CN110869123A - 催化剂和其使用方法 - Google Patents
催化剂和其使用方法 Download PDFInfo
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- CN110869123A CN110869123A CN201880044382.4A CN201880044382A CN110869123A CN 110869123 A CN110869123 A CN 110869123A CN 201880044382 A CN201880044382 A CN 201880044382A CN 110869123 A CN110869123 A CN 110869123A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 108
- 229910052742 iron Inorganic materials 0.000 claims abstract description 54
- 239000010457 zeolite Substances 0.000 claims abstract description 31
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 27
- 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 27
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 claims abstract description 26
- 229910052676 chabazite Inorganic materials 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims 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 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 230000009466 transformation Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 14
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 230000032683 aging Effects 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UOFGPBZQQIAJML-UHFFFAOYSA-N [OH-].C(C1=CC=CC=C1)(C1=CC=CC=C1)C[NH3+] Chemical compound [OH-].C(C1=CC=CC=C1)(C1=CC=CC=C1)C[NH3+] UOFGPBZQQIAJML-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- -1 aluminum alkoxide Chemical class 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- VONZVINFIAPPOK-UHFFFAOYSA-N benzhydryl(dimethyl)azanium hydroxide Chemical compound [OH-].C(C1=CC=CC=C1)(C1=CC=CC=C1)[NH+](C)C VONZVINFIAPPOK-UHFFFAOYSA-N 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000002910 rare earth metals Chemical group 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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Abstract
一种用于转化NOX的催化剂，所述催化剂包含铁菱沸石和铁β沸石；以及降低工艺气体流中的NOX浓度的方法，所述方法包含使所述工艺气体流与所述催化剂接触。所述催化剂特别适用于高温deNOX转化。
Description
本申请要求2017年7月11日提交的美国临时申请第62/530,877号的权益。
