碱金属、碱土类金属的材料等。
沸石,别名也称为分子筛,具有与分子的大小相匹敌的细孔,除了被用作为吸藏材料外,还作为催化剂用于较多的反应。另外,为了中和作为主成分的Al2O3的负电荷而含有阳离子,由于该阳离子在水溶液中与其他的阳离子容易地交换,因此也作为阳离子交换体使用。所以,能够离子交换担载选自碱金属和碱土类金属中的至少一种金属,能够以极高的分散状态担载。
另外,可以认为由于经离子交换担载的金属元素,极高分散地担载在沸石上,因此活性极高,在低温区中的NO和SO2的氧化活性提高。所以可认为排气中的NO和SO2即使在低温区也在吸藏材料上被氧化而成为NOx和SOx,其被吸藏材料吸藏,是即使在低温区也能充分地吸藏NOx和SOx的。
另外,由于沸石中也吸藏排气中的HC,因此也期待所吸藏的HC与NOx的反应。所以NOx净化能力进一步提高。
再者,作为沸石,可以使用镁碱沸石、ZSM-5、丝光沸石、Y型沸石等的沸石等。其中,ZSM-5和丝光沸石由于离子交换能力优异,因此优选从它们之中选择使用。
并且,如果将NOx吸藏还原催化剂配置于在沸石上离子交换担载了选自碱金属、碱土类金属和稀土类元素中的至少一种金属元素的吸藏材料的下游侧,则由于即使在低温区NO也已成为NOx,因此即使存在没有被吸藏材料吸藏掉的NOx,也被下游侧的NOx吸藏还原催化剂吸藏。所以,在低温区的NOx吸藏能力提高,NOx净化能力提高。
涂层中还担载有贵金属,作为该贵金属,可以例举Pt、Rh、Pd、Ir等。其中,特别优选氧化活性高的Pt,另外,贵金属担载量,优选为每1升吸藏催化剂为0.5~2.0g,比该担载量少时,NOx和SOx的吸藏性能不足,即使比该担载量多地担载,效果也饱和,并且成本增高。
吸藏催化剂中的载体基材的形状,可以为颗粒(pellet)状、泡沫状、直流型蜂窝形状、壁流型蜂窝形状等。另外,涂层形成于与排气接触的载体基材表面。壁流型蜂窝形状的载体基材的场合,优选在划分流入侧孔和流出侧孔的隔壁中的细孔的内表面也形成涂层。
为了将吸藏催化剂的载体基材制成为例如直流型蜂窝形状,可以将包含选自Al2O3、ZrO2、TiO2和沸石中的至少一种的粉末,与粘合剂一起形成为粘度高的浆液,将其挤出成型后进行烧成而制造。并且,为了在载体基材的表面形成涂层,将包含选自Al2O3、CeO2、ZrO2、TiO2和沸石中的至少一种的粉末与粘合剂一起形成为粘度比较低的浆液,投入到载体基材中后,抽吸后进行干燥、烧成,然后,依次浸渍溶解了贵金属化合物的溶液和溶解了含吸藏材料元素的化合物的溶液,进行干燥和烧成即可。
为了在涂层中担载吸藏材料,使用溶解了硝酸盐等含吸藏材料元素的化合物的溶液。由于想要使吸藏材料的担载量尽量地多,因此优选溶液中的含吸藏材料元素的化合物的浓度为饱和浓度。另外,由于希望通过一次的处理而大量地担载,因此形成了涂层的状态下的吸水量优选为每1升催化剂至少150g以上,特别优选为200g以上。
另外,优选在吸藏催化剂的载体基材中也含有上述的吸藏材料。由此NOx和SOx的吸藏量进一步增大。即使采用上述的担载法,在载体基材中也含有某种程度的吸藏材料,但希望在用于制造载体基材的浆液中混合MgO、BaO等的吸藏材料粉末。当该场合的吸藏材料粉末的混合量多时,有时载体基材的强度降低或比表面积不到30m2/g。
