skip to main content

Low Temperature Selective Catalytic Reduction (SCR) of NOx Emissions by Mn-doped Cu/Al2O3 Catalysts

1Department of Chemical Engineering & Technology, Indian Institute of Technology (Banaras Hindu University), Varanasi, 221 005, India

2Department of Civil Engineering, Indian Institute of Technology (Banaras Hindu University), Varanasi, 221 005, India

Received: 5 Jan 2017; Revised: 20 May 2017; Accepted: 20 May 2017; Published: 1 Dec 2017; Available online: 27 Oct 2017.
Open Access Copyright (c) 2017 by Authors, Published by BCREC Group under

Citation Format:
Cover Image

The 15 mol% Cu/Al2O3 catalysts with different Mn doping (0.5, 1.0, 1.5, mol%) were prepared using PEG-300 surfactant following evaporation-induced self-assembly (EISA) method. Calcination of precursors were performed in flowing air conditions at 500 ºC. The catalysts were characterized by X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscope Energy Dispersive X-Ray (SEM-EDX), Fourier Transform Infra Red (FTIR), and N2 physisorption. The catalysts activities were evaluated for H2 assisted LPG-SCR of NO in a packed bed tubular flow reactor with 200 mg catalyst under the following conditions: 500 ppm NO, 8 % O2, 1000 ppm LPG, 1 % H2 in Ar with total flow rate of 100 mL/min. Characterization of the catalysts revealed that surface area of 45.6-50.3 m2/g, narrow pore size distribution (1-2 nm), nano-size crystallites, Cu2+ and Mn2+ phases were principal active components. Hydrogen enhanced significantly selective reduction of NO to N2 with LPG over 1.0 mol % Mn-Cu/Al2O3 giving 95.56 % NO reduction at 150 ºC. It was proposed that the synergistic interaction between H2 and LPG substantially widened the NO reduction temperature window and a considerable increase in both activity and selectivity. Negligible loss of catalyst activity was observed for the 50 h of stream on run experiment at 150 ºC. The narrow pore size distribution, thermal stability of the catalyst and optimum Mn doping ensures good dispersion of Cu and Mn over Al2O3 that improved NO reduction in H2-LPG SCR system. 

Fulltext View|Download
Keywords: Mn-doped Cu/Al2O3; Selective Catalytic Reduction; SCR; NOx; H2-LPG; de-NOx

Article Metrics:

  1. Li, Y., Su, J., Ma J., Yu, F., Chen J., Li R. (2015). Novel Straight Synthesis of Super- Microporous Cu/Al2O3 Catalyst with High CH4-SCR-NO Activity. Catalysis Communications, 65: 6-9
  2. Hu, H., Cai, S., Li, H., Huang, L., Shi, L., Zhang, D. (2015). In Situ DRIFTs Investigation of the Low-Temperature Reaction Mechanism over Mn-Doped Co3O4 for the Selective Catalytic Reduction of NOx with NH3. Journal of Physical Chemistry C, 119: 22924-22933
  3. Chen, Y., Borken-Kleefeld, J. (2016). NOx Emissions from Diesel Passenger Cars Worsen with Age. Environmental Science & Technology, 50: 3327-3332
  4. Janssens, T.V.W., Falsig, H., Lundegaard, L.F., Vennestrøm, P.N.R., Rasmussen, S.B., Moses, P.G., Giordanino, F., Borfecchia, E., Lomachenko, K.A., Lamberti C., Bordiga, S., Godiksen, A., Mossin, S., Beato, P. (2015). A Consistent Reaction Scheme for the Selective Catalytic Reduction of Nitrogen Oxides with Ammonia. ACS Catalysis, 5: 2832-2845
  5. Marberger, A., Elsener, M., Ferri, D., Sagar, A., Schermanz, K., Krocher, O. (2015). Generation of NH3 Selective Catalytic Reduction Active Catalysts from Decomposition of Supported FeVO4. ACS Catalysis, 5: 4180-4188
  6. Stere, C.E., Adress, W., Burch, R., Chansai, S., Goguet, A., Graham, W.G., De Rosa, F., Palma, V., Hardacre, C. (2014). Ambient Temperature Hydrocarbon Selective Catalytic Reduction of NOx Using Atmospheric Pressure Nonthermal Plasma Activation of a Ag/Al2O3 Catalyst. ACS Catalysis, 4: 666-673
  7. Kong, M., Liu, Q., Zhu, B., Yang, J., Li, L., Zhou, Q., Ren, S. (2015). Synergy of KCl and Hgel on Selective Catalytic Reduction of NO with NH3 over V2O5-WO3/TiO2 Catalysts. Chemical Engineering Journal, 264: 815-823
  8. Song, Z., Zhang, Q., Ning, P., Liu, X., Zhang, J., Wang, Y., Xu, L., Huang, Z. (2016). Effect of Copper Precursors on the Catalytic Activity of Cu/ZSM-5 Catalysts for Selective Catalytic Reduction of NO by NH3. Research on Chemical Intermediates, 42: 7429-7445
  9. Pia, M., Grossale, A., Nova, I., Tronconi, E., Jirglova, H., Sobalik, Z. (2012). FTIR In Situ Mechanistic Study of the NH3 NO/NO2 “Fast SCR” Reaction over a Commercial Fe-ZSM-5 Catalyst. Catalysis Today, 184: 107-114
  10. Inceesungvorn, B., López-Castro, J., Calvino, J.J., Bernal, S., Meunier, F.C., Hardacre, C., Griffin, K. and Delgado, J.J. (2011). Nano-Structural Investigation of Ag/Al2O3 Catalyst for Selective Removal of O2 with Excess H2 in the Presence of C2H4. Applied Catalysis A: General, 391: 187-193
  11. Kannisto, H., Ingelsten, H.H., Skoglundh, M. (2009). Aspects of the Role of Hydrogen in H2-Assisted HC-SCR over Ag-Al2O3. Topics in Catalysis, 52: 1817-1820
  12. More, P.M., Nguyen, D.L., Granger, P., Dujardin, C., Dongare, M.K., Umbarkar, S.B. (2015). Activation by Pretreatment of Ag-Au/Al2O3 Bimetallic Catalyst to Improve Low Temperature HC-SCR of NOx for Lean Burn Engine Exhaust. Applied Catalysis B: Environmental, 174-175: 145-156
  13. Gálvez, M.E., Ascaso, S., Moliner R., Lázaro, M.J. (2013). Me (Cu,Co,V)-KAl2O3 Supported Catalysts for the Simultaneous Removal of Soot and Nitrogen Oxides from Diesel Exhausts. Chemical Engineering Sciences, 87: 75-90
  14. Jabłońska, M., Palkovits, R. (2016). Nitrogen Oxide Removal over Hydrotalcite-Derived Mixed Metal Oxides. Catalysis Science & Technology, 6: 49-72
