Wood-to-Fuel for California's Transportation Sector using Autothermal Pyrolysis (Progress Report for FRD-17-002)
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The January 2021 progress report is provided, including planned and actual accomplishments for the period.
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We propose to continue to develop a new process for producing CO2-free hydrogen (H2) from inexpensive and domestically-abundant natural gas (NG), while simultaneously reducing H2’s net production cost to $1.0/kg through the sale of valuable crystalline solid carbon co-product. Producing clean hydrogen at this price is a DOE Hydrogen Energy Earthshot goal. Cost effective production of clean H2 is also of commercial relevance to project partners Southern California Gas Company (SoCalGas) and startup company C4-MCP, who aim to further develop, demonstrate at scale, and ultimately deploy the new process technology developed on this project in order to meet regulatory demands in the State of California. In the current project we have focused on i) understanding the catalyst science for thermocatalytic decomposition of methane (TCD), which resulted in the development of a patent pending bimetallic catalyst offering favorable activity, stability, and selectivity under industrially relevant process conditions, ii) developing a novel, patent pending process to enable the separation of produced carbon and catalyst, and re-synthesis of the catalyst using recycled materials, iii) performing limited characterization of the produced carbon materials, and iv) performing detailed process modeling in order to perform techno economic assessment. The additional scope proposed here will accelerate the commercial deployment of TCD for CO2-free H2 and valuable solid carbon nanotubes (CNT) co-product, by i) scaling up the production of CNT co-product using a scalable, fluidized bed reactor (25 g catalyst scale versus the 1 g catalyst scale demonstrated to-date), ii) producing at least 40 g of CNT product, produced via multiple cycles of TCD, carbon-catalyst separation, and catalyst re-synthesis, to enable the production of sufficient quantities of solid carbon so as to explore its market potential, iii) understanding the quality of the co-product CNTs, produced at larger scale, through advanced characterization, and iv) beginning to explore multiple promising high volume carbon product applications (thermoplastics, automotive composites, battery, and cement reinforcement applications).
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Volatile products from thermal decomposition of lignocellulosic biomass have been well characterized, but the solid- and liquid-phase reactions during the early stages of decomposition are largely unknown. Here the initial solid-phase biomass thermal deconstruction reactions were analyzed in situ and with high particle heating rates, delineating how these processes occur. A variety of instrumentation was used to quantify the extent and relative rates of deconstruction, demonstrating that biopolymers resist the thermally energetic conditions to differing degrees, even when ensconced in biomass cell walls. Hemicellulose and the more frangible lignin components decompose and volatilize more readily than cellulose, which temporarily enriches biomass with cellulose. These chemical changes manifest in larger cell wall structural and mechanical property transformations. In all, this investigation concludes that these solid-phase reactions strongly influence the production rates of volatile species and will require additional study before these processes can be modeled precisely to improve yields of desired product.
Volatile organic compounds (VOCs) are emitted from many sources, includingwildland fire. VOCs have received heightened emphasis due to such gases'influential role in the atmosphere, as well as possible health effects. Wehave used extractive infrared (IR) spectroscopy on recent prescribed burnsin longleaf pine stands and herein report the first detection of fivecompounds using this technique. The newly reported IR detections includenaphthalene, methyl nitrite, allene, acrolein and acetaldehyde. We discussthe approaches used for detection, particularly the software methods neededto fit the analyte and multiple (interfering) spectral components within theselected spectral micro-window(s). We also discuss the method's detectionlimits and related parameters such as spectral resolution.
Thermal reaction kinetics of pyrolytic products of proline, leucine, arginine and lysine in aqueous solution
Amino acid stability in pyrolyzed Pleistocene Mercenaria shells, comparing decomposition rates for aqueous solution