Category Archives: Chemical Industry

Is this as good as it gets?

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I’ve had this notion (a conceit, really) that as someone from industry, I should reach out to my colleagues in academia in order to bring some awareness of how chemistry is conducted out in the world.  After many, many conversations, an accumulating pile of work in ACS activities, and a few visits to schools, what I’ve found is not what I expected. I expected a bit more curiosity about how commerce works and perhaps what life is like in a chemical plant. I really thought that my academic associates might be intrigued by the wonders of the global chemical manufacturing complex and product process development.

What I’m finding is more along the lines of polite disinterest. I’ve sensed this all along, but I’d been trying to sustain the hope that if only I could use the right words, I might elicit some interest in how manufacturing works; that I could strike some kind of spark.  But what I’ve found is just how insular the magisterium of academia really is. The walls of the fortress are very thick. We have our curricula firmly in place on the three pillars of chemstry- theory, synthesis, and analysis. In truth, textbooks often set the structure of courses.  A four year ACS certified curriculum cannot spare any room for alternative models like applied science. I certainly cannot begrudge folks for structuring around that reality.

It could easily be argued that the other magisteria of industry and government are the same way.  Well, except for one niggling detail. Academia supplies educated people to the other great domains comprising society.  We seem to be left with the standard academic image of what a chemical scientist should look like going deeply into the next 50 years. Professors are scholars and they produce what they best understand- more scholars in their own image.  This is only natural. I’ve done a bit of it myself.

Here is my sweeping claim (imagine the air overhead roiled with waving hands)-  on a numbers basis, most chemists aren’t that interested in synthesis as they come out of a BA/BS program. That is my conclusion based on interviewing fresh graduates. I’ve interviewed BA/BS chemists who have had undergraduate research experience in nanomaterials and AFM, but could not draw a reaction showing the formation of ethyl acetate.  As a former organic prof, I find that particularly alarming. This is one of the main keepsakes from a year of sophomore organic chemistry.  The good news is that the errant graduate can usually be coached into remembering the chemistry.

To a large extent, industry is concerned with making stuff.  So perhaps it is only natural that most academic chemists (in my sample set) aren’t that keen on anything greater than a superficial view of the manufacturing world. I understand this and acknowledge reality. But it is a shame that institutional inertia is so large in magnitude in this and all endeavors.  Chemical industry really needs young innovators who are willing to start up manufacturing in North America. We could screen such folks and steer them to MIT, but that is lame. Why let MIT have all the fun and the royalties?  We need startups with cutting edge technology, but we also need companies who are able to make fine chemical items of commerce. Have you tried to find a brominator in the USA lately?

The gap between academia and industry is mainly cultural. But it is a big gap, it may not be surmountable, and I’m not sure that the parties want to mix. I’ll keep trying.

ACS Denver Last Day

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I’ve spent much of my time at the Denver meeting talking to vendors in the exposition.  There were some very good pieces of equipment at the show. One company had a GC the size of a sub sandwhich.  Pretty cool. It’s for on-site work and actually comes in Army green and camo. I wish I could remember the name.

The Agilent ICP/MS is truly amazing.  Sub part per trillion capability.  The system uses something called the “helium collision mode” to exclude polyatomic cations from the mass analyzer.  You know those pesky argon chloride cations from sample plasma, right?  The argon polyatomic cations can mimic heavier elements by virtue of their combined atomic mass.  The instrument has an octapole chamber with helium in it that serves to impede the larger polyatomic cations. Clever monkeys.

 

Bleaches and in-process checks of the enlightenment

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In his 1736 publication Smegmatalogia, or the Art of Making Potashes and Soap, and Bleaching of Linens, James Dunbar describes a process for the preparation of potash.  The intended user of the process was the common Scottish farmer. Dunbar was anxious to imbue the common Scot with the ability to “bleach” his own linens.  It is important to realize that the meaning of the word bleach in the early 18th century is different from contemporary use.  The modern use comprises notions of decolorization through oxidation of color bodies to produce a white appearance.  The 18th century concept involves the apparent cleansing and subsequent lightening of a fabric.

