Aluminum Electrolysis Research Articles

Study on dissociation mechanism and process of regenerated cryolite

Solid waste produced in the process of aluminum electrolysis is a substantial secondary source of fluorine, the fluoride electrolyte in aluminum electrolysis carbon slag accounts for about 75%. Regenerative cryolite, extracted from anode carbon residue through flotation or calcination, possesses a significant potential for fluorine recovery. The fluoride in regenerated cryolite is mainly insoluble, making its efficient dissociation crucial for utilizing the solid waste from aluminum electrolysis. This study uses regenerative cryolite and sodium carbonate to examine how roasting temperature, time, and the reagent-to-cryolite ratio (R/C) affect cryolite dissociation. Dissociation efficiency is measured using indices like baking loss, leaching loss, fluoride ion concentration in the leachate, and fluoride ion conversion rate. Optimal dissociation is achieved at 780-820°, 2.0-2.5 hours roasting time, and an R/C ratio of 1.0-1.2. Orthogonal experimental results highlight the predominant influence of R/C, with roasting temperature being the secondary factor and roasting time having the least impact. Notably, at 780°, 2.0 hours, and an R/C ratio of 1.2:1, the fluoride ion conversion rate reaches a peak of 94.23%. This allows for recycling and production of high-value fluoride products, benefiting both the environment and the economy.

Chemical leaching − Flexible precipitation for sustainable recovery of fluoride from aluminum electrolysis multisource hazardous waste

The spent carbon materials, including anode and cathode, generated from the aluminum electrolysis process contain high fluoride levels and are unavoidable hazardous solid wastes. Chemical leaching, as a promising strategy for large-scale industrial treatment, must address the challenge of secondary recovery of the solution. The co-recovery mechanism preparing various fluorides from acidic and alkaline fluoride-aluminum solutions was investigated. In this process, the F/Al molar ratio and the pH value of the substrate environment are critical factors for achieving synergistic recovery. Different acid and alkali adjustment modalities resulted in a diverse array of products. For instance, adding an alkali to an acid solution generated aluminum hydroxyfluoride hydrate, whereas the reverse sequence yielded cryolite. The precipitation mechanism of acidic solutions is characterized by a complex interplay of multiple substances, whereas the process in alkaline solutions is comparatively straightforward. Specifically, as the pH value increases, the sequence of phase transformations progresses through aluminum hydroxyfluoride hydrate, chiolite, aluminum hydroxide, and cryolite. In addition to pH, localized over-alkalinity was the primary factor contributing to impurity generation. The precipitation phase in an alkaline substrate environment is significantly better controlled. During this process, pure cryolite can be synthesized by adjusting the F/Al molar ratio to 6.0 using the neutralization solution. The synergistic synthesis of fluoride from both acidic and alkaline fluorine-containing solutions is not only feasible but also anticipated to effectively address the significant issues of water swelling and secondary solution recovery that are commonly encountered in industrial applications.

Quantitative Analysis of Complex Aluminum Electrolytes by X-Ray Fluorescence.

The future production of electrolytic aluminum will be characterized by low temperature, low carbon emissions, and environmental friendliness, which will result in a more complex electrolyte system. Real-time analysis of electrolytes can significantly enhance the efficiency of the electrolytic process. However, accurately analyzing the composition of complex aluminum electrolytes online has been a technical challenge. This research primarily focuses on determining the ingredient contents of complex aluminum electrolytes based on elemental concentrations measured using X-ray fluorescence (XRF) according to an applicable standard. Calibration curves were established based on 53 standard samples of complex aluminum electrolytes to establish relationships between XRF fluorescence intensity and real concentrations. Analysis conducted on industrial complex electrolytes confirms that these newly constructed curves effectively reduce relative errors to less than 3%. Additionally, a feasible solution is proposed for determining the cryolite ratio (CR) in aluminum electrolytes using XRF. Results demonstrate an average deviation as low as approximately 0.02, fully meeting industrial production requirements. This technique offers numerous benefits including rapid analysis, ease of use, and cost savings.

