Low-temperature Oxidation Reaction Research Articles

Coupling experimental and modeling approaches for understanding diethoxymethane low-temperature oxidation at high pressure

Diethoxymethane (DEM) has attracted significant attention as a potential renewable alternative fuel. The lack of detailed product species distributions for DEM oxdation led to insufficient exploration of its low-temperature oxidation chemistry. In this study, the low-temperature oxidation reactions of DEM were conducted using a jet-stirred reactor (JSR) coupled with synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) under conditions of 10 atm, an equivalence ratio of 0.5, and temperatures ranging from 470 to 850 K. Identification and quantification of various oxygenated species were performed. Additionally, complementing our previous kinetic theoretical studies for low-temperature oxidation of DEM radicals, previously calculated rate constants were incorporated into an earlier DEM combustion model, accompanied by additional adjustments to the rate constants of hydrogen abstraction reactions by C˙2H3 radicals. The modified model exhibits good agreement between the predicted and experimentally obtained product mole fraction distributions. Remarkably, a relatively weak negative temperature coefficient (NTC) was observed under the studied conditions, highlighting differences in the self-ignition behavior of DEM compared to other highly reactive fuels. Analyzing the rates of production (ROP) in the modified model indicates that the use of oxygenated fuels might elevate the production of small-molecule oxygenated pollutants while reducing the formation of carbon soot precursors and consequently curbing soot generation. Moreover, keto-hydroperoxides (KHPs) were detected during the experimental process. This study lays a foundation for further detailed exploration of the DEM oxidation mechanism, aiding in untangling its intricate reaction processes.

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.

Pulsating light emission during the initiation of the low-temperature propane oxidation reaction due to the presence of quantum resonance in the system

Pulsating light emission during the initiation of the low-temperature propane oxidation reaction due to the presence of quantum resonance in the system

APPLICATION OF ATOMIC OXYGEN FOR GASOLINE OCTANE NUMBER DETERMINATION

There is a method that measures the thermal effect of a low-temperature oxidation reaction to determine the octane number of gasoline. The reaction was conducted in the presence of ozone on a thermistor surface at a temperature of the vapor-gas mixture equal to the end boiling point of gasoline in order to lower the analysis temperature. Keywords: low-temperature oxidation, atomic oxygen, gasoline, detonation resistance, octane number, ozone, and thermistor.

APPLICATION OF ATOMIC OXYGEN FOR GASOLINE OCTANE NUMBER DETERMINATION

There is a method that measures the thermal effect of a low-temperature oxidation reaction to determine the octane number of gasoline. The reaction was conducted in the presence of ozone on a thermistor surface at a temperature of the vapor-gas mixture equal to the end boiling point of gasoline in order to lower the analysis temperature. Keywords: low-temperature oxidation, atomic oxygen, gasoline, detonation resistance, octane number, ozone, and thermistor.

Analysis of temperature rise of low temperature adiabatic oxidation of sulfur-containing “coal-like substances”

ABSTRACT Spontaneous combustion of coal is one of the main natural disasters in the process of coal mining, and spontaneous combustion of sulfur-containing coal is an urgent problem to be solved. In order to understand the influence of different sulfur structures and sulfur content on spontaneous combustion tendency of coal, the self-developed synchronous temperature compensation adiabatic oxidation experiment system was used to study the oxidation self-heating performance of a series of sulfur-containing “coal-like materials.” Through the analysis of the heating rate of coal containing specific sulfur structure, it is considered that the time of adiabatic oxidation temperature of different organic sulfur “coal” to rise to 70°C is dimethyl sulfoxide > phenylene sulfide > dibenzothiophene. By analyzing the oxidation temperature rise characteristics of organic sulfur models with different sulfur contents, it is believed that the higher sulfur content, the faster the low temperature oxidation reaction of “coal-like substance,” the faster the temperature rise rate, and the shorter the time to reach the uncontrollable self-heating temperature, so the shorter the spontaneous combustion period. In general, in the stage of low temperature oxidation, active sulfur containing small molecules (dimethyl sulfoxide) promote the oxidation temperature rise, stable structure, larger molecular weight of dibenzothiophene slow down the “coal-like” oxidation temperature rise.

