Minerals Engineering, Vol. 2, No. 1, pp.

93-109, 1989
Printed in Great Britain

MODELLING

0892-6875/89 $3.00 + 0.00

1989 Pergamon Press plc

PULP C H E M I S T R Y IN CALCITE FLOTATION.

OF O L E A T E A D S O R P T I O N USING T H E O R E T I C A L E Q U I L I B R I U M

B.-M.
Div.

ANTTI

CALCULATIONS

and E. F O R S S B E R G

of Mineral

(Received

Processing, Lulea U n i v e r s i t y of Technology,

S-951 87 Lulea, Sweden
I@ April 1@88~ revision 26 September 1@88)

ABSTRACT
The usual method of obtaining calcite concentrates is reverse flotation,
i.e. removal of impurities by flotation. This paper considers the
conditions required for direct flotation of calcite. The reason is that
calcite often occurs as an impurity in apatite and scheelite flotation,
where it floats together with the principal mineral. In this context it
is relevant to understand the mechanisms that control the flotation of
calcite.
Flotation experiments have been performed with oleate as the collector
reagent and water glass as the dispersant and modifier. To be able to
explain what happens in the flotation, solubility and adsorption
experiments have been conducted parallel to, and under the same
conditions as, the flotation experiments.
Theoretical equilibrium calculations have been made with the help of
data from the practical experiments for the purpose of modelling the
adsorption experiments. The calculations point to the existence of a
surface complex, CaOH01, which is important at pH>10 and low oleate
concentrations. Ca(01) 2 is formed at lower pH.
Water glass has a negative effect on oleate adsorption and if the water
glass concentration is high enough, >2000 g/t, calcite is totally
depressed. With theoretical equilibrium calculations it is possible to
predict that silicate ions will form complexes with calcium ions at the
mineral surface.

Ke,ywords
Calcite flotation; pulp
equilibrium calculations

chemistry;

oleate

adsorption

theoretical

INTRODUCTION
Fatty acids and their salts are n o r m a l l y used as c o l l e c t o r reagents for d i r e c t
flotation
of c a l c i t e ,
as w e l l as of o t h e r s a l t - l i k e
minerals
(apatite,
scheelite, b a r i t e and fluorite). Much work has been done o n e x p l a i n i n g
the
m e c h a n i s m of a d s o r p t i o n of these c o l l e c t o r s to m i n e r a l surfaces, as r e v i e w e d
by Hanna and S o m a s u n d a r a n [I].
Somasundaran
[2] s u g g e s t e d that the a d s o r p t i o n of o l e a t e on to c a l c i t e was
e l e c t r o s t a t i c at pH levels b e l o w the p.z.c, and c h e m i c a l at h i g h e r l e v e l s .
Above
the p.z.c,
the mineral
surface
is n e g a t i v e l y
charged,
and with
i n c r e a s i n g a d s o r p t i o n of oleate the zeta p o t e n t i a l falls still farther, w h i c h
is e x p l a i n e d
by specific adsorption
of o l e a t e ,
i.e. c h e m i s o r p t i o n .
This
c o n d i t i o n holds good up to m o n o l a y e r c o v e r a g e of the mineral surface. Similar
results have been o b t a i n e d by M i s h r a [3], Pugh and Stenius [4] and H a n u m a n t h a
Rao et al. [5].
Surface compounds
IR [6,7] and FTIR

that
[8].

support

the

chemisorption

93

theory

have

been

detected

by

94

B.-M. ANTTI and E. FORSSBERG

M a r i n a k i s and S h e r g o l d [9] argue that the a d s o r p t i o n m e c h a n i s m is a c t u a l l y a

p r e c i p i t a t i o n of i n s o l u b l e metal soap w h i c h sticks to t h e m i n e r a l
surface.
They found that f l o t a t i o n depends not only on the amount of oleate abstracted,
but also on the s t r e n g t h with w h i c h the metal soap a d h e r e s to the m i n e r a l
surface.
Water
glass
is t h e m o s t w i d e l y u s e d i n o r g a n i c
depressant
in s e l e c t i v e
f l o t a t i o n of these m i n e r a l systems. B e c a u s e of the c o m p l e x i t y of the silicate
system, the m e c h a n i s m of silicate a d s o r p t i o n has not yet been fully explained.
Various
authors
have suggested
adsorption
of s i l i c a ,
silicate
ions or
a m o r p h o u s SiO 2 [3,10,11,12].
The present authors
h a v e s t u d i e d the c a l c i t e - o l e a t e - s i l i c a t e
system with
reference
to a d s o r p t i o n
of o l e a t e a n d r e l a t e d
flotation
behaviour
as a
function
of pH, o l e a t e c o n c e n t r a t i o n and w a t e r glass concentration. On the
basis of the results of the a d s o r p t i o n e x p e r i m e n t s we have made t h e o r e t i c a l
equilibrium
calculations
to t r y to e x p l a i n how oleate and w a t e r glass are
a d s o r b e d on calcite. The t h e o r e t i c a l m o d e l s h a v e b e e n u s e d to e x p l a i n the
f l o t a t i o n results.

EXPERIMENTS
Material
Limestone
from Norvijaur
grading
84.5% CaCO 3 was
material. The p r i n c i p a l impurity was quartz.

used

as

the

experimental

The m a t e r i a l was r e c e i v e d in a c o a r s e - c r u s h e d state. After fine c r u s h i n g and

q u a r t e r i n g to I kg batches it was w e t - m i l l e d in a stainless steel l a b o r a t o r y
m i l l w i t h i n t e r i o r d i m e n s i o n s of 33 cm by 21 cm in diameter. The g r i n d i n g
charge c o n s i s t e d of s t a i n l e s s steel rods with a total mass of 1 3 . 8 kg. T e n
minutes' g r i n d i n g p r o d u c e d a m a t e r i a l of ks0 = 80 microns.
The m i l l e d m a t e r i a l was dried and stored dry at r o o m
subsequently
u s e d in t h e s o l u b i l i t y
and adsorption
f l o t a t i o n e x p e r i m e n t s the c a l c i t e was mixed w i t h pure
m i c r o n s to make a f l o t a t i o n feed g r a d i n g 10% calcite
surface of the m a t e r i a l was d e t e r m i n e d with n i t r o g e n by

temperature,
and was
experiments.
F o r the
quartz sand (k80 = 180
by mass. T h e s p e c i f i c
the BET method.

Reagents
Sodium oleate from Riedel-De
H a e n (analar grade) was used w i t h o u t further
p u r i f i c a t i o n . The w a t e r glass used was o b t a i n e d from EKA Nobel AB and has a
S i O 2 : N a 2 0 ratio of 3.3.
Method
A series
of s o l u b i l i t y
experiments
was conducted
to s t u d y the r a t e of
d i s s o l u t i o n of calcite. Dried m i l l e d calcite was slurried in d e i o n i z e d w a t e r
w i t h a m a g n e t i c stirrer. The p r o p o r t i o n s of calcite and w a t e r were chosen to
give a pulp with 28% s o l i d s by m a s s . T h e s a m p l e w a s f i l t e r e d at v a r i o u s
intervals
and the filtrate
was analyzed
b o t h for total c a l c i u m by atomic
absorption
spectrophotometry
(AAS) and for [HCO3-] by t i t r a t i o n with 0.05 M
HCl. The pH was m e a s u r e d with a c o m b i n a t i o n electrode.
The adsorption
experiments
w e r e m a d e to i n v e s t i g a t e how the a d s o r p t i o n of
o l e a t e on calcite was a f f e c t e d by w a t e r g l a s s . A c o n d i t i o n i n g
t i m e of 15
minutes
was chosen
to o b t a i n r e s u l t s
relevant
to f l o t a t i o n .
As in t h e
s o l u b i l i t y experiments, the p r o p o r t i o n s of mineral and solution were chosen to
give 28% solids by mass.
Five series of e x p e r i m e n t s were run in w h i c h calcite was c o n d i t i o n e d (a) w i t h
oleate alone, (b) first with silicate s o l u t i o n and then with oleate solution,
a n d (c) w i t h a m i x t u r e of s i l i c a t e and oleate. The pH was kept c o n s t a n t at
10.60.2, and the initial o l e a t e c o n c e n t r a t i o n was v a r i e d b e t w e e n 6.6 x 10 -5
and I x 10 -3 M.
T h e c h o i c e of pH = 1 0 . 6 a v o i d e d p r e c i p i t a t i o n
of a m o r p h o u s silica in the
solutions.
As Fig. 10 s h o w s , S i O ( O H ) 3- w a s the d o m i n a n t species in these
silicate solutions at this pH level.

