Biochars from Olive Stones as Carbonaceous Support in Pt/TiO2-Carbon Photocatalysts and Application in Hydrogen Production from Aqueous Glycerol Photoreforming.

Several biochars were synthesized from olive stones and used as supports for TiO2, as an active semiconductor, and Pt as a co-catalyst (Pt/TiO2-PyCF and Pt/TiO2-AC). A third carbon-supported photocatalyst was prepared from commercial mesoporous carbon (Pt/TiO2-MCF). Moreover, a Pt/TiO2 solid based on Evonik P25 was used as a reference. The biochars used as supports transferred, to a large extent, their physical and chemical properties to the final photocatalysts. The synthesized catalysts were tested for hydrogen production from aqueous glycerol photoreforming. The results indicated that a mesoporous nature and small particle size of the photocatalyst lead to better H2 production. The analysis of the operational reaction conditions revealed that the H2 evolution rate was not proportional to the mass of the photocatalyst used, since, at high photocatalyst loading, the hydrogen production decreased because of the light scattering and reflection phenomena that caused a reduction in the light penetration depth. When expressed per gram of TiO2, the activity of Pt/TiO2-PyCF is almost 4-times higher than that of Pt/TiO2 (1079 and 273 mmol H2/gTiO2, respectively), which points to the positive effect of an adequate dispersion of a TiO2 phase on a carbonaceous support, forming a highly dispersed and homogeneously distributed titanium dioxide phase. Throughout a 12 h reaction period, the H2 production rate progressively decreases, while the CO2 production rate increases continuously. This behavior is compatible with an initial period when glycerol dehydrogenation to glyceraldehyde and/or dihydroxyacetone and hydrogen predominates, followed by a period in which comparatively slower C-C cleavage reactions begin to occur, thus generating both H2 and CO2.

Advanced Biofuels from ABE (Acetone/Butanol/Ethanol) and Vegetable Oils (Castor or Sunflower Oil) for Using in Triple Blends with Diesel: Evaluation on a Diesel Engine.

From a technical and economic point of view, our aim is to provide viable solutions for the replacement of fossil fuels which are currently used in internal combustion diesel engines. In this research, two new biofuels composed of second-generation vegetable oils (SVO),used oil sunflower (SO) or castor oil (CO), and the ABE blend (acetone/butanol/ethanol) were evaluated. ABE is an intermediate product from the fermentation of carbohydrates to obtain bio-butanol. Besides, the ABE blend exhibits suitable properties as biofuel, such asvery low kinematic viscosity, reasonable energy density, low autoignition temperature, and broad flammability limits. Diesel/ABE/SVO triple blends were prepared, characterized and then, tested on a diesel engine, evaluating power output, consumption, and exhaust emissions. The power output was slightly reduced due to the low heating values of ABE blend. Also, engine consumed more fuel with the triple blends than with diesel under low engine loads whereas, at medium and high loads, the fuel consumption was very similar to that of diesel. Regarding exhaust gas emissions, soot wasnotably reduced, and nitrogen oxides (NOx) and carbon monoxide (CO2) emissions were lower or comparable to that of diesel, while the CO emissions increased. The use of these biofuels allows the replacement of high percentagesof diesel without compromising engine power and achievinga significant reduction in pollution emissions. Furthermore, a notable improvement in cold flow properties of the fuel blends is obtained, in comparison with diesel.

Acetone Prospect as an Additive to Allow the Use of Castor and Sunflower Oils as Drop-In Biofuels in Diesel/Acetone/Vegetable Oil Triple Blends for Application in Diesel Engines.

