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Beneficial Use of Carbon Dioxide in Precast Concrete Production

The feasibility of using carbon dioxide as feedstock in precast concrete production is studied. Carbon dioxide reacts with calcium compounds in concrete, producing solid calcium carbonates in binding matrix. Two typical precast products are examined for their capacity to store carbon dioxide during the production. They are concrete blocks and fiber-cement panels. The two products are currently mass produced and cured by steam. Carbon dioxide can be used to replace steam in curing process to accelerate early strength, improve the long-term durability and reduce energy and emission. For a reaction within a 24-hour process window, the theoretical maximum possible carbon uptake in concrete is found to be 29% based on cement mass in the product. To reach the maximum uptake, a special process is developed to promote the reaction efficiency to 60-80% in 4-hour carbon dioxide curing and improve the resistance to freeze-thaw cycling and sulfate ion attack. The process is also optimized to meet the project target of $10/tCO 2 in carbon utilization. By the use of self-concentrating absorption technology, high purity CO 2 can be produced at a price below $40/t. With low cost CO 2 capture and utilization technologies, it is feasible to establish a network for carbon capture and utilization at the vicinity of carbon sources. If all block produces and panel producers in United States could adopt carbon dioxide process in their production in place of steam, carbon utilization in these two markets alone could consume more than 2 Mt CO 2 /year. This capture and utilization process can be extended to more precast products and will continue for years to come.

36 MATERIALS SCIENCE↗

Comparison of Fission Product Release Predictions Using PARFUME with Results from the AGR-1 Irradiation Experiment

This report documents comparisons between post-irradiation examination measurements and model predictions of silver (Ag), cesium (Cs), and strontium (Sr) release from selected tristructural isotropic (TRISO) fuel particles and compacts during the first irradiation test of the Advanced Gas Reactor program that occurred from December 2006 to November 2009 in the Advanced Test Reactor (ATR) at Idaho National Laboratory (INL). The modeling was performed using the particle fuel model computer code PARFUME (PARticle FUel ModEl) developed at INL. PARFUME is an advanced gas-cooled reactor fuel performance modeling and analysis code (Miller 2009). It has been developed as an integrated mechanistic code that evaluates the thermal, mechanical, and physico-chemical behavior of fuel particles during irradiation to determine the failure probability of a population of fuel particles given the particle-to-particle statistical variations in physical dimensions and material properties that arise from the fuel fabrication process, accounting for all viable mechanisms that can lead to particle failure. The code also determines the diffusion of fission products from the fuel through the particle coating layers, and through the fuel matrix to the coolant boundary. The subsequent release of fission products is calculated at the compact level (release of fission products from the compact) but it can be assessed at the particle level by adjusting the diffusivity in the fuel matrix to very high values. Furthermore, the diffusivity of each layer can be individually set to a high value (typically 10-6 m2/s) to simulate a failed layer with no capability of fission product retention. In this study, the comparison to PIE focused on fission product release and because of the lack of failure in the irradiation, the probability of particle failure was not calculated. During the AGR-1 irradiation campaign, the fuel kernel produced and released fission products, which migrated through the successive layers of the TRISO-coated particle and potentially through the compact matrix. The release of these fission products was measured in PIE and modeled with PARFUME.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Metabolic Engineering and Modeling of Metabolic Pathways to Improve Hydrogen Production by Photosynthetic Bacteria

Rising energy demands and the imperative to reduce carbon dioxide (CO 2 ) emissions are driving research on biofuels development. Hydrogen gas (H 2 ) is one of the most promising biofuels and is seen as a future energy carrier by virtue of the fact that 1) it is renewable, 2) does not evolve the “greenhouse gas” CO 2 in combustion, 3) liberates large amounts of energy per unit weight in combustion (having about 3 times the energy content of gasoline), and 4) is easily converted to electricity by fuel cells. Among the various bioenergy strategies, environmental groups and others say that the concept of the direct manufacture of alternative fuels, such as H 2 , by photosynthetic organisms is the only biofuel alternative without significant negative criticism [1]. Biological H 2 production by photosynthetic microorganisms requires the use of a simple solar reactor such as a transparent closed box, with low energy requirements, and is considered as an attractive system to develop as a biocatalyst for H 2 production [2]. Various purple bacteria including Rhodopseudomonas palustris, can utilize organic substrates as electron donors to produce H 2 at the expense of solar energy. Because of the elimination of energy cost used for H 2 O oxidation and the prevention of the production of O 2 that inhibits the H 2 -producing enzymes, the efficiency of light energy conversion to H 2 by anoxygenic photosynthetic bacteria is in principle much higher than that by green algae or cyanobacteria, and is regarded as one of the most promising cultures for biological H 2 production [3]. Here implemented a simple and relatively straightforward strategy for hydrogen production by photosynthetic microorganisms using sunlight, sulfur- or iron-based inorganic substrates, and CO 2 as the feedstock. Carefully selected microorganisms with bioengineered beneficial traits act as the biocatalysts of the process designed to both enhance the system efficiency of CO 2 fixation and the net hydrogen production rate. Additionally we applied metabolic engineering approaches guided by computational modeling for the chosen model microorganisms to enable efficient hydrogen production.

