Search

Aluminum industry depends on coal-tar-pitch as a binder to produce carbon anodes used for aluminum electrolysis. This binder is nonrenewable and mainly composed of polycyclic aromatic hydrocarbons ...

The present work focuses on the gasification of a single carbon-anode particle with CO2, using a detailed reaction-transport model based on the reaction intrinsic kinetics and transport of gaseous species. The model includes the mass conservation equations for the gas components and solid carbon particles, resulting in a set of nonlinear partial differential equations, being solved using numerical techniques. The model may predict the gas generation rate, the gas compositions, and the carbon consumption rate during the gasification of a carbon particle. Five kinetic models were compared to describe the gasification behavior of carbon particles. It was found that the random pore model (RPM) provided the best description of the reactivity of anode particles. The model also predicted the particle shrinkage during the gasification process. The model was validated using experimental results obtained with different particle size ranges, being gasified with CO2 at 1233 K. The experiments were performed in a thermogravimetric analyzer (TGA). Good agreement between the model results and the experimental data showed that this approach could quantify with success the gasification kinetics and the gas distribution within the anode particle. In addition, the Langmuir–Hinshelwood (L–H) model is used in order to capture the inhibition effect of carbon monoxide on the gasification reaction. The effectiveness factor and Thiele modulus simulated for various particle sizes helped assess the evolution of the relative dominance of diffusion and chemical reactions during the gasification process.

Bio-pitch, driven from biomass, is a potential green alternative of coal-tar-pitch in the production of carbon anodes for the aluminum electrolysis process. Information on the wetting capacity of b...

Coal-tar-pitch (CTP) is a fossil carbon material, currently used as a the binder in carbon anode manufacturing process. Regardless of the technical benefits of coal-tar-pitch, it contains polycycli...

In the Hall–Héroult process, prebaked carbon anodes are utilized to produce primary aluminium. The quality of the anode plays a crucial role in the efficiency of electrowinning primary aluminium. In the production of anodes, the anode baking is considered as the stage most frequently causing anode problems. During the baking process, the anode undergoes complex physicochemical transformations. Moreover, the anode at a lower position, imposed by loading pressures from upper anodes, will creep during this process. Thus, the production of high-quality anodes demands efficient control of their baking process. This paper aims to investigate the thermo-chemo-mechanical properties of the anode paste mixture at high temperatures. These properties include kinetic parameters of pitch pyrolysis such as the activation energy and the pre-exponential factor, the thermal expansion coefficient (TEC) and relevant mechanical parameters related to the elastic, the viscoelastic and the viscoplastic behaviours of the anode. For this purpose, experiments consisting of the thermogravimetric analysis, the dilatometry and the creep test were carried out. Based on the obtained results, the forementioned parameters were identified. Relevant mechanical parameters were expressed as a function of a new variable, called the shrinking index, which is related to the volatile released in open and closed pores of the anode. This variable would be used to highlight the chemo-mechanical coupling effect of the anode mixture. New insights into the phenomena such as the expansion due to the increase of the pore pressure and the chemical shrinkage of the anode during the baking process were also gained in this work. These investigations pave the way for modeling the thermo-chemo-poromechanical behaviour of the anode during the baking process.

An in-depth study of the failure of granular materials, which is known as a mechanism to generate defects, can reveal the facts regarding the origin of the imperfections, such as cracks in the carbon anodes. The initiation and propagation of the cracks in the carbon anode, especially the horizontal cracks below the stub-holes, reduce the anode efficiency during the electrolysis process. The failure analysis of coke aggregates can be employed to determine the appropriate recipe and operating conditions in order to avoid the formation of cracks in the carbon anodes. In this paper, it will be shown that a particular failure mode can be responsible for the crack generation in the carbon anodes. The second-order work criterion is employed to analyze the failure of the coke aggregate specimens and the relationships between the second-order work, the kinetic energy, and the instability of the granular material are investigated. In addition, the coke aggregates are modeled by exploiting the discrete element method (DEM) to reveal the micro-mechanical behavior of the dry coke aggregates during the compaction process. The optimal number of particles required for the failure analysis in the DEM simulations is determined. The effects of the confining pressure and strain rate as two important compaction process parameters on the failure are studied. The results reveal that increasing the confining pressure enhances the probability of the diffusing mode of the failure in the specimen. On the other hand, the increase of strain rate augments the chance of the strain localization mode of the failure in the specimen.