Evironmentally friendly comprehensive utilization of retired waste electrolytes of aluminum electrolysis by calcification leaching

Low energy consumption and environmentally friendly recycling methods can extract high-added value and high-demand elements from retired waste fluorinated aluminum electrolytes (RWE-Al), which is crucial for alleviating resource shortages and environmental hazards. This study aims to develop a method for recovering fluorine and aluminum from RWE-Al through calcium leaching transformation combined with acid leaching. Compared to the traditional high-temperature roasting transformation and high-concentration alkali-metal-salt leaching process, this new process only involves one step of low-temperature leaching, purification of fluorine, carbonization of excess calcium, and evaporation extraction of aluminum, avoiding the generation of high energy consumption and secondary hazardous waste (F-containing liquid/ residue). Fluorine and aluminum are effectively separated and purified with extraction rates exceeding 96%. The effects of leaching temperature, CaO addition coefficient, liquid–solid ratio, and leaching time on the leaching process were systematically studied. The effects of acid concentration, liquid–solid ratio, time, and temperature on the acid-leaching process were also investigated. In summary, the comprehensive utilization of RWE-Al by this new process has proved to be feasible.

A Coordinated Emergency Frequency Control Strategy Based on Output Regulation Approach for an Isolated Industrial Microgrid

Constructing isolated industrial microgrids with wind power is beneficial for improving the economic benefits of high-energy-consuming production, such as the electrolytic aluminum industry. Due to the specialized structure of industrial microgrids and the unique characteristics of the electrolytic aluminum load (EAL), the common emergency frequency control methods do not apply to the specific operational requirements of isolated industrial microgrids. Since EALs have huge regulating capacities and fast responses, this paper proposes a coordinated emergency frequency control scheme to deal with power disturbances in isolated industrial microgrids. The coordinated frequency control model of an industrial microgrid considering demand-side participation is derived. With the help of output regulation theory, a practical, feasible coordinated frequency controller is designed by introducing frequency deviation and power disturbance as feedback control signals. The proposed control scheme achieves reserve power distribution between the generation and demand sides. The microgrid frequency can be maintained within a permitted range in the presence of large power imbalances. The simulation results conducted in an actual isolated industrial microgrid validate the effectiveness and dynamic performance of the proposed control scheme.

Study on the wetting characteristics of liquid-Al/ SiO2 interface with Si content in liquid-Al

Aiming to address the issue of aluminum slag adhering to the interior walls of vacuum lifting ladles in the aluminum electrolysis industry, Molecular dynamics simulations are employed to investigate the wetting behavior and adhesion characteristics of aluminum droplets on silica surfaces. Our findings indicate that with an increase in silicon content within the droplets, wetting diminishes and complete wetting of the silica substrate by aluminum droplets is not achieved. The presence of silicon reduces both the melting point temperature and surface tension of aluminum droplets, leading to a significant increase in contact angle and a corresponding decrease in wettability. Moreover, an elevated silicon content within molten aluminum droplets substantially decreases their interaction energy with the substrate surface. The virtual wall method is applied to examine average separation force and work of separation for detaching aluminum droplets from the substrate, revealing that adhesion characteristics are predominantly governed by mutual adhesive forces. This paper presents an atomic-level analysis elucidating how silicon as an alloying element influences adhesion between liquid aluminum and solid surfaces.

