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At least 127 records · Page 7

An Assessment of Kinetic Models for Ammonia Flame Extinction

The growing interest in using ammonia as a carbon-neutral replacement fuel has prompted numerous recent research efforts towards understanding fundamental combustion characteristics and chemical kinetics of ammonia oxidation. Despite these recent efforts, there remains a large deficiency in extinction limit data for ammonia flames, particularly under elevated pressure and temperature conditions relevant to gas turbines. Even the literature reaction mechanisms developed specifically for ammonia have been untested under gas turbine relevant conditions, and existing kinetic models have shown large variations in laminar flame speed, extinction strain rate, and speciation predictions for NH3–H2 mixtures at ambient conditions. Recent work by Thomas and co-workers, for example, compared different ammonia kinetic models in the literature for predicting their extinction strain rate measurements for non-premixed NH3-H2 counterflow flames, and again have highlighted the discrepancies in model predictions. Here, our work has undertaken to further highlight important reaction pathways for ammonia oxidation that may be responsible for these discrepancies for extinction strain rate predictions, as well as elucidate sensitive reaction steps with large uncertainties that require further attention. This work points to a need for an improved understanding of ammonia combustion chemistry as well as new datasets at elevated pressure and temperature conditions to better constrain rate expressions for key reaction steps.

ammonia, flame, combustion, kinetic, kinetics↗

Optimization of a Secondary Air Injector for a Rich-Quench-Lean (RQL) Ammonia Combustor Using Computational Fluid Dynamics

Ammonia has emerged as a promising medium for moving hydrogen around the globe due to its energy density, existing infrastructure for production, transportation, and storage, and multiple applications from fertilizer to power generation. However, one of the most significant challenges with ammonia combustion for power generation is the formation of nitrogen oxides (NOx) during combustion. Several combustion strategies have been developed to minimize the formation of NOx. One such strategy, known as rich-quench-lean (RQL), is a method that combusts NH3 in a fuel-rich environment, followed by a quick mix section and a lean burnout section. Rapid mixing of secondary air before lean burnout is thought to be important to minimize the formation of NOx. A genetic algorithm (GA) is used to parametrically vary the secondary air injector design, including the diameter, count, and angles over a constrained design space. The designs are evaluated using a non-reacting OpenFOAM model, with the objective function being the uniformity index of the secondary air (modeled as a scalar). Optimization campaigns show that traditional correlation-based designs might not be adequate. After running 414 OpenFOAM models, the optimal design is 32, 1 mm diameter, angled air injectors, increasing the uniformity index at the outlet of the quick mix zone by 36.8%. The most promising designs will be manufactured and tested in a small RQL burner setup, which is expected to lead to validation and insight into the practical usage of NH3 combustion for power generation.

ammonia combustion↗

Plants and mycorrhizal symbionts acquire substantial soil nitrogen from gaseous ammonia transport

Nitrogen (N) is an essential nutrient that limits plant growth in many ecosystems. Here we investigate an overlooked component of the terrestrial N cycle – subsurface ammonia (NH 3 ) gas transport and its contribution to plant and mycorrhizal N acquisition. In this work, we used controlled mesocosms, soil incubations, stable isotopes, and imaging to investigate edaphic drivers of NH 3 gas efflux, track lateral subsurface N transport originating from 15 NH 3 gas or 15 N-enriched organic matter, and assess plant and mycorrhizal N assimilation from this gaseous transport pathway. NH3 is released from soil organic matter, travels belowground, and contributes to root and fungal N content. Abiotic soil properties (pH and texture) influence the quantity of NH 3 available for subsurface transport. Mutualisms with arbuscular mycorrhizal (AM) fungi can substantially increase plant NH 3 -N uptake. The grass Brachypodium distachyon acquired 6–9% of total plant N from organic matter-N that traveled as a gas belowground. Colonization by the AM fungus Rhizophagus irregularis was associated with a two-fold increase in total plant N acquisition from subsurface NH 3 gas. NH 3 gas transport and uptake pathways may be fundamentally different from those of more commonly studied soil N species and warrant further research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Economizing on Precious Metals in Three-Way Catalysts: Thermally Stable and Highly Active Single-Atom Rhodium on Cera for NO Abatement under Dry and Industrially Relevant Conditions

