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A Review of Graphite Beneficiation Techniques

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A Review of Graphite Beneficiation Techniques

S. Chehreh Chelgani, M. Rudolph, R. Kratzsch, D. Sandmann & J. Gutzmer

To cite this article: S. Chehreh Chelgani, M. Rudolph, R. Kratzsch, D. Sandmann & J. Gutzmer
(2016) A Review of Graphite Beneficiation Techniques, Mineral Processing and Extractive
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 MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW
2016, VOL. 37, NO. 1, 58–68
http://dx.doi.org/10.1080/08827508.2015.1115992

A Review of Graphite Beneficiation Techniques

S. Chehreh Chelgania,b,c, M. Rudolpha, R. Kratzscha,d, D. Sandmann,e and J. Gutzmera
a
Helmholtz-Zentrum Dresden – Rossendorf, Helmholtz Institute Freiberg for Resource Technology, Freiberg, Germany; bDepartment of Electrical
Engineering and Computer Science, University of Michigan, Ann Arbor, Michigan, USA; cDepartment of Geology and Mining Engineering, Faculty of
Engineering, University of Liberia, Monrovia, Liberia; dDepartment of Mechanical Process Engineering and Minerals Processing, TU Bergakademie
Freiberg, Freiberg, Germany; eDepartment of Mineralogy, TU Bergakademie Freiberg, Freiberg, Germany

ABSTRACT KEYWORDS
Graphite as the most common polymorph of naturally occurring crystalline carbon is required for many Graphite; liberation;
different applications such as batteries, refractories, electrical products, and pencils. Graphite resources flotation; leaching; roasting;
are currently being subjected to intensive exploration to help meet rapidly growing global demand – microwave
and graphite has made it onto the list of critical raw materials as issued by the European Union. Graphite
ore is mostly beneficiated using flotation separation techniques. The increasing demand for high-grade
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graphite products with up to 99.99% carbon has resulted in the development of various approaches to
remove impurities even to parts per million range. This paper considers separation and purification
techniques that are currently employed for graphite mineral beneficiation, and identifies areas in need
of further research.

1. Introduction material is transformed into graphite in response to increasing

temperature and/or pressure in the Earth’s crust) (Mitchell
Graphite is the most common form of naturally occurring
1993; Kwiecińska and Petersen 2004). With the gradual
polymorphs of crystalline carbon – another one being dia-
increase of metamorphism, sedimentary carbonaceous mate-
mond. Natural graphite resources are classified based on a
rial transforms first into an amorphous form of carbon
multitude of properties, including not only grade but also
(Landis 1971; Wakamatsu and Numata 1991). For certain
crystallinity as well as grain (flake) size and shape.
industrial applications (see above) this amorphous carbon
According to these attributes, graphite ores are classified to
may substitute for crystalline graphite. Amorphous carbon
crystalline lump (vein), flake, and microcrystalline (Graffin
resources are hosted by moderately metamorphosed marine
1982; Sutphin and Bliss 1990; Zheng et al. 1996; Li, Zhu,
sedimentary rocks, such as quartzites or phyllites, but also
and Wang 2013). In addition, graphite resources occur in
represent former coal beds. The “grain” size of this amor-
several geological environments that are used to distinguish
phous graphite is typically between +40–70 µm in diameter.
different deposit types (Cameron and Weis 1960; Graffin
Natural graphite may occur in metamorphosed siliceous rocks
1982; Mitchell 1993; Kwiecińska and Petersen 2004).
(typically quartzite) as well as metamorphosed carbonate
Graphite is soft, greasy to the touch, and soils fingers and
rocks. Associated minerals with graphite occur as quartz,
paper (due to small van der Waals energy between sheets of
rock-forming silicates such as amphiboles and feldspars, also
carbon; Schabel and Martins 1992). It has many unique phy-
calcite, sulfides, or magnetite (Mitchell 1993; Bulatovic 2014).
sical and chemical properties such as refractoriness, high-heat
Flake graphite is commercially classified into coarse (+150–
and electrical conductivity, greasiness, high-thermal resis-
850 µm in diameter) and fine flakes (+45–150 µm in diameter:
tance, inertness, and readily soluble in iron. Graphite has
which may be furthermore subdivided into +100–150 µm,
both metallic and nonmetallic properties. These unique prop-
+75–100 µm, and –75 µm; Mitchell 1993). Partial volatiliza-
erties give rise to its major uses in welding rods, desulfurizing
tion and subsequent recrystallization during regional meta-
agents, facings, lubrication, refractories, marking instruments,
morphism are assumed to be responsible for the formation of
electrical products, batteries, brake linings, bearings, conduc-
graphite in veins that crosscut meta-sedimentary host rocks
tive coatings, crucibles, electrodes, and paints (Figure 1)
(gneiss, schist, quartzite, and marble). Vein graphite is highly
(Wakamatsu and Numata 1991; Andrews 1992; Mitchell
crystalline. Generally, the quality of graphite from these
1993; Didolkar et al. 1997; Crossley 2000; Kalyoncu and
deposits is dependent on the characteristics of the original
Taylor 2000; Chang 2002; Dumont 2005; Gredelj et al. 2009;
carbonaceous sediments and on the extent of metamorphic
Kaya and Canbazoğlu 2009).
graphitization (Mitchell 1993; Gredelj et al. 2009; Bulatovic
The formation of graphite is a result of contact or regional
2014).
metamorphism of sedimentary organic matter (e.g. organic

