156 research outputs found
Economic Assessment of the Hydrogenation of CO<sub>2</sub> to Liquid Fuels and Petrochemical Feedstock
To remove high concentrations of CO2 from the off-gas of coal-driven power plants, a new process was proposed. The catalytic hydrogenation of the CO2 leads to the production of C2âââC4 (petrochemical feedstock) and liquid C5+ hydrocarbons (fuel). Thus, environmentally harmful CO2 may be converted sustainably to useful products. On the basis of a process flow sheet, the costs for processing the CO2 are estimated for different plant sizes. The price of hydrogen contributes significantly to the overall production costs. Further price reductions may be achieved by final engineering optimization of the process as a whole and specific unit operations
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Control of coordinatively unsaturated Zr sites in ZrO2 for efficient CâH bond activation
Due to the complexity of heterogeneous catalysts, identification of active sites and the ways for their experimental design are not inherently straightforward but important for tailored catalyst preparation. The present study reveals the active sites for efficient CâH bond activation in C1âC4 alkanes over ZrO2 free of any metals or metal oxides usually catalysing this reaction. Quantum chemical calculations suggest that two Zr cations located at an oxygen vacancy are responsible for the homolytic CâH bond dissociation. This pathway differs from that reported for other metal oxides used for alkane activation, where metal cation and neighbouring lattice oxygen form the active site. The concentration of anion vacancies in ZrO2 can be controlled through adjusting the crystallite size. Accordingly designed ZrO2 shows industrially relevant activity and durability in non-oxidative propane dehydrogenation and performs superior to state-of-the-art catalysts possessing Pt, CrOx, GaOx or VOx species
Elucidating the Nature of Active Sites and Fundamentals for their Creation in Zn-Containing ZrO2-Based Catalysts for Non-Oxidative Propane Dehydrogenation
Ketone Formation from Carboxylic Acids by Ketonic Decarboxylation: The Exceptional Case of the Tertiary Carboxylic Acids
"This is the peer reviewed version of the following article: Oliver-Tomas, Borja, Michael Renz, and Avelino Corma. 2017. Ketone Formation from Carboxylic Acids by Ketonic Decarboxylation: The Exceptional Case of the Tertiary Carboxylic Acids. Chemistry - A European Journal 23 (52). Wiley: 12900 908. doi:10.1002/chem.201702680, which has been published in final form at https://doi.org/10.1002/chem.201702680. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving."[EN] For the reaction mechanism of the ketonic decarboxylation of two carboxylic acids, a -keto acid is favored as key intermediate in many experimental and theoretical studies. Hydrogen atoms in the -position are an indispensable requirement for the substrates to react by following this mechanism. However, isolated observations with tertiary carboxylic acids are not consistent with it and these are revisited and discussed herein. The experimental results obtained with pivalic acid indicate that the ketonic decarboxylation does not occur with this substrate. Instead, it is consumed in alternative reactions such as disintegration into isobutene, carbon monoxide, and water (retro-Koch reaction). In addition, the carboxylic acid is isomerized or loses carbon atoms, which converts the tertiary carboxylic acid into carboxylic acids bearing -proton atoms. Hence, the latter are suitable to react through the -keto acid pathway. A second substrate, 2,2,5,5-tetramethyladipic acid, reacted by following the same retro-Koch pathway. The primary product was the monocarboxylic acid 2,2,5-trimethyl-4-hexenoic acid (and its double bond isomer), which might be further transformed into a cyclic enone or a lactone. The ketonic decarboxylation product, 2,2,5,5-tetramethylcyclopentanone was observed in traces (<0.2% yield). Therefore, it can be concluded that the observed experimental results further support the proposed mechanism for the ketonic decarboxylation via the -keto acid intermediate.The authors thank MINECO (CTQ2015-67591-P and Severo Ochoa program, SEV-2016-0683) and Generalitat Valenciana (PROMETEO II/2013/011 Project) for funding this work. B.O.