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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 343 records · Page 19

Multistep catalytic abiotic CO2 conversion to sugars through C1 intermediates

Carbon dioxide (CO2) to multicarbon (Cn) upgrading for commodity chemicals, fuel production, or artificial food synthesis using renewable energy input is a golden target for researchers in sustainable carbon emission reduction. Here, we explore and analyze a flexible modular roadmap for the task, utilizing sequential electro-, photo-, and organocatalysis to develop a strategy for CO2 conversion using the key and elusive formaldehyde precursor of interest for sugar generation. We study the electrochemical carbon dioxide reduction reaction to methanol in a flow cell and its discontinuous photooxidation to formaldehyde (PMOR) with excellent selectivity. Utilizing a highly active N-heterocyclic carbene catalyst enables tunable generation of C4-C6 aldoses without undesirable byproducts, with carbon conversion yield reaching 60 to 80% for desired pentose, tetrose, and triose product mixtures and over 20% for hexose. This approach presents a roadmap for CO2 valorization, aiming to bridge carbon waste streams with sustainable sugar synthesis and opening broad avenues for green chemical production.

CO2 valorization↗

Computer–aided process intensification: Challenges, trends and opportunities

Chemicals based products and the processes that manufacture them play important roles in sustaining our society. Chemical, biochemical, petrochemical and related processes are characterized by either conversion of specific raw materials to desired chemicals or extraction of desired chemicals from specific raw materials. Well–known examples in the first category are the conversion of methanol and acetic acid to form methyl acetate and water, and, carbon dioxide hydrogenation to methanol via the reverse water gas shift reaction. In the second category, the use of de–methanizer, de–ethanizer, de–propanizer, and so on, separation steps in gas processing plants are well–known. In the conversion–based processes, as the conversions of raw materials are usually not 100% complete, energy intensive downstream separation techniques need to be employed to separate the desired products and recycle the unreacted raw materials. Note that the conversion process itself may also be energy intensive. In the extraction–based processes where product chemicals do not usually represent 100% of the raw material, energy intensive separation techniques are commonly employed to achieve the desired separations. This means that for both categories of processes, energy in different forms need to be supplied and the processes during operation have the potential to produce waste that may lead to negative environmental impacts and cause supply chain issues. Furthermore, planet earth is facing challenges with respect to energy, water, food, and environment, and significant improvements in process efficiencies of new and/or existing processes are needed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterization of Liquid Fuel Evaporation of a Lifted Methanol Spray Flame in a Vitiated Coflow Burner

An experimental investigation of lifted spray flames in a coflow of hot, vitiated gases is presented. The vitiated coflow burner is a spray flame that issues into a coaxial flow of hot combustion products from a lean, premixed H2/Air flame. The spray flame in a vitiated coflow emulates the combustion that occurs in many advanced combustors without the detailed fluid mechanics. Two commercially available laser diagnostic systems are used to characterize the spray flame and to demonstrate the vitiated coflow burner's amenability to optical investigation. The Ensemble Particle Concentration and Size (EPCS) system is used to measure the path-average droplet size distribution and liquid volume fraction at several axial locations while an extractive probe instrument named the Real-time Fuel-air Analyzer (RFA) is used to measure the air to fuel ratio downstream of the spray nozzle with high temporal and spatial resolution. The effect of coflow conditions (stoichiometry) and dilution of the fuel with water was studied with the EPCS optical system. As expected, results show that water retards the evaporation and combustion of fuels. Measurements obtained by the RFA extractive probe show that while the Delavan manufactured nozzle does distribute the fuel over the manufacturer specified spray angle, it unfortunately does not distribute the fuel uniformly, providing conditions that may result in the production of unwanted NOx. Despite some limitations due to the inherent nature of the experimental techniques, the two diagnostics can be readily applied to spray flames in the vitiated coflow environment.

Cabra, Ricardo↗

Hydrothermal catalytic conversion of oleic acid to heptadecane over Ni/ZrO 2

There is growing interest in the substitution of expensive noble metal catalysts with low-cost earth-abundant metals in applications targeting biofuels production from waste organic feedstocks. Here, nickel (Ni) catalysts supported on zirconium dioxide (ZrO 2 ), both with and without copper (Cu) as a co-metal, were tested in hydrothermal reactions of unsaturated and saturated C18 fatty acids as models for waste oil feedstocks. In contrast to recent reports, this study showed no enhancement of nickel's activity for fatty acid conversion to alkane products when Cu was present. Ni/ZrO 2 prepared by metal coprecipitation methods converted 100% of oleic acid with 25% selectivity to heptadecane after 5h of reaction at 350 °C using methanol as a hydrogen donor source, increasing to 41% heptadecane after 20 h. Lower yields were observed with catalysts prepared by wet impregnation and using alternative hydrogen donor sources (glycerol, formic acid). Greater selectivity to heptadecane was also observed at higher temperatures (370 °C) and when the initial fatty acid had greater saturation. Longer term exposure to hydrothermal media led to metal sintering and catalyst deactivation. Findings support a path forward to the development of earth-abundant metal catalysts for the upgrading of waste organic feedstocks.

09 BIOMASS FUELS↗

An evaluation of microorganisms for unconventional food regeneration schemes in CELSS - Research recommendations

The benefits and deficiencies of various candidates for a controlled ecological life support system (CELSS) for manned spacecraft missions of at least 3-14 yr are discussed. Conventional plants are considered unacceptable due to their inefficient production of foodstuffs and overproduction of stems and leafy matter. The alternate concepts are algae and/or bacteria or chemical synthesis of food. Microorganisms are considered the most promising because of their direct use of CO2 and possible utilization of waste streams. Yeasts are cited as the most viable candidates, since a large data base and experience already exists in the commercial food industry. The addition of hydrogen bactria and solar-grown algae is recommended, together with genetic manipulation experiments to tailor the microorganisms to production of foodstuffs closer to the 70 percent carbohydrate, 20 percent protein, and 10 percent lipid optimal food currently accepted. The yeast strain, Hansenula polymorpha, has been successfully grown in methanol and encouraged to produce a 55 percent carbohydrate content.

Stokes, B. O.↗

Pressure Effects on Combustion of Methanol and Methanol-Docecanol Droplets

The objective of this research is to improve understanding of the combustion of binary fuel mixtures in the vicinity of the critical point. Fiber-supported single droplets and two-droplet arrays of methanol and of mixtures of methanol and 1-dodecanol, initially 0.9 mm in diameter, were burned in room-temperature air at pressures from 0.1 MPa to 9.0 MPa in the NASA Lewis 2.2-second drop tower. The work is a continuation of a collaborative Japan-US research effort designed to increase knowledge of high-pressure combustion of fuel sprays, relevant to application in propulsive and power-production devices such as Diesel engines. Some previous publications from this cooperative program may be cited. All of the previous experiments concerned alkanes and alkane mixtures. The new research reported here addresses alcohols and alcohol mixtures, to ascertain the degree to which previous results for alkanes extend to alcohols. There have been many previous experimental studies of methanol droplet combustion and a few of alcohol mixtures, but not at the high pressures of interest here. There is some experimental information on methanol droplet combustion at elevated pressure but none on the alcohol mixtures extending to critical pressures, as in the present study.

Okai, K.↗

Chemical recycling of post-consumer polyester wastes using a tertiary amine organocatalyst

Recycling diverse waste plastics poses challenges due to complex sorting and processing, resulting in high costs and inefficiency. To tackle this, we present a metal-free catalytic sorting method for targeted deconstruction of polyester from post-consumer plastic waste, encompassing textiles, plastic mixtures, and multilayer packaging materials. This method employs N-methylpiperidine, a tertiary amine catalyst in methanol, to depolymerize polyethylene terephthalate (PET). Operating under these conditions (160°C, 1 h), we achieve 100% yields of dimethyl terephthalate and ethylene glycol. This technique also effectively breaks down other polyesters, including polylactic acid, polycarbonate, and polybutylene terephthalate, yielding high-yield monomers at relatively low temperatures. Through comprehensive nuclear magnetic resonance (NMR) analysis, we propose that N-methylpiperidine’s role is in enhancing methanol nucleophilicity and activating PET’s ester bond. Our insights advance the chemical recycling of post-consumer plastic waste, offering a potentially simple and efficient path to closing the polyester production loop.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Alternative Fuels and Their Potential Impact on Aviation

With a growing gap between the growth rate of petroleum production and demand, and with mounting environmental needs, the aircraft industry is investigating issues related to fuel availability, candidates for alternative fuels, and improved aircraft fuel efficiency. Bio-derived fuels, methanol, ethanol, liquid natural gas, liquid hydrogen, and synthetic fuels are considered in this study for their potential to replace or supplement conventional jet fuels. Most of these fuels present the airplane designers with safety, logistical, and performance challenges. Synthetic fuel made from coal, natural gas, or other hydrocarbon feedstock shows significant promise as a fuel that could be easily integrated into present and future aircraft with little or no modification to current aircraft designs. Alternatives, such as biofuel, and in the longer term hydrogen, have good potential but presently appear to be better suited for use in ground transportation. With the increased use of these fuels, a greater portion of a barrel of crude oil can be used for producing jet fuel because aircraft are not as fuel-flexible as ground vehicles.

Daggett, D.↗

Engineering acid-base active sites on an N-doped biochar catalyst for microwave-assisted biodiesel production from waste cooking oil

Acid-base bifunctional catalysts play a crucial role in converting high-free fatty acid (FFA) feedstocks into biodiesel by enabling the simultaneous esterification and transesterification of triglycerides in a single step, thereby minimizing saponification and streamlining the process. In this study, we report the design and development of a novel N-doped acid-base bifunctional biochar catalyst synthesized from renewable biomass precursors- glucose and chitosan. The catalyst’s acidic sites were introduced via surface functionalization with o-sulfobenzoic acid cyclic anhydride, grafting -SO₃H groups onto the carbon framework, while basic sites were generated from amine functionalities (-NH) derived from chitosan, yielding a robust and truly bifunctional surface. The catalyst was characterized and used for the microwave-assisted transesterification of waste cooking oil, and process optimization using response surface methodology (RSM-CCD) yielding a maximum biodiesel yield of 98.8 ± 0.4% under optimal conditions (methanol-to-oil molar ratio 20:1, catalyst loading 5.7 wt%, temperature 99 °C, and reaction time 46.6 min). The catalyst demonstrated good stability, maintaining a yield of 92.2 ± 0.4% after eight reuse cycles. A Life Cycle Assessment (LCA) conducted for 1 kg of biodiesel production revealed a global warming potential of 0.85 kg CO 2 eq and human toxicity potential of 1.59 kg 1,4-DB eq, with the largest environmental contributions arising from catalyst preparation and reuse. In conclusion, this work highlights a green and circular approach to biodiesel production, combining renewable catalyst design, waste feedstock utilization, and quantitative sustainability assessment to guide future developments in sustainable catalysis and biofuel engineering.