CONTACT S. Chehreh Chelgani Schehreh@umich.edu Helmholtz-Zentrum Dresden – Rossendorf, Helmholtz Institute Freiberg for Resource Technology,
Halsbrücker Straße 34, Freiberg 09599, Germany.
© 2016 Taylor & Francis

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Figure 1. Common applications of graphite (Moores 2012; DNI Metals Inc. 2014).
According to the variety of applications, graphite demand
has markedly increased in the last decade. Graphite is one of
the main resources of graphene. Graphene obtained from
high-grade graphite usually has good quality and is highly
conductive (Jagiello et al. 2014). Global consumption of nat-
ural graphite has increased from ~600,000 tons in 2000 to 1.6
M tons in 2015 (Cowie 2012; Graphite One Resources 2015).
Around 45% of all graphite demand generated between 2013
and 2018 will be attributable to China alone, the world’s
leading consumer of these products (Salwan 2015). Graphite
is also fundamental to Europe’s economy, and one of the 21
critical raw materials of the EU (European Commision and
Ad-Hoc Working Group on Defining Critical Raw Materials
2014). China is the top producer of graphite in the world
(Figure 2). Flake graphite makes up 49% of the total graphite
products (mainly extracted in China, Brazil, India, North
Korea, and Canada). Amorphous graphite production is 50%
of the world graphite output (the biggest producers are China
Figure 2. World’s leading graphite producing countries in 2013 (Olson 2015).
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 59
and Mexico). Sri Lanka is the only excellent producer of vein
graphite with less than 1% of the total production of graphite
(Moores 2012; Asbury Carbons 2013; Shaw 2013; Bulatovic
2014; DNI Metals Inc., 2014; Graphite One Resources 2015;
Salwan 2015).
The main properties to determine the graphite product
price are flake size, size distribution, and grade (remaining
level of impurities in the final graphite product) (Mitchell
1993; Gredelj et al. 2009). Graphite products with particle
sizes coarser than 200 μm and with at least 98 wt% or higher
carbon content have the best quality for industry (Bulatovic
2014). As the demand for high-purity natural and synthetic
graphite has increased (forecast to rise by 10–12% per year),
the development of various techniques to produce high-grade
graphite has boosted (Shaw 2013). Graphite is naturally
hydrophobic, and the most used technique for graphite ben-
eficiation is froth flotation (Arbiter 1985; Crossley 2000).
Generally, graphite production from ores is achieved by a
combination of careful crushing, milling, screening, tabling,
flotation, magnetic separation, electrostatic separation, and
leaching (Jean 1927; Andrews 1992; Kaya and Canbazoğlu
2009; SGS Minerals Services 2012).
This paper explores the beneficiation of natural graphite
with regard to the processing methods. It demonstrates how
these techniques are applied to increase graphite value
(grade): comminution (with focus on various types of impu-
rities and liberation, effect of scrubbing attrition), flotation
(various reagents, conventional and column flotation), leach-
ing (chemical leaching, roasting and leaching, and micro-
wave), and other methods (such as gravity separation) for
graphite beneficiation.
2. Comminution
As the size and grade of graphite products are important
parameters in their commercial considerations, it is in the
best interest to maximize the amount of large particles
(flakes), and minimize any processing (crushing–milling)
that will reduce flake sizes (flakes in the size range of 250
µm to 1 mm will demand the highest prices) (Mitchell 1993;
Asbury Carbons 2013; Bulatovic 2014). Liberated graphite is
naturally hydrophobic and floatable, and it is well understood
that to increase the recovery and grade, liberation has the
critical effect (Subramanian and Laskowski 1993; Bulatovic
2014). These facts demonstrate the essential role to study
liberation characteristics and impurities of graphite.
Graphite has a layer structure with pronounced cleavage
parallel to the layers. Properties parallel to the layers are very
different from those normal to the layers. Within the monoa-
tomic layers, carbon atoms share strong covalent bond but the
layers are held together by very weak bonds (van der Waals
bonds) only. These layers are easily disrupted mechanically,
giving graphite its softness (Putnis 1992; Pierson 1993). In the
graphite structure, gangue minerals are deposited between
layers, stacks, or clusters. Such impurities can be associated
with the graphite flake in two ways: mechanically attached to
the surface of flakes, or trapped between adjacent flakes,
which can be called “intercalated” (Kim et al. 2003; Asbury
Carbons 2013). Based on scanning electron microscopy
 60 S. C. CHELGANI ET AL.
(SEM) studies, Kim et al. (2003) distinguished four types (type
I–IV) of solid inclusions in graphite particles. For type I, a
particular impurity is captured between spheroidal graphite
clusters. In type II, a small impurity is lying between clusters,
but it has a micro-textured structure, which is strongly bound
to graphite surfaces. Micro-textured solids showing a strong
adhesion and tangle onto cluster surfaces are classified as type
III. Type IV shows marked flat solids being sandwiched
between the stacks within a graphite cluster. The lowered
melting temperature of impurities during the formation of
graphite is regarded as the main reason of their micro-tex-
tured structure (Kim et al. 2003).
Careful assessment of liberation and distribution of
remaining impurities during beneficiation of graphite ore is
needed to avoid overgrinding and to maximize flake size,
product grade, and recovery. Therefore, graphite beneficiation
requires a combination of careful grinding and screening to
recover coarse graphite particles. Comminution flow sheets
