CFLs and REE

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CFLs contain Rare Earth Elements

Definition

Rare Earth Elements (REE) are a group of the following 17 elements: the Lanthanides (= 15 elements), Sc (Scandium) and Y (Yttrium). The Lanthanides are:

  • La (Lanthanum)
  • Ce (Cerium)
  • Pr (Praseodymium)
  • Nd (Neodymium)
  • Pm (Promethium)
  • Sm (Samarium)
  • Eu (Europium)
  • Gd (Gadolinium)
  • Tb (Terbium)
  • Dy (Dysprosium)
  • Ho (Holmium)
  • Er (Erbium)
  • Tm (Thulium)
  • Yb (Ytterbium)
  • Lu (Lutetium)

Production and demand of rare earths

Source: Öko-Insitut e.V. (Institut für angewandte Ökologie - Institute for Applied Ecology), Study on Rare Earths and Their Recycling, Darmstadt, January 2011:

The world production of rare earths was around 124 000 t REO [Rare Earth Oxide] per year in 2008 and 2009 according to data from the US Geological Survey (USGS). This is quite low compared with the annual primary production of other metals, e.g. 39 Mt aluminium or 22 Mt copper. More than 97 % of the production and a large share of the further processing are located in China. Small amounts are produced in Russia, India, Malaysia, Brazil. Additionally, around 20 000 t REO were illegally produced in China and are not included in the above given USGS data. Due to the high demand for rare earths and the decreasing Chinese exports, there are many activities aimed at the opening of new mines outside of China. The most advanced mining projects are the re-opening of the Mountain Pass mine in California by Molycorp Minerals and the new rare earth mine at Mt Weld in Australia by Lynas with processing in Malaysia. Their operation is scheduled to begin in 2012 and 2011, respectively. (p. 24)

Though the Chinese produce more than 95% of the global production, their share of the reserves is much lower at 38 %. Large deposits are also found in the USA, Australia and states of the former Soviet Union. (p. 7) Rare earth metals are widely distributed across the earth [estimated at 99 million tonnes in REO content]. China holds around 36% of the REE reserves, Russia and other members of the Common wealth of Independent States (CIS) hold 19%, the U.S. holds around 13% and Australia has 5%. (DOE_2010, Critical Materials Strategy, p. 29)

The global demand of around 120 000 t REO in 2008 is expected to increase up to 170 000 - 200 000 t in 2014. (Öko, p. 83) Potential shortages might occur for lanthanum, yttrium and europium with a high degree of probability.

However, Global REO production was estimated at 118,500 tonnes in 2010, with the vast majority of supply originating in China. Around the world, there are many promising mineral deposits that could be developed to meet future growth in demand for rare earths. (DOE 2011, p. 81)

The price for lanthanum, cerium, dysprosium, neodymium, yttrium and europium rose dramatically. See Marc Humpfries, Rare Earth Elements: The Global Supply Chain, September 6, 2011, p. 7.

The demand of REEs increased from 125,000 ton in 2008 to 137,000 ton in 2011. But especially prices have grown to unknown levels. While the market volume of raw materials in 2008 amounted to 2.4 billion euro, in 2011 it rose even to 27 billion euro. With the current consumption, REEs will be exhausted within 30 to 40 years! (De Tijd, April 19, 2012)

It was remarkable that right on the last day the lamps of 60W were tolerated in Europe (31 August 2011), the price of CFLs rose with about 25% (the increase in price earlier in that year included). Reason? The run on rare earths such as europium, terbium en yttrium and the restrictive export policy of China. (Source)

Major risks of REE mining and processing with insufficient environmental techniques