  15. Li, B., Ren, Z., Ma, Z., Huang, X., Liu, F., Zhang, X., Yang, H. (2016). Mechanistic Study of Selective Catalytic Reduction of NO by NH3 over CuO-CeO2 in the Presence of SO2. Catalysis Science & Technology, 6: 1719-1725
  16. Yu, Y., Miao, J., Wang, J., He, C., Chen, J. (2017). Facile Synthesis of CuSO4/TiO2 Catalysts with Superior Activity and SO2 Tolerance for NH3-SCR: Physicochemical Properties and Reaction Mechanism. Catalysis Science & Technology, 7: 1590-1601
  17. Leistner, K., Mihai, O., Wijayanti, K., Kumar, A., Kamasamudram, K., Currier, N.W., Yezerets, A., Olsson, L. (2015). Comparison of Cu/BEA, Cu/SSZ-13 and Cu/SAPO-34 for Ammonia-SCR Reactions. Catalysis Today, 258: 49-55
  18. Turek, W., Plis, A., Costa, P.Da, Krzton, A. (2010) Investigation of Oxide Catalysts Activity in the NOx Neutralisation with Organic Reductants. Applied Surface Science, 256: 5572-5575
  19. Swallow, D. Johnson Matthey Public Limited Company, LONDON. Dec. 27, 2012. Control of Emissions. US Patent Application no. US 2012/0324867 A1
  20. Chmielarz, L., Jabłonska, M. (2015). Advances in Selective Catalytic Oxidation of Ammonia to Dinitrogen: A Review. RSC Advances, 5: 43408-43431
  21. Jeon, J., Lee, J.T., Park, S. (2016). Nitrogen Compounds (NO, NO2, N2O, and NH3) in NOx Emissions from Commercial EURO VI Type Heavy-Duty Diesel Engines with a Urea-Selective Catalytic Reduction System. Energy & Fuels, 30: 6828-6934
  22. Parvulescu, V.I., Grange, P., Delmon, B. (1998). Catalytic Removal of NO. Catalysis Today, 46: 233-316
  23. Kumar, P.A., Reddy, M.P., Ju, L.K., Sook, B.H., Phil, H.H. (2008). Low Temperature Propylene SCR of NO by Copper Alumina Catalyst. Journal of Molecular Catalysis A Chemical, 291: 66-74
  24. Singh P.S., Prasad R., Pandey J. (2015). Development of Green Ag/Al2O3 Catalyst by Mechanochemical Method for Low Temperature H2-LPG-SCR of Lean NOx. International Journal of Advance Research in Science and Engineering, 4: 792-801
  25. Li, Y., Su, J., Ma, J., Yu, F., Chen, J., Li, R. (2015). Novel Straight Synthesis of Super-Microporous Cu/Al2O3 Catalyst with High CH4-SCR-NO Activity. Catalysis Communications, 65: 6-9
  26. Hu, H., Cai, S., Li, H., Huang, L., Shiand, L., Zhang, D. (2015). In Situ DRIFTs Investigation of the Low-Temperature Reaction Mechanism over Mn-Doped Co3O4 for the Selective Catalytic Reduction of NOx with NH3. Journal of Physical Chemistry C, 119: 22924-22933
  27. Lee, T., Bai, H. (2016). Low Temperature Selective Catalytic Reduction of NO x with NH3 over Mn-based Catalyst: A Review. AIMS Environmental Science, 3: 261-289
  28. Qi, G., Yang, R.T., Chang, R. (2004). MnOx-CeO2 Mixed Oxides Prepared by Co-precipitation for Selective Catalytic Reduction of NO with NH3 at Low Temperatures. Applied Catalysis B: Environmental, 51: 93-106
  29. Zhan, S., Qiu, M., Yang, S., Zhu, D., Yua, H., Li,Y. (2014). Facile Preparation of MnO2 Doped Fe2O3 Hollow Nanofibers for Low Temperature SCR of NO with NH3. Journal of Materials Chemistry A, 2: 20486-20493
  30. Weng, X., Zhang, J., Wu, Z., Liu, Y. (2011). Continuous Hydrothermal Flow Syntheses of Transition Metal Oxide Doped CexTiO2 Nanopowders for Catalytic Oxidation of Toluene. Catalysis Today, 175: 386-392
