Category Archives: Chemical Industry

CSB has released final reports on Macondo Disaster and the West, TX, explosion

Leave a reply

The US Chemical Safety Board has approved and released the final report on the Macondo /Deepwater Horizon  blowout and explosion of 4/20/10 in the Gulf of Mexico. The report is in two volumes and does include an animation of the sequence of events. I have found the CSB animations to be particularly helpful in understanding the key features revealed by their investigations.

The CSB recently released their final report on the ammonium nitrate fire and explosion in West, Texas on 4/17/13. A few months after the release of the final report the ATF announced a reward of up to $50,000 for information leading to the arrest of person or persons responsible for the industrial fire and explosion that killed 15 people.

If the forensic aspects of industrial accidents is of interest to you, I’d recommend having a look at the CSB website. Knowledge of various initiation and propagation modes in past industrial accidents is useful for those of us trying to prevent initiating events on our own sites.

Does the oil & gas market have a brain?

Leave a reply

In the course of my professional society memberships I receive an email newsletter called API SmartBrief from the American Petroleum Institute. An article caught my attention today. The API newsletter blurb read-

“Senators say methane rule will have unexpected impact“

“The Obama administration doesn’t understand the full economic effect of new federal rules meant to cut methane emissions from oil and natural gas production, according to a letter signed by Sen. David Vitter, R-La., and colleagues. “Given that so many of our communities are being impacted by current market conditions, [italics added for emphasis] any new regulations impacting oil and natural gas should be based on reliable, transparent data that is devoid of any political considerations,” read the letter sent to Environmental Protection Agency Administrator Gina McCarthy.” 5/23/16

This API summary is sourced from HoumaToday.com.

The alarm expressed by Vitter, API, and unnamed others struck me as amusing. The methane rule will have unexpected impact. Golly Mr. Wizard, tell us more. Naturally, API is beating the drum for petroleum interests. It is their charter, after all. Vitter bemoans the cost impact on workers and communities in his state and, to be sure, that is his job. Thus, the interpenetrating political-industrial partnership seems aligned in their opposition to possible rule making by EPA. Alles ist in Ordnung.

The funny part is that the current market condition cited by Vitter and, I would suppose, API, is the result of years of delirious drilling and hydrofracturing of oil and gas deposits. Perhaps someone of credible standing mentioned that a bubble was forming and that maybe, just maybe, we’ll end up with a glut. If such a voice did arise, it was not widely cited, at least to my knowledge.

So, this self-inflicted malady of excess supply and low prices has crept up on this colossal industry with it’s legions of swingin’ d**ks leasing and drilling methane glory holes. Boom and bust is not new to big oil. Not unexpectedly, OPEC failed to cooperate and reduce their oil production, the greedy bastards. King coal is staggering like a large sauropod after an asteroid impact. And even more dismaying to big petro is that solar, wind, and who knows what else is creeping upwards in power production and taking market share.

With all of this recklessness with oversupply, could it really be that big oil is bad at basic price collusion? Shiver me timbers!

My point is that using a self-inflicted market down-turn to justify reckless disregard in furthering large scale contamination of the atmosphere is a malfeasance of the first magnitude. If the free market gave birth to such an awful turn of events as an oil and gas oversupply, how can we expect the invisible hand of the market to steer us away from certain ecological ruin through destruction of the biosphere from accelerating consumption and advancing overpopulation?

The market is like the male sex organ. It has no brain and seeks only one thing- More.

 

 

Winter Road Trips

4 Replies

Two trips in the last month. First to New Orleans to attend the specialty chemical trade show called Informex. We didn’t have a booth in the expo this year. It hadn’t served a useful purpose for many years, truth be told. I stood in for a sales guy who couldn’t attend. Nice to be back in the field.

Informex is an odd menagerie of buying, selling, drinking, feasting and spy craft. For the first time I was invited to a gathering with a balcony above Bourbon Street.  The hosts supplied ample liquor and Mardi Gras beads so we tossed them from the Royal Sonesta balcony with careless abandon to disinterested stragglers on the street below. No flashing or outrageous behavior to be seen, regrettably. The Sonesta is a 4 star hotel they say. What 4 stars mean on a zero star place like Bourbon Street is beyond me.

The Informex experience varies depending on whether you are a buyer or a seller and if you make a good buy or sale. If you are a buyer, there are lots of free dinners at Antoine’s and the like. If you are a seller, you buy lots of expensive dinners.

There was a lot less trade show junk as in years past. Vendors would give away logo festooned trinkets to ingratiate themselves to passersby (or more realistically, their children). A waste of money usually.

