j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 9 : 1 2 3 1 e1 2 4 1

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Review Article

Calcite in froth flotation - A review

A. Faramarzpour a, M.R. Samadzadeh Yazdi a,**, B. Mohammadi a,

S. Chehreh Chelgani b,*
a
Department of Mining and Metallurgical Engineering, Yazd University, 89195-741, Yazd, Iran
b
Minerals and Metallurgical Engineering, Dept. of Civil, Environmental and Natural Resources Engineering, Luleå
University of Technology, SE-971 87 Luleå, Sweden

article info abstract

Article history: Calcite is a semi-soluble mineral that can be considered one of the main problematic
Received 10 April 2022 gangue phases for several different types of valuable sulfides and oxides. Since froth
Accepted 17 May 2022 flotation is the main beneficiation technique for upgrading these valuable minerals, calcite
Available online 23 May 2022 flotation separation has been widely investigated. Semi solubility property of calcite makes
its flotation complicated. Through the flotation process, calcium particles release cations
Keywords: into the pulp solution, generate similar surface properties throughout ore minerals,
Calcite consume reagents, and lockdown flotation beneficiation. Over the years, to tackle this
Electrical charge complexity, calcite reverse flotation (calcite depression) has become the main technique
Solubility for its rejection; therefore, there is a gap in its direct flotation investigations. In addition,
Multivalent ions the low selectivity of the existing depressants enhanced the importance of detailed calcite
Selective depression surface chemistry analyses and the development of more selective depressants. These
studies can use various cations and explore their interactions with calcite surface
depression. Ultrasonic and leaching pretreatments have been reported to enhance calcite
depression as well, although several rooms are still empty in this area. As a review article,
this study generally discussed the existing challenges in detail and provided suggestions
for future investigation in calcite flotation.
© 2022 The Author(s). Published by Elsevier B.V. This is an open access article under the CC
BY license (http://creativecommons.org/licenses/by/4.0/).

applications; however, it is mostly used as a filler in the

1. Introduction
Calcite ðCaCO3 Þ is one of the most abundant simple carbonate
salts on the earth's surface (4% of the earth's crust is calcium)
[1]. Aragonite is another primary carbonate mineral with the
same formula (CaCO3 ) but has a different mineral structure
(orthorhombic). Aragonite is not thermodynamically stable
under ambient conditions. Thus, it will be eventually con-
verted into calcite (>107 years) [2,3]. Calcite has different
polymer sector, paint, cement, and plastic industries [1,4e7].
Calcite occurs in nature either as high-grade (with >75%
calcite) or low-grade calcite ores (with <30% calcite). Gener-
ally, other carbonates, phosphate, silicate, and iron sulfide
minerals are associated with calcite. Gravity, magnetic, and
flotation separation are the most process normally applied for
the beneficiation of calcite ores [8]. However, flotation is the
main beneficiation method for upgrading and separating
calcium-bearing minerals, including calcite ðCaCO3 Þ, fluorite

* Corresponding author.
** Corresponding author.
E-mail addresses: samadzadehyazdi@yazd.ac.ir (M.R. Samadzadeh Yazdi), saeed.chelgani@ltu.se (S. Chehreh Chelgani).
https://doi.org/10.1016/j.jmrt.2022.05.106
2238-7854/© 2022 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://
creativecommons.org/licenses/by/4.0/).
1232 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 9 : 1 2 3 1 e1 2 4 1

ðCaF2 Þ and apatite ðCa5 ðPO4 Þ3 ðOH;F;ClÞÞ, which its selectivity is
exceptionally complex [5,9e16].
As a routine phenomenon through the flotation separation
process, the calcite flotation recovery decreased by increasing
particle sizes [17e20]. It was reported that negligible calcite
could be recovered by entrainment in the fraction 75e100 mm;
therefore, true flotation should be the main possible flotation
mechanism for this fraction [21]. However, the flotation effi-
ciency of ultrafine calcite particles (20 mm) is very low and is
mostly influenced by the entrainment mechanism [21]. Fatty
acids and their derivatives are typically used as collector re-
agents for direct calcite flotation separation from other salt-
like minerals (apatite, scheelite, barite, and fluorite). Their
adsorption mechanism mainly occurs through the oleate ion's
chemisorption on the mineral surfaces based on concentra-
tion [22e28]. These semi-soluble salt minerals contain various
valent cations (Mono, di, trivalent), affecting separation
selectivity and efficiency markedly [29]. Water glass is the
most widely used inorganic depressant for calcite [25]. How-
ever, selective flocculation might become a possibility for
separating these minerals from calcite, especially when the
particles are too fine for conducting a successful flotation [30].
Exploring all these complexities would be beneficial to
understanding calcite flotation separation better. Therefore,
this comprehensive study reviewed effective parameters such
as zeta potential, different reagents, contact angle measure-
ments, wettability and floatability, pH, and temperature on
the calcite flotation. Compiling these factors would help get an
unequivocal picture of factors' influences on the calcite
flotation efficiency based on data available in the literature.
Assessments indicated that more in-depth investigations
would be required in cases such as acquiring novel and se-
lective reagents, including collectors/depressants, and the
interaction of the calcite flotation parameters. Using bio-
based or bacteria as a selective calcite inhibitor also needs to
be examined, and pretreatment methods also need to be
considered in more detail.
2. Surface properties
and their adsorption could make its surface negative within
the pH range of 6e12 [38].
2.2. Wettability and contact angle
The calcite surface has undergone various hydrolysis and
complex formation reactions of its constituent species. These
reactions determine its electrokinetic and physicochemical
properties as well as its behavior in solution [45]. The water
molecules at the calcite surface form tightly packed monolayer
structures, and the calcite surface is extensively hydrated by
water molecules [4]. The monolayer water adsorption on the
calcite surface occurs through chemisorption and hydrogen
bonding. The adsorption of water molecules on calcite surfaces
exhibits anisotropy, mainly attributed to the differences in
atomic distribution, surface energy, and surface broken bonds
[16]. In general, the contact angle between the calcite surface
and air bubbles could be varied depending on the type of col-
lectors. However, the differences may have resulted from
different measurement techniques, sample preparation pro-
cedures, roughness, origin, the surface structure of a sample,
and the solution pH [46,47].
Gao et al. (2012) showed that the contact angles of the ½214,
½018 and ½104 surfaces were 27.3 , 35.1 , and 42.1 , respec-
tively [16]. The hydrophilicity followed the order,
½214 > ½018 > ½104, which corresponds to the order of the
density of broken bonds [48]. Therefore, the crystal direction
also might represent different contact angle values [49e51].
Calcite surface hydrophobicity is significantly reduced when
calcium chloride and sodium carbonate were added before the
depressant addition and decreased the contact angle from 75
to 9.0 , which indicates the calcite surface developed a strong
hydrophilic tendency [52].
3. Solubility
Calcite is sparingly soluble in pure H2O at low pressures and
temperatures. The widespread occurrence of calcite-bearing
veins in metamorphic rocks and ore deposits indicates that

2.1. Electrical charge

Table 1 e Iso-electric point of calcite in different
The iso-electric point (iep) for pure calcite is varied from 8.5-to conditions (“-” represents pure calcite).
11.5 (Table 1) [31e33]. This variation depends on experimental
iep Reagent References
conditions such as sample preparation methods, conditioning
time, zeta-potential measuring techniques, and mineralogy 10.08 e [39]
9.8 e [37]
[34]. Filippov et al. (2012) indicated that the vaporeliquid
11.4 e [38]
equilibrium of CO2 must be considered an effective factor for
9.2 e [40]
iep assessment since the calcite surface is highly reactive in 9.2 e [41]
the aqueous solution [35]. In general, the principal potential- 9.0 e [42]
determining species for calcite surface are identified as 11.3 e [43]
Ca2þ , HCO þ  2
3 , H , and OH . CO3 ions, the two latter ions have
9.0 e [44]
8.3 Sodium oleate (NaOL) [37]
a significant role above pH 9 [36]. It was documented that the
8.3 Sodium fluorosilicate (SFS) [37]
zeta potential of calcite gradually decreased with the 10.7 Didecyldimethylammonium [44]
increasing pH. After adding SFS (sodium fluorosilicate) and chloride (DDAC)
NaOl (sodium oleate), the calcite iep (mostly at pH 8.8) was 10 Trioctylmethylammonium [44]
shifted to more negative values significantly due to the spe- chloride (TOAC)
cific adsorption of the reagents [37]. However, the addition of 11.3 Odecyltrimethylammonium [44]
chloride (DTAC)
depressants such as lignosulfonate calcium, HPMA, and PASP
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 9 : 1 2 3 1 e1 2 4 1 1233

