Mixture Of NH3 Research Articles

An experimental and kinetic modeling study on the auto-ignition of ammonia/butan-1-ol mixtures

Ignition delay times (IDTs) of ammonia(NH3)/butan-1-ol mixtures with NH3/butan-1-ol mole ratios of 100/0, 95/5, 90/10 and 70/30 were measured behind reflected shock waves in a shock tube over a range of experimental conditions: temperature range of 1100 – 2000 K, pressures of 0.14 and 0.5 MPa, equivalence ratios of 0.5, 1.0 and 2.0. A new NH3/butan-1-ol reaction mechanism, capable of predicting the experimental results reliably, was developed. Chemical kinetic analyses were performed with the model. It is demonstrated that increasing the content of butan-1-ol in the reaction system results in a non-linear trend of shortening on the IDTs of mixtures, adding 5 % molar fraction of butan-1-ol results in shortening rates of over 70 %. As the butan-1-ol blending ratio increases from 5 % to 30 %, the discrepancy in IDT of the mixture between equivalence ratios of 0.5 and 1.0 diminishes while it remains more pronounced between equivalence ratios of 1.0 and 2.0. The presence of butan-1-ol does not change the oxidation pathways of the NH3 mixture. R72(NH3 + M = NH2 + H + M) and R75(NH2 + HO2 = NH3 + O2) are key reactions to activate chain reactions of the NH3 mixture during the initial reaction stage, for a temperature of 1500 K, a pressure of 0.14 MPa, and an equivalence ratio of 1.0. Reactive radicals produced through the process of butan-1-ol oxidation result in a significant increase in the initial dehydrogenation consumption rate of NH3, by a factor of 5 ∼ 6 powers of ten, accelerating chain reactions.

Flame Speed Measurements of Ammonia–Hydrogen Mixtures for Gas-Turbines

Abstract Recent findings from the U.S. Energy Information Administration project an increase in domestic fossil fuel consumption (e.g., petroleum and natural gas) and global greenhouse gas emissions through 2050 (Nalley, S., 2021, “International Energy Outlook 2021 (IEO2021),” IEO2021 Release, CSIS, Center for Strategic and International Studies, Washington, DC, Technical Presentation, pp. 2–12). Consequently, advanced combustion research aims to identify fuels to mitigate fossil fuel consumption while minimizing exhaust emissions. Ammonia (NH3) is one of these candidates, as it has historically been shown to provide high energy potential and zero-carbon emission (CO and CO2) (Hayakawa, A., Goto, T., Mimoto, R., Arakawa, Y., Kudo, T., and Kobayashi, H., 2015, “Laminar Burning Velocity and Markstein Length of Ammonia/Air Premixed Flames at Various Pressures,” Fuel, 159, pp. 98–106). As a hydrogen (H2) carrier, NH3 serves as a possible solution to the U.S. Department of Energy's Hydrogen Program Plan by providing efficient H2 storage and conservation capabilities (U.S. Department of Energy, 2020, “Department of Energy Hydrogen Program Plan,” U.S. Department of Energy, Washington, DC, Report No. DOE/EE-2128). As a result, applied turbine-combustion research of NH3 and H2 fuel has been conducted to identify combustion performance parameters that aid in the design of sustainable turbomachinery (Chiong, M.-C., Chong, C., Ng, J., Mashruk, S., Chong, W., Samiran, N., Mong, G., and Medina, A., 2021, “Advancements of Combustion Technologies in the Ammonia-Fuelled Engines,” Energy Convers. Manage., 244, p. 114460). One of these key combustion parameters is the laminar burning speed (LBS). While abundant literature exists on the combustion of NH3 and H2 fuels, there is not sufficient evidence in high-pressure environments to provide a comprehensive understanding of NH3 and H2 combustion phenomena in turbine-combustor settings. To advance the state of the knowledge, NH3 and H2 mixtures were ignited in a spherical chamber across a range of equivalence ratios at 296 K and 5 atm to understand their flame characteristics and LBS which was determined using a multizone constant volume method. The experimental conditions were selected according to primary turbine-combustor conditions, as much research is needed to support NH3–H2 applicability in turbomachinery for power generation. The effect of H2 addition to NH3 fuel was observed by comparing the LBS for various NH3–H2 mixture compositions. Experimental results revealed increased LBS values for H2 enriched NH3, with the maximum LBS occurring at stoichiometry. The experimental data were accurately predicted by the University of Central Florida (UCF) NH3–H2 mechanism developed for this investigation, while NUI 1.1 simulations overestimated recorded LBS data by a significant margin. This study demonstrates and quantifies the enhancing effect of H2 addition to NH3 fuels via LBS and strengthens the literature surrounding NH3–H2 combustion reactions for future work.

