Kinetic Model for the Direct Conversion of CO2/CO into Light Olefins over an In2O3-ZrO2/SAPO-34 Tandem Catalyst.

An original kinetic model is proposed for the direct production of light olefins by hydrogenation of CO2/CO (COx) mixtures over an In2O3-ZrO2/SAPO-34 tandem catalyst, quantifying deactivation by coke. The reaction network comprises 12 individual reactions, and deactivation is quantified with expressions dependent on the concentration of methanol (as coke precursor) and H2O and H2 (as agents attenuating coke formation). The experimental results were obtained in a fixed-bed reactor under the following conditions: In2O3-ZrO2/SAPO-34 mass ratio, 0/1-1/0; 350-425 °C; 20-50 bar; H2/COx ratio, 1-3; CO2/COx ratio, 0-1; space time, 0-10 gIn2O3-ZrO2 h molC-1, 0-20 gSAPO-34 h molC-1; time, up to 500 h; H2O and CH3OH in the feed, up to 5% vol. The utility of the model for further scale-up studies is demonstrated by its application in optimizing the process variables (temperature, pressure, and CO2/COx ratio). The model predicts an olefin yield higher than 7% (selectivity above 60%), a COx conversion of 12% and a CO2 conversion of 16% at 415 °C and 50 bar, for a CO2/COx = 0.5 in the feed. Additionally, an analysis of the effect of In2O3-ZrO2 and SAPO-34 loading in the configuration of the tandem catalyst is conducted, yielding 17% olefins and complete conversion of CO2 under full water removal conditions.

Study of the Effect of ZnO Functionalization on the Performance of a Fully Formulated Engine Oil.

The automotive sector is demanding higher specifications to achieve maximum efficiency; in this sense a new generation of lubricants with higher thermo-oxidative stability and superior tribological properties is being explored. The formulation of nanolubricants based on the nature of different nanomaterials is one of the most recent approaches, with several gaps to cover, such as dispersion stability, related to the compatibility of proposed nanomaterials with conventional additives and baseoils used in lubricant formulation. This study evaluated the effect of ZnO nanomaterial dispersed in a commercial engine oil using two different approaches; the use of surfactant and nanomaterial surface functionalization to promote higher stability and lower cluster size. Experimental evidence shows a synergetic effect between the tribological protection mechanism and the antioxidant properties in the lubricant. The effect of nanoparticle cluster size, functionalization level, and nanomaterial content are presented.

Flow Boiling Heat Transfer; Experimental Study of Hydrocarbon Based Nanorefrigerant in a Vertical Tube.

Flow boiling is a complex process but very efficient for thermal management in different sectors; enhancing flow boiling heat transfer properties is a research field of great interest. This study proposes the use of various nanomaterials, carbon-based materials, and metal oxides; in n-pentane as a hydrocarbon-based refrigerant to enhance the flow boiling heat transfer coefficient. This thermal property has been experimentally evaluated using a vertical evaporation device of glass with an internal diameter of 20 mm. The results have shown that proposed nanomaterials dispersion in n-pentane has a limited effect on the thermophysical properties and is conditioned by their dispersibility but promotes a significant increment of pentane heat transfer coefficient (h), increasing the overall heat transfer coefficient (U) of the evaporator. The enhanced heat transfer performance is attributed to the behavior of nanoparticles under working conditions and their interaction with the working surface, promoting a higher generation of nucleation sites. The observed behavior suggests a heat transfer mechanism transition from forced convection to nucleate heat transfer, supported by visual observations.

Conditions for the Joint Conversion of CO2 and Syngas in the Direct Synthesis of Light Olefins Using In2O3-ZrO2/SAPO-34 Catalyst.

