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Bench Scale Development and Testing of a Novel Adsorption Process for Post-Combustion CO₂ Capture

A physical sorption process to produce dry CO₂ at high purity (>98%) and high recovery (>90%) from the flue gas taken before or after the FGD was demonstrated both in the lab and in the field (one ton per day scale). A CO₂ recovery of over 94% and a CO₂ purity of over 99% were obtained in the field tests. The process has a moisture, SOX, and Hg removal stage followed by a CO₂ adsorption stage. Evaluations based on field testing, process simulation and detailed engineering studies indicate that the process has the potential for more than 40% reduction in the capital and more than 40% reduction in parasitic power for CO₂ capture compared to MEA. The process has the potential to provide CO₂ at a cost (<$40/tonne) and quality (<1 ppm H₂O, <1 ppm SOX, <10 ppm O₂) suitable for EOR applications which can make CO₂ capture profitable even in the absence of climate legislation. The process is applicable to power plants without SOX, Hg and NOX removal equipment.

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Radiocarbon as a Reactive Tracer for Tracking Permanent CO 2 Storage in Basaltic Rocks

In view of concerns about the long-term integrity and containment of CO 2 storage in geologic reservoirs, many efforts have been made to improve the monitoring, verification and accounting methods for geologically stored CO 2 . Our project aimed to demonstrate that carbon-14 ( 14 C) could be used as a reactive tracer to monitor geochemical reactions and evaluate the extent of mineral trapping of CO 2 in basaltic rocks. The capacity of a storage reservoir for mineral trapping of CO 2 is largely a function of host rock composition. Mineral carbonation involves combining CO 2 with divalent cations including Ca 2+ , Mg 2+ and Fe 2+ . The most abundant geological sources for these cations are basaltic rocks. Based on initial storage capacity estimates, we know that basalts have the necessary capacity to store million to billion tons of CO 2 via in situ mineral carbonation. However, little is known about CO2-fluid-rock reactions occurring in a basaltic storage reservoir during and post-CO 2 injection. None of the common monitoring and verification techniques have been able to provide a surveying tool for mineral trapping. The most direct method for quantitative monitoring and accounting involves the tagging of the injected CO 2 with 14C because 14C is not present in deep geologic reservoirs prior to injection. Accordingly, we conducted two CO 2 injection tests at the CarbFix pilot injection site in Iceland to study the feasibility of 14C as a reactive tracer for monitoring CO 2 -fluid-rock reactions and CO 2 mineralization. Our newly developed monitoring techniques, using 14C as a reactive tracer, have been successfully demonstrated. For the first time, permanent and safe disposal of CO 2 as environmentally benign carbonate minerals in basaltic rocks could be shown. Over 95% of the injected CO 2 at the CarbFix pilot injection site was mineralized to carbonate minerals in less than two years after injection. Our monitoring results confirm that CO 2 mineralization in basaltic rocks is far faster than previously postulated.

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Recovery. Oxygen Transport Membrane-Based OxyCombustion for CO 2 Capture from Power Plants

This Final report documents and summarizes all of the work performed for the DOE award DE-FC26-07NT43088 during the period from April 2007 - June 2012. This report outlines accomplishments for the following tasks: Task 1 – Process and Systems Engineering, Task 2 – OTM Performance Improvement, Task 3 – OTM Manufacturing Development, Task 4 - Laboratory Scale Testing and Task 5 – Project Management.

