Ambient electrical conductivity of carbon cathode materials for aluminum reduction cells

The ambient electrical conductivity (AEC) of carbon cathode materials was investigated in respect to their open porosity, crystal structure and graphite content using hydrostatic method, four-probe technique and X-ray diffraction (XRD), respectively. The AEC is proportional to the specific conductivity (σ0) and the exponential of (1?ε) (ε is porosity) by a quasi-uniform formula based on the percolation theory. Theσ0 can reflect the intrinsic conductivity of the carbon cathodes free of pores, and it depends on the mean crystallite size parallel to the layer (002). The exponentn is dependent on the materials nature of the cathode aggregates, while an averaged value, 4.65, can practically work well with 5 types of cathode materials. The calculation ofσ0 can be extended to the graphitic cathodes containing different aggregates using the simple rule of mixture.

Numerical simulation of coupled thermo-electrical field for 20 kA new rare earth reduction cell

To solve the problems of high energy consumption,low efficiency and short service life of conventional rare earth reduction cells,a 20 kA new rare earth reduction cell(NRERC)was presented.The effects of the anode-cathode distance(ACD)and electrolyte height(EH)on the thermo-electrical behavior of the NRERC were studied by ANSYS.The results illustrate that the cell voltage drop(CVD)and the temperature will rise with a similar tendency when the ACD increases.Also,the temperature rises gradually with EH,but the CVD decreases.Ultimately,when the ACD is 115 mm and the EH is 380 mm,the CVD is 4.61 V and the temperature is 1109.8℃.Under these conditions,the thermal field distribution is more reasonable and the CVD is lower,which is beneficial to the long service life and low energy consumption of the NRERC.

Numerical simulation on electrolyte flow field in 156 kA drained aluminum reduction cells

Based on the commercial CFD software CFX-4.3, two-phase flow of electrolyte in 156 kA drained aluminum reduction cells with a new structure was numerically simulated by multi-fluid model and k-ε turbulence model. The results show that the electrolyte flow in the drained cells is more even than in the conventional cells. Corresponding to center point feeding, the electrolyte flow in the drained cells is more advantageous to the release of anode gas, the dissolution and diffusion of alumina, and the gradient reduction of the electrolyte density and temperature. The average velocity of the electrolyte is 8.3 cm/s, and the maximum velocity is 59.5 cm/s. The average and maximum velocities of the gas are 23.2 cm/s and 61.1 cm/s, respectively. The cathode drained slope and anode cathode distance have certain effects on the electrolyte flow.

Simulation of thermal and sodium expansion stress in aluminum reduction cells

Two finite element(FE) models were built up for analysis of stress field in the lining of aluminum electrolysis cells.Distribution of sodium concentration in cathode carbon blocks was calculated by one FE model of a cathode block.Thermal stress field was calculated by the other slice model of the cell at the end of the heating-up.Then stresses coupling thermal and sodium expansion were considered after 30 d start-up.The results indicate that sodium penetrates to the bottom of the cathode block after 30 d start-up.The semi-graphitic carbon block has the largest stress at the thermal stage.After 30 d start-up the anthracitic carbon has the greatest sodium expansion stress and the graphitized carbon has the lowest sodium expansion stress.Sodium penetration can cause larger deformation and stress in the cathode carbon block than thermal expansion.

Electric field distribution in 75 kA drained aluminum reduction cell

Current distribution in a drained aluminum reduction cell is critical due to its influence on the current efficiency, electrolysis stability, anodes and cathodes integrity. A finite element model was developed to simulate the electric field in a 75 kA drained aluminum reduction cell. The current distribution and influences of the cathode inclination angle and anode-cathode distance (ACD) were studied. The results show that relatively large horizontal current density appears in the aluminum film, and the maximum value reaches 600 kA/m2. As the cathode inclination angle increases from 2° to 15°, the maximum current density of the metal pad increases by 15%, while the maximum current density of the aluminum-wettable coating layer decreases by 27%. The influence of the ACD on the current distribution is not obvious.

