Low-temperature Oxidation Process Research Articles

Synchrotron vacuum ultraviolet photoionization mass spectrometry and modeling study of iso-octane low temperature oxidation at varied pressures

Because of its excellent anti-knock properties, iso-octane has been selected as the main component of gasoline surrogates, and a thorough understanding of its low temperature oxidation process is essential for the development of kinetic models. Although iso-octane has been studied for decades, a comprehensive understanding of its low temperature oxidation chemistry has not been realized, and kinetic models were not well developed. In this work, the previously developed, variable pressure jet-stirred reactor-synchrotron vacuum ultraviolet photoionization mass spectrometry system was used to study the low temperature oxidation of iso-octane at five bar, with an initial fuel mole fraction of 0.01, residence time of 2 s, and equivalence ratio of 0.25. Dozens of oxidation intermediates were qualitatively and quantitatively analyzed, helping to reveal the low temperature oxidation reaction processes of iso-octane and examine the kinetic models. Comparing iso-octane studies at high pressure in the literature, a highly detailed species pool was probed, which included H2O2, carbonyl acids, alkyl hydroperoxides, and keto-hydroperoxides (KHP). By combining the atmospheric pressure data in the literature, the recently developed model of iso-octane low temperature oxidation was examined. Further improvement of the kinetic model was achieved by carefully tuning the reaction rate constant of the KHP decomposition. Finally, according to the variation of mole fraction of products at different pressures, the pressure effects on key reaction pathways were discussed, and the selectivity of products at varied pressure conditions clarified.

The influence of molecular structure on the oxidation reactivity of long-chain ethers: Experimental observation and theoretical analysis

Long-chain ethers have been proposed as promising biofuels for advanced combustion methods, yet their low-temperature oxidation (LTO) characteristics remain poorly understood. In this study, the LTO reactivities of n-heptane and five long-chain ethers with different structures, including dibutyl ether (DBE), diethylene glycol dimethyl ether (DGM), polyoxymethylene dimethyl ethers (PODE), 1,2-dimethoxyethane (1,2-DME), and dipropyleneglycol dimethyl ether (DPGDE) are investigated using a cooperative fuel research (CFR) engine, which is closer to the actual internal combustion engine operating environment. Products formed from LTO of ethers and n-heptane are investigated over a wide range of compress ratios (CRs), and their relationship to the global oxidation reactivity is suggested based on the quantum chemistry calculation. The presence of oxygen atoms in long-chain ethers significantly enhances oxidation reactivity, with the global oxidation reactivity ranking as follows: DGM > DPGDE > 1,2-DME > DBE > PODE > n-heptane. The key intermediate species generated during the LTO of n-heptane include aldehydes, ketones, and cyclic ethers, while oxygen atoms in ethers facilitate the formation of acids. The species pathway analysis and quantum chemistry calculations reveal that (1,5) and (1,6) H-transfers of alkylperoxy radical (ROȮ) are critical chain-propagation channels, playing pivotal roles in the LTO process. The impact of oxygen on oxidation reactivity can be attributed to two primary factors: accelerating the H-abstraction of ȮH and H-transfer of ROȮ by weakening the neighboring C-H bonds, and enhancing the branching ratio of H-transfer of ROȮ. The arrangement of two oxygen atoms between every two carbon atoms (–OCH2CH2O–) is optimal for oxidation reactivity, while the arrangement of oxygen and carbon (–OCH2OCH2–) weakens the oxidation activity due to fewer available hydrogens for H-transfer. The methyl group in branching-chain, exhibit reduced oxidation reactivity due to the strength of C-H bonds. Additionally, for ethers with the same structure, a longer carbon chain allows for more available hydrogens, resulting in stronger oxidation reactivity.

Synergistic effects of copper and oxygen vacancies in enhancing the efficacy of partially crystalline CuMnxOy catalyst for ozone decomposition.

