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DOE OSTI2025

2024 Case Study: Hydrothermal Liquefaction of Biomass Sources at a Wastewater Treatment Facility

A case study was developed for the fiscal year 2024 to examine the potential of wastewater-grown microalgae as a feedstock for hydrothermal liquefaction (HTL) to produce fuels and other products. In this year’s case study, scenarios are investigated in which the algae cultivation process is placed at different points within the water resource recovery facility (WRRF). Additionally, the supply of biomass for HTL is boosted by blending with wastewater solids collected at different locations within the WRRF.

09 BIOMASS FUELS↗
DOE OSTI2024

Development of a Sulfur Tolerant CHG Process (CRADA 442) (Final Report)

The Pacific Northwest Laboratory (PNNL) has developed the Catalytic Hydrothermal Gasification (CHG) technology, which can convert low-value organics dispersed in aqueous streams, such as the aqueous phase byproduct from hydrothermal liquefaction (HTL) of wet wastes, to a mixture of methane, H 2 , and CO 2 . The current CHG catalyst, ruthenium (Ru) on a graphite substrate, was selected for its effectiveness as a reducing catalyst. However, the target waste aqueous feedstock, the HTL aqueous phase from wet wastes, such as sewage sludge, contains a fair amount of sulfur in both organic and inorganic forms. Like many other reduced metal catalysts, Ru is deactivated or poisoned by exposure to sulfur, among other contaminants. In general, a deactivated Ru catalyst cannot be reactivated or restored except by removing and returning it for remanufacturing. Therefore, there is an urgent need for a sulfur-resistant catalyst to enable CHG processing of the HTL aqueous waste stream. PNNL, with support from SoCalGas CRADA, has developed a sulfur resistant CHG catalyst and demonstrated a stable CHG process for converting HTL aqueous phases from wet wastes. Here, we report the major accomplishments of the project: • We have demonstrated that sulfided Ru based catalysts is stable during CHG of HTL aqueous waste stream, with a requirement of activity improvement. • We have developed a new catalyst, with 0.5-2 wt.% Ru loading, showing better activity compared to the baseline 6.7 wt.% RuSx/C catalyst. • With the new catalysts, the single-pass COD reduction is approximately 60% and two-pass COD reduction can reach approximately 85%. • The process is robust in terms of being effective across a wide range of organic species in the feedstock. • Techno-economic analysis was conducted to evaluate the economic impact of catalyst advancement and identify further improvement requirements. This type of catalyst shows great potential to be efficient and robust for CHG with low catalyst cost.

03 NATURAL GAS↗
DOE OSTI2025

Whole Algae Hydrothermal Liquefaction and Upgrading: A review of progress and challenges and insight into the future

This report summarizes the research at Pacific Northwest National Laboratory (PNNL) to evaluate the economic viability and environmental impact of using microalgae to produce fuels and other products via hydrothermal liquefaction (HTL). Over the past several years, PNNL has examined key aspects of feedstock cost and availability, formatting and conversion techniques, and the utilization of all HTL products. Investigations of feedstock cost led to opportunities to work with cost-advantaged algal feedstocks that can be provided at minimal cost for HTL processing. Cost-advantaged algae include wastewater-grown algae and harvested algal blooms. Although farm-cultivated algae offer the best possible biomass composition and scalability for HTL processing, the cost of the feedstock is too high to yield an economically competitive biofuel. Processing cost-advantaged feedstocks creates other unique challenges in adapting HTL to upgrade biomass with higher than typical ash content and less preferred composition (low lipid). Despite the challenges, HTL of cost-advantaged algae results in economically competitive pricing scenarios and significant advantages in reducing net emissions below 70% of the petroleum baseline. The utilization of a variety of potential non-fuel products from algal HTL, such as the use of HTL solids as a cement additive, provides a significant reduction in net emissions by offsetting emissions from other carbon-intense products. This report presents an analysis of the research conducted at PNNL to develop an economically and environmentally beneficial process for algae HTL.

