A hybrid pathway to biojet fuel <i>via</i> 2,3-butanediol

Adhikari, Sushovit; Zhang, Junyan; Guo, Qianying; Unocic, Kinga A.; Tao, Ling; Li, Zhenglong

doi:10.1039/d0se00480d

Cited by 26 publications

(29 citation statements)

References 65 publications

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“…Further, growing concerns about anthropogenic climate change related to CO 2 emissions from petroleumbased operations 7,8 continuously motivate the search for new pathways to produce C 3+ olefins from renewable resources. 9,10 One such renewable feedstock is ethanol, a key C 2 platform chemical due to its commercial availability (∼29 billion gallons globally in 2019 11 ) and emerging ethanol synthesis opportunities from lignocellulosic biomass 12 and CO 2 . 13 Ethanol conversion to C 3+ olefins presents great opportunities to produce sustainable middle distillate fuels for decarbonizing the hard-to-electrify sectors, such as aviation, marine, and heavy-duty trucking.…”

Section: Introductionmentioning

confidence: 99%

“…Light olefins (C 3+ ) serve as critical building blocks for synthesizing a wide variety of commodity chemicals, polymers, and synthetic hydrocarbon fuels (e.g., gasoline, jet, and diesel). − These olefins are traditionally produced through either steam cracking or fluid catalytic cracking of naphtha, contributing to over 95%, 89%, and 95% of ethylene, propene, and butene production, respectively. , The use of shale gas has shifted ethylene production to steam cracking of light paraffins, which primarily generates ethylene with much less C 3+ olefins, , so there is a necessity for on-purpose production of C 3+ olefins. Further, growing concerns about anthropogenic climate change related to CO 2 emissions from petroleum-based operations , continuously motivate the search for new pathways to produce C 3+ olefins from renewable resources. , One such renewable feedstock is ethanol, a key C 2 platform chemical due to its commercial availability (∼29 billion gallons globally in 2019) and emerging ethanol synthesis opportunities from lignocellulosic biomass and CO 2 . Ethanol conversion to C 3+ olefins presents great opportunities to produce sustainable middle distillate fuels for decarbonizing the hard-to-electrify sectors, such as aviation, marine, and heavy-duty trucking …”

Section: Introductionmentioning

confidence: 99%

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Isolated Metal Sites in Cu–Zn–Y/Beta for Direct and Selective Butene-Rich C₃₊ Olefin Formation from Ethanol

et al. 2021

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Direct and selective production of C 3+ olefins from bioethanol remains a critical challenge and important for the production of renewable transportation fuels such as aviation biofuels. Here, we report a Cu−Zn−Y/Beta catalyst for selective ethanol conversion to butene-rich C 3+ olefins (88% selectivity at 100% ethanol conversion, 623 K), where the Cu, Zn, and Y sites are all highly dispersed. The ethanol-to-butene reaction network includes ethanol dehydrogenation, aldol condensation to crotonaldehyde, and hydrogenation to butyraldehyde, followed by further hydrogenation and dehydration reactions to form butenes. Cu sites play a critical role in promoting hydrogenation of the crotonaldehyde CC bond to form butyraldehyde in the presence of hydrogen, making this a distinctive pathway from crotyl alcohol-based ethanol-to-butadiene reaction. Reaction rate measurements in the presence of ethanol and acetaldehyde (543 K, 12 kPa ethanol, 1.2 kPa acetaldehyde, 101.9 kPa H 2 ) over monometallic Zn/ Beta and Y/Beta catalysts indicate that Y sites have higher C−C coupling rates than over Zn sites (initial C−C coupling rate, 6.1 × 10 −3 mol mol Y −1 s −1 vs 1.2 × 10 −3 mol mol Zn −1 s −1 ). Further, Lewis-acidic Y-site densities over Cu−Zn−Y/Beta with varied Y loadings are linearly correlated with the initial C−C coupling rates, suggesting that Lewis-acidic Y sites are the predominant sites that catalyze C−C coupling in Cu−Zn−Y/Beta catalysts. Control experiments show that the dealuminated Beta support is important to form higher density of Lewis-acidic Y sites in comparison with other supports such as silica, or deboronated MWW despite similar atomic dispersion of Y sites and Y−O coordination numbers over these supports, leading to more than 9 times higher C−C coupling rate per mole Y over dealuminated Beta relative to other supports. This study highlights the significance of unique combination of metal sites in contributing to the selective valorization of ethanol to C 3+ olefins, motivating for exploring multifunctional zeolite catalysts, where the presence of multiple sites with varying reactivities and functions allows for controlling the predominant molecular fluxes toward the desired products in complex reactions.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Isolated Metal Sites in Cu–Zn–Y/Beta for Direct and Selective Butene-Rich C₃₊ Olefin Formation from Ethanol

et al. 2021

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“…Efficient catalytic upgrading of renewable feedstocks into carbon-neutral transportation fuels remains critically important for combating CO 2 emissions, especially for producing long-chain (C 8+ ) hydrocarbons required for aviation and heavy-duty diesel fuels. Bioethanol is a widely produced renewable feedstock (∼86 million tons per year worldwide in 2018) that can be valorized into key short-chain (C 3 –C 6 ) olefin intermediates (e.g., propene, 1-butene, isobutene), a class of critical precursors for oligomerization into middle-distillate-range hydrocarbons and commodity chemical production . Direct conversion of ethanol to C 3+ olefins is typically accomplished over either Brønsted acid zeolites , or metal oxides − with limited olefin selectivities due to the formation of aromatics and paraffins, − ethylene, oxygenates, or other side products including CO 2 . , Therefore, a strong need remains for an approach to selective C 3+ olefin production for economically viable liquid renewable fuel generation without significant carbon losses, especially since carbon conversion efficiency is a primary cost driver for renewable fuel production …”

Section: Introductionmentioning

confidence: 99%

Selective Butene Formation in Direct Ethanol-to-C₃₊-Olefin Valorization over Zn–Y/Beta and Single-Atom Alloy Composite Catalysts Using In Situ-Generated Hydrogen

et al. 2021

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The selective production of C3+ olefins from renewable feedstocks, especially via C1 and C2 platform chemicals, is a critical challenge for obtaining economically viable low-carbon middle-distillate transportation fuels (i.e., jet and diesel). Here, we report a multifunctional catalyst system composed of Zn–Y/Beta and “single-atom” alloy (SAA) Pt–Cu/Al2O3, which selectively catalyzes ethanol-to-olefin (C3+, ETO) valorization in the absence of cofed hydrogen, forming butenes as the primary olefin products. Beta zeolites containing predominately isolated Zn and Y metal sites catalyze ethanol upgrading steps (588 K, 3.1 kPa ethanol, ambient pressure) regardless of cofed hydrogen partial pressure (0–98.3 kPa H2), forming butadiene as the primary product (60% selectivity at an 87% conversion). The Zn–Y/Beta catalyst possesses site-isolated Zn and Y Lewis acid sites (at ∼7 wt % Y) and Brønsted acidic Y sites, the latter of which have been previously uncharacterized. A secondary bed of SAA Pt–Cu/Al2O3 selectively hydrogenates butadiene to butene isomers at a consistent reaction temperature using hydrogen generated in situ from ethanol to butadiene (ETB) conversion. This unique hydrogenation reactivity at near-stoichiometric hydrogen and butadiene partial pressures is not observed over monometallic Pt or Cu catalysts, highlighting these operating conditions as a critical SAA catalyst application area for conjugated diene selective hydrogenation at high reaction temperatures (>573 K) and low H2/diene ratios (e.g., 1:1). Single-bed steady-state selective hydrogenation rates, associated apparent hydrogen and butadiene reaction orders, and density functional theory (DFT) calculations of the Horiuti–Polanyi reaction mechanisms indicate that the unique butadiene selective hydrogenation reactivity over SAA Pt–Cu/Al2O3 reflects lower hydrogen scission barriers relative to monometallic Cu surfaces and limited butene binding energies relative to monometallic Pt surfaces. DFT calculations further indicate the preferential desorption of butene isomers over SAA Pt–Cu(111) and Cu(111) surfaces, while Pt(111) surfaces favor subsequent butene hydrogenation reactions to form butane over butene desorption events. Under operating conditions without hydrogen cofeeding, this combination of Zn–Y/Beta and SAA Pt–Cu catalysts can selectively form butenes (65% butenes, 78% C3+ selectivity at 94% conversion) and avoid butane formation using only in situ-generated hydrogen, avoiding costly hydrogen cofeeding requirements that hinder many renewable energy processes.

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“…5−7 2,3-BDO also has value as an initial biofeedstock for fuel applications, with recent work demonstrating a process pathway to produce sustainable aviation fuels by converting 2,3-BDO to C 3+ olefins that are subsequently oligomerized to form jet-range hydrocarbons. 8 Correspondingly, catalytic pathways pertaining to the conversion of 2,3-BDO have been studied with various acid−base catalysts such as alkaline metal oxides, rare-earth metal oxide (REO), and zeolites. 5−7,9−15 The dehydration of 2,3-BDO to 1,3-BDE proceeds via a two-step reaction with the formation of the unsaturated alcohol 3-buten-2-ol (3B2oL) as an intermediate.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Recent research efforts toward the production of biobased fuels and chemicals from renewable resources have been gaining impetus in order to reduce the global dependency on nonrenewable fossil fuels and establish processes that utilize carbon neutral feedstock and energy resources. − 2,3-Butanediol (2,3-BDO) obtained from biomass fermentation/saccharification has garnered significant interest in this direction due to its potential as a sustainable platform molecule for the production of commodity chemicals such as 1,3-butadiene (1,3-BDE), methyl ethyl ketone (MEK), etc. − 2,3-BDO also has value as an initial biofeedstock for fuel applications, with recent work demonstrating a process pathway to produce sustainable aviation fuels by converting 2,3-BDO to C 3+ olefins that are subsequently oligomerized to form jet-range hydrocarbons . Correspondingly, catalytic pathways pertaining to the conversion of 2,3-BDO have been studied with various acid–base catalysts such as alkaline metal oxides, rare-earth metal oxide (REO), and zeolites. − ,− …”

