碳热还原二氧化硫制备硫黄的研究进展

doi:10.16085/j.issn.1000-6613.2015.07.015

摘要/Abstract

摘要： 碳热还原二氧化硫制备硫黄是一种绿色资源化的SO₂治理技术。本文对碳热还原二氧化硫制备硫黄的研究进展进行了综述, 介绍了国内外关于碳与二氧化硫反应机理及反应动力学的研究, 讨论了C/SO₂摩尔比、反应温度、反应时间、反应气氛、碳的类型以及矿物质等因素对碳热还原二氧化硫反应的影响规律。得出了反应实现较高SO₂转化率和S产率所需要的条件。并指出微波辐照条件下, 碳还原二氧化硫的反应优势明显, 研究其反应机理和产物生成规律对于该技术的应用意义重大, 是未来发展的重要方向。

关键词: 二氧化硫, 还原, 硫黄, 微波辐照, 反应动力学, 活性炭

Abstract: Carbothermal reduction of SO₂ to prepare elemental sulfur is a green and sustainable desulfurization technique. In this work, the research progress of this technique was reviewed. The mechanism and the kinetics of the reaction between carbon and SO₂were introduced. The influence factors were also discussed in terms of C/SO₂ molar ratio, reaction temperature, reaction time, reaction atmosphere, form of carbon, and mineral substance. The optimum condition to gain high SO₂ conversation and sulfur yield was obtained, and this work concluded that the reaction between carbon and SO₂ under microwave radiation has remarkable advantage. Therefore, the studies on the exploration of the reaction mechanism and the trends of the products generated are significantly important to the application of this technique.

Key words: sulfur dioxide, reduction, elemental sulfur, microwave radiation, reaction kinetics, activated carbon

中图分类号:

X511

冯太, 赵希强, 张立强, 王涛, 马春元. 碳热还原二氧化硫制备硫黄的研究进展[J]. 化工进展, 2015, 34(07): 1898-1904.

FENG Tai, ZHAO Xiqiang, ZHANG Liqiang, WANG Tao, MA Chunyuan. Progress of carbothermal reduction of SO₂ to elemental sulfur[J]. Chemical Industry and Engineering Progree, 2015, 34(07): 1898-1904.

