Minerals Engineering 84 (2015) 100105

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Recovery of zinc from cyanide tailings by flotation

Xiuli Yang a,b, Xiong Huang b, Tingsheng Qiu a,b,
a
Jiangxi Key Laboratory of Mining Engineering, Jiangxi University of Science and Technology, Jiangxi 341000, China
b
Faculty of Resource and Environmental Engineering, Jiangxi University of Science and Technology, Jiangxi 341000, China

a r t i c l e i n f o a b s t r a c t

Article history: The present research investigates sodium hypochlorite, hydrogen peroxide, sodium metabisulfite and
Received 14 July 2015 copper sulfate as activators to lessen the depressant effect of cyanide. The results indicate that the zinc
Revised 3 October 2015 recovery exceeded 93%, 90%, 85% and 95% at the dosages: sodium hypochlorite 1.5 ml/L, hydrogen perox-
Accepted 6 October 2015
ide 2 ml/L, sodium metabisulfite 1.67
103 mol/L and copper sulfate 2
103 mol/L, respectively.
Available online 24 October 2015
According to the results of FTIR spectrum and zeta potential, it is suggested that the studied marmatite
was depressed due to the adsorption of CN on the surfaces of marmatite by chemical bonds, and more-
Keywords:
over the afore enhanced activators can present ZnACBN bonds on the surfaces of depressed marmatite
Zinc
Cyanide tailings
by oxidation or ionic adsorption, respectively, and hence activate the depressed marmatite for flotation.
Flotation 2015 Elsevier Ltd. All rights reserved.
Activator
Activation mechanism

1. Introduction requirements of environmental protection, but also on economic

Cyanidation tailings are produced from gold plants that use
sodium cyanide as solvent to extract gold (Lv et al., 2015; Zhang
et al., 2013b). The gold industry in China has developed rapidly
due to an increasing gold demand. China produced 451.799 tons
of gold in 2014, up 5.52% over last year. Chinese gold production
has been the highest globally for eight consecutive years. Mean-
while, it is estimated that more than 2.45 million tons of cyanide
tailings are dumped into tailing ponds every year (Li et al.,
2010b; Lv et al., 2015; Wang et al., 2015; Zhang et al., 2013a,
2012). Therefore, about 300 million tons of cyanide tailings have
been stockpiled in China, which causes serious environmental pol-
lution, and even death to wildlife (Adams and Lloyd, 2008; Donato
et al., 2007; Hewitt et al., 2012; Velsquez-Lpez et al., 2011;
Stephen et al., 2009; Zagury et al., 2004). These residues occupy
much land, and tailings storage facilities increase production costs
of gold enterprises (Donato et al., 2007). In addition, these residues
contain many valuable elements, such as zinc, lead, copper and sul-
fide. For example, cyanide tailings from Gaoyao Hetai Gold Plant
(Guangdong Province, China) contains 2.5% Cu, 0.31% Pb, 0.23%
Zn and 15.36% Fe (Shi, 2008) and that from Tianshui Gold Plant
(Gansu Province, China) contains 1.94% Cu, 5.96% Pb, 0.27% Zn
and 24.62% Fe. Therefore cyanidation tailings have been concerned
as a secondary resource rather than waste, not only on the
Corresponding author at: Jiangxi Key Laboratory of Mining Engineering,
Jiangxi University of Science and Technology, Jiangxi 341000, China.
E-mail address: qiutingsheng@163.com (T. Qiu).
requirements.
Mineral compositions differ across different gold plants, but the
total iron content in most cyanide tailings is relatively high. These
tailings can be readily recycled using: magnetizing roastingmag-
netic separation (Li et al., 2010a; Yang et al., 2011), direct
reduction-magnetic separation (Liu et al., 2009; Maweja et al.,
2009) and reduction roasting-water leaching followed by magnetic
separation (Zhang et al., 2012). However, due to the depression of
cyanide, the other minerals, containing metals such as zinc, lead
and copper, are difficult to recycle from cyanide tailings. So the
elimination of depressant remaining from initial processing or
surface species formed during initial processing which will cause
further depression on re-processing is critical for the recovery of
these valuable minerals.
This work focuses on the recovery of zinc which mainly exists in
the form of marmatite in cyanide tailings. Currently the depression
mechanism is not well understood. Some researchers believe that
the marmatite surface become coated with an insoluble hydrophi-
lic Zn(CN)2 compound (Sutherland and Wark, 1955). Other
researchers suggest that the formation of Zn(CN)2 remains in the
solution rather than at the marmatite surface due to weak affinities
between metal cyanide complexes and the parent mineral.
Zinc xanthate complexes are suggested to be responsible for
the hydrophobicity of marmatite in the flotation with xanthate
(Zhu and Zhu, 1996). It is clear that cyanide can depress the
flotation of marmatite. Therefore, in order to recycle zinc from
cyanide tailings, it is necessary to eliminate the depressive effect
of cyanide.

