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

doi:10.11949/0438-1157.20230180

CIESC Journal ›› 2023, Vol. 74 ›› Issue (6): 2639-2646.DOI: 10.11949/0438-1157.20230180

• Energy and environmental engineering • Previous Articles Next Articles

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:2023-07-27 Published:2023-06-05
Contact: Yong HE, Deqing LIANG

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

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)

Abstract

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

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

CLC Number:

TK 123

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.

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.

Figures/Tables 9

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

Fig.2 High-pressure hydrate reaction apparatus

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

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

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

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

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

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

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

References 39

1	Sloan E D, Koh C A. Clathrate Hydrates of Natural Gases[M]. 3rd ed. Boca Raton, FL: CRC Press/Taylor & Francis, 2008.
2	Lee S Y, Holder G D. Methane hydrates potential as a future energy source[J]. Fuel Processing Technology, 2001, 71(1/2/3): 181-186.
3	Hammerschmidt E G. Formation of gas hydrates in natural gas transmission lines[J]. Industrial & Engineering Chemistry, 1934, 26(8): 851-855.
4	Du J F, Wang X S, Liu H, et al. Experiments and prediction of phase equilibrium conditions for methane hydrate formation in the NaCl, CaCl₂, MgCl₂ electrolyte solutions[J]. Fluid Phase Equilibria, 2019, 479: 1-8.
5	Mohammadi A H, Richon D. Phase equilibria of methane hydrates in the presence of methanol and/or ethylene glycol aqueous solutions[J]. Industrial & Engineering Chemistry Research, 2010, 49(2): 925-928.
6	Kim H, Park J, Seo Y, et al. Hydrate risk management with aqueous ethylene glycol and electrolyte solutions in thermodynamically under-inhibition condition[J]. Chemical Engineering Science, 2017, 158: 172-180.
7	Kamal M S, Hussein I A, Sultan A S, et al. Application of various water soluble polymers in gas hydrate inhibition[J]. Renewable and Sustainable Energy Reviews, 2016, 60: 206-225.
8	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.
9	李锐, 宁伏龙, 张凌, 等. 低剂量水合物抑制剂的研究进展[J]. 石油化工, 2018, 47(2): 203-210.
	Li R, Ning F L, Zhang L, et al. Progress in the research of the low dosage hydrate inhibitors[J]. Petrochemical Technology, 2018, 47(2): 203-210.
10	闫柯乐, 吴伟然, 胡绪尧, 等. 天然气水合物动态防控技术研究及现场应用[J]. 应用化工, 2020, 49(4): 997-1001.
	Yan K L, Wu W R, Hu X Y, et al. Study on the natural gas hydrate kinetic control technology and application in SINOPEC[J]. Applied Chemical Industry, 2020, 49(4): 997-1001.
11	Qin H B, Sun Z F, Wang X Q, et al. Synthesis and evaluation of two new kinetic hydrate inhibitors[J]. Energy & Fuels, 2015, 29(11): 7135-7141.
12	唐翠萍, 张雅楠, 梁德青, 等. 聚乙烯己内酰胺链端改性及其对甲烷水合物形成的抑制作用研究[J]. 化工学报, 2022, 73(5): 2130-2139.
	Tang C P, Zhang Y N, Liang D Q, et al. Inhibition effect of chain end modified polyvinyl caprolactam on methane hydrate formation[J]. CIESC Journal, 2022, 73(5): 2130-2139.
13	王佳琪, 张昕宇, 贺佳乐, 等. 动力学水合物抑制剂性能与官能团作用研究进展及展望[J]. 中南大学学报(自然科学版), 2022, 53(3): 772-798.
	Wang J Q, Zhang X Y, He J L, et al. Research progress and prospects of performance of kinetic hydrate inhibitor and effect of functional group[J]. Journal of Central South University (Science and Technology), 2022, 53(3): 772-798.
14	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.
15	隋金昊, 王智, 梁璇玑, 等. 动力学抑制剂与乙二醇协同作用下甲烷水合物再生成[J]. 化工进展, 2022, 41(10): 5373-5380.
	Sui J H, Wang Z, Liang X J, et al. Paired KHI-MEG for synergistic inhibition of methane hydrate reformation[J]. Chemical Industry and Engineering Progress, 2022, 41(10): 5373-5380.
