Preparation and Plugging Performance of Zwitterionic Polymer Gel Micro Spheres
-
摘要: 针对油基钻井液封堵性不足的难题,以N,N-二甲基丙烯酰胺(DAM)、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)和二烯丙基二甲基氯化铵(DMDAAC)为单体,以N,N-亚甲基双丙烯酰胺(MBA)为交联剂,采用悬浮聚合法合成了一种两性离子聚合物凝胶微球。采用核磁共振氢谱对凝胶微球进行了分子结构表征,并考察了单体投料比、交联剂加量、乳化剂加量等对凝胶微球粒径与封堵性能的影响规律,最终将单体投料比优选为DAM∶AMPS∶DMDAAC=7∶1∶2,MBA加量优选为单体总质量的0.2%,乳化剂加量优选为单体总质量的3%,得到的凝胶微球平均粒径在22 μm左右。在油基钻井液中评价了微球的封堵性能,结果表明,凝胶微球在油基钻井液中的适应性良好,能够在高温下封堵尺寸为5~150 μm范围内的漏缝,效果优于氧化沥青与细目碳酸钙,是一种高性能的微米级封堵剂,具有较好的现场应用潜力。Abstract: A kind of zwitterionic polymer gel micro spheres have been prepared through suspension polymerization to address the deficiency of plugging capacity of oil based drilling fluids. The raw materials used in the polymerization include N , N -dimethyl acrylamide (DAM), 2-acrylamido-2-methyl propane sulfonic acid (AMPS) and dimethyl diallyl ammonium chloride (DMDAAC), and the crosslinking agent for the polymerization reaction is N , N -methylene-bis-acrylamide (MBA). Using H-NMR spectrometry, the molecular structure of the polymer gel micro spheres was characterized. Effect of the molar ratio of the monomers and the concentrations of the crosslinking agent and emulsifier on the size distribution and plugging performance of the polymer gel spheres was investigated. The optimum molar ratio of the monomers for the polymerization was determined as: DAM∶AMPS∶DMDAAC = 7∶1∶2, the optimum mass concentration of MBA (based on the total mass of the monomers) was 0.2%, and the optimum concentration of the emulsifier (based on the total mass of the monomers) was 3%. The average particle size of the polymer gel micro spheres is about 22 μm. The plugging capacity of the polymer gel micro spheres was tested in oil based muds, and it was found that the polymer gel micro spheres are suitable very well to use in the oil based muds. At 150 ℃, the polymer gel micro spheres can effectively plug fractures of 5-150 μm, a plugging performance better than the combination of oxidized asphalt and fine calcium carbonate. The test results show that the zwitterionic polymer gel micro spheres are a high-performance millimeter-sized plugging agent with good field application potential.
-
Key words:
- Plugging agent /
- Zwitterionic polymer /
- Gel /
- Micro sphere /
- Oil based mud
-
表 1 不同单体投料比对两性离子聚合物凝胶微球粒径的影响
DAM∶AMPS∶DMDAAC 平均粒径/
μmD50/
μmD90/
μm7∶2.5∶0.5 16.5 14.4 17.8 6∶3.5∶0.5 15.2 13.5 17.4 7∶1∶2 16.1 15.7 17.0 4.5∶4.5∶1 10.9 9.9 12.3 表 2 交联剂加量对微球粒径的影响
交联剂/
%平均粒径/
μmD50/
μmD90/
μm0.2 16.1 15.7 17.0 0.5 15.4 14.1 16.8 1 13.1 12.0 12.9 表 3 乳化剂加量对微球粒径的影响
乳化剂/
%平均粒径/
μmD50/
μmD90/
μm1 36.9 40.6 54.3 3 22.0 20.6 26.1 5 16.1 15.7 17.0 7 13.2 13.9 14.4 表 4 含凝胶微球油基钻井液体系的基本性能
T/
℃AV/
mPa·sPV/
mPa·sYP/
PaGel/
Pa/PaFLHTHP/
mL热滚前 70.0 61 9.20 4.0/6.0 80 ℃、16 h 71.0 63 8.18 4.0/6.0 2.8(80 ℃) 120 ℃、16 h 75.5 68 7.66 3.5/5.0 6.2(120 ℃) 150 ℃、16 h 81.5 75 6.64 3.5/5.0 8.4(150 ℃) 注:热滚时间为16 h,FL HTHP在3.5 MPa下测定 表 5 含氧化沥青与细目碳酸钙的油基钻井液体系的基本性能
封堵剂 实验/
条件AV/
mPa·sPV/
mPa·sYP/
PaGel/
Pa/PaFLHTHP/
mL氧化
沥青热滚前 68.5 58 10.5 4.0/5.5 150 ℃、16 h 75.0 65 10.0 4.0/6.0 5.8 细目
碳酸钙热滚前 64.5 57 7.5 3.0/3.5 150 ℃、16 h 67.5 61 6.5 3.0/3.5 9.1 注:热滚时间为16 h,FL HTHP在3.5 MPa下测定 -
