阳离子超支化聚合物的合成及其在钻井液中的应用研究

发布时间：2018-05-08 20:26

本文选题：阳离子超支化聚合物 + 钻井液　；参考：《西南石油大学》2017年硕士论文

【摘要】：超支化聚合物是一种具有高度分支拓扑结构的树枝状聚合物。因其独特的三维球状结构、表面富集大量的端基使其具有较高的反应活性和较高的吸附能力,同时具有高溶解度、低粘度以及合成操作简单的特点,在涂料、生物医药、生命科学、化妆品、纳米材料以及石油工程等领域都有广泛的研究应用。但在石油工程领域作为泥页岩抑制剂和微孔隙封堵剂的研究未见报道。本文研究端氨基超支化聚合物(HP-NH2)和端季铵盐超支化聚合物(HP-HTC)两种阳离子超支化聚合物的制备,并将其应用于页岩气钻井液-钾钙基聚磺润滑钻井液,以强化该钻井液体系对泥页岩的抑制性和对微孔隙的封堵性。本文以丁二酸酐和二乙烯三胺为原料,四氢呋喃为溶剂,合成了一种以胺基为端基的阳离子型超支化聚合物(HP-NH2),然后以环氧丙基三甲基氯化铵对HP-NH2端基进行改性得到了以季铵盐为端基的阳离子超支化聚合物(HP-HTC)。采用FT-IR红外光谱、TOF LC/MS、1H-NMR、TGA、GPC以及SEM等对单体和超支化聚合物进行结构和性能表征。结果表明AB2单体、HP-NH2以HP-HTC真实被合成。以线性膨胀实验、页岩滚动回收实验、抑制造浆实验以及沉降实验测试了 HP-NH2和HP-HTC的抑制能力,实验结果证明HP-NH2和HP-HTC对粘土的水化分散和水化膨胀有良好的抑制性能,且其抑制性随着端基质量摩尔浓度的增加而增加。其中3%HP-NH2(N=4.77mol/kg)和3%HP-HTC(C=3.89 mol/kg)的线性膨胀率分别为26.9%和22.4%,页岩滚动回收率分别为71.14%和73.03%。以压力传递实验、渗流实验以及API滤失实验测试了 HP-NH2和HP-HTC的封堵能力,实验结果证明HP-NH2和HP-HTC对纳米孔隙以及低渗透岩心有着良好的封堵能力,且其封堵性随着端基质量摩尔浓度的增加而增加。其中API滤失实验表明3%HP-NH2(N=4.77mol/kg)和3%HP-HTC(C=3.889mol/kg)以有效降低滤失量,且其滤失量均约为基浆的50%,同时证明阳离子超支化聚合物不是通过增加滤液粘度来起降滤失作用。本文通过FT-IR光谱测试、XRD测试、Zeta电位测试以及激光粒度分析了 HP-NH2和HP-HTC对粘土水化分散和水化膨胀的抑制机理。分析得到HP-NH2和HP-HTC是通过降低或反转粘土表面Zeta电位、压缩扩散双电层来抑制粘土的水化分散,通过进入粘土层间,置换水化阳离子,且在粘土表面形成水化膜来抑制粘土的水化膨胀。以SEM测试初步分析了 HP-NH2和 HP-HTC的封堵机理,结果表明其可以参与泥饼的形成,封堵泥饼微孔隙来降低滤失量。最后研究了 HP-NH2和HP-HTC加入页岩气钻井液-钾钙基聚磺润滑钻井液后其流变性、抑制性和封堵性的变化。结果表明,在该钻井液体系中HP-NH2和HP-HTC的最佳加量为3%,其动塑比分别为0.36和0.37,且研究表明HP-NH2和HP-HTC的加入对该钻井液体系的抑制性和封堵性有极大的强化,其中HP-NH2对抑制性的强化弱于HP-HTC,对封堵性的强化则强于HP-HTC。
[Abstract]:Hyperbranched polymer is a kind of dendritic polymer with highly branched topology. Because of its unique three-dimensional spherical structure, the surface enriched with a large number of end groups, it has higher reaction activity and higher adsorption capacity, and has the characteristics of high solubility, low viscosity and simple synthesis operation in coatings, biomedicine, Life science, cosmetics, nanomaterials and petroleum engineering have been widely used. However, researches on shale inhibitors and micropore plugging agents in petroleum engineering have not been reported. In this paper, two kinds of cationic hyperbranched polymers (HP-NH2) and quaternary ammonium salt hyperbranched polymers (HP-HTC) were prepared and applied to shale gas drilling fluid, potassium calcium based polysulfonate lubricated drilling fluid. In order to enhance the inhibition of the drilling fluid system to shale and the plugging of micropores. In this paper, using succinic anhydride and diethylenetriamine as raw materials, tetrahydrofuran as solvent, A cationic hyperbranched polymer (HP-NH _ 2) based on amine group was synthesized, and then modified with epichloropropyl trimethylammonium chloride to form a cationic hyperbranched polymer (HP-HTCN) with quaternary ammonium salt as the terminal group. The structure and properties of monomers and hyperbranched polymers were characterized by FT-IR infrared spectra and TOF LC / MS / MS-1H-NMR-TGA GPC and SEM. The results showed that AB2 monomer HP-NH _ 2 was actually