水合物热力学抑制剂临界最低加剂量的计算方法
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摘要
在油气管道输送过程中,低温高压工况易生成水合物从而影响管道输送效率,严重时会引起管道堵塞。在实际工程应用中,通常采用添加热力学抑制剂的方式防止水合物的生成,常用的热力学抑制剂有甲醇、乙二醇等。确定合理的热力学抑制剂加剂量,对于保证管道的安全经济运行具有重要意义。在Chen-Guo双过程水合物热力学模型的基础上,应用Wilson模型确定水-醇溶液中水的活度,建立了含抑制剂体系水合物生成平衡条件的计算方法,并提出采用预估-试算-调整的思路确定管道运行工况点所需抑制剂的临界最低加剂量。实例验证表明,所提方法计算简单,精度高,能够满足实际工程需要。(图6,表6,参23)
During the pipeline transportation of oil and gas, hydrate tends to form in the working condition of low temperature and high pressure and consequently influences the pipeline transportation efficiency and even leads to pipeline blockage. In practical engineering, the formation of hydrate is usually prevented by adding thermodynamic inhibitors.And the commonly used thermodynamic inhibitors include methanol(MeOH), ethylene glycol(EG), and so on. Therefore,the determination of the reasonable dosage of thermodynamic inhibitor is of great significance to the safety and economy of pipeline operation. In this paper, a method for calculating the formation equilibrium condition of hydrate containing inhibitor system was established on the basis of Chen-Guo dual-process hydrate thermodynamic model, after the activity of water in water-alcohol solution was determined in Wilson Model. Then, the idea of estimation-trial-adjustment was proposed to determine the critical minimum dosage of inhibitor in the working condition of pipeline operation. It is verified that the method is simple and accurate, and can meet the needs of practical engineering.(6 Figures, 6 Tables, 23 References)
During the pipeline transportation of oil and gas, hydrate tends to form in the working condition of low temperature and high pressure and consequently influences the pipeline transportation efficiency and even leads to pipeline blockage. In practical engineering, the formation of hydrate is usually prevented by adding thermodynamic inhibitors.And the commonly used thermodynamic inhibitors include methanol(MeOH), ethylene glycol(EG), and so on. Therefore,the determination of the reasonable dosage of thermodynamic inhibitor is of great significance to the safety and economy of pipeline operation. In this paper, a method for calculating the formation equilibrium condition of hydrate containing inhibitor system was established on the basis of Chen-Guo dual-process hydrate thermodynamic model, after the activity of water in water-alcohol solution was determined in Wilson Model. Then, the idea of estimation-trial-adjustment was proposed to determine the critical minimum dosage of inhibitor in the working condition of pipeline operation. It is verified that the method is simple and accurate, and can meet the needs of practical engineering.(6 Figures, 6 Tables, 23 References)
引文
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[10]关昌伦,叶学礼.天然气水合物抑制剂甲醇注入量的计算[J].天然气与石油,1993,1(4):8-29.GUAN C L,YE X L.Calculation of methanol injection amount of gas hydrate inhibitor[J].Natural Gas and Oil,1993,1(4):8-29.
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[12]CHEN G J,GUO T M.Thermodynamic modeling of hydrate formation based on new concepts[J].Fluid Phase Equilibria,1996,122(1/2):43-65.
[13]陈光进,马庆兰,郭天民.气体水合物生成机理和热力学模型的建立[J].化工学报,2000,21(5):626-631.CHEN G J,MA Q L,GUO T M.A new mechanism for hydrate formation and development of thermodynamic model[J].Journal of Chemical Industry and Engineering(China),2000,21(5):626-631.
[14]PENG D Y,ROBINSON D B.A new two-constant equation of state[J].Industrial&Engineering Chemistry Fundamentals,1976,15(1):92-94.
[15]张锦,周诗岽,卢国维,等.水合物反应液中水活度系数模型研究进展[J].应用化学,2016,33(3):277-283.ZHANG J,ZHOU S D,LU G W,et al.Research development of activity coefficient models in hydrate reaction media[J].Chinese Journal of Applied Chemistry,2016,33(3):277-283.
