Deactivation and Regeneration for the SO2-Poisoning of a Cu-SSZ-13 Catalyst in the NH3-SCR Reaction
Abstract
:1. Introduction
2. Results and Discussion
2.1. X-ray Powder Diffraction
2.2. Nitrogen Physisorption Analyses
2.3. Scanning Electron Microscopy
2.4. X–ray Photoelectron Spectra
2.5. H2-Temperature Programmed Reduction (TPR) Measurements
2.6. NH3-TPD Measurements
2.7. Catalytic Performance
3. Experimental
3.1. Catalyst Preparation
3.2. Catalyst Characterization
3.3. Activity Evaluation
4. Conclusions
Author Contributions
Funding
Conflicts of Interest
References
- Zhao, H.W.; Zhao, Y.N.; Liu, M.K.; Li, X.H.; Ma, Y.H.; Yong, X.; Chen, H.; Li, Y.D. Phosphorus modification to improve the hydrothermal stability of a Cu-SSZ-13 catalyst for selective reduction of NOx with NH3. Appl. Catal. B Environ. 2019, 252, 230–239. [Google Scholar] [CrossRef]
- Ryu, T.; Kim, H.; Hong, S.B. Nature of active sites in Cu-LTA NH3-SCR catalysts: A comparative study with Cu-SSZ-13. Appl. Catal. B Environ. 2019, 245, 513–521. [Google Scholar] [CrossRef]
- Zhao, W.Y.; Li, Z.Q.; Wang, Y.; Fan, R.R.; Zhang, C.; Wang, Y.; Guo, X.; Wang, R.; Zhang, S.L. Ce and Zr Modified WO3-TiO2 Catalysts for Selective Catalytic Reduction of NOx by NH3. Catalysts 2018, 8, 375. [Google Scholar] [CrossRef]
- Nova, I.; Tronconi, E. Urea-SCR Technology for deNOx After Treatment of Diesel Exhausts, 1st ed.; Springer: New York, NY, USA, 2014. [Google Scholar]
- Deka, U.; Lezcano-Gonzalez, I.; Weckhuysen, B.M.; Beale, A.M. Local Environment and Nature of Cu Active Sites in Zeolite-Based Catalysts for the Selective Catalytic Reduction of NOx. ACS Catal. 2013, 3, 413–427. [Google Scholar] [CrossRef]
- Zhao, Y.; Hu, J.; Hua, L.; Shuai, S.; Wang, J. Ammonia Storage and Slip in a Urea Selective Catalytic Reduction Catalyst under Steady and Transient Conditions. Ind. Eng. Chem. Prod. Res. Dev. 2011, 50, 11863–11871. [Google Scholar] [CrossRef]
- Hammershøia, P.S.; Jensen, A.D.; Janssens, T.V.W. Impact of SO2-poisoning over the lifetime of a Cu-CHA catalyst for NH3-SCR. Appl. Catal. B Environ. 2018, 238, 104–110. [Google Scholar] [CrossRef]
- Kumar, A.; Smith, M.A.; Kamasamudram, K.; Currier, N.W.; Yezerets, A. Chemical deSOx: An effective way to recover Cu-zeolite SCR catalysts from sulfur poisoning. Catal. Today 2016, 267, 10–16. [Google Scholar] [CrossRef]
- Cheng, Y.; Montreuil, C.; Cavataio, G.; Lambert, C. Sulfur tolerance and DeSOx studies on diesel SCR catalysts. SAE Int. J. Fuels Lubr. 2008, 1, 471–476. [Google Scholar] [CrossRef]
- Dahlin, S.; Nilsson, M.; Bäckström, D.; Bergman, S.L.; Bengtsson, E.; Bernasek, S.L.; Pettersson, L.J. Multivariate analysis of the effect of biodiesel-derived contaminants on V2O5-WO3/TiO2 SCR catalysts. Appl. Catal. B: Environ. 2016, 183, 377–385. [Google Scholar] [CrossRef]
- Shan, Y.L.; Shi, X.Y.; Yan, Z.D.; Li, J.J.; Yu, Y.B.; He, H. Deactivation of Cu-SSZ-13 in the presence of SO2 during hydrothermal aging. Catal. Today 2019, 320, 84–90. [Google Scholar] [CrossRef]
