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Not so rare after all

Jack Lifton says there are plenty of rare earths for our clean technologies and gadgets, it just depends how desperately we want them
EFINERY catalysts, hyhrid car batteries, mohile phones, weapons systems and wind turbines all rely on 17 so-called rare earth elements (REEs), 97% of which are produced hy China. The remainder are sourced from Russia, hidia and Malaysia, meaning that some of the world's dominant users and developers of high-end technology such as Japan and the US are wholly dependent on imports. This vulnerability has caught the attention of the industrial community, governments, and the public at large after China threatened to block exports to Japan during tough diplomatic negotiations in October. It also warned the world that it was considering reducing its exports of REEs in a bid to secure its own future supplies and lessen the harsh environmental impacts of mining and processing the metals. This has led many to ask the sobering question: are there enough REEs to sustain and allow for the spread of a technological consumer society? The answer is yes. REEs did not get their moniker because they are only found in China but because they are distributed in exceedingly low volumes throughout the earth's crust. There is enough to go around to avoid them being monopolised if we are desperate enough not to want it that way.

LIGHT
Lanthanum / 39 ppm / (57) NiMH batteries, industrial catalysis, speciaiist giass Cerium / 66.5 ppm / (58) automotive catalysis, mischmetal lighter flints Praseodymium / 9.2 ppm (59) aerospace components, rare-earth permanent magnets Neodymium / 41.5 ppm (60) rare-earth permanent magnets, lasers, glass

Figure V. Elements and their estimate of crustal abundances, atomic number and selected uses [Estimates of crustal abundances taken from Lide (1997)]

HEAVY
Gadolinium / 6.2 ppm (64) rare-earth permanent magnets. nuclear reactor components Terbium /1.2 ppm (65) phosphors, lasers, fuel cells

Promethium / (less than 1 kg total)(61) nuclear batteries Samarium / 7.05 ppm (62) industrial catalysis, rare-earth permanent magnets Europium / 2 ppm (63) phosphors, lasers

Dysprosium / 5.2 ppm (66) rare-earth permanent magnets, nuclear reactors components Holmium /1.3ppm (67) lasers, nuclear reactor components Erbium / 3.5 ppm (68) lasers, nuclear reactor components /g 1 ) aerospace (21): Thulium / 0.52 p p m (69) lasers, medical imaging Ytterbium / 3.2 ppm (70) medical imaging, steel doping Lutetium / 0.8 ppm (71 ) industrial catalysis compon components, refinery tracii tracing agents Yttrium / 33 ppm / (39): im industrial cataiysis, lasers, cataiy superconductors supen

a history of increasing separation

REEs are found mbted together in varying proportions. Atfirst,the 17 REEs (see Figure 1) were thought to be just one or two until the late 19''' and early 20th centuries when

4 4 during the 1990s, the price of separated REEs from China began to fall and their purity to rise just as western researchers were realising their benefits

the development of optical spectroscopy allowed them to be distinguished from one another well before they could be chemically separated. It wasn't possible to separate them vdthout a cost far in excess of their end-use value until the late 20''' century, for most of them anyway. Thus REEs, until recently, were largely used as unseparated metals, misch (German for "mixed") metals for cigarette lighter fiints and military tracer ammunition. Individual REEs are separated using the tiny differences in their solubility. Solvent exchange separadon is time consuming, labour intensive, and costly. Molycorp Minerals built the world's first commercialscale REE separation plant at Mountain Pass, California, to isolate europium. Europium was the element of choice for producing a red colour generating cathodoluminescent phosphor - and so colour television was commercialised. The 1980s witnessed an increase in demand for rare earth permanent magnets (REPMs) and rechargeable nickel-metal hydride (NiMH) batteries, both of which contain light REE (see Figure 1).

The batteries tended to use mixed REEs or at best, in the case of the magnets, a mixture of praseodymium and neodymium. However, research showed that REEs would have to be completely isolated to take full advantage of their electrical and electronic properties; the problem of high labour costs and time intensive separations remained. Interest arose in China, vdth its low labour costs and significant and accessible domestic deposits of REEs. Furthermore, it became obvious that with less importance placed on environmental or worker safety, China could and would employ some lowcost mining methods that other countries would not. Since manual labour was much cheaper than elsewhere, Chinese companies relied on a huge labour force rather than expensive capital investments in the latest mining and processing machinery, and employed a make do attitude to the equipment it did have to buy. China had a third, and overwhelming advantage, in that its largest deposits of the sought-after rare earth mineral bastnaesite were in the middle of an iron mining region 33

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undergoing intense development. Thus infrastructure was already in place for the rare earth miners, significantly reducing if not removing entirely infrastructure overheads. During the 1990s, the price of separated REE from China began to fall and their purity to rise just as western researchers were realising the benefits of separated REEs. The result was that more and more production and assembly of REPMs and NiMH batteries was outsourced to China along with their manufacturing technology to take double advantage of low labour and raw material costs. Western mines, including the one at Mountain Pass, found it impossible to compete, so were shut down. From the point of view of western free market capitalists, outsourcing to China was globalisation working efficiently to bring down costs and challenge conventional technology - in this case ferrite magnets and lead acid batteries. No one seemed to consider that China would rapidly develop the skills or the internal market to use REEs - at the very least not for generations to come.

