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Molybdenum Metallurgy Review: Hydrometallurgical

Routes to Recovery of Molybdenum From Ores and
Mineral Raw Materials
a a b a
T. A. Lasheen , M. E. El-Ahmady , H. B. Hassib & A. S. Helal
a
Nuclear Materials Authority , P.O Box 540, El Maadi , Cairo , Egypt E-mail:
b
Chemistry department, faculty of Science , Cairo University , Dokki , Giza
Accepted author version posted online: 30 Jan 2014.Published online: 30 Jan 2014.
To cite this article: Mineral Processing and Extractive Metallurgy Review (2014): Molybdenum Metallurgy Review:
Hydrometallurgical Routes to Recovery of Molybdenum From Ores and Mineral Raw Materials, Mineral Processing and
Extractive Metallurgy Review: An International Journal, DOI: 10.1080/08827508.2013.868347
To link to this article: http://dx.doi.org/10.1080/08827508.2013.868347
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A. S. Helal., etal.,
Molybdenum metallurgy review
Molybdenum metallurgy review: hydrometallurgical routes to recovery of

molybdenum from ores and mineral raw materials
T. A. Lasheen1, M. E. El-Ahmady1, H. B. Hassib2, A. S. Helal1,

1
Nuclear Materials Authority, P.O Box 540 El Maadi, Cairo, Egypt2Chemistry
department, faculty of Science, Cairo University, Dokki, Giza+
Address of Corresponding to A. S. Helal: ahmed_samihelal7@yahoo.com,

Downloaded by [Moskow State Univ Bibliote] at 03:28 06 February 2014
lasheen_taysser@yahoo.com
Abstract
For the vigorous growing demand of steel industry, oil and gas industry, corrosion
resistance alloys, cast iron, and catalyst industries, high grade molybdenum ores are
exhausted step by step in the world, thus, much attention have been drawn to recover
molybdenum from low-grade molybdenum ores in recent years. With the increasingly
stringent environmental requirements, the traditional technology shows its shortcoming
due to SO2 emission in the roasting process. This review outlines metallurgical processes
for molybdenum production from various resources, particularly focusing on recent
developments in direct hydrometallurgical and recovery processes to identify potential
sources of molybdenum, products, and by-product such as uranium which can be
economically produced.
Several methods have been extensively reviewed for molybdenum separation and
purification from solution, which are potentially applicable to leach solutions of
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molybdenum ores and raw materials. The main methods include solvent extraction, ion
exchange, membrane based separation, and precipitation. Solvent extraction is highly
selective for recovery of molybdenum and the most promising method recommended for
future research and development. Membrane based separation is next for selective
extraction of molybdenum, purification of molybdenum solutions or co-recovery of other
valuable metals. Ion exchange offers useful means for purification and/or co-recovery of
other base metal impurities, although the scale of application of ion exchange in industry
is limited.
KEYWORDS: molybdenum metallurgy, recovery of molybdenum, solvent extraction,
ion exchange, and membrane based separation
1. INTRODUCTION
Molybdenum is a refractory metallic element used principally as an alloying agent in cast
iron, steel, and superalloys to enhance hardenability, strength, toughness, wear- and
corrosion-resistance, and oil and gas industry.
To achieve desired metallurgical properties, molybdenum, primarily in the form of
molybdic oxide (MoO3, called MoX) or ferromolybdenum (FeMo), is frequently used in
combination with or added to chromium, manganese, nickel, niobium (columbium),
tungsten, or other alloy metals. The versatility of molybdenum in enhancing a variety of
alloy properties has ensured it a significant role in contemporary industrial technology,
which increasingly requires materials that can sustain high stress, expanded temperature
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ranges, and highly corrosive environments. There is significant use of molybdenum as a
refractory metal and in numerous chemical applications, including catalysts, lubricants,
briquettes, and pigments (USGS, 2011).
Molybdenum plays a vital role in the energy industry, and it may become an increasingly
essential factor in green technology, where it is used in high-strength steels for
automobiles to reduce weight and improve fuel economy and safety. Molybdenum may
play a critical role in reducing sulfur in liquid fuels by acting as a cracking agent.
Production of diesel fuels having ultra-low-sulfur levels was expected to more than
double the amount of molybdenum used in oil refineries. Analysts expected global
demand for these types of catalysts to increase by more than 5% annually until 2013. The
need for companies to reduce carbon dioxide emissions from coal-fired power stations
will require plants to run at higher temperatures, resulting in greater demand for higher
grade molybdenum-bearing steels.
Primary molybdenum mines were the first to respond to the recovery in demand in 2010,
but in 2011 byproduct molybdenum mines (54%) outpaced production growth from
primary mines (46%). In 2012, mine capacity was expected to be sufficient to meet
demand, and supply was expected to show dramatic increase during the next coming
years. Approximately 60 new projects and expansions could potentially produce
molybdenum, yielding an additional 240,000 t/yr of molybdenum (Roskill, 2012).
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During the past decade, molybdenum consumption has shown a strong annual average
growth rate, primarily fueled by rapid increases in Chinas industrial growth.
Molybdenum demand continues to be driven largely by the steel sector. As emerging
economies, such as China and India, continue on the path to industrialization, they are
expected to need increasing amounts of molybdenum, and this trend is expected to
contribute to global demand growth in the coming years (Virga and Horn, 2009). Roskill
Information Services Ltd. reported that global demand for molybdenum was expected to
increase at an average of 4.6% until 2016. The principal areas of growth were expected to
increase with the use of stainless and other steels containing molybdenum in oil and gas
production, motor vehicle components, and power plants, and the potential for a new
market from alternative and renewable energy.
Availability of higher grade sulfide moly concentrates will be reduced in the longer term.
At the same time demand for moly products will continue to grow. As a result it is
essential that alternative, economical processing routes for treating materials be
developed. On other hand, low grade ores and raw materials comprise lower grade
sulfides, oxides, uranium by-product. So in this review conventional pyrometallurgical
processes and pyro-pre-treatments for production of major molybdenum products are
briefly outlined. Recent developments in direct hydrometallurgical processes for leaching
and recovery of molybdenum are reviewed in details.
This review also covers various separation and purification techniques including solvent
extraction, ion exchange, membrane based separation, and precipitation for recovery of
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molybdenum from industrial streams to suggest suitable methods and processes for
further research and development.
2. MOLYBDENUM RESOURCES AND MARKET RESEARCH
Molybdenum is the 54th most abundant element in the Earth's crust (0.002 g/kg) and the
25th most abundant element in the oceans, with an average of 10 parts per billion; it is the
42nd most abundant element in the Universe. The Russian Luna 24 mission discovered a
molybdenum-bearing grain (1 0.6 m) in a pyroxene fragment taken from Mare
Crisium on the Moon (Jambor et al., 2002). The main commercial source of molybdenum
is molybdenite (MoS2). Molybdenum is also found in several minerals, such as bright
orange-red to yellow-orange Wulfenite (PbMoO4) and transparent adamantine blue,
greenish brown, yellow to grey Powellite (CaMoO4).
2.1. Molybdenum Reserves
World molybdenum reserves and production capacity were concentrated in a few
countries. In 2011, world mine output was estimated to have been 264,000 t
(molybdenum contained in concentrate), of which, in descending order of production,
China, the United States, Chile, Peru, Mexico, and Canada provided about 94%. In the
United States, mine production of molybdenum concentrate in 2011 increased by 7% to
63,700 metric tons (t) from 59,400 t in 2010. Table (1), shows molybdenum mine
production by country.
In North America, most Canadian reserves of molybdenum were contained in porphyry
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molybdenum and porphyry copper-molybdenum deposits in British Columbia. Other
Canadian reserves were associated with minor porphyry copper-molybdenum deposits in
New Brunswick and Quebec. The La Caridad porphyry copper-molybdenum deposit in
Mexico was a leading producer. Molybdenum reserves in Central America and South
America were associated mainly with large porphyry copper deposits. Of several such
deposits in Chile, the Chuquicamata and El Teniente deposits were among the largest in
the world and accounted for 85% of molybdenum reserves in Chile. Peru also had
substantial reserves. Reserves of molybdenum in China and the Commonwealth of
Independent States (CIS) were thought to be substantial, but definitive information about
the current sources of supply or prospects for future development in these two areas was
lacking (USGS, 2011).
2.2. Molybdenum Production By Commercial Processes
Top molybdenum producing companies: Freeport McMoran Copper & Gold, Codelco,
Grupo Mexico, Rio Tinto, China Moly, Jinduicheng, Antofagasta Plc, Thompson Creek
Metals Company Inc., Antamina S.A. Top molybdenum producing mines: Chuquicamata,
Henderson, Bingham Canyon, Endako, Thompson Creek, Cerro Verde, Questa, Los
Pelambres. moly intermediate materials are largely coming from primary moly and by-
product from sulfide ore processing. These intermediated may be accompanied by several
impurities including mainly copper, iron, vanadium, rhenium, tungsten, and uranium. To
meet market demand several processes have been carried out in order to remove these
impurities. Processes used for treatment of moly intermediate depend mainly on
concentration of molybdenum and concentration of impurities.
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Primary molybdenum production continued at the Ashdown Mine in Nevada, the
Henderson Mine in Colorado, the Questa Mine in New Mexico, and the Thompson Creek
Mine in Idaho. Freeport-McMoRan Copper & Gold Inc. (FCX) announced that its
Henderson Mine produced 17,240 t of molybdenum in 2011, a 5% decrease compared
with 18,140 t produced in 2010. The Henderson underground mine produces high-purity,
chemical-grade molybdenum concentrates, which typically are further processed into

value-added molybdenum chemical products. The Henderson operation consists of a
large underground mining complex feeding a concentrator with the capacity to produce
approximately 32,000 metric tons per day (t/d) of molybdenum. Henderson has the
capacity to produce approximately 18,140 t/yr of molybdenum (USGS, 2011). The
majority of the molybdenum concentrate produced at Henderson is shipped to FCXs Fort
Madison, Iowa, processing facility.
FCX announced that construction activities at its Climax molybdenum mine were
substantially complete. Production from the Climax Mine was expected to ramp up to a
rate of 9,070 t/yr of molybdenum during 2013, and depending on market conditions, may
be increased to 13,600 t/yr of molybdenum (Freeport-McMoRan Copper & Gold Inc.,
2012). Thompson Creek Metals Company Inc. (TCMC) owns the Thompson Creek open
pit molybdenum mine and mill near Challis, ID, a metallurgical roasting facility in
Langeloth, PA, and a 75% share of the Endako open pit mine, mill, and roasting facility
in northern British Columbia, Canada. The molybdenum concentrate produced at the
Thompson Creek Mine is transported to the Langeloth facility, which produces
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ferromolybdenum products, molybdenum trioxide, and other specialty products. The
Langeloth facility also processes non molybdenum catalysts for various customers,
primarily in the food industry. TCMC has two high-grade underground molybdenum
deposits, the Davidson deposit near Smithers, British Columbia, Canada, and the Mount
Emmons deposit near Crested Butte, CO(Thompson Creek Metals Company Inc., 2011).
TCMC announced that its Thompson Creek Mine produced 9,690 t of molybdenum in
2011, a 15% decrease from the record 11,370 t of molybdenum produced in 2010. The
decrease was primarily because of lower grade production from the Thompson Creek
Mine in the second half of 2011. TCMC expected to increase production in 2013 (8,600 t
to 9,980 t of molybdenum) (Thompson Creek Metals Company Inc., 2012).
Molybdenum was produced as a byproduct of copper production at the Bagdad, Mineral
Park, Morenci, and Sierrita Mines in Arizona; the Continental Pit Mine in Montana; the
Robinson Mine in Nevada; the Chino Mine in New Mexico; and the Bingham Canyon
Mine in Utah. The Mission Mine did not produce molybdenum in 2011. In the case of
byproduct molybdenum recovery at a copper mine, all mining costs associated with
producing molybdenum concentrate are allocated to the primary metal (copper). In 2011,
byproduct molybdenite recovery accounted for approximately 54% of the U.S.
molybdenum supply.
The Bagdad operation of FCX includes a 75,000-t/d concentrator that produces copper
and molybdenum concentrates, as well as a pressure leach plant that processes
molybdenum concentrate. In 2011, molybdenum production at Bagdad was 4,540 t, a
43% increase compared with 3,180 t of molybdenum in 2010 (Freeport-McMoRan
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Copper & Gold Inc., 2012). The Sierrita operation of FCX includes a 102,000-t/d
concentrator that produces copper and molybdenum concentrates. It also has
molybdenum facilities consisting of a leaching circuit, two molybdenum roasters, and a
packaging facility. The molybdenum facilities process concentrate from Sierrita,
concentrate from other FCX mines, and concentrate from third-party sources.
Molybdenum production at Sierrita in 2011 was 10,430 t, a 28% increase compared with
8,160 t of molybdenum produced in 2010 (Freeport-McMoRan Copper & Gold Inc.,

