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DOE OSTI2023

Plasma-Coupled Flow Reactor Studies of Low-Temperature Plasma Assisted Kinetics of Methanol Blended with CO2

Ignition technologies based on low-temperature plasmas (LTP) have the potential to operate next generation engines at elevated pressures and increased dilution limits promoting higher efficiencies. From a practical standpoint, research on LTP igniters has shown to enhance combustion and ignition, improve flame stability, and extend the dilution limits of combustion. All of the aforementioned gains are complemented with higher ignition efficiencies. However, the biggest challenge with incorporating this technology into engines is the knowledge gap of how exactly plasma chemistry effects can enhance the basic combustion phenomena. This coupled with the lack of validated kinetic mechanisms for plasma-combustion chemistry is the biggest obstruction to recognize efficient ignition, especially for application relevant fuels and biofuels. In order to comprehensively evaluate the effects of LTP on an oxygenated fuel specific system, this present study examines the kinetics of methanol plasma-assisted pyrolysis and oxidation using a custom-built plasma flow reactor (PFR). Experimental regimes are also further extended to understand the effects of adding CO2 to the mixture and its consequence on reaction kinetics. The PFR is installed with a dielectric-barrier discharge (DBD) configuration to induce LTP into the fuel mixture. Non-equilibrium plasmas are generated by high-voltage pulses (nearing 20 KV) administered by a plasma pulser at high-pulse repetition rates (up to 10 kHz). In order to better understand and isolate plasma chemistry and its effect on neutral chemistry, the experiments were carried out by heavily diluting reactive mixtures in nitrogen at near isothermal conditions. This suppresses the effect of exothermic reactions on chemistry allowing stable intermediates and products to be detected and quantified using ex-situ GC/MS diagnostic methods. Experiments were carried out at 0.5 atm pressure and over a wide range of temperatures from 523 K to 1203 K. Experimental results depicted the enhancement in intermediates production as well as overall lower temperatures required for complete fuel consumption in the plasma specific cases as opposed to their pure thermal counterpart. Formation of oxygenated and nitrile compounds specific to plasma assisted pyrolysis cases illustrated the efficacy of LTP to introduce new reaction pathways accelerating fuel decomposition. Increase in reactivity at lower temperatures is sought to be an effect induced by plasma chemistry postulating the acceleration in intermediates production. The onset of thermal ignition in plasma assisted oxidation is seen 200 K earlier than thermal oxidation highlighting efficient fuel conversion to final byproducts. Enhanced collisional processes afforded by LTP is seen to perturb reaction pathways between oxygenated fuel radicals and N-atoms to alter overall chemical reactivity. New insights into kinetics are gained from this study highlighting governing plasma assisted combustion (PAC) pathways for oxygenated fuel reaction chemistry. The results from this study can be used to develop future mechanisms specific to plasma chemistry which can bridge the mechanistic knowledge gap for LTP ignition so that future engines can adopt LTPs in their design for efficient combustion.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2024

