溴改性金属有机骨架的合成及其对单质汞吸附

doi:10.11949/j.issn.0438-1157.20151730

化工学报 ›› 2016, Vol. 67 ›› Issue (6): 2380-2385.DOI: 10.11949/j.issn.0438-1157.20151730

溴改性金属有机骨架的合成及其对单质汞吸附

张笑¹, 沈伯雄², 池桂龙¹, 朱少文¹, 王泽怿²

1. 南开大学环境科学与工程学院, 天津 300071;
2. 河北工业大学能源与环境学院, 天津 300401

收稿日期:2015-11-18 修回日期:2016-03-18 出版日期:2016-06-05 发布日期:2016-06-05
通讯作者: 沈伯雄
基金资助:
国家自然科学基金项目(51541602)。

Preparation of bromine modified metal-organic frameworks for element mercury adsorption

ZHANG Xiao¹, SHEN Boxiong², CHI Guilong¹, ZHU Shaowen¹, WANG Zeyi²

1. College of Environmental Science and Engineering, Nankai University, Tianjin 300071, China;
2. School of Energy and Environmental Engineering, Hebei University of Technology, Tianjin 300401, China

Received:2015-11-18 Revised:2016-03-18 Online:2016-06-05 Published:2016-06-05
Supported by:
supported by the National Natural Science Foundation of China (51541602).

摘要/Abstract

摘要：

采用溶剂热法制备了溴改性的金属有机骨架(metal organic framework,MOF),通过模拟烟气动态吸附方法对材料单质汞(Hg⁰)吸附性能进行研究。利用X射线衍射(XRD)、X射线光电子能谱(XPS)、综合吸附仪对晶体结构、形貌和组分进行表征。结果表明改性后晶体结构不变,比表面积、孔容下降,溴以共价键固定在材料中。改性前和改性后材料对Hg⁰的吸附效率都有随温度升高而增加趋势。模拟烟气反应床吸附实验证明240℃条件下,溴改性MOF10h内吸附效率高于95%,同等实验条件下,非改性MOF以及传统活性炭吸附剂吸附汞5h后效率低于75%。

关键词: 金属有机骨架载体, 溴改性, 吸附, 单质汞, 烟道气

Abstract:

Bromine modified metal organic framework (MOF) was synthesized by solvothermal method for element mercury (Hg⁰) adsorption. The crystal structure, chemical and texture properties of the modified MOF were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and N₂ adsorption. Covalent bromine was detected on the surface of the modified MOF and the modification process resulted in a lower specific surface area and total pore volume than those of unmodified MOF. Hg⁰ removal efficiencies increased with temperature for both modified MOF and un-modified MOF sorbent. In the dynamic adsorption experiments, which were conducted trying to mimic the flue gas condition, the bromine modified MOF showed a high Hg⁰ removal efficiency of above 95% for 10 h at 240℃, while the efficiency dropped to 75% within 5 h for both unmodified MOF and traditional active carbon sorbent.

Key words: metal-organic frameworks support, bromine modification, absorption, elemental mercury, flue gas

中图分类号:

X511

张笑, 沈伯雄, 池桂龙, 朱少文, 王泽怿. 溴改性金属有机骨架的合成及其对单质汞吸附[J]. 化工学报, 2016, 67(6): 2380-2385.

ZHANG Xiao, SHEN Boxiong, CHI Guilong, ZHU Shaowen, WANG Zeyi . Preparation of bromine modified metal-organic frameworks for element mercury adsorption[J]. CIESC Journal, 2016, 67(6): 2380-2385.

