铜铁基改性活性炭对烟气中二价汞的吸附

doi:10.16085/j.issn.1000-6613.2017-0984

摘要/Abstract

摘要： 随着工业的发展，环境问题日趋严重，而二价汞污染作为环境问题之一受到越来越多的关注。本文采用过体积浸渍法制备了铜基和铁基[CuCl₂，FeCl₃，Cu （NO₃）₂]改性的活性炭，考察了不同浓度以及煅烧温度制备的改性活性炭对模拟烟气中二价汞（HgCl₂）脱除性能的影响。通过吸附穿透实验的对比研究得出，无论是铜基或铁基改性的活性炭都对含氯化汞烟气有很好的吸附效果，并且300℃焙烧的0.01mol/L的氯化铜改性活性炭是深度脱除含氯化汞烟气效果最好的改性活性炭，其吸附量达到了4.55mg/g。在此基础上，进一步利用了XRD、BET、XPS常用表征手段研究了改性前后活性炭的物理化学特性，证明了铜基、铁基改性活性炭吸附氯化汞都是物理吸附与化学吸附共同作用的结果，并给出了相应的解释，以期为后续的科学研究提供一定的思路。

关键词: 烟气, 改性活性炭, 二价汞, 气相吸附

Abstract: With the development of industry, divalent mercury pollution as one of the environmental issues has been paid more and more attention around the world. In this paper, copper and iron-based[CuCl₂, FeCl₃, Cu(NO₃)₂] modified activated carbon were prepared by over-volume impregnation method. The effects of modified activated carbon prepared at different concentrations and calcination temperature on the removal of divalent mercury(HgCl₂) in simulated flue gas were investigated. Through the comparative experiments, both copper-based and iron-based activated carbon have a good adsorption effect on mercury-containing flue gas. The 0.01mol/L of copper chloride modified activated carbon calcined at 300℃ is the best removal of mercury chloride flue gas modified activated carbon, the adsorption capacity reached 4.55mg/g. On this basis, the physical and chemical characteristics were studied by using XRD, BET, SEM/EDS and XPS. It was proved that the adsorption of copper chloride and iron-based activated carbon is the result of the interaction between physical adsorption and chemical adsorption, and the corresponding explanation was given to provide some ideas for the follow-up scientific research.

Key words: flue gas, modified activated carbon, divalent mercury, gas-phase adsorption

中图分类号:

X701.3

胡亚楠, 王学谦, 宁平, 程金换, 陶雷. 铜铁基改性活性炭对烟气中二价汞的吸附[J]. 化工进展, 2018, 37(02): 775-782.

HU Yanan, WANG Xueqian, NING Ping, CHENG Jinhuan, TAO Lei. Adsorption of divalent mercury by copper/iron modified activated carbon[J]. Chemical Industry and Engineering Progress, 2018, 37(02): 775-782.