59 BASIC BIOLOGICAL SCIENCES↗

Commercial Superconducting Electron Linac for Radioisotope Production

The majority of radioisotopes used in the United States today come from foreign suppliers or are generated parasitically in large government accelerators and nuclear reactors. Both of these restrictions limit the availability of radioisotopes and discourage the development and evaluation of new isotopes and for nuclear medicine, science, and industry. Numerous studies have been recommending development of dedicated accelerators for production of radioisotopes for over 20 years (Institute of Medicine, 1995; Reba, et al, 2000; National Research Council, 2007; NSAC 2009). The 2015 NSAC Long Range Plan for Isotopes again identified electron accelerators as an area for continued research and development. Recommendation 1(c) from the 2015 NSAC Isotope report specifically identifies electron accelerators for continued funding for the purpose of producing medical and industrial radioisotopes. Recognizing the pressing need for new production methods of radioisotopes, the United States Congress passed the American Medical Isotope Production Act of 2012 to develop a domestic production of 99 Mo and to eliminate the use of highly enriched uranium (HEU) in the production of 99 Mo. One of the advantages of high power electron linear accelerators (linacs) is they can create both proton- and neutron-rich isotopes by generating high energy x-rays that knock out protons or neutrons from stable atoms or by fission of uranium. This allows for production of isotopes not possible in nuclear reactors. Recent advances in superconducting electron linacs have decreased the size and complexity of these systems such that they are economically competitive with nuclear reactors and large, high energy accelerators. Niowave, Inc. has been developing a radioisotope production facility based on a superconducting electron linac with liquid metal converters.

43 PARTICLE ACCELERATORS↗

Study of Single Top Quark Production Using Bayesian Neural Networks With D0 Detector at the Tevatron

Top quark, the heaviest and most intriguing among the six known quarks, can be created via two independent production mechanisms in {\pp} collisions. The primary mode, strong {\ttbar} pair production from a $gtt$ vertex, was used by the {\d0} and CDF collaborations to establish the existence of the top quark in March 1995. The second mode is the electroweak production of a single top quark or antiquark, which has been observed recently in March 2009. Since single top quarks are produced at hadron colliders through a $Wtb$ vertex, thereby provide a direct probe of the nature of $Wtb$ coupling and of the Cabibbo-Kobayashi-Maskawa matrix element, $V_{tb}$. So this mechanism provides a sensitive probe for several, standard model and beyond standard model, parameters such as anomalous $Wtb$ couplings. In this thesis, we measure the cross section of the electroweak produced top quark in three different production modes, $s+t$, $s$ and $t$-channels using a technique based on the Bayesian neural networks. This technique is applied for analysis of the 5.4 $fb^{-1}$ of data collected by the {\d0} detector. From a comparison of the Bayesian neural networks discriminants between data and the signal-background model using Bayesian statistics, the cross sections of the top quark produced through the electroweak mechanism have been measured as: \[\sigma(p\bar{p}→tb+X,tqb+X) = 3.11^{+0.77}_{-0.71}\;\rm pb\] \[\sigma(p\bar{p}→tb+X) = 0.72^{+0.44}_{-0.43}\;\rm pb\] \[\sigma(p\bar{p}→tqb+X) = 2.92^{+0.87}_{-0.73}\;\rm pb\] % The $s+t$-channel has a gaussian significance of $4.7\sigma$, the $s$-channel $0.9\sigma$ and the $t$-channel~$4.7\sigma$. The results are consistent with the standard model predictions within one standard deviation. By combining these results with the results for two other analyses (using different MVA techniques) improved results \[\sigma(p\bar{p}→tb+X,tqb+X) = 3.43^{+0.73}_{-0.74}\;\rm pb\] \[\sigma(p\bar{p}→tb+X) = 0.68^{+0.38}_{-0.35}\;\rm pb\] \[\sigma(p\bar{p}→tqb+X) = 2.86^{+0.69}_{-0.63}\;\rm pb\] % were obtained with a significance of $5.4\sigma$, $1.8\sigma$ and $5.0\sigma$ respectively for $s+t$, $s$ and $t$-channels. Using this measured cross section and constraining $0 \leq |V_{tb}|^2 \leq 1$, the lower limit has been calculated to be $|V_{tb}| > 0.79$ with 95\% confidence level (C.L.). Another measurement of $tqb$ production cross section is done using the same dataset and discriminant but without any assumption on the $tb$ production rate. From this measurement, we obtain a cross section of $2.90^{+0.59}_{-0.59}$~pb for $t$-channel and corresponding significance of $5.5\sigma$. In addition to the above mentioned work, a search is made for the anomalous $Wtb$ couplings in single top quark production. Within the Standard Model, the $Wtb$ vertex is purely left-handed, and its amplitude is given by the $V_{tb}$, related to weak interaction between a top and a $b$-quark. In a more general way, additional anomalous couplings such as right-handed vectorial couplings and left and right-handed tensorial couplings can also be considered. An analysis based on the Bayesian neural networks method is used to separate the signal from expected backgrounds. We find no evidence for anomalous couplings and set 95\% C.L. limits on these couplings as $|V_{tb} \cdot f_{L_T}|^2<0.06$, $|V_{tb} \cdot f_{R_V}|^2<0.93$ and $|V_{tb} \cdot f_{R_T}|^2<0.13$. This result represents the most stringent direct constraints on anomalous $Wtb$ interactions. This work has been done in collaboration with \d0 experiment but the analyses and results presented in this thesis are my contribution.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Direct production of 99m Tc using a small medical cyclotron

