Investigation on the Adaptability of the Polymer Microspheres for Fluid Flow Diversion in Porous Media

Large amounts of water producing from producers have been a great concern for petroleum engineers. In an attempt to inhibit water production and promote oil productivity, various water control agents and techniques have been devised for enhanced oil recovery purpose for decades with some good successes reported commercially. Mainly field-targeted specifically, however, these chemicals are limited in expansive reservoir applications for failing to tolerate harsh formation conditions of high temperature (HT) and high salinity (HS). Besides, their low injectivity is also another proper impediment. In this presentation, we synthesized a new agent of polymer microspheres using inverse emulsion polymerization technique to divert fluid patterns in deep porous media for reservoirs encountered recovery enhancement problems. These microspheres are made to tolerate HT and HS conditions, and can be pumped into deep pore space with relative ease. With the help of nuclear magnetic resonance (NMR) and nuclear pore membrane filtration techniques, a series of experimental procedures were conducted to test the adaptability of newly produced polymer microspheres to targeted pore structure in enhancing the sweeping efficiency of injection fluids. Both laboratory core tests and NMR data show good characteristics of polymer microspheres in modifying injection profile, demonstrating a good capability to divert fluid flow patterns in deep porous media and enhance oil productivity.     

双甘氨肽分子印迹聚合物微球的吸附性能研究

以双甘氨肽(Gly-Gly)为印迹分子,丙烯酰胺(AM)、二甲基丙烯酸乙二醇酯(EDMA)分别作为功能单体和交联剂,在低温条件下采用乳液聚合于水相中制备了双甘氨肽分子印迹聚合物微球(Gly-Gly-MIPMs)。通过静态、动态平衡吸附和薄层色谱(TLC)分离实验,研究了Gly-Gly-MIPMs的选择吸附性能,并进行了Scatchard模型分析。结果表明,Gly-Gly-MIPMs对Gly-Gly分子具有较好的特异性吸附,最大单位饱和吸附量0.428mmol/g,印迹因子2.19。     

高分子金属微球的磁性能研究

在苯乙烯和丙烯酸共聚物「Ｐ（Ｓｔ－ｃｏ－ＡＡ）」，苯乙烯和４－乙烯吡啶共聚物「Ｐ（Ｓｔ－ｃｏ－４ＶＰ）Ｎｉ、Ｐ（Ｓｔ－ｃｏ－４ＶＰ）Ｃｏ金属微球，研究了它们的交流磁化率，磁滞回线，居里温度等磁性能。结果表明制得的了的微球为软磁材料，热重（ＴＧ）分析了则得Ｐ（Ｓｔ－ｃｏ－ＡＡ）Ｎｉ和Ｐ（Ｓｔ－ｃｏ－４ＶＰ）Ｎｉ的居时温度（Ｔｃ）分别为１７５℃和１８０℃，远远低于块状金属的居里温度值。     

A Platform for Preparation of Monodispersed Fluorescent Conjugated Polymer Microspheres with Core‐Shell Structures

A strategy to prepare stable monodispersed fluorescent microspheres is developed by modifying the Wessling method to synthesize poly(p‐phenylenevinylene) (PPV) on the surface of a highly crosslinked polymer core. The positively charged PPV polymer precursors (pre‐PPV) are adsorbed onto the core with negative charges on the surface and then the insoluble fluorescent PPVs form after thermal elimination. Each individual sphere is found to possess a very smooth surface with an even distribution of fluorescence by microscopic techniques. Very small coefficient of variance (CV) values of emission intensity (<4.0%) and size (<2.3%) are realized for microspheres prepared in the same batch. The spheres are demonstrated to have good thermal stability and photostability.     

