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At least 19 records

Thermodynamic Limits of Redox-Based Thermochemical Processes (REDOTHERM)

Solar thermochemical fuel production is a potential pathway for the production of sustain liquid drop-in fuels, which can help decarbonize the aviation and maritime sectors. In an attempt to analyze the commercial viability of this technology, several studies have been conducted, including system and technoeconomic analysis (TEA) modeling. However, most studies to date simply assume a given redox reactor efficiency, which is significantly higher than demonstrated values to date. While it is widely recognized that utilizing a counter-current flow (CF) configuration could increase the redox reactor efficiency, an over-simplification in the thermodynamic modeling may lead to unphysical results which has been included in multiple publications. The fact that the solar redox reactor is the least developed component in the process chain makes it hard to identify technology gaps and evaluate pathways to deployment at scale using this approach. In this work, a thermodynamic model for a moving oxide system has been developed, in a general form that allows to analyze the system for different redox-active materials, under a wide range of operating conditions, for both parallel and countercurrent flows. The model capabilites are demonstrated, and the model's code will be shared as an open-source on GitHub in the next few months.

chemical looping

REDOTHERM: a thermodynamic modeling framework for redox-based thermochemical processes

Two-step thermochemical redox cycles are being developed as a potential pathway for the production of hydrogen and syngas. While there are many possible reactor and system configurations, moving oxide systems are considered promising in terms of the redox thermodynamics, due to the potential implementation of a countercurrent system that can achieve higher performance compared to other configurations. There is a lack of a robust thermodynamic modeling framework in the field, with multiple models incorporating incorrect thermodynamic assumptions that violate the second law of thermodynamics. We present in this work REDOTHERM, an open-source system model for moving oxides that incorporates the correct thermodynamic limits, as well as various options for the system auxiliary units including product separation, heat recovery, and oxygen removal. The model is agnostic to the energy source, and could be used for solar thermal or other configurations. We highlight the uses of this model, presenting some of the tradeoffs and challenges in redox-active material selection and how they affect the entire thermochemical hydrogen production process. This model could be easily adapted and used for material exploration, system/reactor design, and technoeconomic analysis.

08 HYDROGEN

Solar thermochemical process interface study

The design and analyses of a subsystem of a hydrogen production process are described. The process is based on solar driven thermochemical reactions. The subject subsystem receives sulfuric acid of 60% concentration at 100 C, 1 atm pressure. The acid is further concentrated, vaporized, and decomposed (at a rate of 122 g moles/sec H2SO4) into SO2, O2, and water. The produce stream is cooled to 100 C. Three subsystem options, each being driven by direct solar energy, were designed and analyzed. The results are compared with a prior study case in which solar energy was provided indirectly through a helium loop.

Source record

Thermochemical water decomposition processes

Thermochemical processes which lead to the production of hydrogen and oxygen from water without the consumption of any other material have a number of advantages when compared to other processes such as water electrolysis. It is possible to operate a sequence of chemical steps with net work requirements equal to zero at temperatures well below the temperature required for water dissociation in a single step. Various types of procedures are discussed, giving attention to halide processes, reverse Deacon processes, iron oxide and carbon oxide processes, and metal and alkali metal processes. Economical questions are also considered.

Chao, R. E.

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

Removal of Oxygen from Electronic Materials by Vapor-Phase Processes

Thermochemical analyses of equilibrium partial pressures over oxides with and without the presence of the respective element condensed phase, and hydrogen, chalcogens, hydrogen chalcogenides, and graphite are presented. Theoretical calculations are supplemented with experimental results on the rate of decomposition and/or sublimation/vaporization of the oxides under dynamic vacuum, and on the rate of reaction with hydrogen, graphite, and chalcogens. Procedures of removal of a number of oxides under different conditions are discussed.

Palosz, Witold

Effects of Impurities and Processing on Silicon Solar Cells, Phase 3

Results of the 14th quarterly report are presented for a program designed to assess the effects of impurities, thermochemical processes and any impurity process interactions on the performance of terrestrial silicon solar cells. The Phase 3 effort encompasses: (1) potential interactions between impurities and thermochemical processing of silicon; (2) impurity-cell performance relationships in n-base silicon; (3) effect of contaminants introduced during silicon production, refining or crystal growth on cell performance; (4) effects of nonuniform impurity distributions in large area silicon wafers; and (5) a preliminary study of the permanence of impurity effects in silicon solar cells.

Hopkins, R. H.