synthesized as HP-HTC. The inhibition ability of HP-NH2 and HP-HTC was tested by linear expansion test, shale rolling recovery test, slurry inhibition experiment and sedimentation test. The experimental results show that HP-NH2 and HP-HTC have good inhibition performance on hydration dispersion and hydration expansion of clay. The inhibition increased with the increase of the molar concentration of terminal groups. The linear expansion rates of HP-NH _ 2N _ (4.77 mol / kg) and 3%HP-HTC(C=3.89 mol / kg) were 26.9% and 22.4%, respectively, and the shale rolling recovery rates were 71.14% and 73.03%, respectively. The plugging ability of HP-NH2 and HP-HTC was tested by pressure transfer experiment, seepage experiment and API filtration experiment. The experimental results show that HP-NH2 and HP-HTC have good plugging ability to nanometer pore and low permeability core. The plugging ability increases with the increase of the molar concentration of terminal groups. The API filtration experiment showed that 3HP-NH _ 2N _ (4.77 mol / kg) and 3 ~ (th) HP-HTCU ~ (3.889 mol 路kg ~ (-1) were effective in reducing the filtration loss, and the filtration loss was about 50% of the base pulp. It was also proved that the cationic hyperbranched polymer did not increase the viscosity of the filtrate to take off or decrease the filtration loss. In this paper, the inhibition mechanism of HP-NH2 and HP-HTC on hydration dispersion and hydration expansion of clay was analyzed by means of FT-IR spectra and X-ray diffraction (XRD) measurements of Zeta potential and laser particle size. It is found that HP-NH2 and HP-HTC inhibit the hydration dispersion of clay by decreasing or reversing the Zeta potential on the surface of clay and by compression diffusion double electric layer, and by entering the clay layer, the hydrated cations are replaced. The hydration film is formed on the clay surface to inhibit the hydration expansion of the clay. The plugging mechanism of HP-NH2 and HP-HTC was preliminarily analyzed by SEM test. The results showed that HP-NH2 and HP-HTC could participate in the formation of mud cake and close the micropores of mud cake to reduce filtration loss. Finally, the change of rheology, inhibition and plugging property of HP-NH2 and HP-HTC in shale gas drilling fluid with potassium calcium based polysulfonate lubricated drilling fluid was studied. The results show that the optimum addition of HP-NH2 and HP-HTC in the drilling fluid system is 3 and the dynamic plastic ratio is 0.36 and 0.37, respectively. The results show that the addition of HP-NH2 and HP-HTC can greatly enhance the inhibition and plugging performance of the drilling fluid system. The enhancement of inhibition by HP-NH2 was weaker than that of HP-HTC, and the enhancement of plugging was stronger than that of HP-HTC.
【学位授予单位】：西南石油大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ317;TE254

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