The effect of N2/CO2 blend ratios on the pyrolysis and combustion behaviors of coal particles: Kinetic and thermodynamic analyses

The aim of this work is to investigate the impact of various CO₂/N₂ ratios on coal pyrolysis and combustion properties and to provide theoretical guidance for better preventing and controlling coal spontaneous combustion in the goaf. The dynamic pyrolysis and combustion characteristics of DX coal were analyzed by using a thermal gravimetric analyzer (TGA) in a constant oxygen atmosphere with different CO₂/N₂ blend ratios. The Málek method combining Coats-Redfern and Achar methods was used to determine the most probable mechanism functions. CO₂ containing atmospheres increased characteristic temperatures, burnout rate, maximum mass loss rate and comprehensive combustion performance index compared to O₂/N₂ atmospheres. In stages I-III, a lower apparent activation energy was observed in O₂/CO₂ atmospheres. Apparent activation energy and enthalpy changes showed upward trends in the reaction stage (I→III→IV), whereas Gibbs free energy change and entropy change decreased. The dynamic pyrolysis and combustion of DX coal necessitated increased energy in environment with a CO₂/N₂ ratio of 4:6, revealing the optimal inhibitory effect on DX coal with this particular ratio.     

Statistical modeling of radiolytic (60Co g) degradation of Ofloxacin,antibiotic: Synergetic effect,kinetic studies & assessment of its degraded metabolites

Linear, interactive and quadratic effects of process parameters were studied. Degradation of Ofloxacin (Ofx) was related with G value of irradiation process. The synergistic effect of H₂O₂ on lower dose of g-irradiation was established. The process follows pseudo first order with dose constant (d = 0.232 kGy^–1). The impact of human activities in the past few decades has paved the way for the release of pollutants due to the improper effluent treatment. Recent studies revealed that, Ofloxacin, an antibiotic as one of the major pollutant affecting surface water and ground water. In this study, the radiolytic potential of Ofloxacin was investigated. The effects of pH, dose and concentration of Ofloxacin were analyzed using One Factor At a Time (OFAT) and the interactive effects between the parameters were studied using Face Centered Central Composite Design. The statistically optimised developed model shows 30% degradation at initial antibiotic concentration of 1mM at pH 3.0 and at 2 kGy dose of gamma ray. The process efficiency was evaluated in terms of G value and its correlation with the concentration of antibiotic was also established. The process of degradation was augmented by the addition of H₂O₂ (1.5 mM). The reaction kinetics for the process was evaluated, the dose rate constant and the rate of degradation for the augmented process was found to be 0.232 kGy^-1 and 0.232 mM/kGy, respectively. The degraded metabolites of the radiolytic degradation of Ofloxacin were analyzed through change in pH, reduction in TOC and GC-MS spectrum.     

CODCr测定中硫酸亚铁铵溶液稳定性的探讨

根据氧化－还原反应原理和电化学反应机理，对ＣＯＤｃｒ测定中所使用的硫酸亚铁铵溶液浓度稳定性进行探讨并提出使其稳定的方法。     

废水湿式氧化法影响因素的分析

综述了废水湿式空气氧化法和Ｈ－酸配水的处理试验以及其中影响氧化效率的主要因素及其作用原因，并对其进行了较合面的理论分析和探讨，分析表明：（１）废水性质反应温度和进水ＰＨ值是影响湿式空气氧化处理效率最重要的影响因子；（２）反应时间，压力，搅拌强度，进水有机物浓度、盐效应等也有影响作用；（３）研究湿式氧化反应的影响因素有助于更好地理解反应过程。     

Thermal behaviors, combustion mechanisms, evolved gasses, and ash analysis of spent potlining for a hazardous waste management

An unavoidable but reusable waste so as to enhance a more circular waste utilization has been spent potlining (SPL) generated by the aluminum industry. The combustion mechanisms, evolved gasses, and ash properties of SPL were characterized dynamically in response to the elevated temperature and heating rates. Differential scanning calorimetric (DSC) results indicated an exothermic reaction behavior probably able to meet the energy needs of various industrial applications. The reaction mechanisms for the SPL combustion were best described using the 1.5-, 3- and 2.5-order reaction models. Fluoride volatilization rate of the flue gas was estimated at 2.24%. The SPL combustion emitted CO₂, HNCO, NO, and NO₂ but SO_x. The joint optimization of remaining mass, derivative thermogravimetry, and derivative DSC was achieved with the optimal temperature and heating rate combination of 783.5°C, and 5 °C/min, respectively. Interaction between temperature and heating rate exerted the strongest and weakest impact on DSC and remaining mass, respectively. The fluorine mainly as the formation of substantial NaF and CaF₂ in the residual ash. Besides, the composition and effect of environment of residual solid were evaluated. The ash slagging tendency and its mineral deposition mechanisms were elucidated in terms of turning SPL waste into a benign input to a circular waste utilization.     

