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At least 631 records · Page 35
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Prebiotic properties of Bacillus coagulans MA-13: production of galactoside hydrolyzing enzymes and characterization of the transglycosylation properties of a GH42 β-galactosidase

The spore-forming lactic acid bacterium Bacillus coagulans MA-13 has been isolated from canned beans manufacturing and successfully employed for the sustainable production of lactic acid from lignocellulosic biomass. Among lactic acid bacteria, B. coagulans strains are generally recognized as safe (GRAS) for human consumption. Low-cost microbial production of industrially valuable products such as lactic acid and various enzymes devoted to the hydrolysis of oligosaccharides and lactose, is of great importance to the food industry. Specifically, α- and β-galactosidases are attractive for their ability to hydrolyze not-digestible galactosides present in the food matrix as well as in the human gastrointestinal tract. In this work we have explored the potential of B. coagulans MA-13 as a source of metabolites and enzymes to improve the digestibility and the nutritional value of food. A combination of mass spectrometry analysis with conventional biochemical approaches has been employed to unveil the intra- and extra- cellular glycosyl hydrolase (GH) repertoire of B. coagulans MA-13 under diverse growth conditions. The highest enzymatic activity was detected on β-1,4 and α-1,6-glycosidic linkages and the enzymes responsible for these activities were unambiguously identified as β-galactosidase (GH42) and α-galactosidase (GH36), respectively. Whilst the former has been found only in the cytosol, the latter is localized also extracellularly. The export of this enzyme may occur through a not yet identified secretion mechanism, since a typical signal peptide is missing in the α-galactosidase sequence. A full biochemical characterization of the recombinant β-galactosidase has been carried out and the ability of this enzyme to perform homo- and hetero-condensation reactions to produce galacto-oligosaccharides, has been demonstrated. Probiotics which are safe for human use and are capable of producing high levels of both α-galactosidase and β-galactosidase are of great importance to the food industry. In this work we have proven the ability of B. coagulans MA-13 to over-produce these two enzymes thus paving the way for its potential use in treatment of gastrointestinal diseases.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Use of the lignocellulose-degrading bacterium Caldicellulosiruptor bescii to assess recalcitrance and conversion of wild-type and transgenic poplar

Abstract Background Biological conversion of lignocellulosic biomass is significantly hindered by feedstock recalcitrance, which is typically assessed through an enzymatic digestion assay, often preceded by a thermal and/or chemical pretreatment. Here, we assay 17 lines of unpretreated transgenic black cottonwood ( Populus trichocarpa ) utilizing a lignocellulose-degrading, metabolically engineered bacterium, Caldicellulosiruptor bescii . The poplar lines were assessed by incubation with an engineered C. bescii strain that solubilized and converted the hexose and pentose carbohydrates to ethanol and acetate. The resulting fermentation titer and biomass solubilization were then utilized as a measure of biomass recalcitrance and compared to data previously reported on the transgenic poplar samples. Results Of the 17 transgenic poplar lines examined with C. bescii , a wide variation in solubilization and fermentation titer was observed. While the wild type poplar control demonstrated relatively high recalcitrance with a total solubilization of only 20% and a fermentation titer of 7.3 mM, the transgenic lines resulted in solubilization ranging from 15 to 79% and fermentation titers from 6.8 to 29.6 mM. Additionally, a strong inverse correlation ( R 2 = 0.8) between conversion efficiency and lignin content was observed with lower lignin samples more easily converted and solubilized by C. bescii . Conclusions Feedstock recalcitrance can be significantly reduced with transgenic plants, but finding the correct modification may require a large sample set to identify the most advantageous genetic modifications for the feedstock. Utilizing C. bescii as a screening assay for recalcitrance, poplar lines with down-regulation of coumarate 3-hydroxylase 3 (C3H3) resulted in the highest degrees of solubilization and conversion by C. bescii . One such line, with a growth phenotype similar to the wild-type, generated more than three times the fermentation products of the wild-type poplar control, suggesting that excellent digestibility can be achieved without compromising fitness of the tree.

