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At least 973 records · Page 54

Process Design and Economics for the Conversion of Lignocellulosic Biomass to Hydrocarbon Fuels: Thermochemical Research Pathways with In Situ and Ex Situ Upgrading of Fast Pyrolysis Vapors

This report was developed as part of the U.S. Department of Energy’s Bioenergy Technologies Office’s efforts to enable the development of technologies for the production of infrastructure-compatible, cost-competitive liquid hydrocarbon fuels from biomass. Specifically, this report details two conceptual designs based on projected product yields and quality improvements via catalyst development and process integration. It is expected that these research improvements will be made within the 2022 timeframe. The two conversion pathways detailed are (1) in situ and (2) ex situ upgrading of vapors produced from the fast pyrolysis of biomass. While the base case conceptual designs and underlying assumptions outline performance metrics for feasibility, it should be noted that these are only two of many other possibilities in this area of research. Other promising process design options emerging from the research will be considered for future techno-economic analysis. Both the in situ and ex situ conceptual designs, using the underlying assumptions, project MFSPs of approximately $3.5/gallon gasoline equivalent (GGE). The performance assumptions for the ex situ process were more aggressive with higher distillate (diesel-range) products. This was based on an assumption that more favorable reaction chemistry (such as coupling) can be made possible in a separate reactor where, unlike in an in situ upgrading reactor, one does not have to deal with catalyst mixing with biomass char and ash, which pose challenges to catalyst performance and maintenance. Natural gas was used for hydrogen production, but only when off gases from the process was not sufficient to meet the needs; natural gas consumption is insignificant in both the in situ and ex situ base cases. Heat produced from the burning of char, coke, and off-gases allows for the production of surplus electricity which is sold to the grid allowing a reduction of approximately 5¢/GGE in the MFSP.

09 BIOMASS FUELS↗

Assessment of Gasoline Additive Containing Ditert-butoxypropanol

The Fuels, Engines, and Emissions Research Center completed analysis and testing of the CPS Powershot gasoline additive under the auspices of the Department of Energy’s Technical Assistance for US Small Businesses in Vehicle Technologies. Gas chromatography-mass spectrometry (GC-MS) was used to quantify the makeup of the additive, finding a predominance of 2,3-Ditert-Butoxypropanol, also known as Glyceryl Di-Tert-Butyl Ether (GTBE). Blends of the additive at 2 and 4 volume percent were subjected to a number of standard ASTM tests, including Research Octane Number, Motor Octane Number, distillation, and vapor pressure. Results show a high boiling range and low vapor pressure for the additive, and a very modest octane boosting effect in gasoline with and without ethanol.

54 ENVIRONMENTAL SCIENCES↗

2014 AFCI Glovebox Event Executive Summary

One of the primary INL missions is to support development of advanced fuels with the goal of creating reactor fuels that produce less waste and are easier to store. The Advanced Fuel Cycle Initiative (AFCI) Glovebox in the Fuel Manufacturing Facility (FMF) is used for several fuel fabrication steps that involve transuranic elements, including americium. The AFCI glove box contains equipment used for fuel fabrication, including an arc melter – a small, laboratory-scale version of an electric arc furnace used to make new metal alloys for research – and an americium distillation apparatus. This overview summarizes key findings related to the investigation into the releases of airborne radioactivity that occurred in the AFCI glovebox room in late August and early September 2014. The full report (AFCI Glovebox Radiological Release – Evaluation, Corrective Actions and Testing, INL/INL-15-36996) provides details of the identified issues, corrective actions taken as well as lessons learned

42 ENGINEERING↗

Development of Ultrafiltration Membrane-Separation Technology for Energy-Efficient Water Treatment and Desalination Process

