现代城市的空气污染与防治

随着现代工业的发展,人为造成排入大气中的污染物为数甚多,其中危险最大的有粉尘、硫氧化物、氮化物、一氧化碳等.1.粉尘粉尘主要来自燃料燃烧时产生的烟尘和工矿企业固体粉碎加工中所造成的粉尘.发生源及特征的示踪元素如下:汽车(Ca)、水泥制造(Ca)、煤的燃烧及焦碳制造(Al)、石油燃烧(V)、钢铁冶炼排放物(Mn)、土壤(Se)、海盐(Na).具有上述元素的粉尘对人体健康危害很大,会刺激人的呼吸系统,引起支气管炎、哮喘、肺气肿甚至肺癌等疾病.粉尘由于比表面积大,可吸附其它物质,从而为SO_2、NO这类污染物进一步转化成SO_3、NO_2提供催化作用的条件,更增加了它的危害性.     

通风条件对热塑性材料燃烧行为影响的试验研究

热塑性材料燃烧过程中,固体壁面火和液体油池火同时存在且相互影响.为了研究通风条件对受限空间内热塑性材料熔融流动燃烧行为的影响,选择5 mm厚的聚丙烯板材作为研究对象,设置了6种不同的通风条件,在ISO 9705标准燃烧室内,进行了一系列的大尺寸燃烧试验.试验过程中测量了热释放速率、CO体积分数以及温度场等火灾动力学参数.考虑到通风口宽度变化与高度变化的区别,引入了通风口位置高度的无量纲因子.结果表明,通风条件对热塑性材料的火灾规模有一定影响,并且通风口高度变化的影响比宽度变化的影响更显著.燃烧过程中,热释放速率峰值与修正后的通风因子呈线性关系.     

固体推进剂在压延中燃烧的预防和灭火研究

固体推进剂的组分中既有氧化剂又有燃烧剂,在没有外界氧气的情况下,也能发生燃烧爆炸事故。针对固体推进剂在压延生产中产生燃烧的主要原因,研究了水分和温度对固体推进剂热点形成的影响,提出了防火安全技术措施。针对部分火炸药企业的消防设施不能有效扑灭固体推进剂火灾和阻止燃爆事故的情况,通过对固体推进剂燃烧灭火机理的分析,采用选择不同的喷水压力、喷头孔径、喷头与火焰区的距离、预先燃烧时间等因素,对固体推进剂进行燃烧灭火效果的实验研究,提出了固体推进剂火灾的高速喷水灭火技术的思路和措施。     

静止环境中可燃固体表面火蔓延特性的实验研究

本文通过模拟实验方法研究静止环境下可燃固体材料表面的火蔓延特性,应用火焰结构显示技术连续观察和记录了固体可燃物表面火蔓延的火行为,并利用温度示踪技术连续考察和分析了固体可燃物表面的火蔓延过程,同时研究分析了燃烧试样类型对火蔓延速率的影响,所得结查物理上合理。     

城市生活垃圾中可降解有机物降解规律研究

通过室内降解试验,测定了城市生活垃圾中可降解有机物降解过程中的纤维素及木质素含量,提出采用C/L(纤维素含量/木质素含量)归一化后的相对变化量来表征城市生活垃圾(MSW)的生物降解程度.分析生物降解程度指标随时间的变化规律,结果表明,生物降解程度随着降解时间的增加呈倒"S"型变化,可降解有机物的降解过程是由慢到快再到慢的过程;Slogistic模型可以较好地模拟MSW的降解过程,而模型参数可以反映降解条件对降解速率的影响.Slogistic模型预测的填埋场稳定化时间与实测结果相符,表明了建议的表征降解程度指标及Slogistic模型的合理性与正确性.     

甘蔗渣纳晶纤维素酸法制备工艺的响应面法优化

为了获得甘蔗渣纳晶纤维素酸法制备的最佳工艺条件,基于Box-Behnken试验设计,选取硫酸质量分数、水解时间和水解温度为主要影响因素,采用响应面分析法优化了甘蔗渣纳晶纤维素酸水解制备工艺参数,并建立了二次多项式回归模型.方差分析表明,回归模型较好地反映了纳晶纤维素得率与硫酸质量分数、水解时间、水解温度的关系.甘蔗渣纳晶纤维素最佳的酸水解制备工艺条件为:硫酸质量分数56％,水解时间180 min,水解温度38℃.该条件下纳晶纤维素的得率达到52.93％.酸法制备工艺的响应面优化试验显著提高了甘蔗渣纳晶纤维素的得率,降低了纳晶纤维素的制备成本.     