Solar enhanced oxygen evolution reaction with transition metal telluride

The photo-enhanced electrocatalytic method of oxygen evolution reaction (OER) shows promise for enhancing the effectiveness of clear energy generation through water splitting by using renewable and sustainable source of energy. However, despite benefits of photoelectrocatalytic (PEC) water splitting, its uses are constrained by its low efficiency as a result of charge carrier recombination, a large overpotential, and sluggish reaction kinetics. Here, we illustrate that Nickel telluride (NiTe) synthesized by hydrothermal methods can function as an extremely effective photo-coupled electrochemical oxygen evolution reaction (POER) catalyst. In this study, NiTe was synthesized by hydrothermal method at 145°C within just an hour of reaction time. In dark conditions, the NiTe deposited on carbon cloth substrate shows a small oxygen evolution reaction overpotential (261 mV) at a current density of 10 mA cm –2 , a reduced Tafel slope (65.4 mV dec -1 ), and negligible activity decay after 12 h of chronoamperometry. By virtue of its enhanced photo response, excellent light harvesting ability, and increased interfacial kinetics of charge separation, the NiTe electrode under simulated solar illumination displays exceptional photoelectrochemical performance exhibiting overpotential of 165 mV at current density of 10 mA cm -2 , which is about 96 mV less than on dark conditions. In addition, Density Functional Theory investigations have been carried out on the NiTe surface, the results of which demonstrated a greater adsorption energy for intermediate -OH on the catalyst site. Since the -OH adsorption on the catalyst site correlates to catalyst activation, it indicates the facile electrocatalytic activity of NiTe owing to favorable catalyst activation. DFT calculations also revealed the facile charge density redistribution following intermediate -OH adsorption on the NiTe surface. This work demonstrates that arrays of NiTe elongated nanostructure are a promising option for both electrochemical and photoelectrocatalytic water oxidation and offers broad suggestions for developing effective PEC devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Bipolar Membranes for Ion Management in (Photo)Electrochemical Energy Conversion

Conspectus (Photo)electrochemical energy conversion is important in the development of a carbon-neutral energy economy because it can provide a pathway for mitigating the intermittency of renewable energy sources such as wind and solar. In order to operate efficiently, these technologies, which include photoelectrochemical cells, water and CO 2 electrolyzers, fuel cells, and redox flow batteries, require fast charge transfer kinetics at the electrode/electrolyte interface as well as robust ion management in the electrolyte. In conventional electrolyzers and fuel cells, the electrolyte is strongly acidic or basic and ionic current is carried by H + or OH – ions. In contrast, photoelectrodes and electrocatalysts for water splitting are often studied in buffered solutions. The question of ion balance in these systems led us to analyze the polarization losses due to ion concentration gradients in cells that employed various buffer–membrane combinations. Continuously driving the buffer ions across an ionomer membrane not only lowers the buffer capacity of an aqueous electrolyte but also introduces pH gradients that result in significant energy losses. To address the problem, we and other groups have studied the use of reverse-biased bipolar membranes (BPMs) in (photo)electrolytic cells. BPMs consist of an anion exchange layer (AEL) laminated with a cation exchange layer (CEL) and are usually equipped with a catalytic layer in between to accelerate the water dissociation reaction. At the AEL/CEL interface, water dissociates into protons and hydroxide ions, which replenish those consumed at the cathode and anode. Compared to conventional water electrolyzers with proton/anion exchange membranes (PEM/AEM), BPM electrolyzers provide the unique advantage of continuously operating the cathode and anode under different pH conditions, which is desirable when the two electrode reactions have different pH requirements. BPMs also enable the use of buffered electrolytes at pH values that are optimized for electrode stability and product selectivity in applications such as CO 2 electrolysis. Product crossover losses and CO 2 pumping can be dramatically reduced in BPM-based CO 2 electrolyzers, relative to conventional alkaline membranes, by electrostatic repulsion (of anionic products) and electroosmotic drag (for neutral products). BPM-based gas fed CO 2 electrolyzers can achieve high current density, but they suffer from low Faradaic efficiency (FE) due to the acidic local environment of the CEL. This problem can be mitigated by adding an aqueous buffering layer or by creating a weak acid cation exchange film on the CEL face of the membrane. The use of BPMs in fuel cells and redox flow batteries offers some interesting advantages. Configurations with both reverse and forward bias have been studied, but forward bias has been favored due to material compatibility, reaction kinetics, and thermodynamic considerations. The net reaction at the AEL/CEL interface is the acid–base neutralization reaction, which has a high inherent reaction rate constant, but in the BPM is limited to a nanometric space-charge layer and requires efficient catalysis to achieve high current density. Understanding the mechanism of the acid–base neutralization and the opposite process, the water dissociation reaction, will be essential for improving the performance of forward-biased BPMs. In conclusion, this Account reviews our current understanding of the working mechanisms of BPMs and discusses how we can use them to effectively manage ions for various (photo)electrochemical applications.