-T. is grateful to the CSIC (JAE program) for his PhD fellowship.Oliver-TomĂĄs, B.; Renz, M.; Corma CanĂłs, A. (2017). Ketone Formation from Carboxylic Acids by Ketonic Decarboxylation: The Exceptional Case of the Tertiary Carboxylic Acids. Chemistry - A European Journal. 23(52):12900-12908. https://doi.org/10.1002/chem.201702680S12900129082352Renz, M. (2005). Ketonization of Carboxylic Acids by Decarboxylation: Mechanism and Scope. European Journal of Organic Chemistry, 2005(6), 979-988. doi:10.1002/ejoc.200400546Pham, T. N., Sooknoi, T., Crossley, S. P., & Resasco, D. E. (2013). Ketonization of Carboxylic Acids: Mechanisms, Catalysts, and Implications for Biomass Conversion. ACS Catalysis, 3(11), 2456-2473. doi:10.1021/cs400501hWu, K., Wu, Y., Chen, Y., Chen, H., Wang, J., & Yang, M. (2016). Heterogeneous Catalytic Conversion of Biobased Chemicals into Liquid Fuels in the Aqueous Phase. ChemSusChem, 9(12), 1355-1385. doi:10.1002/cssc.201600013Resasco, D. E., Wang, B., & Crossley, S. (2016). Zeolite-catalysed CâC bond forming reactions for biomass conversion to fuels and chemicals. Catalysis Science & Technology, 6(8), 2543-2559. doi:10.1039/c5cy02271aF. Iliopoulou, E. (2010). Review of C-C Coupling Reactions in Biomass Exploitation Processes. Current Organic Synthesis, 7(6), 587-598. doi:10.2174/157017910794328592Murzin, D. Y., & Simakova, I. L. (2011). Catalysis in biomass processing. Catalysis in Industry, 3(3), 218-249. doi:10.1134/s207005041103007xCliment, M. J., Corma, A., & Iborra, S. (2014). Conversion of biomass platform molecules into fuel additives and liquid hydrocarbon fuels. Green Chemistry, 16(2), 516. doi:10.1039/c3gc41492bSimakova, I. L., & Murzin, D. Y. (2016). Transformation of bio-derived acids into fuel-like alkanes via ketonic decarboxylation and hydrodeoxygenation: Design of multifunctional catalyst, kinetic and mechanistic aspects. Journal of Energy Chemistry, 25(2), 208-224. doi:10.1016/j.jechem.2016.01.004Serrano-Ruiz, J. C., Wang, D., & Dumesic, J. A. (2010). Catalytic upgrading of levulinic acid to 5-nonanone. Green Chemistry, 12(4), 574. doi:10.1039/b923907cCorma, A., Oliver-Tomas, B., Renz, M., & Simakova, I. L. (2014). Conversion of levulinic acid derived valeric acid into a liquid transportation fuel of the kerosene type. Journal of Molecular Catalysis A: Chemical, 388-389, 116-122. doi:10.1016/j.molcata.2013.11.015Corma, A., Renz, M., & Schaverien, C. (2008). Coupling Fatty Acids by Ketonic Decarboxylation Using Solid Catalysts for the Direct Production of Diesel, Lubricants, and Chemicals. ChemSusChem, 1(8-9), 739-741. doi:10.1002/cssc.200800103Neunhoeffer, O., & Paschke, P. (1939). Ăber den Mechanismus der Ketonbildung aus Carbonsäuren. Berichte der deutschen chemischen Gesellschaft (A and B Series), 72(4), 919-929. doi:10.1002/cber.19390720442Farmer, E. H., & Kracovski, J. (1927). CII.âThe effect of gem-dialkyl groups on the formation and stability of the anhydrides of dicarboxylic acids. J. Chem. Soc., 0(0), 680-685. doi:10.1039/jr9270000680Eberson, L. (1966). An anomalous cyclization of 2,2,5,5-tetramethyladipic acid. Tetrahedron Letters, 7(2), 223-226. doi:10.1016/s0040-4039(00)70218-8Rand, L., Wagner, W., Warner, P. O., & Kovac, L. R. (1962). Reactions Catalyzed by Potassium Fluoride. II. The Conversion of Adipic Acid to Cyclopentanone. The Journal of Organic Chemistry, 27(3), 1034-1035. doi:10.1021/jo01050a504Aranda-PĂŠrez, N., Ruiz, M. P., Echave, J., & Faria, J. (2017). Enhanced activity and stability of Ru-TiO2 rutile for liquid phase ketonization. Applied Catalysis A: General, 531, 106-118. doi:10.1016/j.apcata.2016.10.025Bennett, J. A., Parlett, C. M. A., Isaacs, M. A., Durndell, L. J., Olivi, L., Lee, A. F., & Wilson, K. (2017). Acetic Acid Ketonization over Fe
