Modelo de contribución de grupos para laestimación de la ecotoxicidad de líquidos iónicos

Los líquidos iónicos son sales orgánicas líquidas pordebajo de los 100 ºC e incluso a temperatura ambiente(Room Temperature Ionic Liquids, RTILs), con interesantespropiedades que los convierten en compuestos muyatractivos para diferentes aplicaciones. Debido a su muybaja (prácticamente nula) volatilidad, esta nueva familiade compuestos químicos reduce significativamente supotencial como contaminante atmosférico. Sin embargo,un gran número de líquidos iónicos presentan una elevadasolubilidad en agua y su impacto en el medioambienteacuático debe ser evaluado, antes de su aplicación.Asimismo, dado el gran número de compuestos que puedeser sintetizado (más de 10 6 compuestos puros) es necesariodesarrollar modelos matemáticos que permitanrealizar estimaciones del parámetro de interés minimizandolas medidas experimentales y el consecuente consumode tiempo y recursos materiales.En este trabajo, se presenta un modelo de contribuciónde grupos para estimar el impacto de los líquidos iónicossobre el medio ambiente acuático mediante la ecotoxicidad(EC 50), evaluada a través del ensayo homologado conla bacteria bioluminiscente marina  Vibrio fischeri. Para ellose desarrolla un modelo cuantitativo QSAR (QuantitativeStructure Activity Relationship) que relaciona la ecotoxicidadcon la estructura del líquido iónico y permite dirigir laselección de los líquidos iónicos con este criterio

Modeling of amphoteric heavy metals solubility in stabilized/solidified steel foundry dust

The influence of pH on the leaching of metals from waste materials can be described by geochemical and empirical models. These equations may be integrated into dynamic leaching models in order to describe the longterm behavior of waste-derived forms or they can be used to predict the concentration of metals in equilibrium leaching tests at a given pH. The aim of this work is to describe the equilibrium concentration of the main metals (Zn, Pb, and Cr) contained in untreated and stabilized/solidified (S/S) electric arc furnace dust (EAFD) using experimental data obtained from a pH-dependence leaching test (acid neutralization capacity, ANC). EAFD is a hazardous waste generated in steel factories. Steel foundry dust coming from an electric arc furnace was characterized by acid digestion, x-ray fluorescence (XRF), and x-ray diffraction (XRD). The waste mainly contains Zn and Fe, which were identified in zincite and zinc ferrite phases. Pb and Cr were also detected at lower concentrations. Cement/EAFD formulations ranging from 7 to 20% dry wt of cement were prepared and the ANC leaching test was performed. The amphoteric behavior of Zn, Pb, and Cr was described by the geochemical model Visual MINTEQ and by an empirical model developed for these metals. Zinc and lead solubilities were well described by both models; however, Visual MINTEQ failed to describe the chromium behavior quantitatively

Energy embedded in food loss management and in the production of uneaten food: seeking a sustainable pathway

Recently, important efforts have been made to define food loss management strategies. Most strategies have mainly been focused on mass and energy recovery through mixed food loss in centralised recovery models. This work aims to highlight the need to address a decentralised food loss management, in order to manage the different fractions and on each of the different stages of the food supply chain. For this purpose, an energy flow analysis is made, through the calculation of the primary energy demand of four stages and 11 food categories of the Spanish food supply chain in 2015. The energy efficiency assessment is conducted under a resource use perspective, using the energy return on investment (EROI) ratio, and a circular economy perspective, developing an Energy return on investment ? Circular economy index (EROIce), based on a food waste-to-energy-to-food approach. Results suggest that the embodied energy loss consist of 17% of the total primary energy demand, and related to the food categories, the vegetarian diet appears to be the most efficient, followed by the pescetarian diet. Comparing food energy loss values with the estimated energy provided for one consumer, it is highlighted the fact that the food energy loss generated by two to three persons amounts to one person's total daily intake. Moreover, cereals is the category responsible for the highest percentage on the total food energy loss (44%); following by meat, fish and seafood and vegetables. When the results of food energy loss and embodied energy loss are related, it is observed that categories such as meat and fish and seafood have a very high primary energy demand to produce less food, besides that the parts of the food supply chain with more energy recovery potential are the beginning and the end. Finally, the EROIce analysis shows that in the categories of meat, fish and seafood and cereals, anaerobic digestion and composting is the best option for energy recovery. From the results, it is discussed the possibility to developed local digesters at the beginning and end of the food supply chain, as well as to developed double digesters installations for hydrogen recovery from cereals loss, and methane recovery from mixed food loss.This work has been made under the financial support of the Project Ceres-Procom: Food production and consumption strategies for climate change mitigation (CTM2016-76176-C2-1-R) (AEI/FEDER, UE) financed by the Ministry of Economy and Competitiveness of the Government of Spain