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Characterization and Recovery of Rare Earths from Coal and By-Products

Coal is a precious resource, both in the United States and around the world. The United States has a 250-year supply of coal, and generates between 30 - 40% of its electricity through coal combustion. Approximately 1 Gt of coal has been mined annually in the US, although the 2015 total will likely be closer to 900 Mt (http://www.eia.gov/coal/production/quarterly/). Most of the coal is burned for power generation, but substantial quantities are also employed in the manufacture of steel, chemicals, and activated carbons. Coal has a positive impact upon many industries, including mining, power, rail transportation, manufacturing, chemical, steel, activated carbon, and fuels. Everything that is in the earth’s crust is also present within coal to some extent, and the challenge is always to utilize abundant domestic coal in clean and environmentally friendly manners. In the case of the rare earths, these valuable and extraordinarily useful elements are present within the abundant coal and coal by-products produced domestically and world-wide. These materials include the coals, as well as the combustion by-products such as ashes, coal preparation wastes, gasification slags, and mining by-products. All of these materials can be viewed as potential sources of rare earth elements. Most of the common inorganic lanthanide compounds, such as the phosphates found in coal, have very high melting, boiling, and thermal decomposition temperatures, allowing them to concentrate in combustion and gasification by-products. Furthermore, rare earths have been found in interesting concentrations in the strata above and below certain coal seams. Much of the recent research on coal utilization in the United States has focused upon the capture of pollutants such as acid gases, particulates, and mercury, and the greenhouse gas carbon dioxide. The possible recovery of rare earth and other critical elements from abundant coal and by-products is an exciting new research area, representing a dramatic paradigm shift for coal.

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Distributed Fiber Optic Sensor for On-Line Monitoring of Coal Gasifier Refractory Health

This report summarizes technical progress on the program “Distributed Fiber Optic Sensor for On-Line Monitoring of Coal Gasifier Refractory Health,” funded by the National Energy Technology Laboratory of the U.S. Department of Energy, and performed by the Center for Photonics Technology of the Bradley Department of Electrical and Computer Engineering at Virginia Tech. The scope of work entails analyses of traveling grating generation technologies in an optical fiber, as well as the interrogation of the gratings to infer a distributed temperature along the fiber, for the purpose of developing a real-time refractory health condition monitoring technology for coal gasifiers. During the project period, which is from 2011-2015, three different sensing principles were studied, including four-wave mixing (FWM), coherent optical time-domain reflectometer (C-OTDR) and Brillouin optical time-domain analysis (BOTDA). By comparing the three methods, the BOTDA was selected for further development into a complete bench-top sensing system for the proposed high-temperature sensing application. Based on the input from Eastman Chemical, the industrial collaborator on this project, a cylindrical furnace was designed and constructed to simulate typical gasifier refractory temperature conditions in the laboratory, and verify the sensor’s capability to fully monitor refractory conditions on the back-side at temperatures up to 1000°C. In the later stages of the project, the sensing system was tested in the simulated environment for its sensing performance and high-temperature survivability. Through theoretical analyses and experimental research on the different factors affecting the sensor performance, a sensor field deployment strategy was proposed for possible future sensor field implementations.

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The Coal-Seq III Consortium. Advancing the Science of CO 2 Sequestration in Coal Seam and Gas Shale Reservoirs