Stage-wise kinetic analysis of ammonia addition effects on two-stage ignition in dimethyl ether

Abstract Ammonia (NH3) has gained considerable attention as a promising carbon-free hydrogen carrier fuel for internal combustion engines, but its direct use in compression-ignition engines presents challenges, often requiring high-reactivity fuels to ignite the premixed NH3/air mixture and initiate combustion. This study focuses on the ignition process of binary NH3 and dimethyl ether (DME) mixtures, as DME is a carbon-neutral, high-reactivity fuel. A key novelty of this paper is the comparison of the ignition processes of DME and NH3/DME mixtures from a temporal, process-oriented perspective, analyzing chemical kinetics across distinct ignition phases rather than focusing solely on instantaneous reactions at discrete time points. The stage-wise analysis reveals that NH3 has minimal impact on the control mechanism governing the two-stage ignition process of DME. Specifically, DME still largely depends on OH radical proliferation during low-temperature oxidation (LTO), which releases heat as the reaction progresses. As the temperature increases, LTO branching pathways gradually shift to chain-propagation pathways, reducing overall reaction activity. The reactivity and temperature rise rate of the system are then governed by the H2O2 loop mechanism before thermal ignition. However, ammonia significantly extends the ignition delay of DME by competing with OH radicals, which are critical for DME oxidation, thus inhibiting ignition. As the ignition reaction proceeds, ammonia kinetics become more involved. For example, nitrogen-containing species from NH3 oxidation, such as NO, NO2, and NH2, react with CH3OCH2 to form CH3OCHO, reducing the flux through the LTO pathway of DME. While ammonia reaction pathways also produce OH radicals, this occurs at the expense of HO2 and H radicals, leading to H2O2 formation. Overall, these findings demonstrate the substantial impact of ammonia addition on DME ignition, highlighting the need for further research to better understand NH3/DME binary fuel ignition and to optimize the design and operation of NH3/DME dual-fuel engines for improved efficiency and reliability.

Detection of CO2, H2S, NH3, and gas mixtures using a quartz crystal microbalance sensor array with five sensitive materials

The large-scale development of chicken farms has inevitably led to an increase in the emission of harmful gases, which has prompted rapid research development on the detection of harmful gases, such as quartz crystal microbalance (QCM) sensors. In this research, a QCM sensor array modified with ethyl cellulose (EC), polyethyleneimine (PEI), polypyrrole (PPy), tetramethylammonium fluoride tetrahydrate (TMAF), and Nitrogen-doped tungsten carbide supported on carbon nanosheets (WC@NC) was established to detect gas mixtures. By analyzing the relationship between the fundamental frequency shift and the number of sensitive material layers for the QCM sensor, the optimal number of layers was determined. The QCM sensor array consisted of a blank QCM sensor, an 8-layer EC sensor, a 4-layer PEI sensor, a 3-layer PPy sensor, an 8-layer TMAF sensor, and an 8-layer WC@NC sensor. The results showed that the PEI sensor exhibited maximum frequency shifts when detecting gases, while TMAF and WC@NC films had the highest contribution to NH3 detection. TMAF, PEI, and WC@NC played significant roles in the binary classification of exceeding the standard detection of NH3. Additionally, WC@NC and EC sensors played an important role in detecting H2S and CO2, respectively. The QCM sensor array could accurately classify the excessive state of CO2. Overall, the QCM sensor array demonstrated a correct recognition rate of 87.5 %, indicating its potential for classifying the exceedance of NH3, CO2, and H2S gases in gas mixtures. This work provides basic information for research on QCM sensor arrays in gas detection.

Enhancement of Wear and Corrosion Resistance of Ti6Al4V Alloy through Hollow Cathode Discharge-Assisted Plasma Nitriding.

