Int. J. Miner. Process.

70 (2003) 83 97
www.elsevier.com/locate/ijminpro

Study of celestite flotation efficiency using

sodium dodecyl sulfonate collector:
factorial experiment and statistical analysis of data
A. Martinez L. a,b,c,*, A. Uribe S. b, F.R. Carrillo P. a,
J. Coreno A. c, J.C. Ortiz a
a
Universidad Autonoma de Coahuila, Blvd. V. Carranza and Ing. Jose Cardenas s/n, A.P. 935, C.P. 25000,
Saltillo, Coahuila, Mexico
b
CINVESTAV-IPN Unidad Saltillo, Ctra. Saltillo-Monterrey, km. 13, A.P. 663, C.P. 25000,
Saltillo, Coahuila, Mexico
c
Universidad Autonoma del Estado de Hidalgo, Ctra. Pachuca-Tulancingo, km. 4, Cd. Universitaria,
Pachuca, Hidalgo, Mexico
Received 29 May 2002; received in revised form 25 October 2002; accepted 29 October 2002

Abstract

Flotation tests of synthetic mixtures of celestite (SrSO4) and calcite (CaCO3) minerals using
sodium dodecyl sulfonate as collector were carried out using a factorial experimental design 23.
The independent experimental variables included celestite grade in the feed (50% and 90%
SrSO4), conditioning pH (6.5 and 9) and sodium silicate depressant concentration (10
5 and 10
3
M). All experiments were performed at a constant collector concentration (10
4 M) and con-
ditioning time of 15 min. The response variables were recovery and grade of SrSO4 in the con-
centrate.
The factors that had the greatest effect on the grade and recovery of celestite were the celes-
tite grade in the feed (L) and the depressant concentration (C); also the combination of these
factors significantly affected the response variables. The highest celestite yield (96% recovery,
98% grade) was obtained when a 90% of celestite grade in the feed was used.
D 2003 Elsevier Science B.V. All rights reserved.

Keywords: factorial design; calcite; celestite; flotation; sodium dodecyl sulfonate

* Corresponding author. Universidad Autonoma de Coahuila, Blvd. V. Carranza and Ing. Jose Cardenas s/n,
A.P. 935, C.P. 25000, Saltillo, Coahulia, Mexico. Tel.: +52-84-416-92-13; fax: +52-84-439-05-11.
E-mail address: luevanos@uaeh.reduaeh.mx (A. Martinez L.).

0301-7516/03/$ - see front matter D 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0301-7516(02)00152-7
84 A. Martnez L. et al. / Int. J. Miner. Process. 70 (2003) 8397

