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Results for “Hydrothermal carbonization”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records

Pretreatment of Biomass by Selected Type-III Deep Eutectic Solvents and Evaluation of the Pretreatment Effects on Hydrothermal Carbonization

Hydrothermal carbonization (HTC) is a novel thermochemical conversion that converts wet biomass into energy dense solid fuel. Residual moisture under subcritical conditions reacts with a lignin-cellulose-hemicellulose matrix with the major reactions being identified as dehydration and decarboxylation. Among other reaction parameters (e.g., temperature, time, pressure), biomass morphology often plays a key role in HTC. The hypothesis of this study was enhancing the porous structure of biomass without significantly affecting biopolymer composition would augment hydrothermal carbonization (HTC). To prove the hypothesis, two type-III deep eutectic solvents (DESs), namely choline chloride:urea (ChCl:Urea, 1:2 mol/mol) and methyltriphenylphosphonium bromide:ethylene glycol (MTPB:EG, 1:4 mol/mol), were studied to pretreat loblolly pine at room temperature and ambient pressure for 1 h. DES pretreatment shows swelling of the biomass, increasing the surface fiber-to-fiber gap length by 52% and 185% for ChCl:Urea and MPTB:EG pretreatments, respectively. The total pore volume remained intact (2.6 × 10 –3 cm 3 /g), although new small pores evolved, and existing pores were abated with DES pretreatment. Hydrochars prepared from DES pretreated loblolly pine showed a high O/C and H/C ratio resulting in a significant increase of energy content (up to 42%) and a decrease of mass yield (up to 50 wt %), indicating an enhancement of HTC severity due to the alteration of surface morphology by DES. Finally, a preliminary process economics revealed that integrated DES pretreatment-HTC would increase fixed capital investment but decrease the cost of operation and manufacturing than the standalone HTC process.

09 BIOMASS FUELS↗

Achieving high volumetric EDLC carbons via hydrothermal carbonization and cyclic activation

A novel activation method involving hydrothermal carbonization (HTC) and a pressure-induced low temperature oxidation has been demonstrated for cellulose derived HTC char by using hydrogen peroxide as an active di-oxygen source. The optimized porosity versus gravimetric capacitance results from cellulose derived HTC char synthesized at 220 °C. Almost homogeneous and small particle size micro-ellipse/sphere, relatively high surface area and narrow pore size distributions lead to a high bulk density, i.e. 0.73 g cm -3 , of coating type electrodes, which is much denser than those manufactured from steam activated carbons for supercapacitor industry, i.e., 0.52 g cm -3 . The resulting carbon prepared herein achieves a relatively high volumetric capacitance in an organic electrolyte-based supercapacitor reaching a competitive value of industrial system with the features of environment friendly, cost-effective as well as high yield, and less energy consumption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrocoals from waste biomass via catalytic hydrothermal carbonization processing

This study investigates how operating conditions (temperature and residence time) and benzoyl chloride impact hydrochar production from almond shells through hydrothermal carbonization. Carbon content rises while volatile matter decreases with increasing temperature, yielding a hydrochar with an estimated heating value of 28 MJ/kg. Elevated temperatures lower the O/C and H/C atomic ratios of hydrochars. Even at the lowest temperature under scrutiny, catalytic experiments using benzoyl chloride enhance carbonization and fuel ratio across all temperatures. Hydrochars produced through catalytic runs demonstrate elevated fuel ratios relative to those generated through noncatalytic runs, despite operating under the same conditions. These insights reveal the capacity of benzoyl chloride as a catalyst to improve hydrochar properties, suggesting its utility for advancing both the efficiency and effectiveness of hydrothermal carbonization processes.

09 BIOMASS FUELS↗

In-situ ATR-IR monitoring of hydrothermal carbonation of wollastonite

In-situ reaction monitoring allows for the development of reaction models for hydrothermal carbonation reactions, which have recently gained attention due to their importance in CO 2 sequestration and utilization. Here, we measured the carbonation kinetics of wollastonite (β- CaSiO 3 ) powder compacts under hydrothermal conditions (90°C and 2.4atm) with the help of optical fiber-based attenuated total reflectance infrared spectroscopy (ATR-IR). Further, the fiber probe was positioned at the target area to study the reaction chemistry at the desired region of the powder compact. Absorbances of solid reactants and products were monitored throughout the entire reaction in the 1000–1600cm -1 spectral range. ATR-IR enabled the detection of amorphous silica, which allowed all solid reactants (β-CaSiO 3 ) and products (CaCO 3 and SiO 2 ) to be monitored independently and simultaneously. A linear proportionality constant between absorbance and CaCO 3 phase concentration was determined and used to construct a reaction kinetics profile for carbonate formation, which revealed a rapid reaction onset, followed by two distinct slower decaying regimes.

