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.     

Evaluation of Poly(ethylene-terephthalate) Products of Chemical Recycling by Differential Scanning Calorimetry

Poly (ethylene-terephthalate), (PET) bottles waste was chemically recycled by glycolysis and hydrolysis. The depolymerization processes were carried out in different time intervals from 5 to 360 min, in two different molar ratios of PET/EG, 1:5 and 1:18 and at different temperatures. The PET glycolysis leads to formation of bis(2-hydroxy-ethyl)terephthalate (BHET) monomer and PET oligomers with hydroxyl and carboxyl end groups while PET hydrolysis is followed by formation of monomers terephthalic acid (TPA) and ethylene glycol (EG). Fractions of monomers and oligomers were further characterized by FTIR spectroscopy and by differential scanning calorimetry (DSC). The results show that DSC is successful method to describe the different structures of oligomers formed during chemical recycling of PET.     

Safety and kinetic parameters analysis for 1,1,-Di(tert-butylperoxy) cyclohexane mixed with monoammonium phosphate

Runaway reactions by organic peroxides have occurred throughout the world. In this study, we used 1,1,-Di(tert-butylperoxy) cyclohexane (CH) 70 mass% as the main material, which was extensively employed as initiator for styrene in polymerization. Fire extinguishers are the first fire-fighting apparatus when fires occur. If a fire extinguisher has sat idle for a long time, which would cause the extinguishing agent to damp, it cannot achieve the desired effect and be properly handled at the start of the accident, thereby causing more casualties and property losses. CH 70 mass% was employed to mixed with monoammonium phosphate (MAP) for understanding the phenomenon by applying differential scanning calorimetry (DSC). Safety parameters also were carried out for more deeply understanding the basic characteristics for preventing an accident from occurring, in terms of applying CH 70 mass% as the initiator in the manufacturing process.     

混酸中甲苯半间歇硝化过程的危险性研究

为了解甲苯在混酸中硝化的危险性,用差示扫描量热法(DSC)测试甲苯、混酸及一硝基甲苯的热分解情况,用反应量热仪(RC1e)研究搅拌速度、温度及硝酸过用率3因素对目的反应的影响。结果表明,混酸分解温度最低,而当目的反应的3因素出现异常,以及反应过程中发生冷却失效时,均可导致硝化反应体系不稳定,此时若不停止加料,并采取措施,易引起混酸的分解,进一步可引起一硝基甲苯的分解,导致严重后果。     

2,4-二硝基苯酚钠非等温DSC热分解动力学研究

首先用同步热分析仪（STA）测定了一定温度区间内2,4-二硝基酚钠的比热容,利用Origin8.0软件回归比热容随温度变化的方程式,拟合系数为0.913 6,标准偏差为0.005 9。然后分别在空气和氮气气氛下对2,4-二硝基酚钠进行了TG/DSC测试,并与单硝基酚钠（邻、间、对位）的热分解性能进行了比较。通过在氮气气氛不同升温速率下的测试,用Kissinger法得到2,4-二硝基酚钠热分解反应的表观活化能、指前因子等动力学参数。研究表明:2,4-二硝基酚钠在300℃以下具有良好的热稳定性,Kissinger法得到的2,4-二硝基酚钠表观活化能为244.8 kJ/mol,指前因子为2.5×10¹⁸s^-1。     

二氧化硅对膨胀型阻燃聚乙烯的性能影响研究

利用锥形量热仪(CONE)、裂解气相色谱仪(PyGC)、示差扫描量热仪(DSC)等先进的分析测试手段,研究了二氧化硅对膨胀型阻燃聚乙烯阻燃性能的影响、各阻燃剂之间的协同性以及阻燃机理。实验结果显示,阻燃剂的加入可延缓PE的降解过程,降低材料的热释放速率,降低基材在升温过程中的放热量,使基材具有良好的阻燃性;SiO2的适量加入可改善膨胀碳层的耐热性,当SiO2的添加量为6％时,协同阻燃效果最佳。     