Bifunctional catalyst↗

A Novel Catalytic Membrane Reactor for DME Synthesis from Renewable Resources

Production of liquid fuels or chemicals from CO 2 (captured from the air or flue gases) and renewable hydrogen presents a new approach to producing clean fuels domestically. While significant progress has been made in the area of renewable electricity generation from solar and wind, a large gap remains with respect to the production of renewable liquid fuels/chemicals. Other processes for producing liquid fuels/chemicals from renewable electricity are constrained by thermodynamic limitations, making them prohibitively expensive and impractical. The team is overcoming these limitations and developing catalytic membrane reactor processes with high yields and low energy penalties. Supported by the Advanced Research Projects Agency-Energy (ARPA-E) of the US Department of Energy (DOE), GTI Energy and partners have been developing a technology for the production of renewable dimethyl ether (DME) from carbon dioxide (CO 2 ) and renewable hydrogen (H 2 ) using a novel catalytic membrane reactor and demonstration of this system at a scale of 1 kg/day. DME is a clean-burning, non-toxic fuel with a high cetane value (55-60), making it an excellent diesel alternative. DME can be stored as a liquid under moderate pressure, eliminating the need for the high-pressure containers used for CNG or cryogenics, as in the case of LNG. DME is also approved as a renewable fuel under the U.S. Environmental Protection Agency’s Renewable Fuels Standard (RFS), making it eligible for Renewable Identification Numbers (RINs) credits. By producing DME through the catalytic conversion of captured CO 2 and renewable H 2 , this process will produce renewable liquid transportation fuel and a means of large-scale utilization of captured CO 2 . In the DME synthesis process, CO 2 and H 2 are fed to a hollow fiber catalytic membrane reactor at 300-600 psig that contains a bi-functional catalyst that combines two reactions, methanol synthesis (CO 2 + 3H 2 → CH 3 OH + H 2 O) and methanol dehydration (2CH 3 OH → CH 3 OCH 3 + H 2 O), into a one-step process to produce DME. The bifunctional catalyst converts methanol to DME, enabling higher overall CO 2 conversion. A Cu/ZnO/ZrO 2 /Al 2 O 3 (CZZA) catalyst is used for methanol synthesis and is coupled with a zeolite catalyst H-ZSM-5 for dehydration. This one-step process intensifies a process that would otherwise require multiple reaction steps. However, combining these two reactions results in increased water production which inhibits catalytic activity. Here, the Na + -gated, water-transport membrane (Science, vol. 367, pp. 667, 2020), removes water in situ, shifting the thermodynamic equilibrium towards product formation while decreasing kinetic inhibition from water adsorption onto the catalyst surface. The Na + gated, water-transport nanochannel membrane showed H 2 O/CO 2 selectivity of 560 at 250 °C and 300 psig for H 2 O/CO 2 /CO/H 2 /MeOH gas mixtures. The selectivities of H 2 O/H 2 , H 2 O/CO, and H 2 O/MeOH were 190, 170, and 80, respectively. In a laboratory-scale membrane reactor, DME synthesis testing using this membrane, a DME production rate of 440 g DME /kg cat /h was achieved at 260 °C and 550 psig. Compared to the packed bed reactor, the CO 2 conversion and DME production rate in the membrane reactor were 80% and three times higher, respectively. A prototype test system (1 kg/day) was designed, constructed, and tested. A DME production rate of 1.31 kg/day and a DME productivity of 360 g/h/kg were achieved in the prototype membrane reactor. Good stability was demonstrated during 150-h continuous operation and multiple startups/shutdowns tests.

10 SYNTHETIC FUELS↗

A novel 3-D pulsating heat pipe module for high heat-flux applications

This study proposed a novel pulsating heat pipes (PHP) for high-flux thermal module. According to the open literature, the maximum value of the heat flux is 23.7 W∙cm –2 handled by PHP, which is far behind industry requirements. Therefore, the present study proposes a novel 3D PHP suitable for high heat-flux applications. The PHP were experimentally tested for different working fluids, including methanol and water. Furthermore, the experiments were performed to analyze the influence of various operating parameters, such as filling ratio (25–60%), heat load (100–800 W), and air flow rate 100–250 cubic feet per minute (CFM). In this work, the results showed that this PHP can sustain a heat flux up to 70 W∙cm –2 with the maximum case temperature under 80 °C, which is approximately three times higher than the available literature. Furthermore, the performance of the PHP module was compared against the commercial module with wicked heat pipe. The PHP exhibited about 7% higher heat dissipation compared to the commercial module. Since the proposed module uses simple copper tubes in its construction over the wicked structure used in commercial module, the novel 3D PHP module provides additional economic and mass production capability.

3D pulsating heat pipe↗

Direct Alcohol Fuel Cells: A Comparative Review of Acidic and Alkaline Systems

In the last 20 years, direct alcohol fuel cells (DAFCs) have been the subject of tremendous research efforts for the potential application as on-demand power sources. Two leading technologies respectively based on proton exchange membranes (PEMs) and anion exchange membranes (AEMs) have emerged: the first one operating in an acidic environment and conducting protons; the second one operating in alkaline electrolytes and conducting hydroxyl ions. In this review, we present an analysis of the state-of-the-art acidic and alkaline DAFCs fed with methanol and ethanol with the purpose to support a comparative analysis of acidic and alkaline systems, which is missing in the current literature. A special focus is placed on the effect of the reaction stoichiometry in acidic and alkaline systems. Particularly, we point out that, in alkaline systems, OH – participates stoichiometrically to reactions, and that alcohol oxidation products are anions. This aspect must be considered when designing the fuel and when making an energy evaluation from a whole system perspective.