We show for the first time that atomically dispersed Rh cations on ceria, prepared via high-temperature atom trapping synthesis, are the active species for (CO+NO) reaction. This provides a direct link with the organometallic homogeneous Rh(I) complexes capable of catalyzing dry (CO+NO) reaction but without the stability concern. In particular, thermally stable Rh cations in 0.1wt% Rh1/CeO2 achieve full NO conversion with a TOF of ~ 330 hr-1 per Rh atom at 120 °C. Under dry conditions, the main product above 100 °C is N2 with N2O being the minor product. The presence of water promotes low-temperature activity of 0.1wt% Rh1/CeO2 starting at 50 °C with full NO conversion at ~120 °C. In the case with the wet stream, however, ammonia and nitrogen are the main products with only minor N2O amounts. NH3 formation at such low temperatures is attractive because of the potential to use this as a passive SCR system. Because of the uniformity of Rh ions on the support, we are able to observe the intermediates of (CO+NO) reaction via infrared measurements on Rh cations on zeolite and ceria. Furthermore, we show that ammonia formation correlates with the WGS activity of the material and thus, rhodium hydride Rh-H species are involved in this reaction: we detect Rh(CO)Hx species on ceria using isotopic IR measurements. These findings provide new mechanistic understanding for the catalytically active species in TWC catalysis and open up a new avenue for the synthesis of novel emissions control catalysts with 100% atom economy of ultra-expensive precious metals such as Rh.

Khivantsev, Konstantin↗

Atomic Molybdenum for Synthesis of Ammonia with 50% Faradic Efficiency

The electrochemical dinitrogen (N 2 ) reduction reaction (NRR) under ambient conditions has gained significant interest as an environmentally friendly alternative to the traditional Haber–Bosch process for the synthesis of ammonia (NH 3 ). However, up to now, most of the reported NRR electrocatalysts with satisfactory catalytic activities have been hindered by the large overpotential in N 2 activation. The preparation of highly efficient Mo-based NRR electrocatalyst in acidic electrolytes under ambient conditions is demonstrated here, consisting of stabilized single Mo atoms anchored on holey nitrogen-doped graphene synthesized through a convenient potassium-salt-assisted activation method. At -0.05 V versus a reversible hydrogen electrode (RHE), an electrode consisting of the resultant electrocatalyst immobilized on carbon fiber paper can attain an exceptional Faradaic efficiency of 50.2% and a NH3 yield rate of 3.6 µg h -1 mg cat -1 with low overpotentials. Density functional theory calculations further unveil that compared to the original graphene without holes, the edge coordinated Mo atoms and the existence of vacancies on holey graphene lower the overpotential of N 2 reduction, thereby promoting the NRR catalytic activity. Finally, this work could provide new guidelines for future designs in single-atom catalysis that would be beneficial to ambient N 2 fixation, and replacement of classical synthesis processes that are very energy-intensive.

36 MATERIALS SCIENCE↗

Coordination Chemistry of Phosphine Ligands with Pendant Amines

Phosphine ligands with pendant amines have played an important role in the development of molecular electrocatalyst for H2 oxidation and production and for other potential energy storage and utilization reactions, such as CO2 and O2 reduction and NH3 oxidation. The pendant amines facilitate substrate binding, heterolytic bond cleavage and formation, intra- and intermolecular proton transfers, the formation of dihydrogen and hydrogen bonds, and provide a physical mechanism for coupling electron and proton transfer reactions. The structures of the phosphine ligands determine the ability of the pendant amines to participate in these different catalytic steps and the stability of the electrocatalysts as they are cycled between different oxidation states. These different features are illustrated by a detailed comparison of Mn, Fe, and Ni electrocatalysts for H2 oxidation that contain diphosphine ligands with pendant amines.

