Minerals Engineering 17 (2004) 425430

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Flotation of sylvite with dodecylamine and the eect of added

long chain alcohols
M.B.M. Monte a, J.F. Oliveira

b,*

Laboratory for Surface Chemistry, Coordination of Technological Innovation, CETEMCentre for Mineral Technology,
Avenida do Ip^e, 900, Cidade Universit
aria, Ilha do Fund~ao, Rio de Janeiro, RJ 21941-970, Brazil
Department of Metallurgical and Materials Engineering, COPPE/UFRJ, Rio de Janeiro Federal University, Caixa Postal 68505,
Rio de Janeiro, RJ 21945-970, Brazil
Received 30 September 2003; accepted 10 November 2003

Abstract
In the potash production industry, sylvite is selectively oated from halite with the use of cationic collectors. Due to the high
solubility of the KCl and NaCl minerals, the process has to be conducted in saturated brines of these salts and at very high collector
concentration. The understanding of the mechanisms involved in this peculiar selective otation process has progressed well in the
recent years and is briey discussed herein.
Studies of the eect of the addition of long chain alcohols on the dodecylamine adsorption and otation of KCl were undertaken
and the results are presented. Potassium chloride otation with dodecylamine was enhanced by the addition of hexyl and octyl
alcohol with the best results in the concentration range of from 6 to 8 10
3 M. Decyl alcohol had a less eective inuence on KCl
oatability. The surface tension of dodecylamine solution as a function of KCl concentration and the lowering of the amine critical
micelle concentration in KCl saturated solution were also studied and the role of the long chain alcohol addition on the otation
recovery of potassium chloride with dodecylamine is discussed.

2003 Elsevier Ltd. All rights reserved.
Keywords: Non-metallic ores; Flotation collectors; Flotation frothers

1. Introduction
The processing of soluble salt minerals from underground deposits is of great industrial importance because potassium salts together with phosphate rock and
nitrogen products form the three basic commodities
used in fertilizer manufacturing. Underground salt
deposits sometimes present a complex mineralogical
composition involving several salt minerals like carnalite
(KMgCl3 6H2 O), taquidrite and sylvinite. Nonetheless,
most commonly the main potassium mineral is sylvite
(KCl) and sometimes it is only associated with halite
(NaCl) and clay minerals. The selective otation of KCl
from NaCl has been in practice for several decades and
fundamental studies aiming at a better understanding of
the process and its improvement are still under way. The
selective otation of sylvite from halite is generally
accomplished with the use of cationic collectors at a
*
Corresponding author. Tel.: +55-21-2562-8500; fax: +55-21-22906626.
E-mail address: oliveira@metalmat.ufrj.br (J.F. Oliveira).

0892-6875/$ - see front matter
2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2003.11.005

concentration above its solubility limit in saturated

brine (Kramer and Schubert, 1991). Some important
contributions to the understanding of soluble salt otation mechanisms have been presented recently by
Miller et al. (1997) and Laskowski et al. (2000). The
primary aliphatic amines normally used as collector
generally contain 1618 carbon atoms in the chain and
the process eciency is known to improve with chain
length. The use of special long chain amines (1822
carbons) is justied where otation of the coarse KCl
particles may be hindered by brine temperature above
32 C (Seidel et al., 1968).
Because of the high solubility of KCl and NaCl, the
otation process has to be conducted in saturated brines
of these salts. From a fundamental approach, this means
that the thickness of the double layer around the salt
particles is very small and as a consequence the traditional measurement of the surface charge or zeta potential of these minerals is not easily achieved. Due to
their high solubility the equilibrium state of the surface
is also dicult to control. In the last decade, however,
the measurement of KCl and NaCl nonequilibrium

