水合物法分離氣體的促進劑及促進機理研究進展

王蘭云; 謝輝龍; 盧曉冉; 徐永亮; 王燕; 李瑤; 魏建平

doi:10.13374/j.issn2095-9389.2020.07.06.004

水合物法分離氣體的促進劑及促進機理研究進展

doi: 10.13374/j.issn2095-9389.2020.07.06.004

王蘭云^{1, 2, 3},
謝輝龍¹,
盧曉冉¹,
徐永亮^{1, 2, 3, ,},
王燕^{1, 2, 3},
李瑤^{1, 2, 3},
魏建平^{1, 2, 3}

1.
河南理工大學安全科學與工程學院，焦作 454003
2.
河南省瓦斯地質與瓦斯治理重點實驗室—省部共建國家重點實驗室培育基地，焦作 454003
3.
煤炭安全生產與清潔高效利用省部共建協同創新中心，焦作 454003

基金項目: 國家自然科學基金資助項目（51874124，52074108）；中國博士后科學基金特別資助項目（2018T110725）；河南理工大學杰出青年基金資助項目（J2019-5）；河南省高等院校重點科研資助項目（19A440009）

詳細信息

通訊作者:
E-mail：xylcumt@hpu.edu.cn

中圖分類號: TQ028.8
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出版歷程
- 收稿日期: 2020-07-06
- 刊出日期: 2021-01-25

Research progress of promoters and promoting mechanisms for hydrate-based gas separation

WANG Lan-yun^{1, 2, 3},
XIE Hui-long¹,
LU Xiao-ran¹,
XU Yong-liang^{1, 2, 3
, ,},
WANG Yan^{1, 2, 3},
LI Yao^{1, 2, 3},
WEI Jian-ping^{1, 2, 3}

1.
College of Safety Science and Engineering, Henan Polytechnic University, Jiaozuo 454003, China
2.
State Key Laboratory Cultivation Base for Gas Geology and Gas Control, Henan Polytechnic University, Jiaozuo 454003, China
3.
State Collaborative Innovation Center of Coal Work Safety and Clean-efficiency Utilization, Jiaozuo 454003, China

More Information

Corresponding author: E-mail: xylcumt@hpu.edu.cn

摘要

摘要: 目前添加促進劑后水合物形成機理并無統一定論，本文詳細闡述了氣體水合物形成的降低表面張力理論、臨界膠束理論、毛細效應理論、模板效應理論和表面疏水效應理論等促進機理，綜述了傳統促進劑（THF、CP、SDS）、生物環保型促進劑（氨基酸、淀粉），尤其是離子液體在氣體水合物形成相平衡實驗、動力學規律和促進機理方面的應用研究進展，闡述了離子液體半籠型水合促進劑在混合氣體分離方面的研究現狀，指出應從促進劑結構性質及其在水相中的聚集形態入手，研究促進劑?氣體?水之間的分子間作用力，建立各類氣體水合物促進劑的篩選體系。
- 水合物 /
- 氣體分離 /
- 離子液體 /
- 促進機理 /
- 促進劑
Abstract: Unconventional natural gas is a type of high-quality clean energy, which often contains some gases as impurities that cause reductions in its combustion heat value and utilization efficiency. Therefore, developing gas separation technologies to remove or separate these impurity gases and concentrate methane content is necessary. As a newly emerging gas separation technology, hydrate-based gas separation technology currently requires exploration on ways to greatly increase hydration rate to promote its industrial application. Screening green and environmentally-friendly promoters has become a research hotspot in recent decades. Amino acids, starch, and other biological substances have attracted much attention owing to their wide accessibility and environmental protection. Ionic liquids (ILs), which are a new type of lowly volatile and recyclable solvents, exhibit excellent performance in promoting gas hydrates formation and growth. Furthermore, ILs exhibit adjustable and controllable structures, which make them potential promoters in hydrate-based gas separation. Presently, no universally recognized theory on hydrate formation mechanism exists for various promoters. In this paper, different promotion mechanisms of gas hydration were described and discussed in detail, which included surface tension reduction theory, critical micelle theory, capillary effect theory, template effect theory, and surface hydrophobic effect theory. Both traditional promoters (e.g., THF, CP, and SDS) and bio-environmental promoters (e.g., amino acids and starch) were reviewed in the terms of gas hydration equilibrium condition, dynamic regularity, and hydrates-acceleration mechanisms. Particularly, the application of ILs, which are a type of semi-clathrate promoter, in gas hydration was elaborated. Study on the structural properties of promoters, their aggregation morphology in water, and intermolecular interactions between ILs, gases, and water is necessary for the establishment of a promoter-screening system for various gas hydrations.
- hydrate /
- gas separation /
- ionic liquids /
- promoting mechanisms /
- promoters