The growing scarcity of fresh water is a major political and economic challenge in the 21st century. Compared to thermal-based distillation technique of water production, pressure driven membrane-based water purification process, such as ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO), can offer more energy-efficient and environmentally friendly solution to clean water production. Potential applications also include removal of hazardous chemicals (i.e., arsenic, pesticides, organics) from water. Although those membrane-separation technologies have been used to produce drinking water from seawater (desalination) and non-traditional water (i.e., municipal wastewater and brackish groundwater) over the last decades, they still have problems in order to be applied in large-scale operations. Currently, a major huddle of membrane-based water purification technology for large-scale commercialization is membrane fouling and its resulting increases in pressure and energy cost of filtration process. Membrane cleaning methods, which can restore the membrane properties to some degree, usually cause irreversible damage to the membranes. Considering that electricity for creating of pressure constitutes a majority of cost (~50%) in membrane-based water purification process, the development of new nano-porous membranes that are more resistant to degradation and less subject to fouling is highly desired. Styrene-ethylene/butylene-styrene (SEBS) block copolymer is one of the best known block copolymers that induces well defined morphologies. Due to the polarity difference of aromatic styrene unit and saturated ethylene/butylene unit, these two polymer chains self-assemble each other and form different phase-separated morphologies depending on the ratios of two polymer chain lengths. Because the surface of SEBS is hydrophobic which easily causes fouling of membrane, incorporation of ionic group (e,g, sulfonate) to the polymer is necessary to reduces fouling. Recently, sulfonated SEBS became commercially available and has been extensively explored for membrane-mediated water purification technology. The sulfonated block copolymer creates a well developed nano-sale phase-separated morphologies composed of hydrophilic domains (sulfonated polystyrene) and hydrophobic domains (polyethylene/polybutylene). The hydrophilic domains determines transport properties (water transport, salt and/or ion rejection, etc) and the hydrophobic domains provides mechanical stability of the membrane. Unfortunately, a high degree of sulfonation of SEBS induces excessive swelling and deterioration of mechanical stability of the membrane. In an effort to develop robust polymeric membrane materials for water purification technology, phosphonic acid-functionalized SEBS membranes are investigated during this report period. In compare to sulfonated polymers, the corresponding phosphonated polymers are known to swell less because of the formation of extensive hydrogen bonding networks between phosphonates. In addition to the expected better mechanical stability, phosphonated polymers has another advantage over sulfonated polymers for the use water purification membrane; each phosphonate can accommodate two ions while each sulfonate accommodates only one ion. Membrane properties (ion type, ionic density, etc) of new membranes will be studied and their separation performance will be evaluated in water purification and desalination process. Through systematic study of the relationship of chemical structure–surface property–membrane performance, we aim to better understand the nature of membrane fouling and develop more fouling-resistant water purification membranes. The basic understanding of this relationship will lead to the development of advanced membrane materials which can offer a solution to environmentally sustainable production of fresh water.

36 MATERIALS SCIENCE↗

Considerations of the Differences between Bedded and Domal Salt Pertaining to Disposal of Heat-Generating Nuclear Waste

Salt formations hold promise for eternal removal of nuclear waste from our biosphere. Germany and the United States have ample salt formations for this purpose, ranging from flat-bedded formations to geologically mature dome structures. As both nations revisit nuclear waste disposal options, the choice between bedded, domal, or intermediate pillow formations is once again a contemporary issue. For decades, favorable attributes of salt as a disposal medium have been extoled and evaluated, carefully and thoroughly. Yet, a sense of discovery continues as science and engineering interrogate naturally heterogeneous systems. Salt formations are impermeable to fluids. Excavation-induced fractures heal as seal systems are placed or natural closure progresses toward equilibrium. Engineering required for nuclear waste disposal gains from mining and storage industries, as humans have been mining salt for millennia. This great intellectual warehouse has been honed and distilled, but not perfected, for all nuances of nuclear waste disposal. Nonetheless, nations are able and have already produced suitable license applications for radioactive waste disposal in salt. A remaining conundrum is site location. Salt formations provide isolation and geotechnical barriers reestablish impermeability after waste is placed in the geology. Between excavation and closure, physical, mechanical, thermal, chemical, and hydrological processes ensue. Positive attributes for isolation in salt have many commonalities independent of the geologic setting. In some cases, specific details of the environment will affect the disposal concept and thereby define interaction of features, events and processes, while simultaneously influencing scenario development. Here we identify and discuss high-level differences and similarities of bedded and domal salt formations. Positive geologic and engineering attributes for disposal purposes are more common among salt formations than are significant differences. Developing models, testing material, characterizing processes, and analyzing performance all have overlapping application regardless of the salt formation of interest.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Considerations of the Differences between Bedded and Domal Salt Pertaining to Disposal of Heat-Generating Nuclear Waste

