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Article history: Chitosan, a natural biodegradable polymer, was studied as a selective depressant in coppermolybdenum
Received 7 July 2015 sulfide separation by flotation. Although chitosan depressed both molybdenite and chalcopyrite in single
Revised 15 September 2015 mineral flotation, selective flotation was achieved during the flotation of molybdenum-bearing copper
Accepted 16 September 2015
sulfide concentrate at pH 6; the recovery of molybdenum in the froth product was over 70% while the
recovery of copper was less than 24%. Adsorption measurements showed that chitosan had a higher
adsorption density on chalcopyrite than on molybdenite. FTIR and ToF-SIMS measurements were carried
Keywords:
out to confirm the different degrees of interaction of chitosan with molybdenite and chalcopyrite and the
Chitosan
Molybdenite
results showed that chitosan mostly adsorbed on chalcopyrite via amide groups when both molybdenite
Chalcopyrite and chalcopyrite were present in the suspension.
Coppermolybdenum separation 2015 Elsevier Ltd. All rights reserved.
Depressant
1. Introduction Houshyar and Amishahi, 2002; Illum, 1998; Loke et al., 2000;
Majeti and Kumar, 2000; Shin and Yoo, 1998; Wang et al., 2002).
The selective separation of coppermolybdenum sulfide miner- Chitosan has also been explored in the minerals industry, for
als by flotation mostly relies on the use of various depressants. example, chitosan could be used as a depressant to depress
Sodium hydrosulfide, sodium sulfide, cyanide and Nokes reagent chalcopyrite selectively in the flotation separation of copperlead
(thiophosphorus or thioarsenic compounds) are routinely used as and leadiron sulfides (Huang et al., 2013, 2012a,b). Also, chitosan
the selective depressants of chalcopyrite (Bulatovic, 2007; Pearse, modified lipid-based particles were observed to adsorb on silica
2005; Prasad, 1992; Yin et al., 2010), the main copper sulfide min- surfaces (treated with mucin) in the pH range from 4 to 6
eral. However, with the increasingly stringent environmental and (Svensson et al., 2008). However, to our knowledge there is not
safety regulations, it is necessary to replace these high dosage, any report about the application of chitosan in the flotation
low selectivity, and toxic or hazardous reagents with more envi- separation of coppermolybdenum sulfides. Thus, in the present
ronmentally friendly chemicals. study, chitosan was chosen as a depressant in coppermolybdenum
Chitosan, a natural biodegradable and non-toxic polyaminosac- sulfide separation using single minerals and Jiama copper
charide, is made from chitin which is the main component of crus- molybdenum sulfide ore samples to determine its possibility to
tacean shells (Davis, 2011; Wan Ngah et al., 2011). As shown in be an effective selective depressant. Adsorption isotherms, FTIR
Fig. 1 (Crini and Badot, 2008), the structures of chitin and chitosan spectroscopic and ToF-SIMS measurements were conducted to
are b(14)-linked N-acetyl glucosamine and b(14)-linked D- illustrate the interaction mechanisms between chitosan and
glucosamine, respectively. Chitosan has been used in many areas minerals (chalcopyrite and molybdenite).
such as biomedical engineering, healthcare, wastewater treatment,
paper and textile industry, agriculture and food industry, etc. 2. Materials and methods
because of its abundance, biodegradability, biocompatibility and
film-forming ability (Burke et al., 2002; Crini and Badot, 2008; 2.1. Materials
Egger et al., 1999; Gerente et al., 2007; Gonzalez Siso et al., 1997;
2.1.1. Reagents
Corresponding authors. Chitosan with a reported deacetylation degree of 8095% and
E-mail addresses: dzwei@mail.neu.edu.cn (D. Wei), qi.liu@ualberta.ca (Q. Liu). sodium sulfide were acquired from Sinopharm Chemical Reagent
http://dx.doi.org/10.1016/j.mineng.2015.09.013
0892-6875/ 2015 Elsevier Ltd. All rights reserved.
