Modeling thermal analysis for predicting thermal hazards relevant to transportation safety and runaway reaction for 2,2′-azobis(isobutyronitrile)

The pure decomposition behavior of 2,2′-azobis (isobutyronitrile) (AIBN) and its physical phase transformation were examined and discussed. The thermal decomposition of this self-reactive azo compound was explored using differential scanning calorimetry (DSC) to elucidate the stages in the progress of this chemical reaction. DSC was used to predict the kinetic and process safety parameters, such as self-accelerating decomposition temperature (SADT), time to maximum reaction rate under adiabatic conditions (TMR_ad), and apparent activation energy (E_a), under isothermal and adiabatic conditions with thermal analysis models. Moreover, vent sizing package 2 (VSP2) was applied to examine the runaway reaction combined with simulation and experiments for thermal hazard assessment of AIBN. A thorough understanding of this reaction process can identify AIBN as a hazardous and vulnerable chemical during upset situations. The sublimation and melting of AIBN near its apparent onset decomposition temperature contributed to the initial steps of the reaction and explained the exothermic attributes of the peaks observed in the calorimetric investigation.     

The influence of ClO− and acidity in the reaction between H2O2 and CuCl2

The potentially explosive reaction of hydrogen peroxide (H₂O₂) and copper chloride (CuCl₂) was investigated. Pressure tests revealed that the reaction was strongly temperature - dependent and can easily undergo runaway reaction. Nevertheless, there was only a slight pressure increase at the low temperatures studied or when using low concentrations of CuCl₂. Under the conditions generating the slight pressure increase, hypochlorite anions (ClO⁻) are generated and the acidity increases. As the reaction reaches completion, ClO⁻ disappears, and the acidity decreases. Interestingly, the addition of phosphate buffer to maintain the weakly acid conditions led to a runaway reaction, and the use of basic ClO⁻ promoted the exothermic reaction. Based on the results, acidity has a strong impact on the reaction behaviour.     

Thermal hazard accident investigation of hydrogen peroxide mixing with propanone employing calorimetric approaches

Hydrogen peroxide (H₂O₂), historically, due to its broad applications in the chemical industries, has caused many serious fires and explosions around the world. Its thermal hazards may also be incurred by an incompatible reaction with other chemicals, and a runaway reaction may be induced in the last stage. This study applied thermal analytical methods to explore the H₂O₂ leading to these accidents by incompatibility and to discuss what might be formed by the upset situations. Thermal hazard analysis contained a solvent, propanone (CH₃COCH₃, so-called acetone), which was deliberately selected to mix with H₂O₂ for investigating the degree of thermal hazard. Differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2) were employed to evaluate the thermal hazard of H₂O₂. The results indicated that H₂O₂ is highly hazardous while mixed with propanone, as a potential contaminant. The time to maximum rate (TMR) was used as emergency response time in the chemical industries. Therefore, TMR of H₂O₂ was calculated to be 70 min for runaway reaction (after T₀) and TMR of H₂O₂/propanone was discovered to be 27 min only. Fire and explosion hazards could be successfully lessened if the safety-related data are properly imbedded into manufacturing processes.     

汽车尾气净化催化剂Ag/SAPO-34选择性催化还原NO

评价了Ag/SAPO-34分子筛催化剂选择性还原NO的活性,并运用漫反射红外光谱原位研究NO在Ag/SAPO-34催化剂上的选择性催化还原机理.结果表明Ag/SAPO-34有良好的低温活性,在氧气浓度为3.6%和温度为573K～673K时NO还原成N2的转化率达70%;催化剂活性随C3H6浓度的增加而升高,随空速的增加而稍有下降.基于漫反射红外光谱,认为反应机理为:NO、丙烯和氧反应,在Ag/SAPO-34催化剂上生成吸附的有机-氮氧化物,再由这些吸附物种分解成N₂,催化还原的关键是形成有机-氮氧化物中间体.氧的作用是充分促进丙烯活化以及增加NO_x吸附态含量,并且氧的存在是有效产生一系列中间物不可缺少的条件.     

Degradation of antipyrine in the Fenton-like process with a La-doped heterogeneous catalyst

A La-doped Co-Cu-Fe catalyst was synthesized for the antipyrine (ANT) removal. The La-doped catalyst had higher ANT removal than the control (95% vs. 54%). La reduced the particle size and increased the specific surface area of catalyst. The aim of this study was to synthesize a novel lanthanum (La) doped catalyst and to investigate antipyrine removal in wastewater using the Fenton-like process with the catalyst. The La-doped Co-Cu-Fe catalyst was synthesized using the modified hydrothermal method. Results showed that the La-doped catalyst had higher specific surface area and lower particle size than the catalyst without La doping (i.e., the control) (267 vs. 163 m²/g and 14 vs. 32 nm, respectively). Under the conditions of catalyst dosage 0.5 g/L, H₂O₂ concentration 1.70 g/L, and NaHCO₃ 0.1 g/L, the antipyrine removal within 60 min using the Fenton-like process with the La-doped catalyst was much higher than that with the control (95% vs. 54%). The hydroxyl radical concentration with the La-doped catalyst within 60 min was two times higher than that with the control (49.2 vs. 22.1 mg/L). The high catalytic activity of La-doped catalyst was mainly attributed to its high specific surface area based on the X-ray photoelectron spectroscopy result. Our La-doped catalyst should have great potential to remove antipyrine in wastewater using the heterogeneous Fenton-like process.     

