Solution-processable porous graphitic carbon from bottom-up synthesis and low-temperature graphitization
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99 GENERAL AND MISCELLANEOUS↗
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Economic evaluation of infrastructures for thermochemical upcycling of post-consumer plastic waste
Thermochemical technologies, such as pyrolysis, offer a potentially scalable pathway for upcycling diverse types of plastic waste (PW) into value-added chemicals. However, deploying these technologies in waste management infrastructures is not straightforward because such systems involve a wide range of interdependent stakeholders, processing facilities, and products. In this work, we present a holistic optimization framework that integrates value-chain analysis, techno-economic analysis, and life-cycle analysis for investigating the economic viability and environmental benefits of upcycling infrastructures that collect, sort, clean, and process post-consumer PW for producing virgin polymer resins. The framework is applied to a case study in the upper Midwest region of the US. Our analysis reveals that the infrastructures are economically viable and could activate a regional circular economy that generates over 1 billion USD in annual profit. Moreover, our analysis reveals that this economy can reduce the carbon footprint of PW incineration by half. Our framework also determines the inherent values of post-consumer PW and of derived products such as plastic bales and pyrolysis oil; we find that, in these infrastructures, PW becomes a highly valuable feedstock with a market value of 500 USD per tonne. Here, we discuss how this market value can generate incentives that foster more effective waste pre-sorting practices by consumers that can help bypass material recycling facilities and increase total system profit.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Electrocatalytic Hydrotreatment of Bio-Oil: Exploring Interactions Between Functional Groups
Electrocatalytic hydrotreatment (ECH) is being explored as a sustainable route for upgrading bio-oil to renewable fuels and chemicals. Bio-oil, produced by the fast pyrolysis of lignocellulosic biomass, is a complex mixture of compounds with various oxygen-containing functional groups, such as anhydrosugars, carboxylic acids, ketones, aldehydes, furans, phenols and alcohols. The ECH of several bio-oil model compound binary mixtures was conducted to investigate the interactions between these functional groups. Notably, phenolic compound reduction was significantly inhibited in the presence of aldehydes, particularly furfural. A strategy involving the reagent-based reduction of the aldehyde to an alcohol prior to ECH was shown to partially mitigate this inhibitory effect. Additionally, qualitative studies on the ECH of catalytic fast pyrolysis (CFP) oil with low aldehyde content showed promising results. These studies achieved the conversion of cyclopentenones and phenolic compounds present in the CFP oil to cyclopentanols and cyclohexanols, respectively.
09 BIOMASS FUELS↗
Direct measurement of fluorocarbon radicals in the thermal destruction of perfluorohexanoic acid using photoionization mass spectrometry
Thermal destruction is a critical cornerstone of addressing the rampant contamination of natural resources with per- and polyfluoroalkyl substances (PFAS). However, grave concerns associated with stack emissions from incineration exist because mechanistic studies have thus far relied on ex situ analyses of end products and theoretical calculations. Here, we used synchrotron-based vacuum ultraviolet photoionization mass spectrometry to study the pyrolysis of a representative PFAS-perfluorohexanoic acid-and provide direct evidence of fluorocarbon radicals and intermediates. A key reaction pathway from perfluorocarboxylic acids to ketenes via acyl fluorides is proposed. We furthermore propose CF2/CF3 radical-centered pyrolysis mechanisms and explain their roles in the formation of other products that may form in full-scale incinerators. These results have not only unveiled the role of radicals and intermediates in thermal PFAS decomposition and recombination mechanisms but also provide unique insight into improving the safety and viability of industrial PFAS incineration.
Xu, Ming-Gao↗
A computational fluid dynamics model to estimate local quantities in firebrand char oxidation
Firebrand burning is a complex phenomenon that is influenced by several parameters which are difficult to fully explore experimentally. Computational fluid dynamics models capable of predicting local quantities are essential for accurate prediction of char oxidation in firebrands. This article presents a computational fluid dynamics model to estimate firebrand mass loss, diameter change, and surface temperature during char oxidation. The model was validated using previously conducted wind tunnel experiments. These experiments were conducted for firebrands of two different aspect ratios, which were arranged in three different configurations (single, horizontal array, and vertical array), and for four different wind speeds (0.5, 1, 1.5, and 2 m/s). The computational fluid dynamics results were compared with a previous 1 D model. In all the test cases, the computational fluid dynamics model predicted the physical phenomena with significantly improved accuracy compared to a 1 D model. The char oxidation model presented in this article can be coupled with other models to study firebrand generation and trajectory, biomass pyrolysis, fluidized bed reactors, and coal combustion.