218 M. Li et al. / Minerals Engineering 83 (2015) 217222
Feed
P70=74m
Kerosene 50g/t
Sodium butyl xanthate 30g/t
Terpenic oil 50g/t
Rougher 5min
Fig. 1. Structures of the repeating units of chitin and chitosan (Crini and Badot,
2008).
Cleaner 5min
Tailing
Co., LTD, China. The molecular weight of the chitosan ranged from
Cleaner 5min
200,000 to 320,000. The chitosan was dissolved by diluted acetic
acid (1% by weight) before use. Kerosene, terpenic oil and sodium
butyl xanthate were provided by Tieling Flotation Reagents
Factory, China. Zincon monosodium salt, acetic acid and sodium Molybdenum-bearing copper concentrate
acetate were obtained from Fisher Scientific Canada.
Fig. 2. Flotation flowsheet of closed circuit experiment to obtain molybdenum-
bearing copper concentrate.
2.1.2. Minerals
The pure chalcopyrite and molybdenite were obtained from
Yunnan Province and Tibet, China, respectively. The lumps of the
molybdenite and chalcopyrite were crushed manually and hand- tailings. In molybdenum-bearing copper concentrate separation,
picked. The isolated high purity samples were ground in an agate the recovery was calculated from chemical assays of the copper
mortar before sieving to 100 + 45 lm and 45 lm size fractions. and molybdenum contents in the froth and tailings.
The 100 + 45 lm size fraction was used for the flotation tests,
adsorption isotherm measurements and ToF-SIMS. The finer, 2.2.2. Adsorption isotherms measurements
45 lm size fraction was used for FTIR spectroscopic measure- The adsorption studies were performed in a SI-600 shaking
ments. The BET (Brunauer, Emmett, Teller) specific surface area incubator (Jeio Tech, USA) operating at 200 rpm at 25 C. Two
of the 100 + 45 lm size fraction of chalcopyrite and molybdenite grams of a mineral powder (100 + 45 lm) and 50 mL distilled
was 0.29 m2/g and 0.56 m2/g determined by an Autosorb-C water were mixed in a conical flask, to which a given amount of
analyzer (Quantachrome, US). The results of a chemical analysis xanthate or chitosan solution was added. The conditioned suspen-
and X-ray powder diffraction confirmed that the purity of sion was placed in the shaking incubator and shaken for 1 h. After
chalcopyrite was 95.0% and molybdenite 90.2%. filtering, the xanthate concentration of the filtrate was determined
A coppermolybdenum ore sample was obtained from Jiama by UVVis spectroscopy and the residual amount of chitosan in the
copper polymetallic deposit in Tibet, China. It contained 0.90% cop- filtrate was determined by a complexation reaction between the
per and 0.056% molybdenum. The mineralogical analysis showed chitosan and zincon monosodium salt and by UVVis spectroscopy
that copper and molybdenum mainly existed in the form of chal- (Gao et al., 2003). It was assumed that the amount of xanthate or
copyrite and molybdenite respectively and the gangue minerals chitosan depleted from the solution had been adsorbed completely
were primarily quartz, chlorite and calcite. The chemical analysis on to the mineral surface. The amounts of xanthate and chitosan
confirmed that the molybdenum-bearing copper concentrate adsorbed on minerals were determined for different equilibrium
obtained from the coppermolybdenum ore bulk flotation test, concentrations.
conducted following the procedure shown in Fig. 2, contained
22.42% copper and 1.96% molybdenum. 2.2.3. FTIR spectroscopic measurements
One gram of 45 lm chalcopyrite or molybdenite sample was
2.2. Methods ground to about 2 lm in an agate mortar, then placed into a
250 mL conical flask with 100 mL of 1.0 g/L chitosan solution.