I will say that it is possible to consummate deals, agreements, or understanding in a solid face-to-face sit-down with another party. Far faster information exchange and superior to email or video conferencing. Often you can talk to a decision maker in the form of a CEO or sales manager and shake loose a logjam that has been holding up progress.

The other trip was to Long Island for a campus visit. We stayed in a 3.5 star hotel in a 1 star location. The Long Island Railroad (LIRR) was indispensable for getting into Manhattan. The taxi’s in Nassau county apparently don’t have meters- ask about the fare first. The high point was taking in a Broadway show, “If/Then” starring Idina Menzel at the Rodgers Theatre on West 46th Street. Great show. Menzel has some pipes, that’s for sure.

A less than great show was the Empire State Building experience. The view was nice, once you get to the 86th floor. The in between was an expensive and kitschy meandering from a B-grade SkyRide to a walk through the self congratulatory “museum” on the 80th floor. I won’t discuss my raspy encounter with security while trying to sit on the floor.

Magnesium still surprises a fellow

Leave a reply

I have spent some time researching basic magnesium chemistry. Not anything synthetic but more safety and thermochemically related. I am not able to give a lot of particulars motivating the study, but I can say that one should consider that nitrogen over activated magnesium may not be as innocent as you think. While lithium is widely known to react with nitrogen gas to form a passivating nitride layer, the reaction of dinitrogen with magnesium is rarely encountered.

Activated magnesium residues from a Grignard or other magnesium metallation reaction may self-heat to incandescence under a nitrogen atmosphere in the right circumstances. Activated residues left isolated on the reactor wall or other features in a nitrogen blanketed reactor during an aqueous quenching procedure may self-heat to incandescence. In the presence of reactive gas-phase components like water vapor in nitrogen, activated metals can self-heat over an induction period of minutes to hours or longer.

Many metals, including magnesium and aluminum, can be rendered kinetically stable to air or humidity by the formation of a protective oxide layer. Once heated to some onset temperature by a low activation reaction, penetration of the protective layer by reactive gas composition can occur, leading to an exothermic reaction.

Performing a “kill reaction” or a quench of a reactive metal at the bench or at scale is always problematic and requires the skill and close attention of the process chemists and operators. I guess what I’d like to pass on is that nitrogen is not an innocent spectator in the presence of finely divided, activated magnesium. Humid nitrogen can support a combustion reaction to produce nitrided magnesium once preheated to an onset temperature.

If you mean to kill any reactive residues, it is important to apply the quenching agent in such a manner that the heat generated can be readily absorbed in the quenching medium itself. A good example of a quenching agent is water. Often a reactive must be killed slowly due to gas generation or some particular. Adding a quenching agent to a solution or slurry by slow feed or titration may be your best bet. If you have another vessel available, a feed to a chilled quenching agent will also work.  Dribs and drabs of water on a neat reactive material will lead to hotspots that may be incendive.

On the 4-Methylcyclohexanemethanol Spill

1 Reply

The fouling of public waters in West Virginia by 4-methylcyclohexanemethanol (MCHM) is regrettable and my heart goes out to all of the families whose lives have been and are disrupted by the spill. In my judgment the descriptions of the substance found in Wikipedia and ChemSpider seem very evenhanded given what is known presently about the toxicology of the substance. The SymBioSys LASSO numbers found in ChemSpider are reassuring in the sense that the structure of MCHM does not line up well with the receptors in the list. The low scores are suggestive of substrate mismatch with these receptors based on calculation. That is a good thing. So is the relatively high flash point of 80 °C.

There are several uses of this substance. At the large scale its use has been patented as a frothing agent for coal beneficiation (US 4915825). That patent is now expired. It is useful for separating coal particles from inorganic mineral particles. Other uses include the preparation of ester derivatives to produce plasticizers either as a stand alone ester or, as a listing in SciFinder shows, a hydrophobic co-monomer.

From what I have heard in the media, the secondary containment failed, allowing material to discharge into the nearby river. This is easy to figure out. A visual inspection by plant EH&S should have noticed failure of the secondary containment during periodic inspection and flagged it for repairs. The US Chemical Safety Board is investigating and will eventually publish a finding.

It seems to me that the people of WV must be willing to publically demonstrate en mass if anything is to change there. The lack of regulatory oversight on facilities like this is not surprising. It is exactly as intended by the power brokers of the state.

Lithium Fires

Leave a reply

Ran into an interesting recommendation on fighting a lithium fire in Joshi, D.K., et al, Organic Process Research & Development, 2005, 9, 997-1002.

