一步法制备高活性NH3-SCR催化剂Cu-SAPO-34：Si含量的影响

doi:10.11949/0438-1157.20201613

摘要/Abstract

摘要：

NH₃选择性催化还原（NH₃-SCR）可以有效脱除机动车尾气中的氮氧化物（NO_x），开发在中低温下具有高活性且环境友好的低成本催化剂是该技术的关键。以廉价的商品吗啡啉为模板剂，新型络合物Cu-TEPA兼作Cu源和共模板剂，一步水热合成法制备出Cu-SAPO-34分子筛。发现随着Si含量增加，Cu-SAPO-34的结晶度逐渐降低，酸性位点和孤立Cu²⁺的数量逐渐减少。通过固定床实验系统研究了3种Si含量的Cu-SAPO-34在不同空速下的NH₃-SCR性能。结果表明，在气体体积空速（GHSV=40000~120000 h^-1）下，Cu-SAPO-34均表现出较优异的SCR活性；当SiO₂/Al₂O₃摩尔比为0.2时，具有理想的低温活性（转化率>90%）和较宽的温度窗口（225~425℃）。

关键词: 分子筛, 共模板剂, 选择性催化还原, 催化剂活性, Si含量

Abstract:

NH₃ selective catalytic reduction (NH₃-SCR) can effectively remove nitrogen oxides (NO_x) from automobile exhaust. The development of low-cost catalysts with high activity at medium and low temperatures and environmentally friendly is the key to this technology. In this work, by utilizing cheap commercial organic structure guide agent morpholine as template, and copper amine complex (Cu-TEPA) as both Cu source and co-templating agent, a low-cost Cu-SAPO-34 molecular sieve was prepared by one-step hydrothermal synthesis method. It was found that with increasing the Si content, the crystallinity of Cu-SAPO-34 gradually decreases, and the acidic sites and Cu²⁺ ions gradually decrease. The NH₃-SCR performance of Cu-SAPO-34 with three different Si contents under different space velocities was systematically studied through fixed-bed experiments. The results show that under gas volumetric space velocity (GHSV=40000—120000 h^-1), Cu-SAPO-34 shows excellent SCR activity; when the SiO₂/Al₂O₃ molar ratio is 0.2, the prepared SCR catalyst, Cu-SAPO-34 has ideal low-temperature activity with the conversion of more than 90% and wide temperature window (225—425℃). This is attributed to the increase of Si addition, the crystallinity of Cu-SAPO-34 gradually decreases, and the precipitation of acidic sites and Cu²⁺ ions gradually decrease.

Key words: molecular sieves, co-templating agent, selective catalytic reduction, catalyst activation, Si contents

中图分类号:

TQ 028.8

邱爽, 肖永厚, 刘建辉, 贺高红. 一步法制备高活性NH₃-SCR催化剂Cu-SAPO-34：Si含量的影响[J]. 化工学报, 2021, 72(5): 2578-2585.

QIU Shuang, XIAO Yonghou, LIU Jianhui, HE Gaohong. Enhanced NH₃-SCR performance over Cu-SAPO-34 prepared by one-step synthesis: effect of Si contents[J]. CIESC Journal, 2021, 72(5): 2578-2585.