Experimental Study on Low-Temperature-Oxidation Parameters and Simulations of Exothermic Process during Air Injection in Light Oil Reservoirs

Summary The thermal development process for light oil reservoirs using air injection technology is to release heat through low-temperature oxidation (LTO) between the injected air and crude oil and gradually increase the reaction zone’s temperature to displace crude oil. However, existing LTO experimental methods for air injection do not adequately capture the characteristics of LTO and struggle to directly obtain LTO kinetic parameters at low temperatures. In this paper, we used light oil samples from the Huabei Oilfield, China, as the studied objects and proposed innovative methods for obtaining and calculating LTO kinetic parameters. Further, we validated the feasibility of the proposed methods through experimental and numerical simulations. The results indicate that the lower limit temperature at which oxidation parameters can be directly measured through the accelerating rate calorimeter (ARC) experiments is 124°C. We matched the calculations from the ARC experiment curve-extension method for kinetic parameters with the results from both the high-pressure thermogravimetric analyzers (HP-TGA) experiment and the ramped thermal oxidizer (RTO) experiment. The fit between these results indicates that three methods are suitable for obtaining LTO parameters and can be used to derive chemical equations for LTO reactions in numerical simulation models. The simulation results from the reservoir scale indicate that, following air injection into the light oil reservoir, the peak temperature at the leading edge of the high-temperature zone reaches 370.9°C. The interaction between crude oil and air remains in the LTO phase, facilitating a sustained thermal accumulation within the reservoir. This study can provide a reference for reservoir development under similar conditions.

Low temperature oxidation chemistry of n-butylbenzene in n-decane/n-butylbenzene mixture: Product characterization and kinetic modeling study

n-Alkanes and aromatics are two essential components in transportation fuels and have distinct oxidation reactivities. Due to products with different chemical functionalities generated in oxidation of n-alkanes and aromatics, the interaction kinetics may significantly affect the overall reactivity as well as product distributions. This work investigated the oxidation chemistry of the mixture of n-decane and n-butylbenzene, both of which are C10 hydrocarbons commonly used as jet fuel surrogate components. The experiments were conducted in a jet stirred reactor at pressure of 1 atm, the temperature range of 450–850 K, and the equivalence ratios of 0.5, 1.0 and 2.0. Key low temperature oxidation intermediates and radicals, including C10-cyclic ethers, C10-ketohydroperoxides, C10-ketodihydroperoxide, C10-diketohydroperoxide, benzyl hydroperoxide, methyl peroxy radical and methyl hydroperoxide, were detected by using synchrotron vacuum ultraviolet photoionization mass spectrometry. A detailed kinetic model was developed and validated against the speciation data in this work. Results reveal that the reactions of n-decane greatly enhance the low temperature oxidation reactivity of n-butylbenzene by efficiently producing reactive radicals, such as OH radicals. Besides, the reactions of n-butylbenzene play an inhibiting role in low temperature oxidation reactivity of n-decane. The measured intermediates, such as C10-cyclic ethers, C10-ketohydroperoxides and C10-ketodihydroperoxide, provide experimental evidence to validate the first, second and third O2-addition reactions, respectively. Due to the addition of n-decane, the evolution profiles of aromatic intermediates as a function of temperature are quite different from the cases of pure n-butylbenzene oxidation. For example, the formation of benzene, phenol and benzaldehyde at low temperatures is significantly enhanced, whose mole fractions present negative temperature coefficient behaviours. Finally, the reaction pathways of the binary fuel to produce C5C1 alkenes, alkynes, aldehydes, alcohols, acids and peroxides were analysed.

