CN101370567A - 硫化氢产生抑制单元和废气净化催化剂 - Google Patents
硫化氢产生抑制单元和废气净化催化剂 Download PDFInfo
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- CN101370567A CN101370567A CNA2007800022600A CN200780002260A CN101370567A CN 101370567 A CN101370567 A CN 101370567A CN A2007800022600 A CNA2007800022600 A CN A2007800022600A CN 200780002260 A CN200780002260 A CN 200780002260A CN 101370567 A CN101370567 A CN 101370567A
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- sulphur
- hydrogen sulfide
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 title claims description 59
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 112
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 20
- 239000005864 Sulphur Substances 0.000 claims description 110
- 239000000758 substrate Substances 0.000 claims description 56
- 239000011248 coating agent Substances 0.000 claims description 40
- 238000000576 coating method Methods 0.000 claims description 40
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 26
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 25
- 239000002912 waste gas Substances 0.000 claims description 20
- 229910000510 noble metal Inorganic materials 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical group 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 230000003578 releasing effect Effects 0.000 abstract description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 33
- 238000001179 sorption measurement Methods 0.000 description 23
- 239000002002 slurry Substances 0.000 description 21
- 239000000843 powder Substances 0.000 description 19
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 229910052684 Cerium Inorganic materials 0.000 description 13
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 206010013786 Dry skin Diseases 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000010948 rhodium Substances 0.000 description 10
