利用非等温动力学测量数据对煤渣热分解焓熵收敛问题的新见解

IF 3.1 2区 化学 Q2 CHEMISTRY, ANALYTICAL
Bojan Janković , Marija Janković , Ivana Smičiklas , Mihajlo Jović , Ivana Vukanac , Ana Mraković , Nebojša Manić
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引用次数: 0

摘要

这项研究深入探讨了将煤渣作为回收工艺转化为高附加值产品的热化学转化效益。这项研究包括通过非等温热分析测量对过程进行动力学分析,以及其他原材料特征描述。动力学结果表明,分解是通过两个连续的反应步骤进行的(第一个步骤,包括阳起石 P1̅ → I1̅相变,然后产生不协调熔融产物(三元系统:CaO-Al2O3-2SiO2(CAS2),炉渣粘度发生变化),第二个反应包括脱水和形成元麝香石,随后麝香石脱羟基相发生热破坏,八面体 Al-O 键断裂),以及一个单步反应(赤铁矿一氧化碳还原为磁铁矿)。热力学结果表明,存在有物理意义的等动力学温度(Tiso),该温度与二氧化硅反应位点周围环境的活跃振动频率相对应,通过释放出的氢氧根离子(OH-)的催化反应,Si-O 键发生弱化。研究得出结论,在温度 T = Tiso 时,反应过程不再依赖于温度和压力,而是通过焓熵补偿效应(EEC)调节热力学参数之间的变化。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Novel insights into the problem of enthalpy and entropy convergence in thermal decomposition of coal slag using the data from non-isothermal kinetic measurements

Novel insights into the problem of enthalpy and entropy convergence in thermal decomposition of coal slag using the data from non-isothermal kinetic measurements

This study provides insight into benefits of thermo-chemical conversion of coal slag as recovery process into value-added products. This research involves kinetic analysis of process conducted through non-isothermal thermal analysis measurements, with additional raw material characterization. Kinetic results showed that decomposition proceeds through two consecutive reactions steps (first one, including anorthite P1̅ → I1̅ phase transition, and then production of incongruent melting product (ternary system: CaO·Al2O3·2SiO2 (CAS2), where viscosity of slag changes), and second one including dehydration and formation of meta-muscovite, and subsequently, thermal disruption of muscovite de-hydroxylated phase, which proceeds with breaking of octahedral Al–O bonds), and one single-step reaction (attributed to CO-reduction of hematite to magnetite). Thermodynamic results showed an existence of physically meaningful isokinetic temperature (Tiso), which corresponds to active vibrational frequency of surroundings of SiO2 reaction site, manifested through Si‒O bond weakening by catalytic reaction of freed hydroxide ion (OH). It was concluded that at temperature T = Tiso, the course of process loses its dependence on temperature and pressure, regulating changes between thermodynamic parameters, through enthalpy-entropy compensation (EEC) effect.

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来源期刊
Thermochimica Acta
Thermochimica Acta 化学-分析化学
CiteScore
6.50
自引率
8.60%
发文量
210
审稿时长
40 days
期刊介绍: Thermochimica Acta publishes original research contributions covering all aspects of thermoanalytical and calorimetric methods and their application to experimental chemistry, physics, biology and engineering. The journal aims to span the whole range from fundamental research to practical application. The journal focuses on the research that advances physical and analytical science of thermal phenomena. Therefore, the manuscripts are expected to provide important insights into the thermal phenomena studied or to propose significant improvements of analytical or computational techniques employed in thermal studies. Manuscripts that report the results of routine thermal measurements are not suitable for publication in Thermochimica Acta. The journal particularly welcomes papers from newly emerging areas as well as from the traditional strength areas: - New and improved instrumentation and methods - Thermal properties and behavior of materials - Kinetics of thermally stimulated processes
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