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At least 163 records · Page 9

Deposit formation in hydrocarbon rocket fuels: Executive summary

An experimental program was conducted to study deposit formation in hydrocarbon fuels under flow conditions that exist in high-pressure, rocket engine cooling systems. A high pressure fuel coking test apparatus was designed and developed and was used to evaluate thermal decomposition (coking) limits and carbon deposition rates in heated copper tubes for two hydrocarbon rocket fuels, RP-1 and commercial-grade propane. Tests were also conducted using JP-7 and chemically-pure propane as being representative of more refined cuts of the baseline fuels. A parametric evaluation of fuel thermal stability was performed at pressures of 136 atm to 340 atm, bulk fuel velocities in the range 6 to 30 m/sec, and tube wall temperatures in the range 422 to 811K. In addition, the effect of the inside wall material on deposit formation was evaluated in selected tests which were conducted using nickel-plated tubes. The results of the tests indicated that substantial deposit formation occurs with RP-1 fuel at wall temperatures between 600 and 800K, with peak deposit formation occurring near 700K. No improvements were obtained when de-oxygenated JP-7 fuel was substituted for RP-1. The carbon deposition rates for the propane fuels were generally higher than those obtained for either of the kerosene fuels at any given wall temperature. There appeared to be little difference between commercial-grade and chemically-pure propane with regard to type and quantity of deposit. The results of tests conducted with RP-1 indicated that the rate of deposit formation increased slightly with pressure over the range 136 atm to 340 atm. Finally, plating the inside wall of the tubes with nickel was found to significantly reduce carbon deposition rates for RP-1 fuel.

Roback, R.↗

Deposit formation and heat transfer in hydrocarbon rocket fuels

An experimental research program was undertaken to investigate the thermal stability and heat transfer characteristics of several hydrocarbon fuels under conditions that simulate high-pressure, rocket engine cooling systems. The rates of carbon deposition in heated copper and nickel-plated copper tubes were determined for RP-1, propane, and natural gas using a continuous flow test apparatus which permitted independent variation and evaluation of the effect on deposit formation of wall temperature, fuel pressure, and fuel velocity. In addition, the effects of fuel additives and contaminants, cryogenic fuel temperatures, and extended duration testing with intermittent operation were examined. Parametric tests to map the thermal stability characteristics of RP-1, commercial-grade propane, and natural gas were conducted at pressures of 6.9 to 13.8 MPa, bulk fuel velocities of 30 to 90 m/s, and tube wall temperatures in the range of 230 to 810 K. Also, tests were run in which propane and natural gas fuels were chilled to 230 and 160 K, respectively. Corrosion of the copper tube surface was detected for all fuels tested. Plating the inside of the copper tubes with nickel reduced deposit formation and eliminated tube corrosion in most cases. The lowest rates of carbon deposition were obtained for natural gas, and the highest rates were obtained for propane. For all fuels tested, the forced-convection heat transfer film coefficients were satisfactorily correlated using a Nusselt-Reynolds-Prandtl number equation.

Giovanetti, A. J.↗

Studies of the kinetics and mechanisms of perfluoroether reactions on iron and oxidized iron surfaces

