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喀麦隆高岭土热分解的热动力学阐释:机理、热力学研究及其副产物鉴定

Elucidation of the thermo-kinetics of the thermal decomposition of cameroonian kaolin: mechanism, thermodynamic study and identification of its by-products.

作者信息

Fotsop Cyrille Ghislain, Lieb Alexandra, Scheffler Franziska

机构信息

Otto-von-Guericke-University Magdeburg, Chemical Institute, Chair for Industrial Chemistry Universitätsplatz 2 39106 Magdeburg Germany

出版信息

RSC Adv. 2025 Sep 8;15(39):32172-32187. doi: 10.1039/d5ra05149e. eCollection 2025 Sep 5.

Abstract

This work elucidates the thermo-kinetics of the thermal conversion of cameroonian kaolin to metakaolin as the main product. The thermokinetical parameters (activation energy and pre-exponential factor ) for the kaolin conversion were calculated using model-free methods, the Kissinger-Akahira-Sunrose (KAS) and the Flynn-Wall-Ozawa (FWO) method, and differential methods (Kissinger and Ozawa) additionally including iterative procedures for KAS and FWO methods (KAS-Ir; FWO-Ir). The cameroonian kaolin was heat-treated using three different heating rates, 5, 20 and 40 K min, leading to metakaolin samples named MK-(5), MK-(20) and MK-(40). The TGA analysis showed a total mass loss of ∼12.5% in two steps related to the dehydration (step 1) and dehydroxylation (step 2). The of the two steps were most accurately determined using the iterative procedures KAS-Ir and FWO-Ir. The average values were 88.44/88.58 kJ mol for step 1 and 261.85/261.91 kJ mol for step 2, for the KAS-Ir and FWO-Ir models, respectively. The most probable mechanism function was determined by the multiple heating rate method (MHR) and the Coats-Redfern method. The kinetic analyses showed that the dehydroxylation of kaolin is controlled by a random nucleation and subsequent growth mechanism (G) and a second order chemical reaction (F). Thermodynamic parameters, namely the entropy Δ , the enthalpy Δ and Gibbs free energy Δ , were evaluated. The average values of Δ , Δ and Δ using both the KAS-Ir and FWO-Ir models exhibited less than 5% deviation. The obtained metakaolin samples were characterized using X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and Fourier-transform infrared spectroscopy (FT-IR).

摘要

这项工作阐明了喀麦隆高岭土热转化为偏高岭土这一主要产物的热动力学。高岭土转化的热动力学参数(活化能和指前因子)采用无模型方法、基辛格 - 赤平 - 孙罗斯(KAS)法和弗林 - 沃尔 - 小泽(FWO)法进行计算,此外还采用了微分方法(基辛格法和小泽法),包括KAS和FWO方法的迭代程序(KAS - Ir;FWO - Ir)。喀麦隆高岭土采用5、20和40 K/min三种不同的加热速率进行热处理,得到的偏高岭土样品分别命名为MK - (5)、MK - (20)和MK - (40)。热重分析(TGA)表明,在与脱水(步骤1)和脱羟基(步骤2)相关的两个步骤中,总质量损失约为12.5%。这两个步骤的活化能最精确地使用迭代程序KAS - Ir和FWO - Ir确定。对于KAS - Ir和FWO - Ir模型,步骤1的平均活化能值分别为88.44/88.58 kJ/mol,步骤2为261.85/261.91 kJ/mol。最可能的机理函数通过多重加热速率法(MHR)和科茨 - 雷德芬法确定。动力学分析表明,高岭土的脱羟基受随机成核及随后的生长机理(G)和二级化学反应(F)控制。评估了热力学参数,即熵ΔS、焓ΔH和吉布斯自由能ΔG。使用KAS - Ir和FWO - Ir模型得到的ΔS、ΔH和ΔG的平均值偏差小于5%。使用X射线衍射(XRD)、场发射扫描电子显微镜(FE - SEM)和傅里叶变换红外光谱(FT - IR)对所得的偏高岭土样品进行了表征。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/be25/12415547/84a8db468bab/d5ra05149e-f1.jpg

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