Flotacija Oksida Bakra
Flotacija Oksida Bakra
Flotacija Oksida Bakra
a r t i c l e i n f o a b s t r a c t
Article history: Copper oxide minerals are important copper resources, which include malachite, azurite, chrysocolla,
Received 26 December 2021 cuprite, etc. Flotation is the most widely used method for the enrichment of copper oxide minerals in
Received in revised form 21 September the mineral processing industry. In this paper, the surface properties of copper oxide minerals and their
2022
effects on the mineral flotation behavior are systematically summarized. The flotation methods of copper
Accepted 28 September 2022
Available online xxxx
oxide minerals and the interaction mechanism with reagents are reviewed in detail. Flotation methods
include direct flotation (using chelating reagents or a fatty acid as collector), sulfidization flotation (using
xanthate as collector), and activation flotation (using chelating reagents, ammonium/amine salts, metal
Keywords:
Copper oxide minerals
ions, and oxidant for activation). An effective way to realize efficient flotation of copper oxide minerals is
Direct flotation to increase active sites on the surface of copper oxide minerals to enhance the interaction of collector
Sulfidization flotation with the mineral surface. Besides, various perspectives for further investigation on the efficient recovery
Activation flotation of copper oxide minerals are proposed.
Ó 2022 Published by Elsevier B.V. on behalf of China University of Mining & Technology. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2. Surface properties of copper oxide minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3. Flotation methods for copper oxide minerals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.1. Direct flotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.2. Sulfidization flotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4. Activation flotation of copper oxide minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.1. Application of chelating reagents in activation flotation of copper oxide minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.2. Application of ammonium/amine salts in activation flotation of copper oxide minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.3. Effect of metal ions on copper oxide mineral flotation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.4. Application of pre-oxidation in activation flotation of copper oxide minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
5. Summary and prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
1. Introduction
https://doi.org/10.1016/j.ijmst.2022.09.011
2095-2686/Ó 2022 Published by Elsevier B.V. on behalf of China University of Mining & Technology.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Please cite this article as: Q. Feng, W. Yang, S. Wen et al., Flotation of copper oxide minerals: A review, International Journal of Mining Science and Tech-
nology, https://doi.org/10.1016/j.ijmst.2022.09.011
Q. Feng, W. Yang, S. Wen et al. International Journal of Mining Science and Technology xxx (xxxx) xxx
oxide mineral resources have attracted attention [3]. Copper oxide 2. Surface properties of copper oxide minerals
deposits evolve from shallow copper sulfide deposits after long-
term oxidation, and they are widely and abundantly distributed The fresh copper oxide mineral surfaces exposed during crush-
in reserves all over the world [4–7]. However, copper oxide ores ing and grinding have a significant effect on subsequent flotation
tend to have the characteristics of strong surface hydrophilicity, [23–26]. Many dangling bonds exist on fresh mineral surfaces
high combination rate, fine particle size, serious mud problems, because of destruction of the original lattice bonds, and the copper
and complex mineral composition [8,9]. Therefore, it is difficult oxide mineral surface often shows strong polarity because of the
to recover copper oxide resources efficiently by conventional cop- existence of ionic bonds. It is easy for a thick near-mineral hydra-
per sulfide ore separation method. tion shell to form on the mineral surface, which enhances the sur-
Malachite is the most common copper oxide mineral with the face hydrophilicity. Accordingly, it is difficult for the collector to
largest reserves. It is often associated with copper-bearing miner- interact with the copper oxide mineral surface owing to the pres-
als, such as chalcocite and azurite. The chemical formula of mala- ence of a hydration shell [27]. Therefore, to realize efficient flota-
chite is Cu2(OH)2CO3, and its theoretical copper mass fraction is tion recovery of copper oxide minerals, it is of great importance
57.57%. Malachite crystals belong to the monoclinic system, and to investigate the effect of the surface properties of copper oxide
the malachite crystal types are mostly columnar, acicular, and minerals on flotation. The surface properties of copper oxide min-
fibrous [10]. The copper species in the malachite crystal structure erals are given in Table 1.
are Cu(I) and Cu(II). The coordination number of Cu is four; Cu(I) The malachite surface has high electronegativity, and water
is surrounded by 2 OH and 4 O2 groups, and Cu(II) is surrounded molecules in aqueous solution easily adsorb on the malachite sur-
by 4 OH and 2 O2 groups [11]. faces by polarization to generate a stable near-mineral hydration
Chrysocolla is a copper oxide mineral with a complex structure, shell, so it shows high hydrophilicity [41]. The malachite surface
and it is characterized by multiphase inhomogeneity and multiple has good solubility and its mineral/solution interface is unstable.
micropores. The ideal molecular model of the chrysocolla unit cell This leads to unstable collector adsorption on and collector desorp-
is shown in Fig. 1 [12]. However, isomorphism exists in the molec- tion from the malachite surface during flotation. Malachite shows
ular structure of chrysocolla because of impurity-atom doping, different dissolution characteristics for different pulp pH ranges.
