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TAS::89 0227:: TAS Recovery - Recovery Act - Development of Homologous Recombination and Recombineering Technologies for Clostridial-Biotechnologies.
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AN ACID BAKING APPROACH TO ENHANCE RARE EARTH ELEMENT RECOVERY FROM BITUMINOUS COAL SOURCES
Rare earth elements (REE) are a group of 17 elements typically classified as light and heavy rare earth elements, which play a crucial role in developing the latest technologies for energy, defense, and medical sectors. Even though REEs have been found in more than 200 minerals, only bastnaesite, monazite and xenotime are commercially exploited for REE extraction. However, the recent exponential increase in REE demand has spurred countries such as the United States into research for the extraction of REEs from secondary sources such as coal, acid mine drainage, and coal ash. Several coal sources (e.g., Fire Clay seam coal) across the United States have been identified to contain elevated concentrations of rare earth elements (>600 ppm), and various researchers have investigated the feasibility of both physical and hydrometallurgical extraction techniques for rare earth concentration and subsequent extraction. However, both physical and direct leaching were concluded to be inefficient for RE beneficiation and extraction due to low recoveries. Alternatively, thermal treatment provides promising means for RE recovery from bituminous coal sources. The positive impact of thermal treatment/calcination was established to be due to the decarbonization and dehydroxylation of the clays, which released entrapped rare earth elements within the dominant minerals and converted them into an acid-soluble form. Nonetheless, the improvement in recovery was limited to the light REEs (LREEs) with an insignificant increase in the heavy REEs (HREE). It was demonstrated that the light and heavy REEs in the material were associated with difficult-to-leach minerals such as monazite, xenotime, and zircon, which were not decomposed by simple calcination due to their high thermal stability. Hence, roasting in the presence of chemicals was necessary to ensure the decomposition of those REE-containing minerals. As such, this study was focused on the acid baking treatment of bituminous coals with an aim to enhance REE recovery, especially HREEs. Based on the presence of REE minerals like monazite and xenotime, three pre-leach treatment methods, i.e., 1) roasting, 2) direct acid baking, and 3) acid baking after roasting were investigated. Roasting tests at 600 ⁰C revealed that the recovery of light REEs (LREEs) was enhanced while the recovery of HREEs remained relatively unaffected. LREE and HREE recovery values of 38.3% and 21.3%, respectively, were achieved using a 50 g/L sulfuric acid solution at 5% solid concentration and a solution temperature of 75 ⁰C for 2 hours. Comparatively, direct acid baking at 250 °C provided substantial increased LREE and HREE recovery values to approximately 49.4% and 53.0%, respectively, using an equivalent acid dosage. Recoveries were maximized to 77.0% and 79.6% for LREE and HREE, respectively, by roasting followed by acid baking. Similar results were obtained from the treatment of a second bituminous coal source. Due to strong correlations between REE and Al recovery values, tests were performed on kaolinite and illite, which were prominent clay minerals within the source coals. These experiments revealed that the REE recovery improvements were likely a result of dehydroxylation of clays and subsequent release and decomposition of REE-bearing minerals such as monazite, xenotime and zircon. Subsequently, a parametric study was conducted to identify the impact of acid baking parameters on rare earth element recovery. The factors investigated using a three-level statistical experimental program were acid baking time, acid solution concentration, baking temperature, and acid solution-to-solids ratio which were found to significantly impact REE and contaminant element (Al, Fe, and Ca) recovery. An increase in baking temperature up to around 250 ⁰C improved the light and heavy REE recovery values by more than 50 absolute percentage points relative to performances achieved when direct leaching. As aforementioned, acid baking was needed to both decompose the clay minerals and liberate the REE minerals, which allowed access for the acid to solubilize the REEs. Acid concentration of the solution used for acid baking was studied as a means of minimizing the amount of acid needed to achieve a target REE recovery. However, thermo-gravimetric and differential scanning calorimetry analysis (TGA-DSC) of sulfuric acid under oxidizing atmosphere revealed that the addition of water decreased the evaporation temperature, which explains the lower REE recovery values obtained when using acid concentrations less than 100%. Using pure sulfuric acid at an acid-to-solid ratio of 0.8:1 resulted in recovery values of around 70% for both LREEs and HREEs. The decomposition reaction time was relatively quick with 65% of the TREEs recovered within the first 10 minutes. Following the identification of optimum operating conditions through the parametric study, a systematic leaching study was carried out to examine the impact of leaching parameters, such as solid-to-liquid (S/L) ratio, temperature, and time, on REE recovery using acid baking conditions of 1:1 acid to solids ratio at 250 °C for 30 minutes. The