Olefin production via reactive distillation based Olefin metathesis

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2010-12

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Abstract

Reactive distillation is a combination of a traditional multi-stage distillation column with a chemical reaction. The primary benefits of a reactive distillation process are reduced capital costs for equipment and energy in addition to enhanced conversion for equilibrium-limited reactions. One such equilibrium-limited reaction is an olefin metathesis. Olefin metathesis is a catalyzed reaction that breaks the double bond in olefins and rearranges the alkene fragments into new olefinic products. A comprehensive investigation of a reactive distillation based olefin metathesis and supporting experimentation is documented here. A small pilot plant study was performed for pilot scale performance comparison. Bench reactor experimentation was conducted for the purposes of learning detailed information on specific metathesis reactions. Lastly, a process simulation study was completed for comparison in performance with the small pilot plant process. The small pilot plant study involved the design, construction, testing, operation, and optimization of a reactive distillation column. Continuous operation campaigns at two different hydraulic capacities within the reactive zone were performed and their performances were compared. A higher hydraulic capacity proved to be more efficient and more selective for the conversion of medium molecular weight olefins into both lighter and heavier olefinic products. Bench reactor experiments were designed with the intent of investigating specific alpha olefin metathesis reactions and obtaining conversions, selectivities, and yield structures for future simulation work. However, under conditions similar to that within the small pilot plant process, there existed a high frequency of secondary double bond isomerization (possibly due to an isomerization activity for alumina). There was also an observed dependence on temperature for both the primary metathesis and secondary isomerization reactions. A process simulation representative of the small pilot plant process was constructed in AspenPlus. Using a simplified reaction network based on assumptions and analysis of the reactive zone, its performance was compared with that of the small pilot plant process. The simulation performance tended to underpredict overhead compositions, but accurately simulated the bottoms product composition. Because reactive distillation has not been used with a heavy olefin metathesis reaction, this dissertation demonstrates the uniqueness and effectiveness of a reactive distillation based heavy olefin metathesis.

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