CN107486235B - 多孔包覆型铁基分子筛催化剂的制备方法 - Google Patents
多孔包覆型铁基分子筛催化剂的制备方法 Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 32
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 44
- 239000011259 mixed solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 19
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 claims description 13
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- -1 iron modified molecular sieve Chemical class 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 238000012546 transfer Methods 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 3
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 239000011593 sulfur Substances 0.000 abstract description 7
- 230000035939 shock Effects 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 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 16
- 238000000227 grinding Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 229910052720 vanadium Inorganic materials 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229940011182 cobalt acetate Drugs 0.000 description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 3
- 229940071125 manganese acetate Drugs 0.000 description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910017827 Cu—Fe Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- B01J29/00—Catalysts comprising molecular sieves
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- 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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- 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
本发明涉及一种多孔包覆型铁基分子筛催化剂的制备方法，其特征在于所制备的多孔包覆型铁基分子筛催化剂在200～550℃NOx转化率高达65%以上，550℃仍能达到70%以上，展示了较好的高温NOx转化率，能够承受高温热冲击使用要求，具有较强的实际应用价值；另一方面，这种内外包覆结构具有较好的抗硫效果。此外，本发明简化了催化剂制备流程，合成条件易控制，易于工业化应用。
Description
技术领域
本发明涉及多孔包覆型铁基分子筛催化剂的制备方法，属于汽车排放技术领域，尤其属于SCR脱硝的催化剂制备领域。
背景技术
为满足排放法规，Urea-SCR技术已成为中重型柴油机企业首选降低 NOx技术路线，并越来越为人们所接受并成为柴油机尾气 NOx后处理主流研究方向。Urea-SCR技术的核心是催化剂，目前Urea-SCR催化剂包括金属氧化物催化剂、贵金属催化剂和沸石分子筛催化剂。其中贵金属催化剂成本过高且容易与尾气中的硫化物形成硫酸盐而导致催化剂失活。钒基催化剂目前国内使用较普遍，具有应用经验丰富、技术成熟等优点，但是由于钒系催化剂温度窗口窄，且高温时钒基催化剂会分解，产生的V2O5属高毒物质，对人体健康和环境危害较大，因而它只能是一种暂时的过渡技术，不能满足更严格的排放标准要求，欧、美、日等发达国家已经明确禁止使用钒催化剂。
近年来分子筛催化剂由于温度窗口宽、环境友好、NOx活性高等优点在SCR领域取得良好的效果，发达国家已经逐步使用。许多研究发现Fe基或Cu-Fe/zeolite催化剂的De-NOx效率高,在SCR领域具有较广阔的发展前景。然而随着环保法规的日益严格，对NOx限值的要求越来越高，欧VI阶段NOx限值为0.4g/Kwh，相比欧V下降80%，实际上，在不含硫、无尘、无水条件下，很多催化剂都呈现了优异的NOx活性，但是在道路验证时，大多数分子筛催化剂不具高温NOx转化率高、较好的抗硫能力及高温热冲击的要求。
发明内容
鉴于以上所述现有技术中的缺点，本发明的目的在于提供一种多孔包覆型铁基分子筛催化剂的制备方法，首选以Fe复合改性的分子筛催化剂为内层活性中心，通过外层转接导入基团的转接作用将增活剂处理过的过渡金属元素负载在内层活性中心表面，在煅烧过程中，内外层金属间通过化学反应，形成具有较强协同增效的金属活性中心、疏松多孔的结构。这种多孔包覆型铁基分子筛催化剂在200～550℃NOx转化率高达65%以上，550℃仍能达到70%以上，展示了较好的高温NOx转化率，能够承受高温热冲击使用要求，具有较强的实际应用价值；另一方面，这种内外包覆结构具有较好的抗硫效果。此外，本发明简化了催化剂制备流程，合成条件易控制，易于工业化应用。
本发明的技术方案是这样实现的：多孔包覆型铁基分子筛催化剂的制备方法，其特征在于具体步骤如下：(1)将17.5～32.6份铁盐溶于去离子水中，搅拌溶解，加入32.3～43.9份分子筛载体，混合搅拌2～4h；(2)加入1.7～2.3份的氨基甲酸铵，在45～60℃下，搅拌1～3h得到混合液；（3）混合液经90～110℃烘干、530～580℃煅烧4h即得到铁改性分子筛粉末；（4）将18.8～24份过渡金属乙酸盐溶于去离子水配成溶液，再加入1.4～2.3份増活剂、18.8～22份CMC(质量分数1%)外层转接导入剂及1.7～3.5份表面分散剂，在65～105℃强力搅拌2～5h；（5）加入28.9～33.9份铁改性分子筛粉末，于60～115℃下强力搅拌3～6h，得到膏状体；（6）将膏状体于85～120℃烘箱中烘干、480～550℃煅烧4h～6h，即得到一种多孔包覆型铁基分子筛催化剂。
所述过渡金属乙酸盐为La、Co、Mn及Ce金属中的一种或者几种。
所述増活剂为甲酸铵、氨基甲酸铵、草酸铵、甲酰胺、碳酸铵、碳酸氢铵及尿素中一种或者几种。
所述表面分散剂为无水乙醇、丙醇中的一种或者几种。
本发明的积极效果是以Fe复合改性的分子筛催化剂为内层活性中心，通过外层转接导入基团的转接作用将增活剂处理过的过渡金属元素负载在内层活性中心表面，在煅烧过程中，内外层金属间通过化学反应，形成具有较强协同增效的金属活性中心，导入剂全部挥发掉最终形成疏松多孔的结构。这种多孔包覆型铁基分子筛催化剂在200～550℃NOx转化率高达65%以上，550℃仍能达到70%以上，展示了较好的高温NOx转化率，能够承受主动高温热冲击使用要求，具有较强的实际应用价值；此外，这种内外包覆结构具有较好的抗硫效果。
附图说明
图1为实施例1制备催化剂的透射TEM图像；
图2为实施例1和对比例1的NOx转化率测试曲线;
图3为实施例1预硫化处理24h后NOx转化率测试曲线;