Development of a Light-Trapping, Planar-Cavity Receiver for Enclosed Solar Particle Heating

Concentrating solar thermal power (CSP) technology development has recently focused on high efficiency power cycles and chemical reactions that require high operating temperatures. An increase in receiver operating temperatures relative to current commercial CSP technology is necessary to support more efficient, high temperature power cycles or thermochemical processes. Solar receivers operating with heat transfer media temperatures >700 degrees C face various challenges including thermal performance, scalability, thermal-mechanical issues, and receiver service life. In addition, heat transfer media selection for high-temperature processes has been moving towards inert solid particles in Gen3 CSP, and reactive solid media and/or gases in solar thermochemical processes. To overcome the shortcomings and limitations of conventional designs for molten salt or particle receivers and receiver reactors, we introduce a unique light-trapping, planar cavity receiver (LTPCR) configuration and will present the current development progresses to demonstrate receiver feasibility through modeling, testing, and prototype demonstration.

ENGINEERING,SOLAR ENERGY

Prototype Development, Testing, and Modeling for a Solar Light-Trapping Planar-Cavity Particle Receiver (LTPCR)

Many applications for concentrating solar thermal power (CSP) technologies of high efficiency power cycles or thermochemical processes require higher operating temperatures and alternative heat transfer media. Inert solid particles for next-generation CSP and reactive gas and/or solid media for solar thermochemical processes are common options; however, these have significantly lower heat transfer capabilities than thermal oil, molten salt, or molten metal media. Conventional solar receivers operating temperatures >700 degrees Celsius face challenges including thermal performance and thermal-mechanical issues. To overcome these limitations, we have developed a novel light-trapping, planar-cavity receiver (LTPCR) that can heat solid-phase media within an enclosed receiver while maintaining a high aperture solar flux concentration for high efficiency. This paper presents progress on design, fabrication, and testing of a 100 kWt prototype receiver to demonstrate the LTPCR operability and its commercial feasibility.

14 SOLAR ENERGY

Prototype Development, Testing, and Modeling for a Solar Light-Trapping Planar-Cavity Particle Receiver

Many applications for concentrating solar thermal power (CSP) technologies of high efficiency power cycles or thermochemical processes require higher operating temperatures and alternative heat transfer media. Inert solid particles for next-generation CSP and reactive gas and/or solid media for solar thermochemical processes are common options; however, these have significantly lower heat transfer capabilities than thermal oil, molten salt, or molten metal media. Conventional solar receivers operating temperatures >700 degrees Celsius face challenges including thermal performance and thermal-mechanical issues. To overcome these limitations, we have developed a novel light-trapping, planar-cavity receiver (LTPCR) that can heat solid-phase media within an enclosed receiver while maintaining a high aperture solar flux concentration for high efficiency. This paper presents progress on design, fabrication, and testing of a 100 kWt prototype receiver to demonstrate the LTPCR operability and its commercial feasibility.

14 SOLAR ENERGY

Catalytic Upgrading of Pyrolysis Condensables from Postconsumer Polyolefins Using HZSM-5

The conversion of plastic wastes to monomeric olefins is an attractive means for achieving a plastic circular economy. In our study, a fluidized bed reactor converts post-consumer waste high-density polyethylene (HDPE) and polypropylene (PP) to mostly condensed pyrolysis waxes and some oils, preventing carbon loss to gases. The pyrolysis condensables were upgraded to light olefins (C 2 –C 5 ) at carbon yields greater than 76 wt % using the HZSM-5 zeolite catalyst at a post pyrolysis process that employed a micropyrolyzer. These results were comparable to olefin monomer yields from direct ex situ catalytic pyrolysis of the original waste plastics without condensing the vapors, highlighting the potential applicability of this approach in plastic waste recycling. Our results suggest that a centralized catalytic upgrading facility fed by pyrolysis condensables sourced from distributed thermochemical processing plants is a promising pathway to a circular economy. Such an approach enables utilization of available catalytic cracking infrastructure while focusing on setting up distributed thermochemical processing plants close to material recovery facilities. As a result, the energy-dense pyrolysis waxes are more suitable for transportation, contributing to the overall scalability and economic viability of the proposed distributed approach.

10 SYNTHETIC FUELS

Investigation of Flux Spreading in a Light-Trapping, Planar-Cavity Receiver for Enclosed Solar Particle Heating