solid-to-liquid ratio was varied from 1-20% by weight at 25 °C, 50 °C, and 75 °C solution temperatures. The results indicated that reaction time and solution temperature considerably impacted the recovery of heavy and light REEs. Interestingly, LREE recovery reduced from 68% at 5% S/L to 58% at 20%S/L, whereas HREE recovery of 78% remained unaffected. The decrease in the LREE recovery was determined to be due to La and Ce precipitation, likely through isomorphic substitution with calcium in gypsum. The kinetic data indicated that 67% LREE and 77% HREE recovery could be obtained within the first 15 minutes of the reaction, suggesting fast reaction kinetics. Furthermore, raising the solution temperature from 25 °C to 75 °C increased the LREE and HREE recovery from 60% and 32% to 67% and 79%, respectively. The kinetic modeling results demonstrated that the rate-limiting step in the LREE dissolution was diffusion and chemical reaction, whereas the HREE extraction was controlled by only chemical reaction. The leaching study concluded that using 20% S/L at 75 °C for 15 minutes maximized LREE and HREE recovery. The lab-scale precipitation study showed that Fe and Al in solution could be removed at pH 4.5 followed by REE precipitation at pH 6.0 using 6 mol/L NaOH. Finally, the bench-scale data was used to develop a process flowsheet for REE recovery from low-grade bituminous coal sources using acid baking. Finally, based on the proposed flowsheet, a concentrated RE-cake obtained through selective precipitation at pH 6.5 was re-leached using HCl at pH 1.5. The resultant leachate was used to identify the impact of various operating parameters on REE recovery and purity with an aim to maximize REE precipitation efficiency while minimizing the oxalic acid dosage. The operating parameters for this investigation were oxalic acid dosage, iron (III) contamination, solution pH and temperature. The resultant model suggested that oxalic acid dosage and reaction pH are the most significant factors for the REE precipitation efficiency, followed by the interaction of oxalic dosage and Fe concentration. Test results indicated that increasing the oxalic acid concentration from 0g/L to 80g/L improved the REE precipitation efficiency from approximately 4.2% to 95.0%. Furthermore, raising the solution pH from 0.5 to 2.5 considerably enhanced the precipitation efficiency from 0.0% to 98.9%. A solution temperature elevation decreased REE recovery, which indicated an exothermic reaction between REEs and oxalate anions. Finally, a high level of Fe contamination adversely impacted REE precipitation efficiency. The speciation analysis revealed that the dominant iron species in the solution system were Fe-(C₂O₄)₃³⁻, Fe-(C₂O₄)²⁻, and Fe-(C₂O₄)⁺, which consumed the majority of the oxalate anions
Simulation-Based Recovery Action Analysis Using the EMRALD Dynamic Risk Assessment Tool
A recovery action is defined as the action that prevents deviant conditions from producing unwanted effects. It generally indicates a kind of countermeasure performed in response to a failure of human action. The recovery actions especially play an important role in complex systems like nuclear power plants (NPPs), which consist of highly sophisticated controllers to ensure that desired performance and safety must be achieved and maintained. This is because a combination of human error and its recovery failure may be able to cause a catastrophic effect on a system. Analyzing recovery actions has been a critical part of HRA, which is a technique to evaluate human errors and provide human error probabilities (HEPs) for application in probabilistic safety assessment (PSA). If recovery actions are not adequately analyzed and applied to PSA models, the PSA results may be under-estimated or be not able to reasonably account for the failure of human actions in the context of PSA. For this reason, some regulatory documents such as ASME/ANS RA-Sb-2013 by the American Society for Mechanical Engineers and the American Nuclear Society and NUREG-1792 by U.S. Nuclear Regulatory Commission have emphasized the importance of recovery analysis within the HRA. A couple of existing HRA methods, such as the Technique for Human Error-Rate Prediction (THERP), the Cause-Based Decision Tree (CBDT), and the Korean Standard HRA (K-HRA), have respectively suggested their own approaches to the HRA recovery analysis. However, there are a couple of limitations to treating recovery actions using only the current HRA methods available. The biggest limitation is that the existing recovery analysis does not explicitly consider a variety of recovery action types and recovery sequences as they occur in actual NPPs. To handle the limitations of existing recovery analysis, this study proposes a simulation-based recovery analysis method using the Event Modeling Risk Assessment Using Linked Diagram (EMRALD) software. The EMRALD software is a dynamic simulation tool for PSA. It supports realistic and dynamic modeling of human actions as they would be performed at NPPs. It is also favorable to simultaneously model the specific moment at which an action is performed, the time it takes to perform the action, and the failure probability of that action. In this paper, a detailed methodology for modeling recovery actions in the simulation platform is proposed with a couple of examples. Then, outputs from the simulation are discussed as reviewing if this novel approach can complement the challenges of existing recovery analyses.