2012).
FCXs Chino Mine is an open pit copper mining complex located in southwestern New
Mexico in Grant County. The Chino operation consists of a 39,000-t/d concentrator that
produces copper and molybdenum concentrates. During 2011, FCX restarted mining and
milling activities at the Chino Mine, which were suspended in late 2008 (Freeport-
McMoRan Copper & Gold Inc., 2012). Rio Tinto plc (London, United Kingdom)
announced that molybdenum concentrate production at its Bingham Canyon Mine
(operated by Kennecott Utah Copper) was 13,600 t in 2011 compared with 12,900 t of
molybdenum in 2010 (Rio Tinto plc, 2012).
Corporacin Nacional del Cobre de Chile (Codelco), the state-controlled copper and
molybdenum producer, announced that its molybdenum production increased by 4.5% in
2011 to 23,000 t of molybdenum compared with 22,000 t of molybdenum produced in
2010. Antofagasta plc announced that 2011 molybdenum production at its Los Pelambres
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Mine was 9,900 t, a 13% increase compared with 8,800 t of molybdenum produced in
2010 (USGS, 2011).
2.3. Molybdenum Consumption
According to the International Molybdenum Association (IMOA), global molybdenum
consumption reached a new record high of 244,000 t in 2011. The highest usage of
molybdenum in 2011 was in China, where usage increased from 67,400 t in 2010 to
76,200 t in 2011 (Metal-Pages, 2012).
In 2011, IMOA, assisted by the Steel & Metals Market Research Company (Austria),
completed a detailed analysis of molybdenum end uses. According to the study, in 2009,
global molybdenum consumption in all applications was 212,000 t, which included new
and recycled molybdenum. Most recycled molybdenum is introduced as scrap in
steelmaking. The studys analysis was based on more than 250 interviews with key
molybdenum end users. For all applications, approximately 15% of molybdenum input
material originated from scrap. Molybdenum was used in the following end uses
engineering steels (34%), stainless steels (26%), chemical products (13%), tool and high-
speed steels (10%), cast iron (7%), superalloys (5%), and molybdenum metal (5%)
(Kinsman, 2011).
2.4. Molybdenum Prices
In April 2013, the monthly average price for domestic FeMo, as published in Ryans
Notes, in Europe FeMo prices rise to $27-27.20 per kg compared to $26.80-27.10. US
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FeMo suppliers were quoting $12.15-12.20 per lb for truckload quantities. Oxide prices
in Europe and the US firmed to $10.85-11.05 per lb compared to $10.70-10.80 (Ryans
Notes, 2013).
3. MOLYBDENUM PYRO-METALLURGY
The starting material for all pyro-processes of molybdenum is the molybdenite
concentrate. Typical pyro-processes including mainly oxidative roasting, liquation

smelting, plazma smelting (thermal dissociation), and direct reduction of metal sulphide
(Gupta, 1992).
3. 1. Oxidative Roasting
Almost all molybdenite concentrate are first subjected to roasting to yield technical grade
molybdic oxide which forms the basic raw material for all commercially used products of
molybdenum. Roasting process involves a number of chemical reactions (Gupta, 1992).
In the main reaction molybdenite reacts rapidly and exothermically with oxygen and
yields molybdenum trioxide.
MoS2 +3.5O2 MoO3 +2SO2 (1)
Roasting temperature should not exceed 650C, otherwise MoO3 formed may soften or
melt due to local overheating and its high volatility (Amman et al., 1972). Molybdic
oxide begins to sublime at about 593C becomes quite volatile at 704C and melts at
795C (Doheim et al., 1976). Marin et al., (2009) carried out roasting operation of MoS2
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concentrate using small disks with a thin layer of sample in a muffle furnace in air. It was
found that, the rate of oxidation is fairly slow below 440C, and then increases and
remains fairly constant from about 540 C to 640 C. At and above 620C,
melting/glazing started to take place and difficulties were experienced in removing the
samples from the crucible bottoms.
A study by Ammann and Loose (1971) showed molybdenite concentrate roasting by

placing a small sample of concentrate on a porous stainless steel plate and flowing air at a
high flow rate downward through the sample. They carried out measurements between
525C and 635C and concluded that, chemical rate control dominated up to 70 to 80 pct
conversion. Wilkomirsky et al., (1977) investigated oxidation of molybdenum
concentrate in a hot-stage microscope and visually observed the rapid growth of MoO3
crystals outward. The reaction proceeds according to the unreacted core model with
chemical control in the initial stage, followed by an increasing diffusional control once a
solid layer of MoO3 grows progressively over the unreacted core.
Examinations of molybdenum concentrate in various stages of oxidation indicated that in
the early stages MoO2 is formed preferentially to MoO3 (Marin et al., 2009), the
formation of molybdenum trioxide does not proceed to completion. Utigard et al., (2009)
studied oxidation mechanism of molybdenite concentrate in a thermal gravimetric unit on
a small scale in order to develop a better understanding of its oxidation mechanism. The
reaction behavior was found to be very complex due to several gas-solid and solid-solid
reactions that takes place simultaneously. The actual rates vary with the experimental
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conditions such as heating rate, gas flow rate, and sample size (Byung-Su Kim et al.,
2009). The thermodynamics for oxidation of MoO2 or MoO3 are very favorable
(Ammann et al., 1971; Doheim et al., 1976).
Wilkomirsky et al., (2010) studied the kinetics and reaction mechanisms of high
temperature flash oxidation of molybdenite, the results indicate that, at high temperature
the ignitioncombustion proceeds with the generation of gaseous products after

approximately the unreacted core model, with the particles maintaining their shape and
decreasing in thickness until disappearance. The corrected apparent activation energy
calculated at the actual reacting temperature of the particles was 104.0 4 kJ/mol. The
calculated order of reaction with respect to the oxygen was 1.0 0.04.
Fluidized bed roasting of molybdenite has been reported, the heat generated by
the rapid combustion of MoS2 in a fluidized bed may be enough to maintain the required
temperature for the process. On an industrial scale, the quality and effectiveness of
controlling the temperature of the fluidized bed roasting of MoS2 concentrates were
studied by Doheim et al., (1975 and 1976).
Sohn et al., (1983, 1984, 1987, 1988) and Hakobyan et al., (2006) investigated a water-
vapor oxidation process as an alternative to the conventional roasting process. This new
process offers the possibility of lower emission of sulfur containing pollutants by
recovering the sulfur in MoS2 in an elemental form. It also makes it easier to extract
valuable minor elements from the ore. Blanco et al., (2007) studied the thermodynamic
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and the kinetics of oxidation of molybdenite concentrate by water vapor. The kinetics of
the reaction were determined by measuring the weight change of a sample with time in
water vapor at temperatures between 700 C and 1000 C. The reaction rate followed the
shrinking-unreacted-core model under chemical reaction control, which showed
activation energy of 102 kJ/mol.
Ovtsyn et al., (2009) developed a simple method for burning molybdenite, An

