Mechanism of Hg removal by gaseous advanced oxidation process with Fe3O4 and H2O2

doi:10.11949/j.issn.0438-1157.20171236

CIESC Journal ›› 2018, Vol. 69 ›› Issue (5): 1840-1845.DOI: 10.11949/j.issn.0438-1157.20171236

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Mechanism of Hg removal by gaseous advanced oxidation process with Fe₃O₄ and H₂O₂

ZHOU Changsong^1,2, YANG Hongmin¹, SUN Jiaxing¹, QI Dongxu¹, MAO Lin¹, SONG Zijian³, SUN Lushi³

1. School of Energy & Mechanical Engineering, Nanjing Normal University, Nanjing 210042, Jiangsu, China;
2. School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, Jiangsu, China;
3. State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China

Received:2017-09-11 Revised:2018-01-02 Online:2018-05-05 Published:2018-05-05
Supported by:
supported by the National Natural Science Foundation of China (51676101, 51376073), the Natural Science Foundation of Jiangsu Province (BK20161558), the China Postdoctoral Science Foundation (2017M621779) and the College Natural Science Foundation of Jiangsu Province (17KJB470009).

Fe₃O₄协同H₂O₂气相高级氧化单质汞的机理

周长松^1,2, 杨宏旻¹, 孙佳兴¹, 祁东旭¹, 毛琳¹, 宋子健³, 孙路石³

1. 南京师范大学能源与机械工程学院, 江苏南京 210042;
2. 南京师范大学化学与材料科学学院, 江苏南京 210023;
3. 华中科技大学煤燃烧国家重点实验室, 湖北武汉 430074

通讯作者: 周长松
基金资助:
国家自然科学基金项目（51676101，51376073）；江苏省自然科学基金项目（BK20161558）；中国博士后科学基金项目（2017M621779）；江苏省高校自然科学基金项目（17KJB470009）。

Abstract

Abstract:

The decomposition properties of H₂O₂ molecule over Fe₃O₄ (111), (110), and (001) surfaces were systematically investigated by using density functional theory (DFT) calculations. Hg adsorption and oxidation mechanisms over H₂O₂/Fe₃O₄ system were studied. Binding energies, optimized geometries, Mulliken population, and molecular orbital analysis of partial density of states (PDOS) between Hg and H₂O₂/Fe₃O₄ surfaces were proposed. The most favored configurations of H₂O₂ decomposition, which was associated with the generation mechanism of OH groups, as well as the intermediates of Hg species were discussed. The results showed that OH radicals were more likely produced on Fe₃O₄ (111), (001) A, and (110) A surfaces. The oxidative activity of OH produced on different surfaces varies a lot. In addition, Mulliken charge population revealed Hg⁰ oxidation when the systems were in equilibrium because a large number of electrons transferred from Hg⁰ to the surface hydroxyl. The calculated binding energies suggested that the process of HO-Hg-OH and Hg-OH generation were exothermic on Fe₃O₄ surface with H₂O₂. The desorption analysis showed that HO-Hg-OH and Hg-OH intermediates had a lower desorption energy when they detached from the surface.

Key words: mercury, oxidation, density functional theory, radical, surface

摘要：

利用密度泛函理论分别研究了H₂O₂分子在Fe₃O₄（111）、（110）和（001）表面分解特性，并对单质汞在H₂O₂/Fe₃O₄体系的反应特性进行了研究。对比不同构型的结合能、Mulliken电荷转移和分态密度分析，详细讨论了H₂O₂分解产生羟基的规律以及Hg⁰的氧化态中间产物成键特性。结果表明：H₂O₂分子在Fe₃O₄（111）、（001） A和（110） A表面更容易分解产生羟基；不同表面产生的羟基对Hg⁰具有不同的氧化活性；Hg⁰在表面羟基的作用下可有效通过电荷转移实现氧化。对比分析了三种表面汞氧化态中间产物的脱附路径，HO—Hg—OH和Hg—OH的表面脱附是主要的反应路径。

关键词: 汞, 氧化, 密度泛函理论, 自由基, 表面

CLC Number:

TQ534.9

ZHOU Changsong, YANG Hongmin, SUN Jiaxing, QI Dongxu, MAO Lin, SONG Zijian, SUN Lushi. Mechanism of Hg removal by gaseous advanced oxidation process with Fe₃O₄ and H₂O₂[J]. CIESC Journal, 2018, 69(5): 1840-1845.

