金属硫化物吸附剂脱除烟气汞研究进展

doi:10.16085/j.issn.1000-6613.2020-0318

摘要/Abstract

摘要：

工业烟气排放的汞严重危害人体健康及生态环境，金属硫化物是一种新型的高效汞吸附剂，受到广泛关注。本文总结了近年来金属硫化物应用于脱除烟气汞的研究进展。归纳了不同金属硫化物的吸附性能，并对影响吸附性能的常见因素进行了梳理，已有研究表明金属硫化物在复杂的反应条件下仍具有优异的脱汞性能；进一步归纳了金属硫化物的汞吸附机理；总结出活性位和比表面积的调控是当前强化金属硫化物汞吸附性能的常见方法；最后对金属硫化物的再生方法进行了介绍。基于当前研究进展，未来的研究应关注如何强化金属硫化物在高温下的脱汞性能，以及如何在低温条件下实现汞的脱附从而避免当前高温热脱附方法对金属硫化物结构的破坏。

关键词: 污染, 吸附剂, 金属硫化物, 烟道气, 脱汞

Abstract:

Mercury emitted from industrial flue gas does great harm to human health and the ecological environment. Metal sulfide is a new type of high-efficiency mercury adsorbent, which has attracted extensive attention. This paper reviews the recent research progresses on mercury removal from flue gas by metal sulfides. The mercury removal performance of different metal sulfides was summarized, and the main influence factors were combed. Current studies suggest that metal sulfides can give excellent mercury removal performance even under complex reaction conditions. This paper also summarizes the mercury adsorption mechanism of metal sulfides and concludes that the adjustments of active sites and specific surface area of metal sulfides are the common methods to enhance the adsorption performance. Finally, the regeneration methods of metal sulfide are introduced. Based on the current research progress, future studies should focus on how to enhance the mercury removal performance of metal sulfides at high temperature, and meanwhile to achieve mercury desorption at low temperature to avoid the destruction of metal sulfide occurred in the high-temperature thermal desorption method.

Key words: pollution, adsorbents, metal sulfides, flue gas, mercury removal

中图分类号:

X511

黄瑞, 杨阳, 徐文青, 张冀翔, 朱廷钰. 金属硫化物吸附剂脱除烟气汞研究进展[J]. 化工进展, 2020, 39(12): 5243-5251.

Rui HUANG, Yang YANG, Wenqing XU, Jixiang ZHANG, Tingyu ZHU. Research progress of metal sulfide adsorbents for removing mercury in flue gas[J]. Chemical Industry and Engineering Progress, 2020, 39(12): 5243-5251.