To tackle the challenge of ground-level ozone pollution, this study proposed a potential catalytic design approach for ozone decomposition using Cu-Mn bimetallic oxide. This approach is grounded in an understanding of the intrinsic reactivity for catalyst and incorporates a novel potassium-driven low-temperature oxidation process for catalyst synthesis. The research highlights the creation of a highly reactive Cu-Mn oxide phase with extensive defect coverage, leading to significantly increased reaction rates. It also identifies the MnO2(100) facet as a crucial active phase, where oxygen vacancies simultaneously enhance O3 adsorption and decomposition, albeit with a concurrent risk of O2 poisoning due to the stabilization of adsorbed O2. Crucially, the incorporation of Cu offsets the effects of oxygen vacancies, influencing conversion rates and lessening O2 poisoning. The synergistic interplay between Cu and oxygen vacancies elevates the performance of the defect-rich Cu-Mn oxide catalyst. By combining computational and experimental methods, this study not only advances the understanding of the Cu-Mn oxide system for ozone decomposition but also contributes valuable insights into developing more efficient catalysts to mitigate ozone pollution.

Online CO Monitoring During Low Temperature Oxidation of Zonguldak Coals

ABSTRACT During low temperature oxidation of coals, due to half reaction of carbon with oxygen, concentration of CO is readily being increased and it is monitored by the field operators via gas detectors. In this study, low temperature oxidation tests were carried out for 26 samples, which were collected from Zonguldak hardcoal basin. In order to have observation CO concentrations levels during low temperature oxidation, a complete experimental set up was established. The experimental set up abovementioned includes two gas chromatographs (GC HP 5890 and GC HP 6890), one of which (HP 5890) is employed for oven purposes. As in the case of low temperature oxidation testing procedure, a starting temperature and the ramp is defined as 30°C and 0.5 °C/min, respectively. Every 15 minutes, (7.5°C increase) gas sample produced from coal via the process of low temperature oxidation was taken and analyzed by the gas chromatograph. Based on the results obtained, the amount of CO generated at low temperature (at 37.5 °C) was found to be a significant measure for the coal spontaneous combustion liability. As for the indicator gas for the spontaneous combustion of coal, results implied the fact that increase in the amount of CO generated during spontaneous combustion was observed. Due to the abovementioned fact in terms of indicator gas for spontaneous coal combustion, it was found out the fact that the increase in the amount is significant. CO (ppm) result at early temperature was found out to be in very strong relationship with corresponding spontaneous combustion liability test results. The correlation between CPT and CO (ppm) at 37.5°C for 26 coal samples was found out to have a correlation coefficient of 0.82, i.e. R2 = 0.8224. Increase in CO (ppm) was observed with the increase in the environment temperature for each of 26 coal samples studied. Based on the FCC index values (coal spontaneous combustion liability index) calculated for each of 26 coal samples, the correlation between CO (ppm) and the corresponding FCC index values yielded a correlation coefficient of 0.86, (R2 = 0.8585).

A single Mn atom supported by a boron-vacancy in a BN monolayer: An encouraging catalyst for CO oxidation

Single-atom catalysts (SACs) are known for their exceptional activity, primarily attributed to the abundance of low-coordinated metal atoms, which enable efficient activation of robust chemical bonds, including CO bonds. In this work, we explore the prospective utilization of a specific SAC, isolated Mn atoms supported on Boron nitrogen (Mn/BN), for CO oxidation. By analyzing the adsorption/co-adsorption energies of CO, O2, O2+CO, and 2CO, we create a set of screening criteria and conduct a comparative analysis of the chemical processes involved in CO oxidation. The Langmuir-Hinshelwood (LH), Eley-Rideal (ER), termolecular Langmuir-Hinshelwood (TLH) and termolecular Eley-Rideal (TER) mechanisms are investigated. Results indicate the ER and LH mechanisms feature pronouncedly lower barrier of 0.33 and 0.41 eV, respectively, for the rate-limiting step, than those of the TLH (0.72 eV) and TER (3.00 eV) mechanisms, suggesting that the ER and LH mechanisms are favorable at normal temperature. This study offers valuable insights that can inform future developments in the design of low-temperature CO oxidation processes utilizing SACs.