The book begins by detailing the preparation of a solution or extract from ashes called Lee.  To obtain this solution, the “Country-Man” would carefully collect Scottish vegetables such as the wood of oak, ash, beech, “thorns”, juniper trees, and “whins”. Suitable herbs included fern, breckens (or brackens), wormwood, thistles, stinking weed, and hemlock. 

Dunbar is careful to instruct that the vegetation should be burned in the shelter of a house but in such a way as to avoid burning down the house. The purpose of burning the vegatation in a shelter is to avoid having rainwater come into contact with the ashes.  My interpretation of this is that runoff carries away soluble potash.

The ashes are placed in a container and covered with water. The ashes are soaked in water until such time that the Lee “carries an egg on its surface”.  What Dunbar is telling us is that the extraction of the ashes needs to go until the worker obtains in the solution a particular specific gravity- this is a specification. There is some minimum specific gravity of the Lee that will float an egg.  And the higher the specific gravity, the more volume of the egg rises from surface of the Lee. The specification herein is required for the next operation.  In order to carry out a successful saponification of tallow, the Lee solution must be sufficiently concentrated. 

Dunbar then describes steps where the Lee is combined with the ashes of ash, beech, or fern followed by boiling the water off to afford “thickens of pottage“.  The residue is shaped into balls which are then calcined in a fire to afford a substance that may be stored in a dry container for the purpose of making soap. 

The discovery of chlorine in 1774 by Scheele and the subsequent of discovery of chlorine bleaching by Berthollet gave us our modern conceptual notion of bleach and bleaching. The develoment of bleaching powder was made by Scottish chemist Charles Tennant who took a patent in 1799.  Tennant’s associate, Charles MacIntosh, is thought to be a contributor to this invention.  Bleaching liquors and powders soon became an important raw material for the bleaching of paper and fabric.

The procedure described by Dunbar is a chemical process.  It tells the user when the extraction is complete, qualitatively at least, by a folksy means of specific gravity determination. This is really very clever- it uses a common object to do the test and the result is readily apparent.  Bleaching in the early 18th century involved the use of soaps and of urine treatment and bleaching fields- a far cry from what we now think of as bleaching.

Oil Well Torpedoes and Grubbin’ Stumps

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We tend to think of some things as being relatively new. I’m thinking of the gas and oil extraction technique of fracturing, or fracking.  In the 1884 third edition of The Modern High Explosives, Nitro-glycerine and Dynamite by Manuel Eissler, p 311, there is a mention of the practice of exploding nitroglycerine charges at the bottom of oil and water wells to renew or increase the flow. The author states that this is a popular technique in Pennsylvania at the time of writing.

On p 318 of the same book, Eissler describes the economics of blasting stumps. In general, the process of removing stumps was called “grubbing”. Enterprising fellows knowledgeable with nitroglycerine took little time in applying the explosive power of this oily liquid to clearing the land of stumps.  

Eissler describes the economics of explosive grubbing as follows:  Three pounds of No. 1 dynamite cost $1.50, labor cost 20 cents per hour, 25 ft of fuse cost 1 cent per foot, and 17 percussion caps cost 1 cent each.  Grubbing 17 oak stumps cost $22.52 with 99 man hours for chopping and piling the pieces.  Grubbing with an axe took 142 man hours and cost $28.40.  No. 1 dynamite was comprised of 75 % nitroglycerin and 25 % absorbent.

Bertholet’s discovery of potassium chlorate (oxygenized muriate of potash) happened in 1785. He observed

“that it appears to include the elements of thunder in its particles; and Nature seems to have concentrated all her powers of detonation, fulmination, and inflammation in this terrible compound”. 

Eissler goes on to say that attempts to prepare gunpowder or blasting powder with potassium chlorate lead only to loss of life and limb for the luckless experimenters with this compound.  Two of Bertholet’s artisans employed to do experiments with this material were killed in 1788.  The hazards associated with both manufacture and use of compositions of potassium chlorate were too great to allow this substance to see much commercial application by the 1880’s.

