H2O2低温催化氧化法脱硫脱硝中试实验特性

doi:10.16085/j.issn.1000-6613.2023-1289

摘要/Abstract

摘要：

H₂O₂低温催化氧化法脱硫脱硝技术在燃煤电站深度调峰过程中可以应用于低温烟气。本文搭建中试热态实验系统，选取工业蜂窝状TiO₂催化剂，通过X射线衍射（XRD）、X射线荧光光谱（XRF）和扫描电子显微镜（SEM）等对其进行表征，进行脱硫脱硝一体化实验研究，探究各因素对H₂O₂低温催化氧化脱硝效率的影响规律。结果表明：微观下纳米TiO₂颗粒分布均匀、分散性好、纯度高。在单独脱硝实验中，温度对NO氧化和脱除效率影响较小；不采用催化剂时，NO的氧化脱除主要依靠H₂O₂自身的氧化性以及少量H₂O₂分解生成的‧HO₂，效果较差。采用催化剂后，随着H₂O₂/NO摩尔比增加，NO氧化及脱除效率与无催化剂时相比大幅提升。在脱硫脱硝实验中，无催化剂条件下SO₂对NO的氧化和脱除效率有明显促进作用；有催化剂条件下，当H₂O₂/(NO+SO₂)摩尔比为0.5时，NO与SO₂对‧OH的利用存在竞争效应，随着SO₂浓度的增加，NO氧化及脱除效率逐渐提升，SO₂脱除效率逐渐降低。采用蜂窝TiO₂催化剂，当H₂O₂/NO摩尔比为8时，NO氧化效率达90.4%，NO _x 脱除效率达63.7%，SO₂脱除效率可达到100%。

关键词: 氧化, 催化剂, 烟道气, 脱硝, 脱除效率

Abstract:

H₂O₂ low-temperature catalytic oxidative desulfurization and denitrification technology can be applied to low-temperature flue gas in the deep peaking process of coal-fired power stations. In this work, a pilot hot state experimental system was built, industrial honeycomb TiO₂ catalysts were selected with characterizations by XRD, XRF and SEM, and an integrated experimental study of desulfurization and denitrification was carried out to investigate the influence of various factors on the efficiency of low-temperature catalytic oxidative denitrification of H₂O₂. The results showed that the nano-TiO₂ particles were uniformly distributed, well dispersed and highly pure under microscopic conditions. In separate denitrification experiment, temperature had minor effect on the NO oxidation and removal efficiency. When the catalyst was not used, the oxidative removal of NO mainly relied on the oxidizing property of H₂O₂ itself and a small amount of ‧HO₂ generated by the decomposition of H₂O₂, which is less effective. With the increase of H₂O₂/NO molar ratio after the adoption of catalyst, the efficiency of NO oxidation and removal was greatly improved compared with that without catalyst. In the desulfurization and denitrification experiments, the oxidation and removal efficiency of NO was significantly promoted by SO₂ under the uncatalyzed condition. While under the catalyzed condition, there was a competitive effect between NO and SO₂ on the utilization of ‧OH when the molar ratio of H₂O₂/(NO+SO₂) was 0.5, and the oxidation and removal efficiency of NO was gradually enhanced and that of SO₂ was gradually reduced with the increase of SO₂ concentration. With the introduction of honeycomb TiO₂ catalyst, when the H₂O₂/NO molar ratio was 8, the NO oxidation efficiency reached 90.4%, the NO _x removal efficiency reached 63.7%, and the SO₂ removal efficiency could reach 100%.

Key words: oxidation, catalyst, flue gas, denitrification, removal efficiency

中图分类号:

X701

修浩然, 王云刚, 白彦渊, 刘涛, 张兴邦, 张益嘉. H₂O₂低温催化氧化法脱硫脱硝中试实验特性[J]. 化工进展, 2024, 43(9): 4941-4950.

XIU Haoran, WANG Yungang, BAI Yanyuan, LIU Tao, ZHANG Xingbang, ZHANG Yijia. Pilot test of H₂O₂ low temperature catalytic oxidation for desulfurization and denitrification[J]. Chemical Industry and Engineering Progress, 2024, 43(9): 4941-4950.

