不同热模拟实验煤热解产物特征及动力学分析

doi:10.7623/syxb201105010

石油学报 ›› 2011, Vol. 32 ›› Issue (5): 806-814.DOI: 10.7623/syxb201105010

不同热模拟实验煤热解产物特征及动力学分析

王民 1,2,3 卢双舫 1,2 王东良 4 董奇 1 刘敏 1 王雪飞 1

1东北石油大学地球科学学院黑龙江大庆 163318； 2东北石油大学油气藏形成机理与资源评价省重点实验室黑龙江大庆 163318； 3北京大学地球与空间科学学院北京 100871； 4中国石油勘探开发研究院廊坊分院河北廊坊 065007

收稿日期:2010-11-15 修回日期:2011-03-17 出版日期:2011-09-25 发布日期:2011-11-28
通讯作者: 王民
作者简介:王民，男，1981年3月生，2010年毕业于东北石油大学，现为东北石油大学副教授，主要从事油气地球化学和成藏解剖方面的教学和科研工作。
基金资助:
国家自然科学基金项目(No.40972101)、国家重点基础研究发展规划（973）项目(2009CB219306)及国家科技重大专项（2008ZX05007-001）联合资助。

Characteristics and kinetic of coal pyrolysates with different thermal simulation apparatuses

WANG Min 1,2,3 LU Shuangfang 1,2 WANG Dongliang 4 DONG Qi 1 LIU Min 1 WANG Xuefei 1

Received:2010-11-15 Revised:2011-03-17 Online:2011-09-25 Published:2011-11-28

摘要/Abstract

摘要：

利用Rock-Eval-II型热解仪、TG-MS（热失重—质谱联用仪）及金管装置对松辽盆地沙河子组煤样进行了热模拟实验。TG-MS实验中甲烷生成温度对应的 R_o与地质条件下气态烃产物生成时的成熟度接近，而Rock-Eval-II实验中烃气生成时对应的 R_o要远小于地质条件下气态烃产物生成时对应的成熟度。TG-MS实验中煤生甲烷终止温度约为850℃，对应的 R_o 约为5.3%（10℃/min升温速率）。金管实验650℃时（R_o 约为4.9%，升温速率2 ℃/h）煤生气能力尚未结束，气态烃质量产率一直呈增长趋势，同时高温阶段密闭体系中甲烷的来源主要是有机质的初次裂解。煤生气动力学参数在徐家围子地区的应用结果表明，不同生烃装置热裂解实验下获得的动力学参数外推结果差别很大，建议采用TG-MS实验装置模拟地质条件下烃源岩边生气边排出的情况，采用金管装置热裂解实验模拟存在二次裂解的封闭体系下的生气情况。

关键词: 岩石热解, 热失重—质谱, 金管, 动力学, 沙河子组

Abstract:

Coal samples from the Shahezi Formation in the Songliao Basin were pyrolyzed by means of Rock-Eval II, TG-MS (thermogravimetry-mass spectrometry) and gold tube apparatuses, respectively, in order to investigate characteristics and kinetic behaviors of their pyrolysates. Comparative results of pyrolysate yields revealed that the R_o corresponding to methane generation under TG-MS apparatus conditions was close to the maturity value of gaseous hydrocarbons generated under geological conditions, while the maturity of methane generation under Rock-Eval II experiment conditions was much lower than the R_o corresponding to gaseous generation under geological conditions. The termination temperature of methane generation from the coal sample under the TG-MS experiment was about 850℃ (at a heating rate of 10℃/min), and the corresponding R_o was about 5.3% calculated with the extended Easy R_o % model. However, the C_1-5mass yields increased all the time while even at the terminal temperature in the gold tube experiment (with the corresponding R_o of 4.9%, at a heating rate of 2℃/hour and the terminational temperature is about 650℃), indicating a gas-generative potential of the coal sample at higher maturity and the primary cracking of organic matter as the major source of methane in a closed system at this high temperature stage. It might be the recombined reaction of C₆₊liquid hydrocarbons with kerogen or bitumen in a closed environment that formed some new products with high thermal stability, which then generated methane at even higher temperature stage. For an open system, such as in the TG-MS experiment and Rock-Eval experiment, this recombined reaction could not take place because C₆₊liquid components were removed immediately with the carried gas. The geological application of kinetic parameters of gas generation from coals in the Xujiaweizi area showed that a great difference existed in the extrapolation of kinetic parameters obtained from different pyrolyzed apparatuses. Based on these data, the TG-MS apparatuses was recommended to simulate the simultaneous generation and expulsion process of hydrocarbons under geological conditions, while the gold tube apparatus was suitable for simulating a gas generation process of secondary cracking of hydrocarbons in the closed system.

Key words: Rock-Eval, TG-MS, gold tube, kinetics, Shahezi Formation

王民卢双舫王东良董奇刘敏王雪飞. 不同热模拟实验煤热解产物特征及动力学分析[J]. 石油学报, 2011, 32(5): 806-814.

WANG Min LU Shuangfang WANG Dongliang DONG Qi LIU Min WANG Xuefei. Characteristics and kinetic of coal pyrolysates with different thermal simulation apparatuses[J]. Editorial office of ACTA PETROLEI SINICA, 2011, 32(5): 806-814.

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不同热模拟实验煤热解产物特征及动力学分析

Characteristics and kinetic of coal pyrolysates with different thermal simulation apparatuses

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