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Subtask 1.3 – Integrated Carbon Capture and Storage for North Dakota Ethanol Production

The Energy & Environmental Research Center (EERC), in partnership with Red Trail Energy, LLC (RTE), a North Dakota ethanol producer; the North Dakota Industrial Commission (NDIC) Renewable Energy Program (REP); and the U.S. Department of Energy (DOE), conducted a feasibility and implementation study for a commercial carbon capture and storage (CCS) effort. This subtask provided technical support and developed recommended practices of how small-scale industrial CO2 emitters (<1,000,000 tonnes of CO2 emitted annually) may economically deploy CCS. The 64-million-gallon dry mill RTE ethanol facility, emitting an average 180,000 tonnes of CO2 annually, was the subject of the case study. The positive outcome of this research, which shows technical and economic potential for ethanol–CCS in North Dakota, has resulted in RTE acquiring an approved Permit to Drill on December 2, 2019, for a stratigraphic test well in early 2020, a necessary step toward a North Dakota CO2 Storage Facility Permit (SFP) for the RTE CCS effort. Outcomes include 1) validating the Broom Creek Formation as a regional target for CCS, 2) determining the full carbon life cycle of an industrial fuel production facility with CCS, 3) developing a field implementation plan (FIP) for small-scale CCS, and 4) determining the validity and pathway for using CCS to meet low-carbon fuel (LCF) standards. The technical team included the EERC, RTE, Trimeric Corporation, Schlumberger Carbon Services, and Computer Modelling Group (CMG). Findings from activities conducted November 2016 – May 2020 are summarized as follows. Several key steps have been accomplished toward validating the Broom Creek Formation as a CO2 injection and storage target at the RTE CCS site, including verification of the presence and structure of sandstone layers that may comprise the potential CO2 storage reservoir and the several thousand feet of overlying confining zone. Work included site characterization using existing data, interpretation of seismic data within the study area, and geologic modeling simulation of CO2 injection. Interpreted results estimate 3000 feet of confining zone between the Broom Creek Formation (storage target) and the lowermost underground source of drinking water (e.g., the Fox Hills Formation). The thickness of the Broom Creek injection target varies 230–420 ft within the survey area. Results were used to inform the location of a stratigraphic test well and associated characterization test program. No impediments were identified within the targeted CO2 storage complex that would prevent the project from moving forward. A stratigraphic test well is the next step to validate these results and to acquire remaining data necessary to develop a North Dakota CO2 SFP application. The EERC generated full carbon life cycle estimates for CCS integration with the RTE ethanol facility. Results indicated that an average 40% reduction in CO2 emissions is possible through CCS implementation. Approximately half of the carbon in the overall life cycle for a dry mill ethanol plant is generated through the fermentation process and emitted to the atmosphere; this is the CO2 stream targeted for CCS. The remaining carbon is attributed to corn feedstock farming (diesel, fertilizer), energy for fuel processing (natural gas, electricity), and transportation (diesel) of the fuel product. Life cycle carbon estimates are also affected by the anticipated energy consumption of a potential capture facility, which depend on the type of CO2 product generated. For example, a 30%–40% net CO2 emission reduction is estimated if a liquefied CO2 facility were incorporated compared to a 40%–50% net