二氯海因热稳定性研究

为评价二氯海因在储运过程中的热稳定性,采用C80微量热法对二氯海因进行反应放热测试,并计算了该物质在50 L标准包装条件下的自加速分解温度；同时采用克南试验、时间/压力试验对二氯海因在封闭条件下加热和点火的效应进行了研究.结果表明:二氯海因的分解起始温度为202.3℃,分解热为1 168.8 J/g,50 L标准包装下的自加速分解温度为120℃；二氯海因的克南试验极限爆炸直径为2.0mm,在封闭条件下外部加热具有敏感性；时间/压力试验中反应压力从690 kPa升至2 070 kPa,所用时间为260 ms,在封闭条件内部点火时具有爆燃性.     

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。     

汽车安全气囊用药危险性实验研究

为了确定汽车安全气囊用药的危险性,根据其成分组成选取75℃热稳定性实验、时间/压力实验、克南实验、撞击敏感度实验、摩擦敏感度实验以及固体氧化性实验对汽车安全气囊用药进行测试并分析实验结果判断其危险性.实验结果表明:汽车安全气囊用药是热稳定的；时间/压力实验中发生猛烈爆燃,在商业包装正常条件下能够显示爆燃的能力；克南实验极限直径为3.0mm,在封闭条件下加热显示效应；撞击敏感度实验以及摩擦敏感度实验均未出现特殊现象,气囊用药可以以其实验的形式运输；气囊用药具有氧化性.结合相关标准及法规进行综合判断,可以确定汽车安全气囊用药的危险性并且划分危险类别,对保证汽车安全气囊用药的生产、运输、储存等过程的安全具有指导意义.     

BTP-N_2复合气体配比优化及灭火临界条件研究

为了考察一溴三氟丙烯(简称BTP)与氮气(N2)所形成的复合灭火介质的复合比以及不同复合比下的临界灭火条件,开展了以下工作:首先,基于多组分分压原理,探讨了BTP-N2预混技术的可行性;其次,基于燃烧学和气体运动学理论,提出了BTP与N2复合灭火介质的灭火临界条件预测理论模型;再次,依据卤代烷灭火介质的特点和灭火机理,构建了临界灭火试验平台,对不同BTP和N2复合比下的复合气体灭火介质进行灭火临界条件研究;最后,通过实验结果修正和完善预测理论模型。结论:BTP-N2复合灭火介质的灭火临界条件理论值与实验值吻合性较好,因此该预测模型能很好地对复合卤烃灭火介质的临界灭火条件进行估算,为研究卤烃气体与惰性气体复合灭火介质的灭火机理及研发高效清洁灭火介质奠定了基础。     

不同实验标准对几种常见阻燃剂粉尘可爆性影响研究

为研究阻燃剂粉尘可爆性，依据不同实验标准所采用的哈特曼管和20 L球爆炸实验系统，对几种常见阻燃剂粉尘可爆性进行了初步研究。结果表明:按不同标准实验，四溴双酚A、三聚氰胺、二乙基次膦酸铝、赤磷和对二丁基氧化锡均为可爆性粉尘；三氧化二锑、钛白粉、碳酸钙、氢氧化铝和二氧化硅均为不可爆性粉尘；氰尿酸三聚氰胺、球形硅树脂粉以及膨胀石墨的粉尘可爆性结果不一致。对于某些阻燃剂，点火源的起始能量对粉尘可爆性结果有较大影响；某些阻燃剂对爆炸具有抑制效应，抑制程度同物质本身的性质和浓度有关系。     

金属热颗粒引燃可燃堆积材料的实验研究

电焊操作、烟花燃放、工业磨削和高压电线碰撞等过程容易产生高温热颗粒。这些热颗粒一旦接触可燃材料就有可能引燃材料,导致火灾。该文对热颗粒引燃可燃堆积材料的行为进行实验研究,从而为工业堆积材料的火灾防控方法提供参考。实验加热一系列不同直径(6mm,8mm,10mm,12mm,15mm,20mm)的黄铜金属颗粒作为热源,并采用三种常见的工业堆积材料(木粉,炭粉,羟丙基甲基纤维素HPMC)作为可燃材料的代表物,研究不同功率金属热颗粒对材料的引燃行为,分析金属热颗粒引燃材料的临界功率。结果表明,材料本身的性质会影响热颗粒的引燃行为,HPMC的引燃时间最长,木粉的引燃时间最短。随着热颗粒直径的增加,热颗粒引燃三种材料所需的功率值整体呈增大的趋势。由于燃烧空腔的形成,HPMC的引燃临界功率相对较高。     

