Mercury selective adsorption characteristics and SO2 poison performance on CaO

doi:10.11949/j.issn.0438-1157.20170343

Abstract

Abstract:

Using Ca(NO₃)₂ as a precursor and SiO₂ as carrier, a supported CaO adsorbent was prepared. The selective adsorption performances of elemental mercury (Hg⁰) and mercuric chloride (HgCl₂) of the sorbent were conducted in a fixed bed, and the effects of SO₂ on CaO mercury adsorption process were also investigated. At the same time, combined with the program temperature desorption (TPD) and in situ diffuse reflectance infrared spectroscopy (in-situ DRIFT) characterization technology, the selective adsorption mechanism of CaO and the mechanism of SO₂ poisoning were deeply investigated. The mercury adsorption results showed that CaO maintained a breakthrough of nearly 100% for Hg⁰ in pure N₂ atmosphere and doped SO₂ atmosphere, while HgCl₂ manifested 66.0% and 60.3% adsorption efficiency in two atmospheres, respectively, indicating that there was a competitive adsorption relationship between SO₂ and HgCl₂ on CaO surface. The characterized results of CaO before and after adsorption suggested that as compared with Hg⁰, HgCl₂ was able to form monodentate, bidentate and other adsorption structure with the basic sites on the CaO surface. SO₂ and HgCl₂ formed a competitive adsorption relationship in the active sites where the bridged bidentate was easily formed, resulting in the reduction of adsorption efficiency of HgCl₂ on CaO.

Key words: CaO adsorbents, elemental mercury, mercuric chloride, selective adsorption, sulfur poisoning

摘要：

利用Ca（NO₃）₂作为前体，SiO₂为载体，制备了一种担载型CaO吸附剂，在固定床实验装置上分别研究了该吸附剂对元素汞（Hg⁰）和氯化汞（HgCl₂）等不同形态汞的选择性吸附性能，以及SO₂对CaO吸附剂汞形态吸附过程的影响，同时结合程序升温脱附和原位红外漫反射表征技术，深入探究了CaO的选择性吸附机理及SO₂毒化机制。汞形态吸附实验结果表明，在纯N₂气氛和掺杂SO₂气氛下，CaO对Hg⁰均保持了接近100%的穿透率，而对HgCl₂在两种气氛下则分别表现出66.0%和60.3%的吸附效率，说明SO₂与HgCl₂在CaO表面存在竞争吸附关系；吸附实验前后CaO的表征结果显示，与Hg⁰相比，HgCl₂更易与CaO表面各碱性位形成单配位、双配位等多种吸附构型，SO₂与HgCl₂在易形成单配位的活性位上形成竞争吸附关系，进而在一定程度上降低了CaO对HgCl₂的吸附效率。

关键词: CaO吸附剂, Hg, HgCl₂, 选择性吸附, SO₂毒化

CLC Number:

X511

LI Chunfeng, DUAN Yufeng, TANG Hongjian, ZHU Chun, ZHENG Yiwu, WEI Hongqi. Mercury selective adsorption characteristics and SO₂ poison performance on CaO[J]. CIESC Journal, 2017, 68(9): 3565-3572.

李春峰, 段钰锋, 汤红健, 朱纯, 郑逸武, 韦红旗. 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.

