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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↗

A novel chemical looping partial oxidation process for thermochemical conversion of biomass to syngas

The Biomass-to-Syngas (BTS) chemical looping process is an advanced thermochemical biomass conversion process for the production of sustainable fuels and chemicals. The BTS process is novel in that it converts biomass feedstock to high purity syngas with adjustable H 2 :CO molar ratio without needing an air separation unit (ASU), a tar reformer, a steam reformer, or a water-gas-shift (WGS) reactor. In the BTS process, biomass feedstock is partially oxidized to produce syngas by oxygen carriers in a reducer that is operated in a co-current gas-solid moving bed contact mode. The reduced oxygen carriers are regenerated in a fluidized bed combustor via the oxidation reaction with air. The BTS process uses the iron-titanium composite metal oxide (ITCMO) material as the oxygen carrier, which is capable of cracking the volatiles produced in biomass pyrolysis as well as regulating the syngas composition. The co-current moving bed reducer eliminates back-mixing, channeling, or bypassing of solid and gas reactants, resulting in a syngas composition that is close to the thermodynamic equilibrium. In this paper, the rationale of a successful BTS process is discussed along with the thermodynamic characteristics of the ITCMO oxygen carrier, that can effectively react with a woody biomass feedstock, analyzed based on an ASPEN Plus model. Bench scale moving bed reducer experiments are presented, indicating the conversion of wood pellets to syngas with a H 2 :CO ratio of 2, which is suitable for methanol or liquid fuel synthesis. The gas and solid composition produced in the bench scale reducer matches the prediction from the ASPEN Plus thermodynamic model. Furthermore, this model is further used to analyze the performance of the BTS process under autothermal conditions for methanol production, with a comparison with a baseline indirectly heated gasification process.

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↗

Chapter 11: Biochar Production

In production of biochar, thermochemical processes that can be used to treat biomass include pyrolysis, gasification, hydrothermal processing, and combustion. Each of these processes is defined by specific operating conditions (e.g., temperature, presence of oxygen) and feedstock requirements for optimal conversion to the product of primary interest. Each process results in varying fractions of gaseous, liquid, and solid products. Though other publications have emphasized the gaseous bio-energy products of such processes (e.g., bio-oil, synthesis gas or "syngas") with biochar as a co-product, in this discussion, we focus primarily on biochar as the In production of biochar, thermochemical processes that can be used to treat biomass include pyrolysis, gasification, hydrothermal processing, and combustion. Each of these processes is defined by specific operating conditions (e.g., temperature, presence of oxygen) and feedstock requirements for optimal conversion to the product of primary interest. Each process results in varying fractions of gaseous, liquid, and solid products. Though other publications have emphasized the gaseous bio-energy products of such processes (e.g., bio-oil, synthesis gas or "syngas") with biochar as a co-product, in this discussion, we focus primarily on biochar as the main product, with heat and electrical energy as co-products of secondary interest. The reasons for this are as follows: when producing biochar, heat is the simplest form of energy to capture and utilize, electrical energy can be generated from heat energy with a wide range of available technologies small and large; rather than immediately combusting the gases released from biomass, there is potential to refine the gases into bio-oil and syngas. However, much larger investments of capital are needed to build facilities for which gaseous fuel production is the primary goal, as compared to those focused on biochar production with heat and electrical energy co-products. While the economic viability of biochar production will be improved by production of high-value co-products (e.g., wood acids for use in pesticides), the simplest production scheme is one in which biochar and heat are the primary products. Here we aim to provide a broader overview of thermochemical processes and technologies most relevant to biochar production in its current state of commercialization. All biochar is a result of pyrolysis (the reaction) but not all biochar is made with a dedicated pyrolysis reactor (the technology type). Further, all biochar is the result of a lack of complete combustion (the reaction), even biochar produced in a combustion or gasification reactor (the technology type). This is an important distinction to acknowledge in the following sections in which we discuss both thermochemical conversion reactions and technology types.

biochar↗

Proctor and gamble technology process assessment for bioenergy production

P&G intends to replace as much as their current heat and power by renewable energy sources. For 2014, P&G’s total energy including electricity, natural gas and steam is approximately 1,540,000 MMBTU annually (Table 2). The biomass and wastes around P&G facility can be grouped into six categories (Figure 6): (1) Agriculture residue and grass, (2) Refuse (inorganic) solid material, (3) Food waste, (4) Organic waste stream, (5) livestock manure, (6) wastewater and sludge. The six feedstock sources can provide a total energy of 3,520,000 MMBTU per year (Table 10), among which the agriculture residue is the biggest fraction, about 67%, followed by livestock manures 27%. Therefore, the available energy sources around P&G facility are enough to meet their energy needs. These energy feedstocks would be treated by two processes: anaerobic digestion for biogas subsequently for heat and power and thermochemical process (combustion, pyrolysis and gasification) for heat and power (Figure 8 and 9). For AD, a one-stage complete mixing digester is preferable; and fluidized bed reactors are favorable for thermochemical process.

