泡沫复合驱采出液处理用破乳剂的研制
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摘要
近年来大庆油田大规模应用的聚合物驱油技术和正在试验的三元复合驱油和泡沫复合驱油技术（统称化学驱油）矿场试验，分别取得了比水驱提高石油采收率12%、20%和30%以上的好效果，同时化学驱油特别是泡沫复合驱油采出液中残留的碱、表面活性剂、聚合物和天然气也导致采出液油水乳化严重，使油水分离难度明显加大。
本文中以大庆油田泡沫复合驱模拟采出液为介质，研究了泡沫复合驱模拟采出液稳定性及破乳效果的影响因素，即泡沫驱模拟采出液的含水率、乳化程度（包括均化仪的乳化时间及乳化转速）、聚合物含量、碱含量、表活剂含量、气含量七因素对模拟采出液稳定性及破乳效果的影响规律及程度，得到了脱后净化油含水率及污水含油量与各考察因素之间的回归方程；研制出了适合泡沫复合驱采出液破乳脱水的破乳剂FD9808，达到了泡沫复合驱油技术推广应用对破乳剂所要求的技术指标，即脱后净化油含水率≤30％、脱后污水含油量≤2000 mg/L。
本课题中的创新点主要包括：在泡沫复合驱模拟采出液稳定性及其破乳效果影响因素研究及在泡沫复合驱采出液处理用破乳剂配方的研制中合理地引入均匀设计试验法，在最终破乳剂配方的适应性试验中恰当地采用正交试验法，通过多种试验方法的有机结合，从而圆满地完成了该课题的研究工作，研制出了满足泡沫复合驱采出液处理要求的破乳剂FD9808。
本文中得出的主要研究结论包括：
采出液中残留的碱、表面活性剂、聚合物和天然气导致采出液油水乳化严重，油水乳状液稳定性增强，油水分离难度加大；
在泡沫复合驱模拟采出液含水率、聚合物含量、表活剂含量、碱含量及气含量五因素中，对泡沫驱模拟采出液稳定性影响最大的因素是碱含量及气含量，且碱含量及气含量越高，模拟采出液经热沉降后的油中含水率及污水含油量也越高，即模拟采出液越稳
定；
在泡沫复合驱模拟采出液含水率、聚合物含量、表活剂含量、碱含量及气含量五因素中，对泡沫驱模拟采出液破乳效果影响最大的因素是表活剂含量、碱含量及气含量，且表活剂含量越高，模拟采出液经破乳后的脱后净化油含水率越高；而碱含量及气含量越高，模拟采出液经破乳后的脱后污水含油量越高；
研制的破乳剂FD9808，是一种对泡沫复合驱采出液适宜的破乳剂，具有破乳效率高、适应性强的特点，在脱水温度为45℃、沉降时间为30min、加药量在40～60mg/L的条件下，即可达到泡沫复合驱油技术推广应用对破乳剂所要求的技术指标，即脱后净化油含水率≤30％、脱后污水含油量≤2000 mg/L，满足该介质破乳脱水的要求。
该课题成果是针对泡沫复合驱油技术的实际需要而提出来的，是泡沫复合驱油技术推广应用不可缺少的技术手段，其经济效益隐含在泡沫复合驱油技术所获得的经济效益之中。由于破乳剂FD9808的成本较低，用该剂可使处理每方采出液所需的破乳剂费用低于1.1元，随着泡沫复合驱油技术的逐步推广应用，其经济效益将是十分显著的。
The Polymer flooding being applied and the ASP flooding and complex foam flooding being test in Daqing Oilfield have resulted in EOR rates respective 12%, 20% and 30% over water flooding. However, residual alkaline, surfactants, polymer and natural gas in produced liquid have also resulted in tighter crude oil emulsion in produced liquid, leading to poorer oil/water separation of both produced liquid and oily water.
In this work, the influences of stabilization and demulsification efficiency of artificial chemical flooding produced liquid in Daqing Oilfield were systematically studied on artificial chemical flooding produced liquid. Respective relation functions between water cut in oil and oil cut in oily water to their influencing factors were achieved. Demulsifier FD9808, that is compatible to complex foam flooding produced liquid were developed.
Residual alkaline, surfactants, polymer and natural gas in produced liquid have resulted in tighter crude oil emulsion in produced liquid, leading to poorer oil/water separation of both
produced liquid and oily water.
