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Herbaceous Feedstock 2021 State of Technology Report

The U.S. Department of Energy (DOE) promotes the production of advanced liquid transportation fuels from lignocellulosic biomass by funding fundamental and applied research that advances the State of Technology (SOT). As part of its involvement with this mission, Idaho National Laboratory (INL) completes an annual SOT report for biomass feedstock logistics. This report summarizes supply system impacts of Bioenergy Technologies Office (BETO)-funded research and development efforts at INL and INL collaboration with external partners (e.g. Forest Concepts, Purdue University ) that lead to improvements in feedstock supply systems. These include improvements to and observed performance of innovative harvest and collection methods, storage technologies, transportation and handling approaches, and advanced preprocessing technologies. Biomass quality and variability, and the interface between feedstock quality and conversion performance are key drivers in addition to delivered feedstock cost. In this report, we estimate the benefits of R&D technology improvements to individual supply system unit operations and present the status of feedstock logistics technology development for converting herbaceous biomass into biofuels. These analyses are supported by experimental data where possible and help to align the SOT relative to the cost goals defined in the Multi-Year Plan.

09 BIOMASS FUELS↗

Woody Feedstock 2022 State of Technology Report

The U.S. Department of Energy promotes production of advanced liquid transportation fuels from lignocellulosic biomass by funding fundamental and applied research that advances the state of technology (SOT). As part of its involvement in this mission, Idaho National Laboratory completes an annual SOT report for n th -plant and 1 st -plant woody biomass feedstock logistics. The purpose of the SOT is to provide the status of feedstock supply system technology development for woody biomass to biofuels relative to technical targets and cost goals from specific design cases, based on data and experimental results. Conventional feedstock supply systems need to be modified to meet the demands of conversion pathways, specifically to have the ability to adjust the quality of the raw biomass materials. Advanced systems incorporate innovative methods of material handling, preprocessing and supply chain configuration. In advanced designs, variability of the raw biomass can be reduced to produce feedstocks of a uniform format, moving toward biomass commoditization. Against this backdrop, the 2022 Woody SOT for low-ash woody feedstocks utilizes feedstock fractionation by incorporating technologies that can separate the biomass into its anatomical fractions (wood, bark, needle, and extrinsic ash) to reduce impurities and attempt to maximize the retention of usable fractions that satisfy downstream quality considerations. By using a series of air classification steps, this strategy can reduce the extrinsic ash in forest residues, separate out a majority of the incoming needles (which can be supplied to alternate markets), and maximize the retention of whitewood in the usable fraction. The fractionated forest residues are then mixed with clean-pine chips in a 50-50 blend to prepare the feedstock for the desired conversion pathway. The n th -plant analysis estimated the delivered cost for the feedstock at $\$$69.23/dry ton (2016$\$$) which represents a $\$$6.64/dry ton decrease compared to the cost estimate of the 2021 Woody SOT supply system for low-ash woody feedstocks. The quality requirements in the 2022 Woody SOT were identical to those of the 2021 Woody SOT at = 1.00 wt % ash and = 50.51 wt% carbon. The cost savings derive primarily from reductions in dry matter losses during air classification. The GHG emissions for the n th -plant analysis were estimated at 178.39 kg CO2e/dry ton compared to 178.71 kg CO 2 e/dry ton in the 2021 Woody SOT, a decrease of 0.32 kg CO2e/dry ton. The small change stems from an increase in emissions attributed to preprocessing and slightly larger savings in emissions from transportation. In the 1 st -plant analysis of the 2022 Woody SOT system, the average throughput was estimated to be approximately 2,128 dry tons/day or 96.51% of the name plate capacity. During the simulation the daily throughput ranged from 1,090 dry tons/day to 2,200 dry tons/day, or 49.43% to 99.75% of the daily nameplate capacity. After the year of operation 722,403 tons of processed feedstock were produced in total without regard to quality considerations (99.64% of the annual nameplate capacity). The variability in throughput was primarily caused by equipment failures in the system. Regular failures, downtime caused by routine maintenance per manufacturer guidelines, contributed to a majority 62.50% of failures and 62.60% of downtime. Failures due to wear were the other cause of disruption within the system, impacting the rotary shear and orbital screen and accounting for 37.50% of the failures and 37.40% of the total downtime. Ultimately the system was on stream for 87.84% during the simulation period, which is only 2.16 percentage points below the nth-plant assumption for on-stream time. The production cost of the system averaged $\$$71.66/dry ton. The costs ranged from a minimum of $\$$71.23/dry ton to a maximum of $\$$2,115.30/dry ton. When dry matter losses (disposed low-quality fractions as well as other losses such as in grinders) were considered the costs increased to an average of $\$$75.11/dry ton with a minimum of $\$$74.69/dry ton and a maximum of $\$$2,136.86/dry ton...

