CN103874543A - 排出气体净化用催化剂以及排出气体净化用催化剂构成体 - Google Patents
排出气体净化用催化剂以及排出气体净化用催化剂构成体 Download PDFInfo
- Publication number
- CN103874543A CN103874543A CN201280044887.3A CN201280044887A CN103874543A CN 103874543 A CN103874543 A CN 103874543A CN 201280044887 A CN201280044887 A CN 201280044887A CN 103874543 A CN103874543 A CN 103874543A
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- China
- Prior art keywords
- exhaust gas
- catalyst
- aluminium borate
- gas purifying
- quality
- 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.)
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Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- 238000000746 purification Methods 0.000 title abstract 5
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims abstract description 106
- 229910052742 iron Inorganic materials 0.000 claims abstract description 41
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 13
- 239000007769 metal material Substances 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 78
- 238000006073 displacement reaction Methods 0.000 claims description 57
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 abstract description 6
- 229910052763 palladium Inorganic materials 0.000 abstract description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 76
- 239000007789 gas Substances 0.000 description 67
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 35
- 229910052760 oxygen Inorganic materials 0.000 description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 28
- 239000001301 oxygen Substances 0.000 description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 25
- 230000033228 biological regulation Effects 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 12
- 150000002430 hydrocarbons Chemical class 0.000 description 12
- 238000011068 loading method Methods 0.000 description 12
- 238000003860 storage Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000446 fuel Substances 0.000 description 9
