Category Archives: Chemical Industry

Fear and Loathing with Frac Fluids

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There is considerable handwringing over hydraulic fracturing fluids and their potential effects on “the environment”. I use quotes in ironic fashion because I see very little parsing of the issue into relevant components. The chemical insult to the environment is highly dependent on both the substances and the extent of dispersion. But I state the obvious.

There are surface effects at the drill site and there are subsurface effects. A spill on the surface is going to be relatively small due to the limited size of the available tankage on site. I drive by these sites almost daily and can see with my own eyes the scale of the project. A surface spill of materials will be limited in scope.

The subsurface effects are complex, however, and the magnitude of consequences will depend on both the extent of the fluid penetration into aquifers and the nature of the materials in the fluid. Much criticism has been dealt, rightfully I think, over the secrecy claims on the composition of these fluids. The default reply from drillers has rested on trade secrecy. To be sure, the matter of government forcing a company to reveal its art is a serious matter. But the distribution of chemical substances into the environment requires some oversight. Especially when substances are injected into locations where they cannt be readily remediated. The remediation of an aquifer is a serious undertaking which may or may not be effective.

If you want to see what is potentially in frac fluids, go to Google Patents and search “hydraulic fracturing fluid”. A great many patents will be found. This will give the length and breadth of the compositions patented. Of this large list only a few are used in current practice. The potential carrier fluids vary from water to LPG (!). Water is a common component, but brine is said to be preferred. Additives include hydrochloric acid and surfactants. The MSDS documents may be a good source of info. Consider that a substantial threat to ground water may be that it is rendered non-potable rather than outright  toxic.

The Sheri Sangji Case

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Many readers know that research assistant Sheri Sangji died from burns sustained in a laboratory fire in the lab of UCLA professor Patrick Harran. Harran and university Regents are up on felony charges for their part in the incident. I understand that the charges are based on occupational health and safety violations related to the incident.

[The excellent blog Chemjobber has been following this story.  I might add that this blog should be put on your Favorites list if it isn’t already there. The author puts a lot of work into it and it shows.]

Sangji was transferring t-butyllithium when her plastic syringe came apart and a quantity of the pyrophoric solution was splashed on her and ignited. She sustained fatal burns when her clothing caught fire and she died 18 days later.

Syringe techniques are common and the use of plastic syringes in such transfers of lithium alkyls is not unusual or automatically over-dangerous. However, some syringes have what is called a Luer tip where a syringe needle is attached solely by friction.

Another design has a Luer lock where the needle is affixed with a twist of the needle into a friction lock.  The former design, with the tubular tip and no locking mechanism is prone to disconnection under tension and on withdrawl of the needle from the septum on a pressurized bottle, the needle is likely to squirt bottle contents onto the worker. The Luer lock largely prevents this type of accident.

Another failure mode is when the plunger is inadvertantly withdrawn completely from the barrel of the syringe. Minimally, this would release the contents from the barrel, possibly on the operator. If the plunger is pulled completely out while the needle is still in a pressurized bottle, a fountain of liquid may discharge, possibly on the operator.

Syringe plungers with a rubber tip are prone to swelling in organic solvents and may become difficult to move during a single use. If the plunger is pulled with great force, it might release suddenly causing it to come out of the barrel along with the contents.

Other syringes have plungers that provide a seal by plastic-on-plastic pressure. The seal depends on the elasticity of the barrel to accomodate the slightly oversized plunger. These syringes do not come with Luer locks and as such, are not forgiving of less than skillful use.

I do not know exactly what technique Sangji was using. Aldrich distributes literature on the use of a cannula in the transfer of air sensitive liquids. That is fine, but if you want 0.1 to 60 mL of RLi, a syringe is the most expeditious method for delivering a precise aliquot in my opinion.

Experimentalists are often stricken with a cowboy mentality. If you have never had a serious incident with a material, it is easy to get a bit cavalier. But handling metal alkyls is a lot like handling rattle snakes- you have to be careful every single time.

A subsequent post offers suggestions on due diligence for ressearch professors.

Respecting liquid hydrocarbons as a natural wonder

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I just had a conversation with a colleague who is somewhat mainstream in his/her thinking. The question came up as to why can’t we be energy independent.  What is taking so long with the electric cars and natural gas powered … everything? When can we break away from middle eastern petroleum?

In the public sphere, all I hear are the questioners seeking reassurance that there are energy forms out there that will allow us to maintain our current level of consumption. They rarely put it exactly that way, but that is the heart of the issue.

I think multiple generations of people have failed to appreciate the natural wonder of liquid hydrocarbons. The C7-C10 fractions of petroleum, whether directly from the ground or from a cat cracker or reformer, are the motive basis for most of our ground transportation. These liquid hydrocarbons are of a reasonably low vapor pressure and high enough boiling point to allow their use in everything from go-carts and lawn mowers to automobiles and caterpillars.  Teenagers and grandmothers can pump hydrocarbons into an inexpensive and simple tank for use at ambient pressure and temperature. This liquid has a melting point low enough to make it flowable under nearly all earthly conditions.

The high energy density and the liquid state of gasoline is what makes it nearly perfect for propulsion. The energy density of gasoline is 34.8 mega-Joules per liter (MJ/L), as opposed to 21.2 MJ/L for ethanol.

Yeah, gasoline is cheaper per liter than the bottled water inside the convenience store. That perversion is just a temporary historical aberration. This will change.

