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At least 55 records · Page 3

Oxygenate Onboard Separation for Octane-on-Demand

This project further examines the use of Self-Assembled Monolayers on Mesoporous Supports ® SAMMS ® -based sorbent materials as a sorbent for alcohols from alcohol-gasoline blends in the context of an onboard separation approach for use in an octane-on-demand strategy. Several questions were posed by potential industry collaborators seeking to better understand how the SAMMS®-based materials would perform in a more realistic environment. Several conclusions can be made from the work conducted here, with the caveat that these experiments do not represent the results that would be obtained from continuous or long-term use of the sorbent, because of the short duration of the project. Vigorous extractions into warm gasoline did not reveal the presence of additional species in gas chromatographic analysis. Vibration testing for up to eight hours under aggressive conditions did not show particle attrition. Thermal desorption experiments showed that the SAMMS ® have a higher capacity for methanol, approximately 50 weight-percent of the sorbent, than for ethanol, approximately 20 weight-percent of the sorbent, and that the methanol is easier to extract. Testing of the A20 fuel blends was insufficient and requires a slightly more sophisticated approach than was attempted here. Additionally, further work would be needed to assess the rate at which the alcohol is absorbed into the sorbent. The testing conducted here suggests that equilibrium is reached in well under an hour. While this study provides additional insights into the use of SAMMS®-based sorbent materials for onboard alcohol separation, there is room for further work employing a benchtop testing apparatus similar to that described herein.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Device for obtaining separation of oxygen

Permeation membrane of a magnesium-nickel alloy of silver has the ability to permeate oxygen at high temperatures for an extended period of operation without failure. The measured rates of oxygen permeation in a tubular configuration of this alloy are higher than any previous rates published.

Glueckert, A. J.↗

Abort staging characteristics of an external oxygen tank separating from the space shuttle 040-A orbiter (.006 scale model) at Mach numbers of 0.6, 2.0, and 4.0

Experimental aerodynamic investigations were conducted on a .006 scale model of the space shuttle 040-A orbiter and its external fuel tank utilizing the NASA/MFSC dual sting support system in the MFSC 14 x 14 inch Trisonic Wind Tunnel. Normal force, pitching moment and axial force components were recorded simultaneously on the orbiter and the tank at selected tank field positions beneath the orbiter as both models were pitched through an angle of attack range of -5 deg to 20 deg. Incidence angles between orbiter and tank of 0 deg, 5 deg, 10 deg and 15 deg were investigated. During these tests Mach number was set at 0.6, 2.0 and 4.0.

Fossler, I. H.↗

Cloned Hemoglobin Genes Enhance Growth Of Cells

Experiments show that portable deoxyribonucleic acid (DNA) sequences incorporated into host cells make them produce hemoglobins - oxygen-binding proteins essential to function of red blood cells. Method useful in several biotechnological applications. One, enhancement of growth of cells at higher densities. Another, production of hemoglobin to enhance supplies of oxygen in cells, for use in chemical reactions requiring oxygen, as additive to serum to increase transport of oxygen, and for binding and separating oxygen from mixtures of gases.

Khosla, Chaitan↗

Investigations of Physical Processes in Microgravity Relevant to Space Electrochemical Power Systems

NASA has performed physical science microgravity flight experiments in the areas of combustion science, fluid physics, material science and fundamental physics research on the International Space Station (ISS) since 2001. The orbital conditions on the ISS provide an environment where gravity driven phenomena, such as buoyant convection, are nearly negligible. Gravity strongly affects fluid behavior by creating forces that drive motion, shape phase boundaries and compress gases. The need for a better understanding of fluid physics has created a vigorous, multidisciplinary research community whose ongoing vitality is marked by the continuous emergence of new fields in both basic and applied science. In particular, the low-gravity environment offers a unique opportunity for the study of fluid physics and transport phenomena that are very relevant to management of fluid - gas separations in fuel cell and electrolysis systems. Experiments conducted in space have yielded rich results. These results provided valuable insights into fundamental fluid and gas phase behavior that apply to space environments and could not be observed in Earth-based labs. As an example, recent capillary flow results have discovered both an unexpected sensitivity to symmetric geometries associated with fluid container shape, and identified key regime maps for design of corner or wedge-shaped passive gas-liquid phase separators. In this presentation we will also briefly review some of physical science related to flight experiments, such as boiling, that have applicability to electrochemical systems, along with ground-based (drop tower, low gravity aircraft) microgravity electrochemical research. These same buoyancy and interfacial phenomena effects will apply to electrochemical power and energy storage systems that perform two-phase separation, such as water-oxygen separation in life support electrolysis, and primary space power generation devices such as passive primary fuel cell.