图/表 16

图1 H2O2催化氧化脱硝中试热态实验系统

图2 蜂窝状催化剂实物

图3 纳米TiO2的XRD谱图

图4 纳米TiO2的SEM及EDS能谱图

表1 纳米TiO2的XRF分析

主要成分	质量分数/%
CaO	0.032
SiO₂	0.039
P₂O₅	0.044
TiO₂	98.90

图5 NO氧化及脱除效率与H2O2/NO摩尔比之间的关系

图6 无催化剂下NO初始物质的量浓度对NO氧化及脱除效率的影响

图7 H2O2不同喷入位置及其对NO氧化及脱除效率的影响

图8 无催化剂下烟气温度对NO氧化及脱除效率的影响

图9 SO2对脱硫脱硝效率的影响

图10 H2O2质量分数对NO氧化及脱除效率的影响

图11 NO氧化及脱除效率随H2O2/NO摩尔比的变化曲线

图12 烟气温度对NO氧化及脱除效率的影响

图13 NO初始物质的量浓度对NO氧化及脱除效率的影响

图14 空速比对NO氧化及脱除效率的影响

图15 SO2物质的量浓度对脱硫脱硝效率的影响

参考文献 32

1	KRISHNA K, MAKKEE M. Coke formation over zeolites and CeO₂-z eolites and its influence on selective catalytic reduction of NO _x [J]. Applied Catalysis B: Environmental, 2005, 59(1/2): 35-44.
2	WU Zhongbiao, JIANG Boqiong, LIU Yue. Effect of transition metals addition on the catalyst of manganese/titania for low-temperature selective catalytic reduction of nitric oxide with ammonia[J]. Applied Catalysis B: Environmental, 2008, 79(4): 347-355.
3	顾甜, 高凤雨, 唐晓龙, 等. 炭基材料负载型低温NH₃-SCR脱硝催化剂的研究进展[J]. 化工进展, 2019, 38(5): 2329-2338.
	GU Tian, GAO Fengyu, TANG Xiaolong, et al. Research progress on carbon-based material supported catalysts for the selective catalytic reduction of NO _x by NH₃ at low temperature[J]. Chemical Industry and Engineering Progress, 2019, 38(5): 2329-2338.
4	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.
5	樊庆锌, 王明轩, 关心, 等. 某燃煤电厂300MW机组SCR烟气脱硝装置结构优化[J]. 化工进展, 2014, 33(10): 2806-2814.
	FAN Qingxin, WANG Mingxuan, GUAN Xin, et al. Optimal design of a SCR-DeNO _x system for a 300MW coal-fired power plant[J]. Chemical Industry and Engineering Progress, 2014, 33(10): 2806-2814.
6	LIU Yangxian, ADEWUYI Yusuf G. A review on removal of elemental mercury from flue gas using advanced oxidation process: Chemistry and process[J]. Chemical Engineering Research and Design, 2016, 112: 199-250.
7	杨加强, 梅毅, 王驰, 等. 湿法烟气脱硝技术现状及发展[J]. 化工进展, 2017, 36(2): 695-704.
	YANG Jiaqiang, MEI Yi, WANG Chi, et al. Current status and trends on wet flue gas denitration technology[J]. Chemical Industry and Engineering Progress, 2017, 36(2): 695-704.
8	CHEN Luke, HSU Chung-Hao, YANG Chenlu. Oxidation and absorption of nitric oxide in a packed tower with sodium hypochlorite aqueous solutions[J]. Environmental Progress, 2005, 24(3): 279-288.
9	CHU H, LI S Y, CHIEN T W. The absorption kinetics of no from flue gas in a stirred tank reactor with KMnO₄/NaOH solutions[J]. Journal of Environmental Science and Health, Part A, 1998, 33(5): 801-827.
10	JAKUBIAK Maciej P, KORDYLEWSKI. Pilot-scale studies on NO _x removal from flue gas via NO ozonation and absorption into NaOH solution[J]. Chemical and Process Engineering, 2012, 33(3): 345-358.
11	丁杰. H₂O₂/O₃催化分解及其氧化烟气脱硝研究[D]. 南京: 南京理工大学, 2017.
	DING Jie. Reserches on catalytic decomposition of H₂O₂/O₃ and oxidation of flue gas denitration[D]. Nanjing: Nanjing University of Science and Technology, 2017.
12	张杰, 邓云波. NaClO氧化法脱硝及与NaOH同时脱硫脱硝技术研究[J]. 节能与环保, 2020(11): 72-73.
	ZHANG Jie, DENG Yunbo. Study on NaClO xidative denitration and simultaneous desulfurization and denitration with NaOH[J]. Energy Conservation & Environmental Protection, 2020(11): 72-73.
13	DE PAIVA J L, KACHAN G C. Modeling and simulation of a packed column for NO _x absorption with hydrogen peroxide[J]. Industrial & Engineering Chemistry Research, 1998, 37(2): 609-614.
14	苑鹏, 卢凤菊, 梅雪, 等. 高级氧化法在烟气脱硫脱硝脱汞中的应用研究进展[J]. 化工进展, 2016, 35(10): 3313-3322.
	YUAN Peng, LU Fengju, MEI Xue, et al. Recent progress on application of advanced oxidation processes (AOPs) to remove SO₂, NO _x and Hg⁰ from flue gas[J]. Chemical Industry and Engineering Progress, 2016, 35(10): 3313-3322.
15	朱贤. 过氧化氢水溶液强化吸收SO₂/NO _x 及其反应动力学的实验研究[D]. 上海: 上海交通大学, 2010.
	ZHU Xian. Experimental and kinetic study on the enhanced absorption of SO₂/NO _x into aqueous solution containing hydrogen peroxide[D]. Shanghai: Shanghai Jiao Tong University, 2010.