The present paper investigates the feasibility of using acetone (ACE) in triple blends with fossil diesel (D) and straight vegetable oils (SVOs) as alternative fuel for diesel engines. In this respect, ACE is selected as an oxygenated additivedue to its favorable propertiesto be mixed with vegetable oils and fossil diesel. In fact, the very low kinematic viscosity allows reduces the high viscosity of SVOs. ACE's oxygen content, low autoignition temperature, and very low cloud point and pour point values highlight its possibilities as an additive in D/ACE/SVO triple blends. Moreover, ACE can be produced through a renewable biotechnological process, an acetone-butanol-ethanol (ABE) fermentation from cellulosic biomass. The SVOs tested were castor oil (CO), which is not suitable for human consumption, and sunflower oil (SO), used as a standard reference for waste cooking oil. The viscosity measurement of the ACE/SVO double blend was considered crucial to choose the optimum proportion, which better fulfilled the specifications established by European standard EN 590. Moreover, some of the most significant physicochemical properties of D/ACE/SVO triple blends, such as kinematic viscosity, cloud point, pour point, and calorific value, were determined to assess their suitability as fuels. The blends were evaluated in a conventional diesel generator through the study of the following parameters: engine power, smoke emissions, and fuel consumption. Despite the low calorific value of ACE limits its ratio in the mixtures due to engine knocking problems, the experimental results reveal an excellent performance for the blends containing up to 16-18% of ACE and 22-24% of SVO. These blends produce similar engine power as to fossil diesel, but with slightly higher fuel consumption. Considerable reductions in emissions of air pollutants, as well as excellent cold flow properties are also obtained with these triple blends. In summary, the use of these biofuels could achieve a substitution of fossil diesel up to 40%, independently on the SVO employed.

Olive Leaves as Biotemplates for Enhanced Solar-Light Harvesting by a Titania-Based Solid.

Olive leaves (by-product from olive oil production in olive mills) were used as biotemplates to synthesize a titania-based artificial olive leaf (AOL). Scanning electron microscopy (SEM) images of AOL showed the successful replication of trichomes and internal structure channels present in olive leaves. The BET surface area of AOL was 52 m2·g-1. X-ray diffraction (XRD) and Raman spectra revealed that the resulting solid was in the predominantly-anatase crystalline form (7.5 nm average particle size). Moreover, the synthesis led to a red-shift in light absorption as compared to reference anatase (gap energies of 2.98 and 3.2 eV, respectively). The presence of surface defects (as evidenced by X-ray photoelectron spectroscopy, XPS, and electron paramagnetic resonance spectroscopy, EPR) and doping elements (e.g., 1% nitrogen, observed by elemental analysis and XPS) could account for that. AOL was preliminarily tested as a catalyst for hydrogen production through glycerol photoreforming and exhibited an activity 64% higher than reference material Evonik P25 under solar irradiation and 144% greater under ultraviolet radiation, (under voltage) UV.

Microwave-Assisted Glycerol Etherification Over Sulfonic Acid Catalysts.

Glycerol is the main by-product of biodiesel production. For this reason, its valorization into value-added products, by using green procedures, represents an important goal. Different sulfonic acid silica- or titania-based catalysts were prepared, characterized and tested in the glycerol etherification process, assisted by microwaves, in order to obtain biodiesel additives. The surface and structural properties of the catalysts were investigated by means of N2 adsorption isotherms, thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and acid capacity measurements by X-Ray Fluorescence Spectroscopy (XRF). The best performance in terms of activity was achieved in the presence of the sulfonic function directly linked to the amorphous silica. By the correlation of the structure properties of the materials and their activity, the performance of the catalysts was shown to be influenced mainly by the surface area, pore volume and acidity. Recycling experiments performed over the most active systems showed that the sulfonic silica-based materials maintained their performance during several cycles.

Calibration of a Cohesive Model for Fracture in Low Cross-Linked Epoxy Resins.

Polymer-based composites are becoming widely used for structural applications, in particular in the aeronautic industry. The present investigation focuses on the mechanical integrity of an epoxy resin of which possible damage results in limitation or early stages of dramatic failure. Therefore, a coupled experimental and numerical investigation of failure in an epoxy resin thermoset is carried out that opens the route to an overall micromechanical analysis of thermoset-based composites. In the present case, failure is preceded by noticeable plasticity in the form of shear bands similar to observations in ductile glassy polymers. Thus, an elastic-visco-plastic constitutive law initially devoted to glassy polymer is adopted that captures the rate- dependent yield stress followed by softening and progressive hardening at continued deformation. A general rate-dependent cohesive model is used to describe the failure process. The parameters involved in the description are carefully identified and used in a finite element calculation to predict the material's toughness for different configurations. Furthermore, the present work allows investigation of nucleation and crack growth in such resins. In particular, a minimum toughness can be derived from the model which is difficult to evaluate experimentally and allows accounting for the notch effect on the onset of failure. This is thought to help in designing polymer-based composites.