The conditions for promoting the joint conversion of CO2 and syngas in the direct synthesis of light olefins have been studied. In addition, given the relevance for the viability of the process, the stability of the In2O3-ZrO2/SAPO-34 (InZr/S34) catalyst has also been pursued. The CO+CO2 (CO x ) hydrogenation experimental runs were conducted in a packed bed isothermal reactor under the following conditions: 375-425 °C; 20-40 bar; space time, 1.25-20 gcatalyst h molC -1; H2/(CO x ) ratio in the feed, 1-3; CO2/(CO x ) ratio in the feed, 0.5; time on stream (TOS), up to 24 h. Analyzing the reaction indices (CO2 and CO x conversions, yield and selectivity of olefins and paraffins, and stability), the following have been established as suitable conditions: 400 °C, 30 bar, 5-10 gcat h molC -1, CO2/CO x = 0.5, and H2/CO x = 3. Under these conditions, the catalyst is stable (after an initial period of deactivation by coke), and olefin yield and selectivity surpass 4 and 70%, respectively, with light paraffins as byproducts. Produced olefin yields follow propylene > ethylene > butenes. The conditions of the process (low pressure and low H2/CO x ratio) may facilitate the integration of sustainable H2 production with PEM electrolyzers and the covalorization of CO2 and syngas obtained from biomass.

Combined Ex and In Situ Measurements Elucidate the Dynamics of Retained Species in ZSM-5 and SAPO-18 Catalysts Used in the Methanol-to-Olefins Reaction.

The dynamics of the retained species on ZSM-5 and SAPO-18 catalysts are studied by using a combination of temperature-programmed desorption/oxidation, ex situ analysis, and in situ FTIR spectroscopic measurements over the entire conversion range, using fixed-bed and spectroscopic cell reactors, in continuous and discontinuous mode. The results point to the appropriateness of the combined methodologies to track the interconversion of active into deactivating species. A statistically relevant (supported by linear regression and multivariate analysis) association of the observations is found by using the different complementary methodologies. The kinetics of this interconversion depends on the initial conversion (tuned by acidity and space time) and microporous topology, and involve: (i) in the ZSM-5 catalysts, the diffusion of monocyclic aromatics toward the exterior of the zeolite to form coke, and (ii) in the SAPO-18 catalysts, the obstruction of the cavities by aromatics that grow into tetracyclic aromatic islands.

A direct reaction approach for the synthesis of zeolitic imidazolate frameworks: template and temperature mediated control on network topology and crystal size.

The direct acid-base reaction between ZnO/CoO/Co(OH)(2) and imidazolic ligands under moderate heating (100-160 °C), in a closed vessel, leads to the generation of the corresponding zinc/cobalt-imidazolates in a high yield (87-97%) in which network topology is controlled by the addition of small amounts of structure directing agents. Moreover, the fine tuning of the thermal process at the synthetic stage permits us to increase the crystal size, and even to grow X-ray quality single crystals.

Open-framework copper adeninate compounds with three-dimensional microchannels tailored by aliphatic monocarboxylic acids.

A series of isostructural copper(II) coordination polymers containing the nucleobase adenine and different monocarboxylic acids as bridging ligands, [Cu(2)(µ(3)-ade)(2)(µ(2)-OOC(CH(2))(n)CH(3))(2)]·xH(2)O (n from 0 to 5), have been prepared. Single-crystal X-ray analysis of acetate (n = 0) and butanoate (n = 2) compounds shows a covalent three-dimensional network in which the copper(II) centers are bridged by µ-N3,N7,N9-adeninato and µ-O,O'-carboxylato ligands, with crystallization water molecules trapped in the pores, which are decorated by the Watson-Crick faces of the adenine. The tunable permanent porosity of guest-free compounds was confirmed by gas adsorption measurements.

Microporous vanadyl-arsenate with the template incorporated exhibiting sorption and catalytic properties.

(C(5)H(14)N(2))[(VO)(3)(AsO(4))(HAsO(4))(2)(OH)].3H(2)O behaves as a microporous organically templated compound, with reversible adsorption and desorption of N(2) at 77 K, and as an extremely efficient catalyst that catalyzes selective sulfoxide formation from organic sulfides, under mild conditions.

Fe(AsO4): a new iron(III) arsenate synthesized from thermal treatment of (NH4)[Fe(AsO4)F].

The new orthorhombic Fe(AsO4) phase has been synthesized by thermal treatment at 525 degrees C of a new (NH4)[Fe(AsO4)F] compound, with a [Fe(AsO4)F]- skeleton showing channels where the ammonium cations are located. The crystal structure of Fe(AsO4) has been solved from single-crystal data. The structure is formed by layers of edge-sharing dimeric octahedra, and interconnected by chains of alternating FeO6 octahedra and AsO4 tetrahedra.