Hydrometallurgy最新文献

In the present study, the sorption of perrhenate ions from sulfuric acid liquors was studied using three types of polymer ion exchange resins. An anion exchange resin type 1 (a copolymer of 2-methyl-5-vinylpyridine with divinylbenzene (VP-DVB)) as well as two polyfunctional resins containing anion and cation exchange functional groups, namely, type 2 (a carboxylated VP-DVB with pyridine-2-carboxylic acid (picolinic acid) functional group) and type 3 (an aminophosphorylated VP-DVB with pyridine-2-[(methylamino)methyl]phosphonic acid functional group), were studied. The resins before and after rhenium sorption were characterized by FT-IR spectroscopy and XPS spectroscopy. The incorporation of additional acidic functional groups into the polymer matrix of the VP-DVB resins led to a slight decrease in the rhenium anion exchange capacity. At the same time, polyfunctional resins make it possible to strip rhenium with hydrochloric acid. A completely new process for the preconcentration of rhenium as a halide compound, which will contribute to the low-cost production of metallic rhenium, can be implemented using these new polyfunctional resins. Column sorption experiments using real uranium leach liquors demonstrated an exchange capacity of 33.2 mg of Re per gram of resin and a concentration factor in the eluate of ∼2500. The possibility of anion exchange recovery of rhenium from uranium leach liquors by Type 3 resin followed by direct precipitation of potassium hexachlororhenate from hydrochloric acid desorption liquor was demonstrated. The present study provided a new resin for rhenium recovery with excellent adsorption and elution characteristics, which is a promising candidate for practical applications.

In this study, the mineralogy of a novel resource of deep-sea sediments containing rare earth elements (REEs) was investigated, along with the leaching of REEs using hydrochloric acid. The results revealed that, apart from 62.0% of the Ce found in the Mn oxides, the other REEs in the deep-sea sediments mostly existed in hydroxyapatite mineral which can be easily decomposed via a hydrochloric acid leaching. An optimized REEs leaching percentage of 89.5% was achieved using 2.0 mol/L hydrochloric acid as the leaching agent, with a liquid-solid ratio of 4:1, at 60 °C for 30 min. However, Mn oxides remained stable during the leaching process, resulting in a low Ce leaching percentage of 30.7%. Under the optimized conditions, Mn oxides could be decomposed by adding 30% H₂O₂ as a reducing agent, leading to improved leaching percentages of Ce and REEs to 86.6% and 93.2%, respectively. The high leaching efficiency of REEs may further increase the utilization potential of this novel resource.

The key to achieving sustainable metal extraction development is to avoid the generation of high-salt wastewater from the source. Here, a new system for the extraction and separation of lanthanide elements Eu(III), Gd(III) and Tb(III) from the acetic acid solution using HEHEHP (2-ethylhexyl hydrogen-2-ethylhexylphosphonate) was studied. The corresponding parameters including contact time, HEHEHP concentration, concentrations of rare earth metal ions and acetic acid in the initial solution, aqueous/organic phase volume ratio (R_(A/O)), and temperature were considered to optimize the conditions for the separation of different rare earth elements. The results showed that the separation coefficients of Tb(III)/Gd(III) and Gd(III)/Eu(III) in the acetic acid system were approximately 6.2 and 1.7, with HEHEHP of 0.15 mol/L and R_(A/O) of 2:1, and the extraction efficiency of RE(III) reached approximately 73.1%, which was higher than that in the hydrochloric acid and sulfuric acid systems. The mechanism associated with the extraction reaction was evaluated and discussed by the maximum loading capacity method, chromatographic analysis, and FT-IR spectrometric analysis. The mechanism followed a cation exchange reaction and acetic acid did not participate in the extraction process. The feasibility of the separation of Tb(III) from Eu(III) and Gd(III)was also given in terms of the separation coefficients between different elements at different extraction conditions. Since saponification is not necessary in the acetic acid extraction system, it can considerably reduce wastewater discharge to the ecological environment from the source.

Trichloroisocyanuric acid (TCCA), which is used for gold leaching, is an alternative to cyanidation due to its lower toxicity and higher efficiency. This study investigated the gold recovery procedures from highly effective chloride leaching solution using the D301 resin. This approach prevented the inhibition of gold adsorption when using activated carbon. Herein, the optimal conditions for gold adsorption were discussed, including establishing adsorption kinetics and isotherms, and calculating adsorption activation energy. Additionally, SEM (Scanning Electron Microscope), FTIR (Fourier Transform Infrared Spectroscopy), and XPS (X-ray Photoelectron Spectroscopy) techniques were used to reveal the mechanism of gold adsorption using D301 resin. Under optimal conditions (pH 4.0, temperature 25 °C, time 120 min), an average adsorption percentage of 99.2% was achieved. Analysis of the adsorption data confirmed that gold adsorption followed the pseudo-second-order kinetic model and Freundlich adsorption isotherm. The calculated activation energy was 9.69 kJ mol⁻¹, indicating a predominance of physical adsorption involving ion exchange reactions with protonated tertiary amine groups in the D301 resin beads. Furthermore, among various eluents tested in desorption experiments, a solution containing a mixture of thiourea and hydrochloric acid with 0.4 mol L⁻¹ and 0.8 mol L⁻¹, respectively, demonstrated superior efficiency, achieving a successful desorption percentage reaching 95.7 ± 0.3% within 80 min. After three cycles of resin regeneration, the regeneration efficiency reached 91.2% while maintaining an average adsorption percentage of 95.3%.

