Calorimetric studies on the thermal hazard of methyl ethyl ketone peroxide with incompatible substances

In Taiwan, Japan, and China, methyl ethyl ketone peroxide (MEKPO) has caused many severe thermal explosions owing to its thermal instability and reactivity originating from the complexity of its structure. This study focused on the incompatible features of MEKPO as detected by calorimetry. The thermal decomposition and runaway behaviors of MEKPO with about 10wt.% incompatibilities, such as H(2)SO(4), HCl, NaOH, KOH, FeCl(3), and FeSO(4), were analyzed by dynamic calorimeter, differential scanning calorimetry (DSC) and adiabatic calorimeter, vent sizing package 2 (VSP2). Thermokinetic data, such as onset temperature, heat of decomposition, adiabatic temperature rise, and self-heat rate, were obtained and assessed. Experimental data were used for determining the incompatibility rating on hazards. From the thermal curves of MEKPO with assumed incompatible substances detected by DSC, all the onset temperatures in the other tests occurring earlier advanced, especially with alkaline or ferric materials. In some tests, significant incompatible reactions were found. Adiabatic runaway behaviors for simulating the worst case scenario were performed by using VSP2. These calorimetric data led to the same results that the alkaline or ferric solution was the most incompatible with MEKPO.     

Oxidative pyrolysis of organic ion exchange resins in the presence of metal oxide catalysts

Pretreatment of the organic ion exchange resins by oxidative pyrolysis is effective for volume reduction before vitrification. In this work, pyrolysis of two nuclear-grade resins, Purolite NRW100 (cationic) and NRW400 (anionic), was examined using a laboratory-scale theromgravimetric analyzer (TGA) in air. It was shown that the cationic resin was harder to degrade and was less volatile compared to anionic resin. Off-gas data revealed the presence of SO2, CO2, CO, and H2O during oxidative pyrolysis of cationic resin from 30 to 800 degrees C. Trimethylamine, CO2, CO, and ethyl formate were found in the case of anionic resin. In addition, oxidative pyrolysis of the mixed resins (50/50 wt.%) showed the existence of the gases nearly at the temperatures where the gases would evolve if the results of two different resins were superimposed. Several metal salts including CuSO4*5H2O, CuO, and FeSO4*7H2O, as well as the ions Cu2+ pre-loaded on the resins had a catalytic effect on the oxidative pyrolysis of cationic resins, in which the decomposition of functional groups and polymer matrices was enhanced. Such catalytic effect was highlighted by a large decrease in activation energy calculated according to a degradation mechanism involving four consecutive reactions.     

Effects of acetone on methyl ethyl ketone peroxide runaway reaction

Runaway reactions by methyl ethyl ketone peroxide (MEKPO) are an important issue in Asia, due to its unstable structure and extensive heat release during upset situations. This study employed differential scanning calorimetry (DSC) to draw the experimental data for MEKPO 31 mass% and with acetone 99 mass% on three types of heating rate of 2, 4, and 10 degrees C/min; the kinetic and safety parameters were then evaluated via curve fitting. Through the reproducible tests in each condition, the results show that acetone is not a contaminant, because it could increase the activation energy (Ea) and onset temperature (To) when combined with MEKPO, which differs from the hazard information of the material safety data sheet (MSDS).     

Hydroxylamine nitrate self-catalytic kinetics study with adiabatic calorimetry

Hydroxylamine nitrate (HAN) is an important member of the hydroxylamine compound family with applications that include equipment decontamination in the nuclear industry and aqueous or solid propellants. Due to its instability and autocatalytic behavior, HAN has been involved in several incidents at the Hanford and Savannah River Site (SRS) [Technical Report on Hydroxylamine Nitrate, US Department of Energy, 1998]. Much research has been conducted on HAN in different areas, such as combustion mechanism, decomposition mechanism, and runaway behavior. However, the autocatalytic decomposition behavior of HAN at runaway stage has not been fully addressed due to its highly exothermic and rapid decomposition behavior. This work is focused on extracting HAN autocatalytic kinetics and analyzing HAN critical behavior from adiabatic calorimetry measurements. A lumped autocatalytic kinetic model for HAN and associated model parameters are determined. Also the storage and handling critical conditions of diluted HAN solution without metal presence are quantified.     

