Abstract
An investigation on the catalytic performance of various transition-metal ions-exchanged clinoptilolite zeolites in the propane selective catalytic reduction process of NOx (NO+NO2) is reported for the first time. The metallic ions include Zn2+, Fe2+, Cu2+ and Mn2+. The catalytic performance of these materials was compared with the proton form and natural clinoptilolite zeolites. Compared with the raw and H-form clinoptilolite, the ion-exchanged zeolites shift the temperature corresponding to the maximum conversion around 50 °C towards lower temperatures, irrespective of the type of used transition-metal used. The maximum conversion is substantially enhanced especially in the case of Cu2+ and Mn2+-exchanged zeolite. The enhanced activity is attributed to the creation of strong acidic sites, redox centers, enhanced specific surface area and residual extra framework Fe species. Ion-exchange with transition metals results in a distinct effect on the reduction of the CO concentration in the product gas stream. Cu2+ exchanged clinoptilolite resulted in the smallest outlet concentration of CO, i. e. about 81 % reduction with respect to the protonated zeolite form.
Acknowledgements
The authors express their gratitude to the Iran National Science Foundation for the complete funding of the present work under the grant Nr. 89000540.
References
Azar, R. P., and C. Falamaki. 2012. “Removal of Aqueous Fe2+ Using Mno2–Clinoptilolite in a Batch Slurry Reactor: Catalyst Synthesis, Characterization and Modeling of Catalytic Behavior.” Journal of Industrial and Engineering Chemistry 18: 737–743.10.1016/j.jiec.2011.11.112Search in Google Scholar
Baek, S.-C., Y.-J. Lee, K.-W. Jun, and S. B. Hong. 2009. “Influence of Catalytic Functionalities of Zeolites on Product Selectivities in Methanol Conversion.” Energy & Fuels 23: 593–598.10.1021/ef800736nSearch in Google Scholar
Čapek, L., J. Dědeček, and B. Wichterlová. 2004. “Co-Beta Zeolite Highly Active in Propane–Scr-Nox in the Presence of Water Vapor: Effect of Zeolite Preparation and Al Distribution in the Framework.” Journal of Catalysis 227: 352–366.10.1016/j.jcat.2004.08.001Search in Google Scholar
Chen, H.-Y., X. Wang, and W. M. H. Sachtler. 2000. “Reduction of Nox over Various Fe/Zeolite Catalysts.” Applied Catalysis A: General 194–195: 159–168.10.1016/S0926-860X(99)00364-6Search in Google Scholar
Elaiopoulos, K., T. Perraki, and E. Grigoropoulou. 2008. “Mineralogical Study and Porosimetry Measurements of Zeolites from Scaloma Area, Thrace, Greece.” Microporous and Mesoporous Materials 112: 441–449.10.1016/j.micromeso.2007.10.021Search in Google Scholar
Feeley, J.S., M. Deeba, R.J. Farrauto, G. Beri, and A. Haynes. 1995. “Lean Nox Reduction with Hydrocarbons over Ga/S-Zrox and S-Gazr/Zeolite Catalysts.” Applied Catalysis B: Environmental 6: 79–96.10.1016/0926-3373(95)00004-6Search in Google Scholar
Ghasemian, N., C. Falamaki, and M. Kalbasi. 2014a. “Clinoptilolite Zeolite as a Potential Catalyst for Propane-Scr-Nox: Performance Investigation and Kinetic Analysis.” Chemical Engineering Journal 236: 464–470.10.1016/j.cej.2013.10.061Search in Google Scholar
Ghasemian, N., C. Falamaki, M. Kalbasi, and M. Khosravi. 2014b. “Enhancement of the Catalytic Performance of H-Clinoptilolite in Propane–Scr–Nox Process through Controlled Dealumination.” Chemical Engineering Journal 252: 112–119.10.1016/j.cej.2014.04.039Search in Google Scholar
Ghasemian, N., and H. Nourmoradi. 2016. “Experimental Study and Mathematical Modeling of Propane-SCR-Nox Using Group Method of Data Handling and Artificial Neural Network.” International Journal of Chemical Reactor Engineering 14: 559–569.10.1515/ijcre-2015-0159Search in Google Scholar
Katada, N., K. Suzuki, T. Noda, M. B. Park, H.-K. Min, S. B. Hong, and M. Niwa. 2010. “Ammonia IRMS-TPD Characterization of Brønsted Acid Sites in Medium-Pore Zeolites with Different Framework Topologies.” Topics in Catalysis 53: 664–671.10.1007/s11244-010-9503-ySearch in Google Scholar
