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95

Effect of clay slimes 00 correr, molybdeoum flotatioo llom porphyry

ores
S. Bulatovic,D.M. WyslouzilandC. Kant
Lakefield ResearchLimited
185 ConcessionStreet
Lakefield, Ontario, Canada,KOL2HO

ABSTRACT
The presenceo clay adverselyaffects the tIoatability o copper and molybdenum
during processing porphyry copper/molybdenumores. In addition, reagent consumptions
are much higher than when treating clay-free ores.
Ores containing kaoline, brarnmoIIite, iIIite and montmorilIonite were examin~d in
the Iaboratory to determine how cIay mineraIs affect the floatabiIity of copper and
moIybdenum, and to find a possible solution to alleviate the harrnful effect of cIar slimes.
lt was demonstrated that the presenceof cIar mostIy affects floatabiIity o coarse and
middIing particIes,and reducesseIectivity.
The results ofthe researchwork showed that there may be severalpossible ways of
reducing fue detrimental affects of clay slirnes on flotation, some of which include a) use
of alternative flowsheets, b) flotation at reduced pulp density, and c) the use of special

frothers.
The applicability o the fmdings in plant practice are discussed.

Proceedings of
(~opper YY-CobreYY Intemationa! EnvironmentConfcrcn,c
Volume [[-Mineral Processing/Enviroment. Ilc.llth and Sali:!
Editcd by B.I\. Hancock andM.R.L. Pon
The Minerals. Metals & Materials Society. 1')')')

96

VOLUME

11

INTRODUCTION

The role of ciar slime during non-metallic mineral and coal flotation has been
extensively studied (1,2,3) but little is known about the influence of ciar slimes on the
flotation of porphyry copper ores.
In 1994, Lakefield Research initiated an in-house test prograrn to examine the
effect of various clays on flotation of porphyry copper and copper-gold ores. The research
work was conducted on natural ores from Chile, Pero and Indonesia with different types
and levels of cIar contentoIn many porphyry ores, various clays are present,someof which
include: kaolinite, brammollite, chamosite, illite, and montmorillonite.
The presenceof cIar in mineral flotation causesa loss in recovery, possibly due to
fue presence of slime coating on the mineral surface or on air-bubbles. Clays increase
reagent consumption and can create serious frothing (or non-frothing) problems. As a
result large quantities of slime are transferred into fue concentrateduring fue roughing and
scavengingstages.
In the early stagesofresearch on the effect of slirnes (4), it was proposedthat slime
coating is fue result of electrostatic attraction. It was postulated that cIar slirnes have the
opposite chargeto that ofthe mineral surface and therefore they are attractedto the mineral
surface by electrostatic forres.
Other researchers(5,6) proposed that slime coatings on a mineral surface are the
result of chemical interaction. More recent studies (7,8,9) have confinned that electrostatic
forces are responsible for clay coatings on mineral surfaces.It was noted that clay coatings
are less likely to happenin a dispersed system, and that the presenceof soluble ions and
pH may influence clay coatings.
It is believed (10) that ciar particIes mar be floccuIated or aggregatedin severaI
combination: face-to-face, edge-to-edge, and face-to-edge. Tbese associations mar be
affected by changing the charge on the cIay. WhiIe the isoeIectric point on kaoIinite occurs
at pH 3.3 and montmoriIIonite at pH <3.0, fueTeis evidence (11) that the faces of cIays are
a1waysnegativeIycharged, while the edgesexhibit an isoeIectric point at about natural pH.
Studies carried out with various sIimes indicated that ciar induces an "armorcoating" (12) on air-bubbIes, thus preventing attachmentof larger mineral particIes. The
consumption of reagents by cIar mineraIs, and hence the reduction in the recovery of
minerals, was demonstratedon a number of oxide ores (13). CIay mineraIs adsorb much of
the reagentneededto float coarserparticles.
Few published data exist describing the effect of ciar slirnes on porphyry copper
flotation, although it is known that clay slirnes adversely affect (14) the flotation of copper
and molybdenum in severallarge plants.

MINERAL PROCESSING/ENVIRONMENT. HEAL TH ANO SAFETY

EXPERIMENTAL

MATERIAL

97

ANO PROCEOURES

Ore Samples
Ore samples from Chilean copper plants and copper-gold ores from Pero and
Indonesia were used in these studies. They representeda range of different ciar rninerals.
The ores used in thesestudiesand the ciar minerals contained in eachore type are given in
Table l.
Table 1- DescriptionOrales Used in the Study

Escondida
ffienc 1906)
Disputada
(high clay)
Mansa Mina
(Veta 3)
Escondida
(Andesite)
Minas Conga

Batu Hijau

Chile

Chile

Chile

Chile

Peru

lndonesia

Porphyry/Andesite

Kaolinite 12%
Illite 18%
Porphyry/Quartz
MontmoriUonite 10%
!
Illite 4%
Andesite/Quartz
Kaolinite 8%
Illite 4%
Andesite
MontmoriUonite 4%
Brarnmollite 2%
Porphyry/Andesite/Quartz
Kaolinite 22%
~nite 18%

Andesite

Chamosite11.5%
Kaolinite7%
Illite 5%

Initially, the ciar from each ore sample was removed using washing and
sedimentationtechniques. Then the rninus 7 ~m fraction was isolated and analysed by xray diffraction. The relative amountof ciar from eachore was then calculated.
Flotation Procedure
Standard flotation tests, establishedon eachore type, were used in this study. The
grinding fineness used in the operating plants ftom which the ores were obtained was
selectedas the baseline. Grinding tests were performed in a mild steel rod milI. Tests were
carried out in a Denver flotation machineusing standardoperating conditions.
Reagents
In the experimental testwork, standard,technical grade reagentssuchas xanthates,
dithiophosphates,dispersants,depressantsand frothers were used. Reagentswere obtained
from various mining chemical manufacturersand were used "as received".

98

VOLUME

EXPERIMENTAL

11

RESUL TS

Effect ofType and Level ofClay on Copper-Moiybdenum and Copper-Gold Flotation


Standard flotation tests were carried out with ores containing different cIay
minerals using standard reagentconditions. The results obtained are shown in Table II.
Table 11-Standard Flotation Tests on Different Ore Types
Ore Type
~
A
B
C
D
E
F

!eed G~a,de
%:~t
fg
2.3
1.6
0.9
1.2
0.4
0.6

Mo
--9.6
0.01
--5.2
--7.8
-1.2
-1.5

Au

Co~centrat~
Grade%. v./t
~~

-6.2

3.3
2.2

Mo
Au
--70.2
0.06
-45.1
--75.6
--55.4
-5
-3

% Recoverv
Cu

67.3
57.8

Mo
-40
---75
-70

Au-

The highest copper recovery was obtained on the ores that contained kaolinite and
iIIite. However, because of the presence of this cIar, the froth was dry and difficuIt to
remove. Ores containing montmorillonite and chamositegave very Iow copper recoveries.
The froth in these experiments had a fine texture, was poorIy mineraIized and had a short

Iifetime.
Copper recoveries in specific size fractions for ore types A, B and F are presented
in Figure 1 and show that very little copper was recovered from the coarse fractions of"B"
type ore containing montmorillonite clay. Substantially higher recoveries from the coarse
fractions were obtained on the ores containing kaolinite and illite clay slimes.
Experiments were conducted on ore types ~ B and F from which different
amounts of cIar were removed before grinding and flotation. The cIar was removed by
washing fue ore and desliming in a ten-miIIimeter cycIone. In each experiment, a minus 7
~m fraction was removed. The resuIts obtained are presentedin Figure 2 and demonstrate
that montmoriIlonite cIar (ore type B) and chamosite cIar (ore type F) have the most
harrnfuI effect on floatabiIity of copper mineraIs. Kaolinite and illite were not as
detrimentaI, but the aItered frothing properties mar have been the main reason for fue
reduced copper floatabiIity.

MINERAL PROCESSING/ENVIRONMENT. HEAL TH ANO SAFETY

99

Particle size lm]


Figure 1 -Copper Recovery in Size Fraction ofthe Flotation Tail for Various
Clay-Containing Ores
100
90
80
70

60
50
40

o B ore type
\7 F ore type
6
'1'

A ore type

'11'1"

'1"

'1'

10

12

'1"

14

1'"

16

1"

18 20

Clay content in flotation feed [%]


Figure 2 -EfIect of Concentrationof CIar in the Feed on Copper Recovery
from Various CIay-Containing Ores

Effect ofDifferent Dispersants


Experimental work was conductedto examine the effect of different dispersantson
copper t1otation. Previous work with other ores (14) had indicated that improved

100

VOLUME

11

100

'--'
90
Q
Q)
;>-

o
Q
Q)

80

o B ore type

>tO
Q

ie

70

"

F oretype

A ore type

60-

50
o

, ,

'

200

, I

'

400

.,

, I

'

600

..j

800

SHQ additions rgitl


Figure 3 -Effect ofDispersant SHQ on Copper Flotation from
Various Clay-Containing Ores
As shown in Table 111,Calgon glass and sodium silicate were not very effective as
dispersants.However, in a mixture with Quebracho, (SHQ), they had a positive effect on
copper grade and recovery. All ofthe organic polymers, CMC, Quebracho and Daxad 19
resulted in improved selectivity. Additional tests conducted with different levels of
dispersantSHQ are presentedin Figure 3, where it can be seenthat high additions of SHQ
(800 g/t) resulted in a significant increase in copper recovery from ore Type B. An increase
in recovery on ore Types B and Falso occurred at SHQ additions up to 600 g/t, while at
higher additions the recoverywas reduced.
Effect of Sodium Sulphide
It has beenestablishedin numerous studies that sodium sulphide (Na2Se9H2O)can
adsorb on cIar mineral surfaces and this prevents collector adsorption on cIay surfaces.
Sodium sulphide mar algo act as a dispersant.
The effect of sodium sulphide on the flotation of copper from ore types A, B, and E
was examined in more detail by varying the concentrationofthe reagent for each ore type.
The results obtainedare shown in Figure 4.
A significant improvement in copper recoverywas achieved with additions ofNa2S

MINERAL PROCESSING/ENVIRONMENT. HEAL TH ANO SAFETY

101

Table 111: Effect ofDifferent Dispersants


Dispersant
A~~itions
None

-~

OreType

Na2SiO3= 300 g/t

B
C

ConcGrade
Cu %
6.2
5.2

3.3

B
C
~

% Recovery
Cu
45.1
75.6
67.3

8.5
6.2

46.1
76.4

3.6

66.3

CalgonGlass= 300 g/t

B
C

CMC 6CTL = 300 g/t

B
C

10.1
9.1

50.6
80.1

Quebracho'S' = 300 g/t

B
C

6.5

8.8
6.6

70.0

4.2

75.2

B
C

11.3
10.1

49.4
80.5

6.6

69.8

-E

DaxadI9=300g/t
---E

SHQ = 300 g/t

B
C

-E

SHQ = Na.,siOj: Calgon: Quebracho(40:40:20)

6.0
5.3

44.8
70.7

3.1

60.5

50.2
81.4

9.5
7.2

50.3
85.0

4.2

75.1

above 200 g/t. A marked improvementwas acmevedon the ore containing montmorillonite
(ore type B). Another beneficial effect of Na2S in the flotation system of clay-containing
ores is the reduction in collector requirementas can be seenin Figure 5.
At increasedadditionsofNa2S (up to 300 g/t) collector requirementwas reduced.
100

~ 90C
o>
()
Q)

~ 80

~
()

'"
+

70-,

~
o

...

8 60
50

100

200

300

Na2S additions [g/t]

400

102

VOLUME

11

Figure 4 -Effect ofLevel ofNa2S Addition on Copper Recoveryfrom Various


Clay-containing Ores (40 g/t collector additions, pH 9.0)

o o g/t Na2S
1;7 150 g/t Na2S

1:. 300 g/t Na2S

Figure 5 -Effect ofLevel of CoIlector Additions on Copper Flotation from Ore Type B
Using Different Levels ofNa2S Additions
Effect of pH
The effect of pH was examined on ore Type B. Two series of experiments were
performed using 200 g/t Na2S, and without Na2S. The pH was adjusted with lime. The
results obtained are shown in Figure 6.
In the absence of sodium sulphide, a Sharp drop in copper recovery was evident
with increasedpH. The highest recovery was obtained at natural pH. The drop in recovery
with increasing pH was not as significant in the presenceofNa2S.

MINERAL PROCESSING/ENVIRONMENT. HEAL TH ANO SAFETY

103

90

50

Figure 6 -Effect of pH on Copper Flotation from Ore Type B


at Different Levels ofNa2S Additions
Effect of Po Ip Density
The effect of pulp density on copper flotation was examined on ore Types B, E and
F. A reduction in pulp density had a positive effect on copper recovery in all cases(Figure
7). Major ll1provementsin recovery were achieved at a pulp density below 20% solids.
90

~.

/1;;0---

o Boretype

~
'--'

/~

~ F ore type

~ 80
>
o

E ore type

(1)

'""'

70

60

,8

so-~:11
40

35

30

25

20

15

10

Solids in flotation feed [%]

Figure 7 -Effect ofPulp Density on Copper Flotation from Various Clay-containing Ores

104

VOLUME

11

As can be seen in Figure 8, another beneficial effect of flotation at reduced pulp


density is the significant reduction of slime transfer into the concentrate, and consequent
improvement in the concentrategrade.

Figure 8 -Effect ofPulp Density on Copper ConcentrateGrade


and Slime Contentofthe Concentrateftom Ore Type B

Effect of Type of Frother


One of the major problemsin flotation of clay-containing ore is their effect on the
frothing characteristics.The presenceof cIay in the ore can causethe following changes in
fue froth:
(a) Produce a froth that is fmely textured, poorly mineralized and incapable of carrying
coarseparticles.
(b) Completely destroy the ftoth (iron hydroxide clay) and
(c) Create a dry, tlocculated-like froth.
The literature gives very IittIe information on the effect of ciar on frothing
properties, even though frothing probIems are a rnajor contributor to reduced metal
recovery to the float concentrate.Evidence ofthe frothing probIem (18) in many operating
plants is the need to use a blend of two or more frothers. In this study it was observed that
the type of ciar present in a given ore had a significant effect on frothing properties and
froth Stability.

MINERAL PROCESSING/ENVIRONMENT. HEAL TH ANO SAFETY

105

In the presence of montmorillonite and chamosite, the froth is very unstable,


constantly collapsing as the liquid drains in betweenbubbles. The froth has a fine bubble
texture and depletesquickly, evenat high levels of frother addition.
In the case of kaolinite and illite, the froth is dry, with no bubble texture at the
beginning of flotation, and hasthe appearanceof being flocculated. After removal of the
initial froth, the bubbles become large and carry an appreciable amount of slime. Froth
dryness on this ore type can be overcome by using dithiophosphate or thionocarbamateas
the principal collector, reducing xanthateadditions or omitting xanthateentirely.
Experimental work with different frothers, on Type B ore containing
montmorillonite and illite clay, showed that frother type had a significant effect on fue rate
of copper tlotation and recovery. The effect of different frothers on the rate of copper
flotation is shown in Figure 9.
Blends offrothers gave more favorable results than a single frother, and significant
improvements in the late of copper flotation and recovery were achieved with the use of
frother HP700. The copper recovery in various size fractions using different frothers is
shown in Figure 10, and indicates that frother type effects the recovery of the coarsestand
fmest fractions most of all.

Figure 9 -Effect ofType ofFrother on the Rate ofCopper Flotation from Ore Type D

106

VOLUME

II

100

~
L---'

C
Q)

90

80

't)

70

...

60

Q)

50
40
30
='
u

20
10

020

100
Particle size

300
J.lm

Figure 10 -Copper Recoveryin Tailing Size Fraction Using Different Frother from Ore
TypeD
Effect ofFlowsheet Configurations
Because coarse and rniddling particles do not float well in the presenceof clay, it
was postulated that by removing cIay at some point in the circuit, or by separateflotation
of the [me and coarse ore fractions, the recovery of coarse particles rnight be improved.
Along these lines, severalroughing-scavengingflowsheets were designedand tested.
The configurations used in this study included a standard rougher-scavenger
flotation flowsheet (Figure 11), a sand-slime separationflotation flowsheet (Figure 12) and
a split circuit flowsheet (Figure 13), in which the rougher tailing was deslimed before
scavengerflotation. The results obtained with fuese different flowsheet configurations are
shown in Table IV for copperand copper-molybdenum ores and in Table V for a coppergold ore.
These experiments were conducted using the conditions that yielded improved
metallurgical results, i.e.Na2S and natural pH in the rougher-scavengerstages. The
standard flowsheet and fue slime-separation flowsheet gave similar recoveries. The split
circuit flowsheet gave higher copper recoveries on all the ore types of between3 and 5%.
Molybdenum and gold recoveries from fue respective ores were also higher.

MINERAL PROCESSING/ENVIRONMENT, HEALTH ANO SAFETY

Table IV -Effect ofFlowsheet Configuration on Copper and


Copper-MolybdenumOre Flotation
OreType
A
B
D

Ro + ScavConcGrade
Assavs%
Cu
Mo
Figure11 (standard)
12.3
-91.3
Figure12 (sand/slimesep'n) 11.1
-91.1
Figure 13(sDlitcircuit)
12.8
-95.3
Figure11 (standard)
8.8
0.07
Figure12(sand/slimesep'n)
6.8
0.06
Fi re 13 s lit circuit
9.2
0.07
Figure11 (standard)
7.9
-82.3
Figure12(sand/slimesep'n)
6.6
-80.5
Figure 13(sDlitcircuit)
8.2
-85.6
Flowsheet

Ro + ScavConc
% Recoverv
Cu
Mo
85.5
66.3
85.0
65.5
88.2
68.4
-

Table V -Effect ofFlowsheet Configuration on Copper-Gold Flotation


OreType
E
F

Ro + ScavConcGrade
Assavs%. 2/t
Cu
Au
Figure11 (standard)
2.3
6.82
Figure12(sand/slimesep'n)
2.4
6.70
Figure 13(sDlitcircuit)
3.2
9.66
Figure11 (standard)
5.2
13.56
Figure12(sand/slimesep'n)
4.4
12.20
Figure13 (sDlitcircuit)
5.4
13.80
Flowsheet

Ro + Scav.Conc
% Recoverv
Cu
Au
85.2
84.2
84.1
83.2
88.5
89.1
81.5
85.1
80.5
83.2
86.1
88.0