氧化铁粒径对固体推进剂火焰特征参数影响的试验研究

针对5-氨基四氮唑/硝酸锶固体推进剂在实际应用中存在的推进剂火焰偏大、容易在灭火装置喷口处形成外喷火焰的问题,选用了微米氧化铁和纳米氧化铁作为催化剂,分别从火焰形态、质量损失速率、热释放速率、无量纲火焰高度模型几个角度开展研究,对比了两种不同粒径的氧化铁对5-氨基四氮唑/硝酸锶固体推进剂燃烧火焰的优化效果。根据燃烧试验结果,发现不论是富氧燃烧还是贫氧燃烧,在降低推进剂燃烧时的火焰高度方面,微米氧化铁均明显优于纳米氧化铁;在提高质量损失速率方面,微米氧化铁的加速效果也要优于纳米氧化铁。基于传统的液态燃料油池火发展的火焰高度预测模型,将无量纲火焰高度与热释放速率的分析关系应用到固体推进剂燃烧领域,考虑使用无量纲火焰高度的分析方法,对固体推进剂燃烧过程中的火焰高度进行预测,建立了5-氨基四氮唑/硝酸锶固体推进剂的无量纲火焰高度模型,发现不含氧化铁和含有氧化铁的5-氨基四氮唑/硝酸锶固体推进剂燃烧时的火焰高度与热释放速率的n次方成正比,该无量纲拟合可以对固体推进剂火焰高度进行预测。最终,得出了微米氧化铁比纳米氧化铁更适合作为催化剂被用于5-氨基四氮唑/硝酸锶推进剂中,有利于提高固体推进式灭火装置的灭火效果。     

火蔓延及发展过程的计算机模拟

本文对火蔓延及发展过程进行了计算机模拟,建立了描述火焰在不结焦可燃物垂直表面向上蔓延过程的数学物理模型,其中考虑了有关的四个分过程,即(1)可燃物未燃部分的预热;(2)火蔓延或热解区前沿的确定;(3)可燃物的热解以及(4)挥发份燃烧放热。在分别建立描述这些分过程模型的基础上,构成了体现几何尺寸和其它有关因素影响的总括模型,其结果与PMMA竖板上的实验结果进行了对比。     

油田含油污泥掺煤资源化试验研究

为使含油污泥和煤混烧在实际工程中得到应用,实现含油污泥资源化,对含油污泥和煤进行工业分析、元素分析,并对含油污泥的重金属浸出液特性进行分析,同时研究了含油污泥的燃烧特性.结果表明,含油污泥燃烧过程主要分为2个阶段,其中第1阶段为脱水干燥和挥发分析出阶段,在差热分析曲线(DSC曲线)上存在1个吸热峰和1个放热峰,含油污泥减少质量可达75％;第2阶段为挥发分燃烧和固定碳燃烧阶段,在DSC曲线上有1个放热峰,含油污泥的总失重率为92.86％,充分实现了减量化.探讨了掺煤量、粒径和煤种等因素对型煤燃烧性能的影响,发现与含油污泥直接燃烧相比,污泥与大同煤按1∶4质量比混合制得的粒径为15 mm的污泥型小球在马弗炉中燃烧时,起燃时间早,燃烧时间较长,且火焰长度适中稳定,黑烟产生量少,燃烧性能明显改善,同时能够满足在链条炉中燃烧的要求,使含油污泥资源化利用效果更好.     

翼身融合客机应急撤离建模与仿真方法研究

为研究翼身融合(BWB)客机的应急撤离流程及问题，以我国自行设计的BWB客机布局方案为对象，利用智能体建模方法搭建了该客机舱内应急撤离仿真试验模型，进行仿真试验研究。通过4因素3水平正交试验研究了主过道宽度、引导模式、隔板状态、出口数量等因素对该型客机应急撤离效果的影响，并对仿真试验模型进行了优化与验证。结果表明，主过道宽度在区间[48.26, 55.88] cm变化时会显著提高撤离效率；引导因素对撤离效果影响最显著；舱门引导与区域引导相结合的模式下撤离效果最优，撤离时间为108 s。研究形成了基于社会力模型的智能体在BWB客机应急撤离仿真研究中的应用方案，为其改进设计和制定更优应急撤离方案提供了建议和数据依据。     

