ZrO2/TiO2载体协同作用下Fe2O3(104)与CO化学链燃烧特性

doi:10.7503/cjcu20170577

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (3): 506.doi: 10.7503/cjcu20170577

ZrO₂/TiO₂载体协同作用下Fe₂O₃(104)与CO化学链燃烧特性

程伟良¹(), 朱梦倩¹, 覃吴²(), 侯翠翠²

1. 华北电力大学能源动力与机械工程学院, 北京 102206
2. 华北电力大学可再生能源学院, 生物质发电成套设备国家工程实验室, 北京 102206

收稿日期:2017-08-24 出版日期:2018-03-10 发布日期:2018-01-23
作者简介:联系人简介: 覃吴, 男, 博士, 副教授, 主要从事清洁燃烧及新能源材料研究. E-mail:qinwu@ncepu.edu.cn; 程伟良, 男, 博士, 教授, 主要从事清洁燃烧及污染物排放研究. E-mail:cwl@ncepu.edu.cn
基金资助:
国家自然科学基金(批准号: 51476056)和中央高校基本科研专项基金(批准号: 2016YQ07)资助

Chemical Looping Combustion Characteristics of Fe₂O₃(104) and CO Under Synergistic Action of ZrO₂/TiO₂ Carrier^†

CHENG Weiliang^1,^*(), ZHU Mengqian¹, QIN Wu^2,^*(), HOU Cuicui²

1. School of Energy Power and Mechanical Engineering, North China Electric Power University, Beijing 102206, China
2. National Engineering Laboratory for Biomass Power Generation Equipment, School of Renewable Energy,North China Electric Power University, Beijing 102206, China

Received:2017-08-24 Online:2018-03-10 Published:2018-01-23
Contact: CHENG Weiliang,QIN Wu E-mail:cwl@ncepu.edu.cn;qinwu@ncepu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.51476056) and the Fundamental Research Funds for the Central Universities, China(No.2016YQ07)

摘要/Abstract

摘要：

在表面形貌控制增强铁基载氧体Fe₂O₃(104)化学链燃烧反应活性研究的基础上, 进一步研究了TiO₂, ZrO₂载体协同作用下Fe₂O₃(104)与CO化学链燃烧的反应特性. 采用X射线衍射(XRD), 扫描电子显微镜(SEM)和比表面积(BET)等方法对所制备的载氧体Fe₂O₃(104)/TiO₂和Fe₂O₃(104)/ZrO₂进行表征. 研究了700, 800和900℃下载氧体与CO化学链燃烧反应特性. 结果表明, 不同载体对Fe₂O₃(104)与CO发生化学链燃烧反应活性的影响程度不同, ZrO₂作为载体明显促进Fe₂O₃(104)与CO的反应速率. 动力学分析结果显示, Fe₂O₃(104)/TiO₂与CO反应模型属于一级反应, 反应活化能为153.6 kJ/mol; Fe₂O₃(104)/ZrO₂与CO反应模型属于抽缩球体模型, 反应活化能为118.9 kJ/mol.

关键词: 化学链燃烧, 载氧体, Fe2O3(104), 化学反应动力学

Abstract:

This work focused on the synergetic effect of the supports TiO₂ and ZrO₂ on the chemical looping combustion(CLC) between Fe₂O₃(104) and CO. Fe₂O₃(104)/TiO₂ and Fe₂O₃(104)/ZrO₂ were prepared, and characterized by means of XRD, SEM and BET. Then, the CLC reactions between the prepared oxygen carrier and CO were studied under 700, 800 and 900 ℃ in a small CLC reaction system, the results suggest that the supports affect the reactivity of Fe₂O₃(104), and ZrO₂ is more efficient than TiO₂. Furthermore, dynamic analysis shows that the reaction between Fe₂O₃(104)/TiO₂ and CO could be assigned to the first order reaction model with the apparent activation energy(E) being 153.6 kJ/mol, while the reaction between Fe₂O₃(104)/ZrO₂ and CO belongs to the Shrink sphere reaction model with E being 118.9 kJ/mol. This work provides more reasonable dynamic model for the designing of CLC reactor.

