油井缓蚀剂的化学吞吐技术研究
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摘要
随着油田开发,油井含水率不断上升,油井腐蚀越来越严重,解决油井腐蚀的问题越来越迫切。本文提出了一种新的油井缓蚀剂地层放置技术,即油井缓蚀剂的化学吞吐技术,它是指在高含水油井中注入油井缓蚀剂,该油井缓蚀剂将优先进入油层中的高渗透层,随后注入一定量的选择性堵水剂,将缓蚀剂封存于地层的高渗透层中,当驱油的水沿高渗透层迫近油井时,它将在堵水剂前带着封存的缓蚀剂缓慢产出,达到较长时间内减缓油井腐蚀的目的。用失重法和电化学法对市面上效果较好的油井缓蚀剂进行了评价,优选出了缓蚀效果最好的缓蚀剂BS-X。用两相滴定法检测了该缓蚀剂的有效浓度,并考察了它的高温稳定性,结果表明BS-X具有较强的稳定性。对缓蚀剂化学吞吐用堵剂进行了研究,包括不同交联体系冻胶的成冻时间和稳定性,选出了不同成冻时间的堵剂配方,并研究了其它配套工作液如前置液、隔离液和过顶替液。对缓蚀剂化学吞吐进行了室内物理模拟,包括非均质平板模型和可视化模型试验。试验结果表明,被封堵后的缓蚀剂在水驱时以低浓度缓慢释放,可以达到长期减缓油井腐蚀的目的。研究了配套工艺技术,为该技术的现场实施提供了室内研究基础。
As the development of oil field, water ratio increases continuously, production well corrosion becomes more and more serious, the need to resolve oil well corrosion is more and more urgent. This paper raises a new method to reduce production well corrosion, which is the huff and puff technique of corrosion inhibitor in formation. The said technique involves injecting corrosion inhibitor into high water cut production well, this corrosion inhibitor will enter high permeability zone of formation, and then selective plugging off agent is injected to block off corrosion inhibitor in high permeability zone. When the water displacing oil gets close to production well, the corrosion inhibitor will flow out for a long time attaining the aim to slow down production well corrosion. Production well corrosion inhibitor with preferable corrosion control effect in market is evaluated by weight-loss method and electrochemistry method, and then a kind of inhibitor named BS-X with the best corrosion control effect is obtained. Diphase titrate method is used to analysis the effective concentration of BS-X and its high temperature stability is investigated. The result shows that its high temperature stability is well. The block agent used for corrosion inhibitor huff and puff is studied, including gelling time and stability of different crosslink system gel, and then different gelling time composition of block agent is obtained. Other matting working fluids are also studied, including ahead fluid, isolate fluid and subsequent fluid. Corrosion inhibitor huff and puff is stimulated with physical models in laboratory, including inhomogeneous plate model and visualization models. It is shown that blocked corrosion inhibitor produces slowly with low concentration by water flood. This will fulfill the aim to slow down oil well corrosion in a long period. Matting technique is studied, providing laboratory study basis for the field conduct of this technology.
As the development of oil field, water ratio increases continuously, production well corrosion becomes more and more serious, the need to resolve oil well corrosion is more and more urgent. This paper raises a new method to reduce production well corrosion, which is the huff and puff technique of corrosion inhibitor in formation. The said technique involves injecting corrosion inhibitor into high water cut production well, this corrosion inhibitor will enter high permeability zone of formation, and then selective plugging off agent is injected to block off corrosion inhibitor in high permeability zone. When the water displacing oil gets close to production well, the corrosion inhibitor will flow out for a long time attaining the aim to slow down production well corrosion. Production well corrosion inhibitor with preferable corrosion control effect in market is evaluated by weight-loss method and electrochemistry method, and then a kind of inhibitor named BS-X with the best corrosion control effect is obtained. Diphase titrate method is used to analysis the effective concentration of BS-X and its high temperature stability is investigated. The result shows that its high temperature stability is well. The block agent used for corrosion inhibitor huff and puff is studied, including gelling time and stability of different crosslink system gel, and then different gelling time composition of block agent is obtained. Other matting working fluids are also studied, including ahead fluid, isolate fluid and subsequent fluid. Corrosion inhibitor huff and puff is stimulated with physical models in laboratory, including inhomogeneous plate model and visualization models. It is shown that blocked corrosion inhibitor produces slowly with low concentration by water flood. This will fulfill the aim to slow down oil well corrosion in a long period. Matting technique is studied, providing laboratory study basis for the field conduct of this technology.
