CN109482226A - 一步法制备过渡金属改性的分子筛整体式催化剂及方法 - Google Patents
一步法制备过渡金属改性的分子筛整体式催化剂及方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 45
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 25
- -1 transition metal modified molecular sieve Chemical class 0.000 title claims abstract description 13
- 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 47
- 239000002808 molecular sieve Substances 0.000 claims abstract description 43
- 238000000576 coating method Methods 0.000 claims abstract description 38
- 239000011248 coating agent Substances 0.000 claims abstract description 33
- 238000002360 preparation method Methods 0.000 claims abstract description 25
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- 238000001035 drying Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
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- 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 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
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- 230000000996 additive effect Effects 0.000 claims description 5
- 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 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims 1
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- 239000010936 titanium Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 7
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
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- 150000001412 amines Chemical class 0.000 description 1
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- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- LITYQKYYGUGQLY-UHFFFAOYSA-N iron nitric acid Chemical compound [Fe].O[N+]([O-])=O LITYQKYYGUGQLY-UHFFFAOYSA-N 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
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- 238000000746 purification Methods 0.000 description 1
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- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
本发明公开了一步法制备过渡金属改性的分子筛整体式催化剂及方法。该制备方法包括涂层溶液制备、浆料制备、催化剂涂覆、催化剂干燥及煅烧四个连续工艺流程。该工艺特点在于涂层溶液配制后无需过滤、洗涤、干燥、煅烧,直接转入制浆和涂覆流程。该工艺过程简单,制得的分子筛催化剂具有优异的低温活性、水热稳定性,可用于氮氧化物(NOx)选择性还原、碳氢化合物(HC)低温处理,具有广泛的工业应用前景。
Description
技术领域
本发明涉及到一步法制备过渡金属改性的分子筛整体式催化剂及方法,所述制备的分子筛催化剂可应用于柴油机NOx选择性还原和HC低温处理。
背景技术
NOx和HC是柴油机尾气的重要污染物。其中NOx是酸雨、光化学烟雾、臭氧层空洞等环境问题的主要原因,并且对人体健康具有显著的影响。HC对人体的眼睛和呼吸道具有明显的刺激作用,且烃类中含有导致人体致癌的物质。现阶段,采用后处理催化剂可高效降低柴油机尾气中的HC和NOx排放,也是目前最佳的后处理催化净化技术。
近年来,采用催化剂尾气净化技术已经大幅减少了柴油机HC和NOx等尾气排放。然而,柴油机启动时排气温度低,很难达到常规催化剂的起燃温度。因此,冷启动时的尾气排放往往是造成柴油机排放超标的关键原因。
当前,NOx主要采用钒基选择性还原催化剂(SCR)、HC采用Pt基或Pt-Pd基氧化催化剂(DOC)进行处理。这两种催化剂的优势是具有很好的中高温催化性能,但劣势是低温性能不足。
研究表明,针对低温关键技术问题,改性分子筛催化剂材料显现出优异的低温活性。用于金属改性的空白分子筛主要有BEA、MFI、CHA等。改性金属包括Mn、Cu、Pd、Pt、Fe等。[CN102946997A]公开了一种将Cu直接交换进Na+型菱沸石的分子筛粉末材料的制备方法。该技术中的Na+对催化剂活性起着非常显著的影响,如在制备过程中控制不精准,残余的超过一定量的Na+将严重降低催化剂的耐久性。基于离子交换工艺缺点,Ren.L.M等( Chem.Commun. 2011, 47:9783)等以铜胺配合物为模板剂原位合成性能较好的Cu改性SSZ-13分子筛催化粉体材料,但该方法获得的改性分子筛材料含Cu量高,不利于老化性能,需要额外进行降铜含量处理,在工业应用上成本较高,较难实现。[CN107262145A]公开了一种沸石碳氢吸附重整催化剂的制备方法,该技术在自主合成的FAU型分子筛催化材料进行Fe离子重整,进而得到Fe-FAU型沸石碳氢吸附重整催化剂。但该方法中,为了让金属Fe分散的更均匀,采用了低硅铝比的分子筛,硅铝摩尔比为3.7-10。该类型的分子筛抗高温水热老化能力较弱,容易高温水热脱铝导致催化剂失活。[CN1205651A]公布了采用铂族金属元素负载的beta等传统分子筛进行HC吸附氧化处理,然而,此类传统未改性分子筛难以满足高温水热老化需求。
改性分子筛整体式催化剂的制备技术主要为两步法。即先通过配液、洗涤、烘干、煅烧制备改性分子筛涂层粉体材料,然后再将粉体材料进行制浆、涂覆、烘干、煅烧获得整体式催化剂。[106984357A]公开了一种首先通过一步或多步离子交换后、经过滤、烘干、煅烧制得改性分子筛粉体材料,然后再进行制浆、涂覆获得催化剂的方法。[102215960A]公开了具有CHA晶体结构、低二氧化硅与氧化铝比例的沸石催化剂的制备方法,该专利同样采用两步法制备整体式分子筛催化剂。两步法工艺复杂,控制点多,不利于产品质量一致性控制、生产成本高、产能低。
本发明采用一步制备法,获得性能优异的改性分子筛整体式催化剂,该工艺简易,操作性强,具有较高技术创造性和的应用价值。
发明内容
本发明目的在于提供了一种一步法制备过渡金属改性的分子筛整体式催化剂及方法。该制备方法包括涂层溶液制备、浆料制备、催化剂涂覆、催化剂干燥及煅烧四个连续工艺流程。该工艺特点在于涂层溶液配制后无需过滤、洗涤、干燥、煅烧,直接转入制浆和涂覆流程。制得的分子筛整体式催化剂具有优异的低温活性、水热稳定性;
为了达到上述目的,本发明采用的技术方案如下:
步骤一:涂层溶液制备:将一种空白分子筛粉末与一定浓度的过渡金属盐溶液及助剂加入到反应釜中,在30℃-150℃条件下,反应0.5h~8h;
本发明中空白分子筛为Na+型、H+型、NH4 +型中的一种或几种;空白分子筛包括以下一种或是几种:BEA、MFI、AEI、AFX、CHA、LTA,其SiO2与Al2O3的质量比为8.0-15.0;