The Influence of Ozone on the Flame Propagation Behavior of n-Heptane/air and i-Octane/air Premixed Flame in an Engine-Relevant Environment

ABSTRACT The promotional effect of ozone on lean premixed spherical flame propagation in an engine-relevant, high-temperature, high-pressure environment was investigated using an optically accessible rapid compression and expansion machine (RCEM). The laminar burning velocity, burned gas Markstein length, and initial flame development time based on mass fraction burned (MFB), were examined for n-heptane/air and i-octane/air premixture (φ = 0.55) with 15 [ppm] ozone, through self-emission observation of a propagating flame with a high-speed camera and combustion pressure analysis. The results showed that ozone reduced the initial flame development time and increased the laminar burning velocity for n-heptane/air premixture under temperature conditions in which the low-temperature oxidation (LTO) reaction was more clearly pronounced; but ozone did not enhance either the initial flame development or the laminar burning velocity in the case of i-octane/air premixture, where the LTO reaction was weak owing to the fuel molecular structure, even under the same temperature conditions. These results suggest that the enhancement of the LTO reaction by ozone, and the subsequent generation of thermal energy and CO radicals through an H2O2 loop reaction in the pre-flame region, were responsible for the increase in the laminar burning velocity. Furthermore, ozone increased the burned gas Markstein length, flame thickness, and Zeldovich number of the n-heptane/air mixture under the temperature conditions in which the laminar burning velocity was enhanced by ozone. This suggests that the chemical reaction in the reaction zone was more active in response to the increase in flame temperature.

Relationship between low-temperature oxidation activity and second-stage ignition delay: Experimental insights on n-pentanol / hydrogenated catalytic biodiesel blends

N-pentanol exhibits promising potential as a sustainable and eco-friendly biomass energy source. However, certain challenges such as ignition difficulty and unstable combustion exist. This study investigates the influence of low-temperature auto-ignition of n-pentanol/HCB (Hydrogenated Catalytic Biodiesel) blends on ignition and combustion characteristics and evaluates the correlation between low-temperature oxidation and second-stage ignition delay. Results show a linear positive correlation between the HCB content in n-pentanol and its low-temperature oxidation reactivity. The stronger the low-temperature oxidation activity of the blends, the shorter the second-stage ignition delay of blends. When the HCB content in blends is below 40 %, the low-temperature oxidation rate initially increases and then decreases. However, the low-temperature oxidation rate increases again when the HCB content exceeds 40 %. Moreover, the relationship between the initial CO2 generation rate and the HCB blending ratio follows an Exp exponential function under different critical compression ratios. Beyond 43.7 % HCB, an acceleration in the high-temperature combustion rate owing to an increase in the low-temperature oxidation rate again. In addition, the minimum ignition limit of n-pentanol/HCB blends was identified with 40 % HCB blends closely resembling diesel conditions and 50 % HCB blends showing a lower ignition limit, characterized by a critical temperature and pressure of 517.3 K and 8.66 bar, respectively. Furthermore, two distinct conditions for the minimum ignition boundary region of n-pentanol/HCB blends were defined, offering practical insights. In summary, a blend with a 50 % HCB ratio provides a promising solution for the low-temperature ignition and stable combustion of n-pentanol, addressing the challenges of simultaneous use in internal combustion engines.

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.

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.

Low-temperature oxidation of n-butanol in a jet-stirred reactor: Detailed species measurements and modeling studies

