CN109225316A - 一种尾气处理催化剂及其制备方法和用途 - Google Patents
一种尾气处理催化剂及其制备方法和用途 Download PDFInfo
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- CN109225316A CN109225316A CN201811168858.3A CN201811168858A CN109225316A CN 109225316 A CN109225316 A CN 109225316A CN 201811168858 A CN201811168858 A CN 201811168858A CN 109225316 A CN109225316 A CN 109225316A
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- Prior art keywords
- catalyst
- active component
- exhaust gas
- gas treatment
- auxiliary agent
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Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 279
- 238000002360 preparation method Methods 0.000 title claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 39
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000006227 byproduct Substances 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 239000002808 molecular sieve Substances 0.000 claims abstract description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 239000000356 contaminant Substances 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 68
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 47
- 239000012752 auxiliary agent Substances 0.000 claims description 27
- 239000007767 bonding agent Substances 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052703 rhodium Inorganic materials 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000003345 natural gas Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 239000006255 coating slurry Substances 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 32
- 229910000069 nitrogen hydride Inorganic materials 0.000 abstract description 31
- 229910021529 ammonia Inorganic materials 0.000 abstract description 12
- 239000003344 environmental pollutant Substances 0.000 abstract description 12
- 231100000719 pollutant Toxicity 0.000 abstract description 12
- 230000009467 reduction Effects 0.000 abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 41
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 37
- 239000011248 coating agent Substances 0.000 description 31
- 238000000576 coating method Methods 0.000 description 31
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000010948 rhodium Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229910001868 water Inorganic materials 0.000 description 16