本发明中过渡金属为Cu、Ni、Mn、Co中一种或者几种;分子筛和过渡金属盐溶液的质量比为1-50:15-50,过渡金属盐溶液浓度为0.005mol/L-5mol/L。其中以金属元素计算,每种过渡金属质量占分子筛质量的0.05%-5%;
本发明中助剂为过渡金属、稀土金属、碱土金属中一种或者几种,包括:Cr、Sn、Ce、Ba、Sr、Fe;助剂占催化剂总质量的0.01%-10%;
本发明中的涂层溶液的pH为2-7,采用酸或碱进行调节,所选用酸为乙酸、硝酸、盐酸或硫酸中的任意一种或者至少两种的混合物,所选用的碱为乙基类氢氧化铵、有机醇胺类碱的任意一种或者至少两种的混合物;
本发明中涂层溶液加热的温度为30℃-150℃;
步骤二:制浆涂覆:将步骤一中所得涂层溶液中添加一定量的粘结剂、助剂,搅拌均匀,研磨到所需粒径;按80g/L-350g/L的涂层干重量涂覆于载体;涂覆的催化剂干燥完成后,在500℃-800℃下煅烧0.5h-6h,即得到过渡金属改性分子筛整体式催化剂;
本发明采用空白分子筛为原材料,通过涂层溶液制备、浆料制备、催化剂涂覆、催化剂干燥及煅烧四个连续工艺流程一步制得分子筛整体式催化剂。所述方法克服了传统两步法繁杂的工艺问题,制得的分子筛催化剂具有优异的低温活性和水热稳定性;
本发明助剂为过渡金属、稀土金属、碱土金属中一种或者几种,包括:Cr、Sn、Ce、Ba、Sr、Fe;所述助剂占催化剂总质量的0.01%-10%;
本发明添加的粘结剂包括Al2O3、SiO2、TiO2、ZrO2粉体或者胶体中一种或几种;添加的粘结剂按氧化物计算,其添加量为分子筛粉末质量的1%-15%;
本发明浆料粒径控制范围为1μm -20μm;
本发明涂覆方法采用上给料工艺或是下给料工艺;涂覆次数为一次或多次涂覆;
本发明干燥温度为50℃-200℃,干燥时间0.5h-24h;
本发明焙烧的温度为400℃~800℃。
本发明的目的之二在于提供一种过渡金属改性的分子筛整体式催化剂,所述过渡金属改性的分子筛整体式催化剂由如上所述方法制备得到。该催化剂在低温下具备优异的低温活性和水热稳定性。
本发明的目的之三在于提供一种过渡金属改性的分子筛催化剂的用途,所述过渡金属改性的分子筛催化剂可用于柴油机尾气中NOx选择性还原、HC低温处理。
附图说明
图1:新鲜和老化后A和B两种催化剂的NOx选择性还原活性对比。
图2:新鲜和老化后C和D两种催化剂的HC脱附性能对比。
具体实施方式
下面结合附图并通过具体实施方式来进一步说明本发明的技术方案。
为更好地说明本发明,便于理解本发明的技术方案,本发明的典型但非限制性的实施例如下:
实施例1
配制0.03mol/L的硫酸铜溶液,按铜溶液与H-SSZ-13分子筛质量比为18:1的比例配制涂层溶液,将pH调节至4-5并搅拌6h后,添加硝酸铈(Ce添加量按催化剂重量的0.5%计算),搅拌均匀并添加乙基类氢氧化胺调节pH为5-6。将上述浆料研磨,粒径控制在2.5μm-8μm,按150g/L负载量涂覆在堇青石载体上,110℃烘干,涂覆达到负载量后烘干,650℃焙烧3h 制得整体式CeOx/Cu分子筛催化剂,编号记为A。用以对比的,使用传统离子交换方法先制备Cu-SSZ-13粉体材料再进行涂覆制备整体式Cu-SSZ-13催化剂编号为B。
实施例2
配制0.03mol/L的乙酸铜和0.005mol/L硝酸锰混合溶液,按铜溶液与SAPO-18分子筛质量比为18:1的比例配制涂层溶液,将pH调节至4-5并搅拌6h后,添加硝酸铈(Ce添加量按催化剂重量的0.2%计算),搅拌均匀并添加乙基类氢氧化胺调节pH为5-6。将上述浆料研磨,粒径控制在2.5μm-8μm,按160g/L负载量涂覆在堇青石载体上,110℃烘干,涂覆达到负载量后烘干,550℃焙烧3h制得粉末状整体式CeOx/Mn-Cu-SAPO-18催化剂。
实施例3
配制0.14mol/L的硝酸铁溶液和0.005mol/L氢氧化钡混合溶液,按混合溶液与分子筛质量比为2:1的比例添加H型beta分子筛,将pH调节至4-5并搅拌6h后,添加乙基类氢氧化胺调节pH为5-6,按分子筛量添加5%的氧化硅。将上述浆料研磨,粒径控制在1.2μm-8μm,按240g/L负载量涂覆在堇青石载体上,160℃烘干,涂覆达到负载量后烘干,650℃焙烧3h制得Fe/BaO-beta整体式催化剂。
实施例4