Kieger, S., G. Delahay, and B. Coq. 2000. “Influence of Co-Cations in the Selective Catalytic Reduction of NO by NH3 over Copper Exchanged Faujasite Zeolites.” Applied Catalysis B: Environmental 25: 1–9.10.1016/S0926-3373(99)00112-5Search in Google Scholar
Kumar, M.S., M. Schwidder, W. Grünert, and A. Brückner. 2004. “On the Nature of Different Iron Sites and Their Catalytic Role in Fe-ZSM-5 Denox Catalysts: New Insights by a Combined EPR and UV/VIS Spectroscopic Approach.” Journal of Catalysis 227: 384–397.10.1016/j.jcat.2004.08.003Search in Google Scholar
Li, L., F. Zhang, N. Guan, M. Richter, and R. Fricke. 2007. “Selective Catalytic Reduction of NO by Propane in Excess Oxygen over Ircu-ZSM-5 Catalyst.” Catalysis Communications 8: 583–588.10.1016/j.catcom.2006.08.013Search in Google Scholar
Li, Y. J., and J. N. Armor. 1994. “Selective Reduction of Nox by Methane on Co-Ferrierites.” Journal of Catalysis 150: 376–387.10.1006/jcat.1994.1356Search in Google Scholar
Li, Y. J., T. L. Slager, and J. N. Armor. 1994. “Selective Reduction of Nox by Methane on Co-Ferrierites.” Journal of Catalysis 150: 388–399.10.1006/jcat.1994.1357Search in Google Scholar
Li, Z., and M. Flytzani-Stephanopoulos. 1997. “Selective Catalytic Reduction of Nitric Oxide by Methane over Cerium and Silver Ion-Exchanged ZSM-5 Zeolites.” Applied Catalysis A: General 165: 15–34.10.1016/S0926-860X(97)00187-7Search in Google Scholar
Long, R. Q., and R. T. Yang. 2002. “Selective Catalytic Reduction of NO with Ammonia over Fe3+-Exchanged Mordenite (Fe–Mor): Catalytic Performance, Characterization, and Mechanistic Study.” Journal of Catalysis 207: 274–285.10.1006/jcat.2002.3521Search in Google Scholar
Mirodatos, C., and D. Barthomeuf. 1981. “Superacid Sites in Zeolites. Journal of the Chemical Society.” Chemical Communications 1: 39–40.10.1039/c39810000039Search in Google Scholar
Mishima, H., K. Hashmoto, T. Ono, and M. Anpo. 1998. “Selective Catalytic Reduction of NO with NH3 over Natural Zeolites and Its Application to Stationary Diesel Engine Exhaust.” Applied Catalysis B: Environmental 19: 119–126.10.1016/S0926-3373(98)00071-XSearch in Google Scholar
Miyadera, T. 1993. “Alumina-Supported Silver Catalysts for the Selective Reduction of Nitric Oxide with Propene and Oxygen-Containing Organic Compounds.” Applied Catalysis B: Environmental 2: 199–205.10.1016/0926-3373(93)80048-ISearch in Google Scholar
Moreno-Tost, R., J. Santamarı́a-González, E. Rodrı́guez-Castellón, A. Jiménez-López, M. A. Autié, E. González, M. C. Glacial, and C. D. Pozas. 2004. “Selective Catalytic Reduction of Nitric Oxide by Ammonia over Cu-Exchanged Cuban Natural Zeolites.” Applied Catalysis B: Environmental 50: 279–288.10.1016/j.apcatb.2004.01.019Search in Google Scholar
Mosqueda-Jiménez, B. I., A. Jentys, K. Seshan, and J. A. Lercher. 2003. “On the Surface Reactions during NO Reduction with Propene and Propane on Ni-Exchanged Mordenite.” Applied Catalysis B: Environmental 46: 189–202.10.1016/S0926-3373(03)00212-1Search in Google Scholar
Ohtsuka, H., and T. Tabata. 1999. “Effect of Water Vapor on the Deactivation of Pd-Zeolite Catalysts for Selective Catalytic Reduction of Nitrogen Monoxide by Methane.” Applied Catalysis B: Environmental 21: 133–139.10.1016/S0926-3373(99)00014-4Search in Google Scholar
Omidvarborna, H., A. Kumar, and D.-S. Kim. 2015. “Nox Emissions from Low-Temperature Combustion of Biodiesel Made of Various Feedstocks and Blends.” Fuel Processing Technology 140: 113–118.10.1016/j.fuproc.2015.08.031Search in Google Scholar
Royaee, S. J., C. Falamaki, M. Sohrabi, and S. S. Ashraf Talesh. 2008. “A New Langmuir–Hinshelwood Mechanism for the Methanol to Dimethylether Dehydration Reaction over Clinoptilolite-Zeolite Catalyst.” Applied Catalysis A: General 338: 114–120.10.1016/j.apcata.2008.01.011Search in Google Scholar