In order to improve the wear and corrosion resistance of Ti6Al4V alloy, a Ti-N compound layer was formed on the alloy by plasma nitriding at a relatively low temperature (750 °C) and within an economical processing duration (4 h), in a mixture of NH3 and N2 gases with varying ratios. The influence of the gas mixture on the microstructure, phase composition, and properties of the Ti-N layer was investigated. The results indicated that the thickness of the nitrided layer achieved in a mixed atmosphere with optimal proportions of NH3 and N2 (with a ratio of 1:2) was substantially greater than that obtained in an atmosphere of pure NH3. This suggests that appropriately increasing the proportion of N2 in the nitriding atmosphere is beneficial for the growth of the nitrided layer. The experiments demonstrated that the formation of the surface nitrided layer significantly enhances the corrosion and wear resistance of the titanium alloys.

Thermo-Mechanical Properties and Benefits of Borosilicate Glass for SOEC Sealants

Boro-silicate glass materials have ideal properties for sealing oxidizing and reducing environments and electrically insulating solid oxide electrolysis cells (SOEC), while maintaining a glassy phase at high temperatures (750-900°C) to minimize chemo-mechanical degradation and gas permeability 1,2. Glass seals are typically applied as a slurry; hence, they are also expected to have non-wetting properties to prevent glass infiltration into the porous electrode structures during manufacturing 3. During the first startup, the initial temperature ramp serves to evaporate any binder in the slurry and to go through the glass transition phase, which cures the glass and increases hardness to improve resistance to creep. Typical glass materials operate in visco-plastic regimes (i.e., beyond the material’s glass transition temperature) and must be chemically stable while operating in steam-rich and oxygen-rich environments. To fully understand the performance of borosilicate glass seals, optimize the manufacturing, assembly, and maintenance of SOEC, we must be able to measure and analyze the glass material properties (i.e., glass transition temperature, coefficient of thermal expansion, modulus, creep, hardness) at the same operating conditions relevant for SOEC operation. In this work, we characterize the thermo-mechanical properties of borosilicate glass powder and sintered samples at various temperatures (ranging from ambient to 850°C), and at different aging conditions (i.e., atmosphere composition, temperature, and duration). The atmosphere composition is changed between air, steam-N2 mixtures, and H2-N2 mixtures to evaluate the chemical stability of borosilicate glass relating to the possible depletion of boron and silicon via the formation of boron hydroxide and silicon vapor when exposed to steam- and hydrogen-rich environments. The aging temperature and duration is varied to evaluate the crystallization kinetics, particle size growth, and its effect on mechanical properties. We employ a combination of Simultaneous Thermal Analysis - STA (i.e., combined Thermogravimetric Analysis - TGA, Differential Scanning Calorimetry - DSC, Fourier Transform Infrared - FT-IR spectroscopy, and Quadrupole Mass Spectroscopy - QMS), and nanoindentation as characterization techniques, while surface roughness is estimated with a 3D confocal optical microscope.Surface roughness varies between 0.83-1.38 𝜇m ± 1.1-1.76 𝜇m (Sa ± Sq). Both powder and solid samples are analyzed via STA with sequential temperature ramps (constant heating rate at 10 K/min in Ar atmosphere) up to 1500°C to estimate the effect of crystallization and particle size on the glass transition onset. For a sample aged at 850°C for 340 h, the first ramp shows typical DSC exothermic peaks (mW/mg) at around 800°C, with a midpoint glass transition occurring at 900°C. However, on the second ramps, peaks lower to around 500°C and the glass transition is estimated to be around 700°C. Subsequent tests consistently mirrored the trend of the second temperature ramp, showing minimal deviation and influence of crystallization and particle growth. Nanoindentation is performed between room temperature and 600°C to characterize both sintered glass samples “as-received” and aged at temperatures between 750-950°C for 340 h. Comparing a sample aged at 750°C with an “as-received” sample, the elastic moduli equally decreased from 100 GPa at room temperature to 40 GPa at 600°C, with comparable hardness values ranging from 10 GPa at room temperature to 0.5-0.9 GPa at 600°C, respectively. A.G. Sabato, G. Cempura, D. Montinaro, A. Chrysanthou, M. Salvo, E. Bernardo, M. Secco, F. Smeacetto, Journal of Power Sources, 328, 262-270 (2016)Dilshat U. Tulyaganov, Allu Amarnath Reddy, Vladislav V. Kharton, José M.F. Ferreira, Journal of Power Sources, 242, 486-502 (2013)S.-B. Sohn, S.-Y. Choi, G.-H. Kim, H.-S. Song, G.-D. Kim, Stable sealing glass for planar solid oxide fuel cell, J. Non. Cryst. Solids. 297 (2002) 103–112. doi:10.1016/S0022-3093(01)01042-0 Figure 1