配制0.08mol/L的硝酸锰溶液和0.005mol/L硝酸铈混合溶液,按混合溶液与分子筛质量比为2.86:1的比例添加NH3型beta分子筛,调节溶液pH为2-3并搅拌6h后,添加异丙醇胺调节pH为6-7,按分子筛量添加5%的氧化锆。将上述浆料研磨,粒径控制在1μm-10μm,按240g/L负载量涂覆在金属载体上,160℃烘干,涂覆达到负载量后烘干,在650℃空气中焙烧3h 制得Mn-Ce-beta整体式催化剂,编号记为C。用于对比的,使用传统离子交换方法先制备H-beta粉体材料再进行涂覆制备整体式催化剂编号为D。
实施例5
配置0.2mol/L乙酸铜溶液,按混合溶液与分子筛质量比为1.43:1的比例添加LTA分子筛,调节溶液pH为5-6并搅拌3h后,按分子筛量添加3%的氧化铝。将上述浆料研磨,粒径控制在1μm-10μm;浆料按负载量100g/L涂覆在壁流式SiC载体上,160℃烘干,700℃焙烧1h制得Cu-LTA整体式催化剂。
实施例6
配制 0.15mol/L硝酸铈的溶液和0.005mol/L硝酸铁混合溶液,按混合溶液与分子筛质量比为3.33:1的比例添加AFX分子筛,用硝酸调节溶液pH为2-3并搅拌12h后,添加乙基类氢氧化胺调节pH为6-7,按分子筛量添加5%的氧化铝。将上述浆料研磨,粒径控制在1μm-10μm,按200g/L负载量涂覆在堇青石载体上,140℃烘干,550℃焙烧6h制得Ce-Fe-AFX整体式催化剂。
实施例1测试催化剂小样条件如下:
催化剂规格为φ25.4mm×76.2mm,涂层负载量150g/L,反应混合气的组成为:[NO]=[NH3]=500ppm,[O2]=10%,[H2O]=10%,N2平衡气,空速为100,000h-1,反应温度180℃~550℃。NO、NO2、NH3和N2O气体采用红外气体池测定。
将所制备的整体式催化剂的小样在固定床反应器上进行活性考察,新鲜和老化后A和B两种催化剂的催化活性比较如图1 所示。
由图1 可以看出,相比传统离子交换法所制得催化剂B,本发明提供的制备方法所得催化剂A 在低温(<250℃)条件下具有更高的NOx的催化活性和更宽的活性温度窗口。与此同时,催化剂A在800℃水热老化16小时后仍保持很好NOx还原活性。由此可以看出,本发明提供的制备方法制得的催化剂,在所考察的较低温度范围内具有优异的低温活性、水热稳定性和更宽的活性温度窗口。
实施例4测试整体式催化剂小样条件如下:
催化剂规格为φ25.4mm×76.2mm,催化剂涂层负载量240g/L,反应混合气的组成为:[C3H8]=100ppm,[C3H6]=100ppm,[C2H8]=100ppm,[C2H6]=100ppm,[CO]=200ppm,[H2O]=5%,[O2]=8%,[NO]=500ppm,N2作平衡气,空速为60,000h-1,反应前,催化剂温度稳定在50℃,将所有气氛通入催化剂,待催化剂出口浓度和设定值一致时,采用N2吹扫物理吸附的HC类,然后程序升温,450℃进行程序脱附。
将所制备的整体式催化剂的在固定床反应器上进行活性考察,C和D两种催化剂的新鲜和老化后总HC脱附情况如图2 所示。由图2可以看出,相比传统离子交换法所制得催化剂D,本发明提供的制备方法所得催化剂C在低温条件下具有更高HC脱附量,且脱附温度向低温偏移。两种催化剂在在650℃水热老化处理50h后,催化剂C的总HC脱附量几乎不变,而催化剂D脱附量大幅减少。这说明采用本发明制备催化剂水热老化处理后仍保持很好HC吸附能力。
申请人声明,本发明通过上述实施例来阐述本发明的详细方法,但本发明并不局限于上述具体方法,即意味着本发明不必须依赖上述具体方法才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品各原料进行等效替换及添加辅助成分等,均落在本发明的保护范围和公开范围之内。
Claims (10)
1.一种过渡金属改性的分子筛整体式催化剂的制备方法,其特征在于采用一步法制备技术,包括以下步骤:
1)涂层溶液制备:将一种空白分子筛粉末与一定浓度的过渡金属盐溶液及助剂加入到反应釜中,30℃-150℃条件下反应0.5h-8h,所述空白分子筛与过渡金属盐溶液的质量比为1-50:15-50;
2)浆料制备:将1)所述的涂层溶液中添加一定量的粘结剂、助剂,搅拌均匀,研磨到所需粒径;
3)催化剂涂覆:将2)所述的浆料涂覆于整体式载体上,涂层干重为80g/L-350g/L;
4)催化剂干燥、煅烧:将3)所述的催化剂进行干燥、煅烧,即得本发明的分子筛整体式催化剂。
2.如权利要求1所述的方法,其特征在于:所述的步骤1)中涂层溶液为一次性配制,无需多次加工。
