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By J. Andres

"Freeport-McMoRan’s Sierrita operations refines molybdenum disulfide in a ferric chloride leach to remove impurities. To understand bottlenecks in the leach process and the true capacity of the leach system, a cross-functional team was established to look at theoretical models, kinetics of the leaching process, equipment limitations and operational strategies. A series of in-plant tests were run which resulted in a road map for improved throughput. INTRODUCTION Molybdenum, a vital component in the steel industry, is often found in nature as molybdenum disulfide (MoS2). Molybdenum disulfide deposits can exist as standalone components in an ore body, or can also be found within copper porphyry nodes. Processing for these copper/molybdenum porphyry ore bodies involves a first stage of flotation to produce a bulk concentrate before separation of the copper and molybdenum concentrates in a second stage of flotation. In this second stage of flotation, a reagent is added to suppress the copper particles, while allowing the molybdenum disulfide particles to remain hydrophobic and continue to float. This separation is very good at keeping the molybdenum out of the copper concentrate; however a portion of the copper continues to float through the circuit. As a result, there is typically some amount of copper in the final molybdenum concentrate. This copper must be removed in order for the molybdenum disulfide product to meet product quality specifications. Once the raw molybdenum disulfide product has been made, a separate process must be applied to remove any copper, lead, or other impurities remaining in the concentrate. This process usually involves the selective leaching of impurities out of the bulk solid. Gupta mentions three specific types of leaching agents, sodium cyanide, ferric chloride, and hydrochloric acid for the removal of sulfide impurities. Sodium cyanide is useful for the removal of copper compounds such as bornite, covellite, and chalcocite.1 Sodium cyanide solution dissolves these copper compounds, and the remaining molybdenum solids are filtered to produce a pure molybdenum concentrate. Ferric chloride works similar to that of sodium cyanide, but is particularly efficient in removing chalcopyrite and galena compounds. These compounds are easily chlorinated at elevated temperatures, producing copper chloride and lead chloride, through the reactions presented below:"

Jan 1, 2015

By C. H. B. Leitch, T. N. MacAuley, R. L. Linnen, A. E. Williams-Jones

"The Trout Lake stockwork molybdenum deposit is temporally and spatially related to the emplacement of a late Cretaceous granodiorite-tonalite stock in southeastern British Columbia and contains an estimated 49 million tonnes grading O.I9% MoS2- No metal zonation patterns are apparent, with the exception of peripheral tungsten skarn, and exploration was guided largely by geological interpretation. It is typical of the granodiorite, or fluorine-poor type of molybdenum deposit. Molybdenite is contained within a quartz-feldspar vein stockwork and coeval dissemination in igneous (and less commonly metasedimentary) hosts. In general, molybdenite is strongly associated with alkali feldspars, but in detail it is intimately associated with incipient muscovite replacement of albite and K-feldspar; veins that lack feldspars are also typically barren of molybdenite. These textures suggest that fe/dspathic alteration (and precipitation in veins) was an important precursor to mineralization, and the occurrence of similar textures elsewhere (e.g. Henderson) suggest that early feldspathic alteration is important to the genesis of molybdenum deposits in general. Molybdenite deposition at Trout Lake was preceded by contact metamorphism, skarn and potassic alteration, and was overprinted by muscovite-ankerite (phyllic) alteration. Only moderate temperature changes are recorded by the metamorphic and alteration mineral assemblages (350°C to 450°C}; however, with time, fluids became increasingly more acidic and enriched in C02- In light of the intimate molybdenitemuscovite intergrowths, the decrease of pH probably exerted a major control on mineralization.IntroductionGranite-hosted molybdenum deposits can be classified in terms of the composition of the related intrusion, e.g., the granodiorite and granite types of Mutschler et a!. (1981), or the calc-alkaline, alkali-calcic, and alkalic types of Westra and Keith (1981). They have also been classified on the basis of their fluorine contents (Theodore and Menzie, 1984) with the fluorine-rich and -poor varieties roughly corresponding to granite- and granodiorite-type deposits, respectively. For economic reasons, most exploration and research has concentrated on the high-grade/large tonnage granite-type of deposit, exemplified by Climax. F1uorine-poor, granodiorite-type deposits are, however, the most common type in Canada and have been mined in the past (e.g., Endako). In this paper, the authors summarize the research that has been carried out on the fluorinepoor Trout Lake deposit (Boyle and Leitch, 1983; Linnen, 1985; Linnen and Williams-Jones, 1987; 1990) and use what has been learned to develop guidelines for the future exploration of fluorinepoor, granodiorite-type molybdenum deposits."