引文
[1] 中国腐蚀与防护学会.石油工业中的腐蚀与防护[M].北京:化学工业出版社,2001:1～5.
[2] 黄金营,魏慧芳.油井腐蚀因素探讨[J].湖北化工.2003;2 期:41～42.
[3] 卢绮敏.石油工业中的腐蚀与防护[M].北京:化学工业出版社, 2001:38～70.
[4] 魏宝明.金属腐蚀理论及应用[M].北京:化学工业出版社,1984:35～51.
[5] 张学元.油气开发中二氧化碳腐蚀的研究和趋势[J].油田化学,1997;2 期:10～12.
[6] 何晓英.N80 油管钢在酸性溶液中的腐蚀行为[J].腐蚀科学与防护技术,2001;4 期:239～242.
[7] Derek Redmore,Ballwin.Corrosion inhibitors employing phosphate esters of cyclic amidines[P].US:3711403,1973-1-16.
[8] 李章亚.油田腐蚀与防护技术手册[M].北京:石油工业出版社,1999:35～58.
[9] 刘靖.硫酸盐还原菌腐蚀研究进展[J].材料保护,2001;3 期: 8～10.
[10] 化学工业部化工机械研究院主编.腐蚀与防护手册:耐蚀金属材料及防蚀技术[M].北京:化学工业出版社,1990:945～947.
[11] 张玉芳.咪唑啉及其衍生物在CO2 腐蚀介质中的缓蚀行为研 究进展[J].精细石油化工,2001;5 期:49～52.
[12] 张天胜.缓蚀剂[M].北京:化学工业出版社,2002:116～161.
[13] Suzuki K.The study of inhibitor for sour gas service.NACE Corrosion,1982;7:384～389.
[14] 油气田腐蚀与防护手册编委会.油气田腐蚀与防护技术手册[M]. 北京:石油工业出版社,1999:81～87.
[15] Blair CM.The existence of imidazoline corrosion inhibitors discussion.Corrosion,1985;5:616～623.
[16] 赵景茂,顾明广,左禹.CO2 腐蚀的气液双相新型缓蚀剂的开 发[J].腐蚀与防护,2005;2 期:436～438.
[17] Berthier F,DiardJ P.Method for determining the faradaric impedance of an electrode reaction:Application to metal corrosion rate measurements. Corrosion,1995;2:105～109.
[18] Hefter GT.Organic corrosion inhibitors in neutral solutions. Corrosion,1997;8:657～667.
[19] 胡玉辉,胡国林,张仲良等.固体缓蚀剂 GTH 油井防腐技术[J].油田化学,2005;1 期:48～51.
[20] 秦国治,田志明.防腐蚀技术及应用实例[M].北京:化学工业出版社,2002:45～49.
[21] 李章亚.油气田腐蚀与防护手册[M].北京:石油工业出版社,1998:84～88.
[22] Suzuki K.The study of inhibitor for sour gas service.NACE Corrosion, 1982;7:384～389.
[23] Blair CM.The existence of imidazoline corrosion inhibitors discussion.Corrosion,1985;5:616～623.
[24] 黄红兵.近年来油气井缓蚀新技术[J].石油与天然气化工,1998; 4 期,246～251.
[25] 刘世川,赵国仙,张力维.油气开发中二氧化碳腐蚀与防护缓蚀 剂.第十一届全国环世纪学术讨论会,1999,深圳.
[26] Daniel Efird K.Predicting corrosion of steel in crude oil production. Material Performance,1991;3:63～66.
[27] Papavinasam S.Laboratory methodologies for corrosion inhibitor selection.Material Performance,2000;8:58～60.
