Kinetic analysis of catalytic slurry oil pyrolysis using thermogravimetric analysis
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Kinetic analysis of catalytic slurry oil pyrolysis using thermogravimetric analysis Hang An1 · Yue Li1 · Fang Hua1 · Tianyang Li1 · Yan Cheng1 · Yi Cheng1 Received: 18 August 2019 / Accepted: 13 March 2020 © Akadémiai Kiadó, Budapest, Hungary 2020
Abstract Pyrolysis is an important process for converting unconventional fuels, such as heavy oil, residues and oil sand, to high-valueadded light products. And the kinetics in pyrolysis is essential to fully understand and optimize the process. In this work, we present a comprehensive study on the kinetic analysis of the pyrolysis process of catalytic slurry oil (CSO), by-product of fluid catalytic cracking process, using thermogravimetric analysis. Three isoconversional methods were applied for analysis and estimation of parameters for the reaction kinetics. The activation energies calculated using the Ozawa–Flynn–Wall, Friedman and Kissinger–Akahira–Sunose methods are 81.93–131.38 kJ mol−1, 86.57–141.39 kJ mol−1 and 78.72–128.05 kJ mol−1 with conversion from 0.05 to 0.90, respectively. Among the compared methods, Friedman method is free of extra information of reaction model and mathematical assumptions of temperature integral; therefore, it was recommended as the more suitable method for analysis of this process. The activation energy of CSO estimated via the above kinetic analysis was compared with other materials. Keywords Catalytic slurry oil · Thermogravimetric analysis · Isoconversional method · Activation energy
Introduction With the rapid growth of economics of the society, demand for energy for the whole world has been increasing at a high speed. At the same time, the exploitation of crude oil has become more and more difficult. To mitigate the contradiction between increasing demand for energy and short of conventional oil resource, much attention has been paid to exploration of unconventional oil, such as heavy oil in Venezuela and oil sand in Canada, which are rich in reserves at present. General methods for heavy oil processing include thermal cracking, residue fluid catalytic cracking (RFCC), hydrogenation, etc. [1]. However, these processes produce residues of lower quality, which are in large amount and much more difficult for further use. For example, catalytic slurry oil (CSO), which is bottom by-product of the process of FCC and RFCC, is abundant in China with the production of more than 7.5 billion tons per year [2, 3], but most of them end * Yi Cheng [email protected] 1
Department of Chemical Engineering, Tsinghua University, Beijing 100084, People’s Republic of China
up as fuels in refineries. Thermal cracking, or pyrolysis, is one of the common methods for the conversion of unconventional feedstock due to its simple configuration and lower cost than catalytic or hydrogenation process. In decades, much work has been conducted in pyrolysis of crude oil [4, 5], residual oil [6–8], oil shales [9–11], biomass [12, 13], etc., in order to study the pyrolysis kinetics. To get the basic kinetics parameters of the pyrolysis reaction such as E
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