Characterization and electrochemical performance of plasma-nitrided titanium alloy for bipolar plates

Ti-N layer with a thickness about 1 ∼ 2.2 μm was formed on titanium alloys through plasma nitriding at 750 °C in NH3 and a mixture of NH3 and N2 (1:2) for 4 h. SEM and XRD were employed to characterize the microstructure and phase composition of nitrided layer. Electrochemical tests evaluated the anti-corrosion properties of the samples before and after nitrided in a simulated proton exchange membrane fuel cells (PEMFC) environment. Interface contact resistance (ICR) was also measured. Results indicated that the corrosion potential in cathodic conditions was increased from −415 mV for untreated titanium to 148 mV for that nitrided in mixture gas. While, the corrosion current density was reduced from 6.64 μA to 0.86 μA. Under a pressure of 140 N cm−2, the interfacial contact resistance of the untreated sample increased from 22.1 mΩ cm2 before corrosion testing to 40.5 mΩ cm2 after corrosion at cathodic conditions. The nitrided sample, on the other hand, saw its contact resistance rise from 4.5 mΩ cm2 before corrosion to 7.3 mΩ cm2 after corrosion. The Ti-N compound layer effectively diminished the corrosion current density and sustained an exceptionally low ICR under the simulated operating conditions of a bipolar plate.

Competitive Adsorptive Mechanism of H2/N2 in LTA/FAU Zeolites by Molecular Simulations and Experiments.

For industrial tail gas to be converted into high-purity hydrogen, the H2-N2 mixture needs to be separated efficiently. This work examined the adsorption characteristics and competitive mechanisms of H2 and N2 on LTA- and FAU-type zeolites, at 77 K, 298 K, and 0.1-10 bar by thoroughly analyzing results of adsorption capacity experiments and molecular simulations. In the Grand Canonical Monte Carlo (GCMC) simulations, the force field causing a molecular dipole of H2 and the polarization force field of N2 are first applied. The accuracy of the force field was experimentally verified. The findings indicate that N2 and H2 loading on Ca-FAU (Ca-LTA) are higher than Na-FAU (Na-LTA). On NaX at 77 K, the highest adsorption selectivity (N2/H2) is observed; on NaA at 298 K, it is the opposite. The GCMC data findings demonstrate that H2 and N2 have remarkably similar adsorption sites, with framework oxygen atoms and non-framework cations serving as the main adsorption sites for adsorbate molecules. Furthermore, the rate at which H2 diffuses is higher than that of N2. The study of redistribution charge before and after adsorption demonstrated that N2 has a greater affinity for the framework oxygen atoms than H2. This study provides a molecular theoretical foundation for the adsorption behavior of H2-N2 mixture in zeolites.

In-situ inhibition mechanism of SO3 formation over MoS2 modified V2O5/TiO2 catalyst within selective catalytic reduction process

The utilization of commercial vanadium-titanium based catalysts (V2O5/TiO2) within the selective catalytic reduction (SCR) process is a prominent contributor to the emergence of sulfur trioxide (SO3) in coal-fired boiler environments. The direct modification of vanadium-titanium based catalysts has big potential to be an efficacious strategy for in-situ inhibiting SO3 formation. This research evaluates the effectiveness of MoS2 modified V2O5/TiO2 catalyst on SO2 oxidation under diverse conditions, using controlled condensation for SO3 collection. The results showed that V2O5-MoS2/TiO2 catalysts outperformed conventional V2O5/TiO2 catalysts in inhibiting the oxidation from SO2 to SO3 between 200 and 400 °C, with optimal performance at 350 °C. No significant effect was observed on the catalytic oxidation of SO2 when the O2 concentration was lower than that of SO2, whereas the introduction of appropriate quantities of NO promoted the generation of SO3. The excessive inclusion of NH3 nearly doubled the SO3 generation rate, increasing it from 0.284 % to 0.434 %. The NO and NH3 mixture markedly reduced SO3 generation to 0.085 % at a 62 mL/min mixture concentration, just 30 % of the rate without the mixture. Following the reaction of SO2 and O2, the reacted catalyst exhibited reduced pore volume, enhanced thermochemical stability, and lower susceptibility to SO2 catalytic oxidation. The addition of low-valence sulfur improves catalyst reducibility, reduces V5+–OH reactions in various atmospheres, and decreases the formation of sulphate and gaseous SO3. The Mo-S-Mo group also effectively prevents the formation of HSO4− intermediates. Additionally, MoS2 reacts with SO3 via a reduction reaction, significantly lowering the SO3 levels. Finally, in diverse atmospheric conditions, the catalysts maintained their V5+ content and catalytic efficiency, thus improving SCR performance stability.