installation is used in which material is burned in the vortical flow of the oxidizer with
obtaining the cinder. It is established that, at a temperature of 600 C and air consumption
of 100120 m3/h, 98.7% of MoS2 transformed into MoO3 and 85% of Re sublimes in 0.5
h. The sulfur content in the cinder is <1.8%. Upon treating the cinder with a potassium
carbonate solution, up to 96.5% Mo is extracted.
Balgaeva et al., (2007) shown possibility of post-extraction of rhenium from the calcines
obtained upon the roasting of low-grade Almalyk molybdenite concentrates. The
maximum extraction is reached when leaching calcines with dilute solutions of sulfuric
acid in the presence of pyrolusite.
Rajic and Zlatanovic (1988) reported the reaction between MoS2 and NaCl at 470-900 K
in a flow of oxygen. The results showed that, Gaseous compounds containing chloride
and/or chlorine begin to form at 470 K. Yields of those compounds rise at elevated
temperatures. Some new phases were found, but chlorides and oxychlorides of
molybdenum and sodium sulfate were not identified.
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3. 2. Liquation Smelting
Liquation smelting makes it possible to concentrate selectively the rock-forming and
molybdenum ore components, including impurity elements, in immiscible liquid phases.
Thermochemical processing of copper-molybdenum concentrates by liquation smelting is
discussed by Urbazayeva et al., (1999), in which the copper-molybdenum concentrate
was fused with sodium carbonate content in charge 80-100% and lump silicate content
20% in an electrothermic furnace at 950-1150C. Under these conditions, the extraction
of molybdenum into the liquation salt amounts to 80%, and the extraction of copper and
bismuth into the matte amounts to 95% and 100%, respectively. The smelting reaction
can presented as:
MoS2 + 2Na2CO3 + 4O2 Na2MoO4 + 2Na2SO4 + CO + CO2 (2)
3. 3. Plasma Smelting
The possibility of effective application of a plasma technology to decompose the
molybdenum sulphate concentrate, molybdenite, was reported by several investigators
(Huska, 1967; Munz et al., 1975; Gauvin et al., 1981; and Evans et al., 1988). Direct
production of ferro-molybdenum in a three phase 47 kW plasma arc furnace (at 2300C)
in the presence of lime and iron scrap as per reactions (Prasad et al., 2002):
MoS2 + CaO(s) + C(s) + Fe(s) FexMo(1) + CaS(1) + (1-x)FeS2 + (x/2) S2(g) + CO(g)
(3)
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A study by Timoshevsky et al., (2006) showed that, in the case of the real system which
contains quite a few carbon (~26 %), initial feedstock decomposes through a stage of
refractory molybdenum carbide Mo3C2 formation. The correctness of the thermodynamic
calculations has been proven experimentally. It has been demonstrated that, 100 percent
decomposition of molybdenum sulphide is reachable under the found experimental
conditions (the reactor was heated up to 25002600 K, and then the feedstock feeder was
on). The developed technology enables one to prevent the carry-away of companion rare-
earth metals. Specific energy consumptions were of ~ 40 kWh/kg of Mo.
3. 4. Direct Reduction Of Molybdenite
Direct reduction of metal sulphides in the presence of powerful sulfur acceptors like lime
has the inherent advantages of enabling the development of a single step extraction
process, by passing the difficult metallurgical operation of roasting and aiding in SO2
pollution abatement (Parsad, et al., 1997).
MoS2+CaO + (H2, CO or C) Mo + CaS + (H2O, CO2 or CO) (4)
Kay (1965) reported that a high-grade molybdenite concentrate can be reduced by
hydrogen in the presence of lime to the extent of 82.8% at 1255K in 20.2 ks. In another
limited study, Habashi and Dugdale (1973) observed only 40% reduction at 1073K in 3.6
ks using a theoretical amount of lime and a hydrogen flow rate of 3.93cm3s-l.
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Mankhand and Prasad (1982) proposed a leach-reduction-melting approach for the
treatment of even low grade molybdenite concentrates. The resultant metal from this
approach was of 96-97% purity at 1173 K which could be consolidated and refined by
electron beam melting to 99.9% purity. Following such successful attempts further
investigations have been conducted on the carbothermal (Padilla et al., 1997).
Prasad et al., (1993) investigated the reduction of molybdenite in the presence of lime by
different reductants (H2, CO and C), the results showed that, lime tremendously enhances
the reduction rates and drastically reduces sulphur emission into the off-gases. The lime-
scavenged reduction process has been observed to be very complex and it may proceed
through a number of successive and parallel reactions. The process seems to involve a
sulphur-oxygen exchange reaction (as a pre-requisite) resulting in the intermediate
formation of MoO2 and CaMoO4. In carbothermy as well as reduction of molybdenite by
carbon monoxide, complication arises due to in-situ carburization of the product metal.
3. 5. Chlorination
Chlorination of sulfide ore as an alternative to roasting has drawn considerable interest
for the processing of low grade sulfide concentrate. The high reactivity of chlorine,
relatively low temperature operation, and possibilities of recovering sulfur in a
nonpolluting form are some of the advantages that can be harnessed from this process.
The reaction between MoS2 and Cl2 in the presence of oxygen is:
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MoS2 + Cl2 + 3O2 MoO2C12 + 2SO2 (5)
while with MoS2 and C12 alone:
2MoS2 + 7Cl2 2MoC15 + 2S2Cl2 (6)
Senderoff and Labrie (1955) were the first to chlorinate molybdenite concentrate at 823K
to form molybdenum pentachloride for use in the fused salt electrorefining of
molybdenum. Hayer et al., (1968) in their attempt to recover sulfur by chlorination at 675
K ended up with a product consisting of MoCl5 and S2Cl2.
molybdenite concentrate can be successfully processed by direct chlorination, either in a
static bed reactor in the presence of oxygen at 573 K (Nair et al., 1978) or a fluidised-bed
reactor in the presence of oxygen at 300 K (Nair et al., 1987, 1988) However, for an
exothermic reaction, the fluidised bed is more suitable than the static bed. Hence, direct
chlorination of molybdenite concentrate using the fluidised-bed technique is more
favorable, Fig. 1.
4. MOLYBDENUM PYRO-HYDROMETALLURGY
A pyrometallurgical pre-treatment followed by hydrometallurgical processing plays an
important role in the treatment of low grade molybdenum ores. Mingyu Wang and
Xuewen Wang (2010) have recently applied oxidative roasting followed by sulphation
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roasting and water leaching for raw carbonaceous NiMo ores. The results showed that,
during the oxidation roasting process, molybdenum and nickel sulphides are oxidized and
a molybdenum bearing phase powellite (CaMoO4) is generated. After sulphation
roasting, the powellite vanishes. The generated molybdenum and nickel sulphates are
easily leached in water. Under optimum conditions (roasting temperature 240C for 1 h;
32 ml sulphuric acid/100 g roasted NiMo ore, water leaching for 2 h at 98C and a
liquid-to-solid ratio of 2:1), the maximum extraction of molybdenum and nickel was
92.1% and 83.5%, respectively.
In a novel process by Wang et al., (2009) NiMo ore was roasted at 650C for 4 h,
followed by leaching with Na2CO3 and NaOH mixed solution as shown in Fig. 2. The
recovery efficiency of molybdenum reached 92.32%.
Experimental studies by Wang et al., (2011) showed that, the most effective method to
extract molybdenum and nickel from the carbonaceous NiMo ore is calcification
roasting sulphation roastingwater leaching. Adding 36 g CaO to 100 g the raw
carbonaceous NiMo ore cannot only protect the environment against SO2 pollution but
also promote the formation of bunsinite (NiO) during calcification roasting. After
sulphation roasting with 70 ml 98% sulphuric acid at 240C for 2 h, the bunsinite
vanished. The generated molybdenum and nickel sulphates were readily leached in water
and, the maximum extraction of molybdenum and nickel achieved 97.23% and 93.16%,
respectively, at 98 C stirring for 2 h with a liquid/solid ratio of 2:1.
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A study by Berg et al., (2002) showed the treatment of low-grade sulphidic molybdenum
ores by using a combined processing route for a comprehensive recovery of
molybdenum, copper, and other minor elements as shown in Fig. 3. As the first step,
oxidative roasting was used gives 8590% sulphur removal. The final sulphur content at
the roast could be reduced to about 1.92.0% at (620C - 670C) within 55.5 h roasting.
Then both water leaching at 85C for 6 h, at liquid/solid ratio of 2.85 with magnetic
stirring and dilute sulphuric acid leaching with 5.0 and 7.5 vol.% H2SO4 at 60 and 80 C
for 2 h. The liquid to solid ratio is about 2.85. Both copper and molybdenum were
recovered one after another from the filtrates via cementation by iron powder under
controlled temperature and pH conditions. Recovery for both elements was in all cases
over 99%.
Rao et al., (2001) studied the roasting of bulk sulfide float (BSF) of an Indian uranium
ore, The optimum conditions for roasting have been found to be T=823 K, residence time
4 h and addition of 12% Li SO4. Leaching of the roasted mass under these optimum
conditions with water yielded 98% of Cu values, 65% of Ni values, 93% of Co values
and around 50% of Mo values in the leach liquor. Leaching with NaOH solution of the
acid leach residue yielded additional 43% of Mo values into the alkaline leach liquor that
is free of any other metals. Thus, the overall recovery of Mo in both leach liquors is 93%.
Roasting of molybdenite in the presence of lime results in the conversion of molybdenum
and rhenium values into calcium molybdate and calcium perrhenate respectively. The
SO2 generated during roasting is fixed as CaSO4. Calcium perrhenate [Ca(ReO4)2] , being
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water soluble, can be selectively extracted from the calcine by leaching with water, while
calcium molybdate (CaMoO4) can be solubilized by leaching with dilute H2SO4 (singh et
al., 1988). Juneja et al., (1996) extracted molybdenum and rhenium values from low
grade Indian molybdenite concentrate by roasting in the presence of slaked lime and soda
ash, followed by hydrometallurgical treatment of the roasted products. In the lime
roasting process, molybdenum recoveries of around 99% were achieved when a charge
containing a slaked lime to concentrate ratio of 0.875 was roasted at 550C for 1 h and
the calcine was leached twice with 1 M H2SO4 at 80-90C for 2 h. The roasting reaction
in presence of lime can be presented as follows:
2MoS2+ 6Ca (OH)2 + 9O2 2CaMoO4 + 4CaSO4 + 6H2O (7)
CaMoO4 + H2SO4 H2MoO4 + CaSO4 (8)
In the soda ash roasting process, over 99% of the molybdenum could be extracted when a
charge containing a sodium carbonate to concentrate ratio of 1.05 was roasted at 650C
for 1 h and the roasted mass was leached with water at 80-90C for 2 h. The roasting
reaction in presence of soda ash can be presented as follows:
MoS2 + 3Na2CO3 + 9/2O2 = Na2MoO4 + 2Na2SO4+ 3CO2 (9)
Shariat et al. (2001) treated a MoO3 calcine (60.9% Mo, 1.3% Cu, 2.9% Fe, 0.16% S and
1.2% SiO2) by first dissolving it in ammonium hydroxide. The leach liquor was then
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treated with ammonium disulphide to remove Cu and other base metals before
precipitating molybdic acid (H2MoO4) at pH 2. The precipitate was then dissolved again
in ammonium hydroxide from which ammonium paramolybdate (3(NH4)2O.7MoO3) was
re-crystallised at 60C. The final roasted MoO3 product contained less than 1 mg/kg each
of Ca, Fe, Cu, As and 10 mg/kg of Sb.
Two-steps procedure consisting of oxidation roasting and water leaching can be used for
treatment the high-impurity ferromolybdenum (Lihua Shi et al., 2011). Under the
optimum experimental conditions (CaO/Na2CO3 mole ratio of 0.76; Na2CO3 and CaO
added total mole number of 0.57/100g ferromolybdenum powder; oxidation roasting at
700C for 2h; water leaching for 2h at 98C with liquid/solid ratio of 3:1). The extraction
of molybdenum was 97.5%, and the leached rate of impurities phosphorus, arsenic and
silicon were only 16.2%, 18.1% and 41.2% respectively.
5. MOLYBDENUM HYDROMETALLURGY
5. 1. Pressure Oxidative Leaching
Pressure oxidative leaching of MoS2 concentrates in aqueous medium is carried out in a
well agitated solidgasliquid phase system (Kholmogorov, et al., 2002):
MoS2(s) + 4.5O2(G) + 3H2O(L) H2MoO4(S) + 2H2SO4(L) (10)
The breakdown of molybdenite concentrates in aqueous media in an oxygen atmosphere
includes an oxidation process (Kholmogorov, et al., 2005):
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Mo(IV) Mo(VI)(MoS2MoO3 + H2MoO4) (11)
The pressure leaching of MoS2 in dilute HNO3 at about 120 C and under the oxygen
over-pressure was investigated by Kerfoot and Daugherty (Daugherty et al., 1973;
Kerfoot and Stanley, 1976). Both reported that a period of 1 to 4 h is needed for complete
leaching of molybdenite. Smirnov et al., (2010) developed a process for autoclave

oxidative leaching of molybdenite with catalytic additives of nitric acid, the kinetic
parameters of the process are substantially improved, which decreases (compared to
oxidation without a catalyst) the temperature from 240 to180C and the pressure from 4.4
to 2.5 MPa. The process proceeds smoothly, no rejections of nitrogen oxides to the gas
phase are observed, and no uncontrolled temperature and pressure jumps occured. Under
the following conditions of autoclave leaching of molybdenite concentrates, solid/liquid
ratio 1:8, temperature 180C, total pressure on the system 2 2.5 MPA for duration 2 to
4h. The recovery efficiency of molybdenum from concentrate reached 99.6%.
Khoshnevisan et al., (2012) investigated the kinetics of reactions for the pressure
oxidative leaching of a molybdenite concentrate in less than one hour. The results showed
that, Nitric acid concentration was an important parameter in pressure leaching of the
molybdenite concentrate. At least 3540 g/L nitric acid was required for the leaching of
100 g/L molybdenite. An increase in the amount of pulp density decreased the leaching
efficiency of the molybdenum. Also 85% of reacted molybdenite precipitated as
molybdic oxide and remaining 15% is dissolved in the liquor. Data analysis indicated that
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the rate-controlling step for pressure leaching of molybdenite in nitric acid solution is
chemically controlled. The reaction activation energy was calculated to be 68.8 kJ/mol.
Amer (2001) studied the alkaline pressure leaching of Egyptian molybdenite, the results
showed that grain size, concentration of sodium carbonate and oxygen partial pressure
strongly effect hydrometallurgical process. Kinetics of atmospheric leaching
molybdenum from metalliferous black shales by air oxidation in alkali solution was also
investigated by Zhao et al., (2009), the kinetic analysis of the leaching data for various
experimental conditions indicated that, the reaction is controlled by diffusion with the
activation energy of 15 kJ/mol higher than 65C, and controlled by chemical reaction
with the activation energy of 57 kJ/ mol lower than 65C and molybdenum recovery of
about 90% can be reached in about 30 min.
5. 2. Alkali Fusion And Alkali Leaching
The alkali fusion of molybdenite as a pretreatment process makes it possible to increase
the leaching reaction kinetics. Gupta (1922) has given two flow sheets for molybdenite
alkali fusion. In these flow sheets, iron oxide and sodium nitrate were used as oxidant. In
this study, the alkali fusion process of molybdenite with sodium carbonate in the presence
of air was investigated. The products of this process have high solubility in water. Thus,
solutions with a high concentration of molybdenum can be obtained by the addition of
mineral acid and ammonia. Molybdenum could be recovered as ammonium molybdate.
There is no SO2 emission in this process and sulfur is released as sodium sulfate.
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The results obtained by Kahrizsangi et al., (2010) indicated that during the fusion, sodium
molybdate and sodium sulfate are the final reaction products and sodium sulfide is
detected as an intermediate reaction product. By melting at 850C with 5wt% excess
carbonate, the maximum solubility of the products is obtained. The molybdenum is
recovered from the solutions as ammonium molybdate, Fig. 4.
Zhao et al., (2010) reported a novel technology to processed molybdenum ore. It includes
leaching molybdenum by air oxidation in alkaline solution purifying the leach solution
with freshly precipitated nascent Fe(OH)3 and buffer agent NaHCO3. It followed by
ion exchange and crystallizing ammonium molybdate tetrahydrate as shown in Fig. 5.
5. 3. Acidic Leaching
5. 3. 1. Hcl Leaching
Cao et al., (2009) studied hydrochloric acid leaching process of molybdenite ore in
presence of sodium chlorate, The experimental results showed that leaching time, liquid-
to-solid ratio, leaching temperature, agitation speed, sodium chlorate and hydrochloric
acid concentration had significant effect. Optimum process operating parameters were
established as follows: time: 4 h; hydrochloric acid concentration: 20%; liquid-to-solid
ratio: 10:1; temperature: 70 C; agitation speed: 500 rpm, the molar ratio of NaClO3 to
MoS2: 3.21. Under these conditions, the extraction of molybdenum is greater than 98%.
A study by Kumar et al., (2007) showed that leaching molybdenite concentrate
sequentially with dil. HCl (5 wt. %) followed by dil. HF (5 wt. %) or a mixed acid (HF+
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HCl) lixiviant, would achieve a high level of refining in molybdenite product reached
95%. Using PTFE-lined autoclave at 120C for 2 h with a well stirred mixed lixiviant (5
wt.% HF+ HCl) a product containing 97.597.8% MoS2 and 1.65% carbon was obtained.
5. 3. 2. H2so4 Leaching
Arsenic rich ores could be particularly critical for some moly feedstocks. This is
particularly true given the existence of large Cu-Mo resources where arsenic minerals
orpiment and realgar are present. These are naturally flotable & result in high-As
concentrates which are commercially problematic. The old days of roasting these are
gone and hydrometallurgical routes are needed. Landa (1984) investigated leaching
molybdenum and arsenic from uranium ore and mill tailings using Sulfuric acid. Bartecki
and Rycerz (1988a,b) investigated the dissolution of synthetic molybdenum disulphide
MoS2 in aqueous potassium bromate solution in the presence of sulphuric acid. The
results showed that, the dissolution rate of MoS2 was significantly dependent on
temperature. The values of the apparent activation energy of 32.3 kJ/mol supports the
prediction that the dissolution proceeds with chemical control passing in the course of
reaction to conditions of diffusion control. A reaction order of 0.40, 0.40 and 1.11 with
respect to KBrO3, H2SO4 and specific surface of MoS2, respectively, was determined
from leaching experiments. Br- ions act as an initiator of MoS2 dissolution in diluted
H2SO4 solutions.
Antonijevic and Pacovic (1992) studied leaching of molybdenite with H2SO4 in presence
of Na2Cr2O7. The results showed that the reaction was chemically controlled, and the
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reaction rate was first-order relative to the sodium dichromate and sulfuric acid
concentrations. They also leached mixtures of molybdenite with pyrite and chalcopyrite
to simulate the behavior of low-grade molybdenite concentrates, and found that the rate
of molybdenite leaching decreased in the presence of pyrite and chalcopyrite.
Naguman et al., (2009) reported a process for leaching oxidizing molybdenum products,
the results showed that by using molybdenum product roasted at 550C, linear velocity of
the air blown into the roasting reactor ( V= 0.7 m/s), concentration of sulfuric acid was
150 g/l, the cinder weight was 10 g, the process temperature was 8090 C, and the ratio
was L : S = 10 : 1. Extraction efficiency of molybdenum reaches 95%.
Lasheen et al., (2013) investigated the leaching of molybdenum-uranium ore in H2SO4
using H2O2 as oxidizing agent. The results shows that, working 2.5M H2SO4; 0.5M H2O2;
stirring speed 600, solid/liquid ratio 1:14 at 95C for 2h and using particle size -74m,
the extraction efficiency of molybdenum extraction reaches 98.44%, whilst uranium
attained about 98.70%. the rate of molybdenum is chemically controlled and follows the
shrinking core model 1 (1X)1/3=kt with an apparent activation energy of 40.40
kJ/mole.
5. 3. 3. Hno3 Leaching
Nitric acid is used industrially as a reagent for molybdenite leaching and for the
production of molybdenum salts, The dissolution of MoS2 takes place due to the
oxidative power of the leaching agent, according to the following extraction equilibrium
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equations (Gupta et al., 1990; 1992; Solar et al., 1988; Vizsolyi et al., 1980; Valenzuela
et al., 1995)
MoS2 + 18 HNO3 MoO42-+2SO42-+ 18NO2+6H++6H2O (12)
MoS2 + 6 HNO3 MoO42-+2SO42- + 6 H+ + 6 NO (13)