CO2 reduction if a supercritical “injection-grade” CO2 product is generated; i.e., more energy is required to further refine the CO2 stream, affecting the full carbon life cycle estimates. A CCS FIP was developed and initiated at the RTE CCS site, resulting in the development of several guidance documents: a CO2 Capture Process Design Package, a North Dakota CO2 geologic Storage Permits Template, and a Public Outreach Package for CCS in North Dakota. General FIP components include CO2 capture system, pipeline and well designs; monitoring, verification, and accounting (MVA) plans; geologic characterization and testing programs; and permitting and outreach plans. Vendor bids were also acquired for the CO2 liquefaction facility. Near-surface characterization (groundwater and soil gas sampling) and geologic characterization (seismic survey) were initiated to inform development of a UIC Class VI-compliant MVA plan compliant with a North Dakota CO2 SFP. Designs (well and geologic testing) were completed for a stratigraphic test well compliant with a North Dakota CO2 SFP. In addition, the outreach plan was executed, including community open houses, meetings with city/county/state officials, and development of public materials. Although other entities continued to mature incentive programs in 2019–2020, California and the Internal Revenue Service (IRS) currently provide the most advanced economic opportunities for CCS integrated with fuel production. The California Low-Carbon Fuel Standard (LCFS) adopted a CCS Protocol in January 2019, allowing submittal of a design-based pathway (DBP) application for an approved temporary (not certified) carbon intensity value for a fully engineered facility. An ethanol–CCS DBP application to the California LCFS Program (officially approved February 28, 2020) was developed to show that the RTE CCS effort meets LCFS requirements. The approved DBP provides confidence to advance the project and supports potential investments. Other entities continue to mature incentive programs. The IRS issued guidance in February 2020 that addresses the definition of beginning of construction and revenue procedure on partnerships for the Enhancement of Carbon Dioxide Sequestration Credit (a.k.a. Section 45Q) CCS tax credit program; the IRS anticipates issuing further guidance on issues such as secure geologic storage, utilization qualifications, and recapture of claimed credits. Maturing incentive programs coupled with workable permitting regulations provide confidence to advance CCS projects in North Dakota and support financial investment to proceed with designing, constructing, and implementing CCS projects at small-scale fuel production facilities. The largest hurdles for CCS implementation at small-scale industrial systems are often business/economic-related (i.e., not technical). Market uncertainty already exists for agriculture-based alternative fuels such as corn ethanol, for which production has increased by ~33%, and prices have correspondingly lowered since 2015. Passing the Section 45Q tax credit program improves economic feasibility for CCS but may require external investors for a small business to achieve maximum benefits. Public–private partnerships with NDIC and DOE have resulted in foundational technical and regulatory knowledge, growing stakeholder confidence, and a pathway to implementation that enables similar industrial CCS projects in the region to advance. This subtask was funded through the EERC–DOE Joint Program on Research and Development for Fossil Energy-Related Resources Cooperative Agreement No. DE-FE0024233. Nonfederal funding was provided by NDIC and RTE. The authors would also like to thank CMG, ESRI, IHS, Neuralog, and Schlumberger for allowing the use of their software packages in support of this work.

