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The reduced availability of propylene and C4 products from steam crackers continues to provoke on-purpose technologies for light olefins such that almost 30% of propylene in 2025 is predicted to be supplied from unconventional sources. Furthermore, the recent discoveries of natural gas reservoirs have urged interest in the conversion of surplus alkanes and alkenes, especially ethane and ethylene. The direct conversion of ethylene to propylene or a combination of value-added chemicals, including butylenes and oligomers in the range of gasoline and diesel fuel, provides the capability of responding to the fluctuations in the balance between supply and demand of the main petrochemicals. A comprehensive review of heterogeneous catalysts for the gas-phase conversion pathways is presented here in terms of catalytic performances (ethylene conversion and product selectivities), productivities, lifetimes, active sites, physicochemical properties, mechanisms, influence of operating conditions, deactivation and some unresolved/less-advanced aspects of the field. The addressed catalysts cover both zeolitic materials and transition metals, such as tungsten, molybdenum, rhenium and nickel. Efforts in both experimental and theoretical studies are taken into account. Aside from the potential fields of progress, the review reveals very promising performances for the emerging technologies to produce propylene, a mixture of propylene and butenes, or a liquid fuel from ethylene.

Heterogeneous catalysts for gas-phase conversion of ethylene to higher olefins