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BY-PRODUCT MOLYBDENITE RECOVERY IN CHILE

CHEMICAL FACTORS IN THE SELECTIVE FLOTATION OF MOLYBDENITE

H. S. Castro

University de Concepci6n

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Concepci6n, Chile
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C. Henriquez
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For presentation at the SME Annual Meeting

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 1

ABSTRACT

The by-product molybdenite technology in Chile is reviewed. Flowsheets, reagents and some operation features for the
actual six chilean moly plants( Chuquicamata, EI Teniente, EI Salvador, Andina, Las T6rtolas and Pelambres), are
presented. The chemical and physicochemical factors involved in the depression of copper and iron sulfides during the
selective flotation of molybdenite, with sodium sulfide, sodium sulfhydrate, anamol-D and LR-744, are discussed.
Advances in technology to solve problems of excess of lime (precipitation with sulfuric acid); excess of residual flotation
reagents (activated carbon and kerosene); and optimization of depressant consumption (Eh control, nitrogen and low-
oxygen air), are discussed.

INTRODUCTION

Molybdenite, MoS2, occurs in the chilean porphyry copper deposits in concentrations varying between 0.020% -
0.035%. By-product molybdenite technology includes two stages:
1. A CuoMo sulfides bulk flotation; and
2. A molybdenite selective flotation.
It is well known that molybdenite is a mineral with natural floatability, and under conventional flotation technology is
recovered together with copper sulfides. Subsequently, to separate molybdenite a selective flotation from the CuoMo bulk
concentrates is performed by using depressant reagents for copper and iron sulfides (Castro, 1979).
Molybdenite exhibits intrinsic hydrophobicity due to its crystalline structure characterized by layers of trigonal prismatic
coordination polyhedra, where each molybdenum atom is surrounded by a trigonal prism of sulphur atoms. Two types of
chemical bonds can be established: a strong covalent bond between Sand Mo atoms; and weak Van der Waals
interactions between S-Mo-S layers.
This structural feature results in two types of surface sites: sites created by rupture of Van der Waals interactions,
termed "faces"; and sites created by rupture of S-Mo bonds, termed "edges".
Faces are non-polar low surface energy sites, while edges are to some extent ionic sites with a higher surface energy.
Hence, faces are highly hydrophobic sites, while edges are less hydrophobic sites.
Consequently, hydrophobicity and natural floatability of a molybdenite particle is given by the faces/edges surface sites
ratio. Particle size is also important because this ratio decrease with particle size. Thus, coarse particles usually are more
hydrophobic than fine particles, because overgrinding contributes to create edges sites.
Additionally, fine particles of molybdenite « 10 microns) show kinetic limitations by a lower probability of particle/bubble
collision and adhesion.
The aim of this work is to review the chemical factors affecting molybdenite flotation during the step of selective flotation
carried out in the by-product molybdenite plants with special emphasis on the chilean technology.

SELECTIVE FLOTATION OF MOLYBDENITE

The purpose of this process is to obtain the highest copper depression simultaneously with the highest molybdenite
recovery.
This is technically possible due to the intrinsic hydrophobicity of molybdenite. As a result of the action of depressant
reagents, this surface property remains on the molybdenite particles even after the destruction or remotion of the collector
coating. Under these conditions, copper sulfides are depressed while the molybdenite floats property with low dosages
of an oily collector (kerosene, diesel oil ), and some type of alkyl alcohol frother.
 2

A GENERAL VIEW TO THE CHILEAN MOLY PLANTS

In Chile the by-product molybdenite is recovered in the following copper plants: Codelco Divisions: Chuquicamata, EI
Teniente, EI Salvador, and Andina; Cia. Minera Disputada de las Condes- Las T6rtolas; and Pelambres.
The chilean Mo production during 1996 was around 17, 500 metric tons. Projections of Mo production for 1997 are over
20,000 metric tons per year. Table I shows the distribution by plants of Mo produced in 1996.

Table I. Production of Mo in Chile during 1996 and some indexes of metallurgical yield.

Moly plant Capacity Production %Mo %Mo %Mo %RMo %RMo Depressant
tpy tonMo/year in the ore bulk conc. final conc. moly plant global

Chuquicamata 4, 500 9,500 0.035 0.8-1.0 49 85-90 45-50 NaHS

EI Teniente 3,200 2,500 0.020 0.45--0.50 49 65-70 38-42 LR-744
EI Salvador 680 1, 150 0.023 0.7-0.8 50 60 43 Anamol-D
Andina 1,400 2,000 0.025 0.5 50 72 54 NaHS
Las T6rtolas 1,200 2,050 0.02-0.03 0.4 51 72 40-42 NaHS
Pelambres 150 300 0.018-0.02 0.35-0.40 52 65 58 NaHS

The main problems connected to Mo recovery in moly plants are usually linked with:
a).-Fine particles of molybdenite with very low flotation rate.
b).-Molybdenite particles partially depressed by lime excess.
c).-Inadequate use and control of copper depressant reagents.
d).-Frothing excess by residual flotation reagents.
e).-Excess of recirculating load of molybdenite in some circuits.

Several depressant reagents are used in the chilean plants. In most of them, sodium sulfide or sodium hydrosulfide are
preferred, with the exception of the by-product molybdenite plants at EI Salvador, which uses Anamol-D (Na2S-As2DJ);
and at EI Teniente, which uses LR-744 or Nokes Reagent (P2Ss-NaOH).
All these depressants are reducing agents, which is explained in large extend by the presence of hydrosulfide ions
(HS"). Hence, measurements of the redox potential of the pulp (Eh) are the most common way to control the process.
The choice of a copper depressant to be used in a moly plant is not a simple decision. It depends on several factors,
such as: the copper sulfide species to be depressed, the collectors type employed during the bulk flotation stage (copper
plant), etc.
Sodium sulfide and sodium hydrosulfide are considered as universal depressants, i.e. may be used with different copper
sulfides, including: chalcocite, covellite, chalcopyrite, bornite; as well as with a number of different thiol collectors.
However, in some cases and in plant practice, the best metallurgical results can be achieved in the presence of some
secondary depressants, such as: thiophosphate or thioarsenite ions. This explains the use of Anamol-D and LR-744 in
some chilean plants. Thioarsenite ions reinforce the depressant action of hydrosulfide ions on chalcocite and covellite
while thiophosphate ions reinforce the depression of chalcopyrite and bornite.
In general, these types of depressant reagents require high dosages to accomplish its depressant rol, approximately 4-5
Kg/metric ton of bulk concentrate which determines a high operation cost.
One problem with depressants is their high ability to be oxidized (decomposed) by dissolved oxygen in aerated mineral
slurries. The mechanism involved is catalytic and the oxidized products are inactive as depressants.
Consequently, efforts have been devoted to avoid this detrimental side reaction. Last years two technologies have been
implemented in Chile to decrease the depressants consumption.
a).-The use of nitrogen (inert gas) as a flotation gas phase.
b).- The use of hermetiC flotation machines, which produce and operate with low-oxygen recirculated air.

The first method is preferred for moly plants installed next to copper smelters, where nitrogen is produced by oxygen
plants as an inexpensive by-product. The second method functions reasonably well but is difficult to maintain hermetic
cells over a large period of time.
 3

CHEMICAL FACTORS IN THE SELECTIVE FLOTATION OF MOLYBDENITE

COPPER DEPRESSANT REAGENTS

Sodium hydrosulfide and sodium sulfide.

As sodium sulfide is a salt formed by a strong base and a weak acid, it suffers hydrolysis in aqueous media giving
alkaline solutions. Three species are in equilibrium: aqueous ~S(g) , and HS· and S2. ions, whose molar fraction depend
only on pH.
Thus, independently if a solid Na2Sx9H20 or NaHS concentrate solutions, are used as depressants, in alkaline
flotation circuits (pH 10-11.5) the predominant species is in both cases the hydrosulfide ion (HS·). Hence, it may be
considered as the active depressant ion.
It is convenient to take into account this point when different sulfide depressants are experimentally evaluated because
dosages are usually expressed in Kg/metric ton of bulk concentrate. It should be compared in their capability of
generating hydrosulfide ions.
The depression mechanisms involve desorption of collector ions by hydrosulfide ions through a chemical replacement
reaction with formation of CuS on the mineral surface. It must be noted that this is a reversible phenomenon, i.e. the
collector ions desorbed in the first step may be re-adsorbed in a second step, depending on the residual concentration of
hydrosulfide ions.
This concentration decreases with flotation time, as it advances along the flotation circuit. For this reason, the redox
potential Eh is measured in the system (tailings) to avoid the reactivation or restoration of floatability of copper and iron
sulfides at last banks of the circuit. This type of control is usually accomplished by potentiometric measurements wit Pt or
Au electrodes.

LR-744 or Nokes reagent.

It was patented by Chanes Nokes in 1949 and can be prepared in several ways. At EI Teniente Division of Codelco is
prepared by reaction between phosphorus pentasulfide and sodium hydroxide in a 1: 1.3 stoichiometric ratio. This is an
exothermic reaction and the excess of sodium hydroxide avoid gaseous emissions of toxic hydrogen sulfide (~S).
Chemical analysis of the reaction products indicates the presence of hydrosulfide ions and thiophosphate ions.
The reaction mechanism is not completely dilucidated, according to literature the following reactions are the most likely
to occur (Kubierschky 1885; Nickless 1967; and Castro 1981):

(1)

Colorometric analysis of hydrosulfide ions assayed only around 27%. This is a low content compared with the other
depressants, and shows a great difference between LR-744 , and Anamol-D and other reagents based completely on
soluble sulfides.

Anamol-D.
Anamol-D is prepared by chemical reaction between arsenic trioxide and sodium sulfide in a 20%-80% w/w relationship.
The most probable reactions involved are:

(2)

(3)

Note that thioarsenite or thioarseniate ions, after an eventual oxidation by dissolved oxygen, are reaction products
formed in a high excess of hydrosulfide ions.

The flotation rate of molybdenite particles in the presence of Anamol-D is faster as the redox potential is increased
negatively. These findings are valid for the potential range from 0 mV to -500mV (vs. Ag/AgCI reference electrode)
(Sepulveda-Suarez and Castro, 1996). This is an interesting phenomenon which govems the molybdenite flotation.
 4

TECHNOLOGICAL FEATURES AND FLOWSHEETS

Simplified f10wsheets of several chilean by-product molybdenite plants are showed in Figs 1-6.

Some process and flotation machine features are showed in Tables II and III.

Table II. Technological characteristics of the chilean moly plants.

Moly plant Rougher cells 1st cleaner 2nd cleaner Column cells Eh,mV Depressant
cells cells (vs.calomel) dosis, ~ton
Chuquicamata Denver 500 cu ft Denver 2 columns second -550 5.5
open 300 cu ft 72"x72" cleaner
EI Teniente Wemco 100 cu ft Wemco column 2nd, 3rd and -100 5.5 - 6.5
open 60 cu ft 72"x72" 4th cleaners
EI Salvador Agitair-120 Agitair Agitair out of -450 8.7
open 48 cu ft 48 cu ft service
Andina Wemco 300 cu ft Denver Denver 5th cleaner -800 4. 0
closed 22.5 cu ft 22.5 cu ft
Las T6rtolas Wemco 300 cu ft Wemco column 1.5 2nd deaner -450 4.0
closed 300 cu ft m diameter
Pelambres Wemco 300 cu ft column column 1st-4th -350 4.0
open 36" diameter 18" diameter cleaners

In rougher circuits both type of flotation cells are employed: self aerated and air forced machines. Self aerated
machines are mainly hermetic type cells, i.e., closed machines which generate and use low-oxygen air as flotation gas, to
reduce depressant consumption.

Table III. Reagents in chilean moly plants.

Moly plant Oily collector Sulfuric acid Activated Nitrogenllow- pH

carbon oxygen air rougher
glton
Chuquicamata diesel oil yes nitrogen 8.5
EI Teniente diesel/kerosene no 150 no 11.5-12.0
EI Salvador diesel/kerosene no no no 11.5-12.0
Andina diesel oil no no low oxygen air 11.5-12.0
Las T6rtolas diesel oil yes no low oxygen air 7.5
Pelambres kerosene yes no nitrogen 9.5

Conditioning
The feed of moly plant is the Cu-Mo bulk concentrate discharged from a concentrate thickener. Here, part of the
residual flotation reagents are removed in the thickener which discharge a product ranges between 45%-60% solids, and
subsequently the percent solids is adjusted for rougher flotation with fresh water addition. This operation is very important
to avoid excess of frothing during the selective flotation and for obtaining higher copper depression and molybdenum
grade and recovery.
The use of activated carbon in this stage has the same purpose, Le., to decrease the residual concentration of frothers
and collectors which were used in the copper plant. Kerosene additions are also used to regulate frothing excess in the
moly plant.
Rougher flotation must operates at an optimum percent solids and with the purpose to stabilize this variable a large
stirred tank installed between the thickener and the rougher circuit is required. This may have three important objectives:
to adjust the proper percent solids; to control the flow rate to the rougher circuit; and to add sulfuric acid to reactivate
molybdenite partially depressed by lime. Thus, as calcium sulfate is preCipitated the flotation of molybdenite is improved.
Then, a short conditioning time with kerosene or diesel oil and subsequent addition of the copper depressant reagent is
carried out. Usually, the addition of depressant is automatically controlled by Eh measurements in the rougher tailings.

Rougher flotation circuit.

This circuit is the most important. Percent solids is a relevant variable on molybdenite recovery and depressant
consumption. In chilean plants this variable usually ranges between 35%-45% solids.
 5

tr----- a./k Cu - ... Coo_a.

~ CHUQUICAMATA MOLY PLANT
H~04 J~ <-- (NcHS)
J.. ---~

~~-

lI:o CotK.

Fig. 1. Simplified fIowsheet of the Codelco-Chuquicamata by-product molybdenite plant.

r - - - - - .... " " - " " _

EL TENIENTE MOLY PL.A.NT

{LR-7 .....>

Fig. 2. Simplified fIowsheet of the Codelco-EI Teniente by-product molybdenite plant.

 6

r------ Bulk Cu - hlo Concentrate

C:~~~:::~--r------ Cu c.w:.

EL SALVADOR MOLY PLANT

(Anomol - D)

Fig. 3. Simplified flowsheet of the Codelco-El Salvador by-product molybdenite plant.

ANDINA ~OLY PLANT

(NcHS)

Fig. 4. Simplified flowsheet of the Codelco-Andina by-product molybdenite plant.

 7

r---tr;'----- Bulk Cu- Mo Conoantrats

, ---H2SO~

Cu Cone..

Fig. 5. Simplified flowsheet of the Disputada de las Condes-Las T6rtolas by-product molybdenite plant.

. - - - - - Bul: Cu - ..., Ctlnaotn:.Ie

PELAMBRES MOLY PLANT

(NaHS)

Fig. 6. Simplified flowsheet of the Pelambres by-product molybdenite plant.

