钙基脱硫剂用于冶炼烟气脱硫的模拟与实验

doi:10.11949/j.issn.0438-1157.20180048

化工学报 ›› 2018, Vol. 69 ›› Issue (5): 2233-2241.DOI: 10.11949/j.issn.0438-1157.20180048

钙基脱硫剂用于冶炼烟气脱硫的模拟与实验

昌晶¹, 胡修德², 田红景³, 远富启¹, 许静文³, 郭庆杰^2,3

1. 青岛农业大学资源与环境学院, 山东青岛 266109;
2. 省部共建煤炭高效利用与绿色化工国家重点实验室(宁夏大学), 宁夏银川 750021;
3. 青岛科技大学化工学院, 山东青岛 266042

收稿日期:2018-01-15 修回日期:2018-01-23 出版日期:2018-05-05 发布日期:2018-05-05
通讯作者: 田红景
基金资助:
国家自然科学基金项目（51608291，51106077）；山东省自然科学基金项目（ZR2017QB019）；青岛市自主创新计划项目（16-5-1-30-jch）；宁夏引进科技创新团队项目（煤炭清洁利用）；煤炭高效利用与绿色化工国家重点实验室开放课题（2017-K19）。

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

CHANG Jing¹, HU Xiude², TIAN Hongjing³, YUAN Fuqi¹, XU Jingwen³, GUO Qingjie^2,3

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 Online:2018-05-05 Published:2018-05-05
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).

摘要/Abstract

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

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

中图分类号:

X701.7

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.

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.

参考文献 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.

钙基脱硫剂用于冶炼烟气脱硫的模拟与实验

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

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