二乙烯三胺五亚甲基膦酸/Fenton体系氧化脱除NO

doi:10.16085/j.issn.1000-6613.2022-1970

摘要/Abstract

摘要：

针对当前Fenton氧化法脱除燃煤烟气中 NO的过程中H₂O₂大量无效分解生成氧气的缺点，本文采用二乙烯三胺五亚甲基膦酸（DTPMPA）/Fenton系统进行氧化脱除NO的实验研究。结果表明：该系统在NO脱除效率为95.1%的情况下，H₂O₂无效分解占比降低至15.5%。DTPMPA浓度的增加抑制了H₂O₂无效分解，其浓度较低时促进NO脱除而浓度较高时抑制NO脱除；H₂O₂及Fe²⁺浓度的增加均对NO脱除及H₂O₂无效分解有一定的促进作用，但二者浓度过高时亦均对脱除NO有一定抑制作用；降低反应温度对NO脱除影响较小，但会削弱H₂O₂无效分解；SO₂对NO的脱除及H₂O₂无效分解影响甚小。电子自旋共振技术和淬灭剂添加实验结果表明：DTPMPA的添加提高了Fenton系统中·OH自由基和·O $2 -$ 自由基的含量，且·O $2 -$ 自由基为脱除NO的主要活性物质，·O $2 -$ + HO· $→$ O₂ + HO^-为氧气生成的主要途径。反应产物离子色谱表明：NO在反应过程中被氧化为NO $2 -$ 和NO $3 -$ 。

关键词: 芬顿法, 二乙烯三胺五亚甲基膦酸, 自由基, 脱硝, 无效分解

Abstract:

In view of the current Fenton oxidation method to remove NO in coal-fired flue gas, a large amount of H₂O₂ ineffectively decomposes to generate oxygen, the DTPMPA (diethylenetriamine pentamethylphosphonic acid) /Fenton system was used to oxidize and remove NO. The results showed that when NO removal efficiency of the system was 95.1%, the proportion of H₂O₂ ineffective decomposition decreased to 15.5%. The increase of DTPMPA concentration inhibited H₂O₂ineffective decomposition, and it promoted NO removal when the concentration was low but inhibited NO removal when the concentration was high. The increase of H₂O₂ and Fe²⁺ concentrations had a certain promoting effect on NO removal and H₂O₂ ineffective decomposition, but when the concentration of both was too high, it also had a certain inhibitory effect on NO removal. Lower reaction temperature had little effect on NO removal, but weakened H₂O₂ ineffective decomposition. SO₂ had little effect on NO removal and H₂O₂ ineffective decomposition. Electron spin resonance technology and quenching addition experiments showed that the addition of DTPMPA increased the content of ·OH radicals and ·O₂^- radicals in the Fenton system, ·O $2 -$ radicals were the main active species for NO removal, and the main pathway of oxygen generation was ·O $2 -$ + HO· $→$ O₂ + HO^-. Ion chromatography of the reaction products showed that NO was oxidized to NO $2 -$ and NO $3 -$ during the reaction.

Key words: Fenton, diethylenetriamine pentamethylphosphonic acid, radical, denitration, ineffective decomposition

中图分类号:

X701

白志华, 张军. 二乙烯三胺五亚甲基膦酸/Fenton体系氧化脱除NO[J]. 化工进展, 2023, 42(9): 4967-4973.

BAI Zhihua, ZHANG Jun. Oxidative removal of NO in DTPMPA/Fenton system[J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4967-4973.

图/表 12

图1 实验系统装置示意图1—N2钢瓶；2—NO钢瓶；3—SO2钢瓶；4，5，6—减压阀；7，8，9—质量流量计；10—烟气混合罐；11，12—阀门；13—鼓泡反应器；14—恒温水浴锅；15—气体干燥瓶；16—烟气分析仪；17—尾气吸收瓶