HTML全文

圖 1 CH₄、N₂、CO₂、O₂及H₂S在純水中生成水合物的相平衡條件^[19-21]

Figure 1. Hydrate equilibrium curve of CH₄, N₂, CO₂, O₂, and H₂S in pure water^[19-21]

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圖 2 水合物法分離低濃度瓦斯原理

Figure 2. Hydrate-based gas separation principle for low-concentration coalbed-mine methane

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圖 3 降低表面張力理論示意圖

Figure 3. Schematic of reducing surface tension theory

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圖 4 SDS的膠束模型示意圖（a）^[26] 與毛細效應理論示意圖（b）^[32]

Figure 4. Schematic of SDS micelle models (a)^[26] and schematic of capillary theory (b)^[32]

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圖 5 ZIF-61模板效應促進THF水合物的成核（a）^[36] 以及SAP與水形成的環狀結構（b）^[37]

Figure 5. Promotion of THF hydrate nucleation by ZIF-61 due to template effect (a)^[36], and ring structure formed by SAP and water (b)^[37]

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圖 6 固體表面疏水理論示意圖^[41]

Figure 6. Schematic of surface hydrophobicity theory^[41]

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圖 7 氨基酸通過氫鍵嵌入水合物晶體結構示意圖^[66]

Figure 7. Incorporation of amino acids into hydrate crystal lattice through hydrogen bonding^[66]

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圖 8 玉米淀粉分子結構示意圖（a）^[70]與β-環糊精結構示意圖（b）

Figure 8. Schematic of the molecular structure of maize starch (a)^[70] and schematic of β-cyclodextrin structure (b)

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圖 9 TiAAB?38H₂O半水合物晶體結構圖。（a）藍色：容納CH₄或Kr的A型籠；（b）綠色：容納水分子的B型籠

Figure 9. Crystal structure of TiAAB·38H₂O hydrate: (a) blue: A-cage hosting CH₄ or Kr; (b) green: B-cage hosting a water molecule

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圖 10 不同離子液體存在下CO₂,CH₄,N₂水合物相平衡圖^[90-91], 其中[P_{4 4 4 4}]Br，[N_{4 4 4 4}]Br的質量分數都為10%

Figure 10. Phase equilibrium diagram of CO₂, CH₄, and N₂ hydrates in the presence of different ionic liquids^[90-91], the mass fraction of [P_{4 4 4 4}]Br and [N_{4 4 4 4}]Br is 10%

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參考文獻(101)