[28] Mochammad Ajmal.Fatty Acid Corrosion Inhibitors for Mild Steel.Anti-corrosion Methods and Materials,2000;2:77.
[29] Ramachandran S.Molecular modeling of the inhibition of mild steel CO2 corrosion by imidazolines.NACE Corrosion,1998;17:35～40.
[30] Jr Rosser H R . Injection Water Treatment at the Source :Biocide-enhanced Corrosion Inhibitor Squeeze Treatments of Water Supply Wells in a Central Arabia Oilfield,Proceeding-SPE International Symposium on Oilfield Chemistry.SPE 50740:389.
[31] 范树清.金属防锈及其实验方法[M].机械工业出版社,1989: 87～90.
[32] 白宝君,李宇乡,刘翔鄂.国内外化学堵水调剖技术综述[J].断块油气田,1998;5 期:1～4.
[33] 肖传敏,王正良.油田化学堵水调剖综述[J].精细石油化工进展,2003;3 期:43～46.
[34] 李宇乡,唐孝芬,刘双成.我国油田化学堵水调剖剂开发与应用现状[J].油田化学,1995;1 期:88～94.
[35] 李朝霞,雷江西.国外油井控水技术综述[J].国外油田工程,1997;6 期:29～32.
[36] 赵福麟.采油用剂[M].石油大学出版社,2001:57～73.
[37] 赵福麟,王家印,张贵才,等.化学剂吞吐与油井堵水的结合技术[J].石油大学学报,2001;6 期:62～64.
[38] 才程,岳湘安,赵福麟.化学剂吞吐与油井堵水结合技术研究[J].石油学报,2006;3 期:70～74.
[39] 关德,陈建武,商利军.渤海绥内 36-1 油田化学吞吐降粘技术初探[J].中国海上油气(工程),2000;1 期:40～42.
[40] 马广彦.采油井深部结垢防治技术[J].石油勘探与开发,2002;5 期:82～84.
[41] 马广彦.油田难溶垢化学处理技术[J].油田化学,2000;5 期:62～66.
[42] 刘涛,赵明华,童倚勤.新型油井防垢工艺的研究与应用[J].内蒙古石油化工,1 期:159～160.
[43] 中华人民共和国轻工业部.QB 1915-93,阳离子表面活性剂脂肪烷基三甲基卤化铵及脂肪烷基二甲基卤化铵,叶敏、王念甫、朱传家等,1994.
[2] 黄金营,魏慧芳.油井腐蚀因素探讨[J].湖北化工.2003;2 期:41～42.
[3] 卢绮敏.石油工业中的腐蚀与防护[M].北京:化学工业出版社, 2001:38～70.
[4] 魏宝明.金属腐蚀理论及应用[M].北京:化学工业出版社,1984:35～51.
[5] 张学元.油气开发中二氧化碳腐蚀的研究和趋势[J].油田化学,1997;2 期:10～12.
[6] 何晓英.N80 油管钢在酸性溶液中的腐蚀行为[J].腐蚀科学与防护技术,2001;4 期:239～242.
[7] Derek Redmore,Ballwin.Corrosion inhibitors employing phosphate esters of cyclic amidines[P].US:3711403,1973-1-16.
[8] 李章亚.油田腐蚀与防护技术手册[M].北京:石油工业出版社,1999:35～58.
[9] 刘靖.硫酸盐还原菌腐蚀研究进展[J].材料保护,2001;3 期: 8～10.
[10] 化学工业部化工机械研究院主编.腐蚀与防护手册:耐蚀金属材料及防蚀技术[M].北京:化学工业出版社,1990:945～947.
[11] 张玉芳.咪唑啉及其衍生物在CO2 腐蚀介质中的缓蚀行为研 究进展[J].精细石油化工,2001;5 期:49～52.
[12] 张天胜.缓蚀剂[M].北京:化学工业出版社,2002:116～161.
[13] Suzuki K.The study of inhibitor for sour gas service.NACE Corrosion,1982;7:384～389.
[14] 油气田腐蚀与防护手册编委会.油气田腐蚀与防护技术手册[M]. 北京:石油工业出版社,1999:81～87.
