Fiber-reinforced polymers (FRPs) are critical for energy-relevant applications such as wind turbine blades. Despite this, the end-of-life options for FRPs are limited as they are permanently cross-linked thermosets. To enable the circularity of FRPs, we formulated a bio-derivable polyester covalently adaptable network (PECAN), sometimes referred to as a polyester vitrimer, to manufacture FRPs at >1 kg scale, which is accomplished as the resin is infusible (175-425 cP at 25 degrees C viscosity), can be cured at 80 degrees C within 5 h and is depolymerizable via methanolysis yielding high-quality fibers and recoverable hardener. The FRPs exhibit a transverse tensile modulus comparable with today's wind relevant FRPs (10.4-11.9 GPa). Modeling estimates a resin minimum selling price of $2.28/kg and, relative to an epoxy-amine resin, PECAN manufacture requires 19%-21% less supply chain energy and emits 33%-35% less greenhouse gas emissions. Overall, this study suggests that redesigned thermosets can yield beneficial circularity.

We investigate the potential to reduce costs and greenhouse gas emissions of the utilization of direct air capture of CO2 (DAC) for the production of algal biofuel. We examine four integrated designs for a DAC system comprised of solid amine monolith adsorbents delivering CO2 at the required level for algae cultivation with a photobioreactor (PBR)-based fuel production facility. We show that the integration of DAC with this biofuel production facility provides cost and greenhouse gas emissions benefits. Heat integration decreases operating expenses by reducing energy demand for heating requirements. Mass integration, utilizing flue gas CO2 as a carbon source for the PBRs, decreases the DAC system scale, resulting in both capital and operating cost savings. The most advantageous option depends on the interplay of heat and mass integration while matching the diurnal rhythm of algal growth with the inherently steady pace and energy requirements of the DAC system and fuel production. For these technologies, the DAC-PBR mass and energy integration provides an 18 % cost reduction and a 50 % reduction in greenhouse gas emissions for the current state of the technology.

This study presents the results of a preliminary assessment on the technology, economics, and sustainability of using waste plastics as a feedstock to produce low molecular weight olefins via pyrolysis and gasification pathways. We also studied the formation of formaldehyde – an important polymer precursor – via the gasification of waste plastics. Process pathways for recovery of ethylene and propylene and production of formaldehyde from a simulated mixed plastic waste were constructed based on literature data. They included direct and indirect pathways based on either gasification or pyrolysis as the primary conversion step. Results of these studies have shown that significant economic challenges exist of producing olefins via pyrolysis and gasification, with the latter pathway especially difficult. Base costs of pyrolysis naphtha from waste plastics are higher when compared to the same material produced from fossil feedstocks. Base olefin costs for one direct route are two times higher than comparable costs from steam cracking of fossil naphtha. These costs are driven primarily by feedstock costs; some pyrolysis scenarios become more economically feasible when very low feedstock costs are used. Similarly, for gasification, the cost of methanol – the central intermediate – was found to be noticeable higher when produced by gasification of waste plastics compared to current selling prices, which negatively impacts all pathways that go through methanol as the central intermediate. Life-cycle assessment indicates that the production of pyrolysis naphtha from plastics is a carbon intensive operation; no major advantages were found in terms of greenhouse gas emissions for any of the pathways producing C2 and C3 olefins. The results of this study can serve as the baseline for future comparison to other plastic waste valorization processes.

The 2021 state of technology (SOT) assessment for the indirect liquefaction (IDL) of lignocellulosic biomass to high-octane gasoline (HOG) via methanol and dimethyl ether (DME) intermediates details the techno-economic analysis (TEA) results and technical progress of the pathway since the 2020 SOT report. A detailed process description and collection of underlying assumptions is given the 2015 design report. In 2021, research efforts rigorously quantified the selectivity of DME to aromatic compounds. As a result, the overall carbon selectivity to hydrocarbon products was updated based upon new findings. Additionally, research conducted over the past few years resulted in successful lower temperature regeneration of NREL's Cu/BEA catalyst with favorable implications on catalyst longevity. Discussions with an engineering firm resulted in an update to the excess air requirement for process combustors (including the char combustor, tar reformer combustor, and catalyst regenerator) in which excess air was reduced from 20% excess to 10%. The cumulative effect of the above efforts was used to calculate a minimum fuel selling price for the modeled pathway. Sensitivity cases examining federal carbon tax credits from CO2 capture, product selectivity and yield, catalyst lifetime, and other key financial and process parameters were also considered in this assessment.