1. Introduction

The celestite ore is the raw material for the production of strontium carbonate
(SrCO3), which is the main source of strontium and strontium compounds. Depending
on the grade of the ore, which may range from 50% to 60% SrSO4 for important
deposits in Canada, Turkey and Spain to as high as about 90% SrSO4 for deposits in
Mexico (Andrews and Collings, 1991; Luna, 1995), the beneficiation of the ore might
comprise ore selection followed by crushing, sizing, washing, and/or flotation to remove
the gangue minerals (mainly calcite, silica and clays). Upgrading of low-, medium- and
high-grade celestite ores may be done by flotation.
The collectors more commonly used in celestite concentration by flotation are of
anionic type such as the alkaline salts of fatty acids, alkyl sulfuric acids and alkyl
sulfonic acids. Sodium oleate has been widely used in the flotation of semisoluble
salt-type minerals such as calcite, fluorite, barite, celestite and others (Estefan, 1974,
1979; Pugh and Stenius, 1985; Rao and Forssberg, 1992). Sodium oleate is highly
efficient as collector but has the disadvantage of its low selectivity towards the
valuable mineral. Hernainz Bermudez de Castro and Calero de Hoces (1993) and
Hernainz Bermudez de Castro et al. (1996) have carried out floatability studies of pure
celestite and calcite minerals using sodium silicate and quebracho as depressants for
calcite to improve the selectivity of sodium oleate collector towards celestite. Their
results showed that these depressants are also adsorbed on celestite, thus affecting its
floatability.
Other studies on celestite flotation have used alkyl sulfates and alkyl sulfonates as
collectors with the aim of improving the selectivity of the collector towards celestite
(Chibowski et al., 1988; Gonzalez-Caballero et al., 1989). Hernainz Bermudez de
Castro et al. (1997) studied the effect of quebracho on the floatability of celestite and
calcite using sodium dodecyl sulfonate as collector. These authors reported that using
quebracho concentrations lower than 0.12 g/l floatability of calcite was more affected
than that of celestite. Houot et al. (1993) reported celestite concentrates containing
about 95% SrSO4 at around 60% recovery, processing an ore assaying 57.5% SrSO4,
29.3% CaCO3, 5% CaSO42H2O, 7.7% clays and 0.5% BaSO4 by using sodium alkyl
sulfate (C16 or C18) as collector and sodium silicate as depressant for calcite and
clays.
Recently, other flotation studies of pure celestite and calcite minerals (Hernainz
Bermudez de Castro et al., 1997; Martnez-Luevanos et al., 1999, 2000; Lopez-
Valdivieso et al., 2000) have been carried out using quebracho and sodium silicate as
depressants for calcite and sodium dodecyl sulfate and sodium dodecyl sulfonate as
collectors for celestite. The obtained results from those studies indicated that the
floatability of celestite using sodium dodecyl sulfonate and sodium silicate was higher
than using sodium dodecyl sulfate and quebracho (under certain pH values and
depressant concentration and at 10
4 M collector concentration).
It is well known that during the conditioning step the mineral is in contact with all
the process variables, such as pH, concentration and kind of collector and depressant.
Therefore, it is important to elucidate how the combination of these variables affects the
flotation of the valuable mineral (celestite, in the present study).
 A. Martnez L. et al. / Int. J. Miner. Process. 70 (2003) 8397 85

The experimental factorial design is broadly used to study the factors controlling the
separation processes. Its use reduces number of experiments, saving time and material
resources. Additionally, the analysis performed on the results is easier and the experimental
error is reduced (Lazaridis et al., 1995; Montgomery, 1991).
The aim of the present work is to investigate the effect of pH, depressant
concentration and mineral grade in the feed on the selective floatability of celestite by
means of factorial experiments. This study was carried out using synthetic mixtures of
celestite and calcite minerals and sodium dodecyl sulfonate as collector (10
4 M). At
this concentration the best floatability of celestite (99%) was obtained in previous works
using samples of pure minerals (Martnez-Luevanos et al., 1999, 2000).

2. Experimental

2.1. Materials and equipment

High purity calcite and celestite crystals were selected by hand from typical calcite
and celestite deposits of the states of San Luis Potosi and Coahuila, Mexico. Chemical
analysis by atomic emission spectrometry (ICP) showed 99.96% (by weight) CaCO3 and
99.99% SrSO4. For the microflotation studies the crystals were ground in a porcelain
mortar and wet sieved to obtain the
180/ + 150 Am size fraction.
Sodium dodecyl sulfonate (C12H25SO3Na: Aldrich, 99%) was used as collector and
hydrated sodium meta-silicate (Na2SiO39H2O: Fisher, 99%) was used as depressant. A
solution of sodium nitrate (NaNO3: Aldrich, 99.9%) was used to regulate the ionic
strength of the suspensions. Dilute solutions of sodium hydroxide, NaOH, and nitric acid,
HNO3 (analytical grade, Aldrich) were used as pH modifiers. A potentiometer (Orion
Mod. 720A) equipped with a combined electrode was used to monitor the pH. The
potentiometer was calibrated before each test by using buffer solutions of pH 4, 7 and 10
(Merk).

2.2. Methodology

Floatability studies of mixtures of celestite and calcite minerals containing 50% and
90% SrSO4 grade were performed in a modified Hallimond cell of 120 ml. It set of
experiments was designed based on a factorial experiment 23. The independent variables
(factors) chosen at two levels were the celestite grade in the feed (L, 50% and 90%
SrSO4), conditioning pH (pH, 6.5 and 9) and the addition of sodium silicate as calcite
depressant (C, 10
5 and 10
3 M). It is important to mention that celestite ores may
range from 50% to 60% SrSO4 for important deposits in Canada, Turkey and Spain to as
high as about 90% SrSO4 for deposits in Mexico. Due to this, the range of celestite
grade in the feed was selected as one of the independent variable to be studied into the
range from 50% to 90% SrSO4.
The response variables (dependent variables) were the grade and recovery of celestite
in the concentrate. The collector concentration (10
4 M sodium dodecyl sulfonate) was
kept constant. At this concentration, the best floatability of celestite (99%) was obtained
86 A. Martnez L. et al. / Int. J. Miner. Process. 70 (2003) 8397

