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DBL%20Hendrix%20small.png College chemistry, 1983

Derek Lowe The 2002 Model

Dbl%20new%20portrait%20B%26W.png After 10 years of blogging. . .

Derek Lowe, an Arkansan by birth, got his BA from Hendrix College and his PhD in organic chemistry from Duke before spending time in Germany on a Humboldt Fellowship on his post-doc. He's worked for several major pharmaceutical companies since 1989 on drug discovery projects against schizophrenia, Alzheimer's, diabetes, osteoporosis and other diseases. To contact Derek email him directly: derekb.lowe@gmail.com Twitter: Dereklowe

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In the Pipeline

« The Drug Business: A Turbulent Future? | Main | More on T2, and Degrees »

September 18, 2009

175 Times. And Then the Catastrophe.

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Posted by Derek

I noted this item over at C&E News today, a report on a terrible chemical accident at T2 Laboratories in Florida back in 2007. I missed even hearing about this incident at the time, but it appears to have been one of the more violent explosions investigated by the federal Chemical Safety and Hazard Board (CSB). Debris ended up over a mile from the site, and killed four employees, including one of the co-owners, who was fifty feet away from the reactor at the time. (The other co-owner made it through the blast behind a shipping container and suffered a heart attack immediately afterwards, but survived). Here's the full report as a PDF.
T2%20aerial%20shot.jpg
The company was preparing a gasoline additive, methylcyclopentadienyl manganese tricarbonyl (MCMT). To readers outside the field, that sounds like an awful mouthful of a name, but organic chemists will look it over and say "OK, halfway like ferrocene, manganese instead of iron, methyl group on the ring, three CO groups on the other side of the metal. Hmmm. What went wrong with that one?"

Well, the same sort of thing that can go wrong with a lot of reactions, large and small: a thermal runaway. That's always a possibility when a reaction gives off waste heat while it's running (that's called an exothermic reaction, and some are, some aren't - it depends on the energy balance of the bonds being broken versus the bonds being made, among other things). Heating chemical reactions almost invariably speeds them up, naturally, so the heat given off by such a reaction can make it go faster, which makes it give off even more heat, which makes it. . .well,, now you know why it's called a runaway reaction.

On the small scales where I've spent my career, the usual consequence of this is that whatever's fitted on the top of the flask blows off, and the contents geyser out all over the fume hood. One generally doesn't tightly seal the top of a reaction flask, not unless one knows exactly what one is doing, so there's usually a stopper or rubber seal that gives way. I've walked back into my lab, looked at the floor in front of my hood, and wondered "Who on earth left a glass condenser on my floor?", until I walked over to have a look and realized where it came from (and, um, who left it there).

But on a large scale, well, things are always different. For one thing, it's just plain larger. There's more energy involved. And heat transfer is a major concern on scale, because while it's easy to cool off a 25-milliliter flask, where none of the contents are more than a centimeter from the outside wall, cooling off a 2500-gallon reactor is something else again. Needless to say, you're not going to be able to pick it up quickly and stick it into 25,000 gallons of ice water, and even that wouldn't do nearly as much good as you might think. The center of that reactor is a long way from the walls, and cooling those walls down can only do so much - stirring is a major concern on these scales, too.
T2%20agitator.jpg
What's worth emphasizing is that this explosion occurred on the one hundred seventy-fifth time that T2 had run this reaction. No doubt they thought they had everything well under control - have any of you ever run the same reaction a hundred and seventy-five times in a row? But what they didn't know was crucial: the operators had only undergraduate degrees (Update: here's another post on that issue), and the CSB report concludes that the didn't realize that they were walking on the edge of disaster the whole time. As it turns out, the MCMT chemistry was mildly exothermic. But if the reaction got above the normal production temperature (177C), a very exothermic side reaction kicked in. Have I mentioned that the chemistry involved was a stirred molten-sodium reaction? Yep, methylcyclopentadiene dimer, cracking to monomer, metallating with the sodium and releasing hydrogen gas. This was run in diglyme, and if the temperature went up above 199C, the sodium would start reacting energetically with the solvent. Update: corrected these temperature values

Experienced chemists and engineers will recognize that setup for what it is: a black-bordered invitation to disaster. Apparently the T2 chemists had experienced a few close calls in the past, without fully realizing the extent of the problem. On the morning of the explosion, the water cooling line experienced some sort of blockage, and there was (fatally) no backup cooling system in place. Ten minutes later, everything went up. In retrospect, the only thing to do when the cooling went out would have been to run for it and cover as much ground as possible in the ten minutes left, but that's not a decision that anyone usually makes.
T2%20reactor.jpg
Here you see part of the company's reactor vessel, which ended up on some train tracks 400 feet away. The 4-inch-wide shaft of the agitator traveled nearly as far, imbedding itself into the sidewalk like a javelin. My condolences go out to the families of those killed and injured in this terribly preventable accident. The laws of thermodynamics, unfortunately, have no regard for human life at all. They cannot be brushed off or bargained with, and if you do not pay attention to them they can cut you down.

