聚集态结构热模拟演化特征HRTEM分析——以内蒙古伊敏煤为例

High resolution TEM image analysis of the aggregate structural characteristics under heat treatment:A case study of Yimin coal

  • 摘要: 以伊敏煤为研究对象,利用高分辨率透射电子显微镜(HRTEM)对伊敏煤热模拟后4个不同温度点(384,456,528和600 ℃)产物的聚集态结构特征进行了研究,并利用热重质谱联用(TG-MS)实验分析了伊敏煤热解过程中主要气态产物的析出特征。研究结果表明,伊敏煤热模拟过程中,芳香层片的长度、弯曲度、有序性、层间距及堆垛高度等均随温度增加发生了阶段性变化,并与热解过程中气态产物的生成密切相关;384~456 ℃阶段,1×1芳香层片增多,而较大尺寸的芳香层片减少,弯曲度为1.0~1.2的芳香层片增多,较大弯曲度的芳香层片减少,有序性变好,这些现象均与芳香结构内羧基或其他含氧杂环裂解有关,与此同时芳香层片层间距减小,堆垛高度增加;456~528 ℃阶段,体系内芳香甲基或芳香甲基醚键断裂生成甲烷,新形成的芳香结构聚合,导致1×1芳香层片减少,较大尺寸芳香层片增多,弯曲度为1.0~1.2的芳香层片减少,较大弯曲度的芳香层片增多,有序性变好,同时芳香层片层间距减小,堆垛高度增加;528~600 ℃阶段,煤热解以小芳香层片的缩聚反应生成大量H2占主导地位,因此1×1芳香层片大幅减少,较大尺寸芳香层片大幅增多,弯曲度为1.0~1.2的芳香层片减少,较大弯曲度的芳香层片增多,芳香层片有序性变差,芳香层片层间距略有增大,堆垛高度显著增加。

     

    Abstract: The aggregate structural characteristics of Yimin lignite under heat treatment at 384,456,528 and 600 ℃ were examined by HighResolution Transmission Electron Microscopy (HRTEM) technique in this paper.Thermogravimetry coupled with mass spectrometry (TG-MS) was employed to measure the gaseous evolution characteristics from 30 ℃ to 900 ℃.The results indicated that the length,crooked degree,orientation distribution,layer spacing and stacking height of the aromatic fringes varied accordingly with increasing temperature,and were closely related to the gaseous release characteristics during pyrolysis.From 384 ℃ to 456 ℃,1×1 aromatic layers increased while the larger ones decreased,the number of aromatic layer with a crooked degree of 1.0-1.2 increased while the one with more crooked decreased,and the aromatic layer became more oriented.All of those were related to the release of CO2,which evolved by the decomposition of carboxyl or oxygen containing heterocycles linked to the aromatic rings,meanwhile,the spacing distance decreased while the stacking height increased.From 456 ℃ to 528 ℃,the main reaction of coal pyrolysis was the breaking of arylmethyl or alkyl ether bond and the polycondensation of the small aromatic layer which formed in the above stage.Therefore,it caused the reduction of 1×1 aromatic layers and the increase of larger ones,the reduction of aromatic layers with a crooked degree of 1.0-1.2 and the increase of others,the decrease of the aromatic layer spacing distance,the increase of stacking height,and better orientation distribution.From 528 ℃ to 600 ℃,a large amount of H2 was generated from the polycondensation of small aromatic layers.Therefore,1×1 aromatic layers decreased and the larger ones increased,the number of aromatic layer with a crooked degree of 1.0-1.2 decreased while the number of more crooked one increased,the stacking height increased significantly.

     

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