This project describes an investigation towards the production of 99m Tc with a small medical cyclotron. This endeavor addresses the current urgent problem of availability of 99m Tc due to the ongoing production reactor failures and the upcoming Canadian reactor shut down. Currently, 99m Tc is produced via nuclear fission using highly enriched uranium which is a concern due to nuclear proliferation risks. In addition to this, the United States is dependent solely on currently unreliable foreign sources of this important medical isotope. Clearly, a need exists to probe alternative production routes of 99m Tc. In the first year, this project measured cross-sections and production yields of potential pathways to 99m Tc and associated radionuclidic impurities produced via these pathways using a small 15 MeV medical cyclotron. During the second and third years target systems for the production of 99m Tc via the most promising reaction routes were developed and separation techniques for the isolation of 99m Tc from the irradiated target material will be investigated. Systems for the recycling of the enriched target isotopes as well as automated target processing systems were examined in years four and five. This project has the potential to alleviate some of the current crisis in the medical community by developing a technique to produce 99m Tc on location at a university hospital. This technology will be applicable at many other sites in the United States as many other similar, low energy (<20 MeV) cyclotrons (currently used for a few hours per day for the production of [ 18 F]fluorodeoxyglucose) are available for production of 99m Tc though this method, thus leading to job creation and preservation.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Direct production of 99m Tc using a small medical cyclotron

This project describes an investigation towards the production of 99m Tc with a small medical cyclotron. This endeavor addresses the current urgent problem of availability of 99m Tc due to the ongoing production reactor failures and the upcoming Canadian reactor shut down. Currently, 99m Tc is produced via nuclear fission using highly enriched uranium which is a concern due to nuclear proliferation risks. In addition to this, the United States is dependent solely on currently unreliable foreign sources of this important medical isotope. Clearly, a need exists to probe alternative production routes of 99m Tc. In the first year, this project measured cross-sections and production yields of potential pathways to 99m Tc and associated radionuclidic impurities produced via these pathways using a small 15 MeV medical cyclotron. During the second and third years target systems for the production of 99m Tc via the most promising reaction routes were developed and separation techniques for the isolation of 99m Tc from the irradiated target material will be investigated. Systems for the recycling of the enriched target isotopes as well as automated target processing systems were examined in years four and five. This project has the potential to alleviate some of the current crisis in the medical community by developing a technique to produce 99m Tc on location at a university hospital. This technology will be applicable at many other sites in the United States as many other similar, low energy (<20 MeV) cyclotrons (currently used for a few hours per day for the production of [ 18 F]fluorodeoxyglucose) are available for production of 99m Tc though this method, thus leading to job creation and preservation.