Enhanced thermal stability and corrosion resistance of novel high-entropy spinels in cryolite-alumina molten salt applications

The development of spinel oxide materials with high thermal stability and corrosion resistance is essential for thermochemical reactions, particularly in aluminum electrolysis. This study presents the structural design of a family of high-entropy spinels (HESs) with a stable cubic spinel structure (<i>Fd3‾m</i>), specifically formulated as (Cr5/12 Mn5/12 Fe5/12 Co3/8 Y3/8)3O4, (Y = Ni, Cu, or Zn). Our results demonstrate that these high-entropy spinels significantly outperform conventional NiFe₂O₄, exhibiting superior corrosion resistance and thermal properties. Specifically, we observe lower high-temperature weight loss (0.24 %–0.74 % at 1000 °C), reduced thermal conductivity (1.810–2.258 W m−1 K−1 at room temperature), and lower thermal expansion coefficients (8.2 - 10.7 × 10−6 K−1 from 400 °C to 800 °C), while maintaining comparable specific heat capacities (0.51–0.55 J g−1 K−1). Corrosion testing at 800 °C for 20 h in a KF3-AlF3-Al2O3 molten salt environment shows a corrosion layer thickness of less than 150 μm, with minimal corrosion product formation. These findings not only advance our understanding of material properties under extreme conditions but also pave the way for the development of next-generation materials for thermochemical applications, specifically aimed at improving the efficiency of aluminum electrolysis.

Preparation of lithium-ion battery anode materials from graphitized spent carbon cathode derived from aluminum electrolysis

Preparation of lithium-ion battery anode materials from graphitized spent carbon cathode derived from aluminum electrolysis

Pre‐oxidized Recycled MgO–Steel Composite Material for Possible Application in Cryolitic Melts

Recycled MgO–C lining bricks and 316L stainless steel are used to manufacture composite material for inert anode samples for aluminum electrolysis cell. The microstructure of the composite material is characterized after preoxidation thermal treatments at 800, 900, and 1000 °C as well as in its sintered state. Preoxidation (PO) process is designed to enhance the material's corrosion resistance in molten cryolite environments by developing robust Fe–Mg–O, Fe–Cr–O‐ containing phases. Analytical techniques including scanning electron microscopy, electron backscatter diffraction, and energy dispersive X‐ray spectrometry are applied to characterize the phase formation, revealing the potential of these composites for use as inert anodes in aluminum electrolysis cells. PO at 800 °C is not sufficient to form adequate protective oxide layers. Whereas, PO at 900 and 1000 °C leads to the formation of protective oxide layers containing Mg–O Fe–O halite‐like solid solutions and (Cr,Fe)3O4 spinel phase. Sample, preoxidized at 1000 °C is sealed in Mg–Fe–O spinel phase.

Anode process on gold in KF–AlF&lt;sub&gt;3&lt;/sub&gt;–Al&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;3&lt;/sub&gt; melt

In the conditions of resource saving and carbon footprint reduction, the development of oxygen–releasing anodes for technologies of production of important metals and alloys by electrolysis of molten salts seems to be an urgent task. To determine the degree of “inertness” of a particular anode material, data on the kinetics and mechanism of the anode process on a material not subject to oxidation are required. In this connection, the anodic process on gold in the KF–AlF3–Al2O3 melt for electrolytic aluminum production was investigated by cyclic and square–wave voltammetry methods. The influence of temperature (715 and 775 оC) of the melt, the content of Al2O3 in it (from 0.1 to saturation), as well as the polarization rate (0.05–1 V/s) on the kinetics and some features of the mechanism of the investigated process was determined. An assumption is made that oxygen release on gold without dissolution of the substrate takes place in the region of overvoltages from 0 to 0.8 V. It is shown that the process includes the stages of electrochemical adsorption and desorption of the intermediate product, the first of which is limited by the diffusion of electroactive anions to the anode.

Enhanced thermal insulation and corrosion resistance in Ni-Fe cermet through incorporation of high-entropy spinel oxides

The influence of high-entropy spinel oxide (HESO) content on the microstructure, electrical conductivity, and high-temperature corrosion resistance of HESO/NiFe cermets were investigated. The results found that the addition of 10–30 wt% HESO enhanced sintering densification and thermal insulation, although it also resulted in reduced electrical conductivity. Isothermal oxidation tests conducted at 900 °C for 10 hours revealed that cermets containing 30–50 wt% HESO exhibited significantly lower weight gains (0.954–1.167 mg cm⁻²) and oxidation rate constants (0.1057–0.1525 mg² cm⁻⁴ h⁻¹). Furthermore, static corrosion tests in AlF₃-KF-Al₂O₃ molten salt demonstrated that HESO effectively mitigated the erosion of the metallic phase by the fluoride molten salt. This study holds significant potential by providing new insights for the design of inert anodes for aluminum electrolysis and exploring the practical applications of high-entropy oxide materials.