energy storage↗

Pilot Testing of a Modular Oxygen Production System Using Oxygen Binding Adsorbents (Final Report)

In this project, RTI and Air Liquide have focused on the development of innovative oxygen separation materials and technologies based on reversibly binding of oxygen to enable smaller and cheaper air separations. In alignment with that object the team has had multiple achievements to advance the technology including: Synthesized and characterized novel M-CoSalen (RTIO2Sorb-1) material which showed a dynamic oxygen adsorption capacity in excess of 1wt%. Developed synthesis routes for RTIO2Sorb-1 with commercially relevant techniques and produced batches of 0.25kg and over 4 kg of total synthesis. Synthesized and characterized extrudate forms of the RTIO2Sorb-1 with relevant crush strength and maintained dynamic oxygen adsorption capacity in near 1wt%. Developed techniques for forming structured beds in fiber shapes with conventional materials. Developed a model for O 2 sorption processes to analyze various bed configurations and cycle parameters. Studied classic O 2 solid sorbents reported in the literature to learn oxygen binding mechanisms. Design a 10 kg/day O 2 VPSA pilot system with 2 or 4-bed operation. Completed a techno-economic analysis based on the experimental results and modeling. The overall objective of the project was to design, fabricate, and test a modular O 2 production system and perform a techno-economic analysis (TEA) after testing to determine the cost-benefit of the advanced modular air separation system. The goals of this technology development project were to achieve a bed-size factor (BSF) of less than 600 lb-adsorbent/TPD O 2 (ton/day O 2 ) (as compared with the state-of-the-art BSF of 850), and O 2 -purity greater than 95% at a cost that is projected to be equivalent or lower than the current state of the art (SOTA), commercially available large-scale cryogenic air separation systems. To achieve these goals and objective, the project team executed on (1) oxygen binding adsorbent optimization and scale up, (2) adsorbent material formation process studies to form the adsorbent material into structured beds for rapid pressure swing adsorption (PSA) cycles with low pressure drop, fast mass transfer, and low attrition, (3) cycle development studies to optimize the PSA process, and (4) develop simulation tools for rapid cycle modeling and numerical evaluation/optimization.

20 FOSSIL-FUELED POWER PLANTS↗

Electrochemical Solutions for Advanced Life Support

The Oxygen Generating Assembly (OGA) on-board the International Space Station (ISS) employs a polymer electrolyte membrane (PEM) water electrolysis cell stack to electrochemically dissociate water into its two components – oxygen and hydrogen. Oxygen is provided to the cabin atmosphere for crew respiration while the hydrogen is delivered to a carbon dioxide reduction system to recover oxygen as water. The design of the OGA evolved over a number of years to arrive at the system solution that is currently operational on ISS. Future manned missions to space will require advanced technologies that eliminate the need for resupply from earth and feature in-situ resource utilization to sustain crew life and to provide useful materials to the crew. The architects planning such missions should consider all potential solutions at their disposal to arrive at an optimal vehicle solution that minimizes crew maintenance time, launch weight, installed volume and energy consumption demands. Skyre is developing new technologies through funding from NASA, the Department of Energy, and internal investment based on PEM technology that could become an integral part of these new vehicle solutions. At varying stages of Technology Readiness Level (TRL) are: an oxygen concentrator and compressor that can separate oxygen from an air stream and provide an enriched oxygen resource for crew medical use and space suit recharge without any moving parts in the pure oxygen stream; a regenerative carbon dioxide removal system featuring a PEM-based sorbent regenerator; a carbon dioxide reduction system that electrochemically produces organic compounds that could serve as fuels or as a useful intermediary to more beneficial compounds; and an electrochemical hydrogen separator and compressor for hydrogen recycle. The technical maturity of these projects is presented along with pertinent performance test data that could be beneficial in future study efforts.

