Lanthanide mineral monazite

Lanthanide, as a pure metal, is difficult to separate from its ores, and it is often mixed with other elements of the series. It is mosdy obtained through an ion-exchange process from the sands of the mineral monazite, which can contain as much as 25% lanthanum as well as the oxides of several other elements of the series. The metal is malleable and ductile and can be formed into many shapes. Lanthanum is considered the most basic (alkaline) of the rare-earth elements. 

Lanthanum is most commonly obtained from the two naturally occurring rate-earth minerals, monazite and bastnasite. Monazite is a rare earth-thorium phosphate that typically contains lanthanum between 15 to 25%. Bastnasite is a rare earth-fluocarbonate-type mineral in which lanthanum content may vary, usually between 8 to 38%. The recovery of the metal from either of its ores involves three major steps (i) extraction of all rare-earths combined together from the non-rare-earth components of the mineral, (ii) separation or isolation of lanthanum from other lanthanide elements present... 

Terbium is recovered from the minerals, monazite, xenotime, and euxenite. The recovery processes are quite similar to those of other lanthanide elements (See individual lanthanide elements). The metal is separated from other rare... 

Thulium was discovered in 1879 by Cleve and named after Thule, the earliest name for Scandinavia. Its oxide thulia was isolated by James in 1911. Thulium is one of the least abundant lanthanide elements and is found in very small amounts with other rare earths. It occurs in the yttrium-rich minerals xenotime, euxenite, samarskite, gadolinite, loparite, fergusonite, and yttroparisite. Also, it occurs in trace quantities in minerals monazite and... 

Only thorium and uranium have half-lives long enough to survive since the formation of the Earth. Thorium is found together with lanthanides in the phosphate mineral monazite (LnP04), and uranium occurs as pitchblende U303 and carnotite K2(U02)2(V04 )2.3H20. Uranium is principally used as a... 

There are only a few minerals where thorium occurs as a significant constituent. The commercially important ore is the golden-brown, lanthanide phosphate, monazite [13064-1 -8/, LnPO where Ln = Ce, La, or Nd, in which thorium is generally present in a 1—15% elemental composition (7,8). Monazite is widely distributed around the world. Some deposits are quite large. Beach sands from Australia and India contain monazite from which concentrates of lanthanides, titanium, zirconium, and thorium are produced (7). The Travancore deposits in India are the most famous, and have been perhaps one of the most significant sources of commercial thorium. Additional information on the occurrence of thorium in minerals can be found in the literature (7). A review of the mineralogy of thorium is also available (9). 

Many of the f-block elements are extracted from phosphate minerals. Monazite, MPO4, can contain the lanthanide metals, Y and Th, at the cation sites M. The Torbenite and other... 

Thorium is widely distributed in Nature and there are large deposits of the principal mineral, monazite, a complex phosphate containing uranium, cerium, and other lanthanides. The extraction of thorium from monazite is complicated, the main problems being the destruction of the resistant sand and the separation of thorium from cerium and phosphate. One method involves a digestion with sodium hydroxide the insoluble hydroxides are removed and dissolved in hydrochloric acid. When the pH of the solution is adjusted to 5.8, all the thorium and uranium, together with about 3% of the lanthanides, are precipitated as hydroxides. The thorium is recovered by tributyl phosphate extraction from >6M hydrochloric acid solution or by... 

The mineral monazite has the composition LnP04 the anion is effectively (P04) . In nature, the mineral actually consists of a mixture of several slightly different minerals since Ln (representing a lanthanide) can easily be replaced by one or more rare earths, such as Ce, La, Nd, etc., and usually also contains thorium. There is some disagreement on the lattice parameters for monazite in the literature, which may, in part, depend on its purity. There are also two unit cells in use ... 

There are three groups of minerals in which the REE are found. Minerals in the first group contain major quantities of lanthanides. All of these are associated with crystallizations from magmatic mother liquors of pegmatic character (Topp 1965). Important examples are the minerals monazite and xenotime. The second group includes minerals with the REE as minor constituents. Many calcium minerals, such as apatite, are members of this group. Minerals in the third group contain the REE in the bipositive state in small isolated distributions. These are not used as sources of rare earths. 

Nature concentrates lanthanide minerals into commercially useful ores mainly by three processes. Minerals such as monazite are dilute accessories in common rocks, but are fairly resistant to weathering and have high densities. As their host rocks weather away, they remain intact and are moved by water and high-graded into placer deposits as less dense minerals are swept away from them. 

Monazite is a light-lanthanide mineral of composition RPO4. It is a common... 

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. 

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. 

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 most important minerals of the lanthanide elements are monazite (phosphates of La, Ce, Pr, Nd and Sm, as well as thorium oxide) plus cerite and gadolinite (silicates of these elements). Separation is difficult because of the chemical similarity of the lanthanides. Fractional crystallization, complex formation, and selective adsorption and elution using an ion exchange resin (chromatography) are the most successful methods. 

The ores from which rare-earth elements are extracted are monazite, bastnasite, and oxides of yttrium and related fluorocarbonate minerals. These ores are found in South Africa, Australia, South America, India, and in the United States in Cahfomia, Florida, and the Carolinas. Several of the rare-earth elements are also produced as fission by-products during the decay of the radioactive elements uranium and plutonium. The elements of the lanthanide series that have an even atomic number are much more abundant than are those of the series that have an odd atomic number. 

Of all the 17 rare-earths in the lanthanide series, terbium is number 14 in abundance. Terbium can be separated from the minerals xenotime (YPO ) and euxenite, a mixmre of the following (Y, Ca, Er, La, Ce, Y, Th)(Nb, Ta, Ti O ). It is obtained in commercial amount from monazite sand by the ion-exchange process. Monazite may contain as much as 50% rare-earth elements, and about 0.03% of this is terbium. 

Holmium is obtained from monazite, bastnasite and other rare-earth minerals as a by-product during recovery of dysprosium, thulium and other rare-earth metals. The recovery steps in production of all lanthanide elements are very similar. These involve breaking up ores by treatment with hot concentrated sulfuric acid or by caustic fusion separation of rare-earths by ion-exchange processes conversion to halide salts and reduction of the hahde(s) to metal (See Dysprosium, Gadolinium and Erbium). 

Phosphates. The two major phosphate bearing ores are monazite and xenotime, the former being a source of light lanthanides and the latter a source of the heavy rare earths, see Table IV. Deposits in the form of heavy mineral sands are the major source of monazite. They are usually exploited as a byproduct of rutile, ilmenite, and zircon mining operations. 

There are in fact fourteen, and they became known as the rare earths - a misnomer, for some are not particularly rare at all, and they are metals, not earths . A better name is the lanthanides, since they all follow after lanthanum in the Periodic Table. They form an entirely new group, which cannot economically be fitted into Mendeleyev s scheme and is usually depicted as floating freely below it. The lanthanides are, broadly speaking, all rather similar in their chemical behaviour, which is why they were so hard to separate. They are found in minerals such as monazite and bastnasite, the main sources of which are in China and the USA. 

As a metal, europium is very reactive so that one usually finds it under its trivalent, triply oxidized form (Eu3+ ion) in oxides or salts. A divalent form (Eu2+) also displays some stability. Two minerals that contain many of the lanthanide elements, which are separated by liquid-liquid extraction, are commercially important monazite (found in Australia, Brazil, India, Malaysia, and South Africa) and bastnasite (found in China and the United States). 

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