蔗糖对四氢呋喃水合物分解平衡温度影响的实验研究
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摘要
随着油气资源的开采趋于深海,对促进水合物分解的研究在管道解堵和水合物开采方面都具有重要的意义。实验测试得到蔗糖的质量分数分别为0.05%、0.5%、2.4%、9.1%、20.0%、33.3%和39.4%。实验结果表明体系中蔗糖的存在对THF水合物的分解有促进作用,能降低THF水合物的分解平衡温度且分解平衡温度随着蔗糖含量的增加而降低;当蔗糖的质量分数大于27.7%时,THF水合物的分解平衡温度降至冰点以下。热力学模型以液-水合物-气三相逸度平衡为起始点,根据THF水合物的特点对传统的逸度计算模型进行了适当的简化,用基团贡献法计算得到了实验体系下水的活度系数,并利用实验数据拟合得到了模型中用于计算Langmuir常数的两个重要参数,最后选定适用于其他参数的经验公式。用该模型预测得到的水合物分解平衡温度与实验得到的数据相吻合,说明该模型可用于预测常压下的THF+水+蔗糖体系水合物分解平衡温度。本文建立的模型对不同客体水合物的热力学模型的建立也具有指导意义。
As the oil and gas resources exploitation in the deeper sea,the research of promoting the hydrate dissociation has the vital significance in the aspects of solving pipe blockage and hydrate exploitation. Sucrose at 7 concentrations of 0.05,0.5,2.4,9.1,20.0,33.3 and 39.4wt. % was tested. The results showed that sucrose promoted the THF hydrate dissociation,reduced the balance of tetrahydrofuran hydrate dissociation temperature and the reduction of the temperature was along with the increase of sucrose concentration; the equilibrium temperature would below the ice point when the concentration was above 27.7 wt. %. The thermodynamic modelling used the fugacity of three phase equilibria of water liquid-hydrate-gas/vapor as the starting point,and simplified the traditional model of calculating the fugacity which was according to the characteristic of the THF hydrate,and calculated the activity of water in the experimental system by using the UNIFAC group-contribution model,and fitted the two important parameters which were aimed to calculate the Langmuir constant based on the experimental dates,and last,chose the appropriate empirical formulas for calculating the other parameters. A good agreement between the experimental measurements and the model predicting was observed which confirms the accuracy of the model used. The thermodynamic model built in this study also has guiding significance for building other thermodynamic model of hydrate of different guests.
As the oil and gas resources exploitation in the deeper sea,the research of promoting the hydrate dissociation has the vital significance in the aspects of solving pipe blockage and hydrate exploitation. Sucrose at 7 concentrations of 0.05,0.5,2.4,9.1,20.0,33.3 and 39.4wt. % was tested. The results showed that sucrose promoted the THF hydrate dissociation,reduced the balance of tetrahydrofuran hydrate dissociation temperature and the reduction of the temperature was along with the increase of sucrose concentration; the equilibrium temperature would below the ice point when the concentration was above 27.7 wt. %. The thermodynamic modelling used the fugacity of three phase equilibria of water liquid-hydrate-gas/vapor as the starting point,and simplified the traditional model of calculating the fugacity which was according to the characteristic of the THF hydrate,and calculated the activity of water in the experimental system by using the UNIFAC group-contribution model,and fitted the two important parameters which were aimed to calculate the Langmuir constant based on the experimental dates,and last,chose the appropriate empirical formulas for calculating the other parameters. A good agreement between the experimental measurements and the model predicting was observed which confirms the accuracy of the model used. The thermodynamic model built in this study also has guiding significance for building other thermodynamic model of hydrate of different guests.
