This thesis documents the development and application of a computer model for gibbsite, an aluminium tri-hydroxide polymorph. In particular, the work has emphasized the idea of computer modelling techniques combining with ex- observations to provide greater insight than either could separately. Chapter One provides an overview and introduction to the fields of solid state chemistry, crystallization and computer modelling. These ideas are extended in Chapter Two to include a more detailed discussion of the theoretical principles behind the modelling in this project. The development of transferable oxalate and hydroxide potential models, intended primarily for sodium oxalate and gibbsite, is described in Chapter Three. Both ab initio hypersurface fitting and lattice fitting techniques were utilized, with an average structural fitting error of under two percent. In addition, the potentials were used to successfully reproduce several (related) crystal structures, thus establishing the quality of the model. In Chapter Four, the model for gibbsite was employed in generating equilibrium and growth morphologies. The equilibrium morphology was found to give excellent agreement with experiment, with all observed faces present. However, the importance of the prismatic planes is underestimated. Also discussed in the chapter is a method for predicting the phenomenon of crystalline twinning. This technique was successfully applied to a number of systems, including gibbsite and sodium oxalate. In Chapter Five, the equilibrium morphology calculations performed earlier were extended by probing the effects of cation incorporation on the habit of gibbsite. This study was conducted in order to provide a first step in estimating the role of the crystallizing solution. Calculations of the change in surface energy caused by the replacement of a surface proton with a cation from solution ++ / were made. Different crystal habits were constructed by applying a range of defect surface coverage values to each of the faces appearing in the morphology. The resulting defect morphologies were in excellent agreement with crystal habits commonly observed by experimentalists. Also, the work provided an explanation for the earlier underestimation of the prismatic faces. Chapter Six documents molecular simulations of solutions containing the major species known to be present in industrial and experimental Bayer liquors. The structuring in two solutions, one containing sodium hydroxide and the other potassium hydroxide, was probed by constructing graphs of the radial distribution functions. These plots indicated that a significant degree of ion pairing was occurring between the alkali metal cations (Na+ and K+) and the aluminate monomer ([Al(OH)4(subscript)]-). Furthermore, these cations were found to be acting as 'bridges' which stabilize multiple aluminate monomers, allowing them to form clusters. This data was used to assist in explaining vibrational spectra, and to postulate that clustering may be the origin of the fine particle suspensions noted during the induction period.

The 53 million gallons (240,000 tons) of nuclear waste stored at the Hanford site comprises approximately 60% of the nation¡¯s legacy nuclear waste. Previously, processing of the saltcake phases of tank wastes dominated disposal efforts at Hanford. Interest is now being directed at the processing and pretreatment of the sludge phases of the waste. These sludges, consisting of complex combinations of insoluble metal compounds, present many challenges. This thesis deals with experimentation pertaining primarily to aluminum chemistry and the role it plays in pretreatment of Hanford waste sludge. Included is a statistical analysis of an inventory of components within Hanford tanks. A recipe was followed to produce a simulant sludge for further experimentation. The solubility of the aluminum species, gibbsite, thought to be the most common aluminum species in the Hanford tanks, was studied. In addition, the reaction by which gibbsite is transformed to a much less soluble phase, boehmite, was studied in depth. Gibbsite¡¯s transformation to boehmite begins at about 200 ¡ÆC, a temperature higher than that seen by Hanford tanks. However, recent literature suggests that it may be converted to boehmite at lower temperatures. A study of the rate of boehmite formation at temperatures ranging from 80 to 150 ¡ÆC using caustic concentrations of 1.5, 3, and 5 molal is reported. In such a way, the effects of both temperature and caustic loading on the rate of boehmite formation were sought. It was determined that boehmite formed readily at temperatures 120 ¡ÆC and higher. These data supplement existing aluminum chemistry knowledge and will increase the efficiency with which sludge pretreatment and disposal procedures are designed.

