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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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DOE OSTI2018

Increasing the Rate and Extent of Microbial Coal to Methane Conversion through Optimization of Microbial Activity, Thermodynamics, and Reactive Transport (Final Scientific/Technical Report)

Currently, coal bed methane (CBM) wells have a limited lifetime since the rate of methane removal via the installed wells is much faster than the in situ methane production rates. Along with water issues created by large amounts of CBM production water, the short life span of CBM wells is a huge deterrent to the environmental and economic feasibility of CBM production. The process of biogenic methanogenesis can be enhanced via the stimulation of the associated microbial communities that can convert the organic fractions of coal to methane. This process is termed Microbially-Enhanced Coal Bed Methane (MECBM). However, the rates of methane production are still limited and long incubation times are necessary. We hypothesized that the elucidation of chemical and biological parameters that limited MECBM together with thermodynamic considerations would inform strategies to optimize the process under flow conditions. We incorporated microbiological, physicochemical, and engineering processes to develop a more sustainable CBM production scheme with native coal and native microorganisms. The proposed combination of microbial ecology and physiology as well as optimized engineering principles minimized key constraints that impact microbial coal conversion to methane under environmentally relevant conditions. The combined approach for bench-scale tests resulted in more effective and less environmentally burdensome coal-dependent methane production with the potential for H 2 O and CO 2 management.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2017

Ensuring Reliable Natural Gas-Fired Generation with Fuel Contracts and Storage - DOE/NETL-2017/1816

This report finds that natural gas-fired power plants purchase fuel both on the spot market and through firm supply contracts; there do not appear to be clear drivers propelling power plants toward one or the other type. Most natural gas-fired power generators are located near major natural gas transmission pipelines, and most natural gas contracts are currently procured on the spot market. Although there is some regional variation in the type of contract used, a strong regional pattern does not emerge. Whether gas prices are higher with spot or firm contracts varies by both region and year. Natural gas prices that push the generators higher in the supply curve would make them less likely to dispatch. Most of the natural gas generators discussed in this report would be unlikely to enter firm contracts if the agreed price would decrease their dispatch frequency. The price points at which these generators would be unlikely to enter a firm contract depends upon the region that the generator is in, and how dependent that region is on natural gas. The Electric Reliability Council of Texas (ERCOT) is more dependent on natural gas than either Eastern Interconnection or Western Interconnection. This report shows that above-ground storage is prohibitively expensive with respect to providing storage for an extended operational fuel reserve comparable to the amount of on-site fuel storage used for coal-fired plants. Further, both pressurized and atmospheric tanks require a significant amount of land for storage, even to support one day’s operation at full output. Underground storage offers the only viable option for 30-day operational storage of natural gas, and that is limited by the location of suitable geologic formations and depleted fields.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2017

Characterization of Rare Earth Element Minerals in Coal Utilization Byproducts

The United States currently produces over 100 million tons of coal utilization byproducts (CUB) per year in the form of fly ash, bottom ash, slag, and flue gas (American Coal Ash Association (ACCA), 2015). But this “waste material” also contains potentially useful levels of rare earth elements (REE). Rare earth elements are crucial for many existing and emerging technologies, but the U.S. lacks a domestic, sustainable REE source. Our project explored the possibility of developing a supply of REEs for U.S. technologies by extracting REEs from CUBs. This work offers the potential to reduce our dependence on other countries for supply of these critical elements (NETL, REE 2016 Project Portfolio). Geologic and diagenetic history, industrial preparation methods, and the specific combustion process all play major roles in the composition of CUB. During combustion, inorganic mineral phases of coal particles are fluidized at temperatures higher than 1400oC, so inorganic mineral materials are oxidized, fused, disintegrated, or agglomerated into larger spherical and amorphous (non-crystalline) particles. The original mineralogy of the coal-containing rock and heating/cooling of the material significantly affects the composition and morphology of the particles in the combustion byproduct (Kutchko and Kim, 2006). Thus, different types of coal/refuse/ash must be characterized to better understand mineral evolution during the combustion process. Our research focused on developing a working model to address how REE minerals behave during the combustion process: this research should help determine the most effective engineering methods for extracting REEs from CUBs. We used multimodal imaging and image processing techniques to characterize six rock and ash samples from different coal power plants with respect to morphology, grain size, presence of mineral phases, and elemental composition. The results of these characterization activities provided thresholds for realizing the occurrence of REE mineral phases in CUB and allowed us to calculate structural and volumetric estimates of REE. Collectively, the rock and coal ash samples contained minerals such as quartz, kaolinite, muscovite/illite, iron oxide (as hematite or magnetite), mullite, and clinochlore. Trace minerals included pyrite, zircon, siderite, rutile, diopside, foresterite, gypsum, and barite. We identified REE phosphate minerals monazite (Ce,La,Nd,Th)(PO 4 ,SiO 4 ), xenotime (YPO 4 ,SiO 4 ), and apatite (Ca 5 (PO 4 ) 3 (F,Cl,OH) via SEM and electron microprobe analysis: these materials generally occurred as 1-10 μm-long crystals in the rock and ash samples. As has been shown in other studies, amorphous material-aluminosilicate glass or iron oxyhydroxide-are the major components of coal fly and bottom ash. Trace amounts of amorphous calcium oxide and mixed element (e.g., Al-Si-Ca-Fe) slag are also present. Quartz, mullite, hematite, and magnetite are the crystalline phases present. We found that REEs are present as monomineralic grains dispersed within the ash, as well as fused to or encapsulated by amorphous aluminosilicate glass particles. Monazite and xenotime have relatively high melting points (>1800 °C) compared to typical combustion temperatures; our observations indicate that the REE-phosphates, which presumably contribute a large percentage of REE to the bulk ash REE pool, as measured by mass spectroscopy, are largely unaltered by the combustion. Our study shows that conventional coal combustion processes sequester REE minerals into aluminosilicate glass phases, which presents a new engineering challenge for extracting REE from coal ash. The characterization work summarized in this report provides a semi-quantitative assessments of REE in coal-containing rock and CUB. The data we obtained from 2- and 3-D imaging, elemental mapping, volumetric estimates, and advanced high-resolution pixel classification successfully identified the different mineral phases present in CUB. Further, our characterization results can guide techniques for extracting REEs from CUB, or other geologic and engineered materials. Whilst, interpretations will inform future REE separation and extraction techniques and technologies practical for commercial utilization of combustion byproducts generated by power plants.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2018

