钙基脱硫剂用于冶炼烟气脱硫的模拟与实验
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摘要
提出了一种应用钙基脱硫剂脱除冶炼烟道气中高浓度SO_2并回收硫单质的方法。通过热力学模拟多种硫化物与SO_2之间的反应,筛选得出硫化钙(Ca S)适合作为化学链脱硫技术的脱硫剂,它在400~650℃范围内可将SO_2还原为单质硫,生成的固相产物为Ca SO_4而非Ca O。通过固定床反应器内的脱硫实验,发现温度对脱硫率和硫单质回收率影响较大。在400~650℃范围内温度越高,脱硫率和硫单质回收率越大;当温度高于600℃时,脱硫率和硫单质回收率基本相等。提高空速,则会降低脱硫率和硫单质回收率,但两者的差值随空速增大逐渐减小。当烟气中SO2浓度小于1%时,脱硫率维持在99.8%基本不变;SO_2浓度升至3.45%后,平均脱硫率急剧下降至92.1%;SO_2浓度越高,平均脱硫率越低。硫单质回收率随SO_2浓度增大存在一最佳范围。在脱硫反应后期,粒径较大的脱硫剂颗粒脱硫性能较低。SEM照片表明了脱硫剂颗粒随反应温度的升高团聚现象更为明显,XRD表征证明了反应中SO_2气体被还原为升华硫颗粒。
A method was developed to recover elemental sulfur from smelter off-gas with high SO_2 content. Based on thermodynamic simulation of reactions between some sulfides and SO_2, calcium sulfide(Ca S) was demonstrated to be a novel chemical desulfurizer. SO_2 was reduced to elemental sulfur by reacting with Ca S in temperature range from 400℃ to 650℃ and direct solid product was Ca SO4 rather than Ca O. The experimental desulfurization in a fixed bed reactor showed that reaction temperature had a strong effect on SO_2 removal efficiency and sulfur recovery ratio. When temperature was increased within the range of 400℃ and 650℃, both SO_2 removal efficiency and sulfur recovery ratio were raised gradually. When temperature was higher than 600℃, SO_2 removal efficiency was approximately equal to sulfur recovery ratio. Increasing gas velocity reduced SO_2 removal efficiency, sulfur recovery ratio, and difference between these two. SO_2 removal efficiency remained at 99.8% at SO_2 concentration below 1% but dropped sharply to 92.1% at SO_2 concentration up to 3.45%. Average SO_2 removal efficiency declined gradually when SO_2 concentration was continuously increased. With increase of SO_2 concentration, sulfur recovery ratio exhibited an optimal range. At late stage of desulfurization, large particle size of Ca S decreased SO_2 removal efficiency. SEM photos showed that desulfurizer particles agglomerated more obviously at increase of reaction temperature. XRD patterns verified sublimated elemental sulfur particles in the reduction of SO_2 by Ca S.
A method was developed to recover elemental sulfur from smelter off-gas with high SO_2 content. Based on thermodynamic simulation of reactions between some sulfides and SO_2, calcium sulfide(Ca S) was demonstrated to be a novel chemical desulfurizer. SO_2 was reduced to elemental sulfur by reacting with Ca S in temperature range from 400℃ to 650℃ and direct solid product was Ca SO4 rather than Ca O. The experimental desulfurization in a fixed bed reactor showed that reaction temperature had a strong effect on SO_2 removal efficiency and sulfur recovery ratio. When temperature was increased within the range of 400℃ and 650℃, both SO_2 removal efficiency and sulfur recovery ratio were raised gradually. When temperature was higher than 600℃, SO_2 removal efficiency was approximately equal to sulfur recovery ratio. Increasing gas velocity reduced SO_2 removal efficiency, sulfur recovery ratio, and difference between these two. SO_2 removal efficiency remained at 99.8% at SO_2 concentration below 1% but dropped sharply to 92.1% at SO_2 concentration up to 3.45%. Average SO_2 removal efficiency declined gradually when SO_2 concentration was continuously increased. With increase of SO_2 concentration, sulfur recovery ratio exhibited an optimal range. At late stage of desulfurization, large particle size of Ca S decreased SO_2 removal efficiency. SEM photos showed that desulfurizer particles agglomerated more obviously at increase of reaction temperature. XRD patterns verified sublimated elemental sulfur particles in the reduction of SO_2 by Ca S.
引文
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[27]TIAN H J,GUO Q J,YUE X H,et al.Investigation into sulfur release in reductive decomposition of calcium sulfate oxygen carrier by hydrogen and carbon monoxide[J].Fuel Process.Technol.,2010,91(11):1640-1649.
