Thermodynamic properties of Ln-O (Ln = La, Pr, Nd) solid solutions and their deoxidation by molten salt electrolysis

The lanthanide metals lanthanum, praseodymium and neodymium containing 2,200, 2,600, 1,850 mass ppm oxygen, respectively, were deoxidized to 20-30 ppm level at 1,073 K by an electrochemical method. The metal to be deoxidized was used as the cathode in an electrolysis cell which consisted of a graphite anode and molten CaCl2 electrolyte. The calcium metal produced at the cathode by electrolysis effectively deoxidized the lanthanide metal. Calcium oxide produced by deoxidation, dissolved in the melt. The liberation of carbon monoxide/dioxide at the anode was found to prevent accumulation of oxygen in the melt. For a quantitative discussion of the limits of deoxidation achievable by this technique, a thermodynamic investigation of the lanthanide-oxygen (Ln-O ; Ln = La, Pr, Nd) solid solutions was conducted. The lanthanide metal, yttrium and titanium samples were immersed in calcium-saturated CaCl2 melt, containing a small quantity of dissolved CaO, at 1,093 K. The oxygen potential of the melt and the Ln-O solid solutions were obtained from the oxygen content of yttrium samples at equilibrium, and the known thermodynamic properties of yttrium-oxygen solid solution. The results were confirmed by using Y/Y2O3 equilibrium to control the oxygen potential of the molten salt reservoir. The oxygen affinity of the metals was found to decrease in the order : Y > Ti > Nd > Pr > La. The deoxidation results are consistent with the thermodynamic properties of the RE-O solid solutions.

Wastewater Electrolysis Cell for Environmental Pollutants Degradation and Molecular Hydrogen Generation

This study proposes a wastewater electrolysis cell (WEC) for on-site treatment of human waste coupled with decentralized molecular H₂ production. The core of the WEC includes mixed metal oxides anodes functionalized with bismuth doped TiO₂ (BiO_x/TiO₂). The BiO_x/TiO₂ anode shows reliable electro-catalytic activity to oxidize Cl- to reactive chlorine species (RCS), which degrades environmental pollutants including chemical oxygen demand (COD), protein, NH4⁺, urea, and total coliforms. The WEC experiments for treatment of various kinds of synthetic and real wastewater demonstrate sufficient water quality of effluent for reuse for toilet flushing and environmental purposes. Cathodic reduction of water and proton on stainless steel cathodes produced molecular H2 with moderate levels of current and energy efficiency. This thesis presents a comprehensive environmental analysis together with kinetic models to provide an in-depth understanding of reaction pathways mediated by the RCS and the effects of key operating parameters. The latter part of this thesis is dedicated to bilayer hetero-junction anodes which show enhanced generation efficiency of RCS and long-term stability.

Chapter 2 describes the reaction pathway and kinetics of urea degradation mediated by electrochemically generated RCS. The urea oxidation involves chloramines and chlorinated urea as reaction intermediates, for which the mass/charge balance analysis reveals that N₂ and CO₂ are the primary products. Chapter 3 investigates direct-current and photovoltaic powered WEC for domestic wastewater treatment, while Chapter 4 demonstrates the feasibility of the WEC to treat model septic tank effluents. The results in Chapter 2 and 3 corroborate the active roles of chlorine radicals (Cl•/Cl₂^-•) based on iR-compensated anodic potential (thermodynamic basis) and enhanced pseudo-first-order rate constants (kinetic basis). The effects of operating parameters (anodic potential and [Cl^-] in Chapter 3; influent dilution and anaerobic pretreatment in Chapter 4) on the rate and current/energy efficiency of pollutants degradation and H₂ production are thoroughly discussed based on robust kinetic models. Chapter 5 reports the generation of RCS on Ir_0.7Ta_0.3O_y/Bi_xTi_1-xO_z hetero-junction anodes with enhanced rate, current efficiency, and long-term stability compared to the Ir_0.7Ta_0.3O_y anode. The effects of surficial Bi concentration are interrogated, focusing on relative distributions between surface-bound hydroxyl radical and higher oxide.

A vertically aligned carbon nanotube/fiber based electrode for economic hydrogen production by water electrolysis

Electrolysis is the most mature form of hydrogen production. Unfortunately, water electrolysis has not yet achieved the efficiency and the cost levels required for any practical application. In order to enhance the current density, modification of the electrolyte and the electrode morphology are the most popular approaches. Recently there have been numerous reports on how to improve the efficiency of hydrogen production by water splitting [1-3]. On the electrode side, the use of non-platinum high efficiency electrode materials for water splitting will provide a promising future for the hydrogen economy. An ideal electrode for water electrolysis should have good permeability to water and gas. It should also offer good electrical properties with a long life. A porous graphite plate, when coated with titania, for example, is known to provide a simple and economical electrode for water electrolysis [4]. © 2010 IEEE.