16	Zhao X, Qiu Z S, Zhou G W, et al. Synergism of thermodynamic hydrate inhibitors on the performance of poly (vinyl pyrrolidone) in deepwater drilling fluid[J]. Journal of Natural Gas Science and Engineering, 2015, 23: 47-54.
17	Kim J, Shin K, Seo Y, et al. Synergistic hydrate inhibition of monoethylene glycol with poly(vinylcaprolactam) in thermodynamically underinhibited system[J]. The Journal of Physical Chemistry B, 2014, 118(30): 9065-9075.
18	Kelland M A, Dirdal E G, Ree L H S. Solvent synergists for improved kinetic hydrate inhibitor performance of poly(N-vinylcaprolactam)[J]. Energy & Fuels, 2020, 34(2): 1653-1663.
19	Zhang Q, Kawatani R, Ajiro H, et al. Optimizing the kinetic hydrate inhibition performance of N-alkyl-N-vinylamide copolymers[J]. Energy & Fuels, 2018, 32(4): 4925-4931.
20	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.
21	Altamash T, Qureshi M F, Aparicio S, et al. Gas hydrates inhibition via combined biomolecules and synergistic materials at wide process conditions[J]. Journal of Natural Gas Science and Engineering, 2017, 46: 873-883.
22	Wang J L, Sun J S, Wang R, et al. Mechanisms of synergistic inhibition of hydrophilic amino acids with kinetic inhibitors on hydrate formation[J]. Fuel, 2022, 321: 124012.
23	Del Villano L, Kelland M A. An investigation into the kinetic hydrate inhibitor properties of two imidazolium-based ionic liquids on Structure Ⅱgas hydrate[J]. Chemical Engineering Science, 2010, 65(19): 5366-5372.
24	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 & Fuels, 2012, 26(2): 1160-1168.
25	Nakarit C, Kelland M A, Liu D J, et al. Cationic kinetic hydrate inhibitors and the effect on performance of incorporating cationic monomers into N-vinyl lactam copolymers[J]. Chemical Engineering Science, 2013, 102: 424-431.
26	Xiao C W, Adidharma H. Dual function inhibitors for methane hydrate[J]. Chemical Engineering Science, 2009, 64(7): 1522-1527.
27	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.
28	Kim K S, Kang J W, Kang S P. Tuning ionic liquids for hydrate inhibition[J]. Chemical Communications, 2011, 47(22): 6341-6343.
29	Kang S P, Kim E S, Shin J Y, et al. Unusual synergy effect on methane hydrate inhibition when ionic liquid meets polymer[J]. RSC Advances, 2013, 3(43): 19920-19923.
30	Lee W, Shin J Y, Cha J H, et al. Inhibition effect of ionic liquids and their mixtures with poly(N-vinylcaprolactam) on methane hydrate formation[J]. Journal of Industrial and Engineering Chemistry, 2016, 38: 211-216.
31	Shen X D, Zhou X B, Liang D Q. Kinetic effects of ionic liquids on methane hydrate[J]. Energy & Fuels, 2019, 33(2): 1422-1432.
32	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.
	Ren J J, Long Z, Liang D Q. Effect of complex inhibitors containing ionic liquids and PVP K90 on formation of methane hydrate[J]. CIESC Journal, 2020, 71(11): 5256-5264.
33	Ren J J, Lu Z L, Long Z, et al. Experimental study on the kinetic effect of N-butyl-N-methylpyrrolidinium tetrafluoroborate and poly (N-vinyl-caprolactam) on CH₄ hydrate formation[J]. RSC Advances, 2020, 10(26): 15320-15327.
34	Lee W, Shin J Y, Kim 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 & Fuels, 2016, 30(11): 9162-9169.
35	Kang S P, Jung T, Lee J W. Macroscopic and spectroscopic identifications of the synergetic inhibition of an ionic liquid on hydrate formations[J]. Chemical Engineering Science, 2016, 143: 270-275.
36	Long Z, Zhou X B, Lu Z L, et al. Kinetic inhibition performance of N-vinyl caprolactam/isopropylacrylamide copolymers on methane hydrate formation[J]. Energy, 2022, 242: 123056.
37	Abrahamsen E, Kelland M A. Comparison of kinetic hydrate inhibitor performance on structure Ⅰ and structure Ⅱ hydrate-forming gases for a range of polymer classes[J]. Energy & Fuels, 2018, 32(1): 342-351.
38	Stern L A, Lorenson T D. Grain-scale imaging and compositional characterization of cryo-preserved India NGHP 01 gas-hydrate-bearing cores[J]. Marine and Petroleum Geology, 2014, 58: 206-222.
39	Klapp S A, Bohrmann G, Kuhs W F, et al. Microstructures of structure Ⅰ and Ⅱ gas hydrates from the Gulf of Mexico[J]. Marine and Petroleum Geology, 2010, 27(1): 116-125.

