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DOE OSTI2021

Advancing Catalytic Fast Pyrolysis Through Integrated Experimentation and Multi-Scale Computational Modeling

This webinar will highlight recent results from a multi-disciplinary research effort in which integrated reaction testing was coupled with particle- and reactor-scale computational modeling to advance catalytic fast pyrolysis (CFP) for the production of renewable hydrocarbon fuels. Data will be presented from a series of ex situ CFP experiments in which a fixed bed of Pt/TiO2 was utilized with co-fed H2 to upgrade woody biomass pyrolysis vapors. Further discussion will include the application of these data towards the development of (1) a multiscale simulation framework to de-couple apparent kinetics from both intraparticle and reactor-scale transport phenomena and (2) a finite element computational model to understand and predict thermal excursions during catalyst regeneration. Throughout the presentation, the speakers will emphasize synergistic outcomes derived from the collaborative approach and highlight ongoing research efforts to accelerate technology maturation.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2025

Rheology and engine performance of very low sulfur fuel oil blended with 10% fast pyrolysis and hydrothermal liquefaction oils in a 2-stroke crosshead engine

The performance and emissions for a downscaled single-cylinder 2-stroke crosshead engine were determined for a very low sulfur fuel oil (VLSFO) when blended with 10 wt.% fast pyrolysis (FP) or hydrothermal liquefaction (HTL) bio-intermediates. The FP and HTL oils were derived from biomass and were observed to contain lower molecular weight (MW) hydrocarbons than neat VLSFO (which was evaluated as a baseline comparison). The addition of either biofuel reduced the overall viscosity of the VLSFO. Aging tests at 50, 90, and 120°C showed that the dynamic viscosity of VLSFO increased with exposure time up to two weeks. Similar trends were observed for the FP and HTL blends, but a pronounced spike in viscosity occurred for these fuels during the early period of exposure. None of the viscosity increases exceeded the operational limits of fuel system pumps. Engine performance studies were conducted under low, medium and high load operational settings. The relative performance of the test fuels was highly dependent on operating condition. In general, the engine results for the three test fuels were similar, but modest improvements in brake thermal efficiency and brake specific fuel consumption were observed, which may be attributed to the heightened reactivity of low molecular weight fraction of the FP and HTL oils.

09 BIOMASS FUELS↗
DOE OSTI2021

Catalytic Fast Pyrolysis for Chemicals: Cooperative Research and Development, CRADA Number CRD-16-00637 (Final Report)

The purpose of this partnership between the ExxonMobil Chemical Company and NREL is to advance the state of the art for converting biomass to liquid hydrocarbons using catalytic fast pyrolysis (CFP), with particular emphasis on directing and improving yields of such liquid hydrocarbons for uses in commodity chemical markets. CFP of biomass is a promising route for the production of renewable fuels and chemicals, and the key driver for economic viability is carbon yield to valuable products. The majority of prior CFP work has been targeted at fuel production, but this CRADA seeks to pursue routes to chemical co-products, thereby enhancing the overall economic viability of CFP. This project is beneficial to the public because it advances a technology that could one day provide renewable fuels and chemicals to our economy, thus improving the sustainability of our transportation and chemical manufacturing sectors.

09 BIOMASS FUELS↗
DOE OSTI2020

Operando S/TEM Reactions of Pt/TiO 2 Catalysts for Catalytic Fast Pyrolysis

Conversion of lignocellulosic biomass into the transportation fuel is an attractive concept. Using ex situ Catalytic Fast Pyrolysis (CFP) improves to upgrade bio-oils via catalytic deoxygenation of the biomass pyrolysis vapors. Zeolites are often used in this technique as the catalyst; however, in order to reduce minimum fuel selling price and improve carbon yields, ongoing research emphasizes catalyst optimization. By using bifunctional metal-acid catalysts and utilizing hydrogen, it is possible to improve carbon yields by minimizing the carbon-containing light gasses (since oxygen is removed aswater) and by reducing coke formation. Current research and development activities focuses on Pt/TiO 2 catalysts as the most promising catalyst candidates for the hydrodeoxygenation process. Here, our aim is to determine the structure-function relationships of the Pt/TiO 2 catalyst and the role of Pt dispersions within the catalyst on performance, using operando scanning transmission electron microscopy (S/TEM).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Techno-economic and life-cycle analysis of strategies for improving operability and biomass quality in catalytic fast pyrolysis of forest residues

