碱处理改性CeMn/ZSM-5催化剂的NH<sub>3</sub>-SCR性能

赵磊; 王传义; 张婷; 吕海钦; 苑明哲

doi:10.13205/j.hjgc.202408011

碱处理改性CeMn/ZSM-5催化剂的NH₃-SCR性能

doi: 10.13205/j.hjgc.202408011

1. 陕西科技大学环境科学与工程学院, 西安 710000;
2. 广州工业智能研究院, 广州 510000

基金项目:

山东省科技型中小企业创新能力(2022TSGC1081)

广东省“珠江人才计划”高层次人才引进项目(2019CX01L308)

广州市基础研究计划(2023A04J0697,202201011535)

广东省自然科学基金项目(2023A1515010598)

粤广联合基金(2022A1515110642)

详细信息

作者简介:
赵磊(1997-),男,硕士,主要研究方向为环境功能材料脱硝催化剂。384461361@qq.com

通讯作者:
赵磊(1997-),男,硕士,主要研究方向为环境功能材料脱硝催化剂。384461361@qq.com

计量
- 文章访问数: 10
- HTML全文浏览量: 0
- PDF下载量: 3
- 被引次数: 0
出版历程
- 收稿日期: 2023-12-27
- 网络出版日期: 2024-12-02

NH₃-SCR PROPERTIES OF CeMn/ZSM-5 CATALYST MODIFIED BY ALKALI-TREATMENT

1. College of Environmental Science and Engineering, Shaanxi University of Science and Technology, Xi'an 710000, China;
2. Guangzhou Industrial Intelligence Research Institute, Guangzhou 510000, China

摘要

摘要: 氮氧化物NO_x作为大气污染物之一,已经造成了严重的环境问题,危及生态环境和人类健康。用氨选择性催化还原(NH₃-SCR) NO_x已成为脱硝的重要应用技术。区别于传统方式合成的负载型ZSM-5催化剂,采用浸渍后水热的方式一锅法合成Ce、Mn双金属改性ZSM-5催化剂,并在此基础上引入碱处理改性方法对ZSM-5分子筛进行预处理,成功合成了比表面积和孔隙结构等形貌得到改善的CeMn/ZSM-5-OH催化剂,175~350 ℃内NO_x转化率＞90%,且相比CeMn/ZSM-5样品低温段活性提升近40%。碱处理过后的CeMn/ZSM-5-OH催化剂生成了更多的Ce³⁺和Mn⁴⁺,加大了其对反应气体NO和NH₃的吸附性;XPS结果表明晶格氧参与了Ce³⁺和Mn⁴⁺之间的电子转移作用,有利于NO与NH₃的活化,从而推动NH₃-SCR反应的进行。
- ZSM-5 /
- 碱处理 /
- 孔隙结构 /
- 表面酸度 /
- NH₃-SCR
Abstract: Nitrogen oxides, as one of the atmospheric pollutants, have caused serious environmental problems, endangering the ecological environment and human health. Selective catalytic reduction of NO_x with ammonia (NH₃-SCR) has become an important application technology for denitrification. Different from the supported ZSM-5 catalyst synthesized by traditional methods, Ce and Mn bimetallic modified ZSM-5 catalyst was synthesized by one-pot method, and the ZSM-5 molecular sieve was pretreated by alkali. The CeMn/ZSM-5-OH catalyst with improved surface area and pore structure was successfully synthesized. In the performance test, the NO_x conversion rate was beyond 90% in the temperature range of 175 to 350 ℃, and the activity was increased by nearly 40%, compared with that of CeMn/ZSM-5 samples in low temperature section. After alkali-treatment, the CeMn/ZSM-5-OH catalyst generated more Ce³⁺ and Mn⁴⁺, which increased the adsorption performance of NO and NH₃. The results of XPS showed that lattice oxygen participated in the electron transfer between Ce³⁺ and Mn⁴⁺, which was conducive to the activation of NO and NH₃. Thus, the NH₃-SCR reaction was promoted.
- ZSM-5 /
- alkali-treatment /
- pore structure /
- surface acidity /
- NH₃-SCR

HTML全文

参考文献(43)

