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DOE OSTI2023

Torrefaction of almond shell as a renewable reinforcing agent for plastics: techno-economic analyses and comparison to bioethanol process

Abstract In 2016, the US state of California alone produced nearly 3.5 billion kilograms of almonds, accounting for approximately 84% of the world’s almond production. This generated about 2.58 million metric tons (MTs) of almond residues. Almond shells are currently either burned to generate power or disposed of in landfill. Valorizing almond shells and hulls provides an opportunity to replace petroleum-derived products and divert organic material from landfill. Here we demonstrate a detailed techno-economic analysis (TEA) of an almond shell torrefaction process capable of utilizing the 520 000 MTs of almond shells produced annually in California. Our process also includes preprocessing the torrefied biomass to exploit it as a reinforcing agent for plastics. We further compared the revenue generated from the torrefied biomass and bioethanol derived from the same quantity of almond shells. We considered three different torrefaction facility scales to evaluate trade-offs between economies of scale at the facility and trucking costs to deliver almond shells. A facility that takes in 200 000 MT yr –1 of almond shells results in lower per-unit-output basis capital and operating cost relative to other smaller-scale torrefaction facilities, including 10 000 MT yr –1 and 50 000 MT yr –1 , considered for analysis in this study. The large-sale facility results in a minimum selling price (MSP) of the torrefied biomass of $311.4 MT –1 . An analogous TEA on converting almond residues into bioethanol is also investigated. The MSP of almond shell derived ethanol ($1.71 kg −1 ) is higher than that of corn ($0.48 kg −1 ) or cellulosic biomass ($0.88 kg −1 ) derived ethanol. Compared with the bioethanol route, the torrefied almond shells result in three times more revenue if utilized as a reinforcing agent for plastics.

Liu, Dupeng (ORCID:0000000269514064)↗

DOE OSTI2022

Hydrogen bond–induced aqueous-phase surface modification of nanocellulose and its mechanically strong composites

Aqueous-phase surface modification of nanocellulose is desirable because nanocellulose is generally produced via water-based fibrillation. In this study, a hydrogen bond–induced surface modification of cellulose nanofibrils (CNFs) in water was developed. Tannic acid and polyvinylpyrrolidone were chosen to modify the CNFs because of their strong capacity for hydrogen bond formation. By tuning the hydrogen bond formation between CNFs, tannic acid, and polyvinylpyrrolidone, CNFs with different surface hydrophilicity were achieved. Additionally, the modified CNFs can assemble into strong and tough composites owing to the hydrogen bond network in the system. Modified CNFs demonstrated 76% higher tensile strength and 100% higher toughness than those of unmodified CNFs, reaching 162 MPa and 12.7 MJ/m 3 , respectively. This study provides a new water-based modification strategy for the nanocellulose, leading the way toward producing strong nanocellulose composites via noncovalent interaction.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Co-expression of a β-d-xylosidase from Thermotoga maritima and a Family 10 xylanase from A. cellulolyticus significantly improves the xylan degrading activity of the Caldicellulosiruptor bescii exoproteome

Caldicellulosiruptor species are hyperthermophilic, Gram-positive, anaerobes and the most thermophilic cellulolytic bacteria so far described. They have been engineered to convert switchgrass to ethanol without pretreatment and represent a promising platform for the production of fuels, chemicals and materials from plant biomass. Xylooligomers such as xylobiose and xylotriose that result from the breakdown of plant biomass more strongly inhibit cellulase activity than do glucose or cellobiose. High concentrations of xylobiose and xylotriose, are present in C. bescii fermentations after 90 h incubation and removal or breakdown of these types of xylooligomers is crucial to achieve high conversion of plant biomass to product. In previous studies the addition of exogenous β-d-xylosidase substantially improved the performance of glucanases and xylanases in vitro. β-d-Xylosidases are, in fact, essential enzymes in commercial preparations for efficient deconstruction of plant biomass. In addition, the combination of xylanase and β-d-xylosidase is known to exhibit synergistic action on xylan degradation. In spite of its ability to grow efficiently on xylan substrates, no extracellular β-d-xylosidase was identified in the C. bescii genome. Here we report that the co-expression of a thermal stable β-d-xylosidase from Thermotoga maritima and a xylanase from Acidothermus cellulolyticus in a C. bescii strain containing the A. cellulolyticus E1 endoglucanase significantly increased the activity of the exoproteome as well as growth on xylan substrates. The combination of these enzymes also resulted in increased growth on crystalline cellulose in the presence of exogeneous xylan.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2022