Influence of mudstone on coal spontaneous combustion characteristics and oxidation kinetics analysis

To explore the spontaneous combustion characteristics and hazards of the low-temperature oxidation (LTO) stage in the process of spontaneous combustion of coal and mudstone, the pore structure, spontaneous combustion characteristic parameters, and exothermic characteristics of coal and mudstone were tested and studied, and the oxidation kinetic parameters were calculated. The results show that mudstone has a larger specific surface area and pore volume than coal. From the fractal characteristics, the pore structure of mudstone is more complex than that of coal. According to the comparison of theoretical and actual gas generation and oxygen consumption rate curves, it is found that there is an interaction between coal and mudstone in the LTO process. With the increase of mudstone mass ratio, gas production, and its oxygen consumption rate increase. Among them, CM-4 (Coal:Mudstone = 1:1) has the highest exothermic intensity and the exothermic factor (A) and fire coefficient (K) increase with the increase of mudstone content. The apparent activation energy of the mudstone sample is lower than that of the raw coal, indicating that the sample after adding mudstone is more likely to have spontaneous combustion in the LTO stage.

Combined experimental and kinetic modeling study on the low-temperature oxidation of OME3/n-heptane blends

Experimental and kinetic studies on the blending of ethers or diesters with larger alkanes at low temperatures are enormously scarce. In this paper, the low-temperature oxidation (LTO) kinetics model of polyoxymethylene dimethyl ether 3 (OME3)/n-heptane (500 K–950 K) was established by using the jet-stirred reactor (JSR) to conduct the LTO experiments of OME3/n-heptane with different blending ratios. GC/MS was used to detect and quantify 17 kinds of stable products in the LTO process of OME3/n-heptane. The detailed OME3/n-heptane kinetic model was fully verified experimentally. The interaction mechanism of OME3/n-heptane was discussed based on the experiments and corresponding chemical kinetic analysis. Results show that the oxidative decomposition processes of OME3 and n-heptane were significantly different, the LTO and NTC process of OME3 were significantly weaker than those of n-heptane, but the high-temperature reactivity of OME3 was much stronger. In addition, n-heptane significantly promoted the intermediate species CH3OCHO and COCOC*O of OME3, mainly because n-heptane significantly prolonged the LTO of OME3 in the fuel blends. And the NTC process of the fuel blends was mainly dominated by OME3, while the LTO process was more influenced by n-heptane, which resulted in the weakened NTC of n-heptane and the significantly enhanced LTO process of OME3.

Comprehensive evaluation of low-temperature oxidation characteristics of low-rank bituminous coal and oil shale

The coexistence of coal and oil shale mining conditions exacerbates the complexity of coal spontaneous combustion (CSC) prevention, so conducting in-depth research on the spontaneous combustion characteristics of coal, oil shale, and their mixed samples is necessary. A programmed heating system simulated the low-temperature oxidation process of bituminous coal and oil shale under different air volumes. It was found that CO concentration, C2H4 concentration, and Graham's fire coefficient (R1, R2) can be used as indicator gases to predict the CSC process. Compared with oil shale and mixed samples, bituminous coal has a higher CO production rate, oxygen consumption rate, heat release intensity, and lower apparent activation energy during the slow oxidation stage. Meanwhile, bituminous coal also has lower peak values of minimum float coal thickness, lower limit oxygen concentration, and maximal air leakage intensity, which means that bituminous coal in the goaf is more prone to oxidation. However, the abundant free hydrogen bonds in oil shale can stabilize the hydrogen-deficient functional groups of bituminous coal, which weakens the oxidation ability of the mixed sample during the accelerated oxidation stage. In addition, the increased air volume fraction increases the oxygen adsorption efficiency of the mixed sample throughout the low-temperature oxidation process, which means that the M70 sample has a higher CSC risk. The results have enriched the research on the spontaneous combustion characteristics of coal, oil shale, and mixed samples, which may strengthen the management and control of CSC in coal and oil shale co-mining mines.

Study on the evolution characteristics of molecular surface active sites of low-rank coal in low-temperature oxidation stage

