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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Distribution of rare earth and other critical elements in lignites from the Eocene Jackson Group, Texas

Coal is increasingly evaluated as a source of rare earth elements (REEs) in the United States to address the overreliance on imported REEs. The objective of this study was to assess the distribution of REEs in lignites from selected mining areas in the Texas Gulf Coastal Plain region. Thirty-one archived lignite and rock samples previously collected by the U.S. Geological Survey were analyzed for their rare earth element and critical mineral content. These include samples from one core (5400 and 5500 lignite horizons) and two opencast lignite mines (Gibbons Creek 3500 and 4500 horizons, and San Miguel horizons A to D) in the Eocene Jackson Group of the Texas Gulf of Mexico Coastal Plain. Some lithologies in the Gibbons Creek 3500 and 4500 lignite-bearing sections have high total rare earth, yttrium (Y), and scandium (Sc) (REYSc) values, up to 7800 ppm (ash basis) REYSc. The lignite lithologies show an enrichment in rare earths, [samarium (Sm) through gadolinium (Gd)]. The basal Gibbons Creek 3500 lignite bench shows a heavy rare earth element enrichment pattern resembling that often seen in peats through high volatile A bituminous coals. The 5500 lignite sequence, overlying the latter lignite sections, shows a light rare earth enrichment. The San Miguel lignite benches have heavy rare earth enrichments with a negative europium (Eu) anomaly.

58 GEOSCIENCES↗
DOE OSTI2022

Assessment of lignite upgrade and hydrogen evolution via electrolysis

Lignite, considered as the lowest-rank coal, accounts for 45% of the total coal resources worldwide, and its low carbon and high ash contents limit its large-scale application. In order to upgrade lignite effectively, a modified coal electrolytic cell (MCEC) was designed, built, and then evaluated for lignite upgrade and hydrogen production through electrolysis, and the operating conditions were optimized. The results show that the performance of the MCEC outperformed the previous coal electrolytic cell (CEC). The operating temperature and iron concentration significantly impact the average current density per milligram of catalyst (ACDMC). The content of dry fixed carbon and heating value increased by 20.9% (wt%) and 8.15%, respectively, in electrolyzed lignite compared with raw lignite. Besides, 71.5% ash and 39.6% mercury were removed from raw lignite after electrolysis, which is the first report. The Faradaic efficiency (FE) for hydrogen evolution reached 99% using MCEC. In addition, the analysis of spectroscopy methods (SEM, EDX, FTIR, and XRD) revealed that the lignite particles were cracked; the oxygen-containing functional groups increased; the minerals of quartz and hematite formed on the surface of lignite particles after electrolysis. Furthermore, the facts indicate that electrolysis of lignite is a competitive approach for lignite upgrade and hydrogen production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Pilot Scale Testing of Lignite Adsorption Capability and the Benefits for the Recovery of Rare Earth Elements from Dilute Leach Solutions

Naturally occurring organic materials containing humic acids show a strong affinity towards rare earth elements (REE) and other critical elements. Leaching experiments on lignite coal waste produced from construction sand production revealed that the contained REEs were associated with the organic matter. Furthermore, adsorption studies revealed that the lignite waste was capable of extracting REEs from a model solution and increased the REE content of the lignite waste by more than 100%. As such, this study aimed to utilize the lignite waste to adsorb REEs from pregnant leach solutions and acid mine drainage sources having low REE concentrations and subsequently leach the lignite material to produce pregnant leach solutions containing relatively high amounts of REEs, which benefits the performance and economic viability of downstream separation and purification processes. An integrated flowsheet was developed based on this concept and tested at a pilot scale. The pregnant leachate solution (PLS) was generated from a heap leach pad containing 2000 tons of Baker seam coarse refuse. The pilot scale circuit was comprised of aluminum precipitation, adsorption using the waste lignite, and rare earth-critical metal (RE-CM) precipitation stages in succession. The results indicated that the aluminum precipitation stage removed over 88% and 99% of the Al and Fe, respectively. The adsorption stage increased the REE content associated with the waste lignite from 457 ppm to 1065 ppm on a whole mass basis. Furthermore, the heavy REE (HREE) content in the feedstock increased by approximately 250%, which raised the percentage of HREE in the REE distribution by 19 absolute percentage points. In addition to the REEs, concentrations of other critical elements such as Mn, Ni, and Zn also improved by 75%, 37%, and 250%, respectively. Bench-scale tests revealed that increasing the solids concentration in the waste lignite and PLS mix from 1% to 20% by weight enhanced the adsorption efficiency from 32.0% to 99.5%, respectively. As such, a new flowsheet was proposed which provides significantly higher REE concentrations in the PLS that can be fed directly to solvent extraction and/or oxalic acid precipitation and, thereby, enhancing process efficiency and economics.