Idaho National Laboratory Site Natural Resources: Wildland Fire Recovery Framework
As pressures from invasive species, climate change, and anthropogenic impacts increase across the landscape in the western U.S., managing wildland fire recovery to promote healthy sagebrush steppe becomes an increasingly important stewardship responsibility. The Idaho National Laboratory (INL) has developed and implemented wildland fire recovery plans to hasten desirable vegetation re-establishment on several individual fires, but lacks an overarching wildland fire recovery strategy, or framework. The intent of this document is to develop the technical approach and scientific basis for wildland fire recovery at the INL Site and to evaluate the tools available to support it in a comprehensive and broadly applicable format. This wildland fire recovery framework will outline the process of assessing the potential impacts of wildland fire on natural resources, present a range of post-fire recovery options, outline an approach for post-fire monitoring, and provide a template for post-fire recovery plans designed to addresses the specific conditions of each wildland fire. There are numerous benefits to developing a wildland fire recovery framework for the INL Site. The first is streamlining the development of post-fire recovery plans for individual fires. A second benefit is more closely aligning INL’s post-fire planning processes with those of other federal agencies. The development of an INL Site fire recovery framework will also allow resource professionals to consider a broader set of recovery tools than they have before because all proposed tools included in the framework were vetted through the process of scoping and stakeholder review. Finally, this framework is a publicly available document that can be used as a basis for communicating and discussing post-fire natural resource recovery objectives with agency collaborators, conservation partners, and other stakeholders. Through the proactive land stewardship principles outlined in this framework, current INL sustainability initiatives can be enhanced, and future INL mission flexibility will be maintained.
A Markov framework for generalized post-event systems recovery modeling: From single to multihazards
State-dependent models can be used to represent the system recovery process as a series of stochastic transitions from lower to higher functional states. However, the applications of these models have been limited in scope and there is a lack of a generalized recovery modeling framework. A generalized framework would permit a robust forecasting of systems and system-of-systems recovery under multiple hazards, and more broadly, would contribute to community disaster preparedness. This paper develops a generalized post hazard-event recovery modeling framework based on state-dependent Markov-type processes. We then apply the proposed framework to solve a spectrum of problems that range from hind-casting single-system recovery following a single hazard event to forecasting post-event trajectories under multiple hazards and modeling the recovery of a system-of-systems. First, Markov chains are used to hind-cast the observed recovery for a portfolio of buildings affected by the 2014 South Napa, California, earthquake. Next, Markov processes are used to formulate a parametric post hazard-event recovery model, which can be updated using Bayesian statistics when relevant datasets become available. Semi-Markov processes are then used to develop a more general model of single hazard recovery, which accounts for the intensity of the loading and level of damage caused by the event. Semi-Markov processes with non-renewal features are then used to account for multihazard interactions in a post-event recovery model, and applied to a case study that involves a community in Charleston, South Carolina. Lastly, Markov-type processes are combined with Bayesian networks to model the recovery of residential, commercial, educational, and industrial buildings (system-of-systems) following a hazard event. Overall, these applications demonstrate the versatility of the Markov framework towards handling recovery problems with varying levels of complexity.
End-Use Savings Shapes: Measure Documentation: Add Exhaust Air Heat/Energy Recovery
This documentation focuses on a single end-use savings shape measure—Add Exhaust Air Heat/Energy Recovery. This measure adds exhaust air energy recovery or heat recovery to existing air handling units (AHU) with outdoor air. Systems that already have energy/heat recovery are not modified. Furthermore, food service building types are also not modified by this measure due to the added complication of integrating cooking hood exhaust that could cause heat exchanger fouling from kitchen exhaust. In total, this measure is applicable airloops serving ~70% of the floor area in ComStock. In practice, energy/heat recovery systems are retrofitted to existing air delivery systems either as separate systems that provide outdoor air to the AHUs or are directly integrated to an AHU; the modeling approach used in this study is agnostic of the energy recovery type and simply accounts recovery effectiveness, added static pressure, and other controls which are described further in this document. Energy recovery with sensible and latent exchange gets added in humid climate zones, while heat recovery with sensible-only exchange gets added in drier climate zones. Energy recovery is modeled as a fixed membrane plate counterflow heat exchanger, while heat recovery is modeled as a sensible-only fixed aluminum plate counterflow heat exchanger. Both systems include a bypass (for temperature control and economizer lockout) and electric resistance preheat coil for frost prevention.
Long-Term Post-Disturbance Forest Recovery in the Greater Yellowstone Ecosystem Analyzed Using Landsat Time Series Stack
Forest recovery from past disturbance is an integral process of ecosystem carbon cycles, and remote sensing provides an effective tool for tracking forest disturbance and recovery over large areas. Although the disturbance products (tracking the conversion from forest to non-forest type) derived using the Landsat Time Series Stack-Vegetation Change Tracker (LTSS-VCT) algorithm have been validated extensively for mapping forest disturbances across the United States, the ability of this approach to characterize long-term post-disturbance recovery (the conversion from non-forest to forest) has yet to be assessed. Here in this study, the LTSS-VCT approach was applied to examine long-term (up to 24 years) post-disturbance forest spectral recovery following stand-clearing disturbances (fire and harvests) in the Greater Yellowstone Ecosystem (GYE). Using high spatial resolution images from Google Earth, we validated the detectable forest recovery status mapped by VCT by year 2011. Validation results show that the VCT was able to map long-term post-disturbance forest recovery with overall accuracy of ~80% for different disturbance types and forest types in the GYE. Harvested areas in the GYE have higher percentages of forest recovery than burned areas by year 2011, and National Forests land generally has higher recovery rates compared with National Parks. The results also indicate that forest recovery is highly related with forest type, elevation and environmental variables such as soil type. Findings from this study can provide valuable insights for ecosystem modeling that aim to predict future carbon dynamics by integrating fine scale forest recovery conditions in GYE, in the face of climate change. Lastly, with the availability of the VCT product nationwide, this approach can also be applied to examine long-term post-disturbance forest recovery in other study regions across the U.S.
Elemental mercury neurotoxicity and clinical recovery of function: A review of findings, and implications for occupational health
Highlights: • Substantial human studies, both acute and chronic, are available for evaluation. • Elemental mercury induced toxicity often displays substantial recovery. • Numerous examples fail to show full recovery from elemental mercury toxicity. • Recovery from elemental mercury toxicity is affected by age and endpoint. • Few animal studies have been directed to elemental mercury toxicity recovery. This paper assessed approximately 30 studies, mostly involving occupationally exposed subjects, concerning the extent to which those who developed elemental mercury (Hg)-induced central and/or peripheral neurotoxicities from chronic or acute exposures recover functionality and/or performance. While some recovery occurred in the vast majority of cases, the extent of such recoveries varied considerably by individual and endpoint. Factors accounting for the extensive inter-individual variation in toxicity and recovery were not specifically assessed such as age, gender, diet, environmental enrichment, chelation strategies and dose-rate. While the data indicate that psychomotor endpoints often show substantial and relatively rapid (i.e., 2–6 months) recovery and that neuropsychological endpoints display slower and less complete recovery, generalizations are difficult due to highly variable study designs, use of different endpoints measured between studies, different Hg exposures based on blood/urine concentrations and Hg dose-rates, the poor capacity for replicating findings due to the unpredictable/episodic nature of harmful exposures to elemental Hg, and the inconsistency of the initiation of studies after induced toxicities and the differing periods of follow up during recovery periods. Finally, there is strikingly limited animal model literature on the topic of recovery/reversibility of elemental Hg toxicity, a factor which significantly contributes to the overall marked uncertainties for predicting the rate and magnitude of recovery and the factors that affect it.
Free-Spinning and Recovery Characteristics of a 1/19-Scale Model of the North American T-28C Airplane, TED No. NACA AD 3127
An investigation has been conducted in the Langley 20-foot free-spinning tunnel on a l/19-scale model of the North American T-28C airplane to determine the spin and recovery characteristics. The T-28C airplane is similar to the T-28B airplane except for slight modifications for the arresting hook. The lower rear section of the fuselage was cut out and, consequently, the lower part of the rudder was removed to make a smooth fairing with the fuselage. The T-28B airplane had good recovery characteristics; but these modifications, along with the addition of gun packages on the wings, led to poor and unsatisfactory spin-recovery characteristics during demonstration spins of the T-28C airplane. Model test results indicated that without the gun packages installed, satisfactory recoveries could be obtained if the elevators were held full back while the rudder was fully reversed and the ailerons were held neutral. However, with the addition of gun packages to the wings and the corresponding change in loading, recoveries were considered unsatisfactory. Recoveries attempted by using a larger chord or larger span rudder were improved very slightly, but were still considered marginal or unsatisfactory. Strakes placed on the nose of the model were effective in slowing the spin rotation slightly and, in most instances, decreased the turns for recovery slightly. Recovery characteristics were slightly marginal for the full fuel loading when strakes and the extended-chord rudder were installed; but with the wing fuel partly used, recovery characteristics were again considered unsatisfactory or, at least, definitely on the marginal side. The optimum control technique for recovery is movement of the rudder to full against the spin with the stick held full back (elevators full up) and the ailerons held neutral, followed by forward movement of the stick only after the spin rotation ceases. Inverted-spin test results indicate that the airplane will spin steep and fast and that recovery by full rudder reversal will be satisfactory if the ailerons are held neutral.