resulting in chrysocolla not having a fixed chemical formula. Thus, Under acidic conditions, the malachite surfaces are dominated by
chrysocolla is generally described as a mixture of crystalline cop- copper ions, whereas under alkaline conditions, the malachite sur-
per silicate and amorphous silicon dioxide. A microcrystalline faces are dominated by copper-hydroxyl species. Thus, the flota-
structure for chrysocolla has been proposed [13]. Chukhrov et al. tion behavior of malachite can be changed by adjusting the pulp
[14] introduced the concept of a copper silicate crystalline grain. pH [42]. Malachite forms interlayer structures through weak inter-
The chemical formula of chrysocolla is (Cu2 xAlx)H2 xSi2O5(OH)4- molecular forces. Its structural stability is poor, which results in
nH2O, and the copper species in chrysocolla exist in two states. unstable xanthate adsorption on the malachite surface [43–45].
Copper hydroxide and copper silicate contribute to the copper spe- After addition of a sulfidizing reagent, the malachite interlayer
cies in chrysocolla, so chrysocolla shows the dual properties of structure can be connected by Cu-S chemical bonds, the malachite
these compounds. structure stabilizes, and the activity and stability of the copper
Cuprite is usually associated with malachite and chrysocolla. Its atoms on the mineral surface are enhanced (Fig. 2) [46].
chemical formula is Cu2O, and its theoretical copper content is The surface structure of chrysocolla has obvious porous charac-
88.82%. The main metallogenic origin of cuprite is volcanic sedi- teristics, and thus it has a large specific surface area [47]. There are
mentary mineralization. During mineralization, because of the lack many pores on the chrysocolla surface at multiple sites, and it is
of oxygen, the degree of oxidation is insufficient, and cuprite con- difficult for a collector to cover the chrysocolla surface effectively
tains cuprous species. After further oxidation in air, cuprite can
transform to tenorite, so cuprite may exhibit some of the proper-
ties of tenorite in industrial treatment.
Table 1
Representative surface properties of copper oxide minerals.
2
Q. Feng, W. Yang, S. Wen et al. International Journal of Mining Science and Technology xxx (xxxx) xxx
on Eh, but not on the pH. With an increase in the sodium sulfide
dosage, the flotation recovery of cuprite is basically zero at a low
Eh ( 420 mV). The flotation behavior and electrochemical proper-
ties of cuprite can mimic those of chalcocite by controlling pre-
sulfidization of the cuprite surface. Nagaraj et al. [61] obtained a
similar conclusion that the surface properties of sulfidized cuprite
are more like those of chalcocite or digenite than those of
chalcopyrite.
In summary, the surfaces of malachite, chrysocolla, and cuprite
all show high hydrophilicity, and thus they are not predisposed to
float. Malachite has an obvious interlayer structure, and interca-
lated sulfidization occurs during sulfidization, which favors collec-
tion by xanthate. The chrysocolla surface is porous, which is
unfavorable for collector adsorption, and it shows flotation charac-
teristics like those of quartz under alkaline conditions, which
Fig. 3. Slab model of a supercell (221) of the cuprite (1 1 1) surface after
geometry optimization [52]. increases the difficulty of chrysocolla flotation. Fewer free active
copper ions exist on the cuprite surface than on the malachite
and chrysocolla surfaces. Dialkyl dithiophosphates can only form
because of its large specific surface area and porous characteristics a single adsorption layer on the cuprite surface, and the critical fac-
[36]. The surface chemical properties of chrysocolla are mainly tor in its flotation behavior can be changed by sulfidization.
controlled by the free copper ions and silica species on the mineral Because malachite, chrysocolla, and cuprite can form a near-
surface. By changing the pH, the predominant chrysocolla surface mineral hydration shell, it is necessary to add a collector or a reg-
species change accordingly [48]. Under acidic and neutral condi- ulator to modify the mineral surface and achieve hydrophobic
tions, many Cu2+ and CuOH+ species exist on the chrysocolla sur- flotation of these copper oxide minerals.
face, and the chrysocolla surface exhibits properties like that of a
quartz surface in the presence of copper ions. Under alkaline con-
dition, the dominant species on the chrysocolla surface are H3Si2O4 3. Flotation methods for copper oxide minerals
and H2SiO3 , and the chrysocolla surface properties are like those of
a quartz surface [38,48]. The quartz surface is strongly hydrophilic, The flotation methods for copper oxide minerals mainly include
and it does not float under the action of xanthate and fatty-acid direct flotation and sulfidization flotation [62]. Direct flotation
collectors. Cationic amine collectors or anionic collectors are often refers to mineral flotation by direct addition of collectors and a
used for quartz flotation, in which the use of an anionic collector frother to the flotation process without the use of activators. Sul-
requires pre-activation with polyvalent metal ions [49–51]. There- fidization flotation refers to addition of a sulfidizing reagent before
fore, compared with malachite, chrysocolla usually shows poor addition of a collector to change the properties of the mineral sur-
floatability under the same flotation conditions. faces. Through sulfidization, a copper sulfide film with high activity
A slab model of a supercell of the cuprite (1 1 1) surface after is generated on the copper oxide mineral surface. Thus, xanthate
collectors with better selectivity are more likely to interact with
geometry optimization is shown in Fig. 3 [52]. The cuprite surface
is composed of cuprous species and oxygen species, and the copper the sulfidized mineral surface, and the problem of the poor selec-
tivity in direct flotation can be resolved.