Jan 1, 1995

By F. Parada

During copper smelting and converting processes, slag generated is pyrometallurgically cleaned and then disposed, containing around 1 % of this metal. However, important amount of molybdenum initially contained in concentrates also goes to the slag phase. Research on molybdenum recovery from water granulated slags using acid leaching at low temperatures was conducted to find an efficient way for molybdenum extraction with lower magnetite in the slag. However because of the high fayalite content high acid consumption was found. Molybdenum can be recovered from solution using ionic exchange resins, but high silica content interferes with extraction. Some studies addressed to minimize silica extraction as well as alternatives of selective silica precipitation in order to develop a technically feasible process.

Jan 1, 2007

By J. Andres, M. Cross

"Freeport-McMoRan’s Sierrita operations has two natural gas-fired molybdenum roasters for converting molybdenum disulfide into molybdenum trioxide. When these roasters were compared to other similar units within the company during a benchmarking exercise, it showed that increased throughput from the roaster units at Sierrita was possible. A team of site metallurgists, technical experts from other sites, and engineers from the Climax Technology Center was formed to study the potential in more detail. The team investigated many parameters in the roaster, including temperature profiles, roaster chemistry profiles, rabble and drop hole patterns, and operational strategies. The results of these studies and the associated throughput improvements are described in this paper. INTRODUCTION Molybdenum, a vital component for the steel industry, is typically found in nature as molybdenum disulfide (MoS2). MoS2 is typically recovered via flotation processes and is purified through leaching processes. While molybdenum disulfide is a commercial product, it is not the form of molybdenum that the steel industry requires. They require molybdenum in the form of molybdenum trioxide, MoO3. There are multiple ways to refine molybdenum disulfide into molybdenum trioxide. The primary method is the oxidation of molybdenum disulfide in a multiple hearth roaster. The chemistry of converting molybdenum disulfide to molybdenum trioxide is very favorable at increased temperatures, oxidizing the molybdenum through a range of exothermic reactions to ultimately produce MoO3. The chemical reactions that occur in molydenum roasting occur in three zones. These three zones correspond with four different reactions."

Jan 1, 2015

By T. Bednarski, T. McCallum, L. Moya, B. Gay

"Molybdenum recovery by solvent extraction has gained interest partly due to advances in concentrate leach technology. Historically, both molybdenum and rhenium have been produced using amine-based extractants with the ability to co-extract both metals. Alternatively, a phosphinic acid-based extractant (CYANEX® 600) can be used depending on the flow sheet. CYANEX® 600 selectively extracts Mo leaving Re in the raffinate, which is a valuable feature in plants which require rejection of the rhenium from the molybdenum circuit. CYANEX® 600 piloting results are reviewed and compared to commercial experiences with an amine-based extractant. INTRODUCTION Molybdenum is most commonly found as molybdenite (MoS2) in primary porphyry deposits (about 59% of global reserves) and copper porphyries (about 39% of molybdenum reserves)[1]. Recovery from molybdenite traditionally involves flotation (concentrates typically containing 85 – 95% MoS2) followed by roasting to produce MoO3. Solvent extraction is also used to recover molybdenum from acidic aqueous solutions resulting from scrubbing of roaster and smelter off gasses and leaching of molybdenite (uranium ores). Molybdenum is also frequently found in low concentrations in copper leach inventories[2]. More recently, pressure oxidation has gained interest to treat molybdenite concentrates. Molybdenum Chemistry The chemistry of molybdenum is complex with a series of extractable species existing dependent on the pH and oxidation state as shown in Figure 1.Under strongly basic conditions, molybdenum primarily exists as MoO42- while under strongly acidic conditions MoO22+ becomes the predominant species. In between, a number of isopolymolybdates such as Mo7O246- and Mo8O264- are dominant. Equations (1) – (3) demonstrate some of the proposed molybdenum equilibrium reactions[1]."