- 229910052878 cordierite Inorganic materials 0.000 description 15
- 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 group [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 15
- 239000010949 copper Substances 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- 230000000996 additive effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 230000005404 monopole Effects 0.000 description 5
- 239000013618 particulate matter Substances 0.000 description 5
- -1 Beta Chemical compound 0.000 description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
- 229960004424 carbon dioxide Drugs 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000003701 mechanical milling Methods 0.000 description 3
- 238000000034 method 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
- 238000012805 post-processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 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 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000029142 excretion Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical class CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
Classifications
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- B01J29/763—CHA-type, e.g. Chabazite, LZ-218
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- B01D53/8646—Simultaneous elimination of the components
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- B01D53/9436—Ammonia
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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Abstract
本发明公开了一种尾气处理催化剂,该催化剂由载体、第一催化剂和第二催化剂组成,所述第一催化剂和第二催化剂设于所述载体两端,第一催化剂能净化处理尾气中的污染物,第二催化剂能净化处理第一催化剂净化处理后的副产物氨气以及第一催化剂未净化完全的部分污染物;其中,所述第二催化剂为双层结构,下层由储氧材料、氧化铝和第二活性组分组成,所述第二活性组分为Pt与Pd的组合物,或者Ce、Fe、Ni、Cu的组合物;上层由分子筛和第三活性组分组成,所述第三活性组分为Cu,或者Cu、Fe的组合物。本发明的尾气处理催化剂,净化处理效率高,能够显著减少尾气中CH4、CO和NOx的排放,特别是减少副产物NH3的含量,使其能满足国六的排放要求。
Description
技术领域
本发明涉及尾气处理技术领域,特别涉及一种尾气处理催化剂及其制备方法和用途。
背景技术
重型天然气汽车从国五到国六,发动机的燃烧方式从稀薄燃烧升级到当量比燃烧,相应地,后处理催化剂从氧化性催化剂(Methane Oxidation Catalyst,MOC)升级到三效催化剂(Three Way Catalyst,TWC)。TWC在当量燃烧条件下,能将尾气中的HC(包括CH4和NMHC)、CO、和NOx转化为N2、CO2和H2O,但在该催化转化过程中,会产生副产物NH3。
