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通过对塔里木盆地煤及其显微组分以1K/min升温速率在开放体系下进行热模拟实验(Tmax=1200℃),确定了CH4与N2生成动力学参数。根据化学反应动力学原理,当煤岩生成CH4和N2为25个一级平行反应且具有相同频率因子(Ao=1.0×1013s-1)时,生成CH4与N2每个反应对应的活化能可以通过实验数据与理论计算拟合,获得Gaussian型活化能分布特征为:CH4在活化能为42～90kcal/mol内,煤、镜质组、壳质组、丝质组和半丝质组生成CH4的主频活化能分别为60、52、50、70和66kcal/mol;N2在活化能为60～108kcal/mol内,其主频活化能分别为74、108、100、108和102kcal/mol。根据这些实验动力学参数,推测了煤岩在地质升温速率为5.3K/Ma时CH4的转化率:CH4在地质温度为20℃时开始形成;当地质温度为160℃时,煤岩中CH4已生成总量的80%。镜质组和壳质组CH4转化率要高于煤岩。
Through the thermal simulation experiment (Tmax = 1200 ℃) in the open system of coal and its components in Tarim Basin, the kinetic parameters of CH4 and N2 formation were determined. According to the principle of chemical reaction kinetics, when the formation of coal and rock CH4 and N2 for the 25 first-order parallel reaction with the same frequency factor (Ao = 1.0 × 1013s-1), the formation of CH4 and N2 corresponding to each reaction activation energy can be The experimental data and the theoretical calculation fit the obtained Gaussian type activation energy distribution characteristics: CH4 in the activation energy of 42 ~ 90kcal / mol, coal, vitrinite, chitin group, silk group and semi-siliceous group generated CH4 The activation energies are 60, 52, 50, 70 and 66 kcal / mol, respectively. The activation energies of N2 are in the range of 60-108 kcal / mol, and their activation energies are 74, 108, 100, 108 and 102 kcal / mol, respectively. According to these experimental kinetic parameters, the conversion rate of CH4 at the rate of 5.3K / Ma is presumed as: CH4 begins to form when the geological temperature is 20 ℃; when the geological temperature is 160 ℃, CH4 Generate 80% of the total. The conversion of CH4 in vitrinite and chitin groups is higher than that of coal rock.