[1]	Li Y, Zhou D H, Wang W H, et al. Development of unconventional gas and technologies adopted in China. Energy Geosci, 2020, 1(1-2): 55
[2]	Zang X Y, Liang D Q, Wu N Y. Research progress in hydrate-based carbon dioxide separation from natural gas/biogas. Mod Chem Ind, 2015, 35(2): 13 臧小亞, 梁德青, 吳能友. 基于水合物技術分離天然氣/沼氣中CO₂的研究進展. 現代化工, 2015, 35(2):13
[3]	Gu H M, Song G H, Xiao J, et al. Thermodynamic analysis of the biomass-to-synthetic natural gas using chemical looping technology with CaO sorbent. Energy Fuels, 2013, 27(8): 4695
[4]	Chen Q, Liu T B. Biogas system in rural China: Upgrading from decentralized to centralized? Renewable Sustainable Energy Rev, 2017, 78: 933
[5]	Yuan L. Scientific thinking and countermeasures of coalbed methane development and utilization in China. Sci Technol Rev, 2011, 29(22): 3 袁亮. 我國煤層氣開發利用的科學思考與對策. 科技導報, 2011, 29(22):3
[6]	Qu S J, Dong W G, Li X F, et al. Research and application of the low concentrated coal bed methane upgrading technique. J China Coal Soc, 2014, 39(8): 1539 曲思建, 董衛國, 李雪飛, 等. 低濃度煤層氣脫氧濃縮工藝技術開發與應用. 煤炭學報, 2014, 39(8):1539
[7]	Liu J Z, Sun H T, Lei Y, et al. Current situation and development trend of coalbed methane development and utilization technology in coal mine area. J China Coal Soc, 2020, 45(1): 258 劉見中, 孫海濤, 雷毅, 等. 煤礦區煤層氣開發利用新技術現狀及發展趨勢. 煤炭學報, 2020, 45(1):258
[8]	Li Y L, Liu Y S, Yang X, et al. Safety analysis on low concentration coal bed methane enrichment process by proportion pressure swing adsorption. J China Coal Soc, 2012, 37(5): 804 李永玲, 劉應書, 楊雄, 等. 等比例變壓吸附法富集低濃度煤層氣的安全性分析. 煤炭學報, 2012, 37(5):804
[9]	Al-Rabiah A A, Ajbar A M, Soliman M A, et al. Modeling of nitrogen separation from natural gas through nanoporous carbon membranes. J Nat Gas Sci Eng, 2015, 26: 1278
[10]	Hadri N E, Quang D V, Goetheer E L V, et al. Aqueous amine solution characterization for post-combustion CO₂ capture process. Appl Energy, 2017, 185: 1433
[11]	Chen J H, Xiao L, Ling H L. Study on cryogenic liquefaction technique of low concentration coalbed methane. Coal Sci Technol, 2016, 44(6): 134 陳金華, 肖露, 令狐磊. 低濃度煤層氣深冷液化工藝研究. 煤炭科學技術, 2016, 44(6):134
[12]	Li W, Wang Z, Li P Y, et al. Progress in membrane technology for CH₄-N₂ separation. CIESC J, 2016, 67(2): 404 李雯, 王志, 李潘源, 等. 用于甲烷-氮氣體系分離的膜技術研究進展. 化工學報, 2016, 67(2):404
[13]	Chen G J, Sun C Y, Ma Q L. Gas Hydrate Science and Technology. Beijing: Chemical Industry Press, 2008 陳光進, 孫長宇, 馬慶蘭. 氣體水合物科學與技術. 北京: 化學工業出版社, 2008
[14]	Sloan E D. Fundamental principles and applications of natural gas hydrates. Nature, 2003, 426: 353
[15]	Sloan E D, Koh C A, Koh C. Clathrate Hydrates of Natural Gases. 3rd Ed. Florida: CRC Press, 2007
[16]	Li A R, Jiang L L, Tang S Y. An experimental study on carbon dioxide hydrate formation using a gas-inducing agitated reactor. Energy, 2017, 134: 629
[17]	Park S S, Kim N J. Study on methane hydrate formation using ultrasonic waves. J Ind Eng Chem, 2013, 19(5): 1668
