高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (9): 1968-1975.doi: 10.7503/cjcu20180234

• 物理化学 • 上一篇    下一篇

基于转化率法研究冰粉生成乙烯水合物的动力学及THF非常规抑制作用

施伟光1, 卿红霞1, 张尚尚1, 鲁晓怡1, 王晓峰2(), 李本仙2, 徐晓虎3, 刘卫国3, 王俊1, 董朝晖4()   

  1. 1. 东北石油大学化学化工学院, 大庆 163318
    2. 吉林大学无机合成与制备化学国家重点实验室, 长春 130012
    3. 大连理工大学能源与动力学院, 大连 116024
    4. 上海同步辐射光源, 中国科学院上海应用物理研究所, 上海 201204
  • 收稿日期:2018-03-28 出版日期:2018-09-07 发布日期:2018-08-23
  • 作者简介:

    联系人简介: 王晓峰, 男, 博士, 教授, 博士生导师, 主要从事高压固体化学研究. E-mail: wangxf103@jlu.edu.cn; 董朝晖, 女, 博士, 副研究员, 主要从事同步辐射高压实验与分析技术研究. E-mail: dongzhaohui@sinap.ac.cn

  • 基金资助:
    黑龙江省教育厅海外学人项目(批准号: 1254HQ011)资助.

Kinetics and Abnormal Inhibition of THF on Ethylene Hydrate Formation from Ice Powder Based on Conversion Rate

SHI Weiguang1, QING Hongxia1, ZHANG Shangshang1, LU Xiaoyi1, WANG Xiaofeng2,*(), LI Benxian2, XU Xiaohu3, LIU Weiguo3, WANG Jun1, DONG Zhaohui4,*()   

  1. 1. College of Chemistry & Chemical Engineering, Northeast Petroleum University, Daqing 163318, China;
    2. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130023, China
    3. School of Energy and Power Engineering, Dalian University of Technology, Dalian 116024, China
    4. Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204, China
  • Received:2018-03-28 Online:2018-09-07 Published:2018-08-23
  • Contact: WANG Xiaofeng,DONG Zhaohui E-mail:wangxf103@jlu.edu.cn;dongzhaohui@sinap.ac.cn
  • Supported by:
    † Supported by the Overseas Scholar Foundation of Education Department of Heilongjiang Province, China(No.1254HQ011).

摘要:

利用压缩因子Z修正理想气体状态方程, 得到冰粉生成乙烯水合物过程中冰体积的转化率, 并结合Avrami方程与Arrhenius方程研究温度、 压力及四氢呋喃等可控因素对冰粉生成乙烯水合物的影响规律和动力学行为. 结果表明, 乙烯与冰粉反应生成水合物时不存在诱导期, 乙烯在冰粉表面快速成核并在一维方向上等速生长. 在乙烯初始压力为4.90 MPa, 温度在260.05~269.75 K范围内, 冰粉合成乙烯水合物活化能Ea=21.28 kJ/mol, 温度为269.75 K时, 冰粉的最终转化率达19.20%. 随着压力(1.98~4.90 MPa)和温度(250.46~269.75 K)升高, 冰粉转化率也增加. THF降低了冰粉转化率和转化效率, 分子尺寸效应表明THF在冰粉生成乙烯水合物过程中存在非常规抑制作用.

关键词: 冰粉, 乙烯水合物, 动力学, Avrami和Arrhenius方程, 四氢呋喃

Abstract:

The conversion rate of ice powder(α), as a key parameter on evaluation of hydrate formation from ice-gas interface, was calculated by using compressibility non-ideal gas equation. And the Avrami equation and the Arrhenius equation were combined to investigate the kinetic information and influence rule of temperature, pressure, and tetrahydrofuran(THF) on the synthesis of ethylene hydrate from ice. As a result, there is no induction period during the formation of ethylene hydrate from ice. And the ethylene hydrate is rapidly nucleated on the ice surface and grows in the one-dimensional direction with the same rate. The activation energy(Ea) of ethylene hydrate from ice powder is 21.28 kJ/mol at 260.05—269.75 K, which is much lower than that in aqueous phase. The final α is 19.20% under the initial ethylene pressure of 4.90 MPa and 269.75 K. The α rises with the pressure from 1.98 MPa to 4.90 MPa and temperature from 250.46 K to 269.75 K. And THF can reduce α and conversion efficiency of α, which can identify that THF has abnormal inhibition on the formation of ethylene hydrate from ice by molecular size effect.

Key words: Ice powder, Ethylene hydrate, Kinetics, Avrami and Arrhenius equation, Tetrahydrofuran(THF)

中图分类号: