Propene oligomerization over steam dealuminated and boron and phospherous modified ZSM-5
Doctoral Thesis
1991
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University of Cape Town
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Abstract
ZSM-5 was modified with boron and phosphorus compounds in an attempt to improve the selectivity of the catalyst with respect to the linearity of the liquid product of propene oligomerization. Boron was incorporated into the zeolite framework by inclusion in the synthesis gel. Boralite catalysts made in this way and containing very low Al contents had only weak acidity as was evident from only one, low temperature NH3 desorption peak at ca. 190 °C. These catalysts showed poor propene oligomerization activity as a result of the weak acidity arising from the weak B(OH)Si site and reduced catalyst free volume. The latter was ascribed to occluded B₂O₃ species. Activity of these catalysts was proportional to Al, rather than B content. No appreciable selectivity changes were observed for any of these catalysts. In an attempt to enhance the acidity and hence the activity of the boralite catalysts, mild fluorination treatments were carried out. A boralite catalyst containing 550 ppm Al and 1.2 wt% boron was treated with mild HF at room temperature. The activity of the catalyst was significantly reduced. The activity of the catalyst was essentially restored to its former level upon subsequent NH₄F treatment. The catalyst then contained 120 ppm Al and 0.8 wt% boron. Although some activity enhancement was achieved through mild fluorination, the catalyst utilization values (CUV) remained an order of magnitude lower than the CUV of unmodified ZSM-5. Catalytic activity remained proportional to trace Al content.
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Bibliography: pages 203-210.
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Reference:
Andersen, B. 1991. Propene oligomerization over steam dealuminated and boron and phospherous modified ZSM-5. University of Cape Town.