图4为实施例1水热处理32h后NOx转化率测试曲线。
具体实施方式
在下述的具体事例描述中，给出了大量具体的细节以便于更为深刻的理解本发明。然而，对于本领域技术人员来说显而易见的是，本发明可以无需一个或多个这些细节而得以实施。
实施例1
(1)将1200g的硝酸铁溶于去离子水中，搅拌溶解，加入3000gBeta40分子筛载体，混合搅拌2h；(2)加入140g氨基甲酸氨，45℃下，搅拌3h得到混合液；（3）混合液经90℃烘干、530℃煅烧4h、研磨即得到Fe改性分子筛粉末；（4）将2400g的乙酸镧溶于3600g去离子水配成溶液，再加入165g甲酸铵、2400g质量分数为1%CMC及195g乙醇，45℃强力搅拌5h；（5）加入3000g（3）中获得的Fe改性的分子筛粉末，于65℃下强力搅拌3h，得到膏状体；（6）将膏状体于85℃烘箱中烘干、破碎、480℃煅烧6h、研磨，即得到多孔包覆型铁基分子筛催化剂。
图1为实施例1制备的催化剂TEM图像，可以看出外层孔比较丰富，且分布均匀;
采用微反固定床气-固相反应装置模拟尾气对实施例１制备催化剂粉末进行不同温度下SCR转化率测试，测试条件为:NO浓度1000 ppm、O2：5%（体积分数）、NH3：1000 ppm、H2O：8%（体积分数）、氮气为平衡气，空速设定为80000h-1，测试结果如图２所示，该催化剂与对比例在150℃NOX转化率高达78%，200℃时转化率高达98%，显示了优异的低温性能，该催化剂在150℃～450℃NOx转化率高达75%以上。
将实施例1制备的催化剂在在200℃下对新鲜的催化剂进行了预硫化处理24h，温度200℃，气体组分组成为O2 8 vol %，SO2 200ppm，N2平衡气进行测试，结果如图3所示，由图可见，与实施例1制备的新鲜样件相比，NOx转化率略有下降，这表明该催化剂具有较好的耐硫性能。
将实施例1制备的催化剂在650℃下对新鲜的催化剂进行水热处理32h，NO浓度1000 ppm、O2：5%（体积分数）、NH3：1000 ppm、H2O：10%（体积分数）、氮气为平衡气，空速设定为80000h-1，测试结果如图4所示，由图可见与实施例1制备的新鲜样件相比，650℃32hNOx转化率几乎未发生改变，这表明实施例1制备的催化剂具有较好的耐硫性能。
对比例1
(1)将1200g的硝酸铁溶于去离子水中，搅拌溶解，加入3000gBeta40分子筛载体，混合搅拌2h；(2)加入140g氨基甲酸氨，45℃下，搅拌3h得到混合液；（3）混合液经105℃烘干、500℃煅烧4h、研磨即得到Fe改性分子筛粉末。如图2所示，150-450℃，NOx活性没有实施例1中催化剂的高。
实施例2
（1）将3000g的硝酸铁溶于去离子水中，搅拌溶解，加入3000gSapo34分子筛载体，混合搅拌4h；(2)加入213g氨基甲酸铵，60℃下，搅拌2h得到混合液；（3）混合液经110℃烘干、580℃煅烧4h、研磨即得到Fe改性分子筛粉末；（4）将3600g的乙酸铈溶于4800g去离子水配成溶液，再加入375g甲酰胺、3000g质量分数为1%CMC及510g丙醇，105℃强力搅拌6h；（5）加入3000g（3）中获得的Fe改性的分子筛粉末，于105℃下强力搅拌5h，得到膏状体；（6）将膏状体105℃烘箱中烘干、破碎、550℃煅烧4h、研磨，即得到多孔包覆型铁基分子筛催化剂。
实施例3
(1)将2500g的硝酸铁溶于去离子水中，搅拌溶解，加入3000gZSM5分子筛载体，混合搅拌4h；(2)加入185g氨基甲酸铵，60℃下，搅拌1h得到混合液；（3）混合液经105℃烘干、550℃煅烧、研磨即得到Fe改性分子筛粉末；（4）将2500g的乙酸锰溶于4500g去离子水配成溶液，再加入305g草酸铵、2500g质量分数为1.0%CMC及462g无水乙醇，85℃强力搅拌2h；（5）加入3000g（3）中获得的Fe改性的分子筛粉末，于105℃下强力搅拌3h，得到膏状体；（6）将膏状体于120℃烘箱中烘干、破碎、530℃煅烧4h、研磨，即得到多孔包覆型铁基分子筛催化剂。
实施例4