crustal fluids can dissolve and transport significant quantities

of calcium carbonate [53]. In other words, there is a significant
positive correlation between calcite solubility and tempera-
ture (Fig. 1) [51,54]. Therefore, temperature could affect calcite
flotation [19,29,55,56].
Having selectivity through the flotation separation de-
pends partly on the type and concentration of the ionic spe-
cies dissolved in the aqueous phase. These species influence
the surface properties of the minerals subjected to separation,
react with the flotation reagents, and thus affect the whole
flotation system [57]. The dissolved species from one mineral
surface can alter other mineral surfaces' properties, dimin-
ishing their differences in floatability [4]. Calcite dissolution
will produce the following chemical species, H2 CO 3 , HCO3 ,
CO 2þ þ þ
3 , Ca , CaHCO3 , CaOH , CaðOHÞ2ðaqÞ and CaCO3ðaqÞ [36]. In

an open system (PCO2 ¼ 103:5 atm), pH of the solution in the

presence of carbonate minerals is affected by the protonation/
deprotonation reactions of ions and CO2 in the atmosphere
(the Ca2þ concentration is higher in the closed system vs.
open system [58]. Thus, the control of these dissolved species,
especially Ca2þ , in the system would be the key to achieving
selective flotation of carbonates [59e62].
Calcite's surface usually dissolves faster than other com-
panion minerals, and its surface will be covered by
CaSO4 :2H2 O layer. At high pH > 11.5, the calcite solubility was
low; however, the Ca2þ and CaHCO3 concentration will be
increased in the solution by decreasing the pH (Fig. 2) [15]. At pH
above 13, the CaOHþ is the dominant species [12]. In a wide pH
range, the calcite solubility is much higher than other associ-
ated minerals like apatite and smithsonite [12,58]. Calcite
reached the dissolution equilibrium at pH 8:31, eventually [12].
Thereby decreasing the pH make flotation separation prob-
lematic [30,36,44,63,64]. Since calcite dissolution is unavoid-
able, using depressants or complexing agents in the presence of
collector and pH modifiers is a mandatory step to reduce the Ca
ions [65]. The changes in depressant adsorption capacity in
different calcium solubility indicate that the reactivity of the
calcite surface is changed by the addition of Ca2þ [ 52 ]. For-
mation of Ca-oleate (layer due to the oleate adsorption on the
calcite surface also decreased its dissolution in alkaline pHs
Fig. 2 e Species distribution diagram for an open system of
calcite [70].
[34,66,67]. However, the solubility of Ca-oleate is much higher
than Cu/Fe-oleate. This phenomenon markedly decreases the
selectivity of flotation separation of sulfides from carbonate
minerals [68]. Metasilicate ions can adsorb at calcite's cationic
surface sites, inhibit the mineral surface's dissolution, and in-
crease their negative surface potential. Furthermore, silica
adsorption prevents these sites from reacting with collector
species [66,69]. This adsorption is chemical interactions be-
tween Si(OH)4 and SiO(OH)- in the solution and cationic surface
sites [69].
4. Pre-treatment
Pre-treatment and feed preparation techniques could affect
calcite floatability. Zeta potential measurement results indi-
cated that by using ceramic media through the grinding, the
collector (NaOL) adsorption would be higher than ground by
steel media grinding [71]. It was also reported that ultrasonic
treatment might positively affect the calcite flotation separa-
tion [72,73]. The beneficial effect of leaching with sulfuric acid
on flotation separation of carbonate gangue from sulfide
minerals selectively decomposed calcite and improved min-
eral liberation. The process could markedly improve the
flotation efficiency [74].