Methodological Review of Methods and Technology for Utilization of Spent Carbon Cathode in Aluminum Electrolysis

Spent carbon cathode (SCC) is one of the major hazardous solid wastes generated during the overhaul of electrolysis cells in the aluminum production process. SCC is not only rich in carbon resources but also contains soluble fluoride and cyanide, which gives it both recycling value and significant leaching toxicity. In this study, we explore the properties, emissions, and disposal strategies for SCC. Pyrometallurgy involves processes such as vacuum distillation, molten salt roasting, and high-temperature roasting. Hydrometallurgy describes various methods used to separate valuable components from leachate and prepare products. Collaborative disposal plays a positive role in treating SCC alongside other solid wastes. High-value utilization provides an approach to make full use of high-purity carbon-based materials. Finally, we analyze and summarize future prospects for the disposal of SCC. This study aims to contribute to the large-scale treatment and resource utilization of SCC while promoting circular economy principles and green development initiatives.

Lithium recovery from an alumina electrolysis slag leaching solution with strong acidity: Separation of lithium-ion and production of battery grade lithium carbonate

Lithium (Li) with excellent physicochemical properties is widely used in modern industries. However, the shortage and depletion of Li resources has hindered the sustainable economic development. Li recovery from waste resource was an effective approach, in particular, alumina electrolysis slag is exemplified as Li riched solid waste. In this work, separation of Li from alumina electrolysis slag leaching solution (AESLS) via solvent extraction using bis(2-ethylhexyl) hydrogen phosphate (P204) system was explored. Effects of saponification degree, phase ratio, and reaction time on metal ions impurities and Li extraction were investigated. Operational parameters including extraction, scrubbing, saponification and precipitation were optimized. Results showed that the extraction efficiencies of Mg2+, Ca2+, Al3+, Fe3+ and Li+ were 100 %, 100 %, 99.99 %, 100 % and 20.71 %, respectively, under the optimal single extraction conditions. The loss of Li after scrubbing of loaded organic phase using hydrochloric acid was as low as 1.59 %. The P204 extraction process was proved to be a thermodynamic process with spontaneous entropy increase, and the extraction order of metal ions was Al3+ > Fe3+ > Ca2+ > Mg2+ > Li+ according to the extraction driving force (ΔC); The solvent-extracted ligand mechanism was elucidated by infrared spectroscopy and nuclear magnetic resonance. Additionally, battery-grade lithium carbonate was produced. Our study paves a new way for recovery of Li in AESLS.

Simulation and Application of a New Type of Energy-Saving Steel Claw for Aluminum Electrolysis Cells

Aluminum electrolysis is a typical industry with high energy consumption, and the energy saving of aluminum electrolysis cells is conducive to the sustainable development of the ecological environment. The current density distribution on the steel claws of conventional aluminum electrolysis cells is uneven, resulting in a large amount of power loss. Therefore, a new type of current-equalized steel claw (CESC) is designed in this paper. The ANSYS simulation study shows that the CESC can achieve a more uniform current density distribution and reduce the voltage drop by about 36 mV compared with the traditional steel claw (TSC). In addition, the use of CESC optimizes the temperature distribution of the steel claws and reduces the risk of cracking and deformation. The results of the industrial application tests are highly consistent with the simulation results, confirming the accuracy of the simulation results. The economic benefit analysis shows that using CESC saves 114.1 kWh of electricity per ton of aluminum produced. If this technology can be promoted throughout China, it is expected to save up to 4.75 billion kWh of electricity annually. The development of CESC is promising and of great significance for improving the overall technical level of the aluminum electrolysis industry.