[18]	Wang X L, Dennis M. Charging performance of a CO₂ semi-clathrate hydrate based PCM in a lab-scale cold storage system. Appl Therm Eng, 2017, 126: 762
[19]	Adisasmito S, Frank R J, Sloan E D. Hydrates of carbon dioxide and methane mixtures. J Chem Eng Data, 1991, 36(1): 68
[20]	Mohammadi A H, Tohidi, B, Burgass R W. Equilibrium data and thermodynamic modeling of nitrogen, oxygen, and air clathrate hydrates. J Chem Eng Data, 2003, 48(3): 612
[21]	Ward Z T, Deering C E, Marriott R A, et al. Phase equilibrium data and model comparisons for H₂S hydrates. J Chem Eng Data, 2015, 60(2): 403
[22]	Dicharry C, Duchateau C, Asbai H, et al. Carbon dioxide gas hydrate crystallization in porous silica gel particles partially saturated with a surfactant solution. Chem Eng Sci, 2013, 98: 88
[23]	Li Y X, Zhu C, Wang W C. Promoting effects of surfactants on carbon dioxide hydrate formation and the kinetics. Petrochem Technol, 2012, 41(6): 699 doi: 10.3969/j.issn.1000-8144.2012.06.015 李玉星, 朱超, 王武昌. 表面活性劑促進CO₂水合物生成的實驗及動力學模型. 石油化工, 2012, 41(6):699 doi: 10.3969/j.issn.1000-8144.2012.06.015
[24]	Zhang Q D, Li Y X, Wang W C. Influence of chemical additives on hydrate formation and gas storage. Chem Eng Oil Gas, 2014, 43(2): 146 doi: 10.3969/j.issn.1007-3426.2014.02.008 張慶東, 李玉星, 王武昌. 化學添加劑對水合物生成和儲氣的影響. 石油與天然氣化工, 2014, 43(2):146 doi: 10.3969/j.issn.1007-3426.2014.02.008
[25]	Zhang B Y, Wu Q, Wang Y J. Reaction mechanism between surfactant and induction of gas hydrate formation. J Jilin Univ Eng Technol Ed, 2007, 37(1): 239 張保勇, 吳強, 王永敬. 表面活性劑對氣體水合物生成誘導時間的作用機理. 吉林大學學報(工學版), 2007, 37(1):239
[26]	Zhong Y, Rogers R E. Surfactant effects on gas hydrate formation. Chem Eng Sci, 2000, 55(19): 4175
[27]	Wang F, Jia Z Z, Luo S J, et al. Effects of different anionic surfactants on methane hydrate formation. Chem Eng Sci, 2015, 137: 896
[28]	Veluswamy H P, Chen J Y, Linga P. Surfactant effect on the kinetics of mixed hydrogen/propane hydrate formation for hydrogen storage as clathrates. Chem Eng Sci, 2015, 126: 488
[29]	Profio P D, Arca S, Germani R, et al. Surfactant promoting effects on clathrate hydrate formation: Are micelles really involved? Chem Eng Sci, 2005, 60(15): 4141
[30]	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. Chem Eng Sci, 2005, 60(21): 5751
[31]	Lo C, Zhang J S, Somasundaran P, et al. Investigations of surfactant effects on gas hydrate formation via infrared spectroscopy. J Colloid Interface Sci, 2012, 376(1): 173
[32]	Meng H L, Guo R B, Wang F, et al. Effect of different surfactants on methane hydrate formation. Renewable Energy Resour, 2017, 35(3): 329 孟漢林, 郭榮波, 王飛, 等. 不同表面活性劑對甲烷水合物生成的影響. 可再生能源, 2017, 35(3):329
[33]	Yoslim J, Linga P, Englezos P. Enhanced growth of methane-propane clathrate hydrate crystals with sodium dodecyl sulfate, sodium tetradecyl sulfate, and sodium hexadecyl sulfate surfactants. J Cryst Growth, 2010, 313(1): 68
[34]	Zhang J S, Lee S, Lee J W. Kinetics of methane hydrate formation from SDS solution. Ind Eng Chem Res, 2007, 46(19): 6353