- 239000006104 solid solution Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000001354 calcination Methods 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 229910052878 cordierite Inorganic materials 0.000 description 7
- 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 7
- 229910052703 rhodium Inorganic materials 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 230000005764 inhibitory process Effects 0.000 description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PXSIFGRGUVISHI-UHFFFAOYSA-N [Ni].[Ba] Chemical compound [Ni].[Ba] PXSIFGRGUVISHI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- NTWUDWUVKKRQRK-UHFFFAOYSA-N aluminum;cerium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Ce+3] NTWUDWUVKKRQRK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- -1 dinitro diamines Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Abstract
本文公开了一种硫化氢产生抑制单元,其包含:硫吸附部分2,它含有至少包含氧化铈的氧化物,该硫吸附部分2设置在废气的上游侧;和硫释放部分3,它设置在所述硫吸附部分2的下游侧并且具有比所述硫吸附部分2高的表面酸性。吸附在硫吸附部分上的SOx在高温区中释放,但是释放出的SOx难以吸附在硫释放部分3上,因此不会再次被吸附。从而,在不使用环境负担物质例如镍的情况下抑制H2S的产生。
Description
背景技术
1.发明领域
[0001]本发明涉及用于抑制来自车辆等的废气中硫化氢(以下称为“H2S”)产生的单元,以及使用该H2S产生抑制单元的废气净化催化剂。本发明的H2S产生抑制单元可以在高速运转之后发动机空转时抑制H2S的产生。本发明的H2S产生抑制单元可以单独使用,也可以用作废气净化催化剂例如三效催化剂。
2.现有技术的描述
[0002]作为用于净化车辆废气中的HC、CO和NOx的催化剂,已经广泛使用三效催化剂。这种三效催化剂通过在多孔氧化物载体例如氧化铝、氧化铈、氧化锆和氧化铈-氧化锆上负载铂族金属例如Pt和Rh来形成。另外,三效催化剂氧化和净化HC及CO,并且同时还原和净化NOx。由于这些催化反应在氧化组分和还原组分大致等量存在的气氛中有效进行,因此控制具有三效催化剂的车辆发动机中的燃料燃烧以使得它在大约理论空气燃料比(化学计量)(A/F=约14.6±0.2)发生。
[0003]然而,三效催化剂的问题在于,如果将废气氛引去还原的话,废气中的硫氧化物会被还原成H2S,H2S于是被排放到空气中。例如,具有吸附和释放氧的作用的氧化铈构成三效催化剂中的必要组分。然而,在具有包含氧化铈的三效催化剂的车辆发动机中,存在当例如在加速状态下出现的废气氛浓(还原气氛)时产生H2S的问题。
[0004]现在将解释用氧化铈产生H2S的机理。废气中的SO2通过金属催化剂氧化成SOx。氧化铈容易吸附SOx,因为它是具有相对高碱性的氧化物。据信所吸附的SOx在催化剂载体上缓慢富集,并且在还原气氛中还原成H2S。即使痕量的H2S被人的鼻子感觉到,也产生令人不快的感受,因此需要抑制其排放。另外,广泛用作催化剂载体的γ-氧化铝也容易吸附SOx。
[0005]在本文中,可以考虑Ni或Cu氧化物用作三效催化剂的组分。Ni或Cu氧化物可以抑制H2S产生,因为它在氧化气氛中将SO2转化成SO3或SO4以及在还原气氛中储存作为硫化物例如Ni2S3的硫组分。
[0006]例如,日本特开平08-015554公开了通过在载体上负载贵金属而形成的废气净化催化剂,该载体包含镍-钡复合氧化物、氧化铝和氧化铈。载体在贫气氛中通过氧化铝和氧化铈捕获硫氧化物作为硫酸盐,以及在还原气氛中通过该镍-钡复合氧化物捕获H2S。因此,它可以抑制H2S的产生。
[0007]此外,日本专利公开2000-515419或日本专利02598817公开了用氧化铈与NiO、Fe2O3等的混合物作为载体抑制H2S的产生。另外,日本特开平07-194978公开了用包含负载在氧化铈上的Ni和Ca的载体抑制H2S的产生。
