JOM

DOI: 10.1007/s11837-012-0457-3
 2012 TMS

Extraction of Molybdenum from Molybdenite Concentrates

with Hydrometallurgical Processing

KAIXI JIANG,1,2 YUFANG WANG,1 XIAOPING ZOU,1 LEI ZHANG,1

and SANPING LIU1

1.—Beijing General Research Institute of Mining and Metallurgy, Building 23, Zone 18 of ABP,
No. 188, South 4th Ring Road West, Beijing 100160, China. 2.—e-mail: jiangkx@bgrimm.com

Molybdenite concentrates are usually treated by roasting, but low-concen-

tration SO2 pollution is an associated problem. A hydrometallurgical process
with pressure oxidation leaching (POX) and solvent extraction (SX) was
developed in recent years. During POX, the oxidation of molybdenum (Mo) is
above 98%. More than 95% of the rhenium (Re) and 15% to 20% of the Mo are
leached into solution. The sulfur in the concentrate is converted to H2SO4,
which results in high acidity of the solution. SX was used to recover the Re and
Mo from the solution. The extraction of Re and Mo were above 98%. The
loaded organic reagent is stripped with ammonia. More than 98% of the Mo
can be stripped from the organic phase. Compared with the roasting process,
the total recovery of Mo increased from 93% to 97% and that of Re from 60% to
90% when POX and SX are utilized.

INTRODUCTION STATUS OF THE MOLYBDENITE PROCESS

Molybdenum (Mo) is widely used in special steels,
aviation, alloys, chemistry, electronic and medical
industries. Molybdenite is the main resource for the
extraction of Mo, and more than 90% of Mo is pro-
duced from molybdenite. According to a United
States Geological Survey (USGS) report in January
2012, the global Mo reserve was 10,000 kt Mo,
mainly lying in China, the USA, Chile and Peru etc.
China’s reserve is 4300 kt Mo, accounting for 43%
of the global total.1 China’s Mo reserve is mainly
located in the Henan, Shaanxi, Jilin, and Inner
Mongolia Provinces.
China’s Mo industry has expanded sharply in
recent years. China is currently the largest Mo
producer and consumer in the world. According to
statistics of the China Nonferrous Metals Industry
Association, in 2010, China’s molybdenite produc-
tion was 93.6 kt Mo, accounting for 36% of the glo-
bal total, up from 25% in 2006. China’s Mo
production is mainly located in Henan, Shaanxi,
Inner Mongolia, Hebei, and Liaoning Provinces,
accounted for 91% of China’s total. In 2010, China’s
Mo consumption was 60 kt. China’s consumption
increased from 14% in 2006 to 29% of the world’s Mo
in 2010. The main products are ferromolybdenum
and ammonia molybdate.
The main extraction processes for molybdenite
concentrates include direct oxidative roasting,
roasting with lime, and pressure oxidation leaching
(POX).2
Direct Oxidative Roasting
Due to its low cost and easy operation, the direct
oxidative roasting process is widely used around the
world by large manufacturers. The molybdenite is
roasted at 550C to 680C and oxidized into MoO3.
After purification in mixed acid solution, the calcine
is leached with ammonia, and the solution is pre-
cipitated by nitric acid to produce ammonium
molybdate. The main equipment for roasting
includes rotary kilns and multiple-hearth furnaces
in China. The recovery of Mo from roasting opera-
tions is less than 93%. The two largest manufac-
turers in China, Jin Duicheng and Luanchuan, set
up an acid production system in 2009 and 2010,
respectively. Jin Duicheng mixed the low-density
gas with pyrite roasting gas to enhance the SO2
density to produce the acid. Luanchuan introduced
WSA technologies to produce sulfuric acid from low-
density SO2 gas directly. Other plants mainly
absorb the gas with lime. Although the low-density

SO2 off-gas is sent to produce sulfuric acid or to be
absorbed by milk of lime, there is still some SO2
discharged into the air, causing environmental pol-
lution, and the production and investment cost for
off-gas treatment is high.
Rhenium (Re) is an important new material in
national defense, space flight, nuclear energy, and
electronics due to its high melting point, high
strength, plastic properties, and significant creep
resistance. There are no Re ores in the world. Re
mainly coexists with Mo. In this process, Re can be
recovered from the off-gas, but the recovery is less
than 60%.
Roasting with Lime
To solve the SO2 pollution problem and to improve
the Re recovery ratio, roasting with lime was uti-
lized, and the sulfur in the concentrate was con-
verted to calcium sulfate. According to study
results, Re recovery was 70% with the roasting–
leaching–ion exchange process, and the usage of
lime was about twice the weight of the concentrate.
The amount of slag produced was very large.3,4
Pressure Oxidation Leaching Process
Pressure leaching technology is widely used in
nonferrous metallurgy industries, such as for zinc,
aluminum, nickel, gold, etc., due to its high extraction
and short reaction time. Sulfide ores are leached di-
rectly without roasting, which can avoid SO2 pollu-
tion. According to the leaching medium, the pressure
leaching process can be divided into two types: acid
pressure leaching and alkaline pressure leaching.
In the alkaline pressure leaching process, the
concentrate is leached with NaOH or NaCO3 at a
specified temperature and oxygen pressure. The Mo
and Re are leached into the solution from sulfide
minerals according to the reactions
MoS2 þ 6NaOH þ 9=2O2
¼ Na2 MoO4 þ 2Na2 SO4 þ 3H2 O
2ReS2 þ 10NaOH þ 19=2O2
¼ 2NaReO4 þ 4Na2 SO4 þ 5H2 O
Compared with acid oxidation, the reaction tem-
perature, operation pressure, and equipment cost
are lower, and less impurities are contained in the
Table I. Main chemical composition of the Mo concentrate
Element Mo Re S Cu
Content % 44.95 0.067 37.00
Element Zn F Cl
Content % <0.005 <0.03 0.032
Jiang, Wang, Zou, Zhang, and Liu
solution for alkaline processing. However, con-
sumption of sodium hydroxide is very high, which
leads to a high production cost. In 1990, this process
was put into production in Baoji, Shaanxi Province,
China, with designed capacity of 200 t/a of ammo-
nium molybdate. However, due to the high produc-
tion cost, it was soon stopped.
In acid POX, the sulfur in the molybdenite is
oxidized into sulfuric acid instead of SO2 and most
Mo is left in the residue as oxide. Meanwhile, some
impurities are leached into the solution, which can
improve the quality of the products. About 80% of
the Mo is left in the residue in the form of H2MoO4
or MoO3, and the rest is leached into solution in the
form of MoO2(SO4) or Mo2O5(SO4). Most of the Re is
leached into the solution. The main reactions for
pressure oxidation are
MoS2 þ 3H2 O þ 9=2O2 ¼ H2 MoO4 þ 2H2 SO4 (1)
4ReS2 þ 19O2 þ 10H2 O ¼ 4HReO4 þ 8H2 SO4 (2)
In recent years, other research has been carried out
on extraction of molybdenite, e.g., electrochemical
processes, vacuum metallurgy, but these technolo-
gies have not been utilized commercially. This paper
discusses acid pressure oxidation of molybdenite.
MATERIAL
The raw material for this study is molybdenite
concentrate with Mo grade of 44.95% (Table I).
Molybdenum sulfide was the main mineral identi-
fied by x-ray diffractometry. According to chemical
analysis, more than 99% of the Mo exists as sulfide.
Of the concentrate particles, 91.77% are smaller
than 200 mesh.
The Re grade of the concentrate is 0.067%
according to analysis results, which is high for
molybdenites and should be recovered for economic
operation.
EXPERIMENTAL DETAILS AND RESULTS
Pressure Oxidation
Nitric acid or nitrate has been used in the past as
an additive to enhance the reaction efficiency and
decrease the reaction temperature and retention
time. Under 150C with reaction time of 2 h, the Mo
oxidation ratio is above 98%. In 1980, this process
was put into production in the Zhuzhou Hard Alloy
Fe Co Mg
2.3 2.95 <0.003 0.18
Si Al Na K
1.84 2.46 0.19 0.2
Extraction of Molybdenum from Molybdenite Concentrates with Hydrometallurgical Processing
Table II. Water vapor pressure as a function of temperature
Temperature (°C) 150 160 170
Pressure (kPa) 485 630 808
Plant in China. The raw material was supplied by
Baoshan Copper Mine, Hunan Province, with Mo
grade of 43% to 47%. However, due to accidents
during operation, this process was stopped a few
years later. In this process, some NOx is produced
and released, causing environmental pollution.
Reactions involving nitric acid include the following:
MoS2 þ 6HNO3 ¼ H2 MoO4 þ 2H2 SO4 þ 6NO
2NO þ 3=2O2 þ H2 O ¼ 2HNO3
In recent years, to solve the NOx problem, tests of
pressure oxidation without nitrate were carried out
by Beijing General Research Institute of Mining and
Metallurgy (BGRIMM). The effects of temperature,
reaction time, additives, oxygen partial pressure,
etc. on the pressure oxidation of molybdenite were
studied in detail. According to the test results,
active carbon can enhance the reaction speed. With
the addition of active carbon, the leaching ratio and
oxidation ratio of Mo increased accordingly.
Temperature and reaction time are important
factors that affect the oxidation. With the increase
of temperature and oxygen pressure, the leaching or
oxidation increased accordingly. The operation
pressure in this process includes two parts: the
steam pressure and the oxygen pressure. The steam
pressure at different temperatures is presented in
Table II. As the temperature ranges from 150C to
190C, the steam pressure increases by about
200 kPa for every 10C interval. At 220C, the
pressure reached 2366 kPa. Thus, with increasing
temperature, the operation pressure increases
sharply at the same oxygen pressure. The published
studies on pressure oxidation were mainly carried
out at 210C to 230C, with operation pressure of
2 MPa to 2.5 MPa. High temperature, high pres-
sure, and high acidity will cause corrosion of the
equipment. Consequently, low temperature and
moderate conditions are targeted. The effect of
temperature on pressure oxidation in this study is
shown in Fig. 1 (with reaction time of 2 h).
Increasing the temperature from 150C to 210C
increases the Mo oxidation from 23% to 98.75%. In
the range of 180C to 210C, the difference is small.
However, the operation pressure difference between
180C and 210C is 900 kPa. Thus, the temperature
of 180C was chosen.
According to the test results, the optimum condi-
tion for POX is: reaction temperature 180C,
180 190 200 210 220 230
1023 1280 1586 1946 2366 2853
Fig. 1. Effect of temperature on pressure oxidative leaching.
reaction time 4 h, and operation pressure 1.6 MPa.
Under this condition, the oxidation of Mo is more
than 99%. The leaching ratio of Re is above 95%.
About 15% to 20% of the Mo was leached into
solution, the rest being left in the residue. The
composition of the leaching solution is (g/L): Mo
7.23, Cu 3.25, Fe 4.68, H2SO4 131.48, Re 0.072.
Solvent Extraction
During pressure oxidation, about 15% to 20% of
Mo and more than 95% of Re were leached into
solution, and the acid concentration of the leaching
solution is greater than 100 g/L. The Mo concen-
tration in the solution was about 7 g/L. For recovery
of Mo/Re from the solution, three processes were
carried out by BGRIMM: ion exchange, carbon
absorption, and solvent extraction (SX).
Ion exchange is used in some plants in China to
recovery Mo from low-concentration solutions in
which the pH is below 2. The absorption capacity of
the resin is large, but if the pressure leaching
solution is neutralized to pH 2 with lime, more than
20% Mo would be lost in the residue. Ion exchange
under high acidity was also tested, but the absorp-
tion capacity of the resin is reduced below pH 2. At
the same time, the acid in the solution was
absorbed, causing high consumption of hydroxide.
Active carbon was also tested for recovery of Mo
from the solution, but compared with the SX results,
the separation is poor, which leads to high impurity
levels in the stripping solution.
 Jiang, Wang, Zou, Zhang, and Liu

