Insights into the Chemistry of the Homogeneous Thermal Oligomerization of Ethylene to Liquid-Fuel-Range Hydrocarbons

• Published in: Industrial & engineering chemistry research 2023-02, Vol.62 (5), p.2202-2216
• Main Authors: Conrad, Matthew A., Shaw, Alexander, Marsden, Grant, Broadbelt, Linda J., Miller, Jeffrey T.
• Format: Article
• Language: English
• Subjects: Kinetics, Catalysis, and Reaction Engineering
• ISSN: 0888-5885; 1520-5045
• DOI: 10.1021/acs.iecr.2c02172

Thermal, noncatalytic conversion of light olefins (C2 =–C4 =) was originally utilized in the production of motor fuels at several U.S. refineries in the 1920s to 1930s. However, the resulting fuels had relatively low octane number and required harsh operating conditions (T > 450 °C, P > 50 bar), ultimately leading to its succession by solid acid catalytic processes. Despite the early utilization of the thermal reaction, relatively little is known about the reaction products, kinetics, and initiation pathway under liquid-producing conditions. In this study, thermal ethylene oligomerization was investigated near industrial operating conditions, i.e, at temperatures between 300 and 500 °C and ethylene pressures from 1.5 to 43.5 bar. Nonoligomer products such as propylene and/or higher odd carbon products were significant at all reaction temperatures, pressures, and reaction extents. Methane and ethane were minor products (