The Coal-Seq consortium is a government-industry collaborative that was initially launched in 2000 as a U.S. Department of Energy sponsored investigation into CO2 sequestration in deep, unmineable coal seams. The consortium’s objective aimed to advancing industry’s understanding of complex coalbed methane and gas shale reservoir behavior in the presence of multi-component gases via laboratory experiments, theoretical model development and field validation studies. Research from this collaborative effort was utilized to produce modules to enhance reservoir simulation and modeling capabilities to assess the technical and economic potential for CO2 storage and enhanced coalbed methane recovery in coal basins. Coal-Seq Phase 3 expands upon the learnings garnered from Phase 1 & 2, which has led to further investigation into refined model development related to multicomponent equations-of-state, sorption and diffusion behavior, geomechanical and permeability studies, technical and economic feasibility studies for major international coal basins the extension of the work to gas shale reservoirs, and continued global technology exchange. The first research objective assesses changes in coal and shale properties with exposure to CO2 under field replicated conditions. Results indicate that no significant weakening occurs when coal and shale were exposed to CO2, therefore, there was no need to account for mechanical weakening of coal due to the injection of CO2 for modeling. The second major research objective evaluates cleat, Cp, and matrix, Cm, swelling/shrinkage compressibility under field replicated conditions. The experimental studies found that both Cp and Cm vary due to changes in reservoir pressure during injection and depletion under field replicated conditions. Using laboratory data from this study, a compressibility model was developed to predict the pore-volume compressibility, Cp, and the matrix compressibility, Cm, of coal and shale, which was applied to modeling software to enhance model robustness. Research was also conducted to improve algorithms and generalized adsorption models to facilitate realistic simulation of CO2 sequestration in coal seams and shale gas reservoirs. The interaction among water and the adsorbed gases, carbon dioxide (CO2), methane (CH4), and nitrogen (N2) in coalbeds is examined using experimental in situ laboratory techniques to comprehensively model CBM production and CO2 sequestration in coals. An equation of state (EOS) module was developed which is capable of predicting the density of pure components and mixtures involving the wet CBM gases CH4, CO2, and N2 at typical reservoir condition, and is used to inform CO2 injection models. The final research objective examined the effects adsorbed CO2 has on coal strength and permeability. This research studied the weakening or failure of coal by the adsorption of CO2 from empirically derived gas production data to develop models for advanced modeling of permeability changes during CO2 sequestration. The results of this research effort have been used to construct a new and improved model for assessing changes in permeability of coal reservoirs due CO2 injection. The modules developed from these studies and knowledge learned are applied to field validation and basin assessment studies. These data were used to assess the flow and storage of CO2 in a shale reservoir, test newly developed code against large-scale projects, and conduct a basin-oriented review of coal storage potential in the San Juan Basin. The storage potential and flow of CO2 was modeled for shale sequestration of a proprietary Marcellus Shale horizontal gas production well using COMET3 simulation software. Simulation results from five model runs indicate that stored CO2 quantities are linked to the duration of primary production preceding injection. Matrix CO2 saturation is observed to increase in each shale zone after injection with an increase in primary production, and the size of the CO2 plume is also observed to increase in size the longer initial production is sustained. The simulation modules developed around the Coal-Seq experimental work are also incorporated into a pre-existing large-scale numerical simulation model of the Pump Canyon CO2-ECBM pilot in the San Juan Basin. The new model was applied to re-history match the data set to explore the improvements made in permeability prediction against previously published data sets and to validate this module. The assessment of the new data, however, indicates that the impact of the variable Cp is negligible on the overall behavior of the coal for CO2 storage purposes. Applying these new modules, the San Juan Basin and the Marcellus Shale are assessed for their technical ECBM/AGR and CO2 storage potential and the economic potential of these operations. The San Juan Basin was divided into 4 unique geographic zones based on production history, and the Marcellus was divided into nine. Each was assessed based upon each zone’s properties, and simulations were run to assess the potential of full Basin development. Models of a fully developed San Juan Basin suggest the potential for up to 104 Tcf of CO2 storage, and 12.3 Tcf of methane recovery. The Marcellus models suggest 1,248 Tcf of CO2 storage and 924 Tcf of AGR. The economics are deemed favorable where credits cover the cost of CO2 in the San Juan Basin, and in many cases in the Marcellus, but to maximize storage potential, credits need to extend to pay the operator to store CO2.

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Laboratory Scale Coal And Biomass To Drop-In Fuels (CBDF) Production And Assessment

This Final Technical Report describes the work and accomplishments of the project entitled, “Laboratory Scale Coal and Biomass to Drop-In Fuels (CBDF) Production and Assessment.” The main objective of the project was to fabricate and test a lab-scale liquid-fuel production system using coal containing different percentages of biomass such as corn stover and switchgrass at a rate of 2 liters per day. The system utilizes the patented Altex fuel-production technology, which incorporates advanced catalysts developed by Pennsylvania State University. The system was designed, fabricated, tested, and assessed for economic and environmental feasibility relative to competing technologies.