Manned Spacecraft Landing and Recovery
As recent history has tragically demonstrated, a successful space mission is not complete until the crew has safely returned to earth and has been successfully recovered. It is noted that a safe return to earth does not guarantee a successful recovery. The focus of this presentation will be a discussion of the ground operation assets involved in a successful recovery. The author's experience in land and water-based recovery of crewed vehicles and flight hardware at Kennedy Space Center (KSC), Edwards Air Force Base, international landing sites, and the Atlantic Ocean provides for some unique insight into this topic. He has participated in many aspects of Space Shuttle landing and recovery operations including activation of Transatlantic Abort Landing (TAL) sites and Emergency Landing Sites (ELS) as an Operations Test Director, execution of post landing convoy operations as an Orbiter Move Director, Operations Test Director, and Landing and Recovery Director, and recovery of solid rocket boosters, frustum and their parachutes 140 miles offshore in a wide range of sea states as a Retrieval Diver/Engineer. The recovery operations for the Mercury, Gemini, and Apollo were similar from a landing and recovery perspective in th t they all were capsules with limited "flying" capability and had a planned End of Mission (EOM) in an ocean with a descent slowed by parachutes. The general process was to deploy swim teams via helicopters to prepare the capsule for recovery and assist with crew extraction when required. The capsule was then hoisted onto the deck of a naval vessel. This approach required the extensive use and deployment of military assets to support the primary landing zone as well as alternate and contingency locations. The Russian Soyuz capsule also has limited "flying" capability; however, the planned EOM is terrestrial. In addition to use of parachutes to slow the reentry descent, soft-landing rockets on the bottom of the vehicle are employed to cushion the landing. The recovery forces are deployed via helicopters and the capsule is transported by a specialized all-terrain vehicle. The Space Shuttle Orbiter landing and recovery process is considerably different. The added lift capability and maneuverability allow the Orbiter to land at an exact location/runway for a nominal EOM. This allows for a timely response of recovery/contingency rescue forces, centralized staging of personnel and equipment, and assured access by ground vehicles. The well defined landing zone also provides for far more options when selecting landing sites for EOM and emergency returns and the relatively large cross-range capability increases the number of landing opportunities at the preferred sites.
Development of Electrolytic Oxygen Recovery System for Advanced Life Support
The oxygen (O2) recovery system for the International Space Station (ISS) can recover approximately 50 percent of O2 from metabolic carbon dioxide (CO2). Increasing the O2 recovery rate and closing the open loop for future long duration crewed missions in space beyond Low Earth Orbit (LEO) is essential. There are several developmental efforts underway to increase the recovery rate. However, most of these technologies result in a complex, heavy, and power consuming system. The desired exploration O2 recovery system would be reliable and efficient with maximum O2 recovery. Marshall Space Flight Center (MSFC) is currently investigating an electrolytic O2 recovery approach that will increase the O2 recovery to greater than 70 percent as well as lowering the complexity, mass, and power consumption than most other technologies currently under development. The electrolytic O2 recovery system consists of a Microfluidic Electrochemical Reactor (MFECR) that is based on the electrochemical reduction of CO2 to O2 and ethylene (C2H4) using water (H2O) as precursor and operates at standard condition with a theoretical recovery rate of 73 percent. In 2016, NASA’s Game Changing Development Program awarded the University of Texas Arlington (UTA) a grant to initiate the development of the MFECR. Since 2019, MSFC and UTA have been collaborating with the current goals of increasing the O2 recovery efficiency, advancing the technology readiness to a Technology Readiness Level (TRL) 4, and maturing the system to process CO2 of one crew-member. Based on the results from UTA’s initial efforts, the following were identified as key areas of improvement in order to maximize O2 recovery for the system: further development of the anode material and cathode catalyst, model-based cell design optimization, and the addition of a separation system and fuel cell. This paper will present the current developmental efforts of the electrolytic system including MFECR design and overall system enhancements as well as results from single cell stack testing.
