甜菜碱类粘弹性表面活性剂自转向酸酸化技术研究
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摘要
粘弹性表面活性剂自转向酸酸化技术是一种改造非均质地层的新技术,配制简单、破胶容易、对地层伤害小,并且具有缓速和降滤失的优点。当pH值在2左右时,在游离的Ca~(2+)、Mg~(2+)作用下,粘弹性表面活性剂排列结构发生变化使体系粘度增大,迫使酸液从高渗透层转向进入低渗透层。为了更好地服务于自转向酸化作业,分别对粘弹性表面活性剂的选择、自转向酸流变性及与碳酸盐岩的反应动力学以及转向标准进行研究。以油酸、3-二甲胺基丙氨、氯乙酸钠为原料,经酰胺化及季铵化反应合成油酸酰胺丙基甜菜碱作为自转向酸主剂,由正交试验得到反应的最优条件。测定油酸酰胺丙基甜菜碱浓度、温度、pH值、剪切及剪切顺序、无机盐离子浓度等对自转向酸体系粘度的影响;并在合适的条件下进行旋转圆盘实验,测不同转速下的酸岩反应速率,得到自转向酸与碳酸盐岩反应动力学方程;用实验数据绘制酸岩反应临界转速版图,并以此判断实验条件下反应为H~+传质控制;通过计算不同酸浓度下H+有效传质系数,得出有效传质系数与温度的关系不符合阿伦尼乌斯方程。温度较低时,反应速率随温度升高缓慢增加,当体系温度大于70℃时,反应速率迅速增加。基于达西公式推导出自转向酸转向的判别方法,当酸液转向时,R_p-k_o/Φ_o的双对数关系曲线为一条直线。
Viscoelastic surfactant self-diverting acid diversion acidizing technique is a newly developed reservoir stimulation technique,with the advantage of simple preparation,gel breaking easily,small formation damage,slow and lower filtration.When the pH value is about 2,the viscosity of the system increases with the free Ca~(2+),Mg~(2+) chelating with viscoelastic surfactant molecules to make the arrangement of the surfactant molecules changing,then the self-diverting acid turns from the high permeability zone into the low permeability one.The system loses its viscosity by touching with hydrocarbons,water diluting,and mixing with gel breaker. The oleic acid, 3– Dimethylamino propyl ammonia and sodium chloroacetate are used to synthesize the acid amide propyl betaine by amide and quaternary ammonium.In order to better serve the acidizing operation, the rheological analysis of the self-diverting acid is taken,and the effects of the concentration,temperature,pH value,shear and shear history, inorganic ion concentration are measured. The rotating disk reactor is used for the reaction kinetics. And the reaction is dominated by H~+ mass transfer coefficient; The effect of temperature on the diffusion coefficient doesn’t follow Arrhenius law.The reaction rate increases slowly with the temperature rising,when the temperature is above 70oC,the reaction rate increases rapidly.Based on the Darcy law,the diversion criterion is developed.When the self-diverting acid is on the diversion, the log-log curve between Rp and k_o/Φ_o is a line.
Viscoelastic surfactant self-diverting acid diversion acidizing technique is a newly developed reservoir stimulation technique,with the advantage of simple preparation,gel breaking easily,small formation damage,slow and lower filtration.When the pH value is about 2,the viscosity of the system increases with the free Ca~(2+),Mg~(2+) chelating with viscoelastic surfactant molecules to make the arrangement of the surfactant molecules changing,then the self-diverting acid turns from the high permeability zone into the low permeability one.The system loses its viscosity by touching with hydrocarbons,water diluting,and mixing with gel breaker. The oleic acid, 3– Dimethylamino propyl ammonia and sodium chloroacetate are used to synthesize the acid amide propyl betaine by amide and quaternary ammonium.In order to better serve the acidizing operation, the rheological analysis of the self-diverting acid is taken,and the effects of the concentration,temperature,pH value,shear and shear history, inorganic ion concentration are measured. The rotating disk reactor is used for the reaction kinetics. And the reaction is dominated by H~+ mass transfer coefficient; The effect of temperature on the diffusion coefficient doesn’t follow Arrhenius law.The reaction rate increases slowly with the temperature rising,when the temperature is above 70oC,the reaction rate increases rapidly.Based on the Darcy law,the diversion criterion is developed.When the self-diverting acid is on the diversion, the log-log curve between Rp and k_o/Φ_o is a line.