Effects of alloying elements on the electrochemical characteristics of iron aluminides

Effects of alloying elements on the electrochemical characteristics of iron aluminides in the H2SO4, H2SO4+KSCN and HCl solutions were investigated using electrochemical tests. The corrosion morphologies in iron aluminides were analysed by utilising optical microscopy. It was found that the addition of Cr and Mo to iron aluminides increased the corrosion potential, pitting potential and repassivation potential. The active current density, passive current density and reactivation current density decreased as Cr and Mo were added. In the case of Mo addition, the passive current density was slightly higher in the H2SO4 solution than in solutions containing SCN- and Cl-. When B was added to samples, the corrosion potential and repassivation potential decreased, whereas the active current density, passive current density, reactivation current density and pitting potential increased. Iron aluminides containing Mo and Cr showed remarkably improved intergranular and pitting corrosion resistance to SCN- and Cl- solution. On the other hand, B addition accelerated granular and intergranular corrosion by precipitation of borides. This revised version was published online in November 2006 with corrections to the Cover Date.     

Investigation of the decomposition reaction and dust explosion characteristics of crystalline benzoyl peroxides

The benzoyl peroxide (BPO) is widely used in the chemical industry. Many catastrophes have been caused by its thermal instability or reactive incompatibility in storage or thermal decomposition reaction. Thus, its hazard characteristics have to be clearly identified. First of all, the differential scanning calorimeter (DSC) is used to measure the heat of decomposition reaction, which can contribute to understanding the reaction characteristics of benzoyl peroxide. The accelerating rate calorimeter (ARC) is used to measure the rates of temperature and pressure rises of decomposition reaction, and then the kinetics parameters are estimated. Furthermore, the MIKE 3 apparatus and the 20-l-Apparatus are used to measure and analyze the dust explosion characteristics of benzoyl peroxide under room temperature and atmospheric pressure. Finally, Semenov's thermal explosion theory is applied to investigate the critical runaway condition and the stability criterion of decomposition reaction, and to build the relationship of critical temperature, convective heat transfer coefficient, heat transfer surface area and ambient temperature. These results contribute to improving the safety in the reaction, transportation and storage processes of benzoyl peroxide.     

Risk evaluation on the basis of pressure rate measured by automatic pressure tracking adiabatic calorimeter

An automatic pressure tracking adiabatic calorimeter (APTAC) had been employed to obtain the thermokinetic and the vapor pressure data during runaway reactions. The APTAC is an adiabatic calorimeter with a large-scale sample mass and low thermal inertia, and is an extremely useful tool for assessing thermal hazards of reactive chemicals. The data obtained by the APTAC are important information for the design of the safe industrial process. The thermodynamics parameters and the gas production were discussed on the basis of the experimental data of various concentrations and weights of di-tert-butyl peroxide (DTBP)/toluene solution for the purpose of investigating the properties of the APTAC data. The thermal decomposition of DTBP was studied on the basis of the temperature data and the pressure data obtained by the APTAC. The activation energy and the frequency factor of DTBP are nearly constant and the same as the literature values in the concentrations between 20 and 60 wt.%. The pressure rise due to gas production is important data for designing the relief vent of a reactor. The time history of the gas production was investigated with various weights and concentrations. The total gas production index, which had the vapor pressure correction, was 1.0 in the decomposition of DTBP.     

Effects of Cl- and SO2-4 Ions on Corrosion Behavior of X70 Steel

Corrosion behaviors of X70 steel were studied by means of electrochemical experiments and morphology observation.First, through potentiodynamic polarization in solution of various Cl- ions concentration, it was found that Epit began to appear in solution of Cl- concentration above 0.1 mol/L, and there was a critical point of Cl- concentration between 0.05 mol/L and 0.1 mol/L, below which the extent of pitting and general corrosion were trivial, while in solution of Cl- concentration above 0.1 mol/L, general and pitting corrosion became greater as the increasing of Cl- concentration. All of them were confirmed by the SEM observations after anodic polarization. Second, via the potentiodynamic polarization curves of X70 steel in 0.5 mol/L Cl- solution with 0, 0.05, 0.5 and 1 mol/L SO42-ions, it was found SO42- ions were able to inhibit corrosion aroused from Cl- ions, accordingly a model was set up to describe the process. In addition, to further explore the inhibited effect of SO42- ions, EIS was used in solutions of different Cl- and SO42- concentrations, the results revealed that the e(ectrochemical resistance has a relation with the [SO42-]/[Cl-], that was, the bigger the value of [SO42-]/[Cl-], the greater the electrochemical resistance.     