周长松, 杨宏旻, 孙佳兴, 祁东旭, 毛琳, 宋子健, 孙路石. Fe₃O₄协同H₂O₂气相高级氧化单质汞的机理[J]. 化工学报, 2018, 69(5): 1840-1845.

References 32

[1]	DAVID K, MILENA H, NICOLA P, et al. Contribution of contaminated sites to the global mercury budget[J]. Environ. Res., 2013, 125:160-170.
[2]	ZHANG X, SHEN B, SHEN F, et al. The behavior of the manganese-cerium loaded metal-organic framework in elemental mercury and NO removal from flue gas[J]. Chem. Eng. J., 2017, 326:551-560.
[3]	XU Y, ZHONG Q, LIU X. Elemental mercury oxidation and adsorption on magnesite powder modified by Mn at low temperature[J]. J. Hazard. Mater., 2015, 283:252-259.
[4]	ZHAO Y, MA X, XU P, et al. Elemental mercury removal from flue gas by CoFe2O4 catalyzed peroxymonosulfate[J]. J. Hazard. Mater., 2018, 341:228-237.
[5]	ZHENG J, OU J, MO Z, et al. Mercury emission inventory and its spatial characteristics in the pearl river delta region, China[J]. Sci. Total Environ., 2011, 412:214-222.
[6]	谭增强, 邱建荣, 苏胜, 等. 高效脱汞吸附剂的脱汞机理研究[J]. 工程热物理学报, 2012, 33(2):343-347. TAN Z Q, QIU J R, SU S, et al. Study on the mercury removal mechanism of adsorbents[J]. J. Eng. Therm., 2012, 33(2):343-347.
[7]	LI H, ZHU L, WU S, et al. Synergy of CuO and CeO2 combination for mercury oxidation under low-temperature selective catalytic reduction atmosphere[J]. Int. J. Coal Geol., 2017, 170:69-76.
[8]	XU H, QU Z, ZONG C, et al. Catalytic oxidation and adsorption of Hg0 over low-temperature NH3-SCR LaMnO3 perovskite oxide from flue gas[J]. Appl. Catal. B, 2016, 186:30-40.
[9]	LI H, ZHANG W, WANG J, et al. Coexistence of enhanced Hg0 oxidation and induced Hg2+ reduction on CuO/TiO2 catalyst in the presence of NO and NH3[J]. Chem. Eng. J., 2017, 330:1248-1254.
[10]	LI H, WU S, WU C, et al. SCR atmosphere induced reduction of oxidized mercury over CuO-CeO2/TiO2 catalyst[J]. Environ. Sci. Technol., 2015, 49(12):7373-7379.
[11]	李春峰, 段钰锋, 汤红健, 等. CaO对汞的选择性吸附及SO2毒化特性[J]. 化工学报, 2017, 68(9):3565-3572. LI C F, DUAN Y F, TANG H J, et al. Mercury selective adsorption characteristics and SO2 poison performance on CaO[J]. CIESC Journal, 2017, 68(9):3565-3572.
[12]	HE D, WONG C E, TANG W, et al. Faradaic reactions in water desalination by batch-mode capacitive deionization[J]. Environ. Sci. Technol., 2016, 3(5):222-226.
[13]	HAO R, ZHAO Y, YUAN B, et al. Establishment of a novel advanced oxidation process for economical and effective removal of SO2 and NO[J]. J. Hazard. Mater., 2016, 318:224-232.
[14]	MICOLI L, BAGNASCO G, TURCO M, et al. Vapour phase H2O2 decomposition on Mn based monolithic catalysts synthesized by innovative procedures[J]. Appl. Catal. B, 2013, 140/141:516-522.
[15]	DING J, ZHONG Q, ZHANG S, et al. Simultaneous removal of NOx and SO2 from coal-fired flue gas by catalytic oxidation-removal process with H2O2[J]. Chem. Eng. J., 2014, 243:176-182.
[16]	LIU Y, YUSUF G A. A review on removal of elemental mercury from flue gas using advanced oxidation process:chemistry and process[J]. Chem. Eng. Res. Des., 2016, 112:199-250.
[17]	ZHOU C, SUN L, ZHANG A, et al. Fe3-xCuxO4 as highly active heterogeneous Fenton-like catalysts toward elemental mercury removal[J]. Chemosphere, 2015, 125:16-24.