Techno‐economic assessment of single‐stream feedstock logistics supply chain for corn stover and grain

Abstract The state‐of‐technology for corn stover harvest is a multi‐pass system that collects the stover after grain harvest. An alternative is a single‐stream system where the grain and stover are harvested as a bulk material co‐stored and preserved by anerobic fermentation, and finally, co‐transported to a biorefinery. In the present work, four single‐pass whole‐plant bulk systems were compared with a conventional multi‐pass bale system. The single‐stream systems consisted of the harvest of corn grain and a portion of the stover fraction. Four machine configurations were simulated. This work predicted that a multi‐pass bale system would result in a material cost of 111.80 $2021 Mg –1 stover DM delivered to the biorefinery gate. Alternatively, the lowest cost single‐stream system was the self‐propelled forage harvester (SPFH) configured with the whole‐plant header, which delivered feedstock for 74.76 $2021 Mg stover DM –1 . In addition to machine configuration, a sensitivity analysis was performed to understand important drivers of feedstock cost. These analyses revealed that feedstock cost increased with moisture content, fertilizer price, and biorefinery size, and decreased with harvest season length, crop yield, and grower participation. This work demonstrated that single‐stream systems could reduce corn stover feedstock costs in comparison with state‐of‐technology systems. © 2022 The Authors. Biofuels, Bioproducts and Biorefining published by Society of Industrial Chemistry and John Wiley & Sons Ltd.

09 BIOMASS FUELS↗

DOE OSTI2021

Experimental Plan for the Vermiculite Study

Homes in which vermiculite, which can contain asbestos, is present are often deferred under the DOE Weatherization Assistance Program (WAP) because of uncertainty in how to safely weatherize such homes from a client and worker perspective and the potential costs associated with alternative approaches. Recognizing this situation, the Department of Energy (DOE) tasked the Oak Ridge National Laboratory (ORNL) to perform a research project that scientifically identifies the asbestos exposure risks in weatherizing homes with existing vermiculite insulation. Current approaches being used by Grantees and Subgrantees to weatherize homes with existing vermiculite insulation were identified as part of the development of this experimental plan based on a review of Grantee Health and Safety Plans and communications with weatherization program staff from seven states. Other than deferral, these approaches include the following:1.) Abating (i.e., removing) the existing vermiculite using funding sources other than WAP (e.g., state funds, utility funds, the Zonolite Attic Insulation Trust Fund, and possibly homeowner contributions) because abatement is not allowed using WAP funds per Weatherization Program Notice (WPN) 17-7. 2.) Weatherizing the house as normal after testing reveals that the vermiculite contains less than 1% asbestos. 3.) Avoiding areas of the house where vermiculite is installed and weatherizing the remaining areas of the house as normal. 4.) Encapsulating the existing vermiculite insulation in an attic by blowing cellulose or other insulation over it. 5.) Weatherizing the areas of the house where vermiculite is installed using unique/alternative approaches developed specifically for that house. Blower door testing is also impacted by the presence of vermiculite due to the concern of bringing asbestos fibers into the space. Some states address this by performing pressurized blower door tests, whereas other states prohibit blower door testing entirely when vermiculite is present. This research project will focus on gathering data on home occupant and weatherization worker exposures to asbestos before, during, and/or after the weatherization of the homes containing vermiculite insulation using five of the six approaches identified above. Abatement of the existing vermiculite insulation will not be studied because it is not allowed using WAP funding per WPN 17-7 and, thus, is not a sustainable approach for WAP.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Enhancement of the Physical and Mechanical Properties of Cellulose Nanofibril-Reinforced Lignocellulosic Foams for Packaging and Building Applications