07 ISOTOPE AND RADIATION SOURCES↗

Production of High Performance Lubricants from Cellulosic Sugar

Certain classes of fatty acids are valuable raw materials that can used to produce bio-based lubricants; however, their broader use has been limited by the high cost and limited availability. The project described in this report was focused on producing a fatty acid methyl ester (FAME) of a specific chain length from cellulosic sugars. Development of a biological pathway and engineered organisms for production of low-cost FAME from cellulosic sugar is a novel and potentially disruptive technology that is supportive of BETO’s mission to displace all fractions of a barrel of crude oil. The project was organized around four tasks that focus on A) production pathway engineering, B) host strain engineering, C) assembly of production pathway in host strain, and D) fermentation process development. Pathway engineering focused on discovery and improvement of two key pathway enzymes, namely 3-keto acetyl CoA synthase (KAS) and wax ester synthase (WES). Both enzymes were improved using a variety of enzyme engineering and mutagenesis approaches, and assembled into a host strain with relevant additional pathway genes and genome modifications. Assembled strains were evaluated in 2-L benchtop fermenters using a commercially produced cellulosic hydrolysate to supply carbon source for FAME production. These evaluations demonstrated that performance targets and final milestones were met or exceeded for sugar uptake rate, product titer, product specificity, and production rate.

60 APPLIED LIFE SCIENCES↗

Systems Biology Towards a Continuous Platform for Biofuels Production

The goal of our project was to develop Bacillus megaterium as a host for continuous biofuel production coupled with in situ product extraction by supercritical (sc) CO 2 stripping. We aimed to develop a system that utilizes supercritical CO 2 (scCO 2 ) to address challenges associated with microbial contamination, product toxicity, and product recovery that currently limit the potential of advanced biofuel and bio-based chemical production. We proposed an interdisciplinary research and development effort involving bioprocess engineering, systems biology, and chemical separation engineering, centered around a recently isolated microorganism that is tolerant to scCO 2 . To this end we pursued a series of Aims and Sub-Aims with the ultimate goals of 1) determining the systems physiology of B. megaterium during growth under scCO 2 (Aim 1); 2) engineering heterologous butanol production pathways for anaerobic and aerobic expression in B. megaterium (Aims 1 & 2); 3) conducting de novo pathway engineering for biosynthesis of longer chain fuels (Aim 2); and 4) developing and modeling a two-phase stripping chemostat for continuous production of biofuels with in situ scCO 2 extraction (Aim 3).

09 BIOMASS FUELS↗

Removal of High Specific Activity Fission Products from Uranyl Sulfate Waste Solutions

The Savannah River National Laboratory (SRNL) is currently providing support to SHINE Medical Technologies (SHINE) which plans to deploy a low energy, accelerator-based neutron source to fission low enriched U in a uranyl sulfate target solution for 99 Mo production. The 99 Mo is initially separated from the fission products and target solution by an extraction column. Subsequent washing of the column will generate waste solutions containing residual U and fission product activity. A small number of high specific activity fission products (e.g., 90 Sr, 137 Cs, and 144 Ce) in these streams will likely control the classification of the low level waste (LLW). If a sufficient amount of the high specific activity isotopes are separated from the SHINE waste streams and concentrated into a waste form, it would be possible to treat a majority of the wash solutions from the column operations as a lower class of LLW (Class A versus Class B or C or Class B versus Class C). The high specific activity fission product elements could then be dispositioned as a much smaller volume of waste rather than requiring the disposal of the entire waste stream at the higher waste classification. The Savannah River Site (SRS) has experience with using monosodium titanate (MST) and crystalline silicotitanate (CST) to remove Cs and Sr from high salt content waste solutions generated during the reprocessing of nuclear fuels and targets. Both of these materials have worked very well for their intended purposes at the SRS where the fission product elements are removed from highly alkaline waste. On the other hand, SHINE waste streams from the extraction column contain H 2 SO 4 which makes the solution acidic. Additionally, the SRS waste streams do not contain other fission product elements such as transition metals or lanthanides because they precipitate upon neutralization of the SRS waste and are not present in the supernate which is dispositioned as LLW following treatment. As such, there are inherent differences between SHINE and SRS waste treatment strategies. Savannah River National Laboratory was tasked with performing scoping studies to see if MST and CST would remove Sr, Cs, and Ce from an acidic mixed metal simulant solution. Batch contact experiments were performed using MST and two CST type materials. The MST material is a 15 wt % powder in 0.15 M NaOH slurry. The MST showed low adsorption for elements of interest from acidic solution. Furthermore, the powder size makes MST non-ideal for column operations. A CST IE-911 ion exchange material had high Cs adsorption, moderate Sr, and marginal Ce adsorption. Based on adsorption of all species, the ion exchange capacity was found to be 0.032 meq/mL. A bench-top column experiment to measure elemental breakthrough curves was performed using CST IE-911 where chromatographic separations of the mixed simulant were expected to occur. While most elements behaved as expected, the lanthanide series, containing Ce, broke though the column earlier than expected. The second CST material, CST R9120, displayed high adsorption for all elements in the acidic mixed simulant solutions in a batch contact study, and had a calculated loading capacity of 0.091 meq/mL. Future studies to develop a waste treatment flowsheet should focus on CST R9120 to treat SHINE waste solutions.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Biosensor and optogenetics for systems biology of yeast branched-chain alcohol production and tolerance