3
O
4
/SiO
2
for Pyrolysis BioâOil Upgrading. ChemCatChem, 9(9), 1648-1654. doi:10.1002/cctc.201601269Stefanidis, S. D., Karakoulia, S. A., Kalogiannis, K. G., Iliopoulou, E. ., Delimitis, A., Yiannoulakis, H., ⌠Triantafyllidis, K. S. (2016). Natural magnesium oxide (MgO) catalysts: A cost-effective sustainable alternative to acid zeolites for the in situ upgrading of biomass fast pyrolysis oil. Applied Catalysis B: Environmental, 196, 155-173. doi:10.1016/j.apcatb.2016.05.031Lee, Y., Choi, J.-W., Suh, D. J., Ha, J.-M., & Lee, C.-H. (2015). Ketonization of hexanoic acid to diesel-blendable 6-undecanone on the stable zirconia aerogel catalyst. Applied Catalysis A: General, 506, 288-293. doi:10.1016/j.apcata.2015.09.008Baylon, R. A. L., Sun, J., Martin, K. J., Venkitasubramanian, P., & Wang, Y. (2016). Beyond ketonization: selective conversion of carboxylic acids to olefins over balanced Lewis acidâbase pairs. Chemical Communications, 52(28), 4975-4978. doi:10.1039/c5cc10528eWoo, Y., Lee, Y., Choi, J.-W., Suh, D. J., Lee, C.-H., Ha, J.-M., & Park, M.-J. (2017). Role of Anhydride in the Ketonization of Carboxylic Acid: Kinetic Study on Dimerization of Hexanoic Acid. Industrial & Engineering Chemistry Research, 56(4), 872-880. doi:10.1021/acs.iecr.6b04605Ignatchenko, A. V. (2011). Density Functional Theory Study of Carboxylic Acids Adsorption and Enolization on Monoclinic Zirconia Surfaces. The Journal of Physical Chemistry C, 115(32), 16012-16018. doi:10.1021/jp203381hIgnatchenko, A. V., & Kozliak, E. I. (2012). Distinguishing Enolic and Carbonyl Components in the Mechanism of Carboxylic Acid Ketonization on Monoclinic Zirconia. ACS Catalysis, 2(8), 1555-1562. doi:10.1021/cs3002989Pulido, A., Oliver-Tomas, B., Renz, M., Boronat, M., & Corma, A. (2012). Ketonic Decarboxylation Reaction Mechanism: A Combined Experimental and DFT Study. ChemSusChem, 6(1), 141-151. doi:10.1002/cssc.201200419Oliver-Tomas, B., Gonell, F., Pulido, A., Renz, M., & Boronat, M. (2016). Effect of the CÎą substitution on the ketonic decarboxylation of carboxylic acids over m-ZrO2: the role of entropy. Catalysis Science & Technology, 6(14), 5561-5566. doi:10.1039/c6cy00395hWang, S., & Iglesia, E. (2017). Experimental and theoretical assessment of the mechanism and site requirements for ketonization of carboxylic acids on oxides. Journal of Catalysis, 345, 183-206. doi:10.1016/j.jcat.2016.11.006Tosoni, S., & Pacchioni, G. (2016). Acetic acid ketonization on tetragonal zirconia: Role of surface reduction. Journal of Catalysis, 344, 465-473. doi:10.1016/j.jcat.2016.10.002Pacchioni, G. (2014). Ketonization of Carboxylic Acids in Biomass Conversion over TiO2 and ZrO2 Surfaces: A DFT Perspective. ACS Catalysis, 4(9), 2874-2888. doi:10.1021/cs500791wPestman, R., Koster, R. M., van Duijne, A., Pieterse, J. A. Z., & Ponec, V. (1997). Reactions of Carboxylic Acids on Oxides. Journal of Catalysis, 168(2), 265-272. doi:10.1006/jcat.1997.1624Parida, K., & Mishra, H. K. (1999). Catalytic ketonisation of acetic acid over modified zirconia. Journal of Molecular Catalysis A: Chemical, 139(1), 73-80. doi:10.1016/s1381-1169(98)00184-8Orozco, L. M., Renz, M., & Corma, A. (2016). Carbon-Carbon Bond Formation and Hydrogen Production in the Ketonization of Aldehydes. ChemSusChem, 9(17), 2430-2442. doi:10.1002/cssc.201600654Ketones 1982K. Matsuoka K. Tagawa Ketones 1985Miller, A. L., Cook, N. C., & Whitmore, F. C. (1950). The Ketonic