42 ENGINEERING↗

Characterizing Reaction Space in the Continuous-Flow Esterification of Oleic Acid Using a Sulfonated Hydrothermal Carbon Catalyst

Continuous-flow catalytic esterification of free fatty acids (FFA) with methanol in the presence of sulfonated hydrothermal carbon (SHTC) as catalyst was studied. Using a Box-Behnken experimental design protocol, the effects of residence time, methanol:acid molar ratio, and water concentration on the conversion of oleic acid into methyl oleate were investigated. The optimum conditions for achieving esterification greater than 90 % at 100 °C were determined to be 11-minute residence time, a MeOH:FFA molar ratio >14.6 and up to 14.9 % water. The SHTC was used continuously for 4.5 days without a significant decrease in catalytic performance. The results confirmed that SHTC is an effective solid acid catalyst in a continuous flow system for the esterification of FFA.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A geochemical model for the formation of hydrothermal carbonates on Mars

It is often argued that substantially more carbon dioxide and water were degassed from the martian interior than can be found at present in the atmosphere, polar caps and regolith. Calculations have shown that atmospheric escape cannot account for all of the missing volatiles. Suggestions that carbon dioxide is stored as marine or lacustrine deposits, are challenged by Earth-based and spacecraft remote-sensing data. Moreover, recent modelling of the martian atmosphere suggests that rainfall or open bodies of water are in any case unlikely to have persisted for extended periods of time. Hydrothermal carbonates therefore provide a possible solution to this dilemma. Using an accessible terrestrial system (Iceland) as a guide to the underlying processes, and a host rock composition inferred from the least-altered martian meteorite, we present a geochemical model for the formation of carbonates in possible martian hydrothermal systems. Our results suggest that an extensive reservoir of carbonate minerals--equivalent to an atmospheric pressure of carbon dioxide of at least one bar--could have been sequestered beneath the surface by widespread hydrothermal activity in the martian past.

NASA Discipline Exobiology↗

Integration of Air Classification and Hydrothermal Carbonization to Enhance Energy Recovery of Corn Stover

Air classification (AC) is a cost-effective technology that separates the energy-dense light ash fraction (LAF) from the inorganic-rich high ash fraction (HAF) of corn stover. HAF could be upgraded into energy-dense solid fuel by hydrothermal carbonization (HTC). However, HTC is a high-temperature, high-pressure process, which requires additional energy to operate. In this study, three different scenarios (i.e., AC only, HTC only, and integrated AC–HTC) were investigated for the energy recovery of corn stover. AC was performed on corn stover at an 8 Hz fan speed, which yielded 84.4 wt. % LAF, 12.8 wt. % HAF, and 2.8 wt. % below screen particles. About 27 wt. % ash was reduced from LAF by the AC process. Furthermore, HTC was performed on raw corn stover and the HAF of corn stover at 200, 230, and 260 °C for 30 min. To evaluate energy recovery, solid products were characterized in terms of mass yield, ash yield, ultimate analysis, proximate analyses, and higher heating value (HHV). The results showed that the energy density was increased with the increase in HTC temperature, meanwhile the mass yield and ash yield were decreased with the increase in HTC temperature. Proximate analysis showed that fixed carbon increased 18 wt. % for original char and 27 wt. % for HAF char at 260 °C, compared to their respective feedstocks. Finally, the hydrochar resulting from HAF was mixed with LAF and pelletized at 180 bar and 90 °C to densify the energy content. An energy balance of the integrated AC–HTC process was performed, and the results shows that integrated AC with HTC performed at 230 °C resulted in an additional 800 MJ/ton of energy recovery compared to the AC-only scenario.