[28]李桂珍,曹龙文,邓文斌.大冶有色冶炼厂制酸尾气深度脱硫的实践[J].硫酸工业,2015,(4):23-25.LI G Z,CAO L W,DENG W B.Practice of further desulphurization of tail gas from sulphuric acid production in smelter of Daye[J].Sulphuric Acid Industry,2015,(4):23-25.
[29]王娟.基于催化氧化-吸附于一体的燃煤烟气中汞的测定方法及其应用研究[D].上海:上海交通大学,2012:30-33.WANG J.Measurement method and application of mercury in coal-fired flue gas based on the integration of catalytic oxidation and adsorption[D].Shanghai:Shanghai Jiao Tong University,2012:30-33.
[30]朱德力.活性炭纤维协同脱硫脱硝的试验研究[D].武汉:华中科技大学,2015:14-17.ZHU D L.Experimental study on simultaneous desulfurization and denitrification over activated carbon fibers[D].Wuhan:Huazhong University of Science&Technology,2015:14-17.
[31]MERCERA P D L,OMMEN J G V,DOESBURG E B M,et al.Zirconia as a support for catalysts-evolution of the texture and structure on calcination in air[J].Appl.Catal.A-Gen.,1990,57:127-148.
[2]杨彬.多变工况烟气对余热锅炉性能影响的研究[J].冶金能源,2017,36(3):34-37.YANG B.Research on the influence of flue gas on the performance of waste heat boiler[J].Energy for Metallurgical Industry,2017,36(3):34-37.
[3]ASANOV D A,FILYANOVA L A,ZAPASNYI V V,et al.Study of the performance indices of a dust-cleaning system at the Balkhash copper smelter[J].Metallurgist,2016,60(3/4):331-338.
[4]CHANG J,TIAN H J,JIANG J G,et al.Simulation and experimental study on the desulfurization for smelter off-gas using a recycling Cabased desulfurizer[J].Chem.Eng.J.,2016,291:225-237.
[5]ZAGORUIKO A N,VANAG S V.Reverse-flow reactor concept for combined SO2 and co-oxidation in smelter off-gases[J].Chem.Eng.J.,2014,238:86-92.
[6]ALBITAR M,MOHAMED M S,VISINTIN P,et al.Effect of granulated lead smelter slag on strength of fly ash-based geopolymer concrete[J].Constr.Build.Mater.,2015,83:128-135.
[7]WANG M,LIU G R,JIANG X X,et al.Thermochemical formation of polybrominateddibenzo-p-dioxins and dibenzofurans mediated by secondary copper smelter fly ash,and implications for emission reduction[J].Environ.Sci.Technol.,2016,50(14):7470-7479.
[8]《重有色金属冶炼设计手册》编委会.重有色金属冶炼设计手册:铜镍卷[M].北京:冶金工业出版社,1996:735-739.“Heavy non-ferrous metal smelting design manual”Editorial Board.Heavy Non-Ferrous Metal Smelting Design Manual:Copper-Nickel Volumes[M].Beijing:Metallurgical Industry Press,1996:735-739.
[9]张涛,杨德鑫,李娜,等.冶炼烟气制酸废酸废水处理中水综合利用[J].硫酸工业,2017,(2):21-23.ZHANG T,YANG D X,LI N,et al.Comprehensive utilization of neutralized water from waste acid wastewater treatment in smelting gas sulphuric acid production[J].Sulphuric Acid Industry,2017,(2):21-23.
[10]张涛.高浓度冶炼烟气制酸预转化工艺研究与实践[D].兰州:兰州大学,2015:1-3.ZHANG T.The research of sulphuric acid process with pre-conversion technology for high concentration smelter off-gas[D].Lanzhou:Lanzhou University,2015:1-3.
[11]袁俊宏.我国硫与硫铁矿产业现状及市场分析[J].硫酸工业,2016,(5):10-17.YUAN J H.Current situation and market analysis of China’s sulphur and pyrite industry[J].Sulphuric Acid Industry,2016,(5):10-17.
[12]FENG T,HUO M J,ZHAO X Q,et al.Reduction of SO2 to elemental sulfur with H2 and mixed H2/CO gas in an activated carbon bed[J].Chem.Eng.Res.Des.,2017,121:191-199.
[13]FENG T,ZHAO X,WANG T,et al.Reduction of SO2 with CO to elemental sulfur in activated carbon bed[J].Energ.Fuel,2016,30(8):6578-6584.
[14]王郎郎,王学谦,宁平,等.(NH4)2S吸收净化冶炼烟气中SO2回收硫资源的方法[J].化工学报,2014,65(11):4586-4592.WANG L L,WANG X Q,NING P,et al.Methods of SO2 removing from simulated smelting gas with(NH4)2S and sulfur recycling[J].CIESC Journal,2014,65(11):4586-4592.
