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In order for catalytic biomass pyrolysis to be economically sustainable, low cost and highly efficient catalysts are needed. In a previous work, Magnesium oxide (MgO) basic catalysts produced from natural magnesite (MgCO3) were found to be highly efficient alternatives to zeolitic catalysts which apart from their relatively high cost, they are easily deactivated due to biomass alkali deposition. In order to validate these findings in pilot scale, these natural MgO catalysts were investigated in a circulating fluidized bed pilot scale unit and were compared to a commercially available ZSM-5 catalyst. This is to the best of our knowledge the first attempt to evaluate a basic catalyst in biomass fast pyrolysis in a pilot unit employing commercially relevant process technology. The basic sites of the MgO catalysts enhanced ketonization and aldol condensation reactions, as it was verified by 2DGC-TOFMS analyses of the produced bio-oils. Deoxygenation was achieved mainly via formation of CO2, while H2O yield was substantially reduced in comparison to the ZSM-5 catalyst. As a result, bio-oils richer in hydrogen were obtained by the use of MgOs. However, the MgO catalysts led to a significant increase of the catalytically produced coke compared to ZSM-5. The effect of MgO properties, such as surface area and basicity on product yields and bio-oil composition was elaborated. In contrast to the acidic ZSM-5, no alkali metals were found to deposit on MgO, indicating different deactivation mechanisms between acidic and basic catalysts in biomass fast pyrolysis.

Over the last decade, the role of the European Union (EU) High Representative (HR/VP) became increasingly salient. However, a systematic understanding of how this figure’s leadership shaped the character of EU diplomacy and actorness in peacekeeping is lacking. To address this issue, we analyse Catherine Ashton’s leadership (as the first HR/VP post Lisbon Treaty) in the 2013 Kosovo-Serbia agreement, a high point of her tenure. We argue that Ashton’s success is largely due to her hybrid leadership, alternating between transactional and transformational and capitalising on the EU’s presence and opportunities as an international actor. We propose the concept of hybrid leadership as an analytical tool and illustrate its relevance in an empirical case study. Our examination of Ashton’s hybrid leadership contributes to shedding light on the potential role of the future HR/VPs and on how these can reinforce EU leadership, diplomacy, and actorness, contributing to reinforcing the corresponding academic debates. info:eu-repo/semantics/publishedVersion

Among the different metal-promoted catalysts for the conversion of C6 sugars to platform chemicals, Sn-based catalysts have demonstrated high activity for different types of reactions, such as isomerization, retro-aldol conversion and dehydration of glucose or its isomers. The form of Sn species, as oxides or ions, along with the properties of the support are important factors determining the prevalent reaction pathway and product distribution. In this framework, we have studied the conversion of glucose mainly in biphasic (H2O/DMSO) media, using four types of Sn-based catalysts, i.e. Sn(II) and Sn(IV) as homogeneous catalysts (Cl- salts) or as the respective oxides in heterogeneous systems, Sn(IV) as SnO2 supported on γ-Al2O3, zeolites (ZSM-5 and Beta) or mesoporous aluminosilicates (Al-MCM-41), and Snδ+ as ion-exchange cations on the above zeolites. The solid catalysts were characterized by XRD, FT-IR/pyridine, ICP-OES, XRF and N2 porosimetry. Under the studied conditions, the main products obtained were 5-HMF and lactic acid in both the homogeneous and heterogeneous systems. Based on the results obtained, it was concluded that the Lewis acidity offered by Sn oxides promotes the retro-aldol reaction pathway towards lactic acid, while the Lewis acidity offered by γ-Al2O3 enhances the synthesis of both 5-HMF and lactic acid. By combining these two functions, the Sn impregnated γ-Al2O3 catalysts induce further increase of both 5-HMF and lactic acid yields. In case of catalysts that possess Bronsted acidity as well (i.e. Sn ion-exchanged or impregnated zeolites and Al-MCM-41), dehydration reactions are promoted and the product selectivity is shifted towards 5-HMF synthesis. The highest 5-HMF molar yield of 27.5% (at complete glucose conversion) was achieved by Sn20/γ-Al2O3 accompanied by lactic acid at 16.5% molar yield. For this catalyst the effect of the solvent, catalyst concentration and reaction temperature and time, were further evaluated.

