CO在成型催化剂上脱除NOx的反应动力学模型

doi:10.16085/j.issn.1000-6613.2020-1639

化工进展 ›› 2021, Vol. 40 ›› Issue (S1): 245-252.DOI: 10.16085/j.issn.1000-6613.2020-1639

CO在成型催化剂上脱除NO_x的反应动力学模型

李彦霖¹(), 程星星¹(), 赵明亮¹, 王鲁元², 王志强¹

^1.山东大学能源与动力工程学院，燃煤污染物减排国家工程实验室，环境热工技术教育部工程研究中心，山东省能源碳减排技术与资源化利用重点实验室，山东济南 250061
^2.齐鲁工业大学（山东省科学院）能源研究所，能源与动力工程学院，山东济南 250014

收稿日期:2020-08-17 修回日期:2021-01-06 出版日期:2021-10-25 发布日期:2021-11-09
通讯作者: 程星星
作者简介:李彦霖（1997—），男，硕士研究生，研究方向为烟气污染物处理和锂离子电池材料。E-mail：201934147@mail.sdu.edu.cn。
基金资助:
国家重点研发计划(2017YFB0602904)

Kinetic model of NO_x removal by CO onto forming catalysts

LI Yanlin¹(), CHENG Xingxing¹(), ZHAO Mingliang¹, WANG Luyuan², WANG Zhiqiang¹

^1.National Engineering Laboratory for Reducing Emissions from Coal Combustion, Engineering Research Center of Environmental Thermal Technology of Ministry of Education, Shandong Key Laboratory of Energy Carbon Reduction and Resource Utilization, School of Energy and Power Engineering, Shandong University, Jinan 250061, Shandong, China
^2.Energy Research Institute, School of Energy and Power Engineering, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250014, Shandong, China

Received:2020-08-17 Revised:2021-01-06 Online:2021-10-25 Published:2021-11-09
Contact: CHENG Xingxing

摘要/Abstract

摘要：

采用实验和模拟相结合的方法研究了NO_x在固定床反应器中的吸附还原过程。选取商业常用的堇青石和TiO₂为主要的成型催化剂基体材料，以铜铁铈复合型金属氧化物为活性成分，制备了蜂窝成型催化剂，对蜂窝催化剂的吸附性能和脱硝还原活性进行测定。建立了固定床反应器中CO脱除NO_x的反应动力学模型，由于CO法脱硝反应的解耦分解，脱硝反应模型也由吸附模型和还原模型组成。吸附模型由固相和气相的微分质量平衡方程建立，还原模型由一组微分方程组成。通过固定床NO_x吸附曲线和不同温度下NO_x的转化率对模型中的关键参数进行了拟合，得到了CO在成型催化剂上脱除NO_x的反应动力学模型，该模型与实验数据吻合较好。在此基础上，模拟了其他条件下吸附过程的穿透曲线和还原反应的转化率。此模型能较好地揭示CO在蜂窝催化剂上还原NO_x的反应动力学，为CO法成型催化剂脱除NO_x的实验或者工程提供理论指导。

关键词: 选择性催化还原技术, 动力学模型, 模拟, 吸附, 固定床

Abstract:

The adsorption and reduction process of NO_x in a fixed bed reactor was studied by combining experiment and simulation. Commercial cordierite and TiO₂ were selected as the main forming catalyst matrix materials, and copper, iron, cerium compound metal oxide was used as the active component to prepare the honeycomb forming catalyst. The adsorption performance and reduction activity of the honeycomb catalyst were measured. The reaction kinetics model of NO_x removal by CO in fixed bed reactor was established. Due to the decoupling decomposition of CO reduction, the reaction model of removal was also composed of adsorption model and reduction model. The adsorption model is established by the differential mass balance equation of solid and gas phases, and the reduction model is composed of a set of differential equations. The key parameters of the model were fitted by the NO_x adsorption curves of fixed bed and the conversion rates of NO_x at different temperatures. The reaction kinetics model of CO removal of NO_xon the forming catalyst was obtained. The model was in good agreement with the experimental data. On this basis, the penetration curve of adsorption process and the conversion rate of reduction reaction under other conditions were simulated. This model can better reveal the reaction kinetics of NO_x reduction by CO on honeycomb catalyst, and provide theoretical guidance for experiments or engineering.

Key words: selective catalytic reduction, dynamic model, simulation, adsorption, fixed bed

中图分类号:

李彦霖, 程星星, 赵明亮, 王鲁元, 王志强. CO在成型催化剂上脱除NO_x的反应动力学模型[J]. 化工进展, 2021, 40(S1): 245-252.

LI Yanlin, CHENG Xingxing, ZHAO Mingliang, WANG Luyuan, WANG Zhiqiang. Kinetic model of NO_x removal by CO onto forming catalysts[J]. Chemical Industry and Engineering Progress, 2021, 40(S1): 245-252.

图/表 14

图1 成型催化剂活性测试系统

图2 5%~15%水玻璃浓度催化剂吸附拟合曲线

图3 不同温度下NO脱硝转化率的拟合

图4 催化剂表面NOx吸附机理示意图模型假设

图5 不同入口浓度下的吸附容量

表1 不同水玻璃浓度下拟合参数的值

水玻璃质量分数/%	k_F	D_g
5	1.48×10^-8	0.0036
10	2.22×10^-8	0.0066
15	2.96×10^-8	0.0102

表2 推测其他水玻璃浓度下参数的值

水玻璃质量分数/%	k_F	D_g
8	1.924×10^-8	0.0054
13	2.660×10^-8	0.0088

图6 不同水玻璃浓度下的模拟值和实验值对比

图7 模拟不同空速时出口NOx浓度随时间的变化

图8 模拟不同入口NO浓度时出口NOx浓度随时间的变化

表3 不同温度下拟合出的k和NO的转化率

温度/℃	实验NO转换率/%	k的拟合值	拟合NO转化率/%
100	2.37	0.0065	2.36
150	35.21	0.118	35.30
200	58.80	0.258	58.83
250	78.03	0.476	78.05
300	87.14	0.676	87.14
350	96.38	1.181	96.38

图9 不同温度下k的拟合值和实验值的对比

图10 不同CO初始浓度下转化率的模拟（反应条件：T=150℃，GHSV=1500h-1）

图11 不同NO初始浓度下转化率的模拟（反应条件：T=150℃，GHSV=1500h-1）

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CO在成型催化剂上脱除NO_x的反应动力学模型

Kinetic model of NO_x removal by CO onto forming catalysts

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CO在成型催化剂上脱除NOx的反应动力学模型

Kinetic model of NOx removal by CO onto forming catalysts

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CO在成型催化剂上脱除NO_x的反应动力学模型

Kinetic model of NO_x removal by CO onto forming catalysts