http://dx.doi.org/10.1016/j.mineng.2015.10.003
0892-6875/ 2015 Elsevier Ltd. All rights reserved.
 X. Yang et al. / Minerals Engineering 84 (2015) 100105 101

In this study, depressed fully liberated marmatite was chosen as Table 1

the feed to investigate the elimination of depression using the Chemical composition of the marmatite (wt.%).

specified activators at different dosages, including sodium Zn Fe S Purity

hypochlorite, hydrogen peroxide, sodium metabisulfite and copper 53.55 11.03 34.46 99.05
sulfate. Moreover, the activation mechanisms were investigated by
FTIR measurements and zeta potential measurements.
6000
2. Experimental
Marmtite
5000
2.1. Materials

All reagents used in this study were of analytical grade and 4000
locally procured. Pure marmatite was obtained from Zijin Mining

Intensity (cps)
Industry Co., Ltd. in Fujian Province, China. The chemical composi-
3000
tion of the marmatite is shown in Table 1, and the XRD spectrum is
shown in Fig. 1.
Marmatite depressed by free cyanide was made in the labora- 2000
tory by simulating the gold cyanide leaching process. Marmatite
and sodium cyanide 0.4% were added into sealed beaker and
stirred at the speed of 1000 r/min at a pH value of 12 for 36 h. After 1000

filtration and drying, the obtained residues, termed depressed mar-

matite, were prepared for subsequent experiments. The depressed
0
marmatite was difficult to float and the recovery was only 4% 10 20 30 40 50 60 70 80
(1%) under the conditions: butyl xanthate = 5.32
105 mol/L, Two-Theta (deg)
copper sulfate = 8.01
105 mol/L, 2# oil = 10 mg/L and pH = 10.
Fig. 1. XRD spectrum of the marmatite.
2# oil as frother is a kind of compound higher alcohols.

2.2. Experimental procedure

All experiments were carried out in a flotation machine

equipped with a mechanical stirrer and 40 ml flotation cell. A sche-
matic of the reactor is shown in Fig. 2. For each experiment 10 g of
depressed marmatite and 20 ml of distilled water were put into the
beaker and then dispersed ultrasonically for 5 min. The sample was
left to stand for 10 min before the liquid phase was removed and
then the solid phase was diverted into flotation cell. The regulator,
activator, collector and frother were added in order. After stirring
for 4 min at the speed of 1992 r/min, introduction of air to the cell
was made via a hollow standpipe surrounding the impeller shaft,
and then the air stream was sheared into fine bubbles by the
impeller, these bubbles then rose through the pulp to the surface,
where any particles picked up were removed as a mineralized
froth. The mineralized froths were scraped by mechanical scraper
into the breaker while the pulp remaining in the flotation cell
was filtered, dried and weighed. The zinc content was analyzed
by ICP-AES.
The recovery of zinc was calculated, as follows: Fig. 2. Schematic representation of the reactor.