Connecting wastes to resources for clean technologies in the chlor-alkali industry: a life cycle approach

Our current economic model is experiencing increasing demand and increasing pressure on resource utilisation, as valuable materials are lost as waste. Moving towards a circular economy and supporting efficient resource utilisation is essential for protecting the environment. The chlor-alkali industry is one of the largest consumers of salt, and efforts have been made to reduce its electricity use. Furthermore, KCl mining wastes have received increasing attention because they can be transformed into value-added resources. This work studies the influence of using different salt sources on the environmental sustainability of the chlor-alkali industry to identify further improvement opportunities. Rock salt, solar salt, KCl waste salt, vacuum salt and solution-mined salt were studied. Membrane cells in both bipolar and monopolar configurations were studied and compared to the emergent oxygen-depolarised cathode (ODC) technology. Life cycle assessment was applied to estimate the cradle-to-gate environmental impacts. The natural resource (NR) requirements and the environmental burdens (EBs) to the air and water environments were assessed. The total NR and EB requirements were reduced by 20% when vacuum salt was replaced with KCl. Moreover, the environmental impacts estimated for the monopolar membrane using KCl were comparable to those generated for the bipolar membrane using VS. The difference between the monopolar and bipolar scenarios (17%) was slightly higher than that between the bipolar and ODC technologies (12%). This work demonstrates the importance of studying every life cycle stage in a chemical process and the environmental benefit of applying a circular economy, even in energy intensive industries such as the chlor-alkali industry.This work was funded by the Spanish Ministry of Economy and Competitiveness (MINECO), Project CTM2013-43539-R. The authors are grateful for this funding

Modeling of the binodal curve of ionic liquid/salt aqueous systems

Ionic Liquid-based Aqueous Two Phase Systems (ILATPS) are an innovative technique to separate biomolecules that combines the advantages of liquid–liquid extraction and hydrophilic ionic liquids. Most ILATPS are based on ionic liquids and conventional inorganic salts, and the phase envelope, described by the binodal curve, is usually modeled by empirical equations that are used to determine the phase compositions and assess the ionic liquid recyclability. However, these empirical equations may provide a poor extrapolation ability or low accuracy at the extreme regions of the binodal curve or suffer from problems of convergence. Therefore, the aim of this work is the analysis of the binodal curve equations, comparing the models reported in the literature to describe ILATPS and proposing alternative equations to improve accuracy or to reduce the mathematical complexity. For this purpose, a database compiling binodal experimental data of 100 ILATPS has been built, so that the analysis could make it possible to obtain representative conclusions for all these systems. Several models were developed, and different statistical criteria were used to assess the advantages and disadvantages of each one of these models for the binodal curve. The results show that, when accuracy is critical, a proposed model with just an additional parameter reduced more than 25% the residual mean squared error (RMSE) with respect to the commonly used equation, without losing the statistical significance of the parameters. For complex problems where an explicit equation in both the concentration of ionic liquid and of salt is needed, the use of an explicit model developed with 3 adjusted parameters that kept high accuracy (R2 > 0.996 and RMSE < 0.66) is proposed. Finally, the analysis also revealed that a fitting method based on the minimization of relative errors is recommended to increase the accuracy of the binodal curve at high salt concentrations, which is the crucial region for assessing the recyclability of the ionic liquid.This work was developed in the scope of the project CICECO Aveiro Institute of Materials (Ref. FCT UID/CTM/50011/2013), financed by national funds through the FCT/MEC and co-financed by FEDER under the PT2020 Partnership Agreement. The authors also acknowledge FCT for the Post-doctoral grant SFRH/BPD/79263/2011 of S.P.M. Ventura

