煤气脱汞剂的研究进展Research development of sorbents for mercury removal in fuel gas
韩洁茹,常丽萍,王建成,韩丽娜,鲍卫仁
HAN Jie-ru1,CHANG Li-ping1,WANG Jian-cheng1,HAN Li-na2,BAO Wei-ren1(1.Key Laboratory of Coal Science and Technology
摘要(Abstract):
粗煤气的净化是制约煤气化技术应用的瓶颈之一,在煤气化过程中煤中的部分硫、氮和挥发性重金属会随着气化产物一起迁移进入气相中,而影响气体的进一步利用,必须对其进行高效脱除,特别是还原性煤基气体中单质汞的脱除。本文对目前已有的脱汞技术进行了概述,重点介绍载硫活性炭、金属氧化物及贵重金属负载型吸附剂等,并对煤气脱汞技术面临的挑战及发展方向进行了阐述。活性炭吸附法是目前研究最广泛的技术,但是成本较高,有效脱汞温度最高只能达到150℃;以氧化铁为代表的金属氧化物吸附剂在150℃下具有较高的脱硫脱汞能力;贵金属吸附剂在中温(200~350℃)脱汞方面有很大的潜力,且有一定的耐硫性。煤气脱汞与其它污染物(如硫、氯等)联合脱除被认为是具有较好应用前景的技术。
The cleaning technology for the raw gas is one of the key obstacles restraining the development of gasification technology.During the gasification process,parts of sulfur,nitrogen and volatile heavy metal in coal would transfer to gaseous phase together with the gasification products,which further affect the following usage of gas.Thus,it is necessary to remove the components effectively,especially the simple substance of mercury from the coal derived gas.Introduce the current technologies for Hg capture,and the active carbon supported sulfur,metal oxides and noble metal sorbents.Besides,the main challenges of Hg capture and its development direction are also analyzed.The adsorption of Hg with active carbon is well studied,however,its high cost and low working temperature(≤150 ℃) are the main defects.Below 150 ℃,the ferric oxide is a represent of metal oxides performing high desulfurization and Hg capture ability,simultaneously the noble sorbents has great potential for Hg removal between 200 ℃ and 350 ℃.Furthermore,it has a sulfur tolerance to some extent.The combination of removal of Hg and other pollutants(sulfur,chlorine,etc.) has good application prospect.
关键词(KeyWords):
煤气;吸附剂;汞;硫化氢
fuel gas;sorbents;mercury;hydrogen sulfide
基金项目(Foundation): 国家自然科学基金资助项目(21006067,21276170);; 山西省自然科学基金资助项目(2010021008-1,2011021008-4);; 中国博士后面上项目(20110491630)
作者(Author):
韩洁茹,常丽萍,王建成,韩丽娜,鲍卫仁
HAN Jie-ru1,CHANG Li-ping1,WANG Jian-cheng1,HAN Li-na2,BAO Wei-ren1(1.Key Laboratory of Coal Science and Technology
DOI: 10.13226/j.issn.1006-6772.2013.02.007
参考文献(References):
- [1]许世森,危石让.分析评价大型IGCC电站中煤气净化工艺的设备和技术特点[J].洁净煤技术,1999,5(1):47-51.
- [2]Pavlish J H,Sondreal E A,Mann M D,et al.Status reviewof mercury control options for coal-fired power plants[J].Fuel Processing Technology,2003,82(2/3):89-165.
- [3]Granite E J,Pennline H W,Hargis R A,et al.Novel sor-bents for mercury removal from flue gas[J].Industrial&Engineering Chemistry Research,2000,39(4):1020-1029.
- [4]任建莉,周劲松,骆仲涣,等.汞吸附过程的试验研究和数学模型[J].中国电机工程学报,2006,26(11):1-6.
- [5]Yang S,Guo Y,Yan N,et al.Capture of gaseouselemental mercury from flue gas using a magnetic andsulfur poisoning resistant sorbent Mn/γ-Fe2O3 at lowertemperatures[J].Journal of Hazardous Materials,2011,186(1):508-515.
- [6]Wen X,Li C,Fan X,et al.Experimental study of gaseouselemental mercury eemoval with CeO2/γ-Al2O3[J].En-ergy&Fuels,2011,25(7):2939-2944.
- [7]Li H,Wu C-Y,Li Y,Zhang J.CeO2-TiO2 catalysts forcatalytic oxidation of elemental mercury in low-rank coalcombustion flue gas[J].Environ Sci Technol,2011,45(17):7394-7400.
- [8]Liu Y,Yang H,Xu Z,et al.Novel regenerable sorbent formercury capture from flue gases of coal-fired power plant[J].Environmental Science&Technology,2008,42(16):6205-6210.
- [9]Reed G P,Ergüdenler A,Grace J R,et al.Control of gasi-fier mercury emissions in a hot gas filter:the effect oftemperature[J].Fuel,2001,80(5):623-634.
- [10]Krishnan S V,Gullett B K,Jozewicz W.Sorption of ele-mental mercury by activated carbons[J].EnvironmentalScience Technology,1994,28(8):1506-1512.
- [11]Liu W,Vidic R D.Optimization of sulfur impregnationprotocol for fixed bed application of activated carbon-based sorbents for gas-phase mercury removal[J].Envi-ronmental Science and Technology,1998,32(5):531-538.煤质技术《洁净煤技术》2013年第19卷第2期
- [12]Hsi H-C,Rood M J,Rostam-Abadi M,et al.Effects ofsulfur impregnation temperature on the properties andmercury adsorption capacities of activated carbon fibers(ACFs)[J].Environmental Science and Technology,2001,35(13):2785-2791.