References 30

[1]	吴福全, 梁柱, 王雅玲, 等. 全球大气汞排放清单研究现状[J]. 环境监测管理与技术, 2015, 27(3):18-21. WU F Q, LIANG Z, WANG Y L, et al. Study on the status of global atmospheric mercury emission inventory[J]. The Administration and Technique of Environmental Monitoring, 2015, 27(3):18-21.
[2]	王起超, 沈文国, 麻壮伟. 中国燃煤汞排放量估算[J]. 中国环境科学, 1999, 19(4):318-321. WANG Q C, SHEN W G, MA Z W. The estimation of mercury emission from coal combustion in China[J]. China Environmental Science, 1999, 19(4):318-321.
[3]	朱纯, 段钰锋, 尹建军, 等. 卤化铵盐改性生物质稻壳焦的汞吸附特性[J]. 东南大学学报(自然科学版), 2013, 43(1):99-104. ZHU C, DUAN Y F, YIN J J, et al. Mercury adsorption by rice husk char sorbents modified by ammonium halide[J]. Journal of Southeast University(Natural Science Edition), 2013, 43(1):99-104.
[4]	周强, 段钰锋, 冒咏秋, 等. 活性炭汞吸附动力学及吸附机制研究[J]. 中国电机工程学报, 2013, 33(29):10-17. ZHOU Q, DUAN Y F, MAO Y Q, et al. Kinetics and mechanism of activated carbon adsorption for mercury removal[J]. Proceedings of the CSEE, 2013, 33(29):10-17.
[5]	李志超, 段钰锋, 王运军, 等. 300MW燃煤电厂ESP和WFGD对烟气汞的脱除特性[J]. 动力工程, 2013, 41(4):491-498. LI Z C, DUAN Y F, WANG Y J, et al. Mercury removal by ESP and WFGD in a 300 MW coal-fired power plant[J]. Journal of Fuel Chemistry and Technology, 2013, 41(4):491-498.
[6]	王震, 张丙凯, 刘晶, 等. H2O和SO2对汞在MnO2表面吸附影响的机理研究[J]. 工程热物理学报, 2016, 37(6):1335-1339. WANG Z, ZHANG B K, LIU J, et al. The influencing mechanism of H2O and SO2 on elemental mercury adsorption on MnO2 surface[J]. Journal of Engineering Thermophysics, 2016, 37(6):1335-1339.
[7]	钟犁, 肖平, 江建忠, 等. 燃煤电厂大气汞排放监测方法分析及试验研究[J]. 中国电机工程学报, 2012, 32(S1):158-163. ZHONG L, XIAO P, JIANG J Z, et al. Study on several measuring methods of mercury emission from coal-fired power plants[J]. Proceedings of the CSEE, 2012, 32(S1):158-163.
[8]	李辉, 王强, 朱法华. 燃煤电厂汞的排放控制要求与监测方法[J]. 环境工程技术学报, 2011, 1(3):226-231. LI H, WANG Q, ZHU F H. The control requirements and monitoring methods for mercury emission in coal-fired power plants[J]. Journal of Environmental Engineering Technology, 2011, 1(3):226-231.
[9]	任建莉, 周劲松, 骆仲泱, 等. 钙基类吸附剂脱除烟气中气态汞的试验研究[J]. 燃料化学学报, 2006, 34(5):557-561. REN J L, ZHOU J S, LUO Z Y, et al. Ca-based sorbents form mercury vapor removal from flue gas[J]. Journal of Fuel Chemistry and Technology, 2006, 34(5):557-561.
[10]	KRISHNAN S V, BAKHTEYAR H, SEDMAN C B. Mercury sorption mechanisms and control by calcium-based sorbents[C]//The 89th Air & Waste Management Association Annual Meeting. Nashvile, 1996.
[11]	GHORISHI S B, GULLETT B K. An experimental study on mercury sorption by activated carbons and calcium hydroxide[C]//Research Triangle Park. NC, 1997.
[12]	WAUGH E G. Mercury control on coal-fired flue gas using dry carbon-based injection pilot-scale demonstration[C]//The AWMA Annual Meeting. San Diego, CA, 1998.
[13]	KIM B G, LI X, BLOWERS P. Adsorption energies of mercury-containing species on CaO and temperature effects on equilibrium constants predicted by density functional theory calculations[J]. Langmuir, 2009, 25(5):2781-2789.
[14]	赵鹏飞. 固体吸附剂脱除燃煤烟气汞的实验与机理研究[D]. 武汉:华中科技大学, 2010. ZHAO P F. Experimental and mechanism study of elemental mercury removal from coal combustion flue gases by solid sorbents[D]. Wuhan:Huazhong University of Science and Technology, 2010.
