油页岩化学结构的化学渗透脱挥发分模型

Chemical Percolation for Devolatilization Model Based on the Oil Shale Chemical Structure

采用核磁共振碳谱(nuclear magnetic resonance spectra,1 3C-N M R)以及综合热分析仪和傅里叶红外联用技术(thermogravimetric-Fourier transform infrared spectroscopy,TG-FTIR)等手段,通过热解实验研究油页岩化学结构特性,建立适用于油页岩化学结构的化学渗透脱挥发分(chemical percolation for devolatilization,CPD)模型。该文通过13C-NMR对油页岩化学结构进行研究,得到CPD模型的4个输入参数。核磁共振分析表明,区别于煤的化学结构,芳碳含量在油页岩化学结构中所占比例相对较低,窑街样品中芳碳含量为50%,而在兴安盟样品中的含量仅为35%。利用TG-FTIR等手段通过C-R法求得桥键断裂的动力学参数,以窑街和兴安盟油页岩为样品,预测其在加热速率为50℃/min条件下的挥发分曲线。通过后验差法检验模型的预测误差,结果表明预测精度较高,验证了模型预测的合理性。

By using the methods of nuclear magnetic resonance spectra（13C-NMR） and thermogravimetric-Fourier transform infrared spectroscopy（TG-FTIR）, and studying chemical structure characteristics of the oil shale through pyrolysis experiments, chemical percolation for devolatilization（CPD） model applying to chemical structure of oil shale could be established. Four structural parameters of CPD model were derived through studying oil shale chemical structure by 13C-NMR. Nuclear magnetic resonance（NMR） analysis shows that being different from that in chemical structure of coal, proportion of the aromatic carbon in chemical structure of oil shale is relatively low. Proportion of aromatic carbon in Yaojie samples is 50%, while that in Xing＇an samples is only 35%. Kinetic parameters of the bridge bond rupture were obtained by using TG-FTIR and the C-R method. Then with the Yaojie and Xing＇an oil shale samples, the volatile curve in a heating rate of 50 ℃/min can be predicted. This article used the posterior-variance-test to test the prediction error of the model. The result shows that the prediction accuracy is higher, and validates the rationality of the model prediction.