MoS2 + 8 HNO3 MoO42- + 2 NO3- + 4 H+ + 2 SO42- + 6 NO + 2 H2O (14)
MoS2 + 6 HNO3 MoO3.nH2O + 2 H2SO4 + 6 NO + (l-n) H2O (15)
These equations are thermodynamically feasible as shown in the Pourbaix potential-pH
diagram for the MO-S-H2O system (Pourbais, 1966). However, molybdenum chemistry
is rather complicated, because this metal has several oxidation states in aqueous solution.
Mo(V1) is usually stable in oxidative conditions, but since it tends to hydrolyze and to
form polyheteroacids, the number of species present in solution is large and it is not
always possible to identify all of them, which makes it difficult to treat mathematically its
reactions and products. For instance, molybdate anion in acid medium suffers the
following equilibrium reactions:
MoO42- + 2 H+ H2MoO42- (16)
MoO42-+ 4 H+ MoO22+ + 2 H2O (17)
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H2MoO42- MoO3.H2O (18)
During the leaching operation, the precipitation of an important fraction of dissolved
molybdenum takes place. Vizsolyi and Peters (1980) reported that, by means of chemical
analysis, the solid corresponds to MoO3.1/2H2O. This solid, whose precipitation is
accelerated by ammonia addition, after filtering and washing, was leached with
ammonium hydroxide at 60C to obtain ammonium molybdates.
The nitrogen(IV) oxide accelerates the MoS2 oxidation up to 5.5 times in comparison
with NO. The simultaneous formation of NO2 and HNO2 leads to MoS2 oxidation under
the prevailing conditions (Kholmogorov et al., 2005). Specific equipment is needed for
that: for instance, tubular autoclaves are used industrially for MoS2 oxidation in nitric
acid. Such autoclaves provide the necessary contact between the MoS2 species and the
HNO3 oxidant, as well as HNO2, NO2, NO. The molybdenum is mainly present in the
solutions obtained in the form of MoO22+ and [MoO2(SO4)2]2-.
Medvedev et al., (2009) reported a process for direct nitric acid leaching of molybdenite
concentrate, the results showed that The concentrate is decomposed under the intense
mechanical stirring of the pulp at T = 9095C in two stages decomposition by a solution
of sulfuric (100 g/L) and nitric acids (30%) with the subsequent precipitation of calcium
molybdate (CaMoO4 ) from the filtrate.
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5. 4. Electro-Oxidation Dissolution
Jiang (1984) protracted E-pH diagram of Cl-H2O system, when bath voltage is 3.0, pH is
greater than 8, oxidant in electrolyte is mainly NaClO. The concentration of NaClO and
NaClO3 were measured at a liquid-to-solid ratio 25:1 (MoS2, 5 g), concentration of NaCl
4 mol/L, stirring speed 400 rpm, operating potential 3.0 V, anode ampere density 800
A/m2, pH = 9, room temperature, leaching time 240 min, the result is seen in Fig. 6; seen
from which, as the time grows, it was found that the concentration of NaClO firstly
increases and then decreases, and the concentration of ClO3 would gradually increase in
the process of electrolysis when ore sample was not added into the electrolyte; if ore
sample exist in the electrolyte, chlorine ions are mostly oxidized to NaClO, part of which
are farther oxidized in form of NaClO3 existing in the solution. In the electrolysis
process, when pH is 9, NaClO is the mainly oxidant.
The main chemical reactions can be described by the following equation (Barr et al.,
1975; Li, 2002; CAO Zhong-hong et al., 2010).
2NaCl + 2H2O 2NaOH + H2 + Cl2 (19)
2NaOH + Cl2 NaClO + NaCl + H2O (20)
MoS2 + 6NaClO + 4NaOH Na2MoO4 + Na2SO4 + S + 6NaCl + 2H2O (21)
S + 3NaClO + H2O H2SO4 + 3NaCl (22)
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6NaClO+6OH2NaClO3+4NaCl+3/2O2+3H2O (23)
Cao et al., (2010) reported the electro-oxidation of molybdenite concentrate in sodium
carbonate buffer system was studied. The results indicated that, the dissolution rate
increases with increase in temperature and NaCl concentration. When the liquidsolid
ratio is 25, mixing rate, 400 rpm, pH = 9, room temperature, concentration of NaCl, 4
mol/L, then the dissolution rate of molybdenite can achieve 99.97% in 240 min. A
shrinking core model is presented to describe the dissolution and to analyze the data. It
was established that the leaching process is mainly controlled by diffusion through a
porous product layer, the apparent activation energy of this dissolution process was found
to be 8.56 kJ/mol.
Electric-oxidation extraction of molybdenite concentrate in alkaline NaCl electrolyte was
investigated by Hong et al., (2010) the results showed that at liquid-to-solid ratio of 30:1,
stirring speed of 400 r/min, pH=9, room temperature, concentration of NaCl of 4 mol/L,
the leaching efficiency of molybdenite can achieve 99.5% in 240 min. Molybdenite
concentrate cannot be electrooxidized directly on the anode. The leaching process is
mainly controlled by the diffusion through an element sulfur layer, and the apparent
activation energy of this dissolution process is 8.56 kJ/mol.
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5. 5. Hypochlorite Leaching
The main chemical reaction of hypochlorite leaching can be represented as follow
(Warren, 1983; Cao et al., 2009)
MoS2 + 9NaClO + 6NaOH Na2MoO4 + 2Na2SO4 + 9NaCl + 3H2O (24)
A study by Liu Youcai et al., (2011) proved that molybdenum may be effectively
removed from copper concentrate by sodium hypochlorite leaching. The optimum
process operating parameters were: time, 4 h; sodium hydroxide concentration, 10%;
sodium hypochlorite concentration, 8%; liquid to solid ratio, 10:1; temperature, 50 C;
and, agitation speed 500 r/min. Under these conditions the extraction of molybdenum was
greater than 99.9% and the extraction of copper is less than 0.01%. A shrinking particle
model could be used to describe the process of leaching of molybdenum. The apparent
activation energy of the dissolution reaction was found to be approximately 8.8 kJ/mol.
Liu et al., (2011) reported the extraction of molybdenum from low-grade NiMo ore in
sodium hypochlorite solution under mechanical activation. The results show that, the
following parameters such as leaching time, liquid-to-solid ratio, pH value, sodium
hypochlorite and sodium carbonate concentrations have significant effects on the
recovery rate of molybdenum. The recovery rate of molybdenum reaches 96.3%, which is
much higher than conventional agitation system (73.0%). It is suggested that an increase
of surface area and phase transformation under mechanical activation should be
responsible for the improved leaching recovery of molybdenum.
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5. 6. Bioleaching
Molybdenite is extremely resistant to bacterial attack, its bioleaching being characterized
as relatively slow and incomplete (Kelley, 1986; Bryner and Anderson, 1957). Soluble
forms of Mo are toxic to ore leaching bacteria which could be adapted to Mo only
partially (Duncan et al., 1967). These early studies led to the conclusion that commercial
bioleaching of molybdenum sulfides was not practical (Duncan et al., 1967; Tuovinen
and Kelly, 1972). Thermophilic microorganisms were more resistant to dissolved Mo

than mesophilic bacteria such as Acidithiobacillus ferrooxidans (Brierley and Murr,
1973). However, thermophilic microorganisms extracted only 3.3% to 13.3% of Mo from
a concentrate after 30 days of bioleaching.
Silverman and Lundgren, (1959) showed that 1 mmol/L Mo in 9 K medium had a
restrictive impact on Acidithiobacillus ferrooxidans. Their capability of ferrous oxidizing
would be completely suppressed when the Mo concentration in 9 K medium reached 2
mmol/L. Consequently, the dissolution of Mo via the oxidization by the bacterially
generated Fe (III) is hindered. Donati et al., (1992) used Acidithiobacillus ferrooxidans to
leach the low-grade sulfide ore containing Cu and Mo, and the leaching rates of 60% for
Cu but only 0.34% for Mo were obtained at 30 C. There exist several reasons for the
aforementioned phenomenon. It was discovered that Acidithiobacillus ferrooxidans did
not absorb on hydrophobic MoS3, which may inhibit the efficiency of direct bioleaching.
More importantly, the presence of a low concentration of extracted Mo in the solution has
toxic effect on the biological activity of the microbes.
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Romano et al., (2001a,b) have used a mixed culture of mesophilic microorganisms for
bioleaching of molybdenite concentrate. Molybdenum and copper dissolution in their test
were reported lower than 1% and 50%, respectively. Askari et al. (2005) found
Acidithiobacillus ferrooxidans could grow in media containing up to 250 ppm Mo if
pyrite was included as an energy source. Mo extraction from a concentrate (48.53% Mo)
was low ( 1%) after one month of bioleaching, which was attributed in part to Mo
precipitation from solution. high redox potential was more suitable for the reduction of
molybdenum via bioleaching (Askari et al., 2006).
Gregory et al., (2008) investigated bioleaching of molybdenite-containing mine waste
samples and from high purity molybdenite in solutions amended with ferrous sulfate.
Bioleaching of Mo occurred when solution Eh exceeded 750 mV to 800 mV (s.h.e.). The
rate of bioleaching of high purity molybdenite increased with decreasing particle size,
averaging 3.22 mg Mo/m2/d at 24 C. This surface area-based rate is less than 1% of the
bioleaching rate of pyrite. Molybdenite bioleaching increased with temperature by a
factor of approximately 2.5 for each 10 C increase in leaching temperature up to 40C.
Apparent activation energies were 61.2 to 73.4 kJ/mol for bioleaching of high purity
molybdenite and for molybdenite from mineral processing waste streams, respectively.
Jia-wu et al., (2011) The bioleaching of molybdenum from its sulfide ore using a Mo-
resistant thermophilic bacterium sulfolobus metallics combined with a membrane
biological reactor (MBR) was studied. The experimental results showed that the
concentration of Mo can be controlled by filter of the membrane in MBR and the toxicity
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of Mo to microorganism is decreased in the process of bioleaching. It was also evidenced
that there were different leaching rates of Ni and Mo when the concentration of Mo was
different. After leaching for 20 d in the MBR at Mo concentration of 395 mg/L, the
leaching rates of Ni and Mo reached the maximum of 79.57% and 56.23% respectively
under the conditions of 100 g/L of mineral density, 65 C, pH=2 and 1.0 L/min of the
aeration rate. While 75.59% Ni and 54.33% Mo were leached out in column without
membrane under the same conditions.

