ITQ-69: A Germanium-Containing Zeolite and its Synthesis, Structure Determination, and Adsorption Properties

"This is the peer reviewed version of the following article:ITQ-69: A Germanium-Containing Zeolite and its Synthesis, Structure Determination, and Adsorption Properties, which has been published in final form at https://doi.org/10.1002/anie.202100822. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving."[EN] In this work, a new zeolite named as ITQ-69, has been synthesized, characterized and its application as selective adsorbent for industrially relevant light olefins/paraffins separations has been assessed. This material has been obtained as pure germania as well as silica-germania zeolites with different Si/Ge ratios using a diquaternary ammonium cation as organic structure directing agent. Its structure was determined by single-crystal X-Ray diffraction showing a triclinic unit cell forming a tridirectional small pore channel system (8x8x8R). Also, it has been found that Si preferentially occupies some special T sites of the structure as deduced from Rietveld analysis of the powder X-ray diffraction patterns. In addition, the new zeolite ITQ-69 has been found to be stable upon calcination and thus, its adsorption properties were evaluated, showing a promising kinetic selectivity for light olefin separations in the C3 fraction.The authors acknowledge the Spanish Ministry of Science, Innovation and Universities (MCIU) for their funding via project RTI2018-101784-B-I00 and Program Severo Ochoa SEV-2016-0683. AS and EPB thanks for their grants BES-2016-078684 and FPU15/01602, respectively. The Microscopy Service of the UPV is acknowledged for their help in sample characterization. By last, authors would like to thank the use of RIAIDT-USC analytical facilities, especially to Dr. Antonio L. Llamas for extremely useful comments on SCXRD analyses.Sala-Gascon, A.; Pérez-Botella, E.; Jorda Moret, JL.; Cantin Sanz, A.; Rey Garcia, F.; Valencia Valencia, S. (2021). ITQ-69: A Germanium-Containing Zeolite and its Synthesis, Structure Determination, and Adsorption Properties. Angewandte Chemie International Edition. 60(21):11745-11750. https://doi.org/10.1002/anie.2021008221174511750602

A Smart Phone-based Personal Area Network for Remote Monitoring of Biosignals

This paper presents a system whose purpose is to monitor a patient continuously from indoor or outdoor environments. The system is based on a Bluetooth PAN, carried by the patient, whose central node, a smart phone, compiles information about patient’s location and health status. These data are encrypted to be sent to a server through Wifi or GPRS/UMTS. The system provides facilities to access to patient’s data, even from a smart phone by a J2ME application. It also allows to configure remotely the threshold values used to detect emergency situations.Ministerio de Eduación y Ciencia TEC2006-12211-C02-01/TCMMinisterio de Educación y Ciencia TIC2003- 07953-C02-0

