SDS对甲烷水合物生成动力学和微观结构的影响
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摘要
表面活性剂是促进水合物生成的有效手段之一。在高压反应釜中研究了十二烷基硫酸钠(SDS)对水合物生成过程的动力学影响,利用XRD和拉曼光谱探究了SDS存在条件下水合物的微观结构。宏观结果表明SDS缩短了诱导时间,加快了水合物生长速率。微观结果表明SDS没有影响s I型水合物的晶型结构,晶面间距与理想s I型水合物及纯水甲烷对比误差在千分之几。水合物中甲烷在大笼小笼中的拉曼位移分别为2904和2915 cm-1,SDS没有改变大笼小笼结构。大笼绝对占有率(?L)接近饱和时,SDS可以进一步提高小笼绝对占有率(?S),从微观角度证明了SDS可以减少水合数,提高储气率。
Surfactants is one of the effective methods to promote hydrate formation. The influence of Sodium dodecyl sulfate(SDS) on the formation of hydrate was studied in an autoclave. The microscopic properties for SDS hydrate samples were detected with Raman spectroscopy and powder X-ray diffraction. It was found that the presence of SDS decreased the induction time and enhanced the hydrate growth rate. The microcosmic results showed that the presence of SDS did not change the s I-type hydrate lattice structure and had less impact(a few thousandths) on the crystal spacing compared with ideal s I-type structure and pure methane hydrate. The Raman shift of C—H stretching mode from CH4 encapsulated in large and small cages are all 2904 and 2915 cm-1, which illustrate SDS did not change the large and small cages structure. SDS improved the absolute small cages occupancy(?L) as the absolute large cages occupancy(?S) approached saturation, and this is also demonstrated that SDS can reduce hydration number and increase storage capacity.
Surfactants is one of the effective methods to promote hydrate formation. The influence of Sodium dodecyl sulfate(SDS) on the formation of hydrate was studied in an autoclave. The microscopic properties for SDS hydrate samples were detected with Raman spectroscopy and powder X-ray diffraction. It was found that the presence of SDS decreased the induction time and enhanced the hydrate growth rate. The microcosmic results showed that the presence of SDS did not change the s I-type hydrate lattice structure and had less impact(a few thousandths) on the crystal spacing compared with ideal s I-type structure and pure methane hydrate. The Raman shift of C—H stretching mode from CH4 encapsulated in large and small cages are all 2904 and 2915 cm-1, which illustrate SDS did not change the large and small cages structure. SDS improved the absolute small cages occupancy(?L) as the absolute large cages occupancy(?S) approached saturation, and this is also demonstrated that SDS can reduce hydration number and increase storage capacity.
引文
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[27]刘昌岭,李承峰,孟庆国.天然气水合物拉曼光谱研究进展[J].光散射学报,2013,25(4):329-337.LIU C L,LI C F,MENG Q G.Progress of Raman spectroscopic research on natural gas hydrate[J].Chinese Journal of Light Scattering,2013,25(4):329-337.
[28]ZHOU X B,LIANG D Q,LIANG S,et al.Recovering CH4 from natural gas hydrates with the injection of CO2-N2 gas mixtures[J].Energy&Fuels,2015,29(2):1009-1106.
[29]HONG S Y,JIM J I,KIM J H,et al.Kinetic studies on methane hydrate formation in the presence of kinetic inhibitor via in situ Raman spectroscopy[J].Energy&Fuels,2012,26(11):7045-7050.
[30]ZHANG Q,SHEN X D,ZHOU X B,et al.Inhibition effect study of carboxyl-terminated polyvinyl caprolactam on methane hydrate formation[J].Energy&Fuels,2017,31(1):839-846.
[31]吴强,赵子琪,刘传海.SDS影响下煤层气水合物储气特性的Raman光谱分析[J].黑龙江科技大学学报,2016,26(1):25-30.WU Q,ZHAO Z Q,LIU C H.Study on SDS effect on characteristic of gas storage for CMM hydrate via Raman spectroscopy[J].Journal of Heilongjiang Institute of Science and Technology,2016,26(1):25-30.
[32]雷怀彦,官宝聪,刘建辉,等.笼状水合物拉曼光谱特征与结构水合数的耦合关系[J].现代地质,2005,19(1):83-88.LEI H Y,GUAN B C,LIU J H,et al.Coupled relationship among hydrate structure,hydration number,and Raman spectrum[J].Geoscience,2005,19(1):83-88.
[2]SLOAN E D,KOH C.Clathrate Hydrates of Natural Gases[M].3rd ed.New York:CRC Press,2007.
[3]FAN S S,YANG L,WANG Y H,et al.Rapid and high capacity methane storage in clathrate hydrates using surfactant dry solution[J].Chemical Engineering Science,2014,106(6):53-59.
[4]YANG L,CUI G M,LIU D P,et al.Rapid and repeatable methane storage in clathrate hydrates using gel-supported surfactant dry solution[J].Chemical Engineering Science,2016,146:10-18.
[5]LINGA P,KUMAR R,ENGLEZOS P.The clathrate hydrate process for post and pre-combustion capture of carbon dioxide[J].Journal of Hazardous Materials,2007,149(3):625-629.
[6]MAO W L,MAO H K,GONCHAROV A F,et al.Hydrogen clusters in clathrate hydrate[J].Science,2002,297(5590):2247-2249.
[7]KANG S P,LEE H.Recovery of CO2 from flue gas using gas hydrate:thermodynamic verification through phase equilibrium measurements[J].Environmental Science&Technology,2000,34(20):4397-4400.