Section: Introductionmentioning

confidence: 99%

Selective Dehydration of 2,3-Butanediol to 3-Buten-2-ol over In₂O₃ Catalyst

et al. 2021

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The selective dehydration of 2,3-butanediol (2,3-BDO) to 3-buten-2-ol (3B2oL) was investigated over indium oxide (In2O3) catalysts. The effect of different process parameters such as reaction temperature, weight hourly space velocity (WSHV), and carrier gas on the product distribution during the dehydration of 2,3-BDO was demonstrated. Highest selectivity to 3B2oL (70%) was achieved when the reaction was performed under a H2 flow, with 81% single pass conversion of 2,3-BDO. In all these cases, the dehydrogenation of 2,3-BDO was found to be the prevalent side reaction to dehydration. An optimum operating temperature (290 °C) corresponding to the selective formation of 3B2oL was identified, as further increases in temperature promoted other parallel reaction routes, which decreased selectivity toward 3B2oL. Varying the synthesis precursors and calcination temperatures allowed us to prepare In2O3 catalysts with differing ratios and concentrations of acid/base sites, which had a significant impact on both the dehydration and dehydrogenation pathways and provides a way to control the selectivity toward the desired product. Higher calcination temperatures (550 °C) were found to produce optimal acid/base site ratios that not only significantly improved the dehydration rate to the desired 3B2oL product but also suppressed the dehydrogenation rate. On the basis of the catalytic results and corresponding product distribution, the detailed reaction mechanism corresponding to the selective dehydration of 2,3-BDO to 3B2oL is also discussed herein.

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A hybrid pathway to biojet fuel via 2,3-butanediol

Abstract: A new hybrid pathway to biojet fuel via biomass-derived 2,3-butanediol has been demonstrated with high carbon recovery (74–82% of the theoretical maximum efficiency).

Cited by 26 publications

References 65 publications

Isolated Metal Sites in Cu–Zn–Y/Beta for Direct and Selective Butene-Rich C₃₊ Olefin Formation from Ethanol

Isolated Metal Sites in Cu–Zn–Y/Beta for Direct and Selective Butene-Rich C₃₊ Olefin Formation from Ethanol

Selective Butene Formation in Direct Ethanol-to-C₃₊-Olefin Valorization over Zn–Y/Beta and Single-Atom Alloy Composite Catalysts Using In Situ-Generated Hydrogen

Selective Dehydration of 2,3-Butanediol to 3-Buten-2-ol over In₂O₃ Catalyst

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A hybrid pathway to biojet fuel via 2,3-butanediol

Abstract: A new hybrid pathway to biojet fuel via biomass-derived 2,3-butanediol has been demonstrated with high carbon recovery (74–82% of the theoretical maximum efficiency).

Cited by 26 publications

References 65 publications

Isolated Metal Sites in Cu–Zn–Y/Beta for Direct and Selective Butene-Rich C3+ Olefin Formation from Ethanol

Isolated Metal Sites in Cu–Zn–Y/Beta for Direct and Selective Butene-Rich C3+ Olefin Formation from Ethanol

Selective Butene Formation in Direct Ethanol-to-C3+-Olefin Valorization over Zn–Y/Beta and Single-Atom Alloy Composite Catalysts Using In Situ-Generated Hydrogen

Selective Dehydration of 2,3-Butanediol to 3-Buten-2-ol over In2O3 Catalyst

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Isolated Metal Sites in Cu–Zn–Y/Beta for Direct and Selective Butene-Rich C₃₊ Olefin Formation from Ethanol

Isolated Metal Sites in Cu–Zn–Y/Beta for Direct and Selective Butene-Rich C₃₊ Olefin Formation from Ethanol

Selective Butene Formation in Direct Ethanol-to-C₃₊-Olefin Valorization over Zn–Y/Beta and Single-Atom Alloy Composite Catalysts Using In Situ-Generated Hydrogen

Selective Dehydration of 2,3-Butanediol to 3-Buten-2-ol over In₂O₃ Catalyst