Unusually Low Heat of Adsorption of CO2 on AlPO and SAPO Molecular Sieves

[EN] The capture of CO2 from post-combustion streams or from other mixtures, such as natural gas, is an effective way of reducing CO2 emissions, which contribute to the greenhouse effect in the atmosphere. One of the developing technologies for this purpose is physisorption on selective solid adsorbents. The ideal adsorbents are selective toward CO2, have a large adsorption capacity at atmospheric pressure and are easily regenerated, resulting in high working capacity. Therefore, adsorbents combining molecular sieving properties and low heats of adsorption of CO2 are of clear interest as they will provide high selectivities and regenerabilities in CO2 separation process. Here we report that some aluminophosphate (AlPO) and silicoaluminophosphate (SAPO) materials with LTA, CHA and AFI structures present lower heats of adsorption of CO2 (13¿25 kJ/mol) than their structurally analogous zeolites at comparable framework charges. In some cases, their heats of adsorption are even lower than those of pure silica composition (20¿25 kJ/mol). This could mean a great improvement in the regeneration process compared to the most frequently used zeolitic adsorbents for this application while maintaining most of their adsorption capacity, if materials with the right stability and pore size and topology are found.We acknowledge the Spanish Ministry of Sciences, Innovation and Universities (MCIU), State Research Agency (AEI), and the European Fund for Regional Development (FEDER) for their funding via projects Multi2HYcat (EU-Horizon 2020 funded project under grant agreement no. 720783), Program Severo Ochoa SEV-2016-0683 and RTI2018-101033-B-I00 and also Fundacion Ramon Areces for funding through a research contract (CIVP18A3908). EP-B thanks the MCIU for his grant (FPU15/01602). NG-C thanks MCIU for her grant (BES-2016-078178).Pérez-Botella, E.; Martínez-Franco, R.; Gonzalez-Camuñas, N.; Cantin Sanz, A.; Palomino Roca, M.; Moliner Marin, M.; Valencia Valencia, S.... (2020). Unusually Low Heat of Adsorption of CO2 on AlPO and SAPO Molecular Sieves. Frontiers in Chemistry. 8:1-10. https://doi.org/10.3389/fchem.2020.588712S1108Bacsik, Z., Cheung, O., Vasiliev, P., & Hedin, N. (2016). Selective separation of CO2 and CH4 for biogas upgrading on zeolite NaKA and SAPO-56. Applied Energy, 162, 613-621. doi:10.1016/j.apenergy.2015.10.109BaerlocherC. H. McCuskerL. B. Database of Zeolite StructuresBoot-Handford, M. E., Abanades, J. C., Anthony, E. J., Blunt, M. J., Brandani, S., Mac Dowell, N., … Fennell, P. S. (2014). Carbon capture and storage update. Energy Environ. Sci., 7(1), 130-189. doi:10.1039/c3ee42350fBourgogneM. GuthJ.-L. WeyR. Process for the Preparation of Synthetic Zeolites, and Zeolites Obtained by Said Process1985Bui, M., Adjiman, C. S., Bardow, A., Anthony, E. J., Boston, A., Brown, S., … Mac Dowell, N. (2018). Carbon capture and storage (CCS): the way forward. Energy & Environmental Science, 11(5), 1062-1176. doi:10.1039/c7ee02342aCheung, O., Liu, Q., Bacsik, Z., & Hedin, N. (2012). Silicoaluminophosphates as CO2 sorbents. Microporous and Mesoporous Materials, 156, 90-96. doi:10.1016/j.micromeso.2012.02.003Corma, A., Rey, F., Rius, J., Sabater, M. J., & Valencia, S. (2004). Supramolecular self-assembled molecules as organic directing agent for synthesis of zeolites. Nature, 431(7006), 287-290. doi:10.1038/nature02909Dawson, D. M., Griffin, J. M., Seymour, V. R., Wheatley, P. S., Amri, M., Kurkiewicz, T., … Ashbrook, S. E. (2017). A Multinuclear NMR Study of Six Forms of AlPO-34: Structure and Motional Broadening. The Journal of Physical Chemistry C, 121(3), 1781-1793. doi:10.1021/acs.jpcc.6b11908Díaz-Cabañas, M.-J., & Barrett, P. A. (1998). Synthesis and structure of pure SiO2 chabazite: the SiO2 polymorph with the lowest framework density. Chemical Communications, (17), 1881-1882. doi:10.1039/a804800bFischer, M. (2017). Computational evaluation of aluminophosphate zeotypes for CO2/N2 separation. Physical Chemistry Chemical Physics, 19(34), 22801-22812. doi:10.1039/c7cp03841kGarcía, E. J., Pérez-Pellitero, J., Pirngruber, G. D., Jallut, C., Palomino, M., Rey, F., & Valencia, S. (2014). Tuning the Adsorption Properties of Zeolites as Adsorbents for CO2 Separation: Best Compromise between the Working Capacity and Selectivity. Industrial & Engineering Chemistry Research, 53(23), 9860-9874. doi:10.1021/ie500207sGirnus, I., Jancke, K., Vetter, R., Richter-Mendau, J., & Caro, J. (1995). Large AlPO4-5 crystals by microwave heating. Zeolites, 15(1), 33-39. doi:10.1016/0144-2449(94)00004-cGlobal Status Report of CCS2019International Zeolite Association Synthesis CommissionLee, K. B., Beaver, M. G., Caram, H. S., & Sircar, S. (2008). Reversible Chemisorbents for Carbon Dioxide and Their Potential Applications. Industrial & Engineering Chemistry Research, 47(21), 8048-8062. doi:10.1021/ie800795yLee, S.-Y., & Park, S.