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Batch Conversion of Methane to Methanol Using Copper Loaded Mordenite: Influence of the Main Variables of the Process
Conversión de metano a metanol por lotes usando mordenita intercambiada con cobre: influencia de las variables principales del proceso
Keywords:
methane, methanol, mild conditions, copper mordenite, solid state ion exchange, activation temperature, methane pressure, copper weight percent, (en)metano, metanol, condiciones suaves, mordenita de cobre, intercambio iónico en estado sólido, Temperatura de activación, presión de metano, por ciento en peso de cobre, (es)
Due to the demands of oxygenated derivatives of hydrocarbons for the industry, the methane (CH4) to methanol (MeOH) conversion through solid-state catalysis is a current topic, with definite questions and specific challenges. This work shows a statistical model that predicts the quantity of methanol produced through a batch conversion process employing copper-exchanged mordenite in accordance with a full factorial experimental design. Synthesis was performed through solid-state ion exchange from Cu(acac)2 and NH4-Mordenite, obtaining weight percentages (%Cu) of 1%, 3%, and 5%, which was followed by activation through calcination at a range of temperatures (Tcal) between 300-500 °C, as well as a reaction with methane under 2-10 bar pressure (P) in static conditions employing a batch reactor. The quantities of MeOH produced, and their yields were determined through a gas chromatography and mass spectrometry analysis of the reaction samples. Finally, the role and contribution of each of the variables considered in the conversion process were analyzed. By using a nonlinear model, a quadratic dependence with %Cu and P in the studied range of the variables was found, as well as a linear dependence with Tcal. Finally, for this experiment, the highest yields (µmol/g) were obtained with the following conditions: %Cu=3 %, P=6 bar, and Tcal=400 °C.
Debido a la demanda de derivados oxigenados de hidrocarburos para la industria, la conversión de metano (CH4) a metanol (CH3OH) por medio de catálisis en estado sólido es una cuestión de actualidad, precisa y con retos específicos. Este trabajo muestra un modelo estadístico que predice la cantidad de metanol producido por un proceso de conversión por lotes empleando mordenitas intercambiadas con cobre de acuerdo con un diseño experimental factorial. La síntesis fue realizada por intercambio iónico en estado sólido a partir de Cu(acac)2 y NH4-Mordenita, obteniendo porcentajes de intercambio en peso de Cobre (%Cu) de 1 %, 3 % y 5 %, seguido de una activación por calcinación en el rango de temperaturas (Tcal) de 300-500 °C, así como una reacción con metano en el rango de presiones de 2-10 bar (P) bajo condiciones estáticas con un reactor por lotes. Las cantidades de MeOH producidas y sus rendimientos fueron determinados usando análisis de cromatografía de gases y espectrometría de masas de las muestras de la reacción. Finalmente se analizaron el papel y la contribución de cada una de las variables consideradas en el proceso de conversión. Usando un modelo no lineal, se encontró una dependencia cuadrática del %Cu y P en el rango estudiado de cada variable, así como una dependencia lineal con Tcal. Finalmente, para este experimento, los mayores rendimientos (μmol/gr) se obtuvieron con las siguientes condiciones: %Cu=3%, P=6 bar y Tcal=400 °C.
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References
Abashar, M. E. E., and Al-Rabiah, A. A. (2018). Investigation of the efficiency of sorption-enhanced methanol synthesis process in circulating fast fluidized bed reactors. Fuel Processing Technology, 179, 387-398. https://doi.org/10.1016/j.fuproc.2018.07.028
Álvarez, M., Marín, P., and Ordóñez, S. (2020). Direct oxidation of methane to methanol over Cu-zeolites at mild conditions. Molecular Catalysis, 487, 110886. https://doi.org/10.1016/j.mcat.2020.110886
Balasubramanian, R., and Rosenzweig, A. C. (2007). Structural and Mechanistic Insights into Methane Oxidation by Particulate Methane Monooxygenase. Accounts of Chemical Research, 40(7), 573-580. https://doi.org/10.1021/ar700004s