In this project we combined synthetic biology, systems biology, protein engineering and metabolic engineering to study, control, and improve the production of branched chain alcohols (BCAs), a class of advanced biofuels preferred by the DOE, in the yeast Saccharomyces cerevisiae. This involved the development and application of optogenetic systems as a new modality of dynamic control of native and engineered metabolic pathways, using light as inducible or repressible agent. The optogenetic systems include gene circuits for light control of gene expression, as well as light-assembled synthetic organelles and photo-switchable protein binders to control metabolic and protein function with light at the protein level. In addition, we developed the first genetically encoded biosensor for BCA production in yeast, which we used to design high throughput assays to identify highly productive strains, pathways, and enzymes. We also showed that this biosensor can be functionally co-expressed with optogenetic circuits in the same strain, raising the possibility of establishing, for the first time, computer-interfaced closed-loop controls of engineered metabolic pathways. The yeast gene deletion library was also utilized to conduct the first systems-level study on BCA toxicity in yeast, which uncovered key fundamental principles of yeast sensitivity and tolerance to these alcohols, allowing us to design highly tolerant strains with increased BCA production. This project, thus comprises the development of several new technologies, which we integrated to make new discoveries on the dynamics of BCA production and their mechanisms of cellular toxicity and tolerance, as well as to establish new paradigms to engineer and control metabolic pathways and microbial fermentations with light, for the production of BCAs and other products of interest to the DOE.

2-metyl-1-butanol↗

Evaluating Production Implications of Pressure Maintenance in Unconventional Oil and Gas Wells using a Machine Learning Modeling Approach: Case Study in the Permian Basin

This study implements the proprietary machine learning-based model (model) developed under the 2022 study titled “Evaluating the Impact of Proprietary Oil & Gas Data on Machine Learning Model Performance Using a Quasi-Experimental Analytical Approach” for forecasting unconventional oil and gas production using well data from the Permian Basin. The model, developed using an exclusive dataset that includes time series production data from an operator in the Permian Basin, is designed to jointly predict daily oil, gas, and water production for horizontal wells as a function of bottomhole pressure drawdown, spatial placement across the study domain, and well-completion attributes. In this study, the model was explicitly applied to explore its utility to evaluate the impact of varying drawdown strategies on the production forecast of a well in the Permian Basin dataset. Managing pressure drawdown has been identified as a way to improve estimated ultimate recovery (EUR) from unconventional shale wells due to the stress-dependent nature of fractures in shale reservoirs. Research has shown that applying a lower pressure drawdown helps to maintain the reservoir conductivity, resulting in higher productivity over the life of a well. Historic bottomhole pressure data from the well over time was used as a benchmark from which to set more and less aggressive pressure decline rates as bounding modeling cases. All pressure decline rates/strategies were forecasted over 5 years, and the model was used to generate oil, water, and gas prediction over the same timeframe. This report presents the results from the production forecast and discusses potential operational and economic implications, with contrasting perspectives between well productivity and profitability given typical oil and gas economics and the volatility in the oil and gas market.

