DEVELOPMENT OF A CONCEPTUAL MODEL AND PARAMETERIZATION OF A MATHEMATICAL MODEL FOR SEDIMENT PHOSPHORUS DIAGENESIS, SORPTION AND RELEASE FROM ONONDAGA LAKE SYRACUSE, NEW YORK

Eutrophication is a persistent problem in many fresh water lakes. Delay in lake recovery following reductions in external loading of phosphorus, the limiting nutrient in fresh water ecosystems, is often observed. Models have been created to assist with lake remediation efforts, however, the application of management tools to sediment diagenesis is often neglected due to conceptual and mathematical complexity. SED2K (Chapra et al. 2012) is proposed as a "middle way", offering engineering rigor while being accessible to users. An objective of this research is to further support the development and application SED2K for sediment phosphorus diagenesis and release to the water column of Onondaga Lake. Application of SED2K has been made to eutrophic Lake Alice in Minnesota. The more homogenous sediment characteristics of Lake Alice, compared with the industrially polluted sediment layers of Onondaga Lake, allowed for an invariant rate coefficient to be applied to describe first order decay kinetics of phosphorus. When a similar approach was attempted on Onondaga Lake an invariant rate coefficient failed to simulate the sediment phosphorus profile. Therefore, labile P was accounted for by progressive preservation after burial and a rate coefficient which gradual decreased with depth was applied. In this study, profile sediment samples were chemically extracted into five operationally-defined fractions: CaCO3-P, Fe/Al-P, Biogenic-P, Ca Mineral-P and Residual-P. Chemical fractionation data, from this study, showed that preservation is not the only mechanism by which phosphorus may be maintained in a non-reactive state in the profile. Sorption has been shown to contribute substantially to P burial within the profile. A new kinetic approach involving partitioning of P into process based fractions is applied here. Results from this approach indicate that labile P (Ca Mineral and Organic P) is contributing to internal P loading to Onondaga Lake, through diagenesis and diffusion to the water column, while the sorbed P fraction (Fe/Al-P and CaCO3-P) is remaining consistent. Sediment profile concentrations of labile and total phosphorus at time of deposition were also modeled and compared with current labile and total phosphorus, to quantify the extent to which remaining phosphorus which will continue to contribute to internal P loading and influence the trophic status of Onondaga Lake. Results presented here also allowed for estimation of the depth of the active sediment layer and the attendant response time as well as the sediment burden of labile P and associated efflux.

DYNAMICS AND CONTROL OF REACTIVE DISTILLATION PROCESS FOR MONOMER SYNTHESIS OF POLYCARBONATE PLANTS

Polycarbonate (PC) is an important engineering thermoplastic that is currently produced in large industrial scale using bisphenol A and monomers such as phosgene. Since phosgene is highly toxic, a non-phosgene approach using diphenyl carbonate (DPC) as an alternative monomer, as developed by Asahi Corporation of Japan, is a significantly more environmentally friendly alternative. Other advantages include the use of CO2 instead of CO as raw material and the elimination of major waste water production. However, for the production of DPC to be economically viable, reactive-distillation units are needed to obtain the necessary yields by shifting the reaction-equilibrium to the desired products and separating the products at the point where the equilibrium reaction occurs. In the field of chemical reaction engineering, there are many reactions that are suffering from the low equilibrium constant. The main goal of this research is to determine the optimal process needed to shift the reactions by using appropriate control strategies of the reactive distillation system. An extensive dynamic mathematical model has been developed to help us investigate different control and processing strategies of the reactive distillation units to increase the production of DPC. The high-fidelity dynamic models include extensive thermodynamic and reaction-kinetics models while incorporating the necessary mass and energy balance of the various stages of the reactive distillation units. The study presented in this document shows the possibility of producing DPC via one reactive distillation instead of the conventional two-column, with a production rate of 16.75 tons/h corresponding to start reactants materials of 74.69 tons/h of Phenol and 35.75 tons/h of Dimethyl Carbonate. This represents a threefold increase over the projected production rate given in the literature based on a two-column configuration. In addition, the purity of the DPC produced could reach levels as high as 99.5% with the effective use of controls. These studies are based on simulation done using high-fidelity dynamic models.