[1]	余沃晖, 张盼, 赵一明, 等. 低温脱硝催化剂研究进展[J]. 无机盐工业, 2022, 54(10): 57-67 , 120.
[2]	PAN W, HE J, HUANG G, et al. Research progress of the selective catalytic reduction with NH₃ over ZSM-5 zeolite catalysts for NO_x removal[J]. Catalysts, 2023, 13(10): 1381.
[3]	喻成龙, 黄碧纯, 杨颖欣. 分子筛应用于低温NH₃-SCR脱硝催化剂的研究进展[J]. 华南理工大学学报(自然科学版), 2015, 43(3): 143-150.
[4]	骆中璨, 彭波, 夏龙贵, 等. 分子筛ZSM-5改性性能研究进展[J]. 江西化工, 2022, 38(5): 19-24.
[5]	张乾蔚王学涛. 不同金属改性Ce-Mn/ZSM-5催化剂的制备及性能研究[J]. 燃料化学学报, 2019, 47(10): 1265-1272.
[6]	CAO J, XING M, HAN Y, et al. Improving the hydrothermal stability of ZSM-5 zeolites in 1-Octene aromatization by sequential alkali treatment and phosphorus modification[J]. Catalysts, 2022, 12(12): 1629.
[7]	CHENG S, LU S, LIU X, et al. Enhanced activity of alkali-treated ZSM-5 zeolite-supported Pt-Co catalyst for selective hydrogenation of cinnamaldehyde[J]. Molecules, 2023, 28(4): 1730.
[8]	HAN D, CHEN Y LI C. The hydrothermal stability of the alkali-treated ZSM-5 and its catalytic performance in catalytic cracking of VGO[J]. Chemical Papers, 2018. 73(1): 215-220.
[9]	JABŁOŃSKA M, GÓRA-MAREK K, BRUZZESE P C, et al. Influence of framework n(Si)/n(Al) ratio on the nature of Cu species in Cu-ZSM-5 for NH₃-SCR-DeNO_x[J]. ChemCatChem, 2022, 14(18): e202200627.
[10]	ZHAO W, SHEN M, ZHU Y, et al. Insights into synergy of copper and acid sites for selective catalytic reduction of NO with ammonia over zeolite catalysts[J]. Catalysts, 2023, 13(2): 301.
[11]	DOAN T, DANG A, NGUYEN D, et al. Hybrid Cu-Fe/ZSM-5 catalyst prepared by liquid ion-exchange for NO_x removal by NH₃-SCR process[J]. Journal of Chemistry, 2021: 1-15.
[12]	LIU B, ZHENG K, LIAO Z, et al. Fe-encapsulated ZSM-5 zeolite with nanosheet-assembled structure for the selective catalytic reduction of NO_x with NH₃[J]. Industrial & Engineering Chemistry Research, 2020, 59: 8592-9600.
[13]	YUE Y, LIU B, LV N, et al. Direct synthesis of hierarchical FeCu-ZSM-5 zeolite with wide temperature window in selective catalytic reduction of NO by NH₃[J]. ChemCatChem, 2019, 11(19): 4744-4754.
[14]	WANG Y, JI X, MENG H, et al. Fabrication of high-silica Cu/ZSM-5 with confinement encapsulated Cu-based active species for NH₃-SCR[J]. Catalysis Communications, 2020, 138: 105969.
[15]	CHEN Z, LIU L, QU H, et al. The effect of CeO₂ dispersity and active oxygen species on the SCR reaction over Fe-ZSM-5@Ce/meso-SiO₂[J]. Catalysis Letters, 2020, 150: 514-523.
[16]	PENG C, YAN R, PENG H, et al. One-pot synthesis of layered mesoporous ZSM-5 plus Cu ion-exchange: enhanced NH₃-SCR performance on Cu-ZSM-5 with hierarchical pore structures[J]. Journal of Hazardous Materials, 2020, 385: 121593.
[17]	DEVI T G KANNAN M. X-ray diffraction (XRD) studies on the chemical states of some metal species in cellulosic chars and the Ellingham diagrams[J]. Energy & Fuels, 2007, 21(2): 596-601.
[18]	ZHU L, ZHANG L, QU H, et al. A study on chemisorbed oxygen and reaction process of Fe-CuO_x/ZSM-5 via ultrasonic impregnation method for low-temperature NH₃-SCR[J]. Journal of Molecular Catalysis a-Chemical, 2015, 409: 207-215.
[19]	杨全红, 郑经堂, 王茂章, 等. 活性炭纤维对NH₃的吸附研究Ⅰ PAN-ACF孔径结构对NH₃静态吸附的影响[J]. 新型碳材料, 1998(2): 44-49.
[20]	孙爱明, 倪友明, 欧丽娟, 等. 碱处理和Zn改性ZSM-5分子筛上乙醇芳构化性能的研究[J]. 应用化工, 2015, 44(1): 95-98.
[21]	袁方, 厉刚, 胡申林. 碱处理对ZSM-5分子筛膜结构及其催化性能的影响[J]. 石油学报(石油加工), 2014, 30(1): 140-144.
[22]	刘冬梅, 华志远, 马健, 等. 碱处理ZSM-5分子筛上噻吩烷基化性能的研究[J]. 应用化工, 2014, 43(6): 1021-1024.
[23]	JI J, TANG Y, HAN L, et al. Cerium manganese oxides coupled with ZSM-5: a novel SCR catalyst with superior K resistance[J]. Chemical Engineering Journal, 2022, 445: 136530.
[24]	WANG L L, WANG M H, FEI Z Y, et al. Preparation of amorphous MnO_x/TiO₂ catalyst and its performance in low temperature NH₃-SCR[J]. 燃料化学学报 (中英文), 2017, 45(8): 993-1000.