- [13]Korpiel J A,Vidic R D.Effect of sulfur impregnationmethod on activated carbon uptake of gas-phase mercury[J].Environmental Science and Technology,1997,31(8):2319-2325.
- [14]Feng W,Borguet E,Vidic R D.Sulfurization of a carbonsurface for vapor phase mercury removal-II:Sulfur formsand mercury uptake[J].Carbon,2006,44(14):2998-3004.
- [15]Hsi H-C,Rood M J,Rostam-Abadi M,et al.Mercuryadsorption properties of sulfur-impregnated adsorbents[J].Environmental Engineering,2002,128(11):1080-1089.
- [16]张鹏宇,曾汉才,张柳.活化处理的活性炭吸附汞的试验研究[J].电力科学与工程,2004,2(3):1-3.
- [17]Vidic R D,Siler D P.Vapor-phase elemental mercuryadsorption by activated carbon impregnated with chlorideand chelating agents[J].Carbon,2001,39(1):3-14.
- [18]Zeng H,Jin F,Guo J.Removal of elemental mercuryfrom coal combustion flue gas by chloride-impregnatedactivated carbon[J].Fuel,2004,83(1):143-146.
- [19]孙巍,晏乃强,贾金平.载溴活性炭去除烟气中的单质汞[J].中国环境科学,2006,26(3):257-261.
- [20]汪祥胜.天然气和烃油脱汞技术研究进展[J].化学工业与工程技术,2010,31(3):29-32.
- [21]Granite E J,Myers C R,King W P,et al.Sorbents formercury capture from fuel gas with application to gasifi-cation systems[J].Industrial&Engineering ChemistryResearch,2006,45(13):4844-4848.
- [22]Poulston S,Granite E J,Pennline H W,et al.Metal sor-bents for high temperature mercury capture from fuel gas[J].Fuel,2007,86(14):2201-2203.
- [23]Baltrus J P,Granite E J,Rupp E C,et al.Effect of palla-dium dispersion on the capture of toxic components fromfuel gas by palladium-alumina sorbents[J].Fuel,2011,90(5):1992-1998.
- [24]Aboud S,Sasmaz E,Wilcox J.Mercury adsorption onPdAu,PdAg and PdCu alloys[J].Main Group Chemistry,2008,7(3):205-215.
- [25]Gao H,Lin Y S,Li Y,et al.Chemical stability and itsimprovement of palladium-based metallic membranes[J].Industrial&Engineering Chemistry Research,2004,43(22):6920-6930.
- [26]Kamakoti P,Morreale B D,Ciocco M V,et al.Predictionof hydrogen flux through sulfur-tolerant binary alloymembranes[J].Science,2005,307(5709):569-573.
- [27]Babu N S,Lingaiah N,Kumar J V,et al.Studies on alu-mina supported Pd-Fe bimetallic catalysts prepared bydeposition-precipitation method for hydrodechlorination ofchlorobenzene[J].Applied Catalysis A:General,2009,367(1/2):70-76.
- [28]Baltrus J P,Granite E J,Pennline H W,et al.Surfacecharacterization of palladium-alumina sorbents for high-temperature capture of mercury and arsenic from fuel gas[J].Fuel,2010,89(6):1323-1325.
- [29]Baltrus J P,Granite E J,Stanko D C,et al.Surface char-acterization of Pd/Al2O3 sorbents for mercury capturefrom fuel gas[J].Main Group Chemistry,2008,7(3):217-225.
- [30]Han L,Lv X,Wang J,et al.Palladium-Iron bimetal sor-bents for simultaneous capture of hydrogen sulfide andmercury from simulated syngas[J].Energy&Fuels,2012,26(3):1638-1644.
- [31]Rupp E C,Granite E J,Stanko D C.Laboratory scalestudies of Pd/γ-Al2O3 sorbents for the removal of tracecontaminants from coal-derived fuel gas at elevatedtemperatures[J].Fuel,2011,108:131-136.
- [32]Wu S,Azharuddin M,Sasaoka E.Characteristics of theremoval of mercury vapor in coal derived fuel gas over i-ron oxide sorbents[J].Fuel,2006,85(2):213-218.
- [33]Wu S,Oya N,Ozaki M,et al.Development of iron oxidesorbents for Hg0 removal from coal derived fuel gas:Sul-fidation characteristics of iron oxide sorbents and activityfor COS formation during Hg0 removal[J].Fuel,2007,86(17/18):2857-2863.
- [34]Wu S,Ozaki M,Uddin M A,et al.Development of iron-based sorbents for Hg0 removal from coal derived fuelgas:Effect of hydrogen chloride[J].Fuel,2008,87(4/5):467-474.
- [35]Ozaki M,Uddin M A,Sasaoka E,et al.Temperatureprogrammed decomposition desorption of the mercuryspecies over spent iron-based sorbents for mercury re-moval from coal derived fuel gas[J].Fuel,2008,87(17/18):3610-3615.
- [36]Wang J,Zhang Y,Han L,et al.Simultaneous removal ofhydrogen sulfide and mercury from simulated syngas byiron-based sorbents[J].Fuel,2012,103(1):73-79.