Coal-Powered Electric Generating Unit Efficiency and Reliability Dialogue: Summary Report

Coal continues to play a critical role in powering the Nation’s electricity generation, especially for baseload power plants. With aging coal generation assets facing decreased performance due to the state of the equipment, and with challenges exacerbated by the current market pressures on the coal sector, there are opportunities to advance early-stage technologies that can retrofit or replace equipment components. These changes will eventually result in significant improvements in plant performance once further developed and deployed by industry. Research and development in areas such as materials, fluid dynamics, fuel properties and preparation characteristics, and a new generation of plant controls can lead to new components and systems that can help improve the efficiency and reliability of coal-fired power plants significantly, allowing these assets to continue to provide baseload power. Coal stockpiles at electricity generation plants are typically large enough to provide 30 to 60 days of power prior to resupply—significantly enhancing the stability and reliability of the U.S. electricity sector. Falling prices for non-dispatchable renewable energy and mounting environmental regulations, among other factors, have stimulated efforts to improve the efficiency of these coal-fired electric generating units (EGUs). In addition, increased reliance on natural gas and non-dispatchable energy sources has spurred efforts to further increase the reliability of coal EGUs. The Coal Powered EGU Efficiency and Reliability Dialogue brought together stakeholders from across the coal EGU industry to discuss methods for improvement. Participants at the event reviewed performance-enhancing innovations in coal EGUs, discussed the potential for data-driven management practices to increase efficiency and reliability, investigated the impacts of regulatory compliance on coal EGU performance, and discussed upcoming challenges for the coal industry. This report documents the key findings and research suggestions discussed at the event. Discussions at the workshop will aid DOE in developing a set of distinct initiatives that can be pursued by government and industry to realize promising technological pursuits. DOE plans to use the results of the Dialogue coupled with ongoing technical analysis of efficiency opportunities within the coal-fired fleet, and additional studies to develop a comprehensive strategy for capitalizing on thermal efficiency improvements. Expected Power Plant Efficiency Improvements include developing cost-effective, efficient, and reliable technologies for boilers, turbines, and sensors and controls to improve the reliability and efficiency of existing coal-based power plants. The Office of Fossil Energy at DOE plans to work with industry to develop knowledge pertaining to advanced technologies and systems that industry can subsequently develop. These technologies and systems will increase reliability, add operational flexibility and improve efficiency, thereby providing more robust power generation infrastructure. The following table lists the research suggestions and questions for further investigation that were identified by participants in each session of the dialogue.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2018

Improving Competitiveness of U.S. Coal Dialogue

The Improving Competitiveness of U.S. Coal Dialogue held in September 2017 explored a broad range of technical developments that have the potential to improve U.S. coal competitiveness in domestic and overseas markets. The workshop is one in a series of events hosted by DOE to gather expert input on challenges and opportunities for reviving the coal economy. This event brought together coal industry experts to review developments in a broad range of technical areas such as conventional physical (e.g. dense-medium) technologies, and dry coal treatments; thermal, chemical, and bio-oxidation coal upgrading technologies; coal blending; and applications for ultrafine coal and waste streams. The workshop was organized to focus on three main discussion topics: Challenges and Opportunities for Improving U.S. Coal Competitiveness in Overseas Markets, Mineral Processing, and Technologies to Expand the Market Reach of Coal Products. In each session, invited experts delivered presentations to help frame the subsequent group discussion. Throughout the discussions, participants described many possible areas of research and development (R&D) in which DOE involvement could help to produce significant outcomes. In addition, participants discussed a number of open questions—those that the industry has raised or investigated but not yet resolved. In discussing the three topics, the participants suggested potential areas of research and issues for further investigation. As summarized in Table ES-1, these crosscutting suggestions centered on combustion technologies, coal quality, coal processing, environmental issues, and other issues. The discussions at this workshop will serve as an input that DOE considers in developing initiatives that can be pursued by government and industry. This workshop generated strategies that described core research concepts, identified implementation steps, estimated benefits, clarified roles of government and industry, and outlined next steps. While more work is needed, each of these initiatives, included in the sections that follow, details new ideas to increase efficiency and reduce carbon emissions. DOE will integrate the results of this workshop with ongoing research work at the National Laboratories as well as other relevant data sources. This combined information will be used to develop a comprehensive strategy for capitalizing on the opportunity for U.S. coal and mineral competitiveness.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2017

An Advanced Catalytic Solvent for Lower Cost Post-Combustion CO 2 Capture in a Coal-Fired Power Plant

