VAT And Electronic Books

The publishing sector has experienced an important change linked to the emergence of electronics books. This new reality has an impact in the cultural industry and demands the adaptation of public regulations that affect the production and consumption of cultural goods and services. For this purpose, the authors carry out an analysis of the legislation applicable to the cultural sector, focusing on the publication of electronic books, in order to meet the impact of these measures in the economy.The importance of public action is made clear in the protection of copyright and the fight against illegal access, in order not to reduce tax collection, because this could be negative for the support of the worselfare state.The analysis is carried out for the Spanish case, although the results obtained may be extrapolated to the rest of the states of the European Union, given that the regulations are community-based

New Perspectives for Electrodialytic Remediation

Electrodialytic remediation has been widely used for the recovery of different contaminants from numerous matrices, such as, for example, polluted soils, wastewater sludge, fly ash, mine tailing or harbour sediments. The electrodialytic remediation is an enhancement of the electrokinetic remediation technique, and it consists of the use of ion-exchange membranes for the control of the acid and the alkaline fronts generated in the electrochemical processes. While the standard electrodialytic cell is usually built with three-compartment configuration, it has been shown that for the remediation of matrices that require acid environment, a two-compartment cell has given satisfactory removal efficiencies with reduced energy costs. Recycling secondary batteries, with growing demand, has an increasing economic and environmental interest. This work focusses on the proposal of the electrodialytic remediation technique as a possible application for the recycling of lithium-ion cells and other secondary batteries. The recovery of valuable components, such as lithium, manganese, cobalt of phosphorous, based on current recycling processes and the characterization of solid waste is addressed.This work has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No. 778045. Paz-Garcia acknowledges the financial support from the University of Malaga, project: PPIT.UMA.B5.2018/17. Villen-Guzman acknowledges the funding from the University of Malaga for the postdoctoral fellowship PPIT.UMA.A.3.2.2018. Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

Electrodialytic Recovery of Cobalt from Spent Lithium-Ion Batteries

Contribución en congreso científicoRecycling lithium-ion batteries has an increasing interest for economic and environmental reasons. Disposal of lithium-ion batteries imposes high risk to the environment due to the toxicity of some of their essential components. In addition to this, some of these components, such as cobalt, natural graphite and phosphorus, are included in the list of critical raw materials for the European Union due to their strategic importance in the manufacturing industry. Therefore, in the recent years, numerous research studies have been focused on the development of efficient processes for battery recycling and the selective recuperation of these key components. LiCoO2 is the most common material use in current lithium-ion batteries cathodes. In the current work, an electrodialytic method is proposed for the recovery of cobalt from this kind of electrode. In a standard electrodialytic cell, the treated matrix is separated from the anode and the cathode compartments by means of ion-exchange membranes. A cation-exchange membrane (CEM) allows the passage of cations and hinders the passage of anions, while the behaviour of anion-exchange membrane (AEM) does the opposite. A three-compartment electrodialytic cell has been designed and assembled, as depicted in the figure. In the central compartment, a suspension of LiCoO2 is added. Different extracting agents, such as EDTA, HCl and HNO3, are tested to enhanced the dissolution and the selective extraction of the target metal. Dissolved cobalt-containing complexes migrate towards the cathode or the anode compartments depending on the ionic charge of the complexes. While cobalt extraction via extracting agents is an expensive treatment, as it requires the constant addition of chemicals, an efficient electrodialytic cell could allow the recirculation of the extracting agents and the economical optimization of the process.This work has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No. 778045. Paz-Garcia acknowledges the financial support from the University of Malaga, project: PPIT.UMA.B5.2018/17. Villen-Guzman acknowledges the funding from the University of Malaga for the postdoctoral fellowship PPIT.UMA.A.3.2.2018. Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

Acid leaching of LiCoO2 enhanced by reducing agent. Model formulation and validation.

