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At least 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

X-AFm stabilization as a mechanism of bypassing conversion phenomena in calcium aluminate cements

Phase conversion phenomena are often observed in calcium aluminate cements (CACs), when the water-rich hydrates (e.g., CAH{sub 10}, C{sub 2}AH{sub 8}) formed at early ages, at temperatures ≤ 30 °C, expel water in time to form more compact, less water-rich structures (C{sub 3}AH{sub 6}). The phase conversions follow a path regulated by the thermodynamic stabilities (solubilities) of phases. Based on this premise, it is proposed that conversion phenomena in CACs can be bypassed by provoking the precipitation of phases more preferred than those typically encountered along the conversion pathway. Therefore, X-AFm formation (where in this case, X = NO{sub 3}{sup −}) triggered by the sequential addition of calcium nitrate (Ca(NO{sub 3}){sub 2} = CN) additives is identified as a new means of bypassing conversion. A multi-method approach comprising X-ray diffraction (XRD), thermal analytics, and evaluations of the compressive strength is applied to correlate phase balances and properties of CAC systems cured at 25 °C and 45 °C. The results highlight the absence of the C{sub 3}AH{sub 6} phase across all systems and the curing conditions considered, with enhanced strengths being noted, when sufficient quantities of CN are added. The experimental outcomes are supported by insights gained from thermodynamic calculations which highlight thermodynamic selectivity as a means of regulating and controlling the evolutions of solid phase balances using inorganic salts in CACs, and more generally in cementing material systems.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Biogenic coal-to-methane conversion can be enhanced with small additions of algal amendment in field-relevant upflow column reactors

Subsurface coal environments, where biogenic coal-to-methane conversion occurs, are difficult to access, resulting in inherent challenges and expenses for in situ experiments. Previous batch reactor studies provided insights into specific processes, pathways, kinetics, and engineering strategies, but field-relevance is restricted due to limited substrate availability or byproduct accumulation that may influence reactions or metabolisms. In this study, continuous-flow column reactors were used to overcome some batch limitations, improve the understanding of in situ conditions, and increase field-relevance for subsurface engineering technology development. The bench-scale reactor system was constructed to investigate the addition of algal amendment for enhancing microbial coal-to-methane conversion previously developed in batch systems. Four reactor columns were packed with coal and inoculated with a microbial consortium from the same Flowers-Goodale coal bed. Two reactors were amended with 13 C-labeled algal amendment on day 0, and two were unamended. On day 61, one previously amended and one previously unamended reactor were re-amended. Produced gases were captured in a gas trap, and CH 4 and CO 2 were quantified. The reactor amended twice produced 1712.6 µmol CH 4 (4.6% as 13 CH 4 ). The reactor amended only on day 0 produced 1485.5 µmol CH 4 (2.6% as 13 CH 4 ). The reactor amended only on day 61 produced 278.9 µmol CH 4 (3.9% as 13 CH 4 ). The reactor with no amendment produced no measurable gases for the duration of the 172-day experiment. Amendment increased the rate of coal-to-methane conversion and total gas production; most of the produced gases were due to coal conversion with only small contributions (<7%) from amendment conversion.

09 BIOMASS FUELS↗
DOE OSTI2020

The current status of high temperature electrochemistry-based CO 2 transport membranes and reactors for direct CO 2 capture and conversion

The concept of direct CO 2 capture and conversion has attracted significant interest from industries and academia in recent decades due to its potential to address the current grand challenge of global warming/climate change, rapid depletion of fossil fuels and realization of a future carbon neutral ecosystem. The incumbent benchmark technology for CO 2 capture is the post-combustion flue-gas “amine washing”, which is energy intensive and costly for large-scale commercial implementation. The CO 2 conversion technologies, on the other hand, are still at their infancy with many technical challenges to overcome, but primarily being explored in laboratory-scale, low-temperature, solution-based and high-temperature, solid-oxide-based electrochemical cells with renewable electricity perceived as the energy input. In this article, we provide a comprehensive overview on an emergent class of high-temperature electrochemical CO 2 transport membranes that can capture and convert CO 2 into valuable chemicals in single catalytic reactor fashion. The review starts with the chemistry and transport theory of three basic types of membranes purposely designed for different CO 2 feedstocks and downstream conversions. A range of key functional materials used in these membranes and their microstructural/electrochemical properties important to the CO 2 transport are then thoroughly discussed in conjunction with the effects of surface modifications and operating conditions. Several types of combined CO 2 capture and conversion catalytic reactors based on these membranes are also assessed with a focus on their working principles, system configurations and performance demonstrations. Finally, challenges and prospective of these electrochemical CO 2 transport membranes and their associated conversion reactors are candidly discussed for future development.

10 SYNTHETIC FUELS↗
DOE OSTI2018

Understanding Conversion-Type Electrodes for Lithium Rechargeable Batteries

The need/desire to lower the consumption of fossil fuels and its environmental consequences has reached unprecedented levels in recent years. A global effort has been undertaken to develop advanced renewable energy generation and especially energy storage technologies, as they would enable a dramatic increase in the effective and efficient use of renewable (and often intermittent) energy sources. The development of electrical energy storage (EES) technologies with high energy and power densities, long life, low cost, and safe use represents a challenge from both the fundamental science and technological application points of view. While the advent and broad deployment of lithium-ion batteries (LIBs) has dramatically changed the EES landscape, their performance metrics need to be greatly enhanced to keep pace with the ever-increasing demands imposed by modern consumer electronics and especially the emerging automotive markets. Current battery technologies are mostly based on the use of a transition metal oxide cathode (e.g., LiCoO 2 , LiFePO 4 , or LiNiMnCoO 2 ) and a graphite anode, both of which depend on intercalation/insertion of lithium ions for operation. While the cathode material currently limits the battery capacity and overall energy density, there is a great deal of interest in the development of high-capacity cathode materials as well as anode materials. Conversion reaction materials have been identified/proposed as potentially high-energy-density alternatives to intercalation-based materials. Yet, conversion reaction materials react during lithiation to form entirely new products, often with dramatically changed structure and chemistry, by reaction mechanisms that are still not completely understood. This makes it difficult to clearly distinguish the limitations imposed by the mechanism and practical losses from initial particle morphology, synthetic approaches, and electrode preparations. Transition metal compounds such as transition metal oxides, sulfides, fluorides, phosphides, and nitrides can undergo conversion reactions yielding materials with high theoretical capacity (generally from 500 to 1500 mA h g –1 ). Specifically, a number of transition metal oxides and sulfides have shown excellent electrochemical properties as high-capacity anode materials. In addition, some transition metal fluorides have shown great potential as cathode materials for Li rechargeable batteries. In this Account we present mechanistic studies, with emphasis on the use of operando methods, of selected examples of conversion-type materials as both potentially high-energy-density anodes and cathodes in EES applications. We also include examples of the conceptually similar conversion-type reactions involving chalcogens and halogens, with emphasis on the Li–S system. In this case we focus on the problems arising from the low electrical conductivities of elemental sulfur and Li 2 S and the “redox shuttle” phenomena of polysulfides. In addition to mechanistic insights from the use of operando methods, we further cover several key strategies in electrode materials design such as controlling the size, morphology, composition, and architecture.

25 ENERGY STORAGE↗
DOE OSTI2021

Asymmetric Reaction Pathways of Conversion-Type Electrodes for Lithium-Ion Batteries

Metal oxides have been actively explored as promising conversion-type electrode materials for lithium ion batteries due to high deliverable capacity but still notorious for poor cyclability, capacity fading, voltage hysteresis, etc. Yet, the fundamental reason for the undesirable properties of metal oxides behind the repetitive conversion process is still obscure. In this work, we take advantage of synchrotron X-ray techniques as well as transmission electron microscopy to monitor the structural changes during both conversion (lithiation) and reconversion (delithiation) reactions. Difference in diffusion rates of lithium and metal plays a decisive role in determining the reaction pathway. We find lithium accommodation and extraction occur via different reaction routes: lithiation follows a kinetically driven way while delithiation adopts a route close to the thermodynamic ground state path. Thermodynamic structural evolution features the formation of an intermediate phase of Li-Metal (M)-O, suggesting lithium removal accompanies with the Li/M ionic exchange and rearrangement of oxygen framework. The slow diffusion of metal ions and the high kinetic and energy barrier for dissociating the intermediate phase are mainly responsible for uncompleted reconversion reaction, evidenced by remaining Li-M-O phase at the end of charge. Imperfect reconversion reaction eventually limits the utilization of lithium ions over the repeated cycling. Furthermore, this work sheds light on structural changes occurring at metal oxides during both conversion and reconversion processes, which is strongly linked with the performances of conversion-type materials in applications.

25 ENERGY STORAGE↗
DOE OSTI2024

Screening of Cu-Based Catalysts for Selective Methane to Methanol Conversion

Developing selective catalysts for methane conversion to added value chemicals has been considered as a promising approach for efficient utilization of abundant natural gas resources. Here, we present a descriptor-based screening for high methane conversion and methanol selectivity at the interfaces between metal oxide clusters and Cu 2 O/Cu(111) support (MO x /Cu 2 O/Cu(111), M = Mg, Fe, Co, Ni, Cu, Zn, Ti, Zr, Sn, Ce) on exposure to the mixture of CH 4 /O 2 /H 2 O. Wherein, the activation energy of direct methane to methanol conversion, *OH + *CH 4 → *CH 3 OH + *H, and the ratio for adsorption energy of oxygen and water, E ads (O 2 )/E ads (H 2 O), are identified as the effective descriptor for methane conversion and methanol selectivity, respectively. Finally, by providing an exceptional oxygen and hydroxyl sites with high-lying O 2p states, the MgO/Cu 2 O/Cu(111) catalyst is found to be the most promising system among the systems studied, being able to provide the highest methane conversion with high methanol selectivity.

03 NATURAL GAS↗
DOE OSTI2025

Long-Range Metal–Sorbent Interactions Determine CO 2 Capture and Conversion in Dual-Function Materials

Carbon capture and utilization involve multiple energy- and cost-intensive steps. Dual-function materials (DFMs) can reduce these demands by coupling CO 2 adsorption and conversion into a single material with two functionalities: a sorbent phase and a metal for catalytic CO 2 conversion. The role of metal catalysts in the conversion process seems salient from previous work, but the underlying mechanisms remain elusive and deserve deeper investigation to achieve maximum utilization of the two phases. Here, for this work, preformed colloidal Ru nanoparticles were deposited onto a “NaOx”/Al 2 O 3 sorbent to prepare prototypical DFMs with controlled phases for CO 2 capture and hydrogenation to CH 4 . Ru addition was found to double the high-temperature CO 2 adsorption capacity by activating the “NaOx”/Al 2 O 3 sorbent phase during a reductive pretreatment step. Most importantly, low Ru loadings were sufficient to ensure maximum CO 2 adsorption and conversion. This was attributed to the key role of the metal–sorbent interactions, wherein Ru was required to hydrogenate strongly bound CO 2 on the “NaO x ”/Al 2 O 3 sorbent to CH 4 via the H 2 activated on Ru. This interaction facilitated rate-determining carbonate migration and subsequent hydrogenation at the metal–sorbent interface. Overall, Ru controlled the CO 2 hydrogenation reaction rate, while the “NaO x ”/Al 2 O 3 sorbent dictated the CO 2 uptake capacity. By controlling metal–sorbent interactions at the molecular level, we demonstrate the critical role of the two phases and their synergy, facilitating the design of DFMs with maximum CO 2 capture and conversion efficiency.

carbon capture↗
DOE OSTI2016

Size-controlled Intercalation to Conversion Transition in Lithiation of Transition-Metal Chalcogenides – NbSe3

