基于α-FeOOH催化H2O2蒸气的低温烟气脱硝实验

doi:10.16085/j.issn.1000-6613.2019-0630

摘要/Abstract

摘要：

针铁矿是分布广泛、储量丰富的铁氧化物，其主要成分为α-羟基氧化铁（α-FeOOH）。为了探究针铁矿在催化H₂O₂烟气脱硝反应中的性能，本文通过沉淀-水解法制备了α-FeOOH，并在自行搭建的实验台上开展了α-FeOOH催化H₂O₂的低温烟气脱硝实验研究，深入分析了H₂O₂流量、H₂O₂浓度、汽化温度、反应温度和共存气体浓度等工况参数对脱硝性能的影响。采用离子色谱（IC）分析了单独脱硝反应和同时脱硫脱硝反应后的含氧酸成分，结合各项表征分析技术考察了催化剂反应前后的理化特性和稳定性。实验结果显示，随着汽化温度和反应温度的升高，NO的脱除效率先增加后降低；增加H₂O₂浓度对脱硝效率有明显的促进作用。当汽化温度为140℃、反应温度为160℃时，以2.5mL/h注入10mol/L的H₂O₂脱硝效率达到80%。当SO₂浓度为1000μL/L时，脱硝效率提高至86.4%。离子色谱分析结果显示，单独脱硝反应和同时脱硫脱硝反应后含氧酸产物为HNO₃和H₂SO₄。反应前后催化剂的表征结果显示，α-FeOOH在脱硝反应后依然具有良好的稳定性，显示出针铁矿在低温烟气脱硝工艺中的潜在应用前景。

关键词: 催化剂, 汽化, 自由基, 低温烟气脱硝, 脱硝效率

Abstract:

Goethite is an abundantly and widely distributed iron oxide with α-FeOOH as the main component. To investigate the performance of goethite in catalytic denitration of flue gas by H₂O₂, α-FeOOH catalyst was prepared by precipitation-hydrolysis method and then used in the bench scale denitration experiments. The effects of H₂O₂ flow rate, H₂O₂ concentration, vaporization temperature, reaction temperature and coexisting gas concentration on the denitrification performance were analyzed. Ion chromatography (IC) was used to analyze the oxyacid components after denitrification and those after simultaneous desulfurization and denitrification. Various characterization techniques were also used to examine the physicochemical properties and stability of the catalyst before and after the reaction. The results showed that with the increase of vaporization temperature and reaction temperature, the removal efficiency of NO increased firstly and then decreased, and the increase of H₂O₂ concentration had significantly enhanced the denitration efficiency. When the vaporization and reaction temperatures were 140℃ and 160℃ respectively, the denitration efficiency reached 80% by injecting 10mol/L H₂O₂ at a flow rate of 2.5mL/h. When the SO₂ concentration was 1000μL/L, the denitration efficiency increased to 86.4%. The ion chromatography analysis showed that the oxyacid products were HNO₃ and H₂SO₄ after denitration and desulfurization. The characterization results of the catalysts showed that the α-FeOOH still had excellent stability after denitration reaction, which illustrated the potential application prospect of the goethite in low temperature flue gas denitration process.

Key words: catalyst, vapor, radical, low temperature flue gas denitration, denitration efficiency

中图分类号:

X511

何珊珊,熊源泉,杨思源,盖洋洋. 基于α-FeOOH催化H₂O₂蒸气的低温烟气脱硝实验[J]. 化工进展, 2020, 39(3): 1012-1020.

Shanshan HE,Yuanquan XIONG,Siyuan YANG,Yangyang GAI. Low-temperature flue gas denitration by H₂O₂ vapor over α-FeOOH[J]. Chemical Industry and Engineering Progress, 2020, 39(3): 1012-1020.