Concentrating solar thermal power (CSP) technology development has recently focused on increasing the operating temperatures to accommodate high efficiency power cycles and thermochemical processes. Inert solid particles as heat transfer media enable solar receivers to operate above 700 degrees Celsius resulting in increased system thermal efficiency compared to the conventional molten salt based CSP system. An open-cavity falling-particle solar receiver that can efficiently heat particles by direct heating from concentrated solar radiation faces challenges with large particle losses from wind and unable to support thermochemical reactions. A light-trapping, planar cavity reiver (LTPCR) where particles are indirectly heated can significantly minimize the particle losses during the operation, support thermochemical reactions, and offer scalability potential. The LTPCR features an array of vertical planar receiver/absorber panels arranged within a cavity configuration. Concentrated solar radiation from heliostats is focused onto the receiver walls, where heat is indirectly transferred to solid particles flowing inside the receiver channels. Heat transfer occurs through direct contact between the receiver panel walls and particles, and can be enhanced by fluidizing particles with air. This fluidization increases particle-wall contact and extends particle residence time, maximizing heat transfer efficiency. The unique vertical planar receiver structure originated from a near-blackbody tubular light absorber, effectively distributing the incoming solar beam spread across the panel walls and trapping light. This flux spreading effect, driven by cosine projection, converts high incident solar flux into a lower, more uniform heat flux on the panel walls. This redistribution enhances heat transfer efficiency between particle-wall or reaction gases-wall, while preventing localized overheating of the receiver panel. Indirect planar cavity solar receivers completely separate solid particles from the ambient environment that can greatly reduce the thermal losses in heated particles resulting in high efficiency at high temperatures above 700 degrees Celsius. This design ensures no particle losses to the environment during the operation while open-cavity designs can experience significant particle losses from wind. An experimental investigation was conducted to observe flux spreading on the receiver panel wall. A lab-scale prototype planar receiver, fabricated using Haynes 230 alloy, was tested under direct concentrated solar radiation using the high-flux solar furnace (HFSF) facility at NREL. The experiment was performed under normal peak radiative heat fluxes ranging from 800 to 1900 kW/m2. A temperature distribution on the panel wall was measured using a thermal imaging camera (FLIR A 6600). To prevent overheating at the receiver front tip, prism-shaped heat shields (Zircar UNIFROM C1) were placed in front of the receiver, and their influence on flux spreading was also studied. Absorbed flux distribution on the panel wall was modeled using SolTrace. The total solar power and flux distributions delivered from HFSF were determined based on the heliostat mirror optical properties, direct normal irradiance (DNI) on the on-sun testing days, peak flux measurement during the on-sun testing, and shutter/attenuator settings Due to the large incident angles of the solar beam on the panel wall, the angular optical properties of Haynes 230 alloy and Zircar heat shields were incorporated into the model. This flux distribution model was then integrated into a computational fluid dynamics (CFD) simulation to predict the receiver panel wall temperature, which was compared with the experimental measurements. Both prediction and measurements identified a temperature hotspot at the backside of the panel, indicating that the incident solar beam can fully reach to the rear of the receiver. The heat shields positioned at the front of the receiver effectively reduced the excessive temperature rise at the receiver front tip. Overall, the temperature was well distributed over the panel wall, with a minor hotspot at the back of the receiver. The model slightly overpredicted the temperature, possibly due to discrepancies in optical properties of the panel and an underprediction of thermal loss in the receiver. The advancement of the particle LTPCR offers a viable alternative to open-cavity receivers by addressing particle loss issues. Additionally, it presents a pathway for enabling solar thermochemical processes, extending CSP technology beyond power generation to fuel and chemical production.

14 SOLAR ENERGY

Stage efficiency in the analysis of thermochemical water decomposition processes

The procedure for analyzing thermochemical water-splitting processes using the figure of merit is expanded to include individual stage efficiencies and loss coefficients. The use of these quantities to establish the thermodynamic insufficiencies of each stage is shown. A number of processes are used to illustrate these concepts and procedures and to demonstrate the facility with which process steps contributing most to the cycle efficiency are found. The procedure allows attention to be directed to those steps of the process where the greatest increase in total cycle efficiency can be obtained.

Conger, W. L.

Hydrogen as an energy vector

The feasibility of utilizing hydrogen as an energy vector is considered, with special attention given to means of hydrogen production. The state-of-the-art in thermochemical processes is reviewed, and criteria for the technical and economic feasibility of large-scale thermochemical water splitting processes are presented. The production of hydrogen from coal and from photolysis of water is discussed.

Powers, W. D.

Silicon Materials Task of the Low Cost Solar Array Project, Phase 3. Effect of Impurities and Processing on Silicon Solar Cells

The effects of impurities, various thermochemical processes, and any impurity process interactions on the performance of terrestrial silicon solar cells are defined. Determinations of the segregation coefficients of tungsten, tantalum, and cobalt for the Czochralski pulling of silicon single crystals are reported. Sensitive neutron activation analysis was used to determine the metal impurity content of the silicon while atomic absorption was used to measure the metal content of the residual liquid from which the doped crystals were grown. Gettering of Ti doped silicon wafers improved cell performance by one to two percent for the highest temperatures and longest times. The HCl is more effective than POCl3 treatments for deactivating Ti but POCl3 and HCl produced essentially identical results for Mo or Fe.

Hopkins, R. H.

Silicon materials task of the low-cost solar array project. Phase 4: Effects of impurities and processing on silicon solar cells

The effects of impurities, various thermochemical processes, and any impurity-process interactions upon the performance of terrestrial solar cells are defined. The results form a basis for silicon producers, wafer manufacturers, and cell fabricators to develop appropriate cost benefit relationships for the use of less pure, less costly solar grade silicon.

Hopkins, R. H.