[35]	Molokitina N S, Nesterov A N, Podenko L S, et al. Carbon dioxide hydrate formation with SDS: Further insights into mechanism of gas hydrate growth in the presence of surfactant. Fuel, 2019, 235: 1400
[36]	Wang Y H, Lang X M, Fan S S. Accelerated nucleation of tetrahydrofuran (THF) hydrate in presence of ZIF-61. J Nat Gas Chem, 2012, 21(3): 299
[37]	Long F, Fan S S, Wang Y H, et al. Promoting effect of super absorbent polymer on hydrate formation. J Nat Gas Chem, 2010, 19(3): 251
[38]	Lü Q N. Experimental Study on Thermodynamics and Formation Kinetics of Multicomponent Hydrate[Dissertation]. Dalian: Dalian University of Technology, 2018 呂秋楠. 多元水合物熱力學及生成動力學實驗研究[學位論文]. 大連: 大連理工大學, 2018
[39]	Chandler D. Interfaces and the driving force of hydrophobic assembly. Nature, 2005, 437(7059): 640
[40]	Kauzmann W. Some factors in the interpretation of protein denaturation. Adv Protein Chem, 1959, 14: 1
[41]	Nguyen N N, Nguyen A V. Hydrophobic effect on gas hydrate formation in the presence of additives. Energy Fuels, 2017, 31(10): 10311
[42]	Nguyen N N, Nguyen A V. The dual effect of sodium halides on the formation of methane gas hydrate. Fuel, 2015, 156: 87
[43]	Farhang F, Nguyen A V, Hampton M A. Influence of sodium halides on the kinetics of CO₂ hydrate formation. Energy Fuels, 2014, 28(2): 1220
[44]	Sowa B, Zhang X H, Hartley P G, et al. Formation of ice, tetrahydrofuran hydrate, and methane/propane mixed gas hydrates in strong monovalent salt solutions. Energy Fuels, 2014, 28(11): 6877
[45]	Wang M, Sun Z G, Qiu X H, et al. Hydrate dissociation equilibrium conditions for carbon dioxide + tetrahydrofuran. J Chem Eng Data, 2017, 62(2): 812
[46]	Wang M, Sun Z G, Li C H, et al. Equilibrium hydrate dissociation conditions of CO₂ + HCFC141b or cyclopentane. J Chem Eng Data, 2016, 61(9): 3250
[47]	Ding J X, Shi L L, Shen X D, et al. SDS effect on formation kinetics and microstructure of methane hydrate. CIESC J, 2017, 68(12): 4802 丁家祥, 史伶俐, 申小冬, 等. SDS對甲烷水合物生成動力學和微觀結構的影響. 化工學報, 2017, 68(12):4802
[48]	Zhao J Z, Zhao Y S, Shi D X. Experiment on methane concentration from oxygen-containing coal bed gas by THF solution hydrate formation. J China Coal Soc, 2008, 33(12): 1419 doi: 10.3321/j.issn:0253-9993.2008.12.018 趙建忠, 趙陽升, 石定賢. THF溶液水合物技術提純含氧煤層氣的實驗. 煤炭學報, 2008, 33(12):1419 doi: 10.3321/j.issn:0253-9993.2008.12.018
[49]	Yang L. Static Enhancement Technology of Methane Hydrate Formation[Dissertation]. Guangzhou: South China University of Technology, 2013 楊亮. 甲烷水合物生成的靜態強化技術[學位論文]. 廣州: 華南理工大學, 2013
[50]	Zhang Q, Wu Q, Zhang H, et al. Effect of montmorillonite on hydrate-based methane separation from mine gas. J Central South Univ, 2018, 25(1): 38
[51]	Zhao X C. Experimental Study on Formation Characteristics of Coalbed Methane Hydrate at Mesoscopic Scale[Dissertation]. Taiyuan: Taiyuan University of Technology, 2019 趙小晨. 介觀尺度下煤層氣水合物生成特性實驗研究[學位論文]. 太原: 太原理工大學, 2019
