(582h) D-Optimal Estimation of Polyolefin Polymerization Rate Constants Using Experimental Residence Time Studies in Industrial Pilot Plant Equipment

Estimation of polymerization rate constants is industrially important in polymerization reactor design, reactor control, and evaluation of the productivity and product capabilities of new catalyst systems being evaluated for scale up and commercialization. Of particularly fundamental importance are the polymerization and catalyst deactivation rate constants as these parameters dictate how a given catalyst system will behave in a particular reactor size and configuration. Here we use pilot scale continuous stirred reactors to investigate the kinetics of solution ethylene polymerization. A method is developed to allow the estimation of both the apparent propagation rate constant and first-order catalyst deactivation rate constant through carefully conducted residence-time experiments. Because industrial experimentation is expensive, it is critical that the correct experiments be conducted and that the number of experiments be minimized. We show how D-optimal experimental design criteria is used to both design/select the pilot scale equipment and determine the appropriate experimental conditions.