You are currently browsing the category archive for the ‘Chemical Industry’ category.
This post has been updated. Th’ Gaussling, 6/4/16.
If you work with chemicals at the level of chemist in a production environment, chances are at some time in your career you’ll be called upon to help decide when a material is too hazardous to use in manufacture. It can be in regard to raw materials or as the final product. Your organization may have protocols or institutional policies or memories relating to certain classes of substances. Some companies, for instance, will not use diethyl ether in its processes. Others may require hydrocarbon solvents *absolutely* free of BTX. Some companies are so fastidious about worker exposure that the faintest whiff of solvent constitutes a breach. One world class company I know requires R&D chemists to include a process hazard analysis, review, and an inspection for all R&D reactions performed in the hood. Whatever the company, most have fashioned some kind of boundary as to what is permissible to have on site and what isn’t.
Large chemical companies tend to have large EH&S departments with well established SOP’s and protocols with regard to personal protective equipment (PPE) and the measurement of occupational exposure to substances. Larger companies may have an OSHA attorney on retainer and staff members specializing in regulatory compliance.
One might suppose that smaller chemical companies may not have the depth of hazardous material experience that the larger companies have for many reasons. Smaller companies may have smaller capital equipment and a smaller staff. But smaller companies may have a greater organizational freedom which can lead to a great variety of projects. A great variety of projects often means that a great variety of materials are used on site. As such, a smaller company might very well have considerable expertise in a wide variety of chemical substances and, consequently, a wide variety of hazards.
While a smaller chemical company may have considerable expertise in handling its hazardous materials, it may be lacking in infrastructure for administrative controls and regulatory compliance. A wise CEO watches this aspect as closely as the actual operations.
Whether large or small, eventually a company has to draw the line on what hazards it will bring on site. The chemist has some very sober responsibility in this regard. Through the normal ordeal of process development, the diligent synthesis chemist will find the optimum path from raw material to product. All synthesis consists of the exploitation and management of reactivity. But there is always the “deal with the devil”. In exchange for a useful transformation, properly reactive precursors must be prepared and combined. A mishap with a 1-5 liter reaction on the bench top is messy and possibly an immediate threat to the chemist. But that same reaction in a 50 gallon or 5000 gallon pot can turn into the wrath of God if it runs away. The chemists judgment is the first layer of protection in this regard. All process chemists have to develop judgment with respect to what reagents, solvents, and conditions are feasible. Economics and safety come into play.
A runaway reaction poses several kinds of threats to people, equipment, and the viability of the company. There is the immediate thermokinetic threat stemming from the PV=nRT, meaning that energy can be dumped into PV work leading to the high speed disassembly of your equipment. A prompt release of heat and molecules kicked into the gas phase may or may not be controllable. Especially if the runaway leads to non-condensable gases. A runaway has a mechanical component in addition to the chemical action.
An runaway may cause the reactor contents to be abruptly discharged. Several questions should be answered ahead of time. Where do you want the contents to go and what are you going to do with it once it is there? Catchpots and emergency relief systems are common and resources should be invested there.
A question that the wary chemist must ask is this: What if a cloud of my highly useful though reactive compound gets discharged into the air or onto the ground? Do the benefits of this reagent outweigh the downside costs? Even if a release is not the result of a thermokinetic disaster like a runaway, explosion, or fire, a simple release of some materials may be consequential enough to require the evacuation of a neighborhood. Once your materials have left the site in the form of a cloud or a liquid spill and you make the call to the fire department, you have lost control of the incident. Even if nobody gets hurt or exposed, the ensuing “regulatory compliance explosion” may knock you down.
A chemical process incident can have mechanical consequences, chemical release issues, and the matter of fire. Substances that are pyrophoric have automatic ignition problems that may be surprisingly easy to deal with, especially if they are liquid. Liquid transfer systems can be inerted easily and pyrophoric liquids can be transferred airlessly and safely. Pyrophoric solids are another matter. There are few generalizations I can make about pyrophoric solids. Inert solids pose enough handling issues without having the added complication of air/water sensitivity. All I can say about pyrophoric solids- waste or finished product- is that you will need solids handling equipment, a big supply of LN2 and procedures for passivating hot filter cakes. Production glove boxes and Aurora filters are particularly useful. Also required is a space on the plant site where you can open up a container and let the contents burn if needed. If air gets into a container of pyrophoric solids, it’ll begin to get hot. That is when you need to have an open spot where it can smolder or ignite harmlessly and not bring the facility down. Crowded industrial parks are a bad place for such material handling.
When designing a chemical handling space, it is important to think about what happens in a fire. Flammable liquids are under the constant influence of gravity and will run to the low point on a floor. The question you must to ask beforehand is this: Where do I want the burning liquid to go? There are good choices and poor choices. Preferably a stream of burning or flammable liquid should run away from evacuation pathways and exits as well as anywhere other hazardous materials or combustibles may be contained. To some extent this is moot because indoor spaces should be covered by a fire suppression system. But outdoor spaces may be problematic in regard to crowding of a tank farm and drums and cylinders.