GB17691-2018《重型柴油车污染物排放限值及测量方法(中国第六阶段)》,该标准适用于重型天然气汽车和重型柴油车,其中天然气汽车从2019年7月1日起实施该标准。该标准在GB17691-2005的基础上,气态污染物除进一步降低CO、HC和NOx的限值外,还新增了NH3的限值要求。
CO、HC、NOx三种污染物通过TWC可以净化到国六限值以下,但在理论空燃比附近,特别是偏浓的条件下,CO、NO和H2反应生成NH3和H2O,新增的副产物NH3的排放量远远超过了国六排放法规的要求(排放量是限值的5-10倍以上),必须净化新增副产物NH3以满足法规要求。
NH3是一种不稳定的化合物,在一定的温度条件下,很容易被氧化,氧化产物通常是N2、N2O和NO。该反应的难点是NH3氧化为N2的选择性。氨氧化催化剂(Ammonia OxidationCatalyst,简称AOC)在柴油车后处理中已有应用,相对于柴油车,当量燃烧的天然气汽车在相同的工作条件下,尾气温度一般要比柴油车高200℃左右,而用于柴油车的氨氧化催化剂,随着温度升高到450℃以上,NH3氧化为N2的选择性会明显降低,因此,用于天然气汽车的氨氧化催化剂,高温时对NH3氧化为N2的选择性方面的要求显著提高。
为使重型天然气汽车尾气排放满足国六法规,必须开发一种后处理催化剂,可同时将尾气中的HC、CO、NOx、PM和NH3净化到国六限值内。
发明内容
本发明的目的在于克服现有尾气处理催化剂不能有效净化处理尾气新增副产物NH3的缺陷,提供一种能够有效净化处理尾气中烃类化合物、一氧化碳、氮氧化物、颗粒物以及新增副产物NH3的尾气处理催化剂,以及该尾气处理催化剂的制备方法和用途。
为实现上述发明目的,本发明提供了以下技术方案:
一种尾气处理催化剂,该催化剂由载体、第一催化剂和第二催化剂组成,所述第一催化剂和第二催化剂设于所述载体两端,第一催化剂能净化处理尾气中的CH4、NMHC、CO和NOx;第二催化剂能净化处理第一催化剂净化处理后的副产物NH3以及第一催化剂未净化完全的部分污染物;其中,
所述第二催化剂为双层结构,下层由储氧材料、氧化铝和第二活性组分组成,
所述第二活性组分为Pt与Pd的组合物,或者Ce、Fe、Ni、Cu的组合物;
上层由分子筛和第三活性组分组成,
所述第三活性组分为Cu,或者Cu、Fe的组合物。
上述尾气处理催化剂可以为单极分段催化剂或者两极催化剂,由三种催化剂功能区域组成。催化剂前段(或前极)由载体材料和第一催化剂组成,第一催化剂为三效催化剂,主要将尾气中的甲烷、非甲烷碳氢、一氧化碳、氮氧化物和颗粒物等污染物净化处理成二氧化碳、氮气和水;催化剂后段(或后极)由载体材料和第二催化剂组成,其中,第二催化剂分为上下两层:下层为氨氧化催化剂,主要将氨气氧化为氮气和少部分的一氧化氮,上层为被动选择还原型催化剂,主要将氨气和一氧化氮转化为氮气和水,本催化剂后端(或后极)主要将尾气中的原排氨气或者催化剂前段(或前极)净化处理后的新增副产物氨气和催化剂前段(或前极)未净化处理的甲烷、非甲烷碳氢、氮氧化物、一氧化碳等污染物净化处理为二氧化碳、氮气和水。
进一步地,所述第二催化剂上、下两层的总上载量为50~200g/L,其中,上层与下层上载量之比为(0.1~10):1。
优选地,所述第二催化剂下层涂层上载量为0.1~150g/L,上层涂层上载量为0.1~150g/L,上、下两层的总上载量为50~200g/L。
更优选地,所述第二催化剂下层涂层上载量为10~100g/L,上层涂层上载量为10~100g/L,上、下两层的总上载量为100~180g/L。
更优选地,所述第二催化剂下层涂层上载量为30~80g/L,上层涂层上载量为50~100g/L,上、下两层的总上载量为150~180g/L。
进一步地,所述第二活性组分为Pt、Pd的组合物时,Pt与Pd的重量配比为(10~1):(1~0)。
优选地,所述第二活性组分为Pt、Pd的组合物时,Pt与Pd的重量配比为(10~1):(1~0.5)。
更优选地,所述第二活性组分为Pt、Pd的组合物时,Pt与Pd的重量配比为(10~5):(1~0.5)。
进一步地,所述第二催化剂下层中第二活性组分含量为0.1~10g/ft3。
优选地,所述第二催化剂下层中第二活性组分含量为1~10g/ft3。
更优选地,所述第二催化剂下层中第二活性组分含量为1~5g/ft3。
进一步地,所述分子筛为Beta、ZSM-5、SSZ-13或SAPO-34等小孔分子筛中的一种或几种的组合物。
第二催化剂,在理论空燃比条件或略微偏稀(氧气过量)的条件下,采用下层贵金属和上层分子筛分层涂覆形成催化剂。下层采用单Pt或Pt、Pd双金属为主组成的贵金属催化剂或以Ce、Fe、Ni、Cu等过渡金属催化剂,将发动机排放的NH3和三效催化剂副反应产生的NH3主要转化为N2;以及将部分未被三效催化剂转化的CO、CH4和NMHC转化为CO2和H2O;上层采用以Cu或Cu、Fe为活性组分,Beta、ZSM-5、SSZ-13或SAPO-34等小孔分子筛中的一种或多种为载体,制备的催化剂,发生HC-SCR和NH3-SCR反应,将NH3、NOx、CH4等转化为N2、CO2和H2O。第二催化剂的活性组分含量、比例以及涂层上载量可根据发动机的实际尾气排放特点作相应调整。
进一步地,所述第一催化剂由储氧材料、氧化铝、助剂和第一活性组分组成;所述第一活性组分为Pt、Pd和Rh的组合物。
