Influence of zirconium modified carriers on the NH3-SCR performance of manganese-cerium composite catalysts

doi:10.16085/j.issn.1000-6613.2023-1919

Abstract

Abstract:

A hydrothermal method was employed to synthesize cerium-zirconium (Ce _n Zr_1-_n ) supports with different ratios, and a series of composite catalysts were then prepared by impregnating MnO _x as the active component. The catalytic performance of these catalysts in the selective catalytic reduction of NO _x with ammonia (NH₃-SCR) was investigated. The catalysts were characterized by various techniques such as XRD, Raman, SEM, N₂ adsorption-desorption, H₂-TPR, NH₃-TPD, and XPS, to examine their structure, morphology, surface acidity, and surface oxidation state. The results indicated that Ce _n Zr_1-_n prepared by the hydrothermal method exhibited better NH₃-SCR catalytic activity than CeO₂ supports. Similarly, 8Mn/Ce _n Zr_1-_n catalysts show improved performance. Among them, the 8Mn/Ce_0.8Zr_0.2 catalyst exhibited the best catalytic activity, with T₅₀ and T₉₀ of 100.2℃ and 130.2℃, respectively. The working temperature window was 245.5℃ (130.2—377.2℃), and 100% NO conversion rate was maintained between 159.6℃ and 349.0℃. The catalyst demonstrated better low-temperature reduction performance and more acidic sites, which facilitated the adsorption and reduction of reactants at low temperatures. Furthermore, it had a relative high content of high-valence Mn⁴⁺ species on the surface, which contributed to enhancing NH₃-SCR catalytic activity.

Key words: rare earth element, ammonia-selective catalytic reduction, nitrogen oxide, catalysis technology

摘要：

采用水热法合成不同比例的铈锆载体，通过浸渍法将MnO _x 作为活性组分制备一系列复合催化剂，并考察其在以NH₃为还原剂的选择性催化还原NO _x 反应（NH₃-SCR）中的脱硝活性。通过XRD、Raman、SEM、N₂吸脱附、H₂-TPR、NH₃-TPD、XPS等技术手段对催化剂的结构、形貌、表面酸性、表面氧化价态等进行了表征。结果表明，水热法制备的Ce _n Zr_1-_n 较CeO₂载体具有更好的NH₃-SCR催化活性，8Mn/Ce _n Zr_1-_n 催化剂均有性能提升，其中8Mn/Ce_0.8Zr_0.2催化剂具有最佳的催化活性，其T₅₀和T₉₀分别为100.2℃和130.2℃，工作温度窗口为245.5℃（130.2~377.2℃），并且159.6~349.0℃范围内保持100%的NO转化率，具有更好的低温还原性能和更多的酸性位点，有利于反应物在更低的温度被吸附还原；其表面高价的Mn⁴⁺物种相对含量更高，有利于提升NH₃-SCR催化活性。

关键词: 稀土元素, NH₃选择性催化还原, 氮氧化物, 催化技术

CLC Number:

O643

GAO Zihan, YANG Runnong, WANG Zhaoying, SONG Yanhai, QIN Bin, YU Lin. Influence of zirconium modified carriers on the NH₃-SCR performance of manganese-cerium composite catalysts[J]. Chemical Industry and Engineering Progress, 2024, 43(11): 6206-6214.

高梓寒, 杨润农, 王钊颖, 宋燕海, 覃斌, 余林. 锆修饰载体对锰铈复合催化剂NH₃-SCR性能的影响[J]. 化工进展, 2024, 43(11): 6206-6214.

