CN113786841A - 一种抗铅中毒的Fe-Mn-Ce/含钛高炉渣脱硝催化剂 - Google Patents
一种抗铅中毒的Fe-Mn-Ce/含钛高炉渣脱硝催化剂 Download PDFInfo
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- CN113786841A CN113786841A CN202111095508.0A CN202111095508A CN113786841A CN 113786841 A CN113786841 A CN 113786841A CN 202111095508 A CN202111095508 A CN 202111095508A CN 113786841 A CN113786841 A CN 113786841A
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- 239000002893 slag Substances 0.000 title claims abstract description 93
- 239000010936 titanium Substances 0.000 title claims abstract description 78
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 78
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 206010027439 Metal poisoning Diseases 0.000 title claims description 25
- 208000008127 lead poisoning Diseases 0.000 title claims description 25
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 7
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- 238000005470 impregnation Methods 0.000 claims description 6
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- 150000002500 ions Chemical class 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
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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 claims description 5
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- 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
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- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
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- 230000008021 deposition Effects 0.000 claims description 2
- 229940046892 lead acetate Drugs 0.000 claims description 2
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- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 238000006011 modification reaction Methods 0.000 claims description 2
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
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- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 3
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 3
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- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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Abstract
本发明提供一种Fe‑Mn‑Ce/含钛高炉渣脱硝催化剂，具有低温催化活性优良、反应温度窗口宽等特点，并且所用原料价格成本较低，相比稀土金属基催化剂具有明显优势。本发明提供的一种Fe‑Mn‑Ce/含钛高炉渣脱硝催化剂，对于PbO、PbCl2或PbSO4重金属具有明显的抗中毒效果。应用于选择性催化还原烟气脱硝领域，可延长催化剂的实际使用寿命，降低其使用成本。采用“变废为宝”的思想，使高炉副产物含钛高炉渣能得到更大程度地利用，既节约资源，又减少对环境的污染，具有很好的社会效益。
Description
技术领域
本发明涉及一种抗铅中毒的Fe-Mn-Ce/含钛高炉渣脱硝催化剂，属于低温SCR烟气脱硝技术领域。
背景技术
环境中的氮氧化物会引起空气质量的严重污染，如酸雨、光化学烟雾、雾霾等。因此，对氮氧化物的净化控制是十分必要的。选择性催化还原(SCR)脱硝技术因其容易针对烟气组分进行针对性设计，且脱硝效率高，被认为是烟气脱硝最具潜力的技术之一。SCR脱硝技术的核心是催化剂。钢铁、水泥、玻璃等行业生产过程中产生的烟气成分复杂，除水蒸气和SO2之外，还含有碱金属(K，Na)、碱土金属(Ca)、重金属(Pb、Hg、Zn、As)、以及其它有害组分(P、S、Cl)，这些成分会对SCR脱硝催化剂产生磨损、堵塞以及中毒等影响，大大加快了催化剂的失活速率，严重降低了催化剂的使用寿命。据了解，关于脱硝催化剂抗碱金属、碱土金属、SO2及HCl等有害组分中毒的研究已被大量报道。然而，由于重金属具有生理毒性和不同价态等特点，针对提高重金属中毒脱硝催化剂的研究相对较少。其中，铅物种作为典型的重金属，主要以PbO和PbCl2形态存在于烟气中。据报道，某些城市生活垃圾焚烧厂在静电除尘前，粉尘中铅的浓度可达30mg/g，烟气中铅的浓度可达6-40mg/g。因此，有必要提高脱硝催化剂的抗铅中毒能力，进一步延长催化剂在实际脱硝应用中的使用寿命，降低其脱硝运营成本。
发明内容
为了解决现有技术中的问题，本发明提供一种抗铅中毒的Fe-Mn-Ce/含钛高炉渣脱硝催化剂(FMC/slag)，该催化剂具有低温活性高、温度窗口宽以及较好抗铅中毒能力的特点，具有广泛的应用前景。
除特殊说明外，本发明所述份数均为重量份，所述百分比均为质量百分比。
研究发现，钒钛磁铁矿经高炉冶炼所产生的低钛高炉渣，其主要成分为Ti、Al、Si和Ca等。经酸处理后，Ca基本去除，并获得一种组成稳定、性能优良的Ti-Si-Al复合载体，可用于制备SCR低温烟气脱硝催化剂。这不仅可以降低脱硝成本，还能实现钛渣的资源化利用，促进资源循环。Fe、CeO2与MnOx同时负载于Ti-Si-Al复合载体时，Mn在催化剂表面的分散度较好，且出现更多氧空位，催化剂能在较低的温度下达到高脱硝活性和N2选择性，表现出更优越的催化活性；再进行铅中毒处理后，催化剂抗铅中毒能力明显增强，应用于选择性催化还原烟气脱硝领域，可明显延长催化剂的实际使用寿命。
为实现上述目的，本发明的技术方案为：
一种抗铅中毒的Fe-Mn-Ce/含钛高炉渣脱硝催化剂，先将含钛高炉渣进行酸改性预处理制备含钛高炉渣复合载体；然后在含钛高炉渣复合载体上负载铁、锰和铈源前驱体，经烘干、焙烧后制得Fe-Mn-Ce/含钛高炉渣低温脱硝催化剂；最后将Fe-Mn-Ce/含钛高炉渣低温脱硝催化剂进行铅中毒处理，再经烘干、焙烧，获得含铅的Fe-Mn-Ce/含钛高炉渣低温脱硝催化剂。
本发明提供一种低温活性高、温度窗口宽，并且具有较好抗铅中毒能力的Fe-Mn-Ce/含钛高炉渣脱硝催化剂，为SCR烟气脱硝催化剂抗重金属铅中毒的发展提供新解决办法。首先，利用酸溶液改性低钛高炉渣，获得一种组成稳定、性能优良的Ti-Si-Al复合载体。之后，在所述载体上均匀负载铁、锰和铈源前驱体，经烘干、焙烧后即得到一种新型Fe-Mn-Ce/含钛高炉渣脱硝催化剂。最后，对上述制备的催化剂进行铅中毒处理，再经烘干、焙烧，获得含铅的Fe-Mn-Ce/含钛高炉渣脱硝催化剂。
