高等学校化学学报 ›› 2011, Vol. 32 ›› Issue (4): 908.

• 研究论文 • 上一篇    下一篇

基于PC-SAFT方程研究多孔介质中水合物相平衡的预测模型

曾志勇,李小森   

  1. 中国科学院广州能源研究所, 可再生能源与天然气水合物重点实验室, 中国科学院广州天然气水合物研究中心, 广州 510640
  • 收稿日期:2010-11-17 修回日期:2011-01-20 出版日期:2011-04-10 发布日期:2011-03-09
  • 通讯作者: 李小森 E-mail:zengzy@ms.giec.ac.cn
  • 基金资助:

    国家自然科学基金(批准号: 20773133, 51076155)、广东省博士启动基金(批准号: 10451007006006174)、中国科学院知识创新工程重要研究方向项目(批准号: KGCX2-YW-3X6)和广东省科技计划项目(批准号: 2009B050600006)资助.

Hydrate Formation Phase Equilibrium Model in the Porous Media Based on PC\|SAFT Equation of State

ZENG Zhi-Yong, LI Xiao-Sen*   

  1. Guangzhou Center for Gas Hydrate Research, Key Laboratory of Renewable Energy and Gas Hydrate, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China
  • Received:2010-11-17 Revised:2011-01-20 Online:2011-04-10 Published:2011-03-09
  • Contact: LI Xiao-Sen E-mail:zengzy@ms.giec.ac.cn
  • Supported by:

    国家自然科学基金(批准号: 20773133, 51076155)、广东省博士启动基金(批准号: 10451007006006174)、中国科学院知识创新工程重要研究方向项目(批准号: KGCX2-YW-3X6)和广东省科技计划项目(批准号: 2009B050600006)资助.

摘要: 本工作对多孔介质中水合物的形成条件预测模型进行了研究。利用微扰链-统计缔合流体理论状态方程(PC-SAFT)结合van der Waals-Platteuw模型和毛细管Kelvin模型,建立了用于多孔介质中水合物体系的相平衡预测模型。在此模型基础上,针对甲烷水合物和CO2水合物,对界面张力作了进一步的研究。首先,根据多孔介质中相平衡实验数据,回归得到不同条件下的界面张力值,结果发现界面张力随温度升高而单调升高,随孔径的增大而单调减小,并且具有较好的线性关系。因此,本文提出了界面张力与温度和孔径的关联计算公式,并采用遗传算法优化回归了公式的参数。通过考察发现,以关联公式为基础改进后的模型具有良好的计算精度,在整个考察温度和孔径范围内,对于甲烷水合物和CO2水合物的预测压力与实验数据的绝对平均偏差分别为1.66%和2.76%。

关键词: 水合物, 多孔介质, 界面张力, 温度, 孔径

Abstract: This work studies the thermodynamic model of hydrate equilibrium formation conditions in the porous media. Based on the van der Waals-Platteuw model of hydrate and Kelvin equation of capillary, a phase equilibrium computational model was built. Based on this model, the surface tension was further studied for methane and CO2 hydrate. Firstly, values of surface tension were regressed from experimental equilibrium formation conditions. It is shown that the surface tension increases with the temperature increasing and decreases with the pore radius increasing, moreover, it shows a near-line trend. Thus, the surface tension function of temperature and pore radius was proposed. Parameters of the function were optimized from experimental data with genetic algorithm. The result shows that the revised model with the correlated surface tension has a distinct improvement in the predicting the hydrate equilibrium formation conditions, average absolute deviations are 1.66% and 2.76% for methane and CO2 hydrates, respectively.

Key words: gas hydrate, porous media, surface tension, temperature, pore radius

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