09 BIOMASS FUELS↗

U redox state tracked in mineralized hydrothermal carbonate with implications for U-Pb geochronology

U-Pb carbonate geochronology can directly constrain the timing and rates of important geological processes. However, the mechanisms and controls on U incorporation, distribution, and retention in carbonate minerals remain unclear, limiting geological interpretations. Here X-ray absorption spectroscopy (µXAS) and in-situ U-Pb carbonate geochronology are combined to temporally track U distribution and redox state in a porphyry-epithermal system. In this setting, multiple generations of carbonate minerals record fluid conditions and processes which control the solubility and deposition of metals, including U. This novel approach provides the first evidence of both oxidized UO 2 2+ and reduced U 4+ species in temporally distinct generations of carbonate within a single sample. Preservation of two different U oxidation states during discrete precipitation events requires U retentivity within older domains, demonstrating that the U-Pb carbonate geochronometer is robust under hydrothermal conditions. Furthermore, crystal zones with abundant fluid/vapour inclusions linked to boiling processes coincide with relatively high levels of U and favourable U/Pb. Targeting carbonate domains with these textures may therefore increase success in U-Pb geochronology. U-Pb carbonate dating combined with µXAS can track the temporal evolution of processes critical for metal deposition in long-lived and multistage hydrothermal-magmatic ore deposit settings.

58 GEOSCIENCES↗

Macroscale properties and atomic-scale mechanisms of ash removal in low-temperature hydrothermal carbonization

Biogenic ash is a significant impediment to the utilization of agricultural residues in biofuel production. Such challenge can be addressed by various treatments, as demonstrated in this study on the experimental and computational mechanisms involved in the hydrothermal treatment (HT) of wheat straw. A combination of classical (all-atom) molecular dynamics simulations of cellulose carrying silica and calcium species, along with first principles quantum chemical calculations, indicates the dissociation of inorganics from the cellulose with increased HT temperature. Here, this observation is confirmed by experimental evidence of effective ash removal by HT, showing at least 50% removal of sulfur, chlorine, potassium, and calcium, and 12.5% of silica, leading to a reduced total ash content (from 6.7% to 4.2%).Changes in structural features upon HT, such as surface cellular structure and porosity, were revealed, accompanied by an increased specific surface area (from 1.17 to 6.34 m 2 /g). Our simulations suggest that silica binds tightly to the hydrophobic face of cellulose at room temperature, but HT significantly reduces the binding free energy of association with both hydrophobic and hydrophilic surfaces. Most significantly, ash removal leads to an increased calorific value, rising from approximately 16 MJ/kg to about 19 MJ/kg, along with improved thermal behavior. The improved integration combustion index parameter S indicates that the combustion properties improve with ash removal efficiency. The proposed atomic-level mechanism for the observed removal of inorganics during mild HT underscores the potential of such treatment in producing energy-dense wheat straw, a widely available agricultural residue.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modeling Chemical and Isotopic Variations in Lab Formed Hydrothermal Carbonates

Chemical and mineralogical data (e.g. [1]) from Mars suggest that the history of liquid water on the planet was more sporadic in nature than long-lived. The non-equilibrium chemical and isotopic compositions of the carbonates preserved in the martian meteorite ALH84001 are direct evidence of ancient secondary minerals that have not undergone significant diagenesis or stabilization processes typical of long-lived aqueous systems on Earth. Thus secondary minerals and sediments on Mars may primarily record the characteristics of the aqueous environment in which they formed without being significantly overprinted by subsequent diagenetic processes during burial.

Niles, P. B.↗

Hydrothermally carbonized biomass formed via reactive twin-screw extrusion

A biomass-derived thermosetting polymer material being a product of processing a biomass feed material via a twin screw extruder having a length extending between an inlet and an outlet. Hot water from a water heater is injected into at least one inlet along the length of the twin screw extruder, the at least one inlet generally corresponding with a pressure boundary within the twin screw extruder. A pressure-sustaining valve is connected between the length of the twin screw extruder and the outlet, with the valve being adjusted to produce the biomass-derived thermosetting polymer material.

09 BIOMASS FUELS↗

Process and environmental safety of thermochemical conversion of biomass

Biomass presents a promising opportunity for converting waste into valuable energy, fuels, and chemicals through various thermochemical processes, including hydrothermal carbonization, hydrothermal liquefaction, pyrolysis, gasification, and combustion. However, these processes operate under extreme conditions, introducing significant safety hazards that necessitate meticulous management to prevent accidents. This review discusses potential hazards, risk mitigation strategies, and safety management practices, emphasizing the importance of integrated safety measures into the design and operation of these processes. It also highlights the critical need for robust safety engineering and environmental management strategies tailored to each thermo-chemical process. As these processes transition from laboratory to industrial scale, there is an imperative to develop a clear and concise pathway for emerging industries to achieve regulatory compliance, achieve safety certification, and enable effective stewardship of potential fugitive emissions. By addressing safety and environmental concerns, stakeholders can optimize economic benefits, rural development, and achieve sustained domestic energy generation benefits offered by biomass conversion technologies. Further research on plant design optimization, operational safety, environmental evaluation standardization, and innovative waste management solutions will support the safe and effective scaling of these technologies, ultimately contributing to sustainable management and resource recovery.