所述含钛高炉渣复合载体的制备步骤为：以钒钛磁铁矿高炉冶炼后产生的含钛高炉渣作为制备催化剂的原料，将其置于反应器中进行酸改性预处理；改性反应完成后，分离出反应器中的固体成分，并洗涤至中性；再经烘干、研磨得到酸改性后的含钛高炉渣复合载体(主要成分为Ti、Si、Al)。进一步，所述的酸改性溶液选自盐酸、硫酸、醋酸、草酸、磷酸、柠檬酸中的任意一种，摩尔浓度为0.5～4mol/L，优选2mol/L。更进一步，所用原料固液比(g：mL)为1:(8～12)，优选1:10；酸改性预处理温度控制在20～80℃，优选30℃；反应时间为0.5～4h，优选2h。分离出反应器中的固体成分用纯水洗涤至中性，然后在恒温干燥箱中80℃保温12h后研磨至粉状。
所述负载的铁、锰和铈源前驱体分别为硝酸铁、硝酸锰或乙酸锰、硝酸铈。进一步，所负载的前驱体中铁、锰和铈离子摩尔比为2～6:4:1，优选4:4:1；锰、铈氧化物总质量与载体的比例控制在10～20wt％，优选15wt％。制备Fe-Mn-Ce/含钛高炉渣低温脱硝催化剂的方法包括浸渍法、共沉淀法、水热法、溶胶凝胶法，离子交换法、溶剂热法、机械研磨法。用恒温干燥箱中80℃下保温24h，再于空气中焙烧，焙烧的温度控制在400～550℃，优选500℃；焙烧时间为4～6h，优选6h。，焙烧采取程序升温，升温速率控制在10℃/min。
所述铅中毒处理中铅的加入方式包括湿法浸渍、气相吸附、固相沉积等。铅源前驱体为硝酸铅、氯化铅、硫酸铅和醋酸铅中的任意一种，且铅、锰离子摩尔比控制在0.1～1:1，例如0.1：1、0.2:1、0.5:1、1:1。用恒温干燥箱，在80℃下保温24h，再于空气中焙烧，温度控制在400～550℃，例如400℃、500℃、550℃，优选500℃；焙烧时间为4～6h，优选6h，焙烧采取程序升温，升温速率控制在10℃/min。
有益效果：
(1)本发明提供一种抗铅中毒的Fe-Mn-Ce/含钛高炉渣脱硝催化剂，具有低温催化活性优良、反应温度窗口宽等特点，并且所用原料价格成本较低，相比稀土金属基催化剂具有明显优势。
(2)本发明提供的一种抗铅中毒的Fe-Mn-Ce/含钛高炉渣脱硝催化剂，对于PbO、PbCl2或PbSO4重金属具有明显的抗中毒效果。应用于选择性催化还原烟气脱硝领域，可延长催化剂的实际使用寿命，降低其使用成本。
(3)采用“变废为宝”的思想，使高炉副产物含钛高炉渣能得到更大程度地利用，既节约资源，又减少对环境的污染，具有很好的社会效益。
(4)低钛高钛渣经酸改性后，可得到以TiO2-Al2O3-SiO2为主的复合载体，其具有比表面积大、孔结构发达、结构稳定等特点，是用作制备脱硝催化剂的优选原料。
(5)钛渣的净化分离要求不高，耗酸量较低，经济效益显著，并且催化剂的制备方法简单，可操作性强，可重复性高。
附图说明
图1为本发明Fe-Mn-Ce/含钛高炉渣脱硝催化剂制备流程图，其中Pb掺杂的Fe-Mn-Ce/含钛高炉渣脱硝催化剂即本发明抗铅中毒的Fe-Mn-Ce/含钛高炉渣脱硝催化剂；
图2为本发明实施例1、2中所得Fe-Mn-Ce/含钛高炉渣脱硝催化剂的NOx转化率曲线；
图3为本发明实施例1中所得PbO掺杂Fe-Mn-Ce/含钛高炉渣脱硝催化剂的NOx转化率曲线；
图4为本发明实施例2中所得PbCl2掺杂Fe-Mn-Ce/含钛高炉渣脱硝催化剂的NOx转化率曲线。
具体实施方式
下面结合实施例对本发明作进一步说明，但不应该理解为本发明上述主题范围仅限于下述实施例。在不脱离本发明上述技术思想的情况下，根据本领域普通技术知识和惯用手段，做出各种替换和变更，均应包括在本发明的保护范围内。本发明所用原料及试剂均为市售产品。本发明Fe-Mn-Ce/含钛高炉渣脱硝催化剂由于适用于低温环境，又称为Fe-Mn-Ce/含钛高炉渣低温脱硝催化剂。本发明NOx是氮氧化物的常规写法。
实施例1
采用浓度2mol/L且质量分数为37wt％的稀盐酸处理低钛高炉渣(来自中国西部攀钢地区)，于30℃恒温下充分反应2h。随后，利用800r/min的离心机进行固液分离操作，用纯水反复清洗固体成分直至呈中性，再放于80℃干燥12h，并研磨至粉状。原钛渣和酸浸渣的主要化学成分如表1所示。
表1本发明实施例中原钛渣及酸浸渣的成分
