Advances in Colloid and Interface Science 206 (2014) 68–78

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Advances in Colloid and Interface Science

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A review of zinc oxide mineral beneficiation using flotation method

Majid Ejtemaei a, Mahdi Gharabaghi b,⁎, Mehdi Irannajad a
a
Department of Mining & Metallurgical Engineering, Amirkabir University of Technology, Tehran, Iran
b
School of Mining Engineering, College of Engineering, University of Tehran, Tehran, Iran

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

Available online 13 March 2013 In recent years, extraction of zinc from low-grade mining tailings of oxidized zinc has been a matter of dis-
cussion. This is a material which can be processed by flotation and acid-leaching methods. Owing to the sim-
Keywords: ilarities in the physicochemical and surface chemistry of the constituent minerals, separation of zinc oxide
Chemical processes minerals from their gangues by flotation is an extremely complex process. It appears that selective leaching
Collector is a promising method for the beneficiation of this type of ore. However, with the high consumption of
Colloid
leaching acid, the treatment of low-grade oxidized zinc ores by hydrometallurgical methods is expensive
Depressant
Interface, zinc oxide mineral flotation
and complex. Hence, it is best to pre-concentrate low-grade oxidized zinc by flotation and then to employ hy-
drometallurgical methods. This paper presents a critical review on the zinc oxide mineral flotation technique.
In this paper, the various flotation methods of zinc oxide minerals which have been proposed in the literature
have been detailed with the aim of identifying the important factors involved in the flotation process. The
various aspects of recovery of zinc from these minerals are also dealt with here. The literature indicates that
the collector type, sulfidizing agent, pH regulator, depressants and dispersants types, temperature, solid
pulp concentration, and desliming are important parameters in the process. The range and optimum values
of these parameters, as also the adsorption mechanism, together with the resultant flotation of the zinc
oxide minerals reported in the literature are summarized and highlighted in the paper. This review presents
a comprehensive scientific guide to the effectiveness of flotation strategy.
© 2013 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
2. Solution chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3. Flotation of oxidized zinc using sodium sulfide, and flotation with cationic collectors such as amines . . . . . . . . . . . . . . . . . . . . . . 70
3.1. Sulfidizing agent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.2. Depressants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
3.3. Dispersants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
3.4. Concentration of solid pulp . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
3.5. pH regulator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
3.6. Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
4. Flotation of oxidized zinc using fatty acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
4.1. Effect of depressants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
5. Flotation of oxidized zinc using sulfidization and activation using a metal ion, and flotation with a sulfydryl collector such as xanthate . . . . . . 73
6. Flotation of oxidized zinc using other sulfydryl collectors such as mercaptans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
7. Flotation of oxidized zinc using chelating agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
8. Flotation of oxidized zinc using mixed anionic/cationic collectors such as xanthates with amines . . . . . . . . . . . . . . . . . . . . . . . 75
9. Conclusion and recommendation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76

1. Introduction

⁎ Corresponding author. Tel.: +98 2182084556; fax: +98 2188008838. Zinc enjoys tremendous importance owing to its wide application
E-mail addresses: m.gharabaghi@gmail.com, Gharabaghi@ut.ac.ir (M. Gharabaghi). in industries. It ranks fourth in world metal consumption. Metallic

0001-8686/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cis.2013.02.003
 M. Ejtemaei et al. / Advances in Colloid and Interface Science 206 (2014) 68–78
zinc is used in the production of alloys and in the process of galvani-
zation which bestows protection to steel structures. It is also present
as a chemical additive in rubber and paints [1,2].
At present, zinc is produced from zinc sulfide minerals which are
the primary source of zinc, and it is easy to separate the sulfide min-
erals from the gangue using conventional flotation techniques. As sul-
fide ores become depleted with the passage of time, the beneficiation
of oxidized zinc ores has assumed great importance in recent years.
This situation is what drives the urgent need to process these ores
in order to produce a marketable product [3,4].
Using the leach/solvent extraction/electrowinning process route is
the most common method of extraction of zinc from low-grade zinc
oxide deposits. The application of whole-ore-leaching is likely to be
uneconomical, and the separation of the acid-consuming gangue min-
erals prior to leaching is essential to the successful recovery of zinc
from these deposits. This offers numerous advantages for leaching re-
agent consumption, refinery sizing, and site selection, as it could prove
to be economically viable to transport zinc concentrate containing
high Zn grades. It is technically feasible to separate more than 90%
of the acid-consuming gangue minerals from the ROM zinc oxide
ores, and to produce a concentrate yielding a zinc grade to the order
of 25–35% using the flotation method [5].
There are three basic ore varieties of zinc oxide which are of eco-
nomic value: (a) hemimorphite (gangue minerals: dolomite, goethite,
quartz and kaolinite); (b) smithsonite (gangue minerals: goethite,
quartz, calcite, and kaolinite); and (c) willemite (gangue minerals:
quartz, barite, goethite, and feldspar) [6].
Flotation is the most commonly used method for beneficiation and
pretreatment of oxidized zinc minerals, and there have been extensive
investigations conducted on the flotation of zinc oxide ores [3,4,7–13].
Selecting a suitable flotation method greatly depends on the accom-
panying gangues of the main zinc oxide mineral [3]. Some methods
employed for the flotation of the oxide minerals of the base metals
have been reported. The most important methods which have long
been used are as follows:
(i) Sulfidization using sodium sulfide, and flotation with a cationic
collector such as amines [1,3–5,11,12,14–18].
(ii) Using fatty acids [1,3,15,16,19,20].
(iii) Sulfidization and activation using a metal ion and flotation
with a sulfydryl collector such as xanthate [13,21–25].
(iv) Other sulfydryl collectors such as mercaptans [23,25–27].
(v) Chelating agents [21,28–31].
(vi) Mixed anionic/cationic collectors such as xanthates with amines
[1,10,32,33].
Collector steryl amine acetate works well on smithsonite, but it
does not show selectivity toward calamine ores (major zinc bearing
mineral hemimorphite). When smithsonite is present in the ore, bet-
ter results are achieved using a tallow amine emulsion with elevated
additions of fuel oil emulsion. Xanthates, thiocarbonates, mercaptans,
and dithiocarbamates can collect oxidized zinc minerals [6,34,35].
According to Gaudin (1957), the process is not selective enough for
practice, when hexyl or amyl xanthate is used in the collection of
smithsonite. Two series of chelating reagents have been synthesized
to float smithsonite, but it is difficult to use commercially available che-
lating reagents on plant scale and, more than this, it is the lack of a
long-chain hydrocarbon in the molecule which is the major drawback.
Shi and co-workers [20] used anionic collector for flotation of smith-
sonite. According to their results, smithsonite showed high floatability
using sodium oleate as collector between pH 7.0 and 8.0. By increasing
pH, smithsonite flotation recovery decreased from 80% to about 30%
at pH 9.5 [20]. They concluded that carbonate ions can affect the zeta
potential of smithsonite and its floatability was improved with the pH
regulator Na2CO3. This was due to the increase of surface cation sites
and zinc species in the Stern layer. This phenomena improved the ad-
sorption of oleate ions on the interface at 7.0 b pH b 8.7 [20].
69
A mixture of amines and xanthates can also be used as a mixed
collector for smithsonite flotation [33]. A new line of collectors [36]
has been studied. These collectors are based on xanthated fatty acid
(collectors from the DS series (xanthate = 60%, fatty acid = 20%,
and fuel oil = 20%)) and xanthated mixtures of fatty acid and amine
(DAS series (xanthate = 50%, fatty acid = 20%, amine oxide = 20%,
and fuel oil = 10%)). These collectors were tested on a number of
lead oxide zinc ores from Egypt, South America, and Canada. The best
results were obtained using a collector DAS-2, consisting of xanthated
fatty acid + amine. The reagent was prepared by ultrasonic agitation
of xanthate (50%), fatty acid (25%), and amine (25%).
With more and more attention being given to zinc oxide flotation
in order to increase recoveries of Zn, a review of the zinc oxide flota-
tion literature is presented together with some recent findings. This
article gives the overall review of zinc oxide (especially smithsonite)
beneficiation by different flotation reagents. The objectives of this
investigation are to review zinc oxide flotation and to present a quan-
titative analysis of published data in this area. The feasibility of con-
sidering a surface reaction and reagent effects are also considered.
2. Solution chemistry
Some of zinc oxide minerals such as smithsonite are semi-soluble
minerals which may have their surface charge developed by non-
stoichiometric dissolution that results in the hydrolysis of the ions re-
leased to solution [20]. In the semi-soluble mineral flotation, various
ions are hydrolyzed and hydrolysis products of the ions are capable
of readsorption onto the mineral surface. Mineral surface charge
may be determined by interactions between the ions of the crystal
structure and the hydrolysis products [20].
In the zinc sulfide mineral flotation using sulphydryl collectors,
large number of xanthate species such as xanthate ion (ROCS2),
monothiocarbonate (ROCOS −), xanthic acid (ROCS2H), carbon disul-
fide (CS2), and dixanthogen (ROCS2S2COR) are formed in the flotation
[37]. In sphalerite flotation by KAX collector, Zn(OH)AX(s) is the pre-
dominant species at pH 8–10 and below pH 8 Zn(AX)2(s) is predom-
inant [38].
Smithsonite (ZnCO3) being a typical oxide mineral of zinc, is
a semi-soluble salt mineral with a solubility product constant of
1.46 × 10 −10 M, and it is characterized principally by its ionic bond-
ing and moderate solubility in water [39,40].
In the flotation system, water molecules will chemisorpt on the
surface of smithsonite when the smithsonite surface activity in water
increases. The high activity to water dipoles is one of the main factors
for the low natural floatability of smithsonite compared with zinc sul-
fide minerals. This process will decrease the probability of effective re-
agents adsorption on smithsonite surface [3,41].
Solution chemistry of the zinc oxide minerals has been studied by
several investigators. The smithsonite dissolution and hydrolysis reac-
tions of Zn 2+ with equilibrium constants are described below [42–44].
2þ 2−
ZnCO3 ⇔ Zn þ CO3 ð1Þ
2þ þ
Zn þ OH ⇔ ZnOH ð2Þ
2þ
Zn þ 2OH ⇔ ZnðOHÞ2ðaqÞ ð3Þ
Zn
2þ
þ 3OH ⇔ ZnðOHÞ3 ð4Þ
2þ 2−
Zn þ 4OH ⇔ ZnðOHÞ4 ð5Þ
Smithsonite solubility as a function of pH is shown in Fig. 1. Smith-
sonite is a thermodynamically stable solid at pH values less than 7.4.
Smithsonite will partially hydroxylate to hydrozincite in pH ranges
70 M. Ejtemaei et al. / Advances in Colloid and Interface Science 206 (2014) 68–78
Fig. 1. Solubility products of ZnCO3 and Zn(OH)6 2(CO3)2.
Replotted from Stumm and Morgan [41,42].
between 7.4 and 12.4, and above a pH of 12.4, its amorphous form,
(Zn(OH)2), becomes the predominant species [44,45].
According to the results, smithsonite is negatively charged at
pH values greater than 5. In the pH range pH > 9, when an alkali is
added to an aqueous smithsonite suspension, zinc hydroxide is the
stable solid. The point of zero charge for hemimorphite was found
at pH about 3. The zeta potential became more positive as the pH of
the suspension was reduced [48].
3. Flotation of oxidized zinc using sodium sulfide, and flotation
with cationic collectors such as amines
The most common flotation technique used commercially is
sulfidization with Na2S, followed by treatment with conventional col-
lectors, namely amine, containing from 8 to 18 carbon atoms [18,46].
Amine salts and organic ammonium compounds are very sensitive to
the pH of the medium. Besides, they are most active in slightly acidic
solutions and inactive in strongly alkaline and acidic media [47]. The
main flotation characteristics of these collectors are lower selectivity
and higher reagent consumption.
Extensive research work was carried out on Gorno Calamine
ore from Sicily, where several amines (Flotbel 1, Flotbel CA, Flotbel
CH-A, Aeroamine, Armac T, Armac S, Armac CD, Armac 12D, Armac
HTD, Duomac S, Duomac C, Flotigan O, Flotigan S, Diamine DHPL, Di-
amine acetate, and Kokoamine) were tested, but using amines made
from coconut oil gave satisfactory results. The most effective amines
found during this research were Armac C (Akzo Nobel, USA) and
Kokoamine KK (Akzo Nobel, USA). Billi and Quai [22] also used several
amine salts as collectors of smithsonite. These have been investigated
(Armac C, Armac T, Flotigam SA, Flotigam TA, and Armeen TD), of
which Armac C showed the best results [3]. In the case of flotation of
hemimorphite and willemite, it has been reported that the percentage
of zinc recovery by stearyl amine as a collector was maximized at
pH = 10. Willemite floats better than hemimorphite with amine as
collector, especially in the less alkaline pH range. The difference in
behavior could be explained by the chemical and structural compo-
sition of the minerals. Willemite (Zn2SiO4) is a typical nesosilicate
with the tetrahedral group (SiO44−) linked by zinc cations while in
hemimorphite (2ZnO·SiO2·H2O) the zinc atoms are tetrahedrically
coordinated with three oxygen atoms of the silica tetrahedron and
with one hydroxyl ion. As a result, a lower mobility of Zn 2+ cations
in hemimorphite is observed, compared to that of willemite [48].
More favorable conditions for amine adsorption on hemimorphite
would require the loss of the hydration sheath.
Investigators originally reported that for the zinc oxide flotation
circuit, the best results are at pH levels between 10.5 and 11.5, al-
though some ores respond well to the process at lower pH levels. Re-
agent consumptions are usually in the order of 1000–7500 g/t sodium
sulfide or sodium hydrosulfide, and 300–1000 g/t cationic collector,
depending on the degree of ore liberation and the associated gangues
[3,4,17,49,50].
The pH substantially changes the form of the dodecylamine solu-
tion, RNH3+, predominating in equal quantities at pH values less than
neutrality, with RNH3+ and RNH2(aq) being present in equal quantities
at pH 10.6, and the quantum of rapid drop with an increase in pH
(Fig. 2) [51].
According to Fig. 2, it is obvious that amine exists in suspension
mainly in the form of RNH2(aq) in the pH range of 10.5–12. It is
expected that the amine be adsorbed at the smithsonite surfaces
through complex bonding, possibly chelating. Generally, at the flota-
tion pH of around 10, the RNH 3+ is effectively absent, and it can be as-
sumed that the RNH2 gets attached to the zinc on the surface in the
form of ZnS through complexation bonds [28]. This phenomenon is
shown in Fig. 3.
3.1. Sulfidizing agent
The process of sulfidization is converting the surface of the oxide
mineral such as MCO3 (M: metal element) into a sulfide surface.
This process includes the dissolution of Na2S in which HS − and S 2−
ions form in aqueous suspension, with adsorption of HS − and S 2−
ions taking place at the surfaces of the mineral, chemical, and/or elec-
trochemical reactions in which MS (M: metal element, and S: sulfur
element) forms at the surfaces, and also the possible dissolution of
some surface species. Since the sulfidized surface of oxide minerals
is hydrophobic, conventional froth flotation techniques can be used
to separate them from the gangue [17].
Sodium sulfide addition in a stage prior to flotation (pre-sulfidization)
is more efficient as a pH regulator than during flotation, due to ad-
sorption kinetics differences between the collector and the activator
(the former adsorbs faster than the latter). Salum et al. [48] studied
on the role of sodium sulfide in amine flotation of silicate zinc min-
erals. They found that willemite is more soluble than hemimorphite
and, therefore, more strongly affected by sodium sulfide. By addition
of Na2S, the net charge on the silicate zinc ore surface was more neg-
ative with the zeta potential about − 110 mV, comparing to about −
70 mV at the same pH [52]. The replacement, even partial, of sodium
sulfide by other pH regulating agents, such as sodium carbonate and
sodium hydroxide, decreases the recovery and grade of the zinc concen-
trates. Also, hemimorphite requires a conditioning time in sulfidizing
solution two times longer than that for willemite in order that the
same concentration of Zn2+ cations in solution is reached [48].
Sodium sulfide proved to be the most satisfactory sulfidizing agent
in smithsonite flotation, and it is also cheaper than sodium hydrogen
sulfide, besides having the capacity to generate a high pH [9,53]. The
Fig. 2. Species distribution diagram of dodecylamine as a function of pH (total conc. =
5 × 10−5 mol/l).
Replotted from Somasundaran, 2006 [51].
 M. Ejtemaei et al. / Advances in Colloid and Interface Science 206 (2014) 68–78 71