Comments (60) + TrackBacks (0) | Category: Chemical News | Safety Warnings


COMMENTS

1. cookingwithsolvents on September 18, 2009 8:44 AM writes...

Such a tragedy. It's fortunate more people weren't hurt; I'm surprised diglyme could take even 350 C w/ molten Na. . .

What were they after w/ that temperature? Just a faster reaction? Na metalation/Cp cracking can be done at MUCH lower temperatures (like HALF what they were using) eg: Organometallics, 2003, 22 (4), pp 877–878 DOI: 10.1021/om0207865 (yeah I know they didn't want to filter off/isolate the NaCp etc etc in an industrial reactor. I'm just talking reaction temperatures.)

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2. Curious Wavefunction on September 18, 2009 8:47 AM writes...

Wow. I too don't remember reading about this. That javelin thing looks scary as hell. Sometimes I feel it's a miracle things in the lab don't usually blow up. But we clearly take a lot for granted.

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3. processchemist on September 18, 2009 8:59 AM writes...

A predictable tragedy. If you fill with diglyme and sodium metal a 2400 gal *used* reactor for high pressures, tested for 1200 psig in *1962*, you're planning an accident. And the specialized firm that refurbished the reactor, with a downgrading to 600 psig, FITTING THIS BEAST WITH A 4' RUPTURE DISK, is also responsible.
Obviously the market price of the product we're talking about did not justify the heavy investments needed by large scale hazardous chemistry.

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4. Harry on September 18, 2009 10:05 AM writes...

Holy Crap! That's scary as hell, considering that the company I worked for back in the 80's did some process development work on that very product.

I vas only very tangentially involved with it, but the name stuck in my head. I don't remember that the reaction temperatures that we used were that high, but it is close to 20 years ago.

If I'd been scaling something like that up, I believe I'd have done some thermal stability studies (DSC, etc.)

I'm going to go back and look at the report. What the heck were they using as a coolant?

The same company I'm talking about had a massive explosion in the 60's which sheared all the bolts on a clamp-top pfaudler 500 gallon reactor. The head and agitator drive ended up in a parking lot about 300 feet away and the bottom half was driven into and through a 6 inch concrete pad so far that only about one foot was above ground.

No one was injured, luckily. That was something like the 500th batch of this product they had made.

The management tried to warn the other company that made this product. They shrugged it off, saying that they had made this stuff for 10 years with no problem. Two years later they had a similar explosion that killed two employees.

Moral: 1. ALWAYS listen to safety warnings!

2. You NEVER know everything about what you're doing.

My $0.02, YMMV

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5. retread on September 18, 2009 10:16 AM writes...

Ah yes. explosions. The sort of thing that gives chemistry a bad name. However, my freshman chemistry prof (the late Hubert N. Alyea) LOVED them, and each lecture seemed to feature at least one (sometimes unannounced ?? unplanned ??). It was a chemical Haydn surprise symphony (but not on an industrial scale)

Diazomethane anyone?

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6. alig on September 18, 2009 10:20 AM writes...

The temperature was actually 350 F (~200 C) with the violent reaction of sodium w/ diglyme happening at 390 F (~220 C).

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7. Anonymous on September 18, 2009 10:27 AM writes...

I believe that temperatures reported are in Fahrenheit, not Celsius. This means that they will be a bit more in line with people's expectations (#1, #4).

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8. Rhenium on September 18, 2009 10:29 AM writes...

Nice write up of a very sad story.

I remember hearing about this when it happened, the report will make interesting reading for my advanced inorganic chemistry course.

This I think is what happens when research chemists (of which I am one) think they are industrial chemists alas.

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9. Harry on September 18, 2009 10:31 AM writes...

Ahhh thanks Alig, that makes more sense. I haven't been able to get the report downloaded, but I was wondering how you'd use water cooling on a 350C reactor (Sure- pressurized water loop and all that, like a nuclear reactor, but not something I've seen in many chemical plants. Heck you could hook that to a steam turbine and recover power. ).

We ended up passing that one off to another company that had equipment that was better suited for high-pressure chemistry to finish the process development.

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10. Mike on September 18, 2009 10:40 AM writes...

Harry,
The incident you describe sounds like "Automate Yellow 96 Dye. Was that what you were referring to? That was also investigated by the CSB, and the results are posted on the web site. That was also a horrible incident. From the way the CSB descibed it, it was a barely controlled reaction, also.

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11. Harry on September 18, 2009 10:54 AM writes...

No, Mike this was the sulfonation of nitrobenzene using SO3.

In this case, as nearly as we could tell, the SO3 feed ran ahead of the reaction, and unreacted SO3 pooled in the bottom of the reactor until it got deep enough to contact the agitator blades. At that point it was dispersed throughout the reaction mixture, and produced a violent exotherm.

This happened about 1968 as I remember. I wasn't working there at the time, but I talked to a lot of the people that were. I do remember that it shook my Mom's house about a mile away.

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12. Curt Fischer on September 18, 2009 11:13 AM writes...