Phosphine, amines, electrocatalyst, dihydrogen, me↗

Recent advances in hybrid metal oxide–zeolite catalysts for low-temperature selective catalytic reduction of NOx by ammonia

A hybrid catalytic system comprised of metal oxide and Cu or Fe exchanged zeolite components represents a potential advancement of state-of-the-art for selective catalytic reduction (SCR) of NOx by ammonia, including an elegant solution to the current challenge of improving the low-temperature efficiency of SCR catalysts. The idea is to enable in-situ NO oxidation over metal oxide component and concomitant fast SCR over zeolite component in the so-called “bifunctional mechanism”. This review is presented in the wake of growing interest in this innovative catalytic system. We begin this review by presenting key parameters that contribute to the synergy between metal oxide and zeolite components. Then, we discuss the materials selection for both components and their possible interactions in the system, followed by a summary of recent NH3-SCR investigations over multiple metal oxide–zeolite pairs and additional discussion on pairing techniques potentially explorable in upcoming studies. Finally, we end the review by providing the perspectives on future challenges in the development of this catalytic system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Selective catalytic reduction of NOx with NH 3 over Ce-Mn oxide and Cu-SSZ-13 composite catalysts – Low temperature enhancement

A composite catalyst comprised of ceria-manganese oxide and Cu-SSZ-13 components represents a potential solution for improving selective catalytic reduction (SCR) of NOx by ammonia. Here, clarity is provided to the pathway of promotion on these catalysts at low temperatures (< 200 °C), and it is shown that improved performance comes solely from interaction of the oxide phase with Brønsted acid bound NH 3 . We demonstrate that at low temperatures, the catalytic components interact via oxide-derived nitrites/nitrite-precursors (e.g., HONO, N 2 O 3 ) reacting with Brønsted acid bound NH3 from the zeolite. Then, only at elevated temperatures is the influence of the oxide phase on Cu redox in the Cu-SSZ-13 observed. Furthermore, we show how the oxide component has the great potential to circumvent NH 4 NO 3 inhibition on Cu-SSZ-13 in the composite catalysts at low temperatures by bypassing the formation of nitrates from NO 2 disproportionation, thus providing a practical solution to improving low temperature SCR reactivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A comparative study between real-world and laboratory accelerated aging of Cu/SSZ-13 SCR catalysts

Elucidating aging mechanisms in real-world applications is a critical component for developing and maintaining Cu/SSZ-13 SCR catalysts. To reveal gaps between laboratory accelerated aging and real-world aging, herein we report thorough comparative studies between 6 representative catalysts. Here, we apply a wide range of catalyst characterization methods, including surface area/porosity analysis, X-ray diffraction (XRD), H 2 -temperature programmed reduction, NH3-temperaure programmed desorption, solid-state nuclear magnetic resonance (NMR), in situ X-ray photoelectron (XPS) and electron paramagnetic resonance (EPR) spectroscopies, to gain atomic-level knowledge on Cu transformation under different aging protocols. We then correlate such knowledge to SCR, NH 3 /NO oxidation kinetic behavior of the catalysts. We found that sulfur aging plays the most important role in interpreting catalyst degradation during real-world application, including direct sulfur poisoning of isolated Cu II SCR active species to CuSO 4 -like species, the agglomeration of such species to multinuclear CuSO 4 clusters, and eventually, CuO formation during desulfation treatments. Such chemistries convert SCR active Cu to SCR inert Cu moieties without severely deteriorating catalyst support integrity. These characteristics are partially replicated by hydrothermal aging in the presence of SOx but are poorly mimicked by hydrothermal aging alone.

36 MATERIALS SCIENCE↗

A redox model for NO oxidation, NH 3 oxidation and high temperature standard SCR over Cu-SSZ-13

