1. Study of Short-Chain Alcohol and Alcohol-Water Adsorption in MEL and MFI Zeolites
- Author
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Paula Gomez-Alvarez, Eva G. Noya, Enrique Lomba, João Pires, and Susana Valencia
- Subjects
Simulations ,Inorganic chemistry ,Alcohol ,02 engineering and technology ,010402 general chemistry ,01 natural sciences ,Separation ,chemistry.chemical_compound ,Diffusion behaviors ,Adsorption ,Self-Diffusion ,Electrochemistry ,General Materials Science ,Zeolite ,Spectroscopy ,Aqueous solution ,Ethanol ,Hydrogen bond ,Different temperatures ,Surfaces and Interfaces ,021001 nanoscience & nanotechnology ,Condensed Matter Physics ,Phase adsorption ,0104 chemical sciences ,Hydrocarbon mixtures ,chemistry ,Mixtures ,Fermentation ,Methanol ,0210 nano-technology ,Silicalite-1 Zeolite - Abstract
[EN] In this paper, we present a comparative study of the adsorption behavior of short chain alcohols (pure and in aqueous solution) into silicalite-1 (MFI-type zeolite) and silicalite-2 (MEL-type zeolite). For quite some time, silicalite-1 has been the reference material to address the problem of adsorptive-based separation, mostly for hydrocarbon mixtures. Interestingly, being structurally close to silicalite-1, adsorption studies using silicalite-2 are scarce and to the best of our knowledge, a comparative study of their behavior for alcohol water mixtures has not been published to date. We have here resorted to molecular simulation techniques to analyze the adsorption and diffusion phenomena in both zeolites at 25 and 50 degrees C for pure methanol, ethanol, 1-butanol, and water, and for some relevant compositions of alcohol/water mixtures. In addition to the dilute regime in the mixture, our study ranges from intermediate alcohol concentrations to alcohol-rich phases, relevant to alcohol purification processes. Besides, we have performed volumetric and calorimetric measurements of single-component adsorption of alcohols in pure silica MEL zeolite, which were used to validate the model potentials used in the simulations. We observe that the zigzag channels of MFI zeolite are most likely responsible for its somewhat higher affinity for alcohols. This leads to higher adsorption selectivities when compared to those of MEL zeolite. We have also found that the choice of water model strongly conditions water coadsorption into the zeolites and subsequently the predictions of the adsorbent's selectivity in alcohol/water systems. Despite considerable differences for adsorbed pure components, diffusivities of alcohol and water adsorbed from mixtures are relatively similar, as a consequence of the strong hydrogen bonds between hydroxyl groups and water., E.L. and E.G.N. acknowledge the support from the Agencia Estatal de Investigacion and Fondo Europeo de Desarrollo Regional (FEDER) under grants No. FIS2017-89361-C3-2-P and FIS2013-47350-05-4-R S.V. thanks J.A. Vidal-Moya for collecting the NMR data and acknowledges financial support from Spanish government (grants MAT2015-71842-P and SEV-2016-0683). J.P. thanks Fundacao para a Ciencia e a Tecnologia (FCT) for funding the project UID/MULTI/00612/2013 (C.QB.).
- Published
- 2018