2.2.1. Flotation The suspension was adjusted to pH 6 with HCl or NaOH and was
The flowsheet of the coppermolybdenum ore bulk flotation shaken in the shaking incubator for 30 min. The treated mineral
test is described in Fig. 2. Six hundred grams 2 mm ore was solids were then filtered and washed three times with deionized
ground to 70% 74 lm in a U160 180 mm ball mill. The bulk water. The Fourier transform infrared (FTIR) spectra of chitosan,
flotation tests were conducted in a XFD flotation cell, with cell untreated and treated minerals were collected by a Bruker Alpha
volumes of 1500 mL for rougher flotation and 500 mL for cleaner (Thermo, USA) FTIR spectrophotometer.
flotation.
The flotation tests on single minerals and molybdenum-bearing 2.2.4. ToF-SIMS measurements
copper concentrate were carried out using a model XGF-1600 flota- ToF-SIMS are widely used to study the surface chemical of min-
tion machine operating at 1600 rpm with a 30 mL suspension cell. erals subjected to flotation separation (Chehreh Chelgani and Hart,
In a typical test, the mineral slurry was prepared by adding 2 g of a 2014). The ToF-SIMS measurements of the chalcopyritemolybde
single mineral or molybdenum-bearing copper concentrate to nite mixture treated with chitosan were conducted by a ToF-
30 mL of distilled water. The slurry pH was modified to the desired SIMS IV spectrometer at the Alberta Center for Surface Engineering
value by adding either HCl or NaOH solutions. The reagents and Science (ACSES). A high energy beam of Bi+ ions (25 kV) was
(chitosan, kerosene and terpenic oil) were added in sequence and focused on a sample area of 64 lm 64 lm and H+, CH 3 and Na
+
conditioned for 2 min each. The conditioned slurry was floated ions were used as the secondary ion peaks to obtain the positive
for a total of 5 min. Both the froth and tailings products were spectra which is a function of mass. Images were generated by
collected and dried. In single mineral flotation, the recovery was the way described in detail by Huang et al. (2012a). The sample
obtained from the solid weight distribution between froth and was prepared by adding 1.5 g chalcopyrite and 0.5 g molybdenite
M. Li et al. / Minerals Engineering 83 (2015) 217222 219
Recovery/%
60
3.1. Flotation of single minerals
40
Recoveries of molybdenite and chalcopyrite in single mineral
flotation tests with and without chitosan as a depressant at a range
of pH values (412) is presented in Fig. 3. As shown in Fig. 3, both
20
molybdenite and chalcopyrite show high floatability with a high
recovery of more than 85% and 70%, respectively, in the tested
pH range in the absence of chitosan. The recoveries of chalcopyrite
and molybdenite showed the same tendency, i.e., that recoveries 0 2 4 6 8 10
increased in the pH range of 48 but decreased gradually when Concentration/ mg L
-1
60 Molybdenite with CTS plotted in Fig. 6. As shown in Fig. 6 the recovery of copper
Chalcopyrite decreased from 55% to 9% and molybdenum from 80% to 55% as
Molybdenite the chitosan concentration increased from 0.9 mg/L to 8.7 mg/L.
40 It is necessary to note that both the recoveries of copper and
molybdenum and the recovery differences were higher than those
in single mineral flotation (Fig. 4). Fig. 6 also shows that similar
20 recoveries of copper and molybdenum are obtained when
conventional depressant sodium sulfide is used at pH 8 and
concentration 400 mg/L while the concentration of chitosan is
0 6.5 mg/L. The results of molybdenum-bearing copper concentrate
2 4 6 8 10 12 14
flotation show that chitosan is possible to be used as a selective
pH
depressant in coppermolybdenum separation and it is non-
Fig. 3. Flotation of single minerals of chalcopyrite and molybdenite as a function of toxic and less dosage than conventional depressant sodium
pH by kerosene (8.3 mg/L) with or without chitosan (6.5 mg/L). sulfide.