09 BIOMASS FUELS↗

Low-Cost Cellulosic Sugars Produced by NREL's Deacetylation and Mechanical Refining Process

The National Renewable Energy Laboratory has developed a deacetylation and mechanical refining (DMR) process that combines low-severity chemical pretreatment and mechanical refining to sidestep the expenses and challenges of traditional pretreatments, such as hydrothermal and dilute acid technologies. The DMR process is an important step in turning agricultural waste to sustainable aviation fuel.

biofuel↗

Design and Operation of a Multi-Bed Catalytic Micro-Reactor for the Study of Co-Processing of Bio-Oils with VGO

An industry wide shift from fossil-based fuel to renewable fuel sources including biomass, municipal waste, and plastics will require new process monitoring methods to minimize transitional risks including off specification product formation and catalyst deactivation. This project aims to provide a machine learning based process monitoring tool composed of online, slipstream mass spectra for use in biomass refineries and co-processing in existing refineries allowing operators to monitor product qualities and adjust process conditions accordingly. In order to maximize the robustness of the tool, large volumes of data must be collected to fine tune model parameters which consists of both micro and pilot scale mass spectral data. Micro-scale data is collected with a multi-tube micro-reactor housing up to six catalysts in horizontal beds, coupled with a molecular beam mass spectrometer. A pyrolizer equipped with an auto-sampler streamlines the micro-scale data collection process. This type of pyrolizer/micro-reactor configuration does not exist on the market, and therefore had to be created for the purposes of this project. The design and commissioning of this reactor will be presented in detail. This reactor set-up is highly flexible and increases throughput of analysis. For catalyst testing, each bed can be individually selected simply by turning valves. For catalyst reduction and regeneration, simultaneous flow through all six beds is used. The reproducibility of the system was first assessed with whole biomass pyrolysis along with pyrolysis of calibration standards. Initial work on this system evaluated two FCC catalysts, equilibrium catalyst (E-cat), and a proprietary catalyst from Johnson Matthey specifically design for co-processing of bio-oil with vacuum gas oil (VGO). This work used model compounds and VGO which illuminated differences in products produced by the catalysts.

biomass↗

Near-Critical CO 2 -Assisted Liquefaction-Extraction of Biomass and Wastes to Fuels and Value-Added Products

With the growing need for sustainable carbon-neutral liquid fuels, low-grade feedstocks, such as lignocellulosic biomass, and municipal solid wastes offer sufficient potential via thermochemical conversion. But the existing thermochemical means are limited in feed flexibility and scalability and require significant processing (energy and costs) of the intermediates. Bio-oil/biocrude intermediate from fast pyrolysis and hydrothermal techniques is impeded by issues of stability and oxygen content, along with hydrotreating viability. To address these issues, we investigated a novel pathway of near-critical CO 2 -assisted integrated liquefaction-extraction (NILE) technology in conceptual aspects for conversion of various biomass and municipal solid wastes into high-quality biocrude with high compatibility for co-hydrotreating with traditional fossil crude for liquid fuel needs in power and transportation sectors. Using supercritical CO 2 for dewatering wet feedstocks, for liquefaction, and extraction for lighter biocrude has produced biocrude with lower oxygen content by 50%, lowered metal content by 90%, stable viscosity, low acidity, and good aging stability compared to that produced from hydrothermal liquefaction along with higher hydrotreating and co-hydrotreating compatibility. Hydrotreating of the biocrude extract from supercritical CO 2 extraction also was feasible with no detected coke deposition, an oxygen content of 1%, and catalyst deactivation. Here, the validation and capabilities of the NILE concept urge for its further development to obtain sustainable liquid fuels with lower greenhouse gas emissions and costs.

