硝酸铵:悲惨的课程仍在学习

By Dr. Vyto Babrauskas

2020年8月4日,黎巴嫩大部分贝鲁特港口,由于巨大的ammonium nitrate (AN)爆炸。2013年4月17日,德克萨斯州西部镇的一部分在硝酸铵存储设施爆炸时被升级。根据有关贝鲁特灾难的初始信息,我们将在这里研究得克萨斯州可以从德克萨斯州学到的课程,这些课程可能避免了贝鲁特灾难。

硝酸铵灾难和安全措施

在20世纪初期,曾经在硝酸铵制造中经常发生灾难。但是在最近的时候,制造商学会了意识到安全性,与实际制造过程有关的事故很少。灾难继续定期复发的地方是材料在运输或存储中。几年前,我进行的一项研究表明,存储或运输中的100%的A at是由于一个原因:不受控制的火灾(1)。没有其他原因。

有关的

Ammonium Nitrate Explosions: Common Factors in Major Disasters

来自消防工程保险库188金宝搏是正规吗:德克萨斯城爆炸

德克萨斯城灾难

德克萨斯州西部的爆炸:从多次死亡中学到的教训

但是,如果是这种情况,则不难看出所需的解决方案是简单而坚固的。如果我们不受控制的火灾是不可能的,就不会发生事故。这并不难;实际上,这很容易。一个只需要做两件事:

  • Only store the material in a fully non-combustible building.
  • Make sure there are no combustible goods nearby which could ignite and burn.

完成这些事情并不是一个具有挑战性的工程问题。自1880年代(2)以来,我们已经知道如何建立完全非燃烧的结构。而且,它再次不需要先进的技术知识,以确保附近没有任何可燃的东西可以在燃烧时用火焰威胁储存。

Other safety precautions can be marginally helpful(3), but some are genuinely misguided. Foremost of these is the concept of setback distances, intended as a safety zone surrounding an explosion. Looked at very superficially, this might seem to be a good idea, but a closer examination reveals the opposite. Consider first if the management of combustibles is inadequate, there remains a risk of explosion. Obviously, if an explosion is immanent, the surrounding area needs to be cleared of all individuals. This means first-responders need to be sent into an area where they may be blown up. This is not consistent with protecting the lives of the first responders themselves. On the other hand, if combustibles have been successfully managed so that there is no risk of explosion, then explosion-safety setback distances clearly serve no purpose.

灾难的悲伤历史

不幸的是,完全可预防的灾难不断反复出现。在上个世纪,大约有70起主要的大火涉及存储或运输。其中30%导致爆炸,而15%导致生命损失(4)。由于有足够的数据可用,因此可以将这些统计数据视为直接指示如果严重的大火威胁储存的情况会发生的预期后果。我认为,任何涉及死亡人数的风险有15%的活动,认为这是不可接受的风险,但是显然需要更多的教育来传达这一信息。

在美国,最近发生的一场灾难发生在2013年4月17日,当时德克萨斯州西部的一个约有30吨的仓库着火,炸死,爆炸了15人被杀,约260人受伤。该镇的很大一部分被炸毁了,其中包括两所受到严重破坏的学校,需要拆除它们(5)。这场灾难尤其令人沮丧,因为大多数被杀的人是消防员,要么是直接做出回应以协助当地志愿消防部门努力的人。在此之后,我发表了九篇有关AN火/爆炸危害以及如何预防此类灾难的文章。显然,这些信息都没有到达黎巴嫩贝鲁特的官员,因为他们知道死亡的可能性15%,并且只是接受了这种风险,这似乎是不合理的。而且,当然,贝鲁特悲剧的数量级比德克萨斯州的悲剧差,这是非常悲惨的。

德克萨斯与贝鲁特:一些相似之处和一些差异

这两个事件具有至关重要的相似之处:在这两种情况下,很明显,不受控制的火是爆炸的直接原因。在这两种事件中,视频在爆炸前的迅速恶化的火灾中清楚地表明了燃烧。德克萨斯州的可燃材料是木制建筑,以及多种可燃农产品。在贝鲁特事件中,照片表明建筑物本身不可燃。早期的报道并未阐明所有条件,但似乎燃烧了一堆烟花。目前尚不清楚还有什么正在燃烧,但是很明显,爆炸是在大火之前并触发的。