58 GEOSCIENCES↗
DOE OSTI2020

Techno-economic prospects for producing Fischer-Tropsch jet fuel and electricity from lignite and woody biomass with CO 2 capture for EOR

This work explores the prospective techno-economic performance of facilities that produce low- and net-negative-carbon liquid transportation fuels and electricity with CO 2 capture for enhanced oil recovery. The lignite and biomass-to-jet fuel process is based on KBR’s TRIG gasifier, Rectisol (for sulfur removal and CO 2 capture), fixed-bed low temperature Fischer-Tropsch synthesis of liquid fuels, and Brayton/Rankine combined cycles to convert synthesis/refining off-gases and waste heat to electricity. This work leverages a recent, highly-detailed assessment of a prospective first-of-a-kind (FOAK) demonstration facility to develop highly detailed Aspen Plus process simulations for nine prospective N th -of-a-kind (NOAK) plant equipment configurations. Component-level capital costs from the FOAK study are scaled and adjusted to reflective prospective learning-by-doing to estimate capital costs for the NOAK designs. NOAK plant economic performance is found to be largely insensitive to variations in plant configurations and electricity output fraction, but biomass input fraction significantly affects profitability. Facilities that consume only carbon–neutral biomass, with no lignite co-feed, have significantly net-negative carbon emissions and the most favorable prospective economics when carbon emissions are priced. For these facilities, the crude oil price required for plant economic viability falls rapidly from $\$$100/bbl as carbon emission prices increase above $\$$120/tonne CO 2eq . In general, plants that co-fire lignite with biomass are less profitable (than 100% biomass plants) due to their higher net greenhouse gas emissions.

09 BIOMASS FUELS↗
DOE OSTI2023

Characterization of Rare-Earth Elements in Lignite Coal of the Williston Basin: Past Efforts and Ongoing Work

Rare-earth elements (REEs) have been a subject area of high interest for their unique properties. REEs are crucial materials used in an incredible array of consumer goods, energy system components, and military defense applications. While the United States has one operating REE mine, the product is sent overseas for refining into usable metals making the United States 100% import-reliant on these critical materials. This has led the Federal Government to declare the REE market an issue of national security. The Energy and Environmental Research Center (EERC) under funding provided by the Department of Energy (DOE) has undertaken efforts to determine if the lignite coal found in the Williston Basin has the potential to be an ore body containing sufficient quantities of REEs and Critical Minerals (CM) for extraction and processing. In one such effort, the EERC collected over 400 samples from the Williston Basin lignite coal seams including outcrops as well as active mines. Those efforts have been followed up with ongoing work under the U.S. DOE’s Carbon Ore, Rare Earth and Critical Minerals Initiative (CORE-CM) currently ongoing in the Williston Basin as well as other basins in the United States. This ongoing work in the Williston Basin characterizing REEs in coal has focused on the collection of new sampling and analysis of REEs in coal and building upon previous characterization work. This information is being used to understand the spatial distribution of REEs through mapping and 3D modeling. The goals of these efforts are to better understand the mechanisms for distribution of the REEs in lignite coal as well as their concentration and determine knowledge gaps in characterization and to start to build the database required to understand the potential resource in the Williston Basin.