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depend highly on the type of ore to be treated, and liberation
characteristics can be rather complex and variable. During
milling with balls (ball mill), graphite particles are influenced
mainly by the type of impulsive stress, which can be either of
compression or shear type (Chen et al. 1999; Ong and Yang
2000; Janot and Guérard 2002). Through processing by pla-
netary ball mills, where the shear component of the applied
stress is dominant, highly anisotropic particles are obtained,
while amorphous carbon often results from milling with high-
intensity compression (Antisari et al. 2006) (through ball
milling in water, shearing force created by the grinding
media does not effectively transfer to the graphite particle
surface; Kim et al. 2002). The main problem in this procedure
is producing very fine graphite particles. To overcome this
problem, a slow speed tumbling mill equipped with flint
pebbles can be used (Bulatovic 2014). In addition, jet milling
of graphite can reduce the often large particle sizes by high-
intensity impact stress while retaining the flake anisotropic
particle shape (Herstedt et al. 2001).
Moreover, for the last cleaning step when impurities are
attached to the graphite particles and presented in graphite
concentrate, attrition mills have been used in some plants
(Bulatovic 2014). In an attrition mill the graphite particles
are liberated by selectively shearing off the gangue, not stres-
sing the graphite grains, and thus maintaining the crystallinity
of graphite (Kim et al. 2002). It was reported that surface
cleaning with attrition scrubbing could also be an effective
way to improve the selective separation of fine graphite
(Grondin and St-Hilaire 1996; Lu and Forssberg 2001a,
2002; Kaya and Canbazoğlu 2009). The scrubbing process
might also be applied before flotation (Kaya and Canbazoğlu
2007) or after rougher flotation in a wet medium (Grondin
and St-Hilaire 1996; Lu and Forssberg 2001a, 2002; Kim et al.
2003; Aslan et al. 2008).
During attrition, fine graphite is cleaned by rubbing of
individual particles against each other and/or an attrition
medium (Grondin and St-Hilaire 1996; Lu and Forssberg
2001a). To have the suitable effect (improving the flotation
selectivity), the scrubbing time should be maintained at a
moderate level (45 min) (Lu and Forssberg 2001a; Kim et al.
2003). The scrubbing process is mostly considered an effective
way to remove clay minerals, or impurity types I to III (see
above) as these can be removed from the expanded particles
by mechanical impact (Grondin and St-Hilaire 1996; Kim
et al. 2003; Kaya and Canbazoğlu 2007). Scrubbing of the
rougher flotation feed has been found to have a less positive
effect on removing impurities of graphite in comparison to
the scrubbing of rougher concentrate (feed of cleaners) (Lu
and Forssberg 2001a; Kim et al. 2003; Kaya and Canbazoğlu
2007; Aslan et al. 2008). Experiments indicated that attrition
scrubbing can increase the grade of final leaching–roasting
product by 7–9% (Lu and Forssberg 2001a; Kim et al. 2003).
To estimate liberation, various techniques, such as grain
counting or light microscopic examination, X-ray intensity
size (XRD analysis), the mesh of grind, QUEMSCAN techni-
que, and SEM, can be used. Based on established methods for
assessing liberation, light microscopic studies commonly can
reveal the first stage of liberation of graphite mineral grains.
Estimations of the liberation by different methods indicate the
approximate size with various accuracies (under 120–150 µm)
(Klein 1992; Mitchell 1993; Falutsu 1994; Patil et al. 1997;
Kaya and Canbazoğlu 2009; Stinton et al. 2013). Mineral
liberation analysis (MLA) by automated SEM-based image
analysis can be used effectively to characterize graphite raw
materials, and can provide information relevant to understand
the success of graphite beneficiation. In addition, results of
this technique can provide access to valuable data on graphite
and impurities, grain size distribution, and composition of
mineral association, which cannot be obtained by other ana-
lytical tools currently available (Sandmann et al. 2014).
Various investigations indicated that the beneficiation of gra-
phite by different separation techniques (such as flotation) is
strongly related to the liberation information (Jean 1927;
Mitchell 1993; Acharya et al. 1996; Didolkar et al. 1997; Patil
et al. 1997; Kaya and Canbazoğlu 2009; Asbury Carbons 2013;
Spahr et al. 2013; Bulatovic 2014).
3. Flotation
Pure graphite is naturally hydrophobic on the cleavage planes
due to the low surface energy. It is thus not surprising that
graphite was the first ore mineral to be concentrated by
flotation (Bessel Bros., 1877; Mitchell 1993). A German patent
by Bessel brothers was issued in Berlin, and presented a first
true flotation process for the concentration of graphite. In
1877, this patent outlined a process for the flotation of gra-
phite from ores using 1 to 10% of oil and listing more than 16
sources for the oil. The Bessel Brothers produced a concen-
trate containing more than 90% graphite. To reduce costs, in
1886, the Bessel Brothers patented another gas-generating
method for the process by adding acid with carbonates
(Bessel Bros., 1886).
Contact angle (hydrophobicity factor) on the surface of
graphite is relatively large, although it depends on changes
in pH (77° and 88° in the pH range of 2–9) (Arbiter et al.
1975; Solaris et al. 1986; Grabowski and Drzymała 2008; Li
et al. 2014). The iso-electric point for graphite particles was
reported at pH between 2.2 and 4.5. The presence of impu-
rities (gangue minerals and substitution of other elements into
the lattice of graphite) can be the main reason for variation of
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 61

