{"title":"木材非等温热解动力学研究","authors":"S. V. Vasilevich, A. V. Mitrofanov","doi":"10.1134/S0023158424601657","DOIUrl":null,"url":null,"abstract":"<p>Results of a kinetic study of the pyrolysis of woody biomass (<i>Quercus robur</i>) under conditions of continuous heating to a temperature of 873 K at a constant rate of 1.25, 2.5, 5, and 10 K/min have been discussed. An integral method has been used to describe the reaction mechanism and determine the macrokinetic parameters. It has been found that, from a phenomenological point of view, the averaged woody biomass pyrolysis reaction under test conditions corresponds to a three-dimensional diffusion model (1.25 K/min), a model described by the third-order reaction equation (2.5, 5 K/min), and a one-dimensional diffusion model (10 K/min). In this case, the relative standard deviation of the conversion values calculated using this equation from the test data is <11.2%. The division of the averaged reaction into three stages (first stage is completed at a temperature of 390 K; the second, at 579 K; the third, at the completion of the conversion process) leads to agreement between the calculated degree of degradation of the studied biomass samples and the test values in a range of the degree of degradation of 0–1. Although the relative standard deviation does not exceed 3.5%, the division of the averaged reaction into stages does not exclude discrepancies in the values of the determined macrokinetic parameters. It has been shown that the choice of the model that provides the best description of the wood conversion process depends on heating rate during the tests. Owing to this dependence, the macrokinetic parameter values significantly differ from each other. Taking this fact into account, it can be concluded that the selected models and calculated macrokinetic parameters are of a formal nature and cannot be thought of as physicochemical characteristics that are universal with respect to the subject of research. Discrepancies in calculations of macrokinetic parameters that are caused by the effect of heating rate can be eliminated by studying the kinetics of conversion under isothermal conditions (at a constant temperature).</p>","PeriodicalId":682,"journal":{"name":"Kinetics and Catalysis","volume":"65 4","pages":"320 - 335"},"PeriodicalIF":1.3000,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"A Kinetic Study of the Nonisothermal Pyrolysis of Wood\",\"authors\":\"S. V. Vasilevich, A. V. 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The division of the averaged reaction into three stages (first stage is completed at a temperature of 390 K; the second, at 579 K; the third, at the completion of the conversion process) leads to agreement between the calculated degree of degradation of the studied biomass samples and the test values in a range of the degree of degradation of 0–1. Although the relative standard deviation does not exceed 3.5%, the division of the averaged reaction into stages does not exclude discrepancies in the values of the determined macrokinetic parameters. It has been shown that the choice of the model that provides the best description of the wood conversion process depends on heating rate during the tests. Owing to this dependence, the macrokinetic parameter values significantly differ from each other. 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引用次数: 0
摘要
摘要 讨论了在以 1.25、2.5、5 和 10 K/min 的恒定速率连续加热至 873 K 温度的条件下热解木质生物质(柞树)的动力学研究结果。采用积分法描述了反应机理并确定了宏观动力学参数。研究发现,从现象学的角度来看,试验条件下木质生物质热解反应的平均值对应于三维扩散模型(1.25 K/min)、三阶反应方程描述的模型(2.5、5 K/min)和一维扩散模型(10 K/min)。在这种情况下,使用该方程计算出的转化值与测试数据的相对标准偏差为 11.2%。将平均反应分为三个阶段(第一阶段在 390 K 的温度下完成;第二阶段在 579 K 的温度下完成;第三阶段在转化过程完成时完成)使得所研究的生物质样品的降解度计算值与降解度范围为 0-1 的测试值一致。虽然相对标准偏差不超过 3.5%,但将平均反应分为几个阶段并不能排除所测定的宏观动力学参数值之间的差异。试验表明,选择哪种模型能最好地描述木材转化过程取决于试验过程中的加热速率。由于这种依赖性,宏观动力学参数值之间存在很大差异。考虑到这一事实,可以得出结论:所选模型和计算的宏观动力学参数都是形式上的,不能被视为研究对象的通用物理化学特征。通过研究等温条件(恒温)下的转化动力学,可以消除因加热速率的影响而造成的宏观 动力学参数计算上的差异。
A Kinetic Study of the Nonisothermal Pyrolysis of Wood
Results of a kinetic study of the pyrolysis of woody biomass (Quercus robur) under conditions of continuous heating to a temperature of 873 K at a constant rate of 1.25, 2.5, 5, and 10 K/min have been discussed. An integral method has been used to describe the reaction mechanism and determine the macrokinetic parameters. It has been found that, from a phenomenological point of view, the averaged woody biomass pyrolysis reaction under test conditions corresponds to a three-dimensional diffusion model (1.25 K/min), a model described by the third-order reaction equation (2.5, 5 K/min), and a one-dimensional diffusion model (10 K/min). In this case, the relative standard deviation of the conversion values calculated using this equation from the test data is <11.2%. The division of the averaged reaction into three stages (first stage is completed at a temperature of 390 K; the second, at 579 K; the third, at the completion of the conversion process) leads to agreement between the calculated degree of degradation of the studied biomass samples and the test values in a range of the degree of degradation of 0–1. Although the relative standard deviation does not exceed 3.5%, the division of the averaged reaction into stages does not exclude discrepancies in the values of the determined macrokinetic parameters. It has been shown that the choice of the model that provides the best description of the wood conversion process depends on heating rate during the tests. Owing to this dependence, the macrokinetic parameter values significantly differ from each other. Taking this fact into account, it can be concluded that the selected models and calculated macrokinetic parameters are of a formal nature and cannot be thought of as physicochemical characteristics that are universal with respect to the subject of research. Discrepancies in calculations of macrokinetic parameters that are caused by the effect of heating rate can be eliminated by studying the kinetics of conversion under isothermal conditions (at a constant temperature).
期刊介绍:
Kinetics and Catalysis Russian is a periodical that publishes theoretical and experimental works on homogeneous and heterogeneous kinetics and catalysis. Other topics include the mechanism and kinetics of noncatalytic processes in gaseous, liquid, and solid phases, quantum chemical calculations in kinetics and catalysis, methods of studying catalytic processes and catalysts, the chemistry of catalysts and adsorbent surfaces, the structure and physicochemical properties of catalysts, preparation and poisoning of catalysts, macrokinetics, and computer simulations in catalysis. The journal also publishes review articles on contemporary problems in kinetics and catalysis. The journal welcomes manuscripts from all countries in the English or Russian language.