Thanks to Derek for an intelligent and sobering analysis of this tragedy.

However, I really don't understand this line:

the operators had only undergraduate degrees

How is that at all relevant to the disaster? I have a Ph.D. in chemical engineering from a top-ranked university, and I feel comfortable saying that the typical chemical engineering grad school experience would include absolutely no training or experience -- nothing -- that would qualify one to run a dangerous, large-scale operation such as an industrial-scale synthesis of MCMT.

Sure, if your advisor happened to be one of the very few chemical engineering professors who uses large scale equipment, or who specializes in "high-reactivity" materials, maybe you'll learn a thing or two, but not near enough to run off and start up a 2500 gallon prep of MCMT. And anyway, those types of professors and labs are a small minority.

Grad school is not the place to learn proper industrial hygiene or safety for industrial-scale processes. Nor, in my view, should it be.

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13. Derek Lowe on September 18, 2009 11:23 AM writes...

You're right about grad school not being the place to learn such things. But perhaps it could be a place to learn that you don't know them, and that there are things you should know before running a process like this.

What strikes me about this incident is that there was apparently no effort at all to investigate this reaction by any sort of calorimetry beforehand, and not much attention seems to have been paid to the "close calls" that they'd experienced before.

The report says that one of the owners had tried this chemistry out on a one-liter scale (!) several times before they scaled up, and had reported no problems. Something should have tipped these people off that this is horribly insufficient preparation to scale a molten sodium reaction up by a factor of 10,000, and maybe a grad school accident or two might have done the trick. . .

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14. processchemist on September 18, 2009 11:28 AM writes...

"In the first reaction step (called metalation), the process operator fed a mixture of methylcyclopentadiene
(MCPD) dimer20 and diethylene glycol dimethyl ether (diglyme) into the reactor. An outside operator
then hand-loaded blocks of sodium metal through a 6-inch gate valve on top of the reactor"

Poorly designed process in poorly designed plant.
The worst part is the "charge all and heat" thing. The right way to conduct such a reaction is a controlled feed of one of the the reactants (cyclopentadiene) at the required T, but who cares about such details, as long as you can deliver your product...
I'll say nothing about the hand-loading of blocks of sodium metal in a 2500 gal reactor...

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15. philip on September 18, 2009 11:51 AM writes...

I have a PhD now but a number of years ago, when I had only a BS, I read a remarkable book first published in 1917 by D'Arcy Wentworth Thompson (http://en.wikipedia.org/wiki/D%27Arcy_Wentworth_Thompson) called "On Growth and Form". It's mostly about how flies can walk on walls and I can't. But the take home message was that as one scales dimensions linearly, surface area increases by the square and volume increases by the cube. And that has a lot of not immediately obvious consequences. What this means is that if you scale up any exothermic reaction (volume), you need to be very worried about getting rid of the heat (area). I always thought this was what chemical engineering was all about.

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16. Hap on September 18, 2009 12:05 PM writes...

Grad school probably isn't the place to learn large-scale process chemistry (particularly with the lack of emphasis on safety), but it's a really good place to learn what you don't know, and perhaps how to tell what you don't know you don't know. Of course, the owners who tested the reaction should have had some idea of the questions to ask.

This might be one problem with smaller places - the temptation to cut corners is high (because there is little financial margin for error and perhaps less to lose), and the institutional memory and experience that would make clear why those corners shouldn't be cut doesn't exist. The CSB reports are a start for correcting that.

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17. Harry on September 18, 2009 12:11 PM writes...

processchemist@ #14

Couldn't agree more! I don't have time to type it here today, but I was witness to a "feed it all in and add the catalyst" runaway that emptied a 1,000 gallon reactor in about 2 minutes.

This was being run by a couple of chemists who'd developed the process in the lab and had leased our pilot plant to run some scale-ups in a 50 gallon reactor. They then convinced their management to lease the 1,000 gallon reactor to make a large run for their potential customer.

Needless to say, that 'ole surface/volume ratio problem in scale-up caught up to them.

No one hurt, two chemists literally scared white, and a (belated) DSC study that confirmed a side reaction kicking in at about 40C above the normal reaction temperature.

Funny thing, the reaction worked beautifully, if you added two reactants and the catalyst, and fed the third one, controlling the reaction temperature with the feed.

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18. processchemist on September 18, 2009 12:39 PM writes...

@Harry

This case should hit the texbooks, because we're talking about a reaction with emission of flammable/detonating non condenable gases (H2). I learned from the wisests old school industrial chemists that you don't size a chlorination or a dehydratation with SOCl2 on the size of your largest glass lined reactor, but on the size of (and the cooling capacity in) your largest scrubber.
Don't ask me why, but some years ago I was forced to assist a medchem guy that was starting to perform an hydride reduction at -15°C in a 20 l glass reactor (solvent: diethyl ether!). The quench was planned next day, but I was unable to attend. My (written) recomendation was " Don't adjust the dropwise addition of water on the inner T, but on the speed of the hydrogen emission". Two days later I found some broken glassware: about 8 liters/minute of a mixture of H2 and diethyl ether vapours from a 29/32 ground joint connected to a laboratory bubbler did the job. Luckily no fires, explosions, injured people.