n-Butanol is a new generation of liquid biofuel. A detailed understanding of the low-temperature combustion chemistry of n-butanol is instructive for its practical application in advanced low-temperature engines. The high-temperature combustion chemistry of n-butanol has been extensively studied, but its low-temperature combustion chemistry remains underexplored, especially the detailed species distribution. In this work, ozone addition was used to enhance the low-temperature oxidation reaction activity to achieve the oxidation of n-butanol in a jet-stirred reactor (JSR) at atmospheric pressure and in the temperature range of 400–800 K. Synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) was used for detailed measurements of species distribution. The identification of some intermediate species contributed to elucidating and verifying the low-temperature oxidation reaction pathways of n-butanol, such as butanal, C4 hydroxyalkyl hydroperoxides, C4 hydroxyl cyclic ether, and C4 keto-hydroperoxide. Furthermore, the formation of several elusive intermediates was also identified (e.g., C2H4O2, C3H6O2, C4H6On (n = 1∼3), and C4H8O2), highlighting the necessity of further kinetic studies on the low-temperature oxidation of n-butanol. Based on detailed experimental measurements, the n-butanol model was further developed to improve the model predictions by updating the rate constants for the H-atom abstraction reactions of n-butanol by the ȮH radical, adding the detailed butanal sub-mechanism, etc. Especially, the premature formation of CO2 in the present experiment was satisfactorily explained and predicted by the addition of a generally accepted reaction class (i.e., RȮ2 + RȮ2 = RȮ + RȮ + O2 of butanal). Overall, this updated model satisfactorily predicts both the ignition delay time reported in the literature and the species distribution obtained in this work.

Low-temperature oxidative removal of benzene from the air using titanium carbide (MXene)-Supported platinum catalysts

MXenes are an emerging class of two-dimensional (2D) inorganic materials with great potential for versatile applications such as adsorption and catalysis. Here, we describe the synthesis of a platinized titanium carbide MXene (Pt@Ti3C2) catalyst with varying amounts of platinum (0.1%–2 wt.%) for the low-temperature oxidation of benzene, an aromatic volatile organic compound often found in industrial flue gas. A 1% formulation of Pt@Ti3C2–R allowed near-complete (97%) oxidation of benzene to CO2 at 225 °C with a steady-state reaction rate (r) of 0.119 mol g−1·h−1. This low-temperature catalytic oxidation reaction was promoted by an increase in the lattice oxygen (O*)/Pt2+ species (active sites) of 1%Pt@Ti3C2–R from 45.3/34.6% to 71.0/61.1% through pre-thermal reduction under H2 flow, as revealed by X-ray photoelectron spectroscopy, temperature-programmed reduction, and in situ diffuse reflectance infrared Fourier transform spectroscopy analyses. The cataltyic activity of 1% Pt@Ti3C2–R against benzene was assessed under the control of the key process variables (e.g., catalyst mass, flow rate, benzene concentration, relative humidity, and time-on-stream) to help optimize the oxidation reaction process. The results provide new insights into the use of platinum-based 2D MXene catalysts for low-temperature oxidative removal of benzene from the air.

Revealing the low to moderate temperature oxidation kinetics of 1,2,4-trimethylbenzene sensitized by dimethyl ether

Low to moderate temperature oxidation has been a vital topic in the combustion chemistry due to its critical role in controlling the combustion characteristics such as autoignition and pollutant emissions. Low temperature oxidation kinetics of alkanes and oxygenated biofuels have been widely explored, while that of branched aromatics is poorly understood. This work aims to investigate the low to moderate temperature oxidation kinetics of 1,2,4-trimethylbenzene (TMB, C9H12), which is a multi-branched alkylbenzene with weak low temperature oxidation reactivity. To enhance the low temperature oxidation reactivity of TMB, dimethyl ether (DME) was added to efficiently provide chain initiators. The oxidation experiment of TMB/DME mixture was performed with an atmospheric jet stirred reactor coupled with synchrotron vacuum ultraviolet radiation photoionization mass spectrometry. The negative temperature coefficient (NTC) behavior, as well as featured aromatic intermediates, especially phenyl hydroperoxides and unexpected highly oxygenated molecules (HOMs), were observed in the experiment. The detection of these fingerprint aromatic intermediates provide crucial evidence for revealing the low to moderate oxidation kinetics of TMB. In addition, a kinetic model was developed to provide in-depth kinetic analysis. The results demonstrate that the active chain initiators produced from DME oxidation trigger the low temperature chain-branching reactions of TMB. The chain recycling process is further sustained due to the regeneration of active intermediates such as phenyl hydroperoxides and •OH radicals. Aromatic intermediates with chemical compositions of C9H12Ox and C9H10Ox were measured and identified to be key indicators for the low temperature chemistry of TMB. In particular, the aromatic HOMs (C9H12O6 and C9H10O5) are fingerprint intermediates produced from the third O2 addition and subsequent reactions of TMB. Besides, the sensitivity analysis indicates that the interaction kinetics between TMB and DME by sharing the highly sensitive reactions of hydroperoxides and •OH radicals. The present work extends the conceptual reaction schemes proposed in alkanes towards branched aromatics, especially sequential O2 addition reactions that contributing to the formation of phenyl hydroperoxides and HOMs.