海水淡化浓盐水排放中挥发性卤代烃环境安全性评价

对天津大港新泉海水淡化有限公司排放浓盐水的6次水样中11种挥发性卤代烃质量浓度进行分析,依据3个基础营养级水平(藻、蚤、鱼)的急性毒性效应(L(E)C50),采用商值法对海水淡化浓盐水排放中的二氯甲烷、1,2-二氯乙烯、1,1-二氯乙烷、三氯甲烷、1,2-二氯乙烷、四氯化碳、三氯乙烯、二氯一溴甲烷、一氯二溴甲烷、四氯乙烯和三溴甲烷进行了环境安全性评价。结果表明,1,1-二氯乙烷、三氯甲烷和1,2-二氯乙烷3种挥发性卤代烃的环境质量浓度/无影响质量浓度(PEC/PNEC)比值大于1,存在一定生态风险。     

H2O2对含氮消毒副产物二氯乙腈、二溴乙腈去除及影响因素研究

为了解H_2O_2在实际处理饮用水中有机物的效果,研究了过氧化氢(H_2O_2)在常温常压下对氯化消毒副产物二氯乙腈(DCAN)和二溴乙腈(DBAN)去除效果及影响因素的规律,探究了H_2O_2投加量、初始pH值和反应物初始质量浓度对DCAN和DBAN去除效率的影响。结果表明,H_2O_2能较好地氧化降解DCAN和DBAN。当H_2O_2单独去除一种卤乙腈(Haloacetonitriles,HANs)时,加大反应物初始质量浓度促进氧化降解DCAN和DBAN的效果不明显,当反应5 min、反应物初始质量浓度为250μg/L时,DCAN和DBAN的去除率最高;过高或过低的pH值会抑制氧化反应的进行,pH=7. 5时,DCAN和DBAN的去除率达到最大,分别为46. 47%和43. 41%; H_2O_2在一定投加量(15～35 mmol/L)范围内,随H_2O_2浓度增加,DCAN、DBAN的去除率分别呈现先增加后降低和先增加后平缓的趋势,二者的H_2O_2最佳浓度分别为25 mmol/L和30 mmol/L。     

薛湖矿二_2煤顺层钻孔瓦斯抽放的数值模拟与分析

针对我国煤矿绝大部分煤层属于渗透率低,地质条件复杂、瓦斯抽采效果差的特点,运用了FLUENT仿真软件,结合渗流力学理论,以薛湖矿二2煤层为工程背景,模拟顺煤层钻孔抽采的煤层压力、煤层渗透率、抽采负压、钻孔直径、抽采时间等因素,分析顺煤层钻孔瓦斯抽采规律,为类似顺煤层钻孔抽采设计提供科学依据;通过三种尺寸顺层钻孔工业实验,并从施工难易程度和经济效果以及抽放率的角度,确立了采用Φ75mm钻孔的抽放工艺;同时采用高压注水增大煤层透气性的方式进一步提高煤层瓦斯的抽放量。     

苏云金芽胞杆菌基因工程菌BMB696B对实验动物的安全性评估

将来自苏云金芽胞杆菌李氏亚种的营养期杀虫蛋白基因vip83导入苏云金芽胞杆菌高毒菌株YBT-1520,得到广谱、高毒的工程菌BMB696B.室内生物测定显示该工程菌对棉铃虫和甜菜夜蛾具有很高的毒力.然而,国内外还未见有关于营养期杀虫蛋白的毒理学资料的报道,因此工程菌BMB696B的毒理学安全性也无法预测.为了对该工程菌的安全性进行合理的评价,并为该产品的生产和应用过程中安全防护措施的制定提供依据,根据国家标准GB 15670-1995<农药登记毒理学试验方法>,就BMB696B粉剂对实验动物进行了相关的毒理学试验.结果表明,工程菌对Wistar大鼠急性经口LD50大于5 000 mg/kg,急性经皮LD50大于2 000 mg/kg,均属低毒类;对兔皮肤刺激平均指数72 h后为0,皮肤刺激强度为无刺激性;眼刺激平均指数48 h后为O,眼刺激强度为无刺激性;对豚鼠致敏率为0,属Ⅰ级弱致敏物.由此证明,工程菌BMB696B没有经口和经皮的急性毒性、没有急性皮肤和眼刺激性、没有致敏性.     