In this work, a model has been formulated to describe the complex process of LiCoO2 leaching through the participation of competing reactions in acid media including the effect of H2O2 as reducing agent. The model presented here describes the extraction of Li and Co in the presence and absence of H2O2, and it takes into account the different phenomena affecting the controlling mechanisms. In this context, the model predicts the swift from kinetic control to diffusion control. The model has been implemented and solved to simulate the leaching process. To validate the model and to estimate the model parameters, a set of 12 (in triplicate) extraction experiments were carried out varying the concentration of hydrochloric acid (within the range of 0.5–2.5 M) and hydrogen peroxide (range 0–0.6%v/v). The simulation results match fairly well with the experimental data for a wide range of conditions. Furthermore, the model can be used to predict results with different solid-liquid ratios as well as different acid and oxygen peroxide concentrations. This model could be used to design or optimize a LiCoO2 extraction process facilitating the corresponding economical balance of the treatment.This work has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska- Curie grant agreement No. 778045 and the “Proyectos I+D+i en el marco del Programa Operativo FEDER Andalucía 2014–2020”, Project no. UMA18-FEDERJA-279. Cerrillo-Gonzalez acknowledges the FPU grant (FPU18/04295) obtained from the Spanish Ministry of Education. Funding for open access charge: Universidad de Málaga / CBUA

Alternative reducing agents for Lithium-Ion batteries recycling via hydrometallurgical process

Lithium-ion batteries (LIB) are a key factor in the transition to a decarbonised and clean energy system due to their application in the power sector and electric transport. However, a growing demand of these batteries involves two direct problems: an increase in the generation of spent LIBs as well as in the demand of raw materials. Hence, the development of efficient recycling treatment of LIBs is crucial to make them a true enabler of the green transition. Currently, the LIBs recycling process can be divided into pyrometallurgical and hydrometallurgical. The first one is based on the treatment of LIBs at high temperatures to produces metal pyrolysis and metal reduction, while the second method consists in the recovery of metals via acidic leaching. Although pyrometallurgical method is the most used in the industry, hydrometallurgical process presents a series of advantages, such as low energy consumption, high metal recovery and high product purity, that make it more promising in the search of more effective recycling method. In the hydrometallurgical process, the addition of acids and reducing agents is required to dissolve the solid particles and extract the valuable metals. The purpose of this work was to evaluate the effect of alternative reducing agent in the leaching process to maximize the amount of metal (Mn, Li, Ni, Co) recovered from a real LIBs waste. With this aim, the leaching processes were carried out using as reducing agent H2O2, Fe and NH4Cl. According to the experimental results, Fe and NH4Cl enhance the extraction yield as well as the reaction time comparing with the results obtain using H2O2.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Hydrometallurgical extraction of Li and Co from LiCoO2 particles–Experimental and Modeling

The use of lithium-ion batteries as energy storage in portable electronics and electric vehicles is increasing rapidly, which involves the consequent increase of battery waste. Hence, the development of reusing and recycling techniques is important to minimize the environmental impact of these residues and favor the circular economy goal. This paper presents experimental and modeling results for the hydrometallurgical treatment for recycling LiCoO2 cathodes from lithium-ion batteries. Previous experimental results for hydrometallurgical extraction showed that acidic leaching of LiCoO2 particles produced a non-stoichiometric extraction of lithium and cobalt. Furthermore, the maximum lithium extraction obtained experimentally seemed to be limited, reaching values of approximately 65–70%. In this paper, a physicochemical model is presented aiming to increase the understanding of the leaching process and the aforementioned limitations. The model describes the heterogeneous solid–liquid extraction mechanism and kinetics of LiCoO2 particles under a weakly reducing environment. The model presented here sets the basis for a more general theoretical framework that would describe the process under different acidic and reducing conditions. The model is validated with two sets of experiments at different conditions of acid concentration (0.1 and 2.5 M HCl) and solid to liquid ratio (5 and 50 g L−1). The COMSOL Multiphysics program was used to adjust the parameters in the kinetic model with the experimental results.This work has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No. 778045. Paz-Garcia acknowledges financial support from the program “Proyectos I+D+i en el marco del Programa Operativo FEDER Andalucía 2014–2020”, No. UMA18-FEDERJA-279. Cerrillo-Gonzalez acknowledges the FPU grant obtained from the Spanish Ministry of Education. The University of Malaga is acknowledged for the financial support in the postdoctoral fellowship of Villen-Guzman

