Resources from the Ashes: Rare Earth Elements in Coal Waste Byproducts [Slides]
Presented at the University of Oklahoma Department of Geosciences Shell Colloquium Series.
01 COAL, LIGNITE, AND PEAT↗
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Core Model Proposal #368: Adding fugitive CO2 emissions from fossil resources
This Core Model Proposal adds fugitive CO2 emissions from coal, crude oil, and natural gas resources to the data system. It also includes an improved method to replace outlier emissions factors for fossil resources. Lastly, it makes some minor changes to the data system and Model Interface headers to fix some inconsistencies in how resource technologies are named in the XMLs.
core model proposal↗
Sampling and Characterization of Coal Basins as an Alternative Rare-Earth Element Resource
Conference presentation at TechConnect World Innovation Conference & Expo, Washington, D.C., June 13–15, 2022. The University of North Dakota (UND) through the Energy & Environmental Research Center (EERC) and the Institute for Energy Studies teamed with the University of Kentucky Center for Applied Energy Research, Microbeam Technologies Inc., the Kentucky Geological Survey (KGS), the North Dakota Geological Survey (NDGS), and the mining industry to execute a contract with the U.S. Department of Energy National Energy Technology Laboratory (NETL) to obtain and characterize samples of U.S. domestic precombustion coal and coal-related materials with a minimum concentration of 300 parts per million (ppm) total rare-earth elements (TREEs) as the material is removed from the ground, with no processing other than drying.
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Nuclear-Driven Chemical Conversion Pathways
The purpose of this work is to explore the possibilities of using coal as a carbon resource by converting it to fuels and chemicals with heat from a nuclear power plant. While many previous studies have focused on coal gasification, this process requires combusting a portion of the coal and producing heat. By employing pyrolysis over gasification, the energy content in the coal can be preserved. Pyrolysis of coal also results in a large portion of solid char, which can be converted to activated carbon and sold to various markets. This model uses hydrogen produced by nuclear-supplied heat and electricity to convert the syngas stream to methanol, which has many pathways for further processing into fuels, chemicals, and plastics. Specifically, this project focuses on non-fuel products for methanol pathways. The CO2 captured within the refinery model can also be combined with hydrogen to produce more chemical products and reduce CO2 emissions.
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Sustainable Coal Tar Pitch Carbon Fiber Manufacturing
Coal is a versatile resource that has historically propelled the Industrial Revolution, transportation, and energy generation, and continues to meet needs for power. The United States possesses the largest worldwide coal reserves (with a 2019 total production-to-recoverable-reserves ratio of 0.05) that are of high quality and are cost-effective to recover (i.e., $0.03/kg–$0.10/kg). However, the demand of coal for power generation has declined because of a shift to natural gas (because of lower natural gas prices) and to renewable energy sources. This decline has affected the economic viability US coal industry. Historically, domestic demand for coal was driven mostly by the electric power sector, which accounts for about 93% of the total demand, followed by industrial uses (primarily for cement and chemicals at a minimal level) and steel production (coke). The complex, dense carbon chemical structure of coal, abundant domestic supply, and stable, low price gives it great potential for use in a wide range of value-added non-fuel coal products (e.g., nanomaterials at $20,000/kg–$100,000/kg and commercial-grade carbon fiber at $22/kg–$33/kg), as well as in upgraded coal fuels.
