烟气脱硫中间产物CaSO_3无氧热分解的研究
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摘要
为减少烟气脱硫产物的污染和实现钙硫资源的回收利用,同时简化现有的脱硫工艺,提出将烟气脱硫中间产物CaSO_3进行无氧热分解为CaO和SO_2的循环利用途径。本文研究以热分解产物CaO含量为主要考察指标,探究影响CaSO_3热分解的条件。实验结果表明:在无氧高温条件下,CaSO_3热分解为CaO和SO_2,热分解的优化条件为:N_2气氛、热分解温度1150℃、热分解时间2 h、热分解升温速率6℃/min、N_2流量80 m L/min,热分解产物CaO含量为99.32%。烟气脱硫中间产物CaSO_3的无氧热分解,具有明显的环保和经济价值,其应用前景广阔。
To reduce the pollution of flue gas desulfurization products and realize the recycling of calcium and sulfur resources,while simplifying the existing desulfurization process,a recycling route for the desulfurization of the flue gas desulfurization intermediate CaSO_3 to CaO and SO_2 is proposed.Taking the CaO content of thermal decomposition products as the main investigation index,the conditions affecting the thermal decomposition of CaSO_3 were investigated.The experimental results show that under the condition of no oxygen and high temperature,CaSO_3 is thermally decomposed into CaO and SO_2.The optimal conditions for thermal decomposition are:N_2 atmosphere,decomposition temperature of 1150 ℃,holding time of 2 h,heating rate of 6 ℃/min,nitrogen flow rate of 80 m L/min,the thermal decomposition product CaO content was 99.32%.The anaerobic thermal decomposition of flue gas desulfurization intermediate CaSO_3 enjoys a broad prospect of utilization thanks to its obvious values of environmental protection and economy.
To reduce the pollution of flue gas desulfurization products and realize the recycling of calcium and sulfur resources,while simplifying the existing desulfurization process,a recycling route for the desulfurization of the flue gas desulfurization intermediate CaSO_3 to CaO and SO_2 is proposed.Taking the CaO content of thermal decomposition products as the main investigation index,the conditions affecting the thermal decomposition of CaSO_3 were investigated.The experimental results show that under the condition of no oxygen and high temperature,CaSO_3 is thermally decomposed into CaO and SO_2.The optimal conditions for thermal decomposition are:N_2 atmosphere,decomposition temperature of 1150 ℃,holding time of 2 h,heating rate of 6 ℃/min,nitrogen flow rate of 80 m L/min,the thermal decomposition product CaO content was 99.32%.The anaerobic thermal decomposition of flue gas desulfurization intermediate CaSO_3 enjoys a broad prospect of utilization thanks to its obvious values of environmental protection and economy.
引文
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[2]徐兵,顾文飞,杨利香.烧结干法脱硫灰应用于二灰稳定碎石的试验研究[J].粉煤灰,2015,27(1):23-25.Xu B,Gu W F,Yang L X.Experimental study on the effects of inclination situation of the sintered heat pipe on its thermal performance sciencedirect[J].Fly ash,2015,27(1):23-25.
[3]索小丽.焦炉烟道气脱硫脱硝工艺的选择[J].当代化工研究,2017(6):107-108.Suo X L.Selection of Desulfurization and Denitration Technology for Coke Oven Flue Gases[J].Contemporary chemical research,2017(6):107-108.
[4]中国电力报社.2016中国电力行业年度发展报告[N].中国电力报,2016-08-29.
[5]武猛.烧结干法脱硫灰在再生石路基材料中应用[J].中国资源综合利用,2017,35(8):47-49.Wu M.Application of Sintering Dry Desulfurization Ash in Recycled Stone Subgrade Materials[J].Comprehensive utilization of resources in China,2017,35(8):47-49.
[6]汪茜.石灰石湿法脱硫的发展现状综述[J].化工管理,2018(20):162.Wang X.Summary of development status of limestone wet desulfurization[J].Chemical managem-nt,2018(20):162.
[7]姚璐,刘清才,方诗惠,等.半干法烧结烟气脱硫灰的氧化改性[J].环境工程学报,2016,10(6):3147-3151.Yao L,Liu Q C,Fang S H,et al.Oxidation modification of semi-dry desulfurization ash from sintering flue gas[J].Journal of Environmental Engineering,2016,10(6):3147-3151.
