Chemistries and processes for the conversion of ethanol into middle-distillate fuels


Ethanol is presently the most common liquid fuel derived from biomass. One way of meeting the growing demand for heavier middle-distillate fuels — diesel and jet fuels comprising hydrocarbons of typically 8–22 carbon atoms — is to derive these from ethanol. This Review describes the chemistries and processes involved in the conversion of ethanol into diesel and jet fuel drop-in replacements and blendstocks. This conversion of ethanol relies on reactions including dehydration (to olefins), dehydrogenation (to aldehydes), hydrogenation (of C=C and C=O bonds), acid-catalysed olefin oligomerization, metal-catalysed olefin oligomerization, aldolization and ketonization. We discuss the thermodynamics, kinetics, process integration and catalyst development of different approaches. Some routes, particularly those based on olefin oligomerization, have been realized on the pilot scale. Other routes are currently in laboratory stages. This Review provides a framework for understanding how to convert ethanol into distillate-range molecules and the key research problems to be addressed.

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Fig. 1: Many pathways exist to convert EtOH into middle-distillate fuels.
Fig. 2: The possible elimination mechanisms of EtOH dehydration.
Fig. 3: Carbenium chemistries involved in olefin conversion over solid acids
Fig. 4: Thermodynamics of olefin oligomerization and aromatization.
Fig. 5: The hydrocarbon pool mechanism for EtOH transformation
Fig. 6: Block flow diagrams for acid-catalysed conversion of EtOH through C2H4 oligomerization.
Fig. 7: The generalized Cossee–Arlman mechanism for C2H4 oligomerization.
Fig. 8: Computed Schulz–Flory distribution of olefins from C2H4 oligomerization.
Fig. 9: The generalized metallacycle mechanism for C2H4 oligomerization
Fig. 10: Guerbet condensation of primary alcohols affords an alcohol product
Fig. 11: Contact time plots and block flow diagram for the Guerbet coupling of EtOH.
Fig. 12: The direct conversion of EtOH into olefins through an Me2CO intermediate.


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This work was supported by ExxonMobil.

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N.M.E. contributed the majority of the data research, writing and editing of the manuscript. M.D.K. additionally contributed to these areas, as well as to the discussion of content. Substantial discussion of content, reviewing and editing were contributed by J.S.B., J.A.D. and G.W.H.

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Correspondence to George W. Huber.

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Eagan, N.M., Kumbhalkar, M.D., Buchanan, J.S. et al. Chemistries and processes for the conversion of ethanol into middle-distillate fuels. Nat Rev Chem 3, 223–249 (2019).

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