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Category Archives: Chemical Industry
Vannoccio Biringuccio. Sixteenth Century Chronicler of Metallurgy.
By the early 16th century in Europe, metallurgy had become an established cottage industry in numerous locales. Artisans were sourcing copper, tin, zinc, antimony and iron ores for reduction, refinement and alloy production for cannon and bells among other products. While there was no systematic science of chemistry in a form recognizable today, the necessity of constant proportions was understood and exploited to maximize the efficient use of scarce materials. Metallurgists of the 16th century would no doubt share the enthusiasm of developing technology with the same fervor as the technologists of today.
Unfortunately for these 16th century technologists, the contribution of centuries of alchemy produced a confusing array of occult-based practices. These alchemical practices were based on Aristotelian notions of material “qualities” rather than a system of quantitative relationships of and between substances. It is thought that alchemy began with Grecian metalworker’s practical knowledge of metal preparation. Inevitably, this practical art was overprinted with a thick layer of theological mysticsm by the end of the first millenium. By the end of the alchemical age, any systematic theories of matter were blended into a Mulligan stew of early Roman Catholic mysticism, incomprehensible nomenclature, and the false choices set forth by Aristotle in his theory of matter.
Fortunately for 16th century practitioners of the metallurgical arts, several encyclopedic works were published detailing the practical art of smelting and casting of metals and what we now know to be alloys. A prominent early work published in 1540 was the Pirotechnia by Vannoccio Biringuccio (1480-1539). Born in Siena, Italy, over the course of his life Biringuccio traveled extensvely throughout Italy and Germany. His Pirotechnia is a series of books and chapters detailing foundry techniques that he witnessed first hand throughout his travels. He made every attempt to describe methods and techniques in enough detail to accurately capture the technique in question. Above all, he completely drops all the alchemical mysticism and bases his comments on process oriented details such as measured proportions and processing conditions.
Up to this point, what was missing from this very early form of chemistry was a systematic collection of facts and measurements and an accurate chemical model in which to give the facts meaning and predictive value. Biringuccio, and later Agricola, would begin the disengagement of alchemical mysticism and provide a basis of metallurgical technology upon what might be called science. In a real sense, this helps to set into motion the western industrial revolution. Metallic goods would be produced by very pragmatic artisans who would continue to improve their art through the application of rudimentary measurement. While it would be four centuries before atomic theory would be developed to make sense of the manner in which definite proportions operated, systematic methods of assay would begin to appear well before atomic theory. The ability to identify value in ores and quantitate it allowed the mass industrialzation of metals.
Devon Energy Sells Stakes to SINOPEC in Shale Gas Plays
Devon Energy has raised $900 million in cash from Sinopec Group for a stake in Devon shale gas plays. These gas projects include the Utica, Niobrara, and Tuscaloosa formations.
What is interesting is not so much that China has bought its way into the extraction of a resource that the USA has in some abundance. What is more troubling is that China has bought its way up the learning curve in horizontal drilling and fracturing.
According to the article in Bloomburg Businessweek-
China National Petroleum Corp., Sinopec Group and Cnooc Ltd. are seeking to gain technology through partnerships in order to develop China’s shale reserves, estimated to be larger than those in the U.S.
“In these joint ventures, the partner does typically get some education on drilling,” Scott Hanold, a Minneapolis-based analyst for RBC Capital Markets, said today in an interview.
So, the business wizards at Devon in OKC have arranged to sell their drilling magic to the Sinopec for a short term gain on drilling activity. Way to go folks. Gas in the ground is money in the bank. These geniuses have arranged to suck non-renewable energy out of the ground as fast as possible. Once again US technology (IP, which is national treasure) is piped across the Pacific to people who will eventually use it to beat us in the market. Score another triumph for our business leaders!!
The market is like a stomach. It has no brain. It only knows that it wants MORE. Th’ Gaussling.
It’s a banner day for American Business.
Thorium and Rare Earths. A Possible Market Synergy.
If one studies the economic geology of Rare Earth Elements (REE), it becomes clear that REE’s are frequently (usually?) found in deposits rich in other elements. Deposits of zirconium, tantalum and niobium, for instance, are frequently co-located with REE’s.
The REE’s are found in ore bodies that are naturally enriched in either heavies (yttric or HREE’s) or lights, (ceric or LREE’s). The LREE’s seem to be the most common spread of the REE’s. Molycorp’s Mountain Pass bastnasite deposit is a good example of this.
What is not so widely known is that thorium and/or uranium are nearly always found in these deposits. This might be regarded as a good thing except that companies in the REE business seem to be less interested in actinides than lanthanides. The actinide business is fraught with complications related to the natural radioactivity of Th and U. If one is interested in rare metal production, the matter of radioactivity is unwelcome.
However, there is opportunity here if certain institutional thinking is allowed to expand. I refer to the global preference for uranium and plutonium in the nuclear fuel cycle. Nearly the entire world’s nuclear materials infrastructure was directed to the production of yellowcake and separation of U235 from U238 post WWII. While there has been some experimentation with thorium 232 in the US, and there are some limited initiatives in motion, it has been largely neglected in reactor design and the fuel cycle in favor of uranium and plutonium.
Rare earth element mining and processing naturally produces thorium and uranium. At present, those practicing REE extractive metallurgy have every incentive to avoid concentrating the actinide components owing to the radioactivity. However, if there were a coherent program for the development of an efficient thorium fuel program, this natural resource could be efficiently taken from the REE product streams now or in the future.
Our reliance on energy will trend substantially towards electricity. The greater absolute abundance of Th over U, as well as the ability to use 100 % of the predominant isotope makes thorium a good candidate for energy exploitation. The recent boom in REE exploration has uncovered new sources of thorium. The nuclear genie was let out of the bottle nearly 70 years ago. By now we should be a little smarter about how we use it.
Re-thinking start-up opportunities
It is interesting how ones perception of opportunities in the world depend on your context. I have academic colleagues who are in nanotechnology, for instance. When I have spoken of the apparent dearth of entrepreneurialism in chemistry, the sincere feedback I get is that there are nanotech-related startups out there. You know, I don’t doubt this.
What I was unable to articulate to my friends was that we need people willing to start companies for the manufacture of starting materials and intermediates for less cutting edge applications. I’m afraid that the word “start-up” has come to mean “bleeding edge technology”.
Have you ever tried to source specialty silanes or halogenated hydrocarbons for instance? The choices of manufacturers in North America are very slim. There are companies in the USA and Canada who manufacture pharma related materials. But believe it or not, not everyone needs costly cGMP manufactured feedstocks. You can find suppliers of thousands of varieties of boronic acids, esters, and difluorides. But what if you want an alkyl chloride? In my experience there has been a mass extinction of North American halogenators in the last 10 years.
In the previous 5 decades US taxpayers have heavily subsidized US industry by the establishment of a university research complex residing at many dozens of public and private universities. Several generations of faculty at these institutions have written and been awarded a large number of grants over the decades that have produced the scientific talent. Some of the graduates have been the children of those whose combined support via taxed income paid for the complex. Others, in the form of foreign undergraduates, graduate students, and post-docs have been invited to come to the US and take advantage of this rich resource.
I, for one, am in support of sharing the scientific knowledge that has been so expensive in time and money. But what we find is that over the decades, the unstoppable advance of civilization has come to apply the inventions of technology to increase industrial efficiency by reducing the need for labor. Thus, as technology has advanced, the man-hours needed for any given item of commerce has generally declined.
When you combine this natural consequence of invention with a cultural inclination to export industrial production, what you get is a post-industrial civilization that becomes unable to support its previous level of comfort.
The US has been exporting its industrial magic faster than it can adapt to deindustrialization. Whereas in previous times whole cities have grown around manufacturing plants, today we have whole cities substantially abandoned and blighted (like parts of Detroit). Public corporation shareholders who have taken full advantage of the rich infrastructure of the USA have pulled up stakes and moved to Mexico or Asia. This article in Forbes is telling.
The combination of automation plus outsourcing overseas with the absentee landlord management of public corporations has triggered a basic instability in our culture. No one really knows how this will play out.
This is what leads me to urge my colleagues out there to consider starting out on your own. It will be hellishly difficult and will consume 5-15 years of your life. I have been a part of several failed startups myself. It is really hard to do. But let me say this: Avoid starting with a one-act pony, and find a way to have something to sell right away. Not all start-ups have to bring single item, new technology on stream. Find a niche selling high value added, low volume products. Don’t be intimidated by environmental complications and zoning. You have to put your head down and plow through it. Showing up and some hard-headed persistance counts for a lot.
Mercury Processing at the New Idria Smelter
A few Andreas Feninger photos found at the Library of Congress are shown below. The New Idria mine was a productive mine and smelting operation in central California. Note the fellow at the tilted sorting table, physically agitating the mercury from the solid soot and allowing it to run down the table for collection. This is a gravity sorting process. Hard to know what kind of occupational exposure the poor fellow is into.
Worker collecting mercury from soot from smelter at New Idria mine, ca 1942. Library of Congress.
Since the early days of Spanish mercury trade, mercury has been packaged in iron flasks. According to my sources, the 76 lb sizing of the flask was based what laborers and pack animals could plausibly carry all day. In the picture below, a flask is being filled with mercury at the New Idria smelter.
Mercury Filling Station at New Idria Mercury Smelter, 1942. Photo by Andreas Feninger, Library of Congress.
Cinnabar ore was crushed and then roasted in a rotary kiln. This process not only released the sulfur from the cinnabar (HgS), but also decomposed the oxide and volatized the mercury. The mercury vapor was knocked down from the exhaust gas in condensers.
Rotary Kiln at the New Idria Mine and Smelter, 1942. Photo by Andreas Feninger, Library of Congress.
Process development with calorimetry
I’ve turned my attention to reaction calorimetry recently. A reaction calorimeter (i.e., Mettler-Toledo RC1) is an apparatus so constructed as to allow the reaction of chemical substances with the benefit of measuring the heat flux evolved. Reaction masses may absorb heat energy from the surroundings (endothermic) or may evolve heat energy into the surroundings (exothermic).
Calorimetry has been around for a very long time. What is relatively recent is the development of instrumentation, sensor, and automation packages that are sufficiently user friendly that RC can be plausibly used by people like me: chemists who are assigned to implement a technique new to the organization. What I mean by “user friendly” is not this: an instrument that requires the full time attention of a specialist to operate and maintain it.
A user friendly instrument is one engineered and automated to the extent that as many adjustments as possible are performed by the automation and that the resulting sysem is robust enough that operational errors and conflicting settings are flagged prior to commencing a run. A dandy graphic user interface is nice too. Click and drag has become a normal expectation of users.
An instrument that can be operated on demand by existing staff is an instrument that nullifies the need for specialists. Not good for the employment of chemists, but normal in the eternal march of progress. My impression is that RC is largely performed by dedicated staff in safety departments. What the MT RC1 facilitates is the possibility for R&D groups to absorb this function and bring the chemists closer to the thermal reality of their processes. Administratively, it might make more sense for an outside group to do focus on process safety, however.
In industrial chemical manufacture the imperative is the same as for other capitalistic ventures- manufacture the goods with minimal cost inputs to provide acceptable quality. Reactions that are highly exothermic or are prone to initiation difficulties are reactions that may pose operational hazards stemming from the release of hazardous energy. A highly exothermic reaction that initiates with difficulty- or at temperatures that shrink the margin of safe control- is a reaction that should be closely studied by RC, ARC, and DSC.
It is generally desirable for a reaction to initiate and propagate under positive administrative and engineeering controls. Obviously, it is desirable for a reaction to be halted by the application of such controls. Halting or slowing a reaction by adjustment of feed rate or temperature is a common approach. For second order reactions, the careful metering of one reactant to the other (semi-batch) is the most common approach to control of heat evolution.
For first order reactions, control of heat evolution is had by control of the concentration of unreacted compound or by brute force management of heating and cooling.
Safe operation of chemical processing is about controlling the accumulated energy in the reactor. The accumulated energy is the result of accumulated unreacted compounds. Some reactions can be safely conducted in batch form, meaning that all of the reactants are charged to the reactor at once. At t=0, the accumulation of energy is 100 %. A reliable and properly designed heat exchange system is required for safe operation (see CSB report on T2). In light of T2, a backup cooling system or properly designed venting is advised.
The issue I take with the designers of the process performed at T2 is this: They chose to concentrate the accumulated energy by running the reaction as a batch process. This is a philosphical choice. The reaction could have been run as a semibatch process by feeding the MeCp to the Na with a condenser on the vessel. Control of the exotherm could have been had by control of the feed rate and clever use of the evaporative endotherm. A properly sized vent with rupture disc should always be used. These are three layers of protection.
Instead, they chose on a batchwise process relying on a now obviously inadequate pressure relief system, and the proper functioning of water to the jacket.
No doubt the operators of the facility were under price and schedule pressure. The MeCp manganese carbonyl compound they were making is an anti-knock additive for automotive fuels and therefore a commodity product. I have no doubt at all that their margins may have been thin and that resources may not have been there to properly engineer the process. This process has “expedient” written all over it in my view.
Reactions that have a latent period prior to noticeable reaction are especially tricky. Often such reactions can be rendered more reliable by operation at higher temperatures. Running exothermic reactions at elevated temperatures is somewhat counter-intuitive, but the issue of accumulation may be solved.
Disclaimer: The opinions expressed by Th’ Gaussling are his own and do not necessarily represent those of employers past or present (or future).
Power Generation with Mercury Turbine
The South Meadow generating station was operated by the Hartford Electric Company in Hartford, CT. The unit described in the 1931 Pop Sci article used 90 tons of mercury in the boiler. The article states that the South Meadow generator produced as much as 143 kWh from 100 lbs of coal, as opposed to an average of 59 kWh from conventional coal fired plants and 112 kWh from exceptionally efficient coal fired plants. The article describes an incident at the plant where a breech of containment from an explosion in the mercury vapor system occurred, releasing mercury and exposing workers to mercury vapor.
The Schiller Mercury Power Station in Portsmouth, NH, is described in this link.
Mr. Thiel Speaks
When you look for science news at news aggegation sites like Google News or popular publications like, well, any given magazine or newspaper, or (yawn) any given non-fiction television program, what you are likely to find are fluff pieces on topics related to medicine, automobiles, and telecommunications. To people in the news business, scientific progress means new kinds of medicines, better cars, and the latest (n+1)G cell phone or iPad.
It is possible for even successful people to apply pop-culture metrics to economic theory. For instance, the founder of PayPal, Peter Thiel, has written an essay for The National Review in which he questions the motives of scientists as well as their ability to maintain the growth of scientific progress.
The state of true science is the key to knowing whether something is truly rotten in the United States. But any such assessment encounters an immediate and almost insuperable challenge. Who can speak about the true health of the ever-expanding universe of human knowledge, given how complex, esoteric, and specialized the many scientific and technological fields have become? When any given field takes half a lifetime of study to master, who can compare and contrast and properly weight the rate of progress in nanotechnology and cryptography and superstring theory and 610 other disciplines? Indeed, how do we even know whether the so-called scientists are not just lawmakers and politicians in disguise (italics mine), as some conservatives suspect in fields as disparate as climate change, evolutionary biology, and embryonic-stem-cell research, and as I have come to suspect in almost all fields?
The article goes on to paint a picture of failure on the part of the scientific community for not coming up with a Moore’s law style of continuous bounty for the consumer.
Here is where I greatly disagree with Thiel. He cites the stagnation of wages as an indicator of economic progress which, in turn, is an indicator of tepid technological progress.
Let us now try to tackle this very thorny measurement problem from a very different angle. If meaningful scientific and technological progress occurs, then we reasonably would expect greater economic prosperity (though this may be offset by other factors). And also in reverse: If economic gains, as measured by certain key indicators, have been limited or nonexistent, then perhaps so has scientific and technological progress. Therefore, to the extent that economic growth is easier to quantify than scientific or technological progress, economic numbers will contain indirect but important clues to our larger investigation.
… Taken at face value, the economic numbers suggest that the notion of breathtaking and across-the-board progress is far from the mark. If one believes the economic data, then one must reject the optimism of the scientific establishment (italics mine). Peter Thiel, National Review.
This is where Thiel drives into the weeds. He conflates stagnant wages in the post Viet Nam era with a failure of science and technology to produce the kinds of advances he would recognize as worthy.
What is lost on Thiel is the fact that stagnant wages are a kind of benefit to employers and investors as the result of technology. Over this so-called period of stagnation in wages is a complementary increase in productivity. If anything the improvements in technology unseen by Thiel and his ilk have been applied to render human labor obsolete, thereby sustaining profits. China hasn’t gotten all American jobs. Machines have taken over much ot it.
The fact that Thiel scans the horizon from his perch and fails to see this is indicative of a kind of blindness of prosperity. In his world, technology is the internet. Apparently, people like Thiel only register scientific progress as a stream of shiny new consumer electronics, supersonic transport, or brain transplants. The advances in science and technology from the last 20 years are everywhere, not necessarily just in internet technology, cell phones, and Viagra.
Semiconductor technology is now well below the micron scale and heading to the tens of nanometers. Bits of data are heading toward tens to hundreds of electrons per bit. Lithographic fabrication at this scale allows for rules of thumb like Moore’s Law. Growth in component density can multiply parabolically or more as greater acreage of chip surface is consumed in 3 dimensions. Many doublings are possible in this domain.
But parabolic growth in aircraft or land vehicle speed is limited by other physics. A dynamic range of only a few factors of ten in vehicle speed are economically feasible. Fossil fuels are fantastically well suited for use in transportation owing to their high energy density, low cost per kiloJoule, and ability to flow through pipes. Fundamentally new forms of energy storage are hard to find and are expensive. All energy usage is consumption. Science can only go so far in facilitating better forms of consumption for the profligate. Doing work against gravity also consumes lots of energy, so the world of George Jetson never became feasible.
Ordinary automobiles that comprise a part of the stagnancy that Thiel bemoans are coated in highly advanced polymer coatings made from specialty monomers, catalysts, and initiators. The polymeric mechanical assemblies are highly engineered as well as is the robotic assembly of the vehicle. The implementation of automation in the manufacture of plain old cars is just a part of the overall issue of low job growth. In this case, technological advancement => stagnant growth in wages and employment.
Octopole and Quadrupole
Busy week learning to use the new ICPMS. Pretty flippin’ amazing instrument. Reaffirms my admiration for Bill and Dave. A lot of nuances and software to learn, but do-able. Agricola and Biringuccio could’ve used one of these. Of course, they’d have needed 208 VAC single phase power …
Interesting approach to polyatomic ion interferences- run the beam through a He chamber to slow down the large cross section ions and use the octopole to steer the beam into the off-axis chamber exit and into the quadrupole mass filter. Clever monkeys.
Lamentations on Chemistry 