Effect of air in the thermal decomposition of 50 mass% hydroxylamine/water

This paper presents experimental measurements of 50 mass% hydroxylamine (HA)/water thermal decomposition in air and vacuum environments using an automatic pressure tracking adiabatic calorimeter (APTAC). Overall kinetics, onset temperatures, non-condensable pressures, times to maximum rate, heat and pressure rates versus temperature, and mixture vapor pressures for the experiments in vacuum were similar when compared to the corresponding data for HA decomposition in air. Determined was an overall activation energy of 119+/-8 kJ/mol (29+/-2 kcal/mol), which is low compared to 257 kJ/mol (61.3 kcal/mol) required to break the H(2)N-OH bond reported in the literature. The availability of oxygen from air did not affect detected runaway decomposition products, which were H(2), N(2), N(2)O, NO, and NH(3), for samples run in vacuum or with air above the sample. A delta H(rxn) of -117 kJ/mol (28 kcal/mol) was estimated for the HA decomposition reaction under runaway conditions.     

低应力氨基磺酸镀镍在航空维修中的应用

低应力氨基磺酸镀镍尽管在航空零部件制造、维修中应用广泛,但仍需对其存在的应力、氢脆等问题给予足够的关注和严格的工艺控制。为此,采用螺旋收缩测量法定量研究了氨基磺酸盐镀镍层内应力的影响因素,并用静态拉伸法测试了镀镍工艺对高强度钢氢脆性能的影响。结果表明:氨基磺酸镍及硼酸含量对镀层内应力影响较小;使用氨基磺酸或碳酸镍调整溶液p H值都会提高镀层内应力,但不会造成基体发生氢脆,实际生产中应谨慎使用;溶液中的Cl^-、Fe²⁺、Cu²⁺、Cr⁶⁺浓度的增加都会不同程度提高电镀镍层的内应力,尤其Cr6+对镀层外观、内应力、氢脆性能等都会产生很大影响,生产中应注意控制;结合工艺标准的要求及试验数据,给出了推荐的镀镍工艺配方:H3BO340～50 g/L(达到饱和状态),Ni(NH2SO3)2·4H2O 325～345 g/L,Ni2+76.0～80.7 g/L,Cl-3～10 g/L,pH值3～4,湿润剂0.2 m L/L,温度50～55℃,电流密度5.4 A/dm2,Fe²⁺<100 mg/L,Cu²⁺<50 mg/L,Cr⁶⁺<2.5 mg/L。     

Electrochemical detection of chloride by underpotentially deposited silver films on polycrystalline gold

This paper describes an electrochemical method for measuring dilute levels of chloride using an underpotentially deposited (UPD) Ag adlayer on polycrystalline Au substrates as a sensing agent. Specifically, chloride ions adsorb onto the Ag UPD adlayer and effect changes in the electrochemical deposition and stripping characteristics of the silver film. Cyclic voltammograms (CVs) of the native Au/Ag(UPD) electrode in 0.1 M H2SO4(aq) exhibit a primary stripping peak for the Ag UPD adlayer at 550 mV vs Ag(+/0), and chloride adsorption onto the Au/Ag(UPD) surface effects a peak shift to approximately 600 mV vs Ag(+/0), depending on the amount of adsorbed Cl-, as affected by the Cl- concentrations and contact times employed in the derivatization. The chloride-treated electrodes also exhibit a stripping peak at 275 mV that is not observed on the native substrate and increases in intensity with Cl- concentration and derivatization time. The integrated charge density for this latter stripping peak relative to that for the primary stripping peak at 550-610 mV provides a useful metric for quantifying adsorbed Cl- levels, and these values allow measurement of Cl- concentrations in dilute aqueous solutions. For Cl- concentrations between 0.5 and 100 microM, the kinetics of Cl- adsorption followed a transient Langmuir adsorption model and allowed measured surface coverages to be used for determining Cl- solution concentrations. Using contact times of 1 min for Cl- adsorption, the electrodes showed a linear response across Cl- concentrations of 0.5-20 microM.     