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Petrology and geochemistry of the Middle Pennsylvanian (Langsettian) Clintwood coalbed, Pike County, Kentucky
Abstract The Middle Pennsylvanian, Langsettian sub-stage Clintwood coal, along with its correlatives, was one of the more important energy resources in eastern Kentucky. The coal thickens from the NE-SW-trending Belfry anticline in central Pike County to the southeast, towards the Virginia-Kentucky border. Much of the thickness increase is in the bright lithotypes below a dull lithology. The bright lithologies transition from a bright clarain + vitrain + fusain lithology to a clarain + fusain lithology to the southeast. Half of the lithotypes in the three analyzed sections exceed 1000-µg/g Rare earth elements + Y + Sc (REYSc) (ash basis). The La N /Sm N vs. Gd N /Yb N and La N /Sm N vs. Ce N /Ce N * plots suggest that the top lithotype may have had best indication of an oxidizing environment. Positive Gd N /Gd N * and Eu N /Eu N * in some of the lithologies suggests that there may have been a hydrothermal influence in the sediment sources and/or in the diagenesis of the coal. Consideration of La N /Sm N and Zr (µg/g; ash basis), Zr vs. Sr, and V/Cr vs. inertinite/(inertinite + vitrinite) indicates that the dull lithotypes existed in a distinct geochemical environment compared to the brighter lithotypes. The isolation of the dull lithotypes from the bright lithotypes is supported by principal components analysis on inertinite/(inertinite + vitrinite), La N /Sm N , V/Cr, Sr, and either Zr or Ln(100(TiO 2 )/Al 2 O 3 ).
Hower, James C. (ORCID:0000000346942776)↗
M2CT-22IN1202096 Design for Carbon Conversion Product Pathways with Nuclear Power Plant Integration
Coal is a globally abundant resource that historically has been used for power generation via combustion. As the power industry replaces coal with cleaner methods of generation, energy-rich coal could be used in other chemical and fuel applications. This study presents a coal utilization option in which coal combustion is replaced with a carbon-free nuclear power plant and the coal is upgraded to valuable products for a variety of markets. Coal is prepared for conversion first by the pyrolysis process, which will optimize solid, liquid, and gaseous products based on the market size and potential product value, maximizing the monetary value of coal. This process is designed using bituminous coal from the Appalachian region as a basis to provide a pathway to preserve or transition coal-related jobs and create new jobs associated with the clean energy transition. Process modeling in the AspenOne Suite will be used to determine each component’s sensitivities, costs, inputs, and outputs. Dispatch modeling in the FORCE toolset will optimize the entire system and calculate the NPV for the refinery lifetime. Advanced and light-water reactors are considerations to supply the heat, steam, and electricity to the process. This paper focuses on the technical and market analysis used to determine the optimal processes and product pathways for the carbon refinery. Product pathways are on activated carbon, formic acid synthesis, and methanol synthesis for further upgrading to marketable chemical and polymer products.
01 COAL, LIGNITE, AND PEAT↗
M2CT-22IN1202096 Design for Carbon Conversion Product Pathways with Nuclear Power Plant Integration
Coal is a globally abundant resource that historically has been used for power generation via combustion. As the power industry replaces coal with cleaner methods of generation, energy-rich coal could be used in other chemical and fuel applications. This study presents a coal utilization option in which coal combustion is replaced with a carbon-free nuclear power plant and the coal is upgraded to valuable products for a variety of markets. Coal is prepared for conversion first by the pyrolysis process, which will optimize solid, liquid, and gaseous products based on the market size and potential product value, maximizing the monetary value of coal. This process is designed using bituminous coal from the Appalachian region as a basis to provide a pathway to preserve or transition coal-related jobs and create new jobs associated with the clean energy transition. Process modeling in the AspenOne Suite will be used to determine each component’s sensitivities, costs, inputs, and outputs. Dispatch modeling in the FORCE toolset will optimize the entire system and calculate the NPV for the refinery lifetime. Advanced and light-water reactors are considerations to supply the heat, steam, and electricity to the process. This paper focuses on the technical and market analysis used to determine the optimal processes and product pathways for the carbon refinery. Product pathways are on activated carbon, formic acid synthesis, and methanol synthesis for further upgrading to marketable chemical and polymer products.
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Design for Carbon Conversion Product Pathways with Nuclear Power Plant Integration (PCC)
Coal is a globally abundant resource that historically has been used for power generation via combustion. As the power industry replaces coal with cleaner methods of generation, energy rich coal could be used in other chemical and fuel applications. This study presents a coal utilization option in which coal combustion is replaced with a carbon-free nuclear power plant and the coal is upgraded to valuable products for a variety of markets. Coal is prepared for conversion first by the pyrolysis process, which will optimize solid, liquid, and gaseous products based on the market size and potential product value, maximizing the monetary value of coal. This process is designed using bituminous coal from the Appalachian region as a basis to provide a pathway to preserve or transition coal-related jobs and create new jobs associated with the clean energy transition. Process modeling will be used to determine each component’s sensitivities, costs, inputs, and outputs Advanced and light-water reactors are considerations to supply the heat, steam, and electricity to the process. This paper focuses on the technical and market analysis used to determine the optimal processes and product pathways for the carbon refinery. Product pathways are on activated carbon, formic acid synthesis, and methanol synthesis for further upgrading to marketable chemical and polymer products.