5-Hydroxymethylfurfural (5-HMF) is one of the most promising biomass derived platform chemicals. It can be synthesized from biomass carbohydrates, mainly glucose and fructose, via dehydration under acidic conditions. The reaction may be performed either in water, ionic liquids or organic solvents, in particular polar aprotic solvents. In this work, the process modelling of a two-step synthesis of 5-HMF from biomass is presented. Starting from hemicellulose-free biomass, the first step includes the hydrolysis of cellulose towards glucose in the presence of H2SO4 as catalyst, while in a second step glucose is dehydrated to 5-HMF with the aid of Sn20/γ-Αl2O3 catalyst. Hydrolysis is performed in aqueous medium, while dehydration of glucose is taking place in a DMSO/H2O mixture. The overall production of 5-HMF is modelled via the chemical process optimization software ASPEN PLUS™. The optimized process is scaled up at an industrial scale where the heat integration, mass and energy balance calculations are performed.

A novel device for measuring the thermal conductivity of polymeric materials (pure polymers or nanocomposites) is presented here. Its design is based on two cylindrical tanks containing cold and hot water. Each tank wets one side of a disc-shaped polymeric sample. The proper selection of construction materials (aluminum body, Teflon fittings, etc.) and geometry (shape, size, etc.) of the two tanks and of the sample (diameter, thickness) renders the accurate measurement of the low thermal conductivity of several polymeric materials possible. The disc-shaped sample is placed in-between the two cylindrical tanks of the device, filled with cold and hot water. The water temperature in the two tanks is an adjustable operational parameter of the device. Both tank temperatures are recorded and fitted by a proper mathematical model in order to estimate the thermal conductivity of the sample. Extensive experimentation shows a very small scatter of the estimated conductivity values. The device was used to measure thermal conductivity of several polymers such as silicone rubber and epoxy resin prepared with a variety of cross-linkers and cross-linker blends. Moreover, the above polymers are used as matrices for the incorporation of various (nano)additives, like mesoporous silica foams (MCF) and organoclays (I.30E), for the preparation of the relative polymer nanocomposites whose thermal conductivity is measured.

The “ one-pot ” hydrolyltic hydrogenation of cellulose towards C2-C6 sugar alcohols has been recognized as one of the most promising biomass valorization routes for the production of high added-value chemicals. In this work, we studied the performance of Ru and Pt catalysts supported on micro/mesoporous activated carbon, in the hydrolytic hydrogenation of microcrystalline and ball-milled cellulose, in neat water, at 180 °C and at relatively low hydrogen pressure of 2 MPa. The impact of metal loading (1–5 wt.%), metal reduction method (H 2 at 350 °C or NaBH 4 ) and acidification (sulfonation) of the AC support on cellulose conversion and selectivity to the various products were systematically addressed. It was shown that Pt is significantly more selective towards hexitols (sorbitol and mannitol) compared to Ru, in glucose-rich reaction media, such as those offered by the easily hydrolyzed ball-milled cellulose. For example, the 5wt%Pt/AC-SO 3 H catalyst afforded hexitols yield of 69.5 wt.% (at 96.1% conversion) compared to 10.9 wt.% (at 95.2% wt.% conversion) obtained by the corresponding Ru catalyst, the latter being also selective towards glycerol and propane-1,2-diol (propylene glycol). A relatively moderate metal loading, such as in 3 wt.%Ru/AC-SO 3 H, was more favorable for hexitols production (44.5 wt.% yield, at 94.8 wt.% conversion) with Ru catalysts. These results were also verified by glucose hydrogenation experiments that were conducted at the same experimental conditions. Both Pt and Ru exhibited relatively high glucose hydrogenation activity towards hexitols, versus retro-aldol reactions that lead directly to smaller C2–C4 compounds, while the difference in the final product yields between the two metals was attributed to the higher hexitols hydrogenolysis (C C cleavage) reactivity of Ru. HRTEM data showed the formation of metallic crystalline Pt and Ru nanoparticles (≤4 nm, depending on loading) as well as of amorphous oxygen-rich M(O) x δ+ phases, which were also confirmed by the XPS data. The presence of these phases which may be a source of acidity, as well as the bacisity of the parent AC used in this study, were mainly responsible for inducing isomerization, retro-aldol and dehydration reactions leading eventually to increased glycerol and propylene glycol selectivity, as was observed for both low-metal catalysts, i.e. 1 wt.% Pt or Ru/AC.

