To Cyclopropanate or Not To Cyclopropanate? A Look at the Effect of Cyclopropanation on the Performance of Biofuels

Abstract

The cyclopropanated derivatives of three diesel-compatible biofuels;limonene, turpentine, and canola oil methyl ester;were prepared. Their heats of combustion were both calculated using theoretical methods and measured experimentally, and it was found that for all three compounds the specific energy (in kJ/g) was similar to that of the starting materials, while the energy density (in kJ/mL) was 3-4% higher, which is slightly lower than that for the predicted values. For canola oil methyl ester, the effect of cyclopropanation on the accelerated oxidation stability was also studied, and similar trends in viscosity were observed for both the starting material and the cyclopropanated product, while no degradation of the cyclopropane groups was observed and only residual alkene groups had shown any sign of reaction, hinting that the increase in the viscosity observed with unsaturated fatty esters upon oxidation may not be directly related to autoxidation of the fatty acid chains.

Novel Strained Alicyclic Hydrocarbons Based on 5-Methylene-2-norbornene

“…Modern aerospace vehicles have a limited fuel tank capacity, fly long distances without refueling, and operate at high altitudes at extremely low temperatures. The modernized flying vehicles have accordingly changed the requirements for fuel properties, which have a key influence on an aircraft's flight performance [1][2][3][4][5][6][7]. The most important fuel properties are heating value, density, low freezing point, and viscosity.…”

Engineering cyanobacteria for the production of a cyclic hydrocarbon fuel from CO2and H2O

“…Limonene is an attractive choice for biofuel production, given its similar energy density, boiling point, and self-ignition temperature to petrodiesel. 10 The production of limonene from CO 2 , mineralized water, and light using engineered cyanobacteria offers a promising way to produce biofuels while minimizing the human carbon footprint on the environment. To our knowledge, this is the first report of alkene-biofuel production from a filamentous, nitrogen-fixing cyanobacterium.…”

“…9 Due to its cyclic structure, this compound has the potential to be further functionalized through cyclopropanation, in order to increase its energetic content and enhance its value as a fuel. 10 Limonene has also been extensively researched as a possible therapeutic agent, due to its anti-inflammatory and anti-carcinogenic properties. [11][12][13] Global limonene production is far behind the rising demands for biofuels.…”

Thermal cyclodimerization of isoprene for the production of high-performance sustainable aviation fuel

“…21 The densities and volumetric NHOCs of terpenes can be further enhanced through cyclopropanation reactions. [22][23][24][25] Isoprene is a compelling substrate for the preparation of sustainable jet fuel blendstocks. It can be directly produced from biomass sugars via fermentation, 26 by dehydration of biosynthetic 3-methyl-3-buten-1-ol, 27 or from other bio-based substrates including mevalonolactone 28,29 and mesaconic/itaconic acid.…”