Insight into the promotional mechanism of Cu modification towards wide-temperature NH3-SCR performance of NbCe catalyst

doi:10.1016/j.cjche.2022.05.028

Chinese Journal of Chemical Engineering ›› 2022, Vol. 50 ›› Issue (10): 301-309.DOI: 10.1016/j.cjche.2022.05.028

• Catalysis, Kinetics and Reaction Engineering • Previous Articles Next Articles

Insight into the promotional mechanism of Cu modification towards wide-temperature NH₃-SCR performance of NbCe catalyst

Dongqi An¹, Yuyao Yang², Weixin Zou³, Yandi Cai³, Qing Tong⁴, Jingfang Sun⁴, Lin Dong⁵

1 Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering and Jiangsu Key Laboratory of Vehicle Emissions Control, Nanjing University, Nanjing 210093, China;
2 Center for Nanochemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China;
3 Jiangsu Key Laboratory of Vehicle Emissions Control, School of Environment, Nanjing University, Nanjing 210093, China;
4 Jiangsu Key Laboratory of Vehicle Emissions Control, Center of Modern Analysis, Nanjing University, Nanjing 210093, China;
5 Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering and Jiangsu Key Laboratory of Vehicle Emissions Control, School of Environment, Center of Modern Analysis, Nanjing University, Nanjing 210093, China

Received:2022-03-20 Revised:2022-05-19 Online:2023-01-04 Published:2022-10-28
Contact: Jingfang Sun,E-mail:sunjf@nju.edu.cn;Lin Dong,E-mail:donglin@nju.edu.cn
Supported by:
Financial support from the National Natural Science Foundation of China, China (Nos. 21972062, 21976081, 21976111) is gratefully acknowledged.

Insight into the promotional mechanism of Cu modification towards wide-temperature NH₃-SCR performance of NbCe catalyst

Dongqi An¹, Yuyao Yang², Weixin Zou³, Yandi Cai³, Qing Tong⁴, Jingfang Sun⁴, Lin Dong⁵

1 Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering and Jiangsu Key Laboratory of Vehicle Emissions Control, Nanjing University, Nanjing 210093, China;
2 Center for Nanochemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China;
3 Jiangsu Key Laboratory of Vehicle Emissions Control, School of Environment, Nanjing University, Nanjing 210093, China;
4 Jiangsu Key Laboratory of Vehicle Emissions Control, Center of Modern Analysis, Nanjing University, Nanjing 210093, China;
5 Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering and Jiangsu Key Laboratory of Vehicle Emissions Control, School of Environment, Center of Modern Analysis, Nanjing University, Nanjing 210093, China

通讯作者: Jingfang Sun,E-mail:sunjf@nju.edu.cn;Lin Dong,E-mail:donglin@nju.edu.cn
基金资助:
Financial support from the National Natural Science Foundation of China, China (Nos. 21972062, 21976081, 21976111) is gratefully acknowledged.

Abstract

Abstract: A simple strategy of Cu modification was proposed to broaden the operation temperature window for NbCe catalyst. The best catalyst Cu_0.010/Nb₁Ce₃ presented over 90% NO conversion in a wide temperature range of 200-400 ℃ and exhibited an excellent H₂O or/and SO₂ resistance at 275 ℃. To understand the promotional mechanism of Cu modification, the correlation among the “activity-structure-property” were tried to establish systematically. Cu species highly dispersed on NbCe catalyst to serve as the active component. The strong interaction among Cu, Nb and Ce promoted the emergence of NbO₄ and induced more Brønsted acid sites. And Cu modification obviously enhanced the redox behavior of the NbCe catalyst. Besides, EPR probed the Cu species exited in the form of monomeric and dimeric Cu²⁺, the isolated Cu²⁺ acted as catalytic active sites to promote the reaction: Cu²⁺-NO₃^-+NO(g) → Cu²⁺-NO₂^-+NO₂(g). Then the generated NO₂ would accelerate the fast-SCR reaction process and thus facilitated the low-temperature deNO efficiency. Moreover, surface nitrates became unstable and easy to decompose after Cu modification, thus providing additional adsorption and activation sites for NH₃, and ensuring the improvement of catalytic activity at high temperature. Since the NH₃-SCR reaction followed by E-R reaction pathway efficaciously over Cu_0.010/Nb₁Ce₃ catalyst, the excellent H₂O and SO₂ resistance was as expected.