Robot-assisted optimized array design for accurate multi-component gas quantification

Designing sensor arrays is a common strategy for detecting mixtures. However, a sensor array designed based on human experience leads to inaccuracies due to cross-sensitivity and information overlap. This difficulty led to the realization that arrays should be optimized as a whole. The conventional array optimizing method involves selecting the best subarray from a limited sensor pool. However, this method did not consider the vast continuous multi-dimensional variable space of each sensing element’s recipe, thus only generating a simpler array with limited detection capacity. To address this problem, we developed a Robot-assisted Optimized Array Design (ROAD) method. This innovative method holistically optimizes the sensor array across a continuous and vast variable space, overcoming the bottlenecks of high dimensionality and high-quality data collection. We applied ROAD to an optoelectronic nose, tasked with detecting a mixture of CO2, NH3, and water vapor. The method explored an immense space, estimated at the order of 2^(10^7). The implementation of ROAD led to a revolutionary quantitative accuracy, achieving an average relative standard deviation of 1.90%. This advancement has propelled the application of optoelectronic nose from qualitative to quantitative. The successful ROAD of system-wide array optimization has been demonstrated in the optoelectronic nose, validating the potential of the holistically optimized sensor array for accurately quantifying each component in a gas mixture.

Effect of preheating on extending lean extinction limit of ammonia/air combustion in a two-section porous burner

Ammonia utilization is promising way to reduce greenhouse gases emissions. We propose the concept of reactants preheating to achieve stable combustion of lean NH3 in two-layer porous burner, this concept is validated by numerical study with full kinetics. Calculations are conducted over wide range of preheating temperature (Tpre) and mass flow rate (m″) to gain insight in stable map, with special emphasis on effect of Tpre on extending lean extinction limit (LEL). It is shown that Tpre has vital effect in expending LEL. LEL is continually extended for different m″ with preheating, the LEL for NH3/air is successfully extended from equivalence ratio (ϕ) of 0.54 to 0.08 with increasing Tpre from 400 K to 1000 K. It is found that there exist three distinct mechanisms (Ⅰ, Ⅱ and Ⅲ) with respect to ϕ. When ϕ is close to one, self-sustaining combustion is realized without preheating (Ⅲ). The combustion is becoming unstable when ϕ is decreased, stable combustion can only be achieved with preheating (Ⅰ). Flame extinction takes place even with the preheating (Ⅱ) when the Tpre is lower than critical one for the given ϕ. The results present guidelines for burner operating with lean NH3 mixture over wide parameters range.

Optimized global reaction mechanism for H2+NH3+N2 mixtures

Hydrogen and ammonia are playing an increasingly vital role in combustion technologies. Recently, some detailed reaction mechanisms (DRMs) can predict reliable laminar burning velocities (LBVs). Meanwhile, despite their broad applicability in practical combustion engineering, global reaction mechanisms (GRMs) suitable for ammonia and its mixtures with hydrogen or nitrogen have yet to be reported. This study aims to address this gap by investigating new GRMs. Five DRMs were used to calculate the LBVs, and their average values were employed as a reference. First, a single-step GRM was developed for hydrogen (H2 + 0.5O2 → H2O), and another single-step GRM was developed for ammonia (NH3 + 0.75O2 → 0.5N2 + 1.5H2O). However, their combined GRM did not provide reasonable predictions of LBVs for the H2+NH3 mixtures. Therefore, a 4-step GRM was developed consisting of the single-step hydrogen and three additional reactions, i.e., an endothermic ammonia decomposition (NH3 + 0.5O2 → NO + 3H), an exothermic NO reduction (NO + 2H → 0.5N2 + H2O), and an exothermic H recombination (H + H → H2). In conclusion, this 4-step GRM and its revisions could predict reasonable LBVs, flame temperatures, and primary product compositions for mixtures of hydrogen, ammonia, and cracked ammonia gas over a wide range of temperatures (300–600 K) and pressures (1–5 atm).