参考文献

[1] HSI H C, TSAI C Y, KUO T H, et al. Development of low-concentration mercury adsorbents from biohydrogen-generation agricultural residues using sulfur impregnation[J]. Bioresource Technology, 2011, 102(16):7470-7477.
[2] 段宁,柴发合,陈义珍,等.火电厂大气污染物排放标准与火电厂大气污染控制[J].中国能源, 2004, 26(12):20-24. DUAN N, CHAI F H, CHEN Y Z, et al. Heat-engine plant pollutant emission standard and heat-engine plant air pollution control[J]. China Energy Journal, 2004, 26(12):20-24.
[3] 孙青柯,黄亚继,王靓,等. 磁性Fe₃O₄-Ag复合纳米颗粒吸附剂脱汞性能实验研究[J].化工进展, 2017, 36(3):1101-1106. SUN Q K, HUANG Y J, WANG L, et al. Experimental study on mercury removal efficiencies of magnetic Fe₃O₄-Ag composite nanoparticles[J]. Chemical Industry and Engineering Progress, 2017, 36(3):1101-1106.
[4] 王运军,段钰锋,杨立国,等.燃煤电站布袋除尘器和静电除尘器脱汞性能比较[J].燃料化学学报, 2008, 36(1):23-29. WANG Y J, DUAN Y F, YANG L G, et al. Comparison of mercury removal performance between bag filter and electrostatic precipitator in coal-fired power station[J]. Journal of Fuel Chemistry, 2008, 36(1):23-29.
[5] 周琳. 成都经济区大气降尘中铅、镉的环境化学行为研究[D].成都:成都理工大学, 2006. ZHOU L. Study on environmental and chemical behavior of lead and cadmium in atmospheric dustfall in chengdu economic area[D]. Chengdu:Chengdu University of Technology, 2006.
[6] 陶铿.化工生产中汞污染防治[M].北京:石油化学工业出版社, 1978:89. TAO K. Chemical pollution control in chemical production[M]. Beijing:Petrochemical Industry Press, 1978:89.
[7] MERCEDES D S, M. ROSE M T. High-temperature removal of cadmium from a gasification flue gas using solid sorbents[J]. Fuel, 2005, 84(6):717-721.
[8] KLASSON K T, LIMAI M, BOIHEM L L, et al. Feasibility of mercury removal from simulated flue gas by activated chars made from poultry manures[J]. Journal of Environmental Management, 2010, 91(12):2466-2470.
[9] JIAO F, CHENG Y, ZHANG L, et al. Effects of HCl, SO₂ and H₂O in flue gas on the condensation behavior of Pb and Cd vapors inthe cooling section of municipal solid waste incineration[J]. Proceedings of the Combustion Institute, 2011, 33(2):2787-2793.
[10] 崔夏,马丽萍,邓春玲,等. 燃煤烟气中汞去除的研究进展[J].化工进展, 2011, 30(7):1607-1612. CUI X, MA L P, DEND C L, et al. Research progress of removing mercury from coal-fired flue gas[J]. Chemical Industry and Engineering Progress, 2011, 30(7):1607-1612.
[11] HADI P, TO M H, HUI C W, et al. Aqueous mercury adsorption by activated carbons[J]. Water Research, 2015, 73:37-55.
[12] THOMAS K K, LIMA I M. Feasibility of mercury removal from simulated flue gas by activated chars made from poultry manures[J]. Journal of Environmental Management, 2010, 91(12):2466-2470.
[13] WENDT J O L, LEE S J. High-temperature sorbents for Hg, Cd, Pb, and other trace metals:mechanisms and applications[J]. Fuel, 2010, 89(4):894-903.
[14] YANG X F, SHEN Z G. Silica nanoparticles capture atmospheric lead:implications in the treatment of environmental heavy metal pollution[J]. Chemosphere, 2013, 90(2):653-656.
[15] 张郃,赵建涛,房倚天,等. 活性炭催化氧化脱除单质汞的研究[J].燃料化学学报, 2011, 39(5):373-377. ZHANG H, ZAHO J T, FANG Q T, et al. Study on removal of elemental mercury by catalytic oxidation of activated carbon[J]. Journal of Fuel Chemistry, 2011, 39(5):373-377.
[16] QIAO S, CHEN J, LI J, et al. Adsorption and catalytic oxidation of gaseous elemental mercury in flue gas over MnO_x/alumina[J]. Industrial & Engineering Chemistry Research, 2009, 48(7):3317-3322.
[17] LI J, YAN N, QU Z, et al. Catalytic oxidation of elemental mercury over the modified catalyst Mn/α-Al₂O₃ at lower temperatures[J]. Environmental Science & Technology, 2009, 44(1):426-431.