Polymeric perfluoroalkylethers are being considered for use as lubricants in high temperature applications, but have been observed to catalytically decompose in the presence of metals. X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD) were used to explore the decomposition of three model fluorinated ethers on clean polycrystalline iron surfaces and iron surfaces chemically modified with oxygen. Low temperature adsorption of the model fluorinated ethers on the clean, oxygen modified and oxidized iron surfaces was molecular. Thermally activated defluorination of the three model compounds was observed on the clean iron surface at remarkably low temperatures, 155 K and below, with formation of iron fluoride. Preferential C-F bond scission occurred at the terminal fluoromethoxy, CF3O, of perfluoro-1-methoxy-2-ethoxy ethane and perfluoro-1-methoxy-2-ethoxy propane and at CF3/CF2O of perfluoro-1,3-diethoxy propane. The reactivity of the clean iron toward perfluoroalkylether decomposition when compared to other metals is due to the strength of the iron fluoride bond and the strong electron donating ability of the metallic iron. Chemisorption of an oxygen overlayer lowered the reactivity of the iron surface to the adsorption and decomposition of the three model fluorinated ethers by blocking active sites on the metal surface. Incomplete coverage of the iron surface with chemisorbed oxygen results in a reaction which resembles the defluorination reaction observed on the clean iron surface. Perfluoro-1-methoxy-2-ethoxy ethane reacts on the oxidized iron surface at 138 K, through a Lewis acid assisted cleavage of the carbon oxygen bond, with preferential attack at the terminal fluoromethoxy, CF3O. The oxidized iron surface did not passivate, but became more reactive with time. Perfluoro-1-methoxy-2-ethoxy propane and perfluoro-1,3-diethoxy propane desorbed prior to the observation of decomposition on the oxidized iron surface.

Napier, Mary E.↗

Direct Conversion of CO 2 to Olefins over a Cr 2 O 3 /ZSM-5@CaO Cooperative and Bifunctional Material Under Isothermal Conditions

Direct conversion of point-source CO 2 into fine chemicals over cooperative and bifunctional materials (BFMs) – composed of adsorbents and catalysts – has emerged as a promising approach to improve the energy efficiency of the carbon capture and conversion processes. In this study, a bifunctional material consisting of Cr 2 O 3 /ZSM-5 catalyst and CaO adsorbent was developed and tested in the CO 2 -oxidative dehydrogenation of propane (CO 2 –ODHP) for reactive capture of CO 2 in a fixed bed reactor. First, CaO was prepared using two distinct methods: solid-state and citrate sol–gel. The citrate sol–gel method resulted in small and finely-distributed CaO particles, allowing more accessible sites for CO 2 adsorption. Consequently, a high CO 2 adsorption capacity of ~14 mmol/g was achieved with fast adsorption kinetics compared to CaO prepared by the solid-state method. The CaO adsorbent was then combined with the Cr 2 O 3 /ZSM-5 catalyst for BFM synthesis and tested in the CO 2 –ODHP process, targeting propylene production. The BFM was extensively characterized to provide insights into the BFM’s surface chemistry, morphology, and reaction mechanism in the reactive capture process of CO 2 –ODHP. The results revealed that under isothermal adsorption–reaction conditions at 600 °C, a propane conversion of 22.5%, a propylene selectivity of 55.3%, and an olefin selectivity of 67.3% were achieved. The excellent propylene selectivity was attributed to the catalyst acidity and redox property of the Cr 2 O 3 /ZSM-5 catalyst, which facilitated the reaction pathway of propane dehydrogenation in the process of CO 2 –ODHP. Overall, this study renders Cr 2 O 3 /ZSM-5@CaO as promising BFMs with high CO 2 capture capacity and catalytic activity for integrated CO 2 capture and conversion in the ODHP reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Autoignition Delay Time Measurements of Dimethyl Ether at 110 Bar Inside a Shock Tube

Fuel mixtures of propane and dimethyl ether have been proposed as potential diesel substitutes for use in compression-ignition engines. There is an interest in phasing out diesel fuel because its combustion byproducts are harmful to the environment. Propane and dimethyl ether burn cleaner and produce significantly less carbon dioxide than diesel. The combustion of these fuels at engine-relevant conditions must be characterized to create an engine capable of running on propane and dimethyl ether. In this work, IDT measurements of stoichiometric neat DME diluted in 75% argon were completed for temperatures spanning 800-1200K at 110 bar. A shock tube will be used for all experiments in this work. Experimental IDTs were then compared to simulated values using several well-established mechanisms in the literature.