Salt formations hold promise for eternal removal of nuclear waste from our biosphere. Germany and the United States have ample salt formations for this purpose, ranging from flat-bedded formations to geologically mature dome structures. As both nations revisit nuclear waste disposal options, the choice between bedded, domal, or intermediate pillow formations is once again a contemporary issue. For decades, favorable attributes of salt as a disposal medium have been extoled and evaluated, carefully and thoroughly. Yet, a sense of discovery continues as science and engineering interrogate naturally heterogeneous systems. Salt formations are impermeable to fluids. Excavation-induced fractures heal as seal systems are placed or natural closure progresses toward equilibrium. Engineering required for nuclear waste disposal gains from mining and storage industries, as humans have been mining salt for millennia. This great intellectual warehouse has been honed and distilled, but not perfected, for all nuances of nuclear waste disposal. Nonetheless, nations are able and have already produced suitable license applications for radioactive waste disposal in salt. A remaining conundrum is site location. Salt formations provide isolation, and geotechnical barriers reestablish impermeability after waste is placed in the geology. Between excavation and closure, physical, mechanical, thermal, chemical, and hydrological processes ensue. Positive attributes for isolation in salt have many commonalities independent of the geologic setting. In some cases, specific details of the environment will affect the disposal concept and thereby define interaction of features, events and processes, while simultaneously influencing scenario development. Here we identify and discuss high-level differences and similarities of bedded and domal salt formations. Positive geologic and engineering attributes for disposal purposes are more common among salt formations than are significant differences. Developing models, testing material, characterizing processes, and analyzing performance all have overlapping application regardless of the salt formation of interest.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Property Analysis of Ethanol--Natural Gasoline--BOB Blends to Make Flex Fuel

Ten natural gasolines were analyzed for a wide range of properties, including Reid vapor pressure (RVP), benzene, sulfur, distillation, stability, metals, and aromatic content, to determine their quality. Benzene and sulfur content were sufficiently low in all but one of the samples that they could be blended without further upgrading. Four of these samples were selected to blend with blendstock for oxygenate blending (BOB) and ethanol to produce E51, E70, and E83 blends, targeting 7.8 and 9.0-psi finished fuels. The volume of each component in the blend was estimated using the Reddy model, with the assumption that the BOB and natural gasoline blend linearly and behave as a single component in the model calculations. Results show that the Reddy model adequately predicts the RVP of the finished blend for E51 and E70, but significantly underpredicts the RVP of E83 blends by nearly 2 psi. It is hypothesized that the underprediction is a function of the very low aromatic content of the E83 blends, even compared to the E51 and E70 blends.

03 NATURAL GAS↗

Groundwater Pathway Model for the Los Alamos National Laboratory Technical Area 21, Material Disposal Area T

This report consists of four major sections, including this introductory section. Section 2 provides an overview of previous investigations related to the development of the current sitescale model. The methods and data used to develop the 3-D groundwater model and the techniques used to distill that model into a form suitable for use in the GoldSim models are discussed in Section 3. Section 4 presents the results of the model development effort and discusses some of the uncertainties involved. Three attachments that provide details about the components and data used in this groundwater pathway model are also included with this report.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Groundwater Pathway Model for the Los Alamos National Laboratory Technical Area 54, Area G, Revision 1

This report consists of four major sections, including this introductory section. Section 2 provides an overview of previous investigations related to the development of the current sitescale model. The methods and data used to develop the 3-D groundwater model and the techniques used to distill that model into a form suitable for use in the GoldSim models are discussed in Section 3. Section 4 presents the results of the model development effort and discusses some of the uncertainties involved. Eight attachments that provide details about the components and data used in this groundwater pathway model are also included with this report. The groundwater modeling effort reported here is a revision of the work that was conducted in 2005 (Stauffer et al., 2005a) in support of the 2008 Area G performance assessment and composite analysis (LANL, 2008). The revision effort was undertaken primarily to incorporate new geologic information that has been collected since 2003 at, and in the vicinity of, Area G. The new data were used to create a more accurate geologic framework model (GFM) that forms the basis of the numerical modeling of the site’s long-term performance. The groundwater modeling uses mean hydrologic properties of the geologic strata underlying Area G; this revision includes an evaluation of the impacts that natural variability in these properties may have on the model projections.

