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浙江大学学报(工学版)
Journal of ZheJiang University (Engineering Science)  2022, Vol. 56 Issue (6): 1199-1205    DOI: 10.3785/j.issn.1008-973X.2022.06.018
    
Relationship between morphology characteristics of CuCr2O4catalyst and its SCR denitrification activity
Er-hao GAO1,2(),Tian-yu SHOU2,3,Bei HUANG3,Wei WANG1,Yao SHI2
1. School of Environmental and Safety Engineering, Changzhou University, Changzhou 213164, China
2. College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China
3. Zhejiang Feida Environmental Protection Technology Limited Company, Zhuji 311800, China
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Abstract  

The SCR denitrification activities of CuCr2O4 catalysts with various morphologies were tested and compared. The spinel-type CuCr2O4 catalysts with polyhedral, granular and spherical shapes were prepared, respectively. The results showed that polyhedral CuCr2O4 showed the best catalytic activity, with the de-NOx activity reaching 50% at 157 ℃ and maintaining above 99% at 225-320 ℃, and it exhibited good resistance against water vapor and SO2. The de-NOx activities follow the sequence of polyhedral CuCr2O4 > granular CuCr 2O4>spherical CuCr2O4. The effects of morphology on the denitrification performance of CuCr2O4 were analyzed by a series of characterization techniques. N2 sorption-desorption results showed that polyhedral CuCr2O4 had the highest specific surface area (25.5 m2/g) and the largest pore volume (0.154 cm3/g); X-ray photoelectron spectroscopy (XPS) results showed that polyhedral CuCr2O4 possessed the highest ratio of surface reactive oxygen species (49.5%) and Cu+(16.2%); NH3-programmed temperature desorption (NH3-TPD) showed that polyhedral CuCr2O4 had the highest surface acid concentration (0.12 mmol/g) and intensity; H2-programmed temperature reduction (H2-TPR) showed that polyhedral CuCr2O4 had the most reducible and abundant surface active species (3.69 mmol/g), which facilitated the SCR reaction in the low-temperature range. The enhanced surface acidity and redox properties of polyhedral CuCr2O4 makes it exhibit better de-NOx performance.

Key words： CuCr2O4      spinel      morphology      SCR      denitrification performance      catalyst     
Received: 23 July 2021      Published: 30 June 2022
CLC:  X 511  
Fund:  江苏省自然科学基金资助项目(BK20210857)；江苏省普通高校自然科学研究资助项目(21KJB610006)；常州大学科研启动基金资助项目(ZMF21020016)
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Er-hao GAO
Tian-yu SHOU
Bei HUANG
Wei WANG
Yao SHI
Cite this article:

Er-hao GAO,Tian-yu SHOU,Bei HUANG,Wei WANG,Yao SHI. Relationship between morphology characteristics of CuCr2O4catalyst and its SCR denitrification activity. Journal of ZheJiang University (Engineering Science), 2022, 56(6): 1199-1205.

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https://www.zjujournals.com/eng/10.3785/j.issn.1008-973X.2022.06.018     OR     https://www.zjujournals.com/eng/Y2022/V56/I6/1199


CuCr2O4催化剂形貌特征与其SCR脱硝性能的关系

分别制备形貌为多面体状、颗粒状、球状的尖晶石型CuCr2O4催化剂，测试对比不同形貌CuCr2O4催化剂的SCR脱硝性能. 结果表明，多面体状CuCr2O4的催化活性最好，且在157 ℃时脱硝效率达到50%，在225~320 ℃脱硝效率超过99%，具有良好的抗硫、抗水性能. 脱硝活性由大到小依次为多面体状CuCr2O4、颗粒状CuCr2O4、球状CuCr2O4. 采用表征技术分析微观形貌对CuCr2O4脱硝性能的影响. N2吸附-脱附结果显示，多面体状CuCr2O4具有最大的比表面积(25.5 m2/g)和最大的孔容积(0.154 cm3/g)；X射线光电子能谱(XPS)结果显示，多面体状CuCr2O4相较于其他形貌拥有更高比例的表面活性氧(49.5%)和Cu+(16.2%)；NH3-程序升温脱附(NH3-TPD)结果显示，多面体状CuCr2O4拥有最高表面酸浓度(0.12 mmol/g)及酸强度；H2-程序升温还原(H2-TPR)结果显示，多面体状CuCr2O4表面活性物种最易还原且数量最多(3.69 mmol/g)，使得SCR反应在低温段更易进行. 多面体状CuCr2O4的高表面酸性与氧化还原性，使其具有良好的脱硝性能.


关键词： CuCr2O4,  尖晶石,  形貌,  SCR,  脱硝性能,  催化剂 
Fig.1 Denitrification efficiency for CuCr2O4 catalysts
Fig.2 N2O volume fraction and N2 selectivity over CuCr2O4 catalysts
Fig.3 Effects of SO2+H2O on denitrification activity for CuCr2O4 catalysts
Fig.4 Micro-morphology characteristics of CuCr2O4 catalysts
Fig.5 Particle size distribution of CuCr2O4 catalysts
Fig.6 N2 adsorption-desorption isotherms and BJH pore diameter distribution of CuCr2O4 catalysts
催化剂 S/(m2·g?1) d/nm V/(cm3·g?1)
CuCr2O4-P 25.5 10.9 0.154
CuCr2O4-G 21.8 11.5 0.146
CuCr2O4-S 16.7 10.4 0.098
Tab.1 Specific surface area, pore diameter, and pore volume of CuCr2O4 catalysts
Fig.7 XRD patterns for CuCr2O4 catalysts
催化剂 x/%
Cu O Cr Oα/(Oα+Oβ) Cu+/(Cu++Cu2+)
CuCr2O4-P 12.82 66.07 21.11 49.5 16.2
CuCr2O4-G 9.57 66.39 24.04 39.4 7.6
CuCr2O4-S 13.40 63.21 24.44 40.8 10.7
Tab.2 Surface elements molar fractions of CuCr2O4 catalysts
Fig.8 XPS spectra fitting results of O 1s and Cu 2p3/2 of CuCr2O4 catalysts
Fig.9 NH3-TPD profiles for CuCr2O4 catalysts
Fig.10 H2-TPR profiles for CuCr2O4 catalysts
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