Yan, Zhifei↗

DOE OSTI2024

A Catalyst-Like System Enables Efficient Perovskite Solar Cells

High-quality perovskite films are essential for achieving high performance of optoelectronic devices; However, solution-processed perovskite films are known to suffer from compositional and structural inhomogeneity due to lack of systematic control over the kinetics during the formation. Here, in this work, the microscopic homogeneity of perovskite films is successfully enhanced by modulating the conversion reaction kinetics using a catalyst-like system generated by a foaming agent. The chemical and structural evolution during this catalytic conversion is revealed by a multimodal synchrotron toolkit with spatial resolutions spanning many length scales. Combining these insights with computational investigations, a cyclic conversion pathway model is developed that yields exceptional perovskite homogeneity due to enhanced conversion, having a power conversion efficiency of 24.51% for photovoltaic devices. This work establishes a systematic link between processing of precursor and homogeneity of the perovskite films.

14 SOLAR ENERGY↗

DOE OSTI2022

Elucidating the Roles of Local and Nonlocal Rate Enhancement Mechanisms in Plasmonic Catalysis

Plasmonic metal nanoparticles (e.g., Ag, Au, and Cu) constitute a class of materials that interact with light via the excitation of localized surface plasmon resonance (LSPR). Numerous studies have reported substantial enhancements in the rates of chemical reactions on illuminated plasmonic nanoparticle catalysts compared to corresponding systems in the absence of illumination. There are two mechanisms that have been proposed to explain the LSPR-induced chemical reactivity. One mechanism assumes a local plasmon-induced hot charge-carrier-mediated activation of the reactants, while the other assumes an LSPR-induced equilibrium heating of the catalyst, which leads to energy transfer to and chemical reaction of the adsorbed reactants. Here, in this contribution, we developed a setup amenable to accurate in situ catalyst temperature and kinetic reaction rate measurements. We employed this setup to study the LSPR-induced rate enhancement in a case study of the CO oxidation reaction on plasmonic, monometallic Ag nanoparticle catalysts supported on α-Al 2 O 3 . We explored various Ag loadings and clustering levels. Our data show that the equilibrium heating of the catalyst cannot fully explain the illumination-induced plasmonic rate enhancements. This is the case even for high loading and clustering of Ag nanoparticles, where the equilibrium heating significantly increases. Based on the analysis, we propose that local effects, related to the plasmon-induced activation of adsorbates (reactants) via electronic excitation of the reactant or photothermal heating of the reactants that is highly localized to the individual nanoparticles, play a critical role in driving LSPR-induced chemical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1983

Investigation of the Hydrochlorination of SiCl4

The hydrochlorination of silicon tetrachloride with hydrogen and metallurgical grade (m.g.) silicon metal, 3 SiCl4 + 2 H2 + Si yields 4 SiHCl3 was shown to be an efficient process to produce trichlorosilane. A research and development program was carried out to study the hydrochlorination reaction over a wide range of reaction conditions. Equilibrium constant and reaction kinetics measurements were made to provide the basis for a theoretical study on the hydrochlorination process. Thermodynamic properties of the hydrochlorination reaction were also measured. The effects of temperature, pressure, and concentration on the equilibrium constant, K sub p, were studied.