[52]	Seo Y T, Kang S P, Lee H. Experimental determination and thermodynamic modeling of methane and nitrogen hydrates in the presence of THF, propylene oxide, 1, 4-dioxane and acetone. Fluid Phase Equilib, 2001, 189(1-2): 99
[53]	Sizikov A A, Manakov A Y, Aladko E Y. Pressure dependence of gas hydrate formation in triple systems water – 2-Propanol–methane and water-2-Propanol–hydrogen. Fluid Phase Equilib, 2016, 425: 351
[54]	Susilo R, Ripmeester J A, Englezos P. Methane conversion rate into structure H hydrate crystals from ice. AIChE J, 2007, 53(9): 2451
[55]	Mazraeno M S, Varaminian F, Vafaie-Sefti M. Experimental and modeling investigation on structure H hydrate formation kinetics. Energy Convers Manage, 2013, 76: 1
[56]	Chen B, Xin F, Song X F, et al. Enhancement of methane hydrate formation process in phase change slurry. CIESC J, 2016, 67(8): 3202 陳彬, 辛峰, 宋小飛, 等. 相變漿液中甲烷水合物的生成過程強化. 化工學報, 2016, 67(8):3202
[57]	Zhu M G, Sun Z G, Yang M M, et al. Experimental study on promoting HCFC-141b hydrate formation with organic phase change material. Chem Ind Eng Prog, 2017, 36(4): 1265 朱明貴, 孫志高, 楊明明, 等. 有機相變材料促進HCFC-141b水合物生成實驗. 化工進展, 2017, 36(4):1265
[58]	Wang W X, Zeng P Y, Long X Y, et al. Methane storage in tea clathrates. Chem Commun, 2014, 50(10): 1244
[59]	Chen Y F, Yang C H, Chang M S, et al. Foam properties and detergent abilities of the saponins from camellia oleifera. Int J Mol Sci, 2010, 11(11): 4417
[60]	Veluswamy H P, Kumar A, Kumar R, et al. An innovative approach to enhance methane hydrate formation kinetics with leucine for energy storage application. Appl Energy, 2017, 188: 190
[61]	Farhadian A, Varfolomeev M A, Abdelhay Z, et al. Accelerated methane hydrate formation by ethylene diamine tetraacetamide as an efficient promoter for methane storage without foam formation. Ind Eng Chem Res, 2019, 58(19): 7752
[62]	Liu Y, Chen B Y, Chen Y L, et al. Methane storage in a hydrated form as promoted by leucines for possible application to natural gas transportation and storage. Energy Technol, 2015, 3(8): 815
[63]	Veluswamy H P, Hong Q W, Linga P. Morphology study of methane hydrate formation and dissociation in the presence of amino acid. Cryst Growth Des, 2016, 16(10): 5932
[64]	Bhattacharjee G, Choudhary N, Kumar A, et al. Effect of the amino acid l-histidine on methane hydrate growth kinetics. J Nat Gas Sci Eng, 2016, 35: 1453
[65]	Veluswamy H P, Lee P Y, Premasinghe K, et al. Effect of biofriendly amino acids on the kinetics of methane hydrate formation and dissociation. Ind Eng Chem Res, 2017, 56(21): 6145
[66]	Sa J H, Kwak G H, Lee B R, et al. Abnormal incorporation of amino acids into the gas hydrate crystal lattice. Phys Chem Chem Phys, 2014, 16(48): 26730
[67]	Zhang Z E, Li Y F, Zhang W X, et al. Effectiveness of amino acid salt solutions in capturing CO₂: A review. Renewable Sustainable Energy Rev, 2018, 98: 179
[68]	Fakharian H, Ganji H, Far A N, et al. Potato starch as methane hydrate promoter. Fuel, 2012, 94: 356
