International Journal of Mineral Processing 163 (2017) 45–47

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International Journal of Mineral Processing

journal homepage: www.elsevier.com/locate/ijminpro

Utilization of N-carboxymethyl chitosan as selective depressants for

serpentine on the flotation of pyrite
Cheng Zhang, Cheng Liu ⁎, Qiming Feng ⁎, Yanfei Chen
School of Mineral Processing and Bioengineering, Central South University, Changsha 410083, China

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

Article history: Utilization of N-carboxymethyl chitosan (N-CMCh) to limit the detrimental effect of serpentine on the flotation of
Received 27 December 2016 pyrite is presented in this work. Flotation results show that the presence of hydrophilic serpentine slimes results
Received in revised form 17 April 2017 in lower recoveries of the valuable pyrite. Utilization of N-carboxymethyl chitosan can limit the detrimental effect
Accepted 25 April 2017
of serpentine on the flotation of pyrite. Zeta potential measurements illustrate that N-CMCh is with negative
Available online 27 April 2017
charge and the electrostatic interaction between serpentine and N-CMCh is occurred at pH 8.5, then the serpen-
Keywords:
tine zeta potential will be changed from positive to negative, the electro-steric attraction converts into electro-
Serpentine steric repulsion between pyrite and serpentine and the pyrite recovery is improved.
Pyrite © 2017 Elsevier B.V. All rights reserved.
N-CMCh
Flotation separation
Zeta potential

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
2. Experimental. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
2.1. Samples and reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
2.2. Flotation tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
2.3. Zeta potential tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3.1. Flotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3.2. Zeta potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47

1. Introduction
Serpentine often associates with many metal sulfide ore deposits. In
sulfide minerals flotation, many studies demonstrated that serpentine
slime coatings can occur on the valuable mineral surfaces through the
electrostatic attraction, reduce the hydrophobicity of the sulfide particle
and then depress mineral flotation (Basile et al., 2010; Pietrobon et al.,
1997; Feng et al., 2012; Feng et al., 2013). Therefore, efficient flotation
separation of sulfide minerals from magnesium silicate minerals re-
quires selective depressants. Previous studies have shown that CMC is
⁎ Corresponding authors.
E-mail addresses: 145601011@csu.edu.cn (C. Liu), qmfeng@mail.csu.edu.cn (Q. Feng).
the most commonly used depressant for separation of sulfide minerals
from magnesium silicate minerals. CMC depress serpentine slime parti-
cles from sulfide minerals by adsorption on serpentine surface due to
high negative charge density (Edwards et al., 1980; Bremmell et al.,
2005; Wellham et al., 1992).
N-CMCh (see Fig. 1) is a kind of chemical composition, which uses
carboxymethyl replace hydrogen of \\NH2 of chitosan, and consists of
\\CH2COOH groups as CMC (Upadhyaya et al., 2013). In the past de-
cades, much N-CMCh has been synthesized and used in medicine,
chemical industry, biology, environmental protection and many other
areas (Upadhyaya et al., 2013; Chen et al., 2007; Mishra et al., 2011;
Yin et al., 2007), and chitosan has also been explored in the minerals in-
dustry, such as Cu-Pb sulfides and Pb-Fe sulfides separation (Huang et

http://dx.doi.org/10.1016/j.minpro.2017.04.008
0301-7516/© 2017 Elsevier B.V. All rights reserved.
46 C. Zhang et al. / International Journal of Mineral Processing 163 (2017) 45–47
Fig. 1. Structural unit of chitosan and carboxymethyl chitosan (Upadhyaya et al., 2013).
al., 2012; Huang et al., 2013). However, very little research has been
conducted concerning the application of carboxymethyl chitosan on
mineral flotation.
The aim of this work is to determine the effect of serpentine slimes
on pyrite flotation, a new depressant used to limit the detrimental effect
of serpentine on the flotation of pyrite, control studies using CMC are
also performed to evaluate the superiority of the N-CMCh. In order to as-
sess the validity of the results, zeta-potential measurements were used
in this study.
2. Experimental
2.1. Samples and reagents
The serpentine and pyrite samples used for all experiments were ob-
tained from Donghai, Jiangsu Province and Yunfu, Guangdong Province
of China, respectively. The samples were crushed and ground using an
agate mortar − 10 μm (serpentine) and − 74 + 38 μm (pyrite) were
used for the flotation tests. The − 2 μm size fractions were prepared
for zeta potential. The X-Ray Diffraction (XRD) showed the purity of
sample was very high.
Technical grade SBX (Sodium butyl xanthate) with 85% purity was
used as collector, analytical grade MIBC (Methyl Isobutyl Carbinol)
was used as frother. Chemically pure N-CMCh and CMC (obtained
from Aladdin Chemical Reagent Co., Shanghai, China) were used as de-
pressants for serpentine. Analytical grade sodium hydroxide and hydro-
chloric acid were used for the pH adjustment in the experiments, and
water used in all the tests was distilled water.
2.2. Flotation tests
The flotation tests were carried out in a mechanical agitation flota-
tion machine. The mineral suspension was prepared by adding 2.0 g of
mineral to 35 mL of solution. When needed, serpentine would be
added at the beginning of the conditioning period. The pulp was contin-
uously stirred for 3 min using a pH regulator, 3 min with the collector.
The pH of the solution was measured before the flotation, and the flota-
tion was conducted for 4 min. The floated and unfloated particles were
collected, filtered and dried. The flotation recovery was calculated based
on solid weight distributions between the two products. Each micro-flo-
tation test was measured three times, and the average reported as the
final value. The standard deviation, which is presented as an error bar,
was obtained by means of the three measurements per experimental
condition.
2.3. Zeta potential tests
Single minerals zeta measurements were measured in 1 × 10−3 mol/L
KNO3 background electrolyte solution using Coulter Delsa440sx Zeta an-
alyzer instrument. The suspensions containing 0.01% sample were dis-
persed in a beaker magnetically stirred for 15 min at various pH values.
After 20 min of settling, the pH value of the suspension was measured
and the supernatant was obtained for zeta-potential measurements.
The zeta-potential of each sample was measured three times in this
work, and the average was reported as the final value. The standard devi-
ation was obtained as mentioned previously.
3. Results and discussion
3.1. Flotation
The flotation recovery of pyrite in the absence and presence of ser-
pentine as a function of pH is shown in Fig. 2. The flotation recovery of
pyrite in the absence of serpentine was about 90% below pH 9.5.
When the pH was increased, pyrite recovery decreased due to formation
of Fe(OH)3 species on the pyrite surface (Bicak et al., 2007). When ultra-
fine serpentine particles were added prior to collector addition, the re-
covery of pyrite decreased with increasing pH from a maximum recov-
ery of 90% to 19% when 5.0 g/L serpentine had been added, which was
similar to earlier observations (Bremmell et al., 2005). Fig. 2 also
shows that the flotation recovery of pyrite increased with increasing
pH in the presence of 0.02 g/L N-CMCh when serpentine had been
added, when above pH 10, pyrite recovery decreased sharply. The re-
sults indicated that the addition of N-CMCh could restore the recovery
of pyrite which had been depressed by serpentine at pH 7–10.
Fig. 3 shows the effect of N-CMCh or CMC concentration in the
flotation of pyrite/serpentine system at pH 8.5 in the presence of
1 × 10−4 mol/L SBX and 1 × 10−4 mol/L MIBC. A maximum increase
in pyrite recovery was obtained with 0.02 g/L N-CMCh, above 0.02 g/L
N-CMCh, the flotation recovery of pyrite remained constant. It can be