Although the precipitation of aluminium trihydroxide as gibbsite, via the Bayer process has been widely studied, the mechanism of crystal growth is poorly understood. This work focus on the morphology of gibbsite and the relative growth rates of individual crystal faces.Initial work was carried out to characterize aluminium trihydroxide and it was found that bayerite, another polymorph, precipitated at temperatures below 50 [degrees] C and its morphology depended on the method of precipitation. Gibbsite however, precipitated above this temperature and its morphology depended on the type of alkali aluminate solutions used. The method of precipitation does not affect the morphology, only the size of the precipitate formed. The morphology of gibbsite can be altered by the addition of organic compounds which are known to inhibit gibbsite precipitation. Some of these compounds were found to selectively inhibit the growth of individual crystal faces, thus altering the overall morphology of gibbsite. Boehmite, a polymorph of aluminium hydroxide, can be produced by partial dehydration of gibbsite at 300T. The morphology of boehmite consisted of diamond shaped crystals.The influence of cation incorporation on the morphology of gibbsite was studied experimentally and computationally (molecular modelling). These studies showed that there is a linear relationship between the amount of cation incorporated and atomic radii and between the amount of cation incorporated and the defect energy calculated. The equilibrium morphology of gibbsite predicted in the absence of media matched the morphology of gibbsite grown slowly from sodium aluminate, implying that the amount of sodium incorporation is low in these crystals.The growth rates of individual crystal faces were measured in situ, and found to be a function of supersaturation squared for the prismatic faces, possibly indicating ++ / that E growth occurs by spiral growth mechanism. The growth of the basal face was found to follow the spiral growth mechanism below a relative supersaturation of 0.815 and the birth and spread mechanism above this level. The activation energies and kinetic coefficients for the individual prismatic faces were also determined.Growth rate dispersion was observed in these microscopic studies, but the question of size dependency remains unanswered.The overall growth rates of gibbsite crystal, determined using rapid dynamic light scattering, was found to be an exponential function of supersaturation indicative of a birth and spread growth mechanism.

Gibbsite scale growth in pipe fittings is a major problem for an alumina refinery. A recent investigation into the scale growth mechanism at an alumina refinery found almost 60 % more scale growth in a reducer when compared with the connecting straight pipe sections for similar flow conditions. Scale growth occurs where liquor (supersaturated solutions) come in contact with solid surfaces and it is affected by the liquor flow velocity besides other physical and chemical parameters. The present work is dedicated to study the hydro-dynamical aspects of the mechanism of scale growth. In particular, the role of the phenomenon of turbulent bursting, stream wise and cross stream fluctuating velocity components (Ux and Uy) was investigated as the flow moves through the reducer. Particle Image Velocimetry (PIV) technique was used to get a full view of the reducer and the readings close-to-the-wall of the reducer at Reynolds number of 27,000 and 44,000 upstream which corresponds to Reynolds number of 41,500 and 66,000 downstream of the reducer respectively. The results showed an increase in cross stream and a decrease in magnitude of stream wise fluctuating velocity components, whereby we presume that the increased cross stream fluctuating velocity component increases the frequency of impacts of the scaling particles on the wall thus initiating excessive scale growth in the reducer when compared with the connecting straight pipe sections, for similar flow conditions.