Roy, Robert J.↗

A 99 percent purity molecular sieve oxygen generator

Molecular sieve oxygen generating systems (MSOGS) have become the accepted method for the production of breathable oxygen on military aircraft. These systems separate oxygen for aircraft engine bleed air by application of pressure swing adsorption (PSA) technology. Oxygen is concentrated by preferential adsorption in nitrogen in a zeolite molecular sieve. However, the inability of current zeolite molecular sieves to discriminate between oxygen and argon results in an oxygen purity limitations of 93-95 percent (both oxygen and argon concentrate). The goal was to develop a new PSA process capable of exceeding the present oxygen purity limitations. A novel molecular sieve oxygen concentrator was developed which is capable of generating oxygen concentrations of up to 99.7 percent directly from air. The process is comprised of four absorbent beds, two containing a zeolite molecular sieve and two containing a carbon molecular sieve. This new process may find use in aircraft and medical breathing systems, and industrial air separation systems. The commercial potential of the process is currently being evaluated.

Miller, G. W.↗

Polar Bear™ – Innovative Capture of Storage Tank Vapors

Polar Bear™ is a patented technology developed by the Energy & Environmental Research Center (EERC) to capture storage tank vapors and eliminate methane emissions from upstream oil- and gas-producing facilities. Sparked by early commercial investment, the EERC licensed the technology and extended the intellectual property to storage tanks. Polar Bear™ is uniquely engineered and adapted to individual lower-producing facilities where there is otherwise no economic alternative for capturing tank vapors. A high number of small producing oil and gas wells are distributed across the country. The aggregate contributes to a significant volume of emissions. Because of the lack of economy of scale, gas volumes from these facilities are typically not recovered and contribute to methane emissions. Polar Bear™ provides a fit-for-purpose compression solution that addresses cost by reducing complexity with respect to conventional vapor recovery units and eliminating oil changes. Unique to Polar Bear™ is the capability to separate oxygenated gas from storage tank vapors. Storage tanks are designed to “breathe,” allowing gas to enter and escape during internal level and temperature changes. This infiltration of air into the tank headspace imparts undesirable oxygen content with respect to pipeline gathering. Polar Bear™ separates the vapor stream, allowing oxygen-rich gas to be used as fuel on-site while recovering the liquids-rich portion of the gas where oxygen content is minimized. A prototype system was tested to verify process models, evaluate operational performance, and advance the technology readiness level from 5 to 6. Results provide a good match between experimental measurements and process models, indicating the models are useful for future scale-up and field design. Various mixtures of nitrogen and liquefied petroleum gas were tested to understand the mass balance of nitrogen and how it relates to the potential control of oxygen content. Findings indicate that less than 2000 ppm of oxygen is likely to remain in the liquid portion of the gas in field applications. The research and development prepare the technology for field implementation to eliminate routine and fugitive methane emissions from storage tanks.

02 PETROLEUM↗

Development of Enabling Technologies for Chemical Looping Combustion and Chemical Looping with Oxygen Uncoupling (Final Report)

This report summarizes results from the project, “Development of Enabling Technologies for Chemical Looping Combustion and Chemical Looping with Oxygen Uncoupling,” which evaluated several aspects of dual fluidized bed chemical looping combustion and chemical looping with oxygen uncoupling (CLOU). The objective was to provide tools and enabling technologies to help advance fluidized bed chemical looping technology to pilot, demonstration and commercial scale. One focus area is oxygen carriers, which are key to chemical looping combustion. The copper oxygen carrier-coal ash system was systematically evaluated through a combination of thermodynamic modeling and lab-scale experiments, taking into consideration different oxygen carrier support materials and coal types. A method of mapping “safe” and “risk” zones for different combinations was established, and recommendations for target conditions are provided. In addition, a simple solution for limiting negative influence of some coal ashes, namely adding small amounts of calcium to the system, is proposed. In addition, a novel process for recovering and recycling copper from spent oxygen carriers is proposed. A new approach for design and operation of loop seals in a CLOU system was developed, and involves distinct gas injection points and a short horizontal section to help control the fate of the fluidizing gases. For the air-to-fuel reactor loop seal, the upstream side is fluidized with air, ideally input into the side rather than into the bottom, which prevents uncoupling (reduction) of the oxygen carrier before entering the fuel reactor. Also, alternative for separating oxygen carrier particles and gas in circulating fluidized bed-based chemical looping system is proposed. A new reduced reaction scheme for conversion of coal in copper-based CLOU was developed and implemented into CPFD Software’s Barracuda VR package. The resulting model provides higher fidelity than the baseline, especially when it comes to minor reactions that are part of the overall combustion environment. For in-reactor heat extraction, it was determined in this project that the best way to do that in a dual circulating fluidized-bed system is through heat exchange low in the air reactor. The air reactor is the hotter of the two and for a fast-fluidized circulating bed, the lower, more dense section has a higher heat transfer coefficient and offers more consistent particle-wall contact since it doesn’t have the splashing behavior the top of the bed does. It was determined that just the wall surface area in the lower quarter to third of the air reactor is sufficient to control temperatures in both reactors. Finally, consideration was given to a new concept for CLC, which involves a staged fuel reactor with a different type of oxygen carrier in each stage.