5. Calcite flotation

5.1. Direct flotation

As a gangue phase, calcite is mostly depressed. However, it

would directly float in some cases, such as stepwise flotation
separation of pyrochlore from carbonate minerals [75e79].
Fig. 1 e Calcite solubility in water vs. temperature [54]. Direct calcite flotation typically has been conducted on a pH
1234 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 9 : 1 2 3 1 e1 2 4 1

range of 6e10.5. Anionic collectors have been the most often
used reagents for this process (Table 2). It was documented
that fatty acid could be used for the flotation separation of
calcite from apatite, while apatite primarily has been
depressed [80e82]. The adsorption mechanism of anionic
collectors on calcite depends on their concentrations and
could be physic or chemisorption (Eqns. (1) and (2)) [83e91].
The mechanism of the adsorption of anionic collectors on
calcite is influenced by the dissolved ions of the substrate
[58e61]. These ions are capable of forming insoluble metal
soaps in the solution. Thus, carboxylate species of fatty acids
(as anionic collectors) interact with calcite surface cationic
sites, followed by the association of hydrocarbon chains and
the precipitation of multilayers of metal-hydrocarbon chains
on its surface [34,92]. At low concentration, hydroxamic acid
formed a horizontally oriented monolayer and physically
adsorbed on calcite [93]. Lead nitrate as an activator could
improve the calcite flotation when salicyl hydroxamic acid
(SHA) was used as the collector at pH 7e8 (its recovery
increased from 26 to 82%) [94].
CaCO3ðsÞ þ 2RSO
3 4 CaðRSO3 Þ2ðSÞ þ CO3
2
(1)
CaCO3ðsÞ þ 2RCOO 4 CaðRCOO Þ2ðSÞ þ CO2
3 (2)
selective flotation of scheelite from calcite [108]. A mixture of
cationic and anionic collectors (octadecylamine acetate and
sodium amyl xanthate) also could not effectively improve the
direct flotation separation selectivity of calcite from smith-
sonite. While the mixture could float both minerals [109].
Depending on the type of calcite-associated minerals,
different inhibitors are used to prevent them from floating. For
example, it may be possible to float calcite apart from schee-
lite by depressing the scheelite with calcium chloride [98].
Starch and sodium silicate was reported as the main depres-
sant during the calcite direct flotation [9,110,111]. Starch (pure
amylose and amylopectin) could improve the selective flota-
tion separation of calcite from pyrochlore, sulfides, apatite,
quartz, and hematite [99,110]. The amount of sodium silicate
adsorbed on the mineral's surface in the fluorite-calcite-barite
flotation system decreased in fluorite > calcite > barite and
independent of the ratio of the sodium silicate [9,69,111]. It is
reported that at low concentrations of quebracho)
10 ppme150 ppm (zeta potentials of scheelite become more
negative than calcite, which means that quebracho will
depress scheelite rather than calcite in these concentrations
[112,113]. However, it was indicated that at concentrations
above 0.12 g/L, quebracho completely depresses calcite as well
in the pH range 7e10 [114].

Among various amines (Amine D acetate, Armeen 12D,

Amine acetate 12, Amine D, and Rosin Amine D acetate), the
dodecyl amines (DDA) with acetate radicals showed some
selectivity in the high pH values (10e11) over the calcite sur-
face [10,98]. In some cases, like the separation of scheelite
from calcite, the selectivities of cationic collectors were
potentially higher than anionic collectors [44]. Different
adsorption behavior of DDA on scheelite and calcite surfaces
was mainly attributed to cationic species RNHþ 3 of DDA. The
adsorption of neutral species RNH2 and complex precipitates
played essential roles. RNH2 of DDA adsorbed on both schee-
lite and calcite surfaces through N  Ca bonding and hydrogen
bonding between hydrogens of NH2 group and mineral sur-
face oxygens. DDA by a charge-based physisorption collector
has been considered an excellent candidate to achieve the
5.2. Calcite depression
The floatability of variable minerals could be hindered in the
presence of calcite as a gangue phase [115]. Zhang et al. (2016)
indicated that the monazite (as a phosphate rare earth min-
eral “REM”) floatability would be markedly decreased in the
presence of calcite. Using hydroxamic acid as a selective REM
collector could not improve monazite recovery if calcite did
not initially depress [115e118]. It has resulted that even at
alkaline pHs, Ca species (mainly CaOHþ) in different reactions
(Eqs. (3)e(6)) can adsorb onto REMs, forming a hydrophilic
layer on their surface and changing their surface properties
[115,119e122]. Therefore, reverse flotation is the most typical
method for calcite rejection from the process (Table 3).