atomic concentration on the cuprite surface is higher than those of
malachite and chrysocolla. However, the cuprous species on the
cuprite surface have a weaker affinity for sulfide ions than the cup- 3.1. Direct flotation
ric species on malachite and chrysocolla surfaces, which makes it
difficult to sulfidize the cuprite surface sufficiently [53]. In addi- The broken bonds on copper oxide mineral surfaces, such as
tion, the surface solubility of cuprite is lower than those of mala- malachite, are mainly ionic and have strong hydrophilicity, which
chite and chrysocolla, and thus the concentration of free copper makes it difficult for xanthate collectors to be used directly in flota-
ions on the cuprite surfaces is lower, which could change the flota- tion of copper oxide minerals [5]. Therefore, the main direct flota-
tion behavior of cuprite. The surface dissolution behavior changes tion methods for copper oxides are chelating-reagent flotation and
the crystal and surface chemistry of the mineral, and the solution fatty-acid flotation. The chelating collector for copper oxide miner-
chemistry changes as dissolved ions enter the solution [54]. For als usually has strong collecting ability. The copper and hydroxyl-
cuprite, the surface-dissolution process may be advantageous copper species on the copper oxide mineral surface can directly
because it promotes cuprous-to-cupric ion conversion, which acti- form a ring compound with the functional group of the chelating
vates cuprite flotation. A similar activation mechanism has been reagent through covalent and coordination bonding, and thus the
demonstrated in ilmenite flotation studies [55–57]. Buckley et al. chelating reagent can adsorb on the mineral surface [63–65]. For
[58,59] studied the flotation behavior of cuprite under the action mixed oxide-sulfide copper ores, the chelating collector can
of dialkyl dithiophosphates. They found that chemisorption of dia- achieve simultaneous flotation of copper oxide and copper sulfide
lkyl dithiophosphates on the cuprite surface is like that on chal- minerals. However, the limitation of chelating collectors is their
cocite. The difference is that dialkyl dithiophosphates can adsorb lack of selectivity, and they also adsorb to gangue minerals [66].
on the chalcocite surface in multiple layers, whereas dialkyl dithio- Compared with chelating collectors, fatty-acid collectors, such as
phosphates only exist in a single layer on the cuprite surface. The sodium oleate, have obvious cost advantages because of their wide
surface properties of cuprite are easily affected by sulfidization, range of raw materials and easy preparation [67].
and the flotation behavior of cuprite is less affected by a change Hydroxamic acid and its derivatives are often used as collectors
in the redox potential (Eh) before sulfidization, but it is easily for direct flotation of copper oxide minerals [68,69]. Hydroxamic
affected by the pH [60]. When the pulp potential is close to zero, acid can interact with mineral surfaces in two ways: chemical
cuprite can be collected by xanthate only under alkaline condi- adsorption and surface reaction [70]. Hydroxamic acid directly
tions. After sulfidization, the degree of interaction between xan- covalently bonds with metal cations on mineral surfaces by chem-
thate and the cuprite surface in a reducing environment depends ical adsorption to form metal chelates. The metal cations from the
3
Q. Feng, W. Yang, S. Wen et al. International Journal of Mining Science and Technology xxx (xxxx) xxx
Fig. 4. Flotation recovery of malachite and quartz at pH 6, 8, and 9 using benzohydroxamic acid as the collector [33].
Fig. 6. Bonding model of styryl phosphonate mono-isooctyl ester (SPE108) with the
malachite surface cations [29].
4
Q. Feng, W. Yang, S. Wen et al. International Journal of Mining Science and Technology xxx (xxxx) xxx
Fig. 8. Schematic mechanism of co-adsorption of sodium oleate and alcohol on the malachite surface [28].
5
Q. Feng, W. Yang, S. Wen et al. International Journal of Mining Science and Technology xxx (xxxx) xxx
shell and adsorb on the mineral surface. The sulfide film that is
formed on the mineral surface creates new active centers for xan-
thate adsorption after sulfide ions destroy the hydration shell on
the mineral surface. The active sulfidization products on the mala-
chite surface exist in various forms, including CuS, CuS2, and CuSn
(Fig. 9). An increase in the amount of CuSn species in the distribu-
tion of copper sulfide species may enhance malachite sulfidization,
and the content of highly active CuSn species on the malachite sur-
face can be selectively increased by regulating the sulfidization
process conditions [76–78].
