Recent research progress on bio-oil conversion into bio-fuels and raw chemicals: a review

Recent advances in lignocellulosic biomass valorization for producing fuels and commodities (olefins and BTX aromatics) are gathered in this paper, with a focus on the conversion of bio-oil (produced by fast pyrolysis of biomass). The main valorization routes are: (i) conditioning of bio-oil (by esterification, aldol condensation, ketonization, in situ cracking, and mild hydrodeoxygenation) for its use as a fuel or stable raw material for further catalytic processing; (ii) production of fuels by deep hydrodeoxygenation; (iii) ex situ catalytic cracking (in line) of the volatiles produced in biomass pyrolysis, aimed at the selective production of olefins and aromatics; (iv) cracking of raw bio-oil in units designed with specific objectives concerning selectivity; and (v) processing in fluidized bed catalytic cracking (FCC) units. This review deals with the technological evolution of these routes, in terms of catalysts, reaction conditions, reactors, and product yields. A study has been carried out on the current state-of-knowledge of the technological capacity, advantages and disadvantages of the different routes, as well as on the prospects for the implementation of each route within the scope of the Sustainable Refinery. © 2018 Society of Chemical Industry     

Solid state reactions between SiC and Ir

Reactivity between SiC and Ir as a function of SiC-crystallinity was investigated by diffusion bonding technique under a vacuum and over the temperature range of 1200–1450 °C. As reaction products, various Ir-silicides and free unreacted-C were detected. Reactivity is strongly affected by the temperature and SiC-crystallinity involving a series of interactions, from “no reaction” to “massive exothermic reactions”. In particular, interfacial phenomena are more pronounced by the presence of defects and grain boundaries.Solid state reactions result in formation of fine C-precipitates rearranged in a quasi-periodic microstructure. On the contrary, clustering of highly ordered C-precipitates (C-graphitized) occurs after “massive reactions” take place.A relationship between the degree of graphitization (from 1 to multi-layers of graphene), temperature and SiC crystallinity was found by Raman spectroscopy. 2D-layering phenomenon is enhanced in polycrystalline SiC at high temperature.     

Incorporation of Very Insoluble Monomers in Waterborne Coatings

The benefits of polymerizing very insoluble monomers in aqueous media, avoiding the use of energy‐intensive procedures, by implementing two novel synthesis techniques based on the emulsifier combination in emulsion polymerization and on miniemulsification by phase inversion temperature are investigated. The performance of standalone polymers consisting of monomers, namely lauryl methacrylate, isobornyl acrylate, and 1H,1H,2H,2H‐perfluorodecyl acrylate, and of formulated binders with these monomers incorporated either through blending or in situ polymerization, is evaluated with special emphasis on their water‐barrier properties (e.g., uptake, whitening, immersion, and vapor resistance) and on their chemical resistance. The performance of the standalone polymers is found to be similar to that of polymers prepared by high‐shear miniemulsion polymerization, while the performance of the formulated binders is generally superior to a commercial coating formulation based on a binder recommended for water resistance.     

Conceptually new entries into cells

This article summarizes the background and a few preliminary results concerning project 7 of the NCCR Chemical Biology. The general objective is to explore new concepts for cellular uptake, membrane tunneling, sensing and labeling. Emphasis is on the use of dynamic covalent chemistry for counterion activation, slow release of polyions and fluorescent probes, and the generation of activator libraries and polyions that grow and shrink.     

Computational color analysis of paintings for different artists of the XVI and XVII centuries

We have performed a computational color analysis of images of paintings for six master painters: Titian, Rubens, El Greco, Velázquez, Rembrandt, and Vermeer. These painters show the evolution from the renaissance to the baroque style. Different first and second‐order statistical parameters have been obtained and analyzed in order to fix which of them can be common for the different artists and which of them can be representative of a certain period of time or the evolution of the art. The firsts include the orientation and semi‐axes ratio of the ellipses that define the gamut in the chromaticity diagram and the dependencies with the frequency of the power of the Fourier transforms. Most differences among artists can be found in the volume and area of the gamut, the number of discernible colors which is greater for Titian, El Greco and Rubens, compared to Velázquez, Rembrandt and Vermeer, the average value of L* and the number of dark pixels.     