In this report, CAER addresses DOE’s objectives for improvements on post-combustion CO 2 capture through a three-fold approach including 1) advanced solvent, 2) homogeneous catalyst and 3) membrane carbon enrichment system. CAER-B3 solvent was formulated to improve the overall thermodynamics with the addition of a proton receiver while maintaining faster kinetics with the addition of thermally robust primary amine. The EH&S study indicates that CAER-B3 solvent poses little human toxicological or ecological risk in its raw material form. Generation of significant quantities of nitrosamines was deemed unlikely when using B3 solvent for CO 2 capture from coal-derived flue gas. The catalytic solvent caused a 21% reduction in energy demand, achievable via decreasing the liquid flowrate. Cyclic capacity nearly doubled due to the slower flowrate, and therefore, reduced the sensible heat required to remove CO 2 in the stripper. The increased rich loadings achieved by either pre-concentrating membrane or dewatering membrane prior to stripper, in addition to improved cyclic capacity, will lower downstream compression costs, while reducing the energy consumption per unit of CO 2 produced. Moreover, the CAER-B3 solvent demonstrated a greater thermal stability, lessening the rate of amine loss, caused by solvent degradation and emissions, by 50-70%. The CAER developed catalysts with a second order rate constant of 7.5 x 10 4 – 10 5 M -1 s -1 , far beyond those reported to date. The catalyst was designed to be a mimic of the enzyme carbonic anhydrase and increase the rate of CO 2 hydration to produce bicarbonate. As such, a 10-25% improvement in absorption rate was observed over the MEA base case. Enhancements can be imparted to the full scale system to reduce packing height of the absorber column, resulting in significant capital cost savings. Furthermore, the family of CAER catalysts showed less than 10% decomposition over 100 hours at 100 °C, suggesting that these catalysts will be stable in the harsh oxidative and thermal process conditions of an industrial carbon capture unit. Flue gas contaminants, such as NO x and SO x , also did not impact catalytic activity. A method for synthetic production of 500 g/batch was designed, verified, and well-documented, with scaling capabilities up to 500 kg. Two types of membranes were designed and tested for the purpose of increasing the solvent carbon loading prior to entering the stripper column. 500 hour and 100 hour verification studies were completed for the pre-concentrating membrane and zeolite dewatering membrane, respectively. Results demonstrated that a membrane-based CO 2 enrichment step using a commercial CO 2 membrane, or a zeolite dewatering membrane, or both, should be implemented in the carbon capture process to increase the CO 2 partial pressure by 16%, resulting in a stripping energy reduction of 35% relative to DOE Case 12 MEA solvent. Experimental data showed a carbon loading enrichment of 18-40% in comparison to the configuration without the pre-concentrating gas membrane. During the timespan of this project, challenges were identified and addressed so that enhanced performance may be realized long-term. Mitigation implementations included re-configuration of the bench unit with a solvent recovery column and a knock-out drum, as well as an increase in stripper pressure set point. Both changes resulted in a considerable reduction in the rate of solvent loss. Additionally, the membrane synthesis procedure was modified and validated to address zeolite dissolution concerns along with a new separation module. The techno-economic analysis conducted by WorleyParsons indicated the CAER-adCCS hybrid approach may outperform NETL Case 12 with regards to net plant HHV efficiency and cost of electricity.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2018

Validating the MFiX-DEM Model for Flow Regime Prediction in a 3D Spouted Bed

The spout-fluidized bed reactor with relatively large oxygen carrier particles offers several advantages in chemical looping combustion operation using solid fuels. The large difference in size and weight between the oxygen carrier particles and the smaller coal or ash particles allows the oxygen carrier to be easily segregated for recirculation; the increased solids mixing due to dynamic flow pattern in the spout-fluidization regime prevents agglomeration. The primary objective in this work is to determine the effectiveness of the MFiX-DEM model in predicting the flow regime in a spouted bed. Successful validation of the code will allow the user to fine tune the operating conditions of a spouted bed to achieve the desired operating condition.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2018

Advanced SOFC quality control and the role of manufacturing defects on stack reliability

