离子液体与PVP K90复合抑制剂对甲烷水合物的生成影响

doi:10.11949/0438-1157.20200342

化工学报 ›› 2020, Vol. 71 ›› Issue (11): 5256-5264.DOI: 10.11949/0438-1157.20200342

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.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

收稿日期:2020-03-31 修回日期:2020-06-02 出版日期:2020-11-05 发布日期:2020-11-05
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)

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

Junjie REN^1,^2,^3,^4,⁶(),Zhen LONG^1,^2,^3,^4,⁵(),Deqing LIANG^1,^2,^3,^4,⁵

^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

摘要/Abstract

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

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

中图分类号:

TK 123

任俊杰,龙臻,梁德青. 离子液体与PVP K90复合抑制剂对甲烷水合物的生成影响[J]. 化工学报, 2020, 71(11): 5256-5264.

Junjie REN,Zhen LONG,Deqing LIANG. Effect of complex inhibitors containing ionic liquids and PVP K90 on formation of methane hydrate[J]. CIESC Journal, 2020, 71(11): 5256-5264.

图/表 12

图1 实验系统图

Fig.1 Schematic of the experimental apparatus

表1 实验材料表

Table 1 List of the materials used for the experiments

试剂	缩写	摩尔质量/(g·mol^-1)	纯度/%	供应商
N-丁基-N-甲基吡咯烷四氟硼酸盐	[BMP][BF₄]	229.07	≥ 99	中科院兰州化学物理研究所
聚乙烯基吡咯烷酮 K90	PVP K90	360000		梯希爱（上海）化成工业发展有限公司
甲烷气体	CH₄	16	≥ 99.99	佛山市科的气体有限公司
去离子水	H₂O	18		实验室自制

图2 [BMP][BF4] 和 PVP K90的化学结构

Fig.2 Chemical structure of [BMP][BF4] and PVP K90

图3 1.0%(质量) 和2.0%(质量)浓度下不同抑制剂体系中甲烷水合物生成过程压力随时间的变化

Fig.3 Changes of pressures versus time for methane hydrates with solutions containing different inhibitors at 1.0%(mass) and 2.0%(mass)

图4 1.0%(质量)和2.0%(质量)浓度下不同抑制剂体系中甲烷水合物生成诱导时间

Fig.4 Induction time of methane hydrate formation in the presence of 1.0%(mass) and 2.0%(mass) [BMP][BF4] and the mixture of [BMP][BF4] with PVP (ratio of 1∶1)

图5 不同配比下甲烷水合物生成过程压力随时间的变化

Fig.5 Changes of pressures varying with time for methane hydrate formed with 2.0%(mass) composite inhibitors at different ratios

图6 不同配比下甲烷水合物生成初期200 min气体消耗量随时间的变化

Fig.6 Gas consumption curves with time under different ratio of composite inhibitors within the first 200 minutes

图7 CH4在不同体系下生成的水合物晶体PXRD谱图

Fig.7 PXRD patterns for hydrate samples formed from CH4 with different systems

图8 CH4在不同体系中生成的水合物晶体的拉曼光谱图

Fig.8 Raman spectra of the C—H stretching mode for CH4 incorporated into hydrate formed with different systems

表2 甲烷在不同抑制剂体系形成的水合物中大、小笼占有率和水合数

Table 2 Hydrate numbers and cage occupancies of methane hydrate formed in the presence of various inhibitors

反应体系	小笼占有率θ_S	大笼占有率θ_L	水合数n
无 (纯水)	0.936±0.080	0.946±0.041	6.095±0.124
IL	0.832±0.011	0.977±0.004	6.125±0.015
PVP	0.896±0.051	0.971±0.007	6.036±0.048
[PVP+IL](1∶4)	0.947±0.043	0.963±0.011	5.994±0.015
[PVP+IL](1∶2)	0.924±0.035	0.969±0.005	6.003±0.033
[PVP+IL](1∶1)	0.819±0.159	0.944±0.063	6.300±0.072
[PVP+IL](2∶1)	0.905±0.086	0.948±0.048	6.136±0.111
[PVP+IL](4∶1)	0.930±0.098	0.925±0.072	6.211±0.196