-J. (2015). A review on solid adsorbents for carbon dioxide capture. Journal of Industrial and Engineering Chemistry, 23, 1-11. doi:10.1016/j.jiec.2014.09.001Lemishko, T., Valencia, S., Rey, F., Jiménez-Ruiz, M., & Sastre, G. (2016). Inelastic Neutron Scattering Study on the Location of Brønsted Acid Sites in High Silica LTA Zeolite. The Journal of Physical Chemistry C, 120(43), 24904-24909. doi:10.1021/acs.jpcc.6b09012Leung, D. Y. C., Caramanna, G., & Maroto-Valer, M. M. (2014). An overview of current status of carbon dioxide capture and storage technologies. Renewable and Sustainable Energy Reviews, 39, 426-443. doi:10.1016/j.rser.2014.07.093Liu, X., Vlugt, T. J. H., & Bardow, A. (2011). Maxwell–Stefan diffusivities in liquid mixtures: Using molecular dynamics for testing model predictions. Fluid Phase Equilibria, 301(1), 110-117. doi:10.1016/j.fluid.2010.11.019Man, P. P., Briend, M., Peltre, M. J., Lamy, A., Beaunier, P., & Barthomeuf, D. (1991). A topological model for the silicon incorporation in SAPO-37 molecular sieves: Correlations with acidity and catalysis. Zeolites, 11(6), 563-572. doi:10.1016/s0144-2449(05)80006-5Martin, C., Tosi-Pellenq, N., Patarin, J., & Coulomb, J. P. (1998). Sorption Properties of AlPO4-5 and SAPO-5 Zeolite-like Materials. Langmuir, 14(7), 1774-1778. doi:10.1021/la960755cMartínez-Franco, R., Cantín, Á., Vidal-Moya, A., Moliner, M., & Corma, A. (2015). Self-Assembled Aromatic Molecules as Efficient Organic Structure Directing Agents to Synthesize the Silicoaluminophosphate SAPO-42 with Isolated Si Species. Chemistry of Materials, 27(8), 2981-2989. doi:10.1021/acs.chemmater.5b00337Martínez-Franco, R., Li, Z., Martínez-Triguero, J., Moliner, M., & Corma, A. (2016). Improving the catalytic performance of SAPO-18 for the methanol-to-olefins (MTO) reaction by controlling the Si distribution and crystal size. Catalysis Science & Technology, 6(8), 2796-2806. doi:10.1039/c5cy02298cMiyamoto, M., Fujioka, Y., & Yogo, K. (2012). Pure silica CHA type zeolite for CO2 separation using pressure swing adsorption at high pressure. Journal of Materials Chemistry, 22(38), 20186. doi:10.1039/c2jm34597hVan Nordstrand, R. A., Santilli, D. S., & Zones, S. I. (1988). An All-Silica Molecular Sieve That Is Isostructural with AlPO4-5. Perspectives in Molecular Sieve Science, 236-245. doi:10.1021/bk-1988-0368.ch015Palomino, M., Corma, A., Rey, F., & Valencia, S. (2009). New Insights on CO2−Methane Separation Using LTA Zeolites with Different Si/Al Ratios and a First Comparison with MOFs. Langmuir, 26(3), 1910-1917. doi:10.1021/la9026656Pham, T. D., Hudson, M. R., Brown, C. M., & Lobo, R. F. (2014). Molecular Basis for the High CO2Adsorption Capacity of Chabazite Zeolites. ChemSusChem, 7(11), 3031-3038. doi:10.1002/cssc.201402555Prakash, A. M., & Unnikrishnan, S. (1994). Synthesis of SAPO-34: high silicon incorporation in the presence of morpholine as template. Journal of the Chemical Society, Faraday Transactions, 90(15), 2291. doi:10.1039/ft9949002291Riboldi, L., & Bolland, O. (2017). Overview on Pressure Swing Adsorption (PSA) as CO2 Capture Technology: State-of-the-Art, Limits and Potentials. Energy Procedia, 114, 2390-2400. doi:10.1016/j.egypro.2017.03.1385Rubin, E. S., Davison, J. E., & Herzog, H. J. (2015). The cost of CO2 capture and storage. International Journal of Greenhouse Gas Control, 40, 378-400. doi:10.1016/j.ijggc.2015.05.018Schreyeck, L., Stumbe, J., Caullet, P., Mougenel, J.-C., & Marler, B. (1998). The diaza-polyoxa-macrocycle `Kryptofix222’ as a new template for the synthesis of LTA-type AlPO4. Microporous and Mesoporous Materials, 22(1-3), 87-106. doi:10.1016/s1387-1811(98)00082-1Shang, J., Li, G., Singh, R., Gu, Q., Nairn, K. M., Bastow, T. J., … Webley, P. A. (2012). Discriminative Separation of Gases by a «Molecular Trapdoor» Mechanism in Chabazite Zeolites. Journal of the American Chemical Society, 134(46), 19246-19253. doi:10.1021/ja309274ySircar, S., & Myers, A. (2003). Gas Separation by Zeolites. Handbook of Zeolite Science and Technology. doi:10.1201/9780203911167.ch22Tagliabue, M., Farrusseng, D., Valencia, S., Aguado, S., Ravon, U., Rizzo, C., … Mirodatos, C. (2009). Natural gas treating by selective adsorption: Material science and chemical engineering interplay. Chemical Engineering Journal, 155(3), 553-566. doi:10.1016/j.cej.2009.09.010Thommes, M., Kaneko, K., Neimark, A. V., Olivier, J. P., Rodriguez-Reinoso, F., Rouquerol, J., & Sing, K. S. W. (2015). Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure and Applied Chemistry, 87(9-10), 1051-1069. doi:10.1515/pac-2014-1117NIST Chemistry WebBook, SRD 69–Carbon DioxideWilson, S. T., Lok, B. M., Messina, C. A., Cannan, T. R., & Flanigen, E. M. (1982). Aluminophosphate molecular sieves: a new class of microporous crystalline inorganic solids. Journal of the American Chemical Society, 104(4), 1146-1147. doi:10.1021/ja00368a062Young, D., & Davis, M. E. (1991). Studies on SAPO-5: synthesis with higher silicon contents. Zeolites, 11(3), 277-281. doi:10.1016/s0144-2449(05)80232-5Zibrowius, B., Löffler, E., & Hunger, M. (1992). Multinuclear MAS n.m.r. and i.r. spectroscopic study of silicon incorporation into SAPO-5, SAPO-31, and SAPO-34 molecular sieves. Zeolites, 12(2), 167-174. doi:10.1016/0144-2449(92)90079-5Zones, S. I. (1991). Conversion of faujasites to high-silica chabazite SSZ-13 in the presence of N,N,N-trimethyl-1-adamantammonium iodide. Journal of the Chemical Society, Faraday Transactions, 87(22), 3709. doi:10.1039/ft9918703709Zones, S. I., & Van Nordstrand, R. A. (1988). Novel zeolite transformations: The template-mediated conversion of Cubic P zeolite to SSZ-13. Zeolites, 8(3), 166-174. doi:10.1016/s0144-2449(88)80302-