(Öko-Insitut e.V., p. 46)
Risk Affected compartments Relevant Toxic compounds
Overtopping of tailings dam groundwater, surface water, soil Water emissions:
  • in most cases radionuclides, mainly thorium and uranium;
  • heavy metals;
  • acids;
  • fluorides;
Air emissions:
  • in most cases radionuclides, mainly thorium and uranium;
  • heavy metals;
  • HF, HCl, SO2 etc.
Collapse of tailings dam by poor construction groundwater, surface water, soil
Collapse of tailing dam by seismic event groundwater, surface water, soil
Pipe leakage groundwater, surface water, soil
Ground of tailing pond not leak-proof groundwater
Waste rock stockpiles exposed to rainwater groundwater, surface water, soil
Dusts from waste rock and tailings air, soil
No site-rehabilitation after cease of mining operation land-use, long-term contaminated land
Processing without flue gas filters air, soil
Processing without waste water treatment surface water

Meanwhile

  • most of the small illegal mines in China have no environmental technologies at all. There are reports of serious environmental damages and health hazards in their surroundings (Öko-Insitut e.V., p. 47),
  • the tailings from Báiyún Èbó (China) lead to environmental damage and human toxicity. (Öko-Insitut e.V., p. 53)
  • The refining of the rare earth concentrate is a very energy-intensive process and causes air and water emissions. (Öko-Insitut e.V., p. 56) They [The Chinese Society of Rare Earths] estimate at the completion of refining one ton of rare elements, approximately 75 cubic meters of acidic waste water and about one ton of radioactive waste residue are produced. The IAGS reports China produced over 130,000 metric tons of rare earth elements in 2008 alone (IAGS, 2010). (EPA, August 15, 2011)

The mining and further processing of primary earths is associated with nuclear radiation coming from radioactive elements of the natural deposits in most cases. Therefore, primary rare earth processing generally produces radioactive waste. (p. 112)

The Chinese government intends to reduce the environmental harm by installing environmental technologies in the large mines and by reducing the numerous small illegal mines which probably have no environmental technologies at all. (Öko-Insitut e.V., p. 61)

So, a contradiction exists between the development of green technologies and their high environmental pressures in production.

New mines will be opened at:

  • Mountain Pass, California, USA. Molycorp expects to produce approximately 40,000 tonnes per year by the end of 2013. (DOE 2011, p. 81) See also the interesting article concerning this mine.
  • Mount Weld, Australia and processing in Malaysia
  • Knavefjeld, Greenland (construction work planned in 2013, production in 2015). The report "DOE 2011" mentions two selected rare earth projects in Greenland: Greenland Minerals and Energy and Hudson Resources.

In the Kvanefjeld region in southern Greenland, large resources of rare earths with a extra high content of about 14% can be found. A very critical point for environmental hazards in this project is the tailing's management. (Öko-Insitut e.V., p. 58) The interested mining company intends to store the tailings in a natural lake with connection to maritime waters! (p. 61)

Even if the market demand for a particular element would make increased production highly profitable on a tonnage basis, mining companies may be unable to rapidly increase production or quickly open new mines. They are constrained by capital costs typically in the billions of U.S. dollars and by long lead times required for exploration, permitting and facility construction. Some industry experts estimate that a 10-year lead time from initial exploration to the construction of new mines for rare earth elements is typical of the industry. (DOE_2010, p. 92)

12 May 2016: Greenland close to extracting rare earth ore in Kvanefjeld "Greenland Minerals and Energy (GME) started exploration work in the mineral-rich site in 2007 and found deposits of at least 15 rare earth metals that are essential for modern technologies. According to GME's geologists, the incidence of these metals in the site is large enough to cover about 25 percent of the world market's needs for generations to come. However, in order to extract the rare earth ores from Kvanefjeld, GME will also have to mine uranium and locals are worried the radioactive metal could contaminate the surrounding land. In 2013, Greenland's Parliament overturned a ban on uranium mining, but GME must prove the mine is safe and also profitable."

Applications and demand of rare earths for luminescence purposes

About 7% of the REE are globally intended for phosphors and luminescence, in particular for: (Öko-Insitut e.V., p. 63)

  • Energy efficient lighting
  • LED
  • LCD
  • Plasma display
  • Laser

It concerns cerium (Ce), lanthanum (La), europium (Eu), terbium (Tb), yttrium (Y) and gadolinium (Gd).