09 BIOMASS FUELS↗
DOE OSTI2024

Supporting data for Site-specific Design Case Study for Wet Waste Hydrothermal Liquefaction and Biocrude Upgrading to Hydrocarbon Fuels

Hydrothermal liquefaction (HTL) is a thermal process that converts wet biomass to renewable hydrocarbon fuel blendstocks (i.e., renewable naphtha, renewable diesel, and sustainable aviation fuel (SAF)). It can utilize a wide range of pure and blended wet feedstocks, including sewage sludge from water resource recovery facilities (WRRF), food and agriculture wastes, algae, fats, oils and greases (FOG) and blends of dry and wet wastes/feedstocks. Historically, techno-economic analysis (TEA) and annual state of technology (SOT) assessments with standard economic assumptions used by the Bioenergy Technologies Office (BETO) were conducted for the wet waste HTL pathway leveraging experimental data collected from Pacific Northwest National Laboratory’s (PNNL) continuous flow reactor systems. The objective of the SOT assessment has been to guide and track progress of BETO’s HTL research and development (R&D) toward reduced cost and greenhouse gas (GHG) emissions for the pathway. However, gaps exist between BETO’s traditional SOT updates and the needs of key external stakeholders that – if addressed – will accelerate technology adoption. This Business Case Study aims to bridge this gap by providing an updated design, TEA, and LCA based on PNNL’s FY23 R&D with added analyses and information that provide enhanced relevance for stakeholders of the HTL technology. This includes specific siting, regional wet waste resource inventory and transportation cost analyses, fuel market information, sustainable fuel policy impacts, economic metrics of net present value (NPV) and internal rate of return (IRR), greenhouse gas (GHG) emissions analysis, and statistical analysis of cost and technical uncertainties of the HTL plant design. The study focuses on the “Detroit combined statistical area (CSA)” region for siting of a wet waste HTL plant adjacent to the Great Lakes Water Authority (GLWA) facility with guidance from industry participants. Regional resource and siting analyses were conducted to identify feedstock availability, scale, and cost, as well as a beneficial site location. TEA with detailed rigorous capital cost estimation for the specific site application was conducted to evaluate the key economic metrics of most value to industrial partners. These include total capital investment, operating costs, minimum fuel selling price (MFSP) of the biocrude and fuel blendstock, and NPV and internal rate of return IRR with sustainable fuel credits. Life cycle analysis was conducted to evaluate the supply chain greenhouse gas (GHG) emissions for the wet waste HTL process as compared with petroleum derived diesel. This study is also informed by years of R&D and process de-risking learnings and was conducted with a basic engineering HTL plant design and costing that akin to a “first-of-a-kind” plant economics. This differs from our conventional “nth plant ” SOT assessments. Specifically, the HTL process model has been updated with more operationally reliable methods for feed heating and phase separations. Further, we have implemented additional spare equipment for redundancy, a more rigorous installed equipment cost estimation approach, and additional costs associated with feed formatting and delivery, building, piping and site development. An Excel-based cost sheet based on the basic engineering design is also released alongside the report that allows users to conduct customized TEA with their own feed composition and financial assumptions.

Li, Shuyun↗
DOE OSTI2021

Swell Behavior of Elastomers with a Hydrothermal Liquefaction Bio-Crude and a Fast Pyrolysis Bio-Oil

The compatibility of seventeen elastomer materials with two heavy biofuels (fast pyrolysis bio-oil and hydrothermal liquefaction (HTL) bio-crude) and diesel was assessed through volume change measurements. The elastomers included two fluorocarbons, six acrylonitrile rubbers (NBRs), and one each of fluorosilicone, neoprene, polyurethane, silicone, epichlorohydrin rubber (ECO), a blend of polyvinyl chloride and NBR (OZO), styrene butadiene rubber (SBR), hydrogenated NBR (HNBR) and ethylene propylene diene monomer (EPDM). The specimens were immersed in each test fuel for four weeks at 50°C and then measured for volume change. Afterwards, the specimens were dried, and the volume was remeasured. Ingeneral, the bio-oil produced unacceptable swelling in the fluoroelastomers, ECO, OZO, neoprene, polyurethane, SBR, HNBR, EPDM, silicone and five of the NBRs. In most cases, the HTL bio-crude produced lower (though still unacceptable) swelling than the bio-oil. Materials that showed good compatibility with the HTL biocrude were the fluoroelastomers, OZO, and silicone.

Kass, Michael↗
DOE OSTI2022

Hydrothermal liquefaction system

A hydrothermal liquefaction (HTL) system can comprise a biomass slurry source, a first pump in fluid communication with the slurry source and configured to pressurize a biomass slurry stream from the slurry source to a first pressure, a first heat exchanger in fluid communication with the first pump and configured to heat a slurry stream received from the first pump to a first temperature, a second pump in fluid communication with the first heat exchanger and configured to pressurize a slurry stream received from the first heat exchanger to a second pressure higher than the first pressure, a second heat exchanger in fluid communication with the second pump and configured to heat a slurry stream received from the second pump to a second temperature higher than the first temperature, and a HTL reactor configured to produce biocrude from a slurry stream received from the second heat exchanger.

Thorson, Michael R.↗
DOE OSTI2023

Hydrothermal liquefaction system

A hydrothermal liquefaction (HTL) system can comprise a biomass slurry source, a first pump in fluid communication with the slurry source and configured to pressurize a biomass slurry stream from the slurry source to a first pressure, a first heat exchanger in fluid communication with the first pump and configured to heat a slurry stream received from the first pump to a first temperature, a second pump in fluid communication with the first heat exchanger and configured to pressurize a slurry stream received from the first heat exchanger to a second pressure higher than the first pressure, a second heat exchanger in fluid communication with the second pump and configured to heat a slurry stream received from the second pump to a second temperature higher than the first temperature, and a HTL reactor configured to produce biocrude from a slurry stream received from the second heat exchanger.

Thorson, Michael R.↗
DOE OSTI2023

Biofuel Air Emissions Analysis

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

air quality↗
DOE OSTI2024

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

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

Kass, Michael↗
DOE OSTI2025

Extraction of Oil From Camelina Seeds Using Liquefied Dimethyl Ether

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

09 - BIOMASS FUELS↗
DOE OSTI2025

Harvesting Energy from Wastewater by Converting Sewage

This project aims were to develop and demonstrate a scalable, integrated process to convert sewage sludge into renewable natural gas (RNG), enabling wastewater treatment plants (WWTPs) to become net energy producers. The system proposal integrates autothermal hydrothermal liquefaction (AT-HTL), supercritical salt precipitation (SCSP), and hydrothermal gasification (HTG), collectively forming the Supercritical Sludge-to-Gas (SC-S2G) platform. Initially, batch hydrothermal liquefaction reactions were used to screen sewage sludge using AT-HTL (later termed RI-HTL) conversion to biocrude, aqueous and char phases compared to hydrothermal liquefaction (HTL). Significant improvement in biocrude yield using peroxide addition at O:C ratio of 0.05 and under conditions of 300°C for 10 minutes gave 57% biocrude yield and 85% fluid carbon yield (biocrude plus aqueous), while minimizing the loss of carbon to char solids (~7%). Hence, RI-HTL was shown to be effective for conversion of real sewage sludge. The corrosion of the alloy reactor tubes or vessels is an important factor when developing a process that includes an oxidant and a chemically complex feed like sewage sludge. We investigated the corrosion rates on metal alloys at 350°C for 240 hours. Corrosion rates of 0.21 and 0.26 mpy for 304L and 316L stainless steel were measured respectively. The corrosion information obtained in this investigation was utilized by PNNL for design, materials sourcing and construction of the pilot scale continuous flow system.

09 BIOMASS FUELS↗
DOE OSTI2025

Continuous Wet Air Oxidation of the Hydrothermal Liquefaction Aqueous Product from Various Wet Wastes

Wet air oxidation (WAO) offers an effective method for treating waste streams, converting pollutants into benign substances, and holds significant potential for processing the aqueous product from the hydrothermal liquefaction (HTL-AP) of wet wastes, a promising renewable fuel technology. Here, we conducted a comprehensive study of the WAO of HTL-AP from four different wet wastes. Through continuous testing under various conditions, we produced samples with different chemical oxygen demand (COD) levels, enhancing understanding of reaction parameters necessary for substantial COD reduction (>95%). Chemical analysis revealed that alcohols and ketones in the HTL-AP rapidly oxidized to acetic acid through aldehyde intermediates, while acetic acid, other carboxylic acids, and phenols oxidized relatively slowly. The light N-containing compounds were found to exhibit a change in concentration only after the whole sample reaches an 80% COD reduction, indicating their refractory nature under applied conditions. Energy released in the WAO reaction was calculated, and anaerobic toxicity assay demonstrated that WAO treatment enhanced methane production kinetics due to reduced inhibitory effects, suggesting partial oxidative transformation of inhibitory compounds into less toxic derivatives. These findings provide insights into designing effective WAO processes for valorizing HTL aqueous products, addressing key barriers to HTL process commercialization.

anaerobic digestion↗
DOE OSTI2020

Biopower: Impact of Biofuels Deployment to Replace Petroleum Liquids in Stationary Power Applications

