一种低浓度压裂液有机硼交联剂的合成与性能评价
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摘要
针对目前国内压裂液稠化剂使用浓度较高的问题,以十水四硼酸钠为主原料,在NaOH的催化剂作用下,与乙二醇、三乙醇胺和多羟基醇进行络合反应,合成了适用于低浓度压裂液体系下的有机硼交联剂JS2-6,通过红外光谱对交联剂JS2-6以及HPG/JS2-6交联形成的冻胶分别进行了结构表征,研究了该交联剂与较低浓度的羟丙基胍胶所形成压裂液的延缓交联性能、耐温抗剪切性能、滤失性能、破乳性能和摩阻性能。通过实验得到的低浓度压裂液体系配方为:(0.3%～0.35%)HPG+0.2%杀菌剂FHS-18+0.2%助排剂F220+0.3%黏土稳定剂DS-208+0.1%交联促进剂+(0.02%～0.04%)p H调节剂,交联比为100∶(0.2～0.3),体系适用温度为60数150℃。通过调节体系的pH值,有效延长交联时间可达90 s。在温度140℃、剪切速率170 s~(-1)下剪切90 min,压裂液的黏度保持在150 m Pa·s左右,具有优异的耐温耐剪切性能。该体系在120℃时滤失系数最低为7.12×10~(-4)m/min~(1/2),滤失量28 mL,能有效减少地层伤害。在120℃破胶后的破胶液与煤油间的界面张力<1 mN/m,破胶液黏度较低,对地层伤害率低,且具有低摩阻的特点,可达到易排液的使用要求。图9表3参17
In order to solve the problem of high concentration of fracturing fluid thickener in China,organic boron crosslinker JS2-6 was synthesized by using sodium tetraborate decahydrate as main material and complexing with ethylene glycol,triethanolamine and polyhydroxy alcohol under the catalysis of NaOH. The synthesized crosslinking agent JS2-6 was used in low concentration fracturing fluid system. The structure of crosslinking agent JS2-6 and HPG/JS2-6 was characterized by infrared spectroscopy. The delayed crosslinking,temperature and shear resistance,filtration,demulsification and friction properties of the fracturing fluid formed by the crosslinking agent and low concentration hydroxypropyl guanidine gum were studied. The formula of low concentration fracturing fluid system obtained by experiment was as follows:0.3% —0.35% HPG + 0.2% fungicide FHS-18 +0.2% assistant F220+0.3% clay stabilizer DS-208+0.1% cross-linking accelerator+0.02%—0.04% pH regulator,the cross-linking ratio was 100∶(0.2—0.3),and the suitable temperature of the system was 60—150℃. The crosslinking time could be prolonged up to 90 s by adjusting the pH value of the system. After sheared for 90 minutes at the temperature of 140℃ and shearing rate of 170 s~(-1),the viscosity of the fracturing fluid remained about 150 m Pa·s,which indicated that the fracturing system had excellent temperature and shear resistance. The system had the lowest filtration coefficient of 7.12×10~(-4) m/min~(1/2) and a filtration capacity of 28 mL at 120℃,indicating that the system could effectively reduce formation damage. The interfacial tension between gel breaking fluid after gel breaking and kerosene at 120℃ was less than 1 m N/m,in addition,the gel breaking fluid had low viscosity,low formation damage rate and low frictional resistance,which could meet the requirements of easily draining.
In order to solve the problem of high concentration of fracturing fluid thickener in China,organic boron crosslinker JS2-6 was synthesized by using sodium tetraborate decahydrate as main material and complexing with ethylene glycol,triethanolamine and polyhydroxy alcohol under the catalysis of NaOH. The synthesized crosslinking agent JS2-6 was used in low concentration fracturing fluid system. The structure of crosslinking agent JS2-6 and HPG/JS2-6 was characterized by infrared spectroscopy. The delayed crosslinking,temperature and shear resistance,filtration,demulsification and friction properties of the fracturing fluid formed by the crosslinking agent and low concentration hydroxypropyl guanidine gum were studied. The formula of low concentration fracturing fluid system obtained by experiment was as follows:0.3% —0.35% HPG + 0.2% fungicide FHS-18 +0.2% assistant F220+0.3% clay stabilizer DS-208+0.1% cross-linking accelerator+0.02%—0.04% pH regulator,the cross-linking ratio was 100∶(0.2—0.3),and the suitable temperature of the system was 60—150℃. The crosslinking time could be prolonged up to 90 s by adjusting the pH value of the system. After sheared for 90 minutes at the temperature of 140℃ and shearing rate of 170 s~(-1),the viscosity of the fracturing fluid remained about 150 m Pa·s,which indicated that the fracturing system had excellent temperature and shear resistance. The system had the lowest filtration coefficient of 7.12×10~(-4) m/min~(1/2) and a filtration capacity of 28 mL at 120℃,indicating that the system could effectively reduce formation damage. The interfacial tension between gel breaking fluid after gel breaking and kerosene at 120℃ was less than 1 m N/m,in addition,the gel breaking fluid had low viscosity,low formation damage rate and low frictional resistance,which could meet the requirements of easily draining.
