Separation Science and Technology

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Study on comparison adsorption of calcium and

sulfate on scheelite and fluorite surfaces

Zhiguo Zhang, Yijun Cao, Yinfei Liao & Zilong Ma

To cite this article: Zhiguo Zhang, Yijun Cao, Yinfei Liao & Zilong Ma (2018): Study on comparison
adsorption of calcium and sulfate on scheelite and fluorite surfaces, Separation Science and
Technology, DOI: 10.1080/01496395.2018.1534865

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Published online: 19 Oct 2018.

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SEPARATION SCIENCE AND TECHNOLOGY
https://doi.org/10.1080/01496395.2018.1534865

Study on comparison adsorption of calcium and sulfate on scheelite and fluorite

surfaces
Zhiguo Zhanga,b, Yijun Caob,c, Yinfei Liaob, and Zilong Mab
a
School of Chemical Engineering and Technology, China University of Mining and Technology, Xuzhou, China; bChinese National Engineering
Research Center of Coal Preparation and Purification, China University of Mining and Technology, Xuzhou, China; cHenan Province Industrial
Technology Research Institution of Resources and Materials, Zhengzhou University, Zhengzhou, China

ABSTRACT ARTICLE HISTORY

This study investigated the adsorption of calcium and gypsum on scheelite and fluorite using Received 29 November 2017
micro-flotation, X-ray photoelectron spectroscopy, scanning electron microscope with energy- Accepted 8 October 2018
dispersive spectrometer, and zeta potential measurements. Micro-flotation showed scheelite KEYWORDS
recovery is more sensitive to calcium, and gypsum shows stronger inhibition than calcium. Calcium-bearing mineral;
Stick-shape precipitates as sulfate-bearing are only found on fluorite surface in gypsum solution. scheelite; fluorite; calcium;
Change law of the zeta potentials of scheelite and fluorite in gypsum solution is obviously gypsum
different from that in calcium solution. Therefore, we concluded that gypsum would make the
separation of scheelite from fluorite more difficult than calcium.

Introduction flotation rate in the lead rougher when using ethylxanthate

collector alone. They found that the calcium sulfate could
Scheelite is a major source to extract tungsten, which has
adsorb on galena surface, which resulted in a restriction of
been considered as an important strategic material in mod-
the surface exposure of all the sulfide minerals. Dávila-
ern industry. As a calcium-bearing mineral, scheelite is
Pulido et al.[16] presented a study on the depression of
usually associated with fluorite, calcite, and dolomite.[1,2]
sphalerite by gypsum precipitates using zeta potential,
These minerals are of similar surface properties and reac-
micro-flotation, contact angle measurement, and scanning
tivity to conventional fatty acid.[3,4] In addition, with the
electron microscopy. They found that the presence of cal-
complex results of fine-grained dissemination, low-grade
cium and sulfate ions decreased the hydrophobicity of
ores, and diversity of the gangue mineral recently, the
sphalerite activated with Cu. And this depression could
separation of calcium-bearing minerals is still a long-term
be substantially restored with the addition of sodium car-
thorny problem.
bonate, by a mechanism consisting of gypsum dissolution
Nowadays, studies of calcium-bearing mineral separa-
and calcium consumption via calcium carbonate precipita-
tion mostly focus on selective flotation[5,6], research
tion. Deng et al.[17] studied the uptake of copper and
methods[7–9], and novel regents[10–12] based on mineral
xanthate on sphalerite in gypsum supersaturated solution
system as scheelite–fluorite–calcite. However, a scheelite
using zeta potential distribution, atomic absorption spec-
deposit with a novel gangue mineral system[13] was verified
troscopy, and quartz crystal microbalance with dissipation.
in China. In this deposit, a mass of gypsum and fluorite was
Their results indicated that gypsum could retard the
found as gangue minerals. The solubility of gypsum is
adsorption of copper and hence the sequence xanthate
relatively larger than other calcium-bearing minerals.-
[14] adsorption on sphalerite, in the way of competing with
Gypsum is of relatively larger soluble than other cal-
copper species for the reactive surface sites of the sphalerite.
cium-bearing minerals.[14] Thus, it would dissolve into
In this paper, floatability of scheelite and fluorite trea-
calcium and sulfate ions in solution, which would badly
ted in calcium chloride solution and gypsum saturated
influence the flotation of scheelite.
solution was studied using micro-flotation. The mechan-
As we know, several scholars previously have found the
ism of calcium and sulfate adsorption on scheelite and
presence of gypsum in deposits associated with gangue
fluorite surfaces was analyzed using X-ray photoelectron
mineral. Grano et al.[15] focused on the galena flotation
spectroscopy (XPS), scanning electron microscope with
section of the Hilton Concentrator with a problem of low