Many of the challenges faced by the first commercial biorefineries were associated with feedstock handling, quality, and cost. Strategies are needed to enable further expansion of biorefineries and meet the growing demand for bio-based fuels and products. Here, we examine 2 key feedstock challenges and mitigation strategies in the context of a catalytic fast pyrolysis (CFP) biorefinery: (1) the operability of the feed system, which may be improved by modifying the minimum particle size fed to the reactor, and (2) the quality of the biomass, which may be improved by employing air classification to remove undesirable material and increase fuel yields. We conduct techno-economic analysis (TEA) and life-cycle analysis for these strategies, employing a discrete event simulation model for biomass preprocessing combined with a series of correlations developed from literature data and a rigorous CFP conversion model. Our results highlight the importance of balancing increased cost and material losses from preprocessing against improved operability and fuel yields. Economics and sustainability were optimized when operating at the lowest minimum particle size, emphasizing the importance of minimizing material losses while maintaining the operability of the process. Economically, additional costs and material losses from air classification could be acceptable due to improved biomass conversion, and an optimum air classification speed was identified; however, the fuel GHG emissions were minimized when air classification was not used. Valorizing material removed during preprocessing as a coproduct could improve economics and sustainability, decreasing the burden of material losses.

09 - BIOMASS FUELS↗
DOE OSTI2020

Separation of High Purity Oxygenated Aromatics from Catalytic Fast Pyrolysis Organic Streams

Thermochemical conversion of lignocellulosic biomass offers an attractive route to produce fuels and chemicals. Specifically, catalytic fast pyrolysis (CFP) oils have been shown to contain a high concentration of oxygenated aromatics, which can be isolated as value-added co-products. Purification of oxygenated aromatics can be a viable pathway to more economically competitive biorefineries, yet the isolation of highly pure coproduct streams remains technically challenging due to the high chemical heterogeneity of thermochemical process steams. Here, we demonstrate an industrially scalable process for isolating phenol, a widely used precursor to plastics, from CFP oil. Importantly, we leverage standard industrial processes, such as distillation, liquid-liquid extraction, and crystallization, to achieve phenol with 97% purity. In addition, the primary distillation of the CFP oil yielded several other fractions that contain chemicals with the potential to be isolated (e.g. cyclic ketones, cresols, and guaiacols). This work provides a technically feasible path to high purity oxygenated aromatics that has the potential to offset fuel production costs in a biorefinery.

09 BIOMASS FUELS↗
DOE OSTI2021

Deactivation by Potassium Accumulation on a Pt/TiO 2 Bifunctional Catalyst for Biomass Catalytic Fast Pyrolysis

Biomass-derived feedstocks bring significant challenges to the longevity of the catalysts used for their conversion, and alkali metals, for example, K, in the feedstock have been widely ascribed as one of the important factors causing catalyst deactivation. To address this challenge, it is critical to understand the mechanism of catalyst deactivation caused by K accumulation to guide the improvement of catalysts and processes and the development of catalyst regeneration strategies. In this work, we report a deep understanding of the impact of K on a bifunctional Pt/TiO 2 catalyst, which is an efficient catalyst for the ex situ catalytic fast pyrolysis of biomass. We simulated the K-poisoning of Pt/TiO 2 catalysts by purposely loading different amounts of K (100-6000 ppm by weight) on the catalysts. A series of characterization approaches, including scanning transmission electron microscopy, Fourier transform infrared spectroscopy, and chemical titration, were combined with a kinetic assessment of multiple probe reactions to elucidate the mechanism of Pt/TiO 2 deactivation by K accumulation. At low K loadings (<800 ppm), K preferentially poisons the strong Lewis acid sites, leading to significantly reduced activity for acid-catalyzed alcohol dehydration. However, acetone condensation is less sensitive to the poisoning of strong Lewis acid sites. Reactions that occur on Pt sites or at the metal-support interface, including alkene hydrogenation, m-cresol hydrodeoxygenation (HDO), and CO oxidation, were not impacted. At high K loadings (>800 ppm), K starts to accumulate on the Pt-TiO 2 interfacial area, poisoning the interfacial active sites for HDO and CO oxidation reactions. We further found that the poisoning of the Pt/TiO 2 catalyst by K is reversible, and water washing can successfully remove the accumulated K and recover the activities for both alcohol dehydration and m-cresol HDO reactions.