Atrex Energy rolled out first commercial SOFC generator products in 2013. Following that we embarked on implementation of mass production in order to ramp up productivity and lower the costs in the meantime. To ensure the goal of mass production, an accurate, cost effective and consistent quality control methodology needs to be in place. The aim of this DOE funded project is to devise a machine and methodology for cell quality control using modern non-destructive testing methods and cell rejection criterion based on the empirical determination of the role of manufacturing flaws on stack degradation and reliability. The work scope encompasses two goals aimed at 1) developing automatable techniques for objective flaw detection and 2) developing an understanding of the ramifications of flaws on stack and cell reliability. By accomplishing these two goals it is likely that an advanced stage Quality Control (QC) device can be developed. This project scope encompasses: 1) Invention of a high speed automated instrument for spatial mapping of surface and sub-surface imperfections in production cells (ex situ) using modern imaging techniques. 2) Identification of rejection criteria upon which to screen cells from production by: a. Magnification of the effect of production defects on cell degradation through fabrication and testing of micro-cells which encompass these imperfections. b. The long term testing of full size production cells both as single cells and in small stacks, in order to correlate the (in situ) performance and degradation with the imperfection type (identified ex-situ) and hence be able to classify imperfections as actual defects. We first built a defect library with the cells containing imperfections classified and documented. The cells with various imperfections were tested to evaluate the imperfection potential impact on cell electrochemical performance. Evaluations were conducted on minicell, single cell and stack levels. On minicell level, pinhole, scratch, crack, contamination, and pop-out were investigated. We found: (1) none of the imperfections causes calamity type failure, (2) pinholes do not show measurable effect on minicell performance, (3) imperfection such as electrolyte abrasion, scratch, and pop out cause minicell potential to fluctuate by different degrees; the cells with such imperfections exhibit sensitivity of potential to high fuel utilization and “self healing” behavior. On single cell level we evaluated the effect of long crack and high population pinholes. The cell with a long crack does not show performance compromise at start. There is no potential fluctuation or sensitivity to high fuel utilization or catastrophic failure. The voltage degradation due to thermal cycle is slightly higher than normal cells. The cells with high population pinholes perform surprisingly as well as normal cells over a period of 3,500h. Even when subjected to cyclic load condition, the cells 4 show negligible degradation. Our cells appear to have “self immunization” feature which fends off the adversary effects of certain imperfections. Defects were also evaluated on stack level. Two stacks were made each with ten defect cells. The first stack was tested for 13,2000h under steady load condition while the second was tested for 9,000h under transient load conditions. We found: (1) voltage fluctuation and sensitivity to thermal cycle were not observed in contrast to minicell test, (2) of the various cracks examined, including longitudinal cracks, circumferential crack, crack near closed and open ends, none exhibited distinguishable impact on performance, (3) defect cells exhibited higher degradation rates on average under steady load condition; Individually some defect cells performed similarly or better than reference cells, (4) under steady load condition all the cells degrade monotonically with degradation rate increasing with time, (5) under cyclic (transient) load condition, both defect and reference cells exhibit complex dynamic behaviors, (6) fuel loss (leak) was measured occasionally for stack 1, the cells with crack showed the highest fuel loss increase, nevertheless, no correlation with performance degradation could be established with certainty, and (7) no catastrophic failure ever happened other than incremental degradation. Posttest inspection and microanalysis were carried out; the observations are summarized in what follows: (1) Electrolyte pinholes, some scratches and IC porosity became undetectable after testing. (2) The cathode covering the popout defects is intact without any cracking or delamination. (3) The scratch was covered by cathode in pristine state; Ni oxide or NiO-YSZ filled the space where electrolyte was missing. After >10,000h operation, the cathode that used to cover the scratch was missing but the size of the scratch remains unchanged; there is a fairly dense Ni oxide layer on top of the scratch. (4) All of the cracks remain their original dimensions. Current collector kept longitudinal cracks closed which mitigated the adversary effect of crack on cell performance/durability. (5) The crack at open end showed some deterioration manifested by a small oxidation zone in the vicinity of the crack. Wide spectrum of imaging techniques were surveyed and evaluated to detect tubular SOFC defects. Optical methods, with and without assistance of expression technique, were applied to detect all kinds of defects. Thermograph method in combination of CO2 leak, ultra-sound and electric potential was also extensively evaluated to detect surface and under-surface defects such as short circuit. Based on these works, laser camera has been selected to build the final QC machine vision inspection system. The Gocator laser profile sensor was setup to generate 2D surface intensity images of tubular SOFC surface which were analyzed with Sherlock machine vision software supplied by Teledyne Dalsa. The Gocator output was integrated with the Sherlock software and enabled live images to be imported by a Common Vision Blox driver. The Sherlock software was programmed to detect various surface defects from the surface intensity images generated by the Gocator. These measurements are subsequently used to make pass or fail decisions.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2018

Economical and Environmentally Benign Extraction of Rare Earth Elements (REES) from Coal & Coal Byproducts

This final report provides a complete summary of the activities, results, analytical discussion, and overall evaluation of the project titled “Economical and Environmentally Benign Extraction of Rare Earth Elements (REES) from Coal & Coal Byproducts” under DOE Award Number DE-FE-0027155 that started in March 2016 and ended December 2017. Fly ash was selected as the coal-byproduct source material due to fact that it is readily available with no need for extensive methods to obtain the material, it is produced in large quantities (>50 million tons per year) and had REE concentrations similar to other coal-byproducts. The selected fly ash used throughout this project was from the Mill Creek power generating facility operated by Louisville Gas and Electric located in Louisville, KY and was subjected to a variety of physical and chemical characterization tests. Results from fusion extractions showed that the selected fly-ash had a TREE+Y concentration of 480 ppm with critical REEs concentration of 200 ppm. The fly ash had an outlook ratio of 1.25 and an estimated value of $16-$18 worth of salable REEs per 1-tonne of fly ash. Additional characterizations by optical evaluation, QEMSCAN, XRD, size fractionation, and SEM analysis showed the fly ash consisted of small glassy spherules with a size range between 1 to 110 µm (ave. diam. of 13 um), was heterogeneous in chemical composition (main crystalline phases: aluminum oxides and iron oxides) and was primarily an amorphous material (75 to 80%). A simple stepped approach was completed to estimate the total REE resource quantity. The approach included REE characterization of the representative samples, evaluation of fly-ash availability, and final determination estimated resource availability with regards to REE grade on a regional and national scale. This data represents the best available information and is based upon the assumptions that the power generating facility where the fly-ash was obtained will use the same coal sources (actual mines were identified), the coal materials will have relatively consistent REE concentrations, and the REE extraction process developed during this project can achieve 42% REE recovery (validated and confirmed). Calculations indicated that the estimated REE resource is approximately 175,000 tonnes with a current estimated value of $3,330MM. The proposed REE extraction and production process developed during this project used four fundamental steps; 1) fly-ash pretreatment to enhance REE extraction, 2) REE extraction by acid digestion, 3) REE separation/concentration by carbon adsorption and column chromatography, and 4) REE oxide production. Secondary processing steps to manage process residuals and additional processing techniques to produce value-added products were incorporated into the process during the project. These secondary steps were not only necessary to manage residuals, but also provided additional revenue streams that offset operational and capital expenditures. The process produces one value product stream (production of zeolite Na-P1), a solids waste stream, and one liquid stream that met RCRA discharge requirements. Based upon final design criteria and operational parameters, the proposed system could produce approximately 200 grams of REOs from 1-tonne of fly-ash, thereby representing a TREE+Y recovery of 42% (project target of > 25%). A detailed economic model was developed to evaluate both CAPEX and OPEX estimates for systems with varying capacities between 100 kg to 200 tonnes of fly ash processed per day. Using a standard system capacity of 10 tonne/day system, capital costs were estimated at $88/kg fly ash while operating costs were estimated at approximately $450/kg fly ash. This operating cost estimate includes a revenue of $495/tonne of fly ash processed from the value-added product produced from the system (zeolite Na-P1). Although operating cost savings due to zeolite production were significant, the capital + operating cost for a 10 tonne system was more expensive than the total dollar value of REEs present in the fly ash material. Specifically, the estimated cost per 1-tonne of fly ash treated is approximately $540 while the estimated value of REEs in the fly ash is $18-$20/tonne. This is an excessive difference showing that the proposed process is not economically feasible strictly on the basis of REE revenue compared to extraction costs. Although the current proposed system does not produce sufficient quantities of REEs or additional revenue sources to offset operational and capital costs, supplementary factors including US strategic concerns, commercial demands, and defense department requirements must be factored. At this time, the process developed during this project provides foundational information for future development of simple processes that require low capital investment and one that will extract a valuable quality and quantity of REE oxides from industrial waste.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2018