Let there be no misunderstanding: Phosphors accounted for 7% of all REE usage by volume and 32% of the total value in 2008 (Kingsnorth 2010) (U.S. Department of Energy, Critical Materials Strategy, December 2010, p. 21)! Europium and terbium are known as expensive rare earths. (Öko-Insitut e.V., p. 64; 75-76)

Lynas (...) estimates that around 84 % of the phosphors are globally used for lighting, around 12 % for LCD and around 4 % for plasma displays. (p. 76)

Phosphor materials emit light after absorption of energy. They are produced by dotting salt-like host lattices with metal ions in small concentrations. The colour of the light essentially depends on the properties of thes metal ions, also called activators. (...) The temperature of the colour can be adjusted (warm or cold light), depending on the composition. As the spectra of the individual metals are limited, lamps with special requirements use up to eight phosphors, mainly lanthanides (Wickleder 2010). (Öko-Insitut e.V., p. 101) The main drivers for the demand of these REE [La, Y and Eu] are energy efficient lighting. (Öko-Insitut e.V., p. 89-90)

This is confirmed by "DOE 2011", p. 103: High-efficiency fluorescent lighting represents approximately 85% of global demand for rare earth phosphors. Phosphor demand will continue to grow with the increased use of CFLs and higher efficiency LFLs.

Combining Eu phosphor compounds with terbium phosphor compounds produces the white light of helical fluorescent light bulbs and is a primary component in the production of T8 and T5 fluorescent tubes. Demand will increase during the anticipated switch from high-volume halophosphor fluorescent lamps to T8 and T5 linear and compact fluorescent tubes as a result of DOE rulemaking and worldwide trends. Increased demand is expected until light emitting diode (LED) bulbs (which use much less REEs) achieve significant market penetration. (DOE_2010, p. 124)

The growth of rare earth consumption in the sector of lighting is determined by following parameters: (p. 76)

  • The global overall growth including all types of lighting is estimated at 7 % per year by Philips (2008) for the years 2004 to 2011.
  • Incandescent bulbs are going to be phased out due to their high energy demand. For example, the European Union, Australia, Canada and the United States banned the sale of incandescent bulbs in the years ahead in accordance with national law (Jaspersen McKeown 2008, DOE 2010). They will be replaced by other lighting systems, mainly by compact fluorescent lamps (CFL) and halogen lamps. Besides these types, there are numerous other lighting systems. Most of the energy efficient lighting systems include phosphors based on rare earths.
  • Currently LEDs which also contain rare earths still play a minor role in lighting with a market share of 2.4 % in 2008.

Phosphor demand will continue to grow with the increased use of high efficiency linear fluorescent lamps (LFLs) and compact fluorescent lamps (CFLs). (Footnote 81) Because REEs used in lighting need to be very pure (99.999%), the rare earth oxides (REOs) sold to phosphor manufacturers are much more expensive than those used by manufacturers of other REE applications. In the event of a material shortage, producers of REOs would likely divert the available supply of a given element into phosphors rather than the other applications of this element due to the greater profit margins. Therefore, the impact of shortages in overall REE supplies may have a limited effect on the availability of lighting phosphors (Gschneidner, pers. comm.). (DOE_2010, Critical Materials Strategy, p. 86)

LEDs use much less rare earth content than fluorescent light bulbs, while OLEDs and halogen incandescents use no rare earths. (U.S. Department of Energy, Critical Materials Strategy, December 2011, p. 23.)

REEs used in phosphors must be 99.999% pure, necessitating tight control over the manufacturing process. China currently consumes 80% of world’s lighting phosphor supply to produce components for major lighting manufacturers, although it subsequently exports the majority of these components for sale worldwide. The location of the lamp manufacturing process (which includes the production of glass tubes, coating with phosphors and assembly of bulb components) is driven by the labor and transportation costs of different types of bulbs, as well as by local government manufacturing incentives. The presence of impurities of a few parts per million can distort the color characteristics of a given phosphor. In order to achieve these high purities, the purification takes many more separation stages, significantly increasing the cost of the rare earth oxides (REOs) used to produce the phosphors. Suppliers of phosphors used in lighting products generally produce mass quantities of similar phosphor materials for application in television screens, computer monitors and electronic instrumentation (McClear 2008). (DOE_2010, p. 23)

CFLs are manufactured almost exclusively in China and distributed by major lighting manufacturers for sale worldwide. LFLs are still primarily assembled in plants in North America and Europe that are closer to the ultimate points of sale. This arrangement exists because it is much cheaper to ship the raw materials than the LFL bulbs, whose volume consists mostly of air inside the fragile lighting tubes.

