Reactive chemical hazards of diazonium salts

Many diazonium salts are thermally unstable and sensitive to friction and shock. Most diazonium salts are known for their violent decomposition hazard in the solid state. There are many industrial and laboratory incidents caused by this group of chemicals. For safety purposes, the hazards related to the preparation and the handling of diazonium salts are discussed. Twelve cardinal rules are provided:1. Use only a stoichiometric amount of sodium nitrite when generating diazonium salts, avoiding excess sodium nitrite.2. Check for the excess of nitrous acid by starch–potassium iodide papers and neutralize it.3. Minimize the presence of nitrous acid by combining amine and acid first, then subsequently adding the sodium nitrite.4. Keep the temperature below 5 °C.5. Always vent the gases generated.6. Determine the thermal stability of diazonium compounds in your system.7. Understand the explosive properties of diazonium salts. If unknown, always assume they are explosive.8. Never allow the undesired precipitation of diazonium salts out of solution.9. Analyze the residual diazo compounds in the final product, especially for new process conditions.10. Quench the remaining diazonium salts before any further treatments.11. Isolate no more than 0.75 mmol of explosive diazonium salts at one time; also consider the addition of an inert material to stabilize the diazonium salts.12. Use a plastic spatula when handling the solid. The dried powder should not be “scratched” with a metal spatula or ground finely.An example of a testing strategy and data interpretation is provided for a process which has multiple steps and two diazonium compounds. Differential Scanning Calorimetry (DSC) and Heat of Mixing calorimetry (HOM) successfully serve as efficient tests to screen thermal stability and gas generation, identifying the candidates for advanced tests.     

Prediction of thermal hazards of chemical reactions

A large number of products of the chemical industry are produced using potentially hazardous reactions. The experimental investigation of the hazards of all reactions involved in production processes would be very expensive. The primary reactions—desired reactions which are part of the process—and the secondary reactions—undesired successive or side reactions—should both be considered. In this paper the methods of prediction of thermodynamic and kinetic properties of reactions are discussed.Thermodynamic data are of eminent practical importance because low heats of reaction may indicate that no further experimental investigations are necessary. For primary reactions, e.g. polymerization, diazotization and hydrogenation reactions, reaction enthalpies have been obtained by experimental methods. Typical data can be found in the public literature for the different reaction classes. When compared with theoretical thermodynamic data estimated by the chetah computer program, the agreement is satisfactory. chetah implements Benson's second-order group contribution technique (Benson, 1976).For secondary reactions, especially exothermic decomposition reactions, typical heats of reaction—mostly measured by DSC—have been associated with functional groups. Decompositions and other undesired exothermic reactions that proceed from the same functional group, e.g. a nitro group, have about the same heat of reaction.For the estimation using the chetah program, decomposition reactions have to be assumed which are typical for the functional group. The reaction yielding the maximum exothermic reaction energy was selected. The comparison of experimental heats of reaction with estimated data shows satisfactory agreement.In principle it is also possible to predict kinetic data of secondary reactions, but sufficient experimental data are missing.     

Assessment of chemical process hazards in early design stages

A new method called SREST-layer-assessment method with automated software tool is presented that in a hierarchical approach reveals the degree of non-ideality of chemical processes with regard to SHE (safety, health and environment) aspects at different layers: the properties of the chemical substances involved (substance assessment layer (SAL)), possible interactions between the substances (reactivity assessment layer (RAL)), possible hazard scenarios resulting from the combination of substances and operating conditions in the various equipments involved (equipment assessment layer (EAL)), and the safety technologies that are required to run a process safely and in accordance with legal regulations (safety-technology assessment layer (STAL)). In RAL, EAL and STAL the main focus is put on process safety. A case study is used to show the principles of the method. It is demonstrated how the method can be used as a systematic tool to support chemical engineers and chemists in evaluating chemical process safety in early process development stages.     

中小企业化学品职业危害预防控制指南

为了帮助中小企业控制预防控制化学品职业危害,本文详细介绍了国际劳工组织所推行的中小企业化学品职业危害控制指南,包括化学职业卫生管理的主要内容和基本步骤,关键点危险区的确定方法,改进化学品职业危害管理、实施化学品管理的良好规范、制定化学品管理行动计划和编制全面的化学品清单等方法,以达到系统提高化学品管理水平和持续改进的目标和要求.     

存在化学有害因素的小型企业职业危害定性评价研究

小型企业数量多、雇工人数总量大,分散在全国各地,行业分布广,由于其用于控制职业危害的资源和技术都非常有限,这对企业自身的职业危害控制和政府的职业卫生管理来说都是一大难题.本文在参考国外职业危害分级管理方法的基础上,为存在化学危害因素的小型企业建立了一个简便、实用的职业危害定性评价模型.该模型综合考虑了化学有害物质的危害性和接触可能性,并结合具体的实例进行分析,验证了其适用性和可靠性.该方法也适用于管理不够规范、缺乏监测资料和数据的作业场所职业危害评价.     