Table 1
Comparison between different research projects by sulfidizing–amine flotation method.

Feed pH Na2S Collector Conc. R (%) D80 (μ) References

(Zn%) (gr/t) (gr/t) (Zn%)

10.76 11 3500 18-carbon amine 36.28 56.66 74 [17]

7.68 11.5 2000 300 (DDA) 24.5 84.5 140 [49]
8.2 11.5 3000 300 (Armac C) 38.8 84 ~200 [5]
8.2 11.5 4500 1000 (Armac c) 26.4 78 ~100 [5]
16.16 11 3400 356 (amine) 40 70 100–150 [4]
12.64 11 3000 800 (Armac C) 23 87 90 [1]
Fig. 3. Complexation of amines.

high dosage of sodium sulfide results in a pH range of 10.5–12.0 in the
flotation pulp, and flotation results indicate that this pH range is suit-
able for smithsonite flotation [17,28].
From the distribution coefficients of various species in Na2S solu-
tion as a function of pH, it can be found that H2S dominates when
pH b 7.0, whereas HS − dominates when pH > 7.0 and S 2− is at
pH > 13.9 [14,28,42,54]. Furthermore, the optimum pH of flotation
is located in the range where HS − is the predominant species. There-
fore, it can be concluded that HS − species interact with metallic ions
on the mineral surface and forms a sulfidized surface film, thus acti-
vating the flotation of the oxide minerals. The sulfidization reactions
of smithsonite have been experimentally shown as follows [55]:
− −
ZnCO3ðsurf Þ þ HS ⇔ZnSðsurf Þ þ HCO3
− −
ZnðOHÞ2ðsurf Þ þ HS ⇔ZnSðsurf Þ þ H2 O þ OH
After sulfidization, the surface of the mineral becomes less hydro-
philic due to the presence of chemisorbed sulfide ion and thus floats
more efficiently. Under these conditions, the collector requirements
may also be reduced significantly to some magnitude [11].
Adding more amounts of sodium sulfide makes smithsonite zeta
potential more negative, and the value of the isoelectric point de-
creases. The pHIEP of ZnS is around 2 [56]. The pHIEP of smithsonite
drops from 8 to 6.3 because chemical reactions of HS − with metal
ions on the surface of minerals can occur and proceed to form the
metal sulfide film on the surface of smithsonite (Fig. 4) [15].
An excess of sodium sulfide does not depress the floatability of
willemite and hemimorphite with amines [48]. However, the extra
S 2− ion has shown an effect of clear depression on smithsonite flota-
tion [1,3,11,12,15,57,58]. The conditions and reagents' consumption
for some investigations are set out in Table 1.
3.2. Depressants
The choice of gangue depressants is closely related to the gangue
types present in the ore. Usually, the zinc oxide ores have a complex
gangue composition and, therefore, selection of depressants is dic-
tated by the gangue composition present in the ore. Carboxylic acid
is applicable to smithsonite separation from silica or clay minerals
[23], but calcareous material such as calcite or dolomite will float
during smithsonite flotation [59]. Some reagents like sodium silicate
(type N) and starch can be used as calcite depressant at pH =
7.0–10.0 [60,61]. In the cationic flotation of calamine ore (containing
smithsonite, hemimorphite, cerussite, calcite, quartz and iron oxide)
using sodium sulfides and amine in bench flotation, Marabini and
co-workers [28], used the compounds of tripolyphosphate and guar
of methylcarboxylic sodium salt for depressing of SiO2 and methyl-
carboxylate guars for depressing calcite, which exerts the best depress-
ing effect. Moreover, the compounds that showed the best separation
ð6Þ efficiency were tripolyphosphate and guar of methylcarboxylic sodium
salt.
ð7Þ The effects of sodium hexamethaphosphate (SH), sodium silicate
and starch for separation of calcite–smithsonite, as well as sodium sil-
icate and sodium fluoric for separation of quartz–smithsonite in cat-
ionic flotation have been studied [3]. The interaction between SH
and Ca ion in the pulp has been investigated by Hao Ding and Deng
[62]. They found that SH is significantly capable of producing a com-
plex compound with Ca ion, and also its stability and water solubility
are very high. SH could depress calcite in cationic flotation of smith-
sonite. Furthermore, sodium silicate can partly reduce quartz recovery
in cationic flotation [1,3]. Table 2 shows depressants used in cationic
flotation of oxidized zinc minerals.
3.3. Dispersants
Slimes have a marked effect on oxidized zinc flotation and result
in excessive reagent consumption with less selectivity [63,64]. Zinc
oxide ores consist of both primary slimes and secondary slimes
which are created during the crushing and grinding processes. The
major problem in the processing of zinc flotation tailings is the large
volume of fines and slimes with increasing reagent consumption,

Table 2
Depressants used in cationic flotation of oxidized zinc minerals.

Reagents pH Role Selected

references

Tripolyphosphate and guar of 11 SiO2 depressant in [50]

