Monazite processes

Until recently, most U.S. thorium production has been as a by-product of monazite processing from placer deposits in Florida, Georgia, and South Carolina. Some bastnaesite has been mined at Mountain Pass, San Bernardino, California. 

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

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. 

The electrostatic separation method is the exclusive choice in some specific situations, for example in the cases of rutile and ilmenite deposits. These deposits generally contain minerals of similar specific gravities and similar surface properties so that processes such as flotation are unsuitable for concentration. The major application of electrostatic separation is in the processing of beach sands and alluvial deposits containing titanium minerals. Almost all the beach sand plants in the world use electrostatic separation to separate rutile and ilmenite from zircon and monazite. In this context the flowsheet given later (see Figure 2.35 A) may be referred to. Electrostatic separation is also used with regard to a number of other minerals. Some reported commercial separations include those of cassiterite from scheelite, wolframite from quartz, cassiterite from columbite, feldspar from quartz and mica, and diamond from heavy associated minerals. Electrostatic separation is also used in industrial waste recovery. 

Moment of inertia, exponents of dimensions in absolute, gravitational, and engineering systems, 8 584t Momentum balance equation, 21 347-348 Momentum equation, 11 738, 739-743 Momentum flowmeters, 11 671 Monactin, chelating agent, 5 710 Monazite, 5 671 14 636 24 756-757 digestion of, 14 638 processing, 5 673 Monel, 14 14 Monel alloy, 9 595 Monel alloy 400, 17 100 Monel cathodes, 11 837 Monensin, 20 132, 133, 135, 136, 137, 139 Monensin A, 20 120... 

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. 

Although neodymium is the 28th most abundant element on Earth, it is third in abundance of all the rare-earths. It is found in monazite, bastnasite, and allanite ores, where it is removed by heating with sulfuric acid (H SO ). Its main ore is monazite sand, which is a mixture of Ce, La, Th, Nd, Y, and small amounts of other rare-earths. Some monazite sands are composed of over 50% rare-earths by weight. Like most rare-earths, neodymium can be separated from other rare-earths by the ion-exchange process. 

Samarium is the 39th most abundant element in the Earths crust and the fifth in abundance (6.5 ppm) of all the rare-earths. In 1879 samarium was first identified in the mineral samarskite [(Y, Ce U, Fe) (Nb, Ta, Ti )Ojg]. Today, it is mostly produced by the ion-exchange process from monazite sand. Monazite sand contains almost all the rare-earths, 2.8% of which is samarium. It is also found in the minerals gadolmite, cerite, and samarskite in South Africa, South America, Australia, and the southeastern United States. It can be recovered as a byproduct of the fission process in nuclear reactors. 

Gadohnium is the 40th most abundant element on Earth and the sixth most abundant of the rare-earths found in the Earths crust (6.4 ppm). Like many other rare-earths, gadolinium is found in monazite river sand in India and Brazil and the beach sand of Florida as well as in bastnasite ores in southern California. Similar to other rare-earths, gadolinium is recovered from its minerals by the ion-exchange process. It is also produced by nuclear fission in atomic reactors designed to produce electricity. 

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 the 12th most abundant of the rare-earths found in the Earths crust. Although it is the 50th most abundant element on Earth, it is one of the least abundant lanthanide metals. It is found in gadolinite and the monazite sands of South Africa and Austraha and in the beach sands of Florida and the Carolinas in the United States. Monazite sand contains about a 50% mixture of the rare-earths, but only 0.05% by weight is holmium. Today, small quantities of holmium are produced by the ion-exchange process. 

Lutetium is the 60th most abundant element on Earth, and it ranks 15th in the abundance of the rare-earths. It is one of the rarest of the lanthanide series. It is found in monazite sand (India, Australia, Brazil, South Africa, and Florida), which contains small amounts of all the rare-earths. Lutetium is found in the concentration of about 0.0001% in monazite. It is difficult to separate it from other rare-earths by the ion-exchange process. In the pure metallic form, lutetium is difficult to prepare, which makes is very expensive. 

HREE Y, whereas monazite, allanite, synchysite and bastnaesite contain most of the LREE. Based on quantitative data approximately half of the fergusonite mass% is associated mainly with zircon, and <2% of the zircon with fergusonite (i.e., reflecting mass distribution differences in the samples). Therefore, in order to recover the HREE, both minerals must be processed and recovered together. The LREE carriers can be recovered as a group. 

Several other processes also are apphed for the commercial production of europium. In general, all processes are based upon the initial steps involving opening the mineral (bastnasite or monazite) with sulfuric acid or sodium hydroxide, often followed by roasting and solubihzation. In one such process after separation of cerium, the soluble rare earth chloride mixture in HCl solution is pH adjusted and treated with bis(2-ethylhexyl)phosphate to obtain europium sesquioxide, EuaOs. 

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). 

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. 

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... 

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. 

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. 

Major Rare Earths Ore Producers. Australia, Brazil, India and Malaysia are the major monazite producing countries. Together they supplied almost 98% of the total world production of monazite in 1976. Australia and Malaysia have little or no domestic processing facilities beyond concentrating the monazite at the mine. 

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