The exposed metal ions on the mineral surface tend to interact
with the anions in the functional group of the flotation reagent that
have a strong bonding ability with the metal ions in the mineral
lattice, that is, the anion functional group in the flotation reagent
compensates for the unsaturated metal ions on the mineral surface
[79]. This explains the excellent selectivity of surface sulfidization–
xanthate flotation in treatment of copper oxide minerals. During
the sulfidization process of copper oxide minerals, the sulfidization
Fig. 11. Distribution coefficients of various S species in Na2S solution as a function
results can be affected by many factors, such as the type of sulfidiz-
of the pH [89].
ing reagent, structural characteristics of the mineral surface,
sulfidizing-reagent dosage, sulfidization time, pulp Eh, pulp pH,
sulfidization temperature, unavoidable ions, stirring method, and face gaps. Sulfidizing-reagent adsorption is unstable, which makes
speed [80–84]. The specific effects of these factors on sulfidization it more difficult for chrysocolla to be sulfidized than malachite
are as follows. [36]. The lack of active metal ions on the chrysocolla surface that
(1) Type of sulfidizing reagent. Sodium sulfide, ammonium sul- can interact with sulfide ions results in difficulty in sufficiently sul-
fide, sodium hydrosulfide, and sodium polysulfide are common fidizing the chrysocolla surface.
sulfidizing reagents in sulfidization flotation [5,80,85]. Zhou et al. (3) Dosage of the sulfidizing reagent. By adjusting the dosage,
[80] compared the mechanisms of sodium sulfide and disodium the sulfidizing reagent can activate or depress copper oxide min-
tetrasulfide in malachite flotation. Surface analysis showed that eral flotation. It is difficult to generate sufficient copper sulfide spe-
after the interaction of sodium sulfide with the malachite surface, cies on the mineral surface using insufficient sulfidizing reagent,
the main component of the sulfide film is CuS, whereas a mixture which results in a low degree of sulfidization. However, copper
of CuS4 and S0 is generated after the interaction between disodium oxide mineral flotation is depressed using excessive sulfidizing
tetrasulfide and the malachite surface. The sodium sulfide residue reagent due to the competitive adsorption between the collector
on the malachite surface shows a stronger tendency to transform and excessive sulfide ions on the mineral surface (Fig. 10) [85].
to thiosulfate and sulfate than disodium tetrasulfide. Therefore, (4) Sulfidization time. The sulfidization time affects the cover-
disodium tetrasulfide gives better sulfidization results than age and intensity of the sulfide film on the mineral surface. If the
sodium sulfide. However, sodium sulfide is the most common sul- sulfidization time is too short, the sulfidization degree of the min-
fidizing reagent, and it is widely used in industrial production eral surface is insufficient. If the sulfidization time is too long, the
based on cost considerations. activation effect of the sodium sulfide decreases and the sulfide
(2) Structural characteristics of the mineral surface. Chrysocolla, products on the mineral surface may fall off, transfer to the liquid
for example, has a heterogeneous surface, and its surface proper- phase, and depress mineral flotation [86,87].
ties are like those of quartz under alkaline conditions, which is (5) Pulp Eh. Sulfidization and xanthate adsorption are sensitive
unfavorable for interaction of sodium sulfide with the mineral sur- to the pulp Eh because the interaction between the sulfide ions
face [38]. Chrysocolla has a unique multi-microporous structure, and xanthate collector on the mineral surface is performed by
and the sulfidizing reagent can only adsorb in the chrysocolla sur- oxidation-reduction. The sulfidizing reagent is rapidly oxidized
when the pulp potential is too high, which results in sulfidizing-
reagent consumption. When the pulp potential is too low, it is dif-
ficult for xanthate to be oxidized to dixanthogen on the mineral
surface, which leads to a decrease in the mineral flotation recovery.
It has been proposed that on oxidized chalcopyrite, chalcocite-like
species form at 165 mV and covellite-like species form
at 315 mV (vs the standard hydrogen electrode) [88].
(6) Pulp pH. Sodium sulfide first ionizes to S2 in solution, and
then S2 can produce HS and H2S by hydrolysis. Thus, sodium sul-
fide exists in the form of various sulfide species in solution. In
malachite sulfidization flotation tests, malachite is better sul-
fidized and floats at pH 8–10. The dominant species of sodium sul-
fide in this pH range in the pulp is HS (Fig. 11) [76,89]. Under
acidic conditions, xanthates decompose, and malachite shows poor
floatability [90]. When the pH is in the range of 8–10, HS can
strongly interact with the malachite surface, thereby obtaining
an efficiently sulfidized malachite surface. When the pH is higher
than 10, numerous hydroxide anions exist in the pulp, which can
competitively adsorb with xanthate anions on the malachite sur-
Fig. 10. Floatability of malachite sulfidized with different amounts of Na2S and face, thus decreasing the flotation recovery of malachite. Similar
(NH4)2S at different potassium amyl xanthate concentrations [85].