09 BIOMASS FUELS↗

U-gas +Cool GTL™ - A New Integrated Process for Direct Biomass Conversion to Liquid Fuels

The U-Gas gasification technology, marketed by Sungas, is a proven fluid bed gasification technology for biomass conversion. U-Gas has been tested on a wide variety of biomass feeds including wood and waste streams. The U-Gas Technology has successfully converted wood for more than 20 years in a gasification plant in Skive Denmark at the 150t/d size. GTI has also recently developed the Cool GTL process for converting biogas to high quality gasoline, jet, and diesel fuels. The technoeconomics and LCA for the combination of the two technologies results an integrated optimized process, which will be discussed. The Cool GTL process is still in development and the development should be complete by 2023. Cool GTL converts high CO2 content feeds to synthesis gas with a 2-2.4/1 H2/CO ratio suitable for fuels synthesis. The process is based on a novel, highly stabile CO2/steam reforming catalyst. The 2.0-2.4/1 H2/CO synthesis gas ratio is always achieved, independently of feed CO2 content, by adjusting the amount of water added according to the amount of CO2 in the feed. The reformer catalyst has been tested for 500 hours and shows no measurable deactivation. The product from the reformer then goes directly to a low temperature slurry bed Fischer Tropsch reactor with an integrated finishing hydroisomerization reactor which makes hydrocarbon liquids from the synthesis gas. With this configuration no wax is produced. The technoeconomics and carbon intensity for the integration of UGas and the Cool GTL processes will be compared to other biomass conversion approaches. The use of electrolysis to boost H2 in the feed and increase liquid production will also be analyzed as a potential process improvement with sensitivities to the cost of electricity and the use of renewable electricity.

09 BIOMASS FUELS↗

Reducing Coke and Increasing Bio-Oil Yield during Catalytic Fast Pyrolysis of Biomass Using Phosphorus-Modified Zeolite Catalysts

Catalytic fast pyrolysis (CFP) is a promising strategy for producing hydrocarbon transportation fuels from biomass feedstocks. However, catalyst development is needed to increase bio-oil yields and enhance process economics. In this work, we demonstrate how post synthetic modification of formed ZSM-5 with phosphorus shifts CFP selectivity from coke and light gases toward the desired bio-oil product. Microscale experiments demonstrated reduced coke production relative to unmodified ZSM-5 and identified an optimal P loading. Extensive catalyst characterization revealed that P interacted with Al sites to reduce the acid site density, with preferential binding to the strongest acid sites. Insights from the microscale experiments were leveraged to produce kilogram quantities of formed P-ZSM-5 for evaluation in a larger semi-integrated process. These experiments generated liters of bio-oil that was hydrotreated and fractionated into gasoline, diesel, and jet cuts. The phosphorus-modified ZSM-5 improved CFP bio-oil yield, resulting in an 11% relative increase in the carbon yield from biomass to aviation fuel and a 14% decrease in the minimum fuel selling price. These results highlight the impact targeted changes in catalyst acidity, achieved by adding 2.5 wt % P, can have on the carbon efficiency and feasibility of fuel production from biomass feedstocks.