进一步地,所述第一活性组分中Pt、Pd和Rh的重量配比为(0~50):(1~100):(1~10)。
优选地,所述第一活性组分中Pt、Pd和Rh的重量配比为(10~50):(20~100):(3~10)。
优选地,所述第一活性组分中Pt、Pd和Rh的重量配比为(20~50):(50~100):(3~8)。
所述第一催化剂的干基涂层上载量为100~250g/L,第一活性组分的含量为50~200g/ft3。
第一催化剂是采用以Pt、Pd、Rh三种贵金属为主要活性组分的Pt/Pd/Rh型三效催化剂或以Pd、Rh两种贵金属为主要活性组分的Pd/Rh型三效催化剂,在理论空燃比附近,将尾气中的CH4、NMHC、CO、NOx和颗粒物转化为CO2、N2和H2O。第一催化剂的活性组分含量、比例以及涂层上载量可根据发动机的实际尾气排放特点作相应调整。
进一步地,所述第一催化剂与第二催化剂的体积比为(0.5~10):1。
优选地,所述第一催化剂与第二催化剂的体积比为(0.5~5):1。
优选地,所述第一催化剂与第二催化剂的体积比为(1~3):1。
在上述尾气处理催化剂中,所述载体优先为堇青石载体,所述催化材料优选为储氧材料和氧化铝,所述助剂为硝酸铈、硝酸钡等。在所述活性组分中,Pt组分在催化剂中主要起氧化CO和HC的作用,它对NO有一定的还原能力,但是CO的浓度较高或者有SO2存在时,它的效果没有Rh好;Rh组分是催化还原氮氧化物的主要成分,在有氧时,主要还原产物是N2,仅生成少量NH3;无氧或氧含量低于化学计量比时,还原产物除N2外,NH3的生成量大幅提高;Pd组分主要用来转化CO和烃类,对于饱和烃类效果稍差,抗S中毒能力差,易高温烧结,但它的稳定性较高,起燃性好。助剂本身是一些没有催化作用或者活性较低的添加物,能大大提高催化剂的活性、选择性和寿命。铈氧化物是汽车尾气净化催化剂最主要的助剂,其主要作用有:贮存及释放氧气;提高贵金属的分散性,抑制贵金属颗粒与氧化铝形成无活性的固溶体;提高催化剂的抗中毒能力;增加催化剂的稳定性等。
本发明还提供了上述尾气处理催化剂的制备方法,包括如下步骤:
1)第一催化剂制备:
S01.将第一活性组分前躯体浸渍到储氧材料和氧化铝表面,然后于60~120℃干燥2~10小时,在350~600℃的空气气氛中焙烧2~5小时,得到M-1;示例性地,在90℃干燥6小时,在475℃的空气气氛中焙烧3.5小时,得到M-1;
以等体积浸渍法将第一活性组分前驱体浸渍到储氧材料和氧化铝表面,控制浸渍的量使第一活性组分单质占比为0~6%;
S02.将M-1与1~5wt.%的粘接剂混合,球磨制浆,添加0~5wt.%的助剂,所述助剂添加量以助剂氧化物计,即得第一催化剂浆料N-1;示例性地,粘接剂的添加量为3%,助剂的添加量为2.5%;
所述粘接剂包括但不限于铝溶胶和硅溶胶,球磨过程中,控制所得浆料固含量为25~50%;
2)第二催化剂制备:
S01.将第二活性组分前躯体浸渍到储氧材料和氧化铝表面,然后于60~120℃干燥2~10小时,在350~600℃的空气气氛中焙烧2~5小时,得到M-2;示例性地,在90℃干燥6小时,在475℃的空气气氛中焙烧3.5小时,得到M-2;
以等体积浸渍法将第二活性组分前驱体浸渍到储氧材料和氧化铝表面,控制浸渍的量使第二活性组分单质占比为0~1%;
S02.将M-2与1~5wt.%的粘接剂混合,球磨制浆,添加0~5wt.%的助剂,所述助剂添加量以助剂氧化物计,即得第二催化剂下层浆料N-2;示例性地,粘接剂的添加量为3%,助剂的添加量为2.5%;
所述粘接剂包括但不限于铝溶胶和硅溶胶,球磨过程中,控制所得浆料固含量为25~50%;
S03.将第三活性组分前躯体以离子交换法交换到分子筛骨架内,过滤,洗涤,然后于60~120℃干燥2~10小时,在350~650℃的空气气氛中焙烧2~8小时,得到M-3;示例性地,在90℃干燥6小时,在500℃的空气气氛中焙烧5小时,得到M-3;
控制离子交换的量,使第三活性组分单质占比为0~3%;
S04.将M-3与1~5wt.%的粘接剂混合,球磨制浆,添加0~5wt.%的助剂,所述助剂添加量以助剂氧化物计,即得第二催化剂上层浆料N-3;示例性地,粘接剂的添加量为3%,助剂的添加量为2.5%;
所述粘接剂包括但不限于铝溶胶和硅溶胶,球磨过程中,控制所得浆料固含量为25~50%;
3)尾气处理催化剂制备:在载体一端涂覆浆料N-1,在载体另一端一次涂覆浆料N-2和浆料N-3,然后于60~120℃干燥2~10小时,并在350~600℃的空气气氛中焙烧2~8小时,即得尾气处理催化剂。示例性地,在90℃干燥6小时,并在475℃的空气气氛中焙烧5小时,即得尾气处理催化剂。
在上述制备方法中,所述活性组分前驱体是指各活性组分的硝酸盐、硝酸四胺盐或其它无机盐,示例性地,所述活性组分前驱体为硝酸铂、硝酸钯、硝酸铑、硝酸四胺铂、硝酸四胺钯、氯铂酸等。所述活性组分前驱体溶液可以是单一的活性组分前驱体溶液,也可以是多种活性组分前驱体溶液的混合溶液,或者前驱体溶液与助剂盐溶液的混合溶液。
本发明还提供了上述尾气处理催化剂在净化处理天然气汽车尾气中的用途。
与现有技术相比,本发明的有益效果:
本发明的尾气处理催化剂,第一催化剂能净化处理尾气中的NO、HC和CO,第二催化剂能净化处理尾气原排和第一催化剂反应副产物NH3,以及净化前段未反应完全的NO、HC和CO,净化处理效率高,能够显著减少尾气中各污染性气体特别是新增副产物NH3的含量,使其能满足国六的排放要求。
附图说明:
图1为本发明实施例中单极分段尾气处理催化剂结构示意图。
图2为本发明实施例中两极尾气处理催化剂结构示意图。
图3为第一催化剂不同涂层上载量对CH4起燃温度(T50)的影响。
图4为第一催化剂不同贵金属含量对CH4起燃温度(T50)的影响。
图5为第二催化剂不同Pt/Pd比例对NH3起燃温度(T50)的影响。
图6为第二催化剂贵金属不同含量对NH3起燃温度(T50)的影响。
图中标记:1-载体,2-第一催化剂,3-第二催化剂,31-第二催化剂下层,32-第二催化剂上层。
具体实施方式
下面结合试验例及具体实施方式对本发明作进一步的详细描述。但不应将此理解为本发明上述主题的范围仅限于以下的实施例,凡基于本发明内容所实现的技术均属于本发明的范围。
本发明实施例中所使用的仪器和原料均为已知市售产品,通过购买市售产品获得。
基础实施例
如图1或2所示,一种尾气处理催化剂,该催化剂由载体、第一催化剂和第二催化剂组成,所述第一催化剂和第二催化剂设于所述载体两端,第一催化剂能净化处理尾气中的CH4、NMHC、CO和NOx;第二催化剂能净化处理第一催化剂净化处理后的副产物NH3以及第一催化剂未净化完全的部分污染物;其中,
所述第二催化剂3为双层结构,下层31由储氧材料、氧化铝和第二活性组分组成,所述第二活性组分为Pt与Pd的组合物,或者Ce、Fe、Ni、Cu等过渡金属的组合物;上层32由分子筛和第三活性组分组成,所述第三活性组分为Cu,或者Cu、Fe的组合物。
所述第一催化剂2的种类不作特别限定,只要其能将尾气中的甲烷、非甲烷碳氢、一氧化碳、氮氧化物和颗粒物等污染物净化处理成二氧化碳、氮气和水即可。示例性地,所述第一催化剂2为三效催化剂,由储氧材料、氧化铝、助剂和第一活性组分组成;所述第一活性组分为Pt、Pd和Rh的组合物,Pt、Pd和Rh的重量配比为(0~50):(1~100):(1~10),优选地,所述第一活性组分中Pt、Pd和Rh的重量配比为(10~50):(20~100):(3~10),优选地,所述第一活性组分中Pt、Pd和Rh的重量配比为(20~50):(50~100):(3~8)。示例性地,第一活性组分中Pt、Pd和Rh的重量配比可以为0:1:1、50:100:10、15:35:3、35:75:5等;所述第一催化剂2涂覆与载体1表面,干基涂层上载量为100~250g/L,第一活性组分的含量为50~200g/ft3,示例性地,如图3对比了第一催化剂2的涂层上载量是100g/L、150g/L、200g/L、250g/L时CH4的起燃温度(T50);如图4,对比了第一催化剂2的第一活性组分的含量是50g/ft3、100g/ft3、150g/ft3、200g/ft3时CH4的起燃温度(T50)。
所述第二催化剂3上、下两层的总上载量为50~200g/L,其中,上层与下层上载量之比为(0.1~10):1。
优选地,所述第二催化剂下层31涂层上载量为0~150g/L,上层32涂层上载量为0~150g/L,上、下两层的总上载量为50~200g/L。
更优选地,所述第二催化剂下层31涂层上载量为10~100g/L,上层32涂层上载量为10~100g/L,上、下两层的总上载量为100~180g/L。
更优选地,所述第二催化剂下层31涂层上载量为30~80g/L,上层32涂层上载量为50~100g/L,上、下两层的总上载量为150~180g/L。
示例性地,第二催化剂3上下两层的总上载量为100g/L,上层32上载量为50g/L,下层31上载量为50g/L;或者,第二催化剂3上下两层的总上载量为130g/L,上层32上载量为75g/L,下层31上载量为55g/L;或者,第二催化剂3上下两层的总上载量为165g/L,上层32上载量为85g/L,下层31上载量为80g/L;或者,第二催化剂3上下两层的总上载量为180g/L,上层32上载量为100g/L,下层31上载量为80g/L;或者,第二催化剂3上下两层的总上载量为80g/L,上层32上载量为50g/L,下层31上载量为30g/L。
所述第二活性组分为Pt、Pd的组合物时,Pt与Pd的重量配比为(10~1):(1~0)。
优选地,所述第二活性组分为Pt、Pd的组合物时,Pt与Pd的重量配比为(10~1):(1~0.5)。
更优选地,所述第二活性组分为Pt、Pd的组合物时,Pt与Pd的重量配比为(10~5):(1~0.5)。
示例性地,所述第二活性组分中Pt与Pd的重量配比可以为10:1、5:0、2:1、1:1或者1:5。图5对比了所述第二催化剂下层31中第二活性组分Pt与Pd的重量配比是10:1、5:0、2:1、1:1和1:5时NH3的起燃温度(T50)。
所述第二催化剂下层31中第二活性组分含量为0.1~10g/ft3。
优选地,所述第二催化剂下层中第二活性组分含量为1~10g/ft3。
更优选地,所述第二催化剂下层31中第二活性组分含量为1~5g/ft3。
示例性地,所述第二催化剂下层31中第二活性组分含量可以为1g/ft3、2g/ft3、3g/ft3、5g/ft3或者10g/ft3。如图6,对比了所述第二催化剂下层31中第二活性组分Pt与Pd比例为2:1且总量为为1g/ft3、2g/ft3、3g/ft3、5g/ft3和10g/ft3时NH3的起燃温度(T50)。