Pulp chemistry in calcite flotation

95

After 15 and 15+15 minutes' c o n d i t i o n i n g the calcite was filtered off and the
f i l t r a t e was analyzed for Catot, residual oleate and residual silicate. The pH
was m e a s u r e d c o n t i n u o u s l y during the p r o g r e s s of the experiments. Both oleate
c o n c e n t r a t i o n and silicate c o n c e n t r a t i o n w e r e m e a s u r e d s p e c t r o p h o t o m e t r i c a l l y
[I 3,14], and the total calcium content as before by AAS. The c o n c e n t r a t i o n of
d i s s o l v e d c a r b o n d i o x i d e was m e a s u r e d w i t h a specific CO 2 e l e c t r o d e (Orion
9502). T h e q u a n t i t y of o l e a t e a d s o r b e d was c a l c u l a t e d as the d i f f e r e n c e
between
the initial
and residual
concentrations
after
1 5 minutes'
conditioning.
The flotation
experiments
were performed
in a W E M C O f l o t a t i o n c e l l of
F a g e r g r e n type. The q u a n t i t y of m a t e r i a l in each e x p e r i m e n t s w a s I kg (10%
N o r v i j a u r calcite by mass) and 2.4-2.5 litres of pulp liquid. O l e a t e was added
in the form of an 0.5% basic s o l u t i o n , a n d w a t e r g l a s s as a 20% s o l u t i o n
r e c k o n e d on the 37% c o m m e r c i a l product. The pH was a d j u s t e d w i t h NaOH or HCI.
The c o n d i t i o n i n g time for pH a d j u s t m e n t or water glass a d d i t i o n was 10 minutes
in all experiments. The c o l l e c t o r was then added, and the f l o t a t i o n started
after a further 7 minutes' conditioning. After 3 minutes' flotation (conc. I)
one or two drops of frother (methyl isobutyl carbinol, MIBC) were added and
the f l o t a t i o n then continued for a further 3 minutes (conc. II).
The pH was m e a s u r e d c o n t i n u o u s l y during the progress of flotation and was kept
c o n s t a n t u n t i l a i r i n j e c t i o n s t a r t e d . T h e pH u s u a l l y f e l l s l i g h t l y
as
f l o t a t i o n p r o g r e s s e d . The floated products, conc. I and II, were dried and
a n a l y z e d s e p a r a t e l y for calcium. The reported grades and recoveries, however,
refer to the a g g r e g a t e result from each experiment.

RESULTS AND D I S C U S S I O N
Solubility experiments
F i g u r e la s h o w s the c h a n g e in pH and Fig. Ib the c h a n g e in c a l c i u m and
b i c a r b o n a t e c o n c e n t r a t i o n s as a function of time w h e n calcite is c o n d i t i o n e d
in pure w a t e r under c o n d i t i o n s c o r r e s p o n d i n g to those of an open system.

pH

9
LogCi
-2

o
x

[Ca]tot
[HCO ]

-3

'

TIME (hours)

-/.

TIME (hours)

Fig.1
C o n d i t i o n i n g of calcite in water
a. change in pH as a f u n c t i o n of time
b. [Ca]to t and [HCO3-] as a function of time
(broken lines show theoretical
e q u i l i b r i u m c o n c e n t r a t i o n s in an open system)
If pure calcite is in e q u i l i b r i u m with water and the system is open, i.e. in
e q u i l i b r i u m w i t h a t m o s p h e r i c CO 2 (g), then pH = 8.4, log [Ca]to t = -3.4 and
log [HCO3- ] = -3.03 [15,16].
E q u i l i b r a t i o n is e v i d e n t l y slow in this system, and it is the HCO 3- ions that
are the cause. This is a c o n s e q u e n c e of the slow and v a r i a b l e rate at w h i c h
a t m o s p h e r i c CO 2 (g) goes into s o l u t i o n [17]. The c a l c i t e - w a t e r system cannot
t h e r e f o r e be regarded as an open system if the c o n d i t i o n i n g time is less than

96

B.-M. ANTTI and E. FORSSBERG

three hours, as is the case in flotation. In the laboratory scale f l o t a t i o n

e x p e r i m e n t s the dwell time of the calcite in the pulp was of the order of 1520 minutes.
For a completely
closed
system,
i.e.
one shielded
from contact with
a t m o s p h e r i c CO 2 (g), we obtained the f o l l o w i n g t h e o r e t i c a l e q u i l i b r i u m values:
pH -- 9.9-10.0, log [Ca]to t = -3.9 and log [HC03-] = -4.05 [15,16].
F i g u r e s la and Ib show that the c a l c i t e - w a t e r system cannot be regarded as a
closed system even if the c o n d i t i o n i n g time is short. This fact is allowed for
in t h e t h e o r e t i c a l
equilibrium
calculations
on t h i s s y s t e m ,
which
are
d i s c u s s e d later.
Adsorption

experiments

The purpose
of the adsorption
experiments
w a s to i n v e s t i g a t e
h o w the
a d s o r p t i o n of o l e a t e on calcite is a f f e c t e d by water glass. The c o n d i t i o n i n g
times were deliberately
kept shorter than equilibration
time in order to
o b t a i n results r e l e v a n t to flotation. The q u a n t i t i e s of o l e a t e a d s o r b e d
in
each series of e x p e r i m e n t s are shown in Fig. 2 as a function of oleate left in
solution.
4

=h
o
w
m
~2

o
u9
a
<

o
0

10-6

IIIT

10-s

| I I

10-4

OLEATE LEFT IN SOLUTION (moles/I)

Fig.2
A d s o r p t i o n of oleate on calcite
o Na oleate; A 2 x 10 -3 M Na2SiO 3 + Na oleate;
<> 5 x 10 -3 M Na2SiO 3 + Na oleate;
+ Na oleate and 2 x 10 -3 M N a 2 S i O 3 m i x e d before c o n d i t i o n i n g
To c o r r e s p o n d to m o n o l a y e r c o v e r a @ e of the m i n e r a l
s u r f a c e the a d s o r p t i o n
d e n s i t y should be 5 or 8 u m o l e s / m z, d e p e n d i n g on w h e t h e r the a d s o r b e d oleate
ions occur as h y d r a t e d c r y s t a l s (surface area per m o l e c u l e = 20.75 A 2) or as
liquid crystals
(surface area per molecule
= 33 A 2) [18]. With the pulp
d e n s i t y and the r e l a t i v e l y short c o n d i t i o n i n g time used in the e x p e r i m e n t s ,
the plateau
of a d s o r p t i o n
corresponding
to m o n o l a y e r
coverage
is n e v e r
reached.
If we c a l c u l a t e
the e q u i l i b r i u m
concentrations
of Ca 2+ a n d O1- from the
solubility
product
f o r C a ( O l ) 2 (s) [19] and c o m p a r e them with the results
m e a s u r e d in the a d s o r p t i o n e x p e r i m e n t s in pure oleate solution, we find that
the e x p e r i m e n t a l
c o n c e n t r a t i o n s are much h i g h e r than those c o r r e s p o n d i n g to
p r e c i p i t a t i o n of Ca(Ol) 2 (s). This indicates that no p r e c i p i t a t i o n of c a l c i u m
oleate has taken place in the pulp and that the a d s o r p t i o n results c o r r e s p o n d
to real
adsorption
on the mineral
surfaces.
The question
is h o w t h i s
a d s o r p t i o n takes place, and what the mineral surfaces look like a f t e r w a r d s .
Have o l e a t e ions been bonded to the Ca 2+ ions in the lattice (chemisorption),
or has c a l c i u m o l e a t e p r e c i p i t a t e d
in the i n t e r f a c e
between
the m i n e r a l
surface and the ambient
solution?
Attempts
h a v e been made to e x p l a i n the
adsorption
r e s u l t in p u r e o l e a t e
solution
w i t h t h e h e l p of t h e o r e t i c a l
calculations, w h i c h will be r e p o r t e d later.
As far as the effect of water glass on the a d s o r p t i o n of oleate is concerned,
it is e v i d e n t that a d d i t i o n s of s i l i ca t e have an i n h i b i t i n g effect on oleate
a d s o r p t i o n (the s i l i c a t e c o n c e n t r a t i o n s were e q u i v a l e n t to dosages of 1 a n d

Pulp chemistry in calcite flotation

97

2.5 kg w a t e r glass per tonne). The effect of the w a t e r glass is less if it is

added at the same time as the collector, w h i c h implies that the o l e a t e ion
bonds more s t r o n g l y than the silicate ion to the m i n e r a l surface, or that the
a d s o r p t i o n k i n e t i c s for oleate is faster. This means t h a t the r e l a t i o n s h i p
b e t w e e n c o n d i t i o n i n g time for w a t e r glass and c o l l e c t o r is significant, e.g.
if one w i s h e s to d e p r e s s calcite in a f l o t a t i o n process.
Flotation experiments
T h e s a m e p u l p d e n s i t y w a s u s e d in the f l o t a t i o n e x p e r i m e n t s
as in the
s o l u b i l i t y and a d s o r p t i o n experiments. In order to obtain a more r e a l i s t i c a l l y
f l o a t a b l e q u a n t i t y o f m a t e r i a l , the calcite was m i x e d w i t h quartz sand in
p r o p o r t i o n s giving 10% calcite by mass in the feed.
E f f e c t of oleate c o n c e n t r a t i o n
F i g u r e s 3a a n d 3b show the results of f l o t a t i o n e x p e r i m e n t s p e r f o r m e d at a
c o n s t a n t pH of 10 and a constant w a t e r glass c o n c e n t r a t i o n of 2000 g/t. The
c o l l e c t o r c o n c e n t r a t i o n s were varied.

60
PURE CALCITE

(120)
o

50

(290)
o
FEED

(34)
O
[14)
O

4O

LU
C3

100

<

30

nO
0

F38

).,
t~
LU
O

o (68l

2O
( ) g / t Na OLEATE

F12

s0

rv.
w
i,-

10

'

50

'

160

'

1;0

'

200

' 250

' 300

soo,u. 0LEATE =g/tl

50

100

CALCITE RECOVERY (%)

Fig.3
C a l c i t e f l o t a t i o n at pH 10, water glass c o n c e n t r a t i o n 2000 g/t
a. Calcite recovery as a f u n c t i o n of c o l l e c t o r reagent c o n c e n t r a t i o n
b. C o n c e n t r a t i o n and recovery as functions of c o l l e c t o r reagent c o n c e n t r a t i o n
As Fig. 3a shows, calcite r e c o v e r y i n c r e a s e s w i t h c o l l e c t o r c o n c e n t r a t i o n
w i t h i n the interval of c o n c e n t r a t i o n s studied. This is what can be e x p e c t e d as
long as there is not a surplus of c o l l e c t o r reagent relative to the a v a i l a b l e
m i n e r a l s u r f a c e . In this c o n t e x t it is i n t e r e s t i n g to compare the r e c o v e r y
curve with the a d s o r p t i o n i s o t h e r m for pure oleate solution (Fig. 2). A l l o w i n g
for the actual c o l l e c t o r reagent c o n c e n t r a t i o n s and a v a i l a b l e mineral surface,
we find that most of the f l o t a t i o n e x p e r i m e n t s fall w i t h i n the f r a m e w o r k of
the c o n d i t i o n s p r e v a i l i n g in the a d s o r p t i o n e x p e r i m e n t s (Table I).
The probable explanation
of the
collector concentration
is s u c h
ME 211---G

f a c t t h a t r e c o v e r y is h i g h e s t w h e n the
as to c r e a t e c o n d i t i o n s for f o r m a t i o n of

98

B.-M. ANTII and E. FORSSBERG

m u l t i p l e layers on the mineral surface is that the f l o t a t i o n e x p e r i m e n t s were

p e r f o r m e d at high w a t e r glass concentrations. The mineral surface is p a r t l y
b l o c k e d by s i l i c a t e ions, and it t h e r e f o r e takes a higher c o n c e n t r a t i o n of
c o l l e c t o r reagent to make the mineral float.

TABLE 1 Relationship between available mineral surface and collector

reagent concentration in flotation experiments presented in Fig. 3a
Experiment

Calcite

m2/g

F12-14
F23
F38

Sto t

T c oleate

m2

1.09
0.63
0.69

100
100
100

109
63
69

Oleate
~moles/m 2

2.1xi0 -5 - 1.8x10 -4
1.0 x 10 -4
4.3 x 10 -4

0.46-4.0
3.8
15.0

At the h i g h e s t o l e a t e c o n c e n t r a t i o n s we find some loss of s e l e c t i v i t y w i t h

respect to q u a r t z . A c c o r d i n g to the g r a d e - r e c o v e r y
c u r v e (Fig. 3b), the
o p t i m u m amount of c o l l e c t o r reagent seems to be in the region of 120 g oleate
per tonne. This oleate c o n c e n t r a t i o n was t h e r e f o r e used in the other flotation
experiments.
E f f e c t of water glass
To study how the w a t e r glass c o n c e n t r a t i o n affects the f l o t a t i o n of calcite,
the e x p e r i m e n t s w e r e p e r f o r m e d at a c o n s t a n t c o n c e n t r a t i o n
of c o l l e c t o r
r e a g e n t (120 g o l e a t e p e r t o n n e ) a n d a c o n s t a n t pH (10). Figure 4a shows
calcite r e c o v e r y as a f u n c t i o n of water glass concentration, and Fig. 4b shows
the c o r r e s p o n d i n g g r a d e - r e c o v e r y curve.

60
. _

Z_U~E_C..ALCJZ~

..............

o 500
o 2000
o 1000

50

FEED
o0

40,
A

,%

LU
E3
<
IX
(..9

100

o 3000

30

o 4000

0
>-

20'

tU
>
0
O

o 6000

~ so
W

10,
O 9 / t WATER GLASS

2000
&0100
WATER GLASS (g/t)

6000

. . . .
5b . . . .
loo
CALCITE RECOVERY (%)

Fig.4
C a l c i t e flotation at pH 10, oleate c o n c e n t r a t i o n 120 g/t
a. Calcite recovery as a f u n c t i o n of water glass c o n c e n t r a t i o n
b. C o n c e n t r a t i o n and recovery as functions of water glass c o n c e n t r a t i o n

Pulp chemistry in calcite flotation

99

At water glass concentrations below 2000 g/t the silicate system is largely
p r e s e n t in the f o r m of SiO(OH) 3- ions (Fig. 10), w h i l e a m o r p h o u s silica
predominates at water glass concentrations above 2000 g/t. The drastic drop in
f l o t a t i o n recovery that occurs when the water glass concentration is raised
from 2000 to 3000 g/t can be ascribed to precipitation of amorphous silica on
the m i n e r a l s u r f a c e s , w h i c h e f f e c t i v e l y makes them inaccessible to oleate
ions.
In the i n t e r v a l from 0 to 2000 g w a t e r g l a s s per tonne, an i n c r e a s i n g
concentration of silicate ions has an increasingly damping effect on flotation
recovery, which indicates that a surface complex is formed between Ca 2+ on the
mineral surface and silicate. The higher the concentration of silicate ions,
the f e w e r 'free' Ca 2+ p o s i t i o n s in the s u r f a c e lattice are available for
oleate ions.
It is not however possible to get the best selectivity with respect to quartz
without using water glass. According to the grade-recovery curve, the optimum
dosage of water glass is 500 g/t.
The s i g n i f i c a n c e of w a t e r g l a s s as a d i s p e r s a n t has been investigated by
Bohlin [20]. Without water glass, the c a l c i t e p a r t i c l e s in b o t h f l o t a t i o n
pulps and 'pure' systems carry only a weak negative charge (0
-10 mV). At
these potentials the calcite particles can be expected to flocculate and also
to be adsorbed on quartz surfaces [21]. Addition of water glass reduces the
zeta potential of both calcite and quartz and causes the system to disperse.
This dispersion is essential to selective flotation.
Effect of pH
On the basis of the results obtained, the effect of pH was tested when the
oleate concentration was 120 g/t and the water glass c o n c e n t r a t i o n was 500
g/t. For purposes of comparison, some flotation experiments were also made at
various pH levels without water glass.
As Fig. 5 shows, calcite recovery was lower at pH a 10 both with and without
water glass, but selectivity is best at pH = 10 in the system with 500 g water
g l a s s per tonne. Without water glass recovery is better but selectivity is
poorer than when water glass is present in the pulp.
100

6
w
CE

50-

W
kI,I

o 120 g / t
500g/t
x 120 g / t

0 ~W~

Fig.5

r
8

E3

Na OLEATE
WATER GLASS
No OLEATE

,
9

i
10

v
11

t9
O

g,

12
pH
Calcite recovery and CaO grade of flotation
product as a function of pH

THEORETICAL EQUILIBRIUM CALCULATIONS

Method
S O L G A S W A T E R computer software [22] was used for the theoretical equilibrium
calculations. The SOLGASWATER program represents a methodology for calculating
the e q u i l i b r i u m c o m p o s i t i o n s of m u l t i p l e - p h a s e systems. E a c h phase is a

100

B.-M. ANTTI and E. FORSSBERG

homogeneous
p a r t of the system. H o m o g e n e i t y in this context means that the
phase has the same chemical and physical p r o p e r t i e s throughout the system. The
method
of c a l c u l a t i o n
is a p p l i c a b l e
to
d i l u t e s o l u t i o n s or s o l u t i o n s
c o n t a i n i n g an ion medium, which means that the s o l v e n t i s a s s u m e d
to h a v e
c o n s t a n t unit a c t i v i t y and need not be regarded as an independent component of
the system, even though it takes part in chemical reactions. (The activity of
dissolved
substances
is a s s u m e d
to b e p r o p o r t i o n a l
to their
molar
concentrations).
The a l g o r i t h m of the p r o g r a m m i n i m i z e s the total free energy of the system,
w h i c h a c c o r d i n g to t h e r m o d y n a m i c p r i n c i p l e s is lowest at equilibrium; it can
be a p p l i e d to systems c o n t a i n i n g one or more liquid phases w i t h a v a r i a b l e
number of d i s s o l v e d species, one gas phase of constant volume a n d up to 31
solid phases. The d i s s o l v e d species are d i v i d e d into components and complexes,
the c o m p o n e n t s r e p r e s e n t i n g the smallest number of pure substances needed for
u n a m b i g u o u s d e f i n i t i o n of the c o m p o s i t i o n s of all the species (solutes and
solids) in the system.
Input
Every conceivable
s p e c i e s in the system (S 98) must be d e f i n e d before the
c a l c u l a t i o n s start. A f o r m a t i o n constant, Kf, is stated for each species, as
well as its c o m p o s i t i o n in terms of components. The f o r m a t i o n constant of the
c o m p o n e n t s is set at 1.0.
The chosen c o m p o n e n t s of the calcite system are H +, Ca 2+ and CO 2 (aq). Using
k n o w n e q u i l i b r i u m data [23,24], we obtain the f o r m a t i o n c o n s t a n t s for e a c h
species, for example:
K_f for CaOH +
(I)

Ca 2+ + OH- = CaOH +

log K = 1.3

(2)

H20 = H + + OH-

log K = -14.0

(I) + (2) gives

Ca 2+ - H + = CaOH +

log Kf = -12.7

and the c o m p o s i t i o n on the basis of the chosen components is -1,1,0 (compare

t h e l i s t of s p e c i e s of the c a l c i t e s y s t e m in Table 2). In a d d i t i o n it is
n e c e s s a r y to state the total c o n c e n t r a t i o n of each c o m p o n e n t in the system and
h o w it v a r i e s . The total c o n c e n t r a t i o n is the sum of the c o n c e n t r a t i o n s of
each species in w h i c h the c o m p o n e n t is present.
Output
The e q u i l i b r i u m c o m p o s i t i o n of the system can be o b t a i n e d in both tabular and
graphic form. With table p r i n t o u t the u s e r c a n c h o o s e b e t w e e n e q u i l i b r i u m
c o n c e n t r a t i o n , e q u i l i b r i u m a c t i v i t y and the logarithms of those quantities. If
he prefers to p r e s e n t his e q u i l i b r i u m data in graph form he can c h o o s e for
example b e t w e e n d o m i n a n c e and l o g a r i t h m i c diagrams.
Dominance diagrams show which solid phases containing a given component
p r e d o m i n a t e at a given point, or the d o m i n a n t d i s s o l v e d species if no solid
phase are present (Fig. 10). In logarithmic d i a g r a m s the log c o n c e n t r a t i o n s of
all species are plotted against the v a r i a t i o n in c o n c e n t r a t i o n of a selected
c o m p o n e n t (cf. Fig 11).

RESULTS
Conditions
The purpose of the c a l c u l a t i o n s was to simulate the c o n d i t i o n s p r e v a i l i n g in
the s o l u b i l i t y and a d s o r p t i o n experiments. The BET s u r f a c e of the m a t e r i a l
used
in t h e s e e x p e r i m e n t s
v a r i e d b e t w e e n 0.7 a n d 0.9 m 2 / g . In a l l the
c a l c u l a t i o n s the total c o n c e n t r a t i o n
of Ca w a s e q u a t e d w i t h the ' s u r f a c e
molarity' of calcite. This 'surface molarity' can be c a l c u l a t e d from the BET
surface if one makes an a s s u m p t i o n as to how many m o n o l a y e r s take part in the
reaction. Here it was assumed that 5-10 m o n o l a y e r s take part, w h i c h gives a
'surface molarity' for calcite of the order of 1.88 x 10 -2 - 3.76 x 10 -2 M.
For the m e t h o d of c a l c u l a t i n g 'surface molarity', please see A p p e n d i x I.

Pulp chemistry in calcite flotation

TABLE 2

Complete llst of species present in t h e

calclte-oleate-silicate
system

(H +, C a 2+, C O 2 { a q ) ,

Log K F

No.
Fluid

Si(OH}4,

HOl(aq},

Stoichiometry

N a )

matrix

H+

.000

l.O0

.00

.00

.00

.00

.00

Ca 2+

.000

.00

l.O0

.00

.00

.00

.00

Ca0H +

-12.700

-l.O0

l.O0

,00

.00

.00

.00

CO2(aq)

.000

.00

.00

1.00

.00

.00

.00

H C O 3-

-6.382

-l.O0

.00

l.O0

.00

.00

.00

CO32-

-16.681

-2.00

.00

l.O0

.00

.00

.00

[22]

CaC03 (aq)

-13.531

-2.00

l.O0

l.O0

.00

.00

.00

[22]

-5.352

-l.O0

l.O0

l.O0

.00

.00

.00

[22]

.000

.00

.00

.00

l.O0

.00

.00

[22]

[22]

CaHC03-

H2Si

i0

HSi-

-9.860

-l.00

.00

.00 1.00

.00

.00 [22]

ii

Si 2-

-22.960

-2.00

.00

.00 1.00

.00

.00 [22]

12

Si42-

-13.640

-2.00

.00

.00

4.00

.00

.00

[22]

.00

.00

4.00

[22]

13

Si44-

-35.940

-4.00

.00

.00

14

CaSi(aq)

-19.870

-2.00 1.00

.00 1.00

.00

.00 [22]

15

CaHSi +

-9.470

-1.00

l.O0

.00

1.00

.00

.00

[22]

16

Ca(HSi)2

-16.830

-2.00

l.O0

.00

2.00

.00

.00

[22]

17

HOl(aq)

000

.00

.00

.00

.00

l.O0

.00

18

O1-

-4.950

-].00

.00

.00

.00

l.O0

.00

[23]

19

(01)2H-

000

-l.O0

.00

.00

.00

2.00

.00

[23]

20

(01)22-

-5.900

-2.00

.00

.00

.00

2.00

.00

[23]

21

Na +

.00

.00

.00

.00

1.00

.00

.00

.00

[22]

Solid

.000

.00

s
-22.810

-2.00

l.O0

.00

-8.331

-2.00

l.O0

l.O0

,00

.00

.00

[22]

-15.760

-2.00

l.O0

.00

l.O0

.00

.00

[22]

.00

.00

.00

.00

l.O0

.00

[23]

-2.00

l.O0

.00

.00

2.00

.00

This report

l.O0

.00

.00

l.O0

.00

This report

.00

.00

2.00

l.O0

[23]

.00

l.O0

.00

.00

[22]

22

Ca(OH) 2

23

CaCO 3

24

CaSi

25

H01(1)

7.600

26

Ca(Ol)2(s)

4.950

27

CaOHOI

-5.500

-2.00

9.350

-l.O0

.00

2.740

.00

.00

28

NaH(OI) 2

29

SiO 2

(Note:

Calcite

I01

Species

marked

* were

not

included

in the c a l c u l a t i o n s )

system

In the c a l c i t e - w a t e r s y s t e m it is n e c e s s a r y to i n c l u d e the f o l l o w i n g species:

C a 2 + , C a O H +, C O 2 ( a q ) ,
HCO3-,
C O 3 2-, C a C O 3 ( a q ) ,
CaHCO3- , Ca(OH)2(s)
and
CaCO3(s).
S i n c e CO2(g) is i n d i r e c t l y a c o m p o n e n t of this s y s t e m in the f o r m of C O 2 ( a q ) ,
it is of g r e a t i m p o r t a n c e to e s t a b l i s h w h e t h e r the s y s t e m is to be r e g a r d e d as
closed
or open with respect
to t h e a t m o s p h e r e .
T h i s is e v i d e n t
from a
c o n s i d e r a t i o n of Figs. 6a and 6b, w h i c h show h o w the c o n c e n t r a t i o n s of all the
species
concerned
vary with pH at equilibrium
in c l o s e d and o p e n s y s t e m s
respectively.

102

B.-M. ANTTl and E. FORSSBERG

IgC

IgC
0-

0
ii

-1

C02',C02(0q ~

CQ2*

-2

-3

/_j\

co,,o ,

-5

-6:

-8:
0

ib

12

;4

10

12

14

pH

pH
Fig.6

C a l c i t e - w a t e r system. Total CaCO 3 c o n c e n t r a t i o n at 2.88x10 -3 M

a. Closed system b. Open system, PCO2 = 10-3"5 atm

In Fig. 7a the c o r r e s p o n d i n g total c o n c e n t r a t i o n s of C02(aq) are plotted as a

f u n c t i o n of pH. The points marked + c o r r e s p o n d to [CO2]to t values m e a s u r e d in
the s o l u b i l i t y e x p e r i m e n t s with c a l c i t e in d e i o n i z e d w a t e r at d i f f e r e n t pH
levels. The d i f f e r e n c e b e t w e e n these values and their c o u n t e r p a r t s in a closed
system
is c a u s e d by a s m a l l q u a n t i t y of a t m o s p h e r i c
C02(g ) going into
solution. If we make new c a l c u l a t i o n s a l l o w i n g for t h i s p h e n o m e n o n , w h i c h
varies w i t h pH, we o b t a i n values for the total c o n c e n t r a t i o n of CO2(aq) in the
system c o r r e s p o n d i n g to the points m a r k e d o. This c a l c u l a t i o n refers to the
state of the system after 10 minutes' c o n d i t i o n i n g of calcite in water.
Figure 7b shows c o r r e s p o n d i n g data for the total c o n c e n t r a t i o n of Ca in the
system;
the points
marked
+ r e f e r to e x p e r i m e n t a l
d a t a f r o m the s a m e
solubility experiment,
and those marked o are theoretically
calculated
concentrations
w i t h a l l o w a n c e made for d i s s o l v e d a t m o s p h e r i c CO2(g ). These
c o n d i t i o n s apply to the c a l c u l a t i o n s of the calcite system reported in w h a t
follows.
-2

i
/

-2

-3

-3. x
t

~-4-

%
%
%%
%

0
,_J

-5

-6

-5-

-6

pH
Fig.7

'

I
9

+o
+
o

'

I
10

'

I
11

'

12

pH

V a r i a t i o n in: a. log [CO2]to t

b. log [Ca]to t as a function of pH
--- Open system;
-Closed system;
+ E x p e r i m e n t a l values; o T h e o r e t i c a l l y c a l c u l a t e d values

Pulp chemistry in calcite flotation

103

O l e a t e system
The f o l l o w i n g e q u i l i b r i u m are r e l e v a n t to the oleate system [24]:
log K
HOI(1)
HOl(aq)

= HOl(aq)
= H + + O1-

-7.6

(I)

-4.95

(2)

4.0

(3)

4.95

(4)

9.35

(5)

2 O1- = 0122O1- + HOl(aq)

= H(O1) 2-

Na + + H(OI) 2- = NaH(Ol)2(s)

The e q u i l i b r i u m c o n s t a n t s are somewhat u n c e r t a i n owing to the d i f f i c u l t y of

m a k i n g m e a s u r e m e n t s in these systems. W i t h the stated e q u i l i b r i u m data, the
d o m i n a n c e d i a g r a m of the oleate system assumes the aspect shown in Fig. 8. The
area of m i c e l l e f o r m a t i o n is m a r k e d on the basis of the CMC v a l u e of sodium
oleate, w h i c h is of the order of I x 10 -3 M at 20oc [25].

-2

11 /'TMCELLES
I_

-3

,, i,,,,'/o,;-

"6
o

!:t,

0
._1

~'

-5

01"

1'2 13
pH

Fig.8
O l e a t e system, d o m i n a n c e diagram. The d i a g r a m shows areas of
d i s t r i b u t i o n of NaH(Ol)2(s) at three total Na concentrations:
I x 10 -3 M;
5 x 10 -3 M; --- I x 10 -2 M
The
distribution
of O1- and O122ions evidently
depends
only
on
c o n c e n t r a t i o n . If we assume that the d i m e r O122- is o r i e n t e d w i t h its polar
ends as far apart as possible, an o v e r d o s e of oleate may cause the m i n e r a l
surface to b e c o m e h y d r o p h i l i c due to f o r m a t i o n of a charged double layer w h e n
the dimer is bonded to the surface. At high Na + c o n c e n t r a t i o n s there is a risk
of p r e c i p i t a t i o n of NaH(OI)2(s) in the pH interval from 7.5 to 11. W i t h the
oleate c o n c e n t r a t i o n s used for flotation p u r p o s e s (<I x 10 -4 M), it would take
Na + c o n c e n t r a t i o n of the order of 10 -2 M to cause p r e c i p i t a t i o n at pH - 8.
The v a r i a t i o n in log C for the oleate species as a f u n c t i o n of pH is shown in
Fig. 9. With i n c r e a s i n g total c o n c e n t r a t i o n of oleate the p r e c i p i t a t i o n limit
for HOI(1) is d i s p l a c e d towards higher pH levels [4].
Silicate system
The h y d r o l y s i s of silica is very complex and d i f f i c u l t to study. One t h e r e f o r e
finds a great v a r i e t y of e q u i l i b r i u m data, even for the m o n o n u c l e a r h y d r o l y s i s
p r o d u c t s SiO(OH) 3- and S I O 2 ( O H ) 2 2 - [11].
D u r i n g the e i g h t i e s the silicate system has b e e n i n v e s t i g a t e d by partly n e w
t e c h n i q u e s i n c l u d i n g the 29Si method [26]. F o r m a t i o n constants were d e t e r m i n e d
w i t h i n the pH interval 11 ~ pH S 12.2 and the c o n c e n t r a t i o n interval 0.008 & B
0.048 M for the f o l l o w i n g species (B is the total c o n c e n t r a t i o n of Si in the
system):

104

B.-M. ANTTI and E. FORSSBERG

SiO(OH)3-,

SiO2(OH)22-,

Si306(OH)33-

(cyclic),

and a linear tetramer

Si203(0H)42-,
Si305(OH)53-

Si202(OH)5-,
(linear),

Si20(OH) 6,

Si407(OH)53-

(cyclic),

Si44-

Lo( ICi
-301"

HOI(tl

-5

0,j/

-6

.71
-81

X,,.

HOI (aq}

-10 -11 ~
-12

)H

Fig.9

Oleate

system. Log C for species present as a function of pH

Total oleate c o n c e n t r a t i o n I x 10 -5 M

If we allow for these species together with u n d i s s o c i a t e d silica, Si(OH) 4, and

a m o r p h o u s silica, SiO2(am), and calculate a dominance diagram for pH 7-14 and
- l o g [ S i ] t o t = 2 - 3, the r e s u l t is as s h o w n in Fig. 10. F o r t o t a l Si
concentration
of <1 x 10 -2 M, only m o n o n u c l e a r species or amorphous silica
d o m i n a t e throughout the pH range in question.

~.

~3 d

SiOzlam)

J
8

I J

10

11

12

13

1~

pH

Fig.10

Silicate

system,

dominance diagram.

Stability data from

[25]

If the total c o n c e n t r a t i o n of Si is I x 10 -3 M, equilibrium composition of the

s i l i c a t e s y s t e m is s h o w n in Fig. 11. T h e t e n d e n c y to p o l y m e r i z a t i o n
is
e v i d e n t l y of s u b o r d i n a t e importance to the total c o n c e n t r a t i o n s found in a
flotation context.
Calcite-oleate

system t pH = 10.6, variable

Analytical data from

given in Table 3.

the adsorption

oleate c o n c e n t r a t i o n

experiment

with

pure

oleate

solution

are

At pH 10.6 we can assume as a first a p p r o x i m a t i o n that [Cairo t = [Ca 2+] and

that [Ol]to t = [O1-], i.e. that the analyzed total concentrations correspond
to the concentrations of free ions. C a l c u l a t i o n of the ion product for Ca(Ol) 2

Pulp chemistry in calcite flotation

105

gives widely differing results for the different experiments; the difference
between the highest and lowest values is nearly two orders of magnitude. If we
assume instead that the oleate ions at pH 10.6 bond in the first instance to
hydrated calcium ions, CaOH +, and utilize the equilibrium Ca 2+ + OH- = CaOH +
igK = 1.3 t h e n the c o n c e n t r a t i o n of C a O H + can be c a l c u l a t e d for every
experiment. As Table 3 shows, the calculated ion product for CaOHOI is of the
same order of magnitude for all the experiments.

2- 3 l Si (0H)~

SiO(OH);

Si0210H)22"

-5

" -

:+
7

Silicate

Fig.11

TABLE 3

10 pH

11

12

13

14

system. Log C for species present as a function of pH

Total Si concentration I x 10 -3 M

Results of adsorption experiments with pure oleate solution

Analyzed concentrations (M)

[Ca] tot-[Ca 2+] [Ol ] totm[Ol--]

[OH-]

Calculatedconcentrations and ion products

[CaOH+]

[CaOH+] [Ol -]

[Ca2+] [Ol-] 2

5.5"10 -s

3.4"]0 -6

4.9"]0 -4

5.37"10 -7

1.83"10 - 1 2

6.36'10 - 1 6

5.0.]0-s

7.6.10-6

5.2-10 -4

5.24.10 -7

3 . 9 8 . ] 0 -12

2.89.]0-1s

4.0.10 -5

1.1.10 -5

5.2.10 -4

4.15.10 -7

4.56.10-Z2

4.84.10-15

4.5"10 -5

5.5"10 -6

5,1-10 -4

4.60"10 -7

2,53"10 -12

1.36"10 - 1 5

4.5"10 -5

1.9"I0-5

2.5"10-4

2.20"10-7

4.19"10-12

1.62"I0 -14

Mean: 3.42"10-12

In an attempt to adapt theoretical equilibrium calculations to e x p e r i m e n t a l

data, a test was made where only precipitation of CaOHOI was considered, using
the s o l u b i l i t y p r o d u c t c a l c u l a t e d a c c o r d i n g to Table 3 (pK s = 11.5). The
theoretically calculated adsorption isotherm parallelled the experimental one
but gave an adsorption density that was too low for each oleate concentration
(Fig. 12).
C o r r e s p o n d i n g calculations based on precipitation of Ca(Of) 2 at pK s = 15.5
[19] gave adsorption densities that were too high, and a steeper adsorption
isotherm. M o d i f y i n g the solubility products of CaOHOI and Ca(Ol) 2 somewhat
[pK s (CaHOI) = 12.15 and pK s (Ca(Ol) 2) = 14.85] gave very good agreement with
experimental data. In calculating the theoretical a d s o r p t i o n i s o t h e r m b o t h
C a O H O I and Ca(Of) 2 were included as possible solid phases in the system (a
complete list of included species is given in Table 2). Under the prevailing

106

B.-M. ANTTI and E. FORSSBERG

c o n d i t i o n s (pH 10.6; o l e a t e c o n c e n t r a t i o n 6.3 x 10 -5 M - I x 10 -3 M),

only CaOHOI that is formed and a c c o u n t s for a d s o r p t i o n of oleate.