Advanced Ultrasupercritical (AUSC) Materials Thick-Walled Cycling Header Development for ComTest-AUSC (Final Report)

Alstom Power Inc., a wholly owned subsidiary of the General Electric Company (GE) recently completed “Advanced Ultrasupercritical (AUSC) Materials Thick-Walled Cycling Header Development for ComTest-AUSC” under Award No. DE-FE0026183 for the U.S. Department of Energy National Energy Technology Laboratory (DOE NETL). This project developed a design for testing of a high temperature nickel-based superalloy thick-walled header to simulate cycling and flexible plant operation in new and existing plants. The objective was to simulate the expected thermal stresses of a new AUSC plant or a retrofit header in an existing plant to improve flexible dynamic operation while maintaining component integrity and overall power plant reliability. The high performance superalloy materials that enable higher operating temperatures and pressures can support future transformational power technologies including new AUSC plants at 4250-5000 psi, 730°C/760°C or will serve as a replacement component in a repowered or retrofit USC coal powered cycling plant at 3600 psi, 600°C. These alloys can also enable supercritical CO2 cycles, nuclear power, solar power and more efficient natural gas combined cycle units as targeted by the U.S. DOE/NETL Cross-Cutting Research Technology Program Plan. Recently developed advanced nickel alloys such as Inconel 740H (740H) and Haynes 282 (H282) have been successfully tested on a pilot scale for fireside corrosion using steam loop tubing at AUSC temperatures of 760°C in actual operating coal fired boiler. These high strength materials have been demonstrated their adequacy for use in other high temperature boiler components such as superheater tubes. Thick-walled superheater outlet headers which operate at high temperatures and pressure under severe cycling condition are considered as one of the most critical component in the AUSC coal fired boiler. Over the design life of a plant, these headers are exposed to the most severe fatigue and creep damage accumulation and need to be properly designed for the expected cycling in an AUSC plant with flexible operation. These materials need to demonstrate adequate design life of 20 to 30 years for creep and fatigue conditions. The following tasks were performed: 1. A conceptual design was developed of a thick-walled component representative of typical headers with several tube connections and proper flow rates (~100,000 lbs/hr) suitable for Phase II test at 760°C operation. This was based on a process analysis of expected full scale new and component retrofit designs for AUSC; 2. A multi-physics flow and heat transfer computational fluid dynamics (CFD) analysis of the component for proper layout of the header configuration, number and geometry (size) of tubes required for bypass flow, flow rates through the tubing, and sectional pressure drops was performed. Steam to header metal heat transfer film coefficients in the header section and the tubes during the two stages (half load and full load) of the cycling operation were evaluated and used in the stress analysis; 3. Detailed analytical evaluation of the thick-walled pipe and tube connections for mechanical integrity under cycling conditions was performed. This included transient thermal stress analysis and fatigue usage estimation including the tube-to-pipe weld geometries and weld materials; 4. A layout and design of the thick-walled test component was developed and instrumentation required for a test was identified; 5. Continuum Damage Mechanics (CDM) creep prediction models were extended to 740H and H282 and validated with public data on 740H and H282 for use in creep analysis. In addition, detailed creep analyses were performed separately for the design life of the conceptual AUSC superheater outlet header using these General Electric (GE) creep constitutive models. GE was the prime contractor for the project, which was directed by Principal Investigator Robert Schrecengost and Lead Scientist Dr. B. Reddy Ganta. Other collaborative participants in this project included GE Global Research, GE Boiler Engineering, and a Technical Consultant from EPRI.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2018

Indirect Liquefaction of Coal-Biomass Mixture for Production of Jet Fuel with High Productivity and Selectivity