Jan 1, 2017

By T. McCallum, C. Cooper, C. Lewis

"Following a successful solvent extraction (SX) pilot plant demonstration in 2016, CYANEX® 600 has been used commercially to recover molybdenum from concentrate leach liquor since March 2017. Consistent with the piloting results, the commercial plant has achieved expected molybdenum recovery, a significant reduction in base consumption, and a step-change improvement in physical performance. This paper highlights the optimization activities and plant performance from startup through normal operation. INTRODUCTION Historically, tertiary amines have been the most commonly used extractant for molybdenum and rhenium recovery. Tertiary amines utilize a protonation of the ligand combined with an anion exchange mechanism as proposed in equations (1-2). R3N + H+ ???R3NH + (1) 4R3NH+ + Mo8O264- ???(R3NH+)4Mo8O264- (2) In addition to the transfer of Mo and Re, the amine transfers acid and other anions to the strip liquor. The undesirable transfer of other species increases base consumption during stripping, impacting operating costs. Additionally, lower solubility of molybdenum-amine complexes create operational challenges, resulting in diminished physical performance. The presence of colloidal Si in concentrate leach liquors and the formation of Pickering Emulsions adds to the physical plant performance challenges with the amine extractant. CYANEX® 600, a phosphinic acid-based extractant, uses a cation exchange mechanism proposed by equation (3). 2(H2R2) + MoO22+ ??(HR2)2MoO2 + 2H+ (3) The cationic exchange mechanism eliminates chemical transfer of acid and other anionic impurities and avoids some of the physical challenges of the amine extractant (emulsion and 3rd phase formation). In addition, the reagent offers high selectivity for Mo over Re, which may be desirable in certain moly pressure oxidation (POX) flowsheets. Alkali base (ammonium hydroxide, sodium hydroxide, sodium carbonate, etc.) is used for molybdenum stripping. Therefore, reduction or elimination of chemical acid transfer from extract can significantly reduce base consumption in strip. Extensive laboratory and pilot plant testing was completed to evaluate the use of CYANEX® 600 for molybdenum recovery at Freeport-McMoRan’s Bagdad operation. The test work and pilot demonstration confirmed a reduction in base consumption along with improved selectivity. In addition, the evaluation highlighted a step-change improvement in physical performance over the incumbent amine extractant. The decision was made to convert the commercial operation to CYANEX® 600 in March 2017."

Jan 1, 2018

By John Mathews

IT is twenty years since the writer made his first molybdenum steels and others were making them commercially five years earlier but the prevailing opinion seems to be that molybdenum steels are new; from time to time the daily press speaks of important discoveries in Europe and intimates that American steel makers have much to learn in regard to alloy steels. The earlier experiments were largely confined to the use of relatively high percentages of molybdenum in tool steels and permanent magnet steels. Recent developments deal with the types of alloy structural steels used for airplane, automobile, and other engineering requirements; in these, the molybdenum content is usually less than 1 per cent. The earlier types generally have been unsuccessful commercially, but the newer types of steels are becoming of increasing importance. The war showed our dependence on foreign sources for alloying metals; molybdenum alone is widely distributed in the United States and seemingly abundant. Many deposits are not now of commercial interest, owing to location and relatively small amount of ore available, but other deposits are being developed and a stable source of supply seems well assured. In tool and magnet steels, it was early found that 1 part of molybdenum was equivalent to from 2 to 2.5 parts of tungsten. The permanent magnet steels investigated by Madame Curie,1 in 1898, contained from 3.36 to 4.05 per cent. molybdenum; in 1902, Dr. E. L. French and the writer thoroughly tested steels containing from 2:0 to 4.0 per cent. These steels gave satisfactory tests for permanence, but were low in residual density and much more sensitive to hardening than the corresponding tungsten products. We discontinued work with them, therefore, and have no advice that such steels have been used commercially here or abroad.