426

M.B.M. Monte, J.F. Oliveira / Minerals Engineering 17 (2004) 425430

electrophoretic mobility has become possible by the

laser-Doppler electrophoresis technique (Miller and
Yalamanchili, 1992). This nding was a breakthrough
and resulted in a better understanding of the mechanisms involved in the selective otation of the soluble
minerals with cationic collectors. The measurements
made during the initial states of salt dissolution clearly
indicated that KCl is negatively charged whereas NaCl
presents a positive charge. In a subsequently published
paper by the same research group (Yalamanchili et al.,
1993), evidence is presented of the adsorption of positively charged precipitated collector colloids on the
negative KCl surface. The positive charge of the precipitated amine colloid has also been suggested by
Laskowskii et al. (1988). The hydrophobic nature of the
precipitated colloids would impart the oatability to the
KCl particles. This proposed otation mechanism
would occur by heterocoagulation rather than by the
adsorption of collector ions and/or neutral molecular
species as originally suggested by Roman et al. (1968).
A mixed mechanism involving rst the adsorption of
cationic collector on the negative KCl surface and then
the precipitation of colloids on the hydrocarbon chains
of previously adsorbed collector species has been advanced by Fuerstenau et al. (1984). Nonetheless, strong
evidence was presented by Yalamanchili and Miller
(1993) that short range attractive forces are responsible
for heterocoagulation between the hydrophobic collector colloid particles and the hydrophilic alkali halide
particles. However, the forces involved in the heterocoagulation would better be described as a combination of
the hydrophobic force on the collector colloid particles
and hydration force on the KCl surface. The hydrophobic character of the collector colloid surface seems to
be more important than the low value of its surface
charge on the arrangement of water dipoles on the colloid surface.
In this work, studies of the eect of the addition of
long chain alcohols on the dodecylamine adsorption and
on the performance of KCl otation were undertaken
and the results are presented and discussed.

2. Experimental
The potassium chloride sample used in the experimental work was of analytical grade. Nevertheless, the
sample was initially calcined at 450 C thus eliminating
any traces of surface active substances and then stored
in hermetically closed vials. Before the microotation
tests and adsorption experiments the salt sample used
was again dried for 2 h. Double distilled and deionized
water was used throughout the work.
Chloroform and bromo-cresol green were used for
determination of dodecylamine concentration in salt
solutions, and the pH was adjusted with KOH and HCl.

All reagents used, including dodecylamine, hexanol,

octanol, decanol and dodecanol were of analytical
grade.
The dodecylamine solutions at dierent concentrations were prepared using saturated brine solutions of
KCl. The nal desired volume for dilutions was adjusted
with KCl saturated solution.
Adsorption studies were carried out by mixing 15 g of
KCl, in the size range of 208 147 lm, with 40 ml of
KCl saturated dodecylamine solution in stoppered test
tubes radially disposed on a vertical rotating disc. The
system provided about 8 end over and inversions per
minute. After 18 h of conditioning time for obtaining
the adsorption equilibrium concentration, the residual
of KCl saturated dodecylamine concentration in solution was measured as described in Pearce (1961). This
method was originally proposed for the analysis of
amine concentration in water, and it was proved to be
adequate to determine amine concentration in a saturated salt solution, as well. The experiments were conducted both in the presence and absence of the several
long chain alcohols mentioned before, at 25 C and
pH 6.
The microotation testwork was carried out in a
Hallimond tube, using 5 g of ()295 + 208 lm) KCl
particle samples. Amine conditioning and otation time
were both 3 min and a nitrogen gas owrate of 1 ml s
1
was maintained throughout the experiments. The microotation tests using dodecylamine and alcohol were
conducted after simultaneous conditioning of KCl with
these reagents for 2 min.
The surface tension measurements were conducted
according to the Du Nouy-ring method using a Cenco
tensiometer. The nal value adopted in each case was
the determination of eight sequential readings.

3. Results
The inuence of dodecylamine (DDA) concentration
on the KCl oatability in the presence and absence of
octyl alcohol is presented in Fig. 1. It can be seen that
the onset of KCl otation starts at a DDA concentration higher than the limit of solubility of dodecylamine
(6 10
5 M) in saturated solution. With added octyl
alcohol, the otation starts to occur at lower collector
concentrations. The adsorption isotherms shown in Fig.
2 indicate a good correlation with the previous otation
results. It can also be seen that the eect of octyl and
hexyl alcohol is similar, although with octyl alcohol the
adsorption is slightly displaced to lower concentrations.
The inuence of three long chain alcohols on the
oatability of KCl with DDA is shown in Fig. 3.
Compared to the eect of butyl and decyl, octyl alcohol
showed a striking eect indicating that there is an
optimum chain size between those two extremes.

M.B.M. Monte, J.F. Oliveira / Minerals Engineering 17 (2004) 425430

100

100
NoAlcohol
Octanol 5E-3M
Octanol 8E-3M

60
(c)
40

Butanol
Octanol
Decanol

80

Flotation (%)

80

Flotation (%)

427

(b)

60

40

(a)

20

20

0
-6

10

-5

-4

10

10

-3

10

DDA (mol/L)

Fig. 1. The inuence of DDA concentration on the KCl otation

recovery in saturated salt solutions: (a) without alcohol; (b) in the
presence of 5 10
3 M octanol and (c) 8 10
3 M octanol.