Engineering↗
Machine learning enables reconstruction of past fire regimes from charcoal-derived fire intensity and fuel composition
Background Fire is a foundational ecological process that shapes ecosystem structure, diversity, and resilience. Quantifying paleofire regime attributes such as frequency, severity, and intensity is essential for understanding the historical range of variability in fire behavior and its ecological effects. While frequency and severity are often reconstructed in paleofire studies, quantitative reconstructions of fire intensity remain limited. Recent work has shown that maximum pyrolysis temperature—a proxy for fire intensity—and plant species type can be inferred from charcoal using transmission Fourier-transform infrared (FTIR) spectroscopy. However, the sample preparation for transmission FTIR is destructive and time-consuming, limiting application and reuse of materials for other analyses. We evaluated reflectance FTIR spectroscopy as a non-destructive alternative for reconstructing combustion temperature and plant species from laboratory-generated charcoal. We also examined the influence of contrasting airflow environments (ambient air versus nitrogen-rich) on pyrolysis temperature and plant species reconstruction prediction accuracies and compared predictive performance between a novel, neural network–based deep learning model with the traditional modern analogue technique (MAT) using k-nearest neighbor functions. As proof of concept, we apply our enhanced methodology to ancient charcoal to demonstrate applicability at improving long-term fire regime reconstructions and the ability to link paleofire records with contemporary fire ecology. Results Our analysis shows that transmission and reflectance FTIR spectra yield comparable spectral profiles. However, sample preparation for reflectance FTIR is minimal and non-destructive, unlike transmission FTIR which is destructive. We demonstrate that oxygen environments improved reconstruction accuracy relative to nitrogen-rich conditions. Finally, our deep learning neural network (DL) achieved testing accuracies of 98.7% for temperature and 96.2% for species identification, outperforming MAT’s k-NN approach (89.8% and 65.9%, respectively). A Shapley importance analysis identified 5 key spectral regions that greatly influenced the model’s temperature or species categorization. When applied to ancient charcoal, our results show historic fires from the most recent past primarily burned at low intensities (400–500 °C), reflective of natural fire regimes in ponderosa pine forests. Our results corroborate charcoal morphology data that suggests all ancient charcoal originated from burned woody plant types. Conclusions By combining reflectance FTIR spectroscopy with a deep learning approach, we provide the first accuracies high enough to confidently identify both species and temperature from laboratory-produced charcoal, improving quantitative reconstructions of fire intensity and fuel composition from paleofire records. This opens a wide range of research into the link between fire and larger drivers (i.e., climate or human) and greater ecological understanding of fire regimes beyond that of burn scars or recent observations. These methodological improvements have direct relevance for fire management by improving interpretation of historical fire behavior, informing fuel–fire relationships, and providing a scalable analytical framework applicable to both long-term ecological studies and contemporary fire science.
54 ENVIRONMENTAL SCIENCES↗
One-pot catalytic conversion of biomass and alkanes: Kinetically coupling deoxygenation and dehydrogenation pathways
The stoichiometric hydrogen deficiency of carbohydrate feedstock implies that all conversion processes must remove oxygen and concurrently increase hydrogen content to form liquid hydrocarbon products. With support from the DOE Early Career program (DE-SC0008418) we have investigated the use of transition metal carbides for hydrodeoxygenation (HDO) chemistries using CH 4 and H 2 as co-reactants. We report that concurrently processing CH 4 and C 1 -C 3 oxygenates (oxygenate/CH 4 = 0.01-0.1) at 950 K on molybdenum carbide clusters encapsulated in zeolite micropores results in a staged bed with upstream CH 4 reforming and downstream CH 4 dehydroaromatization. Forward rates of CH 4 pyrolysis limited by CH 4 activation are unperturbed by the introduction of oxygenates with a (C/H) eff <0.25 after rigorously accounting for the thermodynamic reversibility caused by the H 2 produced in oxygenate reforming reactions and the fraction of the active catalyst bed deemed unavailable for CH 4 dehydroaromatization. A binomial distribution of 12 C/ 13 C isotopologues of CO is observed upon introduction of CH 3 13 COOH/CH 4 reactants suggesting that the introduction of oxygenates with a (C/H) eff <0.25 results in complete fragmentation of the oxygenate at these temperatures which in turn results in the invariance of forward rates of CH 4 pyrolysis when using CO 2 , HCOOH, or CH 3 COOH co-feeds. The stoichiometric loss of oxygen as CO when co-processing C 1 -C 3 oxygenates and CH 4 at these temperatures demonstrates that (C/H) eff =(C-O)/H is a single valued descriptor for oxygen removal on Mo/HZSM-5 catalysts. Separately, we have demonstrated the utility of transition metal carbides for vapor phase catalytic hydrodeoxygenation using molecular hydrogen with high selectivity for C-O cleavage and near absence of sequential hydrogenation reactions at atmospheric hydrogen pressure and illustrated that the faculty of transition metal carbides for selective hydrodeoxygenation arises due to oxygen-modification of the catalyst in situ. The oxophilic characteristics of these materials engender both the observed acid-metal catalytic bifunctionality and selectivity for hydrodeoxygenation. The evolution of catalyst surface composition and catalytic function under oxidative reaction environments proffers unique challenges in structural characterization of these materials and in this context, we developed and demonstrated the use of chemical titration and chemical transient studies to assess catalytic site identity and densities.