A kinetic model is developed to predict the influence of temperature and hydrothermal aging on the redox of active Cu sites under standard SCR, NO oxidation and NH 3 oxidation conditions over a practically relevant fully-formulated Cu-SSZ-13 catalyst. NO 2 /N 2 production during NO/NH 3 titration of Cu II sites is utilized to identify rate parameters associated with NO-only RHC (reduction half cycle) and NH 3 -only RHC respectively. Integral N 2 formation during subsequent NO + NH 3 titration is consistent with the production of one NO 2 per two CuII sites reduced during NO-only RHC and one N 2 per six Cu II sites reduced during NH 3 -only RHC. Decreased reduction of Cu II sites by NO/NH 3 upon hydrothermal aging, along with the production of one NO 2 per two CuII sites during NO-only RHC, is accordant with the involvement of proximal ZCuOH and oxygen-bridged dimeric Cu II sites. Oxidation of partially solvated and framework coordinated ZCu (Cu I ) sites occurs in presence of O 2 , does not produce N 2 and can lead to the consumption of Brønsted acid sites. A global OHC kinetic model is developed to predict transient and integral N 2 formation during exposure of CuI sites to a mixture of NO and O 2 . The resulting redox kinetic model quantitatively predicts NO and NH 3 consumption during isothermal transient response Cu redox (TRCR) protocols, along with temperature and age dependent steady-state standard SCR and oxidation conditions. The redox model presented in this work synthesizes recent kinetic, spectroscopic and computational findings to provide a foundational description of active site redox during standard SCR, NO oxidation and NH3 oxidation over Cu-SSZ-13.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding the Origin of Negative Temperature Dependence and Activity of N-Coordinated Cobalt Sites During Ethylene Dimerization

The on-demand production of short-chain linear alpha olefins (LAOs; C4-C8) via C2H4 dimerization and oligomerization is industrially attractive, prompting extensive research on designing active, selective, and stable catalysts for industrial use. Cobalt supported on ammoniated carbon (Co(NH3)x/C) catalysts have shown remarkable activity and selectivity in this process. However, critical aspects such as the active phase, active site structure, the role of the catalyst support, cobalt loading effects, and the inverse correlation of the reaction rate with temperature remain inadequately understood. This study systematically explores these factors using a combination of steady-state differential catalytic tests, in situ molecular characterization including diffuse reflectance UV-Vis (DR-UV-Vis), Infrared, and Raman spectroscopies, and ex situ X-ray diffraction (XRD) and high annular aberration-corrected dark field transmission electron microscopy (HAADF-STEM). Various supports (SiO2, Al2O3, NH4-ZSM-5, g-C3N4, and C) and cobalt loadings (1.0-3.0 Co nm-2) were studied to determine the optimal catalyst composition and identify the active phase and sites. Carbon-supported catalysts uniquely produce C4-8 LAOs during C2H4 dimerization, with site-time-yield remaining constant (~10-3 s-1) for 1.0-4.0 Co nm-2 at prolonged reaction times (24-48?h time-on-stream). At higher loadings of 6.0 Co nm-2, the formation of crystalline CoO and Co3O4 phases reduces catalytic activity and LAO selectivity. Our findings show that active catalysts lack crystalline cobalt oxides and instead feature dispersed Co2+ sites, tetra-coordinated to a mix of N/NH3 and O/H2O ligands, which catalyze C2H4 dimerization via the Cossee-Arlman mechanism, exhibiting 1st order dependence on C2H4 concentration. The observed inverse rate-temperature correlation is attributed to compensation effects (i.e., presence of Cremer-Constable relationship) linked to changes in adsorption enthalpic and entropic factors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microwave-Mediated ammonia synthesis over Co 2 Mo 3 N catalysts at low pressures

The Haber-Bosch process for ammonia (NH 3 ) synthesis is a major contributor to greenhouse gas emissions and is responsible for > 2 % of the world’s energy consumption each year encouraging the need for alternative renewable-based options. Here, this study investigates an earth-abundant ternary metal nitride (i.e., Co 2 Mo 3 N) catalyst to develop a renewable-based NH 3 synthesis approach, utilizing an energy-efficient microwave-assisted route. Using a combination of spectroscopic and catalytic measurements coupled with surface analysis techniques, Co 2 Mo 3 N was evaluated as a stable and efficient NH 3 synthesis catalyst. Results presented here demonstrate NH 3 synthesis on Co 2 Mo 3 N at ~420 °C and ambient pressure yield ~0.7 mmolNH3.g cat -1 .h -1 and up to ~12 mmol NH3 .g cat -1 .h -1 at 28 bar under microwave irradiation. Co 2 Mo 3 N displayed an activation energy of ~72 kJ.mol -1 and yielded NH 3 following first-order kinetics with respect to both H 2 and N 2 . These studies illustrate the potential of using this catalyst for a sustainable, cost-effective, and environmentally friendly approach to producing NH 3 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Flame dynamics and kinetic coupling of ammonia and dimethyl-ether in non-premixed cool and warm flames at elevated pressure