Stock market responses to chemical accidents in Japan: An event study

Despite recent major chemical process accidents in Japan, the top management teams of firms still avoid taking costly risk reduction measures because of their low perceived impact on firm performance. The disclosure of information on accident risks might motivate managers to enhance workplace safety because of the subsequent evaluation of firms by investors in stock markets. If the disclosed risk information is newly available for investors, firms with a high risk of accidents would receive a poor evaluation by stock markets and thus managers would take risk reduction measures to prevent stock prices from declining. In this study, we conduct an event study analysis to examine whether accident risk information is already reflected in stock prices, using data on the Japanese chemical industry. The results of our event study show that the estimated cumulative average abnormal returns of firms' stocks are significantly negative after severe accidents actually occurred. This finding implies that risk information is not already reflected in the stock prices of Japanese chemical firms and that the disclosure of accident risk information has the potential to motivate the top management teams of firms to reduce their firms’ accident risk.     

日本、韩国、东盟与我国石棉危害预防控制现状

简要介绍了日本、韩国、东盟各国以及我国石棉危害预防控制工作的现状,提出我国当前形势下应开展石棉危害现状的调研,研究建立石棉使用的许可管理制度,加强温石棉及其替代品危害性研究,并加强有关领域石棉危害预防控制法规政策的制定。     

灾害研究的两大关注点次生灾害与保险

1 次生灾害不容忽视 次生灾害也称二次灾害,指的是在重大自然灾害(原生灾害)发生后,与其伴生或衍生(引发)的灾害.它往往会形成一条灾害链,持续地给人类社会带来深重的灾难.有时,次生灾害带来的危害会远远超过主灾.     

透视我国非煤矿山事故隐患

据国土资源部统计:到2000年底,全国共有各类矿山153,063个。据此估算,非煤矿山约占一半,其从业人员达数百万之多。这数百万人的生死存亡,与矿山的安全状况息息相关。众所周知,矿山是基础产业。由于矿山的自然特点,其伤亡率远远高于其他产业。但是只要加强安全工作,伤亡事故是完全可以大大减少直至销声匿迹的。如美国2001年全国煤矿死亡人数仅为42人,非煤矿山死亡人数仅为30人。     

Computerized hazards analysis : The backbone of a hazards analysis effort/basis for a corporate hazards information exchange

Computerized hazards analysis has many obvious advantages. Criticality codes can be assigned, modified, sorted, grouped, and regrouped. Critical event assignments can be automatically tracked. Graphics capability can show the distribution of various types of hazards dramatically, and the risks involved with each. But, computerized hazards analyses can provide benefits orders of magnitudes beyond those mentioned above. Consider the following: as hazards analyses are performed, i.e., as hazard severity, critical events, and risks are defined for each component and each operator action in your facility, you are relying on the memories of many people for much of your input. The following text includes real life examples of such a situation.     

Process hazards review applied to the use of anhydrous ammonia in agriculture: an example of chemical process safety for small business

Process hazards review (PHR) techniques have generally been applied by large, sophisticated companies in the nuclear, aerospace, and chemical process industries. There remains, however, a large population of smaller distributors and consumers of hazardous materials which could benefit equally from the application of PHR. These consumers unfortunately are generally less sophisticated and individually lack the necessary resources required to apply such state-of-the-art safety techniques.

Where common processes can be identified, it is possible to conduct a more generic PHR that will provide a sound technical basis for recognizing and preventing the development of hazards wherever these processes are used. Some facility-specific issues will always need to be considered, but the existence of the generic PHR should make the conduct of a PHR by each facility considerably easier and less costly.

Researchers from the National Institute for Occupational Safety and Health (NIOSH) contracted with DNV Technica Inc. to lead a hazard and operability study (HAZOP) of agricultural handling of anhydrous ammonia, from the receipt of ammonia at the retail distribution centre to the application of the ammonia by farmers to the fields. The multidisciplinary HAZOP team consisted of representatives from NIOSH, an agricultural chemical trade association, an ammonia producer, state ammonia facility inspectors, a retail distributor, and an equipment manufacturer. Several participants were part-time farmers with ammonia application experience.

Some specific aspects of applying the HAZOP technique in the context of this study, the findings obtained, and the plans to disseminate the important safety information developed during the course of the PHR are discussed. Finally, it is suggested that this approach could prove to be a useful addition to the product stewardship activities of chemical producers.     

