石墨热分解CaSO4反应机理研究Study on the reaction mechanism of thermal decomposition reaction of CaSO4 and graphite
赵亮
ZHAO Liang
摘要(Abstract):
碳(C)热分解硫酸钙(CaSO_4)的反应普遍发生于采用炉内脱硫的循环流化床锅炉中,深入研究其反应机理对于改善炉内固硫性能具有重要意义。基于热重质谱试验,采用等效特征图谱法(ECSA)深入探索了石墨热分解CaSO_4的反应过程;同时结合水平管式炉试验,通过表征反应后的固体产物,综合分析得出石墨热分解CaSO_4过程中各主要反应的温度区间。结果表明:基于热重质谱试验数据结合等效特征图谱法(ECSA)可以很好地解析石墨热分解CaSO_4的主要反应过程; CaSO_4自分解反应发生在1 100℃左右,石墨的加入使得CaSO_4的分解温度降低至900℃左右,同时增大其最快分解速率、缩短完全分解时间; 1 050℃左右,石墨热分解CaSO_4的速率达到最大,但最大分解速率对应的温度与石墨的添加量无关;随着石墨与CaSO_4摩尔比的增加,CaSO_4的分解速率逐渐增大,但起始分解的温度略有降低并趋于稳定;在石墨热分解CaSO_4反应过程中,生成CO_2、SO_2气体和CaO固体的反应为最主要的反应;当反应温度超过1 100℃时,石墨与CaSO_4可能发生生成CaS和CO_2的反应,但其进行程度很小。
The reaction of carbothermal decomposition of calcium sulfate( CaSO_4) generally occurs in circulating fluidized bed boilers that use furnace desulfurization. It is of great significance to in-depth study the reaction mechanism for improving the sulfur fixation performance in the furnace. Based on the experiment of thermogravimetric and mass spectrometry,the equivalent characteristic spectrum( ECSA) method was used to deeply explore the reaction process of graphite thermal decomposition of CaSO_4. Besides,combined with the horizontal tube furnace experiment,the solid product after the reaction was characterized. The temperature range of the main reactions in the decomposition of CaSO_4 was comprehensively analyzed. The results show that based on the experimental data of thermogravimetric mass spectrometry combined with ECSA,the main reaction process of graphite thermal decomposition of CaSO_4 can be well analyzed. The selfdecomposition reaction of CaSO_4 occurs at about 1 100 ℃,and the addition of graphite reduces the decomposition of CaSO_4 temperature to about 900 ℃,while increasing the fastest decomposition rate and shortening the complete weight loss time. At about 1 050 ℃,the rate of thermal decomposition of CaSO_4 by graphite is the fastest,but the temperature corresponding to the maximum decomposition rate is not correlated with the amount of graphite added. With the increase of the molar ratio of graphite and CaSO_4 increases,the fastest reaction rate of the decomposition of CaSO_4 gradually increases,and the temperature of thermal decomposition of CaSO_4 decreases slightly and tends to be stable. In the process of thermal decomposition,the reaction of CO_2,SO_2 and Ca O is the most important reaction product. When the reaction temperature is higher than 1100℃,the reaction between graphite and residual CaSO_4 will also occur to generate Ca S and CO_2,but to a small extent.
关键词(KeyWords):
硫酸钙;热分解;等效特征图谱法;热重质谱;石墨
CaSO_4;thermal decomposition;ECSA;TG-MS;graphite
基金项目(Foundation): 中国科学院战略性先导科技专项资助项目(XDA21000000)
作者(Author):
赵亮
ZHAO Liang
DOI: 10.13226/j.issn.1006-6772.19083001
参考文献(References):
- [1]蔡润夏,柯希玮,葛荣存,等.循环流化床超细石灰石炉内脱硫研究[J].中国电机工程学报,2018,38(10):3042-3048.CAI Runxia,KE Xiwei,GE Rongcun,et al.Thein-situ desulfurization with ultra-fine limestone for circulating fluidized bed boilers[J].Proceedings of the CSEE,2018,38(10):3042-3048.
- [2]杨吉青,周俊虎,程军,等.煤粉炉喷钙脱硫技术的研究进展[J].中国电力,2005,38(11):96-99.YANG Jiqing,ZHOU Junhu,CHENG Jun,et al.Research progress of FGD technology by limestone injection in pulverized-coal fired boilers[J].Electric Power,2005,38(11):96-99.
- [3]MAKARYTCHEV S V,CEN K F,LUO Z Y,et al.High-temperature sulphur removal under fluidized bed combustion conditionsA chemical interpretation[J].Chemical Engineering Science,1995,50(9):1401-1407.