it is

u
O

E
=L
c%

~2-

nO
u~
O
<[

l/J
<
LU
.J
O

--

10-6

Illll

OLEAT

10-s

I I IIII

10-4
LEFT

IN

I III1~

-3

SOLUTION (m01es/I)

Fig.12
A d s o r p t i o n of oleate on calcite (cf. Fig.3)
E x p e r i m e n t a l data;
~ Theor.calc. log Ks(CaOl2) = -15.5
A Theor.calc. log K s ( C a O H O I ) = -11.5;
x Theor.calc. m o d i f i e d solubility constants

The change in the pK s value of CaOHOI from 11.5 to 12.15 can be e x p l a i n e d if

we a l l o w for the fact that the value of 11.5 was c a l c u l a t e d on the basis of
the total c o n c e n t r a t i o n s of c a l c i u m and oleate in the system. As can be seen
f r o m F i g . 9, t h e f r e e o l e a t e
concentration
is l o w e r t h a n t h e t o t a l
c o n c e n t r a t i o n at pH 10.6, and the same is of course also true of the Ca system
(Fig. 6). The a d j u s t e d pK s value for Ca(Ol)2 , 14.85 agrees well with the value
of 14.13 d e t e r m i n e d by n e p h e l o m e t e r [9].
Calcite-oleate

system t pH 8-12 t c o n s t a n t oleate c o n c e n t r a t i o n

If the t h e o r e t i c a l c a l c u l a t i o n s c o r r e s p o n d i n g to the a d s o r p t i o n i s o t h e r m are

correct, there ought also to be a g r e e m e n t b e t w e e n t h e o r e t i c a l and e x p e r i m e n t a l
data if the pH is v a r i e d while the oleate c o n c e n t r a t i o n is kept constant. The
f o r m a t i o n of CaOHOI or Ca(Ol) 2 can further be e x p e c t e d to be pH-dependent. A
series of e x p e r i m e n t s was p e r f o r m e d in w h i c h t h e i n i t i a l c o n c e n t r a t i o n
of
oleate was kept c o n s t a n t at 2 x 10 -4 M while the pH ranged from 8 to 12. The
calcite was c o n d i t i o n e d (a) for 15 minutes in pure oleate solution and (b) for
15 m i n u t e s in s i l i c a t e s o l u t i o n s of v a r y i n g c o n c e n t r a t i o n and then for 15
minutes in oleate solution. The pulp d e n s i t y was 28% solids by mass as before,
and after c o n d i t i o n i n g the sample was filtered and the filtrate was a n a l y z e d
for [Ca]tot, [oleate]to t and [CO2[to t.
In F i g . 13 the total oleate c o n c e n t r a t i o n in the filtrate after 15 minutes
c o n d i t i o n i n g is p l o t t e d against the pH in each experiment. In the runs with
pure oleate and I x 10 -3 M s i l i c a t e the total oleate c o n c e n t r a t i o n rises with
pH up to pH 11, d r o p p i n g sharply thereafter. By contrast we find a continuous
increase of total oleate c o n c e n t r a t i o n with rising pH in the runs with higher
silicate c o n c e n t r a t i o n s (3 and 4).
T h e o r e t i c a l c a l c u l a t i o n s were p e r f o r m e d on the same set of species as before
(Table 2), but the pH was varied from 8 to 12 in steps of 0.5 while the total
oleate c o n c e n t r a t i o n was kept c o n s t a n t at 2 x 10 -4 M. The t h e o r e t i c a l curve
(o-o-o) is p l o t t e d in Fig. 13 and explains well what h a p p e n e d in runs I and 2:
Ca(Ol) 2 falls if pH < 10.35, and CaOHOI falls if pH > 10.35.
T h e s i m i l a r i t y b e t w e e n r u n s I and 2 i n d i c a t e s t h a t the l o w e s t s i l i c a t e
concentration, c o r r e s p o n d i n g to 500 g/t, does not affect oleate p r e c i p i t a t i o n
to any a p p r e c i a b l e extent w i t h i n the pH interval studied. This e x p l a i n s w h y
the g r a d e - r e c o v e r y curve in Fig. 4b peaks at a water glass dosage of 500 g/t.
The d i s p e r s i n g effect of w a t e r glass o u t w e i g h s the d e p r e s s i n g effect at this
c o n c e n t r a t i o n . At h i g h e r s i l i c a t e c o n c e n t r a t i o n s (runs 3 and 4) there is no
precipitation
of C a O H O I . This indicates that CaOHOI is a surface compound.
C a ( O l ) 2, on the o t h e r h a n d , m a y be f o r m e d in the p u l p if the solubility

Pulp chemistry in calcite flotation

107

p r o d u c t is exceeded. If CaOHOl is removed from the list of species in Table 2,

Ca(Ol) 2 will be formed t h r o u g h o u t the pH range, giving a t h e o r e t i c a l curve (xx-x) that agrees well w i t h the e x p e r i m e n t a l data.

-&

-5

(:3
O
-J

O
-6

Ca [01 )z

CaOHOI

'

'

11

12

pH
Fig.13
__

A d s o r p t i o n of oleate on calcite: total oleate c o n c e n t r a t i o n

at e q u i l i b r i u m as a f u n c t i o n of pH
E x p e r i m e n t a l data, 15 min c o n d i t i o n i n g in 2 x 10 -4 M oleate solution
E x p e r i m e n t a l data, 15 min p r e c o n d i t i o n i n g w i t h silicate solution:
I x 10 -3 M;
--- 2 x 10 -3 M;
-x- 3.5 x 10 -3 M
T h e o r e t i c a l c a l c u l a t i o n a l l o w i n g for:
o b o t h CaOHOI and Ca(Ol)2;
+ Ca(Ol) 2 only

The f o r m a t i o n of CaOHOI at p H > 1 0 . 3 5 c a n e x p l a i n t h e r e d u c t i o n in c a l c i t e

r e c o v e r y o b t a i n e d at pH 10 and 11 (Fig. 5) if we bear in mind that the m i n e r a l
surface b e c o m e s less h y d r o p h o b i c if it is c o v e r e d w i t h a l a y e r of C a O H O I
instead of Ca(Ol) 2, w h i c h is o b t a i n e d at lower pH. It seems likely that even
at lower pH levels CaOHOI is formed first and d e p o s i t e d in a m o n o l a y e r on the
mineral surface. Precipitated
Ca(Ol) 2 can then be a d s o r b e d to the m i n e r a l
surface by h y d r o p h o b i c bonds, m a k i n g the surface more w a t e r - r e p e l l e n t .
Calcite-oleate-silicate

system

No t h e o r e t i c a l c a l c u l a t i o n s are given for the c a l c i t e - o l e a t e - s i l i c a t e system.