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Q. Feng, W. Yang, S. Wen et al. International Journal of Mining Science and Technology xxx (xxxx) xxx
to the flotation results of malachite, chrysocolla and cuprite show other mud depressants is required to prevent gangue mineral flota-
good floatability at pH 9 and 9.5, respectively [91,92]. tion [98]. However, sodium silicate and sodium hexametaphos-
(7) Sulfidization temperature. In sulfidization of oxide minerals, phate have an obvious depressive effect on malachite. For copper
an increase in the sulfidization temperature increases the sulfidiza- minerals that have a close symbiotic relationship with gangue
tion degree and efficiency [93]. This may be because increasing the minerals, depressants, such as sodium silicate, make it difficult
temperature increases the Brownian motion of the reagent mole- for locked minerals that contain copper to be floated, which results
cules, which improves the dispersion state of the reagent in the in partial copper resource loss in the tailings. For copper oxide ores
pulp and increase the probability of collision between the mineral that contain weak magnetic copper-bearing minerals, such as
particles and reagent molecules, thus promoting adsorption of the libethenite, and copper-bearing limonite, after sulfidization flota-
reagent on the mineral surface [94]. However, heating sulfidation tion, the flotation tailings can be reseparated by high-gradient
flotation may result in increases of equipment maintenance, pro- magnetic separation. The magnetic separation concentrate can
duction costs, and environmental issues. then be obtained through simple acid leaching to recover the cop-
(8) Unavoidable ions. The unavoidable ions in sulfidization per minerals and improve the copper oxide mineral recovery
flotation of copper oxide minerals mainly originate from dissolu- [99,100].
tion of copper oxide and gangue minerals, depletion of the grinding Sulfidization flotation has wide adaptability to copper oxide
medium, and the flotation water. The unavoidable metal ions can ores. However, direct sulfidization also has some shortcomings
adsorb on the mineral surface by chemical or physical adsorption, during actual production, such as a low sulfidization efficiency,
which affects the floatability of copper oxide minerals. Adsorption poor sulfidization results, and a large dosage of sulfidizing
of specific metal ions, such as Pb2+ and Cu2+, can increase the num- reagents. These shortcomings make it difficult to guarantee effec-
ber of active sites that are conducive to adsorption of subsequent tive recovery of refractory copper oxide minerals, such as chryso-
sulfide ions or collectors, which has a positive effect on mineral colla and cuprite. An increase in the sulfidizing-reagent dosage
flotation [95,96]. This is because the lead-bearing species formed does not give ideal flotation results. An increase in the dosage does
after interaction between Pb2+ and the mineral surface can react not generate sufficient metal sulfide species on the mineral surface,
with sulfide ions to generate lead sulfide species with high activity but it increases the residual sulfide species in the pulp, and it gen-
and low solubility, enhancing adsorption of the collector on the erates black copper sulfide precipitates in the pulp that are not
mineral surface. conducive to flotation. These behaviors lead to copper oxide min-
(9) Concentration of dissolved oxygen. During sulfidization, stir- eral flotation depression. For direct sulfidization flotation of
ring with or without aeration gives different sulfidization results. If chrysocolla (pH=9.0), only a low dosage of sodium sulfide
the oxygen content in the pulp increases, which changes the pulp (110 4 mol/L) needs to be added to activate chrysocolla
potential and accelerates sulfide-ion oxidation, the effective sulfide (Fig. 12) [91]. This could be because the chrysocolla surface has
concentration in the pulp decreases. similar surface properties to quartz, and there are insufficient
For mixed oxide-sulfide copper minerals, xanthate can be active sites on the chrysocolla surface that can interact with sulfide
directly used to recover copper sulfide minerals. Sulfidization–xan- ions, thereby leading to excess sulfide ions in the pulp. The residual
thate flotation can then be used to extract the copper oxide miner- sulfide species in the pulp consume free oxygen, which makes it
als in the tailings of the copper sulfide minerals to meet the difficult for xanthate to interact with the chrysocolla surface, and
flotation requirements of copper minerals with different floatabil- excess sodium sulfide leads to irreversible chrysocolla floatability
ities [97]. According to the characteristics of mixed oxide-sulfide [101].
