Category Archives: Science

Green Innovation Lag

It is not unusual for a long time to elapse between an initial customer inquiry and when commercial quantities of product are loaded on the truck and driven out the gate. I have seen it happen over 1 to 10 years, with 3 years being quite common. The chemical industry is not like the semiconductor business. The paradigm shift period seems much longer. In fact, any given chemical processing technology can last for a large part of a career or more. The last big chemical paradigm shift I have noticed is high throughput experimentation (HTE).  Maybe others have a more recent example.

Green chemistry is considered by many to be a new frontier of opportunity. To its detriment, many of us are unsure of what green chemistry really is and how to implement it in manufacturing. Realistically, for green chemistry to find wide acceptance, it needs to turn a profit or offer some kind of concrete advantage. Pollution avoidance is too abstract. For any new method or technology, there must be a payoff.

It seems simple. Reduce VOC emissions by using aqueous solvent compositions. Increase atom efficiency in transformations. Minimize persistant pollutants, organic or metal. Increase space yields, reduce consumables.  Green chemistry is not so easily demonstrated to the public and it may not be in the public domain. Your green technology may be proprietary, so the ballyhoo factor will collapse to zero. The processor may have to labor down the green path in silence.   

A process changeover to a green process may require many people in several companies to align to the change like compass needles to the north pole. A chemical process change must offer some kind of improvement that, by consensus, is meritorious. There is a good chance that the change will require notification of the customer and possibly even their permission. Customers often want a price concession when there is a process change so they can capture some of the value, so this may mean reduced sales volume and profits for the processor.

The customer may require that the proposed process change will be cause for a new validation of their customers product, in which case, the final user will also have to perform a validation.   In all likelihood, you are proposing a green change to a process that previously offered no problem to the downstream users.

Obviously, the time for green process implementation is at the very beginning of process development. The development chemist must have an existing toolbag of techniques, transformations, and reagents to choose from to go forward with implementation. The best way to get to this point is with curriculum change at the university level. Chemists need to have green chemistry awareness from the beginning of their training. Converting souls when they are already within industry is the hard way to do it.

Microscale labs in the undergrad experience maybe green for the university, but it is hard to see how it translates to the implementation of green technology in industry. The green revolution must come from textbooks that use green transformations in chemistry and engineering coursework. It must come from professors who weave it into their lectures and provide examples of such transformations and practices in the lab experience.

Chemists and engineers from such backgrounds must move into industry and become group leaders and managers. Only at this point will green chemistry become “normal” and expected.

Shermer’s “Mind of the Market”

Google has been posting a series of interesting talks by contemporary authors. This talk is by Michael Shermer, author of Mind of the Market, and editor of the popular magazine Skeptic. It is a lengthy 53 minute video, but I would highly recommend it. I think Shermer has a good grasp on the anthropology of our present world.

This is off-topic, but useful. This link gives a bunch of really good hints on how to save money for your start-up company.

Incident Attenuation in Chemical Plant Design

If you work in a location that handles or processes hazardous materials, eventually you have to come to grips with the matter of risk and accidents. It is possible to design procedures that prevent certain kinds of accidents and casualties.  It is possible to install devices and automated contrivances that can eliminate specific failures and the resulting cascade of multistage calamities that might follow.

Over time and with plenty of thought, a chemical plant can be fool-proofed to a large extent. But in the end, residual margins of safety depend on the man-machine interface. People have to undergo recurrent training and certain staff must be assigned to specialize in safety.

All devices have a failure rate. The rate may be small or large. A device may fail safely or not. Most chemical plants are, to a large extent, hand built. They are fabricated by skilled tradesmen who connect pre-fabricated parts to one-of-a-kind assemblies built on-site. In this way, expertise is captured from the plant designers, contractors, and the manufacturers of the installed equipment.  In the end though, it is up to the designers to assure that there is compatibility and some margin of overdesign in the finished facility.

While it is possible to assemble a facility from the very best equipment, the fascinating question of design for the attenuation of accident propagation is not often discussed, at least openly.  Accidents can usually be reduced to a few characteristic phases. They are initiation, propagation, and termination. 

An incident begins with an initiating event. Some release of hazardous energy is presented to the surroundings that may begin a propagation of undesired events. Events can propagate in series or parallel chains.  Hazardous energy can be electrical, chemical, or mechanical. The initiation is the tipping of a domino as a triggering event that causes the release of other hazardous conditions to ensue. Eventually, the propagation of the hazardous energy release is suppressed, extinguished, or simply exhausted in the termination phase.