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19. Harry on September 18, 2009 1:02 PM writes...

Process chemist- one of my mentors (a very wise old-timer of a chemical engineer) once told me: "You're running this reaction in a one liter flask with a 29/42 joint for a vent to your condenser. If you scaled it up to a 500 gallon reactor with a 6 inch opening for a vent to the condenser, it would be about the same as venting this one liter through a pinhole."

I really don't think that chemical engineering (and chemistry) education talks nearly enough about scale-up. On the other hand, sometimes I don't think that a lot of people are in a receptive state of mind until they've witnessed or participated in a near-disaster or two. That tends to focus the mind wonderfully.

I read about a case a few years ago where someone blew up a 500 gallon reactor simply by neutralizing with sodium carbonate too quickly. Funny- he'd never had that problem in a beaker.

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20. You're Pfizered on September 18, 2009 1:05 PM writes...

If you poked around development organizations, you'd probably find that chemical operators oftentimes don't even have college degrees. Some do, but a fair percentage are simply trained in those particular jobs without extensive chemical knowledge.

It's the engineers/scientists behind the chemistry and equipment that are supposed to be determining what should happen when the process is put together. An operator merely follows an SOP for the bulk process.

Once a massive reaction starts to go supernova, all the Ph.Ds in the world would have a hard time from stopping it.

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21. milkshake on September 18, 2009 1:18 PM writes...

a friend flooded the plant floor with a barrel of dimethylsulfate one night in manufacture of piroxicam, because they did not inspect their giant reactor setup properly and left a drain ventil of the reagent storage reservoir accidentally open. Their boss came in the morning and asked - whats this oily stuff on my shoes?...

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22. RTW on September 18, 2009 1:38 PM writes...

I have to take some exception to your statement that the the operators had "only undergraduate degrees". As being a contributary cause. As if anyone with an MS or PhD would have known better. I have a BS in chemistry and would have known better. OK. I went to a school which was heavily invested in Engineering. Even a LOWLY undergraduate in chemistry at that institution would have had some chemical engineering rub off on them.

Since the training of these operators is not spelled out I can only speculate that they probably had a BA or BS, in a science more than likely not an ACS Acredited degree in Chemistry, certainly no Chemical Engineering degree.

A Chemical Engineer at the plant should have and probably would have gone through an analysis of the Thermodynamics of the process before scaleup and production, and made sure that the proper safety and shutdown/quench procedures where in place. Even if this plant could not afford to hire a full time Chemical Engineer to monitor these processes, they should have at least hired a consultant to come in and evaluate their systems periodicaly.

These small plant specialty companies take shortcuts, are usually complacent after a while with the process, and don't stay vigilant.

I have seen plenty of advertisements around these plant operator positions, few specify a chemical engineering degree with practical experience. (Couldn't afford them if they did) However good plant operators learn to do it right or soon leave such a company, because they feel their saftey is at risk... I have known a few of these folks too. Proper regulation and inspections are the key. When was the last time OSHA cam in there. And do they look at the process or just general safety standards? You can be compliant on the later, but woefully unprepared for the former should it go south on you.

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23. Just passing through on September 18, 2009 1:44 PM writes...

philip on September 18, 2009 11:51 AM wrote:

I have a PhD now but a number of years ago, when I had only a BS, I read a remarkable book first published in 1917 by D'Arcy Wentworth Thompson (http://en.wikipedia.org/wiki/D%27Arcy_Wentworth_Thompson) called "On Growth and Form". ... What this means is that if you scale up any exothermic reaction (volume), you need to be very worried about getting rid of the heat (area). I always thought this was what chemical engineering was all about.
I also recall D'arcy Thompson's work from freshman or sophomore undergraduate days over 40 years ago. I'm not a chemist, or anything related. But I am very surprised that any engineer, chemical or otherwise, would fail to make such a fundamental consideration when scaling up (or scaling down) almost anything.

There are very simple reasons that there are no seagoing mice or flying elephants in nature. Those who scaled up this reaction apparently didn't make those rudimentary considerations.

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24. RTW on September 18, 2009 1:54 PM writes...

OK - I see from the C&EN article the owners were a chemist and chemical engineer. Seems to me the chemical engineer should habe been held accountable (assuming he was the one that survived). There should have been a backup plan in place for the loss of coolant. Pehaps a secondary system, or a method of quickly quencing a reaction. He should have done a thermodynamic study of the chemisty, and known that a runaway reaction could take place. Like I said short cuts.

When I was running reactions on large scale, up to 10L, I use to keep dry ice and even liquid nitrogen near by to rapidly cool something should it end up having an induction period. People thought I was nuts for always sticking a Thermometer in all my reactions and distillation pots!

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25. FormerMolecModeler on September 18, 2009 2:40 PM writes...

Did any legal action result from this? This would be classified as an ultrahazardous activity and thus subject to strict liability.

