钇掺杂三氧化二铁催化剂的脱硝性能研究

doi:10.19964/j.issn.1006-4990.2022-0090

摘要/Abstract

摘要：

为提升三氧化二铁（Fe₂O₃）催化剂的脱硝性能，扩展催化剂的活性温度窗口，采用共沉淀法引入助剂钇（Y）元素对Fe₂O₃催化剂进行改性。通过X射线衍射（XRD）、氮气等温吸-脱附（N₂-BET）、X射线光电子能谱（XPS）、氨气程序升温脱附（NH₃-TPD）、氢气程序升温还原（H₂-TPR）等表征方法对样品进行了表征分析。XRD和N₂-BET结果表明，Y的掺杂使催化剂结构发生变化，比表面积增加、孔径减小。XPS和NH₃-TPD结果证明，Y掺杂Fe₂O₃具有更多的表面吸附氧（O_Ⅰ）、Fe²⁺以及更多的酸量。H₂-TPR结果表明，Y的掺杂使催化剂的氧化还原能力略有下降。测试了不同含量Y掺杂的Fe₂O₃催化剂在150~400 ℃的脱硝性能，其中Fe₉Y₁O _x 催化剂的脱硝活性最佳，在300 ℃达到81.8%。

关键词: 钇, 脱硝催化剂, 三氧化二铁

Abstract:

In order to improve the denitration performance of Fe₂O₃ catalyst and expand the active temperature window of the catalyst，the co-precipitation method was used to introduce the promoter Y to modify the Fe₂O₃ catalyst.The samples were characterized by X-ray diffraction（XRD），N₂ isothermal adsorption desorption（N₂-BET），X-ray photoelectron spectroscopy（XPS），NH₃ temperature programmed desorption（NH₃-TPD） and H₂ temperature programmed reduction（H₂-TPR）.The XRD and N₂-BET results showed that doping of Y changed the catalyst structure，increased the specific surface area and reduced pore size of the catalyst.The XPS and NH₃-TPD demonstrated that Y-doped Fe₂O₃had more surface adsorbed oxygen（O_I），Fe²⁺ and more acid amount.The H₂-TPR results showed that Y doping slightly reduced the redox ability of the catalyst.The denitration performance of Fe₂O₃ catalysts doped with different contents of Y at 150~400 ℃ was tested.Fe₉Y₁O _x catalyst had the best denitration activity，reaching 81.8% at 300 °C.

Key words: yttrium, denitration catalyst, Fe₂O₃

中图分类号:

O643.3

杜沛佞,罗仕忠,谭仁俊,敬方梨. 钇掺杂三氧化二铁催化剂的脱硝性能研究[J]. 无机盐工业, 2022, 54(11): 137-142.

DU Peining,LUO Shizhong,Tan Renjun,JING Fangli. Study on denitration performance of Y doped Fe₂O₃ catalyst[J]. Inorganic Chemicals Industry, 2022, 54(11): 137-142.