Biobased foams have the potential to serve as eco-friendly alternatives to petroleum-based foams, provided they achieve comparable thermomechanical and physical properties. We propose a facile approach to fabricate eco-friendly cellulose nanofibril (CNF)-reinforced thermomechanical pulp (TMP) fiber-based foams via an oven-drying process with thermal conductivity as low as 0.036 W/(m·K) at a 34.4 kg/m3 density. Acrodur®, iron chloride (FeCl3), and cationic polyacrylamide (CPAM) were used to improve the foam properties. Acrodur® did not have any significant effect on the foamability and density of the foams. Mechanical, thermal, cushioning, and water absorption properties of the foams were dependent on the density and interactions of the additives with the fibers. Due to their high density, foams with CPAM and FeCl3 at a 1% additive dosage had significantly higher compressive properties at the expense of slightly higher thermal conductivity. There was slight increase in compressive properties with the addition of Acrodur®. All additives improved the water stability of the foams, rendering them stable even after 24 h of water absorption.

Chemistry↗

DOE OSTI2021

Order-disorder in room-temperature ionic liquids probed via methyl quantum tunneling

Room-temperature ionic liquids are promising candidates for applications ranging from electrolytes for energy storage devices to lubricants for food and cellulose processing to compounds for pharmaceutics, biotransformation, and biopreservation. Due to the ion complexity, many room-temperature ionic liquids readily form amorphous phases upon cooling, even at modest rates. Here, we investigate two commonly studied imidazolium-based room-temperature ionic liquids, 1-ethyl-3-methylimidazolium tetrafluoroborate and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, as well as their mixtures, to demonstrate how the complex interplay between the crystalline and amorphous phases is affected by the processing conditions, such as thermal history, liquid mixing, and applied pressure. We show that quantum tunneling in the cation methyl groups, measured by high-resolution inelastic neutron scattering, can be used to probe the order-disorder in room-temperature ionic liquids (crystalline vs amorphous state) that develops as a result of variable processing conditions.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2022

Nth-plant scenario for forest resources and short rotation woody crops: Biorefineries and depots in the contiguous US

Estimating the US potential of woody material is of vital importance to ensure cost-effective supply logistics and develop a sustainable bioenergy and bioproducts industry. We analyzed a mature conversion technology for woody resources for the contiguous US that takes advantage of economies of scale: the nth-plant. Here, we developed a database to quantify the total accessible woody biomass within a distributed network of preprocessing depots and biorefineries considering both quality specifications for conversion and a target cost to compete with fossil fuels. We considered two categories of woody biomass: 1) forest residues from trees, tops and limbs produced from conventional thinning and timber harvesting operations as well as non-timber tree removal; and 2) short rotation woody crops such as poplar, willow, pine, and eucalyptus. A mixed integer linear programming model was developed to analyze scenarios with woody feedstock blends at variable biomass ash contents and cost targets at the biorefinery. When considering a target cost of 85.51 dollars/dry ton (2016$) at the biorefinery, the maximum accessible biomass from forest residues in 2040 remained constant at 106 million dry tons regardless of ash targets. Including short rotation woody crops as part of the blend increased the total accessible biomass to 153 and 195 million dry tons at ash targets of 1% and 1.75%, respectively. We concluded from our analysis that woody resources could address about 55% of EPA’s (Environmental Protection Agency) target of 16 billion gallons of cellulosic biofuel.