德克萨斯州的A是一种肥料产品,旨在出售给当地农民。贝鲁特的产品被从船上没收,并打算运送到莫桑比克的采矿业务,可能是制造硝酸铵/燃油(ANFO)的成分。这意味着刷子的物理规格略有不同,但这不会影响材料爆炸的倾向。当然,最大的区别是,大约30吨就足以达到德克萨斯州西部的相当大的一部分,而在贝鲁特,涉及约2,750吨。伤亡人数也有很大的差异。在德克萨斯州,事件中有15人死亡。在贝鲁特,官方统计尚未可用,但最初的估计估计约为150。由于贝鲁特的材料有将近两个数量级的材料,因此确实没有两个数量级的死亡人数。

硝酸铵特性

Since AN is not in widespread general usage, it is useful to understand some of its basic properties and traits. Ammonium nitrate (NH43)是一种不可燃烧的化学物质。因此,报道说存储的“点燃”是不正确的,因为只有燃料可以点燃,并且是氧化剂,而不是燃料(6)。但是,罐子爆炸(7),如果数量很大,爆炸可能会大大巨大。现在需要考虑一些细节。由于A是氧化剂,因此可以与各种燃料反应,在此过程中产生热量。但这不是爆炸的方式。典型的爆炸是由于分解过快。除了成为氧化剂外,一个分子还不稳定,并且可以分解,也就是说,分解成碎片。分解可以通过各种方式引起,但到目前为止,最常见的是热。这称为热分解(8)。 Next one can ask: Where does the heat come from? Again, in theory, there are many possibilities. But in practice, what usually happens is that a large, uncontrolled fire occurs nearby, and this proceeds to heat the AN.

如果燃烧的材料非常接近,则会出现另一个并发症。在正常的火灾下,热量上升。然后,如果上方有天花板,热气羽流在天花板上停止并侧向转动。例如,这就是火灾在木结构中传播的方式。但是一个有特殊财产。如果一堆被相邻的火加热,材料将被加热,最终将在169.6ºC(337.3ºF)融化。像液体一样熔融流动。像任何液体一样,它将向下流动并建立一个受重力控制的流动路径。如果这条流动的“河流”然后遇到一些可燃的木材,例如木头或纸板,则燃料会高糖化。高光点火是当该化学物质与其他某些材料接触时,某些非常反应性化学物质会发生什么,而无需任何外部点火源。 Thus, if there is a fire involving wood, cardboard, or other fuels next to a pile of AN, fire spread will be substantively accelerated. Instead of just spreading up-and-across, fire will also spread along a second path, that of the flowing AN “river.” The result can be a much faster fire development than might have been expected for the particular fuel that is burning.

Ammonium nitrate is primarily used in two industries: as an ingredient for explosives-making and as a fertilizer in agriculture. For both applications, the substance is typically sold in the form of “prills,” which are small spherules of about 2 mm diameter. Chemically, the material is identical for both industries, though there are some physical differences, primarily in density and porosity, of the grades sold for explosives-making and for agriculture. But either grade is susceptible to explosion, including its most severe form, detonation. Detonation occurs when a reaction wave moves at a velocity greater than the local speed of sound in the unreacted material.

What might be surprising to individuals who do not work with AN is that it is not classified as an explosive, even though it can explode and these explosions can produce massive loss of life. The U.S. Federal government has a narrow definition (9) of what constitutes an ”explosive,” and AN is not classified as an “explosive” but, rather an “oxidizer.” This practice is the same worldwide, according to guidelines set forth by the UN (10), which specify that AN is classed as an oxidizer and not an explosive, unless the product contains combustible material in excess of a certain limit value. This is for two reasons: (1) AN is a less sensitive explosive than TNT or RDX. This means it requires significantly more energy to be put into the material to initiate an explosion. However, once an explosion is proceeding, this limitation will not offer much solace to the victims. (2) Classifying AN as an explosive is strongly resisted by the agricultural industry, since this would make it more difficult for them to use AN as a fertilizer. This, however, is also a poor reason, since a very similar product, calcium ammonium nitrate (CAN) is available for fertilizer use which shows no significant risk of explosion (11).

Médard(7)在他的评论中得出结论,没有发现纯粹,未加热的纯粹爆炸的案件。另一方面,在实验室研究中,很容易通过大量污染物混合来爆炸(8)。但是,这种污染只是在现实中不会发生。(It is sometimes claimed that the large explosion of AN which occurred in 2001 in Toulouse, France, was due to contamination. However, Guiochon (12), the world’s leading expert on decomposition of AN, found instead that the actual cause was due to a buried, unexploded bomb which detonated beneath the factory). What is inarguable is that the governing cause of AN explosions has always been uncontrolled fire.