引文
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[21]Diedre Taylor,Santhana Kumar.Viscoelastic Surfactantbased Self-divertingAcid For Enhanced Stimulation in Carbonate Reservoirs[R].SPE82263,2003
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[24]Nasr-El-Din,Chesson.Field success in Carbonate Acid Diversion,Utilizing Laboratory Data Generated by Parallel Flow Testing[R].SPE102828,2006
[25]Philippe,Bruno Lecerf,and Yenny CHristant,et al.An Experimentally Validated Wormhole Model for Self-Diverting and Conventional Acids in Carbonate Rocks Under Radial Flow Conditions[R].SPE107854,2007
[26]Al-Ghamdi,A.H.Mahmoud,M.A.Hill,and Nasr-El-Din,et al.Propagation of Viscoelastic Surfactant-Based Acids in Carbonate Cores[R].SPE121713,2009
[27]K.C.Taylor,H.A.Nasr-El-Din,and M.Al-Alawi.Systematic Study of Iron Control Chemicals Used During Well Stimulation[R].SPE54602,1998
[28]Ayman.R.Al-Nakhli,H.A.Nasr-El-Din.Interactions of Iron and Viscoelastic Surfactants During Well Stimulation:A New Formation Damage Mechanism[R].SPE117060,2008
[29]叶艳,吴敏,陈馥,等.粘弹性表面活性剂技术在酸化中的应用[J].石油与天然气工程.2003,32(3):164-166
[30]蔡远红,罗炽臻.表面活性酸粘度影响因素及缓蚀控制[J].钻采工艺,2010,33(2):146-150
[31]汤波.粘弹性表面活性剂在酸液中的作用机理及应用[J].油气田地面工程,2009,28(2):28-30
[32]H.Al-Ghamdi,Nasr-El-Din.Impact of acid additives on the rheological properties of viscoelastic surfactants and their influence on field application.SPE89418,2004
[33]方云.两性表面活性剂[M].北京:中国轻工业出版社,2001:28-30
[34]何元君,张铸勇.烷基酰胺磷酸酯甜菜碱的合成及性能[J].华东理工大学学报,1998,24(6):741-745
[35]方云,方咏梅.两性表面活性剂的合成[J].日用化学工业,2001(4):56-60
[36]毛培坤.表面活性剂产品工业分析[M].北京化学工业出版社,2003:272
[37]钟雷,丁悠丹.表面活性剂及其助剂分析[M].浙江:浙江科学技术出版社,1986:55-56
[38]刘文钦.仪器分析[M].山东泰安:石油大学出版社,1994:203
[39]胡忠前,马喜平,王红,等.粘弹性蠕虫状胶束及其应用[J].高分子通报,2007,8(1):24-27
[40]蒋庆哲,宋昭铮.表面活性剂科学与应用[M].北京:中国石化出版社,2006:103-104
[41]张博,赵立强.加入内部破胶剂的粘弹性表面活性剂转向液在酸处理中的应用[J].国外油气田工程,2010,26(2):18-20
[42]袁恩熙.工程流体力学[M].北京:石油工业出版社,2006:266-269
[43]何春明,陈红军,翟锐,等.VES自转向酸变黏机理研究[J].油气地质与采收率,2010,27(4):84-86
[44]朱永东.酸岩反应动力学实验研究方法评述[J].内蒙古石油化工,2008,10(1):23-25
[45]袁恩熙.工程流体力学[M].北京:石油工业出版社,2006:266-269
[46]张琪.采油工程原理与设计[M].东营:石油大学出版社,2000:294-299
[47]Al.Rabie,Gomaa,and H.A.Nasr-El-Din,et al.Determination of Reaction Rate of In-situ Gelled Acids With Calcite Using the Rotating Disk Apparatus[R].SPE133501,2010
[48]Buisje, Glasbergen.A Semiempirical Model To Model To Calculate Wormhole Grwoth in Carbonate Acidizing[R].SPE96892,2005
[49]赵智勇,丁云宏,赵常青,等.胶凝酸反应动力学实验研究[J].石油与天然气化工,2005,34(5):394-396