Jan 2, 1921

By Rex E. Loesby

The dramatic increase in molybdenum prices from the low of less than $2.50/lb in 1999 to more than $40/lb in 2005 has caught the attention of molybdenum mine owners and exploration project developers. Between 2005 and early 2007, prices pulled back and stabilized within a trading range of $25/lb to $30/lb. This 1,000 percent price increase has motivated most existing producers to expand production and is motivating those with molybdenum prospects to accelerate the development process for earliest possible production. It is still unknown how much new production will come from existing mines, how much production will be needed from new mines if demand continues to grow and how many potential new mines might be available to meet future demand. And of course, the billion dollar question is whether molybdenum prices will remain high, or will they fall back to the low levels seen during the 1980s and 1990s? This article attempts to answer these questions in a way that will help molybdenum project developers and financiers plan for the future.

Jan 1, 2007

By John Stroiazzo, Bernard C. Aubé

Brenda Mines, located 22 km Northwest of Peachland in British Columbia, Canada was an open pit copper- molybdenum mine which closed in 1990 after 20 years of operation. The primary concern in Brenda's tailings and waste rock drainage is molybdenum at a concentration of approximately 3 mg/L. The mine drainage is alkaline and contains little or none of the typically problematic heavy metals. Given that the waters downstream are used for municipal water supply and some irrigation, a discharge limit of 0.25 ma molybdenum was imposed with specific water quality guidelines in the receiving creek. A review of all existing and potential molybdenum removal methods was undertaken prior to mine closure. The chosen process is a two-step iron co-precipitation with clarification and sand filration at a slightly acidic pH. A 4,000 usgpm (912 m3/h) treatment plant was constructed and commissioned in 1998, at a cost of $10.5M. The successful removal of molybdenum from the drainage water is explained with details on some design innovations and operational challenges encountered during plant start-up. Investigated sludge disposal options are discussed although the long term disposal scenario has not yet been finalised.

Jan 1, 2000

By Alan Kissock

MOLYBDENUM is thought of as one of the rarer elements, for though it occurs in almost every country of the world it is seldom found in commercial quantities. In this country, however, there is one deposit which makes the term "rare" a misnomer. There are two commercially mined molybdenum minerals: molybdenite, the sulfide, and wulfenite, a lead molybdate. Of these two only the former is of any con- sequence but wulfenite is of mineralogical interest. It is frequently associated with oxidized lead ores and particularly in arid sections. Deposits, however, are usually quite superficial. It is highly oxidized and yet it does not appear to be an alteration product for it apparently disappears below water level and I know of no case where primary molybdenite, or in fact any molybdenum whatever has been identified below these surface wulfenite occurrences. The genesis of wulfenite would make an !- interesting study.

Jan 1, 1933

In the late 1980s and into the 1990s, the Mountain Pass Mine in California produced about 40 percent of the world?s rare earth elements. At the height of this production, the facility produced up to 54 L/s (850 gpm) of saltwater that was piped to offshore holding ponds where the water was evaporated. In 1998, following a series of waste water pipeline breaches, separations activities were suspended, reducing the Mountain Pass site to just the openpit mine and mill. The environmental concerns were addressed and the affected areas have since been remediated. However, in the years following the breaches, 97 percent of the world?s production of rare earth elements moved to China. By 2011, Molycorp, and the Mountain Pass Mine, had rebounded from the difficult times and were once again in a position to become a significant player in the rare earth industry.

