Category Archives: Chemistry

A few hints on starting a chemical business

I see from the control panel behind the scenes here at the Lamentations on Chemistry control center that in the last few days a few people have found this site with the search words “starting a chemical business”.  I have written a post on this previously and really have little new to add but I will emphasize one important thing:  starting a chemical business is like starting any other business. You have to find a product to sell. Once you do this, it is a matter of pulling together the resources to make it happen.

A few other hints. I would add that the entrepreneur should be wary of much advice from MBA’s. They have B-School sensibilities drawn from academics and nurse considerable dogma about the latest business models that may make the task seem overly complex. Chemical manufacturing is based on a simple concept- buy relatively inexpensive raw materials and use them to make a higher value product for a price that a customer will pay and will afford you a profit.  That’s it.

If you can’t make a gross margin of at least ~50 % (EBITDA), then don’t offer to make the product. There is nothing specific to chemicals about this number, it’s commonly used in manufacturing.  Point is, it is critical to keep costs low. You have pay for employee benefits, taxes, interest, insurance, business trips, analytical costs, and put some money aside for investors and growth. Remember competition will eventually beat down your prices. Be prepared for that. Keep you head on a swivel.

Be an opportunist. Make whatever is profitable. Your pots and pans don’t care if you’re making boronic acids or siloxanes. Don’t offer anything without a front run and an IP search.

Be prepared to grow organically. Stay away from commodities unless you have a big pot of cash and the willingness to go into mass production in a competitive arena.  Pharmaceuticals? Well, it’s an extended nightmare to enter into and I wouldn’t recommend it. But entrepreneurs are characteristically hard headed, so do as you please.

Pick a manufacturing site away from population centers and with zoning that will let you grow. You might have to stay away from desirable urban corridors to do this. The last thing you need is a subdivision next door packed with nosey suburbanites who don’t like the cut of your jib or the smell of fugitive emissions. Take advantage of industrial parks with existing heavy industry.

Make sure that the fire marshal is happy with your operation. Good housekeeping prevents accidents and looks good to insurance underwriters and firemen. 

Resist the temptation to occupy bright and shiny office buildings. Use your resources to attract good people and pay them competitive salaries. If they’re stimulated by the work, they won’t need or miss fancy office spaces.  Use your cash and credit resources to purchase equipment from auctions.  Do your best to keep your D&B rating as good as possible. This will help you get better purchasing terms and conditions from suppliers. Remember that you will need working capital to bridge the gap between ordering raw materials and the receipt of payment from customers.  This is where marginal businesses really get into trouble.

Chemistry isn’t easy

I’m reminded this afternoon of how nothing is simple in chemistry. Everything seems to require a learning curve.  Even in making an apparently simple binary inorganic molecule, nature can put a hitch in yer giddyup.  It’s especially vexing when all you have to determine purity or identity is elemental analysis or perhaps some gravimetric wet chemical method.  I’ve been spoiled rotten by NMR.

Update:  OK. So I have tweaked the reaction conditions and am now able to make this particular metal halide.  I was applying conditions that were too vigorous.  This is an element I’ve never worked with before, so it is new territory for me. Funny how different metals can be … said the organikker.  \;-)

On the manufacture of hazardous materials

How does one decide if a given compound is too hazardous to manufacture at a particular site? The answer to this question is much harder to arrive at than you might imagine.  It is very easy to spout glib, hand waving statements about risk analysis and risk based process safety. It is quite another matter to actually conceive of experiments to tease out the safety data and compile it into knowledge based practice.  For the manufacturer there are two kinds of operating hazards to contend with- 1) physical hazards, and 2) regulatory hazards.  Getting into trouble with either can bring your operation to a halt.

In general, there are two kinds of GO / NO GO approaches to the question of going forward with any given material. One method applies some kind of quantitative risk analysis based on accumulated knowledge combined with hazard thresholds defining acceptable risk. Regulatory compliance and insurance issues may apply, or not.

The other general approach is simply a management decision. The board of directors or CEO decrees that we’ll go forward and do what it takes to operate safely. Or management decrees that we will not go forward with the manufacture. We’ll let someone else have that plum.

I recall being at a propellants conference a few years ago where a representative from a solid propellants manufacturer asked me if we would consider making lead styphnate. I paused for a moment, as if to be carefully weighing my answer, and replied with a flat ‘no’.  The fellow wasn’t surprised and went on his merry way. This was the exercise of an informal method of process safety. Decline to make the obviously hazardous materials.

The threshold for the definition of hazardous materials varies considerably within industries and between them. The spread of hazard types across the manufacturing world is large and perhaps confusing.  Two of the broad types of manufacturing hazards are hazardous energy and toxicity.  Hazardous energy is found in operations with high pressure, flammable materials, mechanical energy, chemical reactivity, electrical energy, and explosive materials which is a combination of chemical reactivity and mechanical energy.

Toxicity

Toxic hazards are a group that cover a wide range of physiological effects and modes of dosing. Toxicity issues relating to manufacture can be a very complex matter and it is best to involve experienced hands to sort out the good sense fom the nonsense. To a large extent, the maufacture of toxic materials is covered by the proper application of personal protection equipment (PPE), good plant hygiene, and a process that keeps toxic materials contained to the greatest extent possible. The pharma people know all about this activity. But in the specialty chemicals business, a good deal of the chemical intermediates that go out the door have poorly understood toxicology.  

Products that are made for dispersal into the environment are subject to much greater oversight by EPA. But the same is not true for a great many chemical intermediates. Chemical intermediates flow through different  regulatory pipelines with some under thorough regulatory scrutiny and others considerably less so. Pharmaceutical intermediates may or may not be covered under FDA GMP rules. Very early intermediates may be items of commerce and not subject to the Byzantine ways of GMP. Later intermediates may have FDA requirements that handcuff you to the bedpost.  It is possible to have a very prosperous career outside of the GMP world.

Chemicals that are not for pharmaceutical or pesticide use may be listed under TSCA.  Chemical Abstracts Service maintains the list and access to entries is had through the CASRN, or the CAS registry number. TSCA is a type of oversight promulgated by the EPA and is intended to provide scrutiny in regard to worker exposure and environmental release during the execution of a chemical process. EPA does consider the toxicology and environmental  literature and is able to model the fate of a release into the air or water by calculation.