Dynamic self-adaptive ANP algorithm and its application to electric field simulation of aluminum reduction cell

Region partition(RP) is the key technique to the finite element parallel computing(FEPC),and its performance has a decisive influence on the entire process of analysis and computation.The performance evaluation index of RP method for the three-dimensional finite element model(FEM) has been given.By taking the electric field of aluminum reduction cell(ARC) as the research object,the performance of two classical RP methods,which are Al-NASRA and NGUYEN partition(ANP) algorithm and the multi-level partition(MLP) method,has been analyzed and compared.The comparison results indicate a sound performance of ANP algorithm,but to large-scale models,the computing time of ANP algorithm increases notably.This is because the ANP algorithm determines only one node based on the minimum weight and just adds the elements connected to the node into the sub-region during each iteration.To obtain the satisfied speed and the precision,an improved dynamic self-adaptive ANP(DSA-ANP) algorithm has been proposed.With consideration of model scale,complexity and sub-RP stage,the improved algorithm adaptively determines the number of nodes and selects those nodes with small enough weight,and then dynamically adds these connected elements.The proposed algorithm has been applied to the finite element analysis(FEA) of the electric field simulation of ARC.Compared with the traditional ANP algorithm,the computational efficiency of the proposed algorithm has been shortened approximately from 260 s to 13 s.This proves the superiority of the improved algorithm on computing time performance.

Resistance optimization of flexes in aluminum reduction cells

The resistance arrangements of the flexes connecting with the cathode bus bar in aluminum reduction cells were generalized as three modes. In each mode the universal method to select proper resistivity of the flexes was induced respectively to insure that the current in local group of flexes was equal. Furthermore, a 350 kA aluminum reduction cell based electric field model was developed by finite element method to evaluate the effect of the method. Suggestions on selection of three modes were also put forward. The results show that the methods of resistance optimization can reduce the current variation about 180 A compared with that in original case.

CFD simulation of effect of anode configuration on gas–liquid flow and alumina transport process in an aluminum reduction cell

Numerical simulations of gas–liquid two-phase flow and alumina transport process in an aluminum reduction cell were conducted to investigate the effects of anode configurations on the bath flow, gas volume fraction and alumina content distributions. An Euler–Euler two-fluid model was employed coupled with a species transport equation for alumina content. Three different anode configurations such as anode without a slot, anode with a longitudinal slot and anode with a transversal slot were studied in the simulation. The simulation results clearly show that the slots can reduce the bath velocity and promote the releasing of the anode gas, but can not contribute to the uniformity of the alumina content. Comparisons of the effects between the longitudinal and transversal slots indicate that the longitudinal slot is better in terms of gas–liquid flow but is disadvantageous for alumina mixing and transport process due to a decrease of anode gas under the anode bottom surface. It is demonstrated from the simulations that the mixing and transfer characteristics of alumina are controlled to great extent by the anode gas forces while the electromagnetic forces(EMFs) play the second role.

Structure optimization of the dispensing house in a combustion train for a thermal bake-out aluminum reduction cell

The fume bake-out aluminum reduction cell is a novel technology possessing such advantages as easy control for the speed of heating-up, well-distributed temperature, and little cathode and anode oxidation. The key equipment of fume bake-out is a combustion train whose one important part is a dispensing house. This work deals with the numerical model and the flow and temperature fields of the dispensing house, which suggests that uniformity of flow and energy distribution is influenced by the position, shape and direction of the nozzle and cross dimension of dispensing house mainly, but is less influenced by entry speed. The parameters of the dispensing house structure are optimised to satisfy the requirements for a combustion train in fume bake-out, and appropriate dimensions are obtained for a dispensing house structure.

THE NUMERICAL SIMULATION OF FLOW IN ALUMINUM REDUCTION CELLS

The electromagnetic force causes a circulation of both cryolite and the metal in the aluminum reduction cells. This motion has the effect of reducing the current efficiency of the cell, and increases the distance between the an- ode and the cathode. Using the time-averaged Navier-Stokes equations and the K-e model of turbulence this paper numerically calculated the distributions of velocities, pressure, turbulent kinetic energy in the cells and deforma- tion of the interface of cryolite and metal. These results may be used to control the process of production and to improve the design of the cells.