Table 2 e Calcite direct flotation conditions.

Mineralogy Depressants Collector pH Recovery (%) Ref
Calcite-Ankerite-dolomite Sodium silicate Aero-6493 7 54 [95]
Calcite Water glass NaOL 10 75 [25]
Calcite Scheelite- Fluorite NaAl NaOL 8 90 [96]
Calcite - Pyrite Thioglycolic acid and citric acid NaOL 10 90 [68]
Calcite -Chalcopyrite Thioglycolic acid and citric acid NaOL 10 90 [68]
Scheelite-Calcite acidified water glass DDA/NaOl 7 22.6 [97]
Scheelite-Calcite CaCl2 DDA 10.9 e [98]
Calcite-pyrochlore Sodium Silicate Fatty acid 8e9 e [99]
Fluorite-Calcite HEDP NaOL 6 e [100]
Calcite e NaOL 11 90 [101]
Calcite e NaOL 12 90 [28]
Calcite e Oleic acid 4.5 33.31 [102]
Calcite e Dodecyl ammine 7.5 58.2 [103]
Calcite e NaOL 10 90 [104]
Calcite e NaOL 8.5 90 [105]
Calcite e Benzohydroxamic acid 7 60 [106]
Calcite e BABP 8e11 90 [107]
Table 3 e Calcite depression through flotation in different conditions.
Flotation system Collectors Dosage Depressants Dosage Additive pH Grade (%) Recovery (%) Ref.
Fluorapatite-calcite NaOl 105 M H3PO4 103 M e 4.5 e z90 [134]
Apatite-calcite NaOL 104 M Sodium polyacrylate 5 mg=l e 7.3 e 8.6 [135]
Apatite-calcite NaOL 20 mg=l Sodium pyrophosphate 120 mg=l e 6.5e9.3 e >90 [136]
Fluorapatite-calcite Oleate and fatty alcohol mixture [Ol] ¼ [PX] ¼ 8  105 M e e e 9 e 67 [137]
Apatite-calcite Coconut oil 700 g=t Cassava starch 400 g=t Flotanol D25 (frother) 10 e 61 (P2O5) [138]
Scheelite-Calcite NaOL 4  105 M Xanthan gum 20 mg=l e 7.9e9.5 e 80 [139]
Scheelite-Calcite NaOL 4  105 M SFS 103 M e 9.5 25.32 (WO3 Þ 80 [37]
Scheelite-Calcite Pb-BHA Pb: 3  104 M NaFa 2 mg=l e 9 36 (WO3 Þ >60 [125]
BHA: 1:5  104 M

j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 9 : 1 2 3 1 e1 2 4 1
Scheelite-Calcite DDA/NaOL 104 M AWG 2  103 M e 7 e >80 [39]
Scheelite-Calcite NaOL 1:2  104 M Carboxymethyl chitosan 30 mg=l e 7 65.21 (WO3 Þ 77.48 [130]
Scheelite-Calcite NaOl 50 mg=l CLSb 20 mg=l e 7 e >90 [7]
Scheelite-Calcite NaOl 2  104 M Sodium phytate 2  105 M e 9.2 56.33 (WO3 Þ 73.23 [140]
Scheelite-Calcite NaOl 1:5  104 M CMC 10 mg=l e 11 70.14 (WO3 Þ 18.92 [28]
Scheelite-Calcite Oleic acid 2  104 M SSc/Fe(II) 500 mg=l Fe (II) 9 62.06 (WO3 Þ 89.82 [132]
Scheelite-Calcite HXMA-8d/NaOl HXMA-8: 2:8  104 M SHMP 50 mg=l e 11 39.47 (WO3 Þ 90.32 [141]
NaOL: 0:7  104 M
Scheelite-Calcite NaOl 3  104 M SS 200 mg=l HXMA-8 8.3 e 84.93 [142]
Scheelite-Calcite Oxidized paraffin soap 600 mg=l AWG 4000 g=t e 9 24.62 (WO3 Þ 83.35 [143]
Scheelite-Calcite NaOl 60 mg=l ASSe 300 mg=l e 7 e 97.5 [26]
Scheelite-Calcite DDA/NaOL 1  104 M SS 300 mg=l e 7 e >80 [97]
DDA: NaOL ¼ 9:1
Scheelite-Calcite Mixed 733/MESf 700 g=t WGg 4500 g=t e 10 65.76 (WO3 Þ 66.04 [144]
Smithsonite-Calcite ODAh 1  104 M FGMi 10 mg=l Na2S 9 41.63 ( ZnÞ 86.63 [145]
Smithsonite-Calcite Potassium lauryl phosphate 2  104 mol 3 LSCj 30 mg=l e 8 e 70 [40]
dm
SmithsoniteeCalcite Oleic acid 500 g=t SS 2000 g=t e 9 e 82 [5]
Smithsonite-Quartz GE609k 10 mg=l SS 200 mg=l e 7e7.5 e 95 [146]
Fluorite-Calcite NaOL 16 mg 3 Polyacrylic acid 7:5 mg 3 e 7 e 70 [41]
dm dm
Fluorite-Calcite Benzhydroxamic acid 50 mg=l e e e 9 e >95 [147]
Fluorite-Calcite NaOL 10 mg=l Polyaspartate 9 mg=l e 7e8 e 90 [148]
Fluorite-Calcite PGl 30 mg=l e e e 9 e z90 [27]
Cassiterite-Calcite SHAm 15 mg=l CMCn 0:05 mg=l Lead nitrate 7e8 e 80 [94]
Barite-Calcite SDSo 2  10 3 g=mg SS 10 3 g=mg NaOl 9 e z95 [149]
Witherite-Calcite NaOL 25 mg=l K2CrO4 15 mg=l e 9 e z80 [150]
Celestite-Calcite NaOL 600 g=t Quebracho 0:0012 g=l e 8 e 83 [114]
Celestite-Calcite SDS 0:1 mM Citric acid 0:02 mM e 9 e 90 [33]
Monazite-Calcite Hydroxamic Acid 2:5  104 M SHMP 1  105 M e 9 e 40 [115]
Monazite-Calcite Octanohydroxamic acid 2:5  104 M Sodium silicate 0:025 g=l e 9 e z90 [151]
bastna€ site-Calcite NaOL 2  104 M xanthan gum 15 mg=l e 8 e 85.09 [121]
bastna€ site-Calcite-Fluorite OHA/NaOL (2:1) Total: 1  104 M Citric acid 3  104 M e 10 e 90 [122]
a
Sodium fluoride.
b
Calcium lignosulphonate.
c
Sodium silicate.
d
Octyl hydroxamic acid.
e
Acidified Sodium Silicate.
f
Sodium fatty acid methyl ester sulfonate.
g
Water glass.
h
Octadecylamine acetate.
i
Fenugreek gum.
j
Lignosulfonate calcium.
k
Alkyl diamine ether.
l
Propyl gallate.