CONTACT Yijun Cao [email protected] Chinese National Engineering Research Center of Coal Preparation and Purification, China University of
Mining and Technology, 221116 Xuzhou, China.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lsst.
© 2018 Taylor & Francis
2 Z. ZHANG ET AL.

energy-dispersive spectrometer (SEM-EDS), and zeta single mineral to 100 mL gypsum saturated solution and
potential measurements. calcium solution. The suspensions would be adjusted to pH
of 9 around and stirred for 30 min under a speed of
800 rpm at room temperature. After 12 hours standing,
Materials and methods the suspension would be rinsed with DI water for three
Experimental minerals and reagents times and dried in vacuum. Blank test samples were pre-
pared using DI water for comparison.
Pure minerals were used to study the influence of ion
adsorption on mineral floatability. All minerals included
scheelite, fluorite, and gypsum were collected through
hand picking from Yunnan, China. X-ray powder diffrac- Zeta potential measurements
tion data and mineral assay confirmed that scheelite, fluor- The zeta potentials of scheelite and fluorite treated
ite, and gypsum samples were 98%, 99%, and 97% pure, before and after were analyzed using a ZetaPALS zeta
respectively. Samples for the micro-flotation tests were dry potential analyzer (Brookhaven, USA). The suspension
ground into −74 μm in a porcelain mill, and −10 μm was prepared by adding 0.05 g mineral samples to
below-sift was used for zeta potential and XPS 40 mL solution with required ion concentration. The
measurements. pH value was adjusted, and the suspension was stirred
Chemically pure reagents of sodium oleate (NaOl, for 20 min. The agitated suspension was sampled to
C18H33O2Na), sodium hydroxide (NaOH), and calcium determine the zeta potential. The results presented are
chloride (CaCl2) were obtained from Sinopharm the average of three independent measurements at least
Chemical Reagent Beijing Co., Ltd, China. The pH with a typical variation of 5%.
was adjusted with NaOH or HCl stock solutions. All
solutions used for adsorption with minerals were pre-
pared in calcium concentration of 1.18 × 10−2 mol/L, Results and discussions
respectively, according to the solubility product of
gypsum.[14] Deionized (DI) water with a resistivity of Micro-flotation tests results
more than 18 MΩ× cm was used for all experiments. It is recognized that dissolved ions in pulp would compli-
cate the floatability and separation selectivity of the
Micro-flotation experiments minerals[18], such as Fe3+ adsorbed on smithsonite[19],
Pb2+ on cassiterite[20] or scheelite[21,22], and Ca2+, Mg2+
The mineral recovery could give the ion influence on calcite and dolomite.[23] As a result of similar active
results on flotation directly. Micro-flotation tests were crystal surface site, sulfate ionized by gypsum could prob-
carried out in an XFG flotation machine at an impeller ably adsorb on scheelite and fluorite surfaces. In this sec-
speed of 1600 rpm with a 40-mL plexiglass cell. The tion, calcium chloride and gypsum were added into
single mineral suspension was prepared by adding 2.0 g flotation pulp to study the influence on mineral recovery
of single mineral to 35 mL of DI water; the mixed and selectivity.
binary mineral suspension was prepared by mixing The flotation conditions were based on our previous
scheelite and fluorite at a 1:1 ration into 35 mL of DI laboratory results, including pH of 9, NaOl dosage of
water. The pH of the mineral suspension was first 2.5 × 10−4 mol/L, and pulp concentration. The flotation
adjusted and stirred for 3 min. Once a desired condi- results of single mineral and mixed binary minerals are
tion modified, the suspension would be agitated for shown in Figs. 1 and 2.
3 min and the pH measured followed. The flotation Figure 1 shows that the scheelite recovery decreases
would last for 4 min to collect the products, then dried, significantly with an increase of calcium concentration in
and weighed. The products would be calculated and both solutions. The fluorite recovery in calcium solution
assayed to determine the grade and recovery. holds the line relatively, while it shows a slightly decrease
with the gypsum solution concentration increased. The
mixed binary mineral flotation in Fig. 2 shows that both
Surface characteristic tests
grade and recovery of scheelite reduce with the addition of
To detect the surface characteristics of the samples treated calcium and further reduce to 36% and 61% around when
in solution before and after, the mineral samples were treated in gypsum saturated solution. The presence of
characterized with measurements of SEM-EDS (Quanta calcium and sulfate would lead a bad performance on
250, FEI, USA) and XPS (Escalab 250Xi, Thermo separation of scheelite from fluorite without using an
Scientific, USA). Samples were prepared by adding 1 g of inhibitor.
 SEPARATION SCIENCE AND TECHNOLOGY 3