Modeling of Three-Phase Flow and Interface Deformation of Metal/Bath in Aluminum Reduction Cell With Cathode Protrusion

Stabilizing the interface wave of the molten aluminum(metal)-electrolyte(bath)is beneficial to shorten the anode-cathode distance(ACD)which is critical to the energy saving.A coupled mathematical model was developed to study the impact of the novel cathode protrusion on the molten fluid motion as well as the metal-bath interface deformation.The molten fluid motion in the aluminum reduction ceils is under the combined effect of the electro-magnetic forces(EMFs)and the gas bubbles generated at the anode.A transient inhomogeneous three-phase model(metal-bath-gas bubble)was established in order to calculate more accurate.The results indicate that the metal-bath interface deformation can be reduced significantly by the novel cathode protrusion which is beneficial to the electric energy saving.Besides,The EMFs decreases as a result of the optimizing of the magnetic field due to the novel cathode convex which is an important driving force for the deformation of the interface.In addition,large vortex in the metal flow field is break up into the small vortex by the cathode protrusion and then dissipated due to the viscous force and the hindering effect of the cathode protrusion.The quantity of the vortex as well as the strength of the vortex reduces significantly in the reduction cell with novel cathode protrusion.

COUPLED SIMULATION OF 3D ELECTRO-MAGNETO-FLOW FIELD IN HALL-HEROULT CELLS USING FINITE ELEMENT METHOD

Two full 3D steady mathematical models are developed by finite element method （FEM） to calcalate coupled physics fields. the electro-magnetic model is built and solved first and so is the fluid motion model with the acquired electromagnetic force as source body forces in Navier-Stokes equations. Effects caused by the ferromagnetic shell, busbar system around, and open boundary problem as well as inside induced current were considered in terms of the magnetic field. Furthermore, a new modeling method is found to set up solid models and then mesh them entirely with so-called structuralized grids, namely hex-mesh. Examples of 75kA prebaked cell with two kinds of busbar arrangements are presented. Results agree with those disclosed in the literature and confirm that the coupled simulation is valid. It is also concluded that the usage of these models facilitates the consistent analysis of the electric field to magnetic field and then flow motion to the greater extent, local distributions of current density and magnetic flux density are very much dependent on the cell structure, the steel shell is a shield to reduce the magnetic field and flow pattern is two dimensional in the main body of the metal pad.

Recent developments in copper-based, non-noble metal electrocatalysts for the oxygen reduction reaction

The high cost of Pt-based catalysts and the sluggish dynamics of the oxygen reduction reaction （ORR） severely hinder the rapid development of fuel cells, Therefore, the search for inexpensive, non-noble metal catalysts to substitute Pt-based catalysts has become a critical issue in the ORR research field, As an earth-abundant element, the use of Cu to catalyze the ORR has been explored with the ultimate target of finding a replacement for Pt-based catalysts in fuel cells. This review mainly focuses on recent research progress with Cu-based ORR catalysts and aims to aid readers＇ understanding of the status of development in this field. The review begins with a general update on the state of knowledge pertaining to ORR, This is followed by an overview of recent research based on Cu nanomaterial catalysts, which comprises Cu complexes, compounds, and other structures. Charting the development of Cu-based ORR catalysts shows that designing Cu-based materials to mimic active enzymes is an effective approach for ORR catalysis. By collecting recent developments in the field, we hope that this review will promote further development of Cu-based ORR catalysts and their application in fuel cells.

