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Mars Atmospheric Conversion to Methane and Water: An Engineering Model of the Sabatier Reactor with Characterization of Ru/Al2O3 for Long Duration Use on Mars

The Atmospheric Processing Module (APM) is a Mars In-Situ Resource Utilization (ISRU) technology designed to demonstrate conversion of the Martian atmosphere into methane and water. The Martian atmosphere consists of approximately 95 carbon dioxide (CO2) and residual argon and nitrogen. APM utilizes cryocoolers for CO2 acquisition from a simulated Martian atmosphere and pressure. The captured CO2 is sublimated and pressurized as a feedstock into the Sabatier reactor, which converts CO2 and hydrogen to methane and water. The Sabatier reaction occurs over a packed bed reactor filled with Ru/Al2O3 pellets. The long duration use of the APM system and catalyst was investigated for future scaling and failure limits. Failure of the catalyst was detected by gas chromatography and temperature sensors on the system. Following this, characterization and experimentation with the catalyst was carried out with analysis including x-ray photoelectron spectroscopy and scanning electron microscopy with elemental dispersive spectroscopy. This paper will discuss results of the catalyst performance, the overall APM Sabatier approach, as well as intrinsic catalyst considerations of the Sabatier reactor performance incorporated into a chemical model.

Ru/Al2O3 Catlayst↗

Mars Atmospheric Conversion to Methane and Water: An Engineering Model of the Sabatier Reactor with Characterization of Ru/Al2O3 for Long Duration Use on Mars

The Atmospheric Processing Module (APM) is a Mars In-Situ Resource Utilization (ISRU) technology designed to demonstrate conversion of the Martian atmosphere into methane and water. The Martian atmosphere consists of approximately 95 carbon dioxide (CO2) and residual argon and nitrogen. APM utilizes cryocoolers for CO2 acquisition from a simulated Martian atmosphere and pressure. The captured CO2 is sublimated and pressurized as a feedstock into the Sabatier reactor, which converts CO2 and hydrogen to methane and water. The Sabatier reaction occurs over a packed bed reactor filled with Ru/Al2O3 pellets. The long duration use of the APM system and catalyst was investigated for future scaling and failure limits. Failure of the catalyst was detected by gas chromatography and temperature sensors on the system. Following this, characterization and experimentation with the catalyst was carried out with analysis including x-ray photoelectron spectroscopy and scanning electron microscopy with elemental dispersive spectroscopy. This paper will discuss results of the catalyst performance, the overall APM Sabatier approach, as well as intrinsic catalyst considerations of the Sabatier reactor performance incorporated into a chemical model.

Catlayst↗

The Search for Life on Mars

For centuries, the planet Mars has been regarded as a possible abode for life. Serious searches for the signatures of life began in the 19th century, and continue via telescopic investigations and landed missions. While early work focused on phenomenology and bordered on fantasy, modern scientific inquiry has emphasized the search for chemical signatures of life in the soil and rocks at the planet's surface, and the search for biomarker gases in the atmosphere. Living systems produce more than 90% of Earth's atmospheric methane; the balance is of geochemical origin. The discovery of methane on Mars will be described, along with the ongoing extended search for clues to its origins. The possible origins of Mars methane will be discussed in the context of terrestrial analogue sites where geologic and biologic methane production now occurs - ranging from sub-permafrost zones in the arctic to hydrothermal vents in the deep ocean. Terrestrial organisms that could prosper on Mars today will be mentioned. I will briefly touch upon experiments conducted by landed spacecraft, ranging from the Viking Life Science Experiments in 1976 to the impending Mars Science laboratory, and the Trace Gas Orbiter and ExoMars missions now being developed for flight in the coming decade.

Mumma, Michael J.↗

Status of Liquid Oxygen/Liquid Methane Injector Study for a Mars Ascent Engine

Preliminary mission studies for human exploration of Mars have been performed at Marshall Space Flight Center (MSFC). These studies indicate that for non-toxic 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 the return vehicle. 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 decrease. NASA/Johnson Space Center has initiated several concept studies (2) 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 state-of-the-art technology will then be applied to the development of a cryogenic propulsion system that will meet the requirements of the planned Mars sample return (MSR) mission. The current baseline propulsion system for the MSR mission uses a storable propellant combination [monomethyl hydrazine/mixed oxides of nitrogen-25(MMH/MON-25)]. However, a mission option that incorporates in-situ propellant production and utilization for the ascent stage is being carefully considered as a subscale precursor to a future human mission to Mars.