09 BIOMASS FUELS↗

DOE OSTI2023

Simple Bioparticle Filtration Device Based on an Ultralow-Fouling Zwitterionic Polyurethane Membrane for Rapid Large-Volume Separation of Plasma and Viruses from Whole Blood

Plasma separation from whole blood is oftent required as an essential first step when performing blood tests with a viral assay. However, developing a point-of-care plasma extraction device with a large output and high virus recovery remains a significant obstacle to the success of on-site viral load tests. Here, we report a portable, easy-to-use, cost-efficient, membrane-filtration-based plasma separation device that enables rapid large-volume plasma extraction from whole blood, designed for point-of-care virus assays. The plasma separation is realized by a low-fouling zwitterionic polyurethane-modified cellulose acetate (PCBU-CA) membrane. The zwitterionic coating on the cellulose acetate membrane can decrease surface protein adsorption by 60% and increase plasma permeation by 46% compared with a pristine membrane. The PCBU-CA membrane, with its ultralow-fouling properties, enables rapid plasma separation. The device can yield a total of 1.33 mL plasma from 10 mL whole blood in 10 min. The extracted plasma is cell-free and exhibits a low hemoglobin level. In addition, our device demonstrated a 57.8% T7 phage recovery in the separated plasma. The results of real-time polymerase chain reaction analysis confirmed that the nucleic acid amplification curve of the plasma extracted by our device is comparable to that obtained by centrifugation. With its high plasma yield and good phage recovery, our plasma separation device provides an excellent replacement for traditional plasma separation protocols for point-of-care virus assays and a broad spectrum of clinical tests.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Heterogeneous Catalysis by Fullerene C 60 : Photocatalytic Dehydro‐Dimerization of Primary Amines and Tetrahydroquinolines Studied Using Thread Spray Mass Spectrometry

Abstract Removal of a catalyst after a catalytic process is a time‐consuming and challenging process. In this paper, a fullerene catalyst coated on cellulose thread is developed and applied it in a heterogeneous photoreaction screening via a thread spray mass spectrometry (MS) platform. The surface of the cellulose thread is modified with NH 2 groups, which subsequently allows immobilization of fullerene C 60 on the thread. The final fullerene functionalized thread is placed in a glass capillary and the solution of the reactant to be interrogated is added. The assembly of thread and glass capillary is placed in front of a mass spectrometer, which serves as an online photoreaction platform after a light source and direct current high voltage are applied. As an ambient ionization approach, the photocatalytic reaction screening platform enabled real‐time MS characterization of products and intermediates and using only nanomole quantities of reactants. Fullerene C 60 is identified to facilitate dehydro‐dimerization reactions from amines. Norharmane shows a unique photo‐oxygenated dimer formation. The functionalized threads immobilized with fullerene C 60 are reusable, confirming the heterogeneous nature of the platform. Thus, this system provided real‐time screening of reactions catalyzed by fullerene C 60 and a means to investigate the reaction mechanism.

Chemistry↗

DOE OSTI2022

Multifunctional polymer composite coatings and adhesives by incorporating cellulose nanomaterials

Regardless of their applications, polymers are still considered mechanically weak and functionally insufficient for certain demanding coating and adhesive uses. To address those issues, nanomaterials have been extensively studied as reinforcing fillers, which have been proven to effectively promote the performance of polymer coatings/adhesives. However, conventional nanofillers are expensive and non-biodegradable. Meanwhile, cellulose nanomaterials (CNMs), a class of nanomaterials produced from biomass feedstocks, can circumvent the drawbacks of conventional nanofillers. Here, this review paper first focuses on the multi-functionalities CNMs bring to polymer coatings, including mechanical reinforcement (wear resistance and hardness enhancement), gas barrier, flame resistance, corrosion resistance, self-healing (controlled-release), optical regulation, self-cleaning/antifouling, and antimicrobial characteristics. Then we discuss the benefits of CNM addition to polymer adhesives, such as mechanical enhancement, curing promotion, volatile organic compound (VOC) suppression, and electrical conductivity. Finally, we provide insights into future research efforts with CNMs. The goal of this paper is to promote the pilot-scale study and commercial use of CNMs as multifunctional additives in green and sustainable polymer composite coating and adhesive formulations.

