CIESC Journal ›› 2018, Vol. 69 ›› Issue (5): 2233-2241.doi: 10.11949/j.issn.0438-1157.20180048

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Simulation and experimental study on smelter off-gas desulfurization using calcium-based desulfurizer

CHANG Jing1, HU Xiude2, TIAN Hongjing3, YUAN Fuqi1, XU Jingwen3, GUO Qingjie2,3   

  1. 1. College of Resources and Environment, Qingdao Agricultural University, Qingdao 266109, Shandong, China;
    2. State Key Laboratory of High-efficiency Coal Utilization and Green Chemical Engineering, Ningxia University, Yinchuan 750021, Ningxia, China;
    3. College of Chemical Engineering, Qingdao University of Science & Technology, Qingdao 266042, Shandong, China
  • Received:2018-01-15 Revised:2018-01-23
  • Supported by:

    supported by the National Natural Science Foundation of China(51608291, 51106077), the Natural Science Foundation of Shandong Province(ZR2017QB019), the Qingdao Independent Innovation Plan (16-5-1-30-jch), the Ningxia Introduction Innovation Team Plan, and the Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering (2017-K19).

Abstract:

A method was developed to recover elemental sulfur from smelter off-gas with high SO2 content. Based on thermodynamic simulation of reactions between some sulfides and SO2, calcium sulfide (CaS) was demonstrated to be a novel chemical desulfurizer. SO2 was reduced to elemental sulfur by reacting with CaS in temperature range from 400℃ to 650℃ and direct solid product was CaSO4 rather than CaO. The experimental desulfurization in a fixed bed reactor showed that reaction temperature had a strong effect on SO2 removal efficiency and sulfur recovery ratio. When temperature was increased within the range of 400℃ and 650℃, both SO2 removal efficiency and sulfur recovery ratio were raised gradually. When temperature was higher than 600℃, SO2 removal efficiency was approximately equal to sulfur recovery ratio. Increasing gas velocity reduced SO2 removal efficiency, sulfur recovery ratio, and difference between these two. SO2 removal efficiency remained at 99.8% at SO2 concentration below 1% but dropped sharply to 92.1% at SO2 concentration up to 3.45%. Average SO2 removal efficiency declined gradually when SO2 concentration was continuously increased. With increase of SO2 concentration, sulfur recovery ratio exhibited an optimal range. At late stage of desulfurization, large particle size of CaS decreased SO2 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 SO2 by CaS.

Key words: flue gas, recovery, reduction, SO2 removal efficiency

CLC Number: 

  • X701.7

[1] 马晓辉, 匡轩毅, 赵军生. 铜冶炼余热高效利用技术研究[J]. 硫酸工业, 2017, (7):28-30. MA X H, KUANG X Y, ZHAO J S. Study on high efficient utilization of waste heat in coppers melting industry[J]. Sulphuric Acid Industry, 2017, (7):28-30.
[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 Ca-based 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 CaSO4 pelletization conditions on a novel process for converting SO2 to elemental sulfur by reaction cycles involving CaSO4/CaS(Ⅰ):CaSO4 pellet 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 CaSO4 pelletization conditions on a novel process for converting SO2 to elemental sulfur by reaction cycles involving CaSO4/CaS(Ⅱ):Reduction of SO2 with CaS[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 CaS and CaSO4[J]. Environ. Sci. Technol., 2002, 36:3020-3024.
[19] BÄR 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:ChemTech 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CaS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 CaS 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.

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