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26. dumbchemist on September 18, 2009 2:56 PM writes...

Oh OK, so you have to have a graduate degree to understand why this is dangerous?

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27. CMCguy on September 18, 2009 3:30 PM writes...

To the point about chemistry education my perspective is that current Universities rarely teaches what is needed in the real world, especially in US compared to EU counterparts. As far a PhDs the system is such a vast majority are prepared to go in a academia positions, which of course are few, and those that go to industry are often ill prepared. While transition to medchem or other research is doable it typically entails much expanded learning to someone who can contribute. Going into process/manufacturing is significantly harder because is greater void to fill. Safety typically is the first lesson (ate least place I have been) but I have seen far to many fresh PhDs come in with attitudes that "they could do anything" and would not listen to older chemists and engineers much less "lowly operators" (who IMO often are very knowledge if asked). One would hope there would be exposure and awareness to industry life provided during undergrad and grad school (although this Blog is a good source and maybe should be assigned as homework) however I see little of that happening.

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28. Fp fan on September 18, 2009 3:31 PM writes...

Ck out the structures in the report for the MCMT - they have drawn a sigma bond to a vinyl carbon - not the pi complex. Must not have been proofread by a chemist.

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29. anonymous on September 18, 2009 4:48 PM writes...

# 15 “I have a PhD now but a number of years ago, when I had only a BS, I read a remarkable book”.....

Is the fact that you have a PhD now but only a BS when you read the book relevant to your point? Perhaps, now that you have a PhD, you no longer have a need to read books because you already know everything?

Actually, I also agree with with RTW (#22) and take offense to statements like “only undergraduate degrees”. I’m guessing that the owners who tried it out on a 1L scale and probably directly supervised those operators actually did have their PhDs and probably a post doc with EJ Corey to boot. A Post hole Digger is not a substitute for intelligence, experience and certainly not for wisdom. But it does seem to provide a wonderful foundation for unbridled arrogance.

To quote Mark Twain, ‘I never let my schooling get in the way of my education’. I read In the Pipeline because Derek and the accompanying commentary tend to be intelligent and genuinely insightful and we share a common profession. Nevertheless, that underlying insipid prejudice towards non-PhDs that ebbs and flows (at times) through these pages as inexorably as it does our industry really tends to nauseate me.

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30. DrCMS on September 18, 2009 5:54 PM writes...

As a PhD chemist with 15 years experience in scale, up currently working in a Contract Manufacturing company I can say in my experience all the new/recent graduates and post-graduates in Chemistry and Chemical Engineering I've met have known very very little about how to safely scale up a new process. Most seem to think you just go bigger and bigger till it goes wrong and then step down in scale to the last one that worked. I will add that the PhD chemists are the least worst at it as they have experience of carrying out unknown lab chemistry. Most undergraduates only get to run reactions that are well known and relatively safe. Which in my experience makes the undergraduate chemists and chemical engineers dangerous if not supervised well and re-educated how to work safely. To those people who do not like me telling the truth about undergrads tough s**t. Universities should teach about safety much more than they currently do but the problem is that the academics do not know much about real process safety.

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31. Philip on September 18, 2009 6:00 PM writes...

To # 29 from # 15

My point was that I was exposed to the information that would make me very careful when scaling up long before I got a PhD. Your sense of "underlying insipid prejudice" from my post is not warranted.

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32. Timothy on September 18, 2009 9:08 PM writes...

If the other students in my organic lab were any indicator of typical undergraduate chemists, I'm afraid for you industrial guys.

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33. Jose on September 18, 2009 11:55 PM writes...

"Yep, methylcyclopentadiene dimer, cracking to monomer, metallating with the sodium and releasing hydrogen gas. This was run in diglyme"

"hello, Mr. Gasoline, I'd like you to meet Mr. Match!"

Staggeringly scary. I had some (med-chem) coworkers do a scaleup in a glass reactor that utilized AlMe3 in staggeringly huge quantities. The addition funnel cracked *before* all the pyrophoric evil was added, so no-one was immolated, but it was a damn close thing.

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34. Anonymous on September 19, 2009 8:58 AM writes...

I knew more chemistry when I finished grad school, but when it comes to lab safety, I picked up a lot of bad habits there that had to be undone when I got a job in industry. If you see a guy with no gloves or goggles and an open can of soda in the fume hood next to his experiment, you're probably looking at a grad student!

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35. Mark on September 19, 2009 3:33 PM writes...

1. I invite all to read the full CSB report (77 pgs)
2. Do the other commercial producers of MCMT (MMT)use a different reaction scheme?

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36. bearing on September 19, 2009 9:14 PM writes...

I have a 1997 BSChE and a 2004 PhD in chemical engineering and I'm wondering what they mean by the "reactive chemical education" courses that they say only 11% of universities now include in undergraduate chemical engineering education. Would my undergraduate organic chemistry lab course plus my (non-lab) kinetics course count as the sort of "reactive chemical education" they are referring to? Or would this be something in addition to that?

