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All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

A Review of the Use of Immobilized Ionic Liquids in the Electrochemical Conversion of CO2

This paper is a review on the application of imidazolium-based ionic liquids tethered to polymer backbones in the electrochemical conversion of CO2 to carbon monoxide and formic acid. These tethered ionic liquids have been incorporated into novel anion ion exchange membranes for CO2 electrolysis, as well as for ionomers that have been incorporated into the cathode catalyst layer, providing a co-catalyst for the reduction reaction. In using these tethered ionic liquids in the cathode catalyst composition, the cell operating current increased by a factor of two or more. The Faradaic efficiencies also increased by 20–30%. This paper provides a review of the literature, in addition to providing some new experimental results from Dioxide Materials, in the electrochemical conversion of CO2 to CO and formic acid.

09 BIOMASS FUELS↗
DOE OSTI2021

Case Study: Hybrid Carbon Conversion Using Low-Carbon Energy Sources in Coal-Producing States

The demand for more carbon efficient power sources and a decrease in natural gas prices has decreased the desire for coal power. This decrease in demand has led to massive job losses in coal mining regions over the past decade. The purpose of this project is to develop a hybrid energy system utilizing both a coal power plant and advanced reactor, which is competitive with natural gas by improving on profitability and decreasing carbon emissions. This report details the problem with a summary of the impact on the coal industry and the availability of renewable energy sources in the Appalachian region. Because of the geography of the region, variable renewable energy sources are not available without significant size and siting restrictions. However, biomass in the form of wood waste is abundant and can be used as a carbon neutral energy source. Combining biomass and coal processing, in addition to thermal power plants, can increase system profits and efficiency by providing peaking power and conversion opportunities for secondary markets. The electric load is based on publicly available demand data from Appalachian Power, which services the western Virginia and southern West Virginia in the Appalachian region. The demand information is combined by service, normalized, and scaled to an average demand of 1000 kW, which will be the basis for sizing the hybrid energy system. A traditional screening curve analysis for a coal plant and advanced reactor shows that the least cost design varies significantly based on the assumed discount rate and capital recovery period. An optimization program to size the design in TEAL based on the load curve gives 10 optimal designs, all with a negative resulting net present value (NPV) and a coal plant capacity of less than 15%. Including profits from selling captured carbon at a flat rate results in a positive NPV; however, the coal capacity factor only increases to about 40%. There are limitations with this optimization as well since the price of CO2 is likely to decrease as more is sold to the conversion market. The suggested design will combine coal power, an advanced reactor, and coal and biomass coprocessing to produce a variety of products that can be sold to the conversion market while increasing system efficiency. The analysis of conversion pathways for coal and biomass reveals that multiple options will need to be included in the analysis to produce the optimal system design. Three systems will be optimized and compared to determine the best design based on the figures of merit of total NPV and cost of carbon avoided. The first system will include a coal power plant and an advanced reactor that will sell electricity to the grid to meet demand and sell captured carbon to the conversion market. The second system adds a high-temperature steam electrolysis plant, which will utilize electricity during times of low demand to produce hydrogen and sell it to the conversion market. The third system adds biomass and coal processing with options for hydrocarbon oils, syngas to be produced for the conversion market, and electricity generation to power components within the system or provide peaking power. This analysis will be based on a new approach that combines traditional screening curve methods with a dispatch algorithm that optimizes the system based on the opportunity cost of different production options. The resulting optimization algorithm should provide results with less processing time than HERON’s decision tree method. The results from this analysis will determine an optimal design and reinforce the benefits of coal power when used in a hybrid energy system. The initial results show that the addition of a secondary market for carbon sales could result in a positive NPV and increases the capacity factor of the coal plant as compared to a design with only sales to the electricity market. The addition of more markets and additional coal consumption from biomass coprocessing could increase NPV further, replace carbon in other markets through the sale of biomass-derived hydrocarbons, and demonstrate the value of coal power technology.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2022