Feole, Ian K.↗
DOE OSTI2024

Lignite-Derived Carbon Materials for Lithium-Ion Battery Anodes

This project involved collaboration between the University of North Dakota (UND) College of Engineering & Mines, Clean Republic, LLC (CR), and the North American Coal Corporation (NACoal) to develop advanced LIBs anodes from lignite-derived carbon materials. The overall goal of the project was to develop advanced anode materials for LIBs from lignite-derived carbon feedstocks.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2025

Recovery and Refining of Rare Earth Elements from Lignite Mine Wastes

The University of North Dakota (UND), in collaboration with a comprehensive team of technical, business and host-site partners, built on prior technology development to complete a front-end engineering and design (FEED) and business planning study to recover and refine rare earth elements (REE) and critical minerals (CM) from North Dakota (ND) lignite mine wastes. The end of project goal was to have an investment quality project and a committed team ready to commercialize the proposed technologies in a future construction and operations phase.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2025

Development of a microwave-assisted downdraft moving-bed gasifier for continuous processing of lignite and biomass chars

This research illustrates a microwave-assisted downdraft moving-bed gasifier for the first time. Such design enables continuous solid gasification process. An adjustable auger was applied to control the solid removal rate and the gas-solid interaction time. Both lignite and biomass chars were investigated to determine the capability of the current system for low-tar feedstocks with different densities. Here, the presented reactor design was able to operate continuously for 3 hours and 20 minutes under 700 ℃ and atmospheric pressure, with air as the gasifying agent. For yellow pine char, the processing rate could reach 34.1 grams per hour with decent syngas production. The downdraft moving-bed design shows better cold gas and syngas production efficiencies compared to the common fixed-bed design, due to controllable residence time and more homogeneous microwave heating. The limitations of the current design and the direction of novel microwave-assisted chemical reactor design were discussed. This novel reactor design provides a way to improve the efficiency of microwave-assisted gasification process and shows its potential to be incorporated into other established chemical reaction processes as a modular add-on.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1981

Discrimination of unique biological communities in the Mississippi lignite belt

Small scale hardcopy LANDSAT prints were manually interpreted and color infrared aerial photography was obtained in an effort to identify and map large contiguous areas of old growth hardwood stands within Mississippi's lignite belt which do not exhibit signs of recent disturbance by agriculture, grazing, timber harvesting, fire, or any natural catastrophe, and which may, therefore, contain unique or historical ecological habitat types. An information system using land cover classes derived from digital LANDSAT data and containing information on geology, hydrology, soils, and cultural activities was developed. Using computer-assisted land cover classifications, all hardwood remnants in the study area which are subject to possible disturbance from surface mining were determined. Twelve rare plants were also identified by botanists.

Miller, W. F.↗
DOE OSTI2023

Particulate from Lignite Coal Combustion and Impact on Carbon Capture Aerosol Emissions

Conference presentation for 47th International Technical Conference on Clean Energy (Clearwater Clean Energy Conference), Clearwater, Florida, July 23–27, 2023. While aerosol formation is recognized as a leading cause of amine losses and degradation from postcombustion CO 2 capture systems, the factors that can lead to aerosol formation vary widely depending on fuel type, plant configuration, and operating conditions. All of these factors require measurement to fully characterize potential sources of aerosol-based amine losses and should be considered prior to implementing full-scale amine-based CO 2 capture.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2022

Coal polymer composites prepared by fused deposition modeling (FDM) 3D printing

Coal is a vital energy resource worldwide, but pollutants and greenhouse gases from its combustion cause environmental problems. To explore the non-combustion approach to use and valorize coal, anthracite and lignite were blended with polyamide 12 (PA 12) through FDM printing in this work and compared in the composites. By adding lignite, Young’s modulus improved with increasing loading to 50 wt% while tensile strength leveled off among the composites, compared to that of PA 12. By contrast, the addition of anthracite decreased the tensile performance at all loadings. Rheology tests and morphology analyses suggested that the interactions between fillers (anthracite and lignite) and PA 12 may cause differences in tensile properties. In addition, the printed lignite composites showed improved thermal conductivity (~ twofold), indicating lignite demonstrates the potential to build functional composites. This work provides a strategy to use lignite in composites by 3D printing for value-added products and reduces the demand for petroleum-based polymers. Overall, our approach diverts lignite from combustion processes and alleviates the negative impact of lignite use on the environment.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Advanced Processing of Coal and Coal Waste to Produce Graphite for Fast-Charging Lithium-Ion Battery Anode