Guenther, Aaron C. [University of Central Florida]↗

Characterization of Multiple Trichloroethene, cis-Dichloroethene and 1,1-Dichloroethene Degrading Propanotrophic Communities

Aerobic cometabolism offers a viable strategy for the remediation of chlorinated solvent plumes at oxic sites where anaerobic approaches are limited. In this study, propane-enriched mixed cultures (derived from agricultural soils and an impacted site sediment) which previously degraded 1,4-dioxane, were evaluated for their capacity to also degrade trichloroethene (TCE), cis-1,2-dichloroethene (cDCE), and 1,1-dichloroethene (1,1-DCE) over successive transfers. Sustained biodegradation of TCE and cDCE was observed across multiple enrichments, and cultures enriched on one compound generally degraded the other. In contrast, 1,1-DCE biodegradation was restricted to a subset of cultures and removal times increased over transfers. Further, 1,1-DCE removal was absent at elevated concentrations, both trends consistent with inhibitory or toxic effects. Whole genome sequencing analyses revealed pronounced substrate-dependent selection of microbial communities, with cDCE-degrading cultures being dominated by Mycobacterium and Mycolicibacterium, whereas TCE-degrading cultures were dominated by Rhodococcus. Rhodococcus metagenome-assembled genomes (MAGs) in the TCE degrading cultures classified as R. opacus or R. wratislaviensis. 1,1-DCE degrading cultures were dominated by Pseudonocardia, although the associated MAGs contained a truncated propane monooxygenase alpha subunit. Functional gene analysis identified both group 5 (prmABCD) and putative group 6 propane monooxygenases. The following KBase narratives contain the quality controlled reads, MAGs (fasta assemblies) and the prokka annotations for each assembly TCE Site 1A and B Propanotrophic MAGs (https://narrative.kbase.us/narrative/254918) TCE Soil 2A and B Propanotrophic MAGs (https://narrative.kbase.us/narrative/254919) TCE Soil T3 A and B Propanotrophic MAGs (https://narrative.kbase.us/narrative/254920) TCE Soil T4 A and B Propanotrophic MAGs (https://narrative.kbase.us/narrative/254921) cDCE Site 1A 1B Propanotrophic MAGs (https://narrative.kbase.us/narrative/254915) cDCE Soils T2 A and B Propanotrophic MAGs (https://narrative.kbase.us/narrative/254927) cDCE Soil T3 A and B Propanotrophic MAGs (https://narrative.kbase.us/narrative/254928) cDCE Soil 4A and B Propanotrophic MAGs (https://narrative.kbase.us/narrative/254942) 1,1-DCE T2 T3 Propanotrophic MAGs (https://narrative.kbase.us/narrative/254903)

59 BASIC BIOLOGICAL SCIENCES↗

A Modeling-Based Flammable Risk Treatment of Refrigerant Leakage from a Commercial R-290 Refrigeration Machine

Because of serious concerns about global warming, manufacturers have started phasing out high global warming potential (GWP) refrigerants in commercial refrigeration equipment (e.g., R-134a). As a potential replacement, propane (R-290) is an environmentally friendly refrigerant for commercial refrigeration equipment because its GWP is only three. However, propane is flammable and is therefore classified as a Class A3 refrigerant per ASHRAE Standards, so safety is a very important consideration when propane-based equipment is designed and deployed in buildings. In the event of a refrigerant leak, flammability of the refrigerant depends on the refrigerant’s local concentration, which is highly affected by the indoor air environment, including temperature and air flow. In this study, a ventilation system attached to a commercial R-290 refrigeration device was designed to eliminate the flammability risk. Moreover, a computational fluid dynamics (CFD) model was developed to investigate the refrigerant leak, thereby evaluating effects of the ventilation system. The CFD model can visualize the flammable zones owing to the leak.