[0008]然而,Ni或Cu由于它是环境负担物质而受限用于车辆废气净化催化剂。另一个问题是当例如将钡加入到三效催化剂中时会使其固有的净化性能变差。
[0009]另外,日本特开平02-020561公开了能够氧化和除去H2S的含铋催化剂。然而,由于这些催化剂在氧化气氛中氧化H2S,它们不能防止在化学计量或还原气氛中H2S的排放。
发明概述
[0010]本发明已完成来解决现有技术中出现的上述问题,并且本发明的目的在于不使用环境负担物质例如镍的情况下抑制H2S的产生。
[0011]为了实现上述目的,一方面,本发明提供一种用于抑制H2S产生的单元,其包含:硫吸附部分,它含有至少包括氧化铈的氧化物,并且设置在废气的上游侧;和硫释放部分,它具有比所述硫吸附部分高的表面酸性,并且设置在所述硫吸附部分的下游侧。
[0012]在另一方面,本发明提供一种废气净化催化剂,它包含硫化氢产生抑制单元和负载在其上的贵金属。
附图简要说明
[0013]从结合附图给出的下面优选实施方案的说明中,本发明的上述以及其它目的和特征将变得明显,其中:
图1是本发明第一实施方案的三效催化剂的示意性横截面图;
图2是本发明第二实施方案的三效催化剂的示意性横截面图;
图3是本发明第四实施方案的三效催化剂的示意性横截面图;和
图4是表示各实施例的H2S排放量的图表,其表示成相对于作为100的比较例H2S排放量的值。
优选实施方案的详细说明
[0014]现在将参照附图详细说明本发明的多种实施方案。
[0015]本发明的H2S产生抑制单元包含硫吸附部分和硫释放部分。所述硫吸附部分包含至少包括氧化铈的氧化物。例如,硫吸附部分可以包含氧化铈粉末与其它氧化物粉末例如氧化铝粉末的混合物,而且还可以包含单独的氧化铈或单独的含氧化铈的复合氧化物。含氧化铈的复合氧化物的实例可以包括氧化铈-氧化锆、氧化铝-氧化铈-氧化锆等。
[0016]作为硫吸附部分的氧化铈,优选使用比表面积小于5m2/g的氧化铈。在这种情况下,氧化铈的氧吸附和释放性能得到保持,同时降低其SOx吸附性能。因此,可以降低浓的程度,同时可以将SOx在被还原成H2S之前释放出,并可以抑制H2S的产生。类似地,当硫吸附部分含有氧化铝时,优选使用比表面积小于γ-氧化铝的θ-氧化铝。
[0017]所述硫释放部分具有比所述硫吸附部分高的酸性。可以使用采取酸性比硫吸附部分中的氧化铈高的氧化物的方法,或提高硫吸附部分的碱性的方法来提高硫释放部分的酸性。酸性比氧化铈高的氧化物的实例可以包括氧化硅、氧化硅-氧化铝复合氧化物、含氧化锆的氧化铝、二氧化钛、二氧化钛-氧化锆复合氧化物等,选自这些氧化物中的一种或多种可以用于本发明中。其中,优选使用二氧化钛,由于二氧化钛具有高酸性,因此SOx难以被吸附于其上。另外,尽管氧化铝或氧化锆具有相对较低的酸性,但是它可以有利地用于本发明中,因为当它涂有二氧化钛时其酸性会提高。
[0018]为了提高硫吸附部分的碱性,将选自例如碱土金属和稀土元素中的至少一种负载在硫吸附部分上。结果,硫吸附部分的碱性得到提高,导致其吸附SOx的能力提高。因此,可以抑制例如在高速运转之后发动机空转时SOx的排放,以至于可以抑制H2S的产生。所述选自碱土金属和稀土元素中的至少一种的负载量对于每升H2S产生抑制单元优选为0.01-0.5mol。少于0.01mol时,负载的金属或元素的效果不会表现出。另一方面,如果该金属或元素的负载量多于0.5mol,其效果饱和,同时当贵金属负载在硫吸附部分上时,贵金属的活性降低。
[0019]硫吸附部分设置在废气的上游侧,而且硫释放部分设置在硫吸附部分的下游侧。例如,可以将小球状的硫吸附部分填充在废气上游侧的排气管中,小球状的硫释放部分可以设置在硫吸附部分的下游侧。作为选择,具有形成在蜂窝基材上的包含例如氧化铈的涂层的蜂窝状硫吸附部分可以设置在废气的上游侧,并且具有形成在蜂窝基材上的包含例如二氧化钛的涂层的蜂窝状硫释放部分可以设置在硫吸附部分的下游侧。构成硫吸附部分的涂层可以形成在一个蜂窝基材上废气上游侧,并且构成硫释放部分的涂层可以形成在该蜂窝基材上在硫吸附部分的下游侧。
[0020]例如,在这样的H2S产生抑制单元的情况下,其中包含硫吸附部分的涂层形成在一个蜂窝基材上废气的上游侧,并且包含硫释放部分的涂层形成在该蜂窝基材上在硫吸附部分的下游侧,包含硫吸附部分的硫吸附层可以形成为该H2S产生抑制单元总长度的1/4-2/3。如果硫吸附层的长度小于该H2S产生抑制单元总长度的1/4,氧化铈的氧吸附和释放效果会过分降低,使得难以缓解浓气氛和抑制H2S的产生。另一方面,如果硫吸附层区域大于该H2S产生抑制单元总区域的2/3,SOx的吸附范围将增加,同时释放出的SOx会再次被吸附,使得难以抑制H2S的产生。
