湿法脱硫吸收塔结垢原因分析与防治
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摘要
某热电厂2×330 MW燃煤亚临界发电机组采用石灰石—石膏湿法烟气脱硫工艺,脱硫系统在长期运行过程中,吸收塔内烟气入口、除雾器、浆液循环泵滤网和氧化空气管道等位置出现明显结垢情况。在对不同垢样分别取样后,借助于X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线能谱分析(EDS)、热重分析(TG)等检测方法对其元素组成、微观形貌及重要离子含量等进行表征,经分析后得出垢样形成原因与垢样在吸收塔内生成位置有较强相关性,因为生成垢样的环境是垢形成的根本原因。垢样根据结垢机理的不同大致可以分为3类:"湿-干"区域垢、结晶结垢和沉积结垢。针对不同类型结垢提出相应解决方案,指出实现脱硫过程氧化反应与pH耦合控制是解决脱硫系统运行问题的关键。
The limestone-gypsum wet flue gas desulfurization process is applied in the 2×330 MW coal-fired subcritical generator set in a thermal power plant. During the long-term operation of the desulfurization system, obvious scaling occurs at the positions of the flue gas inlet, demister, slurry circulating pump filter and oxidizing air pipeline in the absorption tower. The scale samples collected from different sampling points were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), X-ray energy spectrum analysis(EDS), thermogravimetric analysis(TG) and other methods to determine their elemental composition, microstructure and important ion content. After analysis, it was found that the cause of scale formation has a strong correlation with the formation position of the scale in the absorption tower, for the background ions concentration of the formation of scale is the root cause of fouling. Scales can be roughly classified into three categories according to the fouling mechanism, namely the "wet-dry" area scale, crystal scale and sediment scale. According to different types of scaling, the corresponding solutions are proposed. It is pointed out that the oxidation reaction and pH coupling control in the desulfurization process are the solutions to the current operation problems of the system.
The limestone-gypsum wet flue gas desulfurization process is applied in the 2×330 MW coal-fired subcritical generator set in a thermal power plant. During the long-term operation of the desulfurization system, obvious scaling occurs at the positions of the flue gas inlet, demister, slurry circulating pump filter and oxidizing air pipeline in the absorption tower. The scale samples collected from different sampling points were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), X-ray energy spectrum analysis(EDS), thermogravimetric analysis(TG) and other methods to determine their elemental composition, microstructure and important ion content. After analysis, it was found that the cause of scale formation has a strong correlation with the formation position of the scale in the absorption tower, for the background ions concentration of the formation of scale is the root cause of fouling. Scales can be roughly classified into three categories according to the fouling mechanism, namely the "wet-dry" area scale, crystal scale and sediment scale. According to different types of scaling, the corresponding solutions are proposed. It is pointed out that the oxidation reaction and pH coupling control in the desulfurization process are the solutions to the current operation problems of the system.
引文
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[30]SHENCHEN H,ROCHELLE G T.Nitrogen dioxide absorption and sulfite oxidation in aqueous sulfite[J].Environmental Science & Technology,2015,32(13):1994-2003.
[2]杨静.湿法脱硫浆液pH与ORP氧化双控制实验研究[D].保定:华北电力大学,2017.
[3]付红亮.石灰石—石膏湿法脱硫吸收塔结垢原因分析与防治[J].福建建材,2016(10):12-14.
[4]杨杨,樊保国.石灰石湿法脱硫吸收塔内结垢研究[J].锅炉技术,2013,44(5):71-74.
[5]LI Y,ZHOU J,ZHU T,et al.Calcium sulfite oxidation and crystal growth in the process of calcium carbide residue to produce gypsum[J].Waste & Biomass Valorization,2014,5(1):125-131.
[6]杨亿,胡宏,李天祥.硫酸钙结垢与防治措施研究进展[J].广州化工,2014,42(20):11-13.
[7]周利民,张士宾.二水硫酸钙晶体生长及添加剂对它的影响(Ⅰ)——二水硫酸钙成核及生长现象的研究[J].盐科学与化工,2001,30(2):15-17.