In addition to the usual admonitions on the handling of a reactive metal like Li, they warned that water, sand, carbon dioxide, dry chemical, or halon should not be used. Rather, they suggest dry graphite or lithium chloride instead.  This seems quite reasonable to me, having reacted both silica and CO2 with magnesium powder in chemical demonstrations in a previous life. If Mg will reduce SiO2 and CO2, then hot/burning lithium ought to be reactive as well.

A similar recommendation is given in Furr, A.K. CRC Handbook of Laboratory Safety, 5th Edition, p. 299, ISBN 0-8493-2523-4.

Chemical Process Development

2 Replies

Lots of semi-batch process development and safety work going on in my lab. We use our reaction calorimeter for a variety of studies now. Naturally we want to know about energy accumulation with a given feed rate or any unforeseen induction or initiation problems in a reaction. We can also home in on recommendations for safe feed rates of reactants into a reaction mass.

What I am beginning to learn from the RC1 work is that running a reaction at low temperature is frequently done for sketchy reasons. Unless there are selectivity or side product issues, you really have to question why the reaction is specified to be run at low temperature. I think some of it comes from habit gained in grad school.  Low temperature may introduce dangerous situations with abrupt initiation by accumulation of unreacted reagents. Or it may lead to overly long feed time with the associated costs of added plant time and labor.

There are reagent incompatibilities like nBuLi in THF above – 15 C or so. But you’ll find that MeTHF is a bit more tolerant of temperature than is THF.

The precise temperature management capabilities (Tr) of an RC1 including the ability to lock on a temperature or precision ramping gives insight on solubility questions or on freezing points. The instrument also provides heat capacity data for engineering calculations. it is a very useful apparatus.

Suggestions for future customers

2 Replies

Being a grey haired chemist in the manufacturing field, allow me to make a few suggestions regarding the design of custom chemicals. If you as a customer would like to have a custom product that has minimal cost, maximum quality, and minimum variability, please consider the following attributes of an ideal custom synthetic chemical product.

Boundary conditions must be set on my comments:  custom or proprietary product; produced under batch or semi-batch conditions; non-pharma-food-neutriceutical related.

To the greatest extent possible the raw materials for your product are preferably-

  1. existing items of commerce unencumbered by composition of matter or process claims.
  2. available in a grade suitable for direct use.
  3. unencumbered by import restrictions, law enforcement watch lists, and relevant EPA restriction lists.
  4. TSCA and REACH listed already.
  5. those free of problematic isomers.
  6. those not requiring tight fractional distillation to purify.
  7. free of explosaphors like azide or nitro esters.

Your costs are best contained if your product-

  1. does not require enantiomeric purity or is not subject to facile isomerism affecting the specification.
  2. does not require more than one protection/deprotection scheme.
  3. does not require tight fractional distillation for final purity.
  4. does not require bulk high pressure chemistry (shops that can do this are limited).
  5. is air stable.
  6. is soluble enough in process solvents to maximize space yields (if it is, say, <10 wt %, batch costs will start to get high).
  7. does not require solvent changes in a process unit operation.
  8. is amenable to parallel synthetic strategy.
  9. does not require serious chilling of the reaction mixture (say, < -20 C).
  10. has been screened for real purity requirements rather than those based on the desire for tidiness.
  11. can be isolated by a simple Buchner filtration rather than, say, a centrifuge or other more elaborate solids isolation scheme.
  12. can be isolated by simple distillation.

It is important not to underestimate the cost of excess purity. A process may afford 96 % absolute purity on first isolation with say, 1 % solvent and 3.5 % side products or starting materials. The cost of taking this to >99.5 % is often very high in plant time and in product losses from added operations. Maybe you can get by with 98.5 % purity with some constraints on certain contaminants for your application.

Products and their intermediates may be designed in the early development stage to have properties that aid in low cost manufacturing without too much alteration of utility. For example, consider not using an n-octyl ester group in favor of 2-ethylhexyl ester. There are many structural motifs that derive from large scale items of commerce. Products that are strictly polyaromatic with or without hetreroatoms, are zwitterions or salts, or have a large heteroatom-to-carbon ratio, often have organic solubility problems. Will a bit of aliphatic shrubbery in a side group enhance processability? Maybe. If it allows your vendor to have better process economics, that helps everyone.

Does the process require nitromethane as a solvent? Does it require an exotic PGM catalyst that is patented? Do you have to use a patented transformation in the scheme that requires pencil-necks from the University IP office to audit annually? If so, try to find a better way.