09 BIOMASS FUELS↗
DOE OSTI2021

A simplified integrated framework for predicting the economic impacts of feedstock variations in a catalytic fast pyrolysis conversion process

Feedstock attributes of lignocellulosic biomass, such as particle size, compositional makeup, and moisture content, can vary substantially even within pre-processed materials and have a significant effect on conversion in fast pyrolysis-based processes. However, the economic impacts of these attributes are not well understood. To address this, biomass deconstruction phenomena captured with a versatile particle-scale simulation were linked to techno-economic impacts via reduced-order models. Parametric analysis of the particle-scale model, which was validated using literature data, was used in combination with multiple linear regression models to develop correlations between feedstock attributes and yields of pyrolysis oil, gas, and char. Yields were then correlated with the minimum fuel selling price (MFSP) using a techno-economic model, bridging the gap between physics-based biomass conversion simulations and predictions of MFSP for a catalytic fast-pyrolysis process. Empirical correlations derived from the literature regarding the impact of mineral matter (ash) on oil yield were also considered. The model correlations deployed in the integrated framework capture the impacts of variation in feedstock attributes on the MFSP. Variations in ash were shown to have the biggest impact, varying MFSP by -13%/+22% due to catalytic effects and lower relative amounts of convertible lignocellulosic material. It was also found that, if ash can be controlled to low levels, the increased extractives in forest residues can help compensate for some yield losses associated with increased ash. As a result, other inputs considered (particle size, moisture content, and reactor temperature) had relatively negligible effects on process economics within the ranges analyzed considering particle-scale effects alone.

BIOMASS FUELS↗
DOE OSTI2020

Impacts of uncertain feedstock quality on the economic feasibility of fast pyrolysis biorefineries with blended feedstocks and decentralized preprocessing sites in the Southeastern United States

Abstract This study performs techno‐economic analysis and Monte Carlo simulations (MCS) to explore the effects that variations in biomass feedstock quality have on the economic feasibility of fast pyrolysis biorefineries using decentralized preprocessing sites (i.e., depots that produce pellets). Two biomass resources in the Southeastern United States, that is, pine residues and switchgrass, were examined as feedstocks. A scenario analysis was conducted for an array of different combinations, including different pellet ash control levels, feedstock blending ratios, different biorefinery capacities, and different biorefinery on‐stream capacities, followed by a comparison with the traditional centralized system. MCS results show that, with depot preprocessing, variations in the feedstock moisture and feedstock ash content can be significantly reduced compared with a traditional centralized system. For a biorefinery operating at 100% of its designed capacity, the minimum fuel selling price (MFSP) of the decentralized system is $3.97–$4.39 per gallon gasoline equivalent (GGE) based on the mean value across all scenarios, whereas the mean MFSP for the traditional centralized system was $3.79–$4.12/GGE. To understand the potential benefits of highly flowable pellets in decreasing biorefinery downtime due to feedstock handling and plugging problems, this study also compares the MFSP of the decentralized system at 90% of its designed capacity with a traditional system at 80%. The analysis illustrates that using low ash pellets mixed with switchgrass and pine residues generates a more competitive MFSP. Specifically, for a biorefinery designed for 2,000 oven dry metric ton per day, running a blended pellet made from 75% switchgrass and 25% pine residues with 2% ash level, and operating at 90% of designed capacity could make an MFSP between $4.49 and $4.71/GGE. In contrast, a traditional centralized biorefinery operating at 80% of designed capacity marks an MFSP between $4.72 and $5.28.

09 BIOMASS FUELS↗
DOE OSTI2022

Accelerating Catalyst Development for Biofuel Production through Multiscale Catalytic Fast Pyrolysis of Biomass over Mo2C

Advanced catalytic materials play an enabling role in producing renewable fuels and chemicals from biomass, thereby helping meet the global climate-change goals set forth by the Intergovernmental Panel on Climate Change. Herein, we present a multiscale approach to accelerate the catalyst-process development cycle for catalytic fast pyrolysis (CFP) of biomass over Mo2C. Mo2C has been shown to possess co-localized acidic and metallic sites and exhibit high activity for deoxygenation of biomass pyrolysis model compounds. However, critical knowledge gaps remain regarding the effectiveness of this catalyst for CFP of whole biomass. We address these knowledge gaps and demonstrate that Mo2C is effective at deoxygenating biomass-pyrolysis products in the presence of H2 but that it undergoes rapid selective and non-selective deactivation. The knowledge gaps addressed from this integrated study, targeting appropriate experiments across scales and feed types, enabled identification of critical modifications for advancing the CFP catalyst-process development cycle.

biofuels↗
DOE OSTI2024

Liquid–Liquid Equilibrium Prediction in Fast Pyrolysis Bio-Oil Systems: A Framework for Incorporating Bio-Oil Complexity