The most significant influences in five factors of water cut, polyacrylamide content, surfactant content, alkaline content and natural gas content in artificial complex foam flooding produced liquid to stabilization of artificial complex foam flooding produced liquid are alkaline content and natural gas content. The more high alkaline content and natural gas content in artificial complex foam flooding produced liquid are, the more high water cut in oil and oil cut in oily water of artificial produced liquid after thermo-settlement are, namely, the more high stabilization of artificial produced liquid is.
The most significant influences in five factors of water cut, polyacrylamide content, surfactant content, alkaline content and natural gas content in artificial complex foam flooding produced liquid to demulsification efficiency of artificial complex foam flooding produced liquid are surfactant content, alkaline content and natural gas content. The more high surfactant content in artificial complex foam flooding produced liquid is, the more high water cut in oil of artificial produced liquid after
thermo-settlement is. The more high alkaline content and natural gas content in artificial complex foam flooding produced liquid are, the more high oil cut in oily water of artificial produced liquid after thermo-settlement is.
Demulsifier FD9808 is compatible to complex foam flooding produced liquid, features higher demulsification efficiency and more comprehensive compatibility, can meet application requirements of complex foam flooding.
本文中以大庆油田泡沫复合驱模拟采出液为介质，研究了泡沫复合驱模拟采出液稳定性及破乳效果的影响因素，即泡沫驱模拟采出液的含水率、乳化程度（包括均化仪的乳化时间及乳化转速）、聚合物含量、碱含量、表活剂含量、气含量七因素对模拟采出液稳定性及破乳效果的影响规律及程度，得到了脱后净化油含水率及污水含油量与各考察因素之间的回归方程；研制出了适合泡沫复合驱采出液破乳脱水的破乳剂FD9808，达到了泡沫复合驱油技术推广应用对破乳剂所要求的技术指标，即脱后净化油含水率≤30％、脱后污水含油量≤2000 mg/L。
本课题中的创新点主要包括：在泡沫复合驱模拟采出液稳定性及其破乳效果影响因素研究及在泡沫复合驱采出液处理用破乳剂配方的研制中合理地引入均匀设计试验法，在最终破乳剂配方的适应性试验中恰当地采用正交试验法，通过多种试验方法的有机结合，从而圆满地完成了该课题的研究工作，研制出了满足泡沫复合驱采出液处理要求的破乳剂FD9808。
本文中得出的主要研究结论包括：
采出液中残留的碱、表面活性剂、聚合物和天然气导致采出液油水乳化严重，油水乳状液稳定性增强，油水分离难度加大；
在泡沫复合驱模拟采出液含水率、聚合物含量、表活剂含量、碱含量及气含量五因素中，对泡沫驱模拟采出液稳定性影响最大的因素是碱含量及气含量，且碱含量及气含量越高，模拟采出液经热沉降后的油中含水率及污水含油量也越高，即模拟采出液越稳
定；
在泡沫复合驱模拟采出液含水率、聚合物含量、表活剂含量、碱含量及气含量五因素中，对泡沫驱模拟采出液破乳效果影响最大的因素是表活剂含量、碱含量及气含量，且表活剂含量越高，模拟采出液经破乳后的脱后净化油含水率越高；而碱含量及气含量越高，模拟采出液经破乳后的脱后污水含油量越高；
研制的破乳剂FD9808，是一种对泡沫复合驱采出液适宜的破乳剂，具有破乳效率高、适应性强的特点，在脱水温度为45℃、沉降时间为30min、加药量在40～60mg/L的条件下，即可达到泡沫复合驱油技术推广应用对破乳剂所要求的技术指标，即脱后净化油含水率≤30％、脱后污水含油量≤2000 mg/L，满足该介质破乳脱水的要求。
该课题成果是针对泡沫复合驱油技术的实际需要而提出来的，是泡沫复合驱油技术推广应用不可缺少的技术手段，其经济效益隐含在泡沫复合驱油技术所获得的经济效益之中。由于破乳剂FD9808的成本较低，用该剂可使处理每方采出液所需的破乳剂费用低于1.1元，随着泡沫复合驱油技术的逐步推广应用，其经济效益将是十分显著的。
The Polymer flooding being applied and the ASP flooding and complex foam flooding being test in Daqing Oilfield have resulted in EOR rates respective 12%, 20% and 30% over water flooding. However, residual alkaline, surfactants, polymer and natural gas in produced liquid have also resulted in tighter crude oil emulsion in produced liquid, leading to poorer oil/water separation of both produced liquid and oily water.
In this work, the influences of stabilization and demulsification efficiency of artificial chemical flooding produced liquid in Daqing Oilfield were systematically studied on artificial chemical flooding produced liquid. Respective relation functions between water cut in oil and oil cut in oily water to their influencing factors were achieved. Demulsifier FD9808, that is compatible to complex foam flooding produced liquid were developed.