Carbon-like materials such as the anode and the ramming paste play a crucial role in the efficiency of the Hall–Héroult process. The mechanical behavior of these materials during forming processes is complex and still ill-understood. This work aimed to investigate experimentally the mechanical behavior of a carbon paste used in the aluminum industry under different loading conditions. For this purpose, experiments consisting of (1) relaxation tests at different compaction levels, (2) quasi-static cyclic tests at several amplitudes, (3) monotonic compaction tests at varied strain rates, and (4) vibrocompaction tests at different frequencies were carried out. The obtained results highlight some fundamental aspects of the carbon paste behavior such as the strain rate’s effect on the paste compressibility, the hardening-softening behavior under cyclic loadings, the effect of cycling amplitude on the stress state and the paste densification, and the frequency effect on the vibrocompaction process. These results pave the way for the development of reliable rheological models for the modeling and the numerical simulation of carbon pastes forming processes.

The Hall-Héroult process uses prebaked carbon anodes as electrodes. The anode’s quality plays a crucial role in the efficiency of the aluminium production process. During the baking process, the anode undergoes complex physicochemical transformations. Thus, the production of high-quality anodes depends, among others, on the efficient control of their baking process. This paper aims to investigate the evolution of some physical properties of the anode paste mixture during the baking process. These properties include the mass loss fraction, real and apparent densities, the ratio of apparent volume, the permeability, and porosities. For this purpose, experiments consisting of thermogravimetric analysis, dilatometry, air permeability, and helium-pycnometric measurements were carried out. The anode permeability at high temperatures was linked to the air permeability through a permeability correlator due to experimental limitations. Moreover, the real density at high temperatures was estimated by combining real densities of the coal tar pitch and coke aggregates. Different porosities, such as the open porosity and the closed porosity related to the pitch binder, were estimated by taking the permeability at high temperatures into account. In this context, the effect of the permeability correlator, which was introduced to link the permeability at high temperatures to the air permeability, was investigated through a sensitivity analysis. These results allow an estimation of the shrinking index, a new variable introduced to reflect the baking level of the anode mixture, which is linked to the volatile that is released in both open and closed pores. Afterwards, the pore pressure inside closed pores in the coal tar pitch was estimated. The obtained results highlight some new insights related to the baking process of the anode mixture. Moreover, they pave the way for better modeling of the thermo-chemo-mechanical behavior of anodes at high temperatures.

This paper reports on the application of an acousto-ultrasonic (AU) scheme for the inspection of industrial-size carbon anode blocks used in the production of primary aluminium by the Hall-Héroult process. A frequency-modulated wave is used to excite the anode blocks at multiple points. The collected attenuated AU signals are decomposed using the Discrete Wavelet Transform (DTW) after which vectors of features are calculated. Principal Component Analysis (PCA) is utilized to cluster the AU responses of the anodes. The approach allows locating cracks in the blocks and the AU features were found sensitive to crack severity. The results are validated using images collected after cutting some anodes.

Carbon anodes used in Hall–Heroult electrolysis cells are involved in both electrical and chemical processes of the cell. Electrical resistivity of anodes depends on electrical properties of its constituents, of which carbon coke aggregates are the most prevalent. Electrical resistivity of coke aggregates is usually characterized according to the ISO 10143 standardized test method, which consists of measuring the voltage drop in the bed of particles between two electrically conducing plungers through which the current is also applied. Estimation of the electrical resistivity of coke particles from the resistivity of particle bed is a challenging task and needs consideration of the contribution of the interparticle void fraction and the particle/particle contact resistances. In this work, the bed resistivity was normalized by subtracting the interparticle void fraction. Then, the contact size was obtained from discrete element method simulation and the contact resistance was calculated using Holm’s theory. Finally, the resistivity of the coke particles was obtained from the bed resistivity.

Hall-Héroult cell stability is highly affected by anode changing operations. Upon the insertion of a cold anode in the cell, a layer of molten cryolite freezes under the anode. The thickness, microstructure, and chemical composition of this layer vary as a function of time and its location in the cell. To better understand the evolution of the frozen layer, mandatory for the validation of numerical models, a measurement campaign was conducted on the anodes having a few hours of operation in the cell. The macrostructure of the selected frozen bath samples has been investigated using computed tomography while scanning electron microscope (SEM) has been used to qualify its microstructure. An energy-dispersive X-ray spectroscope (EDS) coupled to the SEM has revealed the chemical content. The results showed not only very different macrostructures between samples, but also significantly heterogeneous structure within the same sample. Nevertheless, for all samples, there is a clear distinction between the frozen cryolite and alumina/dusting phases, with the latter surrounding the cryolite matrix.