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Tetrafluoroboric Acid Digestion for Accurate Determination of Rare Earth Elements in Coal and Fly Ash by ICP-MS Analysis
Coal and coal-related fly ash often contain rare earth elements (REEs) that have the potential to be utilized as valuable mineral resources. Accurately determining the REE content in coal and fly ash is crucial for resource evaluation. The conventional approach involves using hydrofluoric acid (HF) to dissolve silicates and release REEs, which, however, prolongs the digestion process due to the additional step of complexing fluoride ions (F−) with boric acid (H3BO3). Determining the correct amount of H3BO3 for neutralization can be challenging, and in some instances, the binding of fluoride ions with certain lanthanides (Lns) hampers the accurate determination of all 14 naturally occurring rare earth elements in a single digestion batch by inductively coupled plasma mass spectrometry (ICP-MS). In this study, we present an alternative method that achieves the accurate determination of all 14 naturally occurring REEs using tetrafluoroboric acid (HBF4) followed by ICP-MS analysis. This approach eliminates the need for an F− complexing step. We tested this method on certified REE reference materials, including NIST 1632e (coal) and NIST 1633c (fly ash), as well as the REE geological reference material USGS AGV-1 (andesite). Our results demonstrated excellent recovery rates (relative standard deviation, RSD < ±10%), with a correlation coefficient (r2) exceeding 0.99. Using this method, we investigated the concentrations of all 14 REEs in coal and fly ash samples collected from various locations in the southwestern USA. This improved digestion technique streamlines the analysis process and enhances the accuracy of REE determination, facilitating a more comprehensive evaluation of REE-rich coal and fly ash deposits for resource exploration.
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Making coal relevant for small scale applications: Modular gasification for syngas/engine CHP applications in challenging environments
Small-scale coal gasification technology, coupled to a reciprocating engine generator, has the potential for making coal a cost competitive resource for meeting the flexible energy needs and resiliency requirements of utilities across the United States. To maintain grid stability and reliability, electrical generation must be regulated to match the load at the proper voltage and frequency. With the expansion of intermittent sources into the grid, such as wind and solar, frequency and voltage regulation become increasingly important and challenging. This work presents the results of a Front End Engineering Design (FEED) effort to detail the engineering and preliminary economics of a small-scale, air blown, fixed-bed gasification process, operating at near-atmospheric pressure, with gas cleanup to provide syngas and pyrolysis liquid fuels for use in reciprocating engine generators for combined heat and power at the University of Alaska Fairbanks. A very detailed assessment of capital and operating costs allows the evaluation of a levelized cost of electricity of 208.06 $/MWh, which can be reduced through the selling of by-products (steam for heating purposes and pyrolysis liquids to be used for power generation in an existing diesel engine). Here, a combined sensitivity analysis, based on the Monte Carlo approach, has been carried out to evaluate the effects of the uncertainties (capital and operating costs and plant annual availability) on the LCOE.
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Exploratory Investigation of Coal in Nonequilibrium Plasma
Coal is an abundant natural resource and there is motivation to find new uses for it that do not intrinsically involve combustion. One approach is to explore new ways of processing coal, and in this work, we focus on the transformation of coal in a nonequilibrium plasma generated from an equimolar mixture of nitrogen and hydrogen. The outcome of the nonequilibrium plasma reaction is fundamentally different than a thermal control reaction carried out using the same gas composition, pressure, and temperature range. The nonequilibrium plasma produces a gas mixture that is enriched in acetylene and its derivatives. Furthermore, when compared to the thermal control experiment, the solid char byproduct of the nonequilibrium plasma has a very reactive surface and is spontaneously combustible at ambient temperature. Experiments performed to characterize the reaction kinetics of coal in the plasma suggest that the mechanism proceeds through a sequential process by which the coal particle temperature rises to a point where devolatilization can occur, the devolatilization reaction happens, followed by parallel reactions of released organic vapors in the plasma phase and surface activation. In conclusion, the reaction rate appears to be limited by the time it takes for the coal particle temperature to rise, consistent with previous results reported for reactions of coal in thermal plasma.
