How Novel is the Bolivian Process to Extract Lithium?
Jul 15, 2012
In this blog I explain why the so-called Bolivian process to extract lithium may be a partial copy of a new method to recover lithium from Salar de Uyuni brines developed by South Korea.
In his nonsensical rebuttal of my recent article entitled "Lithium: The Intangible Value of our Brines” published only in Spanish, the manager of the lithium plant in Bolivia begins with a reference to the following paragraph from it: "The intangible value of Uyuni brines can be found in the potential of concentrations of the various minerals that compose them."
While taking it as a presumptuous and absurd statement, he says about that: (i) "they´re not minerals, but cationic and anionic ions dissolved in water", even though "the brine itself may be considered as a mineral"; (ii) "all the salt brines of the world are at different levels, some with higher concentrations of various ions than others, in time to indicate that the Uyuni brine has average concentrations, i.e. much lower than the Atacama and Hombre Muerto lithium, but higher than that of the salt lakes of China and Iran"; (iii) "it´s not news the operation should be comprehensive;" and (iv) "it´s absolutely not true that the Korean research and its results were only possible for the alleged 'gift for nothing' of the Uyuni brine."
Clearly, to concoct his series of childish statements he had to dust off his yellowish university textbooks as if scientific knowledge had been stalled since then to his taste and patience. His first reasoning seems anchored on the idea that the salts dissolved in water are not minerals, but that the brine (i.e. salts plus water in which they are dissolved) is. Let's start with the first absurdity he pinpoints. Could it be that according to this gentleman sodium chloride (NaCl) which happens to be the main component of the brine is not a mineral? Moreover, what are indeed minerals nowadays?
According to the 1991 edition of Webster's College Dictionary and the 2001 edition of Dictionary of the Spanish Language, minerals are defined as any substance that is found on the surface or in the various layers of the crust of the globe, usually related to inorganic elements with a precise chemical composition and, generally, with a particular crystal structure, but sometimes also including rocks formed by these substances, and certain natural products of organic origin, whose holding is of interest. His confusion is really worrying, given his academic formation. If in his disrupted conception, brines are minerals, then we should also accept that the seawater is a mineral, which is not scientifically proven.
On the second point, he says Uyuni brines have mean concentrations relative to other salt flats. Given that he only refers to lithium, he commits a gross error underestimating the value of other chemical elements such as magnesium, boron and sodium, for example, all contained in the Bolivian brines. Needless to say, this also allows us to question his supposed attachment to a comprehensive approach to evaporite resource exploitation at the largest and highest salt lake of the world. Finally, in his usual style, he maintains that it is false that the Korean research would have been impossible without the Bolivian brines delivered free of charge because "any brine can be replicated artificially, as indeed they did in South Korea to renew their tests once the brine was depleted...". This is really funny.
On the one hand, it is easy to see why the manager of the lithium pilot plant is so committed to underestimating the value of our brines. Now he tries to convince everyone that they were not really necessary because the Koreans could have replicated them. I wonder: What the South Koreans could have been able to replicate without our brines? As the manager is aware of the great mistake he made in giving away these samples without any commitment by the South Koreans, he would like to have us believe that they were not gravitating to the development of the novel processes discovered. Incidentally, I also wonder what happened to our brine samples delivered to Japan, China and France. The manager´s generosity with something that does not belong to him should be subjected to an urgent investigation by the authorities.
On the other, I doubt indeed about the feasibility of replicating the average brines of the Salar de Uyuni, which, according to recent research are composed of more than 34 elements (or anionic and cationic ions in the convoluted technical terms used by the evaporite manager). To that effect, it would require an almost infinite number of combinations of elements and samples extracted from different representative locations, taking into account that the concentrations of the brines of the Salar de Uyuni are highly variable from one area to another, as demonstrated by Francois Risacher more than 20 years ago.
Then I am accused of having no idea what I'm talking about when I say "that the new Korean technology obtained the cathodes of lithium directly from brine without passing through the lithium carbonate." He says that "the Korean process, which is also an adaptation of known processes, not only is not direct, but rather establishes more processes because it first obtains lithium phosphate by precipitation, then in a electrodialysis process gets lithium hydroxide and lastly in a final process through this hydroxide together with other precursors obtains lithiated cathodic materials.”