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.     

Using risk tolerance criteria to determine safety integrity levels for safety instrumented functions

Standards and industry guidelines for Safety Instrumented Systems (SISs) describe the use of hazard and risk analysis to determine the risk reduction required, or Safety Integrity Levels (SILs), of Safety Instrumented Functions (SIFs) with reference to hazardous events and risk tolerance criteria for them. However, significant problems are encountered when putting this approach into practice. There is ambiguity in the meaning of the term hazardous event. Notably, even though it is a key concept in the process-sector-specific SIS standard, IEC 61511/ISA 84, it is not defined in the standard. Consequently, risk tolerance criteria for hazardous events are ill-defined and, therefore, they are not the most appropriate criteria to use. Most current approaches to SIL determination use them and therefore they are flawed fundamentally.An informed decision on the tolerability of risk for a facility cannot be made by determining only the tolerability of risk for individual hazardous events. Rather, the tolerability of the cumulative risk from all hazard scenarios and their hazardous events for a facility must be determined. Such facility risk tolerance criteria are the type used by regulators. This issue applies to all per event risk tolerance criteria. Furthermore, determining the tolerability of risk for a facility based only on the risks of single events, be they hazard scenarios or hazardous events, and comparing them to risk tolerance criteria for the events is not meaningful because there is no consideration of how many such events can actually occur and, therefore, no measure of the total risk. The risks from events should be summed for a facility and compared with overall facility risk tolerance criteria.This paper describes and illustrates SIL determination using a risk model implemented within the framework of Layers of Protection Analysis (LOPA) that overcomes these problems. The approach allows the allocation of risk across companies, facilities, processes, process units, process modes, etc. to be managed easily.     

基于风险的危险品道路运输安全容量研究

为了确定危险品道路运输安全容量，保障危险品道路运输安全，基于风险理念，使用对比研究方法，提出危险品道路运输个人风险基准，建立改进的危险品道路运输定量风险评估模型。结合提出的风险基准，提出危险品运输安全容量确定方法，解决了单一类别和多种类别危险品运输安全容量确定问题。研究结果表明:在某城市化工集聚区的实例应用该方法，能够大幅度降低危险品道路运输潜在生命损失，有助于保障危险品道路运输安全。     

Combining HAZOP with dynamic simulation—Applications for safety education

A quantitative variation of the hazard and operability analysis (HAZOP) procedure is demonstrated. The process is divided into sections and dynamic models of the separate sections are prepared. Those models are used in the framework of the HAZOP procedure to determine the magnitude of the deviations from normal operation conditions that may lead to serious accidents and to test design modification to improve the safety characteristic of the process. A process involving an exothermic reaction conducted in a semi-batch reactor is used to demonstrate the advantages of the proposed procedure and its application for safety education and operator training. The programs used for simulating the reactor are available at: ftp://ftp.bgu.ac.il/shacham/OctanoneProd/.

It is shown that the use of those programs can enhance considerably the safety education by providing tools for systematic screening of process deviation associated with possible hazardous events, determining the threshold values that may lead to such events and enabling the examination of a particular design for the adequate safe range of operation.     

Comparative study of the methodologies based on Standard UNE 60079/10/1 and computational fluid dynamics (CFD) to determine zonal reach of gas-generated Atex explosive atmospheres

This study presents two methodologies which can be used to determine the classification and extended area of hazardous zones caused by gas, vapours and mists. The first is based on UNE 60079/10/1: Electrical apparatus for explosive gas atmospheres – Part 10: Classification of hazardous areas, whilst the second is developed on the basis of Computational Fluid Dynamics (CFD) using the FLUENT software application. Both methodologies were applied in the same case study of differing leakage components from a dairy farm steam boiler room fuelled by liquid natural gas (LNG).The results obtained show that CFD methodology is a powerful tool with a significant capacity for determining the size of an explosive atmosphere for a broad range of exhaust sources. This methodology offers more conservative results than those obtained from the analytical methodology recommended in Standard UNE 60079/10/1. Results obtained using CFD are more useful in enabling the study of turbulence phenomena, boundaries, and diverse initial and contour conditions.In contrast, the Standard UNE 60079/10/1 methodology is less conservative and aims at determining the hypothetical volume V_z of the explosive atmosphere. This volume is a measurement of the ventilation efficiency which is in turn proportional to a massive gas release through an exhaust source divided by the number of air changes in the enclosed area.From the results obtained, it can be confirmed that Standard UNE 60079/10/1 should be revised.     