Application of fiber Bragg grating sensor network in aluminum reduction tank shell temperature monitoring

A fiber Bragg grating temperature sensor network was designed to implement the real-time health monitoring of the aluminum reduction cell. The heat transfer process was simulated using software ANSYS, and an on-line shell monitoring system was established based on optical sensing technology. According to aluminum reduction cell heat transfer theory, the 2D slice finite element model was developed. The relationship between shell temperature and cell status was discussed. Fiber Bragg grating （FBG） was chosen as the temperature sensor in light of its unique advantages. The accuracy of designed FBG temperature sensors exceeds 2 ~C, and good repeatability was exhibited. An interrogation system with 104 sensors based on VPG （volume phase grating） filter was established. Through the long-term monitoring on running state, the status of the aluminum reduction cell, including security and fatigue life could be acquired and estimated exactly. The obtained results provide the foundation for the production status monitoring and fault diagnosis. Long-term test results show good stability and repeatability which are compatible with electrolysis process.

Colloidal Alumina-bonded TiB_2 Coating on Cathode Carbon Blocks in Aluminum Cells

Self-propagating high-temperature synthesis (SHS) with reduction process was used to fabricate TiB2 powder from TiO2-B2O3-Mg system. The colloidal alumina-bonded TiB2 paste was prepared and coated on the cathode carbon blocks. Various properties of the baked paste such as the corrosive resistance, thermal expansion and wettability were tested. Experimental results showed that the colloidal alumina-bonded TiB2 coating could be well wetted by liquid aluminum; and the thermal expansion coefficient of the coated material was 5.8x10(-6) degreesC(-1) at 20-1000 degreesC, which was close to that of the traditional anthracite block cathode (4x10(-6) degreesC(-1)); the electrical resistivity was 8 mu Omega (.)m at 900 degreesC when the content of alumina in the coated material was about 9% in mass fraction. In addition, some other good results such as sodium resistance were also reported.

Influence of phosphoric anions on oxygen reduction reaction activity of platinum, and strategies to inhibit phosphoric anion adsorption

Nation-membrane-based proton exchange fuel cells （PEMFCs） typically operate at below 100 ℃. However, H3PO4-doped polybenzimidazole （PBI）-based PEMFCs can operate at 100-200 ℃. This is advantageous because of accelerated reaction rates and enhanced tolerance to poisons such as CO and S02, which can arise from reformed gas or the atmosphere. However, the strong adsorption of phosphoric anions on the Pt surface dramatically decreases the electrocatalytic activity. This study exploits the ＂third-body effect＂, in which a small amount of organic molecules are pre-adsorbed on the Pt surface to inhibit the adsorption of phosphoric anions. Pre-adsorbate species inhibit the ad- sorption of phosphoric anions, but can also partially occlude active sites. Thus, the optimum pre-adsorbate coverage is studied by correlating the oxygen reduction reaction （ORR） activity of Pt with pre-adsorbate coverage on the Pt surface. The influence of the pre-adsorbate molecule length is investigated using the organic amines, butylamine, octylamine, and dodecylamine, in both 0.1 mol/L HCI04 and 0.1 mol/L H3P04. Such amines readily bond to the Pt surface. In aqueous HCI04 electrolyte, the ORR activity of Pt decreases monotonically with increasing pre-adsorbate coverage. In aqueous H3P04 electrolyte, the ORR activity of Pt initially increases and then decreases with in- creasing pre-adsorbate coverage. The maximum ORR activity in H3P04 occurs at a pre-adsorbate coverage of around 20%. The effect of molecular length of the pre-adsorbate is negligible, but its coverage strongly affects the degree to which phosphoric anion adsorption is inhibited. Butylamine adsorbs to Pt at partial active sites, which decreases the electrochemically active surface area. Ad- sorbed butylamine may also modify the electronic structure of the Pt surface. The ORR activity in the phosphoric acid electrolyte remains relatively low, even when using the pre-adsorbate modified Pt/C catalysts. Further development of the catalyst and electrolyte is required before the commercialization of H3PO4-PBl-based PEMFCs can be realized.