所述第二催化剂上层32中分子筛为Beta、ZSM-5、SSZ-13或SAPO-34等小孔分子筛中的一种或几种的组合物。示例性地,所述分子筛可以为Beta或者ZSM-5与SSZ-13的组合物。
第二催化剂3,在理论空燃比条件或略微偏稀(氧气过量)的条件下,采用下层贵金属和上层分子筛分层涂覆形成催化剂。下层31采用单Pt或Pt、Pd双金属为主组成的贵金属催化剂或以Ce、Fe、Ni、Cu等过渡金属催化剂,将发动机排放的NH3和三效催化剂副反应产生的NH3主要转化为N2;以及将部分未被三效催化剂转化的CO、CH4和NMHC转化为CO2和H2O;上层32采用以Cu或Cu、Fe为活性组分,Beta、ZSM-5、SSZ-13或SAPO-34等小孔分子筛中的一种或多种为载体,制备的催化剂,发生HC-SCR和NH3-SCR反应,将NH3、NOx、CH4等转化为N2、CO2和H2O。第二催化剂的活性组分含量、比例以及涂层上载量可根据发动机的实际尾气排放特点作相应调整。
所述第一催化剂2与第二催化剂3的体积比为(0.5~10):1。
优选地,所述第一催化剂与第二催化剂的体积比为(0.5~5):1。
更优选地,所述第一催化剂2与第二催化剂3的体积比为(1~3):1。
示例性地,所述第一催化剂2与第二催化剂3的体积比可以是1:2、1:1、2:1、3:1或者5:1等。
上述尾气处理催化剂可以为单极分段催化剂或者两极催化剂,由三种催化剂组成,图1所示为单极分段催化剂,图2所示为两极催化剂。催化剂前段(或前极)由载体材料1和第一催化剂2组成,第一催化剂2为三效催化剂,主要将尾气中的甲烷、非甲烷碳氢、一氧化碳、氮氧化物和颗粒物等污染物净化处理成二氧化碳、氮气和水;催化剂后段(或后极)由载体材料1和第二催化剂3组成,其中,第二催化剂3下层为氨氧化催化剂,主要将氨气氧化为氮气和少部分的一氧化氮,上层为被动选择还原型催化剂,主要将氨气和一氧化氮转化为氮气和水,本催化剂后端(或后极)主要将尾气中的原排氨气或者催化剂前段(或前极)净化处理后的新增副产物氨气和催化剂前段(或前极)未净化处理的甲烷、非甲烷碳氢、氮氧化物、一氧化碳等污染物净化处理为二氧化碳、氮气和水。
在上述尾气处理催化剂中,所述载体1优先为堇青石载体,所述催化材料优选为储氧材料和氧化铝,所述助剂为硝酸铈、硝酸钡等。在所述活性组分中,Pt组分在催化剂中主要起氧化CO和HC的作用,它对NOx有一定的还原能力,但是CO的浓度较高或者有SO2存在时,它的效果没有Rh好;Rh组分是催化还原氮氧化物的主要成分,在有氧时,主要还原产物是N2,仅生成少量NH3;无氧或氧含量低于化学计量比时,还原产物除N2外,NH3的生成量大幅提高;Pd组分主要用来转化CO和烃类,对于饱和烃类效果稍差,抗S中毒能力差,易高温烧结,但它的稳定性较高,起燃性好。助剂本身是一些没有催化作用或者活性较低的添加物,能大大提高催化剂的活性、选择性和寿命。铈氧化物是汽车尾气净化催化剂最主要的助剂,其主要作用有:贮存及释放氧气;提高贵金属的分散性,抑制贵金属颗粒与氧化铝形成无活性的固溶体;提高催化剂的抗中毒能力;增加催化剂的稳定性等。
对比例
将硝酸钯和硝酸铑溶液,以等体积浸渍法分别负载到储氧材料(OSM)和氧化铝(Al2O3)上,80℃干燥6h,500℃焙烧2h,其中钯材料记为M1-1,铑材料记为M1-2;
将M1-1与铝溶胶混合,球磨10min,粘接剂占比3%,得到固含量45%的浆料N1-1;
将M1-2与铝溶胶混合,球磨10min,粘接剂占比3%,得到固含量45%的浆料N1-2;
将N1-1涂覆至堇青石载体上,堇青石载体规格为Φ25.4*50.8/400cpsi-4mil,经80℃干燥6h,500℃焙烧2h,得到催化剂C1-1,涂覆量120g/L,贵金属含量145g/ft3;
将N1-2涂覆至C1-1上层,经80℃干燥6h,500℃焙烧2h,得到催化剂C1,上层涂覆量60g/L,上层贵金属含量5g/ft3,催化剂C1总涂敷量180g/L,总贵金属含量150g/ft3。
实施例1
将硝酸钯和硝酸铑溶液,以等体积浸渍法分别负载到储氧材料(OSM)和氧化铝(Al2O3)上,80℃干燥6h,500℃焙烧2h,其中钯材料记为M1-1,铑材料记为M1-2;
将硝酸铂溶液,以等体积浸渍法分别负载到氧化铝(Al2O3)上,80℃干燥6h,500℃焙烧2h,记为M2-1;
将硝酸铜溶液,以离子交换法负载到SSZ-13分子筛上,80℃干燥6h,500℃焙烧2h,记为M2-2;
将M1-1与铝溶胶混合,球磨10min,粘接剂占比3%,得到固含量45%的浆料N1-1;
将M1-2与铝溶胶混合,球磨10min,粘接剂占比3%,得到固含量45%的浆料N1-2;
将M2-1与铝溶胶混合,球磨10min,粘接剂占比3%,得到固含量40%的浆料N2-1;
将M2-2与铝溶胶混合,球磨10min,粘接剂占比5%,得到固含量40%的浆料N2-2;
将N1-1涂覆至堇青石载体的前段1/2,堇青石载体尺寸为Φ25.4*101.6/400cpsi-4mil,经80℃干燥6h,500℃焙烧2h,得到催化剂C2-1,涂覆量120g/L,贵金属含量145g/ft3;