100 element information on mineral surfaces. XPS narrow

90
scan Ca 2p and S 2p spectra of scheelite and fluorite
samples are shown in Figs. 3–5. Analysis of atomic con-
Flotation recovery(%)

80
Scheelite+CaCl2 centrations on scheelite and fluorite surfaces treated before
70 Scheelite+Gypsum and after is shown in Tables 1 and 2.
Fluorite+CaCl2
60 Fluorite+Gypsum According to the XPS results in Fig. 3, the Ca 2p peaks of
scheelite increase 0.51 and 0.16 ev when treated in gypsum
50
saturated solution and calcium solution, respectively. And
40 the Ca 2p peaks of fluorite still increase with 0.30 eV higher
30
when treated in gypsum saturated solution and 0.18 eV
higher when treated in calcium solution. Combined with
0 2 4 6 8 10 12 14
Ca2+concentration(10-3mol/L)
the atomic concentration results in Tables 1 and 2, calcium
concentration on scheelite surface increases in gypsum
Figure 1. Effect of calcium concentration on scheelite and saturated solution, while decreases a little in calcium solu-
fluorite flotation. tion. The calcium concentrations on fluorite surface
The previous studies have found that oleate would pre- increase after treated in both solutions.
cipitate into calcium oleate on calcium-bearing mineral Besides, according to the results of XPS narrow scan S 2p
surfaces in chemical adsorption, followed by the physical spectra in Fig. 5, a trace signal matched with S 2p peaks (S
adsorption of hydrocarbon chains.[24,25] This is mainly 2p 168.5 eV) could be detected on fluorite surface, but
caused by Ca density and activity on mineral surfaces.[26] without any characteristic trace on scheelite surface. In
In addition, it was reported that a mass of calcium existed addition, analysis of atomic concentrations confirms the
in solution would expend approximately 10 times more presence of S on fluorite surface, but not on scheelite sur-
collectors to obtain the same floatability.[27] According to face. The results of XPS suggest that calcium could adsorb
the comparison results, scheelite recovery is more sensitive on the commonly exposed surfaces for both scheelite and
to the presence of calcium than that of fluorite. It is con- fluorite in different degrees. These were previously investi-
sidered that calcium in solution would coat on mineral gated as commonly exposed surfaces of scheelite {112} and
surfaces[28], which would prevent oleate from adsorbing fluorite {111} in the flotation pulp.[29–31] Moreover, the S 2p
with Ca site on mineral surface. Meanwhile, gypsum in signal (S 2p 168.5 eV)[32] found on fluorite surface is
solution shows a stronger inhibition on mineral floatability. considered as new sulfate-bearing forms after treated in
gypsum saturated solution.

XPS analysis results SEM measurement results

Samples treated in both solutions before and after at pH of Some micro-scale transformations would be generated
9 were examined using XPS measurement, to obtain after the uptake of ions on mineral surfaces. In order to
100 100
Grade of scheelite
Recovery of scheelite
80 80
Recovery(%)
Grade(%)

60 60

40 40

20 20

0 0
DI water Gypsum saturated solution Calcium solution

Figure 2. Effect of calcium solution and gypsum saturated solution on mixed binary mineral flotation.
4 Z. ZHANG ET AL.

347
Scheelite +CaCl2

347.35
Scheelite +Gypsum

Counts(s)
346.84
Scheelite

338 340 342 344 346 348 350 352 354 356 358 360 362

Binding energy(eV)

Figure 3. XPS narrow scan Ca 2p spectra of scheelite treated before and after.

347.83
Fluorite
348.13
Fluorite +CaCl2
Counts(s)

348.01
Fluorite +Gypsum

338 340 342 344 346 348 350 352 354 356 358 360 362

Binding energy(eV)
Figure 4. XPS narrow scan Ca 2p spectra of fluorite treated before and after.