The catalytic activity of supported silver nanoparticles on mesoporous silica was studied, for the selective reduction of azines into benzyl hydrazones using sodium borohydride as mild reducing agent. Different sizes of silver nanoparticles supported on mesoporous silica (Ag/HMS) were successfully prepared by two methods, i.e. wet impregnation followed by reduction with hydrogen at 350oC and in situ deposition/reduction with a mixture of amines (ethanolamine and ethylenediamine). The Ag/HMS (amines) catalyst was found to promote the selective 1,2-reduction of aryl-substituted azines, compared to the corresponding 1,4-reduction that occurs in general reduction processes. This catalytic transfer hydrogenation process found to be clear, fast and quantitative (>99% yields and selectivity) towards benzyl hydrazones synthesis under mild conditions. Of great importance is that under the present catalytic conditions reducible functional groups remain intact. Formal kinetics, support the in situ formation of silver-hydride species being responsible for the reduction process. The presence of protic polar methanol enhanced the catalytic activity of Ag/HMS. Based on the recycling studies the catalytic system Ag/HMS-NaBH4 was found to catalyze the selective reduction of azines nine times without significant loss of its activity. Finally, one-pot reaction between the in situ produced benzyl hydrazones and a series of nitrostyrenes readily provided the regioselective synthesis of 1,3,5,-subtituted pyrazoles, highlighting a useful synthetic application of the catalytic protocol.

The thermal and catalytic fast pyrolysis of biomass aims at the production of pyrolysis oil (bio-oil), which can be utilized as a source of chemicals or as a bio-crude for the production of hydrocarbon fuels. We investigated low-cost, naturally derived basic MgO materials as catalysts for the catalytic fast pyrolysis of lignocellulosic biomass as alternatives to classical acidic zeolite catalysts. The MgO catalysts were produced from natural magnesite mineral without any significant treatment besides calcination, crushing and sieving. Their structure, composition, porosity, morphology and surface properties were thoroughly examined by XRD, XRF, N 2 porosimetry, SEM, TEM, TPD-CO 2 and TPD-NH 3 . The physicochemical characteristics of the MgO catalysts depended mainly on the different production conditions (duration and temperature of calcination). Despite their negligible acidity, the MgO catalysts effectively reduced the oxygen content of the produced bio-oil and exhibited similar or even better performance compared to that of an industrial ZSM-5 catalyst formulation ( i.e. non-catalytic pyrolysis: 38.9 wt.% organic bio-oil with 38.7 wt.% O 2 ; ZSM-5 based catalyst: 20.7 wt.% organic bio-oil with 30.9 wt.% O 2 ; selected natural MgO catalysts: 25.7 wt.% organic bio-oil with 31.0 wt.% O 2 or 21.1 wt.% organic bio-oil with 28.4 wt.% O 2 ). The basic sites of the MgO catalysts favored reduction of acids and deoxygenation via ketonization and aldol condensation reactions, as indicated by the product distribution and the composition of the bio-oil. Oxygen was removed mainly via the preferred pathway of CO 2 formation, compared to CO and water as in the case of ZSM-5 zeolite. On the other hand, reaction coke slightly increased over the MgO catalysts as compared to ZSM-5; however, the MgO formed coke was oxidized/burnt at significantly lower temperatures compared to that of ZSM-5, thus enabling MgO regeneration by relatively mild calcination in air. A systematic correlation of product yields and oxygen content of bio-oil with the physicochemical properties of the MgO catalysts has been established.