The University of North Dakota (UND) Energy & Environmental Research Center (EERC), in collaboration with the UND Center for Process Engineering Research (CPER), conducted a project to validate two technologies capable of converting North Dakota lignite and lignite coal waste to high-quality graphite for fast-charging lithium-ion battery (LIB) anode. The project was conducted over about 3 years from April 7, 2022, to July 6, 2025. The two technological paths pursued in this project include path A – direct conversion of coal or coal waste to graphite by the upgraded carbon ores to products (UCOP) process being developed at the EERC and path B – lignite-derived coal tar pitch (CTP) conversion to graphite (CTP2G) process being developed at CPER. The results from this project validate the two technological approaches and are expected to be an integral part of a portfolio of emerging technologies for making high-quality graphite not only from North Dakota lignite, but from all ranks of U.S. domestic coal and coal waste resources. The quality of the graphite produced by these technologies is high enough for various applications, including batteries for the fast-growing electric vehicle industry, energy storage applications, electric arc furnace electrodes for steel production, and graphene production, among others. Although the two technologies can produce high-quality graphite, they are fundamentally different in that the UCOP technology provides a direct path to transform coal to graphite, while the CTP2G technology needs to go through a CTP intermediate and a coking process for the intermediate, which requires a special facility to accomplish. For application in the industry, the UCOP process is designed to be more flexible, with feedstock to include potentially any carbonaceous material such as all coal ranks and biochar, while the CTP2G process is designed to utilize CTP as the starting precursor. The key project accomplishments include the following: • Successful preparation of high-quality synthetic graphite from North Dakota lignite coal/coal wastes and lignite-derived CTP. • Patent application has been filed for the UCOP process and an internal invention disclosure has been filed for the CTP2G process. • The produced graphite performs better than a commercial battery-grade sample in LIB coin cells, especially fast-charging capability, stability, and long-duration cycling. • Coin-type Li-ion half-cells with CTP2G graphite showed excellent performance, with >370 mAh/g capacity, >90% initial coulombic efficiency, and 93%/67% retention at 1C/2C rate, which outperforms commercial graphite in charging speed, stability, and cycling. • Results of fabricated 18650 cells were consistent with the observations in coin cells. • Preliminary techno-economic analysis (TEA) estimates for the UCOP technology indicate a manufacturing cost of about $\$$39/kg based on 50-metric ton/year capacity. • Preliminary TEA estimates for the CTP2G technology indicate a market price of about $\$$7107/ton ($\$$7/kg) based on 22,000-ton/year production capacity.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2021

Subtask 2.6 – Optimization of Aerosol Mitigation Technology for Postcombustion CO 2 Capture

