煤燃烧特性热重试验研究及动力学分析

为了研究煤样挥发分、氧化程度及燃烧时氧气浓度对煤样燃烧难易程度的影响,设计并完成有关相应影响因素的3组热重分析(TGA)试验。采用等转化率法和特征温度分析法进行数据分析。结果表明:特征温度法显示煤燃烧时高挥发分煤样的特征温度较其他煤样低;等转化率法显示高挥发分煤样的各转化率下活化能也均低于其他煤样。2种方法的分析结果一致,都显示挥发分含量高的煤样较其他煤样易于燃烧。分析不同氧化程度下的煤样燃烧热重曲线和不同燃烧时氧浓度情况下的热重曲线得出,氧化程度越高,燃烧时氧浓度越高,煤越早开始燃烧,燃烧速度也越快。     

建筑装璜中几种常用板材热解特性及动力学研究

对建筑装璜中几种常用板材变工况的热解行为进行了热重分析（TG）和差分热重分析（DTG）研究。通过对TG和DTG曲线的分析,深入研究了影响样品热解过程的几个重要因素：升温速率、样品粒径和试样量对热解过程的影响,通过对十种模型的比较,发现热解过程符合两阶段一级反应模型。并得出了各阶段的动力学参数、表观活化能和频率因子。     

四苯基双酚A二磷酸酯及复配纳米SiO2体系阻燃PC/ABS的热动力学分析

利用热分析仪对四苯基双酚A二磷酸酯(BDP)及BDP/纳米SiO2阻燃PC/ABS进行了TG分析,研究了BDP及其复配体系阻燃PC/ABS的降解过程,在动力学理论模型基础上,求出了阻燃PC/ABS的热力学参数-活化能.实验结果表明,与未阻燃PC/ABS相比,阻燃PC/ABS在600℃残炭率增加,15%BDP阻燃PC/ABS的残炭率由未阻燃的16.55%增加到22.16%,15%BDP/7%SiO2阻燃PC/ABS的残炭率增加到25.24%;BDP及其复配体系阻燃PC/ABS活化能显著提高,15%BDP阻燃PC/ABS的活化能由未阻燃的91.55kJ·mol-1提高到143.83kJ·mol-1,15%BDP/7%SiO2阻燃PC/ABS的活化能提高到254.08kJ·mol-1,体系耐热性能好,阻燃效果明显,复配体系阻燃效果进一步提高.     

景区典型树种的热解特性及动力学研究

为了研究山林或景区中不同植物的热稳定性,选取了景区种植数量较多的6种典型树种:女贞、枇杷、竹子、松树、柏树和法桐的枝干和叶作为样品。借助同步热分析仪,在温升速率20℃/min的条件下,对未经干燥处理的样品进行热解特性及热解反应动力学研究。通过TG、DTG以及DSC曲线分析各样品的热解过程,并采用分阶段一级反应动力学模型Coats-Redfern法求得相应参数。研究结果表明:所取样品的热解过程都出现4个明显的热解阶段,即脱水阶段、综纤维素热解阶段、木质素热分解阶段、炭化阶段。根据6个树种的主要热解阶段和动力学分析,6种树种的热稳定性从低到高顺序依次为竹子、女贞、枇杷、法桐、柏树、松树。     

四苯基双酚A二磷酸酯及复配体系阻燃环氧树脂的热动力学分析

采用热分析仪对四苯基双酚A二磷酸酯(BDP)及复配APP体系阻燃环氧树脂(EP)进行TG分析,研究BDP及其复配体系阻燃EP降解的过程,并在动力学理论模型基础上计算阻燃EP的活化能.结果表明,与未阻燃EP相比,阻燃EP在600 ℃时残炭率增加,15% BDP阻燃EP的残炭率由未阻燃的20.41%增加到28.06%,15% BDP+9% APP阻燃EP的残炭率增加到34.78%;BDP及其复配体系阻燃EP的活化能显著提高,15% BDP阻燃EP的活化能由未阻燃的80.39 kJ/mol提高到141.06 kJ/mol,15% BDP+9% APP阻燃EP的活化能提高到199.68 kJ/mol.研究表明,阻燃EP体系耐热性能好,阻燃效果明显,且复配体系阻燃效果进一步提高.     