lignocellulosic biomass; (5) renewable diesel via HTL of a blend of algae and woody biomass; and (6) renewable diesel via combined algae processing (CAP). This technical report focuses on the environmental performance of these six biofuel production pathways in their 2018 SOT cases, as well as in their design cases (future target projections). The results of these renewable hydrocarbon fuel pathways in these SCSA analyses update those for the respective 2015 and 2016 SOT cases (Edward Frank et al. 2016; Hao Cai et al. 2016, 2017; Cai et al. 2018) in the case of IDL, algae CAP, and biochemical conversion pathways. They also provide an opportunity to examine the impact of technology improvements in both biomass feedstock production and biofuel production that have been achieved in 2018 SOTs on the sustainability performance of these renewable transportation fuels, and they reflect updates to Argonne National Laboratory's Greenhouse gases, Regulated Emissions, and Energy use in Transportation (GREET®) model, which was released in October 2018 (Wang et al. 2018). These GREET updates include production of natural gas, electricity, and petroleum-based fuels that can influence biofuels' supply chain greenhouse gas (GHG) (CO2, CH4, and N2O) emissions, water consumption and air pollutant emissions. GHG emissions, water consumption, and 2 nitrogen oxides (NOx) emissions are the main sustainability metrics assessed in this analysis. In this analysis, we define water consumption as the amount of water withdrawn from a freshwater source that is not returned (or returnable) to a freshwater source at the same level of quality. Life-cycle fossil energy consumption and net energy balance, which is the life-cycle fossil energy consumption deducted from the renewable biofuel energy produced, are also assessed.

We have been developing a three-step conversion of biomass-derived syngas to methanol to dimethyl-ether (DME) to non-aromatic hydrocarbons for use as high-octane gasoline and sustainable aviation fuel. This process produces branched alkanes from DME using a Cu/BEA catalyst and is a promising alternative to other syngas conversion processes such as Fischer-Tropsch to linear alkanes and traditional ZSM-5 catalyzed methanol to aromatic gasoline. In this short article we describe some advances in our understanding related to separation and purification via the use of more detailed experimental speciation in an updated process model involving multiple-phase equilibrium-based separation steps. The primary modeled reactor outlet constituents (and wt%) are: C3 and lighter hydrocarbon gases (11.1%), C4s (54.5%), H-2 (1.2%), CO2 (2.9%), water (5.0%), unreacted DME (16.5%), methanol (2.3%) and C5+ hydrocarbons (6.4%). Dimethyl-ether (the primary reactant) and H-2 recycling and reuse are important for the overall process efficiency, and the recycling of C4s is important to increase the C5+ yield via reactivation and homologation. Thus H-2, C4s and DME are targeted for recycling, while methanol and water need to be removed from the product to conform with fuel specifications. Model predictions from Aspen Plus using the NRTL-RK property method indicate a fuel composition with a C5+ content of 97.1 wt%, with the minor constituents 2.4 wt% C4s, 0.3 wt% methanol, 0.1 wt% DME, 0.03 wt% water and 0.01 wt% C3s. These ranges of minor components conform with fuel quality requirements, and the modeled product is amenable for unconstrained blending to boost gasoline octane ratings. (c) 2022 Society of Chemical Industry and John Wiley & Sons, Ltd.

This study assessed the long‐term annual biofuel production capacity potential and price in the United States and shed light on the prospect of biofuel adoption for marine propulsion. A linear programming model was developed to assist the projections and provide insightful analyses. The projected long‐term (2040) maximum annual capacity of biofuels in the United States is 245 million metric tons (Mt) or 65 billion gallons of heavy fuel oil gallon equivalent (HFOGE) when based on the median feedstock availability. Between 2022 (near‐term) and 2040, the potential biofuel capacity increases by over 40%, attributed to increased feedstock availability. At a price range up to $500/t, biodiesel is the main product, and the annual capacity (12 Mt) is limited to feedstock availability constraints. Biodiesel and corn ethanol are the main biofuels at a price range up to $750/t. At a higher price point (above $750/t), the biofuel types and annual capacities increase substantially (218 Mt per year). Biofuels above this price include gasoline‐, jet‐, and diesel‐range blendstocks, as well as bio‐methanol, bio‐propane, and biogas. This study concludes that the US domestic feedstock availability coupled with advanced conversion technologies can produce substantial amounts of biofuels to achieve a critical mass and be impactful as alternative marine fuels. There is also a need to improve the biofuel price for marine shipping adoption. Policies and economic incentives that provide temporary financial support would help facilitate maritime biofuel adoption. © 2022 Alliance for Sustainable Energy, LLC. Biofuels, Bioproducts and Biorefining published by Society of Industrial Chemistry and John Wiley & Sons Ltd.