Sterilization affects soil organic matter chemistry and bioaccumulation of spiked p,p′-DDE and anthracene by earthworms

Laboratory experiments were conducted to assess the effects of soil sterilization on the bioavailability of spiked p,p′-DDE and anthracene to the earthworms Eisenia fetida and Lumbricus terrestris. Physical and chemical changes to soil organic matter (SOM) induced by sterilization were also studied. Uptake of both compounds added after soil was autoclaved or gamma irradiated increased for E. fetida. Sterilization had no effect on bioaccumulation of p,p′-DDE by L. terrestris, and anthracene uptake increased only in gamma-irradiated soils. Analyses by FT-IR and DSC indicate sterilization alters SOM chemistry and may reduce pollutant sorption. Chemical changes to SOM were tentatively linked to changes in bioaccumulation, although the effects were compound and species specific. Artifacts produced by sterilization could lead to inaccurate risk assessments of contaminated sites if assumptions derived from studies carried out in sterilized soil are used. Ultimately, knowledge of SOM chemistry could aid predictions of bioaccumulation of organic pollutants.     

石墨烯对RDX机械感度及爆轰性能的影响

炸药添加剂对改善单质炸药安全与能量特性有重要作用。为研究纳米微颗粒石墨烯(Gr)对黑索今(RDX)热性能、机械感度及爆轰性能的影响,设计不同比例含量的Gr/RDX混合药剂配方,并对其进行差热、撞击感度、摩擦感度、爆速及钢凹深度的测试分析。结果表明:与纯RDX相比,Gr/RDX混合药剂DSC（差示扫描量热）曲线分解峰宽变窄、峰形更尖锐,Gr加速RDX的放热过程;Gr/RDX混合药剂撞击感度与摩擦感度随Gr比例含量的增加呈先降低后升高的趋势,少量Gr可使RDX变得钝感,含量增加时,敏化作用逐渐表现出来;Gr/RDX混合药剂爆速与钢凹深度随Gr比例含量的增加而降低;Gr含量为1%时可显著降低RDX的机械感度,而能量基本不衰减。Gr可作为RDX功能添加剂,在确保能量输出的同时,可降低机械感度、提高安全性。     

Reactive chemical hazards of diazonium salts

Many diazonium salts are thermally unstable and sensitive to friction and shock. Most diazonium salts are known for their violent decomposition hazard in the solid state. There are many industrial and laboratory incidents caused by this group of chemicals. For safety purposes, the hazards related to the preparation and the handling of diazonium salts are discussed. Twelve cardinal rules are provided:1. Use only a stoichiometric amount of sodium nitrite when generating diazonium salts, avoiding excess sodium nitrite.2. Check for the excess of nitrous acid by starch–potassium iodide papers and neutralize it.3. Minimize the presence of nitrous acid by combining amine and acid first, then subsequently adding the sodium nitrite.4. Keep the temperature below 5 °C.5. Always vent the gases generated.6. Determine the thermal stability of diazonium compounds in your system.7. Understand the explosive properties of diazonium salts. If unknown, always assume they are explosive.8. Never allow the undesired precipitation of diazonium salts out of solution.9. Analyze the residual diazo compounds in the final product, especially for new process conditions.10. Quench the remaining diazonium salts before any further treatments.11. Isolate no more than 0.75 mmol of explosive diazonium salts at one time; also consider the addition of an inert material to stabilize the diazonium salts.12. Use a plastic spatula when handling the solid. The dried powder should not be “scratched” with a metal spatula or ground finely.An example of a testing strategy and data interpretation is provided for a process which has multiple steps and two diazonium compounds. Differential Scanning Calorimetry (DSC) and Heat of Mixing calorimetry (HOM) successfully serve as efficient tests to screen thermal stability and gas generation, identifying the candidates for advanced tests.