燃煤电厂镁法脱除烟气中SO2的研究现状与展望

doi:10.16085/j.issn.1000-6613.2017-2563

摘要/Abstract

摘要： 目前，火力发电是许多国家主要的发电方式，控制SO₂排放是治理烟气中污染物的重要工作。本文介绍了目前电厂有应用业绩的几种镁法脱硫技术，并指出现有镁法脱硫方法的弊端，继而提出未来镁法脱硫的发展方向，即基于氧化镁脱硫剂的干法以及半干法脱硫可能会在未来电厂脱硫中得到较大规模的应用。文章指出脱硫效率低是阻碍干法发展的一大问题，而对脱硫剂改性则是提高干法脱硫效率的根本办法之一，将副产品资源化是降低脱硫成本，弥补吸附剂改性费用的有效方法。针对目前日趋严峻的环保要求，现有电厂污染物治理方法针对性过强，未来，实现多烟气一体化脱除是烟气污染物治理的发展方向，干法脱硫可以为多污染物一体化脱除打下基础。本文旨在为推动氧化镁法脱硫提供参考。

关键词: 湿式镁法脱硫, 干式镁法脱硫, MgO循环再生, SO₂资源化, 吸附剂改性

Abstract: Nowadays, coal-fired power generation is applied widely in most countries, and the SO₂ control is important. In this paper, several magnesium methods which have been applied were introduced, and their drawbacks were analyzed. The development direction of magnesium methods were put forward. The dry/semi-dry methods will be used widely in the coal-fired power plants for a generation or more, which might be hindered by the low desulfurization efficiency. According to this, the modified adsorbent is one of fundamental methods. Meanwhile, byproduct reuse can be achieved for the lower cost. The pollution control is aimed at the single pollutant. However, with the severer environmental protection requirement, more and more equipment will be used, which is complicated. So, integrative flue-gas pollutants removal technology will be developed, which based on the dry methods. This paper provides a reference for magnesium desulfurization.

Key words: wet magnesium desulfurization, dry magnesium desulfurization, MgO regeneration, SO₂ reuse, adsorbent modification

中图分类号:

X701.3

马双忱, 别璇, 孙尧, 陈奎续, 朱召平. 燃煤电厂镁法脱除烟气中SO₂的研究现状与展望[J]. 化工进展, 2018, 37(09): 3609-3617.

MA Shuangchen, BIE Xuan, SUN Yao, CHEN Kuixu, ZHU Zhaoping. Present research situation and prospect of magnesium desulfurization in coal-fired power plant[J]. Chemical Industry and Engineering Progress, 2018, 37(09): 3609-3617.