Burning pools of organic liquids radiate considerable energy per sq ft per sec (power in Watts). The temperature of nearby objects will rise rapidly to the flash point and the ceiling spaces will accumulate smoke and hot gas. Drums and cylinders filled with flammable liquids or gases will eventually overpressure and release their contents adding to the mayhem. The release can be in the form of a BLEVE or a flood of flammable liquid leading to a widespread pool fire.
There are resoures available to quantitate the risks of such releases. The American Institute of Chemical Engineers (AIChE) is well organized and provides much literature on the topic of chemical plant safety. In particular I am thinking of Dow’s Chemical Exposure Index Guide, 1994, 1st Edition, AIChE, ISBN 0-8169-0647-5. This handbook takes the reader through calculations aimed at estimating the risk and likelihood of chemical releases.
Also available is Dow’s Fire & Explosion Index and Hazard Classification Guide, 1994, Seventh Edition, AIChE, ISBN 978-0-8169-0623-9. This handbook supports the use of a quantitative risk analysis chart for the use of a risk and hazard index for generating numbers associated with process activities for cost/benefit analysis. It is well worth the addition to your library
Such flammable liquid scenarios can begin many ways. Forklift and maintenance operations are particularly rich in opportunity for a fire. The physical location of flammable liquid storage must be well thought out. Ideally a warehouse fire should not be allowed to spread to capital equipment locations. This helps to keep workers out of harms way and contains the magnitude of the financial disaster as well. Since most chemical plants seem to grow organically over time, unfortunate choices are usually made in regard to incident propagation.
One type of propagation incident can be ameliorated through the clever use of architecture. I am aware of one tragic incident where an explosion occurred in a processing space of a facility that had grown over the years by the addition of contiguous manufacturing and warehouse spaces. A rabbit’s warren of interconnected rooms and hallways accumulated over time. At the moment of the reactor explosion, the room and adjacent spaces were badly damaged by the blast overpressure as you’d expect. However, since the building was interconnected the overpressure propagated throughout many other distant spaces and delivered considerable structural damage to the facility. Overhead doors were bent outwards and windows and man doors blown out. Extensive damage may have been avoided by the simple expedient of providing open air walkways to separated buildings rather than enclosed hallways between adjoining areas. Of course, the benefit of this depends on the who, what, where, when, and how, but eliminating pathways for a blast wave is a cheap and easy way to start.
When is a substance just too hazardous? This is fundamentally a business or policy decision. Ultimately, it is the responsibility of the organizational leadership to draw the line on the risks that are deemed acceptable. It is the ethical responsibility of those knowledgeable and experienced with the proposed chemistries to combine information with pragmatics to provide persuasive feedback to the decision makers in charge.
There are plants that routinely manufacture nitroglycerine, phosgene, chlorine, phosphine and HCN. Workers spend their careers in these places. Most risks can be abated by properly engineered processing and packaging. It really comes down to personal choice. Is that ammonium perchlorate plant that just offered me a job operated safely? These reactive and/or energetic materials all have properties that lead to demand for their use. Somebody is going to supply that demand. We chemists have to look inward and then act with our eyes wide open and our heads on a swivel. Myself? I wouldn’t work in a nitroglycerine factory, but I’m glad that someone does.’
[Added 6/4/16 by Th’ Gaussling] I happened to go back to this post and in doing so read a comment by “Bob”, which you can see in the comment section below. Here is a copy
“I actually believe that as a society should keep the safety rules relaxed a bit in academia. Academia, for better or worse, is our national chemical research institution”
So underpaid grad students, postdocs and staff working at a univeristy are less human, and less deserving of safety than their for profit brethren?
That’s diabolical Mr. Gaussling. Pure evil incarnate. For whose gain do you sacrifice their lives?
I want to address this now better than I did back then. To Bob I say this: Everyone has a right to a safe workplace. Academic institutions as well as industrial operations must use best practices in regard to worker safety. This is axiomatic. Plainly I did not articulate my contention as well as I could have. I will do so now.
We have to assume that junior chemists are likely grow to be senior chemists in an organization. The role of a senior chemist in industry for example, may be quite varied through her/his career. A senior chemist who has stayed in the technical environment will almost unavoidably have been confronted with a large variety of questions in regard to circumstances and outcomes relating to hazardous materials and tricky reactions. Moreover, a senior chemist is likely to have been promoted to a level that also involves supervision, the drafting of SOPs, work instructions, MSDS documents, emergency planning, laboratory design, etc.
In my view, a senior chemist as described above has an ethical and moral responsibility to coworkers, plant operators, material handlers, and customers to oversee chemical safety. A chemist at any level has a responsibility to make known to all involved what dangerous circumstance might arise with any given chemical operation. Either in relation to the hazardous properties of substances that may be released in mishandling, or in regard to hazardous processing conditions that can lead to danger.