热等离子体技术销毁日本遗弃化武红弹装填物研究

针对二战期间日本侵略军在我国遗弃的大量化学武器的危害性,进行了热等离子体技术销毁含砷毒剂的实验,旨在为评价日本遗弃化武的销毁技术选择提供技术支持.所采用的热等离子体处理固体废弃物的实验装置主要由等离子体发生器、等离子体旋转炉、二次燃烧炉、冷却器、文丘里喷淋塔和洗涤喷淋塔等设备组成.利用该装置对日本遗弃化武红弹和红简装填物二苯氰砷和二苯氯砷进行了销毁实验,并用GC-MS法对销毁产物进行分析.结果显示,经处理后未检测出二苯氯砷和二苯氰砷,根据分析方法的检出下限计算出的二苯氯砷和二苯氰砷的销毁去除率均高达99.999 9%.对熔渣进行砷的浸出毒性实验显示,浸出液中砷的质量浓度均低于0.03 mg/L,远低于我国固体废物砷的浸出毒性鉴别标准值1.5 mg/L.但是,等离子体炉在销毁含砷有机毒剂时,固砷效率很差,因此要发挥等离子体技术的优势,还必须加强固砷方法的研究.     

聚焦日本遗弃化学武器防护生命安全刻不容缓

值此中国人民抗日战争及世界反法西斯战争胜利60周年之际，仅发此文悼念日化武器的受害同胞，提醒人们高度关注日本遗弃化学武器带来的伤害，认真做好各项防护工作。     

Globalization and workplace hazards in developing nations

Multinational corporations are rapidly introducing hazardous technological activities into less-developed nations. There is considerable evidence that this feature of global commerce poses risks to health, safety and natural resources, and most immediately endangers the workers involved. The less-developed nations hosting these activities are vulnerable to exploitation of their human resources because they lack the safeguards, expertise, and public pressures that prevent harms to workers in developed nations. This paper presents an evaluation of approaches taken by international and industrial organizations to address workplace hazards by soft law, hard law, codes of conduct, and voluntary self-regulation. Finding that these approaches have repeatedly failed, a new approach is presented for the purpose of assuring that the transfer of technology will be accompanied by the transference of practices for using it safely. The key features of this approach are then considered: defining a standard of care which aims to provide equivalent treatment of worker health and safety across all nations, irrespective of their level of development, and establishing contractual relationships between multinational companies and host countries as a feasible means of implementing the standard and achieving equivalent treatment.     

Risk assessment of antagonistic hazards

This paper considers the risk to major hazard plant from terrorists deliberately causing catastrophic industrial accidents. The United States of America Department of Justice [Assessment of the increased risk of terrorist or other criminal activity associated with posting off-site consequence analysis information on the internet, 2000] reports that “breaching a containment vessel of an industrial facility with an explosive or otherwise causing a chemical release may appear relatively simple to…a terrorist”. They concluded that the risk of such action is “real and credible”.

Analysis of terrorism is often hampered by its being described as ‘irrational’; one corollary would be that it is unpredictable. However, terrorism may usefully be treated as a rational behaviour and in doing so it becomes possible to assess the risks it causes.

We analyse the vulnerability of major hazard plant to terrorist attack and identify nine factors (access, security, visibility, opacity, secondary hazard, robustness, law enforcement response, victim profile, and political value) that might be used as a starting point for more formal risk assessment and management.     

Compression system check-valve failure hazards

Processes that utilize multistage compression systems (olefins plant compression systems, gas processing, integrated refrigeration systems, etc.) have the potential for overpressure due to single or multiple check-valve failure. Catastrophic equipment failure resulting from overpressure can potentially occur due to compression system discharge, interstage, and/or suction check-valve failure, coincident with compressor shutdown. Depending on system design and application, overpressure values approaching or exceeding 300% of equipment design are possible, while for some equipment, even limited overpressure can result in catastrophic vessel failure due to brittle fracture. Additional hazards associated with compression system fail-to-check scenarios include risks associated with excessive flare loading and compressor rotor reverse rotation. In the case of an ethylene refrigeration compressor at a typical ethylene plant, rotor reverse rotation can potentially exceed overspeed limits.This paper provides risk assessment results based on analyses performed on the three primary compression systems in six ethylene plants. The methodologies used for risk identification screening, detailed risk assessment and evaluation of system dynamics are all presented. Alternative methods for mitigating risks are also discussed, along with check-valve reliability data. An overview of applicable overpressure protection requirements defined in the ASME Boiler and Pressure Vessel Code is provided. This paper will be of interest to anyone who designs or operates multistage compression systems in the chemical, petrochemical or refining industries.     

定量风险评价（QRA）中的危险辨识方法

危险辨识是进行定量风险评价（QRA）的关键步骤,QRA分析区域内的危险设备设施可能很多,但并不是每台设备设施都一定要包含并进行定量风险计算,这不仅涉及到QRA的效率和成本问题,也涉及到评价结论准确性、安全投入有效性等问题。本文简要介绍并比较了欧盟ARAMIS和挪威Purple book中推介的2种危险辨识方法,有助于国内QRA分析人员参照比较及提升QRA分析的一致性。     

Characteristics and hazards of electrostatic discharges in air

In the assessment of electrostatic hazards in the process industries, a great deal of emphasis has been placed on the determination of energies in spark discharges. There are, however, other electrostatic discharge phenomena where this approach has severe limitations. The purpose of this paper is to describe the state-of-the-art with respect to electrostatic discharges in gases (air). An in depth review of the literature has been made, and the various types of discharges are tabulated and discussed.