参考文献

[1] 中华人民共和国工业和信息化部. 工业和信息化部、财政部关于联合组织实施工业领域煤炭清洁高效利用行动计划的通知[EB].[2015-03-09]. http://www.miit.gov.cn/n1146285/n1146352/n3054355/n3057542/n3057544/c3607954/content.html. Ministry of Industry and Information Technology of the People's Republic of China. Notice of the action plan of clean and efficient use of coal in the industrial field organized and implemented by Ministry of Industry and Information Technology and Ministry of Finance[EB].[2015-03-09]. http://www.miit.gov.cn/n1146285/n1146352/n3054355/n3057542/n3057544/c3607954/content.html.
[2] 中华人民共和国生态环境部《全面实施燃煤电厂超低排放和节能改造工作方案》[EB].[2015-12-11]. http://www.zhb.gov.cn/gkml/hbb/bwj/201512/t20151215_319170.htm. Ministry of Ecology and Environment of the People's Republic of China. Notice of the printing and distribution of "Work plan for the Fully implementation of ultra-low emissions and energy-saving transformation in the coal-fired power plant"[EB].[2015-12-11] http://www.zhb.gov.cn/gkml/hbb/bwj/201512/t20151215_319170.htm.
[3] 姚胜威. 脱硫超低排放技术在电厂中的应用探讨[J]. 现代制造, 2016(15):84-85. YAO S W. Application of desulfurization ultra-low emission technology in power plant[J]. Modern Manufacturing, 2016(15):84-85.
[4] 马双忱, 于伟静, 贾绍广, 等. 燃煤电厂脱硫废水处理技术研究与应用进展[J]. 化工进展, 2016, 35(1):255-262. MA S C, YU W J, JIA S G, et al. Research and application progresses of flue gas desulfurization (FGD) wastewater treatment technologies in coal-fired plants[J]. Chemical Industry and Engineering Progress, 2016, 35(1):255-262.
[5] CHU P. Technical manual:guidance for assessing wastewater impacts of FGD scrubbers, EPRI Report 1013313[R]. Palo Alto, CA:Electric Power Research Institute, 2006.
[6] 刘秋生. 烟气脱硫废水"零排放"技术应用[J]. 热力发电, 2014(12):114-117. LIU Q S. Application and comparison of zero discharge technology for desulfurization waste water[J]. Thermal Power Generation, 2014(12):114-117.
[7] Environmental Protection Agency. Rulemaking for the steam electric power generating effluent limitations guidelines[R]. EPA-HQOW-2009-0819, 2009.
[8] 国家发展和改革委员会. 火电厂石灰石-石膏湿法脱硫废水水质控制指标:DL/T 997-2006[S]. 北京:中国电力出版社, 2006. National Development and Reform Commission. Discharge standard of wastewater from limestone-gypsum flue gas desulfurization system in fossil fuel power plants:DL/T 997-2006[S]. Beijing:China Electric Power Press, 2006.
[9] 中华人民共和国环境保护部. 国务院关于印发水污染防治行动计划的通知[EB].[2015-04-16].[2015-07-26]. http://zfs.mep.gov.cn/fg/gwyw/201504/t20150416_299146.htm. Ministry of Environmental Protection of the People's Republic of China. Notice of the State Council on the action plan for the prevention and control of water pollution[EB/OL].[2015-04-16].[2015-07-26]. http://zfs.mep.gov.cn/fg/gwyw/201504/t20150416_299146.htm.
[10] 叶春松, 黄建伟, 刘通, 等. 燃煤电厂烟气脱硫废水处理方法与技术进展[J]. 环境工程, 2017, 35(11):10-13. YE C S, HUANG J W, LIU T, et al. Technology progresses and treatment methods of flue gas desulfurization wastewater in coal-fired plants[J]. Environmental Engineering, 2017, 35(11):10-13.
[11] NIE P F, ZHANG H Y, WANG Y. Causes analysis of wet flue gas desulphurization stack rainout for the thermal powerplant without GGH and its countermeasures[J]. Advanced Materials Research, 2013,724/725:1306-1309.
[12] MA S, CHAI J, JIAO K, et al. Environmental influence and countermeasures for high humidity flue gas discharging from power plants[J]. Renewable & Sustainable Energy Reviews, 2017, 73:225-235.
[13] 汪波, 刘全祥. 石灰石-石膏法脱硫工艺中存在的问题探析[J]. 中国环保产业, 2008(11):44-46. WANG B, LIU Q X. Existing problems in limestone-gypsum process of desulfurization technology[J]. China's Environmental Protection Industry, 2008(11):44-46.
[14] YAN L, LU X, WANG Q, et al. Recovery of SO₂ and MgO from by-products of MgO wet flue gas desulfurization.[J]. Environmental Engineering Science, 2014, 31(11):621.
[15] Environmental Protection Agency of USA. Flue gas desulfurization and sulfuric acid production via magnesia scrubbing[R]. EPA-625/2/75/007, 1975
[16] COLLEGE J W, VLNATY J. Removal of SO₂ from SO₂-containing gases. US4626418[P]. 1986-12-02.