While specialty chemicals are subject to TSCA regulations and an approval by EPA, only cursory toxicological examination is customarily performed. TSCA approval is either in the form of a listing or through a low volume exemption. PSM regulations promulgated by OSHA provide regulatory crossfire on the manufacturer in that OSHA regulations require enough safety testing as to provide a safe working environment.  So together, OSHA and EPA cover a great deal of area in manufacturing safety. The rules are meant to be proactive, but they also provide substantial penalties for infractions. There is much more depth to TSCA and PSM than I have mentioned here, obviously. It is important to have people on staff who specialize in regulatory affairs.

Testing for toxicological effects is time and resource consuming. Much planning must go into such testing and it must be started well in advance of plant operations. Substances that pose a potential risk to workers via chronic occupational exposure during manufacture and handling are good candidates for such testing. However, if the substance is not a commodity chemical and if the substance is made only during infrequent campaigns for a limited group of users, it is less than likely that it will have been tested.  The best approach to manufacturing a substance with little data available on toxicity is through the use of precautionary guidelines with layers of protection for the operators. That is, design a process that prevents exposure of the workers to the product and offers redundancy in engineering and administrative controls. The coverage must include production operators, maintenance crews, warehouse workers, chemists, and engineers.

Hazardous Energy

Reactive hazards and hazardous energy issues can and should be investigated by the manufacturer to the greatest extent possible. While such activity can be farmed out to commercial labs, it is very important for management to grasp the benefis of in-house expertise.  Depth of knowledge is important in understanding and preventing  upset conditions. But the accumulation of such depth of knowledge is expensive and subject to throttling by management. It always involves accruing more information than is apparently needed, at least initially.

Science is to a large extent about understanding boundary conditions. In the same way, chemical safety requires understanding the conditions for the release of hazardous energy, decomposition, or other undesirable attributes.  What you’ll find quite often is that a single measurable attribute is not enough to assemble a complete picture of reactive hazards. Most reactive hazards are understood by assemblig a composite of several kinds of experimental results for a more complete appreciation of the dimensions of the reactivity.

To find such boundary conditions one needs to conceive of experiments to tease out the effects. Some kinds of information relating to safety issues can be obtained by instrumentation. Differential Scanning Calorimetry (DSC) is one such technique that gives a quantitative picture of the heat evolution of a substance while it is being heated over a planned temperature range. Thermogravimetric Analysis (TGA) of a test substance gives an indication of mass loss as a function of temperature. Accelerating Rate Calorimetry (ARC) shows heat flows into or out of a sample while recording sample cell pressure.  ARC goes a bit further than DSC in that the evolution of non-condensable gases can be inferred by the shape of a derived Anton curve. ARC also gives an indication of time to maximum rate (TMR), which is a useful parameter in determining the maximum temperature or residence time for a reactive material or mixture. Reaction Calorimetry (RC1)  shows the heat flux profile of an actual reaction mixture over the course of reagnt dosing. RC1 may be used to look for the accumulation of energy in a reactor. There are other tests available, but I cannot attest to them on the basis of personal experience.

Explosivity

Noninstrumental methods of safety appraisal include the tests for explosive properties. There are well defined protocols for explosive testing and they are applied in layers. It is very important for people handling new materials that may have explosive properties to understand the various assays for explosivity. 

Explosivity (or explosability) may be manifested in many ways and there are tests to tease out sensitivity to a measured stimulus. The key point I’m trying to make is that explosivity is a composite property sensitive to multiple kinds of stimulus and physical circumstances. Many materials are explosive only according to a few kinds of tests.

Safety testing for materials that may be energetic include BOM (Bureau of Mines) or BAM fall hammer tests and the BAM friction test. These tests do as the names suggest- look for thresholds for sensitivity to impact or friction.

The Koenen test  looks for explosivity when a material is heated under partial confinement, i.e., material is packed in a metal tube with a small hole in the end. Materials that are merely flammable will decompose and vent through the orifice. Compounds that are explosive may cause the Koenen tube to burst.

The time/pressure test is used in DOT classification and consists of a pressure vessel fitted with nichrome wire and a pressure sensor. The sample is heated with the nichrome wire or flame and the pressure is monitored. A pressure rise from 100 to 300 psi in 30 msec or less is regarded as having rapid deflagration properties and an qualifies as a positive indication for explosivity for transportation purposes. For the process chemical industry, this test gives an indication of the potential for rapid gas formation and the unwanted PV work it may do on your equipment.

There is a  series of tests used for DOT classification of explosive properties that will give useful insight for those who propose to manufacture intended or unintended energetic materials. It is useful to have material tested to assemble the composite picture of the materials sensitivity.  Questions to ask are: 1) does the material show any positive indications at all? 2) If explosive indications are found, is confinement required? 3)  Does the material show any detonability at all? 4) Can you fnd any sensitizers or catalysts to explosivity? 5) Does the material transition from deflagration to detonation? 6)  Is the material sensitive to stimulus by electrostatic discharge (ESD)? 7) What temperature gives a time to maximum rate (TMR) of 24 hours? 8) Do the decomposition products contain non-condensable gases?   There are more questions to ask. Remember not to confuse detonation with explosion.

For the chemist interested in manufacturing a product that has known reactive hazards associated with it, it is useful to have collated the data. The application of knowledge of reactive hazards depends greatly on the kind of equipment to be used and the kind of chemistry to be performed. It is possible nonetheless to make a few useful generalizations.

Accumulation of Hazardous Energy

The execution of a chemical process usually requires that two or more substances be put into physical contact in a solvent. This is a point at which hazardous energy may be evolved. Obviously, for promptly reacting systems the rate of heat generation must be less than the rate of heat removal to avoid a runaway situation. But special care must be taken for reactions that are not prompt and that might allow for the accumulation of unreacted material in the vessel. This unreacted material in a reation vessel represents an accumulation of potentially hazardous energy. Good process R&D will identify reactions with latent periods or reactions that are particularly slow to start. Problematic reactions require good in-process checks to ascertain the state of the rection. Very often, a heat kick is all you need to see to know the reatcion has begun.

Grignard reagent reactions are notorious for being slow to start, tempting operators to “goose” the reaction by adding more RX to the pot. Above about 10 % of RX over Mg, the potential for a runaway initiation is very high.  It is best to limit RX addition to a maximum of 5 %. If no initiation is observed after a reasonable attempt, the chemist must be awakened and hauled to the plant to provide on the spot guidance. Generally, initiation is a matter of time. But but sometimes parlor tricks must be used to activate the Mg. These are well known. It is always best to use these activation tricks prior to addition RX to the pot because otherwise a rapid consumption of RX may occur.

Solids Handling

It is always more desirable to handle sensitive or reactive materials in solution. They can be piped around under inert atmosphere and generally protected from environmental problems. However, sometimes there is no way to avoid the handling of reactive solids. That is, solids that are sensitive to O2 and/or water. The sensitivity may only go as far as quality control and specification problems. Or reactive hazards may be in play.

Solids handling is problematic in certain operations. Charging a reactor with reactive solids requires specialized solids handling equipment. Even non-reactive solids present a problem in handling. Dumping solids into an open manway can result inan  incendive electrostatic disharge. It’s made more serious if there is a flammable solvent in the vessel. Here is th rule- you don’t add solids into a reactor manway of there is the possibility of explosive dusts or flammable solvent in the pot.

Filtration is another problematic operation. Well, let’s say that opening the filter with reactive materials in it is a problem. If you use BuLi orRMgX, you probably have to do a  filtration at some point. Unless you quench the BuLi or RMgX in the pot, you are likely to have a hot filter cake.  While I cannot divulge any particular methods here, I can say that managers have to address this issue one way or another. It is especially exciting if the hot cake is wet with a flammable solvent. So, ESD and other ignition sources must be delt with when the filter is opened. Operators must be grounded and all locations for possible charge isolation must be accounted for.  It is best to open a filter in a location where having a hot cake fire is acceptable.

Filter cakes may be waste or product, depending on the circumstance. Drying operations in the filter must account for the accumulation of electrostatic energy as the material dries. It is important to have decay times for the solids if they are potentially energetic. Energetic materials that accumulate static must be allowed to decay their charge prior to handling. Of course, the prevention of charge accumulation is best. Propellant folks will coat granulated or pelletized product with charcoal or grapite to render the solids conductive.

Packaging

Chemists really hate to have to worry about packaging, but I can attest this is an activity that attracts quality control problems. Obviously reactive materials must be compatible with the  package materials of construction. Containers must seal properly.  Steel drums are useful for many kinds of materials, but the bungs can and do leak with temperature changes, so they can pull in moist air.  In terms of reactive hazards associated with containment, usually some choices have to be made. What kind of leak scenario is plausible and does the proposed container pose any special weaknesses? Drums are notoriously susceptable to being speared by forklifts. Cylinders too. 

What hazards are present for a workman who opens the drum with the hazardous material? Does the operator have to open the drum and put in a dip tube for pumping out the material? Perhaps a cylinder with a built in dip tube is safer.

Another matter to consider, especially with solids, is the issue of static charge generation during filling operations. Is the container or liner  conductive or dissapative? Are ESD procedures in place for safe handling?  Liquids can generate considerable static energy, especially when low dielectric constant liquids travel through a plastic pipe.  Transfer of flammable organic fluids should take place in grounded or bonded conductive pipe to the greatest extent possible to avoid charge isolation.

All equipment should be grounded or bonded via a ground that is periodically tested for integrity. Everything should be at the same potential as the ground.  Cement floors are dissipative, but painted cement floors are not. Wooden pallets and fibreboard packaging are dissipative when sitting on bare concrete.

Extractive metallurgy of the 19th century

The first gold lode discovered in Colorado was found where the town of Gold Hill, Colorado, now sits. Gold Hill is presently at the locus of the Four-Mile Canyon fire west of Boulder. As of  today, more than 170 structures have burned, including a few outhouses.

Today, a single gold mining operation remains active at Gold Hill. The kid and I recently visited the area and I wrote a post about Wall Street, south of Gold Hill.

In the last few years I have been fascinated by what started as a simple question-  How did they get the gold out of the ore in the 19th century?  What has become apparent to me as a chemist is the extent to which reasonably sophisticated multistep extraction schemes were employed by 19th century mills and smelters. Their methods of processing would not be unfamiliar to alchemists who practiced similar arts over 400 years earlier.

The alchemists had techniques of calcination, comminution, lixiviation, and distillation available to them. In using these processes, they were inadvertantly performing reduction and oxidation reactions so as to alter the composition of substances with the hope of improving the prospects for isolation of desirable metals.  The 19th century gold and silver mill operators inherited these techniques and mechanized them. One of the key improvements over their medieval predecessors was that they had reasonably sensitive analytical methods as well as some scientific knowledge of the chemical behavior of materials- we call it chemistry today. As the 19th century American gold rush went forward, there became available new methods of gold and silver extraction involving mercury, chlorine, cyanide, and sodium or potassium sulfide and thiosufate.

Any 21st century chemist will recognize most of the inorganic chemistry of 19th century milling and smelting of metals.  But in those days it was not referred to as chemistry- it was known then as it is today as Extractive Metallurgy.

Much of the technology for extractive metallurgy traces back through European mining engineers who had come to the American gold and silver districts.  Two mining engineers in particular stand out in 19th century Au/Ag metallurgy- Guido Kustel and Philip Argall. More about these fellows at a later date. Suffice it to say that they were prolific problem solvers in a time when mine and mill operators typically had more investor’s money than sense.

Some Milling and Smelting Business Models

Prospectors working alone or with investors backing them would prospect a promising area of ground for gold or silver, looking especially for vein outcroppings. If they has cause for optimism they would file one or more claims for the right to have access to the minerals therein. A patented claim was a claim issued by the federal government as a deed that could be bought or old like a a parcel of land. Most of the land of interest was state or territorial land. Many times a claim was filed based on speculation, and a nearby claim with a vein that might go in the right direction would potentially be valuable.

The miners would begin to develop the claim by digging an adit and drifting horizontally following a vein system, or they might dig a shaft in a promising spot in hopes of intercepting a vein rich in value.  Since they were focused on veins which were visible to the miners, the miners were able to dig along the direction of the vein. In doing so, they could hand sort unproductive rock into a waste pile and collect concentrated ore separately.  But then what?

Some mine operators were wealthy enough to have their own mill or smelter to extract the value. However, the majority of mines would sell their ore to a mill, which might be many miles away. A price based on an assay could be negotiated, and the ore sold outright to the mill. The mill would make its profits by selling the gold or silver it extracted. Sometimes a mine would pay the mill a tolling charge and keep ownership of the gold or silver.

Milling and smelting could be a lucrative business or it could result in a total loss. Mills and smelters were run by companies who had plowed a significant financial investment into+ the operation. They relied on the productivity of the gold or silver district. Not infrequently multiple mills or smelters would appear in a district affording lots of competition for ore.   Milling and smelting was labor and energy intensive. Old photographs often show the mills sitting in a mountainous area clear-cut of trees. Wood was needed for buildings and firewood. Refining operations required many cords of wood to run the furnaces or to generate steam for the stamp mills.  If a mill ran out of fuel, their operations were threatened.

Many mines produced ore that was sold to the mill. Mine operators might be paid for the assayed value per ton of ore delivered, or they might be paid a fraction of what was extracted by the mill. The mill could be just down the hill from the adit or shaft, or it might be many miles away.  As a rule, transportation costs were quite high.  Some districts like Caribou had teamsters who would haul ore by horse drawn wagons to mills some distance away. Other districts had rail transportation.

Naturally, ore samples could be tampered with by miners interested in increasing the apparent value of their ore. Sampling methods were developed to produce representative samples for assay. Mills had assay offices to test for the value in the ore and to measure the fineness of their bullion.  Cuppelation was a standard method of providing a gravimetric determination of the gold content of ore.  More on cuppelation in a later post.

Frito-Lay’s New PLA Rattle Bag

As a veteran of the polylactic acid market invasion (PLA or polylactide) in the late 1990’s, I was heartened to see a new commodity application of PLA packaging appear on the shelves of the hometown grocer.  Well, alright. MArket invasion is overstating it a bit. We were one company among several in the race to grab PLA market share.  The founders of our company were engineers familiar with corn wet milling and the starch business. In the end, the skill set that carried the day was the combination of Cargill’s agribusiness presence and Dow’s massive polymer production business expertise. We were doomed. Our place as a Coors subsidiary with a modest cornstarch and wet mill operation just didn’t give us the gravitas to make the thing happen.

PLA is the polyester of lactic acid monomer, or perhaps more accurately, lactide monomer.  I’m generally in favor of PLA as a replacement polymer for polyolefin materials. PLA ultimately sources from starch fermentation in corn steep liquor.  Our process produced lactic acid using steepliquors as a nutrient source.

One of the reasons I left academics was the unusual chance to be part of a seemingly well funded startup aiming to commercialize a PLA process.  I’ve written about this before and won’t repeat it here. Our operation ultimately shut down within a year of my arrival due to some technology problems and a nervous group of investors- not an uncommon scenario.

My job was to come up with a comonomer for PLA to lower the glass transition temperature (Tg) and to bring down the crystallinity a bit. But first, some background.

One of the issues with PLA as a substitute commodity polymer was its relatively high Tg. PLA’s high Tg caused it to be unsuitable for contact with hot liquids owing to the fact that the polymer lose its rigidity and deform.  Food contact applications are a major commodity market for polymer producers, especially if the value proposition to the consumer is the biodegradability of the product.  Commonly disposable items like coffee and soft drink cups & lids, plastic utensils, straws, and diaper components are cited as ideal applications for green polymers. In order for PLA to be substituted into the disposables market, the matter of price and performance had to be resolved.

Our projections by 1998 were that PLA would be price comparable with nylon, then roughly $1.50 / lb.  Nylon was more expensive than polyolefins/polystyrene by quite a range, so the thinking was that at least initially, PLA would be specialty polymer product selling along the applications margins. PLA would have to grow, gaining acceptance by some kind of consumer.

But what is “some kind of consumer”?  It is easy to fall into the thinking that the crucial polymer consumers are the people buying the finished goods containing the polymer. But that isn’t exactly true. There is another key group of buyers than must be satisfied. And they are tough customers.

A crucial group of people who make buying decisions are actually found upstream of retail level consumers. They are the raw material buyers and they reside at several links on the value chain.

Let’s assume that the producer of a polymer -sold in pellet form- has produced a satisfactory product. It meets rigid specs for quality and performance.  The buyer of pelletized raw polymer is some kind of converter. A converter is a company that buys pelletized polymer and converts it to some variety of higher value product by the process of compounding and extrusion.  The compounder may produce films, filaments, or molded widgets. At this stage, polymer products are referred to as resins.

A compounder may be a producer of resin films or resin widgets who, in turn, supplies another manufacturer who uses the resin products for their own applications. Or, compounding may be integrated into the total manufacturing chain by one operator. A producer of things-that-contain-resin-widgets-or-films may have their own extrusion operation to contain cost.

What is critical to anyone scheming to bring a new polymer into the market is this: you have to sell the new resin to the compounder. If the new resin is more expensive, then the value proposition just got really difficult. A new (replacement) resin must have some kind of added value to the compounder and for the manufacturer downstream to  justify the disruption that its substitution is likely to cause.

What kind of disruption can polymer substitution cause?  All manufactured goods have specifications by which the manufacturer is able to distinguish acceptable from unacceptable quality. Specifications for components usually cite raw material specifications comprising physical or chemical properties, appearance, odor, or even specific commercial brands.  Swapping materials of construction or different compositions is a serious undertaking for a manufacturer of established goods. If it ain’t broke, don’t fix it.

So, a resin substitution may require the persuasion of decision makers in a multicompany value chain to effect a substitution. This is the challenge before any producer of new resins. And PLA was in the same place as it was going to market in the late 1990’s. It takes a giant company with massive resources to effect the adoption of a new resin in the marketplace. Sales efforts have to be focused on the true decision makers. These are the manufacturers of packaging materials and the industrial buyers of resin components. They have to be convinced that any new resin won’t hurt existing sales and that there be some kind of premium for going to the trouble adopting change.

So, the new bag containing Frito-Lay Sunchips is on the market and it is made of PLA. Somewhere along the line a decision has been made to risk the change. I’ll say that the bags seem to have the same appearance as the previous variety.

The only problem is the rattle. The bags have rather a loud rattle due to the considerable crystallinity of PLA.  The way to make the rattle go away is to coploymerize it with a comonomer that increases the amorphous component of the polymer. PLA is made from enantiomerically enriched, biologically derived L-lactic acid. L-Lactic acid is used because it can be made cheaply by fermentation. The bugs only make one enantiomer.

The challenges of successfully incorporating a comonomer are many, and they are not all science related either. A comonomer must participate in ring-opening polymerization and combine with lactide. The relative reaction rates need to be in a range that allows for favorable incorporation without undue increases in reactor residence time. Comonomers can produce compositions varying from blocks of comonomer incorporation to random incorporation. It takes much time and abundant resources to work out the most desirable compositions and their respective economics.

We were using reactive extrusion where the residence time was related to screw speed and length of the extruder. Too much residence time at reaction temperature and the PLA would carmelize or darken. Residual acid is a killer. PLA is very sensitive to residual acid in the lactide. Very small amounts can be ruinous. It shut us down.

Incorporation of a comonomer that is not an agricultural or renewable product will taint the value proposition of “Green”.  Caprolactone is an example of a comonomer that had been explored by others, but [at the time of writing] I’m not aware that there is a Green route to that monomer. I recall that there were patent issues that prevented us from exploring caprolactone. However, there is a good chance that the patent issues have now expired. Nothing is forever, not even patents.

Follow this link for an earlier post on this topic.

The secret life of the industrial chemist

My blogging output volume has dropped to a trickle, and what little of what is posted is just blather.  Despite the relative quiescence of this blog, the blogger himself is busier than a one-legged cat trying to scoot across a frozen pond. Unfortunately, the one-legged cat has to keep mum about the missing legs or why he is on the lake in the first place.  If I don’t stroke out from the chronic cortisol exposure, I’ll write about it all one day.

After some years in the industrial setting I am able to see why there is such a disconnect between academia and industry. The imperatives of the industrial chemist are dramatically different than that for a brother or sister chemist in academia. It is the job of the academic chemist to uncover new phenomena and tell the world about it. Oh yes, and teach a few students along the way.

The industrial chemist’s job is to apply known processes or to uncover them himself for greater profit for the stock holders. The main difference is that the industrial chemist must keep the work secret, or more accurately, out of the public domain.

Why did I use the word ‘disconnect’?  Well, if an industrial chemist wants to collaborate with an academic partner, the matter of secrecy comes up.  If the academic cannot transmute the work into a scholarly publication for inspection by the promotion and tenure committee, then he has effectively been unproductive.  Academics turn funding into publications. Well, except for the 50 % of the money that goes into overhead support.  If an academic does collaborate with an industrial group, there is the very real problem for the academic of how to use the work for career advancement, i.e., publication. Just covering academic labor and materials isn’t really enough (or shouldn’t be) for the university workers.

Another issue arises in regard to intellectual property. That is the matter of secrecy within an academic research group.  Say professor Smith has taken advantage of the Dole-Bayh Act and is performing research with the goal of applying for a patent. This very fact sets the group down a path that requires non-disclosure of results prior to and during the application.   Several things have to be in place in an academic lab that are unusual for the academic setting, but normal for the industrial setting.

First, patent-seeking academics must be very quiet about their work during the critical concept development phases. One of the most disastrous things that can happen to a patent application is confusion relating to the matter of inventorship.  And one way to muddy the inventorship is to be careless about who is involved in technical discussions while the invention is in the formulative phase. In the university setting, group meetings with outsiders or uninvolved group members can lead to unexpected and poorly documented inventive contributions.

Word to the wise: You don’t have to wait for someone to complain about inventorship after the patent is allowed. If your own patent attorney, who is an officer of the court I might add, gets wind that someone was left off the inventors list during prosecution, he/she is duty bound to amend the application, possibly casting doubt in the mind of the examiner on the veracity of earlier signed documents.

Playing games with the list of inventors is the fast track to rejection of the application. All inventors and assignees should clearly understand that your own patent attorney, the one whose boat payment you’re funding, answers to a higher calling, so to speak.  They have obligations and liabilities that you can’t  imagine. Help them get you a patent with the cleanest possible file wrapper.

An academic research group with more members than inventors probably needs to split the invention away from the rest of the group. This is a good opportunity for the patent attorney to school the group members on the patenting process and outline best practices. The research prof should outline a plan to partition the group in a way that disclosure is minimized. Notebooks and meetings should be carefully monitored in any event, but some kind of isolation is always best.

Then the question arises of what to do with thesis work that arose from an incomplete patent project. What does the student get out of it? This is magnified even more if the professor is part of a startup company who intends to use the technology the grad student developed. Again, what does the grad student get of it?  A degree? For development services in getting a startup off the ground?  Good question. Certainly there examples out there where these matters have been worked out.

My views on academic patenting have been expressed previously and I still believe it is terrible public policy.

It is plain that patenting in the academic environment poses special challenges and cultural changes for those hoping to get a patent.  In the industrial setting, such matters are normal and institutionalized.

The American gold rush and relativistic electrons

Exactly why do people value gold? Is all of the allure of gold due to its color? What if gold metal did not have the golden color? Instead, what if it had a silver luster like its neighbors on the periodic table of elements? Would we find it quite so appealing?

There are many reasons why people might desire gold.  The motivation to possess gold would surely vary based upon where in the value chain the metal was encountered.  Gold prospectors might value gold because it was an item of trade. Artisans would value gold for more pragmatic reasons relating workability.  Rulers would value gold because it was an asset that could be put in the treasury and later used to buy influence or fund military adventures. Thieves and plunderers valued gold owing its high value per unit volume  and the ability to offer it in trade virtually anywhere.  

Here is what we can say for sure about gold.  It’s high degree of inertness means that it can retain its golden luster indefinitely and bestow an everlasting aspect. Its malleability and ductility means that metalsmithing with fairly primitive tools was feasible. Gold could be hammered into thin sheets that could be cut, punctured, and otherwise worked by artisans to produce impressive art objects. Gold could be worked to produce all manner of ornamentation for the sake of religiosity, as an ostentatious display of wealth and power, or for coinage. Whatever the context, gold leaves an impression on people, aesthetic or otherwise.

Here is where it all gets interesting. You see, one of the consequences of Einstein’s theory of relativity is that as an object approaches the speed of light, c, its mass increases by an amount defined by a fairly simple mathematical relationship. An object’s rest mass is less than its mass appreciably near lightspeed.  The term “relativistic” refers to effects relating to objects traveling near lightspeed.

It turns out that some of the outer electrons around heavy atoms like gold and mercury are moving at an appreciable fraction of the speed of light- they are relativistic electrons.  If these relativistic electrons are at the outer, valence level, then aspects or behaviors affected by relativity may become apparent by how the atom interacts with light or other atoms. 

