This is a guest post written by a good friend and colleague who retired as an executive from the specialty chemical industry. He is an author and editor of a popular book on a certain variety of organometallic chemistry. It is an honor for me to post his recollections on this site with his permission.
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The TOXCO Story – Part I
I suppose this story begins during the Cold War. The US had developed a triad of defense capabilities to deter Soviet aggression. We had the Air Force B-52 bombers armed with atomic weapons, the submarine based Trident missiles, and the land based ICBMs–first the liquid fuel Atlas rockets and later the solid fuel Minuteman missiles hidden is silos in North Dakota and elsewhere.
Then came 1989, the destruction of the Berlin Wall, the subsequent collapse of the Soviet Union and, suddenly, the Russians were no longer the dreaded foes whom we once feared. Maybe it was time to “stand down” our hair-trigger defense posture.
Those solid fuel Minuteman rockets were designed to be launched on short notice. Firing them required a significant amount of electricity. This was to come from the electric power grid. But our military, recognizing that this source of power could be compromised in the tense times leading up to a nuclear confrontation, needed a backup. As a result, each missile silo was equipped with a diesel powered electric generator, just in case.
But things could go wrong. The diesel fuel might be contaminated, or sabotaged by Russian saboteurs, or any of a number of other problems. So, in an overabundance of precaution, the military insisted on a “backup to the backup”. And what could be better or more reliable as a source of electricity, than a battery. To be sure, these would have to be BIG batteries, bigger and more powerful than any produced thus far, but they would be certain.
And so, the Defense Department commissioned the production of the world’s largest and most powerful batteries. These were based on lithium-thionyl chloride chemistry[1]. Each primary cell contained sheets of elemental lithium, surrounded by gallons of thionyl chloride, a reactive liquid which on contact with water produces a mixture of sulfuric acid and hydrochloric acid—really nasty stuff. These primary cells were each about the size of a coffin and it took three, ganged together to generate the power needed to initiate a missile launch. The government contracted for thousands of them and Union Carbide supplied them.
Apparently, at some point, there was a fatal incident involving a 10,000 amp Minuteman battery being drained and replaced[2] and this contributed to a decision in the early-mid 1990s to dispose of these hazardous items. The DOD issued a Request for Proposals (RFP) which caught the attention of a group of businessmen and entrepreneurs in southern California.
Operating in Orange County, California, headquartered in Anaheim, near Disneyland, were three affiliated companies. Adams Steel was in the ferrous metal recycling business-old washing machines, refrigerators, scrapped cars. Before you scrap a car, you remove the lead-acid battery and the catalytic converter. The battery, containing lead metal, lead salts and sulfuric acid is a hazardous waste and its disposal is regulated by the EPA. The catalytic converter contains precious metals such as platinum, rhodium and iridium. These two items (batteries and catalytic converters) were handled by Kinsbursky Brothers. Non-ferrous metals (common ones such as copper and aluminum and non-common ones like tantalum and gallium from electronic devices) were processed by Alpert & Alpert. The companies had worked together for a number of years.
Principals at Adams Steel and Kinsbursky decided to form a joint venture to bid on the lithium battery disposal opportunity. They created TOXCO for this purpose. It was headed by Terry Adams (the youngest sibling in the Adams family) and Steve Kinsbursky. And they won the bid. The government would pay TOXCO millions of dollars to dispose of these batteries that the government had paid millions of dollars to manufacture some years earlier. Your tax dollars at work.
So, how do you dispose of a lithium-thionyl chloride cell weighing hundreds of pound and filled with dangerous and explosive ingredients? Well, if you are a mechanical engineer, trained at USC (as Terry Adams was), you take a mechanical engineering approach the problem. You have to neutralize the thionyl chloride and the lithium by reaction with water. And reactions take place more slowly (and more safely) at lower temperatures. So, the answer is to chill the cell in liquid nitrogen down to 77°K, put it in a large container filled with water and chop it apart with big mechanical knives (like you chop an automobile into small pieces for scrap). This actually works. Provided you’re certain that the cells have been fully discharged first. But don’t take the military’s word for it. If you do, there may be an embarrassing incident, as there was in 2000, during the disposal process.[3]
Next question. Where do you do this disposal? The TOXCO team discovered that there was an underused industrial site in Trail, British Columbia, on the Canadian side of the Idaho border. It had been part of the Cominco Smelter operations and was one of the most heavily polluted sites in North America[4]. What better place to site a hazardous battery disposal plant? If something went wrong, who would notice?
And so, TOXCO went into business, disposing of lithium batteries, successfully (except for a few incidents like the one incident alluded to above).
One of the by-products of this process was a stream of aqueous lithium salts. These had value and could be recovered and that put TOXCO into the lithium chemicals business. But that’s part II of this story.
The TOXCO Story – Part II
(the Lithchem Story)
This story also begins in the Cold War. Even as the atomic bomb (the uranium and the plutonium fission bomb) was being engineered into reality at Los Alamos in the mid 1940s, plans were being made for the next generation weapon—a fusion bomb.
The first H-bomb, based on the concept of fusing light nuclei, was tested at Eniwetok in the South Pacific in 1953. Improvements in the initial “clunky” design quickly followed. One way to boost the power of the explosion was to surround the core of the bomb with a layer of lithium deuteride, LiD. Lithium is, well, the element lithium, atomic number 3 in the Periodic Chart. And deuterium is the name for “heavy hydrogen”, an atom of hydrogen, atomic number 1, but also containing an uncharged neutron[5]. Provided that the lithium used was of atomic weight 6, the fusion of the lithium(6) and the deuterium(2) would produce two nuclei of helium(4), plus lots of energy.