25 ENERGY STORAGE↗

Engineering Terpene Production Pathways in Methylobacterium extorquens AM1

Terpenes are diverse specialized metabolites naturally found within plants and have important roles in inter-species communication, adaptation and interaction with the environment. Their industrial applications span a broad range, including fragrances, flavors, cosmetics, natural colorants to agrochemicals and therapeutics, yet formal chemical synthesis is economically challenging due to structural complexities. Engineering terpene biosynthesis could represent an alternative in microbial biotechnological workhorses, such as Saccharomyces cerevisiae or Escherichi coli, utilizing sugars or complex media as feedstocks. Host species that metabolize renewable and affordable carbon sources may offer unique sustainable biotechnological alternatives. Methylotrophs are bacteria with the capacity to utilize one-carbon feedstocks, such as methanol or formate. They colonize the phyllosphere (above-ground area) of plants, and many accumulate abundant carotenoid pigments. Methylotrophs have the capacity to take up and use a subset of the rare earth elements known as lanthanides. These metals can enhance one-carbon (methylotrophic) metabolism. Here, we investigated whether manipulating the metabolism enables and enhances terpene production. A carotenoid-deficient mutant potentially liberates carbon, which may contribute to bioproduct accumulation. To test this hypothesis, terpene-producing bacterial strains regulated by two distinct promoters were generated. Wildtype Methylobacterium extorquens, ∆Meta1_3665, a methylotrophic mutant lacking the carotenoid pathway, and an E. coli strain were transformed with an exogenous terpene pathway and grown both in the presence and absence of lanthanides. The extraction, and the comparison of analytical profiles, provided evidence that engineered cultured M. extorquens under control of a native, inducible methylotrophic promoter can yield the sesquiterpene patchoulol when supplemented with lanthanide. In contrast, using a moderate-strength constitutive promoter failed to give production. We demonstrated colonization of the phyllosphere with the engineered strains, supporting the future engineering of selected species of the plant microbiome and with promising implications for the synthetic biology of small molecules.

59 BASIC BIOLOGICAL SCIENCES↗

Diatom volatile organic compound production is driven by diel metabolism and the cell cycle

Introduction: Volatile organic compounds (VOCs) are small, low-vapor-pressure molecules emitted from the surface ocean into the atmosphere. In the atmosphere, VOCs can change OH reactivity and condense onto particles to become cloud condensation nuclei. VOCs are produced by phytoplankton, but the conditions leading to VOC accumulation in the surface ocean are poorly understood.Methods: In this study, VOC accumulation was measured in real time over a 12 h day−12 h night cycle in the model diatom Phaeodactylum tricornutum during exponential growth.Results: Sixty-three m/z signals were produced in higher concentrations than in cell-free controls. All VOCs, except methanol, were continuously produced over 24 h. All VOCs accumulated to higher concentrations during the day compared to the night, and 11 VOCs exhibited distinct accumulation patterns during the morning hours. Twenty-seven VOCs were associated with known metabolic pathways in P. tricornutum, with most VOCs involved in amino acid and fatty acid metabolism.Discussion: Patterns of VOC production were strongly associated with diel shifts in cell physiology and the cell cycle. Diel VOC production patterns give a fundamental understanding of the first steps in VOC accumulation in the surface ocean.