copper minerals from different production areas, bulk flotation of From the perspective of the solution chemistry, excessive sul-
mixed oxide-sulfide copper minerals after sulfidization is also fide species in the pulp compete with xanthate for adsorption on
commonly based on consideration of a stable flotation index and the mineral surface, which makes it difficult for the collector to
convenient operation. Because copper oxide ores usually contain interact with the mineral surface. Excessive sulfidizing reagents
excessive mud, problematic mud circulation and accumulation decrease the mineral/solution interface potential, which is not con-
occurs during flotation. It is difficult for sulfidization flotation to ducive to hydrophobic metal xanthate formation on the mineral
overcome the problems of a mud layer on the mineral surface, surface. From an electrochemistry perspective, compared with
and addition of sodium silicate, sodium hexametaphosphate, and xanthate, sodium sulfide has oxidation–reduction ability at a lower
potential on the mineral surface. This hinders xanthate oxidation
on the mineral surface, and it makes it difficult for xanthate to
interact with the sulfidized surface of copper oxide minerals with
excess sodium sulfide. Therefore, an approach to achieve sufficient
copper oxide mineral sulfidization is to increase the number of
active sites that are conducive to sulfidization, so that sufficient
Table 2
Effective collectors for copper oxide mineral flotation.
Type Name
Xanthate Butyl xanthate [32]
Amyl xanthate [85]
Isoamyl xanthate [102–104]
Chelating reagent Benzohydroxamic acid [33]
Octyl Hydroxamic acid [41]
a-hydroxyoctyl phosphinic acid [35]
2-ethyl-2-hexenal oxime [72]
3-hexyl-4-amino-1,2,4-triazole-5-thione [31]
S-carboxymethyl-O, O’-dibutyldithiophosphate [34,73]
Styryl phosphonate mono-isooctyl ester [29]
Fatty acid Sodium oleate [28,67]
Fig. 12. Chrysocolla flotation recovery as a function of the Na2S dosage and pH [91].
7
Q. Feng, W. Yang, S. Wen et al. International Journal of Mining Science and Technology xxx (xxxx) xxx
and highly active sulfide species are generated on the mineral recovery of the copper concentrate [108]. 1H-Benzotriazole has
surface. an activation effect on sulfidization flotation of copper oxide min-
Effective collectors for direct flotation and sulfidization flotation erals. The possible activation mechanism is that adsorption of 1H-
of copper oxide minerals are listed in Table 2. benzotriazole enhances the surface stability of copper oxide miner-
als, which provides favorable circumstances for adsorption of sul-
fide ions and xanthate [109].
4. Activation flotation of copper oxide minerals
In summary, chelating reagents can activate flotation of copper
oxide minerals in a variety of ways, including by enhancing the
Direct sulfidization flotation of copper oxide minerals has the
mineral surface hydrophobicity and increasing the number of
disadvantage of poor sulfidization degree. Specific chelating
active sites that are conducive to adsorption of subsequent sulfide
reagents, ammonium/amine salts, metal ions, and pre-oxidation
ions and collectors on the mineral surface. Chelating reagents can
can increase the number of active sites on the mineral surface
adsorb on surface areas of copper oxide minerals that are not suf-
and enhance subsequent sulfide-ion and collector adsorption.
ficiently sulfidized and play an auxiliary role to xanthate.
Therefore, sulfidization of copper oxide minerals can be enhanced
by adding specific activators to achieve efficient hydrophobic flota-
tion of copper oxide minerals.
4.2. Application of ammonium/amine salts in activation flotation of
copper oxide minerals
4.1. Application of chelating reagents in activation flotation of copper
oxide minerals Addition of an appropriate amount of ammonium/amine salt in
sulfidization flotation of copper oxide mineral can improve the sul-
The purpose of using a chelating reagent as a copper oxide min- fidization environment, sufficiently sulfidize the copper oxide min-
eral flotation activator is to increase the number of active sites on eral surface, and activate sulfidization flotation of copper oxide
the mineral surface that are favorable for sulfide-ion and collector minerals. Ammonium/amine salt adsorption can increase the num-
adsorption and to enhance the mineral surface hydrophobicity. The ber of active sites on the copper oxide mineral surface and enhance
chelating reagent can interact with metal ions from the copper subsequent sulfidization. In addition, ammonium salt can act as a
oxide mineral surface and form insoluble hydrophobic chelates. buffer in the pulp to eliminate the adverse effects of excessive sul-
This initially enhances the mineral surface hydrophobicity, creates fide ions on copper oxide mineral flotation [110,111].
favorable conditions for the subsequent action of the sulfide ion The combination of ammonium salt and sodium sulfide has
and collector on the copper oxide mineral surface, and thus acti- been widely used in copper oxide mineral flotation. Ammonium
vates copper oxide mineral flotation. salt is an accelerant in sulfidization of copper oxide minerals, and
The chelating reagents and copper oxide minerals are sensitive it can work in three ways: catalyzing sulfidization, enhancing the
to changes in the pH, possibly because the surface solubility of cop- mineral surface hydrophobicity, and stabilizing the sulfide film
per oxide minerals and the chemical activity of the chelating and xanthate adsorption [112]. The residual ion test shows that
reagent change in different pH ranges. Triethanolamine can hinder the ammonium salt is not visibly consumed during sulfidization.