[18]	XU Y, CAO L M, SUN W, et al. In-situ catalytic oxidation of Hg0 via a gas diffusion electrode[J]. Chem. Eng. J., 2017, 310:170-178.
[19]	HAO R, ZHAO Y. Macrokinetics of NO oxidation by vaporized H2O2 association with ultraviolet light[J]. Energy Fuels, 2016, 30:2365-2372.
[20]	FARIBA S, ALI R, ABDOLHOSSAIN M, et al. Green oxidation of alcohols by using hydrogen peroxide in water in the presence of magnetic Fe3O4 nanoparticles as recoverable catalyst[J]. Green Chem. Lett. Rev., 2014, 7(3):257-264.
[21]	周长松, 孙路石, 张安超, 等. 非均相类Fenton催化剂脱汞的实验与机理[J]. 化工学报, 2015, 66(4):1324-1330. ZHOU C S, SUN L S, ZHANG A C, et al. Catalytic removal of Hg0 in flue gas by heterogeneous Fenton-like catalysts[J]. CIESC Journal, 2015, 66(4):1324-1330.
[22]	HUNG C M, CHEN C W, JHUANG Y Z, et al. Fe3O4 magnetic nanoparticles:characterization and performance exemplified by the degradation of methylene blue in the presence of persulfate[J]. J. Adv. Oxid. Technol., 2016, 19(1):43-51.
[23]	JUNGHYUN N, OSMAN I O, SAADULLAH G A, et al. Magnetite Fe3O4 (111) surfaces:impact of defects on structure, stability, and electronic properties[J]. Chem. Mater., 2015, 27(17):5856-5867.
[24]	陈磊, 倪刚, 韩波, 等. Fe3O4 (111)面上的水煤气变换反应机理[J]. 化学学报, 2011, 69(4):393-398. CHEN L, NI G, HAN B, et al. Mechanism of water gas shift reaction on Fe3O4 (111) surface[J]. Acta Chimica Sinica, 2011, 69(4):393-398.
[25]	YANG T, WEN X, REN J, et al. Surface structures of Fe3O4 (111), (110), and (001):a density functional theory study[J]. J. Fuel Chem. Technol., 2010, 38(1):121-128.
[26]	呼小红. 金属氧化物催化臭氧生成羟基自由基机理理论研究[D]. 哈尔滨:哈尔滨工业大学, 2013. HU X H. Mechanism study of hydroxyl radical generation from ozone catalyzed by metal oxide[D]. Harbin:Harbin Institute of Technology, 2013.
[27]	PAYNE M C, ALLAN D C, ARIAS T A, et al. Iterative minimization echniques for ab initio total-energy calculations:molecular dynamics and conjugate gradients[J]. Rev. Mod. Phys., 1992, 64(4):1045-1097.
[28]	PERDEW J P, CHEVARY J A, VOSKO S H, et al. Atoms, molecules, solids, and surfaces:applications of the generalized gradient approximation for exchange and correlation[J]. Phys. Rev. B, 1992, 46:6671-6687.
[29]	LI X, PAIER J. Adsorption of water on the Fe3O4 (111) surface:structures, stabilities, and vibrational properties studied by density functional theory[J]. J. Phys. Chem. C, 2016, 120(2):1056-1065.
[30]	ZHOU C, ZHANG Q, CHEN L, et al. Density functional theory study of water dissociative chemisorption on the Fe3O4 (111) surface[J]. J. Phys. Chem. C, 2010, 114:21405-21410.
[31]	SOMMAR J, GARDFELDT K, DAN S, et al. A kinetic study of the gas-phase reaction between the hydroxyl radical and atomic mercury[J]. Atmos. Environ., 2001, 35(17):3049-3054.
[32]	GUO P, GUO X, ZHENG C G. Roles of γ-Fe2O3 in fly ash for mercury removal:results of density functional theory study[J]. Appl. Surf. Sci., 2010, 256:6991-6996.

Mechanism of Hg removal by gaseous advanced oxidation process with Fe₃O₄ and H₂O₂

Fe₃O₄协同H₂O₂气相高级氧化单质汞的机理

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