09 BIOMASS FUELS↗
Making Coal Relevant for Small Scale Applications: Modular Gasification for Syngas/Engine CHP Applications in Challenging Environments
This Front-End Engineering Design (FEED) study is funded by the US Department of Energy (DOE), and managed by the National Energy Technology Laboratory (NETL) through a Cooperative Agreement awarded to the University of Alaska Fairbanks (UAF) to perform a technical and cost study for the design and installation of a Hamilton-Maurer International (HMI) gasifier for generating a clean syngas for firing in reciprocating engines. An existing diesel engine generator (DEG) and a commercially available spark ignition engine are used to generate electricity with the low-Btu syngas. Other than the HMI gasifier, only commercially available technologies were assumed for this study. An important objective of this design study was to estimate capital and operating costs of small modular coal and coal/biomass fired generating units to provide wind regulation services. Although this study is based on retrofitting an existing coal fired power plant with the HMI gasifier, sufficient data was developed to characterize greenfield units. The original concept was to provide clean syngas and tars/oils from the gasification process to the existing Colt-Pielstick PC2.6B diesel engine generator (9.6 MWe) installed at the UAF Atkinson Power Plant. The intent was to convert the diesel engine to operate in a dual fuel mode, firing both syngas and tars/oils. As the project progressed, Fairbanks Morse Engine (FME), current licensee for the Colt-Pielstick engine line, was not able to develop a modification package for the engine to allow for syngas firing. Although this type of modification is available for firing natural gas, the capability does not extend to syngas. Western Energy Systems, distributor for Innio Jenbacher, was able to offer the Jenbacher Model JMS620 engine. After review of available options, the project team selected a design configuration using two Jenbacher engines rated at 1965 kWe each to fire the syngas, with the oils/tars directed to the Colt Pielstick diesel to be blended with ultra-low sulfur diesel oil (ULSD). The Jenbacher engines are expected to operate at continuous base load, with some load-following ability, while the existing diesel engine will operate in grid support service, with loads varying from a nominal 25% to 100%. An annual capacity factor for the diesel engine is projected to be between 50% and 60%. The overall gasifier and gas clean-up system is sized to produce enough syngas to adequately fuel three Jenbacher Engines for a nominal power output of 5.9 MWe, but this study assumes that only two Jenbacher engines will be installed due to space constraints in the Atkinson Power Plant, and because of expected air emission permit limitations. There is still potential that the excess syngas capacity equivalent to about 2 MWe could be used as supplemental fuel for the DEG. The exhaust from the Jenbacher engines is passed through heat recovery units to generate low pressure steam, thereby providing a significant portion of the steam required for operating the gasifier. The overall performance of the HMI gasifier/engine configuration is summarized as follows: 1) Overall electric efficiency, Jenbacher and diesel engines, based on gasifier fuel production (syngas and pyrolysis liquids) is 35.2% LHV, 2) Overall cogenerating efficiency (electricity plus steam), based on gasifier fuel production (syngas and pyrolysis liquids) is 54.8% LHV, 3) Overall electric efficiency, Jenbacher and diesel engines, based on coal input, is 29.6% LHV, and 4) Overall cogenerating efficiency, electricity plus steam, based on coal input is 46.0%. This project is estimated to have a Bare Erected Cost (BEC) of $\$$ 33.4 million and a Total Plant Cost (TPC) of $\$$ 45.7 million. Based on the original scope, sending both the clean syngas and the oils and tars to the existing diesel engine, the BEC and TPC values would have been $\$$ 23.3 million and $\$$ 32.1 million, respectively. A variable Cost of Electricity (COE) is calculated to reflect only those costs that will be incurred by incremental operation of the system for the HMI gasifier/Jenbacher engine combination. Operation of the diesel engine is determined separately. The variable COE values are: Case 1: 100% Usibelli Coal: (a) HMI gasifier/Jenbacher Engines -- 8.3 cents/kWh; (b) Diesel Engine -- 20.2 cents/kWh, and Case 2: 80% Usibelli Coal + 20% wood chips (proportion based on Btu input, LHV basis): (a) HMI Gasifier/Jenbacher -- 