Compared with other coal types of coal, low - metamorphic coal contains numerous active sites, making it susceptible to spontaneous combustion and posing significant risks during production, transportation, and storage. To further reveal the evolution characteristics and laws of low-rank coal's active sites during the process of low-temperature oxidation of coal (LTOC), X-ray photoelectron spectroscopy (XPS), 13C nuclear magnetic resonance (13C NMR), and Fourier transform infrared (FTIR) experiments were used to determine the basic structural parameters such as the valence state of non-carbon features, types of carbon elements in coal macromolecules, and structure and quantity of functional groups. Combined with molecular modelling software (GaussView 6.0) and macromolecular calculation software (Grimme-XTB), macromolecular models of coal at different temperature points were constructed, and the surface energy field distribution was calculated. The number and energy change information of chemical and physical adsorption sites of low-rank coal during heating were obtained. The results show that during the LTOC, the chemical adsorption sites such as aliphatic hydrocarbons (-CH3/-CH2) have higher reactivity and can be converted into oxygen-containing functional groups (-CHO, –OH, –COOH); the number of physical adsorption sites increased first and then decreased, and reached the maximum at 50 °C. Coal exhibited a higher affinity for O2 at this temperature. The peroxide (-C-O-O-H) undergoes thermal decomposition, leading to H2O and weight loss of coal. The –CO and –COO structures undergo decarboxylation to generate CO, CO2, and other gases. This study comprehensively revealed the evolution of active sites through two key coal oxygen processes, physical and chemical adsorption, based on the gradual temperature elevation of low-rank coal. This holds immense significance for improving and enriching the understanding of the mechanism of coal spontaneous combustion(CSC), preparing more targeted CSC inhibition, and formulating efficient fire prevention and extinguishing measures.

Isothermal low-temperature oxidation behavior and kinetics of heavy oil

In this study, the isothermal low-temperature oxidation (LTO) behavior of heavy oil was investigated by thermogravimetry combined with Fourier transform infrared spectroscopy. Furthermore, the kinetics analysis was conducted using general reaction rate models. The findings revealed that the LTO process of heavy oil could be divided into three distinct phases. The first phase, occurring between 50 and 100 °C, exhibited minimal mass loss and low absorbance of gas-phase products. In the second phase (100–250 °C) the produced gas predominantly consisted of saturated hydrocarbons and substances containing C=O groups. Lastly, in the third phase (250–300 °C), the signals of CO2 and CO in the produced gas were significantly higher compared to the 50–250 °C range, indicating a shift in the oxidation mode of heavy oil from oxygenation to bond cleavage for temperatures higher than 250 °C. Kinetics analysis demonstrated an initial increase in reaction order and reaction rate from 50 to 100 °C, followed by a decrease from 100 to 250 °C, and a final increase from 250 to 300 °C. The negative activation energy observed in the second temperature interval was attributed to the negative temperature coefficient effect. This study provided valuable insights into the isothermal LTO reactions of heavy oil.

Comparative investigation of low temperature oxidized and pyrolyzed cokes from the inferior heavy oil: Structural feather, thermo-oxidation behavior, and kinetics

It was crucial to study the low temperature coking process for the heavy oil, which affected the fuel availability and subsequent in-situ combustion progress. From this perspective, low temperature coking experiments with different atmospheres were accomplished for the inferior heavy oil to obtain oxidized (cokeLTO) and pyrolytic (cokeLTP) cokes, which were further employed to trace structural feathers via joint analysis of elemental analysis, Fourier transform infrared spectrophotometry (FTIR) and X-ray photoelectron spectroscopy (XPS) spectra, and to characterize thermo-oxidative characteristics and kinetics via different thermal analyses (TG-DTG/DSC) and model-free methods. The results showed that a relatively less aliphatic and more aromatic structures were contained in cokeLTO with a relatively higher proportion of C-O, C = O, O-C = O groups and C/H ratio, implying that oxygen atom was served as the promoter to replace hydrogen atom and accelerate macromolecular structure formation. While the decomposition and conversion of N- and S- functional groups were complicated and insensitive to the coking atmosphere. Furthermore, cokeLTO had a more dominant thermo-oxidation behavior than cokeLTP with better exothermic characteristic and lower activation energy distribution. From this study, it could provide a vital piece of updated insights on the role of low temperature oxidation process in coke deposition and feature.

