Monazite, extraction

Molybdenyl acetylacetonate, 6 147 12-Molybdosilicic acid, 1 127 analysis of, 1 128 Monazite, extraction of, 2 38 separation of rare earths from, 2 56... 

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. 

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. 

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. 

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. 

Primary Mined particularly for the molybdenum contained in the ores. In some instances, molybdenum could be the only valuable metal recovered from the ore. The Questa deposit in New Mexico is mined exclusively for molybdenum content. In other deposits molybdenum may be the main product recovered together with one or more products. In these deposits the molybdenum content alone would allow for a profitable operation. The ore at the Climax mine in Colorado is of this type. Currently, monazite, pyrite, tin, and tungsten are recovered from the ore none of these by-products exists singly nor together in sufficient quantity so that the ore could be mined profitably merely for the extraction of one or all of these by-products. 

In 1908, Kamerling-Onnes got the liquefaction of helium (discovered by Janssen e Lockyer during the solar eclipse of 18 August 1868). Kamerlingh-Onnes obtained in Leiden 60 cc of liquid helium extracted from several tons of monazite sable imported from India. Kamerlingh-Onnes himself discovered the X-transition and the superfluidity in 4He and in 1911 the superconductivity of Hg, a particularly pure substance at that time. In the race towards lower and lower temperatures, Kamerling-Onnes, pumping on liquid 4He, obtained 0.7K in 1926. 

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. 

A commercial mixture of several of the rare-earth elements is called didymium (Di). It is neither an element nor a compound, but is used to name the mixture of oxides and salts of most of the rare-earth elements that are extracted from the ore monazite. Another unique substance, called misch metal, is an alloy of iron and several rare-earth elements (La, Ce, and Pr). This mixture is pyrophoric, which means it sparks when scratched. This is why it is used for cigarette-lighter flints. 

Dysprosium is the 43rd most abundant element on Earth and ranks ninth in abundance of the rare-earths found in the Earth s crust. It is a metallic element that is usually found as an oxide (disprosia). Like most rare-earths, it is found in the minerals monazite and allanite, which are extracted from river sands of India, Africa, South America, and Australia and the beaches of Florida. It is also found in the mineral bastnasite in California. 

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... 

Extraction of lanthanum from monazite is discussed below first, followed by that from bastnasite. 

Lutetium is produced commercially from monazite. The metal is recovered as a by-product during large-scale extraction of other heavy rare earths (See Cerium, Erbium, Holmium). The pure metal is obtained by reduction of lutetium chloride or lutetium fluoride by a alkali or alkaline earth metal at... 

Praesodymium may be recovered from its minerals monazite and bastana-site. The didymia extract of rare earth minerals is a mixture of praesodymia and neodymia, primarily oxides of praesodymium and neodymium. Several methods are known for isolation of rare earths. These are applicable to all rare earths including praesodymium. They include solvent extractions, ion-exchange, and fractional crystallization. While the first two methods form easy and rapid separation of rare earth metals, fractional crystaUization is more tedious. Extractions and separations of rare earths have been discussed in detail earlier (see Neodymium and Cerium). 

The monazite sand is heated with sulfuric acid at about 120 to 170°C. An exothermic reaction ensues raising the temperature to above 200°C. Samarium and other rare earths are converted to their water-soluble sulfates. The residue is extracted with water and the solution is treated with sodium pyrophosphate to precipitate thorium. After removing thorium, the solution is treated with sodium sulfate to precipitate rare earths as their double sulfates, that is, rare earth sulfates-sodium sulfate. The double sulfates are heated with sodium hydroxide to convert them into rare earth hydroxides. The hydroxides are treated with hydrochloric or nitric acid to solubihze all rare earths except cerium. The insoluble cerium(IV) hydroxide is filtered. Lanthanum and other rare earths are then separated by fractional crystallization after converting them to double salts with ammonium or magnesium nitrate. The samarium—europium fraction is converted to acetates and reduced with sodium amalgam to low valence states. The reduced metals are extracted with dilute acid. As mentioned above, this fractional crystallization process is very tedious, time-consuming, and currently rare earths are separated by relatively easier methods based on ion exchange and solvent extraction. 