Residual alkaline, surfactants, polymer and natural gas in produced liquid have resulted in tighter crude oil emulsion in produced liquid, leading to poorer oil/water separation of both
produced liquid and oily water.
The most significant influences in five factors of water cut, polyacrylamide content, surfactant content, alkaline content and natural gas content in artificial complex foam flooding produced liquid to stabilization of artificial complex foam flooding produced liquid are alkaline content and natural gas content. The more high alkaline content and natural gas content in artificial complex foam flooding produced liquid are, the more high water cut in oil and oil cut in oily water of artificial produced liquid after thermo-settlement are, namely, the more high stabilization of artificial produced liquid is.
The most significant influences in five factors of water cut, polyacrylamide content, surfactant content, alkaline content and natural gas content in artificial complex foam flooding produced liquid to demulsification efficiency of artificial complex foam flooding produced liquid are surfactant content, alkaline content and natural gas content. The more high surfactant content in artificial complex foam flooding produced liquid is, the more high water cut in oil of artificial produced liquid after
thermo-settlement is. The more high alkaline content and natural gas content in artificial complex foam flooding produced liquid are, the more high oil cut in oily water of artificial produced liquid after thermo-settlement is.
Demulsifier FD9808 is compatible to complex foam flooding produced liquid, features higher demulsification efficiency and more comprehensive compatibility, can meet application requirements of complex foam flooding.
引文
杨承志等. 化学驱提高石油采收率. 北京: 石油工业出版社，1995
冈秦麟. 化学驱油论文集, 北京:石油工业出版社, 1998
杨普华等译. 增效碱驱(复合驱)提高石油采收率译文集, 北京:石油工业出版社, 1993
廖广志, 王启民, 王德民. 化学复合驱原理及应用. 北京: 石油工业出版社, 1999
顾惕人, 朱步瑶, 李外朗, 马季铭, 戴乐蓉, 程虎民. 表面化学. 北京: 科学出版社,1999
朱步瑶, 赵振国. 界面化学基础. 北京:化学工业出版社, 1996
P. 贝歇尔著. 北京大学化学系胶体化学教研室译. 乳状液理论与实践, 北京, 科学出版社, 1978
李葵英. 界面与胶体的物理化学. 哈尔滨: 哈尔滨工业大学出版社, 1998
何勤功, 古大治等. 油田开发用高分子材料. 北京:石油工业出版社,1990
王云峰, 张春光, 侯万国等. 表面活性剂在油气田中的应用. 北京: 石油工业出版社，1995
H.A.巴勒斯, J.H. 赫顿, K.瓦尔特斯: 流变学导引. 北京,中国石化出版社, 1992
赵福麟. 采油化学. 山东东营: 石油大学出版社, 1989
赵福麟. 采油用剂. 山东东营: 石油大学出版社, 1997
丁德磬，孙在春，杨国华，徐梅清. 原油乳状液的稳定与破乳. 油田化学，1998年第15卷第1期，82-86
杨小莉，陆婉珍. 有关原油乳状液稳定性的研究. 油田化学，1998年第15卷第1期，87-96
方开泰.均匀设计与均匀设计表〔M〕.北京：科技出版社，1994.