Figures/Tables 13

References 42

1	BOHON Myles D, RASHIDI Mariam J AL, Mani SARATHY S, et al. Experiments and simulations of NO _x formation in the combustion of hydroxylated fuels[J]. Combustion and Flame, 2015, 162(6): 2322-2336.
2	LIU Zhiming, LI Junhua, Seong Ihl WOO. Recent advances in the selective catalytic reduction of NO _x by hydrogen in the presence of oxygen[J]. Energy & Environmental Science, 2012, 5(10): 8799-8814.
3	王艳, 李兆强, 张丞, 等. CeO₂含量对柴油机商用稀土SCR催化剂脱硝性能的影响[J]. 化工进展, 2020, 39(7): 2662-2669.
	WANG Yan, LI Zhaoqiang, ZHANG Cheng, et al. Influence of CeO₂ contents on the SCR performance of commercial rare earth catalysts[J]. Chemical Industry and Engineering Progress, 2020, 39(7): 2662-2669.
4	DEKA Upakul, Ines LEZCANO-GONZALEZ, WECKHUYSEN Bert M, et al. Local environment and nature of Cu active sites in zeolite-based catalysts for the selective catalytic reduction of NO _x [J]. ACS Catalysis, 2013, 3(3): 413-427.
5	GRANGER Pascal, PARVULESCU Vasile I. Catalytic NO _x abatement systems for mobile sources: From three-way to lean burn after-treatment technologies[J]. Chemical Reviews, 2011, 111(5): 3155-3207.
6	BUSCA Guido, LIETTI Luca, RAMIS Gianguido, et al. Chemical and mechanistic aspects of the selective catalytic reduction of NO by ammonia over oxide catalysts: A review[J]. Applied Catalysis B: Environmental, 1998, 18(1/2): 1-36.
7	KOMPIO Patrick G W A, Angelika BRÜCKNER, HIPLER Frank, et al. A new view on the relations between tungsten and vanadium in V₂O₅-WO₃/TiO₂ catalysts for the selective reduction of NO with NH₃ [J]. Journal of Catalysis, 2012, 286: 237-247.
8	ZHANG Jie, HUANG Zhiwei, DU Yueyao, et al. Atomic-scale insights into the nature of active sites in Fe₂O₃-supported submonolayer WO₃ catalysts for selective catalytic reduction of NO with NH₃ [J]. Chemical Engineering Journal, 2020, 381: 122668.
9	BRANDENBERGER Sandro, Oliver KRÖCHER, TISSLER Arno, et al. The state of the art in selective catalytic reduction of NO _x by ammonia using metal-exchanged zeolite catalysts[J]. Catalysis Reviews, 2008, 50(4): 492-531.
10	ROY Sounak, BAIKER Alfons. NO _x storage-reduction catalysis: From mechanism and materials properties to storage-reduction performance[J]. Chemical Reviews, 2009, 109(9): 4054-4091.
11	FANG Xue, LIU Yongjun, CEN Wanglai, et al. Birnessite as a highly efficient catalyst for low-temperature NH₃-SCR: The vital role of surface oxygen vacancies[J]. Industrial & Engineering Chemistry Research, 2020, 59(33): 14606-14615.
12	MENG Dongmei, ZHAN Wangcheng, GUO Yun, et al. A highly effective catalyst of Sm-MnO _x for the NH₃-SCR of NO _x at low temperature: Promotional role of Sm and its catalytic performance[J]. ACS Catalysis, 2015, 5(10): 5973-5983.
13	TANG Xingfu, LI Junhua, SUN Liang, et al. Origination of N₂O from NO reduction by NH₃ over β-MnO₂ and α-Mn₂O₃ [J]. Applied Catalysis B: Environmental, 2010, 99(1/2): 156-162.
14	GAO Ge, SHI Jianwen, LIU Chang, et al. Mn/CeO₂ catalysts for SCR of NO _x with NH₃: Comparative study on the effect of supports on low-temperature catalytic activity[J]. Applied Surface Science, 2017, 411: 338-346.
15	SHEN Boxiong, WANG Yinyin, WANG Fumei, et al. The effect of Ce-Zr on NH₃-SCR activity over MnO _x (0.6)/Ce_0.5Zr_0.5O₂ at low temperature[J]. Chemical Engineering Journal, 2014, 236: 171-180.
16	DING Shipeng, LIU Fudong, SHI Xiaoyan, et al. Significant promotion effect of Mo additive on a novel Ce-Zr mixed oxide catalyst for the selective catalytic reduction of NO _x with NH₃ [J]. ACS Applied Materials & Interfaces, 2015, 7(18): 9497-9506.
17	Fabien CAN, BERLAND Sébastien, ROYER Sébastien, et al. Composition-dependent performance of Ce _x Zr_1– _x O₂ mixed-oxide-supported WO₃ catalysts for the NO _x storage reduction-selective catalytic reduction coupled process[J]. ACS Catalysis, 2013, 3(6): 1120-1132.
18	MA Lei, WANG Dingsheng, LI Junhua, et al. Ag/CeO₂ nanospheres: Efficient catalysts for formaldehyde oxidation[J]. Applied Catalysis B: Environmental, 2014, 148/149: 36-43.
19	LIU Zhiming, YI Yang, ZHANG Shaoxuan, et al. Selective catalytic reduction of NO _x with NH₃ over Mn-Ce mixed oxide catalyst at low temperatures[J]. Catalysis Today, 2013, 216: 76-81.
20	DANIEL Marlène, LORIDANT Stéphane. Probing reoxidation sites by in situ Raman spectroscopy: Differences between reduced CeO₂ and Pt/CeO₂ [J]. Journal of Raman Spectroscopy, 2012, 43(9): 1312-1319.
21	SHANG Danhong, CAI Wei, ZHAO Wei, et al. Catalytic oxidation of NO to NO₂ over Co-Ce-Zr solid solutions: Enhanced performance of Ce-Zr solid solution by Co[J]. Catalysis Letters, 2014, 144(3): 538-544.