Developing advanced low-temperature combustion engines with ammonia-biofuel blends requires a comprehensive understanding of low-temperature flame dynamics and kinetic interactions between ammonia and oxygenated fuels at elevated pressures. This work aims to study the dynamics and kinetics of non-premixed Dimethyl Ether (DME)/Ammonia (NH 3 ) cool and warm flames, and their reignition to hot flames. A counterflow burner is employed to establish DME/NH 3 cool/warm flames at pressures up to 5 atm. The extinction limits of cool flame and the reignition limits of warm flame to hot flame are measured by varying NH 3 concentrations and compared to simulations to quantitatively examine the effects on DME/NH 3 flames. It is found that NH 3 inhibits low-temperature DME oxidation and results in lower cool flame extinction limits. Warm flames in the presence of NH 3 are observed for the first time, revealing a non-monotonic effect of NH 3 addition: a small amount of NH 3 presence enhances warm flame chemistry and promotes reignition to hot flames, while a high NH 3 concentration weakens the warm flame. This trend is further explained by 0-D PSR kinetic simulations and 1-D S-curve flame dynamic calculations. Three flame transition regimes between cool flames (CF), warm flames (WF), and hot flames (HF) by different levels of NH 3 additions at a specific strain rate are identified, namely WFHF reignition, WF-CF transition, and WF extinction. Reaction sensitivity analyses of OH at low temperatures show that NH3 inhibits DME oxidation through OH consumption via H-abstraction and the kinetic couplings of RO 2 /NH 2 , RO 2 /NO x , R/NO x , and O 2 QOOH/NO x further suppress the low-temperature branching. At intermediate-temperatures, NH 2 /NO x /HO 2 coupling promotes warm flames via the pathway NH 2 → H 2 NO → HNO → NO by converting O 2 → HO 2 → OH. At even higher NH₃ concentrations, radical termination reactions of NH 2 + NO/NO 2 and excessive OH consumption via H-abstraction inhibit the flame. The insights into the kinetic coupling between NH 3 and low-temperature chemistry at elevated pressure and its impact on the dynamics of cool-warm-hot flame transitions will contribute to advancing combustion technologies with reduced emissions and improved energy-efficiency.

42 ENGINEERING↗

Performance of biochar assisted catalysts during hydroprocessing of non-edible vegetable oil: Effect of transition metal source on catalytic activity

Biochar-supported catalysts were developed from nickel (Ni) - and cobalt (Co)- nitrates and hydroxides and tested for the hydrotreatment of carinata oil. Nitrate-based (from water-soluble salts) and hydroxide-based (from water-insoluble salts) catalysts of Ni and Co were prepared via wetness impregnation and aqueous dispersion methods, respectively. The catalysts were characterized using various tools such as, confocal XRF, BET specific surface area analyzer, NH3-TPD, and SEM-EDS. Synchroton method showed nitrate-sourced metals were dispersed mostly in the pores while, the hydroxide-sourced metals were distributed mainly on the catalyst surface. C = C saturation and cracking of triglycerides, decarboxylation, and hydrogenation of aromatic structures appeared to be dominant on the hydroxides of transition metals, hence took place on catalyst surface. Methanation and dehydrogenation (thus aromatization), however, seemed to be a pore phenomenon, catalyzed more over nitrate-based catalysts. A reaction network was proposed based on chemical analysis of upgraded carinata oil and erucic acid model compound. Catalytic cracking followed by hydrotreatment performed better in terms of fuel properties than other approaches in this study.

