新型聚合物缓凝剂的合成与性能研究

发布时间：2019-04-23 20:37

【摘要】：随着油气储量的变化,油气田勘探开发已向深井、超深井和复杂井等方向发展,而深井、超深井固井中存在诸多问题,例如封固段长、上下温差大、顶部水泥浆易出现超缓凝等。在固井施工中,常在水泥浆中添加缓凝剂等外加剂来解决上述问题。传统缓凝剂目前仍存在一些的缺点,如适用温度范围窄、延缓低温下水泥石强度发展等,影响固井质量。针对上述固井中问题以及油井水泥缓凝剂所存在的缺陷,本文在已有聚合物类缓凝剂的基础上,引入长链烷基单体设计设计合成了一种疏水缔合水溶性聚合物缓凝剂。该聚合物以胺基-2-甲基丙磺酸(AMPS)、衣康酸(IA)、丙烯酸(AA)、N,N-二甲基丙烯酰胺(DMAA)和具有长侧链结构的季铵盐(DMAPMA-1-BD)为聚合单体,采用自由基水溶液聚合,合成了一种五元共聚物P(AMPS/IA/AA/DMAA/DMAPMA-1-BD),通过考察各反应条件对聚合物性质的影响,确定了该五元共聚物PAIADD的最佳合成条件。采用红外光谱仪和核磁共振仪对聚合物结构进行表征,结果表明所有单体均已参与聚合反应,利用热失重分析仪对聚合物的热稳定性进行测试,结果表明聚合物分子结构稳定,具有良好的耐热性能。本文对缓凝剂PAIADD进行水泥浆综合性能进行评价,结果表明其能明显的改善水泥体系性能,在高温条件下具有良好的缓凝性,在低温条件下对水泥石的早期强度发展影响较小,一定温度范围内初终凝时间几乎不变。这表明聚合物的相关性能对温度具有一定的响应性,能够适用于大温差环境中,在长封固段固井中具有一定的应用前景。此外利用扫描电镜和X射线衍射仪对缓凝剂PAIADD的缓凝机理进行探究,发现聚合物缓凝剂的作用机理为沉淀机理、钙离子螯合机理以及成核机理中的一种或多种作用的结果,并且在不同温度下其对水泥水化进程的阻碍程度相似。本文还对聚合物性能的温度响应性行为进行探究,流变测试、聚合物流体半径测试以及荧光光谱测试结果表明聚合物分子中存在缔合结构,并且这种结构随着温度的变化而发生变化,这种行为对聚合物的络合能力产生影响,即随着温度的升高,络合能力增强,这一行为通过滴定实验与紫外测试进行的验证。
[Abstract]:With the change of oil and gas reserves, exploration and development of oil and gas fields have developed to deep wells, ultra-deep wells and complex wells, and there are many problems in cementing in deep wells and ultra-deep wells, such as long sealing section and large temperature difference between upper and lower wells. The top cement slurry is easy to appear super-slow setting and so on. In cementing operation, additives such as retarder are often added to cement slurry to solve the above problems. There are still some shortcomings in the traditional retarder, such as narrow applicable temperature range, delaying the development of low-temperature mud and stone strength, and so on, which affect the cementing quality. In view of the problems mentioned above and the defects of oil well cement retarder, a hydrophobic associating water soluble polymer retarder was designed and synthesized by introducing long chain alkyl monomer on the basis of existing polymer retarder. (AA), N, N-dimethylacrylamide (DMAA) and quaternary ammonium salt (DMAPMA-1-BD) with long side chain structure were used as the monomers of the polymer, (AMPS), itaconic acid, (AA), N, N-dimethylacrylamide and ammonium salt (DMAPMA-1-BD) with long side chain structure. A quaternary copolymer P (AMPS/IA/AA/DMAA/DMAPMA-1-BD) was synthesized by free radical aqueous solution polymerization. The effects of reaction conditions on the properties of the copolymer were investigated, and the optimum synthesis conditions of the five-component copolymer PAIADD were determined. The structure of the polymer was characterized by IR spectrometer and NMR. The results showed that all the monomers were involved in the polymerization. The thermal stability of the polymer was tested by thermogravimetric analyzer, and the results showed that the molecular structure of the polymer was stable. It has good heat resistance. The comprehensive properties of cement slurry with retarder PAIADD are evaluated in this paper. The results show that it can obviously improve the performance of cement system and has a good retarding property at high temperature, and has little effect on the early strength development of cement paste at low temperature. The initial and final setting time is almost unchanged within a certain temperature range. The results show that the relative properties of the polymer are sensitive to temperature and can be used in the environment of large temperature difference, and it has a certain application prospect in the cementing of long cementing section. In addition, scanning electron microscopy and X-ray diffractometer were used to investigate the retarder mechanism of PAIADD. It was found that the mechanism of polymer retarder was precipitation mechanism, calcium chelation mechanism and one or more effects in nucleation mechanism. The degree of hindrance to cement hydration process at different temperatures is similar. In this paper, the temperature-responsive behavior of polymer properties, rheological test, polymer fluid radius test and fluorescence spectrum test results show that there are association structures in polymer molecules. And this structure changes with the change of temperature, this behavior has an effect on the complexation ability of the polymer, that is, the complexation ability increases with the increase of temperature, this behavior is verified by titration experiment and ultraviolet test.
【学位授予单位】：天津大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：TE256.6

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