09 BIOMASS FUELS↗
DOE OSTI2022

Fine scale transitions of the microbiota and metabolome along the gastrointestinal tract of herbivorous fishes

Abstract Background Gut microorganisms aid in the digestion of food by providing exogenous metabolic pathways to break down organic compounds. An integration of longitudinal microbial and chemical data is necessary to illuminate how gut microorganisms supplement the energetic and nutritional requirements of animals. Although mammalian gut systems are well-studied in this capacity, the role of microbes in the breakdown and utilization of recalcitrant marine macroalgae in herbivorous fish is relatively understudied and an emerging priority for bioproduct extraction. Here we use a comprehensive survey of the marine herbivorous fish gut microbial ecosystem via parallel 16S rRNA gene amplicon profiling (microbiota) and untargeted tandem mass spectrometry (metabolomes) to demonstrate consistent transitions among 8 gut subsections across five fish of the genus of Kyphosus . Results Integration of microbial phylogenetic and chemical diversity data reveals that microbial communities and metabolomes covaried and differentiated continuously from stomach to hindgut, with the midgut containing multiple distinct and previously uncharacterized microenvironments and a distinct hindgut community dominated by obligate anaerobes. This differentiation was driven primarily by anaerobic gut endosymbionts of the classes Bacteroidia and Clostridia changing in concert with bile acids, small peptides, and phospholipids: bile acid deconjugation associated with early midgut microbiota, small peptide production associated with midgut microbiota, and phospholipid production associated with hindgut microbiota. Conclusions The combination of microbial and untargeted metabolomic data at high spatial resolution provides a new view of the diverse fish gut microenvironment and serves as a foundation to understand functional partitioning of microbial activities that contribute to the digestion of complex macroalgae in herbivorous marine fish.

Sparagon, Wesley J. (ORCID:0000000296274174)↗
DOE OSTI2012

Release of Pleurotus ostreatus Versatile-Peroxidase from Mn 2+ Repression Enhances Anthropogenic and Natural Substrate Degradation

The versatile-peroxidase (VP) encoded by mnp4 is one of the nine members of the manganese-peroxidase (MnP) gene family that constitutes part of the ligninolytic system of the white-rot basidiomycete Pleurotus ostreatus (oyster mushroom). VP enzymes exhibit dual activity on a wide range of substrates. As Mn 2+ supplement to P. ostreatus cultures results in enhanced degradation of recalcitrant compounds and lignin, we examined the effect of Mn 2+ on the expression profile of the MnP gene family. In P. ostreatus (monokaryon PC9), mnp4 was found to be the predominantly expressed mnp in Mn 2+ - deficient media, whereas strongly repressed (to approximately 1%) in Mn 2+ -supplemented media. Accordingly, in-vitro Mn 2+ -independent activity was found to be negligible. We tested whether release of mnp4 from Mn 2+ repression alters the activity of the ligninolytic system. A transformant over-expressing mnp4 (designated OEmnp4) under the control of the β-tubulin promoter was produced. Now, despite the presence of Mn 2+ in the medium, OEmnp4 produced mnp4 transcript as well as VP activity as early as 4 days after inoculation. The level of expression was constant throughout 10 days of incubation (about 0.4-fold relative to β-tubulin) and the activity was comparable to the typical activity of PC9 in Mn 2+ -deficient media. In-vivo decolorization of the azo dyes Orange II, Reactive Black 5, and Amaranth by OEmnp4 preceded that of PC9. OEmnp4 and PC9 were grown for 2 weeks under solid-state fermentation conditions on cotton stalks as a lignocellulosic substrate. [ 14 C]-lignin mineralization, in-vitro dry matter digestibility, and neutral detergent fiber digestibility were found to be significantly higher (about 25%) in OEmnp4-fermented substrate, relative to PC9. We conclude that releasing Mn 2+ suppression of VP4 by over-expression of the mnp4 gene in P. ostreatus improved its ligninolytic functionality.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2015

Enrichment and Broad Representation of Plant Biomass-Degrading Enzymes in the Specialized Hyphal Swellings of Leucoagaricus gongylophorus, the Fungal Symbiont of Leaf-Cutter Ants

Leaf-cutter ants are prolific and conspicuous Neotropical herbivores that derive energy from specialized fungus gardens they cultivate using foliar biomass. The basidiomycetous cultivar of the ants, Leucoagaricus gongylophorus, produces specialized hyphal swellings called gongylidia that serve as the primary food source of ant colonies. Gongylidia also contain lignocellulases that become concentrated in ant digestive tracts and are deposited within fecal droplets onto fresh foliar material as it is foraged by the ants. Although the enzymes concentrated by L. gongylophorus within gongylidia are thought to be critical to the initial degradation of plant biomass, only a few enzymes present in these hyphal swellings have been identified. Here we use proteomic methods to identify proteins present in the gongylidia of three Atta cephalotes colonies. Our results demonstrate that a diverse but consistent set of enzymes is present in gongylidia, including numerous lignocellulases likely involved in the degradation of polysaccharides, plant toxins, and proteins. Overall, gongylidia contained over three-quarters of all lignocellulases identified in the L. gongylophorus genome, demonstrating that the majority of the enzymes produced by this fungus for biomass breakdown are ingested by the ants. We also identify a set of 23 lignocellulases enriched in gongylidia compared to whole fungus garden samples, suggesting that certain enzymes may be particularly important in the initial degradation of foliar material. Our work sheds light on the complex interplay between leaf-cutter ants and their fungal symbiont that allows for the host insects to occupy an herbivorous niche by indirectly deriving energy from plant biomass.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2022

Modular automated bottom-up proteomic sample preparation for high-throughput applications

Manual proteomic sample preparation methods limit sample throughput and often lead to poor data quality when thousands of samples must be analyzed. Automated liquid handler systems are increasingly used to overcome these issues for many of the sample preparation steps. Here, we detail a step-by-step protocol to prepare samples for bottom-up proteomic analysis for Gram-negative bacterial and fungal cells. The full modular protocol consists of three optimized protocols to: (A) lyse Gram-negative bacteria and fungal cells; (B) quantify the amount of protein extracted; and (C) normalize the amount of protein and set up tryptic digestion. These protocols have been developed to facilitate rapid, low variance sample preparation of hundreds of samples, be easily implemented on widely-available Beckman-Coulter Biomek automated liquid handlers, and allow flexibility for future protocol development. By using this workflow 50 micrograms of protein from 96 samples can be prepared for tryptic digestion in under an hour. We validate these protocols by analyzing 47 Pseudomonas putida and Rhodosporidium toruloides samples and show that this modular workflow provides robust, reproducible proteomic samples for high-throughput applications. The expected results from these protocols are 94 peptide samples from Gram-negative bacterial and fungal cells prepared for bottom-up quantitative proteomic analysis without the need for desalting column cleanup and with protein relative quantity variance (CV%) below 15%.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Depth-resolved sagebrush root metabolomics, rhizosphere microbial communities, and geochemistry at the East River Watershed

This data set consists of results from soil nutrient profile, untargeted metabolomics, mass spec imaging, and amplicon sequencing. Data for soil nutrient profile includes common cations (Ca, Mg, Na, and K etc.) extracted from 3 digesting steps – ammonia acetate (for exchangeable cations), nitric acid (for acid dissolved fraction), and hydrofluoric acid/perchloric acid (HF/HClO4) for whole soil digestion. It also includes concentration of organic carbon, inorganic nitrogen (ammonia and nitrate) and phosphorus (Bray-1 P and nitric acid extract), and total nitrogen and phosphorus. Data for untargeted metabolomics includes metabolomic profile for root exudate/tissues and soil extracts from depths at surface soil to saprolite, that were measured using gas chromatography – mass spectrometry (GC-MS), and liquid chromatography – tandem mass spectrometry (LC-MS/MS). Data for mass spec imaging includes spatial distribution of metabolites that were detected and annotated with Fourier transformation ion cyclotron resonance mass spectrometer (FTICR-MS). Data for amplicon sequencing includes the base paired 16S and ITS ribosomal RNA sequences from Miseq Illumina sequencing. All samples were collected from 2 sampling campaign October 2022 and June 2023. Collectively, these datasets enable a mechanistic evaluation of how nutrient acquisition, especially nitrogen and phosphorus, differs between shallow roots operating in soil and deep roots functioning within the fractured bedrock zone. All files are provided as comma-separated values (CSV) fies (.csv) and (GZIP) file (.gz). The compressed .gz FASTQ files can be read directly in R using the dada2 package as part of the amplicon sequence analysis workflow. This work was supported by the Watershed Function Science Focus Area at Lawrence Berkeley National Laboratory funded by the US Department of Energy, Office of Science, Biological and Environmental Research under Contract No. DE-AC02-05CH11231. This research was performed on a project award 60563 (https://dx.doi.org/10.46936/expl.proj.2022.60563/60008727) from the Environmental Molecular Sciences Laboratory, a DOE Office of Science User Facility sponsored by the Biological and Environmental Research program under Contract No. DE-AC05-76RL01830.

EARTH SCIENCE > AGRICULTURE > SOILS > CARBON↗
DOE OSTI2013

Flexible Distributed Energy & Water from Waste for Food and Beverage Industry

Food and beverage plants inherently consume a large quantity of water and generate a high volume of wastewater rich in organic content. On one hand, water discharge regulations are getting more stringent over the time, necessitating the use of different technologies to reduce the amount of wastewater and improve the effluent water quality. On the other hand, growing energy and water costs are driving the plants to extract and reuse valuable energy and water from the wastewater stream. An integrated waste-tovalue system uses a combination of anaerobic digester (AD), reciprocating gas engine/boiler, membrane bioreactor (MBR), and reverse osmosis (RO) to recover valuable energy as heat and/or electricity as well as purify the water for reuse. While individual anaerobic digestion and membrane bioreactors are being used in increasing numbers, there is a growing need to integrate them together in a waste-to-value system for enhanced energy and water recovery. However, currently operation of these systems relies heavily on the plant operator to perform periodic sampling and off-line lab analysis to monitor the system performance, detect any abnormal condition due to variations in the wastewater and decide on appropriate remedial action needed. This leads to a conservative design and operation of these systems to avoid any potential upsets that can destabilize the system.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2014

