Catalytic synthesis of distillate-range ethers and olefins from ethanol through Guerbet coupling and etherification

Eagan, Nathaniel M.; Moore, Benjamin M.; McClelland, Daniel J.; Wittrig, Ashley M.; Canales, Emmanuel; Lanci, Michael P.; Huber, George W.

doi:10.1039/c9gc01290g

Cited by 41 publications

(56 citation statements)

References 75 publications

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“…There have been many studies to achieve better IC engines [1][2][3][4], and using biofuels as an alternative opens an opportunity for reducing emissions [5]. Among various biofuels, low-net carbon emitting ethers in the diesel boiling range can be produced from biomass by various pathways [6][7][8]. They have favorable properties for use in engines, potentially enhancing performance and lowering tailpipe emissions [9].…”

Section: Main Textmentioning

confidence: 99%

Bioderived ether design for low emission and high reactivity transport fuels

Cho

Kim

Etz

et al. 2021

Preprint

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Bioderived ethers have recently drawn attention as a response to increasing demands on clean alternative fuels. A theory-experiment combined approach was introduced for the five ether molecules representing linear, branched, and cyclic ethers to derive rational design principles for low-emission and high-reactivity ethers. Flow reactor experiments and quantum-mechanical calculations were performed at high (750–1100K) and low temperature (400–700K) regimes to investigate the structural effects on their sooting tendency and reactivity, respectively. At a high-temperature regime, ethers’ high sooting tendency is related to increased C3 and C4 hydrocarbon formation compared to C1 and C2 products from oxidation reactions. On the other hand, the reactivity at the low-temperature regime is determined by the activation energies of reaction steps until ketohydroperoxide formation. These studies found that ethers’ sooting tendency and reactivity are relevant to two structural factors: the carbon type (primary to quaternary) and the relative position of ether oxygen atoms to carbon atoms. These factors were utilized to build a multivariate model to predict the cetane number (CN) and yield sooting index (YSI) of 50 different ethers. The model suggests building blocks with specific carbon types that maximize CN and minimize YSI, leading to the design principles of ethers toward low emissions and high reactivity fuels for transport applications. Ethers with a high CN and low YSI were then proposed using the developed model, and through experimental measurements, it was proved that they are promising biodiesel candidates.

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Section: Main Textmentioning

confidence: 99%

Bioderived ether design for low emission and high reactivity transport fuels

Cho

Kim

Etz

et al. 2021

Preprint

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“…Results from fuel property screening enabled the downselection to a promising ether diesel bioblendstock candidate. Building on previous work that has recognized the potential merit of bioderived ethers (36,37), the target compound was synthesized to validate the pathway and compare fuel property measurements against predictions. Continuous solvent-free process conditions were developed to enable liter-scale production, and catalyst design was advanced to improve thermal stability and ether productivity.…”

Section: Synthesis and Scaleupmentioning

confidence: 99%

Performance-advantaged ether diesel bioblendstock production by a priori design

Huq

Huo

Hafenstine

et al. 2019

Proc. Natl. Acad. Sci. U.S.A.

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Lignocellulosic biomass offers a renewable carbon source which can be anaerobically digested to produce short-chain carboxylic acids. Here, we assess fuel properties of oxygenates accessible from catalytic upgrading of these acids a priori for their potential to serve as diesel bioblendstocks. Ethers derived from C2and C4carboxylic acids are identified as advantaged fuel candidates with significantly improved ignition quality (>56% cetane number increase) and reduced sooting (>86% yield sooting index reduction) when compared to commercial petrodiesel. The prescreening process informed conversion pathway selection toward a C11branched ether, 4-butoxyheptane, which showed promise for fuel performance and health- and safety-related attributes. A continuous, solvent-free production process was then developed using metal oxide acidic catalysts to provide improved thermal stability, water tolerance, and yields. Liter-scale production of 4-butoxyheptane enabled fuel property testing to confirm predicted fuel properties, while incorporation into petrodiesel at 20 vol % demonstrated 10% improvement in ignition quality and 20% reduction in intrinsic sooting tendency. Storage stability of the pure bioblendstock and 20 vol % blend was confirmed with a common fuel antioxidant, as was compatibility with elastomeric components within existing engine and fueling infrastructure. Technoeconomic analysis of the conversion process identified major cost drivers to guide further research and development. Life-cycle analysis determined the potential to reduce greenhouse gas emissions by 50 to 271% relative to petrodiesel, depending on treatment of coproducts.

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“…[ 1e , 1g , 1h , 9 ] The main drawback of this methodology is again its reduced applicability, as it is almost limited to primary alcohols to avoid alcohol dehydration to olefin and subsequent alcohol‐to‐olefin hydroaddition, olefin hydration, and/or oligomerization. [1g] Although some efforts have been made to design acid catalysts able to control selectivity towards asymmetrical ethers through this protocol,[ 9d , 9e ] in general it is still only practical for obtaining symmetrical ethers. [ 1e , 1g ]…”

Section: Introductionmentioning

confidence: 99%

Catalytic Reductive Alcohol Etherifications with Carbonyl‐Based Compounds or CO₂ and Related Transformations for the Synthesis of Ether Derivatives

et al. 2021

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Ether derivatives have myriad applications in several areas of chemical industry and academia. Hence, the development of more effective and sustainable protocols for their production is highly desired. Among the different methodologies reported for ether synthesis, catalytic reductive alcohol etherifications with carbonyl‐based moieties (aldehydes/ketones and carboxylic acid derivatives) have emerged in the last years as a potential tool. These processes constitute appealing routes for the selective production of both symmetrical and asymmetrical ethers (including O‐heterocycles) with an increased molecular complexity. Likewise, ester‐to‐ether catalytic reductions and hydrogenative alcohol etherifications with CO2 to dialkoxymethanes and other acetals, albeit in less extent, have undergone important advances, too. In this Review, an update of the recent progresses in the area of catalytic reductive alcohol etherifications using carbonyl‐based compounds and CO2 have been described with a special focus on organic synthetic applications and catalyst design. Complementarily, recent progress made in catalytic acetal/ketal‐to‐ether or ester‐to‐ether reductions and other related transformations have been also summarized.

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Catalytic synthesis of distillate-range ethers and olefins from ethanol through Guerbet coupling and etherification

Abstract: Ethanol can be converted to heavy diesel ethers and jet fuel precursor olefins through sequential Guerbet coupling and dehydration.

Cited by 41 publications

References 75 publications

Bioderived ether design for low emission and high reactivity transport fuels

Bioderived ether design for low emission and high reactivity transport fuels

Performance-advantaged ether diesel bioblendstock production by a priori design

Catalytic Reductive Alcohol Etherifications with Carbonyl‐Based Compounds or CO₂ and Related Transformations for the Synthesis of Ether Derivatives

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Catalytic synthesis of distillate-range ethers and olefins from ethanol through Guerbet coupling and etherification

Abstract: Ethanol can be converted to heavy diesel ethers and jet fuel precursor olefins through sequential Guerbet coupling and dehydration.

Cited by 41 publications

References 75 publications

Bioderived ether design for low emission and high reactivity transport fuels

Bioderived ether design for low emission and high reactivity transport fuels

Performance-advantaged ether diesel bioblendstock production by a priori design

Catalytic Reductive Alcohol Etherifications with Carbonyl‐Based Compounds or CO2 and Related Transformations for the Synthesis of Ether Derivatives

Contact Info

Product

Resources

About

Catalytic Reductive Alcohol Etherifications with Carbonyl‐Based Compounds or CO₂ and Related Transformations for the Synthesis of Ether Derivatives