Category Archives: Chemistry

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.

And then I woke up

And it came to pass that a Being appeared to Th’ Gaussling one afternoon in the laboratory. But this was not a Being in the league of the Angel Michael or Gabriel. This was a somewhat lesser Being. Call him “Ed”. 

While Th’ Gaussling was tending to some matter in the lab, the Being Ed made his presence known by speaking through the vacuum line.

Gauss-ling“, hissed the disembodied voice through the Buchner filter.

Gaussling startled, dropping a few grams of precious crystals on the benchtop, and looked in full circle around him trying to find the source of the voice.  Puzzled, Gaussling stood still for a few moments listening for more sound and then, with a shrug, began to clean up the mess.

“Gaussling, I’m down here” said the voice, a bit more impatiently. “Set the spatula down and look in the filter”.

Sensing a practical joke, Gaussling replied sarcastically “Bugger off! I’m busy. Buncha NIM-rods …”.

With unmistakable urgency, the voice commanded “Look in the Filter!” At that moment, the vacuum pump changed its sound to a quiet tap-tap-tap, indicating that the pressure had dropped. The mercury column in the manometer collapsed and the pump noise became just a whisper.

Gaussling promptly stopped what he was doing and leaned towards the Buchner filter while scanning sideways for pranksters. But the room was empty and the voice had a decidedly raspy edge to it now. As Gaussling peered into the filter he noticed that a voice appeared to eminate from the vibrating filter paper. As the funnel spoke, crystal fragments danced across the flat paper like rice on a snare drum. Gaussling froze and couldn’t manage a breath.

“What do you want?”, Gaussling gasped.  “How can this be happening? Who are you?”

“You may call me Ed. Some of your kind have referred to my species as ‘Angel’ “, Ed replied matter-of-factly. “I think you’ll find that description to be inaccurate.” 

At that moment Ed apparated beside Gaussling in front of the fume hood. There was a rattling pop and the crackle of static discharge with a brown puff of nitrogen dioxide and ozone. Disconcertingly to the traveler, this type of conveyance caused the accumulation of static charge. Gaussling momentarily wondered how many Coulombs of static an Angel could withstand, but then snapped back to matter at hand. 

Still quite shocked, Th’ Gaussling managed to squeek out a few questions. “How did you do that? Where are you from? What do you mean by Angel?”

Ed was always annoyed with such questions. The gosh-wow-sense-of-wonder reaction from these creatures wore thin after a while. As Ed took a moment to adapt to the atmosphere and the pressure, Gaussling looked up and down at the visitor.  It was apparently a he from the outward mannerisms and dress.  Gaussling wouldn’t push the issue of gender right away.

“Dear fellow” Ed said in an impatient and distinctly British tone, “would you kindly relax and set that bottle down? I need to speak with you.  I’m only able to stay for a moment. This kind of travel causes extreme parity violations in the cosmos and is possible only by rather large energy consumption elsewhere, not to mention great discomfort for me.”

“So, you’re Ed? ” Gaussling said awkwardly. “What are you doing here?”

“I have a gift for you,” Ed replied in a matter of fact tone and reached inside his vest. “In fact, here it is.”

Ed pulled out a small vial that appeared to be of glass construction. At the bottom of the glass vial was a powder. It was unremarkable in every way and initially resembled ten thousand other colorless powders.

Ed held up the small vial and grinned. “See, here it is. Oh, my my my. You are going to be very amused.” He could barely contain his glee. Ed held the vial up toward the light but now the powder appeared somewhat different. Gaussling thought he saw a faint iridescent glint to it. A flash of a shimmer of spectrum against the cold fluorescent lights.

“I have come a long distance to give this to you. It is a substance capable of great wonders for those with the curiosity and wisdom to use it properly. But it is also capable of doing great harm. Soon you will see.”

Gaussling stood there, attentive but unable to utter a single word. After a few moments, Gaussling sputtered “What does it do?” 

Ed stood for a moment and then gushed with great delight, “I though you’d never ask. Get me a flask with some liquid in it, any liquid.”

Gaussling grabbed a 250 mL beaker and splashed a bit of acetone in it- 50 mL or so. Gaussling handed the beaker to Ed.