参考文献

1	XU Wen, HUSSAIN Arshad, LIU Yangxian. A review on modification methods of adsorbents for elemental mercury from flue gas[J]. Chemical Engineering Journal, 2018, 346: 692-711.
2	DRANGA Beatrice Andreea, LAZAR Liliana, KOESER Heinz. Oxidation catalysts for elemental mercury in flue gases: a review[J]. Catalysts, 2012, 2(1): 139-170.
3	SHA Qinge, LU Menghua, HUANG Zhijiong, et al. Anthropogenic atmospheric toxic metals emission inventory and its spatial characteristics in Guangdong Province, China[J]. Science of the Total Environment, 2019, 670: 1146-1158.
4	GAO Yanshan, ZHANG Zhang, WU Jingwen, et al. A critical review on the heterogeneous catalytic oxidation of elemental mercury in flue gases[J]. Environmental Science & Technology, 2013, 47(19): 10813-10823.
5	HYLANDER Lars D, HERBERT Roger B. Global emission and production of mercury during the pyrometallurgical extraction of nonferrous sulfide ores[J]. Environmental Science & Technology, 2008, 42(16): 5971-5977.
6	United Nations Environment Programme. Global mercury assessment 2018: report of UNEP Chemicals and Health Branch [R]. Geneva: UNEP, 2019
7	ZHAO Shilin, PUDASAINEE Deepak, DUAN Yufeng, et al. A review on mercury in coal combustion process: content and occurrence forms in coal, transformation, sampling methods, emission and control technologies[J]. Progress in Energy and Combustion Science, 2019, 73: 26-64.
8	SHI Mengting, LUO Guangqian, XU Yang, et al. Using H₂S plasma to modify activated carbon for elemental mercury removal[J]. Fuel, 2019, 254: 115549.
9	Serre SHANNON D, Silcox GEOFFREY D. Adsorption of elemental mercury on the residual carbon in coal fly ash[J]. Industrial & Engineering Chemistry Research, 2000, 39(6): 1723-1730.
10	ZHANG Huawei, LIU Xiuli, WANG Li, et al. Characteristics and stability of mercury vapor adsorption over two kinds of modified semicoke[J]. Scientific World Journal, 2014, 2014: 260141.
11	府师敏, 陈美玲, 卢平. 改性钙基吸附剂脱汞性能的实验研究[J]. 环境工程, 2018, 36(1): 103-107.
11	FU Shimin, CHEN Meiling, LU Ping. Experimental study on mercury adsorption capacity on modified Ca-based sorbents[J]. Environmental Engineering, 2018, 36(1): 103-107.
12	DONG Lu, HUANG Yaji, CHEN Hao, et al. Magnetic γ-Fe₂O₃-loaded attapulgite sorbent for Hg⁰ removal in coal-fired flue gas[J]. Energy & Fuels, 2019, 33(8): 7522-7533.
13	王建英, 马丽萍. 盐酸溶液改性蛭石对气态单质汞的吸附性能[J]. 化工环保, 2008, 28(4): 292-295.
13	WANG Jianying, MA Liping. Study on gas-phase elementary mercury adsorption by HCl-modified vermiculite[J]. Environmental Protection of Chemical Industry, 2008, 28(4): 292-295.
14	HE Chuan, SHEN Boxiong, CHI Guilong, et al. Elemental mercury removal by CeO₂/TiO₂-PILCs under simulated coal-fired flue gas[J]. Chemical Engineering Journal, 2016, 300: 1-8.
15	陈建涛, 马丽萍, 资泽城, 等. 5A分子筛的改性制备及其对汞的吸附研究[J]. 硅酸盐通报, 2014, 33(9): 2164-2169.
15	CHEN Jiantao, MA Liping, ZI Zecheng, et al. Study on the preparation of modified 5A molecular sieve and its adsorption of mercury[J]. Bulletin of the Chinese Ceramic Society, 2014, 33(9): 2164-2169.
16	TONG Li, XU Wenqing, QI Hao, et al. Enhanced effect of O/N groups on the Hg⁰ removal efficiency over the HNO₃-modified activated carbon[J]. Acta Physica-Chimica Sinica, 2015, 31(3): 512-518.
17	SUN Ping, ZHANG Bi, ZENG Xiaobo, et al. Deep study on effects of activated carbon’s oxygen functional groups for elemental mercury adsorption using temperature programmed desorption method[J]. Fuel, 2017, 200: 100-106.
18	LI Na, WEI Hongqi, DUAN Yufeng, et al. Experimental study on mercury adsorption and adsorbent regeneration of sulfur-loaded activated carbon[J]. Energy & Fuels, 2018, 32(10): 11023-11029.
