School of Environmental and Municipal Engineering, Qingdao University of Technology, Qingdao 266033, China.
Technical Test Center of Shengli Oil Field, Dongying 257001, China.
Int J Environ Res Public Health. 2019 Jan 29;16(3):384. doi: 10.3390/ijerph16030384.
As the most significant solid residue generated in the oil production industry, upstream oily sludge was regarded as hazardous waste in China due to its toxicity and ignitability, and to date, the incineration process has been considered the most efficient method in practice. Due to the complicated components of oily sludge, a kinetic model of the incineration process was difficult to build, and is still absent in engineering use. In this study, multiple non-isothermal thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) analysis were applied for the kinetic analysis of upstream oily sludge in air conditions. A viewpoint regarding the rules to sectionalize the reaction stages was raised, and a differential integral method to obtain the incineration kinetic model was provided. The results showed that four stages that were divided based on the weight-loss regions in the TGA curves and the endothermic/exothermic sections in the DSC curves were suitable to obtain an incineration kinetic model of oily sludge. The integral method was beneficial for obtaining the average activation energy of each stage, and the differential method was suitable for gaining the nth-order reaction rate equation and the pre-exponential factor before the operating temperature became lower than 635.968 °C. The average activation energies of stages one, two, three, and four were 60.87 KJ/mol, 78.11 KJ/mol, 98.82 KJ/mol, and 15.96 KJ/mol, respectively. The nth-order reaction rate equations and pre-exponential factors of stages one, two, and three were 0.82, 3.50, and 2.50, and e 13.32 min - 1 , e 19.69 min - 1 , and e 21.00 min - 1 , respectively.
作为石油生产行业产生的最重要的固体残留物，上游含油污泥在中国因其毒性和可燃性而被视为危险废物，迄今为止，焚烧工艺被认为是实践中最有效的方法。由于含油污泥成分复杂，难以建立焚烧过程的动力学模型，在工程应用中仍然不存在。本研究采用多种非等温热重分析（TGA）和差示扫描量热法（DSC）分析方法，对空气条件下上游含油污泥的动力学进行了分析。提出了分段反应阶段的规则观点，并提供了一种获得焚烧动力学模型的微分积分方法。结果表明，根据 TGA 曲线中失重区和 DSC 曲线中吸热/放热段划分的四个阶段，适用于获得含油污泥的焚烧动力学模型。积分法有利于获得各阶段的平均活化能，微分法适用于获得 n 级反应速率方程和操作温度低于 635.968°C 之前的指前因子。第一、二、三、四阶段的平均活化能分别为 60.87KJ/mol、78.11KJ/mol、98.82KJ/mol和 15.96KJ/mol。第一、二、三阶段的 n 级反应速率方程和指前因子分别为 0.82、3.50 和 2.50，e13.32min-1、e19.69min-1和 e21.00min-1。