01 COAL, LIGNITE, AND PEAT↗

Mapping the Capabilities and Attributes of Solid Oxide Electrochemical Systems to Human Spaceflight Needs

NASA is sponsoring the development of a solid oxide electrochemical oxygen separation and compression system. This system is capable of extracting oxygen from a process stream of spacecraft cabin air, and compressing it to >27,000 kPa without mechanical compressors. Process temperatures are >650C, but the materials in contact with the oxygen do not burn. The system is called eCOG-C, Electrochemical Oxygen Generator and Compressor. A system capable of producing high pressure, high purity oxygen may have application as a method of recharging space suit oxygen tanks during human exploration missions. This paper describes the key performance parameters of a space suit oxygen tank recharge system, and places the key performance parameters of eCOG-c in the context of other methods of space suit oxygen tank recharge. This paper compares the eCOG-c configuration to an earlier electrochemical oxygen generator that has been prototyped and tested. Areas of emphasis for eCOG-C development are listed and described.

John Graf↗

Assessment of exchange-correlation functionals on oxygen vacancy formation energies of metal oxides

Oxygen vacancies are a common defect in oxides and play vital roles in many technological applications such as oxygen separation, catalytic reactors, solid oxide fuel cells, and solar thermochemical water splitting. The oxygen vacancy formation energy is directly related to the oxide reduction enthalpy and the vacancy concentration and, therefore, is a key quantity underlying these applications. The complexity of measuring oxygen vacancy formation energies experimentally suggests the utility of calculations based on density functional theory (DFT). However, the calculated results are strongly dependent on the exchange-correlation functionals and other parameters such as the Hubbard U . In this work, we compare the performance of the meta-GGA strongly constrained and appropriately normed (SCAN) functional and the commonly used semilocal generalized gradient approximation (GGA) functionals with experimental values of structural parameters, band gaps, magnetic structures, and oxygen vacancy formation energies for six representative oxides, i.e., CaMnO 3 , SrMnO 3 , LaMnO 3 , YMnO 3 , LaFeO 3 , and CeO 2 . Further, our results show that SCAN usually has better agreement with the experimental lattice constants and band gaps and larger magnetic moments than the commonly used GGA functionals. Although SCAN overestimates the oxygen vacancy formation energies of transition metal oxides and therefore requires unusually large Hubbard U values to reproduce the experimental reduction enthalpies, it does predict the correct oxygen vacancy formation energy of CeO 2 , which challenges the commonly used GGA and hybrid functionals. Our results underscore the challenges that exist in describing these complex oxides by DFT and may shed light on developing more accurate exchange-correlation functionals for oxygen vacancy formation energy calculations.

36 MATERIALS SCIENCE↗

Full system engineering design and operation of an oxygen plant

The production of oxygen from the indigenous resources on Mars is described. After discussing briefly the project's background and the experimental system design, specific experimental results of the electrolytic cell are presented. At the heart of the oxygen production system is a tubular solid zirconia electrolyte cell that will electrochemically separate oxygen from a high-temperature stream of Coleman grade carbon dioxide. Experimental results are discussed and certain system efficiencies are defined. The parameters varied include (1) the cell operating temperature; (2) the carbon dioxide flow rate; and (3) the voltage applied across the cell. The results confirm our theoretical expectations.

Colvin, James↗

Propellant production on Mars - Single cell oxygen production test bed

A study focusing on oxygen production using resources indigenous to Mars is presented. A bank of solid zirconia electrolytic cells that will electrochemically separate oxygen from a high temperature stream of carbon dioxide is at the center of the oxygen production system. The experimental data are discussed with attention given to the cell operating temperature, the carbon dioxide flow rate, and the voltage applied across the cell.

Colvin, James↗

Refrigerator Based on Chemisorption

Reversible chemical reaction generates pressurized oxygen for cooling. Concept for cryogenic refrigerator based on chemical absorption of oxygen by praseodymium/cerium oxide (PCO) compound. Refrigerator produces cryogenic liquid for cooling infrared sensors. Also used for liquefying air and separating oxygen from nitrogen in air. In chemisorption refrigerator, PCO alternately absorbs and desorbs oxygen depending on whether cooled or heated. One pair of compressors accepts oxygen while others releases it. Compressed oxygen liquefied when precooked and expanded.

