通过混酸氧化中温煤焦油沥青制备水溶性沥青,利用热重分析研究水溶性沥青的热解机理。根据Dollimore提出的TG/DTG曲线形状推断水溶性沥青热解反应动力学机理函数,利用Achar-Brindley-Wendworth方程拟合直线计算热解活化能。结果表明,中...通过混酸氧化中温煤焦油沥青制备水溶性沥青,利用热重分析研究水溶性沥青的热解机理。根据Dollimore提出的TG/DTG曲线形状推断水溶性沥青热解反应动力学机理函数,利用Achar-Brindley-Wendworth方程拟合直线计算热解活化能。结果表明,中温煤焦油沥青在170~550℃阶段热转化动力学机理函数符合Dollimore的F1,最概然机理函数f(α)=1-α,反应为一级,活化能32.5 kJ/mol;水溶性沥青在155~460℃阶段热转化属于Dollimore的D_3,最概然机理函数1.5(1-α)^(2/3)[1-(1-α)^(1/3)]^(-1),反应机理是三维扩散,球形对称,活化能是82.8 k J/mol;在465~650℃范围内是亲水基团热解,符合Dollimore的F1,最概然机理函数f(α)=1-α,反应为一级,反应活化能41.6 k J/mol。水溶性沥青热稳定性较中温煤焦油沥青好。展开更多
Investigations on the pyrolysis and kinetic behaviors during pyrolysis of fossil fuel samples, such as coal, are fundamental for developing the related technology and practical application. In this work, pyrolysis beh...Investigations on the pyrolysis and kinetic behaviors during pyrolysis of fossil fuel samples, such as coal, are fundamental for developing the related technology and practical application. In this work, pyrolysis behavior and kinetics in the pyrolysis process of a coal sample were investigated by the thermogravimetric analyzer at a heating rate of 10, 40, 70,100, 200, and 500 °C/min, respectively. The pyrolysis process could be divided into four stages according to the TG/DTG curves. The first stage was mainly attributed to the removal of volatiles, and the second peak was the polycondensation reaction between the volatile components. It was found that more volatiles could be released from coal during pyrolysis at higher heating rate and the higher pyrolysis temperature was necessary for a rapid pyrolysis process. Kinetic analysis revealed that both the model-free(KAS and FWO) and the Coats-Redfern methods were suitable to describing the pyrolysis process, and the variation of activation energy(E) with the two types of kinetic models was consistent during the whole pyrolysis process. Furthermore, the heating rate did not alter the reaction sequence of the whole pyrolysis process, but higher heating rate could make the E value of the initial pyrolysis stage smaller.展开更多
文摘通过混酸氧化中温煤焦油沥青制备水溶性沥青,利用热重分析研究水溶性沥青的热解机理。根据Dollimore提出的TG/DTG曲线形状推断水溶性沥青热解反应动力学机理函数,利用Achar-Brindley-Wendworth方程拟合直线计算热解活化能。结果表明,中温煤焦油沥青在170~550℃阶段热转化动力学机理函数符合Dollimore的F1,最概然机理函数f(α)=1-α,反应为一级,活化能32.5 kJ/mol;水溶性沥青在155~460℃阶段热转化属于Dollimore的D_3,最概然机理函数1.5(1-α)^(2/3)[1-(1-α)^(1/3)]^(-1),反应机理是三维扩散,球形对称,活化能是82.8 k J/mol;在465~650℃范围内是亲水基团热解,符合Dollimore的F1,最概然机理函数f(α)=1-α,反应为一级,反应活化能41.6 k J/mol。水溶性沥青热稳定性较中温煤焦油沥青好。
基金the financial support from the National Natural Science Foundation of China(Grant Nos.21576293 and 21576294)
文摘Investigations on the pyrolysis and kinetic behaviors during pyrolysis of fossil fuel samples, such as coal, are fundamental for developing the related technology and practical application. In this work, pyrolysis behavior and kinetics in the pyrolysis process of a coal sample were investigated by the thermogravimetric analyzer at a heating rate of 10, 40, 70,100, 200, and 500 °C/min, respectively. The pyrolysis process could be divided into four stages according to the TG/DTG curves. The first stage was mainly attributed to the removal of volatiles, and the second peak was the polycondensation reaction between the volatile components. It was found that more volatiles could be released from coal during pyrolysis at higher heating rate and the higher pyrolysis temperature was necessary for a rapid pyrolysis process. Kinetic analysis revealed that both the model-free(KAS and FWO) and the Coats-Redfern methods were suitable to describing the pyrolysis process, and the variation of activation energy(E) with the two types of kinetic models was consistent during the whole pyrolysis process. Furthermore, the heating rate did not alter the reaction sequence of the whole pyrolysis process, but higher heating rate could make the E value of the initial pyrolysis stage smaller.