Preparation and intercalation chemistry of magnesium-iron(III) layered double hydroxides containing exchangeable interlayer chloride and nitrate ions

Layered double hydroxides (LDHs) with Mg²⁺ and Fe³⁺ cations in the brucite-like layers and having chloride or nitrate ions in the interlayer region have been prepared and characterized by powder X-ray diffraction (PXRD), elemental analysis and thermal analysis. Thermal decomposition of the LDH-nitrate occurs in two steps, with loss of water followed by simultaneous dehydroxylation of the layers and loss of NO_x/O₂ arising from the nitrate anions. Thermal decomposition of the LDH-chloride involves an additional step, with chloride ions becoming grafted to the layers, prior to loss of HCl. The interlayer anions may be readily replaced by sulfate, thiosulfate, tartrate and vinylbenzenesulfonate ions suggesting that these materials may be useful precursors to Mg-Fe(III) LDHs intercalated with a variety of inorganic and organic anions.     

Kinetic and chemical characterization of thermal decomposition of dicumylperoxide in cumene

Dicumylperoxide (DCP) is one of the most used peroxides in the polymer industry. It has been reported that its thermal decomposition can result in runaway phenomena and thermal explosions with significant economic losses and injuries to people. In the present paper thermal behaviour of dicumylperoxide in cumene was investigated over the temperature range of 393-433 K under aerated and de-aerated conditions. The results indicated that when oxygen was present, the decomposition rate did not follow a simple pseudo-first order kinetic as previously reported in literature. A satisfactory fit of the experimental data was, in this case, achieved by means of kinetic expression derived under the assumption of an autocatalytic scheme of reaction. The reaction rate was, on the contrary, correctly described by a pseudo-first order kinetic in absence of oxygen. Under both aerated and de-aerated conditions, chemical analysis showed that the decomposition mainly resulted in the formation of acetophenone and dimethylphenylcarbinol with minor occurrence of 2,3-dimethyl-2,3-diphenylbutane. The formation of methane and ethane was also invariably observed while the appearance of cumylhydroperoxide as a reaction intermediate was detected under only aerated conditions. Therefore, two reaction schemes were proposed to explain system behaviour in the presence of oxygen and after its purging.     

硝酸、硫酸对三硝基均苯三酚热分解特性的影响

三硝基均苯三酚（TNPG）在硝化过程中不可避免地会接触到酸根离子。为了探究硝酸、硫酸作用下TNPG的热分解特性,采用差示扫描量热仪（DSC）对合适酸含量的样品在不同升温速率条件下进行测试,并进行动力学分析与预测。DSC测试结果表明,TNPG的起始分解温度为198.35 ℃,硝酸和硫酸都能促进其热分解过程,随着酸含量的增加,起始分解温度降低。无模型法计算得到TNPG的活化能变化范围为97~103 kJ/mol,而酸作用下的TNPG较不稳定,活化能为20~94 kJ/mol（硝酸作用）和135~224 kJ/mol(硫酸作用)。等温预测结果说明,各样品具有自催化分解特性;绝热预测结果表明,每个样品的T_D24分别为137.6 ℃（TNPG）、111.3 ℃（硝酸作用）和140.4 ℃（硫酸作用）。若在合成过程中发生热失控,采取控制措施的时间余量较大;需要将物质在阴凉、干燥、无酸根离子的环境中储存,避免外部火灾的发生。     