Key words: NH₃-SCR, NbCe catalyst, Cu modification, NO₂ promoting effect, Fast-SCR, Flue gas

摘要： A simple strategy of Cu modification was proposed to broaden the operation temperature window for NbCe catalyst. The best catalyst Cu_0.010/Nb₁Ce₃ presented over 90% NO conversion in a wide temperature range of 200-400 ℃ and exhibited an excellent H₂O or/and SO₂ resistance at 275 ℃. To understand the promotional mechanism of Cu modification, the correlation among the “activity-structure-property” were tried to establish systematically. Cu species highly dispersed on NbCe catalyst to serve as the active component. The strong interaction among Cu, Nb and Ce promoted the emergence of NbO₄ and induced more Brønsted acid sites. And Cu modification obviously enhanced the redox behavior of the NbCe catalyst. Besides, EPR probed the Cu species exited in the form of monomeric and dimeric Cu²⁺, the isolated Cu²⁺ acted as catalytic active sites to promote the reaction: Cu²⁺-NO₃^-+NO(g) → Cu²⁺-NO₂^-+NO₂(g). Then the generated NO₂ would accelerate the fast-SCR reaction process and thus facilitated the low-temperature deNO efficiency. Moreover, surface nitrates became unstable and easy to decompose after Cu modification, thus providing additional adsorption and activation sites for NH₃, and ensuring the improvement of catalytic activity at high temperature. Since the NH₃-SCR reaction followed by E-R reaction pathway efficaciously over Cu_0.010/Nb₁Ce₃ catalyst, the excellent H₂O and SO₂ resistance was as expected.

关键词: NH₃-SCR, NbCe catalyst, Cu modification, NO₂ promoting effect, Fast-SCR, Flue gas

Dongqi An, Yuyao Yang, Weixin Zou, Yandi Cai, Qing Tong, Jingfang Sun, Lin Dong. Insight into the promotional mechanism of Cu modification towards wide-temperature NH₃-SCR performance of NbCe catalyst[J]. Chinese Journal of Chemical Engineering, 2022, 50(10): 301-309.