Re-utilization of Industrial CO 2 for Algae Production Using a Phase Change Material

This is the final report of a 36-month Phase II cooperative agreement. Under this project, Touchstone Research Laboratory (Touchstone) investigated the merits of incorporating a Phase Change Material (PCM) into an open-pond algae production system that can capture and re-use the CO 2 from a coal-fired flue gas source located in Wooster, OH. The primary objective of the project was to design, construct, and operate a series of open algae ponds that accept a slipstream of flue gas from a coal-fired source and convert a significant portion of the CO 2 to liquid biofuels, electricity, and specialty products, while demonstrating the merits of the PCM technology. Construction of the pilot facility and shakedown of the facility in Wooster, OH, was completed during the first two years, and the focus of the last year was on operations and the cultivation of algae. During this Phase II effort a large-scale algae concentration unit from OpenAlgae was installed and utilized to continuously harvest algae from indoor raceways. An Algae Lysing Unit and Oil Recovery Unit were also received and installed. Initial parameters for lysing nanochloropsis were tested. Conditions were established that showed the lysing operation was effective at killing the algae cells. Continuous harvesting activities yielded over 200 kg algae dry weight for Ponds 1, 2 and 4. Studies were conducted to determine the effect of anaerobic digestion effluent as a nutrient source and the resulting lipid productivity of the algae. Lipid content and total fatty acids were unaffected by culture system and nutrient source, indicating that open raceway ponds fed diluted anaerobic digestion effluent can obtain similar lipid productivities to open raceway ponds using commercial nutrients. Data were also collected with respect to the performance of the PCM material on the pilot-scale raceway ponds. Parameters such as evaporative water loss, temperature differences, and growth/productivity were tracked. The pond with the PCM material was consistently 2 to 5°C warmer than the control pond. This difference did not seem to increase significantly over time. During phase transitions for the PCM, the magnitude of the difference between the daily minimum and maximum temperatures decreased, resulting in smaller daily temperature fluctuations. A thin layer of PCM material reduced overall water loss by 74% and consistently provided algae densities that were 80% greater than the control pond.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Biorefinery Demonstration Project Final Progress Report

In this project we focused on various aspects of biorefinery technology development including algal-biorefinery technology, thermochemical conversion of biomass to bio-oils and biochar; we tested characteristics and applications of biochars and evaluated nutrient cycling with wastewater treatment by the coupling of algal culture systems and anaerobic digestion. Key results include a method for reducing water content of bio-oil through atomized alcohol addition. The effect included increasing the pH and reducing the viscosity and cloud point of the bio-oil. Low input biochar production systems were evaluated via literature reviews and direct experimental work. Additionally, emissions were evaluated and three biochar systems were compared via a life cycle analysis. Attached growth systems for both algal cultivation and algal harvesting were found to be superior to suspended growth cultures. Nutrient requirements for algal cultivation could be obtained by the recycling of anaerobic digester effluents, thus experimentally showing that these two systems could be directly coupled. Twenty-two journal articles and six intellectual property applications resulted from the cumulative work that this project contributed to programmatically.

09 BIOMASS FUELS↗
DOE OSTI2017

Recovery of Rare Earth Elements from Coal and Coal Byproducts via a Closed Loop Leaching Process: Final Report