引文
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3孟庆国,刘昌岭,业渝光.核磁共振成像原位监测冰融化及四氢呋喃水合物分解的微观过程.应用基础与工程科学学报,2012;20(1):11-20Meng Q G,Liu C L,Ye Y G.In situ monitoring ice melting and tetrahydrofuran hydrates dissociation with magnetic resonance imaging.Journal of Basic Science and Engineering,2012;20(1):11-20
4 Wilson P W,Lester D,Haymet A D J.Heterogeneous nucleation of clathrates from supercooled tetrahydrofuran(THF)/water mixtures,and the effect of an added catalyst.Chemical Engineering Science,2005;60(11):2937-2941
5 Mimachi H,Takeya S,Gotoh Y,et al.Dissociation behaviors of methane hydrate formed from Na Cl solutions.Fluid Phase Equilibria,2016;413:22-27
6 Smith A,Babaee S,Mohamm A H,et al.Clathrate hydrate dissociation conditions for refrigerant+sucrose aqueous solution:experimental measurement and thermodynamic modelling.Fluid Phase Equilibria,2016;1208(1):237-246
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9董福海,臧小亚,樊栓狮,等.注甲醇溶液分解丙烷水合物实验模拟.石油化工高等学校学报,2009;22(3):9-13Dong F H Zang X Y,Fan Q S,et al.Experimental simulation on dissociation behavior of propane hydrate by methanol glycol solution inject ion.Journal of Petrochemical Universities,2009;22(3):9-13
10董福海,臧小亚,李栋梁,等.乙二醇溶液作用下丙烷水合物分解实验研究.西南石油大学学报(自然科学版),2009;31(3):121-125Dong F H,Zang X Y,Li D L,et al.Experimental study on propane hydrates dissociation in presence of ethylene glycol solution.Journal of Southwest Petroleum University(Science&Technology Edition),2009;31(3):121-125
11臧小亚,梁德青,樊栓狮.3A型分子筛对四氢呋喃水合物分解的影响.制冷学报,2007;28(6):29-34Zang X Y,Liang D Q,Fan Q S.Effects of 3A molecular sieve on THF Hydrate decomposition.Journal of Refrigeration,2007;28(6):29-34
12臧小亚,梁德青,樊栓狮,等.5A分子筛粉末对四氢呋喃水合物的生成及分解过程的影响.物理化学学报,2009;25(6):1047-1052Zang X Y,Liang D Q,Fan Q S.Effects of 5A molecular sieve on THF Hydrate decomposition.Acta Physico-Chimica Sinica,2009;25(6):1047-1052
13 Sloan E D,Jr Koh C.Clathrate hydrates of natural gases(third edition).New York:Crc Press,2007
14 Eslamimanesh A,Mohammadi A H,Richon D.Thermodynamic model for predicting phase equilibria of simple clathrate hydrates of refrigerants.Chemical Engineering Science,2011;66(21):5439-5445
15 Dharmawardhana P B,Parrish W R,Sloan E D.Experimental thermodynamic parameters for the prediction of natural gas hydrate dissociation conditions.Le Mans,2000;19(4):410-414
16 Parrish W,Prausnitz J.Dissociation pressures of gas hydrates formed by gas mixtures.Industrial&Engineering Chemistry Process Design&Development,1972;11(3):27-35
17 Mohammadi A H,Richon D.Thermodynamic model for predicting liquid water-hydrate equilibrium of the water-hydrocarbon system.Industrial&Engineering Chemistry Research,2008;47(4):1346-1350
18 Daubert T E,Danner R P,Daubert T E,et al.Data compilation tables of properties of pure compounds.New York:AICh E,1985
19 Fredenslund A,Jones R L,Pransnitz J M.Croup contribution estimation of activity coefficients in nonideal liquid mixture.AICh EJournal,1975;21(6):1086-1099
20李君发.计算活度系数的UNIFAC基团贡献法(Ⅰ).化学工程,1991;19(1):12-23Li J F.UNIFAC group contribution method for estimating activity coefficient(Ⅰ).Chemical Engineering,1991;19(1):12-23
21 Rahim M,Bahman T,Ali D,et al.A new approach in modelling phase equilibria and gas solubility in electrolyte solutions and its applications to gas hydrates.Fluid Phase Equilibria,2004;215(2):163-174
2白小东,张力,李林,等.一种评价水合物抑制剂性能的新方法.石油与天然气化工,2005;34(6):445-447Bai X D,Zhang L,Li L,et al.A new method for evaluation of hydrate inhibitor performance.Chemical Engineering of Oil and Gas,2005;34(6):445-447