Transition metal chalcogenides (TMCs) can either be used as intercalation cathodes or as conversion type anodes for lithium ion batteries, for which two distinctively different lithiation reaction mechanisms govern the electrochemical performance of TMCs. However, it remains elusive that what controls the transition of lithiation mechanisms. Herein, we investigated the lithiation process of NbSe3 ribbons using in situ transmission electron microscopy (TEM) and observed a size dependent transition from intercalation to conversion reaction. The large NbSe3 ribbons can accommodate high concentration of Li+ through intercalation by relaxing its internal spacing, while lithiation of small NbSe3 ribbons proceeds readily to full conversion reaction. We find that the size dependent variation of lithiation mechanism is attributed to the Li+ diffusion in NbSe3 and the accommodation of newly formed phases, i.e., insufficient Li+ diffusion and limited space for accommodating the volume expansion induced by forming new phases in large size ribbons both impede the intercalation-to-conversion transition. These results demonstrate the inherent structural instability of NbSe3 as an intercalation cathode and fast lithiation rate as a promising conversion type anode.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2021

High-Efficiency Conversion of Ionic Liquid-Pretreated Woody Biomass to Ethanol at the Pilot Scale

We report that with a diverse and widely distributed global resource base, woody biomass is a compelling organic feedstock for conversion to renewable liquid fuels. In California, woody biomass comprises the largest fraction of underutilized biomass available for biofuel production, but conversion to fuels is challenged both by recalcitrance to deconstruction and by toxicity toward downstream saccharification and fermentation due to organic acids and phenolic compounds generated during pretreatment. In this study, we optimize pretreatment and scale-up of an integrated one-pot process for deconstruction of California woody biomass using the ionic liquid (IL) cholinium lysinate [Ch][Lys] as a pretreatment solvent. By evaluating the impact of solid loading, solid removal, yeast acclimatization, fermentation temperature, fermentation pH, and nutrient supplementation on final ethanol yields and titers, we achieve nearly full conversion of both glucose and xylose to ethanol with commercial C5-utilizing Saccharomyces cerevisiae. We then demonstrate process scalability in 680 L pilot-scale fermentation, achieving >80% deconstruction efficiency, >90% fermentation efficiency, 27.7 g/L ethanol titer, and >80% ethanol distillation efficiency from the IL-containing hydrolysate post fermentation. This fully integrated process requires no intermediate separations and no intermediate detoxification of the hydrolysate. Using an integrated biorefinery model, current performance results in a minimum ethanol selling price of $\$$8.8/gge. Reducing enzyme loading along with other minor process improvements can reduce the ethanol selling price to $\$$3/gge. This study is the largest scale demonstration of IL pretreatment and biofuel conversion known to date, and the overall biomass-to-ethanol efficiencies are the highest reported to date for any IL-based biomass-to-biofuel conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Direct 2,3-Butanediol Conversion to Butene-Rich C 3+ Olefins over Copper-Modified 2D Pillared MFI: Consequence of Reduced Diffusion Length

2,3-Butanediol (2,3-BDO), a critical C 4 platform chemical derived from biomass, syngas, or CO 2 , can be converted to C 3+ olefins, serving as important renewable feedstocks for producing sustainable aviation fuels to decarbonize the hard-to-electrify air transportation sector. Herein, we report a bifunctional Cu-modified diffusion-free 2D pillared MFI catalyst (Cu/PMFI) which can selectively catalyze 2,3-BDO conversion to butene-rich C 3+ olefins (95% selectivity at 97% conversion, 523 K). 2,3-BDO conversion to butenes over Cu/PMFI primarily occurs via methyl ethyl ketone intermediate while 2-methyl propanal is also observed as another minor dehydration product that leads to butene formation. In comparison with a control mesoporous Cu/ZSM-5 sample prepared by the postsynthetic approach, Cu/PMFI shows favorable C 3+ olefin selectivity (95% over Cu/PMFI vs 80% over Cu/ZSM-5 at ~5.1 h TOS). The coke formation over Cu/PMFI is dramatically suppressed by >50% in contrast to Cu/ZSM-5 in 90 h 2,3-BDO conversion due to the reduced diffusion length. Cu/PMFI also favors butene formation and minimizes nonbutene C 3+ olefins by inhibiting the downstream oligomerization and cracking reactions. This study highlights the usefulness of the diffusion-free 2D PMFI materials in catalytic conversion of biomass-derived platform molecules and the significance of diffusion impact on catalyst coke formation and product distributions.