技术领域
本发明涉及一种催化剂和利用那种催化剂降低工艺气体流中的NOX浓度的方法。
背景技术
氮氧化物是已知的污染气体并且已努力限制这些化合物进入大气中的数量。在许多工业过程的废气和工艺气体流中都发现了这些物质。另外，在轿车、卡车、公共汽车等机动车辆的废气中发现了这些物质。选择性催化还原是一种已知方法，其通过将氮氧化物转化成氮气和水而从工艺气体流中去除这些化合物。
US 20110286914公开了一种不含有机物的含金属沸石β，其中的二氧化硅与氧化铝比率在5至20范围内，且金属含量为至少0.5wt％。已公开的专利申请还公开了一种使用沸石β选择性催化还原废气中的氮氧化物的方法。
US 20130142727公开了一种具有3埃至5埃范围的孔隙开口的微孔结晶材料，其中所述材料包含选自碱土金属族、稀土金属族、碱金属族或其混合物的第一金属，以及选自铁、铜或其混合物的第二金属；并且具有3至10的二氧化硅与氧化铝摩尔比。已公开的专利申请还公开了一种选择性催化还原废气中的氮氧化物的方法。
有利的是开发在这种反应中更有效且更稳定的改进型催化剂，以便所述单元能够在不维护或不更换催化剂的情况下操作更长的持续时间。
发明内容
本发明提供一种降低工艺气体流中的NOX浓度的方法，所述方法包含使工艺气体流与包含铁菱沸石和铁β沸石的催化剂在NOX转化条件下接触。优选的NOX转化条件包括高温。
本发明提供一种用于转化NOX的催化剂，所述催化剂包含铁菱沸石和铁β沸石。
附图说明
图1描述了包含铁菱沸石和铁β沸石的催化剂在不同条件下的NOX转化率。
具体实施方式
本发明提供了用于转化NOX的改进型催化剂。所述催化剂包含铁菱沸石和铁β沸石。
β沸石优选在有机结构导向剂不存在的情况下制备。所得β沸石材料的孔隙中不含任何残余有机物质，因此不需要通常为了去除有机组分而必需的处理。在现有技术的催化剂中，前体材料使用有机结构导向剂，如四乙基氢氧化铵、二苯甲基甲铵和二苯甲基二甲基氢氧化铵。这些化合物的成本以及它们在制造后通常保留在孔隙中的事实是这些铁β沸石材料合成时的问题。
β沸石中的二氧化硅与氧化铝比率优选5至20。二氧化硅与氧化铝比率优选不大于12，且更优选在5至11范围内。β沸石的平均晶体尺寸优选大于0.1微米，更优选0.2至5微米。
使用上述β沸石制备的铁β沸石优选包含至少0.5wt％的铁，更优选1至10wt％的铁。催化剂也可以包含氧化铝。
优选将铁通过一种或多种方法(包括液相或固体离子交换、浸渍或通过直接合成并入)加入催化剂组分(菱沸石和β沸石)中。在一个优选的实施例中，优选将铁通过离子交换加入。
离子交换法中使用的铁通常是铁盐，并且其可以是硝酸铁、氯化铁、氯化亚铁、硫酸亚铁或其混合物。
制备β沸石的一种方法始于制备包含NaOH和氧化铝源的水溶液。氧化铝源可以是铝酸钠、氢氧化铝、氧化铝、硝酸铝、醇化铝或硫酸铝。然后将二氧化硅源加入溶液中。二氧化硅可以包括硅胶、二氧化硅溶胶、二氧化硅水溶胶、烟雾状二氧化硅、反应性无定形固体二氧化硅、硅酸、水玻璃、硅酸钠、偏硅酸钠、胶体硅酸盐、热解法二氧化硅、沉淀硅酸盐、二氧化硅氧化铝和其他类似材料。然后加入β沸石源，并将混合物混合以形成凝胶。β沸石源可以是市售β沸石。加热凝胶以形成产物，并且执行这个步骤直至获得所期望的晶体尺寸和纯度。加热可包括在100至200℃范围内的温度下加热凝胶长达200小时。一旦形成结晶材料，就可以通过分离、洗涤和干燥对其进行处理。分离可以通过本领域技术人员已知的任何方法进行，包括过滤、离心或倾析。可以用任何已知的试剂(包括水或醇)进行洗涤。另外，可以通过例如离子交换将钠从沸石中除去。
在另一个实施例中，可以通过制备种晶、SiO2源和Al2O3源的混合物并且使所述混合物结晶来制备β沸石。种晶可以是β沸石晶体。
菱沸石也优选在有机结构导向剂不存在的情况下制成。这提供了如上关于铁β沸石所述的类似益处。菱沸石可以通过将钠源、钾源、氧化铝源、二氧化硅源和水源混合以形成凝胶并且然后在80至200℃范围内的温度下加热所述凝胶来制备。所形成的结晶产物然后可以与铵交换。
在有机结构导向剂不存在下制备的菱沸石优选具有3至5埃的孔隙开口。菱沸石中的二氧化硅与氧化铝比率优选3至10。铁菱沸石的平均晶体尺寸优选0.3至10微米，优选0.3至5.0微米。
使用上述菱沸石制备的铁菱沸石优选包含0.5至5.0wt％的铁。铁可以通过液相或固体离子交换来加入。或者，可以通过浸渍来加入铁，或者可以在沸石合成步骤中加入铁。
包含铁菱沸石和铁β沸石的催化剂可以呈沟槽形或蜂窝状、金属板型或波纹板型催化剂的形式。或者，催化剂可以填充床形式存在，其可以包括球、卵石、丸粒、片剂或挤出物。催化剂可以微球形式存在。