- 230000006641 stabilisation Effects 0.000 description 9
- 239000002002 slurry Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 7
- 239000004327 boric acid Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000010532 solid phase synthesis reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 4
- 229910001863 barium hydroxide Inorganic materials 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229910001593 boehmite Inorganic materials 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 235000012501 ammonium carbonate Nutrition 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229940044658 gallium nitrate Drugs 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- JTDGCKJDVZEXTK-UHFFFAOYSA-N [Fe+2].B([O-])([O-])[O-].[Al+3] Chemical compound [Fe+2].B([O-])([O-])[O-].[Al+3] JTDGCKJDVZEXTK-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 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
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- -1 plate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Abstract
排出气体净化用催化剂,其包含:含有将硼酸铝中的铝原子的2.5~11.5at%用Fe、Co、Ga或Ni进行了置换的置换硼酸铝的载体、以及担载于该载体的Pd;以及,排出气体净化用催化剂构成体,其包含:含有陶瓷或金属材料的催化剂支撑体、以及在该催化剂支撑体上担载的上述排出气体净化用催化剂的层。
Description
技术领域
本发明涉及排出气体净化用催化剂以及排出气体净化用催化剂构成体,更详细而言,涉及储氧能力优异、高温耐久后的排出气体净化性能、尤其是富相区域的NOX净化性能优异的排出气体净化用催化剂以及排出气体净化用催化剂构成体。
背景技术
从汽车等的内燃机中排放的排出气体中包含烃(HC)、一氧化碳(CO)、氮氧化物(NOX)等有害成分。因而,一直以来,为了净化这些有害成分以进行无害化,使用了三效催化剂。
在这样的三效催化剂中,作为催化剂活性成分而使用Pt、Pd、Rh等贵金属,作为载体而使用了氧化铝、氧化铈、氧化锆、具备吸氧能力的氧化铈-氧化锆复合氧化物等,作为催化剂支撑体而使用由陶瓷或金属材料制成的蜂窝、板、粒料等形状的支撑体。
随着汽车排出气体的法规的强化,作为内燃机排出气体净化用催化剂的主要催化剂活性成分的Pt和Rh的需求增加,价格高涨,尤其是对于Rh,由于其价格变动的影响大,因此在贵金属之中期望用廉价的Pd来进行代替,研究了通过将比较廉价的Pd用作催化剂活性成分,从而削减排出气体净化用催化剂的成本,并提出了各种手段(例如,参照专利文献1、2、3)。另外,还有使用硼酸铝作为载体的例子,通过使压粉体担载催化剂成分来实现气体扩散性的提高,所述压粉体包含用硼酸铝晶须覆盖外侧且在其内部形成有中空部的粉状体(参照专利文献4)。
现有技术文献
专利文献
专利文献1:日本特开平06-099069号公报
专利文献2:日本特开平07-171392号公报
专利文献3:日本特开平08-281071号公报
专利文献4:日本特开2002-370035号公报。
发明内容
发明要解决的课题