Regulation of L-ascorbic acid content in strawberry fruits

Plants have several L-ascorbic acid (AsA) biosynthetic pathways, but the contribution of each one to the synthesis of AsA varyies between different species, organs, and developmental stages. Strawberry (Fragaria×ananassa) fruits are rich in AsA. The pathway that uses D-galacturonate as the initial substrate is functional in ripe fruits, but the contribution of other pathways to AsA biosynthesis has not been studied. The transcription of genes encoding biosynthetic enzymes such as D-galacturonate reductase (FaGalUR) and myo-inositol oxygenase (FaMIOX), and the AsA recycling enzyme monodehydroascorbate reductase (FaMDHAR) were positively correlated with the increase in AsA during fruit ripening. Fruit storage for 72 h in a cold room reduced the AsA content by 30%. Under an ozone atmosphere, this reduction was 15%. Ozone treatment increased the expression of the FaGalUR, FaMIOX, and L-galactose-1-phosphate phosphatase (FaGIPP) genes, and transcription of the L-galactono-1,4-lactone dehydrogenase (FaGLDH) and FAMDHAR genes was higher in the ozone-stored than in the air-stored fruits. Analysis of AsA content in a segregating population from two strawberry cultivars showed high variability, which did not correlate with the transcription of any of the genes studied. Study of GalUR protein in diverse cultivars of strawberry and different Fragaria species showed that a correlation between GalUR and AsA content was apparent in most cases, but it was not general. Three alleles were identified in strawberry, but any sequence effect on the AsA variability was eliminated by analysis of the allele-specific expression. Taken together, these results indicate that FaGalUR shares the control of AsA levels with other enzymes and regulatory elements in strawberry fruit

