Phase evolution of 17(Cu-10Ni)-(NiFe_2O_4-10NiO) cermet inert anode during aluminum electrolysis

17（Cu-10Ni）-（NiFe2O4-10NiO） cermets were prepared by cold pressing and sintering in nitrogen atmosphere, and tested as inert anode for aluminum electrolysis at 960 °C for 10 and 40 h, respectively. Microstructures and phase compositions of the as-sintered and post-electrolyzed samples were investigated. The impurity contents in the electrolyte and the cathode metal were detected in order to investigate the corrosion characteristic of the elements of Fe, Ni and Cu in the anode. A dense NiFe2O4 layer was observed on the surface of anode and thickened with prolonging the electrolysis time. In the newly formed dense ceramic layer, NiO phase disappeared as a result of being swallowed by NiFe2O4 phase, and the metal phase was oxidized during the electrolysis in which Cu element showed a higher dissolution rate than Fe and Ni elements. The formation process of the dense ceramic layer during the electrolysis was presented and explained by using the corrosion mode of the metal phase and the transformation mechanism from NiO phase to NiFe2O4 phase.

Effect of gas bubble on cell voltage oscillations based on equivalent circuit simulation in aluminum electrolysis cell

A method to investigate the effect of gas bubble on cell voltage oscillations was established. The whole aluminum electrolysis cell was treated as a resistance circuit, and the dynamic simulation of the cell equivalent circuit was modeled with Matlab/Simulink simulation software. The time-series signals of cell voltage and anode current were obtained under different bubble conditions, and analyzed by spectral and statistical analysis methods. The simulation results show that higher bubble release frequency has a significant effect on the cell voltage oscillations. When the bubble coverage of one anode block exceeds 80%, the cell voltage may exceed its normal fluctuation amplitude. The simulation also proves that the anode effect detected by computer in actual production is mainly the whole cell anode effect.

Effect of additive BaO on corrosion resistance of xCu/(10NiO-NiFe_2O_4) cermet inert anodes for aluminum electrolysis

xCu/（10NiO-NiFe2O4） cermet and 1BaO-xCu/（10NiO-NiFe2O4） cermet（x=5,10,17） inert anodes were prepared as potential inert anodes for aluminum electrolysis and their corrosion resistance to traditional electrolyte was studied with anodic current density of 1.0 A/cm2 in laboratory electrolysis.The substantial corrosion of metal Cu was observed,many pores appeared on the surface of anode and electrolytes infiltrated inside anodes during the electrolysis.The wear rates of 5Cu/（10NiO-NiFe2O4）,10Cu/（10NiO-NiFe2O4）,17Cu/（10NiO-NiFe2O4）,1BaO-5Cu/（10NiO-NiFe2O4）,1BaO-10Cu/（10NiO-NiFe2O4） and 1BaO-17Cu/（10NiO-NiFe2O4） are 2.15,6.50,8.30,4.88,4.70 and 4.48 cm/a,respectively.The addition of BaO to 10Cu/（10NiO-NiFe2O4） cermet and 17Cu/（10NiO-NiFe2O4） cermet is advantageous because BaO can effectively promote densification and thus improve corrosion resistance.But the addition of BaO to 5Cu/（10NiO-NiFe2O4） cermet is unfavorable to corrosion resistance because additive BaO at the grain boundary of anode accelerates possibly the corrosion of cermet.

Effect of sintering atmosphere on corrosion resistance of Ni/(NiFe_2O_4-10NiO) cermet inert anode for aluminum electrolysis

A comparative study on the corrosion resistance of 17Ni/（NiFe2O4-10NiO） cermet inert anode prepared in differentsintering atmospheres was conducted in Na3AlF6-Al2O3 melt. The results indicate that the corrosion rates of NiFe2O4-based cermetanodes prepared in the vacuum and the atmosphere with oxygen content of 2×10^-3 （volume fraction） are 6.46 and 2.71 cm/a,respectively. Though there is a transition layer with lots of holes or pores, a densified layer is formed on the surface of anode due tosome reactions producing aluminates. For the anode prepared in the atmosphere with oxygen content of 2×10^-3, the thickness of thedensification layer （about 50 μm） is thicker than that （about 30 μm） formed on the surface of anode prepared in the vacuum. Thecontents of NiO and Fe（II） in NiFe2xO4-y-z increase with the decrease of oxygen content in sintering atmosphere, which reduces thecorrosion resistance of the material.

