Minerals Engineering 20 (2007) 609–616

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Floatability of chalcopyrite and molybdenite in the presence

of lignosulfonates. Part II. Hallimond tube flotation
Anita Ansari 1, Marek Pawlik *

The University of British Columbia, Norman B. Keevil Institute of Mining Engineering, 517-6350 Stores Road, Vancouver, BC, Canada V6T 1Z4

Received 15 October 2006; accepted 14 December 2006

Available online 5 February 2007

Abstract

The effect of six lignosulfonates on the Hallimond tube flotation of chalcopyrite and molybdenite was studied as a function of pH,
with the use of common pH modifiers (soda ash, potassium hydroxide, and lime). By comparing the flotation results with the adsorption
data collected in Part I of this contribution, it becomes evident that the depression of chalcopyrite flotation takes places only when ligno-
sulfonates adsorb on the mineral surface and, at the same time, a fraction of the xanthate collector is desorbed from the mineral surface.
These two conditions are met only at high pH adjusted with lime. The depression of the natural floatability of molybdenite is relatively
easy using all six lignosulfonates, but once the mineral is rendered strongly hydrophobic by the addition of an oily collector (dodecane),
the depression of molybdenite by lignosulfonates is very difficult and only calcium lignosulfonates, and the highest molecular weight
sodium salt, produce significant levels of depression. Overall, the results suggest that it is possible to selectively float chalcopyrite from
molybdenite using lignosulfonates by depressing molybdenite. This can be achieved over a wide pH range provided that a pH modifier
other than lime is used for pH control. Although the results showed that chalcopyrite flotation and molybdenite depression can be
achieved under similar physicochemical conditions, further tests with real ores under industrial conditions have to be carried out with
particular attention to the effect of process water quality.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Flotation depressants; Froth flotation; Flotation reagents; Surface modification

1. Introduction rite particles (in addition to affecting the redox conditions

Chalcopyrite (CuFeS2) and molybdenite (MoS2) are the
main copper and molybdenum minerals found in complex
sulfide ores. The usual flotation practice of separating
molybdenite from chalcopyrite relies on a two-stage flota-
tion process. First, a bulk chalcopyrite–molybdenite con-
centrate is produced, which is later refloated to obtain
separate chalcopyrite and molybdenite products. This sec-
ond selective stage requires the use of various depressants
that destroy a xanthate collector coating around chalcopy-
*
Corresponding author. Tel.: +1 604 827 5034; fax: +1 604 822 5599.
E-mail addresses: Anita.Ansari@amec.com (A. Ansari), mpp@mining.
ubc.ca (M. Pawlik).
1
Present address: AMEC, 111 Dunsmuir Street, Suite 400, Vancouver,
BC, Canada V6B 5W3.
of the pulp) and thus, prevent chalcopyrite flotation. The
selectivity of the process is greatly enhanced by the natural
hydrophobicity of molybdenite which is further increased
in practice by the addition of an oily collector. The strategy
of depressing chalcopyrite rather than molybdenite is lar-
gely dictated by mass balance considerations. The amount
of molybdenite in Cu–Mo ores is usually very small com-
pared to the content of chalcopyrite, so the depression of
molybdenite and simultaneous flotation of chalcopyrite
would inevitably lead to the mechanical entrainment of
MoS2 within a large volume of chalcopyrite concentrate.
The natural hydrophobicity of molybdenite results from
its layered crystal structure. The sulfur and molybdenum
atoms within each layer are held together by strong cova-
lent bonds, while the bonds between adjacent layers are
weak van der Waals bonds between sulfur atoms (Leja,

0892-6875/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2006.12.008
610 A. Ansari, M. Pawlik / Minerals Engineering 20 (2007) 609–616
1982). These two types of bonds form the basis of the sur-
face properties of the mineral. The sheet edges formed by
the breaking of the strong bonds between sulfur and
molybdenum atoms are hydrophilic, while the weak sul-
fur–sulfur bonds provide excellent cleavage characteristics
parallel to the sulfur sheets, and are thus, hydrophobic.
Chander and Fuerstenau (1972) determined that the rel-
ative flotation of molybdenite was at a maximum in the pH
range of 5.5–6.5. The natural floatability of molybdenite
can quite easily be depressed by high pH alone, by calcium
ions (Chander and Fuerstenau, 1972), or by ferrous and
ferric species at higher pH values (Castro and Bobadilla,
1995). Among polymeric additives, shear-degraded poly-
acrylamide at acidic pH (Castro and Laskowski, 2004),
dextrin (Wie and Fuerstenau, 1974), and humic acids
(Lai et al., 1984) are known to be strong depressants of
molybdenite.
In the case of chalcopyrite, once the mineral is rendered
hydrophobic by a xanthate collector, its depression can
effectively be achieved by rather drastic chemical treat-
ments. The usual reagents include: sodium bisulfide
(NaHS) in combination with nitrogen gas for flotation,
Noke’s reagent (thiophosphorus or thioarsenic com-
pounds), and cyanides.
In Part I of this study, it was found that lignosulfonates
are capable of adsorbing on both molybdenite and xan-
thate-treated chalcopyrite. It was also observed that the
adsorption of lignosulfonates on chalcopyrite at high pH
was accompanied by a simultaneous desorption of a portion
of ethyl xanthate. Lignosulfonate adsorption on molybde-
nite was rather low at natural pH (4.5) but was greatly
enhanced at high pH adjusted with lime. In general, the
adsorption results pointed towards specific/chemical inter-
actions between lignosulfonates and specifically adsorbed
metallic species on chalcopyrite and molybdenite. When
the mineral surfaces were strongly negatively charged (high
pH adjusted with soda ash or potassium hydroxide), the
adsorption density of the anionic polyelectrolytes decreased
dramatically. In this part, the above observations are corre-
lated with the flotation response of the minerals.
2. Experimental
2.1. Materials
Samples of chalcopyrite and molybdenite were received
from Ward Natural Science Establishment. The prepara-
tion of the samples for testing (grinding and sizing), specific
surface areas, and purity were described in Part I. The chal-
copyrite sample was of excellent quality but the molybde-
nite sample (+38 lm size fraction) contained only 73% of
MoS2, and about 22% quartz and 5% muscovite, as deter-
mined by X-ray diffraction and chemical assays.
The same lignosulfonates, with one exception, as in the
previous study were used in flotation experiments. Their
properties, including the new D-659 reagent, are listed in
Table 1. All samples were supplied by Borregaard–Ligno-
tech USA. The D-659 lignosulfonate was used instead of
the D-701 only in flotation tests with chalcopyrite.
In comparison to the other lignosulfonates, the D-659
can be characterized by low anionicity, as seen from the
contents of sulfonic and carboxylic groups, and a relatively
high molecular weight.
Analytical grade calcium oxide (CaO), potassium
hydroxide (KOH), and soda ash (Na2CO3) were used for
pH adjustments. The potassium salt of ethyl xanthic acid
(KEX) (Acros Organics) was used as the chalcopyrite col-
lector. Potassium nitrate was added to provide constant
ionic strength (0.001 mol/L). Methyl isobutyl carbinol,
MIBC (Cytec Aerofroth 70), was used as the frother.
Dodecane (Sigma Chemicals) was used as a collector in
some flotation tests with molybdenite.
2.2. Hallimond tube flotation
Despite repeated screening, the +38 lm chalcopyrite
fraction contained a significant quantity of very fine poorly
floating particles which had to be removed prior to flota-
tion. About 3.4 g of the 105 + 38 lm size fraction was
weighed on an analytical balance and placed in a 400 mL
beaker. The pre-weighed amount of the mineral was mixed
with 300 mL of distilled water. The mixture was placed for
exactly 1 min in an ultrasonic bath. The beaker was then
quickly removed from the bath and allowed to settle for
15 s. Fine fractions were then removed by decanting the
suspension. This desliming procedure was repeated for an
additional two times, until no slimes were left in suspension
with the last decanting step done with 0.001 M KNO3, the
background electrolyte. Since sulfide minerals generally
have high densities, it is easy to pour off practically the
entire amount of solution leaving only wet mineral parti-
cles on the bottom of the beaker.
About 2.5 g of deslimed chalcopyrite was first condi-
tioned with 80 mL of a 0.001 M KNO3 solution in a
150 mL glass beaker for about 2 min. The pH of the pulp
was adjusted at this point. Afterwards, an aliquot of a
stock xanthate solution was added to achieve a final
collector concentration of 25 mg/L and the mixture was
conditioned for 5 min. Then, a suitable amount of a ligno-
sulfonate stock solution was added to the mixture and the
entire suspension was conditioned for a further 10 min. The
order of reagent addition should be noted: xanthate first,
followed by lignosulfonate. A small aliquot of a stock
MIBC solution was added to the beaker, to achieve a final
frother concentration of 10 mg/L.
After conditioning, the whole mixture was transferred to
a modified Hallimond tube and the tube was filled with
0.001 M KNO3 solution. The pH was readjusted, if neces-
sary, and the pulp was mechanically mixed in the tube for
about 20 s. The total volume of the pulp was 160 mL. All
the tests with chalcopyrite were preformed using com-
pressed air. The flotation time was 90 s to minimize the
mechanical carry-over of poorly floating particles, while
the air-flow rate was maintained at 20 mL/min. The small
 A. Ansari, M. Pawlik / Minerals Engineering 20 (2007) 609–616 611

Table 1
Selected chemical properties of the tested lignosulfonates
Ca (%) Na (%) Total sulfur (%) Sulfonate sulfur (%) Carboxylic groups (%) Molecular weight (kDa)
D-619 0.0 9.0 7.0 6.0 3.2 25
D-648 0.1 15.9 11.1 8.1 7.4 5
D-659 0.0 9.0 4.9 4.2 5.2 30
D-701 8.7 0.3 6.6 5.8 7.2 10
D-748 0.0 7.0 6.5 6.2 3.1 45
D-750 0.0 8.0 3.2 2.7 7.4 6
D-912 8.0 0.1 6.5 5.0 7.2 5.5

amount of MIBC enhanced the kinetics of mineral flota-

tion while stabilizing the formation of smaller, more uni- 100
form-in-size gas bubbles.
The pH was mainly adjusted with lime (CaO). A ‘‘con-

Chalcopyrite Flotation Yield [%]

80
trol’’ test for each type of lignosulfonate was performed
at pH 11 adjusted with KOH for chalcopyrite. Na2CO3
and KOH were also used for pH adjustments in tests with 60
molybdenite. A limited number of experiments were per-
formed for chalcopyrite with lignosulfonates added before
xanthate. The results of these tests are referred to as ‘‘LS 40
D-648 natural pH
first’’ in the figure legends (Figs. 1–6). D-648 pH~9
The same procedure was followed during flotation tests D-648 pH~11
20
with molybdenite, with the exception that nitrogen was D-648 pH~11 (KOH)
used instead of air. When dodecane was used, it was added D-648 natural pH (LS first)
to the flotation mixtures in the form of a freshly prepared 0
aqueous emulsion (0.3 g of dodecane in 1 L of background 0 50 100 150 200
electrolyte) to obtain a final dodecane concentration of Lignosulfonate Concentration [mg/L]
10 mg/L.
Fig. 2. Effect of D-648 lignosulfonate on flotation of chalcopyrite. pH
adjusted with lime (CaO) unless indicated otherwise. KEX concentration
3. Results 25 mg/L.

Figs. 1–6 show the effect of individual lignosulfonates on

the flotation of chalcopyrite. In the case of the D-619 and 100
D-648 reagents (Figs. 1 and 2, respectively), chalcopyrite
depression is only achieved at a high pH adjusted with
Chalcopyrite Flotation Yield [%]

80

D-748 natural pH
100
60 D-748 pH~9
D-748 pH~11
Chalcopyrite Flotation Yield [%]

80 D-748 pH~11 (KOH)

40 D-748 natural pH
(LS first)
60
20

40
D-619 natural pH 0
D-619 pH~9 0 50 100 150 200
20 D-619 pH~11 Lignosulfonate Concentration [mg/L]
D-619 pH~11 (KOH)
Fig. 3. Effect of D-748 lignosulfonate on flotation of chalcopyrite. pH
D-619 natural pH (LS first) adjusted with lime (CaO) unless indicated otherwise. KEX concentration
0 25 mg/L.
0 50 100 150 200
Lignosulfonate Concentration [mg/L]

Fig. 1. Effect of D-619 lignosulfonate on flotation of chalcopyrite. pH

lime, but at a relatively low lignosulfonate dosage. Under
adjusted with lime (CaO) unless indicated otherwise. KEX concentration all other test conditions, these two lignosulfonates do not
25 mg/L. depress the mineral.
612 A. Ansari, M. Pawlik / Minerals Engineering 20 (2007) 609–616

100 100
D-659 natural pH
D-912 natural pH
D-659 pH~9
D-912 pH~9
Chalcopyrite Flotation Yield [%]

Chalcopyrite Flotation Yield [%]

80 D-659 pH~11 80 D-912 pH~11
D-659 pH~11 (KOH)
D-912 pH~11 (KOH)
D-659 natural pH (LS first)
D-912 natural pH (LS first)
60 60

40 40

20 20

0 0
0 50 100 150 200 0 50 100 150 200
Lignosulfonate Concentration [mg/L] Lignosulfonate Concentration [mg/L]

Fig. 4. Effect of D-659 lignosulfonate on flotation of chalcopyrite. pH Fig. 6. Effect of D-912 lignosulfonate on flotation of chalcopyrite. pH
adjusted with lime (CaO) unless indicated otherwise. KEX concentration adjusted with lime (CaO) unless indicated otherwise. KEX concentration
25 mg/L. 25 mg/L.

It is noteworthy that this lignosulfonate (D-912) was the

100 only calcium salt tested on chalcopyrite. The other reagents
were sodium salts.
The depression of chalcopyrite achieved at high pH
Chalcopyrite Flotation Yield [%]

80 adjusted with KOH is never as good as the depression level

achieved in the presence of lime at high pH. Also, at natu-
ral pH, the reverse addition of lignosulfonate (i.e., the addi-
60 tion of lignosulfonate prior to the addition of xanthate),
results in better depression than the addition of xanthate
followed by lignosulfonate.
40
D-750 natural pH The flotation results for molybdenite are shown in Figs.
D-750 pH~9 7–13. Figs. 7–12 illustrate the effect of individual lignosulf-
20 D-750 pH~11 onates on the natural floatability of the molybdenite sam-
D-750 pH~11 (KOH) ple at pH 5 (natural) and pH 8 adjusted with different
D-750 natural pH (LS first) pH modifiers. A preliminary series of tests showed a clear
0
0 50 100 150 200
Lignosulfonate Concentration [mg/L] 50
Fig. 5. Effect of D-750 lignosulfonate on flotation of chalcopyrite. pH
adjusted with lime (CaO) unless indicated otherwise. KEX concentration
Molybdenite Flotation Yield [%]

25 mg/L. 40 D-619 pH~5 (natural)

D-619 pH~8 (CaO)
D-619 pH~8 (Na2CO3)
The D-748 lignosulfonate (Fig. 3) appears to be a better 30
D-619 pH~8 (KOH)
depressant. It produces depression at moderately alkaline
as well as high pH values adjusted with lime. As the pH
20
adjusted with lime increases, lower and lower dosages of
the reagent are required for depression.
Additions of the D-659 and D-750 reagents result in 10
chalcopyrite depression in the presence of lime, both at
high and moderate pH values, using fairly low concentra-
tions of the lignosulfonates (Figs. 4 and 5). 0
The D-912 measurably depresses chalcopyrite flotation 0 10 20 30 40 50
under all test conditions (Fig. 6). It is also clear that its Lignosulfonate Concentration [mg/L]
action is enhanced in the presence of lime, similarly to Fig. 7. Natural floatability of molybdenite in the presence of D-619
the other reagents. lignosulfonate.
 A. Ansari, M. Pawlik / Minerals Engineering 20 (2007) 609–616 613

50 50
D-648 pH~5 (natural)
D-648 pH~8 (CaO) D-701 pH~5 (natural)

Molybdenite Flotation Yield [%]

D-648 pH~8 (Na2CO3) D-701 pH~8 (CaO)
Molybdenite Flotation Yield [%]

40 40
D-648 pH~8 (KOH) D-701 pH~8 (Na2CO3)
D-701 pH~8 (KOH)
30 30

20 20

10 10

0 0
0 10 20 30 40 50 0 10 20 30 40 50
Lignosulfonate Concentration [mg/L] Lignosulfonate Concentration [mg/L]

Fig. 8. Natural floatability of molybdenite in the presence of D-648 Fig. 10. Natural floatability of molybdenite in the presence of D-701
lignosulfonate. lignosulfonate.

50 50
D-748 pH~5 (natural) D-750 pH~5 (natural)
D-748 pH~8 (CaO) D-750 pH~8 (CaO)
Molybdenite Flotation Yield [%]
Molybdenite Flotation Yield [%]

40 D-748 pH~8 (Na2CO3) 40 D-750 pH~8 (Na2CO3)

D-748 pH~8 (KOH) D-750 pH~8 (KOH)

30 30

20 20

10 10

0 0
0 10 20 30 40 50 0 10 20 30 40 50
Lignosulfonate Concentration [mg/L] Lignosulfonate Concentration [mg/L]

Fig. 9. Natural floatability of molybdenite in the presence of D-748 Fig. 11. Natural floatability of molybdenite in the presence of D-750
lignosulfonate. lignosulfonate.

dependence of molybdenite flotation on pH (results not
shown), which is in a very good agreement with the obser-
vations of Chander and Fuerstenau (1972). Above pH
around 8, regardless of the pH modifier used, the mineral
was strongly depressed, so pH 8 was the highest pH value
investigated at which the true effect of lignosulfonates on
flotation could still be seen.
It should be noted that in the absence of lignosulfonates,
the flotation of molybdenite was surprisingly low, consider-
ing that the mineral was pre-concentrated earlier by flota-
tion. The poor grade of the sample (73% MoS2) was
probably responsible for such a result but still a better flo-
tation performance was expected.
As can be seen from Figs. 7 and 8 for the D-619 and D-
648 lignosulfonates, the two poorest depressants of chalco-
pyrite, low concentrations of lignosulfonate were sufficient
to depress molybdenite – note the lignosulfonate con-
centration scales for the chalcopyrite and molybdenite
results – regardless of the pH modifier used.
The D-748 at high enough concentrations was able to
strongly depress molybdenite (Fig. 9). However, this ligno-
sulfonate performed relatively poorly under a natural pH
value.
The D-701, the D-750 and the D-912 induced very
strong depression of molybdenite at very low concentra-
tions (5–10 mg/L) and under all conditions (Figs. 10–12,
respectively). It should also be noted that the D-701 and
D-912 were the two calcium lignosulfonates tested on
molybdenite, while the D-750 was the least anionic reagent
in the series at pH 5.
A series of additional flotation tests were carried out to
show the effect of induced hydrophobicity of molybdenite
614 A. Ansari, M. Pawlik / Minerals Engineering 20 (2007) 609–616

50 sulfonates, it can be seen that the effectiveness of lignosulf-

D-912 pH~5 (natural) onates increases in the order: D-619  D-648 < D-748 <
D-912 pH~8 (CaO) D-750 < D-659 < D-912. At natural pH, only the D-912
Molybdenite Flotation Yield [%]

40 D-912 pH~8 (Na2CO3) and D-659 reagents result in pronounced depression of

D-912 pH~8 (KOH) chalcopyrite. All lignosulfonates are very strong depres-
sants of chalcopyrite flotation at high pH, but only when
30
lime is used for pH adjustment. In comparison to the flota-
tion data at natural pH, the flotation of chalcopyrite at pH
20 11 adjusted with KOH is unaffected by additions of the
D-619 and D-648, and it even improves in the presence
of the D-659 and D750. At a sufficiently high dosage, the
10 D-912 is the strongest depressant of chalcopyrite regardless
of pH conditions.
It is important to recall from Part I of this study that all
0 lignosulfonates gave high and almost the same adsorption
0 10 20 30 40 50 densities at natural pH and at pH 11 adjusted with lime.
Lignosulfonate Concentration [mg/L]
Even though the adsorption characteristics of lignosulfo-
Fig. 12. Natural floatability of molybdenite in the presence of D-912 nates were very similar under those conditions, the flotation
lignosulfonate. results show that the high adsorption of lignosulfonates at
natural pH does not really translate into a strong depressing
effect on chalcopyrite flotation. However, a very similar
100
First lignosulfonate, then dodecane level of adsorption at pH 11 adjusted with lime brings about
First dodecane, then lignosulfonate complete depression of chalcopyrite by all the reagents.
Dodecane only
Molybdenite Flotation Yield [%]

80 Control of pH with soda ash and KOH does not result in

60
40
No dodecane, no lignosulfonate
20
0 take place. When pH is adjusted to a high value using
D-619 D-648 D-701 D-748 D-750 D-912
Lignosulfonate type
Fig. 13. Effect of dodecane and lignosulfonates on floatability of
molybdenite. pH 5.5 (natural), lignosulfonate concentration 50 mg/L,
dodecane dosage 10 mg/L.
on the depressing action of lignosulfonates. The tests were
performed in the presence of 10 mg/L dodecane. The con-
centration of lignosulfonates in all the tests was 50 mg/L to
ensure overdosing of the reagents. The results of these tests
are shown in Fig. 13.
When oil is added to molybdenite, the floatability of the
mineral reaches very high levels (dashed line). Further-
more, if dodecane is introduced ahead of lignosulfonates,
the depression of the mineral is quite poor. Alternatively,
if the mineral is conditioned with lignosulfonate first fol-
lowed by dodecane, the depression is excellent.
4. Discussion
Using the depression level of chalcopyrite flotation at
natural pH as a measure of the depressing power of ligno-
chalcopyrite depression, which correlates very well with
low adsorption of lignosulfonates under these conditions.
Low adsorption of lignosulfonates coupled with the pres-
ence of just the chemically adsorbed xanthate on the min-
eral surface is insufficient to depress the mineral.
At natural pH, the desorption of xanthate does not
occur and the depression of chalcopyrite by lignosulfonates
is not very effective. It is apparent that the desorption of
xanthate alone is not sufficient for depressing chalcopyrite
and a simultaneous adsorption of lignosulfonates must also
KOH, the physically adsorbed xanthate is removed from
the mineral surface but this process in not accompanied
by the adsorption of lignosulfonates. As a result, the flota-
tion of chalcopyrite is not affected. On the other hand,
using lime for pH adjustment induces high lignosulfonate
adsorption and a measurable quantity of xanthate appears
in solution. At high pH using lime, all lignosulfonates gave
high adsorption densities which also resulted in the com-
plete depression of chalcopyrite. Therefore, it can be con-
cluded that it is the combination of xanthate desorption
and lignosulfonate adsorption that leads to the depression
of chalcopyrite flotation. Overall, and consistent with the
adsorption data from Part I, calcium salts of lignosulfo-
nates are stronger depressants of chalcopyrite compared
to sodium salts.
In the case of naturally-hydrophobic molybdenite, the
depression of mineral flotation by lignosulfonates is very
strong even at natural pH, when the adsorption of the
depressants is relatively low. It should also be pointed
out that lignosulfonates are not very effective depressants
of molybdenite when the mineral surface is rendered
strongly hydrophobic by the addition of dodecane. This
 A. Ansari, M. Pawlik / Minerals Engineering 20 (2007) 609–616
suggests that lignosulfonates weakly interact with strongly
hydrophobic surfaces. It is also noteworthy that the two
reagents that significantly reduced the floatability of oil-
covered molybdenite (D-701 and D-912) were the only
calcium salts among the tested reagents. The D-912 ligno-
sulfonate was also the strongest chalcopyrite depressant,
which again shows the importance of polyvalent metal spe-
cies in controlling the adsorption behavior and depressing
action of lignosulfonates. The addition of lignosulfonate
ahead of oil, however, prevents the oil from enhancing
the hydrophobicity of molybdenite. The low adsorption
of lignosulfonates on molybdenite appears to be sufficient
to render the mineral surface hydrophilic and to prevent
the oily collector from attaching and spreading on the
molybdenite surface.
This poor depressing effect towards strongly hydropho-
bic, oil-coated molybdenite also correlates well with the
inability of lignosulfonates to depress chalcopyrite in the
presence of xanthates at natural pH. Dixanthogen, an oily
oxidation product of xanthates, present on the chalcopyrite
surface would likely function in a way similar to dodecane
on the surface of molybdenite.
Overall, the results suggest that it could be possible to
selectively float chalcopyrite from molybdenite by depress-
ing molybdenite with lignosulfonates. This separation can
be achieved over a wide pH range provided that a pH mod-
ifier other than lime, e.g., soda ash, is used for pH control.
A rougher flotation stage could be run at high pH (to
depress pyrite) in the presence of only xanthates to float
chalcopyrite. It could be expected that a portion of natu-
rally-hydrophobic molybdenite will float along chalcopy-
rite. The rougher tailings could then be scavenged for
molybdenite using an oily collector. Any molybdenite
reporting to the rougher (chalcopyrite) concentrate could
be depressed using lignosulfonates in a cleaning stage. Pulp
dilution and the use of flotation columns could potentially
enhance the selectivity of the process. It is also noteworthy
that carbonate anions introduced with soda ash would
mostly precipitate any calcium ions naturally present in
process water thus allowing lignosulfonates to act more
selectively.
A couple of the tested lignosulfonates appear to be par-
ticularly promising as selective depressants. The D-619 and
D-648 lignosulfonates do not affect the flotation of chalco-
pyrite at natural or weakly alkaline pH while at the same
time, they completely depress the natural floatability of
molybdenite.
It should also be pointed out that dixanthogen could to
some extent function as a collector of molybdenite and
could interfere with the depressing action of lignosulfo-
nates by analogy to the molybdenite flotation results
obtained in the presence of dodecane.
5. Conclusions
Depression of chalcopyrite flotation by lignosulfonates
takes place only under high pH conditions when lime is
615
used for pH control. Calcium-hydroxy species, which form
in alkaline solutions, specifically adsorb on the mineral sur-
face, reduce or even reverse the negative surface charge,
and act as adsorption sites for lignosulfonates. The adsorp-
tion of lignosulfonates is accompanied by desorption of the
physically adsorbed xanthate fraction, and this combina-
tion of processes brings about the depression of the
mineral.
The natural floatability of molybdenite can easily be
depressed by any type of lignosulfonates regardless of pH
and all lignosulfonates seem to show a similar affinity
towards the untreated molybdenite surface. Apparently,
the presence of a small amount of strongly hydrophilic
lignosulfonates adsorbed on the surface is sufficient to ren-
der the mineral hydrophilic, although lignosulfonate
adsorption on molybdenite is greatly enhanced at high
pH adjusted with lime. The adsorbed lignosulfonate mole-
cules also prevent the attachment and spreading of an oily
collector over the molybdenite surface and the flotation of
the mineral cannot be improved. On the other hand,
lignosulfonates appear to weakly interact with apolar oils
resulting only in poor depression of dodecane-coated
molybdenite.
Although the tests were performed with the use of single
minerals, the flotation results for molybdenite and chalco-
pyrite indicate that lignosulfonates can be used as selective
depressants under neutral and weakly alkaline pH. Under
these conditions, molybdenite will be depressed while the
flotation of chalcopyrite should not be affected. The use
of lime as a pH modifier is not recommended because of
the activating role of calcium for lignosulfonate adsorp-
tion. In the presence of Ca2+ introduced by lime, the selec-
tivity of depression should be drastically reduced.
Due to the role of calcium ions – polyvalent ions in gen-
eral – in lignosulfonate adsorption and mineral depression,
calcium lignosulfonates are stronger depressants than
sodium salts. However, calcium salts also appear to be less
selective.
Acknowledgement
Financial and in-kind support for this study from
Borregaard Lignotech USA, through a Grant-in-Aid of
Research, is gratefully acknowledged.
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