42 ENGINEERING↗

BETO 2021 Peer Review - Catalytic Upgrading of Pyrolysis Vapors 2.3.1.314

Catalytic fast pyrolysis (CFP) is a versatile pathway for the direct liquefaction of biomass and waste carbon sources to generate a stabilized bio-oil intermediate that can be further processed into renewable fuels, chemicals, and materials. The objective of this project is advance the CFP state-of-technology through integrated catalyst and process development, expand market responsiveness by creating routes to novel co-products, and provide experimental data to inform process modelling and scale-up activities. Research advancements over the past two years include reducing analytical uncertainty by achieving 100 ± 1% carbon balances during reaction testing with woody biomass, improving process efficiency by achieving a 4x increase in catalyst cycle length, demonstrating compatibility with waste feedstocks, and confirming process durability for 100+ reaction cycles. Additionally, this project supported a comprehensive pathway review to evaluate scale-up needs. This review resulted in the early identification of technical risks and informed proactive planning for the BETO 2022 Verification. Other impacts from this project include generation of broadly enabling scientific knowledge (14 publications/18 presentations since 2019), engagement with industry partners (e.g., Johnson Matthey and ExxonMobil), and identification of a promising pathway to market that addresses emerging demands for biogenic refinery feedstocks.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

BETO 2021 Peer Review - Thermochemical Platform Analysis WBS: 2.1.0.302

The objective of the NREL Thermochemical Platform Analysis (WBS 2.1.0.302) project is to inform and guide R&D priorities for thermal and catalytic conversion processes by providing process design and techno-economic analysis (TEA). This is achieved through close collaboration with researchers and external experts, along with the use of both commercially available modeling tools and the development or use of collaboration-derived domain-specific tools and resources, such as refinery integration, kinetic and reactor models, phase equilibrium models, and pertinent bio-products market studies. This project is directly aligned with DOE-BETO goals, with the enabling of technology advancements and cost reduction for biomass derived biofuels being one of its primary objectives. TEA-guided research facilitated by this project has helped achieve significant modeled cost reductions for the ex situ catalytic fast pyrolysis (CFP) pathway and the indirect liquefaction (IDL) pathway for the conversion of syngas to high-octane gasoline (HOG). Cost reduction through refinery integration, development of valuable co-products, and other options are being identified for future research to help reduce the modeled MFSP to $2.50/GGE by 2030. Additional priorities anticipated in the future, such as the use of renewable electricity for liquid fuels and products, and emphasis on waste utilization are also being explored in conjunction with research on catalytic utilization of syngas and other gases (including CO2). Industry-relevant parameters are given deliberate attention as part of the work done under this project to help answer questions important for future commercialization and address associated risks.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Fuel cell and electrolyzer hotbox module using conductive zirconia stacks

Modular pressurized hotbox for use and substitution in a variety of pressurized electrochemical applications to include reversible solid oxide electrolyzer and fuel cells, energy storage systems, renewable fuel production, solid-state hydrogen pumping and liquefaction, and oxygen transport membranes. This is enabled by mixed electronic and ionic conducting compositions of vanadia-yttria and vanadia-calcia stabilized zirconia and a dry powder method of manufacture for ceramic core stacks.

McLarty, Dustin↗

Biofuel Air Emissions Analysis

U.S. has goals to produce 3 billion gallons of sustainable aviation fuel (SAF) annually by 2030, increasing to 35 billion gallons by 2050 to decarbonize the aviation sector. Meeting these production targets will require large number of biorefineries to be set up. However, ability to comply with federal air quality standards is prerequisite to being issued a construction permit. Negotiating the permitting process for a new biorefinery can be quite onerous and cost the investors significant time and money. Although there can be numerous reasons for delayed biorefinery construction, air permitting is fraught with pitfalls because the permitting process relies on precedence, which the future SAF biorefineries lack. NREL's Biofuel Air Emissions Analysis project is unique and innovative in terms of the tools, approaches, and analyses provided. NREL is the only national laboratory that is actively working at the intersection of Federal air quality regulations, emissions and air quality analysis across the supply chain, and process design. This project is focused on providing much needed data and analyses that address biorefinery air permitting. This project develops models and quantitative analyses and measures progress towards meeting air quality regulatory requirements. These models and methods are applied to analyze air permitting related to wastewater sludge to biofuel conversion pathways using hydrothermal liquefaction (HTL), impacts of HTL pathway on local and regional air quality including an assessment of health and equity impacts. In addition to filling research gaps, this project also disseminates the findings to the relevant stakeholders at BETO, other national labs, and regulatory agencies.

air quality↗

Biofuels as Heavy Fuel Oil Substitutes in the Maritime Sector: Findings and Potential Pathways