参考文献

[1] Liu Q L, Wang Q. Pathways to SO₂ emissions reduction in China for 1995—2010:Based on decomposition analysis[J]. Environmental Science & Policy, 2013, 33:405-415.
[2] 袁志国, 刘有智, 宋卫, 等. 并流旋转填料床中磷酸钠法脱除烟气中SO₂[J]. 化工进展, 2014, 33(5):1327-1331.
[3] Xiong Y Y, Niu Y Q, Tan H Z, et al. Experimental study of a zero water consumption wet FGD system[J]. Applied Thermal Engineering, 2014, 63(1):272-277.
[4] 李皎, 廖国权, 马殿学. 石灰石-石膏湿法脱硫系统节能降耗探讨[J]. 电力科技与环保, 2014, 30(3):51-54.
[5] 王学海, 方向晨, 刘忠生. 催化还原二氧化硫为单质硫的研究进展[J]. 化工进展, 2010, 29(7):1209-1214+1240.
[6] 李兵. 粉末活性炭循环流化床吸附脱除烟气中SO₂的实验研究[D].济南:山东大学能源与动力工程学院, 2012.
[7] 张立强, 蒋海涛, 李兵, 等. 粉状活性炭流化床吸附SO₂的实验研究及吸附动力学分析[J]. 煤炭学报, 2012, 37(6):1046-1050.
[8] 张立强, 蒋海涛, 马春元, 等. 烟气脱硫活性炭微波再生特性的实验研究[J]. 燃料化学学报, 2012, 40(11):1366-1371.
[9] Lepose R. Chemistry of sulfur dioxide reduction[J]. Industrial & Engineering Chemistry, 1938, 30(1):92-100.
[10] Klinzing G E, Walker R J. Equilibrium studies of the direct reduction of sulphur dioxide by coal[J]. Fuel, 1984, 63(10):1450-1454.
[11] Ratcliffe C T, Pap G. Chemical reduction of sulphur dioxide to free sulphur with lignite and coal. 2. Kinetics and proposed mechanism[J]. Fuel, 1980, 59(4):244-248.
[12] 邢新艳, 肖勇, 郭彦霞, 等. 添加金属氧化物的V₂O₅/AC在烟气脱SO₂及脱SO₂后H₂再生制备硫磺的活性研究[J]. 燃料化学学报, 2008, 36(3):349-353.
[13] 张跃, 杨守明, 王国良, 等. 用热解还原法生产硫磺的工业实验研究[J]. 硅酸盐通报, 2013, 32(4):767-771.
[14] Stacy W O, Vastola F J, Walker Jr P L. Interaction of sulfur dioxide with active carbon[J]. Carbon, 1968, 6(6):917-923.
[15] Abramowitz H, Insigna R, Rao Y K. Kinetics of reaction of sulfur dioxide with carbon[J]. Carbon, 1976, 14(17):84-86.
[16] Rai Puri B, Singh Hazra R. Carbon-sulphur surface complexes on charcoal[J]. Carbon, 1971, 9(2):123-134.
[17] Blackwood J D, McCarthy D J. The kinetically effective stoichiometry of reactions in the carbon-sulphur dioxide system[J]. Australian Journal of Chemistry, 1973, 26(4):723-731.
[18] Humeres E, Moreira R F P M, Peruch M G B. Reduction of SO₂ on different carbons[J]. Carbon, 2002, 40(5):751-760.
[19] Humeres E, Moreira R F P M, Castro S C. Catalysis and inhibition of the carbon-sulfur reaction[J]. J. Braz. Chem. Soc., 1994, 5(2):69-76.
[20] Humeres E, Peruch M G B, Moreira R F P M, et al. Reactive intermediates of the reduction of SO₂ on activated carbon[J]. Journal of Physical Organic Chemistry, 2003, 16(10):824-830.
[21] Humeres E, Peruch M G B, Moreira R F P M, et al. Reduction of sulfur dioxide on carbons catalyzed by salts[J]. International Journal of Molecular Sciences, 2005, 6(1):130-142.
[22] Humeres E, Castro K M, Moreira R F P M, et al. Reactivity of the
thermally stable intermediates of the reduction of SO₂ on carbons and mechanisms of insertion of organic moieties in the carbon matrix[J]. The Journal of Physical Chemistry C, 2008, 112(2):581-589.
[23] Humeres E, Castro K M, Smaniotto A, et al. Reactivity of the intermediates of the reduction of SO₂. Functionalization of graphite, graphite oxide and graphene oxide[J]. Journal of Physical Organic Chemistry, 2014, 27(4):344-351.
[24] Lepsoe R. Chemistry of sulfur dioxide reduction, kinetics[J]. Industrial & Engineering Chemistry, 1940, 32(7):910-918.