[17] CHEIDEMA M N, TASKINEN P. Decomposition thermodynamics of magnesium sulfate[J]. Industrial & Engineering Chemistry Research, 2011, 50(16):9550-9556.
[18] RODRIGUEZ J A, JIRSAK T, ANDREA F A, et al. Interaction of SO₂ with MgO(100) and Cu/MgO(100):decomposition reactions and the formation of SO₃ and SO₄[J]. J. Phys. Chem. B, 2000, 104(31):7439-7448.
[19] INDUSTRIES M H. Flue gas desulfurization system using the magnesium process[J]. Technical Review, 1995, 32(1):41-42
[20] 袁钢. 回收法氧化镁脱硫关键技术实验研究[D]. 北京:清华大学, 2009. YUAN G. Experimental research on the key technology of flue gas desulfurization with magnesium sulfate recovery[D]. Beijing:Tsinghua University, 2009.
[21] 袁钢, 马永亮, 汪黎东. 氧化镁烟气脱硫反应特性研究[J]. 环境工程学报, 2010, 4(5):1134-1138. YUAN G, MA Y L, WANG L D. Study on the characteristics of flue gas desulfurization by magnesium oxide[J]. Journal of Environmental Engineering, 2010, 4(5):1134-1138.
[22] 崔可, 柴明, 徐康富, 等. 回收法氧化镁湿法烟气脱硫机理和工艺基础研究[J]. 环境科学, 2006, 27(5):846-849. CUI K, CAI M, XU K F, et al. Mechanism and technology of recovery flue gas desulphurization with magnesium oxide[J]. Environmental Science, 2006, 27(5):846-849.
[23] YAN L, LU X, WANG Q, et al. Research on sulfur recovery from the byproducts of magnesia wet flue gas desulfurization[J]. Applied Thermal Engineering, 2014, 65(1/2):487-494.
[24] 吕天宝. 镁法脱硫技术在2×330MW机组上的应用[J]. 电力科技与环保, 2011, 27(4):45-47. LÜ T B. Application research of magnesium desulfurization technology on 2×330MW units[J]. Power Technology and Environmental Protection, 2011, 27(4):45-47.
[25] 孙祥超, 朱哲, 商平. 镁法脱硫技术在荣程钢铁公司的应用[J]. 资源节约与环保, 2014(7):13-14. SUN X C, ZHU Z, SHANG P. The application of magnesium method desulfurization technology in Rongcheng Steel Company[J]. Resource Conservation and Environmental Protection, 2014(7):13-14.
[26] 韩森. 氧化镁法脱硫在太钢发电厂的应用[J]. 山西化工, 2008, 28(3):58-59. HAN S. The application of MgO FGD in power plant of TISCO[J]. Shanxi Chemical Engineering, 2008, 28(3):58-59.
[27] 杨奇. 镁法脱硫在电厂超低排放改造的应用[J]. 信息化建设, 2016(2):203-204. YANG Q. Application of magnesium method desulfurization to ultra-low emission transformation in power plants[J]. Information Construction, 2016(2):203-204.
[28] 武春锦, 吕武华, 梅毅, 等. 湿法烟气脱硫技术及运行经济性分析[J]. 化工进展, 2015, 34(12):4368-4374. WU C J, LÜ W H, MEI Y, et al. Application and running economic analysis of wet flue gas desulfurization[J]. Chemical Industry and Engineering Progress, 2015, 34(12):4368-4374.
[29] JAE L S, JUN H K, JUNG S Y, et al. Regenerable MgO-based SO_x removal sorbents promoted with cerium and iron oxide in RFCC[J]. Ind. Eng. Chem. Res., 2005, 44:9973-9978.
[30] MEHTA M, MUKHOPADHYAY M, CHRISTIAN R, et al. Synthesis and characterization of MgO nanocrystals using strong and weak bases[J]. Powder Technol., 2012, 226:213-221.
[31] RODRIGUEZ J A, JIRSAK T, FREITAG A, et al. Interaction of SO₂ with MgO(100) and Cu/MgO(100):decomposition reactions and the formation of SO₃ and SO₄[J]. J. Phys. Chem. B, 2000, 104:7439-7448.
[32] CHOWDHURY A H, CHOWDHURY I H, NASKAR M K. A facile synthesis of grainy rodlike/porous MgO[J]. Mater. Lett., 2015, 158:190-193.
[33] SATHYAMOORTHY R., MAGESHWARI K, MALI S S, et al. Effect of organic capping agent on the photocatalytic activity of MgO nanoflakes obtained by thermal decomposition route[J]. Ceram. Int. 2013, 39:323-330.
[34] WAQIF M, SAAD A M, BENSITEL M, et al. Comparative study of SO₂ adsorption on metal oxides[J]. J. Chem. Soc. Faraday Trans, 1992, 88:2931-2936.
[35] 刘朋杰, 高宇, 胡筱敏, 等. 新型氧化镁基吸附剂烟气干法脱硫研究[J]. 安全与环境学报, 2008, 8(3):33-36. LIU P J, GAO Y, HU X M, et al. New-featured dry desulphurization analysis on the magnesia-base adsorbent flue gas[J]. Journal of Safety and Environment, 2008, 8(3):33-36.
[36] LI Z S, FANG F, CAJ N S. Characteristic of solid product layer of MgSO in the reaction of MgO with SO₂[J]. Chinese Science:Technical Science, 2010, 53(7):1869-1876.
[37] 马双忱. 烟气循环流化床脱硫技术实验研究[D]. 保定:华北电力大学(保定), 2003. MA S C. Experimental study on flue gas circulating fluidized bed desulfurization technology[D]. Baoding:North China Electric Power University(Baoding), 2003.