Laboratory simulations of ice growth in space: An expected nonuniform ice mantle composition

Context. In dense, cold molecular regions, gas-phase chemical species freeze out onto grain surfaces. These icy condensates become an important reservoir of volatile elements and feedstock for molecular diversity. Aims. While there is a fairly general agreement on the chemical composition of icy mantles, there are differences in how the various molecular components are perceived to be present. Should the materials composing the ice be mixed or are they segregated into distinct chemical zones? Methods. To answer such a question, we performed a few exploratory experiments that allowed the adsorbing surface (mimic dust grains) to slowly relax to very low temperatures while gas-phase mixtures of H2O, NH3, and CO embed onto it. Results. We find that mantles are far from being uniform, and they could evolve into completely mixed ices only if the ambient temperature undergoes a catastrophic collapse. Conclusions. Under the typical conditions of an interstellar dense cloud, ices present a high degree of molecular segregation, with possible consequences on the ice chemistry and the desorption mechanisms.

Electrochemical reduction of cyanide on conjugated copper-organic framework Cu3(HHTP)2 monolayer: A dispersion-corrected DFT investigation

Cyanide containing wastewater can cause livestock death and reduce agricultural production and electrochemical reduction of cyanide (CNRR) is a promising way to eliminate its harm and turn waste into valuable products. However, the reaction mechanism and function of electrocatalysts for CNRR have not been fully understood yet. Herein we identify a two-dimensional (2D) conductive copper-organic framework based on triphenylene (Cu3(HHTP)2) for CNRR according to the computed results from dispersion-corrected density-functional theory (DFT-D). Relatively low limiting potential (0.10 V) and high theoretical Faradaic efficiency (near 100%) were found for Cu3(HHTP)2 in the CNRR process, indicating a pretty good performance of Cu3(HHTP)2 monolayer as an electrocatalyst. Mechanism investigations were carried out and both cyanide N-end and C-end-on adsorption patterns as well as nine possible pathways were explored. Appreciable charge density transfer and the enhanced chemical interactions between Cu and C or N atoms are responsible for the outstanding performance of Cu3(HHTP)2 monolayer. The results reveal that the products of CNRR are a gaseous mixture of CH3CH2, NH3 and CH4 at a lower negative-electrode-potential (−0.27 V < U < −0.10 V) while gaseous NH3 and CH4 become main products at a higher negative-electrode-potential (−1.36 V < U < −0.27 V). This work demonstrates that reaction mechanism analysis is a useful approach to identify the catalyst activity and final products of a reaction.

Effect of gas atmospheres and SiO2 content on preparation and properties of SiO2–Si3N4 composite ceramics via nitridation of diamond-wire saw silicon waste powder

Composite ceramics are applied widely nowadays by combining superior properties of different ceramic materials. In this study, SiO2–Si3N4 composite ceramics with higher mechanical properties and lower dielectric constant were successfully fabricated by nitriding diamond-wire saw silicon waste. The effect of gas atmospheres (N2, NH3, N2–H2) and SiO2 content (0%, 10%, 20%, 30%, 40%) on the microstructure and properties of composite ceramics were studied. It shows that the synthesis of SiO2–Si3N4 composite ceramics can be obtained in the NH3 atmosphere, and it is inevitable to form the Si2N2O phase in N2 and N2–H2 mixture atmospheres. Furthermore, the shrinkage rate and dielectric constant of the ceramics decreased as SiO2 content increased from 0% to 40%. As for the porosity of the sintered ceramics, it first decreased and then increased, with a minimum of 1.73% at the SiO2 content of 20%. However, the flexural strength of the sintered ceramics was the inverse of the porosity, with a maximum of 160.72 MPa at the SiO2 content of 30%. For the sintered ceramic with 30% SiO2, the shrinkage rate, dielectric constant, porosity and flexural strength are 0.3%, 4.62, 1.97% and 160.72 MPa respectively. Thus, this study provides an environment-friendly and value-added approach to recycling photovoltaic waste and reducing the cost of the reactive sintering SiO2–Si3N4 composite ceramics with excellent mechanical and dielectric properties.