[0021]本发明的H2S产生抑制单元可以负载有贵金属例如Pt、Rh、Pd、Ir或Ru,因此可以用作抑制H2S产生的废气净化催化剂,优选用作三效催化剂。另外,所述贵金属在该H2S产生抑制单元上的负载提高该单元的H2S抑制性能。贵金属优选负载在至少所述硫吸附部分上。当贵金属负载在硫吸附部分上时,可以改善氧化铈的氧吸附和释放效果,以减小在废气氛中的波动。因此,容易将废气氛保持在近似化学计量比下,并且表现出三效催化剂的高活性。
[0022]然而,当只有硫吸附部分负载有必要量的贵金属时,则该金属的负载密度提高,以至于在催化剂使用过程中倾向于出现劣化例如晶粒生长。为此,优选将所述贵金属均匀地负载在硫吸附部分和硫释放部分上。
[0023]所述贵金属的负载量优选为0.05-10wt%。如果负载量少于0.05wt%,则该催化剂作为废气净化催化剂不实用,而如果贵金属的负载量多于10wt%,则其效果会饱和,同时增加催化剂的制备涂层。
[0024]在现有含氧化铈的三效催化剂中,氧化铈存在于整个废气中,因此SOx通过废气几乎被均匀地吸附。然而,在本发明的H2S产生抑制单元中,包含碱性氧化铈的硫吸附部分设置在废气的上游侧,并且具有比硫吸附部分高的表面酸性的硫释放部分设置在硫吸附部分的下游侧。因此,废气中的SOx被吸附在上游侧硫吸附部分上,而难以被吸附在硫释放部分上。换句话说,根据本发明的H2S产生抑制单元,SOx的吸附范围比现有技术中的窄,因此H2S的产生得到减少。
[0025]另外,在本发明的H2S产生抑制单元中,吸附在硫吸附部分上的SOx在高温区得到释放,但是释放出的SOx难以吸附在硫释放部分上。因此,防止该释放出的SOx再次被吸附而由其产生H2S。
[0026]此外,在硫吸附部分中,由于氧化铈的氧吸附和释放性能而降低浓气氛的程度,并且使浓度降低的废气与硫释放部分接触。因此,H2S在硫释放部分中变得更难产生。另外,使用负载有贵金属的废气净化催化剂,可以进一步改善氧化铈的氧吸附和释放效果,从而可以进一步抑制H2S的产生。
[0027]因此,本发明的H2S产生抑制单元和废气净化催化剂可以通过其协同作用来有效抑制H2S的产生和排放。
实施例
[0028]以下,将参照实施例和比较例更详细描述本发明。即使在不同的图中,类似标号表示类似单元。
[0029]实施例1
图1示出了本实施例的三效催化剂。该三效催化剂包含堇青石蜂窝基材1,形成在从废气上游侧起该蜂窝基材一半的一侧上的硫吸附层2,以及形成在从废气下游侧起该蜂窝基材1余下一半的一侧上的硫释放层3。硫吸附层2含有氧化铈-氧化锆固溶体,而硫释放层3不含氧化铈-氧化锆固溶体。以下,将描述该三效催化剂的制备方法。
[0030]制备堇青石蜂窝基材1(1.1L体积,103mm直径,130mm长,400cpsi孔室密度和100μm壁厚)。将蜂窝基材1从该蜂窝基材一端起的1/2长的范围(也就是该基材从废气上游侧起一半长度的范围)用浆料洗涂(wash-coat),该浆料包含90重量份θ-氧化铝粉末(100m2/g比表面积)和100重量份氧化铈-氧化锆固溶体粉末(CeO2:ZrO2=1:1摩尔比和85m2/g比表面积)作为主要组分。然后,使涂布的浆料在120℃干燥,并且在650℃煅烧3小时,从而形成硫吸附层2。硫吸附层2的形成量对于每升蜂窝基材1为190g。
[0031]接下来,将蜂窝基材上没有形成硫吸附层2的表面用含有θ-氧化铝粉末作为主要组分的浆料洗涂,并使涂布的浆料在120℃干燥,接着在650℃煅烧3小时,从而形成硫释放层3。硫释放层3的形成量对于每升蜂窝基材1为90g。
[0032]将具有硫吸附层2和硫释放层3的蜂窝基材1浸没在硝酸铑水溶液中以使得它吸附并且负载铑。然后,从溶液中取出基材1并在120℃干燥,接着在500℃煅烧1小时,以使得Rh均匀负载在整个基材1上。另外,在给定量的给定浓度的二硝基二胺合铂溶液中浸渍该蜂窝基材,以使得它吸附并且负载铂。然后,将基材在120℃干燥,接着在500℃煅烧1小时,以使得Pt均匀负载在整个基材1上。Pt和Rh的负载量对于每升蜂窝基材1分别为1.0g和0.2g。
[0033]实施例2
图2示出了本发明实施例2的三效催化剂。该三效催化剂包含堇青石蜂窝基材1,形成在整个蜂窝基材1上的第一涂层20,以及形成在第一涂层20表面上对应于蜂窝基材1一半长度的下游侧范围内的硫释放层3。第一涂层20含有氧化铈-氧化锆固溶体,而硫释放层3不含氧化铈-氧化锆固溶体。硫释放层3的表面酸性比第一涂层高。特别地,在对应于蜂窝基材1一半长度的上游侧范围中暴露的第一涂层20构成硫吸附层2。以下,将描述该三效催化剂的制备方法。