This would only work if you used lithium-6. Unfortunately, the lithium available to us on this planet in mineral form, deposited around the globe, is a mixture of lithium-6 and lithium-7 (the same element, but with one extra neutron). And God, in His infinite wisdom, chose to endow the earth with mostly lithium-7. Of the naturally occurring deposits of lithium, 93% is lithium-7.
So, if you need to use just Li-6, you have to separate it out from the more abundant, naturally occurring Li-7. And the US government proceeded to do just that. Starting in the 1950s, they processed millions of pounds of lithium containing minerals to extract the less abundant isotope that was required for its military purpose. For every hundred pounds of lithium salt they processed, they got, at most, 6 pounds of lithium-6 salt[6].
And what do you do with the “leftover” 94+ pounds. Well, you can’t just turn it back into the lithium chemicals marketplace. For one thing, it’s “depleted” lithium (missing its naturally occurring share of Li-6.) This would be easily noticed by someone using the lithium for routine chemical purposes. The extent of “depletion”, that is, of extraction of the Li-6 would be measureable, and that information was a secret[7]. Moreover, if the quantity of depleted Li were ever realized, that number could be used to infer the number of LiD containing bombs, and that too was a secret.
So, for more than five decades, for more than half a century, the US government simply stockpiled the “by-product” depleted lithium in a warehouse, in the form of the simple salt, lithium hydroxide monohydrate, LiOH•H2O. Millions of pounds of it. Packaged in poly lined, 55 gallon fiber drums.
In later years, the cardboard drums began to deteriorate. Some of them were damaged during handling and relocation. Sometime in the 1980s the decision was made to repack the inventory in bright yellow steel “overpack” drums.
Now comes the early 1990s. The Cold War is over. Our nuclear secrets, at least those from the 1950s, are far less precious. And the Clinton administration is looking through Fibber McGee’s closet[8] to see what can be disposed of, and maybe generate a revenue stream for the government in the process.
What they discover is 100,000,000 pounds of “depleted” lithium hydroxide monohydrate, with a potential market value approaching $1 per pound. And so, it goes out for bids.
The terms of the sealed bid auction were that the final sale would be split 70-30 between the highest bidder (who would get 70% of the inventory) and the second highest bidder (who would get 30%, but at the high bid price).
This was a perfect set up. At that time there were only two lithium companies operating in the US who could handle this quantity of inventory—Lithium Corporation of America[9] and Foote Mineral Company[10]. And both of them knew that there was no incentive for overbidding since even the loser would get 30% of the supply.
And that’s where Lithchem appeared on the scene. The TOXCO team was already in the “recovered lithium” business. All they had to do was bid one penny more per pound than the other two majors and they would be awarded the lion’s share of the inventory. They incorporated Lithchem for that purpose. I’m told that LCA and Foote each bid the same number, somewhere in the 20+ cents per pound range, and Lithchem bid one cent more. As a result, Lithchem became the proud owner of 70,000,000 pounds of depleted lithium hydroxide monohydrate.
Now what? The principal use of LiOH is in the manufacture of high performance lithium greases, used in heavy industrial applications-heavy trucks, railroads, etc. Much of the market for lithium greases is in the third world and quality is less of a concern than price.
Still, to be sold on the open market, the LiOH from the government stockpile had to meet certain specifications. Some of the yellow drums contained beautiful white crystalline powder. Others contained dead cats and cigarette butts. It was “government quality” inventory.
One condition of the bid was that the winning bidder had to remove the inventory from its location in a government warehouse (in southeast Ohio[11]) within 12 months of the successful bid. I had the occasion to visit that warehouse, before the stock was removed and it was a memorable sight.
If you recall the final scene in the movie “Raiders of the Lost Ark”, the Ark of the Covenant is being stored in a gigantic government warehouse, filled floor to ceiling with identical gray boxes. A warehouse stretching far into the next county. Now replace those gray boxes with yellow overpack drums, stacked 6 or 8 high, stretching far into the next county. That’s what it was like. That’s what 70,000,000 pounds of LiOH hydrate looked like.
[1] The lithium – thionyl chloride primary cell has a high voltage (3.5 V) and a high current density.
[2] Battery Hazards and Accident Prevention, By S.C. Levy, P. Bro
[3] In November 2009 a fire broke out at the Trail BC facility in a storage shed containing lithium batteries slated for disposal. It was their sixth fire in fifteen years. Prior to that, a major fire in 1995 destroyed 40,000 kg of batteries at the facility. Three fires occurred in 2000, including one caused by some lithium batteries. This was during the summer when negotiations were underway between Toxco and Atochem for the acquisition of the Ozark business. http://www.cbc.ca/news/canada/british-columbia/trail-battery-recycling-fire-leaves-questions-1.805780
[4] http://en.wikipedia.org/wiki/Teck_Resources
[5] Elements with the same atomic number but different weights are called isotopes. Heavy hydrogen (with an atomic weight 2) is an isotope of hydrogen (atomic number 1). Another example is carbon-14, useful for radiocarbon dating. It’s a heavier version of the more common version of carbon, C-12.
[6] Actually less than 6 pounds. The extraction process was less than perfectly efficient. The actual yield of Li-6 was a closely guarded national secret.
[7] In depleted lithium (with the Li-6 removed), the relative abundance of lithium-6 can be reduced to as little as 20 percent of its normal value, giving the measured atomic mass ranging from 6.94 Da to 7.00 Da.
[8] http://en.wikipedia.org/wiki/Fibber_McGee_and_Molly#The_Closet
[9] Acquired by FMC in 1995 and now known as FMC Lithium.
[10] Now part of the Chemetall Group, a division of Rockwood Holdings.
[11] At the time, it was stored at the DOE enrichment facility in Portsmouth, Ohio.