The sustainable utilization of lignocellulosic biomass as a renewable and abundant source lies at the core of the emerging biobased economy for the production of fuels, materials, and platform chemicals. The first step in the implementation of many biomass valorization technologies is the “pretreatment” that aims at biomass fractionation and recovery of its main structural components, i.e., cellulose, hemicellulose, and lignin, which can be then converted by downstream (bio)catalytic processes to targeted high added value intermediate chemicals or final products. In this respect, hydrothermal pretreatment in pure water (also called liquid hot water or autohydrolysis) offers a method with low operational costs, free of organic solvents and corrosive acids or bases, and with no use of “external” liquid or solid catalysts. In the present work, the hydrothermal pretreatment of three types of lignocellulosic forestry and agricultural residues/byproducts was studied. They are representative of hardwood (residua...

In the current study the effect of different mesoporous silica particles like MCF and SBA-15 on the solid state polymerization (SSP) of poly(ethylene terephthalate) (PET) was investigated. PET nanocomposites containing 1 and 2.5 wt% SBA-15 silica (average pore diameter 4.7 nm) and MCF silica (average pore diameter 14.2 nm) have been prepared by in-situ polymerization. All nanocomposites have been characterized using FTIR spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). SSP was conducted at 220, 230 and 240 °C for 1, 2, 3 and 4 h under vacuum. Intrinsic viscosity (IV) measurements after solid-state polymerization of nanocomposites revealed that PET/SBA-15 nanocomposites exhibited lower IV increase compared to neat PET, while the opposite was observed for PET/MCF nanocomposites, especially for 1 wt% MCF content. A simple kinetic model was employed to predict the time evolution of IV, as well as the carboxyl and hydroxyl content during SSP at different temperatures and reaction times.

Summary We present the technique of minimally invasive harvesting of bone patella tendon bone autografts for ligament reconstructions with 2 horizontal incisions. Technical guidelines as well as hints are described. The advantages and disadvantages of the technique are discussed with respect to current literature findings and the authors' experience with several hundreds of those interventions is reflected.

Catalytic fast pyrolysis (CFP) of lignin with amorphous mesoporous aluminosilicates catalysts yields a high fraction of aromatics and a relatively low amount of char/coke. The relationship between the acidity and porosity of Al-MCM-41, Al-SBA-15, and Al-MSU-J with product selectivity during lignin CFP is determined. The acid sites (mild Brønsted and stronger Lewis) are able to catalyze pyrolysis intermediates towards fewer oxygenated phenols and aromatic hydrocarbons. A generalized correlation of the product selectivity and yield with the aluminum content and acidity of the mesoporous aluminosilicates is hard to establish. Zeolitic strong acid sites are not required to achieve high conversion and selectivity to aromatic hydrocarbon because nanosized MCM-41 produces a high liquid yield and selectivity. The two most essential parameters are diffusion, which is influenced by pore and grain size, and the active site, which may be mildly acidic, but is dominated by Lewis acid sites. Nanosized grains and mild acidity are essential ingredients for a good lignin CFP catalyst.

Isomerization of glucose to fructose is an important reaction with numerous applications in terms of biomass valorization. The reaction is catalyzed enzymatically but may also proceed under alkaline conditions, in which case it is accompanied by low selectivity and formation of byproducts. Solid Lewis acid and basic catalytic materials are being studied as alternative catalysts. In this work, the isomerization of glucose to fructose in aqueous media over homogeneous and heterogeneous catalysts has been investigated. The effect of polar aprotic solvents and their mixtures with water on glucose conversion and fructose selectivity was also studied. Sodium aluminate (NaAlO2) has been proven to be very effective, resulting in high fructose yield (52.1 %) and high selectivity (84.8 %). Among the various solid catalysts tested, MgO afforded glucose conversion of 44 %, with 75.8 % and 33.4 % fructose selectivity and yield, respectively, when the isomerization reaction was conducted in neat H2O.