Elucidating the low temperature chemistry of o-xylene enhanced by the reaction pool of dimethyl ether

The branched aromatic hydrocarbon with short side chains, such as o-xylene, has weak low temperature oxidation reactivity, while it could proceed low temperature chain recycling reactions by blending a fuel component with higher oxidation reactivity. However, the study of low temperature oxidation kinetics of o-xylene is very scarce. Therefore, this work investigated the low temperature oxidation process of o-xylene in an atmospheric jet stirred reactor by adding a biofuel with higher low temperature oxidation reactivity, i.e. dimethyl ether (DME). A series of characteristic low temperature intermediates, such as phenyl hydroperoxides and ketohydroperoxide from the oxidation of o-xylene, were detected by using the synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). The chemical structures of representative low temperature intermediates were determined by comparing the ionization thresholds from measured photoionization efficiency curves with calculated ionization energies. A kinetic model for o-xylene and DME mixture was developed and verified by literature and present experimental data. Rate of production (ROP) and sensitivity analyses were performed, which indicate that the low temperature oxidation chemistry of o-xylene, such as the negative temperature coefficient behavior, is enhanced by the reaction pool of DME. According to the classical low temperature oxidation mechanism of n-alkanes, the low temperature reactions of o-xylene were proposed. In particular, phenyl hydroperoxides and ketohydroperoxides were revealed to be key indicators for the occurrence of first and second O2 addition reactions during the oxidation of o-xylene, respectively. In addition, the sensitivity analysis uncovers the interaction kinetics between the reaction pools of o-xylene and DME, as well as their effects on fuel consumption and products formation. In summary, present evidence elucidates the low temperature chemistry of a representative branched aromatic, which could contribute to the development of future engines and control of combustion pollutants.

Mechanisms of CO and CO2 Production during the Low-Temperature Oxidation of Coal: Molecular Simulations and Experimental Research

The spontaneous combustion of coal caused by oxidation often leads to catastrophic fires. However, the understanding of oxidized carbon gas as a predictor of coal’s spontaneous combustion is still in its infancy. To better study the characteristics of CO2 and CO generation during low-temperature coal oxidation, the chemical reactions and activation energies during the formation of oxidized carbon gases within coal molecules were investigated using the molecular simulation method, and the reaction characteristics at different temperatures were determined. In addition, TG was used to experimentally analyze the variations in coal weight, exothermic conditions, and gas generation patterns. The results show that the low-temperature oxidation process consists of four different phases, each of which is characterized by unique CO and CO2 generation. The results of this study are important for the prevention and prediction of the spontaneous combustion of coal.

Effect of Resveratrol on physicochemical structure evolution of lignite during spontaneous combustion

Studying the evolution of the physicochemical structure of coal during coal spontaneous combustion (CSC) by antioxidants is of great significance for revealing the mechanism of CSC and preventing it. The effects of three concentrations of Resveratrol (RES) on the physicochemical structure evolution of coal during the low-temperature oxidation (L-TO) process of CSC were comprehensively analyzed through low-field nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) experiments. The results showed that the pore cracks in the coal develop more fully with the increase in oxidation temperature. Besides, there was an increase in porosity and permeability, and a full development of pore throat. Based on the T1-T2 2D fluid identification results, it was found that as the oxidation temperature increased, the adsorption capacity and permeability of the coal were stronger. RES can effectively inhibit the CSC process of coal, with a maximum reduction of 23 % in porosity and a maximum reduction of 82 % in permeability. The hydroxyl groups and CH3/CH2 of coal samples treated with RES decreased by a maximum of 42 % and 43 %, respectively. The oxygen-containing functional groups increased by a maximum of 77 %. RES can not only cover on the coal surface to prevent oxygen from seeping into the coal, but also infiltrate into the pores of coal to inhibit the combination of the active functional groups and oxygen molecules.

Low-temperature oxidation characteristics and reaction pathways of crude oil within tight shale during air injection