References

[1] M. Barreau, M.L. Tarot, D. Duprez, X. Courtois, F. Can, Remarkable enhancement of the selective catalytic reduction of NO at low temperature by collaborative effect of ethanol and NH₃ over silver supported catalyst, Appl. Catal. B:Environ., 220 (2018) 19-30
[2] Z. Ma, X. Wu, H. Härelind, D. Weng, B. Wang, Z. Si, NH₃-SCR reaction mechanisms of NbOx/Ce_0.75Zr_0.25O₂ catalyst:DRIFTS and kinetics studies, J. Mol. Catal. A:Chem., 423 (2016) 172-180
[3] T. Zhang, R. Qu, W. Su, J. Li, A novel Ce-Ta mixed oxide catalyst for the selective catalytic reduction of NOx with NH₃, Appl. Catal. B:Environ., 176-177 (2015) 338-346
[4] M.F. Irfan, J.H. Goo, S.D. Kim, Co₃O₄ based catalysts for NO oxidation and NOx reduction in fast SCR process, Appl. Catal. B:Environ., 78 (2008) 267-274
[5] S. Roy, M.S. Hegde, G. Madras, Catalysis for NOx abatement, Appl. Energy, 86 (2009) 2283-2297
[6] S. Ding, F. Liu, X. Shi, H. He, Promotional effect of Nb additive on the activity and hydrothermal stability for the selective catalytic reduction of NOx with NH₃ over CeZrOx catalyst, Appl. Catal. B:Environ., 180 (2016) 766-774
[7] F. Liu, H. He, Y. Ding, C. Zhang, Effect of manganese substitution on the structure and activity of iron titanate catalyst for the selective catalytic reduction of NO with NH₃, Appl. Catal. B:Environ., 93 (2009) 194-204
[8] J.P. Dunn, P.R. Koppula, H. G. Stenger, I.E. Wachs, Oxidation of sulfur dioxide to sulfur trioxide over supported vanadia catalysts, Appl. Catal. B:Environ., 19 (1998) 103-117
[9] P. Li, Y. Xin, Q. Li, Z. Wang, Z. Zhang, L. Zheng, Ce-Ti amorphous oxides for selective catalytic reduction of NO with NH₃:Confirmation of Ce-O-Ti active sites, Environ. Sci. & Technol., 46 (2012) 9600-9605
[10] G. Busca, L. Lietti, G. Ramis, F. Berti, Chemical and mechanistic aspects of the selective catalytic reduction of NOx by ammonia over oxide catalysts:A review, Appl. Catal. B:Environ., 18 (1998) 1-36
[11] M. Stanciulescu, G. Caravaggio, A. Dobri, J. Moir, R. Burich, J.P. Charland, P. Bulsink, Low-temperature selective catalytic reduction of NOx with NH₃ over Mn-containing catalysts, Appl. Catal. B:Environ., 123-124 (2012) 229-240
[12] J.W. Ji, Y. Tang, L. Han, P. Ran, W. Song, Y.D. Cai, W. Tan, J.F. Sun, C.J. Tang, L. Dong, Cerium manganese oxides coupled with ZSM-5:A novel SCR catalyst with superior K resistance, Chem. Eng. J, (2022) 136530
[13] L. Chen, Z. Si, X. Wu, D. Weng, DRIFT study of CuO-CeO₂-TiO₂ mixed oxides for NOx reduction with NH₃ at low temperatures, ACS Appl. Mater. & Inter., 6 (2014) 8134-8145
[14] C. Tang, H. Zhang, L. Dong, Ceria-based catalysts for low-temperature selective catalytic reduction of NO with NH₃, Catal. Sci. & Technol., 6 (2016) 1248-1264
[15] N.-Y. Topsøe, Mechanism of the selective catalytic reduction of nitric oxide by ammonia elucidated by in situ on-line fourier transform infrared spectroscopy, Science, 265 (1994) 1217-1219
[16] H.D. Xu, J.X. Liu, Z.H. Zhang, S. Liu, Q.J. Lin, Y. Wang, S. Dai, Y.Q. Chen, Design and synthesis of highly-dispersed WO₃ catalyst with highly effective NH₃-SCR activity for NOx abatement, ACS Catal., 9 (2019) 11557-11562