It's tempting, always, to blame any apparent lack of practical knowledge among newly minted chemical engineers on the craze for all things "nano-info-bio-eco" that is supplanting basic fundamentals of unit operations like distillation, drying, etc.... but if the undergraduate chemical engineering programs are cutting back on reaction kinetics, perhaps it's even worse than I thought.

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37. bearing on September 19, 2009 9:30 PM writes...

Hmm, to answer my own question, the full report doesn't refer so much to "reactive chemical education" courses as to course components on "reactive hazard awareness." I'm sure now that none of my undergraduate OR graduate ChE courses contained any formal component on "reactive hazard awareness," although lecturers would occasionally tell anecdotes about such things, or perhaps assign a problem with a how-high-will-the-pressure-go theme.

I probably got more safety education in my co-op experience. We had some formal lab safety training in graduate school, but all I remember of that was the video they showed us with pictures of people with nails embedded in their eye sockets.

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38. Jose on September 19, 2009 10:39 PM writes...

After reading the whole report, I am shocked. You can run an insanely reactive process on 9,000L scale in a bargain basement 50 yr old reactor, with no process validation, no scale-up studies, no calorimetry, no redundant systems, no safety controls, and *no preventative maintenance*? Not to mention no concerns about random unexplained thermal spikes when a 4 INCH rupture disk (which couldn't vent a pop bottle) and a municipal water supply are the only things keeping you from catastrophe?

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39. DrCMS on September 20, 2009 4:53 AM writes...

@Jose - Go to the CSB and read the reports on the Sythron, MFG, CAI/Arnel, Bethune Point etc etc. There are lots of detailed investigations that show lots of companies big and small don't have a clue how to run chemical reactions safely.

@bearing - "reactive chemical education" is NOT something the vast majority of undergraduates have. Post graduates might have a tiny bit but not much more. The university system does not include it because you don't need to know it if you stay in academia and that's all they know about.

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40. Harry on September 20, 2009 7:48 AM writes...

People keep mentioning the reactor. I think that the reactor was not really a factor in the genesis of the accident, except as far as the grossly undersized vent retained the pressure.

I'm reasonably sure that the cooling system plumbing and its controls were not part of the reactor, and were added on-site.

Also- there is not a shred of evidence in the report that indicates a structural failure in the reactor until the internal pressure most likely got well above the original pressure rating. Note that the pressure in the test cells was well over 1000 psig when they ruptured. Based on the notion that failure strength is 2+ times working pressure I'd say that in the T2 reactor pressure may have exceeded 2500 psig before it let go. In fact, the strength of the reactor probably contributed to the intensity of the explosion.

My $0.02

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41. bearing on September 20, 2009 9:29 AM writes...

@DrCMS:

@bearing - "reactive chemical education" is NOT something the vast majority of undergraduates have. Post graduates might have a tiny bit but not much more. The university system does not include it because you don't need to know it if you stay in academia and that's all they know about.

"That's all they know about?" I suspect it depends a bit on the university. My undergraduate years were spent at a state university chemical engineering department that mostly feeds industry (only two members of my ChE graduating class that I know of, including yours truly, went directly to grad school). Several of our professors had worked in industry before changing to an academic career.

I wonder if it doesn't have more to do with simply the limitations of time in the ChE curriculum. When I was an undergraduate, ChE's were already the major on campus with more credits required to graduate than any other major. The school cut out non-core requirements left and right -- the technical writing requirement, for example, was in place when I was a freshman and had disappeared by the time I was a senior. General education requirements (foreign language, history, etc) had already been cut to a bare minimum. I honestly think ChE is going to have to become a 5-year bachelor's program if it's not either to become simply a vo-tech discipline stripped of the humanities component that makes it a true university discipline, or the sort of thing that requires students to go on to a master's degree to become hire-able.

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42. bearing on September 20, 2009 9:32 AM writes...

As an aside, what P.E. signed off on this setup? Crazy.

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43. RM on September 20, 2009 3:03 PM writes...

anonymous @ 29: "I read In the Pipeline because Derek and the accompanying commentary tend to be intelligent and genuinely insightful and we share a common profession. Nevertheless, that underlying insipid prejudice towards non-PhDs that ebbs and flows (at times) through these pages as inexorably as it does our industry really tends to nauseate me.

I agree with your first sentence, but what I'm disliking of late is the tendency for commenters to seize upon some small comment by Derek or another commenter, and then jump up and down shouting about how it's indicative of some prejudice.

Sure, a graduate education is no proof of competence, but we don't need dozens of posts whose only content is harping on Derek about it.

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44. DrCMS on September 20, 2009 3:06 PM writes...

@bearing

You said "I suspect it depends a bit on the university"

Well I've met students from quite a few different ones and have yet to meet a NEW graduate who has much clue about process safety. You say you went to a state uni with ex-industry profs yet earlier you admitted you got no process safety training at uni. As far as I can see it does not get taught well if at all at uni.

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45. bearing on September 20, 2009 3:27 PM writes...