[15]	GHORISHI S B, SEDMAN C B. Low concentration mercury sorption mechanisms and control by calcium-based sorbents:application in coal-fired processes[J]. Journal of the Air & Waste Management Association, 1998, 48(12):1191-1198.
[16]	佘敏, 段钰锋, 朱纯, 等. 改性生物质活性焦碳管吸附剂汞吸附性能实验研究[J]. 工程热物理学报, 2015, 36(9):2060-2064. SHE M, DUAN Y F, ZHU C, et al. Experimental study on mercury adsorption of modified biomass activated carbon for sorbents traps[J]. Journal of Engineering Thermophysic, 2015, 36(9):2060-2064.
[17]	TANG H J, DUAN Y F, ZHU C, et al. A novel carbon trap sampling system for coal-fired flue gas mercury measurement[J]. Journal of Southeast University, 2015, 31(2):244-248.
[18]	TANG H J, DUAN Y F, ZHU C, et al. Characteristics of a biomass-based sorbent trap and its application to coal-fired flue gas mercury emission monitoring[J]. International Journal of Coal Geology, 2016, 170:19-27.
[19]	LI Y H, LEE C W, GULLETT B K. Importance of activated carbon's oxygen surface functional groups on elemental mercury adsorption[J]. Fuel, 2003, 82(4):451-457.
[20]	ZENG H C, FENG J, GUO J. Removal of elemental mercury from coal combustion flue gas by chloride-impregnated activated carbon[J]. Fuel, 2004, 83(1):143-146.
[21]	LIU J, QU W Q, ZHENG C G. Theoretical studies of mercury-bromine species adsorption mechanism on carbonaceous surface[J]. Proceedings of the Combustion Institute, 2013, 34(2):2811-2819.
[22]	辛勤. 现代催化研究方法[M]. 北京:北京科技出版社, 2009:18-25. XIN Q. Modern Catalytic Research Methods[M]. Beijing:Beijing Science and Technology Press, 2009:18-25.
[23]	DAVYDOV A A. Infrared Spectroscopy of Adsorbed Species on the Surface of Transition Metal Oxides[M]. Chichester, 1990.
[24]	陈和生, 孙振亚, 邵景昌. 八种不同来源二氧化硅的红外光谱特征研究[J]. 硅酸盐通报, 2011, 30(4):934-937. CHEN H S, SUN Z Y, SHAO J C. Investigation on FT-IR spectroscopy for eight different sources of SiO2[J]. Bulletin of the Chinese Ceramic Society, 2011, 30(4):934-937.
[25]	GHORISHI S B, SEDMAN C B. Combined mercury and sulfur oxides control using calcium-based sorbents[C]//NASA. Washington, DC:1997.
[26]	GHORISHI S B, GULLETT B K. Sorption of mercury species by activated carbons and calcium-based sorbents:effect of temperature, mercury concentration and acid gases[J]. Waste Management & Research, 1998, 16(6):582-593.
[27]	GABER A, ABDEL-RAHIM M A, ABDEL-LATIEF A Y, et al. Influence of calcination temperature on the structure and porosity of nanocrystalline SnO2 synthesized by a conventional precipitation method[J]. Int. J. Electrochem. Sci., 2014, 9(1):81-95.
[28]	RUMAYOR M, DIAZ-SOMOANO M, LOPEZ-ANTON M A, et al. Mercury compounds characterization by thermal desorption[J]. Talanta, 2013, 114:318-322.
[29]	陈明明, 段钰锋, 周强, 等. 烟气组分对汞吸附影响的程序升温脱附[J]. 化工进展, 2016, 35(12):4065-4071. CHEN M M, DUAN Y F, ZHOU Q, et al. Temperature programmed desorption (TPD) studies on the effect of flue gas component on mercury adsorption[J]. Chemical Industry and Engineering Progress, 2016, 35(12):4065-4071.
[30]	PRESTO A A, GRANITE E J. Survey of catalysts for oxidation of mercury in flue gas[J]. Environmental Science & Technology, 2006, 40(18):5601-5609.

Mercury selective adsorption characteristics and SO₂ poison performance on CaO

CaO对汞的选择性吸附及SO₂毒化特性

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