Fe2O3修饰CaSO4/Ben载氧体化学链燃烧反应特性

穆丽颖; 肖慧霞; 张志丰; 蔡志阳; 王亦飞; 于广锁

Fe₂O₃修饰CaSO₄/Ben载氧体化学链燃烧反应特性

华东理工大学资源与环境工程学院，上海市煤气化工程技术研究中心，上海 200237

基金项目: 国家重点发计划（2017YFB0602802）

详细信息

作者简介:
穆丽颖（1995-），女，江苏南通人，硕士生，主要研究方向钙基载氧体化学链燃烧

通讯作者:
王亦飞，E-mail：wangyf@ecust.edu.cn

中图分类号: TQ038.4
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- 被引次数: 0
出版历程
- 收稿日期: 2021-03-13
- 网络出版日期: 2021-05-20

Reaction Performance of CaSO₄/Ben Oxygen Carrier Modified by Fe₂O₃ in Chemical Looping Combustion

School of Resources and Environmental Engineering, East China University of Science and Technology, Shanghai Engineering Research Center of Coal Gasification, Shanghai 200237, China

摘要

摘要: 利用间歇式流化床反应器和热重分析仪分别进行多次循环实验及反应性能测试，研究了Fe₂O₃在化学链燃烧过程中对CaSO₄/Ben载氧体的催化作用，通过对比不同Fe₂O₃含量载氧体与CO的反应活化能进行验证。实验结果表明，Fe₂O₃的添加使CaSO₄/Ben载氧体的比表面积和孔容增加，提高其还原反应速率，并维持系统内较高的CO₂浓度；Fe₂O₃可抑制CaSO₄反应生成CaO和含硫气体，提高CaSO₄/Ben载氧体循环反应的稳定性，w=15%的Fe₂O₃负载量为最佳选择；添加w=15%Fe₂O₃可使CaSO₄/Ben载氧体与CO反应活化能由88.72 kJ/mol降至43.08 kJ/mol，反应活性显著提高。
- 化学链燃烧 /
- 钙基载氧体 /
- Fe₂O₃修饰剂 /
- 催化作用
Abstract: Multiple cycles of experiments and reaction performance tests respectively were conducted using a batch fluidized bed reactor and a thermogravimetric analyzer. The catalytic effect of Fe₂O₃ on CaSO₄/Ben oxygen carriers (OCs) during chemical looping combustion (CLC) was analyzed and the reaction activation energy of OCs with different Fe₂O₃ content and CO were compared to verify. The experimental results showed that the specific surface area and pore volume of CaSO₄/Ben OCs increase with the addition of Fe₂O₃, which improved the reduction reaction rate and maintained the high CO₂ concentration in the system. Fe₂O₃ can inhibit CaSO₄ reaction to generate CaO and sulfur-containing gases, and improve the stability of CaSO₄/Ben OC circulation reaction. w=15% Fe₂O₃ addition was the best choice. The addition of w=15% Fe₂O₃ reduced the activation energy of CaSO₄/Ben OCs reacting with CO from 88.72 kJ/ mol to 43.08 kJ/mol, and the reactivity of CaSO₄/Ben OCs were significantly improved.
- chemical looping combustion /
- Ca-based oxygen carrier /
- Fe₂O₃ modifier /
- catalysis

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图 1 间歇式流化床化学链燃烧系统

Figure 1. Chemical looping combustion system of batch fluidized bed

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图 2 Fe₂O₃负载量对CO平均转化率的影响

Figure 2. Effect of Fe₂O₃ content on CO average conversion

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图 3 反应器出口气体浓度与反应时间的关系曲线

Figure 3. Variation of outlet gas concentration with reaction time

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图 4 载氧体化学链燃烧反应物及产物浓度曲线

Figure 4. Concentration curves of reactants and products in CLC of OCs

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图 5 CO平均转化率随循环次数的变化

Figure 5. CO average conversion rate varies with the number of cycles

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图 6 CaSO₄/Ben-15%Fe载氧体12次循环反应前后的SEM分析

Figure 6. SEM analysis of CaSO₄/Ben-15%Fe OCs before and after 12 ^th cycles

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图 7 CaSO₄/Ben-15%Fe载氧体颗粒反应前后孔径分布情况

Figure 7. Pore size distribution of CaSO₄/Ben-15%Fe oxygen carrier particles before and after reaction

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图 8 CO平均转化率的衰减比

Figure 8. Attenuation ratio of CO average conversion

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图 9 不同载氧体在800 °C下的TG和DTG曲线

Figure 9. TG and DTG curves of different OCs at 800 °C

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图 10 CaSO₄/Ben实验数据和模型结果与反应条件的比较

Figure 10. Comparison of experimental data and model results of CaSO₄/Ben with reaction conditions

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图 11 ln k与1/T的Arrhenius图

Figure 11. Arrhenius Diagrams of ln k and 1/T

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图 12 活化能E随Fe负载量的变化曲线

Figure 12. Change curve of activation energy E with Fe content

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表 1 实验条件

Table 1. Experimental conditions

Related parameters	Gas composition	Gas flow/(L·min⁻¹)	Temperature/℃	Reaction time/min
Reduction stage	φ (CO) 20%, φ (N₂) 80%	1.8	900	20
Oxidation stage	φ (O₂) 10%, φ (N₂) 90%	1.8	900	φ (O₂) 10% (in exhaust gas)

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表 2 新制CaSO₄/Ben和CaSO₄/Ben-15%Fe载氧体颗粒孔径特性

Table 2. Pore size characteristics of newly prepared CaSO₄/Ben and CaSO₄/Ben-15%Fe OCs

Sample	S_BET/(m²·g⁻¹)	V_p/(cm³·g⁻¹)	D_pore/nm
CaSO₄/Ben	2.4548	0.014772	30.4082
CaSO₄/Ben-15%Fe	3.1795	0.022442	32.6607

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表 3 CaSO₄/Ben-15%Fe载氧体颗粒反应前后孔径特性

Table 3. Pore size characteristics of CaSO₄/Ben-15%Fe OCs before and after reaction

Sample	S_BET/(m²·g⁻¹)	V_p/(cm³·g⁻¹)	D/nm
Raw CaSO₄/Ben-15%Fe	3.18	0.022	32.66
CaSO₄/Ben-15%Fe after 12^th cycle	2.67	0.013	27.71

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表 4 不同反应温度对应的最佳拟合值m

Table 4. Best fitting value m corresponding to different reaction temperatures

Temperature/°C	Best fitting value of m	Linear correlation coefficient	Standard deviation
800	1.711	0.946	0.027
850	1.719	0.953	0.030
900	1.750	0.976	0.027
950	1.756	0.991	0.019

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