09 - BIOMASS FUELS↗

Opportunities and challenges in thermochemical conversion of municipal solid waste: A comprehensive review

Recent advancements in thermochemical conversion processes have elucidated new pathways for converting municipal solid waste into valuable resources. This review explores the primary thermochemical conversion methods, including combustion, gasification, pyrolysis, torrefaction, hydrothermal carbonization, and hydrothermal liquefaction, emphasizing their potential roles in waste management and energy recovery. Key challenges including feedstock variability, ash behavior, and scale-up limitations are discussed alongside opportunities for hybrid systems and circular economy integration. A comparative analysis of research publications indicates a significant focus on thermochemical pathways within the broader context of municipal solid waste research, underscoring the growing interest in these technologies. Recent advancements in each thermochemical process, alongside their operational, technical, and economic challenges, are discussed. Comparative data reveal that torrefaction enhances the hydrophobicity and grindability of municipal solid waste components, though its energy densification benefits are more modest than those observed in biomass. Hydrothermal carbonization and liquefaction are highlighted for their ability to process high-moisture and heterogeneous waste streams. The review also synthesizes recent findings on reactor configurations, emissions control, and synergistic effects in co-processing municipal solid waste fractions. The findings underscore the importance of developing standardized protocols for municipal solid waste characterization and the need for innovative hybrid systems to improve efficiency.

99 - GENERAL AND MISCELLANEOUS↗

Chemically Enabled CO 2 -Enhanced Oil Recovery in Multi-Porosity, Hydrothermally Altered Carbonates in the Southern Michigan Basin (Final Technical Report)

This is the Final Technical Report for the project "Chemically Enabled CO 2 -Enhanced Oil Recovery in Multi-Porosity, Hydrothermally Altered Carbonates in the Southern Michigan Basin." Over the course of six years of collaboration between Battelle and project partners, all stated objectives of the program have been completed, including full geological characterization of the TBR trend (See companion report for Task2), laboratory and modeling experiments to determine the optimum composition and design of CO 2 -EOR operations in the TBR trend, execution of a field test of chemically-enhanced CO 2 in a TBR well, and integration of the data and learnings gathered during these efforts into a full-trend development plan. Detailed reporting on these activities, their outcomes, and implications for trend-wide development is provided in the report. This report and encompassed data will provide TBR field operators with detailed information on what worked, what did not work, and how to proceed with production optimization of their TBR assets using chemically-enhanced CO 2 -EOR. CO 2 -EOR is a relatively well understood and broadly implemented strategy for increasing incremental production across the oil and gas industry, but its application has been primarily focused on reservoirs with limited heterogeneity. The intention of this project was show first that the same physical mechanisms that improve recovery factors in homogeneous reservoirs (namely wettability alteration, viscosity alteration, oil swelling, and mobility control) are at play in heterogeneous reservoirs. This was proven by the project’s laboratory studies and dynamic simulations, with the potential exception of mobility control, which needs further study. The second intention was to demonstrate via direct field testing that CO 2 -EOR can work in a strongly heterogeneous reservoir. While the field test strategy implemented during this project did not succeed in producing oil, data gathered during the test sheds light on what may work for field operators who try chemically-enhanced CO 2 -EOR within their own reservoirs, significantly reducing the level of uncertainty carried by first-of-a-kind commercial efforts that could (and should) follow this test. Simultaneously, the project has identified several large-volume ethanol plants and other sources of CO 2 emissions in the region and provided a handrail that CO 2 emitters and field operators can leverage to capture, transport, and inject that CO 2 into their fields. This project has also shown that, in many cases, the economics of CO 2 -EOR in the TBR are attractive. And finally, by completing a project of this scope in the southern Michigan Basin, the project has contributed to the knowledge base and operational experience of field operators, state regulatory agencies, local service companies, and state universities, with CO 2 -EOR projects which should allow follow-on projects to proceed safely and efficiently.

02 PETROLEUM↗