m1
x1
x%
100 1
m0
x0
where x is the recovery of zinc, m1 is the mass of froth product, x1 is
the fraction of zinc in the mineralized froths product, m0 is the orig-
inal mass of depressed marmatite, and x0 is the fraction of zinc in
the original depressed marmatite.
2.3. Analysis
To examine the purity of the monomineral, the sample was ana-
lyzed using a Philips X-ray diffractometry with Cu Ka radiation
generated at 40 kV and 150 mA, X-ray diffraction spectra were
obtained over a 590 2h range and the diffraction patterns
obtained were compared with the JCPDS archives in the PDXL soft-
ware program. To determine the mechanism of depression, the
FTIR spectra of the samples were recorded in the range from 400
to 4000 cm1 with Thermo Electron Co. Chemical composition
was analyzed by inductively coupled plasma-atomic emission
spectroscopy.
3. Results and discussion
Four activators, including sodium hypochlorite, hydrogen
peroxide, sodium metabisulfite and copper sulfate, were used to
activate depressed marmatite. These reagents were expected to
alter the chemical nature of depressed marmatite surfaces so that
they became hydrophobic due to the action of the collector.
3.1. Effect of sodium hypochlorite on zinc recovery in the flotation
process
The effect of sodium hypochlorite on zinc recovery was tested
using sodium hydroxide as regulator to make the pH of pulp
102 X. Yang et al. / Minerals Engineering 84 (2015) 100105

Dosage of hydrogen peroxide (ml/L) OCN H2 O 2e

CN 2OH EH 0:970 V 6
0.0 0.5 1.0 1.5 2.0 2.5 3.0
100
S2
S 2e EH 0:4763 V 7

80 SO2
4 8H 6e
S 4H2 O EH 0:3572 V 8
In addition, the oxidation of ferrous ions to ferric ions by
Zinc recovery (%)

Hydrogen peroxide sodium hypochlorite and dissolved oxygen takes place according
60 to Eq. (9). The ferric ions in re-activated surfaces can be reduced
to ferrous state by xanthate addition (Kocabag, 1983). Simultane-
ously, oxidation of xanthate ion (X) to dixanthogen (X2) takes
40 place according to Eqs. (10)(12) (Bulut and Atak, 2002;
Fuerstenau et al., 1968):
Sodium hypochlorite  
20 Fe2 ClO H2 O
Fe3 Cl OH 9

2FeOH2 2X
2Fe2 X2 2OH 10
0 1 2 3 4 5 6 7 8
Dosage of sodium hypochlorite (ml/L)
2FeOH2 2X
2Fe2 X2 4OH 11
Fig. 3. Effect of sodium hypochlorite and hydrogen peroxide on zinc recovery
(sodium hydroxide as regulator, pH = 9.510, 5.32
105 mol/L butyl xanthate as 2FeOH3 OH 2X
2Fe2 X2 6H2 O 12
collector, 10 mg/L 2# oil as frother, activation time: 3 min).
Therefore, dixanthogen is responsible for the flotation of re-
activated marmatite with xanthate. Moreover, according to the
EhpH diagrams (Wang et al., 1989) and calculated concentra-
9.510, 5.32
105 mol/L butyl xanthate as collector and 10 mg/L
tionpH diagrams for FeXH2O system (Fornasiero and Ralston,
2# oil as frother. If not specifically mentioned, in the following
1992), ferric hydroxy xanthate complexes form successively on
experiments, the activation time was fixed to be 3 min. The results
the surfaces, so ferric hydroxy xanthate complexes is also respon-
in Fig. 3 indicate that the zinc recovery increases with the
sible for the flotation of re-activated marmatite with xanthate.
increased dosage of sodium hypochlorite up until a value of
1.5 ml/L. The zinc recovery at a 1.5 ml/L dosage of sodium
3.2. Effect of hydrogen peroxide on zinc recovery in the flotation
hypochlorite exceeded 93%.
process
This is attributed to the fact that sodium hypochlorite can inhibit
the cyanide adsorption on marmatite by the conversation of cya-
Fig. 3 shows the effect of hydrogen peroxide on zinc recovery
nide into cyanate (Valenzuela et al., 2013). The reaction is shown
using sodium hydroxide as a regulator to achieve a pulp pH of
in Eq. (2). The Gibbs free energy of the reaction was calculated from
9.510, 5.32
105 mol/L butyl xanthate as collector and 10 mg/
the Gibbs free energy of the species in the reaction and it was
L 2# oil as frother. The activation time was fixed at 3 min. It can
364.48 kJ/mol. The thermodynamic data were taken from Langes
be seen from Fig. 3 that the zinc recovery increases with an
handbook of chemistry (Speight, 2005).
increase in hydrogen peroxide dosage up to 2 ml/L. The zinc recov-
 
ClO CN Cl OCN DGH 364:48 kJ=mol 2 ery exceeded 90% at a hydrogen peroxide dosage of 2 ml/L.
Hydrogen peroxide, like sodium hypochlorite, is a strong oxi-
Until cyanide has been completely converted to cyanate, excess
dant. It can oxidize divalent sulfur ions on the surfaces of
sodium hypochlorite can continue to oxidize divalent sulfur ions
depressed marmatite to elemental sulfur, which makes the
on the surface of depressed marmatite into elemental sulfur or a
depressed marmatite surfaces hydrophobic. However, with an
hydrophilic higher valence state sulfur. The reactions and Gibbs
increase in hydrogen peroxide dosage, elemental sulfur is oxidized
free energies of reaction are 423.62 kJ/mol and 302.96 kJ/mol,
further to a high-valence state sulfur, which is hydrophilic. The
respectively.
results can also be explained from the thermodynamics and elec-
 
ClO S2 2H S Cl H2 O DGH 423:62 kJ=mol 3 trochemistry angle with reactions as follows:

H2 O2 CN OCN H2 O DGH 373:14 kJ=mol 13

 1  1
ClO S2 Cl SO2 DGH 302:96 kJ=mol
4 4 4
The activation of sodium hypochlorite was discussed from the
viewpoint of electrochemistry. Half reactions are shown in Eqs.
(5)(8). Data were from the handbook of standard electrode poten-
tials (Wu et al., 1991). The standard electrode potentials of these
equations show that hypochlorite has the greatest oxidizing abil-
ity, followed by elemental sulfur, and cyanide shows the strongest
reducing ability, followed by the divalent sulfur ion. Therefore, it
can be inferred that hypochlorite first destroys cyanide and then
attacks the sulfides. Moreover, because hypochlorite shows a
stronger oxidizing ability than elemental sulfur, the generated
elemental sulfur can be oxidized further to sulfate. This theory is
consistent with the above results.
 
ClO H2 O 2e
Cl OH EH 0:841 V
4
H2 O2 S2 S 2OH DGH 272:51 kJ=mol 14
1 1
H2 O2 S2 H2 O SO2 DGH 311:71 kJ=mol 15
4 4 4
It can be inferred from these Gibbs free energy data that hydro-
gen peroxide can destroy cyanide adsorption on marmatite by the
conversation of cyanide to cyanate. Moreover, it can oxidize diva-
lent sulfur ions on the surfaces of depressed marmatite to elemen-
tal sulfur and sulfate. From an electrochemistry standpoint, the
half reaction of hydrogen peroxide is shown in Eq. (16). By combin-
ing Eqs. (6)(8) and (16), the same behavior results in the sodium
hypochlorite section. However, because of the lower standard elec-
trode potential of hydrogen peroxide than that of hypochlorite,
namely the weaker oxidizing ability of hydrogen peroxide, a higher
5
hydrogen peroxide than hypochlorite concentration is necessary to
 X. Yang et al. / Minerals Engineering 84 (2015) 100105 103

Dosage of copper sulfate (10-3mol/L) Once the depressions effect of cyanide is removed and fresh sur-
0.0 0.5 1.0 1.5 2.0 faces appear, both dixanthogen and hydroxy xanthate complexes
100
are responsible for the flotation of re-activated marmatite with
copper sulfate
xanthate.
90
Sodium metabisulfite 3.4. Effect of copper sulfate on zinc recovery in the flotation process
Zinc recovery (%)

80
The effect of copper sulfate on zinc recovery was investigated
using sodium hydroxide as a regulator to achieve a pulp pH of
70 9.510, 5.32
105 mol/L butyl xanthate as collector and 10 mg/
L 2# oil as frother. The activation time was fixed at 3 min. The
60 results are shown in Fig. 4. In the range investigated, the zinc
recovery increased with an increase in copper sulfate dosage, and
the zinc recovery at a 2
103 mol/L copper sulfate dosage
50
exceeded 95%.
The stability constants of CuCN2 2
4 and ZnCN4 are 2.0
10
30