Jan 1, 2011

The Molycorp operation at Mountain Pass, California, is unique in that it is the only place in the world where bastnasite is mined. The orebody is a metamorphic carbonatite; the mineral of importance is bastnasite, a fluocarbonate containing principally cerium, lanthanum, neodymium, and praseodymium, with small amounts of samarium, gadolinium, and europium. In addition, appreciable quantities of barite, calcite, and strontianite are present. Molycorp had mined and processed the bastnasite ore since the early 1950s at a rate of about 100 tpd by a unique hot flotation process in a plant originally used for cyanidation of gold ore. The concentrate was primarily used in high quality glass polishing, lighter flints, ceramics, and in specialty steel making. Then in the early 1960s, Molycorp and the Colorado School of Mines Research Foundation developed a solvent extraction process to recover europium from the bulk rare earth concentrates. In 1965 a new SX plant was constructed to produce this material for use as a red phosphor in color television tubes. Because of the demand for this material, a new 500 tpd concentrator was designed and constructed in 9 ½ months. Then, because of a sharply increased demand for europium, the plant was expanded to 1200 tpd only four months after completion of the original construction. The crushing section of the new plant was designed similarly to those portable units used in road construction and arrived on the site in ten major pieces. Foundations were concrete piers; and after their completion, the entire crushing plant composed of primary and secondary crushers, conveyors, and a screen was erected in fourteen days by a crew of ten men assisted by a mobile crane. Pit-run ore is loaded into 35-ton trucks by a 7 yd (5.4 cu m) loader, trans- ported to .the crushing plant, and dumped into the 65 -ton concrete pocket. A 42 in. by 20 ft (1.07 m by 6. 1 m) apron feeder feeds ore to the 30 in. by 42 in. (760 rnrn by 1070 mm) single toggle jaw crusher. Crushed ore is trans- ferred by a scissors conveyor to a 5 ft by 14 ft (1.52 m by 4. 27 m) double- deck screen which produces a final ¾ in. (19 rnrn) product with the oversize being treated in a 4 ¼ ft (1. 3 m) standard cone crusher. Cone crusher product is returned to the first scissors conveyor to join the primary crusher product. Dust collection is by a wet scrubber, and an operator's control room is located to overlook the primary. The entire crushing is in the open, and a 30-ton mobile crane is used for maintenance. Molycorp’s two-stage crushing plant is an excellent example of functional design for a small mining and milling operation.

Jan 1, 1978

By Musa D. Manzi, Raymond J. Durrheim, Richard T. Masethe

Large mining-induced seismic events and their aftershocks cause hazardous working conditions, damage infrastructure, delay production and pose a risk to miners in the deep-level gold mines of South Africa. Stress changes affecting pre-existing zones of weakness are the main drivers of large mining-induced seismic events, which are often followed by aftershocks triggered by quasi-static stress transfer within the rockmass. A better understanding of seismic source mechanisms is important if the seismic data is to be used more effectively for mine planning and to reduce the rockburst risk. Four large seismic events (ML≥2.0) associated with the mining of the Ventersdorp Contact Reef (VCR) at Kloof Gold Mine occurred on 13 June 2017. The events and their fore- and aftershocks were studied in detail to establish the circumstances and the cause of the incidents. The local magnitudes ranged from ML 2.3 to ML 3.0, the seismic moment from 0.69 to 2.25 x 1013 Nm and the source radius from 92 – 150 m. The main shocks were preceded by foreshock sequences, which were especially vigorous in the four hours before the main shock. Seismicity was recorded by in-mine arrays of three-component 4.5Hz geophones (detection threshold approx. ML -2.9). Following all four main seismic events, ML 2.3, ML 2.3, ML 2.9 and ML 3.0, the network detected a total number of 300 aftershocks ranging from ML -2.9 to ML 1.6 spread within a 1300 m radius from the centre of the seismic network. The statistical properties of the aftershocks were analysed using three scaling relationships: (i) Gutenberg–Richter frequency magnitude relationship; (ii) modified Omori’s law; and (iii) Båth’s law for the magnitude of the largest aftershock. The geological or mining feature that controlled the failure (e.g., fault, dyke, pillar, abutment) was determined by calculating the orientation of the nodal planes of the large seismic events using moment tensor analysis and studying the aftershock distributions.