Banerjee, R., Proshlyakov, Y., Lipscomb, J. D., and Proshlyakov, D. A. (2015). Structure of the key species in the enzymatic oxidation of methane to methanol. Nature, 518, 431-434. https://doi.org/10.1038/nature14160
Burnett, L., Rysakova, M., Wang, K., González-Carballo, J., Tooze, R. P., and García-García, F. R. (2019). Isothermal cyclic conversion of methane to methanol using copper-exchanged ZSM-5 zeolite materials under mild conditions. Applied Catalysis A: General, 587, 117272. https://doi.org/10.1016/j.apcata.2019.117272
da Silva, M. (2016). Synthesis of methanol from methane: Challenges and advances on the multi-step (syngas) and one-step routes (DMTM). Fuel Processing Technology, 145, 42-61. https://doi.org/10.1016/j.fuproc.2016.01.023
Dalena, F., Senatore, A., Basile, M., Knani, S., Basile, A., and Iulianelli, A. (2018). Advances in Methanol Production and Utilization, with Particular Emphasis toward Hydrogen Generation via Membrane Reactor Technology. Membranes, 8(4), 98. https://doi.org/10.3390/membranes8040098
Dyballa, M., Pappas, D. K., Kvande, K., Borfecchia, E., Arstad, B., Beato, P., Olsbye, U., and Svelle, S. (2019). On How Copper Mordenite Properties Govern the Framework Stability and Activity in the Methane-to-Methanol Conversion. ACS Catalysis, 9(1), 365-375. https://doi.org/10.1021/acscatal.8b04437
Groothaert, M. H., Smeets, P. J., Sels, B. F., Jacobs, P. A., and Schoonheydt, R. A. (2005). Selective Oxidation of Methane by the Bis(μ-oxo)dicopper Core Stabilized on ZSM-5 and Mordenite Zeolites. Journal of the American Chemical Society, 127(5), 1394-1395. https://doi.org/10.1021/ja047158u
Grundner, S., Markovits, M. A. C., Li, G., Tromp, M., Pidko, E. A., Hensen, E. J. M., Jentys, A., Sanchez-Sanchez, M., and Lercher, J. A. (2015). Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol. Nature Communications, 6, 7546. https://doi.org/10.1038/ncomms8546
Hammond, C., Conrad, S., and Hermans, I. (2012). Oxidative methane upgrading. ChemSusChem, 5(9), 1668-1686. https://doi.org/10.1002/cssc.201200299
Jovanovic, Z. R., Lange, J.-P., Ravi, M., Knorpp, A. J., Sushkevich, V. L., Newton, M. A., Palagin, D., and van Bokhoven, J. A. (2020). Oxidation of methane to methanol over Cu-exchanged zeolites: Scientia gratia scientiae or paradigm shift in natural gas valorization? Journal of Catalysis, 385, 238-245. https://doi.org/10.1016/j.jcat.2020.02.001
Latimer, A. A., Kakekhani, A., Kulkarni, A. R., and Nørskov, J. K. (2018). Direct Methane to Methanol: The Selectivity–Conversion Limit and Design Strategies. ACS Catalysis, 8(8), 6894-6907. https://doi.org/10.1021/acscatal.8b00220
Le, H. V., Parishan, S., Sagaltchik, A., Göbel, C., Schlesiger, C., Malzer, W., Trunschke, A., Schomäcker, R., and Thomas, A. (2017). Solid-State Ion-Exchanged Cu/Mordenite Catalysts for the Direct Conversion of Methane to Methanol. ACS Catalysis, 7(2), 1403-1412. https://doi.org/10.1021/acscatal.6b02372
Lomachenko, K. A., Martini, A., Pappas, D. K., Negri, C., Dyballa, M., Berlier, G., Bordiga, S., Lamberti, C., Olsbye, U., Svelle, S., Beato, P., and Borfecchia, E. (2019). The impact of reaction conditions and material composition on the stepwise methane to methanol conversion over Cu-MOR: An operando XAS study. Catalysis Today, 336, 99-108. https://doi.org/10.1016/j.cattod.2019.01.040
Ma, C., Tan, X., Zhang, H., Shen, Q., Sun, N., and Wei, W. (2020). Direct conversion of methane to methanol over Cu exchanged mordenite: Effect of counter ions. Chinese Chemical Letters, 31(1), 235–238. https://doi.org/10.1016/j.cclet.2019.03.039
Narsimhan, K., Michaelis, V. K., Mathies, G., Gunther, W. R., Griffin, R. G., and Román-Leshkov, Y. (2015). Methane to Acetic Acid over Cu-Exchanged Zeolites: Mechanistic Insights from a Site-Specific Carbonylation Reaction. Journal of the American Chemical Society, 137(5), 1825-1832. https://doi.org/10.1021/ja5106927
Newton, M. A., Knorpp, A. J., Sushkevich, V. L., Palagin, D., and van Bokhoven, J. A. (2020). Active sites and mechanisms in the direct conversion of methane to methanol using Cu in zeolitic hosts: a critical examination. Chemical Society Reviews, 49(5), 1449-1486. https://doi.org/10.1039/C7CS00709D
Olivos-Suarez, A. I., Szécsényi, À., Hensen, E. J. M., Ruiz-Martinez, J., Pidko, E. A., and Gascon, J. (2016). Strategies for the Direct Catalytic Valorization of Methane Using Heterogeneous Catalysis: Challenges and Opportunities. ACS Catalysis, 6(5), 2965-2981. https://doi.org/10.1021/acscatal.6b00428