图9 水合物中气体CH4在大、小笼绝对占有率以及水合数与组合型抑制剂配比的关系

Fig.9 Relationship of occupancy of large and small cages by CH4 gas in hydrate and hydration number between different ratio of the compound inhibitor

图10 组合型抑制剂对甲烷水合物生成抑制作用示意图

Fig.10 Schematic diagram of the effect of compound inhibitor on CH4 hydrate formation

参考文献 36

1	Sloan E D, Koh C A. Clathrate Hydrates of Natural Gases[M]. 3rd ed. Boca Raton: CRC Press, 2007: 1-17.
2	Wang Y H, Fan S S, Lang X M. Reviews of gas hydrate inhibitors in gas-dominant pipelines and application of kinetic hydrate inhibitors in China[J]. Chinese Journal of Chemical Engineering, 2019, 27(9): 2118-2132.
3	樊栓狮, 郭凯, 王燕鸿, 等. 天然气水合物动力学抑制剂性能评价方法的现状与展望[J]. 天然气工业, 2018, 38(9): 103-113.
	Fan S S, Guo K, Wang Y H, et al. Present situation and prospect of performance evaluation methods for kinetic hydrate inhibitors (KHIs)[J]. Natural Gas Industry, 2018, 38(9): 103-113.
4	唐翠萍, 戴兴学, 梁德青, 等. 低剂量抑制剂Inhibex501存在下的甲烷水合物相平衡研究[J]. 新能源进展, 2018, 6(1): 42-46.
	Tang C P, Dai X X, Liang D Q, et al. Equilibrium conditions for methane hydrate in the presence of low-dosage hydrate inhibitors aqueous solutions[J]. Advances in New and Renewable Enengy, 2018, 6(1): 42-46.
5	Bavoh C B, Partoon B, Lal B, et al. Inhibition effect of amino acids on carbon dioxide hydrate[J]. Chemical Engineering Science, 2017, 171: 331-339.
6	Ke W, Svartaas T M, Abay H K. An experimental study on sⅠ hydrate formation in presence of methanol, PVP and PVCap in an isochoric cell[C]//Icgh 2011. ICGH, 2011: 17-21.
7	Ke W, Kelland M A. Kinetic hydrate inhibitor studies for gas hydrate systems: a review of experimental equipment and test methods[J]. Energy and Fuels, 2016, 30(12): 10015-10028.
8	Talaghat M R. Experimental investigation of induction time for double gas hydrate formation in the simultaneous presence of the PVP and L-tyrosine as kinetic inhibitors in a mini flow loop apparatus[J]. Journal of Natural Gas Science and Engineering, 2014, 19: 215-220.
9	Schicks J M, Ripmesster J A. The coexistence of two different methane hydrate phases under moderate pressure and temperature conditions: kinetic versus thermodynamic products[J]. Angewandte Chemie - International Edition, 2004, 43(25): 3310-3313.
10	Anderson B J, Tester J W, Borghi G P, et al. Properties of inhibitors of methane hydrate formation via molecular dynamics simulations[J]. Journal of the American Chemical Society, 2005, 127(50): 17852-17862.
11	Kelland M A. History of the development of low dosage hydrate inhibitors[J]. Energy and Fuels, 2006, 20(3): 825-847.
12	Kim J, Shin K, Seo Y, et al. Synergistic hydrate inhibition of monoethylene glycol with poly(vinylcaprolactam) in thermodynamically underinhibited system[J]. Journal of Physical Chemistry B, 2014, 118(30): 9065-9075.
13	Chua P C, Kelland M A. Tetra(iso-hexyl)ammonium bromide - the most powerful quaternary ammonium-based tetrahydrofuran crystal growth inhibitor and synergist with polyvinylcaprolactam kinetic gas hydrate inhibitor[J]. Energy and Fuels, 2012, 26(2): 1160-1168.
14	Xu S R, Fan S S, Fang S T, et al. Excellent synergy effect on preventing CH₄ hydrate formation when glycine meets polyvinylcaprolactam[J]. Fuel, 2017, 206: 19-26.
15	Young W D, Cohen J M, Wolf P F. Enhanced hydrate inhibitors: powerful synergism with glycol ethers[J]. ACS Division of Fuel Chemistry, Preprints, 1997, 42(2): 503-506.
16	Xiao C W, Adidharma H. Dual function inhibitors for methane hydrate[J]. Chemical Engineering Science, 2009, 64(7): 1522-1527.
17	Xiao C W, Wibisono N, Adidharma H. Dialkylimidazolium halide ionic liquids as dual function inhibitors for methane hydrate[J]. Chemical Engineering Science, 2010, 65(10): 3080-3087.