然而,有报告Pd在高温的还原性气氛下会因烧结而导致排出气体净化性能的降低,面向今后的节省贵金属催化剂的设计,抑制Pd的烧结已经成为不可避免的课题。另外,硼酸铝晶须为针状,因此比表面积小,并且无法避免耐久后的贵金属的凝集,耐久性存在问题。
本发明的目的在于,提供储氧能力优异、高温耐久后的排出气体净化性能、尤其是富相区域的NOX净化性能优异的排出气体净化用催化剂。
用于解决问题的手段
本发明人等为了实现上述目的而进行了深入研究,结果发现,将耐热性优异的具有笼(cage)型结构的硼酸铝中的一部分铝原子用Fe、Co、Ga、Ni等原子进行了置换的置换硼酸铝系化合物、尤其是用Fe、Ni进行了置换的硼酸铝系化合物用作Pd的载体时,表现出储氧能力,其富相区域的NOx净化活性与将未置换硼酸铝或La稳定化氧化铝用作Pd的载体时相比大幅提高,从而完成了本发明。
需要说明的是,关于硼酸铝的特性及其制造方法等,例如在Siba P. Ray, “Preparation and Characterization of Aluminum Borate”, J. Am. Ceram. Soc., 75〔9〕, p2605-2609(1992)等中有所记载。
以往,硼酸铝通过化学分析而用式9Al2O3·2B2O3(Al18B4O33)表示,但Martin 等的“Crystal-chemistry of mullite- type aluminoborates Al18B4O33 and Al5BO9:A stoichiometry puzzle”,Journal of Solid State Chemistry 184(2011) 70-80中记载了:根据晶体结构分析,硼酸铝可用Al5BO9(5Al2O3:B2O3、Al20B4O36)、即式10Al2O3·2B2O3来表示,相对于硼酸铝,式9Al2O3·2B2O3(Al18B4O33)和Al5BO9(5Al2O3:B2O3、Al20B4O36)这两者都是允许的(即为同一物质)。
因此,本发明中使用的硼酸铝包括用式10Al2O3·2B2O3(5Al2O3:B2O3、Al20B4O36)表示的硼酸铝、或者用式9Al2O3·2B2O3(Al18B4O33)表示的硼酸铝。
即,本发明的排出气体净化用催化剂的特征在于,其包含:含有将硼酸铝中的铝原子的2.5~11.5at%用Fe、Co、Ga或Ni进行了置换的置换硼酸铝的载体、以及担载于该载体的Pd。此处,本发明中的硼酸铝为氧化铝与氧化硼之比为10:2~9:2的硼酸铝,包括用式10Al2O3·2B2O3(5Al2O3:B2O3、Al20B4O36)表示的硼酸铝、或者用式9Al2O3·2B2O3(Al18B4O33)表示的硼酸铝。所述硼酸铝可以通过X射线衍射来确定为用式10Al2O3·2B2O3表示的硼酸铝,但作为X射线衍射的标准图,还存在式9Al2O3·2B2O3(Al18B4O33),也可确定为式9Al2O3·2B2O3(Al18B4O33)。
可以记载的是,本发明的排出气体净化用催化剂的特征在于,其包含:含有用通式MmAl20-mB4O36(式中,M为Fe、Co、Ga或Ni,m为0.5~2.3)表示的M置换硼酸铝的载体、以及担载于该载体的Pd。
另外,还可以记载的是,本发明的排出气体净化用催化剂的特征在于,其包含:含有用通式MnAl18-nB4O33(式中,M为Fe、Co、Ga或Ni,n为0.45~2.07)表示的M置换硼酸铝的载体、以及担载于该载体的Pd。
本发明的排出气体净化用催化剂中,载体优选为铁置换硼酸铝。
另外,本发明的排出气体净化用催化剂构成体的特征在于,其包含:由陶瓷或金属材料制成的催化剂支撑体、以及在该催化剂支撑体上担载的上述排出气体净化用催化剂的层。
发明效果
本发明的排出气体净化用催化剂的储氧能力优异、高温耐久后的排出气体净化性能、尤其是富相区域的NOX净化性能优异。
附图说明
图1是参考例1中得到的铁置换硼酸铝的XRD图和参考例2中得到的未置换硼酸铝的XRD图。
图2是表示参考例3中得到的铁置换硼酸铝的吸氧放氧行为和参考例4中得到的未置换硼酸铝的吸氧放氧行为的图。
图3是表示由排出气体净化用催化剂的空燃比的变化引起的对CO的催化剂性能的图表。
图4是表示由排出气体净化用催化剂的空燃比的变化引起的对HC的催化剂性能的图表。
图5是表示由排出气体净化用催化剂的空燃比的变化引起的对NOX的催化剂性能的图表。
具体实施方式
本发明的排出气体净化用催化剂中使用的载体是将硼酸铝中的铝原子的2.5~11.5at%用Fe、Co、Ga或Ni进行了置换的置换硼酸铝。这样的置换硼酸铝可以用通式MmAl20-mB4O36(式中,M为Fe、Co、Ga或Ni,m为0.5~2.3)表示,也可以用通式MnAl18-nB4O33(式中,M为Fe、Co、Ga或Ni,n为0.45~2.07)表示。