[16]MA Q L,CHEN G J,GUO T M.Modelling the gas hydrate formation of inhibitor containing systems[J].Fluid Phase Equilibria,2003,205(2):291-302.
[17]马庆兰,陈光进,郭天民.含极性抑制剂体系中水合物生成条件的研究[J].高校化学工程学报,2000,14(1):7-11.MA Q L,CHEN G J,GUO T M.Study on the hydrate formation conditions from system containing polar inhibitor[J].Journal of Chemical Engineering of Chinese Universities,2000,14(1):7-11.
[18]童清木.水中溶解烃的分析方法[J].石油勘探与开发,1985,12(5):36-38.TONG Q M.A method of analysis for the identification and determination of hydrocarbons in underground water[J].Petroleum Exploration and Development,1985,12(5):36-38.
[19]李世伟,胡宗林.烃-水系统的相平衡及轻烃中溶解水量的计算[J].天然气工业,1989,9(2):68-70.LI S W,HU Z L.Calculation of phase equilibrium of hydrocarbon-water system and solubility amount of water in light hydrocarbons[J].Natural Gas Industry,1989,9(2):68-70.
[20]韩广河.烃在醇-水溶液中溶解度的研究[D].青岛:中国石油大学(华东),2003:56-68.HAN G H.Study on solubility of hydrocarbon in alcohol-water solution[D].Qingdao:China University of Petroleum(East China),2003:56-68.
[21]郭天民.多元气-液平衡和精馏[M].北京:石油工业出版社,2002:36-40,51-56,82-120.GUO T M.Multiple gas-liquid equilibrium and rectification[M].Beijing:Petroleum Industry Press,2002:36-40,51-56,82-120.
[22]WILSON G M.Vapor-liquid equilibrium.XI.A new expression for the excess free energy of mixing[J].Journal of the American Chemical Society,1964,86(2):127-130.
[23]史博会,全恺,乔国春,等.榆济输气管道水合物冰堵防治措施[J].油气储运,2014,33(3):274-282.SHI B H,QUAN K,QIAO G C,et al.Prevention measures for hydrate ice blockage in Yu-Ji Gas Pipeline[J].Oil&Gas Storage and Transportation,2014,33(3):274-282.
[2]MASOUDI R,TOHIDI B.Estimating the hydrate stability zone in the presence of salts and/or organic inhibitors using water partial pressure[J].Journal of Petroleum Science&Engineering,2005,46(1/2):23-36.
[3]MASOUDI R,TOHIDI B.On modelling gas hydrate inhibition by salts and organic inhibitors[J].Journal of Petroleum Science&Engineering,2010,74(3/4):132-137.
[4]SLOAN E D,KOH C A,SUM K A,et al.Natural gas hydrates in flow assurance[M].Houston:Gulf Professional Publishing,2010:1-11.
[5]SLOAN E D,KOH C A.Clathrate hydrates of natural gases[M].London:CRC Press,2007:1-9.
[6]郝蕴.天然气水合物抑制剂用量HYSYS软件模拟结果与计算值比较[C].北京:Aspen Tech China 2003信息化论坛,2003:44-51.HAO Y.Comparison of simulated results using HYSYS and calculated values of gas hydrate inhibitor[C].Beijing:AspenTech China 2003 Informatization Forum,2003:44-51.
[7]冯叔初,郭揆常.油气集输与矿场加工[M].北京:中国石油大学出版社,2006:55-70.FENG S C,GUO K C.Oil and gas gathering and transportation and field processing[M].Beijing:China University of Petroleum Press,2006:55-70.
[8]梁金莺,张秀玲.天然气水合物抑制剂注入量计算方法比较[J].中国石油和化工,2012,1(5):37-38.LIANG J Y,ZHANG X L.Comparison of calculation methods for injection amount of gas hydrate inhibitors[J].China Petroleum and Chemical Industry,2012,1(5):37-38.
