Dehydrogenation and oxydehydrogenation of paraffins to olefins

Abstract

Catalytic paraffin dehydrogenation for the production of olefins has been in commercial use since the late 1930s, while catalytic paraffin oxydehydrogenation for olefin production has not yet been commercialized. However, there are some interesting recent developments worthy of further research and development. During World War II, catalytic dehydrogenation of butanes over a chromia-alumina catalyst was practiced for the production of butenes that were then dimerized to octenes and hydrogenated to octanes to yield high-octane aviation fuel. Dehydrogenation employs chromia-alumina catalysts and, more recently, platinum or modified platinum catalysts. Important aspects in dehydrogenation entail approaching equilibrium or near-equilibrium conversions while minimizing side reactions and coke formation. Commercial processes for the catalytic dehydrogenation of propane and butanes attain per-pass conversions in the range of 30–60%, while the catalytic dehydrogenation of C 10–C 14 paraffins typically operates at conversion levels of 10–20%. In the year 2000, nearly 7 million metric tons of C 3–C 4 olefins and 2 million metric tons of C 10–C 14 range olefins were produced via catalytic dehydrogenation. Oxydehydrogenation employs catalysts containing vanadium and, more recently, platinum. Oxydehydrogenation at ∼1000 °C and very short residence time over Pt and Pt-Sn catalysts can produce ethylene in higher yields than in steam cracking. However, there are a number of issues related to safety and process upsets that need to be addressed. Important objectives in oxydehydrogenation are attaining high selectivity to olefins with high conversion of paraffin and minimizing potentially dangerous mixtures of paraffin and oxidant. More recently, the use of carbon dioxide as an oxidant for ethane conversion to ethylene has been investigated as a potential way to reduce the negative impact of dangerous oxidant–paraffin mixtures and to achieve higher selectivity. While catalytic dehydrogenation reflects a relatively mature and well-established technology, oxydehydrogenation can in many respects be characterized as still being in its infancy. Oxydehydrogenation, however, offers substantial thermodynamic advantages and is an area of active research in many fronts.