参考文献 37

1	Liu X S, Wu X D, Weng D, et al. Modification of Cu/ZSM-5 catalyst with CeO₂ for selective catalytic reduction of NO_x with ammonia[J]. Journal of Rare Earths, 2016, 34(10): 1004-1009.
2	Wang J H, Zhao H W, Haller G, et al. Recent advances in the selective catalytic reduction of NO_x with NH₃ on Cu-Chabazite catalysts[J]. Applied Catalysis B: Environmental, 2017, 202: 346-354.
3	Li Y, Cheng H, Li D Y, et al. WO₃/CeO₂-ZrO₂, a promising catalyst for selective catalytic reduction (SCR) of NO_x with NH₃ in diesel exhaust[J]. Chemical Communications, 2008, (12): 1470.
4	An W Z, Zhang Q L, Chuang K T, et al. A hydrophobic Pt/fluorinated carbon catalyst for reaction of NO with NH₃[J]. Industrial & Engineering Chemistry Research, 2002, 41(1): 27-31.
5	Huang L M, Wang X M, Yao S L, et al. Cu-Mn bimetal ion-exchanged SAPO-34 as an active SCR catalyst for removal of NO_x from diesel engine exhausts[J]. Catalysis Communications, 2016, 81: 54-57.
6	Wang C, Wang J, Wang J Q, et al. The effect of sulfate species on the activity of NH₃-SCR over Cu/SAPO-34[J]. Applied Catalysis B: Environmental, 2017, 204: 239-249.
7	Villamaina R, Nova I, Tronconi E, et al. The deactivation of an NH₃-SCR Cu-SAPO catalyst upon exposure to non-oxidizing conditions[J]. Applied Catalysis A: General, 2019, 580: 11-16.
8	Wang D, Jangjou Y, Liu Y, et al. A comparison of hydrothermal aging effects on NH₃-SCR of NO_x over Cu-SSZ-13 and Cu-SAPO-34 catalysts[J]. Applied Catalysis B: Environmental, 2015, 165: 438-445.
9	Petitto C, Delahay G. Selective catalytic reduction of NO_x by NH₃ on Cu-SAPO-34 catalysts: influence of silicium content on the activity of calcined and hydrotreated samples[J]. Chemical Engineering Journal, 2015, 264: 404-410.
10	Liu B, Zhao X H, Mao W T, et al. Pickering emulsion mediated crystallization of hierarchical zeolite SSZ-13 with enhanced NH₃ selective catalytic reduction performance[J]. Microporous and Mesoporous Materials, 2019, 285: 202-214.
11	Jiang H, Guan B, Lin H, et al. Cu/SSZ-13 zeolites prepared by in situ hydrothermal synthesis method as NH₃-SCR catalysts: influence of the Si/Al ratio on the activity and hydrothermal properties[J]. Fuel, 2019, 255: 115587.
12	Wang X H, Zhang R D, Wang H, et al. Strategy on effective synthesis of SSZ-13 zeolite aiming at outstanding performances for NH₃-SCR process[J]. Catalysis Surveys from Asia, 2020, 24(2): 143-155.
13	Chen Z, Fan C, Pang L, et al. One-pot synthesis of high performance Cu-SAPO-18 catalyst for NO reduction by NH₃-SCR: influence of silicon content on the catalytic properties of Cu-SAPO-18[J]. Chemical Engineering Journal, 2018, 348: 608-617.
14	马子然, 王宝冬, 路光杰, 等. 粉煤灰基SAPO-34分子筛脱硝催化剂的合成及其脱硝性能[J]. 化工进展, 2020, 39(10): 4051-4060.
	Ma Z R, Wang B D, Lu G J, et al. Preparation and performance of SAPO-34 based SCR catalyst derived from fly ash[J]. Chemical Industry and Engineering Progress, 2020, 39(10): 4051-4060.
15	Fickel D W, D'Addio E, Lauterbach J A, et al. The ammonia selective catalytic reduction activity of copper-exchanged small-pore zeolites[J]. Applied Catalysis B: Environmental, 2011, 102(3/4): 441-448.
16	Fan D Q, Wang J, Yu T, et al. Catalytic deactivation mechanism research over Cu/SAPO-34 catalysts for NH₃-SCR (Ⅰ): The impact of 950 ℃ hydrothermal aging time[J]. Chemical Engineering Science, 2018, 176: 285-293.
17	Liu J X, Yu F H, Liu J, et al. Synthesis and kinetics investigation of meso-microporous Cu-SAPO-34 catalysts for the selective catalytic reduction of NO with ammonia[J]. Journal of Environmental Sciences, 2016, 48: 45-58.
18	Liu F D, Yu Y B, He H. Environmentally-benign catalysts for the selective catalytic reduction of NO_x from diesel engines: structure-activity relationship and reaction mechanism aspects[J]. Chemical Communications (Cambridge, England), 2014, 50(62): 8445-8463.
19	Zhang D, Yang R T. NH₃-SCR of NO over one-pot Cu-SAPO-34 catalyst: performance enhancement by doping Fe and MnCe and insight into N₂O formation[J]. Applied Catalysis A: General, 2017, 543: 247-256.