[9]梁裕如,张书勤.延长气田天然气水合物抑制剂注入量的确定[J].甘肃科技,2011,27(1):32-34.LIANG Y R,ZHANG S Q.Determination of injection amount of gas hydrate inhibitor in Yanchang Gas Field[J].Gansu Science and Technology,2011,27(1):32-34.
[10]关昌伦,叶学礼.天然气水合物抑制剂甲醇注入量的计算[J].天然气与石油,1993,1(4):8-29.GUAN C L,YE X L.Calculation of methanol injection amount of gas hydrate inhibitor[J].Natural Gas and Oil,1993,1(4):8-29.
[11]陈光进,孙长宇,马庆兰.气体水合物科学与技术[M].北京:化学工业出版社,2008:124-137.CHEN G J,SUN C Y,MA Q L.Science and technology of gas hydrate[M].Beijing:Chemical Industry Press,2008:124-137.
[12]CHEN G J,GUO T M.Thermodynamic modeling of hydrate formation based on new concepts[J].Fluid Phase Equilibria,1996,122(1/2):43-65.
[13]陈光进,马庆兰,郭天民.气体水合物生成机理和热力学模型的建立[J].化工学报,2000,21(5):626-631.CHEN G J,MA Q L,GUO T M.A new mechanism for hydrate formation and development of thermodynamic model[J].Journal of Chemical Industry and Engineering(China),2000,21(5):626-631.
[14]PENG D Y,ROBINSON D B.A new two-constant equation of state[J].Industrial&Engineering Chemistry Fundamentals,1976,15(1):92-94.
[15]张锦,周诗岽,卢国维,等.水合物反应液中水活度系数模型研究进展[J].应用化学,2016,33(3):277-283.ZHANG J,ZHOU S D,LU G W,et al.Research development of activity coefficient models in hydrate reaction media[J].Chinese Journal of Applied Chemistry,2016,33(3):277-283.
[16]MA Q L,CHEN G J,GUO T M.Modelling the gas hydrate formation of inhibitor containing systems[J].Fluid Phase Equilibria,2003,205(2):291-302.
[17]马庆兰,陈光进,郭天民.含极性抑制剂体系中水合物生成条件的研究[J].高校化学工程学报,2000,14(1):7-11.MA Q L,CHEN G J,GUO T M.Study on the hydrate formation conditions from system containing polar inhibitor[J].Journal of Chemical Engineering of Chinese Universities,2000,14(1):7-11.
[18]童清木.水中溶解烃的分析方法[J].石油勘探与开发,1985,12(5):36-38.TONG Q M.A method of analysis for the identification and determination of hydrocarbons in underground water[J].Petroleum Exploration and Development,1985,12(5):36-38.
[19]李世伟,胡宗林.烃-水系统的相平衡及轻烃中溶解水量的计算[J].天然气工业,1989,9(2):68-70.LI S W,HU Z L.Calculation of phase equilibrium of hydrocarbon-water system and solubility amount of water in light hydrocarbons[J].Natural Gas Industry,1989,9(2):68-70.
[20]韩广河.烃在醇-水溶液中溶解度的研究[D].青岛:中国石油大学(华东),2003:56-68.HAN G H.Study on solubility of hydrocarbon in alcohol-water solution[D].Qingdao:China University of Petroleum(East China),2003:56-68.
[21]郭天民.多元气-液平衡和精馏[M].北京:石油工业出版社,2002:36-40,51-56,82-120.GUO T M.Multiple gas-liquid equilibrium and rectification[M].Beijing:Petroleum Industry Press,2002:36-40,51-56,82-120.
[22]WILSON G M.Vapor-liquid equilibrium.XI.A new expression for the excess free energy of mixing[J].Journal of the American Chemical Society,1964,86(2):127-130.
[23]史博会,全恺,乔国春,等.榆济输气管道水合物冰堵防治措施[J].油气储运,2014,33(3):274-282.SHI B H,QUAN K,QIAO G C,et al.Prevention measures for hydrate ice blockage in Yu-Ji Gas Pipeline[J].Oil&Gas Storage and Transportation,2014,33(3):274-282.
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