[18] LI H, WU C Y, LI Y, et al. Superior activity of MnO_x-CeO₂/TiO₂ catalyst for catalytic oxidation of elemental mercury at low flue gas temperatures[J]. Applied Catalysis B:Environmental, 2012, 111:381-388.
[19] ANTOCHSHUK V, OLKHOVYK O, JARONIEC M, et al. Benzoylthiourea-modified mesoporous silica for mercury (Ⅱ) removal[J]. Langmuir, 2003, 19(7):3031-3034.
[20] DABROWSKI A, HUBICKI Z, PODKOSCIELNY P, et al. Selective removal of the heavy metal ions from waters and industrial wastewaters by ion-exchange method[J]. Chemosphere, 2004, 56(2):91-106.
[21] TAWABINI B, AL-KHALDI S, ATIEH M, et al. Removal of mercury from water by multi-walled carbon nanotubes[J]. Water Science & Technology, 2010, 61(3):591-598.
[22] VUKOVIC G D, MARINKOVIC A D, COLIC M, et al. Removal of cadmium from aqueous solutions by oxidized and ethylenediamine-functionalized multi-walled carbon nanotubes[J]. Chemical Engineering Journal, 2010, 157(1):238-248.
[23] ZHAO P, GUO X, ZHENG C. Removal of elemental mercury by iodine-modified rice husk ash sorbents[J]. Journal of Environmental Sciences, 2010, 22(10):1629-1636.
[24] ALIJANI H, SHARIATINIA Z, MASHHADI A A. Water assisted synthesis of MWCNTs over natural magnetic rock:an effective magnetic adsorbent with enhanced mercury (Ⅱ) adsorption property[J]. Chemical Engineering Journal, 2015, 281:468-481.
[25] 韩粉女,钟秦.燃煤烟气脱汞技术的研究进展[J].化工进展, 2011, 30(4):878-885. HAN F N, ZHONG Q. Research progress of coal-fired flue gas mercury removal technology[J]. Chemical Industry and Engineering Progress, 2011, 30(4):878-885.
[26] SKODRAS G, DIAMANTOPOULOU I, PANTOLEONTOS G, et al. Kinetic studies of elemental mercury adsorption in activated carbon fixed bed reactor[J]. Journal of Hazardous Materials, 2008, 158(1):1-13.
[27] LI X, LIU Z Y, LEE J Y. Adsorption kinetic and equilibrium study for removal of mercuric chloride by CuCl₂-impregnated activated carbon sorbent[J]. Journal of Hazardous Materials, 2013, 252/253(10):419-427.
[28] LUO J L, LU J J, NIU Q, et al. Preparation and characterization of benzoic acid-modified activated carbon for removal of gaseous mercury chloride[J]. Fuel, 2015, 160:440-445.
[29] HASSAN A, FABDEL-MOHSEN A M, ELHADITY H. Adsorption of arsenic by activated carbon, calcium alginate and their composite beads[J]. International Journal of Biological Macromolecules, 2014, 68(7):125-130.
[30] LEE S S, LEE J Y, KEENER T C. Bench-scale studies of in-duct mercury capture using cupric chloride-impregnated carbons[J]. Environmental Science & Technology, 2009, 43(8):2957-2962.
[31] 张颖峰,王晖,王波,等.活性炭负载Cu基催化剂催化甲醇氧化羰化合成碳酸二甲酯[J].化工进展, 2011, 30(s1):204-207. ZHANG Y F, WANG H, WANG B, et al. Synthesis of dimethyl carbonate by oxidative carbonylation of methanol catalyzed by Cu-based catalysts supported on activated carbon[J]. Chemical Industry and Engineering Progress, 2011, 30(s1):204-208.
[32] NGUYEN-THANH D, BANDOSZ T J. Activated carbons with metal containing bentonite binders as adsorbents of hydrogen sulfide[J]. Carbon, 2005, 43(2):359-367.
[33] LEE S J, SEO Y C, URNG J, et al. Removal of gas-phase elemental mercury by iodine-and chlorine-impregnated activated carbons[J]. Atmospheric Environment, 2004, 38(29):4887-4893.
[34] TAO S S, LI C T, FAN X P, et al. Activated coke impregnated with cerium chloride used for elemental mercury removal from simulated flue gas[J]. Chemical Engineering Journal, 2012, 210:547-556.