采用浸渍法制备Fe-Mn-Ce/含钛高炉渣低温脱硝催化剂。首先，按照锰、铈氧化物总质量占载体的15wt％，称量8.08g九水硝酸铁(Fe(NO3)3·9H2O)、2.17g六水硝酸铈(Ce(NO3)3·6H2O)、4.65mL硝酸锰溶液(Mn(NO3)2和17.33g酸浸渣载体，混于100mL蒸馏水中搅拌10min，再超声振荡30min。使所用原料充分搅拌，并均匀分散于溶液中。随后，置于80℃水浴锅中均匀搅拌至水分完全蒸干，再转移至80℃干燥箱中干燥24h，最终将样品放于马弗炉中500℃焙烧6h，焙烧采取程序升温，升温速率控制在10℃/min，即获得Fe-Mn-Ce/含钛高炉渣低温脱硝催化剂(FMC/slag)。所得Fe-Mn-Ce/含钛高炉渣脱硝催化剂的NOx转化率曲线如图2所示，与Fe负载前的Mn-Ce/含钛高炉渣脱硝催化剂(MC/slag)做对比，负载Fe后的催化剂脱硝率随温度升高而提升，125℃时的脱硝效率即高于80％，200℃时的脱硝活性达到了99.1％，展现出极好的低温脱硝活性，且其抗铅中毒能力远优于未负载Fe的Mn-Ce/含钛高炉渣脱硝催化剂(MC/slag)。
按照Pb/Mn离子摩尔比为0.5:1，称量3.31g硝酸铅(Pb(NO3)3)、2.78g氯化铅(PbCl2)，分别与23.11gFe-Mn-Ce/含钛高炉渣低温脱硝催化剂粉末混于100mL蒸馏水，搅拌10min，再超声振荡30min。随后，置于80℃水浴锅中均匀搅拌至水分完全蒸干，再转移至80℃干燥箱中干燥24h，最终将样品放于马弗炉中500℃焙烧6h，焙烧采取程序升温，升温速率控制在10℃/min，即分别获得PbO掺杂Fe-Mn-Ce/含钛高炉渣低温脱硝催化剂(PbO-FMC/slag)、PbCl2掺杂Fe-Mn-Ce/含钛高炉渣低温脱硝催化剂(PbCl2-FMC/slag)。PbO掺杂Fe-Mn-Ce/含钛高炉渣低温脱硝催化剂(PbO-FMC/slag)的NOx转化率如图3所示(PbO-Mn-Ce/含钛高炉渣脱硝催化剂[PbO-MC/slag]做对比)，载Fe后的催化剂抗铅中毒能力大大提升，其铅中毒后的脱硝活性远优于未负载Fe的Mn-Ce/含钛高炉渣催化剂(MC/slag)。PbCl2掺杂Fe-Mn-Ce/含钛高炉渣低温脱硝催化剂(PbCl2-FMC/slag)的NOx转化率如图4所示(PbCl2-Mn-Ce/含钛高炉渣脱硝催化剂[PbCl2-MC/slag]做对比)，负载Fe后的催化剂抗铅中毒能力大大提升，其铅中毒后的脱硝活性远优于未负载Fe的Mn-Ce/含钛高炉渣催化剂(MC/slag)。
实施例2
原钛渣和酸浸渣载体(含钛高炉渣复合载体)的制备方法同实施例1。采用浸渍法制备Fe-Mn-Ce/含钛高炉渣低温脱硝催化剂。首先，按照锰、铈氧化物总质量占载体的15wt％，称量4.04g九水硝酸铁(Fe(NO3)3·9H2O)、2.17g六水硝酸铈(Ce(NO3)3·6H2O)、4.65mL硝酸锰溶液(Mn(NO3)2和17.33g酸浸渣载体，混于100mL蒸馏水中搅拌10min，再超声振荡30min。，使所用原料充分搅拌，并均匀分散于溶液中。随后，置于80℃水浴锅中均匀搅拌至水分完全蒸干，再转移至80℃干燥箱中干燥24h，最终将样品放于马弗炉中400℃焙烧6h，焙烧采取程序升温，升温速率控制在10℃/min，即获得Fe-Mn-Ce/含钛高炉渣低温脱硝催化剂。
按照Pb/Mn离子摩尔比为0.5:1，称量2.78g氯化铅(PbCl2)与23.11gFe-Mn-Ce/含钛高炉渣低温脱硝催化剂粉末，混于100mL蒸馏水中搅拌10min，超声振荡30min。随后，置于80℃水浴锅中均匀搅拌至水分完全蒸干，再转移至80℃干燥箱中干燥24h，最终将样品放于马弗炉中400℃焙烧6h，焙烧采取程序升温，升温速率控制在10℃/min，即获得Fe-Mn-Ce/含钛高炉渣PbCl2中毒低温脱硝催化剂。
实施例3
原钛渣和酸浸渣的载体(含钛高炉渣复合载体)的制备方法同实施例1。采用浸渍法制备Fe-Mn-Ce/含钛高炉渣低温脱硝催化剂。首先，按照锰、铈氧化物总质量占载体的20wt％，称量8.08g九水硝酸铁(Fe(NO3)3·9H2O)、2.17g六水硝酸铈(Ce(NO3)3·6H2O)、4.65mL硝酸锰溶液(Mn(NO3)2和13.01g酸浸渣载体，混于100mL蒸馏水中搅拌10min，再超声振荡30min。，使所用原料充分搅拌，并均匀分散于溶液中。随后，置于80℃水浴锅中均匀搅拌至水分完全蒸干，再转移至80℃干燥箱中干燥24h，最终将样品放于马弗炉中500℃焙烧6h，焙烧采取程序升温，升温速率控制在10℃/min，即获得Fe-Mn-Ce/含钛高炉渣低温脱硝催化剂。