The study of mixtures of bio-oil, water and organic solvents in different proportions can serve as a cost-effective analysis of its content due to the formation of immiscible phases. This manuscript attempts to replicate experimentally determined partition coefficients (K OW ) of relevant species present in fast pyrolysis bio-oil (FPBO). A commercial flowsheeting simulator with surrogate bio-oil model representation is used. Concurrently, pyrolytic lignins in FPBO (‘pyrolignin’) do not have an agreed-upon structural representation, and the literature is ripe with wide variations of said representations. Thus, during the description of FPBO, this pyrolignin fraction was modeled using 20 possible structures (phenolic dimers to tetramers), with the goal of determining the structures for which the experimental data are best described. Two cases were considered: Case 1 normalized the reported experimental mass balance, while Case 2 included the unreported fraction in the mass balance to the total pyroligin. Please, add here a comment on the prediction of the Water oil equilibrium. The best KOW predictions for levoglucosan (LVG) were obtained when the system was modeled with no pyrolignin, presenting an MRE under 10% for both systems WO and BO. Among the possible structures, D2 (dimer), F1 (trimer) and I1, and I3 (tetramers) presented MRE ≤ 13% for both cases.

09 BIOMASS FUELS↗
DOE OSTI2022

Techno-Economic Analysis for Co-Processing Fast Pyrolysis Liquid in Fossil Refineries

Recent work at the National Renewable Energy Laboratory (NREL) and throughout the bioenergy community has highlighted incentives associated with co-processing bio-intermediates in existing refineries to reduce capital costs associated with renewable fuels and chemicals production and reduce overall risk for emerging biomass conversion technologies. This presentation summarizes the techno-economic analysis results from the NREL-Petrobras collaboration that focused on refinery integration of fast pyrolysis oil through co-processing in the fluid catalytic cracking (FCC) process. The NREL-Petrobras work highlights the economic opportunity for refiners to engage in co-processing for low-carbon products and introduces the risks for refiners based on variability in crude and fossil-product markets. The NREL-Petrobras results also serve as a basis to inform policy design that reduces economic risk for refinery co-processing and repurposing opportunities. The final topics in the presentation highlight experimental capabilities and emerging analysis approaches at NREL and partner laboratories that support the development and commercial deployment of refinery utilization strategies.

bio-fuels↗
DOE OSTI2021

Supply Chain Sustainability Analysis of Renewable Hydrocarbon Fuels via Indirect Liquefaction, Ex Situ Catalytic Fast Pyrolysis, Hydrothermal Liquefaction, Combined Algal Processing, and Biochemical Conversion: Update of the 2020 State-of-Technology Cases

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) (CO 2 , CH 4 , and N 2 O) emissions, water consumption, and air pollutant emissions. GHG emissions, water consumption, and nitrogen oxides (NO x ) 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.

09 BIOMASS FUELS↗
DOE OSTI2020

Supply Chain Sustainability Analysis of Renewable Hydrocarbon Fuels via Indirect Liquefaction, Ex Situ Catalytic Fast Pyrolysis, Hydrothermal Liquefaction, Combined Algal Processing, and Biochemical Conversion: Update of the 2019 State-of-Technology Cases

This technical report describes the supply chain sustainability analysis (SCSAs) for the production of renewable hydrocarbon transportation fuels via a range of conversion technologies: (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 in the 2019 SOT); (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 2019 SOT cases. The results of these renewable hydrocarbon fuel pathways in these SCSA analyses update those for the respective 2018 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 2019 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 2019. 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 (NO x ) 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.

09 BIOMASS FUELS↗
DOE OSTI2020

Dynamic Life-Cycle Analysis of Fast Pyrolysis Biorefineries: Impacts of Feedstock Moisture Content and Particle Size

The commercialization of biorefineries has been met with significant obstacles due to the technical difficulties of handling solid biomass feedstocks, which are highly variable in physical properties and chemical compositions. An understanding of the principles of unit operations along the supply chain is key to the success of the biofuel industry. This study applies a dynamic life-cycle analysis (DLCA) methodology by developing quantitative relationships between the inputs and outputs for each unit operation based on scientific understanding of the causal effects. Using the DLCA, we assessed system sustainability of drop-in fuel production from fast pyrolysis of pine residues followed by hydro-processing. Life-cycle greenhouse gas (GHG) emissions were calculated for 4641 runs involving two key feedstock parameters: moisture content after field drying and particle size of the feed to pyrolyzer. Moisture contents varied between 25% and 35%, while particle sizes varied between 0.5 and 5 mm in these runs. The life-cycle GHG emissions of these cases vary from 22 to 40 g/MJ. Close examination of each unit operation's contribution to the total GHG emissions reveals that low moisture content after field drying produces savings in energy consumption during feedstock transportation and on-site drying. However, although small particle size leads to overall higher fuel yield, it also requires a significant amount of energy for feedstock size reduction and fuel production. The energy penalty outweighs the benefit of increased fuel yields, especially when fine particles (<1 mm) are used for pyrolysis; thus, small particle size leads to increased GHG emissions overall. The results highlight the trade-offs between the energy demand for preprocessing and the conversion yields, which can be addressed with DLCA.

