Variation of spontaneous ignition delays with temperature and composition for propane-oxygen-nitrogen mixtures at atmospheric pressure
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Rate constants of 15 OH reactions with halogen-substituted alkanes, C1 to C3, were studied using a relative rate technique in the temperature range 283-403 K. Compounds studied were CHF2Cl (22), CHF2Br (22B), CH3F (41), CH2F2 (32), CHF3 (23), CHClFCCl2F (122a), CHCl2CF3 (123), CHClFCF3 (124), CH3CF3 (143a), CH3CH2F (161), CF3CHFCF3 (227ea), CF3CH2CF3 (236fa), CF3CHFCHF2 (236ea), and CHF2CF2CH2F (245ca). Using CH4, CH3CCl3, CF3CF2H, and C2H6 as primary reference standards (JPL 92-20 rate constants), absolute rate constants are derived. Results are in good agreement with previous experimental results for six of the compounds studied, including CHF2Cl, CHF2Br, CH2F2, CH3CF3, CHFClCFCl2, and CF3CHFCF3. For the remainder the relative rate constants are lower than those derived from experiments in which OH loss was used to measure the reaction rate. Comparisons of the derived Arrhenius A factors with previous literature transition-state calculations show order of magnitude agreement in most cases. However, the experimental A factors show a much closer proportionality to the number of H atoms in the molecule than is evident from the transition state calculations. For most of the compounds studied, an A factor of (8 +/- 3)E-13 cm(exp 3)/(molecule s) per C-H bond is observed. A new measurement of the ratio k(CH3CCl3)/k(CH4) is reported that is in good agreement with previous data.
A method of surface flow visualization for use in cryogenic wind tunnels is described which requires injection of a cryogenic liquid onto the model while the tunnel is running. This necessitates the use of a substance that remains liquid over a large range of cryogenic wind tunnel operating temperatures. It is found that propane (C3H8) is a suitable substance. Experiments are conducted in a subsonic cryogenic wind tunnel to assess the practical application of liquid propane flow visualization. The propane is stored in a chamber cooled by liquid nitrogen and when required is pumped through pipes to a gallery inside the model and then out onto the surface through small holes. To color the liquid a suspension of pigment particles is used. Propane is supplied to the cooled chamber in gaseous form from a standard liquefied gas cylinder. The sequence of events is illustrated on a propane temperature-entropy diagram. The use of liquefied propane for flow visualization in a cryogenic tunnel operating at pressures up to 40 atm appears to be feasible. Illustrative examples are provided.
This is the final report in a study examining the impact of launch vehicles for various boost propulsion design options. These options included: differing boost phase engines using different combinations of fuels and coolants to include RP-1, methane, propane (subcooled and normal boiling point), and hydrogen; variable and high mixture ratio hydrogen engines; translating nozzles on boost phase engines; and cross feeding propellants from the booster to second stage. Vehicles examined included a fully reusable two stage cargo vehicle and a single stage to orbit vehicle. The use of subcooled propane as a fuel generated vehicles with the lowest total vehicle dry mass. Engines with hydrogen cooling generated only slight mass reductions from the reference, all-hydrogen vehicle. Cross feeding propellants generated the most significant mass reductions from the reference two stage vehicle. The use of high mixture ratio or variable mixture ratio hydrogen engines in the boost phase of flight resulted in vehicles with total dry mass 20 percent greater than the reference hydrogen vehicle. Translating nozzles for boost phase engines generated a heavier vehicle. Also examined were the design impacts on the vehicle and ground support subsystems when subcooled propane is used as a fuel. The most significant cost difference between facilities to handle normal boiling point versus subcooled propane is 5 million dollars. Vehicle cost differences were negligible. A significant technical challenge exists for properly conditioning the vehicle propellant on the ground and in flight when subcooled propane is used as fuel.
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 811 K. Results indicated that substantial deposit formation occurs with RP-1 fuel at wall temperatures between 600 and 800 K, with peak deposit formation occurring near 700 K. No improvements were obtained when deoxygenated 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. 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, lating the inside wall of the tubes with nickel was found to significantly reduce carbon deposition rates for RP-1 fuel.
The isothermal transmission through activated carbon adsorber beds at 25 C of acetaldehyde-propane and acetylene-ethane mixtures in a helium carrier gas was measured. The inlet concentration of each component was in the range between 10 ppm and 500 ppm. The constant inlet volumetric flow rate was controlled at 200 cc (STP)/min in the acetaldehyde-propane experiments and at 50 cc (STP)/min in the acetaldehyde-ethane experiments. Comparison of experimental results with the corresponding single-component experiments under similar conditions reveals interference phenomena between the components of the mixtures as evidenced by changes in both the adsorption capacity and the dispersion number. Propane was found to displace acetaldehyde from the adsorbed state. The outlet concentration profiles of propane in the binary mixtures tend to become more diffuse than the corresponding concentration profiles of the one-component experiments. Similar features were observed with mixtures of acetylene and ethane; however, the displacement of acetylene by ethane is less pronounced.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
An igniter is described mounted on a vent stack with an upper, flame cage near the top of the stack to ignite emissions from the stack. The igniter is a tube with a lower, open, flared end having a spark plug near the lower end and a solenoid-controlled valve which supplies propane fuel from a supply tank. Propane from the tank is supplied at the top under control of a second, solenoid-controlled valve. The valve controlling the lower supply is closed after ignition at the flame cage. The igniter is economical, practical, and highly reliable.