Growing concerns over the impact of CO 2 emissions from combustion sources on global climate change have prompted numerous research and development projects aimed at developing cost-effective technologies for CO 2 capture. One family of technologies being demonstrated at pilot and full scale globally is postcombustion CO 2 capture (PCCC) systems that employ amine-based solvents. The captured CO 2 can be compressed and permanently stored underground or used for enhanced oil recovery (EOR). The proximity of North Dakota’s lignite-fired fleet of power plants to potential CO 2 storage options creates a unique atmosphere for PCCC within the state. However, the aerosols present in lignite flue gas present a challenge for large-scale PCCC at North Dakota power plants. Aerosols can negatively impact the long-term performance of amine-based solvents for CO 2 capture. Amine-based solvents are volatile, and aerosols provide nucleation sites where amine vapors can condense. Because aerosols cannot be easily captured at the column outlet using conventional technologies, the amine-laden aerosols escape the system and lead to accelerated solvent losses. Moreover, aerosol components can chemically react with amines to form degradation products that can permanently deactivate the amine, cause fouling, and lead to hazardous emissions. Many of the elements that have been shown to catalyze solvent degradation are present in lignite coals and can exacerbate solvent replacement economics. Understanding this issue is critical to the implementation of solvent-based CO 2 capture systems as applied to lignite-fired generation systems. The Energy & Environmental Research Center (EERC) designed and carried out this project to optimize aerosol mitigation technology for PCCC at a lignite-fired power plant. To meet the goal of this project, the following objectives were identified: Determine the effectiveness of a wet electrostatic precipitator (WESP) on collection of aerosols at a low-rank coal-fired power station. Determine the impact of aerosols on the efficiency and degradation products of amine-based carbon capture systems fired with low-rank fuels. Work was conducted at Minnkota Power Cooperative’s (MPC’s) Milton R. Young (MRY) Station Unit 2 using a slipstream of flue gas from the outlet of the plant’s flue gas desulfurization (FGD) unit. To gather initial data for sizing and specifying a WESP for this system, a temporary pilot-scale WESP was rented and installed on-site. Several different conditions were tested to examine the impact of flow rate, voltage, and current on WESP performance. The WESP was effective at removing large particulate (>200 nm) but caused an increase in fine particulate (<75 nm). Fine particulate material at the inlet and outlet of the WESP was collected, analyzed, and showed that crystalline sulfates carried over from the plant’s FGD unit were being converted to fine aerosols and SO 2 was being converted to SO 3 through the WESP. Additionally, the high moisture content of the flue gas stream at this sample location also contributed to an overall increase in aerosol mass under some of the test conditions. Using the results from the rented WESP, the project team installed a smaller-scale WESP upstream of the EERC’s slipstream CO 2 capture system. Flue gas was routed through a pilot-scale FGD unit to remove SO 2 to very low levels (~1 ppm) and then through a direct contact cooler (DCC) to further cool the gas and to remove moisture. The gas exiting the DCC was then routed through the new WESP before passing to the CO 2 absorber columns. Fluor’s amine-based solvent was used to scrub CO 2 from the slipstream through a set of two absorber columns. The rich solvent was regenerated in a stripper column by heating to drive off captured CO 2 . The system operated using a catch-and-release method where the CO 2 was separated to provide data on the process, but the captured CO 2 was released back into the host site stack. Aerosols and sulfur species were measured at multiple locations throughout the pilot-scale system. The inlet FGD and DCC removed much of the particulate matter and gaseous sulfur upstream of the WESP. With this configuration, the WESP achieved >95% particulate capture. The new WESP did not show any of the increases in SO 3 or other aerosol species that had been consistently observed with the larger-scale WESP installed immediately downstream of the plant’s full-scale FGD unit. Particulate samples captured and analyzed from the WESP inlet did not show any presence of crystalline sulfate materials, indicating that the pilot-scale FGD and DCC were efficient at reducing carryover from the plant’s full-scale FGD unit. A set of parametric tests were conducted on the new WESP to assess the impacts of flow rate, voltage, number of online WESP fields, and gas-phase sulfur content on aerosol and sulfur transformations. The results showed that the WESP performed similarly well at all sets of conditions. Sulfur and particulate matter exiting the WESP were further reduced through the absorber column as the amine-based solvent captured some of the residual contaminants. Solvent analysis showed that these species were slowly concentrating in the solvent over the duration of the test. When the WESP was taken offline and the sulfur slip through the FGD allowed to rise, the sulfate content in the solvent rose sharply, showing that the extra FGD and WESP were effective at reducing sulfate and cation uptake. This would be expected to extend amine-based solvent life by slowing the formation of heat-stable salts and other degradation products. This subtask was cofunded through the EERC–U.S. Department of Energy Joint Program on Research and Development for Fossil Energy-Related Resources Cooperative Agreement No. DE-FE0024233. Nonfederal funding was provided by the North Dakota Industrial Commission and MPC.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2023

Demonstration of Scaled-Production of Rare Earth Oxides and Critical Materials from U. S. Coal-Based Sources (Final Report)