20	Ma J, Si Z C, Weng D, et al. Potassium poisoning on Cu-SAPO-34 catalyst for selective catalytic reduction of NO_x with ammonia[J]. Chemical Engineering Journal, 2015, 267: 191-200.
21	Huang S Y, Wang J, Wang J Q, et al. The influence of crystallite size on the structural stability of Cu/SAPO-34 catalysts[J]. Applied Catalysis B: Environmental, 2019, 248: 430-440.
22	Yu Q F, Liu X S, Chen H F, et al. In situ regeneration of sulfated Cu/SAPO-34 catalyst for the selective catalytic reduction of NO_x with NH₃[J]. Reaction Kinetics, Mechanisms and Catalysis, 2019, 128(2): 1065-1077.
23	Chen M Y, Sun Q M, Yang G J, et al. Enhanced performance for selective catalytic reduction of NO_x with NH₃ over nanosized Cu/SAPO-34 catalysts[J]. ChemCatChem, 2019, 11(16): 3865-3870.
24	Huang Z W, Gu X, Wen W, et al. A “smart” hollandite DeNO_x catalyst: self-protection against alkali poisoning[J]. Angewandte Chemie International Edition, 2013, 52(2): 660-664.
25	Yu T, Xu M H, Huang Y, et al. Insight of platinum poisoning Cu/SAPO-34 during NH₃-SCR and its promotion on catalysts regeneration after hydrothermal treatment[J]. Applied Catalysis B: Environmental, 2017, 204: 525-536.
26	Albert K B, Fan C, Pang L, et al. The influence of chemical poisoning, hydrothermal aging and their co-effects on Cu-SAPO-34 catalyst for NO_x reduction by NH₃-SCR[J]. Applied Surface Science, 2019, 479: 1200-1211.
27	王晨, 陈泽翔, 王建强, 等. 基于NH₃-SCR反应铜基小孔分子筛催化剂Na中毒对比研究[J]. 化工学报, 2020, 71(12): 5551-5560.
	Wang C, Chen Z X, Wang J Q, et al. Comparison study of Na poisoning effect on copper-based chabazite micropore catalysts for NH₃-SCR reaction[J]. CIESC Journal, 2020, 71(12): 5551-5560.
28	Wang J, Yu T, Wang X Q, et al. The influence of silicon on the catalytic properties of Cu/SAPO-34 for NO_x reduction by ammonia-SCR[J]. Applied Catalysis B: Environmental, 2012, 127: 137-147.
29	Li X H, Zhao Y N, Zhao H W, et al. The Cu migration of Cu-SAPO-34 catalyst for ammonia selective catalytic reduction of NO_x during high temperature hydrothermal aging treatment[J]. Catalysis Today, 2019, 327: 126-133.
30	李渊, 孙丹, 杨晨芳, 等. 硅溶胶粒径大小对SAPO-34合成及甲醇制烯烃催化性能的影响[J]. 化工进展, 2020, 39(9): 3701-3707.
	Li Y, Sun D, Yang C F, et al. Effect of silica Sol particle size on SAPO-34 synthesis and catalytic performance in methanol to olefin reaction[J]. Chemical Industry and Engineering Progress, 2020, 39(9): 3701-3707.
31	闫春迪, 程昊, 陈海军, 等. 不同Cu交换分子筛脱除柴油机尾气中的NO_x[J]. 环境工程学报, 2015, 9(6): 2967-2973.
	Yan C D, Cheng H, Chen H J, et al. Removal of NO_x from diesel engine exhaust by different Cu²⁺-exchanged zeolites[J]. Chinese Journal of Environmental Engineering, 2015, 9(6): 2967-2973.
32	Velu S, Suzuki K, Vijayaraj M, et al. In situ XPS investigations of Cu_1-_xNi_xZnAl-mixed metal oxide catalysts used in the oxidative steam reforming of bio-ethanol[J]. Applied Catalysis B: Environmental, 2005, 55(4): 287-299.
33	Liu J X, Liu J, Zhao Z, et al. Synthesis of a chabazite-supported copper catalyst with full mesopores for selective catalytic reduction of nitrogen oxides at low temperature[J]. Chinese Journal of Catalysis, 2016, 37(5): 750-759.
34	Hu X Q, Yang M, Fan D Q, et al. The role of pore diffusion in determining NH₃ SCR active sites over Cu/SAPO-34 catalysts[J]. Journal of Catalysis, 2016, 341: 55-61.
35	Liu X S, Wu X D, Weng D, et al. Evolution of copper species on Cu/SAPO-34 SCR catalysts upon hydrothermal aging[J]. Catalysis Today, 2017, 281: 596-604.
36	Yan C D, Cheng H, Yuan Z S, et al. The role of isolated Cu²⁺ location in structural stability of Cu-modified SAPO-34 in NH₃-SCR of NO[J]. Environmental Technology, 2015, 36(2): 169-177.
37	Peng C, Liang J, Peng H G, et al. Design and synthesis of Cu/ZSM-5 catalyst via a facile one-pot dual-template strategy with controllable Cu content for removal of NO_x[J]. Industrial & Engineering Chemistry Research, 2018, 57(44): 14967-14976.

