Abstract
Effect of H2 amount on the activity and selectivity of Chevron–Phillips trimerization system, i.e., chromium(III) tris(2-ethylhexanoate)/2,5-dimethylpyrrole/triethylaluminum (TEA)/tetrachloroethane (TCE), was examined. In this regard, in addition to catalytic ingredients and ethylene monomer, 2.5 and 5 bar H2 were utilized in the oligomerization reactor and the reaction results were compared with those without H2. Results showed that addition of hydrogen has a remarkable effect on polymer formation and catalyst activity so that 147% decrease in polymer formation and 38% increase in activity were observed upon addition of 5 bar H2. However, its effect on 1-hexene selectivity was not pronounced. Then, molecular modeling with DFT method was employed to simulate oligomerization process in molecular level. Energy results revealed that formation of 1-hexene has less energy barrier than the formation of 1-butene and 1-octene which confirms higher selectivity of Chevron–Phillips system toward 1-hexene formation. Furthermore, interaction of hydrogen with catalytic active center was studied via hydrogenolysis of metalacycles. Energy results revealed that it is energetically a facile process so that the bigger the circle, the easier hydrogenolysis.
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The authors thank MOLNAC (www.molnac.unisa.it) for its computer facilities and Iran Polymer and Petrochemical Institute (IPPI) for financial support under Grant number of 43791105.
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Cartesian coordinates of all the species discussed in the text are available free of charge at the journal webpage. Below is the link to the electronic supplementary material.
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Bahri-Laleh, N., Karimi, M., Kalantari, Z. et al. H2 effect in Chevron–Phillips ethylene trimerization catalytic system: an experimental and theoretical investigation. Polym. Bull. 75, 3555–3565 (2018). https://doi.org/10.1007/s00289-017-2228-3
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DOI: https://doi.org/10.1007/s00289-017-2228-3