Lanthanide ores

Ce,La,Nd,Pr)P04 containing some thorium silicate (ThOj 1-18%). The principle lanthanide ore. 

This soft, silver white metal reacts with air and water. The oxide is applied in optical glasses with high refractive indices (special lenses for powerful cameras and telescopes). Used for special effects in optoelectronics and electronics. Lanthanum exhibits catalytic properties. It is a component of flint and battery electrodes. Lanthanum boride (LaB6) is the superior electron-emitter for electron microscopes. Lanthanum is the first of the series of 14 lanthanides, also called the "rare-earth" metals, whose inner N shells are filled with electrons. They do not belong on the "red list" of endangered species they are neither rare nor threatened with depletion. China is particularly rich in lanthanide ores. 

Alumina, alkaline-earth oxides, mixed oxides (spinels), rare-earth oxides, and lanthanide ores are known additives capable of sorbing S-impurities. The properties of these materials can be manipulated to produce catalysts capable of reducing up to -80% S-emissions and meet the refiner needs. It is, however, unlikely that these systems will be capable of satisfying the more stringent environmental S-emission standards expected in the future. Details of the reaction mechanism by which additives and promoters catalyze the oxidative sorption of S-impurities and details of catalyst deactivation have not yet been proposed. This work could provide useful information to help design more efficient S-transfer catalysts. The catalytic control of S-emissions from FCC units has been described in detail in two papers appearing in this volume (46,47) and in the references given (59). 

Mendeleev s Periodic Table made no provision for a lanthanide series. No one could predict how many of these elements would exist and it was not until Moseley s work on X-ray spectra that resulted in the concept of atomic number (1913) that it was known that an element with atomic number 61, situated between neodymium and samarium, remained to be discovered. Although several claims were made for its discovery in lanthanide ores, it was realized that no stable isotopes of element 61 existed and, from the late 1930s, nuclear chemistry was applied to its synthesis. 

Although early attempts to identify it in lanthanide ores were not successful, it has been detected at the level of 4 X 10 gkg in Congolese pitchblende. It has also been detected at a low level in apatite (10 g from 6milhon kg mineral), although it may have originated there from neutron irradiation of neodymium or by spontaneous fission of... 

Lanthanide series Lanthanides are silvery metals with relatively high melting points. Because there is so little variation in properties among inner transition metals, they are found mixed together in nature and are extremely hard to separate. The name of one lanthanide, dysprosium, comes from a Greek word meaning hard to get at. Lanthanide ores were first mined in Ytterby, Sweden. Which four elements are named for this town ... 

Placer deposits of potential future value as lanthanide ores invariably have the lanthanides present in common lanthanide or lanthanide-concentrating minerals (e.g., apatite, allanite, monazite, xenotime, zircon). Most pegmatites of potential value as ore have the lanthanides as common lanthanide-bearing minerals too (those previously mentioned plus fluorite). Alkalic rock complexes may produce commercially useful concentrations of common lanthanide-bearing minerals (e.g., apatite, perovskite) or rare ones (e.g., bastnaesite). 

More than 70% of the world s production of lanthanides since 1973 has come from the bastnaesite-rich carbonatite body at Mountain Pass, California. This ore body, operated by Molycorp, Inc., has the capacity to meet world demand at the present rate for 100 years. No other lanthanide ore body of comparable size and grade is known. The development of the Mountain Pass ore body was a major factor in bringing about the current uses and research into industrial applications of the lanthanides. It made them available in reasonably large quantities at competitive prices. 

Group III with electronic configuration 5s 4d . The principal ore is gadolinite (a silicate also containing lanthanides). Y2O3 containing Eu is used as a red phosphor in colour television. Yttrium iron garnets are used as microwave filters. 

The uranium ore from Elliot Lake, Canada, contains yttrium and lanthanides (see Uranium and uranium compounds). In the Jiangxi province of the People s Repubhc of China a large reserve of a rare-earth-containing clay contains over 1,000,000 t of REO. This ore is characterized by having a low cerium content (<5%) but a high content in samarium, europium, terbium, and yttrium compared to the main base REO ores (Table 6). ... 

Apatite and other phosphorites constitute a substantial resource of rare earths. The REO content is highly variable and ranges from trace amounts to over 1%. Apatite- [1306-05-4] rich tailings of the iron ore at Mineville, New York, have been considered a potential source of yttrium and lanthanides. Rare-earth-rich apatites are found at the Kola Peninsula, Russia, and the Phalaborwa complex in South Africa. In spite of low REO content apatites could become an important source of rare earths because these are processed in large quantities for the manufacturing of fertilisers (qv). 

Oil field uses are primarily imidazolines for surfactant and corrosion inhibition (see Petroleum). Besides the lubrication market for metal salts, the miscellaneous market is comprised of free acids used ia concrete additives, motor oil lubricants, and asphalt-paving applications (47) (see Asphalt Lubrication AND lubricants). Naphthenic acid has also been studied ia ore flotation for recovery of rare-earth metals (48) (see Flotation Lanthanides). 