observe the change, scheelite and fluorite treated in surfaces after treated in calcium solution and gypsum
calcium solution and gypsum saturated solution at pH saturated solution in Fig. 7 are identically coated with
of 9 were examined using SEM-EDS. Blank tests were blank sample obviously. According to Fig. 8, fluorite
prepared using DI water at the same pH value. The surfaces treated in calcium are similar with pure
results are given in Figs. 6–11. mineral blank test. While stick-shape precipitates,
Pure mineral surface typical SEM micrographs are which is likely to the gypsum precipitates in Fig. 6c,
shown in Fig. 6 including (a) scheelite, (b) fluorite, and could be visible on fluorite surface treated in gypsum
(c) gypsum. Typical SEM micrographs of scheelite and saturated solution. The combined EDS results in Figs. 9
fluorite treated in gypsum saturated solution and cal- and 10 and Table 3 show that 0.11% sulfur is detected
cium solution are shown in Figs. 7 and 8, respectively. on fluorite surface but 0% on scheelite surface through
According to the SEM results in Fig. 6, pure scheelite mapping tests. Meanwhile, single spot test results in
surface is coated with microparticles on cleavage plane; Fig. 11 show that 0.13% sulfur is detected on the
fluorite shows a relative clean surface; gypsum in the stick-shape precipitates in Fig. 8f. When we prepared
SEM is mainly shaped in stick or fiber bundle. Through the samples for test, we ensure that gypsum is actually
comparison testing results of SEM with blank, scheelite dissolved in solution.
 SEPARATION SCIENCE AND TECHNOLOGY 5

Flourite treated with gypsum

168.74

Counts(s) 174 172 170 168 166 164 162 160 158 156

Scheelite treated with gypsum

174 172 170 168 166 164 162 160 158 156

Binding energy(eV)
Figure 5. XPS narrow scan S 2p spectra of scheelite and fluorite treated in gypsum saturated solution at pH of 9.

Table 1. Analysis of atomic concentrations on scheelite surface would generate on fluorite surface but not on scheelite
treated before and after. surface when calcium and sulfate existed together.
Conditions
Atoms Before In gypsum In calcium
Concentration (%) W4f 14.15 14.00 13.88
Ca2p 16.96 17.62 16.81 Zeta potential measurement results
O1s 68.89 68.39 69.31
S2p / / / Zeta potential of minerals would be influenced by new
covering when mineral surfaces are coated with ions in
solution. Figure 12 shows the effect of various ion
Table 2. Analysis of atomic concentrations on fluorite surface concentrations on the zeta potential of scheelite and
treated before and after. fluorite at pH of 9.
Conditions As the results shown in Fig. 12, zeta potentials of
Atoms Before In gypsum In calcium scheelite in both solutions suffer the obvious shift
Concentration (%) F1s 66.18 63.99 63.76 toward positive in the presence of calcium.
Ca2p 33.82 35.22 36.24
S2p / 0.79 /
Furthermore, zeta potential of scheelite in gypsum solu-
tion is relatively lower than that in calcium solution.
However, the influence on fluorite zeta potentials in
Based on the sulfate signal (S 2p 168.5 eV) in XPS gypsum solution and calcium solution is quite different.
and SEM-EDS results, the stick-shape precipitates are Zeta potentials of fluorite keep positive charged with
considered to be calcium sulfate precipitates. calcium concentration increased, which means limited
Meanwhile, several scholars have gained the similar effect by calcium. However, zeta potentials of fluorite
SEM results when sphalerite treated in gypsum satu- decrease immediately to isoelectric point (IEP) and
rated solution.[33,34] Here in our study, calcium sulfate keep negatively charged with the addition of gypsum.

a b c

Figure 6. Typical SEM micrographs of (a) scheelite, (b) fluorite, and (c) gypsum.
6 Z. ZHANG ET AL.

Figure 7. Typical SEM micrographs of scheelite treated in (d) gypsum saturated solution and (e) calcium solution.

Figure 8. Typical SEM micrographs of fluorite treated in (f) gypsum saturated solution and (g) calcium solution.

Figure 9. EDS plane scans of scheelite (up) and fluorite (down) treated in gypsum saturated solution.
 SEPARATION SCIENCE AND TECHNOLOGY 7

cps/eV
8 S-KACa-KA W-LA
7
6

5 S

4 W S
W Ca W
Ca
3

2
1

0
2 4 6 8 10 12 14 16 18
keV
cps/eV
F-KA S-KACa-KA
5

4
S
3 F
S Ca
Ca
2

0
2 4 6 8 10 12 14 16 18 20
keV

Figure 10. EDS of scheelite (up) and fluorite (down) treated in gypsum saturated solution.

cps/eV
F-KA S-KACa-KA
5

4
S
3 F
S Ca
Ca
2

0
2 4 6 8 10 12 14 16 18 20
keV

Figure 11. EDS of spot 1 for fluorite treated in gypsum saturated solution.