Enhanced ammonia combustion by partial pre-cracking strategy in a gas turbine model combustor: Flame macrostructures, lean blowout characteristics and exhaust emissions

Cofiring with hydrogen presents a reasonable approach to achieve enhanced ammonia (NH3) combustion without introducing an extra carbon footprint. A promising strategy for NH3/H2 cofiring in gas turbines involves on-site partial pre-cracking of NH3 and burns of NH3/H2/N2 mixtures, eliminating additional hydrogen transportation and storage. This work investigates the effects of the pre-cracking ratio (γ) on flame macrostructures, lean blowout characteristics and exhaust emissions of the partially pre-cracked NH3 flames in a single-swirl gas turbine model combustor. Flow and flame macrostructures were captured using particle image velocimetry (PIV) and OH planar laser-induced fluorescence (OH-PLIF) measurements. Lean blowout limits (ϕLBO) were assessed under varying γ, and emissions at the burner outlet were measured using a Fourier transform infrared spectroscopic (FTIR) gas analyzer. Results show that as γ increases, the flame exhibits a shortened height, strengthened OH fluorescence, amplified core jet velocities and significantly reduced ϕLBO, indicating an effective enhancement of NH3 combustion by partial pre-cracking strategy. Nevertheless, NO and NO2 emissions exhibit a substantial increase with larger γ. Opposite trends of NO and NH3 emissions versus equivalence ratio (ϕ) suggest a trade-off between NO and NH3 emissions, with relatively low NO/NH3 window appearing under slightly-rich (ϕ = 1.0–1.1) conditions. Low NO emissions are also noted under ultra-lean conditions (ϕ = 0.4–0.5) with the penalty of high NH3 and N2O emissions, making it an unacceptable trade-off. Furthermore, the effect of N2 separation from the partially pre-cracked NH3 mixtures was evaluated at γ = 0.4. The results show deteriorating effects on NOx emissions, resulting in 13 % and 21 % increases in peak NO and NO2 emissions, respectively, which implies more feasibility to burn the partially pre-cracked NH3 in a direct manner rather than N2 separation.

Simultaneous OH and OH[formula omitted] measurements during NH3 oxidation in a shock tube

The evolution of the hydroxyl radical in its ground state (OH) and excited state (OH∗) during ammonia (NH3) oxidation was studied behind reflected shocks in a shock tube. Three equivalence ratios were studied (0.5, 1, and 2), with the reactant mixtures of NH3 and oxygen (O2) dilute in 99% argon, over the temperature range 1910 to 2510K, at pressures near 1.4atm. A mid-infrared laser-absorption diagnostic was used to validate pre-shock NH3 concentrations before each experiment. An ultraviolet laser-absorption diagnostic targeting a strong rovibronic transition of OH enabled high-sensitivity, quantitative measurements of OH time-histories, and an emission diagnostic enabled simultaneous, qualitative time–history measurements of OH∗. Post-reflected-shock time-histories were analyzed to extract characteristic ignition timescales, OH rise slopes, and OH post-ignition concentrations, all of which are suitable parameters for kinetic model validation. Measured parameters, including OH and OH∗ ignition delay times (IDTs), revealed key distinctions between ground-state and excited-state OH formation timescales that change across the parameter space studied in this work. Measurements were compared against composite chemical kinetic models assembled from two base oxidation mechanisms, three pyrolysis submodels, and two OH∗ submodels. One combination was found to best predict the experimental data, though no model successfully predicted all measured parameters at all conditions. Detailed rate-of-production analysis revealed that reaction of OH with NH3 serves to depress early-time populations of OH at stoichiometric and lean conditions, leading to earlier OH∗ IDTs relative to OH IDTs. One of the two studied OH∗ submodels was found to better predict measured OH∗ time-histories and IDTs, which was attributed to an improved rate and third-body efficiency for the reaction ▪ . Altogether, the measurements presented in this work represent a valuable source of validation data for NH3 model development and emphasize the utility of laser-absorption diagnostics for such validation.

Multi-speciation and ignition delay time measurements of ammonia oxidation behind reflected shock waves