The project objective was to demonstrate scaled production of high purity rare earth oxides (REO), nominally exceeding 90% grade, from coal refuse sources using innovative technologies that reduce cost and improve environmental outcomes relative to traditional rare earth processing technologies. The project utilized a critical material pilot plant constructed and tested as part of a previous U.S. Department of Energy project. Target performance criteria was a 50% reduction in production cost based on previous optimum values, 150% increase in recovery and greater than 2% concentrates of rare earth oxides, cobalt and manganese. Concentrate production goals were to produce a rare earth mix oxide product at a rate of 200 grams per day having a minimum purity of 50% as well as products of cobalt and manganese having a minimum purity of 2%. A previous pilot plant investigation identified acid cost as the major contributor to an operating cost that made the recovery of rare earth and other critical metals from bituminous coal sources economically challenging. As such, acid cost reduction was a major target using bio-oxidation reactors to produce sulfuric acid from naturally occurring coal pyrite. Based on laboratory data, a bio-oxidation circuit was designed for the pilot plant to produce 7.5 l/min of acid using two 11-m3 (3000 gallon) reactors equipped with 40 hp aerators for air dispersion. The pilot-scale tests revealed that acid concentration equivalent to as high as 1.0 M sulfuric acid could be continuously produced. However, the bio-acid contained exceptionally high iron concentrations, which complicated downstream processing of the pregnant leach solution (PLS). A TEA of the bio-oxidation circuit showed that production cost was approximately $0.13 per kg acid equivalent if produced using a four-day retention time in the reactors. This value represents a 48% reduction from that of purchased bulk sulfuric acid. Calcination (or roasting) studies were conducted on coarse refuse from West Kentucky No. 13 and Fire Clay coal seam sources. The test results revealed the potential to increase recovery by nearly 100% using temperatures between 500°C to 700°C with light REE recovery value being the most improved. Acid baking of the calcined products using sulfuric acid at 250°C increased heavy rare earth recovery from around 40% to 80% while decreasing the acid requirements by over 50%. The existing pilot plant was upgraded for the pilot scale demonstration of REE and CM recovery. The primary feedstocks were West Kentucky No.13 and heap leach pregnant leach solution (PLS) while a secondary feedstock was a lignite waste material from a construction sand operation. The pilot scale operation started with PLS generation through leaching followed by iron and aluminum removal, nominally at 3.3 and 4.5 pH, respectively. Leaching lixiviants used for the test were industrial grade sulfuric acid or bio-acid generated at the pilot scale facility. For most of the tests, the solid feed rate was 200 lb/hr whereas lixiviant was added at 2 gpm to provide an optimal residence time of 45 minutes. Following the contaminant removal step, several different process schematics were tested with the goal of maximizing REE recovery and purity. In the first test, direct processing of aluminum precipitation raffinate for REE recovery using oxalic acid at pH 1.5 was investigated. Overall REE recovery was approximately 45%. Unfortunately, elevated calcium content in the PLS significantly impacted the RE-Oxide product grade. Similarly, high calcium content decreased both the product purity and grades of CM products. As such, a new flowsheet was tested with the same initial process schematic but different precipitation stages for REEs and CMs at pH 6.0 and 9.0, respectively. It was noted that the overlapping precipitation behavior of Co, Ni and Zn with REEs limited the applicability of this process schematic. While this change increased the RE-Oxide grade from 36% in the first test to 87%, the loss of critical metals to the REE cake and bypass of the REEs to the CM cake significantly impacted the recovery of both REEs and CMs. Therefore, the modified process flowsheet combined oxalic acid precipitation stage raffinate and redissolved CM cake filtrate to maximize both the recovery and purity of the products. Consequently, a RE-Oxide product with 85% purity and CM cakes with over 19% Co, 38% Ni, 14% Zn and 9% Mn content were generated with significantly higher recoveries. While the modified process flowsheet improved recoveries and grades, elemental losses observed in separate precipitation and redissolution losses inspired the adaptation of a single precipitation stage at pH 9.0 for both REEs and CMs. This change was anticipated to maximize the REE recovery while minimizing the costs associated with separated redissolution and processing stages. As expected, REE recovery in this new circuit arrangement was over 56% with a product grade of over 87% RE-Oxide content. Similarly, Co, Ni, Mn, and Zn recoveries of 54%, 40%, 67%, and 66%, respectively, were achieved. Unfortunately, the elevated calcium content present in the solution due to its precipitation at pH 9.0 caused a decrease in the CM cake quality. Therefore, the final process flowsheet involved the addition of calcium oxalate precipitation following the oxalic acid precipitation stage, which effectively eliminated calcium contamination of the CM products. Finally, the pilot scale experiments conducted using bio-acid achieved comparable REE leaching recoveries to the conventional sulfuric acid leaching. Elevated iron concentration in the solution caused the co-precipitation of REEs with the iron and aluminum cake, resulting in the REE losses. Furthermore, elevated iron content bypassing the iron and aluminum precipitation stages contaminated the metal sulfide and manganese cake, respectively. A techno-economic analysis was performed based on a commercial facility capable of treating 500 tph of coal-based material. The production cost for West Kentucky No. 13 coarse refuse material ranged from approximately $500-$700/kg of total rare earth oxide whereas the lignite source had significantly lower production cost of $100-$300/kg. The significant difference in cost was due to the easier leaching characteristics of the lignite material and the higher feed concentrations. All process scenarios resulted in a negative net present value (NPV). For the lignite feedstock, laboratory REE leach recovery values were about 30% higher than the pilot plant data. Using the lab leach results, a positive net present value was achieved and the production cost decreased from $100-$300 $/kg to less than $150/kg of total REO.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2023