iso-electric point of graphite (Wark and Cox 1935;
Wakamatsu and Numata 1991; Kim et al. 1995; Patil et al.
2000; Miettinen 2007; Tran et al. 2010).
In spite of graphite’s natural floatability, the separation
from gangue minerals (feldspar, quartz, mica, and carbonate)
is normally improved by the addition of surfactants and
depressants (Raghavan et al. 1992; Mangaiah et al. 2005;
Gredelj et al. 2009; Vasumathi et al. 2015). In graphite flota-
tion, frothers play an essential role. Several studies indicate
that methyl isobutyl carbinol (MIBC) is the most efficient
frother in graphite flotation (Fentaw et al. 2000; SGS
Minerals Services, 2012; Veras et al. 2014). In comparison
with the other most widely used types of frothers, such as
pine oil and polyglycolic ethers, MIBC can obtain higher
surface tension lowering and the smallest bubble sizes, and
as a result is the most efficient frother in preventing critical
coalescence concentration (CCC) (Baltar 2010; Veras et al.
2014). However, it was demonstrated that polyoxypropylene
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superior to an oil base system, can be considered as an
economical reagent for graphite flotation (Vasumathi et al.
2013).
Sodium silicate, quebracho, gelatin, tannic acid, and starch
may be used as depressants. Studies have indicated that
sodium silicate is the most effective depressant – especially
for silicates. With increasing its concentration through the
flotation process, the total carbon content (CT) of graphite
did not change significantly (Park and Dodd 1994; Didolkar
et al. 1997; Kaya and Canbazoğlu 2007; Ravichandran et al.
2012). Moreover, sodium cyanide was considered as a pyrite-
depressant (Gandrud et al. 1934). By adjusting the pH, selec-
tivity can increase through flotation and optimum pH was
reported between 7 and 10 (Arbiter 1985; Crozier 1992;
Didolkar et al. 1997; Kaya and Canbazoğlu 2007;
Ravichandran et al. 2012). Sodium carbonate and lime are
common pH regulators in graphite flotation (Salgado 2001;
Ravichandran et al. 2012).

glycol butyl ether could be a more effective frother than MIBC
for graphite particles in laboratory and on plant scale (Pugh
2000).
In graphite flotation, non-ionic hydrocarbons such as ker-
osene, fuel oil, paraffin, and diesel oil are generally used as
collectors. Kerosene was observed in several studies to be the
best collector for graphite flotation (Mitchell 1993; Deo and
Rao 1995; Didolkar et al. 1997; Kaya and Canbazoğlu 2007;
SGS Minerals Services 2012; Bulatovic 2014). Also, a new eco-
friendly single reagent “Sokem 705C” (ether-alcohol), which is
Generally, graphite flotation is carried out by combining a
simple rougher flotation step with several stages of cleaning
(Acharya et al. 1996; Tarnekar and Ravindranath 1997; Abd
El-Rahiem 2004; Charbonneau and Lauzier 2014).
Conventional and column flotation have been used to float
graphite particles (Figure 3). Experimental studies indicate
that column flotation can give superior performance com-
pared with conventional cell flotation. This is not only
because the number of stages of operation can be reduced,
but also by improving grade and recovery (Table 1). By

Figure 3. A simplified flow sheet of graphite processing.

Table 1. Comparison between conventional and column cell in flotation of graphite.

[spanname=“2to4”]Cell [spanname=“5to7”]Column
Sample FC% of Con. Recovery (%) No. of stages FC% of Con. Recovery (%) No. of stages Reference
Chotanagarpur –144 µm (India) 88.3 95.6 5 88.0 86.0 2 Misra 2003
Tumudibandha (India) 88.4 99.1 4 87.5 99.0 1 Misra 2003
Ganjaudar (India) 88.4 98.7 4 88.0 96.0 1 Misra 2003
Rajunagfena (India) 75.1 95.0 4 80.7 80.1 2 Misra 2003
Um Qureia –45 µm (Egypt) 79.6 86.6 4 78.6 98.3 2 Abd El-Rahiem 2004
Um Qureia +45 µm (Egypt) 45.2 89.2 4 46.1 89.3 2 Abd El-Rahiem 2004
Orissa -210µm (India) 79.0 80.1 5 80.1 80.1 2 Acharya et al. 1996
Note: FC% of Con = % Fixed carbon of concentrate.
 62 S. C. CHELGANI ET AL.