Table 1
Experimental conditions for flotation tests proposed by the experimental factorial design 23
Test Experimental conditions
pH SrSO4 grade [Na2SiO3], M
(during conditioning) in the feed, %
(1) and (1)R 6.5 50 10
5
2 and 2R 6.5 90 10
5
3 and 3R 9.0 50 10
5
4 and 4R 9.0 90 10
5
5 and 5R 6.5 50 10
3
6 and 6R 6.5 90 10
3
7 and 7R 9.0 50 10
3
8 and 8R 9.0 90 10
3
R = Duplicated.

in previous works using samples of pure minerals. The experimental conditions for each
test are given in the Table 1.

2.3. Flotation tests

The flotation tests were done with 2 g of mineral mixture dispersed in 120 ml of
aqueous solution containing the sodium silicate depressant at the desired concentration
(10
5 or 10
3 M) and at the desired pH value (6.5 or 9). pH value was kept constant
during the conditioning time using sodium hydroxide and nitric acid diluted solutions for
the tests where 90% celestite grade in the feed was used. It is worth mentioning that
when 50% celestite grade in the feed was tested, pH value of 6.5 recorded at the
beginning of the conditioning step is quoted. This value changed during conditioning
due to the natural tendency of the system (calcite/water) to attain equilibrium (pH 8.3).
After conditioning the suspension for 3 min, the sodium dodecyl sulfonate collector was
added (10
4 M) and a period of time of 15 min was allowed to elapse as to complete a
total conditioning time of 18 min. Then, the suspension was transferred to the Hallimond
cell where the flotation was carried out during 1 min using nitrogen at a flow rate of 50
ml/min. The ionic strength of solution in all experiments was kept constant (10
2 M
NaNO3). The content of SrSO4 on both the concentrate and the tails was analyzed by
atomic emission spectrometry and gravimetric analysis. Two celestite grades (L) in the
ore mixtures were used: 50% and 90% SrSO4.

3. Results and discussion

3.1. Flotation results

Table 2 shows the chemical and gravimetric analysis of the concentrate and the tails for
each flotation experiment.
Fig. 1 graphically shows all the possible combinations and the results (average of the
two replicas) obtained as a function of (a) celestite grade and (b) celestite recovery in the
 A. Martnez L. et al. / Int. J. Miner. Process. 70 (2003) 8397 87

Table 2
Chemical and gravimetric analysis performed on both the concentrate and the tails of each microflotation tests
Test Concentrate SrSO4 in SrSO4 in the
(CaCO3 + SrSO4), g the feed, g concentrate, g
(1) 0.5285 0.4847 0.4623
2 0.9408 0.8937 0.8864
3 0.7184 0.4783 0.4699
4 0.9332 0.8907 0.8813
5 0.4787 0.4928 0.4202
6 0.9011 0.8837 0.8530
7 0.5342 0.4859 0.4445
8 0.8621 0.8820 0.8475
(1)R 0.5190 0.4782 0.4484
2R 0.9001 0.8909 0.8732
3R 0.6797 0.4896 0.4787
4R 0.9248 0.8883 0.8718
5R 0.4755 0.4788 0.4184
6R 0.8601 0.8914 0.8457
7R 0.5134 0.4873 0.4356
8R 0.8303 0.8813 0.8098

concentrate. Fig. 2 shows the average values of celestite grade (%) in the concentrate as
a function of celestite recovery (%). It can be seen that when a 50% of celestite was
used in the feed celestite was recovered at 95% and the grade of concentrate was about
87%. On the other hand, when feed contained 90% of celestite, recovery and grade
improved to 96% and 98%, respectively.