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Wabash Valley Integrated Gasification Combined Cycle, Coal to Fischer Tropsch Jet Fuel Conversion Study

This reports examines the feasibility of converting the existing Wabash Integrated Gasification Combined Cycle (IGCC) plant into a liquid fuel facility, with the goal of maximizing jet fuel production. The fuels produced are required to be in compliance with Section 526 of the Energy Independence and Security Act of 2007 (EISA 2007 §526) lifecycle greenhouse gas (GHG) emissions requirements, so lifecycle GHG emissions from the fuel must be equal to or better than conventional fuels. Retrofitting an existing gasification facility reduces the technical risk and capital costs associated with a coal to liquids project, leading to a higher probability of implementation and more competitive liquid fuel prices. The existing combustion turbine will continue to operate on low cost natural gas and low carbon fuel gas from the gasification facility. The gasification technology utilized at Wabash is the E-Gas™ Technology and has been in commercial operation since 1995. In order to minimize capital costs, the study maximizes reuse of existing equipment with minimal modifications. Plant data and process models were used to develop process data for downstream units. Process modeling was utilized for the syngas conditioning, acid gas removal, CO 2 compression and utility units. Syngas conversion to Fischer Tropsch (FT) liquids and upgrading of the liquids was modeled and designed by Johnson Matthey Davy Technologies (JM Davy). In order to maintain the GHG emission profile below that of conventional fuels, the CO 2 from the process must be captured and exported for sequestration or enhanced oil recovery. In addition the power utilized for the plant’s auxiliary loads had to be supplied by a low carbon fuel source. Since the process produces a fuel gas with sufficient energy content to power the plant’s loads, this fuel gas was converted to hydrogen and exported to the existing gas turbine for low carbon power production. Utilizing low carbon fuel gas and process steam in the existing combined cycle power plant provides sufficient power for all plant loads. The lifecycle GHG profile of the produced jet fuel is 95% of conventional jet fuel. Without converting the fuel gas to a low carbon fuel gas, the emissions would be 108% of conventional jet fuel and without any GHG mitigation, the profile would be 206%. Oil prices greater than $120 per barrel are required to reach a targeted internal rate of return on equity (IRROE) of 12%. Although capital expenditure is much less than if a greenfield facility was built, the relatively small size of the plant, assumed coal price, and the CTL risk profile used in the economic assumptions lead to a high cost of production. Assuming more favorable factors, the economic oil price could be reduced to $78 per barrel with GHG mitigation and $55 per barrel with no GHG mitigation.

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AREA 2: Novel Materials for Robust Repair of Leaky Wellbores in CO 2 Storage Formations

The potential leakage of hydrocarbon fluids or CO 2 out of subsurface formations through wells with fractured cement or debonded microannuli is a primary concern in oil and gas production and CO 2 storage. The presence of fractures in a cement annulus with apertures on the order of 10–300 microns can pose a significant leakage danger with effective permeability in the range of 0.1–1 mD (millidarcy). Leakage pathways with small apertures are often difficult to repair using conventional oilfield cement, thus a low-viscosity sealant that can be easily placed into these fractures while providing an effective seal is desired. The development of a novel application using pH-triggered polymeric sealants could potentially be the solution to plugging these fractures and that was the research aim of this study. The application is based on the transport and reaction of a low-pH poly(acrylic acid) polymer through fractures in strongly alkaline cement. The pH-sensitive microgels viscosify upon neutralization with cement to become highly swollen gels with substantial yield stress that can block fluid flow. Experiments in a cement fracture determined the effects of the viscosification and gel deposition via real-time visual observation and measurements of pressure gradient and effluent pH. While the pH-triggered gelling mechanism and rheology measurements of the neutralized polymer gel show promising results, the polymer solution in contact with cement undergoes an undesirable reaction known as polymer syneresis. Syneresis is caused by the release of calcium cation from cement that collapses the polymer network. Syneresis produces an unstable calcium-precipitation byproduct that is detrimental to the strength and stability of the gel in place. As a result, gel-sealed leakage pathways that subjected to various degrees of syneresis often failed to hold back pressures. Several chemicals were studied to inhibit polymer syneresis and tested for pretreatment of cement cores to remove calcium and prevent syneresis during polymer placement. A chelating agent, sodium triphosphate (Na 5 P 3 O 10 ), was found to successfully eliminate syneresis without compromising the injectivity of polymer solution during placement. Polymer gel strength is determined by recording the maximum holdback pressure gradients during liquid breakthrough tests after various periods of pretreatment and polymer shut-in time. Cores pretreated with Na 5 P 3 O 10 successfully held up to an average of 80 psi/ft, which is significantly greater than the expected threshold value of about 0.1-5 psi/ft required to prevent flow in a typical CO 2 leakage scenario. The use of such inexpensive, pH-triggered poly-acrylic acid polymer allows long-term robust seal of leaky wellbores under high pH conditions.