Quantification of the resource recovery potential of municipal solid waste incineration bottom ashes
Highlights: • Ferrous and non-ferrous metals were quantified in MSWI bottom ashes. • Metal recovery system efficiencies for bottom ashes were estimated. • Total content of critical elements was determined in bottom ash samples. • Post-incineration recovery is not viable for most critical elements. - Abstract: Municipal solid waste incineration (MSWI) plays an important role in many European waste management systems. However, increasing focus on resource criticality has raised concern regarding the possible loss of critical resources through MSWI. The primary form of solid output from waste incinerators is bottom ashes (BAs), which also have important resource potential. Based on a full-scale Danish recovery facility, detailed material and substance flow analyses (MFA and SFA) were carried out, in order to characterise the resource recovery potential of Danish BA: (i) based on historical and experimental data, all individual flows (representing different grain size fractions) within the recovery facility were quantified, (ii) the resource potential of ferrous (Fe) and non-ferrous (NFe) metals as well as rare earth elements (REE) was determined, (iii) recovery efficiencies were quantified for scrap metal and (iv) resource potential variability and recovery efficiencies were quantified based on a range of ashes from different incinerators. Recovery efficiencies for Fe and NFe reached 85% and 61%, respectively, with the resource potential of metals in BA before recovery being 7.2%ww for Fe and 2.2%ww for NFe. Considerable non-recovered resource potential was found in fine fraction (below 2 mm), where approximately 12% of the total NFe potential in the BA were left. REEs were detected in the ashes, but the levels were two or three orders of magnitude lower than typical ore concentrations. The lack of REE enrichment in BAs indicated that the post-incineration recovery of these resources may not be a likely option with current technology. Based on these results, it is recommended to focus on limiting REE-containing products in waste for incineration and improving pre-incineration sorting initiatives for these elements.
Characterization of Recovery Human Action Mechanisms in Nuclear Power Plants
Recovery human action is defined as the action that prevents deviant conditions from producing unwanted effects. Analyzing recovery actions has been a critical part in human reliability analysis (HRA). However, there are a couple of limitations to treat recovery actions only depending on the current HRA methods. Representatively, the existing recovery analysis does not specifically consider recovery actions as are occurred in actual nuclear power plants (NPPs). The overall goal of this study aims to develop a novel recovery analysis method to account for human action recoveries in context of scenarios as well as complement the limitations of existing recovery analysis. In this paper, the recovery analysis in current HRA methods and their challenges are introduced. A strategy to achieve the goal is introduced with a modified recovery definition. Then, how we have researched the approach will be introduced in the paper.
Effectiveness of supercritical-CO 2 and N 2 huff-and-puff methods of enhanced oil recovery in shale fracture networks using microfluidic experiments
Current oil recovery methods in hydraulically fractured shale reservoirs have a low recovery efficiency of about 10%. The objective of this work is to investigate the effectiveness of nitrogen and supercritical carbon dioxide in the huff-and-puff method for enhanced oil recovery as a means to re-energize reservoirs and improve recovery rates. Here, we conduct direct visualization experiments with a microfluidic system to reveal the mechanisms and to quantify the recovery rates of oil from fracture networks. We compared the effectiveness of water, nitrogen and supercritical carbon dioxide at reservoir conditions in a process mimicking the huff-and-puff method in both dead-end and connected fracture systems. The microfluidic chips were made of glass and placed in a confining pressure system pressurized to 10 MPa, 50 °C. The system was allowed to equilibrate, and then depressurized to simulate huff-and-puff oil recovery. Fluorescence microscope images were continuously taken to visualize and calculate residual oil saturation as a function of pressure drawdown. As the system was depressurized from 10 MPa, gas exsolution from the oil liquid phase, including bubble nucleation, growth, and coalescence, appeared to be the main driver for mobilizing oil from the fracture networks. Injection of supercritical CO 2 resulted in the highest recovery rate with an average end-point recovery of about 90% in the connected fracture network and 60% in the dead-end fracture network. N 2 has lower solubility in oil and hence showed a lower recovery rate of 40% in the connected fracture network and 25% in the dead-end fracture network. Injection of water had no effect on oil mobilization since water is insoluble, immiscible and incompressible. The main mechanism of enhanced recovery was gas exsolution from the liquid phase as pressure was decreased below the bubble point pressure. Because the gas was distributed throughout the oil phase, bubble nucleation, growth, coalescence, and elongation occurred throughout the fracture network. Expansion of the gas forced oil out of the network through piston displacement in continuous oil areas and film flow in the dispersed oil areas. Bubbles began as spheres and grew until they touched the fracture walls where they elongated along the fracture length. The bubble growth rate depended on local mass transfer from liquid to gas phase and gas volume expansion due to pressure drop. The efficiency of the huff-and-puff process is dependent on the solubility and miscibility of the injection fluid with oil. High gas solubility allows for more bubble nucleation, growth and expansion during the depressurization cycle.