Comparison of calculated data for the flammability and the oxidation potential according to ISO 10156 with experimentally determined values

The classification of flammable gas mixtures is based on either testing or calculation methods proposed by the revised international standard ISO 10156. This standard is used for classification of physical hazards in Chapters 2.2 and 2.4 of the UN Globally Harmonized System of Classification and Labelling of Chemicals (GHS) and in the UN Recommendations on Transport of Dangerous Goods (TDG). The test methods of flammability and oxidizing potential in this standard were developed by BAM. Earlier versions of this standard are not based on triangular diagrams and on the reference combustible substance “ethane”. The old material characteristics, especially in case of oxidizing potential, are based mostly on practical experience without any quantifiable test results. First time it is possible to compare experimental results from the CHEMSAFE database with the newly developed calculation method. In this paper the basic principles of the calculation methods are presented and the methods are validated by examples. A comparison of experimental flammability data with classification results gained by the calculation methods of ISO 10156 is demonstrated.     

The “Mini Closed Pressure Vessel Test (MCPVT)” as a screening or classification test for explosive properties of organic peroxides

Tests according to the UN Recommendations on the Transport of Dangerous Goods for the determination of explosive properties of organic peroxides have been compared with screening criteria for explosivity based on measurements in a closed mini-autoclave (MCPVT). It will be shown that an additional screening test may be helpful but the information obtained from the UN tests are more important to characterise the specific properties of a substance under different conditions.     

CEQAT-DGHS interlaboratory tests for chemical safety: Validation of laboratory test methods by determining the measurement uncertainty and probability of incorrect classification including so-called “Shark profiles”

Laboratory test results are of vital importance for correctly classifying and labelling chemicals as “hazardous” as defined in the UN Globally Harmonized System (GHS)/EC CLP Regulation or as “dangerous goods” as defined in the UN Recommendations on the Transport of Dangerous Goods. Interlaboratory tests play a decisive role in assessing the reliability of laboratory test results. Interlaboratory tests performed over the last 10 years have examined different laboratory test methods. After analysing the results of these interlaboratory tests, the following conclusions can be drawn:1There is a need for improvement and validation for all laboratory test methods examined.2To avoid any discrepancy concerning the classification and labelling of chemicals, the use of validated laboratory test methods should be state of the art, with the results accompanied by the measurement uncertainty and (if applicable) the probability of incorrect classification.This paper addresses the probability of correct/incorrect classification (for example, as dangerous goods) on the basis of the measurement deviation obtained from interlaboratory tests performed by the Centre for quality assurance for testing of dangerous goods and hazardous substances (CEQAT-DGHS) to validate laboratory test methods. This paper outlines typical results (e.g. so-called “Shark profiles” – the probability of incorrect classification as a function of the true value estimated from interlaboratory test data) as well as general conclusions and steps to be taken to guarantee that laboratory test results are fit for purpose and of high quality.     

Evaluative comparison of two methods for SADT determination (UN H.1 and H.4)

We present our results on the comparison of two methods for the SADT determination. Both methods, UN test H.1 and UN test H.4 are recommended by the international transport regulations from the UN. But during the last years the applicability of the UN test H.4 has been questioned for solid substances. Therefore, three organic peroxides and one self-reactive substance have been investigated in 5 kg and 20 kg packages as well as in the UN test H.4 in a 500 mL Dewar vessel. The SADT values determined with the different methods match. The UN test H.4 seems to be well suited for solid organic peroxides and self-reactive substances of at least 20 kg or 60 L.     

Validation of the UN test method N.5

Many substances react with water in such a way that flammable gases are formed. For transport issues this reaction may possess a considerable hazard especially if the cargo is wetted by rain or by water from other sources. In the UN Recommendations on the Transport of Dangerous Goods these kinds of problems are addressed. The UN test N.5 “Test method for substances which in contact with water emit flammable gases” corresponds to this hazard. Classification according to the test method is done by measurement of the gas evolution rate of the flammable gas by any suitable procedure. At BAM a gravimetric approach is used to measure the gas evolution rate. In this paper we present the evaluation of the apparatus by means of an absolute calibration routine utilizing a reaction where a known amount of gas is produced as well as the evaluation of important parameters influencing the gas evolution rate using different substances. It can be shown that the apparatus is capable of measuring absolute gas volumes as low as 6 mL with an acceptable error of about 17% as determined from the reaction of Mg with demineralized water.     

