Dans l’optique du développement de procédés propres, cette recherche a consisté à étudier un procédé de réduction du dioxyde de soufre contenu dans des rejets gazeux industriels par absorption dans une solution de lavage contenant un oxydant particulier, le peroxyde d’hydrogène H2O2, qui oxyde irréversiblement le SO2 en acide sulfurique. C’est un procédé a priori intéressant puisqu’il génère des solutions d’acide sulfurique qui, si on parvient à les concentrer suffisamment par recyclage, peuvent être utilisées pour diverses applications industrielles, ou réinjectées dans le procédé produisant le polluant acide, tout résidu polluant liquide étant alors inexistant dans cette technique d’épuration de gaz. En vue de l’application de cette technique, notre travail a permis de progresser dans la connaissance du système SO2-H2O2-H2SO4 par une double étude portant sur la cinétique et la thermodynamique des phénomènes. Finalement, un modèle de dimensionnement assez général, valable dans une large gamme de conditions opératoires industrielles de concentrations en acide sulfurique et en peroxyde d’hydrogène de la solution de lavage et de température de l’effluent à traiter, a été développé et ce afin de réaliser les projets de n’importe quel type de contacteur (colonnes à films, à garnissage ou à pulvérisation) à condition bien entendu de les combiner aux caractéristiques de transfert propres à ces divers contacteurs. A titre d’exemple, nous avons dimensionné dans notre travail une colonne d’absorption à garnissage permettant d’épurer les gaz d’une fonderie de cuivre et produisant un acide sulfurique à 40 % en poids.

Prevention of groundwater contamination by agricultural chemicals requires an understanding of the complex processes that control pesticide movement below the soil surface. Through this understanding it is possible to try to predict which areas may be most vulnerable to contamination. The many models that have been developed to characterize pesticide movement vary widely in their conceptual approach and degree of complexity. A soil properties model was developed in this thesis to determine the relative overall pesticide movement potential in Oregon agricultural soils. Its focus is ease of use in both acquisition of input values and running of the model. The model is based on soil properties important in controlling pesticide movement. It is a rating system model that uses scoring of factors and matrices to weigh the soil values. It is organized into two processes: leaching and sorption. The leaching potential is based on soil permeability and drainage class. The sorption potential is based on organic matter content and texture of the soil surface horizon(s). The interaction of these two processes results in the overall pesticide movement potential. / Graduation date: 1991

Cadmium (Cd) from the soil can accumulate in our bodies via the consumption of our crops and cause serious health problems. While it has been documented that long-term cultivation affects physical and chemical properties of soil, little is known about its effect on the phytoavailability, solid-phase speciation, and profile distribution of soil Cd. The objectives for this study were to determine the effect of long-term cultivation on: (1) a cadmium availability index (CAI) that reflects phytoavailable Cd for durum wheat, and related soil properties, (2) the solid-phase species of soil Cd and relationships between the CAI and the solid-phase species of soil Cd and related solid-phase soil component properties, and (3) the profile distribution of total soil Cd in the past, and the profile distribution of total soil Cd over the next 100 years. One Orthic Chemozemic soil profile was investigated from a virgin and an adjacent long-term cultivated field at eight sites in the Brown, Dark Brown, and Black soil zonesof Saskatchewan, Canada. Long-term cultivation significantly decreased the CAI. A decrease in total Cd, total Zn, and CEC, and an increase in aromaticity of the soil organic matter and soil pH all contributed to the decrease in the CAI. Both the virgin and cultivated soils had the same solid-phase Cd species with the same order of relative abundance: metal-organic complex-bound > easily reducible metal oxide-bound > H2O2 extractable organic-bound > crystalline metal oxide-bound > exchangeable. However, metal-organic complex-bound Cd and H2O2 extractable organic-bound Cd decreased significantly with long-term cultivation. In the virgin soils two solid-phase Cd species correlated significantly with the CAI: exchangeable Cd (r = 0.93) and easily reducible metal oxide-bound Cd (r = -0.88). In the cultivated soils three solid-phase Cd species correlated significantly with the CAI: exchangeable Cd (r = 0.95), metal-organic complex-bound Cd (r = 0.71), and crystalline metal oxide-bound Cd (r = 0.86). For both the virgin and cultivated soils, the concentration of A horizon Cd > C horizon Cd > B horizon Cd. In the past, A horizon Cd concentration decreased significantly with long-term cultivation. However, it is estimated that in 100 years, with the use of phosphate fertilizer made from Idaho ore, the total A horizon Cd content in these soils could be 3.5 times higher and reach a concentration of 1.18 mg Cd kg-1 soil which is in the critical region where the phytoavailability of soil Cd could increase dramatically. The present study has advanced the frontiers of knowledge on the effect of long-term cultivation on the Cd content and distribution in the soil profile, its phytoavailability index, solid-phase species, and the soil properties related to its phytoavailability. Extending research such as this to other major agricultural soil types and farming practices will assist in the development of innovative management strategies to curtail Cd contamination of the terrestrial food chain.