Chemistry is about the behavior of electrons confined to the space in the immediate vicinity of nuclei, or bound electrons. In particular, the electrons outer, valence, electrons. This is the realm of chemistry.  Chemists go about their business manipulating these electrons for fun and profit. Virtually our entire material experience of life is dictated by the manner in which these electrons interact.

In the case of gold, the 6s electrons are moving at a significant fraction of the speed of light. The magnitude is 58 % of c, according to one internet reference. At this velocity, the electron mass has increased by a factor of 1.22 times its rest mass. This being the case, the Bohr radius of the orbital is contracted by 22 %. 

The implication of this perturbation in orbital size is that an electronic transition between the 5d and 6s orbitals shifts out of the UV range and into the visible band. The molar extinction from the UV cutoff to about 500 nm is high enough that metallic gold takes on its characteristic golden hue from the reflected light.

Gold is not the only element to be affected at the valence level by relativistic effects. Mercury is also affected. The contraction of the 6s orbital results in relative inertness of the 6s^2 lone pair and poor interatomic (metallic) bonding, resulting in the unusually low melting point of mercury.  Indeed it is likely that most of the interatomic attraction is due to van der Waals forces, which is notably weak.

The inertness of the 6s lone pair reveals itself in the oxidation states of bismuth, which has stable oxidation states at +3 and +5. Like other pnictogens, bismuth (III) compounds have a lone pair. But unlike nitrogen and phosphorus lone pairs which are reactive and an important part of their ordinary chemistry, bismuth’s 6s lone pair is rather inert and not significantly hybridized. Triarylbismuth (III) compounds are trigonal planar with the lone pair taking spherical s-orbital symmetry.  UV-Vis experiments will show that for some simple BiAr3 compounds, the n->pi* transition has a very low extinction coefficient, unlike the analogous Ph3P.  Exposure to Pd(II), for instance, will show scant indication of coordination in the UV spectrum, again unlike Ph3P.

This is quantum chemistry stuff that the reader can run down later. What is of interest to me in this post is the fact that, without knowing it, gold prospectors, miners, and mill operators of the 19th century took full advantage of certain relativistic effects in their search for gold.

The first relativistic effect the early miners took advantage of was the simple fact that gold is a colored and relatively inert metal. It could be spotted by simple inspection in streams and quartz veins. The color of gold made it impossible to confuse with other metals. Ofcourse, iron pyrite was always a problem, but there were simple ways to test for pyrite.

The other relativistic tool used by miners was amalgamation of gold (and silver). Mercury, being a metallic liquid by virtue of relativistic valence electrons, could be intimately contacted with gold dust or larger particles to form a solution that would remain liquid up to some modest fraction of gold. Mercury, being quite dense, would naturally seek the low points where the gold would also be found. This dissolution could be affected by simple sloshing or by grinding the mercury with the ore in an arrastra or an amalgamation pan.  After agitation, the mercury would pool and could be easily collected.

Later amalgamation techniques would combine aqueous cyanidation of the ore in the presence of mercury in hopes of better gold and silver  recovery. Reduction of gold or silver chloride occured in-situ to provide amalgam.  Amalgamation of ore that had been chlorinated by roasting in the presence of NaCl was a common solution to the serious problem of sulphuretted auriferous or argentiferous ore.

The miners of the 19th century American gold rush certainly didn’t know that their task of extracting gold would be aided by the effects of high velocity electrons. Most people walking around today don’t know or even care about this more than 55 years after the passing of Albert Einstein.  But it goes to show how subtle effects of nature can affect our lives in unexpected ways. And this is just one of many such nuances of physics.

Process development and struggle

One of the hazards of having a degree in chemistry is the appealing idea that you can explain everything and predict everything on the basis of textbook notions on solubility, electronegativity, pKa’s, or molecular orbitals. These are important things to be sure. But in the field, the recall of knowledge isn’t always enough. More often than not you have to collect data and generate new knowledge.

Rationale of a result on the basis of hand waving and a few reference points can seem compelling in a meeting or brainstorming with a colleague to understand a problem. But in the end, nothing can top having solid data from well conceived experiments.

My chemical “intuition” have proven wrong enough times now that I am deeply skeptical of it. After prolonged periods of absence from the lab I find myself resorting to a few cherished rules of thumb in trying to predict the outcome or explain the off-normal result of a process.

In chemical process development there is no substitute for running experiments under well controlled conditions and capturing solid results from trustworthy analytical methods. It is hard work. You may have to prepare calibration standards for chromatographic methods rather than the preferred single-transient nmr spectrum  in deuterochloroform.

We’re all tempted to do the convincing quick and dirty single experiment to finesse the endpoint. Certainly time constraints in the manufacturing environnment produce an inexorable tilt towards shortcuts. But in the end, depth of knowledge is only had by hard work and lots of struggle in the lab. The most important part of science seems to be to frame the most insightful questions.The best questions lead to the best experimental results.

Process Intensification and the Chemical Marketplace

Somewhere along the timeline of a given chemical plant process a manager will (or at least should) ask the question: “can we run this process in a more efficient and safer manner”?  Chemists and engineers may be set to work finding ways to extract more profit from a process.

There are numerous ways any given process may be improved. How that is done specifically depends on the process, obviously. But certain generalities can be made that serve as a guideline in thinking through the process.

In this essay I will limit my comments to batch or semi-batch processing and to specialty and fine chemicals. Continuous processes and commoditized products are out of the scope of this essay.

Batch and Semi-Batch

A batch process is one in which a vessel is charged with raw materials which are allowed to react to form a desired product. A semi-batch process is one in which raw materials are metered into the vessel over the course of the reaction. From a process safety perspective, the big difference between the two is that the batch reaction is the one with all of the reaction energy contained in the vessel from the start. A semi-batch process is one in which the energy is metered in based on the limitations of heat transfer capacity.

Commodity Chemicals

Some chemicals are commodity products and others are specialty or fine products. A commodity chemical is a product which is produced at a large (relative) scale, commonly in a continuous process, and is subject to price pressures generated by national or global scale competition. There are exceptions, naturally. Generic drugs or semiconductor chemicals may be commoditized but manufactured by relatively small scale batch processing though still subject to commodity market dynamics.