Biological and medical sciences↗

Engineered Accumulation of Protocatechuate in Corn Biomass to Enhance Biomanufacturing

The in-planta accumulation of coproducts in crops can enhance the value of lignocellulosic biomass and facilitate a sustainable bioeconomy. Corn stover represents a major renewable source of lignocellulose for the production of advanced biofuels and bioproducts. In this study, we engineered corn with a bacterial gene encoding a dehydroshikimate dehydratase (QsuB) to overproduce protocatechuate (DHBA). Transgenic corn lines accumulate up to 2.9% DHBA on a dry weight basis in leaf and stem biomass. DHBA occurs in the form of glucosides that are extractable from biomass using aqueous methanol as the solvent. The analysis of lignin did not show any evidence for the incorporation of DHBA; however, an increase in the lignin syringyl to guaiacyl ratio and a higher relative abundance of p-coumarate groups compared with total lignin units were observed in QsuB-modified corn. Alkaline hydrolysates prepared from QsuB corn were enriched in DHBA compared to the hydrolysates obtained from wild-type biomass, which contained mostly p-coumarate and ferulate. Using engineered Novosphingobium aromaticivorans as a production host, a 375% improvement in 2-pyrone-4,6-dicarboxylate titers was achieved through biological upgrading of alkaline hydrolysates derived from QsuB corn compared to unmodified biomass. Our data demonstrate an engineering strategy to overproduce DHBA in corn that can facilitate sustainable manufacturing of other valuable bioproducts using stover as a feedstock.

2-pyrone-4,6-dicarboxylate↗

Conversion of syngas into light olefins in one step for process-intensified production of sustainable aviation fuels

Here, we report on a preliminary investigation for direct conversion of syngas into olefins. This technology combines alcohol(s) production and olefin(s) production into a single unit operation to improve process efficiencies due to the overcoming of equilibrium limitations and also to offer capital savings relative to current synthesis approaches including Fischer-Tropsch synthesis, methanol-to-olefins followed by olefins to gasoline/distillate process and alcohol-to-jet process.

10 SYNTHETIC FUELS↗

Methanol Uptake by Low Temperature Aqueous Sulfuric Acid Solutions

The global methanol budget is currently unbalanced, with source terms significantly larger than the sinks terms. To evaluate possible losses of gaseous methanol to sulfate aerosols, the solubility and reactivity of methanol in aqueous sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosols is under investigation. Methanol will partition into sulfate aerosols according to its Henry's law solubility. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H*, for cold (196 - 220 K) solutions ranging between 45 and 70 wt % H2SO4. We have found that methanol solubility ranges from approx. 10(exp 5) - 10(exp 7) M/atm for UT/LS conditions. Solubility increases with decreasing temperature and with increasing sulfuric acid content. Although methanol is slightly more soluble than are acetone and formaldehyde, current data indicate that uptake by clean aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These solubility measurements include uptake due to physical solvation and any rapid equilibria which are established in solution. Reaction between primary alcohols and sulfuric acid does occur, leading to the production of alkyl sulfates. Literature values for the rate of this reaction suggest that formation of CH3OSO3H is not significant over our experimental time scale for solutions below 80 wt % H2SO4. To confirm this directly, results obtained using a complementary equilibrium measurement technique will also be presented.

Iraci, L. T.↗

High-Octane Gasoline from Lignocellulosic Biomass via Syngas and Methanol/Dimethyl Ether Intermediates: 2020 State of Technology

The 2020 state of technology (SOT) serves as an update to the 2019 SOT report and details the techno-economic analysis (TEA) results for producing high-octane gasoline (HOG) via indirect liquefaction (IDL). This report only describes changes to the experimental and analysis results from previous SOTs; more details regarding the full process design can be found in the 2015 design report. The conversion pathway presented in this report includes the gasification of biomass, steam reforming and cleanup of the syngas, followed by the conversion of the syngas to HOG via methanol and dimethyl-ether (DME) intermediates. Research efforts in 2020 included the collection of experimental results over a variety of isobutane (iC4) to DME ratios in the feed of the DME-to-HOG reactor, enabling the TEA to identify the effect on modeled product yield and cost. Additionally, a significant re-build of the Aspen Plus model allowed for better integration of new research, however underlying conceptual and economic assumptions remain the same as those detailed in the 2015 deign report. The 2020 SOT also considers the potential for federal carbon tax credits from CO 2 capture in the acid-gas removal step and the impact on the final minimum fuel selling price.

09 BIOMASS FUELS↗