[15]WANG X Q,XIONG J L,WANG L L,et al.Removal of elemental mercury and divalent mercury with ammonium sulfide in smelting gas containing SO2[C]//4th International Conference on Sustainable Energy and Environmental Engineering.Shenzhen,2015:416-422.
[16]EOB-CHOI M,SOHN H Y,AHMED Y M Z,et al.Effect of Ca SO4pelletization conditions on a novel process for converting SO2 to elemental sulfur by reaction cycles involving Ca SO4/Ca S(Ⅰ):Ca SO4pellet strength and reducibility by hydrogen[J].Chemical Engineering&Technology,2007,30(5):628-634.
[17]EOB-CHOI M,SOHN H Y,AHMED Y M Z,et al.Effect of Ca SO4pelletization conditions on a novel process for converting SO2 to elemental sulfur by reaction cycles involving Ca SO4/Ca S(Ⅱ):Reduction of SO2 with Ca S[J].Chemical Engineering&Technology,2007,30(7):951-954.
[18]SOHN H Y,KIM B S.A new process for converting SO2 to sulfur without generating secondary pollutants through reactions involving Ca S and Ca SO4[J].Environ.Sci.Technol.,2002,36:3020-3024.
[19]B?R J N,ROCHA M I,DE OLIVEIRA E J,et al.Impact of sulfur on catalytic partial oxidation of jet fuel surrogates over Rh/Al2O3[J].Int.J.Hydrogen.Energ.,2016,41(5):3701-3711.
[20]KUTNEY G.Sulfur—History,Technology,Applications&Industry[M].Canada:Chem Tech Publishing,2013:336-338.
[21]SAFADOOST A,DAVOODI M,MANSOORI S A A.Preventing corrosion and tube failure in sulfur condenser during normal operation,startup,and shutdown of the south pars gas processing plant(case study)[J].Nat.Gas Sci.Eng.,2014,19:105-115.
[22]MSILA X,BARNARD W,BILLING D G.Raman spectroscopic study of phosphogypsum thermal reduction with the carbonaceous material[J].Spectrochim.Acta A,2015,149:317-322.
[23]BEN-MANSOUR R,LI H,HABIB M A.Effects of oxygen carrier mole fraction,velocity distribution on conversion performance using an experimentally validated mathematical model of a CLC fuel reactor[J].Appl.Energ.,2017,208:803-819.
[24]ZHAO S,YOU C F.The effect of reducing components on the decomposition of desulfurization products[J].Fuel,2016,181:1238-1243.
[25]ZHENG M,SHEN L H,FENG X Q.In situ gasification chemical looping combustion of a coal using the binary oxygen carrier natural anhydrite ore and natural iron ore[J].Energ.Convers.Manage.,2014,83:270-283.
[26]昌晶,张聪,田红景,等.冶炼烟气干法脱硫过程中Ca S与SO2反应的实验及机理研究[J].高校化学工程学报,2016,30(1):240-247.CHANG J,ZHANG C,TIAN H J,et al.Experimental studies and mechanism of Ca S and SO2 reaction during smelting gas dry desulphurization processes[J].Journal of Chemical Engineering of Chinese Universities,2016,30(1):240-247.
[27]TIAN H J,GUO Q J,YUE X H,et al.Investigation into sulfur release in reductive decomposition of calcium sulfate oxygen carrier by hydrogen and carbon monoxide[J].Fuel Process.Technol.,2010,91(11):1640-1649.
[28]李桂珍,曹龙文,邓文斌.大冶有色冶炼厂制酸尾气深度脱硫的实践[J].硫酸工业,2015,(4):23-25.LI G Z,CAO L W,DENG W B.Practice of further desulphurization of tail gas from sulphuric acid production in smelter of Daye[J].Sulphuric Acid Industry,2015,(4):23-25.
[29]王娟.基于催化氧化-吸附于一体的燃煤烟气中汞的测定方法及其应用研究[D].上海:上海交通大学,2012:30-33.WANG J.Measurement method and application of mercury in coal-fired flue gas based on the integration of catalytic oxidation and adsorption[D].Shanghai:Shanghai Jiao Tong University,2012:30-33.
[30]朱德力.活性炭纤维协同脱硫脱硝的试验研究[D].武汉:华中科技大学,2015:14-17.ZHU D L.Experimental study on simultaneous desulfurization and denitrification over activated carbon fibers[D].Wuhan:Huazhong University of Science&Technology,2015:14-17.
[31]MERCERA P D L,OMMEN J G V,DOESBURG E B M,et al.Zirconia as a support for catalysts-evolution of the texture and structure on calcination in air[J].Appl.Catal.A-Gen.,1990,57:127-148.