[0034]使用与实施例1相同的蜂窝基材1,并且将含有θ-氧化铝粉末(与实施例1相同)和氧化铈-氧化锆固溶体粉末(与实施例1相同)作为主要组分的相同浆料洗涂在整个蜂窝基材1上。然后,使涂布的浆料在120℃干燥,接着在650℃煅烧3小时,从而形成第一涂层20。第一涂层20的形成量对于每升蜂窝结构为190g。
[0035]接下来,在对应于蜂窝基材1一半长度的下游侧上的第一涂层20的表面用浆料洗涂,该浆料含有90重量份θ-氧化铝(100m2/g比表面积)和20重量份TiO2涂布的ZrO2粉末(TiO2:ZrO2=30:70)作为主要组分。然后,使涂布的浆料在120℃干燥,接着在650℃煅烧3小时,从而形成硫释放层3。硫释放层3的形成量对于每升蜂窝基材为20g。另外,用实施例1的相同方法使蜂窝基材负载Pt和Rh。
[0036]实施例3
除了硫释放层3的组成以外,本实施例与实施例1相同。以下,将描述实施例3的三效催化剂的制备方法。
[0037]使用与实施例1相同的蜂窝基材,并且在蜂窝基材从该基材一端起的1/2长度的范围内形成与实施例1相同的硫吸附层2。
[0038]接下来,将浆料洗涂在蜂窝基材从下游侧起一半长度的范围内,该浆料含有90重量份θ-氧化铝粉末(比表面积100m2/g)和20重量份TiO2涂布的ZrO2粉末(TiO2:ZrO2=30:70)作为主要组分。然后,使涂布的浆料在120℃干燥,接着在650℃煅烧3小时,从而形成硫释放层3。硫释放层3的形成量对于每升蜂窝基材1为110g。另外,用实施例1的相同方法使蜂窝基材1负载Pt和Rh。
[0039]实施例4
图3示出了实施例4的三效催化剂。该三效催化剂包含堇青石蜂窝基材1和形成在整个蜂窝基材1上的涂层30。在对应于蜂窝基材一半长度的上游侧范围内的涂层30负载有Ba。因而,涂层的表面酸性在对应于该基材一半长度的下游侧范围内比在对应于该基材一半长度的上游侧范围内要高。硫吸附层2形成在上游侧的一半长度上,硫释放层3形成在下游侧的一半长度上。以下,将描述该三效催化剂的制备方法。
[0040]制备与实施例1相同的蜂窝基材1。将蜂窝基材1从其一端起一半长度的范围洗涂浆料,该浆料含有90重量份θ-氧化铝粉末(与实施例1相同)、100重量份氧化铈-氧化锆固溶体粉末(与实施例1相同)和给定量的硫酸钡粉末作为主要组分。然后,使涂布的浆料在120℃干燥,接着在650℃煅烧3小时,从而形成硫吸附层2。硫吸附层2的形成量对于每升蜂窝基材1为190g。Ba的负载量对于每升蜂窝基材1为0.1mol。
[0041]接下来,将蜂窝基材1从下游侧一端起一半长度的范围用浆料洗涂,该浆料含有90重量份θ-氧化铝粉末(与实施例1相同)和100重量份氧化铈-氧化锆固溶体粉末(与实施例1相同)作为主要组分。然后,使涂布的浆料在120℃干燥,接着在650℃煅烧3小时,从而形成硫释放层3。硫释放层3的形成量对于每升蜂窝基材1为190g。另外,用实施例1的相同方法负载Pt和Rh。
[0042]实施例5
用实施例4的相同方法,实施例5的三效催化剂包含堇青石蜂窝基材1和形成在整个蜂窝基材1上的涂层30。在对应于蜂窝基材一半长度的上游侧的涂层30负载有La。La的负载量对于每升蜂窝基材为0.1mol。因而,涂层30的表面酸性在对应于该蜂窝基材1一半长度的下游侧比上游侧的高。另外,硫吸附层2形成在对应于该基材一半长度的上游侧,硫释放层3形成在对应于该基材一半长度的下游侧。除了用氧化镧粉末代替硫酸钡粉末以外,用实施例4的相同方法制备本实施例的三效催化剂。
[0043]实施例6
用实施例4的相同方法,实施例6的三效催化剂包含堇青石蜂窝基材1和形成在整个蜂窝基材1上的涂层30。在对应于该基材一半长度的上游侧的涂层30负载有Ba和La。Ba和La各自的负载量对于每升蜂窝基材1为0.1mol。因而,涂层30的表面酸性在对应于该蜂窝基材1一半长度的下游侧比上游侧的高。另外,硫吸附层2形成在对应于该基材一半长度的上游侧,硫释放层3形成在对应于该基材一半长度的下游侧。除了使用氧化镧粉末和硫酸钡粉末以外,用实施例4的相同方法制备本实施例的三效催化剂。
[0044]实施例7
除了硫吸附层中所含的氧化铈-氧化锆固溶体的比表面积为3m2/g以外,用实施例1的相同方法进行实施例7。
[0045]比较例
本比较例的三效催化剂包含堇青石蜂窝基材1和形成在整个蜂窝基材1上的涂层30,并且涂层组成在整个基材上均一。以下,将描述该三效催化剂的制备方法。
[0046]使用与实施例1相同的蜂窝基材1,并且将含有90重量份γ-氧化铝粉末(比表面积180m2/g)和100重量份氧化铈-氧化锆固溶体粉末(与实施例1相同)作为主要组分的浆料洗涂在整个蜂窝基材1上。然后,使涂布的浆料在120℃干燥,接着在650℃煅烧3小时,从而形成涂层21。涂层21的形成量对于每升蜂窝基材1为190g。另外,用实施例1的相同方法负载Pt和Rh。
