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分段单步反应法(SSRA)和分布式活化能模型(DAEM)在上游含油污泥热解动力学模型中的应用:构建过程和数据再现性比较。

Application of sectionalized single-step reaction approach (SSRA) and distributed activation energy model (DAEM) on the pyrolysis kinetics model of upstream oily sludge: Construction procedure and data reproducibility comparison.

机构信息

School of Environmental and Municipal Engineering, Qingdao University of Technology, Qingdao 266033, PR China; Jiangsu ATK Environmental Engineering Co., Ltd, Wuxi 214000,PR China.

School of Environmental and Municipal Engineering, Qingdao University of Technology, Qingdao 266033, PR China; Jiangsu ATK Environmental Engineering Co., Ltd, Wuxi 214000,PR China.

出版信息

Sci Total Environ. 2021 Jun 20;774:145751. doi: 10.1016/j.scitotenv.2021.145751. Epub 2021 Feb 11.

Abstract

As the dominant hazardous waste discharged from petroleum industry, the pyrolysis features of the upstream oily sludge (UOS) were scrutinized by way of TGA/DSC. The pyrolysis kinetics model of UOS was systematically constructed by sectionalized single-step reaction approach (SSRA) and distributed activation energy model (DAEM), and the data reproducibility was further evaluated. The results showed that when the pyrolysis operation temperature interval was set from 380 K to 1170 K, two weigh loss step, two endo/exothermic regions and three significant mass-loss peak were respectively emerged in TG, DSC and DTG curves, based on which the TG curves could be sectionalized into three stages. Attributing to the ∆E/E¯ value of each stage was higher than 10% but lower than 20% derived from the activation energy assessment, it is not only revealed three multi-step reactions were carried out in sequence with an individual dominant single-step reaction which was sufficient for the SSRA utilization, but also displayed a well fitted by the Gaussian distribution which satisfied the requirement of DAEM implementation. Based on the five-step construction procedure introduced in this paper, pyrolysis kinetics model of UOS could be successful established and interpret as SSRA-based and DAEM-based piecewise function. The latter exhibited a better performance on the data reproduction than the former because the nRSS value of the reproduced data derived from DAEM-based model was lower than 1.86%. The higher mathematical flexibility of DAEM-based model function was the major attribution to a better data reproducibility, also, it possessed a potential ability in predicting the reaction rate at an arbitrary reaction temperature once the heating ratio was preset.

摘要

作为石油工业排放的主要危险废物,通过 TGA/DSC 研究了上游含油污泥(UOS)的热解特性。通过分段单步反应法(SSRA)和分布活化能模型(DAEM)系统地构建了 UOS 的热解动力学模型,并进一步评估了数据的重现性。结果表明,当热解操作温度间隔设置为 380 K 至 1170 K 时,在 TG、DSC 和 DTG 曲线上分别出现了两个失重步骤、两个内/放热区和三个明显的质量损失峰,基于此,TG 曲线可以分为三个阶段。由于每个阶段的 ∆E/E¯值高于 10%但低于 20%,这是从活化能评估得出的,这不仅表明了三个多步反应依次进行,其中一个主要的单步反应足以满足 SSRA 的使用,而且还显示出符合 DAEM 实施要求的高斯分布拟合良好。基于本文介绍的五步构造程序,可以成功建立 UOS 的热解动力学模型,并解释为基于 SSRA 和基于 DAEM 的分段函数。后者在数据再现方面表现出更好的性能,因为源于基于 DAEM 的模型的再现数据的 nRSS 值低于 1.86%。基于 DAEM 的模型函数具有更高的数学灵活性是数据重现性更好的主要归因,此外,一旦预设了加热比,它还具有在任意反应温度下预测反应速率的潜力。

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