Urea hydrolysis by urease immobilized onto ion exchange resins in a fixed-bed reactor has been studied. A modified Michaelis-Menten rate expression is used to describe the pH-dependent, substrate- and product-inhibited kinetics. Ionic equilibria of product and buffer species are included to account for pH changes generated by reaction. An isothermal, heterogeneous plug-flow reactor model has been developed. An effectiveness factor is used to describe the reaction-diffusion process within the particle phase. The procedure for covalent immobilization of urease onto macroporous cation exchangers is described. Urea conversion data are used to estimate kinetic parameters by a simplex optimization method. The best-fitted parameters are then used to predict the outlet conversions and pH values for systems with various inlet pH values, inlet urea and ammonia concentrations, buffers, particle sizes, and spacetimes. Very good agreement is obtained between experimental data and model predictions. This immobilized urease system exhibits quite different kinetic behavior from soluble urease because the pH near the enzyme active sites is different from that of the pore fluid. This effect results in a shift of the optimal pH value of the V(max) (pH) curve from 6.6 (soluble urease) to ca. 7.6 in dialysate solution, and ca. pH 8.0 in 20mM phosphate buffer. The reactor model is especially useful for estimating intrinsic kinetic parameters of immobilized enzymes and for designing urea removal columns.
The sorption characteristics of Cr(VI) and Cu(II) by ethylenediamine modified rice hull from single and binary metal ion solutions were evaluated under various experimental conditions. Optimal Cr(VI) and Cu(II) removal from single metal ion solutions occurred at pH 2.0 and 5.5, respectively. Simultaneous removal of Cr(VI) and Cu(II) occurred at pH greater than 3.0. The sorption kinetics of Cr(VI) and Cu(II) from single and binary metal ion solutions were studied with reference to metal concentration, agitation rate and particle size. Sorption of Cr(VI) was more rapid than Cu(II). The kinetics of metal ion sorption fitted a pseudo-second order expression. The variation in the initial uptake rates was very small at an agitation rate beyond 150 rpm and sorption was generally independent of particle size. Equilibrium sorption data could be fitted into the Langmuir isotherm equation. Maximum sorption capacities of ethylenediamine modified rice hull for Cr(VI) at pH 2 and Cu(II) at pH 4 in single metal solutions were 0.45 and 0.06 mmol g(-1), respectively. This corresponds to an enhancement factor of 2.6 and 3 fold for Cr(VI) and Cu(II), respectively, compared to natural rice hull. A synergistic effect was observed for sorption of these ions in binary metal solutions.
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