Laboratory-Scale Coal-Derived Graphene Process (Final Report)

The Energy & Environmental Research Center (EERC) conducted a laboratory-scale coal-derived graphene (CDG) project focused on developing a technological process for making graphene from four U.S. domestic coal or coal wastes, including lignite from North Dakota, subbituminous coal from Wyoming, bituminous coal from Utah, and anthracite from Pennsylvania. The project was divided into two performance or budget periods (BPs), with BP1 comprising the up-front laboratory experiments to make graphene materials from coal beginning on May 1, 2020, to April 30, 2022. BP2 was conducted from May 1, 2022, to April 30, 2023, and was focused on analyzing the CDG process economic feasibility and the technical gaps for technological scale-up and commercialization. During this project, a few different coal-derived high-value products have been demonstrated, including graphite, graphene oxide (GO), reduced graphene oxide (rGO), and graphene quantum dots (GQDs). A new graphite microstructure was discovered and named “croissant graphite” because of the exterior morphological and textural resemblance to croissant food items sold in commercial groceries stores. The new graphite structure and the associated preparation from coal or coal waste feedstocks has been the subject of a U.S. patent application. The systematic experimental processes involving coal cleaning, upgrading, and conversion to high-value carbon products culminated into a developed upgraded coal-to-products (UCP) technology that is being pursued for potential fast-track commercialization, if funding is available. It is envisioned that commercialization of the UCP technology would increase consumption of U.S. domestic coals or coal wastes to make environmentally sustainable high-value products for the electronics industry, high-energy-storage applications, and clean energy technologies such as electric vehicle (EV) lithium-ion batteries (LIBs), for which graphite has become a critical mineral commodity. Croissant graphite microstructures, when observed by field emission scanning electron microscopy (FESEM), display wavy surface morphology and often grow from a base that is made of graphitized particles with honeycomb-like layers, which are believed to be graphene layers. While more studies are needed to fully ascertain the mechanisms of the croissant graphite microstructure formation, it is postulated that their growth may begin from curling of the graphene sheets into ribbon-like structures, and continuous growth and densification of the ribbon-like structures forms croissant microstructures. Additional studies are ongoing to evaluate the electrochemical performance of croissant graphite for LIB applications and to determine the experimental conditions necessary to tune on/off croissant formation so that it can be either optimized or suppressed depending on performance evaluation results. In addition to the discovery of croissant graphite, the graphitization process from the four coal ranks in general was successful. X-ray diffraction (XRD) analysis showed that the degree of graphitization (DoG) ranged from 12% to 80% in an early sample set, and further optimization on lignite coal produces a DoG of about 92%, which was spectacular to see as lignite is the lowest-rank coal. Thus, it is expected that the graphitization performance for higher-rank coals will be similar or better when optimized as well. The coal-derived graphite was used to make GO and rGO. Analytical characterization, e.g., by methods such as Raman spectroscopy, XRD, Fourier transform infrared (FTIR) spectroscopy and FESEM, showed that the sequence of converting the coal to graphite, exfoliating it to GO, and then chemically reducing the GO to rGO was successful. Although coal naturally contains aromatic compounds and some relatively small-sized condensed aromatic units, it does not contain graphene sheets. In the UCP process, the aromatic domains in the coals, particularly low-rank coals, are concentrated and condensed further into graphene sheets, which are ordered into a 3D stack during graphitization. The synthesized graphite is then unpacked by methods such as exfoliation to various graphene products. GQDs were synthesized from all four coal types, and their optical properties were demonstrated to be tunable by the coal precursor preprocessing treatments. In all four coal types, enhanced optical properties were observed for the produced GDQs with incremental improvements made to the coal precursors. GQDs produced from raw coal samples displayed lower ultraviolet–visible (UV–Vis) spectroscopy absorbance intensity compared to those obtained from cleaned and upgraded coal residues. The photoluminescence (PL) intensities also varied with pretreatment conditions and with the concentration of GQDs in aqueous solutions. GQDs obtained from anthracite show longer emission wavelengths and can be excited by visible light as opposed to GQDs derived from the other coal ranks. UV fluorescence 3D maps and spectra revealed that the emission wavelength at which the GQDs solutions display the highest intensity was slightly redshifted based on the coal precursor pretreatments. In low-rank coal (lignite and subbituminous) samples, two clusters were observed in the maps for GQDs, which