Fully-Coupled Electric-Thermal-Flow Modeling and Investigation of Dynamic Thermal-Ledge Behavior in Aluminum Electrolysis Cell

Aluminum electrolysis cells (AECs) require effective thermal regulation to operate flexibly alongside renewable energy sources. Prior to implementing thermal regulation strategies, it is essential to predict the dynamic variations in the thermal field and ledge characteristics of a full-scale cell. This study introduces a transient electro-thermal-flow coupling model for a full-scale AEC, aimed at investigating the interactions between ledge distribution and various operational fields, including thermal, electric, and flow fields. The model facilitates the calculation and assessment of the dynamic properties of the ledge and thermal balance under ±15% flexible current variations. Results indicate that during a current increase, ledge melting predominantly occurs in the electrolyte layer, while ledge solidification is primarily observed in the metal layer during a current reduction. Regions with a thicker ledge and faster velocity tend to melt more during current increases and are less likely to return to their original shape and thickness during current reductions, complicating the rapid restoration of thermal equilibrium. To achieve uniform ledge distribution and real-time adaptation to flexible current variations, it is recommended to install distributed cooling devices on the sides of the AEC to enable differential ledge regulation at various locations.

Effects of Sintering Aids and Thickness on Densification and Properties of Magnesia-Aluminum Spinel Transparent Ceramics in the Aluminum Electrolysis Cells

Effects of Sintering Aids and Thickness on Densification and Properties of Magnesia-Aluminum Spinel Transparent Ceramics in the Aluminum Electrolysis Cells

Selective extraction of lithium and solidified fluoride from overhaul slag by the calcium sulfate roasting and water leaching

Overhaul slag is a hazardous waste which is from the process of aluminum electrolysis industry. In this work, a technology of calcium sulfate roasting and water leaching was developed to dispose of overhaul slag. The effects of roasting and leaching parameters were investigated in detail. Under the optimal roasting conditions, the fluorine could be stably solidified into CaF2, and lithium could be converted into soluble NaLi(SO4). The roasted clinker was then subjected to water leaching for the selective extraction of lithium. About 99.74 % of lithium was extracted and 99.82 % of fluoride was solidified by the leaching process under the optimal leaching conditions. After water leaching, the concentration of lithium can reach 2.3 g/L. XRD analysis shows that the main phases of the aqueous solution after evaporation and crystallization are NaLi(SO4) and Na2SO4, and a small amount of impurities can be further removed and concentrated to prepare Li2CO3. The main components of leaching slag are C, Al2O3 and CaF2, which can be used as fast setting cement. The process proposed in this paper is not limited to the recovery of high-value lithium from overhaul slag, and can be applied to the extraction of other valuable waste substances in aluminum industry.

Ultrasound-assisted enhanced leaching of lithium and fluoride compounds from waste cathode carbon: Comprehensive recovery and leaching mechanism

Due to the rapid development of the aluminum industry, waste cathode carbon, as a hazardous solid waste, is inevitably generated during the production process of the aluminum electrolysis industry. Improper treatment of waste cathode carbon will inevitably result in significant environmental damage, affecting both flora and fauna. Therefore, ultrasound-assisted leaching was employed to extract the waste cathode carbon, using a sodium hydroxide solution as the leaching medium to recover valuable metals and electrolytes, thereby mitigating environmental risks and reclaiming resources. Optimal conditions for ultrasonic-assisted alkali leaching were determined through a single-factor experiment: a leaching temperature of 70 °C, a liquid-solid ratio of 7:1, a leaching time of 50 min, an alkali concentration of 100 g/L, and ultrasonic power of 250 W. Under these conditions, the fluoride leaching efficiency reached 89.17 %, and the lithium ion leaching efficiency was 86.33 %. Comparative analyses between traditional leaching methods and the optimized experiments revealed that the advantages of ultrasonic action and cyclic leaching contributed to an increase of 5.28 % in the fluoride leaching efficiency and 11 % in the lithium ion leaching efficiency. Furthermore, ultrasonic-assisted leaching significantly reduces the leaching time to 50 min while achieving a higher rate of impurity removal.

