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Thermodynamics, Mechanism and Kinetics of Metallurgical Processes

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A special issue of Minerals (ISSN 2075-163X). This special issue belongs to the section "Mineral Processing and Extractive Metallurgy".

Deadline for manuscript submissions: closed (30 April 2024) | Viewed by 15815

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Dr. Álvaro Aracena Caipa

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Escuela de Ingeniería Química, Pontificia Universidad Católica de Valparaíso, Avenida Brasil 2162, Valparaiso 2362854, Chile
Interests: thermodynamics and kinetics of extractive metallurgy processes; kinetics of extraction/purification of metals from residues; concentration of elements of interest from dilute solutions

Prof. Dr. Hyunjung Kim

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Department of Earth Resources and Environmental Engineering, Hanyang University, 222 Wangsimni-ro, Seongdong-gu, Seoul 04763, Korea
Interests: (bio)flotation; colloid chemistry in mineral processing; resources recycling; sustainable process development; fate, transformation, and transport of nanomaterials; extractive metallurgy
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Dear Colleagues,

The analysis of factors affecting metallurgical processes, where extraction/concentration/precipitation of useful metal is involved, is of great relevance since product analysis intrinsically generates process optimization. To achieve these goals, each process must be evaluated through a series of experimental studies that involve the processing of empirical data which must agree with the theoretical work. The experimental results must be validated by analysis and interpretation of the solids, liquids, or gases generated by the experimental work; in parallel, those analyses must be supported by detailed and substantiated work using thermodynamic tools. The juxtaposition of experimental and theoretical evaluation produces chemical or thermochemical reaction mechanisms supporting relevant and innovative hypotheses in metallurgical processes. On the other hand, mass transfer mechanisms promote heterogeneous kinetic models, widely used to understand the true incidence of factors such as temperature, reagent/gas concentration, surface area, and porosity level, among others, on the reaction rate, leading to intrinsic impact of the real actors on the evolution of metallurgical treatment.

The critical evaluation of processes based on thermodynamics, heterogeneous kinetics, and reaction mechanisms will affect the basis of the metallurgical structure and backbone of any process, leading in the direction of optimization, economic performance, and specific requirement of each mineral/metal treatment of interest.

This Special Issue aims to bring together studies related to the bridges of this metallurgical backbone such as thermodynamics, reaction mechanisms/mass transfer, and heterogeneous kinetics, as a whole or separately, contributing and generating new ideas for the next generations of extractive metallurgists.

Dr. Álvaro Aracena Caipa
Prof. Dr. Hyunjung Kim
Guest Editors

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Minerals is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2400 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

thermodynamics for high and low temperatures
heterogeneous kinetics
extractive metallurgical processes

Published Papers (12 papers)

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Research

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20 pages, 6589 KiB

Open AccessArticle

A Study on the Production of Anhydrous Neodymium Chloride through the Chlorination Reaction of Neodymium Oxide and Ammonium Chloride

by Joo-Won Yu and Jei-Pil Wang

Minerals 2024, 14(5), 480; https://doi.org/10.3390/min14050480 - 30 Apr 2024

Viewed by 192

Abstract

The chlorination mechanism of neodymium oxide for the production of anhydrous neodymium chloride was analyzed based on the reaction temperature and reaction ratio of ammonium chloride, considering the suppression of the generation of NdOCl, an intermediate product of the reaction process. The results were obtained by distinguishing the shape of the produced NdCl₃(powder and bulk) and the setup of the chlorination equipment, reflecting its sensitivity to moisture and oxygen. The powdered form of NdCl₃ produced at 400 °C and under argon gas flow was identified as NdCl₃·6(H₂O), while the bulk form of NdCl₃ produced by melting at 760 °C after a chlorination process consisted of anhydrous NdCl₃ and NdCl₃∙n(H₂O). The powdered NdCl₃ produced in an argon gas environment with a controlled level of oxygen (below 16.05 ppm) and moisture (below 0.01 ppm) content was identified as single-phase anhydrous NdCl₃ and showed the highest chlorination conversion rate of 98.65%. The addition of overstoichiometric ratios of NH₄Cl in the chlorination process decreased the total amount of impurities (N, H, and O) in the NdCl₃ product and increased the conversion rate of NdCl₃. Full article