Objectives: Through this grant, Battelle proposes to address Area of Interest (AOI) 1 to develop a bench-scale technology to economically separate, extract, and concentrate mixed REEs from coal ash. U.S. coal and coal byproducts provide the opportunity for a domestic source of REEs. The DOE’s National Energy Technology Laboratory (NETL) has characterized various coal and coal byproducts samples and has found varying concentrations of REE ranging up to 1,000 parts per million by weight. The primary project objective is to validate the economic viability of recovering REEs from the coal byproduct coal ash using Battelle’s patented closed-loop Acid Digestion Process (ADP). This will be accomplished by selecting coal sources with the potential to provide REE concentrations above 300 parts per million by weight, collecting characterization data for coal ash samples generated via three different methods, and performing a Techno-Economic Analysis (TEA) for the proposed process. The regional availability of REE-laden coal ash, the regional market for rare earth concentrates, and the system capital and operating costs for rare earth recovery using the ADP technology will be accounted for in the TEA. Limited laboratory testing will be conducted to generate the parameters needed for the design of a bench scale system for REE recovery. The ultimate project outcome will be the design for an optimized, closed loop process to economically recovery REEs such that the process may be demonstrated at the bench scale in a Phase 2 project. Project Description: The project will encompass evaluation of the ADP technology for the economic recovery of REEs from coal and coal ash. The ADP was originally designed and demonstrated for the U.S. Army to facilitate demilitarization of cast-cured munitions via acid digestion in a closed-loop process. Proof of concept testing has been conducted on a sample of Ohio-based Middle Kittanning coal and has demonstrated the feasibility of recovering REEs using the ADP technology. In AOI 1, Ohio coal sources with the potential to provide a consistent source of rare earth element concentrations above 300 parts per million will be identified. Coal sample inventories from West Virginia and Pennsylvania will also be assessed for purposes of comparison. Three methods of preparing the coal ash will be evaluated for their potential to enhance the technical feasibility and economics of REE recovery. Three sources of coal ash are targeted for evaluation of the economics of REE recovery in this project: (1) coal ash from power generation stations, to include fly ash and/or bottom ash, (2) ash generated in a lower temperature ashing process, and (3) ash residual from Battelle’s coal liquefaction process. Making use of residual ash from coal liquefaction processes directly leverages work currently being conducted by Battelle for DOE NETL in response to DE-FOA-0000981 entitled “Greenhouse Gas Emissions Reductions Research and Development Leading to Cost-Competitive Coal-to-Liquids Based Jet Fuel Production.” Using the sample characterization results and regional information regarding REE concentration, availability and cost, a TEA will be developed. The previously generated laboratory testing results for leaching and REE recovery via the ADP will be used to perform the TEA, along with common engineering assumptions for scale up of equipment and labor costs. Finally, upon validation of the economic feasibility of the process by the TEA, limited laboratory testing will be performed to support the design of a bench scale system. In a future project phase, it is envisioned that the bench scale system will be constructed and operated to prove the process on a continuous basis.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2018

Sacrificial Protective Coating Materials that can be Regenerated In-Situ to Enable High Performance Membranes

In the pulp and paper industry, weak black liquor concentration is carried out using energy intensive evaporators. Briefly, after wood digestion, water is evaporated to concentrate weak black liquor to the point where the black liquor can be burned in a recovery boiler, which ultimately leads to the recovery of digestion chemicals. Because it is less energy intensive than heat-driven separation, pressure-driven separation of water from black liquor using membranes could reduce the energy usage by 55 trillion Btu yr -1 and carbon dioxide emissions by more than 11 million metric tons CO 2 per year if the first two evaporators are replaced. However, weak black liquor is a hot, corrosive, and highly fouling feed with organic molecules, colloids, and ions that clog membranes within hours of operation. We have shown that membrane-based concentration of weak black liquor is feasible, but only with our antifouling and anti-clogging technology that is based on a sacrificial Bio-inspired Living Skin concept. This concept is based on a conformal coating that is formed at the membrane surface and within the pores. Weak foulant adhesion dramatically decreases membrane fouling while the superhydrophilicity of the coating increases the water permeability. Moreover, the coating can be completely removed during backflushing, which removes foulants that may irreversibly adhere to the coating over long periods of time. The skin shedding completely regenerates the membrane surface and pores, restoring the original flux. This is followed by in-situ recoating, using the existing membrane plumbing and pumps, which essentially creates a brand new membrane surface.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2018

Final Report for the Project Characterization and Valorization of Aqueous Phases Derived from Liquefaction and Upgrading of Bio-Oils