02 PETROLEUM↗

Multi-Sourced Collaboration for the Production and Refining of Rare Elements and Critical Metals (Final Technical Report)

The project objective was to develop a feasible and cost-effective method for recovering rare earth elements (REEs) and critical materials (CMs) from coal and coal byproducts, resulting in high-purity individually separated REEs and CMs. The targeted REEs included Y, Pr, Nd, Gd, Dy, and Sm, with a purity of over 99.5%, while the CMs included Co, Mn, Ga, Sr, Li, Ni, Zn, and Ge, with a purity of over 90%. The project aimed to design a prototype facility capable of producing 1-3 tonnes/day of high-purity REO mixes. The work was divided into four designated circuits: 1) REE extraction and concentration, 2) REE separation and purification, 3) RE metal production, and 4) CM production. To achieve these goals, the project involved 11 tasks, including technology reviews, research, process flow diagram development, mass balance estimation, and preliminary technical-economic analysis. The project team included researchers from the University of Kentucky, University of Alabama and Virginia Tech as well as process specialists from Argonne National Laboratory. MP Materials provided technical support regarding rare earth markets and processing while Alliance Coal performed resource assessment. The project included a market analysis for Nd/Pr, Tb, Dy, Gd, Y, Co, Mn, Li, Sr, Ga, Ni, Zn, and Ge. These analyses provided insights into the supply and demand trends as well as historic and future projections of market price relative to purity requirements for these elements. Two coal resources were selected for the project: the West Kentucky No. 13 (Baker) Seam and an undisclosed lignite resource in the Illinois coal basin. The estimated quantities of REEs in these resources were calculated based on production samples and drilling data. It was estimated that there is adequate supply for an operation producing one metric ton daily of higher purity mixed rare earth oxides (MREO) for approximately 20 years at a site located in western Kentucky. In Circuit 1, project data was obtained from a pilot heap leach and REE concentration facility. It was concluded that the existing circuit, which generated a MREO concentrate, two types of CM mixed products, and Li- and Sr-containing waters, would be suitable feed for circuits 2-4. Data from the first-of-its-kind coal coarse refuse heap leach pilot pad played a crucial role in estimating reliable elemental concentrations of the pregnant leaching solution (PLS). The average total REE concentration in the PLS was found to be 28.6 ppm. In Circuit 2, several concepts were explored including a novel process referred to as solvent-assisted chromatography (SAC). This concept involved a novel columnar reactor that incorporated multiple mixer/settlers, thereby enabling the operation of counter-flowing aqueous and organic phases. Unfortunately, due to project time constraints, a complete fundamental modeling analysis could not be completed to fully evaluate the technology. Molten salt electrowinning was considered as an alternative for circuit 3 following circuit 2 purification circuit utilizing the novel SAC process. A mass and energy balance of Nd reduction to metal in a fluoride containing molten salt electrolyte was conducted. Comparisons were made with the current state of Asian molten salt electrorefining, and potential improvements in siphoning rare earth metals (REM) from the reactor were presented. A cost estimate was performed for the production of 1 tonne per day, which yielded a total of $2.29 million for the nine electrowinning (EW) cells required. The selected option for circuits 2 and 3 was a plasma distillation process, which initially separates rare earth elements (REEs) from other elements. This is followed by selective electrowinning in various ionic liquids. The selection was made on the basis of thermodynamic modeling and experimental data previously published by a project partner. The combination offers an innovative approach to integrated refining and RE metal production. For Circuit 4, an extensive literature review was conducted for the processing of the CMs. The ultimate decision was to utilize a combined plasma and ionic liquid process as well to produce individual high-purity concentrates of Zn, Ni, Co, Mn, and Mg. A separate flowsheet for Li and Sr was recommended, which would yield carbonates of these elements. Due to the lack of suitable experimental data at this time, a process recommendation could not be provided but several methods have been proposed for consideration. Lastly, a techno-economic analysis (TEA) was conducted to assess the effectiveness of the proposed process for further investigation. The TEA results revealed a capital expense (CapEx) of $737 million and an annual operational expense (OpEx) of $220 million. Due to the selected elements, the hypothetical heap leach pad can produce 1 metric tonne per day of REO equivalent, but a conscious decision was made to only treat targeted REEs, resulting in the production of 0.4 metric tonne of REM. An estimated annual revenue of $90.87 million was projected based on standard market pricing information provided by the funding agency. During the TEA, ten different modules were evaluated for costing purposes. The precipitation circuit was identified as the largest single operational expense, followed by the Mg/Mn process due to the amount of treated metal. In terms of capital expenditures, the heap leach process incurred the highest cost, followed by the Mg/Mn process. The scalability of the plasma process is a crucial consideration since the reactors cannot be scaled beyond the largest demonstrated size due to their reliance on surface area of the slag and vapor phase. The purity estimate for the REEs are generally 98%±2% to produce a metal. The purity level being lower than the project objective was due to the lack of specific experimental data needed to tighten the tolerance of the estimates. Based on literature and previous experience, the CMs are estimated as follows; Ga (95%+, metal), Sr (95%+, carbonate), Li (95%+, carbonate), Ni (98%±2%, metal), Zn (95%+, metal sponge), Ge (95%+, metal), Co (98%±2%, metal), and Mn (98%±2%, metal).

