Solvent-free dehydration, cyclization, and hydrogenation of linalool with a dual heterogeneous catalyst system to generate a high-performance sustainable aviation fuel

Abstract

The development of efficient catalytic methods for the synthesis of bio-based, full-performance jet fuels is critical for limiting the impacts of climate change while enabling a thriving modern society. To help address this need, here, linalool, a terpene alcohol that can be produced via fermentation of biomass sugars, was dehydrated, cyclized, and hydrogenated in a one-pot reaction under moderate reaction conditions. This sequence produced a biosynthetic fuel mixture primarily composed of 1-methyl-4-isopropylcyclohexane (p-menthane) and 2,6-dimethyloctane (DMO). The reaction was promoted by a catalyst composed of commercial Amberlyst-15, H+ form, and 10% Pd/C. Two other terpenoid substrates (1,8-cineole and 1,4-cineole) were subjected to the same conditions and excellent conversion to high purity p-menthane was observed. The fuel mixture derived from linalool exhibits a 1.7% higher gravimetric heat of combustion and 66% lower kinematic viscosity at −20 °C compared to the limits for conventional jet fuel. These properties suggest that isomerized hydrogenated linalool (IHL) can be blended with conventional jet fuel or synthetic paraffinic kerosenes to deliver high-performance sustainable aviation fuels for commercial and military applications.

Systematic Mining and Evaluation of the Sesquiterpene Skeletons as High Energy Aviation Fuel Molecules

“…[ 15 , 16 , 17 ] Similarly, linalool, a colorless liquid with a strong fragrance, has shown potential as a fuel due to its unique molecular structure. [ 18 , 19 , 20 , 21 ] Additionally, pinene's dimers exhibit comparable density and net heat of combustion to JP‐10. [ 22 , 23 ] Sesquiterpenes, like β ‐farnesene, have promising fuel properties and the potential to be blended with other sustainable aviation fuel components to improve overall fuel performance.…”

Biosynthesis Progress of High-Energy-Density Liquid Fuels Derived from Terpenes

“…Linalool, an acyclic monoterpene, is an important fragrance component of lavender, rose and other plants, which can be used to synthesize the traditional HED fuel RJ-4 [30]. Harvey et al used linalool as a raw material to obtain a mixed fuel composed of p-menthane and 2,6-dimethyloctane (DMO) through a one-pot reaction, which had a higher heating value and density than the jet fuel Jet-A [31].…”

“Metafining” of nerolidol with a Grubbs-Hoveyda catalyst to generate high-performance sustainable aviation fuels

“…8–10 This process was further supplemented with dehydration/cyclization reactions to generate additional fuel components. 11,12 Other researchers have focused on the use of unsaturated oils derived from crops like camelina 13 and Amygdalus pedunculata 14 or from microbes. 15 Ethenolysis of the oils with metathesis catalysts can efficiently break down the longer hydrocarbon chains into jet fuel range hydrocarbons.…”