Variable universe fuzzy expert system for aluminum electrolysis

In aluminum electrolytic process, the variables affect the current efficiency and the stability of electrolysis cells. AIF3 addition and aluminum tapping volume are two important factors that affect economic benefits of aluminum electrolytic production. Fuzzy logic provides a suitable mechanism to describe the relationship between the process variables and the current efficiency. Fuzzy expert system based on Mamdani fuzzy inference process for aluminum electrolysis was adopted to adjust A1F3 addition and aluminum tapping volume. A novel variable universe approach was applied in the system to solve the problem that different electrolysis cells have different universes of variables. The system was applied to 300 kA aluminum electrolysis cells in a aluminum plant. Experimental results showed that the electrolyte temperature was kept stably between 945 and 955℃, the current efficiency reached 93.5%, and the DC power consumption was 13 000 kW.h per ton aluminum.

SnO_2-based gas(hydrogen) anodes for aluminum electrolysis

A novel SnO2-based gas anode was developed for aluminum electrolysis in molten cryolite at 850 ＆#176;C to reduce energy consumption and decrease CO2 emissions. Hydrogen was introduced into the anode, participating in the anode reaction. Carbon and aluminum were used as the cathode and reference electrodes, respectively. Cyclic voltammetry was applied in the cell to investigate the electrochemical behavior of oxygen ion on platinum and SnO2-based materials. The potential for oxygen evolution on these electrode materials was determined. Then, galvanostatic electrolysis was performed on the gas anode, showing a significant depolarization effect （a decrease of ~0.8 V of the anode potential） after the introduction of hydrogen, compared with no gas introduction or the introduction of argon. The results indicate the involvement of hydrogen in the anode reaction （three-phase-boundary reaction including gas, electrolyte and electrode） and give the possibility for the utilization of reducing gas anodes for aluminum electrolysis.

Digital characterization and mathematic model of sodium penetration into cathode material for aluminum electrolysis

The sodium expansion curves of semi-graphitic cathode measured with the improved Rapoport-Samoilenko apparatus. The and TiB2/C composite cathode with different TiB2 contents were mathematic model of the sodium expansion was deduced on the basis of the experimental results. The sodium expansion parameter （a） and penetration rate factor （Q）, were introduced into the model The model was validated with the experimental sodium expansion curves self-measured and reported. The results show that the variation tendency of the sodium expansion parameter （a） and penetration rate factor （Q） is consistent with that of the experimental curves. The model is capable of not only conveniently judging the cathode quality, but also favorably establishing a unified standard of the resistance to sodium penetration of cathode.

EFFECT OF Cu-Ni CONTENT ON THE CORROSION RESISTANCE OF(Cu-Ni)/(10NiO-90NiFe_2O_4)CERMET INERT ANODE FOR ALUMINUM ELECTROLYSIS

（Cu-Ni）/（10NiO-90NiFe204） cermet inert anodes containing metal Cu-Ni0, 5, 10, 15 and 20 wt pct were prepared and their corrosion resistance to Na3AlF6-Al2O3 melts was investigated. The results indicate that the content of metal Cu-Ni has little effect on the steady-state concentration of Ni in the electrolyte and the values could not be used to effectively differentiate their corrosion resistance. The steady-state concentration of Fe decreases from 304×10^-6 to 168×10^-6 and that of Cu increases from 21×10^-6 to 71×10^-6 with the content of metal Cu-Ni increasing from 0 to 20 wt pct. Post-examination shows that metallic phase Cu-Ni is corroded preferentially during electrolysis and many pores are left at the anode surface. Considering the corrosion resistance and electrical conductivity, the cermet containing metal Cu-Ni 5 wt pct should be selected and studied further.