Key words: Chemical looping combustion, Oxygen carrier, Fe2O3(104), Chemical reaction kinetics

中图分类号:

O641

TrendMD:

程伟良, 朱梦倩, 覃吴, 侯翠翠. ZrO₂/TiO₂载体协同作用下Fe₂O₃(104)与CO化学链燃烧特性. 高等学校化学学报, 2018, 39(3): 506.

CHENG Weiliang, ZHU Mengqian, QIN Wu, HOU Cuicui. Chemical Looping Combustion Characteristics of Fe₂O₃(104) and CO Under Synergistic Action of ZrO₂/TiO₂ Carrier^†. Chem. J. Chinese Universities, 2018, 39(3): 506.

图/表 11

Fig.1 Schematic progress of chemical-looping combustion

Fig.2 Chemical chain combustion test stand diagram

Fig.3 XRD patterns of the prepared oxygen carrieres Fe2O3(104)/TiO2(A) and Fe2O3(104)/ZrO2(B)The data are denoted as Fe2O3 different crystal face indices.

Fig.4 SEM images of the prepared oxygen carrieres Fe2O3(104)/TiO2(A) and Fe2O3(104)/ZrO2(B)

Table 1 Specific surface and pore size of different oxygen carriers

Oxygen carrier	Surface area/(m²·g^-1)	Pore volume/(mL·g^-1)	Pore diameter/nm
Fe₂O₃(104)/TiO₂	2.918	0.003	12.967
Fe₂O₃(104)/ZrO₂	3.870	0.006	3.400

Fig.5 CO2 generation for the chemical looping combustion between Fe2O3(104)/ZrO2(a) and Fe2O3(104)/TiO2(b) and CO at 700 ℃(A), 800 ℃(B) and 900 ℃(C), respectively

Table 2 CO2 conversion of different oxygen carriers at different time

Temperature/℃	Time/min	Fe₂O₃(104)/TiO₂	Fe₂O₃(104)/ZrO₂
700	6	0.322	0.308
	7	0.309	0.276
	8	0.286	0.245
	16	0.165	0.135
800	6	0.388	0.510
	7	0.348	0.452
	8	0.309	0.410
	16	0.174	0.262
900	6	0.462	0.475
	7	0.409	0.438
	8	0.363	0.401
	16	0.207	0.272

Fig.6 Thermogravimetric curves of Fe2O3(104)/TiO2(a) and Fe2O3(104)/ZrO2(b) and CO at constant temperature(900 ℃), respectirely

Fig.7 Conversion curves of reaction of Fe2O3(104)/TiO2(a) and Fe2O3(104)/ZrO2(b) and CO at 900 ℃, respectrvely

Table 3 Correlation coefficients calculated using different kinetic models

Reaction	Correlation coefficient		Reaction	Correlation coefficient
Reaction	Fe₂O₃(104)/TiO₂		Fe₂O₃(104)/ZrO₂	Fe₂O₃(104)/TiO₂	Fe₂O₃(104)/ZrO₂
Phase interface	0.8474	0.9308	Shrink the sphere	0.9553	0.9953
First order	0.9921	0.9494	Power function law	0.8995	0.9625
Secondary	0.9099	0.1601	Valensi	0.9398	0.9787
Three-stage	0.7816	0.0528	Jander	0.9873	0.9650
Shrink the cylinder	0.9288	0.9875	G-B	0.9607	0.9828

Fig.8 TG curves for chemical looping combustion reaction between CO and oxygen carrier Fe2O3(104)/TiO2(A) and Fe2O3(104)/ZrO2(B), respectively

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ZrO₂/TiO₂载体协同作用下Fe₂O₃(104)与CO化学链燃烧特性

Chemical Looping Combustion Characteristics of Fe₂O₃(104) and CO Under Synergistic Action of ZrO₂/TiO₂ Carrier^†

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