Mercury is a toxic metal that has been released to the environment through numerous industrial activities. It can exist in various solid, aqueous, and gaseous forms. Volatile Hg(0) is frequently present at the source of a spill where it behaves as a dense non-aqueous phase liquid (DNAPL) contaminant that can change oxidation state and speciation via chemical or biological reactions. Mercury speciation is a key factor determining the mobility, bioavailability, and toxicity of Hg in the environment. Previous research has demonstrated that In Situ Thermal Desorption (ISTD) can be used in various modes to treat soil contaminants including Hg(0). The application of ISTD and other remediation processes must incorporate potential speciation during remediation and assess mobility of any mercury remaining in the soil post-remediation. However, research examining the impact of mercury speciation on ISTD processes is limited. The goals of this research are to investigate the fate and transport of mercury in soils from the source where concentrations are expected to be high to dilute solutions associated with down gradient groundwater, lakes, and rivers. For high concentrations of mercury, equilibrium speciation has been investigated to identify potential transformations at high temperatures consistent with those applied in ISTD processes. A model has been developed that describes mercury speciation over a range of environmental conditions. At low mercury concentrations, competitive Hg(II) adsorption on the soil minerals, goethite and gibbsite, has been evaluated over a range of experimental conditions. Models describing Hg(II) adsorption and aqueous speciation have been developed to provide a tool for predicting the fate and transport of residual mercury after thermal remediation applications. The results of these studies demonstrate that ISTD is feasible, but the off-gas speciation will depend on both the applied temperatures and the soil composition and redox conditions of the site. Pure phase mercury was predicted to be vaporized at temperatures well within the range of typical ISTD processes. The adsorption of trace levels of Hg(II) remaining after ISTD was successfully modeled on goethite and gibbsite using the 1-pK CD-MUSIC model. / text

No description available.

Ce travail qui a été effectué au sein du groupe radiochimie de l'IPN Orsay, participe à l'enrichissement des connaissances destinées à la compréhension du comportement des radionucléides à travers l'environnement. Le comportement et l'évolution des radionucléides sont des phénomènes souvent complexes à caractériser expérimentalement qui dépendent des interactions aux interfaces eau / surface minérale, lesquelles peuvent être modélisées grâce à des méthodes théoriques. Lors de cette étude, nous avons choisi d'utiliser des méthodes de dynamique moléculaire (DM), lesquelles permettent de considérer explicitement les effets du solvant, de la température et d'étudier la dynamique de l'ion uranyle. Dans un premier temps, des méthodes de dynamique moléculaire Car-Parrinello basées sur la théorie de la fonctionnelle de la densité (DFT) ont permis de caractériser finement les structures d'équilibres de l'ion uranyle en solution et à l'interface eau/ face (001) de gibbsite. Dans le cas d'un pH faible, les complexes d'adsorption présents à l’interface eau/ face (001) de gibbsite ont été identifiés et comparées aux données expérimentales disponibles. Leurs énergies relatives et les énergies d'activations impliquées dans le processus de sorption ont également été déterminées. Dans un deuxième temps, des méthodes de dynamique moléculaire classique ont été employées afin de modéliser des systèmes de plus grande taille, donc plus réalistes, sur des échelles de temps plus longues. La comparaison des résultats DM Car-Parrinello / DM classique a montré qu’une dynamique classique utilisée avec les potentiels non polarisables de Guilbaud, CLAYFF et SPC/E, permet de modéliser le comportement de l’ion uranyle à l’interface eau/ face (001) de gibbsite. Les longs temps de simulation permettent de mettre en avant le caractère diffusif de l’ion uranyle à l’interface eau/ face (001) de la gibbsite. Enfin, L’effet d’une élévation de la température a été étudié. La rétention de l’ion uranyle diminue avec la température. / This work was performed in the radiochemistry group of the IPN Orsay, it participates in the advancement of knowledge for understanding the behavior of radionuclides through the environment. The behavior and the evolution of the radionuclides, which are often complex phenomena to characterize experimentally, depend on interactions at the interfaces water / mineral surface and can be modeled using theoretical methods. In this study, we chose to use dynamics molecular methods (DM), which can explicitly consider the effects of solvent, temperature and allow to study the dynamics of the uranyl ion. At first, methods of Car-Parrinello dynamics molecular, based on the density functional theory (DFT), were used to characterize the structures of the uranyl ion in solution and at the interface water / (001) face of gibbsite. For low pH condition, the adsorption complexes present at the interface water / (001) face of gibbsite were identified and compared with available experimental data. Their relative energies and activation energies involved in the sorption process were also determined. Secondly, the classical molecular dynamics methods were used to model larger systems, thus more realistic, on longer time scales. Comparing the results DM Car-Parrinello / classical DM showed a classical dynamics, which use the non-polarizable Guilbaud, CLAYFF and SPC/E potentials, can model the behavior of the uranyl ion at the interface water / face (001) of gibbsite. The long simulation times, allow to show particularly the diffusive character of the uranyl ion to the interface water / face (001) of gibbsite. Finally, the effect of temperature rise was studied. Retention of the uranyl ion decreases with temperature.