Mui, J. Y. P.↗

DOE OSTI2025

Iodine recombination in xenon solvent: Clusters in the gas to liquid-like state transition

Supercritical fluids (SCFs) have attracted significant attention as solvents for chemical reactions due to their unique properties, such as high diffusivity, low viscosity, and tunable solvation properties. These properties profoundly influence reaction kinetics and are often attributed to the formation of molecular clusters within SCFs. To study the effect of supercritical solvent on chemical reactivity and dynamics of reactions, one needs to understand the dynamics of clusters in supercritical fluid. Extensive experiments on the photodissociation and recombination of iodine in supercritical fluids served as a model system for understanding these effects. Experimental studies have been complemented by theoretical and computational investigations, which mostly employ Monte Carlo or empirical molecular dynamics simulations. However, computational studies using non-reactive force fields and ab initio approaches present challenges in capturing reactive processes at larger scales within supercritical fluids. Here, in this work, we developed the ReaxFF parameters by training against quantum mechanics data. ReaxFF reactive force field based molecular dynamics simulations were performed, studying the dynamics of a xenon solvent and cage effect at different thermodynamic conditions for the iodine recombination reaction. We show that the conditions near the critical point are the optimal conditions to study the cage effect. We show that the average lifetime of xenon clusters ranging between 5 and 11 ps is comparable to iodine geminate recombination. Our simulation results of iodine recombination in xenon solvent demonstrate the higher probability of iodine molecule formation in the presence of xenon clusters. Finally, we show that the supercritical condition exhibits the highest recombination rate for iodine atoms.

Cage effect↗

NASA NTRS1983

Measuring Epoxy-Curing Kinetics

Key reaction parameters estimated from single run. Single DSC Curve used to construct linearized plot from which kinetic reaction parameters are obtained: vertical axis intercept proportional to activation energy, while slope equals reaction order. DSC methods show promise for rapid screening and estimation of cure kinetic parameters of epoxy resins.

Cizmecioglu, M.↗

DOE OSTI2025

Mechanistic understanding of carbon mineralization in fracture systems using microfluidics

Carbon mineralization in mafic and ultramafic rocks presents an opportunity for permanent carbon storage in the Earth's subsurface. However, due to their lower permeability, pre-existing fracture networks are key for mineralization to occur. Therefore, to fully develop this technology, a mechanistic understanding of the mineralization behavior in fractures with the consideration of hydrodynamic components is required. We use high-pressure microfluidics to investigate key mechanisms influencing dissolution–precipitation in a fracture network. The experiments were conducted in micromodels made of natural rocks with a comb-shaped flow channel to mimic a fracture network. This enabled studying the effect of injection rate on coupled dissolution–precipitation in advection and diffusion-dominated flow paths. We used gypsum carbonation as an analog reaction to allow for realistic experimental time frames due to its rapid reaction kinetics. The experimental work is coupled with high-fidelity numerical simulations to enhance our understanding of the parameters affecting the mineralization reaction. Our results demonstrate the importance of flow rate on the rate and nature of the gypsum carbonation reaction revealing that higher flow rates enable deeper penetration of the mineral precipitation front into the dead-end channels. This is an important finding since for sustained mineralization in a fracture network, precipitation in dead-ends while still allowing for flowing fractures is critical. Detailed characterization of the precipitates showed that lower flow rates led to porous and loose precipitates in the form of aragonite while higher flow rates mimicked supersaturation behavior leading to the formation of calcite. The reactive transport simulations further demonstrated the significance of flow velocity in advection-dominated channels to influence the efficiency of carbon mineralization in diffusion-dominated channels, potentially clogging of dead-end channels. These findings highlight the need for coupling chemical, mechanical, and hydrodynamic processes to evaluate the nature and extent of carbon mineralization in fractured media critical for permanent storage in mafic and ultramafic formations. This research further highlights the need for more investigation in potential subsurface fracture generation techniques to aid carbon mineralization.