01 COAL, LIGNITE, AND PEAT↗

Direct Air Capture of CO 2 and Delivery to Photobioreactors for Algal Biofuel Production (Final Report)

A mobile DAC system was designed and constructed to pair with photobioreactors growing algae for biofuel production. The DAC system was designed as a versatile research system, rather than a compact production unit. The system was constructed and mounted on a mobile skid to facilitate transportation to the algae production site. Within the DAC system, CO 2 was captured using amine-loaded monoliths that allow for high CO 2 uptake with low pressure drop. The CO 2 is collected using a Global Thermostat patented temperature/vacuum swing adsorption (TVSA) process. Amine sorbents and process conditions were optimized to produce 10 to >20 g CO 2 .h-1. The stability of the amine sorbents was also studied, with sorbent modifications made to improve stability to degradation by oxidation. An Algenol-developed Spirulina strain (Arthrospira platensis AB2293) was selected as the production cyanobacterial strain. AB2293 cultured was inoculum for outdoor production following PBR installation by Algenol. The PBR system was composed of three independent PBRs, with each PBR composed of four hanging bags internally recirculated by a liquid turnover pump. The PBRs were operated outdoors in Atlanta, GA, and integrated with the DAC system. Algae were grown with similar productivity using DAC-CO 2 as algae grown using pure CO 2 obtained commercially (Airgas). Throughout the experimental duration, no discoloration was observed, and cellular morphology was consistent between the two experimental treatments. An LCA including lifecycle greenhouse gas emissions, full life cycle inventory of the Algenol system and the DAC system and integrated DAC+PBR system was developed. Lifecycle greenhouse gas emissions were calculated for capture of carbon dioxide using input from Global Thermostat and the National Renewable Energy Laboratory. Three scenarios for energy provision were evaluated: a natural gas combined heat and power system sized to meet the electricity requirement, a natural gas combined heat and power system sized to meet the process heat requirements, and a system without on-site power that procures the electricity from the grid. In all three cases, as expected, the major contributor to the emissions is the energy consumption associated with the desorption step of the DAC process. The LCA quantified the reduced potential energy and greenhouse gas emissions of heat and mass integration of DAC and Algenol compared to unintegrated DAC and Algenol systems. A life cycle assessment of the role of sorbent productivity and lifetime was also developed. The development of more robust, oxidation resistant DAC sorbents may enable small reductions in energy requirements and in lifecycle greenhouse gas emissions and other environmental impacts. NREL performed techno-economic analysis (TEA) to identify the integration scenario most likely to achieve a 15% cost reduction target versus the baseline. Heat and mass integration of DAC and the PBR is critical to minimizing the MFSP. The baseline case utilizes no heat and mass integration, and the DAC system provides 100% of the CO 2 required by the photobioreactors (20 tonnes/hr), operating for 12 hours/day capturing 40 tonnes CO 2 /operating hour. The minimum fuel selling price (MFSP) of ethanol calculated from the baseline case was $10.68/gal ethanol. This corresponds with a targeted MFSP of $9.07/gal ethanol (or 15% reduction). This target was achieved by integration Option 2a with the greatest cost reduction of 17.8% (or $8.78/gal) and integration Option 2b with a cost reduction of 16.4% (or $8.93/gal). Reductions in MFSP are attributed to two primary process considerations: (a) CO 2 storage at night reduces the capital expenses associated with DAC (i.e., increasing on-stream time); and (b) distributed DAC scenarios (DAC-PBR integration Options 2a and 2b) make use of boiler and DAC CHP flue gas CO 2 (free). Direct air capture on-stream time was one of the largest contributors to MFSP reduction.