16	BAVEJA K K, RAO D Subba, SARKAR M K. Kinetics of absorption of nitric oxide in hydrogen peroxide solutions[J]. Journal of Chemical Engineering of Japan, 1979, 12(4): 322-325.
17	HAYWOOD J M, COOPER C D. The economic feasibility of using hydrogen peroxide for the enhanced oxidation and removal of nitrogen oxides from coal-fired power plant flue gases[J]. Journal of the Air & Waste Management Association, 1998, 48(3): 238-246.
18	CHEN Lei, XU Zhiwen, HE Chi, et al. Gas-phase total oxidation of nitric oxide using hydrogen peroxide vapor over Pt/TiO₂ [J]. Applied Surface Science, 2018, 457: 821-830.
19	柏源, 李忠华, 薛建明, 等. 燃煤烟气H₂O₂脱硝性能影响因素的实验研究[J]. 化工进展, 2012, 31(1): 208-212.
	BAI Yuan, LI Zhonghua, XUE Jianming, et al. Experimental study on affecting factors for the performance of denitrification using H₂O₂ solution in coal-fired flue gas[J]. Chemical Industry and Engineering Progress, 2012, 31(1): 208-212.
20	马双忱, 马京香, 赵毅, 等. 采用UV/H₂O₂体系进行烟气脱硫脱硝的实验研究[J]. 中国电机工程学报, 2009, 29(5): 27-31.
	MA Shuangchen, MA Jingxiang, ZHAO Yi, et al. Experimental study on desulfurization and denitrification using UV/H₂O₂ system[J]. Proceedings of the CSEE, 2009, 29(5): 27-31.
21	LIU Yangxian, ZHANG Jun, SHENG Changdong, et al. Simultaneous removal of NO and SO₂ from coal-fired flue gas by UV/H₂O₂ advanced oxidation process[J]. Chemical Engineering Journal, 2010, 162(3): 1006-1011.
22	MA Jinzhu, HE Hong, LIU Fudong. Effect of Fe on the photocatalytic removal of NO _x over visible light responsive Fe/TiO₂ catalysts[J]. Applied Catalysis B: Environmental, 2015(179) 21-28.
23	王琦. 基于TiO₂改性催化剂催化H₂O₂氧化低温脱硝的实验研究[D]. 北京: 华北电力大学, 2018.
	WANG Qi. Experimental study on low temperature H₂O₂-based oxidized denitration catalyzed by TiO₂ modified catalyst[D]. Beijing: North China Electric Power University, 2018.
24	茹晋波. 基于H₂O₂催化预氧化NO的湿法烟气同时脱硫脱硝特性研究[D]. 南京: 东南大学, 2017.
	RU Jinbo. Simultaneous desulfurization and denitrification from flue gas by catalytic preoxidation of NO with H₂O₂ [D]. Nanjing: Southeast University, 2017.
25	JIA Shuaihui, PU Ge, XIONG Weicheng, et al. Investigation on simultaneous removal of SO₂ and NO over a Cu-Fe/TiO₂ catalyst using vaporized H₂O₂: An analysis on SO₂ effect[J]. Industrial & Engineering Chemistry Research, 2021, 60(37): 13474-13484.
26	MENG Fanyu, ZHANG Shule, ZHANG Mingjia, et al. The mechanism of Ce-MCM-41 catalyzed peroxone reaction into ·OH and ·O 2 - radicals for enhanced NO oxidation[J]. Molecular Catalysis, 2022, 518: 112110.
27	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.
28	涂汉超. 含氮生物质气化气燃烧的NO _x 排放特性研究[D]. 杭州: 浙江大学, 2018.
	TU Hanchao. Study on NO _x emission characteristics of biomass gasification gas combustion with nitrogenous compounds[D]. Hangzhou: Zhejiang University, 2018.
29	吕博, 涂淑平, 孙文哲, 等. H₂O₂低温脱硫脱硝研究及应用进展[J]. 应用化工, 2020, 49(10): 2654-2656, 2661.
	Bo LYU, TU Shuping, SUN Wenzhe, et al. Research and application progress of H₂O₂ low temperature desulfurization and denitrification[J]. Applied Chemical Industry, 2020, 49(10): 2654-2656, 2661.
30	QI Yongfeng, GE Panle, WANG Meiting, et al. Experimental investigation and numerical simulation of simultaneous desulfurization and denitrification by H₂O₂ solution assisted with microwave and additive[J]. Chemical Engineering Journal, 2020, 391: 123559.
31	YANG Bingchuan, MA Suxia, CUI Rongji, et al. Novel low-cost simultaneous removal of NO and SO₂ with ·OH from decomposition of H₂O₂ catalyzed by alkali-magnetic modified fly ash[J]. Industrial & Engineering Chemistry Research, 2019, 58(13): 5339-5347.
32	MATTHEWS Ralph W. Hydroxylation reactions induced by near-ultraviolet photolysis of aqueous titanium dioxide suspensions[J]. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 1984, 80(2): 457.

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H₂O₂低温催化氧化法脱硫脱硝中试实验特性

Pilot test of H₂O₂ low temperature catalytic oxidation for desulfurization and denitrification

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