3.2. Statistical analysis of the floatability results

Tables 3 and 4 show the analysis of variance (ANOVA) of the obtained results as a
function of celestite grade and recovery in the concentrate, respectively. The ANOVA
shows that all the variables and their respective combinations affect the celestite grade.
The obtained variation coefficient is 2.23%. On the other hand, the ANOVA of the
results as a function of recovery of SrSO4 shows that the pH variable and its
combinations with the other variables (LpH and LpHC) do not significantly affect
the celestite recovery at the concentrate. The variation coefficient in these studies is
1.3%.
Regression equations can be obtained from the ANOVA performed on the flotation
results as a function of celestite grade and recovery, along with the value analysis of the
calculated contrasts for each factor and their respective combinations (see Appendix A).
These equations can be used to estimate the celestite grade and recovery (%) in the
concentrate within the experimental conditions limits (grade SrSO4 in the feed,
conditioning pH and Na2SiO3 concentration) that were studied in this work:
Celestite grade in the concentrate, %

SrSO4 gradecalculated 89:05 7:05X1
2:68X2 2:48X3 2:73X1 X2

1:37X1 X3 2:03X2 X3
1:35X1 X2 X3 3:1
88 A. Martnez L. et al. / Int. J. Miner. Process. 70 (2003) 8397

Fig. 1. Graphic presentation of the obtained results (average of the two replicas) as a function of: (a) SrSO4 grade
% and (b) SrSO4 recovery % in the concentrate.

Celestite recovery in the concentrate, %

SrSO4 recoverycalculated 95:51 2:27X1
2:67X3 1:07X1 X3 3:2

Fig. 3 was plotted using Eqs. (3.1) and (3.2) within the limits of the experimental
conditions used. This figure presents the region that contains all of the possible celestite
grades that can be obtained as a function of the celestite recovery. Also, the line defining
the best separation curve obtained for different celestite grades in the feed ranging from
50% to 90%. It can be seen that it is possible to obtain celestite concentrates containing
about 98% and 96% of grade and recovery, respectively.
 A. Martnez L. et al. / Int. J. Miner. Process. 70 (2003) 8397 89

Fig. 2. Experimental curves of separation defined by the different possible combinations of the studied variables
in the factorial design 23.

3.3. Validation of the lineal regression equations

A set of additional microflotation experiments using celestite calcite mixtures was

carried out, using experimental conditions within the limits considered in the previously
described factorial design 23. This experiments were performed using 10
4 M sodium
dodecyl sulfonate collector, mixture of celestite (90% grade) and calcite, two concen-
trations of sodium silicate (10
5 and 10
3 M). The conditioning pH was varied from

Table 3
Analysis of variance of the results expressed in grade of SrSO4 (%) in the concentrate
Source of Freedom Sum of Average F F theoretical
variation grades squares squares estimated
a = 0.01 a = 0.05
11.26 5.32
L 1 794.43 794.43 200.96 **
pH 1 115.26 115.26 29.16 **
C 1 98.75 98.75 24.98 **
LpH 1 118.87 118.87 30.07 **
LC 1 30.05 30.05 7.60 *
pHC 1 65.72 65.72 16.62 **
LpHC 1 29.34 29.34 7.42 *
Error 8 31.62 3.95
Total 15 1284.04
Variation coefficient = 2.2.
* Significant to 95% of confidence (a = 0.05).
** Significant to 99% of confidence (a = 0.01).
90 A. Martnez L. et al. / Int. J. Miner. Process. 70 (2003) 8397

Table 4
Analysis of variance of the results expressed in recovery of SrSO4 (%) in the concentrate
Source of Freedom Sum of Average F F theoretical
variation grades squares squares estimated a = 0.01 a = 0.05
11.26 5.32
L 1 82.42 82.42 48.17 **
pH 1 3.50 3.50 2.05 n.s
C 1 114.06 114.06 66.66 **
LpH 1 8.28 8.28 4.84 n.s
LC 1 18.36 18.36 10.73 *
pHC 1 9.83 9.83 5.74 *
LpHC 1 2.97 2.97 1.73 n.s
Error 8 13.69 1.71
Total 15 253.11
n.s = not significant.
Variation coefficient = 1.37%.
* Significant to 95% of confidence (a = 0.05).
** Significant to 99% of confidence (a = 0.01).