Precipitation of gibbsite from supersaturated caustic aluminate solutions has been investigated extensively due to its central role in the commercial Bayer plant, for extracting the alumina compound from bauxite. The primary focus of Bayer process simulation and optimisation is to help maximise the product recovery and the production of a product crystal size distribution (CSD) that meets the product specification and improves downstream process performance. The product CSD is essentially determined by the nucleation, growth and agglomeration kinetics, which occur simultaneously during the precipitation process. These processes are still poorly understood, owing to the high complexity of their mechanisms and of the structure of the caustic aluminate solutions. This research focuses on the modelling and kinetics estimation aspects of simulating gibbsite precipitation. Population balance theory was used to derive different laboratory gibbsite precipitator models, and the discretised population balance models of Hounslow, Ryall & Marshall (1988) and Litster, Smit & Hounslow (1995) were employed to solve the resulting partial integro-differential equations. Gibbsite kinetics rates were determined from literature correlation models and also estimated from the CSD data using the, so-called, differential method. Modelling of nonstationary gibbsite precipitation systems showed that error propagated with the precipitation time scale. The main contribution to the observed error was found to be from the uncertainties in the kinetic parameter estimates, which are estimated from experimental data and used in the simulation. This result showed that care is required when simulating the CSD of non-stationary precipitators over longer time scales, and methods that produce precise estimates of the kinetics rates from the experimental data need to be used. / Kinetics estimation study from repeated batch gibbsite precipitation data showed that the uncertainty in the experimental data coupled with the error incurred from the kinetic parameter estimation procedure used, resulted in large uncertainties in the kinetics estimates. The influences of the experimental design and the kinetics estimation technique on the accuracy and precision of estimates of the nucleation, growth and agglomeration kinetics for the gibbsite precipitation system were investigated. It was found that the operating conditions have a greater impact on the uncertainties in the estimated kinetics than does the precipitator configuration. The kinetics estimates from the integral method, i.e. non-linear parameter optimisation method, describe the gibbsite precipitation data better than those obtained by the differential method. However, both kinetics estimation techniques incurred significant uncertainties in the kinetics estimates, particularly toward the end of the precipitation runs where the kinetics rates are slow. The uncertainties in the kinetics estimates are strongly correlated to the magnitude of kinetics values and are dependent on the change in total crystal numbers and total crystal volume. Batch gibbsite precipitation data from an inhomogeneously-mixed precipitator were compared to a well-mixed precipitation system operated under the same operating conditions, i.e. supersaturation, seed charge, seed type, mean shear rate and temperature. / It was found that the gibbsite agglomeration kinetic estimates were significantly different, and hence, the product CSD, but the gibbsite growth rates were similar. It was also found that a compartmental model approach cannot fully account for the differences in suspension hydrodynamics, and resulted in unsatisfactorily CSD predictions of the inhomogeneously-mixed precipitator. This is attributed to the coupled effects of local energy dissipation rate and solids phase mixing on agglomeration process.

In this research project, systematic studies of polymer-assisted flocculation and dewatering behaviour of colloidal gibbsite (y-Al(OH)3) dispersions, together with polymeric flocculant structure-mediated interfacial chemistry and particle interactions, have been performed. Clear links between flocculation performance, interfacial chemistry, particle interactions, dispersion settling rate and sediment consolidation were established for improved dewaterability.

In this research project, systematic studies of polymer-assisted flocculation and dewatering behaviour of colloidal gibbsite (y-Al(OH)3) dispersions, together with polymeric flocculant structure-mediated interfacial chemistry and particle interactions, have been performed. Clear links between flocculation performance, interfacial chemistry, particle interactions, dispersion settling rate and sediment consolidation were established for improved dewaterability.