220 M. Li et al. / Minerals Engineering 83 (2015) 217222
100
Copper in froth (a) 2.0
Molybdenum in froth
Adsorption density/(mg m )
80
-2
1.6
Recovery/%
60 1.2
40 0.8
20 0.4 Chalcopyrite
Molybdenite
0
2 4 6 8 10 12 14 0 5 10 15 20 25 30 35 40 45 50
-1
pH Concentration/(mg L )
Fig. 5. Flotation of molybdenum-bearing copper concentrate as a function of pH by
kerosene (8.3 mg/L) and chitosan (6.5 mg/L). (b) 1.0
Adsorption density/(mgm )
-2
-1 0.8
Concentration of sodium sulfide/(mg L )
150 200 250 300 350 400 450 500
100 0.6
80
0.4
Recovery/%
60
0.2 Chalcopyrite
Molybdenite
40
0 10 20 30 40 50 60
-1
Concentration/(mg L )
20
Fig. 7. Adsorption density of reagents on chalcopyrite and molybdenite as a
function of concentration at pH 6. (a) depressant chitosan; (b) collector xanthate.
0 2 4 6 8 10
-1
Concentration of chitosan/(mg L )
Copper in froth with chitosan copper concentrate flotation (Fig. 6) than that in single mineral
Molybdenum in froth with chitosan flotation (Fig. 4). Secondly, the adsorption density of xanthate on
Copper in froth with sodlium sulfide molybdenite was higher than that on chalcopyrite. In other words,
Molybdenum in froth with sodium sulfide the surface coverage of molybdenite by xanthate was higher than
Fig. 6. Flotation of molybdenum-bearing copper concentrate as a function of
that of chalcopyrite. The pre-adsorbed xanthate hindered the
chitosan concentration at pH 6 and sodium sulfide concentration at pH 8 by adsorption of chitosan on molybdenite and chalcopyrite. Therefore,
kerosene (8.3 mg/L). the different surface coverage of the molybdenite and chalcopyrite
in molybdenum-bearing copper concentrate may contribute to the
larger differences in molybdenum and copper recoveries from the
3.3. Adsorption of chitosan and xanthate on minerals molybdenum-bearing copper concentrate than from the single
minerals.
The adsorption densities of chitosan and xanthate on single
mineral (chalcopyrite and molybdenite) surfaces as a function of
reagent concentration are shown in Fig. 7a and b respectively. 3.4. FTIR spectra of chalcopyrite and molybdenite treated with
The results in Fig. 7a indicated that adsorption densities of chitosan chitosan
on chalcopyrite and molybdenite increased simultaneously with
the increase of chitosan concentration, and the adsorption density The FTIR spectra of chalcopyrite and molybdenite before and
of chitosan on molybdenite was slightly lower than that on chal- after treatment with chitosan are presented in Figs. 8 and 9,
copyrite which was in agreement with the result of single mineral respectively, together with the spectrum of chitosan, in the spec-
flotation in Fig. 4 where less molybdenite was depressed than chal- tral range of 17001000 cm1. In the spectrum of chitosan, the
copyrite by chitosan. bands at 1655 cm1, 1582 cm1, 1551 cm1 and 1317 cm1 were
As can be seen from Fig. 7b, xanthate adsorbed on both due to C@O stretching (amide I), NAH deformation vibration
molybdenite and chalcopyrite. The residual xanthate from cop- (amine II), NAH in plane deformation (amine III) and CAN stretch-
permolybdenum bulk flotation on molybdenum-bearing copper ing (amine IV) of acetyl groups in chitosan molecules, respectively,
concentrate (molybdenite and chalcopyrite) may lead to higher which were in agreement with previous reports (Amaral et al.,
recoveries of copper and molybdenum in molybdenum-bearing 2005; Huang et al., 2012b; Lawrie et al., 2007; Muzzarelli, 1973).
M. Li et al. / Minerals Engineering 83 (2015) 217222 221
Fig. 10. Positive-ion images of the surface of chalcopyritemolybdenite mixtures (weight ratio 3:1) treated with 6 mg/L chitosan. (a) Image of chalcopyrite (Cu+); (b) Image of
molybdenite (Mo+); (c) Image of chitosan (CH4N+).
222 M. Li et al. / Minerals Engineering 83 (2015) 217222
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