Biochar catalysts↗

Effects of carbon treating on piperazine oxidation in pilot plant testing of PZAS™

From February to June 2019, a pilot plant campaign was run for 2100 h at the National Carbon Capture Center (NCCC) using moderately degraded 5 m PZ with simulated flue gas equivalent to a 0.64 MW natural gas combined cycle. Piperazine with the Advanced Stripper™ (PZAS™) and a baghouse were used, and N 2 sparging was applied at the bottom of the absorber. A carbon bed was activated and showed beneficial effects in removing degradation products and reducing the oxidation rate. The cumulative NH 3 production was 180 mmol/k, indicating a PZ oxidation rate of 0.07 mmol/kg/h (0.3 kg PZ/tonne of CO 2 ). The total formate before turning on the carbon bed was 41 mmol/kg, and the total Fe was 0.1 mmol/kg. Carbon treating reduced NH3 production from 0.1 mmol/kg/h to 0.056 mmol/kg/h after 400 h of operation, reduced the UV-Vis absorbance of the samples at 320 nm, and caused a decrease of dissolved Cr. Bench-scale experiments were performed using the NCCC solvent and the same type of carbon. In bench-scale experiments, the UV-Vis absorbance and the concentration of Fe, Mn, and Cr all decreased. Finally, a linear equilibrium relationship was observed between the UV-Vis absorbance and the carbon loading.

03 NATURAL GAS↗

Challenges in Kinetic modeling of ammonia pyrolysis

Ammonia pyrolysis reactions have implications for its ignition and oxidation in engines and gas turbines. In the present work, the chemistry of ammonia pyrolysis is investigated by kinetic modeling and theory. Rate constants for key reactions are carefully evaluated based on available experimental and theoretical results. The high pressure limit k1,∞ for NH 2 + H (+M) &rlarr; NH 3 (+M) (R1) is calculated to be essentially the collision frequency, indicating that dissociation of ammonia in combustion processes will be at or close to the low pressure limit even at engine and gas turbine conditions. The chemical kinetic model is validated against reported shock tube measurements of NH 3 , NH 2 , and NH in ammonia pyrolysis. Predictions are in good agreement with observations for dilute conditions (≤ 0.5% NH 3 ), but the model appears to underpredict the NH 3 consumption rate at longer times in less dilute mixtures. At short reaction times, thermal dissociation of NH3, together with the NH 3 + H reaction, controls conversion. At longer times, secondary reactions involving NH 2 and NH become important due to their impact on the radical pool. Predictions become sensitive to formation and consumption of diazene (tHNNH and cHNNH). Several of the key steps in the ammonia pyrolysis mechanism are radical-radical reactions that are difficult to measure accurately and challenging to calculate theoretically, and a more comprehensive experimental characterization is desirable to support further model development.

10 SYNTHETIC FUELS↗

Boosting the sodium storage behaviors of carbon materials in ether-based electrolyte through the artificial manipulation of microstructure

The porous carbon blacks rationally designed by a facile yet efficient NH 3 thermal etching route have been investigated as anode materials in an ether-based electrolyte for sodium-ion batteries. The as-synthesized CBN35 carbon black with a 35% weight loss after NH3 thermal etching exhibited a large specific charge capacity of 352 mAh g -1 at 50 mA g -1 and a superior rate capability of 101 mAh g -1 at 16000 mA g -1 , due to its highest microporosity, an appropriate surface area, a desirable microstructure, and a promising hybrid intercalation mechanism. Impressively, even cycled at 1600 mA g -1 over 3200 cycles, an outstanding reversible capacity of 103 mAh g -1 with a negligible 0.0162% capacity loss per cycle can still be achieved. Based on the multimodal characterizations including the structural probes of phase evolution for carbon materials, the electrochemical techniques, and the surface-sensitive XAS measurements, the exceptional electrochemical properties should stem from several merits of modified carbon black system. While the particular microporous structure provides relatively more accessible sodium storage sites, a novel hybrid intercalation mechanism in ether-based electrolyte would incorporate the sodium ion insertion into the disordered structure with the solvated sodium ion species co-intercalation into the graphitic phase. In addition to the diffusion-controlled redox reactions, the noticeable surface-induced pseudocapacitive reactions also significantly contribute to the charge storage upon sodiation and guarantee the rapid migrations of sodium ions/solvated compounds. In conclusion, this system further features a controlled emergence of a robust but thin solid electrolyte interphase layer, which could suppress the side reactions of active electrode with reactive electrolyte, maintain the fragile porous structure upon cycling, and facilitate the migrations of sodium ions and solvated sodium ion compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