Acetylene↗
Williston Basin Carbon Ore, Rare Earths, and Critical Minerals (CORE-CM) Program
The U.S. Department of Energy’s Office of Fossil Energy awarded 13 CORE-CM programs as part of the CORE-CM Initiative, designed to develop the technology and upstream and midstream supply chains to extract rare-earth elements (REEs) and critical minerals (CMs) from the nation’s coal supplies. The intent is to catalyze regional economic growth and job creation while strengthening the use of domestic resources. The Williston Basin CORE-CM Program aims to drive the expansion and transformation of coal and coal-based resource usage within the Williston Basin to produce REEs, CMs, and nonfuel carbon-based products (CBPs). A coalition team of nearly 30 private industry, university, and state, local, and federal government partners was formed for this task. Partners include the University of North Dakota’s Energy & Environmental Research Center, College of Engineering and Mines Research Institute, and Nistler College; North Dakota State University; Montana Tech University; Pacific Northwest National Laboratory; Critical Materials Institute; North Dakota Geological Survey; South Dakota Geological Survey; U.S. Geological Survey; North American Coal Corporation; BNI Energy; Basin Electric Power Cooperative; Minnkota Power Cooperative; and many more. This presentation will focus on the current status and results to date of the Williston Basin CORE-CM Program, with a focus on core sample characterization for REE and CM content.
Folkedahl, Bruce C.↗
Williston Basin Carbon Ore, Rare Earth, and Critical Minerals (CORE-CM) Program
The U.S. Department of Energy’s Office of Fossil Energy awarded 13 CORE-CM programs as part of the CORE-CM Initiative, designed to develop the technology and upstream and midstream supply chains to extract rare-earth elements (REEs) and critical minerals (CMs) from the nation’s coal supplies. The intent is to catalyze regional economic growth and job creation while strengthening the use of domestic resources. The Williston Basin CORE-CM Program aims to drive the expansion and transformation of coal and coal-based resource usage within the Williston Basin to produce REEs, CMs, and nonfuel carbon-based products (CBPs). The work constitutes Phase 1 of a long-term program. The objectives of Phase 1 are to identify the existing knowledge base and gaps and to develop a series of assessments/plans, including an initial basinal assessment; a characterization and data acquisition plan; a waste stream reuse plan; a basinal strategies assessment for infrastructure, industries, and business; a technology assessment, development, and field testing plan; a technology innovation center plan(s); and a stakeholder outreach and education plan. The goal of this project is to initiate the development of a new industry in the resource-rich Williston Basin that will catalyze economic growth and job creation through a coalition team of private industry, university, and state, local, and federal government entities. A coalition team of nearly 30 private industry, university, and state, local, and federal government partners was formed for this program. Partners include the University of North Dakota Energy & Environmental Research Center, Institute for Energy Studies, and Nistler College; North Dakota State University; Montana Tech University; Pacific Northwest National Laboratory; Critical Materials Institute; North Dakota Geological Survey; South Dakota Geological Survey; U.S. Geological Survey; North American Coal Corporation; BNI Energy; Basin Electric Power Cooperative; Minnkota Power Cooperative; and many more.