2,3-butanediol↗
DOE OSTI2016

Valorization of Waste Lipids through Hydrothermal Catalytic Conversion to Liquid Hydrocarbon Fuels with in Situ Hydrogen Production

We demonstrate hydrothermal (300 degrees C, 10 MPa) catalytic conversion of real waste lipids (e.g., waste vegetable oil, sewer trap grease) to liquid hydrocarbon fuels without net need for external chemical inputs (e.g., H2 gas, methanol). A supported bimetallic catalyst (Pt-Re/C; 5 wt % of each metal) previously shown to catalyze both aqueous phase reforming of glycerol (a triacylglyceride lipid hydrolysis coproduct) to H2 gas and conversion of oleic and stearic acid, model unsaturated and saturated fatty acids, to linear alkanes was applied to process real waste lipid feedstocks in water. For reactions conducted with an initially inert headspace gas (N2), waste vegetable oil (WVO) was fully converted into linear hydrocarbons (C15-C17) and other hydrolyzed byproducts within 4.5 h, and H2 gas production was observed. Addition of H2 to the initial reactor headspace accelerated conversion, but net H2 production was still observed, in agreement with results obtained for aqueous mixtures containing model fatty acids and glycerol. Conversion to liquid hydrocarbons with net H2 production was also observed for a range of other waste lipid feedstocks (animal fat residuals, sewer trap grease, dry distiller's grain oil, coffee oil residual). These findings demonstrate potential for valorization of waste lipids through conversion to hydrocarbons that are more compatible with current petroleum-based liquid fuels than the biodiesel and biogas products of conventional waste lipid processing technologies.

09 BIOMASS FUELS↗
DOE OSTI2023

Direct Conversion of Methane to Ethylene and Acetylene over an Iron-Based Metal–Organic Framework

Conversion of methane (CH 4 ) to ethylene (C 2 H 4 ) and/or acetylene (C 2 H 2 ) enables routes to a wide range of products directly from natural gas. However, high reaction temperatures and pressures are often required to activate and convert CH 4 controllably, and separating C 2+ products from unreacted CH 4 can be challenging. Here, we report the direct conversion of CH 4 to C 2 H 4 and C 2 H 2 driven by non-thermal plasma under ambient (25 °C and 1 atm) and flow conditions over a metal–organic framework material, MFM-300(Fe). The selectivity for the formation of C 2 H 4 and C 2 H 2 reaches 96% with a high time yield of 334 μmol g cat –1 h –1 . At a conversion of 10%, the selectivity to C 2+ hydrocarbons and time yield exceed 98% and 2056 μmol g cat –1 h –1 , respectively, representing a new benchmark for conversion of CH 4 . In situ neutron powder diffraction, inelastic neutron scattering and solid-state nuclear magnetic resonance, electron paramagnetic resonance (EPR), and diffuse reflectance infrared Fourier transform spectroscopies, coupled with modeling studies, reveal the crucial role of Fe–O(H)–Fe sites in activating CH 4 and stabilizing reaction intermediates via the formation of an Fe–O(CH 3 )–Fe adduct. In addition, a cascade fixed-bed system has been developed to achieve online separation of C 2 H 4 and C 2 H 2 from unreacted CH 4 for direct use. Integrating the processes of CH 4 activation, conversion, and product separation within one system opens a new avenue for natural gas utility, bridging the gap between fundamental studies and practical applications in this area.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Revisiting Conversion Reaction Mechanisms in Lithium Batteries: Lithiation-Driven Topotactic Transformation in FeF 2