基于升温速率的生物质三组分热解特性研究及动力学比较

为了研究升温速率对生物质三组分的热解特性影响,利用同步热分析-质谱联用仪(Thermogravimetry/Differential Scanning Calorimetry-Mass Spectrum, TG/DSC-MS)对不同升温速率(μ=1℃/min、5℃/min、10℃/min、20℃/min)下的热解试验进行分析,并采用Coats-Redfern法、Doyle法和分布活化能模型(Distribution of Activation Energy Model, DAEM)法对热解动力学参数进行计算与比较。结果显示：1)随升温速率增大,三组分生物炭产率减小,热解气和热解油产率增大。2)随升温速率增大,气体产物最大析出速率增大。其中,当升温速率为1℃/min时,气体产物析出速率变化不大。3)随升温速率增大,三组分热解失重率变化不大。4)随升温速率增大,DTG(Derivative Thermogravimetry)曲线最大失重峰右移,最大热解失重速率减小。5)随升温速率增大,纤维素DSC曲线最大吸热峰右移,峰值增大,吸热峰面积增大。此外,半纤维素和木质素最大放热峰右移,峰值增大,...     

酸碱度对玉米秸秆酶解液光合生物产氢动力学的影响

主要研究p H值对玉米秸秆酶解液光合生物产氢动力学的影响,以生物量干重为指标研究p H值对光合产氢细菌生长的影响,以产氢速率和产氢量为指标研究p H值对光合细菌产氢的影响。利用Logistic模型和MMF模型分别对光合细菌生长和玉米秸秆酶解液光合生物产氢进行了回归模拟,提出了p H值对光合细菌生长动力学和玉米秸秆酶解液产氢动力学的影响规律。结果表明:p H值对光合细菌生长及产氢过程都有显著影响,随碱性增强,光合细菌生物量逐渐增大,当p H值为8时,光合细菌生物量达到最大,为0.543 7 g/L,最佳接种时间为84~96 h;光合细菌产氢量随p H值增加同样呈现先递增再递减的趋势,当p H值为6时,产氢速率和产氢量达到最大,分别为29.72 m L/(L·h)、168.96 m L。     

两种含水率水稻堆垛的着火与蔓延燃烧特性实验研究

粮食安全事关国计民生,近年来粮仓火灾多发,对于粮食火灾安全的基础性研究,显得愈加迫切。基于自主设计的贯穿气流条件下的散粒堆垛引燃与蔓延燃烧特性研究实验平台,针对两种含水率水稻,在不同贯穿气流条件下,开展了引燃与内部蔓延燃烧特性研究。结果表明,水稻含水率对其燃烧特性具有重要影响,即,对于13%含水率水稻,采用高温电热细棒插入堆垛内进行引燃45 min,并未引燃;然而,对于3%含水率水稻,仅引燃4 min,堆垛即形成迅速剧烈蔓延燃烧,中心区域燃烧温度高达1 200℃,最大蔓延速度约0.8 cm/s,引燃前的最大升温速率约200℃/min。此外,结果还表明,贯穿气流条件下,远离中心区域的四周水稻升温较慢且剩余一些最终未引燃,水稻堆垛内部主要呈向下且不断扩大的蔓延燃烧特征。最后,13%含水率水稻被灼热引火源作用结束后形成的碳化圈大小表明,机械通风气调作用对于灼热源的引燃作用具有一定的抑制作用。     

硬木地板材料和棉花秆的变氧浓度热解燃烧表观动力学的实验研究

本文采用TG-FTIR分析方法深入研究了火场中硬木地板材料和棉花秆变氧浓度燃烧过程,深入分析了氧浓度对纤维物质燃烧表观热失重影响;通过大量的动力学参数计算得出了可燃物的表观活化能与实际氧浓度成线性关系;分析了氧浓度对木材燃烧气体产物的影响,并探索了氧浓度影响热解和燃烧的机理。     

基于多小波变换和奇异值分解的声发射信号降噪方法

为了提高起重机故障诊断的准确率,本文将多小波变换(MWT)和奇异值分解(SVD)进行结合,提出了一个回转支承声发射信号降噪新方法.本文采用MWT对声发射信号进行多层次分解,并用SVD算法进行处理,提高了声发射信号的可识别度.最后,采用仿真信号和真实回转支承声发射信号进行测试,结果表明本文所用方法可以有效地去除信号中的噪...     

