ARTICLE | doi:10.20944/preprints202110.0313.v1
Subject: Chemistry And Materials Science, Applied Chemistry Keywords: membrane transport; Cyanex 923; iron(III); manganese (II); separation.
Online: 21 October 2021 (14:10:48 CEST)
The transport of iron(III) from Fe(III)-Mn(II)-HCl mixed solutions through a flat-sheet supported liquid membrane is investigated, being the carrier phase of Cyanex 923 (commercially available phosphine oxide extractant) dissolved in Solvesso 100 (commercially available diluent), as a function of hydrodynamic conditions, concentration of manganese and HCl in the feed phase, and carrier concentration in the membrane phase. A transport model is derived that describes the transport mechanism, consisting of diffusion through a feed aqueous diffusion layer, a fast interfacial chemical reaction, and diffusion of the Fe(III)-Cyanex 923 complex across the membrane phase. The membrane diffusional resistance (Δm) and feed diffusional resistance (Δf) are calculated from the model, and their values are 145 s/cm and 361 s/cm, respectively. It is apparent that the transport of iron(III) is mainly controlled by diffusion through the aqueous feed boundary layer, being the thickness of this layer calculated as 2.9x10-3 cm. Since Mn(II) is not transported through the membrane phase, the present system allows to the purification of this manganese-bearing solutions.
REVIEW | doi:10.20944/preprints202105.0599.v1
Subject: Chemistry And Materials Science, Analytical Chemistry Keywords: organic dyes; adsorption; removal; wastewaters; environment
Online: 25 May 2021 (10:14:49 CEST)
Even in the first quarter of XXI century, the presence of organic dyes in wastewaters is a normal occurrence in a series of countries, and being these compounds toxics, their removal from these waters is of a necessity. Among the separation technologies, adsorption processing appeared as one of the most widely used to reach this goal. The present work reviewed the most recent approaches (first half of 2021 year) about the use of a variety of adsorbents on the removal of, also, a variety of organic dyes of different nature.
REVIEW | doi:10.20944/preprints202003.0032.v1
Subject: Environmental And Earth Sciences, Environmental Science Keywords: mercury(II); adsorption; processing; liquid effluents
Online: 3 March 2020 (02:17:56 CET)
Mercury is a toxic metal, thus, it is an element which has more and more restrictions in its uses, but despite the above, the removal of this metal, from whatever the form in which it is encountered (zero valent metal, inorganic or organic compounds), and from different sources, is of a widespread interest. In the case of Hg(II), or Hg2+, the investigations about the treatment of Hg(II)-bearing liquid effluents (real or in most cases synthetic solutions) appear not to end, and from the various separation technologies, adsorption is the most popular among researchers. In this topic, and in the 2019 year, more than 100 publications had been devote to this field: Hg(II)-removal-adsorption. This work examined all of them.
ARTICLE | doi:10.20944/preprints202001.0262.v1
Subject: Chemistry And Materials Science, Metals, Alloys And Metallurgy Keywords: indium(III); ionic liquid; supported, liquid membrane; Hostarex A324; transport
Online: 23 January 2020 (04:07:43 CET)
The transport of indium(III), from HCl solutions, across a supported liquid membrane in flat-sheet configuration was investigated, being the carrier the ionic liquid HA324H+Cl- (derived from the tertiary amine Hostarex A324 and hydrochloric acid). Different variables affecting the metal transport: hydrodynamic conditions in the source and receiving phases, metal and HCl concentrations in the source phase, and carrier concentration in the membrane phase, were investigated. Also the transport of indium(III) using carriers of various nature: ionic liquids, alcohol, ketone, phosphine oxide and phosphoric ester, was compared. The metal transport was modelled describing the transport mechanism as: diffusion across the source diffusion layer, a fast interfacial chemical reaction, and diffusion of the InCl4--carrier complex through the membrane support. Diffusional parameters for the transport of indium(III), from the experimental data and the model, were estimated.
ARTICLE | doi:10.20944/preprints201911.0332.v1
Subject: Chemistry And Materials Science, Applied Chemistry Keywords: indium(III); ionic liquid; liquid membranes; Hostarex A324; transport
Online: 27 November 2019 (05:04:40 CET)
The transport of indium(III), from HCl solutions, across a supported liquid membrane in flat-sheet configuration was investigated, being the carrier the ionic liquid HA324H+Cl- (derived from the tertiary amine Hostarex A324 and hydrochloric acid). Different variables affecting the metal transport: hydrodynamic conditions in the source and receiving phases, metal and HCl concentrations in the source phase, and carrier concentration in the membrane phase, were investigated. Also the transport of indium(III) using carriers of various nature: ionic liquids, alcohol, ketone, phosphine oxide, etc., was compared. The metal transport was modelled describing the transport mechanism as: diffusion across the source diffusion layer, a fast interfacial chemical reaction, and diffusion of the InCl4--carrier complex through the membrane support. Diffusional parameters for the transport of indium(III), from the experimental data and the model, were estimated.
ARTICLE | doi:10.20944/preprints201911.0203.v1
Subject: Chemistry And Materials Science, Applied Chemistry Keywords: carbon nanotubes; chromium; wastewaters; adsorption
Online: 17 November 2019 (13:17:04 CET)
The present investigation deals with the adsorption of chromium(III) from alkaline media using multi-walled carbon nanotubes. The adsorption of Cr(III) has been studied under various experimental conditions: stirring speed of the aqueous solution, initial metal and adsorbent concentrations, NaOH concentration in the aqueous solution, and temperature. The rate law indicated that chromium adsorption is well represented by the particle diffusion model, whereas the adsorption process fits to the pseudo-second order kinetic model within an exothermic character. Equilibrium data fit to the Langmuir type-2 equilibrium isotherm in an spontaneous process. Chromium(III) can be eluted from metal-loaded nanotubes using acidic solutions, from which fine chromium(III) oxide pigment can be ultimately yielded.