A commodity chemical product is one which has numerous producers offering similar specifications and varying mostly by price, often resulting in strong competition. As a result of the large scale and the great competition, commodity chemicals are often priced at low dollar-per-unit levels. Owing to the basic nature of commodity chemicals in manufacturing, it is not uncommon for commodity chemical sales volume to be an economic indicator.

Here is an important economic point in thinking about commodity vs non-commodity chemicals. Commodity chemicals typically have a cost structure featuring large raw material or energy costs. Commodity processing is all about the dilution of overhead into high volume. Commodity cost structures may be quite immobilized by fixed raw material and/or energy costs.

Commodity chemicals are commonly used for mass production of other goods. Examples of commodity chemicals include NaOH, soda ash, potash, sulfur, sulfuric acid, HCl, chlorine, BTX, ethylene, propylene, butanol, ethanol, methanol, naphtha, methane, hydrogen, ammonia, etc. These are materials bought and sold by the railcar and whose sales volumes indicate the health and vigor of entire nations. Other, lower volume, chemicals are commoditized as well. Additives and treatment chemicals for commodity consumer goods like pigments, solvents, plasticizers, dyes, food processing additives, lubricants, polymer additives, metal treatment chemicals, agrichemicals, etc. These goods are sold on the large scale for their performance modification or other properties.

Specialty and Fine Chemicals

Specialty and fine chemical products are commonly sold in lower volumes for a broad range of manufacturing and formulation activity. There is no sharp line of demarcation between commodity and high volume  fine chemicals. Commoditization is less a manufacturing phenomenon and more of a market phenomenon. The same is true for specialty and fine chemicals.

Specialty and fine chemicals are an important part of the total chemicals market sector. There are tens of thousands of chemical entities on the market. Most are deeply obscure, in demand only by a few researchers. A common growth strategy of  catalog companies is to increase the number of catalog offerings, thus snagging new customers by providing specialized precursors to those who do not want to make a science project out of starting materials. This business strategy has helped to grow the well known chemical catalogs to their immense size.

A specialty chemical is a material that feeds into a particular use, or is valuable or usable only to a particular end user. Commonly, a specialty chemical may be used for a single application by a single customer or a few narrow applications for a few customers. A specialty chemical is often part of an intellectual property package whose use and identity is highly controlled. The specialty chemical, like a fine chemical, may be covered under process patents that limit manufacturing practices.

A specialty chemical may be of technical grade (i.e., 60 to 95 % purity) or it may be highly purified. It might be of a complex composition and specifiable only under bulk properties like viscosity, flash point, or color. Or a specialty chemical might be highly purified and have sharply defined specs requiring spectroscopy, chromatography, XRD, % ee, or elemental analysis. A specialty chemical might also be a fine chemical in the sense that its composition is in the public domain, but its application is just obscure or covered by a patent.

Generally, a fine chemical is a substance whose composition is in the public domain and is refined to some commercially viable level. A fine chemical may be a reagent or a substrate and may be  used by anyone technically qualified to handle it. Very often, the composition of a fine chemical is understood to a high level. Fine chemicals may be starting materials for the manufacture of other substances, or may be used directly in an application where it remains chemically intact at the retail level.  An example would be an emulsion stabilizer or some polymer additive.

Specialty and fine chemicals are not mathematically distinct definitions. The differeces are based on market behavior and intellectual property. Examples exist which may find a home under both definitions. For the most part, a specialty chemicals manufacturer is a producer of customized materials with a limited base of potential customers.

The Prime Directive

Here is the central business imperative of any chemical plant- we want to run the reaction as fast as possible without taking undue risks. Labor costs and other overhead accumulate with process time, Δt. Any given batch fine or specialty plant has x gallons of capacity available for use 24 x 7 every year. The key to profitable operation is to get maximum product output per unit time. That means maximum space yield and/or maximum rate. Decreasing production time is equivalent to increasing plant capacity.

Production risk divides into two principal domains: 1) safety and 2) economic. While it is possible to have an economic risk without a significant safety risk, the practical fact is that all safety risks are also economic risks. So in the execution of a process improvement, very practical thinking has to guide the work.

Cost Drivers

Commoditized chemicals are often disproportionately raw material or energy cost intensive relative to specialty and fine chemicals. High volume, low margin products that have been in a competitive market a while have most likely been optimized such that the labor contribution to overhead has long been minimized. For a given plant, significant improvements to the cost structure may not be easily found in the labor column if the major costs are raw mats. Except as follows. Relocating a plant to a country with lower labor and/or tax costs. Commodity production follows the labor cost gradient from a high-cost labor pool to a lower-cost labor pool.

Process intensification on chemical products that have been commoditized for a long time is difficult. Besides relocation of the manufacturing site, a step change in processing technology may be needed to improve process economics. Fundamentally new chemistry (or catalyst!) or reactor type or in materials handling may be needed to justify a change.

Whereas commoditized chemical costs may be driven by raw material or energy costs, specialty and fine chemicals are most likely to have a cost structure driven by labor and overhead. A dominance by labor cost contribution will be especially true early in the life of the chemical product. The early developmental period in the market life of a fine or specialty product is the time when competition is likely to be minimal and price pressures lowest.

Early in the life of a fine or specialty chemical product is the time when the end user is struggling to understand the market picture. This is the commercial development period. While the end user (customer) is certainly trying to contain costs, low volume may cause the buyer to rely on a single supplier for a time. This gives the vendor a chance to log enough process iterations to bring the production costs more in line with expectations.

When pricing smaller volume products, every effort should be made to pad the costs in anticipation of process upsets and low yields. And for high margin. R&D and scaleup costs are typically highest early in the life of a product. Margins should be high enough early on so that the early production pays for the development. Customers will not be enthused about this. They’ll want you to “partner” with them and get some skin in the game early. Try to avoid this, politely.

A small volume fine or specialty product should be heavy in labor costs. Over time, and as price pressure from customers mount, the vendor should be able to accept price concessions through improvements in labor contribution. This is wiggle room. A smart vendor will never price a new product too close to raw mat cost since the inevitable movement of price is downward.

Low volume specialty or fine chemicals are often not subject to the same sort of pricing dynamiocs as the commodity chemicals. This category of chemical manufacture is more obscure and the products may not be manufactured constantly or in large lots.

Importantly, lower volume fine and specialty chemicals are commonly purchased on a spot buy basis rather than a supply contract. Owing to the lack of long term certainty of cash flow, spot buy prices are always higher than contract prices.