[15] Blair CM.The existence of imidazoline corrosion inhibitors discussion.Corrosion,1985;5:616～623.
[16] 赵景茂,顾明广,左禹.CO2 腐蚀的气液双相新型缓蚀剂的开 发[J].腐蚀与防护,2005;2 期:436～438.
[17] Berthier F,DiardJ P.Method for determining the faradaric impedance of an electrode reaction:Application to metal corrosion rate measurements. Corrosion,1995;2:105～109.
[18] Hefter GT.Organic corrosion inhibitors in neutral solutions. Corrosion,1997;8:657～667.
[19] 胡玉辉,胡国林,张仲良等.固体缓蚀剂 GTH 油井防腐技术[J].油田化学,2005;1 期:48～51.
[20] 秦国治,田志明.防腐蚀技术及应用实例[M].北京:化学工业出版社,2002:45～49.
[21] 李章亚.油气田腐蚀与防护手册[M].北京:石油工业出版社,1998:84～88.
[22] Suzuki K.The study of inhibitor for sour gas service.NACE Corrosion, 1982;7:384～389.
[23] Blair CM.The existence of imidazoline corrosion inhibitors discussion.Corrosion,1985;5:616～623.
[24] 黄红兵.近年来油气井缓蚀新技术[J].石油与天然气化工,1998; 4 期,246～251.
[25] 刘世川,赵国仙,张力维.油气开发中二氧化碳腐蚀与防护缓蚀 剂.第十一届全国环世纪学术讨论会,1999,深圳.
[26] Daniel Efird K.Predicting corrosion of steel in crude oil production. Material Performance,1991;3:63～66.
[27] Papavinasam S.Laboratory methodologies for corrosion inhibitor selection.Material Performance,2000;8:58～60.
[28] Mochammad Ajmal.Fatty Acid Corrosion Inhibitors for Mild Steel.Anti-corrosion Methods and Materials,2000;2:77.
[29] Ramachandran S.Molecular modeling of the inhibition of mild steel CO2 corrosion by imidazolines.NACE Corrosion,1998;17:35～40.
[30] Jr Rosser H R . Injection Water Treatment at the Source :Biocide-enhanced Corrosion Inhibitor Squeeze Treatments of Water Supply Wells in a Central Arabia Oilfield,Proceeding-SPE International Symposium on Oilfield Chemistry.SPE 50740:389.
[31] 范树清.金属防锈及其实验方法[M].机械工业出版社,1989: 87～90.
[32] 白宝君,李宇乡,刘翔鄂.国内外化学堵水调剖技术综述[J].断块油气田,1998;5 期:1～4.
[33] 肖传敏,王正良.油田化学堵水调剖综述[J].精细石油化工进展,2003;3 期:43～46.
[34] 李宇乡,唐孝芬,刘双成.我国油田化学堵水调剖剂开发与应用现状[J].油田化学,1995;1 期:88～94.
[35] 李朝霞,雷江西.国外油井控水技术综述[J].国外油田工程,1997;6 期:29～32.
[36] 赵福麟.采油用剂[M].石油大学出版社,2001:57～73.
[37] 赵福麟,王家印,张贵才,等.化学剂吞吐与油井堵水的结合技术[J].石油大学学报,2001;6 期:62～64.
[38] 才程,岳湘安,赵福麟.化学剂吞吐与油井堵水结合技术研究[J].石油学报,2006;3 期:70～74.
[39] 关德,陈建武,商利军.渤海绥内 36-1 油田化学吞吐降粘技术初探[J].中国海上油气(工程),2000;1 期:40～42.
[40] 马广彦.采油井深部结垢防治技术[J].石油勘探与开发,2002;5 期:82～84.
[41] 马广彦.油田难溶垢化学处理技术[J].油田化学,2000;5 期:62～66.
[42] 刘涛,赵明华,童倚勤.新型油井防垢工艺的研究与应用[J].内蒙古石油化工,1 期:159～160.
[43] 中华人民共和国轻工业部.QB 1915-93,阳离子表面活性剂脂肪烷基三甲基卤化铵及脂肪烷基二甲基卤化铵,叶敏、王念甫、朱传家等,1994.