Oord, R., Schmidt, J. E., and Weckhuysen, B. M. (2018). Methane-to-methanol conversion over zeolite Cu-SSZ-13, and its comparison with the selective catalytic reduction of NOx with NH3. Catalysis Science and Technology, 8(4), 1028-1038. https://doi.org/10.1039/C7CY02461D
Palagin, D., Knorpp, A. J., Pinar, A. B., Ranocchiari, M., and van Bokhoven, J. A. (2017). Assessing the relative stability of copper oxide clusters as active sites of a CuMOR zeolite for methane to methanol conversion: size matters? Nanoscale, 9(3), 1144-1153. https://doi.org/10.1039/C6NR07723D
Pappas, D. K., Borfecchia, E., Dyballa, M., Pankin, I. A., Lomachenko, K. A., Martini, A., Signorile, M., Teketel, S., Arstad, B., Berlier, G., Lamberti, C., Bordiga, S., Olsbye, U., Lillerud, K. P., Svelle, S., and Beato, P. (2017). Methane to Methanol: Structure–Activity Relationships for Cu-CHA. Journal of the American Chemical Society, 139(42), 14961–14975. https://doi.org/10.1021/jacs.7b06472
Sainz-Vidal, A., Balmaseda, J., Lartundo-Rojas, L., and Reguera, E. (2014). Preparation of Cu-mordenite by ionic exchange reaction under milling: A favorable route to form the mono-(μ-oxo) dicopper active species. Microporous and Mesoporous Materials, 185, 113-120. https://doi.org/10.1016/j.micromeso.2013.11.009
Schwarz, H. (2011). Chemistry with methane: Concepts rather than recipes. Angewandte Chemie - International Edition, 50(43), 10096-10115. https://doi.org/10.1002/anie.201006424
Sharma, R., Poelman, H., Marin, G. B., and Galvita, V. V. (2020). Approaches for Selective Oxidation of Methane to Methanol. Catalysts, 10(2), 194. https://doi.org/10.3390/catal10020194
Sheppard, T., Hamill, C. D., Goguet, A., Rooney, D. W., and Thompson, J. M. (2014). A low temperature, isothermal gas-phase system for conversion of methane to methanol over Cu–ZSM-5. Chemical Communications, 50(75), 11053-11055. https://doi.org/10.1039/C4CC02832E
Sushkevich, V. L., Palagin, D., and van Bokhoven, J. A. (2018). The Effect of the Active-Site Structure on the Activity of Copper Mordenite in the Aerobic and Anaerobic Conversion of Methane into Methanol. Angewandte Chemie - International Edition, 57(29), 8906-8910. https://doi.org/10.1002/anie.201802922
Tomkins, P., Mansouri, A., Bozbag, S. E., Krumeich, F., Park, M. B., Alayon, E. M. C., Ranocchiari, M., and Vanbokhoven, J. A. (2016). Isothermal Cyclic Conversion of Methane into Methanol over Copper-Exchanged Zeolite at Low Temperature. Angewandte Chemie - International Edition, 55(18), 5467–5471. https://doi.org/10.1002/anie.201511065
Tomkins, P., Ranocchiari, M., and van Bokhoven, J. A. (2017). Direct Conversion of Methane to Methanol under Mild Conditions over Cu-Zeolites and beyond. Accounts of Chemical Research, 50(2), 418-425. https://doi.org/10.1021/acs.accounts.6b00534
Tomkins, P, Mansouri, A., L. Sushkevich, V., van der Wal, L. I., Bozbag, S. E., Krumeich, F., Ranocchiari, M., and van Bokhoven, J. A. (2019). Increasing the activity of copper exchanged mordenite in the direct isothermal conversion of methane to methanol by Pt and Pd doping. Chemical Science, 10(1), 167-171. https://doi.org/10.1039/C8SC02795A
Vanelderen, P., Vancauwenbergh, J., Tsai, M.-L., Hadt, R. G., Solomon, E. I., Schoonheydt, R. A., and Sels, B. F. (2014). Spectroscopy and Redox Chemistry of Copper in Mordenite. ChemPhysChem, 15(1), 91-99. https://doi.org/10.1002/cphc.201300730
Wulfers, M. J., Teketel, S., Ipek, B., and Lobo, R. F. (2015). Conversion of methane to methanol on copper-containing small-pore zeolites and zeotypes. Chemical Communications, 51(21), 4447-4450. https://doi.org/10.1039/C4CC09645B
Yoshizawa, K. and Shiota, Y. (2006). Conversion of Methane to Methanol at the Mononuclear and Dinuclear Copper Sites of Particulate Methane Monooxygenase (pMMO): A DFT and QM/MM Study. Journal of the American Chemical Society, 128(30), 9873-9881. https://doi.org/10.1021/ja061604r
Zakaria, Z. and Kamarudin, S. K. (2016). Direct conversion technologies of methane to methanol: An overview. Renewable and Sustainable Energy Reviews, 65, 250-261. https://doi.org/https://doi.org/10.1016/j.rser.2016.05.082
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