Apr 26, 2022

By Robert Boehnke, Bernd Mueller

Despite enormous efforts over the last decades there are still many unanswered questions with respect to calculation and modeling of the blast process using appropriate physical laws. Most calculations of explosive charges of a blast design are based on experience, empirical observations or blasting theories with serious shortcomings. This paper presents a new theory for the design and calculation of a rock blast that is based on the momentum. It offers a clear-cut method for the calculation of blast processes. The theoretical results will be compared with on-site measurements by means of a newly developed strain sensor and further measuring equipment. The momentum theory helps better to explain physically the processes of a blast. On the basis of long-term statistical investigations a momentum balance can be carried out with the volume-based blasting momentum and the measurable momentum associated with the muckpile and the remaining rock mass. This type of consideration requires a complex procedure which includes the blastability of the rock masses. Realis tic strain measurements open a new interpretation possibility and judgment criteria for the most probable building damage, the dynamic impact on general types of buildings and also for the blast process itself. The blast-induced stress and the momentum generated could be back-calculated using a geophone profile and the strain sensor. The strain owing to a dynamic impact can be influenced by the changing of the drill-, blast- and shotfiring technique like the until now measured vibration velocity. In this way it is possible today to make a complex preparation, calculation and evaluation of blasts. The new techniques of measuring in connection with the momentum theory bring about an increase of the safety and a clearcut method of improving the blast processes. This procedure offers new possibilities for the precise calculation, simulation and modelling of blasts and resulting vibrations and leads to an increase of the safety as well as economic adaptation of the drill-, blast- and shotfiring techniques to a pre-determined blasting result.

Jan 1, 2003

By Charles S. Ney

"ZINC-LEAD REPLACEMENT deposits straddle the steep-sided valley of Kicking Horse River at a point three miles east of Field, B.c., in Yoho National Park. The Monarch orebodies extend into Mt. Stephen on the south side of the valley, and outcrop at two points, 1,000 and 1,200 feet above the valley floor. The Kicking Horse deposits are in Mt. Field, on the north side of the valley, and they outcrop 200 feet lower.The East Monarch outcrop is said to have been discovered in 1884 during construction of the Canadian Pacific Railway. The larger West Monarch outcrop, 700 feet west of the original discovery, was not reached till 1917 because of its nearly inaccessible location on the cliff face.The Kicking Horse mine was staked in 1906. Little development was done for several decades, and mining was not commenced till 1935.At the East Monarch, mining was commenced soon after location, and several thousand tons of ore were shipped prior to 1912. At this time a gravity concentrator was installed. This was operated till 1924, and a total of 42,000 tons of ore were mined, including about 10,000 tons from the West Monarch. The period from 1928 to 1935 featured flotation milling and the mining of 265,000 tons of ore, mostly from the West Monarch orebody. Intensive exploratory development was carried out in both Monarch and Kicking Horse from 1935 to 1946. Production from both mines in this period totalled 380,000 tons. From 1947 to the time of closure in 1952, considerable new ore was found in both mines and 185,000 tons were milled. Immediate possibilities for finding ore in the Monarch were considered exhausted. Kicking Horse orebodies are known to persist with a low grade of zinc. Total production from the two mines amounts to 842,500 tons grading approximately 7 per cent lead, 10 per cent zinc, and 1.2 ounces per ton silver."