BENCH-SCALE DEVELOPMENT OF A TRANSFORMATIVE MEMBRANE PROCESS FOR PRE-COMBUSTION CO 2 CAPTURE

This final technical report describes work conducted by Membrane Technology and Research, Inc. (MTR) for the Department of Energy, National Energy Technology Laboratory (DOE NETL) on development of the second generation (Gen-2) Proteus™ membrane modules and a pre-combustion membrane process for carbon dioxide (CO 2 ) capture from an Integrated Gasification Combined Cycle (IGCC) plant for power generation (award number DE-FE0031632). The work was conducted from October 1, 2018 through March 30, 2022. The overall goal of this project was to bring a Gen-2 version of the H2-selective Proteus membrane to bench-scale module (component) testing with real syngas. MTR was assisted in this project by Susteon, a technology development company with extensive experience in gasification processes, and the University of North Dakota Energy & Environmental Research Center (EERC), who provided the host site for the slipstream field testing. This report details the work conducted to optimize the Gen-2 Proteus membrane and develop modules capable of operation at 200°C; demonstrate membrane module performance processing coal-derived syngas during a field test at EERC; and optimize integration of a dual-membrane process into an IGCC with carbon capture. Work for this project included membrane optimization and scale-up, module component screening and fabrication of high-temperature lab- and bench-scale modules, design and fabrication of a bench-scale field test membrane skid, operation of the field test skid processing coal-derived syngas at EERC, and a detailed techno-economic analysis (TEA) of the MTR dual-membrane process for IGCC power plant pre-combustion CO 2 capture. This project validated recent membrane technology advancements, mitigates risk in future scale-up activities, and moved the membrane pre-combustion capture technology from TRL-4 to TRL-5. Key results for each major task are discussed in the report.

10 SYNTHETIC FUELS↗
DOE OSTI2022

Hydrogen Based Energy Storage System for Integration with Dispatchable Power Generator (Phase I Feasibility Study)

This project examined the feasibility of integrating hydrogen generation, storage, and use as a means to decarbonize campus activities while retaining the ability to utilize the existing natural gas fired combined heat and power system installed at the campus of the University of California @ Irvine. Analysis of specific potential sites for the integrated system identified a location adjacent to the existing central plant which resulted in minimization of interconnections. A strategy based on use of commercial electrolyzers and gas storage was identified. Primary technology advancements are required for the gas turbine to accommodate higher levels of hydrogen and the integrated controls. The project indicated challenges for adopting the proposed strategy with the present rates and constraints. The availability of a relatively low-cost biogas resource by the campus already decarbonizes the gas turbine to some extent. In the absence of this resource, procurement of electricity directly from large scale renewable operations could facilitate lower electricity costs. Additional solar resources on campus could also help in this regard. The gas turbine cannot be operated below 50% capacity due to air permit constraints. Using the otherwise curtailed gas turbine operation to generate hydrogen via electrolysis by consuming natural gas is not highly efficient and therefore leads to relatively high costs of electricity returned. Several scenarios demonstrate potential for effective decarbonization, yet most involve lower and lower capacity factor for the legacy gas turbine which is not a good use of the asset. A small gas turbine output with higher efficiency operation would help. As would ability to export electricity to the grid. Certainly current rate structures and operational scenarios are less attractive than other possible future structures which should be pushed for in the future.

03 NATURAL GAS↗
DOE OSTI2021

Fuel Stratification Influence on NO x Emission in a Premixed Axial Reacting Jet-in-Crossflow at High Pressure

Three reacting jet-in-crossflow (JiC) methane/air flames were numerically investigated in a lean axially staged combustor at a pressure of five atmospheres. A detailed chemistry Star-CCM+ computational fluid dynamics (CFD) model was used with 53 species considered and the result of turbulence-governed finite-rate modeling was validated with in-house experimental data. An optically accessible test section features three side windows, allowing local flow and flame analysis with particle image velocimetry (PIV) and CH* chemiluminescence as well as pressure, temperature, and species exit measurements. The research objective was to predict and verify NO x formation of the premixed 12.7 mm axial jet. Three headend temperature levels were investigated along with three premixed jets at lean (φ Jet = 0.75), near-stoichiometric (φ Jet = 1.07), and rich (φ Jet = 1.78) axial fuel line equivalence ratio. Based on the matching exit emission concentration, global emission benefits were investigated by adjustment of the fuel stratification. The perfectly premixed methane/air flames of this study were shown to ignite at the lee-side of the jet. For the elevated headend temperature level T = 1800 K, the flame extended beyond the windward jet trajectory and caused high axial NO production. For industry application, a firing temperature of 1920 K was achieved with a NO x optimized fuel split of 25%, combining a lean headend (φ Headend = 0.61) with a rich (φ Jet = 1.78) jet equivalence ratio. As a result, this operating point allowed minimization of the combustor residence time at temperatures above 1700 K as well as combustion in a compact flame at the jet lee-side along the counter rotating vortex pair.