共存离子对Bentonite/LS-g-AM-co-MAH吸附Pb~(2+)的影响

采用自制膨润土/木质素磺酸钠接枝丙烯酰胺-马来酸酐复合吸附树脂(Bentonite/LS-g-AM-co-MAH),研究了外加电解质中竞争阳离子与共存阴离子对Bentonite/LS-g-AM-co-MAH吸附Pb~(2+)的影响。结果表明:竞争阳离子Li~+、Na~+、K~+、Mg~(2+)、Ca~(2+)、Ni ~(2+)、Co~(2+)、Zn~(2+)、Cd~(2+)和Cu~(2+)抑制Pb~(2+)的吸附,抑制作用顺序为Cu~(2+)Cd~(2+)Zn~(2+)Co~(2+)Ni ~(2+)Ca~(2+)Mg~(2+)K~+Na~+Li~+;Fe~(3+)和Al~(3+)在pH=2.0~3.0时抑制Pb~(2+)的吸附,在pH=4.0~6.0时促进Pb~(2+)的吸附,两者的影响顺序为Fe~(3+)Al~(3+)。共存阴离子NO_3~-、Cl~-和Br~-抑制Pb~(2+)的吸附,抑制作用顺序为Br~-Cl~-NO_3~-;SO_4~(2-)和PO_4~(3-)有利于去除Pb~(2+),两者影响基本相同。     

离子色谱法测定饮用水中常见阴离子

本文主要介绍离子色谱法检测饮用水中常见阴离子的方法。本方法采用瑞士万通的761型离子色谱仪。分离柱为METROSEPAnionDual2,淋洗液为2.0mmol/LNaHCO3和1.3mmol/LNa2CO3抑制液为20mmol/LH2SO4在测定范围内,F-、Cl-、NO2-、NO32-;-SO42-的峰面积和质量浓度呈线性关系,相关系数均大于0.999。回收率F-为101.5%,CL-O101.6%,NO2-为108.0%.NO32-为97.7%,SO42-为103.3%。相对标准偏差在0.7%-4.3%之间。     

室内外细粒子PM_(2.5)和总悬浮颗粒物污染水平的对比研究

为了解室内外空气颗粒物PM2.5和总悬浮颗粒物(TSP)的污染状况,自2008年3月24日～4月3日在西安交通大学学生办公室、教师办公室、化学实验室和室外同时采集PM2.5和TSP样品,对其质量浓度及无机水溶性离子组分(Na+、NH4+、K+、Mg2+、Ca2+、Cl-、NO3-和SO42-)进行了分析。结果表明,室内外PM2.5和TSP浓度都远远高于美国空气质量标准规定的35μg/m3。室内外颗粒物浓度具有相同的变化趋势,且室内总体上低于室外。室内PM2.5在TSP中所占比例在65%～85%,室外在40%左右。室内外TSP和PM2.5中二次污染离子SO42-、NO3-和NH4+占总离子质量的50%以上,主要富集在细颗粒中。NH4+、K+和Cl-在总离子中的比例均为室内大于室外,PM2.5中大于TSP。Ca2+、Mg2+主要富集在粗颗粒上,室外含量远远高于室内。     

A系列树脂对金属离子的吸附性能及吸附机理

对前文合成的Ａ系列氮杂聚合物冠醚树脂（多胺交联乙二醇双缩水甘油醚）进行了元素分析、差热分析及红外光谱表征。研究了该系列树脂对Ｃｕ２＋、Ｎｉ２＋、Ｃｏ２＋的静态吸附动力学、等温吸附过程,并根据元素分析,ｐＨ值对吸附性能的影响及吸附前后红外光谱分析结果对其吸附机理作了初步探讨。实验结果表明,Ａ系列树脂具有热稳定性高、吸附速率快、吸附容量大等特点。可广泛应用于脱除污水中的过渡金属离子并可根据其对不同离子的吸附性能差异对金属离子进行有效分离。     

Influence of inorganic ions on MTBE degradation by Fenton's reagent

The effect of selected inorganic anions on the effectiveness of the Fenton advanced oxidative treatment of waters contaminated with methyl t-butyl ether (MTBE) was examined. With respect to the chloride or phosphate ions used, inhibition of oxidation was clearly in evidence, whereas addition of sulfates or perchlorates influenced these rates to a much smaller extent. Anions suppress MTBE decomposition in the following sequence: ClO4- 相似文献