Spent hydrodesulfurization (HDS) catalysts containing large amounts of valuable metals, such as Mo and V, are hazardous solid wastes but also valuable secondary resources. However, the current recovery process suffers from the difficulty of balancing the leaching efficiency of Mo and V and their selectivity over Al. This work focused on the effect of phase transformation during roasting operation on the leaching behavior Mo, V, and Al and adopted an oxidation roasting followed by mixed alkali of Na₂CO₃ and NaOH leaching process to recover Mo and V from spent HDS catalysts. The results indicated that the phase transformation of Mo, V, and Al species during oxidation roasting process played a crucial role in achieving efficient leaching of Mo and V, as well as reducing leaching efficiency of Al. This transformation involved the change in Mo and V species changed from low valent compounds to high valent oxides, and Al₂O₃ from γ-phase to θ- and α-phases. In addition, efficient and selective leaching of 99.3% Mo and 97.8% V was realized, with only 0.03% Al being dissolved, by roasting the spent catalysts at 700 °C for 2 h and then leaching with a mixed solution of 1.2 mol/L Na₂CO₃ and 1.6 mol/L NaOH. The efficient and selective leaching of Mo and V can significantly reduce the burden of subsequent separation and purification, which provided an important prerequisite for the development of a new process for the recovery of Mo and V from HDS spent catalysts in alkaline systems.

The regeneration of failed hydroxyoxime extractants in the copper hydrometallurgy industry is crucial. However, the existing regeneration system has limitations in terms of operability, yield, and environmental friendliness, which restricts its industrial application. This paper presents a clean one-pot ammoximation regeneration system for the in-situ preparation of hydroxylamine for the oximation of aldehydes, catalyzed by TS-1 with NH₃ and H₂O₂. It was tailored based on the characteristics of the degraded organic phase produced by long-term operation at the copper solvent extraction site. The developed system demonstrates an excellent regeneration conversion efficiency (>90%) for the degraded copper-extracted organic phase. Following regeneration, the copper extraction efficiency of the organic phase reaches the same level as the fresh organic phase and maintains good copper extraction stability even after multiple extraction cycles. Moreover, the phase separation performance was improved through optimization. This regeneration system meets the demand for environmentally friendly and resourceful utilization of degraded waste organic phases in copper extraction systems.

The low bio-production of Fe³⁺ as a leaching agent is one of the main limitations to implementing industrial bio-processes at feasibility conditions. The main limitation of the bio-oxidation process of Fe²⁺ is the low oxygen transfer to the aqueous phase because of the low oxygen solubility. This study assesses the effectiveness of the venturi jet as an innovative and intensive aeration device for overcoming the oxygen limitation in a continuous ferrous oxidation process in a fixed-bed reactor with immobilized acidithiobacillus ferrooxidans, in contrast to the conventional diffuser aeration device. Firstly, the influence of the airflow and the influence of the medium concentration were determined for the following parameters for both aeration devices; Volumetric mass transfer coefficient (k_La), Standard Oxygen Transfer Rate (SOTR), Standard Aeration Efficiency (SAE), and Standard Oxygen Transfer Efficiency (SOTE). Then, both aeration devices were compared in a continuous bio-oxidation process in an up-flow packed bio-reactor (UFPB). The system performance was assessed by monitoring temperature, pH, oxidation-reduction potential, and dissolved oxygen concentration for 69 days. Findings displayed that when aerating with the diffuser, the ferrous oxidation rate was restricted by the low dissolved oxygen availability, being about 1 ppm (1 mg L⁻¹). Under these oxygen-limiting conditions, the maximum ferrous (Fe²⁺) oxidation rate was 9.09 g L⁻¹ h⁻¹. However, when aerating with the venturi jet, the dissolved oxygen concentration increased up to 2.70 mg L⁻¹, achieving a maximum of 29.11 g L⁻¹ h⁻¹. So, this study has demonstrated that the change in the aeration device has resulted in an improvement in the process, achieving a 3.5-fold increase in the oxidation rate. Furthermore, the venturi jet offered additional advantages over the diffuser, such as requiring less power to deliver the same amount of air, being unaffected by jarosite precipitates, and not requiring a supply of compressed air.

