Fabrication of Defect-Free P84® Polyimide Hollow Fiber for Gas Separation: Pathway to Formation of Optimized Structure

The elimination of the additional defect healing post-treatment step in asymmetric hollow fiber manufacturing would result in a significant reduction in membrane production cost. However, obtaining integrally skinned polymeric asymmetric hollow fiber membranes with an ultrathin and defect-free selective layer is quite challenging. In this study, P84® asymmetric hollow fiber membranes with a highly thin (~56 nm) defect-free skin were successfully fabricated by fine tuning the dope composition and spinning parameters using volatile additive (tetrahydrofuran, THF) as key parameters. An extensive experimental and theoretical study of the influence of volatile THF addition on the solubility parameter of the N-methylpyrrolidone/THF solvent mixture was performed. Although THF itself is not a solvent for P84®, in a mixture with a good solvent for the polymer, like N-Methyl-2-pyrrolidone (NMP), it can be dissolved at high THF concentrations (NMP/THF ratio > 0.52). The as-spun fibers had a reproducible ideal CO2/N2 selectivity of 40, and a CO2 permeance of 23 GPU at 35 °C. The fiber production can be scaled-up with retention of the selectivity.This research was funded by the European Research Council under the European Union’s Seventh Framework Programme (FP/2007-2013), grant agreement no. 608490, M4CO2 project

Effect of zeolite topology and reactor configuration on the direct conversion of CO2 to light olefins and aromatics

The direct transformation of CO2 into high-value-added hydrocarbons (i.e., olefins and aromatics) has the potential to make a decisive impact in our society. However, despite the efforts of the scientific community, no direct synthetic route exists today to synthesize olefins and aromatics from CO2 with high productivities and low undesired CO selectivity. Herein, we report the combination of a series of catalysts comprising potassium superoxide doped iron oxide and a highly acidic zeolite (ZSM-5 and MOR) that directly convert CO2 to either light olefins (in MOR) or aromatics (in ZSM-5) with high space–time yields (STYC2-C4= = 11.4 mmol·g–1·h–1; STYAROM = 9.2 mmol·g–1·h–1) at CO selectivities as low as 12.8% and a CO2 conversion of 49.8% (reaction conditions: T = 375 °C, P = 30 bar, H2/CO2 = 3, and 5000 mL·g–1·h–1). Comprehensive solid-state nuclear magnetic resonance characterization of the zeolite component reveals that the key for the low CO selectivity is the formation of surface formate species on the zeolite framework. The remarkable difference in selectivity between the two zeolites is further rationalized by first-principles simulations, which show a difference in reactivity for crucial carbenium ion intermediates in MOR and ZSM-5

Zeolite Beta Membranes for the Octane Upgrading of C5/C6 Light Naphta

The zeolite Beta membranes were prepared by secondary growth method in asymmetric tubular Al2O3 supports (Inocermic GmbH, Germany), combining three different types of seeding techniques and crystallization conditions. Figure 1 show SEM micrographs of a typical non-calcined beta membrane synthesized in this work (cross section view). The vapour permeation experiments performed in the apparatus shown in Figure 2 with mixtures of nHEX, 3MP, 23DMB and 22DMB show that permeate flux increase as the degree of branching decreases following the order: nHEX>>3MP>23DMB>22DMB. Approximately one third of the feed stream cross the membranes. Figure 3 shows that in the retentate stream the fractions of monobranched and normal hexane isomers (low RON compounds) decrease while the concentration of dibranched isomers (high RON compounds) is increased in relation to the equimolar feed composition. Consequently, the RON can be boosted in retentate up to 3.8 points. These results demonstrate the potential of the zeolite beta membranes for application in the production of additive-free premium gasoline

Experimental evidence of negative linear compressibility in the MIL-53 metal–organic framework family

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Zeolite Beta membranes for the separation of hexane isomers

The preparation of a-alumina supported zeolite Beta membranes was successfully achieved and sped up by exploring combinations of three seeding techniques and three synthetic methods. The surface of the membranes was completely covered by well intergrown crystals; the thickness of the zeolite layers ranged from 2 to 6 lm depending on the synthesis method used. The quality of the membranes was tested by means of pervaporation of ethanol/1,3,5-triisopropylbenzene (TIPB) mixtures together with permporometry experiments. The performance in the vapour separation of quaternary equimolar mixtures of nhexane (nHEX), 3-methylpentane (3MP), 2,3-dimethylbutane (23DMB) and 2,2-dimethylbutane (22DMB) in the range 343–443 K showed that permeate flux decreases as the branching degree increases following the order: nHEX 3MP > 23DMB > 22DMB. In the retentate, the fractions of monobranched and normal hexane decrease while the concentration of dibranched isomers is increased compared to the feed composition. The influence of the temperature in the permeation fluxes indicates the existence of an activated transport mechanism which favours the permeation of more nHEX and 3MP with regard to their dibranched isomers. The octane number (ON) of the quaternary mixture was enhanced up to 5 points with the best synthesized membrane

Highly dispersed Ptδ+ on TixCe(1−x)O2 as an active phase in preferential oxidation of CO