Intercalation-type electrodes have now been commonly employed in today’s batteries as such materials are capable of storing and releasing lithium reversibly via topotactic transformation, conducive to small structural change, but they have limited interstitial sites to hold Li. In contrast, conversion electrodes feature high Li-storage capacity, but often undergo large structural change during (de)lithiation, resulting in cycling instability. One exception is iron fluoride (FeF 2 ), a conversion-type cathode that exhibits both high capacity and high cycling stability. Herein, we report a lithiation-driven topotactic transformation in a single crystal of FeF2, unveiled by in situ visualization of the spatial and crystallographic correlation between the parent and converted phases. Specifically, conversion in FeF 2 resembles the intercalation process but involves transport of both Li + and Fe 2+ ions within the F-anion array, leading to formation of Fe preferentially along specific crystallographic orientations of FeF 2 . Throughout the process, the F-anion framework is retained, creating a checkerboard-like structure, within which the volume change is largely compensated, thereby enabling the high cyclability in FeF 2 . Lastly, findings from this study, with unique insights into conversion reaction mechanisms, may help to pave the way for designing conversion-type electrodes for the next-generation high energy lithium batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Overcoming the conversion reaction limitation at three-phase interfaces using mixed conductors towards energy-dense solid-state Li–S batteries

Lithium–sulfur (Li–S) all-solid-state batteries (ASSBs) hold great promise for next-generation safe, durable and energy-dense battery technology. However, solid-state sulfur conversion reactions are kinetically sluggish and primarily constrained to the restricted three-phase boundary area of sulfur, carbon and solid electrolytes, making it challenging to achieve high sulfur utilization. Here, in this study, we develop and implement mixed ionic–electronic conductors (MIECs) in sulfur cathodes to replace conventional solid electrolytes and invoke conversion reactions at sulfur–MIEC interfaces in addition to traditional three-phase boundaries. Microscopic and tomographic analyses reveal the emergence of mixed-conducting domains embedded in sulfur at sulfur–MIEC boundaries, helping promote the thorough conversion of active sulfur into Li 2 S. Consequently, substantially improved active sulfur ratios (up to 87.3%) and conversion degrees (>94%) are achieved in Li–S ASSBs with high discharge capacity (>1,450 mAh g –1 ) and long cycle life (>1,000 cycles). The strategy is also applied to enhance the active material utilization of other conversion cathodes.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Erasure conversion in a high-fidelity Rydberg quantum simulator

Minimizing and understanding errors is critical for quantum science, both in noisy intermediate scale quantum (NISQ) devices and for the quest towards fault-tolerant quantum computation. Rydberg arrays have emerged as a prominent platform in this context with impressive system sizes and proposals suggesting how error-correction thresholds could be significantly improved by detecting leakage errors with single-atom resolution, a form of erasure error conversion. However, two-qubit entanglement fidelities in Rydberg atom arrays have lagged behind competitors and this type of erasure conversion is yet to be realized for matter-based qubits in general. Here we demonstrate both erasure conversion and high-fidelity Bell state generation using a Rydberg quantum simulator. When excising data with erasure errors observed via fast imaging of alkaline-earth atoms, we achieve a Bell state fidelity of $\ge 0.997{1}_{-13}^{+10}$ , which improves to $\ge 0.998{5}_{-12}^{+7}$ when correcting for remaining state-preparation errors. We further apply erasure conversion in a quantum simulation experiment for quasi-adiabatic preparation of long-range order across a quantum phase transition, and reveal the otherwise hidden impact of these errors on the simulation outcome. Our work demonstrates the capability for Rydberg-based entanglement to reach fidelities in the 0.999 regime, with higher fidelities a question of technical improvements, and shows how erasure conversion can be utilized in NISQ devices. These techniques could be translated directly to quantum-error-correction codes with the addition of long-lived qubits.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Heterobimetallic zeolite, InV-ZSM-5, enables efficient conversion of biomass derived ethanol to renewable hydrocarbons