Johan Sj?blom, Emulsions and Emulsion Stability, New York: Marcel Dekker, Inc, 1996
Laurier L. Schramm, Emulsions: Fundamentals and Application in the Petroleum Industry, Washington, DC: American Chemical Society, 1992
Ken Arnold, Maurice Stewart, Surface Production Operation Volume I Design of Oil-Handling Systems and Facilities, Houston, Texas: Gulf
Publishing Company, 1986
B.J. Briscoe, C.J. Lawrence, W.G.P. Mietus, A review of Immiscible Fluid Mixing. Advances in Colloid and Interface Science, 81(1999)1-17
O Boen Ho, Electrokinetic Studies on Emulsion Stabilized by Ionic Surfactants: The Electroacoustophoretic Behavior and Estimation of Davies’ HLB Increments, Journal of Colloid and Interface Science, 198, 249-260(1998)
M. Jumaa, B.W. Müller, Influence of the Non-ionic Surfactant PEG-660-12-Hydroxy Stearate on the Surface Properties of Phospholipid Monolayers and Their Effect on Lipid Emulsion Stability, Colloid Polym Sci, 277:347-353(1999)
D. Horn, J. Klingler, W. Schorf, K. Graf, Experimental Progress in the Characterization of Colloidal Systems, Progr Colloid Polym Sci(1998)111:27-33
T. Thieme, S. Abend, G. Lagaly, Aggregation in Pickering Emulsions, Colloid Polym Sci 277:257-260(1999)
David Tambe, Janka Paulis, and Mukul M. Sharma, Factors Controlling the Stability of Colloid-Stabilized Emulsions IV Evaluating the Effectiveness of Demulsifiers, Journal of Colloid and Interface Science 171,463-469(1995)
Marco Vanni, Approximate Population Balance Equations for Aggregation-Breakage Processes, Journal of Colloid and Interface Science ,221,143-160(2000)
Martin Whittle, Brent S. Murray, and Eric Dickson, Simulation of Colloid Particle Scattering: Sensitivity to Attractive Forces, Journal of Colloid and Interface Science,225,367-377(2000)
Dongming Li, Coalescence between Two Small Bubbles or Drops, Journal of Colloid and Interface Science 163, 108-119(1994)
Mikael Jansson, Maria Angeles Pés, Demulsification of Dilute O/W Water Emulsions with Organic Electrolytes, Journal of Colloid and Interface Science 163,512-514(1994)
Alberto Delgado, and H.M. Lee, Brown & Root. The Chronology of Water-Oil Handling Equipment, SPE 39878, paper presented at SPE international Conference and exhibition of Mexico held in Villahermosa, Mexico, March 3-5 1998
K. Parbhakar J. Lewandowski, and L. H. Dao, Simulation Model for Ostwald Ripening Liquids, Journal of Colloid and Interface Science 174,142-1471995)
H.W. Yarranton and J.H. Masliyah, Numerical Simulation of Ostwald Ripening in Emulsions, Journal of Colloid and Interface Science 196,157-1691997)
Hyang Mok Lee, Jin Woo Lee, and O Ok Park, Rheology and Dynamics of Water-in-Oil Emulsions under Steady and Dynamic Shear Flow, Journal of Colloid and Interface Science 185,297-305(1995)
J. Lakatos- Szabó, and I. Lakatos, Effect of Alkaline Materials on Interfacial Rheological Properties of Oil-Water Systems, Colloid Polym Sci, 277:41-47(1999)
Young-Ho Kim, Kalman Koczo, and Darsh T. Wasan, Dynamic Film and Interfacial Tensions in Emulsion and Foam Systems, Journal of Colloid and Interface Science 187,29-44(1997)
Leonid K. Filippov, Dynamic Surface Tension of Aqueous Surfactant Solutions, 1. Diffusion-Convective Controlled Adsorption, Journal of Colloid and Interface Science 163,49-60(1994)
O Boen Ho, Electrokinetic Studies on Emulsions Stabilized by Ionic Surfactants: the Electroacoustophoretic Behavior and Estimation of Davies’s HLB Increment, Journal of Colloid and Interface Science,198,249-260(1998)
康万力，单希林，王凤兰，龙安厚，李俊刚，三元复合驱乳状液的稳定性及其破乳机理研究，第五界国际表面活性剂/洗涤剂研讨会论文集，杭州，1998年9月4日—8日。
Hua Wang and Robert H. Davis, Experiments on Phase Separation of Dilute Dispersions of Coalescing Drops, Journal of Colloid and Interface Science 181, 93-98(1996)
冈秦麟. 化学驱油论文集, 北京:石油工业出版社, 1998
杨普华等译. 增效碱驱(复合驱)提高石油采收率译文集, 北京:石油工业出版社, 1993
廖广志, 王启民, 王德民. 化学复合驱原理及应用. 北京: 石油工业出版社, 1999
顾惕人, 朱步瑶, 李外朗, 马季铭, 戴乐蓉, 程虎民. 表面化学. 北京: 科学出版社,1999
朱步瑶, 赵振国. 界面化学基础. 北京:化学工业出版社, 1996
P. 贝歇尔著. 北京大学化学系胶体化学教研室译. 乳状液理论与实践, 北京, 科学出版社, 1978
李葵英. 界面与胶体的物理化学. 哈尔滨: 哈尔滨工业大学出版社, 1998
何勤功, 古大治等. 油田开发用高分子材料. 北京:石油工业出版社,1990
王云峰, 张春光, 侯万国等. 表面活性剂在油气田中的应用. 北京: 石油工业出版社，1995
H.A.巴勒斯, J.H. 赫顿, K.瓦尔特斯: 流变学导引. 北京,中国石化出版社, 1992
赵福麟. 采油化学. 山东东营: 石油大学出版社, 1989
赵福麟. 采油用剂. 山东东营: 石油大学出版社, 1997
丁德磬，孙在春，杨国华，徐梅清. 原油乳状液的稳定与破乳. 油田化学，1998年第15卷第1期，82-86
杨小莉，陆婉珍. 有关原油乳状液稳定性的研究. 油田化学，1998年第15卷第1期，87-96
方开泰.均匀设计与均匀设计表〔M〕.北京：科技出版社，1994.