03 NATURAL GAS↗
DOE OSTI2022

Reversible Solid Oxide Fuel Cell Systems for Energy Storage and Hydrogen Production

FuelCell Energy (FCE) studied the performance, design, and economics of a reversible solid-oxide fuel cell/electrolyzer integrated with a natural gas-based electricity generation plant and used as an energy storage system. Increased market penetration of renewable energy is challenging for operators of fossilbased plants which are not suited for quick turndown and ramp-up. Process simulations studies show that with utilization of waste heat from the power plant, a high roundtrip efficiency (RTE) around 70% is possible, providing excellent market potential for this energy storage technology, potentially providing improved economics and lifetime for such power plant. The market potential and economics as a function of production volume are analyzed in detail. FCE is continuing the development and commercialization of its solid oxide technology.

08 HYDROGEN↗
DOE OSTI2021

Editors’ Choice—Diffusion Media for Cation Contaminant Transport Suppression into Fuel Cell Electrodes

Polymer electrolyte membrane fuel cells provide an alternative option to fossil fuel-based energy conversion devices. However, the corrosion of fuel cell components, specifically the bipolar plates, introduces contaminants (e.g., Fe, Ni) into the membrane electrode assembly (MEA). These contaminants accelerate the ionomer degradation by acting as a Fenton’s reagent, decreasing the fuel cell’s durability. This study presents the mechanism and the diffusion media properties affecting the transport of cation contaminants into the MEA. Cation contaminant transport was studied after altering the gas diffusion layers (GDLs) wettability, emulating the GDL properties after prolonged operation, by ex situ hydrogen peroxide treatment or in situ electrochemical potential cycling. A GDL with crack-free microporous layer (MPL) showed a lower cation transport rate to the catalyst layer than MPL with cracks after both ex situ and in situ treatment. A novel GDL was developed from modification of the conventional GDL via the addition of a hydrophobic layer to the GDL substrate, which suppressed the contaminant cation transport significantly. This novel GDL also showed improved fuel cell performance.

25 ENERGY STORAGE↗
DOE OSTI2022

Fabrication of Biofunctionalized PVA/PEI Nanofibers for Rare Earth Element Extraction from Coal Mine Tailings

The need for rare earth elements (REEs) for new technology is becoming increasingly stiff with demand at a record high. Biological ligands like lanmodulin and lanthanide binding tags (LBT) have gained noticeable attention for their selective extraction of valuable lanthanide metals in aqueous solution. Building on previous work using microbeads as the extraction media, we propose that nanofibers can improve extraction capabilities. Nanofibers could provide more efficient flow and higher extraction yields due to their high surface area to volume ratio. Relying on thiolmaleimide click chemistry as the biological ligand immobilization route, electrospinning as the nanofiber manufacturing method, and numerous characterization techniques, we produced electrospinning polymer solutions and nanofibers with a maximum neodymium adsorbent capacity of 12.1 μmol/g of extraction media immobilized with LBT. Although the prior work produced an extraction media with an equivalent capacity of ~40 μmol/g, the electrospinning process is much more economical and scalable. This work paves the way for an industrially relevant, environmentally-friendly REE extraction material. Further work is required to produce higher quality nanofibers, to investigate common ion interference with REE adsorbance, and to scale production up to a relevant scale.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2025

Demonstration and technoeconomic analysis of dodecanol production from acetate using metabolically engineered Escherichia coli

