Monazite

Monazite is a primarily reddish-brown phosphate mineral that

contains rare-earth elements. Due to variability in composition,
Monazite
monazite is considered a group of minerals.[3] The most common
species of the group is monazite-(Ce), that is, the cerium-
dominant member of the group.[4] It occurs usually in small
isolated crystals. It has a hardness of 5.0 to 5.5 on the Mohs scale
of mineral hardness and is relatively dense, about 4.6 to 5.7
g/cm3 . There are five different most common "kinds" (actually
separate species) of monazite, depending on relative elemental
composition of the mineral:[5]

monazite-(Ce), (Ce,La,Nd,Th)PO4 (the most common

member),
monazite-(La), (La,Ce,Nd)PO4,
Monazite-(Ce)
monazite-(Nd), (Nd,La,Ce)PO4,
General
monazite-(Sm), (Sm,Gd,Ce,Th)PO4.
Category Phosphate minerals
Monazite-(Pr), (Pr,Ce,Nd,Th)Po4.
(Lower concentrated rare-earths may vary.) Formula (Ce,La,Th)PO4
(repeating unit)
The elements in parentheses are listed in the order of their Strunz 8.AD.50
relative proportion within the mineral: lanthanum is the most classification
common rare-earth element in monazite-(La), and so forth. Silica
(SiO2 ) is present in trace amounts, as well as small amounts of Crystal system Monoclinic
uranium and thorium. Due to the alpha decay of thorium and Crystal class Prismatic (2/m)
uranium, monazite contains a significant amount of helium, (same H–M symbol)
which can be extracted by heating.[6] Space group P21/n

Monazite is an important ore for thorium,[7] lanthanum, and Identification

cerium.[8] It is often found in placer deposits. India, Madagascar, Color Orange, Purple,
and South Africa have large deposits of monazite sands. The Reddish brown, brown,
deposits in India are particularly rich in monazite. pale yellow, pink, blue,
Monazite is radioactive due to the presence of thorium and, less green, gray,
commonly, uranium. The radiogenic decay of uranium and Crystal habit Commonly as prismatic
thorium to lead enables monazite to be dated through monazite or wedge-shaped
geochronology. Monazite crystals often have multiple distinct crystals
zones that formed through successive geologic events that lead to
Twinning Contact twins common
monazite crystallization.[9] These domains can be dated to gain
insight into the geologic history of its host rocks. Cleavage Distinct on [100] poor
on [010]
The name monazite comes from the Greek μονάζειν (to be
Fracture Conchoidal to uneven
solitary), via German Monazit, in allusion to its isolated
crystals.[10] Mohs scale 5.0–5.5
hardness
Luster Resinous, vitreous to
 adamantine
Contents
Streak White
Structure
Diaphaneity Translucent to opaque
Mining history
Specific 4.6–5.7 (4.98–5.43 for
Mineralization and extraction gravity monazite-Ce)
Acid cracking
Optical Biaxial (+)
Alkaline cracking
properties
Extraction of rare-earth metals from monazite ore
Refractive nα = 1.770–1.793
References
index nβ = 1.778–1.800
Further reading nγ = 1.823–1.860
External links Pleochroism Weak
2V angle 10–26°

Structure Melting point 1900–2100

Other Radioactive if
characteristics uranium and/or
thorium-rich, dull brown
cathodoluminescence,
paramagnetic
Magnetism Diamagnetic, very
weakly
References [1][2]

Structure of monazite. Color
scheme: red = O, pale blue = P, dark
gray = Ce(III) and other lanthanides
and actinides.
All monazites adopt the same structure, meaning that the connectivity
of the atoms is very similar to other compounds of the type
M(III)PO4 . The M(III) centers have a distorted coordination sphere
being surrounded by eight oxides with M–O distances around 2.6 Å
in length. The phosphate anion is tetrahedral, as usual. The same
structural motif is observed for lead chromate (PbCrO4 ).[11]

Mining history
Monazite sand from Brazil was first noticed in sand carried in ship's
ballast by Carl Auer von Welsbach in the 1880s. Von Welsbach was
looking for thorium for his newly invented incandescent mantles.
Monazite sand was quickly adopted as the thorium source and
became the foundation of the rare-earth industry.

Postcard view of a monazite mine in
Shelby, North Carolina, showing cart
tracks and a bridge
Monazite sand was also briefly mined in North Carolina, but, shortly
thereafter, extensive deposits in southern India were found. Brazilian
and Indian monazite dominated the industry before World War II,
after which major mining activity transferred to South Africa. There
are also large monazite deposits in Australia.

