CIESC Journal ›› 2020, Vol. 71 ›› Issue (11): 5256-5264.DOI: 10.11949/0438-1157.20200342

• Energy and environmental engineering • Previous Articles     Next Articles

Effect of complex inhibitors containing ionic liquids and PVP K90 on formation of methane hydrate

Junjie REN1,2,3,4,6(),Zhen LONG1,2,3,4,5(),Deqing LIANG1,2,3,4,5   

  1. 1.Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
    2.CAS Key Laboratory of Gas Hydrate, Guangzhou 510640, Guangdong, China
    3.Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, Guangdong, China
    4.Guangzhou Center for Gas Hydrate Research, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
    5.State Key Laboratory of Natural Gas Hydrate, Beijing 100028, China
    6.University of Chinese Academy of Sciences, Beijing 100049, China
  • Received:2020-03-31 Revised:2020-06-02 Online:2020-11-05 Published:2020-11-05
  • Contact: Zhen LONG

离子液体与PVP K90复合抑制剂对甲烷水合物的生成影响

任俊杰1,2,3,4,6(),龙臻1,2,3,4,5(),梁德青1,2,3,4,5   

  1. 1.中国科学院广州能源研究所,广东 广州 510640
    2.中国科学院天然气水合物重点实验室,广东 广州 510640
    3.广东省新能源和可再生能源研究开发与应用重点实验室,广东 广州 510640
    4.中国科学院广州天然气水合物研究中心,广东 广州 510640
    5.天然气水合物国家重点实验室,北京 100028
    6.中国科学院大学,北京 100049
  • 通讯作者: 龙臻
  • 作者简介:任俊杰(1992—),男,硕士研究生,rjj@mail.ustc.edu.cn
  • 基金资助:
    国家自然科学基金项目(51506202);广州市珠江科技新星专题项目(201806010114);国家重点研发计划项目(2017YFC0307306)

Abstract:

Injecting inhibitors is the most commonly used method in the oil and gas industry to solve the problem of blockage caused by hydrate formation during pipeline transportation. However, most of the kinetic hydrate inhibitors (KHIs) are strictly limited by weak inhibition performance and low subcooling. Ionic liquids, a kind of green solvent, have been recognized to act as excellent thermodynamic inhibitors on methane hydrate formation. So, it is proposed to add the ionic liquids into KHIs to improve their overall performance. In this paper, the kinetic effects of an ionic liquid N-butyl-N-methylpyrrolidine tetrafluoroborate ([BMP][BF4]), a commercial kinetic inhibitor polyvinyl pyrrolidone (PVP K90) and their mixtures with different mass ratios on the methane hydrate formation were experimentally studied at 8.0 K subcooling and two concentrations [1.0%(mass) and 2.0%(mass)]. The best mass ratio of the compound inhibitor was determined. Moreover, the crystal structures and cage occupancy characteristics of methane hydrates formed without and with inhibitors at different mass concentrations and composition ratios were measured by using powder X-ray diffraction (PXRD) and low-temperature Laser Raman spectrometers. It was found that the addition of inhibitors did not change the crystal structure of methane hydrate, but affected the cage occupancies and hydration numbers. Based on the results from macroscopic kinetics and microscopic structure tests, the inhibition mechanism of compound inhibitors was proposed.

Key words: hydrate, ionic liquids, kinetics, Raman spectroscopy, microscopic test

摘要:

注入抑制剂是油气行业解决管道输送过程因水合物生成而引发的堵塞问题最常用的方法。但现有大多数动力学抑制剂(KHIs)存在抑制性能不足、高过冷度条件下会失效等问题,可应用场合大大受限。离子液体作为绿色溶剂对甲烷水合物具有良好的热力学抑制作用。为改进KHIs的性能,提出将离子液体与KHIs复合。本文实验考察8.0 K过冷度、两种浓度下[1.0%(质量)、2.0%(质量)]离子液体N-丁基-N-甲基吡咯烷四氟硼酸盐([BMP][BF4])、聚乙烯基吡咯烷酮(PVP K90)以及二者复配构成的复合型抑制剂对甲烷水合物抑制规律,得到了最佳组分配比。利用粉末X射线衍射(PXRD)和低温激光拉曼光谱测量了不同抑制剂体系中形成的甲烷水合物晶体微观结构和晶穴占有率,发现添加抑制剂不会改变sI型甲烷水合物晶体结构,但会影响水合物晶体的大、小笼占有率和水合数。结合宏观动力学实验和微观结构测试结果,揭示离子液体与PVP K90复合抑制剂的抑制机理。

关键词: 水合物, 离子液体, 动力学, 拉曼光谱, 微观测试

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