After I discussed the full report with my husband (BSChE 1996, and unlike me, gainfully employed in industry, at a facility that takes safety very seriously) we concluded that the owners' lack of formal education in reaction hazard analysis was a total red herring. If you read through the full report, you'll find that they enlisted consultants who recommended certain safety precautions -- and then they did not follow those recommendations. They also had experience on the laboratory scale that would have tipped them off to the potential for runaway exotherms on the full scale.

My husband (the gainfully employed industrial chemical engineer) fingers "lack of a safety culture" as the likely primary factor in this particular accident. Reading the full report, I would have to agree. If the owners of company hires experts to tell them how to operate safely and comply with regulatory requirements, and then they ignore those recommendations, I am willing to bet that increased knowledge of chemical reaction hazards is not going to have helped them.

Safety culture is not about specific bits of information; those are necessarily applicable only to narrow circumstances. What is needed is a general approach to safety systems of all kind, one that emphasizes things like "don't take shortcuts; don't disable your safety controls; follow lockout/tagout procedures; if you see someone doing something unsafe, call them on it..." It's sort of a broken-windows theory....Small things like that lead to bigger things like, "Don't remove emergency operating procedures from your operators' documentation" (actual, acknowledged contributing cause to this accident). Are the operators encouraged to think about potential hazards and report them to management? Does the management take safety suggestions seriously? In the case of this plant, it looked very much like that wasn't the case, that the owners had a very cavalier "can't happen to us" attitude. This isn't a problem of not enough chemistry education.

As a commenter above alluded (re the soda can in the lab hood), graduate school engineering and chemistry laboratories are poor schools of safety culture. When was the last time you heard of any research group having regular safety meetings, or of a P.I. opening a group meeting with the question, "What have we done this week to make the lab safer?" or celebrating so many hours without lost-time incidents? That's standard practice in my husband's research lab workplace. Never once saw that in graduate school. I still remember discovering jars of hydrofluoric acid stored on their sides in a drawer in my lab (shudder).

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46. DrCMS on September 20, 2009 3:48 PM writes...

@bearing
I disagree having read the full CSB report and others I think the owners of T2's lack of knowledge of reactive chemical safety meant they could not recognise the problems. Lab scale experiments of the kind they ran prior to the scale up would not give them the info they needed about the knife edge they were on. They did not have the training or background to understand what the hell was going on. They did not decide to cut corners knowing how dangerous it was. They did not have a "lack of a safety culture" they just did not understand process safety at all. Any corners they cut were cut because they did not think were important. They were wrong and paid with their lives and the lives of others.

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47. Sean on September 20, 2009 4:22 PM writes...

Derek, your explanation of a run away reaction is pretty funny...

Was there a break down in regulations that allowed this to happen?

I am unsure if regulation is the answer, but are there measures in place to prevent this from reoccurring? or is it up to the employer and employees to know the risks?

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48. bearing on September 20, 2009 4:45 PM writes...

@DrCMS: "I disagree having read the full CSB report and others I think the owners of T2's lack of knowledge of reactive chemical safety meant they could not recognise the problems."

-- But did you see in the report that a design consultant informed them of the need to run a hazard and operability (HAZOP) analysis? And that if they had hired a consultant to run the HAZOP analysis, that analysis would have included the thermodynamics and kinetics of the reaction as well as the limitations of the heating, cooling, and pressure-relief systems? They did not perform this analysis.

In the end, they WERE ignorant of the reaction's capabilities, but the cause of that ignorance is not ultimately something that was lacking in the engineer-owner's undergraduate education. No undergraduate education can possibly anticipate all runaway-reaction hazards, after all. They were ignorant because they were willfully ignorant -- because they were too cheap to pay for HAZOP analysis that they knew, on the advice of their own hired consultant, that they needed to have.

This is not an undergraduate education problem. This is an attitude problem.

It wasn't the only incidence revealed in the report where the owners were known to have information about safety precautions they should take, and they failed to act on it. They also did not follow the advice of the consultant that they hired to advise them on regulatory requirements or on basic OSHA safety requirements.

A stronger background in chemistry wasn't going to fix these guys' attitudes.

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49. milkshake on September 21, 2009 3:09 AM writes...

It is probably a good thing that Ecotane (aka MCMT) is not used more widely as a gasoline additive in US - not only is burned manganese not nice on the engine, but inhaling Mn oxide dust is known to cause slow and irreversible Parkinson-like CNS damage.

As for these guys blowing themselves up - they clearly were not qualified and equipped for what they undertook: basically there was no safety margin in their process and they had no clue. In any major industrial disasters, there is a whole chain of serious errors that all contribute, beginning with the eagerness of the operators to fool themselves into believing that they have everything under control, and saving money in the wrong places.

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50. Steve on September 21, 2009 7:00 AM writes...

While I do not understand a single thing you folks just said, I live in Jacksonville, Fl. Was downtown that day and heard this explosion, a distance of at least 6-7 miles. I was right on the St. Johns River and the explosion occurred very near the river on the north side of town, somewhat near the airport/zoo for those of you who have driven Interstate 95. Thing freaked out the northside and downtown of Jacksonville.