Regardless of manufacturing and assembly location, major U.S. lighting manufacturers continue to hold the intellectual property rights to formulas for the fluorescent lighting phosphors and invest significantly in research and development (R&D) related to lighting manufacturing. This allows U.S. firms to retain control of the value chain, despite the large role of Chinese firms in the manufacturing process. (DOE_2010, Critical Materials Strategy, p. 23)

Phosphor supply chain

Source: DOE 2011, p. 27-28

  • Mining and separation: More than 90% current extraction and processing in China
  • Phosphor powders: Powders produced in China but major lighting manufacturers in U.S. and Europe hold intellectual property rights.
  • Light Bulb Assembly and Distribution: CFLs assembled in China

Which materials will become critical?

  • According to the analysis of "DOE 2011", p. 116, dysprosium, terbium, europium, neodymium and yttrium are critical in the short term [0 - 5 years]. The same materials remain critical in the medium term [5 - 15 years].
  • Indium and the rare eart elements tellurium, cerium and lanthanum will become near-critical in the short term. Lithium and tellurium will become near-critical in the medium term.

Most new energy efficient lighting systems contain rare earths (compact fluorescent lamp, LED, plasma display, LCD display). ((Öko-Insitut e.V., p. 104) An additional supply risk for most of these applications is the lack of adequate substitutes for many phosphors in the short term. (p. 92) Substitutions are rare, particularly for compact fluorescent lamps. R&D is required for alternative phosphors with high efficiency and high light quality. (p. II, 104)

  • Yttrium (Y): It is a key ingredient in phosphors for both linear fluorescent (LFL) and compact fluorescent (CFL) light bulbs. Demand will increase during the switch from current high-volume, halophosphor fluorescent lamps to T8 and T5 linear and CFLs, as a result of DOE rulemaking and worldwide trends. Demand should continue into the medium term until light emitting diode (LED) bulbs achieve significant market penetration. (DOE_2010, p. 116, DOE 2011, p. 140)
  • There are no substitutes for La as a lighting phosphor in fluorescent light bulbs.(DOE_2010, p. 119)
  • No proven substitute for Eu in fluorescent lamps has been identified. No known substitutes for Eu as a red phosphor in television or LCD screens. (DOE_2010, p. 124, DOE 2011, p. 148) Demand will increase during the switch from high-volume halophosphor fluorescent lamps to T8 and T5 linear and compact fluorescent tubes as a result of U.S. Department of Energy (DOE) rulemaking and worldwide trends. (DOE 2011, p. 148)
  • No current substitutes for Tb as a lighting phosphor in fluorescent bulbs. Ongoing research, particularly in Japan, seeks to reduce Tb required in phosphors (General Electric 2010). (DOE_2010, p. 125, DOE 2011, p. 149)
Element Share of phosphors weight
Lanthanum 8.5%
Cerium 20.0%
Europium 4.5%
Terbium 5.0%
Yttrium 62.0%

Source: DOE 2011, p. 104.

The demand for europium, terbium and yttrium used in lighting phosphors is projected to spike between 2012 and 2014, which coincides with the implementation of new U.S. lighting efficiency standards. There is significant potential for supply-demand mismatches for these elements throughout the short and medium terms. (DOE 2011, p. 77) The U.S. Department of Energy announced today that a team led by Ames Laboratory in Ames, Iowa, has been selected for an award of up to $120 million over five years to establish an Energy Innovation Hub that will develop solutions to the domestic shortages of rare earth metals and other materials critical for U.S. energy security. The new research center, which will be named the Critical Materials Institute (CMI), will bring together leading researchers from academia, from Department of Energy national laboratories, as well as the private sector. (Source)

An interesting summery is REEs: Will We Have Enough?