In a circular bioeconomy, the one-way conversion of petroleum to chemicals and CO 2 is replaced with processes that reduce CO 2 to energy carriers and useful materials that are returned to CO 2 upon combustion. A circular bioeconomy that relies on photosynthesis to generate sugars as the chief energy carrier and precursor to chemical building blocks has yet to overcome many recalcitrant aspects of plant-based photosynthesis, namely, high feedstock costs, arable land scarcity, food competition, and fertilizer overuse. Acetate is a potential sustainable energy carrier because it can be produced from CO 2 either electrocatalytically or by acetogens via the Wood-Ljungdahl pathway. Here, in this work, we conducted a metabolic engineering study of Escherichia coli 's ability to convert acetate into dodecanol as a model oleochemical product. We performed techno-economic and life cycle analyses to determine break-even points with alternative fossil fuel-based strategies and identified critical process performance parameters for supporting an industrial acetate-based bioprocess. These analyses showed that oleochemical yield is the primary driver of minimum oleochemical selling price and carbon intensity. Therefore, to increase yield on acetate, we deleted the aceBAK operon, which facilitates funneling of acetate into biomass instead of product. We performed additional strain engineering to increase flux towards dodecanol and increase acetate uptake. Finally, we demonstrated increased yield in controlled bioreactors, improving from 13% of the maximum theoretical yield to 37%. Rigorous uncertainty analyses assuming a range of market conditions and future technological performances resulted in 88% and 37% of simulated scenarios having lower carbon intensities than fossil fuel-based routes and lower minimum selling prices than the market price.

Acetate↗
DOE OSTI2021

SO3/H2SO4 continuous real-time sensor demonstration at a power plant

We present results from field testing of a new, innovative sensor developed to measure SO3/H2SO4 continuously and in real time at a coal-fired power plant. The system utilizes the sensitivity, specificity, and real-time capabilities of mid-infrared (Mid-IR) laser-based sensor technology, along with a heated, close-coupled cell mounted directly to a power plant duct. Measurements were made by the laser sensor over a 2-day period and compared to results from the accepted method, EPA 8A, which requires a 30-minute collection, labor intensive processing, and off-site analysis at a lab. In contrast to the condensation method, the laser sensor continuously samples flue gas and reports measurements of the concentration of SO3/H2SO4, SO2 ever second with unattended operation. This initial demonstration proved the sensor concept and paves the way for its use for optimizing sorbent injection used to neutralize SO3/H2SO4. Optimized sorbent injection will enable significant cost savings associated with efforts to mitigate the presence and effects of SO3/H2SO4 such as “Blue Plume”, air heater fouling, and duct corrosion. In particular, the real-time, actionable information will enable better control of additive injection in flex conditions and variable fuels.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2022

Cost and Performance Baseline for Fossil Energy Plants Volume 1: Bituminous Coal and Natural Gas to Electricity

This revised report presents an independent assessment of the cost and performance of select fossil energy power systems—integrated gasification combined cycle (IGCC), pulverized coal (PC), and natural gas combined cycle (NGCC) plants—using a systematic, transparent technical and economic approach. The cost and performance of fossil fuel-based generation technologies represented in this report (and the series at large) are important inputs to assessments and determinations of technology combinations to be utilized to meet the projected demands of future power markets. In addition to informing technology comparisons, the reference plant configurations found in this report provide perspective for regulators and policy makers. From a research and development perspective, this report is used to assess goals and metrics and to provide a consistent basis for comparing developing technologies.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2019

Recent developments on polymeric membranes for CO 2 capture from flue gas

Polymeric membranes have been widely considered as one of the next-generation technologies for CO 2 capture from fossil fuel-derived flue gases. This separation modality requires novel polymeric materials that possess efficient CO 2 /N 2 separation properties, as well as chemical and mechanical stability for a multiyear membrane lifetime. In this paper, recent developments in polymeric membranes tailored for post-combustion carbon capture are reviewed. The selected polymeric materials encompass ether oxygen-rich polymers, polynorbornenes, ionic liquid membranes, and facilitated transport membranes. In each of the selected materials, noteworthy research efforts for material design and membrane formation are highlighted. The performances of the selected materials are compared in the CO 2 /N 2 selectivity-CO 2 permeance plot. As the only class of materials reviewed herein that have demonstrated the fabrication of thin-film composite membranes in scale, facilitated transport membranes have shown both high selectivity and permeance at relevant conditions for post-combustion carbon capture. Finally, comprehensive field tests are needed to resolve the technical gap between the material development and the commercial application.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2021