5. 7. Comparative Analysis Of Dissolution Processes
Table 2, shows the most important technological processes which are used or tested in
industry for molybdenum production including mainly critical operating and design
variables.
An ever increasing quantity of lowgrade molybdenite concentrates are being produced
from secondary resources especially as by-product of copper and uranium mining. Such
low grade MoS2 concentrates are not amenable for the extraction by traditional methods.
Several hydrometallurgical processes have been developed for the extraction of
molybdenum satisfying indigenous needs and environmental considerations. Traditional
pyro-routes for the extraction of molybdenum suffer from several inherent limitations
listed below.
a. Large number of processing steps
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This includes roasting, three chemical purification steps, calcination, three-stage
hydrogen reduction and finally metal consolidation.
b Difficulties in reducing the trioxide to metal
A single step reduction is not feasible on account of the high sublimation tendency of the
trioxide even at moderate temperatures, formation of low melting eutectic (550-600C)
which retards its reduction rate and also exothermic nature of the oxide reduction process.
c SO2 pollution
A large volume of low strength SO2 is emitted (from any molybdenite roaster) whose
tolerable level in the environment is very low (5 ppm threshold limit). Consequently,
molybdenite roasters are required to install expensive pollution abatement equipment.
d Low recoveries
5-25% Mo being left over in the residue after trioxide purification stage which
necessitates additional treatment of the residue to improve the overall recovery of Mo
metal.
Direct reduction of molybdenite in the presence of powerful sulfur acceptors like lime
has the inherent advantages of enabling the development of a single step extraction
process, by passing the difficult metallurgical operation of roasting and aiding in SO2
pollution abatement. Plasma smelting has advantage for treating molybdenite
concentrates largely not merely from the increases reduction rates obtained at elevated
temperature but also from the more reactive species available at these temperatures in the
plasma medium.
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Hydrometallurgical processes have advantages of low energy consumption and no
emission of SO2, and become attractive especially for low-grade and complex ores. For
example, alkali fusion of molybdenite enables Mo recovery in various usual forms e.g.,
molybdic oxide and calcium molybdate. Sulphur from the concentrate can be converted
to sulphate and no air pollution problem is envisaged. Direct acidic leaching of
molybdenite has inherent economic merits such as (a) its ability to treat low grade
concentrates; (b) no SO2 pollution; (c) high MoO3 product; (d) possible recovery of Cu,
U, and Re as by-products; and (e) regeneration of the acid.
6. RECOVERY OF MOLYBDENUM FROM LEACH LIQUORS
Table 4, summarize the specifications of molybdenum products required for different
markets. According to concentration of molybdenum required in product and
concentration limit of impurities the process for recovery molybdenum from solution was
chosen.
6 1. Molybdenum chemistry in solution
In aqueous solution the most stable oxidation of molybdenum compound is +IV. Of these
compounds, the ones derived from the oxide MoO3 are the most common. The solubility
of pure MoO3.2H2O varies with temperature, ranging from 2.12 g/L at 15C to 5.185 g/L
at 80C (Gupta, 1992). Ryzhenko (2010) reported the dominance of MoO22+ in dilute
(<1mg/L Mo) acidic solutions (pH<1) as found in groundwater systems (108 M Mo).
Other cationic species such as H6Mo2O82+, H3MoO4+ could also exist in solutions of pH <
2.5 (Olazabal et al., 1992). It is generally believed that onlyMoO4-2 exists at pH > 6.5,
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whereas there are neutral and anionic species such as H2MoO40, Mo6O13-2, Mo6O20-2,
Mo7O21(OH)3-2 in the pH range 2.56.5 (Gupta, 1992).
There is a possibility of re-precipitation of molybdate salts from Mo(VI), Fe(III) and
Cu(II) ions formed during leaching (Gupta, 1992). Iron(II) molybdate FeMoO4 cannot be
formed from an aqueous solution containing Mo(VI) and Fe(II), as Fe(II) is oxidised to
Fe(III) by Mo(VI) (Gupta, 1992). Iron(III) molybdate, Fe2(MoO4)3.H2O, is known to be

sparingly soluble in the pH range 2.54.25 (~0.01 g/L Mo), but outside this range, the
solubility of ferrimolybdate increases (Safarian and Furbish, 1965). Bright green copper
molybdate can be precipitated as CuO.3CuMoO4.5H2O or 2CuMoO4.Cu(OH)2 (Gupta,
1992). Thus, it is important to examine the different species which may be formed or
precipitated during the purification of MoO3 containing Cu and Fe impurities on the basis
of EhpH and species distribution diagrams. Table 3 lists and compares standard Gibbs
free energy data (Gof) (at 25C) for molybdenum species reported by previous
researchers and employed in various data bases (Nam et al., 2011).
Significant differences in Gof of species such as MoO3(s), H2MoO4 and CuMoO4 shown
in Table 3 are expected to be reflected in relevant species distribution diagrams. The
speciation of Mo compounds (at 25C) in the present study was modelled using the
Stabcal program (Huang, 2008). Several solid species such as CuMoO4, Fe2(MoO3)3,
CuFeO2 and CuFe2O4 at pH > 1 can be formed as shown in the EhpH diagram (Fig. 7)
derived for 25 C. The software capability is limited to standard temperature and pressure
conditions, therefore precluding the derivation of these diagrams at 70C. Fig. 8ad
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compares and contrasts the species distribution diagrams for Mo(VI) solutions based on
different data bases. Fig. 8d also shows dissolved Mo(VI) species in acidic solutions and
the precipitation of CuMoO4 at pH > 2.7 and Mo(VI) concentration greater than 0.28 M.
Fig. 8a shows that Mo(VI) can exist as H2MoO4 in highly acidic regions (pH < 0.5).
Thus, the simulation proposes that CuMoO4 could be precipitated alone or with H2MoO4,
MoO3 or MoO3.H2O from the leach solution at higher pH values. At higher
concentrations of Mo (61 g/L or 0.63 M) in the leach liquor, the H2MoO4 species seems
to be predominant within the pH range 05 (Young Nam et al., 2011). The difference in
the regions of stability for solid mixtures of (MoO3+CuMoO4) or (H2MoO4+CuMoO4) in
Fig. 8ad is due to the different values of Gof from different databases (MinteqA2 or
Russian or HSC) available in the Stabcal program (Table 3). Thus, the pH values at
which the precipitation of CuMoO4 takes place are at pH 0.6, 3.3 or 4.2 based on the
three data bases MinteqA2, Russian or HSC, respectively. The standard Gibbs free
energy of formation of ferri-molybdate, Fe2(MoO4)3, of 2,719.968 kJ/mol (Table 3) as
calculated from its formation constant of K=1035.29 (reported by Meima and Comans,
1998) was also included in the modelling. The, simulation based on this value does not
show the precipitation of Fe2(MoO4)3 in the acidic zone in Fig. 8ad, indicating the high
solubility of Fe2(MoO4)3 compared to H2MoO4, MoO3 or CuMoO4.
Molybdenum (VI) solution of 10-3 M or high form anionic aggregates (isopolyions) in
weakly acidic solution, and cationic aggregates in strongly acidic solution. On the other
hand, molybdenum can form mixed aggregates (heteropolyions) with most transition
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metal and non-metals (Pope, 1983). In acid base reactions, molybdenum forms strong
complexes with most organic chelating agents.
6.2. Solvent Extraction
Organic extractants used for the separation of metal ions facilitate the transfer of the
metal ions from the aqueous phase to the organic phase in solvent extraction. Based on
the nature of the organic extractant, the metal ion, and the diluent, effective separation
methods can be devised. These organic extractants broadly fall into three classes,
chelating extractants, solvating extractants, and ion-pair extractants. For the first two
classes, usually nonpolar organic diluent is preferred. On the other hand, polar diluents
are preferred in the case of ion-pair extraction.
6.2. 1. Chelating Extractants
These extractants form chelate complexes, and many of them are weak acids. Usually,
they dissociate at low pH to form anionic ligands that form strong complexes with the
metal ions. Chelating extractants such as beta-diketones, organophosphorous acidic
extractants, hydroxyoximes, have been used extensively for the extraction of
molybdenum from solutions. Beta-diketones such as methyl isobutyl ketone (MIBK) has
been commonly used for the separation of molybdenum ions (Yatiraja et al., 1973;
Caletka and Krivan, 1989).
Organophosphorous acidic extractants such as di-(2-ethylhexyl) phosphoric acid
(D2EHPA), 2-ethylhexyl phosphonic acid (PC-88A), bis(2,4,4-trimethylpentyl)
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dithiophosphinic acid (Cyanex 301), and bis(trimethylpentyl) phosphinic acid (Cyanex-
272) are employed for process applications. Their high organic phase solubility is based
on the fact that they exist predominantly in dimeric form in the organic phase. Extraction
with di(2-ethylhexyl)phosphoric acid (D2EHPA), have been widely used as extraction
agents (Kolarik et al., 1973; Das et al., 1984; Caletka and Krivan, 1989)
Qingyuan and Huihao (1986), have been investigated the extraction behavior of
molybdenum with D2EHPA, the results showed that, When the pH values of the aqueous
solution containing only molybdenum are below 2 or 3, molybdenum is extracted well
with 40% D2EHPA by cation exchange according to the following reaction:
MoO22+( aq) + 2 (HR2PO4)2(org) MoO2(R2PO4)2 . 2HR2PO4(org) + 2 H+(aq) (1)
where (HR2PO4)2 is the dimer of D2EHPA.
Valenzuela, (1995) determined that the extraction of molybdenum with 2-ethylhexyl
phosphonic acid (PC-88A), is highly efficient around pH 0.8, since cationic species of
Mo (VI), feasible to be extracted by PC-88A, are predominant in such pH region. No co-
extraction of others metals was observed at the pH of molybdenum recovery. Pathak et
al., (2010) investigated the extraction of molybdenum (VI) from acidic radioactive waste
(PC-88A)/n-dodecane. The extraction of molybdenum was found to be better than 98%
in a single batch contact using 0.15 M PC-88A (O/A = 1:1) at 2 M HNO3.The kinetics of
extraction was found to be very fast. Even more than 98% extraction of molybdenum was
observed in 20 min of equilibration time.
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Behera et al., (1994) studied the extraction of molybdenum from aqueous HCl medium
using organophosphonic acids. In this process, The extraction is quantitative with Cyanex
301 (92.4%) at 0.1M HCI solution. For PC-88A and Cyanex 272, extraction is 80% and
74%, respectively, at 0.1M HCl concentration and gradually decreases to 38% at 1.0M
HCl solution. Extraction of molybdenum (VI) is poor with Cyanex 302 (52.4%) even at
0.1M acid concentration. the extraction efficiencies of these extractants for molybdenum
follow the order:
Cyanex 301 > PC-88A > Cyanex 272 > Cyanex 302.
The better extracting ability of Cyanex 301 is due to the greater strength of the Mo-S
linkage. The extraction mechanism may be as follow:
MoO2Cl(aq) + RH(org) MoO2ClR(org ) + H+(aq) (2)
Saberyan et al., (2003) reported the extraction of molybdenum from acidic medium with
Cyanex 301, the results showed that, the extraction system reaches equilibrium quickly,
less than 5 min and that the extraction efficiency of molybdenum(VI) is dependent upon
the type and concentration of the aqueous phase acid, extractant concentration, and metal
ion concentration. However, it is independent of the diluent type and temperature.
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Knyazkina et al., (2010) studied the extraction of molybdenum with
bis(trimethylpentyl) phosphinic acid (Cyanex-272), It is shown that the extraction of
Mo(VI) Cyanex 272 proceeds rather slowly; no less than eight minutes are necessary to
establish equilibrium. It is established that, the maximum recovery of molybdenum with
Cyanex 272, similarly to extraction with di-(2-ethylhexyl) phosphoric acid (D2EHPA)
and polyalkylphosphonitrile acids, is attained at pH ~ 2.