1235
m
Salicylhydroxamic acid.
n
Carboxymethyl cellulose.
o
Sodium dodecyl sulfate.
1236 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 9 : 1 2 3 1 e1 2 4 1
REO þ CaðOHÞþ 4REOCaðOHÞ
REO þ CaðOHÞþ 4REO $$$ HOCa
PO þ CaðOHÞþ 4POCaðOHÞ
PO þ CaðOHÞþ 4PO $$$ HOCa
Calcite depression through the flotation of its associated
valuable minerals (such as barite, scheelite, apatite, monazite,
cassiterite, etc.) could be accomplished by depressants (Table
3). Starch is the most common depressant for calcium mineral
separation, which has a higher affinity towards calcite over
apatite, thereby adsorbing more on the calcite surface and
blocking collector adsorption [84,91]. Reagents such as sodium
silicate and starch could be used as calcite depressants at pH
7e10 [5,26,114,123,124]. Sodium silicate and sodium fluo-
rosilicate mainly show chemisorption on the calcite surface.
Chemical reactions occur between SiOðOHÞ2 2 and SiðOHÞ3
species and Ca species on calcite surface [37,125]. For the
flotation of REMs, sodium silicate, disodium sulfide, and so-
dium oxalate can be used for calcite depression [126,127]. It
was reported that quebracho and tannins (as one of the
quebracho derivatives) have a physical adsorption mecha-
nism involving hydrogen bonds on the calcite surface
[128,129]. Chemical interaction is the main adsorption reason
between Ca2þ on calcite surface and the eCOOH in the car-
boxymethyl chitosan [130]. The citric acid (CA) was reported to
have a limited depressive effect on calcite in the sodium
oleate (NaOL) flotation system. However, the addition of Fe(III)
significantly improved the depressive effect of the CA on
calcite [131]. In general, metal ions (such as Al(III), Fe(II), Pb(II),
and Cu(II)) can be used to improve the calcite depression
selectivity [132]. Du Rietz [133] reported the solubility products
of metal hydroxides and metal oleates (Table 4). Collector
species may form stable complexes with these ions, and the
absorption of these complexes on the mineral surface could
make it hydrophilic. At pH 10 and with 104 M sodium oleate,