Electrical resistivity of TiB_2/C composite cathode coating for aluminum electrolysis

The electrical resistivity of TiB2/C cathode composite coating at different temperatures was measured with the electrical conductivity test device; the effects of TiB2 content and kinds of carbonaceous fillers as well as their mean particle size on their electrical resistivities were investigated. The results show that electrical resistivity of the coating decreases with the increase of TiB2 content and the decrease of its mean particle size. When the mass fraction of TiB2 increases from 30% to 60%, the electrical resistivity of the coating at room temperature decreases from 31.2μΩ·m to 23.8μΩ·m. The electrical resistivity of the coating at 960℃ lowers from 76.1μΩ· m to 38.4μΩ·m with the decrease of TiB2 mean particle size from 12μm to 1μm. The kinds of carbonaceous fillers have great influence on the electrical resistivity of TiB2/C composite coating at 960℃, when the graphite, petroleum coke and anthracite are used as fillers, the electrical resistivities of the coating are 20.3μΩ·m, 53.7μΩ·m and 87.2μΩ·m, respectively. For the coating with petroleum coke filler, its electrical resistivity decreases with the increase of the mean particle size of petroleum coke filler. The electrical resistivity at 960℃ decreases from 56.2μΩ·m to 48.2μΩ·m with the mean particle size of petroleum coke increasing from 44μm to 1200μm. However, too big carbonaceous particle size has adverse influence on the abrasion resistance of coating. Its proper mean particle size is 420μm.

EFFECT OF STRUCTURAL PARAMETERS ON THE THERMAL STRESS OF A NiFe_(2)O_(4)-BASED CERMET INERT ANODE IN ALUMINUM ELECTROLYSIS

Inert anode has been a hot issue in the aluminum industry for many decades. With the help of FEA （finite element analysis） software ANSYS, a model was developed to simulate the thermal stress distribution working condition of an inert anode. To reduce its thermal stress, the effect of some parameters on the thermal stress distribution was investigated, including the anode height, the anode radius, the hole depth, the hole radius, and the radius of inner chamfer and outer chamfer. The results showed that in the actual working condition of an inert anode, there existed a large axial tensile stress near the tangent interface between the anode and bath, which was the major cause of anode breaking. Increasing the anode height and reducing the hole depth properly seemed to be beneficial for the stress distribution. With the increase of anode radius, the stress distribution became better first and then deteriorated, the reasonable value was between 0.045 to 0.06m. The hole radius had a significant effect on the stress and a smaller radius would reduce the thermal stress. The effect of the radius of the inner chamfer and the outer chamfer was less than other parameters.

Numerical simulation of busbar configuration in large aluminum electrolysis cell

Various busbar configurations were built and modeled by the custom code based on the commercial package ANSYS for the 500 kA aluminum electrolysis cell.The configuration parameters,such as side riser entry ratio,number of cathode bars connected to each riser,vertical location of side cathode busbar and short side cathode busbar,distance between rows of cells in potline,the number of neighboring cells,ratio of compensation busbar carried passing under cell and its horizontal location under cell along with large magnetohydrodynamic(MHD) computation based on the custom evaluation function were simulated and discussed.The results show that a cell with riser entry ratio of 11:9:8:9:11 and cathode busbar located at the level of aluminum solution,50% upstream cathode current passing under cell for magnetic field compensation,the distance between rows of 50 m is more stable.

Microscopic mechanism of perfluorocarbon gas formation in aluminum electrolysis process

In view of the unclear cause of perfluorocarbons(PFCs)emission in the anode effect stage of aluminum electrolysis,the microscopic formation mechanism of PFCs was studied by density functional theory calculation and X-ray photoelectron spectroscopy(XPS).It is found that the discharge of fluorine containing anions([F]−)on carbon anode first causes the substitution of C—H by C—F and further results in the saturation of aromatic C—C bonds,leading to the appearance of—CF_(3)or—C_(2)F_(5)group through six-carbon-ring opening.Elimination of—CF_(3)and—C_(2)F_(5) with F atom could be a likely mechanism of CF_(4) and C_(2)F_(6) formation.XPS results confirm that different types of—CF_(x) group can be formed on anode surface during electrolysis,and the possibility that[F]−discharges continuously at the C edge and finally forms different C—F bonds in quantum mechanical calculation was verified.