-hydroxy oximes are promising extractants for the effective separation and
recovery of molybdenum(VI) from acidic leach solutions, several patents have described
the extraction of molybdenum (VI) from aqueous solutions using -hydroxy oxime as the
extracting agent (Donell et al., 1968; Ronald et al., 1969; wells et al., 1977). Wells et al.,
(1977) reported that molybdenum (VI) could be extracted selectively from an aqueous
solution containing various other metal values, such as copper, arsenic, iron, bismuth,
antimony, tin and lead, in addition to molybdenum(VI) by LIX 63 dissolved in a
hydrocarbon solvent, where nonylphenol was added to improve the stripping efficiency
of molybdenum(VI) from the loaded organic phase, with an aqueous ammonium
hydroxide strip solution.
Zhang et al., (1996) investigated the extraction of molybdenum from acidic medium with
40% LIX 63 in Exxsol D80, in the presence of various other metals, such as vanadium
(IV), aluminum(Ill), cobalt(II), nickel(II) and iron(Ill). In this process, Molybdenum(VI)
was extracted preferentially and separated completely from the coexisting metals
involved at low pH (e.g., around 1.5) with LIX 63 dissolved in Exxsol D8. Molybdenum
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(VI) in the organic solvent was easily stripped by employing 10% NH4OH as stripping
agent and excellent phase separation performance (rapid phase separation, no formation
of a second organic phase and no generation of an emulsion) in the stripping process was
observed in all cases.
Mohanty et al., (1991) have been early investigated selective extraction of molybdenum
with LIX 622 extractant, a reagent based in the mixture of 5-

dodecylsalicylaldoxime and tridecanol. The order of extraction of Mo(VI) from 1M add
solutions by 5% (v/v) LIX 622 (HL) in benzene is HC1 > HNO3 >HC1O4 >H2SO4 , and
extraction decreases with increasing concentration of HC1 and H2SO4 , and increases
slightly with increasing concentration of HNO3 and HC1O4 . It was found that
molybdenum was extracted into the organic phase by a complex mechanism which
involves the formation of three species (MoO2L2, MoO4H3HL+HSO4- and MoO4H2HL,
where L represents the extractant). The extraction process is dependent on the aqueous
pH, extractant concentration and organic diluents but it is independent of the initial metal
concentration. (Sastre et al., 2000; 2001).
6. 2. 2. Solvating Extractants
Solvating extractants are widely used in the extraction of molybdenum. Usually, the
extraction of metal ions by solvating extractants proceeds via replacement of water
molecules by basic donor atoms (such as O, S, or N) of the neutral ligands. While pH
plays an important role in the extraction of metal ions by the acidic chelating extractants,
counteranions such as NO3, Cl, etc., significantly influence the extraction of metal ions
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by solvating extractants (L) like tri-n-butyl phosphate (TBP), triphenyl phosphine oxide
(TPPO), etc. several investigation have been carried out on the extraction of molybdenum
using TBP (Daugherty, et al., 1973; Komasawa et al., 1987a; 1987b; Cruywagen and
Rypstra, 1985; 1992).
Alamdari et al., (2000) studied thermodynamics extraction of molybdenum from aqueous
sulfuric acid media with TBP dissolved in kerosene. The results showed that, the
molybdenum extraction reaction with TBP is an exothermic reaction. The apparent
standard molar enthalpy for extraction of molybdenum anions is -75.90 kJ/mol and the
apparent standard entropy of molybdenum extraction with TBP from sulfuric acid
aqueous media is -0.21 kJ/mol.
Sato et al., (1990) reported the extraction of molybdenum(VI) from aqueous acid
Solutions by TBP and TOPO (tri-octyl phosphine oxide). The results showed that the
extraction efficiency for molybdenum (VI) of TOPO is larger than that of TBP. However,
the extraction efficiency of TBP is in the order HC1 HNO3 at low aqueous acidity and
HC1 > HNO3 at higher acidity, while that of TOPO is in the order HC1 HNO3 H2SO4
at low aqueous acidity and HC1 > H2SO4 > HNO3 at higher acidity..
Maiorov et al., (2009) reported that the extraction of molybdenum with TBP sharply
increase in the presence of Ti (IV) and Si (IV) macro quantities. Goletskii et al., (2010)
investigated the extraction of molybdenum from supersaturated solutions in nitric acid
with tributyl phosphate solutions. The extractability of Mo in the supersaturation region
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sharply decreases with a decrease in the TBP concentration and with an increase in the
acidity of the aqueous phase. The kinetics of the Mo extraction is described by a first-
order rate equation.
Santosh et al., (1996) presented a new type of solvating extractant triphenylphosphine
oxide (TPPO) dissolved in toluene. The extractions are carried out from the hydrochloric
and hydrobromic acid medium. The extraction of molybdenum is quantitative from 2.54 -
3.10 M hydrochloric acid and from 3.76 - 3.98 M hydrobromic acid with 6% TPPO. The
probable extracted species were solvated salts of the type MoO2Cl2. 2TPPO.
Travkin et al., (2006) studied extraction of molybdenum with hexabutyltriamide of
phosphoric acid from different acidic medium, the results showed that, the extraction of
molybdenum decreases with increasing temperature. Horg = 10.64 kJ , Sorg = 1.69 J
mol-1 K-1.
6.2. 3. Extraction By Ion Pairs
This type of extraction proceeds with the formation of ion-pair species between the
metal-bearing ions and counter ions provided by ligands. Acidic ligands provide anions
by liberating protons, which then complex with the metal cations to form an ion pair. On
the other hand, basic ligands provide cations that complex with aqueous anionic metal
complexes to form ion pairs. Tertiary amines and quaternary ammonium compounds are
the main class of ion pairs extractants. The reported literature reveals a large variety of
extractants based on Tertiary amines and quaternary compounds used for molybdenum
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extraction from various sources (Yonezawa et al., 1977; Hirai et al., 1993; Behera et al.,
1993; Sawant et al., 1997; Voropanova et al., 2004).
The efficiency of molybdenum extraction by amines decreases as follows: quaternary >
tertiary > secondary > primary. Although certain difficulties are encountered in stripping
molybdenum using quaternary ammonium compounds, tertiary amines have found wide
application in practical extraction systems. Among these is tri- n-octyl amine (TOA),
which extracts molybdenum complexes by an anion-exchange reaction (Voropanova et
al., 2004; Bishnoi et al., 2007). Diisododecyl amine (DIDA), was reported as effective as
the widely used extractant TOA, the advantages of DIDA over TOA is that it can be used
without a modifier (Palant et al., 1998 and Gerhardt et al., 2000). More than 99%
molybdenum can be extracted by using 15% v/v technical grade DIDA at a pH of 2 in
aqueous/organic ratio 1:1 (Gerhardt et al., 2001). Primary amine Primene JMT contrary
to tertiary amines enables effective extraction of molybdenum from weak acidic solutions
(Jose Coca et al., 1990; Nekovar et al., 1998; 2000).
A quaternary ammonium salt (Aliquat 336) is widely used for molybdenum extraction
(Vieux et al., 1980; Karagiozov, 1984; Bal et al., 2004). Olazabal et al. (1992) reported
the extraction of molybdenum (VI) by a basic alkylamine (Alamine 336) and Aliquat 336
dissolved in toluene. The results showed that the extractions of Mo(VI) is as a function of
pH when the aqueous solution was equilibrated with 0.1 mol/L Alamine 336 and 0.1
mol/L Aliquat 336 in toluene, respectively, are shown in Figs 9 and 10. As can be seen,
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for the Alamine 336/toluene system, molybdenum is quantitatively extracted in the region
pH<4 and the extraction is suppressed at pH>7.
An et al., (2009a,b) used Alamine 304-1 (10%, v/v), to selectively extract Mo(VI) from
an acid wash liquor containing 1015 g/L Mo(VI), 12 g/L Cu(II) and 2 g/L Fe(III). One-
stage stripping of a loaded organic could be performed using ammonia (12.5%, w/v) for
the complete transfer of the Mo(VI) to the aqueous phase, which would yield a high
purity molybdate solution, where high purity (>99.9%) MoO3. Parhi et al., (2011)
investigated the extraction of molybdenum from the sea nodule leach solution at
equilibrium pH 1.62 with 10 % v/v Alamine 304-1 in two stages at A:O=12:1 phase ratio.
A mixture of 5M NH4OH+2.5 M (NH4)2CO3 showed rapid and very good stripping
efficiency as compared to other ammonical reagents. The stripping of molybdenum in 2-
stages at the phase ratio of A:O=1:16, resulted in quantitative stripping. Subsequently,
pure forms (99.9%) of (NH4)4 Mo2O6 and MoO3 were recovered from the stripped
solution.
Triotylamine (N235), was used as a promising reagent for extraction of molybdenum
from aqueous solution. Zhao et al., (2011) reported the extraction of molybdenum from
the leaching solution of the NiMo ore with N-235. The extraction efficiency of Mo was
99.4% under optimal conditions: N-235 concentration 15 V%, O/A ratio 1:4, feed
solution pH 3, contact time: 5 min, 20C. Yang et al., (2009) study the extraction of
molybdenum from bismuth molybdenum leach liquor. The results showed that 15102
M N235 in kerosene, a 3 min period of equilibration and a pH 0.4 were sufficient for the
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extraction of molybdenum. This molybdenum-loaded organic phase was almost
completely stripped using ammonia solution higher than 10 vol.%. The extraction
kinetics of molybdenum with Triotylamine (N235), showed that the extraction regimes
are mixed controlled (Zhen-Ning et al., 2010).
6. 3. Synergistic Extraction
Synergism refers to the phenomenon where the extraction of metal ions in the presence
of two or more extractants is more than that expected from the sum total of the individual
extractants. Though solvent extraction of molybdenum using a single extractant is
discussed above, there are numerous applications of synergistic extraction using a
combination of suitable extractants. Major advantages of the synergistic extraction
include low ligand inventory and the possibility of extraction from a high concentration
of acids or complexing agents. Several researchers have been early reported the
extraction of molybdenum using synergistic extraction (Urbanski et al., 1976; Karagiozov
and Vasilev, 1979; Maria et al. 1999).
Behera et al., (1993) studied the extraction of molybdenum by using mixture of 5% (v/v)
bis(2,2,4-trimethylpentyl) dithiophosphinic acid (Cyanex 301) and triisodecylamine
(Alamine 310). The extraction efficiency reach 91% and the extraction takes place by
cation exchange:
MoO2(H2PO4)+(aq) + 2HR(org) MoO2R2(org) + H3PO4(aq) + H+(aq)) (7)
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A mixture of D2EHPA and hydrogenated tetra propylene (HTP) was used to extract Mo
from a sulfate leaching solution produced from the treatment of uranium ore (Lecarme et
al., 1997). A (3070, v/v) D2EHPA-HTP solvent was able to selectively extract 99% of
the Mo, leaving other impurities behind, such as P, V and Si.
Xiong et al., (2011) reported the extraction of molybdenum(VI) from chloride media by
mixtures of bis- (3,5-dimethylhexyl-4-methylhexyl) amine N298 and tributylphosphate

(TBP). The stoichiometries of the extracted complexes with the synergistic mixtures have
been determined by numerical methods to be (R2NH2Cl)3/2. H2MoO4.1/4B for Mo(VI).
The logarithm of the equilibrium constant was calculated to be 2.25.
6. 4. Membrane Based Separation
This branch of separation science has gained attention in the past few decades essentially
due to its cost effectiveness in the treatment of industrial effluents, water purification, gas
separation, etc. Carrier-mediated transport of metal ions across liquid membranes is one
of the options for the recovery of valuable metals from various waste streams. (Nakashio
et al., 1993; Noble et al., 1995)
Amongst several membrane-based techniques, supported liquid membranes (SLMs) are
particularly fascinating essentially due to their selectivity and simplicity. However, SLM-
based separations have a major disadvantage of physical stability. Due to the advent of
polymer inclusion membranes (PIM) and HFSLMs, several groups have shown keen
interest in these techniques. Whereas hollow-fiber based separations offer the distinct
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advantage of efficient mass transfer due to large surface-to-volume ratio, PIMs offer the
advantage of carrier immobility. Liquid emulsion membrane (LEM) known to be one of
the most effective methods for separation and concentration when the material being
extracted is present in very low concentration. LEM process involves simultaneous
extraction and stripping in one step (Draxler et al., 1988). A typical process diagram of a
molybdenum LEM system is exhibited in Fig. 11.

Kulkarni et al., (2002) investigated the The removal of molybdenum from its
dilute aqueous solution through liquid surfactant membranes. Aliquat 336, monesan and
sodium hydroxide were used as a carrier, surfactant and stripping agent, respectively. It
was found that molybdenum extraction was maximum when the internal phase
concentration of caustic was kept as 500 molm3 and pH of the feed phase at 4. It was
found that swelling increased with the concentration of surfactant and internal phase base
concentration.
Basualto et al., (2003) reported the extraction of molybdenum(VI) ions using a supported
liquid membrane containing the extractant Alamine 336 (a long-chain tertiary amine) as
mobile carrier. The results showed that the feed solution acidity, the carrier extractant
concentration in the organic liquid film strongly affect on molybdenum extraction as
shown in Fig. 12. The maximal apparent permeability of molybdenum was achieved
when the pH of feed solution is adjusted around a value of 2.0 with sulphuric acid and if
a 1.0 mol/L Na2CO3 is employed as stripping solution. The molybdenum(VI) permeation
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through the liquid membrane was enhanced when a 0.02 mol/L concentration of the
amine carrier in the organic film was used.
Marchese et al., (2004) studied the transport of molybdenum with Alamine 336 using
supported liquid membrane. The experimentally observed results indicate that the highest
extraction of molybdenum occurs when the pH of the feed solution is adjusted to a value
of 2.0. Under such a condition, Mo(VI) exists predominantly as the H2MoO4 (molybdic
acid) species. An equimolar relationship was found between this species and the carrier
agent when they reacted to form the metal complex at interface. An increase in the metal
transport was also observed as the alkalinity of the stripping solution was increased to
around pH 11.5. The results suggest a stripping reaction at the membrane-stripping
solution interface, which produced the rupture of the molybdenum complex, releasing the
Mo(VI) as molybdate ion into the receiving aqueous phase and subsequently the
regeneration of amine carrier extractant as shown in Fig. 13.
Valdes et al., (2009) reported the mass transfer of a membrane-based solvent extraction
process to remove molybdenum(VI) from aqueous solutions. An effective kinetics
relationship was correlated in order to describe the rate of the complex formation at the
aqueousorganic interface. This methodology allows obtaining a local quantification of
the complex formation, which can be used to extrapolate or to scale-up this type of
systems. The availability of the limiting reactant at the interface given by the
hydrodynamic conditions in the membrane contactor and mass transfer in the membrane
pores will establish the maximum trans membrane flux value. The mass transfer flow is
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controlled by the rate of the complex formation and the diffusion through the membrane
pores.
6. 5. Ion Exchange Extraction
Several investigation have been carried out on the extraction of molybdenum using ion
exchange resin (Soylak et al., 1996; Sung et al., 1997; Kekesi et al., 2005)
Henry and Lierde (1998) investigated selective separation of vanadium from