42 ENGINEERING↗

Effect of fuel nitrogen and hydrogen content on emissions in hydrocarbon combustion

How the emissions of nitrogen oxides and carbon monoxide are affected by: (1) the decreased hydrogen content and (2) the increased organic nitrogen content of coal derived fuels is investigated. Previous CRT experimental work in a two stage flame tube has shown the effectiveness of rich lean two stage combustion in reducing fuel nitrogen conversion to nitrogen oxides. Previous theoretical work gave preliminary indications that emissions trends from the flame tube experiment could be predicted by a two stage, well stirred reactor combustor model using a detailed chemical mechanism for propane oxidation and nitrogen oxide formation. Additional computations are reported and comparisons with experimental results for two additional fuels and a wide range of operating conditions are given. Fuels used in the modeling are pure propane, a propane toluene mixture and pure toluene. These give hydrogen contents 18, 11 and 9 percent by weight, respectively. Fuel bound nitrogen contents of 0.5 and 1.0 percent were used. Results are presented for oxides of nitrogen and also carbon monoxide concentrations as a function of primary equivalence ratio, hydrogen content and fuel bound nitrogen content.

Bittker, D. A.↗

Advanced oxygen-hydrocarbon Earth-to-orbit propulsion

Liquid oxygen/hydrocarbon (LO2/HC) rocket engine cycles for a surface to orbit transportation system were evaluated. A consistent engine system data base is established for defining advantages and disadvantages, system performance and operating limits, engine parametric data, and technology requirements for candidate engine systems. Preliminary comparisons of the engine cycles utilizing delivered specific impulse values are presented. Methane and propane staged combustion cycles are the highest LO2/HC performers. The hydrogen cooled LO2/methane dual throat engine was found to be the highest performing. Technology needs identified in the study include: high temperature turbines; oxidizer-rich preburners; LO2, methane, and propane cooling; methane and propane fuel-rich preburners; the HC fuel turbopump; and application of advanced composite materials to the engine system. Parametric sensitivity analysis data are displayed which show the effect of variations in engine thrust, mixture ratio, chamber pressure, area ratio, cycle life, and turbine inlet temperature on specific impulse and engine weight.

Obrien, C. J.↗

Effect of storable propellants on single-stage earth-to-orbit vehicles

A comparison is made between the storable-propellant engine and an equivalent dual-expander engine using oxygen, propane, and hydrogen propellants. The propane and hydrogen dual-expander engine is then compared with previous results with separate propane and hydrocarbon engines. It is shown that the dual-expander reduces vehicle dry mass from 94 to 89 Mg, or 5%. The hydrogen-only thrust of the dual-expander is 0.4 MN, while the separate hydrogen engines have a thrust of 2.3 MN. The low thrust level increases the difficulty of cooling the dual-expander engine, and additional hydrogen flow is added for transpirational cooling. This additional hydrogen flow leads to an increase in the hydrogen tank size. It is also shown that storable propellants increase the dry mass of single-stage earth-to-orbit vehicles by about 20% and the gross mass by about 54%. It is concluded that dual-expander engines should be studied with several thrust splits and thrust levels.

Martin, J. A.↗

Deposit formation in hydrocarbon fuels

The hydrocarbon fuels RP-1, commercial-grade propane, JP-7 and chemically pure propane were subjected to tests in a high pressure fuel coking apparatus in order to evaluate their thermal decomposition limits and carbon deposition rates in heated copper tubes. A fuel thermal stability parametric evaluation was conducted at 136-340 atmospheres, bulk fuel velocities of 6-30 m/sec, and tube wall temperatures of 422-811 K, and the effect of inside wall material on deposit formation was evaluated in tests using nickel-plated tubes. Results show RP-1 deposit formation at wall temperatures between 600 and 800 K, with peak deposit formation near 700 K. Substitution of deoxygenated JP-7 for RP-1 showed no improvement, and the carbon deposition rates for propane fuels were found to be higher than those of either of the kerosene fuels. Nickel plating of the tube walls significantly reduced RP-1 carbon deposition rates.