Decarboxylation Reaction1: The Ketonic Decarboxylation of Trimethylacetic Acid2and Isobutyric Acid. Journal of the American Chemical Society, 72(6), 2732-2735. doi:10.1021/ja01162a107Wang, G., Wang, H., Zhang, H., Zhu, Q., Li, C., & Shan, H. (2016). Highly Selective and Stable NiSn/SiO2Catalyst for Isobutane Dehydrogenation: Effects of Sn Addition. ChemCatChem, 8(19), 3137-3145. doi:10.1002/cctc.201600685Estes, D. P., Siddiqi, G., Allouche, F., Kovtunov, K. V., Safonova, O. V., Trigub, A. L., ⌠CopĂŠret, C. (2016). CâH Activation on Co,O Sites: Isolated Surface Sites versus Molecular Analogs. Journal of the American Chemical Society, 138(45), 14987-14997. doi:10.1021/jacs.6b08705Rodemerck, U., Sokolov, S., Stoyanova, M., Bentrup, U., Linke, D., & Kondratenko, E. V. (2016). Influence of support and kind of VO species on isobutene selectivity and coke deposition in non-oxidative dehydrogenation of isobutane. Journal of Catalysis, 338, 174-183. doi:10.1016/j.jcat.2016.03.003Yokoyama, T., Setoyama, T., Fujita, N., Nakajima, M., Maki, T., & Fujii, K. (1992). Novel direct hydrogenation process of aromatic carboxylic acids to the corresponding aldehydes with zirconia catalyst. Applied Catalysis A: General, 88(2), 149-161. doi:10.1016/0926-860x(92)80212-uRenz, M., & Corma, A. (2004). Ketonic Decarboxylation Catalysed by Weak Bases and Its Application to an Optically Pure Substrate. European Journal of Organic Chemistry, 2004(9), 2036-2039. doi:10.1002/ejoc.200300778Yang, C.-G., Reich, N. W., Shi, Z., & He, C. (2005). Intramolecular Additions of Alcohols and Carboxylic Acids to Inert Olefins Catalyzed by Silver(I) Triflate. Organic Letters, 7(21), 4553-4556. doi:10.1021/ol051065fCoffman, D. D., Jenner, E. L., & Lipscomb, R. D. (1958). Syntheses by Free-radical Reactions. I. Oxidative Coupling Effected by Hydroxyl Radicals. Journal of the American Chemical Society, 80(11), 2864-2872. doi:10.1021/ja01544a068Langhals, E., & Langhals, H. (1990). Alkylation of ketones by use of solid KOH in dimethyl sulfoxide. Tetrahedron Letters, 31(6), 859-862. doi:10.1016/s0040-4039(00)94647-1Giera, H., Huisgen, R., Langhals, E., & Polborn, K. (2002). Massive Steric Hindrance in TwoâThiocarbonyl Ylidesâ: Cycloadditions with Tetra-Acceptor-Substituted Ethylenesvia Zwitterionic Intermediates. Helvetica Chimica Acta, 85(6), 1523-1545. doi:10.1002/1522-2675(200206)85:63.0.co;2-oStothers, J. B., & Tan, C. T. (1974). 13C Nuclear Magnetic Resonance Studies. 34. The 13C Spectra of Several Methylcyclopentanones and -cyclohexanones. Canadian Journal of Chemistry, 52(2), 308-314. doi:10.1139/v74-050Takenaka, K., Mohanta, S. C., Patil, M. L., Rao, C. V. L., Takizawa, S., Suzuki, T., & Sasai, H. (2010). Enantioselective Wacker-Type Cyclization of 2-Alkenyl-1,3-diketones Promoted by Pd-SPRIX Catalyst. Organic Letters, 12(15), 3480-3483. doi:10.1021/ol1013069Dauben, W. G., & Michno, D. M. (1977). Direct oxidation of tertiary allylic alcohols. A simple and effective method for alkylative carbonyl transposition. The Journal of Organic Chemistry, 42(4), 682-685. doi:10.1021/jo00424a023Vatèle, J.-M. (2010). Lewis acid-catalyzed oxidative rearrangement of tertiary allylic alcohols mediated by TEMPO. Tetrahedron, 66(4), 904-912. doi:10.1016/j.tet.2009.11.10
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Entwicklung einer wissensbasierten Optimierstrategie fĂźr die Katalysatorentwicklung mit Hochdurchsatzmethoden : Teilbericht Leibniz-Institut fĂźr Katalyse ; Abschlussbericht fĂźr das Verbundprojekt ; Laufzeit 1.1.2004 - 31.12.2006
[no abstract available
A Genetic Algorithm for Solving Combinatorial Problems and the Effects of Experimental Error - Applied to Optimizing Catalytic Materials
Parallel synthesis and fast catalytic testing of catalyst libraries for oxidation reactions
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