Our results are in agreement with previous reports regulated to IEP when calcium adsorbed on crystal
that scheelite in solution is normally negatively charged- surface.[37–39] Zeta potential of fluorite changes a little
[35]
, and the IEP of fluorite ranges around 6.2–10.5.[36] with calcium concentration, while it reduces sharply to
The presence of calcium in both solutions could strongly IEP in gypsum solution. It is considered that sulfate
influence the zeta potential of scheelite in a similar way, could adsorb on fluorite surface, as gypsum is negatively
caused that zeta potential of scheelite could be easily charged at an extensive pH range.[16]
8 Z. ZHANG ET AL.

Table 3. Results of EDS mapping tests on scheelite and fluorite scheelite from fluorite in gypsum solution than that in
surfaces treated in gypsum saturated solution. calcium solution and DI water. The results of surface
Samples Elements Norm. C [wt.%] Atom. C [at.%] characteristics and zeta potential confirm the adsorp-
Scheelite Calcium 19.95 53.35
Tungsten 80.05 46.65
tion of calcium on both minerals. Besides, the presence
Sulfur 0 0 of sulfate contributes to the adsorption difference
Fluorite Calcium 51.47 33.48
Fluorine 48.39 66.41 between scheelite and fluorite, and sulfate-bearing pre-
Sulfur 0.13 0.11 cipitate would generate on fluorite surface under cer-
tain conditions.
As a kind of calcium-bearing mineral, gypsum has
The results of zeta potential indicate that the adsorp- particular mineral properties compared with traditional
tion of calcium could alter the surface potential of gangue minerals such as calcite, dolomite, and apatite.
scheelite and fluorite. Furthermore, the presence of The presence of gypsum in deposit would lead to the
sulfate in solution contributes to the lower potentials complex ion composition in pulp, which would be a
of scheelite. However, significant reduction of fluorite significant problem in calcium-bearing mineral
potential in gypsum solution is due to the adsorption of separation.
calcium sulfate precipitates. This conclusion fairly
agrees with the results of flotation, XPS, and SEM-
EDS above. Conclusions
The present study introduced a new mineral system of
scheelite and fluorite in gypsum solution and calcium
Discussions
solution. According to the results and discussions, the
Micro-flotation tests were studied to obtain the influ- following conclusions could be drawn:
ence of floatability. SEM-EDS, XPS, and zeta potential
measurements were performed to investigate the (i) Micro-flotation results of single mineral and
adsorption characteristics on mineral surfaces. mixed binary minerals suggested that scheelite
According to the single mineral flotation results, we recovery is more sensitive to calcium than fluorite.
could find that calcium in pulp shows a great inhibition Gypsum dissolved in solution would cause the
on scheelite flotation, but a little effect on fluorite. In separation of scheelite from fluorite harder.
addition, the presence of sulfate could intensify the (ii) Analysis results of XPS and SEM-EDS showed
inhibition in different degrees. For the mixed binary that calcium could adsorb on both mineral sur-
mineral flotation, it would be harder to separate faces. Furthermore, stick-shape precipitates

Scheelite+ CaCl2
50
Scheelite+ Gypsum
Fluorite+ CaCl2
40 Fluorite+ Gypsum

30
Zeta potential(mV)

20

10

-10

-20
0 2 4 6 8 10 12 14
-3
Ions Concentration(10 mol/L)

Figure 12. Effect of ion concentration in gypsum solution and calcium solution on the zeta potential of scheelite and fluorite at pH
of 9.
 SEPARATION SCIENCE AND TECHNOLOGY 9

confirmed as calcium sulfate would generate on carbonate ores. Journal of Mining Science, 48 (4): 746–
fluorite surface under certain conditions. 753. doi:10.1134/S106273914804020X
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(2011) In situ AFM study of potassium oleate adsorp-
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sulfate would lower the potential values. In addi- surface. Minerals Engineering, 24 (5): 387–395.
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sharply to IEP compared with calcium. [8] Kou, J.; Xu, S.; Sun, T.; Sun, C.; Guo, Y.; Wang, C. (2016)
A study of sodium oleate adsorption on Ca2+ activated
The comparison results between minerals in calcium quartz surface using quartz crystal microbalance with
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[9] Gao, Z.Y.; Xie, L.; Cui, X.; Hu, Y.; Sun, W.; Zeng, H.
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This would complement the separation research of face forces of fluorite crystals. Langmuir, 34 (7): 2511–
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Acknowledgements activity relationship and mechanisms of reagents used
The authors thank the Advanced Analysis and Computation in scheelite flotation. Rare Metals, 34 (12): 882–887.
Center of China University of Mining & Technology for the doi:10.1007/s12598-014-0381-5
analytical instruments supports. [12] Gao, Y.S.; Gao, Z.Y.; Sun, W.; Yin, Z.; Wang, J.; Hu, Y.
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