THERMAL SCIENCE

International Scientific Journal

Gabriela Berkowicz

,

Jan Wrona

,

Jerzy Baron

,

Dariusz Bradlo

,

Witold Zukowski

CATALYTIC OXIDATION OF METHANOL IN THE CENOSPHERIC FLUIDIZED BED

ABSTRACT
The process of oxidation of gaseous CH3OH by N2O was carried out over an Ag-Fe2O3-cenosphere catalyst whose structure can be defined as double shell-core catalyst. Preparation of the catalyst was carried out in two stages: thermal decomposition of Fe(CO)5 at above 160°C and then electroless Ag plating. The process of methanol degradation by N2O was carried out in a fluidized bed reactor. The study confirms that it is possible to achieve complete degradation of N2O and CH3OH for the obtained catalyst at above 450°C when the contact time of the reactants with the catalyst is approximately 6 second and when the substrates are used in stoichiometric ratios. More than 60% of the hydrogen contained in CH3OH can be converted to molecular hydrogen at 500°C with a ratio of N2O/CH3OH not greater than 0.6 and with a contact time of reactants with the catalyst of approx. 6 seconds.
KEYWORDS
nitrous oxide, methanol decomposition, core-shell catalyst, Ag/Fe2O3-coated cenospheres, catalytic fluidised bed
PAPER SUBMITTED: 1970-01-01
PAPER REVISED: 2019-02-28
PAPER ACCEPTED: 2019-03-03
PUBLISHED ONLINE: 2019-09-22
DOI REFERENCE: https://doi.org/10.2298/TSCI19S4231B
CITATION EXPORT: view in browser or download as text file
THERMAL SCIENCE YEAR 2019, VOLUME 23, ISSUE Supplement 4, PAGES [1231 - 1240]
REFERENCES
[1] Venkataramanan, M., et al. Causes and Effects of Global Warming, Indian Journal of Science and Technology, 4 (2011), 3, pp. 226-229, 10.17485/ijst/2011/v4i3.17
[2] ***, American Meteorological Society, Climate Change, [www.ametsoc.org/ams/index.cfm/about-ams/ams-statements/statements-of-the-ams-in-force/climate-change/](https://www.ametsoc.org/ams/index.cfm/about-ams/ams-statements/statements-of-the-ams-in-force/climate-change/
[3] ***, US Environmental Protection Agency, Overview of Greenhouse Gases, [www3.epa.gov/climatechange/ghgemissions/gases.html](https://www3.epa.gov/climatechange/ghgemissions/gases.html
[4] ***, US Environmental Protection Agency, Emission Factors for Greenhouse Gas Inventories, [www.epa.gov/sites/production/files/2015-11/documents/emission-factors_nov_2015.pdf](https://www.epa.gov/sites/production/files/2015-11/documents/emission-factors_nov_2015.pdf
[5] Zabilskiy, M., et al., N2O Decomposition Over CuO/CeO2 Catalyst: New Insights into Reaction Mechanism and Inhibiting Action of H2O and NO by Operando Techniques, Applied Catalysis B: Environmental, 197 (2016), Nov., pp. 146-158, 10.1016/j.apcatb.2016.02.024
[6] Ravinshakara, A. R., et al., Nitrous Oxide (N2O): the Dominant Ozone-Depleting Substance Emitted in the 21st Century, Science, 326 (2009), 5949, pp.123-125
[7] ***, European Environment Agency, Atmospheric Concentration of Nitrous Oxide (ppb), 2015 [www.eea.europa.eu/data-and-maps/figures/atmospheric-concentration-of-n2o-ppb-1](http://www.eea.europa.eu/data-and-maps/figures/atmospheric-concentration-of-n2o-ppb-1
[8] Abu-Zied, B. M., et al., Pure and Ni-Substituted Co3O4 Spinel Catalysts for Direct N2O Decomposition, Chinese Journal of Catalysis, 35 (2014), 7, pp. 1105-1112, 10.1016/s1872-2067(14)60058-9
[9] Zhang, B., et al., Role of Aggregated Fe Oxo Species in N2O Decomposition Over Fe/ZSM-5, Chinese Journal of Catalysis, 35 (2014), 12, pp. 1972-1981, 10.1016/s1872-2067(14)60184-4
[10] Ul-Ain B., et al., Catalytic Decomposition of N2O on Cobalt Substituted Barium Hexaferrites, Chinese Journal of Catalysis, 34 (2013), 7, pp. 13571362, 10.1016/s1872-2067(12)60587-7
[11] Wu, M., et al., Effects of Acid Pretreatment on Fe-ZSM-5 and Fe-Beta Catalysts for N2O Decomposi-tion, Chinese Journal of Catalysis, 37 (2016), 6, pp. 898-907, 10.1016/s1872-2067(15)61052-x