The United States Department of Energy has commissioned four national laboratories to evaluate the feasibility of biofuels in the maritime sector. This effort is briefly described including the overall project goals, structure and aims. The large two-stroke crosshead engines used to power large merchant vessels were of particular interest since they can burn lower combustion quality fuels relative to four-stroke engines. This characteristic allows for consideration of pyrolysis oils and hydrothermal liquefaction (HTL) oils which are feedstock agnostic and, in the raw state, are more economical compared to distillate drop-in fuels. Pyrolysis and HTL oils are collectively known as bio-intermediates since they require additional processing for use in distillate fuel systems. The key limiting feature is that these bio-intermediate fuels will cause asphaltene precipitation when blended with heavy fuel oils (HFOs) such as very low sulfur fuel oil (VLSFO) unless they are upgraded to remove water and oxygenates. Economics are the key driver at this point in time, and preliminary techno-economic analyses (TEAs) indicate that bio-intermediates have potentially lower cost relative to other biofuels such as biodiesel and renewable diesel. Additionally, life cycle analyses (LCAs) of feedstocks and pathways show the life cycle carbon reduction benefit relative to heavy fuel oils. In addition to TEA and LCA results, we also present on the technical feasibility of these fuels. These studies have focused on the properties of biofuel blends with VLSFO that are critical to the fuel systems of maritime vessels fueled with HFOs. These properties include the compatibility with fuel system metals, viscosity, and blend stability. Aging studies with blends of VLSFO with biodiesel, HTL, and pyrolysis oils are also presented. Future efforts being planned to conduct additional biofuel testing, including the use of biofuels as pilot fuels in zero carbon shipping options fueled with ammonia and methanol, ship-based demonstrations, and bioresource competition studies.

Kass, Michael↗

Evaluation of Bio-Intermediates and Other Biofuels for use in Marine Engines

This paper presents an overview of the DOE Marine Biofuel Feasibility Study to evaluate the potential of biofuels for ocean-going vessels. These vessels operate on low-cost residual fuel oils (also known as heavy fuel oils or HFO), which require significant heating and purification onboard vessels. The industry is looking at economical alternative fuels that can enhance performance from combustion/emissions, rheology, and other perspectives. Four U.S. national laboratories are collaborating to evaluate a variety of biofuels, including bio-intermediates (pyrolysis and hydrothermal liquefaction oils), biodiesel (fatty acid methyl esters or FAME), bio-residuals (FAME byproducts) for their suitability as fuels for marine diesel engines. Bio-intermediates in particular are of interest because large marine engines that operate on HFO can tolerate lowerquality, more viscous fuels and may be able to utilize these fuels with less upgrading than other applications, presenting economic advantages. The test fuels of interest are examined to determine the minimum level of upgrading required for blend compatibility with market HFOs containing high levels of asphaltenes as well as their impact on the viscosity, polymerization tendency, and combustion properties (particularly cetane number) of the fuel blends in preparation for future evaluation in engine studies.

Kaul, Brian [ORNL] (ORCID:0000000184813620)↗

Extraction of Oil From Camelina Seeds Using Liquefied Dimethyl Ether

With a changing climate and a push for net-zero carbon emissions, sustainable aviation fuel (SAF) is gaining interest worldwide. Due to its compatibility with current infrastructure and potential to reduce emissions by up to 94%, SAF has been identified as the best near-term opportunity to decrease carbon emissions in the aviation industry. SAF can be produced from various renewable feedstocks, with Camelina sativa (L.) seeds standing out due to their high oil content. Conventionally, the oil is extracted using hydrothermal liquefaction (HTL), which involves the pressurized heating of water and biomass up to 400°C, making it incredibly energy-intensive. Conversely, liquefied dimethyl ether (DME) extraction operates at room temperature and is capable of near 100% solvent recycling. In this work, we propose the use of DME extraction as a substitute for HTL, hypothesizing that it can overcome the challenges of current oil extraction methods while maintaining the same oil yields.

09 - BIOMASS FUELS↗

Preservation of Microalgae, Lignocellulosic Biomass Blends by Ensiling to Enable Consistent Year-Round Feedstock Supply for Thermochemical Conversion to Biofuels