Sulfonic Acid Functionalization of Different Zeolites and Their Use as Catalysts in the Microwave-Assisted Etherification of Glycerol with tert-Butyl Alcohol.

The etherification of glycerol with tert-butyl alcohol in the liquid phase, over different sulfonic acid functionalized zeolites, has been studied. The reaction was carried out using microwaves as a way of heating, measured at autogenous pressure and without any solvent. Dealuminated HY and HZSM-5 zeolites by acid treatment were functionalized with two different organosilica precursors: 3-mercaptopropyltrimethoxysilane (M), which incorporates thiol groups, and 2-(4-chlorosulfonylphenyl)ethyltrimethoxysilane (C), which incorporates the sulfonic acid groups directly. The thiol groups were oxidized into sulfonic groups employing hydrogen peroxide. The textural and structural properties of the solids were studied by XRD and N2 adsorption-desorption isotherms, whereas the incorporation of the organosilica in the zeolites was studied by TGA and XPS. The novelty functionalization of M gave rise to solids with the highest acidity, and exhibited the highest yields with more substituted ethers (Yh-GTBE = 13%), at 75 °C and 15 min of reaction time. In addition to the acidity, the textural properties of the zeolites played an important role in their activity; HY, with the largest size of the channels, were more active than the HZSM-5.

Application of Enzymatic Extracts from a CALB Standard Strain as Biocatalyst within the Context of Conventional Biodiesel Production Optimization.

The application of biocatalysts in the transesterification process of triglycerides (TG) allows integrating the glycerol in the form of monoglyceride (MG), sharply increasing the yield and the environmental sustainability of the conventional biodiesel production process. This is known as Ecodiesel. To overcome the inconvenient of the high cost of the currently employed highly purified commercial enzymes, the use of scarcely purified extracts obtained from standard strains of the same species of commercial lipases currently applied in this process is being investigated. Thus, Candidaantarctica type B (CALB) was chosen to determine the optimal conditions of culture of this yeast. The standard strain was obtained from the Spanish Type Microbial Cultures Collection (CECT) and has been used to carry out several studies to elucidate its optimum growth conditions. Through a process of lyophilization with prior dialysis of the liquid cultures, the enzymatic extracts were obtained. The different obtained cultures have been applied as biocatalysts in the 1,3-selective transesterification reaction of sunflower oil with ethanol to obtain Ecodiesel (FAEE + MG). Selectivity and reaction yields were obtained by gas chromatography. Acceptable yields are obtained during the reaction time as well as in successive reactions, demonstrating the feasibility of using these CALB enzymatic extracts as biocatalysts.

Valores de lipidos en una población normal adulta de la ciudad de Santo Domingo, República Dominicana / Levels of lipids in a healthy adult population of Santo Domingo, Dominican Republic

Se encuestaron 1857 personas de 14 barrios de la ciudad de Santo Domingo, seleccionados por muestreo sistemático previa visita a las casas por encuestadores sociales. Se determinaron en ayunas colesterol total, HDL, triglicéridos, ácido úrico y glicemia y los pacientes fueron sometidos a un cuestionario, ex físico, etc. El 74.2 por ciento resultó del sexo femenino y 23.8 por ciento sexo masculino. El promedio de colesterol total fue de 179 +- 46 mg/dL, colesterol HDL 43 +- 12 mg/dL y TG 113 +- 65 mg/dL. El colesterol total fue mas alto en las mujeres y el colesterol HDL también fue más bajo en los hombres. En la clase baja el promedio de colesterol total fue de 173 mg/dL y en la clase alta 203 mg/dL. Según el consenso europeo el 19.49 por ciento tenían un colesterol por encima de los 200 mg/dL y entre 250 y 300 mg/dL el 4,25 por ciento , en tanto que la hipertrigliceridemia fue de 6.40 por ciento . Se establecen por 1ra. vez en Santo Domingo valores de referencia para los adultos por encima de los 20 años en cuanto a lípidos se refiere