Thermal decomposition mechanism of 65% lysine sulfate powder and its thermal stability based on thermal analysis

Lysine is widely used in the fields of food, medicine and feed, which generally appears in the form of lysine sulfate or lysine hydrochloride dust because of the high instability of the free L-lysine. The L-lysine Sulfate is in high risk of decomposition, spontaneous ignition and even the dust explosion, because the control temperature in its production process is high up to 90 °C. Thus, the thermal behaviors and its thermal stability of 65% lysine sulfate are experimentally explored in Air and Nitrogen using the simultaneous TG-DSC measurements. Results show: (1) the decomposition of 65% lysine sulfate can be divided into three stages both in the atmospheres of air and nitrogen, and most of the weight loss occurred in the first two stages, which are related with the decarboxylation and deamination process. (2) The effects of atmosphere on the decomposition of 65% lysine sulfate mainly occur at the third stage. In this stage, the weight loss in nitrogen is only 14.2%, which is much lower than that in air (34.3%), which is related to the oxidative degradation at high temperature. Besides, the active energy is slightly increased in nitrogen compared to that in air. (3) The initial temperatures of the decomposition of the 65% lysine sulfate are 145 °C and 155 °C, for the air and nitrogen atmosphere, respectively, which are much lower than that (260 °C) of the pure lysine.     

Explosibility and thermal decomposition behavior of nitrile rubber dust in industrial processes

The formation of nitrile rubber (NBR) dust clouds during processing can lead to a potential dust explosion under certain conditions. However, the potential explosion hazard posed by NBR dust is usually overlooked by enterprises. In this paper, the explosive properties of NBR dust are investigated using a Hartmann tube, a G-G furnace, and a 20 L explosion chamber. The results showed that NBR dust could cause explosions severe enough to be classified as St-1. In addition, the thermal decomposition behavior of NBR dust under combustion conditions was investigated using a combination of thermogravimetric analysis coupled with Fourier transform infrared spectroscopy (TGA-FTIR). The results indicated that in the early stage, NBR dust mainly undergoes self-thermal decomposition to produce a large amount of combustible gas, which combines with oxygen to form a mixed gas and cause a gas-phase explosion. In addition, the participation of oxygen could lower the initial temperature of NBR dust thermal decomposition. As a result, decomposition occurred more quickly and a large amount of combustible gas was produced, thus expanding the range of dust explosions. Furthermore, these combustible gases exhibit varying degrees of toxicity, seriously affecting the life and health safety of relevant personnel. This work provides theoretical guidance for the development of safe procedures to prevent and address problems during NBR dust processing in enterprises.     

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。     

Relationship between electric spark sensitivity and activation energy of the thermal decomposition of nitramines for safety measures in industrial processes

This study presents a new simple correlation between electric spark sensitivity of nitramines and their activation energies of thermolysis, which are important for safety measures in industrial processes. The new correlation can help to elucidate the mechanism of initiation of energetic materials by electric spark. It can be used to predict the magnitude of electric spark sensitivity of new nitramines, which is difficult to measure. The methodology assumes that electric spark sensitivity of a nitramine with general formula C_aH_bN_cO_d can be expressed as a function of its activation energy of thermal decomposition as well as optimized elemental composition and the contribution of specific molecular structural parameters. The new correlation has the root mean square and the average deviations of 1.37 and 1.09 J, respectively, for 21 nitramines with different molecular structures. The proposed new method is also tested for 16 nitramines so that there is no experimental data of electrostatic sensitivity for them.     