methylcarboxylic sodium salt calamine ores
Sodium silicate (type N) 7–10 SiO2 and CaCO3 depressant [60,61]
in both calamine and
smithsonite ores
Methylcarboxylic guar 11 CaCO3 depressant in [50]
calamine ores
Sodium hexamethaphosphate 11 CaCO3 depressant in [3]
(SH) smithsonite ores
Tripolyphosphate and 11 Fe2O3 depressant in [50]
polycarboxylic calamine ores
Acrylic acid with law 11 CaCO3 depressant in [6]
molecular weight smithsonite ores
Fig. 4. Zeta potential of smithsonite as a function of pH in distilled water, sodium sul-
Tripolyphosphate, celluloses 11 Al depressant in [50]
fide solution, 2.6 × 10−2 M and ZnS (1 × 10−6 M NaCl).
and carboxylate guars calamine ores
Replotted from Somasundaran, 2006 [51].
72 M. Ejtemaei et al. / Advances in Colloid and Interface Science 206 (2014) 68–78
causing the so-called slime-coating phenomenon, that hinders selec-
tivity and, in some cases, renders the process unfeasible. To preclude
this, desliming and using different reagents such as flocculants, coag-
ulants, dispersants, and depressants can be applied [65]. Slimes are
detrimental to flotation and the process usually requires a desliming
step ahead of flotation [1,17,49]. The dispersants used in various in-
vestigations are summarized in Table 3.
3.4. Concentration of solid pulp
The 30–40% solid mass concentration is the best for obtaining good
results in an acceptable flotation performance. On the other hand, a
higher concentration (more than 40%) due to equipment wear and
tear, high consumption of energy, and inferior fluidity of pulp is not
practical [1]. It is usually believed that in the relatively high pulp
concentration, the concentration of reagents is also high, so that the
adsorption of reagents at mineral surfaces is dynamically favorable,
resulting in an increase in the adsorption density of reagents at the
surface. The flotation response is thus enhanced [17]. Keqing and
co-workers [17] have also found that if the concentration of flotation
pulp is below 25%, the flotation response will be extremely poor re-
gardless of the quantity of reagents used.
3.5. pH regulator
Choosing a suitable pH value and modifier is an essential factor in
the controlling of the mineral flotation [66]. An adjustment of pH by
the addition of an acid or an alkali, affects the surfaces of solids, the
extent of ionization or solubility of a surfactant, the concentrations
of inorganic ions, the level of the electrochemical potential, and the
corresponding oxidation–reduction potential [67].
The most widely used agents for regulation of acidic pH are HC1,
H2SO4, HNO3, etc. although the choice is not based solely on economic
criteria since the effect of the Cl−, SO42− and NO3− ions may also greatly
influence on the behavior of certain systems. NaOH, Ca(OH)2, and
Na2CO3 are the agents of choice for alkaline pH, but again, the selection
of one or the other must also take into account the possible influence of
the agent on the system, for example, the effect of CO32− on the precip-
itation of Ca2+ ions present in the medium [68]. Sodium hydroxide
(NaOH) has to be used as the pH regulator, and using sodium carbonate
for adjusting the pH of the pulp in zinc oxide flotation can decrease the
quantum of mineral recovery. This phenomenon can be argued based
on the dominant species diagram for the Na2CO3–ZnCO3 system, that
is at a pH of around 11, using extra Na2CO3, precipitates Zn (OH)2(s),
thus causing a reduction in smithsonite flotation [1].
3.6. Temperature
Many researchers have investigated the effect of temperature on
minerals [1,17,28,69,70]. The sulfidization of smithsonite surface at
40 °C is better than at 20 °C, but if the temperature is increased to
60 °C, the sulfidization efficiency is decreased [28]. Massacci et al.
[70] reported that amine adsorption on smithsonite surface in the
presence of low-concentration sodium sulfide is an endothermic
Table 3
Dispersants used in oxidized zinc minerals flotation.
Dispersant Mineral
Sodium hexamethaphosphate Hemimorphite
Ethylene glycol methacrylate ethylene Smithsonite
dioxybenzonate (EGMEDB)
Sodium hexamethaphosphate Calamine
Sodium silicate + sodium hexametaphosphate Calamine
(50% each)
Sodium hexamethaphosphate Smithsonite
Sodium hexametaphosphate Smithsonite
reaction. However, if the concentration of sodium sulfide is high
and the pH value exceeds 8.5–9.0, there is a marked decrease in the
heat generated [70]. It is appropriate to set the temperature of the
pulp between 25 and 40 °C [1,17]. The fact that the heat generated
decreases indicates that there is a decrease in the amount of adsorbed
amine in high sodium sulfide solution. It may be concluded that it is
not advisable to float smithsonite at very high temperatures, such as
at 60 °C. However, if the temperature of the pulp is too low, say
below 20 °C, the sulfidization and amine adsorption are not sufficient
since the adsorption reactions are endothermic.
4. Flotation of oxidized zinc using fatty acids
The recovery of single mineral flotation is appropriated using oleic
acid at pH around 10.0 [3,15]. The negative zeta potential increases
due to adsorption of oleic anions on the mineral surface when smith-
sonite is treated with oleic acid. As it has been revealed by FTIR anal-
yses, the adsorption of oleic acid on the mineral surface is caused by
an ion exchange mechanism. The maximum adsorption occurs at
pH 10.0, and the resulting flotation recovery was then 93% [15].
Flotation using carboxylic acid is applicable for zinc oxide ore if
the gangue is silica or clay minerals [23]. If there is limestone or dolo-
mite as gangue minerals, these are also floatable during smithsonite
flotation [59]. Laurylamine acetate as a collector can be used after
sulfidizing the mineral with sodium sulfide, but the flotation proper-
ties of minerals depend on the pH levels [14].
The solubility of fatty acids is low and varies according to the
length of the hydrocarbon chain. Important factors like dimerization
equilibrium, micellization, and precipitation are involved and con-
trolled by the pH level in the solution which controls the surface
charge of the adsorption layer itself [23,71,72].
It is known that RCOOH (l) and RCOOH (aq) are the predominant
species, whereas, species such as RCOO−, (RCOO) −2 2 and to a lesser
extent [(RCOO) 2H] − exist in the basic region (Fig. 5).
The maximum adsorption of oleic acid on smithsonite around a pH of
10.0 may be attributed to interaction between RCOO− and zinc on the
smithsonite surface and can be assumed that the adsorption of oleic
acid takes place by an ion exchange mechanism as shown below [15]:
− þ − −
ZnðOHÞ2ðsurf Þ þ RCOO ⇔Zn Rcoo þ OH : ð8Þ
4.1. Effect of depressants
The main problems in anionic flotation of oxidized zinc ores in-
volve the flotation of the main associated gangue minerals (quartz
Reference
[49]
[107]
[65]
[12]
[17]
Fig. 5. Species distribution diagram of oleic acid.
[4]
Replotted from [66].
 M. Ejtemaei et al. / Advances in Colloid and Interface Science 206 (2014) 68–78
and calcite) into concentrate [16]. It is quite critical to use a depressant
which does not have any influence on valuable zinc oxide flotation. It
has been characterized that quartz cannot be floated by oleic at pH 9
due to its negative surface charge. Contrarily, real flotation results
show that there was no separation between smithsonite and quartz,
and both of them have been floated [3]. Ejtemaei et al. [1] used differ-
ent depressants to avert the flotation of quartz in oleic acid flotation.
They found that quartz can be activated by dissolved ions (especially
Pb(II) and Zn(II)) and be floated along with smithsonite. To combat
