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.     

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.     

Suspected flunixin poisoning of a wild Eurasian Griffon Vulture from Spain

Exposure to residues of the nonsteroidal anti‐inflammatory drug (NSAID) diclofenac present in livestock carcasses has caused extensive declines in 3 Gyps vulture species across Asia. The carcass of a wild Eurasian Griffon Vulture (Gyps fulvus) was found in 2012 on an Andalucian (Spain) game hunting reserve and examined forensically. The bird had severe visceral gout, a finding consistent with Gyps vultures from Asia that have been poisoned by diclofenac. Liver and kidney samples from this Eurasian Griffon Vulture contained elevated flunixin (an NSAID) levels (median = 2.70 and 6.50 mg/kg, respectively). This is the first reported case of a wild vulture being exposed to and apparently killed by an NSAID outside Asia. It is also the first reported instance of mortality in the wild resulting from environmental exposure to an NSAID other than diclofenac. Caso de Sospecha de Envenenamiento por Flunixin de un Buitre Leonado en España     

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。     

二氧化硫与1—己烯的光化学反应动力学

利用ＧＣ／ＭＳ方法研究了ＳＯ２与１－己烯在无氧和有氧体系中光化学反应动力学，确定了ＳＯ２与１－己烯光化学反应的级数，给出了２９３－３３３Ｋ温度范围内总的反应速度常数Ｋ，以及Ｋ与温度的关系、反应的活化能和指前因子。另外，对反应物己醛和２－己酮的生成反应速度常数及其活化能也进行了计算和讨论。     

生物膜法降解甲苯废气过程的探讨

采用陶粒为填料的生物滤池降解甲苯废气，并对清水试验和生物膜试验的结果进行分析，发现生物膜法降解甲苯这样的挥发性有机物（VOCs)具有良好的效果，已不再是清水试验中单纯的物理吸收过程，而是伴有生化反应的吸收过程，是以气膜控制为主的传质过程。     

固定化光合细菌处理催化裂化与加氢废水

在２８Ｌ柱式反应器内,沼泽红假单胞菌经软性纤维固定后,连续处理炼油厂催化裂化与加氢废水（此前已经过汽提和厌氧消化预处理）。当反应器进水ＣＯＤ为４７０ｍｇ／Ｌ、废水停留时间为７０ｈ时,出水分离出菌体后,ＣＯＤ小于１００ｍｇ／Ｌ。建立了该处理系统的动力学模型,其参数Ｋｓ＝２９．８ｍｇ／Ｌ,μｍ＝０．０１ｈ－１。     

分光光度法测定COD_(Cr)的试验条件选择

用分光光度法测定水中化学需氧量ＣＯＤＣｒ,通过正交试验选择氧化的最佳选择。试验结果表明对ＣＯＤＣｒ值为５０～１０００ｍｇ／Ｌ的水样：氧化剂Ｋ２Ｃｒ２Ｏ７用量为０．２０～０．４０ｍｏｌ／Ｌ,催化剂Ａｇ２ＳＯ４用量为１０ｇ／ＬＨ２ＳＯ４,消解时间１０ｍｉｎ,加热温度１８０℃。用ＣＯＤＣｒ为１３８ｍｇ／Ｌ的质控标样进行验证试验,其绝对误差为０．５～３．０ｍｇ／Ｌ。与标准方法相比用分光光度法测定ＣＯＤＣｒ具有分析误差小,省时、省力,节约药剂的特点。