25 ENERGY STORAGE↗

DOE OSTI2021

Nonequilibrium information entropy approach to ternary fission of actinides

Ternary fission of actinides probes the state of the nucleus at scission. Light clusters are produced in space and time very close to the scission point. Within the nonequilibrium statistical operator method, a generalized Gibbs distribution is constructed from the information given by the observed yields of isotopes. Using this relevant statistical operator, yields are calculated taking excited states and continuum correlations into account, in accordance with the virial expansion of the equation of state. Furthermore, clusters with mass number A≤10 are well described using the nonequilibrium generalizations of temperature and chemical potentials. Improving the virial expansion, in-medium effects may become of importance in determining the contribution of weakly bound states and continuum correlations to the intrinsic partition function. Yields of larger clusters, which fail to reach this quasiequilibrium form of the relevant distribution, are described by nucleation kinetics, and a saddle-to-scission relaxation time of about 7000 fm/c is inferred. Light-charged particle emission, described by reaction kinetics and virial expansions, may therefore be regarded as a very important tool to probe the nonequilibrium time evolution of actinide nuclei during fission.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

NASA NTRS1991

Kinetics of volatile extraction from carbonaceous chondrites: Dehydration of talc

Carbonaceous chondrites are believed to be the primary constituents of near-Earth asteroids and Phobos and Deimos, and are potential resources of fuels that may be exploited for future planetary missions. Calculations of equilibrium phase relations suggest that talc (Ta) and antigorite (Ant) are likely to be the major hydrous phases in the C1 and C2 meteorites (Ganguly and Saxena, 1989), which constitute the most volatile rich classes of carbonaceous chondrites. The dehydration kinetics of talc are studied as a function of temperature, grain size, composition and fluid fugacity, as part of a systematic study of the reaction kinetics of the volatile bearing phases that are either known or likely to be present in carbonaceous chondrites. The dehydration kinetics were investigated at 1 bar, 775 to 875 C by monitoring the in-situ weight loss as a function of time of a natural talc. The talc platelets had a dimension of 0.8 to 1 micron. The run durations varied from 233.3 hours at 775 C (48 percent dehydration) to 20.8 hours at 875 C (80 pct. dehydration). The results can be adequately represented by a given rate equation. Theoretical analysis suggests that the reduction in the concentration of H2O in the environment of dehydrating talc, as would be encountered in processing chondritic materials, will have negligible effect on the rate of dehydration, unless there is a change of reaction mechanism owing to the presence of other volatile species.

Bose, Kunal↗

DOE OSTI2021

Characterizing Reactive Transport Behavior in a Three-Dimensional Discrete Fracture Network

While several studies have linked network and in-fracture scale properties to conservative transport behavior in subsurface fractured media, studies on reactive transport cases remain relatively underdeveloped. In this study, we explore the behavior of an irreversible kinetic reaction during the interaction of two solute plumes, one consisting of species A and the other species B. When the plumes converge, these species react kinetically to form a new species C via A+B→kC. This reactive system is studied using a three-dimensional discrete fracture network (DFN) model coupled with reactive Lagrangian particle tracking. We find that the interplay of network topology and chemical properties of the reactive solutes controls reactive transport processes. The network topology drives species A and B together, and the chemical properties dictate whether and how quickly a reaction occurs. Results demonstrate that reactions are most likely to occur in high-velocity fractures that make up the network backbone. The interplay between species’ chemical properties and transport is characterized by a non-dimensional Damköhler (Da) number. We show that the spatial distribution of reactions is sensitive to Da, which subsequently influences late-time tailing behavior in outlet breakthrough time distributions. The results of this study provide initial insights into how an irreversible reaction occurs during transport in a fracture network, using a methodology that can be applied to study reactive transport in a wide range of fractured media environments and contexts.

58 GEOSCIENCES↗

DOE OSTI2021

Unraveling the Intermediate Reaction Complexes and Critical Role of Support-Derived Oxygen Atoms in CO Oxidation on Single-Atom Pt/CeO 2

CeO 2 -supported Pt single-atom catalysts have been extensively studied due to their relevance in automobile emission control and for the fundamental understanding of CeO 2 -based catalysts. Though CeO 2 -supported Pt nanoparticles are often more active than their single-atom counterparts, the former could easily redisperse to Pt single atom under oxidizing diesel conditions. Therefore, to maximize the reactivity of every Pt atom, it is important to fully understand the reaction mechanism of CeO 2 -supported Pt single atoms. Here, we report a CO oxidation study on a Pt/CeO 2 single-atom catalyst, where we can account for all of the neighbors using in situ and operando spectroscopy techniques and microcalorimetric measurements. Coupled with density functional theory calculations, we present a comprehensive picture of the dynamics of the surface species, the role of surface intermediates, and explain the observed reaction kinetics. We started with a catalyst containing exclusively single atoms and used in situ/operando spectroscopy to provide evidence for their stability during the reaction and to identify the Pt 1 complexes before and during the reaction and their binding to CO. The results reveal that in the precatalyst, Pt is present as Pt(O) 4 on the CeO 2 (111) step edge sites, but during CO oxidation, we find that two Pt 1 complexes coexist, representing two states of the same active site in the reaction cycle. The dominant state/complex remains Pt(O) 4 , which adsorbs CO very weakly as shown by CO microcalorimetry. The second, minority state/complex, Pt(CO)(O) 3 is generated through the reaction of Pt(O) 4 with CO, and CO is bound strongly to Pt 1 . Labile oxygen adatoms from the CeO 2 surface play a major role in the regeneration of Pt(O) 4 either directly from Pt(O) 3 or by reaction with the strongly adsorbed CO in Pt(CO)(O) 3 . We show that the formation of an oxygen vacancy and generation of a labile O* are not barrierless, which explains the long lifetime of Pt(CO)(O) 3 and its detectability despite being a minority complex. The results help to develop a comprehensive view of the dynamic evolution of Pt 1 complexes along the reaction cycle and provide mechanistic insights to guide the design of Pt-based single-atom catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Controlling the toxicity of biomass-derived difunctional molecules as potential pharmaceutical ingredients for specific activity toward microorganisms and mammalian cells

A biomass-derived difuran compound, denoted as HAH (HMF–acetone–HMF), synthesized by aldol-condensation of 5-hydroxyfurfural (HMF) and acetone, can be partially hydrogenated to provide an electron-rich difuran compound (PHAH) for Diels–Alder reactions with maleimide derivatives. The nitrogen (N) site in the maleimide can be substituted by imidation with amine-containing compounds to control the hydrophobicity of the maleimide moiety in adducts of furans and maleimide by Diels–Alder reaction, denoted as norcantharimides (Diels–Alder adducts). The structural effects on the toxicity of various biomass-derived small molecules synthesized in this manner to regulate biological processes, defined as low molecular weight (≤1000 g mol -1 ) organic compounds, were investigated against diverse microbial and mammalian cell types. The biological toxicity increased when hydrophobic N-substitutions and C[double bond, length as m-dash]C bonds were introduced into the molecular structure. Among the synthesized norcantharamide derivatives, some compounds demonstrated pH-dependent toxicities against specific cell types. Reaction kinetics analyses of the norcantharimides in biological conditions suggest that this pH-dependent toxicity of norcantharimides could arise from retro Diels–Alder reactions in the presence of a Brønsted acid that catalyzes the release of an N-substituted maleimide, which has higher toxicity against fungal cells than the toxicity of the Diels–Alder adduct. These synthetic approaches can be used to design biologically-active small molecules that exhibit selective toxicity against various cell types (e.g., fungal, cancer cells) and provide a sustainable platform for production of prodrugs that could actively or passively affect the viability of infectious cells.

60 APPLIED LIFE SCIENCES↗

NASA NTRS1972

Preparation of pigments for space-stable thermal control coatings

The identification and control of vapor phase reaction kinetics to produce pigments by homogeneous nucleation were achieved. A vapor phase apparatus was designed, fabricated, and calibrated through 1800 C. Vapor phase reactions were analyzed, calculations made, and powders of alumina, rutile, zinc orthotitanate (in a mixed phase), calcium tungstate, and lanthana were produced by homogeneous nucleation. Electron microscopy shows uniform particle morphology and size, and supports anticipated advantages of vapor-phase homogeneous nucleation; namely, purity, freedom from defects, and uniform particle sizing without grinding.