Porous Solids for Adsorption and Separation of Gas and Vapor Mixtures

[ES] En esta tesis se han estudiado las propiedades de diferentes adsorbentes zeolíticos y su uso en separaciones de mezclas fluidas de interés industrial. La selección de los materiales se ha realizado poniendo especial énfasis en los adsorbentes zeolíticos de poro pequeño de baja polaridad, más concretamente, zeolitas pura sílice, aluminofosfatos y silicoaluminofosfatos. Las separaciones que se han considerado están relacionadas principalmente con la producción de energía, procesado del gas natural y del biogás, purificación de hidrógeno, mejora del índice de octano de la gasolina y purificación de biobutanol. Las propiedades de adsorción se han estudiado mediante medidas de isotermas de adsorción de un solo componente, medidas de cinéticas de adsorción de un solo componente y experimentos de adsorción dinámica multicomponente, es decir, experimentos de curvas de ruptura. Las isotermas de adsorción se analizaron en cuanto a forma y capacidad máxima de adsorción y se utilizaron para calcular los calores isostéricos de adsorción, las selectividades termodinámicas y las capacidades de trabajo ideales en procesos hipotéticos de adsorción por oscilación. Las medidas de cinéticas de adsorción han permitido comparar el comportamiento difusional de diferentes adsorbatos en diferentes materiales y calcular las constantes de difusión temporales, que a su vez fueron utilizadas para calcular selectividades cinéticas ideales / factores de separación. Los experimentos de curvas de ruptura se utilizaron para ver cómo se comportan los materiales en condiciones cercanas al caso industrial, para calcular las selectividades reales de mezcla y los parámetros de operación relevantes de procesos de adsorción, es decir, productividad, recuperación y pureza. Las propiedades físicas de los materiales estudiados, como la estructura, el orden cristalino, la conectividad atómica, el tamaño y la forma de las partículas y las propiedades texturales, han sido evaluadas y empleadas para explicar los resultados obtenidos en los experimentos de adsorción. En el capítulo 1, se presenta una introducción general sobre las zeolitas, su síntesis, propiedades y aplicaciones, junto con una introducción acerca de los fenómenos de adsorción y las separaciones industriales de interés para esta tesis. En el capítulo 2 se presentan los objetivos de este trabajo de tesis. En el capítulo 3 se presenta la síntesis de los adsorbentes utilizados, junto con los equipos de caracterización y adsorción y los procedimientos de análisis de datos de adsorción. En el capítulo 4, se estudia la adsorción de gases ligeros en Si-RWR con especial énfasis en la separación de isótopos de hidrógeno y la purificación del hidrógeno presente en la corriente de salida de un proceso de reformado de metano con vapor. En el capítulo 5 estudio las propiedades de adsorción de \ce{CO2} en aluminofosfatos, silicoaluminofosfatos y zeolitas de estructuras LTA, CHA y AFI, y más específicamente los calores isostéricos de adsorción. En el capítulo 6, estudio el efecto del tamaño de poro y la topología de poro en la separación de \ce{CO2} de \ce{CH4} mediante isotermas de compuestos puros y experimentos de ruptura de la mezcla. En el capítulo 7, se estudian las propiedades de adsorción de hidrocarburos de las fracciones C5-C7 en Si-STW con la atención puesta en la separación de hidrocarburos dirramificados de monorramificados y lineales. Se establece una comparación con Si-MFI. En el capítulo 8 se estudia una serie de zeolitas puramente silíceas para la separación de una mezcla de vapores de 1-butanol, acetona, etanol y agua proveniente de un proceso de fermentación. Se han realizado experimentos de adsorción de los compuestos puros, así como de mezclas de ellos mediante curvas de ruptura. Se presta atención a la recuperación de 1-butanol durante el proceso de adsorción, estudiá[CA] En aquesta tesi, s'han estudiat les propietats de diferents adsorbents zeolítics i el seu ús en separacions de mescles de fluids d'interès industrial. La selecció dels materials s'ha dut a terme posant un èmfasi especial en els adsorbents zeolítics de porus petit de baixa polaritat, més concretament, les zeolites pura sílice, aluminofosfats i silicoaluminofosfats. Les separacions que s'han considerat estan relacionades principalment amb la producció d'energia, el processament de gas natural i de biogàs, la purificació d'hidrogen, la millora del nombre d'octans de la gasolina i la purificació de biobutanol. Les propietats d'adsorció s'han estudiat mitjançant isotermes d'adsorció d'un component, cinètiques d'adsorció d'un component i experiments d'adsorció dinàmica multicomponent, és a dir, experiments de corbes de ruptura. Les isotermes d'adsorció es van analitzar en funció de la seva forma i capacitat màxima d'adsorció i es van utilitzar per calcular les calors isostèriques d'adsorció, les selectivitats termodinàmiques i les capacitats de treball ideals en els hipotètics processos d'adsorció per oscil·lació . Les mesures de cinètiques d'adsorció han permès comparar el comportament difusional de diferents adsorbats en diferents materials i calcular constants temporals de difusió, que, al seu torn, s'han utilitzat per al càlcul de selectivitats cinètiques ideals/factors de separació. Els experiments de corbes de ruptura es van utilitzar per, veure com funcionen els materials en condicions properes al cas industrial i per calcular per a cada mescla les selectivitats i els paràmetres d'operació rellevants per a processos d'adsorció, és a dir, la productivitat, la recuperació i la puresa. Les propietats físiques dels materials estudiats, com ara l'estructura, l'ordre cristal·lí, la connectivitat dels àtoms, la mida i la forma de les partícules i les propietats texturals s'han avaluat i s'han utilitzat per explicar els resultats obtinguts en els experiments d'adsorció. En el capítol 1, es proporciona una introducció general sobre les zeolites, la seva síntesi, propietats i aplicacions, juntament amb una introducció referent a fenòmens d'adsorció i separacions industrials