Class-2 hazmat transportation consequence assessment on surrounding population

The transportation of hazardous materials by road is an utmost necessity of the world for the societal benefits, but at the same time the activity is inherently dangerous. Incidents involving hazardous material (hazmat) cargo particularly the class-2 materials can lead to severe consequences in terms of fatalities, injuries, evacuation, property damage and environmental degradation. The rationale behind considering class-2 hazmats is that they pose the greatest danger to the people and property along the transport route because of their storage condition on the transport vessel. They are stored either in pressurized vessels or in cryogenic containers. Any external impact due to collision may cause catastrophic failure of transport vessels, known as BLEVE (Boiling Liquid Expanding Vapour Explosion) with devastating consequences. Further, any continuous release from containment may cause what is known as ‘Unconfined Vapour Cloud Explosion’ (UVCE). Historically frequency of BLEVE occurrence is of the order of 1 × 10⁻⁶ per year or less, but other release scenarios e.g. a large vapour or liquid leaks are more probable and could also have devastating effects on the surrounding population. As such, the paper discussed various event scenarios and the consequences taking examples of a class-2.1 material (1,3 butadiene) and another class-2.3 (ammonia) hazmat. Comparative analysis suggests that per ton basis a rupture of ammonia tanker gives rise to larger impact areas and poses larger lethality risks compared to 1,3 butadiene as far as toxic effects are concerned. Besides, from fireball fatality on similar basis propylene causes higher consequence distance than LPG followed by ethylene oxide and 1,3 butadiene. The impact zone study results may be utilized as inputs for identifying the potential vulnerable area on a GIS enabled map, along a designated State highway route passing through an important industrial corridor in western India.     

我国化学品安全技术说明书(SDS)的管理现状研究

从分析我国化学品安全技术说明书的监管现状出发,研究对比了我国和国外在SDS覆盖化学品的范围、审核监督制度以及信息保密机制等管理技术方面的不同做法;指出我国对化学品安全技术说明书的监管在这三方面存在缺陷和不足;提出加强和完善化学品安全技术说明书的监管是提高我国化学品安全监管水平的重要手段;认为借鉴欧盟、美国和加拿大等国家的先进做法拓宽需要编制SDS的化学品范围、建立化学品安全技术说明书第三方检测制度、加强监督、完善信息保密机制将对促进我国的化学品安全监管水平具有重要意义。     

Real-time response system for the prediction of the atmospheric transport of hazardous materials

Human urge of exploiting earth resources has resulted into unprecedented industrial development in the last century resulting into production of large quantities of hazardous chemicals. Chemical, petrochemical, nuclear, biomedical and pharmaceutical industrial accidents release large quantities of hazardous chemicals into the atmosphere. The accidental discharge during production or storage or transportation have subjected the population to be exposed to exceptionally high concentration levels of hazardous chemicals, taking them by surprise, unprepared with fatal consequences. An emergency planning organization has to be trained to combat this situation in the shortest possible time to minimize the number of causalities. The present paper focuses on computation of dispersion model, using emission source, accident location and online metrological data near to the sources, to provide necessary and accurate results swiftly. The predicted ground level concentrations with the hazardous nature of the chemical, speed and direction of plume, the emergency team will be supplied with all the information in graphical easy to grasp form, superimposed over a GIS map or the latest satellite image of the area.

The emergency team has to be trained for all past scenarios and their preparedness, response and actions must be practiced regularly to be able to abate chemical releases accidentally or intentionally.

Accidental releases of chlorine and ammonia gases in residential and industrial areas are simulated. The predicted ground level concentrations in the effected areas are shown after different time intervals. For low vapor pressure chemical, the dispersion time is large and concentration levels are low but persist for prolonged time while for volatile chemical, the concentrations are high in short time and recovering to safe environment is quick.     

改进广义灰色关联故障树的危化品LSSC可靠性诊断

为了探究影响危化品物流整体运作的关键事故因素,提出一种改进广义关联故障树的危化品LSSC可靠性诊断方法。结合实例构建危化品LSSC系统失效故障树,运用灰色关联技术对以最小割集构造的标准故障模式向量和底事件概率重要度组成的待检模式向量进行相关性分析,得到系统失效概率等级与失效故障模式可能性排序,确定系统关键薄弱环节。研究结果表明:该方法能够快速识别危化品物流运作系统关键事故因素,为危化品LSSC风险等级控制和分级防范措施制定提供参考和借鉴。