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Reactive Transport Models with Geomechanics to Mitigate Risks of CO2 Utilization and Storage

Reactivity of carbon dioxide (CO 2 ), rocks and brine is important in a number of practical situations in carbon dioxide sequestration. Injectivity of CO 2 will be affected by near wellbore dissolution or precipitation. Natural fractures or faults containing specific minerals may reactivate leading to induced seismicity. In this project, we first examined if the reactions between CO 2 , brine and rocks affect the nature of the porous medium and properties including petrophysical properties in the timeframe of the injection operations. This was done by carrying out experiments at sequestration conditions (2000 psi for corefloods and 2400 psi for batch experiments, and 600°C) with three different types of rocks – sandstone, limestone and dolomite. Experiments were performed in batch mode and corefloods were conducted over a two-week period. Batch experiments were performed with samples of differing surface area to understand the impact of surface area on overall reaction rates. Toughreact, a reactive transport model was used to interpret and understand the experimental results. The role of iron in dissolution and precipitation reactions was observed to be significant. Iron containing minerals – siderite and ankerite dissolved resulting in changes in porosity and permeability. Corefloods and batch experiments revealed similar patterns. With the right cationic balance, there is a possibility of precipitation of iron bearing carbonates. The results indicate that during injection operations mineralogical changes may lead to injectivity enhancements near the wellbore and petrophysical changes elsewhere in the system. Limestone and dolomite cores showed consistent dissolution at the entrance of the core. The dissolution led to formation of wormholes and interconnected dissolution zones. Results indicate that near wellbore dissolution in these rock-types may lead to rock failure. Micro-CT images of the cores before and after the experiments revealed that an initial high-permeability pathway facilitated the formation of wormholes. The peak cation concentrations and general trends were matched using Toughreact. Batch reactor modeling showed that the geometric factors obtained using powder data that related effective surface area to the BET surface area had to be reduced for fractured samples and cores. This indicates that the available surface area in consolidated samples is lower than that deduced from powder experiments. Field-scale modeling of reactive transport and geomechanics was developed in parallel at Idaho National Laboratory. The model is able to take into account complex chemistry, and consider interactions of natural fractures and faults. Poroelastic geomechanical considerations are also included in the model.

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An advanced joint inversion system for CO 2 storage modeling with large date sets for characterization and real-time monitoring-enhancing storage performance and reducing failure risks under uncertainties

As large-scale, commercial storage projects become operational, the problem of utilizing information from diverse sources becomes more critically important. In this project, we developed, tested, and applied an advanced joint data inversion system for CO 2 storage modeling with large data sets for use in site characterization and real-time monitoring. Emphasis was on the development of advanced and efficient computational algorithms for joint inversion of hydro-geophysical data, coupled with state-of-the-art forward process simulations. The developed system consists of (1) inversion tools using characterization data, such as 3D seismic survey (amplitude images), borehole log and core data, as well as hydraulic, tracer and thermal tests before CO 2 injection, (2) joint inversion tools for updating the geologic model with the distribution of rock properties, thus reducing uncertainty, using hydro-geophysical monitoring data, and (3) highly efficient algorithms for directly solving the dense or sparse linear algebra systems derived from the joint inversion. The system combines methods from stochastic analysis, fast linear algebra, and high performance computing. The developed joint inversion tools have been tested through synthetic CO 2 storage examples.