In praise of polyolefins

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Being a person nestled in the dark and humid recesses of industry, I find myself boggling at certain things out in the bright and sunny world.  Truly, it boggles my mind how little appreciation people have for polyolefin resins. That is to say, polyethylene, polypropylene and all the myriad copolymers and formulations found thereto.  Ok, let’s throw PVC and polystyrene in the mix as well.

Why do I boggle at this? What makes my head spin in puzzlement? I’m so glad someone asked.  Polyolefin films look innocent enough to be ignored. In their uncompounded state they are clear and colorless or they may be white.  Polyolefin films and extruded components are ubiquitous in packaging and thus are not normally an object of desire. They serve the object of desire. They occupy a lesser state interest in nearly all contexts.   They are made inexpensively enough to be torn asunder from the desired object and tossed wantonly to the side for later clean up.

But if the uneducated user of polyolefins only knew the extent to which modern science and engineering had been carefully applied to the lowly stretch wrap or the roll of 1 mil PE film. If they only knew the scientists and engineers who carefully devised the ethylene crackers to produce high purity ethylene, or if they knew the highly educated people who devise the polymerization process, they might have heard an account of the long march to produce water white films with properties matched to the end use.

Puncture resistance, elongation, fish-eyes, haze, modulus, crystallinity, glass transition temperatures, melt points, low volatiles, melt viscosity and strength- all attributes carefully tended to so that the film appears invisible to the consumer. High gloss, low haze films to make the product look even better.  Low volatiles and residues for food contact use.  Polyolefins engineered for specific densities for the global market.

All of the attributes above to attend to with a continuous polymerization loop that spews 50,000 to 80,000 lbs per hour of pellets into silos and rail cars. Pellets that will eventually go to converters who will blow films and extrude widgets all day long.  All so the consumer product can arrive at its destination wrapped unscuffed and free of dust.

Polyolefin materials are incredibly useful and amazing in their own right. We should have more appreciation for these materials and how they serve our needs.

Seeking simplicity in process scale-up

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My graduate school mentor use to say that you could synthesize anything if you had the right precursors. With enough clever reagent artistry, most small molecules can be assembled, though if only enough for an NMR spectrum.  With chromatography and small glassware, it is not unreasonable to do a few reactions on 1 mg of material and recover enough mass to get a proton and carbon NMR.  Yes, I know that with microfluidics and labs on a chip, much lower quantities can be handled. But I refer to getting your hands on enough material to see.

What most of us who came through graduate chemistry have learned is that there are enough acids, bases, protecting groups, oxidants, reducers, latent functionalities, and catalysts out there to choose from so that some combination should get you to an endpoint in your synthesis.  If not, then  NMR, mass spec, IR, and imagination (with ample hand waving) should at least give an idea of why something won’t work.

Reaction chemistry (not including biochemical transformations!!) can be thought to occupy two broad domains- 1) low temperature, ambient pressure transformations with highly reactive species (preferably named after dead chemists), and 2) high pressure, high temperature transformations with lower reactive species. Most chemists fresh out of school know the former better than the latter. And that drives our problem solving strategies: Finding reactive intermediates that will react between -30 C and 150 C with a 5 lb nitrogen sweep in a kettle reactor.

Sometimes, the dumber brute force approach is worth considering.  What can be done under pressure and at elevated temperature?  Or, what can be done at high temperature and short contact time?  That dusty Parr reactor sitting in the corner may be capable of a goodly bit of magic.  Behind a shield. It is good to visit the high temperature, high pressure world now and then. Of course, our engineering friends already know this.

As far as the search for simplicity goes, consider what merits there may be in thermally driven transformations. Every once in a while it may be a viable avenue for something useful. Try thinking of heat as a kind of reagent. Chemical plants are good at producing heat.

 

Play it forward. Science as an extended subsidy.

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I search chemical abstracts nearly every day. What occurs to me is that this vast treasure of knowledge is substantially the result of tax revenue channeled into scientific research by numerous technologically advanced societies. While at the time of any given publication, the value might seem minimal. But over time people like me, people in applied industrial science, consume this treasure for the purpose of generating new goods and services. Rather than reinvent the wheel, we consult the subsidized results of other workers in the field. Subsidies of the past play forward to subsidies of the future. If we can’t lift an exact procedure from the scientific literature, then often we can apply new substrates to known transformation. 