将N1-2涂覆至C2-1上层,经80℃干燥6h,500℃焙烧2h,得到催化剂C2-2,上层涂覆量60g/L,上层贵金属含量5g/ft3,前端催化剂总涂敷量180g/L,总贵金属含量150g/ft3;
将N2-1涂覆至堇青石载体的后段1/2,经80℃干燥6h,500℃焙烧2h,得到催化剂C2-3,涂覆量60g/L,贵金属含量3g/ft3;
将N2-2涂覆至C2-3的上层,经80℃干燥6h,500℃焙烧2h,得到催化剂C2-4,涂覆量120g/L,后段总涂敷量180g/L。
将以上制备好的催化剂记为C2。
实施例2
将实例1中的N1-1涂覆至堇青石载体的前段2/3,堇青石载体尺寸为Φ25.4*76.2/400cpsi-4mil,经80℃干燥6h,500℃焙烧2h,得到催化剂C3-1,涂覆量120g/L,贵金属含量145g/ft3;
将实例1中的N1-2涂覆至C3-1上层,经80℃干燥6h,500℃焙烧2h,得到催化剂C3-2,上层涂覆量60g/L,上层贵金属含量5g/ft3,前端催化剂总涂敷量180g/L,总贵金属含量150g/ft3;
将实例1中的N2-1涂覆至堇青石载体的后段1/3,经80℃干燥6h,500℃焙烧2h,得到催化剂C3-3,涂覆量60g/L,贵金属含量3g/ft3;
将实例1中的N2-2涂覆至C3-3的上层,经80℃干燥6h,500℃焙烧2h,得到催化剂C3-4,涂覆量120g/L,后段总涂敷量180g/L。
将以上制备好的催化剂记为C3。
实施例3
将实例1中的N1-1涂覆至堇青石载体的前段2/3,堇青石载体尺寸为Φ25.4*76.2/400cpsi-4mil,经80℃干燥6h,500℃焙烧2h,得到催化剂C4-1,涂覆量120g/L,贵金属含量145g/ft3;
将实例1中的N1-2涂覆至C4-1上层,经80℃干燥6h,500℃焙烧2h,得到催化剂C4-2,上层涂覆量60g/L,上层贵金属含量5g/ft3,前端催化剂总涂敷量180g/L,总贵金属含量150g/ft3;
将实例1中的N2-1涂覆至堇青石载体的后段1/3,经80℃干燥6h,500℃焙烧2h,得到催化剂C4-3,涂覆量60g/L,贵金属含量3g/ft3;
将实例1中的N2-2涂覆至C4-3的上层,经80℃干燥6h,500℃焙烧2h,得到催化剂C4-4,涂覆量150g/L,后段总涂敷量210g/L。
将以上制备好的催化剂记为C4。
实施例4
将实例1中的N1-1涂覆至堇青石载体,载体尺寸为Φ25.4*50.8/400cpsi-4mil,经80℃干燥6h,500℃焙烧2h,得到催化剂C5-1,涂覆量120g/L,贵金属含量145g/ft3;
将实例1中的N1-2涂覆至C5-1上层,经80℃干燥6h,500℃焙烧2h,得到催化剂C5-2,上层涂覆量60g/L,上层贵金属含量5g/ft3,前极催化剂总涂敷量180g/L,总贵金属含量150g/ft3;
将实例1中的N2-1涂覆至堇青石载体,载体尺寸为Φ25.4*25.4/400cpsi-4mil,经80℃干燥6h,500℃焙烧2h,得到催化剂C5-3,涂覆量60g/L,贵金属含量3g/ft3;
将实例1中的N2-2涂覆至C5-3的上层,经80℃干燥6h,500℃焙烧2h,得到催化剂C5-4,涂覆量150g/L,后极催化剂总涂敷量210g/L,贵金属含量3g/ft3;
将以上制备好的催化剂记为C5。
将上述实施例及对比例制备的催化剂进行活性评价试验,试验条件如下所示:
模拟天然气发动机尾气气体体积组成:CH4:1000ppm;CO:4000ppm;NO:1000ppm;O2:3500ppm;H2O:10%;CO2:10%;N2为平衡气;空速40000h-1(根据TWC的体积计算的空速)。在450℃时各污染物的转化率如表1所示。
表1不同实施例制备的催化剂在450℃时对各污染物的转化率
从表1可以看出:
1)对比例中制备的催化剂C1对CO、CH4和NO三种污染物均有很高的转化效率,平均转化率超过90%,但是催化剂C1反应副产物NH3排放较高,大幅超过国六法规的排放限值(10ppm);
2)增加了第二催化剂后,催化剂C1、C2、C3和C4的反应副产物NH3的生成量均降至10ppm以下,并且由于第二催化剂对CH4和CO有一定的转化效率,催化剂C1、C2、C3和C4对CH4和CO的转化率有一定程度的提高,但由于第二催化剂氧化NH3的产物有一定量的NO生成,因此,催化剂C1、C2、C3和C4对NO的转换率哟略微降低;
3)实施例1制备的催化剂C2和对比例制备的催化剂C1比较,银催化剂C2增加了第二催化剂,NH3的排放量显著降低;
4)实施例1制备的催化剂C2和实施例2制备的催化剂C3比较,调整第一催化剂和第二催化剂的提及占比,当增加第二催化剂和第一催化剂的比例后,NH3的排放量略微降低,同时CO、CH4和NO的转化率略微升高;
5)实施例2制备的催化剂C3和实施例3制备的催化剂C4比较,调整第二催化剂上层和下层层的含量比例,当增加上层的含量后,NH3的排放量略微降低,同时NO的转化率略微升高,但CO和CH4的转化率略微降低;
6)实施例3制备的催化剂C4和实施例4制备的催化剂C5比较,单极分段催化剂和两极催化剂对比,在氧气含量一样的条件下,活性基本相当,对各污染性气体的转化率基本相同。