Frame assisted H2O electrolysis induced H2 bubbling transfer of large area graphene grown by chemical vapor deposition on Cu

An improved technique for transferring large area graphene grown by chemical vapor deposition on copper is presented. It is based on mechanical separation of the graphene/copper by H2 bubbles during H2O electrolysis, which only takes a few tens of seconds while leaving the copper cathode intact. A semi-rigid plastic frame in combination with thin polymer layer span on graphene gives a convenient way of handling- and avoiding wrinkles and holes in graphene. Optical and electrical characterizations prove the graphene quality is better than that obtained by traditional wet etching transfer. This technique appears to be highly reproducible and cost efficient. © 2013 American Institute of Physics.

Preparation of Pb-Ca-Na master alloy using molten chloride salt electrolysis

An electrolysis technique for co-deposition of Ca2+ and Na+ at the liquid lead cathode was put forward. The experiment was carried out at an electrolysis temperature below 650 degrees C and had a current efficiency of 98%, which are respectively 100 similar to 300 degrees C lower and 15% similar to 30% higher than those reported both at home and abroad.

Magneto-hydro-dynamic analysis of an electrolysis cell for aluminum production

An electrolytic cell for Aluminum production contains molten metal subject to high currents and magnetic flux density. The interaction between these two fields creates electromagnetic forces within the liquid metal and can generate oscillations of the fluid similar to the waves at the free surface of oceans and rivers. The study of this phenomenon requires the simulation of the current density field, of the magnetic flux density field and the solution of the equations of motion of the liquid mass. An attempt to analyze the dynamical behavior of this problem is made by coupling different codes, based on different numerical techniques, in a single tool. The simulations are presented and discussed.

Modeling the dynamics of electromagnetically agitated metallurgical flows: levitation, cold crucible, aluminium electrolysis, etc.

We present practical modelling techniques for electromagnetically agitated liquid metal flows involving dynamic change of the fluid volume and shape during melting and the free surface oscillation. Typically the electromagnetic field is strongly coupled to the free surface dynamics and the heat-mass transfer. Accurate pseudo-spectral code and the k-omega turbulence model modified for complex and transitional flows with free surfaces are used for these simulations. The considered examples include magnetic suspension melting, induction scull remelting (cold crucible), levitation and aluminium electrolysis cells. The process control and the energy savings issues are analysed.

Demonstration thermo-electric and MHD mathematical models of a 500 kA A1 electrolysis cell

In the present study, a 3D full cell quarter thermo-electric model of a 500kA demonstration cell has been developed and solved. In parallel, a non-linear wave MHD model of the same 500 kA demonstration cell has been developed and solved. A preliminary study of the impact of the interactions between the cell thermo-electric and MHD models will be presented.

Time dependent electric, magnetic and hydrodynamic interaction in aluminium electrolysis cells

The waves in commercial cells for electrolytic aluminium production originate at the interface between the liquid aluminium and electrolyte, but their effect can spread into the surrounding busbar network as electric current perturbation, and the total magnetic field acquires a time dependent component. The presented model for the wave development accounts for the nonuniform electric current distribution at the cathode and the whole network of the surrounding busbars. The magnetic field is computed for the continuous current in the fluid zones, all busbars and the ferromagnetic construction elements. When the electric current and the associated magnetic field are computed according to the actual electrical circuit and updated for all times, the instability growth rate is significantly affected. The presented numerical model for the wave and electromagnetic interaction demonstrates how different physical coupling factors are affecting the wave development in the electrolysis cells. These small amplitude self-sustained interface oscillations are damped in the presence of intense turbulent viscosity created by the horizontal circulation velocity field. Additionally, the horizontal circulation vortices create a pressure gradient contributing to the deformation of the interface. Instructive examples for the 500 kA demonstration cell are presented.

Shallow water model for aluminium electrolysis cells with variable top and bottom

The MHD wave instability in commercial cells for electrolytic aluminium production is often described using ‘shallow water’ models. The model [1] is extended for a variable height cathode bottom and anode top to account for realistic cell features. The variable depth of the two fluid layers affects the horizontal current density, the wave development and the stability threshold. Instructive examples for the 500 kA cell are presented.

Impact of the vertical potshell deformation on the MHD cell stability behavior of a 500 kA aluminium electrolysis cell

In previous publications [1,2], it was rationalized that a large vertical potshell deformation may have a negative impact on the operations of very high amperage cells. The MHD-Valdis non-linear Magneto-Hydro-Dynamic model was therefore extended to take into account the displacement of the potshell. The MHD cell stability behavior of a 500 kA cell with a 17.3 meters long potshell was then studied.