The critical role of the operating conditions on the Fenton oxidation of 2-chlorophenol: assessment of PCDD/Fs formation

This work assesses the influence of the operating conditions H2O2dose (20 or 100% of the stoichiometric amount), temperature (20 or 70◦C), and the presence of chloride in the oxidation medium in the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) during Fenton treatment of aqueous samples of 2-chlorophenol, 2-CP, one of the strongest precursor of PCDD/Fs. After 4 h of oxidation in the experiments carried out with 20% H2O2chlorinated phenoxyphenols and biphenyls, which are intermediates in PCDD/Fs formation, as well as PCDD/Fs were observed, resulting in concentrations11 times higher than in the untreated sample. Additionally, when NaCl was also present in the reaction medium, PCDD/Fs were formed at higher extent, with a total concentration 74.4 times higher than in the untreated 2-CP solution. Results depicted a preferential formation of PCDFs over PCDDs, with dominance of lower chlorinated PCDD/Fs (tetra and penta-PCDD/Fs). Besides, the formation of the most toxic PCDD/Fs congeners (2,3,7,8-PCDD/Fs) was not favored under the operating conditions used in this work.Financial support from the projects CTQ2011-25262, CTQ2008-05545 and CTQ2008-00690 (Ministerio de Economía y Competitividad – MINECO (SPAIN) and Fondo Europeo de Desarrollo Regional – FEDER) is gratefully acknowledged

Cu2O-based catalysts for the electrochemical reduction of CO2 at gas-diffusion electrodes

Gas-diffusion electrodes are prepared with commercial Cu2O and Cu2O–ZnO mixtures deposited onto carbon papers and evaluated for the continuous CO2 gas phase electroreduction in a filter-press electrochemical cell. The process mainly produced methanol, as well as small quantities of ethanol and n-propanol. The analysis includes the evaluation of key variables with effect in the electroreduction process: current density (j = 10–40 mA cm−2), electrolyte flow/area ratio (Qe/A = 1–3 ml min−1 cm−2) and CO2 gas flow/area ratio (Qg/A = 10–40 ml min−1 cm−2), using a 0.5 M KHCO3 aqueous solution. The maximum CO2 conversion efficiency to liquid-phase products was 54.8% and 31.4% for Cu2O and Cu2O/ZnO-based electrodes at an applied potential of −1.39 and −1.16 V vs. Ag/AgCl, respectively. Besides, the Cu2O/ZnO electrodes are expected to catalyze the CO2 electroreduction for over 20 h. These results may provide new insights into the application of gas diffusion electrodes to alleviate mass transfer limitations in electrochemical systems for the transformation of CO2 to alcohols.The authors gratefully acknowledge the financial support from the Spanish Ministry of Economy and Competitiveness (MINECO), under the projects CTQ2013-48280-C3-1-R, CTQ2014-55716- REDT and Juan de la Cierva program (JCI-2012-12073)

Learning-by-Doing: The Chem-E-Car Competition® in the University of Cantabria as case study