图2 DTPMPA浓度对NO脱除效率及H2O2无效分解占比的影响（H2O2浓度1mol/L，Fe2+浓度0.005mol/L，反应温度50℃）

图3 H2O2浓度对NO脱除效率及H2O2无效分解占比的影响（Fe2+浓度0.005mol/L，DTPMPA浓度0.014mol/L，反应温度50℃）

图4 Fe2+浓度对NO脱除效率及H2O2无效分解占比的影响（H2O2浓度1mol/L，DTPMPA浓度0.014mol/L，反应温度50℃）

图5 反应温度对NO脱除效率及H2O2无效分解占比的影响（H2O2浓度1mol/L，Fe2+浓度0.005mol/L，DTPMPA浓度0.014mol/L）

图6 SO2对NO脱除效率及H2O2无效分解占比的影响（H2O2浓度1mol/L，Fe2+浓度0.005mol/L，DTPMPA浓度0.014mol/L，反应温度50℃）

图7 ·OH自由基ESR检测图

图8 ·O2-自由基ESR检测图

图9 不同系统添加自由基淬灭剂前后的NO脱除效率（H2O2浓度1mol/L，Fe2+浓度0.005mol/L，DTPMPA浓度0.014mol/L，反应温度50℃）

图10 不同系统添加·OH自由基淬灭剂前后的H2O2无效分解占比（H2O2浓度1mol/L，Fe2+浓度0.005mol/L，DTPMPA浓度0.014mol/L，反应温度50℃）