Roback, R.↗

The mechanisms of flame holding in the wake of a bluff body

The flame holding mechanism for lean methane- and lean propane-air flames is examined under conditions where the recirculation zone is absent. The main objective of this work is to study the holding process in detail in an attempt to determine the mechanism of flame holding and also the conditions where this mechanism is viable and when it fails and blow-off occurs. Inverted flames held in the wake of a flat strip were studied. Experiments with different sizes of flame holders were performed. The velocity flow field was determined using a laser Doppler velocimetry technique. Equation of continuity was used to calculate the flame temperature from the change in area of flow streamlines before and after the flame. Observations of the inverted flame itself were obtained using schlieren and direct photography. Results show that there are different mechanisms operative at the time of blow-off for lean propane and methane flames. Blow-off or extinction occurs for lean propane-air flame in spite of the reaction going to completion and the disparity between the heat loss and the gain in mass diffusion in the reaction zone i.e., Le 1.0 causes the flame to blow-off. For methane-air flame the controlling factor or blow-off is incomplete reaction due to higher blowing rate leading to reduced residence time in the reaction zone.

Strehlow, R. A.↗

High Energy, Low Temperature Gelled Bi-propellant Formulation Preparation Method

A method for preparing a gelled liquid propane (GLP) composition comprises the introduction of liquid propane into an evacuated mixing vessel containing a gellant and mixing the liquid propane with the gellant. A bi-propellant system comprising GLP is particularly well-suited for outer planet missions greater than 3 AU from the sun and also functions in earth and near earth environments. Additives such as powders of boron, carbon, lithium, and/or aluminum can be added improve performance or enhance hypergolicity. The gelling agent can be silicon dioxide, clay, carbon, or organic or inorganic polymers. The bi-propellant system may be, but need not be, hypergolic.

DiSalvo, Roberto↗

Development of a Two-Stage Mars Ascent Vehicle Using In-Situ Propellant Production

Mars Sample Return (MSR) and Mars In-Situ Resource Utilization (ISRU) present two main challenges for the advancement of Mars science. MSR would demonstrate Mars lift-off capability, while ISRU would test the ability to produce fuel and oxidizer using Martian resources, a crucial step for future human missions. A two-stage Mars Ascent Vehicle (MAV) concept was developed to support sample return as well as in-situ propellant production. The MAV would be powered by a solid rocket first stage and a LOX-propane second stage. A liquid second-stage provides higher orbit insertion reliability than a solid second stage as well as a degree of complexity eventually required for manned missions. Propane in particular offers comparable performance to methane without requiring cryogenic storage. The total MAV mass would be 119.9 kg to carry an 11 kg payload to orbit. The feasibility of in-situ fuel and oxidizer production was also examined. Two potential schemes were evaluated for production capability, size and power requirements. The schemes examined utilize CO2 and water as starting blocks to produce LOX and a propane blend. The infrastructure required to fuel and launch the MAV was also explored.

Paxton, Laurel↗

Technoeconomic Analysis of a Microwave-Assisted Novel Process That Converts Polypropylene Plastic Waste to Propylene

Propylene is an important petrochemical that is used in various industries, including the automobile and polymer sectors. Conventionally, propylene has been produced through fluid catalytic cracking, steam cracking, and propane dehydrogenation. In this project, a novel process to produce propylene from polypropylene plastic waste using a microwave reactor is introduced. Propylene production is simulated in Aspen Plus for both the conventional propane dehydrogenation process and the novel design, with heat integration applied to minimize utility demands and the conventional process serving as the base case for comparison. Finally, a tailored technoeconomic analysis is carried out for both simulated cases to estimate important economic indicators. Analysis of the results shows that the novel microwave-assisted process outperforms the conventional route for propylene production, achieving a single-pass conversion of almost 100%, compared with only 33.8% in the conventional plant. The Net Present Value of the novel plant is $\$1720.3$ MM, which is 3.5 times higher than the conventional process, while the Levelized Cost of Propylene is reduced by 40%. Capital and operating expenditure are also improved in the proposed scheme, with reductions of approximately $\$29$ MM and $\$222$ MM/yr, respectively. In addition to cost savings, this novel process also provides a convenient means to recycle waste polypropylene.