No Alcohol
Hexanol 1E-3M
Octanol 1E-3M

12

-5
DDA 2 x 10
-5
DDA 6 x 10

80

Flotation (%)

Adsorption Density (mmol.kg-1)

10

100

(b) (c) (a)

10

Fig. 3. The inuence of alcohol chain length and its concentration on

the recovery of KCl by otation with dodecylamine at a concentration
of 6 10
5 M.

14

12

Alcohol (x10-3 M)

60

40

4
20

0
10-6

10-4

10-5

10-3

DDA (mol/L)
Fig. 2. Adsorption isotherm of dodecylamine on potassium chloride in
its saturated brine at 25 C and pH 6: (a) without alcohol; (b) in the
presence of 10
3 M octyl alcohol (c) and 10
3 M hexyl alcohol.

The results in Fig. 4 are a conrmation of this

observation and show that very high oatability is observed for hexanol concentrations around 4 10
3 M,
for a DDA concentration of 6 10
5 M. This concentration represents the limit of solubility of the DDA
collector above the precipitation point of RNH3 Cls , in
colloidal state (Yalamanchili et al., 1993). However,
when DDA concentration is lowered to 2 10
5 M, no

0
0

Hexanol (x10- 3M)

10

12

Fig. 4. Flotation recovery of KCl as a function of hexanol concentration using dodecylamine as collector: (a) 2 10
5 M and (b) 6 10
5
M.

signicant eect is observed as shown in Fig. 4 and the

otation response is negligible. This is in agreement with
the otation recoveries in the absence of alcohol shown
in Fig. 1.
The results in Fig. 5 show that for a DDA 5 10
5 M
solution, an increase in the potassium chloride concentration lowers the surface tension to around 30 mN m
1 ,
for a KCl concentration close to saturation. This eect is

428

M.B.M. Monte, J.F. Oliveira / Minerals Engineering 17 (2004) 425430

important in potash otation because it shows that, due

to a squeezing out eect of the salt concentration, the
surfactant tends to strongly adsorb at the liquidgas
interface. This fact has an eect on the structure and the
dynamics of the bubble surfaces in the otation aeration
step. This phenomenon is clearly observed also in Fig. 6
that presents surface tension as a function of the logarithm of DDA concentration in water and in a 4 M KCl

100

Surface Tension (mN.m-1)

80

(a)

No surfactant

60

DDA5x10-5 M

4. Discussion

40

(b)

20
0

2
3
4
Potassium Chloride (mol/L)

Fig. 5. The inuence of potassium chloride concentration on the

surface tension of the solutions: (a) without surfactant and (b) in the
presence of 5 10
5 M DDA.

70

Surface Tension (mN.m-1)

solution. According to the Gibbs equation, the

adsorption density C (mol cm
2 ) at the liquid/gas interdc
face is given by C
RT1  d logC
. The application of
Gibbs adsorption isotherm to the data obtained show
that although the surface tension decreases with the
surfactant concentration, the surface excess reaches a
maximum just below the critical micelle concentration
(CMC) (Fig. 7). After CMC, the adsorption at the liquidgas interface also reaches a limit (Shinoda, 1978).
The CMC of a DDA solution in water is around
1.5 10
2 M (Fig. 6). However, Fig. 6 also shows that
for a saturated (4 M KCl) solution, the surface tension
does not decrease after a DDA concentration of 6 10
5
M, which could be considered the CMC of the surfactant. For the saturated salt solution, this value is coincident with the solubility limit of the surfactant or the
onset of precipitation of colloidal DDAHCl (Yalamanchili and Miller, 1993).

DDA

60

DDA + 4M KCl

50

40

30

(b)

(a)
-6

10

-5

10

-4

10

-3

10

-2

10

-1

10

DDA (mol/L)
Fig. 6. The eect of dodecylamine concentration on the surface tension measured at pH 6: (a) in water and (b) in 4 M KCl solution.

Adsorption and microotation studies conducted in

the presence and absence of several alcohols showed
that oatability of KCl with DDA is particularly enhanced in the presence of hexanol. Nevertheless, other
alcohols like octanol and decanol also presented a positive eect (Figs. 14). Dodecanol, on the other hand,
inhibited KCl formation of mixed micelles, as the chain
length of the alcohol approaches that of dodecylamine.
Van der Walls forces between the hydrocarbon chains
would favor micelle formation, lowering the concentration of molecules and ions in solution, and, consequently, decreasing adsorption and oatability.
Experimental results from other investigators (Aleksandrovich and Mitina, 1974), showed that some
alcohols, when added to amines, increased both amine
adsorption on KCl surface and the oatability.
However, the enhancement in DDA adsorption on
the KCl surface caused by alcohols of intermediate
chain length (68 carbons) could not be the only reason
for the high recovery of otation observed in Figs. 3 and
4. It is very likely that due to the low solubility of the
alcohol in the saturated salt solution, a second phase is
formed at the liquidgas interface. This could occur by a
phase separation mechanism, giving rise to a liquid lm
several molecular layers in thickness. The alcohol concentration needed to improve KCl otation is fairly
high. Trial surface tension measurements by the Du
Nouy-ring method were unfruitful, giving unreliable
results, probably due to the formation of a two-phase
system at the airsurface interface.
It is therefore postulated that dodecylamine adsorption would occur also at the interface between the
aqueous solution and organic lm on the bubbles, as
shown in Fig. 8. The fact that only a very narrow range