The investigation of low-temperature oxidation (LTO) of crude oil within tight shale holds significant importance due to its implications for subsequent oxidation reactions and enhanced oil recovery in the process of air injection. In this study, the tight shale sample underwent oxidation at various LTO temperatures, followed by an analysis of the resulting gas composition. Furthermore, the oxidized oil was separated from the tight shale and subjected to characterization using electron paramagnetic resonance, nuclear magnetic resonance, and negative ion electrospray Fourier transform-ion cyclotron resonance mass spectrometry techniques. The primary focus was on examining the distinct LTO reaction pathways observable across different temperature ranges. The findings demonstrated a correlation between LTO temperature and the concentration of free radicals, which predominantly resided on aromatic hydrocarbons, alkanes, and oxygen atoms. Additionally, the proton count of polycyclic aromatic hydrocarbons exhibited a continuous increase from 83 to 350 °C, suggesting intensified aromatization and condensation reactions involving aliphatic and aromatic compounds. With rising LTO temperature, the molecular structure of O2 compounds underwent significant transformations, characterized by increased condensation degree and a decrease in low carbon number molecular structures, while higher equivalent double bonds and carbon number molecular structures became more prevalent. The influence of cycle path 1 diminished at temperatures ranging from 83 to 150 °C and 250 to 350 °C, whereas the significance of cycle paths 2 and 3 increased, resulting in an overall escalation of the oxidation rate with temperature elevation. It was observed that the shale oil LTO process exhibited a negative temperature coefficient within the temperature range of 150-250 °C, emphasizing the criticality of overcoming the energy barrier in this region to achieve stable combustion. This comprehensive investigation provides valuable insights into the mechanisms underlying LTO in crude oil confined within tight shale.

Evolution and oxidation properties of the functional groups of coals after water immersion and air drying

The evolution of functional groups, the gas generation laws in oxidation and temperature increase, and the oxidation kinetics parameters of the coal samples immersed in water for 30 days, 90 days, and 150 days (hereinafter referred to as 30 d coal, 90 d coal, and 150 d coal, respectively) were analyzed through Fourier transform infrared spectrometer, programmed temperature increase test system, and thermal gravimetric analyzer to disclose spontaneous combustion and the influencing mechanism of long-flame coals immersed in water for a long period. Results show that the aliphatic hydrocarbon and the hydroxyl contents of the coal samples increase after water immersion and air drying. In particular, the aliphatic hydrocarbon contents in 30 d coal, 90 d coal, and 150 d coal increase from 12.61 % for raw coal to 15.84 %, 14.08 %, and 13.90 %, respectively, whereas the hydroxyl content increases from 48.75 % for raw coal to 50.77 %, 50.13 %, and 49.23 %, respectively. In the low-temperature oxidation process, the CO output increases, and the apparent activation energy declines. When the temperature is 200 °C, the CO outputs of 30 d coal, 90 d coal, and 150 d coal are 28088, 25421, and 22112 ppm, which are 37.4 %, 24.4 %, and 8.2 % higher than the CO output of raw coal (20437 ppm), respectively. The apparent activation energy decreases from 65.7 kJ mol−1 for raw coal to 61.12 kJ mol−1, 63.08 kJ mol−1, and 64.5 kJ mol−1. According to the comparison of characteristic temperature points, the temperature of the mass extreme (T3) and the temperature of ignition point (T4) of the immersed coal samples both decrease. The T3 values of 30 d coal, 90 d coal, and 150 d coal decrease from 282.71 °C for raw coal to 274.87, 278.33, and 280.50 °C, whereas their T4 values decrease from 424.24 °C for raw coal to 419.23, 420.14, and 423.42 °C, respectively. This study proves that water immersion increases the oxidative activity of coals, thereby simplifying spontaneous combustion.

Study on the variation in key functional groups of coal and the mechanism of CO and CO2 generation under the thermal effect of lean-oxygen conditions

Most closed fire areas in coal mines encounter rapid reignition after unsealing. To prevent the reignition of residual coal, it is necessary to study the impact of the lean oxygen conditions (LOCs) in closed fire areas on the characteristics of coal spontaneous combustion (CSC), evolution of the pore and fissure structures, and generation mechanisms of gases such as CO and CO2. A systematic study was conducted using in situ infrared, synchronous thermal analyzer (STA-DSC), scanning electron microscope (SEM), N2 adsorption, and programmed heating experiments. The results show that during the low-temperature oxidation process (LTOP), the temperature and oxygen concentration had a significant impact on the content variations of functional groups such as –OH, CO, COOH, CH2/CH3, and CC. Moreover, the higher the oxygen concentration, the higher was the effect. The concentration and heat release rate of CO and CO2 generation were positively correlated with the oxygen concentration. As the temperature increased, cracks developed gradually on the coal surface, and micropores transformed into mesopores and macropores. The specific surface area decreased gradually. When the temperature was below 110 ℃, the microstructure of the coal sample did not vary significantly. When the temperature was above 110 ℃, the effect was significant. The higher the oxygen concentration, the more significant was the impact on the pore characteristics of the coal. Two main pathways exist for CO and CO2 generation. CO2 generation requires a higher temperature than that required for CO. The research results provide a theoretical basis for the unsealing of closed fire areas and prevention of reignition.