22	SING K S W. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984)[J]. Pure and Applied Chemistry, 1985, 57(4): 603-619.
23	WU Xiaomin, YU Xiaolong, HUANG Zhiwei, et al. MnOx-decorated VO _x /CeO₂ catalysts with preferentially exposed {110} facets for selective catalytic reduction of NO _x by NH₃ [J]. Applied Catalysis B: Environmental, 2020, 268: 118419.
24	SHEN Boxiong, YAO Yan, CHEN Jianhong, et al. Alkali metal deactivation of Mn-CeO _x /Zr-delaminated-clay for the low-temperature selective catalytic reduction of NO _x with NH₃ [J]. Microporous and Mesoporous Materials, 2013, 180: 262-269.
25	DELIMARIS Dimitrios, IOANNIDES Theophilos. VOC oxidation over MnO _x -CeO₂ catalysts prepared by a combustion method[J]. Applied Catalysis B: Environmental, 2008, 84(1/2): 303-312.
26	LI Hongfeng, LU Guanzhong, DAI Qiguang, et al. Efficient low-temperature catalytic combustion of trichloroethylene over flower-like mesoporous Mn-doped CeO₂ microspheres[J]. Applied Catalysis B: Environmental, 2011, 102(3/4): 475-483.
27	ZHANG Dengsong, ZHANG Lei, SHI Liyi, 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.
28	TAN Hongyi, WANG Jin, YU Shuzhen, et al. Support morphology-dependent catalytic activity of Pd/CeO₂ for formaldehyde oxidation[J]. Environmental Science & Technology, 2015, 49(14): 8675-8682.
29	YOU Xiaochen, SHENG Zhongyi, YU Danqing, et al. Influence of Mn/Ce ratio on the physicochemical properties and catalytic performance of graphene supported MnO _x -CeO₂ oxides for NH₃-SCR at low temperature[J]. Applied Surface Science, 2017, 423: 845-854.
30	PENG Yue, WANG Dong, LI Bing, et al. Impacts of Pb and SO₂ poisoning on CeO₂-WO₃/TiO₂-SiO₂ SCR catalyst[J]. Environmental Science & Technology, 2017, 51(20): 11943-11949.
31	KONG Jiejing, XIANG Ziwei, LI Guiying, et al. Introduce oxygen vacancies into CeO₂ catalyst for enhanced coke resistance during photothermocatalytic oxidation of typical VOCs[J]. Applied Catalysis B: Environmental, 2020, 269: 118755.
32	ZHANG Guodong, HAN Weiliang, DONG Fang, et al. One pot synthesis of a highly efficient mesoporous ceria-titanium catalyst for selective catalytic reduction of NO[J]. RSC Advances, 2016, 6(80): 76556-76567.
33	YU Xiaolong, WU Xiaomin, CHEN Ziyi, et al. Oxygen vacancy defect engineering in Mn-doped CeO₂ nanostructures for nitrogen oxides emission abatement[J]. Molecular Catalysis, 2019, 476: 110512.
34	LI Guangfeng, WANG Qiuyan, ZHAO Bo, et al. Effect of iron doping into CeO₂-ZrO₂ on the properties and catalytic behaviour of Pd-only three-way catalyst for automotive emission control[J]. Journal of Hazardous Materials, 2011, 186(1): 911-920.
35	LIU Xiangwen, ZHOU Kebin, WANG Lei, et al. Oxygen vacancy clusters promoting reducibility and activity of ceria nanorods[J]. Journal of the American Chemical Society, 2009, 131(9): 3140-3141.
36	ZHOU Aiyi, YU Danqing, YANG Liu, et al. Combined effects Na and SO₂ in flue gas on Mn-Ce/TiO₂ catalyst for low temperature selective catalytic reduction of NO by NH₃ simulated by Na₂SO₄ doping[J]. Applied Surface Science, 2016, 378: 167-173.
37	GENUINO Homer C, MENG Yongtao, HORVATH Dayton T, et al. Enhancement of catalytic activities of octahedral molecular sieve manganese oxide for total and preferential CO oxidation through vanadium ion framework substitution[J]. ChemCatChem, 2013, 5(8): 2306-2317.
38	SUN Liang, CAO Qingqing, HU Bingqing, et al. Synthesis, characterization and catalytic activities of vanadium-cryptomelane manganese oxides in low-temperature NO reduction with NH₃ [J]. Applied Catalysis A: General, 2011, 393(1/2): 323-330.
39	DU Haiwei, WANG Yuan, ARANDIYAN Hamidreza, et al. Design and synthesis of CeO₂ nanowire/MnO₂ nanosheet heterogeneous structure for enhanced catalytic properties[J]. Materials Today Communications, 2017, 11: 103-111.
40	TANG Xingfu, LI Yonggang, CHEN Junli, et al. Synthesis, characterization, and catalytic application of titanium-cryptomelane nanorods/fibers[J]. Microporous and Mesoporous Materials, 2007, 103(1/2/3): 250-256.
41	LI Weiman, LIU Haidi, CHEN Yunfa. Promotion of transition metal oxides on the NH₃-SCR performance of ZrO₂-CeO₂ catalyst[J]. Frontiers of Environmental Science & Engineering, 2017, 11(2): 6.
42	ZUO Jianliang, CHEN Zhihang, WANG Furong, et al. Low-temperature selective catalytic reduction of NO _x with NH₃ over novel Mn-Zr mixed oxide catalysts[J]. Industrial & Engineering Chemistry Research, 2014, 53(7): 2647-2655.