- [4]李守信,纪立国,于军玲,等.石灰石-石膏湿法烟气脱硫工艺原理[J].华北电力大学学报(自然科学版),2002,29(4):91-94.LI Shouxin,JI Liguo,YU Junling,et al.Analysis of wet limestone-gypsum FGD technique[J].Journal of North China Electric Power University (Natural Science Edition),2002,29(4):91-94.
- [5]ZHENG S C,CHENG F X,WANG Z J.Production of SO2and lime from phosphogypsum reduced with lignite in a nitrogen atmosphere[J].Advanced Materials Research,2013,803:94-98.
- [6]MA L,NING P,ZHENG S,et al.Reactionmechanism and kinetic analysis of the decomposition of phosphogypsum via a solid-state reaction[J].Industrial&Engineering Chemistry Research,2010,49(8):3597-3602.
- [7]卢平,章静.脱硫石膏还原分解特性的试验研究[J].动力工程报,2012,32(3):222-228.LU Ping,ZHANG Jing.Study on reductive decomposition of FGD gypsums[J].Journal of Chinese Society of Power Engineering,2012,32(3):222-228.
- [8]TAKAHIRO Kato,KENJI Murakami,KATSUYASU Sugawara.Carbon reduction of gypsum produced from flue gas desulfurization[J].Archiv Für Klinische Und Experimentelle Dermatologie,2012,29(1):805-810.
- [9]ZHENG S,NING P,MA L,et al.Reductive decomposition of phosphogypsum with high-sulfur-concentration coal to SO2in an inert atmosphere[J].Chemical Engineering Research and Design,2011,89(12):2736-2741.
- [10]ZHU B,MA L,ZHENG D,et al.Study on thetransmission and transformation of the impurities in the reductive decomposition process of phosphogypsum[J].MMEBC,2016,88:767-773.
- [11]燕春培,郁青春,刘大春,等.真空碳热还原分解硫酸钙热力学分析及实验探究[J].真空科学与技术学报,2014,34(5):517-521.YAN Chunpei,YU Qingchun,LIU Dachun,et al.Decomposition ofcalcium sulphate by carbothermic reduction at reduced Pressures[J].Chinese Journal of Vacuum Science and Technology,2014,34(5):517-521.
- [12]LINDGREN E R,PERSHING D W,KIRCHGESSNER D A,et al.Fuel rich sulfur capture in a combustion environment[J].Environmental Science&Technology,2015,26(26):1427-1433.
- [13]肖海平,周俊虎,曹欣玉,等.Ca SO4在不同气氛下分解特性的实验研究[J].动力工程学报,2004,24(6):889-892.XIAO Haiping,ZHOU Junhu,CAO Xinyu,et al.Experimental study of decomosition behavior of Ca SO4in different atmospheres[J].Power Engineering,2004,24(6):889-892.
- [14]范红宇,曹欣玉,周俊虎,等.不同气氛下煤燃烧固硫化学反应机理研究进展[J].煤炭学报,2003,28(1):74-79.FAN Hongyu,CAO Xinyu,ZHOU Junhu,et al.Development of sulfur capture mechanism during coal combustion process in different atmosphere[J].Journal of China Coal Society,2003,28(1):74-79.
- [15]CHENG J,ZHANG Y,WANG T,et al.Thermogravimetric fourier transform infrared spectroscopy gas chromatography mass/spectrometry study of volatile organic compounds from coal pyrolysis[J].Energy&Fuels,2017,31(7):7042-7051.
- [16]曹勇,夏红德,周托,等.燃煤锅炉灰渣中可燃碳含量的分析方法[J].中国粉体技术,2017,23(3):100-105.CAO Yong,XIA Hongde,ZHOU Tuo,et al.Accurate measurement for unburned carbon in fly ash and slag from coal boilers[J].China Powder Science and Technology,2017,23(3):100-105.
- [17]XIA Hongde,WEI Kai.Equivalent characteristic spectrum analysis in TG-MS system[J].Thermochimica Acta,2015,602:15-21.
- [18]MA L,NIU X,HOU J,et al.Reaction mechanism and influence factors analysis for calcium sulfide generation in the process of phosphogypsum decomposition[J].Thermochimica Acta,2011,526(1/2):163-168.
- [19]韩志东,王建祺.石墨氧化过程的XRD/XPS研究[J].无机化学学报,2003,19(12):1366-1370.HAN Zhidong,WANG Jianqi.XRD/XPS Study onoxidation of graphite[J].Chinese Journal of Inorganic Chemistry,2003,19(12):1366-1370.