ARTICLE | doi:10.20944/preprints202203.0347.v1
Subject: Chemistry And Materials Science, Metals, Alloys And Metallurgy Keywords: Recycled graphite; high-quality graphite; spent batteries; acidic leaching
Online: 25 March 2022 (15:17:53 CET)
Spent batteries recycling is an important way to obtain low-cost graphite. Nevertheless, the obtaining of crystalline graphite with a rather low density of defects is required for many applications. In the present work, high-quality graphites have been obtained from different kinds of spent batteries. Black masses from spent alkaline batteries (batteries black masses, BBM), and lithium-ion batteries from smartphones (smartphone black masses, SBM) and electric and/or hybrid vehicles (lithium-ion black masses, LBM) were used as starting materials. A hydrometallurgical process was then used to obtain recycled graphites by acidic leaching. Different leaching conditions were used depending on the type of the initial black mass. The final solids were characterized by a wide set of complementary techniques.
ARTICLE | doi:10.20944/preprints202010.0627.v1
Subject: Chemistry And Materials Science, Analytical Chemistry Keywords: activated carbon; winemaking waste; wastewater; Cr(VI) removal; adsorption process; Cr(VI) reduction
Online: 30 October 2020 (08:28:29 CET)
A winemaking waste was used as a precursor of activated carbon used in hazardous Cr(VI) removal from solutions. The preparation process consisted of a hydrothermal process, and a chemical activation, of the resulting product, with KOH. The adsorption results showed that the adsorption of Cr(VI) on the obtained activated carbon is strongly dependent on the stirring speed applied to the carbon/solution mixture, pH of the solution, and temperature. The equilibrium isotherm was well fitted to the Langmuir type-II equation, whereas the kinetic can be described by the pseudo-second-order kinetic model. Thermodynamic studies revealed that Cr(VI) adsorption was an exothermic and spontaneous process. Finally, desorption experiments showed that Cr(VI) was effectively desorbed using hydrazine sulfate solutions, and at the same time, the element was reduced to the less hazardous Cr(III) oxidation state.
Subject: Chemistry And Materials Science, Biomaterials Keywords: Mining tailings; Tantalum; X-Ray diffraction; Raman spectroscopy; Scanning electron microscopy.
Online: 23 October 2020 (12:22:54 CEST)
In this work, a deep characterization of the properties of K6Ta10.8O30 microrods has been performed. The starting material used to grow the microrods has been recovered from mining tailings coming from the Penouta Sn-Ta-Nb deposit, located in the north of Spain. The recovered material has been submitted to a thermal treatment to grow the microrods. Then, they have been characterized by scanning electron microscopy, X-ray diffraction, micro-Raman and micro-photoluminescence. The results of our study confirm that the K6Ta10.8O30 microrods have a tetragonal tungsten bronze-like crystal structure, which can be useful for ion-batteries and photocatalysis.
ARTICLE | doi:10.20944/preprints202011.0371.v1
Subject: Chemistry And Materials Science, Analytical Chemistry Keywords: membrane transport; A327H+Cl- ionic liquid; gold; hydrochloric acid; nanoparticles.
Online: 13 November 2020 (10:57:44 CET)
By the use of the tertiary amine A327 and 1 M HCl solution as precursors, the ionic liquid A327H+Cl- was generated and used to investigate its performance in the transport of Au(III) form hydrochloric acid medium. The influence of the stirring speed (600-1800 min-1), ionic liquid concentration (1.25-50% v/v) in the membrane phase and gold concentration (0.01-0.15 g/L) in the feed phase on metal transport have been investigated. An equation which included both equilibrium and kinetics parameters was derived, and the membrane diffusional resistance (Δm) and feed phase diffusional resistance (Δf) was estimated as 9.5x106 s/cm and 307 s/cm, respectively. At carrier concentrations in the 5-50% v/v range and gold concentrations in the 0.01-0.15 g/L range, metal transport is controlled by diffusion of metal species through the feed boundary layer, whereas at the lowest carrier concentrations, membrane diffusion is predominant. From the receiving solutions, gold can be recovered as gold nanoparticles.