  31. Lv, G., Bin, F., Song, C., Wang, K., Song, J. (2013). Promoting Effect of Zirconium Doping on Mn/ZSM-5 for the Selective Catalytic Reduction of NO with NH3. Fuel, 107: 217-224
  32. Jampaiah, D., Ippolito, S.J., Sabri, Y.M., Reddy, B.M., Bhargava, S.K. (2015). Highly Efficient Nanosized Mn and Fe Codoped Ceria-Based Solid Solutions for Elemental Mercury Removal at Low Flue Gas Temperatures. Catalysis Science and Technology, 5: 2913-2924
  33. Meng, D., Zhan, W., Guo, Y., Guo, Y., Wang, L., Lu, G. (2015). A Highly Effective Catalyst of Sm-MnOx for the NH3-SCR of NOx at Low Temperature: Promotional Role of Sm and Its Catalytic Performance. ACS Catalysis, 5: 5973-5983
  34. Vila, F., López Granados, M., Ojeda, M., Fierro, J.L.G., Mariscal, R. (2012). Glycerol Hydrogenolysis to 1,2-propanediol with Cu/g-Al2O3: Effect of the Activation Process. Catalysis Today, 187: 122-128
  35. Li, H., Jiang, X., Huang W., Zheng, X. (2009). Nonthermal-Plasma-Assisted Selective Catalytic Reaction of NO by CH4 over CuO/TiO2/ γ-Al2O3 Catalyst. Energy & Fuel, 23: 2967-2973
  36. Chen, D., Cen, C., Feng, I., Yao, C., Li, W., Tian, S., Xiong, Y. (2016). Co‐catalytic Effect of Al‐Cr Pillared Montmorillonite as A New SCR Catalytic Support. Journal of Chemical Technology & Biotechnology, 91: 2842-2851
  37. Zhang, Y., Zheng, Y., Wang, X., Lu, X. (2015). Preparation of Mn–FeOx/CNTs Catalysts by Redox Co-precipitation and Application in Low-Temperature NO Reduction with NH3. Catalysis Communications, 62: 57-61
  38. Mejía-centeno, I., Castillo, S., Camposeco, R., Marín, J., García, L.A., Fuentes, G.A. (2015). Activity and Selectivity of V2O5/H2Ti3O7, V2O5-WO3/H2Ti3O7 and Al2O3/H2Ti3O7 Model Catalysts during the SCR-NO with NH3. Chemical Engineering Journal, 264: 873-885
  39. Zhong, L., Zhong, Q., Cai, W., Zhang, S., Yu, Y., Ou, M., Song, F. (2016). Promotional Effect and Mechanism Study of Nonmetal-Doped Cr/CexTi1-xO2 for NO Oxidation: Tuning O2 Activation and NO Adsorption Simultaneously. RSC Advances, 6: 21056-21066
  40. Li, Y., Li, Y., Wan, Y., Zhan, S., Tian, Y. (2016). Structure-Performance Relationships of MnO2 Nanocatalyst for the Low-Temperature SCR Removal of NOx under Ammonia. RSC Advances, 6: 54926-54937
  41. Liu, H., Lin, Y., Ma, Z. (2016). Rh2O3/ Mesoporous MOx-Al2O3 (M = Mn, Fe, Co, Ni, Cu, Ba) Catalysts: Synthesis, Characterization and Catalytic Applications. Chinese Journal of Catalysis, 37: 73-82
  42. Richter, M., Bentrup, U., Eckelt, R., Schneider, M., Pohl, M., Fricke, R. (2004). The Effect of Hydrogen on the Selective Catalytic Reduction of NO in Excess Oxygen over Ag/Al2O3. Applied Catalysis B: Environmental, 51: 261
  43. Shimizu, K., Shibata, J., Satsuma, A. (2006). Kinetic and In Situ Infrared Studies on SCR of NO with Propane by Silver–Alumina Catalyst: Role of H2 on O2 Activation and Retardation of Nitrate Poisoning. Journal of Catalysis, 239: 402-409
  44. Bentrup, U., Richter, M., Fricke R. (2005). Effect of H2 Admixture on the Adsorption of NO, NO2 and Propane at Ag/Al2O3 Catalyst as Examined by In Situ FTIR. Applied Catalysis B: Environmental, 55: 213-220

Last update: 2021-07-29 12:26:30

No citation recorded.

Last update: 2021-07-29 12:26:30

No citation recorded.