图/表 14

图1 氧化实验装置图1—质量流量计；2—混气罐；3—三通阀；4—烟气预热器；5—温控单元；6—注射泵；7—催化反应器；8—撞击式吸收器（置于冰水浴中）；9—冷凝管；10—干燥器（含干燥剂无水氯化钙）；11—烟气分析仪；12—KMnO4/NaOH溶液；13—活性炭

图2 H2O2流量对于脱硝效率的影响（H2O2浓度10mol/L；汽化温度140℃；反应温度140℃）

图3 H2O2浓度对于脱硝效率的影响（H2O2流量2.5mL/h；汽化温度140℃；反应温度140℃）

图4 汽化温度对于脱硝效率的影响（H2O2流量2.5mL/h；H2O2浓度10mol/L；反应温度140℃）

图5 反应温度对于脱硝效率的影响（H2O2流量2.5mL/h；H2O2浓度10mol/L；汽化温度140℃）

图6 烟气共存气对脱硝效率的影响（H2O2流量2.5mL/h；H2O2浓度10mol/L；汽化温度140℃；反应温度140℃）

图7 反应时间对脱硝效率的影响（H2O2流量2.5mL/h；H2O2浓度10mol/L；汽化温度140℃；反应温度140℃）

图8 氧化后液相产物的离子色谱图（H2O2流量2.5mL/h；H2O2浓度10mol/L；汽化温度140℃；反应温度140℃；SO21000μL/L）

图9 反应前后催化剂的XRD谱图（H2O2流量2.5mL/h；H2O2浓度10mol/L；汽化温度140℃；反应温度140℃；反应时间8h）

图10 反应前后催化剂SEM图（H2O2流量2.5mL/h；H2O2浓度10mol/L；汽化温度140℃；反应温度140℃；反应时间8h）

图11 反应前后催化剂XPS谱图（H2O2流量2.5mL/h；H2O2浓度10mol/L；汽化温度140℃；反应温度140℃；反应时间8h）

图12 反应前后催化剂FTIR谱图（H2O2流量2.5mL/h；H2O2浓度10mol/L；汽化温度140℃；反应温度140℃；反应时间8h；SO21000μL/L）

图13 催化剂长时间反应前后的N2吸附-解吸等温线和孔径分布曲线（H2O2流量2.5mL/h；H2O2浓度10mol/L；汽化温度140℃；反应温度140℃；反应时间8h）

表1 催化剂反应前后孔结构参数

催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm
反应前	60.346	0.226	14.98
反应后	51.96	0.1844	14.194

