离子液体与动力学抑制剂作用下混合气体水合物生成特性研究

doi:10.11949/0438-1157.20230087

化工学报 ›› 2023, Vol. 74 ›› Issue (4): 1703-1711.DOI: 10.11949/0438-1157.20230087

离子液体与动力学抑制剂作用下混合气体水合物生成特性研究

龙臻¹^,²^,³^,⁴(), 王谨航¹^,²^,³^,⁴^,⁵, 何勇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:2023-02-08 修回日期:2023-03-30 出版日期:2023-04-05 发布日期:2023-06-02
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)

Characteristics study on hydrates formation from gas mixture under ionic liquid together with kinetic hydrate inhibitors

Zhen LONG¹^,²^,³^,⁴(), Jinhang WANG¹^,²^,³^,⁴^,⁵, Yong HE¹^,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, Guangzhou Institute of Energy Conversion, 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:2023-02-08 Revised:2023-03-30 Online:2023-04-05 Published:2023-06-02
Contact: Yong HE, Deqing LIANG

摘要/Abstract

摘要：

利用等温恒容法实验考察了一种高性能离子液体N-丁基-N-甲基吡咯烷四氟硼酸盐（［BMP］［BF₄］）、两种动力学抑制剂（KHIs）［聚乙烯基吡咯烷酮（PVP）和聚乙烯己内酰胺（PVCap）］及［BMP］［BF₄］与KHI的二元混合物对甲烷/乙烷/丙烷三元混合气体水合物生成动力学过程的影响规律。通过分析压力和气相组分变化规律，发现混合气体水合物呈现两步骤生长模式。在高过冷度（>10℃）和高搅拌速率（1000 r/min）条件下，单一添加剂基本失效，而［BMP］［BF₄］可较好协助增强PVCap的抑制性能。粉末X射线衍射和激光拉曼光谱测试结果均显示，所有体系中形成的水合物样品结构同时存在sⅠ型和sⅡ型，抑制剂的添加主要影响两种晶体结构的相对含量和各客体分子的笼子占有率。最后探讨了协同抑制机理。

关键词: 动力学抑制剂, 水合物, 离子液体, 聚合物, 机理

Abstract:

To recognize the synergistic inhibition of ionic liquids, the effects of N-butyl-N-methylpyrrolidine tetrafluoroborate ([BMP][BF₄]), two kinetic inhibitors (KHIs) (poly(N-vinylpyrrolidone) (PVP) and poly(N-vinylcaprolactam) (PVCap) ) and binary mixtures of KHI with [BMP][BF₄] on the hydrate formation process from methane/ethane/propane ternary mixture were investigated by using the isothermal isochoric method. By analyzing the time-dependent variation of pressure and gas phase composition, it was found that synthesized natural gas hydrate grew in a two-step way. At a high subcooling degree (>10℃) and stirring rate (1000 r/min), those tested additives failed when used alone, while an enhanced inhibition performance of PVCap was observed with the assistance of [BMP][BF₄]. Both powder X-ray diffraction and laser Raman spectroscopy test results show that the hydrate samples formed in all systems have sⅠ and sⅡ structures at the same time. The addition of inhibitors mainly affects the relative content of the two crystal structures and the cage occupancy of each guest molecule. Finally, a synergistic inhibition mechanism was proposed.

Key words: kinetic hydrate inhibitor, hydrate, ionic liquid, polymer, mechanism

中图分类号:

TK 123

龙臻, 王谨航, 何勇, 梁德青. 离子液体与动力学抑制剂作用下混合气体水合物生成特性研究[J]. 化工学报, 2023, 74(4): 1703-1711.

Zhen LONG, Jinhang WANG, Yong HE, Deqing LIANG. Characteristics study on hydrates formation from gas mixture under ionic liquid together with kinetic hydrate inhibitors[J]. CIESC Journal, 2023, 74(4): 1703-1711.