18	Villano L D, Kelland M A. An investigation into the kinetic hydrate inhibitor properties of two imidazolium-based ionic liquids on structure II gas hydrate[J]. Chemical Engineering Science, 2010, 65(19): 5366-5372.
19	Kim K S, Kang J W, Kang S P. Tuning ionic liquids for hydrate inhibition[J]. Chemical Communications, 2011, 47(22): 6341-6343.
20	Lee W, Shin J Y, Kin K S, et al. Synergetic effect of ionic liquids on the kinetic inhibition performance of poly(N-vinylcaprolactam) for natural gas hydrate formation[J]. Energy and Fuels, 2016, 30(11): 9162-9169.
21	Lee W, Shin J Y, Kim K S, et al. Kinetic promotion and inhibition of methane hydrate formation by morpholinium ionic liquids with chloride and tetrafluoroborate anions[J]. Energy and Fuels, 2016, 30(5): 3879-3885.
22	Shen X D, Zhou X B, Liang D Q. Kinetic effects of ionic liquids on methane hydrate[J]. Energy and Fuels, 2019, 33(2): 1422-1432.
23	Coquelet C, Chapoy A, Richon D. Development of a new alpha function for the Peng-Robinson equation of state: comparative study of alpha function models for pure gases (natural gas components) and water-gas systems[J]. International Journal of Thermophysics, 2004, 25(1): 133-158.
24	Peng D Y, Robinson D B. A new two-constant equation of state[J]. Industrial and Engineering Chemistry Fundamentals, 1976, 15(1): 59-64.
25	Sangwai J S, Oellrich L. Phase equilibrium of semiclathrate hydrates of methane in aqueous solutions of tetra-n-butyl ammonium bromide (TBAB) and TBAB-NaCl[J]. Fluid Phase Equilibria, 2014, 367: 95-102.
26	Gayet P, Dicharry C, Marion G, et al. Experimental determination of methane hydrate dissociation curve up to 55 MPa by using a small amount of surfactant as hydrate promoter[J]. Chemical Engineering Science, 2005, 60(21): 5751-5758.
27	Nixdorf J, Oellrich L R. Experimental determination of hydrate equilibrium conditions for pure gases, binary and ternary mixtures and natural gases[J]. Fluid Phase Equilibria, 1997, 139(1/2): 325-333.
28	Zhou X B, Long Z, Liang S, et al. In situ Raman analysis on the dissociation behavior of mixed CH₄-CO₂ Hydrates[J]. Energy and Fuels, 2016, 30(2): 1279-1286.
29	Wang J W, Lu H L, Ripmeester J A. Raman spectroscopy and cage occupancy of hydrogen clathrate hydrate from first-principle calculations[J]. Journal of the American Chemical Society, 2009, 131(40): 14132-14133.
30	Schober H, Itoh H, Klapproth A, et al. Guest-host coupling and anharmonicity in clathrate hydrates[J]. European Physical Journal E, 2003, 12(1): 41-49.
31	周雪冰, 刘婵娟, 罗金琼, 等. 甲烷水合物分解过程的微尺度测量[J]. 化工学报, 2019, 70(3): 1042-1047.
	Zhou X B, Liu C J, Luo J Q, et al. Microscopic measurements on methane hydrate dissociation[J]. CIESC Journal, 2019, 70(3): 1042-1047.
32	Lu H L, Moudrakovski I, Riedel M, et al. Occurrence and structural characterization of gas hydrates associated with a cold vent field, offshore Vancouver Island[J]. Journal of Geophysical Research: Solid Earth, 2005, 110(10): 1-9.
33	Uchida T, Hirano T, Ebinuma T, et al. Raman spectroscopic determination of hydration number of methane hydrates[J]. AIChE Journal, 1999, 45(12): 2641-2645.
34	Li Z, Jiang F, Qin H B, et al. Molecular dynamics method to simulate the process of hydrate growth in the presence/absence of KHIs[J]. Chemical Engineering Science, 2017, 164: 307-312.
35	Cheng L W, Liao K, Li Z, et al. The invalidation mechanism of kinetic hydrate inhibitors under high subcooling conditions[J]. Chemical Engineering Science, 2019, 207: 305-316.
36	Kvamme B, Huseby G, Forrisdahl O K. Molecular dynamics simulations of PVP kinetic inhibitor in liquid water and hydrate/liquid water systems[J]. Molecular Physics, 1997, 90(6): 979-992.