“Gaussling, I am going to put a single crystal of this substance into your liquid. Watch …” And with that fluorish, Ed expertly shook a single crystal of this substance into the beaker. The result was immediate and spectacular.

As Gaussling watched in amazement, the list of uses washed over his mind like a storm surge over a levee.  “How can this be happening?” Gaussling gasped.

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.

Ab Initio Chemical Plant Design

So, dear reader. If you were going to design a general/multi-purpose chemical plant capable of doing a wide variety of chemical transformations, what kind of features would you install now that you’ve had some experience in the field? No high pressure vessels, just ambient to 80 or 100 psi. I’m talking about a plant with 50 to 2000 gallon reactors- say, 8 of them. What kind of configurations would be desirable starting from the ground up?

No GMP capacity- too bloody expensive. We don’t want to do API’s.  No gas phase chemistry. No scary oxidation chemistry or energetic materials.  Just the kind of garden variety specialty organic or inorganic compounds and transformations that you might find in the Aldrich catalog.  Synthons, reagents, etc.

One interesting thing to ponder are possibilities with the use of passive architectural features to attenuate the propagation of upset or emergency conditions. 

Literature Swim. The Guo-Liu Catalyst.

Guo & Liu Catalyst

The literature train station is overflowing with diverse catalysts for the large variety of coupling reactions out there, as is the patent literature. Parties scramble to get window seats on the IP Express, the high speed non-stop to that Golden City on the Hill. 

A recent JOC article disclosing an inexpensive catalyst system that struck me as interesting.  The article by Guo and Liu emphasizes economy and so discloses a phosphorus-free bidentate ligand system that affords Heck and Suzuki-type coupled products.  There are pluses and minuses to this system, as is the case for most catalysts.

On the plus side with the Heck and Suzuki reactions, both activated and deactivated aryls gave decent yields. On the minus side, the Heck coupling reaction is a bit slow. A fair amount of energy input was needed- 130 C in DMF over 30 hours. On the Suzuki side, most reported reactions resulted in good yields, except for the aryl chlorides. The relative inertness of chlorides is not particularly unusual, but it may cause this catalyst to be passed over in some applications where the less atom-efficient bromides and iodides have been targeted for replacement.

Finally, the apparent requirement of DMF is rarely happy news. Regardless, I have no doubt that this catalyst will find its way into the future literature and many clever applications will be revealed.  As of this writing, I was unable to find a US patent by inventors Guo and Liu claiming this technology. Since there is a 1 year limit on the filing of a patent application following disclosure, this technology could be in patent prosecution at present. Or not. Wouldn’t it be a happy thing for it to be in the public domain?

Polyolefin Migration

The worlds burgeoning middle class has a voracious appetite for polymers and this has compelled other regions of the world to execute a refining and manufacturing buildup that will cause an upcoming oversupply situation. In particular, Middle Eastern and Asian PE and PP capacity will take a sharp upturn, shifting supply patterns and causing margins to fall. Demand for North American (NAm) polyolefin (PO) products will enter what is projected to be a permanent decline as capacity and market share shifts to other longitudes.

Fortunately for US interests, many PO producers have anticipated this and have diversified through significant structural changes increasing access to the far regions of the world. This fact alone should buffer the upcoming downturn in the industry. Projections I have seen suggest that the NAm PO market should be back up to present levels by 2012 as the new capacity operates as price taker rather than a price maker. Eventually for NAm and the EU, finished goods imports will overtake market growth and a period of decline will ensue.

The new world I am describing is projected to happen in 2009. We are about to feel the gravitational pull of the “New Gulf”. The Old Gulf- Gulf of Mexico- will take a back seat to the Gulf in the Middle East.

One weakness of the New Gulf seems to be ethylene. US capacity for the extraction of ethane from natural gas and its conversion to ethylene is an advantage that will buoy NAm PE business for a while. But once Middle East and Asian operators learn to run their plants efficiently, NAm facilities will face the somber truth of the marketplace. NAm will become a net importer of PO’s. 

Asian demand for PO’s is growing so rapidly that it may never become a net exporter of PP and PE.

One factor that I do not understand yet is the effect on petroleum supplies and the cost pressures therein. Increased capacity giving lower prices could increase petroleum and gas scarcity resulting in increased prices of petro-energy.