N235 was chosen for the SX in this study. The
main reactions for the SX are as follows:
½MoO2 ðSO4 Þ2 2 þ 2Hþ þ 2R3 N
! ðR3 NHÞ2  MoO2  ðSO4 Þ2
2R3 N þ 2Hþ þ SO4 2 ! ðR3 NÞ2 H  HSO4
½MoO2 ðSO4 Þ2 2 þ ðR3 NÞ2 H  HSO4
! ðR3 NHÞ2  MoO2  ðSO4 Þ2 þ SO4 2
ðR3 NHÞ2  MoO2  ðSO4 Þ2 þ 6NH3  H2 O ! 2R3 N
þ ðNH4 Þ2 MoO4 þ 2ðNH4 Þ2 SO4 þ 4H2 O
N235 has been used in production by some plants to
recover Mo and Re from low-density solutions. The
Jiangxi Dexing Plant uses N235 to extract Re from
the roasting fume absorption solution, with pro-
duction capacity of 1400 kg Re/a. There are two
methods for recovery of Mo/Re from the solution.
One is for Mo/Re to be coextracted from the solution,
then separated during stripping. However, tests
showed that this method is difficult to realize. The
other is for Re to be extracted from the solution first,
then Mo is extracted from the raffinate. This second
method was selected. The composition of organic,
phase ratio, reaction time, etc. were tested. The
extraction ratio of Mo and Re were both above 98%.
On the basis of laboratory test results, a pilot test
was carried out in 2010. Pressure oxidation was
performed in a 500-L autoclave with three com-
partments. The Mo oxidation was above 98%. The
composition of the solution was (g/L): Mo 8, H2SO4
130 to 160, Re 0.075. SX was carried out in mixer-
settler equipment, with solution flow rate of 5 L/h to
6 L/h.
Re was extracted from the pressure leaching
solution with 0.5% N235 + 15% isooctanol + 84.5%
sulfonated kerosene. The loaded organic was strip-
ped with ammonia. Mo was extracted from the
stripping solution with 1% Aliquat336. After
two-stage extraction, the Re concentration in the
stripping solution was about 5 g/L and the Mo
concentration was less than 0.01 g/L. The Re solu-
tion was evaporated to produce ammonia perrhe-
nate. The Re extraction recovery was above 97%.
The Mo in the Re raffinate was extracted with 20%
N235 + 5% isooctanol + 75% sulfonated kerosene,
and the loaded organic also was stripped with
ammonia. The Mo concentration in the Re raffinate
was less than 0.1 g/L. The Mo extraction recovery
was above 98%. After organic removal, the Mo
stripping solution can be sent to produce ammo-
nium molybdate. In this study, some measures were
taken to reduce crud formation.
The main components of the Mo raffinate are
sulfuric acid, copper, and iron. The solution can be
sent to leach copper-bearing ores or materials, such
as copper dump leaching for comprehensive usage of
copper and acid. Alternatively, the solution can be
neutralized to recover copper. The pH of the solu-
tion is adjusted to 2 with lime, the loss of Cu in this
process being less than 5%; finally, the solution is
further neutralized or processed using SX to recover
Cu.
The main flowsheet of the process is shown in
Fig. 2.
Products
The pressure oxidation residue was leached with
ammonia, and the ammonia solution was precipitated
Fig. 2. Main flowsheet of the process