d'interès en aquesta tesi. En el capítol 2 es presenten els objectius d'aquest treball de tesi. En el capítol 3 es presenta la síntesi dels adsorbents utilitzats, juntament amb els equips de caracterització i adsorció i els procediments d'anàlisi de dades d'adsorció. En el capítol 4, s'estudia l'adsorció de gasos lleugers a Si-RWR amb especial atenció a la separació d'isòtops d'hidrogen i la purificació de l'hidrogen present en el corrent de sortida d'un procés de reformat de metà amb vapor. En el capítol 5 estudio les propietats d'adsorció de \ce{CO2} en aluminofosfats, silicoaluminofosfats i zeolites d'estructures LTA, CHA i AFI i, més concretament, les seus calors d'adsorció isostèriques. En el capítol 6, estudio l'efecte de la mida i la topologia de porus sobre la separació de \ce{CO2} de \ce{CH4} mitjançant isotermes de components purs i experiments de ruptura de la mescla. En el capítol 7, s'estudien les propietats d'adsorció d'hidrocarburs de les fraccions C5-C7 en Si-STW amb especial atenció a la separació d'hidrocarburs lineals i monorramificats de dirramificats. S'estableix una comparació amb Si-MFI. En el capítol 8 s'estudia una sèrie de zeolites purament silícies per a la separació d'una mescla de vapors de 1-butanol, acetona, etanol i aigua provinent d'un procés de fermentació. S'han realitzat experiments d'adsorció dels compostos purs, així com de mescles d'ells mitjançant corbes de ruptura. Es para atenció a la recuperació de 1-butanol durant el procés d'adsorció, estudiant-se la recuperació del producte desitjat enfront de la puresa d'aquest.[EN] In this thesis, the properties of different zeolitic adsorbents and their use in separations of fluid mixtures of industrial interest have been studied. The selection of the materials has been carried out putting a special emphasis on low polarity small pore zeolitic adsorbents, more specifically, pure silica zeolites, aluminophosphates and silicoaluminophosphates. The separations that have been considered are related mostly to energy production, natural and biogas upgrading, purification of hydrogen, gasoline octane number improvement and purification of biobutanol. The adsorption properties of the zeolitic materials have been studied by single component adsorption isotherm measurements, single component adsorption kinetics measurements and multicomponent dynamic adsorption experiments, i.e. breakthrough experiments. The adsorption isotherms were analysed in terms of their shape, the maximum adsorption capacity and used to calculate isosteric heats of adsorption, ideal thermodynamic selectivities and ideal working capacities in hypothetical swing adsorption processes. The adsorption kinetics measurements have allowed to compare the diffusional behavior of different adsorbates in different materials and to calculate diffusional time constants, which were, in turn, used for calculating ideal kinetic selectivities/separation factors. The breakthrough experiments were used to ultimately see how materials perform at conditions close to the industrial case and to calculate for each material mixture selectivities and relevant swing adsorption process operation parameters, i.e. productivity, recovery and purity. The physical properties of the studied materials, such as structure, crystalline order, atom connectivity, particle size and shape and textural properties have been critically evaluated and used to explain the results obtained in the adsorption studies. In chapter 1, a general introduction on zeolites, their synthesis, properties and applications is provided, together with an introduction on adsorption phenomena and on the industrial separations of interest to this thesis. In chapter 2 the objectives of this thesis work are presented. In chapter 3 the synthesis of the adsorbents used is presented, together with the characterization and adsorption equipment and the adsorption data analysis procedures. In chapter 4, the adsorption of light gases on pure silica RWR zeolite is studied with special focus on the separation of hydrogen isotopes and the purification of hydrogen from steam methane reformery off-gas. In chapter 5 I study the adsorption properties of CO2 on aluminophosphates, silicoaluminophosphates and zeolites of LTA, CHA and AFI structures, and more specifically their isosteric heats of adsorption. In chapter 6, I study the effect of pore size and pore topology on the separation of CO2 from CH4 by means of pure component isotherms and breakthrough experiments of the mixture. In chapter 7, the adsorption properties of C5-C7 hydrocarbons on pure silica STW zeolite are studied with special focus on the separation of dibranched from monobranched and linear hydrocarbons. A comparison with pure silica MFI zeolite (silicalite-1) is established. In chapter 8 a set of pure silica zeolites is studied as adsorbents for the vapor phase separation of 1-butanol from acetone, ethanol and water, typical components of the ABE fermentation broth. Pure component isotherms were measured and breakthrough experiments were carried out using multicomponent mixtures. Special focus is put on the recovery of 1-butanol from the desorption curve, and the dependence of purity with recovery is studied.I would like to thank the Spanish Ministry of Science, Innovation and Universities (MCIU) for my grant FPU15/01602, which has allowed me to carry out this thesis. I thank again the MCIU for paying my short stay in Brussels and for the funding provided through many different projects (RTI2018-101784-B-I00, Program Severo Ochoa SEV-2016-0683; and previous ones), which covered the costs of my research activities and allowed for my assistance to numerous international conferences which completed my training as a scientist. I thank the Instituto de Tecnología Química, the Universitat Politècnica de València (UPV) and the Consejo Superior de Investigaciones Científicas for providing the infrastructure needed for carrying out successful research.Pérez Botella, E. (2021). Porous Solids for Adsorption and Separation of Gas and Vapor Mixtures [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/178978TESI