Johan Sj?blom, Emulsions and Emulsion Stability, New York: Marcel Dekker, Inc, 1996
Laurier L. Schramm, Emulsions: Fundamentals and Application in the Petroleum Industry, Washington, DC: American Chemical Society, 1992
Ken Arnold, Maurice Stewart, Surface Production Operation Volume I Design of Oil-Handling Systems and Facilities, Houston, Texas: Gulf
Publishing Company, 1986
B.J. Briscoe, C.J. Lawrence, W.G.P. Mietus, A review of Immiscible Fluid Mixing. Advances in Colloid and Interface Science, 81(1999)1-17
O Boen Ho, Electrokinetic Studies on Emulsion Stabilized by Ionic Surfactants: The Electroacoustophoretic Behavior and Estimation of Davies’ HLB Increments, Journal of Colloid and Interface Science, 198, 249-260(1998)
M. Jumaa, B.W. Müller, Influence of the Non-ionic Surfactant PEG-660-12-Hydroxy Stearate on the Surface Properties of Phospholipid Monolayers and Their Effect on Lipid Emulsion Stability, Colloid Polym Sci, 277:347-353(1999)
D. Horn, J. Klingler, W. Schorf, K. Graf, Experimental Progress in the Characterization of Colloidal Systems, Progr Colloid Polym Sci(1998)111:27-33
T. Thieme, S. Abend, G. Lagaly, Aggregation in Pickering Emulsions, Colloid Polym Sci 277:257-260(1999)
David Tambe, Janka Paulis, and Mukul M. Sharma, Factors Controlling the Stability of Colloid-Stabilized Emulsions IV Evaluating the Effectiveness of Demulsifiers, Journal of Colloid and Interface Science 171,463-469(1995)
Marco Vanni, Approximate Population Balance Equations for Aggregation-Breakage Processes, Journal of Colloid and Interface Science ,221,143-160(2000)
Martin Whittle, Brent S. Murray, and Eric Dickson, Simulation of Colloid Particle Scattering: Sensitivity to Attractive Forces, Journal of Colloid and Interface Science,225,367-377(2000)
Dongming Li, Coalescence between Two Small Bubbles or Drops, Journal of Colloid and Interface Science 163, 108-119(1994)
Mikael Jansson, Maria Angeles Pés, Demulsification of Dilute O/W Water Emulsions with Organic Electrolytes, Journal of Colloid and Interface Science 163,512-514(1994)
Alberto Delgado, and H.M. Lee, Brown & Root. The Chronology of Water-Oil Handling Equipment, SPE 39878, paper presented at SPE international Conference and exhibition of Mexico held in Villahermosa, Mexico, March 3-5 1998
K. Parbhakar J. Lewandowski, and L. H. Dao, Simulation Model for Ostwald Ripening Liquids, Journal of Colloid and Interface Science 174,142-1471995)
H.W. Yarranton and J.H. Masliyah, Numerical Simulation of Ostwald Ripening in Emulsions, Journal of Colloid and Interface Science 196,157-1691997)
Hyang Mok Lee, Jin Woo Lee, and O Ok Park, Rheology and Dynamics of Water-in-Oil Emulsions under Steady and Dynamic Shear Flow, Journal of Colloid and Interface Science 185,297-305(1995)
J. Lakatos- Szabó, and I. Lakatos, Effect of Alkaline Materials on Interfacial Rheological Properties of Oil-Water Systems, Colloid Polym Sci, 277:41-47(1999)
Young-Ho Kim, Kalman Koczo, and Darsh T. Wasan, Dynamic Film and Interfacial Tensions in Emulsion and Foam Systems, Journal of Colloid and Interface Science 187,29-44(1997)
Leonid K. Filippov, Dynamic Surface Tension of Aqueous Surfactant Solutions, 1. Diffusion-Convective Controlled Adsorption, Journal of Colloid and Interface Science 163,49-60(1994)
O Boen Ho, Electrokinetic Studies on Emulsions Stabilized by Ionic Surfactants: the Electroacoustophoretic Behavior and Estimation of Davies’s HLB Increment, Journal of Colloid and Interface Science,198,249-260(1998)
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