图/表 9

图1 高压水合物反应系统

Fig.1 Schematic diagram of high-pressure gas hydrate reaction

图2 1.0%（质量） PVPK90体系中混合气体水合物生成过程压力-温度变化曲线

Fig.2 Pressure versus temperature curve during CH4/C2H6/C3H8 hydrate formation process with 1.0%（mass） PVPK90

图3 1.0%（质量） PVPK90体系中CH4/C2H6/C3H8水合物生成过程压力和温度随时间变化曲线

Fig.3 Typical changes of pressure and temperature versus time during CH4/C2H6/C3H8 hydrate formed with 1.0%（mass） PVPK90 aqueous solution

图4 1.0%（质量）抑制剂体系中的CH4/C2H6/C3H8水合物的生成过程压力和温度随时间变化曲线

Fig.4 Changes of pressure and temperature versus time during CH4/C2H6/C3H8 hydrate formed with pure water and 1.0%（mass） different inhibitors

表1 反应结束水合物相和气相组分分布及耗气量

Table 1 Gas compositions in vapor phase and hydrate phase at the end of reaction and total gas consumption in the presence of water or various inhibitors

体系	水合物相组分浓度/%(mol)			耗气量/mmol	气相组分浓度/%（mol)
体系	CH₄	C₂H₆	C₃H₈	耗气量/mmol	CH₄	C₂H₆	C₃H₈
纯水	83.77	10.13	6.1	86.5	99.41	0.54	0.05
[BMP][BF₄]	85.07	8.92	6.01	86.4	98.23	1.65	0.12
PVPK90	83.05	10.48	6.47	81.2	99.16	0.77	0.07
PVCap	82.80	10.57	6.63	78.4	98.91	0.97	0.12
PVPK90+[BMP][BF₄]	83.77	9.99	6.24	84.4	99.06	0.88	0.06
PVPCap+[BMP][BF₄]	52.78	23.37	23.85	20.2	96.82	2.83	0.32

图5 CH4/C2H6/C3H8混合气在不同添加剂体系中形成的水合物晶体PXRD衍射谱图a—纯水;b—1.0%(质量) [BMP][BF4]; c—1.0%(质量) PVPK90; d—1.0%(质量)PVCap; e—0.5%(质量) PVPK90+ 0.5%(质量) [BMP][BF4]; f—0.5%(质量) PVCap + 0.5%(质量) [BMP][BF4]

Fig.5 PXRD patterns of CH4/C2H6/C3H8 hydrate formed in the presence of different additives

图6 纯水体系中形成的CH4/C2H6/C3H8混合气体水合物晶体拉曼光谱图（800~1200 cm-1：C—C区域；2800~3000 cm-1：C—H区域；3000~3400 cm-1：O—H区域）

Fig.6 Typical Raman spectrum of CH4/C2H6/C3H8 hydrate formed with pure water （800—1200 cm-1: C—C region； 2800—3000 cm-1: C—H region； 3000—3400 cm-1： O—H region）

表2 客体分子直径与水合物笼子直径比率［1］

Table 2 Ratios of molecular diameters to cage diameters for some guest molecules［1］

客体分子	客体分子直径/Å	sⅠ型水合物		sⅡ型水合物
客体分子	客体分子直径/Å	5¹²	5¹²6²	5¹²	5¹²6⁴
CH₄	4.36	0.855	0.744	0.868	0.655
C₂H₆	5.5	1.08	0.939	1.1	0.826
C₃H₈	6.28	1.23	1.07	1.25	0.943

图7 不同抑制剂体系中生成的CH4/C2H6/C3H8混合气体水合物拉曼光谱图a—纯水; b—1.0%(质量) [BMP][BF4]; c—1.0%(质量) PVPK90;d—1.0%(质量) PVCap; e—0.5%(质量) PVP + 0.5%(质量) [BMP][BF4]; f—0.5%(质量) PVCap + 0.5%(质量) [BMP][BF4]

Fig.7 Raman spectrum of CH4/C2H6/C3H8 hydrate formed in the presence of different inhibitors

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离子液体与动力学抑制剂作用下混合气体水合物生成特性研究

Characteristics study on hydrates formation from gas mixture under ionic liquid together with kinetic hydrate inhibitors

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