Jan 1, 1949

By W. L. Brown

"The properties of Base Metal Mining Corporation are in Yoho Park about 2 1/2 miles northeast of Field; British Columbia; on the main line of the Canadian Pacific railway. There are actually two mines; the Monarch on mount Stephen and the Kicking Horse on mount Field; separated by the steep valley of Kicking Horse river. The outcrops of the orebodies range from 4; 900 feet to 5; 300 feet above sea-level. The concentrator is situated below the Monarch mine and is connected to the main portal by an aerial tramway. The ore from the Kicking Horse mine is conveyed by aerial tramway to a storage bin on the main highway and is then trucked to the concentrator.During the construction of the Canadian Pacific railway through Kicking Horse valley, galena float was found at the base of mount Stephen. The East Monarch outcrop was staked in 1894. The outcrop of the West Monarch ore body on the cliff face of mount Stephen was not discovered until 1916. The Kicking Horse orebodies on mount Field were discovered a few years later. In 1912, a 75-ton concentrator was erected, which operated at intervals until 1924. During this period approximately 42,000 tons were mined and milled, largely from the East Monarch orebody. In 1928, the Base Metal Mining Corporation, Limited, was formed to take over the Monarch and Kicking Horse mines. A 300-ton differential flotation concentrator was erected and production started in the autumn of 1929. In a very short time, however, the low price of metals forced the mill to shut down until August 1933. From 1929 to 1935, when the mill again ceased operation, a total of 256,500 dry tons of ore, averaging 1.59 oz. silver per ton, 9.7 per cent lead, and 12.6 per cent zinc, was mined and milled, largely from the West Monarch orebody. After a period of further underground development, the concentrator reopened in 1940 and is still in operation. From 1940 to the end of 1944, 354,363 tons of ore was milled, averaging 5.32 per cent lead and 10.47 per cent zinc."

Jan 1, 1954

By John B. Mertie

MONAZITE formerly was described as moribund, but, in the light of recent developments, it is no longer so. It is the common source of the rare earths and thorium, both of which are becoming progressively important in industrial and other applications. Moreover, by the action of foreign governments, the sources on which the United States has depended for its supply are now either restricted or cut off entirely. Monazite has thus become a scarce mineral and processors in this country are endeavoring to acquire it from all available sources. RARE EARTHS AND THORIUM The rare earths proper, as defined by spectroscopists, are the oxides of cerium, praseodymium, neodymium, prometheum, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutecium, with atomic numbers ranging respectively from 58 to 71. Chemists include with the rare earths scandium, yttrium, and lanthanum, with atomic numbers respectively of 21, 39, and 57. Thorium, with an atomic number of 90, is analogous to lanthanum, in that it precedes a second group of elements, whose oxides constitute the "rare earths of higher order." These are protactinium, uranium, neptunium, plutonium, americium and curium, with atomic numbers ranging respectively from 91 to 96. The last four mentioned are artificially prepared elements that so far have not been detected in nature. The rare earths with odd atomic numbers, except europium and lutecium, have no natural isotopes; and the two exceptions have only two isotopic forms. Those with even atomic numbers have from 4 to 7 natural isotopes. Samarium148 is radioactive, disintegrating over a half- life of 1.4 X 10 11 years with the emission of alpha rays. Lutecium176 is weakly radioactive, disintegrating over a half-life of 2.4 X 1010 years, with the emission of beta and gamma rays. At least 64 radioactive isotopes of the rare earths proper have been artificially prepared. Thorium is a strongly radioactive element, with a half-life of 1.39 x 1O10 years, which disintegrates through a series of 14 isotopes of 10 elements. The two longest lived and most important of these are