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.
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/preprints202011.0226.v1
Subject: Chemistry And Materials Science, Analytical Chemistry Keywords: activated carbon; hydrothermal carbonization (HTC); exergy analysis; thermoeconomic analysis; circular economy.
Online: 6 November 2020 (08:07:04 CET)
An activated carbon manufacturing process using winemaking waste is analyzed and designed at industrial scale. Starting from experimental research, the chemical transformations and thermodynamics during pruning wood conversion are studied as a basis for plant design. In this way, mass and energy balances of hydrothermal carbonization and physical activation are fulfilled and a thermoeconomic methodology is applied to develop an energy-integrated plant. To achieve this target, a network of heat exchangers is allocated to minimize heat consumption and supply hot domestic water, while a cogeneration cycle is designed to provide electricity and satisfy the remaining heat demand. Furthermore, a sensitivity analysis is carried out to determine the influence of the production scale and other operation parameters, such as annual workload, service life, and capital and feedstock costs, on the economic viability of the plant. The energy balance of the plant indicates that the energy integration design manages to provide 48.9% of the overall process energy demand by crossing hot and cold streams and recovering heat from residual flue gas. On the other hand, the exergy cost analysis identifies the combustion of pruning wood used to provide heat demands as the main source of exergy destruction, confirming the suitability of integration to improve the thermodynamic performance. Including activated carbon production, electricity, and hot domestic water, the exergy efficiency of the plant stands at 11.5%.
ARTICLE | doi:10.20944/preprints202001.0254.v1
Subject: Chemistry And Materials Science, Metals, Alloys And Metallurgy Keywords: adsorption; Lanthanum; Cerium; carbon nanotubes; rare earth
Online: 22 January 2020 (03:21:11 CET)
Since the 1960s Rare earths (REs) applications gradually have expanded to everyday life. REs have great strategic importance in industrial and technological development, so it is expected an increase in their demand. Among the REs the European Commission considered Cerium and Lanthanum as critical raw materials. This research article studies the adsorption of Ce and La onto two carbon nanomaterials, multiwalled carbon nanotubes (MWCNT) and carboxylic functionalized multiwalled carbon nanotubes (MWCNT_ox). The latter has slightly more affinity for REs than MWCNT. The recovery percentage for Ce were 89 and 98% and in the case of for La were 99 and 92% using 0.8 g of MWCNT and 0.2 g of MWCNT_ox respectively. The adsorption process fits a pseudo second-order kinetic model and the Langmuir isotherm best represented the metal uptake.
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/preprints202109.0308.v1
Subject: Engineering, Industrial And Manufacturing Engineering Keywords: coltan; niobium; tantalum; critical raw materials; technological metals; mineral processing.
Online: 17 September 2021 (12:02:04 CEST)
Demand for niobium and tantalum is increasing exponentially as these are essential ingredients for the manufacture of, among others, capacitors in technological devices and ferroniobium. Mine tailings rich in such elements could constitute an important source of Nb and Ta in the future and so alleviate potential supply risks. This paper evaluates the possibility of recovering niobium and tantalum from the slags generated during the tin beneficiation process of mine tailings from the old Penouta mine, located in Spain. To do so, a simulation of the processes that would be required to beneficiate and refine both elements is carried out. After tin carbothermic reduction, the slags are sent to a hydrometallurgical process where at the end niobium oxide and tantalum oxide are obtained. Reagents, water and energy consumption, in addition to emissions, effluents and product yields are assessed. Certain factors were identified as critical, and recirculation was encouraged in the model to maximize production and minimize reagents use and wastes. With this simulation, considering 3000 production hours per year, the metal output from the tailings of the old mine could cover around 1% and 7.4% of the world annual Nb and Ta demand, respectively.
Subject: Chemistry And Materials Science, Metals, Alloys And Metallurgy Keywords: adsorption; carbon nanotubes; rare earth
Online: 21 July 2020 (13:40:39 CEST)
Commercially available oxidized (carboxylic groups) and non-oxidized multiwalled carbon nanotubes were studied as adsorbents of cerium(III) in batch operation mode. Several variables affecting the rare earth adsorption were investigated, including: the stirring speed applied to the system, the pH of the solution and the metal concentration and carbon dosages. Although the removal of cerium from the solution is different and dependent upon the adsorbent type: i) adsorption in non-oxidized multiwalled carbon nanotubes, ii) cation exchange in the case of using oxidized multiwalled carbon nanotubes, the adsorption kinetics, the rate law and the isotherm models are the same for both adsorbents: pseudo-second order, film diffusion and Langmuir Type-1, respectively. Cerium is desorbed from loaded adsorbents using acidic solutions.
ARTICLE | doi:10.20944/preprints202005.0302.v1
Subject: Chemistry And Materials Science, Applied Chemistry Keywords: lanthanum; multiwalled carbon nanotubes; adsorption; recovery
Online: 18 May 2020 (12:35:28 CEST)
The behaviour of oxidized and non-oxidized multiwalled carbon nanotubes in the adsorption of lanthanum(III) from aqueous solutions is described. Metal uptake is studied as a function of several variables such as the stirring speed of the system, pH of the aqueous solution and metal and nanomaterial concentrations. The experimental results are fitted to various kinetics and isotherm models, being the rate law fitted to the film diffusion and particle diffusion models, when the non-oxidized and the oxidized nanomaterials are used to remove lanthanum from the solution, respectively. Sulphuric acid solutions seem to be appropriate to recover the metal from La-loaded nanomaterials.
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/preprints201908.0076.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.