One of the best ways of learning about the phenomenon of accidents is reading about them. A website worth visiting is the US Chemical and Hazard Investigation Board. It is useful for chemists and engineers to study the anlyses of the CSB and gain useful insight into the dynamics of chemical plant accidents.

It is possible to configure a chemical plant in such a manner as to attenuate the propagation of hazardous energy during an incident. In general, a large distance between reservoirs of potential energy is the easiest solution. Explosives manufacturers have known this for a long time. One well known German manufacturer of energetic materials has a manufacturing site spread over a large rural area and has built in bunkers with berms and trees to attenuate the propagation of shockwaves and allow flying fragments to land safely in an uninhabited area.  Fortunately, not many manufacturers have processes and products requiring this kind of design consideration.

Situations of “ordinary” risk magnitude do require some thought, however. Consider the storage of drums of flammable materials. Most companies that handle palletized drums of flammable liquids meet the minimal fire and insurance codes for the handling of these materials.

But consider this. What if a forklift driver spears a drum of solvent with his lift, and then in a panic, backs up and pulls the fork out of the drum resulting in a spill? At this point, policy and regulations are irrelevant. The only question is this-  Where does the liquid and the potential fire go?

Indoor storage of flammable materials requires fire suppression. Fire suppression is not the same as fire extinguishment. It is about knocking down the fire to a manageable level for emergency egress, to suppress the spread of the fire, and for firefighters to make some kind of attempt to extinguish the blaze. This is routine firefighter stuff.

What is less than routine, however, is the issue of BLEVE’s. I have written on this phenomenon previously.  Fire suppression is one thing, but BLEVE’s – Boiling Liquid Expanding Vapor Explosions- are quite another matter to deal with.

This is where a well designed facility with passive architectural features to attenuate the spread of hazardous energy can be helpful. An indoor BLEVE is virtually assured to accelerate the pace of a disaster.  So, in the planning phase of a plant, it is important to consider how energy release during an accident may propagate.  Drummed flammable liquids should be isolated from work areas and egress paths. This is pretty obvious to initial designers, but not necessarily years down the road during an expansion.

Consideration should be given to the anticipated direction in which energy is released. Where possible, energy should be released away from populated areas and away from major capital equipment. A fire in a materials storage area shouldn’t lead to an extended plant shutdown due to damaged process equipment. Segregation is key to plant safety and business viability.

Smoke is a potential killer and there are architectural tricks that can add provide slightly greater safety margins. Ceilings designed to collect and channel smoke out of the space could reduce the likelihood of suffocation of stranded workers and suppress the chances of a flashover. Smoke curtains properly placed can channel smoke away from hallways and the resulting spread.

Another concern is the fate of spilled flammable liquids in a storage area. Where should the spill go? Should the spill be concentrated in a small space or channeled to another space where a fire can burn with lower negative consequence? Nobody likes to pay for an overengineered warehouse, but fire resistant partitions in a solvent storage area can go a long way toward the isolation of a fire and attenuation of a larger scale calamity.

One major plant accident I am familiar with has a number of attributes that other operators would do well to consider.  A 750 gallon reactor explosion resulted in the complete fragmentation of the vessel.  A few pieces ejected from the hole in the roof were found lodged in the walls of neighboring structures off-site.  Fortunately, this reactor was in an enclosed space with no other reactors or stored hazardous materials. In one way, this accident was isolated due to passive attributes. However, the building space was interconnected to other spaces by a series of adjacent rooms and hallways. While fragmentation and fire damage were contained due to the happy fortune of isolation, the shockwave was able to follow all of the connected and enclosed pathways.  The connected pathways were a convenience to the workers, but this feature channeled a pressure wave throughout the entire facility, lifting the roof enough to damage large -remote- sections of it as well as badly damaging overhead doors and windows throughout the facility.

Take home lessons? 1) Leave open space walkways between production and storage buildings and the rest of the facility. Collateral damage is likely to be suppressed with this cheap, passive feature. 2) isolate and dedicate certain vessels to hazardous operations. 3) Store hazardous materials well away from processing areas. Storage and processing have their own hazards and a disaster in one area should not be allowed to propagate to the other.