Monazite was the only significant source of commercial lanthanides,

but concern over the disposal of the radioactive daughter products of thorium, bastnäsite came to displace
monazite in the production of lanthanides in the 1960s due to its much lower thorium content. Increased
interest in thorium for nuclear energy may bring monazite back into commercial use.
Mineralization and extraction
Because of their high density, monazite minerals concentrate in
alluvial sands when released by the weathering of pegmatites. These
so-called placer deposits are often beach or fossil beach sands and
contain other heavy minerals of commercial interest such as zircon
and ilmenite. Monazite can be isolated as a nearly pure concentrate by
the use of gravity, magnetic, and electrostatic separation.

Monazite sand deposits are inevitably of the monazite-(Ce)

composition. Typically, the lanthanides in such monazites contain
Monazite powder about 45–48% cerium, about 24% lanthanum, about 17%
neodymium, about 5% praseodymium, and minor quantities of
samarium, gadolinium, and yttrium. Europium concentrations tend to
be low, about 0.05%. South African "rock" monazite, from Steenkampskraal, was processed in the 1950s and
early 1960s by the Lindsay Chemical Division of American Potash and Chemical Corporation, at the time the
largest producer of lanthanides in the world. Steenkampskraal monazite provided a supply of the complete set
of lanthanides. Very low concentrations of the heaviest lanthanides in monazite justified the term "rare" earth
for these elements, with prices to match. Thorium content of monazite is variable and sometimes can be up to
20–30%. Monazite from certain carbonatites or from Bolivian tin ore veins is essentially thorium-free.
However, commercial monazite sands typically contain between 6 and 12% thorium oxide.

Acid cracking

The original process for "cracking" monazite so as to extract the thorium and lanthanide content was to heat it
with concentrated sulfuric acid to temperatures between 120 and 150 °C for several hours. Variations in the
ratio of acid to ore, the extent of heating, and the extent to which water was added afterwards led to several
different processes to separate thorium from the lanthanides. One of the processes caused the thorium to
precipitate out as a phosphate or pyrophosphate in crude form, leaving a solution of lanthanide sulfates, from
which the lanthanides could be easily precipitated as a double sodium sulfate. The acid methods led to the
generation of considerable acid waste, and loss of the phosphate content of the ore.

Alkaline cracking

A more recent process uses hot sodium hydroxide solution (73%) at about 140 °C. This process allows the
valuable phosphate content of the ore to be recovered as crystalline trisodium phosphate. The
lanthanide/thorium hydroxide mixture can be treated with hydrochloric acid to provide a solution of lanthanide
chlorides, and an insoluble sludge of the less-basic thorium hydroxide.
Extraction of rare-earth metals from monazite ore

The following steps detail the extraction

of rare-earth metals from monazite ore.
The process requires many
neutralizations and filtrations.[12][13]

1. Grinder: Grind monazite ore to

~150 micrometers. Monazite ore
contains 55–60% rare-earth
metal oxides along with 24 to
29% P2O5, 5 to 10% ThO2, and
0.2 to 0.4% U3O8.
2. Digestion: Crushed monazite is
mixed with highly concentrated
sulfuric acid (93% acid) at feed
temperatures of 150 to 180 °C.
The ratio of acid to ore varies
depending on the concentration
of the ore (unable to find ratio
range). The digester is stirred
vigorously with a robust agitator
and operates at temperatures
between 200 and 300 °C. Acid is Process flow diagram for extraction of rare-earth metals from
charged into the reactor and monazite ore using hydrometallurgy
heated before the ore. The
insoluble product coats the
grains of crushed ore. The temperature in the reactor rises due to heat released from the
exothermic reactions. After ~15 minutes, the viscosity of the solution has increased and the
solution is similar to a dough. The product reacts for 3 to 4 hours. It is then removed from the
digester before the solution hardens. The ratio of sulfuric acid to sand removed is 1.6 to 2.5.
 3. Dissolution: The contents of the reactor are cooled to 70 °C and leached with 30 °C water. A
ratio of 10 parts water to mass of ore originally added is used. This leaching process continues
for 12 to 15 hours.
4. Filtration: All solids from step three are filtered off. Such solids include: silica, rutile, zircon,
ilmenite, and undigested monazite residues. The resulting solution is called monazite sulfate.
5. Dilution: Diluted the monazite sulfate with 6–7 parts water at 30 °C.
6. Neutralization: Add NH3(aq) to neutralize to a pH of 1.1 to form a selective precipitate of
thorium-phosphate cake.
7. Filtration: Collect thorium phosphate precipitate during filtration of neutralized monazite
solution.
8. Dryer: Feed thorium-phosphate cake through a dryer at ~120 °C to create concentrated thorium
phosphate.
9. Neutralization: Add NH3(aq) to remaining monazite solution to create rare-earth-metal
precipitate at a pH of 2.3.
10. Filtration: Filtrate out the RE precipitate to yield the concentrated rare-earth metal hydroxides.
11. Neutralization: Add NH3(aq) to remaining filtrate to a pH of 6. This creates a uranium
concentrated precipitate.
12. Filtration: Filter remaining solution to yield uranium concentrate.