Coal to liquids (CTL) and coal-biomass to liquids (CBTL) processes were advanced by testing and demonstrating Southern Research’s sulfur tolerant nickel-based reforming catalyst and Chevron’s highly selective and active cobalt-zeolite hybrid Fischer-Tropsch (FT) catalyst to clean, upgrade and convert syngas predominantly to jet fuel range hydrocarbon liquids, thereby minimizing expensive cleanup and wax upgrading operations. The National Carbon Capture Center (NCCC) operated by Southern Company (SC) at Wilsonville, Alabama served as the host site for the gasifier slip-stream and simulated syngas testing/demonstration. Reformer testing was performed to (1) reform tar and light hydrocarbons, (2) decompose ammonia in the presence H2S, and (3) deliver the required H2 to CO ratio for FT synthesis. FT Testing was performed to produce a product primarily containing C5-C20 liquid hydrocarbons and no C21+ waxy hydrocarbons with productivity greater than 0.7 gC5+/g catalyst/h, and at least 70% diesel and jet fuel range (C8-C20) hydrocarbon selectivity in the liquid product. A novel heat-exchange reactor system was employed to enable the use of the highly active FT catalyst and larger diameter reactors that results in cost reduction for commercial systems. Following laboratory development and testing, SR’s laboratory reformer was modified to operate in a Class 1 Div. 2 environment, installed at NCCC, and successfully tested for 125 hours using raw syngas. The catalyst demonstrated near equilibrium reforming (~90%) of methane and complete reforming/decomposition of tar and ammonia in the presence of up to 380 ppm H2S. For FT synthesis, SR modified and utilized a bench scale skid mounted FT reactor system (SR-CBTL test rig) that was fully integrated with a slip stream from SC/NCCC’s transport gasifier (TRIG). The test-rig developed in a previous project (DE-FE0010231) was modified to receive up to 7.5 lb/h raw syngas augmented with bottled syngas to adjust the H2/CO molar ratio to 2, clean it to cobalt FT catalyst specifications, and produce liquid FT products at the design capacity of up to 6 L/day. Promising Chevron catalyst candidates in the size range from 70-200 μm were loaded onto SR’s 2-inch ID and 4-inch ID bench-scale reactors utilizing IntraMicron’s micro-fiber entrapped catalyst (MFEC) heat exchange reactor technology. During 2 test campaigns, the FT reactors were successfully demonstrated at NCCC using syngas for ~420 hours. The catalyst did not experience deactivation during the tests. SR’s thermo-syphon heat removal system maintained reactor operating temperature along the axis to within ±4 °C. The experiments gave a steady catalyst productivity of 0.7-0.8 g/g catalyst/h, liquid hydrocarbon selectivity of ~75%, and diesel and jet fuel range hydrocarbon selectivity in the liquid product as high as 85% depending on process conditions. A preliminary techno-economic evaluation showed that the SR technology-based 50,000 bpd plant had a 10 % lower total plant cost compared to a conventional slurry reactor based plant. Furthermore, because of the modular nature of the SR technology, it was shown that the total plant cost advantage increases to >35 % as the plant is scaled down to 1000 bpd.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2018

DEFE0023863 Final Report, Technology for GHG Emission Reduction and Cost-Competitive Mil-Spec Jet Fuel Production using CTL

Ceramatec Inc, in collaboration with IntraMicron (IM), the Energy & Environmental Research Center (EERC) and Sustainable Energy Solutions, LLC (SES), have completed a three-year research project integrating their respective proprietary technologies in key areas to demonstrate production of a jet fuel from coal and biomass sources. The project goals and objectives were to demonstrate technology capable of producing a “commercially-viable quantity” of jet fuel and make significant progress toward compliance with Section 526 of the Energy Independence and Security Act of 2007 (EISA 2007 §526) lifecycle greenhouse gas (GHG) emissions requirements. The Ceramatec led team completed the demonstration of nominal 2 bbl/day Fischer-Tropsch (FT) synthesis pilot plant design, capable of producing a nominal 1 bbl/day in the Jet-A/JP-8 fraction. This production rate would have a capacity of 1,000 gallons of jet fuel per month and provide the design basis of a 100 bbl/day module producing over 2,000 gallons of jet fuel per day. Co-gasification of coal-biomass blends enables a reduction of lifecycle greenhouse gas emissions from equivalent conventional petroleum derived fuel basis. Due to limits of biomass availability within an economic transportation range, implementation of a significant biomass feed fraction will require smaller plants than current world scale CTL and GTL FT plants. Hence a down-scaleable design is essential. The pilot plant design leverages Intramicron’s MicroFiber Entrapped Catalyst (MFEC) support which increases the catalyst bed thermal conductivity two orders of magnitude, allowing thermal management of the FT reaction exotherm in much larger reactor tubes. In this project, single tube reactors having 4.5 inch outer diameter and multi-tube reactors having 4 inch outer diameters were operated, with productivities as high as 1.5 gallons per day per linear foot of reactor tube. A significant reduction in tube count results from the use of large diameter reactor tubes, with an associated reduction in reactor cost. The pilot plant was designed with provisions for product collection capable of operating with conventional wax producing FT catalysts but was operated with a Chevron hybrid wax-free FT catalyst. Process simplification enabled by elimination of the wax hydrocracking process unit provides economic advantages in scaling to biomass capable plant sizes. Intramicron also provided a sulfur capture system based on their Oxidative Sulfur Removal (OSR) catalyst process. The integrated sulfur removal and FT systems were operated with syngas produced by the Transport Reactor Development Unit (TRDU) gasifier at the University of North Dakota EERC. SES performed modeling of their cryogenic carbon capture process on the energy, cost and CO2 emissions impact of the Coal-biomass synthetic fuel process.