催化剂名称	T₅₀/℃	T₉₀/℃	最高NO转化率/%	工作温度窗口/℃
Ce	—	—	35.7	—
Ce_0.9Zr_0.1	—	—	48.3	—
Ce_0.8Zr_0.2	364.3	—	53.4	—
Ce_0.7Zr_0.3	—	—	48.8	—
Mn/Ce	104.0	150.4	98.0	150.4~353.5
Mn/Ce_0.9Zr_0.1	102.7	132.3	99.1	132.3~368.1
Mn/Ce_0.8Zr_0.2	100.2	130.2	100.0	130.2~375.7
Mn/Ce_0.7Zr_0.3	112	141.2	99.8	141.2~377.2

催化剂名称	T₅₀/℃	T₉₀/℃	最高NO转化率/%	工作温度窗口/℃
Ce	—	—	35.7	—
Ce_0.9Zr_0.1	—	—	48.3	—
Ce_0.8Zr_0.2	364.3	—	53.4	—
Ce_0.7Zr_0.3	—	—	48.8	—
Mn/Ce	104.0	150.4	98.0	150.4~353.5
Mn/Ce_0.9Zr_0.1	102.7	132.3	99.1	132.3~368.1
Mn/Ce_0.8Zr_0.2	100.2	130.2	100.0	130.2~375.7
Mn/Ce_0.7Zr_0.3	112	141.2	99.8	141.2~377.2

催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm
Ce	117.6	0.196	3.057
Ce_0.8Zr_0.2	125.7	0.183	3.057
Mn/Ce	106.1	0.192	3.063
Mn/Ce_0.8Zr_0.2	104.7	0.147	3.063

催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm
Ce	117.6	0.196	3.057
Ce_0.8Zr_0.2	125.7	0.183	3.057
Mn/Ce	106.1	0.192	3.063
Mn/Ce_0.8Zr_0.2	104.7	0.147	3.063

催化剂	H_总/mmol·g^-1	H_低温/mmol·g^-1	相对酸性位点总量
Ce	1.202	0.639	4.48
Ce_0.8Zr_0.2	1.447	0.848	4.97
Mn/Ce	1.564	1.095	4.94
Mn/Ce_0.8Zr_0.2	1.776	1.211	5.12

Influence of zirconium modified carriers on the NH₃-SCR performance of manganese-cerium composite catalysts

锆修饰载体对锰铈复合催化剂NH₃-SCR性能的影响

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 13

References 42

Related Articles 15

Recommended Articles

Metrics

Comments

催化剂	Ce³⁺/(Ce³⁺+Ce⁴⁺)	Mn⁴⁺/(Mn³⁺+Mn⁴⁺)	O_A/(O_A+O_L)
Ce	0.179	—	0.225
Ce_0.8Zr_0.2	0.204	—	0.264
Mn/Ce	0.224	0.602	0.167
Mn/ Ce_0.8Zr_0.2	0.184	0.658	0.174