3孟庆国,刘昌岭,业渝光.核磁共振成像原位监测冰融化及四氢呋喃水合物分解的微观过程.应用基础与工程科学学报,2012;20(1):11-20Meng Q G,Liu C L,Ye Y G.In situ monitoring ice melting and tetrahydrofuran hydrates dissociation with magnetic resonance imaging.Journal of Basic Science and Engineering,2012;20(1):11-20
4 Wilson P W,Lester D,Haymet A D J.Heterogeneous nucleation of clathrates from supercooled tetrahydrofuran(THF)/water mixtures,and the effect of an added catalyst.Chemical Engineering Science,2005;60(11):2937-2941
5 Mimachi H,Takeya S,Gotoh Y,et al.Dissociation behaviors of methane hydrate formed from Na Cl solutions.Fluid Phase Equilibria,2016;413:22-27
6 Smith A,Babaee S,Mohamm A H,et al.Clathrate hydrate dissociation conditions for refrigerant+sucrose aqueous solution:experimental measurement and thermodynamic modelling.Fluid Phase Equilibria,2016;1208(1):237-246
7 Ngema P T,Naidoo P,Mohammadi A H,et al.Experimental clathrate hydrate dissociation data for systems comprising refrigerant+Ca Cl2aqueous solutions.Journal of Chemical&Engineering Data,2016;61:827-836
8王燕鸿,陈玉娟,包玲,等.聚乙烯唑啉作用下甲烷水合物分解的分子动力学模拟.物理化学学报,2012;28(7):1683-1690Wang Y H,Chen Y J,Bao L,et al.Molecular dynamics simulation of CH4hydrate decomposition in the presence of poly(2-ethyl-2-oxazoline).Acta Physico-Chimica Sinica,2012;28(7):1683-1690
9董福海,臧小亚,樊栓狮,等.注甲醇溶液分解丙烷水合物实验模拟.石油化工高等学校学报,2009;22(3):9-13Dong F H Zang X Y,Fan Q S,et al.Experimental simulation on dissociation behavior of propane hydrate by methanol glycol solution inject ion.Journal of Petrochemical Universities,2009;22(3):9-13
10董福海,臧小亚,李栋梁,等.乙二醇溶液作用下丙烷水合物分解实验研究.西南石油大学学报(自然科学版),2009;31(3):121-125Dong F H,Zang X Y,Li D L,et al.Experimental study on propane hydrates dissociation in presence of ethylene glycol solution.Journal of Southwest Petroleum University(Science&Technology Edition),2009;31(3):121-125
11臧小亚,梁德青,樊栓狮.3A型分子筛对四氢呋喃水合物分解的影响.制冷学报,2007;28(6):29-34Zang X Y,Liang D Q,Fan Q S.Effects of 3A molecular sieve on THF Hydrate decomposition.Journal of Refrigeration,2007;28(6):29-34
12臧小亚,梁德青,樊栓狮,等.5A分子筛粉末对四氢呋喃水合物的生成及分解过程的影响.物理化学学报,2009;25(6):1047-1052Zang X Y,Liang D Q,Fan Q S.Effects of 5A molecular sieve on THF Hydrate decomposition.Acta Physico-Chimica Sinica,2009;25(6):1047-1052
13 Sloan E D,Jr Koh C.Clathrate hydrates of natural gases(third edition).New York:Crc Press,2007
14 Eslamimanesh A,Mohammadi A H,Richon D.Thermodynamic model for predicting phase equilibria of simple clathrate hydrates of refrigerants.Chemical Engineering Science,2011;66(21):5439-5445
15 Dharmawardhana P B,Parrish W R,Sloan E D.Experimental thermodynamic parameters for the prediction of natural gas hydrate dissociation conditions.Le Mans,2000;19(4):410-414
16 Parrish W,Prausnitz J.Dissociation pressures of gas hydrates formed by gas mixtures.Industrial&Engineering Chemistry Process Design&Development,1972;11(3):27-35
17 Mohammadi A H,Richon D.Thermodynamic model for predicting liquid water-hydrate equilibrium of the water-hydrocarbon system.Industrial&Engineering Chemistry Research,2008;47(4):1346-1350
18 Daubert T E,Danner R P,Daubert T E,et al.Data compilation tables of properties of pure compounds.New York:AICh E,1985
19 Fredenslund A,Jones R L,Pransnitz J M.Croup contribution estimation of activity coefficients in nonideal liquid mixture.AICh EJournal,1975;21(6):1086-1099
20李君发.计算活度系数的UNIFAC基团贡献法(Ⅰ).化学工程,1991;19(1):12-23Li J F.UNIFAC group contribution method for estimating activity coefficient(Ⅰ).Chemical Engineering,1991;19(1):12-23
21 Rahim M,Bahman T,Ali D,et al.A new approach in modelling phase equilibria and gas solubility in electrolyte solutions and its applications to gas hydrates.Fluid Phase Equilibria,2004;215(2):163-174