Structure–activity relationships for 1 wt.% Pt catalysts were investigated for a series of TixCe(1−x)O2 (x = 1, 0.98, 0.9, 0.5, 0.2 and 0) supports prepared by the sol–gel method. The catalysts prepared by impregnation were characterized in detail by applying a wide range of techniques as N2-isotherms, XRF, XRD, Raman, XPS, H2-TPR, Drifts, UV–vis, etc. and tested in the preferential oxidation of CO in the presence of H2. Also several reaction conditions were deeply analyzed. A strong correlation between catalyst performance and the electronic properties let us to propose, based in all the experimental results, a plausible reaction mechanism where several redox cycles are involved.Financial support from Generalitat Valenciana and Ministerio de Economía y Competitividad (Spain) through projects PROME-TEOII/2014/004 and MAT2010-21147 is gratefully acknowledged. EOJ also thanks the CNPq – Brazil for her grant. EVRF gratefully acknowledge the Ministerio de Economía y Competitividad (Spain) for his Ramon y Cajal grant (RYC-2012-11427)

High performance mixed matrix membranes (MMMs) composed of ZIF-94 filler and 6FDA-DAM polymer

Carbon capture and storage (CCS) using membranes for the separation of CO2 holds great promise for the reduction of atmospheric CO2 emissions from fuel combustion and industrial processes. Among the different process outlines, post-combustion CO2 capture could be easily implemented in existing power plants. However, for this technology to become viable, new membrane materials have to be developed. In this article we present the development of high performance mixed matrix membranes (MMMs) composed of ZIF-94 filler and 6FDADAM polymer matrix. The CO2/N2 separation performance was evaluated by mixed gas tests (15CO2:85N2) at 25 °C and 1–4 bar transmembrane pressure difference. The CO2 membrane permeability was increased by the addition of the ZIF-94 particles, maintaining a constant CO2/N2 selectivity of ~22. The largest increase in CO2 permeability of ~ 200% was observed for 40 wt% ZIF-94 loading, reaching the highest permeability (2310 Barrer) at similar selectivity among 6FDA-DAM MMMs reported in literature. For the first time, the ZIF-94 metal organic framework crystals with particle size smaller than 500 nm were synthesized using nonhazardous solvent (tetrahydrofuran and methanol) instead of dimethylformamide (DMF) in a scalable process. Membranes were characterized by three non-invasive image techniques, i.e. SEM, AFM and nanoscale infrared imaging by scattering-type scanning near-field optical microscopy (s-SNOM). The combination of these techniques demonstrates a very good dispersion and interaction of the filler in the polymer layer, even at very high loadings.The authors acknowledge the financial support of the European Research Council under the European Union's Seventh Framework Programme (FP/2007–2013), under grant agreement no. 608490, M4CO2 project, and the Spanish Ministry of Economy and Competitiveness (national project MAT2015-65525-R). J.G. gratefully acknowledges support from the European Union Seventh Framework Programme (FP7/2007–2013), ERC Stg, Grant Agreement n. 335746, CrystEng-MOF-MMM

Strengthening the Bolivian pharmacovigilance system: New surveillance strategies to improve care for Chagas disease and tuberculosis.

"Chagas disease (CD) and tuberculosis (TB) are important health problems in Bolivia. Current treatments for both infections require a long period of time, and adverse drug reactions (ADRs) are frequent. This study aims to strengthen the Bolivian pharmacovigilance system, focusing on CD and TB. A situation analysis of pharmacovigilance in the Department of Cochabamba was performed. The use of a new local case report form (CRF) was implemented, together with the CRF established by the Unidad de Medicamentos y Tecnolog\xC3\xADa en Salud (UNIMED), in several healthcare centers. Training and follow-up on drug safety monitoring and ADR reporting was provided to all health professionals involved in CD and TB treatment. A comparative analysis of the reported ADRs using the CRF provided by UNIMED, the new CRF proposal, and medical records, was also performed. Our results showed that out of all patients starting treatment for CD, 37.9% suffered ADRs according to the medical records, and 25.3% of them were classified as moderate/severe (MS). Only 47.4% of MS ADRs were reported to UNIMED. Regarding TB treatment, 9.9% of all patients suffered ADRs, 44% of them were classified as MS, and 75% of MS ADRs were reported to UNIMED. These findings show that the reinforcement of the Bolivian pharmacovigilance system is an ambitious project that should involve a long-term perspective and the engagement of national health workers and other stakeholders at all levels. Continuity and perseverance are essential to achieve a solid ADR reporting system, improving patient safety, drug efficacy and adherence to treatment.

Fe-MOF Materials as Precursors for the Catalytic Dehydrogenation of Isobutane.

We investigate the use of a series of iron-based metal-organic frameworks as precursors for the manufacturing of isobutane dehydrogenation catalysts. Both the as-prepared and spent catalysts were characterized by PXRD, XPS, PDF, ICP-OES, and CHNS+O to determine the physicochemical properties of the materials and the active phases responsible for the catalytic activity. In contrast to the previous literature, our results indicate that (i) the formation of metallic Fe under reaction conditions results in secondary cracking and coke formation; (ii) the formation of iron carbide only contributes to coke formation; and (iii) the stabilization of the Fe2+ species is paramount to achieve stable and selective catalysts. In this sense, promotion with potassium and incorporation of titanium improve the catalytic performance. While potassium is well known to improve the selectivity in iron-catalyzed dehydrogenation reactions, the unprecedented effect of titanium in the stabilization of a nanometric titanomaghemite phase, even under reductive reaction conditions, results in a moderately active and highly selective catalyst for several hours on stream with a remarkable resistance to coke formation