þ
adopting flotation column in the cleaning circuit, the capacity FeS2 þ 5HNO3 ! Fe3þ þ 2SO2 4 þ H þ 2H2 O
of the graphite beneficiation plants has been increased, the þ 5NO (3)
processing cost of the product decreased, and the process
CaSO4  2H2 O þ 2HCl ! CaCl2 þ H2 SO4 þ H2 O (4)
control has reportedly been easier (Andrews 1992; Acharya
et al. 1996; Didolkar et al. 1997; Didolkar et al. 2000; Biswal CaCO3 þ 2HCl ! CaCl2 þ CO2 þ H2 O (5)
et al. 2002; Misra 2003; Abd El-Rahiem 2004; Lyons et al. 4HF þ SiO2 ! SiF4 þ 2H2 O (6)
2014). SiF4 þ 2HF ! H2 SiF6 (7)
Fine graphite can be upgraded to about 95% carbon by SiO2 þ 4HF ! 2H2 O þ SiF4 (8)
flotation, but further upgrading by physical methods is chal- Al2 O3 2SiO2 H2 O þ 14HF ! 2AlF3 þ 2SiF4 þ 9H2 O (9)
lenging. After flotation, the main impurities in the concen-
CaF2 þ H2SO4 ! 2HF þ CaSO4 (10)
trate are minute silicate mineral grains and chemical
compounds of S, K, Na, Ca, Mg, Fe, and Al disseminated in Al2 Si2 O5 ðOHÞ4 þ 6Hþ ! 2Alþ3 þ 2H4 SiO4 þ H2 O: (11)
graphite scales. Leaching of graphite as a pretreatment prior to flotation
has been reported before (Subramanian and Laskowski 1993;
Patnaik et al. 1997), as well as combined with rougher flota-
4. Refining
tion (Letowski 1994). Leaching reduces the content of impu-
4.1. Acid leaching rities and increases graphite hydrophobicity. Flotation test
results on leached and un-leached samples indicated that the
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Chemical purification by means of leaching is the most com-

grade and recoveries of leached samples improved measurably
mon technique to produce high-purity graphite after flotation
(Subramanian and Laskowski 1993; Patnaik et al. 1997).
(Goldberger, Carney, and Reed 1992; Sun and Cheng 1995;
Leaching in froth can be carried out separating the non-
Watanabe et al. 1995; Lu and Forssberg 2002; Kim et al. 2003;
floatable fraction of particles from the floatable fraction
Kaya 2006; Asbury Carbons 2013). Based on the impurities
(Letowski 1994).
remaining, different acids, such as HCl, HF, H2SO4, and
Acid leaching mostly is an effective way to remove part of
HNO3, or a mixture of these, can be used (Table 2)
silicate impurities, while the products usually contain too
(Canbazoğlu 1981; Rivera-Utrilla et al. 1996; Bolat, Sağlam,
much sulfidic sulfur (Letowski 1994; Ge et al. 2010).
and Pişkin 1998; Linares-Solano et al. 2000; Sarici-Özdemir,
Examinations indicated that H2SO4 and HCl are not as effec-
Önal, and Akmil-Başar 2006).
tive as HF in leaching clay minerals. However, HF does not
Various investigations have shown that although finely
remove pyrite, provides insoluble fluoride compounds (CaF2),
powdered graphite was attacked by these acids, only a very
and has environmental problems (Bhima Rao and Patnaik
limited amount of carbon was released into the leach solution.
2004; Kaya and Canbazoğlu 2009). Thus, an additional pur-
Bolat et al. (1998) reported that unlike leaching with HCl,
ification stage would be required to diminish sulfidic sulfur
HNO3, and H2SO4, treatment with HF simultaneously dis-
and rest of impurities before the leaching process.
solved impurities and organic parts and caused a high weight
loss. Reaction of impurities in samples with various acids can
take place as follows (Woodruff and Pausch 1921; Ferris 1967;
4.2. Roasting
Letowski 1994; Patnaik, Patil, and Bhima Rao 1997; Takahashi
et al. 2001; Bhima Rao and Patnaik 2004; Kaya and Roasting is an effective method to eliminate both silicates and
Canbazoğlu 2009): sulfides from graphite concentrates (Letowski 1994; Lu and
Forssberg 2001b; Ge et al. 2010). A roasting process comprises
FeS2 þ 2Hþ ! Fe2þ þ H2 S (1) roasting, water washing, and then acid leaching (Lu and
þ
FeS þ HNO3 þ 3H ! Fe 3þ
þ NO þ 2H2 O þ S (2) Forssberg 2002; Ge et al. 2010; Charbonneau and Lauzier
2014). Direct roasting only at high temperatures (over 500

Table 2. Graphite leaching tests through various conditions.