Formation of spiral structures in rich-hydrogen air flames at elevated pressures

Travelling combustion fronts demonstrate the appearance of a variety of instabilities and structures and thus the revealing of the mechanisms of these phenomena is important both in theoretical and practical aspects. In this work, the mechanism of formation of spiral nonlinear wave structures in the process of propagation of a combustion wave in a rich hydrogen-air mixture at elevated pressure is studied analytically and numerically. A detailed model of the hydrogen oxidation reaction is reduced to a system of partial differential equations for the evolution of H, HO2, O2 and temperature profiles describing both low-temperature and high-temperature reactivity. It is shown to be able to successfully reproduce the characteristics of the diffusive-thermal pulsations emerging with the increase of pressure. A model for the dynamics of the low temperature flame region is separated from the reduced model by using a number of assumptions and appeared to be similar to the Sal'nikov model. It is shown that for the parameter values at which spiral waves are observed, the latter model turns to excitable regime and generates the spiral solutions. Thus it is concluded that the low temperature oxidation processes are responsible for emergence of the spiral structures at the combustion front. We think that the current work is an important step towards understanding the mechanisms of formation of spiral wave structures in expanding combustion fronts.

Molecular composition of low-temperature oxidation products of the heavy oil

Low-temperature oxidation (LTO) is the main reaction that affects fuel formation in the in-situ combustion process, which has important significance for the subsequent combustion propulsion and the successful extraction of crude oil. In this study, heavy oil was subjected to LTO reactions at different temperatures. Three types of reaction products with varying oxidation depths were characterized in terms of the number of oxygen atoms and the polarity of the molecule to reveal the low-temperature oxidation process of the heavy oil. Ketone compounds and acid polyoxides in the oil phase and deep oxidation products with a higher number of oxygen atoms in the coke were identified with increasing oxidation depth. The experimental results showed that the oxidation reaction of the heavy oil changed from kinetic-controlled to diffusion-controlled in the open oxidation system of the heavy oil as the oxidation depth increased. The oxidation reaction of the oil phase reached a maximum and stable value in oxygen content. The molecular compositions of the ketone compound and acid polyoxide did not change significantly with further increase in reaction temperature. The molecular compositions of the deep oxidation products with a higher number of oxygen atoms in the coke phase changed significantly. The coke precursor molecules with a lower oxygen content and condensation degree participated in the coke formation, and the oxidation reaction pathway and the complexity of the oxidation product component also increased.

Co-Ru alloy nanoparticles decorated onto two-dimensional nitrogen doped carbon nanosheets towards hydrogen/oxygen evolution reaction and oxygen reduction reaction

Constructing highly-efficient electrocatalysts toward hydrogen evolution reaction (HER)/oxygen evolution reaction (OER)/oxygen reduction reaction (ORR) with excellent stability is quite important for the development of renewable energy-related applications. Herein, Co-Ru based compounds supported on nitrogen doped two-dimensional (2D) carbon nanosheets (NCN) are developed via one step pyrolysis procedure (Co-Ru/NCN) for HER/ORR and following low-temperature oxidation process (Co-Ru@RuOx/NCN) for OER. The specific 2D morphology guarantees abundant active sites exposure. Furthermore, the synergistic effects arising from the interaction between Co and Ru are crucial in enhancing the catalytic performance. Thus, the resulting Co-Ru/NCN shows remarkable electrocatalytic performance for HER (70 mV at 10 mA cm−2) in 1 M KOH and ORR (half-wave potential E1/2 = 0.81 V) in 0.1 M KOH. Especially, the Co-Ru@RuOx/NCN obtained by oxidation exhibits splendid OER performance in both acid (230 mV at 10 mA cm−2) and alkaline media (270 mV at 10 mA cm−2) coupled with excellent stability. Consequently, the fabricated two-electrode water-splitting device exhibits excellent performance in both acidic and alkaline environments. This research provides a promising avenue for the advancement of multifunctional nanomaterials.