(This article belongs to the Special Issue Thermodynamics, Mechanism and Kinetics of Metallurgical Processes)

16 pages, 3568 KiB

Open AccessArticle

Distribution of Copper, Iron, and Sulfur in Copper Concentrate Particles during Oxidation under Simulated Flash Smelting Conditions

by Manuel Pérez-Tello, Valeria de la Paz-Ojeda, Víctor R. Parra-Sánchez, Eugenia A. Araneda-Hernández, Madrioly C. Fernández-Sagredo and Eduardo A. Villagrán-Guerra

Minerals 2024, 14(3), 315; https://doi.org/10.3390/min14030315 - 16 Mar 2024

Viewed by 634

Abstract

The distribution of copper, iron, and sulfur during the oxidation of La Caridad copper concentrate particles under simulated flash smelting conditions was studied in a laboratory reactor. Six wet-sieved size fractions and the unsieved copper concentrate were oxidized at 1123 K and 40% and 70% O₂ by volume in the process gas during the experiments. Samples of partially oxidized particles were collected at 0.2, 0.8, and 0.9 m from the point of entry and analyzed in a QEMSCAN^® unit to determine the elemental composition within the population of particles. The distribution of the major elements during oxidation was strongly dependent upon the size and chemical composition of the initial particles. Overall, the copper content tended to increase and sulfur content decreased along the reactor length within all sizes. In contrast, the distribution of iron did not follow a general trend, as it was found to increase, decrease, or remain unchanged depending on the particle size. This finding may represent a key feature to further investigate the reaction path followed by particles during flash smelting, especially those associated with particle fragmentation. In general, the larger the particle size was, the larger the change in the content of the major elements within the particle population. Based on the experimental results, particles within a size fraction of <45 µm tended to follow a reaction path consisting of rapid melting followed by the collision and coalescence of reacting droplets during flight. In contrast, particles within the fraction of 45–53 µm tended to react individually. The oxidation behavior of the unsieved concentrate particles showed a combination of both reaction paths. Full article

(This article belongs to the Special Issue Thermodynamics, Mechanism and Kinetics of Metallurgical Processes)

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12 pages, 3013 KiB

Open AccessArticle

Influence of Vanadium–Titanium Sinter Basicity on Cohesive Dripping Properties of Blast Furnace Comprehensive Burden

by Zhe Ning, Xiyu Wang and Songtao Yang

Minerals 2024, 14(3), 293; https://doi.org/10.3390/min14030293 - 11 Mar 2024

Viewed by 691

Abstract

Vanadium–titanium ore possesses significant mining and utilization value. The basicity of vanadium–titanium sinter has a direct impact on the formation, location, thickness, permeability, and heat exchange of the cohesive zone in the blast furnace. This paper investigated the influence of increasing the basicity of the sinter on the comprehensive burden’s cohesive dripping properties in the blast furnace, while keeping the final slag basicity constant. This study was conducted through cohesive dripping property experiments. The findings indicated that as the sinter basicity in the comprehensive burden structure increased and the corresponding increase in the proportion of pellets occurred, the softening performance of the comprehensive burden improved, the cohesive zone became thinner, the lower edge of the cohesive zone shifted upward, and the softening melting properties became better in general. With an increase in the sinter basicity, the dripping difference pressure of the comprehensive burden decreased, and the dripping rate firstly increased and then decreased. An increase in the sinter basicity of the comprehensive burden structure promoted V reduction, and the V element yield and Cr element yield of the sinter were both increased; the optimal sinter basicity was 2.5, and the corresponding pellet proportion was 42%. Full article