Size Time Temperature (° Feed FC Product FC
Sample (µm) Acids (h) C) % % Impurities Reference
Inebolu (Turkey) 150 HCl+HF 4 85 23.5 40.1 Pyrite, clay, quartz Kaya and Canbazoğlu
2009
Akdagmadeni (Turkey) 150 HCl+HF 4 85 37.9 60.5 Calcite, feldspar, clay, Kaya and Canbazoğlu
quartz 2009
Coraklidere (Turkey) 150 HCl+HF 4 85 42.3 59.5 Gypsum, pyrite, clay, quartz Kaya and Canbazoğlu
2009
Birnin Gwari (Nigeria) 75 H2SO4 1 120 90.0 98.0 Apatite, pyrite, clay Nwoke et al. 1997
Tamil Nadu (India) 100 HCl 20 min 40 11.0 13.2 Calcite, quartz Patnaik et al. 1997
Liaoning (China) 200 H2SO4 50 min 100 94.2 99.5 Quartz, clay Kim et al. 2003
+HNO3
Kangwon (South 200 H2SO4 50 min 100 92.9 98.8 Quartz, clay Kim et al. 2003
Korea) +HNO3
Neimeng (China) 100 HCl+HF 4.5 100 88.9 99.9 Quartz, pyrite, clay Ma et al. 1996
Natural graphite 20 NHxFy 4 90 98.5 99.9 Fe, Al Zaghib et al. 2003
(Brazil) +H2SO4
Bogala (Sri Lanka) 53 HCl 1.15 65 98.5 99.4 Fe, Cu, Mg, Ca Amaraweera et al. 2013

to 900°C) would be effective to remove sulfides (thermal
oxidation to SO2) (Sun and Cheng 1995; Liu et al. 2000),
which is costly and restricted in many countries by environ-
mental legislation (Letowski 1994). However, if the material
was treated with an alkali reagent (caustic or alkali roasting),
it has been reported that the process would be effective even
at roasting temperatures much lower than 500°C (Lu and
Forssberg 2002; Charbonneau and Lauzier 2014; Zunairoh
and Santy 2014). Due to the insolubility of calcium silicate,
calcium compounds are not acceptable alkali additives, and
sodium hydroxide (NaOH) has been preferred in the early
application of the process (Dorenfeld 1957). Under high tem-
perature (mostly below 500°C), impurities react with NaOH,
and a part of them dissolve in water. Silicates, for example,
form water-soluble alkali silicates, which then can be elimi-
nated by a simple water-leach (Sun and Cheng 1995). The
solubility of minerals in NaOH takes place in the following
reaction processes (Lu and Forssberg 2002; Bhima Rao and
Downloaded by [University of Michigan] at 02:51 22 February 2016
Patnaik 2004):
FeS þ 2NaOH þ 2O2 ! FeO þ Na2 SO4 þ H2 O
SiO2 þ 2NaOH ! Na2 SiO3 þ H2 O
Al2 O3 þ 2NaOH ! 2NaAlO2 þ H2 O
Fe2 O3 þ NaOH ! FeðOHÞ3 þ NaOH þ H2 O
P2 O5 þ 6NaOH ! 2Na3 PO4 þ 3H2 O
TiO2 þ 2NaOH ! Na2 TiO3 þ H2 O
V2 O5 þ 6NaOH ! 2Na3 VO4 þ 3H2 O:
Other products such as hydroxides of Fe, Al can be neu-
tralized by HCl /H2SO4 in the consequent acid-leaching pro-
cess to form chlorides and dissolve in water. This dissolution
process removes the surface coating of graphite on impurities
as well (Sun and Cheng 1995; Bhima Rao and Patnaik 2004).
Various reactions with HCl can take place as follows
(Bhima Rao and Patnaik 2004; Niu et al. 2007; Ge et al. 2010):
Na2 SiO3 þ 2HCl ! H2SiO3 # þ2NaCl
NaAlðOHÞ4 þ HCl ! AlðOHÞ3 # þNaCl þ H2 O
CaO þ 2HCl ! CaCl2 þ H2 O
MgO þ 2HCl ! MgCl2 þ H2 O
Fe3þ þ 3HCl ! FeCl3 þ 3Hþ
MnO þ 2HCl ! MnCl2 þ H2 O:
Roasting–leaching of flotation products is widely used as
an industrial technique to refine fine graphite (Table 3). With
this technique, the sulfur content at the final product can be
reduced to below 0.05 wt% (Lu and Forssberg 2002). At
present in China, most high-grade graphite products are
Table 3. Various conditions of NaOH caustic roasting.
Size Roasting temperature (° Roasting time
Sample (µm) C)
Shandong (China) +75– 500
150
Hubei Jinchang N/A 1000
(China)
India N/A 500
Township (Canada) +48 400
Sukolilo (Indonesia) –150 300
Woxna (Sweden) –80 250
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 63
produced by the caustic roasting–leaching method (Sun and
Cheng 1995; Kaya 2006). Although this process has many
advantages (lower amount of acid consumption compared
with leaching only and mostly carried out at moderate tem-
peratures (below 500°C); Bhima Rao and Patnaik 2004), dur-
ing this process large amount of caustic soda is consumed.
Based on literature reports, treatment of 1-ton graphite flota-
tion concentrate needs 450–500-kg NaOH and it entails
numerous steps of digestion, washing, and drying of graphite
(Goldberger et al. 1992; Niu et al. 2007). This huge amount of
alkalis leads to environmental issues (especially in wastewater;
Niu et al. 2007). Therefore, it would be necessary to study
other alternative techniques that have the same effect on
removing impurities.
4.3. Microwave treatment
As mentioned above, the commonly applied caustic roasting–
acid leaching technology is not only costly but may also cause
(12) environmental pollution (Li, Zhu, and Wang 2012).
(13) Therefore, production of high-grade graphite by alternative
(14) technologies that are both energy-efficient and environmental
(15) benign is in great demand. In recent years, there has been a
growing interest of microwave heating in mineral beneficia-
(16) tion. Microwave irradiation has many advantages, as it allows
(17) for rapid and selective heating, fast switch on and off, flexible
(18) modular design, and high-energy efficiency while also being
environmentally benign (Matthes, Farrell, and Mackie 1983;
Vasilakos and Magalhaes 1984; Xia and Pickles 1997; Li et al.
2008; Chandrasekaran, Basak, and Srinivasan 2013). The
organic component of graphite is a relatively weak absorber
of microwave energy (Menéndez et al. 2010, 2011), whereas
some minerals (such as pyrite) and water in their structures
readily heat within an applied electric field. Other minerals
appear transparent to the radiation such as quartz (Chen et al.
(19) 1984; McGill, Walkiewicz, and Smyres 1988; Walkiewicz,
(20) Kazonich, and McGill 1988). By applying various microwave
(21) energies, pyrite may be selectively heated and decomposed as
(22) pyrrhotite or iron sulfate (Weng 1993). Furthermore, in
response to the effects of microwave irradiation, the bonds
(23) of sulfur–carbon in organic sulfur compounds are broken and
(24)
the sulfur is released in gaseous form (Zavitsanos and Bleiler
1978; Chehreh Chelgani and Jorjani 2011).
The differences in dielectric properties of the mineral mat-
ter content during microwave irradiation increase the amount
of defects and cracks in the graphite structure. These cracks
will increase the accessible area in the graphite structure for
Leaching temperature (° Leaching time
(h) Acid C) (h) References
1 HCl N/A N/A Sun and Cheng 1995
20min HCl 50 30 min Ge et al. 2010
3 HCl 20 2 Bhima Rao and Patnaik 2004
1 H2SO4 80 30 min Charbonneau and Lauzier
2014
3 H2SO4 20 N/A Zunairoh and Santy 2014
1 H2SO4 20 N/A Lu and Forssberg 2002
 64 S. C. CHELGANI ET AL.
leach liquors and decrease its strength (Li et al. 2008;
Chandrasekaran et al. 2013; Mesroghli et al. 2015). Leaching
experiments with HCl and HNO3 and microwave radiation
lead to increasing grade of graphite from 95 to 99.43%. SEM
and XRD analysis of the products indicated that the morphol-
ogy (shape) remained unchanged during this process. This is
of particular importance to many applications of graphite
(see, for example, Zaghib et al. 2003; Shui et al. 2006; Li
et al. 2012). These results demonstrate that microwave irra-
diation of graphite can be considered as an effective pretreat-
ment prior to chemical leaching or comminution of graphite.
5. Other separation technologies
5.1. Gravity separation
The potential capability of gravity separation methods to
separate impurities from graphite has been examined in
Downloaded by [University of Michigan] at 02:51 22 February 2016
some studies (Laverty, Nicks, and Walters 1994; Tarnekar
and Ravindranath 1997; Li et al. 2013; Rugless 2014). For
example, a graphite pre-float sample (+50–74 µm) has been
subjected to the gravity concentrator of Bartles–Mozley,
resulting in the recovery of 97% of liberated graphite
(Tarnekar and Ravindranath 1997). Based on these results, a