[8]GAGE C L,ROCHELLE G T.Limestone dissolution in flue gas scrubbing:effect of sulfite[J].Air Repair,2016,42(7):926-935.
[9]FU H,JIA C,CHEN Q,et al.Effect of particle size on the transformation kinetics of flue gas desulfurization gypsum to α-calcium sulfate hemihydrate under hydrothermal conditions[J].Particuology,2018,40(5):98-104.
[10]窦焰,刘同海,沈浩,等.反应结晶过程中二水硫酸钙晶粒性能[J].化工学报,2016,67(6):2449-2455.
[11]康静娜.吸收塔结垢阻塞分析及防治措施[C].第四届火电行业化学(环保)专业技术交流会论文集,2013.
[12]徐海,郦和生,王岽.硫酸钙结晶过程及其影响因素研究[J].工业水处理,2011,31(5):67-69.
[13]许小云,刘瑾,樊建明.二水硫酸钙结晶过程研究进展[J].应用化工,2005,34(6):325-327.
[14]刘绍银.湿法脱硫系统结垢的化学机理及运行控制分析[J].热力发电,2011,40(1):70-72.
[15]HONG Z,LIANG L L,HAI-JUN W U.Review of oxidation technology of calcium sulfite in flue gas desulfurization process[J].Electric Power Technology & Environmental Protection,2010.26(2):26-28.
[16]刘亚明,潘丹萍,徐齐胜,等.石灰石石膏法脱硫浆液结晶特性研究[J].高校化学工程学报,2015,29(4):985-991.
[17]苏伟.基于湿法脱硫工艺的硫酸钙结垢特性实验研究[D].哈尔滨:哈尔滨工业大学,2009.
[18]GEORGIN J F,MAACH N,POMMAY J.Sulphate crystallization modelling and surface reactivity in solution[J].Construction and Building Materials,2017,156:266-276.
[19]TENG F,ZENG H,LIU Q.Understanding the Deposition and Surface Interactions of Gypsum[J].Journal of Physical Chemistry C,2011,115(35):17485-17494.
[20]GUAN B,YANG L,WU Z,et al.Preparation of α-calcium sulfate hemihydrate from FGD gypsum in K,Mg-containing concentrated CaCl2 solution under mild conditions[J].Fuel,2009,88(7):1286-1293.
[21]汪潇.脱硫石膏制备硫酸钙晶须媒晶剂的筛选及作用机理研究[D].武汉:华中科技大学,2014.
[22]徐宏建,潘卫国,郭瑞堂,等.金属离子对石膏结晶时间及粒径分布的影响[J].动力工程学报,2010,30(8):628-632.
[23]LI Y,ZHOU J,ZHU T,et al.Calcium sulfite oxidation and crystal growth in the process of calcium carbide residue to produce gypsum[J].Waste & Biomass Valorization,2014,5(1):125-131.
[24]陈曲仙.氟铝杂质离子和有机酸添加剂对脱硫石膏结晶过程的影响实验研究[D].湘潭:湘潭大学,2014.
[25]HAMDONA S K,HADAD U A.Crystallization of calcium sulfate dihydrate in the presence of some metal ions[J].Journal of Crystal Growth,2007,299(1):146-151.
[26]杨俊强,薛明超,杨晓飞,等.电厂湿法烟气脱硫塔底结垢异常分析及解决措施[J].华电技术,2017,39(8):67-69.
[27]李春雨,董越,齐勇,等.石灰石—石膏湿法脱硫系统结垢及飞灰影响特性研究[J].环境工程,2014,32(s1):513-518.
[28]GUAN B,SHEN Z,WU Z,et al.Effect of pH on the preparation of α-Calcium sulfate hemihydrate from FGD gypsum with the hydrothermal method[J].Journal of the American Ceramic Society,2008,91(12):6.
[29]谷俊杰.烟气湿法脱硫亚硫酸钙结垢及GGH堵塞研究分析[D].北京:北京化工大学,2012.
[30]SHENCHEN H,ROCHELLE G T.Nitrogen dioxide absorption and sulfite oxidation in aqueous sulfite[J].Environmental Science & Technology,2015,32(13):1994-2003.
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