107

108

VOLUME

II

Figure 12. Sand-SlimeSeparationFlowsheet

Feed

'If
~

Sand

scavenger

Tailing.~

Slime scavenger
~

~~~~~~~~:~1
"'1
Concentrate

Concentrate

MINERAL PROCESSING/ENVIRONMENT, HEAL TH ANO SAFETY

109

Tbe Practica. Perspective


Research work has demonstrated that different types of clay minerals have a
negative effect on copper/molybdenum and copper/gold flotation. Montmorillonite and
chamosite exhibited the most harrnful effect on floatability. The pH was found to be
critical for copper flotation. Natural pH gave the best metallurgical results with frothers
designed to perforro well at lower pH regions. The difficulties experienced in operating
plants with flotation at low pH is associated with the frother used. Plants frequently
employ frothers, that require a higher pH for proper froth development. In order to
introduce a natural pH, flotation frothers that are less sensitive to variations in pH should
be selected.
It has been shown that lowering pulp density to a region below 20% solids will
improve recovery significantly. Reducing the pulp density to below 20% solids would
require major plant modifications 00 most plaots, so there are limitations in the extent to
which this efIect can be capitalized.
Dispersantsmay be applied with beneficial results, but at increasedoperating costs.
However, adding small quantities ofNa2S would improve flotation recovery and flotation
cate significantly. The additional cost of using Na2S would be offset by a reduction in
collector requirements. In addition, a lower operating pH can be tolerated when using

Na2S.
Perhapsthe most important parameterin the flotation of clay-containing ores is the
selection of frothers. The progress in the development of suitable frothers for claycontaining ores has been very slow. The HP seriesoffrothers (manufactured by SENMIN)
gave
highly
promising results. These frothers contain amine-modified
trialkoxypropyltrioxane, which performswell over a wide range of pH.
Another possible solution is the use of a split circuit t1owsheet, where slime
removal before scavenging could add 3 to 5% in additional copper recovery. Slime
removal can be effectively achieved even with large 750 mm cyclones (15).

CONCLUSIONS

The following mar be concluded from the experimentalwork:


Different cIay minerals affect the floatability of copper and associated valuable
rninerals (i.e. gold, molybdenum) in different ways and, therefore, the cIay minerals in
any plant feed, should be well characterized.
The pulp pH affects the floatability of copper and gold significantly. Under laboratory
conditions, natural pH gave the best metallurgical results.
Some organic dispersants,such as SHQ, have a positive effect on flotation. The rnost
pronounced effect on flotation was achieved by Na2S, which resulted in improved
recoveries and a reduction in collector consumption.

.
5.
6.
7.
9.

10

VOLUME

11

The most significant improvement in floatability resulted from using specific frothers
and natural pH. Perhapswith more collaborative researchin this afea, an improvement
in the floatability o clay-containing ores mar resulto
The split circuit flowsheet configuration mar result in improved recovery in the afea o
4 to 6%.

REFERENCES

1.

D.J. Brown and H.G. Smith, Continuoustesting o frothers, Colliery Eng. 31,
pp245-250,1954

A. Jowett et al., Slime coating o coal in t1otation~ul!,s. Fuel No. 35, pp303-309,
1956

3.

I.N. Plaksin and A.M. Ocolovich, The effect o lime and slimes in flotation
se~arationo some sul!,hides. Publ Nanka, Russia, 1965

4.

G.RM. Del Guidice, A study o slime coatillgs in flotation, Trans. AIME 112,

pp398-409,1934
A.C. Dovenfel~ Slime coatings: how to emlain and control them, Eng. Min.
Journa1154,
pp87-91,1953
S.G. Bankofl: E~riments
1943

with slirne coati!!gs, Trans. AIME 153, pp473-478,

S.C. SUD,'[he mechanismofslime coatillgs, Trans. AIME 153, pp479-492, 1943


8,

D. W. Fuerstenauet al., Iron oxide slime coatings in flotatioD, Trans. AIME 211,

pp792-793,1958
Iwasaki, et al, !ron wash ore slimes. some mineralogical and flotation
characteristics,Trans. AIME 223, pp97-108, 1962

10.

V.I. KIassenand V.A. Mocrousov, An introduction in !he theoa o flotatioD,


Butterworth,London,p493,1969

11.

V.I. KIassen and l. V. Nedogoborab, Slimes in the tlotation Rrocess,Izd. Nedra,


Russia,p245, 1969

12.

w. W. Wenand S.C.Sun,An electrokineticstudyof an aminetlotationof oxidized


~, Trans.AIME 262,ppI74-180, 1977

13.

K.A. Cazerlendand I.B. Uork. Flotation ~rinci~als, Metallurgizdaf, Russia, 1958

MINERAL PROCESSING/ENVIRONMENT. HEALTH ANO SAFETY

14.

S.M. Bulatovic et al., Flotation of oxide con~r ores from Brazil, Report of

Investigation,LR-4680,1996.
15

S.M. Bulatovic, W.T. Yen and A.C.T. Bigg, Improvement in the Qlant~rformance
ofthe SevenConcentratorsfrom Gecamines.Zaire, Report ofInvestigation, Vol. 7,
LR-3150,1984.