Trinh, Huu Ogyic↗

Methane Propulsion Elements for Mars

Human exploration beyond LEO relies on a suite of propulsive elements to: (1) Launch elements into space, (2) Transport crew and cargo to and from various destinations, (3) Provide access to the surface of Mars, (4) Launch crew from the surface of Mars. Oxygen/Methane propulsion systems meet the unique requirements of Mars surface access. A common Oxygen/Methane propulsion system is being considered to reduce development costs and support a wide range of primary & alternative applications.

Percy, Tom↗

Assessment of a 2016 Mission Concept: The Search for Trace Gases in the Atmosphere of Mars

The reported detection of methane in the atmosphere of Mars as well as its potentially large seasonal spatial variations challenge our understanding of both the sources and sinks of atmospheric trace gases. The presence of methane suggests ongoing exchange between the subsurface and the atmosphere of potentially biogenic trace gases, while the spatial and temporal variations cannot be accounted for with current knowledge of martian photochemistry. A Joint Instrument Definition Team (JIDT) was asked to assess concepts for a mission that might follow up on these discoveries within the framework of a series of joint missions being considered by ESA and NASA for possible future exploration of Mars. The following is based on the report of the JIDT to the space agencies (Zurek et al., 2009); a synopsis of the report was presented at the Workshop on Mars Methane held in Frascati, Italy, in November 2009. To summarize, the JIDT believed that a scientifically exciting and credible mission could be conducted within the evolving capabilities of the science/telecommunications orbiter being considered by ESA and NASA for possible launch in the 2016 opportunity for Mars.

Zurek, Richard W.↗

Impact Metamorphism of Subsurface Organic Matter on Mars: A Potential Source for Methane and Surface Alteration

Reports of methane in the Martian atmosphere have spurred speculation about sources for that methane [1-3]. Discussion has centered on cometary/ meteoritic delivery, magmatic/mantle processes, UV-breakdown of organics, serpentinization of basalts, and generation of methane by living organisms. This paper describes an additional possibility: that buried organic remains from past life on Mars may have been generating methane throughout Martian history as a result of heating associated with impact metamorphism.

Oehler, D. Z.↗

Carbon Dioxide Methanation for Human Exploration of Mars: A Look at Catalyst Longevity and Activity Using Supported Ruthenium

Overarching Purpose: To design a carbon dioxide methanation/Sabatier reaction catalyst able to withstand variable conditions including fluctuations in bed temperature and feed flow rates for 480 days of remote operation to produce seven tons of methane. Current Study Purpose: Examine supported Ruthenium as a carbon dioxide methanation catalyst to determine the effects support properties have on the active phase by studying activity and selectivity. Objective: The remote operation of the Mars ISRU (In Situ Resources Utilization) lander to produce rocket fuel prior to crew arrival on the planet to power an ascent vehicle. Constraints: Long-term operation (480 days); Variable conditions: Feed gas flow rates, Feed gas flow ratios, Reactor bed temperature.

SiC↗

Development of Augmented Spark Impinging Igniter System for Methane Engines

The Lunar Cargo Transportation and Landing by Soft Touchdown (Lunar CATALYST) program is establishing multiple no-funds-exchanged Space Act Agreement (SAA) partnerships with U.S. private sector entities. The purpose of this program is to encourage the development of robotic lunar landers that can be integrated with U.S. commercial launch capabilities to deliver payloads to the lunar surface. As part of the efforts in Lander Technologies, NASA Marshall Space Flight Center (MSFC) is developing liquid oxygen (LOX) and liquid methane (LCH4) engine technology to share with the Lunar CATALYST partners. Liquid oxygen and liquid methane propellants are attractive owing to their relatively high specific impulse for chemical propulsion systems, modest storage requirements, and adaptability to NASA's Journey to Mars plans. Methane has also been viewed as a possible propellant choice for lunar missions, owing to the performance benefits and as a technology development stepping stone to Martian missions. However, in the development of methane propulsion, methane ignition has historically been viewed as a high risk area in the development of such an engine. A great deal of work has been conducted in the past decade devoted to risk reduction in LOX/CH4 ignition. This paper will review and summarize the history and results of LOX/CH4 ignition programs conducted at NASA. More recently, a NASA-developed Augmented Spark Impinging (ASI) igniter body, which utilizes a conventional spark exciter system, is being tested with LOX/CH4 to help support internal and commercial engine development programs, such as those in Lunar CATALYST. One challenge with spark exciter systems, especially at altitude conditions, is the ignition lead that transmits the high voltage pulse from the exciter to the spark igniter (spark plug). The ignition lead can be prone to corona discharge, reducing the energy delivered by the spark and potentially causing non-ignition events. For the current work, a commercial compact exciter system, which eliminates this high voltage cabling, was tested at altitude conditions. A modified, conventional exciter system with an improved ignition lead was also recently tested at altitude conditions. This test program demonstrated the capability of these exciter systems to operate at altitude. While more extensive testing may be required, these systems or similar ones may be used for future NASA and commercial engine programs.

methane↗

Design and Development of a Methane Cryogenic Propulsion Stage for Human Mars Exploration

NASA is currently working on the Evolvabe Mars Campaign (EMC) study to outline transportation and mission options for human exploration of Mars. One of the key aspects of the EMC is leveraging current and planned near-term technology investments to build an affordable and evolvable approach to Mars exploration. This leveraging of investments includes the use of high-power Solar Electric Propulsion (SEP) systems, evolved from those currently under development in support of the Asteroid Redirect Mission (ARM), to deliver payloads to Mars. The EMC is considering several transportation options that combine solar electric and chemical propulsion technologies to deliver crew and cargo to Mars. In one primary architecture option, the SEP propulsion system is used to pre-deploy mission elements to Mars while a high-thrust chemical propulsion system is used to send crew on faster ballistic transfers between Earth and Mars. This high-thrust chemical system uses liquid oxygen - liquid methane main propulsion and reaction control systems integrated into the Methane Cryogenic Propulsion Stage (MCPS). Over the past year, there have been several studies completed to provide critical design and development information related to the MCPS. This paper is intended to provide a summary of these efforts. A summary of the current point of departure design for the MCPS is provided as well as an overview of the mission architecture and concept of operations that the MCPS is intended to support. To leverage the capabilities of solar electric propulsion to the greatest extent possible, the EMC architecture pre-deploys to Mars orbit the stages required for returning crew from Mars. While this changes the risk posture of the architecture, it can provide some mass savings by using higher-efficiency systems for interplanetary transfer. However, this does introduce significantly longer flight times to Mars which, in turn, increases the overall lifetime of the stages to as long as 2500 days. This unique aspect to the concept of operations introduces several challenges, specifically related to propellant storage and engine reliability. These challenges and some potential solutions are discussed. Specific focus is provided on two key technology areas; propulsion and cryogenic fluid management. In the area of propulsion development, the development of an integrated methane propulsion system that combines both main propulsion and reaction control is discussed. This includes an overview of potential development paths, areas where development for Mars applications are complementary to development efforts underway in other parts of the aerospace industry, and commonality between the MCPS methane propulsion applications and other Mars elements, including the Mars lander systems. This commonality is a key affordability aspect of the Evolvable Mars Campaign. A similar discussion is provided for cryogenic fluid management technologies including a discussion of how using cryo propulsion in the Mars transportation application not only provides performance benefits but also leverages decades of technology development investments made by NASA and its aerospace contractor community.

Percy, Thomas K.↗

Design and Development of a Methane Cryogenic Propulsion Stage for Human Mars Exploration

NASA is currently working on the Evolvabe Mars Campaign (EMC) study to outline transportation and mission options for human exploration of Mars. One of the key aspects of the EMC is leveraging current and planned near-term technology investments to build an affordable and evolvable approach to Mars exploration. This leveraging of investments includes the use of high-power Solar Electric Propulsion (SEP) systems evolved from those currently under development in support of the Asteroid Redirect Mission to deliver payloads to Mars. The EMC is considering several transportation options that combine solar electric and chemical propulsion technologies to deliver crew and cargo to Mars. In one primary architecture option, the SEP propulsion system is used to pre-deploy mission elements to Mars while a high-thrust chemical propulsion system is used to send crew on faster ballistic transfers between Earth and Mars. This high-thrust chemical system uses liquid oxygen - liquid methane main propulsion and reaction control systems integrated into the Methane Cryogenic Propulsion Stage (MCPS). Over the past year, there have been several studies completed to provide critical design and development information related to the MCPS. This paper is intended to provide a summary of these efforts. A summary of the current point of departure design for the MCPS is provided as well as an overview of the mission architecture and concept of operations that the MCPS is intended to support. To leverage the capabilities of solar electric propulsion to the greatest extent possible, the EMC architecture pre-deploys the required stages for returning crew from Mars. While this changes the risk posture of the architecture, it provides mass savings by using higher-efficiency systems for interplanetary transfer. However, this does introduce significantly longer flight times to Mars which, in turn, increases the overall lifetime of the stages to as long as 3000 days. This unique aspect to the concept of operations introduces several challenges, specifically related to propellant storage and engine reliability. These challenges and some potential solutions are discussed. Specific focus is provided on two key technology areas; propulsion and cryogenic fluid management. In the area of propulsion development, the development of an integrated methane propulsion system that combines both main propulsion and reaction control is discussed. This includes an overview of potential development paths, areas where development for Mars applications are complementary to development efforts underway in other parts of the aerospace industry, and commonality between the MCPS methane propulsion applications and other Mars elements, including the Mars lander systems. This commonality is a key affordability aspect of the Evolvable Mars Campaign. A similar discussion is provided for cryogenic fluid management technologies including a discussion of how using cryo-propulsion in the Mars transportation application not only provides performance benefits but also leverages decades of technology development investments made by NASA and its aerospace contractor community.

Percy, Thomas K.↗

Workshop on Evolution of Martian Volatiles

This volume contains papers that were presented on February 12-14, 1996 at the Evolution for Martian Volatiles Workshop. Topics in this volume include: returned Martian samples; acidic volatiles and the Mars soil; solar EUV Radiation; the ancient Mars Thermosphere; primitive methane atmospheres on Earth and Mars; the evolution of Martian water; the role of SO2 for the climate history of Mars; impact crater morphology; the formation of the Martian drainage system; atmospheric dust-water ice Interactions; volatiles and volcanos; accretion of interplanetary dust particles; Mars' ionosphere; simulations with the NASA Ames Mars General Circulation Model; modeling the Martian water cycle; the evolution of Martian atmosphere; isotopic composition; solar occultation; magnetic fields; photochemical weathering; NASA's Mars Surveyor Program; iron formations; measurements of Martian atmospheric water vapor; and the thermal evolution Models of Mars.

Jakosky, B.↗

LOX/Methane In-Space Propulsion Systems Technology Status and Gaps

Human exploration architecture studies have identified liquid oxygen (LOX)Methane (LCH4) as a strong candidate for both interplanetary and descent ascent propulsion solutions. Significant research efforts into methane propulsion have been conducted for over 50 years, ranging from fundamental combustion mixing efforts to rocket chamber and system level demonstrations. Over the past 15 years NASA and its partners have built upon these early activities that have demonstrated practical components and sub-systems needed to field future methane space transportation elements. These advanced development efforts have formed a foundation of LOXLCH4 propulsion knowledge that has significantly reduced the development risks of future methane based space transportation elements for human exploration beyond earth orbit. As a bipropellant propulsion system, LOXLCH4 has some favorable characteristics for long life and reusability, which are critical to lunar and Mars missions. Non-toxic, non-corrosive, self-venting, and simple to purge. No extensive decontamination process required as with toxic propellants. High vapor pressure provides for excellent vacuum ignition characteristics. Performance is better than current earth storable propellants for human scale spacecraft. Provides the capability for future Mars exploration missions to use propellants that are produced in-situ on Mars Liquid Methane is thermally similar to O2 as a cryogenic propellant, 90,111 K (LO2, LCH4 respectively) instead of the 23 K of LH2. Allows for common components and thus providing cost savings as compared to liquid hydrogen (LH2). Due to liquid methane having a 6x higher density than hydrogen, it can be stored in much smaller volumes. Cryogenic storage aspect of these propellants needs to be addressed. Passive techniques using shielding and orientations to deep space Refrigeration may be required to maintain both oxygen and methane in liquid forms

Propulsion systems↗

Ground and Airborne Methane Measurements Using Optical Parametric Amplifiers

We report on ground and airborne methane measurements with an active sensing instrument using widely tunable, seeded optical parametric generation (OPG). The technique has been used to measure methane, CO2, water vapor, and other trace gases in the near and mid-infrared spectral regions. Methane is a strong greenhouse gas on Earth and it is also a potential biogenic marker on Mars and other planetary bodies. Methane in the Earth's atmosphere survives for a shorter time than CO2 but its impact on climate change can be larger than CO2. Carbon and methane emissions from land are expected to increase as permafrost melts exposing millennial-age carbon stocks to respiration (aerobic-CO2 and anaerobic-CH4) and fires. Methane emissions from c1athrates in the Arctic Ocean and on land are also likely to respond to climate warming. However, there is considerable uncertainty in present Arctic flux levels, as well as how fluxes will change with the changing environment. For Mars, methane measurements are of great interest because of its potential as a strong biogenic marker. A remote sensing instrument that can measure day and night over all seasons and latitudes can localize sources of biogenic gas plumes produced by subsurface chemistry or biology, and aid in the search for extra-terrestrial life. In this paper we report on remote sensing measurements of methane using a high peak power, widely tunable optical parametric generator (OPG) operating at 3.3 micrometers and 1.65 micrometers. We have demonstrated detection of methane at 3.3 micrometers and 1650 nanometers in an open path and compared them to accepted standards. We also report on preliminary airborne demonstration of methane measurements at 1.65 micrometers.

Numata, Kenji↗

Physical Properties and Seasonal Behavior of H2O, HDO, CO2 and Trace Gases on Mars: Quantitative Mapping from Earth-Based Observatories

Since 1997, we have used high-resolution (R greater than 40000) spectrometers on ground based-telescopes to study molecules that have astrobiological significance in Mars' atmosphere. We have used the NASA-IRTF, Keck II, and VLT telescopes in the 1.0-5.0 micron range. The spectrometer is set at a wavelength to detect specific molecules. Spectral/spatial images are produced. Extracts from these images provide column densities centered at latitude/longitude locations (resolution ~400km at sub-Earth point). We have mapped the O2 singlet-Delta emission (a proxy for ozone), HDO, and H2O for seasonal dates throughout the Martian year. Previously undiscovered isotopic bands of CO2 have been identified along with isotopic forms of CO. We are searching for other molecules that have astrobiological importance and have successfully measured methane in Mars' atmosphere.

Novak, Robert E.↗

Generating Aromatics From CO2 on Mars or Natural Gas on Earth

Methane to aromatics on Mars ( METAMARS ) is the name of a process originally intended as a means of converting Martian atmospheric carbon dioxide to aromatic hydrocarbons and oxygen, which would be used as propellants for spacecraft to return to Earth. The process has been demonstrated on Earth on a laboratory scale. A truncated version of the process could be used on Earth to convert natural gas to aromatic hydrocarbon liquids. The greater (relative to natural gas) density of aromatic hydrocarbon liquids makes it more economically feasible to ship them to distant markets. Hence, this process makes it feasible to exploit some reserves of natural gas that, heretofore, have been considered as being "stranded" too far from markets to be of economic value. In the full version of METAMARS, carbon dioxide is frozen out of the atmosphere and fed to a Sabatier reactor along with hydrogen (which, on Mars, would have been brought from Earth). In the Sabatier reactor, these feedstocks are converted to methane and water. The water is condensed and electrolyzed to oxygen (which is liquefied) and hydrogen (which is recycled to the Sabatier reactor). The methane is sent to an aromatization reactor, wherein, over a molybdenum-on-zeolite catalyst at a temperature 700 C, it is partially converted into aromatic hydrocarbons (specifically, benzene, toluene, and naphthalene) along with hydrogen. The aromatics are collected by freezing, while unreacted methane and hydrogen are separated by a membrane. Most of the hydrogen is recycled to the Sabatier reactor, while the methane and a small portion of the hydrogen are recycled to the aromatization reactor. The partial recycle of hydrogen to the aromatization reactor greatly increases the catalyst lifetime and eases its regeneration by preventing the formation of graphitic carbon, which could damage the catalyst. (Moreover, if graphitic carbon were allowed to form, it would be necessary to use oxygen to remove it.) Because the aromatics contain only one hydrogen atom per carbon atom, METAMARS produces four times as much propellant from a given amount of hydrogen as does a related process that includes the Sabatier reaction and electrolysis but not aromatization. In the terrestrial version of METAMARS, the Sabatier reactor and electrolyzer would be omitted, while the hydrogen/ methane membrane-separating membrane, the aromatization reactor, and the unreacted-gas-recycling subsystem would be retained. Natural gas would be fed directly to the aromatization reactor. Because natural gas consists of higher hydrocarbons in addition to methane, the aromatization subprocess should be more efficient than it is for methane alone.

Muscatello, Anthony C.↗