表1 NO3-及NO2-浓度

序号	峰名称	样品量/mg·L^-1
1	NO $2 -$	1.1351
2	NO $3 -$	4.7087

表1 NO3-及NO2-浓度

序号	峰名称	样品量/mg·L^-1
1	NO $2 -$	1.1351
2	NO $3 -$	4.7087

图11 反应产物离子色谱

参考文献 20

1	刘福玉. 新能源电力系统中需求侧响应的关键性问题探讨[J]. 电子测试, 2017(9): 107-108.
	LIU Fuyu. Discussion on key issues of demand side response in new energy power system[J]. Electronic Test, 2017(9): 107-108.
2	张晓波, 郭瑞堂, 潘卫国, 等. NaClO₂/氨水溶液同时脱除SO₂和NO的热力学研究[J]. 电力科技与环保, 2010, 26(4): 15-17.
	ZHANG Xiaobo, GUO Ruitang, PAN Weiguo, et al. Thermodynamic study of NaClO₂/ammonia solution simultaneous removal of SO₂ and NO[J]. Electric Power Technology and Environmental Protection, 2010, 26(4): 15-17.
3	WANG Han, YUAN Bo, HAO Runlong, et al. A critical review on the method of simultaneous removal of multi-air-pollutant in flue gas[J]. Chemical Engineering Journal, 2019, 378: 122155.
4	LIU Yangxian, PAN Jianfeng, DU Min, et al. Advanced oxidative removal of nitric oxide from flue gas by homogeneous photo-Fenton in a photochemical reactor[J]. Chemical Engineering & Technology, 2013, 36(5): 781-787.
5	DING Jie, ZHONG Qin, ZHANG Shule, et al. Simultaneous removal of NO _x and SO₂ from coal-fired flue gas by catalytic oxidation-removal process with H₂O₂ [J]. Chemical Engineering Journal, 2014, 243: 176-182.
6	ZHAO Yi, HAO Runlong, GUO Qing, et al. Simultaneous removal of SO₂ and NO by a vaporized enhanced-Fenton reagent[J]. Fuel Processing Technology, 2015, 137: 8-15.
7	YUAN Peng, EGEDY Attila, Norbert MISKOlCZI, et al. Oxidation removal of NO by in situ Fenton system: Factors and optimization[J]. Fuel, 2018, 233: 519-528.
8	LIU Xuan, WANG Changan, ZHU Tao, et al. Simultaneous removal of NO _x and SO₂ from coal-fired flue gas based on the catalytic decomposition of H₂O₂ over Fe₂(MoO₄)₃ [J]. Chemical Engineering Journal, 2019, 371: 486-499.
9	王凤春, 杨宝玉, 刘敏芹. 影响螯合剂螯合效率的因素[J]. 纸和造纸, 1997(3): 11.
	WANG Fengchun, YANG Baoyu, LIU Minqin. Factors influencing chelating efficiency of chelating agents[J]. Paper and Paper Making, 1997(3): 11.
10	钱学仁, 安显慧, 刘文波, 等. 亚甲基膦酸用作纸浆H₂O₂漂白螯合剂的研究[J]. 中国造纸, 2003, 22(5): 8-11.
	QIAN Xueren, AN Xianhui, LIU Wenbo, et al. Methylenephosphonic acids as the chelants of hydrogen peroxide bleaching [J]. China Pulp & Paper, 2003, 22(5): 8-11.
11	ZHAO Haiqian, DONG Ming, WANG Zhonghua, et al. Roles of free radicals in NO oxidation by Fenton system and the enhancement on NO oxidation and H₂O₂ utilization efficiency[J]. Environmental Technology, 2020, 41(1): 109-116.
12	SUN Shujun, ZHANG Jun, SHENG Changdong, et al. The removal of NO from flue gas by NaOH-catalyzed H₂O₂ system: Mechanism exploration and primary experiment[J]. Journal of Hazardous Materials, 2022, 440: 129788.
13	于冬梅, 陈克复, 赵传山, 等. 重金属离子在碱性H₂O₂溶液中的存在形态及其对H₂O₂的催化分解作用[J]. 中国造纸学报, 2006, 21(2): 78-81.
	YU Dongmei, CHEN Kefu, ZHAO Chuanshan, et al. State of metal in alkaline peroxide solution and its influence on the decomposition of peroxide[J]. Transactions of China Pulp and Paper, 2006, 21(2): 78-81.
14	温学友, 赵毅, 苗志加. Fenton氧化法进行烟气同时脱硫脱硝试验研究及热力学分析[J]. 河南理工大学学报, 2018, 37(4): 68-75.
	WEN Xueyou, ZHAO Yi, MIAO Zhijia. Experimental and thermodynamic analysis on simultaneous desulfurization and denitration of flue gas by Fenton oxidation[J]. Journal of Henan Polytechnic University, 2018, 37(4): 68-75.
15	SUN Shujun, MA Suxia, YANG Bingchuan, et al. NO removal from flue gas by using chlorine dioxide solution[J]. Energy & Fuels, 2019, 33(10): 10004-10010.
16	孙淑君, 张军, 钟辉. Na₂SiO₃/Fenton体系氧化脱除NO的实验研究[J]. 华中科技大学学报, 2022, 50(7): 130-135.
	SUN Shujun, ZHANG Jun, ZHONG Hui. Experimental research on the removal of NO by NO in Na₂SiO₃/Fenton system[J]. Journal of Huazhong University of Science and Technology, 2022, 50(7): 130-135.
17	郭丽娜. 铁基与铈基催化剂的制备及其催化臭氧氧化NO _x 的性能研究[D]. 南京: 南京理工大学, 2018.
	GUO Lina. Study on preparation and performance of ferrum base and ceria base catalysts for the oxidation of NO _x by catalytic ozonation[D]. Nanjing: Nanjing University of Science and Technology, 2018.
18	杨秉川. 碱-磁改性飞灰催化过氧化氢协同脱硫脱硝[D]. 太原: 太原理工大学, 2019.
	YANG Bingchuan. Simultaneous removal NO _x and SO₂ with H₂O₂ catalyzed by alkali-magnetic modified fly ash[D]. Taiyuan: Taiyuan University of Technology, 2019.
19	姜招峰, 郑荧光, 杨翰仪. DMPO与O 2 - ·的自旋加合物的ESR谱分析[J]. 青岛海洋大学学报, 1998, 28(1): 43-47.
	JIANG Zhaofeng, ZHENG Yingguang, YANG Hanyi. ESR spectra of superoxide anion spin adduct of DMPO[J]. Journal of Ocean University of Qingdao, 1998, 28(1): 43-47.
20	NIE Zhou, TIAN Qiu, LIU Yangping, et al. Superoxide anion radical generation in the NaOH/H₂O₂/Fe(Ⅲ) system: A spin trapping ESR study[J]. Magnetic Resonance Chemistry, 2006, 44(1): 38-44.

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