The final products yielded for this process are thorium-phosphate concentrate, RE hydroxides, and uranium
concentrate.

References
1. Mineralienatlas (https://www.mineralienatlas.de/lexikon/index.php/MineralData?mineral=Mona
zite).
2. Monazite (http://rruff.geo.arizona.edu/doclib/hom/monazitece.pdf). Handbook of Mineralogy.
Retrieved on 2011-10-14.
3. Monazite group on Mindat.org (http://www.mindat.org/min-2750.html)
4. Monazite-(Ce) on Mindat.org (https://www.mindat.org/min-2751.html)
5. Monazite group on Mindat.org (http://www.mindat.org/min-2750.html)
6. "Helium From Sand" (https://books.google.com/books?id=S-QDAAAAMBAJ&pg=PA460&dq=P
opular+Mechanics+1931+%22all-metal%22#v=onepage&q=Popular%20Mechanics%20193
1%20%22all-metal%22&f=true), March 1931, Popular Mechanics p. 460.
7. Wolfgang Stoll "Thorium and Thorium Compounds" Ullmann's Encyclopedia of Industrial
Chemistry 2012 Wiley-VCH, Weinheim. doi:10.1002/14356007.a27_001 (https://doi.org/10.100
2%2F14356007.a27_001).
8. McGill, Ian (2005) "Rare Earth Elements" in Ullmann's Encyclopedia of Industrial Chemistry,
Wiley-VCH, Weinheim. doi:10.1002/14356007.a22_607 (https://doi.org/10.1002%2F14356007.
a22_607).
9. Williams, Michael L.; Jercinovic, Michael J.; Hetherington, Callum J. (2007). "Microprobe
Monazite Geochronology: Understanding Geologic Processes by Integrating Composition and
Chronology". Annual Review of Earth and Planetary Sciences. 35 (1): 137–175.
Bibcode:2007AREPS..35..137W (https://ui.adsabs.harvard.edu/abs/2007AREPS..35..137W).
doi:10.1146/annurev.earth.35.031306.140228 (https://doi.org/10.1146%2Fannurev.earth.35.03
1306.140228). ISSN 0084-6597 (https://www.worldcat.org/issn/0084-6597).
10. Oxford English Dictionary, 3rd edition, 2002.
11. Quareni, S.; de Pieri, R. "A three-dimensional refinement of the structure of crocoite, PbCrO4"
Acta Crystallographica 1965, volume 19, pp. 287–289.
12. Gupta, C. K. and T. K. Mukherjee. Hydrometallurgy in Extraction Processes. Boca Raton,
Florida: CRC, 1990. Print.
13. Gupta, C. K., and N. Krishnamurthy. Extraction Metallurgy of Rare Earths. Boca Raton, Florida:
CRC, 2005. Print.

Further reading
J. C. Bailar et al., Comprehensive Inorganic Chemistry, Pergamon Press, 1973.
R. J. Callow, The Industrial Chemistry of the Lanthanons, Yttrium, Thorium and Uranium,
Pergamon Press 1967. LCCN 67-14541 (https://lccn.loc.gov/67014541).
Gupta, C. K. and N. Krishnamurthy, Extactive Metallurgy of Rare Earths, CRC Press, 2005,
ISBN 0-415-33340-7.
Gupta, C. K., and T. K. Mukherjee. Hydrometallurgy in Extraction Processes, Boca Raton,
Florida: CRC Press, 1990. Print.
Price List, Lindsay Chemical Division, American Potash and Chemical Corporation, 1960.
R. C. Vickery, Chemistry of the Lanthanons, Butterworths and Academic Press, 1953.

External links
Monazite (https://web.archive.org/web/19980215073411/http://mineral.galleries.com/minerals/p
hosphat/monazite/monazite.htm)
An Unusual State Of Matter (http://www.roaldhoffmann.com/sites/all/files/an_unusual_state_of_
matter.pdf) Poem about monazite by Roald Hoffman
"British Monazite Mine, Shelby, N.C." in Durwood Barbour Collection of North Carolina
Postcards (P077), North Carolina Collection Photographic Archives, Wilson Library, UNC-
Chapel Hill (https://web.archive.org/web/20120215121509/http://dc.lib.unc.edu/cdm4/item_vie
wer.php?CISOROOT=%2Fnc_post&CISOPTR=3240&CISOBOX=1&REC=1)
radiation (in) paradise – the secret of the sand (https://www.youtube.com/watch?v=vdHHUGwF
oJE) on YouTube; the third in a series of videos about a Monazite beach in Brazil.
Monazite, thorium, and mesothorium (https://archive.org/details/monazitethoriumm00kithiala)
(1915)

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