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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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Catalytic Graphitization of Biocarbon for Lithium‐Ion Anodes: A Minireview

Abstract The demand for electrochemical energy storage is increasing rapidly due to a combination of decreasing costs in renewable electricity, governmental policies promoting electrification, and a desire by the public to decrease CO 2 emissions. Lithium‐ion batteries are the leading form of electrochemical energy storage for electric vehicles and the electrical grid. Lithium‐ion cell anodes are mostly made of graphite, which is derived from geographically constrained, non‐renewable resources using energy‐intensive and highly polluting processes. Thus, there is a desire to innovate technologies that utilize abundant, affordable, and renewable carbonaceous materials for the sustainable production of graphite anodes under relatively mild process conditions. This review highlights novel attempts to realize the aforementioned benefits through innovative technologies that convert biocarbon resources, including lignocellulose, into high quality graphite for use in lithium‐ion anodes.

25 ENERGY STORAGE↗

Percutaneous and skeletal biocarbon implants

Review of carbon implants developed by NASA discussed four different types of implants and subsequent improvements. Improvements could be of specific interest to rehabilitation centers and similar organizations.

Mooney, V.↗

Emerging Technologies for Decarbonizing Silicon Production

Abstract Silicon (Si) is an important material for alloying, solar photovoltaics, and electronics. However, current methods of producing silicon require energy consumption of around 11–13 kWh/kg Si and direct carbon emissions are 4.7–5 tons CO 2 per ton Si which conflicts with global efforts to limit climate change. In this work, we discuss several promising methods for reducing or eliminating carbon emissions from the silicon production process. Such methods include using biocarbon, integrating the current process with carbon capture and utilization/storage (CCU/CCS), metallothermic reduction, hydrogen reduction, and molten salt electrolysis. We present the positive aspects and challenges of each approach. Biocarbon coupled with CCU/CCS is the most industrially mature technology and can be carbon–neutral or -negative but is not carbon-free. Hydrogen directly reducing silicon dioxide is not thermodynamically favorable, but it may be viable to use hydrogen in conjunction with other processes to reduce emissions. Metallothermic and electrochemical methods of production are promising and have the potential to create high-purity silicon with no reduction-related carbon emissions but have only been demonstrated at lab scale. Economic viability will likely be the next determining factor for which technologies are more widely researched and implemented. Graphical Abstract

08 HYDROGEN↗

Comparison of Silicon Decarbonization Methods to Reduce Process Emissions and Energy Consumption

The demand for silicon is rising due to its use in solar cells, electronics, and alloying as part of the green transition. However, these products require silicon metal (metallurgical grade silicon, >98% Si) as their main raw material before undergoing further chemical refining, usually via gas phase in methods such as the Siemens process. Silicon metal is currently produced in a submerged arc furnace via carbothermic reduction of quartz, which results in 10-12 tCO2/tSi. More than 40% of these emissions are process emissions, meaning they do not include contributions from electricity generation or transport. This talk will discuss promising methods to reduce or eliminate these process emissions. These include the use of biocarbon and carbon capture, aluminothermic reduction, electrochemical reduction with molten salts, and use of hydrogen in a modified Siemens process. Biocarbon and carbon capture is a straightforward method to reduce the net carbon emissions of the process, but long-term sustainable production of high-quality charcoal is a challenge. Aluminothermic reduction makes good use of aluminum byproducts such as dross but is perhaps limited in its applications to aluminum-silicon alloy products. Electrochemical reduction is promising as a method of producing high purity Si from quartz, without further need for the Siemens process, but is still in early stages of research and slow processing times are a concern. Finally, the use of hydrogen in a modified Siemens process would also result in a high purity Si product from quartz, however the process has considerable logistical challenges with corrosive and unstable gases at high temperatures. This talk will further expand on the potential merits and challenges of each method, while comparing their potential to reduce emissions and/or energy consumption while meeting global demand.

decarbonization↗

Biogenic carbon capture at pulp mills via sodium spiking and oxy-fuel calcination

Over 13 million metric tons of biogenic carbon dioxide (CO 2 ) are mineralized yearly in United States (US) pulp mill recovery boilers as molten sodium carbonate. The mineralized CO 2 is released downstream in the rotary lime kiln where it can be captured at a relatively low cost for permanent sequestration. The use of biocarbon and bioenergy at pulp mills enables the possibility for atmospheric carbon removal when biogenic CO2 is captured and sequestered. We demonstrate the feasibility of capturing biogenic CO 2 via sodium spiking coupled with oxy-fuel calcination in the rotary lime kiln at existing kraft pulp mills. Sodium (Na) spiking elevates the Na ion loading in the kraft chemical looping process by replacing chlorine-based bleaching with a highly alkaline bleaching sequence. Chemical pulping processes are modeled and simulated to understand the technical limits of implementing sodium spiking in existing pulp mills. Each 1 % of sodium added to the bleaching operations increases the rate of CO 2 mineralization by 4 %, and the maximum increase in sodium content in the kraft process is 9 %. Without sodium spiking, estimated CO 2 capture costs are $131 and $107/mt CO 2 for air and oxy-fuel combustion, respectively. With the implementation of sodium spiking, the cost of CO 2 captured decreases by 27 % and 31 %, showing costs of $96 and $74/mt CO 2 for air and oxy-fuel combustion, respectively. Oxy-fuel combustion reduces the costs of CO 2 capture compared to air combustion, but merged deployment with sodium spiking seems to be the most cost-effective pathway to integrate carbon capture.