13.7 cents/kWh; (b) Diesel Engine -- 20.2 cents/kWh. The incremental cost of operating the gasifier/Jenbacher system increases with co-firing of wood chips due to the high cost of this material, over five times as costly as Usibelli coal delivered to the Atkinson Power building. The diesel cost is constant as the oils and tars are priced at the same value as the ULSD for the purposes of fueling the diesel engine. Section 8 of this report provides details of the O&M costs. The overall power system is configured to be modular and scalable to provide a wide range of generating capacity using the same components. This allows for reduction in cost, risk, schedule time to engineer and construct, and provides some degree of repeatability for air permitting.
01 COAL, LIGNITE, AND PEAT↗
Carbon Fiber Prepreg Recycling- Automated Perform Manufacturing Equipment (Final Technical Report)
Discontinuous fiber composites have a compelling business case as related to light metals such as aluminum and magnesium machined or die cast components. DFC’s have been in commercial production using carbon fiber/epoxy prepreg for both commercial aircraft and for military applications for a number of years and their usage is expanding into automotive and consumer goods components. Reasons for this include significantly lower cost as compared to continuous fiber composites easier design and understanding of the material by metal traditionalists, higher degree of part complexity with relatively simple and low cost molds when compared to high-pressure die casting, and potential for near zero waste. IACMI’s 10-year goals of reduction in carbon fiber reinforced plastics manufacturing cost by 25%, reduction in their embodied energy by 50%, and recyclability of 95% can all be advanced through robust recycling. With recycling We have shown that a 15% contribution in manufacturing cost reduction is feasible, that a significant reduction in embodied energy (over 90% for the recycled fraction) is achievable, and that when combined with primary pyrolysis recycling, the 95% target can be met. Large-scale application of advanced composites began with the aerospace industry, and CRTC’s location in Washington State provided access to a waste stream of nearly 900 tonnes/year that was going to landfill. As the aerospace industry has automated parts production, their material forms have become significantly easier to recycle, and some evidence of this exists for the future automotive and wind turbine components as well. CRTC decided to focus on re-purposing the carbon fiber/epoxy aerospace scrap streams through materials reformatting and reuse, and not on primary recycling (pyrolysis mainly) as this technology is commercially available. The main reasons for this were that it offers a route to effective use of the most widely available and consistent feedstock called edge-trim, as well as allows creation of complex and low-cost parts using rapid and cost-effective compression molding technologies. The reasons also include leading the way for potential automotive pre-preg recycling as the combination of roughly 85% virgin pre-preg and 15% recycled pre-preg directly supports IACMI’s goals and enables significant part cost reduction and a path to zero-waste composite manufacturing at the OEMs or Tier 1’s. The purpose of the project was to develop equipment and technology to transform continuous fiber pre-preg in roll forms into smaller chip-format DFC feedstock, and to determine impacts on moldability and performance based on lessons learned along the path. The availability of scrap from pre-preg manufacturers was a significant value to the program even though the aerospace pre-preg is designed to be autoclave molded thus has handling, tackiness, and processing factors that are not ideal for DFCs. The scope of the project was to develop a Phase 1 system that could identify and resolve some of the major hurdles, determine where to focus effort on building a commercial-scale Phase 2 system, and develop technology for handling a wide variety of incoming scrap materials to produce the most usable product. A chopping system was developed and reduced to practice via an experimental approach that enabled all forms of scrap coming from the pre-preg manufacturers and some forms of the scrap coming from OEM production lines to be very effectively re-purposed. The systems that were developed were not considered to be production robust but rather identified and resolved some of the major technical hurdles, and demonstrated the path towards effective full-scale commercialization.