I’ve used the word hazard(ous) and the word danger(ous). We need some clarity on this. If you Google the words and stop with the dictionary definitions you will be left with the shallow notion that they are synonyms. If you dig deeper, say at the website of the Canadian Centre for Occupational Health and Safety (OSH), you will find a definition of “hazard” that I find particularly useful. To wit:
A hazard is any source of potential damage, harm or adverse health effects on something or someone under certain conditions at work. [italics mine]
The same fuzziness in definition exists for the word danger(ous) as well. A definition I prefer is below:
A dangerous occurrence is an unplanned and undesired occurrence (incident) which has the potential to cause injury and which may or may not cause damage to property, equipment or the environment. [italics mine]
This definition is borrowed from the University College Cork, Ireland (UCC). I believe this is a good definition and it readily sits apart from the definition of hazard above.
The key difference is that a hazard is any source of potential of damage … under certain conditions.. whereas danger is a condition brought on by an unplanned or undesired occurrence. Next, lets consider these terms in the context of chemistry.
On the shelf in the fire cabinet is a glass bottle of phosphorus oxychloride, properly sealed and segregated. As the POCl3 sits on the shelf in the cabinet, I would argue that it is only hazardous. If, however, you pick up the bottle and in walking to the fume hood drop it causing it to break and spill the contents in the open, you’ve caused a dangerous situation. It’s an imminent threat to health and safety.
Conversely, let’s say that you carried the bottle to the hood, used it, then returned it to storage without incident. In the reaction the POCl3 is consumed and in the workup the residual acid chloride is quenched by water. Congratulations! You have taken a hazardous material, used it safely, passivated the actives during workup, and eliminated at least the acute hazard relating to POCl3.
In the first situation, a hazardous material was mishandled and became dangerous. In the second situation, the hazardous material was handled properly, consumed, and residuals passivated. In this case a hazardous material was used safely and to positive effect.
Seem trivial? Well, it’s not. This difference in meaning leads to a confusion that is especially acute among the non-chemist population. But my point leads to the question of how students are taught to use hazardous materials.
I spoke of relaxing safety requirements in academia. An example of such a thing might be the use of diethyl ether. This useful solvent is banned outright in some chemical manufacturing operations across the country owing to the flammability. Even in their R&D labs. This is corporate policy handed down by those responsible for risk management, not scientists. In some industrial labs, woe is he who has an unexpected occurrence like a boil-over or a spill.
I believe that Et2O should remain in academic research labs for both the research value and for the development of valuable lab experience by students and postdocs.
You learn to handle hazardous materials by having the opportunity to handle hazardous materials.
Ether is only a simple example of what I’m trying to communicate. In order for chemists to graduate as experienced scientists with working familiarity in the properties of substances, they must have experience handling and using a large variety of substances, many of which may be substantially hazardous. And by hazardous I mean much more than just toxic. A substance may have a reactive hazard aspect that is a large part of it’s utility. To safely handle substances that pose a reactive hazard, a chemist needs to have experience in using it. And killing it. The chemist must try to gauge the level of reactivity and modify the use of the substance to use it safely. If you’ve made or used a Grignard reagent you know what I mean. Expertise in laboratory chemistry only comes through direct experience.
Hazardous reactive materials do useful things under reasonable conditions. Non-hazardous, unreactive materials find great utility in road and bridge construction.
If we regulate out all of the risk by eliminating hazardous materials in academic chemistry, what kind of scientists and future captains of industry are we producing? What we can do is to put layers of administrative and engineering protection in the space where the hazardous transitions to the dangerous. Academic laboratory safety is promoted by close supervision by experienced people. Limits on the amount of flammables in a lab space, proper syringe use, safe quenching of reactive residues, proper use of pressurized equipment, and a basic assessment of reactive hazards present in an experiment will go a long way to improving academic lab safety. Experienced people usually have a trail of mistakes and mishaps behind them. If we corporatize the academic research experience to a zero risk condition, we may kill the goose that lays the golden egg.
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.
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.
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.
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.
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.
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-
- existing items of commerce unencumbered by composition of matter or process claims.
- available in a grade suitable for direct use.
- unencumbered by import restrictions, law enforcement watch lists, and relevant EPA restriction lists.
- TSCA and REACH listed already.
- those free of problematic isomers.
- those not requiring tight fractional distillation to purify.
- free of explosaphors like azide or nitro esters.
Your costs are best contained if your product-
- does not require enantiomeric purity or is not subject to facile isomerism affecting the specification.
- does not require more than one protection/deprotection scheme.
- does not require tight fractional distillation for final purity.
- does not require bulk high pressure chemistry (shops that can do this are limited).
- is air stable.
- is soluble enough in process solvents to maximize space yields (if it is, say, <10 wt %, batch costs will start to get high).
- does not require solvent changes in a process unit operation.
- is amenable to parallel synthetic strategy.
- does not require serious chilling of the reaction mixture (say, < -20 C).
- has been screened for real purity requirements rather than those based on the desire for tidiness.
- can be isolated by a simple Buchner filtration rather than, say, a centrifuge or other more elaborate solids isolation scheme.
- 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.
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.