油酸改性纳米TiO_2的制备及其驱油性能评价
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摘要
纳米颗粒驱油技术在低渗油藏有较好的驱油效果,但纳米颗粒作为驱油剂在水溶液中的团聚并堵塞地层小孔隙的问题,一直未得到很好的解决。本文使用低成本的油酸对纳米TiO_2进行表面改性,采用红外光谱分析仪、扫描电镜和Zeta电位分析仪分析了改性纳米TiO_2的结构和形貌。并通过低渗透岩心模拟驱油实验优选合理的驱油体系。研究表明,使用油酸对纳米TiO_2表面进行改性,当反应物摩尔比为1∶1,在60℃条件下反应4 h时,改性得到的纳米TiO_2在水溶液中稳定性最好。红外光谱测定证明了油酸基团成功接枝到纳米TiO_2表面。改性后的纳米TiO_2颗粒分散稳定性得到大幅提升,粒径的测试结果显示纳米TiO_2在水溶液中的平均粒径为246.7nm。质量分数为0.05%的改性前后的纳米TiO_2体系在亲水载玻片表面的接触角分别29.95o、81.44o,油水界面张力值分别为0.475和0.74 mN/m,说明改性TiO_2颗粒提高采收率的机理依然是主要依靠改变岩石润湿性和降低油水界面张力两方面。对于渗透率范围在9×10~(-3)数12×10~(-3)μm~2的低渗油藏,合理注入体系为0.1%改性纳米TiO_2+0.05%OP-10,注入体积为0.3 PV,提高采收率达到15%。纳米TiO_2溶液不仅能降低注入水的压力,而且能提高低渗透油藏的采收率。图7表1参18
Nanoparticle flooding technology has a good oil displacement effect in low permeability reservoirs,but the problem of nanoparticles agglomeration in aqueous solution and blocking small pores in the formation has not been well solved. Low-cost oleic acid is used herein to surface modification of nano-TiO_2 for reducing the agglomeration of nanoparticles,and the oil displacement system was optimized through low-permeability core simulation flooding experiment. The results showed that when the molar ratio of oleic acid to nano-TiO_2 was 1∶1 and reacted at 60℃ for 4 h,the obtained modified nano-TiO_2 had the longest stabilized dispersion time in aqueous solution. Infrared spectroscopy confirmed that the oleic acid group was successfully grafted onto the surface of nano-TiO_2. SEM and Zeta potential indicated that the dispersibility and stability of the modified nano-TiO_2 particles was greatly improved. The particle size test results showed that the average particle size of nano-TiO_2 in aqueous solution was 246.7 nm. the contact angle of unmodified nano-TiO_2 and modified nano-TiO_2 system with mass fracion of 0.05% on the surface of hydrophilic slide was 29.95 oand 81.44 o,respectively,and the interfacial tension value was 0.475 and 0.74 mN/m,respectively,which explained the mechanism of enhancing oil recovery of the modified nano-TiO_2 was still mainly relying on changing rock wettability and reducing oil-water interfacial tension. As for the low peameability reservoir with peameability of 9 × 10~(-3)—12×10~(-3)μm~2,the reasonable injection parameters of the displacement system was 0.1% modified nano-TiO_2+ 0.05% OP-10,and the reasonable injection volume was 0.3 PV,at this time,the enhanced oil recovery reached up to 15%. The nano-TiO_2 solution could not only reduce the pressure of the injected water,but also improve the recovery rate of low-permeability core.
