4种硝酸酯热安定性的绝热试验研究

利用绝热加速量热仪(ARC)对硝酸正丙酯(NPN)、硝酸异丙酯(IPN)、太根(TEGDN)、敌根(DEGDN)4种硝酸酯的热稳定性进行了绝热试验研究,得到绝热放热曲线和热分解特征参数。分析了4种物质分解过程的特点,对测试结果进行了修正。计算得到动力学参数和自加速分解温度SADT,以此作为评估热安定性的判据。结果表明,4种硝酸酯在外界热作用下容易发生分解,反应速度较快,伴随明显的热效应和压力效应。4种硝酸酯的热安定性由好到差排序为:IPN、NPN、TEGDN、DEGDN。     

膨胀聚苯乙烯热分解动力学分析和寿命预测

针对既有聚苯乙烯泡沫类外墙外保温系统的防火问题,在空气和氮气气氛下对非阻燃和阻燃型膨胀聚苯乙烯泡沫进行了热重分析。样品由10℃/min、20℃/min、40℃/min和50℃/min四个升温速率从室温加热至800℃。热分解动力学参数由Flynn-Wall-Ozawa(FWO)等转化率方法和多参数非线性回归方法(multivariate non-linear re-gression method)计算,结果表明六溴环十二烷(HBCD)阻燃剂可一定程度上提高EPS的热稳定性。EPS在空气和氮气气氛下热解可认为是单步反应。非阻燃聚苯乙烯泡沫在空气和氮气气氛下的热解过程可由自催化n阶反应机理描述。阻燃EPS在空气气氛下的热解机理为自催化n阶反应,在氮气气氛下则为n阶反应机理。基于动力学参数和反应机理,对聚苯乙烯泡沫在不同温度下的寿命进行了预测。     

红树植物凋落叶分解对土壤可溶性有机质的影响

研究红树林湿地土壤可溶性有机质（DOM）的来源、性质及其归宿对于揭示 DOM 在红树林湿地生物地球化学循环中的作用具有重要意义。采集了木榄（Bruguiera gymnoihiza）、秋茄（Kandelia candel）和桐花树（Aegiceras corniculatum）3种红树植物的新近落叶进行室内48 d分解实验,探讨了凋落叶分解过程对土壤可溶性有机碳（DOC）和可溶性总氮（TDN）含量、C/N比（DOC/TDN）及紫外-可见（UV-Vis）光谱特征（A280、A240/A420和A250/A365比值）的影响。在48 d分解期间,3种红树植物凋落叶的输入均明显增加了土壤DOC的含量,其变化在分解第6 d最为显著,各凋落叶添加组比对照组平均增加了149%（秋茄）~196%（桐花树）,随后各凋落叶添加组土壤DOC含量呈下降趋势。与土壤DOC的变化不同,凋落叶输入后土壤TDN的变化与对照组的差异不明显,但木榄和桐花树添加组的C/N比在分解初期（第6天）显著高于对照组（P<0.05）。凋落叶的输入亦在不同程度上增大了土壤DOM的A280值,降低了DOM的A240/A420和A250/A365比值。与土壤DOC的变化相似,凋落叶输入使DOM的UV-Vis光谱特征在分解初期（第6天）的变化最明显,其中桐花树凋落叶的影响最大,秋茄凋落叶的影响最小。结果表明：凋落叶输入使培养初期土壤DOM的含量和性质发生明显改变,DOM中大分子及芳香类组分增多、团聚化程度增加,DOM 的生物可降解性变小。然而,随着分解的进行,不同凋落叶处理组之间土壤DOM的变化差异性逐渐缩小,并在分解后期与对照组趋近。     

Gliding arc plasma processing for decomposition of chloroform

The decomposition of chloroform (CHCl₃) diluted in air was studied. The experiment was carried out by using a gliding arc plasma. Different values of initial concentrations of chloroform, total gas flow rates, and input power frequencies have been used to investigate this effects on the conversion reaction products both qualitatively and quantitatively. Experimental results indicate that the maximum conversion of chloroform was 97% at a total gas flow rate of 180?L?h^?1 containing 1% chloroform. Using air as carrier gas, decomposition of CHCl₃ produces CCl₄, CO₂, CO, and Cl₂ as the main products. Small amounts of HCl and COCl₂ are also detected. Liquid products were also produced.     

Analysis and decomposition of condensed tannins in tree leaves

The decomposition of leaf litter is controlled by several factors. One factor that may play an important role is the content of condensed tannins (proanthocyanidins). Here we designed a combined method to isolate proanthocyanidins from leaf extracts, to convert them to anthocyanidins, and to quantify individual anthocyanidins exactly with a new, simple, but sensitive high-performance liquid chromatography method. We used this method to show composition of proanthocyanidins and to monitor degradation of proanthocyanidins and individual constituents in leaf litter in an aquatic environment over time. Despite the rapid decrease in the initial concentrations, a fraction of the proanthocyanidins remained detectable for several weeks.     

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.     