[1]	毕丽森, 刘斌, 胡恒祥, 曾涛, 李卓睿, 宋健飞, 吴翰铭. 粗糙界面上纳米液滴蒸发模式的分子动力学研究[J]. 化工学报, 2023, 74(S1): 172-178.
[2]	王琪, 张斌, 张晓昕, 武虎建, 战海涛, 王涛. 氯铝酸-三乙胺离子液体/P₂O₅催化合成伊索克酸和2-乙基蒽醌[J]. 化工学报, 2023, 74(S1): 245-249.
[3]	于宏鑫, 邵双全. 水结晶过程的分子动力学模拟分析[J]. 化工学报, 2023, 74(S1): 250-258.
[4]	金正浩, 封立杰, 李舒宏. 氨水溶液交叉型再吸收式热泵的能量及分析[J]. 化工学报, 2023, 74(S1): 53-63.
[5]	程成, 段钟弟, 孙浩然, 胡海涛, 薛鸿祥. 表面微结构对析晶沉积特性影响的格子Boltzmann模拟[J]. 化工学报, 2023, 74(S1): 74-86.
[6]	肖明堃, 杨光, 黄永华, 吴静怡. 浸没孔液氧气泡动力学数值研究[J]. 化工学报, 2023, 74(S1): 87-95.
[7]	米泽豪, 花儿. 基于DFT和COSMO-RS理论研究多元胺型离子液体吸收SO₂气体[J]. 化工学报, 2023, 74(9): 3681-3696.
[8]	陆俊凤, 孙怀宇, 王艳磊, 何宏艳. 离子液体界面极化及其调控氢键性质的分子机理[J]. 化工学报, 2023, 74(9): 3665-3680.
[9]	郑佳丽, 李志会, 赵新强, 王延吉. 离子液体催化合成2-氰基呋喃反应动力学研究[J]. 化工学报, 2023, 74(9): 3708-3715.
[10]	车睿敏, 郑文秋, 王小宇, 李鑫, 许凤. 基于离子液体的纤维素均相加工研究进展[J]. 化工学报, 2023, 74(9): 3615-3627.
[11]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[12]	宋明昊, 赵霏, 刘淑晴, 李国选, 杨声, 雷志刚. 离子液体脱除模拟油中挥发酚的多尺度模拟与研究[J]. 化工学报, 2023, 74(9): 3654-3664.
[13]	杨绍旗, 赵淑蘅, 陈伦刚, 王晨光, 胡建军, 周清, 马隆龙. Raney镍-质子型离子液体体系催化木质素平台分子加氢脱氧制备烷烃[J]. 化工学报, 2023, 74(9): 3697-3707.
[14]	陈美思, 陈威达, 李鑫垚, 李尚予, 吴有庭, 张锋, 张志炳. 硅基离子液体微颗粒强化气体捕集与转化的研究进展[J]. 化工学报, 2023, 74(9): 3628-3639.
[15]	程业品, 胡达清, 徐奕莎, 刘华彦, 卢晗锋, 崔国凯. 离子液体基低共熔溶剂在转化CO₂中的应用[J]. 化工学报, 2023, 74(9): 3640-3653.

离子液体与PVP K90复合抑制剂对甲烷水合物的生成影响

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

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 12

参考文献 36

相关文章 15

编辑推荐

Metrics

本文评价