W l t h the e q u i l i b r i u m data a v a i l a b l e for C a - s i l i c a t e species it is not p o s s i b l e
to p r o v e a n y e f f e c t o n the f l o t a t i o n of c a l c i t e by m e a n s of t h e o r e t i c a l
c a l c u l a t i o n models.
The a d s o r p t i o n and f l o t a t i o n e x p e r i m e n t s clearly d e m o n s t r a t e that w a t e r glass
has a d e p r e s s i n g effect on c a l c i t e flotation. The i n a b i l i t y of t h e o r e t i c a l
c a l c u l a t i o n s to prove this indicates either that the silicate forms a surface
complex with the c a l c i t e or that the a t t r a c t i o n of w a t e r glass to the calcite
surface is of a s t r i c t l y p h y s i c a l nature. If a surface complex is formed, it
ought to be s t r o n g e r than the c o r r e s p o n d i n g c o m p l e x in solution, and it ought
to be p o s s i b l e to e s t a b l i s h an e q u i l i b r i u m c o n s t a n t for this surface complex
if the c o n s t a n t s of all the d i s s o l v e d complexes are known.
I n v e s t i g a t i o n s of the c a l c i t e - s i l i c a t e system using p o t e n t i o m e t r i c t i t r a t i o n
technique
[27] s h o w t h a t t h e c a l c i u m i o n s at t h e m i n e r a l s u r f a c e
form
c o m p l e x e s w i t h s i l i c a t e species and that the f o r m a t i o n of the c o m p l e x e s is
s t r o n g l y p H - d e p e n d e n t . At a silicate c o n c e n t r a t i o n c o r r e s p o n d i n g to a w a t e r
glass d o s a g e of over 2000 g/t we find an a d s o r p t i o n d e n s i t y c o r r e s p o n d i n g to
8.7 ~ m o l e s / m 2 in the pH interval from 9 to 9.6. At h i g h e r pH levels there is a
sharp increase in a d s o r p t i o n d e n s i t y to 32.6 u m o l e s / m 2. The results of model
c a l c u l a t i o n s show that a 1:1 complex of type CaSi(OH) 4 is formed at pH 9-9.6.

108

B.-M. ANTT] and E. FORSSBERG

At h i g h e r pH levels, negatively charged complexes of type CaSivOv(OH)3y are

formed, where y is of th% order of 3. If we assume that every Si(DH~ 4 molecule
c o v e r s an area of 25 ~2 in a d e n s e l y p a c k e d layer [28], 8.7 ~ m o l e s / m 2
corresponds to 1.3 monolayers on the calcite surface. At h i g h e r pH levels,
where polymerized
silicate
i o n s a r e c h e l a t e d , the a d s o r p t i o n d e n s i t y
corresponds to 2.4 monolayers on the assumption that a molecule of SiO 2 covers
12.3 A z [29].

CONCLUSIONS
The theoretical c a l c u l a t i o n s p o i n t to the e x i s t e n c e of a s u r f a c e c o m p l e x
CaOHOl which plays a significant
p a r t at pH > 10 and at low o l e a t e
c o n c e n t r a t i o n s . At l o w e r pH w h e n the c o n c e n t r a t i o n of C a O H + ions on the
mineral surface is low, Ca(Of) 2 is formed instead.
As early as 1967 Fuerstenau and Miller [7] showed by c o n v e n t i o n a l IR that
different spectra were obtained for calcite floated with lauric acid depending
on pH. At pH 9 the spectrum matched that of calcium laurate, Ca(La)2, while at
pH 12.5 it was thought to indicate the presence of CaOHLa. Readings of calcium
l a u r a t e p r e c i p i t a t e d from a q u e o u s s o l u t i o n at d i f f e r e n t pH levels g a v e
identical spectra. However, in view of this they felt unable to draw any farr e a c h i n g c o n c l u s i o n s from this s i n g l e e x p e r i m e n t . An e x p l a n a t i o n of the
failure to find any difference in the spectra of calcium laurate precipitated
at different pH levels may be that in precipitation there is always a surplus
of l a u r i c a c i d and u n d e r t h o s e c o n d i t i o n s Ca(La)2 is always formed; that
compound is a l s o p r e s u m a b l y less s o l u b l e t h a n the h y d r o x y c o m p o u n d (cf.
calcium oleate/calcium hydroxy oleate). Since ion activities are higher at the
mineral surface than out in the bulk, it is also conceivable that conditions
for precipitation of the hydroxy compound occur only at the mineral surface.
With the help of theoretical equilibrium
d e m o n s t r a t e that the effect exerted by
related to some kind of surface complex.
point to neutral calcium-silica complexes
complexes between calcium and polymerized
pH.

calculations one can also c l e a r l y

silicate ions on the system must be
Preliminary solution chemistry data
at pH 9-9.6, with negatively charged
silicate ions being formed at higher

Generally speaking, there is a great lack of relevant equilibrium data in the

complicated system that a flotation process represents. With knowledge of the
e q u i l i b r i u m c o n s t a n t s of the s u r f a c e c o m p l e x e s that are formed, and with
reliable equilibrium data on the collector reagent, theoretical calculations
can g i v e u s e f u l i n f o r m a t i o n about the chemical mechanisms that control the
flotation process. It is a frequent objection that since the flotation pulp is
not in a state of thermodynamic equilibrium, this method of calculation cannot
be applied to the system. It should be pointed out in this context that the
advantage of the SOLGASWATER computer software is that it enables allowance to
be made for deviation of the system from its equilibrium state, provided that
the parameter causing the deviation is known.
ACKNOWLEDGEMENTS
The authors wish to thank Ms Asa Lundholm for valuable help with the analyses,
and the Swedish National Board for Technical Development (STU) for financial
support.

REFERENCES
I.
2.
3.
4.
5.
6.
7.
8.
9.

Hanna, H.S. & Somasundaran, P. Flotation, A.M. Gaudin Memorial Volume p.

197, New York: AIME (1976}.
Somasundaran, P.J. Colloid Interface Sci., 31, 557 (1969).
Mishra, S.K. Int. J. Min. Proc. 9, 59 (1982).
Pugh, R. & Stenius, P. Int. J. Min. Prec. 15, 193 (1985).
H a n u m a n t h a Rao, K., Antti, B-M. & Forssberg, K.S.E. Colloids Surfaces
(1988) - in press.
Peck, A.S., U.S. Bureau of Mines RI-6202 (1964).
Fuerstenau, M.C. & Miller, J.D. AIME T r a n s a c t i o n s 2 3 8 ,
153 (1967).
Antti, B-M. & Forssberg, K.S.E. - paper submitted, to M i n e r a l s Engineerin 8
Marinakis, K.I. & Shergold, H.L. Int. J. Min. Proc. 14, 161 (1985).

Pulp chemistry in calcite flotation

109

10. K l a s s e n ,

V.I.
& Mokrousov,
V . A . An i n t r o d u c t i o n
to the T h e o r y of
Leja, J. & Poling, G.W. (Transl.). Butterworths, London (1963).
Marinakis, K.I. & Shergold, H.L. Int. J. Min. Proc. 14, 177 (1985).
Fuerstenau, M.C., Gutierrez, G. & Eligillani, D.A. Trans. Am. Inst. Min.
Eng. 241, 319 (1968).
Gregory, G.R.E.C. Analyst 91, 251 (1966).
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& Martell,
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11.
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13.
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20.
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23.
24.
25.
26.
27.
28.
29.

APPENDIX
Calculation

of

'surface molarity'

for calcite.

77 g calcite grading 85% CaCO 3 = 55.3 g CaCO 3

200 ml aqueous solution
BET surface: 0.7 - 0.9 m2/g
Unit cell volume: 367.96x10 -24 cm 3
No. of formula units of CaCO 3 per unit cell: 6
55.3 x (0.7xi04)
Msurf

x 6 x I

3.76 x 10 -3 M

(367.96 x 10-24) 2/3 x (6.023 x 1023 ) x 0.200

g x cm2/g x formula units per unit cell x monolayers

cm 2 per unit cell x formula units per mole x litres

5 monolayers
10 monolayers

take part in reaction = Msurf = 1.88x10 -2 M

take part in reaction = M surf = 3-76x10-2

In t h e c a l c u l a t i o n s ,
surface
molarity
has been
c o r r e s p o n d i n g to a reaction depth of 7.5 monolayers.

M
put

at

2 . 8 x 1 0 -2

M,