Here, direct catalytic conversion of ethanol to hydrocarbon blend-stock can increase biofuels use in current vehicles beyond the ethanol blend-wall of 10–15%. Literature reports describe quantitative conversion of ethanol over zeolite catalysts but high C 2 hydrocarbon formation renders this approach unsuitable for commercialization. Furthermore, the prior mechanistic studies suggested that ethanol conversion involves endothermic dehydration step. Here, we report the complete conversion of ethanol to hydrocarbons over InV-ZSM-5 without added hydrogen and which produces lower C 2 (<13%) as compared to that over H-ZSM-5. Experiments with C 2 H 5 OD and in situ DRIFT suggest that most of the products come from the hydrocarbon pool type mechanism and dehydration step is not necessary. Thus, our method of direct conversion of ethanol offers a pathway to produce suitable hydrocarbon blend-stock that may be blended at a refinery to produce fuels such as gasoline, diesel, JP-8, and jet fuel, or produce commodity chemicals such as BTX.

09 BIOMASS FUELS↗
DOE OSTI2022

Effect of alkali metal addition on catalytic performance of Ag/ZrO 2 /SBA-16 catalyst for single-step conversion of ethanol to butadiene

Here, we describe how adding Na and K to a 4Ag/4ZrO 2 /SBA-16 catalyst enhances catalytic performance for single-bed conversion of ethanol to butadiene. While adding Na and K leads to a slight decrease in conversion (i.e., ~10% loss), the production of desired butadiene is significantly increased with up to 50% improvement in productivity for the 4Ag/4ZrO 2 /SBA-16 catalyst promoted with 0.5% Na. The reasons for this improvement are a beneficial decrease in Lewis acid site concentration and higher Ag dispersion when Na or K are added, which results in decreased activity involving ethanol dehydration to ethylene and diethyl ether. A remarkable butadiene selectivity of 75% was achieved while maintaining high conversion (i.e., 90%) with 0.5Na/4Ag/4ZrO 2 /SBA-16 catalyst. A 72-hour catalyst lifetime study shows that because of higher coke formation from polymerization of desired butadiene, catalyst deactivation occurs more rapidly with the 0.5Na/4Ag/4ZrO 2 /SBA-16 (55% loss in conversion) than with 4Ag/4ZrO 2 /SBA-16 (45% loss in conversion). However, this does not alter the advantageous effect of Na addition because the butadiene yield remained higher throughout the study period for 0.5Na/4Ag/4ZrO 2 /SBA-16. A key finding is that during the reaction, Na limits sintering of Ag particles and promotes selective coking of the acid sites responsible for ethylene and diethyl ether formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Mechanistic insights into the conversion of polyalcohols over Brønsted acid sites

Multi-layered plastic (MLP) films provide excellent properties for food packaging; however, because of the complicated chemistry of the hydrophobic substrates and tightly laminated hydrophilic layers, it is challenging to recycle the MLP films. The selective conversion of polar functional groups in hydrophilic layers with a minimal destruction of the carbon backbone of constituted polymers is considered a promising approach to improve the recyclability of MLP films. Here, in this study, we combine computational and experimental studies to investigate the acid-catalyzed conversion of functional groups in polyalcohols, through which we report potential reaction pathways involved in the conversion of ethylene vinyl alcohol (EVOH), a common copolymer used in MLP films as an oxygen barrier. Using 2,4-pentanediol as a model compound, we show that its conversion proceeds primarily through the dehydration of a hydroxyl group via either a stepwise or a concerted mechanism to form an unsaturated alcohol that can be further converted into a conjugated diene or a saturated ketone; this secondary reaction determines the product selectivity. The rate determining intermediates and transition states are identified, and the activation barriers are calculated, in agreement with experimentally observed product selectivities. This study thus provides insights for the selective conversion of EVOH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