The phosphoric acid produced by the nitric acid method cannot be used as an industrial-grade product as a result of the high calcium nitrate content. It can only be used for fertilizer production due to difficulty of complete removal of calcium nitrate. Herein, an efficient approach for the removal of calcium nitrate from the phosphoric acid produced by the nitric acid process was studied. The proposed process is based on solvent extraction with N, N, N′, N′-tetracyclohexyl-3-oxyglutaramide (TCHDGA). The effects of time, diluent, temperature, impurity ions, and the concentrations of extractant and nitric acid on the extraction of Ca²⁺ were considered. A series of characterization tests involving FT-IR spectroscopy, XPS analysis, slope analysis and X-ray single crystal diffracted analysis revealed that the stoichiometry of the complex is (Ca(NO₃)₂)(TCHDGA)₃. The concentration of Ca²⁺ in phosphoric acid drops below 5 mg/L a three-stage cross-current extraction process. The stripping efficiency of calcium nitrate in the organic phase by water is above 99.9%. The extraction efficiency of Ca²⁺ by TCHDGA remained above 96.8% after ten extraction-stripping cycles, realizing the efficient removal of calcium nitrate in the phosphoric acid produced by nitric acid process without changing the traditional production conditions.

Hydration of In³⁺ is the main factor limiting its extraction efficiency from an aqueous solution during a liquid-liquid extraction process. In this study, KCl was introduced into the aqueous solution to facilitate the formation of InCl₄⁻ of low charge density, which is expected to possess much weaker hydration compared with In³⁺, promoting the solvent extraction of indium. The crown ethers (CEs) with varied cavity sizes, benzo-18-crown-6 (B18C6), benzo-15-crown-5 (B15C5), and benzo-12-crown-4 (B12C4), were synthesized. The extraction performance of the CEs toward indium in the presence of sufficient KCl in the aqueous solution was investigated. The liquid-liquid extraction process was analyzed theoretically based on density functional theory (DFT) from the aspects of thermodynamics, geometric structure optimization, electrostatic potential (ESP), and independent gradient model (IGM). The theoretical evaluations agreed well with the experimental results that the hydration of indium could be significantly weakened through the formation of InCl₄⁻ and the complexation ability of the CEs toward indium is in the order of B18C6 > B15C5 > B12C4. The complexation mechanism between the CEs and indium during the extraction process was further explored with the assistance of ¹H NMR spectrum and SEM-EDS. The results indicate that crown ether coordinates with K⁺ to form [CE-K]⁺ at the two-phase interface, which further associates with InCl₄⁻ to create the complex of CE-KInCl₄, realizing the efficient indium extraction. Moreover, B18C6 showed excellent selectivity toward In³⁺ over the competing ions such as Fe³⁺, Al³⁺, Zn²⁺, Sn²⁺ and Ca²⁺ in a complex system. Indium could be efficiently recovered from the loaded organic phase by using 1 M HCl as the stripping agent with a stripping efficiency of 98.1%.

With a decline in high-grade molybdenum reserves, the development of other types of molybdenum resources have received increasing attention. Vanadium shale is a multi-metal shale and fine-grained sedimentary rock comprising small grains and various minerals. After leaching and extracting vanadium, the solution often contains a low concentration of molybdenum. However, because of the low molybdenum concentration, many processing plants treat it as an acidic wastewater, which wastes molybdenum resources and carries the risk of environmental pollution. The leaching process of vanadium shale mostly involves high-temperature and high-pressure operations, which greatly increase the content of impurity ions such as aluminium and phosphorus in the pregnant leach solution. These impurity ions increase the difficulty in separating and recovering molybdenum. In this study, the adsorption and separation of molybdenum at leach liquor of low molybdenum concentration were investigated. The effects of different factors such as: (i) pH of feed solution, (ii) adsorption time, and (iii) presence of impurity ions, aluminium and phosphorus, on the adsorption and separation of molybdenum using five different anion-exchange resins, D201, D296, D301, D314, and D301R, were investigated. The static adsorption and desorption test results showed a molybdenum adsorption capacity of 222 mg/g at pH = 1.5 by the D301 resin. The desorption efficiency using 20% NH₄OH was 96.1%. The adsorption efficiencies of aluminium and phosphorus were 1.31% and 3.10%, respectively. This is a better choice for separating molybdenum from complex solutions. The experimental results from spectra and theoretical calculations showed that the -NH group of D301 resin was combined with the O atoms of MoO₃·3H₂O, Al(SO₄)₂⁻, and H₂PO₄⁻ by electrostatic attraction. The binding energies of these three species were − 311 kJ/mol, −231 kJ/mol, and − 62.0 kJ/mol respectively, indicating that D301 resin preferentially adsorbed MoO₃·3H₂O. Based on the above results, the D301 resin can adsorb molybdenum(VI) in complex solutions under low pH conditions, and this study is expected to promote the comprehensive recovery of valuable metals from vanadium shale.