40
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
and 5.01
1016, respectively (Yu and Lin, 2011), so copper ions in
-3 the copper sulfate solution can react preferentially with CN to
Dosage of Sodium metabisulfite (10 mol/L)
form a copper complex and the reactions are as follows:
Fig. 4. Effect of sodium metabisulfite and copper sulfate on zinc recovery (sodium Cu2
hydroxide as regulator, pH = 9.510, 5.32
105 mol/L butyl xanthate as collector, ZnCN2
4
Zn
2
4CN
Zn2 CuCN2
4 20
10 mg/L 2# oil as frother, activation time of sodium metabisulfite: 10 min,
activation time of copper sulfate: 3 min). The cyanide in the depressed marmatite surfaces is removed
and fresh surfaces appear. Due to the uptake of free copper ions
on fresh surfaces the surface copper sulfide species form and acti-
vate depressed marmatite (Chandra and Gerson, 2009).
decrease the zinc recovery. This explains why the optimum The activation effect of copper sulfate is best among these acti-
concentration of hydrogen peroxide is 2 ml/L compared with the vators. However, if the cyanide tailings contain chalcopyrite, it is
1.5 ml/L sodium hypochlorite concentration. difficult to separate chalcopyrite and marmatite.
H2 O2 H e OH H2 O EH 0:71 V 16
3.5. Activation mechanism analysis of depressed marmatite

3.3. Effect of sodium metabisulfite on zinc recovery in the flotation
process
The effect of sodium metabisulfite on zinc recovery was
investigated using sodium hydroxide as a regulator to achieve a
pulp pH of 9.510, 5.32
105 mol/L butyl xanthate as collector
and 10 mg/L 2# oil as frother. The activation time was fixed at
10 min. The results are shown in Fig. 4. In the investigated range,
the zinc recovery increased with an increase in sodium metabisul-
fite dosage. When the 1.67
103 mol/L dosage of sodium
metabisulfite was exceeded, the zinc recovery hardly changed. Zinc
recovery exceeded 85% at a sodium metabisulfite dosage of
1.67
103 mol/L.
In aqueous solutions, metabisulfite can form SO2
3 , and the
reaction is as follows:
S2 O2 2
5 H2 O ! 2H 2SO3
The SO23 ion can promote cyanide to cyanate oxidation, with
the reaction as follows:
SO2  
3 2CN 2H 2OCN S H2 O DGH 291:30 kJ=mol
The generated elemental sulfur covers the mineral surfaces.
Moreover, the SO2 3 ion can oxidize divalent sulfur ions to elemen-
tal sulfur, with the reason as shown in Eq. (19). However, it cannot
promote elemental sulfur oxidation. This explains why there is no
downward trend with increasing dosage of sodium metabisulfite in
Fig. 4. Compared with the activation of sodium hypochlorite and
hydrogen peroxide, sodium metabisulfite is activated more slowly,
which can be explained by an activation kinetics study in an article
that will be published soon.
3.5.1. Zeta potential measurements
Mineral surfaces contain broken bonds, which can react with
polar water molecules to cause mineral ion dissolution and disso-
ciation, and hydrogen or hydroxyl ion adsorption on the mineral
surfaces. Therefore, the mineral surfaces are charged. The surface
electrical behavior has a close relationship with floatability.
The ionic radii of S2, Zn2+ and Fe2+ are 0.174 nm, 0.087 nm and
0.083 nm, respectively (Mo and Li, 2012), so the hydration energy
of S2 of marmatite in pure water is lower than that of Zn2+ and
Fe2+. Metal ions enter the water preferentially, which causes the
mineral surfaces to become negatively charged. The effect of pH
on zeta potential on the marmatite surface in pure water and
sodium cyanide solution was investigated and the results are
shown in Fig. 5. The red1 line in Fig. 5 represents the zeta potential
on the marmatite surfaces with pH in pure water. In pure water, the
isoelectric point is 4.4 without the presence of specific absorption. If
17 the pH is less than 4.4, ions on the marmatite surface will include
mainly ZnOH+, FeOH+ and HS, and the zeta potential on the mar-
matite surfaces will be positive because of more positively charged
ions. If the pH value were greater than 4.4, because of more negative
charges on the mineral surfaces, the hydration energy of Zn2+ would
be more than that of S2, and hence Zn2+ would dissolve preferen-
18
tially. The concentrations of ZnOH 3 and ZnOH4
2
increase with
an increase in pH.
The blue line in Fig. 5 represents the zeta potential on the mar-
matite surface with pH value after butyl xanthate addition. Butyl
xanthate absorption on the marmatite surfaces changed the mar-
matite zeta potential. If the pH were below 10, the zeta potential
would shift negatively, and if the pH value were above 10, butyl
xanthate ions and OH would adsorb competitively on the mar-
matite surface.