(This article belongs to the Special Issue Thermodynamics, Mechanism and Kinetics of Metallurgical Processes)

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28 pages, 15669 KiB

Open AccessArticle

Characterization of Kinetics-Controlled Morphologies in the Growth of Silver Crystals from a Primary Lead Melt

by Steven King, Dillon Rajoo, Alexander Norori-McCormac and Alberto Striolo

Minerals 2024, 14(1), 56; https://doi.org/10.3390/min14010056 - 01 Jan 2024

Viewed by 1083

Abstract

Silver, a precious metal, can be recovered as a by-product of the processing of non-ferrous metals such as lead. In this work, silver crystals grown from the controlled cooling of a 10% silver–90% lead melt have been examined to quantify crystal morphologies developed under industrial conditions. X-ray tomography (XCT) is adapted to quantify the size and morphology of silver crystal structures grown from the Ag-Pb melt. The examination utilized high X-ray energies and small sample sizes to mitigate attenuation and enhance image quality. Examination of single crystal dendrites under high magnification demonstrates that silver crystals, even those grown under commercial conditions, yield a Face-Centered Cubic (FCC) crystalline lattice, which could be important for the practical extension of this work to the commercial production of Ag nano-crystals and crystalline supra-molecular structures. The crystals observed are composed of multiple twinned euhedral grains in a variety of dendritic to acicular arrangements, yielding a substantial heterogeneity of crystalline forms. XCT data were used to generate size and shape descriptors for the individual crystals. The results were compared to an equivalent set of descriptors generated from laser sizing examination of a sample of unconsolidated crystals from the same experimental run. The correspondence to within 9% of the crystal equivalent diameters determined independently by the XCT and laser sizing demonstrates a favorable outcome in particle sizing as achieved by visual inspection of XCT results. XCT examination of crystal assemblages identifies small octahedral crystals and larger triangular platelets. The structures expected for FCC crystals grown at thermodynamically controlled conditions are not observed in our systems, suggesting the possibility of the first crystal nuclei form at such conditions, but their growth transition to kinetically controlled mechanisms occurs as their size increases above a threshold cutoff. Based on literature observations, this size threshold is much smaller than the resolution of the XCT instrumentation employed herein. Our characterization data are in fact consistent with thermodynamics/kinetics—and then kinetics-controlled mechanisms—as the crystal size increases. This observation is important because the systems considered here are representative of commercial processes. As such, this work extends prior crystal growth concepts, which were explored in aqueous systems often probed by electrodeposition. Full article

(This article belongs to the Special Issue Thermodynamics, Mechanism and Kinetics of Metallurgical Processes)

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14 pages, 6668 KiB

Open AccessArticle

Effect of Raw Materials on Temperature Development during Prereduction of Comilog and Nchwaning Manganese Ores

by Trine A. Larssen and Merete Tangstad

Minerals 2023, 13(7), 920; https://doi.org/10.3390/min13070920 - 08 Jul 2023

Cited by 1 | Viewed by 739

Abstract

The effect of raw materials on the temperature development and prereduction behavior of Comilog and Nchwaning manganese ores (3.33–4.00 mm or 11.20–15.00 mm) were investigated in a CO-CO₂ atmosphere. Experiments were conducted at a heating rate of 6 °C/min from room temperature to 1000 °C where the ore was mixed with inert material (quartz) in various ratios. A similar heating program gave dissimilar temperature development for Comilog and Nchwaning ores due to differences in oxygen levels and reduction rates. The temperature development, and thus reduction rate, decreased with the increasing amount of inert material in the mix for Comilog ore in size 3.33–4.00 mm. The peak reaction rates observed during reduction were 2.4 wt%/min, 1.0 wt%/min, and 0.8 wt%/min for an ore:quartz weight ratio of 1:0, 1:1, and 1:3, respectively. For Comilog ore in size 11.20–15.00 mm, and Nchwaning ore in both sizes, the temperature development and reduction rates were slightly or insignificantly affected. It was suggested that the effect was low for reactions under a diffusion-controlled kinetic regime. Full article