[50]Daccord,Touboul and Lenormand.Carbonate Acidizing:Toward a Quantitative Model of the Wormholin Phenomenon[R].SPE Prod.Eng.,1989
[51]T.Huang,A.D.Hill,and R.S.Schechter.Reaction Rate and Fluid Loss:The Keys to Wormhole Initiation and Propagation in Carbonate Acidizing[R].SPE65400,2000
[52]M.K.R.Panga,M.Ziauddin,and R.Gandikota,et al.A New Model for Prediciting Wormhole Structure and Formation in Acid Stimulation of Carbonate[R].SPE86517,2004
[2]方少仙,侯方浩.石油天然气储层地质学[M].山东:石油大学出版社,1998:16-24
[3]Gabriel,Erbstoesser.The Design of Buoyant Ball Sealer Treatments[R].SPE13085,1984
[4]Bazin,Charbonnel.Strategy optimization for matrix treatments of horizontal drains in carbonate reservoirsuse of self-gelling acid diverter[R].SPE54720,1999
[5]Nasr-El-Din,Taylor,Al-Haiji.Proagation of cross-linkers used in in-situ gelled Acids in carbonate reservoirs[R].SPE75257,2002
[6]吴信荣,孙建华,尚根华,等.泡沫酸对高温高盐油层适应性动态评价[J].石油天然气学报,2005,27(1):83-88
[7]李松岩.氮气泡沫分流酸化技术研究[D].东营:中国石油大学(华东),2009
[8]何春明.碳酸盐岩储层转向酸化技术现状与最新进展[J].石油钻探技术,2009,37(5):121-126
[9]Majdi Al-Mutawa.Field Cases of a Zero Damaging Stimulation and Diversion Fluid from the Carbonate Formations in North Kuwait[R].SPE80225,2003
[10]刘新全,易明新.粘弹性表面活性剂压裂液[J].油田化学,2001,18(3):273-277
[11]刘俊,郭拥军,刘通义,等.粘弹性表面活性剂研究进展[J].钻井液与完井液,2003,20(3):47-51
[12]赵增迎,杨贤友.VES自转向盐酸液变粘特性研究[J].油田化学,2005,22(4):307-309
[13]袁飞,张健强,王斌,等.VDA-08表面活性剂盐酸体系变粘特性研究[J].新疆石油天然气,2008,4(3):79-83
[14]郑云川,赵立强,刘平礼,等.两性表面活性剂酸液体系在基质酸化及酸压中的应用[J].天然气工业,2005,25(12):71-73
[15]郑云川,赵立强,刘平礼,等.粘弹性表面活性剂胶束酸在砂岩储层分流酸化中的应用[J].石油学报,2006,27(6):93-95
[16]马代鑫,徐赋海,王增林,等.变粘分流酸主剂油酸酰胺丙基甜菜碱的合成[J].特种油气藏,2009,16(3):89-91
[17]马利成,李爱山,张晓云,等.新型粘弹性表面活性自转向酸的研制及性能评价[J].油气地质与采收率,2007,14(5):98-100
[18]刘京,徐建华.清洁自转向酸液的研制及性能评价[J].石油天然气学报,2009,31(3):302-305
[19]Nasr-EI-Din.Rheological Properties of a New Class of Viscoelastic Surfactant[R].SPE121716,2009
[20]F.F.Chang,T.G.Love.New Material and Technique for Matrix Stimulation in High-Water-Cut Oil Wells[R].SPE64006PA,2000
[21]Diedre Taylor,Santhana Kumar.Viscoelastic Surfactantbased Self-divertingAcid For Enhanced Stimulation in Carbonate Reservoirs[R].SPE82263,2003
[22]郑云川.高温非均质砂岩储层变粘胶束酸分流酸化技术及酸岩反应动力学研究[D].南充:西南石油大学,2006
[23]Lungwitz.Diversion and Cleanup of Viscoelastic Surfactant-Based Self-Diverting Acid[R].SPE86504,2004
[24]Nasr-El-Din,Chesson.Field success in Carbonate Acid Diversion,Utilizing Laboratory Data Generated by Parallel Flow Testing[R].SPE102828,2006