[17] S. Liu, P. Yao, Q.J. Lin, S.H. Xu, M.M. Pei, J.L. Wang, H.D. Xu, Y.Q. Chen, Optimizing acid promoters of Ce-based NH₃-SCR catalysts for reducing NOx emissions, Catal. Today., 382 (2021) 34-41
[18] S. Liu, P. Yao, M.M. Pei, Q.J. Lin, S.H. Xu, J.L. Wang, H.D. Xu, Y.Q. Chen, Significant differences of NH₃-SCR performances between monoclinic and hexagonal WO₃ on Ce-based catalysts, Environ. Sci.:Nano., 8 (2021) 2988-3000
[19] R. Qu, X. Gao, K. Cen, J.J.A.C.B.E. Li, Relationship between structure and performance of a novel cerium-niobium binary oxide catalyst for selective catalytic reduction of NO with NH₃, Appl. Catal. B:Environ., 142 (2013) 290-297
[20] W. Tan, C. Wang, S. Yu, Y. Li, S. Xie, F. Gao, L. Dong, F. Liu, Revealing the effect of paired redox-acid sites on metal oxide catalysts for efficient NOx removal by NH₃-SCR, J. Hazard. Mater., 416 (2021) 125826
[21] L. Qi, Q. Yu, Y. Dai, C. Tang, L. Liu, H. Zhang, F. Gao, L. Dong, Y. Chen, Influence of cerium precursors on the structure and reducibility of mesoporous CuO-CeO₂ catalysts for CO oxidation, Appl. Catal. B:Environ., 119-120 (2012) 308-320
[22] Z. Wang, Z. Qu, X. Quan, Z. Li, H. Wang, R. Fan, Selective catalytic oxidation of ammonia to nitrogen over CuO-CeO₂ mixed oxides prepared by surfactant-templated method, Appl. Catal. B:Environ., 134-135 (2013) 153-166
[23] L. Kundakovic, M. Flytzani-Stephanopoulos, Cu- and Ag-modified cerium oxide catalysts for methane oxidation, J. Catal., 179 (1998) 203-221
[24] S. Ali, L. Chen, Z. Li, T. Zhang, R. Li, S. Bakhtiar, X. Leng, F. Yuan, X. Niu, Y.J.A.C.B.E. Zhu, Cu_x-Nb_1.1-x (x=0.45, 0.35, 0.25, 0.15) bimetal oxides catalysts for the low temperature selective catalytic reduction of NO with NH₃, Appl. Catal. B:Environ., 236 (2018) 25-35
[25] X.X. Wang, Y. Shi, S.J. Li, W. Li, Promotional synergistic effect of Cu and Nb doping on a novel Cu/Ti-Nb ternary oxide catalyst for the selective catalytic reduction of NOx with NH₃, Appl. Catal. B:Environ., 220 (2018) 234-250
[26] S. Xie, W. Tan, Y. Li, L. Ma, S.N. Ehrlich, J. Deng, P. Xu, F. Gao, L. Dong, F. Liu, Copper single atom-triggered niobia-ceria catalyst for efficient low-temperature reduction of nitrogen oxides, ACS Catal., 12 (2022) 2441-2453
[27] Y. Wang, W. Yi, J. Yu, J. Zeng, H. Chang, Novel methods for assessing the SO₂ poisoning effect and thermal regeneration possibility of MO_x-WO₃/TiO₂ (M=Fe, Mn, Cu, and V) catalysts for NH₃-SCR, Environ. Sci. & Technol., 54 (2020) 12612-12620
[28] X. Yao, L. Zhang, L. Li, L. Liu, Y. Cao, X. Dong, F. Gao, Y. Deng, C. Tang, Z. Chen, L. Dong, Y. Chen, Investigation of the structure, acidity, and catalytic performance of CuO/Ti_0.95Ce_0.05O₂ catalyst for the selective catalytic reduction of NO by NH₃ at low temperature, Appl. Catal. B:Environ., 150-151 (2014) 315-329
[29] A. Martínez-Arias, M. Fernández-García, L.N. Salamanca, R.X. Valenzuela, J.C. Conesa, J. Soria, Structural and redox properties of ceria in alumina-supported ceria catalyst supports, J. Phys. Chem. B, 104 (2000) 4038-4046
[30] G. Zhang, Z. Yan, Three-component nonlinear Schrödinger equations:Modulational instability, Nth-order vector rational and semi-rational rogue waves, and dynamics, Commun. Nonlinear Sci. Numer. Simul., 62 (2018) 117-133