A.I. Meyers Memorial Ceremony

Friday, 22 February, 2008, CSU held a memorial ceremony in honor of Albert Irving Meyers. Past and present chairmen of the Chemistry Department spoke of their recollections of Al Meyers, the man. Al’s family was present and son Hal Meyers spoke in memory of his father. It was a heartfelt and touching ceremony that ended with a photo montage of Al’s life.

Turnout by former group members was fairly light, but most alumni had considerable distances to travel so this isn’t surprising. I was aware of 6 members in attendance. Former chairman Rod Skogerboe was present. Rod was injured and paralyzed shortly after his retirement. He was in good spirits and spoke well of Al.

I am always interested to hear the way people reflect on their post graduate education. People leave the grad school experience with many kinds of feelings about it. Some are positive and some are negative. Some feel self-actualized and others feel injured.  I think that no matter how you feel about AIM and the other “rock stars” who head the chemical academy, you have to admit that AIM had an abundance of charismatic ability in a field of outspoken characters. Al used the strength of his research productivity along with his “gift of gab” to pursuade the department and the university to excel in chemistry.

The academy produces people who go on to become the parish priests, bishops, and the occasional cardinals of chemistry. It is interesting to meet friends who have gone on to become the directors and VP’s of the field. In my experience, the people who have the most buoyancy are the ones who have an upbeat, can-do attitude and can find a way to get things done. The kind of work/quality ethic that Al expected from his crew really is beneficial to those who don this particular suit. You can see it now in the career trajectories of the many alumni out in the world.

Changing Petrochemical Center of Mass

The Middle East (ME) is currently undergoing a dramatic change in petrochemical supply and refining capacity. Multiple projects in several countries are underway that will offer greater capacity of key hydrocarbon feedstocks as well as fuels. 

The current run up in crude oil prices has produced an abundance of cash for oil producing states in the ME.  Acutely aware of the transient nature of their oil reserves, the cash generated has been applied to infrastructure. Social infrastructure as well as industrial infrastructure has been expanded in the ME with facility no doubt eased by the nationalized nature of the petroleum companies. 

In the USA, a run up in crude oil prices has not resulted in a major uptick in refinery capacity, port expansion, or the birth of new universities. Instead, US oil companies have plowed investment into new discovery activity in an attempt to sustain the current rates of consumption. Profits are channeled into CEO salary packages and to shareholders, who, in turn, go to great lengths to shelter their funds from taxes that support US infrastructure.

Saudi crackers alone are expected to add 14m tonnes/year of extra ethylene capacity by 2015. ME market share of PE and PP is expected to double by 2011. So large will the demand for ethane be that there is considerable skepticism that the full potential of the buildup will be realized.

Since ethylene comes from the cracking of ethane, and presently a large share of ethane comes from natural gas, the question arises as to the effect on natural gas prices as ethane scarcity becomes apparent.  Naphtha crackers are part of the answer to the question of supply. The US has (had) abundant natural gas and a corresponding reliance on the extraction and cracking of ethane from this resource. Elsewhere in the world, a large fraction of ethylene comes from naphtha feedstocks.

And so it is that the Saudis are building crackers to bolster their feedstock supplies. The Dow/Siam Cement JV is also addressing their ethylene supply issue with a second naphtha cracker in Map Ta Phut (ICIS, 2007, December 3-16, p 6).

The largest petrochemical complex in the world is under construction at Ras Tanura in the eastern province of Saudi Arabia.  This US$20 Bn project is being developed jointly by Dow and Saudi Aramco and is expected to come onstream in 2012. The goal is to integrate the existing Ras Tanura and Yanbu refineries into a single operation offering petroleum refining and production of value added hydrocarbons like ethylene.  Clearly, the principals have downstream conversion in mind. The project will have the first naphtha cracker in the ME and will offer ethylene cracking and aromatics capacity as well.

According to the article in ICIS, Basell claims that the ME will be the only net PE and PP exporting region by 2011.  And so it was that the petroleum scare in the first decade of the 2000’s financed and expedited the migration of dominance in the polyolefin industry to the Middle East.