Nanoparticle flooding technology has a good oil displacement effect in low permeability reservoirs,but the problem of nanoparticles agglomeration in aqueous solution and blocking small pores in the formation has not been well solved. Low-cost oleic acid is used herein to surface modification of nano-TiO_2 for reducing the agglomeration of nanoparticles,and the oil displacement system was optimized through low-permeability core simulation flooding experiment. The results showed that when the molar ratio of oleic acid to nano-TiO_2 was 1∶1 and reacted at 60℃ for 4 h,the obtained modified nano-TiO_2 had the longest stabilized dispersion time in aqueous solution. Infrared spectroscopy confirmed that the oleic acid group was successfully grafted onto the surface of nano-TiO_2. SEM and Zeta potential indicated that the dispersibility and stability of the modified nano-TiO_2 particles was greatly improved. The particle size test results showed that the average particle size of nano-TiO_2 in aqueous solution was 246.7 nm. the contact angle of unmodified nano-TiO_2 and modified nano-TiO_2 system with mass fracion of 0.05% on the surface of hydrophilic slide was 29.95 oand 81.44 o,respectively,and the interfacial tension value was 0.475 and 0.74 mN/m,respectively,which explained the mechanism of enhancing oil recovery of the modified nano-TiO_2 was still mainly relying on changing rock wettability and reducing oil-water interfacial tension. As for the low peameability reservoir with peameability of 9 × 10~(-3)—12×10~(-3)μm~2,the reasonable injection parameters of the displacement system was 0.1% modified nano-TiO_2+ 0.05% OP-10,and the reasonable injection volume was 0.3 PV,at this time,the enhanced oil recovery reached up to 15%. The nano-TiO_2 solution could not only reduce the pressure of the injected water,but also improve the recovery rate of low-permeability core.
引文
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[2]吕玉珍,张胜男,杜岳凡,等.油酸修饰对纳米二氧化钛在变压器油中分散性的影响[J].无机材料学报,2013,28(6):594-598.
[3]陈志海.特低渗油藏储层微观孔喉分布特征与可动油评价:以十屋油田营城组油藏为例[J].石油实验地质,2011,33(6):657-661.
[4]贺丽鹏,罗健辉,丁彬,等.特低/超低渗油藏纳米驱油剂的制备与性能[J].油田化学,2018,35(1):81-84.
[5]王瑶.纳米流体在储层岩芯表面的铺展及其驱油机理研究[D].西安:西安石油大学,2015.
[6]张忠林,王成俊.延长油田特低渗油藏新型驱油剂研究进展[J].应用化工,2018,47(6):1246-1249.
[7]姚超,高国生,林西平,等.硅烷偶联剂对纳米二氧化钛表面改性的研究[J].无机材料学报,2006(2):315-321.
[8]吴恒安.纳米流体提高驱油效率的微力学机理研究[C].//中国力学大会——2013论文摘要集.西安:2013:1.
[9]王维.驱油用纳米二氧化硅的制备及改性研究[D].青岛:中国石油大学(华东),2015.
[10]郭璐瑶.纳米二氧化钛分散及其表面改性研究[D].上海:东华大学,2015.
[11] YU H,KOTSMAR C,YOON K Y,et al. Transport and retention of aqueous dispersions of paramagnetic nanoparticles in reservoir rocks[C].//Proceedings of the SPE Improved Oil Recovery Symposium. Tulsa,Oklahoma,April 24-28,2010.
[12]李小培,艾照全,肖宇,等.油酸改性纳米二氧化钛/聚丙烯酸酯复合乳液的制备及表征[J].粘接,2015,36(4):50-53.
[13]沈钟,王国庭.胶体与表面化学[M].北京:化学出版社,1992.
[14]王晓龙. KH-792改性纳米二氧化硅在三次采油中动态界面张力的研究[D].北京交通大学,2010.
[15] EHTESABI H,AHADIAN M M,TAGHIKHANI V. Enhanced heavy oil recovery using TiO2nanoparticles:investigation of deposition during transport in core plug[J]. Energy Fuel,2015,29(1):1-8.
[16]宫军,徐文波,陶洪辉.纳米液驱油技术研究现状[J].天然气工业,2006(5):105-107.
[17]王世禄.纳米二氧化硅的改性及其降压增注性能评价[D].青岛:中国石油大学(华东),2016.
[18]张继超,曹绪龙,汤战宏,等.聚硅材料改善低渗透油藏注水效果实验[J].油气地质与采收率,2003(4):59-60.
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