Jones, Jack A.↗

Unlocking bulk and surface oxygen transport properties of mixed oxide-ion and electron conducting membranes with combined oxygen permeation cell and oxygen probe method

Surface exchange kinetics and bulk diffusion of oxygen are of paramount importance to the activity of oxygen electrocatalysis and performance of electrochemical devices such as fuel cell, metal-air batteries, and oxygen separation membranes. Conventional approaches to obtaining these transport properties are often limited to single property under a specific non-operation related condition. Here we use a combined oxygen permeation cell and oxygen probe methodology to simultaneously attain rates of oxygen surface exchange and bulk conductivity/chemical diffusivity of three representative mixed oxide-ion and electron conductors, namely SrCo 0.9 Ta 0.1 O 3-δ (SCT), La 0.6 Sr 0.4 CoO 3-δ (LSC) and La 0.6 Sr 0.4 FeO 3-δ (LSF), operated under a steady-state oxygen flux. The results explicitly show that SCT exhibit the highest oxide-ion conductivity/chemical diffusivity, fastest rates of surface oxygen exchange kinetics, thus promising to be the best oxygen electrocatalyst. Here, we have also mapped out the distribution of oxygen chemical potential gradient across the membranes and applied B-transport number concept to illustrate the rate-limiting steps in the overall oxygen permeation process.

42 ENGINEERING↗

Substituted ALPO-5 Zeolites as Promising O 2 Sorption Pump Materials: A Density Functional Theory Study

Many chemical processes depend on having an environment that is low in oxygen partial pressure (P O2 < 100 Pa); sorption pumps are a promising route to establishing that environment by either oxygen pumping or oxygen separation from an inert gas. Near ambient sorption-based processes rely on either pressure or thermal swings, requiring no moving parts, no electricity, and neither very high nor very low temperatures. In this work, we use ab initio calculations to explore zeolites as a class of materials for sorption based oxygen pumping/separation. Our calculations indicate that while the neat ALPO-5 zeolite does not adsorb O 2 , O 2 does adsorb on zeolites selectively substituted with transition metals and metalloids and hence, can enable separation and pumping. ALPO-5 substituted with Si, Ge, Sn, Pd, Pt, Ti, V, Cr, Mn, Zr, Mo, Hf, W, Ce, and Pr provides adsorption energies ranging from -0.19 to -3.92 eV, (-) indicates exothermic process. Additionally, we provide a comprehensive understanding of what controls the adsorption energy: 1) the substi-tutions must be able to adopt an oxidation state that is more positive than the cation it replaces, and 2) the size of the pore into which the O 2 adsorbs to the wall. Additionally, we conduct a ther-modynamic analysis of a thermal swing cycle to approximate the optimal O 2 binding energy for 2 low energy O 2 pumping/separation. We find that the minimum energy cost likely occurs when the adsorption energy is in the range of 0.75 – 1.00 eV (72 – 97 kJ·mol -1 ), which corresponds to Ge, V, Pt, or Ce substituted ALPO-5.

36 MATERIALS SCIENCE↗

A tailored multi-functional catalyst for ultra-efficient styrene production under a cyclic redox scheme

Abstract Styrene is an important commodity chemical that is highly energy and CO 2 intensive to produce. We report a redox oxidative dehydrogenation (redox-ODH) strategy to efficiently produce styrene. Facilitated by a multifunctional (Ca/Mn) 1− x O@KFeO 2 core-shell redox catalyst which acts as (i) a heterogeneous catalyst, (ii) an oxygen separation agent, and (iii) a selective hydrogen combustion material, redox-ODH auto-thermally converts ethylbenzene to styrene with up to 97% single-pass conversion and >94% selectivity. This represents a 72% yield increase compared to commercial dehydrogenation on a relative basis, leading to 82% energy savings and 79% CO 2 emission reduction. The redox catalyst is composed of a catalytically active KFeO 2 shell and a (Ca/Mn) 1− x O core for reversible lattice oxygen storage and donation. The lattice oxygen donation from (Ca/Mn) 1− x O sacrificially stabilizes Fe 3+ in the shell to maintain high catalytic activity and coke resistance. From a practical standpoint, the redox catalyst exhibits excellent long-term performance under industrially compatible conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