raising the heat

Car makers then became interested in REPMs, as they allowed motors to be miniaturised, which saved weight and increased fuel efficiency. Encouraged by the potential of high volume application, magnet researchers in the US, lapan, and even China started adapting REPMs to maintain their maximum fiux at the kinds of temperatures typically encountered in a car's engine bay. An alloy of the REE dysprosium and neodymium achieved this, but the theory behind the process was not well understood and the practical know-how was fiercely guarded by the lapanese manufacturers, while at the same time China held a monopoly

on the relatively uncommon heavy REE, dysprosium. There were fears that there would not be enough dysprosium to support the automotive industry's needs. It was well known that uranium ores often contained elevated levels of heavy REEs but their concentration was still so low as to make the metallurgy daunting, and no one was willing to spend money to solve such a problem, which involved the handling of enormous volumes of solvents being methodically mixed with each other and then separated and treated to extract a tiny fraction over and over again, if it involved radioactive species. China's geology once again came to the rescue. In some of its southern provinces, including Sichuan, there are weathered clay deposits where the radioactive species have already been washed away leaving the heavy REEs. This natural "separation" of heavy REEs is unique in the world and has greatly simplified safety. However, if these ionic clays were in the West it is unlikely they would have been developed as their low grades and the lack of supporting infrastructure would have been obstacles too big to overcome. It didn't stop Chinese entrepreneurs who, using cheap unskilled labour, fiood hilltops with chemical reagents and channel them into catch basins made from plastic-lined earthen ponds. The extraction liquor is concentrated by letting it partially evaporate and is then processed with crude tanks and makeshift solvent exchange. Only a small fraction of the heavy REEs are recovered this way, most remain in the process residue.

which is essential for non-incandescent lighting and displays, and 8000 t/y of yttrium, essential for high temperature aircraft and rocket engines. In 2009, China announced it might cease exporting heavy REEs to conserve its remaining reserves for domestic demand, which is growing at an unprecedented rate. On 14 November 2010, China announced it was cutting exports of all basic forms of REEs to conserve them for future use and restore the damaged environment at the mining sites. Such environmental remediation will require a slow down or perhaps even a temporary shutdown of the mines, so that either conservation or stockpiling, or both, might be now necessary to preserve China's domestic security of supply, the Chinese government said. China will not allow foreign firms to come in and improve production efficiencies over fears they might benefit from the information about its natural resources. Meanwhile, Chinese exploration has not found a replacement for ionic clays that could support global demand for heavy REE.

in search of a plan B
Unsurprisingly, the hunt is now on for economically viable sources outside China. Japan's Toyota is pushing the development of a mining complex in Vietnam which would fulfil all of its conceivable needs for light REE for batteries and magnets. Simultaneously other Japanese and Korean companies are looking at deposits around the world with not just light but also heavy potential. The last of the very large non-Chinese producing REE mines to be shut down is in the process of being

a heavy reliance on China

China's ionic clays are the source of 100% of the world's heavy REE. This includes around 1000 t/y of dysprosium, -200 t/y of terbium. 34 www.tcetoday.com december 2010/January 2011

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re-opened at Mountain Pass, California. The rest of the former mines are either too small or too old to be of further economic value if they contain only light REEs. Glohal exploration has found at least half a dozen deposits with significantly high proportions of heavy REEs with promising finds in Australia, Canada, Namibia, Madagascar, South Africa, and the US. The race to develop another source of heavy REEs is on, and is expected to eclipse the competition to develop the more plentiful light REEs. China and Japan produce more than 80% of REPMs used for motors and sensors in today's cleanest vehicles (these devices contain as much as 12% hy weight of dysprosium and demand is projected to grow year-on-year) there is cause to suggest that Chinese and Japanese companies, and REPM manufacturers in particular, the end user community, should take a lead in determining and financing the development of such deposits. However, such developments are unlikely to be profitable if the output is only rare earth concentrates or even initially separated rare earth compounds such as oxides or oxalates. Therefore such mining operations must be vertically integrated into supply chains so that enough value is added to the concentrates and simple separations to make them profitable. This could mean REPM end-users such as the makers of motor vehicles, wind turbines, and weaponry backwardsintegrating their supply chain right into the rare earths mines, or nations that have an economic interest in some or all such types of manufacturing ventures subsidising rare earth mines. Alternatively an investment fund or other strategic institutional investor could buy

one or more heavy mines and hold them as investments for end-users, high value supply chain component makers, or governments.

long view required

No matter which finance or holding solution is chosen, the financial backer must carefully study all the enabling technologies, ie the chemical extraction, separation, and refining to high purity metals of each unique deposit so as to quantify the costs and estimate the chance of success for each proposed venture. A study published in November by the US Geological Survey, in response to a US defence bill, reported that "unfortunately, the times required for development of new mines is on the order of at least a decade': It appears that the future supply of heavy REEs, upon which the largest portion of the revenues and strategic value of the rare earths depends, is itself reliant on the foresight of governments and large industrial enterprises. Quick action must be taken to develop a more diverse range of mines and supply chains if the world wants to continue to use rare earths in their gadgets and clean power technologies. Process and chemical engineers have an integral role to play in developing new and improved extraction processes that allow for cheaper more efficient recovery of these crucial elements. Further along the supply chain, researchers continue to look for suitable replacements for REE and develop processes and practices to recover REEs at the end of a product's life - though this is also a commercial challenge due to the trace amounts they contain, t e e
Pictured: various applications for REEs: lasers, rockets. X-rays, wind turbines, NiMH batteries and mobile phones

Jack Litton (jacklifton@aol.com) is director at Technology Metals Research

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