With mounting concerns over climate change, the utilisation or conversion of carbon dioxide into sustainable, synthetic hydrocarbons fuels, most notably for transportation purposes, continues to attract worldwide interest. This is particularly true in the search for sustainable or renewable aviation fuels. These offer considerable potential since, instead of consuming fossil crude oil, the fuels are produced from carbon dioxide using sustainable renewable hydrogen and energy. We report here a synthetic protocol to the fixation of carbon dioxide by converting it directly into aviation jet fuel using novel, inexpensive iron-based catalysts. We prepare the Fe-Mn-K catalyst by the so-called Organic Combustion Method, and the catalyst shows a carbon dioxide conversion through hydrogenation to hydrocarbons in the aviation jet fuel range of 38.2%, with a yield of 17.2%, and a selectivity of 47.8%, and with an attendant low carbon monoxide (5.6%) and methane selectivity (10.4%). The conversion reaction also produces light olefins ethylene, propylene, and butenes, totalling a yield of 8.7%, which are important raw materials for the petrochemical industry and are presently also only obtained from fossil crude oil. As this carbon dioxide is extracted from air, and re-emitted from jet fuels when combusted in flight, the overall effect is a carbon-neutral fuel. This contrasts with jet fuels produced from hydrocarbon fossil sources where the combustion process unlocks the fossil carbon and places it into the atmosphere, in longevity, as aerial carbon - carbon dioxide.

/pdf/transforming-carbon-dioxide-into-jet-fuel-using-an-organic-1dsmmf21y7.pdf

Transforming carbon dioxide into jet fuel using an organic combustion-synthesized Fe-Mn-K catalyst

One of the main initiatives for fighting climate change is to use carbon dioxide as a resource instead of waste. In this respect, thermocatalytic carbon dioxide hydrogenation to high-added-value chemicals is a promising process. Among the products of this reaction (alcohols, alkanes, olefins, or aromatics), light olefins are interesting because they are building blocks for making polymers, as well as other important chemicals. Olefins are mainly produced from fossil fuel sources, but the increasing demand of plastics boosts the need to develop more sustainable synthetic routes. This review gives a critical overview of the most recent achievements in direct carbon dioxide hydrogenation to light olefins, which can take place through two competitive routes: the modified Fischer-Tropsch synthesis and methanol-mediated synthesis. Both routes are compared in terms of catalyst development, reaction performance, and reaction mechanisms. Furthermore, practical aspects of the commercialization of this reaction, such as renewable hydrogen production and carbon dioxide capture, compression, and transport, are discussed. It is concluded that, to date, the catalysts used in the carbon dioxide hydrogenation reaction give a wide product distribution, which reduces the specific selectivity to lower olefins. More efforts are needed to reach better control of the C/H surface ratio and interactions within the functionalities of the catalyst, as well as understanding the reaction mechanism and avoiding deactivation. Renewable H2 production and carbon dioxide capture and transport technologies are being developed, although they are currently still too expensive for industrial application.

/pdf/a-critical-look-at-direct-catalytic-hydrogenation-of-carbon-3zeyyrrots.pdf

A Critical Look at Direct Catalytic Hydrogenation of Carbon Dioxide to Olefins

The continuous rise in the quantity of CO2 emissions in the atmosphere and the threat it poses to humankind and its environment are issues of great concern to everyone in the world. Also, the declining fossil fuel reserves are an issue of worry considering the increasing demand for energy globally. Therefore, the conversion of CO2 into fuels is a promising and convenient way to minimize global warming caused by the growing concentration of CO2 in the atmosphere and meet the world's high energy demand. The conversion of CO2 into fuels is achieved via various chemical conversion and biological conversion methods. The progress and development made so far in producing environmentally friendly alternative fuels from the conversion of CO2 boost the industrialization of sustainable fuel production. However, the conversion of CO2 into fuels via chemical conversion and biological conversion methods are plagued with some challenges. This article focused on the recent advances, problems, and prospects for future research regarding the conversion of CO2 into fuels. 

Conversion of carbon dioxide into fuels—A review

Recent advances in application of iron-based catalysts for CO hydrogenation to value-added hydrocarbons

Entropy generation rate minimization for hydrocarbon synthesis reactor from carbon dioxide and hydrogen

The thermodynamics of jet fuel range alkane synthesis from carbon dioxide and hydrogen has been investigated. The hydrocarbon synthesis process is divided into three elementary steps, including light olefins formation (C2-C6) from hydrogenation of CO2, α-olefins (C7-C16) synthesis from oligomerization of light olefins, and hydrogenation of α-olefins (C8-C16) to straight-chain paraffin (C8-C16). The enthalpy changes and Gibbs free energy changes of the relevant reactions were calculated, and the equilibrium products distribution was computed based on the Gibbs free energy minimization method. The calculation results show that lower temperature (below 673.15 K), higher pressure (3 MPa), higher molar ratio of H2 to CO2 (3:1-4:1), and introducing a small amount of N2 in the reactants are favorable for the hydrogenation of CO2; lower temperature (below 500 K), higher pressure (2-3 MPa), addition of N2 is favorable for the oligomerization of light olefins; and lower temperature (below 700 K), higher pressure (2-3 MPa), and addition of N2 is favorable for the hydrogenation of α-olefins. The overall positive effect of introducing N2 results from its heat dilution of the process. © 2017 Society of Chemical Industry and John Wiley & Sons, Ltd.

Thermodynamic study of hydrocarbon synthesis from carbon dioxide and hydrogen

Cyclopentanol is a very important chemical intermediate, which has been widely used in the chemical industry, and could be prepared from cyclopentene by two steps: an initial addition-esterification reaction of cyclopentene with acetic acid and the subsequent transesterification reaction with methanol. However, so far, no direct theoretical or experimental work has been reported on this process. In this work, we have carried out the thermodynamic calculation of the indirect process and also validated the thermodynamic prediction through experimental work. The liquid heat capacities of cyclopentanol and cyclopentyl acetate were estimated using the Ruzicka–Domalski group contribution method, the standard enthalpy of formation and standard entropy of gaseous cyclopentyl acetate by the Yoneda group contribution method, the standard vaporization enthalpy of cyclopentyl acetate by the Ducros group contribution method. The enthalpy changes, free energy changes, equilibrium constant and equilibrium conversion of the addition-esterification and transesterification reactions were calculated according to the principles of chemical thermodynamics in the temperature range from 273.15 to 373.15 K. The results showed that both the addition-esterification reaction and transesterification reaction were exothermic, the free energy changes increased with a rise on temperature, which indicated that low temperature was favorable for the reactions in the temperature range from 273.15 to 373.15 K. The optimal addition-esterification reaction conditions were a temperature range from 333.15 to 353.15 K, molar ratios of acetic acid to cyclopentene in the range from 2:1 to 3:1. For the transesterification reaction, the ideal temperature ranges from 323.15 to 343.15 K, with a molar ratio of methanol to cyclopentyl acetate in the range from 3:1 to 4:1. These thermodynamic calculation results for the addition-esterification reaction of cyclopentene and acetic acid experiments results are in good agreement with the experimental results.

/pdf/thermodynamic-analysis-of-synthesis-of-cyclopentanol-from-42s2i87xwd.pdf

Thermodynamic analysis of synthesis of cyclopentanol from cyclopentene and comparison with experimental data

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Thermodynamic study of hydrocarbon synthesis from carbon dioxide and hydrogen

Thermodynamic analysis of synthesis of cyclopentanol from cyclopentene and comparison with experimental data