First, I clarify to the clueless engineer that when I hold that the South Korean technology (called KB3 +) allows for cathodes of lithium directly without passing through the lithium carbonate, I'm not arguing that there aren´t some intermediate processes. All I´m asserting is that this technology doesn´t need to use lithium carbonate as a precursor to manufacture cathodes of lithium - the standard procedure used today- which, considering that this method doesn´t use any kind of evaporation comes to be indeed - although he is not interested in acknowledging it - a scientific and technological advance of great significance for the world. Second, I remind him that the South Koreans call their own process KB3 + "Direct Synthesis of Cathode Materials," because that is precisely what it is. Third, I remark that the first thing the South Koreans get is magnesium hydroxide and calcium carbonate, not lithium phosphate. His failure to mention this first phase of South Korean inclines me to suspect that the pilot plant manager did not want to disclose this information. Why? Possibly because in this way we would have known that the "Bolivian process" would be a partial copy of another South Korean process also developed from our brines.
In fact, as indicated by the current minister of mining and metallurgy in his response to written report request No. 063/2012-2013 dated April 18, 2012 by the Senate, the "Bolivian process", in its latest version, starts "with pumping the crude brine to a liming ground, in which is combined with calcium hydroxide, thereby removing the sulfate ion in its entirety, the magnesium ion in the form of magnesium hydroxide by 30% and the boron in the form of calcium and sodium borate by 70%. It then continues with two stages of solar evaporation which eliminates much of the sodium and potassium. A third chemical phase that is really the core of the investigation of the Bolivian process whereby through chemical and evaporation successive stages the magnesium content is reduced to get the liquor concentrated on lithium, which is treated in the last chemical phase with sodium carbonate to produce lithium carbonate."
Note that the "Bolivian process" presents a great similarity to the process described by six South Korean scientists in the article entitled "Recovery of lithium from Uyuni salar brine" published in February this year in the journal Hydrometallurgy because in both cases calcium hydroxide is used to remove the sulfate and precipitate the magnesium as calcium sulfate and magnesium hydroxide, in time to adsorb the boron.
It should be recognized, however, that there is a significant difference between the two processes: That the South Korean process continues to apply chemicals (sodium oxalate) to further remove calcium and magnesium to achieve a very high level (presumably over 99% as posed by processes KB1, KB2, KB3 and KB3 +) recovery of these elements prior to the application of solar evaporation in the last stage to of obtain the liquor lithium (i.e. lithium chloride with about 6% content of lithium), while the Bolivian process uses chemical and solar evaporation for this task, since in the first phase it only attempts to reduce magnesium by 30%. This divergence of the Bolivian from the Korean process seems to be linked more to the availability or cost of inputs (sodium oxalate) in Bolivia, suggested by the South Koreans, than to the originality of the Bolivian process.
To conclude the explanation of the KB3 +, I must say that after the precipitation of magnesium hydroxide and calcium carbonate, and the adsorption of boron, the South Koreans, using other chemicals and energy, just get lithium phosphate, keeping lithium, calcium, sodium, potassium, chloride and sulfate in the brine so that after applying an electrolysis process - not electrodialysis (as erroneously holds the manager of the pilot plant) - and an unidentified acidic substance to lithium ions they produce lithium hydroxide. The process ends in the manufacture of lithium cathodes through the combination of lithium hydroxide with carbon dioxide and various metals (Co, Ni, Fe, Mn) currently used as cathode elements of batteries. Note that so far no mention at all was made of lithium carbonate because in reality this compound virtually disappears from the production chain of lithium cathodes, becoming, at best, a byproduct of the process.
We should now ask the evaporite manager if he finally understood my point and, above all, who shall be liable for the disrespectful remarks he used in his article to refer to my arguments while abusing his unrestricted access to the government newspaper.
Also, I maintain my argument about the intangible value of our brines, which relates primarily "to the potential of the concentrations of the various minerals that compose them, which only admits the possibility of an integral exploitation of them, creating value added value not only from lithium but also from magnesium, boron and to a lesser extent, potassium." While I can´t ignore the crucial role played by scientific research on this topic, it is clear that I am not referring here to the type of ad hoc research developed to date in the lithium pilot plant.
Regarding the recovery of our brines, he opts for intellectual laziness, arguing that the emphasis should be primarily in the production of "basic salts of potassium and lithium, then boron and magnesium and finally in the lines of industrialization of each of these elements". In Bolivia, he continues, "unlike Chile and Argentina, adding value is faced in the strategic project in the line of industrialization of lithium, with pilot undertakings of lithiated cathodes and lithium-ion batteries".