Table III. Analysis result of ammonia molybdate

Element Mo Al Fe Si Pb K Na Cu

MSA-0* ‡56 £0.0005 £0.0006 £0.0005 £0.0005 £0.010 £0.001 £0.0003

Result 56.47 0.0005 0.0005 0.0005 0.0001 0.003 0.001 0.0002
Element Mg Ni Sb Cd Mn P Sn

MSA-0 £0.0006 £0.0003 £0.0005 £0.0005 £0.0003 £0.0005 £0.0005

Result 0.0001 0.0001 0.0003 0.0005 0.0001 0.0004 0.0001
* GB3460-2007, MSA-0.
Extraction of Molybdenum from Molybdenite Concentrates with Hydrometallurgical Processing
with nitric acid to produce ammonium molybdate. The
product analysis result is presented in Table III.
CONCLUSIONS
The POX–SX process for extraction of Mo from
molybdenite has the advantages of high efficiency
and high recovery. The oxidation of Mo is above
98%. The 20% Mo and 95% Re leached into the
solution are solvent-extracted with N235 to produce
ammonium perrhenate and ammonium molybdate.
The pressure oxidation residue is leached with
ammonia to produce ammonium molybdate. The
total recovery of Mo and Re is above 97% and 90%,
respectively.
REFERENCES
1. J. Liu, J. China Nonferrous Metall. 18 (2011).
2. T. Xiang, Molybdenum Metallurgy (Changsha: Central
South University Press, 2002).
3. M.H. Shariat and M. Hassani, J. Mater. Proc. Technol. 74,
243 (1998).
4. J.M. Juneja, S. Singh, and D.K. Bose, Hydrometallurgy 41,
201 (1996).