碳酸钙垢生长规律及阻垢剂对其影响的EQCM研究

发布时间：2018-07-05 18:10

  本文选题：碳酸钙垢 + 电化学石英晶体微天平　； 参考：《西南石油大学》2015年硕士论文

【摘要】：在工业生产、特别是在油气田生产过程中,结垢现象不仅会导致生产设备及油套管等效率降低,还会加速局部的垢下腐蚀,使其使用寿命下降。延缓和减轻结垢现象对于油田的提高生产效益具有重大意义。垢的成分很多,以碳酸钙(CaCO3)最为常见且危害最大。目前,一般采用投加阻垢剂的方法来延缓或减轻结垢的发生。 本文采用阴极极化加速结垢的方法,使用电化学石英晶体微天平技术(EQCM)对碳酸钙垢的生长进行了多因素的分析；研究了有机膦系类、聚羧酸类和无机磷类等常见阻垢剂的阻垢性能,同时研究了聚合物HPAM的阻垢性能及其与不同阻垢剂的协同作用；在此基础上,分析比较了动、静态溶液体系下,阻垢剂在碳酸钙垢的结垢过程中的动力学行为以及不同流速下阻垢剂对其生长动力学的影响；以X射线衍射分析方法、扫描电子显微镜和X射线能谱分析方法、阴极极化曲线等现代测试方法结果为依据,给出了三种类型阻垢剂的阻垢机理。 本文研究成果如下： 1)阴极电位、温度、Ca2+浓度、流速都能在一定程度上影响碳酸钙垢的结垢量：其中电位对CaCO3形貌影响最大；液体流速对结垢速率的影响最大。 2)在静态溶液体系、温度50℃条件下,得到羟基乙叉二膦酸(HEDP)、膦酰基羧酸(POCA)、氨基三甲叉膦酸(ATMP)和六偏磷酸钠(SHMP)的最优使用浓度；在摩尔浓度和质量浓度两种情况下,四种阻垢剂加入相同浓度后碳酸钙的结垢质量从高到低依次为：SHMP、HEDP、ATMP和POCA。 3)聚合物HPAM具有抑制碳酸钙垢的性能；其与四种阻垢剂在抑垢方面有一定的协同作用,且与有机膦系列阻垢剂发生协同作用最优。 4)在结垢过程中注入阻垢剂时,静态溶液下结垢量与时间图中出现明显的3个阶段：结垢阶段、阻垢剂的扩散和不稳定作用阶段、阻垢剂稳定作用阶段；动态溶液体系下,只存在空白结垢阶段和阻垢剂稳定作用阶段。两个稳定沉积过程的时间与结垢量曲线符合直线方程y=y0+kx,斜率k值可量化其生长动力学。但由于阻垢剂的阻垢机理不同,流速对阻垢剂的性能影响规律不一致。 5)加入ATMP和HEDP使碳酸钙颗粒、晶粒尺寸减小明显；加入POCA使碳酸钙颗粒和晶粒尺寸都有一定程度的减小,且出现中空；SHMP的加入对碳酸钙形貌影响较小。 6) ATMP会在一定程度上抑制碳酸钙垢沉积到石英晶片金面上的电化学反应过程；而四种阻垢剂的添加都在一定程度上抑制了浓度极化过程。
[Abstract]:In industrial production, especially in the production of oil and gas fields, the phenomenon of scaling will not only reduce the efficiency of production equipment and oil casing, but also accelerate the local scale corrosion and decrease its service life. It is of great significance to delay and reduce the scaling phenomenon for improving the production efficiency of oil fields. Calcium carbonate (CaCO3) is the most common and harmful scale. At present, the general use of scale inhibitor to delay or reduce the occurrence of scaling. In this paper, the growth of calcium carbonate scale was analyzed by electrochemical quartz crystal microbalance (EQCM) with the method of accelerated scaling by cathodic polarization, and the organic phosphine series was studied. The scale inhibition properties of polycarboxylic acid and inorganic phosphorus were studied. The scale inhibition of HPAM and its synergistic effect with different scale inhibitors were studied. The dynamic behavior of scale inhibitor in the scaling process of calcium carbonate and the effect of scale inhibitor on the growth kinetics of calcium carbonate scale at different flow rates, X-ray diffraction analysis, scanning electron microscope and X-ray energy spectrum analysis, Based on the results of modern measurement methods such as cathodic polarization curves, the scale inhibition mechanisms of three types of scale inhibitors are given. The results are as follows: 1) cathode potential, temperature and Ca 2 concentration, flow rate can affect the scaling amount of calcium carbonate scale to a certain extent: potential has the greatest influence on the morphology of CaCO3; The effect of liquid flow rate on scaling rate is the greatest. 2) the optimal concentration of hydroxy ethylenediphosphonic acid (HEDP), phosphonyl carboxylic acid (POCA), amino trimethylidene phosphonic acid (ATMP) and sodium hexametaphosphate (SHMP) is obtained in the static solution system at 50 鈩，

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