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Shared Freight Transportation and Energy Commodities Phase One: Coal, Crude Petroleum, & Natural Gas Flows

The Freight Analysis Framework (FAF) integrates data from a variety of sources to create a comprehensive picture of nationwide freight movements among states and major metropolitan areas for all modes of transportation. It provides a national picture of current freight flows to, from, and within the United States, assigns selected flows to the transportation network, and projects freight flow patterns into the future. The latest release of FAF is known as FAF4 with a base year of 2012. The FAF4 origin-destination-commodity-mode (ODCM) matrix is provided at national, state, major metropolitan areas, and major gateways with significant freight activities (e.g., El Paso, Texas). The U.S. Department of Energy (DOE) is interested in using FAF4 database for its strategic planning and policy analysis, particularly in association with the transportation of energy commodities. However, the geographic specification that DOE requires is a county-level ODCM matrix. Unfortunately, the geographic regions in the FAF4 database were not available at the DOE desired detail. Due to this limitation, DOE tasked Oak Ridge National Laboratory (ORNL) to assist in generating estimates of county-level flows for selected energy commodities by mode of transportation.

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Bench-scale Development of an Advanced Solid Sorbent-based CO 2 Capture Process for Coal-fired Power Plants

It is increasingly clear that CO 2 capture and sequestration (CCS) must play a critical role in curbing worldwide CO 2 emissions to the atmosphere. Development of these technologies to cost-effectively remove CO 2 from coal-fired power plants is very important to mitigating the impact these power plants have within the world’s power generation portfolio. Currently, conventional CO 2 capture technologies, such as aqueous-monoethanolamine based solvent systems, are prohibitively expensive and if implemented could result in a 75 to 100% increase in the cost of electricity for consumers worldwide. Solid sorbent CO 2 capture processes – such as RTI’s Advanced Solid Sorbent CO 2 , Capture Process – are promising alternatives to conventional, liquid solvents. Supported amine sorbents – of the nature RTI has developed – are particularly attractive due to their high CO 2 loadings, low heat capacities, reduced corrosivity/volatility and the potential to reduce the regeneration energy needed to carry out CO 2 capture. Previous work in this area has failed to adequately address various technology challenges such as sorbent stability and regenerability, sorbent scale-up, improved physical strength and attrition-resistance, proper heat management and temperature control, proper solids handling and circulation control, as well as the proper coupling of process engineering advancements that are tailored for a promising sorbent technology. The remaining challenges for these sorbent processes have provided the framework for the project team’s research and development and target for advancing the technology beyond lab- and bench-scale testing. Under a cooperative agreement with the US Department of Energy, and part of NETL’s CO 2 Capture Program, RTI has led an effort to address and mitigate the challenges associated with solid sorbent CO 2 capture. The overall objective of this project was to mitigate the technical and economic risks associated with the scale-up of solid sorbent-based CO 2 capture processes, enabling subsequent larger pilot demonstrations and ultimately commercial deployment. An integrated development approach has been a key focus of this project in which process development, sorbent development, and economic analyses have informed each of the other development processes. Development efforts have focused on improving the performance stability of sorbent candidates, refining process engineering and design, and evaluating the viability of the technology through detailed economic analyses. Sorbent advancements have led to a next generation, commercially-viable CO 2 capture sorbent exhibiting performance stability in various gas environments and a physically strong fluidizable form. The team has reduced sorbent production costs and optimized the production process and scale-up of PEI-impregnated, fluidizable sorbents. Refinement of the process engineering and design, as well as the construction and operation of a bench-scale research unit has demonstrated promising CO 2 capture performance under simulated coal-fired flue gas conditions. Parametric testing has shown how CO 2 capture performance is impacted by changing process variables, such as Adsorber temperature, Regenerator temperature, superficial flue gas velocity, solids circulation rate, CO 2 partial pressure in the Regenerator, and many others. Long-term testing has generated data for the project team to set the process conditions needed to operate a solids-based system for optimal performance, with continuous 90% CO 2 capture, and no operational interruptions. Data collected from all phases of testing has been used to develop a detailed techno-economic assessment of RTI’s technology. These detailed analyses show that RTI’s technology has significant economic advantages over current amine scrubbing and potential to achieve the DOE’s Carbon Capture Program’s goal of >90% CO 2 capture rate at a cost of < $40/T-CO 2 captured by 2025. Through this integrated technology development approach, the project team has advanced RTI’s CO 2 capture technology to TRL-4 (nearly TRL-5, with the missing variable being testing on actual, coal-fired flue gas), according to the DOE/FE definitions for Technology Readiness Levels. At a broader level, this project has advanced the whole of the solid sorbent CO 2 capture field, with advancements in process engineering and design, technical risk mitigation, sorbent scale-up optimization, and an understanding of the commercial viability and applicability of solid sorbent CO 2 capture technologies for the U.S. existing fleet of coal-fired power plants.