(1)将2000g硝酸铁溶于去离子水中，搅拌溶解，加入3000g SSZ13分子筛载体，混合搅拌2h；(2)加入175g氨基甲酸铵，45℃下，搅拌2h得到混合液；（3）混合液经110℃烘干、530℃煅烧、研磨即得到Fe改性分子筛粉末；（4）将2568g的乙酸钴溶于3500g去离子水配成溶液，再加入195g氨基甲酸铵、2400g质量分数为1%CMC及231g无水乙醇，60℃强力搅拌3h；（5）加入3000g（3）中获得的Fe改性的分子筛粉末，于85℃下强力搅拌4h，得到膏状体；（6）将膏状体于105℃烘箱中烘干、破碎、550℃煅烧4h、研磨，即得到多孔包覆型铁基分子筛催化剂。
实施例5
(1)将2000g的硝酸铁溶于去离子水中，搅拌溶解，加入3000gBeta25分子筛载体，混合搅拌4h；(2)加入172g氨基甲酸铵，50℃下，搅拌2h得到混合液；（3）混合液经105℃烘干、550℃煅烧、研磨即得到Fe改性分子筛粉末；（4）将1000g的乙酸铈、1000g乙酸锰、1000g乙酸钴溶于4100g去离子水配成溶液，再加入201g碳酸铵、3000g质量分数为1%CMC及350g无水乙醇，70℃强力搅拌5h，得到膏状体；（5）加入3000g（3）中获得的Fe改性的分子筛粉末，于115℃下强力搅拌3h，得到膏状体；（6）将膏状体于115℃烘箱中烘干、破碎、520℃煅烧5h、研磨，即得到多孔包覆型铁基分子筛催化剂。
实施例6
(1)将2550g的硝酸铁溶于去离子水中，搅拌溶解，加入3000gZSM5分子筛载体，混合搅拌4h；(2)加入186g氨基甲酸铵，60℃下，搅拌2h得到混合液；（3）混合液经105℃烘干、530℃煅烧、研磨即得到Fe改性分子筛粉末；（4）将800g的乙酸铈、600g乙酸镧、500g乙酸钴、600g乙酸锰溶于3300g去离子水配成溶液，再加入172g碳酸氢铵、2200g质量分数为1.0%CMC及265g无水乙醇，85℃强力搅拌2h；（5）加入3000g（3）中获得的Fe改性的分子筛粉末，于115℃下强力搅拌3h，得到膏状体；（6）将膏状体于115℃烘箱中烘干、破碎、520℃煅烧4h、研磨，即得到多孔包覆型铁基分子筛催化剂。
实施例7
(1)将2100g的硝酸铁溶于去离子水中，搅拌溶解，加入3000gBeta40分子筛载体，混合搅拌2h；(2)加入143g氨基甲酸铵，60℃下，搅拌3h得到混合液；（3）混合液经110℃烘干、530℃煅烧、研磨即得到Fe改性分子筛粉末；（4）将1400的乙酸镧、1000g的乙酸铈溶于3500g去离子水配成溶液，再加入215g尿素、2400g质量分数为1.0%CMC、150g无水乙醇及63g丙醇，120℃强力搅拌2h；（5）加入3000g（3）中获得的Fe改性的分子筛粉末，于115℃下强力搅拌3h，得到膏状体；（6）将膏状体于115℃烘箱中烘干、破碎、500℃煅烧6h、研磨，即得到多孔包覆型铁基分子筛催化剂。
Claims (1)
1.多孔包覆型铁基分子筛催化剂的制备方法，其特征在于具体步骤如下：(1)将17.5～32.6份铁盐溶于去离子水中，搅拌溶解，加入32.3～43.9份分子筛载体，混合搅拌2～4h；(2)加入1.7～2.3份的氨基甲酸铵，在45～60℃下，搅拌1～3h得到混合液；（3）混合液经90～110℃烘干、530～580℃煅烧4h即得到铁改性分子筛粉末；（4）将18.8～24份过渡金属乙酸盐溶于去离子水配成溶液，再加入1.4～2.3份増活剂、18.8～22份CMC外层转接导入剂及1.7～3.5份表面分散剂，在65～105℃强力搅拌2～5h；（5）加入28.9～33.9份铁改性分子筛粉末，于60～115℃下强力搅拌3～6h，得到膏状体；（6）将膏状体于85～120℃烘箱中烘干、480～550℃煅烧4h～6h，即得到一种多孔包覆型铁基分子筛催化剂；所述的过渡金属乙酸盐为La、Co、Mn及Ce金属中的一种或者几种； 所述的増活剂为甲酸铵、氨基甲酸铵、草酸铵、甲酰胺、碳酸铵、碳酸氢铵及尿素中一种或者几种；所述的表面分散剂为无水乙醇、丙醇中的一种或者几种，所述的CMC质量分数为1%。
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