this problem, they utilized various depressants namely, sodium sili-
cate, sodium sulfide, SH, sodium fluoride, carboxymethyl cellulous
(CMC), and starch. They proved that the CMC was the most successful
quartz depressant among all the others, since it does not have a nega-
tive impact on the recovery of smithsonite [1].
Calcite and dolomite were depressed by citric acid in oleic acid flo-
tation, but this method has not found application in any plant practice
[6]. SH, as a depressant in single mineral separation of smithsonite–
calcite by Hollimond tube in oleic acid flotation showed successful re-
sults. On the other hand, using SH in real oleic acid flotation of zinc
oxide ore the grade of CaO was decreased while the grade of zinc
also fell steeply [3]. To understand the causes of these reverse results
of Hollimond tube and real flotation, we need to thoroughly investi-
gate the influence of dissolved ions on calcite and smithsonite sur-
faces in oleic acid flotation.
5. Flotation of oxidized zinc using sulfidization and activation
using a metal ion, and flotation with a sulfydryl collector such as
xanthate
Xanthates are the most important collectors for sulfide mineral flo-
tation, as well as for oxides (i.e. copper oxide, lead, and zinc minerals).
Sulfidization followed by flotation with xanthate is not used in the
flotation of the zinc silicates, hemimorphite and willemite, due to
the high consumption of sulfidizing agent, the need for activation
with copper sulfate and the low recoveries obtained [48]. Barbery
and Cecil [73] reported that xanthates can be used for the flotation
of oxidized zinc ore. Smithsonite flotation recovery using Hallimond
tube was determined at 81.3% using potassium amyl xanthate (KAX)
at pH around 10.5 [25]. The flotation of zinc oxide minerals is sug-
gested for sulfidization of the smithsonite followed by activation
with CuSO4 and flotation of the activated zinc oxide using xanthate
at pH 10.5 [13]. It is also implied that after pretreatment of the pulp
with sulfidizer followed by reconditioning with CuSO4, zinc oxide flo-
tation can be achieved with a mixture of xanthate/mercaptan collec-
tors [6].
It is evident, unlike with sulfide minerals, that short-chain xan-
thates are not effective in the flotation of their oxide counterparts,
and that the oxides of Zn can be floated by long-chain xanthates
(amyl or higher). The difference is probably related to the greater nat-
ural hydrophilicity of oxides, as compared to sulfides, suggesting the
need for a more hydrophobic collector, and to the mechanism of xan-
thate adsorption [13]. The action of xanthates on sulfide minerals re-
sults in a chemical bond between xanthate and metal. With oxides,
the metal atoms are less likely to form a chemical bond with xanthate
because of the higher ionic character of the bond between metal and
oxygen than that between metal and sulfur [74]. It is suggested that
the action of xanthates on metal oxides is more dependent on an elec-
trostatic mechanism than is the case with sulfides [75]. As the electro-
static bond is weaker than the chemisorption bond, it requires a longer
hydrocarbon chain to form a stable film for hydrophobicity [13].
Xanthate hydrolyzes in solution to form xanthic acid (HX), and
then dissociates.
þ −
HX⇔H þ X
The species distribution of xanthate is given in Fig. 6.
73
Fig. 6. logC–pH diagram for xanthate.
Replotted from [66].
The interaction of amylxanthate with smithsonite surface at pH of
10.5 may be represented by the following reaction [25]:
− 2−
ZnCO3ðsÞ þ 2AXðaqÞ ⇔ZnAX2ðsÞ þ CO3ðaqÞ : ð10Þ
When smithsonite is treated with KAX, the maximum flotation re-
covery occurs at pH 10.5 and amounts to 82%. The effect is markedly
strong so that KAX is predominantly adsorbed on the negatively
charged mineral surface present in an alkaline solution. XPS studies
indicated that, when mineral is activated by copper, an ion exchange
between Zn 2+ and Cu 2+ occurs on the mineral surface resulting in
the formation a surface layer of CuS [76]. The activating effect of sodi-
um sulfide is strongly time dependent. The increase in sulfidization
leads to an increase in hydrophobicity of the mineral surface. The ex-
cess of sodium sulfide acts as depressant for oxidized lead and zinc
minerals because adsorption of divalent sulfide ions on the surface
of lead oxide minerals increases the negative charge which prevents
the adsorption of the collector on to oxidized zinc mineral surfaces
[58].
Separation of zinc oxide from ferric oxide and silica by xanthate
flotation was notably less successful. In fact, more of the second min-
eral floated. Zinc oxide does tend to aggregate at moderately alkaline
pH due to released Zn +2 ions inducing chemical bridging [77], and
this may promote aggregation with and recovery of the second
oxide. In all the systems, the potential for release and transfer of
metal ions which may cause inadvertent activation needs to be con-
sidered. Release and transfer of metal ions and their activation of silica
are well known [1,51,78]. The Cu 2+ activation method produces good
zinc oxide metallurgical results when the ore contains dolomitic/
calcitic gangue minerals. If the ore contains Fe-hydroxides, this method,
however, produces poor results [6]. Generally, flotation of zinc oxide by
xanthates is not selective enough in practice [13,21,23,25].
6. Flotation of oxidized zinc using other sulfydryl collectors such
as mercaptans
Mercaptans find extensive application in many fields. They are flo-
tation agents, condensation agents in peptide synthesis, accelerators
in vulcanization of rubber, inhibitors of radical polymerization and
photo reduction of ketones, and trapping agents for biradicals [79].
Mercaptans can collect oxidized lead, copper, and zinc minerals
[23,26,80]. Hexylmercaptans (HM), with roughly six carbon atoms,
have reasonable solubility in water and can be used as a collector
ð9Þ for oxide-based minerals, e.g. chalcocite, azurite, malachite, calamine,
zincite, smithsonite, and willemite, but the requirement for mercap-
tan to float zinc oxide mineral is very large [23,25,80]. HM, with a
74 M. Ejtemaei et al. / Advances in Colloid and Interface Science 206 (2014) 68–78
formula of CH3 [CH2]5 SH, is a weak acid, and the ionization of a mer-
captan in water is according to the following equation [81]:
− þ
RSH þ H2 O⇔RS þ H3 O :
Gaudin and Harris [82] studied the adsorption of HM on sphalerite,
zincite, and willemite from aqueous solution, zinc minerals, and be-
tween aqueous solution and the gaseous phase. They showed that
the adsorption of mercaptan from the vapor phase prior to flotation
testing was effective in causing flotation. The mechanism for the ad-
sorption of mercaptan on to malachite and chrysocolla could be simi-
lar to the reaction mentioned, and the process could be extended to
the attachment of mercaptan to any base–metal oxide or sulfide min-
eral [83]. It was proposed that the mercaptan S\H bond is destroyed
in the adsorption process. The adsorbed mercaptan reacts with the
surface \OH group forming the zinc mercaptan salt, splitting out a
molecule of water in the process [84]. When using HM, the maximum
flotation recovery amounts to only 79%. This can be explained by the
formation of strong S\Zn bonds on the surface of the smithsonite
mineral particles leading to a weakening of S\H bonds in the HM mol-
ecules [25].
The adsorbed mercaptan reacts with the surface \OH group
forming the zinc mercaptan salt, splitting out a molecule of water in
the process according to the following reaction [84]:
þ −
…Zn…OH þ H þ RS ⇔…Zn…SR þ H2 O:
Table 4 shows the grade and recovery of bench flotation tests for
various amounts of methylmercaptan (MM), ethyl mercaptan (EM)
and HM. The batch flotation tests show the maximum flotation recov-
ery of 75% with the zinc grade of 22.5% using HM at pH 9 [49]. How-
ever, the mercaptan consumption is too high for floating zinc oxide
minerals and it is insufficient for large-scale processes [23,49,80].
7. Flotation of oxidized zinc using chelating agents
Chelating reagents were proposed as flotation collectors by Italian
CNR researchers in 1971 [85]. Chelating reagents are a particular class
of complex reagents consisting of large organic molecules capable
of bonding to the metal ion via two or more functional groups
with the formation of one or more rings. Such ring compounds are
called chelates [37]. Chelating agents are classified as mono- and
multidentates on the basis of the number of donors in their molecule.
The multidentates can form a ring structure with metallic ions and
they are called chelating agents. The active atoms in the chelating
agent are called donor, bonding, or ligand atoms, and examples in-
clude mainly O, N, S and P atoms [51]. The chelates are characterized
by a remarkably high stability and by the selectivity and specificity of
their formation reaction. The reason for their high stability and selec-
tivity depends on electronic and steric factors. In fact, every chelating
reagent is characterized by the presence of at least one group capable
of donating a pair of electrons to the metal to which it bonds. This
leads to the formation of – besides that of a covalent bond – a dative
bond with the formation of a ring. Moreover, often the chelating
groups are also inserted in an aromatic ring. Therefore, these give
rise to the formation of four- to six-membered rings, which are very
stable [29].
Table 4
Grade and recovery of bench flotation tests for various amounts of MM, EM, and HM [49].
Grade & recovery (%) MM (g/t)
1100 1200 1300
Recovery (%) 22 26 29.5
Zn% in conc. 10.2 10.8 11.7
The separation of minerals from one another by flotation depends
mainly on the selective adsorption which surfactants and polymers
exert on them. Reagents with chelating functional groups have re-
ceived increasing attention for this purpose in recent years, being
ð11Þ
known to exhibit excellent metal selectivity in analytical separations.
Chelating agents, because of their metal specificity or selectivity, can
be used as good flotaids and selective flocculants. In addition to the
metal selectivity, chelating agents offer certain advantages over con-
ventional mineral processing reagents even from the synthesis point
of view [66]. Since the collecting action of chelating reagents is direct-
ed towards the cation present on mineral surfaces irrespective of the
mineralogical class, it is expected that these reagents achieve flotation
of zinc, lead, and minerals of either oxides or sulfides in the same way,
i.e., it seemed logical that, using a suitable chelating agent, it might be
well possible to remove the barrier between base-metal sulfide and
oxide minerals which do not respond equally to the same conventional
collectors [29].
A chelating reagent, namely 8-hydroxyquinoline with fuel oil was
used to float mixed oxide–sulfide minerals of Zn and Pb [30]. Fig. 7
shows the reaction of 8-hydroxyquinoline with Zn 2+ of smithsonite,
and flotation recovery of smithsonite in Hallimond tube as a function
of 8-hydroxyquinoline concentration at pH 7.0.
According to Fig. 7, Rinelli and Marabini [30] showed that in
Hallimond tube at a pH of 7.0 and concentration of fuel oil 0.1 g/l,
with increasing 8-hydroxyquinoline concentration, the flotation recov-
ery of smithsonite rose up to 100% in 0.08 g/l of oxine concentration.
ð12Þ The basic theoretical premise of using chelating agents as collector
has been confirmed in microflotation of pure minerals, but some
problems made it difficult to use commercially available chelating re-
agents on the plant scale and, overall, the lack of a long-chain hydro-
carbon in the molecule. Furthermore, there are some limitations to
the functionality of a reagent selected as flotation collector by theo-
retical prediction on the basis of chemical equilibria in solution. In
fact, the theoretical study is based on aqueous solution equilibria,
whereas the action of these reagents as collectors relates to a hetero-
geneous phase system implying the presence of forces of different
types which are not considered in the thermodynamic calculations
[29].
In order to readdress the problems, two series of reagents with a
mixed aliphatic–aromatic structure containing chelating groups for
Pb and Zn have been synthesized to float smithsonite and cerussite
separately [86–89]. Having a mixed aliphatic–aromatic structure for
a chelating reagent is a general structure requisite, which confers
collecting power to chelating reagents. They are thermodynamic
properties of a functional group, and the structural configuration of
the apolar portion [29].
AminoThioPhenole (ATP) has alkyl and alkoxyl chains of various
lengths, positions, and structures. ATPs are collectors for Pb and Zn.
They exert chelating action towards Zn [87]. Chelation occurs through
a weak dative bond of the nitrogen and the saline bond of \SH (Fig. 8).
Single-stage flotation tests were performed using an ATP reagent
[88]. The sample was conditioned for 5 min at pH 8 with sodium
carboxymethyl cellulose for tests with ATP, then a collector was
added, and conditioning was continued for a further 2 min. After ad-
dition of ATP, the pH was adjusted to 11.4. After addition of 25 g/t
Aerofroth for 1 min conditioning, flotation was performed.
The results of cell flotation tests with ATP reagent on an ore grad-
ing of 5.6% Zn (4.5% as smithsonite and 1.1% as sphalerite) and 1.3% Pb
EM (g/t) HM (g/t)
1100 1200 1300 1100 1200 1300
28 31 35 58 65 75
11.8 12 11.9 15.7 18.3 22.5
 M. Ejtemaei et al. / Advances in Colloid and Interface Science 206 (2014) 68–78
Fig. 7. Reaction of 8-hydroxyquinoline with Zn2+ of smithsonite (a), flotation recovery of smithsonite in Hallimond tube as a function of 8-hydroxyquinoline concentration at pH 7 (b).
Replotted from [30].
(as cerussite), demonstrated that 5n-hexyloxy-2-ATP showed the
best results and Zn concentrate grade and recovery reached 24.4
and 82.5%, respectively.
Development and evaluation of the chelating reagent as a flotation
reagent was extensively studied for many years. Some successful at-
tempts have been reported, but industrial application of these re-
agents has not been successful so far.
8. Flotation of oxidized zinc using mixed anionic/cationic
collectors such as xanthates with amines
A process involving the use of mixed anionic and cationic collectors
for sulfide (sphalerite, pentlandite, and pyrrhotite), feldspar–quartz
separation, and zinc oxide, as well as in the flotation of alkali feldspars
and heavy minerals ilmenite, rutile, monazite, and garnet was investi-
gated [1,10,32,33,90–100]. A mixture of armeen C/potassium amyl
xanthate has been used in practice for flotation of zinc oxide ores in
Canada [101].
A system that contains two surfactants of different charge is called
a catanionic system. The attraction between the differentially charged
head groups will lead to a decrease in the area-per-head group [32].
The process and phenomena for adsorption and solubility behavior
of mixtures of anionic and cationic collectors must be taken into con-
sideration at the interface, and also in the solution phase, e.g. forma-
tion of a mixed film at the liquid–gas interface, formation of mixed
micelles, interaction between anions and cations and formation of in-
soluble complexes, and precipitation of molecules by multivalent cat-
ions [35,100,102–104].
The mole ratio of anionic/cationic collectors shows a significant
effect on mineral flotation [1,10,92,93,97–99,105]. The studies of
Hanumantha Rao and Forssberg [92] showing an optimum ratio of
0.25–0.66 using Cn-dioxyethylene sulfate/alkyl diamine, have been
found for microcline flotation. In general, when the mole ratio ex-
ceeds unity, flotation decreases either due to neutralization and the
formation of a nondissociating complex, or due to the adsorption of
Fig. 8. Reaction of ATP with Zn+ of cerussite.
Replotted from [88].
75
excess anions in reverse orientation [105]. Also, preferential feldspar
flotation from quartz in mixed alkyl diamine/sulfonate collectors at
pH 2 is distinguished. The increase in sulfonate concentration beyond
diamine concentration leads to formation of soluble 1:2 diamine–
sulfonate complex or precipitate, and adsorption of these species de-
creases flotation efficiency since the alkyl chains are in chaotic disori-
entation, with a conceivable number of head groups directed towards
the solution phase [99].
In smithsonite flotation, the optimum mixture ratio of the mixed
collector was KAX: DDA, 3:1 at pH 11.5 in the presence of 2000 g/t
sodium sulfide. The presence of KAX increased the DDA adsorption
due to the decrease in the electrostatic head–head repulsion between
the surface and ammonium ions, and increase in the lateral tail–tail
hydrophobic bonds [49].
The flotation results using mixed collector (Armac C + KAX) [1]
showed that at a fixed amount of Armac C, when the KAX concentra-
tion decreased, the recovery was slightly reduced, but it enhanced
the Zn grade. The best result has been reached in 8:1 (Armac C;
KAX) ratio at pH 11 with 64% recovery and 31% zinc grade. The ratio
of Armac C/KAX concentration in the orientation of alkyl chains is per-
ceived to be significant and probably both the collector tails are direct-
ed towards the solution only when the KAX collector concentration
does not exceed Armac C concentration. The increase in KAX concen-
tration up to Armac C concentration leads to the formation of soluble
Armac C–KAX complex or precipitate, and the adsorption of these spe-
cies decreases the Zn grade since the alkyl chains are in a disorderly
orientation with a conceivable number of head groups directed to-
wards the solution phase. Depending on the relative ratio of the col-
lectors when Armac C is added prior to KAX, it may cover the strong
sites, and subsequent addition of KAX may cover the Armac C's polar
head sites. Fig. 9 shows the schematic illustration of mixed collectors'
adsorption.
9. Conclusion and recommendation
As a result of the findings highlighted by this review, the following
general observations can be made.
1. It is possible to produce marketable zinc oxide concentrate using the
flotation technique. Selecting a suitable flotation method strongly
depends on the accompanying gangues of the main zinc oxide.
2. Different methods such as sulfidization using sodium sulfide and
flotation with a cationic collector, sulfidization and activation
using a metal ion and flotation with a xanthate, using fatty acids,
mercaptans, chelating agents, and mixed anionic/cationic collec-
tors such as xanthates with amines, have been used for zinc oxide
mineral flotation. The pH that gives the best results depends on
the flotation conditions and in the amine, oleic acid, xanthate, mer-
captan, chelating, and mixed collectors. It is reported that the best
76 M. Ejtemaei et al. / Advances in Colloid and Interface Science 206 (2014) 68–78
Fig. 9. Schematic illustration of adsorption of cationic anionic mixtures collectors on sulfidized smithsonite surface of physical adsorption of dixanthogen and co-collector complex
formation on Armac C chains [1,106].
results have been gained in the pH ranges of 10.5–11.5, 10.0, 10.5, 9,
11.4, and 10–11, respectively. Regarding solid pulp concentration,
the results showed that solid pulp mass concentration is in the
range of 30–40%, and has produced the best results, and higher or
lower amounts have an adverse effect on the flotation performance.
3. In the flotation of oxidized zinc using sodium sulfide, and flotation
with a cationic collector, using Armac C or dodecylamine, produced
best results. Using an amine emulsion with elevated additions of
fuel oil and pine oil emulsion could be beneficial. It is proper to pre-
pare the pulp temperature between 25 and 40 °C. Sodium hydrox-
References
ide (NaOH) has to be used as pH regulator, but using sodium
carbonate for modifying the pulp pH in cationic flotation can re-
duce Zn recovery. The flotation of zinc oxide minerals by conven-
tional method (i.e. sulfidizing long-chain alkyl amines flotation)
without using depressants is not selective because there are some
similarities in the surface chemistry of the zinc and gangue min-
erals. Furthermore, depressing quartz, due to its highly negative
surface charged at alkali regions, is the main problem in cationic
flotation. Using sodium silicate and sodium hexamethaphosphate
as depressants of quartz and calcite is essential. Slimes can increase
reagent consumption, hindering selectivity and, in some cases, ren-
dering the process unfeasible and it is the major problem in flotation
of zinc oxide minerals. The interactions of the various surfactants
with the mineral surface, as measured by the flotation response,
have shown that sodium hexametaphosphate is the most effective
reagent involving an increase in the degree of dispersion.
4. Oleic acid is the most suitable fatty acid for flotation of oxidized
zinc minerals. In this system, pH is the controlling parameter
which controls the surface charge of adsorption layer and deter-
mines flotation performance. Dissolved ions play a critical role,
and characterization of interaction between dissolved ions and
minerals is indispensable to have a successful selective oleic acid
flotation. Existing calcite minerals in a zinc oxide deposit limit
the utilization of oleic acid flotation for this deposit.
5. It is possible to produce zinc oxide concentrate by using mercap-
tans, or sulfidization and activation using a metal ion, and flotation
with a sulfydryl collector such as xanthate, but they are not selec-
tive enough for practice.
6. Chelating reagents as a flotation reagent have been successfully
used at the laboratory scale, but owing to the lack of a long-chain
hydrocarbon in the molecule industrial application of these re-
agents, it has not been successful so far.
7. More recent studies on the use of zinc oxide flotation using mixed
collectors (Armac C + KAX) indicated that it is quite promising to
produce a suitable concentrate using this method. The sequence of
the collectors' addition is a key parameter.
8. There are still further investigations needed to be made regarding
the effects of depressant type, dissolved ion effects, using mixed
collectors, enhancing the strength of chelating collectors by syner-
gistic effects of other collectors, and understanding the phenomena
of the zinc oxide flotation. With the results of the present study, it
would appear that the mechanisms of zinc oxide flotation are still
to be elucidated. More solution chemistry and adsorption data are
required to elucidate the mechanism of this mineral flotation
with many of these collectors. Interactions occur between these re-
agents and the other chemical parameters existing in the flotation
pulp which complicate the elucidation of the behavior of the re-
spective reagents.
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