Evaluation of fluoride emissions and pollution from an electrolytic aluminum plant located in Yunnan province

The monitoring and evaluation of fluoride pollution are essentially important to make sure that concentrations do not exceed threshold limit, especially for surrounding atmosphere and soil, which are located close to the emission source. This study aimed to describe the atmospheric HF and edaphic fluoride distribution from an electrolytic aluminum plant located in Yunnan province, on which the effects of meteorological conditions, time, and topography were explored. Meanwhile, six types of solid waste genereted from different electrolytic aluminum process nodes were characterized to analyze the fluoride content and formation characteristics. The results showed that fluoride in solid waste mainly existed in the form of Na3AlF6, AlF3, CaF2, and SiF4. Spent electrolytes, carbon residue, and workshop dust are critical contributors to fluoride emissions in the primary aluminum production process, and the fluorine content is 17.14 %, 33.30 %, and 31.34 %, respectively. Unorganized emissions from electrolytic aluminum plants and solid waste generation are the primary sources of fluoride in the environment, among which the edaphic fluoride content increases most at the sampling sites S1 and S7. In addition, the atmospheric HF concentration showed significant correlations with wind speed, varying wildly from March to September, with daily average and hourly maximum HF concentrations of 4.32 μg/m3 and 9.0 μg/m3, respectively. The results of the study are crucial for mitigating fluorine pollution in the electrolytic aluminum industry.

Operando-XRD of Electrochemical Reactors for Selective Li+ Extraction from Brines and Seawater

In times of rising demand of Li for use in Li-ion batteries (LIBs), and ensuring its supply for aluminum electrolysis, ultralight alloys, optics, synthesis, nuclear research, and pharmaceuticals, it is essential to simplify the processing of Li sources in a sustainable manner. Current extraction from ores is complex and requires large energy input while generating high amounts of waste. This causes the danger of making Li a limited resource and even more expensive.[1] A new promising way is the electrochemical extraction of Li by desalination batteries (DBs) from brines or seawater[2]. Thereby, selective extraction of ions can be promoted by the chemistry of the electrode material, e.g., by using FePO4. To further enhance the selectivity, potentiostatic application proved to be useful[3]. DBs are superior to other extraction methods in terms of energy efficiency, and waste generation. Still, varying Li+ concentrations in brines[1b], competitive intercalation of other cations with similar size - especially Na+ [2] -, and degradative effects of anions[4], H2O, and O2 [5] are major challenges to overcome for DBs with FePO4.In this contribution, we focus on the selective extraction of Li+ using FePO4 electrodes by specifically-designed multi-step potentiostatic application. Results are shown for salt solutions containing a mixture of Na+/Li+, and artificial seawater. It is vital to understand the atomic-scale processes so that the electrodes, and electrochemical parameters can be optimized. Therefore, we used operando high-energy X-ray diffraction (HEXRD) microscopy to investigate the crystal structure of FePO4 during the electrochemical process. The experiments showed that the energy barrier for Na+ (de)intercalation was higher than that of Li+ during galvanostatic cycling, i.e., FePO4 is selective for Li+. Using a multi-step potentiostatic procedure, the (de)intercalation process could be enhanced, as evident from our HEXRD results and simultaneous conductivity measurements. Our tentative interpretation is that Li+ is highly selectively (de)intercalated, although electrochemical signatures hinted on a two-step process during deintercalation, which may indicate the intercalation of Na+. To selectively deintercalate the remaining Na+ over Li+, we further optimized the applied potentials. During galvanostatic cycling in artificial seawater, the (de)intercalation potentials were at more positive and more negative potentials, respectively, likely caused by the variety of cations. We expect that our results contribute to the design of high-performance DBs and inspire the exploration of further systems based on our proposed multi-step process.