In the present work we studied the hydrogenation/hydrogenolysis of d -glucose over Pt and Ru catalysts supported on activated micro/mesoporous carbon (AC), under low hydrogen pressure (1.6 MPa) and relatively high reaction temperature, i.e. 180 °C. We also studied the effect of metal content (1–5 wt.%), method of metal pre-treatment/reduction (H 2 at 350 °C or NaBH 4 ) and reaction time (1–12 h). All the Ru and Pt/AC catalysts were very active (conversion ≥97%) with the Pt/AC catalysts being also very selective toward sorbitol (sel. ≥90%) irrespective of metal content, method of reduction and reaction time (up to 12 h). On the other hand, the Ru/AC catalysts exhibited a wide range of sorbitol selectivity values (55–93%) having various C 3 –C 6 sugar alcohols (1,2,5,6-hexanetetrol, arabinitol, threitol, glycerol and 1,2-propanediol) as main by-products. The formation of by-products was dependent on the crystalline/amorphous nature of Ru and Ru(O) x δ + nanoparticles which were in turn affected by the Ru content and the method of reduction.

The application of heterogeneous catalysis in biomass pyrolysis is considered as one of the most promising methods to improve bio‐oil quality by minimizing its undesirable properties (high viscosity, corrosivity, instability, etc.) and producing renewable fuels and high‐value chemicals. Catalytic fast pyrolysis (CFP) of biomass refers both to the “in situ” and “ex situ or two‐stage” upgrading. A plethora of catalytic materials have been investigated in the literature for both approaches, including conventional microporous zeolites, ordered mesoporous aluminosilicates, promoted or not with several transition metals, as well as various metal (nano)oxide catalysts with Lewis acidity. Recently, hybrid micro/mesoporous and basic materials have been also suggested exhibiting most promising results due to combined micro/mesoporosity and adequate balance of acid and basic sites. Optimum catalysts are required to retain deoxygenation, enhance yields of aromatics, and other valuable compounds (such as phenolics), while limiting coke formation. Coke formation is one of the reasons of catalyst deactivation; a very challenging issue during biomass CFP, especially using zeolites. The deactivation process is affected by many factors, including the composition of the feedstock (inorganic minerals present in the feedstock may also deposit on the catalyst), reaction conditions, and the nature/properties of the catalysts used in CFP. Precoking on the surface of zeolites or MgO deposition are among the proposed effective ways to suppress coke formation and thus, catalyst deactivation. This article is categorized under: Bioenergy > Science and Materials Energy Research & Innovation > Science and Materials Energy and Transport > Science and Materials

In this work, two series of biodegradable nanocomposites of poly(ethylene succinate) (PESu) containing either graphene oxide (GO) or organomodified GO (org-GO) with 1-dodecylamine have been prepared and studied. GO was synthesized using a modified Staudenmaier method from of powdered graphite and PESu/GO and PESu/org-GO nanocomposites with GO or org-GO concentrations 0.5, 1 or 2.5 wt% were prepared with the solvent evaporation method. The nanocomposites were characterized with several techniques. Microscopic and XRD study showed intercalated dispersion of GO into PESu matrix while in the case of org-GO fully exfoliated nanocomposites were obtained. Isothermal and nonisothermal crystallization was studied from the melt or from the glass state by using DSC and it was found that nanocomposites crystallized faster than the neat PESu under both conditions. Crystallization rates increased with increasing filler content and it seems that GO have higher crystallisation effect than org-GO. This is due to the stronger interactions that are taking place between PESu and GO, as was confirmed by FTIR and DSC. In the case of the nanocomposites interesting crystalline morphologies and different to those for neat PESu were observed with PLM. Enzymatic hydrolysis studies revealed that nanocomposites have higher hydrolysis rates than neat PESu, while GO accelerates in higher extent the hydrolysis of PESu than org-GO.