[69]	Ganji H, Manteghian M, Mofrad H R. Effect of mixed compounds on methane hydrate formation and dissociation rates and storage capacity. Fuel Process Technol, 2007, 88(9): 891
[70]	Babakhani S M, Alamdari A. Effect of maize starch on methane hydrate formation/dissociation rates and stability. J Nat Gas Sci Eng, 2015, 26: 1
[71]	Lin Y J, Veluswamy H P, Linga P. Effect of eco-friendly cyclodextrin on the kinetics of mixed methane–tetrahydrofuran hydrate formation. Ind Eng Chem Res, 2018, 57(17): 5944
[72]	Mohammad-Taheri M, Moghaddam A Z, Nazari K, et al. Methane hydrate stability in the presence of water-soluble hydroxyalkyl cellulose. J Nat Gas Chem, 2012, 21(2): 119
[73]	Al-Adel S, Dick J A G, El-Ghafari R, et al. The effect of biological and polymeric inhibitors on methane gas hydrate growth kinetics. Fluid Phase Equilib, 2008, 267(1): 92
[74]	Kumar A, Sakpal T, Kumar R. Influence of low-dosage hydrate inhibitors on methane clathrate hydrate formation and dissociation kinetics. Energy Technol, 2015, 3(7): 717
[75]	Karaaslan U, Parlaktuna M. Promotion effect of polymers and surfactants on hydrate formation rate. Energy Fuels, 2002, 16(6): 1413
[76]	Kiran B S, Prasad P S R. Storage of methane gas in the form of clathrates in the presence of natural bioadditives. ACS Omega, 2018, 3(12): 18984
[77]	Lee J D, Wu H J, Englezos P. Cationic starches as gas hydrate kinetic inhibitors. Chem Eng Sci, 2007, 62(23): 6548
[78]	Sa J H, Kwak G H, Lee B R, et al. Hydrophobic amino acids as a new class of kinetic inhibitors for gas hydrate formation. Sci Rep, 2013, 3: 2428
[79]	Sa J H, Kwak G H, Han K, et al. Inhibition of methane and natural gas hydrate formation by altering the structure of water with amino acids. Sci Rep, 2016, 6: 31582
[80]	Fowler D L, Loebenstein W V, Pall D B, et al. Some unusual hydrates of quaternary ammonium salts. J Am Chem Soc, 1940, 62(5): 1140
[81]	Wang W X, Carter B O, Bray C L, et al. Reversible methane storage in a polymer-supported semi-clathrate hydrate at ambient temperature and pressure. Chem Mater, 2009, 21(16): 3810
[82]	Long X J, Wang Y H, Lang X M, et al. Hydrate equilibrium measurements for CH₄, CO₂, and CH₄ + CO₂ in the presence of tetra-n-butyl ammonium bromide. J Chem Eng Data, 2016, 61(11): 3897
[83]	Makino T, Yamamoto T, Nagata K, et al. Thermodynamic stabilities of tetra-n-butyl ammonium chloride + H₂, N₂, CH₄, CO₂, or C₂H₆ semiclathrate hydrate systems. J Chem Eng Data, 2010, 55(2): 839
[84]	Mohammadi A, Manteghian M, Mohammadi A H. Dissociation data of semiclathrate hydrates for the systems of tetra-n-butylammonium fluoride (TBAF) + methane + water, TBAF + carbon dioxide + water, and TBAF + nitrogen +water. J Chem Eng Data, 2013, 58(12): 3545
[85]	Hughes T J, Marsh K N. Methane semi-clathrate hydrate phase equilibria with tetraisopentylammonium fluoride. J Chem Eng Data, 2011, 56(12): 4597