[25]	DONG Y, JIN B, LIU S, et al. Abundant oxygen vacancies induced by the mechanochemical process boost the low-temperature catalytic performance of MnO₂ in NH₃-SCR[J]. Catalysts, 2022, 12(10): 1291.
[26]	ZHANG S, LI H, ZHANG A, et al. Selective catalytic reduction of NO_x by low-temperature NH₃ over Mn_xZr₁ mixed-oxide catalysts[J]. RSC advances, 2022, 12(3): 1341-1351.
[27]	RAMANA S, RAO B G, VENKATASWAMY P, et al. Nanostructured Mn-doped ceria solid solutions for efficient oxidation of vanillyl alcohol[J]. Journal of Molecular Catalysis A: Chemical, 2016, 415: 113-121.
[28]	MU W, ZHU J, ZHANG S, et al. Novel proposition on mechanism aspects over Fe-Mn/ZSM-5 catalyst for NH₃-SCR of NO_x at low temperature: rate and direction of multifunctional electron-transfer-bridge and in situ DRIFTs analysis[J]. Catalysis Science & Technology, 2016, 6(20): 7532-7548.
[29]	YANG S, WANG C, LI J, et al. Low temperature selective catalytic reduction of NO with NH₃ over Mn-Fe spinel: performance, mechanism and kinetic study[J]. Applied Catalysis B: Environmental, 2011, 110: 71-80.
[30]	郝广源井宇. V-Ce/TiO₂脱硝催化剂的SO₂中毒机理研究[J]. 分子催化, 2023, 37(5): 428-438.
[31]	YAO X, MA K, ZOU W, et al. Influence of preparation methods on the physicochemical properties and catalytic performance of MnO_x-CeO₂ catalysts for NH₃-SCR at low temperature[J]. Chinese Journal of Catalysis, 2017, 38(1): 146-159.
[32]	TANG X, LI Y, HUANG X, et al. MnO_x-CeO₂ mixed oxide catalysts for complete oxidation of formaldehyde: effect of preparation method and calcination temperature[J]. Applied Catalysis B: Environmental, 2006, 62(3/4): 265-273.
[33]	WANG X, DUAN R, LIU W, et al. The insight into the role of CeO₂ in improving low-temperature catalytic performance and SO₂ tolerance of MnCoCeO_x microflowers for the NH₃-SCR of NO_x[J]. Applied Surface Science, 2020, 510: 145517.
[34]	XIONG S, PENG Y, WANG D, et al. The role of the Cu dopant on a Mn₃O₄ spinel SCR catalyst: improvement of low-temperature activity and sulfur resistance[J]. Chemical Engineering Journal, 2020, 387: 124090.
[35]	BONINGARI T, ETTIREDDY P R, SOMOGYVARI A, et al. Influence of elevated surface texture hydrated titania on Ce-doped Mn/TiO₂ catalysts for the low-temperature SCR of NO_x under oxygen-rich conditions[J]. Journal of Catalysis, 2015, 325: 145-155.
[36]	MURUGAN B, RAMASWAMY A, SRINIVAS D, et al. Nature of manganese species in Ce_1-xMn_xO_2-δ solid solutions synthesized by the solution combustion route[J]. Chemistry of Materials, 2005, 17(15): 3983-3993.
[37]	FAN Z, SHI J-W, GAO C, et al. Gd-modified MnO_x for the selective catalytic reduction of NO by NH₃: the promoting effect of Gd on the catalytic performance and sulfur resistance[J]. Chemical Engineering Journal, 2018, 348: 820-830.
[38]	ZHANG D, ZHANG L, SHI L, et al. In situ supported MnO_x-CeO_x on carbon nanotubes for the low-temperature selective catalytic reduction of NO with NH₃[J]. Nanoscale, 2013, 5(3): 1127-1136.
[39]	崔立峰, 吕誉, 李云强, 等. CeO₂/ZrO₂对Cu-ZSM-5选择性催化还原NO_x的反应活性及抗老化性能的影响[J]. 燃烧科学与技术, 2023, 29(6): 676-684.
[40]	孙锦昌, 任翠涛, 赵明新, 等. Cu/Hβ催化剂NH₃选择性催化还原NO性能研究[J]. 燃料化学学报(中英文), 2023, 51(6): 823-831.
[41]	PENG C, YAN R, PENG H, et al. One-pot synthesis of layered mesoporous ZSM-5 plus Cu ion-exchange: enhanced NH₃-SCR performance on Cu-ZSM-5 with hierarchical pore structures[J]. J Hazard Mater, 2020, 385: 121593.
[42]	CAO F, SU S, XIANG J, et al. The activity and mechanism study of Fe-Mn-Ce/γ-Al₂O₃ catalyst for low temperature selective catalytic reduction of NO with NH₃[J]. Fuel, 2015, 139: 232-239.
[43]	CAO F, XIANG J, SU S, et al. Ag modified Mn-Ce/γ-Al₂O₃ catalyst for selective catalytic reduction of NO with NH₃ at low-temperature[J]. Fuel Processing Technology, 2015, 135: 66-72.