置换硼酸铝中,硼酸铝中的被置换的铝原子的量不足2.5at%(上述的m不足0.5、n不足0.45)时,存在吸氧能力、高温耐久后的催化剂的排出气体净化性能变得不充分的倾向。硼酸铝中的被置换的铝原子的量超过11.5at%(上述的m超过2.3、n超过2.07)时,存在超过固溶限界而形成杂质相(如果是Fe则为赤铁矿相)的倾向,或者存在比表面积极端降低而无法高分散地担载贵金属的倾向。
上述的M置换硼酸铝例如可以利用下述方法来制造。
<固相法>
将以达到目标化合物即M置换硼酸铝(通式MnAl18-nB4O33)的规定比的方式称量的硼酸溶解在离子交换水中。在该溶液中混合以达到规定比的方式称量的硝酸铁、硝酸钴或者硝酸镓并使其溶解。其后,混合以达到规定比的方式称量的醋酸勃姆石溶胶,加热搅拌。将所得凝胶状产物在120℃左右下干燥12小时以上。干燥后,在空气中在300℃左右下煅烧1小时左右,进而在1000℃左右下煅烧5小时左右,从而可以得到M置换硼酸铝。
具体而言,将以目标化合物即铁置换硼酸铝(Fe1Al17B4O33)达到规定比的方式称量的硼酸溶解在离子交换水中。在该溶液中混合以达到规定比的方式称量的硝酸铁九水合物并使其溶解。其后,混合以达到规定比的方式称量的醋酸勃姆石溶胶,加热搅拌。将所得凝胶状产物在120℃下干燥12小时以上。干燥后,在空气中在300℃下煅烧1小时,进而在1000℃下煅烧5小时,从而得到铁置换硼酸铝。
<反向共沉淀法>
使以达到目标化合物即M置换硼酸铝(通式MnAl18-nB4O33)的规定比的方式称量的硼酸溶解在纯温水中,在该溶液中混合以达到规定比的方式称量的硝酸铝和以达到规定比的方式称量的硝酸铁、硝酸钴或硝酸镓并使其溶解。接着,将该溶液滴加至碳酸铵水溶液中。将所得沉淀物用纯水过滤洗涤,过滤,在120℃左右下干燥一晚,在空气中在300℃左右下煅烧1小时左右后,进而在空气中在1000℃左右下煅烧5小时左右,从而可以得到M置换硼酸铝。
具体而言,将以达到目标化合物即铁置换硼酸铝(Fe1Al17B4O33)的规定比的方式称量的硼酸溶解在离子交换水中。在该溶液中混合以达到规定比的方式称量的硝酸铝九水合物和硝酸铁九水合物并使其溶解。接着,将该溶液滴加至碳酸铵水溶液中。将所得沉淀物用纯水过滤洗涤,在120℃下干燥12小时以上。接着,在空气中在300℃下煅烧1小时后,进而在空气中在1000℃下煅烧5小时,从而得到铁置换硼酸铝。利用该反向共沉淀法制备的铁置换硼酸铝与利用上述固相法制备的铁置换硼酸铝之间未发现差异。
本发明的排出气体净化用催化剂是使包含上述M置换硼酸铝的载体担载Pd而成的。通过使上述M置换硼酸铝担载Pd,会成为储氧能力优异、高温耐久后的排出气体净化性能、尤其是富相区域的NOX净化性能优异的排出气体净化用催化剂,Pd的担载量在换算成Pd金属的质量并以载体质量为基准时优选为0.35~3质量%、更优选为0.4~2质量%。Pd的担载量在换算成Pd金属的质量并以载体质量为基准时不足0.35质量%的情况下,由于贵金属的绝对量少,因此耐久性变差,而超过3质量%的情况下,贵金属的量过多,有时无法进行高分散担载。
本发明的排出气体净化用催化剂例如可以如下制造:将利用前述固相法或反向共沉淀法制造的M置换硼酸铝与Pd化合物(可溶性的Pd化合物、例如硝酸Pd、氯化Pd、硫酸Pd)的溶液以将Pd的担载量换算成Pd金属的质量并以载体的质量为基准时优选达到0.2~3质量%的量比的方式进行混合,其后,使其蒸发干固,在450~650℃下进行煅烧,从而制造。需要说明的是,在本说明书等的记载中,构成“溶液”的溶剂只要能够形成溶液就没有特别限定,通常可以使用水。
本发明的排出气体净化用催化剂构成体是在由陶瓷或金属材料制成的催化剂支撑体上形成并担载上述由本发明的排出气体净化用催化剂制成的层而成的。在这样的排出气体净化用催化剂构成体中,由陶瓷或金属材料制成的催化剂支撑体的形状没有特别限定,通常为蜂窝、板、粒料等形状。在蜂窝形状的情况下,担载于催化剂支撑体的排出气体净化用催化剂的担载量优选为70~200g/L、更优选为100~200g/L。该担载量不足70g/L时,由于担载量不足而存在耐久性变差的倾向。另外,作为这样的催化剂支撑体的材质,例如可列举出氧化铝(Al2O3)、富铝红柱石(3Al2O3-2SiO2)、堇青石(2MgO-2Al2O3-5SiO2)等陶瓷;不锈钢等金属材料。