In a very real sense, a resource like Chemical Abstracts is an engine of ingenuity. It’s content provides the means to innovation by outright disclosure or by sparking the imagination.  This work is enabled by government organizations funding people and institutions for the purpose of placing technology into the public domain.

While industrial or private organizations have the ability to generate a knowledge base as substantial and as in-depth, the fact is that the imperatives of private business are not in the direction of public disclosure. The imperative of the private sector is to channel wealth to the ownership. The free exchange of knowledge, in the context of business, is discouraged in that it amounts to the free distribution of cash. 

I hear people saying or implying that all things government are bad and that the private sector is inherently “more efficient” and therefore more meritorious.  What we have gotten from government subsidized science is an everlasting fountain of knowledge available to all to put into practice for whatever lawful purpose they can envision. 

An efficient life seems like a puritanical and regimented life.  And the application of efficiency will always fall under the control of the dominant social order. Is this really so desirable?  

Intellectual property has two sides. On one side, the generators of intellectual property can have the right to a timed monopoly on their art via patents. On the opposite side, the public treasury releases national treasure in order to educate the citizens who then generate proprietary art that is withheld from public use.  This amounts to a subsidy of the private sector.  It is a subsidy that sees little acknowledgement in the politics of today.  But such a thing has actually worked well for generations.  

What we are seeing in contemporary politics is the attempt to vilify and deconstruct government. But government has been central to the technological and consequently the economic expansion in the post WWII era.  The mechanism of collecting resources and focusing them on the solution of certain kinds of problems cannot be matched by the private sector. How would you operate the Centers for Disease Control on a greed based system like capitalism? 

Libertarians are always acknowledging the fundamental nature of greed and how it can be channeled into the efficient use of goods and services. I don’t disagree. What I take issue with is that greed must then be acknowledged as the dominant and true influencing force in society. We cannot allow this to be true. We must make provisions for tight control of greed. It is a useful but savage animal. 

In my view, the generation of knowledge and expertise is time and resource consuming. In order to have a particular amount of practical expertise on any given thing, you have to turn over a great many stones and learn an amount of art that is in large excess of the problem of the day. This actually applies to a definition of expertise- the ability to deal with problems that at first seem to be bigger than you can get your arms around. Expertise brings knowledge in the form of facts and problem solving skills. In order to attain expertise you have to absorb to information that at the moment seems superfluous.  In the end, the expert has a grasp of the length and breadth of a topic in excess to any given problem.

Our national system of scientific discovery and information abstracting serves to provide the reservoir of information that serves users into the future.  This information forms the basis of economic growth well into the future. As we go forward with the seemingly inevitable deconstruction of government, let us not forget what government has given us.

The Quicksilver Monopoly

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Hydrargyrum, also known as mercury (Hg) or more colloquially as quicksilver, was in the 19th century the object of monopolistic desire by a large banking concern. In 1835 the Rothschilds acquired the rights from the Spanish monarchy to manage the production of quicksilver in the village of Almaden, located approximately halfway between Seville and Madrid.

The Rothschilds, being ever more interested in controlling their bullion trade, understood that the key to the control of the silver market lay in the disposition of quicksilver. The liquid metal was crucial in the extraction and refining of silver. Silver was purified by amalgamation with quicksilver. Control over the distribution and price of quicksilver in America would put the market in their pocket. They were monopolists- it’s what they do.

Quicksilver has been known for more than 2000 years.  Since Roman times it has been known that everything but gold will float on a pool of quicksilver.  Artisans in Idria, an important old-world reserve of cinnabar in what is now Slovenia, observed quicksilver in its native form in1497.  Quicksilver was mined in earnest in Almaden, Spain, since perhaps the 4th century BC or earlier, according to Pliny. 

Alternating conquests transferred control of Almaden from the Romans to the Visigoths to the Moors and to the crown of Spain, among others.  Having been the seat of mercurial desire for two thousand years, the Almaden cinnabar mines have only recently shut down in the name of public health. Spain’s epic quest for silver and gold in the new world was made feasible through it’s own natural abundance of quicksilver.

Quicksilver was discovered in California in 1845. The New Almaden and subsequently the New Idria mines were quickly pressed into production. The smelting of cinnabar (HgS) into fluid quicksilver is simple in concept and relatively uncomplicated in practice.  A stream of hot flue gases are played over a bed of crushed cinnabar. Oxidation of the sulfide to oxide and subsequent thermal decomposition produces mercury vapor which flows to a condenser surface (brick) where it is knocked down into the liquid state and collected.  Simple technology to perform in undeveloped territory.  Quicksilver was sold in 76 pound lots called a flask. This is thought by some to represent what a laborer (or slave) could reasonably carry.

Within a short time the Californian supply of quicksilver robbed the Rothschilds of their monopoly, resulting in strong price pressure on the European suppliers.  For a few decades, the American quicksilver dominated the Pacific rim. Chinese demand for quicksilver or cinnabar for vermilion was strong.  Silver mining in Mexico and the Andean districts to the south was dependent on quicksilver, most of which was controlled by Spain and later Mexico after its independence. Eventually, the Rothschilds regained control of the market, but at a time when cyanidation and chlorination were playing a larger role in gold extraction. The Rothschilds relenquished their hold on Almaden in 1921.

It is interesting to note that quicksilver, so crucial to the isolation and refinement of gold and silver, was discovered a few years before the discovery of placer gold at Sutters Mill. This happy circumstance surely facilitated the prompt extraction of wealth from the gold and silver mining districts that opened up in the west.

Ways to be a chemical entrepreneur

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I had a discussion with some professor friends recently about the subject of entrepreneurialism among chemists.  I made my usual points about how people become captains of industry. Be more like an engineer. Preferably one with an MBA.  Naturally, my professorly friends were unmoved. Having spent their entire careers in academia, they just didn’t know about this. I didn’t expect them to.

After I made a gross generalization about the lack of entrepreneurialism among chemists, one prof pointed out that in her field of research, there were indeed people who were starting ventures.  I do not doubt this. But it made me think.  People, perhaps especially those in higher education or just advanced technology, naturally conclude that an entrepreneurial venture has to be based on new technology.  Yes, we need people to start businesses in nanotechnology or what ever you call the latest iteration of biochemistry. We need to have a constant churn of people trying to put new products and capabilities on the table.

But we also need businesses who are able to make polysubstituted phenols, anilines, pyridines, alcohols, ketones, aldehydes, halides, and all of the other “ordinary” raw materials and intermediates that are now largely made in Asia. We need companies who will make 100 kg or 1 MT of some obscure organic material.  Entrepreneurialism isn’t just about the bleeding edge. It is about having a dream and seizing opportunity.  It can be cookies or chemicals.

For the most part, intermediates have moved to Asia because of the economics of batch processing fine chemicals. And a moribund approach to chemical manufacturing in the USA. Chemical manufacturing in the USA is complicated. There are environmental permits, TSCA, high waste disposal costs, high labor costs, expensive processing equipment, and layers of business structure to manufacture safely and with high quality. A chemist faced with navigating the maze of regulations, engineering details, and business operations is a busy person indeed.  Few people can do all of it alone.

There are two fundamental approaches to starting a technology company- Market pull and technology push.  Market pull is an activity where one builds manufacturing capacity with the intent of filling it by making exsting items of commerce. Technology push is where one intends to construct a new kind of technology in the form of a service or widget. Market pull is an approach wherein customers buy known technology. Technology push is the activity where the customer is asked to buy into a new product or service. In this case, you’re necessarily asking customers to be first adopters or to find new forms of value.

I’ve seen startups fail because their one-act pony didn’t work. Instead of trying to make a go of it with a one-act pony, a whole circus of acts should be going at once.  A batch reactor is capable of making many things. A plant built around one product is entirely dependent on that one product.  Batch reactors occupied with products from many market segments are batch reactors that will remain busy over a variety of market conditions.

Pharmaceutical intermediate manufacturing is a business weighed down with substantial overhead and structural immobility.  It is not automatically a great place to start. The GMP world is very complex and peppered with many operational land mines. Many early intermediates are not covered under GMP. That is a good place to start. 

ISO certification is another area where I take issue. While ISO certification brings good business practices, it also brings layers of administrative structure. It is possible to mimic this structure without formally adopting it. The ISO label on you advertising will impress some buyers, but a surprising niumber will be indifferent. If you want to be in pharma intermediates, this will be necessary.  What an ISO certification says is that you will do what you say you are going to do. That is a good idea regardless.

What has to change is the economics of manufacturing in the USA. One way to do this is automated synthesis.  A good example of a problem:  How would one automate the synthesis of an OLED chemical like 1 MT of 8-hydroxyquinoline? This is an existing item of commerce, so entry into the market means taking share from someone else. You’ll probably have to best the market price by 10 % at minimum to induce someone to switch vendors. 

The chemistry isn’t cutting edge, but the processing economics may be. This is an example of how entrepreneurialism can and should  tackle manufacturing problems and gain a competitive edge. Since labor cost is a huge driver, find a way to shave off labor. An entrepreneur’s competitive edge may be process cost savings alone. You don’t have to wait for a scientific paradigm shift.

Part of success is just showing up. Just having capacity and a knack for a particular transformation can attract buyers. If you are handy with borylation and are flexible, somebody will call and want a quote. And maybe a sample. Pretty soon you have a PO and a deadline.

It is good to consider that an advance may be in the form of processing economics, not just the science.

Thoughts on Process Development. Outsourcing.

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I have not put pen to paper (Okay. Fingers to keys) on process development lately. I can’t discuss much in the way of specifics. But there are some generalizations that can be put on the table for discussion.

When should you outsource a raw material? Depends. Does the process for the raw material match your skill set? Namely, does it require, say, bromination of an olefin or an aromatic ring? This can be deceptively troublesome. It is easy to scribble down a reaction mechanism for a bromination. It can seem like a no-brainer to say “yeah, we can do that”. Same is true for a Sandmeyer or a Friedel-Crafts reaction or some oxidation reaction for instance.

You may not do much of a particular kind of transformation or handle certain reagents enough to have an institutional expertise to safely handle some materials. You may have safety kingpins who will nix some reagents because they don’t like the looks of the MSDS.  Or, your pots and pans may be booked well into the future and you have no opportunity to make the raw material.

The trouble with outsourcing a raw material is that the supplier’s price is your cost which must be passed along to your customer. You may or may not have the margin to play with to do much outsourcing.  If you suddenly need to outsource a raw material, you will have to find a shop that will make the stuff.  Preliminaries include doing a secrecy agreement, a disclosure of the desired material, and possibly disclosing a technology package.  After the disclosures it might transpire that the vendor isn’t interested, they can’t do the job in the desired time frame, or they want too high of a price. Lots of things can go wrong.  Meanwhile, you’re relentlessly screaming down the timeline towards you’re own delivery date. You should be planning your outsourcing 6 to 12 months in advance. Or even 18 months.  Outsourcing always involves the discovery of new failure modes.

Let’s say that they agree to work up a quote. There is the matter of specifications. They’ll need to know some specifications even before they quote a price.  What kind of purity are you needing? Be reasonable now. There is what you want and what you can get by with. OK, you can live with “97 % purity”. What does that mean? Does it include solvent residuals? What about color and haze or mesh size and appearance? If it comes in at 96.8 %, are you sure you want to reject it?  If it can be easily reworked, and you have the time to spare, rejecting the material might be the best choice. But if they are late and you are late, you may have to take the material on waiver.

Apart from the mere chemistry is the matter of TSCA regulations and/or import restrictions. Will your vendor have to file for an LVE (low volume exemption) or is the material already on TSCA?  An LVE will take time even if everything goes well. Need to put these regulatory filings into the timeline.  Want to import bulk Hazardous When Wet materials? Plan on a boat ride across the ocean.

Asking a company to develop a new product for you requires good communication, person to person relationships, and lots of patience.  Your custom vendor may be smaller than you are and may have considerable resources tied up in your order. They’re taking some risks as well. Shoot for win-win.