Estudios de difusión de mezclas de propano y propeno en zeolita Si-LTA (ITQ-29) empleando scattering cuasielástico de neutrones (QENS)

[EN] The separation process of propane-propene mixtures is very important in the petrochemical industry and the development of a non-cryogenic alternative method still remains a challenge. Such alternative process would mean great both energetic and economic savings. One of the possible candidates is adsorptive separation using zeolite adsorbents. In the present work the competitive diffusion of propene in the presence of d8- propane and of propane in the presence of d6-propene in the zeolite ITQ-29 has been studied, in order to characterize the molecular motions of propene and propane at a 3 microscopic scale and calculate its diffusion coefficient at different temperatures. It has been found that the motion can’t be fully explained by free traslational diffusion and that it might be similar to diffusion inside a closed spherical volume, which would correspond to the zeolite cavities. Under the studied conditions propane seems to diffuse faster than propene.Un parámetro clave para conocer la aplicabilidad de un sólido en un proceso de adsorción o separación de gases es el coeficiente de difusión, y concretamente, su evolución con la temperatura. No existe una gran variedad de métodos de medida experimental de dichos coeficientes en sistemas sólido-gas. Uno de ellos, que ha sido desarrollado en las últimas décadas, es el QENS (scattering cuasielástico de neutrones). Se basa en la interacción entre los neutrones y las partículas de gas confinadas en el sólido, en nuestro caso, microporoso (zeolita). Los estudios de difusividad de un gas en mezclas son aún más valiosos que los de los gases puros, si quieren extrapolarse conclusiones a procesos de separación industriales. En este trabajo se obtienen coeficientes de difusión de propano en presencia de propeno (mezcla equimolar) en zeolita ITQ-29 a distintas temperaturas. Se parte de datos experimentales de QENS registrados en LET (ISIS) en 2014. Mediante el tratamiento de los datos, para lo cual no existe software que permita automatizarlo, se derivan los parámetros de interésPérez Botella, E. (2016). Estudios de difusión de mezclas de propano y propeno en zeolita Si-LTA (ITQ-29) empleando scattering cuasielástico de neutrones (QENS). http://hdl.handle.net/10251/76814TFG

Separation of biobutanol from synthetic fermentation mixtures using unidirectional small pore pure silica zeolites