Ammonia (NH3) oxidation was studied using emission and laser absorption diagnostics in a shock tube. Experiments were carried out using stoichiometric mixtures of NH3 and O2 highly dilute in Ar seeded with CO2 at post-reflected-shock conditions from 1700–2500K near 2atm. Five optical diagnostics in the infrared (IR), visible, and ultraviolet (UV) were implemented to measure NH3 (before and after shock-heating), NO, electronically excited amino radicals (NH2∗), electronically excited hydroxyl radicals (OH∗), and temperature during oxidation. To mitigate mixture uncertainty due to NH3 adsorption, a scanned-wavelength laser absorption diagnostic near 10.4μm was developed to measure initial NH3 concentration. A two-color, fixed-wavelength laser absorption diagnostic near 225 nm was developed to measure quantitative NO and NH3 time-histories. A detailed spectroscopic model of the NO A2Σ+←X2Π system was used to provide NO absorption cross-sections at both wavelengths, and NH3 absorption cross-sections were measured at the conditions of interest. Emission from NH2∗ near 600 nm was collected to provide qualitative insight into radical formation prior to ignition, and emission from OH∗ near 308 nm was used to determine ignition delay times (IDTs). A two-color, fixed-wavelength laser absorption diagnostic at 4.17μm and 4.19μm was developed to measure temperature using small quantities of seeded CO2. Measured time-histories are compared against predictions from two kinetic models. Experimental results and model predictions show several discrepancies, both in terms of timescales and absolute quantities. Sensitivity analysis shows that the reactions H + O2⇌ O + OH, NH3 + M ⇌ NH2 + H + M, and NH3 + H ⇌ NH2 + H2 are dominant across all conditions, and that NH3 pyrolysis reactions in general drive much of the chemistry. Direct, low-scatter rate constant measurements of the NH3 + M ⇌ NH2 + H + M reaction and additional multi-speciation measurements of NH3 pyrolysis and oxidation at combustion-relevant temperatures and pressures are recommended.Novelty and significance statementThe novelty of this work is exemplified most strongly by the use of UV laser absorption diagnostics to measure NH3 and NO during high-temperature oxidation of NH3. Simultaneous measurements of temperature via CO2 laser absorption at two wavelengths and light emission from NH2∗ and OH∗ are also novel. Simultaneous, time-resolved, quantitative measurements of NH3, NO, and temperature and qualitative measurements of NH2∗ and OH∗ light emission are of significant utility as a model validation-suited data set. Additionally, the data presented herein and the associated findings provide evidence of current chemical kinetic model deficiencies pertaining to NH3 chemistry and suggest avenues for model improvement.

The Nature of the Spark Is a Pivotal Element in the Design of a Miller-Urey Experiment.

Miller and Urey applied electric sparks to a reducive mixture of CH4, NH3, and water to obtain a complex organic mixture including biomolecules. In this study, we examined the impact of temperature, initial pressure, ammonia concentration, and the spark generator on the chemical profile of a Miller-Urey-type prebiotic broth. We analyzed the broth composition using Gas Chromatography combined with Mass Spectroscopy (GC/MS). The results point towards strong compositional changes with the nature of the spark. Ammonia exhibited catalytic properties even with non-nitrogen-containing compounds. A more elevated temperature led to a higher variety of substances. We conclude that to reproduce such a broth as well as possible, all the studied parameters need to be tightly controlled, the most difficult and important being spark generation.

Influence of thermodynamically consistent data on artificial neural network modeling: Application to NH3 solubility data in room temperature ionic liquids

A general thermodynamic consistency of temperature, pressure, and solubility (T-P-x) data for binary mixtures including, ammonia + Room Temperature Ionic Liquids (ILs), has been studied. Experimental data taken from the literature for 24 binary mixtures of NH3 + ILs including, 108 isothermal data sets altogether. This study set out two main purposes 1) model dependency of thermodynamic consistency analysis applied by equations of state including Generic Redlich Kwong (GRK)/Van der waals berthelot (VdWB), Peng Robinson Stryjek Vera (PRSV)/Panagiotopoulos-Reid (PR) and that done using Peng Robinson / Kwak Mansoori (PR/KM) EoS in other work, Faúndez et al. (2013). 2) Impact of the discarding thermodynamically inconsistent data on Multilayer Perceptron (MLP)-Artificial Neural Network (ANN) modeling precision. The GRK/VdWB model was found to characterize themean averagepressure deviation as less than 2.0 % and the maximum average pressure deviation as 8.5 %, which is an improvement over PRSV/PR (which has deviations of 2.6 % and 9.7 %. The results of the MLP-ANN were categorized into two groups1) MLP-ANN tests were conducted for all data points and 2) MLP-ANN tests were done for excluded thermodynamically inconsistent (TI) data. Themaximum deviationfrom experimental data in the modeling of all data was found to be 13.213 % for the wholeIL + NH3systems, while the maximum deviation for modeling data without TI data was 9.9979 %. Thestatistical characteristicsused to evaluate the agreement between experimental data and modeling data, including R2, MSE, MAE, ARD, and MRD, indicate that the agreement is better for the excluded thermodynamically inconsistent data than for the total data set.