Campbell, W. B.↗

DOE OSTI2023

Chemical looping conversion of CH4/CO2 to syngas on 5wt.%Ni@Ce0.6Zr0.4O2 catalyst: Impact of dynamic accumulation of surface carbon and oxygen vacancies

Syngas, a combination of carbon monoxide (CO) and hydrogen (H2), is a precursor to many chemicals and fuels, contributing to the billion-dollar global hydrocarbon industry. Chemical looping reforming (CLR) of the greenhouse gases methane (CH4) and carbon dioxide (CO2) allows for energy-efficient production of syngas. 5wt.% nickel (Ni) on ceria-zirconia (5wt%Ni@Ce0.6Zr0.4O2) mixed metal oxide catalyst was investigated here to explore pathways for enhanced syngas production on sustainable earth-abundant transition metal supported catalysts. The role of reduction-oxidation (redox) state of the catalyst, and carbon formation on the catalyst surface during chemical looping is explored to drive superior reaction kinetics, conversions, selectivity, and syngas ratios (H2/CO). The bulk and surface structure of the catalyst, along with carbon deposition features were characterized by electron microscopy, X-Ray diffraction, and ex situ Raman spectroscopy. The dynamic evolution of catalysts under CLR reaction conditions and the intrinsic reaction mechanisms were probed with in situ Raman spectroscopy, in situ Fourier transform spectroscopy, dynamic oxygen storage capacity (DOSC), and the Temporal Analysis of Products (TAP) reactor studies. Intrinsic kinetics of syngas production via CLR was correlated to the redox state of catalyst and the participation of nickel-catalyzed multiwalled carbon nanotube (CNT) growth, allowing enhanced CLR reaction performance.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2019

Conversion of acenaphthalene to phenalene via methylation: A theoretical study

Ab initio calculations of the C 13 H 10 and C 13 H 9 potential energy surfaces related to the reaction of 1-acenaphthyl and methyl radicals and secondary isomerization of C 13 H 9 primary radical products have been performed at the chemically accurate G3(MP2,CC)//B3LYP/6-311G** level of theory to unravel the mechanism of conversion of acenaphthalene to phenalene or phenalenyl radical + H. The computed energetics and molecular parameters were utilized in Rice-Ramsperger-Kassel-Marcus Master Equation (RRKM-ME) calculations of reaction rate constants and relative product yields. The 1-acenaphthyl + CH 3 reaction is predicted to proceed by a fast radical-radical recombination mechanism and to predominantly produce collisionally stabilized 1-methylacenaphthalene B1 or a C 13 H 9 benzylic radical A1 + H with exothermicities of 106.8 and 25.2 kcal/mol, respectively. The A1 + H channel is preferable at higher temperatures, whereas the stabilization of 1-methylacenaphthalene is favored at higher pressures. The radical A1 can nearly irreversibly interconvert to phenalenyl radical AP via a 22.7 kcal/mol exothermic isomerization process involving formal insertion of the CH 2 group into a C-C bond of the five-member ring leading to the expansion of this ring to a six-member ring. The rate constants for the H addition reaction to phenalenyl radical to form phenalene and the reverse H loss from phenalene were also computed and the strength of the weakest C-H bond in the CH 2 group of phenalene is evaluated as 62.2 kcal/mol. The analysis of the reaction kinetics allowed us to deduce a mechanism for the conversion of 1-acenaphthyl radical to phenalene or phenalenyl radical + H via methylation involving the formation of A1 via a well-skipping channel or stabilization and dissociation of (or H abstraction from) B1 followed by isomerization of A1 to phenalenyl AP, which can add an H atom producing phenalene. As a result, rate constants for the significant elementary reactions are fitted to modified Arrhenius expressions and are proposed for kinetic modeling of the expansion of a five-member ring on a zigzag edge of PAH to a six-member ring by methylation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Zeolite Membrane Reactor for Pre-Combustion Carbon Dioxide Capture (Final Scientific/Technical Report)

