含聚合物含油污泥作为潜在燃料的燃烧热化学研究

Yuhao Cao , Mulin Zou , Aohan Ran , Peiying Zong , Zhaowei He , Xiang Gou
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引用次数: 0

摘要

油泥所带来的环境和资源问题引发了人们对更清洁、更高效的石油生产的新兴趣。含聚合物含油污泥燃烧过程的研究有望为含油污泥作为替代燃料开辟新的市场。利用热重分析(TGA)研究了POS的燃烧行为、动力学和热力学,并利用x射线荧光(XRF)测量了POS灰的化学成分,以预测灰结垢和结渣。根据TG-DTG曲线,将燃烧研究中POS的质量损失分为四个主要区域。采用无模型法的Flynn-Wall-Ozawa (FWO)和Kissinger-Akahira-Sunose (KAS)联合计算方法确定了第1 ~ 4阶段的活化能,分别为47.89 kJ/mol、66.09 kJ/mol、190.55 kJ/mol和98.37 kJ/mol。建立了四阶段动力学模型(D4→D2→D3→R2)来描述POS的燃烧过程。与其他常规污泥相比,POS的活化能相对较低,更容易发生热化学转化。焓变(ΔH)和活化能(E)的差值表明反应有利于活性配合物的形成。同时,熵的变化(ΔS)表明在POS的第三阶段热力学不平衡,在反应结束时完成了热转化。Gibbs自由能(ΔG)的变化呈逐步增大的趋势,其平均值越低,表明POS的燃烧反应越有利。POS灰分的组成以金属氧化物为主,结渣指数为1.0,结垢指数为9.1,结渣粘度指数为32.0。POS灰具有高结垢和结渣的特点,在燃烧应用中应特别注意。
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Study on polymer-containing oily sludge as a potential fuel by combustion thermochemistry
The environmental and resource issues posed by oil sludge have sparked a renewed interest in cleaner and more efficient oil production. The investigation on the combustion process of polymer-containing oily sludge (POS) is expected to open up new markets for POS as an alternative fuel. TGA was used to examine the combustion behaviour, kinetics, and thermodynamics of POS, and X-ray fluorescence (XRF) was used to measure the chemical composition of POS ash to predict ash fouling and slagging. Based on the TG-DTG curves, the mass loss of POS in combustion studies was split into four major areas. The combined calculation method of model-free methods, Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS), was applied to determine the activation energies from stage 1 to stage 4, which were 47.89 kJ/mol, 66.09 kJ/mol, 190.55 kJ/mol, and 98.37 kJ/mol, respectively. A four-stage kinetic model (D4→D2→D3→R2) was established to describe the combustion process of POS. Compared to other conventional sludges, POS has a relatively low activation energy and is more susceptible to thermochemical transformations. The difference between the enthalpy change (ΔH) and activation energy (E) indicated that the reactions benefit the formation of the activated complex. Meanwhile, the change in entropy (ΔS) implied the thermodynamic disequilibrium in the 3rd stage of POS and completion of the thermal conversion at the end of the reaction. The change in Gibbs free energy (ΔG) increased in a stepwise manner and its lower average value reflected the greater reaction favourability of combustion for POS. The composition of POS ash was mainly metal oxides, with the slagging index, fouling index, and slagging viscosity index of 1.0, 9.1, and 32.0, respectively. POS ash has high fouling and slagging, with special attention in the combustion application.
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