Category Archives: Chemical Industry

Mining Asteroids

The founders of the Silicon Valley startup, Planetary Resources, have announced plans for mining asteroids for valuable metals. Peter Diamandis, Eric Anderson and investors including director James Cameron and Google CEO Larry Page are behind this venture.

I’m trying to be positive here. Perhaps these fellows should visit some earthly mines and see what it takes to break actual rock and extract the value from it.

Earth bound ore bodies near the surface are commonly the result of concentration by hydrothermal flows. In the absence of water-based geothermal concentration processes, or recrystallization of PGM’s in magma chambers, the reality of economically viable ore bodies in asteroids is an open question. A lot of survey work needs to be done to answer this question.

Oh, and one more thing. When you blast rock on a largish planet like earth, the fragments fall back to the ground. This won’t happen on an itty bitty asteroid.

The talk about recovering water from asteroids to subsequently crack and make propellant is a large challenge all by itself.

I predict that civilization will slump back to a 19th century Dickensian-style world of robber barons and sharecroppers before any hardware gets to an asteroid.  Children will ask “Momma, what’s an iPad?” as they walk from their rundown subdivision to a quonset where they strip insulation from wire for copper to barter for food. It’s all so clear now …

Thorium power. Will the US get on board?

Everybody knows by now that China is flush with rare earth elements (REE’s), or at least to the uppermost extent that any country can be. And, everybody knows the market hijinks that China has planned with REE’s, namely, buy all the REE’s you want from them, as long it is in a value-added manufactured good.

What most folks are probably not aware of is that the ore bodies that carry the REE’s (Sc, Y, and the Lanthanides) are usually enriched in thorium and/or uranium.  So much so that no little amount of skill and equipment is needed to separate Th & U from the REE’s. The US and USSR developed much of this separations technology post WWII and for decades thereafter. Much of this art is in the US patent literature. The rest of it is buried in dusty, obscure volumes on library shelves.

The art of REE separation is arcane and somewhat isolated from the rest of inorganic chemistry owing to its specialized nature. Most of the separations art relies on leaching and elaborate solvent exchange schemes.  Ion exchange technology is also highly represented in this domain.  Few chemistry students are exposed to this science and most of the cold war era practitioners are retired, ailing, or deceased.

Chemistry students rarely see this art for another reason. It is generally practiced by engineers and metallurgists who seem to be in a perpetual phase separation from the standard chemistry curriculum. I would argue that this distinction is mainly cultural.

Back to the Chinese. While Americans have been busy yammering about drill-baby-drill, or following the escapades of reality show imbeciles or a thousand other idiotic distractions, we have failed to focus pressure on our government to consider technologies like thorium power or molten salt reactor technology.

While a gullible and frankly, cognitively impaired, vocal minority in the US accept that we have a right to $<3.00/gal gasoline, we are being distracted into the warm feather bed of self-congratulation and delusion about our supposed exceptionalism. I sense that our culture is beginning to show a type of exceptionalism that is not very admirable.

While American voters are being spun up into a frenzy again about commodity oil prices, China has been promulgating its national industrial policies. American industrial policy seems to be about lining the citizens up for accelerating consumption. China’s industrial policy emphasis seems to be about putting infrastructure and capacity in place for exports as well as anticipated internal consumption.

China has a substantial presence in mineral rich Africa. China imports copper ore from Peru and Chile. Not finished copper- but copper ore. China keeps the value added steps for its own coffers. Most distressingly, China is busily working on copper mining in Afganistan while our kids fight and die there in an intractable cultural shooting war. Did you get that?

China is mining in Afganistan and Americans are paying to die there.

While the US pays to make the world safe for commerce, China is spreading out over the world looking for scarce resources like copper under the umbrella of stability.  While China mines copper in Afganistan, the USA consumes copper in Afganistan in the form of brass bullet casings ejected over the landscape. Brass is an alloy of copper and zinc.

Is this a diatribe against all things Chinese? Absolutely not. If anything, China has skillfully mastered it’s range of control and made purposeful, long term plans to reach its goals. Like its plans for Thorium-based molten salt reactors. Thorium power is undergoing a bit more examination now, as described in this Forbes article.

Here is a point I’d like to get across. The present boom in REE exploration and mining is in a good place for thorium extraction. If thorium were to be part of the extracted value rather than a costly sidestream in need of segregation and remediation, then the subsequently improved economics of REE extraction and greater availability might translate to lower REE costs for users of rare earth metal technology.

There is a crucial synergy here that the US would do well to exploit. But it requires vision, long term planning, and regulatory flexibility in the handling, accumulation, and processing of thorium.  These attributes the US now lacks. The current lead pipe doctrines of American politics represents a critical systems failure of our culture. We cannot continue to regard middle-ground compromise as total forfeiture.

Chemistry Lab Accidents Reports from the Chemical Safety Board.

Here is a link to a US Chemical Safety Board video summarizing several recent lab accidents.  If you have never visited or heard of the CSB, here is a link to their web site. Have a look around.

This link is to the case CSB case Study of the Texas Tech explosion with nickel hydrazine perchlorate. It has a nice illustration of the Swiss Cheese Model of safety. This model was devised by British Psychologist James T. Reason at the University of Manchester in 1990.

The degree symbol- Do we really need to keep using it?

I had an evil thought just now as I attempt to write 2 reports simultaneously. Why do we keep using that superscripted circle in front of C (i.e., ºC) that designates “degree”?

What the hell? We don’t use it for the Kelvin temperature scale. And, who knows if the engineers use it for Rankine? The thing is useless like an appendix or a titular chairman. Get rid of it!

What do you think?

Fear and Loathing with Frac Fluids

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

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

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

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

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.

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.