6H 3S 3H2 O DGH 409:77 kJ=mol

1
For interpretation of color in Figs. 58, the reader is referred to the web version of
SO2
3 2S
2
19
this article.
104 X. Yang et al. / Minerals Engineering 84 (2015) 100105

5
10

Zeta potential (mV)

-5
Zeta potential (mV)

-10
-10

Marmatite
-15 -20 Marmatite+NaCN
Marmatite+NaCN+NaClO
Marmatite+sodium cyanide+butyl xanthate Marmatite+NaCN+H2O2
-20
Marmatite -30 Marmatite+NaCN+Na2S2O5
Marmatite+butyl xanthate Marmatite+NaCN+CuSO4
-25 Marmatite+sodium cyanide
-40
2 4 6 8 10 12 14
2 4 6 8 10 12 14
pH pH

Fig. 5. Effect of pH on the zeta potential (cyanide ion concentration: 0.0816 mol/L, Fig. 6. Effect of pH on the zeta potential (cyanide ion concentration: 0.0816 mol/L,
butyl xanthate concentration: 5.32
105 mol/L). sodium hypochlorite: 1.5 ml/L, hydrogen peroxide: 2 ml/L, copper sulfate:
2.08
103 mol/L, sodium metabisulfite: 3.33
103 mol/L).

The pink line in Fig. 5 represents the marmatite surface zeta

potential with pH value after sodium cyanide addition. If the pH
was less than 5, the zeta potential shifted negatively, and if the
pH was more than 8, the zeta potential shifted negatively, which
indicates CN adsorption on the marmatite surface by chemical Marmatite+NaCN
Transmittance (%)

2059.88
bonds.
The variation in zeta potential on the marmatite surfaces with 460.85
2215.92
pH after simultaneous sodium cyanide and butyl xanthate addition
is shown by a black line in Fig. 5. Compared with the zeta potential
when sodium cyanide only was added, if the pH was less than 8,
the zeta potential shifted negatively. Compared with the zeta Marmatite
potential when butyl xanthate only was added, the zeta potential
did not shift much. If the pH were above 8, the opposite resulted.
This indicates that the order of sodium cyanide and butyl xanthate
addition influenced the marmatite surface zeta potential signifi- 4000 3000 2000 1000

cantly. If sodium cyanide were added first, and if the pH were less Wavenumber (cm )
-1

than 8, at the beginning, butyl xanthate ions would adsorb on the

marmatite surfaces until the saturation point was reached. Then, Fig. 7. FTIR spectrum of marmatite and depressed marmatite.

