A comparative study on the autoxidation of dimethyl ether (DME) comparison with diethyl ether (DEE) and diisopropyl ether (DIPE)

The Japanese government is planning to introduce DME as a substituted energy for oil and LNG. Introduction of DME could contribute greatly to both the prevention of global warming and the formation of resource-recycling societies. In these circumstances, a safety assessment of DME is very important when DME is used on a large scale. There is a possibility that prolonged exposure in air induces autoxidation to produce explosive organic peroxides during transportation and storage of DME. Therefore, the reactivity of DME with oxygen and the mechanism of the autoxidation were investigated. Accelerating Rate Calorimetry (ARC) was used to evaluate the thermal stability of DME and DIPE, a known peroxide producers, under adiabatic and various atmospheric conditions. In ARC studies of DME under oxygen, exothermic decompositions were detected although its self-heating rate was low in comparison with DIPE. Oven storage tests were carried out and iodimetry was used to measure the concentration of peroxides produced from DME in comparison with DIPE and DEE. However, no products could be found for DME either by GC/MS or by iodimetry, while some evidence of autoxidation of both DEE and DIPE were obtained from these experiments.     

Carbon Molecular Sieving Membranes Derived from Lignin-Based Materials

Carbon molecular sieving membranes were prepared by pyrolysis of lignocresol derived from lignin by the phase-separation method. Lignocresol membranes formed by a dip process on a porous -alumina tubing were carbonized at 400–800°C under nitrogen atmosphere. The thickness of the membrane formed on the outer surface of the substrate was about 400 nm judging from SEM observation. Gas-evolving behavior of lignocresol was measured using thermogravimetry-mass spectrometry (TG-MS). The gaseous products evolved from lignocresol included a number of fragments with higher molecular weights; whereas those from phenolic resin are mainly due to phenol and methylphenol. These evolved pyrolysis fragments effectively contribute to micropore formation of carbonized lignocresol membranes. Gas permeation rates through the membrane decreased in the order of increasing kinetic molecular diameter of the penetrant gas, and the membrane behaved like a molecular sieve. The permeation properties were dependent on heating conditions, and a pyrolysis temperature of 600°C gave the best membrane performance. Gas selectivities of the membrane prepared at 600°C were 50, 8, 290, and 87 for CO₂/N₂, O₂/N₂, H₂/CH₄, and CO₂/CH₄ at 35°C, respectively.     

密闭压力容器小型循环试验结果

在联合国危险品运输试验和标准建议书(桔皮书)中,系列E涉及评价物质在密闭容器中对剧烈加热的热爆炸敏感性的标准。但是人们一直希望并致力于发展一种定量,可靠,重复性好的方法来评价物质的热爆炸敏感性。本文介绍了一种小型密闭压力容器循环试验的研究及其作为一种筛选试验向联合国提案的最新进展。实验结果表明,几种物质在不同实验室的重复性非常好,其(dP／dt)max平均偏差率在20％以内,表明该小型密闭压力容器作为评价物质热反应危险性的测试方法具有较高的可靠性。     

有机过氧化物热分解激烈度的危险性评价方法

采用小型密闭式压力容器试验(MCPVT)测定了有机过氧化物热分解产生的压力举动，根据压力(P)及其上升速度(dP/dt)考察了有机过氧化物热分解激烈度，并与压力容器试验(PVT)进行比较，寻找MCPVT与PVT之间的关系，给出了热分解激烈度的评价方法。实验结果表明，除热分解前即产生蒸发的物质外，MCPVT的最大压力上升速度(dP/dt)max与PVT的最小孔径(d)有良好的相关性。同时指出，对分解前产生蒸发的物质，不适合用PVT进行热分解激烈度的评价，应采用MCPVT进行评价。