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Molecularly Engineered Energy Materials, an Energy Frontier Research Center

Molecularly Engineered Energy Materials (MEEM) was established as an interdisciplinary cutting-edge UCLA-based research center uniquely equipped to attack the challenge of rationally designing, synthesizing and testing revolutionary new energy materials. Our mission was to achieve transformational improvements in the performance of materials via controlling the nano-and mesoscale structure using selectively designed, earth-abundant, inexpensive molecular building blocks. MEEM has focused on materials that are inherently abundant, can be easily assembled from intelligently designed building blocks (molecules, nanoparticles), and have the potential to deliver transformative economic benefits in comparison with the current crystalline-and polycrystalline-based energy technologies. MEEM addressed basic science issues related to the fundamental mechanisms of carrier generation, energy conversion, as well as transport and storage of charge and mass in tunable, architectonically complex materials. Fundamental understanding of these processes will enable rational design, efficient synthesis and effective deployment of novel three-dimensional material architectures for energy applications. Three interrelated research directions were initially identified where these novel architectures hold great promise for high-reward research: solar energy generation, electrochemical energy storage, and materials for CO 2 capture. Of these, the first two remained throughout the project performance period, while carbon capture was been phased out in consultation and with approval from BES program manager.

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HEAT Sensor: Harsh Environment Adaptable Thermionic Sensor

This document is the final report for the “HARSH ENVIRONMENT ADAPTABLE THERMIONIC SENSOR” project under NETL’s Crosscutting contract DE-FE0013062. This report addresses sensors that can be made with thermionic thin films along with the required high temperature hermetic packaging process. These sensors can be placed in harsh high temperature environments and potentially be wireless and self-powered.

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Effective Exploration of New 760°C-Capability Steels for Coal Energy