58 GEOSCIENCES↗

Final Scientific/Technical Report for Program Title: Solar Powered Dewvaporation Desalination System

Desalination technologies have been used increasingly throughout the world to produce the drinking water from the brackish ground and sea water for the past few decades. Among the commercially available desalination technologies, reverse osmosis (RO) and multi-stage flash distillation are the most widely used technologies globally. However, these technologies are difficult to be directly integrated with green energies without converting them to electricity. Dewvaporation, a desalination process, uses saturated steam as a carrier-gas to evaporate water from saline feeds and form pure condensate. It has the major technical benefit of reusing energy, released from vapor condensation, multiple times. The current proposal has been planned to address this issue. In Phase I, we have successfully demonstrated the feasibility of a new plasmonic nanoparticle based approach through fabrication and evaluation of a solar powered water vapor generation module. The water vapor generation module allows generation of high temperature plasmon on a fiber bundle end, where strong water and plasmon interaction occurs generating water vapor. Plasmon enhanced water evaporation has been realized on plasmonic nanoparticle immobilized substrate with an energy conversion efficiency of over 50%.

14 SOLAR ENERGY↗

Model-Based Extracted Water Desalination System for Carbon Sequestration

Over the last 1.5 years, GE Global Research and Pennsylvania State University defined a model-based, scalable, and multi-stage extracted water desalination system that yields clean water, concentrated brine, and, optionally, salt. The team explored saline brines that ranged across the expected range for extracted water for carbon sequestration reservoirs (40,000 up to 220,000 ppm total dissolved solids, TDS). In addition, the validated the system performance at pilot scale with field-sourced water using GE’s pre-pilot and lab facilities. This project encompassed four principal tasks, in addition to Project Management and Planning: 1) identify a deep saline formation carbon sequestration site and a partner that are suitable for supplying extracted water; 2) conduct a techno-economic assessment and down-selection of pre-treatment and desalination technologies to identify a cost-effective system for extracted water recovery; 3) validate the downselected processes at the lab/pre-pilot scale; and 4) define the scope of the pilot desalination project. Highlights from each task are described below: Deep saline formation characterization The deep saline formations associated with the five DOE NETL 1260 Phase 1 projects were characterized with respect to their mineralogy and formation water composition. Sources of high TDS feed water other than extracted water were explored for high TDS desalination applications, including unconventional oil and gas and seawater reverse osmosis concentrate. Technoeconomic analysis of desalination technologies Techno-economic evaluations of alternate brine concentration technologies, including humidification-dehumidification (HDH), membrane distillation (MD), forward osmosis (FO), turboexpander-freeze, solvent extraction and high pressure reverse osmosis (HPRO), were conducted. These technologies were evaluated against conventional falling film-mechanical vapor recompression (FF-MVR) as a baseline desalination process. Furthermore, a quality function deployment (QFD) method was used to compare alternate high TDS desalination technologies to FF-MVR. High pressure reverse osmosis was found to a be a promising alternative desalination technology. A deep-dive technoeconomic analysis of HPRO was performed, including Capex and Opex estimates, for seawater RO (SWRO). Additionally, two additional cases were explored: 1) a comparison of a SWRO plus HPRO system to the option of doubling the size of a standard seawater RO system to achieve the same total pure water recovery rate; and 2) a flue gas desulfurization wastewater treatment zero-liquid discharge (ZLD) application, where preconcentration with RO (SWRO or SWRO + HPRO) before evaporation and crystallization was compared to FF-MVR and crystallization technologies without RO preconcentration. Pre-pilot process validation Pre-pilot-scale tests were conducted using field production water to validate key process steps for extracted water pretreatment. Approximately 5,000 gallons of field produced water was processed through, microfiltration, ultrafiltration, and steam regenerable sorbent operations. Smaller quantities were processed through microclarification. In addition, analytical methods (purge-and-trap gas chromatography and Hach TOC analytical methods) were validated. Lab-scale HPRO elements were constructed and tested at high pressures, to identify and mitigate technical risks of the technology. Lastly, improvements in RO membrane materials were identified as the necessary next step to achieve further improvement in element performance at high pressure. Scope of Field Pilot A field pilot for extracted water pretreatment was designed.