本发明的排出气体净化用催化剂构成体例如可以通过以下方法来制造。将M置换硼酸铝50~70质量份、优选为50~60质量份、La稳定化氧化铝20~40质量份、优选为20~30质量份、氢氧化钡0~3质量份、优选为1~3质量份、以及氧化铝系粘结剂5~10质量份与Pd化合物的溶液混合,进行湿式粉碎处理而制备浆料。此时,以Pd的担载量在换算成Pd金属的质量并以载体质量为基准时优选达到0.35~3质量%、优选达到0.4~2质量%的量比的方式进行混合。利用公知的方法将所得浆料涂布在由陶瓷或金属材料制成的催化剂支撑体、优选涂布在蜂窝形状的催化剂支撑体上以使排出气体净化用催化剂的担载量优选达到70~200g/L、更优选达到100~200g/L,使其干燥,在450~650℃下进行煅烧,从而得到包含催化剂支撑体、以及在该催化剂支撑体上担载的排出气体净化用催化剂的层的排出气体净化用催化剂构成体。
以下,基于参考例、实施例以及比较例来具体地说明本发明。
参考例1
利用以下示出的固相法制备铁置换硼酸铝(Fe1Al17B4O33)。将以达到目标化合物的规定比的方式称量的硼酸溶解在离子交换水中。在该溶液中混合以达到规定比的方式称量的硝酸铁九水合物并使其溶解。其后,混合以达到规定比的方式称量的醋酸勃姆石溶胶,进行加热搅拌。将所得凝胶状产物在120℃下干燥12小时以上。干燥后,在空气中在300℃下煅烧1小时,进而在1000℃下煅烧5小时,从而得到铁置换硼酸铝。该铁置换硼酸铝的XRD图如图1所示。
参考例2
利用以下示出的固相法制备未置换硼酸铝(Al18B4O33)。将以达到目标化合物的规定比的方式称量的硼酸溶解在离子交换水中。其后,混合以达到规定比的方式称量的醋酸勃姆石溶胶,进行加热搅拌。将所得凝胶状产物在120℃下干燥12小时以上。干燥后,在空气中在300℃下煅烧1小时,进而在1000℃下煅烧5小时,从而得到未置换硼酸铝。该未置换硼酸铝的XRD图如图1所示。通过X射线衍射可以确定该硼酸铝是用式10Al2O3·2B2O3表示的硼酸铝。
另外,作为X射线衍射的标准图,存在式9Al2O3·2B2O3(Al18B4O33),产物也可确定为式9Al2O3·2B2O3(Al18B4O33)。
从图1所示的铁置换硼酸铝的XRD图与未置换硼酸铝的XRD图的比较可以明确:确认了与未置换硼酸铝的情况下的峰相比,铁置换硼酸铝的情况下的峰向低角度侧偏移,可判断硼酸铝中的Al原子被Fe原子置换。
参考例3
利用以下示出的反向共沉淀法制备铁置换硼酸铝(Fe1Al17B4O33)。将以达到目标化合物的规定比的方式称量的硼酸溶解在离子交换水中。在该溶液中混合以达到规定比的方式称量的硝酸铝九水合物和硝酸铁九水合物并使其溶解。接着,将该溶液滴加至碳酸铵水溶液中。将所得沉淀物用纯水过滤洗涤,在120℃下干燥12小时以上。接着,在空气中在300℃下煅烧1小时后,进而在空气中在1000℃下煅烧5小时,从而得到铁置换硼酸铝。利用该反向共沉淀法制备的铁置换硼酸铝与利用参考例1的固相法制备的铁置换硼酸铝之间未发现差异。通过在温度800℃下对还原性气氛:1.4%H2/He与氧化性气氛:0.7%O2/He进行切换时的质量变化来调查该铁置换硼酸铝的吸氧放氧行为,结果如图2所示。
参考例4
通过在温度800℃下对还原性气氛:1.4%H2/He与氧化性气氛:0.7%O2/He进行切换时的质量变化来调查参考例2中得到的未置换硼酸铝的吸氧放氧行为,结果如图2所示。
由图2所示的吸氧放氧行为可以明确:关于对还原性气氛与氧化性气氛进行切换时的质量变化,在铁置换硼酸铝的情况下为0.49%,在未置换硼酸铝情况下为0.18%。因此,与未置换硼酸铝的情况下的储氧能力相比,铁置换硼酸铝的情况下的储氧能力约为2.7倍。
实施例1
在硝酸钯溶液中浸渍参考例3中制造的铁置换硼酸铝载体以使Pd的担载量在换算成Pd金属的质量并以载体质量为基准时达到0.4质量%的量比,其后,在120℃下蒸发干固一晚(约15小时),在空气中在600℃下煅烧3小时,从而制造了本发明的排出气体净化用催化剂(0.4质量%的Pd/Fe1Al17B4O33)。
比较例1
在硝酸钯溶液中浸渍La稳定化氧化铝载体,以使Pd的担载量在换算成Pd金属的质量并以载体质量为基准时达到0.4质量%的量比,其后,在120℃下蒸发干固一晚(约15小时),在空气中在600℃下煅烧3小时,从而制造了比较例1的排出气体净化用催化剂(0.4质量%的Pd/La稳定化氧化铝)。
比较例2