A revised reaction kinetic mechanism for the oxidation of methyl formate

The combustion kinetics of methyl formate (MeFo), a promising oxygenated, highly knock-resistant e-fuel, is investigated in this work. The potential energy surfaces (PESs) of the low-temperature oxidation reactions of MeFo radicals were determined at the CCSD(T)-F12/cc-pVTZ-F12//B2PLYP-D3/cc-pVTZ level of theory and their rate coefficients were obtained with RRKM/master equation. The thermochemical properties of relevant intermediate species were calculated by using the G4 method. A chemical mechanism for the oxidation of MeFo was developed by adding fuel-specific reactions taken from a literature model into a well-validated base mechanism, and incorporating the newly calculated rate constants of elementary reactions and thermochemical properties of species. The fuel-specific mechanism was further revised in terms of reaction channels and rate coefficients for improved prediction accuracy. In particular, the O2 addition to hydroperoxy radicals (QOOH), the isomerization of peroxy hydroperoxy radicals (OOQOOH), the subsequent ketohydroperoxide (KET) decomposition, and the formally direct pathways of MeFo radicals (R) with O2 were added for the completeness of consumption pathways, in conjunction with the reaction channels of alkoxy radicals (RO) and hydroperoxides (ROOH). For good model prediction accuracy of ignition delay times, especially in the high-temperature range, the resulting mechanism was optimized by modifying the rate constants of several important H-atom abstraction reactions of MeFo within their uncertainty limits. The performance of the proposed mechanism is demonstrated through extensive validation against literature data obtained from different experimental configurations. Finally, the underlying reaction pathways of MeFo are explored by means of reaction flux analysis with the newly developed chemical mechanism.Novelty and significance statement: This work proposes a new reaction kinetic mechanism for the oxidation of methyl formate. Quantum chemistry calculation at high level of theory was performed to explore the low-temperature chemistry of MeFo. The reaction mechanism was improved by including missing reaction channels, incorporating theoretically calculated rate and thermochemical data, and modifying rate constants of sensitive reactions. The mechanism has been validated successfully against extensive data available in the literature covering a wide range of conditions and facilities. By using this new mechanism, reaction pathway analysis is performed to provide insights into the oxidation chemistry of MeFo.

Very Low Temperature CO Oxidation over Atomically Precise Au25 Nanoclusters on MnO2.

Atomically precise Au25 nanoclusters have garnered significant interest in the field of heterogeneous catalysis due to their remarkable activity and selectivity. However, for the extensively studied reaction of low-temperature CO oxidation, their performance has not been competitive compared to other known gold nanocatalysts. To address this, we deposited Au25(SR)18 (R = CH2CH2Ph) nanoclusters onto a manganese oxide support (Au25/MnO2), resulting in a very stable and highly active catalyst. By optimizing the pretreatment temperature, we were able to significantly enhance the performance of the Au25/MnO2 catalyst, which outperformed most other gold catalysts. Impressively, 100% conversion of CO was achieved at temperatures as low as -50 °C, with 50% conversion being reached below -70 °C. Furthermore, the existence of ligands could also influence the negative apparent activation energy observed at intermediate temperatures. Analysis using X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), and X-ray diffraction (XRD) techniques indicated that the Au25 nanoclusters remained stable on the catalyst surface even after pretreatment at high temperatures. In-situ modulation excitation spectroscopy (MES) spectra also confirmed that the Au cluster was the active site for CO oxidation, highlighting the potential of atomically precise Au25 nanoclusters as primary active sites at very low temperatures.