Seasonal variation in microalgae productivity is a significant barrier to economical production of algae biofuels and chemicals. Summer production can be 3–5 times higher than in the winter resulting in uneven feedstock supplies at algae biorefineries. A portion of the summer production must be preserved for conversion in the winter in order to maintain a biorefinery running at capacity. Ensiling, a preservation process that utilizes lactic acid fermentation to limit microbial degradation, has been demonstrated to successfully stabilize algae biomass (20% solids) and algae-lignocellulosic blends (40% algae-60% lignocellulosic biomass, dry basis) for over 6 months, resulting in fuel production cost savings with fewer emissions. Preservation of algae as blends could be beneficial to biorefineries that utilize thermochemical approaches to fuel production as co-processing of algae and lignocellulosic biomass has been observed to enhance biocrude yield and improve oil quality. This study conducts a resource assessment of biomass residues in the southern United States to identify materials available during peak algae productivity and in sufficient quantity to meet the algae storage needs of an algae biofuel industry. Eight feedstocks met the quantity threshold but only three, distillers grains, haylage, and yard waste, were also available in season. Storage experiments utilizing both freshwater and marine strains of microalgae – Scenedesmus acutus, Chlorella vulgaris, Chlorella zofingiensis, Nannochloropsis gaditana, and Porphyridium purpureum – and yard waste were conducted for 30 days. Storage losses were less than 10% in all but one case, and the pH of all but one blend was reduced to less than 4.7, indicating that yard waste is a suitable feedstock for blending with algae prior to storage. To better understand whether the benefits to conversion realized by processing blends might be affected by storage, elemental analysis and bomb calorimetry of pre- and post-storage algae-yard waste blends were conducted to characterize changes occurring during storage. Storing algae biomass as blends with lignocellulosic biomass could be an effective method of mitigating seasonal variability in algae biomass production while retaining the synergistic effect of co-processing algae blends in thermochemical conversion.

09 BIOMASS FUELS↗

Thermochemical Conversion of Plastic Waste into Fuels, Chemicals, and Value-Added Materials: A Critical Review and Outlooks

Plastic waste is an emerging environmental issue for our society. Critical action to tackle this problem is to upcycle plastic waste as valuable feedstock. Thermochemical conversion of plastic waste has received growing attention. Although thermochemical conversion is promising for handling mixed plastic waste, it typically occurs at high temperatures (300–800 °C). Catalysts can play a critical role in improving the energy efficiency of thermochemical conversion, promoting targeted reactions, and improving product selectivity. Here this Review aims to summarize the state-of-the-art of catalytic thermochemical conversions of various types of plastic waste. First, general trends and recent development of catalytic thermochemical conversions including pyrolysis, gasification, hydrothermal processes, and chemolysis of plastic waste into fuels, chemicals, and value-added materials were reviewed. Second, the status quo for the commercial implementation of thermochemical conversion of plastic waste was summarized. Finally, the current challenges and future perspectives of catalytic thermochemical conversion of plastic waste including the design of sustainable and robust catalysts were discussed.

chemolysis↗

New strategy for liquefying corn stover pellets

The movement of solid material into and between unit operations within a biorefinery is a bottleneck in reaching design capacity, with formation of biomass slurries needed to introduce feedstock. Corn stover slurries have been achieved from dilute acid, pretreated materials resulting in slurry concentrations of up to about 150 g/L, above which flowability is compromised. We report a new strategy to liquefy corn stover at higher solids concentration (300 g/L) by initially cooking it with the enzyme mimetic maleic acid at 40 mM and 150°C. This is followed by 6 h of enzymatic modification at 1 FPU (2.2 mg protein)/g solids, resulting in a yield stress of 171 Pa after 6 h and 58 Pa in 48 h compared to 6806 Pa for untreated stover. Mimetic treatment of corn stover pellets minimizes the inhibitory effect of xylo-oligomers on hydrolytic enzymes. Furthermore, this strategy allows for the delivery of solid lignocellulosic slurry into a pretreatment reactor by pumping, improving operability of a biorefinery.