36 MATERIALS SCIENCE↗

DOE OSTI2025

High Performance (R-10/inch) Clay-Cellulose-Silica Nanopore Insulation Board For New and Retrofit Buildings (Final Scientific Report)

The objective of Liatris’s 3-year DOE BENEFIT project was to develop and validate a high-performance, lightweight, aerogel-based insulation board of ≥R-10/inch at a cost of ≤$\$$1.50 per board foot using non-flammable inorganic nanocomposites. We have summarized each yearly goal below: Year 1 – Ambient dried inorganic/organic nanocomposite, R-6/inch Year 2 – Processing efficiency and cost down, R-8/inch at $\$$2.0/board-ft Year 3 – Scale up to continuous, pilot production of R-10 at ≤ $\$$1.50/board-ft Over the course of the project period, Liatris has successfully met or exceeded all of the goals outlined above. The project scope over 3 years was extensive, covering method development of ambient dried silica aerogels in Budget Period 1, process formulation and R-value improvement in Budget Period 2, and composite scale up with corporate partners in Budget Period 3. Over the course of the project Liatris has been able to progressively improve the thermal resistance properties from about R-6/in to > R-11/in, 2-3X the performance of conventional insulation products.

36 MATERIALS SCIENCE↗

DOE OSTI2026

Technology Impact and Resource Assessment of Existing and Planned U.S. Biofuel Production: Life Cycle Water Consumption, Water Stress, Land Use, and Criteria Air Pollutants

Biofuels have the potential to strengthen the U.S. energy supply, enhance energy security, and promote economic development. As the United States continues to expand biofuel production, quantifying resource requirements and location-specific constraints is crucial for planning, siting, and technology development to support long-term viability. Accordingly, this work assesses the life cycle resource consumption (water consumption, and land use), water stress and criteria air pollutants associated with expanded U.S. biofuel production over the 2020–2035 period, based on producers’ plans. We perform a bottom-up technology impact assessment and resource assessment by integrating facility-level production statistics with Argonne’s Research and Development (R&D) GREET model and county-level water-stress characterization factors from Available Water Remaining for the United States (AWARE-US) model. Results suggest that by 2035, biofuels could meaningfully contribute to U.S. energy demand, driven primarily by first-generation and waste-based feedstocks with plans for substantial capacity expansion, although cellulosic and e-fuel technologies remain limited. However, growth must be managed to minimize impacts on water resources and land use. These impacts vary by fuel type and facility location, specifically, projected expansion increases water consumption and can elevate water-stress impacts in certain regions like Nebraska, Kansas, Colorado, Idaho, California and North Texas. Direct land use also increases overall, particularly for first-generation feedstocks such as corn and soybeans. These findings underscore the need for continued technological improvements and innovative strategies to manage resource demands as the industry scales and to support complementary deployment within the evolving U.S. energy system.