 8

Theoretically the depressant action of most of the reagents employed in moly plants is favored by the percent solids,
because collector coating removal is easier as the residual hydrosulfide concentration is elevated. However, molybdenite
recovery is also affected by the type of flotation machine and air flow in the cell. Hence, results in plant practice are
controversial, while in some plants is convenient to increase rougher percent solids over 40%; in other plants it is
recommended to decrease around 35% solids. It seems that air forced flotation machines accept a higher % of solids.
However, self aerated hermetiC flotation machines are recommended for low-oxygen air technology.
In chilean moly plants both type of flotation machines are used. In general, the cell size for rougher circuit ranges from
100 cu ft to 500 cu ft.
The use of column cells in rougher circuits have failed and the experience recommend to avoid this choice in plant
design.
Nitrogen is used as flotation gas in Chuquicamata and Pelambres by-product molybdenite plants, while low-oxygen air is
used in Andina and Las Tortolas moly plants.

Eh control
In moly plants where sodium sulfide or sodium hydrosulfide is employed as unique depressant, Eh measurements in
rougher tailings are around -350 mV to -800 mV by using Pt or Au electrodes (vs. Calomel or Ag/AgCI reference
electrodes). In the case of Anamol-D is around -450 mV, but with LR-744 the potential is Significantly less negative or
less reducing: -100mV. This fact is explained by the low content of hydrosulfide ion present in this reagent.
All these redox potential measurements are made in the tailing of the rougher circuit, and at less in two plants are used
to control depressant addition or dosage.

First cleaner circuit.

In chilean moly plants the first cleaner step is carried out in conventional cells from 48 cu ft to 300 cu ft or in column
cells. Then, in this circuit upgrade it is important as is Mo recovery, because the first cleaner tailings are recirculated to
the feed thickener
Column flotation cells as a first cleaner stage were installed in EI Teniente moly plant in 1996, but must be replaced for
a circuit of conventional cells, due to the low Mo recovery obtained, which increased Mo circulating load to the thickener,
and consequently losses of molybdenite in the rougher circuit.

Next cleaner steps.

In chilean moly plants several cleaner stages are used to reach the final concentrate grade, which is around 50%Mo.
These cleaner steps have a counter current configuration. Conventional and column flotation cells are used. However,
when the second cleaner circuit is in column cells, the use of a scavenger conventional circuit to treat the column tailings
is crucial to Mo recovery.

Regrind
The real need of regrind in moly plants is not clear. However, many plants have one or two regrind steps for intermediate
concentrates. In some of them, reasons of liberation with impact on final concentrate grade are admitted. In spite of, this
other plant have recognized that regrind is not used for particle size reduction because majority of molybdenite is
liberated; but it would playa role inducing aUriction between particles with a kind of "cleaning effect".

REFERENCES
Castro, S., 1981, "Selective Flotation of Molybdenite: Depression Mechanisms of Chalcocite wirh Sodium Sulfide,
Anamol-D and Nokes Reagent.", Devolopments in Mineral Processing 2 Part A., (Proc.Thirteenth Intemational Mineral
Processing Congress, Warsow-Poland), J. Laskowski, Ed., Elsevier, pp. 181.

Castro, S., 1979, "Flotation of Molybdenite". International Molvbdenum EnCYclopaedia, A. Sutulov, Ed., Intermet
Publications, Santiago-Chile, pp.161.

Kubierschky, E., 1885, Journal Prakt. Chem. 2, 31.

Nickless, G., Pollard, F.H., and Rogers, D.E., 1967, "Hydrolysis of the Phosphorus Sulfides: Tetraphosphorus
Decasulfides and Tetraphosphorus Tetrasulfides Hexanoide". J. Chem. Soc. A(11), 1721-26.

Nokes, C., 1949, "Differential Froth Flotation of Sulfide Ores"., U.S. Patent N° 2,492,936.

Sepulveda-Suarez, C. and Castro, S.H., 1996, "The Effect of Redox Potential on the Selective Flotation of Molybdenite by
Using Anamol-D as Copper Depressant" .. Electrochemistry in Mineral and Metal Processing IV. , R. Woods, F.M. Doyle
and P. Richarson, Eds., The Electrochemical Society., pp. 98-107.