Jan 1, 1949

By Joseph Hyde Pratt, Douglas B. Sterrett, CHAPEL HILL

I. DESCRIPTION. MONAZITE is one of the minerals which, for a long time, was considered rather rare in its occurrence, but, upon a commercial demand arising for it, prospectors and engineers soon located large deposits of it in the Carolinas and Brazil, and the supply has always been able to meet the demand. During 1908 further sources of supply of monazite have been discovered and developed in Idaho. North and South Carolina, however, are the only States that have thus far put any monazite on the market. Monazite is essentially an anhydrous phosphate of the rare-earth metals, cerium, lanthanum, and didymium (Ce, La, Di)PO;. There is nearly always present a varying but small percentage of thoria, ThO2, and silicic acid, SiO, which are very probably united in the form of a thorium silicate, ThSiO4 Some monazites contain but a fraction of a per cent. of thoria, while others have been recorded that showed the presence of from 18 to 32 per cent. ; but the majority contain from 3 to 9 per cent. of this oxide. It is the presence of the thorium oxide that gives the monazite its commercial value. The analysis occasionally shows also the presence of other constituents, as the yttrium and erbium oxides, zirconia, alumina, magnesia, lime, iron oxides, manganese oxide, and titanium oxide. Monazite is light-yellow, honey-yellow, reddish-, brownish-, or greenish-yellow in color, with a resinous to vitreous luster, and is translucent to subtransparent. It is brittle, with a conchoidal to uneven fracture, and is from 5 to 5.5 in hardness, and from 4.64 to 5.3 in specific gravity. It crystallizes in the monoclinic system, and some crystals have been observed that were 6 in. in length. The more perfect crystals are, however,

Jun 1, 1909

By Spencer S. Shannon

This chapter is concerned with the uses, geology, exploration, evaluation, preparation for markets, and future of 90thorium and 39yttrium, along with 14 rare-earth elements. The rare-earth metals or lanthanides were divided into three categories by Berzelius. The cerium subgroup is comprised of 57lanthanum, 58cerium, 59praseodymium, 60neodymium, and 62samarium. 61Promethium does not occur naturally. The terbium subgroup includes 63europium, 64gadolinium, and 65terbium. The remaining lanthanides are placed in the yttrium subgroup. Strictly speaking, yttrium is not a rare earth. Because the properties of yttrium resemble those of heavy rare earths, its name has been used as a designating adjective. The yttrium subgroup includes 66dysprosium, 67holmium, 68erbium, 69thulium, 70ytterbium, and 67lutetium. Rare-earth elements, especially those of the same subgroup, tend to occur together rather than in discrete minerals.

Jan 1, 1975

By John B. Mertie

More than 200 minerals are known that contain the rare-earths and thorium. Monazite and bastnaesite, however, are the principal commercial sources of the rare-earths, and monazite is the principal source of thorium. Monazite was in demand in earlier years mainly for its content of thorium, which was used in the manufacture of Welsbach gas mantles; but beginning in the latter part of the nineteenth century, the rare-earths became progressively more important than thorium. Recently, however, the tenor of thorium in monazite has again become a matter of commercial interest. Rare-Earths and Thorium The rare-earths proper are defined by spectroscopists as the oxides of 14 elements with atomic numbers ranging from 58 to 71; but more commonly lanthanum, with an atomic number of 57, is also included, in which case these 15 elements are often designated as the lanthanides. Chemists also include scandium and yttrium as elements of the rare-earths. A second group of elements, beginning with actinium and including thorium, protactinium, uranium, and all the transuranium elements so far produced, with atomic numbers ranging from 89 upward, are chemically and structurally related to the lanthanides, and are known as the higher rare-earths or actinides. Berzelius discovered that the lanthanides could be separated roughly into three groups, based upon the solubility of their double salts, R2(SO4)3-K2SO4-2H2O, in excess of K2SO4. This separation, with the substitution of sodium for potassium, is still used commercially. The double salts of the cerium earths were found to be almost insoluble; the terbium earths, partly soluble; and the yttrium earths, completely soluble. Based upon the degree of solubility, scandium belongs with the cerium earths; and yttrium belongs with, and gives its name to, the yttrium earths. These three groups with their atomic numbers are shown below. [ ] The prevailing state of oxidation for the rare-earths is R2O3, but cerium may readily be oxidized to the tetravalent state, in which condition it may be separated chemically from the other cerium earths. Praseodymium and terbium may also exist with the valence IV, and samarium, europium, and ytterbium may have the valence II. Most of the elements of the rare-earths, however, are very difficult to separate, and their initial isolation required the work of many chemists over a period of 150 years.20 Fractional crystallization, fractional precipitation, and ion exchange are the principal methods so far used, and fractional precipitation is now employed commercially on a large scale. Ion exchange columns are

Jan 1, 1960