An acid baking approach to enhance heavy rare earth recovery from bituminous coal-based sources
The recovery of rare earth elements (REEs) from secondary resources, particularly coal-based materials, has recently received attention due to supply and demand imbalance. Research reported to date indicates that a high REE recovery can be realized when treating bituminous coal sources using strong acid solutions of approximately100 g/L or higher. This study introduces an approach to enhance the total rare earth recovery (TREE), especially for heavy rare earth elements (HREEs), from these coal sources at significantly lower acid concentrations. Based on the presence of REE minerals like monazite and xenotime, a detailed investigation was undertaken to quantify three pre-leach treatment methods, i.e., 1) roasting, 2) direct acid baking, and 3) acid baking after roasting. Roasting tests at 600°C revealed that the recovery of light REEs (LREEs) was enhanced while the recovery of HREEs remained relatively unaffected. LREE and HREE recovery values of 38.3% and 21.3%, respectively, were achieved using a 50 g/L (0.5 M) sulfuric acid solution at 5% solid concentration and a solution temperature of 75°C for 2 h. Comparatively, direct acid baking at 250°C provided substantial increases in LREE and HREE recovery values to approximately 49.4% and 53.0%, respectively, using an equivalent acid dosage. Recoveries were maximized to 77.0% and 79.6% for LREE and HREE, respectively, by roasting followed by acid baking. Similar results were obtained from the treatment of a second bituminous coal source. Due to strong correlations between REE and Al recovery values, tests were performed on kaolinite and illite, which were prominent clay minerals within the source coals. In conclusion, these experiments revealed that the REE recovery improvements were likely a result of dehydroxylation of clays and subsequent release and decomposition of REE-bearing minerals such as monazite, xenotime and zircon.
Measuring short-term post-fire forest recovery across a burn severity gradient in a mixed pine-oak forest using multi-sensor remote sensing techniques
Understanding post-fire forest recovery is pivotal to the study of forest dynamics and global carbon cycle. Field-based studies indicated a convex response of forest recovery rate to burn severity at the individual tree level, related with fire-induced tree mortality; however, these findings were constrained in spatial/temporal extents, while not detectable by traditional optical remote sensing studies, largely attributing to the contaminated effect from understory recovery. For this work, we examined whether the combined use of multi-sensor remote sensing techniques (i.e., 1m simultaneous airborne imaging spectroscopy and LiDAR and 2m satellite multi-spectral imagery) to separate canopy recovery from understory recovery would enable to quantify post-fire forest recovery rate spanning a large gradient in burn severity over large-scales. Our study was conducted in a mixed pine-oak forest in Long Island, NY, three years after a top-killing fire. Our studies remotely detected an initial increase and then decline of forest recovery rate to burn severity across the burned area, with a maximum canopy area-based recovery rate of 10% per year at moderate forest burn severity class. More intriguingly, such remotely detected convex relationships also held at species level, with pine trees being more resilient to high burn severity and having a higher maximum recovery rate (12% per year) than oak trees (4% per year). These results are one of the first quantitative evidences showing the effects of fire adaptive strategies on post-fire forest recovery, derived from relatively large spatial-temporal domains. Our study thus provides the methodological advance to link multi-sensor remote sensing techniques to monitor forest dynamics in a spatially explicit manner over large-scales, with important implications for fire-related forest management, and for constraining/benchmarking fire effect schemes in ecological process models.