Bio-inspired carbon electro-catalysts for the oxygen reduction reaction

We report the synthesis, characterisation and catalytic performance of two nature-inspired biomassderived electro-catalysts for the oxygen reduction reaction in fuel cells. The catalysts were prepared via pyrolysis of a real food waste（lobster shells） or by mimicking the composition of lobster shells using chitin and CaCO3 particles followed by acid washing. The simplified model of artificial lobster was prepared for better reproducibility. The calcium carbonate in both samples acts as a pore agent, creating increased surface area and pore volume, though considerably higher in artificial lobster samples due to the better homogeneity of the components. Various characterisation techniques revealed the presence of a considerable amount of hydroxyapatite left in the real lobster samples after acid washing and a low content of carbon（23%）, nitrogen and sulphur（〈1%）, limiting the surface area to 23 m^2/g, and consequently resulting in rather poor catalytic activity. However, artificial lobster samples, with a surface area of ≈200 m^2/g and a nitrogen doping of 2%, showed a promising onset potential, very similar to a commercially available platinum catalyst, with better methanol tolerance, though with lower stability in long time testing over 10,000 s.

Analysis and modeling of alumina dissolution based on heat and mass transfer

A comprehensive heat and mass transfer model of dissolution process of non-agglomerated and agglomerated alumina particles was established in an aluminum reduction cell. An appropriate finite difference method was used to calculate the size dissolution rate, dissolution time and mass of alumina dissolved employing commercial software and custom algorithm based on the shrinking sphere assumption. The effects of some convection and thermal condition parameters on the dissolution process were studied. The calculated results show that the decrease of alumina content or the increase of alumina diffusion coefficient is beneficial for the increase of size dissolution rate and the decrease of dissolution time of non-agglomerated particles. The increase of bath superheat or alumina preheating temperature results in the increase of size dissolution rate and the decrease of dissolution time of agglomerated particles. The calculated dissolution curve of alumina（mass fraction of alumina dissolved） for a 300 k A aluminum reduction cell is in well accordance with the experimental results. The analysis shows that the dissolution process of alumina can be divided into two distinct stages： the fast dissolution stage of non-agglomerated particles and the slow dissolution stage of agglomerated particles, with the dissolution time in the order of 10 and 100 s, respectively. The agglomerated particles were identified to be the most important factor limiting the dissolution process.

Effects of electrolysis process parameters on alumina dissolution and their optimization

The Box–Behnken design and desirability approach were used to investigate and optimize the process parameters for aluminum reduction cells related to alumina dissolution. The bath temperature, alumina content, current and alumina temperature were chosen as the design parameters. The content of cumulative dissolved alumina(CCDA) and the relative deviation from the target content(RDTC) were adopted as the responses. The interactive influence results show that increasing the bath temperature and alumina temperature, as well as decreasing the alumina content, can increase CCDA. Increasing the bath temperature and lowering the current are beneficial for obtaining a more uniform alumina distribution. The optimal operating parameters were determined to be as follows: bath temperature of 958.8 ℃, alumina content of 2.679 wt.%, current of 300 kA and alumina temperature of 200 ℃.

针灸作用机制研究的困惑与出路--针灸调节肠易激综合征肠功能机制研究的系统科学思考

以还原论为主体的研究方法在针刺作用机制探索过程中发挥了巨大作用,但该方法也存在明显的局限性,以针灸调节肠易激综合征(IBS)肠功能机制研究为例,对此进行了反思。认为针灸治疗IBS机制的探索涉及范围广泛、层次多样,但获得的认识多是碎片化的,缺乏对众多环节间相互作用和相互协调的了解。为弥补还原论方法的不足,从系统科学角度探索针灸的作用机制是一种必然的趋势,从系统生物学的角度,特别是从细胞行为组学角度对针灸调节机制的研究思路及其可行性进行探讨,提出了一是基于“中枢神经系统-自主神经系统-胃肠道神经-Cajal间质细胞-平滑肌细胞(CNS-ANS-ENS-ICC-SMC)网络”细胞行为组学的研究,二是基于肠道类器官多种细胞行为组学的研究,以期将针灸调节规律及其机制的认识推进到更深的层次。