3.如权利要求1所述的方法,其特征在于:步骤1)所述的涂层溶液配制后无需过滤、洗涤、干燥、煅烧,直接转入所述2)、3)、4)流程。
4.如权利要求1所述的方法,其特征在于:步骤2)所述浆料粒径控制范围为1μm-20μm。
5.如权利要求1所述的方法,其特征在于,步骤3)所述涂覆方法采用上给料工艺或是下给料工艺。
6.如权利要求1所述的方法,其特征在于,步骤3)涂覆次数为一次或多次涂覆。
7.如权利要求1所述的方法,其特征在于,步骤4)所述干燥温度为50℃-200℃,干燥时间0.5h-24h;
所述的涂层溶液pH为2-7,优选4-6;
所述的加热温度为30℃-150℃,优选60℃~80℃;
步骤4)所述焙烧的温度为400℃~800℃,优选500℃-650℃。
8.一种过渡金属改性的分子筛整体式催化剂的制备方法,其特征在于包括以下步骤:
配制0.03mol/L的硫酸铜溶液,按铜溶液与H-SSZ-13分子筛质量比为18:1的比例配制涂层溶液,将pH调节至4-5并搅拌6h后,添加硝酸铈,Ce添加量按催化剂重量的0.5%计算,搅拌均匀并添加乙基类氢氧化胺调节pH为5-6,将上述浆料研磨,粒径控制在2.5μm-8μm,按150g/L负载量涂覆在堇青石载体上,110℃烘干,涂覆达到负载量后烘干,650℃焙烧3h制得整体式CeOx/Cu分子筛催化剂。
9.一种过渡金属改性的分子筛整体式催化剂,其特征在于:
该催化剂组分包括:过渡金属、空白分子筛、粘结剂、助剂、整体式载体,
该催化剂中的整体式载体包括壁流式或直通式载体,载体材质包括堇青石、碳化硅、钛酸铝、铁铬铝金属;
所述的空白分子筛包括以下一种或是几种:BEA、MFI、AEI、AFX、CHA、LTA,其SiO2与Al2O3质量比为8.0-15.0;所述空白分子筛为Na+型、H+型、NH4 +型中的一种或几种;
所述的过渡金属为Cu、Ni、Mn、Co中的一种或几种;
所述所添加过渡金属盐溶液浓度为0.005mol/L-5mol/L;
以金属元素计算,每种过渡金属质量占分子筛质量的0.05%-5%,优选1.5%-2.5%;
所述助剂为过渡金属、稀土金属、碱土金属的一种或几种,包括Cr、Sn、Ce、Ba、Sr、Fe,助剂占催化剂总质量的0.01%-10%;
所述添加的粘结剂为Al2O3、SiO2、TiO2、ZrO2粉体或者胶体中一种或几种;
所述添加的粘结剂按氧化物计算,其添加量为分子筛粉末质量的1%-15%。
10.权利要求1所述方法制备的分子筛催化剂用于NOx的选择性还原或HC的低温处理。
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CN110404580A (zh) * | 2019-08-08 | 2019-11-05 | 无锡威孚环保催化剂有限公司 | 稀土金属改性的分子筛催化剂及其制备方法 |
CN110947414A (zh) * | 2019-12-12 | 2020-04-03 | 中节能万润股份有限公司 | 一种铜铁双金属负载整体式脱硝催化剂、其制备方法及应用 |
CN111203269A (zh) * | 2020-04-21 | 2020-05-29 | 稀土催化创新研究院(东营)有限公司 | 一种多金属-cha型分子筛催化剂及其制备方法和应用 |
CN111762795A (zh) * | 2020-07-13 | 2020-10-13 | 包头稀土研究院 | 含有稀土元素的分子筛及其生产方法 |
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CN111871456A (zh) * | 2020-08-20 | 2020-11-03 | 江苏博霖环保科技有限公司 | 一步法合成具有cha结构的含铜scr催化剂的制备方法 |
CN112717991A (zh) * | 2020-12-29 | 2021-04-30 | 青岛华世洁环保科技有限公司 | Fe和Cu复合分子筛催化剂的制备方法及应用 |
CN117323969A (zh) * | 2023-11-30 | 2024-01-02 | 中汽研汽车检验中心(天津)有限公司 | 一种高效氮氧化物吸附剂、制备方法及应用 |
CN117323969B (zh) * | 2023-11-30 | 2024-03-15 | 中汽研汽车检验中心(天津)有限公司 | 一种高效氮氧化物吸附剂、制备方法及应用 |
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