在硝酸钯溶液中浸渍参考例2中制造的未置换硼酸铝载体,以使Pd的担载量在换算成Pd金属的质量并以载体质量为基准时达到0.4质量%的量比,其后,在120℃下蒸发干固一晚(约15小时),在空气中在600℃下煅烧3小时,从而制造了比较例2的排出气体净化用催化剂(0.4质量%的Pd/Al18B4O33)。
实施例2
与实施例1同样操作,制造了担载有0.4质量%的Pd的铁置换硼酸铝、担载有0.4质量%的Pd的镓置换硼酸铝、以及担载有0.4质量%的Pd的钴置换硼酸铝。通过在温度800℃下对还原性气氛:1.4%H2/He与氧化性气氛:0.7%O2/He进行切换时的质量变化来调查所得3种排出气体净化用催化剂和比较例2的排出气体净化用催化剂的吸氧放氧行为,结果如表1所示。
实施例3
除了使用硝酸镍六水合物来代替硝酸铁九水合物以外,与实施例1同样操作,制造了担载有0.4质量%的Pd的镍置换硼酸铝。通过在温度800℃下对还原性气氛:1.4%H2/He与氧化性气氛:0.7%O2/He进行切换时的质量变化来调查所得排出气体净化用催化剂和比较例2的排出气体净化用催化剂的吸氧放氧行为,结果如表1所示。
[表1]
由表1的数据可以明确:与未置换硼酸铝的情况下的储氧能力相比,铁、镓或钴置换的硼酸铝的情况下的储氧能力约为2倍。进而,镍置换的硼酸铝的情况下的储氧能力约为未置换硼酸铝的情况下的储氧能力的4倍。
<基于空燃比的变化的催化剂性能评价>
将比较例2中制造的由担载有0.4质量%的Pd的未置换硼酸铝(0.4质量%的Pd/Al18B4O33)制成的比较例的排出气体净化用催化剂、以及实施例1的由担载有0.4质量%的Pd的铁置换硼酸铝(0.4质量%的Pd/Fe1Al17B4O33)制成的实施例的排出气体净化用催化剂、以及实施例3的由担载有0.4质量%的Pd的镍置换硼酸铝(0.4质量%的Pd/Ni1Al17B4O33)制成的实施例的排出气体净化用催化剂分别在包含水蒸气10%的大气气氛中在900℃下进行25小时的耐久处理后,如下操作来评价由这些排出气体净化用催化剂的空燃比的变化引起的催化剂活性的变化。即,使用固定床流通型反应装置,在反应管中放置催化剂粉,使反应管中以W/F=5.0×10-4g·min·cm-3的方式流通假设完全燃烧时因O2浓度的变动而具有13.7~15.0范围内的空燃比(A/F)的模拟排出气体,所述模拟排出气体由CO:0.51%、NO:500ppm、C3H6:1182ppmC、O2:0.1~0.9%、H2O:10%、余量N2构成,使用CO/HC/NO分析仪(HORIBA VA-3000)在扫描速度0.0363/min、测定温度390℃下测定出口气体成分。通过O2浓度的变动从富相测定至贫相,其后再从贫相测定回富相。关于其测定结果,对CO的结果如图3所示、对HC的结果如图4所示、对NOX的结果如图5所示。另外,A/F=13.7时的400℃下的净化率(η400)如表2所示。
[表2]
其结果可知,由担载有0.4质量%的Pd的铁置换硼酸铝(0.4质量%Pd/Fe1Al17B4O33)制成的实施例的排出气体净化用催化剂与未置换的比较例相比,在富相区域的CO和NOx的净化率提高,由担载有0.4质量%的Pd的镍置换硼酸铝(0.4质量%Pd/Ni1Al17B4O33)制成的实施例的排出气体净化用催化剂与比较例相比,HC和NOx的净化率提高。
<耐热后的BET、Pd分散度以及催化剂性能评价>
将比较例2中制造的由担载有0.4质量%的Pd的未置换硼酸铝(0.4质量%的Pd/Al18B4O33)制成的比较例的排出气体净化用催化剂、以及实施例3的由担载有0.4质量%的Pd的镍置换硼酸铝(0.4质量%的Pd/Ni1Al17B4O33)制成的实施例的排出气体净化用催化剂分别在包含水蒸气10%的大气气氛中在900℃下进行25小时的耐久处理后,通过BET法测定这些排出气体净化用催化剂的比表面积。
另外,各个Pd分散度基于公知手段即CO脉冲吸附法(T. Takeguchi、S. Manabe、 R. Kikuchi、K. Eguchi、T. Kanazawa、S. Matsumoto、Applied Catalysis A:293(2005)9l.)进行测定。该Pd分散度是根据式
Pd分散度=相当于CO吸附量的Pd量(摩尔)/所包含的Pd的总量(摩尔)而计算出的值。
进而,使用固定床流通型反应装置,在反应管中放置各净化用催化剂,以W/F=5.0×10-4g·mim·cm-3的方式流通0.05%NO、0.51%CO、0.039%C3H6、0.4%O2、余量为He的模擬排出气体,以10℃/min升温至100℃~500℃,使用CO/HC/NOx分析仪测定100℃~500℃下的出口气体成分。由所得的起燃特性(ライトオフ性能)评价结果求出达到CO、HC以及NOx的50%净化率的温度(T50)。
