Journal of Applied Polymer Science, Vol.57, No.3, 371-384, 1995
Modeling of Transfer Phenomena on Heterogeneous Ziegler Catalysts - Differences Between Theory and Experiment in Olefin Polymerization (an Introduction)
This article begins by briefly reviewing the more important contributions to the area of modeling heat and mass transfer, and particle growth during the polymerization of olefins on Ziegler-Natta catalysts. It is shown that these models are capable of identifying the critical areas involved in heat and mass transfer, and of modeling polymerizations where the observed activity is less than approximately 5,000 g of polymer per gram of catalyst per hour (g/g/h). However, it is not possible to use these models "as-is" to model more modern catalysts whose activity levels can surpass the 50,000 g/g/h mark because they predict prohibitively large concentration gradients inside the growing particles during slurry polymerizations, and temperature gradients outside the particles during polymerization in the gas phase. An analysis of the mass and heat transfer Peclet numbers (Pe) reveals that certain simplifying assumptions may not always be valid. Pe values in the transition range suggest that convection inside the particles during polymerization in the liquid phase may help to explain why observed mass transfer rates are higher than the predicted rates. In an opposite vein, a Pe analysis shows that conductive heat transfer may play an important role at length scales characteristic of those in the early stages of polymerization. A new mechanism for heat transfer at reduced length scales is proposed.
Keywords:MASS-TRANSFER;PROPYLENE POLYMERIZATION;GAS-PHASE;HEAT;FRAGMENTATION;ETHYLENE;MORPHOLOGY;PARTICLES;REACTORS;BEHAVIOR