molybdenum by electrochemical ion exchange. The principle is that V(V) and Mo(VI)
are adsorbed synchronously from neutral solution by Amberlite IRA 94S resin. In the
process, V(V) is selectively desorbed with molybdenum, then it is reduced to V(IV) by a
cathode mixed with ion exchange resin. The further elution of molybdenum with alkaline
solution leads to the recovery of a pure molybdate solution characterized by a molar ratio
of V to Mo of 1/l 000 after a post-precipitation at pH 8.
Liansheng et al., (2001) found that by using the moving packed bed ion exchange resin
(D 290) to remove molybdenum, under the condition that contact time above 100 min,
temperature of the resin layer below 50C, and Mo/WO3 is (0.5-1.5) 10-2 in the feed
liquor, the Mo content in the purified solution can be controlled below 0.005 g/l; the Mo
removal efficiency is above 99%.
Kononova et al., (2003) reported the sorption properties of the acrylic anion exchangers
AN-108P and AN-108TP based on methylacrylate and long-chained cross-linking agent
copolymer by means of the saturation method as well as by electron microscopy, IR and
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electron spectroscopy methods. It was found that AN-108TP is suitable for the selective
Mo(VI) sorption from nitric acid solutions obtained after the breakdown of the
molybdenum-containing ores and concentrates.
Zhongwei Zhao et al., (2010) investigated the extraction of molybdenum from Ni-Mo ore
leach liquor using D314 resin (equal to resin Amberlite IRA 67/68 in USA or resin Ap-49
in Germany). The results showed that at a pH value of 2.5 about 98.4% of Mo can be
retained at the flow rate 180ml/h, and the working exchange capacity of D314 can reach
128.2 mg/ml resin. After desorption by ammonia (7 M) for 45 min, 99.4 g/L
molybdenum solution can be obtained with desorption percent of 99.5%. High quality
ammonium molybdate tetrahydrate can be obtained though re-crystallization.
6. 6. Precipitation
Chemical precipitation method is widely used in the hydrometallurgical processes of
purification, extraction and separation, and is characterized by low cost, easy operation,
large capacity, high efficiency, and friendly environment. Several researchers have been
early investigated selective precipitation of molybdenum from different solution (Meyer
1963; Yatirajam et al., 1975; Warren et al., 1982).
Litz and John (1989) reported precipitation of molybdenum from vanadium/molybdenum
solution. The molybdenum is precipitated in the form of ammonium octamolybdate with
a ratio of vanadium to molybdenum about 1/400 in an initial crystallization and a ratio of
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about 1/1300 in a subsequent recrystallization, and the vanadium content in ammonium
octamolybdate products also reaches 0.05%.
Rokukawa (1993) investigated selective extraction of molybdenum using different
ammonium salts. The results showed that, by using 0.017 g/l CH3COONH4, about 99%
of the molybdenum reported to precipitate.

Li (2012) studied the precipitation of molybdenum using nascent Fe(OH)3 from
complex Ni-Mo leach solution by adding NaHCO3. The experimental results indicate that
above 99% of molybdenum can be extracted in 2h at 251C under the conditions of
mole ratio of Fe3+/Mo 2.2~2.5, mass ratio of NaHCO3/Mo 0.7~1.5. About 92% of Mo in
the Fe(OH)3 precipitation can be leached by NH3H2O, and then about 100g/L Mo of
ammonium molybdate solution was obtained and can be used to produce ammonium
molybdate.
6.7. Comparative Analysis Of Separation And Purification Processes
Table 5, summarize separation and purification processes of molybdenum from leach
liquors, their strength and weakness, and critical operating variables.
Solvent extraction, membrane based separation, ion exchange and precipitation are the
main technologies for the separation and purification of molybdenum from leach
solutions. Precipitation is more economic and simple operation, but, it is difficult to
obtain high purities (>99%) of products by this technology. Membrane based separation
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is used for extraction of molybdenum from molybdenum solutions or co-recovery of
other valuable metals. The scale of application of ion exchange in industry is limited.
Solvent extraction is the well-established unit operation for purification of molybdenum
in their leach solutions. -hydroxy oximes are promising extractants for the effective
separation and recovery of molybdenum(VI) from acidic leach solutions, LIX 63 was
used for selective extraction of molybdenum from an leach liquors containing various
other metal values, such as copper, arsenic, iron, bismuth, antimony, tin. The efficiency
of molybdenum extraction by amines decreases as follows: quaternary > tertiary >
secondary > primary. Although certain difficulties are encountered in stripping
molybdenum using quaternary ammonium compounds, tertiary amines have found wide
application in practical extraction systems. Extraction of molybdenum from the sea
nodule leach solution containing different metal values was achieved at equilibrium pH
1.62 using 10 % v/v Alamine 304-1 for two stages at A:O=12:1 phase ratio. A mixture of
5M NH4OH+2.5 M (NH4)2CO3 showed rapid and very good stripping efficiency as
compared to other ammonical reagents. The stripping of molybdenum in 2-stages at the
phase ratio of A:O=1:16, resulted in quantitative stripping. Subsequently, pure forms
(99.9%) of (NH4)4 Mo2O6 and MoO3 were recovered from the stripped solution.
vanadium is warranted. Triotylamine (N235), was used as a promising reagent for
extraction of molybdenum from aqueous solution containing Ni or Bi.
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7. SUMMARY AND FUTURE RESEARCH AND DEVELOPMENT
Traditional methods of molybdenum extraction, namely flotation / leaching /
roasting of molybdenite concentrate at high temperatures are applicable for high grade
MoS2 concentrates derived from the primary molybdenum ores and as by-product from
Cu-Mo porphyry ores. An ever increasing quantity of complex low grade molybdenite is
being produced from secondary sources as by-product of copper and uranium mining.
Such secondary low-grade MoS2 concentrates require extensive modification in the

already complex conventional routes. Therefore, several researches have been made on
the development of molybdenum extraction routes. Among these methods plasma
smelting and lime-scavenged reduction are useful for high grade concentrate only. On the
other hand, pressure oxidative leaching, alkali fusion, nitric acid break down,
hypochlorite leaching, oxidative roasting followed by sulfuric acid and water leaching,
pyrochlorination, lime-scavenged reduction and bioleaching appear to be suitable for the
treatment of low grade concentrates. Bioleaching offers good prospects for recovering
valuable metals and at the same time generates much less environmental pollution.
However, much more research work is needed for its commercialization. Further R&D
efforts are recommended on five inherently attractive routes for molybdenum
separation,viz, oxidative roasting followed by sulfuric acid and water leaching, lime-
scavenged reduction, pressure oxidative leaching, pyrochlorination, and bioleaching.
Solvent extraction is highly selective for recovery of molybdenum and the most
promising method recommended for future research and development. Among these
extractants Organophosphorous acidic extractants such as di-(2-ethylhexyl) phosphoric
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acid (D2EHPA), 2-ethylhexyl phosphonic acid (PC-88A), bis(2,4,4-trimethylpentyl)
dithiophosphinic acid (Cyanex 301), and bis(trimethylpentyl) phosphinic acid (Cyanex-
272) and -hydroxy oximes such as LIX 63. The extraction efficiencies of
organophosphorous acidic extractants for molybdenum follow the order:
Cyanex 301 > PC-88A > Cyanex 272 > Cyanex 302.
Membrane based separation is next for selective extraction of molybdenum, purification
of molybdenum solutions or co-recovery of other valuable metals. The scale of
application of ion exchange in industry is limited although it can be used to separate
molybdenum completely and to produce high purity products. Precipitation offers low
cost and simple operation, however, high purities (>99%) of molybdenum products
cannot be achieved. Further R&D efforts are recommended on three inherently attractive
routes for molybdenum recovery/purification from solution, viz, solvent extraction with
new chelating extractants, membrane based separation, and ion exchange.
Principal technological schemes of processing of molybdenum-containing raw materials
are illustrated in Fig. 14.
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Table (1): molybdenum mine production by country
Countries Production (MT)
China 94000
US 56000
Chile 39000
Peru 12000
Canada 9100
Mexico 8000
Armenia 4200
Russia 3800
Iran 3700
Mongolia 3000
Uzbekistan 550
Kazakhstan 400
Kyrgyzstan 250
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Table (2): Comparative analysis of processes for molybdenum raw material digestion
Strengths + Critical Operating references
Weaknesses
Pyromet
Oxidative Rhenium by product T = 9095 C, = 2 Balgaeva et al., 2007
Roasting 96.5% Mo is h, (S : L) = 1 : (45). Ovtsyn et al., 2009
extracted, 85% of Re 600 C, air 100120

sublimes in 0.5 h m3/h
Liquation Extraction of Mo, 80-100% Na2CO3, Urbazayeva et al., 1999
Smelting Cu, Bi reach 80%, lump silicate content
95% and 100% 20%, 950-1150C
respectively
Plasma 40 kWh/kg of 26 % C, 2500 Timoshevsky et al.,
Smelting Mo.100% MoS2 2600K 2006
decomposition
Direct SO2 pollution Different reductant Prasad et al., 1997;
Reduction abatement 40% (H2, CO and C) 1993. Habashi and
reduction was 1073K in 3.6 ks Dugdale 1973
obtained hydrogen flow rate of
3.93cm3s-l.
Chlorination SO2 free fluidised-bed reactor Nair et al., 1987, 1988
in the presence of
oxygen at 300K
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Pyro-
Hydromet
Oxidative Extraction of Mo, 240 C for 1 h; 32 ml Mingyu et al., 2010
roasting, Ni reach 92.1% and sulphuric acid/100 g
Sulphation 83.5%, respectively. roasted NiMo ore,
roasting, water water leaching for 2
leaching h at 98C and S/L of

1:2.
Calcification SO2 free, Extraction 36 g CaO to 100 g Xue et al., 2011
roasting, of Mo, Ni reach NiMo ore. 70 ml
Sulphation 97.23% and 93.16%, 98% sulphuric acid at
roasting, respectively. 240C for 2 h
Hydromet
Pressure Extraction of Mo S/L ratio 1:8, 180C, Smirnov et al., 2010
oxidative reach 99.6% 2 2.5 MPA for 2 to
leaching 4h.
Alkali fusion High leaching 850C with 5wt% Kahrizsangi, R., (2010)
and alkali reaction kinetics excess carbonate
leaching
Acidic leaching
HCl Maximum extraction t: 4 h; HCl: 20%; S/L Zhan-fang Cao et al.,
of molybdenum ratio: 1:10; t: 70 C; 2009
(98%) agitation speed: 500
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rpm, the molar ratio
of NaClO3 to MoS2:
3.21.
H2SO4 The reaction was 2M H2SO4, 0.4 M Antonijevic et al., 1992
chemically Na2Cr2O7 for 2h at
controlled, and the 363K
reaction rate was

first-order relative to
the sodium
dichromate and
sulfuric acid
concentrations.
HNO3 High purity of T = 9095C in two Medvedev et al., 2009
CaMoO4 stages decomposition
100 g/L H2SO4 and
30% HNO3
Electro- dissolution rate of S/L ratio: 1:25, NaCl Jiang, 1984; Zhan-fang
oxidation molybdenite reach 4 M, stirring speed Cao et al., 2010
dissolution 99.97%. process is 400 rpm, operating
diffusion controlled potential 3.0 V,
with apparent anode ampere density
activation energy 800 A/m2, pH = 9,
8.56 kJ/mol 25C, t = 240 min.
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Hypochlorite selective extraction time, 4 h; 10% Youcai et al., 2011
leaching of Mo over Cu. NaOH; 8% NaOCl;
Mo> 99.9% while S/L, 1:10; T, 50 C;
Cu = 0.01 and, agitation speed
500 r/min
Bioleaching The rate of Eh 750 mV to 800 Gregory et al., 2008.
bioleaching of high mV (s.h.e.). 3.22 mg Chen et al., 2011

purity molybdenite Mo/m2/d at 24C.
increased with 100 g/L of mineral
decreasing particle density, 65 C, pH=2
size. leaching rates and 1.0 L/min of the
of Ni and Mo aeration rate.
reached 79.57% and
56.23% respectively
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Table(3): standard gibbs free energy data (at 25C) of Mo (IV) species for stabcal
simulation (based on Young Nam et al., 2011) .
Species Standard Gibbs free energy, kJ/mol
MINTEQ Russia NBS HSC
MoO42 (a) 836.2979 838.0552 836.2979 836.1849
HMoO4 (a) 860.8362 866.632 863.5776 868.6193
MoO3 (s) 644.8351 667.9714 667.9714 667.4777

MoO22+ (a) 411.2872 411.2872 - 411.237
H2MoO40 (a) 882.8972 877.1337 - 882.7194
MoO2(OH)+ (a) 645.8840 645.884 -
MoO30(s) 667.7664 667.7664 -
Molybdite
Mo7O246 (a) 5208.051 - - 5250.25
HMo7O245 (a) 5244.506 - -
H2Mo7O244 (a) 5271.802 - -
H3Mo7O243 (a) 5290.333 - -
H2MoO40 (s) 909.7991 - - 912.2668
CuMoO40 (s) 845.4471 809.604 - 810.2609
Fe2(MoO4)30 (s) 2719.968 2719.968 2719.968 2719.968
MoO3H2O0 (s) 916.9152
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Table (4): specifications of molybdenum products required for different markets.
Molybdenum Example
products
specifications
Steel industries Technical molybdic Technical molybdic Ferromolybdenum
oxide-powder oxide- Briquettes industries
Mo:57.00%min. Mo:57.00%min Mo: 65.00% min.