The Characterization and Valorization of Aqueous Phases Derived from Liquefaction and Upgrading of Bio-Oils project developed processes to extract value from the organics within aqueous streams derived from biomass direct liquefaction processes. The focus of the project was twofold. First, we characterized a diverse set of aqueous streams from numerous processes and feedstocks. The characterization effort served to inform this project toward development around the most prevalent compounds to maximize versatility and impact. We analyzed diverse streams from hydrothermal liquefaction of lignocellulosic, algal, and waste feedstocks; catalytic fast-pyrolysis aqueous phases; fast-pyrolysis aqueous phases; and aqueous phases produced by hydroprocessing of fast-pyrolysis bio-oil. Second, thermochemical catalytic processes were developed to convert aqueous-phase organics into useful products. These processes focused mostly on organic acids and specifically acetic acid, which was found to be ubiquitous from the characterization effort. A La x Zr y O z catalyst was discovered and developed for the ketonization of acids to ketones in the condensed aqueous phase. A dual-bed steam reforming process was developed to convert acids and other organics to hydrogen for bio-oil hydroprocessing. The dual-bed reforming process consisted of a ketonization step followed by a steam reforming step with Co as the active metal. The dual-bed process significantly reduced the rate of coke deposition versus direct steam reforming of the organic acids and beneficially produced CH 4 below the equilibrium value. Finally, we demonstrated direct conversion of aqueous-phase organics to olefins over a Zn x Zr y O z catalyst. Each thermochemical catalytic process was demonstrated with process-derived aqueous mixtures. Model compounds were used to benchmark performance and optimize conditions, but emphasis was placed on utilizing “real” aqueous streams whenever possible. A liquid-liquid extraction process using methyl tert-butyl ether as the solvent was developed to segregate dissolved inorganic species and sugars from desirable light oxygenates such as acids and alcohols. Furthermore, a carbon treatment to remove color bodies was employed after it was found the presumably heavy organic chromophore species deactivated catalysts. These economic separation processes allowed for the successful demonstration of stable catalytic processing in the condensed-phase ketonization, dual-bed reforming, and direct olefin production processes for tens to hundreds of hours, which were limited only by the quantity of feed available. Techno-economic analysis of these processes demonstrated the impact possible when capturing “waste” organics as valuable products. The condensed-phase ketonization process for converting aqueous stream acids to ketones followed by reduction and dehydration to olefins sold as a co-product resulted in the reduction of the minimum fuel selling price by about 13% compared to the anaerobic-digestion, aqueous-phase treatment base case (3.74 to 4.29/GGE). The dual-bed reforming process was commensurate in price to the anaerobic digestion base case (4.24 versus 4.29/GGE). However, the need for external natural gas to produce hydrogen for bio-oil hydroprocessing was eliminated, thereby lowering the carbon impact of the process.

09 BIOMASS FUELS↗
DOE OSTI2019

Recovery of Rare Earth Elements from Coal Mining Waste Materials

The objective of this proposed project was to locate coal overburden material that had rare earth elements (REEs) at concentrations of 300 ppm or higher. After securing the feedstock the next goal was to efficiently extract and purify the feedstocks to a purity of greater than 95%. A techno economic analysis was conducted to determine the economic viability of mining and processing REEs associated with Appalachian coal deposits. All aspects of mining, mineral processing, by-product potential, waste management, permitting and economics were examined. Attention was paid to the separation, degree of purification and marketing of Rare Earth elements. Along with REEs we evaluated the economics of the recovery of other metals of interest aong with the REEs. Our site location chosen was at the Jeddo Coal Site near Hazleton, Pennsylvania. The primary site was at the Upper Leigh High Mine. However, that changed to the North Eckley Mine site. We have analyzed a third site that will now be our second alternative to North Eckley. That site is the Highland mine site. This site is in a similar basin as the North Eckley site. During this project we evaluated various acids and extraction conditions. We have settled on using HCl as the acid of choice. One of the advantages of using HCl is it allows for easy removal of the highest contaminating metal, iron. When iron reacts with HCl in the presence of high chlorides it creates the anion complex FeCl 4 -1 . This FeCl 4 -1 complex will bind with an anion exchange resin. Greater than 99.8% of the iron is removed with this technique. Once the FeCl 4 -1 complex is bound to the anion exchange resin it can be released easily by just passing water over it. This water dilutes the FeCl 4 -1 to form FeCl 3 which is not anionic and therefore not attracted to the anion exchange resin. The FeCl 3 solution is a popular water flocculating agent used all over the world for water purification. We plan on this being one of our products produced. One of our goals was to create a multipurpose facility that was capable of handling multiple feedstocks. The proposed multipurpose facility will be able process all coal biproducts and coal products. These include 1.) clays that can easily be leached with ion exchange or acid 2.) Hard mineral deposits that can be leached with high pressure acid digestion 3.) Fly ash can be leached in the high-pressure acid digestion reactor. Fly ash is not a focus of this proposal but, the beneficial aspect of its utilization in this design cannot be overlooked. 4.) Acid Mine Drainage (AMD) Sludge is a high source of REE’s and can easily be dissolved to form a pregnant leach solution. Not shown on this simplified block flow diagram but crucial to its success is the recycle of acids. Our REE separation system is a continuous ion exchange process. The first stage is the separation of the non-REEs from the REEs. This is accomplished because the REEs are relatively larger than most of the non-REEs and typically have higher oxidation states (+3) than the non-REEs. In this step all the elements stick onto the column. However, as the columns are rinsed with various concentrations of acids different elements come off. For example, monovalent elements such as sodium and potassium elute off the column with a 1M HCl solution. Divalent elements such as calcium and magnesium do not elute until a 2M HCl solution is passed over the columns. The trivalent elements (REEs) are not eluted until a much higher concentrated acid is passed of the columns. Iron is also a trivalent, but it was removed in a prior anion exchange system. Aluminum is trivalent too, but it is much smaller than the REE atoms and elutes near the end of the 2 M HCl with the divalents. At the stage 2 and 3 our volume and masses have become too small to run on the continuous system. Therefore, we used a batch chromatography column or a flash chromatography column. The stage 2 process separates these REEs into 3 different fractions. A light, mid and heavy fraction. We calculated that we recovered greater than 90% of the REEs. This third column was packed with a different stationary phase. Five elements were chosen and purified to higher than 95% purity as shown by our internal testing. These elements were shipped to the DOE.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2020