(This article belongs to the Special Issue Thermodynamics, Mechanism and Kinetics of Metallurgical Processes)

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25 pages, 16350 KiB

Open AccessArticle

Recovery of Copper and Gold from Waste Printed Circuit Boards Using Monosodium Glutamate Supplemented with Hydrogen Peroxide

by Natrawee Khetwunchai, Saengchai Akeprathumchai and Paitip Thiravetyan

Minerals 2023, 13(3), 321; https://doi.org/10.3390/min13030321 - 24 Feb 2023

Cited by 2 | Viewed by 2679

Abstract

This study aimed to recover copper and gold from a waste printed circuit board (WPCB) using monosodium glutamate (MSG) supplemented with a clean oxidizer(s) under 30 °C, 150 rpm, and an initial pH of 7.00. The solder mask of WPCBs needed to be removed before leaching. At the first leaching, 93% of copper was selectively leached from solder–mask–free WPCBs within 3 h using 0.75 M MSG with 0.50% (w/v)

H_{2} O_{2}

. Then, gold (86%) was extracted from the first residue for 3 h by 1 M MSG with 0.25% (w/v)

H_{2} O_{2}

. In the downstream process, 98–100% copper could be directly recovered within 5–6 h from the first leachate by electrowinning (EW). However, gold in the second leachate required separation and purification processes before EW. At 4 h, 98% gold was adsorbed onto the activated carbon. Most impurities were removed from gold-loaded activated carbon by pre-elution using 0.05 M EDTA for 0.5 h without gold release. Afterward, 99% gold was eluted by diluted aqua-regia within an hour. Finally, the gold could be harvested perfectly using EW for 2 h. This complete copper and gold recycling process delivers an innovative concept for hydrometallurgical study and has the potential to develop into a practical industry. Full article

(This article belongs to the Special Issue Thermodynamics, Mechanism and Kinetics of Metallurgical Processes)

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13 pages, 6570 KiB

Open AccessArticle

Investigation on Segregation Granulation by Fuel and Flux in Coating

by Lin Wang, Xin Jiang, Qingyu Wang, Mingxing Ai, Xiaowei Yin, Jintao Liu and Fengman Shen

Minerals 2023, 13(2), 134; https://doi.org/10.3390/min13020134 - 17 Jan 2023

Cited by 1 | Viewed by 1150

Abstract

The metallurgical property of sinter is an important factor affecting the smooth operation of blast furnaces (BF), because it has a great impact on the permeability of BF and solid fuel rate. In order to promote the combustion of solid fuel and the mineralization of flux in sintering process, and eventually improve the strength of sintered ore, a series of investigation on segregation granulation by fuel and flux in coating were carried out, including the sinter pot experiments, the morphology analysis, and the discussion combine with phase diagram. The experimental results show that, (1) as the CaO increased from 0% to 40% and coke breeze increased from 0% to 100%, the sintering indices were improved, the tumble strength of sinter increased from 65.8% to 68.4%, the rate of qualified products increased from 77.4% to 81.0%, and the micro-strength of sinter increased from 68.7% to 75.9%. (2) There are three reasons for the high strength of sinter by segregation granulation of fuel and flux in coating, (a) the complete combustion of solid fuel and release the heat, (b) the effective absorb heat and mineralization of flux, and (c) the improvement of fluidity of bonding phase. The outcomes of the present work may provide a new method to improve the strength of sintered ore and give some reference for better understanding segregation granulation process and using it in actual operation. Full article

(This article belongs to the Special Issue Thermodynamics, Mechanism and Kinetics of Metallurgical Processes)

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11 pages, 2332 KiB

Open AccessArticle

Study of the Reaction Mechanisms during the Thermal Decomposition of Arsenic Sulfide (V) at High Temperatures under Non-Isothermal Conditions

by Kristhobal Castro, Eduardo Balladares, Oscar Jerez, Manuel Pérez-Tello and Álvaro Aracena