[0047]测试和分析
下表1概括各催化剂的氧化物结构。
[表1]
上游-半部分(硫吸附层) | 下游-半部分(硫释放层) | |
实施例 1 | θ-Al2O3,CeO2-ZrO2 | θ-Al2O3 |
实施例 2 | θ-Al2O3,CeO2-ZrO2 | θ-Al2O3,CeO2-ZrO2,TiO2/ZrO2 |
实施例 3 | θ-Al2O3,CeO2-ZrO2 | θ-Al2O3,TiO2/ZrO2 |
实施例 4 | θ-Al2O3,CeO2-ZrO2,BaSO4 | θ-Al2O3,CeO2-ZrO2 |
实施例 5 | θ-Al2O3,CeO2-ZrO2,La2O3 | θ-Al2O3,CeO2-ZrO2 |
实施例 6 | θ-Al2O3,CeO2-ZrO2,BaSO4,La2O3 | θ-Al2O3,CeO2-ZrO2 |
实施例 7 | θ-Al2O3,CeO2-ZrO2(3m2/g) | θ-Al2O3, |
比较例 1 | γ-Al2O3,CeO2-ZrO2 | γ-Al2O3,CeO2-ZrO2 |
将各三效催化剂安装于控制在化学计量比下的发动机试验台的排气系统中。然后,发动机在LA#4模式下运转,并且在其中猛踩油门塔板的完全加速模式下加速至80km/hr。接下来,将操作模式转换到空转状态。刚好在转换到空转模式之后,测定排放的H2S量,测量结果示于图4中,其中各实施例的测量值表示成相对于作为100的比较例的值。
[0048]如图4所示,可以看到各实施例的三效催化剂表现出比比较例低的H2S排放。这是由于形成了硫吸附层2和硫释放层3。另外,实施例3表现出比实施例1和2低的值,而实施例6表现出比实施例4和5低的值。这暗示硫吸附层2与硫释放层3之间的酸性差异较大是优选的。另外,实施例7表现出比实施例1低的值,暗示着硫吸附层2中所含的氧化铈的表面积较小是优选的。
[0049]另外,用上述相同方法测试其中从实施例和比较例的三效催化剂中除去Pt和Rh的H2S产生抑制单元。结果,除了所有实施例和比较例在H2S排放上都表现出略有增加之外,实施例与比较例的相对值等于图4中所示的三效催化剂的值。
[0050]尽管已经关于优选的实施方案示出和描述了本发明,但是本领域技术人员应当理解在不背离如下列权利要求中限定的本发明的精神和范围的情况下,可以进行各种变化和改进。
Claims (8)
1.一种硫化氢产生抑制单元,其包含:
硫吸附部分,它含有至少包括氧化铈的氧化物,并且设置在废气的上游侧;和
硫释放部分,它具有的表面酸性比所述硫吸附部分的表面酸性高,并且设置在所述硫吸附部分的下游侧。
2.权利要求1的硫化氢产生抑制单元,其中所述硫释放部分包含二氧化钛。
3.权利要求1的硫化氢产生抑制单元,其中所述硫吸附部分负载有选自碱土金属和稀土元素中的至少一种元素。
4.权利要求3的硫化氢产生抑制单元,其中所述选自碱土金属和稀土元素中的至少一种元素的负载量对于每升硫化氢产生抑制单元为0.01-0.5mol。
5.权利要求1的硫化氢产生抑制单元,其中包含所述硫吸附部分的涂层形成在废气上游侧蜂窝基材上,包含所述硫释放部分的涂层形成在其下游侧,并且所述包含硫吸附部分的涂层形成为硫化氢产生抑制单元的总长度的约1/4-2/3。
6.一种包含硫化氢产生抑制单元的废气净化催化剂,其包含:
硫吸附部分,它含有至少包括氧化铈的氧化物,并且设置在废气的上游侧;和
硫释放部分,它具有的表面酸性比所述硫吸附部分的表面酸性高,并且设置在所述硫吸附部分的下游侧,以及
负载在硫化氢产生抑制单元上的贵金属。
7.权利要求6的废气净化催化剂,其中所述贵金属负载在至少所述硫吸附部分上。
8.权利要求6的废气净化催化剂,其中所述贵金属均匀地负载在所述硫吸附部分和所述硫释放部分上。
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WO2009058569A2 (en) * | 2007-10-31 | 2009-05-07 | Sud-Chemie Inc. | Catalyst for reforming hydrocarbons |
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CN108138618B (zh) | 2015-09-24 | 2020-06-16 | 本田技研工业株式会社 | 内燃机的废气净化系统 |
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