Cosmically, hydrocarbons in the C7-C10 range suitable for automotive use are quite scarce in the local stellar neighborhood.  Some small hydrocarbon molecules like methane have been spotted in the gas giant planets and on Titan. But for the most part, the only supply of hydrocarbons we have are found in porous deposits below the surface of the only place we can get to- Earth.

We should appreciate our hydrocarbon resources for the true natural wonder that it is and be a bit more reluctant to squander it.  I doubt we’ll ever find a source of energy that is as cheap and convenient to use with such a high energy density.  Battery technology may get close, but innovation there is a highly specialized art that is beyond the scope of most shade tree mechanics. Common lead acid batteries require material and energy inputs, like everything else, and have somewhat low energy density and a high weight penalty.

Lithium batteries, with their higher energy density require a variety of manufactured and relatively exotic substances. And, they require lithium which is fairly scarce, both cosmically and on earth. We really should be recycling lithium scrap.  Seriously, we need to have great respect and appreciation for lithium as well. There really isn’t enough lithium to support everyone’s high energy density lifestyle.

Pinch Predicted in the Uranium Market

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According to an article in Mineweb, the remaining cold war era uranium will be consumed in the next few years, leaving the nuclear industry with inadequate supply streams from mining.  Thomas Drolet of Drolet & Associates Energy Services, said that in 2010 mining produced 118 million pounds of uranium against a demand of 190 million pounds. Obviously, the balance was made up from decomissioned nuclear weapons stockpiles. The article did not say whether the numbers represented lbs of U or of U3O8. The oxide is commonly cited in relation to uranium mine production.

Drolet suggests that Japan will have to restart ca 30 of its 50 or so reactors in order to meet power demand.

It is my sense that the Fukushima disaster will not be the stake in the heart of nuclear power. The location of the Fukushima plant and a list of easily identifiable design features allowed the initiation and propagation of the incident. While the future of reactor operation in Japan may be stunted, most reactors elsewhere in the world are not located in tsunami flood zones. Regrettably, some are located in fault zones. But the insatiable demand for kilowatt hours will override everything. Commercial fission will continue into the indefinite future.

Return to fundamentals

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As we labor away on our extractive metallurgy project, I continue to marvel at how even complex extraction schemes reduce to the application of fundamental chemistry and basic unit operations. It is crucial to have a comprehensive understanding of the composition of your ore and the fate of the components as they are exposed to unit operations. The extraction of desired metals from your ore requires extensive use of analytical resources in order to keep the process economics in line.

Extractive metallurgy also requires an extensive knowledge of descriptive inorganic chemistry- something that was glossed over when I was in college. When I took undergraduate inorganic chemistry the emphasis was on ligand field theory, group theory application to symmetry and vibrational modes, coordination complex chemistry, etc. Lots of content that took many lecture hours to cover. Basic reaction chemistry was neglected in favor of admittedly elegant theory.

The fun for me (an organikker) has been in learning lots of descriptive inorganic chemistry and inorganic synthesis.

Extractive metallurgy in practice comes down to a relatively short list of operations. Roasting or calcining, comminution & classification, extraction, dissolution, flocculation, frothing, dewatering and filtration, redox transformations, precipitation, and drying.  Since most of the solution work is water based, the main handles you have to pull are temperature, selective solubility, and pH.

My undergrad coursework in inorganic qualitative analysis, specifically the separation schemes, has been very valuable both in terms of benchwork as well as descriptive chemistry.

Keep China busy- buy an iPhone.

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Thanks to Bill in Michigan for the link on how the US lost out on manufacturing the iPhone. The article is well worth the read. A few of us have been beating this drum for a while. Economics is not a theory of physics. It is entirely about choices people make. But to some, economics has become a mathematical and philosophical validation of greed and a metric of mortal value.

Interestingly, Robert Reich has a parallel and broader editorial on the same general topic.  Reich points out that US corporations are becoming increasingly globalized with “less and less stake in America.”

Reich quotes an Apple executive –

‘An Apple executive says “We don’t have an obligation to solve America’s problems. Our only obligation is making the best product possible.” He might have added “and showing a big enough profits to continually increase our share price.”’

Reich goes on to say that US business investment in R&D is in general decline but…

“… According to the NSF, American firms nearly doubled their R&D investment in Asia over these years, to over $7.5 billion.

GE recently announced a $500 million expansion of its R&D facilities in China. The firm has already invested $2 billion.”

If you read history and understand something of how the industrial revolution has been the deus ex machina of social revolution since the invention of smelting, then unavoidably you must ask what happens if we change the sign of the revolution?  Does the sign of social revolution become negative as well in a nation of negative- or de-industrialization? What happens in a nation when a minority of shareholders absorb value from the stakeholders via tranplantation of the economic engine to another nation? What happens to society when the population grows but the per capita availability of jobs is in decline?  A trip to the Congo or to Gaza might give some useful hints.

Deindustrialization is not nearly the sole culprit. Automation is much to blame for the obsolescence of job descriptions. Automation actually facilitates the export of jobs because the key expertise may be in the design of automated equipment, not its operation.

What made America “great” was not simply its freedom. There was a substantial contribution from a vast continent pregnant with animal, vegetable and mineral resources for the taking. The early allotment of land and mineral resources by the government to settlers, railroads, and mine operators kick started the American economic engine in the mid 19th century.

I am uncomfortable with this strident American exceptionalism viewpoint. Maybe it is the midwesterner in me, but I would prefer to see Americans roll up their sleeves and get busy making things again. Leave the boastful and prideful stuff for the comics. A little more humility and thoughtfulness will get us further and in better condition.

Vannoccio Biringuccio. Sixteenth Century Chronicler of Metallurgy.

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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

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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.

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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.