19	ZHANG Bi, ZENG Xiaobo, XU Ping, et al. Using the novel method of nonthermal plasma to add Cl active sites on activated carbon for removal of mercury from flue gas[J]. Environmental Science & Technology, 2016, 50(21): 11837-11843.
20	QI Hao, XU Wenqing, WANG Jian, et al. Hg⁰ removal from flue gas over different zeolites modified by FeCl₃[J]. Journal of Environmental Sciences, 2015, 28: 110-117.
21	LIU Xi, JIANG Shaojian, LI Hailong, et al. Elemental mercury oxidation over manganese oxide octahedral molecular sieve catalyst at low flue gas temperature[J]. Chemical Engineering Journal, 2019, 356: 142-150.
22	FAN Xiaopeng, LI Caiting, ZENG Guangming, et al. The effects of Cu/HZSM-5 on combined removal of Hg⁰ and NO from flue gas[J]. Fuel Processing Technology, 2012, 104: 325-331.
23	CHALKIDIS Anastasios, JAMPAIAH Deshetti, AMIN Mohamad Hassan, et al. CeO₂-Decorated α-MnO₂ nanotubes: a highly efficient and regenerable sorbent for elemental mercury removal from natural gas[J]. Langmuir, 2019, 35(25): 8246-8256.
24	WU Yinghong, XU Wenqing, YANG Yang, et al. Support effect of Mn-based catalysts for gaseous elemental mercury oxidation and adsorption[J]. Catalysis Science & Technology, 2018, 8(1): 297-306.
25	JAMPAIAH Deshetti, IPPOLITO Samuel J, SABRI Ylias M, et al. Ceria-zirconia modified MnO_x catalysts for gaseous elemental mercury oxidation and adsorption[J]. Catalysis Science & Technology, 2016, 6(6): 1792-1803.
26	XIE Jiangkun, YAN Naiqiang, YANG Shijian, et al. Synthesis and characterization of nano-sized Mn-TiO₂ catalysts and their application to removal[J]. Research on Chemical Intermediates, 2012, 38(8): 2511-2522.
27	ZHANG Xiao, SHEN Boxiong, ZHU Sheaowen, et al. UiO-66 and its Br-modified derivates for elemental mercury removal[J].Journal of Hazardous Materials, 2016, 320: 556-563.
28	MARTELLARO P J, MOORE G A, PETERSON E S, et al. Environmental application of mineral sulfides for removal of gas-phase Hg⁰ and aqueous Hg²⁺[J]. Separation Science and Technology, 2001, 36(5/6): 1183-1196.
29	YANG Zequn, LI Hailong, YANG Jianping, et al. Nanosized copper selenide functionalized zeolitic imidazolate framework-8 (CuSe/ZIF-8) for efficient immobilization of gas-phase elemental mercury[J]. Advanced Functional Materials, 2019, 29(17): 1807191.
30	ZHAO Haitao, MU Xueliang, YANG Gang, et al. Graphene-like MoS₂ containing adsorbents for Hg⁰ capture at coal-fired power plants[J]. Applied Energy, 2017, 207: 254-264.
31	MEI Jian, WANG Chang, KONG Lingnan, et al. Outstanding performance of recyclable amorphous MoS₃ supported on TiO₂ for capturing high concentrations of gaseous elemental mercury: mechanism, kinetics, and application[J]. Environmental Science & Technology, 2019, 53(8): 4480-4489.
32	LIU Hui, YOU Zhiwen, YANG Shu, et al. High-efficient adsorption and removal of elemental mercury from smelting flue gas by cobalt sulfide[J]. Environmental Science and Pollution Research International, 2019, 26(7): 6735-6744.
33	LIU Wei, XU Haomiao, LIAO Yong, et al. Recyclable CuS sorbent with large mercury adsorption capacity in the presence of SO₂ from non-ferrous metal smelting flue gas[J]. Fuel, 2019, 235: 847-854.
34	ZHAO Haitao, FAN Hua, YANG Gang, et al. Integrated dynamic and steady state method and its application on the screening of MoS₂ nanosheet-containing adsorbents for Hg⁰ capture[J]. Energy & Fuels, 2018, 32(4): 5338-5344.
35	LI Hailong, ZHU Lei, WANG Jun, et al. Development of nano-sulfide sorbent for efficient removal of elemental mercury from coal combustion fuel gas[J]. Environmental Science & Technology, 2016, 50(17): 9551-9557.
36	YANG Zequn, LI Haillong, Feng Shihao, et al. Multiform sulfur adsorption centers and copper-terminated active sites of nano-CuS for efficient elemental mercury capture from coal combustion flue gas[J]. Langmuir, 2018, 34(30): 8739-8749.