09 BIOMASS FUELS↗

Advanced Algal Biofoundries for the Production of Polyurethane Precursors

The primary goal of the BEEPs project was to develop a process that could accelerate the development of algae as bioproduction platforms, from initial chemical product concept to an economically viable market supply. Under this program we elected to develop strains of algae that could generate polyurethane precursors, while simultaneously developing basic genetic tools to enable improved algal production systems. This program was specifically designed to incorporate National Laboratories as a means to utilize the expertise and facilities for new bio-production platforms. To that end, we designed a program to collaborate with the Agile BioFoundry at Lawrence Berkeley National Laboratory (LBNL) and computational platforms at Pacific Northwest National Laboratory (PNNL). In addition to these National Laboratory partners, we also had academic partners from UC Davis and Georgia Tech, as well as commercial partners Algenesis Materials and BASF. To achieve these goals, we initially focused on developing the genetic tools and high throughput screening technologies necessary to generate and assess production of polymer precursors (succinic acid) in algae and cyanobacteria, including advanced promoters and biosensors. In parallel, we computationally identified potential production bottlenecks and then used the developed genetic tools to increase production rates and yields. Constant feedback of data was used in conjunction with machine learning, high-throughput cell sorting, and synthetic biology, for additional targeted metabolic engineering. Multiple rounds of tool design, building, testing, and learning were supplied to partners at PNNL and LBNL to develop new models and tools that could expedite bioproduction platform development and increase yield performance. We targeted, and achieved, the FOA requirement yield metric of 20 g/L, as a milestone and deliverable from at least one of our engineered strains for the production of succinic acid.

09 BIOMASS FUELS↗

Energy Dependent Fission Product Yields (2nd year Milestone and Deliverables)

Introduction to the project: One of the Laboratory missions is to provide consistent, high-precision fission product; yield data critical for testing fission models and maintaining the safety and security of the nation’s nuclear weapons stockpile. However, high-quality, energy-differential fission product yield data is missing for certain actinides and neutron energies important to constrain the new U.S. Nuclear Data Program evaluation effort; It has been shown that the reactor antineutrino anomaly may be at least partially caused by roughly 20 fission products. The fission product yield data is missing or incomplete for many of these isotopes, thus it is necessary to accurately determine these values to better constrain the anomaly; Aitor Bracho is measuring very short-lived (seconds to minutes) fission product yields of 235 U and 239 Pu using monoenergetic neutron beams at E n = 60 and 560 keV; Aitor Bracho is using a direct approach utilizing a state-of-the-art rabbit transfer system, superior HPGe detector, and digital acquisition systems for fission decay measurements. The goals of this project: lop experimental capabilities and data analysis techniques to carry out the gamma-ray spectra analysis necessary for fission product yield calculation; Provide high-precision and energy-dependent fission product data supporting fission theory, neutrino physics, and applied physics.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Towards a standard approach to the analysis of carbon products generated from Natural Gas pyrolysis

Conference presentation for the work entitled “A standard approach to the analysis of carbon products generated from Natural Gas pyrolysis”. Pyrolysis of natural gas (NGP) has been proposed as a near term solution for the production of direct CO2 free (turquoise) hydrogen, to help fuel a more sustainable energy future. NGP can serve as a bridging technology while other (green) hydrogen production technologies mature. In order for NGP to be successful, the management of the generated carbon products needs to be carefully considered. Necessary markets need to be considered to incorporate the (turquoise) carbon products that are generated. A large hurdle in addressing the channeling of carbon products into desired markets is determining exactly what is manufactured from the NGP process. In this work an analysis method is presented that combines a suite of techniques for the assessment of the carbon product from Natural Gas Pyrolysis for appropriate identification and quality control.

Riley, Jarrett↗

Engineering Yeast for the Production of Acids and Esters (CRADA Final Report)

NREL and Lygos have a mutual interest in engineering yeast for the production of acids and esters as intermediates towards fuels or bioproducts. In particular, the yeast Pichia kudriavzevii is a fantastic candidate for the production of acid and ester based products including butyric acid and ethyl butyrate. However, the strain is relatively uncommon in the biotechnological space and as such there are not an abundant amount of genetic tools that are publically available. However, Lygos has been working with this species in particular for several years and has developed genetic tools and physiological characteristics and are well versed in engineering this strain for acid based products. While currently focusing on malonic acid-derived products, Lygos is not currently targeting butyric acid and ethyl butyrate but have a long term interest in these molecules and derivatives therein. This CRADA proposal seeks to leverage NREL’s immediate focus on butyric acid and ethyl butyrate, and general bioprocess expertise with Lygos’ specific knowledge on engineering P. kudriavzevii for the production of acid-based products.

09 BIOMASS FUELS↗

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