09 BIOMASS FUELS↗

Comparison of Select Food Waste Utilization Options

This document provides a comparison of several food waste utilization options: landfill gas capture, anaerobic digestion, and composting, across various metrics. These options are the most prevalent pathways for energy and resource recovery. Other options, not considered here, include food donation, animal feed, incineration, and gasification. The table below describes the differences or similarities between these processes and provides information about products, the number of current projects in the United States, capital and operation and maintenance (O&M) costs, job development potential, emissions, and incentives associated with each pathway, as well as other parameters, such as level of complexity, land requirement, and revenue type. Sources for the data in the table are listed in the references at the end of the document.

09 BIOMASS FUELS↗

Spatially Varying Costs of GHG Abatement with Alternative Cellulosic Feedstocks for Sustainable Aviation Fuels

Cellulosic biomass-based sustainable aviation fuels (SAFs) can be produced from various feedstocks. The breakeven price and carbon intensity of these feedstock-to-SAF pathways are likely to differ across feedstocks and across spatial locations due to differences in feedstock attributes, productivity, opportunity costs of land for feedstock production, soil carbon effects, and feedstock composition. We integrate feedstock to fuel supply chain economics and life-cycle carbon accounting using the same system boundary to quantify and compare the spatially varying greenhouse gas (GHG) intensities and costs of GHG abatement with SAFs derived from four feedstocks (switchgrass, miscanthus, energy sorghum, and corn stover) at 4 km resolution across the U.S. rainfed region. We show that the optimal feedstock for each location differs depending on whether the incentive is to lower breakeven price, carbon intensity, or cost of carbon abatement with biomass or to have high biomass production per unit land. The cost of abating GHG emissions with SAF ranges from $\$181$ Mg –1 CO 2 e to more than $\$444$ Mg –1 CO 2 e and is lowest with miscanthus in the Midwest, switchgrass in the south, and energy sorghum in a relatively small region in the Great Plains. While corn stover-based SAF has the lowest breakeven price per gallon, it has the highest cost of abatement due to its relatively high GHG intensity. Furthermore, our findings imply that different types of policies, such as volumetric targets, tax credits, and low carbon fuel standards, will differ in the mix of feedstocks they incentivize and locations where they are produced in the U.S. rainfed region.

09 BIOMASS FUELS↗

Opportunity Assessment for Sustainable Aviation Fuel Production from Woody Biomass via Ex Situ Catalytic Fast Pyrolysis and Refinery Hydroprocessing

Biofuels have become a promising solution to reduce emissions in hard-to-electrify transportation sectors, such as aviation. However, several biofuel conversion pathways will likely be needed to scale sustainable aviation fuel (SAF) production to meet lower carbon intensity goals when biomass feedstock availability constraints are considered. This study evaluates the future potential of the catalytic fast pyrolysis (CFP) pathway to contribute to U.S. SAF production goals as outlined in the U.S. Department of Energy’s (DOE) SAF Grand Challenge, understanding that the CFP pathway is still under development toward maturity and scaleup. National forestland resource data from the DOE’s 2023 Billion Ton Study are integrated with recent experimental results demonstrating end-to-end woody biomass conversion to SAF via CFP and hydroprocessing in a novel bioeconomy optimization framework. U.S. refinery hydroprocessing capacity is also considered with repurposing and coprocessing strategies. Results indicate that the CFP process can contribute up to 4.6 billion gallons of SAF annually by 2040, meeting 13% of the 2050 SAF Grand Challenge target while reducing the carbon intensity (CI) of the U.S. jet fuel pool by 16%. The study further explores optimal processing strategies, suggesting that colocating CFP operations with existing petroleum refineries and repurposing some U.S. hydrocracking capacity may offer significant cost advantages and enhance the commercial viability of the CFP pathway. These results underscore the CFP pathway’s potential to support the global aviation industry’s lower carbon intensity objectives while producing other renewable fuels and products.