36 MATERIALS SCIENCE↗
Process and Applications Development for Recycled Mixed-Stream Composites
The goal of this IACMI Phase II Technical Collaboration Project was to establish the viability of producing affordable, recycled composite parts, which were produced from fibers with the properties in the range of those reclaimed through the controlled pyrolysis technology demonstrated in Phase I. For the purpose of this report, we use the terms “recovered carbon fiber” (rCF) and “recovered glass fiber” (rGF) as the material reclaimed from controlled pyrolysis. This fiber recycling technology utilizes the inherent energy in composites for fuel and preserves the structural value of glass fiber (GF) and carbon fiber (CF) for reuse. It can also be used for recycling other waste streams at the same facility, thus spreading capital risk and recovery across multiple industries and achieving economy of scale. A second goal to be addressed was the viability of using recycled fibers as reinforcing materials in additive manufacturing applications.
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
Thermal Decomposition of Cyclic, Oxygenated Hydrocarbons
This final technical report describes experimental and theoretical studies of the pyrolysis of molecules relevant to the production of biofuels from biomass. The primary goal of the project was to study how chemical structure affects the thermal decomposition mechanism of a series of cyclic, oxygenated hydrocarbons. To accomplish this, the products of thermal decomposition must first be identified. A pulsed hyperthermal nozzle was used to induce gas-phase pyrolysis of the samples at temperatures up to 1600 K. Product detection was accomplished with a matrix-isolation FTIR spectrometer.
09 BIOMASS FUELS↗
ElectroCat: Platinum-Group-Metal-Free Engineered Framework Nano-Structure Catalyst (Final Technical Report)
Traditional synthesis methodologies that produce durable, highly active PGM-free electrocatalysts typically consist of a top-down approach utilizing a nitrogen-coordinating precursor, a metal precursor, and a support material. Nitrogen-coordinated transition metal complexes typically are absorbed onto a support material, which is then activated via high-temperature pyrolysis. Selection of the support and the nitrogen coordinating precursor has long been the focal point of efforts to maximize the number of accessible, catalytically active sites. In this project, GWE in collaboration with SRNL and NU will develop durable, highly active, low-cost, PGM-free electrocatalysts for polymer electrolyte membrane fuel cells designed and synthesized using a unique, bottom-up, rationally designed approach. Electrocatalysts are produced via polymerization reaction followed by a high-temperature pyrolysis step. Additionally, this project focuses on catalyst site and ORR mechanistic modeling to better understand the structure-property relationship.
08 HYDROGEN↗
Enabling Entrained-Flow Gasification of Blends of Coal, Biomass and Plastics (Final Report)
This project demonstrated the technical feasibility of gasifying blends of coal, biomass and mixed waste plastics in a high pressure entrained-flow gasifier for production of hydrogen. This was achieved by creating slurries of coal, biomass pyrolysis liquids and liquefied plastic oil. Specific objectives of the project included (1) determining compositions of coal-biomass-plastic mixtures that produce a stable slurry suitable for pumping to high pressure, (2) designing and testing a novel burner to effectively atomize the mixed feedstock slurry in a pressurized gasifier, and (3) acquiring first-of-a-kind performance data for pressurized, oxygen-blown entrained-flow gasification of slurried blends of coal, biomass and plastic. A key focus of the project was preparation of mixtures of coal, biomass and plastic. To facilitate easy pumping to high pressure, slurries were created using (i) bioliquid resulting from a well-established rapid thermal treatment pyrolysis process, (ii) oil produced from waste plastic via an available thermal conversion process, and (iii) ground coal. Lab-scale tests were conducted to evaluate viscosity and stability/propensity for the mixtures to separate over time. Larger batches of the most promising slurry compositions were prepared and subjected to pumping studies. It was found that mixtures containing less than about 40% coal and less than about 30% plastic oil were stable and of low enough viscosity to facilitate pumping to high pressure. A high-performance hot oxygen burner (HOB) was designed and fabricated for use in an existing 1 ton/day pressurized entrained-flow gasifier. Ex-situ testing demonstrated that the HOB provides excellent atomization of the slurries and creates a very uniform and robust flame. Performance of the HOB in the gasifier was exceptional and resulted in better conversion to syngas than any previous generation of burner. Fabricating the HOB for this project was challenging due to the relatively small scale of the gasifier. Performance in larger-scale systems is expected to be even better. Gasification of mixtures of coal, bioliquid and plastic oil proved to be relatively easy. The gasifier was able to be started up, pressurized and transitioned to the blended slurry feedstock with no technical difficulty. Syngas rich in CO and H 2 , with relatively low concentrations of CO 2 , was produced. During startup and at low gasification temperatures, soot formation was observed, as is typical for gasification of petroleum-based feedstocks. No slag buildup was observed under the conditions tested. The project was successful in demonstrating the technical feasibility of the concept. Future development should broaden the range of feedstocks under consideration, more deeply explore performance of the gasifier, and evaluate scale-up and implementation strategies.