Electrical Conductivity and Corrosion Resistanceof ZnFe _(2)O _(4) Based Materials Used as Inert Anodefor Aluminum Electrolysis

ZnFe 2O 4 and ZnFe 2O 4 based materials were tested to obtain the electrical conductivity and corrosion resistance in melting bath for aluminum electrolysis. The results proved that adequate additives, such as Ni 2O 3 CuO, Cu, ZnO and CeO 2 would increase the electrical conductivity, and the ZnFe 2O 4 based anodes with these additives were of good corrosion resistance. The current density on anode, the mole ratio of NaF/AlF 3 (MR) and the content of alumina in the bath effect the anode corrosion rate in different way.

Effect of electromagnetic force on turbulent flow of molten metal in aluminum electrolysis cells

The standard k-ε model was adopted to simulate the flow field of molten metal in three aluminum electrolysis cells with different anode risers. The Hartman number, Reynolds number and the turbulent Reynolds number of molten metal were calculated quantitatively. The turbulent Reynolds number is in the order of 103 , and Reynolds number is in the order of 104 if taking the depth of molten metal as the characteristic length. The results show that the molten metal flow is the turbulence of high Reynolds number, the turbulent Reynolds number is more appropriate than Reynolds number to be used to describe the turbulent characteristic of molten metal, and Hartman number displays very well that electromagnetic force inhibits turbulent motion of molten metal.

Effect of electromagnetic force and anode gas on electrolyte flow in aluminum electrolysis cell

Based on the commercial computational fluid dynamics software CFX-4.3, electrolyte flow fields in a 156 kA pre-baked anode aluminum electrolysis cell were investigated in three different cases where the electrolyte melt was driven by different kinds of force, i.e. electromagnetic force only, the anode gas drag force only and both of the former two forces. The results show that when electromagnetic force was introduced only, most of the electrolyte moves horizontally; when anode gas drag force was introduced only, the electrolyte flows mainly around each anode with small circulation; when electromagnetic force and anode gas drag force were both introduced together, the structure of the electrolyte flow fields and the velocity of electrolyte are similar to that of the case where only anode gas drag force is used. The electrolyte flow fields are mainly determined by the anode gas drag force.

Improved CFD modeling of full dissolution of alumina particles in aluminum electrolysis cells considering agglomerate formation

The full alumina dissolution process in aluminum electrolysis cells was investigated using an improved computational fluid dynamics(CFD)model based on the previous researches by consideration of agglomerate formation.The results show that the total mass of alumina agglomerate and its maximum size are mainly dependent on the feeding amount and increase with increasing it.Higher superheat can effectively inhibit the agglomerate formation and thus promote the full alumina dissolution behavior.The full alumina dissolution process mainly includes a fast stage and a slow stage,with an average dissolution rate of 17.24 kg/min and 1.53 kg/min,respectively.About 50%(mass percentage)of the total alumina particles,almost all of which are the well-dispersed alumina fine grains,dissolve within the fast dissolution stage of about 10 s.The maximum values of the average dissolution rate and final percentage of the cumulative dissolved alumina mass are obtained with a feeding amount of 1.8 kg for a superheat of 12℃.The formation of the alumina agglomerates and slow dissolution characteristics play a dominant role in the full dissolution of alumina particles.

