CIESC Journal ›› 2020, Vol. 71 ›› Issue (4): 1424-1431.DOI: 10.11949/0438-1157.20190994

• Thermodynamics • Previous Articles     Next Articles

Phonon heat conduction and quantum correction of methane hydrate

Ming LIU1(),Zhe XU2   

  1. 1.Petroleum Engineering and Technology Institute of Shengli Oilfield Branch, the Shandong Provincial Key Laboratory of Heavy Oil Recover, Dongying 257000, Shandong, China
    2.Institute of New Energy, China University of Petroleum, Qingdao 266580, Shandong, China
  • Received:2019-09-02 Revised:2019-12-26 Online:2020-04-05 Published:2020-04-05
  • Contact: Ming LIU

甲烷水合物声子导热及量子修正

刘明1(),徐哲2   

  1. 1.胜利油田分公司石油工程技术研究院,山东省稠油开采技术重点实验室,山东 东营 257000
    2.中国石油大学(华东)新能源学院,山东 青岛 266580
  • 通讯作者: 刘明
  • 作者简介:刘明(1976—),男,高级工程师,upclm@sina.com
  • 基金资助:
    中石化科技攻关项目(P19005-4)

Abstract:

The equilibrium molecular dynamics method was used to simulate the thermal conductivity of methane hydrate, and the thermal conductivity of 30—150 K methane hydrate was given. The studies of thermal transport in hydrate have a lot of significance in hydrate exploitation and gas hydrate storage and transport. In this paper, an equilibrium molecular dynamics simulation for 2×2×2 type I methane hydrate periodic structure is carried out by LAMMPS and the thermal transport process is analyzed. For methane hydrate, CH4 is modeled as OPLS-UA type while H2O is treated by TIP4P/2005 model. The intermolecular interactions are described by the Lennard-Jones potential function and a Coulombic pairwise interaction. During the simulation, the methane hydrate is successively placed into NVT and NPT ensembles to relax for 1 ns respectively, so as to equilibrate the whole system. Then, it is transferred into NVE ensemble to run 2 ns for calculating the thermal conductivity. The thermal conductivity which is much closer to experiments results can be obtained by quantum correlation. When the simulation temperature is lower than Debye temperature, the quantum effect has a great influence on the molecular simulation results. The relaxation time of acoustic phonons and optical phonons are calculated by fitting the autocorrelation function of heat flow. The results show that the phonon relaxation time decreases with the increase of temperature and the acoustic phonon contributes most to heat conductivity. With the increase of the interaction strength between carbon and oxygen atoms, the coupling of vibration between carbon and oxygen atoms becomes stronger, and the thermal conductivity of methane hydrate increases.

Key words: methane hydrate, molecular dynamics simulation, thermal conductivity, phonon modes decomposition, quantum correction

摘要:

采用平衡分子动力学方法模拟了甲烷水合物的导热,给出了30~150 K甲烷水合物的热导率。采用量子修正对分子模拟结果进行处理,可以得到更接近实验值的结果。当模拟温度低于德拜温度时,量子效应对分子模拟结果的影响较大。通过对热流自相关函数拟合得到了声学声子和光学声子的弛豫时间。结果显示,声子弛豫时间随温度增加逐渐减小,声学声子导热在水合物的导热中比重最大。随着碳氧原子之间相互作用力的增加,碳氧原子之间振动的耦合程度增加,甲烷水合物的热导率增加。

关键词: 甲烷水合物, 分子动力学, 热导率, 声子模式分解, 量子修正

CLC Number: