Technoeconomic analysis of oxygen-nitrogen separation for oxygen enrichment using membranes
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Adhikari, Birendra↗
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Concentrating Solar Reduction Reactorfor Oxygen Separation from Air.
Abstract not provided.
Kury, Matthew Wilson↗
Extraction of oxygen from the Mars atmosphere using glow-discharge and permeation techniques
Oxygen can be extracted from carbon dioxide via thermal dissociation at elevated temperatures. However, temperatures in excess of 1000 K are needed to effect significant levels of dissociation. The experiments reported here have examined the feasibility of using a glow-discharge in low-pressure carbon dioxide to produce increased atomic oxygen yields at lower temperatures (on the order of 800 K). The experiments have shown that when silver membranes are used simultaneously as anodes for the glow discharge and as permeable membranes for oxygen separation, oxygen yields which are comparable to the permeation rates for pure oxygen, can be produced. Since the silver membrane can be employed as the electrode interface between Mars atmosphere and a stabilized-zirconia electrochemical pump, glow-discharge enhancement can be considered as a complementary technology which can be used with the zirconia-based oxygen extraction systems described previously by others. Not only can glow-discharge be used to increase oxygen yields at lowered temperatures, but it can also be considered as a possible way to avoid filtration and compression of Mars atmosphere, since the glow-discharge can be sustained in Mars ambient pressures.
Wu, Dongchuan↗
Sample Acquisition and Analytical Chemistry Challenges to Verifying Compliance to Aviators Breathing Oxygen (ABO) Purity Specification
NASA has been developing and testing two different types of oxygen separation systems. One type of oxygen separation system uses pressure swing technology, the other type uses a solid electrolyte electrochemical oxygen separation cell. Both development systems have been subjected to long term testing, and performance testing under a variety of environmental and operational conditions. Testing these two systems revealed that measuring the product purity of oxygen, and determining if an oxygen separation device meets Aviator's Breathing Oxygen (ABO) specifications is a subtle and sometimes difficult analytical chemistry job. Verifying product purity of cryogenically produced oxygen presents a different set of analytical chemistry challenges. This presentation will describe some of the sample acquisition and analytical chemistry challenges presented by verifying oxygen produced by an oxygen separator - and verifying oxygen produced by cryogenic separation processes. The primary contaminant that causes gas samples to fail to meet ABO requirements is water. The maximum amount of water vapor allowed is 7 ppmv. The principal challenge of verifying oxygen produced by an oxygen separator is that it is produced relatively slowly, and at comparatively low temperatures. A short term failure that occurs for just a few minutes in the course of a 1 week run could cause an entire tank to be rejected. Continuous monitoring of oxygen purity and water vapor could identify problems as soon as they occur. Long term oxygen separator tests were instrumented with an oxygen analyzer and with an hygrometer: a GE Moisture Monitor Series 35. This hygrometer uses an aluminum oxide sensor. The user's manual does not report this, but long term exposure to pure oxygen causes the aluminum oxide sensor head to bias dry. Oxygen product that exceeded the 7 ppm specification was improperly accepted, because the sensor had biased. The bias is permanent - exposure to air does not cause the sensor to return to its original response - but the bias can be accounted for by recalibrating the sensor. After this issue was found, continuous measurements of water vapor in the oxygen product were made using an FTIR. The FTIR cell is relatively large, so response time is slow - but moisture measurements were repeatable and accurate. Verifying ABO compliance for oxygen produced by commercial cryogenic processes has a different set of sample acquisition and analytical chemistry challenges. Customers want analytical chemists to conserve as much as possible. Hygrometers are not exposed to hours of continuous flow of oxygen, so they don't bias, but small amounts of contamination in valves can cause a "fail". K bottles are periodically cleaned and recertified - after cleaning residual moisture can cause a "fail". Operators let bottle pressure drop to room pressure, introduce outside air into the bottle, and the subsequent fill will "fail". Outside storage of K‐bottles has allowed enough in‐leakage, so contents will "fail".
Graf, John↗
Ultrathin polyorganosilica membranes synthesized by oxygen-plasma treatment of polysiloxanes for H 2 /CO 2 separation
Oxygen plasma treatment of polydimethylsiloxane (PDMS) induces an ultrathin polyorganosilica (POSi) layer (<10 nm) on top of a PDMS membrane, leading to excellent H 2 /gas separation properties and providing a rapid and scalable way to fabricate robust silica membranes compared with conventional high-temperature and time-consuming sol-gel methods. Here, we thoroughly investigate POSi membranes derived from poly (dimethylsiloxane-co-methylhydroxidesiloxane) (poly (DMS-co-MHOS)) containing -SiOH groups that can be more easily converted to silica networks than the -SiCH 3 in PDMS. Further, the effect of the polysiloxane structure and plasma treatment conditions (including plasma generating powers, oxygen flowrate, chamber pressure, and treatment time) on the silica chemistry, structure, and H 2 /CO 2 separation properties are systematically determined to derive structure/property relationships. An optimized membrane exhibits H 2 permeance of 880 GPU and H 2 /CO 2 selectivity of 67 at 150 °C, superior to state-of-the-art polymeric membranes. The membrane retains H 2 /CO 2 selectivity as high as 46 when challenged with simulated syngas containing 2.8 mol% water vapor at 150 °C, demonstrating the potential of these POSi membranes for practical applications.
36 MATERIALS SCIENCE↗
On-board separation of oxygenates from fuels
Methods for separation of oxygenates or other chemical components from fuels using chemical processes and separations including, but not limited to, onboard applications in vehicles. These separations may take place using a variety of materials and substances whereby a target material of interest is captured, held, and then released at a desired location and under desired conditions. In one set of experiments we demonstrated an enhancement in the separation of diaromatics by >38 times over gasoline and aromatics by >3.5 times over gasoline. This would give an advantage to reducing cold-start emissions, or emissions during transient conditions, in either gasoline or diesel.
Bays, John T.↗
Electrolysis Performance Improvement Concept Study (EPICS) flight experiment phase C/D
The overall purpose of the Electrolysis Performance Improvement Concept Study flight experiment is to demonstrate and validate in a microgravity environment the Static Feed Electrolyzer concept as well as investigate the effect of microgravity on water electrolysis performance. The scope of the experiment includes variations in microstructural characteristics of electrodes and current densities in a static feed electrolysis cell configuration. The results of the flight experiment will be used to improve efficiency of the static feed electrolysis process and other electrochemical regenerative life support processes by reducing power and expanding the operational range. Specific technologies that will benefit include water electrolysis for propulsion, energy storage, life support, extravehicular activity, in-space manufacturing and in-space science in addition to other electrochemical regenerative life support technologies such as electrochemical carbon dioxide and oxygen separation, electrochemical oxygen compression and water vapor electrolysis. The Electrolysis Performance Improvement Concept Study flight experiment design incorporates two primary hardware assemblies: the Mechanical/Electrochemical Assembly and the Control/Monitor Instrumentation. The Mechanical/Electrochemical Assembly contains three separate integrated electrolysis cells along with supporting pressure and temperature control components. The Control/Monitor Instrumentation controls the operation of the experiment via the Mechanical/Electrochemical Assembly components and provides for monitoring and control of critical parameters and storage of experimental data.
Schubert, F. H.↗
Apparatus in the form of a disk for the separation of oxygen from other gases and/or for the pumping of oxygen and the method of removing the oxygen
An apparatus in the form of a disk for the separation of oxygen from gases, or for the pumping of oxygen, uses a substantially circular disk geometry for the solid electrolyte with radial flow of gas from the outside edge of the disk to the center of the disk. The reduction in available surface area as the gas flows toward the center of the disk reduces the oxygen removal area proportionally to provide for a more uniform removal of oxygen.
Suitor, Jerry W.↗
Issues on the production and electrochemical separation of oxygen from carbon dioxide
There is considerable interest in in-situ propellant manufacturing on the moon and Mars. One of the concepts of oxygen production that is being actively pursued is the processing of atmospheric carbon dioxide on Mars to produce oxygen by means of thermal decomposition and electrochemical separation. The key component of such a production facility is the electrochemical separation cell that filters out the oxygen from the gas mixture of carbon dioxide, carbon monoxide, and oxygen. Efficient design of the separation cell and the selection of electrolyte and electrode materials of superior performance for the cell would translate to significant reduction in the power requirement and the mass of the production facility. The objective is to develop the technology required to produce the cells in-house and test various electrolyte and electrode materials systematically until the optimal combination is found. An effective technique was developed for the fabrication of disk shaped cells. Zirconia and Ceria cells were made in-house. Complete modules of the electrochemical cell and housings were designed, fabricated, and tested.
Kaloupis, P.↗
Metal–organic frameworks as O 2 -selective adsorbents for air separations
Oxygen is a critical gas in numerous industries and is produced globally on a gigatonne scale, primarily through energy-intensive cryogenic distillation of air. The realization of large-scale adsorption-based air separations could enable a significant reduction in associated worldwide energy consumption and would constitute an important component of broader efforts to combat climate change. Certain small-scale air separations are carried out using N 2 -selective adsorbents, although the low capacities, poor selectivities, and high regeneration energies associated with these materials limit the extent of their usage. In contrast, the realization of O 2 -selective adsorbents may facilitate more widespread adoption of adsorptive air separations, which could enable the decentralization of O 2 production and utilization and advance new uses for O 2 . Here, we present a detailed evaluation of the potential of metal–organic frameworks (MOFs) to serve as O 2 -selective adsorbents for air separations. Drawing insights from biological and molecular systems that selectively bind O 2 , we survey the field of O 2 -selective MOFs, highlighting progress and identifying promising areas for future exploration. As a guide for further research, the importance of moving beyond the traditional evaluation of O 2 adsorption enthalpy, ΔH, is emphasized, and the free energy of O 2 adsorption, ΔG, is discussed as the key metric for understanding and predicting MOF performance under practical conditions. Based on a proof-of-concept assessment of O 2 binding carried out for eight different MOFs using experimentally derived capacities and thermodynamic parameters, we identify two existing materials and one proposed framework with nearly optimal ΔG values for operation under user-defined conditions. While enhancements are still needed in other material properties, the insights from the assessments herein serve as a guide for future materials design and evaluation. Computational approaches based on density functional theory with periodic boundary conditions are also discussed as complementary to experimental efforts, and new predictions enable identification of additional promising MOF systems for investigation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Oxygen extraction for a mission life support
Research conducted to extract oxygen from air or water with possible applications to oxygen production on Mars, the moon, or the Space Station is discussed. The technology under development involves an electrochemical process which is energy-efficient, regenerative and, in combination with a fuel cell, will provide net positive power, and generate oxygen for life support systems. The history of chemical oxygen separation and details of the oxygen separation technology are presented.
Carnevale, Steven J.↗
Autonomous oxygen production for a Mars return vehicle
The way in which a chemical processor that uses the Martian atmosphere as its only feedstock, thereby reducing the mass that must be launched from earth, can help to return a surface sample from Mars from a single Space Shuttle launch is described. Richter's (1981) study on both the theoretical and experimental aspects of oxygen separation using yttria-stabilized zirconia membranes is cited. Here, separation is accomplished by applying a voltage across the membrane which results in the selective conduction of oxygen ions from one side to the other. It is noted that by using thermal dissociation of the carbon dioxide in the Martian atmosphere to produce oxygen (and carbon monoxide), these zirconia electrolytic cells can be employed to separate oxygen from the atmospheric stream. Descriptions are also given of atmospheric filtration, atmospheric compression, and waste heat recovery, and of the oxygen precooler and oxygen compressor.
Ash, R. L.↗
A Modular Oxygen-Selective System for Combustion Systems
Small-scale modular systems for oxygen generation offer clear benefits, including improved energy efficiency, reduced operating costs, and the flexibility to meet location-specific needs. We propose that a compact modular system could be developed using a solvent-based method for capturing and releasing oxygen, enabling “oxygen on demand” for various combustion technologies. In this project, we aim to develop and demonstrate a modular oxygen-selective approach based on Battelle IPID 31740. The use of designer solvents, which are reversible, single-component solvents capable of dissolving and separating oxygen from air, offers the advantage of unlimited chemical tunability to achieve desirable properties for efficient oxygen separation. We filed U.S. Patent (32845-E, iEdison No. 0685901-23-0184).
36 MATERIALS SCIENCE↗
Electrochemical cell for obtaining oxygen from carbon dioxide atmospheres
For manned missions to Mars to become a reality, an efficient and reliable means of obtaining oxygen from the carbon dioxide-rich atmosphere will be required. Otherwise, the high cost of transporting the oxygen needed to sustain the astronauts will severely restrict the expedition to the martian surface. Recently, the use of electrochemical devices has been explored as a means of obtaining oxygen from the carbon dioxide-rich atmosphere. In these devices, oxygen ions diffuse through solid oxide membranes, thus, separating oxygen from the other gases presented. This phenomenon has only recently been explored as a means of obtaining large quantities of oxygen from toxic atmospheres, although first observed by Walter nernst in 1899. Nernst observed that stabilized zirconia will conduct oxygen ions when an electrical potential is applied across metallic electrodes applied to the ceramic membrane. Diatomic oxygen molecules are dissociated at the positive electrode/electrolyte interface. The oxygen ions enter the ceramic body due to the ion density gradient which is produced by the electrical potential across the electrolytic membrane. Once the ions have diffused through the membrane, they reform diatomic oxygen molecules at the anode. The separation of oxygen from carbon dioxide is achieved by the combination of thermal and electrochemical processes. The thermal decomposition of carbon dioxide (at 1000 C) results in the production of carbon monoxide and oxygen by the reaction.
Hooker, M. W.↗
Oxygen production using solid-state zirconia electrolyte technology
High purity oxygen is required for a number of scientific, medical, and industrial applications. Traditionally, these needs have been met by cryogenic distillation or pressure swing adsorption systems designed to separate oxygen from air. Oxygen separation from air via solid-state zirconia electrolyte technology offers an alternative to these methods. The technology has several advantages over the traditional methods, including reliability, compactness, quiet operation, high purity output, and low power consumption.
Suitor, Jerry W.↗
Material to separate and pump oxygen
A material for separating and pumping oxygen is disclosed. The material is a zeolite doped with a chemical element having an electron density of between 30 kJ/mol and 150 kJ/mol. The material is configured for controllable oxygen desorption between 150° C. and 300° C. and pumping the released oxygen into an area having an ambient pressure of less than 100 pascals.
Wilson, Steven↗
A Cabin Air Separator for EVA Oxygen
Presently, the Extra-Vehicular Activities (EVAs) conducted from the Quest Joint Airlock on the International Space Station use high pressure, high purity oxygen that is delivered to the Space Station by the Space Shuttle. When the Space Shuttle retires, a new method of delivering high pressure, high purity oxygen to the High Pressure Gas Tanks (HPGTs) is needed. One method is to use a cabin air separator to sweep oxygen from the cabin air, generate a low pressure/high purity oxygen stream, and compress the oxygen with a multistage mechanical compressor. A main advantage to this type of system is that the existing low pressure oxygen supply infrastructure can be used as the source of cabin oxygen. ISS has two water electrolysis systems that deliver low pressure oxygen to the cabin, as well as chlorate candles and compressed gas tanks on cargo vehicles. Each of these systems can feed low pressure oxygen into the cabin, and any low pressure oxygen source can be used as an on-board source of oxygen. Three different oxygen separator systems were evaluated, and a two stage Pressure Swing Adsorption system was selected for reasons of technical maturity. Two different compressor designs were subjected to long term testing, and the compressor with better life performance and more favorable oxygen safety characteristics was selected. These technologies have been used as the basis of a design for a flight system located in Equipment Lock, and taken to Preliminary Design Review level of maturity. This paper describes the Cabin Air Separator for EVA Oxygen (CASEO) concept, describes the separator and compressor technology trades, highlights key technology risks, and describes the flight hardware concept as presented at Preliminary Design Review (PDR)
Graf, John C.↗
High temperature seals between ceramic separation membranes and super-alloy housing
One of the concepts for oxygen production from Martian atmospheric carbon dioxide involves the use of tubular electrochemical membranes for oxygen separation. The tubular configuration offers the advantage of being able to separate the oxygen at pressures of up to 500 psi, thereby eliminating the need for a pre-liquefaction oxygen compressor. A key technology that has to be developed in order for the electrochemical separator to combine as a compressor is a high temperature static seal between the ceramic separation cell and the nickel-based super-alloy tube. Equipment was designed and fabricated to test the seals. Efforts are under way to develop a finite element model to study the thermal stresses at the joints and on the seal, and the optimal shape of the seal. The choice of seal materials and the technique to be used to fabricate the seals are also being investigated.
Honea, G.↗