Characterization and CST Batch Contact Equilibrium Testing of Modified Tank 9H Process Supernate Samples in Support of TCCR

The Tank Closure Cesium Removal (TCCR) system uses ion exchange columns filled with crystalline silicotitanate (CST) media to process radioactive waste solutions for the removal of ¹³⁷Cs. TCCR currently focuses on dissolving Savannah River Site (SRS) radioactive tank waste (primarily sodium saltcake solids) within Tank 10H followed by at-tank ion exchange column treatment. Two supernate batches from Tank 10H have been processed through the TCCR unit and processing of a third batch is expected soon. After processing of this supernate batch, plans are to replace the CST columns and process dissolved salt solution from Tank 9H through Tank 10H and then through the new CST columns installed in the TCCR unit. The new columns are expected to contain either a media similar to an archived CST batch (IE-911) or the R9120-B CST media used in the current TCCR columns (the two materials are fundamentally the same; just different specifications, product names, and preconditioning steps). Samples of Tank 9H dissolved saltcake were received at the Savannah River National Laboratory (SRNL) and characterized. The Tank 9H supernate contained a high sodium concentration (~9.6 M Na⁺) and will require dilution to near 6 M [Na⁺] prior to processing through the TCCR unit. The cesium concentration in Tank 9H is currently significantly higher than was observed with Tank 10H. Three dilutions of the Tank 9H supernate were conducted to mimic possible dilutions that could be conducted in the tank farm prior to TCCR processing using inhibited water, sodium hydroxide, and sodium nitrate solutions. Dilution #1 was prepared by diluting the Tank 9H supernate by a factor of 1.6 with inhibited water, Dilution #2 was prepared by diluting the Tank 9H supernate by a factor of 3.7 with a mixed sodium hydroxide/sodium nitrate diluent, and Dilution #3 was prepared by also diluting by a factor of 3.7 but with sodium hydroxide only. All three dilutions have similar Na⁺ concentrations (~6 M), but Dilutions #2 and #3 contain significantly less cesium. Major and key minor components of the diluted Tank 9H supernate samples are provided in Table ES-1. Batch contact equilibrium tests were conducted with the Tank 9H dilutions and the two different CST media batches being considered for use in the new TCCR columns. Results are summarized in Table ES-2 and compared to ZAM model predictions. The highest cesium distribution coefficient and percent removal were observed with Dilution #3. IE-911 CST (an archived CST media batch) was more effective at removing cesium than the more recently prepared R9120-B CST media, though both media samples removed >88% of the cesium and the differences may not be statistically different considering the overall uncertainty. Based on the results, maximum cesium loadings were calculated for each CST media type and Tank 9H dilution. In general, maximum cesium loadings from dilutions of this supernate batch are quite high (approaching 0.1 mmol total Cs⁺/g CST for Dilution #1). The highest calculated maximum ¹³⁷Cs loading for the Tank 9H dilutions using the ZAM model with input of the tank compositions and batch contact results was 207 Ci/kg CST (Dilution #1 with IE-911 CST). In all cases, higher maximum cesium loading values were predicted for IE-911 CST versus R9120-B, although the differences varied considerably between the dilutions. The maximum loading value for IE-911 CST with Tank 9H Dilution #1 was only 7% higher than the maximum loading for R9120-B. The maximum loading value for IE-911 CST with Dilution #3 was 24% higher than the maximum loading for R9120-B. Dilution #2 was intermediate between these values. Note that these maximum loading values are the theoretical calculated values, and actual operating conditions will cause differences. A CST binder dilution (correction) factor near 0.7 (relative to pure powder CST) was required for each batch contact test with IE-911 engineered CST using the three Tank 9H dilutions. Correction factors calculated for R9120-B CST ranged from 0.56 to 0.66 for the three dilutions. Following the batch contact tests, the CST samples were isolated from the Tank 9H solution, washed, dried, and digested in acid following established procedures. The analysis results are provided in Table ES-3. Total cesium loading values determined by CST digestion were similar to the calculated loading values based on solution analysis (Table ES-2) for all samples. In addition, the CST was observed to load calcium (R9120-B sample only), iron, strontium, lead, uranium, and plutonium after contact with the waste supernate, as has been observed previously.