20 FOSSIL-FUELED POWER PLANTS↗

Recommended Research Directions for Improving the Validation of Complex Systems Models.

Improved validation for models of complex systems has been a primary focus over the past year for the Resilience in Complex Systems Research Challenge. This document describes a set of research directions that are the result of distilling those ideas into three categories of research -- epistemic uncertainty, strong tests, and value of information. The content of this document can be used to transmit valuable information to future research activities, update the Resilience in Complex Systems Research Challenge's roadmap, inform the upcoming FY18 Laboratory Directed Research and Development (LDRD) call and research proposals, and facilitate collaborations between Sandia and external organizations. The recommended research directions can provide topics for collaborative research, development of proposals, workshops, and other opportunities.

99 GENERAL AND MISCELLANEOUS↗

Cyber Deterrence and Stability

Throughout the 20th and early 21st centuries, deterrence and arms control have been cornerstones of strategic stability between the superpowers. However, the weaponization of the cyber realm by State actors and the multipolar nature of cyber conflict now undermines that stability. Strategic stability is the state in which nations believe that if they act aggressively to undermine U.S. national interests and the post-World War II liberal democratic order, the consequences will outweigh the benefits. The sense of lawlessness and lack of consequences in the cyber realm embolden States to be more aggressive in taking actions that undermine stability. Accordingly, this paper examines 1) the role of deterrence and arms control in securing cyber stability, and 2) the limitations and challenges associated with these traditional national security paradigms as applied to this emerging threat domain. This paper demonstrates that many 20th-century deterrence and arms control concepts are not particularly applicable in the cyber realm. However, they are not entirely irrelevant. The United States can distill lessons learned from this rich deterrence and arms control experience to develop and deploy a strategy to advance cyber stability.

97 MATHEMATICS AND COMPUTING↗

The Trip Itinerary Optimization Platform: A Framework for Personalized Travel Information

The New Concepts Incubator team at the National Renewable Energy Laboratory (NREL) developed a three-stage online platform for travel diary collection, personal travel plan optimization and travel itinerary visualization. In the first stage, users provide a travel diary for the previous day through an interactive map and calendar interface and survey for travel attitudes and behaviors. One or more days later, users are invited via email to engage in a second stage where they view a personal mobility dashboard displaying recommended travel itineraries generated from a novel framework that optimizes travel outcomes over a sequence of interrelated trips. A week or more after viewing these recommended travel itineraries on the dashboard, users are emailed again to engage in a third stage where they complete a final survey about travel attitudes and behaviors. A usability study of the platform conducted online showed that, in general, users found the system valuable for informing their travel decisions. A total of 274 individuals were recruited through Amazon Mechanical Turk, an online survey platform, to participate in a transportation study using this platform. On average, the platform distilled 65 feasible travel plans per individual into two recommended itineraries, each optimal according to one or more outcomes and dependent on the fixed times and locations from the travel diary. For 45 percent of users, the trip recommendation algorithm returned only a single, typically automobile-centric, itinerary because there were no other viable alternative transportation modes available. Platform users generally agreed that the dashboard was enjoyable and easy to use, and that it would be a helpful tool in adopting new travel behaviors. Users generally agreed most that the time, cost and user preferred recommendations 'made sense' to them, and were most willing to implement these itineraries. Platform users typically expressed low willingness to try the carbon and calories optimized itineraries. Of the platform users who viewed the dashboard, 13 percent reported changing their travel behavior, most adopting the time, calories or carbon optimized itineraries. While the algorithm incorporates a wealth of travel data obtained from online APIs pertaining to a travelers route such as historic traffic condition data, public transit time-tables, and bike path routes, open-ended responses from users expressed an interest in the integration of even more fine-grained traffic data and the ability to dynamically model the effect of changes in travel times. Users also commonly expressed concerns over the safety of walking and biking recommendations. Responses indicate that more information about the amenities available to cyclists and pedestrians (sidewalks, shade from trees, access to food) and routes that avoid areas of perceived elevated danger would reduce barriers to implementing these recommendations. More accurate representations of personal vehicle trips (based on vehicle make and model, implications of parking) and the identification of routes that optimize caloric intensity (seeking out elevation changes or longer walks to public transit) are promising avenues for future research.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Development of a Knowledgebase (MetRxn) of Metabolites, Reactions and Atom Mappings to Accelerate Discovery and Redesign