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DOE OSTI2017

Alstom’s Limestone Chemical Looping Gasification Process for High Hydrogen Syngas Generation

Alstom Power Inc., a wholly owned subsidiary of the General Electric Company (GE), is developing Limestone-based Chemical Looping (LCL™) Processes, utilizing limestone derived calcium sulfate as an oxygen carrier to transport oxygen from air to the fuel. The LCL™ process is a breakthrough technology with the potential to capture CO 2 and SO 2 from new and existing coal-fired power plants at reduced costs while maintaining high plant power generation efficiency. Chemical looping is a next generation advancement to oxy-combustion which would not require the significant investment in a cryogenic distillation type oxygen production plant. Instead of the energy-consuming oxygen plant, chemical looping uses a benign material to directly remove oxygen from the air and bring that oxygen into contact with the fuel. This "game changing" technology is the lowest cost-of-electricity technical approach that GE Power has identified to date for coal power with carbon capture. The technology has significantly lower capital costs compared to a conventional steam power plant with first generation carbon capture technologies. This new power plant concept is based on a hybrid combustion-gasification process utilizing high temperature chemical and thermal looping technology. In the air reactor, a solid oxygen carrier picks up oxygen from air through an oxidation reaction and leaves nitrogen behind. The hot oxygen-carrying solid carrier is then transported to a fuel reactor, where it releases oxygen. The released oxygen then converts the coal in the fuel reactor into combustion gases. The solid carrier is recycled back to the air reactor for regeneration completing the “chemical loop.” The regeneration step produces heat from which steam is produced for power generation while the process results in a concentrated carbon dioxide stream in which the carbon is captured for use or sequestration (CCUS). Limestone as a precursor for the oxygen carrier is abundant, benign, low cost, and is used in CFB and PC boilers for sulfur control. Challenges associated with this carrier include a complex reaction mechanism with possible side reactions leading to the release of SO 2 . The development of the Limestone Chemical Looping Gasification (LCL-G™) technology was co-funded by the Department of Energy under the DOE/NETL Cooperative Agreement No. DE- FE0023497, in parallel with the collaborative combustion (LCL-C™) program. In this report, the LCL-G™ experimental testing from the electrically-heated, once-through, 100 kW Pilot-Scale Test Facility (PSTF) is analysed and reviewed. The PSTF Oxidizer is a 50-foot tall, 100-mm diameter transport reactor, while the PSTF Reducer reactor is based upon a bubbling-bed design. The experimental data from four (4) test campaigns (denoted “Weeks”) are reviewed and discussed. The LCL-G™ (DE-FE0023497) project objectives for gasification are >90% carbon gasified in the Reducer and a H 2 :CO molar generation ratio of 2:1. These project performance metrics were not met by a single coal test, but they were individually approached in two separate tests.

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DOE OSTI2017

Improvement of Alstom's Limestone-Based Chemical Looping Combustion Process for Higher Purity Flue Gas Production

Alstom Power Inc., a wholly owned subsidiary of the General Electric Company (GE), is developing Limestone-based Chemical Looping (LCL™) Processes, utilizing limestone derived calcium sulfate as an oxygen carrier to transport oxygen from air to the fuel. The LCL™ process is a breakthrough technology with the potential to capture CO 2 and SO 2 from new and existing coal-fired power plants at reduced costs while maintaining high plant power generation efficiency. Chemical looping is a next generation advancement to oxy-combustion which would not require the significant investment in a cryogenic distillation type oxygen production plant. Instead of the energy-consuming oxygen plant, chemical looping uses a benign material to directly remove oxygen from the air and bring that oxygen into contact with the fuel. This "game changing" technology is the lowest cost-of-electricity technical approach that GE Power has identified to date for coal power with carbon capture. The technology has significantly lower capital costs compared to a conventional steam power plant with first generation carbon capture technologies. This new power plant concept is based on a hybrid combustion-gasification process utilizing high temperature chemical and thermal looping technology. In the air reactor, a solid oxygen carrier picks up oxygen from air through an oxidation reaction and leaves nitrogen behind. The hot oxygen-carrying solid carrier is then transported to a fuel reactor, where it releases oxygen. The released oxygen then converts the coal in the fuel reactor into combustion gases. The solid carrier is recycled back to the air reactor for regeneration completing the “chemical loop.” The regeneration step produces heat from which steam is produced for power generation while the process results in a concentrated carbon dioxide stream in which the carbon is captured for use or sequestration (CCUS). Limestone as a precursor for the oxygen carrier is abundant, benign, low cost, and is used in CFB and PC boilers for sulfur control. Challenges associated with this carrier include a complex reaction mechanism with possible side reactions leading to the release of SO 2 . The present project (DOE/NETL Cooperative Agreement No. DE-FE0025073) report focuses on coal-fired Limestone Chemical Looping Combustion (LCL-C™) processes that can produce a higher purity flue gas stream and achieve an improved overall performance that will meet the stated DOE goal of generating power from coal while achieving greater than 90% CO2 removal at less than 35% increase in the Levelized Cost of Electricity (LCOE). It builds on the concurrent and synergistic limestone-based chemical looping combustion (LCL-C™) and gasification (LCL-G™) projects with the Department of Energy, that were executed in parallel with the present project. In this report, the LCL-C™ experimental testing from the electrically-heated, once-through, 100 kW Pilot-Scale Test Facility (PSTF) is analysed and reviewed. The PSTF Oxidizer is a 50-foot tall, 100-mm diameter transport reactor, while the PSTF Reducer reactor is based upon a bubbling-bed design. The experimental data from designated test periods (denoted “Weeks”) are reviewed and discussed. The application of high sulfur release in the Reducer (with proper sulfur management) exceeded the LCL-CTM performance targets. Furthermore, the ilmenite blend came within 1 percentage point of meeting all of the performance targets.