[12] Zhang, F., et al., Promotion by Co of a NiO-BaCO3 Catalyst for N2O Decomposition, Chinese Journal of Catalysis, 36 (2015), 3, pp. 344-347, 10.1016/s1872-2067(14)60250-3
[13] Pietrogiacomi, D., et al., N2O Decomposition on CoOx, CuOx, FeOx or MnOx Supported on ZrO2: The Effect of Zirconia Doping with Sulfates or K+ on Catalytic Activity, Applied Catalysis B: Environmental, 187 (2016), June, pp. 218-227, 10.1016/j.apcatb.2016.01.018
[14] Pachatouridou, E., et al., N2O Decomposition Over Ceria-Promoted Ir/Al2O3 Catalysts: The Role of Ceria, Applied Catalysis B: Environmental, 187 (2016), Jan., pp. 259-268, 10.1016/j.apcatb.2016.01.049
[15] Melian-Cabrera, I., et al., Tail Gas Catalyzed N2O Decomposition Over Fe-Beta Zeolite. On the Promot-ing Role of Framework Connected AlO6 Sites in the Vicinity of Fe by Controlled Dealumination During Exchange, Applied Catalysis B: Environmental, 203 (2017), Apr., pp. 218-226, 10.1016/j.apcatb.2016.10.019
[16] Yu, H., et al., Pb0.04Co Catalyst for N2O Decomposition in Presence of Impurity Gases, Applied Catalysis B: Environmental, 185 (2015), Dec., pp. 110-118, 10.1016/j.apcatb.2015.12.011
[17] Zabilskiy, M., et al., Small CuO Clusters on CeO2 Nanospheres as Active Species for Catalytic N2O Decomposition, Applied Catalysis B: Environmental, 163 (2015), Feb., pp. 113-122, 10.1016/j.apcatb.2014.07.057
[18] Franken, T., et al., Investigation Of Potassium Doped Mixed Spinels CuxCo3-xO4 as Catalysts for an Efficient N2O Decomposition in Real Reaction Conditions, Applied Catalysis B: Environmental, 176-177 (2015), Oct., pp. 298-305, 10.1016/j.apcatb.2015.04.002
[19] ***, U.S. Environmental Protection Agency, Inventory of U.S. Greenhouse Gas Emissions and Sinks:1990 - 2014, 1-558 Raport EPA 430-R-16-002, [www.epa.gov/sites/production/files/2016-04/documents/us-ghg-inventory-2016-main-text.pdf](https://www.epa.gov/sites/production/files/2016-04/documents/us-ghg-inventory-2016-main-text.pdf
[20] Reimer, R. A, et al., Abatement of N2O Emissions Produced in the Adipic acid Industry, Environ. Prog., 13 (1994), 2, pp. 134-137
[21] Stefanova, M., et al. Technical Engineering for Catalytic Reduction of Nitrous Oxide Emissions, GSTF Journal of Engineering Technology (JET), 3 (2015), 2, pp. 89-94, 10.5176/2251-3701_3.2.131
[22] Castellan, A., et al., Industrial Production and Use of Adipic Acid, Cat. Today, 9 (1991), 3, pp. 237-254, 10.1016/0920-5861(91)80049-f
[23] Perez-Ramirez, J., Prospects of N2O Emission Regulations in the European Fertilizer Industry, Applied Catalysis B: Environmental, 70 (2007), 1-4, pp. 31-35, 10.1016/j.apcatb.2005.11.019
[24] ***,AEA Technology Environment, Options to Reduce Nitrous Oxide Emissions (Final Report) A report produced for DGXI, 1998 [ec.europa.eu/environment/enveco/climate_change/pdf/nitrous_oxide_emissions.pdf](http://ec.europa.eu/environment/enveco/climate_change/pdf/nitrous_oxide_emissions.pdf
[25] Held, A., et al., Propane-to-Propene Oxide Oxidation on Silica-Supported Vanadium, Journal of Catalysis, 336 (2016), Apr., pp. 23-32
[26] Woods, M. P., et al., Oxygen and Nitrous Oxide as Oxidants: Implications for Ethane Oxidative Dehy-drogenation over Silica-Titania-Supported Molybdenum, The Journal of Physical Chemistry C, 113 (2009), 23, pp. 10112-10119, 10.1021/jp810664u
[27] ***,United State Environmental Protection Agency, The original list of hazardous air pollutants. [www3.epa.gov/airtoxics/188polls.html](https://www3.epa.gov/airtoxics/188polls.html, 10.1016/b978-012497451-7/50010-3
[28] Jacob, D. J., et al., Global Budget of Methanol: Constraints from Atmospheric Observations, Journal of Geophysical Research, 110 (D08303) (2005) Apr., pp. 1-17, 10.1029/2004jd005172