[8]汤志刚,贺志敏,Ebrahim,等.焦炉烟道气双氨法一体化脱硫脱硝:从实验室到工业实验[J].化工学报,2017,68(2):496-508.Tang Z G,He Z M,Ebrahim,et al.Desulfurization and denitration integrative process for coke oven flue gas using dual ammonia solution:from laboratory to industrial test[J].Journal of Chemical Industry and Engineering,2017,68(2):496-508.
[9]Han Q,Luo K B,Li H P,et al.Influence of disodium hydrogen phosphate dodecahydrate on hydrothermal formation of hemihydratecalcium sulfate whiskers[J].Particuology,2014,17(6):131-135.
[10]Ye Z C,Wang W Y,Zhong Q,et al.High temperature desulfurization using fine sorbent particles under boiler injection conditions[J].Fuel,1995,74(5):743-750.
[11]Garea A,Fernandez I,Viguri J R,et al.Flyash/calcium hydroxide mixtures for SO2removal:structural properties and maximum yield[J].Chemical Engineering Journal,1997,66(3):171-179.
[12]袁娟娟,黄萍.快速测试湿法烟气脱硫用石灰石反应活性方法的研究[J].现代化工,2015,35(3):178-180.Yuan J J,Huang P.Study of fast measurement of limestone activity used in wet flue gas desulfurization[J].Modern chemical industry,2015,35(3):178-180.
[13]Matsuzaki R,Masumizu H,Murakami N,et al.The thermal decomposition process of calcium sulfite[J].Bull Chem Soc Jpn,1978,51(1):121-122.
[14]Garaia-Martinez J,Bueno-Lopez A,Garcia-Garcia A,et al.SO2retention at low temperatures by Ca(OH)2-derived Ca O:a model for Ca O regeneration[J].Fuel,2002,81(3):305-313.
[15]王永占.湿法脱硫中间产物亚硫酸钙的氧化特性[D].北京:华北电力大学,2017.
[16]张诚.用固体热载体分解亚硫酸钙回收二氧化硫:CN102-040199A[P].2011-05-04.
[17]吕凯,孟红霞,洪成林,等.利用烟气脱硫中间产物亚硫酸钙与芒硝制备亚硫酸氢钠[J].石河子大学学报(自然科学版),2017,35(5):564-569.LüK,Meng H X,Hong C L,et al.Preparing Na HSO3with CaSO3of flue gas desulfurization and glauber's salt[J].Journal of Shihezi University(Natural Science Edition),2017,35(5):564-569.
[18]侯鹏,周勇敏,杨小月,等.石膏固相还原分解反应研究[J].硅酸盐通报,2015,34(7):1947-1952.Hou P,Zhou Y M,Yang X Y,et al.Solid-phase Reductive Reaction of Dihydrate Gypsum[J].Silicate bulletin,2015,34(7):1947-1952.
[19]卢平,章静.脱硫石膏还原分解特性的试验研究[J].动力工程学报,2012,32(3):222-228.Lu P,Zhang J.Experimental study on reduction decomposition of FGD gypsums[J].Journal of Power Engineering,2012,32(3):222-228.
[20]Fu H L,Guan B H,Wu Z B.Transformation pathways from calcium sulfite toα-calcium sulfate hemihydrate in concentrated CaCl2solutions[J].Fuel,2015,150:602-608.
[21]马双忱,杨静,张立男,等.多相条件下亚硫酸钙氧化及p H、氧化还原电位(ORP)响应[J].化工进展,2017,36(1):383-390.Ma S S,Yang J,Zhang L N,et al.Sulfite oxidation under heterogeneous conditions and responses for p H and oxidation reduction potential(ORP)[J].Chemical progress,2017,36(1):383-390.
[22]赵毅,汪黎东,王小明,等.烟气脱硫产物亚硫酸钙非催化氧化的宏观反应动力学研究[J].中国电机工程学报,2005,25(8):116-126.Zhao Y,Wang L D,Wang X M,et al.Study on the macroscopical uncatalyzed oxidation kinetics of desulfurization residual producte-calcium sulfite[J].Chinese Society for Electrical Engineering,2005,25(8):116-126.