[1]	Cheng CHENG, Zhongdi DUAN, Haoran SUN, Haitao HU, Hongxiang XUE. Lattice Boltzmann simulation of surface microstructure effect on crystallization fouling [J]. CIESC Journal, 2023, 74(S1): 74-86.
[2]	Qi WANG, Bin ZHANG, Xiaoxin ZHANG, Hujian WU, Haitao ZHAN, Tao WANG. Synthesis of isoxepac and 2-ethylanthraquinone catalyzed by chloroaluminate-triethylamine ionic liquid/P₂O₅ [J]. CIESC Journal, 2023, 74(S1): 245-249.
[3]	Ruimin CHE, Wenqiu ZHENG, Xiaoyu WANG, Xin LI, Feng XU. Research progress on homogeneous processing of cellulose in ionic liquids [J]. CIESC Journal, 2023, 74(9): 3615-3627.
[4]	Zehao MI, Er HUA. DFT and COSMO-RS theoretical analysis of SO₂ absorption by polyamines type ionic liquids [J]. CIESC Journal, 2023, 74(9): 3681-3696.
[5]	Junfeng LU, Huaiyu SUN, Yanlei WANG, Hongyan HE. Molecular understanding of interfacial polarization and its effect on ionic liquid hydrogen bonds [J]. CIESC Journal, 2023, 74(9): 3665-3680.
[6]	Jiali ZHENG, Zhihui LI, Xinqiang ZHAO, Yanji WANG. Kinetics of ionic liquid catalyzed synthesis of 2-cyanofuran [J]. CIESC Journal, 2023, 74(9): 3708-3715.
[7]	Minghao SONG, Fei ZHAO, Shuqing LIU, Guoxuan LI, Sheng YANG, Zhigang LEI. Multi-scale simulation and study of volatile phenols removal from simulated oil by ionic liquids [J]. CIESC Journal, 2023, 74(9): 3654-3664.
[8]	Shaoqi YANG, Shuheng ZHAO, Lungang CHEN, Chenguang WANG, Jianjun HU, Qing ZHOU, Longlong MA. Hydrodeoxygenation of lignin-derived compounds to alkanes in Raney Ni-protic ionic liquid system [J]. CIESC Journal, 2023, 74(9): 3697-3707.
[9]	Meisi CHEN, Weida CHEN, Xinyao LI, Shangyu LI, Youting WU, Feng ZHANG, Zhibing ZHANG. Advances in silicon-based ionic liquid microparticle enhanced gas capture and conversion [J]. CIESC Journal, 2023, 74(9): 3628-3639.
[10]	Yepin CHENG, Daqing HU, Yisha XU, Huayan LIU, Hanfeng LU, Guokai CUI. Application of ionic liquid-based deep eutectic solvents for CO₂ conversion [J]. CIESC Journal, 2023, 74(9): 3640-3653.
[11]	Lizhi WANG, Qiancheng HANG, Yeling ZHENG, Yan DING, Jiaji CHEN, Qing YE, Jinlong LI. Separation of methyl propionate + methanol azeotrope using ionic liquid entrainers [J]. CIESC Journal, 2023, 74(9): 3731-3741.
[12]	Jie CHEN, Yongsheng LIN, Kai XIAO, Chen YANG, Ting QIU. Study on catalytic synthesis of sec-butanol by tunable choline-based basic ionic liquids [J]. CIESC Journal, 2023, 74(9): 3716-3730.
[13]	Xudong YU, Qi LI, Niancu CHEN, Li DU, Siying REN, Ying ZENG. Phase equilibria and calculation of aqueous ternary system KCl + CaCl₂ + H₂O at 298.2, 323.2, and 348.2 K [J]. CIESC Journal, 2023, 74(8): 3256-3265.
[14]	Yuanliang ZHANG, Xinqi LUAN, Weige SU, Changhao LI, Zhongxing ZHAO, Liqin ZHOU, Jianmin CHEN, Yan HUANG, Zhenxia ZHAO. Study on selective extraction of nicotine by ionic liquids composite extractant and DFT calculation [J]. CIESC Journal, 2023, 74(7): 2947-2956.
[15]	Chunyu LIU, Huanyu ZHOU, Yue MA, Changtao YUE. Drying characteristics and mathematical model of CaO-conditioned oil sludge [J]. CIESC Journal, 2023, 74(7): 3018-3027.

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

离子液体协同PVCap抑制天然气水合物生成实验研究

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 9

References 39

Related Articles 15

Recommended Articles

Metrics

Comments