抗高温瓜尔胶压裂液复合交联剂的研制及应用
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摘要
为了满足抗高温压裂液体系的应用要求,针对改性羟丙基瓜尔胶压裂液体系,在常温下用"一锅法",以氧氯化锆与硼酸为主要成分、复合多元醇为配位体合成了有机硼锆交联剂。利用单因素实验法优选了制备交联剂的最佳条件,运用红外光谱和核磁共振对所制备的交联剂结构进行了表征,并评价了该交联剂的性能。结果表明,制备有机硼锆交联剂时硼酸与氧氯化锆的最佳摩尔比为4∶1。在羟丙基胍胶溶液质量分数为0. 5%、耐温增强剂质量分数为0. 6%、基液与所制备的有机硼锆交联剂体积比为100∶0. 6的条件下,交联时间为102 s,冻胶在150℃、170 s~(-1)经连续剪切90 min后的黏度在80 m Pa·s以上,表明合成的有机硼锆交联压裂液具有良好的耐温抗剪切性和延缓交联性。对该压裂液体系进行现场试验,取得良好的压裂效果。
In order to meet the application requirement of high temperature fracturing fluid system,organic boron zirconium crosslinking agent for modified hydroxypropyl guar gel fracturing fluid system is synthesized through one-pot method at room temperature with boric acid and zirconium oxychloride as main components,and complex polyols as ligands.The optimum reaction conditions are obtained via single factor experiment method. Infrared spectroscopy and nuclear magnetic resonance are used to characterize the structure of the prepared crosslinking agent and evaluate the performance.The result shows that the best molar ratio of H_3BO_3 to ZrOCl_2 is 4 ∶ 1.The final viscosity of fracturing fluid after continuously shearing 90 min at the speed of 170 s-1 under 150℃ stands above 80 MPa·s when the mass contents of hydroxypropyl guar gel solution and temperature resistance enhancer are 0. 5% and 0. 6% respectively,the volume ratio of guar gels solution and the prepared crosslinking agent is 100 ∶0. 6 and the crosslinking time lasts for 102 s.It is shown that the organic boron zirconium crosslinking agent fracturing fluid system has a good shear resistant and a delayed crosslinking performance.Excellent fracturing effects is achieved which it is evaluated at spot test.
In order to meet the application requirement of high temperature fracturing fluid system,organic boron zirconium crosslinking agent for modified hydroxypropyl guar gel fracturing fluid system is synthesized through one-pot method at room temperature with boric acid and zirconium oxychloride as main components,and complex polyols as ligands.The optimum reaction conditions are obtained via single factor experiment method. Infrared spectroscopy and nuclear magnetic resonance are used to characterize the structure of the prepared crosslinking agent and evaluate the performance.The result shows that the best molar ratio of H_3BO_3 to ZrOCl_2 is 4 ∶ 1.The final viscosity of fracturing fluid after continuously shearing 90 min at the speed of 170 s-1 under 150℃ stands above 80 MPa·s when the mass contents of hydroxypropyl guar gel solution and temperature resistance enhancer are 0. 5% and 0. 6% respectively,the volume ratio of guar gels solution and the prepared crosslinking agent is 100 ∶0. 6 and the crosslinking time lasts for 102 s.It is shown that the organic boron zirconium crosslinking agent fracturing fluid system has a good shear resistant and a delayed crosslinking performance.Excellent fracturing effects is achieved which it is evaluated at spot test.
引文
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[11]胡世平,李建平,韩俊华,等.有机硼锆交联剂的制备与延缓交联效果[J].油田化学,2016,33(1):37-39,62.
[12]肖博,张士诚,肖青香,等.耐高温压裂液配方优选与评价[J].西安石油大学学报(自然科学版),2014,29(1):80-84,9.
[13]李小凡,刘贺,江安,等.超高温有机硼交联剂的研究与应用[J].油田化学,2012,29(1):80-82,115.
[14]郭建春,辛军,王世彬,等.异常高温胍胶压裂液体系研制与应用[J].石油钻采工艺,2010,32(3):64-67.
[15]张玉广,张浩,王贤君,等.新型超高温压裂液的流变性能[J]中国石油大学学报(自然科学版),2012,36(1):165-169.
[2]韩玉婷.有机硼锆交联剂的制备及其在抗高温压裂液体系中的应用[D].成都:西南石油大学,2014.
[3]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.
[4]段贵府,胥云,卢拥军,等.耐超高温压裂液体系研究与现场试验[J].钻井液与完井液,2014,31(3):75-77.
[5]王博.高温压裂液体系研究及应用性能评价[D].西安:西安石油大学,2017.
[6]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,(2):113-115,119.
[7]张文胜,秦利平,任占春,等.压裂液用有机硼锆交联剂OBZ-1[J].油田化学,1996,(3):19-21,27.
[8]Sharif S.Process for preparation and composition of stable aqueous solutions of boron zirconium chelates for high temperature frac fluids:US,US5217632[P].1993-06-08.
[9]Putzig D E.Process to prepare borozirconate solution and use as a cross-linker in hydraulic fracturing fluids:US,US 7795190B2[P].2010-09-07.
[10]Rose J,Bruin T J M D,Chauveteau G,et al. Aqueous zirconium complexes for gelling polymers.A combined X-ray absorption spectroscopy and quantum mechanical study[J]. Journal of Physical Chemistry B,2003,107(13):2910-2920.
[11]胡世平,李建平,韩俊华,等.有机硼锆交联剂的制备与延缓交联效果[J].油田化学,2016,33(1):37-39,62.
[12]肖博,张士诚,肖青香,等.耐高温压裂液配方优选与评价[J].西安石油大学学报(自然科学版),2014,29(1):80-84,9.
[13]李小凡,刘贺,江安,等.超高温有机硼交联剂的研究与应用[J].油田化学,2012,29(1):80-82,115.
[14]郭建春,辛军,王世彬,等.异常高温胍胶压裂液体系研制与应用[J].石油钻采工艺,2010,32(3):64-67.
[15]张玉广,张浩,王贤君,等.新型超高温压裂液的流变性能[J]中国石油大学学报(自然科学版),2012,36(1):165-169.
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