6.5 to 9. Table 5 shows the results of the gravimetric and chemical analysis obtained for
each of the floated samples.
Fig. 4a shows the experimental and calculated results for celestite grade as a function of
pH. The corresponding experimental and calculated results for celestite recovery are
shown in Fig. 4b. The dotted and solid lines present the calculated values of celestite grade
and recovery using Eqs. (3.1) and (3.2), respectively, for the experimental conditions
tested. It can be seen that there is a close resemblance for the calculated and experimental
flotation values for both cases. This correlation is an indicator that Eqs. (3.1) and (3.2) can

Fig. 3. Flotation zone defining all possible combinations of grade vs. recovery of SrSO4 within the range of the
experimental conditions investigated in the present work: SrSO4 in the feed, from 50% to 90%; pH, from 6.5 to 9;
sodium silicate concentration, from 10
5 to 10
3 M.
 A. Martnez L. et al. / Int. J. Miner. Process. 70 (2003) 8397 91

Table 5
Results obtained from both gravimetric and chemical analysis
Experimental Concentrate SrSO4 in SrSO4 in the SrSO4 grade in SrSO4 recovery in
conditions (CaCO3 + SrSO4), g the feed, g concentrate, g the concentrate, % the concentrate, %
(pH, [Na2SiO3])
6.5, 10
3 0.8875 0.8888 0.8551 96.5 96.2
7, 10
3 0.8841 0.8898 0.8562 96.8 96.2
7.5, 10
3 0.8790 0.8902 0.8559 97.1 96.2
8, 10
3 0.8792 0.8903 0.8571 97.3 96.2
9, 10
3 0.8676 0.8868 0.8524 97.9 96.2
6.5, 10
5 0.9223 0.8901 0.8838 95.6 99.4
7, 10
5 0.9208 0.8849 0.8802 95.4 99.4
7.5, 10
5 0.9284 0.8859 0.8819 95.1 99.4
8, 10
5 0.9298 0.8903 0.8845 94.8 99.4
9, 10
5 0.9335 0.8887 0.8826 94.3 99.4

be used to predict celestite grade and recovery within the limits of pH, SrSO4 in the feed
and sodium silicate concentration variables.
Fig. 4a shows that, within the studied pH range at a 10
5 M sodium silicate
concentration, the celestite grade in the concentrate is lower than the that obtained at a
10
3 M concentration, while the recovery is higher (Fig. 4b). It is also seen from Fig.
4a that the celestite grade decreases with increasing pH for the lower sodium silicate
concentration. The opposite tendency is observed for the higher sodium silicate
concentration. On the other hand, it is observed that the celestite recovery does not
depend on the pH (Fig. 4b), which is in accordance with the ANOVA analysis of the
obtained results from the factorial design.

3.4. Thermodynamic approach on floatability results

The ANOVA of the obtained results shows that all of the variables studied, as well as their
respective combinations, affect the SrSO4 grade. These results can also be explained, in part,
as a function of the thermodynamic relationship that exists between pH and the sodium
silicate concentration.
The distribution diagram for silicate species presented in Fig. 5 was plotted considering
the thermodynamic data reported in Table 6 and taken from Wen Qi et al. (1993) and
Marinakis and Shergold (1985). In this figure, it is possible to identify that the silicate species
Si(OH)4(ac) and SiO(OH)3
are predominates into the pH range of the study (from 6.5 to 9).
Also, it is observed that there are more silicate species at 10
3 M sodium silicate (Fig. 5a)
than at lower concentration 10
5 M (Fig. 5b). The silicate species Si(OH)4(ac) and
SiO(OH)3
may be adsorbed on the calcite mineral surface as a function of pH rendering
its surface more hydrophilic, therefore its floatability is decreased and the celestite grade in
the concentrate is increased. However, these same species may be partially displaced from
the calcite surface by the collector ions at the lower silicate concentration (10
5 M) and the
celestite grade decreases with pH. The selective adsorption of these species on the calcite
surface as a function of pH for different sodium silicate concentration has been previously
92 A. Martnez L. et al. / Int. J. Miner. Process. 70 (2003) 8397

Fig. 4. Floatability of celestite as a function of pH: (a) SrSO4 grade and (b) SrSO4 recovery in the concentrate.
The dotted and solid lines shows the values calculated with the Eqs. (3.1) and (3.2), respectively.

demonstrated by using electrokinetic and floatability studies (Martnez-Luevanos et al.,

2000).
On the other hand, the obtained ANOVA results as a function of SrSO4 recovery shows
that the pH variable and its combinations with the sodium silicate concentration, and with
the sodium silicate concentration and celestite grade in the feed, do not significantly affect
the SrSO4 recovery at the concentrate. These results cannot be explained totally by only
considering the thermodynamic relationship that exists between pH and the sodium silicate
 A. Martnez L. et al. / Int. J. Miner. Process. 70 (2003) 8397 93

Fig. 5. Distribution of silicate species as a function of pH at 25 jC at: (a) 10
3 M and (b) 10
5 sodium silicate
concentration.

concentration. It is necessary to consider the solubility equilibrium between cations from

the minerals with anions from dissolution of collector and depressant. Celestite recovery in
the concentrate also can be affected by the type of adsorption mechanism of both the
collector and depressant on the mineral surface.
It is worth mentioning that into the solution ions from the minerals (SrSO4 and CaCO3 are
sparingly soluble salt-type minerals) and ions from dissolution of collector and depressant
94 A. Martnez L. et al. / Int. J. Miner. Process. 70 (2003) 8397

Table 6
Hydrolysis equilibria for silicic acid with corresponding equilibrium constants Kj reported by Wen Qi et al.
(1993) and Marinakis and Shergold (1985)
Equilibrium Log Kj
a
SiO2 (s, amorphous) + 2H2O = Si(OH)4
2.7
Si(OH)4 = SiO(OH)
3 +H
+

9.473
Si(OH)4 = SiO2(OH)22
+ 2H+
22.12
2Si(OH)4 = Si2O3(OH)24
+ 2H+ + H2O
18.00
2Si(OH)4 = Si2O2(OH)
+
5 + H + H2 O
7.75
3

3Si(OH)4 = Si3O5(OH)5 (cyclo) + 3H+ + 2H2O
26.43
3Si(OH)4 = Si3O6(OH)33
(linear) + 3H+ + 3H2O
25.40
4Si(OH)4 = Si4O7(OH)35
(cyclo) + 3H+ + 4H2O
23.42
4Si(OH)4 = Si44
+ 4H+ + xH2O
32.81
5Si(OH)4 = Si55
+ 5H+ + yH2O
41.50
a
Marinakis and Shergold (1985).

are present. These ions can react and the product or products may affect the mineral surfaces
and the flotation response. At sodium dodecyl sulfonate concentration used in the present
work (10
4 M), the precipitation of slightly soluble Sr(C12H25SO3)2 and Ca(C12H25SO3)2
compounds by the reaction of Sr2 + and Ca2 + ions with the C12H25SO3
collector anion takes
place on the celestite and calcite mineral surfaces (Martnez-Luevanos et al., 1999).
Additionally, Sr2 + and Ca2 + ions also can react with silicate species (Si(OH)4(ac),
SiO(OH)3
) to form SrSiO3 and CaSiO3 compounds (Table 7). The reactions that may
occur between Sr2 + or Ca2 + ions and the silicate species Si(OH)4(ac) and SiO(OH)3
, are
shown in Table 7.
Software HSC Chemistry version 3.02 (Outokumpu Research) was used to calculate the
values of reaction standard free energy (DGj) r and the reaction constant (Kj) for most of
the reactions. For Reactions (2) and (4), the values of formation standard free energy
(DGj)f employed were the reported by Garrels and Christ (1990).
The high Kj values mean that the reactions between the Sr2 + or Ca2 + cations and the
silicate species, Si(OH)4(ac) and SiO(OH)3
, will proceed predominantly as they are
written, so the formation SrSiO3 and CaSiO3 is mainly favoured through Reactions (1)
and (3), respectively.
The Sr(C12H25SO3)2, Ca(C12H25SO3)2, SrSiO3 and CaSiO3 compounds can be
involved in the adsorption mechanism of sodium dodecyl sulfonate and sodium silicate
on celestite and calcite affecting the celestite recovery in the concentrate.

Table 7
Equilibria for celestite-silicate and calcite-silicate aqueous solutions
Reaction Kj DGjr (kcal/mol)
Celestite/silicate aqueous solution
Sr2 + + Si(OH)4 (ac) + 2OH
ZSrSiO3 + 3H2O (1) 9.56  1049
68.18
Sr2 + + SiO(OH)


3 + OH ZSrSiO3 + 2H2O (2) 4.33  1010
14.51

Calcite/silicate aqueous solution

Ca2 + + Si(OH)4 (ac) + 2OH
ZCaSiO3 + 3H2O (3) 9.68  1050
69.55
Ca2 + + SiO(OH)


3 + OH ZCaSiO3 + 2H2O (4) 6.18  1010
14.72
 A. Martnez L. et al. / Int. J. Miner. Process. 70 (2003) 8397 95

4. Conclusions

The obtained experimental results and the analysis performed allow us to draw the
following conclusions.
The results of the flotation experiments of celestite and calcite synthetic mixtures
containing a 50% and 90% of SrSO4 suggest that celestite can be selectively separated
from calcite using sodium dodecyl sulfonate as collector and sodium silicate as calcite
depressant.
The statistical analysis performed on the flotation results suggests that it is possible
to obtain celestite concentrates containing about 98% of SrSO4 grade and up to 96%
of SrSO4 recovery. The factors that had the greatest effect on the grade and recovery
of celestite were the celestite grade in the feed (L) and the depressant concentration
(C).
The thermodynamic analysis performed on the systems celestite and calcite/aqueous
solutions confirms the complex role that pH play when it is combined with other variables
such as collector and depressant concentration (sodium dodecyl sulfonate and sodium
silicate, in the present case) on the celestite grade and recovery in the concentrate.

Acknowledgements

The authors thank CONACYT (Mexico) for the financial support received. A. Martnez
L. thanks CONACYT for the scholarship provided.

Appendix A . Analysis of contrasts

The experimental design used in this work was a factorial experimental design 23 with
two replicas for each experiment. The notation used to establish the experimental
conditions for each test is presented in Table AI.1.

Table AI.1
Analysis of contrasts and notation used to establish the experimental conditions for each test
Number Factors Treatment
of test combinations
SrSO4 in the pH [Na2SiO3]
feed grade
1


(1)
2 +

a
3
+
b
4 + +
ab
5

+ c
6 +
+ ac
7
+ + bc
8 + + + abc
+ = High level.

= Low level.
96 A. Martnez L. et al. / Int. J. Miner. Process. 70 (2003) 8397

Valuation of the contrast values: The statistical analysis of the values of the contrasts for
the main effects as well as its interactions (or its combinations), allow to know which of
these values significantly affect the variable of answer. This helps to improve the
efficiency of the processes since one obtains mathematical expressions that allow to
predict the results.
Values of the contrasts for the main effects of the factors SrSO4 grade % in the feed, pH
and sodium silicate concentration (factors A, B, and C, respectively), and contrast values of
its interactions (AB, AC, BC, and ABC), are given by the following expressions:

A=(1/4n) [a
(1) + ab
b + ac
c + abc
bc]

B=(1/4n) [(bc + abc + b + ab)
(c + ac + (1) + a)]
C=(1/4n) [c + ac + bc + abc
(1)
b
a
ab]
AB=(1/4n) [(1) + ab + c + abc
a
b
ac
bc]
AC=(1/4n) [(1) + b + ac + abc
c
bc
a
ab]
BC=(1/4n) [(1) + a + bc + abc
b
ab
c
ac]
ABC=(1/4n) [abc
bc
ac + c
ab + b + a
(1)]

where n is the number of replicas (n = 2, in the present case).

These expressions were evaluated in terms of grade and recovery of SrSO4 in the
concentrate in order to obtain the values of the contrasts for the main effects and its
interactions. The obtained results are presented in Table AI.2.