参考文献 26

[1]	郑刘根, 刘桂建, 齐翠翠, 等. 中国煤中汞的环境地球化学研究 [J]. 中国科学技术大学学报, 2007, 37(8): 953-963. DOI: 10.3969/j.issn.0253-2778.2007.08.021. ZHENG L G, LIU G J, QI C C, et al. Study on environmental geochemistry of mercury in Chinese coals [J]. Journal of University of Science and Technology of China, 2007, 37(8): 953-963. DOI: 10.3969/j.issn.0253-2778.2007.08.021.
[2]	PACYNA E G, PACYN J M, SUNDSETH K, et al. Global emission of mercury to the atmosphere from anthropogenic sources in 2005 and projections to 2020 [J]. Atmospheric Environment, 2010, 44(20): 2487-2499.
[3]	CAO Y, CHENG C M, CHEN C W, et al. Abatement of mercury emissions in the coal combustion process equipped with a fabric filter baghouse [J]. Fuel,2008, 7(15): 3322-3330.
[4]	NOLAN P S, REDINGER K E, AMRHEIN G T, et al. Demonstration of additive use for enhanced mercury emissions control in wet FGD systems [J]. Fuel Processing Technology,2002, 85(6): 587-600.
[5]	张安超, 向军, 孙路石, 等. 新型改性吸附剂制备、表征及脱除单质汞的实验研究 [J]. 化工学报, 2009, 60 (6): 1546-1553. ZHANG A C, XIANG J, SUN L S, et al. Synthesis and characterization of novel modified sorbents and their performance for elemental mercury removal [J]. CIESC Journal, 2009, 60 (6): 1546-1553.
[6]	沈伯雄, 左琛. 燃煤烟气汞排放与控制研究进展 [J]. 安全与环境学报, 2012, 12(2): 100-103. DOI: 101 3969/j. issn. 1009-60941 20121 021024. SHEN B X, ZUO C. Review on the research progress of the mercury emission in flue gas in coal burning [J]. Journal of Safety and Environment, 2012, 12(2): 100-103. DOI: 101 3969/j. issn. 1009-60941 20121 021024.
[7]	SLEMR F, SCHUSTER G, SEILER W. Distribution, speciation, and budget of atmospheric mercury [J].Journal of Atmospheric Chemistry, 1985, 3(4): 407-434.
[8]	赵毅, 刘松涛, 马宵颖, 等. 改性粉煤灰吸收剂对单质汞的脱除研究 [J]. 中国电机工程学报, 2008, 28(20): 55-60. ZHAO Y, LIU S T, MA X Y, et al. Removal of Hg0 by modified fly ash absorbent [J].Proceedings of the CSEE, 2008, 28(20):55-60
[9]	HE C, SHEN B, CHEN J, et al. Adsorption and oxidation of elemental mercury over Ce-MnOx/Ti-PILCs [J].Environmental Science & Technology, 2014, 48(14): 7891-7898.
[10]	张海茹, 吴昊, 刘浩, 等. 活性焦汞吸附特性及动力学机理分析[J]. 化工学报, 2013, 64(3): 1076-1083.DOI:10.3969/j.issn. 0438-1157.2013.03.041. ZHANG H R, WU H, LIU H, et al. Performance and kinetics of mercury adsorption over Tai-Xi activated coke [J]. CIESC Journal, 2013, 64(3): 1076-1083.DOI:10.3969/j.issn.0438-1157.2013.03.041.
[11]	LI G, SHEN B, LI Y, et al. Removal of element mercury by medicine residue derived biochars in presence of various gas compositions [J]. Journal of Hazardous Material, 2015, 298(15): 162-169.
[12]	DE M, AZARGOHAR R, DALAI A. K, et al. Mercury removal by bio-char based modified activated carbons [J].Fuel, 2013, 103(1): 570-578.
[13]	沈伯雄, 蔡记, 陈建宏, 等. KBr和KI改性黏土脱除模拟烟气中的单质汞[J] .化工学报, 2014, 65(2): 711-717. DOI:10.3969/j.issn.0438-1157.2014.02.048. SHEN B X, CAI J, CHEN J H, et al. Removal of element mercury from simulated flue gas by clay modified with KBr and KI [J]. CIESC Journal, 2014, 65(2):711-717. DOI:10.3969/j.issn.0438-1157. 2014.02.048.
[14]	杜雯, 殷立宝, 禚玉群, 等. 100 MW燃煤电厂非碳基吸附剂喷射脱汞实验研究 [J]. 化工学报, 2014, 65(11): 4413-4419. DOI:10.3969/j.issn.0438-1157.2014.11.028. DU W, YIN L B, ZHUO Y Q, et al. Experimental study on mercury capture using non-carbon sorbents in 100 MW coal-fired power plant [J]. CIESC Journal, 2014, 65(11): 4413-4419. DOI:10.3969/j.issn. 0438-1157.2014.11.028.
[15]	SAHA A, ABRAM D N, KUHL K P, et al. An X-ray photoelectron spectroscopy study of surface changes on brominated and sulfur-treated activated carbon sorbents during mercury capture: performance of pellet versus fiber sorbents [J]. Environmental Science & Technology, 2013, 47(23): 13695-13701.
[16]	SUN W, YAN N, JIA J. Removal of elemental mercury in flue gas by brominated activated carbon [J]. China Environmental Science, 2006, 26(3): 257-261.
[17]	BISSON T M, MACLEAN L C W, HU Y, et al. Characterization of mercury binding onto a novel brominated biomass ash sorbent by X-ray absorption spectroscopy [J]. Environmental Science & Technology, 2012, 46(21): 12186-12193.
[18]	FURUKAWA H, CORDOVA K E, O'KEEFFE M, et al. The chemistry and applications of metal-organic frameworks [J]. Science, 2013, 341(6149): 1230444-1230444.
[19]	YEE K K, REIMER N, LIU J, et al. Effective mercury sorption by thiol-laced metal-organic frameworks: in strong acid and the vapor phase [J]. Journal of the American Chemical Society, 2013, 135(21): 7795-7798.
[20]	YAO Y, VELPARI V, ECONOMY J. In search of brominated activated carbon fibers for elemental mercury removal from power plant effluents [J]. Journal of Materials Chemistry A, 2013, 1(39): 12103-12108.
[21]	GARIBAY S J, COHEN S M. Isoreticular synthesis and modification of frameworks with the UiO-66 topology [J]. Chemical Communications, 2010, 46(41): 7700-7702.
[22]	CAVKA J H, JAKOBSEN S, OLSBYE U, et al. A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability [J]. Journal of the American Chemical Society, 2008, 130(42): 13850-13851.
[23]	FREY B L, CORN R M. Covalent attachment and derivatization of poly(L-lysine) monolayers on gold surfaces as characterized by polarization-modulation FT-IR spectroscopy [J]. Analytical Chemistry, 1996, 68(18): 3187-3193.
[24]	DESHPANDE R K, MINNAAR J L, TELFER S G. Thermolabile groups in metal-organic frameworks: suppression of network interpenetration, post-synthetic cavity expansion, and protection of reactive functional groups [J]. Angewandte Chemie, 2010, 122(27): 4702-4706.
[25]	GRANITE E J, PENNLINE H W, HARGIS R A. Novel sorbents for mercury removal from flue gas [J]. Industrial & Engineering Chemistry Research, 2000, 39(4): 1020-1029.
[26]	HUGGINS F E, YAP N, HUFFMAN G P, et al. XAFS characterization of mercury captured from combustion gases on sorbents at low temperatures [J]. Fuel Processing Technology, 2003, 82(2): 167-196.

溴改性金属有机骨架的合成及其对单质汞吸附

Preparation of bromine modified metal-organic frameworks for element mercury adsorption

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