There are several processes for commercial thorium production from monazite sand. They are mostly modifications of the acid or caustic digestion process. Such processes involve converting monazite to salts of different anions by combination of various chemical treatments, recovery of the thorium salt by solvent extraction, fractional crystallization, or precipitation methods. Finally, metalhc thorium is prepared by chemical reduction or electrolysis. Two such industrial processes are outlined briefly below. 

Finely-ground monazite is treated with a 45% NaOH solution and heated at 138°C to open the ore. This converts thorium, uranium, and the rare earths to their water-insoluble oxides. The insoluble residues are filtered, dissolved in 37% HCl, and heated at 80°C. The oxides are converted into their soluble chlorides. The pH of the solution is adjusted to 5.8 with NaOH. Thorium and uranium are precipitated along with small quantities of rare earths. The precipitate is washed and dissolved in concentrated nitric acid. Thorium and uranium are separated from the rare earths by solvent extraction using an aqueous solution of tributyl phosphate. The two metals are separated from the organic phase by fractional crystallization or reduction. 

In one acid digestion process, monazite sand is heated with 93% sulfuric acid at 210°C. The solution is diluted with water and filtered. Filtrate containing thorium and rare earths is treated with ammonia and pH is adjusted to 1.0. Thorium is precipitated as sulfate and phosphate along with a small fraction of rare earths. The precipitate is washed and dissolved in nitric acid. The solution is treated with sodium oxalate. Thorium and rare earths are precipitated from this nitric acid solution as oxalates. The oxalates are filtered, washed, and calcined to form oxides. The oxides are redissolved in nitric acid and the acid solution is extracted with aqueous tributyl phosphate. Thorium and cerium (IV) separate into the organic phase from which cerium (IV) is reduced to metalhc cerium and removed by filtration. Thorium then is recovered from solution. 

If the starting material is gadolinite, ore is digested with hydrochloric or nitric acid. Rare earths dissolve in acid. The solution is treated with sodium oxalate or oxalic acid to precipitate rare earths as oxalates. For euxenite, ore is opened either by fusion with potassium bisulfate or digestion with hydrofluoric acid. If monazite or xenotime is extracted, ore is either heated with sulfuric acid or digested with caustic soda solution at elevated temperatures. 

Third example - Although ceric oxide really represents the active element in polishing media, most of the polishing plants are satisfied with about 50 % pure ceric oxide, which is available in the natural mixture of the light rare eai h elements as they are extracted either from bastnasite or monazite, in order to keep the cost of the product low. 

From 1940 to 1965, the principal source of these rare earth products was the mineral monazite (Th, RE orthophosphate) which fortunately or unfortunately, depending on one s point of view, contains 4-6% thorium. Today, there is essentially no market for thorium in the U.S. The expense of separating out thorium-free rare-earth products from monazite is not only excessive, but bound tightly in governmental red tape because of the mild radioactivity of the thorium. This situation does not apply in France, Brazil, or India, whose governments are wisely stockpiling all extracted thorium for future atomic energy needs. 

Th, thorium, was discovered in 1829 by Jons Jakob Berzelius, who isolated a new oxide from a recently discovered mineral which Jens Esmark had sent to him. He called the oxide thoria and the mineral thorite (ThSi04) after the Scandinavian god Thor. Berzelius subsequently made the metal by the reduction of ThF4 with Na. Th now is extracted from monazite, a phosphate of rare earths and Th. The mineral is heated in concentrated NaOH to give hydrous oxides, which are filtered out. HCl is then added to dissolve the solids and when the pH is adjusted to 3.5, Th02 precipitates and the rare earths remain in solution. The Th02 is solubilized and purified by solvent extraction. 

Because of its lower cost, mesothorium 1 is frequently substituted for radium in therapy and in the manufacture of luminous watch-dials. The commercial process for extracting it from the by-products of monazite sand was long kept secret, but after Soddy and W. Marckwald independently discovered that it is chemically identical with radium, the process for extracting the latter element from pitchblende was adapted so that it could be used for recovering mesothorium 1 (84,94). 

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