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.

Chemical reaction analysis of auto-ignition behavior for mixed fuel of cyclopentane and paraffin

Knocking due to auto-ignition of fuel greatly hinders the performance enhancement of gasoline engines. Since general gasoline is a mixture of many substances, its knock resistance depends largely on the combination of substances contained. Therefore, it is important to comprehend the chemical reaction process up to ignition in mixed fuels. This study performed various analyses of the detailed chemical reaction process for the case where cyclopentane, a representative of naphthene, is mixed with paraffin. The main purpose of this analysis is to discover a mechanism that enhances the antiknock effect by combining fuels. Analysis of the detailed reaction process suggests that in some cases cyclopentane suppresses the subsequent reactions by consuming the OH produced by paraffin during the initial low temperature oxidation. Therefore, mixing cyclopentane into paraffin greatly extends the ignition delay time by suppressing the subsequent exothermic reactions. When added in a low fraction, the ignition suppression effect exceeds that of the general octane booster toluene. On the other hand, analysis of the detailed reaction process under high mixing ratio conditions showed that cyclopentane has an ignition promotion effect. The reason for this phenomenon is that cyclopentane lowers the ignition temperature because it accumulates a large amount of H2O2 as an intermediate product after the initial reactions. Furthermore, H2O2 advances the ignition reactions by generating OH in the subsequent reactions. Additionally, due to the changing behavior of the low-temperature oxidation reaction, the effect of cyclopentane mixing also changes with the temperature range. In other words, cyclopentane has the opposing effects of suppressing and promoting ignition, which results in a complicated phenomenon that changes depending on the mixing ratio with paraffin and temperature.

Time-shift effect of spontaneous combustion characteristics and microstructure difference of dry-soaked coal

The physical and chemical properties of the air-dried residual coal after soaking in the goaf will change, resulting in an increase in its spontaneous combustion tendency. This study aimed to look into the features and mechanism of soaked-dried coal's spontaneous combustion. Five samples of coal were dried to various degrees, and the weight loss features during thermal processing were examined. Based on this, the pore structure and chemical structure characteristics of the coal samples with the highest tendency to spontaneous combustion were quantitatively examined, and the mechanism by which soaking-drying affected the spontaneous combustion heating process of the remaining coal in goaf was investigated in turn. The results show that T1 decreases with the increase of drying time, T2–T6 shows a fluctuating change, and the ignition activation energy of 36-S-Coal is smaller than that of other coal samples. The pore type of 36-S-Coal changes from a one-end closed impermeable pore to an open pore, and the pore group area is large. During the 36 h drying process, the internal channels of the coal were dredged, and a large number of gravels and minerals were precipitated from the pores with the air flow. A large number of gravels were around the pores to form a surface structure that was easy to adsorb various gases. Furthermore, infrared spectroscopy was used to analyze the two coal samples. It was found that soaking and drying did not change the functional group types of coal samples, but the fatty chain degree of 36-S-Coal was reduced to 1.56. It shows that the aliphatic chain structure of coal is changed after 36 h of drying after 30 days of soaking, which leads to the continuous shedding of aliphatic chain branches of residual coal, and the skeleton of coal is looser, which makes the low-temperature oxidation reaction of 36-S-Coal easier. Based on the above results, the coal-oxygen composite mechanism of water-immersed-dried coal is obtained, and it is considered that the key to the spontaneous combustion oxidation process of coal is to provide oxygen atoms and accelerate the formation of peroxides.