since the concentrations of OH and oleate ions (Ol ) were
comparable, the ratio between the product solubilities for
each ion could be used to distinguish which compounds
would form and precipitate; thus, whether or not flotation by
sodium oleate was possible.
6. Bioprocess
Bioprocess uses microorganisms as friendly flocculants,
modifiers, collectors, and depressants. In recent years, the
bacterial affinity for the mineral surface has been studied, and
several works have been done to evaluate the microorgan-
ism's behavior and their interaction with mineral surfaces
[152]. Bacteria can adhere to mineral surfaces and affect
subsequent flotation of the minerals. The amount of cell
adsorption on mineral surfaces depends on their mineralogy
and solution conditions. These differences in cell adsorption
can be used for their separations. Cells and metabolic prod-
ucts of Bacillus polymyxa were successfully used in flocculation
and flotation to remove chalcopyrite from quartz and calcite
[30]. A yeast, Saccharomyces cerevisiae, was effectively used for
(3) the separation of quartz from calcite through microbially
induced flotation and selective flocculation. Yeast cells
(4) exhibited a higher surface affinity towards calcite. Quartz
surfaces were rendered more hydrophobic, and Yeast made
calcite hydrophilic after interaction with grown yeast cells
(5)
and their metabolites [153].
(6)
7. Flocculation and agglomeration
Selective flocculation may become a valuable method for sepa-
rating minerals from the gangue, especially when the particles
are too fine for successful flotation [30]. Polyacrylamide is re-
ported to be a suitable flocculant for calcium-bearing com-
pounds and a poor flocculant for quartz suspensions [154]. Oil
agglomeration also has advantages due to its simplicity and high
recovery. The agglomeration recovery depends on particles'
surface properties and the nature of the agglomerate [42].
Naturally, hydrophilic calcite can be agglomerated with Na
oleate as an anionic collector and kerosene as a bridging liquid.
Calcite can be agglomerated in a narrow pH range (pH 10e11). At
pH 9.9 and below, and at pH 12, calcite agglomeration recovery
was decreased sharply. The maximum agglomeration calcite
recovery was obtained at pH 10. The decrease of the agglomer-
ation recovery at highly alkaline pH values (pH 11 and above)
may be based on both decreasing adsorption of oleate anions
(hydroxyl ion adsorption on the calcite surface) and high elec-
trostatic repulsive forces between kerosene droplets and the
mineral particles [155].
8. Calcite in carrier flotation
As mentioned, the flotation recovery of ultrafine calcite
mainly occurs by the unselective entrainment mechanism
[156e165]. Carrier flotation of these slimes using coarse par-
ticles of other minerals could improve the selectivity
[152e154,166]. Green and Duke used calcite for the carrier
flotation separation of anatase impurity from kaolin clay [167].
The calcite-anatase aggregation mechanism was successful
due to the preferential adsorption and stronger binding of
oleate to calcite-anatase and not kaolinite [168]. Coarse calcite
particles as carriers were also used to separate alunite from
kaolin [169].
9. Summary
Flotation is the most frequent beneficiation method for
separating calcite from other minerals. The low selectivity for
the calcite flotation separation is mainly due to its semi-
solubility in water. Calcite solubility can develop similar sur-
face properties for its associated minerals and lock down the
flotation selectivity. Therefore, several parameters (type of
grinding media, particle size, temperature, pH, reagent types
and their concentration, etc.) must be considered to attain an
efficient calcite flotation separation. For example, increasing
temperature or decreasing pH would promote calcite disso-
lution. Using ceramic media through the grinding would be
increased the calcite collector adsorption compared with the
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 9 : 1 2 3 1 e1 2 4 1
Table 4 e Solubility products of metal hydroxides and
metal oleates at pH 10 [133].
Ca2þ Mg2þ Cu2þ Fe2þ
rKsp ; MðOlÞn 15.4 13.8 19.4 15.4
rKsp ; MðOHÞn 4.9 10.3 18.2 14.8
Ksp ; MðOlÞn 10.5 3.5 1.2 0.6
r [5] Irannajad M, Ejtemaei M, Gharabaghi M. The effect of
Ksp ; MðOHÞn
particles ground by steel media. This fact has to be considered
for selecting the flotation procedure (direct or reverse).
The iso-electric point of pure calcite mainly occurs at pH
8e9 when, at lower pHs, its solubility increases. Therefore, its
flotation (direct or reverse) was frequently examined in the
alkaline pHs. Direct calcite flotation is mostly considered
when carbonatites are the main host of valuable minerals
(such as pyrochlore). Sodium oleate is the typical collector for
direct calcite flotation. However, calcite depression is the
main mechanism for its rejection from the process, and cur-
rent studies mainly focus on using the existing depressant.
However, it was reported that calcite pretreatment by ultra-
sonic, leaching, or calcination could markedly affect its se-
lective depression. More investigations need to be conducted
to address this issue since a limited number of data is pro-
vided about pretreatment. Starch and sodium silicate de-
rivatives are widely used for calcite depression; however,
selectivity would remain a challenge for the process separa-
tion efficiency.
The selectivity performance of depressants through the
reverse calcite flotation would be improved in the presence of
metal ions (such as Al3þ, Fe2þ, Pb2þ, and Cu2þ). Using microor-
ganisms also could promote calcite depression. However,
several rooms are still open to enhance the process selectivity
and make flotation calcite an efficient separation. In order to
tackle these issues, a better understanding of calcite solubility
and depth surface analysis by time-of-flight secondary ion
mass spectrometry (TOF-SIMS) and X-ray photoelectron spec-
troscopy (XPS) would be essential. Outcomes also suggested
that further investigations are demanded to understand the
impacts of flotation condition parameters better. Moreover, the
study and development of collectors/depressants that can
selectively adsorb on the calcite surface at basic pH could be
essential to increasing calcite flotation efficiency.
Declaration of Competing Interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
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As a mineral processor (associate professor),
Dr. Saeed Chelgani is working at the Lulea
university of technology. He has published
over 120 articles in peer-reviewed journals
and two published books. His H-index is over
30. Throughout collaborative projects in
mineral separation and metal extraction
(industry and academia), he has gained a lot
of experience in R&D, industrial teamwork,
and management. He has received the most
prestigious awards in Canada and other
countries (OGS, NSERC, Outstanding researcher & reviewer). He is
an editorial board member of some well-known journals within
his research area.