上述实验说明:本发明的尾气处理催化剂,第一催化剂与第二催化剂相互配合工作,第一催化剂能净化处理尾气中的NO、HC、CO和PM,第二催化剂能净化处理尾气原排和第一催化剂催化副产物NH3,以及净化前段未反应完全的NO、HC和CO,净化处理效率高,能够显著减少尾气中各污染性气体特别是新增副产物NH3的含量,使其能满足国六的排放要求。
实验例
改变实施例1中第一催化剂和第二催化剂的涂覆体积,并进行活性评价试验,实验条件如下所示:
模拟天然气发动机尾气气体体积组成:CH4:1000ppm;CO:4000ppm;NO:1000ppm;O2:3500ppm;H2O:10%;CO2:10%;N2为平衡气;空速40000h-1(根据TWC的体积计算的空速)。试验条件及氨气生成量如表2所示。
表2第一催化剂和第二催化剂体积比对NH3生成量的影响
从表3可以看出,改变第一催化剂和第二催化剂的体积比,将会影响氨气生成量,第一催化剂与第二催化剂体积比优选为(1~3):(1~2)。
Claims (10)
1.一种尾气处理催化剂,其特征在于,所述催化剂由载体、第一催化剂和第二催化剂组成,所述第一催化剂和第二催化剂设于所述载体两端,第一催化剂能净化处理尾气中的CH4、NMHC、CO和NOx;第二催化剂能净化处理第一催化剂净化处理后的副产物NH3以及第一催化剂未净化完全的部分污染物;其中,
所述第二催化剂为双层结构,下层由储氧材料、氧化铝和第二活性组分组成,
所述第二活性组分为Pt与Pd的组合物,或者Ce、Fe、Ni、Cu的组合物;
上层由分子筛和第三活性组分组成,
所述第三活性组分为Cu,或者Cu、Fe的组合物。
2.如权利要求1所述的尾气处理催化剂,其特征在于,所述第二催化剂上、下两层的总上载量为100~300g/L,其中,上层与下层上载量之比为(0.1~10):1。
3.如权利要求1所述的尾气处理催化剂,其特征在于,所述第二活性组分为Pt、Pd的组合物时,Pt与Pd的重量配比为(10~1):(1~0)。
4.如权利要求1所述的尾气处理催化剂,其特征在于,所述第二催化剂下层中第二活性组分含量为0.1~10g/ft3。
5.如权利要求1所述的尾气处理催化剂,其特征在于,所述分子筛为Beta、ZSM-5、SSZ-13或SAPO-34等小孔分子筛中的一种或几种的组合物。
6.如权利要求1所述的尾气处理催化剂,其特征在于,所述第一催化剂由储氧材料、氧化铝、助剂和第一活性组分组成;所述第一活性组分为Pt、Pd和Rh的组合物。
7.如权利要求6所述的尾气处理催化剂,其特征在于,所述第一活性组分中Pt、Pd和Rh的重量配比为(0~50):(1~100):(1~10)。
8.如权利要求1所述的尾气处理催化剂,其特征在于,所述第一催化剂与第二催化剂的体积比为(0.5~10):1。
9.权利要求1~8任一项所述的尾气处理催化剂的制备方法,其特征在于,包括如下步骤:
1)第一催化剂制备:
S01.将第一活性组分前躯体浸渍到储氧材料和氧化铝表面,然后于60~120℃干燥2~10小时,在350~600℃的空气气氛中焙烧2~5小时,得到M-1;
S02.将M-1与1~5wt.%的粘接剂混合,球磨制浆,添加0~5wt.%的助剂,所述助剂添加量以助剂氧化物计,即得第一催化剂浆料N-1;
2)第二催化剂制备:
S01.将第二活性组分前躯体浸渍到储氧材料和氧化铝表面,然后于60~120℃干燥2~10小时,在350~600℃的空气气氛中焙烧2~5小时,得到M-2;
S02.将M-2与1~5wt.%的粘接剂混合,球磨制浆,添加0~5wt.%的助剂,所述助剂添加量以助剂氧化物计,即得第二催化剂下层浆料N-2;
S03.将第三活性组分前躯体以离子交换法交换到分子筛骨架内,过滤,洗涤,然后于60~120℃干燥2~10小时,在350~650℃的空气气氛中焙烧2~8小时,得到M-3;
S04.将M-3与1~5wt.%的粘接剂混合,球磨制浆,添加0~5wt.%的助剂,所述助剂添加量以助剂氧化物计,即得第二催化剂上层浆料N-3;
3)尾气处理催化剂制备:在载体一端涂覆浆料N-1,在载体另一端依次涂覆浆料N-2和浆料N-3,然后于60~120℃干燥2~10小时,并在350~600℃的空气气氛中焙烧2~8小时,即得尾气处理催化剂。
10.权利要求1~8任一项所述的尾气处理催化剂在净化处理天然气汽车尾气中的用途。
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CN113019363B (zh) * | 2021-03-23 | 2022-10-28 | 中自环保科技股份有限公司 | 一种尾气处理催化剂及其用途 |
CN117181237A (zh) * | 2023-01-13 | 2023-12-08 | 昆明贵研催化剂有限责任公司 | 利用含CO和NOx的废气制氨的催化剂、制备方法及制氨的方法 |
CN117181237B (zh) * | 2023-01-13 | 2024-06-11 | 昆明贵研催化剂有限责任公司 | 利用含CO和NOx的废气制氨的催化剂、制备方法及制氨的方法 |
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