其他方面

自贝鲁特爆炸以来,我收到了有关爆炸事件的毒性危害的疑问。爆炸是由材料非常快速分解引起的。分解中涉及的化学反应是复杂的,众多8。原则上,硝酸铵的分解会产生一些可能有毒的反应产物。这些不仅包括硝酸和氨,还包括氮的各种氧化物。在很大的浓度下,其中任何一个都会有毒,甚至可能是致命的,但是爆炸效应使这些物质分散得非常广,并且不会在任何特定位置积聚。因此,尽管可以获得痕量读数,但不可能有任何幸存的人会暴露于有毒化学物质的有害浓度水平。例如,在西部(TX)灾难中,许多与仓库不够近的人受伤,其中许多人住院。但是受伤主要是钝性创伤(来自掉落的物体)或飞行玻璃。没有任何因化学中毒引起的伤害的病例。 One might also ask about the dangers of being exposed to unreacted prills of AN. Here, again, the danger is very modest. AN can be an irritant, especially to mucous membranes, and would be toxic if ingested in sufficient quantities (13), but the latter seems highly improbable. Thus, while there are numerous extremely serious concerns about AN explosions, toxicity is generally not one of the primary concerns.

Conclusions

硝酸铵是一种化学物质,可能是一种非常危险的化学物质,但仅在某些情况下。与任何爆炸性物质一样,它可以被现有的爆炸反应引爆。但是,实际上,最可能的危险是来自火。如果不受控制的火灾会撞击储存的硝酸铵,则该材料可能会爆炸。安全外卖需要尽可能广泛地传播:

请勿将硝酸铵转移到无法安全处理材料的任何存储设施上。存储设施的主要要求是该结构是不可燃烧的,并且没有可燃的商品或可燃结构靠近存储设施,因为这种情况可能会导致无法控制的曝光火灾。


尾注

1. Babrauskas,V。,“储存或运输中硝酸铵肥料的爆炸是可预防的事故”,J.危险材料304,2016,134-149。

2. Freitag,J。K.,的Fireproofing of Steel Buildings,威利,纽约,1899年。

3. Babrauskas,V。,“西部,德克萨斯州硝酸铵爆炸:监管失败”,J.消防科学35,2017,396-414。

4. Babrauskas,V。,“根据新的危险材料代码,消防员会更安全吗?”,188金宝搏是正规吗168:11,2015年11月,66-70。

5.西施肥公司的火与爆炸(15例死亡,260多人受伤),报告2013-02-I-TX,美国化学安全与危害调查委员会,华盛顿,2016年。

6. Babrauskas,V。,Ignition Handbook, Fire Science Publishers/Society of Fire Protection Engineers, Issaquah, Washington, 2003.

7.Médard,L。A.,Accidental Explosions,2卷,埃利斯·霍伍德,英格兰奇切斯特,1989年。

8. Babrauskas,V。和Leggett,D。,“硝酸铵的热分解”,火与材料44、2020、250-268。

9. Code of Federal Regulations, 49 CFR 172.101 Hazardous Materials Table.

10.关于危险货物运输的建议。模型法规。卷。1,联合国,2019年。

11. Babrauskas,V。,“德克萨斯州西部的硝酸铵爆炸:本来可以避免的灾难”,”火与材料42,2018,164-172。

12. Guiochon, G., “On the Catastrophic Explosion of the AZF Plant in Toulouse, September 21, 2001,”8th全球过程安全大会AIChE,休斯顿,德克萨斯州,2012,737 - 759。

13. Wexler,P。,编辑,毒理学百科全书,3rd编辑,学术出版社,伦敦,2014年。

Vyto Babrauskas,Ph.D., earned degrees in physics and structural engineering and a Ph.D. in fire safety. As a researcher at the National Institute of Standards and Technology, he developed devices to measure the heat release rate of products and developed a computer program for modeling the development of room fires. He founded a consulting firm in 1993 and provides fire safety science expertise to fire investigation and litigation. HisIgnition Handbook被广泛用于消防服务,他有两本书即将出版:电火和爆炸Smoldering Fires。他目前位于纽约市,在那里他隶属于约翰·杰伊刑事司法学院。

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