competitive adsorption would occur between butyl xanthate and

cyanide ions. However, if butyl xanthate were added first, and if
the pH value were more than 8, initially, cyanide ions would
adsorb on the marmatite surfaces to saturation, and then compet-
itive adsorption would occur between butyl xanthate and cyanide
ions.
Fig. 6 shows the effect of activators on zeta potential of the mar-
matite surfaces with pH; the blue line in Fig. 6 represents sodium
hypochlorite. Compared with the red line in Fig. 6, because of the
addition of sodium hypochlorite, the zeta potential shifted posi-
tively. This is attributed to S2 and CN oxidation, which destroyed
the chemical bonding adsorption of CN on the marmatite
surfaces.
The pink line in Fig. 6 shows the effect of hydrogen peroxide on
zeta potential with pH. Compared with the red line in Fig. 6,
because of the addition of hydrogen peroxide, the zeta potential
shifted positively and the isoelectric point rose to 7.3. Because
hydrogen peroxide is a strong oxidant, S2 and CN were oxidized
and the chemical bonding adsorption of CN on the marmatite sur-
faces was destroyed.
The green line in Fig. 6 represents the effect of sodium
metabisulfite on zeta potential with pH. Compared with the red
line in Fig. 6, if the pH was less than 8, because of the hydrolysis
of metabisulfite to sulfite, the zeta potential shifted negatively. If
the pH was more than 8, because of the oxidation of cyanide and
divalent sulfur ions to cyanate and elemental sulfur by sulfite,
the zeta potential shifted positively. Moreover, under alkaline con-
ditions, OH adsorbed competitively on the marmatite surfaces,
and weakened cyanide adsorption.
The influence of copper sulfate on zeta potential with pH is
shown by the dark blue line in Fig. 6. Compared with the red line
in Fig. 6, the addition of copper sulfate shifted the zeta potential
negatively, and the isoelectric point decreased to 2.7. This is attrib-
uted to the fact that excess copper substitutes for zinc on the sul-
fide surface, the complexation of copper with hydroxyl ions is
higher than that with zinc (Yu and Lin, 2011), and so the surface
charge is more negative.
3.5.2. FTIR characterization
FTIR measurements were used to investigate the activation
mechanism by changes in functional groups on the marmatite sur-
faces before and after reagent addition.
Fig. 7 represents the FTIR spectrum of marmatite and depressed
marmatite. The band at 2215 cm1 and 2059 cm1 results from
the stretching vibration of CBN of the complex ion between Zn2+
and CN. The band at 460 cm1 is assigned to the stretching
vibration of ZnAC. By comparing the red line with the black line
in Fig. 7, it can be seen that CN on the marmatite surfaces was
available for chemisorption.
 X. Yang et al. / Minerals Engineering 84 (2015) 100105
2059.88
Marmatite+NaCN
2215.92
Transmittance (%)
Marmatite+NaCN+NaClO
Marmatite+NaCN+H2O2
Marmatite+NaCN+Na2S2O5
Marmatite+NaCN+CuSO4
4000 3000 2000
-1
Wavenumber (cm )
Fig. 8. FTIR spectrum of activated marmatite.
The FTIR spectrum of activated marmatite is shown in Fig. 8. By
comparing the blue, pink, green and black lines with the red line in
Fig. 8, the adsorption peaks at 2215 cm1, 2059 cm1 and
460 cm1 disappeared. This indicates that sodium hypochlorite,
hydrogen peroxide and sodium metabisulfite can break ZnACBN
bonds on the depressed marmatite surfaces, and activate the
depressed marmatite. For copper sulfate, copper ions can adsorb
on the depressed marmatite surface, and activate the depressed
marmatite.
4. Conclusions
(1) Sodium hypochlorite, hydrogen peroxide, sodium
metabisulfite and copper sulfate are effective activators,
but the dosage range is small for sodium hypochlorite and
hydrogen peroxide. It is important to strictly control the
dosage of sodium hypochlorite and hydrogen peroxide to
obtain good activation results. Therefore, these activators
have wide application prospect to process cyanide tailings
in gold plants.
(2) The addition of activators changed the isoelectric point and
zeta potential. Compared with the zeta potential of
depressed marmatite, because of the oxidation of CN by
sodium hypochlorite and hydrogen peroxide, the zeta poten-
tial shifted positively. For copper sulfate, because of the
complexation between Cu2+ and CN and the adsorption of
complex ions, the zeta potential shifted negatively. For
sodium metabisulfite, the pH of 8 was a demarcation point
of positive or negative shift in zeta potential.
(3) Marmatite was depressed because of the adsorption of CN
on the marmatite surfaces by chemical bonds. Sodium
hypochlorite, hydrogen peroxide, sodium metabisulfite and
copper sulfate can break ZnACBN bonds on the surfaces of
depressed marmatite by oxidation or ionic adsorption, and
activate the depressed marmatite.
Acknowledgments
This work was financially supported by the Project of National
Natural Science Foundation of China (No. 51474114) and the
Project of Natural Science Foundation of Jiangxi Province (No.
20142BAB206017).
105
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