[1]	FU Wei, NING Shuying, CAI Chen, CHEN Jiayin, ZHOU Hao, SU Yaxin. SCR-C₃H₆ denitrification performance of Cu-modified MIL-100(Fe) catalysts [J]. Chemical Industry and Engineering Progress, 2024, 43(9): 4951-4960.
[2]	LONG Tao, ZHOU Feng, ZHANG Wei, WU Hong, WANG Jian, CHEN Lin. Synthesis and modification of deuterated methanol catalyst used in CO-CO₂ system [J]. Chemical Industry and Engineering Progress, 2024, 43(8): 4411-4420.
[3]	ZHOU Hao, WANG Xurui, ZHAO Huishuang, WEN Nini, SU Yaxin. Selective catalytic reduction of nitric oxide with propylene over CuCe-SAPO-34 catalysts under diesel engine exhaust [J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3093-3099.
[4]	LAI Shini, JIANG Lixia, LI Jun, HUANG Hongyu, KOBAYASHI Noriyuki. Research progress of ammonia blended fossil fuel [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4603-4615.
[5]	LI Jia, FAN Xing, CHEN Li, LI Jian. Research progress of simultaneous removal of NO _x and N₂O from the tail gas of nitric acid production [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3770-3779.
[6]	MA Jingwen, NIU Jiayu, LI Xiufen. Promotion technology of aerobic compost ripening [J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2744-2750.
[7]	ZHAO Qiaonan, LIU Xuemin, LIU Feng, XU Hongtao, LIU Zhaohai, LIAO Xiaowei. Numerical on emissions mechanism of nitrogen oxides in gas-fired boilers blended with hydrogen [J]. Chemical Industry and Engineering Progress, 2023, 42(11): 5637-5647.
[8]	YANG Xigang, CHEN Guoqing, HUANG Linbin, GU Shijun, LI Changsong, ZHANG Yong, JIN Baosheng. Industrial experiment on the effect of SNCR using urea as the reducing agent on the operation of large capacity power station pulverized coal boiler [J]. Chemical Industry and Engineering Progress, 2022, 41(7): 3573-3581.
[9]	LONG Hongming, DING Long, QIAN Lixin, CHUN Tiejun, ZHANG Hongliang, YU Zhengwei. Current situation and development trend of NO _x and dioxins emission reduction in sintering flue gas [J]. Chemical Industry and Engineering Progress, 2022, 41(7): 3865-3876.
[10]	HAN Delin, LI Dan, WANG Tiantian, ZHANG Hai, ZHANG Yang, WANG Suilin. Emission characteristics of swirl premixed combustion stabilized using a displacing bluff body [J]. Chemical Industry and Engineering Progress, 2022, 41(6): 2915-2923.
[11]	WANG Xinyu, HUANG Yaji, XU Ligang, LI Zhiyuan, LI Si, LIU Xiaodong. Numerical simulation on regulating secondary air in same layer to alleviate high temperature corrosion of dual tangential boiler [J]. Chemical Industry and Engineering Progress, 2022, 41(5): 2292-2300.
[12]	YANG Jingrui, WANG Ying, CHEN Hu, LYU Yongkang. Effects of O₂ concentration on adjusting NO _x oxidation ratio cooperated with CABR system denitration performance and microbial community structure [J]. Chemical Industry and Engineering Progress, 2022, 41(11): 6139-6148.
[13]	TAN Xiao, QI Suitao, ZHOU Yiming, SHI Libin, CHENG Guangxu, YI Chunhai, YANG Bolun. Direct catalytic reduction of NO by bimetallic ferromanganese catalyst under non-thermal plasma [J]. Chemical Industry and Engineering Progress, 2022, 41(11): 5850-5857.
[14]	YIN Zijun, SU Sheng, WANG Zhonghui, WANG Lele, AN Xiaoxue, ZHAO Zhigang, CHEN Yifeng, LIU Tao, WANG Yi, HU Song, XIANG Jun. Research progress on the characteristics and control methods of SO₃and NH₄HSO₄ formation in coal-fired flue gas [J]. Chemical Industry and Engineering Progress, 2021, 40(4): 2328-2337.
[15]	Yuehua LIU, Ju SHANGGUAN, Shoujun LIU, Song YANG, Wenguang DU. Nitrogen migration regarding the addition of iron-Ni composite additives during coal pyrolysis [J]. Chemical Industry and Engineering Progress, 2021, 40(1): 164-172.