LOW TEMPERATURE ALUMINUM FLOATING ELECTROLYSIS IN HEAVY ELECTROLYTE Na_3AlF_6-AlF_3-BaC1_2-NaCl BATH SYSTEM

Multiple regression equations of liquidus temperature, electrical conductivity and bath density of the Na_3AlF_6-AlF_3-BaC1_2-NaCl system were obtained from experiments by using orthogonal regression method. The experiments were carried out in 100A cell with low melting point electrolyte, the influences of cathodic current density, electrolytic temperature, density differences of bath and liquid aluminum on current efficiency (CE) were studied; when the electrolyte cryolite ratio was 2.5, w(BaC1_2) and w(NaCl) were 48% and 10%, respectively, CE reached 90% and specific energy consumption was 10.97k Wb/kg/kg. Because of the fact that aluminum metal obtained floated on the surface of molten electrolyte, this electrolysis method was then defined as low temperature aluminum floating electrolysis. The results showed that the new low temperature aluminum electrolysis process in the Na_3AlF_6-AlF_3-BaC1_2-NaCl bath system was practical and promising.

Effect of aluminum-containing additives on the reactivity in air and CO_2 of carbon anode for aluminum electrolysis

Airburn reaction and carboxy reaction result in the excess consumption ofcarbon anode in aluminum electrolysis. To reduce the excess carbon consumption, carbon anode wasdoped with aluminum-containing additives, such as Al, Al_4C_3, AlF_3 and Al_2O_3. Their reactivityin air and CO_2 was determined with an isothermal-gravimetric method to study the effect ofaluminum-containing additives on the reactivity in air and CO_2 of carbon anode. Results shown thatthe airburn reactivity at 450℃ and carboxy reactivity at 970℃ of carbon anode both decreased withAl-containing additives adding, while shown a minimum with the amount of Al_4C_3, AlF_3 and Al_2O_3increasing. However, all Al-containing additives increase the airburn reactivity at 550℃ of carbonanodes. Coke yield measurement and XRD examination with aluminum containing additives doped pitchcokes revealed that the effect of Al-containing additives on the airburn reactivity and carboxyreactivity of carbon anode would result from chemical factors and structural factors.

Electrical conductivity of Cu/(10NiO-NiFe_2O_4) cermet inert anode for aluminum electrolysis

Cu/(10NiO-NiFe2O4) cermets containing mass fractions of Cu of 5%, 10%, 15% and 20% were prepared, and their electrical conductivities were measured at different temperatures. The effects of temperature and content of metal Cu on the electrical conductivity were investigated especially. The results indicate that the metallic phase Cu distributes evenly in 10NiO-NiFe2O4 ceramic matrix. The mechanism of electrical conductivity of Cu/(10NiO-NiFe2O4) cermets obeys the rule of electrical mechanism of semiconductor, the electrical conductivity for cermet containing 5% Cu increases from 2.70 to 20.41 S/cm with temperature increasing from 200 to 900 ℃. The change trend of electrical conductivity with temperature is similar with each other and it increases with increasing temperature and content of metal Cu. At 960 ℃, the electrical conductivity of cermet increases from 2.88 to 82.65 S/cm with the content of metal Cu increasing from 0 to 20%.

Effect of carbon fibre on properties of TiB_2/C composite cathode coating for aluminum electrolysis

The tensile strength,compressive strength and electrical resistivity of TiB2/C composite cathode coating were measured with a hydraulic pressure universal test machine and an electrical resistivity test device,and the effects of carbon fibre content and carbon fibre length on tensile strength,compressive strength and electrical resistivity were investigated.The results show that the tensile strength of coating increases at the beginning and then reduces with the increase of carbon fibre content when the carbon fibre(length of 3 mm)content ranges from 0 to 4.0%;at the carbon fibre content of 1.5%,the tensile strength of coating reaches the maximum,25.6 MPa.For the coating with carbon fibre content of 1.5%,the carbon fibre length has a great influence on tensile strength and compressive strength of coating;when the carbon fibre length is 6 mm,the tensile strength and compressive strength of coating reach the maximum,27.6 MPa and 39.2 MPa,respectively.The electrical resistivity of coating reduces with the rise of temperature and the length of carbon fibre,and the influence of carbon fibre length on electrical resistivity of coating at low temperature(30-200℃)is more obvious than that at high temperature(960℃).