[31] J.H. Kwak, R.G. Tonkyn, D.N. Tran, D. Mei, J.J.A.C. Szanyi, Size-dependent catalytic performance of CuO on gamma-Al₂O₃:NO reduction versus NH₃ oxidation, ACS Catal., 2 (2015) 1432-1440
[32] W. Tan, C. Wang, S. Yu, Y. Li, F.J.J.o.H.M. Liu, Revealing the effect of paired redox-acid sites on metal oxide catalysts for efficient NO removal by NH₃-SCR, J. Hazard. Mater., 416 (2021) 125826
[33] Z.R. Ma, X.D. Wu, Z.C. Si, D.Weng, J. Ma, Impacts of niobia loading on active sites and surface acidity in NbOx/CeO₂-ZrO₂ NH₃-SCR catalysts, Appl. Catal. B:Environ., 179 (2015) 380-394
[34] Z. Chen, C. Fan, L. Pang, S. Ming, P. Liu, T. Li, The influence of phosphorus on the catalytic properties, durability, sulfur resistance and kinetics of Cu-SSZ-13 for NOx reduction by NH₃-SCR, Appl. Catal. B:Environ., 237 (2018) 116-127
[35] A. Aboukais, A. Bennani, C.F. Aissi, M. Guelton, J.C. Vedrine, Microwave frequency behavior of the EPR copper(II) ion pairs spectrum formed in CuCe oxide, Chemistry of Materials, 4 (1992) 977-979
[36] Y. Xiong, L. Li, L. Zhang, Y. Cao, S. Yu, C. Tang, L. Dong, Migration of copper species in Ce_xCu_1-xO₂ catalyst driven by thermal treatment and the effect on CO oxidation, Phys. Chem. Chem. Phys., 19 (2017) 21840-21847
[37] Y. Li, J. Deng, W. Song, J. Liu, Z. Zhao, M. Gao, Y. Wei, L. Zhao, Nature of Cu species in Cu-SAPO-18 catalyst for NH₃-SCR:Combination of experiments and DFT calculations, J. Phys. Chem. C, 120 (2016) 14669-14680
[38] W. Tan, J. Wang, L. Li, A. Liu, G. Song, K. Guo, Y. Luo, F. Liu, F. Gao, L. Dong, Gas phase sulfation of ceria-zirconia solid solutions for generating highly efficient and SO₂ resistant NH₃-SCR catalysts for NO removal, J. Hazard. Mater., 388 (2020) 121729
[39] W.W. Wang, W.Z. Yu, P.P. Du, H. Xu, Z. Jin, R. Si, C. Ma, S. Shi, C.J. Jia, C.H. Yan, Crystal plane effect of ceria on supported copper oxide cluster catalyst for CO oxidation:Importance of metal-support interaction, ACS Catal., 7 (2017) 1313-1329
[40] Q.J. Lin, S. Liu, S.H. Xu, S. Xu, M.M. Pei, P. Yao, H.D. Xu, Y. Dan, Y.Q. Chen, Comprehensive effect of tuning Cu/SAPO-34 crystals using PEG on the enhanced hydrothermal stability for NH₃-SCR. Catal. Sci. Technol., 11 (2021) 7640-7651
[41] L. Chen, J. Li, M. Ge, R. Zhu, Enhanced activity of tungsten modified CeO₂/TiO₂ for selective catalytic reduction of NOx with ammonia, Catal. Today, 153 (2010) 77-83
[42] T. Gu, R. Jin, Y. Liu, H. Liu, X. Weng, Z. Wu, Promoting effect of calcium doping on the performances of MnOx/TiO₂ catalysts for NO reduction with NH₃ at low temperature, Appl. Catal. B:Environ., 129 (2013) 30-38
[43] L. Li, L. Zhang, K. Ma, W. Zou, Y. Cao, Y. Xiong, C. Tang, L. Dong, Ultra-low loading of copper modified TiO₂/CeO₂ catalysts for low-temperature selective catalytic reduction of NO by NH₃, Appl. Catal. B:Environ., 207 (2017) 366-375
[44] X. Yao, R. Zhao, L. Chen, J. Du, C. Tao, F. Yang, L. Dong, Selective catalytic reduction of NOx by NH₃ over CeO₂ supported on TiO₂:Comparison of anatase, brookite, and rutile, Appl. Catal. B:Environ., 208 (2017) 82-93