The anodes used in aluminum production are formed by compaction of a paste composed of binder matrix and coarse particles of petroleum coke (aggregates). Binder matrix composed of a coal tar pitch and fine calcined petroleum coke is usually characterized by coke and/or pitch content and also by the fineness of the coke particles. Since the coke particles are rigid and assumed to be non-deformable during compaction, the deformation behavior of the binder matrix plays a crucial role in the anode paste compaction process. Compaction of binder matrix with different compositions in a rigid closed die was studied in this work. Binder matrix compositions were compacted to a maximum uniaxial pressure of 70 MPa at 150°C. Different strain rates of 2.9 × 10 − 4 s − 1 and 2.9 × 10 − 3 s − 1 enabled us to evaluate the contribution of viscous behavior of the material to the compaction of binder matrix as a function of its composition and deformation rate. A similar experimental compaction procedure with strain rates of 1.8 × 10 − 4 s − 1 and 1.8 × 10 − 3 s − 1 was applied on paste samples with different pitch contents. This study revealed that the compaction of binder matrix and anode paste with conventional compositions is not significantly a time dependent process. Viscous behavior may therefore not have a significant contribution to the compaction of the material.

Baked anodes quality control is still mostly based on core sampling and characterization. Only a small proportion of the production can be tested by this method due to the costly, time consuming, and destructive nature of the analytical techniques. Furthermore, the core properties are not necessarily representative of those of the whole block. A rapid and non-destructive method for anode quality control based on vibration modal analysis is proposed. A number of baked anodes produced under different conditions at the Alcoa Deschambault smelter were selected. These were excited mechanically at different locations and the vibration signals of the blocks were measured by accelerometers. Principal Component Analysis (PCA) was used to cluster the vibration modes of the anodes. It is shown that the proposed approach allows detecting and distinguishing different types of anode internal defects. Some of the tested anodes were cut and imaged in order to confirm the results visually.

Crack propagation in carbon cathode used in the aluminium industry has been investigated through flexural tests on notched specimens. The main parameters of interest were the geometrical evolution of the crack and the stress intensity factor at the tip ends. The latter, in the case of interfacial fracture in two-dimensional geometries, can be related to normal (mode I) and shear (mode II) stresses. In this work, a new methodology has been applied which optically measures the crack tip displacement field by Digital Image Correlation. The stress intensity factors derived from the experimental data are consistent with results available in the literature. Furthermore, the preliminary results showed that characterizing the mode I (opening) only is somehow challenging due to the heterogeneity of such carbonaceous materials.

High quality baked carbon anodes contribute to the optimal performance of aluminum reduction cells. However, the currently decreasing quality and increasing variability of anode raw materials (coke and pitch) make it challenging to manufacture the anodes with consistent overall quality. Intercepting faulty anodes (e.g., presence of cracks and pores) before they are set in reduction cells and deteriorate their performance is therefore important. This is a difficult task, even in modern and well-instrumented anode plants, because lab testing using core samples can only characterize a small proportion of the anode production due to the costly, time-consuming, and destructive nature of the analytical methods. In addition, these results are not necessarily representative of the whole anode block. The objective of this work is to develop a rapid and non-destructive method for quality control of baked anodes using acousto-ultrasonic (AU) techniques. The acoustic responses of anode samples (sliced sections) were analyzed using a combination of temporal features computed from AU signals and principal component analysis (PCA). The AU signals were found sensitive to pores and cracks and were able to discriminate the two types of defects. The results were validated qualitatively by submitting the samples to X-ray Computed Tomography (CT scan).

The aim of this work is to simulate the forming process of green anodes. For this purpose, a nonlinear compressible viscoplastic constitutive law is presented. The concept of natural reference configuration is considered. Within an isothermal thermodynamic framework, a Helmholtz free energy is proposed to take into account the nonlinear compressible deformation process occurring between natural reference configuration and current configuration. A dissipation potential is introduced in order to characterize the irreversible aspect of compaction process. The constitutive law is thus formulated through two equations: (1) an expression of Cauchy stress tensor and (2) a differential equation characterizing the evolution of the natural reference configuration. Material parameters are assumed to be a function of the apparent green density. An experimental study is carried out in order to characterize the compaction behavior of the anode paste. A user's material VUMAT subroutine for finite-element dynamic explicit analysis has been developed and implemented in the abaqus commercial software. To evaluate the model predictive capability, numerical simulations of the compaction forming process of anode paste were performed. Simulation results show that the constitutive law predicts the experimental trends and gives insight of physical responses. This constitutes a first step toward characterizing the anode paste behavior and making a benchmark with experimental results on the forming process of anode paste.

Carbon anodes used in the aluminium industry were imaged through destructive and non-destructive testing (NDT) methods. For the latter case, computed tomography (CT), which has previously been used to map the 3D apparent density distribution, was extended to crack detection. Previous work has shown how to overcome technical hurdles related to crack detection by using percolation-based algorithms operating on low-resolution images of full-scale baked carbon anodes. The previous application to 2D images was extended here to the 3D case. The crack detection algorithm has been performed on anode slices containing several independent macro cracks with different morphologies.