Recycling of rare earths from lighting and luminescence

Guarde et al. (2010) reported on high rare earths contents in fluorescent powders from the recycling of used fluorescent lamps and tubes, particularly yttrium with up to 9 % and smaller amounts of europium (up to 0.6 %), lanthanum (up to 0.5 %), cerium (up to 0.4 %), gadolinium (up to 0.3 %) and terbium (up to 0.2 %). (p. 102) Currently this fraction is disposed. (p. 107)

Belgian newspaper "De Standaard", October 1, 2012: One of the major specialists in the field of recycling of fluorescent lamps is the Belgian waste management company Indaver. In the coming years, this company will be more and more the starting point for the recycling of CFLs, explains spokesman Jos Artois. Until recent years, the mercury-containing powder from fluorescent lamps and energy saving lamps was simply deposited in a landfill. "But since some years we do it no longer. Everything is now stored. Awaiting starting up installations where such substances can be recycled."

One of the leaders in research in the field is the French chemical company Rhodia. The growing interest of Rhodia for the powder in the lamps is explained by the price of rare earth metals. Rhodia, taken over last year by Solvay, invested in its French offices in Saint-Fons (in the Rhone Valley) and La Rochelle (on the Atlantic coast) EUR 15 million in recycling plants. In Saint-Fons, the emphasis lies on the separation of the rare earth metals from the glass remnants. La Rochelle is responsible for the purification of the substances. In this way, fluorescent lamps and CFLs are now completely recycled. But the question remains: How long has mercury been released in the environment before the beginning of the storage of the mercury containing powder?

In the Belgian newspaper De Tijd (October 12, 2012), the following information on this item was distributed:

Today, 90% of CFLs and halogen lamps are already recycled. But Solvay is the first company in the world which is able to recover the six precious earth metals from the until recently discarded residual powder (3 percent of the lamps). The lanthanum, cerium, terbium, yttrium, europium and gadolinium are substances which under the influence of gas, electrodes and UV radiation give light in a CFL.

In Beveren (near Antwerp, Belgium) Indaver processes yearly about 3,000 tons of gas-discharge lamps from Belgium and the Netherlands. 'Since we know that the residual powder contains rare earth metals which can be recycled, we save it,' said spokesman of Indaver Jos Artois. 'Meanwhile, we have submitted a notification dossier to the proper governments to transport the powder to Solvay. The first charge would leave at the end of this year.'

Recycling of rare earths in general

Only a few industrial recycling activities are currently implemented for rare earths. Up to now, there has been no large-scale recycling of rare earths from magnets, batteries, lighting and catalysts. In principle, the recycling processes for the rare earths are quite complex and extensive if re-use is not possible and a physical and chemical treatment is necessary. (p. 110)

On the other hand: Honda starts at the end of April 2012 with the recycling of nickel batteries from their old hybride cars. They are brought to Japan where they are carefully dismantled, heated and pulverized. It is an extremely expensive operation with only one goal: the recycling of rare earths. (De Tijd, 19 april 2012)

More than the half of the world production goes directly to the car industry. Lanthanum and cerium are the most important compounds of catalysts. But especially the rising of hybride and electric motors needs much rare earths. The materials are used in the production of magnets, an indispensable element in electric motors. One Toyota Prius contains 2 kg of REEs. A wind turbine contains about 100 kg neodymium! (De Tijd, 19 april 2012) ENERCON does not use neodymium in their wind energy converters.

Conclusion

CFLs contain not only toxic mercury, they need also some rare earths which are associated with radioactive waste, environmental damages and health hazards in their surroundings. Rare earth elements are not so rare - they are all over the planet - but are often bound with radioactive elements such as thorium and uranium. The cost to produce them are high. The use of REEs cannot be imposed on everyone. The ban on incandescent lamps, which are free from mercury and from the environment damaging rare earths, should be lifted immediately without further delay!

References

Last updated on August 17, 2017