Cu: 0.50% max. Cu: 0.50% max Cu:0.50%max
S: 0.10% max. S: 0.10% max P:0.07%max
C: 0.10% max. C: 0.10% max C: 0.10% max
P: 0.05%max. P:0.05% max S: 0.10% max.
Pb: 0.05%max. Pb: 0.05% max Si: 1.50% max.
Chemical Technical molybdic pure molybdic pure molybdic
industries oxide-high oxide-Sandy grade oxide-floury grade
solubility
Mo: 57.00% min. Mo: 66.60% Mo: 66.60% typical
typical
Cu: 0.50% max. As: 10 ppm max. As: 10 ppm max.
S: 0.10% max. Al: 10 ppm max. Al: 10 ppm max.
P: 0.05% max. Fe: 20 ppm max. Fe: 20 ppm max.
Pb: 0.05% max. C: 50 ppm max. C: 50 ppm max.
K2O: 0.20% max. Na: 10 ppm max. Na: 10 ppm max.
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Solubility in Si: 10ppm max Si: 10 ppm max.
ammonia
98.50% min.
S: 30 ppm max. S: 30 ppm max.
W: 150 ppm max. W: 150 ppm max.
Metallic and Molybdenum Molybdenum metal Molybdenum metal
super alloys dioxide powder Mo% powder high denisty

industries 99.95% min.
Mo% 74.5% min O: 1 ppm max Mo% 99.5% min.
C: 100 ppm max C: 50 ppm max O: 1.5 ppm max
S: 50 ppm max Cu: 10 ppm max C: 100 ppm max
Fe: 50 ppm max Fe: 20 ppm max Cu: 100 ppm max
K: 100 ppm max K: 40 ppm max Fe: 1.0 ppm max
W: 150 ppm max Na: 20 ppm max S: 100 ppm max
Pb: 20 ppm max Si: 1 ppm max
Si: 35 ppm max
W: 150 ppm max
Molybdenum Metal Molybdenum Metal
Briquettes Briquettes Vacuum
Grade
Mo% 99.80% min Mo% 99.80% min.
Fe: 50 ppm max Fe: 50 ppm max
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K: 40 ppm max K: 40 ppm max
Mn: 10 ppm max Mn: 10 ppm max
Na: 20 ppm max N: 50 ppm max
O: 800 ppm max Na: 20 ppm max
Pb: 20 ppm max O: 200 ppm max
S: 10 ppm max Pb: 20 ppm max
Si: 35 ppm max Si: 35 ppm mx

W: 300 ppm max Si: 35 ppm mx
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Table (5): Comparative analysis of processes for molybdenum separation and purification
from leach liquors
Strengths + Critical Operating References
Weaknesses
SX Chelating
extractants
Organophosphates Mo extraction > 0.15 M PC-88A Pathak et al., 2010

98% in 20 min. (O/A = 1:1) at 2 M Saberyan et al.,
Temperature and HNO3. 0.06 M 2003. Knyazkina
diluent Cynaex 301 for 5 et al., (2010)
independent, fast min. pH ~ 2, 0.16
reaction. Mo M Cyanex 272 for
extraction > 93%, 10 min O:A = 1:1
reaction proceeds
rather slowly, H =
19.07 kJ/mol
Oximes Selective extraction 40% LIX 63 in Pingwei Zhang et
of Mo over other Exxsol D80, pH ~ al., 1996
metals, Mo 1.5
extraction > 99.9%
Solvating
extractants
TBP Exothermic 3 M TBP in Alamdari, et al.,
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reaction, H = - kerosene 2000
75.90 kJ/mol, S =
-0.21 kJ/mol
TPPO Selective 6% TPPO in Santosh et al., 1996
separation of Mo toluene, 2.54 - 3.10
from Rh, the M HCl, 3.76 - 3.98
extracted species M HBr.

was MoO2Cl2.
2TPPO
Ion Pairs High purity Alamine 304-1 An et al., 2009a,b
(>99.9%) MoO3 (10%, v/v). pH Parhi et al., 2011
was obtained. pure 1.62, 10 % v/v Zhao et al., 2011
forms (99.9%) of Alamine 304-1 in
(NH4)4 Mo2O6 and two stages at
MoO3 were A:O=12:1. 15% N-
recovered. Mo 235, O/A ratio 1:4,
extraction was feed solution pH 3,
99.4% in 5 min. 5 min
Synergistic Mo extraction was 5% Cyanex 301 + Behera et al., 1993.
extraction 91%. selectively 5% Alamine 310. Brassier-Lecarne et
extract 99% of the (3070, v/v) al., 1997
Mo, leaving other D2EHPA-HTP
impurities behind,
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such as P, V and
Si.
IX
Resins Mo removal ion exchange resin Xiao Liansheng et
efficiency is above (D 290), for100 al., 2001.
99%. Tungesten as min, T of the resin Zhongwei Zhao et
by product. 98.4% layer below 50C, al., 2010.

of Mo can be Amberlite IRA
extracted. Fast 67/68, feed
reaction, high resin solution pH 2.5,
capacity flow rate 180ml/h.
Membrane
Liquid membrane High Mo pH ~ 2, 1.0 mol/L Basualto et al.,
permeation Na2CO3, 0.02M 2003. Jose
alamine 336. Marchese et al.,
2004.
Precipitation 99% of the 0.017 g/l Rokukawa 1993
molybdenum CH3COONH4. Jiangtao Li 2012
reported to mole ratio of
precipitate. Mo Fe+3/Mo 2.2~2.5,
extraction was mass ratio of
99%. NaHCO3/Mo
0.7~1.5, for 2h
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93
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251C.
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Fig. 1. Flow-sheet for the extraction of molybdenum from low-grade molybdenite
concentrate by oxycblorination (based on Nair et al., 1988).

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Fig. 2. Flow sheet of molybdenum extraction from NiMo ore. (based on Wang et al.,
2009).
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Fig. 3. Flow sheet of treatment of low-grade sulphidic molybdenum ores (based on van
den Berg et al., 2002).

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Fig. 4. Flow sheet of the MoO3 production from molybdenite by the alkali fusion process
(based on Kahrizsangi, R. E., 2010).

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Fig. 5. Flow chart of molybdenum extraction from NiMo ore. (based on Zhao, Z., 2010).
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Fig. 6. The concentration of NaClO and NaClO3 in different conditions (based on Jiang,
1984)
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Fig. 7. EhpH diagram based on Stabcal simulation for a solution containing 0.63 M Mo,
0.035 M Cu and 0.13 M Fe (at 25C) (based on Young Nam et al., 2011).
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Fig. 8. Stabcal simulation (for 25 C) for a solution containing 0.63 M Mo, 0.035 M Cu
and 0.13 M Fe using (a) MinteqA2 or (b) Russian database available within the Stabcal
program, (c) HSC database, (d) same as (a) at mg/L range. Solid area is shaded in (a)(d)
(based on Young Nam et al., 2011).

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Fig. 9. Extraction as a function of pH for the systems of V(V) (730 ppm)/ M Alamine
336-toluene and Mo(VI) (2000 ppm)/0.1 M Alamine 336- toluene (based on Olazabal et
al. 1992).
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Fig. 10. Extraction as a function of pH for the systems of V(V) (730 ppm)/0.1 M Aliquat
336-toluene and Mo(VI) (2000 ppm)/0.1 M Aliquat 336-Toluene (based on Olazabal et
al. 1992).
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Fig. 11. Block diagram for molybdenum LEM process. (based on Kulkarni et al., 2002)
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Fig. 12. Dependence of molybdenum extraction on pH and Alamine 336 concentration.
Feed solution: 0.001 mol/L Mo(VI). (based on Carlos Basualto et al., 2003).
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Fig. 13. Schematic representation of the interfacial chemical reactions for Mo
permeation. (based on Jose Marchese et al., 2004)

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Fig. 14. Principal technological schemes of processing of molybdenum-containing raw
materials.
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This article was downloaded by: [Moskow State Univ Bibliote]

On: 06 February 2014, At: 03:28

Mineral Processing and Extractive Metallurgy Review:

Molybdenum Metallurgy Review: Hydrometallurgical

To link to this article: http://dx.doi.org/10.1080/08827508.2013.868347

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Molybdenum metallurgy review

Molybdenum metallurgy review: hydrometallurgical routes to recovery of

T. A. Lasheen1, M. E. El-Ahmady1, H. B. Hassib2, A. S. Helal1,

Address of Corresponding to A. S. Helal: ahmed_samihelal7@yahoo.com,

stringent environmental requirements, the traditional technology shows its shortcoming

for molybdenum production from various resources, particularly focusing on recent

developments in direct hydrometallurgical and recovery processes to identify potential

sources of molybdenum, products, and by-product such as uranium which can be

purification from solution, which are potentially applicable to leach solutions of

exchange, membrane based separation, and precipitation. Solvent extraction is highly

extraction of molybdenum, purification of molybdenum solutions or co-recovery of other

KEYWORDS: molybdenum metallurgy, recovery of molybdenum, solvent extraction,

ion exchange, and membrane based separation

Molybdenum is a refractory metallic element used principally as an alloying agent in cast

corrosion-resistance, and oil and gas industry.

To achieve desired metallurgical properties, molybdenum, primarily in the form of

molybdic oxide (MoO3, called MoX) or ferromolybdenum (FeMo), is frequently used in

combination with or added to chromium, manganese, nickel, niobium (columbium),

tungsten, or other alloy metals. The versatility of molybdenum in enhancing a variety of

alloy properties has ensured it a significant role in contemporary industrial technology,

refractory metal and in numerous chemical applications, including catalysts, lubricants,

briquettes, and pigments (USGS, 2011).

essential factor in green technology, where it is used in high-strength steels for

grade molybdenum-bearing steels.

years. Approximately 60 new projects and expansions could potentially produce

molybdenum, yielding an additional 240,000 t/yr of molybdenum (Roskill, 2012).

growth rate, primarily fueled by rapid increases in Chinas industrial growth.

Molybdenum demand continues to be driven largely by the steel sector. As emerging

expected to need increasing amounts of molybdenum, and this trend is expected to

market from alternative and renewable energy.

essential that alternative, economical processing routes for treating materials be

sulfides, oxides, uranium by-product. So in this review conventional pyrometallurgical

processes and pyro-pre-treatments for production of major molybdenum products are

briefly outlined. Recent developments in direct hydrometallurgical processes for leaching

and recovery of molybdenum are reviewed in details.

further research and development.

2. MOLYBDENUM RESOURCES AND MARKET RESEARCH

molybdenum-bearing grain (1 0.6 m) in a pyroxene fragment taken from Mare

is molybdenite (MoS2). Molybdenum is also found in several minerals, such as bright

orange-red to yellow-orange Wulfenite (PbMoO4) and transparent adamantine blue,

greenish brown, yellow to grey Powellite (CaMoO4).

2.1. Molybdenum Reserves

World molybdenum reserves and production capacity were concentrated in a few

(molybdenum contained in concentrate), of which, in descending order of production,

United States, mine production of molybdenum concentrate in 2011 increased by 7% to

In North America, most Canadian reserves of molybdenum were contained in porphyry

Canadian reserves were associated with minor porphyry copper-molybdenum deposits in

New Brunswick and Quebec. The La Caridad porphyry copper-molybdenum deposit in

substantial reserves. Reserves of molybdenum in China and the Commonwealth of

lacking (USGS, 2011).

2.2. Molybdenum Production By Commercial Processes

impurities. Processes used for treatment of moly intermediate depend mainly on

concentration of molybdenum and concentration of impurities.

Primary molybdenum production continued at the Ashdown Mine in Nevada, the

Henderson Mine produced 17,240 t of molybdenum in 2011, a 5% decrease compared

chemical-grade molybdenum concentrates, which typically are further processed into

value-added molybdenum chemical products. The Henderson operation consists of a