Carbon nanotubes-incorporated MIL-88B-Fe as highly efficient Fenton-like catalyst for degradation of organic pollutants

CNTs were incorporated into MIL-88B-Fe to get a new Fenton-like catalyst (C@M). Fe(II) was introduced in C@M to get a fast initiation of Fenton-like reaction. Fe(II) content in C@M was related with oxygen-containing functional groups on CNTs. C@M shows efficient catalytic degradation of pollutants over a wide pH range. Iron-based metal organic frameworks have been verified to be efficient heterogeneous Fenton catalysts due to their open pore channels and highly uniform distribution of metallic centers. In these catalysts, however, the iron element is mainly in the form of Fe(III), which results in a process required to reduce Fe(III) to Fe(II) to initiate Fenton reaction. To address this problem, carbon nanotubes (CNTs) with electron-rich oxygen-functional groups on the surface were incorporated into the metal organic frameworks (MIL-88B-Fe) to improve Fe(II) content for an enhanced Fenton-like performance. The prepared CNT@MIL-88B-Fe (C@M) showed much stronger catalytic ability toward H₂O₂ than MIL-88B-Fe. The pseudo-first-order kinetic constant for phenol degradation by C@M (0.32 min^–1) was about 7 times that of MIL-88B-Fe, and even higher than or comparable to the values of reported heterogeneous Fenton-like catalysts. Moreover, the Fenton-like system could effectively degrade various kinds of refractory organic pollutants and exhibited excellent catalytic activity over a wide pH range (4–9). XPS analysis confirmed that Fe(II) content of the catalyst gradually increased with CNT loadings. Electron spin resonance analysis showed that the signal intensity (•OH) of C@M was much higher than MIL-88B-Fe, which was consistent with the degradation efficiency of pollutants. Furthermore, the Fe(II) content of the catalyst gradually increased along with the oxygen-functional group content of CNTs. The result demonstrated that oxygen-containing functional groups of CNTs have a significant impact on the enhanced catalytic performance of C@M. This study provides a new insight to enhance Fenton reaction by using nanocarbon materials.     

Alternative method to prevent thermal runaway in case of error on operating conditions continuous reactor

Thermal runaway was studied in a continuous tubular pilot reactor under steady-state regime. Different accident scenarii were conducted by making some errors on reactant concentrations and/or temperature feed. To prevent thermal runaway, control by direct contact by solvent injection was used at different reactor locations. This injection allowed controlling the maximum reaction temperature. A simplified analytical method to estimate the maximum reaction temperature along the reactor was used.Benefit of this control method was the diminution of computational time. Furthermore, by injecting solvent to control maximum reaction temperature, there is no need to shut down the unit. The control method was validated experimentally.     

煤矿照度对人反应时间和可靠度的影响研究

煤矿综采工作面狭窄,工作环境昏暗,照明环境普遍不好,是近年来井下事故多发的重要因素之一。针对目前煤矿综采工作面存在的照度问题,通过控制光照时间和操作难度,利用舒尔特表测算反应时间和操作可靠度,使用SPSS20. 0和Excel进行数据处理,设计试验组和对照组来进行对比试验。结果表明,1)从反应时间来看,0～25 min,试验组平均反应时间的变化趋势与对照组相反,被试者的注意力先下降后上升; 25～55 min,被试者逐渐适应低照度环境,反应时间也在逐渐缩短;被试者在低照度条件下操作55 min后,反应时间随光照时间增加而大幅度增加,超过劳动时间临界值后,视觉疲劳度迅速增加,反应急速减慢,从而可能导致安全事故的发生,影响生产效率,此时应合理安排工人休息。2)从操作难度来看,在简单及正常操作难度时,试验组和对照组操作可靠度变化比较接近,表明低照度条件对一般操作的可靠度影响不明显;在极难操作难度时,低照度条件对可靠度影响明显,在井下生产过程中,低照度环境下应尽量避免安排复杂的机械化操作。3)反应时间与光照时间呈二次函数关系,通过建立回归方程量化了两者的关系,为以后合理安排煤矿工人劳动休息时间提供了理论依据。     

二氧化硫与环己烷的光化学反应

本文研究了ＳＯ２与环己烷在无氧及有氧体系中的光化学反应，观察到了白色烟雾有生成并凝聚，利用ＧＣ和ＧＣ／ＭＳ法确定了部分反应产物－环烯烃、醇、酮、二元酸酯、呋喃衍生物以及硫酸二甲酯等有机化合物，探讨了影响光化学反应的几种因素及反应机理。     

铁聚合反应速率研究

研究了聚合硫酸铁絮凝剂制备中亚铁的氧化反应速率，证明该速率对Ｆｅ＾２＋为零级，对ＮＯ２（ｇ）为一级，因此提高气相中ＮＯ２的分压可大大缩短制备时间。