Low-Temperature Plasma Treatment for Enhanced Recovery of Highly Valued Critical REEs from Coal (Final Report)
The principle objective of this project was to develop a novel process flowsheet using low-temperature plasma treatment (LTP) integrated with conventional hydrometallurgical processes to recover rare earth elements (REEs), especially highly valued REEs (i.e. scandium and critical REEs), from coal and coal byproducts. LTP treatment was used to pretreat the solid feed material prior to leaching in an effort to improve the leaching characteristics of the REEs and potentially reduce acid consumption. Initially, a detailed experimental program was performed on a laboratory LTP furnace to identify a set of process parameter values to be used for assessing the enhanced leaching performance achieved on four specific gravity fractions of West Kentucky No. 13 and Fire Clay coarse coal refuse materials. High-temperature oxidation (HTO)) was also evaluated as a means for improving REE leachability on the same fractions of both coal sources. The lixiviants used to assess leachability improvements included: i) untreated water, ii) 0.1 M ammonium sulfate solution and iii) 1.2 M sulfuric acid solution at a temperature of 75°C. The laboratory data was used to develop multiple process flow sheets using HTO only to produce a rare earth oxide mix concentrate or utilizing both LTP and HTO treatment processes to generate a high purity heavy REO mix concentrate and a light REO mix concentrate. A techno-economic analysis was performed on each circuit. Low-temperature plasma oxidation was found to enhance REE leaching characteristics for all specific gravity (SG) fractions of the West Kentucky No. 13 coarse refuse material. The leaching recovery improvement was preferentially achieved for the heavy REEs with higher values obtained when treating the lower density fraction material. For example, the leaching recovery for the heavy REEs in the untreated 1.6 SG Float fraction material was 8% in a 0.1 M ammonium sulfate solution. After LTP treatment for 32 hours, heavy REE recovery increased to 33%. The corresponding recovery value for the light REEs was 10%. These findings indicate a strong affinity of the heavy REEs with the organic material, which is the component being reduced in content during the LTP treatment. Scanning electron micrographs showed the development of a honeycomb structure with increased LTP treatment with higher surface area as confirmed from BET measurements. Higher surface area promotes improved leaching efficiency due to enhance chemical interactions. When using 1.2 M sulfuric acid, the LTP treatment was found to provide a heavy REE recovery increase from 23% to 53% for the 1.6 SG Float fraction which corresponded to an ash content increase from around 20% to 35%. However, LTP treatment provided no improvement in leaching characteristic for the 2.2 SG sink material in the acid solution, which was likely due to the low organic content. The LTP treatment of the Fire Clay SG fractions provided no improvement in REE leaching characteristic, which may be due to the association with REE minerals such as monazite and REE-associated mineral matter such as clays. High temperature oxidation using temperatures in the range of 600-750OC was found to significantly enhance the leaching characteristics of both the light and heavy REEs for all density fractions in both coarse coal refuse materials. Generally, the increase in light REE recovery for the West Kentucky material was from 15% for the untreated material to 90% for the HTO treated material at 600°C. Recovery values dropped significantly when using temperatures below 600°C and above 750°C. The impact of the excessive temperatures was most likely a result of sintering. For the heavy REEs, HTO significantly improved recovery in the lighter SG fractions, which may be due to an affinity with the organic content. Only limited heavy REE recovery improvement was obtained for the denser SG fractions. Another benefit of HTO is the conversion of calcium-based minerals to a very soluble calcium oxide, which is removable using a mild acid solution, and the conversion of Fe minerals to relatively insoluble minerals such as hematite and magnetite. The pregnant leaching solution produced from the leaching of all SG fractions obtained from both coal sources was treated using two stages of solvent extraction procedurally modeling a rougher-cleaner circuit followed by oxalic acid precipitation. Rare earth oxide products having a purity greater than 97% was produced from nearly all of the SG fractions. A novel process flowsheet was developed based on the selective leaching of heavy REEs that was made possible through LTP treatment of West Kentucky No. 13 coarse refuse followed by salt leaching. In the flowsheet, coal refuse material is ground to a top size of 1mm and then treated by LTP. The treated material is mixed into a 0.1 M ammonium sulfate solution and then filtered to produce a heavy REE enriched pregnant leach solution. The heavy REEs are concentrated by two stages of selective precipitation to produce a heavy REE mix oxalate and then roasted to obtain a heavy REO mix concentrate. The solid residues remaining after salt leaching is dried and then subjected to HTO treatment followed by concentration using selective precipitation and roasting to produce a light REO mix concentrate. An alternative circuit was developed using HTO treatment only to treat 100% of the coarse refuse material followed by selective precipitation and roasting to generate a high purity REO mix product. A techno-economic analysis performed for the treatment of West Kentucky No. 13 and Fire Clay coarse refuse based on a hypothetical 500-tph plant revealed that the net present value for all scenarios was significantly negative. Primary reasons include: i) a substantial decrease in the basket value of the final product relative to the feed and ii) high chemical costs relative to the amount of product generated. The basket value reduction was primarily due to little to no scandium recovery due to poor leaching characteristics when using low acid concentrations as necessitated by the low feed grades. Operating costs were primarily influenced by the chemical costs relative to the kilograms of concentrate produced and feed grade. For the Fire Clay coarse refuse material, the total operating cost was estimated to be $354 per kg of REO produced which was higher than the basket value of the REO product ($276/kg). Approximately 37% of the total cost was the sulfuric acid used during the leaching process. A comparative analysis performed to assess the economic viability of using low-temperature plasma furnaces found that market value enhancement for the generation of both heavy REO and light REO concentrates will be needed in addition to significant technology advancements to reduce the cost of plasma furnaces.