60 APPLIED LIFE SCIENCES↗

Chemical and electrochemical pathways to low-carbon iron and steel

Currently, the iron and steel industry is responsible for 7% of global CO 2 emissions. In this review, we summarize the operational principles of current emissions-intensive steelmaking technologies and review emerging low- and zero-carbon technologies that could substantially reduce emissions. Current technologies that are discussed include blast furnaces, electric arc furnaces, and smelting. Promising low-carbon routes include use of alternative reductants for ore processing (hydrogen direct reduction, hydrogen plasma-smelting, hydrogen smelting, and ammonia-based reduction), electrolytic iron production (with aqueous and molten oxide electrolytes) and biocarbon-based electric arc furnace operation. Advantages of each approach are presented, and remaining research hurdles are identified.

36 MATERIALS SCIENCE↗

Possible limits on the composition of the Archaean Ocean

The potential impact of high carbon dioxide partial pressure on ocean chemistry is examined in order to investigate what constraints are imposed by the known record of chemical sedimentation through time. The evidence consists of the persistence of calcium carbonate and sulfate precipitation throughout almost the entire sedimentary rock record. A uniformitarian point of view that assumes no very great change in the conditions for the deposition of these chemical sediments. The methods of Holland (1972) are used to set limits on the composition of the water from which precipitation occurred. No inconsistencies between the sedimentary rock record and presumed higher partial pressure of carbon dioxide early in earth history, provided that high partial pressure was accompanied by a generally lower pH for seawater, higher concentrations of calcium and biocarbonate ions, and lower concentrations of carbonate and sulfate ions.

Walker, J. C. G.↗

Identification of a volatile phytotoxin from algae

The objectives were to develop a trap system for isolating fractions of volatile algal phytotoxin and to characterize the major components of the isolated phytotoxin fractions. A bioassay using Phaseolus vulgaris seedlings was developed to aid in investigating the properties of the phytotoxin produced by cultures of Euglena gracilis var. bacillaris and Chlorella vulgaris. Two traps were found, 1.0 M hydrochloric acid and 0 C, which removed the phytotoxin from the algal effluent and which could be treated to release that phytotoxin as judged with the bioassay procedure. It was also determined that pretraps of 1.0 M sodium hydroxide and 1.0 M potassium biocarbonate could be used without lowering the phytotoxin effect. Ammonia was identified in trap solutions by ninhydrin reaction, indophenol reaction and derivatization with dansyl chloride and phenylisothiocyanate. Ammonia at the gaseous concentrations detected was found to have the same effects in the bioassay system as the volatile phytotoxin. It is possible that other basic, nitrogen containing compounds which augment the effects of ammonia were present at lower concentrations in the algal effluent.

Garavelli, J. S.↗

Calcification and photosynthesis of the coral acropora cervicornis under calcium limited conditions

Differing hypothesis about the function of calcification are based on an interesting dilemma. Is the purpose of calcification mainly a structural and protective one or does calcification serve other functions? Does photosynthesis increase carbonate ion activity and cause calcification or does calcification increase CO2 levels and stimulate photsynthesis? It is proposed that calcification in corals is not dependent upon photosynthesis but upon calcium levels in the water. Under normal ocean conditions, corals convert a certain percentage of energy to photosynthesis and respiration and another percentage to calcification. As corals become nutrient stressed, particularly calcium limited, the ratio of photosynthesis to calcification shifts towards calcification in order to generate protons. The protons generated during calcification may stimulate photosynthesis and aid in the uptake of nutrients and biocarbonates. The results of the calcification experiment show a trend towards increased calcification and decreased photosynthesis when the coral Acropora cervicornis is calcium limited, but the data are inconclusive and further research is needed.

Rathfon, Megan↗

Prebiotic Polymer Synthesis and the Origin of Glycolytic Metabolism

Our research resulted in several discoveries which contributed to understanding the origin and operation of life. (1) Most importantly, we discovered a new pathway of prebiotic amino acid synthesis in which formaldehyde and glycolaldehyde (formose reaction substrates) react with ammonia to give alanine and homoserine in the presence of thiol catalysts. The thiol-dependent synthesis of amino acids undoubtedly occurs via amino acid thioester intermediates capable of forming peptides. This 'one-pot' reaction system operates under mild aqueous conditions, and like modern amino acid biosynthesis, uses sugar intermediates which are converted to amino acids by energy-yielding redox disproportionation. Preliminary evidence suggests that this type of process can be "evolved" by a serial transfer methods that lead to enrichment of autocatalytic molecules. (2) We established that prebiotic peptide polymers can be made by condensation of amino acid thioesters (homocysteine thiolactone and S-(N-beta-orotidyl- diaminopropionic acid) ethanethiol), and that prebiotic polydisulfide polymers can be generated by oxidation of dithiols with iron(III) in minerals. (3) In our analysis of metabolism we discovered the primary energy source of biosynthesis -- chemical energy made available by the redox disproportionation of substrate carbon groups. We concluded that the energy and reactivity of sugars make them the optimal substrate for the origin and operation of terrestrial (or extraterrestrial) life. (4) Since it is likely that the use of optimal sugar substrates in biosynthesis sets the average oxidation number of functional biocarbon throughout the Universe near 0.0 (the reduction level of formaldehyde), we proposed that a line(s) in the microwave spectrum of formaldehyde could be rationally selected as a frequency for interstellar communication that symbolizes life. (5) Finally, in preparation for the analysis of Martian meteorite samples, we upgraded our HPLC system to one femtomole sensitivity, and developed a new electrophoretic method of sample preparation for HPLC analysis of the meteoritic amino acids. In a sample of the KT boundary layer from Sussex Wyoming, we found about 300 picomoles per gram of meteoritic alpha-aminoisobutyric acid per gram of KT layer.

Weber, Arthur L.↗

Bio-Oil Co-Processing with Refinery Streams

The project seeks to accelerate the adoption of co-processing biomass-derived feedstocks with petroleum streams in operating petroleum refineries to produce biogenic-carbon-containing fuels.

bio-crude↗