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At least 325 records · Page 18

Application of biocatalysts to Space Station ECLSS and PMMS water reclamation

Immobilized enzyme reactors have been developed and tested for potential water reclamation applications in the Space Station Freedom Environmental Control and Life Support System (ECLSS) and Process Materials Management System (PMMS). The reactors convert low molecular weight organic contaminants found in ECLSS and PMMS wastewaters to compounds that are more efficiently removed by existing technologies. Demonstration of the technology was successfully achieved with two model reactors. A packed bed reactor containing immobilized urease was found to catalyze the complete decomposition of urea to by-products that were subsequently removed using conventional ion exchange results. A second reactor containing immobilized alcohol oxidase showed promising results relative to its ability to convert methanol and ethanol to the corresponding aldehydes for subsequent removal. Preliminary assessments of the application of biocatalysts to ECLSS and PMMS water reclamation sytems are presented.

Jolly, Clifford D.↗

Liquid Methane/Liquid Oxygen Injectors for Potential Future Mars Ascent Engines

Preliminary mission studies for human exploration of Mars have been performed at Marshall Space Flight Center (MSFC). These studies indicate that for chemical rockets only a cryogenic propulsion system would provide high enough performance to be considered for a Mars ascent vehicle. Although the mission is possible with Earth-supplied propellants for this vehicle, utilization of in-situ propellants is highly attractive. This option would significantly reduce the overall mass of launch vehicles. Consequently, the cost of the mission would be greatly reduced because the number and size of the Earth launch vehicle(s) needed for the mission would decrease. NASA/Johnson Space Center has initiated several concept studies of in-situ propellant production plants. Liquid oxygen (LOX) is the primary candidate for an in-situ oxidizer. In-situ fuel candidates include methane (CH4), ethylene (C2H4), and methanol (CH3OH). MSFC initiated a technology development program for a cryogenic propulsion system for the Mars human exploration mission in 1998. One part of this technology program is the effort described here: an evaluation of propellant injection concepts for a LOX/liquid methane Mars Ascent Engine (MAE) with an emphasis on light-weight, high efficiency, reliability, and thermal compatibility. In addition to the main objective, hot-fire tests of the subject injectors will be used to test other key technologies including light-weight combustion chamber materials and advanced ignition concepts. This paper will address the results of the liquid methane/LOX injector study conducted at MSFC. A total of four impinging injector configurations were tested under combustion conditions in a modular combustor test article (MCTA), equipped with optically accessible windows. A series of forty hot-fire tests, which covered a wide range of engine operating conditions with the chamber pressure varied from 320 to 510 and the mixture ratio from 1.5 to 3.5, were performed. The test matrix also included a variation in the combustion chamber length for the purpose of investigating its effects on the combustion performance and stability.

Trinh, Huu Phuoc↗

Effects of temperature and time on supercritical methanol Co-Liquefaction of rice straw and linear low-density polyethylene wastes

We report that biofuels are particularly attractive and play an increasingly important role in sustainable energy. However, biofuels originating from lignocellulosic biomass (LCB) are extremely challenging because of their low carbon content, low stability, and high oxygen content. This work evaluates the supercritical methanol (scMeOH) co-liquefaction of rice straw and linear low-density polyethylene (LLDPE) at temperature range of 240-340 °C for 0-2 h, to obtain hydrocarbons (HCs)-rich oil and carbon-rich solid product. Results show that reaction temperature dominated the yield and properties of products, but not the holding time. Among parameters tested, 30.07 wt% oil yield with 75.79% HCs content and 33.05 wt% oil yield with 70.91% HCs content were obtained at 300 °C for 1 h and 1.5 h, respectively. Simultaneously, the remaining solid products were still as high as 53.85 wt% with a carbon content of 79.59% and 48.28 wt% with carbon content of 81.34% under 300 °C for 1 h and 1.5 h, respectively. Ultimate analysis, FT-IR, TGA, and SEM show that solid products could be used as sustainable carbon resources, and solid fuel rather than soil amendment because of risk of micro plastic or adsorbent due to smooth surface without pores.

09 BIOMASS FUELS↗

The Evolution of Volatile Production in Comet C-2009 P1(Garradd) During its 2011-2012 Apparition

We report observations at millimeter and submillimeter wavelengths of comet C/2009 P1 (Garradd) from 2011 December 28 to 2012 April 24, using the Arizona Radio Observatory submillimeter telescope (SMT) and the James Clerk Maxwell Telescope (JCMT). Garradd is a dynamically young long-period comet from the Oort Cloud, with a periodicity of 127,000 years, that reached perihelion on 2011 December 23 (at Heliocentric distance (Rh) = 1.55 Astronomical Units and delta = 20.1 Astronomical Units ) and made its closest approach to the Earth on 2012 March 05 (at Heliocentric distance (Rh) = 1.84 Astronomical Units and delta = 1.26 Astronomical Units). We obtained gas production rates, and molecular abundances relative to water for HCN, ortho-H2CO, CS, CO and CH3OH. A rotational temperature, T (sub rot) approximately equal to 50 degrees Kelvin, was determined by observing multiple methanol lines with the JCMT. By averaging the abundance ratio relative to water from the SMT and the JCMT we derive: CO: 7.03 plus or minus 1.84 percent, HCN: 0.04 plus or minus 0.01 percent, ortho H2CO: 0.14 plus or minus 0.03 percent as a parent molecule (and 0.28 plus or minus 0.06 percent as an extended source), CS: 0.03 plus or minus 0.01 percent and CH3OH: 3.11 for a range from plus 1:86 to minus 0.51 percent. We concluded that Garradd is normal in CH3OH, depleted in HCN, ortho-H2CO and CS and slightly enriched in CO with respect to typically observed cometary mixing ratios. We also studied the temporal evolution of HCN and CO and find that the production of HCN has a trend similar to water (but with short-term variation), with a decrease after perihelion, while that of CO shows contrary behavior: remaining constant or increasing after perihelion.