09 BIOMASS FUELS↗

Challenges and opportunities for alternative fuels in the maritime sector

Amidst a period of historic transformation, the marine shipping sector faces uncertainty regarding its ability to reliably fuel while remaining compliant with new international environmental regulations and targets. Increasingly stringent environmental standards, and heightened regulatory focus on maritime decarbonization are driving infrastructural and technical development for alternative fuels and mixtures, engine concepts, and operating practices. However, the transition to alternative fueling is highly complex and requires both a global outlook that spans diverse stakeholder demographics and coordination with multiple actors across the value chain. To aid stakeholders involved in decision making and research related to the transition, a scoping study was conducted with the goal of outlining the barriers, uncertainties, and possibilities in the short and long term for the transition. Synthesis of these results provides strategic decision support, technical direction, and a set of R&D priorities for maritime stakeholders and the scientific community.

09 BIOMASS FUELS↗

Valorization of lignin from aqueous-based lignocellulosic biorefineries

An additional 100 million tons/year of lignin coproduct will result when lignocellulosic biomass is processed in biorefineries to fiber, sugars, biofuels, and bioproducts. This will double the amount of lignin already generated from pulping and paper production. Unlike pulping that results in lignosulphonate (88% of total) or Kraft lignin (9%), aqueous-based biorefining leaves behind non-sulfonated lignin and aromatic molecules. Furthermore, this new type of lignin provides opportunities for large volume agricultural uses such as controlled-release carriers and soil amendments as well as feedstocks for new chemistries that lead to molecular building blocks for the chemical industry and to precursors for sustainable aviation biofuels.

03 NATURAL GAS↗

Algae Asphalt to Enhance Pavement Sustainability and Performance at Subzero Temperatures

This paper evaluates the potential of algae-derived biobinders as sustainable alternatives for pavement construction. It specifically examines the physicochemical and rheological properties of biomodified binders and their potential to offset carbon emissions when used as partial replacements for conventional petroleum-based asphalt binders. Biosequestration of CO 2 using microalgal cell factories is a promising way of recycling CO 2 into biomass via photosynthesis. Our study demonstrates that incorporating algae-derived binders into asphalt can significantly reduce carbon emissions. Each 1% increase in algae-based biobinder leads to an approximate 4.5% decrease in net carbon emissions. This indicates that a blend containing about 22% biobinder has the potential to achieve carbon neutrality. Blends with higher proportions may even result in net-negative emissions, highlighting a promising strategy for environmentally responsible road construction. In terms of performance, the study shows that certain algae-derived biobinders significantly enhance the cracking resistance of asphalt, particularly under subzero temperatures, by improving its stress-relief capacity. A key contribution of this work is the introduction of polarizability as a novel molecular-level parameter for assessing the compatibility of algae-derived bio-oils with asphalt. By capturing the electronic responsiveness of bio-oil molecules, polarizability serves as a predictive indicator of their interaction potential with asphalt components, providing a new dimension for evaluating the binder performance at the molecular scale. Among the tested materials, the biobinder derived from Haematococcus pluvialis demonstrated particularly strong improvements in resistance to permanent deformation under repeated loading conditions analogous to traffic-induced stress, as well as enhanced resistance to moisture-induced damage. In conclusion, these findings advance the chemistry-driven design of biomass-based binders and highlight a promising pathway toward the development of low-carbon, high-performance, and sustainable infrastructure materials.

Algae↗

An Overview of the Waste-to-Energy System Simulation (WESyS) Model

The leveraging of waste streams for energy and chemical production could add revenue to waste disposal operations, and it presents opportunities for addressing a variety of economic and environmental objectives at the local, state, and national levels. The Waste-to-Energy System Simulation (WESyS) model is a system dynamics model that was created to simulate the development of the U.S. waste-to-energy industry over time. For each of the three primary waste resources modeled (landfills, concentrated animal feeding operations, and publicly owned treatment works), WESyS simulates technically feasible scenarios for use of the waste, including direct conversion to fuels, and anaerobic digestion followed by flaring, electricity generation, combined heat and power, cleanup and compression to compressed natural gas, and cleanup and injection into an existing pipeline. The model allows users to explore numerous plausible future scenarios for the development of the U.S. waste-to-energy industry. This report provides an overview of the WESyS model and documents the key assumptions, equations, and data sources used to create the model.

09 BIOMASS FUELS↗