Leaching of LiCoO2 using H2O2 as reductant

The growing use of Lithium-Ion batteries (LIBs) in the field of electric vehicles and renewable energy storage entails the production of toxic and environmental hazardous wastes. Furthermore, some components in these batteries are classified as Critical Raw Material due to their supply risk and economic importance. Hence, the development of more efficient process to recycle LIBs is gaining importance for economic aspects and environmental protection. In this work, the hydrometallurgical leaching process for the recovery of valuable metals from the cathode active materials of spent LIBs batteries was evaluated. Batch Experiments were carried out using LiCoO2 which is one of the most used cathodes in lithium-ion batteries. The selection of the extracting agent, its concentration, the reducing agent and the solid-liquid ratio are some of the parameters under study in this research. Hydrochloric acid was used as the extracting agent and its concentration was modified from 0.1 M to 2.5 M while solid-liquid ratio (50 g/L), temperature (25 ºC) were fixed in all of them. The percentage of metal extracted was 31% of Co and 66% of Li for 0.1 M HCl solution. Extraction with 2.5M HCl solution was similar, 35% and 71% of Co and Li, respectively, but extracted in just 90 min, unlike the 72 h in the previous test. An experiment using H2O2 as a reducing agent was also performed, reaching a high percentage of metal extracted: 93% of Co and 100% of Li for a 0.6%vol of H2O2 Although tests have been carried out using LiCoO2, the technique can be applied to different kinds of cathode from spent batteries. The results suggested that the recovery of Co and Li is viable at optimized experimental conditions. The results indicated clearly that the dissolution of LiCoO2 particles is faster and more extensive when using more acidic extracting solution and stronger reducing agents, such as hydrogen peroxide.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Use of Aerial Laser Scanning to Assess the Effect on C Sequestration of Oak (Quercus ilex L. subsp. ballota [Desf.]Samp-Q. suber L.) Afforestation on Agricultural Land

Conversion of agricultural lands to forest plantations to mitigate rising atmospheric carbon dioxide (CO2) has been proposed, but it depends on accurate estimation of the on-site carbon (C) stocks distribution. The use of aerial laser scanning (ALS) data is a rapidly evolving technology for the quantification of C stocks. We evaluated the use of allometric models together with high-density ALS data for the quantification of biomass and soil C stocks in a 14-year-old Quercus ilex and Q. suber plantation in Southwestern Spain. In 2010, a field survey was performed and tree dasometric and biomass variables were measured. Forty-five soil profiles (N = 180 soil samples) were taken systematically and the soil organic C content (SOC) was determined. Biomass and soil organic C values were regressed against individual dasometric variables and total tree height was used as a predictor variable. Aerial laser scanning data were acquired with a point density of 12 points m−2. Relationships among ALS metrics and tree height were determined using stepwise regression models and used in the allometric models to estimate biomass and SOC C stocks. Finally, a C stock map of the holm-cork oak cover in the study area was generated. We found a tree total biomass of 27.9 kg tree−1 for holm oak and 41.1 kg tree−1 for cork oak. In the holm oak plantation, the SOC content was 36.90 Mg ha−1 for the layer 0–40 cm (SOC40) under the tree crown and 29.26 Mg ha−1 for the inter-planted area, with significant differences from the reference agricultural land (33.35 Mg ha−1). Linear regression models were developed to predict the biomass and SOC at the tree scale, based on tree height (R2 >0.72 for biomass, and R2 >0.62 for SOC). The overall on-site C stock in the holm-cork oak plantation was 35.11 Mg ha−1, representing a net C stock rise of 0.47 Mg ha−1 yr−1. The ALS data allows a reliable estimation of C stocks in holm and cork oak plantations and high-resolution maps of on-site C stocks are useful for silvicultural planning. The cost of ALS data acquisition has decreased and this method can be generalised to plantations of other Mediterranean species established on agricultural lands at regional scales. However, an increase of filed data and the availability of local biomass and, in particular, SOC will improve accurate quantification of the C stocks from allometric equations, and extrapolation to large planted areas