按照Pb/Mn离子摩尔比为0.5:1，称量3.03g硫酸铅(Pb(SO4)2)与18.78gFe-Mn-Ce/含钛高炉渣低温脱硝催化剂粉末，混于100mL蒸馏水中搅拌10min，超声振荡30min。随后，置于80℃水浴锅中均匀搅拌至水分完全蒸干，再转移至80℃干燥箱中干燥24h，最终将样品放于马弗炉中500℃焙烧6h，焙烧采取程序升温，升温速率控制在10℃/min，即获得Fe-Mn-Ce/含钛高炉渣Pb(SO4)2中毒低温脱硝催化剂。
Claims (10)
1.一种抗铅中毒的Fe-Mn-Ce/含钛高炉渣脱硝催化剂，先将含钛高炉渣进行酸改性预处理制备含钛高炉渣复合载体；然后在含钛高炉渣复合载体上负载铁、锰和铈源前驱体，经烘干、焙烧后制得Fe-Mn-Ce/含钛高炉渣低温脱硝催化剂；最后将Fe-Mn-Ce/含钛高炉渣低温脱硝催化剂进行铅中毒处理，再经烘干、焙烧，获得含铅的Fe-Mn-Ce/含钛高炉渣低温脱硝催化剂。
2.如权利要求1所述催化剂，其特征在于，所述含钛高炉渣复合载体的制备步骤为：以钒钛磁铁矿高炉冶炼后产生的含钛高炉渣作为制备催化剂的原料，将其置于反应器中进行酸改性预处理；改性反应完成后，分离出反应器中的固体成分，并洗涤至中性；再经烘干、研磨得到酸改性后的含钛高炉渣复合载体。
3.如权利要求2所述催化剂，其特征在于：所述酸选自盐酸、硫酸、醋酸、草酸、磷酸、柠檬酸中的任意一种，摩尔浓度为0.5～4mol/L，优选2mol/L。
4.如权利要求2或3所述催化剂，其特征在于：所用原料固液比(g：mL)为1:(8～12)，优选1:10；酸改性预处理温度控制在20～80℃，优选30℃；反应时间为0.5～4h，优选2h。
5.如权利要求4所述催化剂，其特征在于：分离出反应器中的固体成分用纯水洗涤至中性，然后在恒温干燥箱中80℃保温12h后研磨至粉状。
6.如权利要求1-5任一项所述催化剂，其特征在于：所述负载的铁、锰和铈源前驱体分别为硝酸铁、硝酸锰或乙酸锰、硝酸铈。
7.如权利要求6所述催化剂，其特征在于：所负载的前驱体中铁、锰和铈离子摩尔比为2～6:4:1，优选4:4:1；锰、铈氧化物总质量与载体的比例控制在10～20wt％，优选15wt％。
8.如权利要求6或7所述催化剂，其特征在于：用恒温干燥箱中80℃下保温24h，再于空气中焙烧，焙烧的温度控制在400～550℃，优选500℃；焙烧时间为4～6h，优选6h；焙烧采取程序升温，升温速率控制在10℃/min。
9.如权利要求1-8任一项所述催化剂，其特征在于：所述铅中毒处理中铅的加入方式包括湿法浸渍、气相吸附、固相沉积等；铅源前驱体为硝酸铅、氯化铅、硫酸铅和醋酸铅中的任意一种，且铅、锰离子摩尔比控制在0.1～1:1，例如0.1：1、0.2:1、0.5:1、1:1。
10.如权利要求9所述催化剂，其特征在于：用恒温干燥箱，在80℃下保温24h，再于空气中焙烧，温度控制在400～550℃，例如400℃、500℃、550℃，优选500℃；焙烧时间为4～6h，优选6h，焙烧采取程序升温，升温速率控制在10℃/min。
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0272620A2 (de) * | 1986-12-24 | 1988-06-29 | BASF Aktiengesellschaft | Verfahren zur Entfernung von Stickoxiden aus Abgasen, die bei der Verbrennung von Kohle anfallen |
| CN103537279A (zh) * | 2013-10-15 | 2014-01-29 | 北京工业大学 | 一种添加助剂的低温脱硝催化剂及其制备方法 |
| CN104722307A (zh) * | 2015-03-13 | 2015-06-24 | 国家电网公司 | 一种铁基低温scr脱硝催化剂及其制备方法 |
| CN105327698A (zh) * | 2015-11-27 | 2016-02-17 | 攀钢集团攀枝花钢钒有限公司 | 以含钛高炉渣为载体的新型scr烟气脱硝催化剂的制备方法 |
| CN112058271A (zh) * | 2020-06-28 | 2020-12-11 | 重庆大学 | 一种酸改性低钛高炉渣制备scr低温烟气脱硝催化剂的方法 |
| CN112275279A (zh) * | 2020-09-27 | 2021-01-29 | 四川轻化工大学 | 一种铅中毒Mn-Ce碳基SCR低温脱硝催化剂的再生方法 |