series of tests with hydraulic classification (Whirlsizer classi-
fiers) on graphite samples (–150 µm) have been conducted,
and demonstrated that the concentrate derived from a two-
stage classification process required 34% less acid during acid
leaching to remove remaining impurities in comparison with
a concentrate without classification (Laverty et al. 1994).
Dense media separation (DMS) is the most efficient indus-
trial gravity-based separator used for worldwide coal cleaning
(Feng et al. 2003). Generally, the graphite with less gangue
minerals but higher carbon content has lower density, which
is easier to float in DMS. DMS results using ZnCl2 solutions
indicated that microcrystalline graphite (+0.5–25 mm) can be
upgraded and provides a flotation product with 92% recovery
(Li et al. 2013). These results demonstrate the importance of
more studies in this area, and lead to the conclusion that a
great deal of research is still required in the pretreatment of
graphite prior to leaching.
5.2. Film flotation
In industry, there is some demand for fine graphite flakes (–
25 µm). However, processing ultra-fine graphite is compli-
cated (optimum particle size for froth flotation lies between
+25 and 75 µm). They will coat other minerals, which may be
recovered with the graphite concentrate reducing the grade of
the product (Mitchell 1993). Recent investigations show that it
is possible from a mixture of minerals to separate very fine
graphite (–10 µm) selectively by film flotation (Mitchell 1993;
Tran et al. 2010). In this method, the graphite particles appear
to cluster at the air–water interface. As droplets of the particle
suspension (graphite–methanol–water) are continually intro-
duced, the water surface becomes saturated with fine graphite
particles forming a film where some areas appear multi-
layered. As the film breaks on the water surface, cracks are
formed. Results show the size of the aggregates to be
approximately twice the size of the dispersed graphite parti-
cles. About 60% of very fine graphite particles can be recov-
ered at the water surface. The study demonstrates that it is
possible to achieve good selective ultra-fine graphite separa-
tion in mixtures using the film flotation approach for both
batch and continuous process systems and even at a larger
scale (Tran et al. 2010).
5.3. Two-liquid separation
Yet another technology, two-liquid separation methods (two-
liquid flotation or particle extraction) has been considered for
fine graphite purification (–10 µm). This technology is devel-
oped to extract fine particles based on utilizing difference in
surface wettability of minerals in water and oil (Glogner 1903;
Hayashi 1979; Bulatovic 2014). The thermodynamic basis of
the two-liquid separation of fine particles is the same as that
encountered in the flushing of pigments (this method in some
investigations is called the “flushing method”; Lai and
Fuerstenau 1968; Shergold 1982; Hayashi et al. 2000a). Based
on the principle of flushing process, it is expected that fine
graphite is purified, leaving impurities in the aqueous phase,
and graphite particles are transferred from the water suspen-
sion into the oil phase or at the oil–water interface (Hayashi
et al. 2000a, 2000b). After separation, the graphite within the
oil phase is collected and allowed to agglomerate by adding
acetone. Reduction of particle size (increasing liberation) will
improve the efficiency of this technique. Experimental appli-
cation of this technique on very fine graphite particles (–2
µm) showed that impurity concentration is reduced from 8 to
2 wt% (Hayashi et al. 2000a). This effect can improve using a
commercial oscillating two-liquid continuous separator. Ash
content of samples can be reduced from 16 to less than 1.8 wt
% (around 90% impurities removed). With this method, after
the first step, graphite particles in the oil phase are returned to
an aqueous dispersion with the addition of a non-ionic sur-
factant and sodium carbonate (Hayashi et al. 2000b). The
excellent separation performance of two-liquid separation of
fine graphite indicates this opportunity to upscale this proce-
dure to process ultrafine graphite particles.
6. Summary
Demand of graphite (as a source of graphene) is constantly
increasing. This fact has recently motivated the exploration of
new graphite deposits. As these graphite deposits are typically
of lower grade than those currently in production, there is a
strong need for adopting new methods to retain graphite
product quality while containing beneficiation process costs.
Size of graphite particles as an important commercial para-
meter is indicating the essential role of comminution.
Graphite is an exceptionally soft mineral; therefore, determi-
nation of optimum stress intensity ranges for the most effi-
cient grinding process is important, and the techniques which
are able to accurately provide information about the structure
of impurities in the flakes, estimated size of liberation, and
also size distribution would have an essential effect on the
whole process design. In this regard, well-established auto-
mated mineralogy, e.g. MLA analysis, can provide valuable

information and effectively guide the optimization of process
chains for graphite. Froth flotation of graphite as a physical
separation technique is rather well understood. Kerosene as a
collector, MIBC as a frother, and sodium silicate as a depres-
sant are common reagents used for graphite flotation. In
plants, both conventional and column flotation machines are
being used. The flotation column in the cleaning circuit can
improve metallurgical performance and reduce processing
costs. Although quite a number of studies have been carried
out regarding graphite flotation, significant opportunities still
remain, especially for the flotation of fine graphite and the
effects of attrition scrubbing. Froth flotation is reliant on
liberation; however, often impurities are concentrated due to
attaching graphite layers leading to reduced grades. Therefore,
to upgrade flotation products, chemical (leaching combined
with caustic roasting) methods would be required. The caustic
roasting (with NaOH)–acid leaching (with HCl/H2SO4)
method can produce graphite with 99.99% carbon content,
Downloaded by [University of Michigan] at 02:51 22 February 2016
and remove impurities even at parts per million (ppm) range.
Although this technique allows producing high-grade pro-
ducts, it is costly and generates a large quantity of acidic
and alkaline wastewater. The development of alternative ben-
eficiation techniques that are both cost efficient and environ-
mentally benign will be required. One such alternative could
be microwave irradiation.
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