colloidal copper sulfide and copper xanthate formation in solution, Thus, the ammonium salt may not enhance sulfidization by exist-
improve the sulfide-ion interaction with the malachite surface, and ing in the copper oxide mineral surface, but it may act as a ‘‘cata-
improve the xanthate-adsorption capacity and stability on the lyst” to activate sulfidization flotation of copper oxide minerals
malachite surface [105]. Triethanolamine can activate malachite [113]. Using ammonium sulfate as a sulfidization accelerator can
flotation in the existence of excessive sodium sulfide, and the flota- activate malachite flotation, and the depression caused by excess
tion behavior of malachite is not significantly affected by excessive sodium sulfide is weakened in the presence of ammonium sulfate.
sodium sulfide. X-ray photoelectron spectroscopy analysis shows that in the pres-
a-Benzoin oxime, anthranilic acid, cupferron, N-benzoyl-N- ence of excess sodium sulfide, ammonium sulphate weakens the
phenylhydroxylamine, and 8-hydroxyquinoline have an activation depression caused by colloidal copper sulfide in the pulp, the num-
effect on chrysocolla flotation, and they show the best activation ber of active sulfide species on the malachite surface increases, and
ability under weakly acidic conditions [12,106]. Under acidic con- the copper sulfide film on the malachite surface is more compact
ditions (pH<5), the copper ions on the chrysocolla surface tend to and stable. In addition, nitrogen-containing species are not
be released into the pulp and hardly adsorb on the mineral surface. detected on the malachite surface; thus, ammonium sulfate inter-
Conversely, under weakly acidic conditions (pH 5–6), the dissolved acts with the malachite surface in a transition state during sul-
copper ions can adsorb on the chrysocolla surface as Cu(OH)+, fidization flotation of malachite [114]. (NH4)2SO4 has a
which increases the concentration of active copper ions on the dissolution effect on the malachite surface, leading to formation
chrysocolla surface. Surface element analysis and adsorption mea- of lattice imperfections on its surface that provide the conditions
surements show that 8-hydroxyquinoline and xanthate exist on necessary for re-combination of the mineral lattice when sulfide
the chrysocolla surface by co-adsorption, and the presence of 8- ions are subsequently added to the system. Some of the sulfur ions
hydroxyquinoline improves the xanthate adsorption capacity on that should form colloidal copper sulfide are transferred to the
the chrysocolla surface, which enhances the chrysocolla hydropho- malachite surface and form a hydrophobic copper sulfide film
bicity. 2,5-Dithiol-1,3,4-thiodiazole activates sulfidization flotation (Fig. 13). A similar phenomenon has been observed in sulfidization
of copper oxide minerals, and the grade and recovery of the copper flotation of chrysocolla activated by ammonium salt. Ammonium-
concentrate are improved while the sodium-sulfide dosage is phosphate addition facilitates generation of stable crystalline cop-
reduced [107]. The pulp pH is more stable and easier to control per sulfide species on the chrysocolla surface [91]. Newly formed
using 2,5-dithiol-1,3,4-thiodiazole as an activator, which ensures copper sulfide crystals fragments are generated on the surface of
effective recovery of gold, silver, and other associated precious chrysocolla after treatment with ammonium phosphate before sul-
metals. For copper ores with oxidation rates of up to 94%, flotation fidization. However, no obvious nitrogen- or phosphorus-
tests have been performed by sulfidization-xanthate flotation, 2,5- containing species are detected on the chrysocolla surface, which
dithiol-1,3,4-thiodiazole flotation, and sulfidization-2,5-dithiol- indicates that ammonium phosphate can be used as a catalyst to
1,3,4 thiodiazole–xanthate flotation. A combination of sodium sul- participate in the liquid–solid reaction between sodium sulfide
fide and 2,5-dithiol-1,3,4 thiodiazole improves the grade and solution and chrysocolla.
8
Q. Feng, W. Yang, S. Wen et al. International Journal of Mining Science and Technology xxx (xxxx) xxx
9
Q. Feng, W. Yang, S. Wen et al. International Journal of Mining Science and Technology xxx (xxxx) xxx
eral is unsatisfactory. When the ammonium/amine salt dosage is surface is close to the concentration of Zn2+ that is released from
too high, the activation effect of the ammonium/amine salt on sphalerite into the solution, the Cu2+ and Zn2+ radii are similar,
the copper oxide mineral is weakened. With excessive ethylenedi- and Cu2+ can replace Zn2+ on the sphalerite surface. Therefore,
amine phosphate addition, after obtaining a copper ammonium or Cu2+ may first replace Zn2+ on the sphalerite surface, whereafter
copper amine complexing surface, a large amount of ethylenedi- S2 on the sphalerite surface reduces Cu2+ to form copper sulfide
amine phosphate remains in the pulp. The ethylenediamine phos- species [126]. Cu2+ is used as an activator in ilmenite flotation.