The matter of flammable solvent storage and accident attenuation is only partially solved with enclosed flammable materials lockers. It seems to me that some research should be done to advance the level of best practices in this area.

Lunar Eclipse 2008

The eclipsed moon finally made itself visible only minutes from totality this evening. Through the gauzy haze the lopsided apparition loomed in the eastern sky. We pointed the 18 ” telescope at it, but with its narrow field of view we could only gaze at part of the moon at a time. With the haze and the low contrast, only washed out moonscape was visible. An eclipsed moon is best witnessed with the naked eye or from binoculars.

We found Mars and Saturn in open patches of the sky. Saturn was sharper than I’ve seen it in while. The rings and planet in sharp relief against the black velvet background. Titan and a few other moons were to be seen as well. 

A line of visitors queue around the dome and down the stairs to see the planets and M42, the Great Nebula of Orion.  We’re lucky this evening. The clouds parted and the wondrous sky was made visible.

Sentition and the Phenomenous Object

In his Seed article Questioning Consciousness, author Nicholas Humphrey asserts that if we are to understand the phenomenon of consciousness, we must begin to formulate better questions.  Humphrey has written on the problem of consciousness and has been be promoting some new vocabulary and arguments to address this challenge.

The basic question that people have struggled with is this: How does the brain elicit consciousness? Obviously, this is a very hard question to answer. It requires the brain to reason about its own function and within the very constraints of those brain functions.

Naturally people want to find a mechanistic picture and the notion that the brain is a processing system that accepts inputs and delivers outputs is normal. But outputs to what? Well, your consciousness- your eternal, first person, live on the scene, internal-telecast of stimulus and response.

Humphrey defines “Sentition” as real world brain activity. Presumably this includes the sum of electrical and chemical activity that operates within the brain’s distinctive architecture.  Humphrey goes on to define more language to describe our perception of sentition-

The real-world brain activity is the activity that I call “sentition.” In response to sensory stimulation, we react with an evolutionarily ancient form of internalized bodily expression (something like an inner grimace or smile). We then experience this as sensation when we form an inner picture—by monitoring the command signals—of just what we are doing.

Sentition has been subtly shaped in the course of evolution so as to instill our picture of it with those added dimensions of phenomenality. Sentition has, in short, become what I call a “phenomenous object”—defined as “something that when monitored by introspection seems to have phenomenal properties.”

While it may seem trivial, the definition of appropriate terms to describe key attributes of consciousness is critical to how we think about it. New terms may be better as they are not burdened with common usage that distract from the problem.

This article in Seed is not a seminal work. It is a short essay on consciousness and an introduction to some interesting ideas for hackers like myself who realize that the field is very significant. I believe that a comprehensive theory of consciousness is as important as the ToE the physicists are looking for- Theory of Everything.

That Pesky Brazil Nut Effect

The Brazil Nut Effect is a type of equilibration process that granular systems with a distribution of particle sizes will undergo. It occurs with agitation and proceeds in such a manner as to result in a final state with the center of mass as low as possible. The equilibrated state results in the larger particles migrating towards the top and the smaller particles filling the void spaces down low. According to the above Wikipedia site, certain container shapes can suppress or enhance this effect.

In the merchant chemical business, suppliers strive to provide customers with the maximum quality that is feasible.  Some applications require high chemical purity and others require less purity. The trick is to pay for the purity that you need.  Excess purity is an unnecessary expense.

In many applications a chemical substance must be both chemically pure and of a certain specific physical form.  For applications where the solid must be blended to form a suspension, a slurry, or it must dissolve rapidly, a small particle size is often desirable. Particle size control and analysis is an art that many synthetic chemists can go through their entire careers and never encounter.

In the process of filtration, solids often compact along surfaces to afford flakes and angular chunks that may retain their shape until they reach the package. Lumps can arise from incomplete washing and drying and may be indicative of chemical inhomogeneity in the bulk material. 

Chemical products that are used in compounding for very exacting applications- catalysts, coatings, polymer compounding- may have specifications that require the absence of lumps in the bulk solid. Free flowing homogeneous powders can be prepared by milling or sieving or even spray drying. Compounds that are air, moisture, or light sensitive may not respond well to excessive handling. Before you accept business involving powdered products with bulk solid specs, you need to demonstrate that it is art that you can actually perform.

