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

doi:10.11949/j.issn.0438-1157.20180048

Abstract

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

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SO₂并回收硫单质的方法。通过热力学模拟多种硫化物与SO₂之间的反应，筛选得出硫化钙（CaS）适合作为化学链脱硫技术的脱硫剂，它在400～650℃范围内可将SO₂还原为单质硫，生成的固相产物为CaSO₄而非CaO。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；SO₂浓度升至3.45%后，平均脱硫率急剧下降至92.1%；SO₂浓度越高，平均脱硫率越低。硫单质回收率随SO₂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SO₂气体被还原为升华硫颗粒。

关键词: 烟道气, 回收, 还原, 脱硫率

CLC Number:

X701.7

CHANG Jing, HU Xiude, TIAN Hongjing, YUAN Fuqi, XU Jingwen, GUO Qingjie. Simulation and experimental study on smelter off-gas desulfurization using calcium-based desulfurizer[J]. CIESC Journal, 2018, 69(5): 2233-2241.

昌晶, 胡修德, 田红景, 远富启, 许静文, 郭庆杰. 钙基脱硫剂用于冶炼烟气脱硫的模拟与实验[J]. 化工学报, 2018, 69(5): 2233-2241.

References 31

[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.

Related Articles 15

[1]	Congqi HUANG, Yimei WU, Jianye CHEN, Shuangquan SHAO. Simulation study of thermal management system of alkaline water electrolysis device for hydrogen production [J]. CIESC Journal, 2023, 74(S1): 320-328.
[2]	Runmiao GAO, Mengjie SONG, Enyuan GAO, Long ZHANG, Xuan ZHANG, Keke SHAO, Zekang ZHEN, Zhengyong JIANG. Review on greenhouse gas reduction related to refrigerants in cold chain [J]. CIESC Journal, 2023, 74(S1): 1-7.
[3]	Xiaoxiong FAN, Lifang HAO, Chuigang FAN, Songgeng LI. Study on the catalytic denitrification performance of low-temperature NH₃-SCR over LaMnO₃/biochar catalyst [J]. CIESC Journal, 2023, 74(9): 3821-3830.
[4]	Song HE, Qiaomai LIU, Guangshuo XIE, Simin WANG, Juan XIAO. Two-phase flow simulation and surrogate-assisted optimization of gas film drag reduction in high-concentration coal-water slurry pipeline [J]. CIESC Journal, 2023, 74(9): 3766-3774.
[5]	Jiayi ZHANG, Jiali HE, Jiangpeng XIE, Jian WANG, Yu ZHAO, Dongqiang ZHANG. Research progress of pervaporation technology for N-methylpyrrolidone recovery in lithium battery production [J]. CIESC Journal, 2023, 74(8): 3203-3215.
[6]	Ruihang ZHANG, Pan CAO, Feng YANG, Kun LI, Peng XIAO, Chun DENG, Bei LIU, Changyu SUN, Guangjin CHEN. Analysis of key parameters affecting product purity of natural gas ethane recovery process via ZIF-8 nanofluid [J]. CIESC Journal, 2023, 74(8): 3386-3393.
[7]	Qiyu ZHANG, Lijun GAO, Yuhang SU, Xiaobo MA, Yicheng WANG, Yating ZHANG, Chao HU. Recent advances in carbon-based catalysts for electrochemical reduction of carbon dioxide [J]. CIESC Journal, 2023, 74(7): 2753-2772.
[8]	Yuying GUO, Jiaqiang JING, Wanni HUANG, Ping ZHANG, Jie SUN, Yu ZHU, Junxuan FENG, Hongjiang LU. Water-lubricated drag reduction and pressure drop model modification for heavy oil pipeline [J]. CIESC Journal, 2023, 74(7): 2898-2907.
[9]	Tan ZHANG, Guang LIU, Jinping LI, Yuhan SUN. Performance regulation strategies of Ru-based nitrogen reduction electrocatalysts [J]. CIESC Journal, 2023, 74(6): 2264-2280.
[10]	Yanmei ZHANG, Tao YUAN, Jiang LI, Yajie LIU, Zhanxue SUN. Study on the construction of high-efficient SRB mixed microflora and its performance under acid stress [J]. CIESC Journal, 2023, 74(6): 2599-2610.
[11]	Nan HU, Demin TAO, Zhaolan YANG, Xuebing WANG, Xiangxu ZHANG, Yulong LIU, Dexin DING. Remediation of percolate water from uranium tailings reservoir by coupling iron-carbon micro-electrolysis and sulfate reducing bacteria [J]. CIESC Journal, 2023, 74(6): 2655-2667.
[12]	Guohua SHI, Linshen HE, Xiling ZHAO, Shigang ZHANG. Study of removal characteristics of particulate matters within flue gas by spray tower for waste-heat recovery [J]. CIESC Journal, 2023, 74(4): 1735-1745.
[13]	Ruizhe CHEN, Leilei CHENG, Jing GU, Haoran YUAN, Yong CHEN. Research progress in chemical recovery technology of fiber-reinforced polymer composites [J]. CIESC Journal, 2023, 74(3): 981-994.
[14]	Wan XU, Zhenbin CHEN, Huijuan ZHANG, Fangfang NIU, Ting HUO, Xingsheng LIU. Study on synthesis, adsorption and desorption performance of linear temperature-sensitive segment polymer regulated intelligent $R e O 4 -$ ion-imprinted polymer [J]. CIESC Journal, 2023, 74(2): 941-952.
[15]	Shaozhuang WANG, Dunxi YU, Jiayi LI, Jingkun HAN, Xin YU, Fangqi LIU. Effects of torrefaction with flue gas on grindability of corn stalk [J]. CIESC Journal, 2023, 74(2): 861-870.