In the present work, the effective use of polyethylene-grafted maleic anhydride (PE-g-MA) copolymer as a compatibilizer in high-density polyethylene composites containing 10–50 mass% hemp fibers was evaluated through mechanical and thermal properties measurements. The results revealed a significant reinforcement on the tensile strength of the composites as a consequence of the incorporation of the compatibilizer. Less pronounced effects were found on the elongation at break and impact strength of the composites. The notable enhancement of tensile strength on the compatibilized composites was related to the improved adhesion of hemp with the matrix in the presence of PE-g-MA, which was revealed through scanning electron microscopy observations. Furthermore, Fourier transform infrared spectroscopy analyses suggested that covalent bonding occurs between the fibers and the matrix in the highest PE-g-MA concentrations. Differential scanning calorimetry experiments revealed that the presence of compatibilizer increases the crystallinity of the composites. Thermogravimetry studies revealed that for low compatibilizer concentrations the thermal stability of the composites is further reduced, while for the highest concentration, when bonding occurs, it is enhanced. The biodegradation studies of all the composites revealed that the incorporation of compatibilizer enhances the stability of the composites, especially in the higher concentrations, and reduces their final residue.

This study investigates the effect of active metal and the nature and pre-treatment of the support in a series of K-promoted NiMo catalysts supported on activated carbon (AC) for the hydrogenation reaction of CO. The Ni Mo synergistic effect was found to be essential for the activation of CO. The use of activated carbon as support led to a three-fold increase in the selectivity toward higher alcohols, compared to the unsupported material, probably due to a reduction in the crystallinity of the active NiMoO4 phase and its partial transformation from alpha to beta form. Pre-treatment of the activated carbon prior to its use as support with HNO3 aqueous solution led to significant increase in CO conversion, related to the lower amount of ash and the much higher acidity of the acid treated sample. The use of a higher surface area acid-treated support also increases activity, with the K NiMo/AC2a catalyst exhibiting a 45% higher conversion at 280 °C compared to K NiMo/AC1a. The improvement in activity can be ascribed to better dispersion of the active phase on the higher surface area AC support and therefore higher exposure of active Ni O Mo sites. Overall, the K NiMo/AC2a catalyst exhibited the optimum performance, with high CO conversion (25% at 280 °C) and high production of oxygenates, with a space time yield to oxygenates of 141.5 mg/gcatalyst/h at 280 °C. A clear tendency of increasing higher alcohol production with decreasing acidity was evidenced for all K-promoted bimetallic NiMo catalysts.

In the current study the effect of different clay type, as well as clay organomodifier, on solid state polymerization (SSP) of poly(ethylene terephthalate) (PET) was investigated. PET/clay nanocomposites containing Nanomer I.30E, Cloisite 10A and Laponite have been prepared by melt mixing and their structure was studied by X-ray diffraction measurements. Solid state was conducted at 220, 230 and 240 °C for 1, 2, 3 and 4 h under vacuum application. The I.30E organo-clay exhibited the higher immobilized amorphous fraction. This is due to its better dispersion and exfoliation of the clay nanolayers into the PET matrix, compared to the other organoclays. Intrinsic viscosity (IV) measurements after solid-state polymerization of nanocomposites revealed that IV increase is time and temperature dependent. However, nanocomposites exhibited much lower IV increase compared with neat PET. A simple kinetic model was employed to predict the time evolution of IV, as well as the carboxyl and hydroxyl content during SSP. From the experimental measurements and the theoretical simulation results it was proved that the higher aspect ratio of the nano-clay added, leads to higher inactivated hydroxyls end-groups concentration, higher activation energies and lower transesterification and esterification kinetic rate constants. Increased dispersion of the clay nanolayers in the polymer matrix in addition to increased aspect ratio, leads to better gas barrier properties, reducing the diffusivity and thus the removal of the polycondensation byproducts, i.e. water and EG.