On Marketing Chemicals

If you are a marketing person in the chemical industry, the question of how-to and how-much is never far from your mind.  I’m not talking about selling pesticides or drain cleaner to consumers. I’m referring to B2B chemical sales.  Feedstocks, reagents, catalysts, additives, etc.

Management never likes to pay much for advertising and will always be skeptical of the value of ads. Yet, deep within that black heart most managers know that some advertising is necessary.

Sales to the public is demand that can be fairly easily measured. Sales in the public domain are open and lots of nifty and informative stats and trends can be compiled to help plot marketing strategy.

By contrast, sales of products that are not out in the open, or products that are part of a proprietary process leading to another kind of product are things that are somewhat problematic to understand.  Products that are uncommon or are unique to a few limited circumstances are not products that you necessarily want to promote in the mass media.

If a company makes a bracket that is used to hold a fuel flow sensor on a 1998 Buick, chances are that the product will be useless for just about every other application.  But many components on that same Buick are of a general nature and may be found on many kinds of cars.

In chemical marketing, many products are of a general nature and many are highly specific. The marketing approach for highly specialized products is necessarily more focused than that for chemicals of a more general utility. A specialized product requires that marketing people be like a Dachshund- these dogs were bred to go into burrow hole to pull out the critter that lives in there. Marketing specialty chemicals requires the same sort of proclivity.

Where do I find information about who uses what?  I search patents, SciFinder (to see who is publishing with what materials), Google, and I talk to people about what they are looking for. Purchasing people always have a list of troublesome products. Your company should have a decent customer list to draw upon.

Another approach is to do a patent search starting with a particular company AND a key word. While there is absolutely no assurance that the company is actually practicing the art that they patented, it is possible to collect a list of companies that have used your product at one time.

Finally, there is the Johnny Appleseed approach. You simple plant literature at every fertile site you can find, and you do it several times with multiple media. Brochures, emails, cold calls, websites, conferences, and technical literature.  “Technology Push” is hard work. Especially if the economy has taken a dive. It can take 3 months to 3 years for a potential customer to give you a call when they finally decide to make a query.

The marketing of obscure products is spotty business and hazardous to your wallet if you are on commission. The best circumstance is to have a portfolio of products, or a catalog. If your collection is good enough, something will always be in demand.

Droppin’ your pants for chemistry

In my career in the fabulous world of industrial chemistry, I have had to drop my pants exactly twice in the cause of business.  The first and best time was in Japan. We had just been to the science city of Tsukuba near Tokyo. After driving all day in Tokyo traffic and shuffling around at business meetings in comically small sandals, we finally ended up at what I thought was a restaurant. Glad to get out of the car, I followed my running host through the rain and into a stone building out in the countryside. But instead of walking into a dining area, we walked straight in to a locker room!

I was about to protest that I didn’t have a swim suit when it dawned on me that birthday suits were the standard dress wherever we were going. Hmmm. Lordy, I wonder if this is co-ed? Gaijin anatomy would be the featured attraction this evening.

We padded out, barefoot and naked, into a covered outdoor area and straight into the heated pool.  It was delightful. We soaked for 45 minutes and talked about business and life in Japan. All too soon, we got out, showered, dressed, and entered the dining area.

We took our positions on the cushions on the floor by the table and were treated to an incredible meal of exotic food and drink. It was highly civilized, relaxing, and memorable experience.

The next experience is the one time I had to go home without my pants. Some years ago I was making about a kg of some material in a 12 L flask. The reaction proceded normally and all was well until I tried to disassemble the apparatus in preparation for a filtration. The flask slipped from the clamp due to the considerable weight of the halide and dropped a few inches onto the benchtop. The flask broke, discharging the contents onto the hood benchtop.  I can’t say what was in the mixture, but I can say that the solvent and residual halogen were absolutely the least of my worries.

It didn’t take long for me to realize that this was beyond my ability to safely handle without a Hazmo suit and supplied air.  Somehow, in the course of this, I got a smudge of reaction mixture on my pants.  The safety manager looked at me and ordered me to remove the contaminated pants, which I did.

So there I was, standing in my boxer shorts- the ones with the orange and green watermelon print- while the safety manager was standing there shaking his head laughing. He threw a tyvek bunny suit at me and walked out.

We discontinued the reaction after that event. The hazards were just too edgy, even for me.