09 BIOMASS FUELS↗

Procter and Gamble Technology Process Assessment for Bioenergy Production

P&G intends to replace as much as their current heat and power by renewable energy sources. For 2014, P&G’s total energy including electricity, natural gas and steam is approximately 1,540,000 MMBTU annually (Table 2). The biomass and wastes around P&G facility can be grouped into six categories (Figure 6): (1) Agriculture residue and grass, (2) Refuse (inorganic) solid material, (3) Food waste, (4) Organic waste stream, (5) livestock manure, (6) wastewater and sludge. The six feedstock sources can provide a total energy of 3,520,000 MMBTU per year (Table 10), among which the agriculture residue is the biggest fraction, about 67%, followed by livestock manures 27%. Therefore, the available energy sources around P&G facility are enough to meet their energy needs. These energy feedstocks would be treated by two processes: anaerobic digestion for biogas subsequently for heat and power and thermochemical process (combustion, pyrolysis and gasification) for heat and power (Figure 8 and 9). For AD, a one-stage complete mixing digester is preferable; and fluidized bed reactors are favorable for thermochemical process.

09 BIOMASS FUELS↗

Analysis of Solar Receiver Performance for Chemical-Looping Integration With a Concentrating Solar Thermal System

This paper introduces a chemical-looping configuration integrated with a concentrating solar thermal (CST) system. The CST system uses an array of mirrors to focus sunlight, and the concentrated solar flux is applied onto a solar receiver to collect and convert solar energy into thermal energy. The thermal energy then drives a thermal power cycle for electricity generation or provides an energy source to chemical processes for material or fuel production. Considerable interest in CST has been driven by power generation with its capability to store thermal energy for continuous electricity supply or peak shaving. However, CST systems have other potential to convert solar energy into fuel or support thermochemical processes. The chemical-looping configuration integrated with the CST system can be a platform for implementing various solar-thermochemical processes. The chemical-looping configuration integrated with a CST system has potential applications for thermochemical energy storage and solar thermochemical hydrogen production. To use the solar energy efficiently and effectively, a high-temperature reactor receiver is a key component in the chemical-looping system. This paper shows a novel planar-cavity receiver design and its performance analyzed by solar-tracing and thermal-modeling methods for solar integration in a CST system.

14 SOLAR ENERGY↗

Production of sugars from lignocellulosic biomass via biochemical and thermochemical routes

Sugars are precursors to the majority of the world’s biofuels. Most of these come from sugar and starch crops, such as sugarcane and corn grain. Lignocellulosic sugars, although more challenging to extract from biomass, represent a large, untapped, opportunity. In response to the increasing attention to renewable energy, fuels, and chemicals, we review and compare two strategies for extracting sugars from lignocellulosic biomass: biochemical and thermochemical processing. Biochemical processing based on enzymatic hydrolysis has high sugar yield but is relatively slow. Thermochemical processing, which includes fast pyrolysis and solvent liquefaction, offers increased throughput and operability at the expense of low sugar yields.

Energy & Fuels↗

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↗

Investigation of Biomass Fouling on Screw Feeder in Preconversion of Pyrolysis

Biomass is a source of renewable energy and can undergo thermochemical processes to be converted into gaseous and liquid fuels. Thermal decomposition-induced biomass fouling on the screw feeder is a major challenge in preconversion of pyrolysis, leading to plugging of the feed line. Here, this work intends to gain fundamental understanding of the biomass fouling phenomena across the heat gradient on the screw feeder via a combination of materials characterization and thermal simulation. An actual screw feeder that failed because of biomass fouling was examined to reveal the deposit’s morphology, composition, and mechanical properties. Thermal simulations were developed for both the screw feeder and the wood particles being transported using a combined analytical and numerical approach. The simulated temperature profiles correlated well with the deposit observations, based on which potential mitigations were proposed from both the operation and screw design perspectives and supported by preliminary experimental validation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solar to fuels conversion technologies: a perspective

To meet increasing energy needs, while limiting greenhouse gas emissions over the coming decades, power capacity on a large scale will need to be provided from renewable sources, with solar expected to play a central role. While the focus to date has been on electricity generation via photovoltaic (PV) cells, electricity production currently accounts for only about one-third of total primary energy consumption. As a consequence, solar-to-fuel conversion will need to play an increasingly important role and, thereby, satisfy the need to replace high energy density fossil fuels with cleaner alternatives that remain easy to transport and store. The solar refinery concept, in which captured solar radiation provides energy in the form of heat, electricity or photons, used to convert the basic chemical feedstocks CO 2 and H 2 O into fuels, is reviewed as are the key conversion processes based on (1) combined PV and electrolysis, (2) photoelectrochemically driven electrolysis and (3) thermochemical processes, all focused on initially converting H 2 O and CO 2 to H 2 and CO. Recent advances, as well as remaining challenges, associated with solar-to-fuel conversion are discussed, as is the need for an intensive research and development effort to bring such processes to scale.

14 SOLAR ENERGY↗