- Shih, A.J.; Khurana, I.; Li, H.; González, J.; Kumar, A.; Paolucci, C.; Lardinois, T.M.; Jones, C.B.; Caballero, J.D.A.; Kamasamudram, K.; et al. Spectroscopic and kinetic responses of Cu-SSZ-13 to SO2 exposure and implications for NOx selective catalytic reduction. Appl. Catal. A Gen. 2019, 574, 122–131. [Google Scholar] [CrossRef]
- Wijayanti, K.; Leistner, K.; Chand, S.; Kumar, A.; Kamasamudram, K.; Currier, N.W.; Yezerets, A.; Olsson, L. Deactivation of Cu-SSZ-13 by SO2 exposure under SCR conditions. Catal. Sci. Technol. 2016, 6, 2565–2579. [Google Scholar] [CrossRef]
- Kumar, A.; Smith, M.A.; Kamasamudram, K.; Currier, N.W.; An, H.; Yezerets, A. Impact of different forms of feed sulfur on small-pore Cu-zeolite SCR catalyst. Catal. Today 2014, 231, 75–82. [Google Scholar] [CrossRef]
- Zhang, L.; Wang, D.; Liu, Y.; Kamasamudram, K.; Li, J.; Epling, W. SO2 poisoning impact on the NH3-SCR reaction over a commercial Cu-SAPO-34 SCR catalyst. Appl. Catal. B Environ. 2014, 156–157, 371–377. [Google Scholar] [CrossRef]
- Sappok, A.G.; Wong, V.W. Physical Characterization of Ash Species in Diesel Exhaust Entering After Treatment Systems; SAE International 2007-01-0318; Massachusetts Institute of Technology, Sloan Automotive Laboratory: Cambridge, MA, USA, 2007. [Google Scholar]
- Hammershøi, P.S.; Jangjou, Y.; Epling, W.S.; Jensen, A.D.; Janssens, T.V.W. Reversible and irreversible deactivation of Cu-CHA NH3-SCR catalysts by SO2 and SO3. Appl. Catal. B Environ. 2018, 226, 38–45. [Google Scholar] [CrossRef]
- Shen, M.Q.; Zhang, Y.; Wang, J.Q.; Wang, C.; Wang, J. Nature of SO3 poisoning on Cu/SAPO-34 SCR catalysts. J. Catal. 2018, 358, 277–286. [Google Scholar] [CrossRef]
- Fan, C.; Chen, Z.; Pang, L.; Ming, S.J.; Dong, C.Y.; Albert, K.B.; Liu, P.; Wang, J.Y.; Zhu, D.J.; Chen, H.P.; et al. Steam and alkali resistant Cu-SSZ-13 catalyst for the selective catalytic reduction of NOx in diesel exhaust. Chem. Eng. J. 2018, 334, 344–354. [Google Scholar] [CrossRef]
- Liu, X.J.; Li, Y.H.; Zhang, R.R. Ammonia selective catalytic reduction of NO over Ce–Fe/Cu–SSZ-13 catalysts. RSC Adv. 2015, 5, 85453–85459. [Google Scholar] [CrossRef]
- Chen, B.H.; Xu, R.N.; Zhang, R.D.; Liu, N. Economical Way to Synthesize SSZ-13 with Abundant Ion-Exchanged Cu+ for an Extraordinary Performance in Selective Catalytic Reduction (SCR) of NOx by Ammonia. Environ. Sci. Technol. 2014, 48, 13909–13916. [Google Scholar] [CrossRef]
- Su, W.K.; Li, Z.G.; Peng, Y.; Li, J.H. Correlation of the changes in the framework and active Cu sites for typical Cu/CHA zeolites (SSZ-13 and SAPO-34) during hydrothermal aging. Phys. Chem. Chem. Phys. 2015, 17, 29142–29149. [Google Scholar] [CrossRef]
- Ma, L.; Cheng, Y.S.; Cavataio, G.; McCabe, R.W.; Fu, L.X.; Li, J.H. Characterization of commercial Cu-SSZ-13 and Cu-SAPO-34 catalysts with hydrothermal treatment for NH3-SCR of NOx in diesel exhaust. Chem. Eng. J. 2013, 225, 323–330. [Google Scholar] [CrossRef]