[EN] The adsorptive vapour phase separation of 1-butanol from a synthetic ABE (acetone, 1-butanol, ethanol) mixture has been studied for the first time on a set of unidirectional small pore pure silica zeolites with ITW, MTF, RTH and STT structures with different pore size and topology. With this systematic approach, we provide insight into the structural and surface properties that can improve the vapour phase recovery of biobutanol. The influence of operation parameters, such as the temperature (40-80 degrees C), the total flow, and presence/absence of humidity and CO2 have been studied. For this application, adsorbents need to possess pore openings with one of their di-mensions larger than 4.1 angstrom and cavities with diameters above 7 angstrom. Si-STT zeolite presents a remarkable selec-tivity towards 1-butanol, which is not affected by the presence of water or CO2 in the mixture or by an increase in the temperature. Si-STT results an excellent and robust adsorbent for this separation at conditions close to those of the headspace of the ABE fermenter, achieving purities of 90-93% at recoveries between 90 and 96%.The authors want to thank the Spanish Ministry of Science and Innovation and the Spanish Agency of Research for their funding via Project RTI2018-101784-B-I00. The Generalitat Valenciana, Conselleria d'Innovacio, Universitats, Ciencia y Societat Digital is acknowledged for their funding via project Prometeo/2021/077. EP-B acknowledges the Spanish Ministry of Education and Professional Training for the grant FPU15/01602 and the additional funding for the stay EST18/00213. Thanks to Gino V. Baron for measuring and analysing the Ar isotherms on the Si-RTH material. Very special thanks to Miguel Palomino for measuring the vapour isotherms on BelSorp Max II at the ITQ. The Mi-croscopy Service of the UPV is acknowledged for their help in sample characterisation.Pérez-Botella, E.; Claessens, B.; Valencia Valencia, S.; Rey Garcia, F.; Denayer, JF. (2022). Separation of biobutanol from synthetic fermentation mixtures using unidirectional small pore pure silica zeolites. Microporous and Mesoporous Materials. 346:1-10. https://doi.org/10.1016/j.micromeso.2022.11229511034

Insights into Adsorption of Linear, Monobranched, and Dibranched Alkanes on Pure Silica STW Zeolite as a Promising Material for Their Separation

[EN] The adsorption of linear, monobranched and dibranched saturated hydrocarbons in the gasoline range has been studied on pure silica STW zeolite (Si-STW) by using pentane, hexane, and heptane isomers as model adsorbates. Experimental single-component adsorption isotherms and kinetic measurements together with configurational bias Monte Carlo (CBMC) and molecular dynamics (MD) simulations were carried out. Significant differences in both the equilibrium adsorption and especially the adsorption kinetics were found, which suggests that the separation of the quaternary-carbon dibranched isomer is feasible. The adsorption capacities and selectivities surpass those of pure silica MFI (Si-MFI), considered as reference. Altogether, Si-STW is presented as a promising adsorbent for increasing the octane number (ON) of the hydroisomerization product by selectively excluding quaternary-carbon dibranched hydrocarbons.We acknowledge the Spanish Ministry of Sciences, Innovation and Universities (MCIU), State Research Agency (AEI), and the European Fund for Regional Development (FEDER) for their funding via project RTI2018-101784-B-I00 and Program Severo Ochoa SEV-2016-0683. A.S. thanks the MCIU for his grant BES-2016-078684. E.P.B. thanks the MCIU for his grant (FPU15/01602). A.M. thanks the Generalitat Valenciana for a predoctoral fellowship GRISOLIAP/2019/084. A.M. and G.S. thank ASIC-UPV for the computational facilities. The Electron Microscopy Service of the UPV is acknowledged for their help in sample characterization.Pérez-Botella, E.; Misturini, A.; Sala-Gascon, A.; Palomino Roca, M.; Corma Canós, A.; Sastre Navarro, GI.; Valencia Valencia, S.... (2020). Insights into Adsorption of Linear, Monobranched, and Dibranched Alkanes on Pure Silica STW Zeolite as a Promising Material for Their Separation. The Journal of Physical Chemistry C. 124(49):26821-26829. https://doi.org/10.1021/acs.jpcc.0c08517S26821268291244

Discovering HIV related information by means of association rules and machine learning

Acquired immunodeficiency syndrome (AIDS) is still one of the main health problems worldwide. It is therefore essential to keep making progress in improving the prognosis and quality of life of affected patients. One way to advance along this pathway is to uncover connections between other disorders associated with HIV/AIDS-so that they can be anticipated and possibly mitigated. We propose to achieve this by using Association Rules (ARs). They allow us to represent the dependencies between a number of diseases and other specific diseases. However, classical techniques systematically generate every AR meeting some minimal conditions on data frequency, hence generating a vast amount of uninteresting ARs, which need to be filtered out. The lack of manually annotated ARs has favored unsupervised filtering, even though they produce limited results. In this paper, we propose a semi-supervised system, able to identify relevant ARs among HIV-related diseases with a minimal amount of annotated training data. Our system has been able to extract a good number of relationships between HIV-related diseases that have been previously detected in the literature but are scattered and are often little known. Furthermore, a number of plausible new relationships have shown up which deserve further investigation by qualified medical experts