[8]NAM P K,HONG S Y,LEE J W,et al.A new apparatus for seawater desalination by gas hydrate process and removal characteristics of dissolved minerals(Na+,Mg2+,Ca2+,K+,B3+)[J].Desalination,2011,274(1):91-96.
[9]YOON J H,LEE H.Clathrate phase equilibria for the water-phenol-carbon dioxide system[J].AICh E Journal,1997,43(7):1884-1893.
[10]LI H J,WANG L G.Hydrophobized particles can accelerate nucleation of clathrate hydrates[J].Fuel,2015,140:440-445.
[11]SONG Y M,WANG F,LIU G Q,et al.Promotion effect of carbon nanotubes-doped SDS on methane hydrate formation[J].Energy&Fuels,2017,31(2):1850-1857.
[12]VELUSWAMY H P,CHEN J Y,LINGA P.Surfactant effect on the kinetics of mixed hydrogen/propane hydrate formation for hydrogen storage as clathrates[J].Chemical Engineering Science,2015,126:488-499.
[13]ZHONG Y,ROGERS R E.Surfactant effects on gas hydrate formation[J].Chemical Engineering Science,2000,55(19):4175-4187.
[14]WANG F,JIA Z Z,LUO S J,et al.Effects of different anionic surfactants on methane hydrate formation[J].Chemical Engineering Science,2015,137:896-903.
[15]VERRETT J,POSTERARO D,SERVIO P.Surfactant effects on methane solubility and mole fraction during hydrate growth[J].Chemical Engineering Science,2012,84(52):80-84.
[16]QIN X L,WU Q,ZHANG B Y.Effect of sodium dodecyl sulfate on the process of methane hydrate formation[J].Chemistry,2006,69(7):519-523.
[17]ZHONG Y,ROGERS R E.Surfactant effects on gas hydrate formation[J].Chemical Engineering Science,2000,55(19):4175-4187.
[18]李文昭,潘振,马贵阳,等.表面活性剂吸附对促进甲烷水合物生成效果的影响[J].化工学报,2017,68(4):1542-1549.LI W Z,PAN Z,MA G Y,et al.Promotion effects of surfactant adsorption on formation of methane hydrates[J].CIESC Journal,2017,68(4):1542-1549.
[19]LIN W,CHEN G J,SUN C Y,et al.Effect of surfactant on the formation and dissociation kinetic behavior of methane hydrate[J].Chemical Engineering Science,2004,59(21):4449-4455.
[20]VELUSWAMY H P,ANG W J,ZHAO D,et al.Influence of cationic and non-ionic surfactants on the kinetics of mixed hydrogen/tetrahydrofuran hydrates[J].Chemical Engineering Science,2015,132:202-215.
[21]QIN X L,QIANG W,ZHANG B Y.Effect of sodium dodecyl sulfate on the process of methane hydrate formation[J].Chemistry,2006,69(7):519-523.
[22]BISHNOI P R,NATARAJAN V.Formation and decomposition of gas hydrates[J].Fluid Phase Equilibria,1996,117(1/2):168-177.
[23]SKOVBORG P,NG H J,RASMUSSEN P,et al.Measurement of induction times for the formation of methane and ethane gas hydrates[J].Chemical Engineering Science,1993,48(3):445-453.
[24]YOUSUF M,QADRI S B,KNIES D L,et al.Novel results on structural investigations of natural minerals of clathrate hydrates[J].Applied Physics A,2004,78(6):925-939.
[25]MICHAEL T,KIRCHNER,ROLAND B,et al.Gas hydrate single-crystal structure analyses[J].Journal of the American Chemical Society,2004,126(30):9407-9412.
[26]付娟,吴能友,卢海龙,等.激光拉曼光谱在气体水合物研究中的应用[J].光谱学与光谱分析,2015,2015(11):2996-3002.FU J,WU N Y,LU H L,et al.Laser Raman spectroscopy and its application in gas hydrate studies[J].Spectroscopy and Spectral Analysis,2015,2015(11):2996-3002.
[27]刘昌岭,李承峰,孟庆国.天然气水合物拉曼光谱研究进展[J].光散射学报,2013,25(4):329-337.LIU C L,LI C F,MENG Q G.Progress of Raman spectroscopic research on natural gas hydrate[J].Chinese Journal of Light Scattering,2013,25(4):329-337.
[28]ZHOU X B,LIANG D Q,LIANG S,et al.Recovering CH4 from natural gas hydrates with the injection of CO2-N2 gas mixtures[J].Energy&Fuels,2015,29(2):1009-1106.
[29]HONG S Y,JIM J I,KIM J H,et al.Kinetic studies on methane hydrate formation in the presence of kinetic inhibitor via in situ Raman spectroscopy[J].Energy&Fuels,2012,26(11):7045-7050.
[30]ZHANG Q,SHEN X D,ZHOU X B,et al.Inhibition effect study of carboxyl-terminated polyvinyl caprolactam on methane hydrate formation[J].Energy&Fuels,2017,31(1):839-846.
[31]吴强,赵子琪,刘传海.SDS影响下煤层气水合物储气特性的Raman光谱分析[J].黑龙江科技大学学报,2016,26(1):25-30.WU Q,ZHAO Z Q,LIU C H.Study on SDS effect on characteristic of gas storage for CMM hydrate via Raman spectroscopy[J].Journal of Heilongjiang Institute of Science and Technology,2016,26(1):25-30.
[32]雷怀彦,官宝聪,刘建辉,等.笼状水合物拉曼光谱特征与结构水合数的耦合关系[J].现代地质,2005,19(1):83-88.LEI H Y,GUAN B C,LIU J H,et al.Coupled relationship among hydrate structure,hydration number,and Raman spectrum[J].Geoscience,2005,19(1):83-88.