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丙烯酸—丙烯酰胺—丙烯酰氧乙基三甲基氯化铵钻井液降滤失剂合成及其性能的研究

Study on Synthesis and Properties of Drilling Fluid Filtrate Reducer Acrylic Acid-acrylamide-acryloxyethyl Trimethylammonium Chloride

【作者】 孙先长

【导师】 万涛;

【作者基本信息】 成都理工大学 , 应用化学, 2011, 硕士

【摘要】 在传统的阴离子型钻井液降滤失剂制备中,通过引人阳离子单体可以制得聚阳离子型、两性离子降滤失剂,在改善钻井液流变性能、降低水眼粘度、控制井壁稳定以及地层造浆等方面有着阴离子型降滤失剂无法比拟的优点,特别是抗高价金属离子污染能力强,能够满足高压喷射钻井和优快化钻井的需要。从20世纪90年代中期至今,对两性离子多元共聚物降滤失剂的研究取得了可喜进展,新产品层出不穷。然而两性离子共聚物降失水剂的不足之处在于抗温能力。为此,这也给研究者们提出了更高的要求,研制开发耐更高温度的产品以适应超深井钻探的需要。本文尝试以丙烯酸(AA)、丙烯酰胺(AM)、丙烯酰氧乙基三甲基氯化铵(DAC)作为原料单体,去离子水为溶剂,少量过硫酸铵水溶液为还原引发剂,聚合合成一种新的水溶性聚合物钻井液降滤失剂。通过对AA-AM-DAC共聚物物的水溶液比浓粘度及其钻井液表观粘度、塑性粘度、滤失量、动切力的研究,确定了最佳的聚合反应参数:引发剂用量、AA/AM比例、DAC用量、反应温度。分析盐浓度、钙含量、温度对两性离子聚合物钻井液性能的影响;利用红外光谱(FTIR)研究两性离子聚合物中官能团对其钻井液性能的影响;利用热重分析(TGA)验证共聚物的热稳定性;通过热滚试验验证共聚物钻井液的抗温性能;通过页岩滚动回收率试验考查该共聚物的防塌、抑制能力。得到了抗温、抗盐、抗钙,综合性能较好的的水溶性聚合物钻井液降滤失剂,可适用于多种钻井液体系。主要研究成果如下:(1)为得到聚合稳定、聚合反应速率快、分子量高的共聚物,通过优化聚合工艺,得到了最佳的反应聚合参数:AA/AM比例为4:6,丙烯酰氧乙基三甲基氯化铵(DAC)用量为20%,引发剂浓度为1%,聚合反应温度55℃。(2)合成的AA-AM-DAC共聚物具有良好的抗盐性能和高价金属离子污染能力,且抗二价金属阳离子Ca2+能力强于一价阳离子Na+能力。(3)热滚试验表明:聚合物钻井液的滤失量随温度升高而增大,在160℃内增加幅度并不大,表明聚合钻井液降滤失剂具有良好的抗温性能,抗温可达160℃。(4)抑制性评价表明:共聚物具有较强的抑制页岩水化分散能力,且随着加量的增大抑制性增强,不仅一次回收率较高,且二次回收率也处在较高水平,可见共聚物在页岩表面可形成较强的吸附能力。(5)FTIR谱图表明所合成的水溶性聚合物为丙烯酸、丙烯酰胺、丙烯酰氧乙基三甲基氯化铵的共聚物;TGA显示聚合物的起始失重温度为210℃,起始失重率为6.15%,501.4℃时残余质量为14.76%,可见,三元共聚物具有较高的热稳定性。

【Abstract】 Poly cationic and zwitterionic filtrate reducer have some incomparable advantages over the anionic type drilling fluid filtrate reducer in improve the rheological behavior, reduce the bit nozzle viscosity, control well bore stability and mud yield, especially they have great resistance ability to high valence metal ion pollution, they can satisfy the high pressure jet drilling and the optimal-fast drilling program. From the mid 1990s to today, the research about zwitterionic copolymer filtrate reducer made gratifying progress and new products emerge in endlessly. But the A shortcoming of zwitterionic copolymer filtrate reducer is the low temperature resistance. All of this brings out the higher requirements for the researchers to develop higher temperature resistance products which adapt to the need of super deep drilling.This article attempts to use acrylic acid (AA), acrylic amide (AM) and acryloxyethyl trimethylammonium chloride (DAC) as comonomers, deionized water as solvent, ammonium persulfate as the redox initiator to synthesize water soluble copolymers of AA-AM-DAC as drilling fluids filtrate reducer.The properties of AA-AM-DAC drilling fluid as apparent viscosity, plastic viscosity, the filtration, yield point and the AA-AM-DAC water solution properties as reduced viscosity are discussed; the optimum polymerization parameters as initiator consumption, AA/AM mass ratio, DAC consumption, and reaction temperature are established. The effect of the salt concentration, calcium content and temperature to zwitterionic polymer drilling fluid properties was analysed.The molecular structure and the thermal stability of the synthesized water soluble polymers were characterized by fourier transform infrared spectroscopy (FTIR) Analysis and the thermal gravimetric analysis (TGA). The AA-AM-DAC drilling fluid temperature resistance was validated by hot rolling test. The inhibition and preventing collapse capability of the copolymer was verified by the shale rolling recovery test. The termerature resistant, salt resistant, calcium resistant and polymer drilling fluids filtrate reducer which can be used for various drilling fluids system was obtained. The main research achievements are as follows:(1)To achieve the objectives of a stable and rapid polymerization and copolymers with high molecular weight, the polymerization technique was optimized and the optimal polymerization parameters are as follows: AA/AM mass ratio of 4:6; DAC amount of 20%; initiator amount of 1%; polymerization temperature of 55℃.(2)The synthesized AA-AM-DAC polymers has good salt-resistance and high valence metal ion pollution resistance.The ability of resistance to Ca2+ was higher than Na+.(3) The hot rolling test showed: the filtration of the AA-AM-DAC polymer drilling fluid increased slightly with increase temperature at 25-160℃, an indicative of good temperature-resistance of the polymer drilling fluids, temperature- resistance amounted to 160℃.(4) Inhibitory evaluation showed: the copolymer has great inhibited shale hydration dispersed capacity, and the inhibition increased with the copolymer dosage increased. Not only the first recovery rate is high but also the second recovery is high. Strong adsorption capacity of the copolymer on the shale surface was showed.(5) FTIR spectra showed the water soluble polymer was AA/AM/DAC copolymers. TGA showed the onset decomposition temperature of the copolymer was 210℃, the starting decomposition rate at 6.15% and 14.76% residual quality at 501.4℃.So the terpolymer has high thermal stability.

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