Early stage research and development are needed to accelerate the introduction of advanced biofuel and engine technologies. Under the Co-Optima initiative, the U.S. Department of Energy is leveraging capabilities from its nine national laboratories and more than 35 university and industry partners including advanced computational tools, process design, data analysis, and economic and sustainability modeling tools to simultaneously design fuels and engines capable of running efficiently in an affordable, scalable, and sustainable way. In this work, we conducted techno-economic analysis (TEA) and life cycle assessment (LCA) to understand the cost, technology development, and environmental impacts of producing selected bioblendstocks for advanced engines such as multimode (MM) type engines at the commercial scale. We assessed 12 biofuel production pathways from renewable lignocellulosic biomass feedstocks using different conversion technologies (biochemical, thermochemical, or hybrid) to produce target co-optimized biofuels. TEA and LCA were used to evaluate 19 metrics across technology readiness, economic viability, and environmental impact and for each ranked on a set of criteria as favorable, neutral, unfavorable, or unknown. We found that most bioblendstocks presented in this study showed favorable economic metrics, while the technology readiness metrics were mostly neutral. The economic viability results showed potentially competitive target costs of less than $4 per gasoline gallon equivalent (GGE) for six candidates and less than $2.5/GGE for methanol. We identified 10 MM bioblendstock candidates with synergistic blending performance and with the potential to reduce greenhouse gas (GHG) emissions by 60% or more compared to petroleum -derived gasoline. The analysis presented here also provides insights into major economic and sustainability drivers of the production and of the feedstocks for each MM bioblendstock.

As fumigants face increasing regulatory restrictions, resistance, and consumer pushback, it is vital to expand the integrated pest management (IPM) chemical toolkit for stored products. The production of biomass derived insecticides (e.g., bio-oil fraction) from byproducts of biofuel production may be a promising alternative source of chemistries for controlling stored product insects. These potential insecticidal bio-oils were fractionated based on boiling points (ranging from 115 to 230°C in one series and 245-250°C in another). Fractions were analyzed using GC-MS, and were found to be unique in composition. The lethality of these fractions was tested on Tribolium castaneum, Tribolium confusum, and Oryzaephilus surinamensis (L.) (Coleoptera: Silvanidae). Fractions were tested at concentrations ranging from 5-260 mg/ml to screen for efficacy against adults for durations of 2-8 hr sprayed on concrete arenas. In addition, a separate assay evaluated adult emergence of larvae after 6 wk with supplemental food in arenas, while repellency was evaluated against four stored product insect species in a laminar wind tunnel. A greenhouse gas (GHG) emissions life cycle assessment was also performed, which found the use of the bio-oil fraction could reduce GHG emissions associated with the insecticide supply chain by 25-61% relative to a fossil-fuel based insecticide or pyrethroid. While adults were largely unaffected, we found that larval emergence was significantly suppressed compared to controls by roughly half or more. We also determined that there was minimal repellency to most fractions by most species. We conclude that the use of bio-oil fractions is a climate-friendly choice that may support IPM programs.

Biomass catalytic fast pyrolysis (CFP) research was funded by the Bioenergy Technologies Office (BETO) of the U.S. Department of Energy (DOE) to enable technical breakthroughs to help reduce the cost of conversion of biomass to liquid hydrocarbon fuels. The key goals were to achieve a mature plant modeled Minimum Fuel Selling Price of $3/GGE, with greater than 60% greenhouse gas (GHG) reduction over petroleum derived gasoline by 2022. Experimental results at NREL and PNNL, along with lifecycle analysis by ANL show that we achieved these goals based on performance at the bench scale. A Pt/TiO2 catalyst was used in a fixed bed reactor for upgrading pyrolysis vapors from an upstream fast pyrolysis reactor (ex-situ configuration) to produce CFP oil with 16.5% oxygen content. Subsequent co-hydrotreating of 10 vol% of CFP oil with 90 vol% straight run diesel (SRD) at the bench scale yielded greater than 95% carbon efficiency for the CFP oil portion of the feed. Light oxygenated coproducts were recovered from the off gases from the CFP process via adsorption and subsequent desorption. Aspen Plus modeling of purification of the desorbed stream using the UNIFAC property method showed that acetone and methyl-ethyl-ketone can be purified to chemicals grade and sold as coproducts to benefit the economics and reduce GHG emissions attributed to the fuel product. Some of the key risks and uncertainties associated with this process, and potential future work are mentioned in this report.