然而,已知NOx吸藏还原型催化剂中的NOx净化反应包括:在稀薄气氛中将排气中的NOx氧化成为NOx的第1步骤;将NOx吸藏在NOx吸藏元素中的第2步骤;和在理论配比气氛~浓气氛中在催化剂上将从NOx吸藏元素放出的NOx还原的第3步骤。因此,为了NOx净化反应顺利地进行,必须各步骤分别顺利地进行。
然而,可以认为例如在低于300℃的低温区,难以进行NO的氧化反应,第一步骤难以顺利地进行。因此,可以想到在低温区NOx的生成量变少,第2步骤和第3步骤也未顺利地进行,低温区中的NOx净化能力变低。
因此,本发明的排气净装置,为在NOx吸藏还原催化剂的排气上游侧配置了吸藏催化剂的构成。吸藏催化剂中含有的吸藏材料容易吸藏NOx,即使在低温区也吸藏NOx。所以,在低温区基本上不含有NOx的排气被供给到NOx吸藏还原催化剂中,因此基本上不排出NOx。并且,当排气温度上升时,被吸藏的NOx从吸藏材料中脱离,流入到NOx吸藏还原催化剂中,但由于NOx吸藏还原催化剂已达到活化温度,因此上述第1步骤的反应顺利地进行,NOx被高效地还原净化。根据这样的机理,利用本发明的排气净化装置能够确保从低温到高温的较高的NOx净化率。
实施例
以下通过实施例和比较例具体地说明本发明。
实施例1
图1表示本实施例的排气净化装置,在发动机1的排气流路上配置有催化转化器2。对于催化转化器2,在上游侧配置吸藏催化剂3,在吸藏催化剂3的下游侧配置NOx吸藏还原催化剂4。吸藏催化剂3和NOx吸藏还原催化剂4均是直流结构的蜂窝催化剂。
吸藏催化剂3包含由γ-Al2O3形成的直流型的蜂窝基材30、和在其孔壁表面形成的涂层31。蜂窝基材30为体积2L、600孔/平方英寸、比表面积100m2/g。每1升蜂窝基材30形成150g涂层31。
涂层31通过洗涂主要含有γ-Al2O3的浆液而形成,担载了相对于1升蜂窝基材30为2.0g的Pt、和相对于1升蜂窝基材30为2.5摩尔的MgO。首先,洗涂主要含有γ-Al2O3的浆液,进行干燥烧成,形成了氧化铝涂层。接着,使设定浓度的Pt药液以设定量浸渗到氧化铝涂层中,进行烧成从而担载了Pt。然后,浸渗最大量的硝酸镁水溶液(饱和水溶液),进行干燥、烧成从而担载了MgO。所担载的MgO的量,相对于1升蜂窝基材30为100g。
NOx吸藏还原催化剂4包含由堇青石形成的直流型的蜂窝基材40、和在其孔壁表面形成的涂层41。蜂窝基材40为体积3L、400孔/平方英寸、比表面积100m2/g。每1升蜂窝基材40形成150g涂层41。
涂层41包含γ-Al2O3粉末、和担载在γ-Al2O3粉末上的Pt、K以及Ba。每1升蜂窝基材40担载Pt 2g、K 0.1摩尔、Ba 0.1摩尔。
实施例2
作为吸藏催化剂3的蜂窝基材,使用由按γ-Al2O3粉末∶MgO粉末=9∶1的重量比混合的混合粉末形成的蜂窝基材替代γ-Al2O3粉末。蜂窝基材是与实施例1相同的形状,其比表面积为100m2/g。使用该蜂窝基材形成与实施例1同样的氧化铝涂层。每1升蜂窝基材形成150g氧化铝涂层。并且,除了硝酸镁水溶液的浓度不同以外,与实施例1同样地在氧化铝涂层中担载了Pt和MgO,结果Pt和MgO的担载量与实施例1相同。再者,调查了MgO的担载分布,结果在蜂窝基材上担载了1.0摩尔/L,在涂层中担载了1.5摩尔/L。
在催化转化器2中,在上游侧配置所得到的吸藏催化剂,在其下游侧配置与实施例1同样的NOx吸藏还原催化剂4,形成为实施例2的排气净化装置。