[86]	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. Chem Eng Sci, 2010, 65(19): 5366
[87]	Sun Z G, Jiao L J, Zhao Z G, et al. Experimental study on the methane formation conditions with the presence of ionic liquids. Sci Technol Eng, 2013, 13(15): 4361 doi: 10.3969/j.issn.1671-1815.2013.15.041 孫志高, 焦麗君, 趙之貴, 等. 含離子液體體系甲烷水合物形成特性實驗研究. 科學技術與工程, 2013, 13(15):4361 doi: 10.3969/j.issn.1671-1815.2013.15.041
[88]	Cha J H, Ha C, Han S, et al. Experimental measurement of phase equilibrium of hydrate in water plus ionic liquid+CH₄ system. J Chem Eng Data, 2016, 61(1): 543
[89]	Khan M S, Bavoh C B, Partoon B, et al. Thermodynamic effect of ammonium based ionic liquids on CO₂ hydrates phase boundary. J Mol Liquids, 2017, 238: 533
[90]	Mohammadi A H, Eslamimanesh A, Belandria V, et al. Phase equilibria of semiclathrate hydrates of CO₂, N₂, CH₄, or H₂+Tetra-n-butylammonium bromide aqueous solution. J Chem Eng Data, 2011, 56(10): 3855
[91]	Ilani-Kashkouli P, Mohammadi A H, Naidoo P, et al. Hydrate phase equilibria for CO₂, CH₄, or N₂ + tetrabutylphosphonium bromide (TBPB) aqueous solution. Fluid Phase Equilib, 2016, 411: 88
[92]	Shi L L, Liang D Q, Li D L. Phase equilibrium data of tetrabutylphosphonium bromide plus carbon dioxide or nitrogen semiclathrate hydrates. J Chem Eng Data, 2013, 58(7): 2125
[93]	Li X S, Zhan H, Xu C G, et al. Effects of tetrabutyl-(ammonium/phosphonium) salts on clathrate hydrate capture of CO₂ from simulated flue gas. Energy Fuels, 2012, 26(4): 2518
[94]	Suginaka T, Sakamoto H, Iino K, et al. Phase equilibrium for ionic semiclathrate hydrate formed with CO₂, CH₄, or N₂ plus tetrabutylphosphonium bromide. Fluid Phase Equilib, 2013, 344: 108
[95]	Mohammadi A. Pakzad M, Mohammadi A H, et al. Kinetics of (TBAF+CO₂) semi-clathrate hydrate formation in the presence and absence of SDS. Petrol Sci, 2018, 15(2): 375
[96]	Duc N H, Chauvy F, Herri J M. CO₂ capture by hydrate crystallization-A potential solution for gas emission of steelmaking industry. Energy Convers Manage, 2007, 48(4): 1313
[97]	Li S, Bi Y, Yang C L, et al. Double-capture process of CO₂ by gas hydrate and aqueous solution of ionic liquid. Chin J Process Eng, 2014, 14(3): 409 李松, 畢崟, 楊翠蓮, 等. 離子液體水溶液-氣體水合物對CO₂的雙捕獲工藝. 過程工程學報, 2014, 14(3):409
[98]	Fan S S, Li S F, Wang J Q, et al. Efficient capture of CO₂ from simulated flue gas by formation of TBAB or TBAF semiclathrate hydrates. Energy Fuels, 2009, 23(8): 4202
[99]	Fan S S, Long X J, Lang X M, et al. CO₂ capture from CH₄/CO₂ mixture gas with tetra-n-butylammonium bromide semi-clathrate hydrate through a pressure recovery method. Energy Fuels, 2016, 30(10): 8529
[100]	Luo Y, Li X X, Guo G J, et al. Equilibrium conditions of binary gas mixture CH₄ + H₂ in semiclathrate hydrates of tetra-n-butyl ammonium bromide. J Chem Eng Data, 2018, 63(10): 3975
[101]	Horii S, Ohmura R. Continuous separation of CO₂ from a H₂ +CO₂ gas mixture using clathrate hydrate. Appl Energy, 2018, 225: 78