Modeling of LiCoO2 leaching reaction using COMSOL multiphysics

Currently, the most popular LIBs recycling processes are either pyrometallurgical and hydrometallurgical. Although the former is the most used method on an industrial scale, hydrometallurgical has become a promising process due to its recovery rate, high purity of the metals and a lower energy consumption. The main step of the hydrometallurgical process is the leaching, where acid is used as an extracting agent to recover metal from the waste LIBs. Different factors influencing the leaching process are the extracting agent concentration, temperature, solid-liquid ratio, reaction time and reductant agent concentration. Determine the reaction rate and the rate controlling step is essential to optimize leaching parameters and improve the process efficiency. In this work, a mathematical model is presented with the aim of determine the leaching reaction kinetic of LIBs components, namely, LiCoO2 particles. The model is based on a solid-liquid reaction model, in particular on the shrinking core model, due to the formation of Co3O4 in the outer part of the LiCoO2 particle when is used an inorganic acid as extracting agent in absence of an external reducing agent. In this model, the diffusion of the reactant through the product layer and the chemical reaction at the surface of the unreacted core are defined as the rate controlling step. A series of extraction analyses were carried out and their results were used to adjust the formulated model. COMSOL Multiphysics 5.5 program was used to adjust the kinetic model with the experimental results, obtaining as result the value of the kinetics and diffusion constant. The implemented model for simulation of the lithium and cobalt leaching from LiCoO2 reproduces the experimental results, predicting the non-equimolar proportion between Li+ and Co2+ and verifying the hypothesis of the Co3O4 layer formation.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Recovery of Li and Co from LiCoO2 via Hydrometallurgical–Electrodialytic Treatment

Lithium-ion batteries play an important role in our modern society as the main option to power portable electronic devices and electric vehicles. The growing demand for these batteries encourages the development of more efficient recycling processes, aiming to decrease the environmental impact of the spent batteries and recover their valuable components. In this paper, a combined hydrometallurgical-electrodialytic method is proposed for processing battery waste. In the combined technique, the amount of leaching solution is reduced as acid is generated via electrolysis. At the same time, the use of ion-exchange membranes and the possibility of electroplating allows for a selective separation of the target metals. Experiments were performed using LiCoO2, which is one of the most used cathodes in lithium-ion batteries. First, 0.1 M HCl solution was used in batch extractions to study the kinetics of LiCoO2 dissolution, reaching an extraction of 30% and 69% of cobalt and lithium, respectively. Secondly, hydrometallurgical extraction experiments were carried out in three-compartment electrodialytic cells, enhanced with cation-exchange membranes. Experiments yielded to a selective recovery in the catholyte of 62% of lithium and 33% of cobalt, 80% of the latter electrodeposited at the cathode.This work has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No. 778045. Financial support from E3TECH Excellence Network under project CTQ2017-90659-REDT (MCIUN, Spain) is acknowledged. Paz-Garcia acknowledges the financial support from the program “Proyectos I+D+i en el marco del Programa Operativo FEDER Andalucía 2014–2020”, No. UMA18-FEDERJA-279. Villen-Guzman acknowledges the postdoctoral fellowship obtained from the University of Malaga. Cerrillo-Gonzalez acknowledges the FPU grant obtained from the Spanish Ministry of Education