可以通过产生沸石材料细粉的浆料，然后与合适的粘合剂混合来形成催化剂。粘合剂可以包括氧化铝、膨润土、二氧化硅或二氧化硅-氧化铝。然后可以将浆料以蜂窝状或具有多个沟槽的其他形状沉积在合适的衬底上。
催化剂可包含铁菱沸石和铁β沸石的共混物；多个层，其中每个层包含单独的铁菱沸石或铁β沸石组分；或多个区域，其中每个区域包含单独的铁菱沸石或铁β沸石组分。催化剂的共混物可包括一定体积的铁菱沸石和铁β沸石，两者在整个共混物的体积中相对于彼此具有近似相同的比例。在另一个实施例中，催化剂的混合物可以设置在多个层或区域中。
催化剂可以用于降低工艺气体流中的NOX浓度的方法中。在所述方法中，使工艺气体流在转化条件下与催化剂接触。转化条件可以包括250至650℃范围内的温度。
氨、尿素或产生氨的化合物可以在工艺气体与催化剂接触之前或同时加入工艺气体中。产生氨的化合物可以是氨基甲酸铵、甲酸铵、碳酸铵或金属胺络合物。
除了氨之外，接触可以在水的存在下进行。以合并的工艺气体、氨和水流的百分比计算，水可以至少0.5vol.％、优选至少2vol.％的量存在。
实例
实例1
这个实例展现水热老化对于包含铁菱沸石与铁β沸石的催化剂的影响。在300至750℃的多种温度下量测新制催化剂的NOx转化率。催化剂随后通过与11％H2O流在760℃下接触16小时进行水热老化。在300至750℃的多种温度下量测老化催化剂的NOx转化率。催化剂通过与11％H2O流再接触10小时(总共26小时)进一步水热老化。在300至750℃的多种温度下量测催化剂的NOx转化率。
新制催化剂、老化催化剂和进一步老化催化剂的NOx转化率展示于图1中。如图中可见，水热老化对催化剂性能的影响可以忽略。本发明的催化剂相较于其它催化剂展现改进的水热稳定性。
Claims (25)
1.一种降低工艺气体流中的NOX浓度的方法，所述方法包含使所述工艺气体流与包含铁菱沸石和铁β沸石的催化剂在NOX转化条件下接触。
2.根据权利要求1所述的方法，其中所述转化条件包含250至700℃范围内的温度。
3.根据权利要求1所述的方法，其中所述转化条件包含325至675℃范围内的温度。
4.根据权利要求1所述的方法，其中所述转化条件包含480至650℃范围内的温度。
5.根据权利要求1所述的方法，其进一步包含在使所述工艺气体与所述催化剂接触之前或同时，将氨、尿素或产生氨的化合物加入所述工艺气体中。
6.根据权利要求5所述的方法，其中所述产生氨的化合物选自由以下组成的组：氨基甲酸铵、甲酸铵、碳酸铵和金属胺络合物。
7.根据权利要求1所述的方法，其中所述接触是在至少0.5vol.％水的存在下进行。
8.根据权利要求1所述的方法，其中所述接触是在至少2vol.％水的存在下进行。
9.一种用于转化NOX的催化剂，所述催化剂包含铁菱沸石和铁β沸石。
10.根据权利要求9所述的催化剂，其中所述铁菱沸石是在有机结构导向剂不存在的情况下制备。
11.根据权利要求9所述的催化剂，其中所述铁菱沸石具有3至5埃的孔隙开口。
12.根据权利要求9所述的催化剂，其中所述铁菱沸石具有3至10的二氧化硅与氧化铝比率。
13.根据权利要求9所述的催化剂，其中所述铁菱沸石具有0.3至小于10微米的平均晶体尺寸。
14.根据权利要求9所述的催化剂，其中所述铁菱沸石具有0.3至5.0微米的平均晶体尺寸。
15.根据权利要求9所述的催化剂，其中所述铁菱沸石包含0.5至5.0wt％的铁。
16.根据权利要求9所述的催化剂，其中所述铁β是在有机结构导向剂不存在的情况下制备。
17.根据权利要求9所述的催化剂，其中所述铁β具有5至20的二氧化硅与氧化铝比率。
18.根据权利要求9所述的催化剂，其中所述铁β具有5至11的二氧化硅与氧化铝比率。
19.根据权利要求9所述的催化剂，其中所述铁β包含至少0.5wt％的铁。
20.根据权利要求9所述的催化剂，其中所述铁β包含1至10wt％的铁。
21.根据权利要求9所述的催化剂，其中所述铁β具有大于0.1微米的平均晶体尺寸。
22.根据权利要求9所述的催化剂，其中所述铁β具有0.2至5微米的平均晶体尺寸。
23.根据权利要求9所述的催化剂，其中所述铁是通过离子交换加入所述β沸石和所述菱沸石中。
24.根据权利要求23所述的催化剂，其中离子交换法中所用的所述铁是选自由以下组成的组的铁盐：硝酸铁、氯化铁、氯化亚铁、硫酸亚铁和其混合物。
25.根据权利要求9所述的催化剂，其进一步包含氧化铝。
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