Global demand for methanol as both a chemical precursor and a fuel additive is rising. At the same time, numerous renewable methanol production pathways are under development, which, if commercialized, could provide significant environmental benefits over traditional methanol synthesis pathways. However, it is difficult to compare technologies at different maturity levels, with differing feedstocks, and with significant differences in overall process design. Thus, there is a need to harmonize the analyses of renewable pathways using a consistent techno-economic approach to evaluate the potential for commercialization of various pathways. This analysis uses a novel cross-comparison method to assess near-term and long-term viability of both low- and high-maturity level technologies. The techno-economic assessment considers cost factors critical to market acceptance combined with carbon- and energy-efficiency assessments of three renewable pathways compared with a commercial baseline. We find that biomass gasification to methanol represents a near-term viable pathway with a high technology readiness level and commercially competitive market price. If cost-reducing technological improvements can be realized and scaled up in the CO2 electrolysis pathways, the potential for higher carbon efficiencies may help drive market adoption of these more modular, direct conversion pathways in future markets as they present an opportunity to better support global decarbonization efforts through efficient waste carbon utilization.

This report was developed as part of the

Global demand for methanol as both a chemical precursor and a fuel additive is rising.At the same time, numerous renewable methanol production pathways are under development which, if commercialized, could present significant environmental benefits over traditional methanol synthesis pathways.There is a need to harmonize the analyses of renewable pathways using a consistent techno-economic approach to evaluate the potential for commercialization of various pathways.This analysis considers economic and environmental factors critical to market acceptance of three renewable pathways versus a commercial baseline.We suggest that biomass gasification to methanol represents a near-term viable pathway with high technology readiness level and commercially competitive market price.However, longterm solutions should consider CO2 electrolysis pathways which offer further improvements in sustainability metrics to support global decarbonization efforts.

The efficacy, economics, and sustainability of a bio-based insecticide produced from the catalytic fast pyrolysis of biomass is reported. This synergistic approach to fuels and agrochemical production can improve both energy and food sectors.

This technical report describes the SCSAs for the production of renewable hydrocarbon transportation fuels via a range of conversion technologies in the 2020 SOTs: (1) renewable high octane gasoline (HOG) via indirect liquefaction (IDL) of woody lignocellulosic biomass (note that the IDL pathway in this SCSA represents the syngas conversion design); (2) renewable gasoline (RG) and diesel (RD) blendstocks via ex situ catalytic fast pyrolysis of woody lignocellulosic biomass; (3) RD via hydrothermal liquefaction (HTL) of wet sludge from a wastewater treatment plant; (4) renewable hydrocarbon fuels via biochemical conversion of herbaceous lignocellulosic biomass; (5) renewable diesel via HTL of a blend of algae and woody biomass; and (6) renewable diesel via combined algae processing (CAP). This technical report focuses on the environmental performance of these six biofuel production pathways in their 2020 SOT cases. The results of these renewable hydrocarbon fuel pathways in these SCSA analyses update those for the respective 2019 SOT cases. They also provide an opportunity to examine the impact of technology improvements in both biomass feedstock production and biofuel production that have been achieved in 2020 SOTs on the sustainability performance of these renewable transportation fuels. The SCSA results also reflect updates to Argonne National Laboratory's Greenhouse gases, Regulated Emissions, and Energy use in Technologies (GREET®) model, which was released in October 2020. These GREET updates include the production of natural gas, electricity, and petroleum-based fuels that can influence biofuels' supply chain greenhouse gas (GHG) (CO2, CH4, and N2O) emissions, water consumption, and air pollutant emissions. GHG emissions, water consumption, and nitrogen oxides (NOx) emissions are the main sustainability metrics assessed in this analysis. In this analysis, we define water consumption as the amount of water withdrawn from a freshwater source that is not returned (or returnable) to a freshwater source at the same level of quality. Life-cycle fossil energy consumption and net energy balance, which is the life-cycle fossil energy consumption deducted from the renewable biofuel energy produced, are also assessed.

The report focuses on 2019 state of technology (SOT) updates to a 2018 SOT report, which presented research and techno-economic analysis updates of the detailed 2015 design report, along with sensitivity analysis showing the effect of key assumptions and parameters. Relevant developments in 2019 are presented here without repeating the bulk of the material included in the previous reports. The conversion pathway presented in this report includes the gasification of biomass, steam reforming and cleanup of the syngas, followed by the conversion of the syngas to high-octane gasoline (HOG) via methanol and dimethyl-ether (DME) intermediates. Key achievements in 2019 for the DME-to-HOG conversion step include increased DME conversion, while maintaining selectivity towards desirable C5+ hydrocarbon products, reduced aromatics formation, and an increased conversion of co-fed C4 to C5+ (in experiments conducted to simulate the recycle of C4 products).