may suggest that there are potentially two types of fluorophores in solution or two main size populations. The ability to tune the properties of GQDs based on processing methods can be exploited to make GQDs for various optical display or optoelectronics applications. The results also highlight the importance of removing coal-borne impurities to improve the quality of the coal precursor for preparation of graphene products. Coal and/or coal wastes preprocessing methods were developed and applied to clean and upgrade the coal precursors prior to graphitization and subsequent conversion to graphene products. The preprocessing methods involve high specific-gravity separations, mineral acid cleaning (no hydrofluoric acid), and subsequent upgrading by reducing the coal-borne heteroatom (nitrogen, sulfur, and oxygen) content using proprietary chemical agents. Analytical characterization revealed that the preprocessing steps were successful, with ash reductions that range from 38% to 80% and residual ash content that was below the 5 wt% initial target. Based on proximate and ultimate analysis, the heteroatom reduction reactions produced upgraded coal residues with the oxygen content reduced by 8% to 24%, with additional reductions in the nitrogen and sulfur contents. An initial assessment of the waste streams from the UCP process shows very small to negligible environmental impact due to CO 2 , NO x , and SO x because most process steps are performed under inert atmosphere with argon. Consequently, reactive oxygen environments that tend to create these species are avoided. The inorganic and potentially hazardous species are released into aqueous waste streams that are easy to handle for proper disposal. The liquid waste streams were found to contain low-level concentrations of rare-earth elements (REEs), which could be concentrated and recovered as value-added by-products. Additionally, the volatile and gaseous fractions from carbonization and heat treatment contain useful organic compounds that can also be recovered as potential valuable by-products. Thus, the UCP technology is considered an environmentally sustainable and promising emerging technology for making high-value products from coal and coal wastes, with potential additional value-added by-products. Analysis of potential markets for the coal-derived carbon products shows a strong demand in both niche market sectors and across a wide variety of other industrial sectors. Graphite is currently considered a critical mineral commodity that has a large and growing demand in the LIB industry for EV applications. Based on data from Fortune Business Insights (2022) and Marketwatch (2023) reports, the average global graphite market is projected to reach about 33 billion by 2028, growing at a compound annual growth rate (CAGR) of about 7%, with much of this growth expected to be in the LIB industry. GO and rGO have strong market potentials in various application areas, such as coatings for anticorrosion, anti-icing, and antimicrobial protection, thermal barriers, wear resistance, sensors, additive manufacturing such as 3D inks, and others. GQDs are the emerging key player in the bioimaging, photovoltaics, and light-emitting diodes (LEDs) applications, with the potential to replace traditional semiconductor quantum dots (SQDs), which are based on metallic systems that are more toxic and more expensive. Biomedical applications of GQDs are becoming more attractive because of low to no toxicity and extremely low cost compared to SQDs. The major challenges for scale-up and commercialization of coal-derived carbon products such as graphene vary from the inherent attributes of graphene itself to reluctance to accept graphene in new manufacturing processes because of the uncertainty of the unknown. The 2D nature of graphene materials with a thickness of one atom presents significant challenges to proper handling/processing, and process scale-up becomes difficult because it requires high-end, expensive equipment, even for routine handling and analysis for quality assurance and control. Pristine graphene can also be extremely difficult to work into other matrices, thus hindering downstream processibility, especially at large scale. Currently, the cost of graphene and graphene products is still high and presents an economic risk that tends to slow down investment in scaling up emerging technologies. The lack of a standard for graphene materials for quality assurance and quality control poses a great challenge not only for the markets but also for commercialization efforts. A first-look economic feasibility analysis of the UCP technology provided valuable information that suggests the UCP process would be feasible, especially when it is scaled to a pilot scale and could be more competitive at the full scale. Graphitization was found to be the most energy-consuming and most capital-intensive step in the overall process. In small laboratory- and bench-scale experiments, labor is a significant contributor to the total process costs. Although these energy, capital, and labor constraints contribute to a higher selling price for the product, a preliminary economic model suggests that the process would be feasible at large scale when the process is fully integrated, optimized, and automated.

01 COAL, LIGNITE, AND PEAT↗