Polymer Gel Dosimeters with Increased Solubility: A Preliminary Investigation of the NMR and Optical Dose-Response Using Different Crosslinkers and Co-Solvents

Summary: The potential of ten different crosslinkers was investigated, with the aim of improving the performance of polymer gel dosimeters used for detecting radiation dose distributions generated by cancer radiation therapy equipment. Unfortunately, none of the candidate crosslinkers was shown to be more effective than N,N′-methylene-bisacrylamide, the standard crosslinker used in polymer gel dosimetry applications. Two co-solvents, glycerol and isopropanol, were used to increase the solubility of N,N′-methylene-bisacrylamide crosslinker in polymer gel dosimeter recipes. Using isopropanol, the crosslinker solubility increased from approximately from 3 to 10% by weight, enabling the manufacture of polymer gel dosimeters with much higher levels of crosslinking than was previously possible. The new dosimeter recipes can be imaged effectively using nuclear magnetic resonance and optical techniques, and may be suitable for read-out using x-ray CT (Computed Tomography).     

电解质对聚合物分子尺寸、结构形态和渗流特性影响研究

利用动态光散射（DLS）、扫描电镜（SEM）、表观黏度和岩心流动实验等方法,研究了电解质对聚合物分子线团尺寸、结构形态和渗流特性的影响。结果表明,随电解质浓度增大,聚合物分子线团尺寸呈现“减小、增大和再减小”变化趋势。在Ca2+、Mg2+和Na+三种离子中,Ca2+和Mg2+离子对聚合物分子双电层压缩作用更强,因而对聚合物溶液黏度和线团尺寸及其分布影响更大。随着溶剂水电解质浓度的增加,聚合物分子结构形态逐渐由多层次立体无规网状向树枝状和支状转化。在聚合物驱后的后续水驱过程中,注入压力大小受滞留聚合物采出量和仍滞留聚合物分子线团膨胀两因素的影响。聚合物相对分子质量愈大,电解质对聚合物分子线团压缩或和膨胀作用愈强,后续水驱过程中压力升高幅度愈大。聚合物驱和后续水驱所用水的电解质浓度差异愈大,后续水驱阶段压力升高幅度愈大。因此在油田聚合物驱油方案设计时,建议适当增加聚合物驱和后续水驱所用水的电解质浓度差异,这对改善聚合物驱增油效果十分有利。     

Study on the Plugging Ability of Polymer Gel Particle for the Profile Control in Reservoir

Polymer gel particle is a widely used deep profile control agent to plug the water breakthrough channel in reservoir. However, there is still no theoretical model to describe its plugging ability available when it is applicated. Based on the Hertz contact theory and force analysis, the plugging model of polymer gel particle is established at the view of pore throat, and the parameters in the model are achieved by the pore throat experiments. The plugging model is verified by the core experiments. The results show that the plugging strength of polymer gel particle keeps rise with the increasing of the ratio between particle diameter and pore throat size, and then it will stay at a stable value because of the limitation of material strength. The material strength is 0.32 MPa and the particle will be broken when the size ratio is over 3. The plugging strength of the polymer gel particles with the diameters of 30–40 µm and 60–80 µm is 0.12 and 0.31 MPa in the cores with the permeability of 2989.6 × 10^?3 and 3014.7 × 10^?3 µm², respectively, which is consistent perfectly with the theoretical calculation. The plugging model of polymer gel particle is verified to be correct and can be applied to the profile control in reservoir.     

Kinetic Study of the Isotope Exchange Reactions of Malonic Acid and Malonate Ion Using 1H NMR Spectroscopy. Inhibition of Acid and Base

The isotope exchange reactions of malonic acid and a malonate ion were investigated in acidic and basic D₂O solutions, respectively, using ¹H NMR spectroscopy. The isotope exchange reaction of malonic acid is inhibited by the presence of DNO₃ (0–3 M) and DSO₄^? ion (0–0.1 M), whereas it is catalyzed by the presence of DSO₄^? ion (> 0.2 M), D₃PO₄, D₂PO₄^? ion or DPO₄^2– ion. The order of relative reactivity for catalyzing the isotope reaction of malonic acid in D₂O is DPO₄^2– > D₂PO₄^? > D₃PO₄ > DSO₄^? > DNO₃. The rate of the isotope exchange reaction of malonate ion in D₂O decreases to a minimum and then increases with increased [NaOD]₀. The mechanism of the isotope exchange reaction of malonic acid in acidic D₂O is different from the general acid-catalyzed mechanism generally observed for organic acids like acetic and dichloroacetic acids. The bimalonate ion plays an important role in the isotope exchange reactions of this system.