[25] Bejarano C, Jia C Q, Chung K H. Mechanistic study of the carbothermal reduction of sulfur dioxide with oil sand fluid coke[J]. Industrial & Engineering Chemistry Research, 2003, 42(16):3731-3739.
[26] 郑诗礼, 杨松青, 张宏闻, 等. 碳热还原二氧化硫的热力学平衡验证[J]. 环境化学, 1997, 16(4):300-305.
[27] Bejarano C A, Jia C Q, Chung K H. A study on carbothermal reduction of sulfur dioxide to elemental sulfur using oilsands fluid coke[J]. Environmental Science & Technology, 2001, 35(4):800-804.
[28] Bejarano C A. Carbothermal reduction of sulfur dioxide using oil-sands fluid coke[D]. Toronto, Ontario, Canada:Department of Chemical Engineering and Applied Chemistry, University of Toronto, 2000.
[29] Foster Wheeler. Reduction of SO₂ with coal:US, 4147762[P]. 1979
[30] Ratcliffe C T, Pap G. Chemical reduction of sulphur dioxide to free sulphur with lignite and coal. 1. Steady-state reaction chemistry and interaction of volatile components[J]. Fuel, 1980, 59(4):237-243.
[31] 陈忠, 尹爱君, 杨松青, 等. 二氧化硫高温还原制取元素硫的热力学平衡计算[J]. 湖南有色金属, 1996, 12(3):52-55.
[32] 王树森, 凌爱莲, 王志忠, 等. SO₂还原为元素硫的条件研究[J]. 北京工业大学学报, 1992, 18(1):56-61.
[33] 王树森, 凌爱莲, 王志忠, 等. 从含硫废气中回收元素硫[J]. 北京工业大学学报, 1991, 17(4):76-81, 86.
[34] 凌爱莲, 王志忠, 王树森. 排烟脱硫新方法的研究[J]. 北京工业大学学报, 1992, 18(2):74-79.
[35] 刘公召, 梅晓丹, 顾齐欣. 固定床反应器活性炭还原SO₂制单质硫的研究[J]. 化学世界, 2012, (2):72-74+88.
[36] Feng W, Charles Q J. Influence of O₂ and H₂O on carbothermal reduction of SO₂ by oil-sand fluid coke[J]. Environ. Sci. Technol., 2005, 39(24):9710-9714.
[37] 黄卡玛, 杨晓庆. 微波加快化学反应中非热效应研究的新进展[J]. 自然科学进展, 2006, 16(3):273-279.
[38] 赵伟, 刘希涛. 微波-活性炭联合作用在污染控制中的应用[J]. 环境工程学报, 2009, 3(7):1153-1159.
[39] Cha C Y. Microwave induced reactions of SO₂ and NO_x in the char-bed[J]. Res. Chem. Intermed., 1994;20(1):13-28.
[40] 张达欣, 于爱民, 金钦汉. 微波-炭还原法处理二氧化硫的研究[J].微波学报, 1998, 14(4):342-347.
[41] 昌晶, 周震峰, 徐敏, 等. 活性炭加微波还原分解SO₂实验研究[J]. 工业安全与环保, 2008, 34(8):14-16.
[42] 王鑫, 闫淑梅, 刘皓磊. 微波辐射活性炭脱硫技术的实验研究[J]. 吉林电力, 2007, 35(2):12-15.
[43] 马双忱, 赵毅, 马宵颖, 等. 微波诱导催化还原脱硫脱硝实验研究[J]. 中国电机工程学报, 2006, 26(18):121-125.
[44] 马双忱, 赵毅, 马宵颖, 等. 活性炭床加微波辐射脱硫脱硝的研究[J]. 热能动力工程, 2006, 21(4):338-341+433.
[45] Cha C Y, Kim D S. Microwave induced reactions of sulfur dioxide and nitrogen oxides in char and anthracite bed[J]. Carbon, 2001, 39(8):1159-1166.
[46] 马双忱, 靳义净, 金鑫, 等. 烟气共存成分对微波辐照活性炭同时脱硫脱硝的影响研究[J]. 燃料化学学报, 2011, 39(6):460-464.
[47] 赵毅, 刘威, 祝晓雨, 等. 微波辐照活性炭同时脱硫脱硝的试验研究[J]. 动力工程学报, 2013, 33(11):878-882.
[48] Ma S C, Yao J J, Jin X, et al. Kinetic study on desulfurization and denitrification using microwave irradiation over activated carbon[J]. Science China Technological Sciences, 2011, 54(9):2321-2326.
[49] Ighigeanu D, Martin D, Macarie R. Air pollution control by DC, pulse and microwave discharge[J]. Journal of Environmental Protection and Ecology, 2003(4):525-534.
[50] 秦华, 徐岩, 付俊青. 微波诱导等离子体法对燃煤烟气脱硫的研究[J]. 煤质技术, 1999(5):27+29.
[51] Wang X, Wang A, Wang X, et al. Microwave plasma enhanced reduction of SO₂ to sulfur with carbon[J]. Energy & Fuels, 2007, 21(2):867-869.
[52] 马双忱, 高莉, 金鑫, 等. 微波辐照活性炭脱硫脱硝技术研究进展[J]. 环境科学与技术, 2011, 34(8):70-74.
[53] 张跃, 扬守明, 王国良, 等. 低品位硫铁矿生产硫磺的工业实验研究[J]. 无机盐工业, 2011, 43(2):47-49.
[54] 赵希强, 宋占龙, 王涛, 等. 微波技术用于热解的研究进展[J]. 化工进展, 2008, 27(12):1873-1877, 1881.