化学链燃烧中赤铁矿氧载体的本征反应动力学研究

doi:10.3976/j.issn.1002-4026.2017.01.007

山东科学 ›› 2017, Vol. 30 ›› Issue (1): 41-51.doi: 10.3976/j.issn.1002-4026.2017.01.007

化学链燃烧中赤铁矿氧载体的本征反应动力学研究

苏明泽¹, 赵海波², 杜保周¹, 张鹏飞¹, 刘志刚¹

1. 山东省科学院流动与强化传热重点实验室,山东省科学院能源研究所,山东济南250014；
2. 华中科技大学能源与动力工程学院煤燃烧国家重点实验室, 湖北武汉 430074

收稿日期:2016-09-28 出版日期:2017-02-20 发布日期:2017-02-20
作者简介:苏明泽(1989—)，男，硕士，研究方向为化学链燃烧。
基金资助:
国家重点研发计划项目(2016YFB0600801，2016YFB0601300)；国家自然科学基金(51406110)；山东省优秀中青年科学家科研奖励基金(BS2014NJ013)；山东省科学院基础基金(科基合字(2015)第8号)；山东省科学院青年基金(2014QN014)

Experimental investigation for the intrinsic reduction kinetics of a hematite as oxygen carrier in chemical looping combustion

SU Ming-ze¹, ZHAO Hai-bo², DU Bao-zhou¹, ZHANG Peng-fei¹, LIU Zhi-gang¹

1. Key Laboratory for Flow &Enhanced Heat Transfer of Shandong Academy of Sciences, Jinan 250014, China;
2. State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074, China

Received:2016-09-28 Online:2017-02-20 Published:2017-02-20

摘要/Abstract

摘要：

本文对一种化学链燃烧所用赤铁矿氧载体进行了本征还原反应动力学研究。氧载体颗粒的比表面积及孔径分布测试显示此种氧载体的孔隙率为0.031，表明此种氧载体结构致密，孔隙结构不发达。热重反应器上进行的程序升温还原实验结果显示氧载体的还原反应分阶段进行，并确定第一还原阶段的温度测试窗口为400~650 °C。在排除了氧载体颗粒内外扩散的影响后，批次流化床实验分析确定反应的本征活化能为138.55 kJ/mol，指前因子为6.8×1013 s^-1。通过对内外扩散因素的分析，加深了对此种氧载体颗粒与CO的宏观反应特性的认识。本研究结论与前人关于缩核模型、外扩散控制以及较小的表观活化能的研究结论具有良好的相容性。

关键词: 化学链燃烧, 赤铁矿氧载体, 本征反应动力学

Abstract:

In this work, the intrinsic kinetics of the first reduction stage of a hematite as oxygen carrier (OC) reduced by carbon monoxide (CO) has been investigated. For the intrinsic kinetics analysis, the BET surface area and the pore size distribution tests showed that the porosity of this kind of OC was 0.031, which revealed that the OC had dense structure with undeveloped pore structure. The temperature programmed reduction experiments were conducted in the thermo gravimetric analyzer, which showed that the reduction of OC was conducted in stages, and the appropriate experimental temperature range for testing the intrinsic kinetics of the first reduction stage was 400~650 °C. Furthermore, a series of formal experiments were conducted in a batch fluidized bed system with different temperatures and different CO concentrations. The intrinsic activation energy and the preexponential factor were determined as 138.55 kJ/mol and 6.8×1013 s^-1 respectively, after the internal and external diffusion factor been eliminated. The analysis to the internal and external diffusion factors deepened the acknowledgement to the reaction properties of this kind of hematite OC reduced by CO. The researching results of this paper had good compatibility with many previous research conclusions such as shrinking core model, external diffusion control and smaller apparent activation energy.

Key words: intrinsic reduction kinetics, hematite oxygen carrier, chemical looping combustion

中图分类号:

TK16

苏明泽, 赵海波, 杜保周, 张鹏飞, 刘志刚. 化学链燃烧中赤铁矿氧载体的本征反应动力学研究[J]. 山东科学, 2017, 30(1): 41-51.

SU Ming-ze, ZHAO Hai-bo, DU Bao-zhou, ZHANG Peng-fei, LIU Zhi-gang. Experimental investigation for the intrinsic reduction kinetics of a hematite as oxygen carrier in chemical looping combustion[J]. SHANDONG SCIENCE, 2017, 30(1): 41-51.

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化学链燃烧中赤铁矿氧载体的本征反应动力学研究

Experimental investigation for the intrinsic reduction kinetics of a hematite as oxygen carrier in chemical looping combustion

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