09 BIOMASS FUELS↗

DOE OSTI2024

Final Technical Report

The Department of Energy is interested in technologies that support the sustainable production of fuels, chemicals, and other bioproducts from plant biomass, to offset the nation’s reliance on fossil resources. The plant cell wall of energy crops provides the largest reservoir of raw materials for bioproducts. However, the widespread use of plant cell walls is hampered by their complexity and resistance to breakdown. To improve the productivity and cost-effectiveness of using energy crops to generate bioproducts, the fundamental problem of deconstructing plant cell walls must be addressed. This project developed and evaluated an innovative genetic modification technology to produce strategically designed enzymes that specifically accumulate in the plant cell wall. The resulting enzyme-engineered energy crops are expected to grow normally under natural conditions but break down more quickly and easily under high temperature during the production of biobased products. As such, this plant cell wall targeting enzyme engineering effort will reduce the cost of plant cell wall deconstruction and ultimately improve the economics of bioproducts. The overall objective of this project is to develop and evaluate the in-planta enzyme engineering technology to reduce lignocellulose deconstruction cost. The concept was first validated using tobacco plant, a model plant system that is typically used in lab testing for initial concept validation. Then the enzyme optimization was validated using switchgrass, the energy crop to be used to produce bioproducts. There are three specific objectives in this Phase I project: (1) validate the enzyme optimization concept using tobacco plant, a model plant system. (2) validate the enzyme optimization concept using switchgrass. (3) techno-economic analysis (TEA) for further scale-up application. By the end of this project, in-planta enzyme engineering was validated in both tobacco and switchgrass plants, with improved enzyme activity and saccharification efficiency. The in-planta enzyme engineering in Tabacco didn’t have a significant impact on plant growth and development. Transgenic tobacco plants with in-planta cellulose degrading enzymes showed higher biomass digestibility than wild type. Gene construction and transformation in switchgrass was much longer than expected, which delayed the research progress. Besides, in-planta engineering of lignin degrading enzyme is more challenging than cellulose degrading enzyme, in terms of expression detection. Expression of lignin degrading enzyme and cellulose degrading enzyme improved biomass yield and saccharification efficiency of switchgrass, respectively. It is promising to express both genes in switchgrass for optimized overall performance. According to the results of TEA, switchgrass biomass production cost is mainly attributed to by fertility and harvesting. Biomass production profit can increase up to 10-fold depending on biomass price. The PHA production profit is also sensitive to the biomass price. The proposed technology could potentially reduce the biomass deconstruction cost from 33% to 9% of PHA revenue, making the biomass-based PHA competitive to petroleum-based polymers even in case of relatively high biomass price of biomass. Therefore, cultivation of the genetically engineered self-deconstruction switchgrass for Polyhydroxyalkanoate (PHA) production could benefit switchgrass grower and PHA producer with attractive profits for both sectors. This new enzyme optimization approach will be beneficial for bioindustries that use energy crops as feedstocks. It will improve the economic viability of converting energy crops to renewable products that support a sustainable society and helps address the Nation’s long-term strategic needs for renewable products and reduction of reliance on fossil resources.

42 ENGINEERING↗

DOE OSTI2025

Comparison of Mechanical Properties of Lignin/High-Density Polyethylene (HDPE) Composites and Wood/HDPE Composites

Lignin is a plant-derived, the second most abundant natural polymer, and a waste byproduct of the pulp industry. Incorporation of lignin into plastic composites using scalable approaches is commercially favored and low carbon-cost. Potential end applications for lignin plastic composites (LPCs) could be found in buildings and furniture where wood plastic composites (WPCs) are used in various components. This study compares the mechanical properties of LPCs and WPCs, aiming at the examination of the viability of the use of LPCs as alternative materials to WPCs in the building industry. Sodium ligninsulfonate (SLS)-based LPC blended with high-density polyethylene (HDPE) (45 wt.%) and maleic anhydride grafted polyethylene (MAPE) as a compatibilizer (5 wt.%) reached flexural strength (35.17 and 30.92 MPa respectively) and moduli (2.87 and 1.79 GPa respectively) comparable to benchmarking WPCs. Lignin dealkaline (LD)-based LPC exhibited higher ultimate strain but lower strength than SLS-based LPC, probably due to fragmentation during the post-sulfite treatment steps.

cellulose and other wood products↗

DOE OSTI2022

Combustion dynamics of crude and upgraded Thermal DeOxygenation oils in a compression ignition engine

Thermal DeOxygenation (TDO) is a robust thermochemical conversion scheme to produce hydrocarbons from biomass feedstock. The process targets the carbohydrate fraction of biomass to yield a broad mixture of primarily aromatic hydrocarbons within a boiling point range of 348–798 K with low oxygen content (<4 wt%). The resulting materials are amenable to traditional hydrotreating and distillation processes with approximately 70% by mass in the distillate fuel range. The simple conversion scheme combined with commercially viable upgrading routes makes TDO oils a feasible alternative fuel for transportation applications. Here this paper is the first systematic treatment of fit-for-purpose testing of TDO oils in a compression ignition engine. Blends of partially upgraded TDO oils (e.g. whole oil, distilled oil, hydrotreated oil and hydrotreated-distilled oil) are prepared with certified ultra-low sulfur diesel at 5%, 10%, 15% and 20% by volume. The resulting fuels are analyzed for fuel characteristics and combustion dynamics in an instrumented single-cylinder compression ignition engine. All fuel blends at 10% blend level by volume exhibited adequate engine performance. Hydrotreating of the oils is a necessary step to meet cetane number and EPA soot emissions requirements at 20% blend volume. Combined distillation and hydrotreatment meet or exceed all fuel specification and engine performance benchmarks. Partially upgraded TDO oils are suitable fuel options for compression ignition applications.