Thesis (Ph. D.)--University of Washington, 2002. / Vita. Includes bibliographical references (leaves 148-163).

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The Electrolyte Nonrandom Two-Liquid Activity Coefficient model in Aspen PlusTM 2006.5 was used to develop a rigorous and consistent thermodynamic representation for the base sub-component systems associated with aqueous combinations of K₂CO₃, KHCO₃, MEA, and piperazine (PZ) in a mixed-solvent electrolyte system for the application of CO₂ absorption/stripping from coal fired power plants. We developed a new vapor-liquid equilibrium apparatus to measure CO₂, amine, and H2O vapor pressures at 40 and 60 oC. We found that the volatility of MEA and PZ can be approximated at 50 and 20 ppmv at 40°C for any solvent composition studied in this work, over the CO₂ partial pressure range from 0.01 to 0.1 kPa. Very few solvent compositions exhibited a greater differential capacity than 7 m MEA at 60°C; specifically 11 m MEA, 3.5 m MEA + 3.6 m PZ, 7 m MEA + 2 m PZ, 7 m MEA + 3.6 m PZ, and 5 m K+ + 7 m MEA + 3.6 m PZ. Piperazine exhibited a possible maximum differential capacity of 2.21 mole CO₂/kg-H₂O at a concentration of 7.3 m. At the Norwegian University of Science and Technology, Inna Kim determined the differential enthalpy of CO₂ absorption for aqueous combinations of K₂CO₃, KHCO₃, MEA, PZ, and CO₂, based on a consistent experimental method developed for MEA, from 40 to 120°C for use in this work. In addition, we developed a consistent method to measure the specific heat capacity for a number of similar solvent combinations. We found that the enthalpy of CO₂ absorption increased with temperature because the apparent partial heat capacity of CO₂ may be considered small. Finally, by using a differential scanning calorimeter, we determined the dissolution temperature for aqueous mixtures of unloaded piperazine, which inferred an effective operating range for solutions of concentrated piperazine, greater than 5 m PZ, over a loading range between 0.25 to 0.45 mole CO₂/2·mol PZ. Through unit cell x-ray diffraction, we were able to identify and characterize the presence of three solid phases (PZ·6H₂O, KHCO₃, and KvPZ(COO)₂) in aqueous mixture combinations of K₂CO₃, KHCO₃, PZ, and CO₂. / text

Aqueous solution surface tension as a function of vapor-phase solute pressure isotheims were measured at atmospheric pressure for single and binary component benzene, methyl-substituted benzene (i.e., methylbenzene, 1,2-dimethylbenzene, 1,3- dimethylbenzene, 1,4-dimethylbenzene, 1,3,5-trimethylbenzene), and trichloroethene adsorption. Solute-induced surface tension variations were quantified using a dynamic adsorption protocol in conjunction with Axisymmetric Drop Shape Analysis-Profile (ADSA-P) applied to pendant drop tensiometry. For single component adsorption, isotherms were measured at temperatures of 285.2K, 291.2 K, 297.2 K, 298.2 K, 303.2 K, and 315.2 K, for vapor-phase solute pressures ranging from zero to near/at saturated vapor pressure. For binary solute experiments, three intermediate constant vapor-phase mole ratio isotherms were developed for each solute pair (i.e., benzene and each of the five methyl-substituted benzenes) at temperatures of 285.2 K, 291.2 K, 298.2 K. Results for single component adsorption studies indicate that for a given vapor-phase solute pressure, interface-phase solute activity increases with molecular size (mass) among the benzene homologues. Similarly, compounds are more strongly adsorbed at the vapor/water interface as the system temperature decreases. Ideal standard free energy, enthalpy, and entropy changes of adsorption, calculated from limiting isotherm data, suggest specific solute-water interactions and a perturbation of the interface-phase water structure on adsorption. Further analysis of binary solute isotherms indicates that interface-mixing is well described by a two-dimensional application of Raoult's law, implying ideal interface-phase solute-solute interactions. Consideration of the twodimensional second virial coefficients suggests that interface-phase solute molecules engage in attractive interactions, with greater interactions for larger molecular sizes.

M. Tech. Chemical Engineering. / Evaluates the use of modified eccalite as an adsorbent for the efficient removal of vanadium from industrial wastewater. The specific objectives of the study are: i. To determine whether modification of eccalite with a surfactant such as (hexadecyltrimethylammonium bromide HDTMA-Br, CTAB) will gives an optimal performance in vanadium removal from industrial wastewater; ii. To conduct batch adsorption experiments for modified eccalite for the determination of equilibrium adsorption capacity, kinetics, and thermodynamic parameters; iii. To perform column/dynamic adsorption experiments for modified eccalite in order to determine the dynamic adsorption capacity and breakthrough profiles. iv. Fit the experimental data to existing mathematical model describing the sorption process of vanadium removal from wastewater.

No description available.

No description available.