09 BIOMASS FUELS↗

High-Biomass Sorghums as a Feedstock for Renewable Fuels and Chemicals

High-biomass sorghums are intended for use in biorefineries that convert vegetative biomass into renewable fuels and chemicals. The majority of plant biomass consists of cell walls, a complex matrix of cellulose, hemicellulosic polysaccharides and lignin. In the biorefinery, the biomass is ground and then subjected to a thermo-chemical pretreatment (elevated temperature, high pressure, chemical catalysts) that disrupts the cell wall matrix and solubilizes some of the cell wall polymers, followed by enzymatic saccharification of the cellulose, which produces D-glucose. The glucose and sometimes also the xylose derived from the hydrolysis of the hemicellulosic polysaccharides, are subsequently converted to fuels or other useful chemicals by microbial biocatalysts. The genetic improvement of high-biomass sorghums has as its ultimate goals to maximize the yield of fermentable sugars on a per-hectare basis, to minimize the inputs of fertilizer, irrigation, fungicides and pesticides and to reduce the environmental footprint. Breeding strategies thus need to target biomass yield, biomass composition, maturity, pest and disease resistance and nutrient use efficiency. Furthermore, this chapter reviews the genetic basis of these traits and their potential application in breeding programs.

60 APPLIED LIFE SCIENCES↗

Opening pathways for the conversion of woody biomass into sustainable aviation fuel via catalytic fast pyrolysis and hydrotreating

Meeting aggressive decarbonization targets set by the International Civil Aviation Organization (ICAO) will require the rapid development of technologies to produce sustainable aviation fuel (SAF). Catalytic fast pyrolysis (CFP) can support these efforts by opening pathways for the conversion of woody biomass into an upgraded biogenic oil that can be further processed to SAF and other fuels. However, the absence of end-to-end experimental data for the process leads to uncertainty in the yield, product quality, costs, and sustainability of the pathway. The research presented here serves to address these needs through a series of integrated experimental campaigns in which real biomass feedstocks are converted to a final SAF product using large bench-scale continuous reactor systems. For these campaigns, the degree of catalytic upgrading during CFP was varied to produce CFP-oils with oxygen contents of 17 and 20 wt% on a dry basis. The CFP-oils were then hydrotreated and distilled into gasoline, diesel, and SAF fractions. Detailed yield and compositional data were obtained for each step of the process to inform technoeconomic and lifecycle analyses, and the fuel properties of the SAF fraction were evaluated to provide first-of-its-kind insight into the quality of the final product. This research reveals opportunities to optimize process carbon efficiency by tuning the degree of catalytic upgrading during the CFP step and highlights routes to produce a high-quality cycloalkane-rich SAF with 85–92% reduction in greenhouse gas emissions compared to fossil-based pathways.

09 BIOMASS FUELS↗

Lignin Deoxygenation for the Production of Sustainable Aviation Fuel Blendstocks

Lignin is an abundant source of renewable aromatics that has long been targeted for valorization. Traditionally, the inherent heterogeneity and reactivity of lignin has relegated it to direct combustion, but its higher energy density compared with polysaccharides makes it an ideal candidate for biofuel production. This Review critically assesses lignin's potential as a substrate for sustainable aviation fuel blendstocks. Lignin can generate the necessary cyclic compounds for a fully renewable, sustainable aviation fuel when integrated with current paraffinic blends and can meet the current demand 2.5 times over. Using an energy-centric analysis, we show that lignin conversion technologies have the near-term potential to match the enthalpic yields of existing commercial sustainable aviation fuel production processes. Key factors influencing the viability of technologies for converting lignin to sustainable aviation fuel include lignin structure, delignification extent, depolymerization performance, and the development of stable and tunable deoxygenation catalysts.