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51. Jonadab the Unsightly One on September 21, 2009 7:48 AM writes...

Wait, they had an exothermic reaction going, involving a product intended for use as a *fuel additive*. They had this great big exothermic reaction going in a reaction container larger than a man, and the cooling went out, and so they just left the reaction going and stayed in the building? Have I got that straight?

Huh. My only chem class was in high school, but that REALLY doesn't sound like a good idea to me.

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52. Joe on September 21, 2009 7:53 AM writes...

video or it didn't happen

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53. DrM on September 21, 2009 6:19 PM writes...

I didn't know there was a city called "Florida" in India?

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54. ChemEBoss on September 22, 2009 7:17 AM writes...

Do the words 29CFR1910.119 meaning anything to these folks?

I agree with Bearing #48. A properly conducted PHA (HAZOP) with LOPA would have resulted in recommendations that can minimize these types of events. But you have to invest in the safety culture and understand the risks you are taking. If Mgmt feels the investment in people (safety) is not worth it, all bets are off. I interviewed with a company like this one and ran far and fast... when told they reuse the antimony acetate floor sweepings...

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55. Risk-Safety on September 22, 2009 5:01 PM writes...

Managing reactivity hazards is a fairly complex task. I doubt the education of the operators would have prevented the disaster. The important things to look into are hazard identification and risk mitigation measures in place

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56. seb on September 24, 2009 3:05 AM writes...

I don't work. I'm a witch, watch out. Imagine Imperial Japan in the samurai times. You won't even think. Much less express an opinion.

This is not a mouthful. It's called CP'. That's right, "See-Pee-Prime". Although we can do experiments with CP, CP' is made in large quantities, as you can see, so the organometallic chemistry is little affected, except that now you can see that it is. Reminds me of Bosche-Haber, when they thought it was okay to mix ammonia and nitrates, or whatever it was they did when Germany said the word and Bosche reluctantly agreed, and he killed dozens of his workers. That one, not the bombardments. Read the book, "The Alchemy of Air".

So, I'm taking organometallic chem from Bill Evans in 1983 and i'm asking UCI to readmit me. They said no, that UCSD kicks me out and I'm UCSD's problem. I go to UCSD, finish my degree, and lo and behold Evan's lab catches fire and burns down the building. Permit me a laugh.

If you like C&E News on fires, that one is in there. Now this. Again, I laugh.

Laughing, you must agree, means something, in the light of arson, which its not. Check the predictive power of being ahead of time.

The developer of the ChE processes that give us gasoline was way ahead of time, building reactors way outsized. I think he was a witch, too. He had too good of a record. it went too long before it blew up. He beat the odds.

So, theoretically, how does that methyl group figure in the explosion? Is the stuff more or less likely to blow with that methyl on there?

Evan's lab blew from distilling diethyl ether. What proportion of academic labs still do it that way vs. ion-exchange? There are hundreds.

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57. Harry on September 24, 2009 6:49 AM writes...

Re # 56.

Huh???? I've read that comment twice, and it makes less sense the second time around.

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58. Allen on January 20, 2010 6:26 PM writes...

I have been intimately involved for many years with the MMT production process on a commercial scale.

From my experience with this process and understanding of proper safety procedures, T2 Labs critical failure was not having a mechanism in place to interogate the safety of the process after each batch reaction. For example, during several of their batch runs, they observed brief temperature excursions which they never bothered to investigate, "since the respective incident was not repeated the next few runs"!

The other probelem was, although they understood what happened if the process was run right, they did not have a clue as to how catastrophic their process was if things went wrong. This information is absolutely necessary because it prompts the adoption of appropriate safety precautions. In the case of T2 Labs, they strung together three reactions in a one pot process, and for this type of process, the chances of a catastrophic runaway go up exponetially due to potential cross contamination by species whose chemistry is unknown in a large scale reactor.

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59. Riley Corron on January 9, 2013 9:50 AM writes...

Very interesting details you have mentioned, thanks for putting up.

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60. Marlon Wendelin on March 29, 2014 1:38 PM writes...

I live in a 4 unit apartment building [and my] apartment [is] the one with bedbugs... We had someone come treat the apartment... I got the receipt and was told that I was responsible for covering all the expenses of all the apartments-it came to around $1300. (Single mom, working poor) The treatments started late June and the last visit was in August. The problem is this, the bed bugs have returned to the exact same spot as they were listed on the receipt (which had no warranty if they returned). [T]he exterminator... says that it's all my fault... I got some diatomaceous earth [and treated the room]. I'm trying to do everything right. My daughter's bed is metal but the bottom has wood slats. I'm guessing these bugs may have lived in the slats, but after the first spraying, I purchased a whole new set of slats and am living in fear of the same problem. We also have encasements on everything. Her mattress has an encasement on it with a cover over the encasement. Her pillow has the same thing. I have encasements on my mattresses. We did the little cups around the foot of her bed and put the earth in there (this time, when I did it myself).My questions are: do you think the wood is keeping the bedbugs in? And how long before she can sleep in her bed?

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