37	LIU Wei, ZHOU Yongxian, HUA Yinfeng, et al. A sulfur-resistant CuS-modified active coke for mercury removal from municipal solid waste incineration flue gas[J]. Environmental Science and Pollution Research International, 2019, 26(24): 24831-24839.
38	LIAO Yong, XU Haomiao, LIU Wei, et al. One step interface activation of ZnS using cupric ions for mercury recovery from nonferrous smelting flue gas[J]. Environmental Science & Technology, 2019, 53(8): 4511-4518.
39	ZOU Sijie, LIAO Yong, TAN Wei, et al. H₂S-modified natural ilmenite: a recyclable magnetic sorbent for recovering gaseous elemental mercury from flue gas[J]. Industrial & Engineering Chemistry Research, 2017, 56(36): 10060-10068.
40	HUO Qihuang, WANG Yahui, CHEN Huijun, et al. ZnS/AC sorbent derived from the high sulfur petroleum coke for mercury removal[J]. Fuel Process Technology, 2019, 191: 36-43.
41	ZHAO Haitao, YANG Gang, MU Xueliang, et al. Hg⁰ capture over MoS₂nanosheets containing adsorbent: effects of temperature, space velocity, and other gas species[J]. Energy Procedia, 2017, 105: 4408-4413.
42	LI Hailong, ZHU Lei, WANG Jun, et al. Effect of nitrogen oxides on elemental mercury removal by nanosized mineral sulfide[J]. Environmental Science & Technology, 2017, 51(15): 8530-8536.
43	YANG Zequn, LI Hailong, QU Wenqi, et al. Role of sulfur trioxide (SO₃) in gas-phase elemental mercury immobilization by mineral sulfide[J]. Environmental Science & Technology, 2019, 53(6): 3250-3257.
44	KONG Lingnan, ZOU Sijie, MEI Jian, et al. Outstanding resistance of H₂S-modified Cu/TiO₂ to SO₂ for capturing gaseous Hg⁰ from nonferrous metal smelting flue gas: performance and reaction mechanism[J]. Environmental Science & Technology, 2018, 52(17): 10003-10010.
45	LI Hailong, FENG Shihao, YANG Zequn, et al. Density functional theory study of mercury adsorption on CuS surface: effect of typical flue gas components[J]. Energy & Fuels, 2019, 33(2): 1540-1546.
46	LI Hailong, FENG Shihao, QU Wenqi, et al. Adsorption and oxidation of elemental mercury on chlorinated ZnS surface[J]. Energy & Fuels, 2018, 32(7): 7745-7751.
47	ZHAO Jiexia, LI Hailong, YANG Zequn, et al. Dual roles of nano-sulfide in efficient removal of elemental mercury from coal combustion flue gas within a wide temperature range[J]. Environmental Science & Technology, 2018, 52(21): 12926-12933.
48	MU Xueliang, GAO Xiang, ZHAO Haitao, et al. Density functional theory study of the adsorption of elemental mercury on a 1T-MoS₂ monolayer[J]. Journal of Zhejiang University: Science A, 2018, 19(1): 60-67.
49	ZHAO Haitao, MU Xueliang, YANG Gang, et al. Microwave-induced activation of additional active edge sites on the MoS₂ surface for enhanced Hg⁰ capture[J]. Applied Surface Science, 2017, 420: 439-445.
50	QUAN Zongwen, HUANG Wenjun, LIAO Yong, et al. Study on the regenerable sulfur-resistant sorbent for mercury removal from nonferrous metal smelting flue gas[J]. Fuel, 2019, 241: 451-458.
51	SUN Yue, LIU Yuanli, LOU Zimo, et al. Enhanced performance for Hg(Ⅱ) removal using biomaterial (CMC/gelatin/starch) stabilized FeS nanoparticles: stabilization effects and removal mechanism[J]. Chemical Engineering Journal, 2018, 344: 616-624.
52	K Suresh Kumar REDDY, SHOAIBI Ahmed AL, SRINIVASAKANNAN C. Mercury removal using metal sulfide porous carbon complex[J]. Process Safety and Environmental Protection, 2018, 114: 153-158.
53	ZHAO Haitao, YANG Gang, GAO Xiang, et al. Hg⁰ capture over CoMoS/gamma-Al₂O₃ with MoS₂ nanosheets at low temperatures[J]. Environmental Science & Technology, 2016, 50(2): 1056-1064.