42 ENGINEERING↗

DOE OSTI2026

Deacetylation and Mechanical Refining Pathway for the Bioconversion of Sugarcane Bagasse

Advancing lignocellulose biorefining is imperative for the deployment of cellulosic (2G) biofuels. This work investigates the tailoring of the alkaline deacetylation and mechanical refining (DMR) pathway for the bioconversion of sugarcane bagasse. Experiments are conducted at laboratory and pilot scales, varying the pretreatment conditions (70–92 °C; 48–100 g NaOH /kg) and the mechanical refining technologies (PFI and disk refining). The pretreatments selectively solubilize acetyl groups (> 86%) and lignin (10–63%) while mostly preserving structural carbohydrates in the solid phase. Enzymatic hydrolysis generates hydrolysates of clean sugars (glucose and xylose), with sugar yields increasing up to 81% for glucose and 89% for xylose in response to delignification and mechanical refining. Biochemical methane potential assays reveal specific methane productions of up to 568 NmL CH₄ gVS⁻¹ for alkaline liquor monodigestion and 344 NmL CH₄ gVS⁻¹ for co-digestion with sugarcane vinasse from the conventional (1G) sugarcane ethanol, indicating a strong potential for bioenergy recovery from this process stream. Synergies are identified in integrating 1G ethanol, 2G DMR processing of bagasse, and anaerobic co-digestion of 1G vinasse and 2G DMR alkaline liquor. This technology enables sugarcane biorefineries to enhance the co-production of ethanol, methane, and concentrated streams of CO 2 .

09 BIOMASS FUELS↗

DOE OSTI2022

Experimental-based mechanistic study and optimization of hydrothermal liquefaction of anaerobic digestates

Valorization of agricultural and food waste digestates is crucial for sustainable waste management to reduce environmental impacts and improve the economics of commercial farms. Hydrothermal liquefaction (HTL) of anaerobic digestates was evaluated to recover resources by converting them into carbon-dense biocrude oil and a nutrient-rich HTL aqueous phase (HTL-AP) coproduct. The effects of HTL temperature (280–360 °C), reaction time (10–50 min), feedstock pH (2.5–8.5), digestate salt content (1–5 wt%), and digestate cellulose-to-lignin ratio (0.2–1.8) on energy and nutrient recovery were systematically investigated in a set of well-designed experiments following a half-fractional central composite protocol. Response surface analysis combined with HTL product characterization and comparative literature study produced a comprehensive reaction pathway for HTL of anaerobic digestates. Moreover, this analysis revealed the importance of acidic feedstocks (pH 3.00–5.53), high reaction temperatures (337–360 °C), and reaction times <45 or 45–50 min for digestates with Cel/Lig >1 or <1, for maximizing the energy recovered in biocrude (high carbon yield and low heteroatom content) and the amounts of P, NH 3 –N, and Mg distributed in the HTL-AP. Acidic conditions catalyzed biocrude production, inhibited the Maillard reaction (lowering the nitrogen content in biocrude), and partitioned nutrients into the HTL-AP. Higher reaction temperatures coupled with longer reaction times activated hydro-denitrogenation and deoxygenation reactions to improve biocrude quality. Finally, this work provides not only validated methods to achieve targeted resource recovery for specific feedstock compositions using HTL, but also a comprehensive mechanistic understanding of the HTL of biomass waste for controlling target product characteristics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