ARTICLE | doi:10.20944/preprints201909.0185.v1
Subject: Chemistry And Materials Science, Metals, Alloys And Metallurgy Keywords: activated carbon; adsorption; copper; winemaking wastes
Online: 17 September 2019 (11:44:45 CEST)
This article presents the copper ions adsorption process using an activated carbon from winemaking wastes. The pH, temperature, activated carbon amount and initial copper concentration were varied based on a full factorial 2k experimental design. Kinetic and thermodynamic studies were also carried out. The adsorption kinetics was found follow a pseudo-second-order model. The adsorption data fit better to the Langmuir isotherm. The ANOVA demonstrated that both pH of the solution and activated carbon dosage had the greatest influence on copper adsorption. The activation energy was -32 kJ·mol-1 suggesting that the copper adsorption is a physic-sorption process. The best fit to a linear correlation was the moving boundary equation that controls the kinetics for the adsorption copper ions onto the activated carbon. The X-ray photoelectron spectroscopy (XPS) results reveal the existence of different copper species (Cu2+, Cu+ and or Cu0) on the surface of the carbonaceous adsorbent after the adsorption, which could suggest a simultaneous reduction process.
ARTICLE | doi:10.20944/preprints202107.0466.v1
Subject: Chemistry And Materials Science, Biomaterials Keywords: Ferrous chloride; FeCl2·4H2O crystals; pickling waste liquors
Online: 20 July 2021 (16:36:12 CEST)
As a hazardous waste, pickling waste liquor must be properly treated. An alternative consists in promoting the formation of ferrous salts from this residue, due to its higher ferrous content. Since FeCl2·4H2O is widely used in several applications, obtaining pure crystals of this material appears to be an interesting prospect. However, this compound has scarcely been investigated. In the present work, FeCl2·4H2O crystals have been obtained from pickling waste liquors. Their structural and morphological characteristics have been investigated by X-ray diffraction, scanning electron microscopy as well as Mössbauer spectroscopy. In addition, the photoluminescence study of the obtained samples was also assessed. It was observed that after some aging time, the obtained crystals change in colour from green to more yellowish. So, the aged sample has also been evaluated, and their structural characteristics are compared with the original crystals. Despite this, the obtained crystals exhibit a FeCl2·4H2O structure, which is not modified with the aging of the sample.
ARTICLE | doi:10.20944/preprints202210.0372.v1
Subject: Chemistry And Materials Science, Applied Chemistry Keywords: Keywords carbochlorination; spent lithium-ion batteries; circular economy; recycle; LiCl.
Online: 25 October 2022 (02:05:51 CEST)
The abundant use of lithium-ion batteries (LIBs) in a wide variety of electric devices and vehicles will generate a large number of depleted batteries, which contain several valuable metals such as Li, Co, Mn, and Ni present in the structure of the cathode material (LiMO2). The present work investigates chemical, technological, and environmental aspects in the treatment of such wastes, development of a methodology for the extraction of lithium, cobalt, nickel, manganese, and graphite by a carbochlorination pyrometallurgical process. Mixtures of cathode and anode materials (called black mass, mixed oxides of Li, Co, Ni, Mn, and graphite) from different LIBs, carbon black (as reducing agent), and CaCl2 (as chlorinating agent) were used. Non-isothermal thermogravimetric tests up to 850°C and isothermal tests at 700°C of the mixtures in an inert atmosphere were carried out. It was experimentally observed that the LiMO2-C-CaCl2 reaction takes place at 700°C. LiCl, Ni, and Co were obtained as final products, and to a lesser extent, CoO, NiO, and MnO2. CaCO3 was also obtained as a by-product. The obtained results show that carbochlorination is an efficient and effective alternative route for the extraction and recovery of metals from different LIBs, focused on the sustainability and circular economy
ARTICLE | doi:10.20944/preprints202112.0064.v1
Subject: Chemistry And Materials Science, Applied Chemistry Keywords: spent fluid catalytic cracking catalyst; waste slag; leaching; lanthanum oxide; rare earths recovery
Online: 6 December 2021 (12:04:43 CET)
An laboratory procedure has been developed to obtain lanthanum oxide from spent fluid catalytic cracking catalyst, commonly used in the cracking the heavy crude oil process. Two different spent fluid catalytic cracking catalysts, which are mainly formed by silica and alumina, and a certain amount of rare earths were leached under several conditions to recover the rare earth from the solids waste. Subsequently, liquid phases were subjected to a liquid-liquid extraction process, and lanthanum was quantitatively stripped using oxalic acid to obtain the corresponding lanthanum oxalates. After the corresponding thermal treatment, these solids were transformed into lanthanum oxide. Both, lanthanum oxalates and oxides solids have been characterized by wide techniques in order to investigate the purity of the phases.