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DOE OSTI2021

Flowsheet for Conversion of Anion Resin from Nitrate to Sulfate Form for Disposal

Nitrate form anion exchange resins are specifically prohibited for disposal in TRU waste. At some DOE sites, spent resin was mixed with cement to immobilize the resin in a monolith with varying success. At SRS starting in the 1980s, spent anion resin has generally been converted to a more chemically stable form or it was digested with permanganate and transferred as a slurry to the HLW tank farm. In the early years of the site it is reported that over 20 metric tons of organic resin were transferred directly to the tank farm without any attempt to digest it. It appears that in the future conversion to a stable sulfate form could well be the favored disposal path for spent nitrate-form anion resin. This report will document the site history of converting between ionic forms (nitrate to sulfate) and will document process flowsheet conditions for performing that conversion.

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DOE OSTI2021

Characterization of CST Post-Processing AP-105 Hanford Tank Waste

The primary goal of the Tank Side Cesium Removal (TSCR) system, under development by Washington River Protection Solutions, LLC (WRPS), is to remove entrained solids and 137 Cs from the Hanford tank waste supernate to expedite production of low-activity waste. Ion exchange (IX) testing of 10.9 L of waste from Hanford tank 241-AP-105 (AP-105), performed by Pacific Northwest National Laboratory, used a lead-lag-polish column format, with a bed volume of 10 mL per column, to decontaminate tank waste supernate using crystalline silicotitanate (CST) as the IX media. The AP-105 Cs IX processing test, discussed elsewhere, resulted in a shorter transition zone (i.e., steeper load curve) than those defined by wastes from tanks 241-AP-107 and 241-AW-102.1 The shorter transition zone was indicative of a matrix effect retarding Cs capacity. Therefore, aliquots of spent CST from the lead, lag, and polish columns were subjected to a digestion protocol to quantify analytes retained by the CST and extrapolate the impact on Cs capacity. The spent CST was digested using a combination of 5 M HNO 3 and H 2 O 2 with vigorous heating and stirring. Due to the radiation dose accompanying the 137 Cs on the CST columns, a secondary Cs separation by ammonium molybdophosphate embedded in polyacrylonitrile (AMP-PAN) was performed to separate the 137 Cs from the CST so the samples could be contact-handled for analysis outside of a shielded facility.

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DOE OSTI2022

Improving the Economic Viability of Biological Utilization of Coal Power Plant CO 2 by Improved Algae Productivity and Integration with Wastewater Treatment

The overall goal of this project was to improve the cost-effectiveness of systems using algae to capture and beneficially utilize CO 2 from the flue gas of coal-fired power plants. Algal biomass cultivation is an attractive alternative for carbon capture and utilization because it can uptake more CO 2 per land area than any other photosynthetic crop. Also, the resulting biomass can be used to make valuable large-market commodity products, such as biofuels and animal feed. However, the use of algal carbon capture has been limited by several factors including: (1) high costs for growing algae (>$\$1,300$/ton), (2) large land requirements for algae cultivation, and (3) environmental concerns about the large amount of water and nutrient inputs needed for growing algae. This project has taken direct aim at resolving these key limitations and demonstrated several viable approaches to improve the economic and environmental feasibility of algal carbon capture. In particular, this project demonstrated a significant increase in average annual algal productivity from baseline values of 8 g/m 2 -day to above 20 g/m 2 -day. This supports a much lower projected cost of algae production (<$\$500$/ton) and reduces land requirements by more than 50%. Additionally, this project confirmed the ability to grow multiple algae species with wastewater nutrients, which facilitates the potential for substantial new revenue streams for algae cultivation based on tipping fees for nutrient laden wastewater. This study highlighted that there is more potential value in wastewater nutrient treatment credits than in the primary commodity products made from algae. The use of wastewater inputs also mitigates the concerns associated with the large amount of water needed for growing algae. The algal biomass grown for this project using wastewater and simulated flue gas inputs were characterized for potential use as an animal feed ingredient. The algae had a protein content in the range of 35-40%, which is between some common commodity animal feed products— distiller’s grains (~25-30% protein) and soybean meal (45-50% protein). In-vitro digestion tests using cattle rumen fluids, showed that this algae biomass was best suited for use as “bypass protein”, which is digested in the animal intestine. Based on the protein content and amino acid profile of the algae grown in this study, it was estimated to have market value in the range of $\$190$-$\$280$/ton. There is potential for higher value feed products if the algae content of omega-3 fatty acids or antioxidants is accounted for. This project also did small scale demonstration of forward osmosis algae dewatering and nanofiltration of hydrothermal liquefaction aqueous products, which were shown to improve the cost and energy balance for producing algal products. When all the improvements demonstrated in this study were included in techno-economic analysis, it showed there was a viable pathway to profitable algal CO 2 utilization with a payback period in the range of six to ten years.

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