微米化重晶石浓浆用梳型聚合物分散剂的合成及应用
发布时间：2018-10-05 07:14
【摘要】：目前全世界范围内中浅层的石油资源已基本枯竭,现在石油勘探的趋势逐步往陆地深层、海洋深层以及环境恶劣的区域发展,所以对高密度钻井液的研究提出了更高的要求。高密度钻井液研究中最突出的问题是如何调控流变性与沉降稳定性之间的矛盾。常规API重晶石在使用过程中常常会出现因流变性难以控制和固相沉降导致卡钻等严重问题。为了解决这些难题可以使普通API重晶石微米化改性,使其平均粒径小于10μm,这种微米化改性的新型重晶石可以解决深井、大位移井和斜井中出现的重晶石沉降与流变性难以控制之间的矛盾。由于石油钻井过程中常常会遇到盐膏层,电解质污染是不可避免的,所以研发一种既能很好地分散重晶石又能有很好的抗盐能力(耐盐NaCl含量大于30%)的新型分散剂是十分迫切的。所以本论文通过水溶液自由基聚合的方法合成了一种不仅分散效果好,又能抗盐的梳型聚合物重晶石分散剂,并用行星球磨机湿磨API重晶石的方式制备出了聚合物包覆的微米化重晶石浓浆体系。本论文的主要内容包括：1.梳型聚合物的合成及表征本文通过取大单体异戊烯醇聚氧乙烯醚(TPEO)或烯丙醇聚氧乙烯醚(APEO)溶于水中,再配以丙烯酸(AA)、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)两种单体,采用水溶液自由基聚合法得到梳型聚合物分散剂。红外光谱、核磁分析表征了聚合物结构中存在各单体官能团,证实了梳型结构；利用元素分析法确定了聚合物中元素比例,进而计算各结构单元所占比例；利用凝胶色渗透谱仪测试的梳型聚合物分子量在1-2万左右。2.微米化重晶石浓浆的制备及浓浆性能的测试本文利用行星球磨机湿磨API重晶石的方式制备出了固含量高达80%的(2.5g/cmm3)聚合物包覆的微米化重晶石浓浆体系,并用光学显微镜证实了颗粒平均粒径已小于2μm。将浓浆体系用Haake流变仪测试流变性,并与使用直链型重晶石分散剂制备出来的浓浆体系的流变性进行了对比,证实了梳型聚合物分散剂的超强的分散能力和极强的抗盐能力。M-I公司水基钻井液用微米化重晶石浓浆体系最高密度为2.2g/cm3,并且表观粘度为100 mPa.s,而本论文研制的微米化重晶石浓浆体系密度高达2.5g/cm3,表观粘度仅为35 mPa.S。本论文还提供了使用流变仪来预测重晶石浓浆体系沉降趋势的方法及思路,为我们进一步在高密度水基钻井液中更理想地使用微米化重晶石提供了一些理论依据。3.梳型聚合物与重晶石的相互作用研究本文通过吸附、Zeta电势以及流变学等表征手段,研究不同支链密度、长度的梳型聚合物对重晶石分散体系的影响。聚合物通过羧酸与磺酸基团与重晶石颗粒表面钡离子(Ba2+)以形成配位键的方式吸附在重晶石表面,同时侧链向外伸展在水溶液中。随聚合物浓度的增加,聚合物在粘土表面的吸附量增加,颗粒的Zeta电势绝对值也相应增加。对照体系流变实验结果,发现侧链长度的增加,对颗粒表面Zeta电位绝对值的增加贡献不大,并且长的侧链能使重晶石分散体系粘度降低,同时使其体系结构强度降低,即梳型聚合物对重晶石体系具有良好的分散特性。
[Abstract]:At present, the shallow petroleum resources in the world have dried up basically, and now the trend of oil exploration has gradually developed to the deep, deep and bad regions of the land, so the research of high-density drilling fluid has put forward higher requirements. The most prominent problem in the research of high density drilling fluid is how to regulate the contradiction between rheological property and settlement stability. In the process of use, the conventional API Barite often has serious problems such as difficult control of rheological property and settlement of solid phase. In order to solve these problems, it is possible to make the average particle size smaller than 10. m As the salt paste layer is often encountered during petroleum drilling, electrolyte pollution is inevitable, so it is very urgent to develop a new type of dispersant which has good salt resistance (salt tolerance NaCl content greater than 30%). In this paper, an aqueous solution free radical polymerization method is used to synthesize a kind of comb-type polymer Barite dispersing agent with good dispersion effect and anti-salt, which is prepared by wet milling API Barite with planetary ball mill. The main contents of this thesis include: 1. The synthesis and characterization of comb-type polymers is characterized by taking macromonomer isoamylene alcohol polyoxyethylene ether (TPEO) or allyl alcohol polyoxyethylene ether (APEO) in water, and mixing with acrylic acid (AA), 2-propynyl-2-methylpropanic acid (AMPS) monomers, A comb-type polymer dispersant was obtained by free radical polymerization of aqueous solution. The IR spectrum and nuclear magnetic analysis characterize the monomer functional groups in the polymer structure, confirm the comb-type structure, determine the proportion of elements in the polymer by elemental analysis, and then calculate the proportion of the structural units. The molecular weight of comb polymer tested by gel-color penetration spectrometer is about 1-20,000. In this paper, the preparation and slurry properties of micron Barite thick slurry were studied. Using the method of wet milling API Barite of planetary ball mill, the paper prepared a micron-sized Barite thick slurry system with high solid content up to 80% (2.5g/ cmm3). The results show that the average particle size of the particles is less than 2. m The strong dispersing ability and extremely strong salt resistance of the comb-type polymer dispersing agent are confirmed. The highest density of M-I water-based drilling fluid for water-based drilling fluid is 2.2g/ cm3, and the density is 100 mPa.s. The density of the micron-sized Barite concentrate system developed in this paper is up to 2.5g/ cm3, and the density is only 35mPa.s. This paper also provides a method and a train of thought for predicting the settlement tendency of a Barite thick slurry system using a rheometer, which provides some theoretical basis for the more ideal use of micro barytes in high density water-based drilling fluid. The effect of comb-type polymer with different branch density and length on the dispersion system of Barite was studied by means of adsorption, Zeta potential and rheology. The polymer is adsorbed on the surface of the Barite by ionic (Ba2 +) with the surface of the sulfonic acid group and the particle surface of the Barite particles, while the side chains extend outward in the aqueous solution. As the concentration of the polymer increases, the amount of adsorption of the polymer on the surface of the clay increases, and the absolute value of the Zeta potential of the particles also increases accordingly. According to the rheological experiment results of the control system, the increase of the length of the side chain is found, the increase of the absolute value of the Zeta potential of the particle surface is not large, and the long side chain can reduce the viscosity of the Barite dispersion system, and meanwhile, the structure strength is reduced, that is, comb-type polymer has good dispersing property on the Barite system.