09 BIOMASS FUELS↗

Converting polyisoprene rubbers into bio-jet fuels via a cascade hydropyrolysis and vapor-phase hydrogenation process

Producing alternative drop-in bio-jet fuels from biomass provides a promising approach to achieve carbon neutrality. Here, to upcycle biomass-based polyisoprene rubbers into jet-fuel range C 10 cycloalkane, we proposed a cascade hydropyrolysis and vapor-phase hydrogenation process in a flow-through two-stage pressurized fixed-bed reactor. The hydropyrolysis temperature in the first stage is of vital importance for the formation of primary limonene intermediate in the non-catalytic degradation of polyisoprene rubbers, and a reaction temperature of 460 °C maximized limonene yield to 588.6 mg/g for natural rubber and 546.2 mg/g for Eucommia rubber. Over a Pt/C catalyst loaded in the second stage, the limonene intermediate produced from the first-stage reactor can be completely hydrogenated, giving a 642.7 mg/g yield of jet-fuel range C 10 cycloalkane with 83.6% selectivity. The depolymerization mechanism of polyisoprene rubbers was thoroughly studied, and a competitive reaction between limonene hydrogenation and limonene dehydrogenation was observed. This is the first report on producing C 10 cycloalkane from natural rubbers via a cascade hydropyrolysis and hydrogenation process, providing a promising strategy to upcycle polyisoprene rubbers into bio-jet fuels.

30 DIRECT ENERGY CONVERSION↗

ZrO 2 /MWCNT as a Support Platform for Acid and Metal Catalysis in Water: The Investigation of Pd-WO x -ZrO 2 /MWCNT Catalysts (Final Technical Report)

This final technical report covers the final renewal period, 08/01/2019 to 07/31/2020, and the no cost extension 08/01/2020 to 07/31/2021, that was required because of the pandemic interruption. The proposed research was in the area of sustainable recovery of fuels and/or chemicals from biomass; it was by design intended to address fundamental science of the catalysts and that required using a model reaction. The model reaction molecule was phenol because it is a reasonably simply molecule that can be derived from lignin, and requires both hydrogenation and dehydration catalytic reactions that can be performed in water. The needed bifunctional catalyst can be provided by a metal for hydrogenation and by an acid (preferably Brønsted acid) for the dehydration function. Therefore, phenol conversion to an alkane in liquid water at a practical temperature, e.g., 200°C, that will not require extreme pressures, captures many of the complications of biomass derived fuels so it may reveal fundamental science that is relevant to development and implementation of biomass refining.

36 MATERIALS SCIENCE↗

Quantitative Determination of Biomass-derived Renewable Carbon in Fuels from Coprocessing of Bio-oils in Refinery Using a Stable Carbon Isotopic Approach

Increasing renewable carbon incorporation into conventional fuels through coprocessing with vacuum gas oil (VGO, a petroleum refining feedstock) is a critical step in biofuels development, scaling-up, adoption and associated GHG reduction. Optimization of the co-processing parameters maximizes incorporation of the renewable carbon in the fuel products. Quantitative determination of the renewable carbon content in the co-processed products provides direct evaluation of the parameters. The co-processing bio-oil with VGO through hydrocracking (HC) or fluid catalytic cracking (FCC) system resulted in carbon isotopic fractionation that prevented the direct use of the isotope mixing model for quantifying the renewable carbon. Here, we report an algorithm of using a stable carbon isotope approach to quantify the renewable carbon content in co-processing biofuel products through high-precision ?13C analysis. A controlled experiment carried out by blending a fossil diesel (-29.013‰) with a bio-diesel (-30.099‰) at various blending levels up to 98.0/2.0 wt% is presented and has demonstrated the applicability of this approach. The carbon isotope fractionation factors for the bio-oil co-processing were obtained by using a 14C-derived isotope-mixing model. The ?13C method was tested by co-processing 13C-labeled bio-crude and natural woody biomass-derived fast pyrolysis (FP) and catalytic fast pyrolysis (CFP) bio-oils with VGO. The results were verified by 14C accelerator mass spectrometry (AMS) method (ASTM-D6866) and compared with the yield mass balance (YMB) method. Strong agreement between d13C and 14C AMS methods demonstrated the applicability of the ?13C method to quantify renewable carbon content in co-processing fuel products and guide the co-processing optimization

Li, Zhenghua↗