页岩气水基钻井液用超支化聚胺结构与性能研究

发布时间：2018-06-23 11:13

  本文选题：端胺基超支化聚合物 + 抑制剂　； 参考：《西南石油大学》2017年硕士论文

【摘要】：在页岩气钻井过程中,页岩中大量的膨润土矿物遇水易发生水化膨胀、分散,给井壁稳定性带来了一定的隐患。近年来,针对这一问题国内外学者开发了一系列抑制剂并取得了不一的实际效果,这些抑制剂大部分以线性聚合物为基础来抑制膨润土的水化膨胀、分散。为从分子结构上寻求一定的创新性,本文开发出一种超支化结构的聚合物抑制剂,并探讨其结构与性能间的关系。本文以乙二胺和丙烯酸甲酯为原料,通过迈克尔加成反应合成了 AB2单体,并通过AB2单体间的缩聚反应制备出端胺基超支化聚合物Hyperbranched-NH2。在此基础上,以线性膨胀率为评价标准,优化了其最优合成条件为:乙二胺和丙烯酸甲酯的摩尔比为1:1,在100℃、120℃与140℃各聚合2小时。通过红外光谱与核磁共振氢谱分析得知聚合过程为酯与胺的亲核取代,聚合产物Hyperbranched-NH2含有伯胺,仲酰胺等抑制官能团。通过飞行时间质谱仪分析得知合成的Hyperbranched-NH2其分子量主要分布在200-1200这一范围,通过环境扫描电子显微镜发现了 Hyperbranched-NH2含有超支化聚合物典型的“准球型”结构。通过线性膨胀实验、热滚回收实验和流变性实验分别对Hyperbranched-NH2进行了性能评价。结论表明,3%的Hyperbranched-NH2水溶液其2小时和16小时的线性膨胀率分别仅为3.49%和11.42%,110℃热滚16小时后的热滚回收率为60.79%,其抑制效果与常用的抑制剂效果相当。流变性测试结果表明准球型的Hyperbranched-NH2对钻井液基浆体系的粘度影响较小,给其他添加剂的加入提供了较大的空间。在Hyperbranched-NH2和膨润土作用机理分析中,Zeta电位的测试结果表明Hyperbranched-NH2能有效地降低膨润土晶层水化膜厚度与膨润土颗粒Zeta电位的绝对值,黏土颗粒的Zeta电位从-40mV减少为-12.9mV。在红外光谱分析中,证实了Hyperbranched-NH2末端质子化的伯胺官能团与膨润土之间形成了稳定、有序的氢键结构。XRD的测试结果证实了 Hyperbranched-NH2可以插层进入膨润土晶层间阻止其渗透水化,使膨润土的层间距由1.23019nm增加至1.39298nm。在粒径分析中,加入3%Hyperbranched-NH2的基浆其膨润土微粒的中值粒径为8.384nm,相比空白基浆其中值粒径增大了 4.018nm,说明准球型的Hyperbranched-NH2可以桥联分散在水溶液中的膨润土微粒,相比其他抑制剂,其粒径的分布更加窄而均一,说明其与膨润土之间的作用更加均匀、全面。在絮凝试验中,Hyperbranched-NH2也表现出较好的絮凝能力,其絮凝膨润土的效果与SDJA和Ultrahib这些强抑制剂的絮凝能力相当。通过对其他钻井液添加剂的优选、复配与评价,最后确立了一套综合性能良好的钻井液体系:4%膨润土 + 0.24%Na2C03+ 3%Hyperbranched-NH2+ 0.4%FA-367 + 2.5%SPNH + 1.5%SMP-1+0.5%石墨+重晶石。钻井液的综合测试表明,该体系具有优良的抑制性、流变性、降滤失性、润滑性与耐温耐盐性,具有较好的应用前景。
[Abstract]:In the process of shale gas drilling, a large number of bentonite minerals in shale are easily hydrated and dilated in water, which brings some hidden trouble to the stability of wellbore. In recent years, scholars at home and abroad have developed a series of inhibitors and achieved different results. Most of these inhibitors are based on linear polymers to inhibit the hydration expansion and dispersion of bentonite. In order to find a certain innovation in molecular structure, a polymer inhibitor with hyperbranched structure was developed and the relationship between its structure and properties was discussed. In this paper, AB2 monomer was synthesized by Michael addition reaction from ethylenediamine and methyl acrylate, and hyperbranched-NH2 was prepared by condensation reaction between AB2 monomers. On this basis, the linear expansion rate was used as the evaluation standard, and the optimum synthesis conditions were optimized as follows: the molar ratio of ethylenediamine to methyl acrylate was 1: 1, polymerization at 100 鈩，

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