引文
[1]陈静,马政生,田义,等.延长油田压裂液用有机硼交联剂的研究[J].油田化学,2012,29(3):267-270.
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[11]王栋,王俊英,刘洪升,等.水基压裂液高温延缓型有机硼锆交联剂CZB-03的制备[J].油田化学,2004,21(2):113-115.
[12]沈丽,黄文章,向林,等.超高耐温型胍胶交联剂的合成与性能研究[J].石油与天然气化工,2017,46(2):80-84.
[13] ROSE J,DEBRUIN T J M,CHAUVETEAU G,et al. Aqueous zirconium complexes for gelling polymers. A combined X-ray absorption spectroscopy and quantum mechanical study[J]. J Phys Chem B,2003,107(13):2910-2920.
[14]杨亚宇,徐小刚,杨晓春,等.不同pH值小交联胍胶压裂液的性能研究[J].石油与天然气化工,2010,39(5):427-430.
[15]王佳,怡宝安,杨文,等.压裂液用硼交联剂作用机理分析[J].精细石油化工进展,2009,10(8):23-26.
[16]唐萍,林鑫,郑承纲,等.有机硼羟丙基胍胶压裂液的交联动力学研究[J].物理化学进展,2017,6(1):37-43.
[17]邵立民,靳宝军,李爱山,等.非常规油气藏滑溜水压裂液的研究与应用[J].吐哈油气,2012,17(4):383-387.
[2]庄照锋,赵贤,李荆,等. HPG压裂液水不溶物和残渣来源分析[J].油田化学,2009,26(2):139-141.
[3]林波,刘通义,谭浩波,等.新型缔合压裂液黏弹性控制滤失的特性研究[J].西南石油大学学报(自然科学版),2014,36(3):151-156.
[4] WILLIAMS N,KELLY P,BERARD K,et al. Fracturing fluid with low-polymer loading using a new set of boron crosslinkers:laboratory and field studies[C]. SPE 151715,2012.
[5]张颖,陈大均,刘彦锋,等.低浓度胍胶压裂液体系的室内研究[J].应用化工,2013,42(10):1836-1838.
[6] DAWSON J,CRAMER D. Reduced polymer based fracturing fluid:is less really more[C]. SPE 90851,2004.
[7]李永明,刘林,李莎莎,等.含纤维的超低浓度稠化剂压裂液的研究[J].钻井液与完井液,2010,27(2):50-53.
[8]胡忠前,马喜平,何川,等.国外低伤害压裂液体系研究新进展[J].海洋石油,2007,27(3):93-97.
[9] ZUZANIUK V,PRINS R. Synthesis and characterization of silica-supported transition-metal phosphides as HDN catalysts[J]. J Catal,2003,219(1):85-96.
[10]闫海龙,李建山,史俊,等.多羟基醇压裂液体系交联剂研究[J].西安石油大学学报(自然科学版),2009,24(6):52-54.
[11]王栋,王俊英,刘洪升,等.水基压裂液高温延缓型有机硼锆交联剂CZB-03的制备[J].油田化学,2004,21(2):113-115.
[12]沈丽,黄文章,向林,等.超高耐温型胍胶交联剂的合成与性能研究[J].石油与天然气化工,2017,46(2):80-84.
[13] ROSE J,DEBRUIN T J M,CHAUVETEAU G,et al. Aqueous zirconium complexes for gelling polymers. A combined X-ray absorption spectroscopy and quantum mechanical study[J]. J Phys Chem B,2003,107(13):2910-2920.
[14]杨亚宇,徐小刚,杨晓春,等.不同pH值小交联胍胶压裂液的性能研究[J].石油与天然气化工,2010,39(5):427-430.
[15]王佳,怡宝安,杨文,等.压裂液用硼交联剂作用机理分析[J].精细石油化工进展,2009,10(8):23-26.
[16]唐萍,林鑫,郑承纲,等.有机硼羟丙基胍胶压裂液的交联动力学研究[J].物理化学进展,2017,6(1):37-43.
[17]邵立民,靳宝军,李爱山,等.非常规油气藏滑溜水压裂液的研究与应用[J].吐哈油气,2012,17(4):383-387.
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