Stegenga, S., R. Van Soest, F. Kapteijn, and J. A. Moulijn. 1993. “Nitric Oxide Reduction and Carbon Monoxide Oxidation over Carbon-Supported Copper-Chromium Catalysts.” Applied Catalysis B: Environmental 2: 257–275.10.1016/0926-3373(93)80001-TSearch in Google Scholar
Torre-Abreu, C., C. Henriques, F. R. Ribeiro, G. Delahay, and M. F. Ribeiro. 1999. “Selective Catalytic Reduction of NO on Copper-Exchanged Zeolites: The Role of the Structure of the Zeolite in the Nature of Copper-Active Sites.” Catalysis Today 54: 407–418.10.1016/S0920-5861(99)00204-7Search in Google Scholar
Torre-Abreu, C., M. Ribeiro, C. Henriques, and F. Ribeiro. 1997a. “Influence of Cocation on Catalytic Activity of Cumor Catalysts for NO SCR by Propene.” Effect of Water Presence. Catalysis Letters 43: 25–29.10.1023/A:1018997313234Search in Google Scholar
Torre-Abreu, C., M. Ribeiro, C. Henriques, and F. Ribeiro. 1997b. “Selective Catalytic Reduction of NO with Propene over Cumfi Zeolites: Dependence on Si/Al Ratio and Copper Loading.” Applied Catalysis B: Environmental 11: 383–401.10.1016/S0926-3373(96)00057-4Search in Google Scholar
Varga, J., J. Halász, and I. Kiricsi. 1998. “Modified ZSM-5 Zeolite as DENOX Catalyst.” Environmental Pollution 102: 691–695.10.1016/B978-0-08-043201-4.50098-8Search in Google Scholar
Wang, X., and K. Gui. 2013. “Fe2O3 Particles as Superior Catalysts for Low Temperature Selective Catalytic Reduction of NO with NH3.” Journal of Environmental Sciences 25: 2469–2475.10.1016/S1001-0742(12)60331-3Search in Google Scholar
© 2018 Walter de Gruyter GmbH, Berlin/Boston
Articles in the same Issue
- Review
- Role of Different Feedstocks on the Butanol Production Through Microbial and Catalytic Routes
- Research Articles
- Experimental Study of Batch Reactor Performance for Ethyl Acetate Saponification
- Photocatalytic Activity of TiO2 Thin Films: Kinetic and Efficiency Study
- Experimental and Modeling Assessment of Sulfate and Arsenic Removal from Mining Wastewater by Nanofiltration
- CFD-DEM Numerical Simulation and Experimental Validation of Heat Transfer and Two-Component Flow in Fluidized Bed
- Numerical and Experimental Study on a Microfluidic Concentration Gradient Generator for Arbitrary Approximate Linear and Quadratic Concentration Curve Output
- Zn2+, Fe2+, Cu2+, Mn2+, H+ Ion-exchanged and Raw Clinoptilolite Zeolite Catalytic Performance in the Propane-SCR-NOx Process: A Comparative Study
- Adsorption of Congo Red Dye from Aqueous Solutions by Montmorillonite as a Low-cost Adsorbent
- Modeling and Evaluating Zeolite and Amorphous Based Catalysts in Vacuum Gas Oil Hydrocracking Process
- Short Communication
- The Possibility of Hybrid-Bioreactor Heating by the Microwave Radiation
Articles in the same Issue
- Review
- Role of Different Feedstocks on the Butanol Production Through Microbial and Catalytic Routes
- Research Articles
- Experimental Study of Batch Reactor Performance for Ethyl Acetate Saponification
- Photocatalytic Activity of TiO2 Thin Films: Kinetic and Efficiency Study
- Experimental and Modeling Assessment of Sulfate and Arsenic Removal from Mining Wastewater by Nanofiltration
- CFD-DEM Numerical Simulation and Experimental Validation of Heat Transfer and Two-Component Flow in Fluidized Bed
- Numerical and Experimental Study on a Microfluidic Concentration Gradient Generator for Arbitrary Approximate Linear and Quadratic Concentration Curve Output
- Zn2+, Fe2+, Cu2+, Mn2+, H+ Ion-exchanged and Raw Clinoptilolite Zeolite Catalytic Performance in the Propane-SCR-NOx Process: A Comparative Study
- Adsorption of Congo Red Dye from Aqueous Solutions by Montmorillonite as a Low-cost Adsorbent
- Modeling and Evaluating Zeolite and Amorphous Based Catalysts in Vacuum Gas Oil Hydrocracking Process
- Short Communication
- The Possibility of Hybrid-Bioreactor Heating by the Microwave Radiation