On the one hand, there is reason to believe that Bolivia appears to be following in the footsteps of Chile - no wonder the pilot project has hired several technicians of that nationality to pursue the most strategic venture in the history of the country. I wonder if at least they have been careful enough to make them sign a confidentiality agreement not to discuss with our main competitors the technological advances that are made daily in the pilot plant at Llipi Llipi. Additionally, we have yet to know what we need to learn from such technicians, given the particularities of our brines and the physical-climatic conditions (e.g. much lower solar evaporation rates and a rainy season that lasts from 2 to 3 months per year) to which they are subjected.
In this sense, he must probably be convinced by now of doing with magnesium, for example, what Chileans do with it: Use it as material for compacting dirt roads, instead of processing it for use as a substitute for steel and aluminum. ¿Would the lost manager suspect that General Motors´ Advanced Technology Center (China), currently the largest car maker in the world, has just completed the manufacture of a magnesium part which is a true milestone in automotive materials research? For his information, the use of magnesium in the chassis, could not only improve the efficiency of internal combustion vehicles but mainly of electric ones whose main issue is the weight of the battery.
It is imperative to note that the six aforementioned South Korean scientists in their February article earlier this year state that "the value of Mg in the Uyuni brine is as high as for lithium if a chemical grade Mg oxide or hydroxide could be produced.” It goes without saying that the South Koreans are not speaking here of producing these compounds only for use in the manufacture of refractory bricks, as suggested by the director of operations of the lithium pilot plant in a recent article.
On the other hand, he is proud of himself for signing the agreement with the South Koreans to produce cathodes of lithium and turnkey purchasing of a lithium-ion battery pilot plant from a Chinese firm which is completely unknown in the lithium ion battery global market. In this regard, he forgets to mention some details: that in the first case he did not make any effort and was rather pushed by his circumstantial partners, and in the second, all he did was to commit a huge amount of scarce financial resources of the country to acquire a lithium ion battery pilot plant with not exactly cutting-edge technology.
He cites as evidence that lithium extraction system based on solar evaporation is not obsolete the fact that the two companies producing lithium in Chile still use it. What a great discovery! When will he understand that even in Chile they have begun to explore new methods of production due to water scarcity? It should be noted that the latter situation is not at all far from the Bolivian reality, as argued recently by a German geoecologist.
Moreover, his argument regarding the infeasibility of other (relatively more expensive) technologies is meaningless in the current market conditions, characterized by a marked growth in demand for lithium and a clear trend of increasing prices, as was just pointed out by one of these companies. The lack of water, added to the legal problems faced for the expansion of mining areas and that lithium is still not concessionable in Chile, as well as unresolved conflicts between local communities and businesses, and disincentives to foreign investment (by, for example, exchange controls) prevailing in Argentina, give an excellent outlook for Bolivia that unfortunately we will not be able to take advantage of.
At this rate, it is likely that market conditions are more conducive to the eventual market dominance of lithium ore producers which could in turn jeopardize the consolidation of the new techno-economic paradigm with lithium as the key factor that I predicted in January 2008.
He dismisses outright the South Korean and Japanese processes on the grounds that they are experimental. I wonder: who could deny them that character? However, the simplest common sense forces us to believe that they also possess sufficient technological support because they were discovered by companies of these two countries which, inter alia, have managed to successfully extract lithium and other evaporite resources from seawater, some brines, certainly much more complex and poorer than those of Salar de Uyuni.
I will not say more about the South Koreans, except that apparently they have not developed only one process for exploiting the brines of the Salar de Uyuni but at least five, the last of which - as I noted above lines - would keep -oddly- a close relation to the "Bolivian process." In recent days I have wondered whether by any chance the Koreans could have copied the "new" Bolivian process. It would then be compelling for Bolivian authorities to initiate an investigation process followed by the corresponding complaints.
With regard to the Japanese, I have heard they have started work on the Llipi Llipi plant. I understand that even if this information could be confirmed, the project manager will try to deny such a possibility for the simple reason that that could call into question the label of "100% state-managed" of the pilot plant that even the new minister of mining and metallurgy has begun to advocate tooth and nail, even at the cost of the damage that this - essentially rhetoric - position could cause the country.
As the lies have short legs, I'm sure that sooner or later the Bolivian people will begin to unravel this and other mysteries about the most important undertaking in the history of the country.
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