Theoretical and experimental studies on the thermal decomposition of 1-butyl-3-methylimidazolium dibutyl phosphate

Ionic liquid, an organic molten salt, has efficient flame-retardant performance. Few researchers have attempted to study its flame-retardant mechanism. Moreover, thermal stability and pyrolysis products have a great impact on the flame retardancy. Therefore, this paper focused on the phosphate ionic liquid of 1-butyl-3-methylimidazolium dibutyl phosphate ([Bmim][DBP]) and analyzed its thermal decomposition products and characteristics. The major bond energies of [Bmim][DBP] were calculated using B3LYP/6–311++G(d,p)//M06–2X/6–311++G(d,p) level. The experimental results show that the pyrolysis products were as followed: alkane or alkene with a carbon chain length of 1–4; imidazole and its derivatives; esters. Furthermore, Gas chromatography-mass spectrometer and Fourier transform infrared spectrometer were utilized to measure the gaseous products and solid phase products of [Bmim][DBP], which were obtained during thermogravimetric analysis. The results of theoretical and experimental analysis were highly consistent. Finally, the possible flame-retardant mechanism of [Bmim][DBP] was proposed.     

敞开气氛中硝酸铵热分解过程危险特性的实验研究

利用差热分析仪分析和研究了敞开气氛中硝酸铵的热分解过程,通过在硝酸铵样品中加入酸性物质、KCl、有机物等各种杂质,研究硝酸铵热分解过程的影响因素。结果表明,在敞开气氛中,酸性物质和KCl对硝酸铵热分解过程具有催化作用,有机物会降低硝酸铵的热稳定性,研究结论可以为解决硝酸铵的生产、储存和运输过程中的安全问题提供重要参考。     

Explosibility,flammability and the thermal decomposition of Bisphenol A,the main component of epoxy resin

Bisphenol A is one of the basic compounds used in a synthesis of polycarbonates and epoxy resins. Its dust can create an explosive mixture with air under specific circumstances. Therefore, the main goal of this research was to determine explosion characteristics and flammability behaviour of this compound. The complete flammability characteristic requires the determination of the basic parameters of Bisphenol A under fire conditions including Heat Release Rate, speed of combustion, ability to ignite and the temperature of the decomposition range. To establish those parameters, a cone calorimeter was used. The explosion characteristics were tested in a 20-L spherical vessel. Minimum Ignition Energy was tested on MINOR II Apparatus which is a modified Hartman's Tube. In order to identify hazardous substances generated during a fire involving Bisphenol A, a simultaneous thermal analysis that combines thermogravimetry and differential scanning calorimetry was used. The substances obtained from the thermal degradation were analyzed by infrared spectroscope with Fourier transformation. Furthermore, the application of a Purser furnace and gas chromatography with mass spectrometry facilitated the identification of gaseous substances formed during the thermal degradation of Bisphenol A samples.     

两种有机锌络合物处理棉花的霉变及热解行为研究

棉花是纺织业的重要原料,是人民群众生活不可或缺的必需品,同时也是我国进出口重要的商品。研究如何安全有效地进行棉花的储备具有十分重要的现实意义。棉纤维本身含有脂肪、蜡质和果胶等适合微生物生长繁殖的营养物质。在棉花储备中,高的回潮率会加速微生物的繁殖,进而产生热量。热量的累积会引起温度升高以及棉花霉变,不利于棉花的安全有效储存。因此,通过静电吸附法将安全无毒的有机锌络合物附着在棉纤维表面,研究表明,相同条件下,处理棉的霉变状况明显得到抑制。加速发霉条件下,未处理棉的相对于白纸的平均色差值为28.10,而双乙酸锌以及苯甲酸锌防霉处理棉的色差值分别为5.16和5.86,下降了81.6%和79.1%。自然发霉条件下,双乙酸锌以及苯甲酸锌防霉处理棉的色差值分别下降了53.8%和50.7%。同时研究了纯棉以及处理棉氮气下的热分解动力学,相比于未处理棉,双乙酸锌防霉处理后活化能下降了15.8%,而苯甲酸锌防霉处理后活化能下降了10.9%。此外,利用实时红外和热重红外联用技术得到了样品在热解过程中固相以及气相的裂解产物的红外谱图,发现防霉处理能一定程度上抑制棉花热解。     

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.