Petroleum-based liquids are used in a portion of power generation applications in the United States, predominantly in the New England, Middle Atlantic, South Atlantic, and Pacific-Noncontiguous regions. Power plants that burn petroleum liquids, such as distillate or residual fuel oils, are generally used for short periods to accommodate peak electricity demands. The Energy Information Administration (EIA) estimated the U.S. consumption of petroleum liquids for electricity generation at 27 million barrels in 2018, representing a cost of $2.4 billion annually. This study assesses the potential to displace all or part of the petroleum liquids in U.S. power generation with biofuels. The biofuels for this application are assumed to be derived from terrestrial feedstocks, with conversion routes of both fast pyrolysis (bio-oil) and hydrothermal liquefaction (bio-crude). Regional models were used to assess the availability and cost of three different base materials: clean wood, forest residues, and corn stover; each was evaluated in the laboratory at small or experimental scales for conversion to bio-oil or bio-crude. The estimated biofuel production quantities depend on equivalent heating versus the current heavy fuel. In this report, the availability of each type of biomass for each section of the U.S. Census division is estimated using a conservative broker price (in each case) of $ 80 per dry tonne. The results show that the petroleum-liquid power generation in each of the Census Divisions could be supplied by one or more of the feedstocks evaluated. For all regions, clean wood supplies (only) could provide ample supply. For all but two regions (Middle Atlantic and New England), forest residues alone are sufficient. Finally, for all regions but three (Middle Atlantic, New England, and South Atlantic), corn stover alone is adequate. The Minimum Fuel Selling Price (MFSP) of bio-oil and bio-crude were also estimated for each feedstock type and Census Division. This analysis showed that fast pyrolysis bio-oil projections to be lower (14% on average) than current wholesale petroleum-based heating oil prices in each of the regions, assuming 100 dry tonnes/day processing capacity. However, bio-crude predictions were significantly higher (2X) in all cases. The effect of biorefinery size was also quantified. Based on the preliminary results in this study, it is apparent the biofuels could be an economical alternative for current petroleum liquids in U.S. power generation. However, additional research is needed to determine the necessary biofuel characteristics to support existing generation equipment. It is recommended that both power generation and biofuel production stakeholders to be engaged to outline the research and testing needed to identify the technical hurdles to enable the opportunity.

02 PETROLEUM↗
DOE OSTI2020

Balancing Water Sustainability and Productivity Objectives in Microalgae Cultivation: Siting Open Ponds by Considering Seasonal Water-Stress Impact Using AWARE-US

Microalgae have great potential as an energy crop. Scaling-up algal biofuel production in the United States (US) should be done with careful attention to water stress. This study evaluates the regional and seasonal water-stress impact of potential algae-pond deployments in the US. Three site-selection strategies focusing on biomass yield, water-use efficiency (WUE), and water-stress impact, respectively, are applied and compared to meet a US algae biomass production target of 30 million metric tons/yr ash-free dry weight, which converts to 20.8 billion L renewable diesel, via hydrothermal liquefaction. Ranking algae ponds based on biomass yield leads to freshwater consumption of 2.66 km3/yr, resulting in the highest water-stress impact (39.1 US equivalent km3). Under the WUE scenario, water consumption is reduced by 81%, but biomass yield is reduced by 12%. In contrast, adding a water-stress constraint to the biomass-yield ranking reduces water consumption by 50% and water-stress impact by 97%, with a small yield reduction (1.7%). Results show that pond location has a significant effect on water stress and that water stress is not proportional to water consumption or yield. Furthermore, capturing seasonal water patterns is critical for planning because sites in water-abundant regions can have short-term but significant water-stress impacts.

algae, Biofuel, water scarcity footprint, hydrothe↗
DOE OSTI2020

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

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

09 BIOMASS FUELS↗
DOE OSTI2020

Restoring Pre-Industrial CO2 Levels While Achieving Sustainable Development Goals

Unless humanity achieves United Nations Sustainable Development Goals (SDGs) by 2030 and restores the relatively stable climate of pre-industrial CO2 levels (as early as 2140), species extinctions, starvation, drought/floods, and violence will exacerbate mass migrations. This paper presents conceptual designs and techno-economic analyses to calculate sustainable limits for growing high-protein seafood and macroalgae-for-biofuel. We review the availability of wet solid waste and outline the mass balance of carbon and plant nutrients passing through a hydrothermal liquefaction process. The paper reviews the availability of dry solid waste and dry biomass for bioenergy with CO2 capture and storage (BECCS) while generating Allam Cycle electricity. Sufficient wet-waste biomass supports quickly building hydrothermal liquefaction facilities. Macroalgae-for-biofuel technology can be developed and straightforwardly implemented on SDG-achieving high protein seafood infrastructure. The analyses indicate a potential for (1) 0.5 billion tonnes/yr of seafood; (2) 20 million barrels/day of biofuel from solid waste; (3) more biocrude oil from macroalgae than current fossil oil; and (4) sequestration of 28 to 38 billion tonnes/yr of bio-CO2. Carbon dioxide removal (CDR) costs are between 25–33% of those for BECCS with pre-2019 technology or the projected cost of air-capture CDR.

54 ENVIRONMENTAL SCIENCES↗