亚硝酸根—番红O重氮化偶联反应机理研究

研究了在酸性介质中，亚硝酸根离子与番红Ｏ偶联反应的机理，并作为光度分析新方法应用于测定亚硝酸根离子，研究表明，在５２０ｎｍ处，试剂空白同试液吸光度的差值与亚硝酸根离子的含量在２０－５００μｇ／Ｌ范围内的成线性关系。方法用于土壤，环境水样中亚硝酸根离子的测定，结果满意。     

HQSAR and CoMFA approaches in predicting reactivity of halogenated compounds with hydroxyl radicals

Two quantitative structure–activity relationship (QSAR) methods: hologram QSAR (HQSAR) and comparative molecular field analysis (CoMFa) were evaluated for predicting half-lives of the hydroxyl radicals reaction with substituted aromatic compounds. The HQSAR approach, which is topological in nature, results in a mathematical model which was more stable and has a greater predictive ability than the model derived on the 3-D CoMFA approach. Interpretations of the colour coded results of both methods are in good agreement with the proposed mechanism of the hydroxyl radical oxidation of halogenated aromatic compounds in the atmosphere.     

A generalized differential method to calculate lumped kinetic triplet of the nth order model for the global one-step heterogeneous reaction using TG data

Computing kinetic triplet is of importance for the process safety of combustion/gasification industries to establish the chemical reaction scheme and to assess the hazardous risk. Few approaches have been capable of calculating lumped kinetic triplet at one time efficiently, which might be attributed to the fact that the analytical solution for the nonlinear ordinary differential equation (NNODE) for the n^th order reaction model has not been found yet. This paper presents an analytical solution of NNODE to compute kinetic triplet. Results showed that the proposed method (mass fraction curve-fitting error ϕ = 1.49%–2.07%) is more efficient to compute kinetic triplet of the n^th order reaction model, comparing to genetic algorithm (GA) optimization (ϕ = 1.43%–1.81%), Coats-Redfern (ϕ = 2.36%–3.16%), peak-shape, and isoconversional methods. A compensation effect between lnA and E_a is observed due to heating rates. Effects of exported data quality and smooth processing on computation of kinetic triplet are discussed. It is the first time that an analytical solution of NNODE (n^th order model) for global one-step heterogeneous reaction is derived for computing kinetic triplet. This work may help to search for analytical solutions of power-law and Avrami-Erofeev models in the future to efficiently calculate kinetic triplet for accelerating and sigmoidal reaction systems.     

Reaction hazard and mechanism study of H2O2 oxidation of 2-butanol to methyl ethyl ketone using DSC,Phi-TEC II and GC-MS

Methyl ethyl ketone (MEK) oxidation via H₂O₂ with tungsten-based polyoxometalate catalysts has gained much attention with an ever-growing body of knowledge focusing on the development of environmentally benign processes in chemical industry. In this study, two calorimetry techniques, differential scanning calorimetry (DSC) and Phi-TEC II adiabatic calorimetry, were employed to analyze the thermal hazards associated with the 2-butanol oxidation reaction system. Hydrogen peroxide was the oxidant and a tungsten-based polyoxometalate as the catalyst. Gas chromatography-mass spectrometry was used for identification of the organic products. Important thermal kinetic data were obtained including “onset” temperature, heat of reaction, adiabatic temperature rise and self-heat rate. From DSC results, three exothermic peaks were detected with a total heat generation of approximately 1.26 kJ/g sufficiently to induce a thermal runaway. Possible reaction pathway for three stages were proposed based on both DSC and GC-MS results. One exotherm was detected by Phi-TEC II calorimeter and the pressure versus temperature profile together with the DSC and GC-MS data demonstrate the complexity of 2-butanol reaction system under both thermal screening and adiabatic conditions.