Cooperative Research and Development Agreement between National Energy Technology Laboratory and Electric Power Research Institute (EPRI) [Abstract]

Carbon dioxide (CO 2 ) capture from flue gas generated by fossil fuel-fired power plants has been proposed as an efficient approach to limit CO 2 emissions to the atmosphere. Due to the high cyclic CO 2 sorption capacity, well-tuned adsorption chemistry and non-volatility, solid sorbents are widely studied for CO 2 capture processes such as pressure swing adsorption (PSA) and temperature swing adsorption (TSA). Realistic applications of traditional solid sorbent systems face many challenges since moisture and heat management are problematic and solid-solid heat exchange is inefficient. Recently, a novel solid sorbent system, the sorbent polymer composite (SPC), has been developed to overcome those challenges in an energy-saving CO 2 capture process using TSA membrane contactors. A SPC material is comprised of a powdered solid sorbent embedded into a hydrophobic and porous polymer matrix. It allows gases to permeate through and achieve full contact with the sorbents while rejecting water moisture in the CO 2 capture process. In this collaborative research, NETL will conduct performance testing of a novel SPC material and EPRI will conduct a cost analysis based on that performance data.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2022

Separation of CO 2 from Flue Gas and Potential for Geologic Sequestration

The objectives of this study were to review various methods reported in the literature for the separation and geologic sequestration of carbon dioxide and evaluate the potential of TVA fossil fuel-burning plant locations for onsite geologic sequestration of CO 2 from stack emissions. Several conventional and nonconventional technologies for the separation of CO 2 from flue gas, including absorption, adsorption, cryogenic distillation, membranes, hydrate formation and dissociation, and ammonia carbonation, have been reviewed in terms of separation mechanisms, flow diagrams, and costs. Most of the technologies that have been reviewed are still at the research and development stage. Critical information needed to assess and compare these technologies is still lacking. In addition, information on some of the technologies that have been tested at a pilot or industrial scale has not been fully disclosed in the open literature. Because of this lack of data, it is difficult to make a critical assessment of each of the separation technologies. Based on limited information, it was concluded that the most promising methods are membrane separation and the Mitsubishi process for chemical absorption. Both processes involve separating CO 2 at high temperature, minimizing the cost for cooling prior to separation. Physical and chemical geologic formations of CO 2 were also reviewed. It was concluded that due to the geologic time scale of CO 2 sequestration periods, relatively safe conditions, general proximity to CO 2 sources, and extensive knowledge of underground conditions, sequestration of CO 2 in underground aquifers and coal beds is a very promising method of mitigating greenhouse gas emissions. The cost is predicted to be relatively low and the suitable sites are numerous for this application, with many of these sites located close to the plants.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2020

Stability, Combustion, and Compatibility of High-Viscosity Heavy Fuel Oil Blends with a Fast Pyrolysis Bio-Oil

Properties related to the combustion, stability, and compatibility of blends composed of high-viscosity heavy fuel oil (HFO) and highly acidic pyrolysis bio-oil were determined to assess the utility of bio-oil as a marine fuel. The addition of bio-oil was shown to be fully stable with HFO at blend levels up to 50 mass % for up to 2 weeks. Bio-oil concentrations as low as 5 mass % significantly reduced the viscosity of HFO at 25 and 50 °C. Aging studies at 50 and 90 °C showed that the HFO inhibited the polymerization of bio-oil. The heating value and lubricity showed a linear dependency with bio-oil content, and combustion quality was acceptable for blends containing up to 15% bio-oil. The highly acidic bio-oil was found to be corrosive to carbon steel, 2.25Cr-1Mo steel, and 409 stainless steels, but not 304L and 316L. When blended into HFO at levels less than 19 mass %, no measurable corrosion was observed on any of the steel materials, but a 50 mass % concentration produced low-to-moderate corrosion in the carbon steel, 2.25Cr-1Mo steel, and 409 stainless steel grades. The combination of good blend stability, polymerization inhibition, reduced viscosity, and acceptable compatibility for low blend levels suggests that bio-oils may be suitable for use as a marine fuel.

09 BIOMASS FUELS↗