ARTICLE | doi:10.20944/preprints201908.0093.v2
Subject: Chemistry And Materials Science, Food Chemistry Keywords: spent coffee grounds; polyphenols; extraction; subcritical fluid; activated carbon; methylene blue; adsorption.
Online: 20 September 2019 (10:23:51 CEST)
A valorization process of spent coffee grounds (SCG) was studied. Thus, a two-stage process, a stage of extraction of the polyphenols and a stage of obtaining activated carbon (AC) by a carbonization process, was performed. The extraction was carried out with a hydro-alcoholic solution in a pressure reactor, modifying time and temperature. To optimize the extraction of polyphenols, a two-level factorial design with three replications at the central values was used. The best results were obtained by performing the extraction at 80 °C during 30 min, using a mixture of EtOH:H2O 1:1 (v/v) as extraction solution. Caffeine and chlorogenic acid were the most abundant compounds in the analyzed extracts, ranging from 0.09 to 4.8 mg∙g-1 and 0.06 to 9.7 mg∙g-1, respectively. The precursor obtained in the extraction stage were transformed into AC. An experimental design was realized in order to analyze the influence of different variables in the AC obtained process (reaction time and amount of potassium hydroxide used). Actived carbons with BET specific surface (SBET) comprised between 1600 m2∙g-1 and 2330 m2∙g-1 had a microporous surface. Under the optimum conditions, the obtained AC presented a maximum adsorption capacity of methylene blue (qm) between 411 mg∙g-1 and 813 mg∙g-1.
ARTICLE | doi:10.20944/preprints201908.0076.v1
Subject: Chemistry And Materials Science, Applied Chemistry Keywords: dysprosium; activated carbon; spent coffee ground; adsorption
Online: 6 August 2019 (12:23:23 CEST)
This paper describes the physico-chemical study of the adsorption of dysprosium (Dy3+) in aqueous solution onto two types of activated carbons synthesized from spent coffee ground. KOH activated carbon is a microporous material with a specific BET surface area of 2330 m2·g-1 and pores with a diameter of 3.2 nm. Carbon activated with water vapor and N2 is a solid mesoporous, with pores of 5.7 nm in diameter and a specific surface of 982 m2·g-1. A significant dependence of the adsorption capacity on the solution pH was found, while it does not depend significantly neither on the dysprosium concentration nor on the temperature. A maximum adsorption capacity of 31.26 mg·g-1 and 33.52 mg·g-1 for the chemically and physically activated carbons, respectively, were found. In both cases, the results obtained from adsorption isotherms and kinetic study were better fit to a Langmuir model and a pseudo-second-order kinetics. In addition, thermodynamic results indicate that dysprosium adsorption onto both activated carbons is an exothermic, spontaneous and favorable process.
ARTICLE | doi:10.20944/preprints202010.0448.v1
Subject: Chemistry And Materials Science, Analytical Chemistry Keywords: Cellulose; agricultural waste; bioadsorbent; rare earth; terbium adsorption-desorption
Online: 22 October 2020 (09:00:24 CEST)
Preparation of a low-cost cellulose-based bioadsorbent from the cellulosic material extracted from the rose stems (CRS) was carried out; rose stems were considered agricultural wastes. After the required pretreatment of this waste, and its further treatment with an acidic mixture of acetic and nitric acids, the CRS product was yielded. The resulting bioadsorbent was characterized by several techniques, such as X-ray diffraction, which revealed diffraction maxima related to cellulose structure, whose calculated crystallinity index (CrI) was 75 %. In addition, Fourier Transform Infrared spectroscopy (FTIR), 13C Nuclear Magnetic Resonance (NMR), and X-ray Photoelectron Spectroscopy (XPS) showed signs of acetylation of the sample, also, the thermal properties of the solid was evaluated through Thermogravimetric Analysis (TGA). Scanning Electron Microscopy (SEM) showed cellulose fibers before and after the adsorption process, some particles with not regular shapes were also observed. The CRS bioadsorbent was used in the effective adsorption of valuable Tb(III) from aqueous solution. The adsorption data resulted in a better fit to the Freundlich isotherm, and pseudo-second-order kinetic models; however, chemisorption had not been ruled out. Finally, desorption experiments revealed a recovery of terbium ions with an efficiency of 97 % from terbium-loaded bioadsorbent.