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The incorporation of hazard reduction as a chemical design criterion in green chemistry 将减少危害作为绿色化学设计的标准
Pub Date : 2005-03-01 DOI: 10.1016/j.chs.2004.10.001
Nicholas D. Anastas, John C. Warner
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引用次数: 22
Safety of chlorine production and chlorination processes 氯生产和氯化过程的安全
Pub Date : 2005-01-01 DOI: 10.1016/j.chs.2004.08.002
Jean-Louis Gustin

Most chlorine production is obtained by electrolysis of NaCl aqueous solution. Other processes to produce chlorine involve the electrolysis of KCl or HCl aqueous solutions, the electrolysis of molten NaCl at high temperature and the Deacon process. In most cases, chlorine is a by-product in the production of caustic soda, potassium hydroxide, sodium metal or is recovered from HCl using HCl aqueous solution electrolysis or gas–solid reaction in the Deacon process.

Chlorination reactions are part of various processes in the chemical industry, to manufacture heavy chemicals, specialty chemicals, pesticides and pharmaceuticals, in inorganic and organic chemistry. They are valuable tools in organic synthesis.

The hazards of chlorine production and chlorination processes involve:

  • -

    Gas phase explosion, i.e., self-ignition, deflagration and detonation in the gas phase.

  • -

    Runaway reaction or thermal explosion, deflagration and detonation in the condensed phase.

Gas phase explosion hazard with chlorine as an oxidizer is present in the production of chlorine by electrolysis, in gas phase chlorination processes and in chlorination reactions carried out in the condensed phase.

Gas phase chlorination processes are continuous processes operating either in the flammable range like burners or outside the flammable range in loop reactors or loop processes where chlorine is the controlling reactant.

When chlorination is carried out by chlorine injection in the liquid phase, gas phase explosion hazard is related to chlorine evolution in the vapour phase, giving a flammable mixture with the solvent or reaction mixture vapour. Hazard assessment is achieved by comparing the gas phase composition with the flammable area of the gaseous mixture. Self-ignition is also considered because the self-ignition temperature of gaseous fuels in chlorine atmosphere is lower than in air or oxygen and often close to the ambient temperature.

The relevant flammability data is the flammability limits, LFL, UFL, minimum oxidizer concentration (MOC), auto-ignition temperature (AIT), of fuels in chlorine and the explosion characteristics Pmax and KG for deflagration in chlorine.

A collection of flammability data is given for the reader convenience, collected in the literature or obtained in our own experimental facility, a specially designed 20 L Hastelloy C 276 sphere with 200 bar pressure resistance, ambient to 300 °C initial temperature, easily opened for frequent cleaning. This apparatus allows precise determination of the flammability limits, self-ignition temperature, explosion overpressure, rate of pressure rise and flame speed.

Runaway reaction hazards in chlorination reactions are related to a series of dangerous process situations or process deviations such as:

大多数氯的生产是通过电解NaCl水溶液获得的。其他生产氯的方法包括电解氯化钾或盐酸水溶液、高温电解熔融NaCl和Deacon法。在大多数情况下,氯是烧碱、氢氧化钾、金属钠生产过程中的副产品,或在Deacon工艺中使用HCl水溶液电解或气固反应从HCl中回收。氯化反应是化学工业中各种过程的一部分,用于制造无机和有机化学中的重化学品、特种化学品、杀虫剂和药品。它们是有机合成中有价值的工具。氯气生产和氯化过程的危害包括:-气相爆炸,即气相自燃、爆燃和爆轰。-在凝聚态发生失控反应或热爆炸、爆燃和爆轰。以氯为氧化剂的气相爆炸危险存在于电解法生产氯、气相氯化过程和在凝聚相中进行的氯化反应中。气相氯化过程是在可燃范围内(如燃烧器)或可燃范围外(在循环反应器或以氯为控制反应物的循环过程中)操作的连续过程。当在液相中注氯进行氯化时,气相爆炸危险与氯在气相中析出有关,与溶剂或反应混合物蒸气形成可燃混合物。危害评估是通过比较气相组成和气体混合物的可燃区域来实现的。由于气态燃料在含氯气氛中的自燃温度比在空气或氧气中的自燃温度低,往往接近环境温度,因此也考虑自燃。相关的可燃性数据是燃料在氯中的可燃性限值、LFL、UFL、最低氧化剂浓度(MOC)、自燃温度(AIT)以及在氯中爆燃的爆炸特性Pmax和KG。易燃性数据的收集是为了方便读者,从文献中收集或在我们自己的实验设施中获得,一个专门设计的20 L哈氏合金C 276球,耐压200巴,环境至300°C初始温度,容易打开,经常清洗。该仪器可精确测定可燃性极限、自燃温度、爆炸超压、压力上升速率和火焰速度。氯化反应中的失控反应危险与一系列危险的工艺情况或工艺偏差有关,如:-反应起始延迟。-反应混合物不稳定性。-氯胺、三氯化氮、氯亚硝基化合物、次氯酸酒精等不稳定物质的产生和积累。-在水溶液中进行氯化反应时,对不稳定物质进行脱混或分离,因为氯化化合物比初始反应物更难溶于水。从文献和实验室的例子中,全面审查了氯化反应中的失控反应危险。
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引用次数: 9
Happy New Year! 新年快乐!
Pub Date : 2005-01-01 DOI: 10.1016/j.chs.2004.11.002
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引用次数: 1
What are building codes? 什么是建筑规范?
Pub Date : 2005-01-01 DOI: 10.1016/j.chs.2004.09.012
Janet Baum
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引用次数: 12
One for the money, two to make ready 一个拿钱,两个准备
Pub Date : 2005-01-01 DOI: 10.1016/j.chs.2004.11.011
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引用次数: 0
News & Views 新闻及观点
Pub Date : 2005-01-01 DOI: 10.1016/j.chs.2004.11.005
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引用次数: 0
NIOSH education and research centers NIOSH教育和研究中心
Pub Date : 2005-01-01 DOI: 10.1016/j.chs.2004.11.010
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引用次数: 0
Author's Guide 作者指南
Pub Date : 2005-01-01 DOI: 10.1016/S1074-9098(04)00161-3
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引用次数: 0
Mix and match 混合搭配
Pub Date : 2005-01-01 DOI: 10.1016/j.chs.2004.11.009
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引用次数: 0
In Memory—Warren K. Kingsley, 1929–2004 在记忆中——沃伦·k·金斯利1929-2004
Pub Date : 2005-01-01 DOI: 10.1016/j.chs.2004.11.012
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引用次数: 0
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