08 HYDROGEN↗
Developing Platinum-Group-Metal-Free Catalysts for Oxygen Reduction Reaction in Acid: Beyond the Single Metal Site
This project is to develop M (x) -N-C catalysts with dense multiple metal center (MMC) sites to meet the DOE 2025 activity target of 0.044 mA/cm 2 at 0.9 V IR-free ., as well as other goals such as durability. We have made important contributions to both catalyst development and fundamental understandings of the active sites in M-N-C catalysts in this project. We successfully made M (x) -N-C catalysts with some multiple metal center (MMC) sites by combining ionothermal carbonization with chemical vapor deposition (CVD). These catalysts, however, are not as active as the most active single-atom Fe-N-C catalysts made by the similar CVD process, owing likely to the low site density and the presence of inorganic Fe species such as iron carbides and nanoparticles. The most significant accomplishments we achieved in this project are: (1) we unraveled the formation pathway of Fe-N 4 sites during pyrolysis step-by-step and identified the trans-metalation mechanism, in collaboration with Deborah Myers and her colleagues at Argonne National Laboratory (ANL); (2) inspired by this finding, we pioneered the CVD synthesis of M-N-C catalysts (M = Mn, Fe, and Co), in which the Fe-N-C catalyst by CVD demonstrated an ORR activity of 33 mA/cm 2 at 0.9 V in H 2 -O 2 proton exchange membrane fuel cells (PEMFCs), very close to the ultimate goal of 35 mA/cm 2 of our project. This catalyst is the first Fe-N-C catalyst that contains only D1 sites without the D2 sites; whereas D1 and D2 sites have been always identified by Mossbauer in previous Fe-N-C catalysts. This finding helps to understand what the D1 and D2 sites are and their roles in catalyzing the ORR. (3) by improving the mass transport of the carbon matrix prior to the CVD process, the revised Fe-N-C catalyst made by CVD delivered a maximum power density of 0.53 W/cm 2 in H 2 -air PEMFCs. The improvement strategy was partly inspired by the computational modeling work by Adam Weber from LBNL, the Co-PI of this project, by developing, coding, and exercising a continuum level model of transport phenomena within a PGM-free catalyst layer. The model demonstrated that local resistances combined with limited site density of the PGM-free catalyst can result in limiting currents and poor polarization performance. The model also gave design guidance for impact of ECSA and overall catalyst-layer thickness. However, both Fe-N-C and Co-N-C catalysts developed by CVD showed poor durability in PEMFCS, in comparison with the traditional M-N-C catalysts synthesized via regular pyrolysis process. Consequently, we did not achieve the proposed durability targets. Despite so, we believe the FeNC-CVD catalysts with the poor durability and D1 sites only provides an excellent platform to understand the degradation mechanism of Fe-N-C in PEMFCs, the most important challenge in the development of M-N-C catalysts.