09 BIOMASS FUELS↗
DOE OSTI2021

Supply Chain Sustainability Analysis of Renewable Hydrocarbon Fuels via Indirect Liquefaction, Ex Situ Catalytic Fast Pyrolysis, Hydrothermal Liquefaction, Combined Algal Processing, and Biochemical Conversion: Update of the 2020 State-of-Technology Cases

The Department of Energy’s (DOE) Bioenergy Technologies Office (BETO) aims to develop and deploy technologies to transform renewable biomass resources into commercially viable, high-performance biofuels, bioproducts, and biopower through public and private partnerships (U.S. Department of Energy, 2016). BETO and its national laboratory teams conduct in-depth techno-economic assessments (TEA) of biomass feedstock supply and logistics and conversion technologies to produce biofuels. There are two general types of TEAs: A design case outlines a target case (future projection) for a particular biofuel pathway. It enables identification of data gaps and research and development needs and provides goals and benchmarks against which technology progress is assessed. A state of technology (SOT) analysis assesses progress within and across relevant technology areas based on actual results at current experimental scales relative to technical targets and cost goals from design cases, and includes technical, economic, and environmental criteria as available. In addition to developing a TEA for a pathway of interest, BETO also performs a supply chain sustainability analysis (SCSA). The SCSA takes the life-cycle analysis approach that BETO has been supporting for about 20 years. It enables BETO to identify energy consumption, environmental, and sustainability issues that may be associated with biofuel production. Approaches to mitigate these issues can then be developed. Additionally, the SCSA allows for comparison of energy and environmental impacts across biofuel pathways in BETO’s research and development portfolio. 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 [Harris et al. 2021]); (2) renewable gasoline (RG) and diesel (RD) blendstocks via ex situ catalytic fast pyrolysis of woody lignocellulosic biomass [Abhijit et al. 2021]; (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 (Davis et al. 2021; Lin et al. 2021); (5) renewable diesel via HTL of a blend of algae (Davis and Klein, 2021) and woody biomass (Hartley et al. 2020); and (6) renewable diesel via combined algae processing (CAP) (Wiatrowski and Davis, 2021). 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 (Cai et al. 2020). 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 (Wang et al. 2020). These GREET updates include the production of natural gas, electricity, and petroleum-based fuels that can influence biofuels’ supply chain greenhouse gas (GHG) (CO 2 , CH 4 , and N 2 O) emissions, water consumption, and air pollutant emissions. GHG emissions, water consumption, and nitrogen oxides (NO x ) 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.

09 BIOMASS FUELS↗
DOE OSTI2023

The effect of ferrous sulfate pretreatment on the optimal temperature for production of sugars during autothermal pyrolysis

Fast pyrolysis is a promising technology for producing cellulosic sugars from lignocellulosic biomass. Success in this endeavor requires measures that prevent naturally occurring alkali and alkaline earth metals (AAEM) from breaking pyranose and furanose rings in lignocellulosic biomass. This is especially critical for high ash feedstocks like corn stover and other kinds of herbaceous biomass. Pretreating corn stover with ferrous sulfate converts AAEM into thermally stable salts, which passivates the catalytic activity of these metals and dramatically improves sugar yields. AAEM passivation in combination with autothermal (partial oxidative) operation improves the prospects for intensifying the production of sugars via fast pyrolysis. We hypothesized that pretreated biomass pyrolyzed in the presence of oxygen can substantially influence the temperature dependence of pyrolysis kinetics. Here, we found that autothermal (air-blown) pyrolysis of ferrous sulfate pretreated corn stover achieved maximum sugar yield of 15.6 wt% (biomass basis) at 450 °C, whereas the maximum phenolic oil yield of 9.2 wt% (biomass basis) was reached at 500 °C. Considering these tradeoffs in yields of these highly desirable pyrolysis products, the ideal operating temperature is between 450 and 500 °C. These results suggest that two-stage pyrolysis might allow maximum recovery of both sugars and phenolic oil.

09 BIOMASS FUELS↗