参考文献 34

1	钱伯章,李敏.能源结构随能源需求增长而持续多样化——2018年世界能源统计年鉴解读[J].中国石油和化工经济分析,2018 (8):51-54.
	QIAN B Z,LI M.Energy structure continues to diversify as energy demand grows—Interpretation of the 2018 world energy statistics yearbook[J].Economic Analysis of China Petroleum and Chemical Industry,2018 (8):51-54.
2	WU B,XIONG Y Q,RU J B,et al.Removal of NO from flue gas using heat-activated ammonium persulfate aqueous solution in a bubbling reactor[J].RSC Advances,2016,6(40):33919-33930．
3	温学友,赵毅.Fenton反应在燃煤烟气脱硝处理中的应用[J].华北电力大学学报,2018,45(3):95-100.
	WEN X Y,ZHAO Y.Application of Fenton reaction in coal-fired flue gas denitration[J].Journal of North China Electric Power University,2018,45(3):95-100.
4	WANG Z H,ZHOU J H,ZHU Y Q,et al.Simultaneous removal of NO_x, SO₂ and Hg in nitrogen flow in a narrow reactor by ozone injection: experimental results[J].Fuel Processing Technology,2007,88(8):817-823.
5	WU B,XIONG Y Q.A novel low-temperature NO removal approach with ·OH from catalytic decomposition of H₂O₂ over La_1-_xCa_xFeO₃ oxides[J].Journal of Chemical Technology and Biotechnology,2018,93(1):43-53.
6	LIU Y X,PAN J F,TANG A K,et al.A study on mass transfer-reaction kinetics of NO absorption by using UV/H₂O₂/NaOH process[J].Fuel,2013,108:254-260.
7	LIU Y X,PAN J F,ZHANG J,et al.Investigation on the removal of NO from SO₂-containing simulated flue gas by an ultraviolet/Fenton-like reaction[J].Energy and Fuels,2012,26(9):5430-5436.
8	LIU Y X,ZHANG J,WANG Z L.A study on kinetics of NO absorption from flue gas by using UV/Fenton wet scrubbing[J].Chemical Engineering Journal,2012,197:468-474.
9	LIU Y X,ZHANG J,SHENG C D,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.
10	LOUSADA C M,JONSSON M.Kinetics, mechanism, and activation energy of H₂O₂decomposition on the surface of ZrO₂[J].Journal of Physical Chemistry C,2010,114(25):11202-11208.
11	PHAM A L T,LEE C,DOYLE F M,et al.A silica-supported iron oxide catalyst capable of activating hydrogen peroxide at neutral pH values[J].Environmental Science and Technology,2009,43(23):8930-8935.
12	DING J,ZHONG Q,ZHANG S,et al.Simultaneous removal of NO_xand SO₂from coal-fired flue gas by catalytic oxidation removal process with H₂O₂[J].Chemical Engineering Journal,2014,243:176-182.
13	HUANG X M,DING J,ZHONG Q.Catalytic decomposition of H₂O₂ over Fe-based catalysts for simultaneous removal of NO_x and SO₂[J].Applied Surface Science,2015,326:66-72.
14	WU B,XIONG Y Q,GE Y Y.Simultaneous removal of SO₂ and NO from flue gas with ·OH from the catalytic decomposition of gas-phase H₂O₂ over solid-phase Fe₂(SO₄)₃[J].Chemical Engineering Journal,2018,331:343-354.
15	WU B,XIONG Y Q,RU J B,et al.Enhancement of NO absorption in ammonium-based solution using heterogeneous Fenton reaction at low H₂O₂consumption[J].Korean Journal of Chemical Engineering,2016,33(12):3407-3416.
16	WU B,ZHANG S P,HE S S,et al.Follow-up mechanism study on NO oxidation with vaporized H₂O₂ catalyzed by Fe₂O₃ in a fixed-bed reactor[J].Chemical Engineering Journal,2019,356:662-672.
17	邹雪华,陈天虎,刘海波,等.热处理针铁矿的结构与色度演化[J].硅酸盐学报,2013,41(5):669-673.
	ZHOU X H,CHEN T H,LIU H B,et al.Structural and chromatic evolution of goethite by thermal treatment[J].Joural of the Chinese Ceramic Society,2013,41(5):669-673.
18	许俊鸽,李云琴,苑宝玲,等.三维花状结构α-FeOOH协同H₂O₂可见光催化降解双氯芬酸钠[J].环境科学,2015,36(6):2122-2128.
	XU J G,LI Y Q,YUAN B L,et al.Catalytic degradation of diclofenac sodium over the catalyst of 3D flower-like α-FeOOH synergized with H₂O₂ under visible light irradiation[J].Environmental Science,2015,36(6):2122-2128.
19	ZHANG T,LI C J,MA J,et al.Surface hydroxyl groups of synthetic α-FeOOH in promoting ·OH generation from aqueous ozone: property and activity relationship[J].Applied Catalysis B: Environmental,2008,82(1/2):131-137.
20	WU H H,OU X W,DENG D Y,et al.Decolourization of the azo dye Orange G in aqueous solutionvia a heterogeneous Fenton-like reaction catalysed by goethite[J].Environmental Technology,2012,33(14):1545-1552.
21	SUI M H,SHENG L,LU K X,et al.FeOOH catalytic ozonation of oxalic acid and the effect of phosphate binding on its catalytic activity[J].Applied Catalysis B: Environmental,2010,96(1/2):94-100.
22	GUO L N,ZHONG Q,DING J,et al.Low-temperature NO_x (x=1, 2) removal with ·OH radicals from catalytic ozonation over α-FeOOH[J].Ozone: Science and Engineering,2016,38(5):382-394.
23	林志荣,赵玲,董元华,等.针铁矿催化过氧化氢降解PCB28[J].环境科学学报,2011,31(11):2043-2048.
	LIN Z R,ZHAO L,DONG Y H,et al.Degradation of PCB28 by goethite-catalyzed hydrogen peroxide[J].Acta Scientiae Circumstantiae,2011,31(11):2043-2048.
24	YANG S Y,XIONG Y Q,GE Y Y,et al.Heterogeneous Fenton oxidation of nitric oxide by magnetite: kinetics and mechanism[J].Materials Letters,2018,218:257-261.
25	QIAN X,HE P,CHEN J,et al.Fabrication of FeOOH/BiOCl nanocomposites with enhanced visible light photocatalytic activity[J].Journal of Inorganic and General Chemistry,2019,645:906-909.
26	LI K,LIU X,ZHENG T,et al.Tuning MnO₂ to FeOOH replicas with bio-template 3D morphology as electrodes for high performance asymmetric supercapacitors[J].Chemical Engineering Journal,2019,370:136-147.
27	HUANG Y,GAO Y,ZHANG Q,et al.Biocompatible FeOOH-carbon quantum dots nanocomposites for gaseous NO_x removal under visible light: improved charge separation and high selectivity[J].Journal of Hazardous Materials,2018,354:54-62.
28	WEI C Z,QIAO P H,NAN Z D.Size-controlled synthesis of rod-like α-FeOOH nanostructure[J].Materials Science and Engineering C,2012,32(6):1524-1530.
29	朱佳裔.FeOOH/H₂O₂去除水中对氯硝基苯的研究[D].哈尔滨:哈尔滨工业大学,2011.
	ZHU J Y.Study on removal of parachloronitrobenzene in water by FeOOH/H₂O₂ system[D].Harbin:Harbin Institute of Technology,2011.
30	LI Z C,GUAN M Y,LOU Z S,et al.Facile hydrothermal synthesis and electrochemical properties of flowerlike α-FeOOH[J].Micro & Nano Letter,2012,7(1):33-36.
31	LI Z C,CHEN S S,GU A J,et al.Facile hydrothermal synthesis and electrochemical properties of hollow urchin-like α-FeOOH[J].Micro & Nano Letter2012,7(8):757-761.
32	OU P,XU G,REN Z H,et al.Hydrothermal synthesis and characterization of uniform α-FeOOH nanowires in high yield[J].Materials Letters,2008,62(3):914-917.
33	GENG F X,ZHAO Z G,GENG J X,et al.A simple and low-temperature hydrothermal route for the synthesis of tubular α-FeOOH[J].Materials Letters,2007,61(3):4794-4796.
34	盖洋洋,吴波,熊源泉,等.基于凹凸棒土催化双氧水分解的低温燃煤烟气脱硝[J].化工进展,2018,37(4):1608-1615.
	GAI Y Y,WU B,XIONG Y Q,et al.Experimental study of low-temperature flue gas denitrification based on H₂O₂ decomposition attapulgite catalyst[J].Chemical Industry and Eenineering Progress,2018,37(4):1608-1615.