[1] 黄书红,蒲晓林,陈勇,等. 新型无荧光防塌封堵剂HSH的研制及机理研究[J]. 钻井液与完井液,2013,30(1):9-11. doi: 10.3969/j.issn.1001-5620.2013.01.003HUANG Shuhong, PU Xiaolin, CHEN Yong, et al. Preparation and mechanism of a new non fluorescent anti collapse plugging agent HSH[J]. Drilling Fluid & Completion Fluid, 2013, 30(1):9-11. doi: 10.3969/j.issn.1001-5620.2013.01.003 [2] 王力,孟尚志,陈万钢,等. 提高煤层强度的钻井液防塌封堵剂的研制[J]. 钻井液与完井液,2018,35(5):46-49. doi: 10.3969/j.issn.1001-5620.2018.05.009WANG Li, MENG Shangzhi, CHEN Wangang. Development of and study on an anti-sloughing plugging agent used in drilling fluids to strengthen coal beds[J]. Drilling Fluid & Completion Fluid, 2018, 35(5):46-49. doi: 10.3969/j.issn.1001-5620.2018.05.009 [3] 王伟,赵春花,罗健生,等. 抗高温油基钻井液封堵剂PF-MOSHIELD的研制与应用[J]. 钻井液与完井液,2019,36(2):153-159. doi: 10.3969/j.issn.1001-5620.2019.02.004WANG Wei, ZHAO Chunhua, LUO Jiansheng. Development and application of the high temperature plugging agent PF-MOSHIELD for oil base drilling fluids[J]. Drilling Fluid & Completion Fluid, 2019, 36(2):153-159. doi: 10.3969/j.issn.1001-5620.2019.02.004 [4] 林梅钦,董朝霞,彭勃,等. 交联聚丙烯酰胺微球的形状与大小及封堵特性研究[J]. 高分子学报,2011(1):48-54.LIN Meiqin, DONG Zhaoxia, PENG Bo, et al. Shape, size and plugging properties of crosslinked polyacryamide microspheres[J]. Acta Polymerica Sinica, 2011(1):48-54. [5] 王伟吉,邱正松,黄维安,等. 纳米聚合物微球封堵剂的制备及特性[J]. 钻井液与完井液,2016,33(1):33-34.WANG Weiji, QIU Zhengsong, HUANG Wei’an, et al. Preparation and characteristics of nano polymer microspheres used as plugging agent in drilling fluid[J]. Drilling Fluid & Completion Fluid, 2016, 33(1):33-34. [6] 王建华,李建男,闫丽丽,等. 油基钻井液用纳米聚合物封堵剂的研制[J]. 钻井液与完井液,2016,33(6):5-8.WANG Jianhua, LI Jiannan,YAN Lili, et al. Development of nano polymer plugging agent for oil based drilling fluid[J]. Drilling Fluid & Completion Fluid, 2016, 33(6):5-8. [7] 毛程,丁伟,毛涛,等. 磺基甜菜碱型两性离子聚合物的盐溶液性质[J]. 钻井液与完井液,2011,28(5):5-7.MAO Cheng, DING Wei, MAO Tao, et al. Research on performances of sulfobetaine amphoteric copolymer salt solution[J]. Drilling Fluid & Completion Fluid, 2011, 28(5):5-7. [8] 黄文红,马喜平. 两性离子聚合物PADAM的合成及性能评价[J]. 钻井液与完井液,2005,22(5):34-35.HUANG Wenhong, MA Xiping. Synthesis and performance evaluation of zwitterionic polymer PADAM[J]. Drilling Fluid & Completion Fluid, 2005, 22(5):34-35. [9] 姜志高,郑晓宇,郭文峰,等. 反相悬浮聚合法制备交联聚合物微球改善聚合物驱的效果[J]. 油田化学,2016(12):687-691.JIANG Zhigao, ZHENG Xiaoyu, GUO Wenfeng, et al. Preparation of crosslinked polymer microspheres by inverse suspension polymerization to improve the effect of polymer flooding[J]. Oilfield Chemistry, 2016(12):687-691. [10] 蒋官澄,刘凡,任妍君,等. 抗高温抗高钙降滤失剂DF-1的研制与评价[J]. 油田化学,2015,32(1):1-6.JIANG Guancheng, LIU Fan, REN Yanjun, et al. Synthesis and evaluation of high temperature resistant and high calcium tolerant filtrate loss additive DF-1[J]. Oilfield Chemistry, 2015, 32(1):1-6. [11] 李斌,蒋官澄,贺垠博. 一种抗高温抗钙两性离子聚合物分散剂[J]. 钻井液与完井液,2019,36(3):303-307. doi: 10.3969/j.issn.1001-5620.2019.03.007LI Bin, JIANG Guancheng, HE Yinbo. A high temperature calcium resistant amphoteric polymer dispersant[J]. Drilling Fluid & Completion Fluid, 2019, 36(3):303-307. doi: 10.3969/j.issn.1001-5620.2019.03.007 [12] ZHANG X, JIANG G, XUAN Y, et al. Associating copolymer AM/DMDAAC/BA/AMPS as a tackifier in clay-free and water-based drilling fluids[J]. Energy & Fuels, 2017, 31(5):4655-4662. [13] 杨小华. N, N-二甲基丙烯酰胺聚合物的合成及其应用研究进展[J]. 应用化工,2009(10):1509-1510.YANG Xiaohua. Progress in synthesis and application of N , N -dimethylacrylamide polymer[J]. Applied Chemical Industry, 2009(10):1509-1510. [14] 王中华. 钻井液用超支化反相乳液聚合物的合成及其性能[J]. 钻井液与完井液,2014,31(5):14-16. doi: 10.3969/j.issn.1001-5620.2014.05.004WANG Zhonghua. Synthesis and properties of hyperbranched inverse emulsion polymer for drilling fluids[J]. Drilling Fluid & Completion Fluid, 2014, 31(5):14-16. doi: 10.3969/j.issn.1001-5620.2014.05.004 -