phate in the pulp tends to be saturated, which limits the sulfide- The possible activation mechanism of Cu2+ is that Cu2+ interacts
ion interaction with the copper ammonium or copper amine com- with the ilmenite surface through ion exchange, metal hydroxide
plexing surface through the substitution reaction. As a result, precipitation, and oxidation–reduction reaction, and it then forms
insufficient copper sulfide species exist on the mineral surface to Cu(I) and Fe(III) species on the ilmenite surface, which become the
interact with the collector, and copper oxide mineral flotation is active sites for collector adsorption [127]. Pb2+ has been exten-
depressed. sively used as a mineral flotation activator. Sphalerite, ilmenite,
smithsonite, cassiterite, and rare-earth flotation can be activated
by addition of an appropriate concentration of Pb2+ to the pulp
4.3. Effect of metal ions on copper oxide mineral flotation [128–133]. Pb2+ can preferentially adsorb on the mineral surface
as a lead-hydroxyl complex or precipitate to form new active sites
The effect of metal ions on mineral flotation and the mechanism and provide excellent conditions for subsequent collector adsorp-
have become a focus of flotation. Specific metal-ion addition to the tion. Pb-collector complexes are superior in terms of the collecting
pulp can strengthen collector adsorption to activate mineral flota- capacity and selectivity, that is, the lead ions and collector are first
tion [119–122]. During flotation, the metal ions in the pulp can controlled to form high-activity metal-collector complexes in the
physically or chemically adsorb on the mineral surface. Some pulp by coordination and molecule assembly [134]. Iron ions are
metal ions can positively affect mineral flotation by increasing common metal ions in flotation, and they exist in solution as Fe3+
the number of active sites on the mineral surface with which col- and Fe2+. The main source of iron ions in flotation is depletion of
lectors or regulators interact. However, some metal ions can pro- the grinding media and mineral dissolution. Using sodium oleate
duce hydrophilic species on the mineral surface, which is as the collector, Fe3+ interacts with the wolframite and spodumene
unfavorable for flotation and may even cause collector or regulator surfaces as iron hydroxide precipitates and activates wolframite
consumption. The positive or negative influence of metal ions in and spodumene flotation [135,136].
mineral flotation is mainly controlled by the metal-ion concentra- In flotation of copper oxide minerals, the use of specific metal
tion, metal-ion type, mineral surface properties, flotation-reagent ions as flotation activators shows significant potential. Using Pb2+
type, and pulp pH. Metal ions that are introduced into the pulp as an activator of malachite sulfidization flotation, the adsorption
can affect mineral flotation directly or indirectly. Metal ions can ability of sulfide ions and xanthate on the malachite surface is
directly adsorb on the mineral surface or directly interact with enhanced with Pb2+ pretreatment, and the floatability of malachite
reagents on the mineral surface. Alternatively, metal ions can first is improved (Fig. 15) [137]. After interaction of Pb2+ with mala-
hydrolyze in solution and then indirectly interact with the mineral chite, many lead species appear on the mineral surface, which
as a metal-hydroxyl complex or metal hydroxide precipitate [123]. add active sites for subsequent adsorption of sulfide ions, as proven
The research progress of metal-ion-activated flotation is sum- by the discovery of new lead sulfide species after sulfidization. The
marized to provide insight into metal-ion-activated copper oxide effect of Pb2+ on azurite sulfidization flotation and the mechanism
mineral flotation. In practical production, Cu2+ is commonly used of Pb2+ on the azurite surface have been studied. Pb2+ can adsorb
to activate sphalerite to add metal ions artificially to activate min- on the azurite surface and form a Pb―O structure, and the newly
eral flotation [124,125]. There are two main possibilities for the generated Pb―O structure has a strong affinity for sulfide ions.
Cu2+ activation mechanism to activate sphalerite. Cu2+ can directly The Pb2+-modified azurite surface is sufficiently sulfidized, and
interact with dissolved sulfide species on the sphalerite surface to the azurite flotation behavior improves (Fig. 16) [138]. Therefore,
generate copper sulfide species and thus activate sphalerite flota- the purpose of metal-ion-activation is to increase the number of
tion [120]. However, the results of residual-ion-concentration tests active sites on the mineral surface that are conducive to sulfide-
show that the adsorbed concentration of Cu2+ on the sphalerite ion and xanthate adsorption, thereby improving the flotation
behavior of copper oxide minerals.
In summary, addition of active metal ions, such as Pb2+, can
activate copper oxide mineral flotation. The active metal ions can
directly adsorb on the copper oxide mineral surface or indirectly
adsorb on the mineral surface in the form of stable metal-
hydroxyl complexes by dehydration with the copper oxide mineral
surface. This process increases the number of active sites on the
copper oxide mineral surface, enhances subsequent sulfidization,
and increases the flotation recovery of copper oxide minerals.
Fig. 16. Model of the interaction mechanism of lead ions to enhance sulfidization of azurite surfaces [138].
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