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[6]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[7]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[8]	王鹏, 史会兵, 赵德明, 冯保林, 陈倩, 杨妲. 过渡金属催化氯代物的羰基化反应研究进展[J]. 化工进展, 2023, 42(9): 4649-4666.
[9]	张启, 赵红, 荣峻峰. 质子交换膜燃料电池中氧还原反应抗毒性电催化剂研究进展[J]. 化工进展, 2023, 42(9): 4677-4691.
[10]	王伟涛, 鲍婷玉, 姜旭禄, 何珍红, 王宽, 杨阳, 刘昭铁. 醛酮树脂基非金属催化剂催化氧气氧化苯制备苯酚[J]. 化工进展, 2023, 42(9): 4706-4715.
[11]	葛亚粉, 孙宇, 肖鹏, 刘琦, 刘波, 孙成蓥, 巩雁军. 分子筛去除VOCs的研究进展[J]. 化工进展, 2023, 42(9): 4716-4730.
[12]	朱传强, 茹晋波, 孙亭亭, 谢兴旺, 李长明, 高士秋. 固体高分子脱硝剂选择性非催化还原NO _x 特性[J]. 化工进展, 2023, 42(9): 4939-4946.
[13]	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.
[14]	向阳, 黄寻, 魏子栋. 电催化有机合成反应的活性和选择性调控研究进展[J]. 化工进展, 2023, 42(8): 4005-4014.
[15]	王耀刚, 韩子姗, 高嘉辰, 王新宇, 李思琪, 杨全红, 翁哲. 铜基催化剂电还原二氧化碳选择性的调控策略[J]. 化工进展, 2023, 42(8): 4043-4057.

基于α-FeOOH催化H₂O₂蒸气的低温烟气脱硝实验

Low-temperature flue gas denitration by H₂O₂ vapor over α-FeOOH

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 14

参考文献 34

相关文章 15

编辑推荐

Metrics

本文评价