Study of lignocellulosic biomass ignition properties estimation from thermogravimetric analysis

In the last decade, the use of renewable resources has increased significantly in order to reduce the energetic dependence on fossil fuels, as they have an important contribution to the global warning and greenhouse gasses effect. Because of that, research on biofuels has been increased in the last years as its characteristics of use match those of the conventional fuel's: solid biomass can be used instead of coals, and biodiesel could replace diesel. Research on solid biomass ignition properties has been considerably developed because of the amount of industrial accidents related to the treatment and use of solid biomass (self-ignition, dust explosions, etc.). On the other hand, thermogravimetric analysis (TGA) is becoming and important characterization technique as it can be used to determine a wide spectrum of properties, such as kinetics, composition, proximate analysis, etc. This research aims to combine thermal analysis and ignition properties, by using the TGA to obtain the elemental composition of lignocellulosic biomass and compare those results to Minimum Ignition Energy (MIE) values test output, so a relation between composition and MIE can be found.To achieve this aim, biomass samples from different origins have been used: oil palm wastes (empty fruit bunches, mesocarp fiber and palm kernel shell), agricultural wastes (straw chops) and forestry wastes (wood chips and wood powder). Also, raw materials and torrefied biomass were compared. The hemicellulose/cellulose ratio was calculated and compared to different flammability properties, finding out that the greater the ratio and the lower the onset temperature (temperature at which the pyrolysis reaction accelerates), the lower was the minimum ignition energy. From this basis it was possible to define “tendency areas” that grouped the samples whose MIE values were similar. Three tendency areas were found: high minimum ignition energy, medium minimum ignition energy, and low ignition energy.     

Thermal hazard and decomposition kinetics of 1-butyl-2,3-dimethylimidazolium nitrate via TGA/DSC and FTIR

1-Butyl-2,3-dimethylimidazolium nitrate ([Bmmim][NO₃]), a kind of versatile and novel ionic liquids, is widely applied in the modern petrochemical industry. Nevertheless, its thermal hazard safety data at high temperature or thermal disturbance conditions are currently unavailable. Therefore, this study aimed to characterize the thermal risk of [Bmmim][NO₃] through auto-ignition temperature measurements, flash point analysis, thermal gravimetric analysis/differential scanning calorimetry (TGA/DSC), TGA-Fourier transform infrared spectroscopy (TGA-FTIR) and thermal decomposition kinetics analysis. Additionally, [Bmmim][NO₃] was examined using isothermal thermogravimetric analysis at different temperatures (220, 230, 240, 250, 260 and 270 °C). The experimental results show that the flash point of [Bmmim][NO₃] is 305.70 ± 9.30 °C and the auto-ignition temperature is 341.00 ± 21.60 °C with an ignition delay time of 8.6 s. In addition, using the nitrogen atmosphere TGA data to calculate the activation energy according to the Friedman, Kissinger and Flynn-Wall-Ozawa methods, roughly the same results were obtained. Finally, TGA-FTIR results show that [Bmmim][NO₃] produced acetylene, butane, butanol and carbon dioxide during the thermal decomposition process. This study could provide data support and some guidance for the thermal hazard assessment and safety control of [Bmmim][NO₃] during its use and storage.     

Evaluation of thermal reaction for two azo compounds by using 20-L apparatus and calorimetry

Azo compounds are widely involved in the industrial processes of dyes, pigments, initiators, and blowing agents. Unfortunately, these compounds have a bivalent unstable –NN– composition, which can be readily broken when the ambient temperature is elevated. Self-accelerating decomposition might cause a runaway reaction and lead to a fire, explosion, or leakage when the cooling system fails or other events occur. This study investigated the explosion properties, thermal stability parameters, and thermal hazard and mechanism of 2,2′–azobisisobutyronitrile (AIBN) and 2,2′–azobis–2–methylbutyronitrile (AMBN). We used a 20-L apparatus, vent sizing package 2, synchronous thermal analysis, and differential scanning calorimetry under explosive, adiabatic, and dynamic conditions to acquire the explosive curves, thermal curves, and thermodynamic parameters of the substances. Moreover, the differential isoconversional method (Friedman method) and ASTM E698 equation were employed to obtain the apparent activation energy E_a. All the experimental results revealed that AIBN is more dangerous than AMBN. The E_a of AIBN was lower than that of AMBN. The results can be used to construct an azo compound thermal hazard database for use for searches and reference examples by industry and related research areas.     

发泡注浆法合成莫来石轻质耐火材料

以工业废弃物粉煤灰和当地粘土为主要原料,十二烷基苯磺酸钠为发泡剂,采用发泡注浆法制备轻质莫来石耐火材料,研究了烧结温度对耐火材料晶相的影响以及发泡剂的种类、添加量和浆料固含量对轻质耐火材料常温物理性能的影响。结果表明,适当的烧结温度可改善耐火材料的晶相,同时对制品的孔隙率也有一定影响。选择适宜的发泡剂及添加量,在一定的浆料固含量范围内,可以制备容重小,孔隙率高,导热系数小,机械强度适中的轻质耐火材料。