With advances in DNA sequencing and genome annotation techniques, the breadth of metabolic knowledge across all kingdoms of life is increasing. The construction of genome-scale models (GSMs) facilitates this distillation of knowledge by systematically accounting for reaction stoichiometry and directionality, gene to protein to reaction relationships, reaction localization among cellular organelles, metabolite transport costs and routes, transcriptional regulation, and biomass composition. Genome-scale reconstructions available now span across all kingdoms of life, from microbes to whole-plant models, and have become indispensable for driving informed metabolic designs and interventions. A key barrier to the pace of this development is our inability to utilize metabolite/reaction information from databases such as BRENDA [1], KEGG [2], MetaCyc [3], etc. due to incompatibilities of representation, duplications, and errors. Duplicate entries constitute a major impediment, where the same metabolite is found with multiple names across databases and models, which significantly slows downs the collating of information from multiple data sources. This can also lead to serious modeling errors such as charge/mass imbalances [4,5] which can thwart model predictive abilities such as identifying synthetic lethal gene pairs and quantifying metabolic flows. Hence, we created the MetRxn database [6] that takes the next step in integrating data from multiple sources and formats to automatically create a standardized knowledgebase. We subsequently deployed this resource to bring about new paradigms in genome-scale metabolic model reconstruction, metabolic flux elucidation through MFA, modeling of microbial communities, and pathway prospecting. This research has enabled the PI’s group to continue building upon research milestones and reach new ones (see list of MetRxn-related publications below).

59 BASIC BIOLOGICAL SCIENCES↗

Evaluating the Techno-Economic Feasibility of Forward Osmosis Process Utilizing Low Grade Heat: Applications in Power Plant Water, Wastewater, and Reclaimed Water Treatment

Recovering and using uncoverted heat produced during electric power generation holds potential to significantly improve the efficiency of the electric power industry. One potential use of this low-temperature waste heat is on-site water treatment using waste heat driven processes to comply with the 2015 Effluent Limitation Guidelines for the Steam Electric Generating Sector. Ammonia-carbon dioxide forward osmosis (NH 4 HCO 3 FO) is a two-step waste heat driven process that involves a membrane separation process in which an osmotic pressure gradient created by an NH 4 HCO 3 draw solution is used to pull water across the membrane and a distillation column to regenerate the NH 4 HCO 3 draw solution. In this work we estimate the quantity, quality, and spatio-temporal availability of waste heat produced at U.S. coal, nuclear, and natural gas plants. We combine these estimates of waste heat availability with a techno-economic optimization model of NH 4 HCO 3 FO in order to assess the potential of NH 4 HCO 3 FO to treat flue gas desulfurization (FGD) wastewater, gasification wastewater, and boiler feedwater. We find that in 2012, 18.9 billion GJ of waste heat was discharged from the U.S. coal, natural gas, and nuclear fleet, although only 900 million GJ of waste heat was discharged at temperatures suitable for NH 4 HCO 3 FO. A maximum of 1.9 billion m3/yr of water could be produced using this waste heat to drive a NH 4 HCO 3 FO. The costs of waste heat driven NH 4 HCO 3 FO for FGD and gasification wastewater treatment to zero liquid discharge (ZLD) and boiler feedwater treatment are 2.20-2.40/m 3 and 0.35-0.65/m 3 , respectively. With mechanical vapor compression and crystallization for ZLD wastewater treatment and reverse osmosis for boiler feedwater treatment as the cost benchmark technologies, waste heat driven NH 4 HCO 3 FO is cost competitive for ZLD wastewater treatment, but not boiler feedwater treatment.