【学位授予单位】：山东大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TE254.4
本文编号：2252488
[Abstract]:At present, the shallow petroleum resources in the world have dried up basically, and now the trend of oil exploration has gradually developed to the deep, deep and bad regions of the land, so the research of high-density drilling fluid has put forward higher requirements. The most prominent problem in the research of high density drilling fluid is how to regulate the contradiction between rheological property and settlement stability. In the process of use, the conventional API Barite often has serious problems such as difficult control of rheological property and settlement of solid phase. In order to solve these problems, it is possible to make the average particle size smaller than 10. m As the salt paste layer is often encountered during petroleum drilling, electrolyte pollution is inevitable, so it is very urgent to develop a new type of dispersant which has good salt resistance (salt tolerance NaCl content greater than 30%). In this paper, an aqueous solution free radical polymerization method is used to synthesize a kind of comb-type polymer Barite dispersing agent with good dispersion effect and anti-salt, which is prepared by wet milling API Barite with planetary ball mill. The main contents of this thesis include: 1. The synthesis and characterization of comb-type polymers is characterized by taking macromonomer isoamylene alcohol polyoxyethylene ether (TPEO) or allyl alcohol polyoxyethylene ether (APEO) in water, and mixing with acrylic acid (AA), 2-propynyl-2-methylpropanic acid (AMPS) monomers, A comb-type polymer dispersant was obtained by free radical polymerization of aqueous solution. The IR spectrum and nuclear magnetic analysis characterize the monomer functional groups in the polymer structure, confirm the comb-type structure, determine the proportion of elements in the polymer by elemental analysis, and then calculate the proportion of the structural units. The molecular weight of comb polymer tested by gel-color penetration spectrometer is about 1-20,000. In this paper, the preparation and slurry properties of micron Barite thick slurry were studied. Using the method of wet milling API Barite of planetary ball mill, the paper prepared a micron-sized Barite thick slurry system with high solid content up to 80% (2.5g/ cmm3). The results show that the average particle size of the particles is less than 2. m The strong dispersing ability and extremely strong salt resistance of the comb-type polymer dispersing agent are confirmed. The highest density of M-I water-based drilling fluid for water-based drilling fluid is 2.2g/ cm3, and the density is 100 mPa.s. The density of the micron-sized Barite concentrate system developed in this paper is up to 2.5g/ cm3, and the density is only 35mPa.s. This paper also provides a method and a train of thought for predicting the settlement tendency of a Barite thick slurry system using a rheometer, which provides some theoretical basis for the more ideal use of micro barytes in high density water-based drilling fluid. The effect of comb-type polymer with different branch density and length on the dispersion system of Barite was studied by means of adsorption, Zeta potential and rheology. The polymer is adsorbed on the surface of the Barite by ionic (Ba2 +) with the surface of the sulfonic acid group and the particle surface of the Barite particles, while the side chains extend outward in the aqueous solution. As the concentration of the polymer increases, the amount of adsorption of the polymer on the surface of the clay increases, and the absolute value of the Zeta potential of the particles also increases accordingly. According to the rheological experiment results of the control system, the increase of the length of the side chain is found, the increase of the absolute value of the Zeta potential of the particle surface is not large, and the long side chain can reduce the viscosity of the Barite dispersion system, and meanwhile, the structure strength is reduced, that is, comb-type polymer has good dispersing property on the Barite system.
【学位授予单位】：山东大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TE254.4
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