比较例1
作为吸藏催化剂3的蜂窝基材,使用由堇青石粉末形成的蜂窝基材替代γ-Al2O3粉末。蜂窝基材是与实施例1相同的形状,其比表面积为0.1~1m2/g。使用该蜂窝基材形成了与实施例1同样的氧化铝涂层。每1升蜂窝基材形成150g氧化铝涂层。并且,与实施例1同样地在氧化铝涂层中担载了Pt和MnO,结果Pt的担载量与实施例1同样,但MgO的担载量为1.0摩尔/L,比实施例1少。
在催化转化器2中,在上游侧配置所得到的吸藏催化剂,在其下游侧配置与实施例1同样的NOx吸藏还原催化剂4,形成为比较例1的排气净化装置。
比较例2
作为吸藏催化剂3的蜂窝基材,使用由堇青石粉末形成的蜂窝基材替代γ-Al2O3粉末。蜂窝基材是与实施例1相同的形状,其比表面积为0.1~1m2/g,使用该蜂窝基材形成了与实施例1同样的氧化铝涂层。每1升蜂窝基材形成150g氧化铝涂层。并且,与实施例1同样地在氧化铝涂层中担载了Pt和MgO,结果Pt的担载量与实施例1同样,但MgO的担载量为1.25摩尔/L,比实施例1少。
试验例
只将用于各实施例和各比较例的排气净化装置中的吸藏催化剂3分别安装在评价装置中,使表1所示的稀薄恒定的模型气体流入。催化床温度为150℃,模型气体流量为30L/分。并且,分析从催化剂放出的气体,测定NOx吸藏量的结果示于图2。
表1
NO(ppm) | C3H6(ppm) | O2(%) | CO2(%) | H2O(%) | N2 |
150 | 200 | 10 | 10 | 5 | 其余量 |
另外,只将在各实施例和各比较例的排气净化装置中使用的吸藏催化剂3分别安装在评价装置中,使表2所示的稀薄恒定的模型气体流入。催化床温度为400℃,模型气体流量为30L/分。并且,测定使相对于1升蜂窝基材,作为硫为90g相当量的模型气体通过时的吸藏硫量的结果示于图3。
表2
SO2(ppm) | NO(ppm) | C3H6(ppm) | O2(%) | CO2(%) | H2O(%) | N2 |
125 | 200 | 200 | 10 | 10 | 5 | 其余量 |
由图2和图3可知,实施例1和实施例2的吸藏催化剂,在低温区中的NOx吸藏性能优异,并且SOx吸藏性能也优异,这表明起因于MgO的担载量多。
本发明中表示数值范围的“以上”和“以下”均包括本数。
Claims (3)
1.一种排气净化装置,是包含吸藏NOx和SOx的吸藏催化剂、和配置在该吸藏催化剂的排气下游侧的NOx吸藏还原催化剂的排气净化装置,其特征在于,该吸藏催化剂包含蜂窝状载体基材和涂层,所述蜂窝状载体基材由Al2O3、或Al2O3和MgO的混合物形成,且比表面积为100m2/g以上,所述涂层在该载体基材的表面形成,是在包含选自Al2O3、CeO2、ZrO2、TiO2和沸石中的至少一种的载体粉末上担载吸藏NOx和SOx的吸藏材料和贵金属而成的,所述吸藏材料由碱金属和碱土类金属中的至少一种构成,
形成了该涂层的状态下的每升催化剂的吸水量为150g以上。
2.根据权利要求1所述的排气净化装置,所述载体基材中含有所述吸藏材料。
3.根据权利要求1所述的排气净化装置,所述吸藏材料含有选自镁和钡中的至少一种。
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