It is widely known that the Learning-by-Doing (LbD) pedagogical tool is not the most common form of education in Chemical Engineering nowadays. The aim of this work is to describe the application of LbD considering as case of study the participation of undergraduate students from the Chemical Engineering Degree of the University of Cantabria (UC) from Spain in the Chem-E-Car Competition® in the 10th World Congress of Chemical Engineering (WCCE10). The Chem-E-Car Competition® is a world-known student event run by AIChE, which provides chemical engineering undergraduate students with the opportunity to participate in a team-oriented hands-on design and construction of a small prototype car powered by a chemical reaction. Within the context of the WCCE10, the competition gathered 18 teams from different countries all around the world. The UC team ended in the 6th position and won the award to the best inherent safety design. Overall, the benefits outpaced the time cost both for students and the teaching staff. This situation was not clear at the beginning of the project. Prior to this competition, LbD was used as an innovative pedagogical tool for the requested acquisition of competences. The proposal of a multi-annual Final Degree Programme was a win–win situation for all the stakeholders. From a teaching point of view, the LbD let transferable and core competences to be evaluated not only internally, but also externally thanks to the competition. A survey was completed among the students that participated in the project. Competences such as “Problem-solving” and “Adaptation to new situations” were pointed out as those which were developed in a higher level by the students

Continuous electrochemical reduction of carbon dioxide into formate using a tin cathode: comparison with lead cathode

Electrochemical reduction has been pointed out as a promising method for CO2valorisation into useful chemicals. This paper studies the influence of key variables on the performance of an experimental system for continuous electro-reduction of CO2 to formate, when a tin plate is used as working electrode. Particular emphasis is placed on comparing the performance of Sn and Pb as cathodes. As was previously found with Pb, the influence of current density (“j”) using Sn was particularly noteworthy, and when j was raised up to a limit value of 8.5 mA cm−2, important increases of the rate of formate production were observed at the expense of lowering the Faradaic efficiency. However, unlike what was found with Pb, the performance using Sn improved when the electrolyte flow rate/electrode area ratio was increased within the range studied (0.57–2.3 mL min−1 cm−2). In this way, the use of Sn as cathode allowed achieving rates of formate production that were 25% higher than the maximum rates obtained with Pb, together with Faradaic efficiencies close to 70%, which were 15 points higher than those with Pb. These results reinforce the interest in Sn as electrode material in the electro-reduction of CO2 to formate.This work was conducted under the framework of the Spanish Ministry of Science and Innovation Project ENE2010-14828

Permselectivity improvement in membranes for CO2/N2 separation

In this work, small-pore zeolites of different topology (CHA, LTA5, Rho), all with Si/Al ratio of 5, have been added to highly permeable poly(1-trimethylsilyl-1-propyne) (PTMSP) to increase its selectivity and thermal and mechanical stability. Membranes were characterized by TGA, XRD, SEM and CO2 and N2 single gas permeation measurements at different temperatures. TGA reveal that the thermal resistance of the mixed matrix membranes (MMM) is as good as that of pure PTMSP polymer membranes. XRD and SEM results reflect that there is good interaction between the fillers and the membrane matrix, at 5 and 10 wt.% zeolite loadings, while at 20 wt.% a dual layer structure is formed, when Rho zeolite is the filler, because the particle size of Rho is higher than those of LTA5 or CHA, and voids appear that limit the permselectivity performance. In single gas permeation of N2 and CO2, the influence of temperature, zeolite loading and type is analyzed. The selectivity of pure PTMSP is considerably enhanced with the addition of the zeolites and the increase of temperature, and the MMM loaded with 5 wt.% zeolite surpassed the Robeson's upper bound for CO2/N2 separation, without decreasing the permeability too much. Upon increasing temperature from 298 to 333 K, the permselectivity is enhanced even further without loss of permeability. The 5 wt.% loaded membranes were tested in CO2/N2 mixed gas separation experiments at 333 K and 12.5 wt.% CO2 in the feed, and the permselectivity of LTA5- and Rho-PTMSP membranes was further enhanced, compared with the single gas permeation experiments.Financial support from the Spanish Ministry of Economy and Competitiveness (MINECO) under project CTQ2012-31229 at the Universidad de Cantabria and MAT2012-38567-C02-01 and Severo Ochoa SEV-2012-0267 at the ITQ (UPV-CSIC) are gratefully acknowledged. A.F.B. and C.C.C. also thank the MINECO for the Early Stage Researcher (BES2013-064266) and ‘‘Ramón y Cajal’’ tenure-track (RYC2011-0855) contracts, respectively