气体水合物阻聚剂研究进展

doi:10.16085/j.issn.1000-6613.2022-1985

化工进展 ›› 2023, Vol. 42 ›› Issue (9): 4587-4602.DOI: 10.16085/j.issn.1000-6613.2022-1985

气体水合物阻聚剂研究进展

王谨航¹^,²^,³^,⁴^,⁵(), 何勇¹^,²^,³^,⁴, 史伶俐¹^,²^,³^,⁴, 龙臻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:2022-10-25 修回日期:2023-03-05 出版日期:2023-09-15 发布日期:2023-09-28
通讯作者: 龙臻,梁德青
作者简介:王谨航（1999—），男，硕士研究生，研究方向为新型水合物生成抑制技术。E-mail：wangjinhang@tju.edu.cn。
基金资助:
国家自然科学基金(51506202);广东省特支计划(2019BT02L278);广东省重点领域研发计划(2020B111101000403)

Progress of gas hydrate anti-agglomerants

WANG Jinhang¹^,²^,³^,⁴^,⁵(), HE Yong¹^,²^,³^,⁴, SHI Lingli¹^,²^,³^,⁴, LONG Zhen¹^,²^,³^,⁴(), LIANG Deqing¹^,²^,³^,⁴()

^1.Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
^2.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:2022-10-25 Revised:2023-03-05 Online:2023-09-15 Published:2023-09-28
Contact: LONG Zhen, LIANG Deqing

摘要/Abstract

摘要：

由水合物生成与聚集引起的堵塞一直是深水油气流动安全保障领域面临的棘手问题。水合物阻聚剂（AAs）因可防止水合物颗粒聚集而成为降低水合物风险的有效方法之一。本文基于作者课题组在水合物抑制技术方面的研究工作，分别梳理表面活性剂型和固体颗粒型水合物阻聚剂的构效关系。同时，调研国内外宏观-微观-分子不同尺度的阻聚性能测试手段，包括高压搅拌反应釜、摇摆槽、流动轮和流动环路，以及微观力测试仪和分子动力学模拟。基于上述实验装置和分子模拟研究结果，总结了不同类型阻聚剂对水合物的作用机理，特别是乳化和吸附机理。最后分析现有水合物阻聚剂存在的问题，并展望了水合物阻聚剂的未来发展方向。这为将来适用于南海深水油气田的高效、绿色和经济水合物AAs的开发提供重要的技术支持。

关键词: 水合物, 阻聚剂, 表面活性剂, 机理

Abstract:

The blockage caused by hydrate formation and deposit is always a troublesome problem threatening deepwater oil and gas flow assurance. One effective way to mitigate the hydrate risk is injecting hydrate anti-agglomerants (AAs), due to their capability of inhibiting hydrate particles aggregation in oil-water systems. Based on the work of our research group on hydrate inhibition technology, the structure-activity relationship of surfactant- and solid particle-based AAs was reviewed, respectively. At the same time, performance test methods at macro, micro and molecular scales were investigated, including high-pressure stirred reactor, rocking cell, flow wheel and flow loop, micromechanical force apparatus and molecular dynamics simulation. According to the above experimental setups and molecular simulation results, the action mechanism of different types of AAs on hydrates, especially emulsification and adsorption mechanism, was summarized. Finally, the existing drawbacks of hydrate inhibitors were analyzed, and the future development of the aspect was prospected. It will provide important guidance for the design of efficient, green and economical hydrate AAs suitable for deepwater oil and gas fields in the South China Sea in the future.

Key words: hydrate, anti-agglomerant, surfactant, mechanism

中图分类号:

TE39

王谨航, 何勇, 史伶俐, 龙臻, 梁德青. 气体水合物阻聚剂研究进展[J]. 化工进展, 2023, 42(9): 4587-4602.

WANG Jinhang, HE Yong, SHI Lingli, LONG Zhen, LIANG Deqing. Progress of gas hydrate anti-agglomerants[J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4587-4602.

图/表 27

图1 十二烷基-2-(2-己内酯基)乙酰胺（CDDA）

图2 单尾季铵盐R1—长链；R2—正丁基、正戊基或异戊基；X—卤素原子

图3 双尾季铵盐R1—长链；R2—甲基、正丁基、正戊基或异戊基等；X—卤素原子

图4 双-氢化牛油基二甲基氯化铵（Arquad2HT-75，n=13～15）

图5 苄基十二烷基二甲基氯化铵

图6 双子季铵盐类阻聚剂R1、R2—长链；X—卤素原子

图7 皂角树荚果提取液活性部分R1—长链；R2—长链

图8 司盘系列R—长链

图9 吐温系列R—长链

图10 炔二醇乙氧基化合物（Surfynol 420）

图11 羧基甜菜碱类两亲性表面活性剂（R1～R4均是烷基链）

图12 月桂酰胺丙基甜菜碱（LAB-30）

图13 鼠李糖脂

图14 海藻糖脂

图15 椰油酰胺丙基二甲胺

图16 卵磷脂

图17 配置扭矩传感器的高压反应釜

图18 配置PVM/FBRM的高压反应釜[15]1—天然气气瓶；2—高压反应釜；3—水浴；4—压力传感器；5—FBRM探头；6—排液口；7—搅拌装置与电机；8—数据采集系统；9—PVM探头；10—温度传感器

图19 配置黏度计的高压反应釜[70]1—电脑；2—静电计；3—压力传感器；4—反应釜；5—黏度计；6—热电偶；7—转速计；8—出液口；9—气瓶

图20 摇摆槽[74]1—压力表；2—阀门；3—气瓶；4—增压阀；5—压力表；6—缓冲泵；7—滑块；8—温度传感器；9—摇摆横杆；10—压力传感器；11—显示器；12—数据采集仪；13—摇摆槽电机

图21 流动轮[17]

图22 流动环路[77]1—原料储罐；2—磁力泵；3—流量计；4—缓冲罐；5—差压传感器；6—排水阀；7—压力传感器；8—温度传感器；A—支路；B—流量计支路；C—局部低凹路；D—透明段；E—垂直段

图23 微观力测试仪[84]1—低温恒温槽；2—橡胶管线；3—高精度操作平台；4—计算机；5—显微镜；6—操作臂；7—可视化反应装置；8—金属细管；9—环戊烷微量补给单元；10—数字温度计；11—可视化隔离罩

图24 吸附机理

图25 乳化机理

图26 颗粒型AAs阻聚机理

图27 纯水相阻聚机理

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气体水合物阻聚剂研究进展

Progress of gas hydrate anti-agglomerants

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