42 ENGINEERING↗

Elucidating the Competitive Hydrodeoxygenation of Lignin-Derived Oxygenates over Bulk MoO 3 Catalyst through Kinetic Analysis

Ambient pressure hydrodeoxygenation (HDO) of lignin-derived oxygenates over molybdenum oxide-based catalysts is an effective strategy to produce chemicals that can be directly integrated into our existing petrochemical infrastructure. Complexities pertaining to the simultaneous kinetic and mechanistic analysis of HDO have limited research endeavors to single-compound systems. Although valuable insight into the catalytic reaction has been gained through this approach, it provides limited understanding of the competitive adsorption behavior manifest in a realistic multioxygenate reaction environment. To address this shortcoming, simultaneous gas-phase acetone and anisole HDO was performed at 330 °C and ≤1 bar H 2 partial pressure over bulk MoO 3 . Propene, propane, and benzene were the HDO products formed, showing a similar product distribution to the single-compound system. Selectivity to propene and propane was ∼14 times higher than benzene, even at three times higher anisole partial pressure compared to acetone. A negative anisole HDO (−0.97 ± 0.22) rate order with varying acetone partial pressure suggested a strong inhibition effect on anisole HDO by acetone. Conversely, with increasing anisole partial pressure, a rate order of −0.07 ± 0.12 was observed for acetone HDO, implying a weak impact of anisole cofeed on acetone HDO. A kinetic-driven approach was taken to estimate the relative adsorption constants of the oxygenates. Acetone exhibited a 6.4 times higher adsorption propensity on the HDO active site than anisole. Relative adsorption constants for phenolics increased with increasing basicity of the oxygenate but decreased for aliphatic molecules, suggesting a volcano-shaped relationship. The results suggest the possibility of an optimal electron density around the molecule’s oxygen atom to maximize the molecule’s adsorption strength.

acid sites↗

Chemically Amplified, Dry-Develop Poly(aldehyde) Photoresist

The catalytic decomposition of poly(phthalaldehyde) with a photoacid generator can be used as dry-develop photoresist, where the exposed film depolymerizes into small molecules to allow the development of features via controlled vaporization. Higher temperatures enabled shorter dry-development times, but also promoted faster photoacid diffusion that compromised pattern fidelity. Trihexylamine was used as a base quencher to counteract acid diffusion in a phthalaldehyde-propanal co-polymer photoresist. The propanal co-monomer in the polymer improves the vaporization rate because it has a higher vapor pressure than phthalaldehyde. Addition of the base quencher was found to improve the contrast, pattern fidelity, and ease-of-handling of the dry-develop resist in a direct-write UV lithography tool. The dry-development of 4 μ m features was achieved with no appreciable residue. For large area features, a spatially variable exposure method was used to direct the residue away from the exposed area. The gradient exposure method was used to produce 100 μ m features. Plasma etching after dry-development was also used to achieve residue-free dry-developed patterns. These results show the benefits of incorporating base additives into a dry-develop depolymerizable resist system and highlight the need for addressing residue formation.

Materials Science↗

End-Use Savings Shapes Measure Documentation: Economizers

Building on the successfully completed effort to calibrate and validate the U.S. Department of Energy's ResStock™ and ComStock™ models over the past 3 years, the objective of this work is to produce national data sets that empower analysts working for federal, state, utility, city, and manufacturer stakeholders to answer a broad range of analysis questions. The goal of this work is to develop energy efficiency, electrification, and demand flexibility end-use load shapes (electricity, gas, propane, or fuel oil) that cover a majority of the high-impact, market-ready (or nearly market-ready) measures. "Measures" refers to energy efficiency variables that can be applied to buildings during modeling. An end-use savings shape is the difference in energy consumption between a baseline building and a building with an energy efficiency, electrification, or demand flexibility measure applied. It results in a time-series profile that is broken down by end use and fuel (electricity or on-site gas, propane, or fuel oil use) at each time step. ComStock is a highly granular, bottom-up model that uses multiple data sources, statistical sampling methods, and advanced building energy simulations to estimate the annual subhourly energy consumption of the commercial building stock across the United States. The baseline model intends to represent the U.S. commercial building stock as it existed in 2018. The methodology and results of the baseline model are discussed in the final technical report of the End-Use Load Profiles project.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