Effect of Zn addition on the structure and electrochemical properties of co-doped BaCe0.6Zr0.2Ln0.2O3-δ (Ln=Y,Gd, Yb) proton conductors

In this work, BaCe_0.6Zr_0.2Y_0.2-xYb_xO_3-δ and BaCe_0.6Zr_0.2Gd_0.2-xYb_xO_3-δ (x?=?0–0.20), proton conducting materials are prepared by the freeze-drying precursor method. The sintering conditions were optimized by adding Zn(NO₃)₂·6H₂O as sintering additive. The materials are thoroughly characterized by different structural and microstructural techniques, including X-ray diffraction, scanning and transmission electron microscopy, and thermogravimetric-differential thermal analysis. The addition of Zn favours the phase formation and densification at lower sintering temperatures; however, it leads to the segregation of a Zn-rich secondary phase, with general formula BaLn₂ZnO₅ (Ln?Y, Gd and Yb), which is identified and quantified for the first time. All samples with Zn as sintering aid exhibit cubic structure; however, the samples without Zn crystallize with orthorhombic or cubic structure, depending on the composition and thermal treatment. The electrical properties are studied by impedance spectroscopy. A deep analysis of the bulk and grain boundary contributions to the conductivity has revealed that the bulk conductivity remains almost unchanged along both series over Yb-doping; however, the grain boundary resistance decreases. The highest conductivity values are found for the intermediate members of both series, BaCe_0.6Zr_0.2Y_0.1Yb_0.1O_3-δ and BaCe_0.6Zr_0.2Gd_0.1Yb₁O_3-δ, with 33 and 28?mS?cm^?1 at 750?°C, respectively.     

Catalytic activity of Pt‐Re‐Pb/Al2O3 naphtha reforming catalysts

BACKGROUND: The main purpose of the naphtha reforming process is to obtain high octane naphtha, aromatic compounds and hydrogen. The catalysts are bifunctional in nature, having both acid and metal sites. The metal function is supplied by metal particles (Pt with other promoters like Re, Ge, Sn, etc.) deposited on the support. The influence of the addition of Pb to Pt‐Re/Al₂O₃ naphtha reforming catalysts was studied in this work. The catalysts were prepared by co‐impregnation and they were characterized by means of temperature programmed reduction, thermal programmed desorption of pyridine and several test reactions such as cyclohexane dehydrogenation, cyclopentane hydrogenolysis and n‐heptane reforming. RESULTS: It was found that Pb interacts strongly with the (Pt‐Re) active phase producing decay in the metal function activity. Hydrogenolysis is more affected than dehydrogenation. Part of the Pb is deposited over the support decreasing the acidity and the strength of the most acidic sites. CONCLUSION: The n‐heptane reforming reaction shows that Pb modifies the stability and selectivity of the Pt‐Re catalysts. Small Pb additions increase the stability and greatly improve the selectivity to C₇ isomers and aromatics while they decrease the formation of low value products such as methane and gases. Copyright © 2011 Society of Chemical Industry     

Management scenarios for olive oil mill waste based on characterization and leaching tests

BACKGROUND: Olive oil mill waste is a serious environmental problem in the Mediterranean basin given its particular characteristics of high organic content, seasonal and localized generation, and the type of processing involved. RESULTS: Olive mill waste from a three‐phase mill was characterized by means of total analysis, availability and mobility of the pollutants in order to help the decision‐maker about possible options for its valorization and/or disposal. Water content, loss of ignition, total organic carbon, phenol index and metals concentrations were measured to fully characterize the waste. Three leaching tests (NEN 7341, EN 12457 and UNE CEN‐TS 15364 EX) were carried out to evaluate the environmental hazard of the waste material and the leachates were characterized with respect to electric conductivity, pH, heavy metals, anions and organic pollutants (phenol index and total organic carbon) according to European waste directives. The results were compared with EU regulations for inert, non‐hazardous and hazardous waste disposal. CONCLUSION: It was found that not only organic parameters must be taken into account concerning the fate of this waste material, but also the mobility of heavy metals and anions should be studied. Furthermore, stabilization/solidification processes are recommended before landfill disposal of this kind of agro‐waste material. Copyright © 2011 Society of Chemical Industry     

Preparation and characterization of light‐cured methacrylate/montmorillonite nanocomposites

Polymer/clay nanocomposites were prepared from dimethacrylate monomers, commonly used in dental restorative resins, and an organically modified silicate (montmorillonite). The photopolymerization process was hardly affected by the presence of the silicate filler, and thus 2 mm thick samples containing 3 wt% clay were extensively cured. Transmission electron microscopy revealed that the montmorillonite platelets were either intercalated or exfoliated. Nevertheless, for all formulations, intermediate‐sized aggregates of about 1 µm were present and their fraction increased as the amount of filler increased. The presence of the clay was found to have no major effect on the flexural modulus and compressive yield strength of the nanocomposites. Moreover, the water uptake of nanocomposites containing 3 wt% clay was about 10–15% higher than that of unfilled monomers. Modification of the clay surface with alternative organic cations is certainly necessary in order to achieve an optimal dispersion of the clay in the polymer matrix. Copyright © 2010 Society of Chemical Industry