- Wijayanti, K.; Andonova, S.; Kumar, A.; Li, J.; Kamasamudram, K.; Currier, N.W.; Yezerets, A.; Olsson, L. Impact of sulfur oxide on NH3-SCR over Cu-SAPO-34. Appl. Catal. B Environ. 2015, 166–167, 568–579. [Google Scholar] [CrossRef]
- Shen, M.; Wen, H.; Hao, T.; Yu, T.; Fan, D.; Wang, J.; Li, W.; Wang, J. Deactivation mechanism of SO2 on Cu/SAPO-34 NH3-SCR catalysts: Structure and active Cu2+. Catal. Sci. Technol. 2015, 5, 1741–1749. [Google Scholar] [CrossRef]
- Wijayanti, K.; Xie, K.P.; Kumar, A.; Kamasamudram, K.; Olsson, L. Effect of gas compositions on SO2 poisoning over Cu/SSZ-13 used for NH3-SCR. Appl. Catal. B Environ. 2017, 219, 142–154. [Google Scholar] [CrossRef]
- Wang, C.; Wang, J.; Wang, J.Q.; Yu, T.; Shen, M.Q.; Wang, W.L.; Li, W. The effect of sulfate species on the activity of NH3-SCR over Cu/SAPO-34. Appl. Catal. B Environ. 2017, 204, 239–249. [Google Scholar] [CrossRef]
- Shen, M.Q.; Li, X.H.; Wang, J.Q.; Wang, C.; Wang, J. Nature Identification of Cu Active Sites in Sulfur-Fouled Cu/SAPO-34 Regeneration. Ind. Eng. Chem. Res. 2018, 57, 3501–3509. [Google Scholar] [CrossRef]
- Lin, Q.J.; Feng, X.; Zhang, H.L.; Lin, C.L.; Liu, S.; Xu, H.D.; Chen, Y.Q. Hydrothermal deactivation over CuFe/BEA for NH3-SCR. J. Ind. Eng. Chem. 2018, 65, 40–50. [Google Scholar] [CrossRef]
- Li, Y.H.; Deng, J.L.; Song, W.Y.; Liu, J.; Zhao, Z.; Gao, M.L.; Wei, Y.C.; Zhao, L. Nature of Cu Species in Cu–SAPO-18 Catalyst for NH3–SCR: Combination of Experiments and DFT Calculations. J. Phys. Chem. C 2016, 120, 14669–14680. [Google Scholar] [CrossRef]
- Hajjar, R.; Millot, Y.; Man, P.P.; Che, M.; Dzwigaj, S. Two kinds of framework Al sites studied in BEA zeolite by X-ray diffraction, Fourier transform infrared spectroscopy, NMR techniques, and V probe. J. Phys. Chem. C 2008, 112, 20167–20175. [Google Scholar] [CrossRef]
- Muzio, L.; Bogseth, S.; Himes, R.; Chien, Y.C.; Dunn-Rankin, D. Ammonium bisulfate formation and reduced load SCR operation. Fuel 2017, 206, 180–189. [Google Scholar] [CrossRef]
- Li, J.H.; Peng, Y.; Chang, H.Z.; Li, X.; Crittenden, J.C.; Hao, J.M. Chemical poison and regeneration of SCR catalysts for NOx removal from stationary sources. Front. Environ. Sci. Eng. 2016, 10, 413–427. [Google Scholar] [CrossRef]
- Xu, L.W.; Wang, C.Z.; Chang, H.A.; Wu, Q.R.; Zhang, T.; Li, J.H. New Insight into SO2 Poisoning and Regeneration of CeO2−WO3/TiO2 and V2O5−WO3/TiO2 Catalysts for Low-Temperature NH3−SCR. Environ. Sci. Technol. 2018, 52, 7064–7071. [Google Scholar] [CrossRef] [PubMed]
- Yang, G.P.; Du, X.S.; Ran, J.Y.; Wang, X.M.; Chen, Y.R.; Zhang, L. Understanding SO2 Poisoning over Different Copper Species of Cu-SAPO-34 Catalyst: A Periodic DFT Study. J. Phys. Chem. C 2018, 122, 21468–21477. [Google Scholar] [CrossRef]
- Fan, D.Q.; Wang, J.; Yu, T.; Wang, J.Q.; Hu, X.Q.; Shen, M.Q. Catalytic deactivation mechanism research over Cu/SAPO-34 catalysts for NH3-SCR (I): The impact of hydrothermal aging time. Chem. Eng. J. 2018, 176, 285–293. [Google Scholar] [CrossRef]