M.B.M. Monte, J.F. Oliveira / Minerals Engineering 17 (2004) 425430

429

Fig. 7. The eect of increased surfactant concentration on the adsorption density at the airsolution interface.

of alcohol concentration provides a signicant eect is

important. Fig. 5 shows that for 6 10
5 M DDA, a
high oatability is observed in the range of 46 10
3 M
hexanol. This represents a rather high concentration,
two orders of magnitude higher than that for DDA for
which the synergistic eect has been observed. This high
concentration is sucient for a two-phase system formation, but if a too thick layer were formed, the bubble
stability would be aected.
The steep increase in adsorption at an equilibrium
concentration around 10
4 M DDA (Figs. 3 and 4) is in
agreement with the onset of oatability reported in the
literature (Roman et al., 1968). This reinforces the fact
that adsorption of DDA on the KCl surface is fundamental, although a mixed monolayer of aminealcohol
adsorbed on the bubble surfaces, as proposed by Arsentiev and Leja (1970), Leja (1983a,b) and Fuerstenau
and Yamada (1962), could also be involved.

Fig. 8. Schematic representation of a gas bubble surrounded by a

hexanol lm and a dodecylamine monolayer absorbed at the alcohol
water interface.

Fig. 5 represents the classical phenomenon of surface

tension increase with ionic strength. Less commonly
taken into account is the lowering of surface tension
with increase in ionic strength when a surfactant is
present. Curve b in Fig. 5, shows that as the KCl concentration is increased the adsorption of dodecylamine
at the interface leads to a lower surface tension value.
However, application of Gibbs equation to the results of
Fig. 6 shows that close to the CMC the adsorption
density C for DDA in 4 M KCl is 1.99 10
10
mol cm
2 whereas for DDA in water the value of C is
increased to 8.34 10
10 mol cm
2 . These values correspond to a molecular area equivalent to 83.4 and 19.9
2 , respectively. The area occupied by a molecule in a
A
2 (Leja, 1983a,b). So,
monolayer structure is around 23 A
in the second case, the situation approaches that of a
compact monolayer at the liquidair interface. Saturation of the interface in the presence of KCl occurs at a
lower bidimensional concentration and at a larger
molecular area.
The adsorption of DDA in the presence of KCl near
the DDA critical micelle concentration (CMC) is lower
than the value obtained for adsorption from water is
apparently contradictory because one would expect a
squeezing out eect due to KCl presence. The fact is that
due to the lowering of the CMC in the presence of the
salt, micelles are formed at much lower bulk concentration hindering the migration of surfactant molecules to
the interface. The CMC of DDA is decreased from 10
2
M in water to 6 10
5 M in 4 M KCl. This change, which
corresponds to more than two orders of magnitude, can
be explained by the compression of ionic atmosphere
around the charged polar head of dodecylamine as
shown schematically in Fig. 9a and b. This lowers the
repulsion and favors micellization through Van der
Waals interaction between the hydrocarbon chains.

430

M.B.M. Monte, J.F. Oliveira / Minerals Engineering 17 (2004) 425430

References

Fig. 9. (a) Decreased CMC of surfactant in solutions due to high salt

concentration. In saturated salt solutions the compression of the ionic
atmosphere leads to predominance of Van der Waals attraction and
lower CMC. (b) Lower salt concentration leads to increased thickness
of ionic atmosphere, stronger repulsion, increased dispersion of the
surfactant molecules and higher CMC.

5. Conclusion
Studies of adsorption of dodecylamine on KCl surface and Hallimond tube otation showed that the
addition of hexanol could improve signicantly the oatability. Other alcohols with shorter or longer chain
length presented a less distinguished eect. Surface
tension measurement showed that the CMC of dodecylamine is lowered from 1 10
2 M in water to 6 10
5
M in 4 M KCl solution. For a given DDA concentration, the surface tension was shown to decrease with
an increase in the KCl concentration.

Acknowledgements
The authors wish to thank Dr. Claudio Schneider,
CETEM, for revising the English text and for his useful
suggestions.

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