Minerals 2022, 12(11), 1379; https://doi.org/10.3390/min12111379 - 29 Oct 2022

Viewed by 1119

Abstract

The reaction mechanisms during thermal decomposition in As-S systems are complex to describe due to the physicochemical characteristics of arsenic and its sulfides. Non-isothermal tests were carried out in a NETZSCH DTA/TG thermal analysis equipment, and interrupted tests were carried out in a vertical oven adapted for this purpose; both tests were carried out in an inert nitrogen atmosphere. The information obtained experimentally was analyzed and correlated to determine the phases and reaction mechanisms during the thermal decomposition of an arsenic sulfide (V) sample. As a result of this study, the mechanism of thermal decomposition of an arsenic sulfide sample was obtained and the apparent activation energy was determined by the Kissinger and Ozawa methods. Full article

(This article belongs to the Special Issue Thermodynamics, Mechanism and Kinetics of Metallurgical Processes)

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15 pages, 4721 KiB

Open AccessArticle

Studies on Recovery of Valuable Metals by Leaching Lead–Zinc Smelting Waste with Sulfuric Acid

by Chunfu Xin, Hongying Xia, Guiyu Jiang, Qi Zhang, Libo Zhang and Yingjie Xu

Minerals 2022, 12(10), 1200; https://doi.org/10.3390/min12101200 - 23 Sep 2022

Cited by 2 | Viewed by 2202

Abstract

Germanium-containing residues (GCR) are a secondary resource rich in zinc (Zn) and germanium (Ge) produced in the Zn pyrometallurgical process and an important raw material for recovering Zn and Ge. To recycle the residue by hydrometallurgy, sulfuric acid is used to leach the residue under normal pressure. In this study, the experimental conditions (leaching temperature, leaching time, liquid/solid (L/S) mass ratio and initial acidity) were optimized through the experimental design to make the optimized experimental conditions consistent with the current industrial production conditions, so as to maximize the leaching rate of Zn and Ge, and the main reasons for the low leaching rate of germanium were analyzed. The results show that the optimum reaction conditions are as follows: initial acidity 160 g·L⁻¹, leaching temperature 90 °C, L/S mass ratio 5:1, leaching time 60 min and stirring speed 400 r·min⁻¹. Under the optimum reaction conditions, the leaching rates of Zn and Ge are 83.22% and 77.29%, respectively. The reason for the low leaching rates of Zn and Ge in GCR was obtained through atmospheric leaching experiment, electron probe microanalysis (EPMA), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and chemical phase analysis. GCR is mainly composed of phases such as zincite (ZnO), galena (PbS), wurtzite (ZnS) and anglesite (PbSO₄), and the main elements are Zn, lead (Pb), germanium (Ge), oxygen (O), sulfur (S), silicon (Si), aluminum (Al) and Fe. This study can provide a certain reference value for researchers, in order to provide a reference for the large-scale recycling of Zn and Ge resources in the future. Full article

(This article belongs to the Special Issue Thermodynamics, Mechanism and Kinetics of Metallurgical Processes)

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13 pages, 3701 KiB

Open AccessArticle

On the Cobalt Content Upgrade in Nickeliferous Laterites Using Iron (III) Sulfate: A Study Based on Thermodynamics Simulations

by Rodrigo F. M. Souza, Mariana A. A. Tavares, Luiz E. C. Cruz, Víctor A. A. Oliveira, Iranildes D. Santos, Francisco J. Moura and Eduardo A. Brocchi