- Gao, F.; Walter, E.D.; Washton, N.M.; Szanyi, J.; Peden, C.H.F. Synthesis and Evaluation of Cu-SAPO-34 Catalysts for Ammonia Selective Catalytic Reduction. 1. Aqueous Solution Ion Exchange. ACS Catal. 2013, 3, 2083–2093. [Google Scholar] [CrossRef]
- Chen, Z.; Fan, C.; Pang, L.; Ming, S.J.; Liu, P.; Li, T. 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. 2018, 237, 116–127. [Google Scholar] [CrossRef]
- Ming, S.J.; Chen, Z.; Fan, C.; Pang, L.; Guo, W.; Albert, K.B.; Liu, P.; Li, T. The effect of copper loading and silicon content on catalytic activity and hydrothermal stability of Cu-SAPO-18 catalyst for NH3-SCR. Appl. Catal. A Gen. 2018, 559, 47–56. [Google Scholar] [CrossRef]
- Luo, J.Y.; Gao, F.; Kamasamudram, K.; Currier, N.; Peden, C.H.F.; Yezerets, A. New insights into Cu/SSZ-13 SCR catalyst acidity. Part I: Nature of acidic sites probed by NH3 titration. J. Catal. 2017, 348, 291–299. [Google Scholar] [CrossRef]
- Su, W.K.; Li, Z.G.; Zhang, Y.N.; Meng, C.C.; Li, J.H. Identification of sulfate species and their influence on SCR performance of Cu/CHA catalyst. Catal. Sci. Technol. 2017, 7, 1523–1528. [Google Scholar] [CrossRef]
Samples | SBET (m2/g) a | ΔS (%) b | VT (mL/g) c | Pore Size (nm) d |
---|---|---|---|---|
F-Cu | 760 | - | 0.2747 | 0.6044 |
S-Cu | 673 | 11.4 | 0.2478 | 0.6430 |
R-450 | 706 | 7.1 | 0.2593 | 0.6529 |
R-500 | 718 | 5.5 | 0.2630 | 0.6173 |
R-550 | 704 | 7.4 | 0.2571 | 0.5839 |
R-600 | 715 | 5.9 | 0.2619 | 0.6539 |
R-650 | 726 | 4.5 | 0.2704 | 0.5775 |
R-700 | 726 | 4.5 | 0.2692 | 0.6640 |
Samples | Atomic Ratio of Cusur (%) | Integral Areas | Cu+/Cu2+ | ||||
---|---|---|---|---|---|---|---|
Cu2+ | Cu2+ in CuO | Dispersed Cu2+ Ions | Cu+ | S | |||
F-Cu | 0.60 | 1649.8 | 577.3 | 694.0 | 2570.1 | 0 | 0.89 |
S-Cu | 0.31 | 859.4 | 334.8 | 263.4 | 1026.1 | 1613.2 | 0.70 |
R-450 | 0.34 | 1162.8 | 392.4 | 481.7 | 887.4 | 1371.8 | 0.43 |
R-500 | 0.33 | 700.4 | 0.2 | 238.2 | 439.7 | 1242.2 | 0.47 |
R-550 | 0.40 | 1277.0 | 162.2 | 183.2 | 958.3 | 1075.3 | 0.59 |
R-600 | 0.36 | 1071.2 | 254.4 | 373.3 | 1402.9 | 843.1 | 0.82 |
R-650 | 0.41 | 1147.9 | 207.0 | 207.0 | 1332.1 | 522.8 | 0.84 |
R-700 | 0.39 | 821.6 | 261.7 | 380.4 | 971.5 | 0 | 0.66 |
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Wang, Y.; Li, Z.; Fan, R.; Guo, X.; Zhang, C.; Wang, Y.; Ding, Z.; Wang, R.; Liu, W. Deactivation and Regeneration for the SO2-Poisoning of a Cu-SSZ-13 Catalyst in the NH3-SCR Reaction. Catalysts 2019, 9, 797. https://doi.org/10.3390/catal9100797
Wang Y, Li Z, Fan R, Guo X, Zhang C, Wang Y, Ding Z, Wang R, Liu W. Deactivation and Regeneration for the SO2-Poisoning of a Cu-SSZ-13 Catalyst in the NH3-SCR Reaction. Catalysts. 2019; 9(10):797. https://doi.org/10.3390/catal9100797
Chicago/Turabian StyleWang, Yan, Zhaoqiang Li, Rongrong Fan, Xin Guo, Cheng Zhang, Yu Wang, Zhiyong Ding, Rong Wang, and Wei Liu. 2019. "Deactivation and Regeneration for the SO2-Poisoning of a Cu-SSZ-13 Catalyst in the NH3-SCR Reaction" Catalysts 9, no. 10: 797. https://doi.org/10.3390/catal9100797