[38] VALLEZERMENO R D, FORMOSA J, APARICIO J A, et al. Transposition of wet flue gas desulfurization using MgO by-products:from laboratory discontinuous batch reactor to pilot scrubber[J]. Fuel Processing Technology, 2015, 138:30-36.
[39] 高宇. 纳米氧化镁基吸附剂烟气同时脱硫脱硝研究[D]. 沈阳:东北大学, 2010. GAO Y. Study on simultaneous desulfurization and denitrification of flue gas with nano magnesium oxide adsorbents[D]. Shenyang:Northeastern University, 2010.
[40] 高鹏. 中温MgO基脱硫剂的研究[D]. 西安:西北大学, 2011. GAO P. Study on MgO-based desulfurizer on medium temperature[D]. Xi'an:Northwest University, 2011.
[41] 杨凯宁. FCC过程中MgO基硫转移剂的研究[D]. 西安:西北大学, 2010. YANG K N. Study of sulfur transfer based on MgO in FCC process[D]. Xi'an Northwest University, 2010.
[42] VALLEZERMENO R D, MONTIANOREDONDO J D, FORMOSA J, et al. Reutilization of MgO byproducts from the calcination of natural magnesite in dry desulfurization:a closed-loop process[J]. Energy & Fuels, 2015, 29(6):63-72
[43] 闫丽云. 氧化镁湿法烟气脱硫副产品再生循环利用的研究[D]. 重庆:重庆大学, 2014. YAN L Y. Research on regenerative cycle and utilization of MgO wet flue gas desulfurization byproducts[D]. Chongqing:Chongqing University, 2014.
[44] KANG W, ZHOU Y, SHEN Z, et al. Optimization of pyrolysis for MgO recycling in magnesia-based flue gas desulfurization[J]. Asian Journal of Chemistry, 2013, 25(3):1250-1254.
[45] WANG K, REEBER R R. A simplified model for predicting high pressure thermal expansion of MgO[J]. Geophysical Research Letters, 1995, 22(10):1297-1300.
[46] ROCHE, E G, PRASAD J. Magnesium oxide recovery:WO2007070973[P]. 2007-06-28.
[47] KAY H. Treatment of nickeliferous oxidic materials for the recovery of nickel values:US3466144[P]. 1969-09-09.
[48] PLEWA J, STEINDOR J. Kinetics of reduction of magnesium sulphate by carbon oxide[J]. Journal of Thermal Analysis, 1987, 32:1809-1820.
[49] ZAMBRANO A. Production of high purity and high surface area magnesium oxide:WO8102153[P]. 1981-08-06.
[50] WYNN N P. Procede d'extraction du nickel de minerais lateriques:FR2448577[P]. 1980-01-14.
[51] SCHEIDEMA M S M, TASKINEN P, METSÄRINTA M L. Reductive decomposition of magnesium sulfate[C]//European Metallurgical Conference, EMC, 2011.
[52] SHEN Z G, GUO S P, KANG W Z, et al. The kinetics of oxidation inhibition of magnesium sulfite in the wet flue gas desulphurization process[J]. Energy Sources Part A:Recovery Utilization & Environmental Effects, 2013, 35(20):1883-1890.
[53] 曾坤. 湿法烟气脱硫副产物亚硫酸盐的氧化动力学研究[D]. 上海:华东理工大学, 2012. ZENG K. The experiment research of oxidation kinetics of sulfite in the process of wet magnesium flue gas desulfurization(FGD)[D]. Shanghai:East China University of Technology, 2012.
[54] WANG L, MA Y, YUAN G, et al. Study on the reaction characteristics of flue gas desulfurization by magnesia[C]//International Conference on Bioinformatics and Biomedical Engineering, IEEE, 2009:1-3.
[55] 马强. 烟气中多种污染物超低排放的活性分子氧化及一体化脱除机理研究[D]. 杭州:浙江大学, 2016. MA Q. Study on active molecule oxidation and removal mechanism of ultra-low emissions of flue gas polutants[D]. Hangzhou:Zhejiang University, 2016.
[56] DERENNE S, SARTORELLI P, BUSTARD J, et al. Toxecon clean coal demonstration for mercury and multi-pollutant control at the Presque Isle Power Plant[J]. Fuel Processing Technology, 2009, 90(11):1400-1405.
[57] MOKHTAR M M, TAIB M R, HASSIM M H. Decision analysis of multi-pollutant control strategy for coal-fired power plant in Malaysia[J]. Clean Technologies & Environmental Policy, 2016(5):1-7.
[58] 方朝君, 闫常峰, 余美玲. 同时脱硫脱硝技术的应用与发展现状[J]. 化工进展, 2010, 29(s1):361-365. FANG Z J, YAN C F, YU M L. The application and development of simultaneous desulfurization and denitrification technology[J]. Chemical Industry and Engineering Progress, 2010, 29(s1):361-365.

燃煤电厂镁法脱除烟气中SO₂的研究现状与展望

Present research situation and prospect of magnesium desulfurization in coal-fired power plant

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