Table AI.2
Values of the contrasts for the main effects and its combinations
Contrasts SrSO4 grade, % SrSO4 recovery, %
A 14.09 4.54
B
5.37 0.93
AB 4.97
5.34
C 5.45
1.44
AC
2.74 2.14
BC 4.054
1.57
ABC
2.71 0.86

References

Andrews, P.R.A., Collings, R.K., 1991. Celestite in Canada. CIM Bull. 84 (95), 36 39.
Chibowski, E., Bilinski, B., Wojcik, W., Cabrerizo, M.A., Gonzalez-Caballero, F., 1988. Correlations between
adsorption and desorption of ionic collectors on celestite surface and its flotability. J. Adhes. Sci. Technol.,
46 56.
Estefan, S.F., 1974. Radiometric study of the adsorption of chromate ions in anionic flotation of barite and
celestite minerals. Powder Technol. 8, 19 22.
Estefan, S.F., 1979. Phosphate activation in cationic flotation of celestite. Tenside Deterg. 16 (6), 306 308.
Garrels, R.M., Christ, C.L., 1990. Solutions, Minerals and Equilibria. Jones and Bartlett Publisher Inc., USA,
p. 450.
Gonzalez-Caballero, F., Cabrerizo, M.A., Bruque, J.M., Delgado, A., 1989. Flotation properties of celestite in
aqueous solutions of ionic surfactants. Int. J. Miner. Process. 26, 51 63.
 A. Martnez L. et al. / Int. J. Miner. Process. 70 (2003) 8397 97

Hernainz Bermudez de Castro, F., Calero de Hoces, M., 1993. Influence of quebracho and sodium silicate in
flotation of celestite and calcite with sodium oleate. Int. J. Miner. Process. 37, 283 298.
Hernainz Bermudez de Castro, F., Calero de Hoces, M., Galvez Borrego, A., 1996. The effect of pH modifier on
the flotation of celestite with sodium oleate and quebracho. Chem. Eng. Sci. 51, 4289 4294.
Hernainz Bermudez de Castro, F., Galvez Borrego, A., Calero de Hoces, M., 1997. Flotacion de celestita y calcita
con dodecil sulfonato sodico y quebracho. Afinidad LIV (470), 287 290.
Houot, R., Joussemet, R., Fabre, F., 1993. Celestite ore upgradingfrom laboratory to mill. Proc. XVIII Interna-
tional Miner. Process., Sydney, pp. 1053 1059.
Lazaridis, N.K., Stalidis, G.A., Matis, K.A., 1995. Application of the factorial design to flotation experiments. In:
Matis, K.A. (Ed.), Flotation Science and Engineering. Marcel Dekker, USA, p. 441.
Lopez-Valdivieso, A., Robledo-Cabrera, A., Uribe-Salas, A., 2000. Flotation of celestite with the anionic col-
lector sodium dodecyl sulfate. Effect of carbonate ions. Int. J. Miner. Process. 60 (2), 79 90.
Luna, A.E., 1995. Situacion actual de la minera. CAMIMEX IX (3), 14.
Marinakis, K.I., Shergold, H.L., 1985. Influence of sodium silicate addition on the adsorption of oleic acid by
fluorite, calcite and barite. Int. J. Miner. Process. 14, 177 193.
Martnez-Luevanos, A., Uribe-Salas, A., Lopez-Valdivieso, A., 1999. Mechanism of adsorption of sodium
dodecyl sulfonate on celestite and calcite. Miner. Eng. 12 (8), 919 936.
Martnez-Luevanos, A., Uribe-Salas, A., Nava-Alonso, F.C., Lopez-Valdivieso, A., 2000. The role of quebracho
and sodium silicate modifiers on the flotation of celestite and calcite with sodium dodecyl sulfonate. Afinidad
LVII (485), 357 362.
Montgomery, D.C., 1991. Diseno y Analisis de Experimentos, 3rd ed. Iberoamericana, Mexico, p. 589.
Pugh, R., Stenius, P., 1985. Solution chemistry studies and flotation behavior of apatite, calcite and fluorite
minerals with sodium oleate collector. Int. J. Miner. Process. 15, 193 218.
Rao, K.H., Forssberg, K.S.E., 1992. Interactions of anionic collectors in flotation of semi-soluble salt minerals.
In: Mavros, P., Matis, K.A. (Eds.), Innovations in Flotation Technology. Kluwer Academic Publishing,
Netherlands, pp. 331 335.
Wen Qi, G., Klauber, C., Warren, L.J., 1993. Mechanism of action of sodium silicate in the flotation of apatite
from hematite. Int. J. Miner. Process. 39, 251 273.