[1]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[2]	韩奎奎, 谭湘龙, 李金芝, 杨婷, 张春, 张永汾, 刘洪全, 于中伟, 顾学红. 四通道中空纤维MFI分子筛膜用于二甲苯异构体分离[J]. 化工学报, 2023, 74(6): 2468-2476.
[3]	王子健, 柯明, 李佳涵, 李舒婷, 孙巾茹, 童燕兵, 赵治平, 刘加英, 任璐. 短b轴ZSM-5分子筛制备方法及应用研究进展[J]. 化工学报, 2023, 74(4): 1457-1473.
[4]	王荣, 王永洪, 张新儒, 李晋平. 6FDA型聚酰亚胺炭分子筛气体分离膜的构筑及其应用[J]. 化工学报, 2023, 74(4): 1433-1445.
[5]	白宇恩, 张彬瑞, 刘东阳, 赵亮, 高金森, 徐春明. ZSM-5分子筛酸性能和孔结构的协同作用对C₅烯烃催化裂解性能的影响[J]. 化工学报, 2023, 74(1): 438-448.
[6]	郑涛, 刘海燕, 张睿, 孟祥海, 岳源源, 刘植昌. 基于分子筛绿色合成的天然硅铝矿物介尺度活化研究进展[J]. 化工学报, 2022, 73(6): 2334-2351.
[7]	王婵, 肖国锡, 郭小雪, 徐人威, 岳源源, 鲍晓军. 基于介尺度结构解聚-重组装的Beta分子筛的绿色合成及应用[J]. 化工学报, 2022, 73(6): 2690-2697.
[8]	王旭, 张乐瑶, 张昊轩, 演嘉辉, 吴玉帅, 吴冬, 陈汇勇, 马晓迅. 中空孔结构对W掺杂MFI分子筛丙酮吸附行为的研究[J]. 化工学报, 2022, 73(3): 1194-1206.
[9]	苏畅, 冯晓博, 张立云, 陈峰, 赵小燕, 曹景沛. 四乙基氢氧化铵改性对HMOR分子筛结构及二甲醚羰基化性能的影响[J]. 化工学报, 2022, 73(2): 712-721.
[10]	王吴玉, 史玉竹, 严龙, 张兴华, 马隆龙, 张琦. 负载型Co基双功能催化剂上戊酸酯生物燃料的制备[J]. 化工学报, 2022, 73(2): 689-698.
[11]	赵丽文, 刘桂莲. 苯加氢制环己烯装置能量系统集成及催化剂再生周期优化[J]. 化工学报, 2022, 73(12): 5494-5503.
[12]	张超, 陈健, 殷文华, 沈圆辉, 钮朝阳, 余秀鑫, 张东辉, 唐忠利. 变压吸附氢气纯化过程瞬态分析[J]. 化工学报, 2022, 73(1): 308-321.
[13]	高文莉, 辛忠. Fe对Ni/SBA-16催化CO低温甲烷化促进作用的研究[J]. 化工学报, 2022, 73(1): 241-254.
[14]	李腾飞, 缪赟, 杨柳, 王龙耀, 朱铧丞. 微波强化Y型分子筛离子交换技术[J]. 化工学报, 2021, 72(S1): 406-412.
[15]	王伟, 钱伟鑫, 马宏方, 应卫勇, 张海涛. 吡啶修饰H-MOR上二甲醚羰基化吸附-扩散理论研究[J]. 化工学报, 2021, 72(9): 4786-4795.

一步法制备高活性NH₃-SCR催化剂Cu-SAPO-34：Si含量的影响

Enhanced NH₃-SCR performance over Cu-SAPO-34 prepared by one-step synthesis: effect of Si contents

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献 37

相关文章 15

编辑推荐

Metrics

本文评价