Kay, John P.↗
Williston Basin Carbon Ore, Rare Earth, and Critical Minerals (CORE-CM) Program
The U.S. Department of Energy’s (DOE’s) Office of Fossil Energy awarded 13 Carbon Ore, Rare-Earth and Critical Minerals (CORE-CM) programs as part of the CORE-CM Initiative, designed to develop the technology and upstream and midstream supply chains to extract rare-earth elements (REEs) and CMs from the nation’s coal supplies. The intent is to catalyze regional economic growth and job creation while strengthening the use of domestic resources. The Williston Basin CORE-CM Program aims to drive the expansion and transformation of coal and coal-based resource usage within the Williston Basin to produce REEs, CMs, and nonfuel carbon-based products (CBPs). The work constitutes Phase 1 of a long-term program. The objectives of Phase 1 are to identify the existing knowledge base and gaps and to develop a series of assessments/plans, including an initial basinal assessment; a characterization and data acquisition plan; a waste stream reuse plan; a basinal strategies assessment for infrastructure, industries, and business; a technology assessment, development, and field-testing plan; a technology innovation center plan(s); and a stakeholder outreach and education plan. Originally, the CORE-CM programs were to do little if any sample collection as part of the Phase 1 program. As part of the ongoing interactions with DOE regarding the progress of the 13 CORE-CM programs, DOE has decided to extend Phase 1 with additional funding to allow all of the Phase 1 CORE-CM programs to collect and characterize more samples that have potential to be sources of REEs and CMs. The goal of this project is to initiate the development of a new industry in the resource-rich Williston Basin that will generate economic growth and job creation through a coalition team of private industry; university; and state, local, and federal government entities. A coalition team of nearly 30 private industry; university; and state, local, and federal government partners was formed for this program. Partners include the University of North Dakota Energy & Environmental Research Center, Institute for Energy Studies, and Nistler College; North Dakota State University; Montana Tech University; Pacific Northwest National Laboratory; Critical Materials Institute; North Dakota Geological Survey; South Dakota Geological Survey; U.S. Geological Survey; North American Coal Corporation; BNI Energy; Basin Electric Power Cooperative; Minnkota Power Cooperative; and many more.
Kay, John P.↗
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↗
Technoeconomic and life cycle energy analysis of carbon fiber manufactured from coal via a novel solvent extraction process
Coal is a versatile energy resource and was a driver of the industrial revolution that transformed the economies of Europe and North America and the trajectory of civilization. In this work, a technoeconomic analysis was performed for a coal-to-carbon-fiber manufacture process developed at the University of Kentucky’s Center for Applied Energy Research. According to this process, coal, with decant oil as the solvent, was converted to mesophase pitch via solvent extraction, and the mesophase pitch was subsequently converted to carbon fiber. The total cost to produce carbon fibers from coal and decant oil via the solvent extraction process was estimated to be $\$$11.50/kg for 50,000-tow pitch carbon fiber with a production volume of 3750 MT/year. The estimated carbon fiber cost was significantly lower than the current commercially available PAN-based carbon fiber price ($\$$20–$\$$30/kg). With decant oil recycling rates of 50% and 70% in the solvent extraction process, the manufacturing cost of carbon fiber was estimated to be $\$$9.90/kg and $\$$9.50/kg of carbon fiber, respectively. A cradle-to-gate energy assessment revealed that carbon fiber derived from coal exhibited an embodied energy of 510 MJ/kg, significantly lower than that of conventionally produced carbon fiber from PAN. This notable difference is primarily attributed to the substantially higher conversion rate of coal-based mesophase pitch fibers into carbon fiber, surpassing PAN fibers by 1.6 times. These findings indicate that using coal for carbon fiber production through solvent extraction methods could offer a more energy-efficient and cost-competitive alternative to the traditional PAN based approach.
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Coal-based graphene oxide-like materials: A comprehensive review
Coal is the most abundant energy and hydrocarbon resource in the United States which has been primarily used for power generation. With the increasing retirement of coal power plants and transition to a low-carbon emission economy, the future use of coal will likely shift to a feedstock source for production of valuable materials for different applications. In this review, the latest research reported on production of graphene-like materials in a powder form from coal is compiled and discussed. Here, this review includes: 1) brief background information on graphene and related materials (GRM); 2) relevant material, resource, economic, and socioeconomic information regarding suitability of coal as a potential feedstock for production of GRM; 3) a summary of common approaches for coal upgrading for preparation of more suitable precursors for production of GRM; 4) a compilation and analysis of the reported routes and methods for preparation of GRM from coal and coal derivatives; and 5) reported potential applications of coal-based GRM.
36 MATERIALS SCIENCE↗