08 HYDROGEN↗
Numerical Simulation of Biogenic Fluid Catalytic Cracking (BFCC) Regenerators at Different Scales with MFIX-Exa
Catalytic Fast Pyrolysis (CFP) is a process that converts biomass into liquid intermediates suitable for transportation fuels by rapidly heating it in the presence of a catalyst, aiming to produce stable oils with reduced oxygen content. During CFP, the catalyst can become deactivated by the accumulation of coke, a carbon-rich deposit formed from the decomposition of biomass components. Unlike in petroleum refining, regenerating coked catalysts from biomass pyrolysis requires specific approaches due to the different chemical nature of the coke formed. An experimental technique, Temperature Programmed Oxidation (TPO), was used to study the de-coking process by gradually increasing temperature while monitoring the production of CO and CO2, which provides data for kinetic modeling. Utilizing data from TPO experiments, coke combustion kinetic model was developed to describe the rate of coke removal at different temperatures, allowing for simulation of regeneration processes. Then kinetic model is integrated into MFIX-Exa for the simulation of Biogenic Fluid Catalytic Cracker (BFCC) regenerator at different scales, enabling analysis of catalyst flow, temperature distribution, and regeneration efficiency under various operating conditions.
biogenic fluid catalytic cracking↗
Low-Temperature Plasma Assisted Kinetics Study of Ethanol
Non-equilibrium plasma assisted kinetics of ethanol at 0.5 atm over a temperature range of 523-1203 K were studied at stoichiometric conditions by using a plasma flow reactor (PFR). The effects of plasma chemistry on fuel and its influence on neutral chemistry is decoupled with both experimental and modelling efforts. Enhanced reactivity was observed experimentally in both plasma-assisted oxidation and pyrolysis cases with fuel consumption beginning at temperatures as low as 523 K. Absolute fuel consumption was observed at temperatures nearly 200 K earlier than pure thermal reactions highlighting the effectiveness of non-equilibrium plasma to promote reactivity. Furthermore, modelling results illustrated the effect of electron impact reactions towards accelerating fuel consumption and promoting low temperature chemistry by generating excited state N2 and reactive O and OH radicals.
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
Efficient Leaching of Metal Ions from Spent Li-Ion Battery Combined Electrode Coatings Using Hydroxy Acid Mixtures and Regeneration of Lithium Nickel Manganese Cobalt Oxide
Extensive use of Li-ion batteries in electric vehicles, electronics, and other energy storage applications has resulted in a need to recycle valuable metals Li, Mn, Ni, and Co in these devices. In this work, an aqueous mixture of glycolic and lactic acid is shown as an excellent leaching agent to recover these critical metals from spent Li-ion laptop batteries combined with cathode and anode coatings without adding hydrogen peroxide or other reducing agents. An aqueous acid mixture of 0.15 M in glycolic and 0.35 M in lactic acid showed the highest leaching efficiencies of 100, 100, 100, and 89% for Li, Ni, Mn, and Co, respectively, in an experiment at 120 °C for 6 h. Subsequently, the chelate solution was evaporated to give a mixed metal-hydroxy acid chelate gel. Pyrolysis of the dried chelate gel at 800 °C for 15 h could be used to burn off hydroxy acids, regenerating lithium nickel manganese cobalt oxide, and the novel method presented to avoid the precipitation of metals as hydroxide or carbonates. The Li, Ni, Mn, and Co ratio of regenerated lithium nickel manganese cobalt oxide is comparable to this metal ratio in pyrolyzed electrode coating and showed similar powder X-ray diffractograms, suggesting the suitability of α-hydroxy carboxylic acid mixtures as leaching agents and ligands in regeneration of mixed metal oxide via pyrolysis of the dried chelate gel.
Electrochemistry↗
Cleanup and Conversion of Biomass Liquefaction Aqueous Phase to C3–C5 Olefins over ZnxZryOz Catalyst
The viability of using a ZnxZryOz mixed oxide catalyst for the direct production of C4 olefins from the aqueous phase derived from three different bio-oils was explored. The aqueous phases derived from (i) hydrothermal liquefaction of corn stover, (ii) fluidized bed fast pyrolysis of horse litter, and (iii) screw pyrolysis of wood pellets were evaluated as feedstocks. While exact compositions vary, the primary constituents for each feedstock are acetic acid and propionic acid. Continuous processing, based on liquid–liquid extraction, for the cleanup of the inorganic contaminants contained in the aqueous phase was also demonstrated. Complete conversion of the carboxylic acids was achieved over ZnxZryOz catalyst for all the feedstocks investigated. The main reaction products from each of the feedstocks include isobutene (>30% selectivity) and CO2 (>23% selectivity). Activity loss from coking was also observed, thereby rendering deactivation of the ZnxZryOz catalyst, however, complete recovery of catalyst activity was observed following regeneration. Finally, the presence of H2 in the feed was found to facilitate hydrogenation of intermediate acetone, thereby increasing propene production and, consequently, decreasing isobutene production.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