离子液体协同PVCap抑制天然气水合物生成实验研究

doi:10.11949/0438-1157.20230180

化工学报 ›› 2023, Vol. 74 ›› Issue (6): 2639-2646.DOI: 10.11949/0438-1157.20230180

离子液体协同PVCap抑制天然气水合物生成实验研究

龙臻¹^,²^,³^,⁴(), 王谨航¹^,²^,³^,⁴^,⁵, 任俊杰¹, 何勇¹^,²^,³^,⁴(), 周雪冰¹^,²^,³^,⁴, 梁德青¹^,²^,³^,⁴()

^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.天然气水合物国家重点实验室，北京 100028
^5.中国科学院大学，北京 100049

收稿日期:2023-03-01 修回日期:2023-05-16 出版日期:2023-06-05 发布日期:2023-07-27
通讯作者: 何勇,梁德青
作者简介:龙臻（1986—），女，博士，副研究员，longzhen@ms.giec.ac.cn
基金资助:
国家自然科学基金项目(51506202);广东省特支计划项目(2019BT02L278);广东省重点领域研发计划项目(2020B111101000403);广东省基金面上项目(2020A1515010374)

Experimental study on inhibition effect of natural gas hydrate formation by mixing ionic liquid with PVCap

Zhen LONG¹^,²^,³^,⁴(), Jinhang WANG¹^,²^,³^,⁴^,⁵, Junjie REN¹, Yong HE¹^,²^,³^,⁴(), Xuebing ZHOU¹^,²^,³^,⁴, Deqing LIANG¹^,²^,³^,⁴()

^1.Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
^2.CAS Key Laboratory of Gas Hydrate, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
^3.Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, Guangdong, China
^4.State Key Laboratory of Natural Gas Hydrate, Beijing 100028, China
^5.University of Chinese Academy of Sciences, Beijing 100049, China

Received:2023-03-01 Revised:2023-05-16 Online:2023-06-05 Published:2023-07-27
Contact: Yong HE, Deqing LIANG

摘要/Abstract

摘要：

利用自制的高压反应釜实验研究了离子液体N-丁基-N-甲基吡咯烷四氟硼酸盐([BMP][BF₄])、动力学抑制剂聚乙烯己内酰胺(PVCap）及其二元复合物对CH₄/C₂H₆/C₃H₈混合气体水合物生成动力学的影响，发现在任何浓度下(0.25%~2.0%，质量分数)，[BMP][BF₄]对混合气体水合物抑制能力远弱于PVCap，但对PVCap具有显著协同效应，且随着PVCap占比增大而增强。粉末X射线衍射(PXRD)和低温激光拉曼光谱测试结果证实，所有体系中形成的样品中均含sⅡ型和sⅠ型两种结构水合物，含PVCap体系中sⅡ/sⅠ水合物相对含量降低。低温冷冻电镜（Cryo-SEM）观测结果显示，添加单一PVCap及其与[BMP][BF₄]的混合物会使水合物晶体的微观形貌更粗糙且多孔。

关键词: 水合物, 离子液体, 聚合物, 微观结构, 协同效应

Abstract:

An investigation on the effect of an ionic liquid N-butyl-N-methylpyrrolidine tetrafluoroborate ([BMP][BF₄]), a commercial kinetic hydrate inhibitor poly(N-vinylcaprolactam) (PVCap) and their binary mixture on the hydrate formation process from methane/ethane/propane ternary mixture was carried out by using a self-designed high-pressure apparatus. It was found that at any concentration [0.25%—2.0% (mass)], [BMP][BF₄] had a much weaker inhibitory effect on mixed gas hydrate than PVCap, but had a significant synergistic effect on PVCap, which was enhanced as the proportion of PVCap increased. Moreover, with the increasing proportion of PVCap, the compound inhibitor performed better. Both powder X-ray diffraction patterns and low-temperature Raman spectra indicated that sⅠ and sⅡ hydrates coexisted in all tested systems. The inhibitors containing PVCap reduced the relative contents of sⅠ and sⅡ hydrates in the samples. The images observed from scanning electron cryomicroscopy (Cryo-SEM) indicated that the presence of PVCap and its mixture with [BMP]BF₄] made the formed hydrates more coarse and porous.

Key words: hydrate, ionic liquid, polymer, microstructure, synergistic effect

中图分类号:

TK 123

龙臻, 王谨航, 任俊杰, 何勇, 周雪冰, 梁德青. 离子液体协同PVCap抑制天然气水合物生成实验研究[J]. 化工学报, 2023, 74(6): 2639-2646.

Zhen LONG, Jinhang WANG, Junjie REN, Yong HE, Xuebing ZHOU, Deqing LIANG. Experimental study on inhibition effect of natural gas hydrate formation by mixing ionic liquid with PVCap[J]. CIESC Journal, 2023, 74(6): 2639-2646.

图/表 9

图1 PVCap和[BMP][BF4]分子结构式

Fig.1 Molecular structures of PVCap and [BMP][BF4]

图2 高压水合物反应釜测试系统

Fig.2 High-pressure hydrate reaction apparatus

图3 0.25%(质量) [BMP][BF4]体系中CH4/C2H6/C3H8气体水合物生成过程压力-温度变化

Fig.3 Experimental procedure showing the pressure and temperature conditions for CH4/C2H6/C3H8 gas hydrate formation at 0.25% (mass) [BMP][BF4]

图4 不同抑制剂体系中CH4/C2H6/C3H8混合气体水合物生成过程压力随时间的变化

Fig.4 Changes of pressure with time during CH4/C2H6/C3H8 hydrate formed with pure water and different inhibitors

图5 不同浓度抑制剂体系中的CH4/C2H6/C3H8混合气体水合物的生成诱导时间

Fig.5 Induction time for CH4/C2H6/C3H8 hydrate formation at different concentraions of inhibitors

图6 不同配比组合抑制剂体系中CH4/C2H6/C3H8混合气体水合物生成过程压力随时间的变化

Fig.6 Variation of pressure with time during CH4/C2H6/C3H8 gas hydrate formation in the presence of 0.25% (mass) compound inhibitor with different composition ratios

图7 不同体系中生成的CH4/C2H6/C3H8混合气体水合物PXRD谱图a—纯水；b—0.25%(质量) [BMP][BF4]；c—0.25%(质量) PVCap；d—0.25%(质量) [BMP][BF4]+PVCap (1∶2)

Fig.7 PXRD patterns of CH4/C2H6/C3H8 gas hydrate formed in different systems

图8 不同体系中生成的CH4/C2H6/C3H8混合气体水合物Raman谱图a—纯水；b—0.25%(质量) [BMP][BF4]；c—0.25%(质量) PVCap；d—0.25%(质量) [BMP][BF4]+PVCap (1∶2)

Fig.8 Raman spectra of CH4/C2H6/C3H8 hydrate formed in different systems

图9 不同倍数下冰晶和不同体系中水合物的微观形貌

Fig.9 Cryo-SEM images of ice crystal with different magnifications and of hydrates formed in the presence of different inhibitors

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离子液体协同PVCap抑制天然气水合物生成实验研究

Experimental study on inhibition effect of natural gas hydrate formation by mixing ionic liquid with PVCap

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