{"title":"铁矿氧载体化学环化氧化还原反应的模拟与实验研究","authors":"Wang Hui, Lei Liu, Kexin Li, Di Zhong","doi":"10.1002/eng2.13064","DOIUrl":null,"url":null,"abstract":"<p>Developing a reliable kinetic model for these redox reactions is crucial for understanding and improving oxygen carriers practical in chemical looping applications. The traditional pore model assumes that the solid product forms a continuous layer uniformly covering the solid reactant surface during the gas–solid reactions, in the result the model fails to capture the kinetic transitions caused by the actual solid structure change. We integrated product island growth theory into random pore model (RPM). The model assumes the oxygen carrier has randomly distributed and overlapped pores, involving surface chemical reactions, product island growth, product layer diffusion, internal gas diffusion, and external gas diffusion to the particle surface. The model was verified using data of a natural iron ore from micro-fluidized bed thermogravimetric analysis (MFB-TGA) experiments. The kinetic parameters include chemical reaction rate constant (<span></span><math>\n <semantics>\n <mrow>\n <msub>\n <mi>k</mi>\n <mi>s</mi>\n </msub>\n </mrow>\n <annotation>$$ {k}_{\\mathrm{s}} $$</annotation>\n </semantics></math>), critical product layer thickness (<span></span><math>\n <semantics>\n <mrow>\n <msub>\n <mi>h</mi>\n <mi>C</mi>\n </msub>\n </mrow>\n <annotation>$$ {h}_{\\mathrm{C}} $$</annotation>\n </semantics></math>), and product layer diffusion coefficient (<span></span><math>\n <semantics>\n <mrow>\n <msub>\n <mi>D</mi>\n <mi>P</mi>\n </msub>\n </mrow>\n <annotation>$$ {D}_{\\mathrm{P}} $$</annotation>\n </semantics></math>). The reduction reaction rate is primarily governed by the chemical reaction, while both surface chemical reactions and product layer diffusion significantly influence the oxidation reaction. The reduction reaction, with an activation energy of 84.2 kJ/mol, is more temperature-sensitive than the oxidation reaction, which has an activation energy of 41.88 kJ/mol. Reaction temperature, particle size, and reactant gas concentration significantly impact the reaction rate and conversion of iron ore oxygen carriers. The model effectively predicts and analyzes the redox behavior of natural iron ore oxygen carrier, providing insights to optimize its performance.</p>","PeriodicalId":72922,"journal":{"name":"Engineering reports : open access","volume":"7 2","pages":""},"PeriodicalIF":2.0000,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/eng2.13064","citationCount":"0","resultStr":"{\"title\":\"Modeling and Experimental Researches on Redox Reactions of Iron Ore Oxygen Carriers in Chemical Looping\",\"authors\":\"Wang Hui, Lei Liu, Kexin Li, Di Zhong\",\"doi\":\"10.1002/eng2.13064\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Developing a reliable kinetic model for these redox reactions is crucial for understanding and improving oxygen carriers practical in chemical looping applications. The traditional pore model assumes that the solid product forms a continuous layer uniformly covering the solid reactant surface during the gas–solid reactions, in the result the model fails to capture the kinetic transitions caused by the actual solid structure change. We integrated product island growth theory into random pore model (RPM). The model assumes the oxygen carrier has randomly distributed and overlapped pores, involving surface chemical reactions, product island growth, product layer diffusion, internal gas diffusion, and external gas diffusion to the particle surface. The model was verified using data of a natural iron ore from micro-fluidized bed thermogravimetric analysis (MFB-TGA) experiments. The kinetic parameters include chemical reaction rate constant (<span></span><math>\\n <semantics>\\n <mrow>\\n <msub>\\n <mi>k</mi>\\n <mi>s</mi>\\n </msub>\\n </mrow>\\n <annotation>$$ {k}_{\\\\mathrm{s}} $$</annotation>\\n </semantics></math>), critical product layer thickness (<span></span><math>\\n <semantics>\\n <mrow>\\n <msub>\\n <mi>h</mi>\\n <mi>C</mi>\\n </msub>\\n </mrow>\\n <annotation>$$ {h}_{\\\\mathrm{C}} $$</annotation>\\n </semantics></math>), and product layer diffusion coefficient (<span></span><math>\\n <semantics>\\n <mrow>\\n <msub>\\n <mi>D</mi>\\n <mi>P</mi>\\n </msub>\\n </mrow>\\n <annotation>$$ {D}_{\\\\mathrm{P}} $$</annotation>\\n </semantics></math>). The reduction reaction rate is primarily governed by the chemical reaction, while both surface chemical reactions and product layer diffusion significantly influence the oxidation reaction. The reduction reaction, with an activation energy of 84.2 kJ/mol, is more temperature-sensitive than the oxidation reaction, which has an activation energy of 41.88 kJ/mol. Reaction temperature, particle size, and reactant gas concentration significantly impact the reaction rate and conversion of iron ore oxygen carriers. The model effectively predicts and analyzes the redox behavior of natural iron ore oxygen carrier, providing insights to optimize its performance.</p>\",\"PeriodicalId\":72922,\"journal\":{\"name\":\"Engineering reports : open access\",\"volume\":\"7 2\",\"pages\":\"\"},\"PeriodicalIF\":2.0000,\"publicationDate\":\"2025-02-10\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://onlinelibrary.wiley.com/doi/epdf/10.1002/eng2.13064\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Engineering reports : open access\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/eng2.13064\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"COMPUTER SCIENCE, INTERDISCIPLINARY APPLICATIONS\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Engineering reports : open access","FirstCategoryId":"1085","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/eng2.13064","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"COMPUTER SCIENCE, INTERDISCIPLINARY APPLICATIONS","Score":null,"Total":0}
引用次数: 0
摘要
为这些氧化还原反应建立一个可靠的动力学模型对于理解和改进氧载体在化学环中的实际应用至关重要。传统的孔隙模型假设在气固反应过程中,固体生成物在固体反应物表面形成均匀的连续层,因此该模型未能捕捉到实际固体结构变化所引起的动力学转变。我们将产品岛生长理论整合到随机孔隙模型(RPM)中。模型假设载氧体孔隙随机分布、重叠,涉及表面化学反应、产物岛生长、产物层扩散、内部气体扩散、外部气体向颗粒表面扩散。利用某天然铁矿微流化床热重分析(MFB-TGA)实验数据对模型进行了验证。动力学参数包括化学反应速率常数(k s $$ {k}_{\mathrm{s}} $$)、临界生成物层厚度(h C $$ {h}_{\mathrm{C}} $$)、和产品层扩散系数(dp $$ {D}_{\mathrm{P}} $$)。还原反应速率主要受化学反应控制,而表面化学反应和产物层扩散对氧化反应均有显著影响。还原反应的活化能为84.2 kJ/mol,比氧化反应的活化能为41.88 kJ/mol对温度更敏感。反应温度、粒度、反应物气体浓度对铁矿石氧载体的反应速率和转化率有显著影响。该模型有效地预测和分析了天然铁矿氧载体的氧化还原行为,为优化其性能提供了见解。
Modeling and Experimental Researches on Redox Reactions of Iron Ore Oxygen Carriers in Chemical Looping
Developing a reliable kinetic model for these redox reactions is crucial for understanding and improving oxygen carriers practical in chemical looping applications. The traditional pore model assumes that the solid product forms a continuous layer uniformly covering the solid reactant surface during the gas–solid reactions, in the result the model fails to capture the kinetic transitions caused by the actual solid structure change. We integrated product island growth theory into random pore model (RPM). The model assumes the oxygen carrier has randomly distributed and overlapped pores, involving surface chemical reactions, product island growth, product layer diffusion, internal gas diffusion, and external gas diffusion to the particle surface. The model was verified using data of a natural iron ore from micro-fluidized bed thermogravimetric analysis (MFB-TGA) experiments. The kinetic parameters include chemical reaction rate constant (), critical product layer thickness (), and product layer diffusion coefficient (). The reduction reaction rate is primarily governed by the chemical reaction, while both surface chemical reactions and product layer diffusion significantly influence the oxidation reaction. The reduction reaction, with an activation energy of 84.2 kJ/mol, is more temperature-sensitive than the oxidation reaction, which has an activation energy of 41.88 kJ/mol. Reaction temperature, particle size, and reactant gas concentration significantly impact the reaction rate and conversion of iron ore oxygen carriers. The model effectively predicts and analyzes the redox behavior of natural iron ore oxygen carrier, providing insights to optimize its performance.