seen from Fig. 3 that above 0.02 g/L CMC slightly reduced pyrite recov-
ery. The recovery of pyrite reached the highest points of 90% with the
addition of 0.04 g/L N-CMCh, compared with 66% with the addition of
0.02 g/L CMC. The effects of CMC were less obvious than N-CMCh.
3.2. Zeta potential
In order to investigate the reaction mechanism of dissolve species on
the pyrite surface, zeta-potential tests were carried out. The zeta poten-
tial of pyrite and serpentine in the absence and presence of N-CMCh
were measured as a function of pH value shown in Fig. 4. The results
in Fig. 4 demonstrate that the isoelectric point (IEP) of serpentine and
pyrite occurred at pH 11.6 and pH 2.8 without reagent, respectively.
The charge of serpentine surface is positive below pH 11.6, while the
charge of pyrite is negative above pH 3, similar to the research of Feng
(Feng et al., 2012). Flotation of nickel sulfide ores is routinely performed
around pH 8.5, however, zeta potential of serpentine and pyrite are op-
posite at pH 8.5. The hydrophilic micro-fine serpentine particles will
Fig. 2. Flotation recovery of pyrite as a function of pH under different conditions.
[Pyrite] = 50 g/L [Serpentine] = 5 g/L, [N-CMCh] = 0.02 g/L, [SBX] = 1 × 10− 4 M,
[MIBC] = 1 × 10−4 M.
 C. Zhang et al. / International Journal of Mineral Processing 163 (2017) 45–47
Fig. 3. Flotation recovery of pyrite as a function of depressant concentration at pH 8.5.
[Pyrite] = 50 g/L [Serpentine] = 5 g/L, [SBX] = 1 × 10−4 M, [MIBC] = 1 × 10−4 M.
attach to the pyrite particle surface by electrostatic attraction and may
reduce collector adsorption. As is shown in Fig. 4, 0.02 g/L N-CMCh
changed the zeta potential of serpentine to negative at all pH values
and decreased the zeta potential of pyrite blow pH 6. However, it had
negligible effect on the zeta potential of pyrite, both pyrite and serpen-
tine are negatively charged at pH 8.5 in the presence of N-CMCh, and re-
pulsion occurred between micro-fine serpentine and pyrite though
electrostatic attraction.
N-CMCh has a group of carboxymethyl (see Fig. 1). Due to the nega-
tive charge of N-CMCh in aqueous solution (Miranda et al., 2009; Sayin
et al., 2008), it was possible to absorb on positive charge minerals sur-
face by electrostatic interactions. At pH 8.5, pyrite surface with negative
charge and serpentine surface with positive charge, respectively. In ad-
dition of N-CMCh decreases the zeta potential of serpentine significantly
but influences the zeta potential of pyrite slightly at pH 8.5. Therefore,
adsorption of N-CMCh on serpentine takes place, and might through
electrostatic force. The zeta potential of serpentine is less negative in
the presence of CMC than in the presence of N-CMCh. The effects of
CMC were less obvious than that of N-CMCh may be attributed the
carboxymethyl combine with different atom. Carboxymethyl combine
with N atom in N-CMCh and O in CMC, respectively. Previous study
Fig. 4. Zeta-potential of pyrite and serpentine as a function of pH under different condition.
[KNO3] = 1 × 10−3 M, [N-CMCh] = 0.02 g/L, [CMC] = 0.02 g/L.
47
indicated that N-CMC complexed metal ions by \\NH\\ and \\COOH
groups (Ding, 2014), the mechanism of depression of serpentine with
N-CMC is possibly due to the formation of Mg(II) complexes by N-
CMC. Many reports indicated that higher CMC concentration signifi-
cantly reduced pyrite recovery (Bicak et al., 2007). Therefore, by con-
trast, N-CMCh is a proper depressant in flotation of pyrite/serpentine
system.
4. Conclusion
The micro-flotation tests demonstrate serpentine slimes strongly
depress the flotation recovery of the pyrite in the presence of SBX, the
detrimental effect of lizardite on the flotation of pyrite can be efficiently
depressed by the utilization of N-CMCh. Zeta-potential measurements
result shows the serpentine surface potential changes from positive to
negative and slightly effect the pyrite surface charge in the presence of
N-CMCh. Electrostatic interactions occurred between the negatively
charged N-CMCh and the positively charged surface of serpentine.
Under these solutions, the electro-steric attraction will convert into
electro-steric repulsion between pyrite and serpentine. Thus, N-CMCh
might be potential depressants to limit the detrimental effect of serpen-
tine slimes on the flotation of pyrite.
Acknowledgement
The authors acknowledge the support of the Major State Basic Re-
search Development Program of China (973 program) (2014CB643402).
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