20 FOSSIL-FUELED POWER PLANTS↗

A Hybrid Catalytic Route to Fuels from Biomass Syngas

LanzaTech partnered with the Pacific Northwest National Laboratory (PNNL), Imperium Aviation Fuels, InEnTec, Orochem Technologies, the University of Delaware, Michigan Technological University, the National Renewable Energy Laboratory, and The Boeing Company, to develop a cost-effective hybrid conversion technology for catalytic upgrading of biomass-derived syngas to sustainable alternative jet fuel (SAJF) meeting the price, quality and environmental requirements of the aviation industry. Alternative “synthetic paraffinic kerosene” (SPK) blendstock produced from syngas via “Fischer-Tropsch” (F-T) or from lipids via “hydroprocessing of esters and fatty acids” (HEFA) are currently being used in commercial jet fuel blends containing at least 50% petroleum-based fuel. This project developed an alternative route to SAJF from ethanol, a type of “alcohol to jet” (ATJ) SPK. The project objective was to demonstrate a pathway that combines syngas fermentation to ethanol with catalytic upgrading of ethanol to sustainable alternative jet fuel and shows attractive overall system economics to drive down the price of biomass-derived jet fuel. The hybrid pathway was to be demonstrated on three biomass feedstocks: corn stover, woody biomass, and third biomass feedstock, cellulosic residues. The objective also included the co-production of chemicals, exemplified by 2,3-Butanediol (2,3-BDO), which can be converted to key chemical intermediates. The team successfully demonstrated that biomass syngas fermentation followed by catalytic conversion is a viable alternative to the Fischer-Tropsch process and produces a fuel with properties comparable to F-T and HEFA SPKs. Plasma gasification and gas fermentation were successfully integrated and demonstrated in continuous fermentations on waste wood, corn stover, and cellulosic bagasse. Gas fermentation was demonstrated to produce ethanol suitable for catalytic upgrading, isolating the upgrading from variations in biomass feed, syngas composition, and impurities. Ethanol feedstocks from all three types of biomass were demonstrated to be comparable to grain derived ethanol and suitable for the LT-PNNL ATJ process. The LT-PNNL ATJ catalytic upgrading process was demonstrated at lab scale for over 2000 hours of continuous operation on a single catalyst load. LanzaTech scaled up the ATJ process, producing 4000 gallons of jet and 600 gallons of diesel for testing and a future proving flight. The LT-PNNL ATJ process, at lab and pilot scale, using commercial grain-based ethanol and steel mill waste gas-based ethanol (“Lanzanol”), produces high-quality fuel-range distillates containing primarily normal paraffins and isoparaffins. The LT-PNNL ATJ fuel has equivalent properties to previously-approved SPKs such as F-T, HEFA, and ATJ from isobutanol, and conforms with critical properties needed to blend with conventional jet fuel. The project showed that the 2,3-BDO fermentation co-product can be separated economically utilizing Simulated Moving Bed (SMB) technology. 2,3-BDO can be catalytically converted to 1,3-butadiene (BD) in a two-step process with at least 70% yield, producing a chemical intermediate suitable for downstream applications. Technoeconomic and life cycle analyses of the biomass to jet process with and without 2,3-BDO production showed that capital costs are sensitive to the proportion of the 2,3-BDO co-product and biomass feedstock. The co-product 2,3-BDO, converted through to BD, significantly reduces the cash cost of production of the hydrocarbon fuels. Life cycle GHG emissions of ATJ SPK produced from biomass using a steam gasification system are projected to be significantly lower than those of conventional jet fuel. The project demonstrated that a high quality ATJ SPK, can be produced from biomass via a hybrid gas fermentation/catalytic route. Validation of the LT-PNNL ATJ process using a variety of ethanol feedstocks demonstrated the viability of a future model of distributed ATJ production, in which ethanol may be produced at multiple facilities from local feedstocks and shipped to a central facility for conversion. The project demonstrated that co-production of chemicals has the potential to reduce jet cost of production, thereby accelerating commercial production of SAJF from biomass.

09 BIOMASS FUELS↗

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.

01 COAL, LIGNITE, AND PEAT↗