A meaningful and advanced method concerning the management of waste electrical and electronic equipment (WEEE) becomes a necessity, mainly due to their increased production, applications and their short life. Thermal methods have been an attractive option and for this reason the investigation of pyrolysis and catalytic pyrolysis as a potential method for the recycling of polycarbonate (PC) based plastics has been the aim of the current study. Nine different catalysts with variations in properties (such as porosity and acidity/basicity) were introduced in a bench scale pyrolysis system together with the polycarbonate polymeric material and the pyrolysis fractions were collected and analyzed. The liquid product consisted mainly of phenols and substituted phenols as well as the original monomer and, due to the commercial value of these products in the chemical industry, it is expected to enhance the economic viability of the process. Results showed a reduction in the degradation temperature in the presence of all catalytic materials, depending on the pore characteristics and the acidic nature of the solid. It seems that in the presence of the basic catalysts, PC degradation leads to lower molecular weight compounds and high phenolic fractions in the liquid produced. In terms of reduction in the production of the monomer, pore size rather than acidity appears to be the determining factor.

The valorization of various types of low-quality vegetable oils with relatively high content of free fatty acids (FFA) is a research field of increased interest. The esterification of oleic acid, a highly abundant FFA in waste oils, with trimethylolpropane (TMP) towards the production of the corresponding triesters, which can be used in lubricants or hydraulic fluids, was studied in this work. The catalysts tested were various meso/macroporous oxides, such as ZrO2, 3.5%SiO2-ZrO2, SiO2-Al2O3, SBA-15 and Al-SBA-15 with varying textural and acidic properties and the corresponding supported heteropoly acid catalysts, prepared by the use of phosphotungstic (H3PW12O40) and tungstosilicic (H4SiW12O40) acids. The catalysts were characterized by ICP-AES, XRD, FT-IR, N-2 porosimetry and FT-IR coupled with pyridine adsorption. The main product at 200 degrees C and after 6 h of reaction was the triester (TE) of oleic acid with selectivity values ranging from 85% to 99% at conversion degrees of 82% to 96%. The two aluminosilicate catalysts that combine Bronsted and Lewis acidity (i.e. SiO2-Al2O3 and Al-SBA-15) showed slightly higher yields of triester (similar to 83%) compared to the rest oxides (similar to 78%), while the Bronsted acidity induced by the two heteropoly acids, especially by PW, provided very high reactivity and selectivity towards triesters, irrespective of the type of support used, reaching triester yield values of 95% (96.2% conversion, 98.7% selectivity) with the 20%PW/ZrO2 catalyst, The most stable catalysts against leaching of heteropoly acids were those supported on 3.5%SiO2-ZrO2 and SiO2-Al2O3. (C) 2017 Elsevier B.V. All rights reserved.

Brazil’s resettlement programmes have been praised for demonstrating the country’s commitment to refugee protection but the number resettled remains small compared with international need. Brazil needs to address the financing of such programmes if it is to ensure their sustainability and growth.

This work is a systematic review of the literature over the past decade of the application of activated carbon (microporous or mesoporous) as adsorbents for the removal of heavy metals, focusing especially on lead (Pb) and arsenic (As) ions from the aqueous phase. Classical examples from our lab are also given. Activated carbon is known to provide a high surface area for adsorption. Generally, surface modification is typically required, such as oxidation, treatment with ammonia or even impregnation with ferric ion, etc. and the adsorbent material may originate from various sources. The pristine materials, after modification and those after batch-wise adsorption, were characterized by available techniques (BET analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, thermal analyses, X-ray photoelectron spectroscopy). Adsorption isotherms, thermodynamics and kinetics of the process are also discussed. Selected studies from the literature are examined in comparison with other adsorbents. The role of chemistry in the metals adsorption/removal was investigated.