Comets: individual↗

Methanol to aromatics: isolated zinc phosphate groups on HZSM-5 zeolite enhance BTX selectivity and catalytic stability

HZSM-5 zeolite combined with unique zinc and phosphorus species, yields excellent selectivity (~85%) to BTX (benzene, toluene, xylenes) in aromatic products. It was found that both zinc and phosphorus species were highly distributed in the pores of the zeolite channel network to form isolated zinc phosphate groups, which directly bond to the surface of zeolite, leading to a strong Lewis acidic center and an optimized surface acidity distribution favorable for BTX formation and the hydrothermal stability of the catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical identity of carbon substrates drives differences in denitrification and N 2 O reduction within agricultural soils

Rates of nitrous oxide (N 2 O) production from agricultural soils are highly variable across space and time. Improving predictions of N 2 O emissions will require improving our understanding of the drivers of denitrification and the sources of variability in the rates of N 2 O production between soils and over time. While the amount of available carbon (C) is a known control on denitrification and N 2 O reduction, relatively little attention has been paid to the effect of the chemical identity of C substrates on rates of denitrification and N 2 O reduction. We investigated the effects of twelve different C-substrate additions on the production and reduction of N 2 O in five soils taken from two distinct agricultural locations in Michigan under multiple land uses. We provided additions of glucose, cellulose, N-acetyl-glucosamine, chitin, amino acids, protein, vanillyl alcohol, lignin, citrate, succinate, methanol, and water in laboratory denitrification potential assays to determine the effects of denitrifier C preference on denitrification rates. We found that amino acids, protein, and organic acids stimulated the greatest rates of denitrification potential across all land uses. Similarly, we found these same substrates caused the most N 2 O reduction, resulting in the lowest net concentrations of N 2 O. Soils from agricultural rotations without cover crops had overall lower rates of denitrifier activity, leading to less net N 2 O production compared to soils from other land uses. In general, C-utilization patterns were similar among all soils, and C-substrate identity had a much stronger effect than land use. Here, we demonstrate that the chemical identity of available C gives rise to wide variability in rates of denitrification and N 2 O reduction.

60 APPLIED LIFE SCIENCES↗

Pairing Ga/Al-Zeolites with tailored acidity as tandem catalysts for the conversion of alcohols to olefins

Zeolites are versatile catalysts owing to their tunable acidity where the active site(s) can be placed within the crystal framework or as extra-framework species in confined pores. A common approach to tailor Brønsted acidity is heteroatom exchange involving the replacement of framework aluminum with alternative elements. Introduction of heteroatoms often results in less acidic catalysts that can be used in tandem reactions for targeted reactive intermediates. Here, in this study, we prepare a series of three different zeolites with MWW, CHA, and MFI frameworks as aluminosilicates and gallosilicates to demonstrate their performance in alcohol dehydration reactions. The two reactions examined in this study are methanol conversion to dimethyl ether and ethanol conversion to ethylene. Our findings reveal that Ga-zeolites exhibit superior performance with Ga-MCM-22 (MWW) achieving nearly 100% alcohol conversion and selectivity to desired products at contact times that are significantly less than most dehydration catalysts reported in literature. The unique properties of Ga-zeolites are attributed to their reduced acid site strength via a direct (one-pot) synthesis that avoids conventional time-intensive, multi-step post-synthesis modifications of Al-zeolites. Here we demonstrate the use of Ga-zeolites as tandem catalysts when paired with a downstream Al-zeolite in a dual-bed reactor configuration to convert cheaper reagents (alcohols) upstream to more desired intermediates as feeds for downstream catalysts to produce light olefins. We demonstrate that dual beds using Ga-zeolite – Al-ZSM-5 (upstream–downstream) pairings outperform single bed configurations with Al-ZSM-5 or a physical mixture (Ga-/Al-zeolite) for methanol to hydrocarbons reactions, with notable improvements in catalyst lifetime and increased light olefins selectivity. Similarly, dual beds using Ga-zeolite – Al-SSZ-13 (upstream–downstream) pairings result in improved performance for ethanol to propylene reactions with significant increases in propylene selectivity (>20 %) compared to a conventional single bed configuration of Al-SSZ-13. Overall, this study offers a new perspective on the use of heteroatom-exchanged zeolite catalysts in tandem reactions as a means of capitalizing on their reduced acid site strength and suggests differences in the intrinsic acidity of zeolite crystal structures.

42 ENGINEERING↗

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↗

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↗