Minerals 2022, 12(9), 1156; https://doi.org/10.3390/min12091156 - 13 Sep 2022

Cited by 1 | Viewed by 1746

Abstract

Nickel (Ni) and cobalt (Co) are relevant technological metals for the future of the lithium-ion battery (LIB) industry. Based on the current and projected demand for these, an increased interest in developing processing routes to exploit lateritic occurrences has been observed, as these are reported as critical raw materials for future mineral–metallurgical industry. However, the content of Ni and Co in such ores is minimal and requires impracticable mineral-processing operations for concentration before metal extraction. It was identified that information regarding the sulfation roasting of this material is scarce on what concerns the iron sulfates interaction as a function of the temperature. Based on that context, the present work has its purposes associated with the proposition of an alternative chemical pretreatment to upgrade the content of metals of technological interest in lateritic ores through a simple roast–leach process. Thus, the chemical interactions between the mineral sample and iron (III) sulfate (Fe₂(SO₄)₃) through thermodynamic simulations and experimental procedures were explored. The latter included specific water leaching practices for the selective concentration of metals. The equilibrium calculations indicate that Fe₂(SO₄)₃ and FeSO₄ tend to decompose at lower temperatures, and considering the higher stability of other metal sulfates, it could be an interesting reagent in this type of process. Regarding the experimental results, the characterization of materials indicates a recovery of Co as high as 73.4 wt.% after sulfation roasting at 500 °C followed by water leaching, with the full content of Iron (Fe) being reported in the insoluble phase. Based on these findings, the present development could be an interesting alternative to consider within operations for the chemical upgrade of cobalt in such types of mineralogical occurrences. Full article

(This article belongs to the Special Issue Thermodynamics, Mechanism and Kinetics of Metallurgical Processes)

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Review

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14 pages, 1065 KiB

Open AccessReview

An Overview of the Behavior of Concentrates with Arsenic, Antimony, and Bismuth under Roasting Conditions

by Alvaro Aracena, Miguel Véliz, Oscar Jerez, Eduardo Balladares and Manuel Pérez-Tello

Minerals 2023, 13(7), 942; https://doi.org/10.3390/min13070942 - 14 Jul 2023

Cited by 3 | Viewed by 1193

Abstract

It is well-known that the mining industry in Chile and the world is searching for eco-friendly, highly efficient mineral treatments. This is because the content of toxic elements such as arsenic, antimony, and bismuth have increased in the copper concentrates in the last years. This trend has affected the market of this metal, as well as increased the potential of producing solid wastes that represent a threat to the environment. In this paper, a review on the fundamentals of the current treatments aimed at removing arsenic, antimony, and bismuth from copper concentrates under roasting conditions is presented. The literature survey included the research conducted from 2000 until now and is focused on the different types of roasting of copper concentrates reported in the literature. A summary of the experimental conditions and major findings of each work is discussed. Depending on the type of roasting, the behavior of arsenic, antimony, and bismuth species during the experiments is analyzed. Full article

(This article belongs to the Special Issue Thermodynamics, Mechanism and Kinetics of Metallurgical Processes)

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Other

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10 pages, 3155 KiB

Open AccessBrief Report

Copper Sulfation from Enargite Roasting Using Coal and Fayalite Slag Mixture

by Miguel Véliz, Alvaro Aracena, Oscar Jerez, Manuel Pérez-Tello and Eduardo Balladares

Minerals 2023, 13(12), 1489; https://doi.org/10.3390/min13121489 - 28 Nov 2023

Viewed by 818

Abstract

In this work, the roasting of an enargite mix was carried out in oxidative conditions. The temperature range of the study was 773–973 K. The mixture had a 4:6:6 molar ratio of enargite, magnetite and coal, respectively. The roasting was made in an open atmosphere. The time was 1 h for each isothermal test. The effect of temperature and weight loss were studied. The results indicate that the temperature affects the products. At 773–873 K, the copper phases were sulfates. When the temperature was increased to 973 K, all the present phases were oxidized, and no arsenic phase was encountered in the XRDs. Therefore, this process is an excellent alternative for roasting copper concentrates with enargite, removing arsenic in the gas phase and generating a calcine that could then go to lixiviation to finally recover the copper through electrowinning. Full article

(This article belongs to the Special Issue Thermodynamics, Mechanism and Kinetics of Metallurgical Processes)

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