This is where a smart buyer is worth their weight in gold. Instead of having their own company take the burden of particle sizing, they make the vendor do it. And if the vendor fails, find another.

Where the Brazil Nut Effect seems to enter my life is when the product finally arrives at the customers facility.  If your nice powder had even a single hidden clump in it, you can bet that on arrival it has migrated to the surface to greet the frowning customer. I have received digital photographs of this from customers who wished to drive home the point. So, you just buck up and apologize as sweetly as you can manage and give them your FedEx number so they can send it back.

Bis, Tris, Tetrakis

For many seasons, Th’ Gaussling was the keeper of part numbers and nomenclature in his village.  Fellow peasants would stumble out from the dark and dank mines to plead for new part numbers and names for the new products. As always, outsiders are surprised to learn that this is an actual “job”, but in fact it is. When you make new stuff, eventually you have to call it something. And what you call it has to be recognizable to the barbarian tribes outside the walls.

Peasants and grandees alike would take the names in gratitude for the everpresent fear was that they themselves would be called to toil in the muck of nomenclature as I have.

The dark world of nomenclature is split into two hemispheres- IUPAC and CAS. I don’t know what the deal is with Beilstein. It seems to be a sinking ship with a few deckhands polishing the brass knobs as the bow submerges.  Arguably, CAS has become the default system for nomenclature and identification in much of the world. The CASRN is increasingly the standard for unambiguous substance identification. The US EPA relies upon CAS to keep track of the TSCA inventory. Chemical sellers all over the world rely on the CASRN system to identify products and as a search term to attract internet search engines to their websites.

The major problem that I have encountered is that nomenclature from the 9th collective index (9CI) is often incompatible with our accounting system. The system does not accomodate Greek letters (kappa and eta) and the numbering system leads to sorting and format problems with list generation and subsequent retrieval. The complex system of numbering schemes and nested hierarchies plays havoc with the system as well, if for no other reason than the character count exceeds what is permissable in the data field.

Even more troublesome, the complex names are largely inaccessable to non-chemists. It is very hard for administrative assistants and temps to comprehend accounting data when they are fundamentally unsure of what the identity of the product is and why various materials show up in the bill of materials. To non-technical folks on the business side, chemical names are often just a complicated character string that is prone to data entry errors.

I’ll have to admit that nomenclature from earlier indices (6CI to 8CI) is often more user friendly in this regard. So when it is time to choose a name, 9CI doesn’t always win. This is a propagation step in the retention of obsolete nomenclature and I am guilty as hell of keeping it going.

Unhappy Chemicals

We all have experiences with chemicals that stick in our memory. Experiences where we have witnessed just what chemical potential really means.  Proton or electron transfer can be downright frightening sometimes. Rude and abrupt phase changes or angry exotherms. Sometimes nature rages back at our feeble attempts to take the dragon out for a walk on a short leash.

I can name many exciting materials, but I think that chlorosulfonic acid is one of the more exciting and obnoxious substances that isn’t explosive or neurotoxic.  What are your favorites?

Archaic Chemical Terms

There are interesting sites out there that list antiquated chemical terms. One apparently authoritative site lists 18th Century chemical terms (compiled by Jon Eklund of Smithsonian Studies in History and Technology). 

Some terms seem to remain quite useful, some are hopelessly irrelevant, and others are just odd.  Naturally, I am attracted to the odd words. Have a look for yourself. Here are a few good ones copied verbatum from early in the alphabet-

Cohobation –Repeated distillations, or any cyclic process in which a liquid is vaporized and condensed as, for example, in refluxing.
Cucurbit – The lower part of an alembic. Shorter, more squat and ovoid than a matrass.
Decrepitation – Rapid physical decomposition of some crystals when heated. Characterized by a crackling noise.
Dephlegmation – To remove water from a solution, usually one of an acid or alcohol. There is a sense of purifying about the term, as opposed to simple concentration.
Desquamation – The process of removing scaly crusts which form on a surface.
Dulcification – Any process in which a caustic substance is rendered less corrosive.
Empyreumatic – Tasting or smelling or burnt organic matter.
Exalt – To make more spiritous, volatile, or generally more active; activate.

I wonder if any of these would get through the peer review process if one were to try to use them in a procedure submitted for publication? Perhaps if Roald Hoffmann used them, I suppose.