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参考文献 19

1	LIU Fudong, SHAN Wenpo, LIAN Zhihua, et al.The smart surface modification of Fe₂O₃ by WO _x for significantly promoting the selective catalytic reduction of NO _x with NH₃ [J].Applied Catalysis B：Environmental,2018,230: 165-176.
2	JIANG Haoxi, ZHANG Lu, ZHAO Jing, et al.Study on MnO _x -FeO _y composite oxide catalysts prepared by supercritical antisolvent process for low-temperature selective catalytic reduction of NO _x [J].Journal of Materials Research,2016,31(6):702-712.
3	XIONG Zhibo, HU Qiang, LIU Dunyu, et al.Influence of partial substitution of iron oxide by titanium oxide on the structure and activity of iron-cerium mixed oxide catalyst for selective catalytic reduction of NO _x with NH₃ [J].Fuel,2016,165: 432-439.
4	GUO Kai, JI Jiawei, OSUGA R, et al.Construction of Fe₂O₃ loaded and mesopore confined thin-layer titania catalyst for efficient NH₃-SCR of NO _x with enhanced H₂O/SO₂ tolerance[J].Applied Catalysis B：Environmental,2021,287.Doi:10.1016/j.apcatb.2021.119982. doi: 10.1016/j.apcatb.2021.119982
5	LI Xiang, LI Junhua, PENG Yue, et al.Selective catalytic reduction of NO with NH₃ over novel iron-tungsten mixed oxide catalyst in a broad temperature range[J].Catalysis Science & Technology,2015,5(9):4556-4564.
6	LIU Fudong, HE Hong, ZHANG Changbin, et al.Selective catalytic reduction of NO with NH₃ over iron titanate catalyst：Catalytic performance and characterization[J].Applied Catalysis B：Environmental,2010,96(3/4):408-420.
7	XIONG Zhibo, LU Chunmei, GUO Dongxu, et al.Selective catalytic reduction of NO _x with NH₃ over iron-cerium mixed oxide catalyst：Catalytic performance and characterization[J].Journal of Chemical Technology & Biotechnology,2013,88(7):1258-1265.
8	QU Weiye, CHEN Yaxin, HUANG Zhiwei, et al.Active tetrahedral iron sites of γ-Fe₂O₃ catalyzing NO reduction by NH₃ [J].Environmental Science & Technology Letters,2017,4(6):246-250.
9	WU Jiahui, JIN Shuangling, WEI Xudong, et al.Enhanced sulfur resistance of H₃PW₁₂O₄₀-modified Fe₂O₃ catalyst for NH₃-SCR：Synergistic effect of surface acidity and oxidation ability[J].Chemical Engineering Journal,2021,412.Doi:10.1016/j.cej.2021.128712. doi: 10.1016/j.cej.2021.128712
10	WANG Huimin, NING Ping, ZHANG Yaqing, et al.Highly efficient WO₃-FeO _x catalysts synthesized using a novel solvent-free method for NH₃-SCR[J].Journal of Hazardous Materials,2020,388.Doi:10.1016/j.jhazmat.2019.121812. doi: 10.1016/j.jhazmat.2019.121812
11	XIE Shangzhi, LI Lulu, JIN Lijian, et al.Low temperature high activity of M（M=Ce，Fe，Co，Ni） doped M-Mn/TiO₂ catalysts for NH₃-SCR and in situ DRIFTS for investigating the reaction mechanism[J].Applied Surface Science,2020,515.Doi:10.1016/j.apsusc.2020.146014. doi: 10.1016/j.apsusc.2020.146014
12	WU Xu, WANG Ruonan, DU Yali, et al.Performance enhancement of NH₃-SCR via employing hydrotalcite-like precursor to induce the decoration of NiO by TiO₂ phase[J].Molecular Catalysis,2019,467: 150-160.
13	SUN Peng, HUANG Shuxian, GUO Ruitang, et al.The enhanced SCR performance and SO₂ resistance of Mn/TiO₂ catalyst by the modification with Nb：A mechanistic study[J].Applied Surface Science,2018,447: 479-488.
14	ZHANG Kai, WANG Jingjing, GUAN Pufang, et al.Low-temperature NH₃-SCR catalytic characteristic of Ce-Fe solid solutions based on rare earth concentrate[J].Materials Research Bulletin,2020,128.Doi:10.1016/j.materresbull.2020.110871. doi: 10.1016/j.materresbull.2020.110871
15	SUN Chuanzhi, CHEN Wei, JIA Xuanxuan, et al.Comprehensive understanding of the superior performance of Sm-modified Fe₂O₃ catalysts with regard to NO conversion and H₂O/SO₂ resistance in the NH₃-SCR reaction[J].Chinese Journal of Catalysis,2021,42(3):417-430.
16	LIU Zhiming, SU Hang, CHEN Biaohua, et al.Activity enhancement of WO₃ modified Fe₂O₃ catalyst for the selective catalytic reduction of NO _x by NH₃ [J].Chemical Engineering Journal,2016,299: 255-262.
17	REN Zhaoyong, TENG Yunfei, ZHAO Leyu, et al.Keggin-tungstophosphoric acid decorated Fe₂O₃ nanoring as a new catalyst for selective catalytic reduction of NO _x with ammonia[J].Catalysis Today,2017,297: 36-45.
18	YANG Jie, REN Shan, ZHANG Tianshi, et al.Iron doped effects on active sites formation over activated carbon supported Mn-Ce oxide catalysts for low-temperature SCR of NO[J].Chemical Engineering Journal,2020,379.Doi:10.1016/j.cej.2019.122398. doi: 10.1016/j.cej.2019.122398
19	CHOU Chenyu, LOBO R F.Direct conversion of CO₂ into methanol over promoted indium oxide-based catalysts[J].Applied Catalysis A：General,2019,583.Doi:10.1016/j.apcata.2019.117144. doi: 10.1016/j.apcata.2019.117144

样品	BET比表面积/ （m²·g^-1）	孔容/ （cm³·g^-1）	平均孔径/ nm
Fe₂O₃	18.4	0.12	26.3
Y₁Fe₁₅O _x	49.9	0.15	12.1
Y₁Fe₉O _x	115.4	0.14	4.8
Y₁Fe₅O _x	110.0	0.13	4.8

样品	NH₃含量/（mmol·g^-1）
样品	Peak1	Peak2	Peak3	总含量
Fe₂O₃	0.008	0.008	0.008	0.024
Y₁Fe₁₅O _x	0.020	0.047	—	0.067
Y₁Fe₉O _x	0.023	0.100	—	0.123
Y₁Fe₅O _x	0.025	0.090	—	0.115

样品	n（O_Ⅰ）/n（O_Ⅱ）/n（O_Ⅲ）	n（Fe²⁺）/n（Fe³⁺）
Fe₂O₃	14.0/78.5/7.6	58.0/42
Y₁Fe₁₅O _x	24.4/66.9/8.7	56.0/44
Y₁Fe₉O _x	30.2/63.6/6.2	62.8/37.2
Y₁Fe₅O _x	27.1/65/7.9	50.6/49.4

样品	H₂ 消耗量/（mmol·g^-1）			总量/ （mmol·g^-1）
样品	100~510 ℃	510~680 ℃	680~800 ℃	总量/ （mmol·g^-1）
Fe₂O₃	2.9	13.4	5.2	21.5
Y₁Fe₁₅O _x	9.5	7.8	2.3	19.6
Y₁Fe₉O _x	5.9	4.7	5.1	15.7
Y₁Fe₅O _x	3.5	6.6	1.0	11.1

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