Insight into the promotional mechanism of Cu modification towards wide-temperature NH₃-SCR performance of NbCe catalyst

Insight into the promotional mechanism of Cu modification towards wide-temperature NH₃-SCR performance of NbCe catalyst

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Yaoyao Peng, Lei Song, Siru Lu, Ziyu Su, Kui Ma, Siyang Tang, Shan Zhong, Hairong Yue, Bin Liang. Superior resistance to alkali metal potassium of vanadium-based NH₃-SCR catalyst promoted by the solid superacid SO₄^2--TiO₂ [J]. Chinese Journal of Chemical Engineering, 2023, 55(3): 246-256.
[2]	Shan Liu, Wenqi Zhong, Xi Chen, Li Sun, Lukuan Yang. Multiobjective economic model predictive control using utopia-tracking for the wet flue gas desulphurization system [J]. Chinese Journal of Chemical Engineering, 2023, 54(2): 343-352.
[3]	An Wang, Zhongyu Hou. Improving the energy efficiency of surface dielectric barrier discharge devices for plasma nitric oxide conversion utilizing active flow control [J]. Chinese Journal of Chemical Engineering, 2023, 53(1): 270-279.
[4]	Heping Xie, Yunpeng Wang, Tao Liu, Yifan Wu, Wenchuan Jiang, Cheng Lan, Zhiyu Zhao, Liangyu Zhu, Dongsheng Yang. Electrochemical CO₂ mineralization for red mud treatment driven by hydrogen-cycled membrane electrolysis [J]. Chinese Journal of Chemical Engineering, 2022, 43(3): 14-23.
[5]	Zhihao Yi, Jie Sun, Jigang Li, Tian Zhou, Shouping Wei, Hongjia Xie, Yulin Yang. High efficient removal of HCN over porous CuO/CeO₂ micro-nano spheres at lower temperature range [J]. Chinese Journal of Chemical Engineering, 2021, 38(10): 155-164.
[6]	Jiangyuan Qu, Nana Qi, Kai Zhang, Lifeng Li, Pengcheng Wang. Wet flue gas desulfurization performance of 330 MW coal-fired power unit based on computational fluid dynamics region identification of flow pattern and transfer process [J]. Chinese Journal of Chemical Engineering, 2021, 29(1): 13-26.
[7]	Tong Tao, Shitao Wang, Yixin Qu, Dapeng Cao. Displacement of shale gas confined in illite shale by flue gas: A molecular simulation study [J]. Chinese Journal of Chemical Engineering, 2021, 29(1): 295-303.
[8]	Baowei Wang, Shumei Yao, Yeping Peng. Simultaneous desulfurization and denitrification of flue gas by pre-ozonation combined with ammonia absorption [J]. Chinese Journal of Chemical Engineering, 2020, 28(9): 2457-2466.
[9]	Jing Gao, Qiang Li, Fuli Liu. Calcium sulfate whisker prepared by flue gas desulfurization gypsum: A physical-chemical coupling production process [J]. Chinese Journal of Chemical Engineering, 2020, 28(8): 2221-2226.
[10]	Lan Li, Xiaoting Huang, Quanda Jiang, Luyue Xia, Jiawei Wang, Ning Ai. New process development and process evaluation for capturing CO₂ in flue gas from power plants using ionic liquid [emim][Tf₂N] [J]. Chinese Journal of Chemical Engineering, 2020, 28(3): 721-732.
[11]	Lukuan Yang, Wenqi Zhong, Li Sun, Xi Chen, Yingjuan Shao. Dynamic optimization oriented modeling and nonlinear model predictive control of the wet limestone FGD system [J]. Chinese Journal of Chemical Engineering, 2020, 28(3): 832-845.
[12]	Dong Sun, Guangzhi Xin, Lu Yao, Lin Yang, Xia Jiang, Wenju Jiang. Manganese leaching in high concentration flue gas desulfurization process with semi-oxidized manganese ore [J]. Chinese Journal of Chemical Engineering, 2020, 28(2): 571-578.
[13]	Lan Yang, Xiang Zhang, Qing Kan, Binran Zhao, Xiaoxun Ma. Effect of gas composition on nitric oxide removal from simulated flue gas with DBD-NPC method [J]. Chinese Journal of Chemical Engineering, 2019, 27(12): 3017-3026.
[14]	Chunlai Liu, Jing Li, Changlin Yang, Zhenheng Diao, Chengxue Wang. A composite absorption liquid for simultaneous desulfurization and denitrification in flue gas [J]. Chinese Journal of Chemical Engineering, 2019, 27(10): 2566-2573.
[15]	Xinglei Zhao, Qian Cui, Baodeng Wang, Xueliang Yan, Surinder Singh, Feng Zhang, Xing Gao, Yonglong Li. Recent progress of amine modified sorbents for capturing CO₂ from flue gas [J]. Chin.J.Chem.Eng., 2018, 26(11): 2292-2302.