Water-gas shift (WGS) reaction followed by carbon dioxide (CO 2 ) separation is a critical step in the integrated gasification combined cycle (IGCC) process for fossil-fuel-fired electrical power generation with CO 2 capture. To intensify the IGCC process hydrogen-permselective zeolite membrane reactor offers promise to replace the conventional energy-intensive fixed-bed reactors and solvent-based CO 2 capture units. The objectives of this project were to develop a bench-scale zeolite membrane reactor (total membrane area: 932 cm 2 for a 21-tube membrane bundle) for the water-gas-shift reaction of raw syngas from an oxygen-blown coal-gasifier for H 2 production with simultaneous CO 2 separation at the capability of about 2 kilograms H 2 per day (equivalent to 2 kW IGCC power plant) and to demonstrate significant progress toward achieving overall performance goal of 90% CO 2 capture rate with 95% CO 2 purity at the cost of electricity 30% less than the baseline carbon capture approaches. This report summarizes results obtained in this project on scaling up the zeolite membrane reactor by a factor of 200 in membrane area, tests of the bench-scale zeolite membrane reactor for the water-gas-shift reaction at high temperature and high-pressure, and techno-economic analysis of the integration of the zeolite membrane reactor in IGCC power plant for the electrical generation with CO 2 capture. With effective pore modification by catalytic cracking deposition of MDES (methyldiethoxysilane), fabrication of MFI-type zeolite membranes was successfully scaled-up from a lab-scale disk type to bench-scale multiple-tube bundles on low-cost alumina supports. A Co-Mo based sour shift catalyst was evaluated and used in the zeolite membrane reactors for water-gas-shift reaction. The reaction kinetic and gas-permeation equations were developed and employed in mathematic models to guide/predict experiments/performance of zeolite membrane reactors for water-gas shift reaction. Multiple-tube zeolite membrane bundles and reactors were designed, fabricated and tested for gas separation and water-gas-shift reactions with real raw syngas from a coal-fired gasifier operated at high temperature and pressure. The zeolite membrane reactors demonstrated good long-term thermal and chemical stability and constant H 2 permeance (>300 GPU) together with a Knudsen selectivity (~4.7) for H 2 over CO 2 in the field test (cumulative time >28 hours) with high-sulfur coal-derived syngas. The zeolite-membrane-reactor integrated IGCC process was designed using the performance experimentally measured by the University of Cincinnati team with a single-tube zeolite membrane reactor that offers a CO conversion >98% with more than 90% of CO 2 and H 2 captured. With the above integrative approaches, a techno-economic analysis for a cost-benefit comparison was performed to uncover features that determine the power output, capital expenditure, operating expenditure, cost of electricity and cost of CO 2 capture in a 550-MW zeolite-membrane-reactor integrated IGCC process. The integration of the zeolite membrane reactor in IGCC could provide a significant reduction of 80% and 27% in the power consumption for Selexol™ Acid Gas Removal and CO 2 compression, respectively, which lowers the total auxiliary power consumption by 12.5%. However, the low pressure required at permeate stream for maintaining the driving force of hydrogen permeation through the zeolite membrane costs a huge power in permeate compressor, compensating the power consumption reduction achieved with the membrane reactor. Thus, for coal-fired IGCC for electricity generation with 90% CO 2 captured, the integration of the membrane reactor could provide a CO conversion ~99% and a significant drop in cost-of-electricity using zeolite membrane with H 2 permeance >600 GPU and the H 2 /CO 2 selectivity over 70.

01 COAL, LIGNITE, AND PEAT↗