[25]Philippe,Bruno Lecerf,and Yenny CHristant,et al.An Experimentally Validated Wormhole Model for Self-Diverting and Conventional Acids in Carbonate Rocks Under Radial Flow Conditions[R].SPE107854,2007
[26]Al-Ghamdi,A.H.Mahmoud,M.A.Hill,and Nasr-El-Din,et al.Propagation of Viscoelastic Surfactant-Based Acids in Carbonate Cores[R].SPE121713,2009
[27]K.C.Taylor,H.A.Nasr-El-Din,and M.Al-Alawi.Systematic Study of Iron Control Chemicals Used During Well Stimulation[R].SPE54602,1998
[28]Ayman.R.Al-Nakhli,H.A.Nasr-El-Din.Interactions of Iron and Viscoelastic Surfactants During Well Stimulation:A New Formation Damage Mechanism[R].SPE117060,2008
[29]叶艳,吴敏,陈馥,等.粘弹性表面活性剂技术在酸化中的应用[J].石油与天然气工程.2003,32(3):164-166
[30]蔡远红,罗炽臻.表面活性酸粘度影响因素及缓蚀控制[J].钻采工艺,2010,33(2):146-150
[31]汤波.粘弹性表面活性剂在酸液中的作用机理及应用[J].油气田地面工程,2009,28(2):28-30
[32]H.Al-Ghamdi,Nasr-El-Din.Impact of acid additives on the rheological properties of viscoelastic surfactants and their influence on field application.SPE89418,2004
[33]方云.两性表面活性剂[M].北京:中国轻工业出版社,2001:28-30
[34]何元君,张铸勇.烷基酰胺磷酸酯甜菜碱的合成及性能[J].华东理工大学学报,1998,24(6):741-745
[35]方云,方咏梅.两性表面活性剂的合成[J].日用化学工业,2001(4):56-60
[36]毛培坤.表面活性剂产品工业分析[M].北京化学工业出版社,2003:272
[37]钟雷,丁悠丹.表面活性剂及其助剂分析[M].浙江:浙江科学技术出版社,1986:55-56
[38]刘文钦.仪器分析[M].山东泰安:石油大学出版社,1994:203
[39]胡忠前,马喜平,王红,等.粘弹性蠕虫状胶束及其应用[J].高分子通报,2007,8(1):24-27
[40]蒋庆哲,宋昭铮.表面活性剂科学与应用[M].北京:中国石化出版社,2006:103-104
[41]张博,赵立强.加入内部破胶剂的粘弹性表面活性剂转向液在酸处理中的应用[J].国外油气田工程,2010,26(2):18-20
[42]袁恩熙.工程流体力学[M].北京:石油工业出版社,2006:266-269
[43]何春明,陈红军,翟锐,等.VES自转向酸变黏机理研究[J].油气地质与采收率,2010,27(4):84-86
[44]朱永东.酸岩反应动力学实验研究方法评述[J].内蒙古石油化工,2008,10(1):23-25
[45]袁恩熙.工程流体力学[M].北京:石油工业出版社,2006:266-269
[46]张琪.采油工程原理与设计[M].东营:石油大学出版社,2000:294-299
[47]Al.Rabie,Gomaa,and H.A.Nasr-El-Din,et al.Determination of Reaction Rate of In-situ Gelled Acids With Calcite Using the Rotating Disk Apparatus[R].SPE133501,2010
[48]Buisje, Glasbergen.A Semiempirical Model To Model To Calculate Wormhole Grwoth in Carbonate Acidizing[R].SPE96892,2005
[49]赵智勇,丁云宏,赵常青,等.胶凝酸反应动力学实验研究[J].石油与天然气化工,2005,34(5):394-396
[50]Daccord,Touboul and Lenormand.Carbonate Acidizing:Toward a Quantitative Model of the Wormholin Phenomenon[R].SPE Prod.Eng.,1989
[51]T.Huang,A.D.Hill,and R.S.Schechter.Reaction Rate and Fluid Loss:The Keys to Wormhole Initiation and Propagation in Carbonate Acidizing[R].SPE65400,2000
[52]M.K.R.Panga,M.Ziauddin,and R.Gandikota,et al.A New Model for Prediciting Wormhole Structure and Formation in Acid Stimulation of Carbonate[R].SPE86517,2004