Well, it depends …

4 Replies

Getting technical people to offer insight and advice can range from simple to vexing. Following a recent purchase of an unusual type of spectrometer we found ourselves in need of advice regarding consumables and sample preparation. Going into this installation I believed, naively, that our set up to operate the new instrument would be eased by patient advice from the seller.  I was mistaken.

I could whine on about deficiencies in this or that, but instead I’ll get to my point. Consider the following exchange-

Q:  What sort of electrode should we use to run this mineral sample?

A:  Well, that depends.

Q:  It depends upon what?

A:  Well, it depends on the type of matrix you have and the concentration of the desired metals.

Q:  How do we decide on what kind of electrode to use?

A:  We do not have experience with that element or that matrix. And there are many kinds of graphite widgets, many for specific uses. The widget company did not return your email because they are small and would prefer to talk to their customers.

Q:  So, how do we get started?

A:  You’ll have to prepare bracketing calibration standards that match your matrix as closely as possible.

Q:  What can you tell us about buying or the preparation of calibration standards? Are there any special materials we can use as diluents or any preferred methods?

A:  There are no manufacturers of these solid calibration standards anymore. We bought out the inventory of the last one.

Q:  So we can compound our own standards at concentrations close to the spec of the inventory you hoarded bought out?

A:  Well, yes, I suppose. It depends on your capabilities ….

And on it went.  Eventually we extracted the information we needed and are moving forward.

Here is my point. Everything “depends”.  A little louder.  EVERYTHING DEPENDS. For crying out loud!  This is one of the fundamental theorems of life. We technical people have to get past this barrier when a questioner asks for help.

A few sentences of advice-

On the assumption that everything depends, offer a hint to the questioner in the form of a range of possibilities. Open with insightful examples or a recitation of common practices. Do not sit there, Sphinx-like, while the questioner sputters and struggles with finding the best questions. Offer some guidance by way of general performance boundaries.

The technical service folks we spoke with were very much in the quandary of Buridan’s Ass. In this fable, a donkey was in between two identically appealing piles of hay. In the end he starved to death because there was no good reason to pick one over the other.

In the case of the tech service folks, one pile of hay was to offer zero advice and make no errors. The other pile of hay was to offer frank advice and satisfy the customer. Having been in this position, I know that offering advice has it’s appeal, but it may be fraught with liability. Telling people how to run their equipment can have negative consequences- thus the reluctance to speak. But sellers are there to service their customers. They should use words and pictures to help their customers get started.

The Company Joules

6 Replies

We will soon have a new HEL Phi-TEC Adiabatic Reaction Calorimeter up and running. Hopefully this will help solve some nagging questions I have about the thermal stability of certain compounds. Time to maximum rate (TMR) is a useful parameter and ARC testing helps to find this value.

I have spent  a good deal of time with the Mettler-Toledo RC1 and have found it to be very useful in process development. There is a tendency for chemists to design exothermic reactions to start at low temperature and at perhaps some point raise the temperature to take the reaction to completion. The RC1 will indicate accumulation of energy in a vessel following a charge. By varying the temperature of the reaction mass and modulating the dosing rate it is possible to find a reaction temperature and feed rate that affords a steady state (or manageable, at least) output of power with minimal energy accumulation.

With the reactions I have been studying it has become apparent that sometimes a preference for low temperature (-30 C to 0 C) by the chemist may in fact be based on habit rather than need.

Naturally, the thermal picture is not the entirety of the problem. Product stability in the reaction mass and residence time at temperature play a role in how the process is configured. But a reaction calorimeter can help find threshold temperatures below which the reaction substantially shuts down.

The RC1 measures heat of reaction in Joules and power in Watts. After some time on the instrument one comes to view a reaction mass as a power generator or an absorber. Power is reported in Watts and is indicated by the magnitude of the deflection of the power curve from baseline.  Joules of energy are calculated from the area under the power curve.

The instrument has a calibration routine where it determines the Cp of the vessel contents. If you have the reaction mass, heat of reaction, and Cp, you can calculate the adiabatic temperature rise for a given dose of reactant. This is an extremely useful element in sketching out the safe operating parameter space of a reaction.

Safety is a political concept. Safety has no basis in physics. It is an artifact of anthropology. It is a fuzzy construct defined by a magnitude of “likelihood” and type of consequence individuals and organizations are willing to absorb to obtain a particular outcome.  But when you sit down in a meeting with thermokinetic data and solid interpretation, all of the stakeholders in a plant can brainstorm and home in on a fairly rational and agreed upon process profile. This is politics at its finest- data driven and substantially rational.