它们的结果如表3所示。
[表3]
其结果可知:由担载有0.4质量%的Pd的镍置换硼酸铝(0.4质量%的Pd/Ni1Al17B4O33)制成的实施例的排出气体净化用催化剂的耐久后的比表面积与未置换的情况为同等水平,Pd分散性高。另外,由担载有0.4质量%的Pd的镍置换硼酸铝(0.4质量%的Pd/Ni1Al17B4O33)制成的实施例的排出气体净化用催化剂的低温活性高,与未置换的情况相比,CO、HC以及NOx的T50的温度为低温。
实施例4
在硝酸Pd溶液中添加利用参考例1中记载的方法制造的铁置换硼酸铝(Fe1Al17B4O33)55质量份、La稳定化氧化铝25质量份、氢氧化钡2质量份以及氧化铝系粘结剂8质量份,实施湿式粉碎处理,得到含Pd的浆料。此时,以Pd担载浓度相对于固体成分达到0.7质量%的方式添加硝酸Pd溶液。将所得浆料以达到100g/L的量的方式涂布于陶瓷蜂窝基材并干燥,进行煅烧,从而得到本发明的蜂窝催化剂(排出气体净化用催化剂构成体)。
比较例3
在硝酸Pd溶液中添加La稳定化氧化铝88质量份、氢氧化钡2质量份以及氧化铝系粘结剂8质量份,实施湿式粉碎处理,得到含Pd的浆料。此时,以Pd担载浓度相对于固体成分达到0.7质量%的方式添加硝酸Pd溶液。将所得浆料以达到100g/L的量的方式涂布于陶瓷蜂窝基材并干燥,进行煅烧,从而得到比较例的蜂窝催化剂(排出气体净化用催化剂构成体)。
比较例4
在硝酸Pd溶液中添加利用固相法制备的硼酸铝(Al18B4O33)55质量份、La稳定化氧化铝25质量份、氢氧化钡2质量份以及氧化铝系粘结剂8质量份,实施湿式粉碎处理,得到含Pd的浆料。此时,以Pd担载浓度相对于固体成分达到0.7质量%的方式添加硝酸Pd溶液。将所得浆料以达到100g/L的量的方式涂布于陶瓷蜂窝基材并干燥,进行煅烧,从而得到比较例的蜂窝催化剂(排出气体净化用催化剂构成体)。
<基于空燃比的变化的催化剂性能评价>
使用具有表4所示的组成和空燃比(A/F)且由CO、CO2、C3H6、H2、O2、NO、H2O以及余量的N2制成的假设完全燃烧的模拟排气来实施评价。另外,将蜂窝催化剂放置在保持为1000℃的电炉中,周期性地流通具有表4所示的组成和空燃比的模拟排气(50s)和空气(50s),进行25小时的耐久处理,对处理后的蜂窝催化剂评价净化性能。
[表4]
关于催化剂的λ扫描,对表4所示的模擬排气进行λ=0.4~1.5的扫描,以SV=100,000h-1的方式使实施例4、比较例3以及比较例4的陶瓷蜂窝催化剂中流通模擬排气,使用CO/HC/NOX分析仪测定400℃下的出口气体成分,评价各陶瓷蜂窝催化剂的性能。其结果,对CO的结果如表5所示、对HC的结果如表6所示、对NOX的结果如表7所示。
[表5]
[表6]
[表7]
从表7的数据可以明确:铁置换硼酸铝的富相区域的NOx净化性能在A/F=14.2时为38%、在A/F=14.4时为44%,与La稳定化氧化铝和硼酸铝相比是优异的。另外,从表6的数据可以明确:铁置换硼酸铝的富相区域的HC净化性能在A/F=14.2时为41%、在A/F=14.4时为87%,与La稳定化氧化铝和硼酸铝相比是优异的。可推测,这是由于1分子硼酸铝中的18个铝原子中的一部分、优选以平均计为0.5~2个被Fe原子置换,因而储氧能力提高,从而带来富相区域的性能的提高的缘故。
Claims (5)
1.排出气体净化用催化剂,其特征在于,其包含:含有将硼酸铝中的铝原子的2.5~11.5at%用Fe、Co、Ga或Ni进行了置换的置换硼酸铝的载体、以及担载于该载体的Pd。
2.排出气体净化用催化剂,其特征在于,其包含:含有用通式MmAl20-mB4O36表示的M置换硼酸铝的载体、以及担载于该载体的Pd,式MmAl20-mB4O36中,M为Fe、Co、Ga或Ni,m为0.5~2.3。
3.排出气体净化用催化剂,其特征在于,其包含:含有用通式MnAl18-nB4O33表示的M置换硼酸铝的载体、以及担载于该载体的Pd,式MnAl18-nB4O33中,M为Fe、Co、Ga或Ni,n为0.45~2.07。
4.根据权利要求1、2或3所述的排出气体净化用催化剂,其特征在于,载体为铁置换硼酸铝。
5.排出气体净化用催化剂构成体,其特征在于,其包含:由陶瓷或金属材料制成的催化剂支撑体、以及在该催化剂支撑体上担载的权利要求1、2、3或4所述的排出气体净化用催化剂的层。
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