Monazites

At this date, the principal ore minerals for the REEs are monazite, bastnaesite, and xenotime. The first REE mineral to be used was gadolinite, and from this mineral, several of the REE were first isolated, but it was not applied on an industrial scale. The first REE ore mineral from which REE were extracted for industrial use was monazite. 

Voncken, The Rare Earth Elements, SpringerBriefs in Earth Sciences, DOI 10.1007/978-3-319-26809-5 2 

Monazite occurs generally as a minor mineral in granites and granodiorites and associated pegmatites, and also occurs in many metamorphic rocks. 

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It is recovered commercially from monazite sand, which contains about 3%, and from bastnasite, which contains about 0.2%. Wohler obtained the impure element in 1828 by reduction of the anhydrous chloride with potassium. The metal is now produced commercially by reduction of the fluoride with calcium metal. It can also be prepared by other techniques. 

Lanthanum is found in rare-earth minerals such as cerite, monazite, allanite, and bastnasite. Monazite and bastnasite are principal ores in which lanthanum occurs in percentages up to 25 percent and 38 percent respectively. Misch metal, used in making lighter flints, contains about 25 percent lanthanum. 

Cerium is the most abundant so-called rare-earths metal. It is found in a number of minerals including ahanite (also known as orthite), monazite, bastnasite, cerhe, and samarskite. Monazite and bastnasite are presently the two more important sources of cerium. 

Large deposits of monazite (found on the beaches of Travancore, India and in river sands in Brazil), ahanite (in the western United States), and bastnasite (in Southern California) will supply cerium, thorium, and the other rare-earth metals for many years to come. 

Thorium occurs in thorite and in thorianite. Large deposits of thorium minerals have been reported in New England and elsewhere, but these have not yet been exploited. Thorium is now thought to be about three times as abundant as uranium and about as abundant as lead or molybdenum. Thorium is recovered commercially from the mineral monazite, which contains from 3 to 9% Th02 along with rare-earth minerals. 

As with other rare-earth metals, except for lanthanum, europium ignites in air at about 150 to I8O0C. Europium is about as hard as lead and is quite ductile. It is the most reactive of the rare-earth metals, quickly oxidizing in air. It resembles calcium in its reaction with water. Bastnasite and monazite are the principal ores containing europium. 

The element occurs along with other rare-earth elements in a variety of minerals. Monazite and bastnasite are the two principal commercial sources of the rare-earth metals. It was prepared in relatively pure form in 1931. 

Gr. neos, new, and didymos, twin) In 1841, Mosander, extracted from cerite a new rose-colored oxide, which he believed contained a new element. He named the element didymium, as it was an inseparable twin brother of lanthanum. In 1885 von Welsbach separated didymium into two new elemental components, neodymia and praseodymia, by repeated fractionation of ammonium didymium nitrate. While the free metal is in misch metal, long known and used as a pyrophoric alloy for light flints, the element was not isolated in relatively pure form until 1925. Neodymium is present in misch metal to the extent of about 18%. It is present in the minerals monazite and bastnasite, which are principal sources of rare-earth metals. 

Gadolinium is found in several other minerals, including monazite and bastnasite, both of which are commercially important. With the development of ion-exchange and solvent extraction techniques, the availability and prices of gadolinium and the other rare-earth metals have greatly improved. The metal can be prepared by the reduction of the anhydrous fluoride with metallic calcium. 

Ytterby, a village in Sweden) Discovered by Mosander in 1843. Terbium is a member of the lanthanide or "rare earth" group of elements. It is found in cerite, gadolinite, and other minerals along with other rare earths. It is recovered commercially from monazite in which it is present to the extent of 0.03%, from xenotime, and from euxenite, a complex oxide containing 1% or more of terbia. 

L. Holmia, for Stockholm). The special absorption bands of holmium were noticed in 1878 by the Swiss chemists Delafontaine and Soret, who announced the existence of an "Element X." Cleve, of Sweden, later independently discovered the element while working on erbia earth. The element is named after cleve s native city. Holmia, the yellow oxide, was prepared by Homberg in 1911. Holmium occurs in gadolinite, monazite, and in other rare-earth minerals. It is commercially obtained from monazite, occurring in that mineral to the extent of about 0.05%. It has been isolated by the reduction of its anhydrous chloride or fluoride with calcium metal. 