Cost effective and high performance alloys that are capable of operating at 760 °C or higher for extended periods of time under a very aggressive environment are critically required for the design and development of advanced ultrasupercritical (AUSC) boilers and steam turbines. Finely dispersed Laves phase precipitates have been shown by Takeyama and co-workers to be a viable strengthening mechanism in high temperature austenitic steels. There is currently no straightforward theory that can predict what other intermetallic phases can serve as potent precipitation-strengthening phases for steels; thus we employed a highly effective dual-anneal diffusion multiple (DADM) approach to screen for viable strengthening precipitates over a wide range of compositions. From the Fe-Co-Cr-Ni-Mo DADMs, the Fe-Cr-Mo based Chi phase was identified as a new strengthening phase for high temperature ferritic steels; and from the Fe-Mn-Cr-Nb-Ni-Mo-FeAl DADMs, the Laves phase was identified as a viable strengthening precipitate in Fe-Mn and Fe-Ni based austenitic steels. After identification of viable strengthening phases from the DADMs that covered compositions in the basic ternary and quaternary systems, we employed computation thermodynamics to perform multicomponent alloy design and optimization. For the new the Chi-phase strengthened steels, we performed thermodynamic calculations to vary the volume fraction of the Chi phase and introduced Nb and carbon to promote the formation of stable carbides for grain size control during solution heat treatment. For the Fe-Ni-Mn based austenitic steels, we performed extensive parametric optimization of compositions in order to reduce the expensive Ni content, add Cr and Al for oxidation resistance, and balance the alloying contents (Ni, Mn, Cr, Al, Mo) to suppress the ferritic phase and promote the austenitic matrix phase. Four steels (two ferritic + two austenitic) were designed and tested. The two Chi-phase strengthened ferritic steels exhibited excellent oxidation resistance and good creep-rupture strength at moderate temperatures, considering their ferritic matrix that usually results in lower creep resistance than austenitic steels. These steels showed brittleness and sample-to-sample variability in ductility. The low ductility might be due to the macro segregation during solidification or the significant grain growth during the solution heat treatments. We believe there is no inherent brittleness based on the chemistry of the steels. The creep-rupture performance of the steels is comparable to the 9Cr steels. Due to their ferritic matrix, the new Chi-phase strengthened ferritic steels may not be suited for the 760 °C AUSC applications, but they are very good candidates for intermediate temperature applications due to their outstanding oxidation resistance and high strength. Further study is required to find the source of low and highly variable ductility. We believe the compositions of the Chi-phase strengthened steels are not inherently brittle. The Chi-phase strengthened ferritic steels may also be excellent candidates for intermediate-temperature and room-temperature cast stainless steels, thus we highly recommend further investigations. The two Mn-containing austenitic steels based on the Laves phase showed good ductility, excellent oxidation resistance (slightly inferior to the two ferritic steels) at high temperatures and moderate creep strength. The creep-strength of the two austenitic steels based on the Larson-Miller parameters is higher than that of the traditional 316 stainless steels, but lower than the alumina-forming alloys (AFAs) developed at Oak Ridge National Laboratories. We do not recommend high priority in further studying these compositions unless higher Cr alloys are required for hot-corrosion resistance.

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SOFC Systems with Improved Reliability and Endurance

The overall goal of this U.S. Department of Energy (DOE) sponsored project was the development of Solid Oxide Fuel Cell (SOFC) technology suitable for ultra-efficient central power generation systems utilizing coal and natural gas fuels and featuring greater than 90% carbon dioxide capture. The specific technical objective of this project was to demonstrate, via analyses and testing, progress towards adequate stack life (≥ 4 years) and stack performance stability (degradation rate ≤ 0.2% per 1000 hours) in a low-cost SOFC stack design. This final technical report summarizes the progress made during the project period of 27 months. Significant progress was made in the areas of cell and stack technology development, stack module development, sub-scale module tests, and Proof-of-Concept Module unit design, fabrication and testing. The work focused on cell and stack materials and designs, balance-of-plant improvements, and performance evaluation covering operating conditions and fuel compositions anticipated for commercially-deployed systems. In support of performance evaluation under commercial conditions, this work included the design, fabrication, siting, commissioning, and operation of a ≥ 50 kWe proof-of-concept module (PCM) power plant, based upon SOFC cell and stack technology developed to date by FuelCell Energy, Inc. (FCE) under the Office of Fossil Energy’s Solid Oxide Fuel Cells program. The PCM system was operated for at least 1000 hours on natural gas fuel at FCE’s facility. The factory cost of the SOFC stack was estimated to be at or below the DOE’s high-volume production cost target (2011 $).

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