There are a number of minerals in which thorium is found. Thus a number of basic process flow sheets exist for the recovery of thorium from ores (10). The extraction of mona ite from sands is accompHshed via the digestion of sand using hot base, which converts the oxide to the hydroxide form. The hydroxide is then dissolved in hydrochloric acid and the pH adjusted to between 5 and 6, affording the separation of thorium from the less acidic lanthanides. Thorium hydroxide is dissolved in nitric acid and extracted using methyl isobutyl ketone or tributyl phosphate in kerosene to yield Th(N02)4,... 

Bastnasite has been identified in various locations on several continents. The largest recognized deposit occurs mixed with monazite and iron ores in a complex mineralization at Baiyunebo in Inner MongoHa, China. The mineral is obtained as a by-product of the iron ore mining. The other commercially viable bastnasite source is the Mountain Pass, California deposit where the average Ln oxide content of the ore is ca 9%. This U.S. deposit is the only resource in the world that is minded solely for its content of cerium and other lanthanides. 

The production of cerium derivatives begins with ore beneficiation and production of a mineral concentrate. Attack on that concentrate to create a suitable mixed lanthanide precursor for later separation processes follows. Then, depending on the relative market demand for different products, there is either direct production of a cerium-rich material, or separation of the mixed lanthanide precursor into individual pure lanthanide compounds including compounds of pure cerium, or both. The starting mineral determines how the suitable mixed lanthanide precursor is formed. In contrast the separation... 

An alternative commercial form of a metallic mixed lanthanide-containing material is rare-earth siUcide [68476-89-1/, produced in a submerged electric-arc furnace by the direct reduction of ore concentrate, bastnasite, iron ore, and quart2. The resulting alloy is approximately 1/3 mischmetal, 1/3 sihcon, and 1/3 iron. In addition there are some ferro-alloys, such as magnesium—ferrosilicons, derived from cerium concentrate, that contain a few percent of cerium. The consumption of metallic cerium is overwhelmingly in the mixed lanthanide form in ferrous metallurgy. 

The minerals on which the work was performed during the nineteenth century were indeed rare, and the materials isolated were of no interest outside the laboratory. By 1891, however, the Austrian chemist C. A. von Welsbach had perfected the thoria gas mantle to improve the low luminosity of the coal-gas flames then used for lighting. Woven cotton or artificial silk of the required shape was soaked in an aqueous solution of the nitrates of appropriate metals and the fibre then burned off and the nitrates converted to oxides. A mixture of 99% ThOz and 1% CeOz was used and has not since been bettered. CeOz catalyses the combustion of the gas and apparently, because of the poor thermal conductivity of the ThOz, particles of CeOz become hotter and so brighter than would otherwise be possible. The commercial success of the gas mantle was immense and produced a worldwide search for thorium. Its major ore is monazite, which rarely contains more than 12% ThOz but about 45% LnzOz. Not only did the search reveal that thorium, and hence the lanthanides, are more plentiful than had previously been thought, but the extraction of the thorium produced large amounts of lanthanides for which there was at first little use. 

Apart from the unstable (half-life 2.623 y) of which traces occur in uranium ores, the lanthanides are actually not rare. Cerium (66 ppm in the earth s crust) is the twenty-sixth most abundant of all elements, being half as abundant as Cl and 5 times as abundant as Pb. Even Tm (0.5 ppm), the rarest after Pm, is rather more abundant in the earth s crust than is iodine. 

The separation of basic precipitates of hydrous Th02 from the lanthanides in monazite sands has been outlined in Fig. 30.1 (p. 1230). These precipitates may then be dissolved in nitric acid and the thorium extracted into tributyl phosphate, (Bu"0)3PO, diluted with kerosene. In the case of Canadian production, the uranium ores are leached with sulfuric acid and the anionic sulfato complex of U preferentially absorbed onto an anion exchange resin. The Th is separated from Fe, A1 and other metals in the liquor by solvent extraction. 

Rare earth (RE) is a generic name for 14 metallic elements of the lanthanide series. These elements have similar chemical propenies and are usually supplied as a mixture of oxides extracted from ores such as bastnaesite or monazite. 

The basis for the claim of discovery of an element has varied over the centuries. The method of discovery of the chemical elements in the late eightenth and the early nineteenth centuries used the properties of the new sustances, their separability, the colors of their compounds, the shapes of their crystals and their reactivity to determine the existence of new elements. In those early days, atomic weight values were not available, and there was no spectral analysis that would later be supplied by arc, spark, absorption, phosphorescent or x-ray spectra. Also in those days, there were many claims, e.g., the discovery of certain rare earth elements of the lanthanide series, which involved the discovery of a mineral ore, from which an element was later extracted. The honor of discovery has often been accorded not to the person who first isolated the element but to the person who discovered the original mineral itself, even when the ore was impure and that ore actually contained many elements. The reason for this is that in the case of these rare earth elements, the earth now refers to oxides of a metal not to the metal itself This fact was not realized at the time of their discovery, until the English chemist Humphry Davy showed that earths were compounds of oxygen and metals in 1808. 

Lanthanides are also found as minor components in other ores, particularly in association with uranium or in phosphate rock. These are often coextracted with the major product and can be economically recovered from the waste streams resulting from the uranium or phosphoric acid extraction. 

The elements in the lanthanide series are also called rare-earth elements they are not scarce or rare, but at one time they were thought to be rare because they were very difficult to find and extract from their ores, difficult to separate from each other, and difficult to identify. Chemical elements that have similar physical and chemical properties tend to occur together in the same ores and minerals. 

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