Ytterbium occurs along with other rare earths in a number of rare minerals. It is commercially recovered principally from monazite sand, which contains about 0.03%. Ion-exchange and solvent extraction techniques developed in recent years have greatly simplified the separation of the rare earths from one another. 

Uranium, not as rare as once thought, is now considered to be more plentiful than mercury, antimony, silver, or cadmium, and is about as abundant as molybdenum or arsenic. It occurs in numerous minerals such as pitchblende, uraninite, carnotite, autunite, uranophane, and tobernite. It is also found in phosphate rock, lignite, monazite sands, and can be recovered commercially from these sources. 

Monazite concentrate Monazol Monazoline Moncheite Moncut Mondo Mond process... 

The heavy mineral sand concentrates are scmbbed to remove any surface coatings, dried, and separated into magnetic and nonmagnetic fractions (see Separation, magnetic). Each of these fractions is further spHt into conducting and nonconducting fractions in an electrostatic separator to yield individual concentrates of ilmenite, leucoxene, monazite, mtile, xenotime, and zircon. Commercially pure zircon sand typically contains 64% zirconium oxide, 34% siUcon oxide, 1.2% hafnium oxide, and 0.8% other oxides including aluminum, iron, titanium, yttrium, lanthanides, uranium, thorium, phosphoms, scandium, and calcium. 

Whereas certain rocks of igneous origin formed by melting and recrystallization can include minerals enriched in the lanthanides (4), cerium is usually present as a trace element rather than as an essential component. Only a few minerals in which cerium is an essential stmcture-defining component occur in economically significant deposits. Two minerals supply the world s cerium, bastnasite [68909-13-7] LnFCO., and monazite [1306-41 -8] (Ln,Th)PO. ... 

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. 

Several countries supply monazite concentrates for the world market. Extensive deposits along the coast of western AustraUa are worked for ilmenite and are the primary source of world monazite. Other regions of AustraUa, along with India and Brazil, also supply the mineral. Because monazite contains thorium [7440-29-1], India and Brazil have embargoed its export for many years. In the United States, commerce in the mineral is regulated by the Nuclear Regulatory Commission. 

Ion bomliardment Heaw -mineral concentrate Conductor minerals (ilmenite, riitilej from non-condiictor minerals (zircon, monazite, ahiminiim. silicates, (piartz and others j Roll 120 -1.0 + 0.04 2.5 3-6... 

Scandium is very widely but thinly distributed and its only rich mineral is the rare thortveitite, Sc2Si20v (p. 348), found in Norway, but since scandium has only small-scale commercial use, and can be obtained as a byproduct in the extraction of other materials, this is not a critical problem. Yttrium and lanthanum are invariably associated with lanthanide elements, the former (Y) with the heavier or Yttrium group lanthanides in minerals such as xenotime, M "P04 and gadolinite, M M SijOio (M = Fe, Be), and the latter (La) with the lighter or cerium group lanthanides in minerals such as monazite, M P04 and bastnaesite, M C03F. This association of similar metals is a reflection of their ionic radii. While La is similar in size to the early lanthanides which immediately follow it in the periodic table, Y , because of the steady fall in ionic radius along the lanthanide series (p. 1234), is more akin to the later lanthanides. 

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. 

There are over 100 minerals known to contain lanthanides but the only two of commercial importance are monazite, a mixed La, Th, Ln phosphate, and bastnaesite, an La, Ln fluorocarbonate (M C03F). Monazite is widely but sparsely distributed in many rocks but, because of its high density and inertness, it is concentrated by weathering into sands on beaches and river beds, often in the presence of other... 

The bulk of both monazite and bastnaesite is made up of Ce, La, Nd and Pr (in that order) but, whereas monazite typically contains around 5-10% Th02 and 3% yttrium earths, these and the heavy lanthanides are virtually absent in bastnaesite. Although thorium is only weakly radioactive it is contaminated with daughter elements such as Ra which are more active and therefore require careful handling during the processing of monazite. This is a complication not encountered in the processing of bastnaesite. 

Thorium is widely but rather sparsely distributed and its only commercial sources are monazite sands (see p. 1229) and the mineral conglomerates of Ontario. The former are found in India, South Africa, Brazil, Australia and Malaysia, and in exceptional cases may contain up to 20% Th02 but more usually contain less than 10%. In the Canadian ores the thorium is present as uranothorite, a mixed Th,U silicate, which is accompanied by pitchblende. Even though present as only 0.4% Th02, the recovery of Th, as a co-product of the recovery of uranium, is viable. 

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. 

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