On the determination of the laminar burning velocity from closed vessel gas explosions

A methodology to determine the laminar burning velocity from closed vessel gas explosions is explored. Unlike other methods which have been used to measure burning velocities from closed vessel explosions, this approach belongs to the category which does not involve observation of a rapidly moving flame front. Only the pressure–time curve is required as experimental input. To verify the methodology, initially quiescent methane–air mixtures were ignited in a 20-l explosion sphere and the equivalence ratio was varied from 0.67 to 1.36. The behavior of the pressure in the vessel was measured as a function of time and two integral balance models, namely, the thin-flame and the three-zone model, were fitted to determine the laminar burning velocity. Data on the laminar burning velocity as a function of equivalence ratio, pressure and temperature, measured by a variety of other methods have been collected from the literature to enable a comparison. Empirical correlations for the effect of pressure and temperature on the laminar burning velocity have been reviewed and two were selected to be used in conjunction with the thin-flame model. For the three-zone model, a set of coupled correlations has been derived to describe the effect of pressure and temperature on the laminar burning velocity and the laminar flame thickness. Our laminar burning velocities are seen to fall within the band of data from the period 1953–2003. A comparison with recent data from the period 1994–2003 shows that our results are 5–10% higher than the laminar burning velocities which are currently believed to be the correct ones for methane–air mixtures. Based on this observation it is concluded that the methodology described in this work should only be used under circumstances where more accurate methods can not be applied.     

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。     

Azodicarboxylates: Explosive properties and DSC measurements

A large number of azodicarboxylates and their derivatives are produced and used in the chemical industries. The versatile applications of these azodicarboxylates in research institutes and in the chemical industries for chemical synthesis arouse additional hazards. The intent of this paper is to obtain first knowledge about the structure–response relationship regarding the explosive properties and the thermal hazards of different versatile used azodicarboxylates. The substances are examined with the differential scanning calorimetry (DSC). Furthermore, different laboratory test methods, based on the UN Recommendations on the Transport of Dangerous Goods, are applied to determine the explosive properties of the mentioned substances. On the basis of the obtained results, the known influence of the nitrogen content within the molecule regarding their thermal behaviour could be confirmed. The measured heat of decomposition appeared to be proportional to the nitrogen content within the group of the aliphatic and the aromatic azodicarboxylates. To emphasize this dependency, further investigations should be done. The long term objective of this research is to develop structure–response relationships of the explosive properties and the thermal hazards originating from azodicarboxylates.     

二溴海因危险性试验研究

为评价二溴海因(简称DBDMH)在使用、储运过程中的危险性,采用75℃热稳定性试验对二溴海因在高热条件下的稳定性进行了研究,采用C600微量热法测试了二溴海因的放热起始温度、分解热,并依据《联合国关于危险货物运输的建议书-试验和标准手册》对其爆炸性进行了筛选,通过固体氧化性试验和家兔皮肤刺激性/腐蚀性试验分别对二溴海因的氧化性和皮肤刺激性进行了测试。结果表明:二溴海因在75℃热稳定性试验过程中没有出现着火或爆炸,未出现自加热迹象,不属于太不稳定不能运输的物质;其分解反应只有一步,起始反应温度大约为157℃,分解热为384.8J/g,不属于爆炸品;二溴海因具有氧化性,根据《联合国关于危险货物运输的建议书-规章范本》其包装级别为Ⅱ级;在家兔皮肤刺激性/腐蚀性试验中未见不可逆损伤,对皮肤具有强刺激性。     

大容积无缝气瓶瓶口外螺纹修复方法及安全分析

为确定不同瓶口壁厚气瓶的外螺纹修复方式，采用数值和理论方法，通过分析外螺纹修复后气瓶的瓶体应力分布、周向转动和轴向窜动情况，对直接加工和采用热套工艺加装衬环2种瓶口外螺纹修复方式的安全性进行评价。结果表明:针对内螺纹规格为3-1/4″-8UN的气瓶，当采用直接加工方式将外螺纹修复至4-1/2″-8UN时，气瓶最大应力位于气瓶筒体上，此时气瓶可安全使用；当已修复至4-1/2″-8UN的瓶口外螺纹再次出现磨损时，直接加工的修复方式会对气瓶的安全使用造成影响，应采用热套工艺加装衬环方式修复瓶口螺纹。