[1]	王胜岩, 邓帅, 赵睿恺. 变电吸附二氧化碳捕集技术研究进展[J]. 化工进展, 2023, 42(S1): 233-245.
[2]	王莹, 韩云平, 李琳, 李衍博, 李慧丽, 颜昌仁, 李彩侠. 城市污水厂病毒气溶胶逸散特征研究现状与未来展望[J]. 化工进展, 2023, 42(S1): 439-446.
[3]	李宁, 李金科, 董金善. 乙烯裂解炉多孔介质燃烧器的研究与开发[J]. 化工进展, 2023, 42(S1): 73-83.
[4]	葛全倩, 徐迈, 梁铣, 王凤武. MOFs材料在光电催化领域应用的研究进展[J]. 化工进展, 2023, 42(9): 4692-4705.
[5]	徐杰, 夏隆博, 罗平, 邹栋, 仲兆祥. 面向膜蒸馏过程的全疏膜制备及其应用进展[J]. 化工进展, 2023, 42(8): 3943-3955.
[6]	王云刚, 焦健, 邓世丰, 赵钦新, 邵怀爽. 冷凝换热与协同脱硫性能实验分析[J]. 化工进展, 2023, 42(8): 4230-4237.
[7]	杨静, 李博, 李文军, 刘晓娜, 汤刘元, 刘月, 钱天伟. 焦化污染场地中萘降解菌的分离及降解特性[J]. 化工进展, 2023, 42(8): 4351-4361.
[8]	张雪伟, 黄亚继, 许月阳, 程好强, 朱志成, 李金壘, 丁雪宇, 王圣, 张荣初. 碱性吸附剂对燃煤烟气中SO₃的吸附特性[J]. 化工进展, 2023, 42(7): 3855-3864.
[9]	陆洋, 周劲松, 周启昕, 王瑭, 刘壮, 李博昊, 周灵涛. CeO₂/TiO₂吸附剂煤气脱汞产物的浸出规律[J]. 化工进展, 2023, 42(7): 3875-3883.
[10]	徐伟, 李凯军, 宋林烨, 张兴惠, 姚舜华. 光催化及其协同电化学降解VOCs的研究进展[J]. 化工进展, 2023, 42(7): 3520-3531.
[11]	王久衡, 荣鼐, 刘开伟, 韩龙, 水滔滔, 吴岩, 穆正勇, 廖徐情, 孟文佳. 水蒸气强化纤维素模板改性钙基吸附剂固碳性能及强度[J]. 化工进展, 2023, 42(6): 3217-3225.
[12]	何川, 吴国勋, 李昂, 张发捷, 卞子君, 卢承政, 王丽朋, 赵民. 垃圾焚烧脱硝催化剂钙镁失活与活性恢复特性[J]. 化工进展, 2023, 42(5): 2413-2420.
[13]	张宁, 吴海滨, 李钰, 李剑锋, 程芳琴. 漂浮型光催化材料的制备及其在水处理领域的应用研究进展[J]. 化工进展, 2023, 42(5): 2475-2485.
[14]	赵重阳, 赵磊, 石详文, 黄俊, 李治尧, 沈凯, 张亚平. O₂/H₂O/SO₂ 对改性富铁凹凸棒石高温吸附PbCl₂ 的影响[J]. 化工进展, 2023, 42(4): 2190-2200.
[15]	郭帅帅, 陈锦路, 金梁程龙, 陶醉, 陈小丽, 彭国文. 基于海水提铀的多孔芳香框架材料研究进展[J]. 化工进展, 2023, 42(3): 1426-1436.