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DOE OSTI2017

Alstom’s Chemical Looping Combustion Technology for CO 2 Capture for New and Retrofit Coal-Fired Power Plants

Cold Flow Modeling (CFM) is a critical tool to understand solid transport, corresponding process stability, and the impact on the performance of the LCL-CTM technology. As such it plays a central role in the development of the LCL-CTM process and deserves a standalone report in the final reporting on Phase II of the collaboration with DOE under award DE FE0009484. The 40-Foot Cold Flow Model (CFM) was constructed before the 3 MWth Prototype. The purpose of the CFM is to: develop design and operational information to design the Prototype help resolve solids transport problems that occur with the Prototype provide Prototype operator training. This report provides a review on the use of the CFM to achieve better understanding, design, and operation of solid transport for the LCL-CTM technology. Significant progress was made by iteratively designing, operating, and testing between the CFM and the Prototype scale. Fundamental understanding of the transport of reactive solids was acquired based on the reported effort. Unfortunately, the technical gaps identified for Phase II of the LCL-CTM technology development could not all be eliminated and the transport of solids under high fuel load remained unstable at the Prototype scale. The nature of the iterative learning going back and forth between CFM and Prototype scale became cost-prohibitive and forced the project to pivot at a relatively late date in the project. The LCL-CTM process switched from a Transport reactor design to a Bubbling Fluidized Bed (BFB) design in order to successfully achieve all process criteria but at the 100-kWth scale to accommodate the residual funding. The CFM remains a very relevant tool for future LCL-CTM process development. While the LCL-CTM technology still must be demonstrated under scale up conditions (and the success of the BFB testing would push to scale up in that configuration), the CFM will remain a preferred tool for troubleshooting and reducing the technical gaps of LCL-CTM.

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DOE OSTI2017

Final Technical Report: Plasma Arc Gasification Based Rare Earth Element Recovery from Coal Fly Ash

Southern Research, as the primary awardee, with sub-awardees ArcSec Technologies, LLC (ArcSec) and Reaction Engineering International (REI) have investigated a plasma arc based thermal process intended to concentrate rare earth elements (REE) from coal fly ash. Successful demonstration of the technology would contribute to the effort for realizing a competitive, domestic REE value chain thereby reducing U.S. dependence on foreign supply, maintaining national security interests, and creating opportunities for economic growth. The originally proposed concept included two technology options – 1) a smelting process and 2) a smelting plus vaporization and condensation process. For both options, coal fly ash would be smelted in a plasma arc heated furnace under reducing conditions to separate ash into molten slag and reduced metal (primarily iron) phases. During smelting, it was expected that the REE would also be reduced to metals and partition mostly to the iron phase. During the first year of work, sample coal ash feedstocks were acquired and characterized, feasibility of the smelting process was evaluated in bench-scale experiments, and the vaporization/condensation process was investigated through equilibrium and CFD modeling studies. From the feedstock characterization, REE content for the coal ash samples obtained was measured to be in the range of 302 – 1219 ppm with average at 537 ppm. Though it was successfully demonstrated that ash could be separated into slag and metal phases, the bench-scale experiments were only marginally successful at collecting REE in the metal phase. Producing REE concentrates near the DOE goal of 2%, however, has not been achieved. From the modeling studies, the vaporization/condensation process was predicted to be effective for separating individual REE and producing enriched metal fractions with total REE content higher than 2%, provided the smelting process performed as intended. Supplemental smelting experiments and thermodynamic modeling studies, conducted during the second year of work, indicated a number of technical modifications that could lead to producing higher REE concentrates from coal ash. The strategy shifted to reducing as much of the ash oxides to metals as possible, leaving the REE more concentrated in the remaining slag. Results from later experiments based on the modified approach showed improvements in REE recovery and concentration levels in smelted products. SEM-EDS analyses on product specimens showed agglomerations of reduced metal REE crystals at much larger length-scales as compared to REE content in raw ash.

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DOE OSTI2017

Advancing Coal Catalytic Gasification to Promote Optimum Syngas Production

An investigation was pursued to improve the use of low rank sub-bituminous coal by using suitable catalysts to advance gasification and create cleaner synthesis gas. Bench- and pilot-scale experiments were performed to measure key reactive properties and verify the use of red mud catalyst. The experiments provided reaction data for the development of kinetic models and validation data for CFD simulations. The reaction kinetics were analyzed to provide an understanding of the major pathways involved and identify the necessary reaction mechanisms needed for the computational models. The reaction kinetics model was implemented into the computational fluid dynamics (CFD) code MFiX to simulate, predict and validate the chemistry model with the experiments. It was shown that red mud as a catalyst lowered methane formation during coal gasification. Additional benefits were that red mud destroyed tars formation, promoted water gas shift reaction resulting in a syngas rich in hydrogen. In the presence of red mud catalyst, biomass feedstocks high in ash did not form clinker in the fluidized bed because it prevented the formation of eutectic mixtures. The reaction kinetics model was reasonably robust and the CFD predictions using the model were in good agreement with the experiments.

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