Process Intensification. The benefits.

The business of making a reaction execute in a shorter time or in a higher batch space yield or batch chemical yield is called process intensification. The idea of intensification is to produce more product per unit batch volume of processing equipment and/or per unit batch time. Every chemical plant has a fixed number of operable reactor gallon hours per year.  Given that conventional chemical batch reactors are fixtures that are very expensive to modify or change out, it is desirable to focus effort on getting the maximum product out of those limited reactor gallon hours.

In a competitive market, one way to grow is to find advantageous economies of scale and pass some of that improvement along in the form of more attractive pricing.  The ability to maximize the throughput of product in fixed equipment is the ability to dilute overhead expenses into a greater number of kgs of product and direct more cash into the profit column.

Process intensification almost always involves doing something faster, hotter, at higher pressure, or in increased concentration. That is the intensification part. An exception might be an alternate process that affords a higher chemical or space yield, or faster rxn rate without undue risks.  One should always be on the lookout for these plums.

Process Intensification. The down side.

The attactive part of process intensification is quite plain. But there is a down side that may or may not be apparent in any given intensification project. It is a change that could bring plant operations closer to the release of hazardous energy.

The question that any process intensification project should squarely address is the matter of the accumulation of hazardous energy. This can be manifested in many ways.

For example, you increase the concentration of your reaction mixture in your process. This is a space yield intensifying improvement that has the benefit of advantageous bimolecular kinetics. You get more product per batch and you increase the reaction rate by increasing the reagent concentrations.  Reagent feed times are nominally increased, but probably not to a deleterious extent.

Naturally, there are consequences to consider. Is there an induction period to look out for? The thermal consequences of this may be magnified at higher space yields.

Does the intensified process produce excessive and unwanted side products?

Does the process generate a precipitate or increase the viscosity of the reaction mass? Increased viscosity has a deleterious effect on heat transfer and mixing efficiency. Slurry formation may be enhanced and consequently produce problems with discharge and pumping of the reactor contents. Filtration may be problematic as well.

Furthermore, as a result of reagent addition the reaction mixture may have a greater density that the initial solution in the vessel, diminishing power transfer efficiency in agitation. Effectively you may end up vortexing an inner band of reaction mass with poor flow along heat transfer surfaces.

Cavitation at the impeller tips may occur and attenuate the efficiency of heat transfer. Heating a viscous two phase reaction mass may lead to localized overheating along the reactor  jacket if it is rigged for heat. I have seen this lead to flash boiling of volatile solvents along the jacket surface with an increase in pot pressure.

Another form of process intensifiaction is through the application of higher reaction temperature and/or pressure. Increasing the reaction temperature could be as easy as using a higher boiling s0lvent. Or it could entail higher pressure as well. Whereas most operations can easily accommodate a higher boiling solvent, higher pressure will require specialized pressure vessels. These are less common, in fact, they are part of a manufacturing subspecialty in their own right.

To summarize, intensify a commodity chemical process is more likely to involve  addressing raw materials, energy inputs, and material handling.  Conversely, while specialty and fine chemical processing could benefit from the above areas of concern, unit labor cost is likely to be a target for process improvement. Labor cost is something that can be minimized most easily by process intensification and quite likely without fundamental equipment changes.

From time to time, all processes should be re-examined for efficiency and safety improvements. But the operator should expect consequences in any process change.

A chemist’s encounter with boneheads and the disreputable

One of the things that happens to a chemist in the sales department is the business of taking odd phone calls. Someone out there will scan the internets for information on some particular substance or product and find the number of your company switchboard. The person at the front desk  will spend a moment with the caller and then connect them with someone like myself.

During my business development time I have been amused, surprised, pestered, annoyed, and yes, a little frightened.  I have fielded calls from a prisoner wanting expert witnessing (his planned appeal was based on a false premise), illicit drug makers wanting bulk intermediates sent to their motorcycle or chrome shops, and crooked characters wanting items on the MCA list sent to their garage operations.

I am not a member of the law enforcement fraternity. God knows these characters have never asked for my help.  There is precious little I can personally do in the fight against drug crime. But foiling those who would profit from poisoning the nervous systems of our citizens is something that can be done by chemists.

I have spoken with misguided people on the dark side of chemistry who are on the fast track to prison. And, I have taken calls from parents of K-12 students wanting energetic or otherwise hazardous materials for their science fair project. In this case, we’ll have a polite discussion about safety and I’ll offer some alternatives.

I have been yelled at by frustrated foreign nationals for my refusal to quote on items on the munitions list or the State Department’s official shit list of bad actors. Some were persistant buggers, but I extracted satisfaction in interfering with their sourcing plans. The front lines in illegal technology transfer or illegal synthetic drugs is not in the offices of the authorities. It is on the phones and emails messages of companies who sell materials or devices that facilitate the activity.

It turns out that knowingly selling substances to suspicious characters is not only morally wrong or makes you an accessory, but it is just plain bad business. Long term stability for you and your company requires compliance with the code. Selling materials that may be used for illicit purposes by unqualified buyers is only an open invitation for trouble.

Trolling for organizational weaknesses happens all of the time and all over the business world. Industrial espionage, attempts at illegal export/import of controlled materials, and raw material sourcing attempts for illicit or controlled substances. You have to keep your head on a swivel and qualify your customers.  

Trade shows are particularly bad for spying and competitive intelligence gathering. Companies who can afford large trade show booths will have an enclosed room to meet privately with potential customers. That way watchful eyes will have a harder time figuring out what they’re up to.

Few experienced business development people are shy about asking questions, especially yukking it up over a business dinner and drinks. When in doubt about giving information, just shut your yap, shrug your shoulders, and grin.

Always be up front and honest when it comes to withholding confidential information. Even, or perhaps especially, when you have an NDA in place.  You do not want to get in the habit of discussing sensitive topics in social settings. Leave that for meetings in the conference room where your cohorts can participate and everyone can hear what was disclosed. Savvy business people on either side will halt conversation on the spot if they believe that proprietary information is being divulged inappropriately.

As to the matter of gaming the system, I’ll offer that it’s always better in the long run to avoid planting misinformation. It is better to be regarded as uninformed or unhelpful rather than as a liar in the sales world. You can eventually slough off the reputation of being a bit uninformed or rude. But once branded as a liar, even in a field of liars, it is a stink that will follow you for the rest of your career in sales.