| CN112337477A (zh) * | 2020-11-10 | 2021-02-09 | 黑河学院 | 一种高性能Fe﹑Ce﹑Mn﹑Ti四组分催化剂制备及用途 |
| CN112844366A (zh) * | 2021-01-12 | 2021-05-28 | 上海大学 | 抗多重中毒的nh3-scr催化剂及其制备方法 |
-
2021
- 2021-09-17 CN CN202111095508.0A patent/CN113786841B/zh active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0272620A2 (de) * | 1986-12-24 | 1988-06-29 | BASF Aktiengesellschaft | Verfahren zur Entfernung von Stickoxiden aus Abgasen, die bei der Verbrennung von Kohle anfallen |
| CN103537279A (zh) * | 2013-10-15 | 2014-01-29 | 北京工业大学 | 一种添加助剂的低温脱硝催化剂及其制备方法 |
| CN104722307A (zh) * | 2015-03-13 | 2015-06-24 | 国家电网公司 | 一种铁基低温scr脱硝催化剂及其制备方法 |
| CN105327698A (zh) * | 2015-11-27 | 2016-02-17 | 攀钢集团攀枝花钢钒有限公司 | 以含钛高炉渣为载体的新型scr烟气脱硝催化剂的制备方法 |
| CN112058271A (zh) * | 2020-06-28 | 2020-12-11 | 重庆大学 | 一种酸改性低钛高炉渣制备scr低温烟气脱硝催化剂的方法 |
| CN112275279A (zh) * | 2020-09-27 | 2021-01-29 | 四川轻化工大学 | 一种铅中毒Mn-Ce碳基SCR低温脱硝催化剂的再生方法 |
| CN112337477A (zh) * | 2020-11-10 | 2021-02-09 | 黑河学院 | 一种高性能Fe﹑Ce﹑Mn﹑Ti四组分催化剂制备及用途 |
| CN112844366A (zh) * | 2021-01-12 | 2021-05-28 | 上海大学 | 抗多重中毒的nh3-scr催化剂及其制备方法 |
Non-Patent Citations (4)
| Title |
|---|
| GEHUA LI ET AL.: ""Significantly enhanced Pb resistance of a Comodified Mn-Ce-Ox/TiO2 catalyst for low temperature NH3-SCR of NOx"", vol. 10, pages 6368 - 6377 * |
| QUAN XU ET AL.: ""Facile preparation of high-performance Fe-doped Ce-Mn/TiO2 catalysts for the low-temperature selective catalytic reduction of NOx with NH3"", vol. 7, pages 48785 - 48792 * |
| 张丹等: ""中低温Fe2O3-MnO2-CeO2/ TiO2脱硝催化剂的 合成、表征及催化活性"", vol. 32, pages 172 - 176 * |
| 张瀚丹: ""Mn-Ce/低钛高炉渣低温脱硝催化剂铅中毒机制与再生研究"", 《CNKI优秀硕士学问论文全文库》, pages 1 - 109 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115193446A (zh) * | 2022-07-12 | 2022-10-18 | 北京科技大学 | 一种选择性催化脱除NOx的催化剂的制备方法 |
| CN115193446B (zh) * | 2022-07-12 | 2023-10-20 | 北京科技大学 | 一种选择性催化脱除NOx的催化剂的制备方法 |
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