[29] Araiza, D. G., et al., Partial Oxidation of Methanol Over Copper Supported on Nanoshaped Ceria for Hydrogen Production, Catalysis Today, 282 (2017), 2, pp. 185-194, 10.1016/j.cattod.2016.06.055
[30] Chen, W.-H., et al., Hydrogen Production from Methanol Partial Oxidation Over Pt/Al2O3 Catalyst with Low Pt Content, Energy, 88 (2015), Aug., pp. 399-407, 10.1016/j.energy.2015.05.055
[31] Chang, F. W., et al., Applied Catalysis A: General, 302 (2006), 2, pp. 157-167
[32] Tsoncheva, T., et al., Nanostructured Copper-Zirconia Composites as Catalysts for Methanol Decompo-sition, Applied Catalysis B: Environmental, 165 (2015), Apr., pp. 599-610, 10.1016/j.apcatb.2014.10.058
[33] Marban, G., et al., A Highly Active, Selective and stable Copper/Cobalt-Structured Nanocatalyst for Methanol Decomposition, Applied Catalysis B: Environmental, 99 (2010), 1-2, pp. 257-264, 10.1016/j.apcatb.2010.06.028
[34] Mo, L., et al., Selective Production of Hydrogen from Partial Oxidation of Methanol Over Supported Silver Catalysts Prepared by Method of Redox Coprecipitation, C. Today, 148 (2009), 1-2, pp. 124-129, 10.1016/j.cattod.2009.04.002
[35] Tian, C., et al., Understanding of Physicochemical Properties and Formation Mechanisms of fine Particular Matter Generated from Canadian Coal Combustion, Fuel, 165 (2016), Feb., pp. 224-234, 10.1016/j.fuel.2015.10.037
[36] Yao, Z. T., et al., A Comprehensive Review on the Applications of Coal Fly Ash, Earth-Science Reviews, 141 (2015), Feb., pp. 105-121, 10.1016/j.earscirev.2014.11.016
[37] Vassilev, S. V., et al., Phase-Mineral and Chemical Composition of Coal Fly Ashes as a Basis for their Multicomponent Utilization. 2. Characterization of Ceramic Cenosphere and Salt Concentrates, Fuel, 83 (2004), 4-5, pp. 585-603, 10.1016/j.fuel.2003.10.003
[38] Aixiang, Z., et al., Electroless Ni-P Coating of Cenospheres Using Silver Nitrate Activator, Surface & Coatings Technology, 197 (2005), 2-3, pp. 142-147, 10.1016/j.surfcoat.2005.01.009
[39] Li, Y., Ash Cenosphere Formation, Fragmentation and its Contribution to Particulate Matter Emission during Solid Fuels Combustion 2012, Ph. D. thesis, Department of Chemical Enginering, Curtin Univer-sity, Perth, western Australia, Australia
[40] Berkowicz, G., et al., Cenospheres as an Innovative Fluidised Bed Material, Technical Transactions Chemistry, 113 (2016), 1-Ch, pp. 3-10, 10.4467/2353737xct.16.041.5303
[41] Berkowicz, G., et al. Oxidative Decomposition of Methanol in a Vibroacoustic Fluidized Bed of Ag-coated Cenosphere Core-shell Catalyst, Polish Journal of Chemical Technology, 18 (2016), 4, pp. 70-74, 10.1515/pjct-2016-0073
[42] Wang, P., et al., Deposition of Iron on Graphite Felts by Thermal Decomposition of Fe(CO)5 for Anodic Modification of Microbial Fuel Cells, International Journal of Electrochemical Science, 8 (2013), 4, pp. 4712-4722, 10.1016/s1452-3981(23)14634-7
[43] Bowker, M., et al., Methanol Oxidation on Fe2O3 Catalysts and the Effects of Surface Mo, Faraday Discussions, 188 (2016), July, pp. 387-398
[44] ***,National Toxicology Program, Department of Health and Human Services, Report on Carcinogens, Thirteenth Edition, Formaldehyde, [ntp.niehs.nih.gov/ntp/roc/content/profiles/formaldehyde.pdf](https://ntp.niehs.nih.gov/ntp/roc/content/profiles/formaldehyde.pdf
[45] Wachs, I. E., et al., The Oxidation of Methanol on a Silver (110) Catalyst, Catalyst Surface Science, 76 (1978), 2, pp. 531-558, 10.1016/0039-6028(78)90113-9
[46] Schwaner, A. L., et al., The Thermal and Electron-Induced Chemistry of N20/Ag(111), Surface Science, 351 (1996), 1-3, pp. 228-232
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Catalytic oxidation of methanol in the cenospheric fluidized bed

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